In the title molecule, C
15H
16O
3, the non-H atoms of the benzoate group, the
p-carbonyl, the attached ring C and its substituent methyl group lie on a mirror plane bisecting the five-membered ring, in which the C=C double bond is
cis configured. Owing to symmetry considerations, the dihedral angle between the aromatic and the cyclopentyl rings is exactly 90°. There is an intermolecular C—H
O hydrogen bond, which links molecules into a one-dimensional supramolecular chain along the
c axis in a head-to-tail fashion. These supramolecular chains, in turn, interact with each other along the
b axis through weak π–π contacts between neighboring aromatic rings [
CgCg and interplanar distances of 3.70 (1) and 3.33 (1) Å].
Supporting information
CCDC reference: 672954
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.002 Å
- R factor = 0.041
- wR factor = 0.116
- Data-to-parameter ratio = 16.1
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.61 Ratio
PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.29 Ratio
0 ALERT level A = In general: serious problem
2 ALERT level B = Potentially serious problem
0 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
1 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
The preparation of the titled compound was conducted by the reaction of
commercially available compounds, methyl 3-cyclopene carboxylate with LDA/MeI,
reduction with LiAlH4 and oxidation by pyridinium chlorochromate (PCC).
After reaction with methyl 4-carboxylate phenylmagnesium bromide at -40°C,
the target compound was obtained by oxidation with PCC.
Hydrogen atoms were positioned geometrically and allowed to ride on their parent
atoms, with C—H = 0.93 Å for Csp2 and 0.96 Å for methyl.
Uiso(H) = xUeq(C), where x = 1.2 for Csp2 and 1.5 for
methyl.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).
Methyl 4-[(1-methylcyclopent-3-en-1-yl)carbonyl]benzoate
top
Crystal data top
C15H16O3 | Z = 4 |
Mr = 244.28 | F(000) = 520 |
Orthorhombic, Pnma | Dx = 1.270 Mg m−3 |
Hall symbol: -P 2ac 2n | Mo Kα radiation, λ = 0.71073 Å |
a = 16.6215 (6) Å | µ = 0.09 mm−1 |
b = 6.6520 (2) Å | T = 173 K |
c = 11.5581 (5) Å | Block, colourless |
V = 1277.94 (8) Å3 | 0.54 × 0.12 × 0.06 mm |
Data collection top
Nonius KappaCCD diffractometer | 1290 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 28.0°, θmin = 2.2° |
Detector resolution: 10 pixels mm-1 | h = −21→21 |
ϕ and\ w scans | k = −8→8 |
22416 measured reflections | l = −15→15 |
1656 independent reflections | |
Refinement top
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0595P)2 + 0.2712P] where P = (Fo2 + 2Fc2)/3 |
1656 reflections | (Δ/σ)max < 0.001 |
103 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C15H16O3 | V = 1277.94 (8) Å3 |
Mr = 244.28 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 16.6215 (6) Å | µ = 0.09 mm−1 |
b = 6.6520 (2) Å | T = 173 K |
c = 11.5581 (5) Å | 0.54 × 0.12 × 0.06 mm |
Data collection top
Nonius KappaCCD diffractometer | 1290 reflections with I > 2σ(I) |
22416 measured reflections | Rint = 0.043 |
1656 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.116 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
1656 reflections | Δρmin = −0.22 e Å−3 |
103 parameters | |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.82779 (7) | 0.3482 (2) | 0.16325 (12) | 0.0432 (4) | |
H1 | 0.8704 | 0.4256 | 0.1362 | 0.052* | |
C2 | 0.75151 (7) | 0.4356 (2) | 0.21171 (12) | 0.0426 (4) | |
H2A | 0.7191 | 0.4960 | 0.1512 | 0.051* | |
H2B | 0.7631 | 0.5363 | 0.2701 | 0.051* | |
C3 | 0.70802 (10) | 0.2500 | 0.26576 (15) | 0.0365 (4) | |
C4 | 0.72151 (14) | 0.2500 | 0.39724 (19) | 0.0798 (10) | |
H4A | 0.7782 | 0.2500 | 0.4132 | 0.120* | |
H4B | 0.6974 | 0.1322 | 0.4303 | 0.120* | 0.50 |
H4C | 0.6974 | 0.3678 | 0.4303 | 0.120* | 0.50 |
C5 | 0.61758 (10) | 0.2500 | 0.24182 (14) | 0.0274 (4) | |
C6 | 0.58474 (9) | 0.2500 | 0.11956 (13) | 0.0226 (3) | |
C7 | 0.63221 (9) | 0.2500 | 0.01907 (14) | 0.0263 (4) | |
H7 | 0.6880 | 0.2500 | 0.0251 | 0.032* | |
C8 | 0.59613 (9) | 0.2500 | −0.08943 (14) | 0.0265 (4) | |
H8 | 0.6279 | 0.2500 | −0.1556 | 0.032* | |
C9 | 0.51238 (9) | 0.2500 | −0.09965 (13) | 0.0222 (3) | |
C10 | 0.46505 (9) | 0.2500 | −0.00022 (13) | 0.0237 (3) | |
H10 | 0.4093 | 0.2500 | −0.0066 | 0.028* | |
C11 | 0.50064 (9) | 0.2500 | 0.10786 (14) | 0.0242 (3) | |
H11 | 0.4685 | 0.2500 | 0.1737 | 0.029* | |
C12 | 0.47066 (10) | 0.2500 | −0.21404 (13) | 0.0255 (3) | |
C13 | 0.48394 (13) | 0.2500 | −0.41695 (15) | 0.0426 (5) | |
H13A | 0.5245 | 0.2500 | −0.4760 | 0.064* | |
H13B | 0.4510 | 0.3678 | −0.4248 | 0.064* | 0.50 |
H13C | 0.4510 | 0.1322 | −0.4248 | 0.064* | 0.50 |
O1 | 0.56999 (7) | 0.2500 | 0.32202 (10) | 0.0398 (3) | |
O2 | 0.39814 (7) | 0.2500 | −0.22520 (10) | 0.0359 (3) | |
O3 | 0.52206 (7) | 0.2500 | −0.30386 (9) | 0.0336 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0253 (6) | 0.0566 (8) | 0.0478 (8) | −0.0081 (6) | −0.0026 (5) | −0.0008 (7) |
C2 | 0.0302 (6) | 0.0424 (8) | 0.0552 (8) | −0.0084 (6) | −0.0042 (6) | −0.0145 (6) |
C3 | 0.0266 (8) | 0.0542 (12) | 0.0287 (9) | 0.000 | −0.0049 (7) | 0.000 |
C4 | 0.0403 (12) | 0.165 (3) | 0.0340 (11) | 0.000 | −0.0146 (9) | 0.000 |
C5 | 0.0280 (8) | 0.0281 (8) | 0.0261 (8) | 0.000 | −0.0006 (6) | 0.000 |
C6 | 0.0228 (7) | 0.0197 (7) | 0.0254 (7) | 0.000 | 0.0010 (6) | 0.000 |
C7 | 0.0179 (7) | 0.0301 (8) | 0.0309 (8) | 0.000 | 0.0012 (6) | 0.000 |
C8 | 0.0229 (7) | 0.0302 (8) | 0.0263 (8) | 0.000 | 0.0060 (6) | 0.000 |
C9 | 0.0222 (7) | 0.0176 (7) | 0.0266 (8) | 0.000 | 0.0004 (6) | 0.000 |
C10 | 0.0183 (7) | 0.0206 (8) | 0.0322 (8) | 0.000 | 0.0025 (6) | 0.000 |
C11 | 0.0224 (7) | 0.0224 (8) | 0.0277 (8) | 0.000 | 0.0058 (6) | 0.000 |
C12 | 0.0285 (8) | 0.0200 (8) | 0.0280 (8) | 0.000 | −0.0011 (6) | 0.000 |
C13 | 0.0543 (12) | 0.0505 (12) | 0.0230 (8) | 0.000 | −0.0031 (8) | 0.000 |
O1 | 0.0332 (7) | 0.0607 (9) | 0.0256 (6) | 0.000 | 0.0036 (5) | 0.000 |
O2 | 0.0262 (6) | 0.0459 (8) | 0.0355 (7) | 0.000 | −0.0061 (5) | 0.000 |
O3 | 0.0352 (7) | 0.0415 (7) | 0.0242 (6) | 0.000 | 0.0016 (5) | 0.000 |
Geometric parameters (Å, º) top
C1—C1i | 1.307 (3) | C7—C8 | 1.390 (2) |
C1—C2 | 1.5030 (18) | C7—H7 | 0.9300 |
C1—H1 | 0.9300 | C8—C9 | 1.397 (2) |
C2—C3 | 1.5612 (17) | C8—H8 | 0.9300 |
C2—H2A | 0.9700 | C9—C10 | 1.393 (2) |
C2—H2B | 0.9700 | C9—C12 | 1.493 (2) |
C3—C5 | 1.529 (2) | C10—C11 | 1.382 (2) |
C3—C4 | 1.536 (3) | C10—H10 | 0.9300 |
C3—C2i | 1.5612 (17) | C11—H11 | 0.9300 |
C4—H4A | 0.9600 | C12—O2 | 1.2123 (19) |
C4—H4B | 0.9600 | C12—O3 | 1.3444 (19) |
C4—H4C | 0.9600 | C13—O3 | 1.453 (2) |
C5—O1 | 1.219 (2) | C13—H13A | 0.9600 |
C5—C6 | 1.515 (2) | C13—H13B | 0.9600 |
C6—C7 | 1.404 (2) | C13—H13C | 0.9600 |
C6—C11 | 1.404 (2) | | |
| | | |
C1i—C1—C2 | 112.76 (8) | C11—C6—C5 | 116.65 (13) |
C1i—C1—H1 | 123.6 | C8—C7—C6 | 120.25 (13) |
C2—C1—H1 | 123.6 | C8—C7—H7 | 119.9 |
C1—C2—C3 | 103.51 (12) | C6—C7—H7 | 119.9 |
C1—C2—H2A | 111.1 | C7—C8—C9 | 120.41 (14) |
C3—C2—H2A | 111.1 | C7—C8—H8 | 119.8 |
C1—C2—H2B | 111.1 | C9—C8—H8 | 119.8 |
C3—C2—H2B | 111.1 | C10—C9—C8 | 119.54 (14) |
H2A—C2—H2B | 109.0 | C10—C9—C12 | 117.93 (13) |
C5—C3—C4 | 108.82 (15) | C8—C9—C12 | 122.53 (14) |
C5—C3—C2 | 112.52 (9) | C11—C10—C9 | 120.27 (13) |
C4—C3—C2 | 109.16 (10) | C11—C10—H10 | 119.9 |
C5—C3—C2i | 112.52 (9) | C9—C10—H10 | 119.9 |
C4—C3—C2i | 109.16 (10) | C10—C11—C6 | 120.87 (14) |
C2—C3—C2i | 104.54 (14) | C10—C11—H11 | 119.6 |
C3—C4—H4A | 109.5 | C6—C11—H11 | 119.6 |
C3—C4—H4B | 109.5 | O2—C12—O3 | 123.34 (14) |
H4A—C4—H4B | 109.5 | O2—C12—C9 | 123.79 (14) |
C3—C4—H4C | 109.5 | O3—C12—C9 | 112.87 (13) |
H4A—C4—H4C | 109.5 | O3—C13—H13A | 109.5 |
H4B—C4—H4C | 109.5 | O3—C13—H13B | 109.5 |
O1—C5—C6 | 118.40 (14) | H13A—C13—H13B | 109.5 |
O1—C5—C3 | 120.05 (15) | O3—C13—H13C | 109.5 |
C6—C5—C3 | 121.55 (14) | H13A—C13—H13C | 109.5 |
C7—C6—C11 | 118.66 (14) | H13B—C13—H13C | 109.5 |
C7—C6—C5 | 124.69 (13) | C12—O3—C13 | 114.69 (14) |
| | | |
C1i—C1—C2—C3 | 10.60 (11) | C5—C6—C7—C8 | 180.0 |
C1—C2—C3—C5 | −138.49 (12) | C6—C7—C8—C9 | 0.0 |
C1—C2—C3—C4 | 100.59 (14) | C7—C8—C9—C10 | 0.0 |
C1—C2—C3—C2i | −16.10 (17) | C7—C8—C9—C12 | 180.0 |
C4—C3—C5—O1 | 0.0 | C8—C9—C10—C11 | 0.0 |
C2—C3—C5—O1 | −121.11 (10) | C12—C9—C10—C11 | 180.0 |
C2i—C3—C5—O1 | 121.11 (10) | C9—C10—C11—C6 | 0.0 |
C4—C3—C5—C6 | 180.0 | C7—C6—C11—C10 | 0.0 |
C2—C3—C5—C6 | 58.89 (10) | C5—C6—C11—C10 | 180.0 |
C2i—C3—C5—C6 | −58.89 (10) | C10—C9—C12—O2 | 0.0 |
O1—C5—C6—C7 | 180.0 | C8—C9—C12—O2 | 180.0 |
C3—C5—C6—C7 | 0.0 | C10—C9—C12—O3 | 180.0 |
O1—C5—C6—C11 | 0.0 | C8—C9—C12—O3 | 0.0 |
C3—C5—C6—C11 | 180.0 | O2—C12—O3—C13 | 0.0 |
C11—C6—C7—C8 | 0.0 | C9—C12—O3—C13 | 180.0 |
Symmetry code: (i) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1ii | 0.96 | 2.45 | 3.339 (2) | 153 |
Symmetry code: (ii) x, y, z−1. |
Experimental details
Crystal data |
Chemical formula | C15H16O3 |
Mr | 244.28 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 173 |
a, b, c (Å) | 16.6215 (6), 6.6520 (2), 11.5581 (5) |
V (Å3) | 1277.94 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.54 × 0.12 × 0.06 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 22416, 1656, 1290 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.660 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.116, 1.06 |
No. of reflections | 1656 |
No. of parameters | 103 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.22 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C13—H13A···O1i | 0.96 | 2.45 | 3.339 (2) | 153.3 |
Symmetry code: (i) x, y, z−1. |
As one aspect of the green chemistry, photochemistry has attracted widespread interest and attention. During the course of our investigation on solid-state organic photochemistry (Braga et al., 2004; Xia et al., 2005; Xia et al., 2006, Yang et al., 2005), the title compound C~15~H~16Õ~3~ (I) was synthesized and its crystal structure is presented in this paper.
The asymmetric unit of the title compound contains sixteen non-hydrogen atoms of which two carbon lie in general position and the remaining thirteen plus two carbonyl and one ester O atoms lie onto a mirror plane (Fig. 1). Geometric parameters are in the usual ranges. The C=C double bond in the pentagonal ring is cis configured, and the deviation of C3 from the plane defined by C2, C1, C1ii and C2ii [symmetry code (ii) x, 0.5 - y, z] is 0.28 (1) Å. Due to symmetry considerations, the dihedral angle between the aromatic and the cyclopentyl rings is exactly 90°. As shown in Fig. 2 and Table 1, there is an intermolecular H-bond between C13 and O1i [symmetry code: (i) x, y, z - 1] which leads to a 1-D supramolecular chain along c-axis in a head-to-tail fashion. These supramolecular chains, in turn, interact with each other along the b-axis through weak π-π contacts between neighboring aromatic rings, with Cg···Cg and interplanar distances of 3.70 (1) and 3.33 (1) Å (Fig. 3).