Eth­yl 4-chloro-3-oxo-2-(phenyl­hydrazono)butyrate

The title compound, C₁₂H₁₃ClN₂O₃, adopts a keto–hydrazo tautomeric form stabilized by an intra­molecular N—H...O hydrogen bond. The configuration around the C=N bond is trans. The dihedral angle between the aromatic ring and the aliphatic chain is 5.52 (9)°. Symmetry-related mol­ecules are linked via C—H...O hydrogen bonds to form chains along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.092
• Data-to-parameter ratio = 15.1

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Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Ethyl 4-chloro-3-oxo-2-(phenylhydrazono)butyrate

Crystal data

C12H13ClN2O3	F(000) = 560
Mr = 268.69	Dx = 1.384 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7493 reflections
a = 5.6856 (8) Å	θ = 1.9–27.1°
b = 10.9674 (10) Å	µ = 0.30 mm^−1
c = 20.704 (3) Å	T = 296 K
β = 92.306 (12)°	Plate, yellow
V = 1290.0 (3) Å^3	0.52 × 0.42 × 0.13 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	2516 independent reflections
Radiation source: fine-focus sealed tube	1424 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 2.0°
ω scans	h = −6→7
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −13→13
Tmin = 0.860, Tmax = 0.962	l = −24→25
7849 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 0.82	w = 1/[σ^2(Fo^2) + (0.0519P)^2] where P = (Fo^2 + 2Fc^2)/3
2516 reflections	(Δ/σ)max = 0.001
167 parameters	Δρmax = 0.17 e Å^−3
0 restraints	Δρmin = −0.17 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
C1	0.0174 (3)	0.72494 (17)	0.65632 (9)	0.0512 (4)
C2	−0.0252 (3)	0.67855 (18)	0.59470 (9)	0.0611 (5)
H2	0.0752	0.6204	0.5782	0.073*
C3	−0.2157 (4)	0.7187 (2)	0.55814 (10)	0.0676 (6)
H3	−0.2440	0.6873	0.5168	0.081*
C4	−0.3653 (4)	0.80462 (19)	0.58154 (10)	0.0670 (6)
H4	−0.4949	0.8309	0.5565	0.080*
C5	−0.3220 (4)	0.85150 (19)	0.64242 (10)	0.0658 (5)
H5	−0.4225	0.9102	0.6584	0.079*
C6	−0.1305 (3)	0.81230 (16)	0.68019 (9)	0.0570 (5)
H6	−0.1018	0.8445	0.7213	0.068*
C7	0.5344 (3)	0.55964 (16)	0.70680 (9)	0.0512 (4)
C8	0.6179 (3)	0.61235 (18)	0.76931 (9)	0.0532 (4)
C9	0.9217 (4)	0.6245 (2)	0.85134 (9)	0.0675 (5)
H9A	0.8858	0.7110	0.8510	0.081*
H9B	1.0915	0.6155	0.8521	0.081*
C10	0.8285 (4)	0.5680 (2)	0.91027 (10)	0.0849 (7)
H10A	0.8978	0.6071	0.9479	0.127*
H10B	0.8669	0.4828	0.9111	0.127*
H10C	0.6607	0.5777	0.9098	0.127*
C11	0.6597 (4)	0.46411 (16)	0.67139 (9)	0.0538 (4)
C12	0.5435 (4)	0.42834 (19)	0.60645 (9)	0.0644 (5)
H12A	0.4966	0.5015	0.5830	0.077*
H12B	0.4028	0.3812	0.6138	0.077*
Cl1	0.73347 (12)	0.34221 (6)	0.55934 (3)	0.0957 (3)
N1	0.2109 (3)	0.68571 (15)	0.69546 (8)	0.0548 (4)
N2	0.3444 (3)	0.59871 (14)	0.67505 (7)	0.0517 (4)
O1	0.5090 (2)	0.69194 (14)	0.79586 (6)	0.0712 (4)
O2	0.8199 (2)	0.56811 (12)	0.79256 (6)	0.0629 (4)
O3	0.8393 (3)	0.41558 (13)	0.69109 (7)	0.0751 (4)
H1	0.241 (4)	0.715 (2)	0.7320 (11)	0.081 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0448 (10)	0.0579 (11)	0.0508 (10)	−0.0048 (9)	0.0004 (8)	0.0050 (9)
C2	0.0576 (12)	0.0749 (13)	0.0510 (11)	0.0070 (10)	0.0028 (9)	−0.0015 (10)
C3	0.0694 (14)	0.0818 (14)	0.0511 (11)	0.0071 (11)	−0.0052 (10)	−0.0006 (10)
C4	0.0584 (12)	0.0760 (14)	0.0655 (13)	0.0072 (11)	−0.0118 (10)	0.0077 (11)
C5	0.0628 (12)	0.0607 (12)	0.0737 (14)	0.0084 (10)	−0.0008 (11)	0.0012 (10)
C6	0.0551 (11)	0.0598 (11)	0.0556 (11)	−0.0028 (9)	−0.0031 (9)	−0.0034 (9)
C7	0.0489 (11)	0.0558 (10)	0.0487 (10)	−0.0034 (9)	−0.0017 (8)	0.0047 (8)
C8	0.0484 (11)	0.0610 (11)	0.0500 (11)	−0.0038 (10)	0.0011 (9)	0.0021 (9)
C9	0.0628 (12)	0.0764 (13)	0.0622 (12)	−0.0050 (11)	−0.0126 (10)	−0.0099 (11)
C10	0.1010 (17)	0.0989 (17)	0.0543 (13)	−0.0119 (14)	−0.0025 (12)	−0.0100 (12)
C11	0.0603 (12)	0.0510 (10)	0.0497 (10)	0.0009 (9)	−0.0046 (9)	0.0037 (8)
C12	0.0713 (13)	0.0652 (12)	0.0557 (11)	0.0086 (10)	−0.0081 (10)	−0.0044 (9)
Cl1	0.1100 (5)	0.1103 (5)	0.0657 (4)	0.0388 (4)	−0.0112 (3)	−0.0241 (3)
N1	0.0474 (9)	0.0662 (10)	0.0505 (9)	0.0002 (8)	−0.0004 (7)	−0.0014 (8)
N2	0.0487 (9)	0.0553 (9)	0.0511 (9)	−0.0031 (8)	0.0017 (7)	0.0041 (7)
O1	0.0629 (9)	0.0918 (10)	0.0581 (8)	0.0152 (8)	−0.0060 (7)	−0.0165 (7)
O2	0.0596 (8)	0.0716 (8)	0.0563 (8)	0.0046 (7)	−0.0128 (6)	−0.0081 (7)
O3	0.0826 (10)	0.0731 (9)	0.0678 (9)	0.0233 (8)	−0.0205 (8)	−0.0111 (7)

Geometric parameters (Å, º)

C1—C6	1.379 (2)	C8—O2	1.320 (2)
C1—C2	1.386 (3)	C9—O2	1.463 (2)
C1—N1	1.407 (2)	C9—C10	1.485 (3)
C2—C3	1.369 (3)	C9—H9A	0.97
C2—H2	0.93	C9—H9B	0.97
C3—C4	1.371 (3)	C10—H10A	0.96
C3—H3	0.93	C10—H10B	0.96
C4—C5	1.374 (3)	C10—H10C	0.96
C4—H4	0.93	C11—O3	1.208 (2)
C5—C6	1.383 (3)	C11—C12	1.525 (3)
C5—H5	0.93	C12—Cl1	1.759 (2)
C6—H6	0.93	C12—H12A	0.97
C7—N2	1.314 (2)	C12—H12B	0.97
C7—C11	1.478 (3)	N1—N2	1.300 (2)
C7—C8	1.478 (2)	N1—H1	0.83 (2)
C8—O1	1.214 (2)
C6—C1—C2	119.90 (18)	O2—C9—H9A	109.4
C6—C1—N1	118.7 (2)	C10—C9—H9A	109.4
C2—C1—N1	121.4 (2)	O2—C9—H9B	109.4
C3—C2—C1	119.72 (18)	C10—C9—H9B	109.4
C3—C2—H2	120.1	H9A—C9—H9B	108.0
C1—C2—H2	120.1	C9—C10—H10A	109.5
C2—C3—C4	120.95 (19)	C9—C10—H10B	109.5
C2—C3—H3	119.5	H10A—C10—H10B	109.5
C4—C3—H3	119.5	C9—C10—H10C	109.5
C3—C4—C5	119.4 (2)	H10A—C10—H10C	109.5
C3—C4—H4	120.3	H10B—C10—H10C	109.5
C5—C4—H4	120.3	O3—C11—C7	124.2 (2)
C4—C5—C6	120.68 (19)	O3—C11—C12	120.96 (17)
C4—C5—H5	119.7	C7—C11—C12	114.79 (17)
C6—C5—H5	119.7	C11—C12—Cl1	111.9 (1)
C1—C6—C5	119.37 (19)	C11—C12—H12A	109.2
C1—C6—H6	120.3	Cl1—C12—H12A	109.2
C5—C6—H6	120.3	C11—C12—H12B	109.2
N2—C7—C11	112.7 (2)	Cl1—C12—H12B	109.2
N2—C7—C8	122.6 (2)	H12A—C12—H12B	107.9
C11—C7—C8	124.6 (2)	N2—N1—C1	119.4 (2)
O1—C8—O2	123.4 (2)	N2—N1—H1	118.4 (16)
O1—C8—C7	121.7 (2)	C1—N1—H1	122.3 (16)
O2—C8—C7	114.83 (17)	N1—N2—C7	123.8 (2)
O2—C9—C10	111.38 (17)	C8—O2—C9	117.21 (15)
C6—C1—C2—C3	−0.8 (3)	C8—C7—C11—O3	3.0 (3)
N1—C1—C2—C3	179.82 (17)	N2—C7—C11—C12	−1.0 (2)
C1—C2—C3—C4	0.1 (3)	C8—C7—C11—C12	−177.49 (16)
C2—C3—C4—C5	0.5 (3)	O3—C11—C12—Cl1	−14.3 (2)
C3—C4—C5—C6	−0.4 (3)	C7—C11—C12—Cl1	166.23 (13)
C2—C1—C6—C5	0.8 (3)	C6—C1—N1—N2	176.26 (15)
N1—C1—C6—C5	−179.77 (17)	C2—C1—N1—N2	−4.3 (3)
C4—C5—C6—C1	−0.2 (3)	C1—N1—N2—C7	176.93 (16)
N2—C7—C8—O1	2.9 (3)	C11—C7—N2—N1	−177.27 (14)
C11—C7—C8—O1	179.03 (16)	C8—C7—N2—N1	−0.8 (3)
N2—C7—C8—O2	−175.68 (15)	O1—C8—O2—C9	−3.9 (3)
C11—C7—C8—O2	0.4 (3)	C7—C8—O2—C9	174.68 (15)
N2—C7—C11—O3	179.46 (18)	C10—C9—O2—C8	86.7 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3^i	0.93	2.43	3.282 (3)	152
N1—H1···O1	0.83 (2)	1.99 (2)	2.630 (2)	133 (2)

Symmetry code: (i) −x+1, y+1/2, −z+3/2.