catena-Poly[[chlorido(methyl phenyl sulfide-κS)mercury(II)]-μ-chlorido]

Vigo, L.; Salin, P.; Oilunkaniemi, R.; Laitinen, R.S.

doi:10.1107/S1600536808013718

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page m809

doi:10.1107/S1600536808013718

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catena-Poly[[chlorido(methyl phenyl sulfide-κS)mercury(II)]-μ-chlorido]

Ludmila Vigo,^a Pekka Salin,^a Raija Oilunkaniemi ^a and Risto S. Laitinen ^a ^*

^aDepartment of Chemistry, PO Box 3000, FI-90014 University of Oulu, Finland
^*Correspondence e-mail: risto.laitinen@oulu.fi

(Received 2 May 2008; accepted 8 May 2008; online 14 May 2008)

The title compound, [HgCl₂(C₇H₈S)]_n, was isolated from the reaction of MeSPh with HgCl₂. The Hg^II atom has a distorted tetrahedral geometry and is coordinated by one S atom and three Cl atoms. Two of the Cl atoms act as bridging ligands between the Hg atoms, forming a two-dimensional polymeric structure.

Related literature

For related literature, see: Peindy et al. (2005 ).

Experimental

Crystal data

[HgCl₂(C₇H₈S)]
M_r = 395.68
Orthorhombic, P b c a
a = 5.9616 (12) Å
b = 14.935 (3) Å
c = 22.142 (4) Å
V = 1971.4 (7) Å³
Z = 8
Mo Kα radiation
μ = 16.30 mm⁻¹
T = 150 (2) K
0.25 × 0.10 × 0.08 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SHELXTL; Sheldrick 2008 ) T_min = 0.106, T_max = 0.355 (expected range = 0.081–0.271)
9374 measured reflections
1760 independent reflections
1562 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.092
S = 1.07
1760 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 2.22 e Å⁻³
Δρ_min = −1.51 e Å⁻³

Table 1
Selected bond lengths (Å)

Hg1—Cl1	2.3429 (18)
Hg1—S1	2.4548 (17)
Hg1—Cl2	2.6050 (17)
Hg1—Cl2ⁱ	2.742 (2)
Symmetry code: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808013718/sg2244sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013718/sg2244Isup2.hkl

checkCIF report

Comment top

Crystals of [HgCl₂(MeSPh)]_n (I) were isolated from the reaction of MeSPh with HgCl₂ in EtOH. The asymmetric unit of I consists of one Hg atom, MeSPh ligand and two chlorine atoms. The mercury(II) atom has distorted tetrahedral geometry and is coordinated to one sulfur atom and three chlorine atoms. Two of the chlorine atoms act as bridging ligands between the mercury atoms forming a two-dimensional polymeric structure. The Hg - Cl bond lenghts are 2.6050 (17) and 2.742 (2) Å for the bridging chlorines and 2.3429 (18) Å for the terminal chlorine, The Hg - S bond length is 2.4548 (17) Å. The bond parameters can be compared to those in [{PhS(CH₂)SPh}Hg₂Cl₄]_n where Hg atom has a similar coordination environment (Peindy et al. (2005)]

Related literature top

For related literature, see: Peindy et al. (2005)

Experimental top

The addition of MeSPh (0.603 g; 4.85 mmol) to HgCl₂ (0.283 g: 1.04 mmol) in 10 ml EtOH gave at first a clear solution followed by precipitation of colourless crystals. Decomposition of the crystals took place upon removal of the solvent. Crystals suitable for crystal structure determination were picked from the reaction solution.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of I indicating the numbering of the atoms. The thermal ellipsoids have been drawn at 50% probability.
	Fig. 2. The packing of polymer chains.

catena-Poly[[chlorido(methyl phenyl sulfide-κS)mercury(II)]-µ-chlorido] top

Crystal data top

[HgCl₂(C₇H₈S)]	F(000) = 1440
M_r = 395.68	D_x = 2.666 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1562 reflections
a = 5.9616 (12) Å	θ = 3.7–25.4°
b = 14.935 (3) Å	µ = 16.30 mm⁻¹
c = 22.142 (4) Å	T = 150 K
V = 1971.4 (7) Å³	Needle, colourless
Z = 8	0.25 × 0.10 × 0.08 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	1760 independent reflections
Radiation source: fine-focus sealed tube	1562 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ scans, and ω scans with κ offsets	θ_max = 25.5°, θ_min = 3.7°
Absorption correction: multi-scan (SHELXTL; Sheldrick 2008)	h = −7→7
T_min = 0.106, T_max = 0.355	k = −18→16
9374 measured reflections	l = −23→26

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.035	H-atom parameters constrained
wR(F²) = 0.092	w = 1/[σ²(F_o²) + (0.0473P)² + 8.371P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1760 reflections	Δρ_max = 2.22 e Å⁻³
102 parameters	Δρ_min = −1.51 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (3)

Crystal data top

[HgCl₂(C₇H₈S)]	V = 1971.4 (7) Å³
M_r = 395.68	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 5.9616 (12) Å	µ = 16.30 mm⁻¹
b = 14.935 (3) Å	T = 150 K
c = 22.142 (4) Å	0.25 × 0.10 × 0.08 mm

Data collection top

Bruker–Nonius KappaCCD diffractometer	1760 independent reflections
Absorption correction: multi-scan (SHELXTL; Sheldrick 2008)	1562 reflections with I > 2σ(I)
T_min = 0.106, T_max = 0.355	R_int = 0.063
9374 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.07	Δρ_max = 2.22 e Å⁻³
1760 reflections	Δρ_min = −1.51 e Å⁻³
102 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

	x	y	z	U_iso*/U_eq
Hg1	0.04378 (5)	0.284473 (18)	0.188615 (12)	0.03063 (19)
Cl1	0.0758 (3)	0.43434 (12)	0.15855 (8)	0.0366 (4)
Cl2	0.0860 (3)	0.26914 (14)	0.30526 (7)	0.0327 (4)
S1	0.1319 (3)	0.13004 (11)	0.15897 (7)	0.0284 (4)
C1	0.0764 (12)	0.1286 (5)	0.0799 (3)	0.0282 (15)
C2	−0.1212 (14)	0.1616 (5)	0.0562 (3)	0.0353 (16)
H2	−0.2335	0.1856	0.0820	0.042*
C3	−0.1532 (14)	0.1592 (5)	−0.0055 (3)	0.0405 (18)
H3	−0.2899	0.1802	−0.0223	0.049*
C4	0.0143 (15)	0.1260 (6)	−0.0432 (4)	0.045 (2)
H4	−0.0072	0.1256	−0.0857	0.054*
C5	0.2088 (15)	0.0941 (5)	−0.0191 (3)	0.0417 (19)
H5	0.3216	0.0711	−0.0451	0.050*
C6	0.2443 (13)	0.0948 (4)	0.0425 (3)	0.0343 (15)
H6	0.3804	0.0728	0.0591	0.041*
C7	−0.0891 (15)	0.0613 (6)	0.1887 (3)	0.0371 (18)
H11A	−0.2345	0.0881	0.1787	0.056*
H11B	−0.0737	0.0570	0.2327	0.056*
H11C	−0.0796	0.0013	0.1709	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0363 (3)	0.0265 (2)	0.0291 (2)	−0.00098 (11)	−0.00083 (10)	−0.00019 (10)
Cl1	0.0428 (10)	0.0268 (9)	0.0401 (10)	−0.0015 (7)	0.0006 (8)	0.0041 (7)
Cl2	0.0319 (8)	0.0446 (10)	0.0217 (8)	0.0000 (8)	−0.0009 (6)	0.0017 (7)
S1	0.0325 (9)	0.0279 (8)	0.0247 (8)	0.0024 (7)	−0.0007 (7)	−0.0011 (6)
C1	0.035 (4)	0.028 (3)	0.021 (3)	−0.003 (3)	0.001 (3)	0.002 (3)
C2	0.048 (4)	0.028 (4)	0.030 (4)	0.005 (3)	−0.002 (3)	−0.004 (3)
C3	0.052 (5)	0.038 (4)	0.031 (4)	−0.003 (4)	−0.003 (3)	0.000 (3)
C4	0.067 (5)	0.042 (4)	0.024 (4)	−0.013 (4)	−0.003 (4)	0.001 (3)
C5	0.058 (5)	0.039 (4)	0.029 (4)	−0.002 (4)	0.009 (4)	−0.004 (3)
C6	0.043 (4)	0.028 (3)	0.033 (4)	0.002 (3)	0.006 (3)	−0.002 (3)
C7	0.046 (4)	0.030 (4)	0.036 (4)	−0.011 (4)	0.002 (3)	0.003 (3)

Geometric parameters (Å, º) top

Hg1—Cl1	2.3429 (18)	C3—C4	1.392 (12)
Hg1—S1	2.4548 (17)	C3—H3	0.9500
Hg1—Cl2	2.6050 (17)	C4—C5	1.362 (12)
Hg1—Cl2ⁱ	2.742 (2)	C4—H4	0.9500
Cl2—Hg1ⁱⁱ	2.742 (2)	C5—C6	1.381 (10)
S1—C1	1.782 (7)	C5—H5	0.9500
S1—C7	1.795 (8)	C6—H6	0.9500
C1—C2	1.381 (10)	C7—H11A	0.9800
C1—C6	1.393 (10)	C7—H11B	0.9800
C2—C3	1.380 (10)	C7—H11C	0.9800
C2—H2	0.9500

Cl1—Hg1—S1	143.53 (7)	C2—C3—H3	119.9
Cl1—Hg1—Cl2	110.97 (7)	C4—C3—H3	119.9
S1—Hg1—Cl2	99.31 (6)	C5—C4—C3	120.1 (7)
Cl1—Hg1—Cl2ⁱ	100.08 (6)	C5—C4—H4	120.0
S1—Hg1—Cl2ⁱ	98.49 (6)	C3—C4—H4	120.0
Cl2—Hg1—Cl2ⁱ	92.28 (5)	C4—C5—C6	120.9 (7)
Hg1—Cl2—Hg1ⁱⁱ	97.92 (6)	C4—C5—H5	119.5
C1—S1—C7	102.5 (3)	C6—C5—H5	119.5
C1—S1—Hg1	103.6 (2)	C5—C6—C1	118.6 (7)
C7—S1—Hg1	106.4 (3)	C5—C6—H6	120.7
C2—C1—C6	121.1 (6)	C1—C6—H6	120.7
C2—C1—S1	121.8 (5)	S1—C7—H11A	109.5
C6—C1—S1	117.0 (5)	S1—C7—H11B	109.5
C3—C2—C1	119.0 (7)	H11A—C7—H11B	109.5
C3—C2—H2	120.5	S1—C7—H11C	109.5
C1—C2—H2	120.5	H11A—C7—H11C	109.5
C2—C3—C4	120.2 (8)	H11B—C7—H11C	109.5

Cl1—Hg1—Cl2—Hg1ⁱⁱ	−77.75 (8)	C7—S1—C1—C6	−120.4 (6)
S1—Hg1—Cl2—Hg1ⁱⁱ	81.56 (7)	Hg1—S1—C1—C6	129.1 (5)
Cl2ⁱ—Hg1—Cl2—Hg1ⁱⁱ	−179.453 (9)	C6—C1—C2—C3	1.3 (11)
Cl1—Hg1—S1—C1	−40.3 (3)	S1—C1—C2—C3	179.5 (6)
Cl2—Hg1—S1—C1	173.5 (2)	C1—C2—C3—C4	−1.6 (11)
Cl2ⁱ—Hg1—S1—C1	79.7 (2)	C2—C3—C4—C5	1.3 (12)
Cl1—Hg1—S1—C7	−147.9 (3)	C3—C4—C5—C6	−0.6 (12)
Cl2—Hg1—S1—C7	65.8 (3)	C4—C5—C6—C1	0.3 (11)
Cl2ⁱ—Hg1—S1—C7	−28.0 (3)	C2—C1—C6—C5	−0.6 (10)
C7—S1—C1—C2	61.4 (7)	S1—C1—C6—C5	−178.9 (5)
Hg1—S1—C1—C2	−49.2 (6)

Symmetry codes: (i) x−1/2, y, −z+1/2; (ii) x+1/2, y, −z+1/2.

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₇H₈S)]
M_r	395.68
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	5.9616 (12), 14.935 (3), 22.142 (4)
V (Å³)	1971.4 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	16.30
Crystal size (mm)	0.25 × 0.10 × 0.08

Data collection
Diffractometer	Bruker–Nonius KappaCCD diffractometer
Absorption correction	Multi-scan (SHELXTL; Sheldrick 2008)
T_min, T_max	0.106, 0.355
No. of measured, independent and observed [I > 2σ(I)] reflections	9374, 1760, 1562
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.092, 1.07
No. of reflections	1760
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	2.22, −1.51

Computer programs: COLLECT (Nonius, 1998), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Berndt, 1999), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Hg1—Cl1	2.3429 (18)	Hg1—Cl2	2.6050 (17)
Hg1—S1	2.4548 (17)	Hg1—Cl2ⁱ	2.742 (2)

Symmetry code: (i) x−1/2, y, −z+1/2.

Acknowledgements

Financial support from the Academy of Finland is gratefully acknowledged.

References

Brandenburg, K. & Berndt, M. (1999). DIAMOND. Crystal Impact GmbH, Bonn, Germany. Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. London: Academic Press. Google Scholar
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