1-Butyl-3-(1-naphthyl­meth­yl)benzimidazolium hemi{di-μ-iodido-bis­[diiodidomercurate(II)]} dimethyl sulfoxide monosolvate

Wang, Z.-Q.; Shen, G.; Zheng, Z.-Y.; Wu, X.-M.; Liu, Q.-X.

doi:10.1107/S1600536809046376

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1639

doi:10.1107/S1600536809046376

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1-Butyl-3-(1-naphthylmethyl)benzimidazolium hemi{di-μ-iodido-bis[diiodidomercurate(II)]} dimethyl sulfoxide monosolvate

Zhi-Qiang Wang,^a Gang Shen,^a Zhan-Ying Zheng,^b Xiu-Mei Wu ^a and Qing-Xiang Liu ^a ^*

^aTianjin Key Laboratory of Structure and Performance of Functional Molecules, College of Chemistry and Life Science, Tianjin Normal University, Tianjin 300387, People's Republic of China, and ^bState Key Laboratory of Element-Organic Chemistry, Nankai University, Tianjin 300071, People's Republic of China
^*Correspondence e-mail: qxliu@eyou.com

(Received 19 October 2009; accepted 4 November 2009; online 21 November 2009)

In the title compound, (C₂₂H₂₃N₂)[Hg₂I₆]_0.5·(CH₃)₂SO, the 1-butyl-3-(1-naphthylmethyl)benzimidazolium anion lies across a centre of inversion. The dihedral angle between the benzimidazolium and naphthalene ring systems is 81.9 (3)°. In the crystal structure, π–π stacking interactions are observed between the imidazolium ring and the unsubstituted benzene ring of the naphthalene ring system, with a centroid–centroid separation of 3.510 (5) Å. In the centrosymmetric anion, the Hg(II) atoms are in a distorted tetrahedral coordination. The dimethyl sulfoxide solvent molecule is disordered over two sites with occupancies of 0.615 (9) and 0.385 (9).

Related literature

For background to the chemistry of imidazolium compounds, see: Arduengo et al. (1991 ); Garrison & Youngs (2005 ). For a related structure, see: Liu et al. (2003 ).

Experimental

Crystal data

(C₂₂H₂₃N₂)[Hg₂I₆]_0.5·C₂H₆OS
M_r = 974.85
Monoclinic, P 2₁ /c
a = 12.0565 (13) Å
b = 13.7312 (16) Å
c = 18.378 (2) Å
β = 102.089 (2)°
V = 2975.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 8.38 mm⁻¹
T = 296 K
0.28 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.110, T_max = 0.158
14876 measured reflections
5253 independent reflections
3641 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.111
S = 1.03
5253 reflections
327 parameters
60 restraints
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −1.71 e Å⁻³

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809046376/ci2946sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809046376/ci2946Isup2.hkl

checkCIF report

Comment top

Since the discovery of free stable N-heterocyclic carbene (NHC) (Arduengo et al., 1991), the carbene chemistry based on imidazol-2-ylidene (imy) or benzimidazol-2-ylidene (bimy) have been receiving considerable attention, owing to their inherent stability, their interesting characteristics of structure and bonding, and their potential for synthesis and as catalysts in organic reactions (Garrison & Youngs, 2005). We report here the synthesis and crystal structure of the title compound (Fig. 1).

The dihedral angle between benzimidazolium and naphthalene ring systems is 81.9 (3)°. The butyl group and 1-naphthylmethyl group lie on the same side of benzimidazole ring system. The N—C and C—N—C angles agree with those observed in 1-(9-anthracenylmethyl)-3-ethylimidazolium iodide (Liu et al., 2003).

The [Hg₂I₆]^2- anionic unit lies across a centre of inversion, in which atoms Hg1, I2, Hg1A and I2A are coplanar, with I2—Hg1—I2A and Hg1—I2—Hg1A angles of 94.29 (2)° and 85.71 (2)°, respectively. All Hg—I bond distances fall in the regular range of 2.6792 (9)–2.8943 (4) Å.

Related literature top

For background to the chemistry of imidazolium compounds, see: Arduengo et al. (1991); Garrison & Youngs (2005). For a related structure, see: Liu et al. (2003).

Experimental top

A solution of 1-iodobutane (1.583 g, 8.6 mmol) and 1-(1-naphthylmethyl)benzimidazole (1.860 g, 7.2 mmol) in THF (100 ml) was stirred for five days under refluxing, and a pale yellow precipitate was formed. The product was filtred and washed with THF. The powder of benzimidazolium iodide are obtained by recrystallization from methanol/diethyl ether [3.5 g (91%), m.p 188–190°C]. A mixture of benzimidazolium iodide (0.199 g, 0.45 mmol) and mercury(II) iodide (0.245 g, 0.54 mmol) in THF (20 ml) and dichloromethane (20 ml) was refluxed for 24 h. A brown solution was formed and the solvent was removed with a rotary evaporator. Water (30 ml) was added to the residue and the solution was extracted with CH₂Cl₂ (30 ml). The extracting solution was dried with anhydrate MgSO₄, then the solution was concentrated to 10 ml and diethyl ether (5 ml) was added. A pale yellow powder was obtained, and isolation by filtration yielded the title compound [yield 0.401 g (83%), m.p 235–237°C). ¹H NMR (300 MHZ, DMSO-d6): 0.97 (t, J = 5.4, 3H, CH₃), 1.46 (m, 2H, CH₂), 2.03 (m, 2H, CH₂), 4.55 (t, J = 7.2, 2H, CH₂), 6.31 (s, 2H, CH₂), 7.43 (t, J = 6.0, 1H, PhH), 7.55 (d, J = 6.0, 2H, PhH), 7.63 (d, J = 6.3, 4H, PhH), 7.65 (t, J = 8.8, 1H, PhH), 7.91 (d, J = 8.4, 2H, PhH), 8.13 (d, J = 8.4, 1H, PhH), 11.23 (s, 1H, bimiH) (bimi: benzimidazole). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an CH₂Cl₂ solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of the title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity. Only the major component of the disordered DMSO molecule is shown.

1-Butyl-3-(1-naphthylmethyl)benzimidazolium hemi{di-µ-iodido-bis[diiodidomercurate(II)]} dimethyl sulfoxide monosolvate top

Crystal data top

(C₂₂H₂₃N₂)[Hg₂I₆]_0.5·C₂H₆OS	F(000) = 1800
M_r = 974.85	D_x = 2.177 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3658 reflections
a = 12.0565 (13) Å	θ = 2.3–23.9°
b = 13.7312 (16) Å	µ = 8.38 mm⁻¹
c = 18.378 (2) Å	T = 296 K
β = 102.089 (2)°	Block, yellow
V = 2975.0 (6) Å³	0.28 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5253 independent reflections
Radiation source: fine-focus sealed tube	3641 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.110, T_max = 0.158	k = −16→11
14876 measured reflections	l = −21→21

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0474P)² + 6.0193P] where P = (F_o² + 2F_c²)/3
5253 reflections	(Δ/σ)_max = 0.001
327 parameters	Δρ_max = 1.16 e Å⁻³
60 restraints	Δρ_min = −1.71 e Å⁻³

Crystal data top

(C₂₂H₂₃N₂)[Hg₂I₆]_0.5·C₂H₆OS	V = 2975.0 (6) Å³
M_r = 974.85	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.0565 (13) Å	µ = 8.38 mm⁻¹
b = 13.7312 (16) Å	T = 296 K
c = 18.378 (2) Å	0.28 × 0.26 × 0.22 mm
β = 102.089 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5253 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3641 reflections with I > 2σ(I)
T_min = 0.110, T_max = 0.158	R_int = 0.044
14876 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	60 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.03	Δρ_max = 1.16 e Å⁻³
5253 reflections	Δρ_min = −1.71 e Å⁻³
327 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Hg1	0.61164 (3)	0.57544 (3)	0.95810 (2)	0.07147 (16)
I1	0.83044 (5)	0.51958 (4)	0.98219 (4)	0.06220 (19)
I2	0.47338 (6)	0.40737 (6)	0.90484 (4)	0.0883 (3)
I3	0.53530 (6)	0.73713 (6)	0.88235 (5)	0.0985 (3)
N1	−0.0121 (6)	0.4144 (4)	0.2680 (3)	0.0446 (15)
N2	0.0684 (5)	0.3180 (4)	0.3578 (3)	0.0433 (15)
C1	−0.1740 (8)	0.6136 (6)	0.2289 (5)	0.059 (2)
H1	−0.2223	0.5783	0.1922	0.071*
C2	−0.2176 (9)	0.6929 (7)	0.2618 (6)	0.071 (3)
H2	−0.2938	0.7092	0.2468	0.085*
C3	−0.1503 (9)	0.7452 (7)	0.3148 (5)	0.065 (3)
H3	−0.1804	0.7969	0.3370	0.078*
C4	−0.0332 (8)	0.7225 (6)	0.3373 (4)	0.051 (2)
C5	0.0393 (9)	0.7759 (6)	0.3924 (5)	0.063 (2)
H5	0.0099	0.8269	0.4158	0.076*
C6	0.1503 (10)	0.7553 (7)	0.4125 (5)	0.071 (3)
H6	0.1966	0.7916	0.4495	0.085*
C7	0.1962 (9)	0.6798 (7)	0.3781 (5)	0.071 (3)
H7	0.2732	0.6658	0.3922	0.085*
C8	0.1289 (7)	0.6259 (6)	0.3235 (5)	0.057 (2)
H8	0.1614	0.5769	0.2999	0.068*
C9	0.0119 (7)	0.6431 (5)	0.3025 (4)	0.0476 (19)
C10	−0.0635 (7)	0.5867 (5)	0.2488 (4)	0.0460 (19)
C11	−0.0249 (7)	0.4955 (6)	0.2146 (4)	0.052 (2)
H11A	−0.0801	0.4782	0.1700	0.063*
H11B	0.0470	0.5078	0.2005	0.063*
C12	0.0855 (7)	0.3871 (5)	0.3116 (4)	0.0431 (18)
H12	0.1560	0.4131	0.3096	0.052*
C13	−0.0978 (6)	0.3588 (5)	0.2866 (4)	0.0412 (17)
C14	−0.2127 (8)	0.3544 (6)	0.2578 (5)	0.058 (2)
H14	−0.2478	0.3943	0.2189	0.069*
C15	−0.2726 (8)	0.2872 (8)	0.2901 (6)	0.069 (3)
H15	−0.3506	0.2823	0.2728	0.083*
C16	−0.2195 (9)	0.2262 (7)	0.3481 (6)	0.070 (3)
H16	−0.2632	0.1813	0.3677	0.084*
C17	−0.1077 (8)	0.2305 (6)	0.3763 (5)	0.057 (2)
H17	−0.0729	0.1902	0.4151	0.068*
C18	−0.0465 (7)	0.2981 (5)	0.3446 (4)	0.0445 (18)
C19	0.1555 (8)	0.2795 (6)	0.4189 (4)	0.058 (2)
H19A	0.2299	0.2893	0.4078	0.070*
H19B	0.1442	0.2101	0.4239	0.070*
C20	0.1505 (8)	0.3299 (6)	0.4918 (5)	0.059 (2)
H20A	0.0752	0.3207	0.5016	0.071*
H20B	0.2039	0.2981	0.5315	0.071*
C21	0.1762 (9)	0.4371 (7)	0.4943 (5)	0.072 (3)
H21A	0.2527	0.4460	0.4867	0.086*
H21B	0.1250	0.4684	0.4532	0.086*
C22	0.1665 (9)	0.4881 (8)	0.5648 (5)	0.084 (3)
H22A	0.0898	0.4837	0.5715	0.126*
H22B	0.1870	0.5553	0.5619	0.126*
H22C	0.2165	0.4579	0.6062	0.126*
S1	0.5566 (4)	0.8983 (4)	0.1687 (3)	0.0831 (19)	0.615 (9)
O1	0.6734 (8)	0.9226 (16)	0.1578 (11)	0.132 (10)	0.615 (9)
C23	0.5144 (19)	0.9966 (15)	0.2185 (12)	0.127 (11)	0.615 (9)
H23A	0.5567	0.9953	0.2689	0.191*	0.615 (9)
H23B	0.4349	0.9912	0.2181	0.191*	0.615 (9)
H23C	0.5285	1.0568	0.1954	0.191*	0.615 (9)
C24	0.4652 (16)	0.921 (2)	0.0812 (8)	0.160 (13)	0.615 (9)
H24A	0.4795	0.8736	0.0457	0.241*	0.615 (9)
H24B	0.4790	0.9850	0.0645	0.241*	0.615 (9)
H24C	0.3877	0.9157	0.0861	0.241*	0.615 (9)
S1'	0.5614 (7)	0.9773 (6)	0.1314 (4)	0.089 (3)	0.385 (9)
O1'	0.6753 (11)	0.943 (2)	0.1700 (14)	0.100 (11)	0.385 (9)
C23'	0.481 (2)	0.995 (2)	0.2005 (13)	0.077 (9)	0.385 (9)
H23D	0.5145	1.0455	0.2339	0.116*	0.385 (9)
H23E	0.4789	0.9355	0.2278	0.116*	0.385 (9)
H23F	0.4046	1.0133	0.1772	0.116*	0.385 (9)
C24'	0.485 (2)	0.8777 (19)	0.0855 (15)	0.112 (12)	0.385 (9)
H24D	0.5197	0.8569	0.0454	0.168*	0.385 (9)
H24E	0.4083	0.8968	0.0659	0.168*	0.385 (9)
H24F	0.4866	0.8250	0.1200	0.168*	0.385 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0457 (2)	0.0806 (3)	0.0874 (3)	0.00266 (18)	0.01229 (19)	0.0094 (2)
I1	0.0479 (3)	0.0505 (3)	0.0878 (4)	0.0062 (3)	0.0134 (3)	−0.0007 (3)
I2	0.0773 (5)	0.1162 (6)	0.0770 (5)	−0.0384 (4)	0.0289 (4)	−0.0373 (4)
I3	0.0758 (5)	0.1001 (6)	0.1121 (6)	0.0222 (4)	0.0029 (4)	0.0270 (5)
N1	0.060 (4)	0.042 (4)	0.034 (3)	0.004 (3)	0.015 (3)	−0.001 (3)
N2	0.051 (4)	0.041 (3)	0.041 (4)	0.007 (3)	0.014 (3)	0.001 (3)
C1	0.075 (6)	0.050 (5)	0.053 (5)	0.005 (4)	0.013 (5)	0.016 (4)
C2	0.085 (7)	0.057 (6)	0.076 (7)	0.021 (5)	0.027 (6)	0.018 (5)
C3	0.099 (8)	0.047 (5)	0.060 (6)	0.015 (5)	0.039 (6)	0.002 (5)
C4	0.075 (6)	0.039 (4)	0.046 (5)	0.001 (4)	0.029 (4)	0.012 (4)
C5	0.091 (8)	0.048 (5)	0.059 (6)	−0.007 (5)	0.035 (5)	0.002 (4)
C6	0.108 (9)	0.053 (6)	0.057 (6)	−0.018 (6)	0.025 (6)	−0.002 (5)
C7	0.073 (6)	0.057 (6)	0.080 (7)	−0.015 (5)	0.012 (5)	0.009 (5)
C8	0.068 (6)	0.043 (5)	0.068 (6)	−0.002 (4)	0.036 (5)	0.010 (4)
C9	0.065 (5)	0.038 (4)	0.046 (5)	0.002 (4)	0.026 (4)	0.016 (4)
C10	0.070 (6)	0.043 (4)	0.028 (4)	0.008 (4)	0.014 (4)	0.009 (3)
C11	0.068 (5)	0.052 (5)	0.038 (4)	0.005 (4)	0.012 (4)	0.004 (4)
C12	0.047 (5)	0.044 (4)	0.038 (4)	0.000 (3)	0.009 (4)	−0.003 (4)
C13	0.046 (4)	0.042 (4)	0.039 (4)	0.003 (3)	0.016 (4)	−0.008 (4)
C14	0.069 (6)	0.055 (5)	0.050 (5)	0.009 (5)	0.014 (4)	−0.009 (4)
C15	0.047 (5)	0.086 (7)	0.075 (7)	−0.012 (5)	0.015 (5)	−0.027 (6)
C16	0.076 (7)	0.069 (6)	0.071 (6)	−0.017 (5)	0.029 (6)	−0.004 (5)
C17	0.071 (6)	0.055 (5)	0.049 (5)	−0.008 (4)	0.024 (5)	0.002 (4)
C18	0.057 (5)	0.042 (4)	0.038 (4)	0.003 (4)	0.017 (4)	−0.006 (4)
C19	0.064 (5)	0.053 (5)	0.056 (5)	0.006 (4)	0.008 (4)	0.007 (4)
C20	0.062 (5)	0.063 (6)	0.048 (5)	−0.004 (4)	0.002 (4)	0.010 (4)
C21	0.079 (7)	0.080 (7)	0.058 (6)	−0.003 (5)	0.018 (5)	0.004 (5)
C22	0.099 (8)	0.098 (8)	0.058 (6)	−0.015 (7)	0.022 (6)	−0.016 (6)
S1	0.078 (3)	0.085 (3)	0.094 (3)	0.016 (2)	0.036 (2)	0.019 (2)
O1	0.119 (11)	0.140 (11)	0.139 (11)	0.006 (5)	0.033 (5)	−0.008 (5)
C23	0.128 (12)	0.129 (12)	0.127 (12)	0.003 (5)	0.030 (5)	−0.004 (5)
C24	0.159 (13)	0.161 (13)	0.161 (13)	0.004 (5)	0.033 (6)	−0.001 (5)
S1'	0.093 (4)	0.086 (5)	0.098 (5)	0.007 (3)	0.043 (3)	0.009 (3)
O1'	0.090 (12)	0.107 (12)	0.108 (12)	0.004 (5)	0.028 (5)	−0.008 (5)
C23'	0.077 (10)	0.079 (10)	0.077 (10)	0.002 (5)	0.019 (5)	−0.004 (5)
C24'	0.110 (13)	0.111 (13)	0.114 (13)	0.002 (5)	0.024 (6)	−0.003 (5)

Geometric parameters (Å, º) top

Hg1—I3	2.6792 (9)	C15—C16	1.402 (13)
Hg1—I1	2.6933 (7)	C15—H15	0.93
Hg1—I2	2.8943 (5)	C16—C17	1.341 (12)
Hg1—I2	2.8943 (4)	C16—H16	0.93
I2—Hg1	2.8943 (4)	C17—C18	1.387 (11)
N1—C12	1.331 (9)	C17—H17	0.93
N1—C13	1.384 (9)	C19—C20	1.519 (12)
N1—C11	1.472 (9)	C19—H19A	0.97
N2—C12	1.318 (9)	C19—H19B	0.97
N2—C18	1.383 (9)	C20—C21	1.503 (12)
N2—C19	1.466 (10)	C20—H20A	0.97
C1—C10	1.357 (11)	C20—H20B	0.97
C1—C2	1.400 (13)	C21—C22	1.498 (13)
C1—H1	0.93	C21—H21A	0.97
C2—C3	1.339 (13)	C21—H21B	0.97
C2—H2	0.93	C22—H22A	0.96
C3—C4	1.420 (13)	C22—H22B	0.96
C3—H3	0.93	C22—H22C	0.96
C4—C5	1.400 (12)	S1—O1	1.5010 (9)
C4—C9	1.428 (11)	S1—C23	1.7650 (9)
C5—C6	1.342 (14)	S1—C24	1.7750 (9)
C5—H5	0.93	C23—H23A	0.96
C6—C7	1.387 (14)	C23—H23B	0.96
C6—H6	0.93	C23—H23C	0.96
C7—C8	1.368 (12)	C24—H24A	0.96
C7—H7	0.93	C24—H24B	0.96
C8—C9	1.403 (11)	C24—H24C	0.96
C8—H8	0.93	S1'—O1'	1.484 (10)
C9—C10	1.423 (11)	S1'—C24'	1.761 (10)
C10—C11	1.518 (11)	S1'—C23'	1.771 (9)
C11—H11A	0.97	C23'—H23D	0.96
C11—H11B	0.97	C23'—H23E	0.96
C12—H12	0.9300	C23'—H23F	0.96
C13—C14	1.376 (11)	C24'—H24D	0.96
C13—C18	1.392 (10)	C24'—H24E	0.96
C14—C15	1.380 (13)	C24'—H24F	0.96
C14—H14	0.93

I3—Hg1—I1	122.65 (3)	C17—C16—H16	119.0
I3—Hg1—I2	111.97 (3)	C15—C16—H16	119.0
I1—Hg1—I2	107.66 (3)	C16—C17—C18	116.6 (9)
I3—Hg1—I2ⁱ	103.69 (3)	C16—C17—H17	121.7
I1—Hg1—I2ⁱ	112.94 (3)	C18—C17—H17	121.7
I2—Hg1—I2ⁱ	94.29 (2)	N2—C18—C17	131.3 (8)
Hg1—I2—Hg1ⁱ	85.71 (2)	N2—C18—C13	106.5 (6)
C12—N1—C13	108.0 (6)	C17—C18—C13	122.1 (8)
C12—N1—C11	124.8 (7)	N2—C19—C20	110.9 (7)
C13—N1—C11	127.1 (7)	N2—C19—H19A	109.5
C12—N2—C18	108.4 (6)	C20—C19—H19A	109.5
C12—N2—C19	124.8 (7)	N2—C19—H19B	109.5
C18—N2—C19	126.4 (7)	C20—C19—H19B	109.5
C10—C1—C2	122.1 (9)	H19A—C19—H19B	108.0
C10—C1—H1	118.9	C21—C20—C19	115.3 (8)
C2—C1—H1	118.9	C21—C20—H20A	108.4
C3—C2—C1	120.4 (9)	C19—C20—H20A	108.4
C3—C2—H2	119.8	C21—C20—H20B	108.4
C1—C2—H2	119.8	C19—C20—H20B	108.4
C2—C3—C4	120.6 (8)	H20A—C20—H20B	107.5
C2—C3—H3	119.7	C22—C21—C20	115.6 (9)
C4—C3—H3	119.7	C22—C21—H21A	108.4
C5—C4—C3	121.9 (8)	C20—C21—H21A	108.4
C5—C4—C9	119.0 (8)	C22—C21—H21B	108.4
C3—C4—C9	119.1 (8)	C20—C21—H21B	108.4
C6—C5—C4	121.6 (9)	H21A—C21—H21B	107.4
C6—C5—H5	119.2	C21—C22—H22A	109.5
C4—C5—H5	119.2	C21—C22—H22B	109.5
C5—C6—C7	120.1 (10)	H22A—C22—H22B	109.5
C5—C6—H6	119.9	C21—C22—H22C	109.5
C7—C6—H6	119.9	H22A—C22—H22C	109.5
C8—C7—C6	120.5 (10)	H22B—C22—H22C	109.5
C8—C7—H7	119.8	O1—S1—C23	106.2 (8)
C6—C7—H7	119.8	O1—S1—C24	105.2 (7)
C7—C8—C9	121.2 (9)	C23—S1—C24	98.3 (6)
C7—C8—H8	119.4	S1—C23—H23A	109.5
C9—C8—H8	119.4	S1—C23—H23B	109.5
C8—C9—C10	124.0 (7)	H23A—C23—H23B	109.5
C8—C9—C4	117.5 (8)	S1—C23—H23C	109.5
C10—C9—C4	118.6 (8)	H23A—C23—H23C	109.5
C1—C10—C9	119.2 (7)	H23B—C23—H23C	109.5
C1—C10—C11	118.8 (8)	S1—C24—H24A	109.5
C9—C10—C11	122.0 (7)	S1—C24—H24B	109.5
N1—C11—C10	110.3 (6)	H24A—C24—H24B	109.5
N1—C11—H11A	109.6	S1—C24—H24C	109.5
C10—C11—H11A	109.6	H24A—C24—H24C	109.5
N1—C11—H11B	109.6	H24B—C24—H24C	109.5
C10—C11—H11B	109.6	O1'—S1'—C24'	108.6 (8)
H11A—C11—H11B	108.1	O1'—S1'—C23'	107.1 (8)
N2—C12—N1	110.6 (7)	C24'—S1'—C23'	98.1 (7)
N2—C12—H12	124.7	S1'—C23'—H23D	109.5
N1—C12—H12	124.7	S1'—C23'—H23E	109.5
C14—C13—N1	132.3 (8)	H23D—C23'—H23E	109.5
C14—C13—C18	121.2 (8)	S1'—C23'—H23F	109.5
N1—C13—C18	106.5 (6)	H23D—C23'—H23F	109.5
C13—C14—C15	116.1 (8)	H23E—C23'—H23F	109.5
C13—C14—H14	122.0	S1'—C24'—H24D	109.5
C15—C14—H14	122.0	S1'—C24'—H24E	109.5
C14—C15—C16	122.0 (8)	H24D—C24'—H24E	109.5
C14—C15—H15	119.0	S1'—C24'—H24F	109.5
C16—C15—H15	119.0	H24D—C24'—H24F	109.5
C17—C16—C15	121.9 (9)	H24E—C24'—H24F	109.5

I3—Hg1—I2—Hg1ⁱ	−106.63 (3)	C18—N2—C12—N1	0.0 (8)
I1—Hg1—I2—Hg1ⁱ	115.73 (3)	C19—N2—C12—N1	−172.5 (6)
I2ⁱ—Hg1—I2—Hg1ⁱ	0.0	C13—N1—C12—N2	−0.7 (8)
C10—C1—C2—C3	0.0 (13)	C11—N1—C12—N2	174.5 (6)
C1—C2—C3—C4	1.3 (13)	C12—N1—C13—C14	−177.3 (8)
C2—C3—C4—C5	180.0 (8)	C11—N1—C13—C14	7.7 (12)
C2—C3—C4—C9	0.2 (12)	C12—N1—C13—C18	1.1 (8)
C3—C4—C5—C6	−178.7 (8)	C11—N1—C13—C18	−174.0 (6)
C9—C4—C5—C6	1.1 (12)	N1—C13—C14—C15	178.6 (7)
C4—C5—C6—C7	0.4 (13)	C18—C13—C14—C15	0.4 (11)
C5—C6—C7—C8	0.1 (14)	C13—C14—C15—C16	−0.8 (13)
C6—C7—C8—C9	−2.0 (13)	C14—C15—C16—C17	0.9 (14)
C7—C8—C9—C10	−176.8 (7)	C15—C16—C17—C18	−0.6 (13)
C7—C8—C9—C4	3.4 (11)	C12—N2—C18—C17	177.9 (8)
C5—C4—C9—C8	−2.9 (10)	C19—N2—C18—C17	−9.7 (13)
C3—C4—C9—C8	176.9 (7)	C12—N2—C18—C13	0.7 (8)
C5—C4—C9—C10	177.3 (7)	C19—N2—C18—C13	173.1 (7)
C3—C4—C9—C10	−2.9 (10)	C16—C17—C18—N2	−176.7 (8)
C2—C1—C10—C9	−2.8 (12)	C16—C17—C18—C13	0.1 (12)
C2—C1—C10—C11	175.5 (7)	C14—C13—C18—N2	177.5 (7)
C8—C9—C10—C1	−175.6 (7)	N1—C13—C18—N2	−1.1 (7)
C4—C9—C10—C1	4.2 (10)	C14—C13—C18—C17	−0.1 (11)
C8—C9—C10—C11	6.1 (11)	N1—C13—C18—C17	−178.7 (7)
C4—C9—C10—C11	−174.1 (6)	C12—N2—C19—C20	95.8 (9)
C12—N1—C11—C10	−97.1 (9)	C18—N2—C19—C20	−75.3 (9)
C13—N1—C11—C10	77.2 (9)	N2—C19—C20—C21	−63.9 (10)
C1—C10—C11—N1	−102.6 (8)	C19—C20—C21—C22	177.5 (8)
C9—C10—C11—N1	75.7 (9)

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	(C₂₂H₂₃N₂)[Hg₂I₆]_0.5·C₂H₆OS
M_r	974.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	12.0565 (13), 13.7312 (16), 18.378 (2)
β (°)	102.089 (2)
V (Å³)	2975.0 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	8.38
Crystal size (mm)	0.28 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.110, 0.158
No. of measured, independent and observed [I > 2σ(I)] reflections	14876, 5253, 3641
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.111, 1.03
No. of reflections	5253
No. of parameters	327
No. of restraints	60
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.16, −1.71

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This project was supported by the National Science Foundation of China (grant No. 20872111) and the Natural Science Foundation of Tianjin (grant No. 07JCYBJC00300).

References

Arduengo, A. J. III, Harlow, R. L. & Kline, M. (1991). J. Am. Chem. Soc. 113, 361–363. CSD CrossRef CAS Web of Science Google Scholar
Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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Liu, Q. X., Xu, F. B., Li, Q. S., Zeng, X. S., Leng, X. B., Chou, Y. L. & Zhang, Z. Z. (2003). Organometallics, 22, 309–314. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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