N′-(5-Bromo-2-hy­droxy­benzyl­idene)-4-methyl­benzohydrazide

Yang, D.-S.

doi:10.1107/S1600536811043960

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page o3090

doi:10.1107/S1600536811043960

Open

access

N′-(5-Bromo-2-hydroxybenzylidene)-4-methylbenzohydrazide

De-Suo Yang ^a ^*

^aDepartment of Chemistry and Chemical Engineering, Baoji University of Arts and Sciences, Baoji 721007, People's Republic of China
^*Correspondence e-mail: desuoyang@yahoo.com.cn

(Received 19 October 2011; accepted 23 October 2011; online 29 October 2011)

The molecule of the title compound, C₁₅H₁₃BrN₂O₂, displays an E conformation with respect to the C=N double bond and the dihedral angle between the planes of the benzene rings is 3.1 (2)°. An intramolecular O—H⋯N interaction generates an S(6) ring. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, forming C(4) chains along the c-axis direction.

Related literature

For a related structure and background references, see: Yang (2008 ). For reference bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₃BrN₂O₂
M_r = 333.18
Monoclinic, P 2₁ /n
a = 5.8290 (15) Å
b = 31.914 (3) Å
c = 7.6440 (11) Å
β = 91.535 (2)°
V = 1421.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.89 mm⁻¹
T = 298 K
0.27 × 0.23 × 0.23 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.509, T_max = 0.556
11208 measured reflections
3095 independent reflections
1794 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.147
S = 1.03
3095 reflections
186 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.77 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	1.94	2.653 (5)	146
N2—H2⋯O2ⁱ	0.90 (1)	2.00 (2)	2.856 (5)	159 (5)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811043960/hb6461sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811043960/hb6461Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811043960/hb6461Isup3.cml

checkCIF report

Comment top

As part of our ongoing studies of hydrazone compounds (Yang, 2008), the crystal structure of the title new hydrazone compound is reported.

In the title compound, Fig. 1, the molecule displays an E configuration with respect to the C═N double bond. The two benzene rings form a dihedral angle of 3.1 (2)°. All the bond lengths are within normal ranges (Allen et al., 1987). The C7═N1 bond length of 1.267 (5) Å, conforms to the value for a double bond. The bond length of 1.346 (6) Å between atoms C8 and N2, is intermediate between a C—N single bond and a C═N double bond, because of conjugation effects in the molecule.

In the crystal structure, molecules are linked through N—H···O hydrogen bonds (Table 1), forming chains along the c axis (Fig. 2).

Related literature top

For a related structure and background references, see: Yang (2008). For reference bond lengths, see: Allen et al. (1987).

Experimental top

5-Bromo-2-hydroxybenzaldehyde (0.1 mmol, 20.1 mg) and 4-methylbenzohydrazide (0.1 mmol, 15.0 mg) were dissolved in CHCl₃ (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Colourless blocks of the title compound were formed by gradual evaporation of the solvent over a period of a week at room temperature.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of the title compound showing displacement ellipsoids drawn at the 30% probability level. Hydrogen bond is shown as a dashed line.
	Fig. 2. Molecular packing as viewed along the a axis. Hydrogen bonds are shown as dashed lines.

N'-(5-Bromo-2-hydroxybenzylidene)-4-methylbenzohydrazide top

Crystal data top

C₁₅H₁₃BrN₂O₂	F(000) = 672
M_r = 333.18	D_x = 1.557 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2291 reflections
a = 5.8290 (15) Å	θ = 2.5–24.1°
b = 31.914 (3) Å	µ = 2.89 mm⁻¹
c = 7.6440 (11) Å	T = 298 K
β = 91.535 (2)°	Block, colorless
V = 1421.5 (4) Å³	0.27 × 0.23 × 0.23 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3095 independent reflections
Radiation source: fine-focus sealed tube	1794 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 27.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→7
T_min = 0.509, T_max = 0.556	k = −40→36
11208 measured reflections	l = −9→9

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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0437P)² + 2.875P] where P = (F_o² + 2F_c²)/3
3095 reflections	(Δ/σ)_max = 0.001
186 parameters	Δρ_max = 0.90 e Å⁻³
1 restraint	Δρ_min = −0.77 e Å⁻³

Crystal data top

C₁₅H₁₃BrN₂O₂	V = 1421.5 (4) Å³
M_r = 333.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.8290 (15) Å	µ = 2.89 mm⁻¹
b = 31.914 (3) Å	T = 298 K
c = 7.6440 (11) Å	0.27 × 0.23 × 0.23 mm
β = 91.535 (2)°

Data collection top

Bruker SMART CCD diffractometer	3095 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	1794 reflections with I > 2σ(I)
T_min = 0.509, T_max = 0.556	R_int = 0.039
11208 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	1 restraint
wR(F²) = 0.147	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.90 e Å⁻³
3095 reflections	Δρ_min = −0.77 e Å⁻³
186 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	0.79558 (13)	0.008223 (19)	0.78795 (10)	0.0890 (3)
N1	0.6602 (6)	0.20499 (12)	0.6325 (5)	0.0457 (9)
N2	0.7868 (7)	0.24095 (12)	0.6598 (5)	0.0495 (10)
O1	0.2871 (5)	0.16182 (12)	0.5406 (5)	0.0637 (9)
H1	0.3660	0.1829	0.5528	0.096*
O2	0.5871 (6)	0.27644 (10)	0.4522 (4)	0.0613 (9)
C1	0.6256 (7)	0.13181 (14)	0.6772 (5)	0.0414 (10)
C2	0.4073 (8)	0.12798 (16)	0.5996 (6)	0.0490 (11)
C3	0.3068 (9)	0.08853 (18)	0.5819 (7)	0.0621 (14)
H3	0.1613	0.0861	0.5300	0.075*
C4	0.4188 (10)	0.05350 (18)	0.6397 (7)	0.0643 (14)
H4	0.3497	0.0273	0.6280	0.077*
C5	0.6353 (9)	0.05702 (16)	0.7156 (6)	0.0542 (12)
C6	0.7349 (8)	0.09550 (15)	0.7348 (6)	0.0485 (11)
H6	0.8800	0.0974	0.7878	0.058*
C7	0.7427 (8)	0.17169 (14)	0.6988 (6)	0.0460 (11)
H7	0.8808	0.1728	0.7625	0.055*
C8	0.7419 (7)	0.27557 (14)	0.5644 (6)	0.0432 (10)
C9	0.8885 (7)	0.31259 (13)	0.6038 (5)	0.0405 (10)
C10	1.1045 (7)	0.30975 (15)	0.6837 (6)	0.0470 (11)
H10	1.1659	0.2836	0.7120	0.056*
C11	1.2287 (8)	0.34575 (16)	0.7212 (6)	0.0534 (12)
H11	1.3736	0.3434	0.7742	0.064*
C12	1.1425 (8)	0.38513 (15)	0.6819 (6)	0.0476 (11)
C13	0.9283 (8)	0.38744 (15)	0.6002 (6)	0.0507 (12)
H13	0.8673	0.4135	0.5707	0.061*
C14	0.8044 (8)	0.35190 (14)	0.5619 (6)	0.0471 (11)
H14	0.6609	0.3543	0.5066	0.056*
C15	1.2769 (9)	0.42404 (17)	0.7256 (7)	0.0656 (15)
H15A	1.2479	0.4323	0.8437	0.098*
H15B	1.2311	0.4461	0.6469	0.098*
H15C	1.4377	0.4185	0.7141	0.098*
H2	0.897 (7)	0.2419 (17)	0.744 (5)	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.1148 (6)	0.0476 (3)	0.1037 (6)	0.0021 (3)	−0.0128 (4)	−0.0034 (3)
N1	0.041 (2)	0.051 (2)	0.044 (2)	−0.0050 (18)	−0.0146 (17)	−0.0014 (19)
N2	0.053 (2)	0.046 (2)	0.048 (2)	−0.0066 (18)	−0.0245 (18)	0.0062 (18)
O1	0.0426 (19)	0.080 (3)	0.067 (2)	−0.0050 (18)	−0.0158 (17)	0.002 (2)
O2	0.068 (2)	0.053 (2)	0.060 (2)	0.0059 (17)	−0.0395 (18)	−0.0024 (16)
C1	0.038 (2)	0.055 (3)	0.031 (2)	−0.010 (2)	−0.0030 (19)	−0.005 (2)
C2	0.048 (3)	0.063 (3)	0.036 (2)	−0.001 (2)	−0.001 (2)	0.000 (2)
C3	0.049 (3)	0.081 (4)	0.056 (3)	−0.026 (3)	−0.007 (2)	−0.009 (3)
C4	0.073 (4)	0.060 (3)	0.060 (3)	−0.024 (3)	0.002 (3)	−0.007 (3)
C5	0.061 (3)	0.057 (3)	0.045 (3)	−0.008 (2)	0.001 (2)	−0.008 (2)
C6	0.054 (3)	0.054 (3)	0.037 (3)	−0.009 (2)	−0.006 (2)	−0.005 (2)
C7	0.045 (3)	0.051 (3)	0.041 (3)	−0.003 (2)	−0.012 (2)	0.001 (2)
C8	0.045 (3)	0.046 (3)	0.038 (2)	0.006 (2)	−0.006 (2)	−0.004 (2)
C9	0.045 (2)	0.047 (3)	0.029 (2)	0.001 (2)	−0.0058 (19)	0.0038 (19)
C10	0.043 (3)	0.050 (3)	0.048 (3)	0.005 (2)	−0.007 (2)	0.007 (2)
C11	0.044 (3)	0.066 (3)	0.050 (3)	−0.004 (2)	−0.006 (2)	0.007 (3)
C12	0.053 (3)	0.052 (3)	0.038 (3)	−0.012 (2)	0.004 (2)	0.003 (2)
C13	0.057 (3)	0.046 (3)	0.049 (3)	0.006 (2)	0.002 (2)	0.004 (2)
C14	0.051 (3)	0.047 (3)	0.042 (3)	0.002 (2)	−0.008 (2)	0.005 (2)
C15	0.071 (4)	0.058 (3)	0.067 (4)	−0.015 (3)	−0.003 (3)	0.000 (3)

Geometric parameters (Å, º) top

Br1—C5	1.891 (5)	C6—H6	0.9300
N1—C7	1.267 (5)	C7—H7	0.9300
N1—N2	1.377 (5)	C8—C9	1.484 (6)
N2—C8	1.346 (6)	C9—C14	1.381 (6)
N2—H2	0.899 (10)	C9—C10	1.388 (6)
O1—C2	1.358 (6)	C10—C11	1.384 (6)
O1—H1	0.8200	C10—H10	0.9300
O2—C8	1.228 (5)	C11—C12	1.384 (7)
C1—C6	1.389 (6)	C11—H11	0.9300
C1—C2	1.395 (6)	C12—C13	1.383 (6)
C1—C7	1.452 (6)	C12—C15	1.501 (7)
C2—C3	1.394 (7)	C13—C14	1.372 (6)
C3—C4	1.362 (7)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.379 (7)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.365 (6)	C15—H15C	0.9600

C7—N1—N2	116.3 (3)	O2—C8—C9	122.1 (4)
C8—N2—N1	120.4 (3)	N2—C8—C9	116.2 (4)
C8—N2—H2	119 (4)	C14—C9—C10	118.2 (4)
N1—N2—H2	120 (3)	C14—C9—C8	118.5 (4)
C2—O1—H1	109.5	C10—C9—C8	123.2 (4)
C6—C1—C2	117.9 (4)	C11—C10—C9	120.0 (4)
C6—C1—C7	119.0 (4)	C11—C10—H10	120.0
C2—C1—C7	123.1 (4)	C9—C10—H10	120.0
O1—C2—C3	118.3 (4)	C12—C11—C10	121.6 (4)
O1—C2—C1	121.9 (4)	C12—C11—H11	119.2
C3—C2—C1	119.8 (5)	C10—C11—H11	119.2
C4—C3—C2	120.9 (5)	C13—C12—C11	117.7 (4)
C4—C3—H3	119.6	C13—C12—C15	121.1 (5)
C2—C3—H3	119.6	C11—C12—C15	121.2 (4)
C3—C4—C5	119.6 (5)	C14—C13—C12	121.0 (4)
C3—C4—H4	120.2	C14—C13—H13	119.5
C5—C4—H4	120.2	C12—C13—H13	119.5
C6—C5—C4	120.0 (5)	C13—C14—C9	121.3 (4)
C6—C5—Br1	120.3 (4)	C13—C14—H14	119.3
C4—C5—Br1	119.7 (4)	C9—C14—H14	119.3
C5—C6—C1	121.8 (4)	C12—C15—H15A	109.5
C5—C6—H6	119.1	C12—C15—H15B	109.5
C1—C6—H6	119.1	H15A—C15—H15B	109.5
N1—C7—C1	121.2 (4)	C12—C15—H15C	109.5
N1—C7—H7	119.4	H15A—C15—H15C	109.5
C1—C7—H7	119.4	H15B—C15—H15C	109.5
O2—C8—N2	121.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.94	2.653 (5)	146
N2—H2···O2ⁱ	0.90 (1)	2.00 (2)	2.856 (5)	159 (5)

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

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃BrN₂O₂
M_r	333.18
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	5.8290 (15), 31.914 (3), 7.6440 (11)
β (°)	91.535 (2)
V (Å³)	1421.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.89
Crystal size (mm)	0.27 × 0.23 × 0.23

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.509, 0.556
No. of measured, independent and observed [I > 2σ(I)] reflections	11208, 3095, 1794
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.147, 1.03
No. of reflections	3095
No. of parameters	186
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)	0.90, −0.77

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), 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	1.94	2.653 (5)	146
N2—H2···O2ⁱ	0.899 (10)	2.00 (2)	2.856 (5)	159 (5)

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

Acknowledgements

The author acknowledges the project supported by the Office of Science and Technology of Shanxi Province (grant No. 2009 K01–51) and the project supported by the Key Research Item of Baoji University of Arts and Sciences (grant No. ZK1040).

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 (2002). SAINT, SMART and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, D.-S. (2008). Acta Cryst. E64, o1850. Web of Science CSD CrossRef IUCr Journals Google Scholar