(2E)-1-(3-Bromo­phen­yl)-3-(4,5-dimeth­oxy-2-nitro­phen­yl)prop-2-en-1-one

Jerry P Jasinski; Ray J Butcher; C S Chidan Kumar; H S Yathirajan; A N Mayekar

doi:10.1107/S1600536810041292

. 2010 Oct 23;66(Pt 11):o2936–o2937. doi: 10.1107/S1600536810041292

(2E)-1-(3-Bromophenyl)-3-(4,5-dimethoxy-2-nitrophenyl)prop-2-en-1-one

Jerry P Jasinski ^a,^*, Ray J Butcher ^b, C S Chidan Kumar ^c, H S Yathirajan ^c, A N Mayekar ^d

PMCID: PMC3009291 PMID: 21589107

Abstract

In the title compound, C₁₇H₁₄BrNO₅, the dihedral angle between the 3-bromo-substituted benzene ring and the 4,5-dimethoxy-2-nitro-phenyl ring is 15.2 (1)°. The dihedral angles between the mean plane of the propenone group and the mean planes of the 3-bromo-substituted benzene and 4,5-dimethoxy-2-nitrophenyl rings are 6.9 (6) and 20.5 (5)°, respectively. Weak intermolecular C—H⋯O interactions contribute to crystal stability and π–π interactions [centroid–centroid distances = 3.7072 (18) and 3.6326 (18) Å] are also observed.

Related literature

For the biological activity of chalcones, see: Liu et al. (2003 ▶); Nielson et al. (1998 ▶); Rajas et al. (2002 ▶); Dinkova-Kostova et al. (1998 ▶). For their non-linear optical properties, see: Goto et al. (1991 ▶); Uchida et al. (1998 ▶);Tam et al. (1989 ▶); Indira et al. (2002 ▶); Sarojini et al. (2006 ▶). For the effect of bulky substituents on the spontaneous polarization of non-centrosymmetric crystals, see: Fichou et al. (1988 ▶). For the influence of the steric effect of the substituent on the molecular hyperpolarizability, see: Cho et al. (1996 ▶). For related structures, see: Butcher et al. (2007a ▶,b ▶,c ▶); Jasinski et al. (2010a ▶,b ▶,c ▶,d ▶,e ▶); Dutkiewicz et al. (2010 ▶); Kant et al. (2009 ▶); Yathirajan et al. (2007 ▶).

Experimental

Crystal data

C₁₇H₁₄BrNO₅
M _r = 392.20
Orthorhombic,
a = 6.8547 (2) Å
b = 8.3205 (2) Å
c = 27.1509 (6) Å
V = 1548.54 (7) Å³
Z = 4
Cu Kα radiation
μ = 3.88 mm⁻¹
T = 123 K
0.55 × 0.12 × 0.06 mm

Data collection

Oxford Diffraction Xcalibur Diffractometer with Ruby Gemini detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.490, T _max = 1.000
9914 measured reflections
3069 independent reflections
3011 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.086
S = 1.07
3069 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.42 e Å⁻³
Absolute structure: Flack (1983 ▶), 1228 Friedel pairs
Flack parameter: 0.08 (2)

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED; 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 datablocks I. DOI: 10.1107/S1600536810041292/lx2178sup1.cif

e-66-o2936-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810041292/lx2178Isup2.hkl

e-66-o2936-Isup2.hkl^{(150.6KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯O5ⁱ	0.98	2.46	3.383 (3)	157
C17—H17B⋯O3ⁱⁱ	0.98	2.48	3.116 (4)	123

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

Acknowledgments

CSC thanks the University of Mysore for the research facilities and HSY thanks the University of Mysore for sabbatical leave. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

Chalcones have displayed an impressive array of biological activities, among which antimalarial (Liu et al., 2003), antiprotozoal (Nielson et al., 1998), nitric oxide inhibition (Rajas et al., 2002) and anticancer activities (Dinkova-Kostova et al., 1998) have been cited in the literature. Among several organic compounds reported for non-linear optical (NLO) properties, chalcone derivatives are notable materials for their excellent blue-light transmittance and good crystallizability. They provide the necessary configuration to show NLO properties, with two planar rings connected through a conjugated double bond (Goto et al., 1991; Uchida et al., 1998; Tam et al., 1989; Indira et al., 2002, Sarojini et al., 2006). Substitution on either of the benzene rings greatly influences the non-centrosymmetric crystal packing. It is speculated that, in order to improve the activity, more bulky substituents should be introduced to increase the spontaneous polarization of non-centrosymmetric crystals (Fichou et al., 1988). The molecular hyperpolarizability is strongly influenced, not only by the electronic effect, but also by the steric effect of the substituent (Cho et al., 1996). The crystal structure studies of 2,3-dibromo-1-(2,4-dichlorophenyl)-3-(4,5-dimethoxy-2-nitrophenyl) propan-1-one (Yathirajan et al., 2007); (2E)-1-(4-methylphenyl)-3-(4-nitrophenyl)prop-2-en-1-one (Butcher et al., 2007a); (E)-3-(4-fluorophenyl)-1-(4-methylphenyl)prop-2-en-1-one (Butcher et al., 2007b); (2E)-3-(2-bromo-5-methoxyphenyl)-1-(2,4-dichlorophenyl) prop-2-en-1-one (Butcher et al., 2007c); (E)-3-(4-bromophenyl)-1-(3,4-dichlorophenyl)prop-2-en-1-one (Kant et al., 2009); (2E)-3-(4-bromophenyl)-1-(3-chlorophenyl) prop-2-en-1-one (Jasinski et al., 2010a); (2E)-1-(4-bromophenyl)-3-(4-fluorophenyl)prop-2-en-1-one (Dutkiewicz et al., 2010); (2E)-1-(2-bromophenyl)-3-(4-chlorophenyl) prop-2-en-1-one (Jasinski et al., 2010b); (2E)-1-(2-bromophenyl)-3-(4-methoxyphenyl)prop-2-en-1-one (Jasinski et al., 2010c); (2E)-1-(2-bromophenyl)-3- (3,4,5-trimethoxyphenyl)prop-2-en-1-one (Jasinski et al., 2010d) and (2E)-1-(2-bromophenyl)-3-(4-bromophenyl)prop-2-en-1-one (Jasinski et al., 2010e) have been reported. In continuation of our work on chalcones, the present paper reports the synthesis and crystal structure of a new chalcone, C₁₇H₁₄BrNO₅.

In the title compound the dihedral angle between the 3-bromo-substituted benzene ring and the 4,5-dimethoxy-2-nitro-phenyl ring is 15.2 (1)° (Fig. 2). The dihedral angles between the mean plane of the propenone group and the mean planes of the 3-bromo-substituted benzene and 4,5-dimethoxy-2-nitro-phenyl rings is 6.9 (6)° and 20.5 (5)°, respectively. While no classic hydrogen bonds are observed, weak intermolecular C—H···O (Table 1, Fig. 3) hydrogen bond interactions contribute to crystal stability.

Experimental

1-(3-Bromophenyl)ethanone (1.99 g, 0.01 mol) was mixed with 4,5-dimethoxy-2-nitrobenzaldehyde (2.11 g, 0.01 mol) and dissolved in methanol (30 ml). To this, 3 ml of KOH (40%) was added and the reaction mixture was stirred for 6 h (Fig. 1). The resulting crude solid was filtered, washed successively with distilled water and finally recrystallized from ethanol (95%) to give the pure chalcone. Pale yellow, small needle shaped crystals suitable for X-ray diffraction studies were grown by the slow evaporation of the dimethylformamide solution at room temperature (m.p.: 409–411 K).