A NEW 3-DIMENSIONALLY NONMOLECULAR CD-S LATTICE IN CRYSTALLINE CD7(SC6H4CH3-2)14(DMF)2

Bis(2-methylbenzenethiolato)cadmium crystallizes from DMF as Cd7(SC6H4CH3-2)14(DMF)2(5) and has a three-dimensionally nonmolecular crystal structure quite different from those of Cd(SC6H5)2and 4-substituted Cd(SC6H4X)2. The crystals (tetragonal, P432,2, a = b = 14.028 (1) Å, c = 55.295 (8) Å, V = 10880.7 (1.9) Å3, Z = 8 (X Cd3.5S7C49H49,.C3H7NO), 4311 independent observed (I/σ(I) >3) data (Mo Kα), R = 0.034) contain |Cd3(μ-SAr)3(DMF)} cycles, in which the DMF carbonyl oxygen atom has asymmetric secondary coordination (Cd-O = 2.72, 2.95, 2.99 Å) to the three Cd atoms with tetrahedral Cd(μ-SAr)4/2primary coordination. The Cd3cycles are linked by (μ-SAr) ligands and spiro Cd atoms. The unique structural feature of these three-dimensionally nonmolecular linkages is the occurrence of large open elongated macrocycles, ca. 28 Å long and 14 Å wide, around which the pathway with the smallest number of connections involves 24 Cd atoms and 24 bridging thiolate ligands. Adamantanoid cages are absent. © 1990, American Chemical Society. All rights reserved.