(E)-1-[1-(6-Bromo-2-oxo-2H-chromen-3-yl)ethyl­idene]thio­semicarbazide

Arshad, A.; Osman, H.; Chan, K.L.; Goh, J.H.; Fun, H.-K.

doi:10.1107/S1600536810019240

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Pages o1491-o1492

https://doi.org/10.1107/S1600536810019240

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(E)-1-[1-(6-Bromo-2-oxo-2H-chromen-3-yl)ethylidene]thiosemicarbazide

Afsheen Arshad,^a Hasnah Osman,^a ‡ Kit Lam Chan,^b Jia Hao Goh ^c § and Hoong-Kun Fun ^c ^*¶

^aSchool of Chemical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bSchool of Pharmaceutical Sciences, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, and ^cX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: hkfun@usm.my

(Received 22 May 2010; accepted 22 May 2010; online 29 May 2010)

The title compound, C₁₂H₁₀BrN₃O₂S, exists in an E configuration with respect to the C=N bond. The approximately planar 2H-chromene ring system [maximum deviation = 0.059 (1) Å] is inclined at a dihedral angle of 17.50 (5)° with respect to the mean plane through the thiosemicarbazide unit and an intramolecular N—H⋯N hydrogen bond generates an S(5) ring. In the crystal structure, adjacent molecules are linked by N—H⋯S hydrogen bonds, forming [010] chains built up from R₂²(8) loops, such that each S atom accepts two such bonds. These chains are further interconnected into sheets parallel to the ab plane via short Br⋯O interactions [3.0732 (13) Å] and a π–π aromatic stacking interaction [3.7870 (8) Å] is also observed.

Related literature

For general background to and applications of the title thiosemicarbazide compound, see: Anderson et al. (2002 ); Chulian et al. (2009 ); Desai et al. (1984 ); Finn et al. (2004 ); Hofmanová et al. (1998 ); Hoult & Payá (1996 ); Kimura et al. (1985 ); Laffitte et al. (2002 ); Mitscher (2002 ); Moffett (1964 ); Pillai et al. (1999 ); Shukla et al. (1984 ); Tassies et al. (2002 ); Weber et al. (1998 ). For the preparation, see: Moamen et al. (2009 ). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ). For a related structure, see: Arshad et al. (2010 ). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₂H₁₀BrN₃O₂S
M_r = 340.20
Triclinic, $[P \overline 1]$
a = 6.3796 (6) Å
b = 8.1260 (7) Å
c = 13.3756 (12) Å
α = 106.697 (2)°
β = 95.095 (2)°
γ = 98.925 (2)°
V = 649.57 (10) Å³
Z = 2
Mo Kα radiation
μ = 3.33 mm⁻¹
T = 100 K
0.73 × 0.20 × 0.15 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.196, T_max = 0.637
19355 measured reflections
5036 independent reflections
4733 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.021
wR(F²) = 0.084
S = 1.17
5036 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.73 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2N3⋯N1	0.82 (3)	2.15 (3)	2.6004 (17)	114 (3)
N2—H1N2⋯S1ⁱ	0.73 (3)	2.70 (3)	3.4094 (13)	165 (3)
N3—H1N3⋯S1ⁱⁱ	0.81 (2)	2.49 (2)	3.3010 (13)	175.6 (19)
Symmetry codes: (i) -x-1, -y+1, -z+1; (ii) -x-1, -y, -z+1.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810019240/hb5461sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019240/hb5461Isup2.hkl

checkCIF report

Comment top

Thiosemicarbazide compounds exhibit various biological activities such as anti-bacterial, anti-fungal and especially anti-tuberculosis (Shukla et al., 1984, Desai et al., 1984). Apart from this, coumarins constitute an important class of compounds found throughout the plant kingdom and are known to have diverse activities such as anti-coagulants (Anderson et al., 2002, Tassies et al., 2002), anti-bacterial (Mitscher, 2002, Laffitte et al., 2002), anti-fungal (Moffett, 1964) and cytotoxicity (Weber et al., 1998) properties. The coumarin moiety and related derivatives are also reported to have importance as vasodilators (Hoult & Payá, 1996), anti-mutagenic agents (Pillai et al., 1999), scavengers of reactive oxygen species (Finn et al., 2004), as well as lipoxygenese and cyclooxygenese inhibitors (Kimura et al., 1985, Hofmanová et al., 1998). The title compound exhibits very good anti-bacterial activity against Escherichia coli and Bacillus. subtilus (Chulian et al., 2009). The objective of this study is to synthesize new derivatives of coumarin-thiosemicarbazide compounds. We present in this paper the crystal structure of this title compound.

The title thiosemicarbazide compound (Fig. 1) exists in a cis configuration with respect to the Schiff base C10═N1 bond [N1═C10 = 1.2890 (15) Å; torsion angle C9–C10–N1–N2 = 178.83 (10)°]. The 2H-chromene ring system (C1-C9/O1) is approximately planar, with a maximum deviation of 0.059 (1) Å at atom C9. The mean plane through the thiosemicarbazide moiety (N1/N2/C11/N3/S1) forms dihedral angle of 17.50 (5)° with the 2H-chromene ring system. Bond lengths and angles are consistent to a closely related structure (Arshad et al., 2010).

In the crystal structure, pairs of intermolecular N2—H1N2···S1 and N3—H1N3···S1 hydrogen bonds (Table 1) form bifurcated acceptor hydrogen bonds which generate two different R²₂(8) hydrogen bond ring motifs with zig-zag formation (Fig. 2, Bernstein et al., 1995). These hydrogen bonds link adjacent molecules into two-molecule wide chains along the b axis. Intermolecular short Br···O interactions [Br1···O2ⁱⁱⁱ = 3.0732 (13) Å; (iii) x+1, y-1, z] interconnect these chains into two-dimensional planes parallel to the ab plane (Fig. 3). The crystal structure is further stabilized by weak Cg1···Cg1 interactions involving the centroid of the C2-C7 benzene ring [Cg1···Cg1^iv = 3.7870 (8) Å; (iv) -x+1, -y, -z].

Related literature top

For general background to and applications of the title thiosemicarbazide compound, see: Anderson et al. (2002); Chulian et al. (2009); Desai et al. (1984); Finn et al. (2004); Hofmanová et al. (1998); Hoult et al. (1996); Kimura et al. (1985); Laffitte et al. (2002); Mitscher (2002); Moffett (1964); Pillai et al. (1999); Shukla et al. (1984); Tassies et al. (2002); Weber et al. (1998). For the preparation, see: Moamen et al. (2009). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995). For a related structure, see: Arshad et al. (2010). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Experimental top

Coumarin thiosemicarbazone was prepared by cyclocondensation of 5-bromosalicylaldehyde with ethylacetoacetate and the resulting acetyl coumarin intermediate was then treated with thiosemicarbazide to get the title compound as reported in the literature with some modifications (Moamen et al., 2009). The methanol solution of thiosemicarbazide (5.00 mmol) was added to a solution of 6-bromo-(3-acethylcoumarin) (5.00 mmol) in hot methanol (10 ml) while stirring. The resulting solution was refluxed for 1 h and then pH of the solution was adjusted to 4–5 by adding glacial acetic acid. The solution was again refluxed for 4 h. The title compound was recrystallized from ethyl acetate:ethanol (2:1) to give yellow needles of (I).

Structure description top

For general background to and applications of the title thiosemicarbazide compound, see: Anderson et al. (2002); Chulian et al. (2009); Desai et al. (1984); Finn et al. (2004); Hofmanová et al. (1998); Hoult et al. (1996); Kimura et al. (1985); Laffitte et al. (2002); Mitscher (2002); Moffett (1964); Pillai et al. (1999); Shukla et al. (1984); Tassies et al. (2002); Weber et al. (1998). For the preparation, see: Moamen et al. (2009). For graph-set descriptions of hydrogen-bond ring motifs, see: Bernstein et al. (1995). For a related structure, see: Arshad et al. (2010). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing 50 % probability displacement ellipsoids for non-H atoms.
	Fig. 2. Part of the crystal structure of (I), showing molecules being linked into an infinite chain incorporating zig-zag shaped R²₂(8) ring motifs along the b axis.
	Fig. 3. The crystal structure of (I), viewed along the b axis, showing a two-molecule-wide plane parallel to the ab plane. Hydrogen atoms not involved in intermolecular interactions (dashed lines) have been omitted for clarity.

(E)-1-[1-(6-Bromo-2-oxo-2H-chromen-3- yl)ethylidene]thiosemicarbazide top

Crystal data top

C₁₂H₁₀BrN₃O₂S	Z = 2
M_r = 340.20	F(000) = 340
Triclinic, P1	D_x = 1.739 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3796 (6) Å	Cell parameters from 9969 reflections
b = 8.1260 (7) Å	θ = 2.7–35.1°
c = 13.3756 (12) Å	µ = 3.33 mm⁻¹
α = 106.697 (2)°	T = 100 K
β = 95.095 (2)°	Needle, yellow
γ = 98.925 (2)°	0.73 × 0.20 × 0.15 mm
V = 649.57 (10) Å³

Data collection top

Bruker APEXII DUO CCD diffractometer	5036 independent reflections
Radiation source: fine-focus sealed tube	4733 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 33.5°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.196, T_max = 0.637	k = −12→12
19355 measured reflections	l = −20→20

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)] = 0.021	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ²(F_o²) + (0.0569P)² + 0.0443P] where P = (F_o² + 2F_c²)/3
5036 reflections	(Δ/σ)_max = 0.001
185 parameters	Δρ_max = 0.73 e Å⁻³
0 restraints	Δρ_min = −0.56 e Å⁻³

Crystal data top

C₁₂H₁₀BrN₃O₂S	γ = 98.925 (2)°
M_r = 340.20	V = 649.57 (10) Å³
Triclinic, P1	Z = 2
a = 6.3796 (6) Å	Mo Kα radiation
b = 8.1260 (7) Å	µ = 3.33 mm⁻¹
c = 13.3756 (12) Å	T = 100 K
α = 106.697 (2)°	0.73 × 0.20 × 0.15 mm
β = 95.095 (2)°

Data collection top

Bruker APEXII DUO CCD diffractometer	5036 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	4733 reflections with I > 2σ(I)
T_min = 0.196, T_max = 0.637	R_int = 0.020
19355 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.021	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	Δρ_max = 0.73 e Å⁻³
5036 reflections	Δρ_min = −0.56 e Å⁻³
185 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

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 > 2sigma(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
Br1	0.831903 (19)	−0.130575 (15)	0.134917 (9)	0.01986 (5)
S1	−0.52737 (6)	0.26734 (4)	0.52668 (3)	0.02208 (7)
O1	0.39540 (15)	0.46915 (12)	0.12143 (7)	0.01830 (16)
O2	0.14155 (19)	0.62282 (15)	0.15561 (9)	0.0270 (2)
N1	−0.08889 (17)	0.33908 (13)	0.34997 (8)	0.01559 (17)
N2	−0.24110 (18)	0.37175 (14)	0.41584 (8)	0.01611 (17)
N3	−0.2610 (2)	0.08895 (15)	0.41915 (9)	0.0204 (2)
C1	0.2259 (2)	0.50976 (16)	0.17462 (10)	0.0177 (2)
C2	0.48940 (19)	0.32942 (15)	0.12434 (9)	0.01509 (18)
C3	0.6564 (2)	0.29964 (17)	0.06532 (10)	0.0179 (2)
H3A	0.7011	0.3720	0.0255	0.022*
C4	0.75479 (19)	0.15951 (17)	0.06722 (9)	0.0178 (2)
H4A	0.8675	0.1375	0.0288	0.021*
C5	0.68424 (19)	0.05161 (16)	0.12688 (9)	0.01630 (19)
C6	0.51529 (19)	0.07869 (15)	0.18374 (9)	0.01632 (19)
H6A	0.4670	0.0031	0.2210	0.020*
C7	0.41777 (18)	0.22285 (15)	0.18420 (9)	0.01446 (18)
C8	0.25545 (18)	0.27089 (15)	0.24813 (9)	0.01512 (18)
H8A	0.2113	0.2048	0.2915	0.018*
C9	0.16407 (18)	0.41112 (15)	0.24698 (9)	0.01454 (18)
C10	−0.00056 (18)	0.46198 (15)	0.31560 (9)	0.01494 (18)
C11	−0.33190 (19)	0.23856 (15)	0.44883 (9)	0.01633 (19)
C12	−0.0508 (2)	0.64307 (16)	0.34349 (10)	0.0196 (2)
H12A	−0.0674	0.6814	0.4167	0.029*
H12B	−0.1814	0.6417	0.3013	0.029*
H12C	0.0641	0.7218	0.3302	0.029*
H1N2	−0.308 (5)	0.438 (4)	0.420 (3)	0.060 (9)*
H1N3	−0.317 (3)	0.005 (3)	0.4346 (16)	0.019 (4)*
H2N3	−0.164 (5)	0.094 (4)	0.383 (3)	0.057 (9)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02111 (7)	0.01997 (7)	0.02278 (7)	0.01169 (5)	0.00823 (5)	0.00757 (5)
S1	0.02734 (16)	0.01628 (13)	0.03123 (16)	0.01088 (11)	0.02016 (13)	0.01232 (11)
O1	0.0205 (4)	0.0197 (4)	0.0223 (4)	0.0104 (3)	0.0121 (3)	0.0121 (3)
O2	0.0334 (5)	0.0302 (5)	0.0330 (5)	0.0205 (4)	0.0192 (4)	0.0220 (4)
N1	0.0174 (4)	0.0165 (4)	0.0162 (4)	0.0071 (3)	0.0086 (3)	0.0062 (3)
N2	0.0191 (4)	0.0145 (4)	0.0197 (4)	0.0078 (3)	0.0116 (3)	0.0078 (3)
N3	0.0264 (5)	0.0157 (4)	0.0259 (5)	0.0104 (4)	0.0158 (4)	0.0099 (4)
C1	0.0197 (5)	0.0189 (5)	0.0199 (5)	0.0086 (4)	0.0097 (4)	0.0096 (4)
C2	0.0157 (4)	0.0162 (4)	0.0162 (4)	0.0063 (4)	0.0057 (3)	0.0066 (4)
C3	0.0181 (5)	0.0216 (5)	0.0186 (5)	0.0077 (4)	0.0089 (4)	0.0092 (4)
C4	0.0166 (5)	0.0219 (5)	0.0176 (5)	0.0078 (4)	0.0075 (4)	0.0063 (4)
C5	0.0164 (4)	0.0176 (5)	0.0172 (4)	0.0084 (4)	0.0054 (4)	0.0053 (4)
C6	0.0173 (5)	0.0163 (4)	0.0186 (5)	0.0071 (4)	0.0068 (4)	0.0069 (4)
C7	0.0154 (4)	0.0149 (4)	0.0154 (4)	0.0055 (3)	0.0058 (3)	0.0058 (3)
C8	0.0158 (4)	0.0155 (4)	0.0171 (4)	0.0060 (4)	0.0068 (4)	0.0069 (4)
C9	0.0158 (4)	0.0152 (4)	0.0156 (4)	0.0059 (3)	0.0068 (3)	0.0064 (3)
C10	0.0155 (4)	0.0155 (4)	0.0167 (4)	0.0061 (4)	0.0065 (4)	0.0065 (3)
C11	0.0198 (5)	0.0146 (4)	0.0184 (5)	0.0068 (4)	0.0090 (4)	0.0072 (4)
C12	0.0234 (5)	0.0159 (5)	0.0248 (5)	0.0092 (4)	0.0121 (4)	0.0090 (4)

Geometric parameters (Å, º) top

Br1—C5	1.8965 (11)	C3—C4	1.3879 (17)
S1—C11	1.6957 (12)	C3—H3A	0.9300
O1—C2	1.3722 (14)	C4—C5	1.3969 (17)
O1—C1	1.3770 (14)	C4—H4A	0.9300
O2—C1	1.2091 (15)	C5—C6	1.3827 (16)
N1—C10	1.2890 (15)	C6—C7	1.4079 (15)
N1—N2	1.3738 (14)	C6—H6A	0.9300
N2—C11	1.3516 (15)	C7—C8	1.4307 (16)
N2—H1N2	0.73 (3)	C8—C9	1.3613 (15)
N3—C11	1.3288 (15)	C8—H8A	0.9300
N3—H1N3	0.81 (2)	C9—C10	1.4846 (16)
N3—H2N3	0.82 (3)	C10—C12	1.5033 (16)
C1—C9	1.4665 (16)	C12—H12A	0.9600
C2—C3	1.3917 (16)	C12—H12B	0.9600
C2—C7	1.3930 (15)	C12—H12C	0.9600

C2—O1—C1	122.75 (9)	C5—C6—H6A	120.6
C10—N1—N2	119.10 (10)	C7—C6—H6A	120.6
C11—N2—N1	117.19 (10)	C2—C7—C6	118.95 (10)
C11—N2—H1N2	111 (3)	C2—C7—C8	118.13 (10)
N1—N2—H1N2	128 (3)	C6—C7—C8	122.83 (10)
C11—N3—H1N3	119.9 (15)	C9—C8—C7	121.52 (10)
C11—N3—H2N3	112 (2)	C9—C8—H8A	119.2
H1N3—N3—H2N3	128 (3)	C7—C8—H8A	119.2
O2—C1—O1	116.08 (11)	C8—C9—C1	119.13 (10)
O2—C1—C9	126.61 (11)	C8—C9—C10	120.96 (10)
O1—C1—C9	117.31 (10)	C1—C9—C10	119.90 (10)
O1—C2—C3	117.34 (10)	N1—C10—C9	113.79 (10)
O1—C2—C7	120.50 (10)	N1—C10—C12	124.38 (10)
C3—C2—C7	122.16 (10)	C9—C10—C12	121.81 (10)
C4—C3—C2	118.48 (11)	N3—C11—N2	117.80 (11)
C4—C3—H3A	120.8	N3—C11—S1	122.45 (9)
C2—C3—H3A	120.8	N2—C11—S1	119.74 (9)
C3—C4—C5	119.89 (10)	C10—C12—H12A	109.5
C3—C4—H4A	120.1	C10—C12—H12B	109.5
C5—C4—H4A	120.1	H12A—C12—H12B	109.5
C6—C5—C4	121.73 (10)	C10—C12—H12C	109.5
C6—C5—Br1	119.11 (9)	H12A—C12—H12C	109.5
C4—C5—Br1	119.11 (9)	H12B—C12—H12C	109.5
C5—C6—C7	118.75 (10)

C10—N1—N2—C11	179.07 (11)	C5—C6—C7—C8	−174.14 (11)
C2—O1—C1—O2	−171.47 (12)	C2—C7—C8—C9	3.45 (17)
C2—O1—C1—C9	7.73 (18)	C6—C7—C8—C9	179.96 (12)
C1—O1—C2—C3	178.59 (11)	C7—C8—C9—C1	3.09 (18)
C1—O1—C2—C7	−1.23 (18)	C7—C8—C9—C10	−178.55 (11)
O1—C2—C3—C4	179.76 (11)	O2—C1—C9—C8	170.56 (14)
C7—C2—C3—C4	−0.43 (19)	O1—C1—C9—C8	−8.54 (18)
C2—C3—C4—C5	0.48 (19)	O2—C1—C9—C10	−7.8 (2)
C3—C4—C5—C6	0.93 (19)	O1—C1—C9—C10	173.08 (11)
C3—C4—C5—Br1	−176.32 (9)	N2—N1—C10—C9	178.83 (10)
C4—C5—C6—C7	−2.35 (18)	N2—N1—C10—C12	0.63 (18)
Br1—C5—C6—C7	174.90 (9)	C8—C9—C10—N1	−18.82 (16)
O1—C2—C7—C6	178.81 (11)	C1—C9—C10—N1	159.52 (11)
C3—C2—C7—C6	−0.99 (18)	C8—C9—C10—C12	159.43 (12)
O1—C2—C7—C8	−4.54 (17)	C1—C9—C10—C12	−22.22 (17)
C3—C2—C7—C8	175.65 (11)	N1—N2—C11—N3	2.93 (17)
C5—C6—C7—C2	2.34 (18)	N1—N2—C11—S1	−177.80 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N1	0.82 (3)	2.15 (3)	2.6004 (17)	114 (3)
N2—H1N2···S1ⁱ	0.73 (3)	2.70 (3)	3.4094 (13)	165 (3)
N3—H1N3···S1ⁱⁱ	0.81 (2)	2.49 (2)	3.3010 (13)	175.6 (19)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀BrN₃O₂S
M_r	340.20
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.3796 (6), 8.1260 (7), 13.3756 (12)
α, β, γ (°)	106.697 (2), 95.095 (2), 98.925 (2)
V (Å³)	649.57 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.33
Crystal size (mm)	0.73 × 0.20 × 0.15

Data collection
Diffractometer	Bruker APEXII DUO CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.196, 0.637
No. of measured, independent and observed [I > 2σ(I)] reflections	19355, 5036, 4733
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.777

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.021, 0.084, 1.17
No. of reflections	5036
No. of parameters	185
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.73, −0.56

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2N3···N1	0.82 (3)	2.15 (3)	2.6004 (17)	114 (3)
N2—H1N2···S1ⁱ	0.73 (3)	2.70 (3)	3.4094 (13)	165 (3)
N3—H1N3···S1ⁱⁱ	0.81 (2)	2.49 (2)	3.3010 (13)	175.6 (19)

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

Footnotes

‡Additional correspondence author, e-mail: ohasnah@usm.my.

§Thomson Reuters ResearcherID: C-7576-2009.

¶Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for a Short-term Grant (No. 304/PKIMIA/639004) to conduct this research. AA thanks the Pakistan Government and PCSIR for financial scholarship support. HKF and JHG thank USM for the Research University Golden Goose grant (No. 1001/PFIZIK/811012). JHG also thanks USM for the award of a USM fellowship.

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