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In the mol­ecule of (2,7-di­meth­oxy­naphthalen-1-yl)(3-fluoro­phenyl)methanone, C19H15FO3, (I), the dihedral angle between the plane of the naphthalene ring system and that of the benzene ring is 85.90 (5)°. The mol­ecules exhibit axial chirality, with either an R- or an S-stereogenic axis. In the crystal structure, each enantio­mer is stacked into a columnar structure and the columns are arranged alternately to form a stripe structure. A pair of (meth­oxy)C-H...F hydrogen bonds and [pi]-[pi] inter­actions between the benzene rings of the aroyl groups link an R- and an S-isomer to form a dimeric pair. These dimeric pairs are piled up in a columnar fashion through (benzene)C-H...O=C and (benzene)C-H...OCH3 hydrogen bonds. The analogous 1-benzoyl­ated compound, namely (2,7-di­meth­oxy­naphthalen-1-yl)(phenyl)methanone [Kato et al. (2010). Acta Cryst. E66, o2659], (II), affords three independent mol­ecules having slightly different dihedral angles between the benzene and naphthalene rings. The three independent mol­ecules form separate columns and the three types of column are connected to each other via two C-H...OCH3 hydrogen bonds and one C-H...O=C hydrogen bond. Two of the three columns are formed by the same enantio­meric isomer, whereas the remaining column consists of the counterpart isomer. In the case of the fluorinated 1-benzoyl­ated naphthalene analogue, namely (2,7-di­meth­oxy­naphthalen-1-yl)(4-fluoro­phenyl)methanone [Watanabe et al. (2011). Acta Cryst. E67, o1466], (III), the mol­ecular packing is similar to that of (I), i.e. it consists of stripes of R- and S-enantio­meric columns. A pair of C-H...F hydrogen bonds between R- and S-isomers, and C-H...O=C hydrogen bonds between R(or S)-isomers, are also observed. Con­sequently, the stripe structure is apparently induced by the formation of R...S dimeric pairs stacked in a columnar fashion. The pair of C-H...F hydrogen bonds effectively stabilizes the dimeric pair of R- and S-enantio­mers. In addition, the co-existence of C-H...F and C-H...O=C hydrogen bonds makes possible the formation of a structure with just one independent mol­ecule.

Supporting information

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Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229615005720/yf3082sup1.cif
Contains datablocks I, global

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Structure factor file (CIF format) https://doi.org/10.1107/S2053229615005720/yf3082Isup2.hkl
Contains datablock I

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CCDC reference: 1055291

Introduction top

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 ππ stacking. Instead, it affords the opportunity to reveal normally hidden nonbonding inter­molecular inter­actions. We have recently reported the relationship between (aromatic)C—H···OC 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.

Experimental top

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.

Synthesis and crystallization top

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).

Spectroscopic and analytical data top

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 (CO), 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.

Refinement top

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.

Results and discussion top

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—(CO)—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 ππ 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···OC 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···OC 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···OC hydrogen bond [C52—H52···O3(x, y + 1, z - 1) = 2.46 Å] (Fig. 10). Two independent molecules, connected by a C—H···OC 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···OC 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···OC 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 ππ 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···OC 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···OC hydrogen bonds restricts the spatial organization of the molecular structurem without affording independent molecules as in (II).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The stripe structure of the S-isomeric column and the R-isomeric column in the crystal structure of (I), showing (a) the molecular alignment viewed down the a axis, (b) the molecular alignment viewed along the c axis and (c) the molecular alignment viewed down the b axis.
[Figure 3] Fig. 3. A partial view of the crystal packing of (I), showing the intercolumnar C—H···F hydrogen bonds and ππ interaction [dashed lines; see Table 2 for details; symmetry code: (i) -x + 1, -y, -z].
[Figure 4] Fig. 4. A partial view of the crystal packing of (I), showing the intracolumnar C—H···OCH3 and C—H···OC hydrogen bonds [dashed lines; see Table 2 for details; symmetry codes: (ii) x, -y + 1/2, z + 1/2; (iii) x, y + 1, z.]
[Figure 5] Fig. 5. The molecular structures of the independent molecules of (II), (a) molecule A, (b) molecule B and (c) molecule C, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 6] Fig. 6. The molecular structure of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 7] Fig. 7. The column structure of the fluoro-free analogue, (II), showing the molecular alignment viewed down the b axis. The three independent molecules are shown as different colours: molecule A is pink, molecule B is pale blue and molecule C is yellow. [Diagram very fuzzy; revise?]
[Figure 8] Fig. 8. The stripe structure of the fluoro-bearing analogue, (III), showing the molecular alignment viewed down the b axis. [Diagram very fuzzy; revise?]
[Figure 9] Fig. 9. A partial view of the crystal packing of the fluoro-free analogue, (II), showing the intracolumnar C—H···OC hydrogen bonds (dashed lines; see Table 3 for details).
[Figure 10] Fig. 10. A partial view of the crystal packing of the fluoro-free analogue, (II), showing the intermolecular C—H···OCH3 hydrogen bonds (black dotted lines) and C—H···OC hydrogen bond (green double-dotted line) between independent molecules A, B and C (see Table 3 for details). [No green line visible - please send revised plot as necessary]
[Figure 11] Fig. 11. A partial view of the crystal packing of the fluoro-bearing analogue, (III), showing the intracolumnar C—H···OC interaction (dashed lines; see Table 3 for details).
[Figure 12] Fig. 12. A partial view of the crystal packing of the fluoro-bearing analogue, (III), showing the intercolumnar C—H···F interaction (dashed lines; see Table 3 for details).
(2,7-Dimethoxynaphthalen-1-yl)(3-fluorophenyl)methanone top
Crystal data top
C19H15FO3F(000) = 648
Mr = 310.31Dx = 1.350 Mg m3
Monoclinic, P21/cCu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ybcCell parameters from 20127 reflections
a = 11.0057 (2) Åθ = 4.1–68.2°
b = 7.64555 (14) ŵ = 0.82 mm1
c = 18.6746 (3) ÅT = 193 K
β = 103.671 (1)°Block, colourless
V = 1526.85 (5) Å30.80 × 0.60 × 0.35 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2785 independent reflections
Radiation source: fine-focus sealed tube2335 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.043
Detector resolution: 10.000 pixels mm-1θmax = 68.2°, θmin = 4.1°
ω scansh = 1313
Absorption correction: numerical
(NUMABS; Higashi, 1999)
k = 98
Tmin = 0.560, Tmax = 0.762l = 2222
23103 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-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 reflectionsΔρmax = 0.19 e Å3
211 parametersΔρmin = 0.14 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0090 (6)
Crystal data top
C19H15FO3V = 1526.85 (5) Å3
Mr = 310.31Z = 4
Monoclinic, P21/cCu Kα radiation
a = 11.0057 (2) ŵ = 0.82 mm1
b = 7.64555 (14) ÅT = 193 K
c = 18.6746 (3) Å0.80 × 0.60 × 0.35 mm
β = 103.671 (1)°
Data collection top
Rigaku R-AXIS RAPID
diffractometer
2785 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)
2335 reflections with I > 2σ(I)
Tmin = 0.560, Tmax = 0.762Rint = 0.043
23103 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.101H-atom parameters constrained
S = 1.04Δρmax = 0.19 e Å3
2785 reflectionsΔρmin = 0.14 e Å3
211 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
F10.45548 (8)0.03160 (13)0.12994 (4)0.0599 (3)
O10.01902 (9)0.12098 (15)0.09759 (6)0.0544 (3)
O20.41064 (10)0.11752 (14)0.35964 (5)0.0537 (3)
O30.30109 (8)0.30703 (13)0.10728 (5)0.0462 (3)
C10.14582 (11)0.12474 (17)0.18076 (7)0.0364 (3)
C20.02776 (12)0.10296 (18)0.16903 (8)0.0431 (3)
C30.07532 (12)0.0672 (2)0.22790 (9)0.0509 (4)
H30.15610.05060.21910.061*
C40.05808 (13)0.05659 (19)0.29775 (9)0.0509 (4)
H40.12780.03230.33740.061*
C50.07923 (16)0.0708 (2)0.38521 (8)0.0552 (4)
H50.00930.05270.42550.066*
C60.19403 (16)0.0865 (2)0.39830 (8)0.0558 (4)
H60.20420.08030.44740.067*
C70.29944 (14)0.11226 (18)0.33908 (8)0.0449 (3)
C80.28575 (12)0.12826 (17)0.26824 (7)0.0387 (3)
H80.35690.14910.22910.046*
C90.16555 (12)0.11380 (16)0.25330 (7)0.0369 (3)
C100.06016 (13)0.08062 (18)0.31260 (8)0.0444 (3)
C110.25103 (11)0.16428 (17)0.11525 (6)0.0342 (3)
C120.29267 (10)0.02169 (17)0.06054 (6)0.0329 (3)
C130.35546 (11)0.06424 (18)0.01137 (7)0.0365 (3)
H130.36910.18260.02660.044*
C140.39675 (11)0.0711 (2)0.05924 (7)0.0403 (3)
C150.38375 (12)0.2443 (2)0.03965 (7)0.0447 (3)
H150.41590.33380.07430.054*
C160.32245 (13)0.28471 (19)0.03199 (8)0.0460 (3)
H160.31280.40340.04730.055*
C170.27496 (12)0.15229 (18)0.08157 (7)0.0397 (3)
H170.23010.18090.13010.048*
C180.10079 (14)0.0980 (3)0.08165 (11)0.0645 (5)
H18A0.13090.02090.09510.077*
H18B0.09370.11650.02890.077*
H18C0.15990.18280.11000.077*
C190.52317 (14)0.1292 (2)0.30333 (8)0.0548 (4)
H19A0.52650.03280.26840.066*
H19B0.59530.12190.32550.066*
H19C0.52510.24090.27740.066*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
F10.0617 (5)0.0772 (7)0.0330 (4)0.0012 (4)0.0041 (4)0.0020 (4)
O10.0358 (5)0.0747 (8)0.0550 (6)0.0034 (5)0.0151 (4)0.0050 (5)
O20.0659 (7)0.0591 (7)0.0387 (5)0.0010 (5)0.0176 (5)0.0001 (5)
O30.0456 (5)0.0382 (5)0.0484 (6)0.0036 (4)0.0014 (4)0.0004 (4)
C10.0327 (6)0.0341 (7)0.0386 (7)0.0013 (5)0.0009 (5)0.0018 (5)
C20.0358 (7)0.0415 (8)0.0490 (8)0.0021 (6)0.0044 (6)0.0052 (6)
C30.0303 (7)0.0463 (9)0.0696 (10)0.0003 (6)0.0011 (6)0.0048 (7)
C40.0422 (7)0.0398 (8)0.0577 (9)0.0006 (6)0.0144 (6)0.0003 (7)
C50.0646 (10)0.0492 (9)0.0393 (8)0.0004 (7)0.0130 (7)0.0042 (7)
C60.0739 (11)0.0547 (10)0.0337 (7)0.0023 (8)0.0025 (7)0.0030 (7)
C70.0573 (8)0.0383 (7)0.0377 (7)0.0018 (6)0.0085 (6)0.0003 (6)
C80.0435 (7)0.0349 (7)0.0339 (7)0.0001 (5)0.0016 (5)0.0000 (5)
C90.0396 (7)0.0289 (7)0.0372 (7)0.0023 (5)0.0008 (5)0.0011 (5)
C100.0462 (8)0.0346 (7)0.0432 (7)0.0017 (6)0.0077 (6)0.0012 (6)
C110.0308 (6)0.0365 (7)0.0352 (6)0.0015 (5)0.0074 (5)0.0031 (5)
C120.0268 (5)0.0399 (7)0.0318 (6)0.0008 (5)0.0064 (5)0.0012 (5)
C130.0305 (6)0.0438 (8)0.0351 (7)0.0007 (5)0.0074 (5)0.0037 (5)
C140.0312 (6)0.0591 (9)0.0295 (6)0.0007 (6)0.0045 (5)0.0018 (6)
C150.0374 (7)0.0513 (9)0.0445 (8)0.0038 (6)0.0079 (6)0.0130 (6)
C160.0493 (8)0.0393 (8)0.0475 (8)0.0000 (6)0.0075 (6)0.0016 (6)
C170.0402 (7)0.0403 (8)0.0358 (7)0.0005 (6)0.0036 (5)0.0017 (6)
C180.0429 (8)0.0728 (12)0.0842 (12)0.0041 (8)0.0278 (8)0.0094 (9)
C190.0557 (9)0.0645 (10)0.0469 (8)0.0002 (7)0.0178 (7)0.0039 (7)
Geometric parameters (Å, º) top
F1—C141.3597 (14)C8—C91.4193 (18)
O1—C21.3670 (17)C8—H80.9500
O1—C181.4296 (16)C9—C101.4243 (18)
O2—C71.3671 (17)C11—C121.4902 (17)
O2—C191.4254 (18)C12—C171.3876 (18)
O3—C111.2158 (15)C12—C131.3957 (17)
C1—C21.3779 (18)C13—C141.3726 (19)
C1—C91.4242 (18)C13—H130.9500
C1—C111.5031 (17)C14—C151.373 (2)
C2—C31.408 (2)C15—C161.3834 (19)
C3—C41.364 (2)C15—H150.9500
C3—H30.9500C16—C171.3881 (19)
C4—C101.405 (2)C16—H160.9500
C4—H40.9500C17—H170.9500
C5—C61.348 (2)C18—H18A0.9800
C5—C101.422 (2)C18—H18B0.9800
C5—H50.9500C18—H18C0.9800
C6—C71.415 (2)C19—H19A0.9800
C6—H60.9500C19—H19B0.9800
C7—C81.3720 (19)C19—H19C0.9800
C2—O1—C18118.16 (12)O3—C11—C1121.32 (11)
C7—O2—C19118.29 (10)C12—C11—C1117.63 (11)
C2—C1—C9120.37 (12)C17—C12—C13120.01 (12)
C2—C1—C11117.96 (12)C17—C12—C11120.49 (11)
C9—C1—C11121.65 (11)C13—C12—C11119.42 (11)
O1—C2—C1115.43 (12)C14—C13—C12117.60 (13)
O1—C2—C3123.52 (13)C14—C13—H13121.2
C1—C2—C3121.04 (13)C12—C13—H13121.2
C4—C3—C2119.33 (13)F1—C14—C15117.95 (12)
C4—C3—H3120.3F1—C14—C13118.24 (13)
C2—C3—H3120.3C15—C14—C13123.80 (12)
C3—C4—C10121.70 (13)C14—C15—C16117.99 (13)
C3—C4—H4119.1C14—C15—H15121.0
C10—C4—H4119.1C16—C15—H15121.0
C6—C5—C10121.60 (13)C15—C16—C17120.20 (13)
C6—C5—H5119.2C15—C16—H16119.9
C10—C5—H5119.2C17—C16—H16119.9
C5—C6—C7120.09 (14)C12—C17—C16120.32 (12)
C5—C6—H6120.0C12—C17—H17119.8
C7—C6—H6120.0C16—C17—H17119.8
O2—C7—C8125.30 (13)O1—C18—H18A109.5
O2—C7—C6114.06 (12)O1—C18—H18B109.5
C8—C7—C6120.64 (14)H18A—C18—H18B109.5
C7—C8—C9120.16 (12)O1—C18—H18C109.5
C7—C8—H8119.9H18A—C18—H18C109.5
C9—C8—H8119.9H18B—C18—H18C109.5
C8—C9—C1122.75 (11)O2—C19—H19A109.5
C8—C9—C10119.12 (12)O2—C19—H19B109.5
C1—C9—C10118.09 (12)H19A—C19—H19B109.5
C4—C10—C5122.23 (13)O2—C19—H19C109.5
C4—C10—C9119.46 (13)H19A—C19—H19C109.5
C5—C10—C9118.30 (13)H19B—C19—H19C109.5
O3—C11—C12121.05 (11)
C18—O1—C2—C1179.33 (13)C6—C5—C10—C4177.05 (14)
C18—O1—C2—C31.6 (2)C6—C5—C10—C92.1 (2)
C9—C1—C2—O1178.24 (11)C8—C9—C10—C4176.53 (12)
C11—C1—C2—O10.32 (18)C1—C9—C10—C41.23 (19)
C9—C1—C2—C30.9 (2)C8—C9—C10—C52.67 (19)
C11—C1—C2—C3179.45 (12)C1—C9—C10—C5179.57 (12)
O1—C2—C3—C4178.06 (13)C2—C1—C11—O3110.35 (14)
C1—C2—C3—C41.0 (2)C9—C1—C11—O368.19 (17)
C2—C3—C4—C100.0 (2)C2—C1—C11—C1270.12 (15)
C10—C5—C6—C70.5 (2)C9—C1—C11—C12111.34 (13)
C19—O2—C7—C84.3 (2)O3—C11—C12—C17153.87 (12)
C19—O2—C7—C6175.16 (13)C1—C11—C12—C1725.67 (16)
C5—C6—C7—O2176.97 (14)O3—C11—C12—C1322.92 (17)
C5—C6—C7—C82.5 (2)C1—C11—C12—C13157.54 (11)
O2—C7—C8—C9177.52 (12)C17—C12—C13—C140.58 (17)
C6—C7—C8—C91.9 (2)C11—C12—C13—C14177.39 (10)
C7—C8—C9—C1178.35 (12)C12—C13—C14—F1178.48 (10)
C7—C8—C9—C100.71 (19)C12—C13—C14—C152.44 (18)
C2—C1—C9—C8177.44 (12)F1—C14—C15—C16179.10 (11)
C11—C1—C9—C84.06 (19)C13—C14—C15—C161.82 (19)
C2—C1—C9—C100.23 (19)C14—C15—C16—C170.69 (19)
C11—C1—C9—C10178.28 (12)C13—C12—C17—C161.79 (18)
C3—C4—C10—C5179.68 (14)C11—C12—C17—C16174.97 (11)
C3—C4—C10—C91.2 (2)C15—C16—C17—C122.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C19—H19A···F1i0.982.553.2767 (16)131
C15—H15···O2ii0.952.503.3917 (18)156
C16—H16···O3iii0.952.473.4086 (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 formulaC19H15FO3
Mr310.31
Crystal system, space groupMonoclinic, P21/c
Temperature (K)193
a, b, c (Å)11.0057 (2), 7.64555 (14), 18.6746 (3)
β (°) 103.671 (1)
V3)1526.85 (5)
Z4
Radiation typeCu Kα
µ (mm1)0.82
Crystal size (mm)0.80 × 0.60 × 0.35
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionNumerical
(NUMABS; Higashi, 1999)
Tmin, Tmax0.560, 0.762
No. of measured, independent and
observed [I > 2σ(I)] reflections
23103, 2785, 2335
Rint0.043
(sin θ/λ)max1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.101, 1.04
No. of reflections2785
No. of parameters211
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C19—H19A···F1i0.982.553.2767 (16)131
C15—H15···O2ii0.952.503.3917 (18)156
C16—H16···O3iii0.952.473.4086 (18)169
Symmetry codes: (i) x+1, y, z; (ii) x, y+1/2, z+1/2; (iii) x, y+1, z.
Intermolecular interactions (Å) for compounds (I), (II) and (III). top
(I)(II)(III)
Intracolumnar (between the same isomers)
C—H···OCC16—H16···O1iii2.47
C34—H34···O62.41
C54—H54···O92.58
C14—H14···O12.35
Intercolumnar (between the R and S isomer)
C—H···FC19—H19A···F1i2.55
C19—H19B···F12.61
C—H···OC15—H15···O3ii2.50
C56—H56A···O52.54
C36—H36···O22.56
ππCg3···Cg33.89
Intercolumnar (between the same isomers)
C—H···OCC52—H52···O32.46
C19—H19B···O92.59
Symmetry codes: (i) -x + 1, -y, -z; (ii) x, -y + 1/2, z + 1/2; (iii) x, y + 1, z.
 

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