Bis(μ-N-benzyl-N-tetra­decyl­dithio­carbamato-κ2 S:S′)bis­[(N-benzyl-N-tetra­decyl­dithio­carbamato-κ2 S,S′)zinc(II)]

Chun-Man Jia; Wen-Bing Yuan; Qiang Lin; Qi Zhang; Jie Pei

doi:10.1107/S1600536809011155

. 2009 Mar 31;65(Pt 4):m471. doi: 10.1107/S1600536809011155

Bis(μ-N-benzyl-N-tetradecyldithiocarbamato-κ² S:S′)bis[(N-benzyl-N-tetradecyldithiocarbamato-κ² S,S′)zinc(II)]

Chun-Man Jia ^a, Wen-Bing Yuan ^a, Qiang Lin ^a, Qi Zhang ^a,^*, Jie Pei ^a

PMCID: PMC2969063 PMID: 21582401

Abstract

In the title compound, [Zn₂(C₂₂H₃₆NS₂)₄], two bidentate dithiocarbamate groups chelate directly to the Zn^II atoms, whereas the two remaining dithiocarbamate ligands bridge the Zn atoms via a crystallographic inversion centre. The Zn atoms show a strongly distorted tetrahedral geometry. Adding the long S⋯S distance with the inversion centre being in the middle, the resulting five-coordinate geometry around the Zn atoms can be considered to be between distorted rectangular pyramidal and trigonal bipyramidal, with a calculated τ value of 0.31. In this dimer complex, two inversion-related tetradecyl carbon chains exhibit all-trans conformations, and the other two chains show a cis conformation at the end of the chains.

Related literature

For related centrosymmetric dimeric Zn^II structures, see: Baba, Farina, Othman et al. (2001 ▶); Baba, Farina, Kassim et al. (2001 ▶); Shaheen et al. (2006 ▶). For an analysis of five-coordinate metal atoms in the crystalline state, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Zn₂(C₂₂H₃₆NS₂)₄]
M _r = 1645.29
Triclinic,
a = 11.007 (1) Å
b = 11.640 (1) Å
c = 18.818 (2) Å
α = 85.645 (4)°
β = 76.913 (4)°
γ = 73.263 (4)°
V = 2248.7 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 153 K
0.43 × 0.10 × 0.10 mm

Data collection

Rigaku SPIDER diffractometer
Absorption correction: empirical (using intensity measurements) (ABSCOR; Higashi, 1995 ▶) T _min = 0.734, T _max = 0.928
15746 measured reflections
7979 independent reflections
7057 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.087
S = 1.01
7979 reflections
462 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 2004 ▶); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011155/si2160sup1.cif

e-65-0m471-sup1.cif^{(34.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011155/si2160Isup2.hkl

e-65-0m471-Isup2.hkl^{(390.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Enhanced figure: interactive version of Fig. 1

Table 1. Selected geometric parameters (Å, °).

Zn1—S4	2.3396 (6)
Zn1—S2	2.3398 (6)
Zn1—S3	2.3711 (6)
Zn1—S1	2.4420 (6)
Zn1—S3ⁱ	2.8879 (6)

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S4—Zn1—S2	136.18 (2)
S1—Zn1—S3ⁱ	154.92 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to the National Natural Science Foundation of China (grant No. 20761003, 20871061) and the National 973 Introducing Program (grant No. 2008CB617512) for financial support.

supplementary crystallographic information

Comment

Some crystal structures of centrosymmetric dimeric zinc^II–dithiocarbamate complexes have been reported, and this family compounds involve the similar ligands such as ethylisopropyldithiocarbamate (Baba, Farina, Othman et al., 2001), ethylbutyldithiocarbamate (Baba, Farina, Kassim et al., 2001) and piperidine-1-dithiocarbamate (Shaheen et al.,2006).

In the title complex (I), representing another member of dimeric dithiocarbamate complexes, two inversion related tetradecyl carbon chains exhibit all trans-conformations, and the other two chains show a cis-conformation at the end of the chains. The Zn–S bond lengths are within the sum of the covalent radii of 2.47 Å (S = 1.02 Å, Zn = 1.45 Å) (Table 1), and they agree with the values found in the literatures (Baba, Farina, Othman et al., 2001; 2001b; Shaheen et al., 2006). However, two of the six tetrahedral angles [S2–Zn1–S1=75.71°(2) and S4–Zn1–S2=136.18°(2)] differ greatly from the ideal value, 109.5°. Consequently, the longer distance of 2.8879 (6) Å for Zn1–S3A may be considered, which expands the view of a strongly distorted tetrahedral ZnS₄ evironment: if the symmetry related atom S3A (symmetry code: 2-x, -y, 1-z) is added to the Zn environment, a rectangular pyramidal or a trigonal bipyramidal geometry can be calculated by using the formula τ = (β - α)/60, which is applicable to five-co-ordinate structures within the structural continuum between trigonal bipyramidal and rectangular pyramidal (Addison et al., 1984). In this structure, the "rectangular" unit consists of S1, S2 S4, S3A, and S3 is considered as the axial atom. The largest angles within the four atoms S1-S3A are β = 154.92 (2)° for S1–Zn1–S3A and α = 136.18 (2)° for S2–Zn1–S4. As a result, τ is (154.92-136.18)/60 = 0.31, indicating a 69% rectangular pyramidal geometry.

Experimental

White crystals of (I) were obtained by slow evaporation of a solution in dichloromethane (10 ml) of benzyl(tetradecyl)carbamatodithioic acid (0.076 g, 0.2 mmol) and Zn(OAc)₂ (0.022 g, 0.1 mmol).