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Acta Crystallogr Sect E Struct Rep Online. 2009 October 1; 65(Pt 10): o2501.
Published online 2009 September 19. doi:  10.1107/S1600536809037350
PMCID: PMC2970472

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

Abstract

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 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2501-scheme1.jpg

Experimental

Crystal data

  • C12H9BrN2OS·0.06H2O
  • M r = 310.30
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2501-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

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).

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

There exist solvent accessible volume if only two Schiff base molecules are refined. Therefore, the largest difference peak was taken as a water O-atom and refined anisotropically with an occupancy factor of 0.125. Its presumed H atoms could not be located.

The other H-atoms were positioned geometrically with N—H = 0.86, C—H = 0.93 Å for aromatic H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C, N).

Figures

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.

Crystal data

C12H9BrN2OS·0.06H2OF(000) = 1236
Mr = 310.30Dx = 1.622 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4719 reflections
a = 8.8348 (4) Åθ = 2.3–25.5°
b = 18.3446 (10) ŵ = 3.38 mm1
c = 15.6788 (6) ÅT = 296 K
β = 90.274 (2)°Cut needle, colourless
V = 2541.1 (2) Å30.28 × 0.14 × 0.12 mm
Z = 8

Data collection

Bruker Kappa APEXII CCD diffractometer4719 independent reflections
Radiation source: fine-focus sealed tube2848 reflections with I > 2σ(I)
graphiteRint = 0.048
Detector resolution: 7.80 pixels mm-1θmax = 25.5°, θmin = 2.3°
ω scansh = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −22→21
Tmin = 0.573, Tmax = 0.664l = −18→18
13354 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0274P)2 + 0.0751P] where P = (Fo2 + 2Fc2)/3
4719 reflections(Δ/σ)max = 0.001
316 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.41 e Å3

Special details

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)

xyzUiso*/UeqOcc. (<1)
Br10.14491 (5)0.59765 (2)0.12678 (2)0.0630 (2)
S10.17094 (11)0.36619 (5)0.06330 (5)0.0498 (3)
O10.1624 (3)0.11321 (12)0.15983 (13)0.0533 (9)
N10.2332 (3)0.19770 (14)0.25615 (14)0.0408 (10)
N20.2058 (3)0.25339 (15)0.19887 (15)0.0417 (10)
C10.2702 (3)0.07061 (17)0.28937 (17)0.0336 (11)
C20.1990 (4)0.00419 (18)0.28690 (18)0.0451 (14)
C30.2485 (4)−0.05279 (19)0.3370 (2)0.0556 (14)
C40.3746 (5)−0.0433 (2)0.3873 (2)0.0596 (14)
C50.4483 (4)0.0227 (2)0.39020 (19)0.0510 (16)
C60.3950 (4)0.08002 (18)0.34119 (18)0.0414 (11)
C70.2158 (3)0.12853 (18)0.22989 (19)0.0370 (12)
C80.2124 (3)0.31748 (18)0.22827 (19)0.0424 (11)
C90.1899 (3)0.37935 (18)0.17201 (18)0.0393 (11)
C100.1825 (3)0.45039 (18)0.1922 (2)0.0449 (11)
C110.1601 (3)0.49531 (17)0.1202 (2)0.0396 (11)
C120.1528 (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)
O20.3874 (3)0.24667 (12)0.40780 (13)0.0479 (9)
N30.2504 (3)0.31281 (14)0.50045 (14)0.0415 (10)
N40.1274 (3)0.31373 (15)0.44655 (14)0.0434 (11)
C130.5098 (4)0.28364 (18)0.53558 (17)0.0366 (11)
C140.5227 (4)0.3363 (2)0.59883 (19)0.0513 (14)
C150.6512 (4)0.3403 (2)0.6488 (2)0.0640 (18)
C160.7682 (4)0.2919 (3)0.6359 (2)0.0684 (19)
C170.7573 (4)0.2400 (2)0.5739 (3)0.0623 (17)
C180.6284 (4)0.23582 (18)0.5242 (2)0.0497 (14)
C190.3774 (4)0.27852 (17)0.47561 (19)0.0360 (12)
C200.0191 (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)
O30.911 (2)0.0164 (9)0.1129 (9)0.048 (7)0.125
H1N0.260890.207130.307640.0489*
H20.11612−0.002460.250910.0537*
H30.19721−0.097070.336750.0669*
H40.41062−0.082020.419920.0714*
H50.533230.028780.424760.0612*
H60.443470.124980.343240.0496*
H80.231660.324970.285970.0509*
H100.191110.468070.247580.0536*
H120.139320.47887−0.006570.0548*
H3A0.246310.333860.549390.0496*
H140.444000.369130.607540.0619*
H150.659000.375640.691190.0765*
H160.854920.294670.669540.0818*
H170.836600.207590.565150.0746*
H180.621290.200090.482320.0594*
H200.029210.381940.519780.0592*
H22−0.234690.443310.472970.0597*
H24−0.400300.322540.281560.0676*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0723 (3)0.0383 (2)0.0784 (3)−0.0020 (2)−0.0096 (2)0.0086 (2)
S10.0682 (7)0.0444 (6)0.0368 (5)0.0061 (5)−0.0025 (4)0.0047 (4)
O10.0733 (18)0.0508 (16)0.0357 (13)−0.0143 (13)−0.0168 (12)0.0050 (11)
N10.0569 (19)0.0380 (18)0.0274 (14)0.0006 (14)−0.0068 (12)0.0069 (13)
N20.0497 (19)0.0413 (18)0.0340 (15)0.0028 (14)−0.0042 (12)0.0099 (14)
C10.037 (2)0.038 (2)0.0259 (17)0.0035 (16)0.0034 (14)−0.0021 (14)
C20.055 (3)0.042 (2)0.0382 (19)−0.0052 (18)0.0015 (16)−0.0039 (17)
C30.085 (3)0.031 (2)0.051 (2)−0.007 (2)0.013 (2)−0.0002 (18)
C40.087 (3)0.040 (2)0.052 (2)0.021 (2)0.010 (2)0.0125 (18)
C50.052 (3)0.056 (3)0.045 (2)0.013 (2)−0.0027 (17)0.0107 (18)
C60.042 (2)0.042 (2)0.0403 (19)−0.0007 (16)0.0022 (16)0.0043 (16)
C70.040 (2)0.038 (2)0.033 (2)−0.0064 (16)0.0003 (16)0.0030 (16)
C80.050 (2)0.042 (2)0.0351 (19)0.0037 (17)−0.0027 (15)0.0030 (17)
C90.043 (2)0.040 (2)0.0349 (19)0.0040 (16)−0.0029 (15)0.0067 (15)
C100.048 (2)0.044 (2)0.0427 (19)0.0001 (18)−0.0074 (16)−0.0004 (18)
C110.038 (2)0.0307 (19)0.050 (2)−0.0035 (15)−0.0044 (16)0.0094 (17)
C120.048 (2)0.045 (2)0.045 (2)0.0010 (18)−0.0016 (16)0.0156 (17)
Br20.0563 (3)0.0776 (3)0.0934 (3)0.0089 (2)−0.0164 (2)0.0157 (2)
S20.0563 (7)0.0660 (7)0.0454 (5)−0.0039 (5)−0.0074 (4)−0.0029 (5)
O20.0560 (16)0.0536 (16)0.0340 (12)−0.0029 (12)0.0005 (11)−0.0139 (12)
N30.0431 (19)0.054 (2)0.0273 (15)0.0011 (14)−0.0061 (13)−0.0039 (12)
N40.0431 (19)0.057 (2)0.0301 (16)−0.0010 (15)−0.0055 (14)0.0019 (13)
C130.041 (2)0.041 (2)0.0277 (18)−0.0029 (16)−0.0016 (15)0.0054 (15)
C140.046 (2)0.066 (3)0.042 (2)0.0023 (19)−0.0008 (17)−0.0057 (18)
C150.055 (3)0.097 (4)0.040 (2)−0.010 (2)−0.0129 (19)−0.006 (2)
C160.051 (3)0.100 (4)0.054 (3)−0.010 (3)−0.017 (2)0.027 (2)
C170.053 (3)0.063 (3)0.071 (3)0.007 (2)−0.002 (2)0.026 (2)
C180.056 (3)0.042 (2)0.051 (2)0.0013 (19)0.0012 (19)0.0075 (17)
C190.042 (2)0.034 (2)0.032 (2)−0.0060 (16)0.0004 (16)0.0047 (15)
C200.053 (3)0.061 (3)0.034 (2)−0.005 (2)−0.0064 (18)0.0022 (17)
C210.050 (2)0.054 (2)0.0313 (19)−0.0032 (19)−0.0050 (17)0.0022 (16)
C220.051 (3)0.056 (2)0.042 (2)−0.002 (2)−0.0031 (18)0.0011 (18)
C230.048 (2)0.056 (3)0.043 (2)−0.0053 (19)−0.0058 (17)0.0147 (19)
C240.050 (3)0.070 (3)0.049 (2)−0.016 (2)−0.0162 (17)0.011 (2)
O30.058 (13)0.047 (12)0.039 (10)−0.005 (9)−0.010 (8)0.021 (8)

Geometric parameters (Å, °)

Br1—C111.885 (3)C2—H20.9300
Br2—C231.880 (4)C3—H30.9300
S1—C91.729 (3)C4—H40.9300
S1—C121.705 (3)C5—H50.9300
S2—C211.726 (3)C6—H60.9300
S2—C241.706 (4)C8—H80.9300
O1—C71.226 (4)C10—H100.9300
O2—C191.217 (4)C12—H120.9300
N1—N21.381 (4)C13—C141.389 (4)
N1—C71.343 (4)C13—C191.500 (5)
N2—C81.264 (4)C13—C181.379 (5)
N1—H1N0.8600C14—C151.378 (5)
N3—N41.374 (4)C15—C161.378 (6)
N3—C191.346 (4)C16—C171.364 (6)
N4—C201.273 (4)C17—C181.379 (5)
N3—H3A0.8600C20—C211.444 (5)
C1—C21.372 (5)C21—C221.348 (5)
C1—C71.492 (4)C22—C231.399 (5)
C1—C61.377 (4)C23—C241.338 (5)
C2—C31.378 (5)C14—H140.9300
C3—C41.373 (5)C15—H150.9300
C4—C51.375 (5)C16—H160.9300
C5—C61.384 (5)C17—H170.9300
C8—C91.451 (4)C18—H180.9300
C9—C101.343 (5)C20—H200.9300
C10—C111.411 (4)C22—H220.9300
C11—C121.344 (4)C24—H240.9300
C9—S1—C1291.19 (16)N2—C8—H8120.00
C21—S2—C2491.20 (17)C9—C10—H10124.00
N2—N1—C7118.7 (2)C11—C10—H10124.00
N1—N2—C8116.3 (2)S1—C12—H12124.00
N2—N1—H1N121.00C11—C12—H12124.00
C7—N1—H1N121.00C14—C13—C19123.5 (3)
N4—N3—C19119.1 (2)C14—C13—C18118.4 (3)
N3—N4—C20115.0 (2)C18—C13—C19118.0 (3)
C19—N3—H3A120.00C13—C14—C15120.5 (3)
N4—N3—H3A120.00C14—C15—C16119.9 (3)
C6—C1—C7122.3 (3)C15—C16—C17120.3 (3)
C2—C1—C6119.6 (3)C16—C17—C18119.8 (3)
C2—C1—C7118.0 (3)C13—C18—C17121.2 (3)
C1—C2—C3120.9 (3)O2—C19—C13121.2 (3)
C2—C3—C4119.1 (3)O2—C19—N3122.8 (3)
C3—C4—C5120.9 (3)N3—C19—C13116.0 (3)
C4—C5—C6119.4 (3)N4—C20—C21121.3 (3)
C1—C6—C5120.1 (3)S2—C21—C20121.3 (3)
N1—C7—C1116.5 (3)C20—C21—C22127.7 (3)
O1—C7—C1121.2 (3)S2—C21—C22110.9 (3)
O1—C7—N1122.3 (3)C21—C22—C23112.8 (3)
N2—C8—C9120.0 (3)Br2—C23—C22122.7 (3)
S1—C9—C8120.2 (2)Br2—C23—C24124.0 (3)
C8—C9—C10128.5 (3)C22—C23—C24113.4 (3)
S1—C9—C10111.3 (2)S2—C24—C23111.7 (3)
C9—C10—C11112.7 (3)C13—C14—H14120.00
C10—C11—C12113.0 (3)C15—C14—H14120.00
Br1—C11—C10123.2 (2)C14—C15—H15120.00
Br1—C11—C12123.8 (2)C16—C15—H15120.00
S1—C12—C11111.9 (2)C15—C16—H16120.00
C3—C2—H2120.00C17—C16—H16120.00
C1—C2—H2120.00C16—C17—H17120.00
C4—C3—H3120.00C18—C17—H17120.00
C2—C3—H3120.00C13—C18—H18119.00
C5—C4—H4120.00C17—C18—H18119.00
C3—C4—H4120.00N4—C20—H20119.00
C4—C5—H5120.00C21—C20—H20119.00
C6—C5—H5120.00C21—C22—H22124.00
C1—C6—H6120.00C23—C22—H22124.00
C5—C6—H6120.00S2—C24—H24124.00
C9—C8—H8120.00C23—C24—H24124.00
C12—S1—C9—C8−179.4 (2)N2—C8—C9—C10175.0 (3)
C12—S1—C9—C10−0.1 (2)S1—C9—C10—C110.5 (3)
C9—S1—C12—C11−0.3 (3)C8—C9—C10—C11179.7 (3)
C24—S2—C21—C22−0.5 (3)C9—C10—C11—Br1−179.94 (19)
C21—S2—C24—C230.8 (3)C9—C10—C11—C12−0.8 (4)
C24—S2—C21—C20176.9 (3)Br1—C11—C12—S1179.84 (17)
C7—N1—N2—C8174.8 (3)C10—C11—C12—S10.7 (4)
N2—N1—C7—O1−7.3 (4)C18—C13—C14—C15−0.1 (5)
N2—N1—C7—C1170.5 (2)C19—C13—C14—C15−176.5 (3)
N1—N2—C8—C9178.0 (2)C14—C13—C18—C17−0.3 (5)
C19—N3—N4—C20−171.6 (3)C19—C13—C18—C17176.4 (3)
N4—N3—C19—O2−1.6 (5)C14—C13—C19—O2159.0 (3)
N4—N3—C19—C13176.5 (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—C31.5 (5)C18—C13—C19—N3164.4 (3)
C7—C1—C2—C3176.7 (3)C13—C14—C15—C160.2 (5)
C2—C1—C6—C50.2 (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—C130.4 (6)
C6—C1—C7—N1−34.0 (4)N4—C20—C21—S211.7 (5)
C2—C1—C7—N1150.9 (3)N4—C20—C21—C22−171.4 (3)
C6—C1—C7—O1143.9 (3)S2—C21—C22—C230.1 (4)
C1—C2—C3—C4−2.6 (5)C20—C21—C22—C23−177.1 (3)
C2—C3—C4—C52.1 (5)C21—C22—C23—Br2−179.1 (3)
C3—C4—C5—C6−0.5 (5)C21—C22—C23—C240.5 (4)
C4—C5—C6—C1−0.7 (5)Br2—C23—C24—S2178.73 (19)
N2—C8—C9—S1−5.8 (4)C22—C23—C24—S2−0.9 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O20.862.062.878 (3)160
N3—H3A···O1i0.862.122.951 (3)162
C6—H6···O20.932.503.231 (4)136
C20—H20···O1i0.932.493.282 (4)143

Symmetry codes: (i) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5098).

References

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