2-Bromo-1-phenyl­ethanone

Betz, R.; McCleland, C.; Marchand, H.

doi:10.1107/S1600536811014644

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1207

doi:10.1107/S1600536811014644

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2-Bromo-1-phenylethanone

Richard Betz,^a ^* Cedric McCleland ^a and Harold Marchand ^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 19 April 2011; online 22 April 2011)

The title compound, C₈H₇BrO, is a halogenated derivative of acetophenone. The molecule shows noncrystallographic C_s symmetry. The intracyclic C—C—C angles cover the range 118.8 (2)–120.4 (3)°. In the crystal structure, C—H⋯O contacts connect the molecules into undulating sheets perpendicular to the crystallographic c axis.

Related literature

For the crystal structure of α-chloro-acetophenone, see: Barrans & Maisseu (1966 ); Grossert et al. (1984 ). For the crystal structure of α-iodo-acetophenone, see: Lere-Porte et al. (1982 ). For the crystal structures of coordination compounds using the title compound as a ligand, see: Laube et al. (1991 ). For details of graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ); Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₇BrO
M_r = 199.05
Orthorhombic, P 2₁ 2₁ 2₁
a = 4.1459 (2) Å
b = 9.6731 (5) Å
c = 18.8178 (9) Å
V = 754.66 (6) Å³
Z = 4
Mo Kα radiation
μ = 5.37 mm⁻¹
T = 200 K
0.54 × 0.43 × 0.09 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2010 ) T_min = 0.588, T_max = 1.000
7436 measured reflections
1867 independent reflections
1692 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.072
S = 1.08
1867 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.66 e Å⁻³
Absolute structure: Flack (1983 ), with 736 Friedel pairs
Flack parameter: 0.015 (14)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H21⋯O1ⁱ	0.99	2.46	3.317 (4)	145
C2—H22⋯O1ⁱⁱ	0.99	2.44	3.268 (4)	141
C8—H8⋯O1ⁱ	0.95	2.60	3.442 (3)	148
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014644/fy2008sup1.cif

Supporting information file. DOI: 10.1107/S1600536811014644/fy2008Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014644/fy2008Isup3.hkl

checkCIF report

Comment top

Derivatives of acetophenone are widely used in preparative organic chemistry. At the beginning of a comprehensive study about the effects of various substituents on benzo-annulated seven-membered ring systems, the molecular structure of the title compound was determined to enable comparisons with acetophenone-derived target compounds.

Intracyclic C—C—C angles span a range from 118–120°. The smallest angle is found on the C atom bearing the carbonylic substituent while the second smallest one is found on the C atom in para-position. The atoms of the aliphatic substituent are nearly coplanar with the aromatic system and its conjugated carbonyl group, the least-squares planes defined by their respective atoms intersect at an angle of only 4.18 (15)°.

In the crystal structure, C—H···O contacts can be observed which stem from both H atoms of the methylene group as well as one of the H atoms in ortho-position to the substituent on the phenyl ring. The carbonylic O atom serves as threefold acceptor (Fig. 2). Describing these contacts in terms of graph-set analysis necessitates a C(4)C(4)C(5) descriptor on the unitary level. In total, the molecules are connected to waved sheets perpendicular to the crystallographic c axis. The shortest distance between the centroids of two π-systems was measured at 5.8289 (17) Å.

The packing of the compound in the crystal is shown in Fig. 3.

Related literature top

For the crystal structure of α-chloro-acetophenone, see: Barrans & Maisseu (1966); Grossert et al. (1984). For the crystal structure of α-iodo-acetophenone, see: Lere-Porte et al. (1982). For the crystal structures of coordination compounds using the title compound as a ligand, see: Laube et al. (1991). For details of graph-set analysis of hydrogen bonds, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

The compound was obtained commercially (Schuchardt). Crystals suitable for the X-ray diffraction study were taken directly from the provided batch.

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., 2008); 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. Intermolecular contacts, viewed along [00\=1]. Symmetry operators: ⁱ -x + 1, y + 1/2, -z + 1/2; ⁱⁱ -x + 2, y + 1/2, -z + 1/2; ⁱⁱⁱ -x + 1, y - 1/2, -z + 1/2; ^iv -x + 2, y - 1/2, -z + 1/2.
	Fig. 3. Molecular packing of the title compound, viewed along [\=100] (anisotropic displacement ellipsoids drawn at 50% probability level).

2-Bromo-1-phenylethanone top

Crystal data top

C₈H₇BrO	F(000) = 392
M_r = 199.05	D_x = 1.752 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5571 reflections
a = 4.1459 (2) Å	θ = 2.4–28.2°
b = 9.6731 (5) Å	µ = 5.37 mm⁻¹
c = 18.8178 (9) Å	T = 200 K
V = 754.66 (6) Å³	Platelet, colourless
Z = 4	0.54 × 0.43 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	1867 independent reflections
Radiation source: fine-focus sealed tube	1692 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 28.3°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2010)	h = −4→5
T_min = 0.588, T_max = 1.000	k = −12→12
7436 measured reflections	l = −25→24

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0377P)² + 0.0956P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1867 reflections	Δρ_max = 0.42 e Å⁻³
91 parameters	Δρ_min = −0.66 e Å⁻³
0 restraints	Absolute structure: Flack (1983), with 736 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.015 (14)

Crystal data top

C₈H₇BrO	V = 754.66 (6) Å³
M_r = 199.05	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 4.1459 (2) Å	µ = 5.37 mm⁻¹
b = 9.6731 (5) Å	T = 200 K
c = 18.8178 (9) Å	0.54 × 0.43 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	1867 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2010)	1692 reflections with I > 2σ(I)
T_min = 0.588, T_max = 1.000	R_int = 0.037
7436 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	H-atom parameters constrained
wR(F²) = 0.072	Δρ_max = 0.42 e Å⁻³
S = 1.08	Δρ_min = −0.66 e Å⁻³
1867 reflections	Absolute structure: Flack (1983), with 736 Friedel pairs
91 parameters	Absolute structure parameter: 0.015 (14)
0 restraints

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

	x	y	z	U_iso*/U_eq
Br1	0.94179 (9)	0.02569 (3)	0.353315 (15)	0.04357 (12)
O1	0.7669 (6)	−0.1520 (2)	0.22942 (12)	0.0462 (6)
C1	0.6825 (7)	−0.0344 (3)	0.21549 (14)	0.0288 (5)
C2	0.7424 (7)	0.0837 (3)	0.26609 (14)	0.0302 (6)
H21	0.5345	0.1292	0.2771	0.036*
H22	0.8828	0.1527	0.2426	0.036*
C3	0.5113 (6)	−0.0030 (2)	0.14809 (12)	0.0269 (5)
C4	0.4564 (9)	−0.1109 (3)	0.10021 (14)	0.0361 (6)
H4	0.5303	−0.2014	0.1111	0.043*
C5	0.2955 (9)	−0.0866 (3)	0.03729 (16)	0.0416 (7)
H5	0.2609	−0.1604	0.0049	0.050*
C6	0.1839 (9)	0.0449 (4)	0.02105 (16)	0.0400 (7)
H6	0.0712	0.0610	−0.0221	0.048*
C7	0.2374 (8)	0.1525 (3)	0.06797 (14)	0.0355 (7)
H7	0.1621	0.2426	0.0569	0.043*
C8	0.4002 (7)	0.1294 (3)	0.13102 (14)	0.0303 (6)
H8	0.4366	0.2039	0.1629	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04576 (18)	0.04907 (17)	0.03589 (16)	−0.00752 (13)	−0.01195 (14)	0.01138 (12)
O1	0.0662 (17)	0.0267 (9)	0.0455 (12)	0.0095 (11)	−0.0047 (13)	0.0036 (8)
C1	0.0309 (13)	0.0263 (11)	0.0293 (13)	0.0013 (11)	0.0051 (11)	0.0042 (10)
C2	0.0328 (15)	0.0308 (12)	0.0270 (12)	−0.0025 (12)	−0.0040 (12)	0.0023 (11)
C3	0.0288 (13)	0.0273 (12)	0.0246 (11)	−0.0022 (8)	0.0046 (12)	0.0001 (9)
C4	0.0474 (17)	0.0269 (11)	0.0341 (14)	−0.0029 (13)	0.0083 (15)	−0.0029 (9)
C5	0.052 (2)	0.0408 (15)	0.0325 (15)	−0.0080 (16)	0.0017 (16)	−0.0121 (13)
C6	0.0385 (16)	0.0567 (19)	0.0247 (13)	−0.0042 (14)	−0.0012 (13)	0.0008 (12)
C7	0.0393 (18)	0.0386 (14)	0.0286 (14)	0.0046 (13)	0.0011 (14)	0.0028 (11)
C8	0.0360 (16)	0.0288 (12)	0.0262 (13)	−0.0008 (11)	0.0026 (12)	−0.0005 (9)

Geometric parameters (Å, º) top

Br1—C2	1.922 (3)	C4—H4	0.9500
O1—C1	1.219 (3)	C5—C6	1.388 (5)
C1—C3	1.485 (4)	C5—H5	0.9500
C1—C2	1.508 (4)	C6—C7	1.382 (4)
C2—H21	0.9900	C6—H6	0.9500
C2—H22	0.9900	C7—C8	1.383 (4)
C3—C4	1.397 (3)	C7—H7	0.9500
C3—C8	1.399 (3)	C8—H8	0.9500
C4—C5	1.379 (4)

O1—C1—C3	120.8 (2)	C3—C4—H4	119.8
O1—C1—C2	121.6 (3)	C4—C5—C6	120.4 (3)
C3—C1—C2	117.6 (2)	C4—C5—H5	119.8
C1—C2—Br1	112.88 (19)	C6—C5—H5	119.8
C1—C2—H21	109.0	C7—C6—C5	119.7 (3)
Br1—C2—H21	109.0	C7—C6—H6	120.1
C1—C2—H22	109.0	C5—C6—H6	120.1
Br1—C2—H22	109.0	C6—C7—C8	120.3 (3)
H21—C2—H22	107.8	C6—C7—H7	119.8
C4—C3—C8	118.8 (2)	C8—C7—H7	119.8
C4—C3—C1	118.4 (2)	C7—C8—C3	120.4 (2)
C8—C3—C1	122.8 (2)	C7—C8—H8	119.8
C5—C4—C3	120.4 (3)	C3—C8—H8	119.8
C5—C4—H4	119.8

O1—C1—C2—Br1	−2.6 (4)	C1—C3—C4—C5	179.4 (3)
C3—C1—C2—Br1	176.40 (19)	C3—C4—C5—C6	−0.5 (5)
O1—C1—C3—C4	−1.6 (4)	C4—C5—C6—C7	0.7 (5)
C2—C1—C3—C4	179.4 (3)	C5—C6—C7—C8	−0.3 (5)
O1—C1—C3—C8	177.7 (3)	C6—C7—C8—C3	−0.2 (4)
C2—C1—C3—C8	−1.3 (4)	C4—C3—C8—C7	0.3 (4)
C8—C3—C4—C5	0.0 (4)	C1—C3—C8—C7	−179.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H21···O1ⁱ	0.99	2.46	3.317 (4)	145
C2—H22···O1ⁱⁱ	0.99	2.44	3.268 (4)	141
C8—H8···O1ⁱ	0.95	2.60	3.442 (3)	148

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

Experimental details

Crystal data
Chemical formula	C₈H₇BrO
M_r	199.05
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	200
a, b, c (Å)	4.1459 (2), 9.6731 (5), 18.8178 (9)
V (Å³)	754.66 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.37
Crystal size (mm)	0.54 × 0.43 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2010)
T_min, T_max	0.588, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7436, 1867, 1692
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.072, 1.08
No. of reflections	1867
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.66
Absolute structure	Flack (1983), with 736 Friedel pairs
Absolute structure parameter	0.015 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H21···O1ⁱ	0.99	2.46	3.317 (4)	145
C2—H22···O1ⁱⁱ	0.99	2.44	3.268 (4)	141
C8—H8···O1ⁱ	0.95	2.60	3.442 (3)	148

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

Acknowledgements

The authors thank Mr Benjamin Wilson for helpful discussions.

References

Barrans, Y. & Maisseu, J. (1966). C. R. Acad. Sci. Ser. C, 262, 91–92. CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2010). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, USA. Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Grossert, J. S., Dubey, P. K., Gill, G. H., Cameron, T. S. & Gardner, P. A. (1984). Can. J. Chem. 62, 798–807. CrossRef CAS Web of Science Google Scholar
Laube, T., Weidenhaupt, A. & Hunziker, R. (1991). J. Am. Chem. Soc. 113, 2561–2567. CrossRef CAS Google Scholar
Lere-Porte, J.-P., Bonniol, A., Petrissans, J. & Brianso, M.-C. (1982). Acta Cryst. B38, 1035–1037. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar