4-Phenyl-1H-imidazole-2(3H)-thione

Owczarzak, A.M.; Kubicki, M.

doi:10.1107/S1600536812020090

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1686

doi:10.1107/S1600536812020090

Open

access

4-Phenyl-1H-imidazole-2(3H)-thione

Anita M. Owczarzak ^a and Maciej Kubicki ^a ^*

^aDepartment of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznań, Poland
^*Correspondence e-mail: mkubicki@amu.edu.pl

(Received 12 April 2012; accepted 4 May 2012; online 12 May 2012)

In the asymmetric unit of the title compound, C₉H₈N₂S, there are four symmetry-independent molecules (Z′ = 4). The geometrical features of these molecules are quite similar: in the normal probability plots the R² correlation factors for bond lengths and angles are generally around 0.95. The twist angles between the imidazole and phenyl rings (which are planar within 3σ) range from 9.0 (6) to 13.1 (5)°. In the crystal, pairs of independent molecules are joined by linear N—H⋯S and weak C—H⋯S hydrogen bonds, forming infinite ribbons, of the type ∼ABABAB∼ and ∼CDCDCD∼, propagating along [110]. Second-order hydrogen-bonded R₂²(8) rings are formed via interweaving infinite C₂²(8) chains.

Related literature

For related structures, see: Conde et al. (1977 ); Raper et al. (1984 ). For general background to thioamides, see: Martindale (1982 ); Hussain et al. (1990 ); Buxeraud (1995 ). For normal probability plots, see: Abrahams & Keve (1971 ); International Tables for X-ray Crystallography (1974 ). For a description of the Cambridge Structural Database, see: Allen (2002 ). For graph-set notation, see: Bernstein et al. (1995 ); Etter et al. (1990 ).

Experimental

Crystal data

C₉H₈N₂S
M_r = 176.23
Monoclinic, C c
a = 11.7578 (5) Å
b = 11.8071 (5) Å
c = 25.1339 (18) Å
β = 91.858 (6)°
V = 3487.4 (3) Å³
Z = 16
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 295 K
0.2 × 0.16 × 0.03 mm

Data collection

Agilent Xcalibur, Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.928, T_max = 1.000
11682 measured reflections
5247 independent reflections
4168 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.165
S = 1.08
5247 reflections
433 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.27 e Å⁻³
Absolute structure: Flack (1983 ), 1447 Friedel pairs
Flack parameter: 0.01 (13)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A⋯S2B	0.86	2.44	3.274 (6)	163
N3A—H3A⋯S2Bⁱ	0.86	2.50	3.350 (5)	172
C42A—H42A⋯S2Bⁱ	0.93	2.85	3.723 (9)	156
N1B—H1B⋯S2Aⁱⁱ	0.86	2.46	3.290 (5)	163
N3B—H3B⋯S2A	0.86	2.48	3.343 (5)	176
C42B—H42B⋯S2A	0.93	2.79	3.686 (9)	161
N1C—H1C⋯S2D	0.86	2.45	3.288 (5)	166
N3C—H3C⋯S2Dⁱⁱ	0.86	2.50	3.348 (5)	172
C42C—H42C⋯S2Dⁱⁱ	0.93	2.89	3.741 (8)	153
N1D—H1D⋯S2Cⁱ	0.86	2.43	3.271 (6)	166
N3D—H3D⋯S2C	0.86	2.50	3.353 (6)	172
C42D—H42D⋯S2C	0.93	2.85	3.766 (9)	169
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: XP (Sheldrick, 2008) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812020090/nk2157sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812020090/nk2157Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812020090/nk2157Isup3.cml

checkCIF report

Comment top

Heterocyclic thioamides are an important class of N, S-donor ligands, which display both hard and soft donor sites. They form a huge variety of coordination compounds and consequently have wide-ranging applications: for instance, as analytical reagents or metal corrosion inhibitors. They are also used as biologically active molecules (e.g. Hussain et al., 1990, and references therein). Among the anti-thyroidal agents most widely used for the treatment of Graves' disease are some derivatives of imidazole-2-thiol as N-methylimidazoline-2-thione (Methimazole) as well as other thioamides, e.g. 3-methyl-2-thioxo-4-imidazoline-1-carboxylate (Carbimazole) and propylthiouracil (Martindale, 1982, Buxeraud, 1995). Here we present the crystal structure of simple thioamide, 4-phenyl-1,3-dihydro-2H-imidazole-2-thione (1, Scheme 1), which turned out to crystallize with Z'=4.

The Cambridge Structural Database (Allen, 2002) contains only a handful of 1,3-dihydroimidazole-2-thione derivatives. These are mainly S-metal complexes and few simple organic derivatives, for instance 1,3-dihydro-2H-imidazole-2-thione hydrate (Raper et al., 1984) and 4-formyl-1,3-dihydro-2H-imidazole-2-thione (Conde et al., 1977).

The asymmetric part of the unit cell of 1 contains four independent molecules, Fig. 1 shows one of them. These molecules are similar; the results of the normal probability plot analysis (International Tables for X-ray Crystallography, 1974; Abrahams & Keve, 1971) for bond lengths and angles show that there are no systematical differences between the molecules, and the actual differences are only of statistical nature: R² correlation factors for bond lengths and angles are generally around 0.95.

Overall conformation of the molecules can be described here by the dihedral angles between two almost perfectly planar (within 3 s.u.'s) rings, imidazole and phenyl. These angles are relatively small - thanks partially at least to the lack of the sterical hindrance - and range from 9.0 (6)° for molecule B to 13.1 (5)° for molecule C. The bond length and angles are typical, with the C—S bond distance confirming its double-bond character, the mean value of this length is 1.694 (4) Å.

In the crystal structure the pairs of molecules A—B and C—D create identical but independent motifs. They are joined into infinite ribbons (along [110]) by means of relatively short and linear N—H···S hydrogen bonds (Table 1, Fig. 2), and additionally by weaker, secondary C—H···S hydrogen bonds. Using graph-set notation (Etter, et al., 1990, Bernstein et al., 1995), one can identify the second-order rings R²₂(8) which are made by interweaving C²₂(8) chains. These almost independent ribbons combine together to make the overall three-dimensional structure (Fig. 3).

Related literature top

For related crystal structures, see: Conde et al. (1977); Raper et al. (1984). For general literature on thioamides, see: Martindale (1982); Hussain et al. (1990); Buxeraud (1995). For literature on normal probability plots, see: Abrahams & Keve (1971); International Tables for X-ray Crystallography (1974); for the Cambridge Structural Database, see: Allen (2002); and for graph-set notation, see: Bernstein et al. (1995);; Etter et al. (1990).

Experimental top

The title compound was prepared by adding hydrochloric acid to acetonitrile solution of 4-phenyl-imidazole-2-thiol in molar ratio 1:1. After a few minutes colourless, thin crystals of 1, suitable for single-crystal X-ray analysis appeared and were filtered off.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Anisotropic displacement ellipsoid representation of the molecule 1 A,The ellipsoids are drawn at the 50% probability level.
	Fig. 2. The hydrogen-bonded ribbon of molecules A and B (molecules C and D are joined into almost identical structure). Hydrogen bonds are shown as dashed lines, symmetry codes:; (i) -1/2 + x,-1/2 + y,z; (ii) 1/2 + x,1/2 + y,z..
	Fig. 3. The crystal packing as seen approximately along c-direction, hydrogen bonds are drawn as dashed lines. Symmetry-independent molecules are shown with different colours.

4-Phenyl-1H-imidazole-2(3H)-thione top

Crystal data top

C₉H₈N₂S	F(000) = 1472
M_r = 176.23	D_x = 1.343 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 4788 reflections
a = 11.7578 (5) Å	θ = 2.4–26.9°
b = 11.8071 (5) Å	µ = 0.31 mm⁻¹
c = 25.1339 (18) Å	T = 295 K
β = 91.858 (6)°	Plate, yellow
V = 3487.4 (3) Å³	0.2 × 0.16 × 0.03 mm
Z = 16

Data collection top

Xcalibur, Eos diffractometer	5247 independent reflections
Radiation source: Enhance (Mo) X-ray Source	4168 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 16.1544 pixels mm^-1	θ_max = 27.0°, θ_min = 2.5°
ω–scan	h = −14→9
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −14→14
T_min = 0.928, T_max = 1.000	l = −30→30
11682 measured reflections

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)] = 0.065	H-atom parameters constrained
wR(F²) = 0.165	w = 1/[σ²(F_o²) + (0.073P)² + 5.346P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
5247 reflections	Δρ_max = 0.80 e Å⁻³
433 parameters	Δρ_min = −0.27 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1447 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (13)

Crystal data top

C₉H₈N₂S	V = 3487.4 (3) Å³
M_r = 176.23	Z = 16
Monoclinic, Cc	Mo Kα radiation
a = 11.7578 (5) Å	µ = 0.31 mm⁻¹
b = 11.8071 (5) Å	T = 295 K
c = 25.1339 (18) Å	0.2 × 0.16 × 0.03 mm
β = 91.858 (6)°

Data collection top

Xcalibur, Eos diffractometer	5247 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	4168 reflections with I > 2σ(I)
T_min = 0.928, T_max = 1.000	R_int = 0.045
11682 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	H-atom parameters constrained
wR(F²) = 0.165	Δρ_max = 0.80 e Å⁻³
S = 1.08	Δρ_min = −0.27 e Å⁻³
5247 reflections	Absolute structure: Flack (1983), 1447 Friedel pairs
433 parameters	Absolute structure parameter: 0.01 (13)
2 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1A	0.4989 (5)	0.4546 (4)	0.8218 (2)	0.0444 (12)
H1A	0.4424	0.4129	0.8115	0.053*
C2A	0.5332 (5)	0.5485 (5)	0.7969 (3)	0.0345 (13)
S2A	0.47435 (12)	0.60428 (14)	0.74045 (7)	0.0458 (4)
N3A	0.6236 (4)	0.5869 (4)	0.8257 (2)	0.0371 (11)
H3A	0.6619	0.6464	0.8179	0.045*
C4A	0.6471 (5)	0.5183 (5)	0.8695 (2)	0.0360 (13)
C41A	0.7430 (6)	0.5375 (5)	0.9085 (3)	0.0411 (15)
C42A	0.8265 (8)	0.6105 (8)	0.8996 (4)	0.070 (3)
H42A	0.8229	0.6528	0.8684	0.084*
C43A	0.9180 (9)	0.6267 (9)	0.9345 (4)	0.079 (3)
H43A	0.9745	0.6785	0.9263	0.095*
C44A	0.9258 (7)	0.5679 (8)	0.9802 (4)	0.067 (2)
H44A	0.9857	0.5797	1.0046	0.080*
C45A	0.8436 (9)	0.4911 (8)	0.9894 (4)	0.072 (3)
H45A	0.8495	0.4460	1.0197	0.086*
C46A	0.7474 (7)	0.4777 (7)	0.9534 (3)	0.0558 (19)
H46A	0.6890	0.4280	0.9613	0.067*
C5A	0.5680 (6)	0.4349 (5)	0.8665 (3)	0.0428 (14)
H5A	0.5613	0.3750	0.8902	0.051*
N1B	0.0966 (4)	0.3495 (5)	0.7179 (2)	0.0435 (13)
H1B	0.0559	0.2940	0.7286	0.052*
C2B	0.1929 (5)	0.3860 (5)	0.7428 (2)	0.0378 (14)
S2B	0.25122 (12)	0.33365 (14)	0.79993 (7)	0.0466 (4)
N3B	0.2285 (4)	0.4711 (4)	0.7131 (2)	0.0358 (11)
H3B	0.2896	0.5091	0.7199	0.043*
C4B	0.1546 (5)	0.4916 (5)	0.6695 (2)	0.0348 (13)
C41B	0.1702 (6)	0.5816 (6)	0.6307 (3)	0.0422 (15)
C42B	0.2505 (8)	0.6634 (9)	0.6382 (4)	0.076 (3)
H42B	0.2988	0.6638	0.6682	0.091*
C43B	0.2579 (9)	0.7492 (9)	0.5979 (5)	0.096 (4)
H43B	0.3120	0.8059	0.6032	0.116*
C44B	0.1938 (8)	0.7536 (9)	0.5539 (4)	0.062 (2)
H44B	0.2034	0.8092	0.5283	0.075*
C45B	0.1127 (9)	0.6719 (8)	0.5484 (4)	0.076 (3)
H45B	0.0639	0.6736	0.5186	0.091*
C46B	0.0997 (8)	0.5848 (7)	0.5859 (3)	0.067 (2)
H46B	0.0439	0.5298	0.5805	0.081*
C5B	0.0719 (6)	0.4130 (5)	0.6731 (3)	0.0442 (15)
H5B	0.0098	0.4034	0.6496	0.053*
N1C	0.5331 (4)	0.2879 (4)	0.7138 (2)	0.0469 (13)
H1C	0.5905	0.3287	0.7238	0.056*
C2C	0.4983 (5)	0.1952 (5)	0.7392 (3)	0.0364 (13)
S2C	0.55718 (13)	0.14044 (14)	0.79617 (7)	0.0481 (4)
N3C	0.4080 (4)	0.1579 (4)	0.7113 (2)	0.0368 (11)
H3C	0.3689	0.0991	0.7192	0.044*
C4C	0.3853 (5)	0.2275 (5)	0.6673 (2)	0.0376 (14)
C41C	0.2895 (5)	0.2125 (6)	0.6298 (3)	0.0425 (15)
C42C	0.1987 (7)	0.1387 (7)	0.6398 (3)	0.053 (2)
H42C	0.1989	0.0963	0.6710	0.064*
C43C	0.1101 (8)	0.1297 (8)	0.6034 (4)	0.074 (3)
H43C	0.0504	0.0803	0.6099	0.089*
C44C	0.1083 (9)	0.1948 (7)	0.5560 (4)	0.070 (3)
H44C	0.0477	0.1890	0.5314	0.084*
C45C	0.1965 (7)	0.2658 (8)	0.5470 (3)	0.0518 (19)
H45C	0.1962	0.3091	0.5161	0.062*
C46C	0.2816 (7)	0.2737 (7)	0.5813 (3)	0.055 (2)
H46C	0.3408	0.3226	0.5735	0.066*
C5C	0.4655 (6)	0.3088 (6)	0.6699 (3)	0.0482 (16)
H5C	0.4733	0.3683	0.6461	0.058*
N1D	0.9343 (5)	0.3980 (5)	0.8200 (2)	0.0492 (14)
H1D	0.9739	0.4548	0.8099	0.059*
C2D	0.8402 (5)	0.3599 (5)	0.7950 (3)	0.0371 (13)
S2D	0.77977 (13)	0.41209 (14)	0.73786 (7)	0.0503 (4)
N3D	0.8053 (4)	0.2707 (4)	0.8242 (2)	0.0398 (12)
H3D	0.7458	0.2307	0.8168	0.048*
C4D	0.8767 (5)	0.2527 (5)	0.8668 (2)	0.0381 (14)
C41D	0.8657 (6)	0.1604 (6)	0.9059 (3)	0.0421 (15)
C42D	0.7813 (7)	0.0797 (7)	0.9028 (3)	0.061 (2)
H42D	0.7277	0.0843	0.8748	0.073*
C43D	0.7718 (9)	−0.0058 (9)	0.9380 (4)	0.084 (3)
H43D	0.7117	−0.0570	0.9356	0.101*
C44D	0.8559 (8)	−0.0141 (8)	0.9782 (4)	0.064 (2)
H44D	0.8535	−0.0735	1.0024	0.077*
C45D	0.9391 (7)	0.0611 (7)	0.9825 (3)	0.054 (2)
H45D	0.9929	0.0559	1.0103	0.065*
C46D	0.9459 (7)	0.1450 (7)	0.9465 (3)	0.0522 (19)
H46D	1.0072	0.1947	0.9491	0.063*
C5D	0.9591 (6)	0.3327 (6)	0.8646 (3)	0.0519 (17)
H5D	1.0205	0.3419	0.8884	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1A	0.047 (3)	0.034 (3)	0.051 (3)	−0.008 (2)	−0.005 (3)	0.003 (2)
C2A	0.026 (3)	0.029 (3)	0.049 (3)	−0.008 (2)	0.001 (3)	0.009 (2)
S2A	0.0409 (9)	0.0470 (9)	0.0487 (9)	−0.0178 (7)	−0.0117 (7)	0.0096 (7)
N3A	0.036 (3)	0.036 (3)	0.040 (3)	−0.001 (2)	−0.001 (2)	0.009 (2)
C4A	0.036 (3)	0.035 (3)	0.037 (3)	−0.003 (3)	−0.001 (2)	0.003 (2)
C41A	0.044 (4)	0.040 (3)	0.039 (4)	0.006 (3)	0.002 (3)	0.006 (3)
C42A	0.062 (6)	0.087 (6)	0.059 (5)	0.002 (5)	−0.031 (4)	0.014 (5)
C43A	0.076 (6)	0.090 (6)	0.070 (6)	−0.033 (5)	−0.015 (5)	0.023 (5)
C44A	0.042 (4)	0.090 (6)	0.067 (5)	−0.015 (4)	−0.016 (4)	0.011 (5)
C45A	0.089 (7)	0.064 (5)	0.061 (5)	−0.012 (5)	−0.029 (5)	0.020 (4)
C46A	0.046 (4)	0.071 (5)	0.049 (4)	−0.009 (4)	−0.014 (3)	0.007 (4)
C5A	0.045 (4)	0.043 (3)	0.040 (3)	−0.010 (3)	0.000 (3)	0.002 (3)
N1B	0.035 (3)	0.043 (3)	0.052 (3)	−0.021 (2)	−0.004 (2)	0.002 (2)
C2B	0.039 (3)	0.031 (3)	0.044 (3)	0.002 (3)	0.003 (3)	0.000 (3)
S2B	0.0386 (9)	0.0488 (9)	0.0516 (9)	−0.0184 (7)	−0.0101 (7)	0.0157 (7)
N3B	0.023 (2)	0.039 (3)	0.045 (3)	−0.011 (2)	0.000 (2)	−0.005 (2)
C4B	0.035 (3)	0.039 (3)	0.031 (3)	0.002 (3)	−0.002 (2)	0.002 (2)
C41B	0.037 (4)	0.045 (4)	0.044 (4)	0.000 (3)	−0.005 (3)	−0.001 (3)
C42B	0.080 (7)	0.088 (6)	0.058 (5)	−0.014 (5)	−0.036 (5)	0.041 (5)
C43B	0.082 (7)	0.078 (6)	0.128 (10)	−0.036 (5)	−0.018 (7)	0.038 (6)
C44B	0.062 (5)	0.072 (6)	0.052 (5)	0.009 (4)	−0.001 (4)	0.022 (4)
C45B	0.107 (8)	0.077 (6)	0.042 (4)	−0.004 (6)	−0.030 (5)	0.024 (4)
C46B	0.082 (6)	0.066 (5)	0.052 (5)	−0.011 (4)	−0.013 (4)	0.013 (4)
C5B	0.042 (4)	0.043 (4)	0.047 (4)	−0.011 (3)	−0.011 (3)	0.001 (3)
N1C	0.039 (3)	0.042 (3)	0.059 (4)	−0.018 (2)	−0.002 (3)	0.005 (3)
C2C	0.031 (3)	0.035 (3)	0.042 (3)	−0.006 (2)	−0.003 (3)	−0.007 (3)
S2C	0.0442 (10)	0.0442 (9)	0.0550 (10)	−0.0178 (8)	−0.0112 (7)	0.0072 (8)
N3C	0.029 (3)	0.035 (2)	0.046 (3)	−0.014 (2)	0.002 (2)	−0.007 (2)
C4C	0.036 (3)	0.036 (3)	0.041 (3)	0.001 (3)	0.005 (3)	−0.003 (3)
C41C	0.033 (3)	0.049 (4)	0.046 (4)	−0.009 (3)	−0.006 (3)	−0.007 (3)
C42C	0.052 (5)	0.057 (5)	0.051 (4)	−0.017 (3)	0.000 (4)	0.020 (4)
C43C	0.052 (5)	0.074 (6)	0.094 (7)	−0.024 (4)	−0.024 (5)	0.016 (5)
C44C	0.093 (7)	0.059 (5)	0.055 (5)	−0.005 (5)	−0.038 (5)	0.008 (4)
C45C	0.047 (4)	0.069 (5)	0.039 (4)	−0.008 (4)	0.001 (3)	0.005 (3)
C46C	0.063 (5)	0.051 (4)	0.052 (4)	−0.006 (3)	0.010 (4)	0.016 (3)
C5C	0.050 (4)	0.046 (4)	0.049 (4)	−0.009 (3)	−0.004 (3)	0.012 (3)
N1D	0.043 (3)	0.049 (3)	0.054 (4)	−0.008 (3)	−0.004 (3)	0.008 (3)
C2D	0.022 (3)	0.040 (3)	0.050 (3)	−0.011 (2)	0.005 (2)	−0.006 (3)
S2D	0.0433 (10)	0.0495 (10)	0.0578 (10)	−0.0173 (7)	−0.0051 (8)	0.0106 (8)
N3D	0.039 (3)	0.034 (3)	0.046 (3)	−0.006 (2)	0.004 (2)	0.004 (2)
C4D	0.033 (3)	0.040 (3)	0.042 (3)	0.000 (3)	0.002 (3)	−0.009 (3)
C41D	0.043 (4)	0.039 (3)	0.044 (4)	−0.001 (3)	0.006 (3)	−0.003 (3)
C42D	0.061 (5)	0.059 (5)	0.062 (5)	−0.024 (4)	−0.022 (4)	0.017 (4)
C43D	0.085 (7)	0.091 (6)	0.074 (6)	−0.043 (5)	−0.034 (5)	0.039 (5)
C44D	0.073 (6)	0.055 (5)	0.064 (5)	0.003 (4)	0.010 (4)	0.019 (4)
C45D	0.036 (4)	0.075 (5)	0.050 (4)	0.004 (4)	0.005 (3)	−0.006 (4)
C46D	0.043 (4)	0.059 (4)	0.055 (4)	−0.012 (3)	−0.004 (3)	0.000 (3)
C5D	0.045 (4)	0.054 (4)	0.055 (4)	−0.012 (3)	−0.011 (3)	0.006 (3)

Geometric parameters (Å, º) top

N1A—C2A	1.342 (7)	N1C—C2C	1.338 (8)
N1A—C5A	1.385 (8)	N1C—C5C	1.361 (9)
N1A—H1A	0.8600	N1C—H1C	0.8600
C2A—N3A	1.345 (8)	C2C—N3C	1.329 (8)
C2A—S2A	1.691 (6)	C2C—S2C	1.698 (7)
N3A—C4A	1.388 (8)	N3C—C4C	1.397 (8)
N3A—H3A	0.8600	N3C—H3C	0.8600
C4A—C5A	1.355 (9)	C4C—C5C	1.345 (9)
C4A—C41A	1.487 (9)	C4C—C41C	1.456 (9)
C41A—C46A	1.331 (10)	C41C—C42C	1.407 (9)
C41A—C42A	1.331 (11)	C41C—C46C	1.416 (10)
C42A—C43A	1.378 (13)	C42C—C43C	1.368 (13)
C42A—H42A	0.9300	C42C—H42C	0.9300
C43A—C44A	1.343 (14)	C43C—C44C	1.419 (13)
C43A—H43A	0.9300	C43C—H43C	0.9300
C44A—C45A	1.351 (12)	C44C—C45C	1.358 (12)
C44A—H44A	0.9300	C44C—H44C	0.9300
C45A—C46A	1.434 (12)	C45C—C46C	1.303 (12)
C45A—H45A	0.9300	C45C—H45C	0.9300
C46A—H46A	0.9300	C46C—H46C	0.9300
C5A—H5A	0.9300	C5C—H5C	0.9300
N1B—C2B	1.346 (8)	N1D—C2D	1.333 (8)
N1B—C5B	1.377 (8)	N1D—C5D	1.383 (9)
N1B—H1B	0.8600	N1D—H1D	0.8600
C2B—N3B	1.328 (8)	C2D—N3D	1.355 (8)
C2B—S2B	1.688 (6)	C2D—S2D	1.697 (7)
N3B—C4B	1.397 (8)	N3D—C4D	1.355 (8)
N3B—H3B	0.8600	N3D—H3D	0.8600
C4B—C5B	1.349 (9)	C4D—C5D	1.355 (9)
C4B—C41B	1.458 (9)	C4D—C41D	1.476 (9)
C41B—C42B	1.359 (12)	C41D—C42D	1.377 (10)
C41B—C46B	1.377 (11)	C41D—C46D	1.378 (11)
C42B—C43B	1.437 (13)	C42D—C43D	1.350 (12)
C42B—H42B	0.9300	C42D—H42D	0.9300
C43B—C44B	1.318 (14)	C43D—C44D	1.393 (13)
C43B—H43B	0.9300	C43D—H43D	0.9300
C44B—C45B	1.360 (13)	C44D—C45D	1.323 (12)
C44B—H44B	0.9300	C44D—H44D	0.9300
C45B—C46B	1.407 (12)	C45D—C46D	1.345 (12)
C45B—H45B	0.9300	C45D—H45D	0.9300
C46B—H46B	0.9300	C46D—H46D	0.9300
C5B—H5B	0.9300	C5D—H5D	0.9300

C2A—N1A—C5A	109.9 (5)	C2C—N1C—C5C	110.9 (5)
C2A—N1A—H1A	125.0	C2C—N1C—H1C	124.6
C5A—N1A—H1A	125.0	C5C—N1C—H1C	124.6
N1A—C2A—N3A	105.7 (5)	N3C—C2C—N1C	105.7 (6)
N1A—C2A—S2A	126.3 (5)	N3C—C2C—S2C	128.0 (5)
N3A—C2A—S2A	127.9 (4)	N1C—C2C—S2C	126.3 (5)
C2A—N3A—C4A	111.4 (5)	C2C—N3C—C4C	110.6 (5)
C2A—N3A—H3A	124.3	C2C—N3C—H3C	124.7
C4A—N3A—H3A	124.3	C4C—N3C—H3C	124.7
C5A—C4A—N3A	105.1 (6)	C5C—C4C—N3C	105.4 (6)
C5A—C4A—C41A	130.7 (6)	C5C—C4C—C41C	130.1 (6)
N3A—C4A—C41A	124.2 (6)	N3C—C4C—C41C	124.4 (6)
C46A—C41A—C42A	118.5 (8)	C42C—C41C—C46C	116.1 (7)
C46A—C41A—C4A	119.1 (7)	C42C—C41C—C4C	122.4 (7)
C42A—C41A—C4A	122.4 (6)	C46C—C41C—C4C	121.5 (6)
C41A—C42A—C43A	123.3 (9)	C43C—C42C—C41C	119.7 (7)
C41A—C42A—H42A	118.4	C43C—C42C—H42C	120.2
C43A—C42A—H42A	118.4	C41C—C42C—H42C	120.2
C44A—C43A—C42A	120.1 (9)	C42C—C43C—C44C	120.6 (8)
C44A—C43A—H43A	119.9	C42C—C43C—H43C	119.7
C42A—C43A—H43A	119.9	C44C—C43C—H43C	119.7
C43A—C44A—C45A	117.7 (9)	C45C—C44C—C43C	118.9 (8)
C43A—C44A—H44A	121.2	C45C—C44C—H44C	120.5
C45A—C44A—H44A	121.2	C43C—C44C—H44C	120.5
C44A—C45A—C46A	121.3 (9)	C46C—C45C—C44C	120.5 (8)
C44A—C45A—H45A	119.3	C46C—C45C—H45C	119.7
C46A—C45A—H45A	119.3	C44C—C45C—H45C	119.7
C41A—C46A—C45A	119.0 (8)	C45C—C46C—C41C	124.1 (8)
C41A—C46A—H46A	120.5	C45C—C46C—H46C	118.0
C45A—C46A—H46A	120.5	C41C—C46C—H46C	118.0
C4A—C5A—N1A	107.9 (6)	C4C—C5C—N1C	107.5 (6)
C4A—C5A—H5A	126.1	C4C—C5C—H5C	126.3
N1A—C5A—H5A	126.1	N1C—C5C—H5C	126.3
C2B—N1B—C5B	111.1 (5)	C2D—N1D—C5D	110.1 (6)
C2B—N1B—H1B	124.5	C2D—N1D—H1D	125.0
C5B—N1B—H1B	124.5	C5D—N1D—H1D	125.0
N3B—C2B—N1B	104.8 (6)	N1D—C2D—N3D	105.5 (6)
N3B—C2B—S2B	129.0 (5)	N1D—C2D—S2D	126.5 (5)
N1B—C2B—S2B	126.2 (5)	N3D—C2D—S2D	128.0 (5)
C2B—N3B—C4B	111.9 (5)	C2D—N3D—C4D	111.1 (5)
C2B—N3B—H3B	124.0	C2D—N3D—H3D	124.5
C4B—N3B—H3B	124.0	C4D—N3D—H3D	124.5
C5B—C4B—N3B	105.1 (5)	C5D—C4D—N3D	106.5 (6)
C5B—C4B—C41B	130.8 (6)	C5D—C4D—C41D	128.3 (6)
N3B—C4B—C41B	124.2 (6)	N3D—C4D—C41D	125.2 (6)
C42B—C41B—C46B	119.4 (7)	C42D—C41D—C46D	115.1 (7)
C42B—C41B—C4B	121.9 (7)	C42D—C41D—C4D	123.5 (7)
C46B—C41B—C4B	118.7 (6)	C46D—C41D—C4D	121.2 (6)
C41B—C42B—C43B	117.5 (9)	C43D—C42D—C41D	123.8 (8)
C41B—C42B—H42B	121.2	C43D—C42D—H42D	118.1
C43B—C42B—H42B	121.2	C41D—C42D—H42D	118.1
C44B—C43B—C42B	124.9 (9)	C42D—C43D—C44D	117.1 (8)
C44B—C43B—H43B	117.6	C42D—C43D—H43D	121.5
C42B—C43B—H43B	117.6	C44D—C43D—H43D	121.5
C43B—C44B—C45B	116.0 (8)	C45D—C44D—C43D	121.2 (8)
C43B—C44B—H44B	122.0	C45D—C44D—H44D	119.4
C45B—C44B—H44B	122.0	C43D—C44D—H44D	119.4
C44B—C45B—C46B	122.7 (9)	C44D—C45D—C46D	119.9 (9)
C44B—C45B—H45B	118.6	C44D—C45D—H45D	120.0
C46B—C45B—H45B	118.6	C46D—C45D—H45D	120.0
C41B—C46B—C45B	119.5 (8)	C45D—C46D—C41D	122.7 (7)
C41B—C46B—H46B	120.3	C45D—C46D—H46D	118.6
C45B—C46B—H46B	120.3	C41D—C46D—H46D	118.6
C4B—C5B—N1B	107.2 (6)	C4D—C5D—N1D	106.9 (6)
C4B—C5B—H5B	126.4	C4D—C5D—H5D	126.6
N1B—C5B—H5B	126.4	N1D—C5D—H5D	126.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S2B	0.86	2.44	3.274 (6)	163
N3A—H3A···S2Bⁱ	0.86	2.50	3.350 (5)	172
C42A—H42A···S2Bⁱ	0.93	2.85	3.723 (9)	156
N1B—H1B···S2Aⁱⁱ	0.86	2.46	3.290 (5)	163
N3B—H3B···S2A	0.86	2.48	3.343 (5)	176
C42B—H42B···S2A	0.93	2.79	3.686 (9)	161
N1C—H1C···S2D	0.86	2.45	3.288 (5)	166
N3C—H3C···S2Dⁱⁱ	0.86	2.50	3.348 (5)	172
C42C—H42C···S2Dⁱⁱ	0.93	2.89	3.741 (8)	153
N1D—H1D···S2Cⁱ	0.86	2.43	3.271 (6)	166
N3D—H3D···S2C	0.86	2.50	3.353 (6)	172
C42D—H42D···S2C	0.93	2.85	3.766 (9)	169

Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₉H₈N₂S
M_r	176.23
Crystal system, space group	Monoclinic, Cc
Temperature (K)	295
a, b, c (Å)	11.7578 (5), 11.8071 (5), 25.1339 (18)
β (°)	91.858 (6)
V (Å³)	3487.4 (3)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.2 × 0.16 × 0.03

Data collection
Diffractometer	Xcalibur, Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.928, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11682, 5247, 4168
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.165, 1.08
No. of reflections	5247
No. of parameters	433
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.27
Absolute structure	Flack (1983), 1447 Friedel pairs
Absolute structure parameter	0.01 (13)

Computer programs: CrysAlis PRO (Agilent, 2011), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), XP (Sheldrick, 2008) and Mercury (Macrae et al., 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A···S2B	0.86	2.44	3.274 (6)	162.5
N3A—H3A···S2Bⁱ	0.86	2.50	3.350 (5)	172.4
C42A—H42A···S2Bⁱ	0.93	2.85	3.723 (9)	156.2
N1B—H1B···S2Aⁱⁱ	0.86	2.46	3.290 (5)	162.9
N3B—H3B···S2A	0.86	2.48	3.343 (5)	175.5
C42B—H42B···S2A	0.93	2.79	3.686 (9)	160.9
N1C—H1C···S2D	0.86	2.45	3.288 (5)	165.5
N3C—H3C···S2Dⁱⁱ	0.86	2.50	3.348 (5)	171.6
C42C—H42C···S2Dⁱⁱ	0.93	2.89	3.741 (8)	152.5
N1D—H1D···S2Cⁱ	0.86	2.43	3.271 (6)	166.0
N3D—H3D···S2C	0.86	2.50	3.353 (6)	171.8
C42D—H42D···S2C	0.93	2.85	3.766 (9)	169.3

Symmetry codes: (i) x+1/2, y+1/2, z; (ii) x−1/2, y−1/2, z.

References

Abrahams, S. C. & Keve, E. T. (1971). Acta Cryst. A27, 157–165. CrossRef CAS IUCr Journals Web of Science Google Scholar
Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, Oxfordshire, England. Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Buxeraud, J. (1995). Traite de Chimie Therapeutique, Vol. 4, ch. 18. Paris: Tec et Doc Lavoisier. Google Scholar
Conde, A., Moreno, E. & Márquez, R. (1977). Acta Cryst. B33, 794–797. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hussain, M. S., Al-Arfaj, A. R. & Hossain, M. L. (1990). Transition Met. Chem. 15, 264–269. CSD CrossRef CAS Web of Science Google Scholar
International Tables for X-ray Crystallography (1974). Vol. IV. Birmingham: Kynoch Press. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Martindale, W. (1982). The Extra Pharmacopoeia, 28th ed. London: The Pharmaceutical Press. Google Scholar
Raper, E. S., Jackson, A. R. W. & Gardiner, D. J. (1984). Inorg. Chim. Acta, 84, L1–L4. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 6| June 2012| Page o1686

doi:10.1107/S1600536812020090

Open

access