3-Chloro-N′-(3,5-dibromo-2-hy­droxy­benzyl­idene)benzohydrazide methanol monosolvate

Li, T.-Y.; Qu, Y.-G.

doi:10.1107/S1600536811000742

organic compounds

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doi:10.1107/S1600536811000742

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3-Chloro-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide methanol monosolvate

Tian-Yi Li ^a ^* and Yue-Gang Qu ^a

^aSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: cooperationwell@126.com

(Received 31 December 2010; accepted 6 January 2011; online 12 January 2011)

The title Schiff base compound, C₁₄H₉Br₂ClN₂O₂·CH₃OH, features an intramolecular O—H⋯N hydrogen bond, which contributes to the planarity of the molecule: the dihedral angle between the two benzene rings is 4.6 (2)°. In the crystal, pairs of adjacent molecules are linked through intermolecular N—H⋯O and O—H⋯O hydrogen bonds, forming dimers. The methanol solvent molecule is linked by intermolecular O—H⋯O hydrogen bonds.

Related literature

For Schiff base compounds derived from the reaction of aldehydes with benzohydrazides, see: Pouralimardan et al. (2007); Dinda et al. (2002 ); Podyachev et al. (2007 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₉Br₂ClN₂O₂·CH₄O
M_r = 464.54
Triclinic, $[P \overline 1]$
a = 8.8560 (18) Å
b = 9.3810 (19) Å
c = 11.205 (2) Å
α = 95.634 (3)°
β = 110.952 (3)°
γ = 99.392 (3)°
V = 845.2 (3) Å³
Z = 2
Mo Kα radiation
μ = 4.97 mm⁻¹
T = 298 K
0.18 × 0.17 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.468, T_max = 0.486
7213 measured reflections
3504 independent reflections
2423 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.117
S = 1.03
3504 reflections
214 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3ⁱ	0.90 (4)	1.98 (2)	2.852 (4)	165 (5)
O3—H3⋯O2ⁱⁱ	0.82	1.98	2.769 (4)	161
O1—H1⋯N1	0.82	1.85	2.566 (4)	146
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x, y, z-1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811000742/hg2785sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811000742/hg2785Isup2.hkl

checkCIF report

Comment top

In the last few years, a number of Schiff bases derived from the reaction of aldehydes with benzohydrazides were prepared and structurally characterized (Pouralimardan et al., 2007; Dinda et al., 2002). As a continuation of the work, in the present paper, the structure of the title Schiff base compound, (Fig. 1) is reported.

In the title compound, there is an O—H···N hydrogen bond, which contributes to the planarity of the molecule. The dihedral angle between the two benzene rings is 4.6 (2)°. All the bond lengths are within normal values (Allen et al., 1987). The adjacent two molecules are linked through intermolecular N—H···O and O—H···O hydrogen bonds (Table 1) to form a dimer (Fig. 2). The methanol solvate is linked by intermolecular O—H···O hydrogen bonds.

Related literature top

For Schiff base compounds derived from the reaction of aldehydes with benzohydrazides, see: Pouralimardan et al. (2007); Dinda et al. (2002); Podyachev et al. (2007). For reference bond lengths, see: Allen et al. (1987).

Experimental top

3,5-dibromo-2-hydroxybenzaldehyde (0.280 g, 1 mmol) and 3-chlorobenzohydrazide (0.171 g, 1 mmol) were dissolved in 30 ml absolute methanol. The mixture was stirred at reflux for 10 min, and cooled to room temperature. The clear colorless solution was left to slow evaporation in air for three days, yielding colorless block-shaped crystals, which were collected by filtration and washed with methanol.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-hydrogen atoms. Hydrogen bonds are drawn as dashed lines.
	Fig. 2. The molecular packing of the title compound. Hydrogen bonds are drawn as dashed lines.

3-Chloro-N'-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide methanol monosolvate top

Crystal data top

C₁₄H₉Br₂ClN₂O₂·CH₄O	Z = 2
M_r = 464.54	F(000) = 456
Triclinic, P1	D_x = 1.825 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8560 (18) Å	Cell parameters from 2168 reflections
b = 9.3810 (19) Å	θ = 2.5–25.9°
c = 11.205 (2) Å	µ = 4.97 mm⁻¹
α = 95.634 (3)°	T = 298 K
β = 110.952 (3)°	Block, colorless
γ = 99.392 (3)°	0.18 × 0.17 × 0.17 mm
V = 845.2 (3) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3504 independent reflections
Radiation source: fine-focus sealed tube	2423 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→11
T_min = 0.468, T_max = 0.486	k = −11→11
7213 measured reflections	l = −14→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.050P)² + 0.0441P] where P = (F_o² + 2F_c²)/3
3504 reflections	(Δ/σ)_max < 0.001
214 parameters	Δρ_max = 0.61 e Å⁻³
1 restraint	Δρ_min = −0.71 e Å⁻³

Crystal data top

C₁₄H₉Br₂ClN₂O₂·CH₄O	γ = 99.392 (3)°
M_r = 464.54	V = 845.2 (3) Å³
Triclinic, P1	Z = 2
a = 8.8560 (18) Å	Mo Kα radiation
b = 9.3810 (19) Å	µ = 4.97 mm⁻¹
c = 11.205 (2) Å	T = 298 K
α = 95.634 (3)°	0.18 × 0.17 × 0.17 mm
β = 110.952 (3)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3504 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2423 reflections with I > 2σ(I)
T_min = 0.468, T_max = 0.486	R_int = 0.036
7213 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	1 restraint
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.61 e Å⁻³
3504 reflections	Δρ_min = −0.71 e Å⁻³
214 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br1	0.29523 (6)	0.00200 (5)	1.38779 (5)	0.0684 (2)
Br2	−0.39950 (6)	−0.16848 (6)	1.18451 (5)	0.0754 (2)
Cl1	−0.12376 (13)	0.68386 (11)	0.50390 (9)	0.0538 (3)
N1	0.0467 (4)	0.2942 (3)	0.9916 (3)	0.0375 (7)
N2	0.0405 (4)	0.3784 (3)	0.8978 (3)	0.0386 (7)
O1	0.2266 (3)	0.1922 (3)	1.1849 (3)	0.0496 (7)
H1	0.2078	0.2450	1.1295	0.074*
O2	0.3090 (3)	0.4803 (3)	1.0115 (3)	0.0533 (7)
O3	0.2945 (3)	0.6052 (3)	0.2405 (3)	0.0578 (8)
H3	0.3060	0.5530	0.1826	0.087*
C1	−0.0709 (5)	0.1171 (4)	1.0859 (3)	0.0338 (8)
C2	0.0834 (4)	0.1111 (4)	1.1785 (3)	0.0346 (8)
C3	0.0872 (4)	0.0173 (4)	1.2683 (3)	0.0388 (8)
C4	−0.0538 (5)	−0.0650 (4)	1.2702 (3)	0.0439 (9)
H4	−0.0484	−0.1259	1.3316	0.053*
C5	−0.2040 (5)	−0.0563 (4)	1.1797 (4)	0.0420 (9)
C6	−0.2136 (5)	0.0304 (4)	1.0871 (3)	0.0392 (8)
H6	−0.3162	0.0315	1.0246	0.047*
C7	−0.0839 (4)	0.2091 (4)	0.9867 (3)	0.0356 (8)
H7	−0.1856	0.2058	0.9212	0.043*
C8	0.1846 (4)	0.4709 (4)	0.9153 (3)	0.0349 (8)
C9	0.1854 (4)	0.5574 (4)	0.8114 (3)	0.0341 (8)
C10	0.0427 (4)	0.5745 (3)	0.7138 (3)	0.0349 (8)
H10	−0.0608	0.5274	0.7088	0.042*
C11	0.0560 (5)	0.6615 (4)	0.6248 (3)	0.0388 (8)
C12	0.2061 (5)	0.7299 (4)	0.6284 (4)	0.0503 (10)
H12	0.2126	0.7875	0.5667	0.060*
C13	0.3475 (5)	0.7129 (5)	0.7242 (4)	0.0560 (11)
H13	0.4504	0.7598	0.7279	0.067*
C14	0.3379 (5)	0.6269 (4)	0.8146 (4)	0.0459 (9)
H14	0.4345	0.6151	0.8785	0.055*
C15	0.4103 (6)	0.5924 (6)	0.3610 (4)	0.0718 (14)
H15A	0.5198	0.6338	0.3671	0.108*
H15B	0.4020	0.4907	0.3691	0.108*
H15C	0.3882	0.6438	0.4293	0.108*
H2	−0.060 (3)	0.383 (5)	0.842 (4)	0.086*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0442 (3)	0.0852 (4)	0.0707 (3)	0.0200 (2)	0.0048 (2)	0.0458 (3)
Br2	0.0454 (3)	0.0852 (4)	0.0891 (4)	−0.0070 (2)	0.0186 (3)	0.0470 (3)
Cl1	0.0495 (6)	0.0638 (6)	0.0440 (6)	0.0160 (5)	0.0074 (5)	0.0251 (5)
N1	0.0416 (18)	0.0382 (16)	0.0383 (17)	0.0134 (14)	0.0164 (15)	0.0195 (13)
N2	0.0362 (18)	0.0394 (16)	0.0402 (18)	0.0099 (14)	0.0104 (15)	0.0198 (14)
O1	0.0347 (15)	0.0582 (17)	0.0538 (17)	0.0050 (13)	0.0113 (13)	0.0294 (13)
O2	0.0344 (15)	0.078 (2)	0.0455 (16)	0.0117 (14)	0.0079 (13)	0.0314 (14)
O3	0.0395 (16)	0.079 (2)	0.0466 (17)	0.0142 (15)	0.0039 (14)	0.0187 (15)
C1	0.042 (2)	0.0317 (18)	0.0286 (18)	0.0103 (15)	0.0115 (16)	0.0120 (14)
C2	0.0297 (19)	0.0355 (19)	0.039 (2)	0.0093 (15)	0.0112 (17)	0.0104 (15)
C3	0.036 (2)	0.041 (2)	0.0352 (19)	0.0115 (17)	0.0050 (17)	0.0148 (16)
C4	0.046 (2)	0.041 (2)	0.046 (2)	0.0125 (18)	0.015 (2)	0.0217 (18)
C5	0.037 (2)	0.041 (2)	0.046 (2)	0.0011 (17)	0.0141 (19)	0.0136 (17)
C6	0.033 (2)	0.042 (2)	0.040 (2)	0.0082 (17)	0.0081 (17)	0.0134 (16)
C7	0.033 (2)	0.0370 (19)	0.0334 (19)	0.0102 (16)	0.0061 (16)	0.0127 (15)
C8	0.0312 (19)	0.0416 (19)	0.036 (2)	0.0130 (16)	0.0136 (17)	0.0146 (15)
C9	0.036 (2)	0.0349 (19)	0.0340 (19)	0.0109 (16)	0.0136 (17)	0.0081 (15)
C10	0.032 (2)	0.039 (2)	0.0345 (19)	0.0081 (16)	0.0123 (17)	0.0110 (16)
C11	0.043 (2)	0.038 (2)	0.036 (2)	0.0135 (17)	0.0119 (18)	0.0121 (16)
C12	0.054 (3)	0.054 (2)	0.056 (2)	0.018 (2)	0.028 (2)	0.029 (2)
C13	0.037 (2)	0.068 (3)	0.070 (3)	0.008 (2)	0.026 (2)	0.031 (2)
C14	0.031 (2)	0.057 (2)	0.052 (2)	0.0115 (18)	0.0152 (19)	0.0227 (19)
C15	0.045 (3)	0.104 (4)	0.055 (3)	0.007 (3)	0.005 (2)	0.031 (3)

Geometric parameters (Å, º) top

Br1—C3	1.889 (3)	C4—H4	0.9300
Br2—C5	1.895 (4)	C5—C6	1.368 (5)
Cl1—C11	1.743 (4)	C6—H6	0.9300
N1—C7	1.274 (4)	C7—H7	0.9300
N1—N2	1.367 (4)	C8—C9	1.484 (4)
N2—C8	1.359 (5)	C9—C14	1.387 (5)
N2—H2	0.90 (4)	C9—C10	1.389 (4)
O1—C2	1.342 (4)	C10—C11	1.374 (4)
O1—H1	0.8200	C10—H10	0.9300
O2—C8	1.218 (4)	C11—C12	1.363 (6)
O3—C15	1.404 (5)	C12—C13	1.373 (6)
O3—H3	0.8200	C12—H12	0.9300
C1—C6	1.392 (5)	C13—C14	1.373 (5)
C1—C2	1.403 (5)	C13—H13	0.9300
C1—C7	1.457 (4)	C14—H14	0.9300
C2—C3	1.396 (5)	C15—H15A	0.9600
C3—C4	1.366 (5)	C15—H15B	0.9600
C4—C5	1.375 (5)	C15—H15C	0.9600

C7—N1—N2	120.4 (3)	O2—C8—N2	121.2 (3)
C8—N2—N1	115.9 (3)	O2—C8—C9	121.3 (3)
C8—N2—H2	125 (3)	N2—C8—C9	117.4 (3)
N1—N2—H2	118 (3)	C14—C9—C10	118.8 (3)
C2—O1—H1	109.5	C14—C9—C8	117.5 (3)
C15—O3—H3	109.5	C10—C9—C8	123.7 (3)
C6—C1—C2	119.2 (3)	C11—C10—C9	119.4 (3)
C6—C1—C7	119.5 (3)	C11—C10—H10	120.3
C2—C1—C7	121.3 (3)	C9—C10—H10	120.3
O1—C2—C3	118.8 (3)	C12—C11—C10	121.7 (3)
O1—C2—C1	123.0 (3)	C12—C11—Cl1	119.3 (3)
C3—C2—C1	118.3 (3)	C10—C11—Cl1	119.0 (3)
C4—C3—C2	122.0 (3)	C11—C12—C13	119.2 (3)
C4—C3—Br1	119.6 (3)	C11—C12—H12	120.4
C2—C3—Br1	118.4 (3)	C13—C12—H12	120.4
C3—C4—C5	118.8 (3)	C12—C13—C14	120.4 (4)
C3—C4—H4	120.6	C12—C13—H13	119.8
C5—C4—H4	120.6	C14—C13—H13	119.8
C6—C5—C4	121.2 (3)	C13—C14—C9	120.5 (4)
C6—C5—Br2	120.2 (3)	C13—C14—H14	119.7
C4—C5—Br2	118.6 (3)	C9—C14—H14	119.7
C5—C6—C1	120.4 (4)	O3—C15—H15A	109.5
C5—C6—H6	119.8	O3—C15—H15B	109.5
C1—C6—H6	119.8	H15A—C15—H15B	109.5
N1—C7—C1	118.7 (3)	O3—C15—H15C	109.5
N1—C7—H7	120.6	H15A—C15—H15C	109.5
C1—C7—H7	120.6	H15B—C15—H15C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.90 (4)	1.98 (2)	2.852 (4)	165 (5)
O3—H3···O2ⁱⁱ	0.82	1.98	2.769 (4)	161
O1—H1···N1	0.82	1.85	2.566 (4)	146

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉Br₂ClN₂O₂·CH₄O
M_r	464.54
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.8560 (18), 9.3810 (19), 11.205 (2)
α, β, γ (°)	95.634 (3), 110.952 (3), 99.392 (3)
V (Å³)	845.2 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	4.97
Crystal size (mm)	0.18 × 0.17 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.468, 0.486
No. of measured, independent and observed [I > 2σ(I)] reflections	7213, 3504, 2423
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.03
No. of reflections	3504
No. of parameters	214
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.61, −0.71

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3ⁱ	0.90 (4)	1.976 (17)	2.852 (4)	165 (5)
O3—H3···O2ⁱⁱ	0.82	1.98	2.769 (4)	161
O1—H1···N1	0.82	1.85	2.566 (4)	146

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2005). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dinda, R., Sengupta, P., Ghosh, S., Mayer-Figge, H. & Sheldrick, W. S. (2002). J. Chem. Soc. Dalton Trans. pp. 4434–4439. Web of Science CSD CrossRef Google Scholar
Podyachev, S. N., Litvinov, I. A., Shagidullin, R. R., Buzykin, B. I., Bauer, I., Osyanina, D. V., Avvakumova, L. V., Sudakova, S. N., Habicher, W. D. & Konovalov, A. I. (2007). Spectrochim. Acta Part A, 66, 250–261. CSD CrossRef CAS Google Scholar
Pouralimardan, O., Chamayou, A.-C., Janiak, C. & Hosseini-Monfared, H. (2007). Inorg. Chim. Acta 360, 1599–1608. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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3-Chloro-N′-(3,5-di­bromo-2-hy­dr­oxy­benzyl­­idene)benzohydrazide methanol monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

3-Chloro-N′-(3,5-dibromo-2-hydroxybenzylidene)benzohydrazide methanol monosolvate