Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010297/ci6035sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010297/ci6035Isup2.hkl |
CCDC reference: 170782
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.
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.
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.
Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (Johnson, 1976). |
C12H11FO3 | F(000) = 464 |
Mr = 222.22 | Dx = 1.450 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 11.662 (3) Å | θ = 7.7–12.0° |
b = 7.579 (2) Å | µ = 0.12 mm−1 |
c = 12.038 (6) Å | T = 173 K |
β = 106.89 (3)° | Block, pale yellow |
V = 1018.0 (5) Å3 | 0.40 × 0.32 × 0.24 mm |
Z = 4 |
Rigaku AFC-7R diffractometer | Rint = 0.031 |
Radiation source: rotating anode | θmax = 27.5°, θmin = 3.2° |
Graphite monochromator | h = −15→15 |
ω–2θ scans | k = 0→9 |
5024 measured reflections | l = 0→15 |
2337 independent reflections | 3 standard reflections every 400 reflections |
1565 reflections with I > 2σ(I) | intensity decay: 0.0% |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-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 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
C12H11FO3 | V = 1018.0 (5) Å3 |
Mr = 222.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.662 (3) Å | µ = 0.12 mm−1 |
b = 7.579 (2) Å | T = 173 K |
c = 12.038 (6) Å | 0.40 × 0.32 × 0.24 mm |
β = 106.89 (3)° |
Rigaku AFC-7R diffractometer | Rint = 0.031 |
5024 measured reflections | 3 standard reflections every 400 reflections |
2337 independent reflections | intensity decay: 0.0% |
1565 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.38 e Å−3 |
2337 reflections | Δρmin = −0.32 e Å−3 |
146 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
F6 | 0.36000 (12) | 0.1145 (2) | 0.00284 (12) | 0.0509 (4) | |
O5 | 0.23937 (13) | −0.1620 (2) | 0.06247 (13) | 0.0402 (4) | |
H5 | 0.3176 | −0.1684 | 0.0695 | 0.073 (3)* | |
O32A | 0.04052 (12) | 0.15289 (19) | 0.41985 (11) | 0.0314 (3) | |
O32 | −0.11619 (12) | −0.0296 (2) | 0.36502 (11) | 0.0342 (3) | |
H32 | −0.0842 | −0.0760 | 0.4423 | 0.073 (3)* | |
C1 | 0.09856 (18) | 0.5251 (3) | 0.14278 (17) | 0.0333 (4) | |
H1A | 0.0662 | 0.5975 | 0.0722 | 0.073 (3)* | |
H1B | 0.1597 | 0.5944 | 0.2006 | 0.073 (3)* | |
C2 | 0.00044 (18) | 0.4654 (3) | 0.19153 (16) | 0.0327 (4) | |
C3A | 0.08575 (15) | 0.2142 (3) | 0.14264 (15) | 0.0266 (4) | |
C3 | −0.00712 (16) | 0.2884 (3) | 0.18979 (16) | 0.0289 (4) | |
C4 | 0.11510 (16) | 0.0408 (3) | 0.12578 (16) | 0.0292 (4) | |
H4 | 0.0714 | −0.0539 | 0.1455 | 0.059 (2)* | |
C5 | 0.20955 (17) | 0.0074 (3) | 0.07958 (16) | 0.0308 (4) | |
C6 | 0.26941 (17) | 0.1515 (3) | 0.05030 (16) | 0.0347 (5) | |
C7A | 0.14990 (17) | 0.3558 (3) | 0.11480 (15) | 0.0302 (4) | |
C7 | 0.24293 (18) | 0.3237 (3) | 0.06758 (16) | 0.0351 (5) | |
H7 | 0.2870 | 0.4180 | 0.0478 | 0.059 (2)* | |
C21 | −0.0742 (2) | 0.5945 (3) | 0.2344 (2) | 0.0455 (6) | |
H21A | −0.0481 | 0.7148 | 0.2245 | 0.088 (3)* | |
H21B | −0.0649 | 0.5726 | 0.3168 | 0.088 (3)* | |
H21C | −0.1586 | 0.5804 | 0.1899 | 0.088 (3)* | |
C31 | −0.09584 (17) | 0.1772 (3) | 0.22691 (17) | 0.0330 (5) | |
H31A | −0.1671 | 0.2501 | 0.2238 | 0.073 (3)* | |
H31B | −0.1221 | 0.0795 | 0.1706 | 0.073 (3)* | |
C32 | −0.04910 (17) | 0.1002 (2) | 0.34646 (16) | 0.0264 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
F6 | 0.0418 (7) | 0.0709 (10) | 0.0505 (8) | −0.0040 (7) | 0.0298 (6) | −0.0011 (7) |
O5 | 0.0331 (8) | 0.0409 (9) | 0.0477 (9) | 0.0019 (6) | 0.0134 (7) | −0.0044 (7) |
O32A | 0.0296 (7) | 0.0368 (8) | 0.0285 (7) | −0.0035 (6) | 0.0094 (5) | 0.0053 (6) |
O32 | 0.0363 (7) | 0.0382 (8) | 0.0295 (7) | −0.0079 (6) | 0.0119 (6) | 0.0036 (6) |
C1 | 0.0392 (10) | 0.0310 (10) | 0.0267 (9) | −0.0047 (8) | 0.0047 (8) | 0.0054 (8) |
C2 | 0.0340 (10) | 0.0365 (11) | 0.0240 (9) | 0.0026 (9) | 0.0027 (7) | 0.0047 (8) |
C3A | 0.0259 (9) | 0.0329 (10) | 0.0198 (8) | −0.0026 (7) | 0.0047 (7) | 0.0057 (7) |
C3 | 0.0266 (9) | 0.0360 (10) | 0.0235 (9) | 0.0002 (8) | 0.0065 (7) | 0.0066 (7) |
C4 | 0.0269 (9) | 0.0326 (10) | 0.0271 (9) | −0.0050 (8) | 0.0063 (7) | 0.0037 (8) |
C5 | 0.0281 (9) | 0.0370 (12) | 0.0254 (9) | −0.0020 (8) | 0.0049 (7) | −0.0003 (8) |
C6 | 0.0279 (9) | 0.0534 (13) | 0.0252 (9) | −0.0043 (9) | 0.0116 (8) | 0.0014 (9) |
C7A | 0.0323 (10) | 0.0349 (11) | 0.0215 (8) | −0.0058 (8) | 0.0048 (7) | 0.0049 (8) |
C7 | 0.0355 (10) | 0.0430 (12) | 0.0280 (10) | −0.0121 (9) | 0.0111 (8) | 0.0050 (8) |
C21 | 0.0464 (13) | 0.0442 (13) | 0.0425 (13) | 0.0134 (10) | 0.0077 (10) | 0.0009 (10) |
C31 | 0.0267 (9) | 0.0432 (12) | 0.0296 (10) | 0.0012 (8) | 0.0089 (8) | 0.0082 (8) |
C32 | 0.0273 (9) | 0.0275 (9) | 0.0291 (9) | 0.0038 (7) | 0.0153 (7) | 0.0018 (8) |
F6—C6 | 1.368 (2) | C3a—C7a | 1.403 (3) |
O5—C5 | 1.361 (3) | C3a—C3 | 1.473 (3) |
O32a—C32 | 1.223 (2) | C3—C31 | 1.500 (3) |
O32—C32 | 1.316 (2) | C4—C5 | 1.394 (3) |
C1—C7a | 1.495 (3) | C5—C6 | 1.396 (3) |
C1—C2 | 1.500 (3) | C6—C7 | 1.371 (3) |
C2—C3 | 1.344 (3) | C7a—C7 | 1.385 (3) |
C2—C21 | 1.498 (3) | C31—C32 | 1.501 (3) |
C3a—C4 | 1.388 (3) | ||
C7a—C1—C2 | 103.33 (17) | C6—C5—C4 | 118.00 (19) |
C3—C2—C21 | 127.96 (19) | F6—C6—C5 | 116.63 (19) |
C3—C2—C1 | 110.43 (18) | F6—C6—C7 | 119.61 (18) |
C21—C2—C1 | 121.6 (2) | C5—C6—C7 | 123.76 (18) |
C4—C3a—C7a | 121.20 (18) | C7—C7a—C3a | 119.93 (19) |
C4—C3a—C3 | 131.18 (17) | C7—C7a—C1 | 131.01 (18) |
C7a—C3a—C3 | 107.61 (18) | C3a—C7a—C1 | 109.05 (17) |
C2—C3—C3a | 109.57 (17) | C6—C7—C7a | 117.88 (18) |
C2—C3—C31 | 127.18 (19) | C32—C31—C3 | 114.48 (16) |
C3a—C3—C31 | 123.24 (18) | O32a—C32—O32 | 123.14 (17) |
C3a—C4—C5 | 119.20 (18) | O32a—C32—C31 | 124.20 (18) |
O5—C5—C6 | 122.11 (18) | O32—C32—C31 | 112.65 (17) |
O5—C5—C4 | 119.88 (18) |
Experimental details
Crystal data | |
Chemical formula | C12H11FO3 |
Mr | 222.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 11.662 (3), 7.579 (2), 12.038 (6) |
β (°) | 106.89 (3) |
V (Å3) | 1018.0 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.40 × 0.32 × 0.24 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5024, 2337, 1565 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.141, 1.02 |
No. of reflections | 2337 |
No. of parameters | 146 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 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.
F6—C6 | 1.368 (2) | C3a—C7a | 1.403 (3) |
O5—C5 | 1.361 (3) | C3a—C3 | 1.473 (3) |
O32a—C32 | 1.223 (2) | C3—C31 | 1.500 (3) |
O32—C32 | 1.316 (2) | C4—C5 | 1.394 (3) |
C1—C7a | 1.495 (3) | C5—C6 | 1.396 (3) |
C1—C2 | 1.500 (3) | C6—C7 | 1.371 (3) |
C2—C3 | 1.344 (3) | C7a—C7 | 1.385 (3) |
C2—C21 | 1.498 (3) | C31—C32 | 1.501 (3) |
C3a—C4 | 1.388 (3) | ||
C7a—C1—C2 | 103.33 (17) | C6—C5—C4 | 118.00 (19) |
C3—C2—C21 | 127.96 (19) | F6—C6—C5 | 116.63 (19) |
C3—C2—C1 | 110.43 (18) | F6—C6—C7 | 119.61 (18) |
C21—C2—C1 | 121.6 (2) | C5—C6—C7 | 123.76 (18) |
C4—C3a—C7a | 121.20 (18) | C7—C7a—C3a | 119.93 (19) |
C4—C3a—C3 | 131.18 (17) | C7—C7a—C1 | 131.01 (18) |
C7a—C3a—C3 | 107.61 (18) | C3a—C7a—C1 | 109.05 (17) |
C2—C3—C3a | 109.57 (17) | C6—C7—C7a | 117.88 (18) |
C2—C3—C31 | 127.18 (19) | C32—C31—C3 | 114.48 (16) |
C3a—C3—C31 | 123.24 (18) | O32a—C32—O32 | 123.14 (17) |
C3a—C4—C5 | 119.20 (18) | O32a—C32—C31 | 124.20 (18) |
O5—C5—C6 | 122.11 (18) | O32—C32—C31 | 112.65 (17) |
O5—C5—C4 | 119.88 (18) |
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).