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Centrosymmetric hydrogen-bonding between carb­oxy substituents links enanti­omers of the title compound, C15H19BrO3, into dimers. Close contacts that originate from axially arranged methyl substituents in positions 2 and 6 induce distortions, which are evident from a widening of the endocyclic bond angle at the ring O atom [122.6 (6)°] and a flattening of the tetra­hydro­pyran chair.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806012621/lh2031sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806012621/lh2031Isup2.hkl
Contains datablock I

CCDC reference: 608442

Key indicators

  • Single-crystal X-ray study
  • T = 303 K
  • Mean [sigma](C-C) = 0.015 Å
  • R factor = 0.069
  • wR factor = 0.217
  • Data-to-parameter ratio = 17.6

checkCIF/PLATON results

No syntax errors found



Alert level A RINTA01_ALERT_3_A The value of Rint is greater than 0.20 Rint given 0.252 PLAT020_ALERT_3_A The value of Rint is greater than 0.10 ......... 0.25
Alert level B PLAT026_ALERT_3_B Ratio Observed / Unique Reflections too Low .... 34 Perc.
Alert level C RADNW01_ALERT_1_C The radiation wavelength lies outside the expected range for the supplied radiation type. Expected range 0.71065-0.71075 Wavelength given = 0.71093 PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.80 mm PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C11 PLAT331_ALERT_2_C Small Average Phenyl C-C Dist. C8 -C16 1.37 Ang. PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 15
2 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 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 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: CAD-4 Diffractometer Control Software (Enraf–Nonius, 1993); cell refinement: CAD-4 Diffractometer Control Software; data reduction: CAD-4 Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON2002 (Spek, 2003) and ORTEP-3 (Farrugia, 1997, 2005); software used to prepare material for publication: SHELXL97.

cis-5-Bromo-2,2,6-trimethyl-trans-6-phenyltetrahydropyran-3-carboxylic acid top
Crystal data top
C15H19BrO3F(000) = 672
Mr = 327.21Dx = 1.431 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71093 Å
a = 9.955 (2) ÅCell parameters from 25 reflections
b = 9.875 (3) Åθ = 2.7–13.6°
c = 15.896 (2) ŵ = 2.71 mm1
β = 103.62 (1)°T = 303 K
V = 1518.7 (6) Å3Plate, colourless
Z = 40.80 × 0.32 × 0.05 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer
1024 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.252
Graphite monochromatorθmax = 26.0°, θmin = 2.5°
ω/2θ scansh = 122
Absorption correction: ψ scan
(North et al., 1968)
k = 120
Tmin = 0.221, Tmax = 0.877l = 1919
3621 measured reflections3 standard reflections every 120 min
2977 independent reflections intensity decay: 10.0%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.069Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.217H-atom parameters constrained
S = 0.96 w = 1/[σ2(Fo2) + (0.0855P)2 + 2.55P]
where P = (Fo2 + 2Fc2)/3
2977 reflections(Δ/σ)max = 0.004
169 parametersΔρmax = 0.83 e Å3
6 restraintsΔρmin = 0.57 e Å3
Special details top

Experimental. Spectroscopic analysis: 1H NMR (CDCl3, 400 MHz, δ, p.pm.): 1.46 (s, 3H), 1.53 (s, 3H), 1.89 (s, 3H), 2.44 (dt, Jd = 13.1 Hz, Jt = 3.8 Hz, 1H), 2.70 (q, J = 13.1 Hz, 1H), 2.89 (dd, J = 3.8 and 13.1 Hz, 1H), 4.04 (dd, J = 3.8 and 13.1 Hz, 1H), 7.26–7.36 (m, 3H), 7.61 (mc, 2 H); 13C NMR (CDCl3, 63 MHz, δ, p.p.m.): 20.7, 24.6, 31.4, 32.0, 53.7, 56.7, 74.2, 78.5, 125.1, 127.6, 128.0, 145.5, 176.6.

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
xyzUiso*/Ueq
Br10.38978 (10)0.14319 (13)0.33663 (7)0.0822 (5)
O10.0929 (5)0.1055 (6)0.4028 (4)0.0577 (17)
O30.4929 (7)0.3429 (7)0.4850 (5)0.095 (2)
O20.3307 (7)0.4851 (8)0.4237 (5)0.105
H20.38890.53900.44920.158*
C80.0492 (8)0.1009 (11)0.3311 (6)0.059 (3)
C60.1613 (8)0.0203 (10)0.3927 (5)0.054 (2)
C20.1678 (8)0.2259 (10)0.4405 (6)0.058 (3)
C40.3706 (8)0.1259 (11)0.3934 (6)0.067 (3)
H4A0.44070.14520.36180.080*
H4B0.41640.09720.45140.080*
C120.0457 (10)0.2421 (13)0.3306 (7)0.078 (3)
H120.11430.29030.36870.093*
C110.3787 (9)0.3606 (11)0.4385 (6)0.071 (3)
C70.2106 (9)0.0939 (10)0.4799 (6)0.066 (3)
H7A0.28990.04810.51420.099*
H7B0.13770.09380.51020.099*
H7C0.23480.18550.46980.099*
C30.2867 (9)0.2491 (11)0.3974 (6)0.068 (3)
H30.24610.27660.33760.082*
C90.0553 (9)0.3306 (11)0.4200 (7)0.084 (3)
H9A0.01600.30790.44910.126*
H9B0.09290.41780.43930.126*
H9C0.01710.33300.35870.126*
C160.0516 (10)0.0380 (13)0.2717 (6)0.086 (3)
H160.05100.05610.26890.103*
C50.2761 (7)0.0152 (10)0.3483 (5)0.061 (3)
H50.23260.04730.28990.073*
C100.2195 (9)0.2174 (12)0.5400 (6)0.080 (3)
H10A0.30570.16940.55430.120*
H10B0.23240.30720.56370.120*
H10C0.15240.17040.56370.120*
C140.1573 (11)0.2484 (16)0.2184 (8)0.092 (4)
H140.22660.29820.18200.110*
C130.0568 (11)0.3102 (12)0.2752 (7)0.078 (3)
H130.05660.40430.27710.094*
C150.1566 (11)0.1088 (15)0.2145 (8)0.098 (4)
H150.22450.06270.17460.118*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.0662 (6)0.1083 (10)0.0694 (7)0.0119 (7)0.0106 (4)0.0101 (8)
O10.052 (3)0.058 (5)0.065 (4)0.002 (3)0.015 (3)0.002 (3)
O30.076 (4)0.064 (6)0.122 (6)0.017 (4)0.026 (4)0.012 (4)
O20.0780.0670.1450.0110.0250.023
C80.039 (5)0.074 (9)0.067 (6)0.006 (5)0.017 (4)0.006 (6)
C60.067 (6)0.056 (7)0.037 (5)0.002 (5)0.010 (4)0.009 (5)
C20.044 (5)0.062 (7)0.068 (6)0.019 (5)0.011 (4)0.003 (6)
C40.057 (5)0.090 (9)0.055 (6)0.015 (6)0.017 (4)0.016 (6)
C120.077 (7)0.081 (10)0.073 (7)0.005 (7)0.012 (6)0.006 (7)
C110.054 (5)0.068 (8)0.085 (7)0.019 (6)0.007 (5)0.019 (7)
C70.081 (6)0.059 (7)0.055 (6)0.001 (5)0.013 (4)0.004 (5)
C30.067 (6)0.074 (9)0.056 (6)0.011 (6)0.000 (4)0.006 (6)
C90.067 (6)0.070 (9)0.107 (8)0.000 (6)0.006 (5)0.008 (7)
C160.079 (7)0.088 (9)0.081 (7)0.014 (7)0.001 (6)0.024 (7)
C50.035 (4)0.092 (9)0.055 (5)0.002 (5)0.011 (4)0.006 (5)
C100.078 (6)0.095 (9)0.072 (7)0.005 (6)0.027 (5)0.012 (7)
C140.065 (7)0.108 (12)0.101 (9)0.007 (7)0.015 (6)0.038 (9)
C130.079 (7)0.062 (9)0.097 (8)0.015 (6)0.029 (7)0.023 (7)
C150.082 (8)0.096 (12)0.100 (9)0.003 (7)0.011 (6)0.010 (8)
Geometric parameters (Å, º) top
Br1—C51.965 (9)C11—C31.481 (13)
O1—C61.444 (10)C7—H7A0.9600
O1—C21.455 (10)C7—H7B0.9600
O3—C111.214 (10)C7—H7C0.9600
O2—C111.320 (11)C3—H30.9800
O2—H20.8200C9—H9A0.9600
C8—C161.355 (13)C9—H9B0.9600
C8—C121.395 (14)C9—H9C0.9600
C8—C61.525 (12)C16—C151.401 (14)
C6—C51.518 (10)C16—H160.9300
C6—C71.539 (11)C5—H50.9800
C2—C91.502 (13)C10—H10A0.9600
C2—C31.518 (11)C10—H10B0.9600
C2—C101.546 (12)C10—H10C0.9600
C4—C31.486 (13)C14—C131.327 (15)
C4—C51.508 (12)C14—C151.380 (16)
C4—H4A0.9700C14—H140.9300
C4—H4B0.9700C13—H130.9300
C12—C131.358 (14)C15—H150.9300
C12—H120.9300
C6—O1—C2122.6 (6)C11—C3—C2112.4 (8)
C11—O2—H2109.5C4—C3—C2113.7 (8)
C16—C8—C12116.2 (9)C11—C3—H3107.0
C16—C8—C6121.2 (10)C4—C3—H3107.0
C12—C8—C6122.6 (9)C2—C3—H3107.0
O1—C6—C5106.2 (7)C2—C9—H9A109.5
O1—C6—C8103.2 (6)C2—C9—H9B109.5
C5—C6—C8109.8 (7)H9A—C9—H9B109.5
O1—C6—C7111.4 (7)C2—C9—H9C109.5
C5—C6—C7114.4 (7)H9A—C9—H9C109.5
C8—C6—C7111.2 (8)H9B—C9—H9C109.5
O1—C2—C9100.9 (6)C8—C16—C15122.7 (12)
O1—C2—C3108.4 (7)C8—C16—H16118.7
C9—C2—C3114.8 (9)C15—C16—H16118.7
O1—C2—C10113.1 (8)C4—C5—C6113.6 (7)
C9—C2—C10108.1 (8)C4—C5—Br1108.2 (5)
C3—C2—C10111.2 (7)C6—C5—Br1111.9 (7)
C3—C4—C5108.7 (7)C4—C5—H5107.6
C3—C4—H4A110.0C6—C5—H5107.6
C5—C4—H4A110.0Br1—C5—H5107.6
C3—C4—H4B110.0C2—C10—H10A109.5
C5—C4—H4B110.0C2—C10—H10B109.5
H4A—C4—H4B108.3H10A—C10—H10B109.5
C13—C12—C8120.8 (10)C2—C10—H10C109.5
C13—C12—H12119.6H10A—C10—H10C109.5
C8—C12—H12119.6H10B—C10—H10C109.5
O3—C11—O2119.3 (9)C13—C14—C15118.6 (11)
O3—C11—C3123.7 (10)C13—C14—H14120.7
O2—C11—C3117.0 (8)C15—C14—H14120.7
C6—C7—H7A109.5C14—C13—C12123.0 (12)
C6—C7—H7B109.5C14—C13—H13118.5
H7A—C7—H7B109.5C12—C13—H13118.5
C6—C7—H7C109.5C14—C15—C16118.7 (11)
H7A—C7—H7C109.5C14—C15—H15120.6
H7B—C7—H7C109.5C16—C15—H15120.6
C11—C3—C4109.4 (8)
C2—O1—C6—C550.3 (9)O1—C2—C3—C11173.5 (8)
C2—O1—C6—C8165.8 (7)C9—C2—C3—C1174.6 (11)
C2—O1—C6—C774.8 (9)C10—C2—C3—C1148.6 (12)
C16—C8—C6—O129.3 (10)O1—C2—C3—C448.5 (10)
C12—C8—C6—O1152.3 (8)C9—C2—C3—C4160.5 (8)
C16—C8—C6—C583.6 (10)C10—C2—C3—C476.4 (10)
C12—C8—C6—C594.8 (10)C12—C8—C16—C151.9 (15)
C16—C8—C6—C7148.8 (8)C6—C8—C16—C15179.6 (9)
C12—C8—C6—C732.8 (11)C3—C4—C5—C658.7 (10)
C6—O1—C2—C9169.5 (7)C3—C4—C5—Br1176.3 (6)
C6—O1—C2—C348.5 (10)O1—C6—C5—C453.0 (9)
C6—O1—C2—C1075.3 (9)C8—C6—C5—C4163.9 (8)
C16—C8—C12—C132.2 (14)C7—C6—C5—C470.3 (10)
C6—C8—C12—C13179.3 (8)O1—C6—C5—Br1175.9 (5)
O3—C11—C3—C421.4 (14)C8—C6—C5—Br173.2 (8)
O2—C11—C3—C4159.7 (8)C7—C6—C5—Br152.6 (9)
O3—C11—C3—C2105.9 (11)C15—C14—C13—C121.0 (17)
O2—C11—C3—C273.0 (12)C8—C12—C13—C140.8 (16)
C5—C4—C3—C11177.8 (7)C13—C14—C15—C161.3 (18)
C5—C4—C3—C255.7 (10)C8—C16—C15—C140.2 (17)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O3i0.821.812.622 (10)174
Symmetry code: (i) x+1, y1, z+1.
 

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