Ethyl 3-benzoyl-2-hydroxy­prop-2-enoate

Abstract

In the title compound, C₁₂H₁₂O₄, the dihedral angle between the plane through the phenyl ring and the mean plane of the side chain is approximately 14°. The mol­ecules, which contain an intra­molecular O—H⋯O hydrogen bond, are linked end-to-end by weak C—H⋯O inter­molecular hydrogen-bonding contacts, forming infinite one-dimensional chain systems in the crystal structure.

Related literature

For related literature, see: Davey & Ribbons (1975 ▶); Emerson et al. (1991 ▶); Aliev et al. (2000a ▶,b ▶); Bernstein et al. (1995 ▶); Desiraju & Steiner (2001 ▶).

Experimental

Crystal data

• C₁₂H₁₂O₄

• M _r = 220.22

• Monoclinic,

• a = 9.872 (4) Å

• b = 13.498 (5) Å

• c = 8.843 (3) Å

• β = 105.464 (6)°

• V = 1135.7 (7) ų

• Z = 4

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 294 (2) K

• 0.26 × 0.22 × 0.20 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.975, T _max = 0.981

• 6252 measured reflections

• 2316 independent reflections

• 1405 reflections with I > 2σ(I)

• R _int = 0.028

Refinement

• R[F ² > 2σ(F ²)] = 0.049

• wR(F ²) = 0.151

• S = 1.02

• 2316 reflections

• 147 parameters

• 2 restraints

• H-atom parameters constraned

• Δρ_max = 0.20 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

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
O2—H2A⋯O1	0.82	1.80	2.518 (2)	146
C5—H5⋯O3i	0.93	2.67	3.405 (3)	137
C11—H11A⋯O1ii	0.97	2.68	3.571 (4)	153

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

1,3-Diketones are substrates for carbon-carbon bond hydrolysis by beta-ketolases. The 2,4-diketo acids examined for hydrolysis by acetopyruvate hydrolase from rat liver (EC 3.7.1.5) all have aliphatic side chains.(Davey & Ribbons, 1975) The acetopyruvate hydrolases cleave 2,4-diketopentanoic acid into pyruvate and acetate (Emerson et al., 1991). Cleavage of analogues such as 2,4-diketo-4-phenylbutanoic acid was not reported. In order to discover the hydrolysis process of analogues, the title compound was synthesized.

In the title compound, the C—O and C—C bond lengths are in the normal range, and the dihedral angle between the plane of the phenyl ring and the mean plane of the side chain is approximately 14 °. The corresponding torsion angle C1—C6—C7—C8 is -14.0 (3) °. The molecule contains the typical O—H···O intra-molecular hydrogen bond graph set S(6) (Bernstein et al., 1995). As shown in Figure 2, these monomers are associated end-to-end to form the R²₂(10) ring system, which is generated by different weak C—H···O hydrogen bonds (Table 1). These hydrogen bonds connect the molecules due to translational symmetry to assembly a chain system along the c direction. Similarly, the S(6) intra-molecular hydrogen bond type is also observed in 2-hydroxy-4-oxo-4-phenyl-3(Z)-butenic acid and 4-hydroxy-2-oxo-6-phenyl-3(Z),5(E)-hexadienic acid, but the monomer of the former is extended by the R²₂(8) (Bernstein et al. 1995) inter-molecular H-bonds, related by a centre of inversion to form a two-dimensional layer with head-to-tail packing architecture (Aliev et al., 2000a,b). Head-to-tail packing is also observed in the structure of the title compound, and long H···O distances (Table 1) in weak intermolecular C—H···O contacts are extensively discussed in the literature (Desiraju & Steiner, 2001).

Experimental

Sodium (2.3 g, 103 mmol) was added to absolute ethanol (133 ml). The mixture was cooled to -273 K and a mixture of diethyl oxalate (14.0 g, 96 mmol) and the ketone (96 mmol) was added slowly over a period of 20 min. A precipitate formed and stirring was continued for 4 h at room temperature. The precipitate was filtered, washed with absolute ethanol (20 ml) and dissolved in 2 N sulfuric acid (150 ml) and ether-extracted (3x150 ml), dried over Na₂SO₄ and ether removed. The residue was distilled under reduced pressure. The residue was recrystallized from ethanol and single crystals of the title compound suitable for X-ray measurements were obtained by recrystallization from acetone at room temperature. Elemental analysis (%) calcd for 1, C₁₈H₂₂CuN₄O₈: C 65.45, H 5.49; found: C 65.52, H 5.54.

Refinement

H atoms were positioned geometrically and treated as riding with distances C–H = 0.93–0.97 Å, and O–H = 0.82 Å. The respective U_iso(H)=1.2Ueq(aromatic C and CH₂), U_iso(H)=1.5Ueq(CH₃), U_iso(H)=1.5(U_eq)(hydroxyl O).

Figures

Fig. 1.

An ORTEP view of the labelled title molecule with 30% thermal ellipsoids. The intramolecular hydrogen bond is indicated by a dashed line.

Fig. 2.

View of the one-dimensional weak hydrogen bonded chain structure.

Crystal data

C12H12O4	F000 = 464
Mr = 220.22	Dx = 1.288 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1800 reflections
a = 9.872 (4) Å	θ = 2.6–26.2º
b = 13.498 (5) Å	µ = 0.10 mm−1
c = 8.843 (3) Å	T = 294 (2) K
β = 105.464 (6)º	Block, yellow
V = 1135.7 (7) Å3	0.26 × 0.22 × 0.20 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2316 independent reflections
Radiation source: fine-focus sealed tube	1405 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.028
T = 294(2) K	θmax = 26.4º
phi and ω scans	θmin = 2.1º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −12→11
Tmin = 0.975, Tmax = 0.981	k = −16→15
6252 measured reflections	l = −9→10

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049	H-atom parameters constrained
wR(F2) = 0.151	w = 1/[σ2(Fo2) + (0.0635P)2 + 0.3304P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
2316 reflections	Δρmax = 0.20 e Å−3
147 parameters	Δρmin = −0.21 e Å−3
2 restraints	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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
O1	0.58450 (15)	0.67082 (13)	0.25001 (17)	0.0695 (5)
O2	0.43270 (15)	0.65232 (14)	0.43639 (17)	0.0714 (5)
H2A	0.4506	0.6651	0.3531	0.107*
O3	0.62879 (18)	0.56869 (16)	0.80268 (18)	0.0871 (6)
O4	0.40548 (14)	0.61835 (11)	0.71546 (15)	0.0558 (4)
C1	0.9543 (2)	0.62744 (16)	0.4355 (3)	0.0589 (6)
H1	0.9547	0.6290	0.5407	0.071*
C2	1.0792 (2)	0.6156 (2)	0.3952 (3)	0.0708 (7)
H2	1.1633	0.6099	0.4732	0.085*
C3	1.0797 (3)	0.61223 (19)	0.2404 (3)	0.0726 (7)
H3	1.1636	0.6025	0.2136	0.087*
C4	0.9558 (3)	0.6232 (2)	0.1241 (3)	0.0721 (7)
H4	0.9566	0.6216	0.0192	0.087*
C5	0.8304 (2)	0.63658 (17)	0.1634 (3)	0.0603 (6)
H5	0.7473	0.6453	0.0849	0.072*
C6	0.8285 (2)	0.63697 (14)	0.3204 (2)	0.0479 (5)
C7	0.6913 (2)	0.64484 (15)	0.3590 (2)	0.0490 (5)
C8	0.6759 (2)	0.62196 (16)	0.5096 (2)	0.0516 (5)
H8A	0.7552	0.6022	0.5926	0.062*
C9	0.5473 (2)	0.62671 (15)	0.5400 (2)	0.0497 (5)
C10	0.5333 (2)	0.60126 (17)	0.7012 (2)	0.0536 (5)
C11	0.3828 (2)	0.5971 (2)	0.8685 (2)	0.0641 (6)
H11A	0.4489	0.6341	0.9496	0.077*
H11B	0.3962	0.5270	0.8920	0.077*
C12	0.2353 (3)	0.6269 (2)	0.8617 (3)	0.0833 (8)
H12A	0.2239	0.6966	0.8405	0.125*
H12B	0.2164	0.6126	0.9604	0.125*
H12C	0.1710	0.5906	0.7799	0.125*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0472 (9)	0.1101 (13)	0.0500 (9)	0.0117 (8)	0.0109 (7)	0.0164 (9)
O2	0.0429 (9)	0.1209 (15)	0.0501 (9)	0.0102 (8)	0.0119 (7)	0.0166 (9)
O3	0.0623 (11)	0.1483 (18)	0.0514 (10)	0.0333 (11)	0.0161 (8)	0.0217 (10)
O4	0.0470 (8)	0.0774 (10)	0.0453 (8)	0.0045 (7)	0.0163 (6)	0.0043 (7)
C1	0.0463 (12)	0.0808 (16)	0.0507 (12)	0.0012 (11)	0.0151 (10)	0.0017 (11)
C2	0.0464 (13)	0.1006 (19)	0.0671 (15)	0.0019 (12)	0.0183 (11)	0.0075 (13)
C3	0.0546 (15)	0.0928 (19)	0.0803 (17)	0.0009 (13)	0.0353 (13)	0.0072 (14)
C4	0.0713 (17)	0.0946 (19)	0.0593 (14)	−0.0037 (13)	0.0326 (13)	0.0025 (13)
C5	0.0531 (13)	0.0767 (16)	0.0518 (13)	0.0000 (11)	0.0150 (10)	0.0068 (11)
C6	0.0455 (12)	0.0522 (12)	0.0480 (11)	−0.0005 (9)	0.0159 (9)	0.0019 (9)
C7	0.0419 (11)	0.0555 (12)	0.0492 (12)	0.0020 (9)	0.0117 (9)	−0.0019 (9)
C8	0.0420 (12)	0.0697 (14)	0.0424 (11)	0.0090 (9)	0.0101 (9)	0.0013 (10)
C9	0.0448 (11)	0.0597 (13)	0.0430 (11)	0.0042 (9)	0.0093 (9)	−0.0018 (9)
C10	0.0456 (12)	0.0693 (14)	0.0455 (12)	0.0050 (10)	0.0115 (10)	−0.0013 (10)
C11	0.0679 (15)	0.0823 (16)	0.0462 (12)	0.0021 (12)	0.0220 (11)	0.0012 (11)
C12	0.0776 (18)	0.104 (2)	0.0825 (18)	0.0151 (15)	0.0469 (15)	0.0085 (15)

Geometric parameters (Å, °)

O1—C7	1.274 (2)	C4—H4	0.9300
O2—C9	1.299 (2)	C5—C6	1.394 (3)
O2—H2A	0.8200	C5—H5	0.9300
O3—C10	1.199 (2)	C6—C7	1.486 (3)
O4—C10	1.321 (2)	C7—C8	1.415 (3)
O4—C11	1.458 (2)	C8—C9	1.367 (3)
C1—C2	1.381 (3)	C8—H8A	0.9572
C1—C6	1.386 (3)	C9—C10	1.509 (3)
C1—H1	0.9300	C11—C12	1.496 (3)
C2—C3	1.371 (3)	C11—H11A	0.9700
C2—H2	0.9300	C11—H11B	0.9700
C3—C4	1.380 (3)	C12—H12A	0.9600
C3—H3	0.9300	C12—H12B	0.9600
C4—C5	1.383 (3)	C12—H12C	0.9600
C9—O2—H2A	109.5	C8—C7—C6	122.28 (18)
C10—O4—C11	116.17 (16)	C9—C8—C7	120.88 (19)
C2—C1—C6	120.5 (2)	C9—C8—H8A	118.4
C2—C1—H1	119.7	C7—C8—H8A	120.8
C6—C1—H1	119.7	O2—C9—C8	123.66 (19)
C3—C2—C1	120.2 (2)	O2—C9—C10	116.41 (18)
C3—C2—H2	119.9	C8—C9—C10	119.93 (18)
C1—C2—H2	119.9	O3—C10—O4	125.0 (2)
C2—C3—C4	120.2 (2)	O3—C10—C9	122.62 (19)
C2—C3—H3	119.9	O4—C10—C9	112.41 (17)
C4—C3—H3	119.9	O4—C11—C12	107.37 (18)
C3—C4—C5	120.1 (2)	O4—C11—H11A	110.2
C3—C4—H4	119.9	C12—C11—H11A	110.2
C5—C4—H4	119.9	O4—C11—H11B	110.2
C4—C5—C6	120.1 (2)	C12—C11—H11B	110.2
C4—C5—H5	120.0	H11A—C11—H11B	108.5
C6—C5—H5	120.0	C11—C12—H12A	109.5
C1—C6—C5	118.92 (19)	C11—C12—H12B	109.5
C1—C6—C7	122.10 (19)	H12A—C12—H12B	109.5
C5—C6—C7	118.96 (19)	C11—C12—H12C	109.5
O1—C7—C8	119.81 (18)	H12A—C12—H12C	109.5
O1—C7—C6	117.88 (18)	H12B—C12—H12C	109.5
C6—C1—C2—C3	−0.6 (4)	O1—C7—C8—C9	0.4 (3)
C1—C2—C3—C4	1.7 (4)	C6—C7—C8—C9	−177.77 (19)
C2—C3—C4—C5	−0.7 (4)	C7—C8—C9—O2	−0.4 (3)
C3—C4—C5—C6	−1.3 (4)	C7—C8—C9—C10	179.55 (19)
C2—C1—C6—C5	−1.4 (3)	C11—O4—C10—O3	1.2 (3)
C2—C1—C6—C7	176.9 (2)	C11—O4—C10—C9	−179.21 (18)
C4—C5—C6—C1	2.3 (3)	O2—C9—C10—O3	173.6 (2)
C4—C5—C6—C7	−176.0 (2)	C8—C9—C10—O3	−6.3 (3)
C1—C6—C7—O1	167.8 (2)	O2—C9—C10—O4	−6.0 (3)
C5—C6—C7—O1	−13.9 (3)	C8—C9—C10—O4	174.08 (19)
C1—C6—C7—C8	−14.0 (3)	C10—O4—C11—C12	176.8 (2)
C5—C6—C7—C8	164.3 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1	0.82	1.80	2.518 (2)	146
C5—H5···O3i	0.93	2.67	3.405 (3)	137
C11—H11A···O1ii	0.97	2.68	3.571 (4)	153

Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1.