Abstract
The Schiff base, C20H14BrClN2O2, displays a trans conformation with respect to the C=N double bond. The aromatic rings at either end of the –C(=O)–NH–N=C– fragment are nearly parallel [dihedral angle = 3.4 (5)°]. The hydroxy group forms an intramolecular hydrogen bond to the imino N atom.
Related literature
The chemistry of aroylhydrazones continues to attract much attention due to their ability to coordinate to metal ions (Singh et al., 1982 ▶; Salem, 1998 ▶) and their biological activity (Singh et al., 1982 ▶; Carcelli et al., 1995 ▶).
Experimental
Crystal data
C20H14BrClN2O2
M r = 429.69
Triclinic,
a = 7.3664 (8) Å
b = 10.6894 (11) Å
c = 12.3029 (14) Å
α = 71.976 (2)°
β = 82.228 (2)°
γ = 85.466 (2)°
V = 912.05 (17) Å3
Z = 2
Mo Kα radiation
μ = 2.42 mm−1
T = 273 K
0.20 × 0.16 × 0.13 mm
Data collection
Bruker SMART area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.644, T max = 0.744
4841 measured reflections
3189 independent reflections
2467 reflections with I > 2σ(I)
R int = 0.015
Refinement
R[F 2 > 2σ(F 2)] = 0.034
wR(F 2) = 0.085
S = 1.04
3189 reflections
237 parameters
H-atom parameters constrained
Δρmax = 0.32 e Å−3
Δρmin = −0.44 e Å−3
Data collection: SMART (Bruker, 1996 ▶); cell refinement: SAINT (Bruker, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.
Supplementary Material
Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027949/ng2613sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027949/ng2613Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O1—H1⋯N1 | 0.82 | 1.84 | 2.554 (3) | 145 |
Acknowledgments
This project was supported by the Postgraduate Foundation of Xi’an Polytechnic University (grant No. Y05–2–09).
supplementary crystallographic information
Comment
The chemistry of aroylhydrazones continues to attract much attention due to their coordination ability to metal ions (Singh et al., 1982; Salem, 1998) and their biological activity (Singh et al., 1982; Carcelli et al., 1995). As an extension of work on the structural characterization of aroylhydrazone derivatives,the title compound, (I),was synthesized and its crystal structure is reported here.
The title molecule displays a trans conformation with respect to the C7=N1 double bond (Fig. 1). The crystal structure is stabilized by intramolecular O—H···N hydrogen bonds (Table).
Experimental
4-chlorobenzohydrazide(0.02 mol,3.42 g) was dissolved in anhydrous ethanol (50 ml), and 1-(5-bromo-2-hydroxyphenyl)ethanone (0.02 mol, 4.30 g) was added. The reaction mixture was refluxed for 6 h with stirring, then the resulting precipitate was collected by filtration, washed several times with ethanol and dried in vacuo (yield 85%). The compound (2.0 mmol,0.68 g) was dissolved in dimethylformamide (30 ml) and kept at room temperature for 30 d to obtain yellow single crystals suitable for X-ray diffraction.
Refinement
All H atoms were positioned geometrically and treated as riding on their parent atoms,with C—H(aromatic) = 0.93 Å, O—H = 0.82 Å, and N—H = 0.86 Å and with Uiso(H) =1.2Ueq(Caromatic,N).
Figures
Fig. 1.
The molecular structure of compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Crystal data
| C20H14BrClN2O2 | Z = 2 |
| Mr = 429.69 | F(000) = 432 |
| Triclinic, P1 | Dx = 1.565 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
| a = 7.3664 (8) Å | Cell parameters from 1806 reflections |
| b = 10.6894 (11) Å | θ = 2.8–25.3° |
| c = 12.3029 (14) Å | µ = 2.42 mm−1 |
| α = 71.976 (2)° | T = 273 K |
| β = 82.228 (2)° | Block, yellow |
| γ = 85.466 (2)° | 0.20 × 0.16 × 0.13 mm |
| V = 912.05 (17) Å3 |
Data collection
| Bruker SMART area-detector diffractometer | 3189 independent reflections |
| Radiation source: fine-focus sealed tube | 2467 reflections with I > 2σ(I) |
| graphite | Rint = 0.015 |
| φ and ω scans | θmax = 25.1°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→8 |
| Tmin = 0.644, Tmax = 0.744 | k = −8→12 |
| 4841 measured reflections | l = −14→14 |
Refinement
| 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.085 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0366P)2 + 0.3768P] where P = (Fo2 + 2Fc2)/3 |
| 3189 reflections | (Δ/σ)max = 0.001 |
| 237 parameters | Δρmax = 0.32 e Å−3 |
| 0 restraints | Δρmin = −0.43 e Å−3 |
Special details
| 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)
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.36717 (5) | 1.17236 (4) | 1.00467 (3) | 0.06975 (17) | |
| Cl1 | 0.08513 (13) | 0.47987 (9) | 0.23226 (8) | 0.0729 (3) | |
| O1 | 0.3069 (3) | 1.25145 (19) | 0.50596 (17) | 0.0627 (6) | |
| H1 | 0.2882 | 1.1830 | 0.4931 | 0.094* | |
| O2 | 0.2209 (3) | 1.0374 (2) | 0.33927 (17) | 0.0587 (6) | |
| N1 | 0.2632 (3) | 1.0045 (2) | 0.55663 (18) | 0.0454 (6) | |
| N2 | 0.2388 (3) | 0.9007 (2) | 0.51767 (19) | 0.0480 (6) | |
| H2 | 0.2367 | 0.8215 | 0.5636 | 0.058* | |
| C1 | 0.3457 (4) | 1.1936 (3) | 0.8483 (2) | 0.0465 (7) | |
| C2 | 0.3209 (4) | 1.0858 (3) | 0.8134 (2) | 0.0432 (6) | |
| H2A | 0.3141 | 1.0027 | 0.8673 | 0.052* | |
| C3 | 0.3060 (3) | 1.0998 (2) | 0.6988 (2) | 0.0389 (6) | |
| C4 | 0.3189 (4) | 1.2264 (3) | 0.6188 (2) | 0.0455 (7) | |
| C5 | 0.3465 (4) | 1.3328 (3) | 0.6566 (3) | 0.0540 (8) | |
| H5 | 0.3564 | 1.4163 | 0.6036 | 0.065* | |
| C6 | 0.3595 (4) | 1.3169 (3) | 0.7695 (3) | 0.0534 (8) | |
| H6 | 0.3775 | 1.3891 | 0.7932 | 0.064* | |
| C7 | 0.2801 (4) | 0.9829 (3) | 0.6636 (2) | 0.0397 (6) | |
| C8 | 0.2759 (4) | 0.8493 (2) | 0.7500 (2) | 0.0380 (6) | |
| C9 | 0.4302 (4) | 0.7655 (3) | 0.7577 (2) | 0.0474 (7) | |
| H9 | 0.5367 | 0.7920 | 0.7083 | 0.057* | |
| C10 | 0.4261 (5) | 0.6424 (3) | 0.8389 (3) | 0.0544 (8) | |
| H10 | 0.5296 | 0.5861 | 0.8433 | 0.065* | |
| C11 | 0.2707 (5) | 0.6030 (3) | 0.9127 (3) | 0.0524 (8) | |
| H11 | 0.2690 | 0.5206 | 0.9677 | 0.063* | |
| C12 | 0.1173 (4) | 0.6854 (3) | 0.9054 (3) | 0.0534 (8) | |
| H12 | 0.0117 | 0.6586 | 0.9557 | 0.064* | |
| C13 | 0.1186 (4) | 0.8074 (3) | 0.8242 (2) | 0.0485 (7) | |
| H13 | 0.0134 | 0.8620 | 0.8190 | 0.058* | |
| C14 | 0.2180 (4) | 0.9262 (3) | 0.4043 (2) | 0.0415 (6) | |
| C15 | 0.1925 (4) | 0.8100 (3) | 0.3660 (2) | 0.0394 (6) | |
| C16 | 0.1873 (4) | 0.6816 (3) | 0.4374 (2) | 0.0548 (8) | |
| H16 | 0.2020 | 0.6634 | 0.5147 | 0.066* | |
| C17 | 0.1604 (5) | 0.5797 (3) | 0.3946 (3) | 0.0593 (8) | |
| H17 | 0.1600 | 0.4931 | 0.4423 | 0.071* | |
| C18 | 0.1345 (4) | 0.6076 (3) | 0.2821 (2) | 0.0480 (7) | |
| C19 | 0.1422 (4) | 0.7332 (3) | 0.2085 (3) | 0.0555 (8) | |
| H19 | 0.1275 | 0.7504 | 0.1312 | 0.067* | |
| C20 | 0.1724 (4) | 0.8337 (3) | 0.2515 (2) | 0.0491 (7) | |
| H20 | 0.1792 | 0.9193 | 0.2021 | 0.059* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0901 (3) | 0.0740 (3) | 0.0629 (2) | 0.00901 (19) | −0.02581 (18) | −0.04231 (19) |
| Cl1 | 0.0828 (6) | 0.0743 (6) | 0.0825 (6) | −0.0160 (5) | −0.0070 (5) | −0.0520 (5) |
| O1 | 0.1015 (18) | 0.0392 (12) | 0.0457 (12) | −0.0063 (12) | −0.0087 (11) | −0.0094 (9) |
| O2 | 0.0902 (16) | 0.0397 (12) | 0.0469 (12) | −0.0099 (11) | −0.0193 (11) | −0.0075 (10) |
| N1 | 0.0639 (15) | 0.0360 (13) | 0.0407 (13) | −0.0063 (11) | −0.0108 (11) | −0.0149 (10) |
| N2 | 0.0763 (17) | 0.0328 (13) | 0.0384 (12) | −0.0087 (11) | −0.0132 (11) | −0.0115 (10) |
| C1 | 0.0478 (16) | 0.0488 (18) | 0.0520 (16) | 0.0021 (13) | −0.0122 (13) | −0.0270 (14) |
| C2 | 0.0476 (16) | 0.0391 (15) | 0.0463 (16) | −0.0007 (12) | −0.0086 (13) | −0.0167 (13) |
| C3 | 0.0420 (15) | 0.0330 (14) | 0.0442 (15) | −0.0023 (11) | −0.0072 (12) | −0.0144 (12) |
| C4 | 0.0516 (17) | 0.0392 (16) | 0.0470 (17) | −0.0034 (13) | −0.0054 (13) | −0.0149 (13) |
| C5 | 0.068 (2) | 0.0306 (15) | 0.0629 (19) | −0.0036 (14) | −0.0084 (16) | −0.0122 (14) |
| C6 | 0.0555 (18) | 0.0443 (18) | 0.072 (2) | −0.0012 (14) | −0.0137 (15) | −0.0313 (16) |
| C7 | 0.0448 (15) | 0.0379 (15) | 0.0390 (15) | −0.0021 (12) | −0.0059 (12) | −0.0150 (12) |
| C8 | 0.0512 (16) | 0.0305 (14) | 0.0368 (14) | −0.0066 (12) | −0.0078 (12) | −0.0143 (11) |
| C9 | 0.0522 (18) | 0.0433 (17) | 0.0482 (16) | −0.0037 (14) | −0.0039 (13) | −0.0161 (13) |
| C10 | 0.064 (2) | 0.0395 (17) | 0.0618 (19) | 0.0082 (15) | −0.0187 (17) | −0.0169 (15) |
| C11 | 0.077 (2) | 0.0326 (16) | 0.0472 (17) | −0.0099 (15) | −0.0152 (16) | −0.0066 (13) |
| C12 | 0.063 (2) | 0.0460 (18) | 0.0503 (17) | −0.0166 (16) | −0.0007 (15) | −0.0128 (14) |
| C13 | 0.0518 (18) | 0.0431 (17) | 0.0523 (17) | −0.0014 (13) | −0.0086 (14) | −0.0158 (14) |
| C14 | 0.0458 (16) | 0.0412 (17) | 0.0382 (15) | −0.0038 (12) | −0.0082 (12) | −0.0109 (13) |
| C15 | 0.0433 (15) | 0.0388 (15) | 0.0380 (14) | −0.0041 (12) | −0.0084 (12) | −0.0122 (12) |
| C16 | 0.083 (2) | 0.0445 (17) | 0.0403 (16) | −0.0140 (15) | −0.0156 (15) | −0.0112 (13) |
| C17 | 0.084 (2) | 0.0423 (17) | 0.0538 (19) | −0.0151 (16) | −0.0114 (17) | −0.0132 (14) |
| C18 | 0.0465 (16) | 0.0549 (19) | 0.0530 (17) | −0.0078 (14) | −0.0055 (13) | −0.0300 (15) |
| C19 | 0.069 (2) | 0.064 (2) | 0.0417 (16) | −0.0029 (16) | −0.0131 (14) | −0.0250 (15) |
| C20 | 0.0633 (19) | 0.0458 (17) | 0.0373 (15) | −0.0027 (14) | −0.0085 (13) | −0.0102 (13) |
Geometric parameters (Å, °)
| Br1—C1 | 1.893 (3) | C8—C13 | 1.386 (4) |
| Cl1—C18 | 1.740 (3) | C9—C10 | 1.384 (4) |
| O1—C4 | 1.344 (3) | C9—H9 | 0.9300 |
| O1—H1 | 0.8200 | C10—C11 | 1.368 (4) |
| O2—C14 | 1.210 (3) | C10—H10 | 0.9300 |
| N1—C7 | 1.285 (3) | C11—C12 | 1.372 (4) |
| N1—N2 | 1.370 (3) | C11—H11 | 0.9300 |
| N2—C14 | 1.364 (3) | C12—C13 | 1.376 (4) |
| N2—H2 | 0.8600 | C12—H12 | 0.9300 |
| C1—C6 | 1.375 (4) | C13—H13 | 0.9300 |
| C1—C2 | 1.380 (4) | C14—C15 | 1.491 (4) |
| C2—C3 | 1.390 (4) | C15—C20 | 1.378 (4) |
| C2—H2A | 0.9300 | C15—C16 | 1.382 (4) |
| C3—C4 | 1.407 (4) | C16—C17 | 1.385 (4) |
| C3—C7 | 1.476 (3) | C16—H16 | 0.9300 |
| C4—C5 | 1.392 (4) | C17—C18 | 1.359 (4) |
| C5—C6 | 1.363 (4) | C17—H17 | 0.9300 |
| C5—H5 | 0.9300 | C18—C19 | 1.368 (4) |
| C6—H6 | 0.9300 | C19—C20 | 1.381 (4) |
| C7—C8 | 1.493 (4) | C19—H19 | 0.9300 |
| C8—C9 | 1.385 (4) | C20—H20 | 0.9300 |
| C4—O1—H1 | 109.5 | C11—C10—H10 | 119.8 |
| C7—N1—N2 | 119.3 (2) | C9—C10—H10 | 119.8 |
| C14—N2—N1 | 118.3 (2) | C10—C11—C12 | 119.8 (3) |
| C14—N2—H2 | 120.8 | C10—C11—H11 | 120.1 |
| N1—N2—H2 | 120.8 | C12—C11—H11 | 120.1 |
| C6—C1—C2 | 120.4 (3) | C11—C12—C13 | 120.4 (3) |
| C6—C1—Br1 | 119.3 (2) | C11—C12—H12 | 119.8 |
| C2—C1—Br1 | 120.2 (2) | C13—C12—H12 | 119.8 |
| C1—C2—C3 | 120.9 (3) | C12—C13—C8 | 120.4 (3) |
| C1—C2—H2A | 119.6 | C12—C13—H13 | 119.8 |
| C3—C2—H2A | 119.6 | C8—C13—H13 | 119.8 |
| C2—C3—C4 | 118.4 (2) | O2—C14—N2 | 121.2 (2) |
| C2—C3—C7 | 119.9 (2) | O2—C14—C15 | 122.5 (2) |
| C4—C3—C7 | 121.8 (2) | N2—C14—C15 | 116.3 (2) |
| O1—C4—C5 | 117.2 (2) | C20—C15—C16 | 118.5 (3) |
| O1—C4—C3 | 123.5 (2) | C20—C15—C14 | 117.1 (2) |
| C5—C4—C3 | 119.3 (3) | C16—C15—C14 | 124.4 (2) |
| C6—C5—C4 | 121.3 (3) | C15—C16—C17 | 120.5 (3) |
| C6—C5—H5 | 119.3 | C15—C16—H16 | 119.8 |
| C4—C5—H5 | 119.3 | C17—C16—H16 | 119.8 |
| C5—C6—C1 | 119.7 (3) | C18—C17—C16 | 119.3 (3) |
| C5—C6—H6 | 120.2 | C18—C17—H17 | 120.4 |
| C1—C6—H6 | 120.2 | C16—C17—H17 | 120.4 |
| N1—C7—C3 | 116.0 (2) | C17—C18—C19 | 121.8 (3) |
| N1—C7—C8 | 123.7 (2) | C17—C18—Cl1 | 118.7 (2) |
| C3—C7—C8 | 120.2 (2) | C19—C18—Cl1 | 119.5 (2) |
| C9—C8—C13 | 118.9 (2) | C18—C19—C20 | 118.4 (3) |
| C9—C8—C7 | 120.4 (2) | C18—C19—H19 | 120.8 |
| C13—C8—C7 | 120.7 (2) | C20—C19—H19 | 120.8 |
| C10—C9—C8 | 120.1 (3) | C15—C20—C19 | 121.5 (3) |
| C10—C9—H9 | 120.0 | C15—C20—H20 | 119.2 |
| C8—C9—H9 | 120.0 | C19—C20—H20 | 119.2 |
| C11—C10—C9 | 120.4 (3) | ||
| C7—N1—N2—C14 | 178.9 (2) | C13—C8—C9—C10 | −0.3 (4) |
| C6—C1—C2—C3 | −1.2 (4) | C7—C8—C9—C10 | 179.2 (3) |
| Br1—C1—C2—C3 | −179.6 (2) | C8—C9—C10—C11 | −0.6 (4) |
| C1—C2—C3—C4 | 0.7 (4) | C9—C10—C11—C12 | 0.7 (4) |
| C1—C2—C3—C7 | 179.8 (2) | C10—C11—C12—C13 | 0.1 (4) |
| C2—C3—C4—O1 | 179.8 (3) | C11—C12—C13—C8 | −1.0 (4) |
| C7—C3—C4—O1 | 0.8 (4) | C9—C8—C13—C12 | 1.1 (4) |
| C2—C3—C4—C5 | 0.2 (4) | C7—C8—C13—C12 | −178.4 (3) |
| C7—C3—C4—C5 | −178.9 (3) | N1—N2—C14—O2 | 0.0 (4) |
| O1—C4—C5—C6 | 179.7 (3) | N1—N2—C14—C15 | 179.8 (2) |
| C3—C4—C5—C6 | −0.7 (4) | O2—C14—C15—C20 | 0.2 (4) |
| C4—C5—C6—C1 | 0.2 (5) | N2—C14—C15—C20 | −179.6 (2) |
| C2—C1—C6—C5 | 0.7 (4) | O2—C14—C15—C16 | −179.6 (3) |
| Br1—C1—C6—C5 | 179.2 (2) | N2—C14—C15—C16 | 0.5 (4) |
| N2—N1—C7—C3 | 180.0 (2) | C20—C15—C16—C17 | −0.7 (5) |
| N2—N1—C7—C8 | 0.4 (4) | C14—C15—C16—C17 | 179.1 (3) |
| C2—C3—C7—N1 | 178.4 (2) | C15—C16—C17—C18 | −1.6 (5) |
| C4—C3—C7—N1 | −2.5 (4) | C16—C17—C18—C19 | 2.9 (5) |
| C2—C3—C7—C8 | −2.0 (4) | C16—C17—C18—Cl1 | −175.6 (2) |
| C4—C3—C7—C8 | 177.1 (2) | C17—C18—C19—C20 | −1.7 (5) |
| N1—C7—C8—C9 | 79.9 (3) | Cl1—C18—C19—C20 | 176.7 (2) |
| C3—C7—C8—C9 | −99.7 (3) | C16—C15—C20—C19 | 1.9 (4) |
| N1—C7—C8—C13 | −100.6 (3) | C14—C15—C20—C19 | −177.9 (3) |
| C3—C7—C8—C13 | 79.9 (3) | C18—C19—C20—C15 | −0.7 (5) |
Hydrogen-bond geometry (Å, °)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O1—H1···N1 | 0.82 | 1.84 | 2.554 (3) | 145 |
Footnotes
Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2613).
References
- Bruker (1996). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
- Carcelli, M., Mazza, P., Pelizzi, G. & Zani, F. (1995). J. Inorg. Biochem.57, 43–62. [DOI] [PubMed]
- Salem, A. A. (1998). Microchem. J.60, 51–66.
- Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
- Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
- Singh, R. B., Jain, P. & Singh, R. P. (1982). Talanta, 29, 77–84. [DOI] [PubMed]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809027949/ng2613sup1.cif
Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027949/ng2613Isup2.hkl
Additional supplementary materials: crystallographic information; 3D view; checkCIF report