N′-[(E)-1-(5-Bromo-2-hydroxy­phen­yl)ethyl­idene]benzohydrazide

Abstract

The C=N double bond in the title compound, C₁₅H₁₃BrN₂O₂, is trans E configured and the dihedral angle between the aromatic ring planes is 22.3 (1)°. The crystal structure is stabilized by intra­molecular O—H⋯O and inter­molecular N—H⋯O hydrogen bonds.

Related literature

For aroylhydrazones and their biological activity, see: Singh et al. (1982 ▶); Salem (1998 ▶); Carcelli et al. (1995 ▶).

Experimental

Crystal data

• C₁₅H₁₃BrN₂O₂

• M _r = 333.18

• Monoclinic,

• a = 7.3761 (15) Å

• b = 28.270 (6) Å

• c = 8.6089 (13) Å

• β = 116.928 (12)°

• V = 1600.5 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 2.57 mm⁻¹

• T = 298 (2) K

• 0.12 × 0.08 × 0.06 mm

Data collection

• Siemens SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.748, T _max = 0.861

• 8028 measured reflections

• 2830 independent reflections

• 1490 reflections with I > 2σ(I)

• R _int = 0.062

Refinement

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 0.188

• S = 1.01

• 2830 reflections

• 183 parameters

• H-atom parameters constrained

• Δρ_max = 0.87 e Å⁻³

• Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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

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	1.85	2.522 (6)	138
N2—H2⋯O2i	0.86	2.14	2.889 (6)	146

Symmetry code: (i) .

supplementary crystallographic information

Comment

The chemistry of aroylhydrazones continues to attract much attention due to their coordination ability to metal ions (Singh et al., 1982; Salem, 1998) and their biological activity (Singh et al., 1982; Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives, the title compound was synthesized and its crystal structure is reported here.

The title molecule displays a trans configured C=N double bond (Fig. 1). The crystal structure is stabilized by intramolecular O—H···O and intermolecular N—H···O hydrogen bonds (Table 1. and Fig. 2).

Experimental

Benzoylhydrazine (0.02 mol, 2.72 g) was dissolved in anhydrous ethanol (50 ml), and 1-(5-bromo-2-hydroxyphenyl)ethanone (0.02 mol, 4.30 g) was added. The reaction mixture was refluxed for 6 h with stirring, then the resulting precipitate was collected by filtration, washed several times with ethanol and dried in vacuo (yield 85%). The compound (2.0 mmol, 0.67 g) was dissolved in dimethylformamide (30 ml) and kept at room temperature for 30 d to obtain yellow single crystals suitable for X-ray diffraction.

Refinement

All H atoms were positioned geometrically and treated as riding on their parent atoms,with C—H(methyl) = 0.96 Å, C—H(aromatic) = 0.93 Å, O—H = 0.82 Å, and N—H = 0.86 Å and with U_iso(H) =1.5U_eq(C_methyl,O) and 1.2U_eq(C_aromatic,N).

Figures

Fig. 1.

The molecular structure the title compound showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

The crystal packing of the title compound. Dashed lines show hydrogen bonds.

Crystal data

C15H13BrN2O2	F000 = 672
Mr = 333.18	Dx = 1.383 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1189 reflections
a = 7.3761 (15) Å	θ = 2.9–20.7º
b = 28.270 (6) Å	µ = 2.57 mm−1
c = 8.6089 (13) Å	T = 298 (2) K
β = 116.928 (12)º	Block, yellow
V = 1600.5 (5) Å3	0.12 × 0.08 × 0.06 mm
Z = 4

Data collection

Siemens SMART CCD area-detector diffractometer	2830 independent reflections
Radiation source: fine-focus sealed tube	1490 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.062
T = 298(2) K	θmax = 25.1º
φ and ω scans	θmin = 3.0º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.748, Tmax = 0.861	k = −33→33
8028 measured reflections	l = −7→10

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.068	H-atom parameters constrained
wR(F2) = 0.188	w = 1/[σ2(Fo2) + (0.089P)2 + 0.7896P] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max = 0.002
2830 reflections	Δρmax = 0.87 e Å−3
183 parameters	Δρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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 takeninto account individually in the estimation of e.s.d.'s in distances, anglesand torsion angles; correlations between e.s.d.'s in cell parameters are onlyused 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	0.81952 (14)	1.00196 (2)	0.69361 (11)	0.0935 (4)
O1	0.6647 (7)	0.79484 (14)	0.7321 (5)	0.0613 (11)
H1	0.6183	0.7820	0.6365	0.092*
O2	0.3297 (6)	0.70963 (13)	0.4419 (5)	0.0602 (11)
N1	0.4384 (6)	0.79657 (14)	0.4079 (5)	0.0391 (10)
N2	0.3180 (6)	0.76994 (15)	0.2660 (5)	0.0416 (10)
H2	0.2720	0.7810	0.1620	0.050*
C1	0.6935 (8)	0.84139 (19)	0.7143 (6)	0.0442 (13)
C2	0.6016 (8)	0.86503 (17)	0.5556 (6)	0.0390 (12)
C3	0.6426 (8)	0.91292 (19)	0.5540 (7)	0.0497 (14)
H3	0.5829	0.9294	0.4491	0.060*
C4	0.7677 (8)	0.9363 (2)	0.7018 (8)	0.0555 (15)
C5	0.8592 (10)	0.9132 (2)	0.8592 (8)	0.0655 (17)
H5	0.9461	0.9293	0.9598	0.079*
C6	0.8202 (9)	0.8661 (2)	0.8654 (8)	0.0658 (18)
H6	0.8789	0.8503	0.9716	0.079*
C7	0.4633 (7)	0.84066 (17)	0.3902 (6)	0.0370 (12)
C8	0.2737 (8)	0.72504 (18)	0.2962 (7)	0.0430 (13)
C9	0.1524 (8)	0.69622 (19)	0.1385 (7)	0.0460 (13)
C10	0.0099 (8)	0.7153 (2)	−0.0181 (7)	0.0509 (14)
H10	−0.0132	0.7477	−0.0273	0.061*
C11	−0.0978 (9)	0.6865 (2)	−0.1603 (8)	0.0581 (16)
H11	−0.1931	0.6994	−0.2649	0.070*
C12	−0.0621 (10)	0.6383 (2)	−0.1449 (9)	0.0641 (17)
H12	−0.1335	0.6186	−0.2400	0.077*
C13	0.0790 (11)	0.6191 (2)	0.0110 (9)	0.0618 (16)
H13	0.1027	0.5866	0.0200	0.074*
C14	0.1832 (9)	0.64743 (19)	0.1507 (7)	0.0496 (14)
H14	0.2760	0.6342	0.2557	0.060*
C15	0.3682 (9)	0.86765 (19)	0.2249 (6)	0.0535 (15)
H15A	0.4673	0.8733	0.1836	0.080*
H15B	0.3186	0.8973	0.2445	0.080*
H15C	0.2571	0.8498	0.1395	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.1011 (7)	0.0462 (5)	0.0962 (7)	−0.0133 (4)	0.0123 (5)	−0.0172 (4)
O1	0.073 (3)	0.058 (3)	0.040 (2)	−0.003 (2)	0.014 (2)	0.0092 (19)
O2	0.103 (3)	0.040 (2)	0.041 (2)	0.000 (2)	0.037 (2)	0.0038 (17)
N1	0.051 (3)	0.036 (3)	0.029 (2)	0.002 (2)	0.0173 (19)	−0.0012 (19)
N2	0.054 (3)	0.037 (3)	0.032 (2)	−0.006 (2)	0.019 (2)	−0.0022 (19)
C1	0.043 (3)	0.045 (3)	0.037 (3)	−0.003 (2)	0.011 (2)	0.004 (2)
C2	0.034 (3)	0.039 (3)	0.044 (3)	0.002 (2)	0.017 (2)	−0.005 (2)
C3	0.047 (3)	0.049 (3)	0.040 (3)	0.008 (3)	0.009 (3)	−0.005 (3)
C4	0.047 (3)	0.048 (4)	0.062 (4)	0.001 (3)	0.015 (3)	−0.014 (3)
C5	0.064 (4)	0.067 (4)	0.051 (4)	−0.005 (3)	0.013 (3)	−0.020 (3)
C6	0.062 (4)	0.079 (5)	0.040 (3)	0.002 (3)	0.008 (3)	−0.003 (3)
C7	0.044 (3)	0.037 (3)	0.028 (3)	0.004 (2)	0.014 (2)	−0.001 (2)
C8	0.064 (4)	0.032 (3)	0.041 (3)	0.006 (3)	0.031 (3)	0.000 (2)
C9	0.057 (3)	0.043 (3)	0.049 (3)	−0.009 (3)	0.033 (3)	−0.004 (3)
C10	0.057 (3)	0.040 (3)	0.053 (4)	−0.006 (3)	0.022 (3)	0.004 (3)
C11	0.058 (4)	0.052 (4)	0.055 (4)	−0.013 (3)	0.017 (3)	−0.006 (3)
C12	0.070 (4)	0.062 (4)	0.064 (4)	−0.024 (3)	0.034 (4)	−0.027 (3)
C13	0.082 (4)	0.041 (3)	0.079 (5)	−0.009 (3)	0.050 (4)	−0.011 (3)
C14	0.066 (4)	0.036 (3)	0.053 (3)	−0.004 (3)	0.033 (3)	−0.003 (3)
C15	0.071 (4)	0.036 (3)	0.034 (3)	0.001 (3)	0.006 (3)	0.002 (2)

Geometric parameters (Å, °)

Br1—C4	1.902 (6)	C6—H6	0.9300
O1—C1	1.353 (6)	C7—C15	1.482 (7)
O1—H1	0.8200	C8—C9	1.485 (7)
O2—C8	1.210 (6)	C9—C10	1.389 (7)
N1—C7	1.279 (6)	C9—C14	1.394 (7)
N1—N2	1.366 (5)	C10—C11	1.382 (7)
N2—C8	1.365 (6)	C10—H10	0.9300
N2—H2	0.8600	C11—C12	1.384 (8)
C1—C2	1.391 (7)	C11—H11	0.9300
C1—C6	1.397 (8)	C12—C13	1.383 (9)
C2—C3	1.389 (7)	C12—H12	0.9300
C2—C7	1.492 (7)	C13—C14	1.358 (8)
C3—C4	1.358 (7)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.376 (8)	C15—H15A	0.9600
C5—C6	1.367 (9)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C1—O1—H1	109.5	O2—C8—C9	122.1 (5)
C7—N1—N2	120.1 (4)	N2—C8—C9	115.7 (4)
C8—N2—N1	117.2 (4)	C10—C9—C14	118.9 (5)
C8—N2—H2	121.4	C10—C9—C8	123.5 (5)
N1—N2—H2	121.4	C14—C9—C8	117.6 (5)
O1—C1—C2	123.2 (4)	C11—C10—C9	120.7 (6)
O1—C1—C6	117.0 (5)	C11—C10—H10	119.6
C2—C1—C6	119.8 (5)	C9—C10—H10	119.6
C3—C2—C1	117.8 (5)	C10—C11—C12	119.1 (6)
C3—C2—C7	119.9 (4)	C10—C11—H11	120.4
C1—C2—C7	122.3 (5)	C12—C11—H11	120.4
C4—C3—C2	121.6 (5)	C13—C12—C11	120.4 (5)
C4—C3—H3	119.2	C13—C12—H12	119.8
C2—C3—H3	119.2	C11—C12—H12	119.8
C3—C4—C5	120.9 (6)	C14—C13—C12	120.2 (6)
C3—C4—Br1	120.2 (5)	C14—C13—H13	119.9
C5—C4—Br1	118.9 (4)	C12—C13—H13	119.9
C6—C5—C4	118.9 (6)	C13—C14—C9	120.7 (6)
C6—C5—H5	120.6	C13—C14—H14	119.7
C4—C5—H5	120.6	C9—C14—H14	119.7
C5—C6—C1	121.0 (6)	C7—C15—H15A	109.5
C5—C6—H6	119.5	C7—C15—H15B	109.5
C1—C6—H6	119.5	H15A—C15—H15B	109.5
N1—C7—C15	125.8 (4)	C7—C15—H15C	109.5
N1—C7—C2	114.2 (4)	H15A—C15—H15C	109.5
C15—C7—C2	120.0 (5)	H15B—C15—H15C	109.5
O2—C8—N2	122.2 (5)
C7—N1—N2—C8	−170.7 (5)	C1—C2—C7—N1	−0.3 (7)
O1—C1—C2—C3	179.8 (5)	C3—C2—C7—C15	−0.6 (7)
C6—C1—C2—C3	0.8 (8)	C1—C2—C7—C15	179.6 (5)
O1—C1—C2—C7	−0.4 (8)	N1—N2—C8—O2	3.3 (7)
C6—C1—C2—C7	−179.4 (5)	N1—N2—C8—C9	−176.6 (4)
C1—C2—C3—C4	−0.2 (8)	O2—C8—C9—C10	149.0 (5)
C7—C2—C3—C4	−180.0 (5)	N2—C8—C9—C10	−31.1 (7)
C2—C3—C4—C5	0.2 (9)	O2—C8—C9—C14	−30.3 (8)
C2—C3—C4—Br1	−180.0 (4)	N2—C8—C9—C14	149.6 (5)
C3—C4—C5—C6	−0.8 (9)	C14—C9—C10—C11	−0.8 (8)
Br1—C4—C5—C6	179.3 (5)	C8—C9—C10—C11	179.9 (5)
C4—C5—C6—C1	1.5 (10)	C9—C10—C11—C12	0.0 (8)
O1—C1—C6—C5	179.4 (6)	C10—C11—C12—C13	0.3 (9)
C2—C1—C6—C5	−1.5 (9)	C11—C12—C13—C14	0.3 (9)
N2—N1—C7—C15	1.2 (8)	C12—C13—C14—C9	−1.2 (9)
N2—N1—C7—C2	−178.9 (4)	C10—C9—C14—C13	1.4 (8)
C3—C2—C7—N1	179.5 (5)	C8—C9—C14—C13	−179.3 (5)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.82	1.85	2.522 (6)	138
N2—H2···O2i	0.86	2.14	2.889 (6)	146

Symmetry codes: (i) x, −y+3/2, z−1/2.