Acta Cryst. (2009). E65, o2085 [ doi:10.1107/S1600536809030220 ]
The title compound, C14H9BrCl2N2O, was synthesized by the reaction of 2,4-dichlorobenzaldehyde with an equimolar quantity of 3-bromobenzohydrazide in methanol. The molecule displays an E configuration about the C=N bond. The dihedral angle between the two benzene rings is 5.3 (2)°. In the crystal structure, molecules are linked through intermolecular N-H
O and C-HO hydrogen bonds, forming chains running along the c axis.
The title compound was prepared by refluxing equimolar quantities of 2,4-chlorobenzaldehyde with 3-bromobenzohydrazide in methanol. Colourless block-shaped crystals 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 and constrained to ride on their parent atoms, with C-H distances of 0.93 Å, and with Uiso(H) set at 1.2Ueq(C).
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).
![[Figure 1]](./ci2871fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. |
![[Figure 2]](./ci2871fig2thm.gif)
| Fig. 2. The molecular packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines. C-bound H atoms have been omitted for clarity. |
| C14H9BrCl2N2O | F(000) = 736 |
| Mr = 372.04 | Dx = 1.687 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 1215 reflections |
| a = 12.140 (2) Å | θ = 2.2–24.5° |
| b = 14.356 (3) Å | µ = 3.17 mm−1 |
| c = 8.452 (2) Å | T = 298 K |
| β = 96.019 (3)° | Block, colourless |
| V = 1464.9 (5) Å3 | 0.20 × 0.20 × 0.18 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2350 independent reflections |
| Radiation source: fine-focus sealed tube | 1561 reflections with I > 2σ(I) |
| graphite | Rint = 0.048 |
| ω scans | θmax = 24.2°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −13→13 |
| Tmin = 0.570, Tmax = 0.600 | k = −16→15 |
| 6615 measured reflections | l = −4→9 |
| 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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.027P)2 + 1.2965P] where P = (Fo2 + 2Fc2)/3 |
| 2350 reflections | (Δ/σ)max = 0.001 |
| 184 parameters | Δρmax = 0.64 e Å−3 |
| 1 restraint | Δρmin = −0.76 e Å−3 |
| C14H9BrCl2N2O | V = 1464.9 (5) Å3 |
| Mr = 372.04 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.140 (2) Å | µ = 3.17 mm−1 |
| b = 14.356 (3) Å | T = 298 K |
| c = 8.452 (2) Å | 0.20 × 0.20 × 0.18 mm |
| β = 96.019 (3)° |
| Bruker SMART CCD area-detector diffractometer | 2350 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2001) | 1561 reflections with I > 2σ(I) |
| Tmin = 0.570, Tmax = 0.600 | Rint = 0.048 |
| 6615 measured reflections | θmax = 24.2° |
| R[F2 > 2σ(F2)] = 0.042 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.094 | Δρmax = 0.64 e Å−3 |
| S = 1.01 | Δρmin = −0.76 e Å−3 |
| 2350 reflections | Absolute structure: ? |
| 184 parameters | Flack parameter: ? |
| 1 restraint | Rogers parameter: ? |
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 | 0.63560 (5) | 0.68952 (3) | 0.11003 (7) | 0.0796 (3) | |
| Cl1 | 0.77292 (12) | −0.09489 (8) | 0.12692 (16) | 0.0724 (4) | |
| Cl2 | 1.00210 (13) | −0.17858 (10) | −0.36215 (18) | 0.0857 (5) | |
| N1 | 0.7760 (3) | 0.1874 (2) | −0.0336 (4) | 0.0359 (8) | |
| N2 | 0.7287 (3) | 0.2522 (2) | 0.0607 (4) | 0.0371 (8) | |
| O1 | 0.6990 (2) | 0.34967 (18) | −0.1509 (3) | 0.0505 (8) | |
| C1 | 0.8471 (3) | 0.0368 (3) | −0.0658 (5) | 0.0376 (10) | |
| C2 | 0.8405 (3) | −0.0571 (3) | −0.0332 (5) | 0.0422 (10) | |
| C3 | 0.8859 (4) | −0.1247 (3) | −0.1250 (6) | 0.0494 (12) | |
| H3 | 0.8792 | −0.1877 | −0.1025 | 0.059* | |
| C4 | 0.9409 (4) | −0.0953 (3) | −0.2499 (6) | 0.0511 (12) | |
| C5 | 0.9513 (4) | −0.0029 (3) | −0.2835 (5) | 0.0503 (12) | |
| H5 | 0.9904 | 0.0157 | −0.3670 | 0.060* | |
| C6 | 0.9041 (3) | 0.0622 (3) | −0.1940 (5) | 0.0434 (11) | |
| H6 | 0.9100 | 0.1249 | −0.2192 | 0.052* | |
| C7 | 0.7967 (3) | 0.1081 (3) | 0.0279 (5) | 0.0380 (10) | |
| H7 | 0.7803 | 0.0953 | 0.1307 | 0.046* | |
| C8 | 0.6924 (3) | 0.3329 (3) | −0.0095 (5) | 0.0359 (10) | |
| C9 | 0.6420 (3) | 0.4015 (3) | 0.0939 (4) | 0.0339 (9) | |
| C10 | 0.6578 (3) | 0.4950 (3) | 0.0618 (5) | 0.0378 (10) | |
| H10 | 0.7001 | 0.5125 | −0.0188 | 0.045* | |
| C11 | 0.6103 (4) | 0.5617 (3) | 0.1505 (5) | 0.0471 (12) | |
| C12 | 0.5449 (4) | 0.5370 (3) | 0.2661 (5) | 0.0567 (13) | |
| H12 | 0.5120 | 0.5826 | 0.3237 | 0.068* | |
| C13 | 0.5282 (4) | 0.4437 (4) | 0.2965 (5) | 0.0548 (13) | |
| H13 | 0.4832 | 0.4266 | 0.3741 | 0.066* | |
| C14 | 0.5781 (3) | 0.3756 (3) | 0.2123 (5) | 0.0422 (11) | |
| H14 | 0.5685 | 0.3129 | 0.2353 | 0.051* | |
| H2 | 0.732 (4) | 0.243 (3) | 0.1660 (16) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0888 (4) | 0.0329 (3) | 0.1108 (5) | 0.0064 (3) | −0.0197 (3) | −0.0116 (3) |
| Cl1 | 0.0879 (10) | 0.0444 (7) | 0.0906 (10) | −0.0053 (7) | 0.0363 (8) | 0.0120 (7) |
| Cl2 | 0.0982 (11) | 0.0673 (9) | 0.0926 (10) | 0.0235 (8) | 0.0146 (9) | −0.0379 (8) |
| N1 | 0.048 (2) | 0.0266 (18) | 0.0342 (19) | 0.0030 (16) | 0.0087 (16) | −0.0037 (16) |
| N2 | 0.059 (2) | 0.0253 (18) | 0.0288 (18) | 0.0078 (16) | 0.0119 (18) | −0.0020 (16) |
| O1 | 0.084 (2) | 0.0390 (17) | 0.0310 (18) | 0.0149 (15) | 0.0173 (16) | 0.0037 (13) |
| C1 | 0.041 (2) | 0.034 (2) | 0.037 (2) | 0.0047 (19) | −0.001 (2) | −0.0054 (19) |
| C2 | 0.042 (3) | 0.035 (2) | 0.049 (3) | 0.003 (2) | 0.003 (2) | −0.003 (2) |
| C3 | 0.050 (3) | 0.032 (2) | 0.064 (3) | 0.004 (2) | −0.003 (3) | −0.007 (2) |
| C4 | 0.047 (3) | 0.049 (3) | 0.056 (3) | 0.015 (2) | −0.003 (2) | −0.022 (2) |
| C5 | 0.058 (3) | 0.048 (3) | 0.047 (3) | 0.005 (2) | 0.011 (2) | −0.010 (2) |
| C6 | 0.056 (3) | 0.035 (2) | 0.039 (3) | 0.000 (2) | 0.005 (2) | −0.001 (2) |
| C7 | 0.050 (3) | 0.033 (2) | 0.031 (2) | 0.001 (2) | 0.006 (2) | −0.0001 (19) |
| C8 | 0.043 (3) | 0.029 (2) | 0.036 (3) | −0.0030 (18) | 0.007 (2) | −0.0020 (19) |
| C9 | 0.040 (2) | 0.034 (2) | 0.028 (2) | 0.0036 (19) | 0.0027 (19) | −0.0033 (18) |
| C10 | 0.041 (2) | 0.032 (2) | 0.039 (2) | 0.0013 (19) | 0.001 (2) | −0.003 (2) |
| C11 | 0.055 (3) | 0.032 (2) | 0.050 (3) | 0.011 (2) | −0.013 (2) | −0.009 (2) |
| C12 | 0.066 (3) | 0.060 (3) | 0.043 (3) | 0.030 (3) | 0.001 (3) | −0.013 (3) |
| C13 | 0.050 (3) | 0.077 (4) | 0.039 (3) | 0.019 (3) | 0.012 (2) | 0.000 (3) |
| C14 | 0.047 (3) | 0.042 (2) | 0.038 (3) | 0.005 (2) | 0.006 (2) | 0.002 (2) |
| Br1—C11 | 1.897 (4) | C5—C6 | 1.365 (5) |
| Cl1—C2 | 1.741 (4) | C5—H5 | 0.93 |
| Cl2—C4 | 1.740 (4) | C6—H6 | 0.93 |
| N1—C7 | 1.265 (4) | C7—H7 | 0.93 |
| N1—N2 | 1.388 (4) | C8—C9 | 1.489 (5) |
| N2—C8 | 1.354 (5) | C9—C14 | 1.380 (5) |
| N2—H2 | 0.897 (10) | C9—C10 | 1.386 (5) |
| O1—C8 | 1.230 (4) | C10—C11 | 1.380 (5) |
| C1—C2 | 1.380 (5) | C10—H10 | 0.93 |
| C1—C6 | 1.394 (5) | C11—C12 | 1.369 (6) |
| C1—C7 | 1.467 (5) | C12—C13 | 1.382 (6) |
| C2—C3 | 1.391 (6) | C12—H12 | 0.93 |
| C3—C4 | 1.374 (6) | C13—C14 | 1.386 (6) |
| C3—H3 | 0.93 | C13—H13 | 0.93 |
| C4—C5 | 1.365 (6) | C14—H14 | 0.93 |
| C7—N1—N2 | 116.3 (3) | N1—C7—H7 | 120.6 |
| C8—N2—N1 | 117.2 (3) | C1—C7—H7 | 120.6 |
| C8—N2—H2 | 123 (3) | O1—C8—N2 | 122.8 (3) |
| N1—N2—H2 | 119 (3) | O1—C8—C9 | 120.9 (3) |
| C2—C1—C6 | 117.1 (4) | N2—C8—C9 | 116.3 (3) |
| C2—C1—C7 | 122.5 (4) | C14—C9—C10 | 120.2 (3) |
| C6—C1—C7 | 120.4 (4) | C14—C9—C8 | 123.0 (4) |
| C1—C2—C3 | 122.3 (4) | C10—C9—C8 | 116.8 (4) |
| C1—C2—Cl1 | 120.1 (3) | C11—C10—C9 | 119.5 (4) |
| C3—C2—Cl1 | 117.6 (3) | C11—C10—H10 | 120.3 |
| C4—C3—C2 | 117.9 (4) | C9—C10—H10 | 120.3 |
| C4—C3—H3 | 121.1 | C12—C11—C10 | 121.0 (4) |
| C2—C3—H3 | 121.1 | C12—C11—Br1 | 119.7 (3) |
| C5—C4—C3 | 121.4 (4) | C10—C11—Br1 | 119.3 (4) |
| C5—C4—Cl2 | 120.0 (4) | C11—C12—C13 | 119.4 (4) |
| C3—C4—Cl2 | 118.5 (4) | C11—C12—H12 | 120.3 |
| C4—C5—C6 | 119.8 (4) | C13—C12—H12 | 120.3 |
| C4—C5—H5 | 120.1 | C12—C13—C14 | 120.6 (4) |
| C6—C5—H5 | 120.1 | C12—C13—H13 | 119.7 |
| C5—C6—C1 | 121.5 (4) | C14—C13—H13 | 119.7 |
| C5—C6—H6 | 119.2 | C9—C14—C13 | 119.4 (4) |
| C1—C6—H6 | 119.2 | C9—C14—H14 | 120.3 |
| N1—C7—C1 | 118.8 (4) | C13—C14—H14 | 120.3 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.90 (1) | 2.11 (3) | 2.898 (4) | 146 (4) |
| C7—H7···O1i | 0.93 | 2.32 | 3.134 (5) | 146 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1i | 0.90 (1) | 2.11 (3) | 2.898 (4) | 146 (4) |
| C7—H7···O1i | 0.93 | 2.32 | 3.134 (5) | 146 |
| Symmetry codes: (i) x, −y+1/2, z+1/2. |
The Vital Foundation of Ankang University (project No. 2008AKXY012) and the Special Scientific Research Foundation of the Education Office of Shanxi Province (Project No. 02 J K202) are gratefully acknowledged.
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Study on the crystal structures of hydrazone derivatives is a hot topic in structural chemistry. In the last few years, 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; Cao & Lu, 2009a,b; Qu & Cao, 2009; Cao & Wang, 2009), the title new hydrazone compound derived from the reaction of 2,4-dichlorobenzaldehyde with an equimolar quantity of 3-bromobenzohydrazide is reported.
In the title compound (Fig. 1), the dihedral angle between the two benzene rings is 5.3 (2)°. The molecule displays an E configuration about the C═N bond. In the crystal structure, molecules are linked through intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) to form chains running along the c axis (Fig. 2).