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

Abstract

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,

• a = 5.8290 (15) Å

• b = 31.914 (3) Å

• c = 7.6440 (11) Å

• β = 91.535 (2)°

• V = 1421.5 (4) ų

• 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[F ² > 2σ(F ²)] = 0.060

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811043960/hb6461Isup3.cml

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

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) .

supplementary crystallographic information

Comment

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).

Experimental

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.

Refinement

Atom H2 was located in a difference Fourier map and refined isotropically, with N—H distance restrained to 0.90 (1) Å. Other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with O—H distance of 0.82 Å, C—H distances of 0.93–0.96 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O1 and C15).

Figures

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.

Crystal data

C15H13BrN2O2	F(000) = 672
Mr = 333.18	Dx = 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

Bruker SMART CCD diffractometer	3095 independent reflections
Radiation source: fine-focus sealed tube	1794 reflections with I > 2σ(I)
graphite	Rint = 0.039
ω scans	θmax = 27.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −7→7
Tmin = 0.509, Tmax = 0.556	k = −40→36
11208 measured reflections	l = −9→9

Refinement

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(Fo2) + (0.0437P)2 + 2.875P] where P = (Fo2 + 2Fc2)/3
3095 reflections	(Δ/σ)max = 0.001
186 parameters	Δρmax = 0.90 e Å−3
1 restraint	Δρmin = −0.77 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) x+1/2, −y+1/2, z+1/2.