STRUCTURES OF ZINC(II) WITH TETRADENTATE N2S2 LIGATION

trans-3,3'-(1,2-Cyclohexanediyldinitrilo)-bis(2-methylpropane-2-thiolato)]zinc(II), [Zn(C14H28-N2S2)], Zn(2), M(r) = 353.89, monoclinic, C2/c, a = 17.914 (4), b = 9.440 (1), c = 10.877 (2) angstrom, beta = 110.19 (2)-degrees, V = 1726 (1) angstrom 3, Z = 4, D(m) = 1.35 (1), D(x) = 1.360 Mg m-3, mu(Mo K-alpha, lambda = 0.71073 angstrom) = 0.17 mm-1, F(000) = 752, T = 298 (1) K, R(F) = 0.026, wR(F) = 0.037 for 1290 reflections. 3,3'-(1,2-Cyclohexa-1,4-dienediyldinitrilo)bis(2-methylpropane-2-thiolato)]zinc(II), [Zn(C14H24N2S2)], Zn(3), M(r) = 349.86, monoclinic, P2(1)/c, a = 9.760 (2), b = 17.326 (3), c = 10.530 (2) angstrom, beta = 91.49 (2)-degrees, V = 1780 (1) angstrom 3, Z = 4, D(m) = 1.31 (1), D(x) = 1.305 Mg m-3, mu(Mo K-alpha, lambda = 0.71073 angstrom) = 0.16 mm-1, F(000) = 736, T = 297 (1) K, R(F) = 0.050, wR(F) = 0.062 for 1723 reflections. The structures consist of discrete complexes with distorted-tetrahedral ZnS2(thiolate)N2(amine) coordination geometries. Zn-S [2.2533 (6) angstrom for Zn(2); 2.259 (1), 2.253 (1) angstrom for Zn(3)] and Zn-N [2.101 (2) angstrom for Zn(2); 2.088 (4), 2.128 (4) angstrom for Zn(3)] distances are close to those reported for similar structures with bidentate N(amine)S(thiolate) ligands. The N,S chelate rings in both structures exhibit the envelope conformation with the tetrasubstituted C atoms comprising the flaps. In Zn(3), the central N,N chelate ring adopts the envelope conformation, while in Zn(2), the corresponding ring is gauche. The cyclohexane ring in Zn(2) shows the expected chair conformation, while the cyclohexa-1,4-diene ring in Zn(3) is planar to +/- 0.07 angstrom.