(2,2′-Dimethyl-4,4′-bi-1,3-thia­zole-κ² N,N′)bis(thio­cyanato-κS)mercury(II)

Abstract

The Hg^II atom in the title compound, [Hg(SCN)₂(C₈H₈N₂S₂)], is chelated by the bidentate heterocycle through the N atoms and is coordinated by the S atoms of two thiocyanate anions, resulting in a considerably distorted tetra­hedral coordination geometry.

Related literature

There are several examples of mercuric thio­cyanate–α,α′-dimine type of adducts which exist as four-coordinate, tetra­hedral mol­ecules. For the 4,4′,5,5′-tetra­methyl-2,2′-biimidazole adduct, see: Mahjoub et al. (2003 ▶); Morsali (2006 ▶). For the 2,2′-diamino-4,4′-bithia­zole adduct, see: Morsali et al. (2003 ▶). For the 2,2′-biquinoline adduct, see: Morsali et al. (2004 ▶); Ramazani et al. (2004 ▶). For the 2,2′-diphenyl-4,4′-bithia­zole adduct, see: Mahjoub & Morsali (2003 ▶).

Experimental

Crystal data

• [Hg(NCS)₂(C₈H₈N₂S₂)]

• M _r = 513.03

• Monoclinic,

• a = 17.3764 (3) Å

• b = 12.0534 (2) Å

• c = 7.0601 (1) Å

• β = 100.676 (1)°

• V = 1453.10 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 11.16 mm⁻¹

• T = 118 K

• 0.22 × 0.06 × 0.04 mm

Data collection

• Bruker SMART APEX diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.274, T _max = 0.640

• 10030 measured reflections

• 3330 independent reflections

• 2982 reflections with I > 2σ(I)

• R _int = 0.030

Refinement

• R[F ² > 2σ(F ²)] = 0.022

• wR(F ²) = 0.054

• S = 1.04

• 3330 reflections

• 174 parameters

• H-atom parameters constrained

• Δρ_max = 1.17 e Å⁻³

• Δρ_min = −1.32 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2 (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2009 ▶).

Supplementary Material

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

Table 1. Selected geometric parameters (Å, °).

Hg1—S3	2.413 (1)
Hg1—S4	2.421 (1)
Hg1—N1	2.430 (3)
Hg1—N2	2.476 (3)

S3—Hg1—S4	149.25 (4)
S3—Hg1—N1	95.66 (8)
S3—Hg1—N2	105.84 (8)
S4—Hg1—N1	113.49 (8)
S4—Hg1—N2	94.04 (8)
N1—Hg1—N2	69.1 (1)

supplementary crystallographic information

Experimental

A solution of 2,2'-dimethyl-4,4'-bithiazole (0.13 g, 0.66 mmol) in methanol (10 ml) was added to a solution of mercuric thiocyanate (0.21 g, 0.66 mmol) in methanol (5 ml). Crystals were obtained by diffusing the methanol solution into DMSO for a week (yield: 80%; m.p. 456 K).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95–0.98 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2–1.5U_eq(C).

The crystal diffracted strongly owing to the extremely heavy metal atom; however, its presence introduced severe absorption problems that could not be corrected analytically as the crystal did not have regular faces. The final difference Fourier map had a large peak/hole in the vicinity of the mercury atom.

Figures

Fig. 1.

Thermal ellipsoid plot (Barbour, 2001) of Hg(SCN)2(C10H8N2S2); ellipsoids are drawn at the 70% probability level and H atoms of arbitrary radius.

Crystal data

[Hg(NCS)2(C8H8N2S2)]	F(000) = 960
Mr = 513.03	Dx = 2.345 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4390 reflections
a = 17.3764 (3) Å	θ = 2.4–28.3°
b = 12.0534 (2) Å	µ = 11.16 mm−1
c = 7.0601 (1) Å	T = 118 K
β = 100.676 (1)°	Block, colorless
V = 1453.10 (4) Å3	0.22 × 0.06 × 0.04 mm
Z = 4

Data collection

Bruker SMART APEX diffractometer	3330 independent reflections
Radiation source: fine-focus sealed tube	2982 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω scans	θmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
Tmin = 0.274, Tmax = 0.640	k = −15→15
10030 measured reflections	l = −8→9

Refinement

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0213P)2 + 2.1611P] where P = (Fo2 + 2Fc2)/3
3330 reflections	(Δ/σ)max = 0.001
174 parameters	Δρmax = 1.17 e Å−3
0 restraints	Δρmin = −1.31 e Å−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Hg1	0.272849 (8)	0.578858 (12)	0.74895 (2)	0.01665 (6)
S1	0.37984 (5)	0.20867 (8)	0.65772 (15)	0.0156 (2)
S2	0.03250 (6)	0.34937 (8)	0.73374 (16)	0.0192 (2)
S3	0.34553 (7)	0.58014 (9)	1.07522 (18)	0.0287 (3)
S4	0.20772 (7)	0.68035 (9)	0.46884 (17)	0.0241 (2)
N1	0.30803 (18)	0.3905 (3)	0.6768 (5)	0.0132 (7)
N2	0.16170 (18)	0.4504 (3)	0.7495 (5)	0.0147 (7)
N3	0.4178 (2)	0.7908 (3)	1.1095 (6)	0.0317 (9)
N4	0.1421 (2)	0.4986 (3)	0.2409 (6)	0.0270 (8)
C1	0.4453 (2)	0.4223 (3)	0.6435 (7)	0.0221 (9)
H1A	0.4274	0.4900	0.5719	0.033*
H1B	0.4807	0.3815	0.5755	0.033*
H1C	0.4730	0.4421	0.7729	0.033*
C2	0.3765 (2)	0.3514 (3)	0.6592 (6)	0.0149 (8)
C3	0.2837 (2)	0.2028 (3)	0.6837 (6)	0.0148 (8)
H3	0.2549	0.1364	0.6912	0.018*
C4	0.2545 (2)	0.3082 (3)	0.6921 (6)	0.0128 (8)
C5	0.1758 (2)	0.3395 (3)	0.7151 (5)	0.0124 (7)
C6	0.1123 (2)	0.2727 (3)	0.7042 (6)	0.0163 (8)
H6	0.1121	0.1949	0.6834	0.020*
C7	0.0890 (2)	0.4686 (3)	0.7608 (6)	0.0158 (8)
C8	0.0558 (2)	0.5793 (3)	0.7950 (7)	0.0207 (9)
H8A	0.0831	0.6090	0.9186	0.031*
H8B	−0.0001	0.5716	0.7980	0.031*
H8C	0.0626	0.6301	0.6910	0.031*
C9	0.3879 (2)	0.7054 (3)	1.0890 (6)	0.0201 (9)
C10	0.1696 (2)	0.5709 (3)	0.3354 (6)	0.0188 (9)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Hg1	0.01515 (8)	0.01369 (8)	0.01971 (10)	−0.00045 (5)	−0.00039 (6)	−0.00147 (6)
S1	0.0154 (5)	0.0132 (4)	0.0188 (5)	0.0017 (3)	0.0049 (4)	−0.0005 (4)
S2	0.0120 (5)	0.0188 (5)	0.0271 (6)	−0.0016 (4)	0.0043 (4)	0.0004 (4)
S3	0.0367 (6)	0.0183 (5)	0.0249 (6)	−0.0089 (4)	−0.0108 (5)	0.0058 (5)
S4	0.0294 (6)	0.0140 (5)	0.0254 (6)	−0.0040 (4)	−0.0044 (5)	0.0029 (4)
N1	0.0118 (16)	0.0143 (15)	0.0133 (17)	−0.0004 (12)	0.0023 (12)	−0.0001 (13)
N2	0.0144 (16)	0.0150 (16)	0.0147 (18)	−0.0021 (12)	0.0029 (13)	0.0006 (13)
N3	0.036 (2)	0.025 (2)	0.031 (2)	−0.0093 (17)	−0.0018 (18)	−0.0027 (18)
N4	0.028 (2)	0.0228 (19)	0.027 (2)	−0.0006 (16)	−0.0031 (16)	−0.0014 (17)
C1	0.0134 (19)	0.018 (2)	0.035 (3)	0.0010 (15)	0.0055 (18)	0.0017 (19)
C2	0.0156 (19)	0.0140 (18)	0.014 (2)	0.0022 (14)	0.0011 (15)	−0.0001 (16)
C3	0.0145 (19)	0.0154 (19)	0.015 (2)	−0.0006 (14)	0.0037 (15)	−0.0014 (16)
C4	0.0134 (18)	0.0146 (18)	0.0099 (19)	0.0005 (14)	0.0013 (14)	0.0004 (15)
C5	0.0137 (18)	0.0140 (18)	0.0092 (19)	0.0008 (14)	0.0010 (14)	0.0022 (15)
C6	0.0129 (18)	0.0169 (19)	0.020 (2)	0.0005 (14)	0.0050 (15)	−0.0002 (17)
C7	0.0174 (19)	0.0133 (18)	0.017 (2)	0.0022 (15)	0.0037 (15)	0.0009 (16)
C8	0.018 (2)	0.018 (2)	0.027 (2)	0.0052 (16)	0.0064 (17)	−0.0023 (18)
C9	0.017 (2)	0.021 (2)	0.022 (2)	0.0007 (16)	0.0020 (16)	−0.0014 (18)
C10	0.0113 (19)	0.019 (2)	0.026 (2)	0.0012 (15)	0.0019 (16)	0.0042 (18)

Geometric parameters (Å, °)

Hg1—S3	2.413 (1)	N4—C10	1.146 (6)
Hg1—S4	2.421 (1)	C1—C2	1.490 (5)
Hg1—N1	2.430 (3)	C1—H1A	0.9800
Hg1—N2	2.476 (3)	C1—H1B	0.9800
S1—C2	1.721 (4)	C1—H1C	0.9800
S1—C3	1.716 (4)	C3—C4	1.374 (5)
S2—C6	1.711 (4)	C3—H3	0.9500
S2—C7	1.731 (4)	C4—C5	1.455 (5)
S3—C9	1.675 (4)	C5—C6	1.356 (5)
S4—C10	1.684 (4)	C6—H6	0.9500
N1—C2	1.308 (5)	C7—C8	1.491 (5)
N1—C4	1.379 (5)	C8—H8A	0.9800
N2—C7	1.299 (5)	C8—H8B	0.9800
N2—C5	1.389 (5)	C8—H8C	0.9800
N3—C9	1.150 (5)
S3—Hg1—S4	149.25 (4)	C1—C2—S1	123.0 (3)
S3—Hg1—N1	95.66 (8)	C4—C3—S1	110.0 (3)
S3—Hg1—N2	105.84 (8)	C4—C3—H3	125.0
S4—Hg1—N1	113.49 (8)	S1—C3—H3	125.0
S4—Hg1—N2	94.04 (8)	C3—C4—N1	113.7 (3)
N1—Hg1—N2	69.1 (1)	C3—C4—C5	127.4 (3)
C2—S1—C3	90.37 (19)	N1—C4—C5	118.9 (3)
C6—S2—C7	90.33 (19)	C6—C5—N2	114.4 (3)
C9—S3—Hg1	102.01 (16)	C6—C5—C4	127.7 (4)
C10—S4—Hg1	97.89 (15)	N2—C5—C4	117.9 (3)
C2—N1—C4	112.8 (3)	C5—C6—S2	110.0 (3)
C2—N1—Hg1	128.7 (3)	C5—C6—H6	125.0
C4—N1—Hg1	117.1 (2)	S2—C6—H6	125.0
C7—N2—C5	112.2 (3)	N2—C7—C8	124.8 (4)
C7—N2—Hg1	131.5 (3)	N2—C7—S2	113.0 (3)
C5—N2—Hg1	116.0 (2)	C8—C7—S2	122.2 (3)
C2—C1—H1A	109.5	C7—C8—H8A	109.5
C2—C1—H1B	109.5	C7—C8—H8B	109.5
H1A—C1—H1B	109.5	H8A—C8—H8B	109.5
C2—C1—H1C	109.5	C7—C8—H8C	109.5
H1A—C1—H1C	109.5	H8A—C8—H8C	109.5
H1B—C1—H1C	109.5	H8B—C8—H8C	109.5
N1—C2—C1	123.8 (3)	N3—C9—S3	176.2 (4)
N1—C2—S1	113.1 (3)	N4—C10—S4	177.9 (4)
S4—Hg1—S3—C9	−25.10 (19)	C2—S1—C3—C4	0.0 (3)
N1—Hg1—S3—C9	136.75 (17)	S1—C3—C4—N1	0.4 (4)
N2—Hg1—S3—C9	−153.45 (17)	S1—C3—C4—C5	−179.5 (3)
S3—Hg1—S4—C10	−173.66 (15)	C2—N1—C4—C3	−0.7 (5)
N1—Hg1—S4—C10	26.10 (17)	Hg1—N1—C4—C3	−168.8 (3)
N2—Hg1—S4—C10	−42.80 (16)	C2—N1—C4—C5	179.2 (3)
S3—Hg1—N1—C2	−67.8 (3)	Hg1—N1—C4—C5	11.1 (4)
S4—Hg1—N1—C2	102.2 (3)	C7—N2—C5—C6	−1.3 (5)
N2—Hg1—N1—C2	−172.6 (4)	Hg1—N2—C5—C6	−176.0 (3)
S3—Hg1—N1—C4	98.2 (3)	C7—N2—C5—C4	177.8 (3)
S4—Hg1—N1—C4	−91.8 (3)	Hg1—N2—C5—C4	3.1 (4)
N2—Hg1—N1—C4	−6.6 (3)	C3—C4—C5—C6	−10.6 (7)
S3—Hg1—N2—C7	98.2 (4)	N1—C4—C5—C6	169.5 (4)
S4—Hg1—N2—C7	−58.1 (4)	C3—C4—C5—N2	170.4 (4)
N1—Hg1—N2—C7	−171.8 (4)	N1—C4—C5—N2	−9.5 (5)
S3—Hg1—N2—C5	−88.4 (3)	N2—C5—C6—S2	0.9 (4)
S4—Hg1—N2—C5	115.3 (3)	C4—C5—C6—S2	−178.1 (3)
N1—Hg1—N2—C5	1.7 (2)	C7—S2—C6—C5	−0.3 (3)
C4—N1—C2—C1	−178.9 (4)	C5—N2—C7—C8	−179.5 (4)
Hg1—N1—C2—C1	−12.4 (6)	Hg1—N2—C7—C8	−5.8 (6)
C4—N1—C2—S1	0.6 (4)	C5—N2—C7—S2	1.0 (4)
Hg1—N1—C2—S1	167.11 (18)	Hg1—N2—C7—S2	174.69 (19)
C3—S1—C2—N1	−0.3 (3)	C6—S2—C7—N2	−0.4 (3)
C3—S1—C2—C1	179.2 (4)	C6—S2—C7—C8	−179.9 (4)