Non-bonded Interactions Involving Oxygen in 2-Nitrobenzenethiolato Compounds: Structures of 2,4-(O 2 N) 2 C 6 H 3 SX (X = NMe 2 or C 6 H 4 NO 2 -2) and Ph 3 MSC 6 H 4 NO 2 -2 (M = Ge,Sn or Pb)

Abstract

Crystal structures are reported for 2,4-(O₂N)₂C₆H₃X (2: X = NMe₂; 3: X = C₆H₄NO₂-2) and Ph₃MSC₆H₄NO₂-2 (4: M = Ge; 5; M = Sn; 6: M = Pb). Compound 2 is triclinic, Pbar1, a = 7.931(5), b = 8.159(7), c = 9.090(7) Å, a = 100.35(6), β = 81.00(6), γ = 110.74(6)°, D_x = 1.500 Mg.m⁻³, Z = 2, observed reflections = 834, R = 0.066 (Rw = 0.049). Compound 3 is orthorhombic, P2₁2₁2₁, a = 11.1424(18), b = 11.8067(18), c = 20.363(3) Å, D_x = 1.593 Mg.m⁻³, Z = 8, observed reflections = 925, R = 0.061 (Rw = 0.074). Compound 4 is monoclinic, P2₁/a, a = 14.73(4), b = 10.091(5), c = 15.526(4) Å, β = 107.43(7), D_x = 1.382 Mg.m⁻³, Z = 4, observed reflections = 2034, R1 = 0.0426 (wR2 = 0.0834). Compound 5 is orthorhombic, Pbca, a = 15.489(10), b = 15.701(5), c = 17.558(7) Å, D_x = 1.569 Mg.m⁻³, Z = 8, observed reflections = 2537,R1 = 0.0327 (wR2 = 0.0700). Compound 6 is orthorhombic, Pbca, a = 15.569(5), b = 15.702(3), c = 17.651(6) Å, D_x = 1.825 Mg.m⁻³, Z = 8, observed reflections = 2536, R1 = 0.0323 (wR2 = 0.0737). There are short non-bonded S—O interactions and near linear O—S—X angles in both 2 and 3; values are 2.166(6) Å and 177.1(3)° for 2; 2.582(14) Å and 177.1(8)°, and 2.609(13) Å and 177.9(6) (in two independent molecules) for 3. The S—O interaction in 3 involves the ortho nitro group of the dinitrophenyl ring. Intramolecular S—O interactions are absent in 4 – 6; however there are weak intermolecular M—O bonding in 5 and 6, which results in molecules being linked into chains; the geometries at the metal centres in 5 and 6 are distorted trigonal bipyramidal with Sn—O and Pb—O bond lengths of 3.337(3) and 3.180(5) Å, respectively, and S_axial—M—O_axial angles of 173.19(5) and 173.96(9)°, respectively. Compound 4 is essentially tetrahedral.