Ethyl (Z)-2-chloro-2-[2-(4-meth­oxy­phenyl)hydrazin-1-yl­idene]acetate

Asiri, A.M.; Arshad, M.N.; Zayed, M.E.M.; Alamry, K.A.; Shafiq, M.

doi:10.1107/S1600536812044285

organic compounds

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ISSN: 2056-9890

Volume 68| Part 12| December 2012| Page o3274

doi:10.1107/S1600536812044285

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Ethyl (Z)-2-chloro-2-[2-(4-methoxyphenyl)hydrazin-1-ylidene]acetate

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

^aChemistry Department and the, Center of Excellence for Advanced Materials Research (CEAMR), 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, ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and ^dDepartment of Chemistry, Government College University, 38000, Faisalabad, Pakistan
^*Correspondence e-mail: aasiri2@kau.edu.sa, hafizshafique@hotmail.com

(Received 18 October 2012; accepted 25 October 2012; online 3 November 2012)

The molecule of the title compound, C₁₁H₁₃ClN₂O₃, is planar (r.m.s. deviation = 0.0587 Å for non-H atoms) and adopts a Z conformation about the C=N double bond. In the crystal, molecules are linked via an N—H⋯O hydrogen bond, forming zigzag chains propagating along [010]. These chains are consolidated by C—H⋯O hydrogen bonds.

Related literature

For closely related structures, see: Asiri et al. (2011a ,b ). For graph-set notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₃ClN₂O₃
M_r = 256.68
Monoclinic, P 2₁
a = 4.7480 (2) Å
b = 9.9256 (4) Å
c = 13.3084 (4) Å
β = 91.468 (3)°
V = 626.98 (4) Å³
Z = 2
Cu Kα radiation
μ = 2.71 mm⁻¹
T = 296 K
0.23 × 0.11 × 0.06 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ) T_min = 0.860, T_max = 1.000
3153 measured reflections
1824 independent reflections
1685 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.109
S = 1.07
1824 reflections
159 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 466 Friedel pairs
Flack parameter: 0.01 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2ⁱ	0.97 (4)	2.11 (4)	3.053 (3)	164 (3)
C6—H6⋯O2ⁱ	0.93	2.59	3.368 (3)	141
Symmetry code: (i) $[-x+2, y-{\script{1\over 2}}, -z+1]$ .

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/S1600536812044285/su2515sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812044285/su2515Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812044285/su2515Isup3.cml

checkCIF report

Comment top

The present structure analysis is a continuation of our interest in related compounds already reported by our group, that is, 1-Chloro-1-[(4-methoxyphenyl)hydrazinylidene]propan-2-one (Asiri et al., 2011a) and 1-Chloro-1-[(4-methylphenyl)hydrazinylidene]propan-2-one (Asiri et al., 2011b).

In the title compound, Fig. 1, the methoxy aromatic ring (C1—C6) is oriented at a dihedral angle of 3.05 (2) ° with respect to the mean plane of the ester moiety (N1/N2/C7-Cl1; planar to within 0.0 \%A). The molecule adopts a Z conformation around the C7═N2 double bond.

In the crystal, N-H···O and C-H···O hydrogen bonds connect the molecules to form zigzag chains along the b axis, enclosing six membered R¹₂(6) ring motifs (Bernstein et al., 1995) - see Table 1 and Fig. 2.

Related literature top

For closely related structures, see: Asiri et al. (2011a,b). For graph-set notation, see: Bernstein et al. (1995).

Experimental top

The molecule was synthesised according to the literature procedure (Asiri et al., 2011a) and recrystallized from ethanol giving yellow needle-like crystals.

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. A view of the molecular structure of the title molecule with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A partial view along the a axis of the crystal packing of the title compound. The N-H···O and C-H···O hydrogen bonds are shown as dashed lines - see Table 1 for details.

Ethyl (Z)-2-chloro-2-[2-(4-methoxyphenyl)hydrazin-1-ylidene]acetate top

Crystal data top

C₁₁H₁₃ClN₂O₃	F(000) = 268
M_r = 256.68	D_x = 1.360 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: P 2yb	Cell parameters from 2064 reflections
a = 4.7480 (2) Å	θ = 4.5–75.6°
b = 9.9256 (4) Å	µ = 2.71 mm⁻¹
c = 13.3084 (4) Å	T = 296 K
β = 91.468 (3)°	Needle, yellow
V = 626.98 (4) Å³	0.23 × 0.11 × 0.06 mm
Z = 2

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer	1824 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	1685 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.018
ω scans	θ_max = 75.8°, θ_min = 5.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −5→5
T_min = 0.860, T_max = 1.000	k = −12→9
3153 measured reflections	l = −16→16

Refinement top

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)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.109	w = 1/[σ²(F_o²) + (0.0575P)² + 0.0434P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1824 reflections	Δρ_max = 0.16 e Å⁻³
159 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 466 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (2)

Crystal data top

C₁₁H₁₃ClN₂O₃	V = 626.98 (4) Å³
M_r = 256.68	Z = 2
Monoclinic, P2₁	Cu Kα radiation
a = 4.7480 (2) Å	µ = 2.71 mm⁻¹
b = 9.9256 (4) Å	T = 296 K
c = 13.3084 (4) Å	0.23 × 0.11 × 0.06 mm
β = 91.468 (3)°

Data collection top

Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer	1824 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	1685 reflections with I > 2σ(I)
T_min = 0.860, T_max = 1.000	R_int = 0.018
3153 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.109	Δρ_max = 0.16 e Å⁻³
S = 1.07	Δρ_min = −0.20 e Å⁻³
1824 reflections	Absolute structure: Flack (1983), 466 Friedel pairs
159 parameters	Absolute structure parameter: 0.01 (2)
1 restraint

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	1.03853 (17)	0.46169 (11)	0.45757 (5)	0.0873 (3)
O1	0.1393 (5)	0.2136 (3)	0.96956 (16)	0.0895 (7)
O2	1.4090 (4)	0.6817 (2)	0.52714 (16)	0.0785 (6)
O3	1.2764 (5)	0.6800 (2)	0.68691 (15)	0.0735 (6)
N1	0.7239 (5)	0.3882 (3)	0.63734 (15)	0.0607 (5)
N2	0.9085 (4)	0.4860 (2)	0.64964 (14)	0.0566 (5)
C1	0.5738 (5)	0.3420 (3)	0.72120 (18)	0.0542 (5)
C2	0.6135 (6)	0.4022 (3)	0.81488 (19)	0.0616 (6)
H2	0.7405	0.4728	0.8235	0.074*
C3	0.4620 (6)	0.3557 (3)	0.89470 (19)	0.0675 (7)
H3	0.4869	0.3960	0.9574	0.081*
C4	0.2750 (6)	0.2509 (3)	0.8836 (2)	0.0656 (7)
C5	0.2349 (6)	0.1908 (3)	0.7907 (2)	0.0666 (7)
H5	0.1083	0.1199	0.7824	0.080*
C6	0.3865 (6)	0.2378 (3)	0.7097 (2)	0.0637 (7)
H6	0.3604	0.1979	0.6469	0.076*
C7	1.0590 (6)	0.5288 (3)	0.57810 (18)	0.0584 (6)
C8	1.2652 (6)	0.6375 (3)	0.59250 (18)	0.0605 (6)
C9	1.4822 (8)	0.7834 (4)	0.7110 (2)	0.0894 (10)
H9A	1.6681	0.7533	0.6923	0.107*
H9B	1.4376	0.8647	0.6734	0.107*
C10	1.4804 (13)	0.8107 (5)	0.8152 (3)	0.1310 (18)
H10A	1.2976	0.8430	0.8329	0.197*
H10B	1.6195	0.8780	0.8315	0.197*
H10C	1.5228	0.7297	0.8520	0.197*
C11	−0.0364 (8)	0.1011 (4)	0.9655 (3)	0.0903 (11)
H11A	−0.1846	0.1157	0.9162	0.135*
H11B	−0.1166	0.0869	1.0301	0.135*
H11C	0.0709	0.0233	0.9473	0.135*
H1N	0.712 (7)	0.330 (5)	0.579 (3)	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1022 (6)	0.1004 (6)	0.0602 (4)	−0.0065 (5)	0.0182 (3)	−0.0155 (4)
O1	0.0895 (14)	0.112 (2)	0.0679 (12)	−0.0237 (15)	0.0142 (10)	0.0084 (13)
O2	0.0887 (14)	0.0810 (15)	0.0666 (11)	−0.0067 (12)	0.0164 (9)	0.0181 (10)
O3	0.0847 (13)	0.0763 (13)	0.0597 (10)	−0.0197 (11)	0.0073 (9)	0.0004 (9)
N1	0.0667 (12)	0.0627 (13)	0.0528 (11)	−0.0039 (11)	0.0032 (9)	−0.0050 (9)
N2	0.0595 (11)	0.0586 (14)	0.0518 (9)	0.0038 (10)	0.0020 (8)	0.0034 (9)
C1	0.0548 (13)	0.0542 (13)	0.0537 (12)	0.0056 (11)	0.0003 (9)	−0.0011 (10)
C2	0.0642 (14)	0.0615 (15)	0.0591 (14)	−0.0054 (13)	0.0007 (10)	−0.0026 (11)
C3	0.0701 (16)	0.0773 (19)	0.0551 (13)	−0.0018 (15)	0.0021 (11)	−0.0052 (13)
C4	0.0605 (14)	0.0745 (18)	0.0619 (15)	0.0016 (14)	0.0031 (11)	0.0094 (13)
C5	0.0634 (15)	0.0655 (17)	0.0708 (15)	−0.0077 (14)	−0.0009 (11)	0.0018 (13)
C6	0.0685 (16)	0.0640 (16)	0.0583 (14)	−0.0046 (14)	−0.0035 (11)	−0.0065 (12)
C7	0.0618 (14)	0.0601 (15)	0.0533 (12)	0.0101 (12)	0.0053 (10)	0.0017 (10)
C8	0.0687 (15)	0.0577 (15)	0.0554 (12)	0.0069 (13)	0.0042 (10)	0.0079 (11)
C9	0.106 (3)	0.083 (2)	0.0788 (19)	−0.026 (2)	0.0017 (17)	0.0007 (17)
C10	0.191 (5)	0.103 (3)	0.098 (3)	−0.042 (4)	−0.014 (3)	−0.020 (3)
C11	0.081 (2)	0.088 (3)	0.103 (2)	−0.006 (2)	0.0184 (18)	0.020 (2)

Geometric parameters (Å, º) top

Cl1—C7	1.737 (3)	C3—H3	0.9300
O1—C4	1.378 (3)	C4—C5	1.381 (4)
O1—C11	1.394 (5)	C5—C6	1.393 (4)
O2—C8	1.202 (3)	C5—H5	0.9300
O3—C8	1.325 (3)	C6—H6	0.9300
O3—C9	1.447 (4)	C7—C8	1.466 (4)
N1—N2	1.315 (3)	C9—C10	1.414 (5)
N1—C1	1.416 (3)	C9—H9A	0.9700
N1—H1N	0.97 (4)	C9—H9B	0.9700
N2—C7	1.277 (3)	C10—H10A	0.9600
C1—C6	1.370 (4)	C10—H10B	0.9600
C1—C2	1.391 (3)	C10—H10C	0.9600
C2—C3	1.378 (4)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.373 (4)	C11—H11C	0.9600

C4—O1—C11	118.3 (3)	N2—C7—C8	122.1 (2)
C8—O3—C9	116.5 (2)	N2—C7—Cl1	122.8 (2)
N2—N1—C1	119.3 (2)	C8—C7—Cl1	115.10 (19)
N2—N1—H1N	124 (2)	O2—C8—O3	124.1 (3)
C1—N1—H1N	115 (2)	O2—C8—C7	124.3 (3)
C7—N2—N1	122.4 (2)	O3—C8—C7	111.6 (2)
C6—C1—C2	119.8 (2)	C10—C9—O3	109.4 (3)
C6—C1—N1	119.7 (2)	C10—C9—H9A	109.8
C2—C1—N1	120.5 (3)	O3—C9—H9A	109.8
C3—C2—C1	119.1 (3)	C10—C9—H9B	109.8
C3—C2—H2	120.5	O3—C9—H9B	109.8
C1—C2—H2	120.5	H9A—C9—H9B	108.2
C4—C3—C2	121.3 (2)	C9—C10—H10A	109.5
C4—C3—H3	119.4	C9—C10—H10B	109.5
C2—C3—H3	119.4	H10A—C10—H10B	109.5
C3—C4—O1	115.4 (3)	C9—C10—H10C	109.5
C3—C4—C5	119.9 (2)	H10A—C10—H10C	109.5
O1—C4—C5	124.8 (3)	H10B—C10—H10C	109.5
C4—C5—C6	119.1 (3)	O1—C11—H11A	109.5
C4—C5—H5	120.5	O1—C11—H11B	109.5
C6—C5—H5	120.5	H11A—C11—H11B	109.5
C1—C6—C5	120.9 (2)	O1—C11—H11C	109.5
C1—C6—H6	119.6	H11A—C11—H11C	109.5
C5—C6—H6	119.6	H11B—C11—H11C	109.5

C1—N1—N2—C7	177.1 (2)	C2—C1—C6—C5	−0.1 (4)
N2—N1—C1—C6	−178.3 (2)	N1—C1—C6—C5	−179.6 (3)
N2—N1—C1—C2	2.2 (4)	C4—C5—C6—C1	0.1 (4)
C6—C1—C2—C3	−0.2 (4)	N1—N2—C7—C8	−179.7 (2)
N1—C1—C2—C3	179.4 (3)	N1—N2—C7—Cl1	−0.6 (4)
C1—C2—C3—C4	0.5 (5)	C9—O3—C8—O2	−1.8 (4)
C2—C3—C4—O1	179.4 (3)	C9—O3—C8—C7	177.3 (3)
C2—C3—C4—C5	−0.4 (5)	N2—C7—C8—O2	−179.3 (3)
C11—O1—C4—C3	−175.0 (3)	Cl1—C7—C8—O2	1.5 (4)
C11—O1—C4—C5	4.9 (5)	N2—C7—C8—O3	1.6 (4)
C3—C4—C5—C6	0.1 (5)	Cl1—C7—C8—O3	−177.6 (2)
O1—C4—C5—C6	−179.7 (3)	C8—O3—C9—C10	−176.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2ⁱ	0.97 (4)	2.11 (4)	3.053 (3)	164 (3)
C6—H6···O2ⁱ	0.93	2.59	3.368 (3)	141

Symmetry code: (i) −x+2, y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃ClN₂O₃
M_r	256.68
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	4.7480 (2), 9.9256 (4), 13.3084 (4)
β (°)	91.468 (3)
V (Å³)	626.98 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	2.71
Crystal size (mm)	0.23 × 0.11 × 0.06

Data collection
Diffractometer	Agilent SuperNova (Dual, Cu at zero, Atlas) CCD diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2012)
T_min, T_max	0.860, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	3153, 1824, 1685
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.109, 1.07
No. of reflections	1824
No. of parameters	159
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.20
Absolute structure	Flack (1983), 466 Friedel pairs
Absolute structure parameter	0.01 (2)

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
N1—H1N···O2ⁱ	0.97 (4)	2.11 (4)	3.053 (3)	164 (3)
C6—H6···O2ⁱ	0.93	2.59	3.368 (3)	141

Symmetry code: (i) −x+2, y−1/2, −z+1.

Acknowledgements

We would like to 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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