Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615005720/yf3082sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229615005720/yf3082Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615005720/yf3082Isup3.pdf | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615005720/yf3082Isup4.pdf | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615005720/yf3082Isup5.pdf | |
Portable Document Format (PDF) file https://doi.org/10.1107/S2053229615005720/yf3082Isup6.pdf | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229615005720/yf3082Isup7.cml |
CCDC reference: 1055291
Racemates generally afford three types of racemic crystalline solids, i.e. racemic mixtures (conglomerates), racemic compounds and racemic solid solutions (Jacques et al., 1994). The arrangements of R- and S-isomers in racemic crystals can be explained by the relative affinity between the R(or S)-enantiomers, and that between the R- and S-enantiomers. A conglomerate is a 1:1 mixture of chiral crystals, half composed of R-enantiomers and half composed of S-enantiomers. A racemic compound is composed of pairs of R- and S-isomers. A racemic solid solution includes equal quantities of R- and S-enantiomers, but there is no periodicity present. The frequencies of these three types of racemic crystal in racemates are 5–10% for conglomerates, 90% for racemic compounds and <5% for racemic solid solutions. Since there is a chance that racemic compounds, which are the most frequent form of racemic crystal, may afford conglomerates by spontaneous crystallization, their design is one of the important challenges for crystal engineering (Sakamoto et al., 2008; Kondepudi et al., 1993).
The prediction and design of desired interactions between enantiomers are difficult in practice. Therefore, detailed information about molecular interactions based on systematic structural studies of suitable model compounds should be valuable. Recently, the authors have found that diaroylation at the peri-positions (1- and 8-positions) of naphthalene derivatives proceeds smoothly by choice of a suitable acidic mediator (Okamoto & Yonezawa, 2009; Okamoto et al., 2011). In the solid state, the molecules of the peri-aroylnaphthalene compounds thus obtained have noncoplanar aromatic rings. The two aroyl groups are attached to the naphthalene ring in a perpendicular fashion and are oriented in opposite directions (Nakaema et al., 2008; Watanabe et al., 2010).
The noncoplanarity of peri-aroylnaphthalene compounds means a reduction in π-conjugation, inevitably resulting in a lower contribution from π–π stacking. Instead, it affords the opportunity to reveal normally hidden nonbonding intermolecular interactions. We have recently reported the relationship between (aromatic)C—H···O═C interactions and (aromatic)C—H···π interactions in organic crystals found in a systematic comparison of peri-aroylnaphthalene analogues (Okamoto et al., 2014; Yoshiwaka et al., 2014).
Furthermore, peri-aroylnaphthalene molecules exhibit axial chirality, with either an R,R or an S,S stereogenic axis. Information on molecular interactions between R,R(S,S)-isomers, and between R,R- and S,S-isomers, is important for designing racemic compounds. However, peri-aroylnaphthalene compounds might not be the best models because their internal steric repulsion presumably restricts the formation of intermolecular interactions. To the best of our knowledge, 1-aroylated naphthalene compounds have essentially the same noncoplanar structure as their 1,8-diaroylated naphthalene homologues in the crystalline state (Kato et al., 2010; Watanabe et al., 2011). On the other hand, the dihedral angle between the benzene and naphthalene rings of 1-aroylated naphthalene is smaller than that of the 1,8-diaroylated naphthalene analogue. These results for 1-aroylated naphthalene compounds set a high expectation of the formation of a variety of interactions in the crystal structure, based on their flexible molecular conformations. Herein, we report the X-ray crystal structure of (2,7-dimethoxynaphthalen-1-yl)(3-fluorophenyl)methanone [or 1-(3-fluorobenzoyl)-2,7-dimethoxynaphthalene], (I), and discuss the correlation between molecular structure, crystal packing and nonbonding intermolecular interactions through a comparison with analogous molecules.
All reagents were of commercial quality and were used as received. Solvents were dried and purified using standard techniques (Armarego et al., 1996). 2,7-Dimethoxynaphthalene was prepared according to the literature method of Domasevitch et al. (2012). The 1H NMR spectrum was recorded on a JEOL JNM-AL300 spectrometer (300 MHz). Chemical shifts for 1H NMR are expressed in p.p.m. relative to an internal standard of Me4Si (δ 0.00). The 13C NMR spectrum was recorded on a JEOL JNM-AL300 spectrometer (75 MHz). Chemical shifts for 13C NMR are expressed in p.p.m. relative to CDCl3 (δ 77.0). The IR spectrum was recorded on a JASCO FT–IR 4100 spectrometer. The high-resolution FAB mass spectrum was recorded on a JEOL MStation (JMS700) ion-trap mass spectrometer in positive-ion mode.
3-Fluorobenzoyl chloride (1.1 mmol, 0.132 ml), aluminium chloride (AlCl3, 1.3 mmol, 173 mg) and dichloromethane (CH2Cl2, 2.0 ml) were placed in an examiner-shaped flask and stirred at 273 K. To the reaction mixture was added 2,7-dimethoxynaphthalene (1.0 mmol, 188 mg). The reaction mixture was stirred at 273 K for 4 h, and it was then poured into methanol (10 ml) and water (20 ml). The mixture was extracted with CHCl3 (10 ml × 3). The combined extracts were washed with 2 M aqueous NaOH followed by washing with brine. The organic layers thus obtained were dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give a cake. The crude product was purified by recrystallization from hexane (isolated yield 48%). The isolated product was then crystallized from CHCl3–hexane (1:3 v/v) to give single crystals (m.p. 359.0–363.5 K).
1H NMR (300 MHz, CDCl3, δ, p.p.m.): 3.73 (3H, s), 3.78 (3H, s), 6.79 (1H, d, J = 2.4 Hz), 7.02 (1H, dd, J = 2.4, 9.0 Hz), 7.16 (1H, d, J = 9.0 Hz), 7.26 (1H, m), 7.38 (1H, m), 7.59 (2H, m), 7.73 (1H, d, J = 9.0 Hz), 7.88 (1H, d, J = 9.0 Hz). 13C NMR (75 MHz, CDCl3, δ, p.p.m.): 55.17, 56.23, 101.84, 110.04, 115.80 (JC—F = 22.2 Hz), 117.14, 120.28 (JC—F = 21.5 Hz), 120.98, 124.32, 125.28, 129.74, 130.14 (JC—F = 7.2 Hz), 131.39, 132.94, 140.28 (JC—F = 6.45 Hz), 155.15, 158.97, 162.85 (JC—F = 245.9 Hz), 196.82. IR (KBr, ν, cm-1): 1665 (C═O), 1590, 1513, 1486 (Ar, naphthalene), 1226 [(Ar)C—O—C]. HRMS (FAB; m-NBA) m/z: [M+H]+, calculated for C19H15FO3: 310.0986; found: 310.1005.
All H atoms were located in a difference Fourier map and subsequently refined as riding atoms, with C—H = 0.95 (aromatic) or 0.98 Å (methyl), and with Uiso(H) = 1.2Ueq(C). The positions of the methyl H atoms were rotationally optimized.
The aroyl group of the title compound, (I), is perpendicular to the plane of the naphthalene ring, similar to other 1-aroylated naphthalene analogues (Fig. 1). The dihedral angle between the benzene and naphthalene rings is 85.90 (5)° [torsion angle C2—C1—C11—O1 = -110.35 (15)°]. The benzene ring is slightly tilted to the bridging C—(C═O)—C plane [dihedral angle 25.04 (7)°; torsion angle C17—C12—C11—O1 = -153.87 (12)°]. The methoxy group adjacent to the aroyl group is oriented to the exo side of the molecule and the other methoxy group is directed to the endo side. The molecules exhibit axial chirality, with either an R- or an S-stereogenic axis. In the crystal structure, the column composed of R-enantiomers and that composed of S-enantiomers are alternately arranged in a stripe structure (Fig. 2). R- and S-isomers are linked into dimeric pairs by a pair of C—H···F hydrogen bonds between the methoxy groups and the F atoms, and by π–π interactions between the benzene rings of the aroyl groups [C19—H19···F1iii = 2.55 Å and Cg3···Cg3iii = 3.89 Å; symmetry code: (iii) -x + 1, -y, -z; Cg3 is the centroid of the ???? ring; Table 2 and Fig. 3]. The dimeric pairs are piled up into columns along the b axis by C—H···O═C and C—H···OCH3 hydrogen bonds between R(or S)-enantiomers [C16—H16···O1ii = 2.47 Å and C15—H15···O3i = 2.50 Å; symmetry codes: (i) x, -y + 1/2, z + 1/2; (ii) x, y + 1, z; Table 2 and Fig. 4]. No other significant intermolecular interactions are observed in the structure. Therefore, the formation of the dimeric pairs of R- and S-enantiomers, piled up in a columnar fashion, apparently induces the stripe structure.
Several years ago, we reported the crystal structures of 1-aroylated naphthalene analogues, namely: (2,7-dimethoxynaphthalen-1-yl)(phenyl)methanone (or 1-benzoyl-2,7-dimethoxynaphthalene) (Kato et al., 2010), (II) (Fig. 5), and (2,7-dimethoxynaphthalen-1-yl)(4-fluorophenyl)methanone [or 1-(4-fluorobenzoyl)-2,7-dimethoxynaphthalene] (Watanabe et al., 2010), (III) (Fig. 6). The dihedral angles between the benzene and naphthalene rings become closer to 90° in the order of compound (II) [three conformers: 75.34 (7), 86.47 (7) and 76.55 (6)°], compound (III) [80.46 (4)°] and compound (I) [85.90 (5)°]. The order indicates that the internal steric repulsion in (I) is the largest in these three 1-aroylated naphthalene compounds. The nonfluorinated analogue, (II), forms an apparently different molecular packing (Fig. 7), whereas the fluorinated analogue, (III), has a packing similar to that of (I) (Fig. 8). Table 3 shows the nonbonding distances in the title compound, (I), the nonfluorinated analogue, (II), and the fluorinated analogue, (III).
In the crystal structure of (II), the three independent molecules have slightly different dihedral angles between the benzene and naphthalene rings (see above). Each of the three independent molecules is piled up via C—H···O═C hydrogen bonds between the benzene rings and the carbonyl groups to give columns [C34—H34···O6(x, y + 1, z - 1) = 2.41 Å and C54—H54···O9(x, y + 1, z - 1) = 2.58 Å; Fig. 9]. The three types of column are connected to each other by two C—H···OCH3 hydrogen bonds [C36—H36···O2(x, y, z) = 2.56 Å and C56—H56···O5(x, y + 1, z - 1) = 2.54 Å] and one C—H···O═C hydrogen bond [C52—H52···O3(x, y + 1, z - 1) = 2.46 Å] (Fig. 10). Two independent molecules, connected by a C—H···O═C hydrogen bond, are the same enantiomer, and the third independent molecule, linked to the other two by two C—H···OCH3 hydrogen bonds, is the counterpart enantiomer, viz. the intercolumnar C—H···O═C interactions connect columns of identical enantiomers to each other.
In the crystal structure of (III), a stripe structure composed of R- and S-enantiomeric columns is observed, as in (I) (Fig. 8). Intracolumnar C—H···O═C hydrogen bonds [C14—H14···O1(x, y + 1, z) = 2.35 Å; Fig. 11] between R(S)-isomers, and intercolumnar C—H···F hydrogen bonds between R- and S-isomers [C19—H19···F1(-x + 2, -y + 2, -z + 1) = 2.61 Å; Fig. 12] are also observed. However, the R···S dimeric pair has no π–π interactions, unlike (I).
Consequently, (I) and (III) form stripe structures in their crystalline state. A pair of C—H···F hydrogen bonds is observed between the R- and S-enantiomers, and C—H···O═C hydrogen bonds exist between the R(S)-isomers. No other significant interactions are observed in the structures. Under these circumstances, the stripe structure is apparently induced by the formation of dimeric pairs of R- and S-enantiomers piled up in a columnar fashion. The pair of C—H···F hydrogen bonds plays a fundamental role in the stabilization of the dimeric pair of R- and S-enantiomers. Also, the co-existence of C—H···F hydrogen bonds with C—H···O═C hydrogen bonds restricts the spatial organization of the molecular structurem without affording independent molecules as in (II).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2010); program(s) used to solve structure: SIR2004 (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C19H15FO3 | F(000) = 648 |
Mr = 310.31 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/c | Cu Kα radiation, λ = 1.54187 Å |
Hall symbol: -P 2ybc | Cell parameters from 20127 reflections |
a = 11.0057 (2) Å | θ = 4.1–68.2° |
b = 7.64555 (14) Å | µ = 0.82 mm−1 |
c = 18.6746 (3) Å | T = 193 K |
β = 103.671 (1)° | Block, colourless |
V = 1526.85 (5) Å3 | 0.80 × 0.60 × 0.35 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 2785 independent reflections |
Radiation source: fine-focus sealed tube | 2335 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.043 |
Detector resolution: 10.000 pixels mm-1 | θmax = 68.2°, θmin = 4.1° |
ω scans | h = −13→13 |
Absorption correction: numerical (NUMABS; Higashi, 1999) | k = −9→8 |
Tmin = 0.560, Tmax = 0.762 | l = −22→22 |
23103 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.036 | H-atom parameters constrained |
wR(F2) = 0.101 | w = 1/[σ2(Fo2) + (0.0576P)2 + 0.1828P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2785 reflections | Δρmax = 0.19 e Å−3 |
211 parameters | Δρmin = −0.14 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0090 (6) |
C19H15FO3 | V = 1526.85 (5) Å3 |
Mr = 310.31 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 11.0057 (2) Å | µ = 0.82 mm−1 |
b = 7.64555 (14) Å | T = 193 K |
c = 18.6746 (3) Å | 0.80 × 0.60 × 0.35 mm |
β = 103.671 (1)° |
Rigaku R-AXIS RAPID diffractometer | 2785 independent reflections |
Absorption correction: numerical (NUMABS; Higashi, 1999) | 2335 reflections with I > 2σ(I) |
Tmin = 0.560, Tmax = 0.762 | Rint = 0.043 |
23103 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
2785 reflections | Δρmin = −0.14 e Å−3 |
211 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 | ||
F1 | 0.45548 (8) | 0.03160 (13) | 0.12994 (4) | 0.0599 (3) | |
O1 | 0.01902 (9) | −0.12098 (15) | −0.09759 (6) | 0.0544 (3) | |
O2 | 0.41064 (10) | −0.11752 (14) | −0.35964 (5) | 0.0537 (3) | |
O3 | 0.30109 (8) | −0.30703 (13) | −0.10728 (5) | 0.0462 (3) | |
C1 | 0.14582 (11) | −0.12474 (17) | −0.18076 (7) | 0.0364 (3) | |
C2 | 0.02776 (12) | −0.10296 (18) | −0.16903 (8) | 0.0431 (3) | |
C3 | −0.07532 (12) | −0.0672 (2) | −0.22790 (9) | 0.0509 (4) | |
H3 | −0.1561 | −0.0506 | −0.2191 | 0.061* | |
C4 | −0.05808 (13) | −0.05659 (19) | −0.29775 (9) | 0.0509 (4) | |
H4 | −0.1278 | −0.0323 | −0.3374 | 0.061* | |
C5 | 0.07923 (16) | −0.0708 (2) | −0.38521 (8) | 0.0552 (4) | |
H5 | 0.0093 | −0.0527 | −0.4255 | 0.066* | |
C6 | 0.19403 (16) | −0.0865 (2) | −0.39830 (8) | 0.0558 (4) | |
H6 | 0.2042 | −0.0803 | −0.4474 | 0.067* | |
C7 | 0.29944 (14) | −0.11226 (18) | −0.33908 (8) | 0.0449 (3) | |
C8 | 0.28575 (12) | −0.12826 (17) | −0.26824 (7) | 0.0387 (3) | |
H8 | 0.3569 | −0.1491 | −0.2291 | 0.046* | |
C9 | 0.16555 (12) | −0.11380 (16) | −0.25330 (7) | 0.0369 (3) | |
C10 | 0.06016 (13) | −0.08062 (18) | −0.31260 (8) | 0.0444 (3) | |
C11 | 0.25103 (11) | −0.16428 (17) | −0.11525 (6) | 0.0342 (3) | |
C12 | 0.29267 (10) | −0.02169 (17) | −0.06054 (6) | 0.0329 (3) | |
C13 | 0.35546 (11) | −0.06424 (18) | 0.01137 (7) | 0.0365 (3) | |
H13 | 0.3691 | −0.1826 | 0.0266 | 0.044* | |
C14 | 0.39675 (11) | 0.0711 (2) | 0.05924 (7) | 0.0403 (3) | |
C15 | 0.38375 (12) | 0.2443 (2) | 0.03965 (7) | 0.0447 (3) | |
H15 | 0.4159 | 0.3338 | 0.0743 | 0.054* | |
C16 | 0.32245 (13) | 0.28471 (19) | −0.03199 (8) | 0.0460 (3) | |
H16 | 0.3128 | 0.4034 | −0.0473 | 0.055* | |
C17 | 0.27496 (12) | 0.15229 (18) | −0.08157 (7) | 0.0397 (3) | |
H17 | 0.2301 | 0.1809 | −0.1301 | 0.048* | |
C18 | −0.10079 (14) | −0.0980 (3) | −0.08165 (11) | 0.0645 (5) | |
H18A | −0.1309 | 0.0209 | −0.0951 | 0.077* | |
H18B | −0.0937 | −0.1165 | −0.0289 | 0.077* | |
H18C | −0.1599 | −0.1828 | −0.1100 | 0.077* | |
C19 | 0.52317 (14) | −0.1292 (2) | −0.30333 (8) | 0.0548 (4) | |
H19A | 0.5265 | −0.0328 | −0.2684 | 0.066* | |
H19B | 0.5953 | −0.1219 | −0.3255 | 0.066* | |
H19C | 0.5251 | −0.2409 | −0.2774 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0617 (5) | 0.0772 (7) | 0.0330 (4) | 0.0012 (4) | −0.0041 (4) | −0.0020 (4) |
O1 | 0.0358 (5) | 0.0747 (8) | 0.0550 (6) | −0.0034 (5) | 0.0151 (4) | −0.0050 (5) |
O2 | 0.0659 (7) | 0.0591 (7) | 0.0387 (5) | 0.0010 (5) | 0.0176 (5) | 0.0001 (5) |
O3 | 0.0456 (5) | 0.0382 (5) | 0.0484 (6) | 0.0036 (4) | −0.0014 (4) | −0.0004 (4) |
C1 | 0.0327 (6) | 0.0341 (7) | 0.0386 (7) | −0.0013 (5) | 0.0009 (5) | −0.0018 (5) |
C2 | 0.0358 (7) | 0.0415 (8) | 0.0490 (8) | −0.0021 (6) | 0.0044 (6) | −0.0052 (6) |
C3 | 0.0303 (7) | 0.0463 (9) | 0.0696 (10) | 0.0003 (6) | −0.0011 (6) | −0.0048 (7) |
C4 | 0.0422 (7) | 0.0398 (8) | 0.0577 (9) | 0.0006 (6) | −0.0144 (6) | −0.0003 (7) |
C5 | 0.0646 (10) | 0.0492 (9) | 0.0393 (8) | −0.0004 (7) | −0.0130 (7) | 0.0042 (7) |
C6 | 0.0739 (11) | 0.0547 (10) | 0.0337 (7) | −0.0023 (8) | 0.0025 (7) | 0.0030 (7) |
C7 | 0.0573 (8) | 0.0383 (7) | 0.0377 (7) | −0.0018 (6) | 0.0085 (6) | −0.0003 (6) |
C8 | 0.0435 (7) | 0.0349 (7) | 0.0339 (7) | −0.0001 (5) | 0.0016 (5) | 0.0000 (5) |
C9 | 0.0396 (7) | 0.0289 (7) | 0.0372 (7) | −0.0023 (5) | −0.0008 (5) | −0.0011 (5) |
C10 | 0.0462 (8) | 0.0346 (7) | 0.0432 (7) | −0.0017 (6) | −0.0077 (6) | 0.0012 (6) |
C11 | 0.0308 (6) | 0.0365 (7) | 0.0352 (6) | −0.0015 (5) | 0.0074 (5) | 0.0031 (5) |
C12 | 0.0268 (5) | 0.0399 (7) | 0.0318 (6) | −0.0008 (5) | 0.0064 (5) | 0.0012 (5) |
C13 | 0.0305 (6) | 0.0438 (8) | 0.0351 (7) | 0.0007 (5) | 0.0074 (5) | 0.0037 (5) |
C14 | 0.0312 (6) | 0.0591 (9) | 0.0295 (6) | 0.0007 (6) | 0.0045 (5) | −0.0018 (6) |
C15 | 0.0374 (7) | 0.0513 (9) | 0.0445 (8) | −0.0038 (6) | 0.0079 (6) | −0.0130 (6) |
C16 | 0.0493 (8) | 0.0393 (8) | 0.0475 (8) | 0.0000 (6) | 0.0075 (6) | −0.0016 (6) |
C17 | 0.0402 (7) | 0.0403 (8) | 0.0358 (7) | 0.0005 (6) | 0.0036 (5) | 0.0017 (6) |
C18 | 0.0429 (8) | 0.0728 (12) | 0.0842 (12) | −0.0041 (8) | 0.0278 (8) | −0.0094 (9) |
C19 | 0.0557 (9) | 0.0645 (10) | 0.0469 (8) | −0.0002 (7) | 0.0178 (7) | −0.0039 (7) |
F1—C14 | 1.3597 (14) | C8—C9 | 1.4193 (18) |
O1—C2 | 1.3670 (17) | C8—H8 | 0.9500 |
O1—C18 | 1.4296 (16) | C9—C10 | 1.4243 (18) |
O2—C7 | 1.3671 (17) | C11—C12 | 1.4902 (17) |
O2—C19 | 1.4254 (18) | C12—C17 | 1.3876 (18) |
O3—C11 | 1.2158 (15) | C12—C13 | 1.3957 (17) |
C1—C2 | 1.3779 (18) | C13—C14 | 1.3726 (19) |
C1—C9 | 1.4242 (18) | C13—H13 | 0.9500 |
C1—C11 | 1.5031 (17) | C14—C15 | 1.373 (2) |
C2—C3 | 1.408 (2) | C15—C16 | 1.3834 (19) |
C3—C4 | 1.364 (2) | C15—H15 | 0.9500 |
C3—H3 | 0.9500 | C16—C17 | 1.3881 (19) |
C4—C10 | 1.405 (2) | C16—H16 | 0.9500 |
C4—H4 | 0.9500 | C17—H17 | 0.9500 |
C5—C6 | 1.348 (2) | C18—H18A | 0.9800 |
C5—C10 | 1.422 (2) | C18—H18B | 0.9800 |
C5—H5 | 0.9500 | C18—H18C | 0.9800 |
C6—C7 | 1.415 (2) | C19—H19A | 0.9800 |
C6—H6 | 0.9500 | C19—H19B | 0.9800 |
C7—C8 | 1.3720 (19) | C19—H19C | 0.9800 |
C2—O1—C18 | 118.16 (12) | O3—C11—C1 | 121.32 (11) |
C7—O2—C19 | 118.29 (10) | C12—C11—C1 | 117.63 (11) |
C2—C1—C9 | 120.37 (12) | C17—C12—C13 | 120.01 (12) |
C2—C1—C11 | 117.96 (12) | C17—C12—C11 | 120.49 (11) |
C9—C1—C11 | 121.65 (11) | C13—C12—C11 | 119.42 (11) |
O1—C2—C1 | 115.43 (12) | C14—C13—C12 | 117.60 (13) |
O1—C2—C3 | 123.52 (13) | C14—C13—H13 | 121.2 |
C1—C2—C3 | 121.04 (13) | C12—C13—H13 | 121.2 |
C4—C3—C2 | 119.33 (13) | F1—C14—C15 | 117.95 (12) |
C4—C3—H3 | 120.3 | F1—C14—C13 | 118.24 (13) |
C2—C3—H3 | 120.3 | C15—C14—C13 | 123.80 (12) |
C3—C4—C10 | 121.70 (13) | C14—C15—C16 | 117.99 (13) |
C3—C4—H4 | 119.1 | C14—C15—H15 | 121.0 |
C10—C4—H4 | 119.1 | C16—C15—H15 | 121.0 |
C6—C5—C10 | 121.60 (13) | C15—C16—C17 | 120.20 (13) |
C6—C5—H5 | 119.2 | C15—C16—H16 | 119.9 |
C10—C5—H5 | 119.2 | C17—C16—H16 | 119.9 |
C5—C6—C7 | 120.09 (14) | C12—C17—C16 | 120.32 (12) |
C5—C6—H6 | 120.0 | C12—C17—H17 | 119.8 |
C7—C6—H6 | 120.0 | C16—C17—H17 | 119.8 |
O2—C7—C8 | 125.30 (13) | O1—C18—H18A | 109.5 |
O2—C7—C6 | 114.06 (12) | O1—C18—H18B | 109.5 |
C8—C7—C6 | 120.64 (14) | H18A—C18—H18B | 109.5 |
C7—C8—C9 | 120.16 (12) | O1—C18—H18C | 109.5 |
C7—C8—H8 | 119.9 | H18A—C18—H18C | 109.5 |
C9—C8—H8 | 119.9 | H18B—C18—H18C | 109.5 |
C8—C9—C1 | 122.75 (11) | O2—C19—H19A | 109.5 |
C8—C9—C10 | 119.12 (12) | O2—C19—H19B | 109.5 |
C1—C9—C10 | 118.09 (12) | H19A—C19—H19B | 109.5 |
C4—C10—C5 | 122.23 (13) | O2—C19—H19C | 109.5 |
C4—C10—C9 | 119.46 (13) | H19A—C19—H19C | 109.5 |
C5—C10—C9 | 118.30 (13) | H19B—C19—H19C | 109.5 |
O3—C11—C12 | 121.05 (11) | ||
C18—O1—C2—C1 | 179.33 (13) | C6—C5—C10—C4 | 177.05 (14) |
C18—O1—C2—C3 | −1.6 (2) | C6—C5—C10—C9 | −2.1 (2) |
C9—C1—C2—O1 | 178.24 (11) | C8—C9—C10—C4 | −176.53 (12) |
C11—C1—C2—O1 | −0.32 (18) | C1—C9—C10—C4 | 1.23 (19) |
C9—C1—C2—C3 | −0.9 (2) | C8—C9—C10—C5 | 2.67 (19) |
C11—C1—C2—C3 | −179.45 (12) | C1—C9—C10—C5 | −179.57 (12) |
O1—C2—C3—C4 | −178.06 (13) | C2—C1—C11—O3 | 110.35 (14) |
C1—C2—C3—C4 | 1.0 (2) | C9—C1—C11—O3 | −68.19 (17) |
C2—C3—C4—C10 | 0.0 (2) | C2—C1—C11—C12 | −70.12 (15) |
C10—C5—C6—C7 | −0.5 (2) | C9—C1—C11—C12 | 111.34 (13) |
C19—O2—C7—C8 | −4.3 (2) | O3—C11—C12—C17 | 153.87 (12) |
C19—O2—C7—C6 | 175.16 (13) | C1—C11—C12—C17 | −25.67 (16) |
C5—C6—C7—O2 | −176.97 (14) | O3—C11—C12—C13 | −22.92 (17) |
C5—C6—C7—C8 | 2.5 (2) | C1—C11—C12—C13 | 157.54 (11) |
O2—C7—C8—C9 | 177.52 (12) | C17—C12—C13—C14 | 0.58 (17) |
C6—C7—C8—C9 | −1.9 (2) | C11—C12—C13—C14 | 177.39 (10) |
C7—C8—C9—C1 | −178.35 (12) | C12—C13—C14—F1 | 178.48 (10) |
C7—C8—C9—C10 | −0.71 (19) | C12—C13—C14—C15 | −2.44 (18) |
C2—C1—C9—C8 | 177.44 (12) | F1—C14—C15—C16 | −179.10 (11) |
C11—C1—C9—C8 | −4.06 (19) | C13—C14—C15—C16 | 1.82 (19) |
C2—C1—C9—C10 | −0.23 (19) | C14—C15—C16—C17 | 0.69 (19) |
C11—C1—C9—C10 | 178.28 (12) | C13—C12—C17—C16 | 1.79 (18) |
C3—C4—C10—C5 | 179.68 (14) | C11—C12—C17—C16 | −174.97 (11) |
C3—C4—C10—C9 | −1.2 (2) | C15—C16—C17—C12 | −2.5 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···F1i | 0.98 | 2.55 | 3.2767 (16) | 131 |
C15—H15···O2ii | 0.95 | 2.50 | 3.3917 (18) | 156 |
C16—H16···O3iii | 0.95 | 2.47 | 3.4086 (18) | 169 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, −y+1/2, z+1/2; (iii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C19H15FO3 |
Mr | 310.31 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 193 |
a, b, c (Å) | 11.0057 (2), 7.64555 (14), 18.6746 (3) |
β (°) | 103.671 (1) |
V (Å3) | 1526.85 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.82 |
Crystal size (mm) | 0.80 × 0.60 × 0.35 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.560, 0.762 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23103, 2785, 2335 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.602 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.101, 1.04 |
No. of reflections | 2785 |
No. of parameters | 211 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.14 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku, 2010), SIR2004 (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
C19—H19A···F1i | 0.98 | 2.55 | 3.2767 (16) | 131 |
C15—H15···O2ii | 0.95 | 2.50 | 3.3917 (18) | 156 |
C16—H16···O3iii | 0.95 | 2.47 | 3.4086 (18) | 169 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x, −y+1/2, z+1/2; (iii) x, y+1, z. |
(I) | (II) | (III) | ||
Intracolumnar (between the same isomers) | ||||
C—H···O═C | C16—H16···O1iii | 2.47 | ||
C34—H34···O6 | 2.41 | |||
C54—H54···O9 | 2.58 | |||
C14—H14···O1 | 2.35 | |||
Intercolumnar (between the R and S isomer) | ||||
C—H···F | C19—H19A···F1i | 2.55 | ||
C19—H19B···F1 | 2.61 | |||
C—H···O | C15—H15···O3ii | 2.50 | ||
C56—H56A···O5 | 2.54 | |||
C36—H36···O2 | 2.56 | |||
π–π | Cg3···Cg3 | 3.89 | ||
Intercolumnar (between the same isomers) | ||||
C—H···O═C | C52—H52···O3 | 2.46 | ||
C19—H19B···O9 | 2.59 |
Symmetry codes: (i) -x + 1, -y, -z; (ii) x, -y + 1/2, z + 1/2; (iii) x, y + 1, z. |