organic compounds
N′-[(E)-5-Bromo-2-hydroxy-3-methoxybenzylidene]-4-methoxybenzohydrazide monohydrate
aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, and bDepartment of Chemistry, Faculty of Science, Eastern University, Sri Lanka, Chenkalady, Sri Lanka
*Correspondence e-mail: eesans@yahoo.com
In the title compound, C16H15BrN2O4·H2O, the hydrazide molecule is nearly planar, with a largest deviation from the mean plane through the non-H atoms of 0.106 (4) Å and a dihedral angle between the benzene rings of 1.98 (16)°. This molecule adopts an E conformation about the C=N bond and an intramolecular O—H⋯N hydrogen bond increases the rigidity. In the crystal, some molecules of the title hydrazide are replaced by molecules of its 6-bromo isomer, and the Br atom from this admixture molecule was refined to give a partial occupancy of 0.0523 (13). The hydrazide and water molecules are linked through classical N—H⋯O and O—H⋯O hydrogen bonds, forming layers parallel to (110). C—H⋯π interactions are also present.
Related literature
For the biological activity of hydrazone compounds, see: Metwally et al. (2006); Cukurovali et al. (2006). For the synthesis of related compounds, see: Emmanuel et al. (2011); Mangalam & Kurup (2011). For standard bond lengths, see: Allen et al. (1987). For related structures, see: Tan (2012); Hou & Bi (2012); Shen et al. (2012).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010).
Supporting information
https://doi.org/10.1107/S1600536812033806/yk2067sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812033806/yk2067Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812033806/yk2067Isup3.cml
The title compound was prepared by adapting a reported procedure (Emmanuel et al., 2011; Mangalam & Kurup, 2011) by refluxing a mixture of methanolic solutions of 4-methoxybenzhydrazide (0.1661 g, 1 mmol) and 5-bromo-3-methoxysalicylaldehyde (0.2309 g, 1 mmol) for 4 h. The formed crystals were collected, washed with few drops of methanol and dried over P4O10 in vacuo. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation from its methanolic solution. They contains approximately 5% of the 6-bromo isomer of the title compound.
Bromine atoms Br1A and Br1B were refined freely, with the sum of their occupancy factors constrained to 1.0. All H atoms on C except of H1A and H1B were placed in calculated positions, with C—H bond distances 0.93–0.97 Å and Uiso=1.2Ueq (1.5 for CH3). The H1A atom was refined with restrained distance C1—H1A using DFIX instruction and with occupancy factor equal to that of Br1A. The H1B was placed in calculated position with occupancy factor equal to that of Br1B, and its coordinates were fixed. Hydrogen atoms attached to O and N atoms were located from difference maps, and the (N,O)—H distances were restrained using DFIX instructions.
Aroylhydrazones derived from the condensation reactions of aroylhydrazides with
show excellent biological properties (Cukurovali et al., 2006; Metwally et al., 2006). As an extention of the work on the structures of hydrazone derivatives (Tan, 2012; Hou & Bi, 2012; Shen et al., 2012), we report here the of a new aroylhydrazone compound. The molecular structure of the title compound is shown in Fig. 1.The molecule adopts an E conformation about the C7═N1 bond and exists in keto form with C8═O3 bond length of 1.216 (2) Å, which is very close to a normal C═O bond length 1.21 Å (Allen et al., 1987).
In the crystal, approximately 5% of molecules of the title hydrazide are replaced by molecules of its 6-bromo isomer, and the Br1B atom of this admixture molecule was included in the
Since the molecule of 6-bromo isomer is likely nonplanar due to sterical tensions, it does not occupy exactly the same position as the molecule of 5-bromo isomer. As a result, Br1B deviates by 0.58 (4) Å from the mean plane of C1–C6 benzene ring, and the distance C1—Br1B is 1.67 (5) Å, that is much smaller than the typical bond length C—Br. On this reason, geometric parameters involving Br1B are not included in the cif-file.Parallel arrangement of molecules in crystal is shown in Fig. 2. Adjacent molecules are linked through classical N—H···O and O—H···O hydrogen bonds, and a C—H···π interaction between one of the methyl H atoms and the phenyl ring of the adjacent molecule is also observed (see Table 1, Fig. 3). Weak π···π interactions are also present with a shortest separation between benzene ring centroids of 4.973 (3) Å.
For the biological activity of hydrazone compounds, see: Metwally et al. (2006); Cukurovali et al. (2006). For the synthesis of related compounds, see: Emmanuel et al. (2011); Mangalam & Kurup (2011). For standard bond lengths, see: Allen et al. (1987). For related structures, see: Tan (2012); Hou & Bi (2012); Shen et al. (2012).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).Fig. 1. The structure of asymmetric unit of C16H15BrN2O4.H2O with atom labelling scheme and thermal ellipsoids drawn at the 50% probability level. Bromine and hydrogen atoms of the admixture molecule are omitted. | |
Fig. 2. Packing diagram of the title compound. | |
Fig. 3. Hydrogen bonds and C—H···π interactions in the crystal structure of C16H15BrN2O4.H2O. |
C16H15BrN2O4·H2O | F(000) = 808 |
Mr = 397.22 | Dx = 1.570 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4929 reflections |
a = 4.9730 (4) Å | θ = 2.9–25.6° |
b = 13.5721 (12) Å | µ = 2.47 mm−1 |
c = 24.907 (2) Å | T = 296 K |
β = 90.921 (4)° | Block, brown |
V = 1680.8 (2) Å3 | 0.40 × 0.30 × 0.25 mm |
Z = 4 |
Bruker Kappa APEXII CCD area-detector diffractometer | 2939 independent reflections |
Radiation source: fine-focus sealed tube | 2268 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.036 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.9° |
ω and φ scan | h = −5→5 |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | k = −16→16 |
Tmin = 0.414, Tmax = 0.539 | l = −29→29 |
12692 measured reflections |
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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.043P)2 + 0.7865P] where P = (Fo2 + 2Fc2)/3 |
2939 reflections | (Δ/σ)max < 0.001 |
247 parameters | Δρmax = 0.52 e Å−3 |
6 restraints | Δρmin = −0.34 e Å−3 |
C16H15BrN2O4·H2O | V = 1680.8 (2) Å3 |
Mr = 397.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.9730 (4) Å | µ = 2.47 mm−1 |
b = 13.5721 (12) Å | T = 296 K |
c = 24.907 (2) Å | 0.40 × 0.30 × 0.25 mm |
β = 90.921 (4)° |
Bruker Kappa APEXII CCD area-detector diffractometer | 2939 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 2268 reflections with I > 2σ(I) |
Tmin = 0.414, Tmax = 0.539 | Rint = 0.036 |
12692 measured reflections |
R[F2 > 2σ(F2)] = 0.035 | 6 restraints |
wR(F2) = 0.094 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.52 e Å−3 |
2939 reflections | Δρmin = −0.34 e Å−3 |
247 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 | Occ. (<1) | |
O1W | 0.6146 (7) | 0.53984 (18) | 0.20575 (11) | 0.0857 (8) | |
H1W | 0.479 (6) | 0.521 (3) | 0.1873 (16) | 0.129* | |
H2W | 0.651 (9) | 0.496 (2) | 0.2293 (14) | 0.129* | |
Br1A | 0.86593 (7) | 0.06757 (2) | 0.072139 (15) | 0.06810 (16) | 0.9477 (13) |
H1A | 0.476 (8) | 0.0862 (12) | 0.1601 (13) | 0.058 (11)* | 0.9477 (13) |
Br1B | 0.5677 (14) | 0.0463 (4) | 0.1799 (3) | 0.064 (3) | 0.0523 (13) |
H1B | 0.7630 | 0.1200 | 0.0880 | 0.058 (11)* | 0.0523 (13) |
O1 | 0.5501 (5) | 0.43453 (15) | 0.08852 (9) | 0.0653 (6) | |
O2 | 0.2111 (4) | 0.39584 (17) | 0.16439 (9) | 0.0629 (6) | |
O3 | −0.2919 (5) | 0.39947 (18) | 0.27910 (10) | 0.0789 (7) | |
O4 | −1.0445 (4) | 0.21328 (16) | 0.45317 (8) | 0.0616 (6) | |
N1 | 0.0049 (5) | 0.2680 (2) | 0.22932 (9) | 0.0554 (6) | |
N2 | −0.1688 (5) | 0.2415 (2) | 0.26906 (9) | 0.0528 (6) | |
C1 | 0.4937 (6) | 0.1490 (2) | 0.14527 (12) | 0.0534 (7) | |
C2 | 0.6652 (6) | 0.1699 (2) | 0.10475 (11) | 0.0502 (7) | |
C3 | 0.6936 (6) | 0.2646 (2) | 0.08475 (11) | 0.0514 (7) | |
H3 | 0.8149 | 0.2775 | 0.0576 | 0.062* | |
C4 | 0.5407 (6) | 0.3389 (2) | 0.10554 (11) | 0.0489 (7) | |
C5 | 0.3586 (5) | 0.3192 (2) | 0.14656 (11) | 0.0478 (7) | |
C6 | 0.3366 (6) | 0.2237 (2) | 0.16659 (11) | 0.0492 (7) | |
C7 | 0.1512 (6) | 0.1998 (2) | 0.20906 (11) | 0.0559 (7) | |
H7 | 0.1382 | 0.1354 | 0.2216 | 0.067* | |
C8 | −0.3172 (6) | 0.3134 (2) | 0.29184 (11) | 0.0511 (7) | |
C9 | −0.5107 (5) | 0.2833 (2) | 0.33332 (10) | 0.0444 (6) | |
C10 | −0.6695 (6) | 0.3560 (2) | 0.35495 (12) | 0.0514 (7) | |
H10 | −0.6532 | 0.4202 | 0.3424 | 0.062* | |
C11 | −0.8522 (6) | 0.3363 (2) | 0.39472 (12) | 0.0514 (7) | |
H11 | −0.9568 | 0.3866 | 0.4088 | 0.062* | |
C12 | −0.8775 (5) | 0.2411 (2) | 0.41334 (11) | 0.0459 (7) | |
C13 | −0.7265 (6) | 0.1670 (2) | 0.39097 (12) | 0.0530 (7) | |
H13 | −0.7489 | 0.1024 | 0.4025 | 0.064* | |
C14 | −0.5433 (6) | 0.1873 (2) | 0.35177 (12) | 0.0515 (7) | |
H14 | −0.4406 | 0.1367 | 0.3375 | 0.062* | |
C15 | 0.7560 (7) | 0.4612 (2) | 0.05349 (14) | 0.0685 (9) | |
H15A | 0.9270 | 0.4437 | 0.0692 | 0.103* | |
H15B | 0.7503 | 0.5310 | 0.0473 | 0.103* | |
H15C | 0.7317 | 0.4272 | 0.0200 | 0.103* | |
C16 | −1.2105 (6) | 0.2868 (3) | 0.47648 (13) | 0.0702 (9) | |
H16A | −1.0998 | 0.3387 | 0.4908 | 0.105* | |
H16B | −1.3132 | 0.2581 | 0.5048 | 0.105* | |
H16C | −1.3305 | 0.3131 | 0.4495 | 0.105* | |
H21 | −0.165 (7) | 0.1796 (9) | 0.2766 (13) | 0.067 (10)* | |
H2 | 0.116 (8) | 0.375 (4) | 0.1910 (13) | 0.130 (18)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1W | 0.122 (2) | 0.0518 (14) | 0.0830 (19) | −0.0127 (14) | −0.0071 (16) | 0.0124 (12) |
Br1A | 0.0682 (2) | 0.0490 (2) | 0.0875 (3) | 0.00715 (17) | 0.01531 (18) | −0.00284 (18) |
Br1B | 0.080 (5) | 0.040 (4) | 0.072 (5) | −0.002 (3) | −0.010 (3) | 0.004 (3) |
O1 | 0.0735 (14) | 0.0462 (12) | 0.0770 (14) | 0.0028 (10) | 0.0238 (12) | 0.0056 (11) |
O2 | 0.0632 (14) | 0.0619 (13) | 0.0643 (14) | 0.0019 (11) | 0.0177 (11) | −0.0062 (11) |
O3 | 0.0930 (18) | 0.0588 (14) | 0.0854 (17) | 0.0022 (13) | 0.0209 (14) | 0.0284 (12) |
O4 | 0.0562 (12) | 0.0676 (14) | 0.0615 (12) | 0.0041 (11) | 0.0159 (10) | 0.0053 (11) |
N1 | 0.0516 (14) | 0.0730 (18) | 0.0415 (13) | −0.0144 (13) | 0.0024 (11) | 0.0006 (12) |
N2 | 0.0566 (15) | 0.0569 (17) | 0.0453 (13) | −0.0085 (13) | 0.0100 (11) | 0.0035 (12) |
C1 | 0.0563 (18) | 0.0503 (18) | 0.0536 (17) | −0.0071 (15) | 0.0001 (14) | 0.0039 (15) |
C2 | 0.0459 (16) | 0.0512 (17) | 0.0536 (17) | −0.0003 (13) | −0.0002 (13) | −0.0052 (14) |
C3 | 0.0462 (16) | 0.0546 (18) | 0.0535 (17) | −0.0059 (14) | 0.0074 (13) | −0.0012 (14) |
C4 | 0.0508 (16) | 0.0435 (16) | 0.0526 (16) | −0.0040 (13) | 0.0049 (13) | −0.0019 (13) |
C5 | 0.0460 (15) | 0.0545 (18) | 0.0431 (15) | −0.0040 (13) | 0.0025 (12) | −0.0071 (13) |
C6 | 0.0466 (16) | 0.0577 (18) | 0.0434 (15) | −0.0107 (14) | −0.0012 (12) | −0.0007 (13) |
C7 | 0.0575 (18) | 0.0621 (19) | 0.0481 (16) | −0.0116 (16) | 0.0041 (14) | 0.0027 (15) |
C8 | 0.0568 (17) | 0.0482 (18) | 0.0483 (16) | −0.0048 (14) | −0.0034 (13) | 0.0089 (14) |
C9 | 0.0444 (15) | 0.0444 (15) | 0.0442 (15) | −0.0014 (12) | −0.0037 (12) | 0.0050 (12) |
C10 | 0.0540 (17) | 0.0422 (16) | 0.0579 (17) | 0.0009 (13) | −0.0047 (14) | 0.0044 (13) |
C11 | 0.0476 (16) | 0.0480 (17) | 0.0586 (18) | 0.0083 (13) | −0.0014 (14) | −0.0048 (14) |
C12 | 0.0390 (14) | 0.0509 (17) | 0.0478 (15) | 0.0006 (12) | −0.0022 (12) | 0.0001 (13) |
C13 | 0.0577 (17) | 0.0416 (16) | 0.0600 (18) | −0.0024 (13) | 0.0070 (14) | 0.0041 (13) |
C14 | 0.0557 (17) | 0.0428 (16) | 0.0562 (17) | 0.0023 (13) | 0.0092 (14) | 0.0008 (13) |
C15 | 0.074 (2) | 0.0533 (19) | 0.079 (2) | −0.0056 (16) | 0.0200 (18) | 0.0094 (17) |
C16 | 0.0533 (19) | 0.093 (3) | 0.065 (2) | 0.0132 (18) | 0.0134 (16) | −0.0010 (18) |
O1W—H1W | 0.85 (3) | C5—C6 | 1.394 (4) |
O1W—H2W | 0.86 (3) | C6—C7 | 1.451 (4) |
Br1A—C2 | 1.901 (3) | C7—H7 | 0.9300 |
O1—C4 | 1.366 (3) | C8—C9 | 1.480 (4) |
O1—C15 | 1.404 (4) | C9—C10 | 1.379 (4) |
O2—C5 | 1.352 (3) | C9—C14 | 1.393 (4) |
O2—H2 | 0.87 (3) | C10—C11 | 1.381 (4) |
O3—C8 | 1.217 (3) | C10—H10 | 0.9300 |
O4—C12 | 1.357 (3) | C11—C12 | 1.379 (4) |
O4—C16 | 1.425 (4) | C11—H11 | 0.9300 |
N1—C7 | 1.285 (4) | C12—C13 | 1.378 (4) |
N1—N2 | 1.372 (3) | C13—C14 | 1.374 (4) |
N2—C8 | 1.353 (4) | C13—H13 | 0.9300 |
N2—H21 | 0.861 (14) | C14—H14 | 0.9300 |
C1—C2 | 1.362 (4) | C15—H15A | 0.9600 |
C1—C6 | 1.390 (4) | C15—H15B | 0.9600 |
C1—H1A | 0.93 (4) | C15—H15C | 0.9600 |
C2—C3 | 1.386 (4) | C16—H16A | 0.9600 |
C3—C4 | 1.370 (4) | C16—H16B | 0.9600 |
C3—H3 | 0.9300 | C16—H16C | 0.9600 |
C4—C5 | 1.402 (4) | ||
H1W—O1W—H2W | 108 (2) | N2—C8—C9 | 117.3 (2) |
C4—O1—C15 | 117.8 (2) | C10—C9—C14 | 118.0 (3) |
C5—O2—H2 | 108 (3) | C10—C9—C8 | 117.3 (2) |
C12—O4—C16 | 117.9 (2) | C14—C9—C8 | 124.7 (3) |
C7—N1—N2 | 117.5 (3) | C9—C10—C11 | 122.0 (3) |
C8—N2—N1 | 117.9 (3) | C9—C10—H10 | 119.0 |
C8—N2—H21 | 128 (2) | C11—C10—H10 | 119.0 |
N1—N2—H21 | 114 (2) | C12—C11—C10 | 119.2 (3) |
C2—C1—C6 | 119.6 (3) | C12—C11—H11 | 120.4 |
C2—C1—H1A | 123 (2) | C10—C11—H11 | 120.4 |
C6—C1—H1A | 117 (2) | O4—C12—C13 | 115.9 (3) |
C1—C2—C3 | 121.9 (3) | O4—C12—C11 | 124.5 (3) |
C1—C2—Br1A | 120.3 (2) | C13—C12—C11 | 119.6 (3) |
C3—C2—Br1A | 117.8 (2) | C14—C13—C12 | 120.8 (3) |
C4—C3—C2 | 119.1 (3) | C14—C13—H13 | 119.6 |
C4—C3—H3 | 120.5 | C12—C13—H13 | 119.6 |
C2—C3—H3 | 120.5 | C13—C14—C9 | 120.3 (3) |
O1—C4—C3 | 124.1 (2) | C13—C14—H14 | 119.9 |
O1—C4—C5 | 115.7 (2) | C9—C14—H14 | 119.9 |
C3—C4—C5 | 120.3 (3) | O1—C15—H15A | 109.5 |
O2—C5—C6 | 123.5 (2) | O1—C15—H15B | 109.5 |
O2—C5—C4 | 116.9 (3) | H15A—C15—H15B | 109.5 |
C6—C5—C4 | 119.6 (3) | O1—C15—H15C | 109.5 |
C1—C6—C5 | 119.6 (3) | H15A—C15—H15C | 109.5 |
C1—C6—C7 | 118.9 (3) | H15B—C15—H15C | 109.5 |
C5—C6—C7 | 121.5 (3) | O4—C16—H16A | 109.5 |
N1—C7—C6 | 119.7 (3) | O4—C16—H16B | 109.5 |
N1—C7—H7 | 120.1 | H16A—C16—H16B | 109.5 |
C6—C7—H7 | 120.1 | O4—C16—H16C | 109.5 |
O3—C8—N2 | 121.5 (3) | H16A—C16—H16C | 109.5 |
O3—C8—C9 | 121.2 (3) | H16B—C16—H16C | 109.5 |
C7—N1—N2—C8 | 177.9 (3) | C1—C6—C7—N1 | 179.8 (3) |
C6—C1—C2—C3 | 1.7 (5) | C5—C6—C7—N1 | −0.7 (4) |
C6—C1—C2—Br1A | −176.3 (2) | N1—N2—C8—O3 | −2.6 (4) |
C1—C2—C3—C4 | −1.4 (4) | N1—N2—C8—C9 | 177.9 (2) |
Br1A—C2—C3—C4 | 176.5 (2) | O3—C8—C9—C10 | 3.1 (4) |
C15—O1—C4—C3 | −10.0 (4) | N2—C8—C9—C10 | −177.4 (2) |
C15—O1—C4—C5 | 170.6 (3) | O3—C8—C9—C14 | −177.1 (3) |
C2—C3—C4—O1 | −179.3 (3) | N2—C8—C9—C14 | 2.4 (4) |
C2—C3—C4—C5 | 0.1 (4) | C14—C9—C10—C11 | 1.6 (4) |
O1—C4—C5—O2 | 0.6 (4) | C8—C9—C10—C11 | −178.5 (3) |
C3—C4—C5—O2 | −178.8 (3) | C9—C10—C11—C12 | −0.2 (4) |
O1—C4—C5—C6 | −179.7 (3) | C16—O4—C12—C13 | −178.2 (3) |
C3—C4—C5—C6 | 0.9 (4) | C16—O4—C12—C11 | 1.8 (4) |
C2—C1—C6—C5 | −0.6 (4) | C10—C11—C12—O4 | 178.2 (3) |
C2—C1—C6—C7 | 178.8 (3) | C10—C11—C12—C13 | −1.9 (4) |
O2—C5—C6—C1 | 179.0 (3) | O4—C12—C13—C14 | −177.5 (3) |
C4—C5—C6—C1 | −0.6 (4) | C11—C12—C13—C14 | 2.5 (4) |
O2—C5—C6—C7 | −0.4 (4) | C12—C13—C14—C9 | −1.1 (4) |
C4—C5—C6—C7 | 179.9 (3) | C10—C9—C14—C13 | −0.9 (4) |
N2—N1—C7—C6 | 179.5 (2) | C8—C9—C14—C13 | 179.2 (3) |
Cg2 is the centroid of the C9–C14 benzene ring |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O1Wi | 0.86 (1) | 1.96 (2) | 2.820 (4) | 174 (3) |
O2—H2···N1 | 0.87 (3) | 1.83 (3) | 2.595 (3) | 146 (5) |
O1W—H1W···O2 | 0.85 (3) | 2.23 (3) | 2.974 (4) | 147 (4) |
O1W—H2W···O3ii | 0.86 (3) | 1.82 (3) | 2.675 (3) | 177 (4) |
C16—H16C···Cg2iii | 0.96 | 2.70 | 3.517 (3) | 144 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H15BrN2O4·H2O |
Mr | 397.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 4.9730 (4), 13.5721 (12), 24.907 (2) |
β (°) | 90.921 (4) |
V (Å3) | 1680.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.47 |
Crystal size (mm) | 0.40 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.414, 0.539 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12692, 2939, 2268 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.094, 1.06 |
No. of reflections | 2939 |
No. of parameters | 247 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.52, −0.34 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2010), SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
Cg2 is the centroid of the C9–C14 benzene ring |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O1Wi | 0.861 (14) | 1.963 (15) | 2.820 (4) | 174 (3) |
O2—H2···N1 | 0.87 (3) | 1.83 (3) | 2.595 (3) | 146 (5) |
O1W—H1W···O2 | 0.85 (3) | 2.23 (3) | 2.974 (4) | 147 (4) |
O1W—H2W···O3ii | 0.86 (3) | 1.82 (3) | 2.675 (3) | 177 (4) |
C16—H16C···Cg2iii | 0.960 | 2.6989 | 3.517 (3) | 143.56 |
Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1, y, z. |
Acknowledgements
The authors are grateful to the Sophisticated Analytical Instruments Facility, Cochin University of Science and Technology, Kochi-22, India, for providing the single-crystal X-ray diffraction data. PRR thanks the Council of Scientific and Industrial Research, New Delhi, India, for a Junior Research Fellowship.
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.
Aroylhydrazones derived from the condensation reactions of aroylhydrazides with aldehydes show excellent biological properties (Cukurovali et al., 2006; Metwally et al., 2006). As an extention of the work on the structures of hydrazone derivatives (Tan, 2012; Hou & Bi, 2012; Shen et al., 2012), we report here the crystal structure of a new aroylhydrazone compound. The molecular structure of the title compound is shown in Fig. 1.
The molecule adopts an E conformation about the C7═N1 bond and exists in keto form with C8═O3 bond length of 1.216 (2) Å, which is very close to a normal C═O bond length 1.21 Å (Allen et al., 1987).
In the crystal, approximately 5% of molecules of the title hydrazide are replaced by molecules of its 6-bromo isomer, and the Br1B atom of this admixture molecule was included in the refinement. Since the molecule of 6-bromo isomer is likely nonplanar due to sterical tensions, it does not occupy exactly the same position as the molecule of 5-bromo isomer. As a result, Br1B deviates by 0.58 (4) Å from the mean plane of C1–C6 benzene ring, and the distance C1—Br1B is 1.67 (5) Å, that is much smaller than the typical bond length C—Br. On this reason, geometric parameters involving Br1B are not included in the cif-file.
Parallel arrangement of molecules in crystal is shown in Fig. 2. Adjacent molecules are linked through classical N—H···O and O—H···O hydrogen bonds, and a C—H···π interaction between one of the methyl H atoms and the phenyl ring of the adjacent molecule is also observed (see Table 1, Fig. 3). Weak π···π interactions are also present with a shortest separation between benzene ring centroids of 4.973 (3) Å.