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

Abstract

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,

• a = 14.083 (3) Å

• b = 6.3928 (13) Å

• c = 9.922 (2) Å

• β = 122.29 (3)°

• V = 755.1 (4) ų

• 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[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 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

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811036014/xu5318Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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%).

Refinement

H atoms were positioned geometrically with C—H = 0.93 and N—H = 0.86 Å, and constrained to ride on their parent atoms with U_iso(H) = 1.2U_eq(C,N).

Figures

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.

Crystal data

C6H6N4S2	F(000) = 408
Mr = 198.29	Dx = 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

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

Refinement

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(Fo2) + (0.1134P)2 + 0.6898P] where P = (Fo2 + 2Fc2)/3
S = 1.18	(Δ/σ)max < 0.001
1007 reflections	Δρmax = 0.82 e Å−3
56 parameters	Δρmin = −0.56 e Å−3
0 restraints	Extinction correction: SHELXL
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.11 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

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

Symmetry codes: (ii) x, −y, z+1/2.