Ethyl 2-[(3-chloro-phen-yl)hydrazono]-3-oxobutanoate.

The mol-ecule of the title oxobutanoate derivative, C(12)H(13)ClN(2)O(3), adopts a keto-hydrazo tautomeric form and is roughly planar, the angle between the benzene ring and the mean plane through the hydrazone and aliphatic chain being 1.49 (6)°. This planarity is further aided by the formation of an intra-molecular N-H⋯O hydrogen bond which generates an S(6) ring motif. The aromatic ring and aliphatic chain have a trans configuration with respect to the N-N bond. In the crystal packing, centrosymmetric R(2) (2)(16) dimers are formed through pairs of weak C-H⋯O(3-oxo) inter-actions. These dimers are linked together through weak C-H⋯O(carboxyl-ate C=O) inter-actions into ribbons along the b-axis direction. These ribbons are stacked along the a-axis direction. The crystal also exhibits Cl⋯Cl [3.4988 (6) Å] and C⋯O [3.167 (2)-3.335 (2) Å] short contacts.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For background to the bioactivity and applications of oxobutanoate derivatives, see: Alpaslan et al. (2005a ▶,b ▶); Stancho et al. (2008 ▶). For related structures, see: Alpaslan et al. (2005a ▶,b ▶); Fun et al. (2009 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer, (1986 ▶).

Experimental

Crystal data

C12H13ClN2O3

M = 268.69

Triclinic,

a = 4.0826 (2) Å

b = 10.3196 (4) Å

c = 15.1469 (6) Å

α = 88.336 (3)°

β = 87.033 (3)°

γ = 83.734 (2)°

V = 633.31 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.30 mm−1

T = 120 K

0.39 × 0.11 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.890, T max = 0.981

11030 measured reflections

3678 independent reflections

2732 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.139

S = 1.05

3678 reflections

169 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.75 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901784X/fb2150sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901784X/fb2150Isup2.hkl

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

C12H13ClN2O3	Z = 2
Mr = 268.69	F(000) = 280
Triclinic, P1	Dx = 1.409 Mg m−3
Hall symbol: -P 1	Melting point: 360 K
a = 4.0826 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3196 (4) Å	Cell parameters from 3678 reflections
c = 15.1469 (6) Å	θ = 1.4–30.0°
α = 88.336 (3)°	µ = 0.30 mm−1
β = 87.033 (3)°	T = 120 K
γ = 83.734 (2)°	Needle, yellow
V = 633.31 (5) Å3	0.39 × 0.11 × 0.06 mm

Bruker APEXII CCD area-detector diffractometer	3678 independent reflections
Radiation source: sealed tube	2732 reflections with I > 2σ(I)
graphite	Rint = 0.036
φ and ω scans	θmax = 30.0°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −5→5
Tmin = 0.890, Tmax = 0.981	k = −14→14
11030 measured reflections	l = −18→21

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0778P)2 + 0.1165P] where P = (Fo2 + 2Fc2)/3
3678 reflections	(Δ/σ)max = 0.001
169 parameters	Δρmax = 0.75 e Å−3
0 restraints	Δρmin = −0.27 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
Cl1	1.05405 (13)	1.38226 (4)	0.08494 (3)	0.02972 (15)
O1	0.6525 (4)	0.66454 (13)	0.29235 (9)	0.0307 (3)
O2	0.6912 (3)	0.82739 (12)	0.19234 (8)	0.0233 (3)
O3	1.2031 (4)	0.86080 (13)	0.46009 (9)	0.0300 (3)
N1	1.1619 (4)	1.03691 (14)	0.33708 (10)	0.0199 (3)
N2	0.9988 (3)	0.95997 (13)	0.29359 (10)	0.0189 (3)
C1	1.1244 (4)	1.20062 (16)	0.21705 (11)	0.0207 (3)
H1A	1.0155	1.1475	0.1826	0.025*
C2	1.1889 (4)	1.32389 (17)	0.18746 (12)	0.0207 (3)
C3	1.3528 (4)	1.40505 (16)	0.23737 (12)	0.0226 (4)
H3A	1.3904	1.4880	0.2163	0.027*
C4	1.4591 (4)	1.35961 (17)	0.31912 (12)	0.0229 (4)
H4A	1.5732	1.4120	0.3528	0.027*
C5	1.3972 (4)	1.23677 (16)	0.35144 (12)	0.0206 (3)
H5A	1.4676	1.2069	0.4065	0.025*
C6	1.2282 (4)	1.15919 (16)	0.30004 (11)	0.0185 (3)
C7	0.9369 (4)	0.84466 (16)	0.32803 (11)	0.0190 (3)
C8	1.0544 (4)	0.79195 (17)	0.41344 (12)	0.0222 (4)
C9	1.0059 (5)	0.65572 (17)	0.44501 (13)	0.0260 (4)
H9A	1.1162	0.6367	0.4991	0.039*
H9B	1.0961	0.5950	0.4010	0.039*
H9C	0.7745	0.6484	0.4551	0.039*
C10	0.7486 (4)	0.76823 (16)	0.27083 (11)	0.0201 (3)
C11	0.5170 (5)	0.75610 (17)	0.13154 (12)	0.0248 (4)
H11A	0.3238	0.7247	0.1613	0.030*
H11B	0.6596	0.6819	0.1089	0.030*
C12	0.4174 (5)	0.8497 (2)	0.05750 (14)	0.0331 (4)
H12A	0.3063	0.8057	0.0148	0.050*
H12B	0.6103	0.8817	0.0297	0.050*
H12C	0.2719	0.9214	0.0807	0.050*
H1N1	1.211 (6)	1.016 (3)	0.3940 (17)	0.043 (7)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0420 (3)	0.0212 (2)	0.0261 (2)	−0.00346 (18)	−0.00707 (18)	0.00680 (16)
O1	0.0434 (8)	0.0159 (6)	0.0353 (7)	−0.0126 (6)	−0.0079 (6)	0.0038 (5)
O2	0.0281 (6)	0.0170 (6)	0.0259 (6)	−0.0066 (5)	−0.0059 (5)	0.0027 (5)
O3	0.0436 (8)	0.0185 (6)	0.0290 (7)	−0.0051 (6)	−0.0111 (6)	0.0037 (5)
N1	0.0242 (7)	0.0112 (6)	0.0246 (8)	−0.0018 (5)	−0.0046 (6)	0.0020 (5)
N2	0.0187 (7)	0.0114 (6)	0.0264 (7)	−0.0006 (5)	−0.0016 (6)	−0.0006 (5)
C1	0.0244 (8)	0.0139 (8)	0.0245 (8)	−0.0038 (6)	−0.0033 (7)	−0.0013 (6)
C2	0.0242 (8)	0.0145 (8)	0.0225 (8)	0.0019 (6)	−0.0025 (7)	0.0036 (6)
C3	0.0271 (9)	0.0108 (7)	0.0303 (9)	−0.0052 (6)	−0.0001 (7)	0.0018 (6)
C4	0.0249 (9)	0.0138 (8)	0.0310 (9)	−0.0042 (6)	−0.0045 (7)	−0.0044 (7)
C5	0.0220 (8)	0.0158 (8)	0.0238 (8)	0.0000 (6)	−0.0039 (6)	0.0007 (6)
C6	0.0198 (8)	0.0105 (7)	0.0249 (8)	−0.0006 (6)	0.0001 (6)	0.0008 (6)
C7	0.0203 (8)	0.0114 (7)	0.0253 (8)	−0.0016 (6)	−0.0012 (6)	0.0014 (6)
C8	0.0250 (8)	0.0149 (8)	0.0257 (9)	0.0009 (6)	−0.0005 (7)	0.0019 (6)
C9	0.0306 (9)	0.0157 (8)	0.0310 (9)	−0.0004 (7)	−0.0026 (7)	0.0052 (7)
C10	0.0195 (8)	0.0153 (8)	0.0254 (8)	−0.0014 (6)	−0.0012 (6)	0.0005 (6)
C11	0.0276 (9)	0.0185 (8)	0.0292 (9)	−0.0049 (7)	−0.0045 (7)	−0.0031 (7)
C12	0.0368 (11)	0.0286 (10)	0.0349 (11)	−0.0045 (8)	−0.0116 (9)	0.0023 (8)

Cl1—C2	1.7432 (18)	C4—H4A	0.9300
O1—C10	1.210 (2)	C5—C6	1.391 (2)
O2—C10	1.340 (2)	C5—H5A	0.9300
O2—C11	1.455 (2)	C7—C8	1.472 (2)
O3—C8	1.241 (2)	C7—C10	1.485 (2)
N1—N2	1.303 (2)	C8—C9	1.502 (2)
N1—C6	1.414 (2)	C9—H9A	0.9600
N1—H1N1	0.91 (3)	C9—H9B	0.9600
N2—C7	1.330 (2)	C9—H9C	0.9600
C1—C2	1.384 (2)	C11—C12	1.501 (3)
C1—C6	1.388 (2)	C11—H11A	0.9700
C1—H1A	0.9300	C11—H11B	0.9700
C2—C3	1.390 (2)	C12—H12A	0.9600
C3—C4	1.385 (2)	C12—H12B	0.9600
C3—H3A	0.9300	C12—H12C	0.9600
C4—C5	1.390 (2)
C10—O2—C11	115.77 (13)	C8—C7—C10	121.60 (14)
N2—N1—C6	120.27 (15)	O3—C8—C7	119.29 (15)
N2—N1—H1N1	119.6 (16)	O3—C8—C9	118.90 (16)
C6—N1—H1N1	119.7 (16)	C7—C8—C9	121.80 (15)
N1—N2—C7	120.48 (15)	C8—C9—H9A	109.5
C2—C1—C6	117.59 (15)	C8—C9—H9B	109.5
C2—C1—H1A	121.2	H9A—C9—H9B	109.5
C6—C1—H1A	121.2	C8—C9—H9C	109.5
C1—C2—C3	122.41 (16)	H9A—C9—H9C	109.5
C1—C2—Cl1	119.40 (13)	H9B—C9—H9C	109.5
C3—C2—Cl1	118.17 (13)	O1—C10—O2	123.08 (16)
C4—C3—C2	118.50 (15)	O1—C10—C7	124.24 (16)
C4—C3—H3A	120.8	O2—C10—C7	112.67 (14)
C2—C3—H3A	120.8	O2—C11—C12	106.71 (14)
C3—C4—C5	120.83 (15)	O2—C11—H11A	110.4
C3—C4—H4A	119.6	C12—C11—H11A	110.4
C5—C4—H4A	119.6	O2—C11—H11B	110.4
C4—C5—C6	118.93 (16)	C12—C11—H11B	110.4
C4—C5—H5A	120.5	H11A—C11—H11B	108.6
C6—C5—H5A	120.5	C11—C12—H12A	109.5
C1—C6—C5	121.71 (15)	C11—C12—H12B	109.5
C1—C6—N1	121.53 (15)	H12A—C12—H12B	109.5
C5—C6—N1	116.75 (15)	C11—C12—H12C	109.5
N2—C7—C8	124.09 (15)	H12A—C12—H12C	109.5
N2—C7—C10	114.25 (15)	H12B—C12—H12C	109.5
C6—N1—N2—C7	179.76 (15)	N1—N2—C7—C8	−2.8 (3)
C6—C1—C2—C3	0.4 (3)	N1—N2—C7—C10	179.91 (14)
C6—C1—C2—Cl1	−178.31 (13)	N2—C7—C8—O3	4.8 (3)
C1—C2—C3—C4	0.9 (3)	C10—C7—C8—O3	−178.06 (16)
Cl1—C2—C3—C4	179.64 (13)	N2—C7—C8—C9	−173.83 (16)
C2—C3—C4—C5	−1.3 (3)	C10—C7—C8—C9	3.3 (3)
C3—C4—C5—C6	0.4 (3)	C11—O2—C10—O1	−2.8 (2)
C2—C1—C6—C5	−1.3 (3)	C11—O2—C10—C7	178.04 (14)
C2—C1—C6—N1	177.53 (16)	N2—C7—C10—O1	−175.72 (16)
C4—C5—C6—C1	0.9 (3)	C8—C7—C10—O1	6.9 (3)
C4—C5—C6—N1	−177.98 (16)	N2—C7—C10—O2	3.4 (2)
N2—N1—C6—C1	−0.3 (2)	C8—C7—C10—O2	−173.96 (15)
N2—N1—C6—C5	178.63 (15)	C10—O2—C11—C12	168.38 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	0.91 (3)	1.87 (3)	2.564 (2)	132 (3)
C3—H3A···O1i	0.93	2.54	3.211 (2)	129
C5—H5A···O3ii	0.93	2.52	3.433 (2)	166

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	0.91 (3)	1.87 (3)	2.564 (2)	132 (3)
C3—H3A⋯O1i	0.93	2.54	3.211 (2)	129
C5—H5A⋯O3ii	0.93	2.52	3.433 (2)	166

Symmetry codes: (i) ; (ii) .