Crystal structure of 4,6-di-amino-2-sulfanyl-idene-1,2-di-hydro-pyridine-3-carbo-nitrile.

The title compound, C6H6N4S, crystallizes with two independent mol-ecules, A and B, in the asymmetric unit. Both independent mol-ecules are almost planar [maximum deviations of 0.068 (6) Å in mol-ecule A and 0.079 (6) Å in mol-ecule B]. In the crystal, mol-ecules A and B are linked by N-H⋯S, N-H⋯N and C-H⋯S hydrogen bonds, forming a three-dimensional network.

Related literature

For the synthesis of polyfuntional pyridines, see: Attaby et al. (1995 ▶); Asadov et al. (2003 ▶). For various biological properties of pyridine scaffold compounds, see: Abdel-Rahman et al. (2002 ▶); Rao et al. (2006 ▶). For the synthesis of 3-cyano­pyridine-2(1H)-thio­nes, see: Fahmy & Mohareb (1986 ▶); Schmidt & Kubitzek (1960 ▶). For the use of 3-cyano­pyridine-2(1H)-thi­ones in the synthesis of bio-active compounds, see: Taylor et al. (1983 ▶); Gangiee et al. (1991 ▶); Amr et al. (2003 ▶); Abu-Shanab et al. (2002 ▶); Awad et al. (1962 ▶); El-Gaby (2004 ▶); Miky & Zahkoug (1997 ▶; Guerrera et al. (1993 ▶); Krauze et al. (1999 ▶). For a similar crystal structure, see: Eyduran et al. (2007 ▶). For the synthesis of the title compound, see: Abu-Shanab (1999 ▶). For standard bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C6H6N4S

M = 166.21

Orthorhombic,

a = 26.252 (8) Å

b = 4.3670 (14) Å

c = 12.523 (4) Å

V = 1435.7 (8) Å3

Z = 8

Mo Kα radiation

μ = 0.38 mm−1

T = 150 K

0.32 × 0.12 × 0.04 mm

Data collection

Bruker APEX 2000 CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS: Bruker, 2011 ▶) T min = 0.518, T max = 0.928

11662 measured reflections

3412 independent reflections

2027 reflections with I > 2σ(I)

R int = 0.137

Refinement

R[F 2 > 2σ(F 2)] = 0.064

wR(F 2) = 0.117

S = 0.87

3412 reflections

199 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.42 e Å−3

Δρmin = −0.34 e Å−3

Absolute structure: Flack (1983 ▶), 1573 Friedel pairs

Absolute structure parameter: 0.01 (13)

Data collection: SMART (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814018029/hg5399sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018029/hg5399Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814018029/hg5399Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814018029/hg5399fig1.tif

The title mol­ecule showing the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S1600536814018029/hg5399fig2.tif

Packing viewed down the b axis showing the hydrogen bonding as dashed lines.

CCDC reference: 1018166

Additional supporting information: crystallographic information; 3D view; checkCIF report

C6H6N4S	F(000) = 688
Mr = 166.21	Dx = 1.538 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 748 reflections
a = 26.252 (8) Å	θ = 2.3–23.4°
b = 4.3670 (14) Å	µ = 0.38 mm−1
c = 12.523 (4) Å	T = 150 K
V = 1435.7 (8) Å3	Needle, pale yellow
Z = 8	0.32 × 0.12 × 0.04 mm

Bruker APEX 2000 CCD area-detector diffractometer	3412 independent reflections
Radiation source: fine-focus sealed tube	2027 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.137
phi and ω scans	θmax = 28.7°, θmin = 1.6°
Absorption correction: multi-scan (SADABS: Bruker, 2011)	h = −34→33
Tmin = 0.518, Tmax = 0.928	k = −5→5
11662 measured reflections	l = −16→16

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.064	w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.117	(Δ/σ)max < 0.001
S = 0.87	Δρmax = 0.42 e Å−3
3412 reflections	Δρmin = −0.34 e Å−3
199 parameters	Absolute structure: Flack (1983), 1573 Friedel pairs
1 restraint	Absolute structure parameter: 0.01 (13)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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.

	x	y	z	Uiso*/Ueq
S1	0.27967 (6)	0.5692 (5)	0.10895 (15)	0.0332 (6)
S1A	0.59399 (6)	0.7628 (4)	0.41599 (15)	0.0279 (5)
N1	0.28114 (18)	0.2124 (13)	−0.0607 (4)	0.027 (2)
N2	0.1365 (2)	0.4860 (15)	0.1504 (5)	0.039 (2)
N3	0.1288 (2)	0.0258 (14)	−0.0735 (5)	0.037 (2)
N4	0.2980 (2)	−0.1066 (15)	−0.2027 (5)	0.040 (2)
C1	0.2513 (3)	0.3403 (15)	0.0166 (5)	0.026 (2)
C2	0.1995 (2)	0.2719 (16)	0.0115 (5)	0.025 (2)
C3	0.1797 (2)	0.0835 (15)	−0.0684 (5)	0.025 (2)
C4	0.2122 (2)	−0.0471 (17)	−0.1416 (6)	0.030 (3)
C5	0.2637 (2)	0.0167 (17)	−0.1372 (6)	0.027 (3)
C6	0.1661 (2)	0.3946 (18)	0.0905 (6)	0.031 (3)
N1A	0.59425 (19)	1.1254 (12)	0.5874 (4)	0.0230 (17)
N2A	0.4628 (2)	0.4521 (15)	0.4637 (5)	0.038 (2)
N3A	0.45527 (19)	0.8585 (13)	0.7032 (4)	0.0327 (19)
N4A	0.6065 (2)	1.4593 (13)	0.7299 (4)	0.0277 (19)
C1A	0.5677 (3)	0.9133 (16)	0.5295 (5)	0.025 (2)
C2A	0.5201 (2)	0.8249 (16)	0.5670 (5)	0.023 (2)
C3A	0.5005 (3)	0.9504 (16)	0.6643 (5)	0.022 (2)
C4A	0.5300 (2)	1.1636 (15)	0.7195 (6)	0.026 (2)
C5A	0.5760 (2)	1.2555 (16)	0.6797 (5)	0.026 (2)
C6A	0.4896 (2)	0.6151 (16)	0.5089 (6)	0.025 (2)
H1	0.31370	0.25940	−0.06120	0.0320*
H4	0.19930	−0.18060	−0.19500	0.0360*
H31	0.11670	−0.09500	−0.12370	0.0450*
H32	0.10800	0.10930	−0.02670	0.0450*
H41	0.33050	−0.06070	−0.19550	0.0480*
H42	0.28820	−0.23400	−0.25310	0.0480*
H1A	0.62450	1.18140	0.56440	0.0270*
H4A	0.51800	1.24540	0.78520	0.0310*
H33	0.44400	0.93300	0.76400	0.0400*
H34	0.43690	0.72390	0.66770	0.0400*
H43	0.59690	1.53930	0.79120	0.0330*
H44	0.63580	1.51200	0.70130	0.0330*

	U11	U22	U33	U12	U13	U23
S1	0.0253 (9)	0.0437 (12)	0.0307 (10)	−0.0029 (9)	−0.0017 (8)	−0.0139 (10)
S1A	0.0223 (8)	0.0385 (10)	0.0229 (8)	0.0018 (9)	0.0020 (8)	0.0010 (9)
N1	0.016 (3)	0.037 (4)	0.027 (4)	−0.001 (3)	−0.001 (2)	−0.005 (3)
N2	0.026 (3)	0.054 (5)	0.037 (4)	0.002 (3)	−0.001 (3)	−0.011 (3)
N3	0.024 (3)	0.054 (4)	0.034 (4)	−0.004 (3)	−0.002 (3)	−0.020 (4)
N4	0.029 (3)	0.057 (5)	0.034 (4)	−0.009 (3)	0.004 (3)	−0.020 (3)
C1	0.031 (4)	0.025 (4)	0.021 (4)	0.003 (3)	0.000 (3)	−0.001 (3)
C2	0.023 (4)	0.031 (4)	0.021 (4)	0.005 (3)	−0.003 (3)	−0.006 (3)
C3	0.022 (3)	0.028 (4)	0.025 (4)	−0.002 (3)	0.001 (3)	−0.001 (4)
C4	0.025 (4)	0.034 (5)	0.030 (4)	−0.005 (3)	0.000 (3)	−0.017 (4)
C5	0.026 (4)	0.036 (5)	0.020 (4)	−0.003 (3)	0.001 (3)	−0.008 (3)
C6	0.023 (4)	0.040 (5)	0.031 (5)	0.001 (3)	−0.001 (3)	−0.007 (4)
N1A	0.022 (3)	0.027 (3)	0.020 (3)	−0.003 (3)	−0.001 (2)	0.002 (3)
N2A	0.035 (4)	0.042 (4)	0.036 (4)	−0.009 (3)	0.001 (3)	−0.003 (3)
N3A	0.021 (3)	0.049 (4)	0.028 (3)	−0.004 (3)	0.005 (3)	−0.012 (3)
N4A	0.026 (3)	0.032 (4)	0.025 (3)	−0.003 (3)	−0.002 (2)	0.000 (3)
C1A	0.028 (4)	0.023 (4)	0.023 (4)	0.004 (3)	−0.003 (3)	0.001 (3)
C2A	0.019 (3)	0.026 (4)	0.025 (4)	0.002 (3)	−0.002 (3)	0.004 (3)
C3A	0.018 (3)	0.026 (4)	0.023 (4)	0.006 (3)	0.000 (3)	0.003 (3)
C4A	0.027 (4)	0.025 (4)	0.026 (4)	0.002 (3)	0.001 (3)	−0.001 (3)
C5A	0.023 (4)	0.026 (4)	0.030 (4)	0.000 (3)	−0.008 (3)	0.009 (4)
C6A	0.020 (4)	0.024 (4)	0.032 (4)	0.006 (3)	0.005 (3)	0.007 (4)

S1—C1	1.700 (7)	N1A—C5A	1.374 (8)
S1A—C1A	1.711 (7)	N1A—C1A	1.367 (9)
N1—C1	1.365 (9)	N2A—C6A	1.150 (9)
N1—C5	1.363 (9)	N3A—C3A	1.345 (9)
N2—C6	1.151 (9)	C4—H4	0.9500
N3—C3	1.361 (7)	N4A—C5A	1.352 (8)
N4—C5	1.332 (9)	C1A—C2A	1.390 (9)
C1—C2	1.394 (9)	N1A—H1A	0.8800
N1—H1	0.8800	C2A—C3A	1.432 (9)
C2—C3	1.396 (9)	C2A—C6A	1.418 (9)
C2—C6	1.426 (9)	C3A—C4A	1.394 (10)
C3—C4	1.376 (9)	N3A—H34	0.8800
N3—H31	0.8800	N3A—H33	0.8800
N3—H32	0.8800	C4A—C5A	1.367 (8)
N4—H41	0.8800	N4A—H43	0.8800
N4—H42	0.8800	N4A—H44	0.8800
C4—C5	1.382 (8)	C4A—H4A	0.9500
C1—N1—C5	124.2 (5)	C5—C4—H4	120.00
S1—C1—N1	118.1 (6)	S1A—C1A—N1A	119.7 (5)
S1—C1—C2	125.8 (5)	S1A—C1A—C2A	122.5 (5)
N1—C1—C2	116.1 (6)	N1A—C1A—C2A	117.9 (6)
C1—N1—H1	118.00	C1A—N1A—H1A	118.00
C5—N1—H1	118.00	C5A—N1A—H1A	118.00
C1—C2—C3	121.5 (6)	C1A—C2A—C3A	120.3 (6)
C1—C2—C6	119.2 (6)	C1A—C2A—C6A	120.9 (6)
C3—C2—C6	119.3 (5)	C3A—C2A—C6A	118.8 (6)
N3—C3—C2	120.6 (5)	N3A—C3A—C2A	120.8 (6)
C3—N3—H31	120.00	C3A—N3A—H33	120.00
C3—N3—H32	120.00	C3A—N3A—H34	120.00
H31—N3—H32	120.00	H33—N3A—H34	120.00
C2—C3—C4	119.4 (5)	C2A—C3A—C4A	118.6 (6)
N3—C3—C4	120.0 (6)	N3A—C3A—C4A	120.7 (6)
C5—N4—H42	120.00	C5A—N4A—H44	120.00
C5—N4—H41	120.00	C5A—N4A—H43	120.00
C3—C4—C5	119.8 (6)	C3A—C4A—C5A	120.4 (7)
H41—N4—H42	120.00	H43—N4A—H44	120.00
N1—C5—N4	117.3 (5)	N1A—C5A—N4A	117.2 (5)
N4—C5—C4	123.8 (7)	N4A—C5A—C4A	123.2 (6)
N1—C5—C4	118.9 (6)	N1A—C5A—C4A	119.6 (6)
N2—C6—C2	175.5 (7)	N2A—C6A—C2A	176.7 (6)
C1A—N1A—C5A	123.3 (5)	C3A—C4A—H4A	120.00
C3—C4—H4	120.00	C5A—C4A—H4A	120.00
C5—N1—C1—S1	177.7 (5)	C5A—N1A—C1A—S1A	−179.5 (5)
C5—N1—C1—C2	−3.0 (10)	C5A—N1A—C1A—C2A	−0.5 (10)
C1—N1—C5—C4	3.5 (10)	C1A—N1A—C5A—C4A	2.6 (9)
C1—N1—C5—N4	−175.4 (6)	C1A—N1A—C5A—N4A	179.1 (6)
S1—C1—C2—C6	−1.5 (10)	S1A—C1A—C2A—C6A	−3.5 (10)
S1—C1—C2—C3	179.3 (5)	S1A—C1A—C2A—C3A	178.0 (5)
N1—C1—C2—C3	0.0 (10)	N1A—C1A—C2A—C3A	−1.1 (10)
N1—C1—C2—C6	179.2 (6)	N1A—C1A—C2A—C6A	177.5 (6)
C1—C2—C3—N3	−178.3 (6)	C1A—C2A—C3A—N3A	−177.7 (6)
C6—C2—C3—C4	−176.9 (7)	C6A—C2A—C3A—C4A	−178.1 (6)
C1—C2—C3—C4	2.4 (10)	C1A—C2A—C3A—C4A	0.5 (10)
C6—C2—C3—N3	2.4 (10)	C6A—C2A—C3A—N3A	3.7 (10)
N3—C3—C4—C5	178.8 (7)	N3A—C3A—C4A—C5A	179.8 (6)
C2—C3—C4—C5	−1.9 (10)	C2A—C3A—C4A—C5A	1.6 (10)
C3—C4—C5—N4	177.9 (7)	C3A—C4A—C5A—N4A	−179.4 (6)
C3—C4—C5—N1	−0.9 (11)	C3A—C4A—C5A—N1A	−3.2 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1Ai	0.88	2.44	3.293 (5)	163
N1A—H1A···S1ii	0.88	2.80	3.579 (5)	149
N3—H31···N4Aiii	0.88	2.44	3.300 (8)	165
N3—H32···N2Aiv	0.88	2.39	3.077 (8)	135
N3A—H33···S1Aii	0.88	2.53	3.392 (6)	168
N3A—H34···N2v	0.88	2.20	2.981 (8)	148
N4—H41···S1Ai	0.88	2.75	3.536 (6)	149
N4—H42···S1vi	0.88	2.63	3.424 (6)	151
N4—H42···N2vi	0.88	2.62	3.083 (9)	114
N4A—H44···S1ii	0.88	2.53	3.353 (6)	157
C4—H4···S1vi	0.95	2.74	3.551 (8)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1A i	0.88	2.44	3.293 (5)	163
N1A—H1A⋯S1ii	0.88	2.80	3.579 (5)	149
N3—H31⋯N4A iii	0.88	2.44	3.300 (8)	165
N3—H32⋯N2A iv	0.88	2.39	3.077 (8)	135
N3A—H33⋯S1A ii	0.88	2.53	3.392 (6)	168
N3A—H34⋯N2v	0.88	2.20	2.981 (8)	148
N4—H41⋯S1A i	0.88	2.75	3.536 (6)	149
N4—H42⋯S1vi	0.88	2.63	3.424 (6)	151
N4—H42⋯N2vi	0.88	2.62	3.083 (9)	114
N4A—H44⋯S1ii	0.88	2.53	3.353 (6)	157
C4—H4⋯S1vi	0.95	2.74	3.551 (8)	143

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .