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Acta Crystallogr Sect E Struct Rep Online. 2009 April 1; 65(Pt 4): o801.
Published online 2009 March 19. doi:  10.1107/S1600536809009647
PMCID: PMC2968918

N′-(3-Bromo-5-chloro-2-hydroxy­benzyl­idene)-2-chloro­benzohydrazide methanol solvate

Abstract

In the title compound, C14H9BrCl2N2O2·CH4O, the dihedral angle between the two benzene rings is 49.2 (2)° and an intra­molecular O—H(...)N hydrogen bond occurs. In the crystal struture, mol­ecules are linked by O—H(...)O and N—H(...)O hydrogen bonds.

Related literature

For related structures, see: Fun et al. (2008 [triangle]); Ali et al. (2007 [triangle]); Zhi & Yang (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o801-scheme1.jpg

Experimental

Crystal data

  • C14H9BrCl2N2O2·CH4O
  • M r = 420.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o801-efi1.jpg
  • a = 11.221 (4) Å
  • b = 9.642 (3) Å
  • c = 15.908 (5) Å
  • β = 97.537 (5)°
  • V = 1706.3 (10) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.74 mm−1
  • T = 298 K
  • 0.17 × 0.15 × 0.12 mm

Data collection

  • Bruker SMART 1000 CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.653, T max = 0.735
  • 9257 measured reflections
  • 3666 independent reflections
  • 2345 reflections with I > 2σ(I)
  • R int = 0.035

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.103
  • S = 1.02
  • 3666 reflections
  • 214 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.49 e Å−3
  • Δρmin = −0.46 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809009647/hb2928sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009647/hb2928Isup2.hkl

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

supplementary crystallographic information

Comment

Recently, the crystal structures of hydrazone compounds have been widely studied (Fun et al., 2008; Ali et al., 2007; Zhi & Yang, 2007). In this paper, the structure of the title compound, (I), is described.

The title compound consists of a hydrazone molecule and a methanol molecule (Fig. 1). The dihedral angle between the two benzene rings is 49.2 (2)°. The methanol molecule is linked to the hydrazone molecule through an intramolecular O–H···O hydrogen bond (Table 1).

Experimental

The compound was prepared by the reaction of equimolar quantities (1.0 mmol each) of 3-bromo-5-chloro-2-hydroxybenzaldehyde and 2-chlorobenzohydrazide in methanol (100 ml) for 2 h at room temperature. The solution was kept in air for a week, forming yellow blocks of (I).

Refinement

The N-bound H atom was located in a difference Fourier map and was refined with an N–H distance restraint of 0.90 (1) Å. Other H atoms were placed in calculated positions (C–H = 0.93–0.96 Å, O–H = 0.82 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O and C15).

Figures

Fig. 1.
The molecular structure of (I), showing 30% probability displacement ellipsoids for the non-hydrogen atoms. Hydrogen bonds are indicated by dashed lines.

Crystal data

C14H9BrCl2N2O2·CH4OF(000) = 840
Mr = 420.08Dx = 1.635 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2864 reflections
a = 11.221 (4) Åθ = 2.3–24.0°
b = 9.642 (3) ŵ = 2.74 mm1
c = 15.908 (5) ÅT = 298 K
β = 97.537 (5)°Block, yellow
V = 1706.3 (10) Å30.17 × 0.15 × 0.12 mm
Z = 4

Data collection

Bruker SMART 1000 CCD diffractometer3666 independent reflections
Radiation source: fine-focus sealed tube2345 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 27.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −14→14
Tmin = 0.653, Tmax = 0.735k = −12→7
9257 measured reflectionsl = −20→19

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)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0477P)2 + 0.4564P] where P = (Fo2 + 2Fc2)/3
3666 reflections(Δ/σ)max < 0.001
214 parametersΔρmax = 0.49 e Å3
1 restraintΔρmin = −0.45 e Å3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > 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*/Ueq
Br1−0.32199 (3)0.42107 (4)0.05220 (3)0.06886 (17)
Cl1−0.23673 (8)0.95108 (9)−0.05322 (6)0.0633 (3)
Cl20.49315 (8)0.21596 (9)0.18697 (6)0.0627 (3)
N10.1502 (2)0.5525 (2)0.14404 (16)0.0412 (6)
N20.2713 (2)0.5514 (3)0.17335 (16)0.0421 (6)
O1−0.06054 (19)0.4397 (2)0.12117 (14)0.0502 (6)
H10.01130.44510.13880.075*
O20.25707 (19)0.3476 (2)0.24068 (15)0.0588 (6)
O30.1088 (2)0.2995 (3)0.36033 (16)0.0635 (6)
H30.12650.34110.31880.095*
C1−0.0179 (2)0.6676 (3)0.06979 (17)0.0372 (7)
C2−0.0965 (3)0.5573 (3)0.07949 (18)0.0379 (7)
C3−0.2162 (3)0.5705 (3)0.04383 (18)0.0422 (7)
C4−0.2581 (3)0.6892 (3)0.00215 (18)0.0467 (8)
H4−0.33840.6963−0.02100.056*
C5−0.1803 (3)0.7973 (3)−0.00500 (19)0.0440 (7)
C6−0.0613 (3)0.7871 (3)0.02778 (18)0.0432 (7)
H6−0.00940.86060.02180.052*
C70.1096 (3)0.6595 (3)0.10313 (18)0.0416 (7)
H70.16090.73230.09450.050*
C80.3161 (3)0.4461 (3)0.22296 (19)0.0397 (7)
C90.4474 (3)0.4648 (3)0.25564 (19)0.0407 (7)
C100.5333 (3)0.3652 (3)0.24473 (18)0.0428 (7)
C110.6517 (3)0.3836 (4)0.2764 (2)0.0564 (9)
H110.70840.31630.26830.068*
C120.6858 (3)0.5040 (4)0.3207 (2)0.0635 (10)
H120.76610.51730.34230.076*
C130.6033 (3)0.6032 (4)0.3332 (2)0.0596 (10)
H130.62710.68310.36360.072*
C140.4840 (3)0.5842 (3)0.3004 (2)0.0510 (8)
H140.42780.65210.30850.061*
C15−0.0087 (4)0.3311 (6)0.3718 (4)0.1076 (17)
H15A−0.00860.40560.41180.161*
H15B−0.04590.25090.39280.161*
H15C−0.05270.35870.31860.161*
H20.313 (3)0.628 (3)0.162 (2)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0512 (2)0.0795 (3)0.0725 (3)−0.0221 (2)−0.00436 (17)0.0152 (2)
Cl10.0609 (6)0.0508 (5)0.0712 (6)0.0094 (4)−0.0180 (4)0.0155 (4)
Cl20.0639 (5)0.0534 (5)0.0687 (6)0.0050 (4)0.0001 (4)−0.0110 (5)
N10.0336 (13)0.0412 (14)0.0463 (14)0.0017 (11)−0.0044 (11)−0.0008 (12)
N20.0308 (13)0.0403 (14)0.0524 (15)−0.0008 (11)−0.0044 (11)0.0080 (13)
O10.0432 (12)0.0457 (13)0.0583 (14)−0.0038 (10)−0.0059 (11)0.0127 (11)
O20.0429 (12)0.0537 (14)0.0781 (17)−0.0067 (12)0.0015 (11)0.0232 (13)
O30.0563 (14)0.0545 (15)0.0815 (18)0.0038 (12)0.0158 (12)−0.0002 (13)
C10.0387 (16)0.0364 (16)0.0347 (15)0.0018 (13)−0.0019 (13)−0.0008 (13)
C20.0409 (16)0.0401 (16)0.0315 (15)0.0009 (14)0.0002 (12)0.0011 (13)
C30.0393 (16)0.0503 (19)0.0365 (16)−0.0029 (15)0.0025 (13)−0.0018 (15)
C40.0357 (16)0.065 (2)0.0379 (17)0.0051 (17)−0.0002 (13)0.0001 (16)
C50.0471 (17)0.0391 (17)0.0434 (18)0.0091 (15)−0.0032 (14)0.0033 (15)
C60.0443 (17)0.0383 (17)0.0448 (17)−0.0007 (14)−0.0024 (14)0.0006 (15)
C70.0361 (16)0.0420 (17)0.0438 (18)−0.0011 (14)−0.0056 (13)0.0011 (15)
C80.0371 (16)0.0413 (17)0.0397 (16)0.0020 (14)0.0014 (13)0.0037 (15)
C90.0381 (16)0.0418 (17)0.0404 (17)0.0004 (14)−0.0020 (13)0.0077 (14)
C100.0435 (17)0.0456 (17)0.0376 (17)0.0022 (15)−0.0012 (14)0.0030 (14)
C110.0411 (18)0.064 (2)0.062 (2)0.0125 (17)−0.0019 (16)0.0058 (19)
C120.0423 (19)0.076 (3)0.067 (2)−0.002 (2)−0.0128 (17)0.004 (2)
C130.055 (2)0.053 (2)0.065 (2)0.0002 (18)−0.0144 (18)−0.0064 (18)
C140.0508 (19)0.0451 (19)0.054 (2)0.0036 (16)−0.0054 (16)0.0038 (16)
C150.066 (3)0.105 (4)0.155 (5)0.020 (3)0.027 (3)0.001 (4)

Geometric parameters (Å, °)

Br1—C31.883 (3)C4—H40.9300
Cl1—C51.749 (3)C5—C61.372 (4)
Cl2—C101.735 (3)C6—H60.9300
N1—C71.272 (4)C7—H70.9300
N1—N21.378 (3)C8—C91.508 (4)
N2—C81.343 (4)C9—C141.387 (4)
N2—H20.91 (3)C9—C101.388 (4)
O1—C21.348 (3)C10—C111.369 (4)
O1—H10.8200C11—C121.386 (5)
O2—C81.212 (3)C11—H110.9300
O3—C151.388 (5)C12—C131.364 (5)
O3—H30.8200C12—H120.9300
C1—C61.387 (4)C13—C141.383 (5)
C1—C21.404 (4)C13—H130.9300
C1—C71.461 (4)C14—H140.9300
C2—C31.393 (4)C15—H15A0.9600
C3—C41.374 (4)C15—H15B0.9600
C4—C51.374 (4)C15—H15C0.9600
C7—N1—N2116.8 (2)O2—C8—N2123.8 (3)
C8—N2—N1118.7 (2)O2—C8—C9123.5 (3)
C8—N2—H2125 (2)N2—C8—C9112.7 (3)
N1—N2—H2116 (2)C14—C9—C10118.3 (3)
C2—O1—H1109.5C14—C9—C8119.1 (3)
C15—O3—H3109.5C10—C9—C8122.5 (3)
C6—C1—C2119.7 (3)C11—C10—C9121.4 (3)
C6—C1—C7119.0 (3)C11—C10—Cl2118.3 (3)
C2—C1—C7121.3 (3)C9—C10—Cl2120.2 (2)
O1—C2—C3119.2 (3)C10—C11—C12119.0 (3)
O1—C2—C1122.6 (3)C10—C11—H11120.5
C3—C2—C1118.2 (3)C12—C11—H11120.5
C4—C3—C2121.6 (3)C13—C12—C11121.0 (3)
C4—C3—Br1119.5 (2)C13—C12—H12119.5
C2—C3—Br1118.9 (2)C11—C12—H12119.5
C3—C4—C5119.4 (3)C12—C13—C14119.6 (3)
C3—C4—H4120.3C12—C13—H13120.2
C5—C4—H4120.3C14—C13—H13120.2
C6—C5—C4120.7 (3)C13—C14—C9120.7 (3)
C6—C5—Cl1120.4 (2)C13—C14—H14119.6
C4—C5—Cl1118.8 (2)C9—C14—H14119.6
C5—C6—C1120.4 (3)O3—C15—H15A109.5
C5—C6—H6119.8O3—C15—H15B109.5
C1—C6—H6119.8H15A—C15—H15B109.5
N1—C7—C1119.8 (3)O3—C15—H15C109.5
N1—C7—H7120.1H15A—C15—H15C109.5
C1—C7—H7120.1H15B—C15—H15C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1···N10.821.862.585 (3)146
O3—H3···O20.822.042.727 (3)141
N2—H2···O3i0.91 (3)1.93 (3)2.830 (4)176 (4)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2928).

References

  • Ali, H. M., Zuraini, K., Wan Jefrey, B. & Ng, S. W. (2007). Acta Cryst. E63, o1729–o1730.
  • Bruker (2001). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Fun, H.-K., Jebas, S. R., Sujith, K. V., Patil, P. S. & Kalluraya, B. (2008). Acta Cryst. E64, o1907–o1908. [PMC free article] [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhi, F. & Yang, Y.-L. (2007). Acta Cryst. E63, o4471.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography