1,3-Bis(biphenyl-4-yl)-2,2-dibromo-3-oxopropyl acetate

Jerry P Jasinski; James A Golen; B P Siddaraju; B Narayana; H S Yathirajan

doi:10.1107/S1600536811056169

. 2012 Jan 11;68(Pt 2):o362–o363. doi: 10.1107/S1600536811056169

1,3-Bis(biphenyl-4-yl)-2,2-dibromo-3-oxopropyl acetate

Jerry P Jasinski ^a,^*, James A Golen ^a, B P Siddaraju ^b, B Narayana ^c, H S Yathirajan ^b

PMCID: PMC3275044 PMID: 22346989

Abstract

In the title compound, C₂₉H₂₂Br₂O₃, the dihedral angles between the mean planes of the benzene rings within each biphenyl group are 26.7 (8) and 30.9 (8)°. The mean planes of the terminal and inner benzene rings of the biphenyl groups bonded through a propan-1-one group in the V-shaped molecule are oriented at angles of 66.1 (7) and 60.0 (8)°, respectively. The two Br atoms are opposite the propen-1-one group. Weak intermolecular C—H⋯O and C—H⋯π interactions are observed in the crystal structure.

Related literature

For chalcone derivatives exhibiting non-linear optical effects, see: Indira et al. (2002 ▶); Tam et al. (1989 ▶); Uchida et al. (1998 ▶). For the improvement of molecular first-order hyperpolarizabilities, see: Zhao et al. (2002 ▶). For related dibromo chalcone structures, see: Butcher et al. (2007 ▶); Narayana et al. (2007 ▶); Sarojini et al. (2007 ▶); Yathirajan et al. (2007 ▶); For the synthesis of various chalcone derivatives, see: Samshuddin et al. (2011 ▶); Jasinski et al. (2010 ▶).

Experimental

Crystal data

C₂₉H₂₂Br₂O₃
M _r = 578.29
Monoclinic,
a = 12.0497 (14) Å
b = 20.842 (2) Å
c = 9.9482 (10) Å
β = 98.743 (10)°
V = 2469.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.31 mm⁻¹
T = 173 K
0.20 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2010 ▶) T _min = 0.557, T _max = 0.733
22652 measured reflections
5881 independent reflections
3640 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.130
S = 1.02
5881 reflections
308 parameters
H-atom parameters constrained
Δρ_max = 0.72 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2010 ▶); 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.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811056169/tk5043sup1.cif

e-68-0o362-sup1.cif^{(22.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811056169/tk5043Isup2.hkl

e-68-0o362-Isup2.hkl^{(287.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811056169/tk5043Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg4 is the centroid of the C24–C29 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1C⋯O1ⁱ	0.98	2.41	3.336 (6)	158
C17—H17A⋯O3ⁱⁱ	0.95	2.47	3.369 (5)	158
C20—H20A⋯Cg4ⁱⁱⁱ	0.95	2.82	3.707 (4)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

BPS thanks the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

Among several organic compounds exhibiting NLO effects, chalcone derivatives are important materials for their excellent blue light transmittance and good crystallizability. It has been observed that substitution of a bromo group on either of the phenyl rings greatly influences non-centrosymmetric crystal packing (Uchida et al., 1998; Tam et al., 1989; Indira et al., 2002). Bromo substituents can obviously improve molecular first-order hyperpolarizabilities and can effectively reduce dipole-dipole interactions between molecules (Zhao et al., 2002). Chalcone derivatives usually have lower melting points, which can be a drawback when their crystals are used in optical instruments. Chalcone dibromides usually have higher melting points and are thermally stable. In order to synthesize the dibromo derivative of this chalcone, (2E)-1,3-di(biphenyl-4-yl)prop-2-en-1-one was brominated using bromine in acetic acid. But instead of the dibromo derivative of this chalcone, a new product 2,2-dibromo-1,3-di(biphenyl-4-yl)-3-oxopropyl acetate (I) has been obtained.

The crystal structures of some dibromo chalcones viz., 2,3-dibromo-3-(5-bromo-2-methoxyphenyl)-1-(2,4-dichlorophenyl) propan-1-one (Narayana et al., 2007), 2,3-dibromo-3-(4-bromo-6-methoxy -2-naphthyl)-1-(4-methoxyphenyl)propan-1-one (Sarojini et al., 2007), 2,3-dibromo-3-(5-bromo-6-methoxy-2-naphthyl)-1-(2,4-dichlorophenyl) propan-1-one (Yathirajan et al., 2007) and (2Z)-2-bromo-3-[3,5-dibromo-4-(ethylamino)phenyl]-1- (2,4-dichlorophenyl)prop-2-en-1-one (Butcher et al., 2007) have been reported. In continuation of our work on synthesis of various derivatives of chalcone (Samshuddin et al., 2011; Jasinski et al., 2010), the title chalcone dibromide, (I), was prepared and its crystal structure is reported.

In the crystal structure of (I), the dihedral angles between the mean planes of the benzene rings within each biphenyl group are 26.7 (8)° and 30.9 (8)° (Fig. 1). The mean planes of the terminal and inner benzene rings of the biphenyl groups bonded through a propan-1-one group in the V-shaped molecule are oriented at angles of 66.1 (7) and 60.0 (8)°, respectively. The two bromine atoms are opposite the propen-1-one group extending in an apical configuration. Weak C—H···O and C—H···Cg π-ring intermolecular interactions are observed in the crystal structure (Table 1, Fig. 2).

Experimental

To a solution of (2E)-1,3-di(biphenyl-4-yl)prop-2-en-1-one (3.60 g, 0.01 mol) in acetic acid (25 ml), bromine (1.60 g, 0.01 mol) in acetic acid (10 ml) was added slowly with stirring at 273 K. After completion of the addition of the bromine solution, the reaction mixture was stirred for 5 h. The solid obtained was filtered and recrystallized from acetone. Single crystals were grown from its methanol solution by slow evaporation. The yield of the compound was 86%. (m.p.: 445 K).