N'-[(E)-(4-Bromo-2-thien-yl)methyl-idene]benzohydrazide 0.06-hydrate.

The title compound, C(12)H(9)BrN(2)OS·0.06H(2)O, is a hydrated Schiff base derived from benzoic hydrazide and 4-bromo-thio-phene-2-carboxaldehide. The two Schiff base mol-ecules in the asymmetric unit differ crystallographically: in one mol-ecule the dihedral angle between the benzene ring and thio-phene ring is 49.88 (11)°, whereas the other mol-ecule the rings are almost coplanar with an r.m.s. deviation for the non-H atoms of 0.025 Å. In the crystal, mol-ecules form polymeric sheets linked by N-H⋯O and C-H⋯O hydrogen bonds. The water mol-ecule 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 = 310.30

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.077

S = 1.00

4719 reflections

316 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.42 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809037350/hb5098sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C12H9BrN2OS·0.06H2O	F(000) = 1236
Mr = 310.30	Dx = 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

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

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(Fo2) + (0.0274P)2 + 0.0751P] where P = (Fo2 + 2Fc2)/3
4719 reflections	(Δ/σ)max = 0.001
316 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.41 e Å−3

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.

	x	y	z	Uiso*/Ueq	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*

	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)

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)

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

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) .