2-Bromo-1-mesitylethanone

Chen, L.; Xu, Q.-B.; Song, G.-L.; Zhu, H.-J.

doi:10.1107/S1600536809012276

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1083

doi:10.1107/S1600536809012276

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2-Bromo-1-mesitylethanone

Lei Chen,^a Qing-Bing Xu,^a Guang-Liang Song ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 31 March 2009; accepted 1 April 2009; online 22 April 2009)

In the molecule of the title compound, C₁₁H₁₃BrO, the adjacent C atoms are almost coplanar with the aromatic ring [maximum deviation 0.035 (3) Å]. In the crystal structure, weak intermolecular C—H⋯O interactions link the molecules into chains along the b axis. A very weak C—H⋯π interaction is also present.

Related literature

The title compound is used to synthesize organic electronic devices, see: Rose et al. (2008 ). For a related structure, see: Guss (1953 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₃BrO
M_r = 241.12
Orthorhombic, P b c a
a = 15.379 (3) Å
b = 8.2820 (17) Å
c = 17.374 (4) Å
V = 2212.9 (8) Å³
Z = 8
Mo Kα radiation
μ = 3.68 mm⁻¹
T = 294 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.527, T_max = 0.710
3509 measured reflections
2002 independent reflections
805 reflections with I > 2σ(I)
R_int = 0.099
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.095
S = 1.00
2002 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9B⋯Oⁱ	0.96	2.52	3.462 (7)	166
C11—H11A⋯Oⁱ	0.97	2.36	3.308 (7)	167
C7—H7C⋯Cg1ⁱⁱ	0.96	2.94	3.722 (3)	140
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (ii) -x, -y+1, -z+1. Cg1 is the centroid of the C1–C6 ring.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012276/hk2660sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012276/hk2660Isup2.hkl

checkCIF report

Comment top

The title compound is used to synthesize organic electronic devices and medical intermediates (Rose et al., 2008). We report herein the crystal structure of the title compound, which is interested to us in the field.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Ring A (C1-C6) is, of course, planar. Atoms C7, C8, C9 and C10 are -0.012 (2), -0.019 (3), -0.035 (3) and -0.006 (3) Å away from the ring plane of A, respectively.

In the crystal structure, weak intermolecular C-H···O interactions (Table 1) link the molecules into chains along the b axis, in which they may be effective in the stabilization of the structure. There also exists a weak C—H···π interaction (Table 1).

Related literature top

The title compound is used to synthesize organic electronic devices and medical intermediates, see: Rose et al. (2008). For a related structure, see: Guss (1953). For bond-length data, see: Allen et al. (1987). Cg1 is the centroid of the C1–C6 ring.

Experimental top

The title compound, (m.p. 323-324 K), was prepared according to the literature method (Guss, 1953). Crystals suitable for X-ray analysis were obtained by dissolving the title compound (0.2 g) in ethyl acetate (50 ml) and evaporating the solvent slowly at room temperature for about 3 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

2-bromo-1-mesitylethanone top

Crystal data top

C₁₁H₁₃BrO	F(000) = 976
M_r = 241.12	D_x = 1.447 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 15.379 (3) Å	θ = 10–13°
b = 8.2820 (17) Å	µ = 3.68 mm⁻¹
c = 17.374 (4) Å	T = 294 K
V = 2212.9 (8) Å³	Needle, colorless
Z = 8	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	805 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.099
Graphite monochromator	θ_max = 25.3°, θ_min = 2.3°
ω/2θ scans	h = 0→18
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
T_min = 0.527, T_max = 0.710	l = −20→12
3509 measured reflections	3 standard reflections every 120 min
2002 independent reflections	intensity decay: 1%

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.022P)²] where P = (F_o² + 2F_c²)/3
2002 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₁₃BrO	V = 2212.9 (8) Å³
M_r = 241.12	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 15.379 (3) Å	µ = 3.68 mm⁻¹
b = 8.2820 (17) Å	T = 294 K
c = 17.374 (4) Å	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	805 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.099
T_min = 0.527, T_max = 0.710	3 standard reflections every 120 min
3509 measured reflections	intensity decay: 1%
2002 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.00	Δρ_max = 0.28 e Å⁻³
2002 reflections	Δρ_min = −0.29 e Å⁻³
118 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Br	0.22106 (4)	0.01688 (8)	0.59900 (4)	0.0758 (3)
O	0.1783 (3)	−0.1396 (5)	0.7510 (3)	0.0853 (16)
C1	−0.0250 (4)	0.1475 (7)	0.8818 (4)	0.0557 (19)
H1A	−0.0852	0.1583	0.8816	0.067*
C2	0.0138 (4)	0.0860 (6)	0.8160 (4)	0.0461 (16)
C3	0.1038 (4)	0.0675 (6)	0.8208 (4)	0.0458 (17)
C4	0.1509 (4)	0.1135 (7)	0.8840 (4)	0.0462 (17)
C5	0.1083 (4)	0.1744 (7)	0.9464 (4)	0.0540 (18)
H5A	0.1400	0.2040	0.9898	0.065*
C6	0.0180 (5)	0.1932 (7)	0.9465 (4)	0.062 (2)
C7	−0.0290 (3)	0.2598 (7)	1.0151 (4)	0.079 (2)
H7A	−0.0903	0.2624	1.0048	0.119*
H7B	−0.0088	0.3672	1.0255	0.119*
H7C	−0.0181	0.1924	1.0590	0.119*
C8	−0.0388 (3)	0.0364 (6)	0.7488 (3)	0.0630 (18)
H8A	−0.0989	0.0601	0.7583	0.094*
H8B	−0.0319	−0.0774	0.7403	0.094*
H8C	−0.0196	0.0944	0.7040	0.094*
C9	0.2492 (3)	0.0917 (7)	0.8895 (3)	0.068 (2)
H9A	0.2692	0.1304	0.9385	0.101*
H9B	0.2769	0.1517	0.8491	0.101*
H9C	0.2633	−0.0207	0.8843	0.101*
C10	0.1514 (4)	−0.0002 (8)	0.7513 (3)	0.0459 (15)
C11	0.1681 (3)	0.1137 (7)	0.6882 (3)	0.0592 (19)
H11A	0.2057	0.1991	0.7069	0.071*
H11B	0.1135	0.1628	0.6729	0.071*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0835 (6)	0.0705 (5)	0.0734 (5)	−0.0009 (5)	0.0146 (4)	−0.0066 (5)
O	0.111 (4)	0.057 (3)	0.088 (4)	0.040 (3)	0.016 (3)	0.015 (3)
C1	0.033 (4)	0.044 (4)	0.090 (6)	0.000 (3)	0.021 (4)	0.011 (4)
C2	0.037 (5)	0.036 (4)	0.065 (5)	0.002 (3)	0.000 (4)	−0.005 (4)
C3	0.044 (5)	0.030 (4)	0.064 (5)	−0.002 (3)	0.011 (4)	−0.009 (3)
C4	0.026 (4)	0.041 (4)	0.072 (6)	−0.004 (3)	0.005 (4)	0.001 (4)
C5	0.047 (5)	0.050 (4)	0.065 (5)	−0.008 (4)	−0.004 (4)	0.002 (4)
C6	0.087 (7)	0.039 (4)	0.059 (6)	−0.005 (5)	0.016 (5)	0.002 (4)
C7	0.075 (6)	0.084 (5)	0.079 (7)	0.015 (4)	0.011 (5)	0.009 (5)
C8	0.049 (4)	0.054 (4)	0.085 (5)	0.000 (4)	−0.021 (4)	0.002 (4)
C9	0.048 (5)	0.080 (5)	0.075 (5)	−0.016 (3)	−0.015 (4)	0.014 (4)
C10	0.038 (4)	0.038 (4)	0.061 (4)	−0.005 (4)	−0.016 (3)	0.010 (5)
C11	0.042 (4)	0.065 (5)	0.070 (5)	0.002 (3)	0.003 (4)	0.003 (4)

Geometric parameters (Å, º) top

Br—C11	1.925 (6)	C6—C7	1.499 (8)
O—C10	1.226 (6)	C7—H7A	0.9600
C1—C6	1.358 (9)	C7—H7B	0.9600
C1—C2	1.387 (8)	C7—H7C	0.9600
C1—H1A	0.9300	C8—H8A	0.9600
C2—C3	1.396 (7)	C8—H8B	0.9600
C2—C8	1.479 (7)	C8—H8C	0.9600
C3—C4	1.369 (8)	C9—H9A	0.9600
C3—C10	1.519 (8)	C9—H9B	0.9600
C4—C5	1.364 (7)	C9—H9C	0.9600
C4—C9	1.526 (7)	C10—C11	1.470 (7)
C5—C6	1.399 (7)	C11—H11A	0.9700
C5—H5A	0.9300	C11—H11B	0.9700

C6—C1—C2	125.2 (6)	H7B—C7—H7C	109.5
C6—C1—H1A	117.4	C2—C8—H8A	109.5
C2—C1—H1A	117.4	C2—C8—H8B	109.5
C1—C2—C3	114.7 (6)	H8A—C8—H8B	109.5
C1—C2—C8	121.2 (6)	C2—C8—H8C	109.5
C3—C2—C8	124.0 (6)	H8A—C8—H8C	109.5
C4—C3—C2	122.8 (6)	H8B—C8—H8C	109.5
C4—C3—C10	119.0 (6)	C4—C9—H9A	109.5
C2—C3—C10	118.1 (6)	C4—C9—H9B	109.5
C5—C4—C3	119.1 (6)	H9A—C9—H9B	109.5
C5—C4—C9	118.0 (6)	C4—C9—H9C	109.5
C3—C4—C9	122.8 (6)	H9A—C9—H9C	109.5
C4—C5—C6	121.3 (6)	H9B—C9—H9C	109.5
C4—C5—H5A	119.4	O—C10—C11	122.8 (6)
C6—C5—H5A	119.4	O—C10—C3	120.9 (5)
C1—C6—C5	116.8 (7)	C11—C10—C3	116.1 (6)
C1—C6—C7	121.8 (7)	C10—C11—Br	114.0 (4)
C5—C6—C7	121.4 (8)	C10—C11—H11A	108.7
C6—C7—H7A	109.5	Br—C11—H11A	108.7
C6—C7—H7B	109.5	C10—C11—H11B	108.7
H7A—C7—H7B	109.5	Br—C11—H11B	108.7
C6—C7—H7C	109.5	H11A—C11—H11B	107.6
H7A—C7—H7C	109.5

C6—C1—C2—C3	2.1 (9)	C9—C4—C5—C6	−178.0 (5)
C6—C1—C2—C8	178.8 (6)	C2—C1—C6—C5	−0.8 (10)
C1—C2—C3—C4	−3.0 (8)	C2—C1—C6—C7	179.6 (6)
C8—C2—C3—C4	−179.6 (6)	C4—C5—C6—C1	0.2 (9)
C1—C2—C3—C10	179.6 (5)	C4—C5—C6—C7	179.9 (6)
C8—C2—C3—C10	3.0 (8)	C4—C3—C10—O	77.5 (8)
C2—C3—C4—C5	2.6 (9)	C2—C3—C10—O	−105.0 (7)
C10—C3—C4—C5	180.0 (5)	C4—C3—C10—C11	−98.3 (6)
C2—C3—C4—C9	179.4 (5)	C2—C3—C10—C11	79.2 (7)
C10—C3—C4—C9	−3.3 (8)	O—C10—C11—Br	8.5 (8)
C3—C4—C5—C6	−1.2 (9)	C3—C10—C11—Br	−175.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Oⁱ	0.96	2.52	3.462 (7)	166
C11—H11A···Oⁱ	0.97	2.36	3.308 (7)	167
C7—H7C···Cg1ⁱⁱ	0.96	2.94	3.722 (3)	140

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃BrO
M_r	241.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	15.379 (3), 8.2820 (17), 17.374 (4)
V (Å³)	2212.9 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.68
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.527, 0.710
No. of measured, independent and observed [I > 2σ(I)] reflections	3509, 2002, 805
R_int	0.099
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.095, 1.00
No. of reflections	2002
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.29

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9B···Oⁱ	0.96	2.52	3.462 (7)	166
C11—H11A···Oⁱ	0.97	2.36	3.308 (7)	167
C7—H7C···Cg1ⁱⁱ	0.96	2.94	3.722 (3)	140

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for the data collection.

References

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