Methyl 4,4′′-difluoro-5′-meth­oxy-1,1′:3′,1′′-terphenyl-4′-carboxyl­ate

Hoong-Kun Fun; Tze Shyang Chia; S Samshuddin; B Narayana; B K Sarojini

doi:10.1107/S1600536811048719

. 2011 Nov 23;67(Pt 12):o3390. doi: 10.1107/S1600536811048719

Methyl 4,4′′-difluoro-5′-methoxy-1,1′:3′,1′′-terphenyl-4′-carboxylate

Hoong-Kun Fun ^a,^*,^‡, Tze Shyang Chia ^a, S Samshuddin ^b, B Narayana ^b, B K Sarojini ^c

PMCID: PMC3239031 PMID: 22199879

Abstract

In the title compound, C₂₁H₁₆F₂O₃, the pendant fluorobenzene rings form dihedral angles of 22.22 (12) and 50.74 (11)° with the central benzene ring. In the crystal, molecules are linked by C—H⋯O hydrogen bonds into chains along the a axis. The crystal structure also features C—H⋯π interactions.

Related literature

For a related structure and background to terphenyls, see: Fun et al. (2011 ▶). For further related structures, see: Betz et al. (2011a ▶,b ▶). For further synthetic details, see: Kotnis (1990 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶). For reference bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₂₁H₁₆F₂O₃
M _r = 354.34
Orthorhombic,
a = 8.1270 (1) Å
b = 9.4681 (1) Å
c = 22.3297 (3) Å
V = 1718.21 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.26 × 0.20 × 0.18 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.973, T _max = 0.982
11903 measured reflections
2851 independent reflections
2411 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.102
S = 1.13
2851 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.28 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/S1600536811048719/hb6516sup1.cif

e-67-o3390-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048719/hb6516Isup2.hkl

e-67-o3390-Isup2.hkl^{(140KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811048719/hb6516Isup3.cml

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

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

Cg1 and Cg2 are the centroids of the C13—C18 and C7–C12 benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2ⁱ	0.95	2.57	3.310 (3)	135
C1—H1A⋯Cg1ⁱⁱ	0.95	2.76	3.367 (3)	123
C19—H19A⋯Cg2ⁱⁱⁱ	0.98	2.62	3.466 (2)	144

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

Acknowledgments

HKF and TSC thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSC thanks the Malaysian Government and USM for the award of the post of Research Officer under the Research University Grant (1001/PSKBP/8630013). BN thanks the UGC for financial assistance through an SAP and BSR one-time grant for the purchase of chemicals. SS thanks Mangalore University for research facilities.

supplementary crystallographic information

Comment

As part of our ongonig studies of terphenyls (Fun et al., 2011), the title compound was prepared and its crystal structure is reported. The precursor of the title compound was prepared from 4,4'-difluoro chalcone by several steps.

The molecular structure of the title compound is shown in Fig. 1. The least-squares planes of the two fluorophenyl rings (C1–C6 & C13–C18) make dihedral angles of 22.22 (12) and 50.74 (11)°, respectively, with the least-squares plane of the central benzene ring(C7–C12) in the terphenyl moiety. Bond lengths (Allen et al., 1987) and angles are within normal ranges and are comparable to related structures (Betz et al., 2011a,b).

In the crystal structure, (Fig. 2), the molecules are interconnected by C1—H1A···O2 hydrogen bonds (Table 1) into infinite chains along a axis. The crystal structure is further stabilized by C—H···π interactions, involving the centroids of C7–C12 and C13—C18 benzene rings.

Experimental

The title compound was prepared by the aromatization of a cyclohexenone derivative, methyl 4,6-bis(4-fluorophenyl)-2-oxocyclohex-3-ene-1-carboxylate, using iodine and methanol at reflux condition (Kotnis, 1990). Colourless blocks of (I) were grown from methanol by slow evaporation method (m.p.: 401 K).