Acta Cryst. (2008). E64, o2070 [ doi:10.1107/S1600536808031395 ]
The title compound, C18H13BrN2O2, was synthesized by the reaction of 2-hydroxy-1-naphthaldehyde with 4-bromobenzohydrazide. This Schiff base molecule has an E configuration about the C=N bond and is almost planar, the dihedral angle between the mean planes through the substituted benzene ring and the naphthyl system being 6.6 (2)°. There is an intramolecular O-H
N hydrogen bond involving the naphthyl hydroxy substituent and the N' atom of the hydrazide group. In the crystal structure, molecules are linked through intermolecular N--HO hydrogen bonds to form chains extending along the b direction.
4-Bromobenzaldehyde (0.1 mmol, 18.5 mg) and 2-hydroxy-1-naphthaldehyde (0.1 mmol, 17.2 mg) were dissolved in methanol (20 ml). The mixture was stirred at reflux for 1 h and cooled to room temperature. After keeping the solution in air for alomost two weeks, yellow block-like crystals of the title compound were formed.
Atom H1 was located from 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 calculated positions and treated as riding atoms, with C–H = 0.93 Å, O–H = 0.82 Å, and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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]](./su2066fig1thm.gif)
| Fig. 1. The molecular structure of the title compound with displacement parameters drawn at the 30% probability level. |
![[Figure 2]](./su2066fig2thm.gif)
| Fig. 2. A persepctive view along the a axis of the crystal packing of the title compound. |
| C18H13BrN2O2 | F(000) = 372 |
| Mr = 369.21 | Dx = 1.627 Mg m−3 |
| Monoclinic, Pc | Mo Kα radiation, λ = 0.71073 Å |
| a = 6.185 (2) Å | Cell parameters from 1589 reflections |
| b = 4.7638 (19) Å | θ = 2.6–24.5° |
| c = 25.689 (10) Å | µ = 2.74 mm−1 |
| β = 95.449 (7)° | T = 298 K |
| V = 753.5 (5) Å3 | Block, yellow |
| Z = 2 | 0.30 × 0.30 × 0.28 mm |
| Bruker SMART CCD area-detector diffractometer | 3119 independent reflections |
| Radiation source: fine-focus sealed tube | 2443 reflections with I > 2σ(I) |
| graphite | Rint = 0.034 |
| ω scans | θmax = 27.0°, θmin = 1.6° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −7→7 |
| Tmin = 0.494, Tmax = 0.514 | k = −6→6 |
| 5817 measured reflections | l = −32→32 |
| 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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | w = 1/[σ2(Fo2) + ] |
| S = 0.90 | (Δ/σ)max = 0.001 |
| 3119 reflections | Δρmax = 0.31 e Å−3 |
| 212 parameters | Δρmin = −0.24 e Å−3 |
| 3 restraints | Absolute structure: Flack (1983), 1493 Friedel pairs |
| Primary atom site location: structure-invariant direct methods | Flack parameter: 0.026 (12) |
| C18H13BrN2O2 | V = 753.5 (5) Å3 |
| Mr = 369.21 | Z = 2 |
| Monoclinic, Pc | Mo Kα radiation |
| a = 6.185 (2) Å | µ = 2.74 mm−1 |
| b = 4.7638 (19) Å | T = 298 K |
| c = 25.689 (10) Å | 0.30 × 0.30 × 0.28 mm |
| β = 95.449 (7)° |
| Bruker SMART CCD area-detector diffractometer | 3119 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2443 reflections with I > 2σ(I) |
| Tmin = 0.494, Tmax = 0.514 | Rint = 0.034 |
| 5817 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.101 | Δρmax = 0.31 e Å−3 |
| S = 0.90 | Δρmin = −0.24 e Å−3 |
| 3119 reflections | Absolute structure: Flack (1983), 1493 Friedel pairs |
| 212 parameters | Flack parameter: 0.026 (12) |
| 3 restraints |
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. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 1.08310 (11) | 0.22527 (11) | 1.13545 (4) | 0.0685 (2) | |
| O1 | 0.2012 (5) | −0.3701 (5) | 0.99811 (12) | 0.0474 (7) | |
| O2 | −0.3678 (6) | −0.2844 (6) | 0.91908 (13) | 0.0509 (8) | |
| H2 | −0.2458 | −0.2481 | 0.9327 | 0.076* | |
| N1 | 0.1759 (5) | 0.0647 (6) | 0.96274 (13) | 0.0379 (7) | |
| N2 | −0.0057 (5) | −0.0129 (6) | 0.93167 (12) | 0.0377 (7) | |
| C18 | 0.7851 (7) | 0.2520 (7) | 1.04481 (17) | 0.0407 (9) | |
| H18 | 0.8775 | 0.3902 | 1.0342 | 0.049* | |
| C1 | 0.8295 (7) | 0.1191 (9) | 1.09188 (16) | 0.0433 (9) | |
| C2 | 0.6996 (7) | −0.0854 (9) | 1.10869 (16) | 0.0480 (10) | |
| H2A | 0.7329 | −0.1711 | 1.1410 | 0.058* | |
| C3 | 0.5173 (7) | −0.1632 (8) | 1.07685 (17) | 0.0432 (10) | |
| H3 | 0.4282 | −0.3052 | 1.0875 | 0.052* | |
| C4 | 0.4659 (6) | −0.0328 (7) | 1.02954 (15) | 0.0340 (8) | |
| C5 | 0.6012 (6) | 0.1770 (7) | 1.01362 (16) | 0.0369 (8) | |
| H5 | 0.5673 | 0.2669 | 0.9818 | 0.044* | |
| C6 | 0.2705 (6) | −0.1305 (8) | 0.99609 (15) | 0.0350 (8) | |
| C7 | −0.0776 (6) | 0.1545 (8) | 0.89501 (16) | 0.0357 (8) | |
| H7 | −0.0023 | 0.3190 | 0.8893 | 0.043* | |
| C8 | −0.2727 (6) | 0.0903 (7) | 0.86278 (15) | 0.0361 (8) | |
| C9 | −0.4138 (6) | −0.1175 (8) | 0.87700 (16) | 0.0399 (9) | |
| C10 | −0.6139 (7) | −0.1627 (9) | 0.8477 (2) | 0.0513 (11) | |
| H10 | −0.7084 | −0.2975 | 0.8587 | 0.062* | |
| C11 | −0.6716 (6) | −0.0146 (9) | 0.80394 (19) | 0.0527 (11) | |
| H11 | −0.8065 | −0.0462 | 0.7857 | 0.063* | |
| C12 | −0.5319 (7) | 0.1866 (8) | 0.78536 (19) | 0.0459 (10) | |
| C13 | −0.5851 (8) | 0.3322 (10) | 0.7382 (2) | 0.0558 (12) | |
| H13 | −0.7177 | 0.2963 | 0.7191 | 0.067* | |
| C14 | −0.4491 (8) | 0.5229 (10) | 0.71980 (18) | 0.0596 (12) | |
| H14 | −0.4861 | 0.6156 | 0.6883 | 0.071* | |
| C15 | −0.2513 (8) | 0.5774 (10) | 0.74925 (17) | 0.0568 (11) | |
| H15 | −0.1576 | 0.7101 | 0.7372 | 0.068* | |
| C16 | −0.1927 (6) | 0.4422 (8) | 0.79472 (15) | 0.0441 (9) | |
| H16 | −0.0587 | 0.4806 | 0.8129 | 0.053* | |
| C17 | −0.3314 (6) | 0.2444 (7) | 0.81494 (17) | 0.0377 (9) | |
| H1 | 0.209 (11) | 0.245 (4) | 0.969 (3) | 0.080* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0451 (2) | 0.0994 (4) | 0.0583 (3) | −0.0070 (3) | −0.00903 (17) | −0.0151 (3) |
| O1 | 0.0489 (17) | 0.0246 (13) | 0.068 (2) | −0.0093 (12) | −0.0010 (14) | 0.0020 (13) |
| O2 | 0.055 (2) | 0.0432 (16) | 0.055 (2) | −0.0164 (13) | 0.0070 (15) | −0.0067 (14) |
| N1 | 0.0431 (18) | 0.0268 (15) | 0.0425 (18) | −0.0060 (14) | −0.0022 (14) | −0.0048 (13) |
| N2 | 0.0343 (15) | 0.0308 (15) | 0.0473 (19) | −0.0038 (13) | 0.0002 (13) | −0.0074 (14) |
| C18 | 0.036 (2) | 0.043 (2) | 0.044 (2) | −0.0092 (17) | 0.0070 (17) | −0.0058 (17) |
| C1 | 0.036 (2) | 0.047 (2) | 0.046 (3) | −0.0004 (18) | 0.0002 (17) | −0.0128 (19) |
| C2 | 0.050 (2) | 0.050 (3) | 0.042 (2) | 0.000 (2) | −0.0038 (19) | 0.0053 (19) |
| C3 | 0.044 (2) | 0.035 (2) | 0.051 (3) | −0.0049 (17) | 0.0040 (19) | 0.0034 (17) |
| C4 | 0.038 (2) | 0.0274 (18) | 0.037 (2) | −0.0041 (15) | 0.0040 (15) | −0.0030 (15) |
| C5 | 0.038 (2) | 0.0343 (19) | 0.038 (2) | −0.0062 (15) | 0.0045 (16) | −0.0027 (15) |
| C6 | 0.038 (2) | 0.0250 (18) | 0.043 (2) | −0.0006 (16) | 0.0105 (17) | −0.0058 (16) |
| C7 | 0.035 (2) | 0.0306 (18) | 0.041 (2) | −0.0062 (15) | 0.0040 (16) | −0.0041 (16) |
| C8 | 0.036 (2) | 0.0308 (18) | 0.041 (2) | −0.0011 (16) | 0.0023 (16) | −0.0111 (16) |
| C9 | 0.041 (2) | 0.035 (2) | 0.044 (2) | −0.0055 (17) | 0.0084 (17) | −0.0101 (17) |
| C10 | 0.038 (2) | 0.049 (2) | 0.068 (3) | −0.0138 (19) | 0.008 (2) | −0.015 (2) |
| C11 | 0.031 (2) | 0.060 (3) | 0.064 (3) | −0.0061 (18) | −0.0082 (18) | −0.023 (2) |
| C12 | 0.038 (2) | 0.044 (2) | 0.055 (3) | 0.0017 (17) | −0.0037 (19) | −0.0178 (18) |
| C13 | 0.049 (3) | 0.057 (3) | 0.057 (3) | 0.009 (2) | −0.013 (2) | −0.015 (2) |
| C14 | 0.067 (3) | 0.068 (3) | 0.043 (3) | 0.010 (3) | −0.003 (2) | −0.001 (2) |
| C15 | 0.059 (3) | 0.066 (3) | 0.046 (3) | −0.002 (2) | 0.008 (2) | −0.001 (2) |
| C16 | 0.038 (2) | 0.051 (3) | 0.044 (2) | −0.0058 (18) | 0.0023 (17) | −0.0005 (19) |
| C17 | 0.033 (2) | 0.036 (2) | 0.043 (2) | 0.0018 (15) | 0.0005 (16) | −0.0104 (16) |
| Br1—C1 | 1.907 (4) | C7—C8 | 1.430 (5) |
| O1—C6 | 1.222 (5) | C7—H7 | 0.9300 |
| O2—C9 | 1.350 (5) | C8—C9 | 1.391 (5) |
| O2—H2 | 0.8200 | C8—C17 | 1.448 (6) |
| N1—C6 | 1.359 (5) | C9—C10 | 1.403 (6) |
| N1—N2 | 1.366 (4) | C10—C11 | 1.346 (7) |
| N1—H1 | 0.89 (3) | C10—H10 | 0.9300 |
| N2—C7 | 1.281 (5) | C11—C12 | 1.404 (6) |
| C18—C1 | 1.369 (6) | C11—H11 | 0.9300 |
| C18—C5 | 1.375 (6) | C12—C13 | 1.407 (7) |
| C18—H18 | 0.9300 | C12—C17 | 1.419 (6) |
| C1—C2 | 1.359 (6) | C13—C14 | 1.354 (7) |
| C2—C3 | 1.379 (6) | C13—H13 | 0.9300 |
| C2—H2A | 0.9300 | C14—C15 | 1.400 (7) |
| C3—C4 | 1.375 (5) | C14—H14 | 0.9300 |
| C3—H3 | 0.9300 | C15—C16 | 1.353 (6) |
| C4—C5 | 1.389 (5) | C15—H15 | 0.9300 |
| C4—C6 | 1.490 (5) | C16—C17 | 1.406 (6) |
| C5—H5 | 0.9300 | C16—H16 | 0.9300 |
| C9—O2—H2 | 109.5 | C9—C8—C17 | 118.1 (3) |
| C6—N1—N2 | 117.7 (3) | C7—C8—C17 | 120.8 (3) |
| C6—N1—H1 | 118 (5) | O2—C9—C8 | 122.7 (4) |
| N2—N1—H1 | 121 (5) | O2—C9—C10 | 116.6 (4) |
| C7—N2—N1 | 118.0 (3) | C8—C9—C10 | 120.8 (4) |
| C1—C18—C5 | 118.7 (4) | C11—C10—C9 | 121.2 (4) |
| C1—C18—H18 | 120.7 | C11—C10—H10 | 119.4 |
| C5—C18—H18 | 120.7 | C9—C10—H10 | 119.4 |
| C2—C1—C18 | 122.5 (4) | C10—C11—C12 | 121.3 (4) |
| C2—C1—Br1 | 118.8 (3) | C10—C11—H11 | 119.4 |
| C18—C1—Br1 | 118.7 (3) | C12—C11—H11 | 119.4 |
| C1—C2—C3 | 118.6 (4) | C11—C12—C13 | 121.9 (4) |
| C1—C2—H2A | 120.7 | C11—C12—C17 | 119.0 (4) |
| C3—C2—H2A | 120.7 | C13—C12—C17 | 119.1 (4) |
| C4—C3—C2 | 120.7 (4) | C14—C13—C12 | 121.9 (4) |
| C4—C3—H3 | 119.7 | C14—C13—H13 | 119.0 |
| C2—C3—H3 | 119.7 | C12—C13—H13 | 119.0 |
| C3—C4—C5 | 119.3 (4) | C13—C14—C15 | 118.4 (4) |
| C3—C4—C6 | 118.4 (3) | C13—C14—H14 | 120.8 |
| C5—C4—C6 | 122.2 (4) | C15—C14—H14 | 120.8 |
| C18—C5—C4 | 120.2 (4) | C16—C15—C14 | 121.8 (5) |
| C18—C5—H5 | 119.9 | C16—C15—H15 | 119.1 |
| C4—C5—H5 | 119.9 | C14—C15—H15 | 119.1 |
| O1—C6—N1 | 122.3 (3) | C15—C16—C17 | 121.0 (4) |
| O1—C6—C4 | 122.4 (3) | C15—C16—H16 | 119.5 |
| N1—C6—C4 | 115.3 (3) | C17—C16—H16 | 119.5 |
| N2—C7—C8 | 120.5 (3) | C16—C17—C12 | 117.7 (4) |
| N2—C7—H7 | 119.8 | C16—C17—C8 | 122.7 (4) |
| C8—C7—H7 | 119.8 | C12—C17—C8 | 119.5 (4) |
| C9—C8—C7 | 121.1 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.89 (3) | 1.99 (3) | 2.841 (4) | 160 (6) |
| O2—H2···N2 | 0.82 | 1.86 | 2.580 (4) | 145 |
| Symmetry codes: (i) x, y+1, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1i | 0.89 (3) | 1.99 (3) | 2.841 (4) | 160 (6) |
| O2—H2···N2 | 0.82 | 1.86 | 2.580 (4) | 145 |
| Symmetry codes: (i) x, y+1, z. |
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Schiff base compounds have been found to have potential pharmacological and antitumor properties (Brückner et al., 2000; Harrop et al., 2003; Ren et al., 2002). Recently, a few Schiff base compounds obtained from the reaction of aldehydes with benzohydrazides have been reported (Diao et al., 2008; Diao et al., 2007; Diao, 2007; Li et al., 2007; Huang et al., 2007). As a further study of such compounds, we report here on the structure of the title compound.
The title compound, a Schiff base synthesized by the reaction of 2-hydroxy-1-naphthaldehyde with 4-bromobenzohydrazide, is almost planar (Fig. 1), with the dihedral angle between the mean planes of the substituted benzene ring and the naphthyl ring being only 6.6 (2)°. The torsion angles C4—C6—N1—N2 and C8—C7—N2—N1 are 0.9 (3) and 2.9 (3)°, respectively. There is an intramolecular O-H···N hydrogen bond involving the naphthyl hydroxyl substituent and the NH H-atom of the hydrazide group (Table 1).
In the crystal molecules are linked via N–H···O intermolecular hydrogen bonds (Table 1), to form chains extending in the b direction (Fig. 2).