cyclo-Tetrakis(μ2-3-sulfidopropyl-κ3 C 1,S:S)tetrakis[chloridocobalt(III)]

Shafique Ahmad Awan; M Nawaz Tahir; Iram Khushi Muhammad; Saeed Ahmad; Muhammad Ilyas Tariq

doi:10.1107/S1600536811013067

This article has been retracted.

Retraction in: Acta Crystallogr Sect E Struct Rep Online. 2012 May 26;68(Pt 6):e13 See also: PMC Retraction Policy

. 2011 Apr 13;67(Pt 5):m576–m577. doi: 10.1107/S1600536811013067

cyclo-Tetrakis(μ₂-3-sulfidopropyl-κ³ C ¹,S:S)tetrakis[chloridocobalt(III)]

Shafique Ahmad Awan ^a, M Nawaz Tahir ^b,^*, Iram Khushi Muhammad ^c, Saeed Ahmad ^c, Muhammad Ilyas Tariq ^d

PMCID: PMC3089308 PMID: 21754303

Abstract

In the centrosymmetric title compound, [Co₄Cl₄(C₃H₆S)]₄], the two independent Co^III ions are each coordinated in a distorted tetrahedral geometry by one C, one Cl and two S atoms. The molecules are stabilized by C—H⋯Cl hydrogen bonds. In the crystal, intermolecular C—H⋯Cl and C—H⋯S hydrogen bonds with R ₂ ²(8), R ₄ ²(8) and R ₂ ²(6) ring motifs generate a polymeric network.

Related literature

For related background see: Shahid et al. (2009 ▶); Altaf et al. (2010 ▶). For related structures, see: Duan et al. (1997 ▶); Tremel et al. (1992 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Co₄Cl₄(C₃H₆S)]₄]
M _r = 674.07
Monoclinic,
a = 23.6135 (12) Å
b = 7.8465 (3) Å
c = 16.8693 (9) Å
β = 130.440 (4)°
V = 2378.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 3.54 mm⁻¹
T = 296 K
0.24 × 0.16 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.675, T _max = 0.683
13736 measured reflections
2152 independent reflections
1782 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.125
S = 1.04
2152 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013067/si2349sup1.cif

e-67-0m576-sup1.cif^{(22.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013067/si2349Isup2.hkl

e-67-0m576-Isup2.hkl^{(103.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—Cl1	2.228 (2)
Co1—S1	2.3570 (17)
Co1—S2	2.318 (2)
Co1—C3	2.038 (6)
Co2—Cl2	2.236 (3)
Co2—S1	2.305 (2)
Co2—S2ⁱ	2.3648 (16)
Co2—C6ⁱ	2.051 (6)
S1—C1	1.826 (7)
S2—C4	1.837 (8)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯S2ⁱⁱ	0.97	2.57	3.539 (8)	175
C3—H3B⋯Cl2ⁱⁱⁱ	0.97	2.74	3.512 (7)	138
C3—H3B⋯Cl2^iv	0.97	2.81	3.412 (6)	121
C6—H6A⋯Cl1ⁱ	0.97	2.62	3.379 (7)	135
C6—H6B⋯Cl1^v	0.97	2.48	3.343 (7)	148

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

The authors acknowledge the provision of funds for the purchase of the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

Comment

Recently, we have reported the crystal structure of zinc(II) and mercury(II) complexes of pyrrolidinedithiocarbamate (PDTC) (Shahid et al., 2009) & (Altaf, et al., 2010). In the present study, we attempted to prepare a cobalt(II) complex with PDTC, but surprisingly the title compound (I, Fig. 1) was isolated, the crystal structure of which is being presented.

The crystal structure of (II) i.e, tetranuclear molecular square[Co(HL)]₄⁴⁺ [H₂L = tetra(2-pyridyl)thiocarbazone] (Duan et al., 1997) and (III) i.e., bis(tetraethylammonium) hexakis(µ₂-phenylthiolato)-tetrachloro-tetra -cobalt acetonitrile solvate (Tremel et al., 1992) have been published which are related to the title compound (I).

The crystal structure of the title compound (I) is centrosymmetric. The coordination around two independent Coⁱⁱⁱ ions is distorted tetrahedral from one C, Cl and two S-atoms. The range of Co—C [2.038 (6)–2.051 (6) Å] is shorter compared to Co—S [2.305 (2)–2.3648 (16) Å]. The Co—Cl bonds have values of 2.228 (2) and 2.236 (2) Å. The important bond distances are given in Table 1. The molecules are stabilized in the form of a polymeric network due to C—H···Cl and C—H···S intermolecular H-bonds (Table 2) forming R₂²(8), R₄²(8) and R₂²(6) ring motifs (Bernstein et al., 1995).

Experimental

The title compound was prepared by adding two equivalents of ammonium pyrrolidinedithiocarbamate (PDTC) in 15 ml methanol to a solution of CoCl₂.6H₂O in 10 ml methanol. The addition of PDTC in the pink colored metal ion solution resulted in the formation of green precipitates immediately. After stirring for half an hour, the precipitates were filtered off and dried. The blackish brown crystals of the title compound (I) were prepared by dissolving 0.03 g precipitates in 3 ml DMSO on heating in a vial and then cooling the resulting solution at room temperature.