In the crystal structures of the fully and partially fluorinated flavone derivatives 5,6,7,8-tetrafluoro-2-(2,3,4,5,6-pentafluorophenyl)-4
H-1-benzopyran-4-one, C
15HF
9O
2, (I), and 5,6,7,8-tetrafluoro-2-phenyl-4
H-1-benzopyran-4-one, C
15H
6F
4O
2, (II), the pentafluorophenyl group and the pyranone moiety in (I) are twisted due to repulsion of the F substituents, and a CO(δ
−)
π(δ
+) intermolecular interaction is observed between the carbonyl O atom and the pentafluorophenyl group. In (II), on the other hand, the phenyl group and the pyranone moiety are almost coplanar, and arene–perfluoroarene interactions are observed in the head-to-tail intermolecular columnar stacking between the phenyl group and the tetrafluorophenylene moiety.
Supporting information
CCDC references: 779963; 779964
The two fluorinated flavone derivatives were obtained from the elimination
process of the corresponding dibenzoylmethanide derivatives. Crystals of (I)
and (II) were obtained in poor yield from the synthetic processes involving
bis(pentafluorobenzoyl)methane and benzoylpentafluorobenzoylmethane,
respectively (Uhlemann et al., 1972; Hori et al.,
2009). The
compounds were crystallized by slow evaporation of an MeOH solution to give
crystals suitable for X-ray crystallography.
For the disordered structure of (II), after refinement of the major component
with unit occupancy, it was noted in a difference map in the molecular plane
that there were a large number of small maxima in the 0.2–0.7 e Å-3
range, which could be seen to be a minor component of (II) related to the
major component by an approximate twofold rotation about the molecular length.
The various minor peaks were then labelled B atoms to correspond
exactly with the major A component. Refinement then continued with the
major and minor occupancies refined as linked free variables, with the SAME
command (SHELXL97; Sheldrick, 2008) employed to force the
geometry of
the minor component to conform with that of the major component. Atoms of the
minor B component were refined isotropically, with one global
Uiso value for the ring atoms and another Uiso value for the
exocyclic atoms.
In both (I) and (II) all H atoms were placed in geometrically idealized
positions and refined as riding, with aromatic C—H = 0.95 Å and with
Uiso(H) = 1.2Ueq(C).
For both compounds, data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
(I) 5,6,7,8-tetrafluoro-2-(2,3,4,5,6-pentafluorophenyl)-4
H-1-benzopyran-4-one
top
Crystal data top
C15HF9O2 | F(000) = 752 |
Mr = 384.16 | Dx = 1.929 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4991 reflections |
a = 6.2221 (7) Å | θ = 3.2–27.7° |
b = 25.234 (3) Å | µ = 0.21 mm−1 |
c = 8.4624 (9) Å | T = 100 K |
β = 95.355 (1)° | Plate, pale yellow |
V = 1322.8 (2) Å3 | 0.30 × 0.20 × 0.06 mm |
Z = 4 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2998 independent reflections |
Radiation source: fine-focus sealed tube | 2433 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ϕ and ω scans | h = −8→8 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −32→32 |
Tmin = 0.939, Tmax = 0.987 | l = −10→10 |
14615 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0399P)2 + 0.7568P] where P = (Fo2 + 2Fc2)/3 |
2998 reflections | (Δ/σ)max < 0.001 |
235 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.20 e Å−3 |
Crystal data top
C15HF9O2 | V = 1322.8 (2) Å3 |
Mr = 384.16 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.2221 (7) Å | µ = 0.21 mm−1 |
b = 25.234 (3) Å | T = 100 K |
c = 8.4624 (9) Å | 0.30 × 0.20 × 0.06 mm |
β = 95.355 (1)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2998 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2433 reflections with I > 2σ(I) |
Tmin = 0.939, Tmax = 0.987 | Rint = 0.026 |
14615 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.31 e Å−3 |
2998 reflections | Δρmin = −0.20 e Å−3 |
235 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell esds are taken into
account individually in the estimation of esds in distances, angles and
torsion angles; correlations between esds in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | x | y | z | Uiso*/Ueq | |
O1 | 0.47044 (17) | 0.28350 (4) | 0.86414 (13) | 0.0216 (2) | |
O2 | 0.9748 (2) | 0.35152 (5) | 0.66183 (15) | 0.0342 (3) | |
C1 | 0.8208 (3) | 0.33202 (7) | 0.7199 (2) | 0.0260 (4) | |
C2 | 0.7914 (3) | 0.27518 (7) | 0.7334 (2) | 0.0253 (4) | |
H2 | 0.8937 | 0.2522 | 0.6925 | 0.030* | |
C3 | 0.6258 (2) | 0.25388 (6) | 0.80134 (18) | 0.0209 (3) | |
C4 | 0.4829 (3) | 0.33742 (6) | 0.85302 (18) | 0.0212 (3) | |
C5 | 0.6485 (3) | 0.36368 (7) | 0.78325 (19) | 0.0236 (3) | |
C6 | 0.6374 (3) | 0.41904 (7) | 0.7765 (2) | 0.0291 (4) | |
C7 | 0.4739 (3) | 0.44657 (7) | 0.8372 (2) | 0.0315 (4) | |
C8 | 0.3146 (3) | 0.41949 (7) | 0.9084 (2) | 0.0292 (4) | |
C9 | 0.3195 (3) | 0.36525 (7) | 0.9166 (2) | 0.0245 (3) | |
C10 | 0.5833 (3) | 0.19674 (6) | 0.81544 (19) | 0.0212 (3) | |
C11 | 0.3860 (3) | 0.17514 (6) | 0.75820 (19) | 0.0215 (3) | |
C12 | 0.3425 (3) | 0.12197 (7) | 0.7676 (2) | 0.0246 (4) | |
C13 | 0.4990 (3) | 0.08787 (7) | 0.8354 (2) | 0.0264 (4) | |
C14 | 0.6979 (3) | 0.10787 (7) | 0.8915 (2) | 0.0268 (4) | |
C15 | 0.7377 (3) | 0.16150 (7) | 0.8818 (2) | 0.0242 (3) | |
F1 | 0.78575 (19) | 0.44679 (4) | 0.70727 (14) | 0.0413 (3) | |
F2 | 0.4661 (2) | 0.49931 (4) | 0.82780 (14) | 0.0431 (3) | |
F3 | 0.15662 (19) | 0.44623 (4) | 0.96917 (14) | 0.0392 (3) | |
F4 | 0.16640 (16) | 0.33909 (4) | 0.98643 (12) | 0.0293 (2) | |
F5 | 0.23387 (15) | 0.20657 (4) | 0.68324 (12) | 0.0276 (2) | |
F6 | 0.15002 (16) | 0.10308 (4) | 0.70889 (13) | 0.0344 (3) | |
F7 | 0.45777 (18) | 0.03650 (4) | 0.84682 (13) | 0.0369 (3) | |
F8 | 0.84812 (18) | 0.07552 (4) | 0.96071 (13) | 0.0380 (3) | |
F9 | 0.93097 (16) | 0.17974 (4) | 0.94313 (13) | 0.0340 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0211 (6) | 0.0197 (6) | 0.0247 (6) | −0.0012 (4) | 0.0064 (5) | −0.0009 (4) |
O2 | 0.0305 (7) | 0.0442 (8) | 0.0292 (7) | −0.0115 (6) | 0.0092 (5) | 0.0026 (6) |
C1 | 0.0244 (8) | 0.0339 (9) | 0.0196 (8) | −0.0064 (7) | 0.0010 (7) | 0.0009 (7) |
C2 | 0.0210 (8) | 0.0322 (9) | 0.0231 (8) | 0.0011 (7) | 0.0039 (6) | −0.0012 (7) |
C3 | 0.0194 (8) | 0.0246 (8) | 0.0185 (8) | 0.0022 (6) | 0.0012 (6) | −0.0013 (6) |
C4 | 0.0247 (8) | 0.0201 (8) | 0.0182 (8) | −0.0020 (6) | −0.0013 (6) | −0.0002 (6) |
C5 | 0.0253 (8) | 0.0260 (9) | 0.0189 (8) | −0.0052 (7) | −0.0020 (6) | 0.0010 (6) |
C6 | 0.0329 (9) | 0.0270 (9) | 0.0261 (9) | −0.0101 (7) | −0.0040 (7) | 0.0050 (7) |
C7 | 0.0424 (11) | 0.0204 (8) | 0.0292 (9) | −0.0010 (7) | −0.0090 (8) | 0.0015 (7) |
C8 | 0.0348 (10) | 0.0263 (9) | 0.0255 (9) | 0.0057 (7) | −0.0034 (7) | −0.0038 (7) |
C9 | 0.0266 (8) | 0.0259 (9) | 0.0209 (8) | −0.0015 (7) | 0.0011 (6) | −0.0003 (6) |
C10 | 0.0220 (8) | 0.0235 (8) | 0.0184 (8) | 0.0022 (6) | 0.0043 (6) | −0.0017 (6) |
C11 | 0.0203 (8) | 0.0232 (8) | 0.0212 (8) | 0.0057 (6) | 0.0025 (6) | −0.0006 (6) |
C12 | 0.0237 (8) | 0.0244 (8) | 0.0256 (9) | 0.0003 (7) | 0.0011 (7) | −0.0044 (7) |
C13 | 0.0350 (9) | 0.0183 (8) | 0.0261 (9) | 0.0039 (7) | 0.0045 (7) | −0.0016 (6) |
C14 | 0.0290 (9) | 0.0285 (9) | 0.0225 (8) | 0.0120 (7) | 0.0007 (7) | 0.0022 (7) |
C15 | 0.0216 (8) | 0.0306 (9) | 0.0202 (8) | 0.0021 (7) | 0.0007 (6) | −0.0013 (7) |
F1 | 0.0439 (7) | 0.0325 (6) | 0.0472 (7) | −0.0155 (5) | 0.0033 (5) | 0.0115 (5) |
F2 | 0.0594 (8) | 0.0186 (5) | 0.0490 (7) | −0.0013 (5) | −0.0074 (6) | 0.0034 (5) |
F3 | 0.0461 (7) | 0.0310 (6) | 0.0403 (7) | 0.0138 (5) | 0.0032 (5) | −0.0063 (5) |
F4 | 0.0301 (5) | 0.0306 (5) | 0.0288 (5) | 0.0025 (4) | 0.0112 (4) | 0.0003 (4) |
F5 | 0.0219 (5) | 0.0231 (5) | 0.0365 (6) | 0.0045 (4) | −0.0039 (4) | 0.0008 (4) |
F6 | 0.0295 (6) | 0.0246 (5) | 0.0473 (7) | −0.0035 (4) | −0.0056 (5) | −0.0024 (5) |
F7 | 0.0458 (7) | 0.0190 (5) | 0.0453 (7) | 0.0035 (4) | 0.0001 (5) | 0.0011 (4) |
F8 | 0.0386 (6) | 0.0334 (6) | 0.0400 (6) | 0.0132 (5) | −0.0067 (5) | 0.0068 (5) |
F9 | 0.0249 (5) | 0.0380 (6) | 0.0369 (6) | 0.0008 (4) | −0.0080 (4) | 0.0023 (5) |
Geometric parameters (Å, º) top
O1—C4 | 1.3666 (19) | C8—F3 | 1.334 (2) |
O1—C3 | 1.3679 (19) | C8—C9 | 1.371 (2) |
O2—C1 | 1.220 (2) | C9—F4 | 1.3404 (19) |
C1—C2 | 1.452 (2) | C10—C15 | 1.388 (2) |
C1—C5 | 1.478 (2) | C10—C11 | 1.389 (2) |
C2—C3 | 1.339 (2) | C11—F5 | 1.3474 (18) |
C2—H2 | 0.9500 | C11—C12 | 1.373 (2) |
C3—C10 | 1.472 (2) | C12—F6 | 1.3404 (19) |
C4—C9 | 1.385 (2) | C12—C13 | 1.383 (2) |
C4—C5 | 1.401 (2) | C13—F7 | 1.3266 (19) |
C5—C6 | 1.399 (2) | C13—C14 | 1.379 (2) |
C6—F1 | 1.337 (2) | C14—F8 | 1.3343 (19) |
C6—C7 | 1.371 (3) | C14—C15 | 1.380 (2) |
C7—F2 | 1.334 (2) | C15—F9 | 1.3459 (19) |
C7—C8 | 1.387 (3) | | |
| | | |
C4—O1—C3 | 118.08 (12) | F3—C8—C7 | 120.04 (16) |
O2—C1—C2 | 122.66 (17) | C9—C8—C7 | 120.05 (17) |
O2—C1—C5 | 123.48 (16) | F4—C9—C8 | 120.06 (15) |
C2—C1—C5 | 113.86 (14) | F4—C9—C4 | 119.95 (14) |
C3—C2—C1 | 122.57 (16) | C8—C9—C4 | 119.99 (16) |
C3—C2—H2 | 118.7 | C15—C10—C11 | 116.44 (15) |
C1—C2—H2 | 118.7 | C15—C10—C3 | 122.51 (15) |
C2—C3—O1 | 123.20 (15) | C11—C10—C3 | 121.03 (14) |
C2—C3—C10 | 125.37 (15) | F5—C11—C12 | 117.95 (14) |
O1—C3—C10 | 111.41 (13) | F5—C11—C10 | 119.51 (14) |
O1—C4—C9 | 115.44 (14) | C12—C11—C10 | 122.45 (15) |
O1—C4—C5 | 123.26 (15) | F6—C12—C11 | 120.04 (15) |
C9—C4—C5 | 121.29 (15) | F6—C12—C13 | 120.17 (15) |
C6—C5—C4 | 116.99 (16) | C11—C12—C13 | 119.79 (16) |
C6—C5—C1 | 124.03 (15) | F7—C13—C14 | 120.38 (15) |
C4—C5—C1 | 118.97 (15) | F7—C13—C12 | 120.30 (16) |
F1—C6—C7 | 117.74 (16) | C14—C13—C12 | 119.32 (16) |
F1—C6—C5 | 120.50 (17) | F8—C14—C13 | 119.77 (16) |
C7—C6—C5 | 121.74 (16) | F8—C14—C15 | 120.29 (16) |
F2—C7—C6 | 120.51 (17) | C13—C14—C15 | 119.89 (15) |
F2—C7—C8 | 119.58 (17) | F9—C15—C14 | 118.10 (15) |
C6—C7—C8 | 119.90 (16) | F9—C15—C10 | 119.77 (15) |
F3—C8—C9 | 119.91 (17) | C14—C15—C10 | 122.10 (15) |
| | | |
O2—C1—C2—C3 | 177.97 (16) | O1—C4—C9—F4 | 1.5 (2) |
C5—C1—C2—C3 | −1.7 (2) | C5—C4—C9—F4 | −178.19 (15) |
C1—C2—C3—O1 | −0.2 (3) | O1—C4—C9—C8 | −178.58 (15) |
C1—C2—C3—C10 | 178.40 (15) | C5—C4—C9—C8 | 1.7 (3) |
C4—O1—C3—C2 | 1.7 (2) | C2—C3—C10—C15 | 53.2 (2) |
C4—O1—C3—C10 | −177.04 (13) | O1—C3—C10—C15 | −128.04 (16) |
C3—O1—C4—C9 | 179.09 (14) | C2—C3—C10—C11 | −124.98 (18) |
C3—O1—C4—C5 | −1.2 (2) | O1—C3—C10—C11 | 53.74 (19) |
O1—C4—C5—C6 | 178.39 (14) | C15—C10—C11—F5 | −175.78 (14) |
C9—C4—C5—C6 | −1.9 (2) | C3—C10—C11—F5 | 2.5 (2) |
O1—C4—C5—C1 | −0.8 (2) | C15—C10—C11—C12 | 0.8 (2) |
C9—C4—C5—C1 | 178.92 (15) | C3—C10—C11—C12 | 179.10 (15) |
O2—C1—C5—C6 | 3.3 (3) | F5—C11—C12—F6 | −2.7 (2) |
C2—C1—C5—C6 | −176.97 (16) | C10—C11—C12—F6 | −179.26 (15) |
O2—C1—C5—C4 | −177.56 (16) | F5—C11—C12—C13 | 176.28 (15) |
C2—C1—C5—C4 | 2.2 (2) | C10—C11—C12—C13 | −0.3 (3) |
C4—C5—C6—F1 | −177.89 (15) | F6—C12—C13—F7 | −1.9 (2) |
C1—C5—C6—F1 | 1.3 (3) | C11—C12—C13—F7 | 179.20 (15) |
C4—C5—C6—C7 | 0.9 (3) | F6—C12—C13—C14 | 178.36 (15) |
C1—C5—C6—C7 | 180.00 (16) | C11—C12—C13—C14 | −0.6 (3) |
F1—C6—C7—F2 | −0.6 (3) | F7—C13—C14—F8 | −1.4 (2) |
C5—C6—C7—F2 | −179.34 (15) | C12—C13—C14—F8 | 178.35 (15) |
F1—C6—C7—C8 | 179.17 (15) | F7—C13—C14—C15 | −178.79 (15) |
C5—C6—C7—C8 | 0.4 (3) | C12—C13—C14—C15 | 1.0 (3) |
F2—C7—C8—F3 | −1.0 (2) | F8—C14—C15—F9 | 0.2 (2) |
C6—C7—C8—F3 | 179.22 (16) | C13—C14—C15—F9 | 177.58 (15) |
F2—C7—C8—C9 | 179.07 (16) | F8—C14—C15—C10 | −177.87 (15) |
C6—C7—C8—C9 | −0.7 (3) | C13—C14—C15—C10 | −0.5 (3) |
F3—C8—C9—F4 | −0.4 (3) | C11—C10—C15—F9 | −178.43 (14) |
C7—C8—C9—F4 | 179.51 (15) | C3—C10—C15—F9 | 3.3 (2) |
F3—C8—C9—C4 | 179.75 (15) | C11—C10—C15—C14 | −0.4 (2) |
C7—C8—C9—C4 | −0.4 (3) | C3—C10—C15—C14 | −178.64 (16) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···F5i | 0.95 | 2.42 | 3.3126 (19) | 157 |
Symmetry code: (i) x+1, y, z. |
(II) 5,6,7,8-tetrafluoro-2-phenyl-4
H-1-benzopyran-4-one
top
Crystal data top
C15H6F4O2 | F(000) = 592 |
Mr = 294.20 | Dx = 1.679 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1813 reflections |
a = 7.5400 (11) Å | θ = 2.8–27.8° |
b = 6.4742 (10) Å | µ = 0.15 mm−1 |
c = 23.920 (4) Å | T = 100 K |
β = 94.635 (2)° | Prismatic, pale yellow |
V = 1163.9 (3) Å3 | 0.30 × 0.20 × 0.10 mm |
Z = 4 | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2654 independent reflections |
Radiation source: fine-focus sealed tube | 1979 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.021 |
Detector resolution: 8.333 pixels mm-1 | θmax = 27.9°, θmin = 1.7° |
ϕ and ω scans | h = −9→9 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −8→5 |
Tmin = 0.955, Tmax = 0.985 | l = −31→26 |
6192 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0373P)2 + 0.4193P] where P = (Fo2 + 2Fc2)/3 |
2654 reflections | (Δ/σ)max = 0.001 |
238 parameters | Δρmax = 0.25 e Å−3 |
57 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C15H6F4O2 | V = 1163.9 (3) Å3 |
Mr = 294.20 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.5400 (11) Å | µ = 0.15 mm−1 |
b = 6.4742 (10) Å | T = 100 K |
c = 23.920 (4) Å | 0.30 × 0.20 × 0.10 mm |
β = 94.635 (2)° | |
Data collection top
Bruker APEXII CCD area-detector diffractometer | 2654 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1979 reflections with I > 2σ(I) |
Tmin = 0.955, Tmax = 0.985 | Rint = 0.021 |
6192 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 57 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
2654 reflections | Δρmin = −0.16 e Å−3 |
238 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are
estimated using the full covariance matrix. The cell esds are taken into
account individually in the estimation of esds in distances, angles and
torsion angles; correlations between esds in cell parameters are only used
when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1A | 0.9015 (2) | 0.2512 (3) | 1.05707 (7) | 0.0227 (4) | 0.938 (2) |
C2A | 0.8533 (2) | 0.2554 (3) | 0.99739 (7) | 0.0227 (4) | 0.938 (2) |
H2A | 0.8876 | 0.1422 | 0.9754 | 0.027* | 0.938 (2) |
C3A | 0.7625 (2) | 0.4110 (3) | 0.97134 (7) | 0.0214 (4) | 0.938 (2) |
C4A | 0.7530 (2) | 0.5915 (3) | 1.05683 (7) | 0.0220 (4) | 0.938 (2) |
C5A | 0.8444 (2) | 0.4355 (3) | 1.08735 (7) | 0.0216 (4) | 0.938 (2) |
C6A | 0.8793 (2) | 0.4668 (3) | 1.14526 (7) | 0.0247 (4) | 0.938 (2) |
C7A | 0.8271 (2) | 0.6452 (3) | 1.17037 (7) | 0.0273 (4) | 0.938 (2) |
C8A | 0.7384 (2) | 0.7974 (3) | 1.13874 (8) | 0.0274 (4) | 0.938 (2) |
C9A | 0.6996 (2) | 0.7709 (3) | 1.08234 (7) | 0.0247 (4) | 0.938 (2) |
C10A | 0.7074 (3) | 0.4292 (3) | 0.91119 (7) | 0.0223 (4) | 0.938 (2) |
C11A | 0.6345 (3) | 0.6102 (3) | 0.88843 (8) | 0.0264 (4) | 0.938 (2) |
H11A | 0.6195 | 0.7258 | 0.9120 | 0.032* | 0.938 (2) |
C12A | 0.5831 (3) | 0.6239 (3) | 0.83139 (9) | 0.0315 (4) | 0.938 (2) |
H12A | 0.5338 | 0.7488 | 0.8162 | 0.038* | 0.938 (2) |
C13A | 0.6037 (3) | 0.4563 (4) | 0.79684 (8) | 0.0309 (5) | 0.938 (2) |
H13A | 0.5676 | 0.4658 | 0.7579 | 0.037* | 0.938 (2) |
C14A | 0.6769 (3) | 0.2744 (3) | 0.81867 (9) | 0.0293 (5) | 0.938 (2) |
H14A | 0.6912 | 0.1596 | 0.7947 | 0.035* | 0.938 (2) |
C15A | 0.7295 (2) | 0.2597 (3) | 0.87568 (8) | 0.0267 (4) | 0.938 (2) |
H15A | 0.7804 | 0.1351 | 0.8906 | 0.032* | 0.938 (2) |
F1A | 0.96454 (16) | 0.32372 (19) | 1.17779 (5) | 0.0344 (3) | 0.938 (2) |
F2A | 0.86160 (17) | 0.6723 (2) | 1.22578 (4) | 0.0377 (3) | 0.938 (2) |
F3A | 0.69073 (17) | 0.97080 (19) | 1.16361 (5) | 0.0369 (3) | 0.938 (2) |
F4A | 0.61061 (17) | 0.91801 (18) | 1.05211 (5) | 0.0315 (3) | 0.938 (2) |
O1A | 0.71037 (15) | 0.58076 (18) | 1.00029 (5) | 0.0232 (3) | 0.938 (2) |
O2A | 0.9843 (2) | 0.1084 (2) | 1.08037 (7) | 0.0288 (3) | 0.938 (2) |
C1B | 0.667 (4) | 0.830 (3) | 1.0454 (8) | 0.030 (3)* | 0.062 (2) |
C2B | 0.643 (3) | 0.757 (3) | 0.9885 (8) | 0.030 (3)* | 0.062 (2) |
H2B | 0.5796 | 0.8433 | 0.9618 | 0.036* | 0.062 (2) |
C3B | 0.703 (4) | 0.580 (3) | 0.9704 (7) | 0.030 (3)* | 0.062 (2) |
C4B | 0.8116 (16) | 0.4950 (19) | 1.0635 (4) | 0.030 (3)* | 0.062 (2) |
C5B | 0.759 (3) | 0.681 (2) | 1.0859 (5) | 0.030 (3)* | 0.062 (2) |
C6B | 0.792 (3) | 0.719 (3) | 1.1430 (5) | 0.030 (3)* | 0.062 (2) |
C7B | 0.877 (2) | 0.571 (3) | 1.1777 (4) | 0.030 (3)* | 0.062 (2) |
C8B | 0.929 (3) | 0.385 (3) | 1.1552 (5) | 0.030 (3)* | 0.062 (2) |
C9B | 0.897 (3) | 0.347 (2) | 1.0981 (5) | 0.030 (3)* | 0.062 (2) |
C10B | 0.688 (3) | 0.497 (3) | 0.9101 (4) | 0.030 (3)* | 0.062 (2) |
C11B | 0.740 (3) | 0.335 (3) | 0.9042 (5) | 0.030 (3)* | 0.062 (2) |
H11B | 0.7858 | 0.2649 | 0.9372 | 0.036* | 0.062 (2) |
C12B | 0.743 (5) | 0.222 (4) | 0.8524 (10) | 0.030 (3)* | 0.062 (2) |
H12B | 0.7891 | 0.0865 | 0.8497 | 0.036* | 0.062 (2) |
C13B | 0.672 (6) | 0.336 (5) | 0.8071 (12) | 0.030 (3)* | 0.062 (2) |
H13B | 0.6754 | 0.2806 | 0.7704 | 0.036* | 0.062 (2) |
C14B | 0.595 (5) | 0.526 (6) | 0.8135 (11) | 0.030 (3)* | 0.062 (2) |
H14B | 0.5324 | 0.5926 | 0.7825 | 0.036* | 0.062 (2) |
C15B | 0.611 (5) | 0.621 (5) | 0.8660 (11) | 0.030 (3)* | 0.062 (2) |
H15B | 0.5732 | 0.7586 | 0.8717 | 0.036* | 0.062 (2) |
F1B | 0.753 (4) | 0.889 (4) | 1.1709 (11) | 0.078 (6)* | 0.062 (2) |
F2B | 0.918 (4) | 0.575 (4) | 1.2335 (7) | 0.078 (6)* | 0.062 (2) |
F3B | 1.016 (4) | 0.234 (4) | 1.1855 (10) | 0.078 (6)* | 0.062 (2) |
F4B | 0.952 (6) | 0.165 (5) | 1.0780 (16) | 0.078 (6)* | 0.062 (2) |
O1B | 0.783 (2) | 0.442 (3) | 1.0078 (6) | 0.030 (3)* | 0.062 (2) |
O2B | 0.602 (6) | 0.989 (5) | 1.0642 (15) | 0.078 (6)* | 0.062 (2) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1A | 0.0189 (9) | 0.0217 (9) | 0.0273 (10) | −0.0016 (7) | 0.0015 (7) | 0.0002 (8) |
C2A | 0.0235 (9) | 0.0196 (8) | 0.0253 (9) | −0.0001 (7) | 0.0026 (7) | −0.0032 (7) |
C3A | 0.0183 (8) | 0.0213 (9) | 0.0252 (9) | −0.0028 (7) | 0.0046 (7) | −0.0021 (7) |
C4A | 0.0194 (8) | 0.0216 (9) | 0.0254 (9) | −0.0032 (7) | 0.0047 (7) | −0.0007 (7) |
C5A | 0.0182 (8) | 0.0223 (9) | 0.0248 (9) | −0.0029 (7) | 0.0042 (7) | 0.0000 (7) |
C6A | 0.0210 (9) | 0.0266 (10) | 0.0266 (9) | −0.0025 (7) | 0.0019 (7) | 0.0041 (8) |
C7A | 0.0275 (10) | 0.0315 (10) | 0.0231 (9) | −0.0077 (8) | 0.0026 (7) | −0.0035 (8) |
C8A | 0.0270 (10) | 0.0229 (10) | 0.0333 (10) | −0.0037 (8) | 0.0094 (8) | −0.0062 (8) |
C9A | 0.0222 (9) | 0.0218 (9) | 0.0303 (10) | −0.0015 (7) | 0.0039 (7) | 0.0006 (8) |
C10A | 0.0171 (8) | 0.0225 (10) | 0.0274 (9) | −0.0008 (7) | 0.0023 (7) | 0.0005 (7) |
C11A | 0.0252 (10) | 0.0246 (9) | 0.0288 (10) | −0.0005 (8) | −0.0012 (9) | 0.0017 (9) |
C12A | 0.0318 (10) | 0.0305 (11) | 0.0314 (11) | 0.0010 (9) | −0.0032 (9) | 0.0074 (9) |
C13A | 0.0290 (10) | 0.0395 (14) | 0.0240 (10) | −0.0013 (10) | 0.0011 (8) | 0.0028 (9) |
C14A | 0.0280 (10) | 0.0336 (12) | 0.0266 (11) | −0.0002 (11) | 0.0047 (10) | −0.0038 (9) |
C15A | 0.0232 (9) | 0.0264 (10) | 0.0308 (11) | 0.0034 (8) | 0.0048 (8) | 0.0002 (8) |
F1A | 0.0384 (7) | 0.0349 (7) | 0.0290 (6) | 0.0033 (6) | −0.0025 (5) | 0.0035 (5) |
F2A | 0.0477 (8) | 0.0426 (7) | 0.0226 (6) | −0.0054 (6) | 0.0012 (5) | −0.0085 (5) |
F3A | 0.0446 (8) | 0.0283 (6) | 0.0389 (7) | −0.0027 (5) | 0.0102 (5) | −0.0121 (5) |
F4A | 0.0348 (6) | 0.0227 (7) | 0.0371 (7) | 0.0048 (5) | 0.0041 (5) | 0.0005 (5) |
O1A | 0.0245 (6) | 0.0206 (6) | 0.0244 (7) | 0.0032 (5) | 0.0012 (5) | 0.0001 (5) |
O2A | 0.0308 (9) | 0.0273 (8) | 0.0277 (7) | 0.0047 (6) | −0.0014 (6) | 0.0017 (6) |
Geometric parameters (Å, º) top
C1A—O2A | 1.224 (2) | C1B—O2B | 1.241 (18) |
C1A—C2A | 1.445 (2) | C1B—C2B | 1.438 (17) |
C1A—C5A | 1.478 (2) | C1B—C5B | 1.497 (16) |
C2A—C3A | 1.342 (2) | C2B—C3B | 1.316 (17) |
C2A—H2A | 0.9500 | C2B—H2B | 0.9500 |
C3A—O1A | 1.373 (2) | C3B—O1B | 1.370 (17) |
C3A—C10A | 1.470 (2) | C3B—C10B | 1.534 (15) |
C4A—O1A | 1.366 (2) | C4B—O1B | 1.373 (14) |
C4A—C9A | 1.387 (2) | C4B—C5B | 1.3900 |
C4A—C5A | 1.395 (2) | C4B—C9B | 1.3900 |
C5A—C6A | 1.404 (2) | C5B—C6B | 1.3900 |
C6A—F1A | 1.340 (2) | C6B—F1B | 1.333 (17) |
C6A—C7A | 1.374 (3) | C6B—C7B | 1.3900 |
C7A—F2A | 1.341 (2) | C7B—F2B | 1.346 (16) |
C7A—C8A | 1.382 (3) | C7B—C8B | 1.3900 |
C8A—F3A | 1.334 (2) | C8B—F3B | 1.352 (16) |
C8A—C9A | 1.368 (3) | C8B—C9B | 1.3900 |
C9A—F4A | 1.342 (2) | C9B—F4B | 1.352 (17) |
C10A—C11A | 1.387 (3) | C10B—C11B | 1.1373 |
C10A—C15A | 1.406 (3) | C10B—C15B | 1.409 (17) |
C11A—C12A | 1.391 (3) | C11B—C12B | 1.438 (18) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—C13A | 1.380 (3) | C12B—C13B | 1.383 (19) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.385 (3) | C13B—C14B | 1.374 (19) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.392 (3) | C14B—C15B | 1.395 (19) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C15A—H15A | 0.9500 | C15B—H15B | 0.9500 |
| | | |
O2A—C1A—C2A | 122.87 (16) | O2B—C1B—C2B | 126 (2) |
O2A—C1A—C5A | 122.99 (17) | O2B—C1B—C5B | 118 (2) |
C2A—C1A—C5A | 114.13 (16) | C2B—C1B—C5B | 114.7 (15) |
C3A—C2A—C1A | 123.44 (16) | C3B—C2B—C1B | 125.2 (18) |
C3A—C2A—H2A | 118.3 | C3B—C2B—H2B | 117.4 |
C1A—C2A—H2A | 118.3 | C1B—C2B—H2B | 117.4 |
C2A—C3A—O1A | 121.50 (16) | C2B—C3B—O1B | 119.8 (15) |
C2A—C3A—C10A | 127.42 (16) | C2B—C3B—C10B | 127.6 (16) |
O1A—C3A—C10A | 111.08 (14) | O1B—C3B—C10B | 112.5 (13) |
O1A—C4A—C9A | 115.13 (15) | O1B—C4B—C5B | 124.3 (9) |
O1A—C4A—C5A | 123.22 (15) | O1B—C4B—C9B | 115.7 (9) |
C9A—C4A—C5A | 121.65 (16) | C5B—C4B—C9B | 120.0 |
C4A—C5A—C6A | 117.23 (16) | C6B—C5B—C4B | 120.0 |
C4A—C5A—C1A | 118.63 (16) | C6B—C5B—C1B | 124.0 (8) |
C6A—C5A—C1A | 124.13 (16) | C4B—C5B—C1B | 116.0 (8) |
F1A—C6A—C7A | 117.90 (16) | F1B—C6B—C5B | 127.5 (13) |
F1A—C6A—C5A | 121.11 (16) | F1B—C6B—C7B | 112.5 (14) |
C7A—C6A—C5A | 120.99 (16) | C5B—C6B—C7B | 120.0 |
F2A—C7A—C6A | 120.15 (17) | F2B—C7B—C8B | 110.6 (13) |
F2A—C7A—C8A | 119.64 (17) | F2B—C7B—C6B | 129.4 (13) |
C6A—C7A—C8A | 120.20 (17) | C8B—C7B—C6B | 120.0 |
F3A—C8A—C9A | 120.11 (17) | F3B—C8B—C9B | 116.0 (13) |
F3A—C8A—C7A | 119.46 (17) | F3B—C8B—C7B | 124.0 (13) |
C9A—C8A—C7A | 120.43 (17) | C9B—C8B—C7B | 120.0 |
F4A—C9A—C8A | 120.02 (16) | F4B—C9B—C8B | 117.9 (16) |
F4A—C9A—C4A | 120.50 (16) | F4B—C9B—C4B | 122.1 (16) |
C8A—C9A—C4A | 119.48 (16) | C8B—C9B—C4B | 120.0 |
C11A—C10A—C15A | 119.01 (17) | C11B—C10B—C15B | 123.9 (14) |
C11A—C10A—C3A | 121.58 (17) | C11B—C10B—C3B | 116.0 (8) |
C15A—C10A—C3A | 119.41 (17) | C15B—C10B—C3B | 120.1 (17) |
C10A—C11A—C12A | 120.62 (19) | C10B—C11B—C12B | 127.2 (15) |
C10A—C11A—H11A | 119.7 | C10B—C11B—H11B | 116.4 |
C12A—C11A—H11A | 119.7 | C12B—C11B—H11B | 116.4 |
C13A—C12A—C11A | 120.08 (18) | C13B—C12B—C11B | 112 (2) |
C13A—C12A—H12A | 120.0 | C13B—C12B—H12B | 124.0 |
C11A—C12A—H12A | 120.0 | C11B—C12B—H12B | 124.0 |
C12A—C13A—C14A | 120.22 (18) | C14B—C13B—C12B | 122 (2) |
C12A—C13A—H13A | 119.9 | C14B—C13B—H13B | 119.0 |
C14A—C13A—H13A | 119.9 | C12B—C13B—H13B | 119.0 |
C13A—C14A—C15A | 120.1 (2) | C13B—C14B—C15B | 119 (2) |
C13A—C14A—H14A | 120.0 | C13B—C14B—H14B | 120.4 |
C15A—C14A—H14A | 120.0 | C15B—C14B—H14B | 120.4 |
C14A—C15A—C10A | 119.99 (19) | C14B—C15B—C10B | 115.2 (19) |
C14A—C15A—H15A | 120.0 | C14B—C15B—H15B | 122.4 |
C10A—C15A—H15A | 120.0 | C10B—C15B—H15B | 122.4 |
C4A—O1A—C3A | 119.06 (13) | C3B—O1B—C4B | 119.8 (14) |
| | | |
O2A—C1A—C2A—C3A | −179.99 (18) | O2B—C1B—C2B—C3B | −175 (4) |
C5A—C1A—C2A—C3A | −0.9 (2) | C5B—C1B—C2B—C3B | −4 (5) |
C1A—C2A—C3A—O1A | 0.8 (3) | C1B—C2B—C3B—O1B | 5 (5) |
C1A—C2A—C3A—C10A | −179.91 (17) | C1B—C2B—C3B—C10B | −177 (3) |
O1A—C4A—C5A—C6A | −179.94 (16) | O1B—C4B—C5B—C6B | 179.1 (12) |
C9A—C4A—C5A—C6A | 0.4 (2) | C9B—C4B—C5B—C6B | 0.0 |
O1A—C4A—C5A—C1A | 1.3 (2) | O1B—C4B—C5B—C1B | 0 (2) |
C9A—C4A—C5A—C1A | −178.33 (16) | C9B—C4B—C5B—C1B | −180 (2) |
O2A—C1A—C5A—C4A | 178.99 (17) | O2B—C1B—C5B—C6B | −7 (4) |
C2A—C1A—C5A—C4A | −0.1 (2) | C2B—C1B—C5B—C6B | −178.4 (18) |
O2A—C1A—C5A—C6A | 0.3 (3) | O2B—C1B—C5B—C4B | 173 (3) |
C2A—C1A—C5A—C6A | −178.82 (16) | C2B—C1B—C5B—C4B | 1 (3) |
C4A—C5A—C6A—F1A | 179.20 (15) | C4B—C5B—C6B—F1B | 179 (3) |
C1A—C5A—C6A—F1A | −2.1 (3) | C1B—C5B—C6B—F1B | −2 (2) |
C4A—C5A—C6A—C7A | −0.8 (2) | C4B—C5B—C6B—C7B | 0.0 |
C1A—C5A—C6A—C7A | 177.92 (16) | C1B—C5B—C6B—C7B | 180 (2) |
F1A—C6A—C7A—F2A | 0.0 (3) | F1B—C6B—C7B—F2B | 2 (3) |
C5A—C6A—C7A—F2A | 179.99 (16) | C5B—C6B—C7B—F2B | −179 (2) |
F1A—C6A—C7A—C8A | −179.83 (16) | F1B—C6B—C7B—C8B | −179 (2) |
C5A—C6A—C7A—C8A | 0.1 (3) | C5B—C6B—C7B—C8B | 0.0 |
F2A—C7A—C8A—F3A | 1.1 (3) | F2B—C7B—C8B—F3B | −3 (3) |
C6A—C7A—C8A—F3A | −179.07 (16) | C6B—C7B—C8B—F3B | 178 (3) |
F2A—C7A—C8A—C9A | −178.98 (16) | F2B—C7B—C8B—C9B | 178.9 (17) |
C6A—C7A—C8A—C9A | 0.9 (3) | C6B—C7B—C8B—C9B | 0.0 |
F3A—C8A—C9A—F4A | −1.2 (3) | F3B—C8B—C9B—F4B | 1 (3) |
C7A—C8A—C9A—F4A | 178.82 (16) | C7B—C8B—C9B—F4B | 179 (3) |
F3A—C8A—C9A—C4A | 178.74 (15) | F3B—C8B—C9B—C4B | −179 (2) |
C7A—C8A—C9A—C4A | −1.2 (3) | C7B—C8B—C9B—C4B | 0.0 |
O1A—C4A—C9A—F4A | 0.9 (2) | O1B—C4B—C9B—F4B | 2 (3) |
C5A—C4A—C9A—F4A | −179.48 (15) | C5B—C4B—C9B—F4B | −179 (3) |
O1A—C4A—C9A—C8A | −179.11 (15) | O1B—C4B—C9B—C8B | −179.2 (11) |
C5A—C4A—C9A—C8A | 0.5 (3) | C5B—C4B—C9B—C8B | 0.0 |
C2A—C3A—C10A—C11A | −171.40 (18) | C2B—C3B—C10B—C11B | −176 (3) |
O1A—C3A—C10A—C11A | 8.0 (2) | O1B—C3B—C10B—C11B | 2 (3) |
C2A—C3A—C10A—C15A | 8.3 (3) | C2B—C3B—C10B—C15B | 4 (5) |
O1A—C3A—C10A—C15A | −172.29 (16) | O1B—C3B—C10B—C15B | −179 (3) |
C15A—C10A—C11A—C12A | 0.3 (3) | C15B—C10B—C11B—C12B | 2 (3) |
C3A—C10A—C11A—C12A | −179.96 (17) | C3B—C10B—C11B—C12B | −179 (3) |
C10A—C11A—C12A—C13A | 0.3 (3) | C10B—C11B—C12B—C13B | −1 (4) |
C11A—C12A—C13A—C14A | −0.5 (3) | C11B—C12B—C13B—C14B | −5 (6) |
C12A—C13A—C14A—C15A | 0.2 (3) | C12B—C13B—C14B—C15B | 9 (7) |
C13A—C14A—C15A—C10A | 0.4 (3) | C13B—C14B—C15B—C10B | −8 (6) |
C11A—C10A—C15A—C14A | −0.6 (3) | C11B—C10B—C15B—C14B | 3 (5) |
C3A—C10A—C15A—C14A | 179.63 (18) | C3B—C10B—C15B—C14B | −177 (3) |
C9A—C4A—O1A—C3A | 178.19 (14) | C2B—C3B—O1B—C4B | −4 (4) |
C5A—C4A—O1A—C3A | −1.5 (2) | C10B—C3B—O1B—C4B | 178 (2) |
C2A—C3A—O1A—C4A | 0.4 (2) | C5B—C4B—O1B—C3B | 2 (3) |
C10A—C3A—O1A—C4A | −179.02 (14) | C9B—C4B—O1B—C3B | −179 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12A—H12A···F2Ai | 0.95 | 2.48 | 3.198 (2) | 132 |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C15HF9O2 | C15H6F4O2 |
Mr | 384.16 | 294.20 |
Crystal system, space group | Monoclinic, P21/n | Monoclinic, P21/n |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 6.2221 (7), 25.234 (3), 8.4624 (9) | 7.5400 (11), 6.4742 (10), 23.920 (4) |
β (°) | 95.355 (1) | 94.635 (2) |
V (Å3) | 1322.8 (2) | 1163.9 (3) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.21 | 0.15 |
Crystal size (mm) | 0.30 × 0.20 × 0.06 | 0.30 × 0.20 × 0.10 |
|
Data collection |
Diffractometer | Bruker APEXII CCD area-detector diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.939, 0.987 | 0.955, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14615, 2998, 2433 | 6192, 2654, 1979 |
Rint | 0.026 | 0.021 |
(sin θ/λ)max (Å−1) | 0.649 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.094, 1.05 | 0.040, 0.094, 1.03 |
No. of reflections | 2998 | 2654 |
No. of parameters | 235 | 238 |
No. of restraints | 0 | 57 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.20 | 0.25, −0.16 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···F5i | 0.95 | 2.42 | 3.3126 (19) | 157.1 |
Symmetry code: (i) x+1, y, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12A—H12A···F2Ai | 0.95 | 2.48 | 3.198 (2) | 132.0 |
Symmetry code: (i) x−1/2, −y+3/2, z−1/2. |
Selected bond distances (Å) and angles (°) of (I), molecule A of (II) and
flavone top | (I) | (IIA) | Flavone-1a | Flavone-2a |
C1-O2 | 1.220 (2) | 1.224 (2) | 1.235 (2) | 1.232 (2) |
C1-C2 | 1.452 (2) | 1.445 (2) | 1.445 (2) | 1.448 (2) |
C2-C3 | 1.339 (2) | 1.342 (2) | 1.353 (2) | 1.354 (2) |
C5-C1 | 1.478 (2) | 1.478 (2) | 1.476 (2) | 1.475 (2) |
C1-C5-C6 | 124.03 (15) | 124.13 (16) | 122.29 (16) | 121.82 (16) |
C2-C1-C5 | 113.86 (14) | 114.13 (16) | 114.69 (15) | 114.18 (15) |
C3-O1-C4 | 118.08 (12) | 119.06 (13) | 119.26 (13) | 119.10 (13) |
Notes: (a) two crystallographically independent molecules, denoted flavone-1
and flavone-2, are observed at 150 K (Waller et al., 2003). |
Flavone derivatives are one of the very important yellow pigments in natural plants. In particular, related compounds with the flavone framework have been widely investigated as unique biologically active reagents (Havsteen, 1983; Das & Rosazza, 2006). More than 100 flavone derivatives and nine naphthoflavone derivatives were found in a search of the Cambridge Structural Database (CSD, Version 5.30 of November 2008; Allen, 2002) and the crystal structure of flavone was determined by Waller et al. (2003). However, only two kinds of fluorinated flavone derivatives have been reported to date: 3-[1-(2,2-dimethylhydrazinylidene)ethyl]-6,7-difluoro-2-phenyl-4H-1-benzopyran-4-one (Vales et al., 2001) and 3-(4-fluorophenyl)-1H-naphtho[2,1-b]pyran-1-one (Neuman et al., 1989). Here, we report the first perfluorinated derivatives of the flavone framework, synthesized in order to understand the influence of fluorination effects on molecular structure and crystal packing, 5,6,7,8-tetrafluoro-2-(2,3,4,5,6-pentafluorophenyl)-4H-1-benzopyran-4-one, (I), and 5,6,7,8-tetrafluoro-2-phenyl-4H-1-benzopyran-4-one, (II).
Fully fluorinated aromatic compounds show an interaction with anion species (Quiñonero et al., 2002) and/or aromatic hydrocarbons (Patrick & Prosser, 1960; Williams, 1993; Hori et al., 2009), based on reversion of the charge orientation of the quadrupole moments compared with aromatic compounds. Accordingly, the three compounds (I), (II) and the non-fluorinated flavone (Waller et al., 2003) show completely different arrangements in these molecular packings. For example, three kinds of electrostatic interactions, dipole–π, arene–perfluoroarene and π–π interactions, are dominantly observed in (I), (II) and flavone, respectively.
The molecular structures of (I) and (II) are shown in Fig. 1. The molecule of (II) was found to be slightly disordered, with site-occupancy ratios of 0.938 (2) and 0.062 (2), respectively, for components A and B; only the major component, A, is shown here. In Fig. 2, the relationship between the disordered components A and B is shown. The minor B component is related to the major A component by an approximate twofold rotation about the molecular length. This sort of disorder is often found in planar molecules with weak intermolecular contacts (Ferguson et al., 1999). Hereinafter, we only discuss the major component, A. The hydrogen-bond geometries of (I) and component A of (II) are summarized in Tables 1 and 2, respectively. Selected bond lengths and angles for (I), component A of (II) and flavone (two crystallographically independent molecules, flavone-1 and flavone-2) are given in Table 3.
In the molecular structure of (I), the benzopyranone ring system (rings A and C) is planar and the r.m.s. deviation of atoms C1–C9/O1 is 0.018 Å. The pentafluorophenyl group and the pyranone moiety are highly twisted with respect to each other and the dihedral angle between the planes of the two rings defined by atoms C10–C15 (ring B) and C1–C3/O1/C4/C5 (ring C) is 52.78 (4)° (Fig. 1). On the other hand, in component A of (II), the phenyl group and the pyranone moiety are almost coplanar and the dihedral angle between the planes of the two rings defined by rings B and C is 7.88 (8)°, the benzopyranone ring system also being planar (r.m.s. deviation of the ten atoms is 0.015 Å). The difference can be explained by the repulsion of the F-substitution on atom C15. The carbonyl double bonds in (I) and component A of (II) are slightly [Text missing?] but significantly more localized than those in non-fluorinated flavone (Table 3). The C1—C5—C6 bond angles in the fluorinated compounds, (I) and component A of (II), are larger than those of non-fluorinated flavone. This is considered to be due to basic steric effects and electrostatic repulsion between atoms O2 and F1. Due to the influence of the F-substitution at F1, the C2—C1—C5 and C3—O1—C4 bond angles of the two fluorinated compounds are smaller than those of the non-fluorinated flavone (Table 3). The r.m.s. deviations of the structural overlay (Macrae et al., 2006) of the 12 atoms in the benzopyranone ring system (C1–C10/O1/O2) in (I), (II) and flavone are small, e.g. 0.04 Å between (I) and flavone-1 and (I) and flavone-2, and 0.03 Å between (II) and flavone-1, (II) and flavone-2, and (I) and (II).
The crystal packings of (I), (II) and flavone are quite different, as shown in Figs. 3, 4 and 5, respectively. In the crystal structure of (I), no remarkable intermolecular π–π stacking is observed for either the pentafluorophenyl group or the pyranone moiety, while the π planes of the pentafluorophenyl (B) and tetrafluorobenzopyranone (A and C) rings are arranged in an anti-parallel way. Carbonyl atom O2 at (x, y, z) interacts closely with a pentafluorophenyl group at (x + 1/2, -y + 1/2, z - 1/2), and vice versa the pentafluorophenyl group at (x, y, z) interacts with another carbonyl atom O2iii [symmetry code: (iii) x - 1/2, -y + 1/2, z + 1/2]; the O2···CgBii distance [symmetry code: (ii) x + 1/2, -y + 1/2, z - 1/2] is 2.9228 (15) Å, where CgB is the centroid of the pentafluorophenyl ring B. Thus, the negative charge orientation of the O atom and the positive charge of the centroid of the fluorinated ring interact, which can be classified as a dipole–π interaction. Accordingly, the molecules are in a head-to-tail arrangement diagonally in the ac plane. Intermolecular C—F···π interactions are also observed, with distances between the F atoms and the ring centroids F4···CgB, F6···CgA and F9···CgC of 3.0765 (13), 3.1580 (13), and 3.1332 (13) Å, respectively. Intermolecular interactions induced by fluorination are also observed, which are the weak hydrogen bond (Desiraju, 1996; Thalladi et al., 1998) C2—H2···F5i [symmetry code: (i) x + 1, y, z; Table 1] and the dipole–dipole interaction between C1═ O2 and C9i—F4i [the C1···F4i and O2···C9i short intermolecular distances are 2.973 (2) and 2.916 (2) Å, respectively].
Intermolecular π–π interactions were clearly observed in the crystal structures of (II) and flavone, which are highly coplanar molecules. Both crystals show remarkable π–π stacking along the a axis to give columnar layers. In the layers, the carbonyl C═O groups are arranged in an interdigitating manner by the dipole–dipole repulsion in both structures. However, the structures of (II) and flavone are clearly different in their stacking positions. In (II), phenyl group B and tetrafluorophenylene moiety A interact closely by head-to-tail arrangement of the molecules, clearly showing an arene–perfluoroarene interaction; the intermolecular distances between the two centroids of the rings, CgC···CgCii [symmetry code: (ii) -x + 2, -y + 1, -z + 2] and CgA···CgBiii [symmetry code: (iii) -x + 1, -y + 1, -z + 2] are 3.5015 (11) and 3.5371 (12) Å, respectively. The corresponding perpendicular distances are 3.3605 (6) and 3.4481 (6) Å, respectively. In contrast, the phenyl groups are overlapped by a head-to-head arrangement of the flavones (Waller et al., 2003), showing π–π stacking; the intermolecular distances CgC···CgCi [symmetry code: (i) x + 1/2, -y + 3/2, -z + 1] and CgB···CgBi are 3.7904 (15) and 3.8128 (15) Å, respectively. The corresponding perpendicular distances are 3.4176 (7) and 3.4707 (7) Å, respectively. Thus, the phenyl group preferentially interacts with the tetrafluorophenylene moiety through an arene–perfluoroarene interaction, as opposed to with the phenyl group through a π–π interaction. In addition, the weak intermolecular hydrogen bond C12A—H12A···F2Ai [symmetry code: (i) x - 1/2, -y + 3/2, z - 1/2] [Not the same symop (i) as above - please clarify] is observed in (II), as shown in Table 2. Intermolecular C—F···π interactions are also observed in (II), of the form C6A—F1A···CgBii, with F1A···CgBii = 3.3769 (16) Å and the C6A—F1A···CgBii angle = 86.32 (9)°.