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Acta Crystallogr Sect E Struct Rep Online. 2010 February 1; 66(Pt 2): o489–o490.
Published online 2010 January 30. doi:  10.1107/S1600536810003120
PMCID: PMC2979963

tert-Butyl 2-benzoyl-2-methyl­propanoate

Abstract

The title compound, C15H20O3, is bent with a dihedral angle of 67.28 (9)° between the mean planes of the phenyl ring and a group encompassing the ester functionality (O=C—O—C). In the crystal, mol­ecules related by inversion symmetry are connected by weak C—H(...)O inter­actions into infinite chains. On one side of the mol­ecule there are two adjacent inter­actions between neighbouring mol­ecules involving the H atoms of methyl groups from the dimethyl groups and the O atoms of the ketone; on the other side, there are also two inter­actions to another adjacent mol­ecule involving the H atoms on the phenyl rings and the carbonyl O atoms of the ester functionality.

Related literature

For the synthesis, spectroscopic characterization and reactivity of the title compound, see: Logue (1974 [triangle]); Logue et al. (1975 [triangle]). For related structures, see: Crosse et al. (2010a [triangle],b [triangle]); Gould et al. (2010 [triangle]). For the syntheses and characterization of structurally similar indanone-derived β-keto ester derivatives, see: Mouri et al. (2009 [triangle]); Noritake et al. (2008 [triangle]); Rigby & Dixon (2008 [triangle]). For weak hydrogen-bonded inter­actions, see: Karle et al. (2009 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o489-scheme1.jpg

Experimental

Crystal data

  • C15H20O3
  • M r = 248.31
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o489-efi1.jpg
  • a = 8.616 (3) Å
  • b = 8.696 (3) Å
  • c = 11.310 (5) Å
  • α = 73.25 (4)°
  • β = 72.25 (3)°
  • γ = 66.05 (3)°
  • V = 724.3 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 291 K
  • 0.40 × 0.35 × 0.30 mm

Data collection

  • Enraf–Nonius TurboCAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.965, T max = 0.979
  • 2735 measured reflections
  • 2548 independent reflections
  • 1689 reflections with I > 2σ(I)
  • R int = 0.015
  • 3 standard reflections every 166 min intensity decay: 1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.043
  • wR(F 2) = 0.119
  • S = 1.02
  • 2548 reflections
  • 164 parameters
  • H-atom parameters constrained
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.12 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 [triangle]); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 [triangle]); program(s) used to solve structure: SIR2004 (Burla et al., 2005 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and Mercury (Macrae et al., 2008 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810003120/zl2265sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003120/zl2265Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

Financial assistance from the Chemistry Department of Michigan Technological University is acknowledged.

supplementary crystallographic information

Comment

Treatment of 2,2-disubstituted t-butyl β-keto esters with trifluoroacetic acid at room temperature quantitatively generates the corresponding 2,2-disubstituted β-keto acids, which were used to probe the nature of the transition state for the thermal decarboxylation of β-keto acids (Logue et al., 1975). Structurally similar indanone-derived β-keto ester derivatives have been prepared recently (Mouri et al., 2009; Noritake et al., 2008; Rigby & Dixon, 2008). The directing nature of weak C—H···O H-bonds has been noted to be of importance to afford the three dimensional structure observed in these kinds of molecules (Karle et al., 2009).

In this contribution we present the solid state structure of one such 2,2-disubstituted β-keto acid, i.e. the title compound being the unsubstituted phenyl derivative. This is the first paper in a series of four dealing with substituted derivatives (H– (this paper), CH3–, Cl- and NO2– on the para-position of the phenyl ring) of the title compound. A more detailed comparison of all four substitution compounds will be given in the fourth paper of this series (Crosse et al., 2010a).

The molecule, Fig. 1, displays a bent geometry with a dihedral angle between the mean planes of the phenyl ring and a plane composed of the ester functionality of 67.28 (9)°. Molecules are linked by weak C—H···O hydrogen bonds generating infinite chains parallel to the c axis as shown in Fig. 2. On one side of the molecule there are two adjacent interactions between neighbouring molecules involving H-atoms on methyl groups from the dimethyl moiety and O-atoms on the ketone; on the other side there are also two interactions to another adjacent molecule involving H-atoms on the phenyl rings and the carbonyl O-atoms on the ester functionality.The phenyl rings are not involved in intercalation or stacking interactions either within or between the chains. Instead neighbouring t-butyl groups on adjacent chains exhibit hydrophobic stacking.

Experimental

Crystals of the material were synthesized as reported earlier and were grown by evaporation of a solution in hexane (Logue, 1974). IR (neat, cm-1): 3439 (br), 3077 (m), 2980 (s), 2938 (m), 1729 (s), 1683 (s), 1598 (m) 1580 (m), 1447 (m), 1388 (m), 1367 (m), 1279 (s), 1156 (s), 987 (m), 928 (m), 845 (m), 796 (m), 709 (s). 1H NMR (CDCl3,) δ: 1.26 (s, 9H), 1.49 (s, 6H), 7.39 (t, 2H, J=6.8 Hz), 7.49 (t, 1H, J=7.6 Hz), 7.85 (d, 2H, J=7.2 Hz). 13C NMR (CDCl3) δ: 24.1, 27.7, 54.3, 81.9, 128.5, 128.9, 132.7, 135.7, 174.2, 198.4.

Refinement

All H atoms were placed at calculated positions, with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and refined using a riding model with Uiso(H) constrained to be 1.5 Ueq(C) for methyl groups and 1.2 Ueq(C) for all other C atoms. The quality of the data as reflected by only 66% of the reflections observed, large ADP's and inaccurate C—C bond lengths is low. The data had been collected on a 30 year old single point detector instrument not equipped with a low temperature device as part of a class project with undergraduate students. Due to the time constraints imposed by the class schedule a maximum exposure time of 60 s had to be alloted for measuring each reflection.

Figures

Fig. 1.
ORTEP-3 (Farrugia, 1997) drawing of the title compound with displacement ellipsoids drawn at the 50% probability level.
Fig. 2.
A Mercury (Macrae et al., 2008) illustration of the H-bonded linkages in the title compound using blue dashed lines showing the relationships between non-interacting chains.

Crystal data

C15H20O3Z = 2
Mr = 248.31F(000) = 268
Triclinic, P1Dx = 1.139 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.616 (3) ÅCell parameters from 25 reflections
b = 8.696 (3) Åθ = 10–15°
c = 11.310 (5) ŵ = 0.08 mm1
α = 73.25 (4)°T = 291 K
β = 72.25 (3)°Prism, colourless
γ = 66.05 (3)°0.40 × 0.35 × 0.30 mm
V = 724.3 (5) Å3

Data collection

Enraf–Nonius TurboCAD-4 diffractometer1689 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590Rint = 0.015
graphiteθmax = 25.0°, θmin = 1.9°
non–profiled ω/2τ scansh = 0→10
Absorption correction: ψ scan (North et al., 1968)k = −9→10
Tmin = 0.965, Tmax = 0.979l = −12→13
2735 measured reflections3 standard reflections every 166 min
2548 independent reflections intensity decay: 1%

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.119w = 1/[σ2(Fo2) + (0.0496P)2 + 0.1543P] where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
2548 reflectionsΔρmax = 0.12 e Å3
164 parametersΔρmin = −0.12 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.064 (6)

Special details

Experimental. Number of psi-scan sets used was 5. Theta correction was applied. Averaged transmission function was used. No Fourier smoothing was applied.
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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)

xyzUiso*/Ueq
C11.0848 (3)−0.3377 (3)0.8308 (3)0.0843 (7)
H11.1732−0.41150.87270.101*
C21.1205 (3)−0.2955 (3)0.7023 (3)0.0828 (7)
H21.2336−0.33890.65680.099*
C30.9887 (3)−0.1880 (3)0.6390 (2)0.0663 (6)
H31.0133−0.16190.55110.08*
C40.8198 (2)−0.1190 (2)0.70634 (18)0.0499 (5)
C50.7874 (3)−0.1610 (3)0.83672 (19)0.0572 (5)
H50.6759−0.11440.88350.069*
C60.9192 (3)−0.2718 (3)0.8982 (2)0.0715 (6)
H60.8953−0.30170.9860.086*
C70.6830 (3)−0.0021 (3)0.63224 (18)0.0535 (5)
O10.7093 (2)−0.0062 (2)0.52144 (14)0.0808 (5)
C80.5114 (2)0.1223 (2)0.69448 (18)0.0521 (5)
C90.4249 (3)0.2636 (3)0.5920 (2)0.0755 (7)
H9B0.50240.32360.54190.113*
H9C0.31910.34250.63140.113*
H9A0.39930.21270.53870.113*
C100.3865 (3)0.0253 (3)0.7712 (2)0.0707 (6)
H10A0.3667−0.02820.71660.106*
H10B0.27790.10430.80750.106*
H10C0.4368−0.06080.83750.106*
C110.5454 (2)0.2112 (2)0.77688 (18)0.0505 (5)
O20.4621 (2)0.2339 (2)0.88045 (14)0.0736 (5)
O30.67818 (16)0.26535 (16)0.71377 (11)0.0533 (4)
C120.7438 (3)0.3557 (3)0.7690 (2)0.0616 (6)
C130.8897 (3)0.3905 (4)0.6630 (3)0.0942 (9)
H13A0.8450.45480.58850.141*
H13B0.97830.28380.64550.141*
H13C0.93840.45510.68760.141*
C140.6027 (4)0.5217 (3)0.7977 (3)0.1024 (10)
H14A0.55580.58520.7240.154*
H14B0.65030.5880.82140.154*
H14C0.5120.49770.86590.154*
C150.8130 (4)0.2379 (4)0.8824 (3)0.1046 (10)
H15A0.89520.13140.85930.157*
H15B0.71860.21680.94820.157*
H15C0.86920.29020.91210.157*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0638 (15)0.0716 (16)0.103 (2)−0.0149 (12)−0.0227 (14)−0.0031 (14)
C20.0506 (13)0.0702 (15)0.104 (2)−0.0101 (12)0.0024 (13)−0.0182 (14)
C30.0647 (14)0.0601 (13)0.0670 (13)−0.0244 (12)0.0047 (11)−0.0175 (11)
C40.0526 (11)0.0448 (10)0.0568 (11)−0.0232 (9)−0.0039 (9)−0.0154 (9)
C50.0517 (11)0.0579 (12)0.0588 (12)−0.0185 (10)−0.0068 (10)−0.0128 (10)
C60.0676 (15)0.0702 (14)0.0704 (14)−0.0210 (12)−0.0186 (12)−0.0048 (12)
C70.0608 (12)0.0618 (12)0.0526 (11)−0.0349 (10)−0.0080 (9)−0.0165 (9)
O10.0838 (11)0.1121 (13)0.0602 (10)−0.0381 (10)−0.0145 (8)−0.0314 (9)
C80.0507 (11)0.0547 (11)0.0587 (11)−0.0244 (9)−0.0149 (9)−0.0099 (9)
C90.0812 (16)0.0708 (15)0.0853 (16)−0.0268 (12)−0.0395 (13)−0.0069 (12)
C100.0558 (12)0.0752 (15)0.0921 (16)−0.0357 (11)−0.0118 (11)−0.0172 (12)
C110.0473 (11)0.0503 (11)0.0544 (11)−0.0187 (9)−0.0091 (9)−0.0101 (9)
O20.0743 (10)0.0925 (11)0.0624 (9)−0.0433 (9)0.0091 (8)−0.0310 (8)
O30.0550 (8)0.0628 (8)0.0547 (8)−0.0329 (7)−0.0061 (6)−0.0173 (6)
C120.0660 (13)0.0680 (13)0.0706 (14)−0.0348 (11)−0.0167 (11)−0.0229 (11)
C130.0884 (18)0.121 (2)0.106 (2)−0.0729 (18)−0.0038 (15)−0.0332 (17)
C140.097 (2)0.0794 (18)0.154 (3)−0.0341 (16)−0.0215 (19)−0.0580 (18)
C150.119 (2)0.130 (2)0.100 (2)−0.064 (2)−0.0581 (19)−0.0060 (18)

Geometric parameters (Å, °)

C1—C21.360 (3)C9—H9A0.96
C1—C61.368 (3)C10—H10A0.96
C1—H10.93C10—H10B0.96
C2—C31.387 (3)C10—H10C0.96
C2—H20.93C11—O21.197 (2)
C3—C41.391 (3)C11—O31.336 (2)
C3—H30.93O3—C121.479 (2)
C4—C51.381 (3)C12—C151.504 (3)
C4—C71.505 (3)C12—C141.507 (3)
C5—C61.382 (3)C12—C131.514 (3)
C5—H50.93C13—H13A0.96
C6—H60.93C13—H13B0.96
C7—O11.212 (2)C13—H13C0.96
C7—C81.535 (3)C14—H14A0.96
C8—C111.522 (3)C14—H14B0.96
C8—C101.540 (3)C14—H14C0.96
C8—C91.540 (3)C15—H15A0.96
C9—H9B0.96C15—H15B0.96
C9—H9C0.96C15—H15C0.96
C2—C1—C6120.1 (2)C8—C10—H10B109.5
C2—C1—H1119.9H10A—C10—H10B109.5
C6—C1—H1119.9C8—C10—H10C109.5
C1—C2—C3120.2 (2)H10A—C10—H10C109.5
C1—C2—H2119.9H10B—C10—H10C109.5
C3—C2—H2119.9O2—C11—O3125.43 (18)
C2—C3—C4120.3 (2)O2—C11—C8125.07 (17)
C2—C3—H3119.8O3—C11—C8109.46 (16)
C4—C3—H3119.8C11—O3—C12122.50 (15)
C5—C4—C3118.4 (2)O3—C12—C15109.11 (18)
C5—C4—C7123.82 (18)O3—C12—C14109.65 (17)
C3—C4—C7117.79 (18)C15—C12—C14113.7 (2)
C4—C5—C6120.6 (2)O3—C12—C13102.51 (16)
C4—C5—H5119.7C15—C12—C13110.8 (2)
C6—C5—H5119.7C14—C12—C13110.4 (2)
C1—C6—C5120.3 (2)C12—C13—H13A109.5
C1—C6—H6119.8C12—C13—H13B109.5
C5—C6—H6119.8H13A—C13—H13B109.5
O1—C7—C4119.24 (19)C12—C13—H13C109.5
O1—C7—C8119.62 (19)H13A—C13—H13C109.5
C4—C7—C8121.14 (16)H13B—C13—H13C109.5
C11—C8—C7110.39 (15)C12—C14—H14A109.5
C11—C8—C10111.49 (17)C12—C14—H14B109.5
C7—C8—C10109.80 (16)H14A—C14—H14B109.5
C11—C8—C9106.87 (16)C12—C14—H14C109.5
C7—C8—C9109.79 (17)H14A—C14—H14C109.5
C10—C8—C9108.42 (17)H14B—C14—H14C109.5
C8—C9—H9B109.5C12—C15—H15A109.5
C8—C9—H9C109.5C12—C15—H15B109.5
H9B—C9—H9C109.5H15A—C15—H15B109.5
C8—C9—H9A109.5C12—C15—H15C109.5
H9B—C9—H9A109.5H15A—C15—H15C109.5
H9C—C9—H9A109.5H15B—C15—H15C109.5
C8—C10—H10A109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C5—H5···O2i0.932.663.317 (3)128
C9—H9A···O1ii0.962.653.557 (3)158

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+1, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2265).

References

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