organic compounds
N′-(3-Chlorobenzylidene)-4-hydroxybenzohydrazide
aH.E.J. Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and bPCSIR Labortories Complex, Karachi, Shahrah-e-Dr. Salmuzzaman Siddiqui, Karachi 75280, Pakistan
*Correspondence e-mail: dr.sammer.yousuf@gmail.com
The molecule of the title compound, C14H11ClN2O2 adopts an E conformation of the azomethine double bond and the dihedral angle between the benzene rings is 38.96 (13)°. In the crystal, molecules are linked by N—H⋯O and O—H⋯O (with the ketone O atom as acceptor) and C—H⋯O (with the hydroxy O atom as acceptor) hydrogen bonds, forming a three-dimensional network.
Related literature
For a related structure and background to the chemistry of the N-acylhydrazone unit, see: Taha et al. (2012). For a related structure, see: Hao (2009).
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); 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: SHELXL97.
Supporting information
10.1107/S1600536812048325/hb6997sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812048325/hb6997Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812048325/hb6997Isup3.cml
The title compound was synthesized by refluxing a mixture of 3-chlorobenzaldehyde (2 mmol, 0.23 ml), methanol (20 ml) and 3 drops of acetic acid. 4-hydroxybenzohydrazide (2 mmol, 0.304 g) was added into above mentioned mixture at ambient temperature and refluxed for 3 h with vigorous stirring. Progress of the reaction mixture was monitored by thin layer
After the completion of the reaction (TLC Analysis), the solvent of the reaction mixture was slowly evaporated at room temperature by keeping it in an open atmosphere in order to obtained colourless blocks (0.44 g, 80.3% yield).H atoms on phenyl ring and methine carbon were positioned 0.93 Å (CH) and constrained to ride on their parent atoms with Uiso(H)= 1.2Ueq(CH). The H atoms on the nitrogen (N–H= 0.79 (3) Å) and oxygen (O–H= 0.89 (2) Å) atoms were located in difference fourier maps and refined isotropically.
Data collection: SMART (Bruker, 2000); cell
SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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: SHELXL97 (Sheldrick, 2008).C14H11ClN2O2 | Dx = 1.457 Mg m−3 |
Mr = 274.70 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 1415 reflections |
a = 9.0900 (8) Å | θ = 2.5–23.8° |
b = 9.9396 (9) Å | µ = 0.30 mm−1 |
c = 13.8615 (12) Å | T = 293 K |
V = 1252.40 (19) Å3 | Block, colorles |
Z = 4 | 0.27 × 0.11 × 0.10 mm |
F(000) = 568 |
Bruker SMART APEX CCD diffractometer | 2274 independent reflections |
Radiation source: fine-focus sealed tube | 1980 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scan | θmax = 25.5°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −11→11 |
Tmin = 0.923, Tmax = 0.970 | k = −10→12 |
6999 measured reflections | l = −15→16 |
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | w = 1/[σ2(Fo2) + (0.0383P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
2274 reflections | Δρmax = 0.21 e Å−3 |
180 parameters | Δρmin = −0.20 e Å−3 |
1 restraint | Absolute structure: Flack (1983), 1060 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.12 (9) |
C14H11ClN2O2 | V = 1252.40 (19) Å3 |
Mr = 274.70 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 9.0900 (8) Å | µ = 0.30 mm−1 |
b = 9.9396 (9) Å | T = 293 K |
c = 13.8615 (12) Å | 0.27 × 0.11 × 0.10 mm |
Bruker SMART APEX CCD diffractometer | 2274 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1980 reflections with I > 2σ(I) |
Tmin = 0.923, Tmax = 0.970 | Rint = 0.037 |
6999 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.081 | Δρmax = 0.21 e Å−3 |
S = 1.02 | Δρmin = −0.20 e Å−3 |
2274 reflections | Absolute structure: Flack (1983), 1060 Friedel pairs |
180 parameters | Absolute structure parameter: 0.12 (9) |
1 restraint |
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 | ||
Cl1 | 0.75369 (7) | 0.98855 (8) | 0.02100 (8) | 0.0540 (2) | |
O1 | 1.15017 (17) | 0.62769 (17) | 0.54009 (13) | 0.0374 (4) | |
O2 | 0.8459 (2) | 0.6183 (2) | 0.95100 (14) | 0.0518 (6) | |
H2B | 0.874 (4) | 0.549 (3) | 0.971 (2) | 0.059 (11)* | |
N1 | 1.0036 (2) | 0.7862 (2) | 0.41778 (15) | 0.0339 (5) | |
N2 | 0.9609 (2) | 0.7697 (2) | 0.51292 (16) | 0.0340 (5) | |
H2A | 0.878 (3) | 0.799 (2) | 0.529 (2) | 0.032 (7)* | |
C1 | 0.8540 (3) | 0.9246 (3) | 0.19819 (17) | 0.0353 (6) | |
H1B | 0.7633 | 0.9546 | 0.2206 | 0.042* | |
C2 | 0.8869 (3) | 0.9307 (3) | 0.10113 (19) | 0.0359 (6) | |
C3 | 1.0208 (3) | 0.8895 (3) | 0.06536 (19) | 0.0391 (7) | |
H3A | 1.0407 | 0.8931 | −0.0004 | 0.047* | |
C4 | 1.1252 (3) | 0.8426 (3) | 0.1302 (2) | 0.0437 (7) | |
H4A | 1.2175 | 0.8169 | 0.1078 | 0.052* | |
C5 | 1.0943 (3) | 0.8336 (3) | 0.2265 (2) | 0.0405 (7) | |
H5A | 1.1654 | 0.8008 | 0.2686 | 0.049* | |
C6 | 0.9579 (3) | 0.8729 (2) | 0.26244 (17) | 0.0317 (6) | |
C7 | 0.9198 (3) | 0.8545 (2) | 0.36386 (18) | 0.0354 (6) | |
H7A | 0.8344 | 0.8927 | 0.3887 | 0.043* | |
C8 | 1.0415 (3) | 0.6900 (2) | 0.57049 (19) | 0.0307 (6) | |
C9 | 0.9925 (2) | 0.6764 (2) | 0.67131 (18) | 0.0301 (6) | |
C10 | 1.0357 (3) | 0.5631 (3) | 0.72305 (19) | 0.0349 (6) | |
H10A | 1.0971 | 0.5003 | 0.6938 | 0.042* | |
C11 | 0.9897 (3) | 0.5416 (3) | 0.81628 (18) | 0.0357 (6) | |
H11A | 1.0196 | 0.4651 | 0.8496 | 0.043* | |
C12 | 0.8986 (3) | 0.6348 (3) | 0.85996 (18) | 0.0364 (6) | |
C13 | 0.8576 (3) | 0.7497 (3) | 0.81142 (19) | 0.0446 (7) | |
H13A | 0.7991 | 0.8137 | 0.8419 | 0.053* | |
C14 | 0.9029 (3) | 0.7698 (3) | 0.71824 (18) | 0.0400 (6) | |
H14A | 0.8735 | 0.8471 | 0.6857 | 0.048* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0529 (4) | 0.0712 (5) | 0.0378 (4) | 0.0143 (4) | −0.0044 (4) | 0.0075 (4) |
O1 | 0.0349 (9) | 0.0442 (10) | 0.0330 (11) | 0.0057 (8) | 0.0062 (8) | −0.0020 (8) |
O2 | 0.0712 (14) | 0.0554 (15) | 0.0289 (12) | 0.0118 (11) | 0.0139 (10) | 0.0100 (11) |
N1 | 0.0393 (12) | 0.0384 (12) | 0.0240 (12) | −0.0034 (10) | 0.0052 (9) | 0.0007 (9) |
N2 | 0.0333 (11) | 0.0452 (13) | 0.0237 (12) | 0.0008 (10) | 0.0092 (11) | 0.0022 (11) |
C1 | 0.0346 (13) | 0.0401 (15) | 0.0311 (16) | 0.0029 (12) | 0.0072 (11) | 0.0000 (11) |
C2 | 0.0440 (15) | 0.0345 (15) | 0.0292 (15) | 0.0000 (11) | −0.0006 (12) | 0.0019 (11) |
C3 | 0.0500 (16) | 0.0418 (16) | 0.0255 (15) | 0.0020 (13) | 0.0134 (12) | 0.0053 (12) |
C4 | 0.0408 (15) | 0.0499 (18) | 0.0403 (19) | 0.0084 (13) | 0.0128 (13) | 0.0071 (14) |
C5 | 0.0395 (14) | 0.0500 (17) | 0.0321 (16) | 0.0065 (13) | 0.0040 (12) | 0.0058 (13) |
C6 | 0.0386 (14) | 0.0308 (14) | 0.0257 (15) | −0.0007 (11) | 0.0042 (11) | 0.0033 (12) |
C7 | 0.0364 (14) | 0.0384 (16) | 0.0315 (16) | 0.0025 (12) | 0.0065 (12) | −0.0004 (13) |
C8 | 0.0299 (12) | 0.0322 (14) | 0.0299 (15) | −0.0051 (11) | −0.0001 (10) | −0.0018 (11) |
C9 | 0.0295 (13) | 0.0356 (15) | 0.0252 (15) | −0.0020 (11) | −0.0003 (10) | −0.0020 (11) |
C10 | 0.0355 (13) | 0.0359 (15) | 0.0332 (16) | 0.0057 (12) | 0.0009 (12) | −0.0021 (12) |
C11 | 0.0401 (14) | 0.0357 (16) | 0.0313 (16) | 0.0039 (12) | −0.0037 (12) | 0.0073 (12) |
C12 | 0.0380 (14) | 0.0457 (17) | 0.0253 (15) | −0.0034 (12) | 0.0009 (12) | 0.0010 (13) |
C13 | 0.0578 (17) | 0.0432 (16) | 0.0327 (16) | 0.0138 (13) | 0.0094 (13) | −0.0026 (14) |
C14 | 0.0520 (16) | 0.0368 (15) | 0.0311 (16) | 0.0105 (13) | 0.0046 (12) | 0.0051 (12) |
Cl1—C2 | 1.741 (3) | C5—C6 | 1.392 (3) |
O1—C8 | 1.240 (3) | C5—H5A | 0.9300 |
O2—C12 | 1.359 (3) | C6—C7 | 1.460 (3) |
O2—H2B | 0.79 (3) | C7—H7A | 0.9300 |
N1—C7 | 1.265 (3) | C8—C9 | 1.473 (3) |
N1—N2 | 1.384 (3) | C9—C10 | 1.392 (3) |
N2—C8 | 1.342 (3) | C9—C14 | 1.396 (3) |
N2—H2A | 0.84 (2) | C10—C11 | 1.375 (3) |
C1—C2 | 1.380 (3) | C10—H10A | 0.9300 |
C1—C6 | 1.396 (3) | C11—C12 | 1.382 (4) |
C1—H1B | 0.9300 | C11—H11A | 0.9300 |
C2—C3 | 1.376 (3) | C12—C13 | 1.377 (4) |
C3—C4 | 1.388 (4) | C13—C14 | 1.370 (4) |
C3—H3A | 0.9300 | C13—H13A | 0.9300 |
C4—C5 | 1.368 (4) | C14—H14A | 0.9300 |
C4—H4A | 0.9300 | ||
C12—O2—H2B | 109 (2) | N1—C7—H7A | 120.2 |
C7—N1—N2 | 117.2 (2) | C6—C7—H7A | 120.2 |
C8—N2—N1 | 118.9 (2) | O1—C8—N2 | 121.9 (2) |
C8—N2—H2A | 122.6 (19) | O1—C8—C9 | 121.2 (2) |
N1—N2—H2A | 117.6 (19) | N2—C8—C9 | 117.0 (2) |
C2—C1—C6 | 119.4 (2) | C10—C9—C14 | 117.6 (2) |
C2—C1—H1B | 120.3 | C10—C9—C8 | 118.6 (2) |
C6—C1—H1B | 120.3 | C14—C9—C8 | 123.9 (2) |
C3—C2—C1 | 122.0 (2) | C11—C10—C9 | 121.6 (2) |
C3—C2—Cl1 | 118.9 (2) | C11—C10—H10A | 119.2 |
C1—C2—Cl1 | 119.1 (2) | C9—C10—H10A | 119.2 |
C2—C3—C4 | 118.1 (2) | C10—C11—C12 | 119.3 (2) |
C2—C3—H3A | 120.9 | C10—C11—H11A | 120.3 |
C4—C3—H3A | 120.9 | C12—C11—H11A | 120.3 |
C5—C4—C3 | 120.9 (2) | O2—C12—C13 | 117.2 (2) |
C5—C4—H4A | 119.6 | O2—C12—C11 | 122.5 (2) |
C3—C4—H4A | 119.6 | C13—C12—C11 | 120.3 (2) |
C4—C5—C6 | 120.9 (3) | C14—C13—C12 | 120.0 (2) |
C4—C5—H5A | 119.5 | C14—C13—H13A | 120.0 |
C6—C5—H5A | 119.5 | C12—C13—H13A | 120.0 |
C5—C6—C1 | 118.5 (2) | C13—C14—C9 | 121.1 (2) |
C5—C6—C7 | 121.4 (2) | C13—C14—H14A | 119.4 |
C1—C6—C7 | 120.0 (2) | C9—C14—H14A | 119.4 |
N1—C7—C6 | 119.6 (2) | ||
C7—N1—N2—C8 | 175.3 (2) | N1—N2—C8—C9 | 179.5 (2) |
C6—C1—C2—C3 | −1.2 (4) | O1—C8—C9—C10 | −21.1 (3) |
C6—C1—C2—Cl1 | 177.28 (19) | N2—C8—C9—C10 | 157.1 (2) |
C1—C2—C3—C4 | −1.0 (4) | O1—C8—C9—C14 | 159.9 (2) |
Cl1—C2—C3—C4 | −179.4 (2) | N2—C8—C9—C14 | −21.9 (3) |
C2—C3—C4—C5 | 2.0 (4) | C14—C9—C10—C11 | 1.4 (4) |
C3—C4—C5—C6 | −0.8 (4) | C8—C9—C10—C11 | −177.6 (2) |
C4—C5—C6—C1 | −1.4 (4) | C9—C10—C11—C12 | −0.1 (4) |
C4—C5—C6—C7 | 175.4 (3) | C10—C11—C12—O2 | 178.3 (2) |
C2—C1—C6—C5 | 2.3 (4) | C10—C11—C12—C13 | −1.7 (4) |
C2—C1—C6—C7 | −174.4 (2) | O2—C12—C13—C14 | −177.8 (3) |
N2—N1—C7—C6 | −178.8 (2) | C11—C12—C13—C14 | 2.3 (4) |
C5—C6—C7—N1 | −9.2 (4) | C12—C13—C14—C9 | −1.0 (4) |
C1—C6—C7—N1 | 167.4 (2) | C10—C9—C14—C13 | −0.8 (4) |
N1—N2—C8—O1 | −2.3 (3) | C8—C9—C14—C13 | 178.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.84 (2) | 2.20 (2) | 3.026 (3) | 169 (3) |
O2—H2B···O1ii | 0.79 (3) | 2.01 (3) | 2.739 (3) | 154 (3) |
C4—H4A···O2iii | 0.93 | 2.55 | 3.216 (3) | 128 |
Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) −x+2, −y+1, z+1/2; (iii) x+1/2, −y+3/2, z−1. |
Experimental details
Crystal data | |
Chemical formula | C14H11ClN2O2 |
Mr | 274.70 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 293 |
a, b, c (Å) | 9.0900 (8), 9.9396 (9), 13.8615 (12) |
V (Å3) | 1252.40 (19) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.30 |
Crystal size (mm) | 0.27 × 0.11 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.923, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6999, 2274, 1980 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.081, 1.02 |
No. of reflections | 2274 |
No. of parameters | 180 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.21, −0.20 |
Absolute structure | Flack (1983), 1060 Friedel pairs |
Absolute structure parameter | 0.12 (9) |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1i | 0.84 (2) | 2.20 (2) | 3.026 (3) | 169 (3) |
O2—H2B···O1ii | 0.79 (3) | 2.01 (3) | 2.739 (3) | 154 (3) |
C4—H4A···O2iii | 0.93 | 2.55 | 3.216 (3) | 128 |
Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) −x+2, −y+1, z+1/2; (iii) x+1/2, −y+3/2, z−1. |
Acknowledgements
The authors are thankful to the Higher Education Commission (HEC) Pakistan (project No. 20–2073) and Pakistan Academy of Sciences (PAS) for their financial support.
References
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Hao, Y.-M. (2009). Acta Cryst. E65, o2098. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Taha, M., Naz, H., Rahman, A. A., Ismail, N. H. & Yousuf, S. (2012). Acta Cryst. E68, o2846. 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.
As part of our ongoing studies of the N-acylhydrazone moiety (Taha et al., 2012), we now describe the structure of the title compound, which is similar to that of the previously published N'-(2-Chlorobenzylidene)-4-hydroxybenzohydrazide (Hao, 2009) with the difference that 2-chlorobenzne ring is replaced by 3-chlorophenyl ring (C1–C6). In the crystal, N2—H2A···O1, O2—H2B···O1,and C4—H4A···O2 hydrogen bonds link the moleucles into a three-dimensional-network (Table 2 and Fig. 2).