Основной целью серии «Химия» является пропаганда научных исследований, выполненных на высоком уровне, по разным отраслям химической науки.
Structural features of tris(2-metoxy-5-bromophenyl)antimony bis[2,5-difluorobenzoate] solvate with benzene and octane [(2-MeO)(Br-5)C6H4]3Sb[OC(O)C6H3F2-2,5]2 ∙ ½PhH ∙ ½C8H18 and tri(para-tolyl)antimony bis[2-furancarboxylate] (4-MeC6H4)3Sb[OC(O)C4H3O]2.
The structure of tris[(2-methoxy)(5-bromophenyl)antimony] bis[2,5-difluorobenzoate] solvate [(2-MeO)(Br-5)C6H4]3Sb[OC(O)C6H3F2-2,5)]2 ∙ ½PhH ∙ ½C8H18 (1) and tri(para-tolyl)antimony bis(2-furancarboxylate) (4-MeC6H4)3Sb[OC(O)C4H4O]2 (2), obtained by oxidative addition reaction from triarylantimony and 2,5-difluorobenzoic/2-furancarboxylic acid in the presence of tertiary butyl hydroperoxide in ether, was established by X-ray diffraction analysis (XRD). According to the X-ray diffraction data, crystals 1 [C42H36Br3F4O7Sb, M 1090.19; triclinic system, symmetry group P-1; cell parameters: a = 12.899(11), b = 13.655(11), c = 14.558(14) Å; a = 100.48(5)°, β = 96.66(3)°, g = 116.57(3)°; V = 2197(3) Å3; Z = 2; rcal = 1.648 g/cm3; 2q: 6.092-49.572°; total reflections 38047; independent reflections 7448; number of specified parameters 546; Rint = 0.0464; GOOF 1.052; R1 = 0.0460, wR2 = 0.1218; residual electron density (max/min): 1.14/-1.07 e/Å3]; 2 [C31H27O6Sb, M 617.28; triclinic system, symmetry group P-1; cell parameters: a = 10.287(4), b = 11.776(6), c = 12.872(5) Å; a = 83.83(2)°, β = 83.694(16)°, g = 64.150(15)°; V = 1391,7(10) Å3, Z = 2; rcalc = 1.473 g/cm3; 2q: 5.62-77.32 degrees; total reflections 103088; independent reflections 15758; number of specified parameters 346; Rint = 0.0388; GOOF 1.020; R1 = 0.0409, wR2 = 0.0935; residual electron density (max/min): 1.12/-0.71 e/Å3] consist of trigonal bipyramidal molecules with electronegative ligands in axial positions. The Sb–C bond lengths vary in the range of 2.106(5)−2.112(5) Å for 1 and lower than in 2: 2.1108(18)−2.119(2) Å; the OSbO bond angles take values of 179.06(14)° and 177.07(4)°, respectively. The Sb–O distances in 1 (2.095(4) and 2.105(4) Å) are shorter than in 2 (2.1394(14) and 2.1566(14) Å). The Sb∙∙∙O intramolecular contacts between the central metal atom and carbonyl oxygen atom in 1 (3.113(6) and 3.130(6) Å) are significantly greater than in 2 (2.771(5) and 2.818(5) Å) and do not exceed the sum of ther van der Waals radii (3.7 Å). In addition, crystal 1 contains short contacts between the antimony atom and oxygen atom of the methoxy groups (3.067(6), 3.166(6), and 3.221(6) Å). Complete tables of atomic coordinates, bond lengths and bond angles for structures have been deposited in the Cambridge Structural Data Bank (No. 2060559 (1), No. 1979824 (2), deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Clarification of the Vinpocetine structure by X-ray analysis
The structure of a semi-synthetic alkaloid Vinpocetine was clarified with the use of the X-ray diffraction method with a lower value of the divergence factor (R-factor) compared to that previously described in the literature. The Vinpocetine crystal was obtained by slow evaporation of its solution in methanol. According to the X-ray diffraction data, the fragment of the linear tetrahydrocarboline system of the Vinpocetine molecule is characterized by nitrogen atom N(2) of the hydrogenated pyridine ring exiting from the common plane of the remaining atoms by 0.653 Å. In its turn, the angular tetrahydropyrido[1,2-a]indole system is distinguished by carbon atoms C(13) and C(14) exiting from the plane by 0.806 and 0.327 Å, respectively. Yet another six-membered cycle is located at the 83.9 ° angle in relation to the tetracyclic system of indolo[3,2,1-de][1,5]naphthyridine and has a chair conformation. In the present study the torsion angle of the C(12)-C(13)-C(14)-C(15) bonds (–85.5°) and the orientation of the ethyl substituent, characterized by the corresponding C(14)-C(13)-C(18)-C(19) torsion angle (67.65°) are redefined. The main structural motif of organization of molecules in the crystal is formation of double ribbons along the b axis by means of weak hydrogen bonds of the C-H…O type (the D-H…A distance is 2.66 Å, DHA 121°, the D…A distance is 2.27 Å).
The effect of temperature modes of curing on the parameters of the molecular mesh of epoxy and polyester copolymers
Establishment of formation regularities and structure of mesh polymers, as well as methods of their regulated synthesis allow rational management of technological processes in production and processing of materials based on them. The possibility of directional variation of crosslinking parameters of epoxy and polyester resins using polyamide hardener has been determined. For this purpose the influence of temperature modes of curing, mixing technology and the ratio of initial components has been studied. Initially the values of Huggins constants have been calculated, for this purpose the use of chloroform, xylene, and dimethylformamide has been investigated. On the basis of the obtained results, the selection of a solvent, providing optimal swelling criteria for the synthesized copolymer, has been carried out. Experimental data describing the swelling process of the copolymer samples have been obtained. With the use of Flory equation, the parameters of structural meshes of the developed polymer compositions have been calculated
Synthesis and heterocyclization of 3-cinnamyl-sulfanyl-4-methyl-1,2,4-triazole
In the present paper the interaction between 4-methyl-1,2,4-triazole-3-thiol (1) and trans-cinnamyl chloride (2) under various conditions (i-PrOH–КOH, i-PrOH–Na, MeOH–Na, Me2CO–K2CO3) has been studied for the first time. As a result, individual 4-methyl-3-cinnamylsulfanyl-1,2,4-triazole (3) has been synthesized. It has been found that selectivity of the alkylation reac-tions of compound 1 does not depend on the reaction conditions (solvent, base), however, target product 3 has been obtained in the highest yield (89 %) in the MeOH–Na system. The structure of synthesized compound 3 has been studied and proved by mass spectrometry (GC–MS), as well as ¹H, ¹³C NMR spectroscopy. General predictable directions for fragmentation of the molecular ion of S-derivative 3, which are accompanied by elimination of methyl, benzyl, and triazolylsulfide radicals, have been revealed. The evidence that alkylation reaction occurs at the sulfur atom is the presence of signals for the –SCH2– protons at δ 4.06 ppm in the 1Н NMR spectra of compound 3. Heterocyclization of 4-methyl-3-cinnamylsulfanyl-1,2,4-triazole 3 has been studied for the first time under the action of iodine and bromine in various solvents (iodination in chloroform, ace-tone, dichloromethane, ethanol; bromination in chloroform, dichloromethane), and at different ra-tios substrate : iodine (1 : 2) and substrate : bromine (1 : 1.5). It has been found that the interaction of compound 3 with iodine proceeds regioselective-ly, regardless of the reaction conditions, and it is accompanied by the linear annelation of the thia-zinium ring and formation of a bicyclic fused heterocyclic system. As a result, new iodine-containing [1,2,4]triazolo[5,1-b][1,3]thiazinium systems have been synthesized: 6-iodo-3-methyl-7-phenyl-6,7-dihydro-5H-[1,2,4]triazolo[5,1-b][1,3]thiazinium polyiodide and iodide (4, 5). In contrast to iodination reactions, the interaction of cinnamyl sulfide 3 with bromine proceeds non-regioselectively under the indicated conditions: in addition to the bromocyclization product, 6-bromo-3-methyl-7-phenyl-6,7-dihydro-5Н-[1,2,4]triazolo[5,1-b][1,3]thiazinium bromide (6), the bromine addition product, 3-[(2,3-dibromo-3-phenylpropyl)sulfanyl]-4-methyl-1,2,4-triazole (7), has been obtained. The evidence for heterocyclization reactions of compound 3 is the absence of signals for the cinnamyl protons and the presence of a more complicated splitting pattern of sig-nals for the thiazinium ring protons in the 1H NMR spectra of heterocyclization products 4, 5, and 6.
Synthesis, chemical properties and possibility of practical application of s-derivatives of condensed 1,2,4-triazine-3-thiones
The review presents systematized information concerning various methods of synthesis, chemical properties and possibilities of practical application of condensed 1,2,4-triazine-3-thiones and their S-derivatives, based on the analysis of literature published mainly from 1970 to 2024
Formation of onium compounds of antimony in oxidative addition reactions
The interaction of tris(3-trifluoromethylphenyl)antimony with 2,4-dimethylbenzene¬sulfonic acid in the presence of tert-butyl hydroperoxide (molar ratio 1:2:1) in ether yielded 12% tetrakis(3-trifluoromethylphenyl)antimony 2,4-dimethylbenzenesulfonate (1), which was identified by IR spectroscopy and X-ray structural analysis. The X-ray diffraction analysis was performed on a Bruker D8 QUEST diffractometer. The crystallographic characteristics of the unit cell of the compound are as follows: monoclinic space group P21/c, a = 12.160(8), b = 14.561(11), c = 21.755(14) Å, β = 97.333(18), V = 3821(5) Å3, Z = 4, ρcalc = 1.543 g/cm3,  = 0.869 mm1, F(000) = 1760, crystal size 0.560.150.1 mm, data collection range for 2θ, deg: 6.0649.28, index range –14 ≤ h ≤ 12, –17 ≤ k ≤ 17, –25 ≤ l ≤ 25, the number of measured reflections is 23742, the number of independent reflections is 6398, Rint = 0.0828, GOOF = 1.017, the number of parameters is 480, R1 = 0.0568, wR2 = 0.1414. According to the X-ray diffraction data, the antimony atoms in the compound have a distorted trigonal bipyramidal coordination with the oxygen atom of the sulfonate group in axial position. The CSbO axial angle is 174.08(18)º. The sum of the CSbC equatorial angles is 352.8(2)º, the Sb–Ceq distances [2.121(6), 2.121(6), 2.122(6) Å] are significantly shorter than the Sb–Cax [2.129(7) Å] and Sb–O [2.463(4) Å] bond lengths. Complete tables of atomic coordinates, bond lengths, and bond angles have been deposited with the Cambridge Crystallographic Data Center (No. 2417629; deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).
Bimetallic complexes with the Ag–Sb bonds: synthesis and structure features
Tri(para-tolyl)antimony reacts with silver nitrate in a methanol/acetonitrile mixture at room temperature in both 3:1 and 4:1 molar ratios to form the ionic complex [(p-Tol3Sb)4Ag][NO3] (1). The reaction product of triphenylantimony with silver nitrate under the same conditions is nitratotris(triphenylstibine)silver (Ph3Sb)3AgNO3 (2), regardless of their molar ratio. An attempt to replace the nitrate ligand in the (Ph3Sb)3AgNO3 complex with a carboxylate ligand under the action of 2-methoxybenzoic acid (molar ratio 1:1) and the addition of triethylamine resulted in the crystallization of the adduct of the composition (Ph3Sb)3AgOC(O)C6H4OMe-2·(Ph3Sb)3AgNO3·2СН3ОН (3) from the reaction mixture with a yield of 84 %. Complexes 1–3 were characterized by IR spectroscopy and X-ray diffraction analysis (XRD). According to XRD data, the Ag and Sb atoms in 1–3 have a tetrahedral coordination distorted to varying degrees with the angles between the bonds deviating from the theoretical value of 109.5°. The average Ag–Sb distances in 1–3 are 2.747, 2.732, 2.726 Å, respectively. The SbC bonds vary in the ranges of 2.128(3)2.145(3) Å (1), 2.127(5)2.147(5) Å (2), 2.124(6)2.156(6) Å (3). In ionic compound 1, the nitrate anion is planar and includes the C2 symmetry axis coinciding with one of the NO bonds; the O–N bonds are 1.148(6) and 2×1.164(4) Å, the bond angles are 110.4(7)° and 2×124.8(4)°. In 2 the Ag–O distance is 2.306(13) Å. In crystal 3 there are two identical fragments of (Ph3Sb)3Ag, in which the OC(O)C6H4OMe-2 and NO3 groups have an occupancy of 50%. The Ag–O distances with the nitrate and carboxylate groups are 2.263(14) and 2.352(18) Å, respectively. Each fragment contains one molecule of solvate methanol.
Structure of organic and organoelemental compounds. Part 6.
Tetraphenylantimony carboxylates Ph4SbOC(O)R (R=CHF2 (1), CF2CF2CF3 (2), C6H4Cl-2 (3), C6H4Br-3 (4), C6H3F2-2,5 (5), C6H3F2-2,3 (6), C6F4H (7), C6F5 (8) have been synthesized by the interaction of equimolar amounts of pentaphenylantimony with carboxylic acids in benzene; their structures have been characterized. In these carboxylates, the antimony atoms have a distorted trigonal-bipyramidal coordination with the oxygen atom of carboxyl groups in the axial position. The presence of a coordination bond between the central atom and carbonyl oxygen atom suggests an increase in the coordination number of the antimony atom to 6. Analysis of the structural data of tetraphenylantimony carboxylates shows that the distortion of the trigonal-bipyramidal configuration of molecules 1–8 manifests itself to varying degrees. The C=O bond lengths (1.197(3)1.284(7) Å) are shorter than the CO bond lengths (1.196(18)1.231(8) Å), while the lengths of double bonds in carboxylic acids are (1.2261.229 Å). The SbC distances in molecules 18 are in the range of 2.095(6)2.167 Å, and the SbCax distance (2.154(3) Å (2)  2.174(4) Å (5)) is higher than the Sb–Ceq equatorial bonds. In addition, there are intramolecular contacts between the antimony atom and the carbonyl oxygen (3.100(5) Å (5)  3.517(6) Å (2)), which is less than the sum of the van der Waals radii of these atoms (3.700 Å). The maximum equatorial angle on the side of the Sb∙∙∙O=C contact (120.7(2)130.67(14)) is less than the other two equatorial angles. Complete tables of atomic coordinates, bond lengths and valence angles have been deposited with the Cambridge Crystallographic Data Centre (No 2115014 (1), 1876829 (2), 2214913 (3), 2214921 (4), 2115013 (5), 2233398 (6), 1919918 (7), 1821410 (8); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Synthesis and structure of alkyltriphenylphosphonium arenesulfonates [Ph3PEt][OSO2С6H4(СOOH-2)], [Ph3PС3H5-cyclo][OSO2Naf-1], [Ph3PСH2СN][OSO2С6H2(Me3-2,4,6], [Ph3PCH2C≡CH][OSO2C6H4(COOH-2)], [Ph3PCH2OH][OSO2C6H3(OH- 4)(COOH-3)], [Ph3PCH2OH] [OSO2С6H3(Cl2-2,5] ∙ H2O
Alkyltriphenylphosphonium arenesulfonates [Ph3PEt][OSO2С6H4(СOOH-2)] (1), [Ph3PС3H5-cyclo][OSO2Naf-1] (2), [Ph3PСH2СN][OSO2С6H2(Me3-2,4,6] (3), [Ph3PCH2C≡CH][OSO2C6H4(COOH-2)] (4), [Ph3PCH2OH][OSO2C6H3(OH-4)(COOH-3)] (5), [Ph3PCH2OH] [OSO2С6H3(Cl2-2,5] ∙ H2O (6) were obtained by substitution reaction from tetraorganylphosphonium halides and arenesulfonic acids in water, yielding up to 90%. The structure of complexes 1–6 was proven by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction data, crystals of the complexes have ionic structure and consist of tetraorganylphosphonium cations and arenesulfonate anions. Crystals (1) [Ph3PEt][OSO2С6H4(СOOH-2)], C27H25O5PS, M 492.50; triclinic syngony, symmetry group P–1; cell parameters: a = 8.645(6), b = 11.385(6), c = 13.194(7) Å;  = 74.954(17), β = 73.72(3),  = 89.24, V = 1201.3(12) Å3; Z = 2; calc = 1.362 g/cm3; 2: 5.9665.22 deg.; total reflections 63751; independent reflections 8716; number of refined parameters 309: Rint = 0.0466; GOOF 1.091; R1 = 0.0500, wR2 = 0.1129; residual electron density (max/min): 0.23/0.45 e/Å3], (2) [Ph3PС3H5-cyclo][OSO2Naf-1], C62H54O6P2S2, M 1021.11; orthorhombic syngony, symmetry group P-ca21; cell parameters: a = 18.215(11), b = 21.189(12), c = 13.330(8) Å;  = β =  = 90.00; V = 5145(5) Å3, Z = 4; calc = 1.318 g/cm3; 2: 5.7456.66 deg.; total reflections 94209; independent reflections 12754; number of refined parameters 649: Rint = 0.01669; GOOF 1.016; R1 = 0.0759, wR2 = 0.1639; residual electron density (max/min): 0.72/0.35 e/Å3], (3) [Ph3PСH2СN][OSO2С6H2(Me3-2,4,6], C29H28NO3PS, M 501.55; monoclinic syngony, symmetry group P21/c; cell parameters: a = 13.033(18), b = 14.544(12), c = 13.941(13) Å; β = 101.30(4) deg., V = 2591(5) Å3, Z = 4; calc = 1.286 g/cm3: 2: 5.5458.88 deg.; total reflections 109265; independent reflections 7027; number 319 parameters to be refined; Rint = 0.0444; GOOF 1.051; R1 = 0.0408, wR2 = 0.1047; residual electron density (max/min): 0.22/0.51 e/Å3], (4) [Ph3PCH2C≡CH][OSO2C6H4(COOH-2)], C28H23O5PS, M 502.49; triclinic syngony, symmetry group P–1; cell parameters: a = 8.065(5), b = 12.708(6), c = 12.844(6) Å;  = 100.120(19), β = 91.87(3),  = 99.88(2), V = 1274.0(12) Å3; Z = 2; calc = 1.310 g/cm3; 2: 5.8857 deg.; total reflections 72756; independent reflections 6448; number of refined parameters 332; Rint = 0.0369; GOOF 1.044; R1 = 0.0393, wR2 = 0.0991; residual electron density (max/min); 0.27/0.37 e/Å3], (5) [Ph3PCH2OH][OSO2C6H3(OH-4)(COOH-3)], C27H22NO6PS, M 519.49; triclinic syngony, symmetry group P–1; cell parameters: a = 8.578(4), b = 12.727(8), c = 12.854(5) Å;  = 64.259(19), β = 83.41(2),  = 88.26(3), V = 1255,3(12) Å3; Z = 2; calc = 1.374 g/cm3; 2: 5.6270.34 deg.; total reflections 84712; independent reflections 11044; number of refined parameters 335; Rint = 0.0413; GOOF 1.020; R1 = 0.0518, wR2 = 0.1269; residual electron density (max/min); 0.75/0.45 e/Å3]; (6) [Ph3PCH2OH][OSO2С6H3(Cl2-2,5]∙H2O, C50H44Cl4O9P2S2, M 1056.71; monoclinic syngony, symmetry group P21/n; cell parameters: a = 9.120(5), b = 12.936(8), c = 21.094(13) Å; β = 90.32(2), V = 2489(3) Å3; Z = 4; calc = 1.410 g/cm3; 2: 5.7857 deg.; total reflections 56284; independent reflections 6307; number of refined parameters 323; Rint = 0.0503; GOOF 1.034; R1 = 0.0476, wR2 = 0.1156; residual electron density (max/min): 0.51/0.47 e/Å3].
Oxidation of tris(2-methoxyphenyl)antimony with tert-butyl hydroperoxide in the presence of carboxylic acid
Oxidation of tris(2-methoxyphenyl)antimony with tert-butyl hydroperoxide in the presence of a carboxylic acid in tetrahydrofuran or diethyl ether leads to formation of tris(2-methoxyphenyl)antimony bis(chloroacetate) (2-MeOC6H4)3Sb[OC(O)CH2Cl]2 (1), tris(2-methoxyphenyl)antimony bis(2-methoxybenzoate) (2-MeOC6H4)3Sb[OC(O)C6H4(OMe-2)]2 (2), tris(2-methoxyphenyl)antimony bis(2,3-difluorobenzoate) [(2-MeOC6H4]3Sb[OC(O)C6H3F2-2,3]2 (3) and tris(2-methoxyphenyl)antimony bis(pentafluorobenzoate) solvate with benzene [(2-MeOC6H4]3Sb[OC(O)C6F5]2 ∙ ½ PhH (4). Compounds 14 isolated after recrystallization from a benzene-octane mixture in the form of single crystals, were characterized by IR spectroscopy and X-ray diffraction (XRD) analysis. The IR spectra contain bands characterizing vibrations of carbonyl groups (1697, 1624, 1655, 1668 cm–1), the SbC3 fragment (440–447 cm–1), the Sb–O bonds (575–536 cm–1), respectively. According to the XRD data, crystals 1 and 4 belong to the triclinic syngony, symmetry group P–1; crystals 2 and 3 belong to the monoclinic syngony, symmetry group P21/n. The uncertainty factors for refinement of the structural data are R1 = 0.0502 (1), R1 = 0.0437 (2), R1 = 0.0409 (3), R1 = 0.0333 (4). In trigonal bipyramidal molecules with electronegative ligands in axial positions, the Sb−C distances are 2.0966(17)−2.1194(18) Å for 1, 2.104(2)−2.126(2) Å for 2, 2.0889(19)−2.1134(19) Å for 3, and 2.109(2)−2.123(2) Å for 4; the OSbO bond angles take the values of 175.15(5)° (1), 171.42(6)° (2), 176.97(6)° (3), and 164.47(6)° (4). The Sb−O distances in 1 [2.1088(15) and 2.1269(15) Å] are comparable with those observed in 2 [2.1137(17) and 2.1232(18) Å], in 3 [2.0880(14) and 2.1063(14) Å] and are slightly different for 4 [2.1035(17) and 2.1460(17) Å]. The solvate molecules of benzene in 4 bind neighboring dicarboxylate molecules [the C∙∙∙H and Cl∙∙∙H distances are 2.84 Å and 3.06 Å, which is less than the sum of the covalent radii of the partner atoms. The antimony atom coordinates the carbonyl oxygen atoms from the side of small equatorial angles (115.31(9) and 119.59(9)), while the Sb∙∙∙O=C intramolecular contacts are 3.374(3) and 3.296(3) Å, which is greater than the Sb∙∙∙OMe intramolecular contacts (3.0793.172 Å). It should be noted that a similar difference in the Sb∙∙∙O and Sb∙∙∙OMe intramolecular contacts is also observed in the first three molecules of the complexes [3.296(3), 3.374(3) Å and 3.1023.167 Å for 1, 3.010(3), 3.164(3) Å and 3.0583.202 Å for 2 and 3.190(3), 3.233(3) Å and 3.056-3.120 Å for 3]. The Sb∙∙∙O=C intramolecular contacts between the central metal atom and carbonyl oxygen atom are the largest in 1 and 4, which can be explained by the presence of electroacceptor carboxylate ligands. Complete tables of atomic coordinates, bond lengths and bond angles for the structures have been deposited with the Cambridge Crystallographic Data Centre (No. 2416266 (1), No. 2415652 (2), No. 2415732 (3), No. 2415648 (4), deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Tris[(2-methoxy)(5-bromo)phenyl]antimony dicarboxylates [(2-MеO)(5-Br)C6H3]3Sb[oC(O)C6H3F2-2,3]2, [(2-MеO)(5-Br)C6H3]3Sb[OC(O)CH2OC6H2Cl3-2,4,5]2 ∙ ½ TolH
Tris[(2-methoxy)(5-bromo)phenyl]antimony dicarboxylates [(2-MeO)(5-Br)C6H3]3Sb[OC(O)C6H3F2-2,3]2 (1), [(2-MeO)(5-Br)C6H3]3Sb[OC(O)CH2OC6H2Cl3-2,4,5]2 ∙ ½ TolH (2) were synthesized by interaction of tris[(2-methoxy)(5-bromo)phenyl]antimony and carboxylic acid in the presence of tert-butyl hydroperoxide (molar ratio 1:2:1) in ether at room temperature and structurally characterized after recrystallization from toluene. Crystallographic characteristics of 1 [C35H24Br3F4O7Sb, M = 994.00; triclinic syngony, space group P–1; cell parameters: a = 9.596(13) Å, b = 11.592(18) Å, c = 17.57(3) Å; a = 73.44(7)°, β = 86.25(7)°, g = 87.23(7)°, V = 1868(5) Å3, Z = 2; rcalc = 1.767 g/cm3; m = 4.011 mm–1; F(000) = 964.0; collection area by 2q: 5.54–48.88°; –11 ≤ h ≤ 11, –13 ≤ k ≤ 13, –20 ≤ l ≤ 20; total reflections 44182; independent reflections 6118 (Rint = 0.0341); GOOF = 1.039; R-factor = 0.0378]; 2 [C81H60Br6Cl12O18Sb2, M = 2469.61; triclinic system, space group Р–1; cell parameters: a = 12.214(7) Å, b = 14.000(9) Å, c = 15.358(6) Å; a = 95.32(2)°, β = 97.333(17)°, g = 111.15(3)°, V = 2402(2) Å3, Z = 1; rcalc = 1.707 g/cm3; m = 3.453 mm–1; F(000) = 1206.0; collection area by 2q: 5.84–56.998°; –16 ≤ h ≤ 16, –18 ≤ k ≤ 18, –20 ≤ l ≤ 20; total reflections 74550; independent reflections 12138 (Rint = 0.0588); GOOF = 1.019 ; R-factor = 0.0384]. From the X-ray diffraction data it follows that crystals 1–2 consist of trigonal-bipyramidal molecules with the oxygen atoms of carboxylate ligands in axial positions (solvate molecules of toluene are present in crystal 2). The OSbO angles in 1 and 2 are 172.78(12)°, 175.51(8)°, the Sb-С equatorial bond lengths are 2.111(5)-2.130(5), 2.108(3)-2.126(3) Å; and the Sb-O axial lengths equal 2.096(4), 2.133(4) Å; 2.099(3), 2.121(3) Å, respectively. Due to the bidentate nature of the carboxylate ligands in structures 1 and 2 there are intramolecular contacts between the Sb and O atoms of the carbonyl groups [3.056(5), 3.070(5) Å; 3.129(4), 3.129(4) Å]. The formation of intramolecular contacts Sb⋅⋅⋅O(=C) occurs within two different CSbC equatorial angles, as a result of which the CSbC equatorial angles differ slightly from each other [108.44(19)-129.16(19)° for 1; 112.46(12)-123.88(11)° for 2]. In addition, in molecules 1 and 2 there are intramolecular contacts Sb⋅⋅⋅OMe, which are 3.043(6)-3.172(6) Å, 3.097(4)-3.189(4) Å, respectively, therefore it can be considered that the coordination number of the central metal atom increases to CN = 10. Complete tables of atomic coordinates, bond lengths and valence angles of compounds 1 and 2 are deposited in the Cambridge Crystallographic Data Centre (CCDC No. 2060290, No. 2067753 deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Assessment of the metal atom coordination sphere occupation degree in triarylantimony dicarboxylates and μ2-oxo-bis[(carboxylato)triarylantimony]
On the basis of the X-ray diffraction analysis data for forty triarylantimony dicarboxy¬lates and seven μ2-oxo-bis[(carboxylato)triarylantimony], a quantitative assessment of the metal atom coordination sphere occupation degree in the model of ligand solid angles was carried out for the first time to identify the relationship between the coordination space (G-factor) occupation degree and the presence of intramolecular interactions leading to distortion of molecular geometric characteristics. The G-factor (%) for triarylantimony dicarboxylate molecules varied within the range of 80.19–94.90%. The most typical values of the G-factor are from 86 to 88.5%. The most saturated coordination spheres of a central atom (more than 90%) were found for the compounds containing methoxy groups in aryl ligands, which coordinate oxygen atoms to the antimony atom. High values of the G-factor (89.41–91.34%) have been found in structures in which the coordination sphere saturation is due to the Sb⋅⋅⋅O(=С) strong non-valent interactions (2.543(1)–2.856(6) Å). Steric congestion leads to distortion of the molecular geometric characteristics, in particular to an increase in one of the CSbC equatorial angles up to 159.3(1)º. In compounds of the general formula [Ar3SbOC(O)R]2O, the G-factor varies within the range from 86.95 to 91.05%, which is 2–4% higher than in triarylantimony dicarboxylates with similar carboxylate ligands. The G-factor of molecules with a linear structure of the Sb–O–Sb central fragment is smaller on average than with an angular one. Complete tables of atomic coordinates, bond lengths and bond angles are deposited in the Cambridge Crystallographic Data Centre (№ 1821409 (1), 1979844 (2), 1980334 (3), 2121388 (4), 850119 (5), 2089436 (6), 2127828 (7), 1573780 (8), 1573014 (9), 1573486 (10),1883064 (11),1883072 (12), 2055551 (13), 1883065 (14), 1883074 (15), 1573983 (16), 1031560 (17), 2055594 (18), 1015668 (19), 1010868 (20), 1919919 (21), 1880056 (22), 1884115 (23), 1462857 (24), 1576023 (25), 1478437 (26), 1576022 (27), 1457885 (28), 1457894 (29), 1576967 (30), 2178731 (31), 1462849 (32), 2045964 (33), 2060290 (34), 2074511 (35), 2048157 (36), 2041587 (37), 2055804 (38), 2051941 (39), 2077192 (40), 1840588 (41), 2217059 (42), 2225642 (43), 2233180 (44), 2233088 (45), 1841803 (46), 1840585 (47); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
The chemistry of organoelement compounds continues to be steadily developed and to develop related fields of chemical science. A wide range of synthetic methods developed on the basis of organoelement chemistry in recent decades still allows obtaining new and functionally useful materials. The abundance of works devoted to the complete synthesis of complex natural molecules is also due to developments in the field of organoelement chemistry. Nevertheless, the lack of reference information concerning the latest achievements in this branch of chemistry significantly reduces the possibilities of its comprehensive study. This problem has been previously raised by V.V. Sharutin and V.S. Senchurin in their monograph “Named Reactions in Chemistry of Organoelement Compounds”, but since its publication more than ten years have gone by. In order to fill the gap that has arisen during this period, this review describes the latest cases of using named reactions involving organoelement compounds (including those not mentioned in the monograph): Bruylants, Nicholas, Ferrier, Vorbrüggen, Arbuzov–Michaelis, Atherton–Todd, Birum–Oleksyszyn, Petasis, Rauhut–Currier, Chan–Evans–Lam, Staudinger, Kinugasa, Lu, Pauson–Khand, Rautenstrauch, Corey–Seebach, Kukhtin–Ramirez, Grieco–Sharpless, Hudrlik–Peterson, Zweifel, Doyle–Kirmse, McKenna, Nesmeyanov–Vol’kenau–Bolesova, Soai, Trofimov–Gusarova and some others. For the completeness of presentation, the paper provides typical schemes, supposed mechanisms, and, if possible, the limits of their applicability and shortcomings. The reactions are conditionally divided into groups according to their type and features of the proceeding.
Semyonov Vladimir Viktorovich (1951-2025)
Synthesis of tetraphenylantimony 3-fluorophenylacetate from pentaphenylantimony and triphenylantimony bis(3-fluorophenyl acetate)
The interaction of equimolar amounts of pentaphenylantimony and bis(3-fluorophenylacetato)triphenylantimony in benzene yielded 92% tetraphenylantimony 3-fluorophenylacetate (1), which was identified by IR spectroscopy and X-ray structural analysis. X-ray diffraction analysis was performed on a D8 QUEST diffractometer from Bruker. The crystallographic characteristics of the unit cell of the compound are as follows: monoclinic space group Cc, a = 10,2427(6), b = 17,7825(7), c = 14,6472(5) Å, β = 95,260(4), V = 2656,60(17) Å3, Z = 4, ρcalc = 1,458 g/cm3,  = 1,072 mm1, F(000) = 1176,0, crystal size 0,320,20,09 mm, data collection range for 2θ, deg: 6,95256,992, index range –13 ≤ h ≤ 12, –19 ≤ k ≤ 23, –19 ≤ l ≤ 19, number of measured reflections 9906, number of independent reflections 4334, Rint = 0,0228, GOOF = 1,139, number of parameters 330, R1 = 0,0350, wR2 = 0,1042. According to X-ray diffraction data, the antimony atoms in the compound have a distorted trigonal-bipyramidal coordination with the oxygen atom of the carboxylate group in the axial position. The axial angle CSbO is 175,9(2)º. The sum of the equatorial angles CSbC is 357,1(9)°, the Sb–Ceq distances [2,109(7), 2,117(5), 2,146(5) Å] are significantly shorter than the Sb–Cax [2,194(7) Å] and Sb–O [2,244(4) Å] bond lengths. The organization of molecules in the crystal of compound 1 is due to hydrogen bonds and CH∙∙∙π-interactions of the rings of the aryl and carboxyl ligands. Complete tables of atomic coordinates, bond lengths, and bond angles have been deposited with the Cambridge Crystallographic Data Center (No. 2055555; deposit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk/data_request/cif).
Synthesis and crystal structure of M- and W-type manganese-substituted strontium hexaferrite
The article is devoted to the synthesis and study of the structure of strontium hexaferrite and manganese doped strontium hexaferrite. The samples were obtained at various temperatures in the range of 1100–1300 °C by solid-state reaction. An X-ray diffraction (XRD) analysis was carried out and the dependence of the lattice parameters of the main phases on the synthesis temperature was determined. It was found that at 1300 °C strontium carbonate and iron (III) oxide form a pure M-type strontium hexaferrite SrFe12O19, however, at the same temperature, but the addition of manganese (III) oxide to the charge leads to a change in the type of ferrite from M- to W-type.
The approaches to modeling of self-healing for polydimethylsiloxanes after electrical breakdown
A new approach is proposed for analyzing the efficiency of self-healing of polydimethylsiloxane polymers with bubble-shaped defects that occur after low-power electrical breakdown in polydimethylsiloxane samples. The rheological characteristics of the samples were close to those of amorphous gel-like materials with fairly high transparency. Simulation modeling of the bubble-shaped defect disappearance process was performed, taking into account the dissolution of gases (hydrogen, oxygen, nitrogen, carbon monoxide) in the sample and the effect of surface tension forces on the defect boundary. It is shown that, for small sample sizes, hydrogen and carbon monoxide that occur as a result of electrical breakdown are quickly replaced by nitrogen and oxygen dissolved in the sample due to contact with the atmosphere. It has been established that efficient self-healing of a polydimethylsiloxane sample after a low-power electrical breakdown is possible only with the simultaneous action of both surface tension and good gas solubility in the sample. Based on the simulation model, a method for analyzing the efficiency of self-healing of the continuity of a polymer material medium is proposed. The method is based on comparing the rate of change in the shape and volume of bubble-shaped defects after an electrical breakdown and the rate of change in mechanical defects. This information can be obtained by analyzing photographs of defects taken in light transmitted through the defect. The mechanical nature of the defects is used as a reference level relative to which the effect of electrical breakdown can be analyzed. The considered method allows one to easily perform direct measurements of the dynamics of defect change and is therefore especially effective in collecting statistical data on the self-healing of transparent amorphous materials.
Electrochemical determination of acetaminophen by a sensor based on samarium ferrite and carbon nitride
Currently, the detection of drugs in biological samples is a lengthy and time-consuming process that requires the use of expensive equipment. Acetaminophen is an effective antipyretic agent and a painkiller. Detection of acetaminophen in biological samples is important due to widespread use of this drug for medicinal purposes. In this paper an electrochemical approach is considered for the detection of acetaminophen in water. The use of a carbon paste electrode modified with SmFeO3/g-C3N4 composite material makes determination easy and fast, thanks to the best combinations of properties. The detection limit of acetaminophen for the proposed electrode is 500 nM, the maximum is 230 µM
Diphenylbismuth arenesulfonates Ph2BiOSO2R
The corresponding diphenylbismuth arenesulfonates have been synthesized by the interaction of equimolar amounts of triphenylbismuth with mesitylenesulfonic, naphthalene-1-sulfonic, (1S)-(+)-camphor-10-sulfonic and 2,5-dichlorobenzenesulfonic acids (1:1 molar) in ether and the structural characteristics have been found for diphenylbismuth mesitylenesulfonate (1), diphenylbismuth naphthalene-1-sulfonate (2); they are coordination polymers in which the bismuth atoms have a distorted trigonal-bipyramidal coordination with the oxygen atoms of the sulfonate groups in the axial positions (the Bi–O distances are 2.404(4), 2.500(4) Å for 1 and 2.398(14)2.435(13) Å for 2) and the carbon atoms of phenyl substituents in the equatorial positions (the Bi–C distances are 2.221(18)2.250(18) Å). The third position in the equatorial plane is occupied by an unshared electron pair. According to the X-ray diffraction data, crystals 1 [C21H21BiO3S, M 562.42; monoclinic syngony, symmetry group P21/n; cell parameters: a = 11.821(5), b = 9.056(5), c = 19.275(9) Å;  = 90.00, β = 99.083(17),  = 90.00; V = 2037.5(17) Å3; Z = 4; calc = 1.833 g/cm3; /mm1 8.772; F(000) 1080.0; 2 5.757 deg.; total reflections 38408; independent reflections 5147; number of refined parameters 239; Rint = 0.0572; GOOF 1.084; R1 = 0.0339, wR2 = 0.0690; residual electron density (max/min): 2.16/2.47 e/Å3], 2 [C44H34O6S2Bi2, M 1140.79; monoclinic syngony, symmetry group P21/c; cell parameters: a = 17.098(8), b = 11.939(6), c = 19.818(8) Å;  = 90.00, β = 90.070(17),  = 90.00; V = 4045(3) Å3; Z = 4; calc = 1.873 g/cm3; /mm1 8.838; F(000) 2176.0; 2 5.8455.98 deg.; total reflections 120306; independent reflections 9672; number of refined parameters 487; Rint = 0.1780; GOOF 1.207; R1 = 0.1183, wR2 = 0.2024; residual electron density (max/min): 1.84/4.84 e/Å3].
The effect of curing temperature modes on the physico-chemical characteristics of modified epoxy resin
Epoxy resins are the leading resins used in the field of composite materials. Despite the unique characteristics, guaranteeing high volumes of consumption, these resins have certain disadvantages: high viscosity, low resistance to atmospheric influence. In order to reduce negative technological factors when epoxy resin is used as a thermosetting binder for composition, less viscous epoxyamine resin was studied. To impart elastic properties, a modification of this resin was carried out with two components: polyester based on sebacic acid and polyamide hardener. Curing of compositions was carried out at different temperature modes. The formation of a cross-linked polymer product, as well as the influence of temperature modes on the degree of curing of polymer films, was described. Important physico-mechanical and operational characteristics of the obtained samples were investigated. The correlation between the obtained parameters and temperature modes of composite processing was determined.
Synthesis and structure of organometallic coordination polymer based on lanthanum(III) and brominated terphenyl dicarboxylic acid
A new organometallic coordination polymer {La2(6BrTerPDC)3DMSO3} (2) was obtained by a solvothermal synthesis (in DMSO/1,4-dioxane solution) between lanthanum(III) nitrate and brominated terphenyl dicarboxylic acid derivative 6BrTerPDC (1). The structure of compound 2 was solved for the first time by direct methods using the X-ray diffraction analysis data. Crystallogra¬phic data: C36H30Br9LaO9S3, М 1560.88; space group P ; cell parameters: a = b = 26.822(4) Å, c = 8.6710(17) Å, α = β = 90°, γ = 120°, V = 5402.3(19) Å3, F (000) = 1476.0, absorption coefficient μ = 4.399 мм–1, crystal size 0.2 × 0.02 × 0.02 mm, reflection index intervals –21 ≤ h ≤ 32, –32 ≤ k ≤ 32, –10 ≤ l ≤ 9, total reflections 17717, independent reflections 6459, Rint 0.1072, residual electron density 1.31/–0.62 e/Å3. The unit cell consists of two structurally independent La3+ cations. Relatively high factor R1 = 0.1942 is associated with disorder in the arrangement and degree of occupancy of the bromine atoms. This is a consequence of the fact that in the process of bromination of dimethyl ester of terphenyl dicarboxylic acid, bromine is attached both to the central and peripheral aromatic rings of the acid, forming many homologs, presumably mono-, di-, tri-, tetra-, penta-, and hexabromo derivatives, inclu¬ding position isomers.
Synthesis and structure of tetraorganylphosphonium arenesulfonates [Ph3PEt][OSO2С6H2Me3-2,4,6], [Ph3PEt][OSO2C6H3(OH-4)(COOH-3)], [Me4P][OSO2С10H5(OH-1)(NO2)2-2,4], [Ph3PCH2C≡CH] [OSO2C6H3(OH-4)(COOH-3)]
Tetraorganylphosphonium arenesulfonates [Ph3PEt][OSO2С6H2Me3-2,4,6] (1), [Ph3PEt][OSO2C6H4)(COOH-2)] (2), [Me4P][OSO2С10H5(OH-1)(NO2)2-2,4] (3), [Ph3PCH2C≡CH][OSO2C6H3(OH-4)(COOH-3)] (4) were obtained by substitution reaction from tetraorganylphosphonium halides and arenesulfonic acids in water with a yield of up to 90 %. The structure of complexes 1–4 was proven by IR spectroscopy and X-ray diffraction analysis. According to X-ray diffraction data, the crystals of the complexes have an ionic structure and consist of tetraorganylphosphonium cations and arenesulfonate anions. Crystals (1) [Ph3PEt][OSO2С6H2Me3-2,4,6], C29H31O3PS, M 490,57; monoclinic system, symmetry group P21/c; cell parameters: a = 13,05(2), b = 14,624(18), c = 13,69(2) Å; β = 99,07(7), V = 2579(7) Å3; Z = 8; cal = 1,263 g/cm3; 2 6,0256,9; total reflections 53758; independent reflections 6447; number of specified parameters 311; Rint = 0,0787; GOOF 1,130; R1 = 0,0473, wR2 = 0,1127; residual electron density (max/min): 0,21/0,49 e/Å3], (2) [Ph3PEt][OSO2C6H4)(COOH-2)], C27H25O5PS, M 492,50; triclinic system, symmetry group P–1; cell parameters: a = 8,645(6), b = 11,385(6), c = 13,194(7) Å;  = 74,954(17), β = 73,72(3),  = 89,24(3); V = 1201,3(12) Å3, Z = 2; cal = 1,362 g/cm3; 2 5,9665,22; total reflections 63751; independent reflections 8716; number of specified parameters 309; Rint = 0,0466; GOOF 1,019; R1 = 0,0500, wR2 = 0,1129; residual electron density (max/min): 0,23/0.45 e/Å3], (3) [Me4P][OSO2С10H5(OH-1)(NO2)2-2,4], C14H17N2O8PS, M 404, 33; monoclinic syngony, symmetry group P21/n; cell parameters: a = 7,927(6), b = 8,303(8), c = 26,780(19) Å; β = 93,62(2), V = 1759(2) Å3, Z = 4; cal = 1,527 g/cm3; 2 6,6656,64; total reflections 44090; independent reflections 4338; number of specified parameters 243; Rint = 0,0746; GOOF 1,054; R1 = 0,0550, wR2 = 0,1141; residual electron density (max/min): 0,38/0,35 e/Å3], (4) [Ph3PCH2C≡CH][OSO2C6H3(OH-4)(COOH-3)], C56H46O12P2S2, M 1036,99; monoclinic syngony, symmetry group P21/c; cell parameters: a = 17,888(7), b = 19,340(9), c = 15,858(7) Å; β = 113,031(4), V = 5049(4) Å3; Z = 4; cal = 1,364 g/cm3; 2 5,9656,66; total reflections 84469; independent reflections 12502; number of specified parameters 655; Rint = 0,0862; GOOF 1,025; R1 = 0,0548, wR2 = 0,1173; residual electron density (max/min): 0,54/0,40 e/Å3].
Structure of tri(para-tolyl)bismuth dicarboxylates p-Tol3Bi[OC(O)CH2Cl]2 and p-Tol3Bi[OC(O)C6H3F2-2,5]2 ∙ TolH
By reacting tri(para-tolyl)bismuth with chloroacetic and 2,5-difluorobenzoic acids in ether in the presence of tert-butyl hydroperoxide, tri(para-tolyl)bismuth dicarboxylates were synthesized. After recrystallization from toluene, they were isolated as p-Tol3Bi[OC(O)CH2Cl]2 (1) and solvate p-Tol3Bi[OC(O)C6H3F2-2,5]2 ∙ TolH (2), the structure of which was proven by X-ray diffraction analysis (XRD). Crystallographic characteristics of 1 [C25H25O4Сl2Bi, M = 669,33; triclinic syngony, space group P-1; cell parameters: a = 10,370(6) Å, b = 11,731(4) Å, c = 12,746(6) Å;  = 106,77(2), β = 103,90(2),  = 108,764(18), V = 1307,5(10) Å3, Z = 2; calc = 1,700 g/cm3;  = 6,973 mm–1; F(000) = 648,0; region collection at 2q: 6,34–71,62; –17 ≤ h ≤ 17, –19 ≤ k ≤ 19, –20 ≤ l ≤ 20; total reflections 83762; independent reflections 12095 (Rint = 0,0546); GOOF = 1,035; R-factor = 0,0353], 2 [C42H35BiF4O4, M = 888,68; triclinic syngony, space group P–1; cell parameters: a = 9,403(4) Å, b = 11,009(6) Å, c = 18,757(8) Å;  = 78,80(2), β = 88,918(17),  = 66,61(2), V = 1744,5(15) Å3, Z = 2; calc = 1,692 g/cm3;  = 5,118 mm–1; F(000) = 876,0; collection area by 2q: 6,22–54,362; –12 ≤ h ≤ 12, –14 ≤ k ≤ 14, –24 ≤ l ≤ 24; total reflections 40062; independent reflections 7698 (Rint = 0,0337); GOOF = 1,054; [R-factor = 0,0268]. From the X-ray diffraction data it follows that the bismuth atoms in 1 and 2 have a distorted trigonal-bipyramidal coordination with the oxygen atoms of the carboxyl groups in the axial positions (OBiO 170,91(6) and 170,49(15), respectively; BiO 2,2875(19) Å, 2,292(2) Å for 1 and 2,262(3) Å, 2,317(3) Å for 2) and equatorial tolyl ligands (BiC 2,188(3)2,210(2) Å for 1 and 2,198(4)2,219(4) Å for 2). The presence of a coordination bond between the central metal atom and the carbonyl oxygen atom [Bi∙∙∙O=C 2,991(3) Å, 2,997(3) Å in 1 and 2,879(3) Å, 2,922(3) Å in 2] allows us to speak about an increase in the coordination number of the bismuth atom to 7. In structures 1 and 2, the maximum equatorial angle on the side of the Bi∙∙∙O=C contact (139,21(9) and 142,18(15)) is significantly larger than the other two equatorial angles. Complete tables of atomic coordinates, bond lengths and bond angles for compounds 1 and 2 have been deposited with the Cambridge Crystallographic Data Centre (CCDC 1913595 and 2051942; depos-it@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Phase formation of layered titanate-niobates KA2Ti2NbO10, A=Bi(III), Pr(III)
Layered perovskite-like compounds related to Dion–Jacobson phases with unique structural features have potential applications in various fields of science and technology, which makes these materials the subject of active research in recent years. Synthesis of Dion–Jacobson phases is carried out in various ways, including standard solid-state synthesis, hydrothermal synthesis, sol-gel method, molten salt synthesis, and others. At present, the most common method is the solid-state synthesis, due to simple interaction of compounds and an easy way to control the composition of the initial mixture. However, it is reported that not every compound with the Dion–Jacobson structure can be obtained by this method, which indicates the need for correct selection of heat treatment conditions and precursors. Thus, the aim of this study is to investigate the possibility of forming layered perovskite-like phases with the Dion-Jacobson structure of the KA2Ti2NbO10 composition, A=Bi(III), Pr(III), using the solid-state synthesis from the initial mixture of different compositions during heat treatment in a muffle furnace. The conditions of high-temperature annealing have been selected based on the data of differential thermal and thermogravimetric analysis. It has been shown that replacing bismuth(III) oxide in the initial mixture with a high-melting praseodymium(III, IV) mixed oxide increases the temperature of obtaining a single-phase sample. It has been found that a decrease in the radius of the A-site cation in the Dion–Jacobson phase structure leads to a decrease in the symmetry of the unit cell from a tetragonal one, in the case of A=Bi(III), to orthorhombic one for A=Pr(III). The decrease of the unit cell volume with a decrease of the A-cation ionic radius has been established. The obtained phases have been studied using diffraction and spectroscopic methods.
Interaction of hexachloroplatinum hydrocacid with 2,2'-bipyridine and 1,2,3,4-tetrahydroacridine-9-carboxylic acid. Structure of reaction products
The product of the reaction of hexachloroplatinic acid with 2,2'-bipyridine in a water-acetonitrile mixture at room temperature is 2,2'-bipyridinium hexachloroplatinate(IV) [C10N2H8∙H]+2[PtCl6]2– (I). Under the same conditions, hexachloroplatinic acid protonates 1,2,3,4-tetrahydroacridine-9-carboxylic aсid at the nitrogen atom to form the dihydrate [C28N2О4H30∙H]+2[PtCl6]2–2Н2О (II). New complexes with hexachloroplatinate anions were characterized by X-ray diffraction analysis at 293(2) K (Bruker D8 Quest, MoKα radiation, λ = 0.71073 Å, graphite monochromator). Centrosymmetric [PtCl6]2 anions in complexes I and II have similar geometric characteristics (the PtCl bonds are 2.3211(9)2.3340(8) Å, the ClPtCl angles are 89.71(3)90.31(3)). Cation I is 2,2'-bipyridine molecule protonated at one of the nitrogen atoms with a weak intramolecular hydrogen bond NHN (2.20 Å). In complex II, the cation is 1,2,3,4-tetrahydroacridine-9-carboxylic acid protonated at the nitrogen atom of the heterocycle. The short contacts observed in crystal I are caused by weak intermolecular bonds of the NHCl (2.69 Å) and CHCl (2.85–2.94 Å) types, with each anion surrounded by eight cations and each cation surrounded by four anions. In crystal II chain-like structural units can be distinguished. In these chains the anion forms hydrogen bonds ОНCl (2.34 Å) through the carboxyl groups with two cations, which are bound to water molecules through the protonated nitrogen atom NHO (1.91 Å). The chains are connected to each other by weaker interactions, among which are the hydrogen bonds ОНCl (2.54 and 2.77 Å) between water molecules and anions.
New binuclear aryl compounds of antimony
The structures of five binuclear aryl antimony compounds (Ar3SbX)2O [Ar = 3-FC6H4, X = OC(O)CF2Br (1), Ar = 4-FC6H4, X = OC6H2Br3-2,4,6 ∙ 0,5C8H18 (2), Ar = 4-MeC6H4, X = OC(O)CH2Cl (3), Ar = 4-MeC6H4, X = OC(O)CH2Br (4), Ar = Ph, X = OC(O)C6HF4 (5)] were determined by X-ray diffraction analysis (X-ray diffraction) on a D8 Quest Bruker automatic four-circle diffractometer (Mo Kα radiation, λ = 0.71073 Å, graphite monochromator) at 293 K. Crystals (1) C40H24O5F10Br2Sb2, M 1177.91; monoclinic syngony, symmetry group C2/c; cell parameters: a = 24.808(9), b = 10.837(3), c = 32.215(10) Å; β = 96.711(19), V = 8601(5) Å3; Z = 8; calc = 1.819 g/cm3; 2 5.7468.08 deg.; total reflections 95957; independent reflections 14384; number of refined parameters 532; Rint = 0.0898; GOOF 1.771; R1 = 0.1705, wR2 = 0.4519; residual elec-tron density (max/min); 2.34/4.78 e/Å3], (2) C52H37O3F6Br6Sb2, M 1546.78; triclinic syngony, symmetry group P–1; cell parameters: a = 12.325(5), b = 13.749(6), c = 17.774(8) Å;  = 83.259(16), β = 80.26(3),  = 65.894(15) deg., V = 2706(2) Å3, Z = 2; calc = 1.898 g/cm3; 2 6.0659.14 deg.; total reflections 144892; independent reflections 15098; number of refined pa-rameters 623; Rint = 0.0646; GOOF 1.010; R1 = 0.0379, wR2 = 0.0791; residual electron density (max/min); 0.92/1.45 e/Å3], (3) C69H69O7,5Cl3Sb3, M 1489.84; triclinic syngony, symmetry group P–1; cell parameters: a = 10.474(7), b = 11.179(6), c = 29.736(14) Å;  = 88.899(18), β = 82.542(19),  = 76.22(3); V = 3353(3) Å3, Z = 2; calc = 1.476 g/cm3; 2 5.5651.62 deg.; total reflections 65830; inde-pendent reflections 12738; number of refined parameters 754; Rint = 0.0510; GOOF 1.037; R1 = 0.0383, wR2 = 0.0803; residual electron density (max/min): 0.83/1.13 e/Å3], (4) C69H69O7,5Br3Sb3, M 1623.22; triclinic syngony, symmetry group P–1; cell parameters: a = 10.585(7), b = 11.255(7), c = 29.712(18) Å;  = 88.41(3), β = 82.43(3),  = 75.01(3); V = 3389(4) Å3, Z = 2; calc = 1.591 g/cm3; 2 5.5833.64 deg.; total reflections 14830; independent reflections 3789; number of re-fined parameters 754; Rint = 0.0327; GOOF 1.049; R1 = 0.0354, wR2 = 0.0852; residual electron density (max/min): 0.76/0.93 e/Å3], (5) C450H288F72O45Sb18, M 9974.83; triclinic syngony, sym-metry group P–1; cell parameters: a = 12.045(12), b = 24.31(3), c = 36.66(4) Å;  = 101.75(5), β = 98.50(3),  = 98.52(5); V = 10216(19) Å3, Z = 1; calc = 1.6213 g/cm3; 2 5.640.58 deg.; total reflections 99411; independent reflections 19647; number of refined parameters 2519; Rint = 0.0516; GOOF 1.099; R1 = 0.0576, wR2 = 0.1076; residual electron density (max/min): 1.78/1.26 e/Å3].
Structure of organic and organoelemental compounds. Part 5
The structure of five organic compounds was determined using X-ray diffraction analysis. X-ray diffraction analysis of compounds was carried out on an automatic four-circle diffractometer D8 Quest Bruker (Mo Kα radiation, λ = 0,71073 Å, graphite monochromator) at 293 K. Crystals (Ph4Sb)2CO3 (1): C49H40O3Sb2, M 920.31; triclinic syngony, symmetry group P-1; cell parameters: a = 10.114(7), b = 13.975(8), c = 15.607(13) Å;  = 73.98(3), β = 79.86(5),  = 74.39(3); V = 2030(2) Å3; Z = 2; calc = 1.506 g/cm3; 2 5.852.98 deg.; total reflections 46058; independent reflections 8373; number of refined parameters 488; Rint = 0.0263; GOOF 1.131; R1 = 0.0235, wR2 = 0.0520; residual electron density (max/min) 0.85/0.55 e/Å3]; p-Tol4SbOC6H3(Cl-2)(F-4) (2): C34H31ClFOSb, M 631.79; triclinic syngony, symmetry group P–1; cell parameters: a = 10.104(10), b = 11.932(14), c = 13.582(18) Å;  = 84.41(6), β = 71.39(5),  = 74.70(5); V = 1497(3) Å3, Z = 2; calc = 1.402 g/cm3; 2 6.1463.32 deg.; total reflections 93012; independent reflections 9959; number of refined parameters 347; Rint = 0.0322; GOOF 1.049; R1 = 0.0299, wR2 = 0.0713; residual electron density (max/min); 1.20/0.72 e/Å3], Ph4SbOC(O)CF2CF2C(O)OSbPh4∙PhH (3): C58H46F4O4Sb2, M 1126.47; monoclinic syngony, symmetry group C2; cell parameters: a = 26.096(18), b = 10.011(9), c = 38.74(3) Å; β = 90.63(3); V = 10119(14) Å3, Z = 4; calc = 1.479 g/cm3; 2 6.04654.31 deg.; total reflections 124576; independent reflections 22324; number of refined parameters 1209; Rint = 0.0670; GOOF 1.039; R1 = 0.0465, wR2 = 0.0739; residual electron density (max/min); 0.52/0.53 e/Å3]; [Ph4Sb(DMSO)][PdBr3(DMSO)] (4): C28H32Br3O2PdS2Sb, M 932.52; orthorhombic syngony, symmetry group P212121; cell parameters:  = 9.430(6), b = 15.859(11), c = 22.186(13) Å;  = 90.00 = β = 90.00,  = 90.00; V = 3183(4) Å3; Z = 8; calc = 1.867 g/cm3; 2 5.6843.98 deg.; total reflections 28787; independent reflections 4023; number of refined parameters 339; Rint = 0.0291; GOOF 1.044; R1 = 0.0186, wR2 = 0.0431; residual electron density (max/min); 0.7/0.59 e/Å3]; [Ph3PAm]2[Bi2I8](MeOCH2CH2OMe) (5): C25H31BiI4OP, M 1095.05; triclinic syngony, symmetry group P–1; cell parameters: a = 11.026(6), b = 12.875(8), c = 13.419(6) Å;  = 62.580(15), β = 76.155(14),  = 79.07(2); V = 1634.8(14) Å3; Z = 2; calc = 2.225 g/cm3; 2 5.9867.58 deg.; total reflections 93637; independent reflections 13068; number of refined parameters 291; Rint = 0.0454; GOOF 1.064; R1 = 0.0367, wR2 = 0.0693; residual electron density (max/min); 1.03/2.04 e/Å3].
Synthesis and structure of tri(para-tolyl)antimony bis(2-carboxybenzenesulfonate) p-Tol3Sb[OSO2С6H4(COOH)-2]2.
Reaction of tri(p-tolyl)antimony with 2-sulfobenzoic acid in ether in the presence of hydrogen peroxide in ether leads to tri(para-tolyl)antimony bis(2-carboxybenzenesulfonate) p Tol3Sb[OSO2С6H4(COOH)-2]2 (1). According to X-ray diffraction analysis, the antimony atoms in centrosymmetric complex 1 have a distorted trigonal bipyramidal coordination with tolyl substituents in the equatorial plane and arenesulfonate ligands in axial positions, while the CSbО axial angle equals 177.96(12)°. Molecules 1 in the crystal have their own (non-crystallographic) C2 symmetry. The second order axis can be drawn through the Sb(1)C(11)C(14)C(15) atoms. The arenesulfonate substituents are located on one side of the axial axis O(1)Sb(1)O(1’), and their aryl groups form a “stack” with the tolyl substituent C(11)–C(17). In crystal 1 there are contacts of the central atom with the oxygen atoms of the arenesulfonate groups (3.639(9) Å), which are slightly less than the sum of the van der Waals radii of the Sb and S atoms (3.7 Å). In the crystal, molecules 1 are combined into dimers using hydrogen bonds between the carbonyl oxygen atoms and the hydrogen atoms of neighboring carboxyl groups (C=O∙∙∙HOC(O) is 1,85 Å). According to the X-ray diffraction data, the crystallographic characteristics of 1 [C35H31O10S2Sb, M = 797.47; monoclinic system, sp. gr. C2/c; cell parameters: a = 14.819(9) Å, b = 15.728(11) Å, c = 14.707(9) Å; β = 93.00(2)°, V = 3423(4) Å3, Z = 4; rcalc = 1.547 g/cm3; m = 0.985 mm–1; F(000) = 1616.0; collection region by 2q: 6.84–53.34°; –18 ≤ h ≤ 16, –16 ≤ k ≤ 19, –17 ≤ l ≤ 18; total reflections 6622; independent reflections 3221 (Rint = 0.0433); GOOF = 1.021; R-factor = 0.0381]. Complete tables of atomic coordinates, bond lengths, and bond angles of compound 1 have been deposited in the Cambridge Structural Data Center (CCDC 2336248; deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Synthesis and structure of a tri-p-tolylantimony derivative of glycolic acid
Interaction of tri-p-tolylantimony with tert-butylhydroperoxide and glycolic acid (1:1:2) led to 2,2,2-tri-p-tolyl-1,3-dioxa-2λ5-stibolan-4-one in 75% yield. Its structure was evaluated by NMR and X-ray methods. Unlike the previously described similar reaction of triphenylantimony with hydrogen peroxide and lactic acid, during this reaction it is a cyclometallic compound that is formed, and not the corresponding dicarboxylate, which becomes obvious from the spectrum pattern, in which there is no signal of the hydroxyl group. The C23H23O3Sb crystals are described by the rhombic symmetry group Pbca with cell parameters: a = 15.01871(11), b = 15.37651(11), c = 17.04701(12) Å, Z = 8. Using the structural parameter τ, it has been concluded that the coordination of the antimony atom in this organometallic compound is close to trigonal-bipyramidal (according to the X-ray data, τ = 0.77). The XRD data, including the coordinates of atoms, bond lengths and valence angles, are deposited in the Cambridge Structural Database (CCDC 2370604).
Synthesis and structure of benzyl- and (4-carboxybutyl)triphenylphosphonium nitrates
Interaction of benzyl- and (4-carboxybutyl)triphenylphosphonium bromides with nitric acid synthesized phosphorus complexes [Ph3PCH2Ph]NO3 (1) and [Ph3P(CH2)4COOH]NO3 (2), respectively. The obtained compounds were characterized by IR spectroscopy and X-ray diffraction analysis. According to the X-ray diffraction data, benzyltriphenylphosphonium nitrate (1) [C25H22NO3P, M = 415.41; triclinic crystal system, P–1 space group; cell parameters: a = 9.573(7) Å, b = 10.272(10) Å, c = 12.066(11) Å;  = 105.42(4), β = 107.06(4),  = 92.73(4), V = 1083.3(16) Å3, Z = 2; calc = 1.273 g/cm3;  = 0.153 mm–1; F(000) = 436.0; 2q 5.68–54.32; –12 ≤ h ≤ 12, –13 ≤ k ≤ 13, –15 ≤ l ≤ 15; collected reflections 26281; independent reflections 4802 (Rint = 0.0345); GOOF = 1.038; R-factor 0.0451] and 4-carboxybutyltriphenylphosphonium nitrate (2) [C23H24NO5P, M = 425.40; monoclinic crystal system, P21/n space group; cell parameters: a = 8.937(16) Å, b = 17.86(3) Å, c = 13.71(2) Å;  = 90.00, β = 95.04(11),  = 90.00, V = 2180(6) Å3, Z = 4; calc = 1.296 g/cm3;  = 0.160 mm–1; F(000) = 896.0; 2q 5.72–55.48; –11 ≤ h ≤ 11, –22 ≤ k ≤ 23, –17 ≤ l ≤ 17; collected reflections 18882; independent reflections 4732 (Rint = 0.0952); GOOF = 1.040; R-factor 0.0729] have an ionic structure and consist of organyltriphenylphosphonium cations with a slightly distorted tetrahedral-coordinated phosphorus atom (the CPC angles vary in the range 107.10(8)–111.56(10) for 1 and 107.62(10)–111.99(16) for 2; the P–C distances are 1.791(2)–1.803(2) Å and 1.786(4)–1.803(4) Å, respectively) and planar trigonal nitrate anions (the sums of the ONO angles are 359.6 and 360). The structural organization in crystal 1 is determined only by the interionic hydrogen bonds C–H∙∙∙O–NO2 (2.24–2.61 Å). Crystal 2, in addition to the C–H∙∙∙O–NO2 interactions (2.12–2.72 Å), also contains the O–H∙∙∙O–NO2 contacts (2.12 and 2.42 Å), C–H∙∙∙O=C (2,63 Å), as well as C–H∙∙∙NO3 (2.60 Å). Complete tables of atomic coordinates, bond lengths, and bond angles of nitrates 1 and 2 are deposited with the Cambridge Crystallographic Data Centre (CCDC 2331486 (1), 2331490 (2); deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).