Crystal structure of bis-(thio-cyanato-κS)bis-(thio-urea-κS)mercury(II).

In the title complex, [Hg(NCS)2(CH4N2S)2], the Hg(II) atom is four-coordinated having an irregular four-coordinate geometry composed of four thione S atoms of two thio-cyanate groups and two thio-urea groups. The S-Hg-S angles are 172.02 (9)° for the trans-thio-cyanate S atoms and 90.14 (5)° for the cis-thio-urea S atoms. The mol-ecular structure is stabilized by an intra-molecular N-H⋯S hydrogen bond, which forms an S(6) ring motif. In the crystal, mol-ecules are linked by a number of N-H⋯N and N-H⋯S hydrogen bonds, forming a three-dimensional framework. The first report of the crystal structure of this compound appeared in 1966 [Korczynski (1966 ▶). Rocz. Chem. 40, 547-569] with an extremely high R factor of 17.2%, and no mention of how the data were collected.

Related literature

For literature on thio­urea- and thio­cyanate-based metal–organic crystalline materials and their derivatives, see: Ramesh et al. (2012 ▸); Shihabuddeen Syed et al. (2013 ▸). For the concept of hard and soft acids and bases, see: Ozutsumi et al. (1989 ▸); Bell et al. (2001 ▸). For the crystal structures of similar compounds, see: Nawaz et al. (2010 ▸); Safari et al. (2009 ▸); Shihabuddeen Syed et al. (2013 ▸). For the first report of the crystal structure of the title compound, see: Korczynski (1966 ▸).

Experimental

Crystal data

[Hg(NCS)2(CH4N2S)2]

M = 468.99

Orthorhombic,

a = 8.5359 (5) Å

b = 9.0337 (5) Å

c = 15.7575 (10) Å

V = 1215.07 (12) Å3

Z = 4

Mo Kα radiation

μ = 13.33 mm−1

T = 293 K

0.20 × 0.20 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▸) T min = 0.176, T max = 0.240

19798 measured reflections

2397 independent reflections

2158 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.075

S = 1.15

2397 reflections

137 parameters

1 restraint

H-atom parameters constrained

Δρmax = 1.44 e Å−3

Δρmin = −1.03 e Å−3

Absolute structure: Flack (1983 ▸), 1149 Freidel pairs.

Absolute structure parameter: 0.034 (12)

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015000584/su5058sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015000584/su5058Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015000584/su5058fig1.tif

A view of the mol­ecular structure of the title complex, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. The intra­molecular N—H⋯S hydrogen bond is shown as a double dashed line (see Table 1 for details).

Click here for additional data file.

a . DOI: 10.1107/S2056989015000584/su5058fig2.tif

The crystal packing of the title complex, viewed along the a axis. Hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1043131

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Hg(NCS)2(CH4N2S)2]	F(000) = 872
Mr = 468.99	Dx = 2.564 Mg m−3
Orthorhombic, Pbc21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2b	Cell parameters from 2397 reflections
a = 8.5359 (5) Å	θ = 2.4–31.2°
b = 9.0337 (5) Å	µ = 13.33 mm−1
c = 15.7575 (10) Å	T = 293 K
V = 1215.07 (12) Å3	Block, colourless
Z = 4	0.20 × 0.20 × 0.15 mm

Bruker Kappa APEXII CCD diffractometer	2397 independent reflections
Radiation source: fine-focus sealed tube	2158 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.058
ω and φ scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→10
Tmin = 0.176, Tmax = 0.240	k = −11→11
19798 measured reflections	l = −19→19

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.029	w = 1/[σ2(Fo2) + (0.0237P)2 + 4.6956P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.075	(Δ/σ)max = 0.001
S = 1.15	Δρmax = 1.44 e Å−3
2397 reflections	Δρmin = −1.02 e Å−3
137 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.0082 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1149 Freidel pairs.
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.034 (12)

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 esds 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	0.25569 (4)	0.89378 (3)	0.72851 (8)	0.0374 (1)
S1	0.4564 (2)	1.1691 (2)	0.69569 (13)	0.0336 (6)
S2	−0.0283 (2)	1.0924 (2)	0.76929 (13)	0.0334 (6)
S3	0.2017 (3)	0.8900 (3)	0.57967 (14)	0.0329 (7)
S4	0.3068 (3)	0.8610 (3)	0.87589 (15)	0.0353 (7)
N1	0.6053 (9)	1.0000 (9)	0.5700 (5)	0.041 (3)
N2	0.0984 (9)	1.2628 (8)	0.9017 (5)	0.037 (3)
N3	0.6051 (8)	0.9346 (7)	0.8444 (5)	0.034 (2)
N4	0.5630 (8)	0.7508 (9)	0.9391 (4)	0.039 (2)
N5	−0.0507 (8)	1.0248 (7)	0.5262 (4)	0.031 (2)
N6	−0.0982 (7)	0.8404 (8)	0.6204 (5)	0.032 (2)
C1	0.5444 (9)	1.0700 (9)	0.6213 (5)	0.026 (2)
C2	0.0478 (9)	1.1927 (9)	0.8463 (5)	0.025 (2)
C3	0.5073 (8)	0.8485 (9)	0.8853 (5)	0.026 (2)
C4	0.0009 (9)	0.9200 (8)	0.5772 (4)	0.022 (2)
H3A	0.70430	0.92670	0.85300	0.0410*
H3B	0.57020	0.99910	0.80900	0.0410*
H4A	0.66240	0.74400	0.94710	0.0460*
H4B	0.50010	0.69370	0.96640	0.0460*
H5A	−0.14960	1.04050	0.52150	0.0370*
H5B	0.01460	1.07740	0.49760	0.0370*
H6A	−0.19710	0.85630	0.61570	0.0380*
H6B	−0.06470	0.77190	0.65370	0.0380*

	U11	U22	U33	U12	U13	U23
Hg1	0.0319 (2)	0.0600 (2)	0.0205 (2)	−0.0029 (1)	−0.0073 (2)	0.0032 (3)
S1	0.0359 (11)	0.0344 (10)	0.0304 (10)	−0.0005 (9)	−0.0003 (8)	−0.0009 (9)
S2	0.0319 (11)	0.0370 (10)	0.0314 (11)	0.0017 (9)	0.0016 (9)	−0.0026 (9)
S3	0.0231 (10)	0.0548 (14)	0.0209 (11)	0.0038 (9)	−0.0006 (9)	−0.0002 (9)
S4	0.0243 (11)	0.0616 (14)	0.0200 (11)	0.0005 (10)	0.0013 (9)	−0.0005 (10)
N1	0.035 (4)	0.051 (5)	0.038 (4)	0.000 (4)	0.003 (4)	−0.005 (4)
N2	0.039 (4)	0.035 (4)	0.037 (5)	0.002 (3)	−0.002 (3)	0.002 (3)
N3	0.026 (4)	0.033 (4)	0.044 (4)	−0.001 (3)	−0.005 (3)	0.011 (3)
N4	0.041 (4)	0.044 (4)	0.031 (4)	0.010 (3)	−0.005 (3)	0.009 (3)
N5	0.031 (4)	0.031 (4)	0.030 (4)	0.000 (3)	−0.003 (3)	0.006 (3)
N6	0.026 (3)	0.036 (4)	0.033 (4)	−0.001 (3)	−0.007 (3)	0.007 (3)
C1	0.024 (4)	0.032 (4)	0.022 (4)	−0.004 (3)	−0.004 (3)	0.008 (3)
C2	0.025 (4)	0.036 (4)	0.015 (4)	0.003 (3)	0.005 (3)	0.011 (3)
C3	0.028 (4)	0.031 (4)	0.019 (4)	0.008 (3)	−0.002 (3)	−0.010 (3)
C4	0.028 (4)	0.026 (4)	0.012 (4)	0.001 (3)	−0.005 (3)	−0.001 (3)

Hg1—S1	3.0641 (18)	N4—C3	1.313 (11)
Hg1—S2	3.0836 (18)	N5—C4	1.318 (9)
Hg1—S3	2.390 (3)	N6—C4	1.302 (10)
Hg1—S4	2.381 (3)	N3—H3A	0.8600
S1—C1	1.655 (8)	N3—H3B	0.8600
S2—C2	1.648 (8)	N4—H4A	0.8600
S3—C4	1.736 (8)	N4—H4B	0.8600
S4—C3	1.722 (7)	N5—H5A	0.8600
N1—C1	1.151 (11)	N5—H5B	0.8600
N2—C2	1.162 (11)	N6—H6A	0.8600
N3—C3	1.310 (10)	N6—H6B	0.8600
S1—Hg1—S2	90.14 (5)	C3—N3—H3A	120.00
S1—Hg1—S3	87.35 (8)	C3—N3—H3B	120.00
S1—Hg1—S4	99.39 (8)	H3A—N3—H3B	120.00
S2—Hg1—S3	93.51 (8)	S3—C4—N5	117.1 (6)
S2—Hg1—S4	90.75 (8)	S3—C4—N6	122.9 (6)
S3—Hg1—S4	172.02 (9)	N5—C4—N6	119.9 (7)
Hg1—S1—C1	86.2 (3)	C3—N4—H4A	120.00
Hg1—S2—C2	99.4 (3)	C3—N4—H4B	120.00
Hg1—S3—C4	102.1 (2)	H4A—N4—H4B	120.00
Hg1—S4—C3	105.9 (3)	C4—N5—H5A	120.00
S1—C1—N1	179.4 (8)	C4—N5—H5B	120.00
S2—C2—N2	178.4 (8)	H5A—N5—H5B	120.00
S4—C3—N3	123.5 (6)	C4—N6—H6A	120.00
S4—C3—N4	117.4 (6)	C4—N6—H6B	120.00
N3—C3—N4	119.1 (7)	H6A—N6—H6B	120.00
S2—Hg1—S1—C1	−145.2 (3)	S2—Hg1—S3—C4	−26.2 (3)
S3—Hg1—S1—C1	−51.7 (3)	S1—Hg1—S4—C3	−55.8 (3)
S4—Hg1—S1—C1	124.0 (3)	S2—Hg1—S4—C3	−146.1 (3)
S1—Hg1—S2—C2	−56.6 (3)	Hg1—S3—C4—N6	−53.0 (7)
S3—Hg1—S2—C2	−144.0 (3)	Hg1—S3—C4—N5	129.8 (5)
S4—Hg1—S2—C2	42.8 (3)	Hg1—S4—C3—N4	−139.9 (6)
S1—Hg1—S3—C4	−116.2 (3)	Hg1—S4—C3—N3	42.8 (8)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···S1	0.86	2.55	3.404 (7)	174
N3—H3A···N2i	0.86	2.37	3.103 (10)	143
N4—H4A···N2i	0.86	2.17	2.952 (10)	151
N4—H4B···N1ii	0.86	2.56	3.085 (11)	121
N5—H5A···N1iii	0.86	2.26	3.025 (10)	149
N5—H5A···S4iv	0.86	2.80	3.384 (7)	126
N5—H5B···N2v	0.86	2.21	3.025 (10)	158
N6—H6A···N1iii	0.86	2.25	3.019 (10)	149
N6—H6B···S2vi	0.86	2.56	3.419 (8)	172

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N3H3BS1	0.86	2.55	3.404(7)	174
N3H3AN2i	0.86	2.37	3.103(10)	143
N4H4AN2i	0.86	2.17	2.952(10)	151
N4H4BN1ii	0.86	2.56	3.085(11)	121
N5H5AN1iii	0.86	2.26	3.025(10)	149
N5H5AS4iv	0.86	2.80	3.384(7)	126
N5H5BN2v	0.86	2.21	3.025(10)	158
N6H6AN1iii	0.86	2.25	3.019(10)	149
N6H6BS2vi	0.86	2.56	3.419(8)	172

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .