(Thio­cyanato-κS)­tris­(thio­urea-κS)mercury(II) chloride

A Shihabuddeen Syed; K Rajarajan; M NizamMohideen

doi:10.1107/S1600536813011847

. 2013 May 4;69(Pt 6):i33. doi: 10.1107/S1600536813011847

(Thiocyanato-κS)tris(thiourea-κS)mercury(II) chloride

A Shihabuddeen Syed ^a, K Rajarajan ^b,^*, M NizamMohideen ^c,^*

PMCID: PMC3684862 PMID: 23794964

Abstract

In the title salt, [Hg(NCS)(CH₄N₂S)₃]Cl, the Hg²⁺ ion is coordinated in a severely distorted tetrahedral manner by three thiourea groups and one thiocyanate anion through their S atoms. The S—Hg—S angles vary widely from 87.39 (5) to 128.02 (4)°. Weak intramolecular N—H⋯S hydrogen bonds are observed, which form S(6) ring motifs. In the crystal, the ions are linked by N—H⋯N and weak N—H⋯Cl interactions, generating a three-dimensional network.

Related literature

For background to mercury(II) complexes with thiourea and thiocyanate ligands, see: Nawaz et al. (2010 ▶). For hard and soft acids and bases, see: Ozutsmi et al. (1989 ▶); Bell et al. (2001 ▶). For related structures, see: Safari et al. (2009 ▶); Nawaz et al. (2010 ▶); Ramesh et al. (2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Hg(NCS)(CH₄N₂S)₃]Cl
M _r = 522.49
Orthorhombic,
a = 8.2175 (3) Å
b = 16.3257 (8) Å
c = 22.6793 (10) Å
V = 3042.6 (2) Å³
Z = 8
Mo Kα radiation
μ = 10.83 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.140, T _max = 0.221
38987 measured reflections
5125 independent reflections
3579 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.082
S = 1.05
5125 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 2.17 e Å⁻³
Δρ_min = −1.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(20.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011847/jj2165sup1.cif

e-69-00i33-sup1.cif^{(20.5KB, cif)}

Click here for additional data file.^{(246KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011847/jj2165Isup2.hkl

e-69-00i33-Isup2.hkl^{(246KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.86	2.48	3.277 (4)	155
N1—H1B⋯S2	0.86	2.76	3.475 (5)	142
N2—H2A⋯Cl1ⁱ	0.86	2.55	3.335 (4)	152
N3—H3B⋯Cl1	0.86	2.61	3.320 (5)	141
N4—H4B⋯Cl1ⁱⁱ	0.86	2.51	3.370 (5)	175
N5—H5B⋯Cl1	0.86	2.54	3.363 (4)	161
N5—H5A⋯N7ⁱⁱⁱ	0.86	2.11	2.933 (7)	160

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

Acknowledgments

The authors thank Dr Babu Vargheese, SAIF, IIT, Madras, India, for his help in collecting the X-ray intensity data. KR thanks the University Grants Commission, Government of India, for financial support granted under a Major Research Project [F. No.41–1008/2012 (SR)].

supplementary crystallographic information

Comment

This work is part of a research project concerning the investigation of thiourea (N₂H₄CS) and thiocyanate (SCN) based metal organic crystalline materials and their derivatives (Ramesh et al., 2012). Transition metal thiourea and thiocyanate coordination complexes are candidate materials for device applications including their nonlinear optical properties. As ligands, both thiourea and thiocyanate are interesting due to their potential formation of metalcoordination complexes as they exhibit multifunctional coordination modes due to the presence of 'S' and 'N' donor atoms. With reference to the hard and soft acids and bases) concept (Ozutsmi et al., 1989; Bell et al., 2001), thesoft cations show a pronounced affinity for coordination with the softer ligands, while hard cations prefer coordination with harder ligands. Several crystallographic reports about mercury(II) complexes usually consist of discrete monomeric molecules with tetrahedral (somewhat distorted) coordination environments around mercury(II) (Nawaz et al., 2010). Here, we report the synthesis and structure of the title salt, [(SC(2NH₂))₃(SCN^-)Hg(²⁺]⁺ . Cl^-,(I).

In (I), the Hg²⁺ ion is coordinated to three softer S atoms of thiourea and one softer S atom of a thiocyanate anion in addition to the isolated chlorine ion (Fig. 1). Intramolecular N—H···S hydrogen bonds are observed which form S(6) ring motifs (Bernstein et al., 1995). Bond distances and angles are in agreement with those reported for related compounds (Safari et al., 2009; Nawaz et al., 2010). The S—Hg—S angles vary widely from 87.39 (5)° to 128.02 (4)°, indicative of a distorted tetrahedral arrangement. The SCN^- moiety is planar [to within 0.007 (1) Å] with the C—N and C—S bond lengths corresponding to the values intermediate between single and double bonds. The S2—C4—N7 unit is nearly linear with a bond angle of 177.9 (6)°. In the crystal, the ions are stabilized by weak N—H···Cl, and N—H···N intermolecular interactions (Table.1) which form a three-dimensional network (Fig. 2).

Experimental

A mixture of thiourea, ammonium thiocyanate and mercury (II) choloride were dissolved in aqueous solution in the molar ratio 3:1:1 and thoroughly mixed for an hour to obtain a homogenous mixture. The solution was allowed to evaporate slowly at ambient temperature. Colourless single crystals suitable for single-crystal XRD were obtained in 12 days.