Structural studies of metal dithiocarbamates. Part IV. The crystal and molecular structure of cadmium(II)NN-diethyldithiocarbamate

Abstract

The crystal and molecular structure of cadmium( II) NN-diethyldithiocarbamate has been determined from threedimensional X-ray data and refined by anisotropic least-squares methods to a final R value of 0.084. Crystals are monoclinic, space group P2Jc. with a = 10.1 66, b = 10.746, c = 16.71 7 A, 13 = 11 1" 53'. In the solid state the complex is binuclear, the two halves of the molecule being related by a centre of symmetry, and should be formulated as [Cd2(S2CNEt2)4]. Two of the four NN-diethyldithiocarbamate groups act as bridging ligands, giving rise to a puckered eight-membered ring which comprises two cadmium, four sulphur, and two carbon atoms. The two symmetry-related cadmium atoms are five-co-ordinate, the co-ordination polyhedron being intermediate between a tetragonal pyramid and a trigonal bipyramid. The five cadmium-sulphur bond distances range from 2.536 to 2.800 A.

Bis(μ-diethyldithiocarbamato)-1κS,1:2κ2S';2κS,1:2κ2S'-bis(ethylzinc)

“…The structure is similar to those recently reported for a neopentylzincdiselenocarbamate dimer (Malik, Motevalli, Walsh & O'Brien, 1992), a methylzincdithioearbamate dimer (Hursthouse, Malik, Motevalli & O'Brien, 1991) and methyl-or ethylzinediselenocarbamate dimers (Hursthouse, Malik, Motevalli & O'Brien, 1992a). The structure also resembles the dimeric units found in bis(thiocarbamates) and bis(selenocarbamates) (Bonamico, Mazzone, Vaciago & Zambonelli, 1965;Bonamico & Dessy, 1971;Domenico, Torelli, Vaciago & Zambonelli, 1968;Hursthouse, Malik, Motevalli & O'Brien, 1992b) but with the alkyl group replacing the chelating-only earbamate group. The bond distances and angles are similar to those in other alkylzincdithiocarbamates.…”

Refinement of the crystal structure of dimeric bis(N,N-diethyldithiocarbamato) cadmium(II), [Cd(S2CNEt2)2]2

“…New data are presented for dimeric [Cd(S2CNEt2)2]2 [2,3], The cadmium centre is five coordinated, being chelated by two almost symmetrically coordinating dithiocarbamate ligands, one of which forms a bridge to the centrosymmetrically related cadmium centre. coupled with the range of S2'-Cd-S angles of 97.73(1)° to 107.13(2)°, suggest that the coordination geometry is best described as square pyramidal.…”

Serendipitous compositional and structural diversity in urotropine adducts of binary cadmium xanthates

“…2 -tridentate [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34]. This dramatic difference in structural outcomes is rationalised in terms of the significant contribution of the canonical structure shown in Fig.…”

“…In the crystal packing, molecules self-assemble into a supramolecular layer in the ab-plane being connected by C-H The structures of one-dimensional, zigzag coordination polymers 1 and 2 complement the sole previous example of a linear coordination polymer constructed from Cd(S2COiPr)2 and a bridging 4,4ꞌ-bipyridine ligand, [Cd(S2COiPr)2(4,4ꞌ-bipy)]n [46]. The zero-dimensional aggregate seen in 3 has only one precedent in the literature, namely in the structure of [{Cd(S2COEt)2}2L2], where L is the S-bound thiourea derivative, bis(4-methoxyphenyl)thiourea [78] but resembles the almost universally adopted structural motif adopted by binary cadmium dithiocarbamates [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34]. As revealed in the previously mentioned review of the inverse coordination propensities of hmta in non-silver containing coordination polymers [67], µ2-, µ4-and µ4-bridging modes have been observed but terminally bound examples are comparatively rare in this context.…”