organic compounds
N′-Benzylidene-2-chloro-N-(4-chlorophenyl)acetohydrazide
aDepartment of Studies in Physics, University of Mysore, Manasagangotri, Mysore 570 006, India, and bDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri, Mangalore 574 199, India
*Correspondence e-mail: dr@physics.uni-mysore.ac.in
In the title compound, C15H12Cl2N2O, the atoms not making up the chlorobenzene ring are approximately coplanar (r.m.s. deviation = 0.073 Å). The dihedral angle between these 13 atoms and the chlorobenzene ring is 67.37 (10)°. The C=O and Csp2—Cl groups are almost eclipsed [Cl—C—C=O = −6.5 (3)°]. In the crystal, C(6) chains linked by C—H⋯O hydrogen bonds result in [100] chains.
CCDC reference: 974925
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2013); cell SAINT (Bruker, 2013); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).
Supporting information
CCDC reference: 974925
https://doi.org/10.1107/S1600536813032790/hb7168sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813032790/hb7168Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536813032790/hb7168Isup3.cml
4-Chlorophenylhydrazine (0.01 mol) was stirred with benzaldehyde (0.01 mol) in methanol (10 mL) in presence of few drops of acetic acid. The resulting precipitate was filtered and washed with chilled methanol and dried. The resulting Schiff base, 1-benzylidene-2-(4-chlorophenyl)hydrazine (0.01 mol) and triethylamine (0.01 mol) was taken in dioxane solvent. Chloroacetylchloride (0.01 mol) was added to the above mixture at 0–5°C. After completion of the reaction, the mixture was poured on to ice cold water. The precipitated solid was filtered, washed with water and recrystallized from ethanol. Brown blocks were obtained from a 1:2 mixture of DMF and ethanol solution by slow evaporation.
All the H atoms were fixed geometrically (C—H= 0.93–0.96 Å) and allowed to ride on their parent atoms with Uiso(H) =1.5Ueq(C-methyl) and = 1.2Ueq(C) for other H atoms.
Schiff bases are important class of compounds in medicinal chemistry, showing e.g.: antimicrobal (Shyma et al., 2013), and anticonvulsant (Nithinchandra et al., 2013) activities. As part of our studies in this area, we now describe the structure of the title compound, (I), (Fig. 1).
The dihedral angle between the benzene ring is 63.18° (13) and the molecules are linked to one another with hydrogen bonds C3—H3···O1 (Table 1, Fig. 2) along a-axis.
For background to
see: Nithinchandra et al. (2013); Shyma et al. (2013).Data collection: APEX2 (Bruker, 2013); cell
SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: PLATON (Spek, 2009).C15H12Cl2N2O | F(000) = 632 |
Mr = 307.17 | Dx = 1.389 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2ybc | Cell parameters from 2424 reflections |
a = 5.8548 (5) Å | θ = 3.1–64.9° |
b = 8.8892 (7) Å | µ = 3.95 mm−1 |
c = 28.273 (2) Å | T = 296 K |
β = 93.574 (4)° | Block, brown |
V = 1468.6 (2) Å3 | 0.24 × 0.23 × 0.23 mm |
Z = 4 |
Bruker X8 Proteum diffractometer | 2424 independent reflections |
Radiation source: Bruker MicroStar microfocus rotating anode | 2059 reflections with I > 2σ(I) |
Helios multilayer optics monochromator | Rint = 0.061 |
Detector resolution: 10.7 pixels mm-1 | θmax = 64.9°, θmin = 3.1° |
φ and ω scans | h = −3→6 |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | k = −10→10 |
Tmin = 0.451, Tmax = 0.464 | l = −32→32 |
10066 measured reflections |
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)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0867P)2 + 0.4858P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2424 reflections | Δρmax = 0.46 e Å−3 |
182 parameters | Δρmin = −0.45 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0091 (10) |
C15H12Cl2N2O | V = 1468.6 (2) Å3 |
Mr = 307.17 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 5.8548 (5) Å | µ = 3.95 mm−1 |
b = 8.8892 (7) Å | T = 296 K |
c = 28.273 (2) Å | 0.24 × 0.23 × 0.23 mm |
β = 93.574 (4)° |
Bruker X8 Proteum diffractometer | 2424 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2013) | 2059 reflections with I > 2σ(I) |
Tmin = 0.451, Tmax = 0.464 | Rint = 0.061 |
10066 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.145 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.46 e Å−3 |
2424 reflections | Δρmin = −0.45 e Å−3 |
182 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | 0.88967 (18) | 1.37204 (11) | 0.24673 (3) | 0.0826 (4) | |
Cl2 | 0.20082 (12) | 0.83970 (9) | −0.00451 (2) | 0.0605 (3) | |
O1 | 0.3525 (3) | 1.0325 (2) | 0.07342 (7) | 0.0507 (6) | |
N1 | 0.6637 (3) | 0.9050 (2) | 0.10193 (7) | 0.0379 (6) | |
N2 | 0.8010 (3) | 0.7816 (2) | 0.09360 (7) | 0.0374 (6) | |
C1 | 0.8254 (5) | 1.2311 (3) | 0.20500 (9) | 0.0492 (9) | |
C2 | 0.9644 (5) | 1.2137 (3) | 0.16799 (9) | 0.0474 (8) | |
C3 | 0.9104 (4) | 1.1056 (3) | 0.13393 (9) | 0.0428 (8) | |
C4 | 0.7207 (4) | 1.0156 (3) | 0.13769 (8) | 0.0365 (7) | |
C5 | 0.5846 (5) | 1.0340 (3) | 0.17556 (9) | 0.0483 (8) | |
C6 | 0.6354 (5) | 1.1429 (3) | 0.20918 (10) | 0.0563 (10) | |
C7 | 0.4802 (4) | 0.9266 (3) | 0.06984 (8) | 0.0372 (7) | |
C8 | 0.4559 (4) | 0.8111 (3) | 0.03078 (9) | 0.0433 (8) | |
C9 | 0.9704 (4) | 0.7535 (3) | 0.12257 (8) | 0.0419 (8) | |
C10 | 1.1217 (4) | 0.6259 (3) | 0.11428 (9) | 0.0394 (7) | |
C11 | 1.0788 (5) | 0.5252 (3) | 0.07751 (9) | 0.0472 (8) | |
C12 | 1.2319 (5) | 0.4110 (3) | 0.07002 (12) | 0.0588 (10) | |
C13 | 1.4303 (5) | 0.3975 (3) | 0.09870 (13) | 0.0617 (10) | |
C14 | 1.4735 (5) | 0.4958 (3) | 0.13506 (12) | 0.0611 (10) | |
C15 | 1.3196 (5) | 0.6093 (3) | 0.14347 (10) | 0.0501 (9) | |
H2 | 1.09330 | 1.27390 | 0.16590 | 0.0570* | |
H3 | 1.00200 | 1.09370 | 0.10850 | 0.0510* | |
H5 | 0.45790 | 0.97230 | 0.17830 | 0.0580* | |
H6 | 0.54240 | 1.15640 | 0.23430 | 0.0680* | |
H8A | 0.45510 | 0.71110 | 0.04450 | 0.0520* | |
H8B | 0.58570 | 0.81810 | 0.01120 | 0.0520* | |
H9 | 0.99860 | 0.81410 | 0.14910 | 0.0500* | |
H11 | 0.94640 | 0.53450 | 0.05780 | 0.0570* | |
H12 | 1.20130 | 0.34280 | 0.04550 | 0.0710* | |
H13 | 1.53430 | 0.32140 | 0.09320 | 0.0740* | |
H14 | 1.60730 | 0.48650 | 0.15440 | 0.0730* | |
H15 | 1.34880 | 0.67480 | 0.16880 | 0.0600* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1113 (8) | 0.0867 (6) | 0.0492 (5) | −0.0170 (5) | 0.0013 (4) | −0.0269 (4) |
Cl2 | 0.0502 (5) | 0.0824 (6) | 0.0476 (4) | −0.0035 (3) | −0.0079 (3) | 0.0018 (3) |
O1 | 0.0393 (10) | 0.0575 (11) | 0.0555 (11) | 0.0166 (9) | 0.0053 (8) | −0.0058 (8) |
N1 | 0.0360 (11) | 0.0419 (11) | 0.0361 (10) | 0.0096 (9) | 0.0041 (8) | −0.0049 (8) |
N2 | 0.0371 (11) | 0.0385 (10) | 0.0374 (10) | 0.0085 (9) | 0.0078 (8) | −0.0007 (8) |
C1 | 0.0585 (17) | 0.0553 (15) | 0.0333 (12) | 0.0032 (13) | −0.0010 (11) | −0.0035 (11) |
C2 | 0.0422 (15) | 0.0547 (15) | 0.0451 (14) | −0.0037 (12) | 0.0022 (11) | −0.0007 (11) |
C3 | 0.0374 (14) | 0.0517 (14) | 0.0406 (13) | 0.0050 (11) | 0.0124 (10) | −0.0020 (10) |
C4 | 0.0366 (13) | 0.0412 (12) | 0.0320 (11) | 0.0071 (10) | 0.0049 (9) | −0.0017 (9) |
C5 | 0.0489 (15) | 0.0581 (16) | 0.0395 (13) | −0.0045 (12) | 0.0150 (11) | −0.0031 (11) |
C6 | 0.0636 (19) | 0.0707 (18) | 0.0363 (13) | −0.0025 (15) | 0.0164 (12) | −0.0100 (12) |
C7 | 0.0316 (13) | 0.0444 (13) | 0.0366 (12) | 0.0043 (11) | 0.0109 (9) | 0.0023 (10) |
C8 | 0.0421 (14) | 0.0516 (14) | 0.0366 (12) | 0.0030 (11) | 0.0061 (10) | −0.0022 (10) |
C9 | 0.0455 (14) | 0.0452 (13) | 0.0352 (12) | 0.0088 (11) | 0.0033 (10) | −0.0027 (10) |
C10 | 0.0369 (13) | 0.0397 (12) | 0.0420 (13) | 0.0076 (10) | 0.0060 (10) | 0.0035 (10) |
C11 | 0.0434 (15) | 0.0474 (14) | 0.0510 (15) | 0.0059 (12) | 0.0035 (11) | −0.0056 (11) |
C12 | 0.0563 (18) | 0.0488 (15) | 0.0724 (19) | 0.0063 (13) | 0.0139 (15) | −0.0121 (13) |
C13 | 0.0497 (18) | 0.0458 (15) | 0.091 (2) | 0.0124 (13) | 0.0147 (16) | 0.0043 (15) |
C14 | 0.0450 (16) | 0.0559 (16) | 0.081 (2) | 0.0102 (14) | −0.0062 (14) | 0.0127 (15) |
C15 | 0.0516 (17) | 0.0460 (14) | 0.0519 (15) | 0.0089 (12) | −0.0042 (12) | 0.0031 (11) |
Cl1—C1 | 1.746 (3) | C11—C12 | 1.379 (4) |
Cl2—C8 | 1.762 (3) | C12—C13 | 1.380 (4) |
O1—C7 | 1.210 (3) | C13—C14 | 1.361 (5) |
N1—N2 | 1.389 (3) | C14—C15 | 1.383 (4) |
N1—C4 | 1.435 (3) | C2—H2 | 0.9300 |
N1—C7 | 1.376 (3) | C3—H3 | 0.9300 |
N2—C9 | 1.271 (3) | C5—H5 | 0.9300 |
C1—C2 | 1.374 (4) | C6—H6 | 0.9300 |
C1—C6 | 1.372 (4) | C8—H8A | 0.9700 |
C2—C3 | 1.383 (4) | C8—H8B | 0.9700 |
C3—C4 | 1.378 (3) | C9—H9 | 0.9300 |
C4—C5 | 1.384 (4) | C11—H11 | 0.9300 |
C5—C6 | 1.376 (4) | C12—H12 | 0.9300 |
C7—C8 | 1.508 (4) | C13—H13 | 0.9300 |
C9—C10 | 1.467 (4) | C14—H14 | 0.9300 |
C10—C11 | 1.383 (4) | C15—H15 | 0.9300 |
C10—C15 | 1.388 (4) | ||
N2—N1—C4 | 123.31 (18) | C10—C15—C14 | 120.3 (3) |
N2—N1—C7 | 115.78 (19) | C1—C2—H2 | 120.00 |
C4—N1—C7 | 120.46 (19) | C3—C2—H2 | 120.00 |
N1—N2—C9 | 118.9 (2) | C2—C3—H3 | 120.00 |
Cl1—C1—C2 | 118.9 (2) | C4—C3—H3 | 120.00 |
Cl1—C1—C6 | 119.6 (2) | C4—C5—H5 | 120.00 |
C2—C1—C6 | 121.6 (3) | C6—C5—H5 | 120.00 |
C1—C2—C3 | 119.2 (3) | C1—C6—H6 | 121.00 |
C2—C3—C4 | 120.0 (2) | C5—C6—H6 | 120.00 |
N1—C4—C3 | 119.8 (2) | Cl2—C8—H8A | 109.00 |
N1—C4—C5 | 120.4 (2) | Cl2—C8—H8B | 110.00 |
C3—C4—C5 | 119.8 (2) | C7—C8—H8A | 109.00 |
C4—C5—C6 | 120.5 (3) | C7—C8—H8B | 109.00 |
C1—C6—C5 | 118.9 (3) | H8A—C8—H8B | 108.00 |
O1—C7—N1 | 121.0 (2) | N2—C9—H9 | 120.00 |
O1—C7—C8 | 124.1 (2) | C10—C9—H9 | 120.00 |
N1—C7—C8 | 115.0 (2) | C10—C11—H11 | 120.00 |
Cl2—C8—C7 | 110.76 (17) | C12—C11—H11 | 120.00 |
N2—C9—C10 | 120.2 (2) | C11—C12—H12 | 120.00 |
C9—C10—C11 | 122.5 (2) | C13—C12—H12 | 120.00 |
C9—C10—C15 | 118.5 (2) | C12—C13—H13 | 120.00 |
C11—C10—C15 | 118.9 (2) | C14—C13—H13 | 120.00 |
C10—C11—C12 | 120.2 (3) | C13—C14—H14 | 120.00 |
C11—C12—C13 | 120.3 (3) | C15—C14—H14 | 120.00 |
C12—C13—C14 | 119.9 (3) | C10—C15—H15 | 120.00 |
C13—C14—C15 | 120.4 (3) | C14—C15—H15 | 120.00 |
C4—N1—N2—C9 | 9.3 (3) | C2—C3—C4—C5 | 0.1 (4) |
C7—N1—N2—C9 | −178.4 (2) | N1—C4—C5—C6 | −178.2 (2) |
N2—N1—C4—C3 | 65.1 (3) | C3—C4—C5—C6 | 0.9 (4) |
N2—N1—C4—C5 | −115.8 (3) | C4—C5—C6—C1 | −1.2 (4) |
C7—N1—C4—C3 | −106.8 (3) | O1—C7—C8—Cl2 | −6.5 (3) |
C7—N1—C4—C5 | 72.3 (3) | N1—C7—C8—Cl2 | 174.25 (17) |
N2—N1—C7—O1 | −178.6 (2) | N2—C9—C10—C11 | −5.1 (4) |
N2—N1—C7—C8 | 0.6 (3) | N2—C9—C10—C15 | 172.5 (2) |
C4—N1—C7—O1 | −6.1 (3) | C9—C10—C11—C12 | 177.1 (3) |
C4—N1—C7—C8 | 173.1 (2) | C15—C10—C11—C12 | −0.4 (4) |
N1—N2—C9—C10 | −178.7 (2) | C9—C10—C15—C14 | −176.1 (3) |
Cl1—C1—C2—C3 | −177.9 (2) | C11—C10—C15—C14 | 1.5 (4) |
C6—C1—C2—C3 | 0.6 (4) | C10—C11—C12—C13 | −0.9 (4) |
Cl1—C1—C6—C5 | 178.9 (2) | C11—C12—C13—C14 | 1.1 (5) |
C2—C1—C6—C5 | 0.4 (4) | C12—C13—C14—C15 | 0.0 (5) |
C1—C2—C3—C4 | −0.8 (4) | C13—C14—C15—C10 | −1.3 (4) |
C2—C3—C4—N1 | 179.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.93 | 2.40 | 3.256 (3) | 154 |
Symmetry code: (i) x+1, y, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.93 | 2.40 | 3.256 (3) | 154 |
Symmetry code: (i) x+1, y, z. |
Acknowledgements
The authors are thankful to the IOE, University of Mysore, for providing the single-crystal X-ray diffraction facility. VN is grateful to the UGC for the award of an RFSMS Fellowship. RD acknowledges the UGC, New Delhi, for financial support under the Major Research Project Scheme [UGC MRP No. F.41–882/2012 (SR) dated 01/07/2012].
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.
Schiff bases are important class of compounds in medicinal chemistry, showing e.g.: antimicrobal (Shyma et al., 2013), and anticonvulsant (Nithinchandra et al., 2013) activities. As part of our studies in this area, we now describe the structure of the title compound, (I), (Fig. 1).
The dihedral angle between the benzene ring is 63.18° (13) and the molecules are linked to one another with hydrogen bonds C3—H3···O1 (Table 1, Fig. 2) along a-axis.