(4-Fluoro­phen­yl)[8-(4-fluoro­benzo­yl)-2,7-diphen­oxy­naphthalen-1-yl]methan­one

Daichi Hijikata; Kosuke Sasagawa; Sayaka Yoshiwaka; Akiko Okamoto; Noriyuki Yonezawa

doi:10.1107/S160053681204408X

. 2012 Oct 31;68(Pt 11):o3246. doi: 10.1107/S160053681204408X

(4-Fluorophenyl)[8-(4-fluorobenzoyl)-2,7-diphenoxynaphthalen-1-yl]methanone

Daichi Hijikata ^a, Kosuke Sasagawa ^a, Sayaka Yoshiwaka ^a, Akiko Okamoto ^a,^*, Noriyuki Yonezawa ^a

PMCID: PMC3515324 PMID: 23284544

Abstract

In the title compound, C₃₆H₂₂F₂O₄, the aromatic rings of the benzoyl and phenoxy groups make dihedral angles of 72.07 (5), 73.24 (5), 62.49 (5) and 77.96 (6)° with the naphthalene ring system. In the crystal, C—H⋯O hydrogen bonds and C—H⋯π interactions are observed.

Related literature

For information on electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶, 2012 ▶). For the structures of closely related compounds, see: Watanabe et al. (2010 ▶); Sakamoto et al. (2012 ▶).

Experimental

Crystal data

C₃₆H₂₂F₂O₄
M _r = 556.54
Orthorhombic,
a = 22.3058 (4) Å
b = 14.6047 (3) Å
c = 16.8302 (3) Å
V = 5482.76 (18) Å³
Z = 8
Cu Kα radiation
μ = 0.80 mm⁻¹
T = 193 K
0.50 × 0.30 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.691, T _max = 0.925
96215 measured reflections
5011 independent reflections
4671 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.091
S = 1.06
5011 reflections
380 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: Il Milione (Burla et al., 2007 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(37KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681204408X/rz5018sup1.cif

e-68-o3246-sup1.cif^{(37KB, cif)}

Click here for additional data file.^{(240.6KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204408X/rz5018Isup2.hkl

e-68-o3246-Isup2.hkl^{(240.6KB, hkl)}

Click here for additional data file.^{(10KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681204408X/rz5018Isup3.cml

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

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

Cg is the centroid of the C31–C36 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O3ⁱ	0.95	2.40	3.3477 (15)	172
C13—H13⋯Cg ⁱⁱ	0.95	2.87	3.6924 (15)	145

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

Acknowledgments

The authors express their gratitude to Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, for his technical advice. This work was partially supported by the Ogasawara Foundation for the Promotion of Science & Engineering, Tokyo, Japan.

supplementary crystallographic information

Comment

In the course of our study on electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, peri-aroylnaphthalene compounds have proven to be formed regioselectively with the aid of suitable acidic mediators (Okamoto & Yonezawa, 2009; Okamoto et al., 2011). As one of applications, the authors have integrated the resulting molecular unit to poly(ether ketone) backbone via nucleophilic aromatic substitution polycondensation (Okamoto et al., 2012). The poly(ether ketone)s composed of 1,8-diaroylenenaphthalene units show unique thermal properties and solubility for organic solvents. These curious features of the polymers can be explained on the basis of structural features of the 1,8-diaroylene naphthalene units. Under these circumstances, the authors have stimulated the X-ray crystal structural study of several 1,8-diaroylated naphthalene analogues exemplified by (2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorophenyl)dimethanone (Watanabe et al., 2010) and 1,8-dibenzoylnaphthalene-2,7-diyl dibenzoate (Sakamoto et al., 2012). These molecules have essentially the same non-coplanar features. The aroyl groups at the 1,8-positions of the naphthalene rings in these molecules are twistedly bonded in an almost perpendicular fashion, but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene rings. As a part of our continuous study on the molecular structures of this kind of homologous molecules, the X-ray crystal structure of title compound, 1,8-bis(4-fluorobenoyl)-2,7-diphenoxynaphthalene, is discussed in this article.

The molecular structure of the title compound is displayed in Fig. 1. Two benzoyl groups at 1,8-positions of the naphthalene ring are situated in opposite directions, anti orientation. The benzene rings of the benzoyl groups make dihedral angles of 72.07 (5) and 73.24 (5)° with the naphthalene ring, respectively. The dihedral angles between the phenyl rings of phenoxy groups and the naphthalene ring system are 62.49 (5) and 77.96 (6)°, respectively. The crystal packing is stabilized by an intermolecular C—H···O hydrogen bond between the oxygen atom (O3) of the carbonyl group of the adjacent molecule and one hydrogen atom (H6) on the naphthalene ring along the c axis (C6—H6···O3ⁱ = 2.40 Å; Fig. 2 and Table 1). The C—H···π interaction (C13—H13···Cgⁱⁱ = 2.87 Å; Fig. 3 and Table 1) also contributes to the stabilization of the aromatic ring alignments and the crystal structure.

Experimental

To a 10 ml flask, 1,8-bis(4-fluorobenzoyl)-2,7-dihydroxynaphthalene (1.0 mmol, 404 mg), benzeneboronic acid (4.0 mmol, 487 mg), Cu(OAc)₂ (2.0 mmol, 363 mg), activated 4 Å molecular sieves (1.0 g), pyridine (8.0 mmol, 632 mg), methylene chloride (4.0 ml) were placed. The reaction mixture was stirred at room temperature for 48 h. After the reaction, the mixture was extracted with CHCl₃. The combined extracts were washed with saturated NH₄Cl_aq and 2M aqueous HCl followed by washing with brine. The organic layers thus obtained were dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give cake. The crude product was purified by column chromatography (silica gel, hexane/CHCl₃, 1:1 v/v) to give the title compound (isolated yield 46%). Furthermore, the isolated product was crystallized from methanol to give single crystal.

¹HNMR δ (300 MHz, CDCl₃): 6.81(4H, d, J=7.5 Hz), 7.01(4H, t, J=8.5 Hz), 7.05(2H, t, J=7.5 Hz), 7.08(2H, d, J=8.9 Hz), 7.22(4H, t, J=7.5 Hz), 7.81(4H, dd, J=8.5, 5.5 Hz), 7.90(2H, d, J=8.9 Hz) p.p.m..

¹³CNMR δ (75 MHz, CDCl₃): 115.18(d, ²J_C—F=22.4 Hz), 117.21, 118.92, 123.92, 124.65, 127.85, 129.69, 130.65, 131.76(d, ³J_C—F=10.1 Hz), 132.12, 134.87(d, ⁴J_C—F=2.1 Hz), 153.73, 155.79, 165.64(d, ¹J_C—F=255.7 Hz), 194.64 p.p.m..

IR (KBr): 1666 (C=O), 1594, 1504, 1486 (Ar, naphthalene), 1262 (=C—O—C) cm^-1.

HRMS (m/z): [M + H]⁺ calcd for C₃₆H₂₃F₂O₄, 557.1564 found, 557.1569.

m.p. 441.9–443.6 K