(Z)-Ethyl 4-chloro-2-[2-(2-chloro­phen­yl)hydrazono]-3-oxobutanoate

The title compound, C₁₂H₁₂Cl₂N₂O₃, adopts a keto-hydrazo tautomeric form stabilized by an intra­molecular hydrogen bond. The mol­ecule can be considered as consisting of two connected fragments, viz. a chloro­phenyl­hydrazone group, with a Z configuration, and an oxobutanoate group. The mol­ecule is roughly planar, the dihedral angle between the benzene ring and the plane including the aliphatic chain being 4.7 (2)°.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C)= 0.004 Å
• R factor = 0.046
• wR factor = 0.128
• Data-to-parameter ratio = 17.3

checkCIF/PLATON results

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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: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(Z)-Ethyl 4-chloro-2-[2-(2-chlorophenyl)hydrazono]-3-oxobutanoate

Crystal data

C12H12Cl2N2O3	Z = 2
Mr = 303.14	F(000) = 312
Triclinic, P1	Dx = 1.472 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 4.466 (5) Å	Cell parameters from 10737 reflections
b = 9.248 (5) Å	θ = 2.3–27.1°
c = 17.078 (5) Å	µ = 0.48 mm^−1
α = 95.000 (5)°	T = 296 K
β = 94.336 (5)°	Prism, colourless
γ = 102.054 (5)°	0.48 × 0.21 × 0.14 mm
V = 684.0 (9) Å^3

Data collection

Stoe IPDS-II diffractometer	1545 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.091
Graphite monochromator	θmax = 27.2°, θmin = 2.3°
Detector resolution: 6.67 pixels mm^-1	h = −5→5
ω scans	k = −11→11
12555 measured reflections	l = −21→21
2986 independent 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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.059P)^2] where P = (Fo^2 + 2Fc^2)/3
2986 reflections	(Δ/σ)max < 0.001
173 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.22 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	0.9839 (6)	0.7823 (3)	0.77560 (15)	0.0515 (6)
C2	1.1347 (6)	0.8924 (3)	0.73342 (17)	0.0603 (7)
C3	1.3874 (6)	0.9969 (3)	0.76799 (19)	0.0673 (8)
H3	1.4859	1.0703	0.7391	0.081*
C4	1.4924 (7)	0.9926 (4)	0.8442 (2)	0.0751 (9)
H4	1.6641	1.0624	0.8674	0.090*
C5	1.3426 (7)	0.8831 (4)	0.88768 (18)	0.0707 (9)
H5	1.4142	0.8806	0.9400	0.085*
C6	1.0906 (7)	0.7792 (3)	0.85378 (16)	0.0624 (7)
H6	0.9912	0.7068	0.8831	0.075*
C7	0.3283 (6)	0.4805 (3)	0.74887 (14)	0.0507 (6)
C8	0.2037 (6)	0.4731 (3)	0.66561 (15)	0.0558 (7)
C9	−0.1599 (7)	0.3485 (4)	0.56098 (16)	0.0684 (8)
H9A	0.0001	0.3462	0.5258	0.082*
H9B	−0.2525	0.4321	0.5514	0.082*
C10	−0.3954 (8)	0.2076 (4)	0.5475 (2)	0.0867 (11)
H10A	−0.3000	0.1258	0.5564	0.130*
H10B	−0.4885	0.1949	0.4941	0.130*
H10C	−0.5503	0.2107	0.5833	0.130*
C11	0.1857 (6)	0.3839 (3)	0.80598 (15)	0.0563 (7)
C12	0.3633 (7)	0.4045 (4)	0.88698 (16)	0.0716 (9)
H12A	0.4077	0.5090	0.9070	0.086*
H12B	0.5578	0.3751	0.8822	0.086*
N1	0.7262 (5)	0.6773 (2)	0.73902 (13)	0.0563 (6)
H1	0.6685	0.6785	0.6899	0.068*
N2	0.5752 (5)	0.5785 (2)	0.77951 (12)	0.0529 (6)
O1	0.3132 (5)	0.5626 (2)	0.62157 (11)	0.0729 (6)
O2	−0.0319 (4)	0.3621 (2)	0.64287 (10)	0.0672 (6)
O3	−0.0582 (5)	0.2969 (3)	0.79184 (11)	0.0814 (7)
Cl1	1.0007 (2)	0.89767 (10)	0.63575 (5)	0.0843 (3)
Cl2	0.1590 (2)	0.29945 (11)	0.95506 (4)	0.0862 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0444 (14)	0.0510 (16)	0.0543 (15)	0.0007 (12)	0.0039 (11)	0.0037 (12)
C2	0.0526 (16)	0.0604 (18)	0.0642 (17)	0.0039 (14)	0.0036 (13)	0.0080 (14)
C3	0.0540 (17)	0.0599 (19)	0.081 (2)	−0.0029 (14)	0.0024 (15)	0.0083 (16)
C4	0.0602 (18)	0.068 (2)	0.085 (2)	−0.0027 (16)	−0.0056 (16)	−0.0050 (17)
C5	0.0656 (19)	0.077 (2)	0.0610 (18)	0.0074 (16)	−0.0131 (14)	−0.0047 (16)
C6	0.0606 (17)	0.0631 (18)	0.0578 (16)	0.0024 (14)	0.0004 (13)	0.0056 (14)
C7	0.0461 (14)	0.0536 (16)	0.0464 (13)	0.0002 (12)	−0.0025 (11)	0.0035 (11)
C8	0.0519 (15)	0.0603 (17)	0.0513 (15)	0.0057 (13)	−0.0020 (12)	0.0065 (13)
C9	0.0686 (18)	0.079 (2)	0.0475 (15)	−0.0016 (16)	−0.0105 (13)	0.0088 (14)
C10	0.085 (2)	0.088 (2)	0.070 (2)	−0.0092 (19)	−0.0237 (17)	0.0053 (17)
C11	0.0544 (16)	0.0601 (18)	0.0485 (14)	0.0014 (14)	−0.0015 (12)	0.0056 (12)
C12	0.0640 (18)	0.089 (2)	0.0515 (16)	−0.0090 (16)	−0.0026 (13)	0.0173 (15)
N1	0.0523 (13)	0.0586 (14)	0.0521 (12)	−0.0016 (11)	0.0002 (10)	0.0110 (11)
N2	0.0486 (12)	0.0570 (14)	0.0508 (12)	0.0044 (11)	0.0037 (10)	0.0101 (10)
O1	0.0770 (13)	0.0761 (14)	0.0527 (11)	−0.0111 (11)	−0.0092 (9)	0.0173 (10)
O2	0.0673 (12)	0.0734 (14)	0.0475 (10)	−0.0106 (10)	−0.0094 (9)	0.0080 (9)
O3	0.0691 (13)	0.0949 (17)	0.0607 (12)	−0.0257 (12)	−0.0089 (10)	0.0189 (11)
Cl1	0.0843 (6)	0.0919 (6)	0.0685 (5)	−0.0045 (5)	−0.0028 (4)	0.0287 (4)
Cl2	0.0856 (6)	0.1055 (7)	0.0529 (4)	−0.0156 (5)	0.0006 (4)	0.0212 (4)

Geometric parameters (Å, º)

C1—C2	1.387 (4)	C8—O2	1.315 (3)
C1—C6	1.388 (4)	C9—O2	1.455 (3)
C1—N1	1.405 (3)	C9—C10	1.482 (4)
C2—C3	1.379 (4)	C9—H9A	0.9700
C2—Cl1	1.737 (3)	C9—H9B	0.9700
C3—C4	1.356 (4)	C10—H10A	0.9600
C3—H3	0.9300	C10—H10B	0.9600
C4—C5	1.396 (4)	C10—H10C	0.9600
C4—H4	0.9300	C11—O3	1.205 (3)
C5—C6	1.370 (4)	C11—C12	1.518 (3)
C5—H5	0.9300	C12—Cl2	1.765 (3)
C6—H6	0.9300	C12—H12A	0.9700
C7—N2	1.313 (3)	C12—H12B	0.9700
C7—C11	1.470 (4)	N1—N2	1.301 (3)
C7—C8	1.478 (3)	N1—H1	0.8600
C8—O1	1.218 (3)
C2—C1—C6	118.8 (2)	O2—C9—H9A	110.4
C2—C1—N1	119.8 (2)	C10—C9—H9A	110.4
C6—C1—N1	121.4 (2)	O2—C9—H9B	110.4
C3—C2—C1	120.9 (3)	C10—C9—H9B	110.4
C3—C2—Cl1	120.0 (2)	H9A—C9—H9B	108.6
C1—C2—Cl1	119.1 (2)	C9—C10—H10A	109.5
C4—C3—C2	120.0 (3)	C9—C10—H10B	109.5
C4—C3—H3	120.0	H10A—C10—H10B	109.5
C2—C3—H3	120.0	C9—C10—H10C	109.5
C3—C4—C5	119.9 (3)	H10A—C10—H10C	109.5
C3—C4—H4	120.0	H10B—C10—H10C	109.5
C5—C4—H4	120.0	O3—C11—C7	123.8 (2)
C6—C5—C4	120.4 (3)	O3—C11—C12	121.1 (3)
C6—C5—H5	119.8	C7—C11—C12	115.1 (2)
C4—C5—H5	119.8	C11—C12—Cl2	112.4 (2)
C5—C6—C1	119.9 (3)	C11—C12—H12A	109.1
C5—C6—H6	120.0	Cl2—C12—H12A	109.1
C1—C6—H6	120.0	C11—C12—H12B	109.1
N2—C7—C11	113.4 (2)	Cl2—C12—H12B	109.1
N2—C7—C8	122.5 (2)	H12A—C12—H12B	107.9
C11—C7—C8	124.1 (2)	N2—N1—C1	119.9 (2)
O1—C8—O2	122.9 (2)	N2—N1—H1	120.0
O1—C8—C7	122.4 (2)	C1—N1—H1	120.0
O2—C8—C7	114.8 (2)	N1—N2—C7	122.5 (2)
O2—C9—C10	106.7 (2)	C8—O2—C9	116.9 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.95	2.608 (3)	132
C12—H12B···O3^i	0.97	2.56	3.426 (5)	148

Symmetry code: (i) x+1, y, z.