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The title compound, C
14H
18BrFO, is a hexasubstituted tetrahydropyran with two halogen atoms attached in β and four C substituents in α positions with respect to the ether O atom. The C
C distance [3.183 (7) Å] between the two 1,3-diaxially oriented α-methyl groups falls below the sum of the van der Waals radii. The magnitude of the bond angle at oxygen [122.6 (3)°] and a comparatively small displacement of this atom [0.490 (5) Å] from the mean plane of four C atoms of the tetrahydropyran ring indicate a marked flattening of the heterocyclic ring in its
1C4 conformation.
Supporting information
CCDC reference: 282351
Key indicators
- Single-crystal X-ray study
- T = 303 K
- Mean (C-C) = 0.007 Å
- R factor = 0.073
- wR factor = 0.188
- Data-to-parameter ratio = 18.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.76 mm
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ?
PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.94 Ratio
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 7
PLAT412_ALERT_2_C Short Intra XH3 .. XHn H7A .. H9B .. 1.84 Ang.
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
5 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis RED (Oxford Diffraction, 2002); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON2002 (Spek, 1990, 2003) and ORTEP-3 (Farrugia, 1997,
2005); software used to prepare material for publication: SHELXL97.
3-
trans-Bromo-5-
cis-fluoro-2,6,6-trimethyl-2-phenyltetrahydropyran
top
Crystal data top
C14H18BrFO | Dx = 1.452 Mg m−3 |
Mr = 301.19 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 2925 reflections |
a = 9.410 (1) Å | θ = 2.8–21.8° |
b = 12.605 (1) Å | µ = 2.98 mm−1 |
c = 23.229 (2) Å | T = 303 K |
V = 2755.3 (4) Å3 | Rod, colorless |
Z = 8 | 0.76 × 0.16 × 0.16 mm |
F(000) = 1232 | |
Data collection top
Oxford Diffraction Xcalibur (TM) with Sapphire CCD detector diffractometer | 2809 independent reflections |
Radiation source: fine-focus sealed tube | 1991 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.082 |
rotation method data acquisition using ω scans | θmax = 26.4°, θmin = 4.1° |
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2002) | h = −11→11 |
Tmin = 0.312, Tmax = 0.717 | k = −15→9 |
16564 measured reflections | l = −29→29 |
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)] = 0.073 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.20 | w = 1/[σ2(Fo2) + (0.079P)2 + 0.7239P] where P = (Fo2 + 2Fc2)/3 |
2809 reflections | (Δ/σ)max = 0.015 |
155 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −0.66 e Å−3 |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R- factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C2 | 0.1631 (4) | 0.1499 (3) | 0.14921 (17) | 0.0315 (9) | |
C3 | 0.1287 (5) | 0.2675 (3) | 0.1375 (2) | 0.0407 (11) | |
H3 | 0.0777 | 0.2713 | 0.1008 | 0.049* | |
C4 | 0.2591 (5) | 0.3370 (3) | 0.1327 (2) | 0.0529 (13) | |
H4A | 0.2312 | 0.4096 | 0.1247 | 0.064* | |
H4B | 0.3116 | 0.3359 | 0.1686 | 0.064* | |
C5 | 0.3501 (6) | 0.2957 (4) | 0.0849 (2) | 0.0585 (14) | |
H5 | 0.4375 | 0.3379 | 0.0830 | 0.070* | |
C6 | 0.3891 (5) | 0.1795 (4) | 0.0910 (2) | 0.0501 (13) | |
C7 | 0.5072 (5) | 0.1677 (5) | 0.1368 (3) | 0.0674 (17) | |
H7A | 0.4745 | 0.1960 | 0.1728 | 0.081* | |
H7B | 0.5902 | 0.2059 | 0.1245 | 0.081* | |
H7C | 0.5304 | 0.0940 | 0.1414 | 0.081* | |
C8 | 0.4392 (7) | 0.1307 (6) | 0.0357 (3) | 0.092 (2) | |
H8A | 0.5213 | 0.1682 | 0.0220 | 0.110* | |
H8B | 0.3648 | 0.1350 | 0.0074 | 0.110* | |
H8C | 0.4633 | 0.0577 | 0.0421 | 0.110* | |
C9 | 0.2240 (5) | 0.1302 (4) | 0.20895 (19) | 0.0492 (12) | |
H9A | 0.1566 | 0.1527 | 0.2375 | 0.059* | |
H9B | 0.3106 | 0.1696 | 0.2134 | 0.059* | |
H9C | 0.2430 | 0.0559 | 0.2136 | 0.059* | |
C10 | 0.0334 (4) | 0.0816 (3) | 0.13574 (19) | 0.0344 (10) | |
C11 | −0.0370 (5) | 0.0221 (4) | 0.1772 (2) | 0.0465 (12) | |
H11 | −0.0055 | 0.0236 | 0.2152 | 0.056* | |
C12 | −0.1522 (5) | −0.0388 (4) | 0.1629 (2) | 0.0542 (13) | |
H12 | −0.1962 | −0.0795 | 0.1911 | 0.065* | |
C13 | −0.2038 (5) | −0.0409 (4) | 0.1079 (2) | 0.0545 (13) | |
H13 | −0.2837 | −0.0810 | 0.0989 | 0.065* | |
C14 | −0.1349 (5) | 0.0177 (4) | 0.0660 (2) | 0.0515 (12) | |
H14 | −0.1676 | 0.0163 | 0.0282 | 0.062* | |
C15 | −0.0180 (5) | 0.0780 (4) | 0.0801 (2) | 0.0442 (12) | |
H15 | 0.0273 | 0.1171 | 0.0515 | 0.053* | |
O1 | 0.2635 (3) | 0.1178 (2) | 0.10504 (12) | 0.0401 (8) | |
F1 | 0.2735 (4) | 0.3093 (3) | 0.03384 (14) | 0.0906 (12) | |
Br1 | 0.00284 (6) | 0.32459 (5) | 0.19737 (3) | 0.0713 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C2 | 0.038 (2) | 0.031 (2) | 0.025 (2) | 0.0034 (17) | −0.0004 (18) | −0.0006 (17) |
C3 | 0.042 (3) | 0.040 (2) | 0.041 (3) | 0.007 (2) | −0.002 (2) | −0.003 (2) |
C4 | 0.058 (3) | 0.033 (2) | 0.069 (4) | −0.003 (2) | −0.013 (3) | 0.004 (2) |
C5 | 0.054 (3) | 0.066 (3) | 0.056 (4) | −0.024 (3) | −0.006 (3) | 0.010 (3) |
C6 | 0.040 (3) | 0.060 (3) | 0.051 (3) | −0.013 (2) | 0.006 (2) | −0.007 (2) |
C7 | 0.040 (3) | 0.069 (4) | 0.093 (5) | 0.003 (2) | −0.008 (3) | −0.008 (3) |
C8 | 0.068 (4) | 0.125 (5) | 0.082 (5) | −0.027 (4) | 0.039 (4) | −0.038 (4) |
C9 | 0.050 (3) | 0.057 (3) | 0.041 (3) | 0.002 (2) | −0.013 (2) | 0.003 (2) |
C10 | 0.036 (2) | 0.033 (2) | 0.035 (2) | 0.0046 (18) | 0.0027 (19) | 0.0027 (19) |
C11 | 0.052 (3) | 0.055 (3) | 0.033 (2) | −0.004 (2) | 0.000 (2) | 0.004 (2) |
C12 | 0.047 (3) | 0.064 (3) | 0.052 (3) | −0.014 (3) | 0.011 (2) | 0.009 (3) |
C13 | 0.038 (3) | 0.070 (3) | 0.056 (3) | −0.006 (3) | −0.003 (2) | 0.000 (3) |
C14 | 0.047 (3) | 0.065 (3) | 0.042 (3) | −0.003 (2) | −0.009 (2) | 0.002 (2) |
C15 | 0.047 (3) | 0.049 (3) | 0.036 (3) | −0.008 (2) | −0.001 (2) | 0.004 (2) |
O1 | 0.0352 (17) | 0.0423 (16) | 0.0429 (18) | −0.0031 (13) | 0.0082 (14) | −0.0069 (14) |
F1 | 0.093 (3) | 0.120 (3) | 0.058 (2) | −0.018 (2) | −0.0036 (19) | 0.039 (2) |
Br1 | 0.0697 (5) | 0.0639 (5) | 0.0802 (5) | 0.0222 (3) | 0.0101 (3) | −0.0192 (3) |
Geometric parameters (Å, º) top
C2—O1 | 1.452 (5) | C7—H7C | 0.9600 |
C2—C9 | 1.521 (6) | C8—H8A | 0.9600 |
C2—C10 | 1.527 (6) | C8—H8B | 0.9600 |
C2—C3 | 1.541 (5) | C8—H8C | 0.9600 |
C3—C4 | 1.512 (6) | C9—H9A | 0.9600 |
C3—Br1 | 1.963 (4) | C9—H9B | 0.9600 |
C3—H3 | 0.9800 | C9—H9C | 0.9600 |
C4—C5 | 1.496 (7) | C10—C15 | 1.382 (6) |
C4—H4A | 0.9700 | C10—C11 | 1.390 (6) |
C4—H4B | 0.9700 | C11—C12 | 1.369 (7) |
C5—F1 | 1.400 (6) | C11—H11 | 0.9300 |
C5—C6 | 1.516 (7) | C12—C13 | 1.366 (7) |
C5—H5 | 0.9800 | C12—H12 | 0.9300 |
C6—O1 | 1.452 (5) | C13—C14 | 1.385 (7) |
C6—C8 | 1.501 (7) | C13—H13 | 0.9300 |
C6—C7 | 1.545 (7) | C14—C15 | 1.377 (6) |
C7—H7A | 0.9600 | C14—H14 | 0.9300 |
C7—H7B | 0.9600 | C15—H15 | 0.9300 |
| | | |
O1—C2—C9 | 110.7 (3) | H7A—C7—H7C | 109.5 |
O1—C2—C10 | 102.6 (3) | H7B—C7—H7C | 109.5 |
C9—C2—C10 | 113.3 (3) | C6—C8—H8A | 109.5 |
O1—C2—C3 | 106.3 (3) | C6—C8—H8B | 109.5 |
C9—C2—C3 | 113.4 (3) | H8A—C8—H8B | 109.5 |
C10—C2—C3 | 109.8 (3) | C6—C8—H8C | 109.5 |
C4—C3—C2 | 113.5 (4) | H8A—C8—H8C | 109.5 |
C4—C3—Br1 | 109.2 (3) | H8B—C8—H8C | 109.5 |
C2—C3—Br1 | 110.8 (3) | C2—C9—H9A | 109.5 |
C4—C3—H3 | 107.7 | C2—C9—H9B | 109.5 |
C2—C3—H3 | 107.7 | H9A—C9—H9B | 109.5 |
Br1—C3—H3 | 107.7 | C2—C9—H9C | 109.5 |
C5—C4—C3 | 108.6 (4) | H9A—C9—H9C | 109.5 |
C5—C4—H4A | 110.0 | H9B—C9—H9C | 109.5 |
C3—C4—H4A | 110.0 | C15—C10—C11 | 117.7 (4) |
C5—C4—H4B | 110.0 | C15—C10—C2 | 119.3 (4) |
C3—C4—H4B | 110.0 | C11—C10—C2 | 122.9 (4) |
H4A—C4—H4B | 108.4 | C12—C11—C10 | 120.7 (5) |
F1—C5—C4 | 106.9 (4) | C12—C11—H11 | 119.6 |
F1—C5—C6 | 108.8 (4) | C10—C11—H11 | 119.6 |
C4—C5—C6 | 113.9 (4) | C11—C12—C13 | 121.4 (5) |
F1—C5—H5 | 109.0 | C11—C12—H12 | 119.3 |
C4—C5—H5 | 109.0 | C13—C12—H12 | 119.3 |
C6—C5—H5 | 109.0 | C12—C13—C14 | 118.7 (5) |
O1—C6—C8 | 103.2 (4) | C12—C13—H13 | 120.6 |
O1—C6—C5 | 109.9 (4) | C14—C13—H13 | 120.6 |
C8—C6—C5 | 113.0 (5) | C15—C14—C13 | 120.1 (5) |
O1—C6—C7 | 112.3 (4) | C15—C14—H14 | 119.9 |
C8—C6—C7 | 108.9 (5) | C13—C14—H14 | 119.9 |
C5—C6—C7 | 109.3 (4) | C14—C15—C10 | 121.3 (4) |
C6—C7—H7A | 109.5 | C14—C15—H15 | 119.3 |
C6—C7—H7B | 109.5 | C10—C15—H15 | 119.3 |
H7A—C7—H7B | 109.5 | C6—O1—C2 | 122.6 (3) |
C6—C7—H7C | 109.5 | | |
| | | |
O1—C2—C3—C4 | −52.9 (5) | C3—C2—C10—C15 | 62.9 (5) |
C9—C2—C3—C4 | 69.0 (5) | O1—C2—C10—C11 | 130.5 (4) |
C10—C2—C3—C4 | −163.2 (4) | C9—C2—C10—C11 | 11.0 (6) |
O1—C2—C3—Br1 | −176.3 (2) | C3—C2—C10—C11 | −116.9 (4) |
C9—C2—C3—Br1 | −54.3 (4) | C15—C10—C11—C12 | 0.8 (7) |
C10—C2—C3—Br1 | 73.5 (4) | C2—C10—C11—C12 | −179.4 (4) |
C2—C3—C4—C5 | 58.7 (5) | C10—C11—C12—C13 | −1.7 (8) |
Br1—C3—C4—C5 | −177.1 (3) | C11—C12—C13—C14 | 1.8 (8) |
C3—C4—C5—F1 | 65.5 (5) | C12—C13—C14—C15 | −1.0 (7) |
C3—C4—C5—C6 | −54.8 (6) | C13—C14—C15—C10 | 0.1 (7) |
F1—C5—C6—O1 | −72.1 (5) | C11—C10—C15—C14 | 0.0 (7) |
C4—C5—C6—O1 | 47.1 (6) | C2—C10—C15—C14 | −179.8 (4) |
F1—C5—C6—C8 | 42.6 (6) | C8—C6—O1—C2 | −167.4 (5) |
C4—C5—C6—C8 | 161.8 (5) | C5—C6—O1—C2 | −46.6 (5) |
F1—C5—C6—C7 | 164.2 (4) | C7—C6—O1—C2 | 75.4 (5) |
C4—C5—C6—C7 | −76.7 (5) | C9—C2—O1—C6 | −74.9 (5) |
O1—C2—C10—C15 | −49.8 (5) | C10—C2—O1—C6 | 163.9 (4) |
C9—C2—C10—C15 | −169.2 (4) | C3—C2—O1—C6 | 48.7 (5) |
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