Crystal structure of 4,6-di­amino-2-sulfanyl­idene-1,2-di­hydro­pyridine-3-carbo­nitrile

Shaaban K Mohamed; Mehmet Akkurt; Kuldip Singh; Bahgat R M Hussein; Mustafa R Albayati

doi:10.1107/S1600536814018029

. 2014 Aug 9;70(Pt 9):o993–o994. doi: 10.1107/S1600536814018029

Crystal structure of 4,6-diamino-2-sulfanylidene-1,2-dihydropyridine-3-carbonitrile

Shaaban K Mohamed ^a,^b, Mehmet Akkurt ^c, Kuldip Singh ^d, Bahgat R M Hussein ^e, Mustafa R Albayati ^f,^*

PMCID: PMC4186145 PMID: 25309298

Abstract

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

Keywords: crystal structure, polyfuntional pyridines, 3-cyanopyridine-2(1H)-thiones, hydrogen bonding

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 _r = 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
Δρ_max = 0.42 e Å⁻³
Δρ_min = −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 ▶).

Supplementary Material

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

e-70-0o993-sup1.cif^{(23KB, cif)}

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

e-70-0o993-Isup2.hkl^{(187.3KB, hkl)}

Click here for additional data file.^{(2.9KB, cml)}

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

Click here for additional data file.^{(963.5KB, tif)}

. 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.^{(1.6MB, tif)}

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

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⋯N2^v	0.88	2.20	2.981 (8)	148
N4—H41⋯S1A ⁱ	0.88	2.75	3.536 (6)	149
N4—H42⋯S1^vi	0.88	2.63	3.424 (6)	151
N4—H42⋯N2^vi	0.88	2.62	3.083 (9)	114
N4A—H44⋯S1ⁱⁱ	0.88	2.53	3.353 (6)	157
C4—H4⋯S1^vi	0.95	2.74	3.551 (8)	143

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

Acknowledgments

Manchester Metropolitan University, Erciyes University and the University of Leicester are gratefully acknowledged for supporting this study.

supplementary crystallographic information

S1. Comment

Polyfunctional pyridines are highly reactive reagents that have been used extensively in heterocyclic synthesis (Attaby et al., 1995; Asadov et al., 2003). 3-Cyano-pyridine-2(1H)-thiones compounds (Fahmy & Mohareb 1986; Schmidt & Kubitzek, 1960) have also gained considerable interest due to their importance as intermediates for the synthesis of the biologically active deazafolic acid and deaza amino protein ring system (Taylor et al., 1983; Gangiee et al., 1991). In addition, 3-Cyano-2(1H)-pyridinethiones and their related compounds were found to be very reactive substances for the synthesis of many different heterocyclic systems which exhibited biological activities such as antibacterial, pesticidal, antifungal, acaricidal and neurotropic activities (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; Abdel-Rahman et al., 2002; Rao et al., 2006). In light of these observations we report in this study the synthesis and crystal structure of the title compound.

In the title compound (Fig. 1), the asymmetric unit contains two independent molecules (A and B). Molecules A and B both are almost planar (Fig. 3), with the maximum deviations of -0.068 (6) Å for N4 in molecule A and 0.079 (6) Å for N2A in molecule B. The bond lengths of molecules A and B are comparable to those of the previously published structures (Eyduran et al., 2007; Allen et al., 1987).

In the crystal, the N—H···S, N—H···N and C—H···S hydrogen bonds connect the molecules, forming a three dimensional network (Table 1, Fig. 2). In addition, C—H···π interactions and π-π stacking interactions are not observed.

S2. Experimental

The title compound was prepared according to the reported method (Abu-Shanab, 1999). Crystals of the product were obtained in excellent yield (79%) and recrystallized from butanol to afford yellow needles (M.p. 583 K) in a sufficient quality for X-ray diffraction studies.