1,8-Bis(4-fluoro­benzo­yl)naphthalen-2,7-diyl dimethane­sulfonate

Daichi Hijikata; Rei Sakamoto; Katsuhiro Isozaki; Noriyuki Yonezawa; Akiko Okamoto

doi:10.1107/S1600536813006788

. 2013 Mar 16;69(Pt 4):o544. doi: 10.1107/S1600536813006788

1,8-Bis(4-fluorobenzoyl)naphthalen-2,7-diyl dimethanesulfonate

Daichi Hijikata ^a, Rei Sakamoto ^a, Katsuhiro Isozaki ^b, Noriyuki Yonezawa ^a, Akiko Okamoto ^a,^*

PMCID: PMC3629596 PMID: 23634083

Abstract

The molecule of the title compound, C₂₆H₁₈F₂O₈S₂, lies across a crystallographic twofold rotation axis. The benzene rings of the 4-fluorobenzoyl groups make dihedral angles of 78.93 (12)° with the naphthalene ring system. An intramolecular C—H⋯π interaction occurs. In the crystal, a number of C—H⋯O interactions link the molecules, forming a three-dimensional structure.

Related literature

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶). For the crystal structures of closely related compounds, see: Watanabe et al. (2010 ▶); Tsumuki et al. (2011 ▶); Hijikata et al. (2010 ▶, 2012 ▶); Sasagawa et al. (2013 ▶).

Experimental

Crystal data

C₂₆H₁₈F₂O₈S₂
M _r = 560.52
Monoclinic,
a = 7.376 (3) Å
b = 16.468 (7) Å
c = 20.075 (9) Å
β = 96.123 (6)°
V = 2424.4 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 173 K
0.10 × 0.10 × 0.05 mm

Data collection

Rigaku Saturn70 diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.945, T _max = 0.945
8755 measured reflections
2360 independent reflections
1617 reflections with I > 2σ(I)
R _int = 0.074

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.120
S = 1.03
2360 reflections
173 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 2006 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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.^{(23.9KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813006788/su2570sup1.cif

e-69-0o544-sup1.cif^{(23.9KB, cif)}

Click here for additional data file.^{(116.1KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006788/su2570Isup2.hkl

e-69-0o544-Isup2.hkl^{(116.1KB, hkl)}

Click here for additional data file.^{(9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813006788/su2570Isup3.cml

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

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

Cg is the centroid of the C8–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14A⋯Cg	0.98	2.87	3.805 (4)	160
C14—H14B⋯O1ⁱ	0.98	2.45	3.399 (4)	163
C14—H14C⋯O4ⁱⁱ	0.98	2.46	3.304 (4)	144
C12—H12⋯O4ⁱⁱⁱ	0.95	2.50	3.285 (4)	140
C4—H4⋯O1^iv	0.95	2.54	3.415 (4)	153

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

Acknowledgments

The authors express their gratitude to Associate Professor Hikaru Takaya and Professor Masaharu Nakamura, Institute for Chemical Research, Kyoto University, for their kind advice. This work was partially supported by the Collaborative Research Program of the Institute for Chemical Research, Kyoto University (grant No. 2012–72).

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). Under these circumstances, the authors have stimulated the X-ray crystal structural study of 1,8-diaroylated 2,7-dimethoxynaphthalene analogues exemplified by 1,8-bis(4-fluorobenzoyl)-2,7-dimethoxynaphthalene [(2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorophenyl)dimethanone; Watanabe et al., 2010] and 2,7-dimethoxy-1,8-bis(2-naphthoyl)naphthalene {[2,7-dimethoxy-8-(2-naphthoyl)naphthalen-1-yl](naphthalen-2-yl)methanone; Tsumuki et al., 2011}.

Accordingly, to the best of our knowledge, these molecules have essentially the same non-coplanar features, namely: The aroyl groups at the 1,8-positions of the naphthalene ring are bonded in an almost perpendicular fashion and oriented in opposite directions (anti-orientation), but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene ring. Recently, the authors have described the crystal structures of 1,8-diaroylated 2,7-dimethoxynaphthalene analogues, in which the two aroyl groups are situated in the same direction (syn-orientation), that is, 2,7-dimethoxy-1,8-bis(4-phenoxybenzoyl)naphthalene (Hijikata et al., 2010) and 2,7-dimethoxy-1,8-bis(4-isopropoxybenzoyl)naphthalene [{2,7-dimethoxy-8-[4-(propan-2-yloxy)benzoyl]naphthalen-1-yl}[4-(propan-2-yloxy)phenyl]methanone; Sasagawa et al., 2013].

The authors then investigated the correlation between the aroyl groups and the neighbouring groups in the spatial organization of 1,8-diaroylnaphthalenes. In the crystal structure of 1,8-bis(4-fluorobenzoyl)-2,7-diphenoxynaphthalene [(4-fluorophenyl)[8-(4-fluorobenzoyl)-2,7-diphenoxynaphthalen-1-yl]methanone; Hijikata et al., 2012], two phenoxy groups are asymmetrically situated with respect to the adjacent aroyl groups. One phenoxy group is horizontal to the aroyl group, whereas another phenoxy group leans toward the naphthalene ring. As a part of our continuous study on the molecular structures of this kind of homologous molecules, the crystal structure of title compound is presented herein.

The molecule of the title compound lies across a crystallographic 2-fold axis, Fig. 1, so that the asymmetric unit contains one-half of the molecule. Thus, the two aroyl groups are situated in an anti orientation and twisted away from the naphthalene ring. The benzene ring of the aroyl group make a dihedral angle of 78.93 (12) ° with the naphthalene ring. The dihedral angle between the benzene rings of the aroyl groups is 21.55 (15) °. There are two intramolecular C—H···π interactions in the molecule involving one methyl H atom (H14A) of the methanesulfonyl group and the phenyl ring of the 4-fluorobenzoyl group (Fig. 1 and Table 1).

In the crystal, the ketonic carbonyl oxygen atom (O1) and the sulfonyl oxygen atom (O4) are involved in C—H···O interactions (Fig. 2 and Table 1). These interactions contribute to the stabilization of the packing and lead to the formation a three-dimensional structure (Fig. 2 and Table 1).

Experimental

1,8-bis(4-fluorobenzoyl)-2,7-dihydroxynaphthalene (1.0 mmol, 404 mg), methanesulfonyl chloride (2.4 mmol, 487 mg), pyridine (10.0 mmol, 791 mg), and methylene chloride (2.5 ml) were placed in a 10 ml flask. The mixture was stirred at room temperature for 24 h. After the reaction, the mixture was extracted with CHCl₃. The combined extracts were washed with 2 M 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 recrystallization from AcOEt–hexane (v/v= 2:1) [55% isolated yield; M.p. 507.4 K], giving colourless block-like crystals. Spectroscopic data for the title compound are available in the archived CIF.