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Mol­ecules of the title compound, (+)-(1R,4R)-3-benzoyl-1,7,7-trimethyl­bicyclo­[2.2.1]heptan-2-one, C17H20O2, crystallize in the diketo form. One of the carbonyl groups is involved in a weak intra­molecular C—H...O inter­action [C...O = 2.778 (3) Å]. 3-Benzoyl­camphor is a rare example of a structurally characterized β-diketone that crystallizes both in the diketo and the enol forms. According to density functional theory (DFT) calculations, the diketo tautomer is destabilized by 17.4 kJ mol−1 over the previously reported [Niemeyer & Gan (2005). Acta Cryst. E61, o2363–o2365] enol form.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536806039808/om2056sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536806039808/om2056Isup2.hkl
Contains datablock I

CCDC reference: 628043

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.044
  • wR factor = 0.110
  • Data-to-parameter ratio = 9.9

checkCIF/PLATON results

No syntax errors found



Alert level C ABSMU01_ALERT_1_C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.077 Value of mu given = 0.080 PLAT482_ALERT_4_C Small D-H..A Angle Rep for C13 .. O1 .. 98.50 Deg.
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 27.00 From the CIF: _reflns_number_total 1781 Count of symmetry unique reflns 1781 Completeness (_total/calc) 100.00% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT791_ALERT_1_G Confirm the Absolute Configuration of C1 = . R PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . R
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Computing details top

Data collection: P3 (Siemens, 1989); cell refinement: P3; data reduction: XDISK (Siemens, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 1998).

(+)-(1R,4R)-3-benzoyl-1,7,7-trimethylbicyclo[2.2.1]heptan-2-one top
Crystal data top
C17H20O2Dx = 1.207 Mg m3
Mr = 256.33Melting point = 360–362 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 50 reflections
a = 9.124 (3) Åθ = 5.0–12.5°
b = 12.398 (3) ŵ = 0.08 mm1
c = 12.472 (4) ÅT = 173 K
V = 1410.8 (7) Å3Prism, colorless
Z = 40.45 × 0.20 × 0.20 mm
F(000) = 552
Data collection top
Rebuilt Syntex P21/Siemens P3 four-circle
diffractometer
Rint = 0.027
Radiation source: fine-focus sealed tubeθmax = 27.0°, θmin = 2.3°
Graphite monochromatorh = 111
ω scansk = 115
2337 measured reflectionsl = 115
1781 independent reflections2 standard reflections every 198 reflections
1458 reflections with I > 2σ(I) intensity decay: 1.1%
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)] = 0.044Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.110Only H-atom displacement parameters refined
S = 1.03 w = 1/[σ2(Fo2) + (0.0553P)2 + 0.2946P]
where P = (Fo2 + 2Fc2)/3
1781 reflections(Δ/σ)max < 0.001
179 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.17 e Å3
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
xyzUiso*/Ueq
O10.9198 (2)0.11441 (15)0.27852 (15)0.0407 (5)
O20.9631 (2)0.09562 (16)0.39933 (17)0.0399 (5)
C10.7200 (3)0.1434 (2)0.3299 (2)0.0284 (6)
C20.8369 (3)0.07348 (19)0.38033 (18)0.0265 (5)
C30.7619 (3)0.03482 (18)0.40830 (19)0.0269 (5)
H3A0.76620.04640.48760.031 (5)*
C40.6007 (3)0.0119 (2)0.3745 (2)0.0303 (6)
H4A0.52600.05870.41040.031 (5)*
C50.5952 (4)0.0135 (2)0.2512 (2)0.0399 (7)
H5A0.64010.08010.22210.044 (4)*
H5B0.49330.00750.22470.044 (4)*
C60.6867 (3)0.0877 (2)0.2213 (2)0.0378 (7)
H6A0.63020.13620.17370.044 (4)*
H6B0.77860.06670.18460.044 (4)*
C70.5860 (3)0.1108 (2)0.3999 (2)0.0302 (6)
C80.6052 (4)0.1380 (2)0.5187 (2)0.0397 (7)
H8A0.59370.21590.52910.061 (4)*
H8B0.53110.09960.56090.061 (4)*
H8C0.70320.11590.54230.061 (4)*
C90.4415 (3)0.1594 (2)0.3608 (3)0.0445 (7)
H9A0.43650.23540.38200.061 (4)*
H9B0.43620.15390.28250.061 (4)*
H9C0.35930.12000.39280.061 (4)*
C100.7586 (4)0.2626 (2)0.3227 (2)0.0411 (7)
H10A0.77880.29060.39470.061 (4)*
H10B0.84550.27180.27750.061 (4)*
H10C0.67620.30230.29130.061 (4)*
C110.8336 (3)0.12968 (19)0.3518 (2)0.0273 (5)
C120.7969 (3)0.24187 (19)0.3865 (2)0.0275 (6)
C130.8540 (3)0.3277 (2)0.3272 (2)0.0331 (6)
H130.91550.31360.26730.047 (4)*
C140.8217 (4)0.4333 (2)0.3552 (2)0.0408 (7)
H140.86040.49130.31420.047 (4)*
C150.7335 (4)0.4541 (2)0.4424 (2)0.0417 (7)
H150.71180.52650.46140.047 (4)*
C160.6764 (4)0.3705 (2)0.5022 (2)0.0410 (7)
H160.61580.38560.56230.047 (4)*
C170.7075 (3)0.2638 (2)0.4746 (2)0.0351 (7)
H170.66790.20620.51570.047 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0505 (12)0.0323 (10)0.0394 (10)0.0020 (10)0.0161 (10)0.0025 (8)
O20.0332 (11)0.0341 (10)0.0525 (12)0.0038 (9)0.0052 (10)0.0017 (10)
C10.0331 (14)0.0219 (11)0.0302 (12)0.0014 (11)0.0034 (11)0.0022 (10)
C20.0328 (14)0.0240 (11)0.0229 (11)0.0007 (11)0.0023 (11)0.0011 (10)
C30.0347 (14)0.0207 (10)0.0252 (11)0.0009 (11)0.0005 (12)0.0013 (10)
C40.0293 (13)0.0234 (12)0.0381 (14)0.0025 (11)0.0027 (12)0.0008 (10)
C50.0427 (16)0.0334 (13)0.0435 (15)0.0014 (14)0.0093 (15)0.0073 (12)
C60.0469 (17)0.0375 (14)0.0291 (12)0.0057 (14)0.0021 (12)0.0013 (12)
C70.0333 (14)0.0231 (12)0.0341 (13)0.0033 (11)0.0035 (12)0.0005 (11)
C80.0536 (19)0.0297 (13)0.0359 (14)0.0082 (14)0.0096 (14)0.0053 (12)
C90.0348 (16)0.0390 (16)0.0595 (19)0.0065 (13)0.0006 (15)0.0024 (15)
C100.0443 (17)0.0222 (12)0.0568 (17)0.0026 (13)0.0041 (16)0.0085 (12)
C110.0311 (13)0.0242 (12)0.0265 (11)0.0026 (12)0.0018 (12)0.0005 (10)
C120.0289 (14)0.0222 (11)0.0313 (12)0.0000 (10)0.0047 (11)0.0011 (10)
C130.0350 (15)0.0289 (13)0.0356 (14)0.0062 (12)0.0006 (13)0.0033 (11)
C140.0463 (17)0.0251 (13)0.0509 (16)0.0091 (13)0.0044 (16)0.0051 (12)
C150.0479 (18)0.0232 (12)0.0541 (16)0.0028 (13)0.0060 (16)0.0078 (12)
C160.0483 (18)0.0294 (13)0.0455 (15)0.0050 (14)0.0051 (15)0.0061 (12)
C170.0445 (17)0.0250 (12)0.0357 (14)0.0021 (13)0.0070 (13)0.0015 (11)
Geometric parameters (Å, º) top
O1—C111.220 (3)C8—H8B0.9800
O2—C21.206 (3)C8—H8C0.9800
C1—C21.511 (4)C9—H9A0.9800
C1—C101.523 (3)C9—H9B0.9800
C1—C61.551 (4)C9—H9C0.9800
C1—C71.556 (4)C10—H10A0.9800
C2—C31.547 (3)C10—H10B0.9800
C3—C111.519 (3)C10—H10C0.9800
C3—C41.556 (4)C11—C121.495 (3)
C3—H3A1.0000C12—C171.395 (4)
C4—C51.539 (4)C12—C131.397 (3)
C4—C71.560 (3)C13—C141.387 (4)
C4—H4A1.0000C13—H130.9500
C5—C61.552 (4)C14—C151.377 (4)
C5—H5A0.9900C14—H140.9500
C5—H5B0.9900C15—C161.379 (4)
C6—H6A0.9900C15—H150.9500
C6—H6B0.9900C16—C171.396 (4)
C7—C91.529 (4)C16—H160.9500
C7—C81.530 (4)C17—H170.9500
C8—H8A0.9800
C2—C1—C10114.7 (2)C7—C8—H8A109.5
C2—C1—C6104.3 (2)C7—C8—H8B109.5
C10—C1—C6115.2 (2)H8A—C8—H8B109.5
C2—C1—C799.95 (19)C7—C8—H8C109.5
C10—C1—C7117.8 (2)H8A—C8—H8C109.5
C6—C1—C7102.8 (2)H8B—C8—H8C109.5
O2—C2—C1128.7 (2)C7—C9—H9A109.5
O2—C2—C3125.1 (2)C7—C9—H9B109.5
C1—C2—C3106.2 (2)H9A—C9—H9B109.5
C11—C3—C2112.1 (2)C7—C9—H9C109.5
C11—C3—C4115.0 (2)H9A—C9—H9C109.5
C2—C3—C4101.5 (2)H9B—C9—H9C109.5
C11—C3—H3A109.3C1—C10—H10A109.5
C2—C3—H3A109.3C1—C10—H10B109.5
C4—C3—H3A109.3H10A—C10—H10B109.5
C5—C4—C3107.4 (2)C1—C10—H10C109.5
C5—C4—C7102.3 (2)H10A—C10—H10C109.5
C3—C4—C7101.8 (2)H10B—C10—H10C109.5
C5—C4—H4A114.6O1—C11—C12120.4 (2)
C3—C4—H4A114.6O1—C11—C3120.3 (2)
C7—C4—H4A114.6C12—C11—C3119.3 (2)
C4—C5—C6102.3 (2)C17—C12—C13119.2 (2)
C4—C5—H5A111.3C17—C12—C11122.7 (2)
C6—C5—H5A111.3C13—C12—C11118.1 (2)
C4—C5—H5B111.3C14—C13—C12120.4 (3)
C6—C5—H5B111.3C14—C13—H13119.8
H5A—C5—H5B109.2C12—C13—H13119.8
C1—C6—C5104.8 (2)C15—C14—C13120.0 (3)
C1—C6—H6A110.8C15—C14—H14120.0
C5—C6—H6A110.8C13—C14—H14120.0
C1—C6—H6B110.8C14—C15—C16120.5 (2)
C5—C6—H6B110.8C14—C15—H15119.7
H6A—C6—H6B108.9C16—C15—H15119.7
C9—C7—C8108.7 (2)C15—C16—C17120.1 (3)
C9—C7—C1113.3 (2)C15—C16—H16119.9
C8—C7—C1113.4 (2)C17—C16—H16119.9
C9—C7—C4113.2 (2)C12—C17—C16119.8 (2)
C8—C7—C4113.7 (2)C12—C17—H17120.1
C1—C7—C494.1 (2)C16—C17—H17120.1
C10—C1—C2—O213.1 (4)C2—C1—C7—C456.1 (2)
C6—C1—C2—O2113.8 (3)C10—C1—C7—C4179.0 (2)
C7—C1—C2—O2140.2 (3)C6—C1—C7—C451.1 (2)
C10—C1—C2—C3164.8 (2)C5—C4—C7—C961.7 (3)
C6—C1—C2—C368.3 (2)C3—C4—C7—C9172.7 (2)
C7—C1—C2—C337.8 (2)C5—C4—C7—C8173.6 (3)
O2—C2—C3—C1161.6 (3)C3—C4—C7—C862.6 (3)
C1—C2—C3—C11120.4 (2)C5—C4—C7—C155.8 (3)
O2—C2—C3—C4175.1 (2)C3—C4—C7—C155.1 (2)
C1—C2—C3—C42.9 (2)C2—C3—C11—O113.1 (3)
C11—C3—C4—C547.3 (3)C4—C3—C11—O1102.1 (3)
C2—C3—C4—C573.9 (2)C2—C3—C11—C12167.2 (2)
C11—C3—C4—C7154.4 (2)C4—C3—C11—C1277.6 (3)
C2—C3—C4—C733.1 (2)O1—C11—C12—C17175.3 (3)
C3—C4—C5—C667.4 (3)C3—C11—C12—C175.0 (4)
C7—C4—C5—C639.3 (3)O1—C11—C12—C135.3 (4)
C2—C1—C6—C574.8 (3)C3—C11—C12—C13174.4 (2)
C10—C1—C6—C5158.6 (3)C17—C12—C13—C140.3 (4)
C7—C1—C6—C529.2 (3)C11—C12—C13—C14179.1 (3)
C4—C5—C6—C16.1 (3)C12—C13—C14—C150.4 (4)
C2—C1—C7—C9173.6 (2)C13—C14—C15—C160.2 (5)
C10—C1—C7—C961.5 (3)C14—C15—C16—C170.1 (5)
C6—C1—C7—C966.3 (3)C13—C12—C17—C160.0 (4)
C2—C1—C7—C861.9 (3)C11—C12—C17—C16179.4 (3)
C10—C1—C7—C863.0 (3)C15—C16—C17—C120.2 (5)
C6—C1—C7—C8169.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O10.952.472.778 (3)99
 

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