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Acta Cryst. (2007). E63, o3376    [ doi:10.1107/S1600536807029959 ]

2-(3-Oxocyclohex-1-enyl)benzoic acid

F. T. Vieira, D. C. Menezes, G. M. de Lima and N. L. Speziali

Abstract top

The title compound, C13H13NO3, crystallizes with two molecules in the asymmetric unit. The values of the relevant C-C, C=C and C-N bond lengths indicate that the molecules exist in the enamine tautomeric form. In each molecule, the cyclohexene ring adopts a slightly distorted envelope conformation. Molecules are linked by intermolecular O-H...O hydrogen bonds between carboxyl and C=O groups. There is also an intramolecular N-H...O hydrogen bond in each molecule.

Comment top

The preparation of the title compound has been reported in the literature in a condensation reaction with isopropylidene malonate (Strozhev & Lielbriedis, 1990). The compound was obtained in 37% yield and no X-ray crystallographic determination has hitherto been performed. A search of the Cambridge Structural Database (Version 5.28; Allen, 2002) yielded no hits.

The title compound crystallizes with two molecules per asymmetric unit. In each molecule the cyclohexene ring adopts a slightly distorted envelope conformation, with C9 and C9' as flap atoms. The bond distances C1—N, N—C7, C7═C12, C12—C11, C1'—N,' N'—C7', C7'═C12' and C12'—C11' (Table 1 and Fig. 1) clearly indicate that the enamine tautomer is present in the crystal structure, rather than the imine normally expected from a Schiff base reaction. The C—N—C bond angles, 131.6 (3)° and 130.7 (3)°, are typical of Nsp3.

The X-ray crystallographic determination has revealed that the title compound exists in the solid state in a pseudo-polymeric arrangement, held together by intermolecular O—H···O hydrogen bonds. These connect carboxyl and C═O groups of neighbouring molecules.

Related literature top

For related literature, see: Allen (2002); Strozhev & Lielbriedis (1990).

Experimental top

To a round-bottomed flask charged with 2-aminobenzoic acid (2.74 g, 0.02 mol) dissolved in methanol (20 ml) was slowly added a solution of 1,3-cyclohexadione (2.24 g, 0.02 mol) in 20 ml of methanol. The mixture was refluxed and stirred for 4 h; it was observed that the colour changed from colourless to yellow. The solution was cooled to room temperature and the solvent was removed in vacuum; the yellow solid was washed with diethyl ether. X-ray quality crystals were obtained after slow evaporation of a methanol/water (9:1) solution. Yield 75%. IR (ν/cm−1): 1376 (νC—N). 1H-NMR: (δ): 7.97–7.92 d (C3), 7.4 m (C5, C6), 7.09 t (C4), 2.51–2.48 m (C11), 2.26–2.27 m (C9), 1.95–1.92 m (C10). 13C-NMR (δ): 201. 9 (C12), 170.4 (C1), 165.4 (C8), 141.9 (C7), 134.6 (C3), 133.6 (C5), 125.5 (C6), 124.64 (C4), 122.58 (C2), 100.94 (C13), 37.12 (C11), 31.07 (C9), 22.92 (C10). Elemental analysis(%) for C13H13NO3 found (calc.): C 67.21 (67.52), H 5.43 (5.66), N 5.96 (6.05).

Refinement top

Most H atoms were detected in a Fourier difference map; nevertheless, their positions were subsequently calculated and they were constrained to ride on their parent atoms, with O—H = 0.82 Å, N—H = 0.86 Å, C—H = 0.93 Å for Csp2 and C—H = 0.97Å for methylene. Uiso(H) = xUeq(carrier atom), where x = 1.2 for C, N and 1.5 for O. In the absence of significant anomalous scattering effects, Friedel pairs were merged.

Computing details top

Data collection: XSCANS (Siemens, 1991); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1990); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound, showing the atom-numbering scheme and the intermolecular hydrogen bond (dashed line) Displacement ellipsoids are drawn at the 50% probability level.
2-(3-Oxocyclohex-1-enyl)benzoic acid top
Crystal data top
C13H13NO3Dx = 1.345 Mg m−3
Mr = 231.24Melting point = 183.7–185.5 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
a = 11.3867 (11) ÅCell parameters from 38 reflections
b = 13.0719 (9) Åθ = 4.8–12.5°
c = 15.3389 (14) ŵ = 0.10 mm−1
V = 2283.2 (3) Å3T = 293 K
Z = 8Prismatic, colorless
F(000) = 9760.2 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer		Rint = 0.015
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 2.1°
graphiteh = −1→13
ω / 2θ scansk = −3→15
2549 measured reflectionsl = −4→18
2266 independent reflections3 standard reflections every 247 reflections
1800 reflections with I > 2σ(I) intensity decay: 4%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.132H-atom parameters constrained
S = 0.93 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
2266 reflections(Δ/σ)max = 0.018
307 parametersΔρmax = 0.18 e Å−3
1 restraintΔρmin = −0.25 e Å−3
Crystal data top
C13H13NO3V = 2283.2 (3) Å3
Mr = 231.24Z = 8
Orthorhombic, Pna21Mo Kα radiation
a = 11.3867 (11) ŵ = 0.10 mm−1
b = 13.0719 (9) ÅT = 293 K
c = 15.3389 (14) Å0.2 × 0.2 × 0.2 mm
Data collection top
Siemens P4
diffractometer		Rint = 0.015
2549 measured reflectionsθmax = 25.5°
2266 independent reflections3 standard reflections every 247 reflections
1800 reflections with I > 2σ(I) intensity decay: 4%
Refinement top
R[F2 > 2σ(F2)] = 0.046H-atom parameters constrained
wR(F2) = 0.132Δρmax = 0.18 e Å−3
S = 0.93Δρmin = −0.25 e Å−3
2266 reflectionsAbsolute structure: ?
307 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.5835 (3)0.4550 (2)0.7105 (2)0.0678 (9)
O20.4210 (2)0.4172 (2)0.7836 (2)0.0644 (9)
H2O0.41130.47920.78040.097*
C130.5183 (3)0.3924 (3)0.7441 (3)0.0452 (9)
C60.5421 (3)0.2797 (3)0.7469 (2)0.0402 (8)
C50.4676 (3)0.2177 (3)0.7959 (3)0.0465 (9)
H50.40340.24710.82380.056*
C40.4865 (3)0.1147 (3)0.8043 (3)0.0502 (10)
H40.43590.07430.83730.060*
C30.5822 (3)0.0721 (3)0.7627 (3)0.0499 (10)
H30.59640.00240.76880.060*
C20.6568 (3)0.1297 (3)0.7128 (2)0.0426 (8)
H20.72040.09900.68520.051*
C10.6372 (3)0.2350 (3)0.7033 (2)0.0376 (8)
N0.7126 (3)0.2982 (2)0.6544 (2)0.0455 (8)
H10.70750.36210.66710.055*
C70.7918 (3)0.2764 (3)0.5909 (2)0.0403 (8)
C80.8719 (3)0.3646 (3)0.5703 (3)0.0443 (9)
H8A0.93320.36780.61420.053*
H8B0.82730.42770.57360.053*
C90.9286 (4)0.3574 (3)0.4812 (3)0.0530 (11)
H9A0.98990.40860.47600.064*
H9B0.87040.37040.43640.064*
C100.9808 (4)0.2511 (3)0.4687 (3)0.0519 (11)
H10A1.01050.24500.40960.062*
H10B1.04640.24240.50830.062*
C110.8926 (3)0.1686 (3)0.4848 (3)0.0394 (8)
C120.8009 (3)0.1860 (3)0.5470 (3)0.0400 (8)
H120.74630.13460.55770.048*
O30.9019 (2)0.08747 (19)0.4442 (2)0.0554 (7)
O1'0.6639 (3)0.9504 (2)0.5383 (2)0.0723 (10)
O2'0.8124 (2)0.9080 (2)0.4533 (2)0.0649 (9)
H2O'0.82780.96900.45850.097*
C13'0.7225 (3)0.8857 (3)0.5014 (3)0.0429 (9)
C6'0.6979 (3)0.7738 (3)0.5042 (2)0.0382 (8)
C5'0.7693 (3)0.7071 (3)0.4574 (2)0.0453 (9)
H5'0.83500.73270.42880.054*
C4'0.7451 (3)0.6040 (3)0.4525 (3)0.0484 (9)
H4'0.79510.56020.42230.058*
C3'0.6461 (4)0.5666 (3)0.4926 (3)0.0505 (10)
H3'0.62760.49760.48740.061*
C2'0.5738 (3)0.6299 (3)0.5405 (3)0.0483 (10)
H2'0.50750.60290.56750.058*
C1'0.5988 (3)0.7339 (3)0.5491 (3)0.0393 (8)
N'0.5268 (2)0.8004 (2)0.5962 (2)0.0455 (8)
H1'0.53400.86380.58240.055*
C7'0.4468 (3)0.7814 (3)0.6606 (2)0.0382 (8)
C8'0.3695 (3)0.8713 (3)0.6803 (3)0.0442 (9)
H8'A0.30730.87460.63720.053*
H8'B0.41550.93360.67550.053*
C9'0.3153 (4)0.8663 (3)0.7703 (3)0.0522 (10)
H9'A0.25700.91990.77660.063*
H9'B0.37540.87660.81420.063*
C10'0.2581 (3)0.7627 (3)0.7830 (3)0.0554 (12)
H10C0.22850.75770.84210.066*
H10D0.19180.75660.74360.066*
C11'0.3422 (3)0.6767 (3)0.7664 (2)0.0408 (8)
C12'0.4342 (3)0.6921 (3)0.7048 (3)0.0414 (8)
H12'0.48720.63930.69460.050*
O3'0.3271 (2)0.5937 (2)0.8042 (2)0.0561 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0716 (18)0.0402 (15)0.092 (2)0.0011 (13)0.0372 (18)0.0043 (16)
O20.0588 (17)0.0435 (16)0.091 (2)0.0050 (13)0.0285 (17)−0.0018 (16)
C130.0461 (19)0.045 (2)0.045 (2)0.0024 (17)0.0071 (18)−0.0055 (18)
C60.0461 (19)0.0359 (18)0.038 (2)−0.0023 (17)−0.0044 (17)−0.0062 (17)
C50.049 (2)0.041 (2)0.049 (2)−0.0028 (17)0.0085 (19)0.0007 (18)
C40.060 (2)0.044 (2)0.046 (2)−0.0035 (18)0.008 (2)0.0064 (18)
C30.063 (2)0.0385 (19)0.048 (2)0.0012 (17)−0.007 (2)0.0031 (18)
C20.0444 (19)0.0402 (19)0.043 (2)0.0068 (15)−0.0017 (17)−0.0013 (17)
C10.0384 (17)0.0371 (17)0.037 (2)−0.0025 (14)−0.0024 (17)−0.0030 (16)
N0.0464 (17)0.0346 (15)0.0555 (19)−0.0008 (13)0.0066 (15)−0.0099 (15)
C70.0339 (17)0.0378 (17)0.049 (2)−0.0029 (14)−0.0030 (16)−0.0041 (18)
C80.0448 (19)0.0363 (18)0.052 (2)−0.0058 (15)−0.0018 (17)−0.0042 (17)
C90.065 (2)0.042 (2)0.052 (3)−0.0191 (19)0.008 (2)−0.0043 (19)
C100.049 (2)0.047 (2)0.059 (3)−0.0076 (18)0.015 (2)−0.0035 (19)
C110.0401 (17)0.0319 (18)0.046 (2)−0.0004 (14)0.0026 (16)0.0001 (16)
C120.0359 (16)0.0380 (17)0.046 (2)−0.0066 (14)0.0041 (17)0.0014 (17)
O30.0650 (17)0.0355 (14)0.0656 (18)0.0000 (12)0.0215 (15)−0.0052 (14)
O1'0.0770 (19)0.0384 (15)0.101 (3)−0.0051 (14)0.037 (2)−0.0025 (17)
O2'0.0670 (18)0.0403 (15)0.087 (2)−0.0120 (13)0.0299 (18)−0.0014 (15)
C13'0.0424 (19)0.041 (2)0.045 (2)0.0014 (16)0.0018 (18)0.0038 (17)
C6'0.0377 (17)0.0398 (18)0.037 (2)0.0003 (15)−0.0006 (16)0.0032 (17)
C5'0.049 (2)0.048 (2)0.038 (2)−0.0001 (17)0.0035 (18)0.0046 (17)
C4'0.063 (2)0.0412 (18)0.041 (2)0.0035 (17)0.004 (2)−0.0007 (17)
C3'0.066 (2)0.0405 (19)0.045 (2)−0.0042 (17)−0.001 (2)−0.0029 (18)
C2'0.046 (2)0.049 (2)0.050 (2)−0.0092 (16)0.0038 (18)0.001 (2)
C1'0.0395 (17)0.0369 (17)0.041 (2)−0.0013 (14)−0.0009 (18)0.0038 (17)
N'0.0452 (16)0.0347 (15)0.057 (2)0.0013 (13)0.0130 (16)0.0070 (14)
C7'0.0365 (17)0.0368 (18)0.041 (2)−0.0046 (15)−0.0048 (16)−0.0014 (17)
C8'0.0465 (19)0.0352 (18)0.051 (2)0.0062 (15)−0.0039 (17)0.0052 (17)
C9'0.063 (2)0.036 (2)0.058 (3)0.0126 (18)0.008 (2)0.0006 (19)
C10'0.051 (2)0.048 (2)0.067 (3)0.0101 (18)0.020 (2)0.003 (2)
C11'0.0426 (19)0.0365 (19)0.043 (2)−0.0018 (15)−0.0009 (17)0.0003 (17)
C12'0.0393 (17)0.0324 (17)0.053 (2)0.0041 (14)0.0028 (18)0.0022 (17)
O3'0.0614 (17)0.0407 (15)0.0662 (19)0.0029 (12)0.0232 (16)0.0095 (13)
Geometric parameters (Å, °) top
O1—C131.219 (5)O1'—C13'1.216 (4)
O2—C131.304 (4)O2'—C13'1.295 (4)
O2—H2O0.8200O2'—H2O'0.8200
C13—C61.498 (5)C13'—C6'1.490 (5)
C6—C51.393 (5)C6'—C5'1.392 (5)
C6—C11.401 (5)C6'—C1'1.421 (5)
C5—C41.370 (6)C5'—C4'1.378 (5)
C5—H50.9300C5'—H5'0.9300
C4—C31.379 (6)C4'—C3'1.374 (6)
C4—H40.9300C4'—H4'0.9300
C3—C21.370 (5)C3'—C2'1.380 (6)
C3—H30.9300C3'—H3'0.9300
C2—C11.402 (5)C2'—C1'1.395 (5)
C2—H20.9300C2'—H2'0.9300
C1—N1.407 (5)C1'—N'1.396 (5)
N—C71.359 (5)N'—C7'1.366 (5)
N—H10.8600N'—H1'0.8600
C7—C121.364 (5)C7'—C12'1.358 (5)
C7—C81.504 (5)C7'—C8'1.500 (5)
C8—C91.514 (6)C8'—C9'1.513 (6)
C8—H8A0.9700C8'—H8'A0.9700
C8—H8B0.9700C8'—H8'B0.9700
C9—C101.524 (6)C9'—C10'1.515 (5)
C9—H9A0.9700C9'—H9'A0.9700
C9—H9B0.9700C9'—H9'B0.9700
C10—C111.494 (5)C10'—C11'1.499 (5)
C10—H10A0.9700C10'—H10C0.9700
C10—H10B0.9700C10'—H10D0.9700
C11—O31.234 (4)C11'—O3'1.242 (4)
C11—C121.433 (5)C11'—C12'1.425 (5)
C12—H120.9300C12'—H12'0.9300
C13—O2—H2O109.5C13'—O2'—H2O'109.5
O1—C13—O2123.1 (4)O1'—C13'—O2'122.8 (3)
O1—C13—C6124.3 (4)O1'—C13'—C6'124.5 (3)
O2—C13—C6112.6 (3)O2'—C13'—C6'112.7 (3)
C5—C6—C1119.0 (4)C5'—C6'—C1'119.0 (3)
C5—C6—C13118.5 (3)C5'—C6'—C13'119.4 (3)
C1—C6—C13122.4 (3)C1'—C6'—C13'121.6 (3)
C4—C5—C6121.8 (4)C4'—C5'—C6'121.6 (4)
C4—C5—H5119.1C4'—C5'—H5'119.2
C6—C5—H5119.1C6'—C5'—H5'119.2
C5—C4—C3118.5 (4)C3'—C4'—C5'119.1 (4)
C5—C4—H4120.8C3'—C4'—H4'120.4
C3—C4—H4120.8C5'—C4'—H4'120.4
C2—C3—C4121.8 (4)C4'—C3'—C2'121.0 (4)
C2—C3—H3119.1C4'—C3'—H3'119.5
C4—C3—H3119.1C2'—C3'—H3'119.5
C3—C2—C1119.9 (4)C3'—C2'—C1'120.8 (4)
C3—C2—H2120.0C3'—C2'—H2'119.6
C1—C2—H2120.0C1'—C2'—H2'119.6
C6—C1—C2118.9 (4)C2'—C1'—N'122.4 (3)
C6—C1—N118.7 (3)C2'—C1'—C6'118.3 (3)
C2—C1—N122.3 (3)N'—C1'—C6'119.2 (3)
C7—N—C1131.6 (3)C7'—N'—C1'130.7 (3)
C7—N—H1114.2C7'—N'—H1'114.6
C1—N—H1114.2C1'—N'—H1'114.6
N—C7—C12125.9 (3)C12'—C7'—N'126.0 (3)
N—C7—C8113.2 (3)C12'—C7'—C8'120.7 (3)
C12—C7—C8121.0 (3)N'—C7'—C8'113.3 (3)
C7—C8—C9113.6 (3)C7'—C8'—C9'112.9 (3)
C7—C8—H8A108.8C7'—C8'—H8'A109.0
C9—C8—H8A108.8C9'—C8'—H8'A109.0
C7—C8—H8B108.8C7'—C8'—H8'B109.0
C9—C8—H8B108.8C9'—C8'—H8'B109.0
H8A—C8—H8B107.7H8'A—C8'—H8'B107.8
C8—C9—C10109.7 (4)C8'—C9'—C10'109.3 (4)
C8—C9—H9A109.7C8'—C9'—H9'A109.8
C10—C9—H9A109.7C10'—C9'—H9'A109.8
C8—C9—H9B109.7C8'—C9'—H9'B109.8
C10—C9—H9B109.7C10'—C9'—H9'B109.8
H9A—C9—H9B108.2H9'A—C9'—H9'B108.3
C11—C10—C9112.0 (3)C11'—C10'—C9'112.0 (3)
C11—C10—H10A109.2C11'—C10'—H10C109.2
C9—C10—H10A109.2C9'—C10'—H10C109.2
C11—C10—H10B109.2C11'—C10'—H10D109.2
C9—C10—H10B109.2C9'—C10'—H10D109.2
H10A—C10—H10B107.9H10C—C10'—H10D107.9
O3—C11—C12122.3 (3)O3'—C11'—C12'122.3 (3)
O3—C11—C10118.6 (3)O3'—C11'—C10'119.2 (3)
C12—C11—C10119.0 (3)C12'—C11'—C10'118.4 (3)
C7—C12—C11121.4 (3)C7'—C12'—C11'122.0 (3)
C7—C12—H12119.3C7'—C12'—H12'119.0
C11—C12—H12119.3C11'—C12'—H12'119.0
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O3'0.821.812.562 (4)151
N—H1···O10.861.982.665 (4)136
O2'—H2O'···O3i0.821.782.562 (4)160
N'—H1'···O1'0.861.982.659 (4)135
Symmetry codes: (i) x, y+1, z.
Table 1
Selected geometric parameters (Å) top
C1—N1.407 (5)C1'—N'1.396 (5)
N—C71.359 (5)N'—C7'1.366 (5)
C7—C121.364 (5)C7'—C12'1.358 (5)
C11—C121.433 (5)C11'—C12'1.425 (5)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2O···O3'0.821.812.562 (4)151
N—H1···O10.861.982.665 (4)136
O2'—H2O'···O3i0.821.782.562 (4)160
N'—H1'···O1'0.861.982.659 (4)135
Symmetry codes: (i) x, y+1, z.
Acknowledgements top

This work was partially supported by the Brazilian agencies CAPES, CNPq and FAPEMIG.

references
References top

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