2-Chloro-1,2-diphenyl­ethanone (desyl chloride)

Betz, R.; McCleland, C.; Hosten, E.

doi:10.1107/S1600536811014541

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1199

doi:10.1107/S1600536811014541

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2-Chloro-1,2-diphenylethanone (desyl chloride)

Richard Betz,^a ^* Cedric McCleland ^a and Eric Hosten ^a

^aNelson Mandela Metropolitan University, Summerstrand Campus, Department of Chemistry, University Way, Summerstrand, PO Box 77000, Port Elizabeth 6031, South Africa
^*Correspondence e-mail: richard.betz@webmail.co.za

(Received 5 April 2011; accepted 18 April 2011; online 22 April 2011)

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 π–π contact is 4.258 (1) Å.

Related literature

For the crystal structure of benzoin, see: Haisa et al. (1980 ); Sole et al. (1998 ). For the crystal structure of 2-phenylacetophenone, see: Rieker et al. (1993 ). For the crystal structure of 2-chloroacetophenone, see: Grossert et al. (1984 ). Structures containing similar angles were retrieved from the Cambridge Structural Database (Allen, 2002 ).

Experimental

Crystal data

C₁₄H₁₁ClO
M_r = 230.68
Monoclinic, P 2₁ /c
a = 12.6233 (11) Å
b = 5.8227 (5) Å
c = 15.6745 (14) Å
β = 97.317 (3)°
V = 1142.72 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 200 K
0.53 × 0.29 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
9777 measured reflections
2816 independent reflections
2366 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.104
S = 1.07
2816 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; 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 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014541/ld2009sup1.cif

Supporting information file. DOI: 10.1107/S1600536811014541/ld2009Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014541/ld2009Isup3.hkl

checkCIF report

Comment top

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.

Related literature top

For the crystal structure of benzoin, see: Haisa et al. (1980); Sole et al. (1998). For the crystal structure of 2-phenylacetophenone, see: Rieker et al. (1993). For the crystal structure of 2-chloroacetophenone, see: Grossert et al. (1984). Structures containing similar angles were retrieved from the Cambridge Structural Database (Allen, 2002).

Experimental top

The compound was synthesized by reacting benzoin with thionyl chloride. Crystals suitable for X-ray diffraction were obtained upon recrystallization from ethanol.

Computing details top

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).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and anisotropic displacement ellipsoids drawn at 50% probability level.
	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).

2-Chloro-1,2-diphenylethanone top

Crystal data top

C₁₄H₁₁ClO	F(000) = 480
M_r = 230.68	D_x = 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

Data collection top

Bruker APEXII CCD diffractometer	2366 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.024
Graphite monochromator	θ_max = 28.3°, θ_min = 2.6°
ϕ and ω scans	h = −16→16
9777 measured reflections	k = −7→6
2816 independent reflections	l = −20→20

Refinement top

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(F_o²) + (0.0471P)² + 0.3595P] where P = (F_o² + 2F_c²)/3
2816 reflections	(Δ/σ)_max < 0.001
145 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₁₄H₁₁ClO	V = 1142.72 (17) Å³
M_r = 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)°

Data collection top

Bruker APEXII CCD diffractometer	2366 reflections with I > 2σ(I)
9777 measured reflections	R_int = 0.024
2816 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.07	Δρ_max = 0.36 e Å⁻³
2816 reflections	Δρ_min = −0.42 e Å⁻³
145 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Experimental details

Crystal data
Chemical formula	C₁₄H₁₁ClO
M_r	230.68
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	200
a, b, c (Å)	12.6233 (11), 5.8227 (5), 15.6745 (14)
β (°)	97.317 (3)
V (Å³)	1142.72 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.53 × 0.29 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	9777, 2816, 2366
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.104, 1.07
No. of reflections	2816
No. of parameters	145
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.42

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2006), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Acknowledgements

The authors thank Mr Neil van der Vyver for helpful discussions.

References

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