Dicyanidobis(N,N'-dimethythio-urea-κS)mercury(II).

In the title complex, [Hg(CN)(2)(C(3)H(8)N(2)S)(2)], the Hg(II) atom is located on a twofold rotation axis. It is four-coordinate having an irregular tetra-hedral geometry composed of two cyanide C atoms [Hg-C = 2.090 (6) Å] and two thione S atoms of N,N'-dimethyl-thio-urea (dmtu) [Hg-S = 2.7114 (9) Å]. The NC-Hg-CN bond angle of 148.83 (13)° has the greatest deviation from the ideal tetra-hedral geometry. The mol-ecular structure is stabilized by intra-molecular N-H⋯S inter-actions involving dmtu units related by the twofold symmetry. In the crystal, inter-molecular N-H⋯N(CN) hydrogen-bonding inter-actions link symmetry-related mol-ecules into a two-dimensional network in (110).

Related literature

For the biological applications of mercury(II) complexes of thi­o­nes, see: Akrivos (2001 ▶); Bell et al. (2001 ▶); Popovic et al. (2000 ▶). For background to mercury(II) complexes of thio­urea and its derivatives, see: Ahmad et al. (2009 ▶); Jiang et al. (2001 ▶); Lobana et al. (2008 ▶); Mufakkar et al. (2010 ▶); Nawaz et al. (2010 ▶); Popovic et al. (2000 ▶); Wu et al. (2004 ▶). For the crystal structures of cyanide complexes of d 10 metals, see: Ahmad et al. (2009 ▶); Altaf et al. (2010 ▶); Fettouhi et al. (2010 ▶); Hanif et al. (2007 ▶).

Experimental

Crystal data

[Hg(CN)2(C3H8N2S)2]

M = 460.98

Monoclinic,

a = 18.1161 (11) Å

b = 7.7533 (5) Å

c = 14.0553 (8) Å

β = 128.533 (3)°

V = 1544.32 (16) Å3

Z = 4

Mo Kα radiation

μ = 10.23 mm−1

T = 173 K

0.40 × 0.31 × 0.25 mm

Data collection

Stoe IPDS 2 diffractometer

Absorption correction: multi-scan (MULscanABS embedded in PLATON; Spek, 2009 ▶) T min = 0.270, T max = 1.000

8116 measured reflections

1451 independent reflections

1411 reflections with I > 2σ(I)

R int = 0.049

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.036

S = 1.14

1451 reflections

88 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.68 e Å−3

Δρmin = −1.97 e Å−3

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2009 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030424/wm2389sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030424/wm2389Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Hg(CN)2(C3H8N2S)2]	F(000) = 872
Mr = 460.98	Dx = 1.983 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 12331 reflections
a = 18.1161 (11) Å	θ = 1.9–26.1°
b = 7.7533 (5) Å	µ = 10.23 mm−1
c = 14.0553 (8) Å	T = 173 K
β = 128.533 (3)°	Block, colourless
V = 1544.32 (16) Å3	0.40 × 0.31 × 0.25 mm
Z = 4

Stoe IPDS 2 diffractometer	1451 independent reflections
Radiation source: fine-focus sealed tube	1411 reflections with I > 2σ(I)
graphite	Rint = 0.049
φ– + ω– scans	θmax = 25.6°, θmin = 2.9°
Absorption correction: multi-scan (MULscanABS embedded in PLATON; Spek, 2009)	h = −21→21
Tmin = 0.270, Tmax = 1.000	k = −9→9
8116 measured reflections	l = −17→17

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)] = 0.017	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.036	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0129P)2 + 2.6833P] where P = (Fo2 + 2Fc2)/3
1451 reflections	(Δ/σ)max < 0.001
88 parameters	Δρmax = 0.68 e Å−3
0 restraints	Δρmin = −1.97 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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.

	x	y	z	Uiso*/Ueq
Hg1	0.50000	−0.21587 (2)	0.25000	0.0231 (1)
S1	0.37952 (6)	0.02195 (11)	0.08082 (7)	0.0255 (3)
N1	0.3941 (2)	0.1650 (4)	0.2640 (3)	0.0277 (9)
N2	0.2450 (2)	0.0856 (4)	0.1004 (2)	0.0241 (8)
N3	0.3776 (3)	−0.3173 (4)	0.3370 (3)	0.0441 (12)
C1	0.3355 (2)	0.0948 (4)	0.1535 (3)	0.0210 (9)
C2	0.3657 (3)	0.2174 (5)	0.3367 (3)	0.0386 (13)
C3	0.1748 (2)	0.0052 (5)	−0.0168 (3)	0.0306 (11)
C4	0.4229 (3)	−0.2883 (4)	0.3084 (3)	0.0295 (10)
H1N	0.449 (3)	0.161 (5)	0.296 (3)	0.024 (10)*
H2A	0.31970	0.31150	0.29540	0.0580*
H2B	0.42120	0.25690	0.41680	0.0580*
H2C	0.33710	0.11910	0.34680	0.0580*
H2N	0.227 (3)	0.128 (5)	0.134 (3)	0.030 (10)*
H3A	0.17870	0.05510	−0.07770	0.0460*
H3B	0.11180	0.02530	−0.04110	0.0460*
H3C	0.18680	−0.11920	−0.01060	0.0460*

	U11	U22	U33	U12	U13	U23
Hg1	0.0209 (1)	0.0274 (1)	0.0294 (1)	0.0000	0.0197 (1)	0.0000
S1	0.0249 (5)	0.0344 (4)	0.0242 (4)	0.0067 (3)	0.0188 (4)	0.0020 (3)
N1	0.0244 (18)	0.0359 (17)	0.0275 (13)	0.0008 (14)	0.0185 (14)	−0.0045 (12)
N2	0.0225 (16)	0.0279 (15)	0.0273 (13)	0.0015 (11)	0.0181 (12)	−0.0035 (11)
N3	0.040 (2)	0.058 (2)	0.054 (2)	−0.0070 (17)	0.0389 (19)	0.0028 (16)
C1	0.0236 (18)	0.0192 (15)	0.0255 (14)	0.0042 (12)	0.0179 (14)	0.0031 (11)
C2	0.041 (3)	0.050 (2)	0.0352 (18)	−0.0019 (18)	0.0288 (19)	−0.0128 (16)
C3	0.022 (2)	0.0341 (19)	0.0336 (16)	−0.0025 (15)	0.0163 (16)	−0.0047 (14)
C4	0.028 (2)	0.0288 (17)	0.0344 (16)	−0.0018 (15)	0.0207 (16)	0.0009 (14)

Hg1—S1	2.7114 (9)	N3—C4	1.139 (8)
Hg1—C4	2.090 (6)	N1—H1N	0.80 (6)
Hg1—S1i	2.7114 (9)	N2—H2N	0.79 (5)
Hg1—C4i	2.090 (6)	C2—H2A	0.9800
S1—C1	1.736 (4)	C2—H2B	0.9800
N1—C1	1.335 (5)	C2—H2C	0.9800
N1—C2	1.459 (7)	C3—H3A	0.9800
N2—C1	1.314 (6)	C3—H3B	0.9800
N2—C3	1.452 (4)	C3—H3C	0.9800
S1—Hg1—C4	99.05 (11)	S1—C1—N1	119.6 (3)
S1—Hg1—S1i	94.31 (3)	Hg1—C4—N3	175.3 (3)
S1—Hg1—C4i	102.01 (9)	N1—C2—H2A	109.00
S1i—Hg1—C4	102.01 (9)	N1—C2—H2B	110.00
C4—Hg1—C4i	148.83 (13)	N1—C2—H2C	109.00
S1i—Hg1—C4i	99.05 (11)	H2A—C2—H2B	109.00
Hg1—S1—C1	96.84 (11)	H2A—C2—H2C	109.00
C1—N1—C2	123.8 (4)	H2B—C2—H2C	109.00
C1—N2—C3	124.7 (3)	N2—C3—H3A	109.00
C1—N1—H1N	117 (3)	N2—C3—H3B	110.00
C2—N1—H1N	118 (3)	N2—C3—H3C	109.00
C3—N2—H2N	117 (3)	H3A—C3—H3B	110.00
C1—N2—H2N	118 (3)	H3A—C3—H3C	109.00
S1—C1—N2	121.1 (3)	H3B—C3—H3C	109.00
N1—C1—N2	119.3 (4)
C4—Hg1—S1—C1	32.52 (15)	C2—N1—C1—S1	−174.9 (3)
S1i—Hg1—S1—C1	−70.39 (13)	C2—N1—C1—N2	6.6 (5)
C4i—Hg1—S1—C1	−170.60 (16)	C3—N2—C1—S1	4.6 (5)
Hg1—S1—C1—N1	60.6 (3)	C3—N2—C1—N1	−177.0 (3)
Hg1—S1—C1—N2	−121.0 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1i	0.80 (6)	2.67 (5)	3.415 (4)	157 (4)
N2—H2N···N3ii	0.79 (5)	2.21 (6)	2.951 (7)	155 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1i	0.80 (6)	2.67 (5)	3.415 (4)	157 (4)
N2—H2N⋯N3ii	0.79 (5)	2.21 (6)	2.951 (7)	155 (4)

Symmetry codes: (i) ; (ii) .