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Acta Cryst. (2009). E65, m372    [ doi:10.1107/S1600536809006904 ]

(2,2'-Dimethyl-4,4'-bi-1,3-thiazole-[kappa]2N,N')bis(thiocyanato-[kappa]S)mercury(II)

N. Safari, V. Amani, A. Abedi, B. Notash and S. W. Ng

Abstract top

The HgII 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 top

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 top

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 top

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 Uiso(H) set to 1.2–1.5Ueq(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.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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: pubCIF (Westrip, 2009).

Figures top
[Figure 1] 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.
(2,2'-Dimethyl-4,4'-bi-1,3-thiazole- κ2N,N')bis(thiocyanato-κS)mercury(II) top
Crystal data top
[Hg(NCS)2(C8H8N2S2)]F(000) = 960
Mr = 513.03Dx = 2.345 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4390 reflections
a = 17.3764 (3) Åθ = 2.4–28.3°
b = 12.0534 (2) ŵ = 11.16 mm−1
c = 7.0601 (1) ÅT = 118 K
β = 100.676 (1)°Block, colorless
V = 1453.10 (4) Å30.22 × 0.06 × 0.04 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		3330 independent reflections
Radiation source: fine-focus sealed tube2982 reflections with I > 2σ(I)
graphiteRint = 0.030
ω scansθmax = 27.5°, θmin = 1.2°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −22→22
Tmin = 0.274, Tmax = 0.640k = −15→15
10030 measured reflectionsl = −8→9
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.022Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-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 parametersΔρmax = 1.17 e Å−3
0 restraintsΔρmin = −1.31 e Å−3
Crystal data top
[Hg(NCS)2(C8H8N2S2)]V = 1453.10 (4) Å3
Mr = 513.03Z = 4
Monoclinic, P21/cMo Kα radiation
a = 17.3764 (3) ŵ = 11.16 mm−1
b = 12.0534 (2) ÅT = 118 K
c = 7.0601 (1) Å0.22 × 0.06 × 0.04 mm
β = 100.676 (1)°
Data collection top
Bruker SMART APEX
diffractometer		3330 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2982 reflections with I > 2σ(I)
Tmin = 0.274, Tmax = 0.640Rint = 0.030
10030 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.022H-atom parameters constrained
wR(F2) = 0.054Δρmax = 1.17 e Å−3
S = 1.04Δρmin = −1.31 e Å−3
3330 reflectionsAbsolute structure: ?
174 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hg10.272849 (8)0.578858 (12)0.74895 (2)0.01665 (6)
S10.37984 (5)0.20867 (8)0.65772 (15)0.0156 (2)
S20.03250 (6)0.34937 (8)0.73374 (16)0.0192 (2)
S30.34553 (7)0.58014 (9)1.07522 (18)0.0287 (3)
S40.20772 (7)0.68035 (9)0.46884 (17)0.0241 (2)
N10.30803 (18)0.3905 (3)0.6768 (5)0.0132 (7)
N20.16170 (18)0.4504 (3)0.7495 (5)0.0147 (7)
N30.4178 (2)0.7908 (3)1.1095 (6)0.0317 (9)
N40.1421 (2)0.4986 (3)0.2409 (6)0.0270 (8)
C10.4453 (2)0.4223 (3)0.6435 (7)0.0221 (9)
H1A0.42740.49000.57190.033*
H1B0.48070.38150.57550.033*
H1C0.47300.44210.77290.033*
C20.3765 (2)0.3514 (3)0.6592 (6)0.0149 (8)
C30.2837 (2)0.2028 (3)0.6837 (6)0.0148 (8)
H30.25490.13640.69120.018*
C40.2545 (2)0.3082 (3)0.6921 (6)0.0128 (8)
C50.1758 (2)0.3395 (3)0.7151 (5)0.0124 (7)
C60.1123 (2)0.2727 (3)0.7042 (6)0.0163 (8)
H60.11210.19490.68340.020*
C70.0890 (2)0.4686 (3)0.7608 (6)0.0158 (8)
C80.0558 (2)0.5793 (3)0.7950 (7)0.0207 (9)
H8A0.08310.60900.91860.031*
H8B−0.00010.57160.79800.031*
H8C0.06260.63010.69100.031*
C90.3879 (2)0.7054 (3)1.0890 (6)0.0201 (9)
C100.1696 (2)0.5709 (3)0.3354 (6)0.0188 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.01515 (8)0.01369 (8)0.01971 (10)−0.00045 (5)−0.00039 (6)−0.00147 (6)
S10.0154 (5)0.0132 (4)0.0188 (5)0.0017 (3)0.0049 (4)−0.0005 (4)
S20.0120 (5)0.0188 (5)0.0271 (6)−0.0016 (4)0.0043 (4)0.0004 (4)
S30.0367 (6)0.0183 (5)0.0249 (6)−0.0089 (4)−0.0108 (5)0.0058 (5)
S40.0294 (6)0.0140 (5)0.0254 (6)−0.0040 (4)−0.0044 (5)0.0029 (4)
N10.0118 (16)0.0143 (15)0.0133 (17)−0.0004 (12)0.0023 (12)−0.0001 (13)
N20.0144 (16)0.0150 (16)0.0147 (18)−0.0021 (12)0.0029 (13)0.0006 (13)
N30.036 (2)0.025 (2)0.031 (2)−0.0093 (17)−0.0018 (18)−0.0027 (18)
N40.028 (2)0.0228 (19)0.027 (2)−0.0006 (16)−0.0031 (16)−0.0014 (17)
C10.0134 (19)0.018 (2)0.035 (3)0.0010 (15)0.0055 (18)0.0017 (19)
C20.0156 (19)0.0140 (18)0.014 (2)0.0022 (14)0.0011 (15)−0.0001 (16)
C30.0145 (19)0.0154 (19)0.015 (2)−0.0006 (14)0.0037 (15)−0.0014 (16)
C40.0134 (18)0.0146 (18)0.0099 (19)0.0005 (14)0.0013 (14)0.0004 (15)
C50.0137 (18)0.0140 (18)0.0092 (19)0.0008 (14)0.0010 (14)0.0022 (15)
C60.0129 (18)0.0169 (19)0.020 (2)0.0005 (14)0.0050 (15)−0.0002 (17)
C70.0174 (19)0.0133 (18)0.017 (2)0.0022 (15)0.0037 (15)0.0009 (16)
C80.018 (2)0.018 (2)0.027 (2)0.0052 (16)0.0064 (17)−0.0023 (18)
C90.017 (2)0.021 (2)0.022 (2)0.0007 (16)0.0020 (16)−0.0014 (18)
C100.0113 (19)0.019 (2)0.026 (2)0.0012 (15)0.0019 (16)0.0042 (18)
Geometric parameters (Å, °) top
Hg1—S32.413 (1)N4—C101.146 (6)
Hg1—S42.421 (1)C1—C21.490 (5)
Hg1—N12.430 (3)C1—H1A0.9800
Hg1—N22.476 (3)C1—H1B0.9800
S1—C21.721 (4)C1—H1C0.9800
S1—C31.716 (4)C3—C41.374 (5)
S2—C61.711 (4)C3—H30.9500
S2—C71.731 (4)C4—C51.455 (5)
S3—C91.675 (4)C5—C61.356 (5)
S4—C101.684 (4)C6—H60.9500
N1—C21.308 (5)C7—C81.491 (5)
N1—C41.379 (5)C8—H8A0.9800
N2—C71.299 (5)C8—H8B0.9800
N2—C51.389 (5)C8—H8C0.9800
N3—C91.150 (5)
S3—Hg1—S4149.25 (4)C1—C2—S1123.0 (3)
S3—Hg1—N195.66 (8)C4—C3—S1110.0 (3)
S3—Hg1—N2105.84 (8)C4—C3—H3125.0
S4—Hg1—N1113.49 (8)S1—C3—H3125.0
S4—Hg1—N294.04 (8)C3—C4—N1113.7 (3)
N1—Hg1—N269.1 (1)C3—C4—C5127.4 (3)
C2—S1—C390.37 (19)N1—C4—C5118.9 (3)
C6—S2—C790.33 (19)C6—C5—N2114.4 (3)
C9—S3—Hg1102.01 (16)C6—C5—C4127.7 (4)
C10—S4—Hg197.89 (15)N2—C5—C4117.9 (3)
C2—N1—C4112.8 (3)C5—C6—S2110.0 (3)
C2—N1—Hg1128.7 (3)C5—C6—H6125.0
C4—N1—Hg1117.1 (2)S2—C6—H6125.0
C7—N2—C5112.2 (3)N2—C7—C8124.8 (4)
C7—N2—Hg1131.5 (3)N2—C7—S2113.0 (3)
C5—N2—Hg1116.0 (2)C8—C7—S2122.2 (3)
C2—C1—H1A109.5C7—C8—H8A109.5
C2—C1—H1B109.5C7—C8—H8B109.5
H1A—C1—H1B109.5H8A—C8—H8B109.5
C2—C1—H1C109.5C7—C8—H8C109.5
H1A—C1—H1C109.5H8A—C8—H8C109.5
H1B—C1—H1C109.5H8B—C8—H8C109.5
N1—C2—C1123.8 (3)N3—C9—S3176.2 (4)
N1—C2—S1113.1 (3)N4—C10—S4177.9 (4)
S4—Hg1—S3—C9−25.10 (19)C2—S1—C3—C40.0 (3)
N1—Hg1—S3—C9136.75 (17)S1—C3—C4—N10.4 (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—C1026.10 (17)Hg1—N1—C4—C3−168.8 (3)
N2—Hg1—S4—C10−42.80 (16)C2—N1—C4—C5179.2 (3)
S3—Hg1—N1—C2−67.8 (3)Hg1—N1—C4—C511.1 (4)
S4—Hg1—N1—C2102.2 (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—C498.2 (3)C7—N2—C5—C4177.8 (3)
S4—Hg1—N1—C4−91.8 (3)Hg1—N2—C5—C43.1 (4)
N2—Hg1—N1—C4−6.6 (3)C3—C4—C5—C6−10.6 (7)
S3—Hg1—N2—C798.2 (4)N1—C4—C5—C6169.5 (4)
S4—Hg1—N2—C7−58.1 (4)C3—C4—C5—N2170.4 (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—S20.9 (4)
S4—Hg1—N2—C5115.3 (3)C4—C5—C6—S2−178.1 (3)
N1—Hg1—N2—C51.7 (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—S10.6 (4)C5—N2—C7—S21.0 (4)
Hg1—N1—C2—S1167.11 (18)Hg1—N2—C7—S2174.69 (19)
C3—S1—C2—N1−0.3 (3)C6—S2—C7—N2−0.4 (3)
C3—S1—C2—C1179.2 (4)C6—S2—C7—C8−179.9 (4)
Table 1
Selected geometric parameters (Å, °) top
Hg1—S32.413 (1)Hg1—N12.430 (3)
Hg1—S42.421 (1)Hg1—N22.476 (3)
S3—Hg1—S4149.25 (4)S4—Hg1—N1113.49 (8)
S3—Hg1—N195.66 (8)S4—Hg1—N294.04 (8)
S3—Hg1—N2105.84 (8)N1—Hg1—N269.1 (1)
Acknowledgements top

We thank Shahid Beheshti University and the University of Malaya for supporting this study.

references
References top

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