(Thio-cyanato-κS)-tris-(thio-urea-κS)mercury(II) chloride.

In the title salt, [Hg(NCS)(CH4N2S)3]Cl, the Hg(2+) ion is coordinated in a severely distorted tetra-hedral manner by three thio-urea groups and one thio-cyanate anion through their S atoms. The S-Hg-S angles vary widely from 87.39 (5) to 128.02 (4)°. Weak intra-molecular N-H⋯S hydrogen bonds are observed, which form S(6) ring motifs. In the crystal, the ions are linked by N-H⋯N and weak N-H⋯Cl inter-actions, generating a three-dimensional network.

Related literature

For background to mercury(II) complexes with thio­urea and thio­cyanate ligands, see: Nawaz et al. (2010 ▶). For hard and soft acids and bases, see: Ozutsmi et al. (1989 ▶); Bell et al. (2001 ▶). For related structures, see: Safari et al. (2009 ▶); Nawaz et al. (2010 ▶); Ramesh et al. (2012 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

[Hg(NCS)(CH4N2S)3]Cl

M = 522.49

Orthorhombic,

a = 8.2175 (3) Å

b = 16.3257 (8) Å

c = 22.6793 (10) Å

V = 3042.6 (2) Å3

Z = 8

Mo Kα radiation

μ = 10.83 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.140, T max = 0.221

38987 measured reflections

5125 independent reflections

3579 reflections with I > 2σ(I)

R int = 0.057

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.082

S = 1.05

5125 reflections

155 parameters

H-atom parameters constrained

Δρmax = 2.17 e Å−3

Δρmin = −1.21 e Å−3

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, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813011847/jj2165sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011847/jj2165Isup2.hkl

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

[Hg(NCS)(CH4N2S)3]Cl	F(000) = 1968
Mr = 522.49	Dx = 2.281 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 5125 reflections
a = 8.2175 (3) Å	θ = 2.4–31.2°
b = 16.3257 (8) Å	µ = 10.83 mm−1
c = 22.6793 (10) Å	T = 293 K
V = 3042.6 (2) Å3	Block, colorless
Z = 8	0.30 × 0.25 × 0.20 mm

Bruker Kappa APEXII CCD diffractometer	5125 independent reflections
Radiation source: fine-focus sealed tube	3579 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
ω and φ scans	θmax = 31.8°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −12→6
Tmin = 0.140, Tmax = 0.221	k = −23→24
38987 measured reflections	l = −32→33

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0291P)2 + 7.0058P] where P = (Fo2 + 2Fc2)/3
5125 reflections	(Δ/σ)max = 0.001
155 parameters	Δρmax = 2.17 e Å−3
0 restraints	Δρmin = −1.21 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	1.2410 (5)	0.1993 (3)	0.42350 (17)	0.0280 (8)
C2	1.0389 (5)	0.3016 (3)	0.2771 (2)	0.0321 (9)
C3	0.7067 (6)	0.0234 (3)	0.43089 (19)	0.0333 (9)
C4	1.2429 (7)	−0.0184 (3)	0.3691 (2)	0.0498 (13)
N1	1.3113 (5)	0.1934 (3)	0.37245 (16)	0.0488 (12)
H1A	1.4063	0.2142	0.3671	0.059*
H1B	1.2628	0.1687	0.3439	0.059*
N2	1.3169 (5)	0.2370 (3)	0.46633 (17)	0.0445 (10)
H2A	1.4119	0.2575	0.4604	0.053*
H2B	1.2718	0.2414	0.5004	0.053*
N3	1.0072 (6)	0.3302 (3)	0.32922 (19)	0.0511 (11)
H3A	1.0352	0.3794	0.3383	0.061*
H3B	0.9582	0.2999	0.3547	0.061*
N4	1.1131 (6)	0.3476 (3)	0.2386 (2)	0.0541 (12)
H4A	1.1409	0.3967	0.2477	0.065*
H4B	1.1342	0.3287	0.2040	0.065*
N5	0.6681 (6)	0.0872 (3)	0.46201 (18)	0.0496 (11)
H5A	0.6676	0.0844	0.4999	0.060*
H5B	0.6430	0.1324	0.4448	0.060*
N6	0.7440 (8)	−0.0438 (3)	0.4576 (2)	0.0667 (15)
H6A	0.7430	−0.0458	0.4955	0.080*
H6B	0.7698	−0.0865	0.4375	0.080*
N7	1.2853 (8)	−0.0407 (4)	0.4142 (2)	0.0779 (18)
Hg1	0.92567 (2)	0.123362 (12)	0.340864 (7)	0.03933 (7)
S1	1.05319 (12)	0.15817 (7)	0.43857 (4)	0.0313 (2)
S2	1.18864 (19)	0.01386 (9)	0.30317 (6)	0.0529 (4)
S3	0.70350 (17)	0.02592 (8)	0.35487 (5)	0.0430 (3)
S4	0.98486 (18)	0.20568 (7)	0.25448 (5)	0.0411 (3)
Cl1	0.66976 (13)	0.27345 (7)	0.39858 (4)	0.0323 (2)

	U11	U22	U33	U12	U13	U23
C1	0.025 (2)	0.034 (2)	0.0245 (18)	0.0005 (16)	−0.0007 (15)	0.0005 (16)
C2	0.029 (2)	0.028 (2)	0.040 (2)	−0.0008 (16)	0.0019 (17)	−0.0016 (17)
C3	0.039 (3)	0.029 (2)	0.031 (2)	−0.0060 (18)	0.0015 (18)	0.0054 (17)
C4	0.060 (3)	0.044 (3)	0.046 (3)	0.022 (3)	0.006 (2)	−0.005 (2)
N1	0.032 (2)	0.090 (3)	0.0248 (18)	−0.021 (2)	0.0068 (15)	−0.010 (2)
N2	0.036 (2)	0.066 (3)	0.0310 (19)	−0.019 (2)	0.0034 (16)	−0.0137 (19)
N3	0.061 (3)	0.037 (2)	0.055 (3)	−0.013 (2)	0.019 (2)	−0.0159 (19)
N4	0.076 (3)	0.030 (2)	0.057 (3)	−0.015 (2)	0.024 (2)	−0.0046 (19)
N5	0.078 (3)	0.034 (2)	0.037 (2)	0.007 (2)	0.002 (2)	0.0028 (18)
N6	0.123 (5)	0.037 (3)	0.040 (2)	0.026 (3)	0.002 (3)	0.008 (2)
N7	0.110 (5)	0.079 (4)	0.044 (3)	0.043 (4)	0.005 (3)	0.008 (3)
Hg1	0.04559 (12)	0.04260 (11)	0.02981 (9)	−0.01684 (8)	−0.00241 (7)	0.00517 (7)
S1	0.0253 (5)	0.0458 (6)	0.0226 (4)	−0.0040 (4)	0.0020 (4)	−0.0053 (4)
S2	0.0672 (10)	0.0556 (8)	0.0358 (6)	0.0222 (7)	−0.0004 (6)	−0.0097 (6)
S3	0.0545 (8)	0.0436 (7)	0.0310 (5)	−0.0259 (6)	−0.0047 (5)	0.0018 (5)
S4	0.0683 (8)	0.0323 (6)	0.0227 (5)	−0.0161 (6)	−0.0053 (5)	0.0020 (4)
Cl1	0.0305 (5)	0.0362 (5)	0.0301 (5)	−0.0054 (4)	−0.0013 (4)	0.0004 (4)

C1—N1	1.297 (5)	N2—H2B	0.8600
C1—N2	1.309 (5)	N3—H3A	0.8600
C1—S1	1.717 (4)	N3—H3B	0.8600
C2—N3	1.297 (6)	N4—H4A	0.8600
C2—N4	1.302 (6)	N4—H4B	0.8600
C2—S4	1.707 (4)	N5—H5A	0.8600
C3—N6	1.290 (6)	N5—H5B	0.8600
C3—N5	1.298 (6)	N6—H6A	0.8600
C3—S3	1.725 (4)	N6—H6B	0.8600
C4—N7	1.141 (7)	Hg1—S4	2.4250 (11)
C4—S2	1.647 (6)	Hg1—S3	2.4422 (12)
C4—S2	1.647 (6)	Hg1—S1	2.5162 (10)
N1—H1A	0.8600	Hg1—S2	2.9320 (14)
N1—H1B	0.8600	Hg1—S2	2.9320 (14)
N2—H2A	0.8600
N1—C1—N2	119.0 (4)	C2—N4—H4B	120.0
N1—C1—S1	123.3 (3)	H4A—N4—H4B	120.0
N2—C1—S1	117.7 (3)	C3—N5—H5A	120.0
N3—C2—N4	119.9 (4)	C3—N5—H5B	120.0
N3—C2—S4	123.4 (4)	H5A—N5—H5B	120.0
N4—C2—S4	116.7 (4)	C3—N6—H6A	120.0
N6—C3—N5	119.1 (4)	C3—N6—H6B	120.0
N6—C3—S3	119.6 (4)	H6A—N6—H6B	120.0
N5—C3—S3	121.4 (4)	S4—Hg1—S3	128.02 (4)
N7—C4—S2	177.9 (6)	S4—Hg1—S1	120.18 (4)
N7—C4—S2	177.9 (6)	S3—Hg1—S1	110.11 (4)
C1—N1—H1A	120.0	S4—Hg1—S2	87.39 (5)
C1—N1—H1B	120.0	S3—Hg1—S2	101.05 (5)
H1A—N1—H1B	120.0	S1—Hg1—S2	95.02 (4)
C1—N2—H2A	120.0	S4—Hg1—S2	87.39 (5)
C1—N2—H2B	120.0	S3—Hg1—S2	101.05 (5)
H2A—N2—H2B	120.0	S1—Hg1—S2	95.02 (4)
C2—N3—H3A	120.0	C1—S1—Hg1	106.69 (14)
C2—N3—H3B	120.0	C4—S2—Hg1	97.45 (18)
H3A—N3—H3B	120.0	C3—S3—Hg1	97.71 (15)
C2—N4—H4A	120.0	C2—S4—Hg1	108.55 (16)
N1—C1—S1—Hg1	−14.6 (4)	S2—Hg1—S2—C4	0 (9)
N2—C1—S1—Hg1	166.6 (3)	N6—C3—S3—Hg1	−115.5 (4)
S4—Hg1—S1—C1	−32.03 (16)	N5—C3—S3—Hg1	66.4 (4)
S3—Hg1—S1—C1	161.59 (16)	S4—Hg1—S3—C3	−160.34 (16)
S2—Hg1—S1—C1	57.87 (16)	S1—Hg1—S3—C3	4.69 (17)
S2—Hg1—S1—C1	57.87 (16)	S2—Hg1—S3—C3	104.27 (17)
S2—C4—S2—Hg1	0 (100)	S2—Hg1—S3—C3	104.27 (17)
S4—Hg1—S2—S2	0.00 (8)	N3—C2—S4—Hg1	−17.9 (5)
S3—Hg1—S2—S2	0.00 (8)	N4—C2—S4—Hg1	163.4 (4)
S1—Hg1—S2—S2	0.00 (8)	S3—Hg1—S4—C2	138.25 (16)
S4—Hg1—S2—C4	150.5 (2)	S1—Hg1—S4—C2	−25.45 (17)
S3—Hg1—S2—C4	−81.2 (2)	S2—Hg1—S4—C2	−119.74 (17)
S1—Hg1—S2—C4	30.5 (2)	S2—Hg1—S4—C2	−119.74 (17)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.86	2.48	3.277 (4)	155
N1—H1B···S2	0.86	2.76	3.475 (5)	142
N2—H2A···Cl1i	0.86	2.55	3.335 (4)	152
N3—H3B···Cl1	0.86	2.61	3.320 (5)	141
N4—H4B···Cl1ii	0.86	2.51	3.370 (5)	175
N5—H5B···Cl1	0.86	2.54	3.363 (4)	161
N5—H5A···N7iii	0.86	2.11	2.933 (7)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.86	2.48	3.277 (4)	155
N1—H1B⋯S2	0.86	2.76	3.475 (5)	142
N2—H2A⋯Cl1i	0.86	2.55	3.335 (4)	152
N3—H3B⋯Cl1	0.86	2.61	3.320 (5)	141
N4—H4B⋯Cl1ii	0.86	2.51	3.370 (5)	175
N5—H5B⋯Cl1	0.86	2.54	3.363 (4)	161
N5—H5A⋯N7iii	0.86	2.11	2.933 (7)	160

Symmetry codes: (i) ; (ii) ; (iii) .