(2,2′-Dimethyl-4,4′-bi-1,3-thia­zole-κ2N,N′)diiodidomercury(II)

Abedi, A.; Yahyazade Bali, E.

doi:10.1107/S1600536810029302

metal-organic compounds

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Volume 66| Part 8| August 2010| Page m1023

https://doi.org/10.1107/S1600536810029302

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(2,2′-Dimethyl-4,4′-bi-1,3-thiazole-κ²N,N′)diiodidomercury(II)

Anita Abedi ^a ^* and Effat Yahyazade Bali ^a

^aDepartment of Chemistry, Islamic Azad University, North Tehran Branch, Tehran, Iran
^*Correspondence e-mail: anita_abedi@yahoo.com

(Received 18 July 2010; accepted 22 July 2010; online 31 July 2010)

In the title compound, [HgI₂(C₈H₈N₂S₂)], the Hg^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 2,2′-dimethyl-4,4′-bithiazole ligand and two I atoms. In the crystal structure, adjacent molecules are connected by π–π contacts between the thiazole rings [centroid–centroid distance = 3.591 (3) Å].

Related literature

For metal complexes with the 2,2′-dimethyl-4,4′-bithiazole ligand, see: Al-Hashemi et al. (2009 ); Khavasi et al. (2008 ); Notash et al. (2008 ). For related structures, see: Safari et al. (2009 ); Tadayon Pour et al. (2008 ); Yousefi et al. (2008 ).

Experimental

Crystal data

[HgI₂(C₈H₈N₂S₂)]
M_r = 650.67
Orthorhombic, P b c a
a = 12.9059 (10) Å
b = 14.8605 (11) Å
c = 14.9432 (11) Å
V = 2865.9 (4) Å³
Z = 8
Mo Kα radiation
μ = 15.31 mm⁻¹
T = 100 K
0.18 × 0.16 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.085, T_max = 0.191
27850 measured reflections
3135 independent reflections
2746 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.058
S = 1.00
3135 reflections
138 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −1.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Hg1—N1	2.397 (4)
Hg1—N2	2.408 (4)
Hg1—I1	2.6600 (4)
Hg1—I2	2.6592 (4)

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029302/hy2334sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029302/hy2334Isup2.hkl

checkCIF report

Comment top

Khavasi et al. (2008) reported the synthesis and structure of 2,2'-dimethyl-4,4'-bithiazole (dm4bt) by single crystal X-ray diffraction methods. Dm4bt is a good bidentate ligand, and numerous complexes with dm4bt have been prepared, such as those of zinc (Khavasi et al., 2008), thallium (Notash et al., 2008), cadmium (Notash et al., 2008) and copper (Al-Hashemi et al., 2009). For further investigation of dm4bt, we synthezised the title complex, and report herein its crystal structure.

In the title compound (Fig. 1), the Hg^II atom is four-coordinated in a distorted tetrahedral geometry by two N atoms from a 2,2'-dimethyl-4,4'-bithiazole ligand and two I atoms. The Hg—N and Hg—I bond lengths and angles (Table 1) are within normal range of [Hg(SCN)₂(dm4bt)] (Safari et al., 2009), [HgI₂(4,4'-dmbpy)] (Yousefi et al., 2008) and [HgI₂(5,5'-dmbpy)] (Tadayon Pour et al., 2008) (4,4'-dmbpy = 4,4'-dimethyl-2,2'-bipyridine; 5,5'-dmbpy = 5,5'-dimethyl-2, 2'-bipyridine). In the crystal structure, π–π contacts (Fig. 2) between the thiazole rings, Cg2···Cg3ⁱ [symmetry code: (i) 1-x, 1-y, -z. Cg2 and Cg3 are centroids of the S1, C1, N1, C3, C2 ring and the S2, C5, C4, N2, C6 ring], stabilize the structure, with a centroid–centroid distance of 3.591 (3) Å.

Related literature top

For metal complexes with the 2,2'-dimethyl-4,4'-bithiazole ligand, see: Al-Hashemi et al. (2009); Khavasi et al. (2008); Notash et al. (2008). For related structures, see: Safari et al. (2009); Tadayon Pour et al. (2008); Yousefi et al. (2008).

Experimental top

A solution of 2,2'-dimethyl-4,4'-bithiazole (0.20 g, 1.00 mmol) in methanol (15 ml) was added to a solution of HgI₂ (0.46 g, 1.00 mmol) in methanol (15 ml) at room temperature. Crystals suitable for X-ray diffraction experiment were obtained after one week by methanol diffusion to a colorless solution of the title compound in DMSO (yield: 0.48 g, 73.8%).

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing diagram of the title compound.

(2,2'-Dimethyl-4,4'-bi-1,3-thiazole-κ²N,N')diiodidomercury(II) top

Crystal data top

[HgI₂(C₈H₈N₂S₂)]	D_x = 3.016 Mg m⁻³
M_r = 650.67	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 4823 reflections
a = 12.9059 (10) Å	θ = 4–27°
b = 14.8605 (11) Å	µ = 15.31 mm⁻¹
c = 14.9432 (11) Å	T = 100 K
V = 2865.9 (4) Å³	Prism, colorless
Z = 8	0.18 × 0.16 × 0.11 mm
F(000) = 2304

Data collection top

Bruker APEXII CCD diffractometer	3135 independent reflections
Radiation source: fine-focus sealed tube	2746 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
φ and ω scans	θ_max = 27.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −16→16
T_min = 0.085, T_max = 0.191	k = −18→18
27850 measured reflections	l = −19→19

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.058	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.030P)² + 3.P] where P = (F_o² + 2F_c²)/3
3135 reflections	(Δ/σ)_max = 0.002
138 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −1.36 e Å⁻³

Crystal data top

[HgI₂(C₈H₈N₂S₂)]	V = 2865.9 (4) Å³
M_r = 650.67	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.9059 (10) Å	µ = 15.31 mm⁻¹
b = 14.8605 (11) Å	T = 100 K
c = 14.9432 (11) Å	0.18 × 0.16 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	3135 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2746 reflections with I > 2σ(I)
T_min = 0.085, T_max = 0.191	R_int = 0.060
27850 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	0 restraints
wR(F²) = 0.058	H-atom parameters constrained
S = 1.00	Δρ_max = 0.74 e Å⁻³
3135 reflections	Δρ_min = −1.36 e Å⁻³
138 parameters

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

	x	y	z	U_iso*/U_eq
Hg1	0.510845 (16)	0.378820 (14)	0.225249 (14)	0.01739 (7)
I1	0.59477 (3)	0.23923 (3)	0.14062 (3)	0.02478 (10)
I2	0.46410 (3)	0.41700 (2)	0.39435 (2)	0.02213 (9)
S1	0.61688 (11)	0.68779 (9)	0.15627 (10)	0.0197 (3)
S2	0.24214 (11)	0.45250 (10)	0.00224 (9)	0.0209 (3)
N1	0.5553 (3)	0.5267 (3)	0.1740 (3)	0.0169 (9)
N2	0.3846 (3)	0.4293 (3)	0.1177 (3)	0.0158 (9)
C1	0.6287 (4)	0.5813 (4)	0.2004 (4)	0.0177 (11)
C2	0.5076 (4)	0.6562 (4)	0.1008 (4)	0.0203 (12)
H2A	0.4678	0.6948	0.0637	0.024*
C3	0.4849 (4)	0.5682 (4)	0.1169 (4)	0.0181 (11)
C4	0.3987 (4)	0.5150 (4)	0.0821 (3)	0.0166 (11)
C5	0.3287 (4)	0.5378 (4)	0.0189 (4)	0.0186 (11)
H5A	0.3278	0.5936	−0.0121	0.022*
C6	0.3056 (4)	0.3887 (4)	0.0811 (4)	0.0177 (11)
C7	0.7144 (5)	0.5550 (4)	0.2603 (4)	0.0271 (13)
H7A	0.6860	0.5350	0.3178	0.041*
H7B	0.7602	0.6066	0.2700	0.041*
H7C	0.7537	0.5057	0.2330	0.041*
C8	0.2714 (5)	0.2959 (4)	0.1047 (4)	0.0260 (13)
H8A	0.2584	0.2923	0.1692	0.039*
H8B	0.3257	0.2528	0.0882	0.039*
H8C	0.2076	0.2815	0.0721	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.01885 (11)	0.01823 (11)	0.01509 (11)	0.00215 (8)	−0.00002 (8)	0.00063 (8)
I1	0.0298 (2)	0.0248 (2)	0.01979 (19)	0.01150 (16)	0.00339 (16)	0.00036 (15)
I2	0.0271 (2)	0.0226 (2)	0.01672 (18)	0.00144 (15)	0.00188 (14)	−0.00428 (14)
S1	0.0204 (7)	0.0173 (7)	0.0214 (7)	0.0005 (5)	−0.0012 (5)	0.0021 (5)
S2	0.0201 (7)	0.0259 (8)	0.0166 (7)	0.0026 (5)	−0.0042 (5)	0.0006 (6)
N1	0.018 (2)	0.019 (2)	0.013 (2)	0.0015 (18)	0.0012 (18)	0.0033 (18)
N2	0.016 (2)	0.018 (2)	0.013 (2)	0.0047 (17)	0.0009 (17)	−0.0022 (18)
C1	0.018 (3)	0.021 (3)	0.014 (3)	0.002 (2)	0.000 (2)	0.000 (2)
C2	0.015 (3)	0.025 (3)	0.021 (3)	0.005 (2)	0.000 (2)	−0.001 (2)
C3	0.017 (3)	0.026 (3)	0.011 (3)	0.005 (2)	0.004 (2)	0.001 (2)
C4	0.015 (3)	0.022 (3)	0.013 (3)	0.002 (2)	0.001 (2)	−0.003 (2)
C5	0.020 (3)	0.018 (3)	0.018 (3)	0.002 (2)	0.007 (2)	−0.003 (2)
C6	0.018 (3)	0.019 (3)	0.016 (3)	0.004 (2)	0.001 (2)	−0.005 (2)
C7	0.027 (3)	0.027 (3)	0.028 (3)	−0.004 (2)	−0.010 (3)	0.006 (3)
C8	0.028 (3)	0.023 (3)	0.027 (3)	−0.001 (2)	−0.007 (3)	0.000 (3)

Geometric parameters (Å, º) top

Hg1—N1	2.397 (4)	C2—C3	1.361 (8)
Hg1—N2	2.408 (4)	C2—H2A	0.9500
Hg1—I1	2.6600 (4)	C3—C4	1.462 (8)
Hg1—I2	2.6592 (4)	C4—C5	1.349 (7)
S1—C2	1.701 (6)	C5—H5A	0.9500
S1—C1	1.721 (6)	C6—C8	1.491 (8)
S2—C5	1.708 (6)	C7—H7A	0.9800
S2—C6	1.720 (6)	C7—H7B	0.9800
N1—C1	1.309 (7)	C7—H7C	0.9800
N1—C3	1.390 (7)	C8—H8A	0.9800
N2—C6	1.304 (7)	C8—H8B	0.9800
N2—C4	1.393 (7)	C8—H8C	0.9800
C1—C7	1.475 (8)

N1—Hg1—N2	70.32 (15)	N1—C3—C4	118.4 (5)
N1—Hg1—I2	99.35 (11)	C5—C4—N2	114.2 (5)
N2—Hg1—I2	114.46 (10)	C5—C4—C3	128.5 (5)
N1—Hg1—I1	117.74 (11)	N2—C4—C3	117.3 (5)
N2—Hg1—I1	101.61 (10)	C4—C5—S2	110.7 (4)
I2—Hg1—I1	135.280 (14)	C4—C5—H5A	124.7
C2—S1—C1	90.4 (3)	S2—C5—H5A	124.7
C5—S2—C6	89.9 (3)	N2—C6—C8	124.1 (5)
C1—N1—C3	112.5 (5)	N2—C6—S2	113.9 (4)
C1—N1—Hg1	130.2 (4)	C8—C6—S2	122.1 (4)
C3—N1—Hg1	116.5 (3)	C1—C7—H7A	109.5
C6—N2—C4	111.4 (4)	C1—C7—H7B	109.5
C6—N2—Hg1	131.7 (4)	H7A—C7—H7B	109.5
C4—N2—Hg1	116.9 (3)	C1—C7—H7C	109.5
N1—C1—C7	124.1 (5)	H7A—C7—H7C	109.5
N1—C1—S1	113.0 (4)	H7B—C7—H7C	109.5
C7—C1—S1	122.9 (4)	C6—C8—H8A	109.5
C3—C2—S1	110.9 (4)	C6—C8—H8B	109.5
C3—C2—H2A	124.5	H8A—C8—H8B	109.5
S1—C2—H2A	124.5	C6—C8—H8C	109.5
C2—C3—N1	113.2 (5)	H8A—C8—H8C	109.5
C2—C3—C4	128.4 (5)	H8B—C8—H8C	109.5

N2—Hg1—N1—C1	174.2 (5)	C1—N1—C3—C2	0.1 (7)
I2—Hg1—N1—C1	61.5 (5)	Hg1—N1—C3—C2	171.1 (4)
I1—Hg1—N1—C1	−92.7 (5)	C1—N1—C3—C4	180.0 (5)
N2—Hg1—N1—C3	5.1 (3)	Hg1—N1—C3—C4	−9.0 (6)
I2—Hg1—N1—C3	−107.6 (4)	C6—N2—C4—C5	0.4 (6)
I1—Hg1—N1—C3	98.2 (4)	Hg1—N2—C4—C5	176.8 (4)
N1—Hg1—N2—C6	174.7 (5)	C6—N2—C4—C3	−179.8 (5)
I2—Hg1—N2—C6	−93.8 (5)	Hg1—N2—C4—C3	−3.5 (6)
I1—Hg1—N2—C6	59.1 (5)	C2—C3—C4—C5	8.0 (9)
N1—Hg1—N2—C4	−0.7 (3)	N1—C3—C4—C5	−171.9 (5)
I2—Hg1—N2—C4	90.8 (3)	C2—C3—C4—N2	−171.8 (5)
I1—Hg1—N2—C4	−116.3 (3)	N1—C3—C4—N2	8.4 (7)
C3—N1—C1—C7	−179.2 (5)	N2—C4—C5—S2	0.3 (6)
Hg1—N1—C1—C7	11.3 (8)	C3—C4—C5—S2	−179.5 (4)
C3—N1—C1—S1	−0.4 (6)	C6—S2—C5—C4	−0.6 (4)
Hg1—N1—C1—S1	−169.9 (2)	C4—N2—C6—C8	179.5 (5)
C2—S1—C1—N1	0.4 (4)	Hg1—N2—C6—C8	3.9 (8)
C2—S1—C1—C7	179.3 (5)	C4—N2—C6—S2	−0.9 (6)
C1—S1—C2—C3	−0.4 (4)	Hg1—N2—C6—S2	−176.6 (2)
S1—C2—C3—N1	0.2 (6)	C5—S2—C6—N2	0.9 (4)
S1—C2—C3—C4	−179.6 (4)	C5—S2—C6—C8	−179.5 (5)

Experimental details

Crystal data
Chemical formula	[HgI₂(C₈H₈N₂S₂)]
M_r	650.67
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	100
a, b, c (Å)	12.9059 (10), 14.8605 (11), 14.9432 (11)
V (Å³)	2865.9 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	15.31
Crystal size (mm)	0.18 × 0.16 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.085, 0.191
No. of measured, independent and observed [I > 2σ(I)] reflections	27850, 3135, 2746
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.058, 1.00
No. of reflections	3135
No. of parameters	138
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −1.36

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Hg1—N1	2.397 (4)	Hg1—I1	2.6600 (4)
Hg1—N2	2.408 (4)	Hg1—I2	2.6592 (4)

Acknowledgements

We are grateful to the Islamic Azad University, North Tehran Branch, for financial support.

References

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