organic compounds
(Z)-Ethyl 2-chloro-2-[2-(4-methylphenyl)hydrazinylidene]acetate
aChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, bCenter of Excellence for Advanced Materials Research (CEAMR), Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and cDepartment of Chemistry, Government College University, Faisalabad 38000, Pakistan
*Correspondence e-mail: aasiri2@kau.edu.sa, sthbukhari@yahoo.co.uk
The molecule of the title compound, C11H13ClN2O2, is approximately planar (r.m.s. deviation = 0.099 Å for non-H atoms) and adopts a Z conformation about the C=N double bond. In the crystal, molecules are linked by N—H⋯O and C—H⋯O hydrogen bonds to the same O-atom acceptor, forming zigzag chains propagating along [010]. These interactions give rise to R21(6) loops.
Experimental
Crystal data
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2012); cell CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
10.1107/S1600536812046521/hb6984sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046521/hb6984Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812046521/hb6984Isup3.cml
The molecule was synthesised according to the literature procedure (Asiri et al., 2011) and recrystallized from ethanol under slow evaporation giving yellow needles.
The N—H H atom was located in a difference Fourier map and refined with Uiso(H) = 1.2Ueq(N). The C-bound H-atoms were included in calculated positions and treated as riding atoms: C-H = 0.93, 0.96 and 0.97 Å for CH(aromatic), CHmethyl, and CHmethylene H atoms, respectively, with Uiso(H) = k × Ueq(parent C-atom), where k = 1.5 for CHmethyl H atoms and = 1.2 for other H atoms.
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: WinGX (Farrugia, 2012).C11H13ClN2O2 | F(000) = 504 |
Mr = 240.68 | Dx = 1.324 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54184 Å |
Hall symbol: -P 2ybc | Cell parameters from 6552 reflections |
a = 4.6152 (1) Å | θ = 4.4–75.9° |
b = 9.9444 (1) Å | µ = 2.71 mm−1 |
c = 26.3152 (3) Å | T = 296 K |
β = 90.692 (1)° | Needle, yellow |
V = 1207.66 (3) Å3 | 0.41 × 0.14 × 0.13 mm |
Z = 4 |
Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer | 2436 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 2224 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.019 |
ω scans | θmax = 76.1°, θmin = 4.8° |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | h = −4→5 |
Tmin = 0.692, Tmax = 1.000 | k = −12→12 |
9526 measured reflections | l = −32→33 |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0563P)2 + 0.2618P] where P = (Fo2 + 2Fc2)/3 |
2436 reflections | (Δ/σ)max < 0.001 |
150 parameters | Δρmax = 0.28 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C11H13ClN2O2 | V = 1207.66 (3) Å3 |
Mr = 240.68 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 4.6152 (1) Å | µ = 2.71 mm−1 |
b = 9.9444 (1) Å | T = 296 K |
c = 26.3152 (3) Å | 0.41 × 0.14 × 0.13 mm |
β = 90.692 (1)° |
Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer | 2436 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012) | 2224 reflections with I > 2σ(I) |
Tmin = 0.692, Tmax = 1.000 | Rint = 0.019 |
9526 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.28 e Å−3 |
2436 reflections | Δρmin = −0.23 e Å−3 |
150 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 | ||
Cl1 | 0.43464 (11) | 0.05667 (5) | 0.234472 (17) | 0.07524 (19) | |
O1 | 0.1041 (3) | 0.28559 (14) | 0.27188 (5) | 0.0730 (4) | |
O2 | 0.2685 (3) | 0.27966 (12) | 0.35220 (4) | 0.0641 (3) | |
N1 | 0.8092 (3) | −0.02052 (14) | 0.31951 (5) | 0.0541 (3) | |
N2 | 0.6346 (3) | 0.08135 (12) | 0.32924 (5) | 0.0508 (3) | |
C1 | 0.9873 (3) | −0.07483 (15) | 0.35803 (6) | 0.0491 (3) | |
C2 | 1.0086 (4) | −0.01791 (17) | 0.40583 (6) | 0.0579 (4) | |
H2 | 0.9035 | 0.0590 | 0.4136 | 0.070* | |
C3 | 1.1886 (4) | −0.07686 (18) | 0.44203 (6) | 0.0621 (4) | |
H3 | 1.2034 | −0.0379 | 0.4741 | 0.074* | |
C4 | 1.3468 (3) | −0.19164 (17) | 0.43198 (6) | 0.0574 (4) | |
C5 | 1.3267 (4) | −0.24428 (17) | 0.38355 (7) | 0.0626 (4) | |
H5 | 1.4356 | −0.3199 | 0.3755 | 0.075* | |
C6 | 1.1496 (4) | −0.18777 (17) | 0.34674 (6) | 0.0592 (4) | |
H6 | 1.1393 | −0.2255 | 0.3144 | 0.071* | |
C7 | 0.4608 (3) | 0.12591 (16) | 0.29498 (6) | 0.0518 (3) | |
C8 | 0.2603 (3) | 0.23844 (16) | 0.30433 (6) | 0.0546 (4) | |
C9 | 0.0576 (5) | 0.3840 (2) | 0.36460 (8) | 0.0774 (5) | |
H9A | 0.1042 | 0.4668 | 0.3470 | 0.093* | |
H9B | −0.1354 | 0.3560 | 0.3541 | 0.093* | |
C10 | 0.0685 (7) | 0.4052 (3) | 0.41932 (10) | 0.1069 (9) | |
H10A | 0.0065 | 0.3250 | 0.4363 | 0.160* | |
H10B | −0.0572 | 0.4783 | 0.4281 | 0.160* | |
H10C | 0.2634 | 0.4263 | 0.4297 | 0.160* | |
C11 | 1.5322 (5) | −0.2579 (2) | 0.47260 (8) | 0.0768 (5) | |
H11A | 1.4576 | −0.3460 | 0.4797 | 0.115* | |
H11B | 1.5289 | −0.2045 | 0.5030 | 0.115* | |
H11C | 1.7278 | −0.2653 | 0.4609 | 0.115* | |
H1 | 0.799 (5) | −0.063 (2) | 0.2915 (10) | 0.092* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0816 (3) | 0.0890 (3) | 0.0549 (3) | 0.0032 (2) | −0.0103 (2) | −0.0051 (2) |
O1 | 0.0795 (8) | 0.0712 (8) | 0.0680 (7) | 0.0077 (6) | −0.0172 (6) | 0.0174 (6) |
O2 | 0.0687 (7) | 0.0615 (7) | 0.0618 (7) | 0.0123 (5) | −0.0083 (5) | 0.0025 (5) |
N1 | 0.0542 (7) | 0.0577 (7) | 0.0502 (7) | 0.0023 (6) | −0.0021 (6) | −0.0015 (6) |
N2 | 0.0478 (7) | 0.0507 (7) | 0.0539 (7) | −0.0047 (5) | −0.0002 (5) | 0.0055 (5) |
C1 | 0.0459 (7) | 0.0495 (7) | 0.0520 (8) | −0.0049 (6) | 0.0007 (6) | 0.0022 (6) |
C2 | 0.0621 (9) | 0.0567 (8) | 0.0549 (8) | 0.0072 (7) | 0.0012 (7) | −0.0032 (7) |
C3 | 0.0664 (10) | 0.0685 (10) | 0.0513 (9) | 0.0011 (8) | −0.0026 (7) | −0.0048 (7) |
C4 | 0.0508 (8) | 0.0597 (9) | 0.0615 (9) | −0.0048 (7) | −0.0038 (7) | 0.0064 (7) |
C5 | 0.0611 (10) | 0.0557 (9) | 0.0709 (10) | 0.0073 (7) | −0.0042 (8) | −0.0039 (7) |
C6 | 0.0639 (10) | 0.0575 (9) | 0.0561 (9) | 0.0035 (7) | −0.0023 (7) | −0.0083 (7) |
C7 | 0.0502 (8) | 0.0552 (8) | 0.0499 (8) | −0.0079 (6) | −0.0021 (6) | 0.0064 (6) |
C8 | 0.0549 (8) | 0.0529 (8) | 0.0557 (8) | −0.0078 (6) | −0.0039 (7) | 0.0122 (6) |
C9 | 0.0837 (13) | 0.0655 (11) | 0.0826 (13) | 0.0187 (10) | −0.0084 (10) | 0.0009 (9) |
C10 | 0.137 (2) | 0.0947 (17) | 0.0889 (17) | 0.0374 (16) | 0.0124 (15) | −0.0014 (13) |
C11 | 0.0738 (12) | 0.0788 (12) | 0.0773 (12) | 0.0022 (9) | −0.0163 (10) | 0.0121 (10) |
Cl1—C7 | 1.7377 (16) | C4—C11 | 1.512 (2) |
O1—C8 | 1.2056 (19) | C5—C6 | 1.380 (2) |
O2—C8 | 1.325 (2) | C5—H5 | 0.9300 |
O2—C9 | 1.462 (2) | C6—H6 | 0.9300 |
N1—N2 | 1.3215 (19) | C7—C8 | 1.475 (2) |
N1—C1 | 1.405 (2) | C9—C10 | 1.456 (3) |
N1—H1 | 0.85 (2) | C9—H9A | 0.9700 |
N2—C7 | 1.2788 (19) | C9—H9B | 0.9700 |
C1—C2 | 1.382 (2) | C10—H10A | 0.9600 |
C1—C6 | 1.384 (2) | C10—H10B | 0.9600 |
C2—C3 | 1.386 (2) | C10—H10C | 0.9600 |
C2—H2 | 0.9300 | C11—H11A | 0.9600 |
C3—C4 | 1.382 (2) | C11—H11B | 0.9600 |
C3—H3 | 0.9300 | C11—H11C | 0.9600 |
C4—C5 | 1.380 (2) | ||
C8—O2—C9 | 114.85 (13) | N2—C7—Cl1 | 123.01 (13) |
N2—N1—C1 | 120.49 (13) | C8—C7—Cl1 | 114.63 (11) |
N2—N1—H1 | 121.5 (16) | O1—C8—O2 | 124.26 (16) |
C1—N1—H1 | 117.4 (16) | O1—C8—C7 | 123.24 (16) |
C7—N2—N1 | 120.52 (14) | O2—C8—C7 | 112.49 (13) |
C2—C1—C6 | 119.67 (15) | C10—C9—O2 | 107.95 (17) |
C2—C1—N1 | 122.27 (14) | C10—C9—H9A | 110.1 |
C6—C1—N1 | 118.05 (14) | O2—C9—H9A | 110.1 |
C1—C2—C3 | 119.20 (15) | C10—C9—H9B | 110.1 |
C1—C2—H2 | 120.4 | O2—C9—H9B | 110.1 |
C3—C2—H2 | 120.4 | H9A—C9—H9B | 108.4 |
C4—C3—C2 | 122.08 (16) | C9—C10—H10A | 109.5 |
C4—C3—H3 | 119.0 | C9—C10—H10B | 109.5 |
C2—C3—H3 | 119.0 | H10A—C10—H10B | 109.5 |
C5—C4—C3 | 117.41 (15) | C9—C10—H10C | 109.5 |
C5—C4—C11 | 121.23 (17) | H10A—C10—H10C | 109.5 |
C3—C4—C11 | 121.35 (17) | H10B—C10—H10C | 109.5 |
C6—C5—C4 | 121.77 (16) | C4—C11—H11A | 109.5 |
C6—C5—H5 | 119.1 | C4—C11—H11B | 109.5 |
C4—C5—H5 | 119.1 | H11A—C11—H11B | 109.5 |
C5—C6—C1 | 119.83 (15) | C4—C11—H11C | 109.5 |
C5—C6—H6 | 120.1 | H11A—C11—H11C | 109.5 |
C1—C6—H6 | 120.1 | H11B—C11—H11C | 109.5 |
N2—C7—C8 | 122.34 (14) | ||
C1—N1—N2—C7 | −176.05 (13) | C2—C1—C6—C5 | 1.3 (2) |
N2—N1—C1—C2 | −6.0 (2) | N1—C1—C6—C5 | −179.88 (15) |
N2—N1—C1—C6 | 175.21 (14) | N1—N2—C7—C8 | 179.40 (13) |
C6—C1—C2—C3 | −1.3 (2) | N1—N2—C7—Cl1 | 1.1 (2) |
N1—C1—C2—C3 | 179.99 (15) | C9—O2—C8—O1 | 3.6 (2) |
C1—C2—C3—C4 | −0.4 (3) | C9—O2—C8—C7 | −175.40 (14) |
C2—C3—C4—C5 | 2.0 (3) | N2—C7—C8—O1 | 176.63 (15) |
C2—C3—C4—C11 | −177.38 (17) | Cl1—C7—C8—O1 | −4.9 (2) |
C3—C4—C5—C6 | −1.9 (3) | N2—C7—C8—O2 | −4.4 (2) |
C11—C4—C5—C6 | 177.44 (17) | Cl1—C7—C8—O2 | 174.06 (11) |
C4—C5—C6—C1 | 0.3 (3) | C8—O2—C9—C10 | 172.7 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.93 | 2.52 | 3.331 (2) | 145 |
N1—H1···O1i | 0.85 (2) | 2.30 (2) | 3.1120 (18) | 161 (2) |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C11H13ClN2O2 |
Mr | 240.68 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 4.6152 (1), 9.9444 (1), 26.3152 (3) |
β (°) | 90.692 (1) |
V (Å3) | 1207.66 (3) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 2.71 |
Crystal size (mm) | 0.41 × 0.14 × 0.13 |
Data collection | |
Diffractometer | Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.692, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9526, 2436, 2224 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.630 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.113, 1.06 |
No. of reflections | 2436 |
No. of parameters | 150 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.28, −0.23 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), WinGX (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···O1i | 0.93 | 2.52 | 3.331 (2) | 145 |
N1—H1···O1i | 0.85 (2) | 2.30 (2) | 3.1120 (18) | 161 (2) |
Symmetry code: (i) −x+1, y−1/2, −z+1/2. |
Acknowledgements
The authors thank the Deanship of Scientific Research at King Abdulaziz University for the support of this research via a Research Group Track Grant (No. 3-102/428).
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.
The present structure (I) is related to compounds already reported by our group, that is, (Z)-Ethyl 2-chloro-2-(2-(4-methoxyphenyl)hydrazono)acetate (II) (Asiri et al., 2012) and 1-Chloro-1-[(4-methylphenyl)hydrazinylidene]propan-2-one (III) (Asiri et al., 2011).
The title compound, Fig. 1, and II contain methyl and methoxy groups respectively at para positions of aromatic ring, which make them different from each other. The aromatic ring (C1—C6) is oriented at a dihedral angle of 9.49 (8)° with respect to the mean plane of the ester moiety (N1/N2/O1/O2 C7-Cl0; r.m.s. deviation 0.0454 Å), while the same angle in II is 3.05 (2) °. The spatial arrangements of different functional groups around the C7═N2 double bond give rise to trans isomer i.e. Z conformation.
In the crystal, N—H···O and C—H···O hydrogen bonds connect the molecules along the b axis to form zigzag chains, enclosing six membered R12(6) ring motifs - see Table. 1 and Fig. 2.