organic compounds
N′-(3-Fluorobenzylidene)-4-hydroxy-3-methoxybenzohydrazide methanol monosolvate
aCollege of Biology and Chemical Engineering, Jiaxing University, Jiaxing Zhejiang 314001, People's Republic of China, and School of Pharmaceutical Sciences, Zhejiang University, Hangzhou Zhejiang 310058, People's Republic of China
*Correspondence e-mail: zongqs@iccas.ac.cn
In the title compound, C15H13FN2O3·CH3OH, the dihedral angle between the benzene rings of the benzohydrazone molecule is 5.3 (3)°. The C atom of the methoxy group is almost coplanar with its attached ring [deviation = 0.017 (2) Å]. The r.m.s. deviation of the 21 non-H atoms of the hydrazone molecule is 0.106 Å. In the crystal, the components are linked by Om—H⋯Oh, Nh—H⋯Om and Oh—H⋯Oh (m = methanol and h = hydrazone) hydrogen bonds, forming (001) layers.
Related literature
For related structures, see: Horkaew et al. (2012); Fun et al. (2011); Zhang (2011).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); 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.
Supporting information
10.1107/S1600536812012196/hb6695sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812012196/hb6695Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812012196/hb6695Isup3.cml
3-Fluorobenzaldehyde (0.124 g, 1 mmol) and 4-hydroxy-3-methoxybenzohydrazide (0.182 g, 1 mmol) were mixed in methanol. The mixture was stirred at room temperature for 1 h to give a colorless solution. Colourless blocks were obtained by slow evaporation from the solution in air.
H1 was located from an electronic map and restrained with N—H distance of 0.90 (1) Å. All other H atoms were placed at calculated positions and refined using a riding model approximation, with C—H = 0.93 or 0.96 Å, O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C and O).
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008).C15H13FN2O3·CH4O | Dx = 1.323 Mg m−3 |
Mr = 320.32 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 8503 reflections |
a = 14.9566 (18) Å | θ = 2.5–26.0° |
b = 11.1123 (16) Å | µ = 0.10 mm−1 |
c = 19.351 (2) Å | T = 298 K |
V = 3216.1 (7) Å3 | Block, colorless |
Z = 8 | 0.20 × 0.18 × 0.17 mm |
F(000) = 1344 |
Bruker APEXII CCD diffractometer | 3270 independent reflections |
Radiation source: fine-focus sealed tube | 2588 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ϕ and ω scans | θmax = 26.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −18→17 |
Tmin = 0.980, Tmax = 0.983 | k = −13→13 |
22845 measured reflections | l = −24→24 |
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0956P)2 + 0.5869P] where P = (Fo2 + 2Fc2)/3 |
3270 reflections | (Δ/σ)max < 0.001 |
215 parameters | Δρmax = 0.28 e Å−3 |
1 restraint | Δρmin = −0.34 e Å−3 |
C15H13FN2O3·CH4O | V = 3216.1 (7) Å3 |
Mr = 320.32 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.9566 (18) Å | µ = 0.10 mm−1 |
b = 11.1123 (16) Å | T = 298 K |
c = 19.351 (2) Å | 0.20 × 0.18 × 0.17 mm |
Bruker APEXII CCD diffractometer | 3270 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2588 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.983 | Rint = 0.030 |
22845 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 1 restraint |
wR(F2) = 0.161 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.28 e Å−3 |
3270 reflections | Δρmin = −0.34 e Å−3 |
215 parameters |
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 | ||
F1 | 0.62214 (8) | 1.20264 (15) | 0.71230 (10) | 0.0899 (5) | |
N1 | 0.27077 (9) | 0.93828 (13) | 0.59540 (8) | 0.0396 (4) | |
N2 | 0.33902 (9) | 1.00033 (12) | 0.62766 (8) | 0.0390 (3) | |
O1 | 0.02644 (7) | 0.56459 (11) | 0.42821 (6) | 0.0430 (3) | |
H1A | −0.0236 | 0.5933 | 0.4332 | 0.064* | |
O2 | 0.19271 (8) | 0.52220 (13) | 0.40048 (7) | 0.0540 (4) | |
O3 | 0.37143 (7) | 0.80593 (11) | 0.55390 (8) | 0.0497 (4) | |
O4 | 0.39737 (10) | 0.57101 (14) | 0.59772 (13) | 0.0833 (6) | |
H4 | 0.3917 | 0.6416 | 0.5862 | 0.125* | |
C1 | 0.38310 (11) | 1.16625 (15) | 0.69775 (9) | 0.0397 (4) | |
C2 | 0.35539 (13) | 1.26065 (17) | 0.73975 (10) | 0.0500 (5) | |
H2 | 0.2946 | 1.2747 | 0.7460 | 0.060* | |
C3 | 0.41710 (15) | 1.33379 (19) | 0.77229 (11) | 0.0585 (5) | |
H3 | 0.3976 | 1.3964 | 0.8004 | 0.070* | |
C4 | 0.50739 (14) | 1.31446 (19) | 0.76342 (12) | 0.0601 (6) | |
H4A | 0.5494 | 1.3629 | 0.7854 | 0.072* | |
C5 | 0.53336 (13) | 1.22155 (18) | 0.72118 (11) | 0.0533 (5) | |
C6 | 0.47444 (12) | 1.14675 (16) | 0.68772 (10) | 0.0449 (4) | |
H6 | 0.4947 | 1.0851 | 0.6593 | 0.054* | |
C7 | 0.31604 (11) | 1.09122 (16) | 0.66320 (9) | 0.0419 (4) | |
H7 | 0.2558 | 1.1105 | 0.6674 | 0.050* | |
C8 | 0.29236 (10) | 0.84020 (15) | 0.55851 (9) | 0.0361 (4) | |
C9 | 0.21891 (10) | 0.77204 (14) | 0.52525 (9) | 0.0351 (4) | |
C10 | 0.24240 (10) | 0.68253 (15) | 0.47763 (9) | 0.0383 (4) | |
H10 | 0.3023 | 0.6698 | 0.4670 | 0.046* | |
C11 | 0.17751 (10) | 0.61309 (15) | 0.44635 (9) | 0.0371 (4) | |
C12 | 0.08669 (10) | 0.63371 (14) | 0.46134 (8) | 0.0341 (4) | |
C13 | 0.06435 (10) | 0.72117 (16) | 0.50909 (9) | 0.0381 (4) | |
H13 | 0.0046 | 0.7337 | 0.5201 | 0.046* | |
C14 | 0.12929 (10) | 0.79028 (15) | 0.54072 (9) | 0.0379 (4) | |
H14 | 0.1129 | 0.8492 | 0.5724 | 0.046* | |
C15 | 0.28296 (14) | 0.4987 (2) | 0.38116 (13) | 0.0658 (6) | |
H15A | 0.3077 | 0.5685 | 0.3591 | 0.099* | |
H15B | 0.2847 | 0.4318 | 0.3498 | 0.099* | |
H15C | 0.3173 | 0.4798 | 0.4216 | 0.099* | |
C16 | 0.48620 (15) | 0.5484 (2) | 0.61393 (16) | 0.0715 (7) | |
H16A | 0.5145 | 0.6218 | 0.6283 | 0.107* | |
H16B | 0.5164 | 0.5171 | 0.5740 | 0.107* | |
H16C | 0.4892 | 0.4906 | 0.6507 | 0.107* | |
H1 | 0.2134 (9) | 0.965 (2) | 0.5972 (14) | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0391 (7) | 0.0999 (11) | 0.1307 (13) | −0.0092 (7) | −0.0109 (7) | −0.0398 (10) |
N1 | 0.0252 (6) | 0.0355 (8) | 0.0580 (9) | −0.0004 (5) | −0.0071 (6) | −0.0071 (6) |
N2 | 0.0296 (7) | 0.0345 (7) | 0.0529 (8) | −0.0032 (5) | −0.0072 (6) | −0.0026 (6) |
O1 | 0.0290 (6) | 0.0475 (7) | 0.0524 (7) | −0.0020 (5) | −0.0040 (5) | −0.0134 (6) |
O2 | 0.0345 (7) | 0.0598 (9) | 0.0676 (8) | 0.0074 (6) | −0.0031 (6) | −0.0287 (7) |
O3 | 0.0231 (6) | 0.0446 (7) | 0.0815 (9) | 0.0013 (5) | −0.0042 (5) | −0.0166 (6) |
O4 | 0.0364 (8) | 0.0443 (9) | 0.169 (2) | −0.0031 (6) | −0.0031 (9) | 0.0085 (10) |
C1 | 0.0402 (9) | 0.0368 (9) | 0.0422 (9) | −0.0020 (7) | −0.0044 (7) | −0.0019 (7) |
C2 | 0.0479 (10) | 0.0492 (10) | 0.0528 (11) | −0.0004 (8) | 0.0039 (8) | −0.0106 (9) |
C3 | 0.0659 (13) | 0.0514 (12) | 0.0583 (12) | −0.0030 (10) | −0.0009 (10) | −0.0193 (9) |
C4 | 0.0610 (13) | 0.0533 (12) | 0.0659 (13) | −0.0158 (10) | −0.0114 (10) | −0.0157 (10) |
C5 | 0.0407 (10) | 0.0546 (12) | 0.0646 (12) | −0.0063 (8) | −0.0064 (9) | −0.0086 (10) |
C6 | 0.0410 (9) | 0.0414 (9) | 0.0524 (10) | −0.0009 (7) | −0.0061 (8) | −0.0082 (8) |
C7 | 0.0318 (8) | 0.0421 (9) | 0.0519 (10) | 0.0004 (7) | −0.0022 (7) | −0.0057 (8) |
C8 | 0.0257 (7) | 0.0332 (8) | 0.0494 (9) | 0.0012 (6) | −0.0016 (6) | 0.0000 (7) |
C9 | 0.0266 (7) | 0.0331 (8) | 0.0456 (9) | −0.0006 (6) | −0.0026 (6) | −0.0007 (7) |
C10 | 0.0241 (7) | 0.0397 (9) | 0.0511 (9) | 0.0034 (6) | −0.0009 (7) | −0.0044 (7) |
C11 | 0.0301 (8) | 0.0390 (9) | 0.0421 (9) | 0.0038 (6) | −0.0014 (6) | −0.0065 (7) |
C12 | 0.0263 (7) | 0.0354 (8) | 0.0407 (8) | −0.0018 (6) | −0.0038 (6) | −0.0006 (7) |
C13 | 0.0233 (7) | 0.0430 (10) | 0.0480 (9) | 0.0009 (6) | 0.0005 (6) | −0.0063 (7) |
C14 | 0.0281 (8) | 0.0375 (9) | 0.0482 (9) | 0.0011 (6) | −0.0001 (6) | −0.0074 (7) |
C15 | 0.0436 (11) | 0.0745 (15) | 0.0794 (14) | 0.0136 (10) | 0.0079 (10) | −0.0270 (12) |
C16 | 0.0519 (13) | 0.0620 (14) | 0.1007 (19) | −0.0047 (10) | −0.0152 (12) | 0.0040 (13) |
F1—C5 | 1.355 (2) | C4—H4A | 0.9300 |
N1—C8 | 1.342 (2) | C5—C6 | 1.374 (3) |
N1—N2 | 1.3809 (19) | C6—H6 | 0.9300 |
N1—H1 | 0.910 (10) | C7—H7 | 0.9300 |
N2—C7 | 1.269 (2) | C8—C9 | 1.481 (2) |
O1—C12 | 1.3465 (19) | C9—C14 | 1.388 (2) |
O1—H1A | 0.8200 | C9—C10 | 1.401 (2) |
O2—C11 | 1.364 (2) | C10—C11 | 1.380 (2) |
O2—C15 | 1.425 (2) | C10—H10 | 0.9300 |
O3—C8 | 1.2456 (19) | C11—C12 | 1.408 (2) |
O4—C16 | 1.388 (3) | C12—C13 | 1.382 (2) |
O4—H4 | 0.8200 | C13—C14 | 1.381 (2) |
C1—C2 | 1.390 (3) | C13—H13 | 0.9300 |
C1—C6 | 1.397 (2) | C14—H14 | 0.9300 |
C1—C7 | 1.466 (2) | C15—H15A | 0.9600 |
C2—C3 | 1.382 (3) | C15—H15B | 0.9600 |
C2—H2 | 0.9300 | C15—H15C | 0.9600 |
C3—C4 | 1.378 (3) | C16—H16A | 0.9600 |
C3—H3 | 0.9300 | C16—H16B | 0.9600 |
C4—C5 | 1.373 (3) | C16—H16C | 0.9600 |
C8—N1—N2 | 117.91 (13) | C14—C9—C10 | 119.18 (14) |
C8—N1—H1 | 121.0 (17) | C14—C9—C8 | 123.21 (15) |
N2—N1—H1 | 121.0 (17) | C10—C9—C8 | 117.57 (14) |
C7—N2—N1 | 116.24 (14) | C11—C10—C9 | 120.62 (14) |
C12—O1—H1A | 109.5 | C11—C10—H10 | 119.7 |
C11—O2—C15 | 117.69 (14) | C9—C10—H10 | 119.7 |
C16—O4—H4 | 109.5 | O2—C11—C10 | 125.62 (14) |
C2—C1—C6 | 119.33 (16) | O2—C11—C12 | 114.55 (14) |
C2—C1—C7 | 119.46 (16) | C10—C11—C12 | 119.83 (15) |
C6—C1—C7 | 121.18 (16) | O1—C12—C13 | 123.90 (14) |
C3—C2—C1 | 120.74 (18) | O1—C12—C11 | 117.05 (14) |
C3—C2—H2 | 119.6 | C13—C12—C11 | 119.04 (14) |
C1—C2—H2 | 119.6 | C14—C13—C12 | 121.15 (14) |
C4—C3—C2 | 120.40 (19) | C14—C13—H13 | 119.4 |
C4—C3—H3 | 119.8 | C12—C13—H13 | 119.4 |
C2—C3—H3 | 119.8 | C13—C14—C9 | 120.15 (15) |
C5—C4—C3 | 117.95 (18) | C13—C14—H14 | 119.9 |
C5—C4—H4A | 121.0 | C9—C14—H14 | 119.9 |
C3—C4—H4A | 121.0 | O2—C15—H15A | 109.5 |
F1—C5—C4 | 117.99 (17) | O2—C15—H15B | 109.5 |
F1—C5—C6 | 118.35 (18) | H15A—C15—H15B | 109.5 |
C4—C5—C6 | 123.66 (19) | O2—C15—H15C | 109.5 |
C5—C6—C1 | 117.91 (17) | H15A—C15—H15C | 109.5 |
C5—C6—H6 | 121.0 | H15B—C15—H15C | 109.5 |
C1—C6—H6 | 121.0 | O4—C16—H16A | 109.5 |
N2—C7—C1 | 120.97 (15) | O4—C16—H16B | 109.5 |
N2—C7—H7 | 119.5 | H16A—C16—H16B | 109.5 |
C1—C7—H7 | 119.5 | O4—C16—H16C | 109.5 |
O3—C8—N1 | 120.98 (15) | H16A—C16—H16C | 109.5 |
O3—C8—C9 | 121.10 (15) | H16B—C16—H16C | 109.5 |
N1—C8—C9 | 117.89 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.91 (1) | 2.03 (1) | 2.916 (2) | 164 (2) |
O4—H4···O3 | 0.82 | 1.95 | 2.772 (2) | 176 |
O1—H1A···O3ii | 0.82 | 1.94 | 2.7504 (17) | 168 |
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, −y+3/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H13FN2O3·CH4O |
Mr | 320.32 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 298 |
a, b, c (Å) | 14.9566 (18), 11.1123 (16), 19.351 (2) |
V (Å3) | 3216.1 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.20 × 0.18 × 0.17 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.980, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22845, 3270, 2588 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.161, 1.12 |
No. of reflections | 3270 |
No. of parameters | 215 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.34 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.910 (10) | 2.031 (12) | 2.916 (2) | 164 (2) |
O4—H4···O3 | 0.82 | 1.95 | 2.772 (2) | 176 |
O1—H1A···O3ii | 0.82 | 1.94 | 2.7504 (17) | 168 |
Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x−1/2, −y+3/2, −z+1. |
Acknowledgements
The author thanks the Excellent Yong Teachers Program (No. 00511024) and the China Postdoctoral Science Foundation (No. 2011M500989) for financial support.
References
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fun, H.-K., Horkaew, J. & Chantrapromma, S. (2011). Acta Cryst. E67, o2644–o2645. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Horkaew, J., Chantrapromma, S., Anantapong, T., Kanjana-Opas, A. & Fun, H.-K. (2012). Acta Cryst. E68, o1069–o1070. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2004). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, Z. (2011). Acta Cryst. E67, o1630. Web of Science CSD CrossRef IUCr Journals Google Scholar
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.
In this paper, the title new benzohydrazide compound, (I), which crystallised as a methanol solvate, is reported.
The dihedral angle between the benzene rings C1–C6 and C9–C14 of the benzohydrazone molecule is 5.3 (3)°. The bond lengths in the benzohydrazone molecule are comparable to those in similar benzohydrazone compounds (Horkaew et al., 2012; Fun et al., 2011; Zhang, 2011). In the crystal, the benzohydrazone molecules are linked by methanol molecules through hydrogen bonds (Table 1), to form layers parallel to the ab plane (Fig. 2).