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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 12| December 2011| Page o3365
https://doi.org/10.1107/S1600536811048495

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

Jian-Guo Changa*

aDepartment of Materials Science and Chemical Engineering, Taishan University, 271021 Taian, Shandong, People's Republic of China
*Correspondence e-mail: tsucjg@163.com

(Received 31 October 2011; accepted 15 November 2011; online 19 November 2011)

The title compound, C15H12BrClN2O2, was synthesized by the condensation of 1-(5-bromo-2-hy­droxy­phen­yl)ethanone with 2-chloro­benzohydrazide in anhydrous ethanol. The Schiff base mol­ecule displays a trans configuration with respect to the C=N double bond. The dihedral angle between the two benzene rings is 13.74 (3)°. The mol­ecular conformation is stabilized by an intra­molecular O—H⋯N and the crystal structure by inter­molecular N—H⋯O hydrogen bonds.

Related literature

For further details of the chemistry of the title compound, see: Carcelli et al. (1995[Carcelli, M., Mazza, P., Pelizzi, G. & Zani, F. (1995). J. Inorg. Biochem. 57, 43-62.]); Salem (1998[Salem, A. A. (1998). Microchem. J. 60, 51-66.]). For a related structure, see: Chang (2008[Chang, J.-G. (2008). Acta Cryst. E64, o198.]).

[Scheme 1]

Experimental

Crystal data

  • C15H12BrClN2O2

  • Mr = 367.62

  • Monoclinic, P 21 /n

  • a = 14.861 (3) Å

  • b = 4.837 (1) Å

  • c = 21.310 (4) Å

  • β = 106.099 (4)°

  • V = 1471.7 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.98 mm−1

  • T = 298 K

  • 0.15 × 0.10 × 0.06 mm
Data collection

  • Bruker APEXII CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.664, Tmax = 0.842

  • 7095 measured reflections

  • 2605 independent reflections

  • 1514 reflections with I > 2σ(I)

  • Rint = 0.052
Refinement

  • R[F2 > 2σ(F2)] = 0.043

  • wR(F2) = 0.119

  • S = 1.05

  • 2605 reflections

  • 191 parameters

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.42 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O2—H2⋯N2 0.82 1.82 2.530 (4) 144
N1—H1⋯O1i 0.86 2.16 2.858 (4) 138
Symmetry code: (i) x, y+1, z.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: XP in SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536811048495/pk2360sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811048495/pk2360Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536811048495/pk2360Isup3.cml

checkCIF report


Comment top

The chemistry of aroylhydrazones continues to attract much attention due to their ability to coordinate to metal ions (Salem, 1998) and their biological activity (Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives (Chang, 2008), the title compound, (I), was synthesized and its crystal structure is reported here.

The title molecule displays a trans conformation with respect to the C8=N2 double bond (Fig. 1). The dihedral angle between the two benzene rings is 13.74 (3) °. The crystal structure is stabilized by an intramolecular O—H···N and by intermolecular N—H···O hydrogen bonds. (see Table 1 and Figs. 1 & 2.).

Related literature top

For further details of the chemistry of the title compound, see: Carcelli et al. (1995); Salem (1998). For a related structure, see: Chang (2008).

Experimental top

2-chlorobenzohydrazide (0.01 mol,1.71 g) was dissolved in anhydrous ethanol (40 ml), and 1-(5-bromo-2-hydroxyphenyl)ethanone (0.01 mol, 2.15 g) was added. The reaction mixture was refluxed for 4 h with stirring, then the resulting precipitate was collected by filtration, washed several times with ethanol and dried in vacuo (yield 85%). The compound (1.0 mmol, 0.36 g) was dissolved in dimethylformamide (10 ml) and kept at room temperature for 30 d to obtain colourless single crystals suitable for X-ray diffraction.

Refinement top

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, N—H =0.86 Å and with Uiso(H) = 1.5Ueq(Cmethyl, O) and 1.2Ueq(Caromatic, N).

Structure description top

The chemistry of aroylhydrazones continues to attract much attention due to their ability to coordinate to metal ions (Salem, 1998) and their biological activity (Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives (Chang, 2008), the title compound, (I), was synthesized and its crystal structure is reported here.

The title molecule displays a trans conformation with respect to the C8=N2 double bond (Fig. 1). The dihedral angle between the two benzene rings is 13.74 (3) °. The crystal structure is stabilized by an intramolecular O—H···N and by intermolecular N—H···O hydrogen bonds. (see Table 1 and Figs. 1 & 2.).

For further details of the chemistry of the title compound, see: Carcelli et al. (1995); Salem (1998). For a related structure, see: Chang (2008).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of compound (I). Displacement ellipsoids are drawn at the 30% probability level. Dashed lines show intramolecular O–H···N hydrogen bonds.
[Figure 2] Fig. 2. Packing diagram of (I), Showing intermolecular N—H···O hydrogen bonds as dashed lines.
N'-[(E)-1-(5-Bromo-2-hydroxyphenyl)ethylidene]- 2-chlorobenzohydrazide top
Crystal data top
C15H12BrClN2O2F(000) = 736
Mr = 367.62Dx = 1.655 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1463 reflections
a = 14.861 (3) Åθ = 2.9–22.6°
b = 4.837 (1) ŵ = 2.98 mm−1
c = 21.310 (4) ÅT = 298 K
β = 106.099 (4)°Block, colourless
V = 1471.7 (5) Å30.15 × 0.10 × 0.06 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2605 independent reflections
Radiation source: fine-focus sealed tube1514 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
φ and ω scansθmax = 25.1°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −17→12
Tmin = 0.664, Tmax = 0.842k = −5→5
7095 measured reflectionsl = −25→25
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.043Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.049P)2 + 0.1072P]
where P = (Fo2 + 2Fc2)/3
2605 reflections(Δ/σ)max < 0.001
191 parametersΔρmax = 0.31 e Å−3
0 restraintsΔρmin = −0.42 e Å−3
Crystal data top
C15H12BrClN2O2V = 1471.7 (5) Å3
Mr = 367.62Z = 4
Monoclinic, P21/nMo Kα radiation
a = 14.861 (3) ŵ = 2.98 mm−1
b = 4.837 (1) ÅT = 298 K
c = 21.310 (4) Å0.15 × 0.10 × 0.06 mm
β = 106.099 (4)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer		2605 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1514 reflections with I > 2σ(I)
Tmin = 0.664, Tmax = 0.842Rint = 0.052
7095 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0430 restraints
wR(F2) = 0.119H-atom parameters constrained
S = 1.05Δρmax = 0.31 e Å−3
2605 reflectionsΔρmin = −0.42 e Å−3
191 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
xyzUiso*/Ueq
Br10.10714 (4)0.26900 (11)0.07214 (2)0.0735 (3)
Cl10.30550 (9)0.2243 (3)0.53343 (6)0.0666 (4)
O10.1050 (2)−0.4214 (6)0.45813 (14)0.0539 (8)
O2−0.0140 (2)−0.3493 (7)0.27979 (16)0.0590 (9)
H20.0073−0.28260.31630.089*
N10.1335 (2)0.0122 (7)0.43053 (16)0.0427 (9)
H10.15650.17290.44270.051*
N20.0972 (2)−0.0529 (7)0.36469 (16)0.0422 (9)
C10.2301 (3)0.0827 (8)0.5746 (2)0.0408 (11)
C20.1587 (3)−0.0978 (8)0.5449 (2)0.0383 (10)
C30.1083 (3)−0.2171 (8)0.5835 (2)0.0501 (12)
H30.0615−0.34440.56510.060*
C40.1260 (4)−0.1510 (11)0.6491 (3)0.0591 (14)
H40.0914−0.23400.67430.071*
C50.1939 (4)0.0354 (11)0.6766 (2)0.0629 (14)
H50.20460.08360.72030.076*
C60.2466 (3)0.1522 (10)0.6402 (2)0.0544 (13)
H60.29350.27810.65930.065*
C70.1312 (3)−0.1848 (8)0.4744 (2)0.0398 (11)
C80.1261 (3)0.0878 (8)0.3226 (2)0.0379 (11)
C90.1998 (3)0.3071 (9)0.3396 (2)0.0505 (12)
H9A0.17150.48470.32750.076*
H9B0.24570.27370.31650.076*
H9C0.22940.30360.38580.076*
C100.0828 (3)0.0126 (8)0.25362 (19)0.0383 (10)
C110.1075 (3)0.1475 (9)0.2027 (2)0.0451 (11)
H110.15230.28680.21320.054*
C120.0688 (3)0.0840 (10)0.1384 (2)0.0523 (13)
C130.0016 (3)−0.1209 (11)0.1220 (2)0.0579 (14)
H13−0.0257−0.16450.07830.070*
C14−0.0251 (4)−0.2602 (10)0.1702 (3)0.0629 (14)
H14−0.0704−0.39780.15870.075*
C150.0147 (3)−0.1986 (9)0.2358 (2)0.0451 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1016 (5)0.0720 (4)0.0474 (3)0.0180 (3)0.0216 (3)0.0081 (3)
Cl10.0595 (9)0.0796 (10)0.0582 (8)−0.0267 (7)0.0123 (6)−0.0046 (7)
O10.081 (2)0.0263 (18)0.0544 (19)−0.0110 (15)0.0179 (16)−0.0075 (15)
O20.070 (2)0.048 (2)0.059 (2)−0.0214 (16)0.0164 (19)−0.0124 (18)
N10.061 (3)0.0243 (19)0.039 (2)−0.0107 (17)0.0094 (18)−0.0010 (17)
N20.055 (3)0.030 (2)0.037 (2)−0.0065 (17)0.0073 (18)−0.0052 (17)
C10.041 (3)0.036 (2)0.042 (3)0.001 (2)0.006 (2)−0.001 (2)
C20.042 (3)0.030 (2)0.041 (2)0.007 (2)0.009 (2)0.002 (2)
C30.058 (3)0.036 (3)0.056 (3)−0.008 (2)0.015 (3)−0.002 (2)
C40.069 (4)0.054 (3)0.059 (3)0.000 (3)0.027 (3)0.006 (3)
C50.073 (4)0.066 (4)0.049 (3)0.003 (3)0.017 (3)−0.005 (3)
C60.057 (3)0.047 (3)0.054 (3)−0.001 (2)0.007 (3)−0.009 (2)
C70.043 (3)0.025 (3)0.051 (3)0.0008 (19)0.013 (2)−0.001 (2)
C80.038 (3)0.028 (2)0.045 (3)0.0042 (19)0.007 (2)−0.006 (2)
C90.054 (3)0.047 (3)0.045 (3)−0.011 (2)0.005 (2)0.001 (2)
C100.041 (3)0.031 (2)0.041 (3)0.005 (2)0.008 (2)−0.005 (2)
C110.054 (3)0.036 (3)0.043 (3)0.003 (2)0.009 (2)−0.007 (2)
C120.060 (3)0.046 (3)0.045 (3)0.017 (3)0.006 (2)−0.002 (2)
C130.065 (4)0.055 (3)0.044 (3)0.017 (3)−0.002 (3)−0.011 (3)
C140.060 (4)0.061 (4)0.056 (3)−0.001 (3)−0.003 (3)−0.014 (3)
C150.040 (3)0.042 (3)0.049 (3)−0.001 (2)0.005 (2)−0.004 (2)
Geometric parameters (Å, º) top
Br1—C121.889 (5)C5—C61.368 (7)
Cl1—C11.743 (4)C5—H50.9300
O1—C71.228 (5)C6—H60.9300
O2—C151.346 (5)C8—C101.477 (5)
O2—H20.8200C8—C91.495 (6)
N1—C71.342 (5)C9—H9A0.9600
N1—N21.393 (4)C9—H9B0.9600
N1—H10.8600C9—H9C0.9600
N2—C81.291 (5)C10—C111.399 (6)
C1—C21.384 (5)C10—C151.413 (6)
C1—C61.392 (6)C11—C121.366 (6)
C2—C31.383 (6)C11—H110.9300
C2—C71.505 (6)C12—C131.382 (7)
C3—C41.386 (6)C13—C141.376 (7)
C3—H30.9300C13—H130.9300
C4—C51.359 (7)C14—C151.391 (7)
C4—H40.9300C14—H140.9300
C15—O2—H2109.5N2—C8—C9124.6 (4)
C7—N1—N2117.6 (3)C10—C8—C9120.3 (4)
C7—N1—H1121.2C8—C9—H9A109.5
N2—N1—H1121.2C8—C9—H9B109.5
C8—N2—N1118.1 (3)H9A—C9—H9B109.5
C2—C1—C6120.6 (4)C8—C9—H9C109.5
C2—C1—Cl1122.5 (3)H9A—C9—H9C109.5
C6—C1—Cl1116.9 (3)H9B—C9—H9C109.5
C3—C2—C1117.7 (4)C11—C10—C15116.8 (4)
C3—C2—C7115.8 (4)C11—C10—C8121.4 (4)
C1—C2—C7126.5 (4)C15—C10—C8121.8 (4)
C2—C3—C4121.4 (4)C12—C11—C10123.0 (4)
C2—C3—H3119.3C12—C11—H11118.5
C4—C3—H3119.3C10—C11—H11118.5
C5—C4—C3119.9 (5)C11—C12—C13119.3 (5)
C5—C4—H4120.1C11—C12—Br1120.9 (4)
C3—C4—H4120.1C13—C12—Br1119.8 (4)
C4—C5—C6120.2 (5)C14—C13—C12119.9 (5)
C4—C5—H5119.9C14—C13—H13120.0
C6—C5—H5119.9C12—C13—H13120.0
C5—C6—C1120.1 (5)C13—C14—C15121.1 (5)
C5—C6—H6120.0C13—C14—H14119.5
C1—C6—H6120.0C15—C14—H14119.5
O1—C7—N1122.2 (4)O2—C15—C14117.1 (4)
O1—C7—C2121.3 (4)O2—C15—C10123.1 (4)
N1—C7—C2116.4 (3)C14—C15—C10119.8 (5)
N2—C8—C10115.1 (4)
C7—N1—N2—C8−156.6 (4)N1—N2—C8—C93.2 (6)
C6—C1—C2—C3−3.5 (6)N2—C8—C10—C11−179.9 (4)
Cl1—C1—C2—C3174.4 (3)C9—C8—C10—C11−1.5 (6)
C6—C1—C2—C7178.1 (4)N2—C8—C10—C15−0.1 (6)
Cl1—C1—C2—C7−4.0 (6)C9—C8—C10—C15178.3 (4)
C1—C2—C3—C42.4 (6)C15—C10—C11—C120.2 (6)
C7—C2—C3—C4−179.0 (4)C8—C10—C11—C12−179.9 (4)
C2—C3—C4—C50.2 (7)C10—C11—C12—C130.5 (7)
C3—C4—C5—C6−1.8 (8)C10—C11—C12—Br1−178.7 (3)
C4—C5—C6—C10.7 (7)C11—C12—C13—C14−0.6 (7)
C2—C1—C6—C52.0 (7)Br1—C12—C13—C14178.6 (4)
Cl1—C1—C6—C5−175.9 (4)C12—C13—C14—C150.0 (7)
N2—N1—C7—O15.5 (6)C13—C14—C15—O2−178.6 (4)
N2—N1—C7—C2−172.0 (3)C13—C14—C15—C100.8 (7)
C3—C2—C7—O1−35.1 (6)C11—C10—C15—O2178.4 (4)
C1—C2—C7—O1143.3 (4)C8—C10—C15—O2−1.4 (7)
C3—C2—C7—N1142.5 (4)C11—C10—C15—C14−0.9 (6)
C1—C2—C7—N1−39.1 (6)C8—C10—C15—C14179.2 (4)
N1—N2—C8—C10−178.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N20.821.822.530 (4)144
N1—H1···O1i0.862.162.858 (4)138
Symmetry code: (i) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC15H12BrClN2O2
Mr367.62
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)14.861 (3), 4.837 (1), 21.310 (4)
β (°) 106.099 (4)
V (Å3)1471.7 (5)
Z4
Radiation typeMo Kα
µ (mm−1)2.98
Crystal size (mm)0.15 × 0.10 × 0.06
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.664, 0.842
No. of measured, independent and
observed [I > 2σ(I)] reflections		7095, 2605, 1514
Rint0.052
(sin θ/λ)max (Å−1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.119, 1.05
No. of reflections2605
No. of parameters191
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.31, −0.42

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···N20.821.822.530 (4)143.8
N1—H1···O1i0.862.162.858 (4)137.5
Symmetry code: (i) x, y+1, z.
 

Acknowledgements

This project was supported by the Postgraduate Foundation of Taishan University (No·Y05–2–09)

References

First citationBruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationCarcelli, M., Mazza, P., Pelizzi, G. & Zani, F. (1995). J. Inorg. Biochem. 57, 43–62.  CrossRef CAS PubMed Web of Science Google Scholar
 First citationChang, J.-G. (2008). Acta Cryst. E64, o198.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSalem, A. A. (1998). Microchem. J. 60, 51–66.  Web of Science CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 67| Part 12| December 2011| Page o3365
https://doi.org/10.1107/S1600536811048495
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