organic compounds
(E)-N′-(3,5-Dibromo-2-hydroxybenzylidene)-2-methoxybenzohydrazide
aDepartment of Chemistry, Ankang University, Ankang Shanxi 725000, People's Republic of China
*Correspondence e-mail: guobiao_cao@126.com
The title compound, C15H12Br2N2O3, was synthesized by the reaction of 3,5-dibromo-2-hydroxybenzaldehyde with an equimolar quantity of 2-methoxybenzohydrazide in methanol. The dihedral angle between the two benzene rings is 3.4 (2)° and intramolecular O—H⋯N and N—H⋯O hydrogen bonds are observed in the molecule. The crystal studied was an with a 0.513 (19):0.487 (19) domain ratio.
Related literature
For related structures, see: Mohd Lair et al. (2009); Fun et al. (2008); Li & Ban (2009); Zhu et al. (2009); Yang (2007); You et al. (2008). For our previous work in this area, see: Qu et al. (2008); Yang et al. (2008). For reference structural data, see: Allen et al. (1987).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2007); cell 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
10.1107/S1600536809022168/hb5004sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809022168/hb5004Isup2.hkl
The title compound was prepared by refluxing equimolar quantities of 3,5-dibromo-2-hydroxybenzaldehyde with 2-methoxybenzohydrazide in methanol. Colorless blocks of (I) were formed by slow evaporation of the solution in air.
Atom H2 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 (C–H = 0.93-0.96 Å, O–H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(O and methyl C). The crystal studied was an
with a 0.513 (19):0.487 (19) domain ratio.Data collection: SMART (Bruker, 2007); cell
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).Fig. 1. The molecular structure of (I) with ellipsoids drawn at the 30% probability level and hydrogen bonds indicated by dashed lines. |
C15H12Br2N2O3 | F(000) = 840 |
Mr = 428.09 | Dx = 1.850 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 2250 reflections |
a = 10.886 (1) Å | θ = 2.4–25.9° |
b = 12.956 (2) Å | µ = 5.29 mm−1 |
c = 10.965 (2) Å | T = 298 K |
β = 96.476 (3)° | Block, colorless |
V = 1536.6 (4) Å3 | 0.30 × 0.30 × 0.27 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 2208 independent reflections |
Radiation source: fine-focus sealed tube | 1992 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω scans | θmax = 27.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −9→13 |
Tmin = 0.300, Tmax = 0.329 | k = −16→16 |
4623 measured reflections | l = −13→13 |
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)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.125 | w = 1/[σ2(Fo2) + (0.0877P)2 + 0.6851P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
2208 reflections | Δρmax = 0.35 e Å−3 |
204 parameters | Δρmin = −0.62 e Å−3 |
3 restraints | Absolute structure: Flack (1983), 531 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.513 (19) |
C15H12Br2N2O3 | V = 1536.6 (4) Å3 |
Mr = 428.09 | Z = 4 |
Monoclinic, Cc | Mo Kα radiation |
a = 10.886 (1) Å | µ = 5.29 mm−1 |
b = 12.956 (2) Å | T = 298 K |
c = 10.965 (2) Å | 0.30 × 0.30 × 0.27 mm |
β = 96.476 (3)° |
Bruker SMART CCD diffractometer | 2208 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1992 reflections with I > 2σ(I) |
Tmin = 0.300, Tmax = 0.329 | Rint = 0.030 |
4623 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.125 | Δρmax = 0.35 e Å−3 |
S = 1.05 | Δρmin = −0.62 e Å−3 |
2208 reflections | Absolute structure: Flack (1983), 531 Friedel pairs |
204 parameters | Absolute structure parameter: 0.513 (19) |
3 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
Br1 | 0.39963 (8) | −0.26669 (6) | −0.15520 (7) | 0.0501 (2) | |
Br2 | 0.48191 (8) | −0.46448 (6) | 0.30371 (8) | 0.0556 (3) | |
O1 | 0.5231 (5) | −0.0896 (4) | −0.0108 (4) | 0.0388 (11) | |
H1 | 0.5797 | −0.0514 | 0.0166 | 0.058* | |
O2 | 0.6295 (7) | 0.1701 (5) | 0.0431 (5) | 0.0548 (16) | |
O3 | 0.7666 (6) | 0.2128 (4) | 0.4081 (5) | 0.0466 (14) | |
N1 | 0.6150 (6) | 0.0066 (5) | 0.1793 (5) | 0.0341 (12) | |
N2 | 0.6578 (6) | 0.0982 (4) | 0.2312 (5) | 0.0360 (12) | |
C1 | 0.5608 (6) | −0.1684 (5) | 0.1883 (6) | 0.0300 (13) | |
C2 | 0.5188 (6) | −0.1713 (5) | 0.0627 (6) | 0.0306 (13) | |
C3 | 0.4675 (7) | −0.2629 (5) | 0.0147 (7) | 0.0351 (14) | |
C4 | 0.4612 (7) | −0.3510 (5) | 0.0854 (8) | 0.0389 (15) | |
H4 | 0.4296 | −0.4122 | 0.0504 | 0.047* | |
C5 | 0.5026 (7) | −0.3458 (5) | 0.2081 (7) | 0.0369 (15) | |
C6 | 0.5533 (7) | −0.2572 (5) | 0.2625 (8) | 0.0360 (16) | |
H6 | 0.5818 | −0.2559 | 0.3456 | 0.043* | |
C7 | 0.6101 (7) | −0.0736 (5) | 0.2472 (6) | 0.0343 (14) | |
H7 | 0.6369 | −0.0714 | 0.3307 | 0.041* | |
C8 | 0.6631 (7) | 0.1797 (6) | 0.1527 (6) | 0.0332 (14) | |
C9 | 0.7136 (7) | 0.2793 (5) | 0.2082 (7) | 0.0354 (15) | |
C10 | 0.7100 (8) | 0.3626 (6) | 0.1268 (8) | 0.0458 (18) | |
H10 | 0.6764 | 0.3535 | 0.0458 | 0.055* | |
C11 | 0.7548 (10) | 0.4567 (7) | 0.1642 (12) | 0.063 (3) | |
H11 | 0.7503 | 0.5115 | 0.1090 | 0.076* | |
C12 | 0.8069 (9) | 0.4715 (7) | 0.2835 (11) | 0.059 (2) | |
H12 | 0.8380 | 0.5358 | 0.3088 | 0.071* | |
C13 | 0.8126 (8) | 0.3906 (7) | 0.3647 (9) | 0.052 (2) | |
H13 | 0.8486 | 0.4003 | 0.4449 | 0.062* | |
C14 | 0.7652 (7) | 0.2940 (6) | 0.3286 (7) | 0.0386 (15) | |
C15 | 0.8276 (10) | 0.2211 (8) | 0.5282 (8) | 0.062 (3) | |
H15A | 0.9101 | 0.2462 | 0.5248 | 0.093* | |
H15B | 0.8309 | 0.1545 | 0.5668 | 0.093* | |
H15C | 0.7833 | 0.2682 | 0.5748 | 0.093* | |
H2 | 0.692 (9) | 0.097 (9) | 0.310 (3) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0682 (5) | 0.0405 (4) | 0.0380 (4) | −0.0037 (4) | −0.0105 (3) | −0.0106 (3) |
Br2 | 0.0651 (5) | 0.0333 (4) | 0.0706 (6) | 0.0050 (4) | 0.0171 (4) | 0.0194 (4) |
O1 | 0.059 (3) | 0.029 (2) | 0.027 (2) | −0.007 (2) | −0.006 (2) | 0.0006 (18) |
O2 | 0.079 (4) | 0.043 (3) | 0.039 (3) | −0.015 (3) | −0.011 (3) | 0.005 (3) |
O3 | 0.060 (4) | 0.044 (3) | 0.033 (3) | −0.015 (3) | −0.007 (2) | −0.007 (2) |
N1 | 0.042 (3) | 0.030 (3) | 0.030 (3) | −0.006 (2) | 0.001 (2) | −0.005 (2) |
N2 | 0.050 (3) | 0.028 (3) | 0.029 (3) | −0.010 (3) | −0.003 (2) | −0.003 (2) |
C1 | 0.034 (3) | 0.026 (3) | 0.030 (3) | −0.001 (2) | 0.002 (2) | 0.002 (2) |
C2 | 0.036 (3) | 0.024 (3) | 0.031 (3) | 0.002 (2) | 0.000 (3) | 0.000 (2) |
C3 | 0.036 (4) | 0.034 (3) | 0.033 (4) | 0.003 (3) | −0.004 (3) | −0.003 (3) |
C4 | 0.038 (4) | 0.028 (3) | 0.050 (4) | 0.002 (3) | 0.004 (3) | −0.007 (3) |
C5 | 0.040 (4) | 0.028 (3) | 0.044 (4) | 0.005 (3) | 0.010 (3) | 0.006 (3) |
C6 | 0.039 (4) | 0.026 (3) | 0.042 (4) | 0.000 (3) | 0.002 (3) | 0.005 (3) |
C7 | 0.044 (4) | 0.029 (3) | 0.029 (3) | 0.001 (3) | −0.001 (3) | −0.001 (2) |
C8 | 0.035 (3) | 0.038 (4) | 0.025 (3) | −0.004 (3) | 0.000 (3) | −0.004 (3) |
C9 | 0.038 (4) | 0.032 (4) | 0.038 (4) | −0.005 (3) | 0.011 (3) | −0.008 (3) |
C10 | 0.051 (5) | 0.040 (4) | 0.048 (4) | 0.000 (3) | 0.010 (3) | 0.000 (3) |
C11 | 0.063 (6) | 0.034 (4) | 0.096 (8) | −0.003 (4) | 0.026 (6) | 0.005 (5) |
C12 | 0.056 (5) | 0.036 (4) | 0.088 (7) | −0.013 (4) | 0.018 (5) | −0.020 (4) |
C13 | 0.046 (4) | 0.046 (5) | 0.065 (5) | −0.016 (4) | 0.012 (4) | −0.030 (4) |
C14 | 0.035 (4) | 0.037 (3) | 0.045 (4) | −0.007 (3) | 0.008 (3) | −0.013 (3) |
C15 | 0.061 (6) | 0.086 (7) | 0.037 (4) | −0.011 (5) | −0.005 (4) | −0.007 (4) |
Br1—C3 | 1.925 (7) | C5—C6 | 1.379 (10) |
Br2—C5 | 1.889 (7) | C6—H6 | 0.9300 |
O1—C2 | 1.335 (8) | C7—H7 | 0.9300 |
O1—H1 | 0.8200 | C8—C9 | 1.504 (10) |
O2—C8 | 1.222 (8) | C9—C14 | 1.388 (11) |
O3—C14 | 1.366 (10) | C9—C10 | 1.398 (11) |
O3—C15 | 1.411 (11) | C10—C11 | 1.359 (13) |
N1—C7 | 1.282 (9) | C10—H10 | 0.9300 |
N1—N2 | 1.375 (8) | C11—C12 | 1.380 (17) |
N2—C8 | 1.367 (9) | C11—H11 | 0.9300 |
N2—H2 | 0.90 (5) | C12—C13 | 1.372 (14) |
C1—C2 | 1.401 (9) | C12—H12 | 0.9300 |
C1—C6 | 1.417 (9) | C13—C14 | 1.394 (10) |
C1—C7 | 1.461 (9) | C13—H13 | 0.9300 |
C2—C3 | 1.389 (10) | C15—H15A | 0.9600 |
C3—C4 | 1.386 (11) | C15—H15B | 0.9600 |
C4—C5 | 1.372 (11) | C15—H15C | 0.9600 |
C4—H4 | 0.9300 | ||
C2—O1—H1 | 109.5 | O2—C8—N2 | 120.7 (6) |
C14—O3—C15 | 120.5 (7) | O2—C8—C9 | 122.7 (6) |
C7—N1—N2 | 119.5 (6) | N2—C8—C9 | 116.6 (6) |
C8—N2—N1 | 116.3 (5) | C14—C9—C10 | 118.7 (7) |
C8—N2—H2 | 125 (7) | C14—C9—C8 | 126.3 (7) |
N1—N2—H2 | 118 (7) | C10—C9—C8 | 114.9 (7) |
C2—C1—C6 | 120.5 (6) | C11—C10—C9 | 121.1 (9) |
C2—C1—C7 | 121.3 (6) | C11—C10—H10 | 119.4 |
C6—C1—C7 | 118.1 (6) | C9—C10—H10 | 119.4 |
O1—C2—C3 | 119.2 (6) | C10—C11—C12 | 120.3 (9) |
O1—C2—C1 | 122.8 (6) | C10—C11—H11 | 119.8 |
C3—C2—C1 | 117.9 (6) | C12—C11—H11 | 119.8 |
C4—C3—C2 | 122.3 (7) | C13—C12—C11 | 119.6 (8) |
C4—C3—Br1 | 118.8 (5) | C13—C12—H12 | 120.2 |
C2—C3—Br1 | 118.9 (5) | C11—C12—H12 | 120.2 |
C5—C4—C3 | 118.5 (6) | C12—C13—C14 | 120.9 (9) |
C5—C4—H4 | 120.8 | C12—C13—H13 | 119.6 |
C3—C4—H4 | 120.8 | C14—C13—H13 | 119.6 |
C4—C5—C6 | 122.4 (6) | O3—C14—C9 | 118.4 (6) |
C4—C5—Br2 | 117.3 (5) | O3—C14—C13 | 122.2 (7) |
C6—C5—Br2 | 120.3 (6) | C9—C14—C13 | 119.4 (8) |
C5—C6—C1 | 118.3 (7) | O3—C15—H15A | 109.5 |
C5—C6—H6 | 120.9 | O3—C15—H15B | 109.5 |
C1—C6—H6 | 120.9 | H15A—C15—H15B | 109.5 |
N1—C7—C1 | 117.5 (6) | O3—C15—H15C | 109.5 |
N1—C7—H7 | 121.3 | H15A—C15—H15C | 109.5 |
C1—C7—H7 | 121.3 | H15B—C15—H15C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O3 | 0.90 (5) | 1.97 (9) | 2.617 (8) | 128 (9) |
O1—H1···N1 | 0.82 | 1.93 | 2.535 (7) | 130 |
Experimental details
Crystal data | |
Chemical formula | C15H12Br2N2O3 |
Mr | 428.09 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 298 |
a, b, c (Å) | 10.886 (1), 12.956 (2), 10.965 (2) |
β (°) | 96.476 (3) |
V (Å3) | 1536.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 5.29 |
Crystal size (mm) | 0.30 × 0.30 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.300, 0.329 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4623, 2208, 1992 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.639 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.125, 1.05 |
No. of reflections | 2208 |
No. of parameters | 204 |
No. of restraints | 3 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.35, −0.62 |
Absolute structure | Flack (1983), 531 Friedel pairs |
Absolute structure parameter | 0.513 (19) |
Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O3 | 0.90 (5) | 1.97 (9) | 2.617 (8) | 128 (9) |
O1—H1···N1 | 0.82 | 1.93 | 2.535 (7) | 130 |
Acknowledgements
The Vital Foundation of Ankang University (project No. 2008AKXY012), and the Special Scientific Research Foundation of the Education Office of Shanxi Province (Project No. 02JK202) are gratefully acknowledged.
References
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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.
Study on the crystal structures of hydrazone derivatives is a hot topic in structural chemistry. In the last few years, the crystal structures of a large number of hydrazone compounds have been reported (Mohd Lair et al., 2009; Fun et al., 2008; Li & Ban, 2009; Zhu et al., 2009; Yang, 2007; You et al., 2008). As a continuation of our work in this area (Qu et al., 2008; Yang et al., 2008), the title new hydrazone compound, (I), derived from the reaction of 3,5-dibromo-2-hydroxybenzaldehyde with an equimolar quantity of 2-methoxybenzohydrazide is reported.
In compound (I), Fig. 1, the dihedral angle between the two benzene rings is 3.4 (2)°. Intramolecular N2—H2···O3 and O1—H1···N1 hydrogen bonds, (Table 1) are observed in the molecule. All the bond lengths are within normal values (Allen et al., 1987).