4-Carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide

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

doi:10.1107/S1600536810015576

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1241

https://doi.org/10.1107/S1600536810015576

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4-Carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide

Hriday Bera,^a Anton V. Dolzhenko,^a ^* Geok Kheng Tan,^b Lip Lin Koh ^b 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 20 April 2010; accepted 27 April 2010; online 30 April 2010)

The molecular structure of the title compound, C₁₃H₁₈N₄O₃S, (systematic name: ethyl N-{2-[4-(dimethylamino)benzoyl]hydrazinethiocarbonyl}carbamate) is stabilized by intramolecular N—H⋯O=C hydrogen bonding arranged in an S(6) graph-set motif. In the crystal, inversion dimers connected via intermolecular N—H⋯S=C hydrogen bonds [R₂²(8) graph-set motif] form sheets parallel to the ( $[\overline{1}]$ 21) plane. Dimers are also formed by the molecules via weak intermolecular N—H⋯S=C hydrogen bonds [R₂²(10) graph-set motif] connecting the sheets.

Related literature

For examples of bioactive 1,4-diacyl substituted thiosemicarbazides and their metal complexes, see: Angelusiu et al. (2009 ); Cunha et al. (2007 ); Qandil et al. (2006 ). For 4-aroyl-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazides as high affinity anion receptors, see: Liu & Jiang (2008 ). For the structures of related carbethoxythioureas, see: Dolzhenko et al. (2010a ,b ). For the structures of related 1,4-diacyl thiosemicarbazides, see: Ali et al. (2004 ); Xue et al. (2006 ); Yamin & Yusof (2003 ); Yusof et al. (2003 ). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₃H₁₈N₄O₃S
M_r = 310.37
Triclinic, $[P \overline 1]$
a = 7.876 (4) Å
b = 8.184 (4) Å
c = 12.086 (6) Å
α = 82.290 (12)°
β = 74.769 (11)°
γ = 84.469 (11)°
V = 743.3 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.24 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ) T_min = 0.946, T_max = 0.982
5201 measured reflections
3379 independent reflections
2839 reflections with I > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.081
wR(F²) = 0.218
S = 1.18
3379 reflections
205 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯S1ⁱ	0.82 (6)	2.53 (6)	3.342 (3)	173 (5)
N3—H3N⋯S1ⁱⁱ	0.80 (4)	2.64 (5)	3.385 (4)	156 (4)
N2—H2N⋯O2	0.86 (5)	2.02 (5)	2.653 (4)	130 (4)
Symmetry codes: (i) -x+1, -y+2, -z+2; (ii) -x, -y+2, -z+2.

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: https://doi.org/10.1107/S1600536810015576/ds2029sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810015576/ds2029Isup2.hkl

checkCIF report

Comment top

1,4-Diacyl substituted thiosemicarbazides and their metal complexes have been demonstrated to possess a potent antimicrobial activity (Angelusiu et al., 2009; Cunha et al., 2007; Qandil et al., 2006). In continuation of our structural investigations of the carbethoxythioureas derivatives (Dolzhenko et al., 2010a,b), we report herein molecular and crystal structure of 4-carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide (Figure 1 and 2). The compound is a structural analogue of 4-aroyl-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazides reported recently as high affinity anion receptors (Liu & Jiang, 2008).

4-Carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide was prepared by nucleophilic addition of 4-(N,N-dimethylamino)benzhydrazide to ethoxycarbonyl isothiocyanate in DMF at room temperature (Figure 3).

The molecule of 4-carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide adopts similar to the previously reported (Ali et al., 2004; Xue et al., 2006; Yamin & Yusof, 2003;. Yusof et al., 2003) for the related 1,4-diacyl substituted thiosemicarbazides configuration with the thiocarbonyl group pointed to the side opposite of the carbonyl groups. In the thiourea fragment, (E)- and (Z)-configurations observed across the C4—N1 and C4—N2 bonds, respectively. This configuration is stabilized by the strong intramolecular hydrogen bonding between N(2)—H and O2═C3 arranged in the S(6) graph-set motif (Bernstein et al., 1995).

The thiourea C4—N2 bond is significantly shorter (1.315 (5) Å) than other C—N bonds of the molecule. The planarity of the molecule is affected by some twisting at the hydrazine N2—N3 fragment [—C4—N2—N3—C6— torsion angle is 166.5 (33)°].

In the crystal, the molecules form sheets parallel to the (121) plane (Figure 2). In the sheets, atom N1 of one molecule is involved in a intermolecular N(1)—H···S═C interaction with the thiocarbonyl atom S1 of adjacent molecule making pair with the R₂²(8) graph-set motif. Dimmers are also formed by molecules via week intermolecular N(3)—H···S═C hydrogen bonds arranged in R₂²(10)graph-set motifs connecting the sheets between each other.

Related literature top

For examples of bioactive 1,4-diacyl substituted thiosemicarbazides and their metal complexes, see: Angelusiu et al. (2009); Cunha et al. (2007); Qandil et al. (2006). For 4-aroyl-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazides as high affinity anion receptors, see: Liu & Jiang (2008). For the structures of related carbethoxythioureas, see: Dolzhenko et al. (2010a,b). For the structures of related 1,4-diacyl thiosemicarbazides, see: Ali et al. (2004); Xue et al. (2006); Yamin & Yusof (2003); Yusof et al. (2003). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

Experimental top

To a fine suspension of 4-(N,N-dimethylamino)benzhydrazide in (0.54 g, 3.0 mmol) in anhydrous DMF (4 ml), ethoxycarbonyl isothiocyanate (0.37 ml, 3.3 mmol) was added. After stirring the mixture for 5 h at ambient temperature, cold water (50 ml) was added. The precipitated product was filtered, washed with cold water and recrystallized from toluene. Yield 0.83 g (89%), m.p. 201 °C (PhMe).

¹H NMR (300 MHz, DMSO-d₆): δ 1.26 (t, 3H, CH₃, J 7.2 Hz), 2.99 (s, 6H, N(CH₃)₂), 4.21 (q, 2H, CH₂, J 7.2 Hz), 6.74 (d, 2H, Ar, J 8.7 Hz), 7.78 (d, 2H, Ar, J 8.7 Hz), 10.56 (s, 1H, NH), 11.34 (s, 1H, NH), 11.41 (s, 1H, NH).

¹³C NMR (75 MHz, DMSO-d₆): δ 15.2, 40.1 (2 C), 62.7, 111.3 (2 C), 118.6, 129.6 (2 C), 153.1, 153.8, 165.0, 179.8.

Structure description top

For examples of bioactive 1,4-diacyl substituted thiosemicarbazides and their metal complexes, see: Angelusiu et al. (2009); Cunha et al. (2007); Qandil et al. (2006). For 4-aroyl-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazides as high affinity anion receptors, see: Liu & Jiang (2008). For the structures of related carbethoxythioureas, see: Dolzhenko et al. (2010a,b). For the structures of related 1,4-diacyl thiosemicarbazides, see: Ali et al. (2004); Xue et al. (2006); Yamin & Yusof (2003); Yusof et al. (2003). For the graph-set analysis of hydrogen bonding, see: Bernstein et al. (1995).

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 4-carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing in the cell (view along axis c)
	Fig. 3. Synthesis of 4-carbethoxy-1-[4-(N,N-dimethylamino)benzoyl]thiosemicarbazide

Ethyl N-{2-[4-(dimethylamino)benzoyl]hydrazinethiocarbonyl}carbamate top

Crystal data top

C₁₃H₁₈N₄O₃S	Z = 2
M_r = 310.37	F(000) = 328
Triclinic, P1	D_x = 1.387 Mg m⁻³
Hall symbol: -P 1	Melting point: 474 K
a = 7.876 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.184 (4) Å	Cell parameters from 644 reflections
c = 12.086 (6) Å	θ = 2.5–27.4°
α = 82.290 (12)°	µ = 0.23 mm⁻¹
β = 74.769 (11)°	T = 100 K
γ = 84.469 (11)°	Rod, colourless
V = 743.3 (7) Å³	0.24 × 0.10 × 0.08 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3379 independent reflections
Radiation source: fine-focus sealed tube	2839 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
φ and ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −9→10
T_min = 0.946, T_max = 0.982	k = −10→10
5201 measured reflections	l = −12→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)] = 0.081	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.218	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	w = 1/[σ²(F_o²) + (0.0987P)² + 1.3625P] where P = (F_o² + 2F_c²)/3
3379 reflections	(Δ/σ)_max < 0.001
205 parameters	Δρ_max = 0.84 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

C₁₃H₁₈N₄O₃S	γ = 84.469 (11)°
M_r = 310.37	V = 743.3 (7) Å³
Triclinic, P1	Z = 2
a = 7.876 (4) Å	Mo Kα radiation
b = 8.184 (4) Å	µ = 0.23 mm⁻¹
c = 12.086 (6) Å	T = 100 K
α = 82.290 (12)°	0.24 × 0.10 × 0.08 mm
β = 74.769 (11)°

Data collection top

Bruker SMART APEX CCD diffractometer	3379 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	2839 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.982	R_int = 0.031
5201 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.081	0 restraints
wR(F²) = 0.218	H atoms treated by a mixture of independent and constrained refinement
S = 1.18	Δρ_max = 0.84 e Å⁻³
3379 reflections	Δρ_min = −0.45 e Å⁻³
205 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	0.25106 (11)	0.89905 (11)	1.00357 (7)	0.0123 (3)
O1	0.6976 (3)	1.2062 (3)	0.7276 (2)	0.0147 (6)
O2	0.4814 (3)	1.1658 (3)	0.6437 (2)	0.0152 (6)
O3	0.1155 (3)	0.9455 (3)	0.6162 (2)	0.0146 (6)
N1	0.4741 (4)	1.0685 (4)	0.8327 (3)	0.0106 (6)
H1N	0.534 (7)	1.072 (7)	0.878 (5)	0.037 (15)*
N2	0.2296 (4)	0.9931 (4)	0.7882 (3)	0.0123 (6)
H2N	0.262 (6)	1.043 (6)	0.719 (4)	0.017 (11)*
N3	0.0781 (4)	0.9079 (4)	0.8084 (3)	0.0138 (7)
H3N	0.005 (6)	0.926 (5)	0.866 (4)	0.011 (10)*
N4	−0.6011 (4)	0.5754 (4)	0.7533 (3)	0.0218 (8)
C1	0.9562 (5)	1.3511 (5)	0.6447 (3)	0.0151 (8)
H1A	0.9156	1.4354	0.6979	0.023*
H1B	1.0341	1.3997	0.5730	0.023*
H1C	1.0207	1.2596	0.6803	0.023*
C2	0.7995 (5)	1.2877 (5)	0.6182 (3)	0.0138 (7)
H2A	0.7274	1.3800	0.5879	0.017*
H2B	0.8385	1.2083	0.5601	0.017*
C3	0.5467 (5)	1.1491 (4)	0.7259 (3)	0.0109 (7)
C4	0.3184 (4)	0.9900 (4)	0.8667 (3)	0.0119 (7)
C6	0.0248 (4)	0.8950 (4)	0.7109 (3)	0.0109 (7)
C7	−0.1384 (4)	0.8092 (4)	0.7270 (3)	0.0108 (7)
C8	−0.2115 (5)	0.8174 (4)	0.6328 (3)	0.0122 (7)
H8	−0.1558	0.8778	0.5619	0.015*
C9	−0.3619 (5)	0.7403 (5)	0.6401 (3)	0.0137 (7)
H9	−0.4079	0.7473	0.5743	0.016*
C10	−0.4491 (5)	0.6506 (4)	0.7447 (3)	0.0127 (7)
C11	−0.3746 (5)	0.6417 (5)	0.8393 (3)	0.0145 (7)
H11	−0.4295	0.5811	0.9104	0.017*
C12	−0.2221 (5)	0.7201 (5)	0.8304 (3)	0.0124 (7)
H12	−0.1742	0.7129	0.8955	0.015*
C13	−0.6896 (5)	0.4845 (5)	0.8622 (4)	0.0228 (9)
H13A	−0.6084	0.3962	0.8853	0.034*
H13B	−0.7933	0.4363	0.8527	0.034*
H13C	−0.7266	0.5600	0.9219	0.034*
C14	−0.6706 (5)	0.5756 (5)	0.6535 (3)	0.0172 (8)
H14A	−0.6649	0.6861	0.6103	0.026*
H14B	−0.7935	0.5456	0.6789	0.026*
H14C	−0.6004	0.4953	0.6037	0.026*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0110 (4)	0.0190 (5)	0.0080 (4)	−0.0039 (3)	−0.0034 (3)	−0.0013 (3)
O1	0.0134 (12)	0.0172 (13)	0.0144 (13)	−0.0080 (10)	−0.0040 (10)	0.0009 (10)
O2	0.0169 (13)	0.0166 (13)	0.0141 (13)	−0.0069 (10)	−0.0066 (10)	0.0008 (10)
O3	0.0172 (13)	0.0185 (13)	0.0092 (12)	−0.0073 (10)	−0.0032 (10)	−0.0018 (10)
N1	0.0119 (14)	0.0123 (14)	0.0092 (14)	−0.0051 (11)	−0.0045 (12)	−0.0004 (11)
N2	0.0122 (14)	0.0179 (15)	0.0072 (14)	−0.0068 (12)	−0.0028 (11)	0.0024 (12)
N3	0.0067 (13)	0.0220 (17)	0.0128 (16)	−0.0060 (12)	−0.0001 (12)	−0.0032 (13)
N4	0.0201 (17)	0.0303 (19)	0.0176 (17)	−0.0149 (15)	−0.0078 (14)	0.0034 (14)
C1	0.0134 (16)	0.0133 (17)	0.0183 (19)	−0.0044 (13)	−0.0034 (14)	0.0004 (14)
C2	0.0167 (17)	0.0143 (17)	0.0107 (17)	−0.0068 (14)	−0.0019 (14)	−0.0010 (13)
C3	0.0129 (16)	0.0051 (15)	0.0149 (17)	−0.0016 (12)	−0.0018 (13)	−0.0045 (12)
C4	0.0110 (16)	0.0113 (16)	0.0133 (17)	0.0005 (13)	−0.0031 (13)	−0.0024 (13)
C6	0.0109 (15)	0.0101 (16)	0.0122 (17)	−0.0015 (13)	−0.0016 (13)	−0.0050 (13)
C7	0.0091 (15)	0.0122 (16)	0.0104 (16)	−0.0028 (13)	−0.0004 (13)	−0.0012 (13)
C8	0.0130 (16)	0.0089 (16)	0.0142 (17)	0.0012 (13)	−0.0012 (13)	−0.0048 (13)
C9	0.0164 (17)	0.0180 (18)	0.0108 (17)	−0.0025 (14)	−0.0078 (14)	−0.0064 (14)
C10	0.0129 (16)	0.0119 (16)	0.0144 (18)	−0.0030 (13)	−0.0040 (14)	−0.0025 (13)
C11	0.0159 (17)	0.0163 (18)	0.0106 (17)	−0.0069 (14)	−0.0024 (14)	0.0028 (14)
C12	0.0111 (16)	0.0180 (18)	0.0096 (16)	−0.0035 (13)	−0.0049 (13)	−0.0004 (13)
C13	0.0180 (19)	0.025 (2)	0.026 (2)	−0.0121 (16)	−0.0032 (16)	−0.0026 (17)
C14	0.0189 (18)	0.0167 (18)	0.021 (2)	−0.0042 (14)	−0.0125 (15)	−0.0029 (15)

Geometric parameters (Å, º) top

S1—C4	1.690 (4)	C2—H2A	0.9900
O1—C3	1.325 (4)	C2—H2B	0.9900
O1—C2	1.465 (4)	C6—C7	1.479 (5)
O2—C3	1.219 (4)	C7—C12	1.394 (5)
O3—C6	1.221 (4)	C7—C8	1.396 (5)
N1—C3	1.374 (5)	C8—C9	1.372 (5)
N1—C4	1.379 (4)	C8—H8	0.9500
N1—H1N	0.82 (6)	C9—C10	1.414 (5)
N2—C4	1.315 (5)	C9—H9	0.9500
N2—N3	1.390 (4)	C10—C11	1.407 (5)
N2—H2N	0.86 (5)	C11—C12	1.389 (5)
N3—C6	1.371 (5)	C11—H11	0.9500
N3—H3N	0.80 (4)	C12—H12	0.9500
N4—C10	1.372 (5)	C13—H13A	0.9800
N4—C14	1.450 (5)	C13—H13B	0.9800
N4—C13	1.458 (5)	C13—H13C	0.9800
C1—C2	1.507 (5)	C14—H14A	0.9800
C1—H1A	0.9800	C14—H14B	0.9800
C1—H1B	0.9800	C14—H14C	0.9800
C1—H1C	0.9800

C3—O1—C2	116.3 (3)	O3—C6—C7	123.2 (3)
C3—N1—C4	127.1 (3)	N3—C6—C7	116.7 (3)
C3—N1—H1N	112 (4)	C12—C7—C8	118.4 (3)
C4—N1—H1N	121 (4)	C12—C7—C6	123.7 (3)
C4—N2—N3	122.1 (3)	C8—C7—C6	117.9 (3)
C4—N2—H2N	124 (3)	C9—C8—C7	121.6 (3)
N3—N2—H2N	114 (3)	C9—C8—H8	119.2
C6—N3—N2	114.1 (3)	C7—C8—H8	119.2
C6—N3—H3N	119 (3)	C8—C9—C10	120.6 (3)
N2—N3—H3N	114 (3)	C8—C9—H9	119.7
C10—N4—C14	121.0 (3)	C10—C9—H9	119.7
C10—N4—C13	120.2 (3)	N4—C10—C11	121.3 (3)
C14—N4—C13	118.7 (3)	N4—C10—C9	121.0 (3)
C2—C1—H1A	109.5	C11—C10—C9	117.7 (3)
C2—C1—H1B	109.5	C12—C11—C10	121.0 (3)
H1A—C1—H1B	109.5	C12—C11—H11	119.5
C2—C1—H1C	109.5	C10—C11—H11	119.5
H1A—C1—H1C	109.5	C11—C12—C7	120.7 (3)
H1B—C1—H1C	109.5	C11—C12—H12	119.7
O1—C2—C1	106.0 (3)	C7—C12—H12	119.7
O1—C2—H2A	110.5	N4—C13—H13A	109.5
C1—C2—H2A	110.5	N4—C13—H13B	109.5
O1—C2—H2B	110.5	H13A—C13—H13B	109.5
C1—C2—H2B	110.5	N4—C13—H13C	109.5
H2A—C2—H2B	108.7	H13A—C13—H13C	109.5
O2—C3—O1	126.1 (3)	H13B—C13—H13C	109.5
O2—C3—N1	125.2 (3)	N4—C14—H14A	109.5
O1—C3—N1	108.7 (3)	N4—C14—H14B	109.5
N2—C4—N1	116.4 (3)	H14A—C14—H14B	109.5
N2—C4—S1	123.9 (3)	N4—C14—H14C	109.5
N1—C4—S1	119.7 (3)	H14A—C14—H14C	109.5
O3—C6—N3	120.0 (3)	H14B—C14—H14C	109.5

C4—N2—N3—C6	−166.5 (3)	N3—C6—C7—C8	169.8 (3)
C3—O1—C2—C1	176.1 (3)	C12—C7—C8—C9	0.0 (5)
C2—O1—C3—O2	−4.1 (5)	C6—C7—C8—C9	179.5 (3)
C2—O1—C3—N1	176.4 (3)	C7—C8—C9—C10	0.6 (5)
C4—N1—C3—O2	1.2 (6)	C14—N4—C10—C11	−175.8 (3)
C4—N1—C3—O1	−179.3 (3)	C13—N4—C10—C11	0.3 (6)
N3—N2—C4—N1	174.8 (3)	C14—N4—C10—C9	4.3 (6)
N3—N2—C4—S1	−6.0 (5)	C13—N4—C10—C9	−179.5 (4)
C3—N1—C4—N2	−0.2 (5)	C8—C9—C10—N4	178.9 (3)
C3—N1—C4—S1	−179.4 (3)	C8—C9—C10—C11	−0.9 (5)
N2—N3—C6—O3	5.2 (5)	N4—C10—C11—C12	−179.1 (4)
N2—N3—C6—C7	−178.5 (3)	C9—C10—C11—C12	0.8 (5)
O3—C6—C7—C12	165.6 (4)	C10—C11—C12—C7	−0.3 (6)
N3—C6—C7—C12	−10.6 (5)	C8—C7—C12—C11	−0.1 (5)
O3—C6—C7—C8	−13.9 (5)	C6—C7—C12—C11	−179.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···S1ⁱ	0.82 (6)	2.53 (6)	3.342 (3)	173 (5)
N3—H3N···S1ⁱⁱ	0.80 (4)	2.64 (5)	3.385 (4)	156 (4)
N2—H2N···O2	0.86 (5)	2.02 (5)	2.653 (4)	130 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₃H₁₈N₄O₃S
M_r	310.37
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	7.876 (4), 8.184 (4), 12.086 (6)
α, β, γ (°)	82.290 (12), 74.769 (11), 84.469 (11)
V (Å³)	743.3 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.23
Crystal size (mm)	0.24 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2001)
T_min, T_max	0.946, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	5201, 3379, 2839
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.081, 0.218, 1.18
No. of reflections	3379
No. of parameters	205
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.84, −0.45

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
N1—H1N···S1ⁱ	0.82 (6)	2.53 (6)	3.342 (3)	173 (5)
N3—H3N···S1ⁱⁱ	0.80 (4)	2.64 (5)	3.385 (4)	156 (4)
N2—H2N···O2	0.86 (5)	2.02 (5)	2.653 (4)	130 (4)

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

Acknowledgements

This work was supported by the National Medical Research Council, Singapore (NMRC/NIG/0019/2008).

References

Ali, H., Yusof, M. S., Khamis, N. A., Mardi, A. S. & Yamin, B. M. (2004). Acta Cryst. E60, o1656–o1658. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Angelusiu, M. V., Almajan, G. L., Rosu, T., Negoiu, M., Almajan, E.-R. & Roy, J. (2009). Eur. J. Med. Chem. 44, 3323–3329. Web of Science CrossRef PubMed CAS 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
Bruker (2001). SMART and SAINT. Bruker AXS GmbH, Karlsruhe, Germany. Google Scholar
Cunha, S., Macedo, F. C. Jr, Costa, G. A. N., Rodrigues, M. T. Jr, Verde, R. B. V., de Souza Neta, L. C., Vencato, I., Lariucci, C. & Sa, F. P. (2007). Monatsh. Chem. 138, 511–516. Web of Science CSD CrossRef CAS Google Scholar
Dolzhenko, A. V., Tan, G. K., Koh, L. L., Dolzhenko, A. V. & Chui, W. K. (2010a). Acta Cryst. E66, o425. Web of Science CSD CrossRef IUCr Journals Google Scholar
Dolzhenko, A. V., Tan, G. K., Koh, L. L., Dolzhenko, A. V. & Chui, W. K. (2010b). Acta Cryst. E66, o549–o550. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, W.-X. & Jiang, Y.-B. (2008). J. Org. Chem. 73, 1124-1127. Web of Science CrossRef PubMed CAS Google Scholar
Qandil, A. M., Tumah, H. N. & Hassan, M. A. (2006). Acta Pharm. Sci. 48, 95–107. CAS 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
Xue, S.-J., Bian, W.-D., Wang, Q.-D. & Chai, A. (2006). Acta Cryst. E62, o4842–o4843. Web of Science CSD CrossRef IUCr Journals Google Scholar
Yamin, B. M. & Yusof, M. S. M. (2003). Acta Cryst. E59, o124–o126. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Yusof, M. S. M., Yamin, B. M. & Shamsuddin, M. (2003). Acta Cryst. E59, o810–o811. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar