Acta Cryst. (2011). E67, o1199 [ doi:10.1107/S1600536811014541 ]
The title compound, C14H11ClO, is a racemic derivative of benzoin. Its carbonyl group adopts a nearly eclipsed conformation with the Cl substituent characterized by a dihedral angle of 17.5 (2)°. The closest intermolecular ![[pi]](/logos/entities/pi_rmgif.gif)
- contact is 4.258 (1) Å.
The compound was synthesized by reacting benzoin with thionyl chloride. Crystals suitable for X-ray diffraction were obtained upon recrystallization from ethanol.
Carbon-bound H-atoms were placed in calculated positions (C—H 0.99 Å for the methylene group and C—H 0.95 Å for aromatic carbon atoms) and were included in the refinement in the riding model approximation, with U(H) set to 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./ld2009fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids drawn at 50% probability level. |
![[Figure 2]](./ld2009fig2thm.gif)
| Fig. 2. Statistical distribution of O=C—C—Cl dihedral angles (data based on CSD search including all deposited crystal structures up to November 2010). |
| C14H11ClO | F(000) = 480 |
| Mr = 230.68 | Dx = 1.341 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 5815 reflections |
| a = 12.6233 (11) Å | θ = 2.6–28.3° |
| b = 5.8227 (5) Å | µ = 0.31 mm−1 |
| c = 15.6745 (14) Å | T = 200 K |
| β = 97.317 (3)° | Rod, colourless |
| V = 1142.72 (17) Å3 | 0.53 × 0.29 × 0.16 mm |
| Z = 4 |
| Bruker APEXII CCD diffractometer | 2366 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.024 |
| graphite | θmax = 28.3°, θmin = 2.6° |
| φ and ω scans | h = −16→16 |
| 9777 measured reflections | k = −7→6 |
| 2816 independent reflections | l = −20→20 |
| Refinement on F2 | Primary atom site location: structure-invariant direct methods |
| Least-squares matrix: full | Secondary atom site location: difference Fourier map |
| R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.104 | H-atom parameters constrained |
| S = 1.07 | w = 1/[σ2(Fo2) + (0.0471P)2 + 0.3595P] where P = (Fo2 + 2Fc2)/3 |
| 2816 reflections | (Δ/σ)max < 0.001 |
| 145 parameters | Δρmax = 0.36 e Å−3 |
| 0 restraints | Δρmin = −0.42 e Å−3 |
| C14H11ClO | V = 1142.72 (17) Å3 |
| Mr = 230.68 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 12.6233 (11) Å | µ = 0.31 mm−1 |
| b = 5.8227 (5) Å | T = 200 K |
| c = 15.6745 (14) Å | 0.53 × 0.29 × 0.16 mm |
| β = 97.317 (3)° |
| Bruker APEXII CCD diffractometer | 2366 reflections with I > 2σ(I) |
| 9777 measured reflections | Rint = 0.024 |
| 2816 independent reflections | θmax = 28.3° |
| R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
| wR(F2) = 0.104 | Δρmax = 0.36 e Å−3 |
| S = 1.07 | Δρmin = −0.42 e Å−3 |
| 2816 reflections | Absolute structure: ? |
| 145 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| x | y | z | Uiso*/Ueq | ||
| Cl1 | 0.36760 (3) | 0.54577 (9) | 0.02422 (2) | 0.05873 (16) | |
| O1 | 0.19610 (9) | 0.8528 (2) | 0.05035 (8) | 0.0585 (3) | |
| C1 | 0.17721 (11) | 0.6644 (2) | 0.07711 (8) | 0.0369 (3) | |
| C2 | 0.26188 (10) | 0.4753 (2) | 0.08663 (8) | 0.0361 (3) | |
| H2 | 0.2277 | 0.3291 | 0.0637 | 0.043* | |
| C11 | 0.07080 (10) | 0.6085 (2) | 0.10402 (7) | 0.0318 (3) | |
| C12 | 0.04806 (11) | 0.4010 (2) | 0.14191 (9) | 0.0369 (3) | |
| H12 | 0.1014 | 0.2853 | 0.1511 | 0.044* | |
| C13 | −0.05239 (11) | 0.3628 (3) | 0.16633 (10) | 0.0436 (3) | |
| H13 | −0.0673 | 0.2221 | 0.1931 | 0.052* | |
| C14 | −0.13073 (11) | 0.5290 (3) | 0.15188 (10) | 0.0454 (3) | |
| H14 | −0.1996 | 0.5017 | 0.1682 | 0.054* | |
| C15 | −0.10909 (12) | 0.7350 (3) | 0.11366 (10) | 0.0456 (3) | |
| H15 | −0.1632 | 0.8486 | 0.1032 | 0.055* | |
| C16 | −0.00869 (11) | 0.7752 (2) | 0.09067 (8) | 0.0395 (3) | |
| H16 | 0.0063 | 0.9181 | 0.0655 | 0.047* | |
| C21 | 0.30932 (9) | 0.4355 (2) | 0.17883 (8) | 0.0313 (3) | |
| C22 | 0.36130 (11) | 0.2294 (2) | 0.20111 (10) | 0.0411 (3) | |
| H22 | 0.3639 | 0.1128 | 0.1590 | 0.049* | |
| C23 | 0.40932 (12) | 0.1938 (3) | 0.28445 (11) | 0.0485 (4) | |
| H23 | 0.4461 | 0.0542 | 0.2991 | 0.058* | |
| C24 | 0.40391 (12) | 0.3604 (3) | 0.34634 (10) | 0.0483 (4) | |
| H24 | 0.4364 | 0.3348 | 0.4036 | 0.058* | |
| C25 | 0.35139 (12) | 0.5639 (3) | 0.32497 (9) | 0.0451 (3) | |
| H25 | 0.3470 | 0.6780 | 0.3677 | 0.054* | |
| C26 | 0.30485 (11) | 0.6021 (2) | 0.24116 (8) | 0.0372 (3) | |
| H26 | 0.2697 | 0.7436 | 0.2265 | 0.045* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0447 (2) | 0.0974 (4) | 0.0365 (2) | −0.0071 (2) | 0.01475 (15) | −0.00083 (19) |
| O1 | 0.0538 (6) | 0.0513 (7) | 0.0703 (8) | −0.0085 (5) | 0.0077 (6) | 0.0241 (6) |
| C1 | 0.0385 (6) | 0.0400 (7) | 0.0312 (6) | −0.0051 (5) | 0.0003 (5) | 0.0047 (5) |
| C2 | 0.0319 (6) | 0.0449 (7) | 0.0321 (6) | −0.0058 (5) | 0.0068 (5) | −0.0049 (5) |
| C11 | 0.0332 (6) | 0.0338 (6) | 0.0271 (5) | −0.0019 (5) | −0.0011 (4) | 0.0001 (5) |
| C12 | 0.0344 (6) | 0.0325 (6) | 0.0429 (7) | −0.0001 (5) | 0.0020 (5) | 0.0033 (5) |
| C13 | 0.0412 (7) | 0.0392 (7) | 0.0508 (8) | −0.0069 (6) | 0.0075 (6) | 0.0037 (6) |
| C14 | 0.0335 (7) | 0.0558 (9) | 0.0472 (8) | −0.0025 (6) | 0.0066 (6) | −0.0046 (7) |
| C15 | 0.0403 (7) | 0.0479 (8) | 0.0474 (8) | 0.0116 (6) | 0.0010 (6) | −0.0026 (6) |
| C16 | 0.0459 (7) | 0.0355 (7) | 0.0358 (7) | 0.0032 (6) | 0.0003 (5) | 0.0031 (5) |
| C21 | 0.0268 (5) | 0.0337 (6) | 0.0339 (6) | −0.0021 (5) | 0.0063 (4) | −0.0003 (5) |
| C22 | 0.0364 (7) | 0.0336 (7) | 0.0539 (8) | 0.0008 (5) | 0.0081 (6) | −0.0030 (6) |
| C23 | 0.0386 (7) | 0.0413 (8) | 0.0646 (10) | 0.0038 (6) | 0.0026 (6) | 0.0153 (7) |
| C24 | 0.0422 (7) | 0.0584 (9) | 0.0423 (7) | −0.0050 (7) | −0.0018 (6) | 0.0155 (7) |
| C25 | 0.0503 (8) | 0.0510 (9) | 0.0335 (7) | −0.0008 (7) | 0.0029 (6) | −0.0026 (6) |
| C26 | 0.0413 (7) | 0.0348 (7) | 0.0351 (6) | 0.0041 (5) | 0.0031 (5) | −0.0002 (5) |
| Cl1—C2 | 1.7997 (13) | C15—C16 | 1.381 (2) |
| O1—C1 | 1.2092 (18) | C15—H15 | 0.9500 |
| C1—C11 | 1.4941 (18) | C16—H16 | 0.9500 |
| C1—C2 | 1.529 (2) | C21—C26 | 1.3829 (18) |
| C2—C21 | 1.5100 (18) | C21—C22 | 1.3910 (18) |
| C2—H2 | 1.0000 | C22—C23 | 1.384 (2) |
| C11—C12 | 1.3921 (18) | C22—H22 | 0.9500 |
| C11—C16 | 1.3929 (18) | C23—C24 | 1.379 (2) |
| C12—C13 | 1.3883 (19) | C23—H23 | 0.9500 |
| C12—H12 | 0.9500 | C24—C25 | 1.378 (2) |
| C13—C14 | 1.381 (2) | C24—H24 | 0.9500 |
| C13—H13 | 0.9500 | C25—C26 | 1.3871 (19) |
| C14—C15 | 1.384 (2) | C25—H25 | 0.9500 |
| C14—H14 | 0.9500 | C26—H26 | 0.9500 |
| O1—C1—C11 | 121.31 (13) | C14—C15—H15 | 120.1 |
| O1—C1—C2 | 121.41 (13) | C15—C16—C11 | 120.67 (13) |
| C11—C1—C2 | 117.27 (11) | C15—C16—H16 | 119.7 |
| C21—C2—C1 | 113.02 (10) | C11—C16—H16 | 119.7 |
| C21—C2—Cl1 | 108.91 (9) | C26—C21—C22 | 119.22 (12) |
| C1—C2—Cl1 | 109.90 (10) | C26—C21—C2 | 121.45 (12) |
| C21—C2—H2 | 108.3 | C22—C21—C2 | 119.30 (12) |
| C1—C2—H2 | 108.3 | C23—C22—C21 | 120.13 (13) |
| Cl1—C2—H2 | 108.3 | C23—C22—H22 | 119.9 |
| C12—C11—C16 | 119.03 (12) | C21—C22—H22 | 119.9 |
| C12—C11—C1 | 123.44 (12) | C24—C23—C22 | 120.25 (14) |
| C16—C11—C1 | 117.52 (12) | C24—C23—H23 | 119.9 |
| C13—C12—C11 | 120.11 (13) | C22—C23—H23 | 119.9 |
| C13—C12—H12 | 119.9 | C25—C24—C23 | 119.92 (14) |
| C11—C12—H12 | 119.9 | C25—C24—H24 | 120.0 |
| C14—C13—C12 | 120.18 (14) | C23—C24—H24 | 120.0 |
| C14—C13—H13 | 119.9 | C24—C25—C26 | 120.06 (14) |
| C12—C13—H13 | 119.9 | C24—C25—H25 | 120.0 |
| C13—C14—C15 | 120.10 (13) | C26—C25—H25 | 120.0 |
| C13—C14—H14 | 120.0 | C21—C26—C25 | 120.40 (13) |
| C15—C14—H14 | 120.0 | C21—C26—H26 | 119.8 |
| C16—C15—C14 | 119.89 (13) | C25—C26—H26 | 119.8 |
| C16—C15—H15 | 120.1 | ||
| O1—C1—C2—C21 | 104.41 (15) | C12—C11—C16—C15 | −0.8 (2) |
| C11—C1—C2—C21 | −74.29 (14) | C1—C11—C16—C15 | 179.73 (12) |
| O1—C1—C2—Cl1 | −17.47 (17) | C1—C2—C21—C26 | −21.38 (17) |
| C11—C1—C2—Cl1 | 163.83 (9) | Cl1—C2—C21—C26 | 101.06 (13) |
| O1—C1—C11—C12 | −174.40 (14) | C1—C2—C21—C22 | 160.45 (11) |
| C2—C1—C11—C12 | 4.30 (18) | Cl1—C2—C21—C22 | −77.11 (13) |
| O1—C1—C11—C16 | 5.09 (19) | C26—C21—C22—C23 | −1.02 (19) |
| C2—C1—C11—C16 | −176.21 (11) | C2—C21—C22—C23 | 177.18 (12) |
| C16—C11—C12—C13 | −0.4 (2) | C21—C22—C23—C24 | 1.4 (2) |
| C1—C11—C12—C13 | 179.07 (12) | C22—C23—C24—C25 | −0.6 (2) |
| C11—C12—C13—C14 | 1.1 (2) | C23—C24—C25—C26 | −0.6 (2) |
| C12—C13—C14—C15 | −0.6 (2) | C22—C21—C26—C25 | −0.2 (2) |
| C13—C14—C15—C16 | −0.6 (2) | C2—C21—C26—C25 | −178.35 (13) |
| C14—C15—C16—C11 | 1.3 (2) | C24—C25—C26—C21 | 1.0 (2) |
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Bruker (2010). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Grossert, J. S., Dubey, P. K., Gill, G. H., Cameron, T. S. & Gardner, P. A. (1984). Can. J. Chem. 62, 798–807.
Haisa, M., Kashino, S. & Morimoto, M. (1980). Acta Cryst. B36, 2832–2834.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
Rieker, T. P., Haltiwanger, C., Eidman, K., Walba, D. W., Clark, N. A. & Larson, A. C. (1993). Acta Cryst. C49, 406–408.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Sole, S., Gornitzka, H., Guerret, O. & Bertrand, G. (1998). J. Am. Chem. Soc. 120, 9100–9101.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
The title compound was studied as a reference structure for a series of transition-metal complexes employing it as a ligand.
Bond lengths and angles are usual. The torsion angle O=C—C—Cl is 17.5 (2) °. A statistics of values for the similar angles reported in the CSD (Allen, 2002) shows that this eclipsed conformation is the most preferable for α-cloroketones (Fig. 1 and Fig. 2). However, possibly due to steric hindrances from the bulky phenyl group next to the Cl substituent, the dihedral value is somewhat distorted in comparison to the molecular structure of 2-chloroacetophenone (Grossert et al. (1984)), where the respective angle was found at 2.4 °.
Unlike the crystal structure of 2-chloroacetophenone, which is dominated by strong C–H···O and C–H···Cl contacts, the crystal structure of the title compound does not show any intermolecular contacts whose range falls short of the sum of van-der-Waals radii. The closest π···π-contact was measured at 4.258 (1) Å.