(E)-6-Bromo-3-{2-[2-(2-chloro­benzyl­idene)hydrazin­yl]thia­zol-5-yl}-2H-chromen-2-one dimethyl sulfoxide monosolvate

Arshad, A.; Osman, H.; Lam, C.K.; Hemamalini, M.; Fun, H.-K.

doi:10.1107/S1600536811011160

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Pages o1009-o1010

doi:10.1107/S1600536811011160

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(E)-6-Bromo-3-{2-[2-(2-chlorobenzylidene)hydrazinyl]thiazol-5-yl}-2H-chromen-2-one dimethyl sulfoxide monosolvate

Afsheen Arshad,^a Hasnah Osman,^a ‡ Chan Kit Lam,^b Madhukar Hemamalini ^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 19 March 2011; accepted 25 March 2011; online 31 March 2011)

In the title compound C₁₉H₁₁N₃O₂SClBr·C₂H₆OS, the molecule adopts an E configuration about the central C=N double bond. The chromene ring system and the thiazole ring are approximately planar, with maximum deviations of 0.027 (2) and 0.003 (1) Å, respectively. The central thiazole ring makes dihedral angles of 21.82 (9) and 5.88 (7)° with the chloro-substituted phenyl ring and the chromene ring, respectively. In the crystal, molecules are connected via N—H⋯O, N—H⋯S and C—H⋯O hydrogen bonds, forming supramolecular chains along the c axis. An intramolecular C—H⋯O hydrogen bond occurs. π–π interactions are observed between the thiazole and phenyl rings [centroid–centroid distance = 3.6293 (10) Å]. A short Br⋯Cl contact of 3.37 (6) Å also occurs.

Related literature

For details and applications of coumarin derivatives, see Liebig et al. (1974 ); Pathak et al. (1981 ); Hwu et al. (2008 ); Lee et al. (2003 ); Siddiqui et al. (2009 ). For the synthesis of the title compound, see: Tian et al. (1997 ); Yaragatti et al. (2010 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ).

Experimental

Crystal data

C₁₉H₁₁BrClN₃O₂S·C₂H₆OS
M_r = 538.86
Monoclinic, P 2₁ /c
a = 6.5806 (4) Å
b = 15.7789 (9) Å
c = 20.9378 (13) Å
β = 90.684 (2)°
V = 2173.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.24 mm⁻¹
T = 100 K
0.49 × 0.09 × 0.06 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.406, T_max = 0.870
37791 measured reflections
6392 independent reflections
5013 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.069
S = 1.00
6392 reflections
290 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.86 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N1⋯S2	0.85 (2)	2.81 (2)	3.5932 (17)	153 (2)
N2—H1N1⋯O3	0.85 (2)	1.97 (2)	2.808 (2)	169 (3)
C11—H11⋯O2	0.92 (2)	2.34 (3)	2.869 (2)	116.3 (19)
C13—H13A⋯O3	0.93	2.55	3.318 (2)	140
C17—H17A⋯O3ⁱ	0.93	2.60	3.285 (2)	131
C20—H20C⋯O2ⁱⁱ	0.96	2.47	3.431 (2)	176
Symmetry codes: (i) $[-x-1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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: 10.1107/S1600536811011160/sj5124sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011160/sj5124Isup2.hkl

checkCIF report

Comment top

Coumarin derivatives have remarkable medicinal value due to their potential chemotherapeutic (Liebig et al., 1974), fungicidal (Pathak et al., 1981), antiviral (Hwu et al., 2008) and anticoagulant (Lee et al., 2003) properties. Furthermore, coumarins with a variety of substituted thiazole rings exhibit promising biological activities. Recently, some coumarins incorporating thiazolyl semicarbazones which act as anticonvulsant agents were reported (Siddiqui et al., 2009). The title compound (I) is a new derivative of hydrazinyl thiazolyl coumarin. We present here its crystal structure.

The asymmetric unit of the title compound (Fig. 1) consists of one (E)-6-bromo-3-(2-(2-(2-chlorobenzylidene)hydrazinyl)thiazol-5-yl)- 2H-chromen-2-one molecule and one dimethylsulfoxide solvent molecule. The chromene (O1/C1–C9) ring system and thiazole (S1/N1/C10–C12) ring are approximately planar, with maximum deviations of 0.027 (2) Å for atom C9 and 0.003 (1)Å for atom N1, respectively. The molecule adopts an E configuration about the central C13═N3 double bond. The central thiazole (S1/N1/C10–C12) ring makes dihedral angles of 21.82 (9)° and 5.88 (7)° with the chloro-substituted phenyl (C14–C19) ring and the chromene (O1/C1–C9) ring, respectively.

In the crystal structure, (Fig. 2), the molecules are connected via N2—H1N1···S2, N2—H1N1···O3, C13—H13A···O3, C17—H17A···O3 and C20—H20C···O2 (Table 1) hydrogen bonds to form one dimensional supramolecular chains along the c-axis. An intramolecular C11—H11···O2 hydrogen bond stabilizes the molecular structure. π···π interactions are observed between the thiazole (S1/N1/C10–C12) and phenyl (C2–C7) rings [centroid-centroid distance = 3.6293 (10)) Å; -1+x, y, z]. A short Br···Cl contact of 3.37 Å also occurs.

Related literature top

For details and applications of coumarin derivatives, see Liebig et al. (1974); Pathak et al. (1981); Hwu et al. (2008); Lee et al. (2003); Siddiqui et al. (2009). For the synthesis of the title compound, see: Tian et al. (1997); Yaragatti et al. (2010). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986).

Experimental top

2-chlorobenzylidene thiosemicarbazone (Tian et al., 1997) and 6-bromo-3-(2-bromoacetyl)-2H-chromen-2-one (Yaragatti et al., 2010) were synthesized as reported in the literature. Title compound (I) was prepared by reacting 2-chlorobenzylidene thiosemicarbazone (2.5 mmol) with 6-bromo-3-(2-bromoacetyl)-2H- chromen-2-one (2.5 mmol) in chloroform-ethanol (3:1) mixture. The reaction mixture was refluxed for 2–3 hours at 60°C to yield a dense yellow precipitate. The mixture was cooled in ice bath and basified with ammonia to pH 7–8. The title compound (I) was recrystallized from DMSO as yellow needle-like crystals.

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 asymmetric unit of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. The intramolecular hydrogen bond is shown as a dashed line.
	Fig. 2. The crystal packing of the title compound (I).

(E)-6-Bromo-3-{2-[2-(2-chlorobenzylidene)hydrazinyl]thiazol-5-yl}- 2H-chromen-2-one dimethyl sulfoxide monosolvate top

Crystal data top

C₁₉H₁₁BrClN₃O₂S·C₂H₆OS	F(000) = 1088
M_r = 538.86	D_x = 1.646 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9665 reflections
a = 6.5806 (4) Å	θ = 2.8–29.9°
b = 15.7789 (9) Å	µ = 2.24 mm⁻¹
c = 20.9378 (13) Å	T = 100 K
β = 90.684 (2)°	Needle, yellow
V = 2173.9 (2) Å³	0.49 × 0.09 × 0.06 mm
Z = 4

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	6392 independent reflections
Radiation source: fine-focus sealed tube	5013 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 30.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
T_min = 0.406, T_max = 0.870	k = −22→22
37791 measured reflections	l = −29→28

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0237P)² + 1.8103P] where P = (F_o² + 2F_c²)/3
6392 reflections	(Δ/σ)_max = 0.002
290 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.86 e Å⁻³

Crystal data top

C₁₉H₁₁BrClN₃O₂S·C₂H₆OS	V = 2173.9 (2) Å³
M_r = 538.86	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.5806 (4) Å	µ = 2.24 mm⁻¹
b = 15.7789 (9) Å	T = 100 K
c = 20.9378 (13) Å	0.49 × 0.09 × 0.06 mm
β = 90.684 (2)°

Data collection top

Bruker APEXII DUO CCD area-detector diffractometer	6392 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	5013 reflections with I > 2σ(I)
T_min = 0.406, T_max = 0.870	R_int = 0.059
37791 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.59 e Å⁻³
6392 reflections	Δρ_min = −0.86 e Å⁻³
290 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 s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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
Br1	1.24046 (3)	0.503519 (12)	0.413433 (9)	0.02077 (6)
S1	0.06464 (7)	0.92776 (3)	0.44296 (2)	0.01447 (9)
Cl1	−0.43250 (7)	0.82410 (3)	0.14834 (2)	0.01568 (9)
S2	0.19587 (8)	0.69303 (3)	0.22076 (2)	0.01861 (10)
O1	0.85351 (19)	0.78959 (8)	0.55746 (6)	0.0141 (3)
O2	0.6219 (2)	0.88767 (8)	0.57238 (6)	0.0178 (3)
O3	0.0131 (2)	0.67996 (9)	0.26280 (7)	0.0221 (3)
N1	0.2804 (2)	0.79823 (9)	0.40883 (7)	0.0124 (3)
N2	−0.0151 (2)	0.81708 (10)	0.34770 (8)	0.0151 (3)
N3	−0.1775 (2)	0.86848 (9)	0.33469 (7)	0.0140 (3)
C1	0.6516 (3)	0.73061 (11)	0.44975 (8)	0.0134 (3)
H1A	0.5825	0.7093	0.4142	0.016*
C2	0.8397 (3)	0.69208 (11)	0.46917 (8)	0.0131 (3)
C3	0.9315 (3)	0.62551 (11)	0.43607 (9)	0.0151 (4)
H3A	0.8693	0.6027	0.3998	0.018*
C4	1.1151 (3)	0.59407 (11)	0.45784 (9)	0.0154 (4)
C5	1.2114 (3)	0.62663 (12)	0.51219 (9)	0.0160 (4)
H5A	1.3353	0.6045	0.5260	0.019*
C6	1.1216 (3)	0.69197 (11)	0.54534 (9)	0.0155 (4)
H6A	1.1836	0.7141	0.5818	0.019*
C7	0.9373 (3)	0.72427 (11)	0.52342 (8)	0.0130 (3)
C8	0.6760 (3)	0.82992 (11)	0.53893 (8)	0.0126 (3)
C9	0.5713 (3)	0.79729 (11)	0.48163 (8)	0.0127 (3)
C10	0.3801 (3)	0.83652 (11)	0.46033 (8)	0.0123 (3)
C11	0.2874 (3)	0.90653 (11)	0.48441 (9)	0.0146 (3)
C12	0.1142 (3)	0.83956 (11)	0.39565 (8)	0.0129 (3)
C13	−0.2802 (3)	0.84836 (11)	0.28434 (8)	0.0135 (3)
H13A	−0.2395	0.8028	0.2594	0.016*
C14	−0.4611 (3)	0.89708 (10)	0.26614 (8)	0.0119 (3)
C15	−0.5571 (3)	0.95147 (11)	0.30911 (8)	0.0140 (3)
H15A	−0.5063	0.9561	0.3506	0.017*
C16	−0.7256 (3)	0.99838 (11)	0.29128 (9)	0.0165 (4)
H16A	−0.7852	1.0351	0.3204	0.020*
C17	−0.8065 (3)	0.99079 (11)	0.22969 (9)	0.0174 (4)
H17A	−0.9203	1.0222	0.2177	0.021*
C18	−0.7171 (3)	0.93639 (11)	0.18634 (9)	0.0159 (4)
H18A	−0.7713	0.9305	0.1454	0.019*
C19	−0.5458 (3)	0.89069 (10)	0.20465 (8)	0.0124 (3)
C20	0.1935 (3)	0.60863 (12)	0.16416 (9)	0.0197 (4)
H20A	0.0794	0.6153	0.1356	0.030*
H20B	0.1828	0.5555	0.1862	0.030*
H20C	0.3170	0.6097	0.1402	0.030*
C21	0.4090 (3)	0.66012 (13)	0.26810 (10)	0.0248 (4)
H21A	0.4260	0.6980	0.3036	0.037*
H21B	0.5291	0.6610	0.2426	0.037*
H21C	0.3864	0.6037	0.2836	0.037*
H11	0.337 (4)	0.9398 (15)	0.5171 (11)	0.028 (6)*
H1N1	0.009 (4)	0.7740 (15)	0.3243 (11)	0.025 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.01991 (10)	0.02102 (9)	0.02135 (10)	0.00864 (8)	−0.00087 (7)	−0.00287 (8)
S1	0.0134 (2)	0.01564 (19)	0.0143 (2)	0.00403 (17)	−0.00280 (17)	−0.00214 (16)
Cl1	0.0156 (2)	0.01753 (19)	0.01388 (19)	0.00135 (17)	−0.00127 (16)	−0.00306 (15)
S2	0.0189 (2)	0.01360 (19)	0.0234 (2)	−0.00134 (18)	0.00188 (19)	0.00019 (17)
O1	0.0126 (6)	0.0165 (6)	0.0132 (6)	0.0020 (5)	−0.0029 (5)	−0.0014 (5)
O2	0.0173 (7)	0.0198 (6)	0.0162 (6)	0.0021 (5)	−0.0036 (5)	−0.0055 (5)
O3	0.0189 (7)	0.0204 (7)	0.0271 (8)	−0.0024 (6)	0.0065 (6)	−0.0067 (6)
N1	0.0112 (7)	0.0138 (7)	0.0121 (7)	0.0003 (6)	−0.0023 (6)	−0.0013 (5)
N2	0.0135 (7)	0.0161 (7)	0.0157 (7)	0.0036 (6)	−0.0049 (6)	−0.0032 (6)
N3	0.0109 (7)	0.0161 (7)	0.0149 (7)	0.0021 (6)	−0.0014 (6)	0.0019 (6)
C1	0.0133 (8)	0.0157 (8)	0.0111 (8)	−0.0001 (7)	−0.0035 (7)	−0.0002 (6)
C2	0.0110 (8)	0.0149 (8)	0.0134 (8)	−0.0003 (7)	−0.0014 (7)	0.0007 (6)
C3	0.0139 (9)	0.0170 (8)	0.0145 (8)	0.0017 (7)	−0.0028 (7)	−0.0008 (7)
C4	0.0153 (9)	0.0145 (8)	0.0164 (9)	0.0031 (7)	0.0011 (7)	−0.0002 (7)
C5	0.0125 (8)	0.0189 (8)	0.0166 (9)	0.0025 (7)	−0.0028 (7)	0.0038 (7)
C6	0.0146 (9)	0.0183 (8)	0.0136 (8)	−0.0008 (7)	−0.0031 (7)	0.0017 (7)
C7	0.0126 (8)	0.0135 (8)	0.0128 (8)	0.0000 (7)	−0.0004 (7)	−0.0004 (6)
C8	0.0104 (8)	0.0151 (8)	0.0123 (8)	−0.0010 (7)	−0.0004 (6)	0.0014 (6)
C9	0.0110 (8)	0.0150 (8)	0.0120 (8)	−0.0016 (7)	−0.0019 (7)	0.0016 (6)
C10	0.0103 (8)	0.0147 (8)	0.0117 (8)	0.0000 (7)	−0.0017 (6)	0.0010 (6)
C11	0.0128 (8)	0.0162 (8)	0.0147 (8)	0.0009 (7)	−0.0038 (7)	−0.0002 (7)
C12	0.0136 (8)	0.0125 (7)	0.0125 (8)	−0.0001 (7)	0.0002 (7)	0.0005 (6)
C13	0.0123 (8)	0.0135 (8)	0.0146 (8)	0.0010 (7)	−0.0017 (7)	−0.0004 (6)
C14	0.0103 (8)	0.0125 (7)	0.0129 (8)	−0.0014 (6)	−0.0013 (6)	0.0010 (6)
C15	0.0123 (8)	0.0168 (8)	0.0128 (8)	−0.0018 (7)	−0.0015 (7)	0.0013 (7)
C16	0.0159 (9)	0.0165 (8)	0.0172 (8)	0.0010 (7)	−0.0001 (7)	−0.0018 (7)
C17	0.0151 (9)	0.0181 (8)	0.0189 (9)	0.0032 (7)	−0.0022 (7)	0.0015 (7)
C18	0.0154 (9)	0.0178 (8)	0.0144 (8)	0.0004 (7)	−0.0043 (7)	0.0006 (7)
C19	0.0123 (8)	0.0115 (7)	0.0134 (8)	−0.0011 (6)	−0.0002 (7)	−0.0009 (6)
C20	0.0185 (9)	0.0228 (9)	0.0179 (9)	0.0006 (8)	0.0018 (8)	−0.0019 (7)
C21	0.0217 (10)	0.0269 (10)	0.0257 (10)	−0.0002 (9)	−0.0036 (8)	−0.0055 (8)

Geometric parameters (Å, º) top

Br1—C4	1.8986 (18)	C5—H5A	0.9300
S1—C11	1.7273 (18)	C6—C7	1.389 (2)
S1—C12	1.7413 (18)	C6—H6A	0.9300
Cl1—C19	1.7524 (18)	C8—C9	1.469 (2)
S2—O3	1.5130 (15)	C9—C10	1.467 (2)
S2—C20	1.7826 (19)	C10—C11	1.362 (2)
S2—C21	1.785 (2)	C11—H11	0.92 (2)
O1—C7	1.372 (2)	C13—C14	1.464 (2)
O1—C8	1.382 (2)	C13—H13A	0.9300
O2—C8	1.206 (2)	C14—C15	1.399 (2)
N1—C12	1.300 (2)	C14—C19	1.400 (2)
N1—C10	1.393 (2)	C15—C16	1.381 (2)
N2—C12	1.356 (2)	C15—H15A	0.9300
N2—N3	1.366 (2)	C16—C17	1.394 (3)
N2—H1N1	0.85 (2)	C16—H16A	0.9300
N3—C13	1.286 (2)	C17—C18	1.385 (3)
C1—C9	1.356 (2)	C17—H17A	0.9300
C1—C2	1.434 (2)	C18—C19	1.388 (2)
C1—H1A	0.9300	C18—H18A	0.9300
C2—C7	1.394 (2)	C20—H20A	0.9600
C2—C3	1.399 (2)	C20—H20B	0.9600
C3—C4	1.379 (2)	C20—H20C	0.9600
C3—H3A	0.9300	C21—H21A	0.9600
C4—C5	1.394 (2)	C21—H21B	0.9600
C5—C6	1.380 (3)	C21—H21C	0.9600

C11—S1—C12	88.12 (9)	C10—C11—S1	110.64 (13)
O3—S2—C20	106.51 (9)	C10—C11—H11	125.6 (15)
O3—S2—C21	105.18 (10)	S1—C11—H11	123.7 (15)
C20—S2—C21	98.77 (9)	N1—C12—N2	123.02 (16)
C7—O1—C8	122.92 (13)	N1—C12—S1	116.29 (13)
C12—N1—C10	109.50 (15)	N2—C12—S1	120.68 (13)
C12—N2—N3	118.35 (15)	N3—C13—C14	120.14 (16)
C12—N2—H1N1	120.9 (16)	N3—C13—H13A	119.9
N3—N2—H1N1	120.6 (16)	C14—C13—H13A	119.9
C13—N3—N2	114.80 (15)	C15—C14—C19	117.24 (16)
C9—C1—C2	121.96 (16)	C15—C14—C13	121.77 (15)
C9—C1—H1A	119.0	C19—C14—C13	120.99 (16)
C2—C1—H1A	119.0	C16—C15—C14	121.46 (16)
C7—C2—C3	118.67 (16)	C16—C15—H15A	119.3
C7—C2—C1	117.67 (16)	C14—C15—H15A	119.3
C3—C2—C1	123.65 (16)	C15—C16—C17	120.03 (17)
C4—C3—C2	119.21 (16)	C15—C16—H16A	120.0
C4—C3—H3A	120.4	C17—C16—H16A	120.0
C2—C3—H3A	120.4	C18—C17—C16	119.91 (17)
C3—C4—C5	121.69 (17)	C18—C17—H17A	120.0
C3—C4—Br1	119.54 (14)	C16—C17—H17A	120.0
C5—C4—Br1	118.76 (14)	C17—C18—C19	119.39 (16)
C6—C5—C4	119.52 (17)	C17—C18—H18A	120.3
C6—C5—H5A	120.2	C19—C18—H18A	120.3
C4—C5—H5A	120.2	C18—C19—C14	121.95 (16)
C5—C6—C7	119.07 (16)	C18—C19—Cl1	118.43 (13)
C5—C6—H6A	120.5	C14—C19—Cl1	119.61 (13)
C7—C6—H6A	120.5	S2—C20—H20A	109.5
O1—C7—C6	117.31 (15)	S2—C20—H20B	109.5
O1—C7—C2	120.85 (15)	H20A—C20—H20B	109.5
C6—C7—C2	121.84 (17)	S2—C20—H20C	109.5
O2—C8—O1	116.07 (15)	H20A—C20—H20C	109.5
O2—C8—C9	126.89 (16)	H20B—C20—H20C	109.5
O1—C8—C9	117.03 (15)	S2—C21—H21A	109.5
C1—C9—C10	121.02 (15)	S2—C21—H21B	109.5
C1—C9—C8	119.48 (16)	H21A—C21—H21B	109.5
C10—C9—C8	119.50 (16)	S2—C21—H21C	109.5
C11—C10—N1	115.44 (15)	H21A—C21—H21C	109.5
C11—C10—C9	128.05 (16)	H21B—C21—H21C	109.5
N1—C10—C9	116.52 (15)

C12—N2—N3—C13	172.62 (17)	C1—C9—C10—C11	−175.39 (19)
C9—C1—C2—C7	1.4 (3)	C8—C9—C10—C11	5.5 (3)
C9—C1—C2—C3	−177.32 (18)	C1—C9—C10—N1	4.1 (3)
C7—C2—C3—C4	−0.2 (3)	C8—C9—C10—N1	−174.95 (16)
C1—C2—C3—C4	178.50 (17)	N1—C10—C11—S1	0.4 (2)
C2—C3—C4—C5	0.3 (3)	C9—C10—C11—S1	179.94 (15)
C2—C3—C4—Br1	179.80 (14)	C12—S1—C11—C10	−0.06 (15)
C3—C4—C5—C6	0.0 (3)	C10—N1—C12—N2	−179.95 (17)
Br1—C4—C5—C6	−179.46 (14)	C10—N1—C12—S1	0.6 (2)
C4—C5—C6—C7	−0.4 (3)	N3—N2—C12—N1	−175.07 (16)
C8—O1—C7—C6	176.78 (16)	N3—N2—C12—S1	4.4 (2)
C8—O1—C7—C2	−3.3 (3)	C11—S1—C12—N1	−0.32 (15)
C5—C6—C7—O1	−179.58 (16)	C11—S1—C12—N2	−179.80 (16)
C5—C6—C7—C2	0.5 (3)	N2—N3—C13—C14	178.34 (15)
C3—C2—C7—O1	179.92 (16)	N3—C13—C14—C15	−16.2 (3)
C1—C2—C7—O1	1.1 (3)	N3—C13—C14—C19	164.06 (17)
C3—C2—C7—C6	−0.2 (3)	C19—C14—C15—C16	−1.4 (3)
C1—C2—C7—C6	−178.99 (17)	C13—C14—C15—C16	178.83 (17)
C7—O1—C8—O2	−178.27 (16)	C14—C15—C16—C17	1.4 (3)
C7—O1—C8—C9	2.8 (2)	C15—C16—C17—C18	−0.3 (3)
C2—C1—C9—C10	179.09 (16)	C16—C17—C18—C19	−0.8 (3)
C2—C1—C9—C8	−1.8 (3)	C17—C18—C19—C14	0.8 (3)
O2—C8—C9—C1	−179.01 (18)	C17—C18—C19—Cl1	−178.63 (14)
O1—C8—C9—C1	−0.3 (2)	C15—C14—C19—C18	0.3 (3)
O2—C8—C9—C10	0.1 (3)	C13—C14—C19—C18	−179.91 (17)
O1—C8—C9—C10	178.85 (15)	C15—C14—C19—Cl1	179.71 (13)
C12—N1—C10—C11	−0.6 (2)	C13—C14—C19—Cl1	−0.5 (2)
C12—N1—C10—C9	179.78 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N1···S2	0.85 (2)	2.81 (2)	3.5932 (17)	153 (2)
N2—H1N1···O3	0.85 (2)	1.97 (2)	2.808 (2)	169 (3)
C11—H11···O2	0.92 (2)	2.34 (3)	2.869 (2)	116.3 (19)
C13—H13A···O3	0.93	2.55	3.318 (2)	140
C17—H17A···O3ⁱ	0.93	2.60	3.285 (2)	131
C20—H20C···O2ⁱⁱ	0.96	2.47	3.431 (2)	176

Symmetry codes: (i) −x−1, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₉H₁₁BrClN₃O₂S·C₂H₆OS
M_r	538.86
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.5806 (4), 15.7789 (9), 20.9378 (13)
β (°)	90.684 (2)
V (Å³)	2173.9 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.24
Crystal size (mm)	0.49 × 0.09 × 0.06

Data collection
Diffractometer	Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.406, 0.870
No. of measured, independent and observed [I > 2σ(I)] reflections	37791, 6392, 5013
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.069, 1.00
No. of reflections	6392
No. of parameters	290
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.86

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
N2—H1N1···S2	0.85 (2)	2.81 (2)	3.5932 (17)	153 (2)
N2—H1N1···O3	0.85 (2)	1.97 (2)	2.808 (2)	169 (3)
C11—H11···O2	0.92 (2)	2.34 (3)	2.869 (2)	116.3 (19)
C13—H13A···O3	0.93	2.55	3.318 (2)	140
C17—H17A···O3ⁱ	0.93	2.60	3.285 (2)	131
C20—H20C···O2ⁱⁱ	0.96	2.47	3.431 (2)	176

Symmetry codes: (i) −x−1, y+1/2, −z+1/2; (ii) x, −y+3/2, z−1/2.

Footnotes

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

§Thomson Reuters ResearcherID: A-3561-2009.

Acknowledgements

AA, HO, CKL thank the Malaysian Government and Universiti Sains Malaysia (USM) for a grant [1001/PKimia/811133] to conduct this work. AA also thanks Universiti Sains Malaysia for a fellowship. HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship.

References

Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst. 19, 105–107. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hwu, J., Singha, R., Hong, S., Chang, Y., Das, A., Vliegen, I., De Clercq, E. & Neyts, J. (2008). Antivir. Res. 77, 157–162. Web of Science CrossRef PubMed CAS Google Scholar
Lee, Y., Lee, S., Jin, J. & Yun-Choi, H. (2003). Arch. Pharmacal Res. 26, 723–726. CrossRef Google Scholar
Liebig, H., Pfetzing, H. & Grafe, A. (1974). Arzneim-Forsch. 24, 887–892. CAS Google Scholar
Pathak, R. B., Jahan, B. & Bahel, S. C. (1981). Bokin Bobai. 9, 477–480. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siddiqui, N., Arshad, M. & Khan, S. (2009). Acta. Pol.-Pharm. Drug Res. 66, 161–167. CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tian, Y., Duan, C., Zhao, C., You, X., Mak, T. C. W. & Zhang, Z. (1997). Inorg. Chem. 36, 1247–1252. CSD CrossRef PubMed CAS Web of Science Google Scholar
Yaragatti, N. B., Kulkarni, M. V., Ghate, M. D., Hebbar, S. S. & Hegde, G. R. (2010). J. Sulfur Chem. 31, 123–133. CrossRef CAS Google Scholar

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