N-Carbethoxy-N′-[3-(4-methylphenyl)-1H-1,2,4-triazol-5-yl]thiourea

Dolzhenko, A.V.; Tan, G.K.; Koh, L.L.; Dolzhenko, A.V.; Chui, W.K.

doi:10.1107/S1600536810004289

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 3| March 2010| Pages o549-o550

doi:10.1107/S1600536810004289

Open

access

N-Carbethoxy-N′-[3-(4-methylphenyl)-1H-1,2,4-triazol-5-yl]thiourea

Anton V. Dolzhenko,^a ^* Geok Kheng Tan,^b Lip Lin Koh,^b Anna V. Dolzhenko ^a and Wai Keung Chui ^a

^aDepartment of Pharmacy, Faculty of Science, National University of Singapore, 18 Science Drive 4, Singapore 117543, Singapore, and ^bDepartment of Chemistry, Faculty of Science, National University of Singapore, 3 Science Drive 3, Singapore 117543, Singapore
^*Correspondence e-mail: phada@nus.edu.sg

(Received 25 January 2010; accepted 3 February 2010; online 6 February 2010)

The title compound, [systematic name: ethyl ({[3-(4-methylphenyl)-1H-1,2,4-triazol-5-yl]amino}carbonothioyl)carbamate], C₁₃H₁₆N₅O₂S, exists in the 3-aryl-5-thioureido-1H-1,2,4-triazole tautomeric form. The molecular structure is stabilized by intramolecular hydrogen bonding (N—H⋯S=C between the endocyclic N-bound H atom and the thioureido S atom, and N—H⋯O=C within the ethoxycarbonylthiourea unit), both arranged in an S(6) graph-set motif. The mean planes of the phenyl and 1,2,4-triazole rings make a dihedral angle of 6.59 (10)°. In the crystal structure, the molecules form two types of centrosymmetric dimers connected by intermolecular hydrogen bonds; in the first, the N—NH triazole sides of two molecules are connected [R²₂(6) graph-set motif] and the second is an N—H⋯S=C interaction between the imide H atoms and the thiocarbonyl S atoms [R²₂(8) graph-set motif]. Together, they form a network parallel to the (111) plane.

Related literature

For the synthesis, tautomerism and structures of related 1,2,4-triazoles, see: Dolzhenko et al. (2009a ,b ,c , 2010 ); Buzykin et al. (2006 ). For related carbethoxythioureas, see: Dolzhenko et al. (2010); Huang et al. (2009 ); Lin et al. (2004 , 2007 ); Su et al. (2006 ); Zhang et al. (2003 , 2007 ). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₅N₅O₂S
M_r = 305.36
Triclinic, $[P \overline 1]$
a = 6.8430 (5) Å
b = 8.7789 (6) Å
c = 12.2563 (9) Å
α = 90.780 (1)°
β = 99.425 (1)°
γ = 101.279 (1)°
V = 711.52 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.56 × 0.46 × 0.24 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.877, T_max = 0.945
9015 measured reflections
3243 independent reflections
3088 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.095
S = 1.07
3243 reflections
204 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N3ⁱ	0.865 (19)	2.316 (19)	2.9719 (15)	132.8 (16)
N2—H2N⋯S1	0.865 (19)	2.660 (19)	3.1116 (11)	113.8 (15)
N4—H4N⋯O1	0.830 (19)	1.929 (18)	2.6274 (14)	141.2 (17)
N5—H5N⋯S1ⁱⁱ	0.856 (18)	2.576 (19)	3.4119 (11)	165.7 (16)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810004289/kp2249sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810004289/kp2249Isup2.hkl

checkCIF report

Comment top

Recently, we reported the crystal structure of N-carbethoxy-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thiourea (Dolzhenko et al., 2010). Herein, in continuation of our investigations on annular tautomerism of 1,2,4-triazoles (Figs 3 and 4) in solutions (Dolzhenko et al., 2009a) and crystalline state (Dolzhenko et al., 2009b,c, 2010), we study the similar compound with methyl group presented in para-position of the phenyl ring. The electron donating effect of the methyl group might shift the tautomeric equilibrium towards the 5-aryl-3-thioureido-1H-1,2,4-triazole tautomeric form (Buzykin et al., 2006; Dolzhenko et al., 2009a). However, we found that this effect is not sufficient to alter the structure. Analogously to N-carbethoxy-N'-(3-phenyl-1H-1,2,4-triazol-5-yl)thiourea (Dolzhenko et al., 2010), the title compound crystallizes with similar molecular structure (Fig. 1) and packing (Fig. 2). The N2—H···S1 hydrogen bonding between the endocyclic N(3)H proton of the triazole ring and the thioureido sulfur S1 atom (Fig.1 and Table 1) arranged in a S(6) graph-set motif (Bernstein et al., 1995) is believed to be an essential factor stabilizing the tautomer. The triazole ring is planar with an r.m.s. deviation of 0.0069 Å. It makes a dihedral angle of 6.59 (10)° with the phenyl ring. The C10—N4 bond is significantly shorter (1.3414 (16) Å) than other C—N bonds of the carbethoxythiourea group (1.384–1.385 Å). Similarly to the previously reported related structures (Dolzhenko et al., 2010; Huang et al., 2009; Lin et al., 2007; Lin et al., 2004; Su et al., 2006; Zhang et al., 2007; Zhang et al., 2003), the carbethoxythiourea group of the title compound adopts (Z)-configuration across the thiourea C10—N4 bond and (E)-configuration across the C11—N5 bond. The strong intramolecular N4—H···O1═C11 hydrogen bonding arranged in common for carbethoxythioureas (Dolzhenko et al., 2010; Huang et al., 2009; Lin et al., 2007; Lin et al., 2004; Su et al., 2006; Zhang et al., 2007; Zhang et al., 2003) S(6) graph-set motif stabilizes this configuration.

In the crystal, the molecules form two types of centrosymmetric dimmers (Fig. 2, Table 1). The N3—N2H sides of two molecules are connected by intermolecular hydrogen bonds making the R²₂(6) graph-set motif. Atom N5 is also involved in the intermolecular N—H···S interaction with the thiocarbonyl atom S1 of adjacent molecule making another pair with the R²₂(8) graph-set motif similar to that observed in other carbethoxythioureas (Dolzhenko et al., 2010; Huang et al., 2009; Lin et al., 2007; Lin et al., 2004; Su et al., 2006; Zhang et al., 2007; Zhang et al., 2003). Together, these hydrogen bonds connect molecules in a network parallel to the (111) plane.

Related literature top

For the synthesis, tautomerism and structures of related 1,2,4-triazoles, see: Dolzhenko et al. (2009a,b,c, 2010); Buzykin et al. (2006). For related carbethoxythioureas, see: Dolzhenko et al. (2010); Huang et al. (2009); Lin et al. (2004, 2007); Su et al. (2006); Zhang et al. (2003, 2007). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

The title compound (I) was synthesized by nucleophilic addition of 3(5)-amino-5(3)-(4-methylphenyl)-1H-1,2,4-triazole (Dolzhenko et al., 2009a) to ethoxycarbonyl isothiocyanate in DMF solution at room temperature (Fig. 3). Single crystals suitable for crystallographic analysis were grown by recrystallization from ethanol.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of I with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing in the cell viewed along the axis c.
	Fig. 3. Synthesis of N-carbethoxy-N'-[3-(4-methylphenyl)-1H-1,2,4-triazol-5- yl]thiourea.
	Fig. 4. Annular tautomerism in N-carbethoxy-N'-[3(5)-(4-methylphenyl)-1(4)H-1,2,4-τriazol-5(3)-yl]thiourea.

ethyl ({[3-(4-methylphenyl)-1H-1,2,4-triazol-5-yl]amino}carbonothioyl)carbamate top

Crystal data top

C₁₃H₁₅N₅O₂S	Z = 2
M_r = 305.36	F(000) = 320
Triclinic, P1	D_x = 1.425 Mg m⁻³
Hall symbol: -P 1	Melting point: 489 K
a = 6.8430 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7789 (6) Å	Cell parameters from 6864 reflections
c = 12.2563 (9) Å	θ = 2.4–27.5°
α = 90.780 (1)°	µ = 0.24 mm⁻¹
β = 99.425 (1)°	T = 100 K
γ = 101.279 (1)°	Block, colourless
V = 711.52 (9) Å³	0.56 × 0.46 × 0.24 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3243 independent reflections
Radiation source: fine-focus sealed tube	3088 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 27.5°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −8→8
T_min = 0.877, T_max = 0.945	k = −11→11
9015 measured reflections	l = −15→15

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0529P)² + 0.328P] where P = (F_o² + 2F_c²)/3
3243 reflections	(Δ/σ)_max = 0.001
204 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₁₃H₁₅N₅O₂S	γ = 101.279 (1)°
M_r = 305.36	V = 711.52 (9) Å³
Triclinic, P1	Z = 2
a = 6.8430 (5) Å	Mo Kα radiation
b = 8.7789 (6) Å	µ = 0.24 mm⁻¹
c = 12.2563 (9) Å	T = 100 K
α = 90.780 (1)°	0.56 × 0.46 × 0.24 mm
β = 99.425 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	3243 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	3088 reflections with I > 2σ(I)
T_min = 0.877, T_max = 0.945	R_int = 0.021
9015 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.44 e Å⁻³
3243 reflections	Δρ_min = −0.31 e Å⁻³
204 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
S1	0.23286 (5)	0.36065 (4)	0.52820 (2)	0.01721 (11)
O1	0.17169 (14)	0.49382 (11)	0.16661 (8)	0.0193 (2)
O2	−0.10045 (14)	0.57606 (10)	0.20980 (8)	0.0174 (2)
N1	0.62121 (16)	0.25023 (12)	0.28575 (9)	0.0155 (2)
N2	0.51358 (16)	0.16832 (13)	0.43785 (9)	0.0162 (2)
H2N	0.440 (3)	0.145 (2)	0.4885 (16)	0.029 (5)*
N3	0.65581 (16)	0.08284 (13)	0.42368 (9)	0.0173 (2)
N4	0.35689 (16)	0.35967 (12)	0.33186 (9)	0.0156 (2)
H4N	0.343 (3)	0.390 (2)	0.2676 (16)	0.024 (4)*
N5	0.09899 (17)	0.48816 (13)	0.34439 (9)	0.0163 (2)
H5N	0.016 (3)	0.512 (2)	0.3841 (15)	0.022 (4)*
C1	1.3339 (2)	−0.07535 (17)	0.13315 (12)	0.0239 (3)
H1A	1.4199	−0.1231	0.1888	0.036*
H1B	1.4169	0.0132	0.1036	0.036*
H1C	1.2688	−0.1521	0.0728	0.036*
C2	1.17417 (19)	−0.02005 (15)	0.18576 (11)	0.0180 (3)
C3	1.0630 (2)	0.08361 (15)	0.13251 (11)	0.0184 (3)
H3	1.0898	0.1204	0.0628	0.022*
C4	0.91420 (19)	0.13361 (14)	0.17991 (11)	0.0169 (3)
H4	0.8391	0.2029	0.1420	0.020*
C5	0.87416 (18)	0.08280 (14)	0.28277 (10)	0.0149 (2)
C6	0.98549 (19)	−0.01994 (14)	0.33704 (11)	0.0169 (3)
H6	0.9604	−0.0554	0.4073	0.020*
C7	1.13279 (19)	−0.07028 (15)	0.28828 (11)	0.0180 (3)
H7	1.2069	−0.1405	0.3258	0.022*
C8	0.71732 (18)	0.13779 (14)	0.33214 (10)	0.0144 (2)
C9	0.49501 (18)	0.26348 (14)	0.35425 (10)	0.0143 (2)
C10	0.23405 (18)	0.40227 (14)	0.39616 (10)	0.0144 (2)
C11	0.06534 (19)	0.51753 (14)	0.23292 (11)	0.0156 (2)
C12	−0.1632 (2)	0.59864 (16)	0.09263 (11)	0.0197 (3)
H12A	−0.2036	0.4972	0.0505	0.024*
H12B	−0.0510	0.6633	0.0622	0.024*
C13	−0.3400 (2)	0.67920 (17)	0.08463 (12)	0.0234 (3)
H13A	−0.4464	0.6170	0.1192	0.035*
H13B	−0.3926	0.6911	0.0066	0.035*
H13C	−0.2958	0.7819	0.1229	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.02084 (18)	0.01893 (17)	0.01474 (17)	0.00843 (12)	0.00598 (12)	0.00253 (11)
O1	0.0225 (5)	0.0213 (5)	0.0182 (4)	0.0100 (4)	0.0082 (4)	0.0051 (4)
O2	0.0192 (4)	0.0177 (4)	0.0178 (4)	0.0082 (3)	0.0049 (3)	0.0034 (3)
N1	0.0169 (5)	0.0127 (5)	0.0181 (5)	0.0040 (4)	0.0049 (4)	0.0016 (4)
N2	0.0162 (5)	0.0182 (5)	0.0172 (5)	0.0076 (4)	0.0066 (4)	0.0035 (4)
N3	0.0169 (5)	0.0190 (5)	0.0195 (5)	0.0089 (4)	0.0067 (4)	0.0042 (4)
N4	0.0183 (5)	0.0161 (5)	0.0147 (5)	0.0070 (4)	0.0051 (4)	0.0029 (4)
N5	0.0187 (5)	0.0170 (5)	0.0166 (5)	0.0089 (4)	0.0067 (4)	0.0019 (4)
C1	0.0195 (6)	0.0250 (7)	0.0298 (7)	0.0071 (5)	0.0087 (5)	−0.0045 (6)
C2	0.0151 (6)	0.0157 (6)	0.0232 (6)	0.0021 (5)	0.0050 (5)	−0.0045 (5)
C3	0.0209 (6)	0.0161 (6)	0.0195 (6)	0.0026 (5)	0.0082 (5)	0.0005 (5)
C4	0.0179 (6)	0.0143 (6)	0.0197 (6)	0.0044 (5)	0.0050 (5)	0.0020 (5)
C5	0.0147 (6)	0.0127 (5)	0.0176 (6)	0.0023 (4)	0.0043 (5)	−0.0010 (4)
C6	0.0182 (6)	0.0155 (6)	0.0172 (6)	0.0037 (5)	0.0032 (5)	0.0013 (5)
C7	0.0167 (6)	0.0148 (6)	0.0225 (6)	0.0054 (5)	0.0011 (5)	−0.0004 (5)
C8	0.0142 (5)	0.0130 (5)	0.0161 (6)	0.0028 (4)	0.0026 (4)	0.0002 (4)
C9	0.0143 (5)	0.0122 (5)	0.0165 (6)	0.0029 (4)	0.0027 (4)	−0.0005 (4)
C10	0.0153 (6)	0.0114 (5)	0.0167 (6)	0.0025 (4)	0.0036 (4)	0.0000 (4)
C11	0.0181 (6)	0.0109 (5)	0.0186 (6)	0.0038 (4)	0.0043 (5)	0.0014 (4)
C12	0.0219 (6)	0.0217 (6)	0.0176 (6)	0.0091 (5)	0.0034 (5)	0.0042 (5)
C13	0.0197 (6)	0.0241 (7)	0.0286 (7)	0.0090 (5)	0.0048 (5)	0.0060 (5)

Geometric parameters (Å, º) top

S1—C10	1.6649 (13)	C1—H1C	0.9800
O1—C11	1.2173 (16)	C2—C7	1.3915 (19)
O2—C11	1.3260 (15)	C2—C3	1.3988 (18)
O2—C12	1.4578 (15)	C3—C4	1.3889 (17)
N1—C9	1.3184 (16)	C3—H3	0.9500
N1—C8	1.3701 (15)	C4—C5	1.3943 (17)
N2—C9	1.3364 (16)	C4—H4	0.9500
N2—N3	1.3704 (14)	C5—C6	1.3984 (17)
N2—H2N	0.865 (19)	C5—C8	1.4691 (17)
N3—C8	1.3261 (16)	C6—C7	1.3903 (17)
N4—C10	1.3414 (16)	C6—H6	0.9500
N4—C9	1.3839 (15)	C7—H7	0.9500
N4—H4N	0.830 (19)	C12—C13	1.5067 (18)
N5—C11	1.3840 (16)	C12—H12A	0.9900
N5—C10	1.3853 (16)	C12—H12B	0.9900
N5—H5N	0.856 (18)	C13—H13A	0.9800
C1—C2	1.5088 (17)	C13—H13B	0.9800
C1—H1A	0.9800	C13—H13C	0.9800
C1—H1B	0.9800

C11—O2—C12	114.69 (10)	C7—C6—C5	120.07 (12)
C9—N1—C8	102.36 (10)	C7—C6—H6	120.0
C9—N2—N3	109.09 (10)	C5—C6—H6	120.0
C9—N2—H2N	130.3 (12)	C6—C7—C2	121.48 (12)
N3—N2—H2N	119.7 (12)	C6—C7—H7	119.3
C8—N3—N2	102.49 (10)	C2—C7—H7	119.3
C10—N4—C9	129.41 (11)	N3—C8—N1	114.56 (11)
C10—N4—H4N	116.0 (12)	N3—C8—C5	123.37 (11)
C9—N4—H4N	114.5 (12)	N1—C8—C5	122.06 (11)
C11—N5—C10	126.49 (11)	N1—C9—N2	111.46 (11)
C11—N5—H5N	117.7 (12)	N1—C9—N4	120.65 (11)
C10—N5—H5N	115.0 (12)	N2—C9—N4	127.77 (11)
C2—C1—H1A	109.5	N4—C10—N5	114.73 (11)
C2—C1—H1B	109.5	N4—C10—S1	125.77 (9)
H1A—C1—H1B	109.5	N5—C10—S1	119.49 (9)
C2—C1—H1C	109.5	O1—C11—O2	125.35 (12)
H1A—C1—H1C	109.5	O1—C11—N5	125.32 (12)
H1B—C1—H1C	109.5	O2—C11—N5	109.33 (11)
C7—C2—C3	118.02 (11)	O2—C12—C13	106.66 (11)
C7—C2—C1	121.23 (12)	O2—C12—H12A	110.4
C3—C2—C1	120.75 (12)	C13—C12—H12A	110.4
C4—C3—C2	121.03 (12)	O2—C12—H12B	110.4
C4—C3—H3	119.5	C13—C12—H12B	110.4
C2—C3—H3	119.5	H12A—C12—H12B	108.6
C3—C4—C5	120.49 (12)	C12—C13—H13A	109.5
C3—C4—H4	119.8	C12—C13—H13B	109.5
C5—C4—H4	119.8	H13A—C13—H13B	109.5
C4—C5—C6	118.90 (11)	C12—C13—H13C	109.5
C4—C5—C8	119.80 (11)	H13A—C13—H13C	109.5
C6—C5—C8	121.30 (11)	H13B—C13—H13C	109.5

C9—N2—N3—C8	1.76 (13)	C4—C5—C8—N1	−6.63 (18)
C7—C2—C3—C4	−0.71 (19)	C6—C5—C8—N1	173.24 (11)
C1—C2—C3—C4	179.27 (12)	C8—N1—C9—N2	0.94 (14)
C2—C3—C4—C5	0.84 (19)	C8—N1—C9—N4	−175.31 (11)
C3—C4—C5—C6	−0.36 (19)	N3—N2—C9—N1	−1.78 (15)
C3—C4—C5—C8	179.52 (11)	N3—N2—C9—N4	174.14 (12)
C4—C5—C6—C7	−0.23 (19)	C10—N4—C9—N1	−171.44 (12)
C8—C5—C6—C7	179.89 (11)	C10—N4—C9—N2	13.0 (2)
C5—C6—C7—C2	0.36 (19)	C9—N4—C10—N5	−173.84 (12)
C3—C2—C7—C6	0.11 (19)	C9—N4—C10—S1	6.13 (19)
C1—C2—C7—C6	−179.87 (12)	C11—N5—C10—N4	7.69 (18)
N2—N3—C8—N1	−1.24 (14)	C11—N5—C10—S1	−172.28 (10)
N2—N3—C8—C5	179.33 (11)	C12—O2—C11—O1	5.70 (18)
C9—N1—C8—N3	0.24 (14)	C12—O2—C11—N5	−174.54 (10)
C9—N1—C8—C5	179.68 (11)	C10—N5—C11—O1	−12.6 (2)
C4—C5—C8—N3	172.75 (12)	C10—N5—C11—O2	167.62 (11)
C6—C5—C8—N3	−7.38 (19)	C11—O2—C12—C13	−174.72 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N3ⁱ	0.865 (19)	2.316 (19)	2.9719 (15)	132.8 (16)
N2—H2N···S1	0.865 (19)	2.660 (19)	3.1116 (11)	113.8 (15)
N4—H4N···O1	0.830 (19)	1.929 (18)	2.6274 (14)	141.2 (17)
N5—H5N···S1ⁱⁱ	0.856 (18)	2.576 (19)	3.4119 (11)	165.7 (16)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₅N₅O₂S
M_r	305.36
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.8430 (5), 8.7789 (6), 12.2563 (9)
α, β, γ (°)	90.780 (1), 99.425 (1), 101.279 (1)
V (Å³)	711.52 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.56 × 0.46 × 0.24

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.877, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	9015, 3243, 3088
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.095, 1.07
No. of reflections	3243
No. of parameters	204
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.31

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···N3ⁱ	0.865 (19)	2.316 (19)	2.9719 (15)	132.8 (16)
N2—H2N···S1	0.865 (19)	2.660 (19)	3.1116 (11)	113.8 (15)
N4—H4N···O1	0.830 (19)	1.929 (18)	2.6274 (14)	141.2 (17)
N5—H5N···S1ⁱⁱ	0.856 (18)	2.576 (19)	3.4119 (11)	165.7 (16)

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

Acknowledgements

This work was supported by the National Medical Research Council, Singapore (grant No. NMRC/NIG/0019/2008).

References

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
Bruker (2001). SMART and SAINT. Bruker AXS GmbH, Karlsruhe, Germany. Google Scholar
Buzykin, B. I., Mironova, E. V., Nabiullin, V. N., Gubaidullin, A. T. & Litvinov, I. A. (2006). Russ. J. Gen. Chem. 76, 1471–1486. Web of Science CrossRef CAS Google Scholar
Dolzhenko, A. V., Pastorin, G., Dolzhenko, A. V. & Chui, W. K. (2009a). Tetrahedron Lett. 50, 2124–2128. Web of Science CrossRef CAS Google Scholar
Dolzhenko, A. V., Tan, G. K., Koh, L. L., Dolzhenko, A. V. & Chui, W. K. (2009b). Acta Cryst. E65, o126. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dolzhenko, A. V., Tan, G. K., Koh, L. L., Dolzhenko, A. V. & Chui, W. K. (2009c). Acta Cryst. E65, o125. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dolzhenko, A. V., Tan, G. K., Koh, L. L., Dolzhenko, A. V. & Chui, W. K. (2010). Acta Cryst. E66, o425. Web of Science CSD CrossRef IUCr Journals Google Scholar
Huang, B., Kung, P.-P., Rheingold, A. L., DiPasquale, A. & Yanovsky, A. (2009). Acta Cryst. E65, o1249. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lin, Q., Wei, T. B. & Zhang, Y. M. (2007). Phosphorus Sulfur Silicon Relat. Elem. 182, 863–871. Web of Science CSD CrossRef CAS Google Scholar
Lin, Q., Zhang, Y.-M., Wei, T.-B. & Wang, H. (2004). Acta Cryst. E60, o580–o582. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, B. Q., Liu, G. L., Sheng, L., Wang, X. Q. & Xian, L. (2006). Phosphorus Sulfur Silicon Relat. Elem. 181, 745–750. Web of Science CSD CrossRef CAS Google Scholar
Zhang, Y.-M., Wei, T.-B., Xian, L., Lin, Q. & Yu, K.-B. (2003). Acta Cryst. E59, o905–o906. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhang, B., Xian, L. & Xiang, X. M. (2007). Z. Kristallogr. New Cryst. Struct. 222, 447–448. CAS Google Scholar