(2,2′-Dimethyl-4,4′-bi-1,3-thia­zole-κ2N,N′)bis(thio­cyanato-κS)mercury(II)

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

doi:10.1107/S1600536809006904

metal-organic compounds

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Volume 65| Part 4| April 2009| Page m372

doi:10.1107/S1600536809006904

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(2,2′-Dimethyl-4,4′-bi-1,3-thiazole-κ²N,N′)bis(thiocyanato-κS)mercury(II)

Nasser Safari,^a Vahid Amani,^a Anita Abedi,^a Behrouz Notash ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran, Iran, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 25 February 2009; accepted 25 February 2009; online 6 March 2009)

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, P 2₁ /c
a = 17.3764 (3) Å
b = 12.0534 (2) Å
c = 7.0601 (1) Å
β = 100.676 (1)°
V = 1453.10 (4) Å³
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[F² > 2σ(F²)] = 0.022
wR(F²) = 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

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)

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006904/xu2488sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809006904/xu2488Isup2.hkl

checkCIF report

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).

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

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
M_r = 513.03	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0213P)² + 2.1611P] where P = (F_o² + 2F_c²)/3
3330 reflections	(Δ/σ)_max = 0.001
174 parameters	Δρ_max = 1.17 e Å⁻³
0 restraints	Δρ_min = −1.32 e Å⁻³

Crystal data top

[Hg(NCS)₂(C₈H₈N₂S₂)]	V = 1453.10 (4) Å³
M_r = 513.03	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.3764 (3) Å	µ = 11.16 mm⁻¹
b = 12.0534 (2) Å	T = 118 K
c = 7.0601 (1) Å	0.22 × 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)
T_min = 0.274, T_max = 0.640	R_int = 0.030
10030 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.022	0 restraints
wR(F²) = 0.054	H-atom parameters constrained
S = 1.04	Δρ_max = 1.17 e Å⁻³
3330 reflections	Δρ_min = −1.32 e Å⁻³
174 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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)

Experimental details

Crystal data
Chemical formula	[Hg(NCS)₂(C₈H₈N₂S₂)]
M_r	513.03
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	118
a, b, c (Å)	17.3764 (3), 12.0534 (2), 7.0601 (1)
β (°)	100.676 (1)
V (Å³)	1453.10 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	11.16
Crystal size (mm)	0.22 × 0.06 × 0.04

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.274, 0.640
No. of measured, independent and observed [I > 2σ(I)] reflections	10030, 3330, 2982
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.022, 0.054, 1.04
No. of reflections	3330
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.17, −1.32

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), pubCIF (Westrip, 2009).

Selected geometric parameters (Å, º) top

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

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

Acknowledgements

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

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