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

Abstract

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 R ₂ ¹(6) loops.

Related literature  

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

Experimental  

Crystal data  

• C₁₁H₁₃ClN₂O₂

• M _r = 240.68

• Monoclinic,

• a = 4.6152 (1) Å

• b = 9.9444 (1) Å

• c = 26.3152 (3) Å

• β = 90.692 (1)°

• V = 1207.66 (3) ų

• 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[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 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

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
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) .

supplementary crystallographic information

Comment

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.

Experimental

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

Refinement

The N—H 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), CH_methyl, and CH_methylene H atoms, respectively, with U_iso(H) = k × U_eq(parent C-atom), where k = 1.5 for CH_methyl H atoms and = 1.2 for other H atoms.

Figures

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.

Crystal data

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

Data collection

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

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

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	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 (Ų)

	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)

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)

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.