metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

Di­chloridobis(N,N,N′,N′-tetra­methyl­thio­urea-κS)mercury(II)

aDepartment of Chemistry, University of Engineering and Technology, Lahore 54890, Pakistan, and bDepartment of Chemistry, King Fahd University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
*Correspondence e-mail: saeed_a786@hotmail.com

(Received 8 July 2010; accepted 14 July 2010; online 17 July 2010)

In the title compound, [HgCl2(C5H12N2S)2], the HgII atom is located on a twofold rotation axis and is bonded in a distorted tetra­hedral coordination mode to two chloride ions and to two tetra­methyl­thio­urea (tmtu) mol­ecules through their S atoms. The crystal structure is stabilized by C—H⋯N and C—H⋯S hydrogen bonds.

Related literature

For background to Hg(II) complexes with thio­urea ligands, see: Ahmad et al. (2009[Ahmad, S., Sadaf, H., Akkurt, M., Sharif, S. & Khan, I. U. (2009). Acta Cryst. E65, m1191-m1192.]); Chieh (1977[Chieh, C. (1977). Can. J. Chem. 55, 1583-1587.]); Lobana et al. (2008[Lobana, T. S., Sharma, R., Sharma, R., Sultana, R. & Butcher, R. J. (2008). Z. Anorg. Allg. Chem. 634, 718-723.]); Popovic et al. (2000[Popovic, Z., Pavlovic, G., Matkovic-Calogovic, D., Soldin, Z., Rajic, M., Vikic-Topic, D. & Kovacek, D. (2000). Inorg. Chim. Acta, 306, 142-152.], 2002[Popovic, Z., Soldin, Z. G., Pavlovic, G., Matkovic-Calogovic, D., Mrvos-Sermek, D. & Rajic, M. (2002). Struct. Chem. 13, 425-436.]). The structure of the title compound is isotypic with [Cd(tmtu)2Br2] (Nawaz et al., 2010a[Nawaz, S., Sadaf, S., Fettouhi, M., Fazal, A. & Ahmad, S. (2010a). Acta Cryst. E66, m950.]) and [Cd(tmtu)2I2] (Nawaz et al., 2010b[Nawaz, S., Sadaf, S., Fettouhi, M., Fazal, A. & Ahmad, S. (2010b). Acta Cryst. E66, m951.]).

[Scheme 1]

Experimental

Crystal data
  • [HgCl2(C5H12N2S)2]

  • Mr = 535.94

  • Monoclinic, C 2/c

  • a = 18.7418 (12) Å

  • b = 9.5920 (6) Å

  • c = 13.5177 (9) Å

  • β = 130.834 (1)°

  • V = 1838.6 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 8.88 mm−1

  • T = 293 K

  • 0.29 × 0.24 × 0.11 mm

Data collection
  • Bruker SMART APEX area detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.183, Tmax = 0.442

  • 12167 measured reflections

  • 2281 independent reflections

  • 2103 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.020

  • wR(F2) = 0.040

  • S = 1.07

  • 2281 reflections

  • 92 parameters

  • H-atom parameters constrained

  • Δρmax = 0.72 e Å−3

  • Δρmin = −0.79 e Å−3

Table 1
Selected bond lengths (Å)

Hg1—Cl1 2.5028 (8)
Hg1—S1 2.5329 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C2—H2A⋯N2 0.96 2.52 2.849 (6) 100
C3—H3A⋯S1 0.96 2.68 2.996 (6) 100
C5—H5A⋯S1 0.96 2.62 3.024 (5) 105

Data collection: SMART (Bruker, 2008[Bruker (2008). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

The coordination chemistry of mercury(II) complexes with thiourea type ligands has been the subject of several recent studies because of the importance of such systems as structural models in biology (Popovic et al., 2000; 2002). Mercury(II) is known form a wide variety of 1:1 and 1:2 complexes of the types LHgX2 (Popovic et al., 2002) and L2HgX2 (Ahmad et al., 2009; Chieh, 1977: Lobana et al., 2008), where X is a halide or pseudohalide, having structural arrangements entirely based on tetrahedral or pseudo-tetrahedral environments. We have recently reported the crystal structure of a Hg(CN)2 complex of N,N'-dibutylthiourea (dbtu) (Ahmad et al., 2009). Herein we report on the crystal structure of a mercury(II) chloride complex of tetramethylthiourea (tmtu), [Hg(C5H12N2S2)2Cl2], (I) .

The crystal structure of (I) consists of discrete molecular species in which the mercury atom is located on a twofold rotation axis (Fig. 1) and is bonded in a distorted tetrahedral coordination mode to two chloride ions and to two tetramethylthiourea (tmtu) molecules. The Hg—S and Hg—Cl bond lengths are 2.5329 (7) and 2.5028 (8) Å, respectively. The bond angles around Hg are in the range expected for a tetrahedral coordination, with the S—Hg—S angle (120.75 (4)°) having the largest deviation from the ideal value. The main cause of this deviation is the steric interaction between the —CH3 groups. The SCN2— moiety of Tmtu is essentially planar with the C—N and C—S bond lengths corresponding to the values intermediate between single and double bonds.

The structure of the title compound is isotypic with [Cd(tmtu)2Br2] (Nawaz et al., 2010a) and [Cd(tmtu)2I2] (Nawaz et al., 2010b).

For a more detailed description of the structure, see: Nawaz et al. (2010a).

Related literature top

For background to Hg(II) complexes with thiourea ligands, see: Ahmad et al. (2009); Chieh (1977); Lobana et al. (2008); Popovic et al. (2000, 2002). The structure of the title compound is isotypic with [Cd(tmtu)2Br2] (Nawaz et al., 2010a) and [Cd(tmtu)2I2] (Nawaz et al., 2010b).

Experimental top

To 0.27 g (1.0 mmol) mercury(II) chloride in 10 ml methanol was added two equivalents of tetramethylthiourea in 15 ml methanol. A clear solution was obtained that was stirred for 30 minutes. The colorless solution was filtered and the filtrate was kept at room temperature for crystallization. As a result, a white crystalline product was obtained, that was finally washed with methanol and dried.

Refinement top

H atoms were placed in calculated positions with a C—H distance of 0.96 Å and Uiso(H) = 1.5 Ueq(C).

Structure description top

The coordination chemistry of mercury(II) complexes with thiourea type ligands has been the subject of several recent studies because of the importance of such systems as structural models in biology (Popovic et al., 2000; 2002). Mercury(II) is known form a wide variety of 1:1 and 1:2 complexes of the types LHgX2 (Popovic et al., 2002) and L2HgX2 (Ahmad et al., 2009; Chieh, 1977: Lobana et al., 2008), where X is a halide or pseudohalide, having structural arrangements entirely based on tetrahedral or pseudo-tetrahedral environments. We have recently reported the crystal structure of a Hg(CN)2 complex of N,N'-dibutylthiourea (dbtu) (Ahmad et al., 2009). Herein we report on the crystal structure of a mercury(II) chloride complex of tetramethylthiourea (tmtu), [Hg(C5H12N2S2)2Cl2], (I) .

The crystal structure of (I) consists of discrete molecular species in which the mercury atom is located on a twofold rotation axis (Fig. 1) and is bonded in a distorted tetrahedral coordination mode to two chloride ions and to two tetramethylthiourea (tmtu) molecules. The Hg—S and Hg—Cl bond lengths are 2.5329 (7) and 2.5028 (8) Å, respectively. The bond angles around Hg are in the range expected for a tetrahedral coordination, with the S—Hg—S angle (120.75 (4)°) having the largest deviation from the ideal value. The main cause of this deviation is the steric interaction between the —CH3 groups. The SCN2— moiety of Tmtu is essentially planar with the C—N and C—S bond lengths corresponding to the values intermediate between single and double bonds.

The structure of the title compound is isotypic with [Cd(tmtu)2Br2] (Nawaz et al., 2010a) and [Cd(tmtu)2I2] (Nawaz et al., 2010b).

For a more detailed description of the structure, see: Nawaz et al. (2010a).

For background to Hg(II) complexes with thiourea ligands, see: Ahmad et al. (2009); Chieh (1977); Lobana et al. (2008); Popovic et al. (2000, 2002). The structure of the title compound is isotypic with [Cd(tmtu)2Br2] (Nawaz et al., 2010a) and [Cd(tmtu)2I2] (Nawaz et al., 2010b).

Computing details top

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound with atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H-atoms were omitted for clarity.
Dichloridobis(N,N,N',N'-tetramethylthiourea- κS)mercury(II) top
Crystal data top
[HgCl2(C5H12N2S)2]F(000) = 1032
Mr = 535.94Dx = 1.936 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 12167 reflections
a = 18.7418 (12) Åθ = 2.6–28.3°
b = 9.5920 (6) ŵ = 8.88 mm1
c = 13.5177 (9) ÅT = 293 K
β = 130.834 (1)°Colourless, plate
V = 1838.6 (2) Å30.29 × 0.24 × 0.11 mm
Z = 4
Data collection top
Bruker SMART APEX area detector
diffractometer
2281 independent reflections
Radiation source: normal-focus sealed tube2103 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ω scansθmax = 28.3°, θmin = 2.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2424
Tmin = 0.183, Tmax = 0.442k = 1212
12167 measured reflectionsl = 1818
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.020H-atom parameters constrained
wR(F2) = 0.040 w = 1/[σ2(Fo2) + (0.0109P)2 + 2.5249P]
where P = (Fo2 + 2Fc2)/3
S = 1.07(Δ/σ)max = 0.002
2281 reflectionsΔρmax = 0.72 e Å3
92 parametersΔρmin = 0.79 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00244 (8)
Crystal data top
[HgCl2(C5H12N2S)2]V = 1838.6 (2) Å3
Mr = 535.94Z = 4
Monoclinic, C2/cMo Kα radiation
a = 18.7418 (12) ŵ = 8.88 mm1
b = 9.5920 (6) ÅT = 293 K
c = 13.5177 (9) Å0.29 × 0.24 × 0.11 mm
β = 130.834 (1)°
Data collection top
Bruker SMART APEX area detector
diffractometer
2281 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2103 reflections with I > 2σ(I)
Tmin = 0.183, Tmax = 0.442Rint = 0.031
12167 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0200 restraints
wR(F2) = 0.040H-atom parameters constrained
S = 1.07Δρmax = 0.72 e Å3
2281 reflectionsΔρmin = 0.79 e Å3
92 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
xyzUiso*/Ueq
Hg11.00000.703186 (17)0.25000.04539 (7)
Cl11.14323 (5)0.55933 (9)0.34397 (8)0.0591 (2)
S11.02994 (5)0.83371 (9)0.43697 (7)0.04983 (18)
N10.91286 (18)0.7622 (3)0.4747 (3)0.0482 (6)
N20.84430 (16)0.8798 (3)0.2830 (2)0.0488 (6)
C10.92029 (18)0.8240 (3)0.3933 (3)0.0367 (5)
C20.8466 (3)0.8103 (4)0.4900 (4)0.0704 (10)
H2A0.81920.89710.44460.106*
H2B0.87930.82320.58120.106*
H2C0.79770.74210.45420.106*
C30.9842 (3)0.6647 (4)0.5756 (4)0.0769 (11)
H3A1.01310.61820.54680.115*
H3B0.95490.59700.59140.115*
H3C1.03130.71490.65480.115*
C40.7491 (2)0.8240 (5)0.2114 (4)0.0802 (12)
H4A0.75310.73290.24410.120*
H4B0.71740.81790.12000.120*
H4C0.71440.88470.22310.120*
C50.8518 (3)0.9798 (4)0.2094 (4)0.0774 (11)
H5A0.91211.02500.26690.116*
H5B0.80271.04830.17110.116*
H5C0.84540.93230.14140.116*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.05014 (10)0.04849 (10)0.05259 (11)0.0000.04018 (9)0.000
Cl10.0519 (4)0.0599 (5)0.0652 (5)0.0126 (3)0.0381 (4)0.0065 (4)
S10.0386 (3)0.0716 (5)0.0453 (4)0.0091 (3)0.0300 (3)0.0142 (3)
N10.0611 (15)0.0488 (13)0.0566 (14)0.0005 (11)0.0480 (13)0.0002 (11)
N20.0439 (13)0.0560 (15)0.0465 (13)0.0051 (11)0.0295 (11)0.0020 (11)
C10.0415 (13)0.0364 (13)0.0415 (13)0.0023 (10)0.0312 (12)0.0061 (10)
C20.085 (2)0.081 (3)0.092 (3)0.011 (2)0.078 (2)0.014 (2)
C30.098 (3)0.070 (2)0.076 (2)0.015 (2)0.063 (2)0.024 (2)
C40.0387 (17)0.116 (3)0.070 (2)0.0013 (18)0.0292 (17)0.015 (2)
C50.088 (3)0.081 (3)0.069 (2)0.027 (2)0.054 (2)0.029 (2)
Geometric parameters (Å, º) top
Hg1—Cl1i2.5028 (8)C2—H2B0.9600
Hg1—Cl12.5028 (8)C2—H2C0.9600
Hg1—S12.5329 (7)C3—H3A0.9600
Hg1—S1i2.5329 (7)C3—H3B0.9600
S1—C11.730 (3)C3—H3C0.9600
N1—C11.336 (3)C4—H4A0.9600
N1—C21.460 (4)C4—H4B0.9600
N1—C31.461 (4)C4—H4C0.9600
N2—C11.327 (3)C5—H5A0.9600
N2—C51.453 (4)C5—H5B0.9600
N2—C41.466 (4)C5—H5C0.9600
C2—H2A0.9600
Cl1i—Hg1—Cl1113.08 (4)H2A—C2—H2C109.5
Cl1i—Hg1—S1104.08 (3)H2B—C2—H2C109.5
Cl1—Hg1—S1107.56 (3)N1—C3—H3A109.5
Cl1i—Hg1—S1i107.56 (3)N1—C3—H3B109.5
Cl1—Hg1—S1i104.08 (3)H3A—C3—H3B109.5
S1—Hg1—S1i120.75 (4)N1—C3—H3C109.5
C1—S1—Hg1101.20 (9)H3A—C3—H3C109.5
C1—N1—C2122.2 (3)H3B—C3—H3C109.5
C1—N1—C3121.9 (3)N2—C4—H4A109.5
C2—N1—C3114.4 (3)N2—C4—H4B109.5
C1—N2—C5121.5 (3)H4A—C4—H4B109.5
C1—N2—C4122.9 (3)N2—C4—H4C109.5
C5—N2—C4114.2 (3)H4A—C4—H4C109.5
N2—C1—N1119.5 (2)H4B—C4—H4C109.5
N2—C1—S1121.6 (2)N2—C5—H5A109.5
N1—C1—S1118.9 (2)N2—C5—H5B109.5
N1—C2—H2A109.5H5A—C5—H5B109.5
N1—C2—H2B109.5N2—C5—H5C109.5
H2A—C2—H2B109.5H5A—C5—H5C109.5
N1—C2—H2C109.5H5B—C5—H5C109.5
Symmetry code: (i) x+2, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···N20.962.522.849 (6)100
C3—H3A···S10.962.682.996 (6)100
C5—H5A···S10.962.623.024 (5)105

Experimental details

Crystal data
Chemical formula[HgCl2(C5H12N2S)2]
Mr535.94
Crystal system, space groupMonoclinic, C2/c
Temperature (K)293
a, b, c (Å)18.7418 (12), 9.5920 (6), 13.5177 (9)
β (°) 130.834 (1)
V3)1838.6 (2)
Z4
Radiation typeMo Kα
µ (mm1)8.88
Crystal size (mm)0.29 × 0.24 × 0.11
Data collection
DiffractometerBruker SMART APEX area detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.183, 0.442
No. of measured, independent and
observed [I > 2σ(I)] reflections
12167, 2281, 2103
Rint0.031
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.020, 0.040, 1.07
No. of reflections2281
No. of parameters92
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.72, 0.79

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top
Hg1—Cl12.5028 (8)Hg1—S12.5329 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···N20.962.522.849 (6)100
C3—H3A···S10.962.682.996 (6)100
C5—H5A···S10.962.623.024 (5)105
 

Acknowledgements

We gratefully acknowledge King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia, for providing the X-ray facility.

References

First citationAhmad, S., Sadaf, H., Akkurt, M., Sharif, S. & Khan, I. U. (2009). Acta Cryst. E65, m1191–m1192.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationBruker (2008). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChieh, C. (1977). Can. J. Chem. 55, 1583-1587.  CrossRef CAS Web of Science Google Scholar
First citationLobana, T. S., Sharma, R., Sharma, R., Sultana, R. & Butcher, R. J. (2008). Z. Anorg. Allg. Chem. 634, 718–723.  Web of Science CSD CrossRef CAS Google Scholar
First citationNawaz, S., Sadaf, S., Fettouhi, M., Fazal, A. & Ahmad, S. (2010a). Acta Cryst. E66, m950.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationNawaz, S., Sadaf, S., Fettouhi, M., Fazal, A. & Ahmad, S. (2010b). Acta Cryst. E66, m951.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationPopovic, Z., Pavlovic, G., Matkovic-Calogovic, D., Soldin, Z., Rajic, M., Vikic-Topic, D. & Kovacek, D. (2000). Inorg. Chim. Acta, 306, 142–152.  Web of Science CSD CrossRef CAS Google Scholar
First citationPopovic, Z., Soldin, Z. G., Pavlovic, G., Matkovic-Calogovic, D., Mrvos-Sermek, D. & Rajic, M. (2002). Struct. Chem. 13, 425–436.  Web of Science CSD CrossRef CAS Google Scholar
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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