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The bicylic system in the title compound, C12H11FO3, is effectively planar, with the methyl­carboxyl­ic acid residue being located above and perpendicular to this portion of the mol­ecule. The crystal structure is stabilized via a network of hydrogen-bonding and C—H...π interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010297/ci6035sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010297/ci6035Isup2.hkl
Contains datablock I

CCDC reference: 170782

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.047
  • wR factor = 0.141
  • Data-to-parameter ratio = 16.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

The nine atoms comprising the bicyclic system in the title compound, (I) (Fig. 1), are coplanar, with the maximum deviation out of their least-squares plane of 0.012 (2) Å being found for the C5 atom. The distribution of bond distances (Table 1) suggests extensive delocalization of π-electron density over all non-H atoms comprising the bicyclic system. The respective C1—C2—C3—C31, C2—C3—C31—C32 and C3—C31—C32—O32a torsion angles of -177.75 (18), -99.4 (2) and 17.1 (3)° show that the methylcarboxylic acid residue lies to one side and approximately perpendicular to the five-membered ring. In the crystal structure, centrosymmetrically related molecules associate via the familiar carboxylic acid dimer motif (Fig. 1) so that O32—H···O32ai is 1.69 Å, O32···O32ai is 2.652 (2) Å and the angle at H is 175° [symmetry code: (i) -x, -y, 1 - z]. The O32a atom also forms a weaker interaction with the hydroxyl-H atom so that O5—H···O32aii is 2.11 Å, O5···O32aii is 2.878 (3) Å and the angle at H is 143° [symmetry code: (ii) 1/2 - x, -1/2 + y, 1/2 - z]. In addition, the hydroxyl-H atom also forms an intramolecular interaction with the fluoride so that H···F6 is 2.39 Å with an angle at H of 103 Å.

The structure also features C—H···π interactions of note. Each of the ring methylene H atoms participates in a C—H···π contact so that this group bridges the six-membered ring of one molecule via H1B (the C—H1B···ring centroid distance is 2.70 Å with an angle at H of 160° for symmetry operation 1/2 - x, 1/2 + y, 1/2 - z) and the five-membered ring of another via H1A (2.75 Å, 151° for -x, 1 - y, -z).

Experimental top

The title compound< (I), was prepared from 4-(chloromethyl)-2-fluoro-1-methoxybenzene in an eight-step sequence. The key features of this synthesis were addition of a malonic ester enolate and a Friedel–Crafts ring closure, followed by addition of an acetate enolate and dehydration. Recrystallization from ethyl acetate/hexane (2:1) gave colourless crystals, m.p. 443–445 K (decomposition). 1H NMR (CDCl3, 300 MHz): δ 2.08, s, 3H; 3.26, s, 2H; 3.50, s, 2H; 6.88, d, J = 8 Hz, 1H; 7.08, d, J = 10 Hz, 1H.

Refinement top

The C-bound H atoms were placed in geometrically calculated positions and included in the final refinement in the riding model approximation with an overall thermal parameter, Uiso, with 1.25Uiso for CH2 and 1.5Uiso for CH3. The O—H atoms were located from a difference map and were assigned 1.25Uiso.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976).
(I) top
Crystal data top
C12H11FO3F(000) = 464
Mr = 222.22Dx = 1.450 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 11.662 (3) Åθ = 7.7–12.0°
b = 7.579 (2) ŵ = 0.12 mm1
c = 12.038 (6) ÅT = 173 K
β = 106.89 (3)°Block, pale yellow
V = 1018.0 (5) Å30.40 × 0.32 × 0.24 mm
Z = 4
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.031
Radiation source: rotating anodeθmax = 27.5°, θmin = 3.2°
Graphite monochromatorh = 1515
ω–2θ scansk = 09
5024 measured reflectionsl = 015
2337 independent reflections3 standard reflections every 400 reflections
1565 reflections with I > 2σ(I) intensity decay: 0.0%
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0743P)2 + 0.3569P]
where P = (Fo2 + 2Fc2)/3
2337 reflections(Δ/σ)max < 0.001
146 parametersΔρmax = 0.38 e Å3
0 restraintsΔρmin = 0.32 e Å3
Crystal data top
C12H11FO3V = 1018.0 (5) Å3
Mr = 222.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 11.662 (3) ŵ = 0.12 mm1
b = 7.579 (2) ÅT = 173 K
c = 12.038 (6) Å0.40 × 0.32 × 0.24 mm
β = 106.89 (3)°
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.031
5024 measured reflections3 standard reflections every 400 reflections
2337 independent reflections intensity decay: 0.0%
1565 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 1.02Δρmax = 0.38 e Å3
2337 reflectionsΔρmin = 0.32 e Å3
146 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*/Ueq
F60.36000 (12)0.1145 (2)0.00284 (12)0.0509 (4)
O50.23937 (13)0.1620 (2)0.06247 (13)0.0402 (4)
H50.31760.16840.06950.073 (3)*
O32A0.04052 (12)0.15289 (19)0.41985 (11)0.0314 (3)
O320.11619 (12)0.0296 (2)0.36502 (11)0.0342 (3)
H320.08420.07600.44230.073 (3)*
C10.09856 (18)0.5251 (3)0.14278 (17)0.0333 (4)
H1A0.06620.59750.07220.073 (3)*
H1B0.15970.59440.20060.073 (3)*
C20.00044 (18)0.4654 (3)0.19153 (16)0.0327 (4)
C3A0.08575 (15)0.2142 (3)0.14264 (15)0.0266 (4)
C30.00712 (16)0.2884 (3)0.18979 (16)0.0289 (4)
C40.11510 (16)0.0408 (3)0.12578 (16)0.0292 (4)
H40.07140.05390.14550.059 (2)*
C50.20955 (17)0.0074 (3)0.07958 (16)0.0308 (4)
C60.26941 (17)0.1515 (3)0.05030 (16)0.0347 (5)
C7A0.14990 (17)0.3558 (3)0.11480 (15)0.0302 (4)
C70.24293 (18)0.3237 (3)0.06758 (16)0.0351 (5)
H70.28700.41800.04780.059 (2)*
C210.0742 (2)0.5945 (3)0.2344 (2)0.0455 (6)
H21A0.04810.71480.22450.088 (3)*
H21B0.06490.57260.31680.088 (3)*
H21C0.15860.58040.18990.088 (3)*
C310.09584 (17)0.1772 (3)0.22691 (17)0.0330 (5)
H31A0.16710.25010.22380.073 (3)*
H31B0.12210.07950.17060.073 (3)*
C320.04910 (17)0.1002 (2)0.34646 (16)0.0264 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F60.0418 (7)0.0709 (10)0.0505 (8)0.0040 (7)0.0298 (6)0.0011 (7)
O50.0331 (8)0.0409 (9)0.0477 (9)0.0019 (6)0.0134 (7)0.0044 (7)
O32A0.0296 (7)0.0368 (8)0.0285 (7)0.0035 (6)0.0094 (5)0.0053 (6)
O320.0363 (7)0.0382 (8)0.0295 (7)0.0079 (6)0.0119 (6)0.0036 (6)
C10.0392 (10)0.0310 (10)0.0267 (9)0.0047 (8)0.0047 (8)0.0054 (8)
C20.0340 (10)0.0365 (11)0.0240 (9)0.0026 (9)0.0027 (7)0.0047 (8)
C3A0.0259 (9)0.0329 (10)0.0198 (8)0.0026 (7)0.0047 (7)0.0057 (7)
C30.0266 (9)0.0360 (10)0.0235 (9)0.0002 (8)0.0065 (7)0.0066 (7)
C40.0269 (9)0.0326 (10)0.0271 (9)0.0050 (8)0.0063 (7)0.0037 (8)
C50.0281 (9)0.0370 (12)0.0254 (9)0.0020 (8)0.0049 (7)0.0003 (8)
C60.0279 (9)0.0534 (13)0.0252 (9)0.0043 (9)0.0116 (8)0.0014 (9)
C7A0.0323 (10)0.0349 (11)0.0215 (8)0.0058 (8)0.0048 (7)0.0049 (8)
C70.0355 (10)0.0430 (12)0.0280 (10)0.0121 (9)0.0111 (8)0.0050 (8)
C210.0464 (13)0.0442 (13)0.0425 (13)0.0134 (10)0.0077 (10)0.0009 (10)
C310.0267 (9)0.0432 (12)0.0296 (10)0.0012 (8)0.0089 (8)0.0082 (8)
C320.0273 (9)0.0275 (9)0.0291 (9)0.0038 (7)0.0153 (7)0.0018 (8)
Geometric parameters (Å, º) top
F6—C61.368 (2)C3a—C7a1.403 (3)
O5—C51.361 (3)C3a—C31.473 (3)
O32a—C321.223 (2)C3—C311.500 (3)
O32—C321.316 (2)C4—C51.394 (3)
C1—C7a1.495 (3)C5—C61.396 (3)
C1—C21.500 (3)C6—C71.371 (3)
C2—C31.344 (3)C7a—C71.385 (3)
C2—C211.498 (3)C31—C321.501 (3)
C3a—C41.388 (3)
C7a—C1—C2103.33 (17)C6—C5—C4118.00 (19)
C3—C2—C21127.96 (19)F6—C6—C5116.63 (19)
C3—C2—C1110.43 (18)F6—C6—C7119.61 (18)
C21—C2—C1121.6 (2)C5—C6—C7123.76 (18)
C4—C3a—C7a121.20 (18)C7—C7a—C3a119.93 (19)
C4—C3a—C3131.18 (17)C7—C7a—C1131.01 (18)
C7a—C3a—C3107.61 (18)C3a—C7a—C1109.05 (17)
C2—C3—C3a109.57 (17)C6—C7—C7a117.88 (18)
C2—C3—C31127.18 (19)C32—C31—C3114.48 (16)
C3a—C3—C31123.24 (18)O32a—C32—O32123.14 (17)
C3a—C4—C5119.20 (18)O32a—C32—C31124.20 (18)
O5—C5—C6122.11 (18)O32—C32—C31112.65 (17)
O5—C5—C4119.88 (18)

Experimental details

Crystal data
Chemical formulaC12H11FO3
Mr222.22
Crystal system, space groupMonoclinic, P21/n
Temperature (K)173
a, b, c (Å)11.662 (3), 7.579 (2), 12.038 (6)
β (°) 106.89 (3)
V3)1018.0 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.12
Crystal size (mm)0.40 × 0.32 × 0.24
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5024, 2337, 1565
Rint0.031
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.141, 1.02
No. of reflections2337
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.38, 0.32

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997), SIR97 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
F6—C61.368 (2)C3a—C7a1.403 (3)
O5—C51.361 (3)C3a—C31.473 (3)
O32a—C321.223 (2)C3—C311.500 (3)
O32—C321.316 (2)C4—C51.394 (3)
C1—C7a1.495 (3)C5—C61.396 (3)
C1—C21.500 (3)C6—C71.371 (3)
C2—C31.344 (3)C7a—C71.385 (3)
C2—C211.498 (3)C31—C321.501 (3)
C3a—C41.388 (3)
C7a—C1—C2103.33 (17)C6—C5—C4118.00 (19)
C3—C2—C21127.96 (19)F6—C6—C5116.63 (19)
C3—C2—C1110.43 (18)F6—C6—C7119.61 (18)
C21—C2—C1121.6 (2)C5—C6—C7123.76 (18)
C4—C3a—C7a121.20 (18)C7—C7a—C3a119.93 (19)
C4—C3a—C3131.18 (17)C7—C7a—C1131.01 (18)
C7a—C3a—C3107.61 (18)C3a—C7a—C1109.05 (17)
C2—C3—C3a109.57 (17)C6—C7—C7a117.88 (18)
C2—C3—C31127.18 (19)C32—C31—C3114.48 (16)
C3a—C3—C31123.24 (18)O32a—C32—O32123.14 (17)
C3a—C4—C5119.20 (18)O32a—C32—C31124.20 (18)
O5—C5—C6122.11 (18)O32—C32—C31112.65 (17)
O5—C5—C4119.88 (18)
 

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