2-Bromo-1-chloro­phenyl-3-(4-methoxy­phen­yl)prop-2-en-1-one

Harrison, W.T.A.; Yathirajan, H.S.; Sarojini, B.K.; Narayana, B.; Vijaya Raj, K.K.

doi:10.1107/S1600536806010464

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 4| April 2006| Pages o1578-o1579

https://doi.org/10.1107/S1600536806010464

2-Bromo-1-chlorophenyl-3-(4-methoxyphenyl)prop-2-en-1-one

William T. A. Harrison,^a ^* H. S. Yathirajan,^b B. K. Sarojini,^c B. Narayana ^d and K. K. Vijaya Raj ^d

^aDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore-570 006, India, ^cDepartment of Chemistry, P. A. College of Engineering, Nadupadavu, Mangalore-574 153, India, and ^dDepartment of Chemistry, Mangalore University, Mangalagangotri-574 199, India
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 21 March 2006; accepted 22 March 2006; online 29 March 2006)

The geometrical parameters for the title compound, C₁₆H₁₂BrClO₂, are normal. The observed bond lengths and angles imply that there is little electronic conjugation between the two benzene ring systems. An intramolecular C—H⋯Br interaction may help to establish the molecular conformation. The crystal packing results in a centrosymmetric structure.

Comment

Many chalcone (C₁₅H₁₂O) derivatives crystallize as non-centrosymmetric structures and display significant non-linear optical (NLO) properties (Uchida et al., 1998 ). The title compound, (I), (Fig. 1), was prepared as part of our ongoing studies in this area (Harrison et al., 2005 ). However, (I) crystallizes in a centrosymmetric space group, thus it has a zero NLO response (Watson et al., 1993 ).

The geometrical parameters for (I) are normal (Allen et al., 1987 ) and consistent with those of other chalcone derivatives (Moorthi et al., 2005 ; Patil et al., 2006 ). The molecule of (I) is distinctly twisted about the C4—C7 and C7—C8 bonds (Table 1). This twisting, and the C4—C7 and C7—C8 bond lengths of greater than 1.48 Å, imply that there is limited electronic conjugation between the two aromatic ring systems. The dihedral angle between the benzene ring mean planes (C1–C6 and C10–C15) is 53.35 (6)°. C7 and O2 deviate from the former mean plane by 0.176 (3) and 0.895 (3) Å, respectively. By contrast, the terminal methyl atom C16 is almost co-planar with the C10–C15 ring [deviation = 0.045 (4) Å].

A PLATON (Spek, 2003 ) analysis of (I) indicated a possible intramolecular C—H⋯Br interaction (Table 2) that might help to maintain near coplanarity between the C8/C9/Br1 fragment and the C10-benzene ring. The predicted (Bondi, 1964 ) van der Waals contact distance for H and Br is 3.05 Å. There are no π⋯π stacking interactions in the crystal structure of (I).

Figure 1
View of (I)

, showing 50% displacement ellipsoids (arbitrary spheres for the H atoms). The possible C—H⋯Br interaction is indicated by a dashed line.

Experimental

2,3-Dibromo-1-chlorophenyl-3-(4-methoxyphenyl)-2-propan-1-one (4.32 g, 0.01 mol) was mixed with triethylamine (5 ml, 0.05 mol) in toluene (100 ml). The reaction was stirred for 24 hrs. and the precipitated triethylamine hydrobromide was removed by filtration. The solvent was removed under reduced pressure and the resulting solid mass obtained on cooling was collected by filtration. The crude product was recrystallized from ethanol to yield blocks of (I) in 60% yield. M.p.: 403 K. Analysis for C₁₆H₁₂BrClO₂: calc. C 54.65, H 3.44%, found: C 54.53, H 3.64%.

Crystal data

C₁₆H₁₂BrClO₂
M_r = 351.62
Monoclinic, P 2₁ /c
a = 13.9793 (3) Å
b = 8.8780 (1) Å
c = 11.4870 (3) Å
β = 96.7094 (10)°
V = 1415.87 (5) Å³
Z = 4
D_x = 1.650 Mg m⁻³
Mo Kα radiation
Cell parameters from 3426 reflections
θ = 2.9–27.5°
μ = 3.09 mm⁻¹
T = 120 (2) K
Block, colourless
0.55 × 0.37 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer
ω and φ scans
Absorption correction: multi-scan SADABS (Bruker, 2003 ) T_min = 0.266, T_max = 0.573
19150 measured reflections
3249 independent reflections
2906 reflections with I > 2σ(I)
R_int = 0.039
θ_max = 27.5°
h = −18 → 18
k = −11 → 11
l = −14 → 14

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.060
S = 1.04
3249 reflections
183 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0257P)² + 1.1891P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.58 e Å⁻³
Extinction correction: SHELXL
Extinction coefficient: 0.0135 (6)

Table 1
Selected geometric parameters (Å, °)

C4—C7	1.494 (2)
C7—C8	1.488 (2)
C8—C9	1.346 (2)
C9—C10	1.460 (2)

C3—C4—C7—O2	33.7 (2)
O2—C7—C8—Br1	19.6 (2)
C8—C9—C10—C15	−2.9 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15⋯Br1	0.95	2.62	3.3339 (18)	132

H atoms were positioned geometrically (C—H = 0.95–0.98 Å) and refined as riding with U_iso(H) = 1.2U_eq(carrier) or 1.5U_eq(methyl carrier). The methyl group was rotated to fit the electron density.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997 ); data reduction: HKL SCALEPACK and DENZO (Otwinowski & Minor 1997), SCALEPACK and SORTAV (Blessing 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536806010464/bt2039sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806010464/bt2039Isup2.hkl

Computing details top

Data collection: Collect (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO and SCALEPACK (Otwinowski & Minor 1997) & SORTAV (Blessing 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

(I) top

Crystal data top

C₁₆H₁₂BrClO₂	F(000) = 704
M_r = 351.62	D_x = 1.650 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3426 reflections
a = 13.9793 (3) Å	θ = 2.9–27.5°
b = 8.8780 (1) Å	µ = 3.09 mm⁻¹
c = 11.4870 (3) Å	T = 120 K
β = 96.7094 (10)°	Block, colourless
V = 1415.87 (5) Å³	0.55 × 0.37 × 0.18 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	3249 independent reflections
Radiation source: fine-focus sealed tube	2906 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω and φ scans	θ_max = 27.5°, θ_min = 2.9°
Absorption correction: multi-scan SADABS (Bruker, 2003)	h = −18→18
T_min = 0.266, T_max = 0.573	k = −11→11
19150 measured reflections	l = −14→14

Refinement top

Refinement on F²	Secondary atom site location: none
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.024	H-atom parameters constrained
wR(F²) = 0.060	w = 1/[σ²(F_o²) + (0.0257P)² + 1.1891P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3249 reflections	Δρ_max = 0.36 e Å⁻³
183 parameters	Δρ_min = −0.58 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0135 (6)

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
C1	0.06540 (12)	0.5985 (2)	0.21192 (16)	0.0146 (3)
C2	0.05661 (13)	0.6274 (2)	0.32927 (17)	0.0168 (4)
H2	0.0102	0.6973	0.3505	0.020*
C3	0.11671 (12)	0.5522 (2)	0.41443 (16)	0.0155 (4)
H3	0.1113	0.5701	0.4949	0.019*
C4	0.18529 (12)	0.45017 (19)	0.38280 (15)	0.0121 (3)
C5	0.19221 (12)	0.4226 (2)	0.26447 (15)	0.0133 (3)
H5	0.2387	0.3531	0.2428	0.016*
C6	0.13172 (12)	0.4960 (2)	0.17835 (15)	0.0142 (3)
H6	0.1357	0.4764	0.0978	0.017*
C7	0.23978 (12)	0.35782 (19)	0.47705 (15)	0.0126 (3)
C8	0.34100 (12)	0.31417 (19)	0.46523 (15)	0.0125 (3)
C9	0.39851 (12)	0.39414 (19)	0.40209 (15)	0.0124 (3)
H9	0.3665	0.4779	0.3636	0.015*
C10	0.49874 (12)	0.38168 (19)	0.37913 (15)	0.0124 (3)
C11	0.52953 (12)	0.4872 (2)	0.30057 (15)	0.0147 (3)
H11	0.4856	0.5621	0.2685	0.018*
C12	0.62195 (13)	0.4858 (2)	0.26810 (15)	0.0163 (4)
H12	0.6408	0.5586	0.2146	0.020*
C13	0.68678 (13)	0.3769 (2)	0.31473 (16)	0.0164 (4)
C14	0.65847 (13)	0.2725 (2)	0.39495 (18)	0.0196 (4)
H14	0.7032	0.1993	0.4280	0.024*
C15	0.56618 (13)	0.2744 (2)	0.42692 (16)	0.0167 (4)
H15	0.5482	0.2026	0.4817	0.020*
C16	0.81160 (14)	0.4659 (2)	0.20706 (19)	0.0240 (4)
H16A	0.8783	0.4420	0.1956	0.036*
H16B	0.8083	0.5691	0.2367	0.036*
H16C	0.7706	0.4571	0.1321	0.036*
O1	0.77892 (10)	0.36308 (15)	0.28995 (13)	0.0228 (3)
O2	0.20035 (9)	0.31697 (15)	0.56104 (11)	0.0184 (3)
Cl1	−0.00923 (3)	0.69297 (5)	0.10428 (4)	0.02141 (11)
Br1	0.382362 (13)	0.14483 (2)	0.558415 (16)	0.01882 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0103 (8)	0.0151 (8)	0.0181 (9)	−0.0012 (7)	−0.0002 (6)	0.0050 (7)
C2	0.0142 (8)	0.0156 (9)	0.0214 (9)	0.0031 (7)	0.0053 (7)	0.0006 (7)
C3	0.0159 (9)	0.0162 (9)	0.0150 (8)	−0.0007 (7)	0.0044 (7)	−0.0014 (7)
C4	0.0087 (8)	0.0131 (8)	0.0145 (8)	−0.0024 (6)	0.0015 (6)	0.0007 (6)
C5	0.0099 (8)	0.0142 (8)	0.0161 (8)	0.0003 (6)	0.0032 (6)	−0.0009 (6)
C6	0.0122 (8)	0.0174 (9)	0.0130 (8)	−0.0016 (7)	0.0012 (6)	0.0005 (7)
C7	0.0122 (8)	0.0127 (8)	0.0129 (8)	−0.0026 (6)	0.0014 (6)	−0.0019 (6)
C8	0.0125 (8)	0.0119 (8)	0.0125 (8)	0.0021 (6)	−0.0012 (6)	0.0003 (6)
C9	0.0126 (8)	0.0114 (8)	0.0127 (8)	0.0002 (6)	−0.0011 (6)	0.0005 (6)
C10	0.0106 (8)	0.0135 (8)	0.0129 (8)	−0.0023 (6)	0.0002 (6)	−0.0015 (6)
C11	0.0129 (8)	0.0159 (9)	0.0147 (8)	0.0003 (7)	−0.0008 (7)	0.0019 (7)
C12	0.0152 (8)	0.0186 (9)	0.0153 (8)	−0.0025 (7)	0.0029 (7)	0.0016 (7)
C13	0.0117 (8)	0.0171 (9)	0.0210 (9)	−0.0015 (7)	0.0045 (7)	−0.0033 (7)
C14	0.0151 (9)	0.0150 (9)	0.0290 (10)	0.0038 (7)	0.0034 (7)	0.0039 (7)
C15	0.0144 (9)	0.0146 (9)	0.0214 (9)	−0.0008 (7)	0.0032 (7)	0.0034 (7)
C16	0.0180 (9)	0.0257 (10)	0.0304 (11)	−0.0012 (8)	0.0114 (8)	0.0021 (8)
O1	0.0129 (6)	0.0220 (7)	0.0355 (8)	0.0016 (5)	0.0106 (6)	0.0050 (6)
O2	0.0164 (6)	0.0233 (7)	0.0161 (6)	−0.0004 (5)	0.0053 (5)	0.0043 (5)
Cl1	0.0155 (2)	0.0261 (2)	0.0222 (2)	0.00535 (18)	0.00078 (17)	0.00994 (18)
Br1	0.01765 (11)	0.01849 (11)	0.02112 (11)	0.00434 (7)	0.00564 (7)	0.00930 (7)

Geometric parameters (Å, º) top

C1—C6	1.385 (2)	C9—H9	0.9500
C1—C2	1.392 (3)	C10—C11	1.403 (2)
C1—Cl1	1.7375 (18)	C10—C15	1.406 (2)
C2—C3	1.384 (3)	C11—C12	1.386 (2)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.398 (2)	C12—C13	1.390 (3)
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.395 (2)	C13—O1	1.357 (2)
C4—C7	1.494 (2)	C13—C14	1.396 (3)
C5—C6	1.387 (2)	C14—C15	1.382 (3)
C5—H5	0.9500	C14—H14	0.9500
C6—H6	0.9500	C15—H15	0.9500
C7—O2	1.221 (2)	C16—O1	1.432 (2)
C7—C8	1.488 (2)	C16—H16A	0.9800
C8—C9	1.346 (2)	C16—H16B	0.9800
C8—Br1	1.8963 (17)	C16—H16C	0.9800
C9—C10	1.460 (2)

C6—C1—C2	121.89 (17)	C10—C9—H9	112.6
C6—C1—Cl1	118.98 (14)	C11—C10—C15	117.48 (15)
C2—C1—Cl1	119.13 (14)	C11—C10—C9	116.02 (15)
C3—C2—C1	118.74 (16)	C15—C10—C9	126.49 (16)
C3—C2—H2	120.6	C12—C11—C10	122.22 (17)
C1—C2—H2	120.6	C12—C11—H11	118.9
C2—C3—C4	120.46 (16)	C10—C11—H11	118.9
C2—C3—H3	119.8	C11—C12—C13	119.26 (16)
C4—C3—H3	119.8	C11—C12—H12	120.4
C5—C4—C3	119.64 (16)	C13—C12—H12	120.4
C5—C4—C7	121.48 (15)	O1—C13—C12	125.05 (16)
C3—C4—C7	118.33 (15)	O1—C13—C14	115.33 (16)
C6—C5—C4	120.44 (16)	C12—C13—C14	119.61 (16)
C6—C5—H5	119.8	C15—C14—C13	120.84 (17)
C4—C5—H5	119.8	C15—C14—H14	119.6
C1—C6—C5	118.83 (16)	C13—C14—H14	119.6
C1—C6—H6	120.6	C14—C15—C10	120.58 (16)
C5—C6—H6	120.6	C14—C15—H15	119.7
O2—C7—C8	121.10 (16)	C10—C15—H15	119.7
O2—C7—C4	119.78 (15)	O1—C16—H16A	109.5
C8—C7—C4	119.11 (14)	O1—C16—H16B	109.5
C9—C8—C7	123.07 (16)	H16A—C16—H16B	109.5
C9—C8—Br1	124.08 (13)	O1—C16—H16C	109.5
C7—C8—Br1	112.66 (12)	H16A—C16—H16C	109.5
C8—C9—C10	134.71 (16)	H16B—C16—H16C	109.5
C8—C9—H9	112.6	C13—O1—C16	117.81 (15)

C6—C1—C2—C3	0.6 (3)	C4—C7—C8—Br1	−159.02 (12)
Cl1—C1—C2—C3	−179.65 (14)	C7—C8—C9—C10	177.38 (18)
C1—C2—C3—C4	0.4 (3)	Br1—C8—C9—C10	2.7 (3)
C2—C3—C4—C5	−0.8 (3)	C8—C9—C10—C11	176.46 (19)
C2—C3—C4—C7	−172.42 (16)	C8—C9—C10—C15	−2.9 (3)
C3—C4—C5—C6	0.2 (3)	C15—C10—C11—C12	1.4 (3)
C7—C4—C5—C6	171.47 (16)	C9—C10—C11—C12	−178.08 (16)
C2—C1—C6—C5	−1.3 (3)	C10—C11—C12—C13	−0.1 (3)
Cl1—C1—C6—C5	178.99 (13)	C11—C12—C13—O1	179.83 (17)
C4—C5—C6—C1	0.9 (3)	C11—C12—C13—C14	−1.2 (3)
C5—C4—C7—O2	−137.69 (17)	O1—C13—C14—C15	−179.67 (17)
C3—C4—C7—O2	33.7 (2)	C12—C13—C14—C15	1.2 (3)
C5—C4—C7—C8	40.9 (2)	C13—C14—C15—C10	0.0 (3)
C3—C4—C7—C8	−147.67 (16)	C11—C10—C15—C14	−1.3 (3)
O2—C7—C8—C9	−155.64 (17)	C9—C10—C15—C14	178.08 (18)
C4—C7—C8—C9	25.8 (2)	C12—C13—O1—C16	−1.7 (3)
O2—C7—C8—Br1	19.6 (2)	C14—C13—O1—C16	179.23 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15···Br1	0.95	2.62	3.3339 (18)	132

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection. One of the authors (BKS) thanks AICTE, Government of India, New Delhi for financial assistance under the 'Career Award for Young Teachers' Scheme.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L. Orpen, A. G. & Taylor, R. (1987).J. Chem. Soc. Perkin Trans. 2. p.p. S1–19. CrossRef Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–000. CrossRef CAS Google Scholar
Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Harrison, W. T. A., Yathirajan, H. K., Sarojini, B. K., Narayana, B. & Anilkumar, H. G. (2005). Acta Cryst. C61, o728–o730. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Moorthi, S. S., Chinnakali, K., Nanjundan, S., Radhika, R., Fun, H.-K. & Yu, X.-L. (2005). Acta Cryst. E61, o480–o482. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter, Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Patil, P. S., Ng, S.-L., Razak, I. A., Fun, H.-K. & Dharmaprakask, S. M. (2006). Acta Cryst. E62, o1465–o1465. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Uchida, T., Kozawa, K., Sakai, T., Aoki, M., Yoguchi, H., Abduryim, A. & Watanabe, Y. (1998). Mol. Cryst. Liq. Cryst. 315, 135–140. Web of Science CrossRef Google Scholar
Watson, G. J. R., Turner, A. B. & Allen, S. (1993). Organic Materials for Non-linear Optics III, edited by G. J. Ashwell & D. Bloor. RSC Special Publication No. 137, pp 112–117. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.