organic compounds
3-Acetyl-2-fluoro-6H-benzo[c]chromen-6-one
aSchool of Pharmaceutical Sciences, University of Shizuoka, 52-1 Yada, Suruga-ku, Shizuoka 422-8526, Japan
*Correspondence e-mail: ishi206@u-shizuoka-ken.ac.jp
The title compound, C15H9FO3, was obtained in a one-pot synthesis by Suzuki–Miyaura cross-coupling and nucleophilic of 4′-chloro-2′,5′-difluoroacetophenone with o-(methoxycarbonyl)phenylboronic acid. The contains two crystallographically independent molecules related by a non-crystallographic inversion centre. There are face-to-face stacking interactions between the aromatic rings of the benzoate and acetophenone units of the symmetry-independent molecules [centroid–centroid distances = 3.870 (3) and 3.986 (3) Å]. In the crystal, molecules are further assembled via stacking interactions along the a-axis direction. One of the molecules interacts with its inversion equivalent [centroid–centroid distance between the aromatic rings of the benzoate and acetophenone units = 3.932 (3) Å], and the other interacts with its twofold axis equivalent [centroid–centroid distance between the aromatic rings of acetophenone units = 3.634 (3) Å].
CCDC reference: 992229
Related literature
For background to this study, see: Dias et al. (2009); Ishikawa & Fujii (2011). For related compounds and structures, see: Bringmann & Menche (2001); Robinson et al. (1991); Siegel et al. (2010); Dasari et al. (2012). For the biological activity of related compounds, see: Sun et al. (2006).
Experimental
Crystal data
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Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell WinAFC Diffractometer Control Software; data reduction: WinAFC Diffractometer Control Software; program(s) used to solve structure: SIR2008 (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure.
Supporting information
CCDC reference: 992229
10.1107/S1600536814005959/fy2113sup1.cif
contains datablocks General, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005959/fy2113Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005959/fy2113Isup3.cml
In a Schlenk tube under nitrogen atmosphere, the mixture of 4'-chloro-2',5'-difluoroacetophenone (1.0 g, 0.0052 mol), o-(methoxycarbonyl)phenylboronic acid (0.83 g, 0.0046 mol), K2CO3 (0.87 g, 0.0063 mol) and Pd(PPh3)4 (0.15 g, 0.00013 mol) in 30 ml of DMF were stirred at 100 °C for 18 h. After cooling to room temperature and filtration, ethyl acetate and water were added to the filtrate. The organic phase was separated, washed with water and brine, dried with MgSO4, and was slowly evaporated to give the pink solid (yield: 14%). 1H NMR (400 MHz, CDCl3): d = 2.71 (d, 3H, J = 4.8 Hz), 7.71 (t, 1H, J = 8.0 Hz), 7.82 (d, 1H, J = 11.2 Hz), 7.88 (t, 1H, J = 8.0 Hz), 7.91 (d, 1H, J = 8.0 Hz), 7.08 (d, 1H, J = 8.0 Hz), 8.46 (d, 1H, J = 8.0 Hz). DART-MS calcd for [C15H9FO3 + H+]: 257.061, found 257.081. Single crystals suitable for X-ray diffraction were obtained by recrystalization of an ethyl acetate solution of the title compound at room temperature.
The hydrogen atoms were placed in geometrical positions [C–H 0.95 Å for phenyl, C–H 0.98 Å for methyl, Uiso(H) = 1.2Ueq(C)], and refined using a riding model.
Data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell
WinAFC Diffractometer Control Software (Rigaku, 1999); data reduction: WinAFC Diffractometer Control Software (Rigaku, 1999); program(s) used to solve structure: SIR2008 (Burla et al., 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalStructure (Rigaku, 2010); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).C15H9FO3 | F(000) = 2112.00 |
Mr = 256.23 | Dx = 1.510 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -C 2yc | Cell parameters from 25 reflections |
a = 26.005 (19) Å | θ = 15.6–17.4° |
b = 13.169 (4) Å | µ = 0.12 mm−1 |
c = 13.297 (8) Å | T = 100 K |
β = 98.02 (6)° | Block, pink |
V = 4509 (5) Å3 | 0.40 × 0.34 × 0.25 mm |
Z = 16 |
Rigaku AFC-7R diffractometer | θmax = 27.5° |
ω scans | h = −18→33 |
6119 measured reflections | k = 0→17 |
5160 independent reflections | l = −17→16 |
3534 reflections with F2 > 2σ(F2) | 3 standard reflections every 150 reflections |
Rint = 0.017 | intensity decay: −0.4% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0742P)2 + 2.0957P] where P = (Fo2 + 2Fc2)/3 |
5160 reflections | (Δ/σ)max = 0.001 |
343 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C15H9FO3 | V = 4509 (5) Å3 |
Mr = 256.23 | Z = 16 |
Monoclinic, C2/c | Mo Kα radiation |
a = 26.005 (19) Å | µ = 0.12 mm−1 |
b = 13.169 (4) Å | T = 100 K |
c = 13.297 (8) Å | 0.40 × 0.34 × 0.25 mm |
β = 98.02 (6)° |
Rigaku AFC-7R diffractometer | Rint = 0.017 |
6119 measured reflections | 3 standard reflections every 150 reflections |
5160 independent reflections | intensity decay: −0.4% |
3534 reflections with F2 > 2σ(F2) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.137 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.35 e Å−3 |
5160 reflections | Δρmin = −0.28 e Å−3 |
343 parameters |
Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
F1A | 0.31263 (5) | 1.07390 (8) | 0.04611 (8) | 0.0259 (3) | |
F1B | 0.44773 (4) | 0.42794 (8) | 0.02258 (8) | 0.0251 (3) | |
O1A | 0.31217 (5) | 0.78443 (9) | −0.24820 (9) | 0.0216 (3) | |
O2A | 0.31393 (5) | 0.62794 (10) | −0.30292 (10) | 0.0246 (3) | |
O3A | 0.30739 (5) | 1.15534 (10) | −0.25742 (9) | 0.0234 (3) | |
O1B | 0.42805 (5) | 0.71154 (10) | 0.31463 (9) | 0.0202 (3) | |
O2B | 0.42512 (5) | 0.86817 (10) | 0.37147 (10) | 0.0258 (3) | |
O3B | 0.44045 (6) | 0.33924 (11) | 0.31809 (10) | 0.0277 (4) | |
C1A | 0.31365 (6) | 0.82575 (13) | −0.06925 (12) | 0.0150 (4) | |
C2A | 0.31386 (7) | 0.90307 (13) | 0.00280 (13) | 0.0171 (4) | |
C3A | 0.31233 (7) | 1.00254 (14) | −0.02744 (13) | 0.0175 (4) | |
C4A | 0.31038 (7) | 1.03261 (13) | −0.12886 (13) | 0.0167 (4) | |
C5A | 0.31047 (7) | 0.95538 (13) | −0.20015 (13) | 0.0181 (4) | |
C6A | 0.31227 (7) | 0.85494 (13) | −0.17052 (13) | 0.0171 (4) | |
C7A | 0.31431 (6) | 0.71708 (13) | −0.04513 (13) | 0.0152 (4) | |
C8A | 0.31428 (7) | 0.64746 (14) | −0.12495 (13) | 0.0175 (4) | |
C9A | 0.31458 (7) | 0.54330 (14) | −0.10615 (14) | 0.0217 (4) | |
C10A | 0.31479 (7) | 0.50751 (14) | −0.00851 (14) | 0.0207 (4) | |
C11A | 0.31461 (7) | 0.57649 (14) | 0.07141 (14) | 0.0195 (4) | |
C13A | 0.31366 (7) | 0.68230 (14) | −0.23014 (14) | 0.0201 (4) | |
C14A | 0.30814 (7) | 1.14026 (13) | −0.16662 (13) | 0.0176 (4) | |
C15A | 0.30670 (9) | 1.22769 (15) | −0.09546 (14) | 0.0283 (5) | |
C1B | 0.44025 (6) | 0.67388 (14) | 0.14047 (13) | 0.0165 (4) | |
C2B | 0.44531 (7) | 0.59797 (14) | 0.06830 (13) | 0.0186 (4) | |
C3B | 0.44303 (7) | 0.49787 (14) | 0.09551 (13) | 0.0175 (4) | |
C4B | 0.43642 (7) | 0.46580 (14) | 0.19314 (13) | 0.0174 (4) | |
C5B | 0.43176 (7) | 0.54154 (14) | 0.26455 (13) | 0.0176 (4) | |
C6B | 0.43337 (7) | 0.64274 (14) | 0.23804 (13) | 0.0168 (4) | |
C14B | 0.43523 (7) | 0.35764 (14) | 0.22744 (14) | 0.0199 (4) | |
C7B | 0.44059 (6) | 0.78242 (14) | 0.11788 (13) | 0.0176 (4) | |
C12B | 0.44570 (7) | 0.82098 (15) | 0.02167 (14) | 0.0205 (4) | |
C11B | 0.44476 (7) | 0.92443 (15) | 0.00505 (15) | 0.0235 (4) | |
C10B | 0.43892 (8) | 0.99194 (15) | 0.08315 (16) | 0.0252 (5) | |
C9B | 0.43407 (7) | 0.95588 (15) | 0.17896 (15) | 0.0234 (4) | |
C12A | 0.31442 (6) | 0.67979 (14) | 0.05381 (13) | 0.0170 (4) | |
C13B | 0.42922 (7) | 0.81498 (14) | 0.29949 (14) | 0.0203 (4) | |
C15B | 0.42691 (9) | 0.27294 (15) | 0.15133 (15) | 0.0289 (5) | |
C8B | 0.43480 (7) | 0.85080 (14) | 0.19627 (13) | 0.0177 (4) | |
H1A | 0.3151 | 0.8866 | 0.0727 | 0.0205* | |
H2A | 0.3093 | 0.9720 | −0.2700 | 0.0217* | |
H3A | 0.3146 | 0.4968 | −0.1607 | 0.0260* | |
H4A | 0.3151 | 0.4365 | 0.0043 | 0.0248* | |
H5A | 0.3146 | 0.5520 | 0.1386 | 0.0234* | |
H6A | 0.3144 | 0.7258 | 0.1088 | 0.0204* | |
H7A | 0.2788 | 1.2171 | −0.0539 | 0.0339* | |
H8A | 0.3003 | 1.2906 | −0.1345 | 0.0339* | |
H9A | 0.3401 | 1.2327 | −0.0512 | 0.0339* | |
H1B | 0.4503 | 0.6159 | 0.0011 | 0.0223* | |
H2B | 0.4275 | 0.5234 | 0.3320 | 0.0211* | |
H6B | 0.4498 | 0.7758 | −0.0323 | 0.0246* | |
H5B | 0.4481 | 0.9499 | −0.0606 | 0.0282* | |
H4B | 0.4383 | 1.0630 | 0.0706 | 0.0302* | |
H3B | 0.4303 | 1.0018 | 0.2326 | 0.0280* | |
H7B | 0.4272 | 0.2078 | 0.1870 | 0.0346* | |
H8B | 0.4547 | 0.2738 | 0.1086 | 0.0346* | |
H9B | 0.3933 | 0.2820 | 0.1087 | 0.0346* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1A | 0.0483 (7) | 0.0158 (6) | 0.0137 (6) | −0.0002 (5) | 0.0051 (5) | −0.0042 (5) |
F1B | 0.0400 (7) | 0.0202 (6) | 0.0162 (6) | 0.0028 (5) | 0.0074 (5) | −0.0029 (5) |
O1A | 0.0361 (8) | 0.0167 (7) | 0.0129 (6) | −0.0005 (6) | 0.0073 (6) | −0.0025 (5) |
O2A | 0.0370 (8) | 0.0195 (7) | 0.0184 (7) | 0.0000 (6) | 0.0079 (6) | −0.0055 (6) |
O3A | 0.0351 (8) | 0.0206 (7) | 0.0148 (6) | −0.0002 (6) | 0.0048 (6) | 0.0026 (6) |
O1B | 0.0272 (7) | 0.0195 (7) | 0.0146 (6) | 0.0014 (6) | 0.0049 (5) | −0.0027 (5) |
O2B | 0.0309 (8) | 0.0260 (8) | 0.0206 (7) | 0.0018 (6) | 0.0041 (6) | −0.0072 (6) |
O3B | 0.0417 (9) | 0.0235 (8) | 0.0177 (7) | 0.0027 (7) | 0.0032 (6) | 0.0033 (6) |
C1A | 0.0149 (8) | 0.0161 (9) | 0.0141 (8) | −0.0004 (7) | 0.0027 (6) | −0.0002 (7) |
C2A | 0.0211 (9) | 0.0177 (9) | 0.0122 (8) | −0.0010 (7) | 0.0017 (7) | −0.0006 (7) |
C3A | 0.0228 (9) | 0.0165 (9) | 0.0134 (8) | −0.0001 (7) | 0.0027 (7) | −0.0040 (7) |
C4A | 0.0172 (9) | 0.0163 (9) | 0.0169 (9) | −0.0003 (7) | 0.0035 (7) | 0.0017 (7) |
C5A | 0.0244 (9) | 0.0178 (9) | 0.0125 (8) | 0.0005 (7) | 0.0047 (7) | 0.0021 (7) |
C6A | 0.0204 (9) | 0.0165 (9) | 0.0149 (8) | −0.0009 (7) | 0.0043 (7) | −0.0050 (7) |
C7A | 0.0142 (8) | 0.0146 (9) | 0.0167 (8) | −0.0006 (7) | 0.0022 (7) | −0.0013 (7) |
C8A | 0.0173 (9) | 0.0184 (9) | 0.0172 (9) | −0.0001 (7) | 0.0038 (7) | −0.0010 (7) |
C9A | 0.0244 (10) | 0.0188 (10) | 0.0218 (9) | 0.0001 (8) | 0.0031 (8) | −0.0025 (8) |
C10A | 0.0236 (9) | 0.0138 (9) | 0.0247 (10) | −0.0001 (7) | 0.0040 (8) | 0.0010 (8) |
C11A | 0.0172 (9) | 0.0206 (10) | 0.0203 (9) | −0.0003 (7) | 0.0013 (7) | 0.0028 (7) |
C13A | 0.0227 (9) | 0.0190 (9) | 0.0188 (9) | 0.0014 (8) | 0.0039 (7) | −0.0028 (8) |
C14A | 0.0198 (9) | 0.0158 (9) | 0.0171 (9) | −0.0001 (7) | 0.0024 (7) | 0.0010 (7) |
C15A | 0.0486 (13) | 0.0186 (10) | 0.0184 (10) | 0.0013 (9) | 0.0075 (9) | −0.0017 (8) |
C1B | 0.0143 (8) | 0.0193 (9) | 0.0157 (8) | 0.0001 (7) | 0.0017 (7) | −0.0009 (7) |
C2B | 0.0190 (9) | 0.0235 (10) | 0.0134 (8) | 0.0017 (7) | 0.0029 (7) | 0.0013 (7) |
C3B | 0.0196 (9) | 0.0194 (10) | 0.0140 (8) | 0.0019 (7) | 0.0035 (7) | −0.0042 (7) |
C4B | 0.0184 (9) | 0.0188 (10) | 0.0150 (8) | 0.0017 (7) | 0.0021 (7) | −0.0010 (7) |
C5B | 0.0200 (9) | 0.0211 (10) | 0.0118 (8) | 0.0005 (7) | 0.0031 (7) | 0.0017 (7) |
C6B | 0.0165 (8) | 0.0195 (9) | 0.0145 (8) | 0.0007 (7) | 0.0022 (7) | −0.0026 (7) |
C14B | 0.0214 (9) | 0.0200 (10) | 0.0189 (9) | 0.0027 (8) | 0.0047 (7) | 0.0015 (8) |
C7B | 0.0134 (8) | 0.0179 (9) | 0.0213 (9) | −0.0007 (7) | 0.0016 (7) | −0.0010 (7) |
C12B | 0.0195 (9) | 0.0233 (10) | 0.0190 (9) | −0.0009 (8) | 0.0036 (7) | 0.0013 (8) |
C11B | 0.0231 (10) | 0.0233 (10) | 0.0244 (10) | −0.0015 (8) | 0.0038 (8) | 0.0029 (8) |
C10B | 0.0241 (10) | 0.0184 (10) | 0.0331 (11) | −0.0025 (8) | 0.0037 (8) | 0.0021 (8) |
C9B | 0.0227 (10) | 0.0188 (10) | 0.0282 (10) | −0.0007 (8) | 0.0023 (8) | −0.0042 (8) |
C12A | 0.0161 (8) | 0.0181 (9) | 0.0165 (9) | 0.0002 (7) | 0.0014 (7) | −0.0000 (7) |
C13B | 0.0191 (9) | 0.0203 (10) | 0.0209 (9) | −0.0001 (7) | 0.0010 (7) | −0.0037 (8) |
C15B | 0.0417 (12) | 0.0212 (11) | 0.0248 (10) | −0.0034 (9) | 0.0085 (9) | −0.0041 (8) |
C8B | 0.0156 (8) | 0.0196 (10) | 0.0177 (9) | −0.0010 (7) | 0.0010 (7) | −0.0016 (7) |
F1A—C3A | 1.356 (3) | C3B—C4B | 1.398 (3) |
F1B—C3B | 1.355 (3) | C4B—C5B | 1.394 (3) |
O1A—C6A | 1.389 (3) | C4B—C14B | 1.497 (3) |
O1A—C13A | 1.366 (3) | C5B—C6B | 1.381 (3) |
O2A—C13A | 1.205 (3) | C14B—C15B | 1.501 (3) |
O3A—C14A | 1.221 (3) | C7B—C12B | 1.400 (3) |
O1B—C6B | 1.384 (3) | C7B—C8B | 1.401 (3) |
O1B—C13B | 1.378 (3) | C12B—C11B | 1.380 (3) |
O2B—C13B | 1.203 (3) | C11B—C10B | 1.391 (3) |
O3B—C14B | 1.218 (3) | C10B—C9B | 1.382 (3) |
C1A—C2A | 1.398 (3) | C9B—C8B | 1.403 (3) |
C1A—C6A | 1.396 (3) | C13B—C8B | 1.478 (3) |
C1A—C7A | 1.466 (3) | C2A—H1A | 0.950 |
C2A—C3A | 1.369 (3) | C5A—H2A | 0.950 |
C3A—C4A | 1.400 (3) | C9A—H3A | 0.950 |
C4A—C5A | 1.391 (3) | C10A—H4A | 0.950 |
C4A—C14A | 1.502 (3) | C11A—H5A | 0.950 |
C5A—C6A | 1.379 (3) | C15A—H7A | 0.980 |
C7A—C8A | 1.402 (3) | C15A—H8A | 0.980 |
C7A—C12A | 1.404 (3) | C15A—H9A | 0.980 |
C8A—C9A | 1.394 (3) | C2B—H1B | 0.950 |
C8A—C13A | 1.470 (3) | C5B—H2B | 0.950 |
C9A—C10A | 1.381 (3) | C12B—H6B | 0.950 |
C10A—C11A | 1.399 (3) | C11B—H5B | 0.950 |
C11A—C12A | 1.380 (3) | C10B—H4B | 0.950 |
C14A—C15A | 1.494 (3) | C9B—H3B | 0.950 |
C1B—C2B | 1.405 (3) | C12A—H6A | 0.950 |
C1B—C6B | 1.396 (3) | C15B—H7B | 0.980 |
C1B—C7B | 1.461 (3) | C15B—H8B | 0.980 |
C2B—C3B | 1.370 (3) | C15B—H9B | 0.980 |
F1A···C14A | 2.947 (3) | C7B···H3B | 3.2949 |
F1A···C15A | 2.755 (3) | C12B···H1B | 2.7190 |
F1B···C14B | 2.938 (3) | C12B···H4B | 3.2637 |
F1B···C15B | 2.766 (3) | C11B···H3B | 3.2631 |
O1A···C7A | 2.835 (3) | C10B···H6B | 3.2652 |
O2A···C6A | 3.473 (3) | C9B···H5B | 3.2572 |
O2A···C9A | 2.842 (3) | C12A···H1A | 2.7352 |
O3A···C5A | 2.739 (3) | C12A···H4A | 3.2710 |
O1B···C7B | 2.839 (3) | C13B···H3B | 2.6177 |
O2B···C6B | 3.480 (3) | C8B···H6B | 3.2710 |
O2B···C9B | 2.847 (3) | C8B···H4B | 3.2636 |
O3B···C5B | 2.759 (3) | H1A···H6A | 2.1726 |
C1A···C4A | 2.835 (3) | H3A···H4A | 2.3321 |
C1A···C13A | 2.854 (3) | H4A···H5A | 2.3464 |
C2A···C5A | 2.775 (3) | H5A···H6A | 2.3231 |
C2A···C12A | 3.017 (3) | H1B···H6B | 2.1521 |
C3A···C6A | 2.720 (3) | H6B···H5B | 2.3225 |
C3A···C15A | 3.097 (3) | H5B···H4B | 2.3346 |
C6A···C8A | 2.798 (3) | H4B···H3B | 2.3356 |
C7A···C10A | 2.802 (3) | F1A···H2Ai | 2.5325 |
C8A···C11A | 2.772 (3) | F1A···H4Aii | 3.2972 |
C9A···C12A | 2.785 (3) | F1A···H4B | 3.2409 |
C1B···C4B | 2.834 (3) | F1A···H9Bxi | 3.4807 |
C1B···C13B | 2.859 (3) | F1B···H4A | 3.4268 |
C2B···C5B | 2.783 (3) | F1B···H1Biii | 2.7751 |
C2B···C12B | 3.002 (3) | F1B···H2Biv | 2.5957 |
C3B···C6B | 2.725 (3) | O1A···H7Avii | 3.4018 |
C3B···C15B | 3.096 (3) | O1A···H8Avii | 3.1165 |
C6B···C8B | 2.797 (3) | O1A···H7Biv | 3.2290 |
C7B···C10B | 2.797 (3) | O1A···H9Biv | 3.1562 |
C12B···C9B | 2.793 (3) | O2A···H4Aiv | 2.7044 |
C11B···C8B | 2.767 (3) | O2A···H5Aiv | 2.4943 |
F1A···O1Ai | 3.312 (2) | O2A···H7Avii | 3.0891 |
F1A···C5Ai | 3.404 (3) | O2A···H9Biv | 2.7803 |
F1A···C10Aii | 3.452 (4) | O3A···H1Avi | 2.3615 |
F1A···C10B | 3.427 (4) | O3A···H6Avi | 2.3950 |
F1B···F1Biii | 3.436 (3) | O1B···H8Ai | 3.4828 |
F1B···O1Biv | 3.300 (2) | O1B···H9Ai | 3.1774 |
F1B···O3Bv | 3.548 (3) | O2B···H9Ai | 2.8892 |
F1B···C10A | 3.581 (4) | O2B···H5Bi | 2.6011 |
F1B···C2Biii | 3.202 (3) | O2B···H4Bi | 2.7742 |
F1B···C3Biii | 3.569 (3) | O3B···H1Bix | 2.4828 |
F1B···C5Biv | 3.422 (3) | O3B···H6Bix | 2.4851 |
O1A···F1Avi | 3.312 (2) | O3B···H8Bv | 2.8952 |
O1A···O3Avii | 3.553 (3) | C1A···H6Aii | 3.3663 |
O1A···C15Avii | 3.556 (4) | C1A···H6B | 3.5681 |
O1A···C15Biv | 3.517 (4) | C2A···H2Ai | 3.4573 |
O2A···O3Avii | 3.381 (3) | C3A···H2Ai | 3.4521 |
O2A···O3Biv | 3.482 (3) | C3A···H4Aii | 3.4635 |
O2A···C4Avii | 3.469 (3) | C3A···H5Aii | 3.4979 |
O2A···C10Aiv | 3.267 (3) | C3A···H4B | 3.4446 |
O2A···C11Aiv | 3.170 (3) | C4A···H5Aii | 3.4212 |
O2A···C14Avii | 3.148 (4) | C5A···H3Aviii | 3.5531 |
O2A···C15Avii | 3.494 (4) | C5A···H5Aii | 3.4644 |
O2A···C4Biv | 3.423 (3) | C5A···H3Bvi | 3.4070 |
O2A···C14Biv | 3.130 (4) | C7A···H6Aii | 3.4191 |
O2A···C15Biv | 3.347 (4) | C7A···H6B | 3.5890 |
O3A···O1Aviii | 3.553 (3) | C8A···H1Aii | 3.5566 |
O3A···O2Aviii | 3.381 (3) | C9A···H1Aii | 3.5823 |
O3A···O2Bvi | 3.308 (3) | C9A···H2Avii | 3.5341 |
O3A···C2Avi | 3.307 (3) | C9A···H8Axii | 3.3639 |
O3A···C8Aviii | 3.330 (4) | C9A···H2Biv | 3.2766 |
O3A···C13Aviii | 3.149 (4) | C10A···H8Axii | 3.3066 |
O3A···C12Avi | 3.343 (3) | C13A···H5Aiv | 3.5463 |
O3A···C13Bvi | 3.177 (4) | C13A···H7Avii | 3.5091 |
O3A···C8Bvi | 3.454 (4) | C13A···H8Avii | 3.5439 |
O1B···F1Bix | 3.300 (2) | C13A···H7Biv | 3.5973 |
O1B···C1Bv | 3.429 (4) | C13A···H9Biv | 3.2166 |
O1B···C7Bv | 3.534 (3) | C14A···H1Avi | 3.5145 |
O2B···O3Ai | 3.308 (3) | C14A···H6Avi | 3.4911 |
O2B···C4Ai | 3.257 (3) | C15A···H4Axi | 3.0480 |
O2B···C14Ai | 3.015 (3) | C15A···H7Axiii | 3.2645 |
O2B···C15Ai | 3.413 (4) | C15A···H9Bxi | 3.3534 |
O2B···C12Bv | 3.515 (4) | C1B···H6A | 3.3130 |
O2B···C11Bi | 3.259 (3) | C2B···H2Bv | 3.5280 |
O2B···C10Bi | 3.341 (3) | C2B···H2Biv | 3.4978 |
O3B···F1Bv | 3.548 (3) | C3B···H4A | 3.4747 |
O3B···O2Aix | 3.482 (3) | C3B···H5A | 3.5387 |
O3B···C8Aix | 3.473 (4) | C3B···H1Biii | 3.5481 |
O3B···C13Aix | 3.282 (4) | C3B···H2Bv | 3.3883 |
O3B···C2Bix | 3.413 (3) | C3B···H2Biv | 3.4818 |
O3B···C14Bv | 3.380 (4) | C4B···H5A | 3.3476 |
O3B···C12Bix | 3.420 (3) | C5B···H3Aix | 3.3708 |
O3B···C15Bv | 3.526 (4) | C5B···H5A | 3.2682 |
C1A···C11Aii | 3.572 (4) | C6B···H5A | 3.4023 |
C1A···C12B | 3.478 (4) | C6B···H6A | 3.4987 |
C1A···C12Aii | 3.366 (4) | C14B···H8Bv | 3.5242 |
C2A···O3Ai | 3.307 (3) | C7B···H1A | 3.5150 |
C2A···C10Aii | 3.558 (4) | C7B···H6A | 3.3517 |
C2A···C11Aii | 3.360 (4) | C12B···H8Biii | 3.5381 |
C2A···C12B | 3.570 (4) | C11B···H5Bx | 3.2354 |
C2A···C11B | 3.412 (4) | C11B···H4Bx | 3.3387 |
C2A···C10B | 3.481 (4) | C10B···H1A | 3.4919 |
C2A···C12Aii | 3.491 (4) | C10B···H5Bx | 3.0902 |
C3A···C10Aii | 3.408 (4) | C10B···H7Bxi | 3.1932 |
C3A···C11Aii | 3.433 (4) | C9B···H1A | 3.3449 |
C3A···C11B | 3.562 (4) | C9B···H2Ai | 3.5370 |
C3A···C10B | 3.416 (4) | C9B···H7Bxi | 3.3247 |
C4A···O2Aviii | 3.469 (3) | C13B···H9Ai | 3.3158 |
C4A···O2Bvi | 3.257 (3) | C15B···H9Axii | 3.3075 |
C5A···F1Avi | 3.404 (3) | C15B···H4Bxii | 2.9956 |
C7A···C12Aii | 3.600 (4) | C8B···H1A | 3.3457 |
C8A···O3Avii | 3.330 (4) | C8B···H6A | 3.5852 |
C8A···O3Biv | 3.473 (4) | H1A···O3Ai | 2.3615 |
C10A···F1Aii | 3.452 (4) | H1A···C8Aii | 3.5566 |
C10A···F1B | 3.581 (4) | H1A···C9Aii | 3.5823 |
C10A···O2Aix | 3.267 (3) | H1A···C14Ai | 3.5145 |
C10A···C2Aii | 3.558 (4) | H1A···C7B | 3.5150 |
C10A···C3Aii | 3.408 (4) | H1A···C10B | 3.4919 |
C10A···C3B | 3.430 (4) | H1A···C9B | 3.3449 |
C11A···O2Aix | 3.170 (3) | H1A···C8B | 3.3457 |
C11A···C1Aii | 3.572 (4) | H1A···H2Ai | 2.8209 |
C11A···C2Aii | 3.360 (4) | H2A···F1Avi | 2.5325 |
C11A···C3Aii | 3.433 (4) | H2A···C2Avi | 3.4573 |
C11A···C1B | 3.511 (4) | H2A···C3Avi | 3.4521 |
C11A···C2B | 3.417 (4) | H2A···C9Aviii | 3.5341 |
C11A···C3B | 3.468 (4) | H2A···C9Bvi | 3.5370 |
C13A···O3Avii | 3.149 (4) | H2A···H1Avi | 2.8209 |
C13A···O3Biv | 3.282 (4) | H2A···H3Aviii | 3.2422 |
C13A···C14Avii | 3.318 (4) | H2A···H3Bvi | 3.1616 |
C13A···C14Biv | 3.330 (4) | H3A···C5Avii | 3.5531 |
C13A···C15Biv | 3.578 (4) | H3A···C5Biv | 3.3708 |
C14A···O2Aviii | 3.148 (4) | H3A···H2Avii | 3.2422 |
C14A···O2Bvi | 3.015 (3) | H3A···H5Aiv | 2.7443 |
C14A···C13Aviii | 3.318 (4) | H3A···H8Axii | 2.7692 |
C14A···C13Bvi | 3.296 (4) | H3A···H2Biv | 2.9605 |
C15A···O1Aviii | 3.556 (4) | H4A···F1Aii | 3.2972 |
C15A···O2Aviii | 3.494 (4) | H4A···F1B | 3.4268 |
C15A···O2Bvi | 3.413 (4) | H4A···O2Aix | 2.7044 |
C1B···O1Bv | 3.429 (4) | H4A···C3Aii | 3.4635 |
C1B···C11A | 3.511 (4) | H4A···C15Axii | 3.0480 |
C1B···C6Bv | 3.478 (4) | H4A···C3B | 3.4747 |
C1B···C12A | 3.315 (4) | H4A···H7Axii | 3.1032 |
C2B···F1Biii | 3.202 (3) | H4A···H7Aii | 3.3081 |
C2B···O3Biv | 3.413 (3) | H4A···H8Axii | 2.6554 |
C2B···C11A | 3.417 (4) | H4A···H9Axii | 2.8826 |
C2B···C12A | 3.550 (4) | H4A···H9B | 3.0698 |
C3B···F1Biii | 3.569 (3) | H5A···O2Aix | 2.4943 |
C3B···C10A | 3.430 (4) | H5A···C3Aii | 3.4979 |
C3B···C11A | 3.468 (4) | H5A···C4Aii | 3.4212 |
C3B···C5Bv | 3.564 (4) | H5A···C5Aii | 3.4644 |
C4B···O2Aix | 3.423 (3) | H5A···C13Aix | 3.5463 |
C4B···C4Bv | 3.439 (4) | H5A···C3B | 3.5387 |
C4B···C5Bv | 3.539 (4) | H5A···C4B | 3.3476 |
C5B···F1Bix | 3.422 (3) | H5A···C5B | 3.2682 |
C5B···C3Bv | 3.564 (4) | H5A···C6B | 3.4023 |
C5B···C4Bv | 3.539 (4) | H5A···H3Aix | 2.7443 |
C6B···C1Bv | 3.478 (4) | H6A···O3Ai | 2.3950 |
C6B···C6Bv | 3.436 (4) | H6A···C1Aii | 3.3663 |
C14B···O2Aix | 3.130 (4) | H6A···C7Aii | 3.4191 |
C14B···O3Bv | 3.380 (4) | H6A···C14Ai | 3.4911 |
C14B···C13Aix | 3.330 (4) | H6A···C1B | 3.3130 |
C14B···C14Bv | 3.338 (4) | H6A···C6B | 3.4987 |
C7B···O1Bv | 3.534 (3) | H6A···C7B | 3.3517 |
C7B···C12A | 3.541 (3) | H6A···C8B | 3.5852 |
C7B···C13Bv | 3.437 (4) | H6A···H8Ai | 3.4894 |
C12B···O2Bv | 3.515 (4) | H7A···O1Aviii | 3.4018 |
C12B···O3Biv | 3.420 (3) | H7A···O2Aviii | 3.0891 |
C12B···C1A | 3.478 (4) | H7A···C13Aviii | 3.5091 |
C12B···C2A | 3.570 (4) | H7A···C15Axiii | 3.2645 |
C11B···O2Bvi | 3.259 (3) | H7A···H4Axi | 3.1032 |
C11B···C2A | 3.412 (4) | H7A···H4Aii | 3.3081 |
C11B···C3A | 3.562 (4) | H7A···H7Axiii | 2.3789 |
C11B···C11Bx | 3.513 (4) | H7A···H8Axiii | 3.4586 |
C11B···C10Bx | 3.568 (4) | H7A···H9Bxi | 3.5311 |
C10B···F1A | 3.427 (4) | H8A···O1Aviii | 3.1165 |
C10B···O2Bvi | 3.341 (3) | H8A···O1Bvi | 3.4828 |
C10B···C2A | 3.481 (4) | H8A···C9Axi | 3.3639 |
C10B···C3A | 3.416 (4) | H8A···C10Axi | 3.3066 |
C10B···C11Bx | 3.568 (4) | H8A···C13Aviii | 3.5439 |
C12A···O3Ai | 3.343 (3) | H8A···H3Axi | 2.7692 |
C12A···C1Aii | 3.366 (4) | H8A···H4Axi | 2.6554 |
C12A···C2Aii | 3.491 (4) | H8A···H6Avi | 3.4894 |
C12A···C7Aii | 3.600 (4) | H8A···H7Axiii | 3.4586 |
C12A···C1B | 3.315 (4) | H9A···O1Bvi | 3.1774 |
C12A···C2B | 3.550 (4) | H9A···O2Bvi | 2.8892 |
C12A···C7B | 3.541 (3) | H9A···C13Bvi | 3.3158 |
C13B···O3Ai | 3.177 (4) | H9A···C15Bxi | 3.3075 |
C13B···C14Ai | 3.296 (4) | H9A···H4Axi | 2.8826 |
C13B···C7Bv | 3.437 (4) | H9A···H8Bxi | 3.4545 |
C13B···C8Bv | 3.560 (4) | H9A···H9Bxi | 2.4573 |
C15B···O1Aix | 3.517 (4) | H1B···F1Biii | 2.7751 |
C15B···O2Aix | 3.347 (4) | H1B···O3Biv | 2.4828 |
C15B···O3Bv | 3.526 (4) | H1B···C3Biii | 3.5481 |
C15B···C13Aix | 3.578 (4) | H1B···H2Biv | 2.8982 |
C8B···O3Ai | 3.454 (4) | H1B···H8Biii | 3.3691 |
C8B···C13Bv | 3.560 (4) | H2B···F1Bix | 2.5957 |
C8B···C8Bv | 3.491 (4) | H2B···C9Aix | 3.2766 |
F1A···H1A | 2.4909 | H2B···C2Bv | 3.5280 |
F1A···H7A | 2.4029 | H2B···C2Bix | 3.4978 |
F1A···H9A | 2.6103 | H2B···C3Bv | 3.3883 |
F1B···H1B | 2.4933 | H2B···C3Bix | 3.4818 |
F1B···H8B | 2.3248 | H2B···H3Aix | 2.9605 |
F1B···H9B | 2.7313 | H2B···H1Bix | 2.8982 |
O1A···H2A | 2.4865 | H6B···O3Biv | 2.4851 |
O2A···H3A | 2.5592 | H6B···C1A | 3.5681 |
O3A···H2A | 2.4215 | H6B···C7A | 3.5890 |
O3A···H7A | 3.0157 | H6B···H8Biii | 2.8843 |
O3A···H8A | 2.4418 | H5B···O2Bvi | 2.6011 |
O3A···H9A | 2.9370 | H5B···C11Bx | 3.2354 |
O1B···H2B | 2.4889 | H5B···C10Bx | 3.0902 |
O2B···H3B | 2.5683 | H5B···H5Bx | 3.2248 |
O3B···H2B | 2.4589 | H5B···H4Bx | 2.9805 |
O3B···H7B | 2.4465 | H5B···H3Bvi | 2.7987 |
O3B···H8B | 2.9877 | H4B···F1A | 3.2409 |
O3B···H9B | 2.9789 | H4B···O2Bvi | 2.7742 |
C1A···H2A | 3.2801 | H4B···C3A | 3.4446 |
C1A···H6A | 2.7070 | H4B···C11Bx | 3.3387 |
C2A···H6A | 2.7263 | H4B···C15Bxi | 2.9956 |
C3A···H2A | 3.2398 | H4B···H5Bx | 2.9805 |
C3A···H7A | 2.9637 | H4B···H7Bxi | 2.4979 |
C3A···H9A | 3.1414 | H4B···H8Bxi | 2.8437 |
C4A···H1A | 3.2863 | H4B···H9Bxi | 3.1786 |
C4A···H7A | 2.7925 | H3B···C5Ai | 3.4070 |
C4A···H8A | 3.4078 | H3B···H2Ai | 3.1616 |
C4A···H9A | 2.8948 | H3B···H5Bi | 2.7987 |
C6A···H1A | 3.2511 | H3B···H3Bv | 3.5899 |
C7A···H1A | 2.7258 | H3B···H7Bxi | 2.7783 |
C7A···H3A | 3.2839 | H7B···O1Aix | 3.2290 |
C7A···H5A | 3.2698 | H7B···C13Aix | 3.5973 |
C8A···H4A | 3.2650 | H7B···C10Bxii | 3.1932 |
C8A···H6A | 3.2750 | H7B···C9Bxii | 3.3247 |
C9A···H5A | 3.2564 | H7B···H4Bxii | 2.4979 |
C10A···H6A | 3.2716 | H7B···H3Bxii | 2.7783 |
C11A···H3A | 3.2606 | H8B···O3Bv | 2.8952 |
C13A···H3A | 2.6106 | H8B···C14Bv | 3.5242 |
C14A···H2A | 2.6100 | H8B···C12Biii | 3.5381 |
C1B···H2B | 3.2806 | H8B···H9Axii | 3.4545 |
C1B···H6B | 2.7023 | H8B···H1Biii | 3.3691 |
C2B···H6B | 2.7078 | H8B···H6Biii | 2.8843 |
C3B···H2B | 3.2438 | H8B···H4Bxii | 2.8437 |
C3B···H8B | 2.9691 | H9B···F1Axii | 3.4807 |
C3B···H9B | 3.1384 | H9B···O1Aix | 3.1562 |
C4B···H1B | 3.2882 | H9B···O2Aix | 2.7803 |
C4B···H7B | 3.4063 | H9B···C13Aix | 3.2166 |
C4B···H8B | 2.8340 | H9B···C15Axii | 3.3534 |
C4B···H9B | 2.8334 | H9B···H4A | 3.0698 |
C6B···H1B | 3.2603 | H9B···H7Axii | 3.5311 |
C14B···H2B | 2.6109 | H9B···H9Axii | 2.4573 |
C7B···H1B | 2.7190 | H9B···H4Bxii | 3.1786 |
C7B···H5B | 3.2652 | ||
C6A—O1A—C13A | 122.05 (14) | C1B—C7B—C8B | 118.13 (16) |
C6B—O1B—C13B | 122.21 (15) | C12B—C7B—C8B | 118.71 (18) |
C2A—C1A—C6A | 117.24 (16) | C7B—C12B—C11B | 120.18 (18) |
C2A—C1A—C7A | 124.22 (16) | C12B—C11B—C10B | 120.84 (19) |
C6A—C1A—C7A | 118.54 (15) | C11B—C10B—C9B | 120.14 (19) |
C1A—C2A—C3A | 119.90 (17) | C10B—C9B—C8B | 119.31 (18) |
F1A—C3A—C2A | 117.02 (16) | C7A—C12A—C11A | 120.21 (17) |
F1A—C3A—C4A | 119.66 (16) | O1B—C13B—O2B | 116.95 (17) |
C2A—C3A—C4A | 123.32 (17) | O1B—C13B—C8B | 117.28 (16) |
C3A—C4A—C5A | 116.53 (16) | O2B—C13B—C8B | 125.76 (18) |
C3A—C4A—C14A | 125.70 (16) | C7B—C8B—C9B | 120.82 (17) |
C5A—C4A—C14A | 117.78 (16) | C7B—C8B—C13B | 121.36 (17) |
C4A—C5A—C6A | 120.66 (17) | C9B—C8B—C13B | 117.82 (17) |
O1A—C6A—C1A | 122.04 (16) | C1A—C2A—H1A | 120.044 |
O1A—C6A—C5A | 115.62 (16) | C3A—C2A—H1A | 120.053 |
C1A—C6A—C5A | 122.34 (16) | C4A—C5A—H2A | 119.672 |
C1A—C7A—C8A | 118.28 (16) | C6A—C5A—H2A | 119.667 |
C1A—C7A—C12A | 123.01 (16) | C8A—C9A—H3A | 119.881 |
C8A—C7A—C12A | 118.70 (17) | C10A—C9A—H3A | 119.871 |
C7A—C8A—C9A | 120.54 (17) | C9A—C10A—H4A | 120.235 |
C7A—C8A—C13A | 120.99 (17) | C11A—C10A—H4A | 120.235 |
C9A—C8A—C13A | 118.47 (17) | C10A—C11A—H5A | 119.615 |
C8A—C9A—C10A | 120.25 (17) | C12A—C11A—H5A | 119.611 |
C9A—C10A—C11A | 119.53 (18) | C14A—C15A—H7A | 109.473 |
C10A—C11A—C12A | 120.77 (18) | C14A—C15A—H8A | 109.469 |
O1A—C13A—O2A | 116.56 (17) | C14A—C15A—H9A | 109.471 |
O1A—C13A—C8A | 118.09 (16) | H7A—C15A—H8A | 109.473 |
O2A—C13A—C8A | 125.34 (18) | H7A—C15A—H9A | 109.470 |
O3A—C14A—C4A | 118.58 (16) | H8A—C15A—H9A | 109.470 |
O3A—C14A—C15A | 120.17 (16) | C1B—C2B—H1B | 120.248 |
C4A—C14A—C15A | 121.25 (16) | C3B—C2B—H1B | 120.241 |
C2B—C1B—C6B | 117.54 (17) | C4B—C5B—H2B | 119.735 |
C2B—C1B—C7B | 123.51 (17) | C6B—C5B—H2B | 119.726 |
C6B—C1B—C7B | 118.94 (17) | C7B—C12B—H6B | 119.910 |
C1B—C2B—C3B | 119.51 (17) | C11B—C12B—H6B | 119.911 |
F1B—C3B—C2B | 116.95 (16) | C12B—C11B—H5B | 119.574 |
F1B—C3B—C4B | 119.61 (17) | C10B—C11B—H5B | 119.585 |
C2B—C3B—C4B | 123.44 (17) | C11B—C10B—H4B | 119.936 |
C3B—C4B—C5B | 116.74 (17) | C9B—C10B—H4B | 119.926 |
C3B—C4B—C14B | 125.49 (17) | C10B—C9B—H3B | 120.341 |
C5B—C4B—C14B | 117.76 (17) | C8B—C9B—H3B | 120.351 |
C4B—C5B—C6B | 120.54 (17) | C7A—C12A—H6A | 119.901 |
O1B—C6B—C1B | 122.04 (17) | C11A—C12A—H6A | 119.891 |
O1B—C6B—C5B | 115.73 (16) | C14B—C15B—H7B | 109.477 |
C1B—C6B—C5B | 122.23 (17) | C14B—C15B—H8B | 109.477 |
O3B—C14B—C4B | 119.10 (17) | C14B—C15B—H9B | 109.459 |
O3B—C14B—C15B | 120.32 (18) | H7B—C15B—H8B | 109.474 |
C4B—C14B—C15B | 120.57 (16) | H7B—C15B—H9B | 109.468 |
C1B—C7B—C12B | 123.16 (17) | H8B—C15B—H9B | 109.472 |
C6A—O1A—C13A—O2A | −179.30 (15) | O3A—C14A—C15A—H9A | −112.0 |
C6A—O1A—C13A—C8A | 1.3 (3) | C4A—C14A—C15A—H7A | −51.9 |
C13A—O1A—C6A—C1A | −0.3 (3) | C4A—C14A—C15A—H8A | −171.9 |
C13A—O1A—C6A—C5A | −179.78 (14) | C4A—C14A—C15A—H9A | 68.1 |
C6B—O1B—C13B—O2B | −178.78 (14) | C2B—C1B—C6B—O1B | 179.93 (14) |
C6B—O1B—C13B—C8B | 1.9 (3) | C2B—C1B—C6B—C5B | 0.4 (3) |
C13B—O1B—C6B—C1B | −0.0 (3) | C6B—C1B—C2B—C3B | 0.4 (3) |
C13B—O1B—C6B—C5B | 179.59 (14) | C6B—C1B—C2B—H1B | −179.6 |
C2A—C1A—C6A—O1A | 179.71 (15) | C2B—C1B—C7B—C12B | 0.4 (3) |
C2A—C1A—C6A—C5A | −0.9 (3) | C2B—C1B—C7B—C8B | 179.50 (14) |
C6A—C1A—C2A—C3A | 0.5 (3) | C7B—C1B—C2B—C3B | −178.09 (14) |
C6A—C1A—C2A—H1A | −179.5 | C7B—C1B—C2B—H1B | 1.9 |
C2A—C1A—C7A—C8A | −179.67 (14) | C6B—C1B—C7B—C12B | −178.07 (14) |
C2A—C1A—C7A—C12A | 1.0 (3) | C6B—C1B—C7B—C8B | 1.0 (2) |
C7A—C1A—C2A—C3A | −178.92 (14) | C7B—C1B—C6B—O1B | −1.5 (3) |
C7A—C1A—C2A—H1A | 1.1 | C7B—C1B—C6B—C5B | 178.91 (13) |
C6A—C1A—C7A—C8A | 0.9 (3) | C1B—C2B—C3B—F1B | 179.49 (14) |
C6A—C1A—C7A—C12A | −178.41 (14) | C1B—C2B—C3B—C4B | −0.8 (3) |
C7A—C1A—C6A—O1A | −0.8 (3) | H1B—C2B—C3B—F1B | −0.5 |
C7A—C1A—C6A—C5A | 178.61 (14) | H1B—C2B—C3B—C4B | 179.2 |
C1A—C2A—C3A—F1A | −180.00 (15) | F1B—C3B—C4B—C5B | −179.91 (13) |
C1A—C2A—C3A—C4A | 0.2 (3) | F1B—C3B—C4B—C14B | 1.6 (3) |
H1A—C2A—C3A—F1A | 0.0 | C2B—C3B—C4B—C5B | 0.3 (3) |
H1A—C2A—C3A—C4A | −179.8 | C2B—C3B—C4B—C14B | −178.12 (15) |
F1A—C3A—C4A—C5A | 179.66 (14) | C3B—C4B—C5B—C6B | 0.4 (3) |
F1A—C3A—C4A—C14A | −0.4 (3) | C3B—C4B—C5B—H2B | −179.6 |
C2A—C3A—C4A—C5A | −0.5 (3) | C3B—C4B—C14B—O3B | 164.33 (17) |
C2A—C3A—C4A—C14A | 179.39 (16) | C3B—C4B—C14B—C15B | −16.6 (3) |
C3A—C4A—C5A—C6A | 0.2 (3) | C5B—C4B—C14B—O3B | −14.1 (3) |
C3A—C4A—C5A—H2A | −179.8 | C5B—C4B—C14B—C15B | 164.96 (15) |
C3A—C4A—C14A—O3A | 178.88 (17) | C14B—C4B—C5B—C6B | 179.01 (14) |
C3A—C4A—C14A—C15A | −1.3 (3) | C14B—C4B—C5B—H2B | −1.0 |
C5A—C4A—C14A—O3A | −1.2 (3) | C4B—C5B—C6B—O1B | 179.62 (15) |
C5A—C4A—C14A—C15A | 178.62 (15) | C4B—C5B—C6B—C1B | −0.8 (3) |
C14A—C4A—C5A—C6A | −179.75 (15) | H2B—C5B—C6B—O1B | −0.4 |
C14A—C4A—C5A—H2A | 0.3 | H2B—C5B—C6B—C1B | 179.2 |
C4A—C5A—C6A—O1A | 179.99 (15) | O3B—C14B—C15B—H7B | −0.9 |
C4A—C5A—C6A—C1A | 0.5 (3) | O3B—C14B—C15B—H8B | −120.9 |
H2A—C5A—C6A—O1A | −0.0 | O3B—C14B—C15B—H9B | 119.1 |
H2A—C5A—C6A—C1A | −179.5 | C4B—C14B—C15B—H7B | −180.0 |
C1A—C7A—C8A—C9A | −179.62 (13) | C4B—C14B—C15B—H8B | 60.0 |
C1A—C7A—C8A—C13A | 0.1 (3) | C4B—C14B—C15B—H9B | −60.0 |
C1A—C7A—C12A—C11A | 179.45 (13) | C1B—C7B—C12B—C11B | 178.81 (14) |
C1A—C7A—C12A—H6A | −0.6 | C1B—C7B—C12B—H6B | −1.2 |
C8A—C7A—C12A—C11A | 0.1 (3) | C1B—C7B—C8B—C9B | −179.09 (13) |
C8A—C7A—C12A—H6A | −179.9 | C1B—C7B—C8B—C13B | 0.8 (3) |
C12A—C7A—C8A—C9A | −0.3 (3) | C12B—C7B—C8B—C9B | 0.1 (3) |
C12A—C7A—C8A—C13A | 179.41 (14) | C12B—C7B—C8B—C13B | 179.99 (14) |
C7A—C8A—C9A—C10A | 0.1 (3) | C8B—C7B—C12B—C11B | −0.3 (3) |
C7A—C8A—C9A—H3A | −179.9 | C8B—C7B—C12B—H6B | 179.7 |
C7A—C8A—C13A—O1A | −1.2 (3) | C7B—C12B—C11B—C10B | 0.2 (3) |
C7A—C8A—C13A—O2A | 179.49 (16) | C7B—C12B—C11B—H5B | −179.8 |
C9A—C8A—C13A—O1A | 178.53 (15) | H6B—C12B—C11B—C10B | −179.8 |
C9A—C8A—C13A—O2A | −0.8 (3) | H6B—C12B—C11B—H5B | 0.2 |
C13A—C8A—C9A—C10A | −179.54 (15) | C12B—C11B—C10B—C9B | 0.1 (3) |
C13A—C8A—C9A—H3A | 0.5 | C12B—C11B—C10B—H4B | −179.9 |
C8A—C9A—C10A—C11A | 0.1 (3) | H5B—C11B—C10B—C9B | −179.9 |
C8A—C9A—C10A—H4A | −179.9 | H5B—C11B—C10B—H4B | 0.1 |
H3A—C9A—C10A—C11A | −179.9 | C11B—C10B—C9B—C8B | −0.4 (3) |
H3A—C9A—C10A—H4A | 0.1 | C11B—C10B—C9B—H3B | 179.6 |
C9A—C10A—C11A—C12A | −0.2 (3) | H4B—C10B—C9B—C8B | 179.6 |
C9A—C10A—C11A—H5A | 179.7 | H4B—C10B—C9B—H3B | −0.4 |
H4A—C10A—C11A—C12A | 179.8 | C10B—C9B—C8B—C7B | 0.3 (3) |
H4A—C10A—C11A—H5A | −0.2 | C10B—C9B—C8B—C13B | −179.66 (15) |
C10A—C11A—C12A—C7A | 0.1 (3) | H3B—C9B—C8B—C7B | −179.7 |
C10A—C11A—C12A—H6A | −179.9 | H3B—C9B—C8B—C13B | 0.4 |
H5A—C11A—C12A—C7A | −179.9 | O1B—C13B—C8B—C7B | −2.3 (3) |
H5A—C11A—C12A—H6A | 0.1 | O1B—C13B—C8B—C9B | 177.64 (13) |
O3A—C14A—C15A—H7A | 128.0 | O2B—C13B—C8B—C7B | 178.43 (16) |
O3A—C14A—C15A—H8A | 8.0 | O2B—C13B—C8B—C9B | −1.6 (3) |
Symmetry codes: (i) x, −y+2, z+1/2; (ii) −x+1/2, −y+3/2, −z; (iii) −x+1, −y+1, −z; (iv) x, −y+1, z−1/2; (v) −x+1, y, −z+1/2; (vi) x, −y+2, z−1/2; (vii) −x+1/2, y−1/2, −z−1/2; (viii) −x+1/2, y+1/2, −z−1/2; (ix) x, −y+1, z+1/2; (x) −x+1, −y+2, −z; (xi) x, y+1, z; (xii) x, y−1, z; (xiii) −x+1/2, −y+5/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C15H9FO3 |
Mr | 256.23 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 100 |
a, b, c (Å) | 26.005 (19), 13.169 (4), 13.297 (8) |
β (°) | 98.02 (6) |
V (Å3) | 4509 (5) |
Z | 16 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.40 × 0.34 × 0.25 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 6119, 5160, 3534 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.137, 1.01 |
No. of reflections | 5160 |
No. of parameters | 343 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.28 |
Computer programs: WinAFC Diffractometer Control Software (Rigaku, 1999), SIR2008 (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), CrystalStructure (Rigaku, 2010).
Acknowledgements
This work was partly supported by Grants-in-Aid (No. 24590141 to YI) for Scientific Research from the Japan Society for the Promotion of Science. We acknowledge the University of Shizuoka for instrumental support, and thank Professor Kei Manabe (University of Shizuoka, Japan) for helpful discussions.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Aryl diketo acids are known to inhibit influenza virus metalloenzyme endonuclease by chelating its metal center (Dias et al.,2009). According to our inhibitor design targeting this metalloenzyme (Ishikawa & Fujii, 2011), we tried to synthesize a biphenyl derivative with acetyl, methoxycarbonyl and difluoro groups by Suzuki-Miyaura cross-coupling reaction of 4'-chloro-2',5'-difluoroacetophenone with o-(methoxycarbonyl)phenylboronic acid in N,N-dimethylformamide (DMF) in the presence of Pd(PPh3)4 and K2CO3. Usual work-up yielded a pink solid, which was not fully analyzed by 1H NMR and MS.
The crystallographic analysis revealed that it is an unexpected biphenyl lactone derivative shown in Fig.1, which should be formed as a result of intramolecular cyclization by additional nucleophilic substitution reaction of the hydrolyzed carboxylate with the proximal fluoride group after the intermolecular cross-coupling reaction. This result well accounts for the 1H NMR and MS spectra. The asymmetric unit of the title compound contains two crystallographically independent molecules related by a non-crystallographic inversion centre. The biphenyl lactone rings are essentially planar, and the mean atomic deviations from the corresponding least-square planes composed of the non-hydrogen atoms of the rings are 0.0137 and 0.0188 Å for molecules A and B, respectively. In addition, face-to-face stacking interactions between the aromatic rings of the benzoate and acetophenone units are observed [centroid–centroid distances = 3.870 (3) and 3.986 (3) Å]. In the crystal, the molecules are further assembled via stacking interaction along the a-axis direction. Molecule A interacts with its inversion equivalent [centroid-centroid distance between the aromatic rings of the benzoate and acetophenone units = 3.932 (3) Å], and molecule B interacts with its twofold axis equivalent [centroid-centroid distance between the aromatic rings of acetophenone units = 3.634 (3) Å].
Biphenyl lactone is a key structural motif found in many natural products and pharmaceuticals (Bringmann et al., 2001). The crystal structures (Robinson et al.,1991; Siegel et al., 2010, Dasari et al., 2012) and biological activity (Sun et al., 2006) of the related compounds are reported.