The crystal and molecular structure of the complex of zinc(II) with di-μ-diallyldithiocarbamate-bis(diallyldithiocarbamate)

Abstract

The structure of {Zn[S2CN(C3H5)2]2}2 was solved by X-ray structural analysis. The heavy atom method was used in interpretation of the structure. The dimeric compound crystallizes in the triclinic system with a space group of P1 and lattice parameters of a = 0.8218(2), b = 0.9462(6), c = 1.2942(9) nm, α = 77.70(5), β = 77.46(4), γ = 78.25(4)°. The experimentally determined density value for Z = 2 is 1.42 Mg m-3 and the calculated value is 1.44 Mg m-3. In the dimeric molecule each Zn atom is coordinated by five sulfur atoms at distances of Zn-S1 0.2346, Zn-S2 0.2339, Zn-S3 0.2468, Zn-S4 0.2846, Zn-S'4 0.2387 nm in a deformed trigonal bipyramid. The coordination number of Zn can be expressed as 3 + 1 + 1. The distance between two zinc atoms is 0.3580 nm.

Molecular architecture and supramolecular association in the zinc-triad 1,1-dithiolates. Steric control as a design element in crystal engineering?

“…The dinuclear motif (III) is adopted by 33 structures, with the majority containing zinc. A total of 15 zinc dithiocarbamates, 20,[31][32][33][34][35][36][37][38][39][40][41][42] one dithiophosphinate 43 and two dithiobenzoates 44 adopt this motif. For cadmium, seven dithiocarbamates [45][46][47][48][49][50][51][52] one dithiophosphate, 53 and three dithiophosphinate [54][55][56][57] compounds conform to this motif albeit with minor modifications for the dithiocarbamate sub-set (see below).…”

Mixed crystal of bis(μ2‐N,N‐di‐n‐butyldithiocarbamato‐S,S,S′)‐bis(N,N‐di‐n‐butyldithiocarbamato‐S,S′)‐di‐zinc(II) and bis(μ2‐N,N‐di‐n‐butyldithiopercarbamato‐S,O,O′)‐bis(N,N‐di‐n‐butyldithiocarbamato‐S,S′)‐di‐zinc(II)

“…Analogous centrosymmetric dimers shown in scheme 2 were also found in following pure zinc dithiocarbamates having less bulky ligands connected to the nitrogen atoms: bis(µ 2 -N,N-diallyldithiocarbamato-S,S,S')-bis(N,N-diallyldithiocarbamato-S,S')-di-zinc(II) [16], bis(µ 2 -N-butyl-N-ethyldithiocarbamato-S,S,S')-bis(N-butyl-N-ethyldithiocarbamato-S,S')-di-zinc(II) [17] , bis(µ 2 -N-methyl-N-phenyldithiocarbamato-S,S,S')-bis(N-methyl-N-phenyldithiocarbamato-S,S')-di-zinc(II) [18], bis(µ 2 -N,N-di-n-propyldithiocarbamato-S,S,S')-bis(N,N-di-n-propyldithio-carbamato-S,S')-di-zinc(II) [19] and bis(µ 2 -N-ethyl-N-isopropyldithiocarbamato-S,S,S')-bis(N-ethyl-N-isopropyldithiocarbamato-S,S')-di-zinc(II) [20]. In contrast to these compounds the zinc dithiocarbamate structures bis(N,N-dicylohexyldithiocarbamato)zinc(II) [21], bis(N-nbutyl-N-(3,5-di-tert-butyl-2-hydroxybenzyl)dithiocarbamato)zinc(II) [22], bis(N,N-dibenzyldithiocarba-mato) zinc(II) [23], and bis(N-cyclohexyl-N-methyldithiocarbamato)zinc(II) [24] feature more voluminous ligands.…”

“…X-ray crystal structure analysis Crystal data were collected at 293(2) K on an Enraf-Nonius CAD-4 diffractometer for a crystal of dimensions 0. 20 (3) 9447 (1) 252 (1) 3004 (1) 94(1) S (4) 10794 (6) 5143 (7) -658(9) -943(15) 560(30) C (7) 7364 ( (11) 10328 (4) 1407 (4) 4706 (5) 145(3) C (12) 10523 (4) 2018 (4) 4248 (7) 178(4) C (13) 10154 (5) 2789 (5) 4106 (9) 236(6) C (14) 10493 (7) 3428 (6) 3958 (15) 404(14) C (15) 11378 (3) 493 (6) 5801 (4) 160(4) C (16) 11986 (2) 708 (5) 5762 (5) 125(3) C (17) 12712 (3) 449 (6) 6741 (5) 160(4) C (18) 13312 (4) 691 (8) …”

Structural Organization of Nickel(II), Zinc(II), and Copper(II) Complexes with Diisobutyldithiocarbamate: EPR, 13C and 15N CP/MAS NMR, and X-Ray Diffraction Studies

“…Two of them, namely, terminal bidentate ligands, form four-membered chelate rings [ZnS 2 C], while the other two (bridging ligands) connect the adjacent Zn atoms. The resulting dimer includes an elongated nonplanar eight-membered chelate ring [Zn 2 S 4 C 2 ] in the chair [21][22][23][24][25][27][28][29][30][31] or tub conformation [19,20,26]. The coordination polyhedron of the zinc atom is a distorted tetrahedron or a trigonal bipyramid composed of sulfur atoms.…”

“…In contrast to nickel, zinc forms binuclear molecular structures [Zn 2 ( S 2 CNR 2 ) 4 ] [19][20][21][22][23][24][25][26][27][28][29][30][31] (R = CH 3 [19,20], C 2 H 5 [21][22][23], C 3 H 7 [24], i -C 3 H 7 [25], C 4 H 9 [26], and CH 2 CH = CH 2 [27] or R 2 = ( CH 2 ) 4 [28], ( CH 2 ) 6 [29] , CH 3 and C 2 H 5 , CH 3 and C 3 H 7 , CH 3 and i -C 3 H 7 , CH 3 and C 4 H 9 [30], and C 2 H 5 and cyclo -C 6 H 11 [31]), in which the dithiocarbamate ligands are structurally nonequivalent in pairs. Two of them, namely, terminal bidentate ligands, form four-membered chelate rings [ZnS 2 C], while the other two (bridging ligands) connect the adjacent Zn atoms.…”