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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): o1104.
Published online 2008 May 17. doi:  10.1107/S1600536808014086
PMCID: PMC2961582

Benzoyl­methyl pyridine-4-carboxyl­ate

Abstract

In the crystal structure of the title compound, C14H11NO3, isolated from the reaction of 2-bromo-1-phenyl­ethanone and pyridine-4-carboxylic acid using triethyl­amine as a base to deprotonate the organic acid, the mol­ecular packing is stabilized by C—H(...)π inter­actions involving the phenyl and pyridine rings. The C—C—O—C torsion angle for the linkage between the two carbonyl groups is −80.8 (2)°, and the planes of the phenyl and pyridyl rings form a dihedral angle of 65.8 (1)°.

Related literature

For related literature, see: Allen et al. (1987 [triangle]); Hendrickson & Kandall (1970 [triangle]); Pavel et al. (1993 [triangle]).

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Object name is e-64-o1104-scheme1.jpg

Experimental

Crystal data

  • C14H11NO3
  • M r = 241.24
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1104-efi1.jpg
  • a = 8.0863 (6) Å
  • b = 9.2130 (7) Å
  • c = 9.3291 (8) Å
  • α = 106.738 (7)°
  • β = 114.495 (8)°
  • γ = 96.549 (6)°
  • V = 583.52 (8) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 173 (2) K
  • 0.30 × 0.17 × 0.12 mm

Data collection

  • Bruker APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.971, T max = 0.988
  • 4945 measured reflections
  • 2011 independent reflections
  • 1099 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.074
  • S = 0.82
  • 2011 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.11 e Å−3
  • Δρmin = −0.13 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808014086/cf2193sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014086/cf2193Isup2.hkl

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

Acknowledgments

We acknowledge the financial support of the National Natural Science Foundation of China (Nos. 20572061 and 20732004) and the Ministry of Science and Technology (No. 2006DFA43030).

supplementary crystallographic information

Comment

The title compound was synthesized for a study of protection of the carboxyl group. The phenacyl group has been proved to be an important reagent for protecting carboxyl functions during synthesis in the presence of other esters (Hendrickson et al., 1970).

The title compound (I) was obtained by the reaction of 2-bromo-1-phenylethanone and pyridine-4-carboxylic acid using triethylamine as a base to deprotonate the organic acid. An X-ray crystal structure determination of compound (I) was carried out to determine its conformation. Bond lengths and angles are in agreement with values reported in the literature (Allen et al., 1987). The torsion angle C7-C8-O9-C10 [-80.8 (2)Å] describes the conformation of the phenyl group with respect to the pyridyl group; the planes of the benzene ring and the pyridine ring form a dihedral angle of 65.8 (1)Å.

In the crystal structure of (I), the phenyl and pyridyl rings make a dihedral angle of 65.8 (1)° and the C7—C8—O9—C10 torsion angle is -80.8 (2)° (Fig. 1). The packing of the aromatic rings is shown in Fig. 2. Two head-to-tail molecules (M and Mi) are linked by C—H···π interactions with typical geometry (Pavel et al., 1993), leading to the formation of a linear chain. The distance between CgA and CgBi is 6.102 (3) Å and the angles between the lines through the centroids of the two rings and the normal through CgA is 79.5 (1)° and through CgBi is 76.8 (1)°. The linear chains are further stabilized by other C—H···π interactions (M and Mii; Mi and Mii), generating sheets parallel to (010). The corresponding values for the phenyl ring in M and the pyridyl ring in Mii are 4.857 (3) Å, 69.3 (1)° and 13.7 (1)°. For the phenyl ring in Mii and the pyridyl ring in Mi they are 4.954 (3) Å, 69.4 (1)° and 16.6 (1)°. C—H···π interactions between two sheets (M and Miii) also provide stability for the crystal structure. The corresponding values for the two adjacent aromatic rings in M and Miii are 4.721 (3)Å, 14.5 (1)° and 66.4 (1)°. CgA and CgB stand for the centroids of phenyl and pyridyl rings respectively. [Symmetry codes: (i) x - 1, y, z + 1; (ii) x - 1, y, z; (iii) -x, 1 - y, 2 - z.]

Experimental

The title compound was prepared by a method based on one described by Hendrickson & Kandall (1970). Triethylamine (1.0 ml, 7.5 mmol) was added dropwise to a mixture of 2-bromo-1-phenylethanone (995 mg, 5 mmol) and pyridine-4-carboxylic acid (615 mg, 5 mmol) in freshly distilled tetrahydrofuran (20 ml) at room temperature under argon and stirred overnight. The precipitate was collected at the pump and washed with ethyl acetate. The filtrate and washings were combined and back-washed successively with 1/3 of the volume each of 10% citric acid, 10% sodium bicarbonate, and water and then dried. Solvent was distilled off in vacuo and the residue recrystallized repeatedly from ethyl acetate-petroleum ether, giving 1.04 g (86%) as colourless needles.

Refinement

The hydrogen atoms were positioned geometrically (C—H = 0.93, 0.98, 0.97 or 0.96Å for aromatic, tertiary, methylene or methyl H atoms respectively) and were included in the refinement in the riding model approximation. The displacement parameters of methyl H atoms were set to 1.5Ueq(C), while those of other H atoms were set to 1.2Ueq(C).

Figures

Fig. 1.
The molecular structure of (I) with the atom-labelling scheme, showing 50% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radius.
Fig. 2.
A view of the C—H···π interactions motif of (I). CgA and CgB are the centroids of the benzene and pyridine rings respectively. The C—H···π interactions are shown as dashed ...

Crystal data

C14H11NO3Z = 2
Mr = 241.24F000 = 252
Triclinic, P1Dx = 1.373 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.0863 (6) ÅCell parameters from 1153 reflections
b = 9.2130 (7) Åθ = 2.4–32.7º
c = 9.3291 (8) ŵ = 0.10 mm1
α = 106.738 (7)ºT = 173 (2) K
β = 114.495 (8)ºNeedle, colorless
γ = 96.549 (6)º0.30 × 0.17 × 0.12 mm
V = 583.52 (8) Å3

Data collection

Bruker APEX CCD diffractometer2011 independent reflections
Radiation source: fine-focus sealed tube1099 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.042
Detector resolution: 16.1903 pixels mm-1θmax = 25.0º
T = 173(2) Kθmin = 2.4º
[var phi] and ω scansh = −9→9
Absorption correction: multi-scan(SADABS; Bruker, 2001)k = −10→9
Tmin = 0.971, Tmax = 0.988l = −10→11
4945 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H-atom parameters constrained
wR(F2) = 0.074  w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3
S = 0.82(Δ/σ)max < 0.001
2011 reflectionsΔρmax = 0.11 e Å3
163 parametersΔρmin = −0.13 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
C1−0.1339 (2)0.7322 (2)1.1693 (2)0.0306 (5)
C2−0.3294 (2)0.6903 (2)1.0760 (2)0.0329 (5)
H2−0.38800.64990.95550.039*
C3−0.4385 (2)0.7073 (2)1.1574 (3)0.0359 (5)
H3−0.57210.67801.09310.043*
C4−0.3540 (3)0.7668 (2)1.3323 (3)0.0412 (5)
H4−0.42960.77811.38810.049*
C5−0.1609 (3)0.8098 (2)1.4261 (3)0.0428 (5)
H5−0.10300.85231.54650.051*
C6−0.0511 (3)0.7910 (2)1.3450 (2)0.0395 (5)
H60.08230.81861.41010.047*
C7−0.0110 (3)0.7152 (2)1.0855 (3)0.0382 (5)
O70.15653 (19)0.7341 (2)1.16374 (19)0.0670 (5)
C8−0.1064 (2)0.6727 (3)0.8971 (2)0.0435 (6)
H8B−0.20710.57320.84250.052*
H8A−0.16610.75590.87010.052*
O90.02347 (17)0.65426 (17)0.82904 (17)0.0437 (4)
C100.1269 (3)0.7883 (3)0.8448 (3)0.0385 (5)
O100.1180 (2)0.91629 (19)0.9139 (2)0.0649 (5)
C110.2487 (3)0.7577 (3)0.7621 (2)0.0313 (5)
C120.2426 (2)0.6074 (2)0.6700 (2)0.0320 (5)
H120.16090.51720.65850.038*
C130.3593 (2)0.5930 (2)0.5953 (2)0.0364 (5)
H130.35370.49000.53090.044*
N140.4789 (2)0.7134 (2)0.6074 (2)0.0396 (5)
C150.4825 (3)0.8565 (3)0.6977 (3)0.0420 (5)
H150.56700.94470.70900.050*
C160.3708 (3)0.8837 (2)0.7753 (2)0.0383 (5)
H160.37790.98810.83720.046*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0319 (10)0.0331 (13)0.0341 (12)0.0088 (9)0.0194 (9)0.0165 (11)
C20.0308 (10)0.0375 (13)0.0332 (12)0.0093 (10)0.0170 (10)0.0140 (11)
C30.0365 (11)0.0362 (13)0.0503 (14)0.0156 (10)0.0285 (11)0.0220 (12)
C40.0579 (13)0.0397 (14)0.0509 (15)0.0211 (12)0.0400 (12)0.0257 (13)
C50.0564 (14)0.0438 (14)0.0335 (12)0.0140 (12)0.0244 (12)0.0165 (12)
C60.0389 (12)0.0429 (14)0.0373 (13)0.0097 (11)0.0170 (11)0.0176 (12)
C70.0326 (11)0.0475 (14)0.0450 (13)0.0155 (11)0.0221 (11)0.0238 (12)
O70.0326 (8)0.1257 (16)0.0589 (10)0.0276 (10)0.0249 (8)0.0486 (12)
C80.0364 (11)0.0638 (16)0.0409 (13)0.0164 (12)0.0272 (11)0.0188 (13)
O90.0439 (8)0.0525 (10)0.0496 (9)0.0144 (8)0.0353 (8)0.0186 (9)
C100.0416 (12)0.0492 (15)0.0369 (13)0.0197 (12)0.0232 (11)0.0225 (13)
O100.0978 (12)0.0517 (11)0.0899 (13)0.0419 (10)0.0749 (11)0.0320 (11)
C110.0336 (10)0.0400 (12)0.0291 (11)0.0155 (10)0.0188 (9)0.0163 (11)
C120.0328 (10)0.0362 (13)0.0321 (11)0.0091 (10)0.0192 (10)0.0133 (11)
C130.0422 (11)0.0408 (14)0.0342 (12)0.0177 (11)0.0229 (10)0.0144 (11)
N140.0452 (10)0.0467 (13)0.0401 (11)0.0170 (10)0.0269 (9)0.0216 (10)
C150.0492 (12)0.0411 (14)0.0425 (13)0.0081 (12)0.0264 (12)0.0188 (12)
C160.0501 (12)0.0354 (13)0.0390 (12)0.0159 (11)0.0274 (11)0.0153 (11)

Geometric parameters (Å, °)

C1—C61.387 (2)C8—H8B0.990
C1—C21.390 (2)C8—H8A0.990
C1—C71.495 (2)O9—C101.343 (2)
C2—C31.378 (2)C10—O101.196 (2)
C2—H20.950C10—C111.488 (2)
C3—C41.380 (3)C11—C161.376 (2)
C3—H30.950C11—C121.386 (3)
C4—C51.374 (3)C12—C131.384 (2)
C4—H40.950C12—H120.950
C5—C61.381 (2)C13—N141.330 (2)
C5—H50.950C13—H130.950
C6—H60.950N14—C151.334 (2)
C7—O71.204 (2)C15—C161.375 (2)
C7—C81.499 (3)C15—H150.950
C8—O91.4371 (19)C16—H160.950
C6—C1—C2118.97 (16)O9—C8—H8A109.2
C6—C1—C7119.22 (17)C7—C8—H8A109.2
C2—C1—C7121.80 (17)H8B—C8—H8A107.9
C3—C2—C1120.25 (18)C10—O9—C8115.55 (15)
C3—C2—H2119.9O10—C10—O9123.68 (17)
C1—C2—H2119.9O10—C10—C11124.4 (2)
C2—C3—C4120.10 (18)O9—C10—C11111.85 (18)
C2—C3—H3119.9C16—C11—C12118.45 (16)
C4—C3—H3119.9C16—C11—C10118.77 (19)
C5—C4—C3120.23 (17)C12—C11—C10122.77 (19)
C5—C4—H4119.9C13—C12—C11117.82 (17)
C3—C4—H4119.9C13—C12—H12121.1
C4—C5—C6119.85 (19)C11—C12—H12121.1
C4—C5—H5120.1N14—C13—C12124.53 (18)
C6—C5—H5120.1N14—C13—H13117.7
C5—C6—C1120.57 (18)C12—C13—H13117.7
C5—C6—H6119.7C13—N14—C15116.29 (15)
C1—C6—H6119.7N14—C15—C16123.75 (19)
O7—C7—C1122.35 (18)N14—C15—H15118.1
O7—C7—C8120.97 (16)C16—C15—H15118.1
C1—C7—C8116.67 (15)C15—C16—C11119.15 (18)
O9—C8—C7112.06 (15)C15—C16—H16120.4
O9—C8—H8B109.2C11—C16—H16120.4
C7—C8—H8B109.2
C6—C1—C2—C30.0 (3)C8—O9—C10—O101.7 (3)
C7—C1—C2—C3179.89 (17)C8—O9—C10—C11−176.62 (16)
C1—C2—C3—C40.3 (3)O10—C10—C11—C165.1 (3)
C2—C3—C4—C50.2 (3)O9—C10—C11—C16−176.53 (18)
C3—C4—C5—C6−1.0 (3)O10—C10—C11—C12−173.9 (2)
C4—C5—C6—C11.4 (3)O9—C10—C11—C124.4 (3)
C2—C1—C6—C5−0.9 (3)C16—C11—C12—C13−0.5 (3)
C7—C1—C6—C5179.23 (19)C10—C11—C12—C13178.58 (17)
C6—C1—C7—O78.4 (3)C11—C12—C13—N140.9 (3)
C2—C1—C7—O7−171.5 (2)C12—C13—N14—C15−0.5 (3)
C6—C1—C7—C8−171.7 (2)C13—N14—C15—C16−0.3 (3)
C2—C1—C7—C88.4 (3)N14—C15—C16—C110.6 (3)
O7—C7—C8—O91.8 (3)C12—C11—C16—C15−0.2 (3)
C1—C7—C8—O9−178.06 (16)C10—C11—C16—C15−179.31 (19)
C7—C8—O9—C10−80.8 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4···CgBi0.953.864.766 (3)160
C2—H2···CgBii0.952.893.640 (3)137
C6—H6···CgBiii0.953.003.752 (3)137
C12—H12···CgAiv0.952.883.572 (3)130

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CF2193).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  • Bruker (2001). SAINT, SMART and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Hendrickson, J. B. & Kandall, C. (1970). Tetrahedron Lett.5, 343–344.
  • Pavel, H., Heinrich, L. S. & Edward, W. S. (1993). J. Am. Chem. Soc.116, 3500–3506.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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