(E)-1-(4,4′′-Difluoro-5′-meth­oxy-1,1′:3′,1′′-terphenyl-4′-yl)-3-(6-meth­oxy­naphthalen-2-yl)prop-2-en-1-one

Hoong-Kun Fun; Madhukar Hemamalini; S Samshuddin; B Narayana; B K Sarojini

doi:10.1107/S1600536811047660

. 2011 Nov 16;67(Pt 12):o3327–o3328. doi: 10.1107/S1600536811047660

(E)-1-(4,4′′-Difluoro-5′-methoxy-1,1′:3′,1′′-terphenyl-4′-yl)-3-(6-methoxynaphthalen-2-yl)prop-2-en-1-one

Hoong-Kun Fun ^a,^*,^‡, Madhukar Hemamalini ^a, S Samshuddin ^b, B Narayana ^b, B K Sarojini ^c

PMCID: PMC3238976 PMID: 22199825

Abstract

In the title compound, C₃₃H₂₄F₂O₃, the central benzene ring makes dihedral angles of 44.71 (10), 47.80 (10) and 63.68 (9)° with the two fluoro-substituted benzene rings and the naphthalene ring system, respectively. In the crystal, molecules are connected via intermolecular C—H⋯F and C—H⋯O hydrogen bonds. Furthermore, the crystal structure is stabilized by weak C—H⋯π and π–π interactions [centroid–centroid distance = 3.6816 (13) Å].

Related literature

For applications of chalcones, see: Dhar (1981 ▶); Dimmock et al. (1999 ▶); Satyanarayana et al. (2004 ▶); Sarojini et al. (2006 ▶); Liu (2006 ▶); Astruc (2002 ▶). For related structures, see: Samshuddin, Narayana et al. (2011 ▶); Samshuddin, Butcher et al. (2011 ▶); Fun et al. (2010a ▶,b ▶); Jasinski et al. (2010a ▶,b ▶); Baktır et al. (2011a ▶,b ▶).

Experimental

Crystal data

C₃₃H₂₄F₂O₃
M _r = 506.52
Monoclinic,
a = 6.9524 (5) Å
b = 33.024 (2) Å
c = 11.6030 (9) Å
β = 107.267 (1)°
V = 2544.0 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.36 × 0.16 × 0.08 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.967, T _max = 0.993
53824 measured reflections
7441 independent reflections
4312 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.180
S = 1.02
7441 reflections
345 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811047660/is5005sup1.cif

e-67-o3327-sup1.cif^{(25.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047660/is5005Isup2.hkl

e-67-o3327-Isup2.hkl^{(356.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047660/is5005Isup3.cml

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

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

Cg1, Cg3 and Cg4 are the centroids of the C1–C3/C8–C10, C14–C19 and C20–C25 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C28—H28A⋯O2ⁱ	0.93	2.53	3.363 (3)	148
C32—H32C⋯F1ⁱⁱ	0.96	2.40	3.275 (4)	152
C33—H33A⋯F2ⁱⁱⁱ	0.96	2.48	3.404 (3)	162
C32—H32A⋯Cg1^iv	0.96	2.82	3.767 (4)	168
C24—H24A⋯Cg3^v	0.93	2.83	3.461 (3)	126
C33—H33B⋯Cg3^vi	0.96	2.91	3.556 (3)	126
C7—H7A⋯Cg4ⁱⁱⁱ	0.93	2.85	3.548 (3)	133

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

Acknowledgments

HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH also thanks Universiti Sains Malaysia for a post-doctoral research fellowship. BN thanks the UGC for financial assistance under an SAP and BSR one-time grant for the purchase of chemicals. SS thanks Mangalore University for research facilities.

supplementary crystallographic information

Comment

Chalcones are highly reactive substances of varied nature. They have been reported to possess many interesting pharmacological properties (Dhar, 1981) including anti-inflammatory, antimicrobial, antifungal, antioxidant, cytotoxic, antitumor and anticancer activities (Dimmock et al., 1999; Satyanarayana et al., 2004). Chalcones also find application as organic nonlinear optical materials (NLO) for their SHG conversion efficiency (Sarojini et al., 2006). The basic skeleton of chalcones which possess α,β-unsaturated carbonyl group is a useful synthone for the synthesis of various biodynamic cyclic derivatives such as pyrazoline, benzodiazepine, 2,4,6-triarylpyridine, isoxazoline and cyclohexenone derivatives. Polysubstituted aromatics are key structures of great efficacy in synthetic, medicinal and natural product chemistry. In recent years, it has been reported that some terphenyls exhibit considerable biological activities, e.g., potent anticoagulant, immunosuppressants, anti-thrombotic, neuroprotective, specific 5-lipoxygenase inhibitory and cytotoxic activities (Liu, 2006). Due to their promising biological activities and important properties, terphenyls have generated increasing research interests. As such, the synthesis of polysubstituted aromatics has been a fascinating area in organic chemistry (Astruc, 2002).

In view of the pharmacological importance of terphenyls and chalcones, and in continuation of our work on synthesis of various derivatives of 4,4'-difluorochalcone (Samshuddin, Narayana et al., 2011; Samshuddin, Butcher et al., 2011; Fun et al., 2010a,b; Jasinski et al., 2010a,b; Baktır et al., 2011a,b), the title compound (I) is prepared and its crystal structure is reported. The precursor of the title compound was prepared from 4,4'-difluorochalcone using several steps.

The asymmetric unit of the title compound as shown in Fig. 1. The naphthalene (C1–C10) ring system is approximately planar with a maximum deviation of 0.055 (2) Å for atom C10. The central benzene (C14–C19) ring makes dihedral angles of 44.71 (10), 47.80 (10) and 63.68 (9)° with the attached two fluoro-substituted benzene (C20–C25 and C26–C31) rings and the naphthalene (C1–C10) ring system, respectively.

In the crystal structure, (Fig. 2), the molecules are connected via intermolecular C—H···F and C—H···O hydrogen bonds. Furthermore, the crystal structure is stabilized by a weak π–π interaction between the benzene (C26–C31) rings [Cg···Cg(-x, -y, 2 - z) = 3.6816 (13) Å] and C—H···π (Table 1) interactions, involving the centroids of the C1–C3/C8–C10 (Cg1), C14–C19 (Cg3) and C20–C25 (Cg4) rings.

Experimental

To a mixture of 1-(4,4''-difluoro-5'-methoxy-1,1':3',1''-terphenyl-4'-yl) ethanone (0.338 g, 0.001 mol) and 6-methoxy-2-naphthaldehyde (0.188 g, 0.001 mol) in 30 ml ethanol, 0.5 ml of 10% sodium hydroxide solution was added and stirred at 5–10 °C for 3 hours. The precipitate formed was collected by filtration and purified by recrystallization from ethanol. Single crystals were grown from DMF by slow evaporation method and the yield of the compound was 84% (m.p. 479K).