(E)-N′-(5-Bromo-2-hy­droxy­benzyl­idene)-3-methyl­benzohydrazide

Guo, H.-C.; Liu, S.-Y.; Wang, X.-L.

doi:10.1107/S1600536811025426

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1878

doi:10.1107/S1600536811025426

Open

access

(E)-N′-(5-Bromo-2-hydroxybenzylidene)-3-methylbenzohydrazide

Hai-Chang Guo,^a Shi-Yong Liu ^a ^* and Xiao-Ling Wang ^b

^aCollege of Chemistry & Pharmacy, Taizhou University, Taizhou Zhejiang 317000, People's Republic of China, and ^bDepartment of Chemistry, Liaoning Normal University, Dalian 116029, People's Republic of China
^*Correspondence e-mail: liushiyong2010@yahoo.cn

(Received 15 June 2011; accepted 28 June 2011; online 2 July 2011)

In the title molecule, C₁₅H₁₃BrN₂O₂, an intramolecular O—H⋯N hydrogen bond influences the molecular conformation; the two benzene rings form a dihedral angle of 13.6 (3)°. In the crystal, intermolecular N—H⋯O hydrogen bonds link the molecules into chains along the a axis and weak intermolecular C—H⋯O hydrogen bonds further link these chains into layers parallel to the ac plane.

Related literature

For applications of hydrazone compounds, see: Hillmer et al. (2010 ); Raj et al. (2007 ). For the crystal structures of related hydrazone compounds, see: Vijayakumar et al. (2009 ); Liu & You (2010 ); Liu & Wang (2010 ). For related structures, see: Xu et al. (2009 ); Shafiq et al. (2009 ).

Experimental

Crystal data

C₁₅H₁₃BrN₂O₂
M_r = 333.18
Monoclinic, P 2₁ /n
a = 7.138 (3) Å
b = 27.404 (10) Å
c = 7.859 (3) Å
β = 112.297 (5)°
V = 1422.4 (9) Å³
Z = 4
Mo Kα radiation
μ = 2.89 mm⁻¹
T = 298 K
0.13 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.705, T_max = 0.761
6807 measured reflections
3045 independent reflections
1489 reflections with I > 2σ(I)
R_int = 0.056

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.106
S = 0.99
3045 reflections
185 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.90 (1)	2.02 (2)	2.890 (4)	163 (4)
O1—H1⋯N1	0.82	1.89	2.605 (4)	146
C14—H14⋯O1ⁱⁱ	0.93	2.44	3.226 (4)	143
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y, z+1.

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/S1600536811025426/cv5119sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025426/cv5119Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025426/cv5119Isup3.cml

checkCIF report

Comment top

Considerable attention has been focused on hydrazones and their medicinal applications (Hillmer et al., 2010; Raj et al., 2007). The crystal structures of such compounds are of particular interest (Vijayakumar et al., 2009). As a continuation of our work with hydrazone compounds (Liu & You, 2010; Liu & Wang, 2010), we report herein the crystal structure of the title compound, (I).

In (I) (Fig. 1), two benzene rings are inclined with a dihedral angle of 13.6 (3) °. All the bond lengths are comparable to those observed in related structures (Xu et al., 2009; Shafiq et al., 2009), and those we reported previously (Liu & You, 2010; Liu & Wang, 2010).

In the crystal structure, molecules are linked through N–H···O hydrogen bonds (Table 1), to form one-dimensional chains running along the a axis (Fig. 2). Weak intermolecular C—H···O hydrogen bonds (Table 1) link further these chains into layers parallel to ac plane.

Related literature top

For applications of hydrazone compounds, see: Hillmer et al. (2010); Raj et al. (2007). For the crystal structures of related hydrazone compounds, see: Vijayakumar et al. (2009); Liu & You (2010); Liu & Wang (2010). For related structures, see: Xu et al. (2009); Shafiq et al. (2009).

Experimental top

The title compound was prepared by the condensation reaction of 5-bromosalicylaldehyde (0.05 mol, 10.0 g) and 3-methylbenzohydrazide (0.05 mol, 7.5 g) in anhydrous methanol (100 ml) at ambient temperature. Colourless block-shaped single crystals suitable for X-ray structural determination were obtained by slow evaporation of the solution for 5 d.

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). Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms are shown as spheres of arbitrary radius and the intramolecular hydrogen bond is drawn as a dashed line.
	Fig. 2. A portion of the crystal packing viewed along the c axis. N—H···O hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in N—H···O hydrogen bonding were omitted.

(E)-N'-(5-Bromo-2-hydroxybenzylidene)-3-methylbenzohydrazide top

Crystal data top

C₁₅H₁₃BrN₂O₂	F(000) = 672
M_r = 333.18	D_x = 1.556 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 983 reflections
a = 7.138 (3) Å	θ = 2.5–24.5°
b = 27.404 (10) Å	µ = 2.89 mm⁻¹
c = 7.859 (3) Å	T = 298 K
β = 112.297 (5)°	Block, colourless
V = 1422.4 (9) Å³	0.13 × 0.10 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	3045 independent reflections
Radiation source: fine-focus sealed tube	1489 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ω scans	θ_max = 27.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→8
T_min = 0.705, T_max = 0.761	k = −29→35
6807 measured reflections	l = −7→10

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0322P)² + 0.1905P] where P = (F_o² + 2F_c²)/3
3045 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.32 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₅H₁₃BrN₂O₂	V = 1422.4 (9) Å³
M_r = 333.18	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.138 (3) Å	µ = 2.89 mm⁻¹
b = 27.404 (10) Å	T = 298 K
c = 7.859 (3) Å	0.13 × 0.10 × 0.10 mm
β = 112.297 (5)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3045 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1489 reflections with I > 2σ(I)
T_min = 0.705, T_max = 0.761	R_int = 0.056
6807 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	1 restraint
wR(F²) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.32 e Å⁻³
3045 reflections	Δρ_min = −0.36 e Å⁻³
185 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.82155 (9)	1.017416 (16)	0.22011 (7)	0.0691 (2)
N1	0.7539 (5)	0.78962 (11)	0.4049 (4)	0.0343 (8)
N2	0.7822 (5)	0.76007 (11)	0.5550 (4)	0.0354 (8)
O1	0.6966 (5)	0.80234 (9)	0.0601 (4)	0.0539 (9)
H1	0.7095	0.7865	0.1525	0.081*
O2	0.6037 (4)	0.69873 (9)	0.3697 (3)	0.0444 (8)
C1	0.7856 (6)	0.86760 (13)	0.2857 (5)	0.0313 (9)
C2	0.7363 (6)	0.85015 (13)	0.1057 (5)	0.0365 (10)
C3	0.7251 (7)	0.88254 (15)	−0.0339 (5)	0.0474 (12)
H3	0.6992	0.8709	−0.1518	0.057*
C4	0.7520 (7)	0.93154 (15)	0.0010 (6)	0.0498 (12)
H4	0.7406	0.9531	−0.0938	0.060*
C5	0.7957 (6)	0.94894 (14)	0.1761 (6)	0.0430 (11)
C6	0.8154 (6)	0.91721 (13)	0.3166 (5)	0.0386 (10)
H6	0.8496	0.9293	0.4352	0.046*
C7	0.8052 (6)	0.83446 (14)	0.4357 (5)	0.0358 (10)
H7	0.8558	0.8460	0.5559	0.043*
C8	0.7035 (6)	0.71426 (13)	0.5232 (5)	0.0327 (10)
C9	0.7491 (6)	0.68420 (13)	0.6938 (5)	0.0320 (10)
C10	0.7697 (6)	0.63410 (14)	0.6820 (5)	0.0367 (10)
H10	0.7537	0.6202	0.5694	0.044*
C11	0.8140 (6)	0.60430 (13)	0.8356 (6)	0.0386 (10)
C12	0.8309 (6)	0.62636 (16)	1.0002 (6)	0.0514 (12)
H12	0.8573	0.6069	1.1038	0.062*
C13	0.8099 (7)	0.67597 (16)	1.0153 (6)	0.0498 (12)
H13	0.8230	0.6897	1.1275	0.060*
C14	0.7689 (6)	0.70533 (14)	0.8605 (5)	0.0400 (11)
H14	0.7548	0.7389	0.8688	0.048*
C15	0.8392 (8)	0.55033 (15)	0.8246 (7)	0.0644 (14)
H15A	0.7782	0.5400	0.6987	0.097*
H15B	0.7747	0.5340	0.8959	0.097*
H15C	0.9808	0.5424	0.8722	0.097*
H2	0.879 (5)	0.7674 (15)	0.664 (3)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0954 (5)	0.0325 (3)	0.0780 (4)	0.0030 (3)	0.0314 (3)	0.0053 (2)
N1	0.038 (2)	0.0305 (18)	0.034 (2)	0.0021 (15)	0.0127 (17)	0.0075 (14)
N2	0.037 (2)	0.0333 (19)	0.0296 (19)	−0.0013 (16)	0.0062 (17)	0.0078 (15)
O1	0.084 (2)	0.0348 (17)	0.0420 (17)	−0.0091 (16)	0.0230 (18)	−0.0069 (13)
O2	0.054 (2)	0.0402 (17)	0.0278 (16)	−0.0026 (13)	0.0030 (15)	−0.0019 (12)
C1	0.028 (3)	0.034 (2)	0.035 (2)	0.0047 (18)	0.0148 (19)	0.0009 (18)
C2	0.036 (3)	0.031 (2)	0.040 (3)	0.0017 (18)	0.012 (2)	−0.0017 (19)
C3	0.067 (4)	0.046 (3)	0.031 (2)	−0.002 (2)	0.020 (2)	−0.001 (2)
C4	0.060 (3)	0.046 (3)	0.045 (3)	0.005 (2)	0.021 (3)	0.016 (2)
C5	0.047 (3)	0.028 (2)	0.053 (3)	0.0012 (19)	0.017 (2)	0.0012 (19)
C6	0.040 (3)	0.034 (2)	0.036 (2)	0.0017 (19)	0.009 (2)	0.0013 (19)
C7	0.035 (3)	0.035 (2)	0.034 (2)	0.0006 (19)	0.010 (2)	0.0022 (18)
C8	0.032 (3)	0.031 (2)	0.034 (2)	0.0023 (18)	0.011 (2)	0.0027 (18)
C9	0.032 (3)	0.032 (2)	0.029 (2)	−0.0009 (17)	0.008 (2)	0.0021 (17)
C10	0.034 (3)	0.037 (2)	0.037 (2)	0.0035 (18)	0.012 (2)	0.0017 (18)
C11	0.031 (3)	0.034 (2)	0.052 (3)	0.0041 (19)	0.016 (2)	0.009 (2)
C12	0.050 (3)	0.056 (3)	0.041 (3)	−0.008 (2)	0.010 (2)	0.018 (2)
C13	0.059 (3)	0.057 (3)	0.033 (3)	−0.010 (2)	0.017 (2)	−0.001 (2)
C14	0.047 (3)	0.035 (2)	0.038 (2)	−0.005 (2)	0.016 (2)	−0.0043 (19)
C15	0.073 (4)	0.039 (3)	0.084 (4)	0.003 (2)	0.033 (3)	0.014 (2)

Geometric parameters (Å, º) top

Br1—C5	1.904 (4)	C6—H6	0.9300
N1—C7	1.279 (4)	C7—H7	0.9300
N1—N2	1.381 (4)	C8—C9	1.501 (5)
N2—C8	1.359 (4)	C9—C10	1.388 (5)
N2—H2	0.899 (10)	C9—C14	1.390 (5)
O1—C2	1.359 (4)	C10—C11	1.391 (5)
O1—H1	0.8200	C10—H10	0.9300
O2—C8	1.222 (4)	C11—C12	1.391 (5)
C1—C6	1.383 (5)	C11—C15	1.496 (5)
C1—C2	1.406 (5)	C12—C13	1.378 (6)
C1—C7	1.452 (5)	C12—H12	0.9300
C2—C3	1.390 (5)	C13—C14	1.394 (5)
C3—C4	1.369 (5)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.375 (5)	C15—H15A	0.9600
C4—H4	0.9300	C15—H15B	0.9600
C5—C6	1.371 (5)	C15—H15C	0.9600

C7—N1—N2	117.6 (3)	O2—C8—C9	122.6 (3)
C8—N2—N1	117.9 (3)	N2—C8—C9	114.1 (3)
C8—N2—H2	120 (3)	C10—C9—C14	120.0 (3)
N1—N2—H2	120 (3)	C10—C9—C8	118.4 (3)
C2—O1—H1	109.5	C14—C9—C8	121.6 (3)
C6—C1—C2	118.3 (3)	C9—C10—C11	121.2 (4)
C6—C1—C7	120.7 (3)	C9—C10—H10	119.4
C2—C1—C7	120.9 (3)	C11—C10—H10	119.4
O1—C2—C3	117.6 (4)	C10—C11—C12	117.6 (4)
O1—C2—C1	122.7 (3)	C10—C11—C15	121.5 (4)
C3—C2—C1	119.6 (3)	C12—C11—C15	120.9 (4)
C4—C3—C2	120.4 (4)	C13—C12—C11	122.4 (4)
C4—C3—H3	119.8	C13—C12—H12	118.8
C2—C3—H3	119.8	C11—C12—H12	118.8
C3—C4—C5	120.1 (4)	C12—C13—C14	119.2 (4)
C3—C4—H4	119.9	C12—C13—H13	120.4
C5—C4—H4	119.9	C14—C13—H13	120.4
C6—C5—C4	120.1 (4)	C9—C14—C13	119.7 (4)
C6—C5—Br1	120.4 (3)	C9—C14—H14	120.2
C4—C5—Br1	119.5 (3)	C13—C14—H14	120.2
C5—C6—C1	121.3 (4)	C11—C15—H15A	109.5
C5—C6—H6	119.3	C11—C15—H15B	109.5
C1—C6—H6	119.3	H15A—C15—H15B	109.5
N1—C7—C1	121.0 (3)	C11—C15—H15C	109.5
N1—C7—H7	119.5	H15A—C15—H15C	109.5
C1—C7—H7	119.5	H15B—C15—H15C	109.5
O2—C8—N2	123.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.90 (1)	2.02 (2)	2.890 (4)	163 (4)
O1—H1···N1	0.82	1.89	2.605 (4)	146
C14—H14···O1ⁱⁱ	0.93	2.44	3.226 (4)	143

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x, y, z+1.

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)	7.138 (3), 27.404 (10), 7.859 (3)
β (°)	112.297 (5)
V (Å³)	1422.4 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.89
Crystal size (mm)	0.13 × 0.10 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.705, 0.761
No. of measured, independent and observed [I > 2σ(I)] reflections	6807, 3045, 1489
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.106, 0.99
No. of reflections	3045
No. of parameters	185
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)	0.32, −0.36

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
N2—H2···O2ⁱ	0.899 (10)	2.017 (16)	2.890 (4)	163 (4)
O1—H1···N1	0.82	1.89	2.605 (4)	146
C14—H14···O1ⁱⁱ	0.93	2.44	3.226 (4)	143

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) x, y, z+1.

Acknowledgements

The authors acknowledge the Undergraduate Innovation Group Project of Zhejiang Province (project no. 2010R428015).

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Hillmer, A. S., Putcha, P., Levin, J., Hogen, T., Hyman, B. T., Kretzschmar, H., McLean, P. J. & Giese, A. (2010). Biochem. Biophys. Res. Commun. 391, 461–466. Web of Science CrossRef PubMed CAS Google Scholar
Liu, S.-Y. & Wang, X. (2010). Acta Cryst. E66, o1775. Web of Science CSD CrossRef IUCr Journals Google Scholar
Liu, S.-Y. & You, Z. (2010). Acta Cryst. E66, o1652. Web of Science CSD CrossRef IUCr Journals Google Scholar
Raj, K. K. V., Narayana, B., Ashalatha, B. V., Kumari, N. S. & Sarojini, B. K. (2007). Eur. J. Med. Chem. 42, 425–429. PubMed CAS Google Scholar
Shafiq, Z., Yaqub, M., Tahir, M. N., Hussain, A. & Iqbal, M. S. (2009). Acta Cryst. E65, o2898. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vijayakumar, S., Adhikari, A., Kalluraya, B. & Chandrasekharan, K. (2009). Opt. Mater. 31, 1564–1569. Web of Science CrossRef CAS Google Scholar
Xu, L., Huang, S.-S., Zhang, B.-J., Wang, S.-Y. & Zhang, H.-L. (2009). Acta Cryst. E65, o2412. Web of Science CSD CrossRef IUCr Journals Google Scholar