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

Weng, Q.; Zou, C.

doi:10.1107/S1600536809009647

organic compounds

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Volume 65| Part 4| April 2009| Page o801

doi:10.1107/S1600536809009647

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

Qianfeng Weng ^a ^* and Cunjie Zou ^a

^aCollege of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China
^*Correspondence e-mail: qianfeng_weng@163.com

(Received 16 March 2009; accepted 16 March 2009; online 19 March 2009)

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 ); Ali et al. (2007 ); Zhi & Yang (2007 ).

Experimental

Crystal data

C₁₄H₉BrCl₂N₂O₂·CH₄O
M_r = 420.08
Monoclinic, P 2₁ /n
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 ) 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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.103
S = 1.02
3666 reflections
214 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.82	1.86	2.585 (3)	146
O3—H3⋯O2	0.82	2.04	2.727 (3)	141
N2—H2⋯O3ⁱ	0.91 (3)	1.93 (3)	2.830 (4)	176 (4)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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/S1600536809009647/hb2928sup1.cif

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (I), showing 30% probability displacement ellipsoids for the non-hydrogen atoms. Hydrogen bonds are indicated by dashed lines.

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

Crystal data top

C₁₄H₉BrCl₂N₂O₂·CH₄O	F(000) = 840
M_r = 420.08	D_x = 1.635 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2864 reflections
a = 11.221 (4) Å	θ = 2.3–24.0°
b = 9.642 (3) Å	µ = 2.74 mm⁻¹
c = 15.908 (5) Å	T = 298 K
β = 97.537 (5)°	Block, yellow
V = 1706.3 (10) Å³	0.17 × 0.15 × 0.12 mm
Z = 4

Data collection top

Bruker SMART 1000 CCD diffractometer	3666 independent reflections
Radiation source: fine-focus sealed tube	2345 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
T_min = 0.653, T_max = 0.735	k = −12→7
9257 measured reflections	l = −20→19

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0477P)² + 0.4564P] where P = (F_o² + 2F_c²)/3
3666 reflections	(Δ/σ)_max < 0.001
214 parameters	Δρ_max = 0.49 e Å⁻³
1 restraint	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₄H₉BrCl₂N₂O₂·CH₄O	V = 1706.3 (10) Å³
M_r = 420.08	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.221 (4) Å	µ = 2.74 mm⁻¹
b = 9.642 (3) Å	T = 298 K
c = 15.908 (5) Å	0.17 × 0.15 × 0.12 mm
β = 97.537 (5)°

Data collection top

Bruker SMART 1000 CCD diffractometer	3666 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2345 reflections with I > 2σ(I)
T_min = 0.653, T_max = 0.735	R_int = 0.035
9257 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	1 restraint
wR(F²) = 0.103	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.49 e Å⁻³
3666 reflections	Δρ_min = −0.46 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	−0.32199 (3)	0.42107 (4)	0.05220 (3)	0.06886 (17)
Cl1	−0.23673 (8)	0.95108 (9)	−0.05322 (6)	0.0633 (3)
Cl2	0.49315 (8)	0.21596 (9)	0.18697 (6)	0.0627 (3)
N1	0.1502 (2)	0.5525 (2)	0.14404 (16)	0.0412 (6)
N2	0.2713 (2)	0.5514 (3)	0.17335 (16)	0.0421 (6)
O1	−0.06054 (19)	0.4397 (2)	0.12117 (14)	0.0502 (6)
H1	0.0113	0.4451	0.1388	0.075*
O2	0.25707 (19)	0.3476 (2)	0.24068 (15)	0.0588 (6)
O3	0.1088 (2)	0.2995 (3)	0.36033 (16)	0.0635 (6)
H3	0.1265	0.3411	0.3188	0.095*
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	−0.3384	0.6963	−0.0210	0.056*
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	−0.0094	0.8606	0.0218	0.052*
C7	0.1096 (3)	0.6595 (3)	0.10313 (18)	0.0416 (7)
H7	0.1609	0.7323	0.0945	0.050*
C8	0.3161 (3)	0.4461 (3)	0.22296 (19)	0.0397 (7)
C9	0.4474 (3)	0.4648 (3)	0.25564 (19)	0.0407 (7)
C10	0.5333 (3)	0.3652 (3)	0.24473 (18)	0.0428 (7)
C11	0.6517 (3)	0.3836 (4)	0.2764 (2)	0.0564 (9)
H11	0.7084	0.3163	0.2683	0.068*
C12	0.6858 (3)	0.5040 (4)	0.3207 (2)	0.0635 (10)
H12	0.7661	0.5173	0.3423	0.076*
C13	0.6033 (3)	0.6032 (4)	0.3332 (2)	0.0596 (10)
H13	0.6271	0.6831	0.3636	0.072*
C14	0.4840 (3)	0.5842 (3)	0.3004 (2)	0.0510 (8)
H14	0.4278	0.6521	0.3085	0.061*
C15	−0.0087 (4)	0.3311 (6)	0.3718 (4)	0.1076 (17)
H15A	−0.0086	0.4056	0.4118	0.161*
H15B	−0.0459	0.2509	0.3928	0.161*
H15C	−0.0527	0.3587	0.3186	0.161*
H2	0.313 (3)	0.628 (3)	0.162 (2)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0512 (2)	0.0795 (3)	0.0725 (3)	−0.0221 (2)	−0.00436 (17)	0.0152 (2)
Cl1	0.0609 (6)	0.0508 (5)	0.0712 (6)	0.0094 (4)	−0.0180 (4)	0.0155 (4)
Cl2	0.0639 (5)	0.0534 (5)	0.0687 (6)	0.0050 (4)	0.0001 (4)	−0.0110 (5)
N1	0.0336 (13)	0.0412 (14)	0.0463 (14)	0.0017 (11)	−0.0044 (11)	−0.0008 (12)
N2	0.0308 (13)	0.0403 (14)	0.0524 (15)	−0.0008 (11)	−0.0044 (11)	0.0080 (13)
O1	0.0432 (12)	0.0457 (13)	0.0583 (14)	−0.0038 (10)	−0.0059 (11)	0.0127 (11)
O2	0.0429 (12)	0.0537 (14)	0.0781 (17)	−0.0067 (12)	0.0015 (11)	0.0232 (13)
O3	0.0563 (14)	0.0545 (15)	0.0815 (18)	0.0038 (12)	0.0158 (12)	−0.0002 (13)
C1	0.0387 (16)	0.0364 (16)	0.0347 (15)	0.0018 (13)	−0.0019 (13)	−0.0008 (13)
C2	0.0409 (16)	0.0401 (16)	0.0315 (15)	0.0009 (14)	0.0002 (12)	0.0011 (13)
C3	0.0393 (16)	0.0503 (19)	0.0365 (16)	−0.0029 (15)	0.0025 (13)	−0.0018 (15)
C4	0.0357 (16)	0.065 (2)	0.0379 (17)	0.0051 (17)	−0.0002 (13)	0.0001 (16)
C5	0.0471 (17)	0.0391 (17)	0.0434 (18)	0.0091 (15)	−0.0032 (14)	0.0033 (15)
C6	0.0443 (17)	0.0383 (17)	0.0448 (17)	−0.0007 (14)	−0.0024 (14)	0.0006 (15)
C7	0.0361 (16)	0.0420 (17)	0.0438 (18)	−0.0011 (14)	−0.0056 (13)	0.0011 (15)
C8	0.0371 (16)	0.0413 (17)	0.0397 (16)	0.0020 (14)	0.0014 (13)	0.0037 (15)
C9	0.0381 (16)	0.0418 (17)	0.0404 (17)	0.0004 (14)	−0.0020 (13)	0.0077 (14)
C10	0.0435 (17)	0.0456 (17)	0.0376 (17)	0.0022 (15)	−0.0012 (14)	0.0030 (14)
C11	0.0411 (18)	0.064 (2)	0.062 (2)	0.0125 (17)	−0.0019 (16)	0.0058 (19)
C12	0.0423 (19)	0.076 (3)	0.067 (2)	−0.002 (2)	−0.0128 (17)	0.004 (2)
C13	0.055 (2)	0.053 (2)	0.065 (2)	0.0002 (18)	−0.0144 (18)	−0.0064 (18)
C14	0.0508 (19)	0.0451 (19)	0.054 (2)	0.0036 (16)	−0.0054 (16)	0.0038 (16)
C15	0.066 (3)	0.105 (4)	0.155 (5)	0.020 (3)	0.027 (3)	0.001 (4)

Geometric parameters (Å, º) top

Br1—C3	1.883 (3)	C4—H4	0.9300
Cl1—C5	1.749 (3)	C5—C6	1.372 (4)
Cl2—C10	1.735 (3)	C6—H6	0.9300
N1—C7	1.272 (4)	C7—H7	0.9300
N1—N2	1.378 (3)	C8—C9	1.508 (4)
N2—C8	1.343 (4)	C9—C14	1.387 (4)
N2—H2	0.91 (3)	C9—C10	1.388 (4)
O1—C2	1.348 (3)	C10—C11	1.369 (4)
O1—H1	0.8200	C11—C12	1.386 (5)
O2—C8	1.212 (3)	C11—H11	0.9300
O3—C15	1.388 (5)	C12—C13	1.364 (5)
O3—H3	0.8200	C12—H12	0.9300
C1—C6	1.387 (4)	C13—C14	1.383 (5)
C1—C2	1.404 (4)	C13—H13	0.9300
C1—C7	1.461 (4)	C14—H14	0.9300
C2—C3	1.393 (4)	C15—H15A	0.9600
C3—C4	1.374 (4)	C15—H15B	0.9600
C4—C5	1.374 (4)	C15—H15C	0.9600

C7—N1—N2	116.8 (2)	O2—C8—N2	123.8 (3)
C8—N2—N1	118.7 (2)	O2—C8—C9	123.5 (3)
C8—N2—H2	125 (2)	N2—C8—C9	112.7 (3)
N1—N2—H2	116 (2)	C14—C9—C10	118.3 (3)
C2—O1—H1	109.5	C14—C9—C8	119.1 (3)
C15—O3—H3	109.5	C10—C9—C8	122.5 (3)
C6—C1—C2	119.7 (3)	C11—C10—C9	121.4 (3)
C6—C1—C7	119.0 (3)	C11—C10—Cl2	118.3 (3)
C2—C1—C7	121.3 (3)	C9—C10—Cl2	120.2 (2)
O1—C2—C3	119.2 (3)	C10—C11—C12	119.0 (3)
O1—C2—C1	122.6 (3)	C10—C11—H11	120.5
C3—C2—C1	118.2 (3)	C12—C11—H11	120.5
C4—C3—C2	121.6 (3)	C13—C12—C11	121.0 (3)
C4—C3—Br1	119.5 (2)	C13—C12—H12	119.5
C2—C3—Br1	118.9 (2)	C11—C12—H12	119.5
C3—C4—C5	119.4 (3)	C12—C13—C14	119.6 (3)
C3—C4—H4	120.3	C12—C13—H13	120.2
C5—C4—H4	120.3	C14—C13—H13	120.2
C6—C5—C4	120.7 (3)	C13—C14—C9	120.7 (3)
C6—C5—Cl1	120.4 (2)	C13—C14—H14	119.6
C4—C5—Cl1	118.8 (2)	C9—C14—H14	119.6
C5—C6—C1	120.4 (3)	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	119.8 (3)	O3—C15—H15C	109.5
N1—C7—H7	120.1	H15A—C15—H15C	109.5
C1—C7—H7	120.1	H15B—C15—H15C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.86	2.585 (3)	146
O3—H3···O2	0.82	2.04	2.727 (3)	141
N2—H2···O3ⁱ	0.91 (3)	1.93 (3)	2.830 (4)	176 (4)

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

Experimental details

Crystal data
Chemical formula	C₁₄H₉BrCl₂N₂O₂·CH₄O
M_r	420.08
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	11.221 (4), 9.642 (3), 15.908 (5)
β (°)	97.537 (5)
V (Å³)	1706.3 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.74
Crystal size (mm)	0.17 × 0.15 × 0.12

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.653, 0.735
No. of measured, independent and observed [I > 2σ(I)] reflections	9257, 3666, 2345
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.02
No. of reflections	3666
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)	0.49, −0.46

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.86	2.585 (3)	146
O3—H3···O2	0.82	2.04	2.727 (3)	141
N2—H2···O3ⁱ	0.91 (3)	1.93 (3)	2.830 (4)	176 (4)

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

References

Ali, H. M., Zuraini, K., Wan Jefrey, B. & Ng, S. W. (2007). Acta Cryst. E63, o1729–o1730. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fun, H.-K., Jebas, S. R., Sujith, K. V., Patil, P. S. & Kalluraya, B. (2008). Acta Cryst. E64, o1907–o1908. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhi, F. & Yang, Y.-L. (2007). Acta Cryst. E63, o4471. Web of Science CSD CrossRef IUCr Journals Google Scholar

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

References

organic compounds

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