3-Bromo-N′-[(E)-4-hydroxy­benzyl­idene]benzohydrazide

Abstract

The title compound, C₁₄H₁₁BrN₂O₂, was synthesized by the reaction of 4-hydroxy­benzaldehyde with an equimolar quantity of 3-bromo­benzohydrazide in methanol. The dihedral angle between the two benzene rings is 40.1 (2)°. In the crystal structure, mol­ecules are linked through inter­molecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds to form a three-dimensional network.

Related literature

For related structures, see: Cao (2007a ▶,b ▶).

Experimental

Crystal data

• C₁₄H₁₁BrN₂O₂

• M _r = 319.16

• Orthorhombic,

• a = 7.5576 (11) Å

• b = 11.7337 (18) Å

• c = 15.021 (2) Å

• V = 1332.0 (3) ų

• Z = 4

• Mo Kα radiation

• μ = 3.08 mm⁻¹

• T = 298 (2) K

• 0.20 × 0.17 × 0.16 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.577, T _max = 0.638

• 7740 measured reflections

• 2757 independent reflections

• 2145 reflections with I > 2σ(I)

• R _int = 0.038

Refinement

• R[F ² > 2σ(F ²)] = 0.030

• wR(F ²) = 0.059

• S = 0.97

• 2757 reflections

• 176 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.17 e Å⁻³

• Δρ_min = −0.29 e Å⁻³

• Absolute structure: Flack (1983 ▶), with 1154 Friedel pairs

• Flack parameter: 0.006 (9)

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.

Supplementary Material

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⋯O2i	0.82	1.95	2.750 (2)	166
O1—H1⋯N1i	0.82	2.56	3.003 (3)	116
N2—H2A⋯O1ii	0.904 (10)	2.136 (14)	3.007 (3)	162 (3)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

We have recently reported some transition metal complexes with Schiff base ligands (Cao, 2007a,b). We report herein the crystal structure of the title compound, (I), derived from the reaction of 4-hydroxybenzaldehyde with an equimolar quantity of 3-bromobenzohydrazide in methanol.

In compound (I), Fig. 1, the dihedral angle between the two benzene rings is 40.1 (2)°. In the crystal structure, molecules are linked through intermolecular O—H···O, O—H···N, and N—H···O hydrogen bonds, Table 1, to form a three-dimensional network, Figure 2.

Experimental

The compound was prepared by refluxing equimolar quantities of 4-hydroxybenzaldehyde with 3-bromobenzohydrazide in methanol. Colourless block-like crystals were formed when the solution was evaporated in air for about a week.

Refinement

H2A was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å. The other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93 Å, the O—H distance 0.82 Å, and with U_iso(H) set at 1.2U_eq(C) and 1.5U_eq(O).

Figures

Fig. 1.

The molecular structure of (I) with ellipsoids drawn at the 30% probability level.

Fig. 2.

The molecular packing of (I), viewed along the a axis. Hydrogen bonds are drawn as dashed lines.

Crystal data

C14H11BrN2O2	F000 = 640
Mr = 319.16	Dx = 1.591 Mg m−3
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1827 reflections
a = 7.5576 (11) Å	θ = 2.3–24.5º
b = 11.7337 (18) Å	µ = 3.09 mm−1
c = 15.021 (2) Å	T = 298 (2) K
V = 1332.0 (3) Å3	Block, colourless
Z = 4	0.20 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2757 independent reflections
Radiation source: fine-focus sealed tube	2145 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.038
T = 298(2) K	θmax = 26.6º
ω scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2001)	h = −9→9
Tmin = 0.577, Tmax = 0.638	k = −10→14
7740 measured reflections	l = −18→18

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.031	w = 1/[σ2(Fo2) + (0.0151P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.059	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 0.17 e Å−3
2757 reflections	Δρmin = −0.29 e Å−3
176 parameters	Extinction correction: none
1 restraint	Absolute structure: Flack (1983), with 1154 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.006 (9)
Secondary atom site location: difference Fourier map

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	0.04594 (5)	0.39161 (3)	0.901456 (17)	0.06805 (13)
O1	0.1347 (3)	−0.14174 (14)	0.15827 (10)	0.0414 (5)
H1	0.0663	−0.1163	0.1208	0.062*
O2	0.0446 (3)	0.45672 (13)	0.48129 (10)	0.0435 (4)
N1	0.1134 (3)	0.23480 (18)	0.46451 (12)	0.0380 (6)
N2	0.1329 (3)	0.29110 (18)	0.54514 (12)	0.0372 (5)
C1	0.1401 (3)	0.0602 (2)	0.38450 (14)	0.0310 (6)
C2	0.0757 (3)	0.1044 (2)	0.30437 (14)	0.0343 (6)
H2	0.0339	0.1789	0.3024	0.041*
C3	0.0735 (3)	0.03889 (19)	0.22853 (14)	0.0331 (6)
H3	0.0315	0.0692	0.1754	0.040*
C4	0.1341 (3)	−0.0726 (2)	0.23148 (14)	0.0309 (6)
C5	0.1975 (3)	−0.1177 (2)	0.31015 (15)	0.0357 (6)
H5	0.2381	−0.1925	0.3120	0.043*
C6	0.2003 (3)	−0.0514 (2)	0.38585 (15)	0.0352 (6)
H6	0.2432	−0.0820	0.4387	0.042*
C7	0.1494 (3)	0.1299 (2)	0.46504 (15)	0.0348 (6)
H7	0.1829	0.0958	0.5183	0.042*
C8	0.0976 (3)	0.4039 (2)	0.54681 (14)	0.0339 (6)
C9	0.1227 (3)	0.4615 (2)	0.63473 (15)	0.0333 (6)
C10	0.0837 (3)	0.4069 (2)	0.71421 (14)	0.0373 (6)
H10	0.0457	0.3315	0.7143	0.045*
C11	0.1020 (4)	0.4657 (2)	0.79290 (15)	0.0405 (7)
C12	0.1571 (4)	0.5781 (2)	0.79396 (18)	0.0482 (8)
H12	0.1689	0.6169	0.8476	0.058*
C13	0.1942 (4)	0.6314 (2)	0.7149 (2)	0.0516 (8)
H13	0.2320	0.7068	0.7151	0.062*
C14	0.1760 (4)	0.5743 (2)	0.63504 (17)	0.0425 (7)
H14	0.1995	0.6116	0.5817	0.051*
H2A	0.195 (4)	0.257 (2)	0.5890 (15)	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0960 (3)	0.0793 (2)	0.02888 (14)	0.0102 (2)	0.00631 (17)	−0.00726 (16)
O1	0.0589 (13)	0.0376 (10)	0.0276 (8)	0.0034 (9)	−0.0034 (9)	−0.0093 (8)
O2	0.0655 (12)	0.0350 (10)	0.0301 (8)	0.0023 (10)	−0.0072 (10)	0.0018 (8)
N1	0.0566 (16)	0.0338 (13)	0.0237 (10)	0.0039 (11)	−0.0060 (10)	−0.0063 (9)
N2	0.0581 (16)	0.0306 (13)	0.0230 (11)	0.0104 (11)	−0.0077 (10)	−0.0070 (9)
C1	0.0354 (14)	0.0340 (13)	0.0236 (13)	−0.0019 (11)	−0.0012 (10)	−0.0033 (10)
C2	0.0435 (16)	0.0295 (12)	0.0298 (11)	−0.0011 (13)	0.0013 (11)	−0.0003 (11)
C3	0.0424 (16)	0.0334 (14)	0.0235 (11)	0.0021 (12)	−0.0035 (11)	0.0015 (10)
C4	0.0343 (14)	0.0348 (15)	0.0238 (12)	−0.0046 (11)	0.0011 (11)	−0.0070 (10)
C5	0.0470 (17)	0.0258 (14)	0.0343 (12)	0.0036 (13)	−0.0010 (11)	−0.0011 (12)
C6	0.0452 (16)	0.0362 (14)	0.0243 (13)	0.0032 (11)	−0.0068 (11)	0.0013 (11)
C7	0.0414 (15)	0.0393 (17)	0.0238 (11)	0.0003 (13)	−0.0026 (11)	−0.0027 (11)
C8	0.0370 (16)	0.0361 (15)	0.0287 (12)	−0.0032 (13)	0.0000 (10)	−0.0013 (12)
C9	0.0362 (15)	0.0342 (15)	0.0297 (12)	0.0039 (12)	−0.0045 (11)	−0.0069 (11)
C10	0.0434 (17)	0.0381 (14)	0.0304 (12)	0.0049 (13)	−0.0038 (11)	−0.0097 (12)
C11	0.0450 (18)	0.0456 (17)	0.0308 (13)	0.0094 (13)	−0.0012 (11)	−0.0093 (12)
C12	0.0512 (19)	0.055 (2)	0.0388 (15)	0.0096 (15)	−0.0131 (14)	−0.0196 (14)
C13	0.054 (2)	0.0368 (17)	0.0644 (19)	0.0002 (14)	−0.0103 (15)	−0.0221 (15)
C14	0.0483 (18)	0.0370 (17)	0.0421 (15)	−0.0020 (13)	−0.0031 (13)	−0.0037 (12)

Geometric parameters (Å, °)

Br1—C11	1.896 (3)	C5—C6	1.378 (3)
O1—C4	1.367 (3)	C5—H5	0.9300
O1—H1	0.8200	C6—H6	0.9300
O2—C8	1.230 (3)	C7—H7	0.9300
N1—C7	1.260 (3)	C8—C9	1.495 (3)
N1—N2	1.387 (2)	C9—C14	1.384 (4)
N2—C8	1.351 (3)	C9—C10	1.387 (3)
N2—H2A	0.904 (10)	C10—C11	1.376 (3)
C1—C6	1.386 (3)	C10—H10	0.9300
C1—C2	1.398 (3)	C11—C12	1.382 (4)
C1—C7	1.462 (3)	C12—C13	1.371 (4)
C2—C3	1.374 (3)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.381 (4)
C3—C4	1.386 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.381 (3)
C4—O1—H1	109.5	N1—C7—H7	119.0
C7—N1—N2	115.88 (19)	C1—C7—H7	119.0
C8—N2—N1	117.51 (19)	O2—C8—N2	122.9 (2)
C8—N2—H2A	121.7 (19)	O2—C8—C9	121.4 (2)
N1—N2—H2A	119 (2)	N2—C8—C9	115.7 (2)
C6—C1—C2	118.5 (2)	C14—C9—C10	120.1 (2)
C6—C1—C7	120.0 (2)	C14—C9—C8	118.2 (2)
C2—C1—C7	121.4 (2)	C10—C9—C8	121.7 (2)
C3—C2—C1	120.7 (2)	C11—C10—C9	119.1 (2)
C3—C2—H2	119.7	C11—C10—H10	120.5
C1—C2—H2	119.7	C9—C10—H10	120.5
C2—C3—C4	119.8 (2)	C10—C11—C12	121.3 (2)
C2—C3—H3	120.1	C10—C11—Br1	119.1 (2)
C4—C3—H3	120.1	C12—C11—Br1	119.65 (19)
O1—C4—C5	117.4 (2)	C13—C12—C11	119.1 (2)
O1—C4—C3	122.4 (2)	C13—C12—H12	120.4
C5—C4—C3	120.2 (2)	C11—C12—H12	120.4
C6—C5—C4	119.7 (2)	C12—C13—C14	120.7 (3)
C6—C5—H5	120.2	C12—C13—H13	119.6
C4—C5—H5	120.2	C14—C13—H13	119.6
C5—C6—C1	121.1 (2)	C13—C14—C9	119.7 (3)
C5—C6—H6	119.5	C13—C14—H14	120.1
C1—C6—H6	119.5	C9—C14—H14	120.1
N1—C7—C1	122.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2i	0.82	1.95	2.750 (2)	166
O1—H1···N1i	0.82	2.56	3.003 (3)	116
N2—H2A···O1ii	0.904 (10)	2.136 (14)	3.007 (3)	162 (3)

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