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

Abstract

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,

• a = 4.7480 (2) Å

• b = 9.9256 (4) Å

• c = 13.3084 (4) Å

• β = 91.468 (3)°

• V = 626.98 (4) ų

• 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[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 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)

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 ▶).

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

The NH H atom was located in a difference Fourier map and refined with U_iso(H) = 1.2U_eq(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), CH₃, and CH₂ H atoms, respectively, with U_iso(H) = k × U_eq(parent C-atom), where k = 1.5 for CH₃ H atoms and = 1.2 for other H atoms.

Figures

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.

Crystal data

C11H13ClN2O3	F(000) = 268
Mr = 256.68	Dx = 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

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	Rint = 0.018
ω scans	θmax = 75.8°, θmin = 5.6°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −5→5
Tmin = 0.860, Tmax = 1.000	k = −12→9
3153 measured reflections	l = −16→16

Refinement

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(Fo2) + (0.0575P)2 + 0.0434P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
1824 reflections	Δρmax = 0.16 e Å−3
159 parameters	Δρmin = −0.20 e Å−3
1 restraint	Absolute structure: Flack (1983), 466 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.01 (2)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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)

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)

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.