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In the title mol­ecule, C15H16O3, 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 [Cg...Cg and interplanar distances of 3.70 (1) and 3.33 (1) Å].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052658/bg2118sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052658/bg2118Isup2.hkl
Contains datablock I

CCDC reference: 672954

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](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

Comment top

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).

Related literature top

For related literature, see: Braga et al. (2004); Xia et al. (2005, 2006); Yang et al. (2005).

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. View of the title compound, with displacement ellipsoids drawn at the 50% probability level [symmetry code: (ii) x, 1/2 - y, z].
[Figure 2] Fig. 2. The one-dimensional supramolecular chain along c-axis linked by intermolecular C—H···O bonds [symmetry code: (i) x, y, z - 1].
[Figure 3] Fig. 3. A couple of neighboring chains showing the weak π-π contacts between interleaving aromatic rings linking them along the b-axis
Methyl 4-[(1-methylcyclopent-3-en-1-yl)carbonyl]benzoate top
Crystal data top
C15H16O3Z = 4
Mr = 244.28F(000) = 520
Orthorhombic, PnmaDx = 1.270 Mg m3
Hall symbol: -P 2ac 2nMo Kα radiation, λ = 0.71073 Å
a = 16.6215 (6) ŵ = 0.09 mm1
b = 6.6520 (2) ÅT = 173 K
c = 11.5581 (5) ÅBlock, colourless
V = 1277.94 (8) Å30.54 × 0.12 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
1290 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.043
Graphite monochromatorθmax = 28.0°, θmin = 2.2°
Detector resolution: 10 pixels mm-1h = 2121
ϕ and\ w scansk = 88
22416 measured reflectionsl = 1515
1656 independent reflections
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.22 e Å3
Crystal data top
C15H16O3V = 1277.94 (8) Å3
Mr = 244.28Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 16.6215 (6) ŵ = 0.09 mm1
b = 6.6520 (2) ÅT = 173 K
c = 11.5581 (5) Å0.54 × 0.12 × 0.06 mm
Data collection top
Nonius KappaCCD
diffractometer
1290 reflections with I > 2σ(I)
22416 measured reflectionsRint = 0.043
1656 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.116H-atom parameters constrained
S = 1.06Δρmax = 0.27 e Å3
1656 reflectionsΔρmin = 0.22 e Å3
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
xyzUiso*/UeqOcc. (<1)
C10.82779 (7)0.3482 (2)0.16325 (12)0.0432 (4)
H10.87040.42560.13620.052*
C20.75151 (7)0.4356 (2)0.21171 (12)0.0426 (4)
H2A0.71910.49600.15120.051*
H2B0.76310.53630.27010.051*
C30.70802 (10)0.25000.26576 (15)0.0365 (4)
C40.72151 (14)0.25000.39724 (19)0.0798 (10)
H4A0.77820.25000.41320.120*
H4B0.69740.13220.43030.120*0.50
H4C0.69740.36780.43030.120*0.50
C50.61758 (10)0.25000.24182 (14)0.0274 (4)
C60.58474 (9)0.25000.11956 (13)0.0226 (3)
C70.63221 (9)0.25000.01907 (14)0.0263 (4)
H70.68800.25000.02510.032*
C80.59613 (9)0.25000.08943 (14)0.0265 (4)
H80.62790.25000.15560.032*
C90.51238 (9)0.25000.09965 (13)0.0222 (3)
C100.46505 (9)0.25000.00022 (13)0.0237 (3)
H100.40930.25000.00660.028*
C110.50064 (9)0.25000.10786 (14)0.0242 (3)
H110.46850.25000.17370.029*
C120.47066 (10)0.25000.21404 (13)0.0255 (3)
C130.48394 (13)0.25000.41695 (15)0.0426 (5)
H13A0.52450.25000.47600.064*
H13B0.45100.36780.42480.064*0.50
H13C0.45100.13220.42480.064*0.50
O10.56999 (7)0.25000.32202 (10)0.0398 (3)
O20.39814 (7)0.25000.22520 (10)0.0359 (3)
O30.52206 (7)0.25000.30386 (9)0.0336 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0253 (6)0.0566 (8)0.0478 (8)0.0081 (6)0.0026 (5)0.0008 (7)
C20.0302 (6)0.0424 (8)0.0552 (8)0.0084 (6)0.0042 (6)0.0145 (6)
C30.0266 (8)0.0542 (12)0.0287 (9)0.0000.0049 (7)0.000
C40.0403 (12)0.165 (3)0.0340 (11)0.0000.0146 (9)0.000
C50.0280 (8)0.0281 (8)0.0261 (8)0.0000.0006 (6)0.000
C60.0228 (7)0.0197 (7)0.0254 (7)0.0000.0010 (6)0.000
C70.0179 (7)0.0301 (8)0.0309 (8)0.0000.0012 (6)0.000
C80.0229 (7)0.0302 (8)0.0263 (8)0.0000.0060 (6)0.000
C90.0222 (7)0.0176 (7)0.0266 (8)0.0000.0004 (6)0.000
C100.0183 (7)0.0206 (8)0.0322 (8)0.0000.0025 (6)0.000
C110.0224 (7)0.0224 (8)0.0277 (8)0.0000.0058 (6)0.000
C120.0285 (8)0.0200 (8)0.0280 (8)0.0000.0011 (6)0.000
C130.0543 (12)0.0505 (12)0.0230 (8)0.0000.0031 (8)0.000
O10.0332 (7)0.0607 (9)0.0256 (6)0.0000.0036 (5)0.000
O20.0262 (6)0.0459 (8)0.0355 (7)0.0000.0061 (5)0.000
O30.0352 (7)0.0415 (7)0.0242 (6)0.0000.0016 (5)0.000
Geometric parameters (Å, º) top
C1—C1i1.307 (3)C7—C81.390 (2)
C1—C21.5030 (18)C7—H70.9300
C1—H10.9300C8—C91.397 (2)
C2—C31.5612 (17)C8—H80.9300
C2—H2A0.9700C9—C101.393 (2)
C2—H2B0.9700C9—C121.493 (2)
C3—C51.529 (2)C10—C111.382 (2)
C3—C41.536 (3)C10—H100.9300
C3—C2i1.5612 (17)C11—H110.9300
C4—H4A0.9600C12—O21.2123 (19)
C4—H4B0.9600C12—O31.3444 (19)
C4—H4C0.9600C13—O31.453 (2)
C5—O11.219 (2)C13—H13A0.9600
C5—C61.515 (2)C13—H13B0.9600
C6—C71.404 (2)C13—H13C0.9600
C6—C111.404 (2)
C1i—C1—C2112.76 (8)C11—C6—C5116.65 (13)
C1i—C1—H1123.6C8—C7—C6120.25 (13)
C2—C1—H1123.6C8—C7—H7119.9
C1—C2—C3103.51 (12)C6—C7—H7119.9
C1—C2—H2A111.1C7—C8—C9120.41 (14)
C3—C2—H2A111.1C7—C8—H8119.8
C1—C2—H2B111.1C9—C8—H8119.8
C3—C2—H2B111.1C10—C9—C8119.54 (14)
H2A—C2—H2B109.0C10—C9—C12117.93 (13)
C5—C3—C4108.82 (15)C8—C9—C12122.53 (14)
C5—C3—C2112.52 (9)C11—C10—C9120.27 (13)
C4—C3—C2109.16 (10)C11—C10—H10119.9
C5—C3—C2i112.52 (9)C9—C10—H10119.9
C4—C3—C2i109.16 (10)C10—C11—C6120.87 (14)
C2—C3—C2i104.54 (14)C10—C11—H11119.6
C3—C4—H4A109.5C6—C11—H11119.6
C3—C4—H4B109.5O2—C12—O3123.34 (14)
H4A—C4—H4B109.5O2—C12—C9123.79 (14)
C3—C4—H4C109.5O3—C12—C9112.87 (13)
H4A—C4—H4C109.5O3—C13—H13A109.5
H4B—C4—H4C109.5O3—C13—H13B109.5
O1—C5—C6118.40 (14)H13A—C13—H13B109.5
O1—C5—C3120.05 (15)O3—C13—H13C109.5
C6—C5—C3121.55 (14)H13A—C13—H13C109.5
C7—C6—C11118.66 (14)H13B—C13—H13C109.5
C7—C6—C5124.69 (13)C12—O3—C13114.69 (14)
C1i—C1—C2—C310.60 (11)C5—C6—C7—C8180.0
C1—C2—C3—C5138.49 (12)C6—C7—C8—C90.0
C1—C2—C3—C4100.59 (14)C7—C8—C9—C100.0
C1—C2—C3—C2i16.10 (17)C7—C8—C9—C12180.0
C4—C3—C5—O10.0C8—C9—C10—C110.0
C2—C3—C5—O1121.11 (10)C12—C9—C10—C11180.0
C2i—C3—C5—O1121.11 (10)C9—C10—C11—C60.0
C4—C3—C5—C6180.0C7—C6—C11—C100.0
C2—C3—C5—C658.89 (10)C5—C6—C11—C10180.0
C2i—C3—C5—C658.89 (10)C10—C9—C12—O20.0
O1—C5—C6—C7180.0C8—C9—C12—O2180.0
C3—C5—C6—C70.0C10—C9—C12—O3180.0
O1—C5—C6—C110.0C8—C9—C12—O30.0
C3—C5—C6—C11180.0O2—C12—O3—C130.0
C11—C6—C7—C80.0C9—C12—O3—C13180.0
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···O1ii0.962.453.339 (2)153
Symmetry code: (ii) x, y, z1.

Experimental details

Crystal data
Chemical formulaC15H16O3
Mr244.28
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)173
a, b, c (Å)16.6215 (6), 6.6520 (2), 11.5581 (5)
V3)1277.94 (8)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.54 × 0.12 × 0.06
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
22416, 1656, 1290
Rint0.043
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.116, 1.06
No. of reflections1656
No. of parameters103
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.27, 0.22

Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···O1i0.962.453.339 (2)153.3
Symmetry code: (i) x, y, z1.
 

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