Literature DB >> 21583848

Ethyl 2-[(4-chloro-phen-yl)hydrazono]-3-oxobutanoate.

Hoong-Kun Fun, Suchada Chantrapromma, Mahesh Padaki, Arun M Isloor.

Abstract

The mol-ecule of the title oxobutanoate derivative, C(12)H(13)ClN(2)O(3), is nearly planar; the inter-planar angle between the benzene ring and the mean plane through the hydrazono-3-oxobutanoate unit is 2.69 (3)°. An intra-molecular N-H⋯O hydrogen bond generates an S(6) ring motif. In the crystal packing, C-H⋯O(3-oxo) inter-actions link mol-ecules into dimers. The dimers thus formed are linked through C-H⋯O(carboxyl-ate C=O) inter-actions, leading to the formation of ribbons along the [01] direction, which are stabilized via Cl⋯Cl [3.2916 (3) Å] contacts. The ribbons are stacked via C⋯O contacts [3.2367 (12)-3.3948 (12) Å].

Entities: CellLine Chemical Disease Species

Year: 2009 PMID： 21583848 PMCID： PMC2977712 DOI： 10.1107/S1600536809012951

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For hydrogen-bond motifs, see Bernstein et al. (1995 ▶). For background to the bioactivity and applications of oxobutanoate derivatives, see: Alpaslan et al. (2005 ▶); Billington et al. (1979 ▶); Stancho et al. (2008 ▶). For the synthesis, see Amir & Agarwal (1997 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C12H13ClN2O3 M = 268.69 Monoclinic, a = 4.0259 (1) Å b = 17.0892 (4) Å c = 18.4934 (5) Å β = 96.802 (1)° V = 1263.38 (6) Å3 Z = 4 Mo Kα radiation μ = 0.30 mm−1 T = 100 K 0.77 × 0.13 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.799, T max = 0.982 38796 measured reflections 4723 independent reflections 3972 reflections with I > 2σ(I) R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.037 wR(F 2) = 0.108 S = 1.06 4723 reflections 165 parameters H-atom parameters constrained Δρmax = 0.53 e Å−3 Δρmin = −0.24 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/S1600536809012951/tk2415sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012951/tk2415Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₂H₁₃ClN₂O₃	F(000) = 560
M_r = 268.69	D_x = 1.413 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 365 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.0259 (1) Å	Cell parameters from 4723 reflections
b = 17.0892 (4) Å	θ = 1.6–32.9°
c = 18.4934 (5) Å	µ = 0.30 mm⁻¹
β = 96.802 (1)°	T = 100 K
V = 1263.38 (6) Å³	Needle, brown
Z = 4	0.77 × 0.13 × 0.06 mm

Bruker APEXII CCD area-detector diffractometer	4723 independent reflections
Radiation source: sealed tube	3972 reflections with I > 2σ(I)
graphite	R_int = 0.039
φ and ω scans	θ_max = 32.9°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −6→6
T_min = 0.799, T_max = 0.982	k = −26→25
38796 measured reflections	l = −28→28

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.108	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0602P)² + 0.255P] where P = (F_o² + 2F_c²)/3
4723 reflections	(Δ/σ)_max = 0.002
165 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.24 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 100.0 (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	U_iso*/U_eq
Cl1	1.33403 (7)	0.917736 (14)	0.966487 (14)	0.02331 (8)
O1	1.1283 (2)	0.43897 (5)	0.92388 (4)	0.02458 (17)
O2	0.4082 (2)	0.41534 (4)	0.74203 (5)	0.02490 (17)
O3	0.40449 (18)	0.54627 (4)	0.73206 (4)	0.01834 (15)
N1	1.0478 (2)	0.58595 (5)	0.89744 (5)	0.01680 (16)
H1	1.1461	0.5484	0.9277	0.020*
N2	0.8324 (2)	0.56553 (5)	0.84259 (4)	0.01607 (15)
C1	0.9700 (2)	0.72408 (6)	0.86488 (5)	0.01779 (18)
H1A	0.8269	0.7109	0.8235	0.021*
C2	1.0384 (3)	0.80222 (6)	0.88190 (5)	0.01815 (18)
H2A	0.9413	0.8418	0.8521	0.022*
C3	1.2535 (2)	0.82023 (5)	0.94400 (5)	0.01668 (17)
C4	1.4070 (2)	0.76234 (6)	0.98899 (5)	0.01816 (18)
H4A	1.5530	0.7756	1.0299	0.022*
C5	1.3393 (2)	0.68425 (6)	0.97197 (5)	0.01727 (17)
H5A	1.4408	0.6447	1.0013	0.021*
C6	1.1185 (2)	0.66568 (5)	0.91065 (5)	0.01550 (17)
C7	0.7628 (2)	0.49093 (5)	0.82808 (5)	0.01602 (17)
C8	0.9246 (2)	0.42509 (6)	0.86964 (5)	0.01779 (18)
C9	0.8553 (3)	0.34161 (6)	0.84741 (6)	0.02176 (19)
H9A	0.9875	0.3074	0.8804	0.033*
H9B	0.9116	0.3337	0.7989	0.033*
H9C	0.6223	0.3304	0.8486	0.033*
C10	0.5100 (2)	0.47889 (6)	0.76369 (5)	0.01646 (17)
C11	0.1696 (2)	0.53891 (6)	0.66655 (5)	0.01926 (18)
H11A	−0.0131	0.5044	0.6752	0.023*
H11B	0.2804	0.5174	0.6272	0.023*
C12	0.0397 (3)	0.61975 (7)	0.64728 (6)	0.0245 (2)
H12A	−0.1123	0.6175	0.6032	0.037*
H12B	0.2235	0.6536	0.6403	0.037*
H12C	−0.0749	0.6397	0.6861	0.037*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.03064 (14)	0.01473 (12)	0.02328 (13)	−0.00497 (9)	−0.00211 (9)	−0.00104 (8)
O1	0.0277 (4)	0.0185 (3)	0.0251 (4)	0.0003 (3)	−0.0070 (3)	0.0031 (3)
O2	0.0306 (4)	0.0165 (3)	0.0254 (4)	−0.0037 (3)	−0.0057 (3)	−0.0015 (3)
O3	0.0185 (3)	0.0163 (3)	0.0190 (3)	−0.0001 (2)	−0.0030 (2)	0.0012 (2)
N1	0.0185 (4)	0.0146 (3)	0.0163 (4)	−0.0003 (3)	−0.0018 (3)	0.0001 (3)
N2	0.0163 (3)	0.0162 (3)	0.0156 (3)	−0.0012 (3)	0.0012 (3)	−0.0015 (3)
C1	0.0200 (4)	0.0162 (4)	0.0162 (4)	−0.0009 (3)	−0.0022 (3)	0.0005 (3)
C2	0.0203 (4)	0.0157 (4)	0.0176 (4)	−0.0005 (3)	−0.0011 (3)	0.0010 (3)
C3	0.0191 (4)	0.0137 (4)	0.0170 (4)	−0.0018 (3)	0.0014 (3)	−0.0006 (3)
C4	0.0187 (4)	0.0179 (4)	0.0169 (4)	−0.0016 (3)	−0.0023 (3)	0.0007 (3)
C5	0.0178 (4)	0.0163 (4)	0.0169 (4)	0.0000 (3)	−0.0014 (3)	0.0011 (3)
C6	0.0163 (4)	0.0135 (4)	0.0165 (4)	−0.0005 (3)	0.0012 (3)	−0.0003 (3)
C7	0.0168 (4)	0.0147 (4)	0.0162 (4)	−0.0008 (3)	0.0002 (3)	0.0008 (3)
C8	0.0189 (4)	0.0155 (4)	0.0189 (4)	−0.0003 (3)	0.0019 (3)	0.0015 (3)
C9	0.0250 (5)	0.0149 (4)	0.0248 (5)	0.0003 (4)	0.0001 (4)	0.0017 (3)
C10	0.0170 (4)	0.0162 (4)	0.0160 (4)	−0.0005 (3)	0.0015 (3)	0.0001 (3)
C11	0.0186 (4)	0.0216 (4)	0.0169 (4)	0.0008 (3)	−0.0012 (3)	0.0006 (3)
C12	0.0238 (5)	0.0235 (5)	0.0253 (5)	0.0032 (4)	−0.0016 (4)	0.0039 (4)

Cl1—C3	1.7386 (9)	C4—H4A	0.9300
O1—C8	1.2412 (12)	C5—C6	1.3924 (13)
O2—C10	1.2121 (12)	C5—H5A	0.9300
O3—C10	1.3378 (12)	C7—C8	1.4703 (13)
O3—C11	1.4514 (11)	C7—C10	1.4864 (13)
N1—N2	1.3018 (11)	C8—C9	1.5017 (14)
N1—C6	1.4072 (12)	C9—H9A	0.9600
N1—H1	0.9104	C9—H9B	0.9600
N2—C7	1.3258 (12)	C9—H9C	0.9600
C1—C2	1.3918 (14)	C11—C12	1.5049 (15)
C1—C6	1.3964 (13)	C11—H11A	0.9700
C1—H1A	0.9300	C11—H11B	0.9700
C2—C3	1.3885 (13)	C12—H12A	0.9600
C2—H2A	0.9300	C12—H12B	0.9600
C3—C4	1.3895 (13)	C12—H12C	0.9600
C4—C5	1.3906 (14)

C10—O3—C11	115.60 (8)	C8—C7—C10	122.13 (8)
N2—N1—C6	119.81 (8)	O1—C8—C7	119.05 (9)
N2—N1—H1	119.4	O1—C8—C9	119.11 (9)
C6—N1—H1	120.7	C7—C8—C9	121.82 (9)
N1—N2—C7	121.37 (8)	C8—C9—H9A	109.5
C2—C1—C6	119.32 (9)	C8—C9—H9B	109.5
C2—C1—H1A	120.3	H9A—C9—H9B	109.5
C6—C1—H1A	120.3	C8—C9—H9C	109.5
C3—C2—C1	119.14 (9)	H9A—C9—H9C	109.5
C3—C2—H2A	120.4	H9B—C9—H9C	109.5
C1—C2—H2A	120.4	O2—C10—O3	123.32 (9)
C2—C3—C4	121.80 (9)	O2—C10—C7	124.16 (9)
C2—C3—Cl1	119.38 (7)	O3—C10—C7	112.52 (8)
C4—C3—Cl1	118.82 (7)	O3—C11—C12	106.97 (8)
C3—C4—C5	119.11 (9)	O3—C11—H11A	110.3
C3—C4—H4A	120.4	C12—C11—H11A	110.3
C5—C4—H4A	120.4	O3—C11—H11B	110.3
C4—C5—C6	119.48 (9)	C12—C11—H11B	110.3
C4—C5—H5A	120.3	H11A—C11—H11B	108.6
C6—C5—H5A	120.3	C11—C12—H12A	109.5
C5—C6—C1	121.12 (9)	C11—C12—H12B	109.5
C5—C6—N1	117.30 (8)	H12A—C12—H12B	109.5
C1—C6—N1	121.57 (8)	C11—C12—H12C	109.5
N2—C7—C8	124.07 (8)	H12A—C12—H12C	109.5
N2—C7—C10	113.78 (8)	H12B—C12—H12C	109.5

C6—N1—N2—C7	179.20 (9)	N1—N2—C7—C8	−2.05 (15)
C6—C1—C2—C3	0.13 (15)	N1—N2—C7—C10	179.71 (9)
C1—C2—C3—C4	1.12 (16)	N2—C7—C8—O1	3.50 (16)
C1—C2—C3—Cl1	−178.83 (8)	C10—C7—C8—O1	−178.40 (10)
C2—C3—C4—C5	−1.00 (15)	N2—C7—C8—C9	−175.28 (10)
Cl1—C3—C4—C5	178.94 (8)	C10—C7—C8—C9	2.81 (15)
C3—C4—C5—C6	−0.36 (15)	C11—O3—C10—O2	−3.29 (14)
C4—C5—C6—C1	1.61 (15)	C11—O3—C10—C7	177.01 (8)
C4—C5—C6—N1	−177.46 (9)	N2—C7—C10—O2	−178.82 (10)
C2—C1—C6—C5	−1.49 (15)	C8—C7—C10—O2	2.90 (16)
C2—C1—C6—N1	177.54 (9)	N2—C7—C10—O3	0.88 (12)
N2—N1—C6—C5	177.14 (9)	C8—C7—C10—O3	−177.40 (9)
N2—N1—C6—C1	−1.93 (15)	C10—O3—C11—C12	170.62 (9)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.91	1.87	2.5721 (12)	132
C2—H2A···O2ⁱ	0.93	2.45	3.3536 (13)	164
C5—H5A···O1ⁱⁱ	0.93	2.53	3.4293 (12)	163

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.91	1.87	2.5721 (12)	132
C2—H2A⋯O2ⁱ	0.93	2.45	3.3536 (13)	164
C5—H5A⋯O1ⁱⁱ	0.93	2.53	3.4293 (12)	163

Symmetry codes: (i) ; (ii) .

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1. A short history of SHELX.

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Authors: D C Billington; B T Golding; S B Primrose
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