Abstract
C26H20F2O4, monoclinic, P21/n (no. 14), a = 10.3707(2) Å, b = 12.0232(2) Å, c = 15.7744(3) Å, β = 90.907(1)°, V = 1966.65(6) Å3, Z = 4, R gt (F) = 0.0371, wR ref (F 2) = 0.1013, T = 193.15 K.
Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Colorless block |
| Size: | 0.35 × 0.20 × 0.10 mm |
| Wavelength: | Cu Kα radiation (1.54187 Å) |
| μ: | 0.93 mm−1 |
| Diffractometer, scan mode: | Rigaku R-AXIS RAPID, ω |
| θ max, completeness: | 68.2°, 99% |
| N(hkl)measured, N(hkl)unique, R int: | 36,085, 3566, 0.022 |
| Criterion for I obs, N(hkl)gt: | I obs > 2 σ(I obs), 3380 |
| N(param)refined: | 306 |
| Programs: | Rigaku [1, 2], SHELX [3, 4], ORTEP-III [5] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | U iso*/U eq |
|---|---|---|---|---|
| C1 | 0.98369 (13) | 0.31411 (11) | 0.17894 (8) | 0.0258 (3) |
| C2 | 1.07530 (13) | 0.39373 (12) | 0.19528 (9) | 0.0291 (3) |
| C3 | 1.20809 (14) | 0.36570 (12) | 0.18799 (9) | 0.0325 (3) |
| H3 | 1.2716 | 0.4212 | 0.1985 | 0.039* |
| C4 | 1.24645 (13) | 0.26042 (13) | 0.16621 (9) | 0.0322 (3) |
| H4 | 1.3357 | 0.2446 | 0.1607 | 0.039* |
| C5 | 1.17750 (13) | 0.06201 (12) | 0.13210 (9) | 0.0327 (3) |
| H5 | 1.2636 | 0.0361 | 0.1276 | 0.039* |
| C6 | 1.07676 (14) | −0.01071 (12) | 0.11942 (9) | 0.0320 (3) |
| H6 | 1.0950 | −0.0861 | 0.1063 | 0.038* |
| C7 | 0.94611 (13) | 0.02378 (11) | 0.12541 (9) | 0.0277 (3) |
| C8 | 0.92073 (12) | 0.13242 (11) | 0.14637 (8) | 0.0254 (3) |
| C9 | 1.02378 (13) | 0.20590 (11) | 0.15880 (8) | 0.0257 (3) |
| C10 | 1.15442 (13) | 0.17505 (12) | 0.15186 (9) | 0.0286 (3) |
| C11 | 0.83781 (13) | 0.31780 (11) | 0.18745 (8) | 0.0262 (3) |
| C12 | 0.76872 (13) | 0.40893 (11) | 0.13776 (9) | 0.0293 (3) |
| C13a | 0.63866 (14) | 0.43100 (13) | 0.14949 (10) | 0.0368 (3) |
| H13 | 0.5923 | 0.3858 | 0.1879 | 0.044* |
| C14 | 0.57381 (18) | 0.51553 (15) | 0.10789 (13) | 0.0512 (5) |
| H14 | 0.4852 | 0.5288 | 0.1183 | 0.061* |
| C15 | 0.6396 (2) | 0.58053 (15) | 0.05091 (13) | 0.0562 (5) |
| H15 | 0.5963 | 0.6391 | 0.0218 | 0.067* |
| C16 | 0.76816 (19) | 0.56041 (14) | 0.03620 (11) | 0.0473 (4) |
| H16 | 0.8133 | 0.6047 | −0.0034 | 0.057* |
| C17b | 0.83134 (16) | 0.47555 (12) | 0.07931 (10) | 0.0355 (3) |
| H17 | 0.9200 | 0.4625 | 0.0686 | 0.043* |
| C18 | 0.79264 (12) | 0.19123 (11) | 0.16029 (8) | 0.0256 (3) |
| C19 | 0.70565 (12) | 0.18631 (11) | 0.08137 (9) | 0.0254 (3) |
| C20 | 0.58102 (13) | 0.14344 (12) | 0.08438 (10) | 0.0318 (3) |
| H20 | 0.5483 | 0.1188 | 0.1371 | 0.038* |
| C21 | 0.50367 (15) | 0.13599 (13) | 0.01195 (11) | 0.0380 (4) |
| H21 | 0.4187 | 0.1070 | 0.0158 | 0.046* |
| C22 | 0.54886 (15) | 0.17018 (13) | −0.06560 (10) | 0.0392 (4) |
| H22 | 0.4957 | 0.1643 | −0.1150 | 0.047* |
| C23 | 0.67255 (15) | 0.21313 (12) | −0.07087 (9) | 0.0343 (3) |
| H23 | 0.7052 | 0.2375 | −0.1236 | 0.041* |
| C24 | 0.74705 (13) | 0.21969 (11) | 0.00204 (9) | 0.0277 (3) |
| C25 | 1.09837 (18) | 0.58978 (13) | 0.18453 (12) | 0.0463 (4) |
| H25A | 1.0631 | 0.6587 | 0.2079 | 0.056* |
| H25B | 1.1911 | 0.5862 | 0.1970 | 0.056* |
| H25C | 1.0839 | 0.5885 | 0.1230 | 0.056* |
| C26 | 0.86957 (15) | −0.15402 (12) | 0.07840 (10) | 0.0342 (3) |
| H26A | 0.7886 | −0.1954 | 0.0721 | 0.041* |
| H26B | 0.9098 | −0.1464 | 0.0229 | 0.041* |
| H26C | 0.9280 | −0.1942 | 0.1170 | 0.041* |
| F1Ab | 0.57062 (9) | 0.36665 (9) | 0.20276 (7) | 0.0457 (3) |
| F1Ba | 0.9303 (15) | 0.4543 (14) | 0.0459 (9) | 0.043 (4) |
| F2 | 0.86876 (8) | 0.26034 (7) | −0.00543 (5) | 0.0346 (2) |
| O1 | 0.81215 (10) | 0.32802 (10) | 0.27618 (6) | 0.0338 (2) |
| H1 | 0.783 (2) | 0.3883 (19) | 0.2849 (14) | 0.060 (7)* |
| O2 | 0.72549 (10) | 0.14048 (9) | 0.22742 (7) | 0.0334 (2) |
| H2 | 0.746 (2) | 0.1767 (19) | 0.2702 (15) | 0.060 (7)* |
| O3 | 1.03595 (10) | 0.49682 (8) | 0.22181 (7) | 0.0367 (3) |
| O4 | 0.84373 (9) | −0.04593 (8) | 0.11230 (7) | 0.0321 (2) |
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aOccupancy: 0.06, bOccupancy: 0.94.
Source of material
The title compound was prepared via Zn-mediated reductive coupling reaction [6] of 1,8-bis(2-fluorobenzoyl)-2,7-dimeth-oxynaphthalene. The starting material was synthesized by reference to the literature [7]. In a 10 mL two-necked round-bottomed flask, 1,8-bis(2-fluorobenzoyl)-2,7-dimeth-oxynaphthalene (86 mg, 0.2 mmol), zinc (78 mg, 1.2 mmol), zinc chloride (27 mg, 0.2 mmol) and DMAc (0.4 mL) were stirred at 373 K under nitrogen atmosphere. After stirring for 4 h, the reaction mixture was poured into water (30 mL). The resulting aqueous solution was extracted with chloroform (20 mL × three times). The combined organic extracts were washed with 2 M HCl aq (20 mL × three times) and brine (20 mL × three times) successively. The organic layer thus obtained was dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give a cake. Then the cake was dissolved in chloroform (2 mL) and the solution was added drop-wisely to hexane (200 mL) for reprecipitation. The precipitates were collected by suction filtration (quant.). Colorless block crystals of title compound were obtained by crystallization from ethyl acetate (68% yield). 1 H NMR δ (300 MHz, CDCl3): 8.09 (1H, dddd, J = 8.1, 8.1, 2.4 and 2.4 Hz), 7.88 (d, 1H, J = 9.0 Hz), 7.77 (d, 1H, J = 8.7 Hz), 7.29 (d, 1H, J = 9.0 Hz), 7.14 (d, 1H, J = 8.7 Hz), 7.05 (ddd, 1H, J = 7.8, 7.8 and 1.5 Hz), 7.02–6.88 (m, 3H), 6.76 (ddd, 1H, J = 7.8, 7.8 and 1.5 Hz), 6.59 (ddd, 1H, J = 1, 12.0 and 0.9 Hz), 6.25 (ddd, 1H, J = 11.4, 7.8 and 0.9 Hz), 4.48 (s, 1H), 4.31 (d, 1H, J = 6.6 Hz), 3.90 (s, 3H), 3.66 (s, 3H) ppm; 13 C NMR δ (75 MHz, CDCl3): 160.79 (J C–F = 247 Hz), 158.67 (J C–F = 246 Hz), 153.53, 153.09, 139.44 (pseudo s, J C–F = 2.9 Hz), 130.73 (J C–F = 10.1 Hz), 130.66, 129.43 (J C–F = 8.6 Hz), 128.73 (J C–F = 7.9 Hz), 128.34, 128.02, 127.94 (J C– F = 12.2 Hz), 127.32 (J C–F = 7.2 Hz), 127.16, 123.76, 123.00 (J C–F = 2.8 Hz), 122.53 (J C–F = 2.8 Hz), 122.17, 115.17 (J C–F = 23.0 Hz), 114.43, 114.10 (J C–F = 23.0 Hz), 113.61, 89.95 (pseudo s), 85.66 (J C–F = 2.85 Hz), 56.56, 56.16 ppm. IR (KBr): 3505 (O–H), 3464 (O–H), 1630 (Ar), 1581 (Ar), 1504 (Ar), 1485, 1225, 1040 cm−1. HRMS (m/z): [M+H–H2O]+ calcd. for C26H19F2O3, 417.1302, found, 417.1318. m.p. = 450–451 K.
Experimental details
All H atoms were found in a difference map and were subsequently refined as riding atoms, with C–H = 0.95 (aromatic) and 0.98 (methyl) Å, and with U iso(H) = 1.2U eq(C).
Comment
Weak interactions such as non-classical hydrogen bond [8], [9], [10], [11] are ordinarily latent, however, crystals of non-coplanarly accumulated aromatic rings compounds can expectingly pull out weak interactions by depressing π⋯π stacking. Such a skeleton is embodied in title pinacol, which is reductively coupling product of peri-aroylnaphthalene compounds [12], [13], [14], [15], [16], [17]. In the title molecular structure, two 2-fluorophenyl groups are oriented in a same direction against the acenaphthene ring (Figure). The cyclopentane moiety (C1–C9–C8–C18–C11 ring) and the naphthalene moiety (C1–C10 ring) of the acenaphthene ring are almost coplanar (dihedral angle = 2.06°; C1–C11–C18–C8 = 3.78(12)°). The dihedral angles between fluorobenzene rings and the naphthalene ring are 55.62° [C12–C17 ring; C1–C11–C12–C13 = −170.79(13)°] and 86.70° [C19–C24 ring; C8–C18–C19–C20 = 124.74(13)°], respectively. The dihedral angle between the best planes of the two fluorobenzene rings is 51.34(8)°. Three kinds of intramolecular non-covalent bonding interactions are observed: O–H⋯O classical hydrogen bond between hydroxy groups at 1,2-positions [1.95(2) Å, H2⋯O1], C–H⋯O non-classical hydrogen bond between H20 atom of 2-fluorophenyl moiety and oxygen atom of hydroxy group (2.32 Å, H20⋯O2), and C–F⋯π interaction between F2 atom and cyclopentane moiety [2.7602(10) Å, F2⋯Cg1; Cg1 = C1–C9–C8–C18–C11 ring]. On the other 2-fluorophenyl group, the fluorine atom is disordered over two positions with site occupancies of 0.94 and 0.06 [F1A and F1B]. Therefore, the title compound is postulated as a mixture of two components, i.e., endo-exo (F2 and F1A/H17; major component) and endo-endo (F2 and F1B/H13; minor one) types. In the crystal packing, intermolecular classical hydrogen bond between hydroxy and methoxy groups links molecules into two-fold helical molecular aggregation along the b-axis [2.25(2) Å, H1⋯O4; symmetry code: 3/2−x, 1/2+y, 1/2−z]. The two-fold helical molecular aggregations are further gathered by two bidirectional forces: the C–H⋯π non-classical hydrogen bond between a methoxy group and the naphthalene ring along c-axis [2.66 Å, H26B⋯Cg3; Cg3 = C5–C10 ring; symmetry code: 2−x, −y, −z] and a C–H⋯O non-classical hydrogen bond between the H22 atom of the 2-fluorophenyl group and the hydroxy oxygen along a-axis [2.54 Å, H22⋯O1; symmetry code: −1/2+x, 1/2−y, −1/2+z]. The hydroxy group (O2–H) that shares its hydrogen atom with the other hydroxy group (O1–H) also makes a non-classical hydrogen bond with the hydrogen atom (H–C20) forming a warped six–five–five fused tricyclic structure, at the end of which the fluorine atom (F2) occupying the opposite o-position intramolecularly interacts with the cyclopentane moiety. On the other phenyl group, the o-positioned hydrogen and fluorine atoms are free from effective interactions, which induces comparably stable two components as displayed in disorder of two atoms.
Funding source: JSPS KAKENHI
Award Identifier / Grant number: JP20K05473
Funding source: Tokyo Ohka Foundation for The Promotion of Science and Technology
Award Identifier / Grant number: 216065
Acknowledgments
The authors express their gratitude to Mr Hirokazu Shiomichi and Mr Genta Takahara, Department of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture and Technology, for their technical supports.
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Research funding: JSPS KAKENHI, grant number JP20K05473 and Tokyo Ohka Foundation for The Promotion of Science and Technology, grant number 216065.
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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