2-[(1H-Imidazol-2-yl)disulfan­yl]-1H-imidazole

Feizbakhsh Bazargani, M.; Talavat, L.; Naderi, S.; Khavasi, H.R.

doi:10.1107/S1600536811036014

organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page o2585

https://doi.org/10.1107/S1600536811036014

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2-[(1H-Imidazol-2-yl)disulfanyl]-1H-imidazole

Mona Feizbakhsh Bazargani,^a Laleh Talavat,^a Soheila Naderi ^a and Hamid Reza Khavasi ^a ^*

^aDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: h-khavasi@sbu.ac.ir

(Received 1 September 2011; accepted 4 September 2011; online 14 September 2011)

In the title molecule, C₆H₆N₄S₂, a twofold rotation axis passes through the mid-point of the S—S bond. The C—S—S—C torsion angle is 83.62 (17)°. π–π stacking between imidazole rings of adjacent molecules is observed in the crystal structure, the centroid–centroid distance being 3.447 (2) Å. Intermolecular N—H⋯S hydrogen bonding results in the formation of a linear chain in the c-axis direction.

Related literature

For related imidazole disulfide compounds, see: Robina et al. (1990 ); Figueroa et al. (2007 ); Chernovyants et al. (2008 ).

Experimental

Crystal data

C₆H₆N₄S₂
M_r = 198.29
Monoclinic, C 2/c
a = 14.083 (3) Å
b = 6.3928 (13) Å
c = 9.922 (2) Å
β = 122.29 (3)°
V = 755.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.64 mm⁻¹
T = 298 K
0.45 × 0.25 × 0.15 mm

Data collection

STOE IPDS II diffractometer
Absorption correction: multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005 ) T_min = 0.823, T_max = 0.906
4116 measured reflections
1007 independent reflections
948 reflections with I > 2σ(I)
R_int = 0.112

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.185
S = 1.18
1007 reflections
56 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1ⁱ	0.86	2.44	3.227 (3)	153
Symmetry code: (i) $[x, -y, z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811036014/xu5318sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811036014/xu5318Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811036014/xu5318Isup3.cml

checkCIF report

Comment top

There have been little attention to crystal structure determination of imidazole disulfides. The crystal structure of 2,2-Dithio-bis(1-p-tolyl-1H-imidazole-4-carboxaldehyde) (Robina et al., 1990), bis(1-Phenylimidazol-2-yl)disulfide (Figueroa et al., 2007), bis(1 - t-Butylimidazol-2-yl)disulfide (Figueroa et al., 2007) and 2,2-Dithiobis(1-methylimidazol-3-ium-2-yl) bis(tri-iodide) di-iodine (Chernovyants et al., 2008) have reported previously. Here we report the crystal structure of 2-(2-(1H-imidazol-2-yl)disulfanyl)-1H-imidazole. The asymmetric unit of the title compound, (I), contains one half-molecule and a twofold rotation axis passes through the middle of S—S bond (Fig. 1). The S—S bond distance is 2.0713 (14) Å. In this compound the imidazole rings are of course planar and the angle between these rings is 21.83 (19) °. The torsion angle of C1—S1—S1a—C1a (a: -x,y,-z + 1/2) is 83.62 (17) °. The ineramolecular N—H···S hydrogen bonds (Table 1) result in the formation of a linear chain in c-direction. Further pi-pi interaction between imidazole rings of adjacent chains in a-direction (cg···cg distance of 3.4466 (19) Å, sym code; -x, 1 - y, 1 - z) results in the formation of a supramolecular structure.

Related literature top

For related imidazole disulfide compounds, see: Robina et al. (1990); Figueroa et al. (2007); Chernovyants et al. (2008).

Experimental top

The title compound has been synthsized during the stirring of 1H-imidazole-2-thiol with thallium(I) acetate in 2:1 molar ration in methanol. The suitable crystals for X-ray analysis were obtained by slow evaporation from methanol solution after one week (yield; 75.5%).

Structure description top

For related imidazole disulfide compounds, see: Robina et al. (1990); Figueroa et al. (2007); Chernovyants et al. (2008).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

2-[(1H-Imidazol-2-yl)disulfanyl]-1H-imidazole top

Crystal data top

C₆H₆N₄S₂	F(000) = 408
M_r = 198.29	D_x = 1.744 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1007 reflections
a = 14.083 (3) Å	θ = 3.4–23°
b = 6.3928 (13) Å	µ = 0.64 mm⁻¹
c = 9.922 (2) Å	T = 298 K
β = 122.29 (3)°	Prism, colorless
V = 755.1 (4) Å³	0.45 × 0.25 × 0.15 mm
Z = 4

Data collection top

STOE IPDS II diffractometer	1007 independent reflections
Graphite monochromator	948 reflections with I > 2σ(I)
Detector resolution: 0.15 pixels mm^-1	R_int = 0.112
rotation method scans	θ_max = 29.2°, θ_min = 3.4°
Absorption correction: multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005)	h = −19→19
T_min = 0.823, T_max = 0.906	k = −8→6
4116 measured reflections	l = −13→13

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.185	w = 1/[σ²(F_o²) + (0.1134P)² + 0.6898P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
1007 reflections	Δρ_max = 0.82 e Å⁻³
56 parameters	Δρ_min = −0.56 e Å⁻³
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.11 (3)

Crystal data top

C₆H₆N₄S₂	V = 755.1 (4) Å³
M_r = 198.29	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 14.083 (3) Å	µ = 0.64 mm⁻¹
b = 6.3928 (13) Å	T = 298 K
c = 9.922 (2) Å	0.45 × 0.25 × 0.15 mm
β = 122.29 (3)°

Data collection top

STOE IPDS II diffractometer	1007 independent reflections
Absorption correction: multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005)	948 reflections with I > 2σ(I)
T_min = 0.823, T_max = 0.906	R_int = 0.112
4116 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.185	H-atom parameters constrained
S = 1.18	Δρ_max = 0.82 e Å⁻³
1007 reflections	Δρ_min = −0.56 e Å⁻³
56 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
S1	0.08686 (5)	0.07449 (9)	0.32168 (6)	0.0337 (4)
N1	0.13136 (17)	0.4761 (4)	0.4347 (2)	0.0319 (5)
N2	0.11134 (18)	0.2432 (4)	0.5892 (2)	0.0350 (6)
H2A	0.1006	0.129	0.625	0.042*
C1	0.11109 (17)	0.2743 (4)	0.4570 (2)	0.0281 (5)
C2	0.1440 (2)	0.5734 (4)	0.5611 (3)	0.0335 (6)
H2	0.1585	0.7155	0.5821	0.04*
C3	0.13289 (18)	0.4382 (4)	0.6536 (2)	0.0280 (5)
H3	0.139	0.4723	0.7491	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0385 (5)	0.0326 (5)	0.0294 (5)	0.00531 (19)	0.0178 (4)	−0.00166 (17)
N1	0.0407 (10)	0.0348 (11)	0.0256 (9)	−0.0026 (8)	0.0213 (7)	−0.0020 (7)
N2	0.0451 (11)	0.0375 (11)	0.0271 (10)	0.0024 (8)	0.0226 (8)	0.0042 (7)
C1	0.0300 (10)	0.0334 (11)	0.0222 (10)	0.0028 (8)	0.0147 (8)	0.0011 (7)
C2	0.0382 (12)	0.0369 (14)	0.0260 (11)	−0.0032 (8)	0.0175 (9)	−0.0040 (7)
C3	0.0316 (10)	0.0373 (13)	0.0180 (9)	0.0023 (7)	0.0151 (8)	−0.0010 (7)

Geometric parameters (Å, º) top

S1—C1	1.750 (2)	N2—C3	1.359 (3)
S1—S1ⁱ	2.0713 (14)	N2—H2A	0.86
N1—C2	1.324 (3)	C2—C3	1.329 (3)
N1—C1	1.364 (3)	C2—H2	0.93
N2—C1	1.324 (3)	C3—H3	0.93

C1—S1—S1ⁱ	101.62 (7)	N1—C1—S1	122.51 (16)
C2—N1—C1	102.96 (19)	N1—C2—C3	110.0 (2)
C1—N2—C3	102.12 (19)	N1—C2—H2	125
C1—N2—H2A	128.9	C3—C2—H2	125
C3—N2—H2A	128.9	C2—C3—N2	110.52 (19)
N2—C1—N1	114.4 (2)	C2—C3—H3	124.7
N2—C1—S1	123.13 (18)	N2—C3—H3	124.7

C3—N2—C1—N1	0.1 (3)	S1ⁱ—S1—C1—N1	−93.68 (18)
C3—N2—C1—S1	−179.85 (15)	C1—N1—C2—C3	0.5 (3)
C2—N1—C1—N2	−0.4 (3)	N1—C2—C3—N2	−0.4 (3)
C2—N1—C1—S1	179.60 (17)	C1—N2—C3—C2	0.2 (3)
S1ⁱ—S1—C1—N2	86.31 (19)

Symmetry code: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱⁱ	0.86	2.44	3.227 (3)	153

Symmetry code: (ii) x, −y, z+1/2.

Experimental details

Crystal data
Chemical formula	C₆H₆N₄S₂
M_r	198.29
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	14.083 (3), 6.3928 (13), 9.922 (2)
β (°)	122.29 (3)
V (Å³)	755.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.64
Crystal size (mm)	0.45 × 0.25 × 0.15

Data collection
Diffractometer	STOE IPDS II
Absorption correction	Multi-scan (X-RED and X-SHAPE; Stoe & Cie, 2005)
T_min, T_max	0.823, 0.906
No. of measured, independent and observed [I > 2σ(I)] reflections	4116, 1007, 948
R_int	0.112
(sin θ/λ)_max (Å⁻¹)	0.686

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.185, 1.18
No. of reflections	1007
No. of parameters	56
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.82, −0.56

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1ⁱ	0.86	2.44	3.227 (3)	153

Symmetry code: (i) x, −y, z+1/2.

Acknowledgements

The authors wish to acknowledge Shahid Beheshti University, G. C., for financial support.

References

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