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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 5| May 2013| Page o651
https://doi.org/10.1107/S1600536813008581

(4-Eth­­oxy­benzo­yl)[8-(4-eth­­oxy­benzo­yl)-2,7-di­meth­­oxy­naphthalen-1-yl]methanone

Kosuke Sasagawa,a Rei Sakamoto,a Daichi Hijikata,a Noriyuki Yonezawaa and Akiko Okamotoa*

aDepartment of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture & Technology, Koganei, Tokyo 184-8588, Japan
*Correspondence e-mail: aokamoto@cc.tuat.ac.jp

(Received 5 March 2013; accepted 28 March 2013; online 5 April 2013)

The title mol­ecule, C30H28O6, possesses crystallographically imposed twofold symmetry, with two central C atoms in the naphthalene unit lying on the rotation axis along [001]. The 4-eth­oxy­benzoyl groups at the peri positions of the naphthalene ring system are disordered over two sets of sites with occupancies of 0.769 (4) and 0.231 (4). They are directed in opposite directions from the naphthalene plane (anti orientation). For the major component, the dihedral angle between the aroyl benzene ring and the naphthalene ring system is 75.62 (13)° [minor component 75.5 (4)°], and that between the aroyl benzene rings is 32.58 (15)°. In the crystal, mol­ecules are linked via C—H⋯O and C—H⋯π inter­actions, forming a three-dimensional network.

Related literature

For formation reactions of aroylated naphthalene compounds via electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009[Okamoto, A. & Yonezawa, N. (2009). Chem. Lett. 38, 914-915.]); Okamoto et al. (2011[Okamoto, A., Mitsui, R., Oike, H. & Yonezawa, N. (2011). Chem. Lett. 40, 1283-1284.]). For the structures of closely related compounds, see: Hijikata et al. (2010[Hijikata, D., Takada, T., Nagasawa, A., Okamoto, A. & Yonezawa, N. (2010). Acta Cryst. E66, o2902-o2903.]); Sasagawa et al. (2011[Sasagawa, K., Muto, T., Okamoto, A., Oike, H. & Yonezawa, N. (2011). Acta Cryst. E67, o3354.], 2012[Sasagawa, K., Hijikata, D., Sakamoto, R., Okamoto, A. & Yonezawa, N. (2012). Acta Cryst. E68, o3348.]); Sasagawa, Sakamoto et al. (2013[Sasagawa, K., Sakamoto, R., Kusakabe, T., Okamoto, A. & Yonezawa, N. (2013). Acta Cryst. E69, o146.]); Sasagawa, Takeuchi et al. (2013[Sasagawa, K., Takeuchi, R., Kusakabe, T., Yonezawa, N. & Okamoto, A. (2013). Acta Cryst. E69, o444-o445.]).

[Scheme 1]

Experimental

Crystal data

  • C30H28O6

  • Mr = 484.52

  • Orthorhombic, F d d d

  • a = 19.6446 (4) Å

  • b = 21.5251 (4) Å

  • c = 22.9585 (4) Å

  • V = 9708.0 (3) Å3

  • Z = 16

  • Cu Kα radiation

  • μ = 0.75 mm−1

  • T = 193 K

  • 0.60 × 0.50 × 0.50 mm
Data collection

  • Rigaku R-AXIS RAPID diffractometer

  • Absorption correction: numerical (NUMABS; Higashi, 1999[Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.662, Tmax = 0.706

  • 40441 measured reflections

  • 2230 independent reflections

  • 2113 reflections with I > 2σ(I)

  • Rint = 0.025
Refinement

  • R[F2 > 2σ(F2)] = 0.041

  • wR(F2) = 0.099

  • S = 1.15

  • 2230 reflections

  • 238 parameters

  • 20 restraints

  • H-atom parameters constrained

  • Δρmax = 0.20 e Å−3

  • Δρmin = −0.31 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C8–C13 and C1-C6 rings, respectively
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C16—H16C⋯O1i 0.98 2.51 3.4919 (16) 175
C14—H14C⋯Cg1i 0.98 2.83 3.716 (2) 151
C15—H15B⋯Cg2i 0.99 2.80 3.6831 (19) 149
Symmetry code: (i) [-x+1, y+{\script{1\over 4}}, z+{\script{1\over 4}}].

Data collection: PROCESS-AUTO (Rigaku, 1998[Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: PROCESS-AUTO; data reduction: PROCESS-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813008581/gk2562sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813008581/gk2562Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813008581/gk2562Isup3.cml

checkCIF report


Comment top

In the course of our study on selective electrophilic aromatic aroylation of the naphthalene ring core, 1,8-diaroylnaphthalene compounds have proved to be formed regioselectively by the aid of a suitable acidic mediator (Okamoto & Yonezawa, 2009, Okamoto et al., 2011). Recently, we have reported the X-ray crystal structures of 1,8-diaroylated 2,7-dimethoxynaphthalene derivatives such as 1,8-bis(4-butoxylbenzoyl)-2,7-dimethoxynaphthalene [{8-[4-(butoxy)benzoyl]-2,7-dimethoxynaphthalen-1-yl}[4-(butoxy)phenyl]methanone] (Sasagawa et al., 2011), 1,8-bis(4-methoxybenzoyl)-2,7-dimethoxynaphthalene [{2,7-dimethoxy-8-(4-methoxybenzoyl)-naphthalen-1-yl}(4-methoxyphenyl)-methanone chloroform monosolvate] (Sasagawa, Sakamoto et al., 2013) and 1,8-bis(4-isobutylbenzoyl)-2,7-dimethoxynaphthalene [{2,7-dimethoxy-8-[4-(2-methylpropyl)benzoyl]-naphthalen-1-yl}{4-(2-methylpropyl)phenyl-methanone}] (Sasagawa et al., 2012).

The aroyl groups in these compounds are almost perpendicularly attached to the naphthalene rings and oriented in opposite directions (anti-orientation). According to the authors' knowledge, most 1,8-diaroylnaphthalene derivatives have anti-oriented structures. Recently, we have also clarified another structure of the 1,8-diaroylnaphthalene derivatives, where the two aroyl groups are situated in same direction (syn-orientation), 2,7-dimethoxy-1,8-bis(4-phenoxybenzoyl)naphthalene (Hijikata et al., 2010) and 1,8-bis(4-isopropoxybenzoyl)-2,7-dimethoxynaphthalene [{2,7-dimethoxy-8-[4-(propan-2-yloxy)-benzoyl]naphthalen-1-yl}[4-(propan-2-yloxy)phenyl]methanone] (Sasagawa, Takeuchi et al., 2013). As a part of our ongoing studies on the molecular structures of these kinds of homologous molecules, the X-ray crystal structure of the title compound, 1,8-diaroylated naphthalene bearing ethoxy groups on the aroyl moieties, is discussed herein.

The molecular structure of the title compound is displayed in Fig 1. The title molecule lies on a crystallographic twofold axis so that the asymmetric unit contains one-half of the molecule. Thus, two 4-ethoxybenzoyl groups are situated in anti-orientation and are twisted away from the attached naphthalene ring. The dihedral angle between the best planes of the 4-ethoxyphenyl groups and the naphthalene ring system is 75.62 (13)° [or 75.5 (4)° for minor position].

The torsion angles along the bond between the naphthalene ring system and the bridging carbonyl moiety, C2—C1—C7—O1, is -109.85 (12)° , whereas that between the phenyl group and the bridging carbonyl moiety (O1—C7—C8—C9) is -169.0 (4)°.

In the crystal, C—H···O and two kinds of C—H···π interactions link the molecules and form a three-dimensional network (Table 1, Fig 2; symmetry code: -x + 1, y + 1/4, z + 1/4): a C—H···O interaction between a hydrogen atom of the methyl moiety in the ethoxy group and the oxygen atom of the carbonyl moiety (C16—H16···O1 = 2.51 Å), a C—H···π interaction between a hydrogen atom of the methoxy group and the π-system of benzene ring (C14—H14C···Cg1 = 2.83 Å; Cg1 is the centroid of C8-C13 ring), and a C—H···π interactions between a hydrogen atom of the methylene moiety in the ethoxy group and the π-system of naphthalene ring (C15—H15B···Cg2 = 2.80 Å; Cg2 is the centroid of C1-C6 ring).

Related literature top

For formation reactions of aroylated naphthalene compounds via electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009); Okamoto et al. (2011). For the structures of closely related compounds, see: Hijikata et al. (2010); Sasagawa et al. (2011, 2012); Sasagawa, Sakamoto et al. (2013); Sasagawa, Takeuchi et al. (2013).

Experimental top

The title compound was prepared by SN2 reaction of 1,8-bis(4-hydroxybenzoyl)-2,7-dimethoxynaphthalene (2.0 mmol, 857 mg), which was obtained via SNAr reaction of 1,8-bis(4-fluorobenzoyl)-2,7-dimethoxynaphthalene with sodium hydroxide, with ethyl iodide (6.0 mmol, 936 mg) and potassium carbonate (5.6 mmol, 774 mg) in N,N-dimethylformamide (DMF; 5.0 ml). After the reaction mixture was stirred at 328 K for 6 h, it was poured into water (30 ml) and the mixture was extracted with CHCl3 (10 ml × 3). The combined extracts were washed with brine. The organic layers thus obtained were dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give cake (93% yield). The crude product was purified by recrystallization from ethyl acetate (isolated yield 56%). Furthermore, the isolated product was crystallized from ethyl acetate to give single crystal. (m.p. = 473.6—477.6 K). Spectroscopic data for the title compound is available in the archived CIF.

Refinement top

All H atoms were found in a difference map and were subsequently refined as riding atoms, with C—H = 0.95 (aromatic), 0.98 (methyl) and 0.99 (methylene) Å with Uĩso(H) = 1.2Ueq(C) or 1.5 Ueq(C). The 4-ethoxybenzene group is disordered over two positions with atoms C7/C7' and C16/C16' completely overlapping. The coordinates and anisotropic displacement parameters of these atomic pairs were constrained with EXYZ and EADP instructions of SHELXL-97 (Sheldrick, 2008). Moreover restraints were imposed on the geometry of the minor orientation with the instruction SAME. The occupancies of the two postions refined at 0.769 (4) and 0.231 (4).

Structure description top

In the course of our study on selective electrophilic aromatic aroylation of the naphthalene ring core, 1,8-diaroylnaphthalene compounds have proved to be formed regioselectively by the aid of a suitable acidic mediator (Okamoto & Yonezawa, 2009, Okamoto et al., 2011). Recently, we have reported the X-ray crystal structures of 1,8-diaroylated 2,7-dimethoxynaphthalene derivatives such as 1,8-bis(4-butoxylbenzoyl)-2,7-dimethoxynaphthalene [{8-[4-(butoxy)benzoyl]-2,7-dimethoxynaphthalen-1-yl}[4-(butoxy)phenyl]methanone] (Sasagawa et al., 2011), 1,8-bis(4-methoxybenzoyl)-2,7-dimethoxynaphthalene [{2,7-dimethoxy-8-(4-methoxybenzoyl)-naphthalen-1-yl}(4-methoxyphenyl)-methanone chloroform monosolvate] (Sasagawa, Sakamoto et al., 2013) and 1,8-bis(4-isobutylbenzoyl)-2,7-dimethoxynaphthalene [{2,7-dimethoxy-8-[4-(2-methylpropyl)benzoyl]-naphthalen-1-yl}{4-(2-methylpropyl)phenyl-methanone}] (Sasagawa et al., 2012).

The aroyl groups in these compounds are almost perpendicularly attached to the naphthalene rings and oriented in opposite directions (anti-orientation). According to the authors' knowledge, most 1,8-diaroylnaphthalene derivatives have anti-oriented structures. Recently, we have also clarified another structure of the 1,8-diaroylnaphthalene derivatives, where the two aroyl groups are situated in same direction (syn-orientation), 2,7-dimethoxy-1,8-bis(4-phenoxybenzoyl)naphthalene (Hijikata et al., 2010) and 1,8-bis(4-isopropoxybenzoyl)-2,7-dimethoxynaphthalene [{2,7-dimethoxy-8-[4-(propan-2-yloxy)-benzoyl]naphthalen-1-yl}[4-(propan-2-yloxy)phenyl]methanone] (Sasagawa, Takeuchi et al., 2013). As a part of our ongoing studies on the molecular structures of these kinds of homologous molecules, the X-ray crystal structure of the title compound, 1,8-diaroylated naphthalene bearing ethoxy groups on the aroyl moieties, is discussed herein.

The molecular structure of the title compound is displayed in Fig 1. The title molecule lies on a crystallographic twofold axis so that the asymmetric unit contains one-half of the molecule. Thus, two 4-ethoxybenzoyl groups are situated in anti-orientation and are twisted away from the attached naphthalene ring. The dihedral angle between the best planes of the 4-ethoxyphenyl groups and the naphthalene ring system is 75.62 (13)° [or 75.5 (4)° for minor position].

The torsion angles along the bond between the naphthalene ring system and the bridging carbonyl moiety, C2—C1—C7—O1, is -109.85 (12)° , whereas that between the phenyl group and the bridging carbonyl moiety (O1—C7—C8—C9) is -169.0 (4)°.

In the crystal, C—H···O and two kinds of C—H···π interactions link the molecules and form a three-dimensional network (Table 1, Fig 2; symmetry code: -x + 1, y + 1/4, z + 1/4): a C—H···O interaction between a hydrogen atom of the methyl moiety in the ethoxy group and the oxygen atom of the carbonyl moiety (C16—H16···O1 = 2.51 Å), a C—H···π interaction between a hydrogen atom of the methoxy group and the π-system of benzene ring (C14—H14C···Cg1 = 2.83 Å; Cg1 is the centroid of C8-C13 ring), and a C—H···π interactions between a hydrogen atom of the methylene moiety in the ethoxy group and the π-system of naphthalene ring (C15—H15B···Cg2 = 2.80 Å; Cg2 is the centroid of C1-C6 ring).

For formation reactions of aroylated naphthalene compounds via electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009); Okamoto et al. (2011). For the structures of closely related compounds, see: Hijikata et al. (2010); Sasagawa et al. (2011, 2012); Sasagawa, Sakamoto et al. (2013); Sasagawa, Takeuchi et al. (2013).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: PROCESS-AUTO (Rigaku, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); 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 with displacement ellipsoids drawn at the 50% probability level. Symmetry code for generation of unlabeled atoms: -x + 5/4, -y + 1/4, z.
[Figure 2] Fig. 2. Intermolecular C—H···O interaction between the methyl group in the ethoxy group and the ketonic carbonyl group, C—H···π interaction between the methoxy group and the benzene ring, and that between the methylene moiety of the ethoxy group and the naphthalene group [symmetry code: -x + 1, y + 1/4, z + 1/4 along the a axis (dashed lines).
(4-Ethoxybenzoyl)[8-(4-ethoxybenzoyl)-2,7-dimethoxynaphthalen-1-yl]methanone top
Crystal data top
C30H28O6F(000) = 4096
Mr = 484.52Dx = 1.326 Mg m−3
Orthorhombic, FdddCu Kα radiation, λ = 1.54187 Å
Hall symbol: -F 2uv 2vwCell parameters from 37043 reflections
a = 19.6446 (4) Åθ = 3.6–68.2°
b = 21.5251 (4) ŵ = 0.75 mm−1
c = 22.9585 (4) ÅT = 193 K
V = 9708.0 (3) Å3Block, colorless
Z = 160.60 × 0.50 × 0.50 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2230 independent reflections
Radiation source: fine-focus sealed tube2113 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
Detector resolution: 10.000 pixels mm-1θmax = 68.2°, θmin = 3.6°
ω scansh = −23→23
Absorption correction: numerical
(NUMABS; Higashi, 1999)		k = −25→25
Tmin = 0.662, Tmax = 0.706l = −27→27
40441 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.15 w = 1/[σ2(Fo2) + (0.0506P)2 + 5.2333P]
where P = (Fo2 + 2Fc2)/3
2230 reflections(Δ/σ)max = 0.001
238 parametersΔρmax = 0.20 e Å−3
20 restraintsΔρmin = −0.31 e Å−3
Crystal data top
C30H28O6V = 9708.0 (3) Å3
Mr = 484.52Z = 16
Orthorhombic, FdddCu Kα radiation
a = 19.6446 (4) ŵ = 0.75 mm−1
b = 21.5251 (4) ÅT = 193 K
c = 22.9585 (4) Å0.60 × 0.50 × 0.50 mm
Data collection top
Rigaku R-AXIS RAPID
diffractometer		2230 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)		2113 reflections with I > 2σ(I)
Tmin = 0.662, Tmax = 0.706Rint = 0.025
40441 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.04120 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.15Δρmax = 0.20 e Å−3
2230 reflectionsΔρmin = −0.31 e Å−3
238 parameters
Special details top

Experimental. Spectroscopic Data: 1H NMR δ (300 MHz, CDCl3): 1.42 (6H, t, J = 7.2 Hz), 3.71 (6H, s), 4.05 (4H, q, J = 7.2 Hz), 6.78 (4H, br), 7.20 (2H, d, J = 9.3 Hz), 7.64 (4H, br), 7.92 (2H, d, J = 9.3 Hz) p.p.m 13C NMR δ (75 MHz, CDCl3): 14.7, 56.4, 63.4, 111.2, 113.5, 121.8, 125.6, 129.6, 131.3, 131.6, 131.9, 155.9, 162.4, 194.9 p.p.m IR (KBr): 2980 (CH3), 2938 (CH2), 1658 (C=O), 1601, 1511, 1474 (Ar) cm-1 HRMS (m/z): [M+H]+ calcd. for C30H29O6, 485.1964 , found, 485.1995

m.p. = 473.6—477.6 K

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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*/UeqOcc. (<1)
O10.62404 (4)0.04943 (4)0.43348 (3)0.0512 (2)
O20.49033 (5)0.01158 (5)0.34362 (4)0.0625 (3)
C10.57676 (5)0.08569 (5)0.34527 (5)0.0422 (3)
C20.53143 (6)0.05038 (6)0.31286 (5)0.0496 (3)
C30.53080 (7)0.05265 (6)0.25136 (5)0.0569 (3)
H30.49830.02940.22970.068*
C40.57734 (7)0.08853 (6)0.22388 (5)0.0568 (4)
H40.57780.08910.18250.068*
C50.62500.12500.25413 (7)0.0485 (4)
C60.62500.12500.31675 (6)0.0415 (3)
C70.57588 (5)0.07524 (5)0.41049 (5)0.0420 (3)0.769 (4)
C80.5170 (3)0.0946 (3)0.4472 (2)0.0379 (8)0.769 (4)
C90.4673 (2)0.1329 (2)0.42483 (14)0.0446 (7)0.769 (4)
H90.46970.14510.38510.054*0.769 (4)
C100.41390 (10)0.15410 (10)0.45895 (16)0.0444 (6)0.769 (4)
H100.38030.18090.44310.053*0.769 (4)
C110.41044 (13)0.13542 (12)0.51683 (15)0.0430 (5)0.769 (4)
C120.45874 (12)0.09486 (11)0.53927 (10)0.0485 (6)0.769 (4)
H120.45520.08070.57840.058*0.769 (4)
C130.51175 (15)0.07517 (14)0.50485 (12)0.0431 (6)0.769 (4)
H130.54520.04800.52060.052*0.769 (4)
O30.36167 (7)0.15461 (6)0.55517 (6)0.0562 (5)0.769 (4)
C150.31301 (10)0.19884 (8)0.53540 (10)0.0497 (5)0.769 (4)
H15A0.28360.18030.50500.060*0.769 (4)
H15B0.33620.23560.51880.060*0.769 (4)
C160.27090 (7)0.21734 (7)0.58794 (6)0.0606 (4)0.769 (4)
H16A0.25090.18010.60560.091*0.769 (4)
H16B0.23450.24560.57570.091*0.769 (4)
H16C0.30010.23820.61650.091*0.769 (4)
C140.43576 (8)−0.01802 (9)0.31315 (8)0.0809 (5)
H14A0.40350.01350.29940.121*
H14B0.4123−0.04690.33940.121*
H14C0.4540−0.04100.27970.121*
C7'0.57588 (5)0.07524 (5)0.41049 (5)0.0420 (3)0.231 (4)
C8'0.5121 (10)0.1018 (12)0.4338 (7)0.041 (3)0.231 (4)
C9'0.4664 (6)0.1408 (6)0.4061 (4)0.036 (2)0.231 (4)
H9'0.47430.15050.36630.044*0.231 (4)
C10'0.4103 (3)0.1663 (3)0.4325 (4)0.0432 (18)0.231 (4)
H10'0.38020.19260.41150.052*0.231 (4)
C11'0.3988 (3)0.1525 (3)0.4911 (5)0.0376 (15)0.231 (4)
C12'0.4409 (4)0.1139 (4)0.5219 (3)0.0413 (17)0.231 (4)
H12'0.43190.10360.56140.050*0.231 (4)
C13'0.4977 (5)0.0900 (5)0.4926 (5)0.052 (3)0.231 (4)
H13'0.52830.06440.51380.062*0.231 (4)
O3'0.3435 (2)0.1813 (2)0.51409 (16)0.0478 (14)0.231 (4)
C15'0.3322 (3)0.1786 (3)0.5762 (2)0.0493 (17)0.231 (4)
H15C0.37210.19510.59740.059*0.231 (4)
H15D0.32430.13520.58870.059*0.231 (4)
C16'0.27090 (7)0.21734 (7)0.58794 (6)0.0606 (4)0.231 (4)
H16D0.27910.25990.57460.091*0.231 (4)
H16E0.26150.21760.62990.091*0.231 (4)
H16F0.23170.20000.56710.091*0.231 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0481 (5)0.0616 (5)0.0440 (4)0.0054 (4)−0.0029 (3)0.0054 (4)
O20.0588 (5)0.0675 (6)0.0612 (6)−0.0130 (4)−0.0051 (4)−0.0125 (4)
C10.0418 (6)0.0462 (6)0.0386 (6)0.0093 (5)−0.0023 (4)−0.0038 (4)
C20.0472 (6)0.0521 (7)0.0493 (6)0.0085 (5)−0.0060 (5)−0.0076 (5)
C30.0621 (7)0.0598 (8)0.0489 (7)0.0135 (6)−0.0169 (6)−0.0130 (6)
C40.0716 (8)0.0628 (8)0.0360 (6)0.0231 (7)−0.0098 (6)−0.0067 (5)
C50.0581 (9)0.0513 (9)0.0361 (8)0.0211 (8)0.0000.000
C60.0434 (8)0.0459 (8)0.0351 (7)0.0150 (6)0.0000.000
C70.0422 (6)0.0431 (6)0.0407 (6)−0.0017 (4)−0.0011 (4)−0.0020 (4)
C80.0411 (12)0.0420 (16)0.031 (2)−0.0027 (8)0.0015 (16)−0.0001 (18)
C90.0487 (13)0.0489 (14)0.0362 (16)0.0005 (10)0.0024 (13)0.0050 (13)
C100.0433 (10)0.0475 (10)0.0423 (17)0.0031 (7)0.0035 (12)0.0059 (12)
C110.0444 (13)0.0454 (13)0.0393 (14)−0.0013 (9)0.0061 (13)0.0015 (11)
C120.0561 (12)0.0547 (12)0.0347 (11)0.0017 (9)0.0047 (9)0.0065 (8)
C130.0458 (12)0.0476 (14)0.0361 (12)0.0041 (9)−0.0003 (9)0.0026 (9)
O30.0581 (8)0.0647 (8)0.0458 (8)0.0093 (6)0.0157 (6)0.0059 (6)
C150.0448 (10)0.0496 (9)0.0546 (11)−0.0029 (7)0.0069 (9)0.0007 (8)
C160.0530 (7)0.0703 (8)0.0584 (7)−0.0021 (6)0.0148 (6)−0.0092 (6)
C140.0606 (9)0.0851 (11)0.0969 (12)−0.0146 (8)−0.0120 (8)−0.0230 (9)
C7'0.0422 (6)0.0431 (6)0.0407 (6)−0.0017 (4)−0.0011 (4)−0.0020 (4)
C8'0.056 (6)0.049 (7)0.018 (5)−0.011 (4)−0.005 (4)0.005 (4)
C9'0.033 (3)0.043 (4)0.033 (5)0.005 (2)0.001 (3)0.000 (4)
C10'0.046 (3)0.052 (4)0.031 (4)0.000 (2)−0.003 (3)0.007 (3)
C11'0.039 (4)0.047 (3)0.027 (4)−0.003 (3)−0.004 (3)0.008 (3)
C12'0.047 (4)0.053 (5)0.024 (3)0.010 (3)−0.004 (3)0.017 (3)
C13'0.054 (5)0.046 (5)0.055 (6)0.007 (3)−0.022 (4)0.015 (3)
O3'0.042 (2)0.070 (3)0.032 (2)0.009 (2)0.0069 (17)−0.0009 (18)
C15'0.049 (3)0.068 (4)0.031 (3)−0.015 (3)0.002 (2)0.001 (3)
C16'0.0530 (7)0.0703 (8)0.0584 (7)−0.0021 (6)0.0148 (6)−0.0092 (6)
Geometric parameters (Å, º) top
O1—C71.2175 (13)C13—H130.9500
O2—C21.3595 (16)O3—C151.423 (3)
O2—C141.4300 (16)C15—C161.516 (3)
C1—C21.3871 (16)C15—H15A0.9900
C1—C61.4293 (13)C15—H15B0.9900
C1—C71.5141 (15)C16—H16A0.9800
C2—C31.4130 (17)C16—H16B0.9800
C3—C41.353 (2)C16—H16C0.9800
C3—H30.9500C14—H14A0.9800
C4—C51.4054 (15)C14—H14B0.9800
C4—H40.9500C14—H14C0.9800
C5—C4i1.4054 (15)C8'—C9'1.384 (12)
C5—C61.438 (2)C8'—C13'1.402 (12)
C6—C1i1.4293 (13)C9'—C10'1.372 (12)
C7—C81.492 (3)C9'—H9'0.9500
C8—C91.377 (4)C10'—C11'1.395 (9)
C8—C131.391 (4)C10'—H10'0.9500
C9—C101.387 (4)C11'—O3'1.357 (8)
C9—H90.9500C11'—C12'1.371 (8)
C10—C111.390 (3)C12'—C13'1.401 (12)
C10—H100.9500C12'—H12'0.9500
C11—O31.365 (3)C13'—H13'0.9500
C11—C121.389 (3)O3'—C15'1.443 (7)
C12—C131.374 (4)C15'—H15C0.9900
C12—H120.9500C15'—H15D0.9900
C2—O2—C14117.70 (12)C12—C13—C8120.7 (3)
C2—C1—C6120.28 (11)C12—C13—H13119.7
C2—C1—C7116.22 (10)C8—C13—H13119.7
C6—C1—C7123.27 (10)C11—O3—C15117.9 (3)
O2—C2—C1116.05 (11)O3—C15—C16106.77 (16)
O2—C2—C3122.35 (11)O3—C15—H15A110.4
C1—C2—C3121.52 (12)C16—C15—H15A110.4
C4—C3—C2118.67 (12)O3—C15—H15B110.4
C4—C3—H3120.7C16—C15—H15B110.4
C2—C3—H3120.7H15A—C15—H15B108.6
C3—C4—C5122.59 (11)C15—C16—H16A109.5
C3—C4—H4118.7C15—C16—H16B109.5
C5—C4—H4118.7H16A—C16—H16B109.5
C4—C5—C4i120.77 (15)C15—C16—H16C109.5
C4—C5—C6119.61 (8)H16A—C16—H16C109.5
C4i—C5—C6119.61 (8)H16B—C16—H16C109.5
C1—C6—C1i125.46 (13)C9'—C8'—C13'114.9 (10)
C1—C6—C5117.27 (7)C10'—C9'—C8'124.2 (9)
C1i—C6—C5117.27 (7)C10'—C9'—H9'117.9
O1—C7—C8119.0 (2)C8'—C9'—H9'117.9
O1—C7—C1119.18 (10)C9'—C10'—C11'118.1 (6)
C8—C7—C1121.8 (2)C9'—C10'—H10'121.0
C9—C8—C13118.9 (3)C11'—C10'—H10'121.0
C9—C8—C7120.4 (3)O3'—C11'—C12'124.0 (9)
C13—C8—C7120.7 (3)O3'—C11'—C10'114.1 (7)
C8—C9—C10121.5 (3)C12'—C11'—C10'121.9 (6)
C8—C9—H9119.3C11'—C12'—C13'117.1 (6)
C10—C9—H9119.3C11'—C12'—H12'121.5
C9—C10—C11118.8 (2)C13'—C12'—H12'121.5
C9—C10—H10120.6C12'—C13'—C8'123.9 (8)
C11—C10—H10120.6C12'—C13'—H13'118.1
O3—C11—C12115.5 (3)C8'—C13'—H13'118.1
O3—C11—C10124.3 (3)C11'—O3'—C15'119.3 (7)
C12—C11—C10120.21 (18)O3'—C15'—H15C110.5
C13—C12—C11119.9 (2)O3'—C15'—H15D110.5
C13—C12—H12120.1H15C—C15'—H15D108.7
C11—C12—H12120.1
C14—O2—C2—C1170.15 (11)O1—C7—C8—C13−10.0 (8)
C14—O2—C2—C3−12.94 (18)C1—C7—C8—C13168.8 (5)
C6—C1—C2—O2176.11 (8)C13—C8—C9—C102.3 (10)
C7—C1—C2—O21.54 (14)C7—C8—C9—C10−176.7 (4)
C6—C1—C2—C3−0.83 (16)C8—C9—C10—C11−0.7 (7)
C7—C1—C2—C3−175.40 (11)C9—C10—C11—O3177.9 (3)
O2—C2—C3—C4−174.32 (11)C9—C10—C11—C12−1.8 (4)
C1—C2—C3—C42.42 (18)O3—C11—C12—C13−177.0 (2)
C2—C3—C4—C5−1.88 (17)C10—C11—C12—C132.7 (3)
C3—C4—C5—C4i179.78 (13)C11—C12—C13—C8−1.2 (6)
C3—C4—C5—C6−0.22 (13)C9—C8—C13—C12−1.3 (10)
C2—C1—C6—C1i178.75 (11)C7—C8—C13—C12177.6 (4)
C7—C1—C6—C1i−7.09 (7)C12—C11—O3—C15176.67 (16)
C2—C1—C6—C5−1.25 (11)C10—C11—O3—C15−3.0 (3)
C7—C1—C6—C5172.91 (7)C11—O3—C15—C16−173.45 (13)
C4—C5—C6—C11.79 (7)C13'—C8'—C9'—C10'−1 (4)
C4i—C5—C6—C1−178.21 (7)C8'—C9'—C10'—C11'0 (2)
C4—C5—C6—C1i−178.21 (7)C9'—C10'—C11'—O3'178.0 (8)
C4i—C5—C6—C1i1.79 (7)C9'—C10'—C11'—C12'−1.2 (12)
C2—C1—C7—O1109.85 (12)O3'—C11'—C12'—C13'−177.1 (7)
C6—C1—C7—O1−64.54 (14)C10'—C11'—C12'—C13'2.0 (11)
C2—C1—C7—C8−68.9 (4)C11'—C12'—C13'—C8'−2 (2)
C6—C1—C7—C8116.7 (4)C9'—C8'—C13'—C12'2 (3)
O1—C7—C8—C9168.9 (5)C12'—C11'—O3'—C15'8.7 (8)
C1—C7—C8—C9−12.3 (9)C10'—C11'—O3'—C15'−170.5 (5)
Symmetry code: (i) −x+5/4, −y+1/4, z.
Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C8–C13 and C1-C6 rings, respectively
D—H···AD—HH···AD···AD—H···A
C16—H16C···O1ii0.982.513.4919 (16)175
C14—H14C···Cg1ii0.982.833.716 (2)151
C15—H15B···Cg2ii0.992.803.6831 (19)149
Symmetry code: (ii) −x+1, y+1/4, z+1/4.

Experimental details

Crystal data
Chemical formulaC30H28O6
Mr484.52
Crystal system, space groupOrthorhombic, Fddd
Temperature (K)193
a, b, c (Å)19.6446 (4), 21.5251 (4), 22.9585 (4)
V (Å3)9708.0 (3)
Z16
Radiation typeCu Kα
µ (mm−1)0.75
Crystal size (mm)0.60 × 0.50 × 0.50
Data collection
DiffractometerRigaku R-AXIS RAPID
Absorption correctionNumerical
(NUMABS; Higashi, 1999)
Tmin, Tmax0.662, 0.706
No. of measured, independent and
observed [I > 2σ(I)] reflections		40441, 2230, 2113
Rint0.025
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.099, 1.15
No. of reflections2230
No. of parameters238
No. of restraints20
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.20, −0.31

Computer programs: PROCESS-AUTO (Rigaku, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top
Cg1 and Cg2 are the centroids of the C8–C13 and C1-C6 rings, respectively
D—H···AD—HH···AD···AD—H···A
C16—H16C···O1i0.982.513.4919 (16)175
C14—H14C···Cg1i0.982.833.716 (2)151
C15—H15B···Cg2i0.992.803.6831 (19)149
Symmetry code: (i) −x+1, y+1/4, z+1/4.
 

Acknowledgements

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

References

First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
 First citationHigashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationHijikata, D., Takada, T., Nagasawa, A., Okamoto, A. & Yonezawa, N. (2010). Acta Cryst. E66, o2902–o2903.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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 First citationRigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan.  Google Scholar
 First citationSasagawa, K., Hijikata, D., Sakamoto, R., Okamoto, A. & Yonezawa, N. (2012). Acta Cryst. E68, o3348.  CSD CrossRef IUCr Journals Google Scholar
 First citationSasagawa, K., Muto, T., Okamoto, A., Oike, H. & Yonezawa, N. (2011). Acta Cryst. E67, o3354.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSasagawa, K., Sakamoto, R., Kusakabe, T., Okamoto, A. & Yonezawa, N. (2013). Acta Cryst. E69, o146.  CSD CrossRef IUCr Journals Google Scholar
 First citationSasagawa, K., Takeuchi, R., Kusakabe, T., Yonezawa, N. & Okamoto, A. (2013). Acta Cryst. E69, o444–o445.  CSD CrossRef CAS IUCr Journals Google Scholar
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ISSN: 2056-9890
Volume 69| Part 5| May 2013| Page o651
https://doi.org/10.1107/S1600536813008581
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