Crystal structure of di­chlorido­bis­(N,N′-di­methyl­thio­urea-κS)mercury(II)

Shaheen, M.A.; Munawar, A.; Sadaf, H.; Tahir, M.N.; Isab, A.A.; Ahmad, S.

doi:10.1107/S2056989015015406

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Volume 71| Part 9| September 2015| Pages 1061-1063

https://doi.org/10.1107/S2056989015015406

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Crystal structure of dichloridobis(N,N′-dimethylthiourea-κS)mercury(II)

Muhammad Ashraf Shaheen,^a Aisha Munawar,^b Haseeba Sadaf,^b Muhammad Nawaz Tahir,^c ^* Anvarhusein A. Isab ^d and Saeed Ahmad ^b

^aDepartment of Chemistry, University of Sargodha, Sargodha, Punjab, Pakistan, ^bDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan, ^cDepartment of Physics, University of Sargodha, Sargodha, Punjab, Pakistan, and ^dDepartment of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
^*Correspondence e-mail: dmntahir_uos@yahoo.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 6 August 2015; accepted 18 August 2015; online 22 August 2015)

The molecular structure of the title compound, [HgCl₂(C₃H₈N₂S)₂], has point group symmetry 2, with the twofold rotation axis passing through the Hg^II atom. The latter is coordinated by two Cl atoms and two N,N′-dimethylthiourea (Dmtu) ligands through their S atoms, defining a distorted tetrahedral coordination sphere with bond angles in the range 102.47 (4)–118.32 (4)°. Intra- and intermolecular hydrogen bonds of the type N—H⋯Cl with S(6) and R₂²(12) ring motifs are present. The intermolecular contacts make up polymeric chains extending parallel to [101].

Keywords: crystal structure; mercury; dimethylthiourea; hydrogen bonding.

CCDC reference: 1419298

1. Chemical context

X-ray structural studies of mercury(II) complexes with thiourea ligands (L) or derivatives thereof have shown that in combination with a halide or pseudohalide X, some of the complexes exist as mononuclear species [HgX₂L₂] (Popović et al., 2000 ), while the others exist in a dimeric or polymeric form as [HgX₂L]_n (Bell et al., 2001 ) in the solid state. In both types of complexes, monomeric (1:2) or polymeric (1:1), the coordination environment around Hg^II is distorted tetrahedral or pseudo-tetrahedral. We have recently reported the crystal structures of HgCl₂ and Hg(CN)₂ complexes with methylthiourea as an auxiliary ligand (Isab et al., 2011 ), N,N′-dimethylthiourea (Malik et al., 2010a ), N,N′-diethylthiourea (Mufakkar et al., 2010 ), N,N′-dibutylthiourea (Ahmad et al., 2009 ) and tetramethylthiourea (Nawaz et al., 2010 ).

In this article, we report on synthesis and crystal structure of HgCl₂ with dimethylthiourea (Dmtu) as an additional ligand, [HgCl₂(C₃H₈N₂S)₂], (I).

2. Structural comments

The mercury atom in complex (I) lies on a twofold rotation axis (Fig. 1). It exhibits a distorted tetrahedral coordination environment defined by two S atoms of symmetry-related Dmtu ligands and two Cl atoms. The S—Hg—S bond angle is 118.32 (4)°. At 102.47 (4)°, the Cl—Hg—Cl bond angle is significantly smaller, which can be attributed to the bulkier Dmtu ligands. The Hg—S, Hg—Cl and other bond lengths (Table 1) have similar values compared with other [HgCl₂L₂] complexes (Ahmad et al., 2009; Isab et al., 2011; Malik et al., 2010a; Mufakkar et al., 2010; Popović et al., 2000). In (I), the N—(C=S)—N skeleton of the Dmtu ligand is essentially planar with an r.m.s. deviation of 0.0135 Å.

Table 1
Selected bond lengths (Å)

Hg1—S1	2.4622 (7)	Hg1—Cl1	2.5589 (7)

Figure 1
The molecular structure of compound (I)

. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small circles of arbitrary radius. [Symmetry code: (i) −x + 1, y, −z + $[{3\over 2}]$ .]

3. Supramolecular features

From a supramolecular point of view, adjacent molecules are connected by intermolecular N2—H2⋯Cl1 hydrogen bonds (Table 2, Fig. 2) into R₂²(12) ring motifs (Bernstein et al., 1995 ). The supramolecular chains formed this way extend parallel to [101]. Additional intramolecular hydrogen bonds N1—H1⋯Cl1 (Table 2) with S(6) loop motifs (Bernstein et al., 1995) are also present.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl1	0.86	2.37	3.223 (3)	170
N2—H2⋯Cl1ⁱ	0.86	2.49	3.270 (3)	151
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Crystal packing of compound (I)

viewed approximately along [010]. N—H⋯Cl hydrogen bonds are shown as dashed lines (see Table 2

for details).

4. Database survey

A systematic search in the Cambridge Structural Database (Groom & Allen, 2014 ) revealed a total of 25 hits for mercury chloride complexes with thiourea ligands. The title compound is isotypic with the Zn and Cd analogues [ZnCl₂(Dmtu)₂] (Burrows et al., 2004 ) and [CdCl₂(Dmtu)₂] (Malik et al., 2010b ) and with [CdBr₂(Dmtu)₂] (Ahmad et al., 2011 ). The Hg^II atom in the structure of (I) shows an equivalent degree of distortion from the tetrahedral configuration as the metals in [Zn(Dmtu)₂Cl₂] and [Hg(tetramethylthiourea)₂Cl₂] (Nawaz et al., 2010) in which the bond angles at the metal atom vary from 104.35 (2) to 113.30 (2)° and from 104.08 (4) to 120.75 (4)°, respectively. However, in [CdCl₂(Dmtu)₂] and [CdBr₂(Dmtu)₂], the coordination spheres around Cd deviate only slightly from ideal tetrahedral values. On the other hand in [Hg(Dmtu)₂(CN)₂], the Hg^II atom exhibits a severely distorted tetrahedral coordination sphere with bond angles in the range 94.31 (2) to 148.83 (13)° (Malik et al., 2010a).

5. Synthesis and crystallization

For the preparation of title complex, 0.27 g (1 mmol) HgCl₂ dissolved in 4 ml dimethylsulfoxide were mixed with two equivalents of N,N′-dimethylthiourea in 10 ml acetonitrile. After stirring for 15 minutes, the resulting solution was filtered and the filtrate kept at room temperature. After one day colourless crystals were obtained. Yield ca. 60%.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms were positioned geometrically (C—H = 0.96 Å, N—H= 0.86 Å) and refined as riding with U_iso(H) = 1.5U_eq(C) and U_iso(H) = 1.2U_eq(N).

Table 3
Experimental details

Crystal data
Chemical formula	[HgCl₂(C₃H₈NS)₂]
M_r	479.84
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	13.1434 (12), 8.9971 (3), 12.6596 (9)
β (°)	107.955 (4)
V (Å³)	1424.12 (17)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	11.45
Crystal size (mm)	0.36 × 0.18 × 0.16

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2007 )
T_min, T_max	0.106, 0.265
No. of measured, independent and observed [I > 2σ(I)] reflections	12262, 1721, 1556
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.018, 0.038, 1.06
No. of reflections	1721
No. of parameters	71
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008 ), SHELXL2014/6 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1419298

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989015015406/wm5202sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015406/wm5202Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/6 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).

Dichloridobis(N,N'-dimethylthiourea-κS)mercury(II) top

Crystal data top

[HgCl₂(C₃H₈NS)₂]	F(000) = 904
M_r = 479.84	D_x = 2.238 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.1434 (12) Å	Cell parameters from 1556 reflections
b = 8.9971 (3) Å	θ = 3.0–28.0°
c = 12.6596 (9) Å	µ = 11.45 mm⁻¹
β = 107.955 (4)°	T = 296 K
V = 1424.12 (17) Å³	Lath, colourless
Z = 4	0.36 × 0.18 × 0.16 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1721 independent reflections
Radiation source: fine-focus sealed tube	1556 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
Detector resolution: 7.50 pixels mm^-1	θ_max = 28.0°, θ_min = 3.0°
ω scans	h = −16→17
Absorption correction: multi-scan (SADABS; Bruker, 2007)	k = −11→11
T_min = 0.106, T_max = 0.265	l = −16→16
12262 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.018	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.038	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0168P)² + 0.595P] where P = (F_o² + 2F_c²)/3
1721 reflections	(Δ/σ)_max = 0.001
71 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Hg1	0.5000	0.37748 (2)	0.7500	0.04175 (6)
Cl1	0.60610 (6)	0.19941 (10)	0.66623 (6)	0.05387 (19)
S1	0.36846 (7)	0.51777 (8)	0.60297 (6)	0.04873 (19)
N1	0.40138 (19)	0.3089 (3)	0.4670 (2)	0.0464 (6)
H1	0.4588	0.2910	0.5206	0.056*
N2	0.24749 (19)	0.4417 (3)	0.4042 (2)	0.0433 (5)
H2	0.2332	0.3894	0.3446	0.052*
C1	0.3374 (2)	0.4131 (3)	0.4824 (2)	0.0362 (6)
C2	0.3824 (3)	0.2226 (4)	0.3672 (3)	0.0553 (8)
H2A	0.4381	0.1500	0.3772	0.083*
H2B	0.3819	0.2870	0.3066	0.083*
H2C	0.3146	0.1732	0.3513	0.083*
C3	0.1704 (3)	0.5533 (4)	0.4096 (3)	0.0580 (9)
H3A	0.1572	0.5471	0.4800	0.087*
H3B	0.1048	0.5371	0.3509	0.087*
H3C	0.1978	0.6501	0.4015	0.087*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.04156 (10)	0.04908 (9)	0.02828 (9)	0.000	0.00146 (7)	0.000
Cl1	0.0503 (4)	0.0684 (5)	0.0368 (4)	0.0220 (4)	0.0044 (3)	−0.0017 (3)
S1	0.0591 (5)	0.0440 (4)	0.0315 (4)	0.0151 (3)	−0.0031 (3)	−0.0054 (3)
N1	0.0395 (14)	0.0570 (14)	0.0344 (13)	0.0126 (11)	−0.0007 (11)	−0.0056 (11)
N2	0.0425 (14)	0.0480 (12)	0.0308 (12)	0.0096 (11)	−0.0011 (11)	−0.0027 (11)
C1	0.0366 (16)	0.0375 (13)	0.0314 (14)	0.0001 (10)	0.0059 (12)	0.0026 (10)
C2	0.056 (2)	0.0626 (19)	0.0429 (18)	0.0096 (15)	0.0091 (16)	−0.0154 (15)
C3	0.051 (2)	0.067 (2)	0.0443 (19)	0.0258 (17)	−0.0017 (15)	−0.0002 (16)

Geometric parameters (Å, º) top

Hg1—S1	2.4622 (7)	N2—C3	1.444 (4)
Hg1—S1ⁱ	2.4622 (7)	N2—H2	0.8600
Hg1—Cl1	2.5589 (7)	C2—H2A	0.9600
Hg1—Cl1ⁱ	2.5589 (7)	C2—H2B	0.9600
S1—C1	1.732 (3)	C2—H2C	0.9600
N1—C1	1.313 (4)	C3—H3A	0.9600
N1—C2	1.438 (4)	C3—H3B	0.9600
N1—H1	0.8600	C3—H3C	0.9600
N2—C1	1.312 (4)

S1—Hg1—S1ⁱ	118.32 (4)	N2—C1—S1	118.1 (2)
S1—Hg1—Cl1	110.67 (2)	N1—C1—S1	122.1 (2)
S1ⁱ—Hg1—Cl1	106.79 (3)	N1—C2—H2A	109.5
S1—Hg1—Cl1ⁱ	106.79 (3)	N1—C2—H2B	109.5
S1ⁱ—Hg1—Cl1ⁱ	110.67 (2)	H2A—C2—H2B	109.5
Cl1—Hg1—Cl1ⁱ	102.47 (4)	N1—C2—H2C	109.5
C1—S1—Hg1	107.88 (9)	H2A—C2—H2C	109.5
C1—N1—C2	124.8 (3)	H2B—C2—H2C	109.5
C1—N1—H1	117.6	N2—C3—H3A	109.5
C2—N1—H1	117.6	N2—C3—H3B	109.5
C1—N2—C3	125.7 (3)	H3A—C3—H3B	109.5
C1—N2—H2	117.2	N2—C3—H3C	109.5
C3—N2—H2	117.2	H3A—C3—H3C	109.5
N2—C1—N1	119.8 (3)	H3B—C3—H3C	109.5

C3—N2—C1—N1	−179.5 (3)	C2—N1—C1—S1	−177.2 (2)
C3—N2—C1—S1	−0.5 (4)	Hg1—S1—C1—N2	159.3 (2)
C2—N1—C1—N2	1.8 (5)	Hg1—S1—C1—N1	−21.6 (3)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.86	2.37	3.223 (3)	170
N2—H2···Cl1ⁱⁱ	0.86	2.49	3.270 (3)	151

Symmetry code: (ii) x−1/2, −y+1/2, z−1/2.

Acknowledgements

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

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