Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109025141/gz3166sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025141/gz3166Iasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025141/gz3166Ibsup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025141/gz3166IIsup4.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025141/gz3166Icsup5.hkl |
CCDC references: 746078; 746079; 746080; 746081
HFPD (98% pure) was purchased from Aldrich (Milwaukee, Wisconsin, USA) and used without further purification. Twinned crystals of HFPD were grown by slow evaporation of a methanol solution under ambient conditions. A specimen was glued with epoxy cement to the tip of a 0.15 mm glass fiber and mounted on a Bruker SMART 1000 CCD Platform diffractometer equipped with an Oxford Cryosystems Cryostream 600 cryostat. Form (Ia) was placed on the diffractometer at 283 K and the data collected. Form (Ib) was obtained by supercooling the metastable phase (I) at 1 K min-1 to 173 K. This crystalline phase persisted throughout the data collection at 173 K. In order to obtain phase (II) at 173 K, the flow of the cryostat was blocked to allow the specimen to warm to room temperature for about 1 s, then the blockage was removed, which allowed the specimen to return to 173 K. Initial indexing revealed that the phase change to phase (II) had taken place. Data collection on phase (II) was completed. After this the cryostat was warmed at 1 K min-1 to 283 K. The specimen returned to phase (I) and a final data collection on form (Ic) was completed.
DSC measurements were obtained from a fine-powdered sample of HFPD using a TA Instruments Q1000 DSC with a 5 K min-1 temperature ramp. Temperature-dependent XRD data were collected from a fine-powdered sample of HFPD on a Bruker GADDS microdiffractometer with Cu Kα radiation, coupled to a locally built cryostat with an Omega temperature controller.
Aliphatic H atoms were treated as riding on the host C atoms, with C—H = 0.96 Å and Uiso(H) = 1.2Ueq(C) for forms (Ia) and (Ic), and with C—H = 0.98 Å and Uiso(H) = 1.2Ueq(C) for forms (Ib) and (II). Hydroxyl H atoms were initially located in the difference Fourier maps and thereafter treated as idealized, torsionally refined on the host O atoms with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O) for forms (Ia) and (Ic), and with O—H = 0.84 Å and Uiso(H) = 1.5Ueq(O) for forms (Ib) and (II).
For all compounds, data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 2007); data reduction: SHELXL97 (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
C5H6F6O2 | Z = 2 |
Mr = 212.10 | F(000) = 212 |
Triclinic, P1 | Dx = 1.852 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9343 (10) Å | Cell parameters from 2985 reflections |
b = 6.8918 (14) Å | θ = 3.1–27.3° |
c = 11.342 (2) Å | µ = 0.23 mm−1 |
α = 81.943 (3)° | T = 283 K |
β = 85.847 (3)° | Block, colourless |
γ = 86.529 (3)° | 0.35 × 0.20 × 0.17 mm |
V = 380.41 (13) Å3 |
Bruker SMART 1000 CCD Platform diffractometer | 1721 independent reflections |
Radiation source: normal-focus sealed tube | 1419 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and ϕ scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | h = −6→6 |
Tmin = 0.924, Tmax = 0.962 | k = −8→8 |
4125 measured reflections | l = 0→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0415P)2 + 0.0467P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1721 reflections | Δρmax = 0.18 e Å−3 |
240 parameters | Δρmin = −0.17 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with Friedel pairs merged |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.2 (9) |
C5H6F6O2 | γ = 86.529 (3)° |
Mr = 212.10 | V = 380.41 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.9343 (10) Å | Mo Kα radiation |
b = 6.8918 (14) Å | µ = 0.23 mm−1 |
c = 11.342 (2) Å | T = 283 K |
α = 81.943 (3)° | 0.35 × 0.20 × 0.17 mm |
β = 85.847 (3)° |
Bruker SMART 1000 CCD Platform diffractometer | 1721 independent reflections |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | 1419 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.962 | Rint = 0.030 |
4125 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.085 | Δρmax = 0.18 e Å−3 |
S = 1.03 | Δρmin = −0.17 e Å−3 |
1721 reflections | Absolute structure: Flack (1983), with Friedel pairs merged |
240 parameters | Absolute structure parameter: 0.2 (9) |
3 restraints |
Experimental. Cell Refinement: Component Input RLV.Excl Used WorstRes BestRes Min.2 T h Max.2 T h 1.1 (1) 1735 0 1735 6.8149 0.7751 5.978 54.578 1.2 (2) 1250 0 1250 6.2110 0.7751 6.560 54.578 A l l 2985 0 2985 6.8149 0.7751 5.978 54.578 Orientation ('UB') matrix (Component 1.1 (1)): 0.0162457 0.1294415 0.0284999 0.0405288 - 0.0689863 0.0808592 0.1987223 - 0.0041799 - 0.0247312 Orientation ('UB') matrix (Component 1.2 (2)): 0.0474380 - 0.1294389 - 0.0285336 0.0559408 0.0690027 - 0.0808352 0.1897823 0.0039865 0.0247708 Rotated from first domain by 179.8 degrees about reciprocal axis 1.000 0.083 0.167 and real axis 1.000 - 0.003 - 0.001 Twin Law (SAINT V7.34 A, final) Transforms h1.1(1)->h1.2(2) 1.00009 - 0.00091 0.00018 0.16753 - 1.00005 0.00028 0.33368 - 0.00111 - 0.99974 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.3765 (5) | 0.3523 (3) | 0.90099 (18) | 0.0563 (6) | |
F2 | −0.0362 (5) | 0.4571 (3) | 0.86504 (19) | 0.0584 (6) | |
F3 | 0.5165 (4) | 0.3433 (3) | 0.67348 (18) | 0.0526 (5) | |
F4 | 0.0988 (4) | 0.3953 (3) | 0.62393 (17) | 0.0519 (5) | |
F5 | 0.4549 (5) | 0.7076 (3) | 0.76595 (17) | 0.0522 (5) | |
F6 | 0.0646 (4) | 0.7516 (3) | 0.68813 (19) | 0.0512 (5) | |
O1 | 0.0272 (5) | 0.0550 (4) | 0.9524 (2) | 0.0562 (7) | |
H1A | 0.1665 | 0.0221 | 0.9870 | 0.084* | |
O2 | 0.4688 (5) | 0.9323 (3) | 0.5413 (3) | 0.0549 (7) | |
H2A | 0.3260 | 0.9856 | 0.5175 | 0.082* | |
C1 | 0.0965 (8) | 0.1346 (5) | 0.8331 (3) | 0.0462 (8) | |
H1C | −0.0575 | 0.1306 | 0.7851 | 0.055* | |
H1B | 0.2469 | 0.0567 | 0.8008 | 0.055* | |
C2 | 0.1757 (7) | 0.3437 (4) | 0.8276 (3) | 0.0351 (7) | |
C3 | 0.2749 (6) | 0.4355 (4) | 0.7014 (3) | 0.0340 (6) | |
C4 | 0.3128 (7) | 0.6583 (4) | 0.6782 (3) | 0.0360 (7) | |
C5 | 0.4488 (8) | 0.7260 (5) | 0.5572 (3) | 0.0462 (8) | |
H5A | 0.6291 | 0.6626 | 0.5505 | 0.055* | |
H5B | 0.3440 | 0.6893 | 0.4954 | 0.055* | |
F7 | 0.5778 (5) | 0.3478 (3) | 0.39487 (19) | 0.0582 (6) | |
F8 | 0.9767 (5) | 0.4681 (3) | 0.37434 (19) | 0.0611 (6) | |
F9 | 0.5653 (5) | 0.3397 (3) | 0.1640 (2) | 0.0574 (6) | |
F10 | 0.9901 (4) | 0.4079 (3) | 0.13014 (18) | 0.0544 (6) | |
F11 | 0.4958 (5) | 0.7054 (3) | 0.26218 (18) | 0.0592 (6) | |
F12 | 0.9052 (5) | 0.7597 (3) | 0.1881 (2) | 0.0588 (6) | |
O3 | 0.9736 (5) | 0.0629 (4) | 0.4573 (2) | 0.0557 (7) | |
H3A | 0.8233 | 0.0396 | 0.4902 | 0.084* | |
O4 | 0.5230 (5) | 0.9298 (3) | 0.0374 (2) | 0.0515 (6) | |
H4A | 0.6651 | 0.9849 | 0.0172 | 0.077* | |
C6 | 0.9447 (8) | 0.1424 (5) | 0.3375 (3) | 0.0500 (9) | |
H6A | 0.8318 | 0.0603 | 0.3010 | 0.060* | |
H6B | 1.1219 | 0.1444 | 0.2945 | 0.060* | |
C7 | 0.8167 (7) | 0.3490 (5) | 0.3285 (3) | 0.0374 (7) | |
C8 | 0.7630 (6) | 0.4399 (4) | 0.2002 (3) | 0.0357 (7) | |
C9 | 0.6836 (7) | 0.6604 (4) | 0.1766 (3) | 0.0364 (7) | |
C10 | 0.5773 (8) | 0.7240 (5) | 0.0538 (3) | 0.0446 (8) | |
H10B | 0.7115 | 0.6881 | −0.0073 | 0.053* | |
H10A | 0.4122 | 0.6581 | 0.0469 | 0.053* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0692 (14) | 0.0586 (13) | 0.0408 (11) | −0.0200 (10) | −0.0213 (10) | 0.0108 (9) |
F2 | 0.0677 (14) | 0.0506 (12) | 0.0477 (12) | 0.0152 (10) | 0.0187 (11) | 0.0059 (9) |
F3 | 0.0527 (12) | 0.0384 (11) | 0.0598 (13) | 0.0091 (9) | 0.0147 (10) | 0.0027 (9) |
F4 | 0.0701 (14) | 0.0490 (12) | 0.0385 (11) | −0.0176 (10) | −0.0159 (10) | 0.0000 (9) |
F5 | 0.0735 (15) | 0.0394 (11) | 0.0453 (11) | −0.0121 (10) | −0.0187 (10) | 0.0004 (8) |
F6 | 0.0446 (11) | 0.0391 (10) | 0.0632 (13) | 0.0102 (9) | 0.0036 (9) | 0.0071 (9) |
O1 | 0.0499 (15) | 0.0498 (15) | 0.0603 (17) | −0.0061 (12) | −0.0028 (12) | 0.0242 (12) |
O2 | 0.0514 (15) | 0.0392 (13) | 0.0668 (17) | −0.0063 (11) | −0.0057 (13) | 0.0202 (12) |
C1 | 0.054 (2) | 0.0359 (18) | 0.0461 (19) | −0.0071 (15) | −0.0054 (16) | 0.0077 (14) |
C2 | 0.0404 (16) | 0.0312 (15) | 0.0318 (15) | −0.0002 (12) | −0.0018 (13) | 0.0010 (12) |
C3 | 0.0381 (16) | 0.0317 (16) | 0.0313 (15) | 0.0004 (12) | −0.0028 (12) | −0.0013 (12) |
C4 | 0.0389 (16) | 0.0289 (16) | 0.0386 (16) | −0.0003 (13) | −0.0054 (13) | 0.0014 (13) |
C5 | 0.049 (2) | 0.0396 (18) | 0.0452 (19) | −0.0052 (15) | 0.0008 (15) | 0.0105 (14) |
F7 | 0.0599 (13) | 0.0578 (13) | 0.0476 (11) | 0.0072 (10) | 0.0146 (10) | 0.0121 (9) |
F8 | 0.0879 (16) | 0.0501 (12) | 0.0477 (12) | −0.0182 (11) | −0.0308 (11) | 0.0048 (9) |
F9 | 0.0689 (15) | 0.0390 (11) | 0.0672 (14) | −0.0118 (10) | −0.0328 (12) | 0.0015 (10) |
F10 | 0.0584 (13) | 0.0554 (13) | 0.0428 (11) | 0.0154 (10) | 0.0070 (9) | 0.0033 (9) |
F11 | 0.0799 (16) | 0.0458 (12) | 0.0445 (11) | 0.0172 (11) | 0.0110 (11) | 0.0038 (9) |
F12 | 0.0654 (14) | 0.0392 (11) | 0.0728 (15) | −0.0166 (10) | −0.0277 (12) | 0.0068 (10) |
O3 | 0.0521 (15) | 0.0493 (16) | 0.0578 (16) | −0.0015 (12) | −0.0087 (12) | 0.0225 (12) |
O4 | 0.0486 (14) | 0.0383 (13) | 0.0605 (16) | 0.0024 (11) | −0.0047 (12) | 0.0169 (11) |
C6 | 0.053 (2) | 0.0425 (19) | 0.050 (2) | 0.0009 (16) | −0.0096 (16) | 0.0101 (15) |
C7 | 0.0428 (17) | 0.0367 (17) | 0.0310 (15) | −0.0052 (13) | −0.0035 (13) | 0.0033 (13) |
C8 | 0.0400 (16) | 0.0339 (16) | 0.0327 (15) | −0.0051 (13) | −0.0045 (13) | 0.0001 (12) |
C9 | 0.0408 (16) | 0.0323 (16) | 0.0349 (15) | −0.0016 (13) | −0.0033 (13) | 0.0003 (12) |
C10 | 0.052 (2) | 0.0387 (18) | 0.0391 (17) | −0.0019 (15) | −0.0089 (15) | 0.0097 (14) |
F1—C2 | 1.348 (4) | F7—C7 | 1.352 (4) |
F2—C2 | 1.347 (4) | F8—C7 | 1.351 (4) |
F3—C3 | 1.355 (4) | F9—C8 | 1.348 (4) |
F4—C3 | 1.346 (4) | F10—C8 | 1.352 (4) |
F5—C4 | 1.351 (4) | F11—C9 | 1.348 (4) |
F6—C4 | 1.353 (4) | F12—C9 | 1.348 (4) |
O1—C1 | 1.413 (4) | O3—C6 | 1.406 (4) |
O1—H1A | 0.8200 | O3—H3A | 0.8200 |
O2—C5 | 1.417 (4) | O4—C10 | 1.416 (4) |
O2—H2A | 0.8200 | O4—H4A | 0.8200 |
C1—C2 | 1.508 (5) | C6—C7 | 1.515 (5) |
C1—H1C | 0.9700 | C6—H6A | 0.9700 |
C1—H1B | 0.9700 | C6—H6B | 0.9700 |
C2—C3 | 1.540 (4) | C7—C8 | 1.536 (4) |
C3—C4 | 1.541 (4) | C8—C9 | 1.538 (4) |
C4—C5 | 1.508 (5) | C9—C10 | 1.521 (4) |
C5—H5A | 0.9700 | C10—H10B | 0.9700 |
C5—H5B | 0.9700 | C10—H10A | 0.9700 |
C1—O1—H1A | 109.5 | C6—O3—H3A | 109.5 |
C5—O2—H2A | 109.5 | C10—O4—H4A | 109.5 |
O1—C1—C2 | 110.1 (3) | O3—C6—C7 | 110.9 (3) |
O1—C1—H1C | 109.6 | O3—C6—H6A | 109.5 |
C2—C1—H1C | 109.6 | C7—C6—H6A | 109.5 |
O1—C1—H1B | 109.6 | O3—C6—H6B | 109.5 |
C2—C1—H1B | 109.6 | C7—C6—H6B | 109.5 |
H1C—C1—H1B | 108.2 | H6A—C6—H6B | 108.0 |
F2—C2—F1 | 107.0 (3) | F8—C7—F7 | 106.5 (3) |
F2—C2—C1 | 110.6 (3) | F8—C7—C6 | 110.5 (3) |
F1—C2—C1 | 110.0 (2) | F7—C7—C6 | 109.4 (3) |
F2—C2—C3 | 107.9 (2) | F8—C7—C8 | 108.2 (2) |
F1—C2—C3 | 108.0 (3) | F7—C7—C8 | 108.4 (3) |
C1—C2—C3 | 113.2 (2) | C6—C7—C8 | 113.6 (2) |
F4—C3—F3 | 107.0 (2) | F9—C8—F10 | 107.1 (2) |
F4—C3—C2 | 108.4 (3) | F9—C8—C7 | 107.2 (2) |
F3—C3—C2 | 107.5 (2) | F10—C8—C7 | 107.9 (2) |
F4—C3—C4 | 107.2 (2) | F9—C8—C9 | 108.6 (3) |
F3—C3—C4 | 107.8 (2) | F10—C8—C9 | 107.2 (2) |
C2—C3—C4 | 118.5 (2) | C7—C8—C9 | 118.3 (2) |
F5—C4—F6 | 106.3 (2) | F11—C9—F12 | 106.9 (3) |
F5—C4—C5 | 110.8 (3) | F11—C9—C10 | 110.2 (3) |
F6—C4—C5 | 109.3 (3) | F12—C9—C10 | 109.6 (3) |
F5—C4—C3 | 108.5 (2) | F11—C9—C8 | 108.8 (2) |
F6—C4—C3 | 108.1 (2) | F12—C9—C8 | 107.9 (2) |
C5—C4—C3 | 113.5 (3) | C10—C9—C8 | 113.2 (3) |
O2—C5—C4 | 110.1 (3) | O4—C10—C9 | 109.4 (3) |
O2—C5—H5A | 109.6 | O4—C10—H10B | 109.8 |
C4—C5—H5A | 109.6 | C9—C10—H10B | 109.8 |
O2—C5—H5B | 109.6 | O4—C10—H10A | 109.8 |
C4—C5—H5B | 109.6 | C9—C10—H10A | 109.8 |
H5A—C5—H5B | 108.2 | H10B—C10—H10A | 108.2 |
O1—C1—C2—F2 | −63.2 (3) | O3—C6—C7—F8 | 61.7 (4) |
O1—C1—C2—F1 | 54.8 (4) | O3—C6—C7—F7 | −55.2 (4) |
O1—C1—C2—C3 | 175.6 (3) | O3—C6—C7—C8 | −176.4 (3) |
F2—C2—C3—F4 | −75.9 (3) | F8—C7—C8—F9 | −168.9 (3) |
F1—C2—C3—F4 | 168.8 (3) | F7—C7—C8—F9 | −53.8 (3) |
C1—C2—C3—F4 | 46.7 (3) | C6—C7—C8—F9 | 68.0 (3) |
F2—C2—C3—F3 | 168.7 (3) | F8—C7—C8—F10 | 76.0 (3) |
F1—C2—C3—F3 | 53.4 (3) | F7—C7—C8—F10 | −168.9 (3) |
C1—C2—C3—F3 | −68.6 (3) | C6—C7—C8—F10 | −47.1 (3) |
F2—C2—C3—C4 | 46.4 (4) | F8—C7—C8—C9 | −45.8 (4) |
F1—C2—C3—C4 | −68.9 (3) | F7—C7—C8—C9 | 69.3 (3) |
C1—C2—C3—C4 | 169.1 (3) | C6—C7—C8—C9 | −168.9 (3) |
F4—C3—C4—F5 | 170.8 (3) | F9—C8—C9—F11 | 77.7 (3) |
F3—C3—C4—F5 | −74.3 (3) | F10—C8—C9—F11 | −166.9 (3) |
C2—C3—C4—F5 | 47.8 (4) | C7—C8—C9—F11 | −44.7 (4) |
F4—C3—C4—F6 | 55.9 (3) | F9—C8—C9—F12 | −166.7 (3) |
F3—C3—C4—F6 | 170.8 (3) | F10—C8—C9—F12 | −51.3 (3) |
C2—C3—C4—F6 | −67.0 (3) | C7—C8—C9—F12 | 70.9 (3) |
F4—C3—C4—C5 | −65.5 (3) | F9—C8—C9—C10 | −45.2 (4) |
F3—C3—C4—C5 | 49.3 (3) | F10—C8—C9—C10 | 70.2 (3) |
C2—C3—C4—C5 | 171.5 (3) | C7—C8—C9—C10 | −167.6 (3) |
F5—C4—C5—O2 | −59.3 (3) | F11—C9—C10—O4 | 61.0 (4) |
F6—C4—C5—O2 | 57.5 (4) | F12—C9—C10—O4 | −56.4 (4) |
C3—C4—C5—O2 | 178.3 (3) | C8—C9—C10—O4 | −176.9 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O4i | 0.82 | 1.93 | 2.740 (3) | 168 |
O2—H2A···O3ii | 0.82 | 1.93 | 2.742 (4) | 169 |
O3—H3A···O2iii | 0.82 | 1.96 | 2.758 (4) | 165 |
O4—H4A···O1iv | 0.82 | 1.94 | 2.746 (4) | 166 |
Symmetry codes: (i) x, y−1, z+1; (ii) x−1, y+1, z; (iii) x, y−1, z; (iv) x+1, y+1, z−1. |
C5H6F6O2 | Z = 2 |
Mr = 212.10 | F(000) = 212 |
Triclinic, P1 | Dx = 1.893 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8848 (12) Å | Cell parameters from 2983 reflections |
b = 6.8723 (16) Å | θ = 3.0–27.3° |
c = 11.259 (3) Å | µ = 0.23 mm−1 |
α = 82.261 (3)° | T = 173 K |
β = 84.711 (3)° | Block, colourless |
γ = 85.640 (3)° | 0.35 × 0.20 × 0.17 mm |
V = 372.16 (15) Å3 |
Bruker SMART 1000 CCD Platform diffractometer | 1686 independent reflections |
Radiation source: normal-focus sealed tube | 1480 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω and ϕ scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | h = −6→6 |
Tmin = 0.923, Tmax = 0.961 | k = −8→8 |
3947 measured reflections | l = 0→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.122 | w = 1/[σ2(Fo2) + (0.0854P)2 + 0.0298P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
1686 reflections | Δρmax = 0.40 e Å−3 |
240 parameters | Δρmin = −0.29 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with Friedel pairs merged |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.3 (10) |
C5H6F6O2 | γ = 85.640 (3)° |
Mr = 212.10 | V = 372.16 (15) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.8848 (12) Å | Mo Kα radiation |
b = 6.8723 (16) Å | µ = 0.23 mm−1 |
c = 11.259 (3) Å | T = 173 K |
α = 82.261 (3)° | 0.35 × 0.20 × 0.17 mm |
β = 84.711 (3)° |
Bruker SMART 1000 CCD Platform diffractometer | 1686 independent reflections |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | 1480 reflections with I > 2σ(I) |
Tmin = 0.923, Tmax = 0.961 | Rint = 0.033 |
3947 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.122 | Δρmax = 0.40 e Å−3 |
S = 1.04 | Δρmin = −0.29 e Å−3 |
1686 reflections | Absolute structure: Flack (1983), with Friedel pairs merged |
240 parameters | Absolute structure parameter: −0.3 (10) |
3 restraints |
Experimental. Component Input RLV.Excl Used WorstRes BestRes Min.2 T h Max.2 T h 1.1 (1) 1605 0 1605 6.7955 0.7737 5.995 54.686 1.2 (2) 1378 0 1378 6.7955 0.7766 5.995 54.465 A l l 2983 0 2983 6.7955 0.7737 5.995 54.686 Orientation ('UB') matrix (Component 1.1 (1)): 0.0133849 0.1289912 0.0302185 0.0377542 - 0.0706471 0.0810191 0.2020896 - 0.0050161 - 0.0247419 Orientation ('UB') matrix (Component 1.2 (2)): 0.0537601 - 0.1289860 - 0.0302345 0.0571219 0.0706611 - 0.0810090 0.1905037 0.0049533 0.0247554 Twin Law (Cell_Now): Rotated from first domain by 179.9 degrees about reciprocal axis 1.000 0.099 0.215 and real axis 1.000 - 0.004 0.001 Twin Law (SAINT V7.34 A, final) Transforms h1.1(1)->h1.2(2) 1.00006 - 0.00028 0.00005 0.21342 - 1.00016 0.00006 0.42525 - 0.00073 - 0.99977 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.3711 (6) | 0.3503 (4) | 0.9025 (2) | 0.0301 (6) | |
F2 | −0.0469 (6) | 0.4571 (4) | 0.8647 (2) | 0.0317 (6) | |
F3 | 0.5296 (5) | 0.3425 (3) | 0.6734 (2) | 0.0286 (6) | |
F4 | 0.1100 (6) | 0.3939 (3) | 0.6206 (2) | 0.0290 (6) | |
F5 | 0.4496 (6) | 0.7080 (3) | 0.7693 (2) | 0.0294 (6) | |
F6 | 0.0585 (5) | 0.7516 (3) | 0.6880 (2) | 0.0278 (5) | |
O1 | 0.0202 (6) | 0.0523 (5) | 0.9502 (3) | 0.0313 (7) | |
H1A | 0.1620 | 0.0160 | 0.9864 | 0.047* | |
O2 | 0.4757 (7) | 0.9336 (4) | 0.5440 (3) | 0.0317 (7) | |
H2A | 0.3269 | 0.9882 | 0.5207 | 0.048* | |
C1 | 0.0978 (9) | 0.1320 (6) | 0.8312 (4) | 0.0255 (9) | |
H1C | −0.0564 | 0.1276 | 0.7806 | 0.031* | |
H1B | 0.2574 | 0.0522 | 0.7986 | 0.031* | |
C2 | 0.1729 (8) | 0.3420 (6) | 0.8264 (3) | 0.0195 (8) | |
C3 | 0.2815 (8) | 0.4349 (5) | 0.6998 (3) | 0.0198 (8) | |
C4 | 0.3145 (9) | 0.6584 (5) | 0.6790 (3) | 0.0210 (8) | |
C5 | 0.4612 (9) | 0.7262 (6) | 0.5574 (4) | 0.0256 (9) | |
H5A | 0.6494 | 0.6617 | 0.5515 | 0.031* | |
H5B | 0.3598 | 0.6891 | 0.4926 | 0.031* | |
F7 | 0.5710 (6) | 0.3459 (4) | 0.3951 (2) | 0.0324 (6) | |
F8 | 0.9717 (6) | 0.4723 (4) | 0.3751 (2) | 0.0339 (6) | |
F9 | 0.5703 (5) | 0.3388 (3) | 0.1626 (2) | 0.0312 (6) | |
F10 | 1.0003 (5) | 0.4075 (4) | 0.1284 (2) | 0.0299 (6) | |
F11 | 0.4882 (6) | 0.7061 (4) | 0.2649 (2) | 0.0352 (7) | |
F12 | 0.9030 (6) | 0.7614 (4) | 0.1871 (2) | 0.0329 (6) | |
O3 | 0.9808 (7) | 0.0655 (5) | 0.4580 (3) | 0.0324 (7) | |
H3A | 0.8349 | 0.0132 | 0.4865 | 0.049* | |
O4 | 0.5126 (6) | 0.9315 (4) | 0.0388 (3) | 0.0278 (7) | |
H4A | 0.6568 | 0.9883 | 0.0133 | 0.042* | |
C6 | 0.9560 (10) | 0.1436 (6) | 0.3373 (4) | 0.0271 (9) | |
H6A | 0.8453 | 0.0580 | 0.2993 | 0.033* | |
H6B | 1.1410 | 0.1468 | 0.2934 | 0.033* | |
C7 | 0.8193 (9) | 0.3494 (6) | 0.3286 (3) | 0.0219 (8) | |
C8 | 0.7674 (8) | 0.4399 (5) | 0.1990 (3) | 0.0206 (8) | |
C9 | 0.6794 (9) | 0.6611 (5) | 0.1765 (3) | 0.0211 (8) | |
C10 | 0.5725 (9) | 0.7241 (6) | 0.0538 (3) | 0.0232 (8) | |
H10B | 0.7128 | 0.6877 | −0.0101 | 0.028* | |
H10A | 0.4038 | 0.6562 | 0.0473 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0343 (15) | 0.0326 (13) | 0.0233 (12) | −0.0104 (11) | −0.0121 (10) | 0.0073 (10) |
F2 | 0.0336 (14) | 0.0283 (13) | 0.0274 (13) | 0.0073 (11) | 0.0089 (11) | 0.0048 (10) |
F3 | 0.0267 (13) | 0.0230 (12) | 0.0317 (13) | 0.0060 (10) | 0.0075 (10) | 0.0014 (10) |
F4 | 0.0394 (15) | 0.0294 (13) | 0.0201 (12) | −0.0114 (11) | −0.0097 (11) | −0.0003 (10) |
F5 | 0.0404 (16) | 0.0222 (12) | 0.0272 (12) | −0.0053 (10) | −0.0125 (11) | −0.0006 (9) |
F6 | 0.0233 (12) | 0.0243 (12) | 0.0325 (13) | 0.0045 (10) | −0.0005 (10) | 0.0034 (10) |
O1 | 0.0248 (17) | 0.0320 (17) | 0.0327 (18) | −0.0053 (13) | −0.0034 (13) | 0.0148 (13) |
O2 | 0.0274 (17) | 0.0222 (15) | 0.0418 (18) | −0.0015 (12) | −0.0046 (14) | 0.0103 (13) |
C1 | 0.030 (2) | 0.0212 (19) | 0.024 (2) | −0.0084 (16) | −0.0036 (17) | 0.0051 (16) |
C2 | 0.0162 (18) | 0.0231 (19) | 0.0183 (16) | 0.0010 (14) | −0.0033 (14) | 0.0008 (14) |
C3 | 0.0185 (19) | 0.0219 (19) | 0.0188 (17) | −0.0013 (14) | −0.0024 (15) | −0.0013 (14) |
C4 | 0.024 (2) | 0.0166 (18) | 0.0222 (18) | 0.0003 (15) | −0.0044 (15) | −0.0004 (14) |
C5 | 0.025 (2) | 0.0218 (19) | 0.027 (2) | −0.0026 (16) | 0.0006 (17) | 0.0071 (16) |
F7 | 0.0298 (15) | 0.0341 (14) | 0.0264 (12) | 0.0059 (11) | 0.0077 (10) | 0.0102 (10) |
F8 | 0.0476 (17) | 0.0296 (13) | 0.0266 (13) | −0.0086 (12) | −0.0181 (12) | 0.0025 (10) |
F9 | 0.0380 (16) | 0.0224 (12) | 0.0358 (14) | −0.0077 (11) | −0.0180 (12) | 0.0001 (10) |
F10 | 0.0294 (14) | 0.0320 (13) | 0.0243 (12) | 0.0063 (11) | 0.0031 (10) | 0.0021 (10) |
F11 | 0.0462 (18) | 0.0293 (13) | 0.0245 (12) | 0.0120 (12) | 0.0063 (12) | 0.0029 (10) |
F12 | 0.0346 (15) | 0.0246 (12) | 0.0413 (15) | −0.0108 (11) | −0.0168 (12) | 0.0041 (11) |
O3 | 0.0283 (18) | 0.0314 (18) | 0.0335 (17) | −0.0029 (13) | −0.0061 (14) | 0.0129 (13) |
O4 | 0.0230 (16) | 0.0228 (14) | 0.0343 (16) | −0.0012 (11) | −0.0064 (13) | 0.0114 (12) |
C6 | 0.030 (2) | 0.0194 (19) | 0.030 (2) | 0.0013 (16) | −0.0062 (17) | 0.0046 (16) |
C7 | 0.022 (2) | 0.0226 (19) | 0.0197 (17) | −0.0039 (15) | −0.0030 (15) | 0.0032 (14) |
C8 | 0.0169 (18) | 0.0233 (19) | 0.0210 (18) | −0.0005 (14) | −0.0039 (15) | 0.0004 (14) |
C9 | 0.0213 (19) | 0.0210 (18) | 0.0210 (17) | −0.0026 (15) | −0.0064 (15) | 0.0011 (14) |
C10 | 0.029 (2) | 0.0209 (19) | 0.0183 (17) | −0.0008 (16) | −0.0064 (16) | 0.0055 (15) |
F1—C2 | 1.360 (5) | F7—C7 | 1.365 (5) |
F2—C2 | 1.357 (5) | F8—C7 | 1.352 (5) |
F3—C3 | 1.352 (5) | F9—C8 | 1.352 (5) |
F4—C3 | 1.347 (4) | F10—C8 | 1.349 (5) |
F5—C4 | 1.355 (5) | F11—C9 | 1.352 (5) |
F6—C4 | 1.362 (5) | F12—C9 | 1.358 (5) |
O1—C1 | 1.408 (5) | O3—C6 | 1.405 (5) |
O1—H1A | 0.8400 | O3—H3A | 0.8400 |
O2—C5 | 1.419 (5) | O4—C10 | 1.424 (5) |
O2—H2A | 0.8400 | O4—H4A | 0.8400 |
C1—C2 | 1.508 (6) | C6—C7 | 1.512 (5) |
C1—H1C | 0.9900 | C6—H6A | 0.9900 |
C1—H1B | 0.9900 | C6—H6B | 0.9900 |
C2—C3 | 1.546 (5) | C7—C8 | 1.543 (5) |
C3—C4 | 1.541 (5) | C8—C9 | 1.542 (5) |
C4—C5 | 1.518 (6) | C9—C10 | 1.519 (5) |
C5—H5A | 0.9900 | C10—H10B | 0.9900 |
C5—H5B | 0.9900 | C10—H10A | 0.9900 |
C1—O1—H1A | 109.5 | C6—O3—H3A | 109.5 |
C5—O2—H2A | 109.5 | C10—O4—H4A | 109.5 |
O1—C1—C2 | 110.6 (3) | O3—C6—C7 | 110.7 (3) |
O1—C1—H1C | 109.5 | O3—C6—H6A | 109.5 |
C2—C1—H1C | 109.5 | C7—C6—H6A | 109.5 |
O1—C1—H1B | 109.5 | O3—C6—H6B | 109.5 |
C2—C1—H1B | 109.5 | C7—C6—H6B | 109.5 |
H1C—C1—H1B | 108.1 | H6A—C6—H6B | 108.1 |
F2—C2—F1 | 106.5 (3) | F8—C7—F7 | 106.8 (3) |
F2—C2—C1 | 110.8 (4) | F8—C7—C6 | 111.0 (3) |
F1—C2—C1 | 109.6 (3) | F7—C7—C6 | 109.2 (3) |
F2—C2—C3 | 108.1 (3) | F8—C7—C8 | 108.0 (3) |
F1—C2—C3 | 107.9 (3) | F7—C7—C8 | 107.8 (3) |
C1—C2—C3 | 113.7 (3) | C6—C7—C8 | 113.7 (3) |
F4—C3—F3 | 107.5 (3) | F10—C8—F9 | 107.4 (3) |
F4—C3—C4 | 107.7 (3) | F10—C8—C9 | 107.9 (3) |
F3—C3—C4 | 108.1 (3) | F9—C8—C9 | 108.1 (3) |
F4—C3—C2 | 107.9 (3) | F10—C8—C7 | 107.7 (3) |
F3—C3—C2 | 107.2 (3) | F9—C8—C7 | 107.2 (3) |
C4—C3—C2 | 118.1 (3) | C9—C8—C7 | 118.1 (3) |
F5—C4—F6 | 106.5 (3) | F11—C9—F12 | 106.6 (3) |
F5—C4—C5 | 110.9 (3) | F11—C9—C10 | 110.7 (3) |
F6—C4—C5 | 109.6 (3) | F12—C9—C10 | 109.7 (3) |
F5—C4—C3 | 108.8 (3) | F11—C9—C8 | 108.9 (3) |
F6—C4—C3 | 108.0 (3) | F12—C9—C8 | 107.3 (3) |
C5—C4—C3 | 112.8 (3) | C10—C9—C8 | 113.3 (3) |
O2—C5—C4 | 109.3 (3) | O4—C10—C9 | 109.1 (3) |
O2—C5—H5A | 109.8 | O4—C10—H10B | 109.9 |
C4—C5—H5A | 109.8 | C9—C10—H10B | 109.9 |
O2—C5—H5B | 109.8 | O4—C10—H10A | 109.9 |
C4—C5—H5B | 109.8 | C9—C10—H10A | 109.9 |
H5A—C5—H5B | 108.3 | H10B—C10—H10A | 108.3 |
O1—C1—C2—F2 | −62.4 (4) | O3—C6—C7—F8 | 61.8 (5) |
O1—C1—C2—F1 | 54.9 (4) | O3—C6—C7—F7 | −55.7 (5) |
O1—C1—C2—C3 | 175.7 (3) | O3—C6—C7—C8 | −176.2 (3) |
F2—C2—C3—F4 | −76.6 (4) | F8—C7—C8—F10 | 77.1 (4) |
F1—C2—C3—F4 | 168.6 (3) | F7—C7—C8—F10 | −167.8 (3) |
C1—C2—C3—F4 | 46.8 (4) | C6—C7—C8—F10 | −46.5 (4) |
F2—C2—C3—F3 | 168.0 (3) | F8—C7—C8—F9 | −167.6 (3) |
F1—C2—C3—F3 | 53.2 (3) | F7—C7—C8—F9 | −52.5 (4) |
C1—C2—C3—F3 | −68.6 (4) | C6—C7—C8—F9 | 68.8 (4) |
F2—C2—C3—C4 | 45.7 (5) | F8—C7—C8—C9 | −45.3 (5) |
F1—C2—C3—C4 | −69.1 (4) | F7—C7—C8—C9 | 69.8 (4) |
C1—C2—C3—C4 | 169.1 (3) | C6—C7—C8—C9 | −168.9 (3) |
F4—C3—C4—F5 | 170.4 (3) | F10—C8—C9—F11 | −165.6 (3) |
F3—C3—C4—F5 | −73.8 (4) | F9—C8—C9—F11 | 78.6 (4) |
C2—C3—C4—F5 | 48.0 (5) | C7—C8—C9—F11 | −43.2 (5) |
F4—C3—C4—F6 | 55.2 (4) | F10—C8—C9—F12 | −50.6 (4) |
F3—C3—C4—F6 | 171.0 (3) | F9—C8—C9—F12 | −166.4 (3) |
C2—C3—C4—F6 | −67.2 (4) | C7—C8—C9—F12 | 71.8 (4) |
F4—C3—C4—C5 | −66.1 (4) | F10—C8—C9—C10 | 70.7 (4) |
F3—C3—C4—C5 | 49.7 (4) | F9—C8—C9—C10 | −45.1 (4) |
C2—C3—C4—C5 | 171.5 (3) | C7—C8—C9—C10 | −167.0 (3) |
F5—C4—C5—O2 | −59.4 (4) | F11—C9—C10—O4 | 60.7 (4) |
F6—C4—C5—O2 | 57.9 (4) | F12—C9—C10—O4 | −56.7 (4) |
C3—C4—C5—O2 | 178.2 (3) | C8—C9—C10—O4 | −176.5 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O4i | 0.84 | 1.89 | 2.717 (4) | 169 |
O2—H2A···O3ii | 0.84 | 1.90 | 2.732 (5) | 169 |
O3—H3A···O2iii | 0.84 | 1.91 | 2.740 (5) | 171 |
O4—H4A···O1iv | 0.84 | 1.91 | 2.733 (4) | 166 |
Symmetry codes: (i) x, y−1, z+1; (ii) x−1, y+1, z; (iii) x, y−1, z; (iv) x+1, y+1, z−1. |
C5H6F6O2 | Z = 2 |
Mr = 212.10 | F(000) = 212 |
Triclinic, P1 | Dx = 1.914 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.8641 (12) Å | Cell parameters from 2983 reflections |
b = 5.7380 (14) Å | θ = 3.7–26.4° |
c = 13.325 (3) Å | µ = 0.24 mm−1 |
α = 82.814 (3)° | T = 173 K |
β = 87.274 (3)° | Block, colourless |
γ = 86.435 (4)° | 0.35 × 0.20 × 0.17 mm |
V = 367.98 (16) Å3 |
Bruker SMART 1000 CCD Platform diffractometer | 1652 independent reflections |
Radiation source: normal-focus sealed tube | 1289 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
ω and ϕ scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | h = −6→6 |
Tmin = 0.922, Tmax = 0.961 | k = −7→7 |
5181 measured reflections | l = 0→17 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0784P)2 + 0.0456P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
1652 reflections | Δρmax = 0.39 e Å−3 |
242 parameters | Δρmin = −0.39 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.8 (14) |
C5H6F6O2 | γ = 86.435 (4)° |
Mr = 212.10 | V = 367.98 (16) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.8641 (12) Å | Mo Kα radiation |
b = 5.7380 (14) Å | µ = 0.24 mm−1 |
c = 13.325 (3) Å | T = 173 K |
α = 82.814 (3)° | 0.35 × 0.20 × 0.17 mm |
β = 87.274 (3)° |
Bruker SMART 1000 CCD Platform diffractometer | 1652 independent reflections |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | 1289 reflections with I > 2σ(I) |
Tmin = 0.922, Tmax = 0.961 | Rint = 0.050 |
5181 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | H-atom parameters constrained |
wR(F2) = 0.138 | Δρmax = 0.39 e Å−3 |
S = 1.04 | Δρmin = −0.39 e Å−3 |
1652 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
242 parameters | Absolute structure parameter: −0.8 (14) |
3 restraints |
Experimental. Component Input RLV.Excl Used WorstRes BestRes Min.2 T h Max.2 T h 1.1 (1) 908 0 908 5.4700 0.7982 7.450 52.874 1.2 (2) 897 0 897 5.4700 0.8086 7.450 52.143 1.3 (3) 604 0 604 6.6051 0.8188 6.168 51.445 1.4 (4) 559 0 559 6.6051 0.8188 6.168 51.445 A l l 2968 0 2968 6.6051 0.7982 6.168 52.874 Rotated from first domain by 179.9 degrees about reciprocal axis 1.000 0.050 0.132 and real axis 1.000 - 0.011 - 0.001 Twin law to convert hkl from first to 1.001 - 0.023 - 0.002 this domain (SHELXL TWIN matrix): 0.101 - 1.001 0.001 0.264 - 0.009 - 1.000 Rotated from first domain by 179.7 degrees about reciprocal axis 0.006 0.500 1.000 and real axis -0.100 1.000 0.354 Twin law to convert hkl from first to -1.001 0.017 0.003 this domain (SHELXL TWIN matrix): -0.122 0.170 0.415 - 0.221 2.344 - 0.169 Rotated from first domain by 178.8 degrees about reciprocal axis 0.001 - 0.355 1.000 and real axis 0.003 1.000 - 0.499 Twin law to convert hkl from first to -1.001 0.012 0.005 this domain (SHELXL TWIN matrix): -0.018 - 0.168 - 0.414 - 0.047 - 2.340 0.169 Transforms h1.1(1)->h1.2(2) 0.99992 - 0.00149 0.00057 0.14591 - 0.99984 - 0.00021 0.26476 0.00010 - 1.00010 Transforms h1.1(1)->h1.3(3) -0.99962 - 0.00371 0.00198 - 0.00894 - 0.16980 - 0.41492 0.03379 - 2.33871 0.16956 Transforms h1.1(1)->h1.4(4) -0.99930 - 0.00421 0.00197 - 0.13586 0.16973 0.41551 - 0.29414 2.33869 - 0.16941 Transforms h1.2(2)->h1.3(3) -0.99978 0.00520 - 0.00255 - 0.14358 0.17009 0.41476 - 0.26254 2.33946 - 0.17018 Transforms h1.2(2)->h1.4(4) -0.99954 0.00570 - 0.00255 - 0.00110 - 0.16980 - 0.41543 0.00218 - 2.33904 0.16989 Transforms h1.3(3)->h1.4(4) 0.99969 0.00010 0.00021 0.14486 - 1.00079 - 0.00014 0.26043 0.00071 - 1.00045 SAINT V7.34 A final UB matrices: Orientation ('UB') matrix (Component 1.1 (1)): -0.0496655 - 0.1562083 - 0.0173567 - 0.0403009 0.0728058 - 0.0702953 0.1959462 - 0.0352862 - 0.0220666 Orientation ('UB') matrix (Component 1.2 (2)): -0.0770598 0.1563497 0.0172780 - 0.0482976 - 0.0727383 0.0702760 0.1849840 0.0350176 0.0221629 Orientation ('UB') matrix (Component 1.3 (3)): 0.0511716 0.0673395 0.0618221 0.0375258 0.1523325 - 0.0422504 - 0.1961485 0.0568526 0.0112710 Orientation ('UB') matrix (Component 1.4 (4)): 0.0770344 - 0.0673223 - 0.0617684 0.0485787 - 0.1521777 0.0422631 - 0.1850317 - 0.0568346 - 0.0112963 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.4059 (8) | 0.3817 (6) | 0.8853 (2) | 0.0346 (9) | |
F2 | −0.0025 (8) | 0.5432 (6) | 0.8558 (3) | 0.0348 (9) | |
F3 | 0.4761 (7) | 0.2581 (6) | 0.7018 (3) | 0.0320 (8) | |
F4 | 0.0464 (7) | 0.3487 (6) | 0.6670 (2) | 0.0333 (9) | |
F5 | 0.5090 (8) | 0.7370 (6) | 0.7351 (3) | 0.0328 (8) | |
F6 | 0.0999 (7) | 0.7996 (6) | 0.6739 (2) | 0.0304 (8) | |
O1 | −0.0047 (9) | 0.1011 (7) | 0.9698 (3) | 0.0310 (10) | |
H1A | 0.1369 | 0.0484 | 1.0007 | 0.047* | |
O2 | 0.4994 (10) | 0.9049 (7) | 0.5273 (3) | 0.0347 (10) | |
H2A | 0.3564 | 0.9660 | 0.4995 | 0.052* | |
F7 | 0.5730 (8) | 0.3695 (6) | 0.3820 (3) | 0.0354 (9) | |
F8 | 0.9676 (8) | 0.5310 (6) | 0.3562 (2) | 0.0359 (9) | |
F9 | 0.5695 (7) | 0.2604 (5) | 0.1976 (2) | 0.0307 (8) | |
F10 | 0.9979 (7) | 0.3423 (6) | 0.1650 (2) | 0.0306 (8) | |
F11 | 0.4824 (7) | 0.7441 (6) | 0.2379 (2) | 0.0310 (8) | |
F12 | 0.8956 (7) | 0.7916 (6) | 0.1720 (2) | 0.0291 (8) | |
O3 | 0.9963 (9) | 0.0837 (7) | 0.4664 (3) | 0.0311 (10) | |
H3A | 0.8441 | 0.0523 | 0.4959 | 0.047* | |
O4 | 0.5023 (9) | 0.9131 (7) | 0.0305 (3) | 0.0332 (10) | |
H4A | 0.6488 | 0.9785 | 0.0115 | 0.050* | |
C1 | 0.0582 (14) | 0.1288 (10) | 0.8631 (4) | 0.0270 (13) | |
H1C | −0.1113 | 0.1178 | 0.8260 | 0.032* | |
H1B | 0.1930 | 0.0020 | 0.8459 | 0.032* | |
C2 | 0.1767 (12) | 0.3656 (10) | 0.8321 (4) | 0.0235 (12) | |
C3 | 0.2586 (12) | 0.4082 (10) | 0.7184 (4) | 0.0208 (10) | |
C4 | 0.3345 (12) | 0.6552 (9) | 0.6731 (4) | 0.0207 (11) | |
C5 | 0.4570 (14) | 0.6668 (10) | 0.5657 (4) | 0.0289 (13) | |
H5A | 0.6347 | 0.5729 | 0.5652 | 0.035* | |
H5B | 0.3303 | 0.6001 | 0.5223 | 0.035* | |
C6 | 0.9648 (13) | 0.1191 (10) | 0.3606 (4) | 0.0258 (12) | |
H6A | 0.8558 | −0.0062 | 0.3404 | 0.031* | |
H6B | 1.1480 | 0.1111 | 0.3251 | 0.031* | |
C7 | 0.8208 (13) | 0.3554 (9) | 0.3311 (4) | 0.0243 (12) | |
C8 | 0.7657 (12) | 0.4043 (10) | 0.2170 (4) | 0.0223 (11) | |
C9 | 0.6752 (12) | 0.6559 (10) | 0.1733 (4) | 0.0237 (12) | |
C10 | 0.5647 (13) | 0.6744 (10) | 0.0673 (4) | 0.0262 (12) | |
H10B | 0.7043 | 0.6053 | 0.0213 | 0.031* | |
H10A | 0.3965 | 0.5850 | 0.0691 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.040 (2) | 0.044 (2) | 0.0214 (16) | −0.0159 (18) | −0.0070 (15) | −0.0015 (15) |
F2 | 0.049 (2) | 0.0239 (18) | 0.0297 (18) | 0.0036 (17) | 0.0077 (17) | −0.0031 (14) |
F3 | 0.042 (2) | 0.0209 (16) | 0.0306 (16) | 0.0067 (16) | 0.0077 (15) | −0.0006 (13) |
F4 | 0.044 (2) | 0.038 (2) | 0.0187 (16) | −0.0135 (18) | −0.0080 (15) | −0.0018 (14) |
F5 | 0.043 (2) | 0.0260 (17) | 0.0305 (18) | −0.0124 (16) | −0.0071 (15) | −0.0016 (13) |
F6 | 0.034 (2) | 0.0251 (17) | 0.0302 (18) | 0.0023 (15) | 0.0056 (15) | 0.0020 (14) |
O1 | 0.035 (2) | 0.036 (2) | 0.020 (2) | −0.009 (2) | −0.0002 (17) | 0.0071 (18) |
O2 | 0.032 (2) | 0.033 (3) | 0.035 (3) | −0.003 (2) | 0.0000 (19) | 0.0097 (19) |
F7 | 0.036 (2) | 0.039 (2) | 0.0289 (18) | 0.0031 (17) | 0.0069 (15) | −0.0010 (15) |
F8 | 0.059 (3) | 0.0256 (19) | 0.0253 (18) | −0.0107 (18) | −0.0128 (17) | −0.0016 (14) |
F9 | 0.044 (2) | 0.0182 (16) | 0.0315 (17) | −0.0095 (16) | −0.0101 (16) | −0.0018 (13) |
F10 | 0.0352 (19) | 0.034 (2) | 0.0205 (15) | 0.0046 (16) | 0.0050 (14) | −0.0022 (13) |
F11 | 0.040 (2) | 0.0272 (17) | 0.0242 (16) | 0.0049 (16) | 0.0060 (15) | −0.0026 (13) |
F12 | 0.0360 (19) | 0.0243 (16) | 0.0278 (17) | −0.0115 (15) | −0.0086 (14) | 0.0013 (13) |
O3 | 0.036 (2) | 0.032 (2) | 0.023 (2) | −0.002 (2) | −0.0036 (17) | 0.0060 (18) |
O4 | 0.030 (2) | 0.030 (2) | 0.037 (3) | −0.0068 (19) | −0.0035 (19) | 0.0084 (19) |
C1 | 0.038 (3) | 0.026 (3) | 0.016 (3) | −0.010 (3) | 0.001 (2) | 0.003 (2) |
C2 | 0.026 (3) | 0.025 (3) | 0.019 (3) | −0.002 (2) | 0.004 (2) | −0.001 (2) |
C3 | 0.025 (3) | 0.021 (3) | 0.016 (2) | 0.001 (2) | −0.004 (2) | −0.0018 (18) |
C4 | 0.027 (3) | 0.017 (2) | 0.017 (2) | 0.000 (2) | 0.003 (2) | 0.000 (2) |
C5 | 0.043 (4) | 0.026 (3) | 0.016 (3) | 0.003 (3) | 0.005 (2) | −0.001 (2) |
C6 | 0.033 (3) | 0.022 (3) | 0.020 (3) | 0.004 (3) | −0.006 (2) | 0.004 (2) |
C7 | 0.037 (3) | 0.020 (3) | 0.017 (2) | −0.007 (2) | 0.000 (2) | −0.002 (2) |
C8 | 0.023 (3) | 0.026 (3) | 0.019 (2) | −0.009 (2) | 0.001 (2) | −0.0042 (19) |
C9 | 0.026 (3) | 0.023 (3) | 0.022 (3) | −0.006 (2) | 0.006 (2) | −0.003 (2) |
C10 | 0.033 (3) | 0.028 (3) | 0.017 (3) | −0.004 (3) | −0.001 (2) | 0.002 (2) |
F1—C2 | 1.364 (7) | O4—C10 | 1.415 (7) |
F2—C2 | 1.357 (7) | O4—H4A | 0.8400 |
F3—C3 | 1.350 (6) | C1—C2 | 1.511 (8) |
F4—C3 | 1.350 (6) | C1—H1C | 0.9900 |
F5—C4 | 1.355 (6) | C1—H1B | 0.9900 |
F6—C4 | 1.368 (6) | C2—C3 | 1.541 (6) |
O1—C1 | 1.431 (6) | C3—C4 | 1.529 (7) |
O1—H1A | 0.8400 | C4—C5 | 1.519 (7) |
O2—C5 | 1.421 (7) | C5—H5A | 0.9900 |
O2—H2A | 0.8400 | C5—H5B | 0.9900 |
F7—C7 | 1.358 (6) | C6—C7 | 1.503 (8) |
F8—C7 | 1.354 (6) | C6—H6A | 0.9900 |
F9—C8 | 1.354 (6) | C6—H6B | 0.9900 |
F10—C8 | 1.348 (6) | C7—C8 | 1.545 (7) |
F11—C9 | 1.360 (6) | C8—C9 | 1.533 (7) |
F12—C9 | 1.362 (6) | C9—C10 | 1.525 (7) |
O3—C6 | 1.414 (6) | C10—H10B | 0.9900 |
O3—H3A | 0.8400 | C10—H10A | 0.9900 |
C1—O1—H1A | 109.5 | C4—C5—H5B | 109.8 |
C5—O2—H2A | 109.5 | H5A—C5—H5B | 108.2 |
C6—O3—H3A | 109.5 | O3—C6—C7 | 109.7 (4) |
C10—O4—H4A | 109.5 | O3—C6—H6A | 109.7 |
O1—C1—C2 | 109.3 (4) | C7—C6—H6A | 109.7 |
O1—C1—H1C | 109.8 | O3—C6—H6B | 109.7 |
C2—C1—H1C | 109.8 | C7—C6—H6B | 109.7 |
O1—C1—H1B | 109.8 | H6A—C6—H6B | 108.2 |
C2—C1—H1B | 109.8 | F8—C7—F7 | 106.8 (4) |
H1C—C1—H1B | 108.3 | F8—C7—C6 | 111.1 (5) |
F2—C2—F1 | 105.9 (4) | F7—C7—C6 | 109.9 (4) |
F2—C2—C1 | 111.2 (5) | F8—C7—C8 | 108.3 (4) |
F1—C2—C1 | 109.5 (4) | F7—C7—C8 | 107.2 (5) |
F2—C2—C3 | 108.9 (4) | C6—C7—C8 | 113.2 (4) |
F1—C2—C3 | 108.0 (4) | F10—C8—F9 | 107.3 (4) |
C1—C2—C3 | 113.0 (4) | F10—C8—C9 | 107.2 (4) |
F3—C3—F4 | 107.7 (4) | F9—C8—C9 | 107.9 (5) |
F3—C3—C4 | 107.8 (4) | F10—C8—C7 | 108.1 (5) |
F4—C3—C4 | 107.7 (4) | F9—C8—C7 | 107.7 (4) |
F3—C3—C2 | 107.2 (4) | C9—C8—C7 | 118.2 (4) |
F4—C3—C2 | 107.5 (5) | F11—C9—F12 | 106.0 (4) |
C4—C3—C2 | 118.5 (4) | F11—C9—C10 | 110.3 (5) |
F5—C4—F6 | 106.3 (4) | F12—C9—C10 | 109.6 (4) |
F5—C4—C5 | 110.9 (5) | F11—C9—C8 | 108.8 (4) |
F6—C4—C5 | 109.2 (4) | F12—C9—C8 | 108.1 (5) |
F5—C4—C3 | 108.8 (4) | C10—C9—C8 | 113.8 (5) |
F6—C4—C3 | 107.7 (4) | O4—C10—C9 | 110.0 (5) |
C5—C4—C3 | 113.6 (4) | O4—C10—H10B | 109.7 |
O2—C5—C4 | 109.5 (4) | C9—C10—H10B | 109.7 |
O2—C5—H5A | 109.8 | O4—C10—H10A | 109.7 |
C4—C5—H5A | 109.8 | C9—C10—H10A | 109.7 |
O2—C5—H5B | 109.8 | H10B—C10—H10A | 108.2 |
O1—C1—C2—F2 | −58.7 (6) | O3—C6—C7—F8 | 60.5 (6) |
O1—C1—C2—F1 | 57.9 (6) | O3—C6—C7—F7 | −57.5 (6) |
O1—C1—C2—C3 | 178.4 (5) | O3—C6—C7—C8 | −177.4 (5) |
F2—C2—C3—F3 | 167.7 (4) | F8—C7—C8—F10 | 78.0 (5) |
F1—C2—C3—F3 | 53.1 (5) | F7—C7—C8—F10 | −167.1 (4) |
C1—C2—C3—F3 | −68.2 (6) | C6—C7—C8—F10 | −45.7 (6) |
F2—C2—C3—F4 | −76.7 (5) | F8—C7—C8—F9 | −166.4 (4) |
F1—C2—C3—F4 | 168.7 (5) | F7—C7—C8—F9 | −51.5 (5) |
C1—C2—C3—F4 | 47.4 (6) | C6—C7—C8—F9 | 69.8 (6) |
F2—C2—C3—C4 | 45.5 (7) | F8—C7—C8—C9 | −43.9 (7) |
F1—C2—C3—C4 | −69.1 (6) | F7—C7—C8—C9 | 71.0 (6) |
C1—C2—C3—C4 | 169.7 (5) | C6—C7—C8—C9 | −167.6 (5) |
F3—C3—C4—F5 | −75.7 (5) | F10—C8—C9—F11 | −166.0 (4) |
F4—C3—C4—F5 | 168.3 (4) | F9—C8—C9—F11 | 78.8 (5) |
C2—C3—C4—F5 | 46.2 (6) | C7—C8—C9—F11 | −43.6 (7) |
F3—C3—C4—F6 | 169.5 (4) | F10—C8—C9—F12 | −51.2 (5) |
F4—C3—C4—F6 | 53.5 (5) | F9—C8—C9—F12 | −166.5 (4) |
C2—C3—C4—F6 | −68.6 (6) | C7—C8—C9—F12 | 71.1 (6) |
F3—C3—C4—C5 | 48.4 (6) | F10—C8—C9—C10 | 70.7 (6) |
F4—C3—C4—C5 | −67.5 (6) | F9—C8—C9—C10 | −44.6 (6) |
C2—C3—C4—C5 | 170.3 (5) | C7—C8—C9—C10 | −166.9 (5) |
F5—C4—C5—O2 | −61.8 (6) | F11—C9—C10—O4 | 61.1 (6) |
F6—C4—C5—O2 | 54.9 (6) | F12—C9—C10—O4 | −55.3 (6) |
C3—C4—C5—O2 | 175.2 (5) | C8—C9—C10—O4 | −176.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O4i | 0.84 | 1.93 | 2.746 (6) | 163 |
O2—H2A···O3ii | 0.84 | 1.89 | 2.714 (6) | 167 |
O3—H3A···O2iii | 0.84 | 1.93 | 2.733 (6) | 160 |
O4—H4A···O1iv | 0.84 | 1.90 | 2.736 (6) | 175 |
Symmetry codes: (i) x, y−1, z+1; (ii) x−1, y+1, z; (iii) x, y−1, z; (iv) x+1, y+1, z−1. |
C5H6F6O2 | Z = 2 |
Mr = 212.10 | F(000) = 212 |
Triclinic, P1 | Dx = 1.867 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 4.9215 (18) Å | Cell parameters from 2985 reflections |
b = 6.871 (3) Å | θ = 3.1–27.3° |
c = 11.314 (4) Å | µ = 0.23 mm−1 |
α = 81.973 (5)° | T = 283 K |
β = 85.839 (5)° | Block, colourless |
γ = 86.562 (5)° | 0.35 × 0.20 × 0.17 mm |
V = 377.3 (2) Å3 |
Bruker SMART 1000 CCD Platform diffractometer | 1729 independent reflections |
Radiation source: normal-focus sealed tube | 1200 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and ϕ scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | h = −6→6 |
Tmin = 0.924, Tmax = 0.962 | k = −8→8 |
5825 measured reflections | l = 0→14 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.129 | w = 1/[σ2(Fo2) + (0.0647P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
1729 reflections | Δρmax = 0.27 e Å−3 |
242 parameters | Δρmin = −0.30 e Å−3 |
3 restraints | Absolute structure: Flack (1983), with Friedel pairs merged |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.2 (14) |
C5H6F6O2 | γ = 86.562 (5)° |
Mr = 212.10 | V = 377.3 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 4.9215 (18) Å | Mo Kα radiation |
b = 6.871 (3) Å | µ = 0.23 mm−1 |
c = 11.314 (4) Å | T = 283 K |
α = 81.973 (5)° | 0.35 × 0.20 × 0.17 mm |
β = 85.839 (5)° |
Bruker SMART 1000 CCD Platform diffractometer | 1729 independent reflections |
Absorption correction: multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | 1200 reflections with I > 2σ(I) |
Tmin = 0.924, Tmax = 0.962 | Rint = 0.030 |
5825 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.129 | Δρmax = 0.27 e Å−3 |
S = 1.02 | Δρmin = −0.30 e Å−3 |
1729 reflections | Absolute structure: Flack (1983), with Friedel pairs merged |
242 parameters | Absolute structure parameter: 0.2 (14) |
3 restraints |
Experimental. Cell Refinement: Component Input RLV.Excl Used WorstRes BestRes Min.2 T h Max.2 T h 1.1 (1) 872 0 872 6.7949 0.7985 5.996 52.850 1.2 (2) 921 0 921 5.5897 0.7985 7.290 52.850 1.3 (3) 560 0 560 6.7949 0.9132 5.996 45.801 1.4 (4) 616 0 616 6.7949 0.8768 5.996 47.820 A l l 2969 0 2969 6.7949 0.7985 5.996 52.850 Rotated from first domain by 179.9 degrees about reciprocal axis 1.000 0.069 0.137 and real axis 1.000 0.002 0.004 Rotated from first domain by 179.2 degrees about reciprocal axis -0.003 - 0.790 1.000 and real axis 0.002 1.000 - 0.507 Rotated from first domain by 179.6 degrees about reciprocal axis -0.004 0.505 1.000 and real axis -0.174 1.000 0.792 Twin Laws, (SAINT V7.34 A) Transforms h1.1(1)->h1.2(2) 1.00002 - 0.00060 0.00028 0.16662 - 1.00021 0.00021 0.33540 - 0.00060 - 0.99945 Transforms h1.1(1)->h1.3(3) -0.99914 - 0.00285 0.00167 - 0.00216 0.22271 - 0.61154 0.00804 - 1.55587 - 0.22238 Transforms h1.2(2)->h1.3(3) -0.99904 0.00345 - 0.00195 - 0.17019 - 0.22293 0.61178 - 0.32586 1.55560 0.22274 Transforms h1.1(1)->h1.4(4) -0.99962 - 0.00354 0.00177 - 0.16330 - 0.22294 0.61172 - 0.34161 1.55406 0.22281 Transforms h1.2(2)->h1.4(4) -0.99960 0.00414 - 0.00205 0.00476 0.22326 - 0.61201 - 0.00787 - 1.55359 - 0.22327 Transforms h1.3(3)->h1.4(4) 1.00048 - 0.00030 0.00040 0.16560 - 0.99979 - 0.00013 0.33387 0.00000 - 0.99945 SAINT V7.34 A final UB matrices: Orientation ('UB') matrix (Component 1.1 (1)): -0.0477110 - 0.1218109 - 0.0313513 - 0.0370147 0.0794615 - 0.0787042 0.1948454 - 0.0225065 - 0.0287094 Orientation ('UB') matrix (Component 1.2 (2)): -0.0784969 0.1218321 0.0313470 - 0.0501602 - 0.0794627 0.0786809 0.1814754 0.0223873 0.0287776 Orientation ('UB') matrix (Component 1.3 (3)): 0.0481961 0.0217619 0.0813463 0.0362060 0.1401732 - 0.0311011 - 0.1948779 0.0391977 0.0204199 Orientation ('UB') matrix (Component 1.4 (4)): 0.0790404 - 0.0218297 - 0.0813253 0.0491009 - 0.1401953 0.0311274 - 0.1815292 - 0.0390809 - 0.0204636 |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.3772 (8) | 0.3503 (5) | 0.9006 (3) | 0.0554 (9) | |
F2 | −0.0361 (8) | 0.4585 (5) | 0.8657 (3) | 0.0578 (10) | |
F3 | 0.5158 (7) | 0.3432 (4) | 0.6736 (3) | 0.0520 (9) | |
F4 | 0.0978 (7) | 0.3959 (4) | 0.6240 (2) | 0.0493 (9) | |
F5 | 0.4547 (7) | 0.7081 (4) | 0.7663 (3) | 0.0507 (9) | |
F6 | 0.0633 (7) | 0.7519 (4) | 0.6880 (3) | 0.0499 (8) | |
O1 | 0.0258 (8) | 0.0554 (6) | 0.9525 (4) | 0.0526 (11) | |
H1A | 0.1633 | 0.0081 | 0.9847 | 0.079* | |
O2 | 0.4685 (8) | 0.9323 (5) | 0.5412 (4) | 0.0524 (11) | |
H2A | 0.3204 | 0.9856 | 0.5238 | 0.079* | |
C1 | 0.0969 (12) | 0.1348 (7) | 0.8327 (5) | 0.0444 (14) | |
H1C | −0.0563 | 0.1301 | 0.7841 | 0.053* | |
H1B | 0.2490 | 0.0572 | 0.8009 | 0.053* | |
C2 | 0.1741 (11) | 0.3442 (7) | 0.8279 (4) | 0.0328 (11) | |
C3 | 0.2738 (11) | 0.4366 (7) | 0.7015 (5) | 0.0349 (11) | |
C4 | 0.3107 (11) | 0.6572 (7) | 0.6778 (4) | 0.0342 (12) | |
C5 | 0.4493 (13) | 0.7253 (8) | 0.5572 (5) | 0.0451 (14) | |
H5A | 0.6304 | 0.6621 | 0.5513 | 0.054* | |
H5B | 0.3460 | 0.6879 | 0.4948 | 0.054* | |
F7 | 0.5767 (8) | 0.3475 (5) | 0.3947 (3) | 0.0557 (9) | |
F8 | 0.9766 (8) | 0.4687 (5) | 0.3739 (3) | 0.0591 (10) | |
F9 | 0.5658 (7) | 0.3398 (4) | 0.1642 (3) | 0.0566 (10) | |
F10 | 0.9916 (7) | 0.4074 (5) | 0.1304 (3) | 0.0535 (9) | |
F11 | 0.4964 (8) | 0.7054 (5) | 0.2624 (3) | 0.0589 (10) | |
F12 | 0.9064 (7) | 0.7594 (5) | 0.1875 (3) | 0.0574 (10) | |
O3 | 0.9746 (8) | 0.0630 (6) | 0.4575 (4) | 0.0529 (11) | |
H3A | 0.8235 | 0.0415 | 0.4907 | 0.079* | |
O4 | 0.5217 (8) | 0.9288 (5) | 0.0373 (4) | 0.0522 (11) | |
H4A | 0.6648 | 0.9859 | 0.0262 | 0.078* | |
C6 | 0.9462 (13) | 0.1427 (8) | 0.3366 (5) | 0.0468 (14) | |
H6A | 0.8334 | 0.0601 | 0.2998 | 0.056* | |
H6B | 1.1240 | 0.1452 | 0.2936 | 0.056* | |
C7 | 0.8179 (11) | 0.3482 (8) | 0.3281 (4) | 0.0384 (12) | |
C8 | 0.7648 (10) | 0.4409 (7) | 0.2002 (4) | 0.0334 (11) | |
C9 | 0.6840 (11) | 0.6597 (7) | 0.1765 (4) | 0.0350 (12) | |
C10 | 0.5802 (12) | 0.7235 (8) | 0.0538 (4) | 0.0417 (13) | |
H10B | 0.7169 | 0.6891 | −0.0071 | 0.050* | |
H10A | 0.4165 | 0.6557 | 0.0458 | 0.050* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.066 (2) | 0.060 (2) | 0.0419 (18) | −0.0187 (17) | −0.0239 (17) | 0.0049 (14) |
F2 | 0.071 (2) | 0.048 (2) | 0.0441 (18) | 0.0170 (18) | 0.0207 (18) | 0.0066 (15) |
F3 | 0.053 (2) | 0.0411 (18) | 0.056 (2) | 0.0121 (16) | 0.0149 (17) | 0.0000 (15) |
F4 | 0.070 (2) | 0.0502 (19) | 0.0310 (16) | −0.0183 (17) | −0.0144 (16) | −0.0047 (13) |
F5 | 0.069 (2) | 0.0411 (17) | 0.0446 (18) | −0.0077 (17) | −0.0206 (18) | −0.0038 (13) |
F6 | 0.0439 (18) | 0.0386 (17) | 0.061 (2) | 0.0102 (15) | 0.0048 (16) | 0.0033 (14) |
O1 | 0.047 (2) | 0.048 (3) | 0.056 (3) | −0.008 (2) | −0.006 (2) | 0.0229 (19) |
O2 | 0.050 (2) | 0.041 (2) | 0.060 (3) | −0.001 (2) | −0.005 (2) | 0.013 (2) |
C1 | 0.054 (4) | 0.035 (3) | 0.042 (3) | −0.005 (3) | −0.009 (3) | 0.005 (2) |
C2 | 0.036 (3) | 0.034 (3) | 0.028 (2) | −0.002 (2) | −0.002 (2) | 0.000 (2) |
C3 | 0.036 (3) | 0.037 (3) | 0.033 (3) | 0.001 (2) | −0.006 (2) | −0.005 (2) |
C4 | 0.036 (3) | 0.033 (3) | 0.034 (3) | 0.004 (2) | −0.010 (2) | −0.001 (2) |
C5 | 0.055 (4) | 0.040 (3) | 0.037 (3) | −0.003 (3) | −0.007 (3) | 0.009 (2) |
F7 | 0.056 (2) | 0.055 (2) | 0.0464 (19) | 0.0101 (17) | 0.0166 (17) | 0.0084 (14) |
F8 | 0.084 (3) | 0.053 (2) | 0.0439 (18) | −0.0129 (19) | −0.0309 (19) | −0.0022 (15) |
F9 | 0.069 (2) | 0.0412 (18) | 0.063 (2) | −0.0131 (17) | −0.034 (2) | −0.0003 (16) |
F10 | 0.057 (2) | 0.059 (2) | 0.0388 (18) | 0.0153 (17) | 0.0075 (16) | 0.0006 (14) |
F11 | 0.081 (3) | 0.0460 (18) | 0.0425 (18) | 0.0188 (19) | 0.0096 (19) | 0.0025 (14) |
F12 | 0.062 (2) | 0.0465 (18) | 0.065 (2) | −0.0193 (17) | −0.0247 (19) | 0.0062 (16) |
O3 | 0.047 (2) | 0.056 (3) | 0.050 (2) | −0.001 (2) | −0.011 (2) | 0.017 (2) |
O4 | 0.049 (2) | 0.041 (2) | 0.061 (3) | 0.0033 (19) | −0.011 (2) | 0.013 (2) |
C6 | 0.049 (3) | 0.045 (3) | 0.043 (3) | −0.003 (3) | −0.006 (3) | 0.006 (2) |
C7 | 0.040 (3) | 0.042 (3) | 0.034 (3) | −0.007 (2) | −0.003 (2) | −0.004 (2) |
C8 | 0.030 (2) | 0.037 (3) | 0.033 (3) | −0.003 (2) | −0.006 (2) | −0.002 (2) |
C9 | 0.040 (3) | 0.029 (3) | 0.034 (3) | 0.001 (2) | −0.003 (2) | 0.001 (2) |
C10 | 0.050 (3) | 0.039 (3) | 0.034 (3) | 0.000 (3) | −0.008 (3) | 0.005 (2) |
F1—C2 | 1.346 (6) | F7—C7 | 1.359 (6) |
F2—C2 | 1.342 (6) | F8—C7 | 1.349 (6) |
F3—C3 | 1.357 (6) | F9—C8 | 1.352 (6) |
F4—C3 | 1.343 (6) | F10—C8 | 1.347 (6) |
F5—C4 | 1.363 (6) | F11—C9 | 1.348 (6) |
F6—C4 | 1.351 (6) | F12—C9 | 1.348 (6) |
O1—C1 | 1.416 (6) | O3—C6 | 1.415 (7) |
O1—H1A | 0.8200 | O3—H3A | 0.8200 |
O2—C5 | 1.417 (6) | O4—C10 | 1.412 (6) |
O2—H2A | 0.8200 | O4—H4A | 0.8200 |
C1—C2 | 1.502 (7) | C6—C7 | 1.505 (8) |
C1—H1C | 0.9700 | C6—H6A | 0.9700 |
C1—H1B | 0.9700 | C6—H6B | 0.9700 |
C2—C3 | 1.540 (6) | C7—C8 | 1.531 (6) |
C3—C4 | 1.521 (6) | C8—C9 | 1.523 (6) |
C4—C5 | 1.507 (7) | C9—C10 | 1.513 (7) |
C5—H5A | 0.9700 | C10—H10B | 0.9700 |
C5—H5B | 0.9700 | C10—H10A | 0.9700 |
C1—O1—H1A | 109.5 | C6—O3—H3A | 109.5 |
C5—O2—H2A | 109.5 | C10—O4—H4A | 109.5 |
O1—C1—C2 | 109.7 (4) | O3—C6—C7 | 110.5 (5) |
O1—C1—H1C | 109.7 | O3—C6—H6A | 109.5 |
C2—C1—H1C | 109.7 | C7—C6—H6A | 109.5 |
O1—C1—H1B | 109.7 | O3—C6—H6B | 109.5 |
C2—C1—H1B | 109.7 | C7—C6—H6B | 109.5 |
H1C—C1—H1B | 108.2 | H6A—C6—H6B | 108.1 |
F2—C2—F1 | 107.5 (4) | F8—C7—F7 | 106.3 (4) |
F2—C2—C1 | 111.5 (4) | F8—C7—C6 | 110.9 (5) |
F1—C2—C1 | 109.3 (4) | F7—C7—C6 | 109.8 (4) |
F2—C2—C3 | 107.8 (4) | F8—C7—C8 | 107.6 (4) |
F1—C2—C3 | 107.7 (4) | F7—C7—C8 | 108.2 (4) |
C1—C2—C3 | 112.9 (4) | C6—C7—C8 | 113.8 (4) |
F4—C3—F3 | 106.8 (4) | F10—C8—F9 | 107.0 (4) |
F4—C3—C4 | 107.0 (4) | F10—C8—C9 | 107.8 (4) |
F3—C3—C4 | 108.1 (4) | F9—C8—C9 | 108.3 (4) |
F4—C3—C2 | 108.2 (4) | F10—C8—C7 | 107.6 (4) |
F3—C3—C2 | 107.3 (4) | F9—C8—C7 | 106.6 (4) |
C4—C3—C2 | 118.9 (3) | C9—C8—C7 | 119.0 (4) |
F6—C4—F5 | 105.9 (4) | F11—C9—F12 | 106.8 (4) |
F6—C4—C5 | 109.6 (4) | F11—C9—C10 | 110.6 (4) |
F5—C4—C5 | 110.2 (4) | F12—C9—C10 | 109.0 (4) |
F6—C4—C3 | 108.6 (4) | F11—C9—C8 | 109.0 (4) |
F5—C4—C3 | 108.5 (4) | F12—C9—C8 | 107.6 (4) |
C5—C4—C3 | 113.9 (4) | C10—C9—C8 | 113.5 (4) |
O2—C5—C4 | 110.2 (5) | O4—C10—C9 | 109.8 (4) |
O2—C5—H5A | 109.6 | O4—C10—H10B | 109.7 |
C4—C5—H5A | 109.6 | C9—C10—H10B | 109.7 |
O2—C5—H5B | 109.6 | O4—C10—H10A | 109.7 |
C4—C5—H5B | 109.6 | C9—C10—H10A | 109.7 |
H5A—C5—H5B | 108.1 | H10B—C10—H10A | 108.2 |
O1—C1—C2—F2 | −62.5 (5) | O3—C6—C7—F8 | 61.9 (6) |
O1—C1—C2—F1 | 56.1 (6) | O3—C6—C7—F7 | −55.2 (6) |
O1—C1—C2—C3 | 176.0 (5) | O3—C6—C7—C8 | −176.7 (4) |
F2—C2—C3—F4 | −76.6 (5) | F8—C7—C8—F10 | 77.0 (5) |
F1—C2—C3—F4 | 167.7 (4) | F7—C7—C8—F10 | −168.6 (4) |
C1—C2—C3—F4 | 46.9 (5) | C6—C7—C8—F10 | −46.2 (5) |
F2—C2—C3—F3 | 168.4 (4) | F8—C7—C8—F9 | −168.5 (5) |
F1—C2—C3—F3 | 52.7 (5) | F7—C7—C8—F9 | −54.1 (5) |
C1—C2—C3—F3 | −68.0 (5) | C6—C7—C8—F9 | 68.2 (6) |
F2—C2—C3—C4 | 45.6 (6) | F8—C7—C8—C9 | −45.8 (6) |
F1—C2—C3—C4 | −70.1 (5) | F7—C7—C8—C9 | 68.6 (6) |
C1—C2—C3—C4 | 169.2 (4) | C6—C7—C8—C9 | −169.1 (4) |
F4—C3—C4—F6 | 56.3 (5) | F10—C8—C9—F11 | −166.7 (4) |
F3—C3—C4—F6 | 171.0 (4) | F9—C8—C9—F11 | 77.9 (5) |
C2—C3—C4—F6 | −66.6 (6) | C7—C8—C9—F11 | −43.9 (6) |
F4—C3—C4—F5 | 170.9 (4) | F10—C8—C9—F12 | −51.2 (5) |
F3—C3—C4—F5 | −74.4 (5) | F9—C8—C9—F12 | −166.6 (4) |
C2—C3—C4—F5 | 48.0 (6) | C7—C8—C9—F12 | 71.5 (6) |
F4—C3—C4—C5 | −66.1 (5) | F10—C8—C9—C10 | 69.5 (5) |
F3—C3—C4—C5 | 48.6 (5) | F9—C8—C9—C10 | −45.9 (6) |
C2—C3—C4—C5 | 171.1 (5) | C7—C8—C9—C10 | −167.8 (4) |
F6—C4—C5—O2 | 56.5 (6) | F11—C9—C10—O4 | 59.6 (6) |
F5—C4—C5—O2 | −59.6 (6) | F12—C9—C10—O4 | −57.5 (6) |
C3—C4—C5—O2 | 178.3 (4) | C8—C9—C10—O4 | −177.4 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1A···O4i | 0.82 | 1.93 | 2.736 (5) | 169 |
O2—H2A···O3ii | 0.82 | 1.93 | 2.728 (6) | 166 |
O3—H3A···O2iii | 0.82 | 1.96 | 2.756 (6) | 164 |
O4—H4A···O1iv | 0.82 | 1.96 | 2.741 (6) | 158 |
Symmetry codes: (i) x, y−1, z+1; (ii) x−1, y+1, z; (iii) x, y−1, z; (iv) x+1, y+1, z−1. |
Experimental details
(Ia) | (Ib) | (II) | (Ic) | |
Crystal data | ||||
Chemical formula | C5H6F6O2 | C5H6F6O2 | C5H6F6O2 | C5H6F6O2 |
Mr | 212.10 | 212.10 | 212.10 | 212.10 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 283 | 173 | 173 | 283 |
a, b, c (Å) | 4.9343 (10), 6.8918 (14), 11.342 (2) | 4.8848 (12), 6.8723 (16), 11.259 (3) | 4.8641 (12), 5.7380 (14), 13.325 (3) | 4.9215 (18), 6.871 (3), 11.314 (4) |
α, β, γ (°) | 81.943 (3), 85.847 (3), 86.529 (3) | 82.261 (3), 84.711 (3), 85.640 (3) | 82.814 (3), 87.274 (3), 86.435 (4) | 81.973 (5), 85.839 (5), 86.562 (5) |
V (Å3) | 380.41 (13) | 372.16 (15) | 367.98 (16) | 377.3 (2) |
Z | 2 | 2 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.23 | 0.23 | 0.24 | 0.23 |
Crystal size (mm) | 0.35 × 0.20 × 0.17 | 0.35 × 0.20 × 0.17 | 0.35 × 0.20 × 0.17 | 0.35 × 0.20 × 0.17 |
Data collection | ||||
Diffractometer | Bruker SMART 1000 CCD Platform diffractometer | Bruker SMART 1000 CCD Platform diffractometer | Bruker SMART 1000 CCD Platform diffractometer | Bruker SMART 1000 CCD Platform diffractometer |
Absorption correction | Multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | Multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | Multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) | Multi-scan (TWINABS, Version 2008/1; Sheldrick, 2008) |
Tmin, Tmax | 0.924, 0.962 | 0.923, 0.961 | 0.922, 0.961 | 0.924, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4125, 1721, 1419 | 3947, 1686, 1480 | 5181, 1652, 1289 | 5825, 1729, 1200 |
Rint | 0.030 | 0.033 | 0.050 | 0.030 |
(sin θ/λ)max (Å−1) | 0.651 | 0.650 | 0.649 | 0.649 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.085, 1.03 | 0.041, 0.122, 1.04 | 0.054, 0.138, 1.04 | 0.049, 0.129, 1.02 |
No. of reflections | 1721 | 1686 | 1652 | 1729 |
No. of parameters | 240 | 240 | 242 | 242 |
No. of restraints | 3 | 3 | 3 | 3 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.17 | 0.40, −0.29 | 0.39, −0.39 | 0.27, −0.30 |
Absolute structure | Flack (1983), with Friedel pairs merged | Flack (1983), with Friedel pairs merged | Flack (1983), with how many Friedel pairs? | Flack (1983), with Friedel pairs merged |
Absolute structure parameter | 0.2 (9) | −0.3 (10) | −0.8 (14) | 0.2 (14) |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 2007), SHELXL97 (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008).
The first row of data for each hydrogen bond are based on riding H-atom positions and the second row on a D—H bond length extended to 0.983 Å along the D—H vector from the refinement. |
D—H···A | D—H | H···A | D···A | D—H···A |
(Ia) | ||||
O1—H1A···O4i | 0.82 | 1.93 | 2.740 (3) | 168.3 |
0.983 | 1.773 | 167.3 | ||
O2—H2A···O3ii | 0.82 | 1.93 | 2.742 (4) | 169.4 |
0.983 | 1.772 | 168.4 | ||
O3—H3A···O2iii | 0.82 | 1.96 | 2.758 (4) | 165.2 |
0.983 | 1.800 | 163.9 | ||
O4—H4A···O1iv | 0.82 | 1.94 | 2.746 (4) | 165.5 |
0.983 | 1.787 | 164.2 | ||
(Ib) | ||||
O1—H1A···O4i | 0.84 | 1.89 | 2.717 (4) | 169.4 |
0.983 | 1.747 | 168.6 | ||
O2—H2A···O3ii | 0.84 | 1.90 | 2.732 (5) | 169.1 |
0.983 | 1.762 | 168.3 | ||
O3—H3A···O2iii | 0.84 | 1.91 | 2.740 (5) | 171.1 |
0.983 | 1.766 | 170.4 | ||
O4—H4A···O1iv | 0.84 | 1.91 | 2.733 (4) | 165.7 |
0.983 | 1.773 | 164.6 | ||
(II) | ||||
O1—H1A···O4i | 0.84 | 1.93 | 2.746 (6) | 162.5 |
0.983 | 1.798 | 161.1 | ||
O2—H2A···O3ii | 0.84 | 1.89 | 2.714 (6) | 166.9 |
0.983 | 1.751 | 165.8 | ||
O3—H3A···O2iii | 0.84 | 1.93 | 2.733 (6) | 159.6 |
0.983 | 1.796 | 157.9 | ||
O4—H4A···O1iv | 0.84 | 1.90 | 2.736 (6) | 175.2 |
0.983 | 1.756 | 174.8 | ||
(Ic) | ||||
O1—H1A···O4i | 0.82 | 1.93 | 2.736 (5) | 169.3 |
0.983 | 1.766 | 168.3 | ||
O2—H2A···O3ii | 0.82 | 1.93 | 2.728 (6) | 166.1 |
0.983 | 1.768 | 164.8 | ||
O3—H3A···O2iii | 0.82 | 1.96 | 2.756 (6) | 164.0 |
0.983 | 1.802 | 162.6 | ||
O4—H4A···O1iv | 0.82 | 1.96 | 2.741 (6) | 157.9 |
0.983 | 1.814 | 156.0 |
Symmetry codes: (i) x, y - 1, z + 1; (ii) x - 1, y + 1, z; (iii) x, y - 1, z; (iv) x + 1, y + 1, z - 1. |
(Ia) | (Ib) | (II) | (Ic) | |
O1—C1—C2—C3 | 175.6 (3) | 175.6 (3) | 178.4 (5) | 176.0 (5) |
C1—C2—C3—C4 | 169.1 (3) | 169.1 (3) | 169.7 (5) | 169.2 (4) |
C2—C3—C4—C5 | 171.5 (3) | 171.5 (3) | 170.3 (5) | 171.1 (5) |
C3—C4—C5—O2 | 178.3 (3) | 178.2 (3) | 175.2 (5) | 178.4 (4) |
O3—C6—C7—C8 | -176.4 (3) | -176.2 (4) | -177.4 (5) | -176.7 (4) |
C6—C7—C8—C9 | -168.9 (3) | -168.9 (3) | -167.6 (5) | -169.1 (5) |
C7—C8—C9—C10 | -167.6 (3) | -167.0 (4) | -166.9 (5) | -167.8 (4) |
C8—C9—C10—O4 | -176.9 (3) | -176.5 (3) | -176.4 (5) | -177.4 (4) |
(Ia) | (Ib) | (II) | (Ic) | |
F1···F2vi/F2···F1v | 3.014 (4) | 2.969 (4) | 3.070 (5) | 3.009 (6) |
F2···F10viii/F10···F2vii | 2.990 (3) | 2.971 (4) | 4.138 (4) | 2.979 (5) |
F3···F4vi/F4···F3v | 2.922 (3) | 2.881 (4) | 2.860 (5) | 2.913 (5) |
F3···F5iii/F5···F3ix | 4.383 (3) | 4.387 (3) | 2.963 (5) | 4.367 (4) |
F4···F8v/F8···F4vi | 2.905 (3) | 2.877 (3) | 4.173 (4) | 2.903 (4) |
F7···F8v/F8···F7vi | 3.048 (4) | 3.010 (4) | 3.054 (6) | 3.037 (6) |
F9···F10v/F10···F9vi | 2.893 (3) | 2.841 (4) | 2.836 (5) | 2.881 (5) |
F11···F12v/F12···F11vi | 3.077 (4) | 3.048 (4) | 3.013 (5) | 3.071 (6) |
Symmetry codes: (iii) x, y - 1, z; (iv) x + 1, y + 1, z - 1; (v) x - 1, y, z; (vi) x + 1, y, z; (vii) x + 1, y, z - 1; (viii) x - 1, y, z + 1; (ix) x, y + 1, z. |
The D—H bond length is extended to 0.983 Å along the D—H vector obtained from refinement |
C—H···F | (Ia) | (Ib) | (II) | (Ic) |
C1—H1B···F5iii | 2.535 | 2.457 | 2.545 | 2.525 |
C1—H1C···F3v | 2.677 | 2.618 | 2.599 | 2.675 |
C5—H5A···F6vi | 2.888 | 2.737 | 2.570 | 2.809 |
C6—H6A···F12vi | 2.499 | 2.456 | 2.590 | 2.487 |
C6—H6B···F9vi | 2.752 | 2.683 | 2.628 | 2.730 |
C10—H10A···F10v | 2.711 | 2.639 | 2.564 | 2.709 |
C10—H10B···F2vii | 2.416 | 2.348 | 2.535 | 2.394 |
Symmetry codes: (iii) x, y - 1, z; (v) x - 1, y, z; (vi) x + 1, y, z; (vii) x + 1, y, z - 1. |
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Enantiotropic phase transitions provide important information regarding the physical properties of the same material in different crystalline forms. These require two polymorphs that are each thermodynamically stable over a range of temperature and pressure, where variation of either will lead to a phase transition to the other polymorph (Herbstein, 2006). Single-crystal-to-single-crystal transitions of crystalline solids have been observed for solid-state phase transitions of enantiotropic polymorphs (Caira et al., 2004; Lim & Jeong, 2001; Asadov, 1967), pressure-dependent transitions between polymorphs (Fabbiani et al., 2005), solid-state geometric isomerizations (Agmon & Kaftory, 1994), topochemical reactions (Enkelmann & Wegner, 1993), solid-state polymerizations (Okada et al., 1994) and pseudo-polymorphic transitions of guest-inclusion compounds (Atwood et al., 2002; Ananchenko et al., 2006). There are reports of enantiotropic phase transitions accompanying a change of crystal system and space group while becoming twinned (Choe et al., 2000; Colombo et al., 2000; Guzei et al., 2009; Jadzewski et al., 2001; Reger et al., 2001; Schweitzer et al. 2000). In the majority of these reports, the higher-temperature phase is also the higher-symmetry minimal nonisomorphic supergroup of the pair, while the lower-temperature phase becomes twinned in a maximal nonisomorphic subgroup. The present study is quite different, because there is no change in symmetry as the phase (I) to phase (II) transition occurs, but rather a sliding of the two unique diol molecules within the unit cell to the other polymorphic form.
The material of interest in this study, 2,2,3,3,4,4-hexafluoropentane-1,5-diol, HFPD, has been used as a reagent to prepare fluorinated polymers and as a precursor to cyclic and acyclic polyfluorosiloxanes (Johncock & Hewins, 1975; Elias et al., 1994; Adhikari et al., 1999; Patel et al., 1994). The solid-state chemistry of fluorocarbons has been a subject of interest because of their unique properties in molecular solids (Reichenbächer et al., 2005). HFPD has also been crystallized within the channels of nanocrystals (Ha et al., 2005), where the initial report of the cell constants for both HFPD phases was presented.
Displacement ellipsoid drawings of all four structure determinations are shown in Fig. 1. All C—C, C—O and C—F distances of the two unique HFPD molecules appear to be in normal ranges for all four structure determinations presented here. However, the basic structural features of these two HFPD polymorphs are unique among reported diol structures (Allen, 2002). The space group for both is P1, with Z = 2 and Z' = 2. The molecules are arranged in intersecting C11(2) and C11(8) chains to form infinite R44(20) sheets (Bernstein et al. 1995; Etter, 1990; Etter et al., 1990; Grell et al., 1999). Both phases exhibit strong pseudo-symmetry as a pseudo c-glide reflection perpendicular to the a-axis and pseudo-twofold symmetry perpendicular to the layers.
Initial twinned-crystal diffraction studies (not presented here) suggested the phase transition temperature was below the 283 K used for forms (Ia) and (Ic), and above the 173 K used for form (Ib) and (II). This was later confirmed by other means (see below). The packing diagrams for forms (Ib) and (II) at 173 K are shown in Fig. 2. The crystal structures of both phases (I) and (II) of HFPD are composed of stacked infinite molecular sheets. These sheets, parallel to the (012) planes of each polymorph, have in-plane hydrogen bonding between primary hydroxyl groups. The hydrogen bonds, along with corrected H-atom positions based on normalized O—H distances, are presented in Table 1. The hydrogen-bonding network forms a rigid substructure that does not appear to change appreciably throughout the course of the study. Hydrogen bonds are reported with both distances and angles derived from riding O-bound H-atom positions (Sheldrick, 2008) and with normalized H-atom positions (Thalladi et al., 1998). The only minor differences are observed as slightly shorter D···A and H···A normalized distances for forms (Ib) and (II), both at 173 K. The phase transition does not impose any substantial change on the hydrogen-bonding scheme, even though the unit cell undergoes a radical change.
The torsion angle analyses for each HFPD backbone are presented in Table 2. These vary considerably from planar zigzag hydrocarbon chains, where the expected values are approximately 180° (Dunitz, 2004). There are two types in this list. The first type incorporates the O atom of a hydroxyl group, a –CH2– group and the two adjacent –CF2– groups. The other type has a –CH2– group and three adjacent –CF2– groups. The average O—C—C—C torsion angle is 176.9 (11)°, while the average C—C—C—C torsion angle is 169.1 (15)°. Each of the two unique molecules is twisted by a different angle, averaging 25.7 (5) and 30.6 (12)° for respective molecules over the four structures presented here. This implies each HFPD molecule is twisted considerably from the aforementioned zigzag hydrocarbon chains. This twisting imposes chirality on each HFPD molecule. Given the presence of the pseudo-glide reflection operation and the two unique HFPD molecules in the unit cell, each HFPD molecule is a pseudo-enantiomer of the other. While respective molecules have about a 5° difference in the twist of the diol fragments, the weighted r.m.s. deviations for superposition of the enantiomers for all non-H atoms are 0.0393 for (Ia), 0.0474 for (Ib), 0.0399 for (II) and 0.0387 Å for (Ic).
The hydroxyl functionalities for phases (I) and (II) are effectively enclosed within the substructure, preventing non-bonded contacts with any F atoms. Similarly, the F atoms only take part in non-bonded contacts with C—F F atoms and C—H H atoms. This is strikingly similar to the property of mutual phobicity between fluorocarbons and hydrocarbons as described by Dunitz (2004). These functional groups tend to segregate within crystal structures when no overriding structural feature imposes an unfavorable contact. It appears the same reasoning is applicable to HFPD, which has the three different functional groups of hydroxyl, hydrocarbon and fluorocarbon.
While non-bonded contacts between hydroxyl groups and both hydrocarbon and fluorocarbon groups are surprisingly absent due to the efficient packing, there is a mixture of both F···F and C—H···F close contacts that appears to govern the enantiotropic phase transition. Table 3 presents all significant F···F non-bonded contacts throughout this study. Pairs of C—F bonds involved in single F···F intermolecular contacts are tracked through all structure determinations if at least one is less than 3.10 Å. All of these F···F intermolecular contacts shrink by 1.2 (4)% upon cooling of form (Ia) at 283 K to form (Ib) at 173 K, which follows the contraction of the unit-cell volume. The average F···F intermolecular contacts increase from 3.1 (5) Å in form (Ib) to 3.3 (6) Å in form (II), due to a lack of one less than 3.10 Å in form (II). Two of the eight F···F intermolecular contacts in this group for both forms (Ib) and (II) are less than 2.90 Å, which is considered to be the limit for an F···F van der Waals contact (Rowland & Taylor, 1996; Bondi, 1964). Overall, the F···F intermolecular contacts are more favorable for form (II) at 173 K.
A similar situation is found for C—H···F close contacts in this study. Table 4 presents all significant C—H···F close contacts throughout the series. Form (Ia) at 283 K has three C—H···F close contacts less than 2.54 Å, one of which is less than 2.42 Å. C—H···F close contacts may be mildly stabilizing at distances greater than 2.54 Å (Rowland & Taylor, 1996), but rarely ever form (Dunitz & Taylor, 1997). In the few confirmed instances, the lower limit of a C—H···F close contact is approximately 2.36 Å when the hybridization of the C—H fragment is either sp2 or sp3 (Thalladi et al., 1998; Howard et al., 1996). Upon cooling form (Ia) to the metastable form (Ib) at 173 K, these three close contacts decrease on average by 0.06 (2) Å. The shortest of the three C—H···F close contacts is within the van der Waals limit at 2.348 Å. These C—H···F close contacts provide addtional impetus for the enantiotropic phase transition to form (II). All C—H···F close contacts in form (II) are found in a narrower range of 2.535–2.628 Å, thereby avoiding any of the short C—H···F close contacts found in form (Ib). The result of the enantiotropic phase change is a slight increase in the density of form (II) of about 1.1% at this temperature.
The enantiotropic phase transition of HFPD was confirmed with differential scanning calorimetry (DSC) and powder X-ray diffraction (XRD). By DSC analyses, the room-temperature stable phase (I) of HFPD transformed to the low-temperature stable phase (II) by cooling to 253 K, as exhibited in Fig. 3. Phase (II) reversibly transformed to phase (I) at 275–283 K by heating. Phase (I) melted to a liquid phase at 354 K. The enthalpy change of the phase transition of phase (II) to phase (I) was 0.44 (1) kJ mol-1, while the enthalpy change on melting phase (I) to a liquid phase was 29.7 (3) kJ mol-1. The observed enthalpy change for the solid-state phase transition is relatively small compared with other organic crystal structures (Yu et al., 2000; Cingolani & Berchiesi, 1974; Petropavlov et al., 1988; Steele et al., 2002). Typical values of enthalpy changes for similar phase transitions fall in the range 1–10 kJ mol-1, which is larger than the observed enthalpy change from phase (II) to (I) of HFPD. The small value of the enthalpy change can be attributed to the modest change in the crystal structure during the solid-state transition. Temperature-dependent XRD confirmed the phase transition between phases (I) and (II) that was observed in the single-crystal of HFPD, as depicted in Fig. 4. Although the reflections of the (012) and (101) planes of phases (I) and (II) are nearly indistinguishable by 2θ positions alone, disappearance of the 010, 002 and 101 reflections of phase (I) and appearance of the corresponding reflections of phase (II) were clearly observed at 263–253 K during cooling from room temperature to 243 K. The reflections of phase (I) were obtained again when the crystalline powder was heated to room temperature.
It is of interest to compare these polymorphic HFPD diol structures with studies of the packing motifs of all diol structures (Taylor & Macrae, 2001). Both primary mono-alcohols and primary–primary diols are much more likely to form chain structures rather than ring structures. Chains are also favored for any diol with one primary alcohol. When considering all diols, including secondary and tertiary, the frequencies of chain and ring structures are very similar. The HFPD polymorphs break this trend because these form two-dimensional sheets, despite being primary–primary diols. One point in common with primary–primary diol ring structures is that virtually all ring structures have four hydrogen bonds. A study of vicinal diols restates the observation that Z' > 1 structures are relatively common if each O atom is involved in more than one hydrogen bond (Brock, 2002).
The single specimen examined as part of this study, and a number of other unreported investigations of HFPD by the authors, were always twinned by nonmerohedry. These specimens were crystallized at temperatures higher than the phase transition, whether these were prepared by recrystallization from methanol, as was done in this study, or by sublimation. Diagrams of the twinning domains are presented in Fig. 5 for phase (I) and Fig. 6 for phase (II). Each twin domain depicted in these two diagrams is drawn with the (012) plane in the page and with the [100] axis parallel to the horizontal axis. The O atoms of each of the unique HFPD molecules are indicated, while the unit-cell axes are shown on the right.
The two twin components of form (Ia) refined to a 0.724 (5):0.276 (5) ratio, with the second twin component corresponding to a 180° rotation about the [100] axis, as shown in Fig. 5(a) and (b). However, the assignment of the twin law does not take into account the possibility of racemic twinning in addition to this twin domain found by nonmerohedry. A twin law with only a 180° rotation about the [100] axis does not bring the composition plane into registry with the reference twin domain unless the enantiomorph is used. Therefore, the permutation of the twofold rotation in [100] and the inversion necessary to provide the enantiomorph is effectively a reflection in the (011) plane. Diffraction data acquired with molybdenum radiation prevents the determination of absolute configuration when F is the heaviest atom. However, this twin law provides for a seamless composition plane, or interface, between the respective twin domains. Form (Ib) can be isolated by carefully cooling the specimen to 173 K, which will preserve the same two twin domains as in form (Ia), but these refined to a 0.597 (5):0.403 (5) ratio. It appears that there is some conversion of the reference individual to the minor individual as the temperature is reduced. A momentary warming by blocking the cryostat flow and recooling causes the phase transition from form (Ib) to form (II). Form (II) contains the same two twin domains as form (Ib), as shown in Fig. 6(a) and (b), but two additional twin components are discovered, concomitant with the enantiotropic phase transition, as shown in Fig. 6(c) and (d). The ratio of twin components for form (II) is 0.339 (6):0.408 (6):0.141 (5):0.112 (4). It is presumed that the appearance of the third and fourth twin components is due to deformation in conjunction with the (Ib) to (II) phase transition. The relationship between twin component pairs 1 and 3 and 2 and 4 is a 180° rotation about the perpendicular to the (012) plane, thereby exploiting the twofold pseudosymmetry within the layer structure. The relationship between twin component pair 3 and 4 is the same as that between pair 1 and 2, described above. Finally, when form (II) is warmed back to 283 K, all four twin domains present are retained in form (Ic) after the phase (II) to phase (I) transition occurs. The ratio of twin components for (Ic) is 0.333 (6):0.434 (6):0.110 (5):0.122 (4). These two additional twin domains present in (Ic) are shown in Fig. 5(c) and 5(d).
The phase transition between phases (I) and (II) is accomplished by a sliding of the (012) layers in the [013] direction, as shown in Fig. 7. The contraction of the unit cell in form (Ia) on cooling to form (Ib), coupled with several unfavorable close contacts in form (Ib), as discussed above, precipitates the phase transition to form (II), whereby all layers slide by approximately 1.83 (5) Å.