(Z)-Ethyl 2-chloro-2-[2-(4-methyl­phen­yl)hydrazinyl­idene]acetate

Asiri, A.M.; Arshad, M.N.; Zayed, M.E.M.; Alamry, K.A.; Bokhari, T.H.

doi:10.1107/S1600536812046521

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3420

doi:10.1107/S1600536812046521

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(Z)-Ethyl 2-chloro-2-[2-(4-methylphenyl)hydrazinylidene]acetate

Abdullah M. Asiri,^a,^b ^* Muhammad Nadeem Arshad,^b Mohie E. M. Zayed,^a Khalid A. Alamry ^a,^b and Tanveer Hussain Bokhari ^c ^*

^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

(Received 4 November 2012; accepted 10 November 2012; online 24 November 2012)

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.

Related literature

For related structures, see: Asiri et al. (2011 , 2012 ).

Experimental

Crystal data

C₁₁H₁₃ClN₂O₂
M_r = 240.68
Monoclinic, P 2₁ /c
a = 4.6152 (1) Å
b = 9.9444 (1) Å
c = 26.3152 (3) Å
β = 90.692 (1)°
V = 1207.66 (3) Å³
Z = 4
Cu Kα radiation
μ = 2.71 mm⁻¹
T = 296 K
0.41 × 0.14 × 0.13 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.692, T_max = 1.000
9526 measured reflections
2436 independent reflections
2224 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.113
S = 1.06
2436 reflections
150 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046521/hb6984sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046521/hb6984Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812046521/hb6984Isup3.cml

checkCIF report

Comment top

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.

Related literature top

For related structures, see: Asiri et al. (2011, 2012).

Experimental top

The molecule was synthesised according to the literature procedure (Asiri et al., 2011) and recrystallized from ethanol under slow evaporation giving yellow needles.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: 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).

Figures top

	Fig. 1. Molecular structure of the title molecule with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. A perspective view of the crystal packing of the title compound showing N-H···O and C-H···O hydrogen bonds as dashed lines - see Table 1 for details.

(Z)-Ethyl 2-chloro-2-[2-(4-methylphenyl)hydrazinylidene]acetate top

Crystal data top

C₁₁H₁₃ClN₂O₂	F(000) = 504
M_r = 240.68	D_x = 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

Data collection top

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	R_int = 0.019
ω scans	θ_max = 76.1°, θ_min = 4.8°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −4→5
T_min = 0.692, T_max = 1.000	k = −12→12
9526 measured reflections	l = −32→33

Refinement top

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(F_o²) + (0.0563P)² + 0.2618P] where P = (F_o² + 2F_c²)/3
2436 reflections	(Δ/σ)_max < 0.001
150 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₁H₁₃ClN₂O₂	V = 1207.66 (3) Å³
M_r = 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)°

Data collection top

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)
T_min = 0.692, T_max = 1.000	R_int = 0.019
9526 measured reflections

Refinement top

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	Δρ_max = 0.28 e Å⁻³
2436 reflections	Δρ_min = −0.23 e Å⁻³
150 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.692, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	9526, 2436, 2224
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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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