N′-[(E)-(4-Bromo-2-thien­yl)methyl­idene]benzohydrazide 0.06-hydrate

Shafiq, Z.; Yaqub, M.; Tahir, M.N.; Hussain, A.; Iqbal, M.S.

doi:10.1107/S1600536809037350

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2501

doi:10.1107/S1600536809037350

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N′-[(E)-(4-Bromo-2-thienyl)methylidene]benzohydrazide 0.06-hydrate

Zahid Shafiq,^a Muhammad Yaqub,^a M. Nawaz Tahir,^b ^* Abid Hussain ^a and M. Saeed Iqbal ^c

^aDepartment of Chemistry, Bahauddin Zakariya University, Multan 60800, Pakistan, ^bDepartment of Physics, University of Sargodha, Sargodha, Pakistan, and ^cDepartment of Chemistry, Government College University, Lahore, Pakistan
^*Correspondence e-mail: dmntahir_uos@yahoo.com

(Received 12 September 2009; accepted 15 September 2009; online 19 September 2009)

The title compound, C₁₂H₉BrN₂OS·0.06H₂O, is a hydrated Schiff base derived from benzoic hydrazide and 4-bromothiophene-2-carboxaldehide. The two Schiff base molecules in the asymmetric unit differ crystallographically: in one molecule the dihedral angle between the benzene ring and thiophene ring is 49.88 (11)°, whereas the other molecule the rings are almost coplanar with an r.m.s. deviation for the non-H atoms of 0.025 Å. In the crystal, molecules form polymeric sheets linked by N—H⋯O and C—H⋯O hydrogen bonds. The water molecule of crystallization is partially occupied and its H atoms could not be located.

Related literature

For a related structure, see: Aldoshin et al. (1991 ).

Experimental

Crystal data

C₁₂H₉BrN₂OS·0.06H₂O
M_r = 310.30
Monoclinic, P 2₁ /c
a = 8.8348 (4) Å
b = 18.3446 (10) Å
c = 15.6788 (6) Å
β = 90.274 (2)°
V = 2541.1 (2) Å³
Z = 8
Mo Kα radiation
μ = 3.38 mm⁻¹
T = 296 K
0.28 × 0.14 × 0.12 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.573, T_max = 0.664
13354 measured reflections
4719 independent reflections
2848 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.077
S = 1.00
4719 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2	0.86	2.06	2.878 (3)	160
N3—H3A⋯O1ⁱ	0.86	2.12	2.951 (3)	162
C6—H6⋯O2	0.93	2.50	3.231 (4)	136
C20—H20⋯O1ⁱ	0.93	2.49	3.282 (4)	143
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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 global, I. DOI: 10.1107/S1600536809037350/hb5098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809037350/hb5098Isup2.hkl

checkCIF report

Comment top

The title compound (I, Fig. 1), has been prepared for complexation with various metals and with hope that it will be biologically active as well. The biological studies of (I) are under progress.

The crystal structure of (I) differs from (II) (N'-2-(thienylidene))benzhydrazide (Aldoshin et al., 1991) due to bromo substitution.

The title compound consist of two crystallographically different molecules and fractional part of O-atom which occupies the solvent accessible area. The fractional O-atom may be part of methanol, ethanol or water from air. The molecules are stabilized in the form of polymeric sheets due to H-bondings (Table 1, Fig. 2) which extend along the c axis. In one molecule the benzene ring A (C1—C6) and the thiophene ring B (C9—C10, S1) are oriented at a dihedral angle of 49.88 (11)° whereas in the other molecule both rings are nearly planar with an r.m.s. deviation of 0.025 Å.

Related literature top

For a related structure, see: Aldoshin et al. (1991).

Experimental top

To a hot stirred solution of benzoic hydrazide (1.36 g, 0.01 mol) in ethanol (15 ml) was added 4-bromo-2-thiophencarboxaldehide (1.91 g, 0.01 mol). The resultant mixture was then heated under reflux. After an hour precipitates were formed. The reaction mixture was further heated about 30 min for the completion of the reaction which was monitored through TLC. The reaction mixture was cooled to room temperature, filtered and washed with hot ethanol. The crude material was recrystallized in hot methanol to affoard colourless needles of (I).

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. View of (I) with displacement ellipsoids drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radius.
	Fig. 2. The partial packing of (I) which shows that molecules form polymeric chains which are extending along the crystallographic c axis.

N'-[(E)-(4-Bromo-2-thienyl)methylidene]benzohydrazide 0.06-hydrate top

Crystal data top

C₁₂H₉BrN₂OS·0.06H₂O	F(000) = 1236
M_r = 310.30	D_x = 1.622 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4719 reflections
a = 8.8348 (4) Å	θ = 2.3–25.5°
b = 18.3446 (10) Å	µ = 3.38 mm⁻¹
c = 15.6788 (6) Å	T = 296 K
β = 90.274 (2)°	Cut needle, colourless
V = 2541.1 (2) Å³	0.28 × 0.14 × 0.12 mm
Z = 8

Data collection top

Bruker Kappa APEXII CCD diffractometer	4719 independent reflections
Radiation source: fine-focus sealed tube	2848 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 7.80 pixels mm^-1	θ_max = 25.5°, θ_min = 2.3°
ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)	k = −22→21
T_min = 0.573, T_max = 0.664	l = −18→18
13354 measured reflections

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0274P)² + 0.0751P] where P = (F_o² + 2F_c²)/3
4719 reflections	(Δ/σ)_max = 0.001
316 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₁₂H₉BrN₂OS·0.06H₂O	V = 2541.1 (2) Å³
M_r = 310.30	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.8348 (4) Å	µ = 3.38 mm⁻¹
b = 18.3446 (10) Å	T = 296 K
c = 15.6788 (6) Å	0.28 × 0.14 × 0.12 mm
β = 90.274 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	4719 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2848 reflections with I > 2σ(I)
T_min = 0.573, T_max = 0.664	R_int = 0.048
13354 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 1.00	Δρ_max = 0.28 e Å⁻³
4719 reflections	Δρ_min = −0.42 e Å⁻³
316 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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 > σ(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	Occ. (<1)
Br1	0.14491 (5)	0.59765 (2)	0.12678 (2)	0.0630 (2)
S1	0.17094 (11)	0.36619 (5)	0.06330 (5)	0.0498 (3)
O1	0.1624 (3)	0.11321 (12)	0.15983 (13)	0.0533 (9)
N1	0.2332 (3)	0.19770 (14)	0.25615 (14)	0.0408 (10)
N2	0.2058 (3)	0.25339 (15)	0.19887 (15)	0.0417 (10)
C1	0.2702 (3)	0.07061 (17)	0.28937 (17)	0.0336 (11)
C2	0.1990 (4)	0.00419 (18)	0.28690 (18)	0.0451 (14)
C3	0.2485 (4)	−0.05279 (19)	0.3370 (2)	0.0556 (14)
C4	0.3746 (5)	−0.0433 (2)	0.3873 (2)	0.0596 (14)
C5	0.4483 (4)	0.0227 (2)	0.39020 (19)	0.0510 (16)
C6	0.3950 (4)	0.08002 (18)	0.34119 (18)	0.0414 (11)
C7	0.2158 (3)	0.12853 (18)	0.22989 (19)	0.0370 (12)
C8	0.2124 (3)	0.31748 (18)	0.22827 (19)	0.0424 (11)
C9	0.1899 (3)	0.37935 (18)	0.17201 (18)	0.0393 (11)
C10	0.1825 (3)	0.45039 (18)	0.1922 (2)	0.0449 (11)
C11	0.1601 (3)	0.49531 (17)	0.1202 (2)	0.0396 (11)
C12	0.1528 (4)	0.45763 (18)	0.0468 (2)	0.0460 (12)
Br2	−0.53100 (5)	0.45182 (2)	0.37441 (3)	0.0758 (2)
S2	−0.15815 (11)	0.29933 (6)	0.33933 (5)	0.0559 (4)
O2	0.3874 (3)	0.24667 (12)	0.40780 (13)	0.0479 (9)
N3	0.2504 (3)	0.31281 (14)	0.50045 (14)	0.0415 (10)
N4	0.1274 (3)	0.31373 (15)	0.44655 (14)	0.0434 (11)
C13	0.5098 (4)	0.28364 (18)	0.53558 (17)	0.0366 (11)
C14	0.5227 (4)	0.3363 (2)	0.59883 (19)	0.0513 (14)
C15	0.6512 (4)	0.3403 (2)	0.6488 (2)	0.0640 (18)
C16	0.7682 (4)	0.2919 (3)	0.6359 (2)	0.0684 (19)
C17	0.7573 (4)	0.2400 (2)	0.5739 (3)	0.0623 (17)
C18	0.6284 (4)	0.23582 (18)	0.5242 (2)	0.0497 (14)
C19	0.3774 (4)	0.27852 (17)	0.47561 (19)	0.0360 (12)
C20	0.0191 (4)	0.3547 (2)	0.47003 (19)	0.0494 (16)
C21	−0.1191 (4)	0.35979 (19)	0.42087 (18)	0.0451 (11)
C22	−0.2347 (4)	0.4067 (2)	0.4320 (2)	0.0497 (14)
C23	−0.3549 (4)	0.3943 (2)	0.3754 (2)	0.0490 (14)
C24	−0.3311 (4)	0.3383 (2)	0.3225 (2)	0.0564 (16)
O3	0.911 (2)	0.0164 (9)	0.1129 (9)	0.048 (7)	0.125
H1N	0.26089	0.20713	0.30764	0.0489*
H2	0.11612	−0.00246	0.25091	0.0537*
H3	0.19721	−0.09707	0.33675	0.0669*
H4	0.41062	−0.08202	0.41992	0.0714*
H5	0.53323	0.02878	0.42476	0.0612*
H6	0.44347	0.12498	0.34324	0.0496*
H8	0.23166	0.32497	0.28597	0.0509*
H10	0.19111	0.46807	0.24758	0.0536*
H12	0.13932	0.47887	−0.00657	0.0548*
H3A	0.24631	0.33386	0.54939	0.0496*
H14	0.44400	0.36913	0.60754	0.0619*
H15	0.65900	0.37564	0.69119	0.0765*
H16	0.85492	0.29467	0.66954	0.0818*
H17	0.83660	0.20759	0.56515	0.0746*
H18	0.62129	0.20009	0.48232	0.0594*
H20	0.02921	0.38194	0.51978	0.0592*
H22	−0.23469	0.44331	0.47297	0.0597*
H24	−0.40030	0.32254	0.28156	0.0676*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0723 (3)	0.0383 (2)	0.0784 (3)	−0.0020 (2)	−0.0096 (2)	0.0086 (2)
S1	0.0682 (7)	0.0444 (6)	0.0368 (5)	0.0061 (5)	−0.0025 (4)	0.0047 (4)
O1	0.0733 (18)	0.0508 (16)	0.0357 (13)	−0.0143 (13)	−0.0168 (12)	0.0050 (11)
N1	0.0569 (19)	0.0380 (18)	0.0274 (14)	0.0006 (14)	−0.0068 (12)	0.0069 (13)
N2	0.0497 (19)	0.0413 (18)	0.0340 (15)	0.0028 (14)	−0.0042 (12)	0.0099 (14)
C1	0.037 (2)	0.038 (2)	0.0259 (17)	0.0035 (16)	0.0034 (14)	−0.0021 (14)
C2	0.055 (3)	0.042 (2)	0.0382 (19)	−0.0052 (18)	0.0015 (16)	−0.0039 (17)
C3	0.085 (3)	0.031 (2)	0.051 (2)	−0.007 (2)	0.013 (2)	−0.0002 (18)
C4	0.087 (3)	0.040 (2)	0.052 (2)	0.021 (2)	0.010 (2)	0.0125 (18)
C5	0.052 (3)	0.056 (3)	0.045 (2)	0.013 (2)	−0.0027 (17)	0.0107 (18)
C6	0.042 (2)	0.042 (2)	0.0403 (19)	−0.0007 (16)	0.0022 (16)	0.0043 (16)
C7	0.040 (2)	0.038 (2)	0.033 (2)	−0.0064 (16)	0.0003 (16)	0.0030 (16)
C8	0.050 (2)	0.042 (2)	0.0351 (19)	0.0037 (17)	−0.0027 (15)	0.0030 (17)
C9	0.043 (2)	0.040 (2)	0.0349 (19)	0.0040 (16)	−0.0029 (15)	0.0067 (15)
C10	0.048 (2)	0.044 (2)	0.0427 (19)	0.0001 (18)	−0.0074 (16)	−0.0004 (18)
C11	0.038 (2)	0.0307 (19)	0.050 (2)	−0.0035 (15)	−0.0044 (16)	0.0094 (17)
C12	0.048 (2)	0.045 (2)	0.045 (2)	0.0010 (18)	−0.0016 (16)	0.0156 (17)
Br2	0.0563 (3)	0.0776 (3)	0.0934 (3)	0.0089 (2)	−0.0164 (2)	0.0157 (2)
S2	0.0563 (7)	0.0660 (7)	0.0454 (5)	−0.0039 (5)	−0.0074 (4)	−0.0029 (5)
O2	0.0560 (16)	0.0536 (16)	0.0340 (12)	−0.0029 (12)	0.0005 (11)	−0.0139 (12)
N3	0.0431 (19)	0.054 (2)	0.0273 (15)	0.0011 (14)	−0.0061 (13)	−0.0039 (12)
N4	0.0431 (19)	0.057 (2)	0.0301 (16)	−0.0010 (15)	−0.0055 (14)	0.0019 (13)
C13	0.041 (2)	0.041 (2)	0.0277 (18)	−0.0029 (16)	−0.0016 (15)	0.0054 (15)
C14	0.046 (2)	0.066 (3)	0.042 (2)	0.0023 (19)	−0.0008 (17)	−0.0057 (18)
C15	0.055 (3)	0.097 (4)	0.040 (2)	−0.010 (2)	−0.0129 (19)	−0.006 (2)
C16	0.051 (3)	0.100 (4)	0.054 (3)	−0.010 (3)	−0.017 (2)	0.027 (2)
C17	0.053 (3)	0.063 (3)	0.071 (3)	0.007 (2)	−0.002 (2)	0.026 (2)
C18	0.056 (3)	0.042 (2)	0.051 (2)	0.0013 (19)	0.0012 (19)	0.0075 (17)
C19	0.042 (2)	0.034 (2)	0.032 (2)	−0.0060 (16)	0.0004 (16)	0.0047 (15)
C20	0.053 (3)	0.061 (3)	0.034 (2)	−0.005 (2)	−0.0064 (18)	0.0022 (17)
C21	0.050 (2)	0.054 (2)	0.0313 (19)	−0.0032 (19)	−0.0050 (17)	0.0022 (16)
C22	0.051 (3)	0.056 (2)	0.042 (2)	−0.002 (2)	−0.0031 (18)	0.0011 (18)
C23	0.048 (2)	0.056 (3)	0.043 (2)	−0.0053 (19)	−0.0058 (17)	0.0147 (19)
C24	0.050 (3)	0.070 (3)	0.049 (2)	−0.016 (2)	−0.0162 (17)	0.011 (2)
O3	0.058 (13)	0.047 (12)	0.039 (10)	−0.005 (9)	−0.010 (8)	0.021 (8)

Geometric parameters (Å, º) top

Br1—C11	1.885 (3)	C2—H2	0.9300
Br2—C23	1.880 (4)	C3—H3	0.9300
S1—C9	1.729 (3)	C4—H4	0.9300
S1—C12	1.705 (3)	C5—H5	0.9300
S2—C21	1.726 (3)	C6—H6	0.9300
S2—C24	1.706 (4)	C8—H8	0.9300
O1—C7	1.226 (4)	C10—H10	0.9300
O2—C19	1.217 (4)	C12—H12	0.9300
N1—N2	1.381 (4)	C13—C14	1.389 (4)
N1—C7	1.343 (4)	C13—C19	1.500 (5)
N2—C8	1.264 (4)	C13—C18	1.379 (5)
N1—H1N	0.8600	C14—C15	1.378 (5)
N3—N4	1.374 (4)	C15—C16	1.378 (6)
N3—C19	1.346 (4)	C16—C17	1.364 (6)
N4—C20	1.273 (4)	C17—C18	1.379 (5)
N3—H3A	0.8600	C20—C21	1.444 (5)
C1—C2	1.372 (5)	C21—C22	1.348 (5)
C1—C7	1.492 (4)	C22—C23	1.399 (5)
C1—C6	1.377 (4)	C23—C24	1.338 (5)
C2—C3	1.378 (5)	C14—H14	0.9300
C3—C4	1.373 (5)	C15—H15	0.9300
C4—C5	1.375 (5)	C16—H16	0.9300
C5—C6	1.384 (5)	C17—H17	0.9300
C8—C9	1.451 (4)	C18—H18	0.9300
C9—C10	1.343 (5)	C20—H20	0.9300
C10—C11	1.411 (4)	C22—H22	0.9300
C11—C12	1.344 (4)	C24—H24	0.9300

C9—S1—C12	91.19 (16)	N2—C8—H8	120.00
C21—S2—C24	91.20 (17)	C9—C10—H10	124.00
N2—N1—C7	118.7 (2)	C11—C10—H10	124.00
N1—N2—C8	116.3 (2)	S1—C12—H12	124.00
N2—N1—H1N	121.00	C11—C12—H12	124.00
C7—N1—H1N	121.00	C14—C13—C19	123.5 (3)
N4—N3—C19	119.1 (2)	C14—C13—C18	118.4 (3)
N3—N4—C20	115.0 (2)	C18—C13—C19	118.0 (3)
C19—N3—H3A	120.00	C13—C14—C15	120.5 (3)
N4—N3—H3A	120.00	C14—C15—C16	119.9 (3)
C6—C1—C7	122.3 (3)	C15—C16—C17	120.3 (3)
C2—C1—C6	119.6 (3)	C16—C17—C18	119.8 (3)
C2—C1—C7	118.0 (3)	C13—C18—C17	121.2 (3)
C1—C2—C3	120.9 (3)	O2—C19—C13	121.2 (3)
C2—C3—C4	119.1 (3)	O2—C19—N3	122.8 (3)
C3—C4—C5	120.9 (3)	N3—C19—C13	116.0 (3)
C4—C5—C6	119.4 (3)	N4—C20—C21	121.3 (3)
C1—C6—C5	120.1 (3)	S2—C21—C20	121.3 (3)
N1—C7—C1	116.5 (3)	C20—C21—C22	127.7 (3)
O1—C7—C1	121.2 (3)	S2—C21—C22	110.9 (3)
O1—C7—N1	122.3 (3)	C21—C22—C23	112.8 (3)
N2—C8—C9	120.0 (3)	Br2—C23—C22	122.7 (3)
S1—C9—C8	120.2 (2)	Br2—C23—C24	124.0 (3)
C8—C9—C10	128.5 (3)	C22—C23—C24	113.4 (3)
S1—C9—C10	111.3 (2)	S2—C24—C23	111.7 (3)
C9—C10—C11	112.7 (3)	C13—C14—H14	120.00
C10—C11—C12	113.0 (3)	C15—C14—H14	120.00
Br1—C11—C10	123.2 (2)	C14—C15—H15	120.00
Br1—C11—C12	123.8 (2)	C16—C15—H15	120.00
S1—C12—C11	111.9 (2)	C15—C16—H16	120.00
C3—C2—H2	120.00	C17—C16—H16	120.00
C1—C2—H2	120.00	C16—C17—H17	120.00
C4—C3—H3	120.00	C18—C17—H17	120.00
C2—C3—H3	120.00	C13—C18—H18	119.00
C5—C4—H4	120.00	C17—C18—H18	119.00
C3—C4—H4	120.00	N4—C20—H20	119.00
C4—C5—H5	120.00	C21—C20—H20	119.00
C6—C5—H5	120.00	C21—C22—H22	124.00
C1—C6—H6	120.00	C23—C22—H22	124.00
C5—C6—H6	120.00	S2—C24—H24	124.00
C9—C8—H8	120.00	C23—C24—H24	124.00

C12—S1—C9—C8	−179.4 (2)	N2—C8—C9—C10	175.0 (3)
C12—S1—C9—C10	−0.1 (2)	S1—C9—C10—C11	0.5 (3)
C9—S1—C12—C11	−0.3 (3)	C8—C9—C10—C11	179.7 (3)
C24—S2—C21—C22	−0.5 (3)	C9—C10—C11—Br1	−179.94 (19)
C21—S2—C24—C23	0.8 (3)	C9—C10—C11—C12	−0.8 (4)
C24—S2—C21—C20	176.9 (3)	Br1—C11—C12—S1	179.84 (17)
C7—N1—N2—C8	174.8 (3)	C10—C11—C12—S1	0.7 (4)
N2—N1—C7—O1	−7.3 (4)	C18—C13—C14—C15	−0.1 (5)
N2—N1—C7—C1	170.5 (2)	C19—C13—C14—C15	−176.5 (3)
N1—N2—C8—C9	178.0 (2)	C14—C13—C18—C17	−0.3 (5)
C19—N3—N4—C20	−171.6 (3)	C19—C13—C18—C17	176.4 (3)
N4—N3—C19—O2	−1.6 (5)	C14—C13—C19—O2	159.0 (3)
N4—N3—C19—C13	176.5 (3)	C14—C13—C19—N3	−19.1 (5)
N3—N4—C20—C21	−178.4 (3)	C18—C13—C19—O2	−17.4 (5)
C6—C1—C2—C3	1.5 (5)	C18—C13—C19—N3	164.4 (3)
C7—C1—C2—C3	176.7 (3)	C13—C14—C15—C16	0.2 (5)
C2—C1—C6—C5	0.2 (5)	C14—C15—C16—C17	−0.1 (6)
C7—C1—C6—C5	−174.8 (3)	C15—C16—C17—C18	−0.3 (6)
C2—C1—C7—O1	−31.2 (4)	C16—C17—C18—C13	0.4 (6)
C6—C1—C7—N1	−34.0 (4)	N4—C20—C21—S2	11.7 (5)
C2—C1—C7—N1	150.9 (3)	N4—C20—C21—C22	−171.4 (3)
C6—C1—C7—O1	143.9 (3)	S2—C21—C22—C23	0.1 (4)
C1—C2—C3—C4	−2.6 (5)	C20—C21—C22—C23	−177.1 (3)
C2—C3—C4—C5	2.1 (5)	C21—C22—C23—Br2	−179.1 (3)
C3—C4—C5—C6	−0.5 (5)	C21—C22—C23—C24	0.5 (4)
C4—C5—C6—C1	−0.7 (5)	Br2—C23—C24—S2	178.73 (19)
N2—C8—C9—S1	−5.8 (4)	C22—C23—C24—S2	−0.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.86	2.06	2.878 (3)	160
N3—H3A···O1ⁱ	0.86	2.12	2.951 (3)	162
C6—H6···O2	0.93	2.50	3.231 (4)	136
C20—H20···O1ⁱ	0.93	2.49	3.282 (4)	143

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₉BrN₂OS·0.06H₂O
M_r	310.30
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	8.8348 (4), 18.3446 (10), 15.6788 (6)
β (°)	90.274 (2)
V (Å³)	2541.1 (2)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.38
Crystal size (mm)	0.28 × 0.14 × 0.12

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.573, 0.664
No. of measured, independent and observed [I > 2σ(I)] reflections	13354, 4719, 2848
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.077, 1.00
No. of reflections	4719
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.42

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
N1—H1N···O2	0.86	2.06	2.878 (3)	160
N3—H3A···O1ⁱ	0.86	2.12	2.951 (3)	162
C6—H6···O2	0.93	2.50	3.231 (4)	136
C20—H20···O1ⁱ	0.93	2.49	3.282 (4)	143

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

AH greatfully acknowledges the Higher Education Commission, Islamabad, Pakistan, for providing him with a scholarship under the Indigenous PhD Program (PIN 063–121531-PS3–127).

References

Aldoshin, S. M., Chuev, I. I., Atovmyan, L. O., Nedzvetskii, V. S. & Kulikov, A. S. (1991). Russ. Chem. Bull. 40, 87–90. Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar