3-trans-Bromo-5-cis-fluoro-2,6,6-trimethyl-2-phenyl­tetra­hydro­pyran

The title compound, C₁₄H₁₈BrFO, 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.

Key indicators

• Single-crystal X-ray study
• T = 303 K
• Mean [sigma](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

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Computing details

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

Crystal data

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) Å^3	Rod, colorless
Z = 8	0.76 × 0.16 × 0.16 mm
F(000) = 1232

Data collection

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

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.073	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.188	H-atom parameters constrained
S = 1.20	w = 1/[σ^2(Fo^2) + (0.079P)^2 + 0.7239P] where P = (Fo^2 + 2Fc^2)/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

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 (Ų)

	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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)