Bis(1,3-dibutylthiourea)dicyanido­mercury(II)

Saeed Ahmad; Haseeba Sadaf; Mehmet Akkurt; Shahzad Sharif; Islam Ullah Khan

doi:10.1107/S1600536809035594

. 2009 Sep 9;65(Pt 10):m1191–m1192. doi: 10.1107/S1600536809035594

Bis(1,3-dibutylthiourea)dicyanidomercury(II)

Saeed Ahmad ^a,^*, Haseeba Sadaf ^a, Mehmet Akkurt ^b,^*, Shahzad Sharif ^c, Islam Ullah Khan ^c

PMCID: PMC2970451 PMID: 21577723

Abstract

In the title compound, [Hg(CN)₂(C₉H₂₀N₂S)₂], the Hg atom lies on a twofold rotation axis. There is only half a molecule in the asymmetric unit. The Hg atom has a distorted tetrahedral coordination involving the S atoms of two 1-butyl-3-propylthiourea groups and the C atoms of the two CN⁻ anions. In the crystal packing, adjacent molecules are connected by intermolecular N—H⋯N and N—H⋯S hydrogen bonds, forming infinite chains in three dimensions.

Related literature

For the coordination chemistry of thiourea-type ligands, see: Nadeem et al. (2009 ▶, 2008 ▶); Zoufalá et al. (2007 ▶); Khan et al. (2007 ▶); Hanif et al. (2007 ▶); Fuks et al. (2005 ▶); Moro et al. (2009 ▶); Matesanz & Souza (2007 ▶). For crystallographic reports about mercury(II) complexes containing thioamides, see: Popovic et al. (2000 ▶, 2002 ▶); Pavlović et al. (2000 ▶); Jiang et al. (2001 ▶); Wu et al. (2004 ▶). For the spectroscopy and structural chemistry of cyanide complexes of silver(I) and gold(I) with thiones, see: Hanif et al. (2007 ▶); Wu et al. (2004 ▶); Ahmad, Isab & Ashraf (2002 ▶); Ahmad, Isab & Perzanowski (2002 ▶); Ashraf et al. (2002 ▶); Ahmad & Isab (2001 ▶); Ahmad (2004 ▶).

Experimental

Crystal data

[Hg(CN)₂(C₉H₂₀N₂S)₂]
M _r = 629.31
Monoclinic,
a = 17.4692 (3) Å
b = 9.5928 (2) Å
c = 17.4699 (4) Å
β = 111.540 (1)°
V = 2723.12 (10) Å³
Z = 4
Mo Kα radiation
μ = 5.82 mm⁻¹
T = 296 K
0.14 × 0.15 × 0.17 mm

Data collection

Bruker Kappa APEXII CCD area-detector diffractometer
Absorption correction: none
15120 measured reflections
3372 independent reflections
2918 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.044
S = 1.02
3372 reflections
134 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035594/bt5052sup1.cif

e-65-m1191-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035594/bt5052Isup2.hkl

e-65-m1191-Isup2.hkl^{(162.1KB, 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
N2—H2⋯S1ⁱ	0.86	2.68	3.479 (2)	155
N3—H3⋯N1ⁱⁱ	0.86	2.20	2.991 (3)	153
C7—H7B⋯S1	0.97	2.67	3.070 (3)	105

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

supplementary crystallographic information

Comment

The coordination chemistry of thiourea type ligands has been the subject of several recent studies because of the relevance of their binding sites to those in living systems (Nadeem et al., 2009; Nadeem et al., 2008; Zoufalá et al., 2007; Khan et al., 2007; Hanif et al., 2007; Fuks et al., 2005; Moro et al., 2009; Matesanz & Souza, 2007). Crystallographic reports about mercury (II) complexes containing thioamides establish that these ligands are coordinated via the sulfur atom(Popovic et al., 2000, 2002; Pavlović, Popović, Soldin et al., 2000; Jiang et al., 2001; Wu et al., 2004). We have been involved in investigating the spectral and structural chemistry of cyanido complexes of silver (I) and gold (I) with thiones with emphasis onligand scrambling reactions (Hanif et al., 2007; Wu et al., 2004; Ahmad, Isab & Ashraf, 2002; Ahmad, Isab & Perzanowski, 2002; Ashraf et al., 2002; Ahmad & Isab, 2001; Ahmad, 2004). As a part ofextension of our work towards complexation of Hg (CN)₂ with thiones, we report here the crystal structures of [(N,N^/-dibutylthiourea)₂Hg(CN)₂], (I).

In the title compound (I), (Fig. 1), the Hg anion lies on a twofold rotation axes paralel to the b axis in space group C2/c and one half of the molecule to the other half are connected by this symmetry operation. The Hg atom has a distorted tetrahedral coordination by the S atoms of two N,N^/-dibutylthiourea groups and the C atoms of the two CN groups. The bond distances Hg—S and Hg—C are 2.7424 (7) Å and 2.072 (3) Å, and the bond angles C—Hg—C, S—Hg—S and C—Hg—C are 150.51 (11)°, 95.55 (2)° and 100.45 (8)°. All bond lengths and bond angles in (I) are in the range of expected values.

In the crystal packing, the adjacent molecules are connected by intermolecular N—H···N and N—H···S hydrogen bonds (Table 1). In Fig. 2, the packing and hydrogen bonding of (I) are shown viewed down b axis.

Experimental

For the preparation of the title complex, Hg (CN)₂ was prepared first by the reaction of 1 mmol HgCl₂ in methanol with 2 mmole of KCN in water. Then 0.253 g (1 mmole) Hg (CN)₂ dissolved in15 ml methanol was mixed with 2 equivalents of N,N^/-dibutylthiourea in 15 methanol. After stirring for 15 minutes, the resulting mixture was filtered and filtrate was kept at room temperature. After 24 h white crystals were obtained.