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

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.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.010 Å
• R factor = 0.035
• wR factor = 0.093
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT733_ALERT_1_B Torsion Calc  -179.45(7), Rep  -179.45(1) ......       7.78 su-Ra
              CL2 -HG1 -CL2 -HG1    6.556   1.555   1.555   6.656

Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Hg1    --  Cl2     ..       8.37 su
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...         10
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.76

Alert level G
ABSTM02_ALERT_3_G  When printed, the submitted absorption T values will be
            replaced by the scaled T values. Since the ratio of scaled T's
            is identical to the ratio of reported T values, the scaling
            does not imply a change to the absorption corrections used in
            the study.
            Ratio of Tmax expected/reported      0.764
            Tmax scaled      0.271 Tmin scaled      0.081

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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.

S3. Refinement

H atoms were positioned geometrically and refined using a riding model with C—H = 0.95 - 0.98 Å and with U_iso(H) = 1.2 U_eq(C).

Computing details

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

	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]

Crystal data

[HgCl2(C7H8S)]	F(000) = 1440
Mr = 395.68	Dx = 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) Å^3	Needle, colourless
Z = 8	0.25 × 0.10 × 0.08 mm

Data collection

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

Refinement

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

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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—Cl2^i	2.742 (2)	C4—H4	0.9500
Cl2—Hg1^ii	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—Cl2^i	100.08 (6)	C5—C4—H4	120.0
S1—Hg1—Cl2^i	98.49 (6)	C3—C4—H4	120.0
Cl2—Hg1—Cl2^i	92.28 (5)	C4—C5—C6	120.9 (7)
Hg1—Cl2—Hg1^ii	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—Hg1^ii	−77.75 (8)	C7—S1—C1—C6	−120.4 (6)
S1—Hg1—Cl2—Hg1^ii	81.56 (7)	Hg1—S1—C1—C6	129.1 (5)
Cl2^i—Hg1—Cl2—Hg1^ii	−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)
Cl2^i—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)
Cl2^i—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.