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Acta Cryst. (2008). E64, o807    [ doi:10.1107/S1600536808007009 ]

1,8-Dibenzoyl-2,7-dimethoxynaphthalene

K. Nakaema, S. Watanabe, A. Okamoto, K. Noguchi and N. Yonezawa

Abstract top

The molecule of the title compound, C26H20O4, is located on a twofold rotation axis. The two benzoyl groups are situated in an anti orientation. The dihedral angle between the mean planes of the phenyl ring and the naphthalene ring system is 80.25 (6)°. The phenyl and carbonyl groups in each benzoyl group are almost coplanar. The molecular packing is stabilized by weak C-H...O hydrogen bonds and a [pi]-[pi] stacking interaction between the phenyl rings [centroid-centroid and interplanar distances of 3.6383 (10) and 3.294 Å, respectively].

Comment top

The molecules with naphthalene frame, especially, peri-substituted naphthalenes, have received much attention as unique structured aromatic core compounds for variety of the functional materials. Therefore, structural analyses of peri-substituted naphthalenes have been actively performed (Cohen et al., 2004; Gore & Henrick, 1980). Recently, we have reported the structure of 1,8-bis(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Nakaema et al., 2007). In this paper, the crystallographical structural characteristics of a 1,8-diphenylated naphthalene derivative having two methoxy groups at the 2,7-positions are described as the most simple homolog of the previously reported compound. The title compound was successfully synthesized by regioselective electrophilic aromatic substitution reaction of 2,7-dimethoxynaphthalene with benzoic acid.

ORTEPIII (Burnett & Johnson, 1996) plot of title compound is displayed in Fig. 1. The molecule of (I) lies across a crystallographic 2-fold axis so that the asymmetric unit contains one-half of the molecules. Thus, the two benzoyl groups are situated in anti orientation. The benzoyl groups are twisted away from the naphthalene moiety, and the dihedral angle is 80.25 (6)°. The torsion angles between the carbonyl groups and the naphthalene ring are -76.73 (18)° [C6—C1—C7—O1], and those between the carbonyl groups and the phenyl groups are 179.75 (15)° [C13—C8—C7—O1].

In the crystal structure, the molecular packing of (I) is mainly stabilized by van der Waals interaction. In addition, the packing of the molecule is stabilized by relatively weak C—H···O hydrogen bonding, namely, C12—H12···O1i [symmetry code: (i) x, -y+1, z + 1/2], C14—H14B···O1ii [symmetry code: (ii) -x+1/2, y - 1/2, -z+1/2], and a π—π stacking interaction. In the packing, the molecules are arranged by C—H···O hydrogen bonding along the c axis of the unit cell, and by a π—π stacking interaction perpendicular the bc plane of the unit cell (Fig. 2).

Related literature top

For related literature, see: Cohen et al. (2004); Gore & Henrick (1980); Nakaema et al. (2007).

Experimental top

The title compound was prepared by electrophilic aromatic diaroylation reaction of 2,7-dimethoxynaphthalene with benzoic acid. White single crystals suitable for X-ray diffraction were obtained by recrystallization from ethanol.

Refinement top

All H atoms were found in a difference map and were subsequently refined as riding atoms, with C—H = 0.95 (aromatic) and 0.98 Å (methyl), and with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), with the atom-labeling scheme and displacement ellipsoids drawn at the 50% probability level. The symbol "_2" refers to symmetry code: -x, y, -z+1/2.
[Figure 2] Fig. 2. A partial packing diagram of the title compound, viewed down the b axis. The dashed lines indicate hydrogen bonds (blue dashed lines) and π—π stacking interactions (green dashed lines).
1,8-Dibenzoyl-2,7-dimethoxynaphthalene top
Crystal data top
C26H20O4F000 = 832
Mr = 396.42Dx = 1.334 Mg m−3
Monoclinic, C2/cCu Kα radiation
λ = 1.54187 Å
Hall symbol: -C 2ycCell parameters from 10115 reflections
a = 13.9677 (4) Åθ = 3.2–68.1º
b = 10.2145 (3) ŵ = 0.72 mm−1
c = 14.6966 (4) ÅT = 93 (2) K
β = 109.711 (2)ºNeedle, colorless
V = 1973.95 (10) Å30.50 × 0.10 × 0.10 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1807 independent reflections
Radiation source: rotating anode1461 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
Detector resolution: 10.00 pixels mm-1θmax = 68.2º
T = 93(2) Kθmin = 5.5º
ω scansh = −16→16
Absorption correction: numerical
(NUMABS; Higashi, 1999)		k = −12→12
Tmin = 0.838, Tmax = 0.930l = −17→17
17362 measured reflections
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.039  w = 1/[σ2(Fo2) + (0.0579P)2 + 0.9602P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.115(Δ/σ)max < 0.001
S = 1.08Δρmax = 0.19 e Å−3
1807 reflectionsΔρmin = −0.21 e Å−3
139 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00121 (18)
Secondary atom site location: difference Fourier map
Crystal data top
C26H20O4V = 1973.95 (10) Å3
Mr = 396.42Z = 4
Monoclinic, C2/cCu Kα
a = 13.9677 (4) ŵ = 0.72 mm−1
b = 10.2145 (3) ÅT = 93 (2) K
c = 14.6966 (4) Å0.50 × 0.10 × 0.10 mm
β = 109.711 (2)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		1807 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)		1461 reflections with I > 2σ(I)
Tmin = 0.838, Tmax = 0.930Rint = 0.027
17362 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.039139 parameters
wR(F2) = 0.115H-atom parameters constrained
S = 1.08Δρmax = 0.19 e Å−3
1807 reflectionsΔρmin = −0.21 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.11104 (8)0.59739 (10)0.22559 (7)0.0399 (3)
O20.26822 (8)0.39816 (11)0.37874 (9)0.0530 (4)
C10.09424 (11)0.39621 (13)0.29711 (10)0.0325 (3)
C20.18262 (12)0.32529 (15)0.33814 (11)0.0393 (4)
C30.18231 (14)0.18652 (16)0.33535 (12)0.0470 (4)
H30.24360.13850.36260.056*
C40.09246 (14)0.12359 (15)0.29280 (11)0.0463 (4)
H40.09190.03060.29190.056*
C50.00000.19109 (19)0.25000.0383 (5)
C60.00000.33146 (18)0.25000.0319 (4)
C70.10671 (10)0.54368 (14)0.29822 (10)0.0313 (3)
C80.11341 (10)0.61894 (13)0.38633 (10)0.0316 (3)
C90.12438 (11)0.75478 (14)0.38552 (11)0.0368 (4)
H90.12760.79700.32910.044*
C100.13055 (12)0.82794 (16)0.46611 (12)0.0431 (4)
H100.13840.92030.46520.052*
C110.12535 (12)0.76686 (17)0.54845 (12)0.0448 (4)
H110.12960.81730.60400.054*
C120.11397 (12)0.63233 (17)0.54997 (11)0.0447 (4)
H120.11020.59060.60640.054*
C130.10816 (11)0.55857 (15)0.46934 (10)0.0376 (4)
H130.10060.46620.47070.045*
C140.36309 (13)0.3343 (2)0.42144 (14)0.0592 (5)
H14A0.41710.39990.44470.071*
H14B0.37710.27830.37330.071*
H14C0.36060.28050.47580.071*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0505 (6)0.0371 (6)0.0351 (6)−0.0020 (4)0.0185 (5)0.0020 (4)
O20.0393 (6)0.0456 (7)0.0658 (8)0.0087 (5)0.0068 (5)−0.0046 (6)
C10.0421 (8)0.0273 (7)0.0311 (7)0.0034 (6)0.0161 (6)0.0006 (5)
C20.0446 (9)0.0366 (8)0.0366 (8)0.0058 (6)0.0134 (7)−0.0009 (6)
C30.0591 (10)0.0375 (9)0.0442 (9)0.0160 (7)0.0170 (8)0.0021 (7)
C40.0708 (12)0.0281 (8)0.0428 (9)0.0076 (7)0.0227 (8)0.0014 (6)
C50.0583 (13)0.0268 (10)0.0342 (11)0.0000.0212 (10)0.000
C60.0454 (11)0.0266 (9)0.0278 (10)0.0000.0177 (9)0.000
C70.0307 (7)0.0306 (7)0.0330 (8)0.0011 (5)0.0116 (6)0.0022 (6)
C80.0300 (7)0.0312 (7)0.0333 (8)−0.0003 (5)0.0101 (6)−0.0011 (6)
C90.0415 (8)0.0320 (7)0.0367 (8)0.0012 (6)0.0130 (6)0.0018 (6)
C100.0453 (9)0.0353 (8)0.0478 (10)0.0000 (6)0.0143 (7)−0.0069 (7)
C110.0426 (9)0.0515 (10)0.0415 (9)−0.0001 (7)0.0157 (7)−0.0136 (7)
C120.0493 (9)0.0534 (10)0.0356 (9)−0.0040 (7)0.0199 (7)−0.0013 (7)
C130.0408 (8)0.0359 (8)0.0381 (8)−0.0025 (6)0.0159 (6)0.0013 (6)
C140.0465 (10)0.0653 (11)0.0578 (11)0.0221 (9)0.0070 (8)−0.0151 (9)
Geometric parameters (Å, °) top
O1—C71.2197 (16)C8—C91.396 (2)
O2—C21.3633 (19)C9—C101.378 (2)
O2—C141.4194 (19)C9—H90.9500
C1—C21.382 (2)C10—C111.385 (2)
C1—C61.4264 (17)C10—H100.9500
C1—C71.5158 (19)C11—C121.384 (2)
C2—C31.418 (2)C11—H110.9500
C3—C41.360 (2)C12—C131.383 (2)
C3—H30.9500C12—H120.9500
C4—C51.4110 (19)C13—H130.9500
C4—H40.9500C14—H14A0.9800
C5—C61.434 (3)C14—H14B0.9800
C7—C81.4814 (19)C14—H14C0.9800
C8—C131.3908 (19)
C2—O2—C14119.52 (13)C13—C8—C7122.02 (13)
C2—C1—C6120.72 (14)C9—C8—C7118.88 (13)
C2—C1—C7115.70 (13)C10—C9—C8120.44 (14)
C6—C1—C7123.36 (13)C10—C9—H9119.8
O2—C2—C1115.29 (13)C8—C9—H9119.8
O2—C2—C3123.51 (14)C9—C10—C11120.00 (15)
C1—C2—C3121.19 (15)C9—C10—H10120.0
C4—C3—C2118.62 (15)C11—C10—H10120.0
C4—C3—H3120.7C12—C11—C10120.09 (15)
C2—C3—H3120.7C12—C11—H11120.0
C3—C4—C5122.54 (15)C10—C11—H11120.0
C3—C4—H4118.7C13—C12—C11120.05 (15)
C5—C4—H4118.7C13—C12—H12120.0
C4i—C5—C4121.50 (19)C11—C12—H12120.0
C4i—C5—C6119.25 (10)C12—C13—C8120.31 (14)
C4—C5—C6119.25 (10)C12—C13—H13119.8
C1—C6—C1i124.75 (17)C8—C13—H13119.8
C1—C6—C5117.62 (9)O2—C14—H14A109.5
C1i—C6—C5117.62 (9)O2—C14—H14B109.5
O1—C7—C8121.63 (13)H14A—C14—H14B109.5
O1—C7—C1118.49 (12)O2—C14—H14C109.5
C8—C7—C1119.88 (12)H14A—C14—H14C109.5
C13—C8—C9119.10 (13)H14B—C14—H14C109.5
C14—O2—C2—C1−179.05 (14)C4—C5—C6—C1i177.70 (9)
C14—O2—C2—C3−0.3 (2)C2—C1—C7—O197.99 (16)
C6—C1—C2—O2178.29 (11)C6—C1—C7—O1−76.73 (16)
C7—C1—C2—O23.43 (18)C2—C1—C7—C8−81.97 (16)
C6—C1—C2—C3−0.5 (2)C6—C1—C7—C8103.32 (14)
C7—C1—C2—C3−175.33 (14)O1—C7—C8—C13179.76 (13)
O2—C2—C3—C4−179.86 (14)C1—C7—C8—C13−0.29 (19)
C1—C2—C3—C4−1.2 (2)O1—C7—C8—C90.4 (2)
C2—C3—C4—C51.1 (2)C1—C7—C8—C9−179.69 (12)
C3—C4—C5—C4i−179.31 (17)C13—C8—C9—C100.4 (2)
C3—C4—C5—C60.69 (17)C7—C8—C9—C10179.81 (13)
C2—C1—C6—C1i−177.80 (14)C8—C9—C10—C11−0.3 (2)
C7—C1—C6—C1i−3.35 (9)C9—C10—C11—C120.0 (2)
C2—C1—C6—C52.20 (14)C10—C11—C12—C130.2 (2)
C7—C1—C6—C5176.65 (9)C11—C12—C13—C8−0.2 (2)
C4i—C5—C6—C1177.70 (9)C9—C8—C13—C12−0.1 (2)
C4—C5—C6—C1−2.30 (9)C7—C8—C13—C12−179.53 (13)
C4i—C5—C6—C1i−2.30 (9)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O1ii0.952.603.4987 (19)159
C14—H14B···O1iii0.982.393.344 (2)164
Symmetry codes: (ii) x, −y+1, z+1/2; (iii) −x+1/2, y−1/2, −z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C12—H12···O1i0.952.603.4987 (19)159
C14—H14B···O1ii0.982.393.344 (2)164
Symmetry codes: (i) x, −y+1, z+1/2; (ii) −x+1/2, y−1/2, −z+1/2.
Acknowledgements top

This work was partially supported by the Ogasawara Foundation for the Promotion of Science & Engineering, Tokyo, Japan.

references
References top

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