N′-(4-Bromo­phenyl­sulfon­yl)isonicotino­hydrazide

Khan, I.U.; Ashfaq, M.; Arshad, M.N.; Ahmad, H.; Mustafa, G.

doi:10.1107/S1600536809028475

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o1991

doi:10.1107/S1600536809028475

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N′-(4-Bromophenylsulfonyl)isonicotinohydrazide

Islam Ullah Khan,^a Muhammad Ashfaq,^a Muhammad Nadeem Arshad,^a ^* Hamad Ahmad ^a and Ghulam Mustafa ^b

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore, Pakistan, and ^bDepartment of Chemistry, University of Gujrat, Gujrat, Pakistan
^*Correspondence e-mail: mnachemist@hotmail.com

(Received 3 July 2009; accepted 18 July 2009; online 25 July 2009)

The title compound, C₁₂H₁₀BrN₃O₃S, crystallizes with two crystallographically independent molecules in the asymmetric unit. The dihedral angles between the two six-membered rings in the molecules are 34.1 (3) and 45.1 (2)°. In the crystal structure, molecules are connected via N—H⋯O and N—H⋯N hydrogen bonding.

Related literature

For general background to isonicotinic acid hydrazides, see: Carlton (1967 ). For a related structure, see: Wang et al. (2008 ). For the synthesis and biological activity of isoniazid and hydrazide derivatives, see: Lourenco et al. (2008 ); Kucukguzel et al. (2003 ); Carvalho et al. (2008 ), For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₂H₁₀BrN₃O₃S
M_r = 356.20
Monoclinic, P 2₁ /c
a = 10.1229 (6) Å
b = 19.0440 (12) Å
c = 15.0640 (7) Å
β = 96.862 (2)°
V = 2883.2 (3) Å³
Z = 8
Mo Kα radiation
μ = 3.01 mm⁻¹
T = 296 K
0.36 × 0.30 × 0.15 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.349, T_max = 0.641
29398 measured reflections
6601 independent reflections
3473 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.146
S = 1.01
6601 reflections
373 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.88 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4ⁱ	0.76 (4)	2.15 (4)	2.882 (4)	165.09
N3—H3⋯N4ⁱⁱ	0.78 (4)	2.10 (4)	2.868 (5)	168.21
N6—H6⋯O6ⁱⁱⁱ	0.83 (4)	2.26 (4)	2.998 (4)	147.35
N5—H5⋯N1^iv	0.83 (4)	2.03 (4)	2.847 (4)	168.32
N3—H3⋯O1	0.78 (4)	2.49 (4)	2.732 (4)	100 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1; (iv) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ) and PLATON.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809028475/nc2151sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028475/nc2151Isup2.hkl

checkCIF report

Comment top

Isonicotinic acid hydrazide(INH) commonly known as isoniazid is a drug being used for the treatment of tuberclosis (TB) for long time (Carlton, 1967). Different approaches have been made for the synthesis of biologically active derivatives of isoniazid (Lourenco et al., 2008), (Kucukguzel et al., 2007), (Carvalho, et al.. 2008) and their crystallographic studies (Wang et al., 2008). In this context we report the crystal structure of title compound (N'-[(4-bromophenyl)sulfonyl]pyridine-4-carbohydrazide) a sulfonamide derivative of Isoniazid.

The title compound crystallizes with two crystallographically independent molecules in the asymmetric unit. The dihedral angle in each of these molecules amount to 34.1 (3) ° in molecule A, while it is 45.1 (2) ° (Fig. 1).

In the crystal structure the molecules are connected via intermolecular and intramolecular N–H···O and N–H···N hydrogen bonding (Fig. 2 and Tab. 1). One of the two indpenendent molecules is connected into dimers via N–H···O hydrogen bonding of the sulfonamide group into R₂²(8) rings (Bernstein et al., 1995). These dimers are further linked by additional N–H···O and N–H···N hydrogen bonding.

Related literature top

For general background to isonicotinic acid hydrazide, see: Carlton et al. (1967). For a related structure, see: Wang et al. (2008). For the biological activity of isoniazidderivatives, see: Lourenco et al. (2008); Kucukguzel et al. (2003); Carvalho et al. (2008), For graph-set notation, see: Bernstein et al. (1995).

Experimental top

To the solution of Isoniazid (0.5 g, 3.646 mmol) in distilled water (10 ml), 4-Bromobenzenesulfonyl chloride(0.9316 g, 3.65 mmol) was suspended. The reaction mixture was stirred at room temperature for 4 hrs at constant pH 8–9, which was adjusted by 1M sodium carbonate solution. After completion of the reaction which was observed by the consumption of suspended 4-Bromobenzenesulfonyl chloride, the pH was adjusted at 2–3 using 1 N HCl solution, which results the formation of a light yellow coloured precipitate, which was filtered off and dried. The prodcut was recrystallized from methanol.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The structure of (I) with labeling and displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Unit cell packing for (I) with hydrogen bonding shown as dashed lines.

N'-(4-Bromophenylsulfonyl)isonicotinohydrazide top

Crystal data top

C₁₂H₁₀BrN₃O₃S	F(000) = 1424
M_r = 356.20	D_x = 1.641 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5184 reflections
a = 10.1229 (6) Å	θ = 2.1–22.9°
b = 19.0440 (12) Å	µ = 3.01 mm⁻¹
c = 15.0640 (7) Å	T = 296 K
β = 96.862 (2)°	Needle, white yellow
V = 2883.2 (3) Å³	0.36 × 0.30 × 0.15 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	6601 independent reflections
Radiation source: fine-focus sealed tube	3473 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −13→11
T_min = 0.349, T_max = 0.641	k = −24→23
29398 measured reflections	l = −17→19

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0597P)² + 2.5287P] where P = (F_o² + 2F_c²)/3
6601 reflections	(Δ/σ)_max = 0.001
373 parameters	Δρ_max = 1.06 e Å⁻³
0 restraints	Δρ_min = −0.88 e Å⁻³

Crystal data top

C₁₂H₁₀BrN₃O₃S	V = 2883.2 (3) Å³
M_r = 356.20	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.1229 (6) Å	µ = 3.01 mm⁻¹
b = 19.0440 (12) Å	T = 296 K
c = 15.0640 (7) Å	0.36 × 0.30 × 0.15 mm
β = 96.862 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6601 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	3473 reflections with I > 2σ(I)
T_min = 0.349, T_max = 0.641	R_int = 0.053
29398 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	0 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 1.06 e Å⁻³
6601 reflections	Δρ_min = −0.88 e Å⁻³
373 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 > 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	0.01531 (7)	0.40221 (5)	0.59324 (5)	0.1083 (3)
Br2	1.07622 (6)	0.14607 (4)	0.37352 (6)	0.1046 (3)
S1	0.46424 (10)	0.38694 (6)	0.33172 (7)	0.0392 (3)
S2	0.46755 (9)	0.10499 (5)	0.43498 (6)	0.0328 (2)
O1	0.1616 (3)	0.49151 (15)	0.28196 (19)	0.0467 (7)
O2	0.4756 (3)	0.31692 (15)	0.2999 (2)	0.0510 (8)
O3	0.5802 (3)	0.42527 (17)	0.3664 (2)	0.0566 (9)
O4	0.2996 (2)	0.20910 (13)	0.59686 (17)	0.0376 (7)
O5	0.3909 (3)	0.16199 (14)	0.39574 (18)	0.0420 (7)
O6	0.4282 (3)	0.03415 (14)	0.41370 (17)	0.0413 (7)
N1	−0.2166 (3)	0.3447 (2)	0.1433 (3)	0.0533 (10)
N2	0.2699 (3)	0.41007 (18)	0.2107 (2)	0.0340 (8)
H2	0.270 (4)	0.383 (2)	0.174 (3)	0.041*
N3	0.3969 (3)	0.43457 (18)	0.2456 (2)	0.0353 (8)
H3	0.398 (4)	0.474 (2)	0.259 (3)	0.042*
N4	0.5582 (4)	0.42464 (18)	0.6902 (2)	0.0474 (9)
N5	0.5095 (3)	0.17527 (17)	0.5802 (2)	0.0327 (8)
H5	0.590 (4)	0.176 (2)	0.600 (3)	0.039*
N6	0.4645 (3)	0.11035 (17)	0.5443 (2)	0.0336 (8)
H6	0.493 (4)	0.077 (2)	0.577 (3)	0.040*
C1	0.0288 (4)	0.4054 (2)	0.1991 (3)	0.0352 (9)
C2	0.0182 (4)	0.3454 (3)	0.1500 (4)	0.0685 (16)
H2A	0.0942	0.3235	0.1342	0.082*
C3	−0.1055 (5)	0.3172 (3)	0.1236 (4)	0.0732 (17)
H3A	−0.1102	0.2761	0.0900	0.088*
C4	−0.2061 (5)	0.4033 (3)	0.1895 (4)	0.0774 (18)
H4	−0.2837	0.4244	0.2038	0.093*
C5	−0.0851 (4)	0.4357 (3)	0.2184 (4)	0.0668 (15)
H5A	−0.0828	0.4775	0.2505	0.080*
C6	0.1592 (4)	0.4400 (2)	0.2344 (3)	0.0351 (9)
C7	0.3474 (4)	0.3869 (2)	0.4092 (2)	0.0368 (9)
C8	0.2620 (4)	0.3310 (2)	0.4126 (3)	0.0453 (11)
H8	0.2713	0.2909	0.3786	0.054*
C9	0.1620 (5)	0.3355 (3)	0.4677 (3)	0.0574 (13)
H9	0.1031	0.2984	0.4711	0.069*
C10	0.1508 (5)	0.3954 (3)	0.5172 (3)	0.0559 (13)
C11	0.2374 (5)	0.4504 (3)	0.5151 (3)	0.0557 (13)
H11	0.2291	0.4899	0.5504	0.067*
C12	0.3362 (4)	0.4468 (2)	0.4607 (3)	0.0460 (11)
H12	0.3953	0.4840	0.4581	0.055*
C13	0.4719 (4)	0.29175 (19)	0.6327 (2)	0.0301 (8)
C14	0.5961 (4)	0.3167 (2)	0.6178 (3)	0.0482 (11)
H14	0.6526	0.2894	0.5877	0.058*
C15	0.6342 (5)	0.3825 (2)	0.6483 (3)	0.0556 (12)
H15	0.7183	0.3984	0.6390	0.067*
C16	0.4389 (4)	0.4011 (2)	0.7026 (3)	0.0424 (10)
H16	0.3832	0.4305	0.7306	0.051*
C17	0.3926 (4)	0.3353 (2)	0.6764 (2)	0.0363 (9)
H17	0.3089	0.3205	0.6881	0.044*
C18	0.4181 (4)	0.22155 (19)	0.6023 (2)	0.0288 (8)
C19	0.6340 (4)	0.1167 (2)	0.4150 (2)	0.0346 (9)
C20	0.6736 (4)	0.1792 (3)	0.3808 (3)	0.0514 (11)
H20	0.6125	0.2151	0.3669	0.062*
C21	0.8050 (5)	0.1878 (3)	0.3674 (3)	0.0654 (14)
H21	0.8330	0.2298	0.3443	0.078*
C22	0.8945 (5)	0.1344 (3)	0.3881 (3)	0.0606 (14)
C23	0.8545 (5)	0.0717 (3)	0.4216 (3)	0.0581 (13)
H23	0.9158	0.0357	0.4350	0.070*
C24	0.7237 (4)	0.0623 (2)	0.4352 (3)	0.0477 (11)
H24	0.6957	0.0201	0.4576	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0866 (5)	0.1511 (8)	0.0966 (5)	0.0053 (5)	0.0490 (4)	−0.0107 (5)
Br2	0.0489 (3)	0.1069 (6)	0.1655 (7)	−0.0228 (3)	0.0441 (4)	−0.0377 (5)
S1	0.0289 (5)	0.0374 (6)	0.0504 (6)	0.0021 (4)	0.0004 (4)	−0.0027 (5)
S2	0.0309 (5)	0.0262 (5)	0.0410 (5)	0.0004 (4)	0.0034 (4)	−0.0016 (4)
O1	0.0373 (16)	0.0419 (19)	0.0602 (18)	0.0023 (13)	0.0028 (14)	−0.0199 (15)
O2	0.0537 (18)	0.0331 (17)	0.0663 (19)	0.0106 (14)	0.0074 (15)	−0.0016 (15)
O3	0.0308 (16)	0.064 (2)	0.072 (2)	−0.0041 (15)	−0.0075 (14)	−0.0053 (17)
O4	0.0277 (14)	0.0306 (16)	0.0552 (17)	−0.0032 (12)	0.0079 (12)	0.0012 (13)
O5	0.0397 (16)	0.0371 (17)	0.0483 (16)	0.0046 (13)	0.0015 (13)	0.0059 (13)
O6	0.0444 (16)	0.0295 (17)	0.0488 (16)	−0.0045 (13)	0.0005 (13)	−0.0060 (13)
N1	0.0282 (19)	0.061 (3)	0.070 (3)	−0.0053 (18)	0.0023 (17)	−0.004 (2)
N2	0.0266 (17)	0.030 (2)	0.045 (2)	−0.0025 (14)	0.0027 (15)	−0.0088 (15)
N3	0.0266 (17)	0.0263 (19)	0.052 (2)	−0.0036 (15)	0.0010 (14)	−0.0082 (17)
N4	0.047 (2)	0.030 (2)	0.062 (2)	−0.0042 (17)	−0.0051 (18)	−0.0024 (18)
N5	0.0257 (16)	0.0244 (19)	0.047 (2)	−0.0017 (14)	0.0003 (14)	−0.0068 (15)
N6	0.0396 (19)	0.0233 (19)	0.0373 (18)	−0.0021 (15)	0.0028 (14)	0.0028 (15)
C1	0.029 (2)	0.038 (2)	0.038 (2)	−0.0023 (17)	0.0013 (16)	−0.0056 (18)
C2	0.019 (2)	0.076 (4)	0.110 (4)	0.002 (2)	0.005 (2)	−0.043 (3)
C3	0.039 (3)	0.070 (4)	0.109 (4)	−0.003 (3)	0.000 (3)	−0.045 (3)
C4	0.030 (3)	0.089 (5)	0.115 (5)	0.005 (3)	0.016 (3)	−0.032 (4)
C5	0.034 (3)	0.067 (4)	0.101 (4)	−0.001 (2)	0.013 (3)	−0.039 (3)
C6	0.033 (2)	0.029 (2)	0.042 (2)	0.0000 (18)	0.0043 (18)	0.0011 (19)
C7	0.036 (2)	0.032 (2)	0.040 (2)	0.0027 (18)	−0.0041 (17)	0.0008 (19)
C8	0.050 (3)	0.035 (3)	0.050 (3)	−0.001 (2)	0.004 (2)	−0.003 (2)
C9	0.054 (3)	0.054 (3)	0.064 (3)	−0.014 (2)	0.007 (2)	0.007 (3)
C10	0.053 (3)	0.068 (4)	0.047 (3)	0.010 (3)	0.009 (2)	0.002 (3)
C11	0.064 (3)	0.056 (3)	0.046 (3)	0.010 (3)	0.002 (2)	−0.009 (2)
C12	0.050 (3)	0.042 (3)	0.044 (2)	0.001 (2)	−0.006 (2)	−0.004 (2)
C13	0.0307 (19)	0.025 (2)	0.034 (2)	−0.0031 (16)	0.0013 (16)	0.0014 (17)
C14	0.036 (2)	0.031 (2)	0.080 (3)	0.0004 (19)	0.017 (2)	−0.007 (2)
C15	0.039 (2)	0.036 (3)	0.091 (4)	−0.010 (2)	0.009 (2)	−0.004 (3)
C16	0.055 (3)	0.032 (3)	0.041 (2)	0.007 (2)	0.005 (2)	−0.0044 (19)
C17	0.038 (2)	0.031 (2)	0.040 (2)	−0.0023 (18)	0.0058 (18)	−0.0013 (18)
C18	0.029 (2)	0.025 (2)	0.031 (2)	−0.0024 (16)	0.0007 (16)	0.0026 (16)
C19	0.034 (2)	0.031 (2)	0.040 (2)	−0.0039 (18)	0.0096 (17)	−0.0066 (18)
C20	0.044 (3)	0.048 (3)	0.063 (3)	−0.003 (2)	0.008 (2)	0.004 (2)
C21	0.059 (3)	0.059 (4)	0.081 (4)	−0.021 (3)	0.019 (3)	−0.004 (3)
C22	0.037 (3)	0.068 (4)	0.079 (3)	−0.008 (3)	0.018 (2)	−0.023 (3)
C23	0.043 (3)	0.052 (3)	0.081 (3)	0.005 (2)	0.011 (2)	−0.017 (3)
C24	0.044 (3)	0.033 (3)	0.068 (3)	−0.001 (2)	0.015 (2)	−0.001 (2)

Geometric parameters (Å, º) top

Br1—C10	1.893 (5)	C4—H4	0.9300
Br2—C22	1.891 (4)	C5—H5A	0.9300
S1—O2	1.426 (3)	C7—C8	1.376 (6)
S1—O3	1.427 (3)	C7—C12	1.392 (6)
S1—N3	1.661 (4)	C8—C9	1.386 (6)
S1—C7	1.758 (4)	C8—H8	0.9300
S2—O5	1.421 (3)	C9—C10	1.375 (7)
S2—O6	1.432 (3)	C9—H9	0.9300
S2—N6	1.654 (3)	C10—C11	1.370 (7)
S2—C19	1.760 (4)	C11—C12	1.369 (6)
O1—C6	1.213 (5)	C11—H11	0.9300
O4—C18	1.216 (4)	C12—H12	0.9300
N1—C3	1.306 (6)	C13—C17	1.375 (5)
N1—C4	1.313 (6)	C13—C14	1.387 (5)
N2—C6	1.343 (5)	C13—C18	1.495 (5)
N2—N3	1.409 (4)	C14—C15	1.375 (6)
N2—H2	0.75 (4)	C14—H14	0.9300
N3—H3	0.77 (4)	C15—H15	0.9300
N4—C15	1.322 (6)	C16—C17	1.379 (5)
N4—C16	1.323 (5)	C16—H16	0.9300
N5—C18	1.348 (5)	C17—H17	0.9300
N5—N6	1.403 (4)	C19—C20	1.375 (6)
N5—H5	0.83 (4)	C19—C24	1.386 (6)
N6—H6	0.83 (4)	C20—C21	1.379 (6)
C1—C5	1.351 (6)	C20—H20	0.9300
C1—C2	1.359 (6)	C21—C22	1.372 (7)
C1—C6	1.513 (5)	C21—H21	0.9300
C2—C3	1.377 (6)	C22—C23	1.376 (7)
C2—H2A	0.9300	C23—C24	1.376 (6)
C3—H3A	0.9300	C23—H23	0.9300
C4—C5	1.393 (7)	C24—H24	0.9300

O2—S1—O3	120.34 (19)	C9—C8—H8	120.6
O2—S1—N3	106.87 (17)	C10—C9—C8	119.3 (4)
O3—S1—N3	104.46 (18)	C10—C9—H9	120.3
O2—S1—C7	108.10 (19)	C8—C9—H9	120.3
O3—S1—C7	110.28 (19)	C11—C10—C9	121.9 (4)
N3—S1—C7	105.78 (17)	C11—C10—Br1	118.2 (4)
O5—S2—O6	120.20 (17)	C9—C10—Br1	119.9 (4)
O5—S2—N6	107.03 (17)	C12—C11—C10	119.4 (4)
O6—S2—N6	104.08 (17)	C12—C11—H11	120.3
O5—S2—C19	108.57 (18)	C10—C11—H11	120.3
O6—S2—C19	109.09 (18)	C11—C12—C7	119.3 (4)
N6—S2—C19	107.09 (17)	C11—C12—H12	120.4
C3—N1—C4	116.3 (4)	C7—C12—H12	120.4
C6—N2—N3	120.9 (3)	C17—C13—C14	117.6 (4)
C6—N2—H2	124 (3)	C17—C13—C18	118.3 (3)
N3—N2—H2	115 (3)	C14—C13—C18	124.1 (3)
N2—N3—S1	112.5 (3)	C15—C14—C13	118.7 (4)
N2—N3—H3	114 (3)	C15—C14—H14	120.6
S1—N3—H3	109 (3)	C13—C14—H14	120.6
C15—N4—C16	117.0 (4)	N4—C15—C14	123.9 (4)
C18—N5—N6	118.1 (3)	N4—C15—H15	118.1
C18—N5—H5	125 (3)	C14—C15—H15	118.1
N6—N5—H5	114 (3)	N4—C16—C17	123.5 (4)
N5—N6—S2	113.2 (2)	N4—C16—H16	118.2
N5—N6—H6	111 (3)	C17—C16—H16	118.2
S2—N6—H6	120 (3)	C13—C17—C16	119.2 (4)
C5—C1—C2	117.5 (4)	C13—C17—H17	120.4
C5—C1—C6	118.0 (4)	C16—C17—H17	120.4
C2—C1—C6	124.5 (4)	O4—C18—N5	123.8 (3)
C1—C2—C3	119.7 (4)	O4—C18—C13	121.0 (3)
C1—C2—H2A	120.2	N5—C18—C13	115.2 (3)
C3—C2—H2A	120.2	C20—C19—C24	121.0 (4)
N1—C3—C2	123.8 (5)	C20—C19—S2	120.1 (3)
N1—C3—H3A	118.1	C24—C19—S2	118.9 (3)
C2—C3—H3A	118.1	C19—C20—C21	119.2 (5)
N1—C4—C5	123.6 (4)	C19—C20—H20	120.4
N1—C4—H4	118.2	C21—C20—H20	120.4
C5—C4—H4	118.2	C22—C21—C20	120.1 (5)
C1—C5—C4	119.0 (5)	C22—C21—H21	120.0
C1—C5—H5A	120.5	C20—C21—H21	120.0
C4—C5—H5A	120.5	C21—C22—C23	120.7 (4)
O1—C6—N2	122.8 (4)	C21—C22—Br2	120.8 (4)
O1—C6—C1	121.0 (3)	C23—C22—Br2	118.5 (4)
N2—C6—C1	116.2 (3)	C24—C23—C22	119.8 (5)
C8—C7—C12	121.3 (4)	C24—C23—H23	120.1
C8—C7—S1	120.1 (3)	C22—C23—H23	120.1
C12—C7—S1	118.4 (3)	C23—C24—C19	119.2 (4)
C7—C8—C9	118.8 (4)	C23—C24—H24	120.4
C7—C8—H8	120.6	C19—C24—H24	120.4

C6—N2—N3—S1	97.7 (4)	Br1—C10—C11—C12	−180.0 (3)
O2—S1—N3—N2	60.2 (3)	C10—C11—C12—C7	−0.6 (6)
O3—S1—N3—N2	−171.2 (3)	C8—C7—C12—C11	−0.7 (6)
C7—S1—N3—N2	−54.8 (3)	S1—C7—C12—C11	173.8 (3)
C18—N5—N6—S2	103.9 (3)	C17—C13—C14—C15	1.0 (6)
O5—S2—N6—N5	−55.9 (3)	C18—C13—C14—C15	179.4 (4)
O6—S2—N6—N5	175.8 (2)	C16—N4—C15—C14	−0.1 (7)
C19—S2—N6—N5	60.3 (3)	C13—C14—C15—N4	−1.2 (7)
C5—C1—C2—C3	−1.4 (8)	C15—N4—C16—C17	1.7 (6)
C6—C1—C2—C3	177.8 (5)	C14—C13—C17—C16	0.4 (6)
C4—N1—C3—C2	1.2 (9)	C18—C13—C17—C16	−178.1 (3)
C1—C2—C3—N1	−0.1 (10)	N4—C16—C17—C13	−1.8 (6)
C3—N1—C4—C5	−0.8 (9)	N6—N5—C18—O4	3.7 (5)
C2—C1—C5—C4	1.7 (8)	N6—N5—C18—C13	−175.0 (3)
C6—C1—C5—C4	−177.5 (5)	C17—C13—C18—O4	16.8 (5)
N1—C4—C5—C1	−0.7 (9)	C14—C13—C18—O4	−161.5 (4)
N3—N2—C6—O1	4.6 (6)	C17—C13—C18—N5	−164.5 (3)
N3—N2—C6—C1	−174.9 (3)	C14—C13—C18—N5	17.2 (5)
C5—C1—C6—O1	3.2 (6)	O5—S2—C19—C20	10.3 (4)
C2—C1—C6—O1	−176.0 (5)	O6—S2—C19—C20	143.0 (3)
C5—C1—C6—N2	−177.3 (4)	N6—S2—C19—C20	−105.0 (4)
C2—C1—C6—N2	3.5 (6)	O5—S2—C19—C24	−170.3 (3)
O2—S1—C7—C8	−16.3 (4)	O6—S2—C19—C24	−37.6 (4)
O3—S1—C7—C8	−149.7 (3)	N6—S2—C19—C24	74.4 (4)
N3—S1—C7—C8	97.9 (3)	C24—C19—C20—C21	−0.7 (7)
O2—S1—C7—C12	169.1 (3)	S2—C19—C20—C21	178.7 (4)
O3—S1—C7—C12	35.7 (4)	C19—C20—C21—C22	0.0 (7)
N3—S1—C7—C12	−76.7 (3)	C20—C21—C22—C23	0.6 (8)
C12—C7—C8—C9	1.1 (6)	C20—C21—C22—Br2	−178.2 (4)
S1—C7—C8—C9	−173.4 (3)	C21—C22—C23—C24	−0.5 (8)
C7—C8—C9—C10	−0.1 (7)	Br2—C22—C23—C24	178.3 (4)
C8—C9—C10—C11	−1.2 (7)	C22—C23—C24—C19	−0.2 (7)
C8—C9—C10—Br1	−179.7 (3)	C20—C19—C24—C23	0.8 (6)
C9—C10—C11—C12	1.6 (7)	S2—C19—C24—C23	−178.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.76 (4)	2.15 (4)	2.882 (4)	165.09
N3—H3···N4ⁱⁱ	0.78 (4)	2.10 (4)	2.868 (5)	168.21
N6—H6···O6ⁱⁱⁱ	0.83 (4)	2.26 (4)	2.998 (4)	147.35
N5—H5···N1^iv	0.83 (4)	2.03 (4)	2.847 (4)	168.32
N3—H3···O1	0.78 (4)	2.49 (4)	2.732 (4)	100 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀BrN₃O₃S
M_r	356.20
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	10.1229 (6), 19.0440 (12), 15.0640 (7)
β (°)	96.862 (2)
V (Å³)	2883.2 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.01
Crystal size (mm)	0.36 × 0.30 × 0.15

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.349, 0.641
No. of measured, independent and observed [I > 2σ(I)] reflections	29398, 6601, 3473
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.146, 1.01
No. of reflections	6601
No. of parameters	373
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.06, −0.88

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.76 (4)	2.15 (4)	2.882 (4)	165.09
N3—H3···N4ⁱⁱ	0.78 (4)	2.10 (4)	2.868 (5)	168.21
N6—H6···O6ⁱⁱⁱ	0.83 (4)	2.26 (4)	2.998 (4)	147.35
N5—H5···N1^iv	0.83 (4)	2.03 (4)	2.847 (4)	168.32
N3—H3···O1	0.78 (4)	2.49 (4)	2.732 (4)	100 (3)

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

Acknowledgements

The authors acknowledge the Higher Education Commission of Pakistan for providing a grant for the project of strengthening the Materials Chemistry Laboratory at GC University, Lahore, Pakistan.

References

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