Study of the crystal structures of alkyltriphenylphosphonium 2,4-dinitrobenzenesulfonates [Ph3PAlk][OSO2C6H3(NO2)2-2,4)], Alk = C3H5-cyclo, (CH2)2OH, CH2OH, CH2С(O)Me

Abstract

Reactions of alkyltriphenylphosphonium bromides with 2,4-dinitrobenzenesulfonic acid in water lead to formation of ionic alkyltriphenylphosphonium 2,4-dinitrobenzenesulfonates [Ph3PAlk][OSO2C6H3(NO2)2-2,4] (Alk = C3H5-cyclo (1), (CH2)2OH (2), CH2OH (3), CH2С(O)Me (4)). Crystals 1 [C27H23N2O7PS, M 550.50; monoclinic system, symmetry group P-1; cell parameters: a = 9.354(11) Å, b = 9.764(10) Å, c = 15.416(17) Å;  = 106.29(4), β = 94.67(5),  = 97.98)6), V = 1328(3) Å3, Z = 2; calc = 1.377 g/cm3], 2 [C26H23N2O8PS, M 554.49; monoclinic system, symmetry group P21/c; cell parameters: a = 13.049(7) Å, b = 14.816(10) Å, c = 13.261(7) Å;  = 90.00, β = 93.901(15),  = 90.00, V = 2558(2) Å3, Z = 4; calc = 1.440 g/cm3], 3 [C25H21N2O8PS, M 540.47; triclinic system, symmetry group P-1; cell parameters: a = 9.086(14) Å, b = 10.95(2) Å, c = 13.17(2) Å;  = 86.20(9), β = 71.93(6),  = 89.51(11), V = 1243(4) Å3, Z = 2; calc = 1.444 g/cm3], 4 [C27H23N2O8PS, M 566.50; triclinic syngony, symmetry group P-1; cell parameters: a = 9.746(10) Å, b = 11.371(11) Å, c = 13.657(10) Å;  = 66.78(3), β = 86.30(3),  = 74.46(5), V = 1339(2) Å3, Z = 2; calc = 1.405 g/cm3]. According to the X-ray diffraction data, the phosphorus atoms in cations 1–4 have a distorted tetrahedral coordination, while the sulfonate anions have a normal geometry with a tetrahedral sulfur atom. The P–C bond lengths vary in the range 1.768(3)−1.830(3) Å; the CPC bond angles take on values of 105.54(9)°−112.42(9)°. In the arenesulfonate anions of the complexes, the S–C distances are close to each other [1.794(2)–1.807(3) Å], the S–O bonds are practically aligned [1.363(4)–1.495(4) Å]. The structural organization in complexes 1–4 is mainly due to weak intermo-lecular contacts of the O···H type: 2.31–2.71 Å (1), 2.35–2.64 Å (2), 2.38 –2.70 Å (3), 2.24–2.90 Å (4).