(2,2′-Dimethyl-4,4′-bi-1,3-thia­zole-κ² N,N′)diiodidomercury(II)

Abstract

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,

• a = 12.9059 (10) Å

• b = 14.8605 (11) Å

• c = 14.9432 (11) Å

• V = 2865.9 (4) ų

• 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[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 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

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.

Supplementary Material

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

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)

supplementary crystallographic information

Comment

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.

Experimental

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%).

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.95 (CH) and 0.98 (CH₃) Å and with U_iso(H) = 1.2(1.5 for methyl)U_eq(C).

Figures

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.

Crystal data

[HgI2(C8H8N2S2)]	Dx = 3.016 Mg m−3
Mr = 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

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

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.058	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.030P)2 + 3.P] where P = (Fo2 + 2Fc2)/3
3135 reflections	(Δ/σ)max = 0.002
138 parameters	Δρmax = 0.74 e Å−3
0 restraints	Δρmin = −1.36 e Å−3

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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)