Crystal structure of 2,7-dieth­oxy-1,8-bis­(4-nitro­benzo­yl)naphthalene

Mohri, S.; Ohisa, S.; Noguchi, K.; Yonezawa, N.; Okamoto, A.

doi:10.1107/S1600536814018674

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages 138-141

doi:10.1107/S1600536814018674

Open

access

Crystal structure of 2,7-diethoxy-1,8-bis(4-nitrobenzoyl)naphthalene

Saki Mohri,^a Shinji Ohisa,^a Keiichi Noguchi,^b Noriyuki Yonezawa ^a and Akiko Okamoto ^a ^*

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

Edited by H. Ishida, Okayama University, Japan (Received 17 July 2014; accepted 18 August 2014; online 23 August 2014)

The title compound, C₂₈H₂₂N₂O₈, possesses crystallographically imposed twofold symmetry, with the two central carbon atoms of the naphthalene unit lying on the rotation axis. The two benzoyl groups in the molecule are twisted away from the attached naphthalene unit with a C—C—C=O torsion angle of 49.05 (15)° between the naphthalene unit and the carbonyl group. The dihedral angle between the naphthalene ring system and the benzene ring is 77.17 (5)°. In the crystal, pairs of C—H⋯O=C hydrogen bonds link the molecules into a double-column structure along the c axis. The molecules are further linked by C—H⋯O=N hydrogen bonds, forming a three-dimensional network. C—H⋯π interactions between the methylene group and the naphthalene unit and π–π interactions between the naphthalene ring systems [centroid–centroid distances of 3.7858 (7)–3.7860 (7) Å] are also observed.

Keywords: crystal structure; peri-aroylnaphthalene; naphthalene diketone; non-coplanarly accumulated aromatic-rings structure; spatial organization.

CCDC reference: 1019755

1. Chemical context

Molecules with non-coplanarly accumulated aromatic rings, such as biphenyl and binaphthyl derivatives, have been in the limelight as unique building blocks affording characteristic optical and electronic properties (Hatano et al., 2013 ; Park et al., 2010 ; Vaghi et al., 2013 ) and asymmetric molecular environments (Bulman Page et al., 2012 ; Jayalakshmi et al., 2012 ; Kano et al., 2006 ; Wang et al., 2014 ). peri-Substituted naphthalenes have also much attention as characteristic aromatic ring core compounds and the structural analyses have been actively performed (Cohen et al., 2004 ; Jing et al., 2005 ).

In the course of our study on selective electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, peri-aroylnaphthalene compounds have proved to be formed regioselectively with the aid of a suitable acidic mediator (Okamoto & Yonezawa, 2009 ; Okamoto et al., 2011 ). According to X-ray crystal analysis, the resulting 1,8-diaroylnaphthalene and 1-monoaroylnaphthalene compounds have non-coplanarly accumulated aromatic-ring structures in their crystals. The aroyl groups at the 1,8-positions (or 1-position) of the naphthalene ring system in the molecules are situated in a perpendicular fashion to the naphthalene ring system, as shown in 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008 ), 1,8-dibenzoyl-2,7-diethoxynaphthalene (Isogai et al., 2013 ) and 1-(4-nitrobenzoyl)-2,7-dimethoxynaphthalene (Watanabe et al., 2010 ). As a part of our continuous study on the molecular structures of this kind of molecules, the X-ray crystal structure of the title compound is reported here.

2. Structural commentary

The title molecule lies on a crystallographic twofold axis running through atoms C5 and C6 of the naphthalene unit so that the asymmetric unit consists of one half-molecule (Fig. 1). In the molecule, two aroyl groups are non-coplanarly attached to the naphthalene ring system. The torsion angles of the benzene ring and the naphthalene ring system with the ketonic carbonyl moiety (O1—C7—C8—C13 and C6—C1—C7—O1) are 26.83 (17) and 49.05 (15)°, respectively. The dihedral angle between the benzene ring and the naphthalene ring system is 77.17 (5)°. The benzene ring and the nitro group are approximately coplanar with a dihedral angle of 5.0 (2)°.

Figure 1
The molecular structure of the title compound with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal, the molecular packing of the title compound is mainly stabilized by a pair of C—H⋯O=C hydrogen bonds between the benzene ring and the ketonic carbonyl group (C13—H13⋯O1ⁱ; details and symmetry code in Table 1), which make an R₂²(10) ring motif (Fig. 2). The molecules are stacked through these interactions in a double-column along the c axis. The molecules are also linked by C—H⋯O=N interactions between the benzene ring and the nitro group (C10—H10⋯O3ⁱⁱ; Table 1), forming a three-dimensional network and thus resulting in the interpenetration of the naphthalene unit into the adjacent double-column. π–π interactions between the interpenetrating naphthalene ring systems are observed; the interplanar distance is 3.5326 (4) Å and the centroid–centroid distances are 3.7860 (7), 3.7859 (7) and 3.7858 (7) Å, respectively, for Cg1⋯Cg1^vi, Cg1⋯Cg2^vii and Cg2⋯Cg2^viii, where Cg1 and Cg2 are the centroids of the six-membered C1–C6 and C1^v–C4^v/C5/C6 rings, respectively [symmetry codes: (v) −x + 1, y, −z + $[{1\over 2}]$ ; (vi) −x + 1, −y + 1, −z; (vii) x, −y + 1, z − $[{1\over 2}]$ ; (viii) −x + 1, −y + 1, −z + 1]. C—H⋯π interactions between the methylene group and the naphthalene ring system (C14—H14B⋯Cg1ⁱⁱⁱ and C14—H14B⋯Cg2^iv; Table 1 and Fig. 3) are also observed.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the six-membered C1–C6 and C1^v–C4^v/C5/C6 rings, respectively. [Symmetry code: (v) −x + 1, y, −z + $[{1\over 2}]$ .]

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1ⁱ	0.95	2.50	3.2129 (17)	132
C10—H10⋯O3ⁱⁱ	0.95	2.59	3.360 (2)	138
C14—H14B⋯Cg1ⁱⁱⁱ	0.99	2.81	3.6284 (15)	140
C14—H14B⋯Cg2^iv	0.99	2.81	3.6284 (15)	140
Symmetry codes: (i) -x+1, -y, -z; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y, z-{\script{1\over 2}}]$ ; (iv) -x, -y, -z+1.

Figure 2
A crystal packing view of the title compound, showing the intermolecular C—H⋯O=C and C—H⋯O=N interactions. [Symmetry codes: (i) 1 − x, −y, −z; (ii) $[{3\over 2}]$ − x, $[{1\over 2}]$ + y, $[{1\over 2}]$ − z.]

Figure 3
A crystal packing view of the title compound, showing the intermolecular C—H⋯π interactions (dashed lines) and π–π interactions (double dashed lines).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Allen, 2002 ) showed 39 and 29 structures containing the 1,8-diaroylnaphthalene (including 1,8-dialkanoylnaphthalene) and 1,8-diaroyl-2,7-dialkoxynaphthalene units, respectively. The title compound has a non-coplanarly accumulated aromatic-rings structure, as found in the nitro group-free 1,8-dibenzoylnaphthalene homologues and the nitro-group-bearing 1-benzoylnaphthalene homologue, viz. 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008) and 1,8-dibenzoyl-2,7-diethoxynaphthalene (Isogai et al., 2013), and 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe et al., 2010). The dihedral angle between the benzene ring and the naphthalene ring system [77.17 (5)°] is close to those of the three homologues [68.42 (5) and 71.69 (5)° for 1,8-dibenzoyl-2,7-diethoxynaphthalene; 83.59 (5)° for 1,8-dibenzoyl-2,7-dimethoxynaphthalene; 61.97 (5)° for 1-(4-nitrobenzoyl)-2,7-dimethoxynaphthalene]. On the other hand, the torsion angle between the carbonyl group and the benzene ring is different from the homologues, i.e., the title compound [26.83 (17)°] > 1-(4-nitrobenzoyl)-2,7-dimethoxynaphthalene [−13.29 (17)°] >> 1,8-dibenzoyl-2,7-diethoxynaphthalene [1.58 (17)° and 1.44 (17)°] > 1,8-dibenzoyl-2,7-dimethoxynaphthalene [0.4 (2)°]. Although the C—H⋯O=C interactions between the benzene ring and the ketonic carbonyl group are observed in all of four homologues, the C—H⋯O=N interaction is observed only in the title compound.

5. Synthesis and crystallization

To a 10 ml flask, 4-nitrobenzoic acid (3.96 mmol, 735 mg), aluminium chloride (4.35 mmol, 580 mg) and methyl chloride (3.0 ml) were placed and stirred at 273 K. To reaction mixture thus obtained, 2,7-diethoxynaphthalene (0.6 mmol, 130 mg) was added. After the reaction mixture was stirred at 273 K for 48 h, it was poured into ice-cold water (10 ml). The aqueous layer was extracted with CHCl₃ (10 ml×3). The combined extracts were washed with 2 M aqueous NaOH 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 reprecipitation (CHCl₃/methanol) (isolated yield 27%). Finally, the isolated product was crystallized from CHCl₃-hexane (v/v = 2:1) to give single crystals.

¹H NMR (300 MHz, CDCl₃): δ 0.91 (6H, t, J = 5.2 Hz), 3.98 (4H, q, J = 5.2 Hz), 7.18 (2H, d, J = 6.9 Hz), 7.91 (4H, d, J = 6.6 Hz), 8.00 (2H, d, J = 6.9 Hz), 8.26 (4H, d, J = 6.6 Hz); ¹³C NMR (75 MHz, CDCl₃): δ 14.39, 64.90, 111.96, 119.88, 123.50, 125.48, 129.74, 130.82, 133.44, 144.19, 150.06, 156.77, 197.28; IR (KBr cm⁻¹): 1662 (C=O), 1603, 1515, 1472 (Ar, naphthalene), 1229 (=C—O—C); HRMS (m/z): [M + H]⁺ Calculated for C₂₈H₂₂N₂O₈, 515.1410; found, 515.1449; m.p. = 556.4–568.5 K.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were located in a difference Fourier map and were subsequently refined as riding atoms, with C—H = 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methylene), and with U_iso(H) = 1.2U_eq(C). The positions of methyl H atoms were rotationally optimized.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₈H₂₂N₂O₈
M_r	514.48
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	193
a, b, c (Å)	23.5359 (16), 10.2522 (5), 10.3605 (11)
β (°)	97.257 (14)
V (Å³)	2479.9 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.86
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Numerical (NUMABS; Higashi, 1999 )
T_min, T_max	0.674, 0.847
No. of measured, independent and observed [I > 2σ(I)] reflections	21420, 2272, 2118
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.02
No. of reflections	2272
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.26
Computer programs: PROCESS-AUTO (Rigaku, 1998 ), CrystalStructure (Rigaku, 2010 ), SIR2004 (Burla et al., 2007 ), SHELXL97 (Sheldrick, 2008 ) and ORTEPIII (Burnett & Johnson, 1996 ).

Supporting information

CCDC reference: 1019755

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814018674/is5370sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814018674/is5370Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814018674/is5370Isup3.pdf

Supporting information file. DOI: 10.1107/S1600536814018674/is5370Isup4.pdf

Supporting information file. DOI: 10.1107/S1600536814018674/is5370Isup5.pdf

Supporting information file. DOI: 10.1107/S1600536814018674/is5370Isup6.cml

checkCIF report

Chemical context top

Molecules with non-coplanarly accumulated aromatic rings, such as biphenyl and binaphthyl derivatives, have been in the limelight as unique building blocks affording characteristic optical and electronic properties (Hatano et al., 2013; Park et al., 2010; Vaghi et al., 2013) and asymmetric molecular environments (Bulman Page et al., 2012; Jayalakshmi et al., 2012; Kano et al., 2006; Wang et al., 2014). peri-Substituted naphthalenes have also much attention as characteristic aromatic ring core compounds and the structural analyses have been actively performed (Cohen et al., 2004; Jing et al., 2005).

In the course of our study on selective electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, peri-aroylnaphthalene compounds have proved to be formed regioselectively with the aid of suitable acidic mediator (Okamoto & Yonezawa, 2009; Okamoto et al., 2011). According to X-ray crystal analysis, the resulting 1,8-diaroylnaphthalene and 1-monoaroylnaphthalene compounds have non-coplanarly accumulated ring structures in their crystals. The aroyl groups at the 1,8-positions (or 1-position) of the naphthalene ring system in the molecules are situated in perpendicular fashion to the naphthalene ring system, as shown in 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008), 1,8-dibenzoyl-2,7-diethoxynaphthalene (Isogai et al., 2013) and 1-(4-nitrobenzoyl)-2,7-dimethoxynaphthalene (Watanabe et al., 2010). As a part of our continuous study on the molecular structures of this kind of molecules, the X-ray crystal structure of the title compound is reported here.

Structural commentary top

Supramolecular features top

In the crystal, the molecular packing of the title compound is mainly stabilized by a pair of C—H···O═C hydrogen bonds between the benzene ring and the ketonic carbonyl group (C13—H13···O1ⁱ; details and symmetry code in Table 1), which make an R²₂(10) ring motif (Fig. 2). The molecules are stacked through these interactions in a double-column along the c axis. The molecules are also linked by C—H···O═N interactions between the benzene ring and the nitro group (C10—H10···O3ⁱⁱ; Table 1), forming a three-dimensional network and thus resulting in the interpenetration of the naphthalene unit into the adjacent double-column. π–π interactions between the interpenetrating naphthalene ring systems are observed; the interplanar distance is 3.5326 (4) Å and the centroid–centroid distances are 3.7860 (7), 3.7859 (7) and 3.7858 (7) Å, respectively, for Cg1···Cg1^vi, Cg1···Cg2^vii and Cg2···Cg2^viii, where Cg1 and Cg2 are the centroids of the six-membered C1–C6 and C1^v–C4^v/C5/C6 rings, respectively [symmetry codes: (v) -x+1, y, -z+1/2; (vi) -x+1, -y+1, -z; (vii) x, -y+1, z-1/2; (viii) -x+1, -y+1, -z+1]. C—H···π interactions between the methylene group and the naphthalene ring system (C14—H14B···Cg1ⁱⁱⁱ and C14—H14B···Cg2^iv; Table 1 and Fig. 3) are also observed.

Database survey top

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Allen, 2002) showed 39 and 29 structures containing the 1,8-diaroylnaphthalene (including 1,8-dialkanoylnaphthalene) and 1,8-diaroyl-2,7-dialkoxynaphthalene units, respectively. The title compound has a non-coplanarly accumulated aromatic-rings structure, as found in the nitro group-free 1,8-dibenzoylnaphthalene homologues and the nitro-group-bearing 1-benzoylnaphthalene homologue, viz. 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008) and 1,8-dibenzoyl-2,7-diethoxynaphthalene (Isogai et al., 2013), and 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe et al., 2010). The dihedral angle between the benzene ring and the naphthalene ring system [77.17 (5)°] is close to those of the three homologues [68.42 (5) and 71.69 (5)° for 1,8-dibenzoyl-2,7-diethoxynaphthalene; 83.59 (5)° for 1,8-dibenzoyl-2,7-dimethoxynaphthalene; 61.97 (5)° for 1-(4-nitrobenzoyl)-2,7-dimethoxynaphthalene]. On the other hand, the torsion angle between the carbonyl group and the benzene ring is different from the homologues, i.e., the title compound [26.83 (17)°] > 1-(4-nitrobenzoyl)-2,7-dimethoxynaphthalene [-13.29 (17)°] >> 1,8-dibenzoyl-2,7-diethoxynaphthalene [1.58 (17)° and 1.44 (17)°] > 1,8-dibenzoyl-2,7-dimethoxynaphthalene [0.4 (2)°]. Although the C—H···O═ C interactions between the benzene ring and the ketonic carbonyl group are observed in all of four homologues, the C—H···O═N interaction is observed only in the title compound.

Synthesis and crystallization top

¹H NMR (300 MHz, CDCl₃): δ 0.91 (6H, t, J = 5.2 Hz), 3.98 (4H, q, J = 5.2 Hz), 7.18 (2H, d, J = 6.9 Hz), 7.91 (4H, d, J = 6.6 Hz), 8.00 (2H, d, J = 6.9 Hz), 8.26 (4H, d, J = 6.6 Hz); ¹³C NMR (75 MHz, CDCl₃): δ 14.39, 64.90, 111.96, 119.88, 123.50, 125.48, 129.74, 130.82, 133.44, 144.19, 150.06, 156.77, 197.28; IR (KBr cm^-1): 1662 (C═O), 1603, 1515, 1472 (Ar, naphthalene), 1229 (═C—O—C); HRMS (m/z): [M + H]⁺ Calculated for C₂₈H₂₂N₂O₈, 515.1410; found, 515.1449; m.p. = 556.4–568.5 K.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were located in a difference Fourier map and were subsequently refined as riding atoms, with C—H = 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methylene), and with U_iso(H) = 1.2 U_eq(C). The positions of methyl H atoms were rotationally optimized.

Related literature top

For related literature, see: Bulman Page, Bartlett, Chan, Day, Parker, Buckley, Rassias, Slawin, Allin & Lacour (2012); Burnett & Johnson (1996); Cohen et al. (2004); Hatano et al. (2013); Isogai et al. (2013); Jayalakshmi et al. (2012); Jing et al. (2005); Kano et al. (2006); Nakaema et al. (2008); Okamoto & Yonezawa (2009); Okamoto et al. (2011); Park et al. (2010); Vaghi et al. (2013); Wang et al. (2014); Watanabe et al. (2010).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku, 2010); program(s) used to solve structure: SIR2004 (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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering. The displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A crystal packing view of the title compound, showing the intermolecular C—H···O═C and C—H···O═N interactions. [Symmetry codes: (i) 1 - x, -y, -z; (ii) 3/2 - x, 1/2 + y, 1/2 - z.]
	Fig. 3. A crystal packing view of the title compound, showing the intermolecular C—H···π interactions (dashed lines) and π–π interactions (double dashed lines).

2,7-Diethoxy-1,8-bis(4-nitrobenzoyl)naphthalene top

Crystal data top

C₂₈H₂₂N₂O₈	F(000) = 1072
M_r = 514.48	D_x = 1.378 Mg m⁻³
Monoclinic, C2/c	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -C 2yc	Cell parameters from 1640 reflections
a = 23.5359 (16) Å	θ = 3.8–67.5°
b = 10.2522 (5) Å	µ = 0.86 mm⁻¹
c = 10.3605 (11) Å	T = 193 K
β = 97.257 (14)°	Block, yellow
V = 2479.9 (3) Å³	0.50 × 0.40 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2272 independent reflections
Radiation source: rotating anode	2118 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
Detector resolution: 10.000 pixels mm^-1	θ_max = 68.2°, θ_min = 3.8°
ω scans	h = −28→27
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −12→12
T_min = 0.674, T_max = 0.847	l = −12→12
21420 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0552P)² + 1.320P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
2272 reflections	Δρ_max = 0.21 e Å⁻³
175 parameters	Δρ_min = −0.26 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0031 (2)

Crystal data top

C₂₈H₂₂N₂O₈	V = 2479.9 (3) Å³
M_r = 514.48	Z = 4
Monoclinic, C2/c	Cu Kα radiation
a = 23.5359 (16) Å	µ = 0.86 mm⁻¹
b = 10.2522 (5) Å	T = 193 K
c = 10.3605 (11) Å	0.50 × 0.40 × 0.20 mm
β = 97.257 (14)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2272 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	2118 reflections with I > 2σ(I)
T_min = 0.674, T_max = 0.847	R_int = 0.044
21420 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.02	Δρ_max = 0.21 e Å⁻³
2272 reflections	Δρ_min = −0.26 e Å⁻³
175 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.48373 (3)	0.18553 (8)	0.10345 (8)	0.0365 (2)
O2	0.60134 (4)	0.37631 (9)	0.01960 (9)	0.0428 (3)
O3	0.72391 (7)	−0.19473 (16)	0.10952 (14)	0.0991 (6)
O4	0.76491 (5)	−0.08350 (14)	0.27145 (16)	0.0812 (4)
N1	0.72522 (6)	−0.10377 (14)	0.18632 (14)	0.0584 (4)
C1	0.53601 (5)	0.37563 (12)	0.16932 (11)	0.0305 (3)
C2	0.57104 (5)	0.44716 (13)	0.09761 (11)	0.0347 (3)
C3	0.57153 (5)	0.58479 (13)	0.10108 (12)	0.0397 (3)
H3	0.5962	0.6327	0.0528	0.048*
C4	0.53620 (5)	0.64790 (13)	0.17435 (12)	0.0396 (3)
H4	0.5359	0.7406	0.1746	0.048*
C5	0.5000	0.58029 (16)	0.2500	0.0346 (4)
C6	0.5000	0.44053 (16)	0.2500	0.0303 (4)
C7	0.53051 (5)	0.23260 (12)	0.14003 (11)	0.0306 (3)
C8	0.58275 (5)	0.14797 (11)	0.15282 (11)	0.0325 (3)
C9	0.63069 (5)	0.17560 (12)	0.24136 (12)	0.0368 (3)
H9	0.6313	0.2522	0.2932	0.044*
C10	0.67737 (5)	0.09281 (13)	0.25474 (13)	0.0415 (3)
H10	0.7099	0.1102	0.3164	0.050*
C11	0.67537 (6)	−0.01629 (13)	0.17554 (14)	0.0422 (3)
C12	0.62879 (6)	−0.04532 (13)	0.08520 (14)	0.0455 (3)
H12	0.6288	−0.1204	0.0314	0.055*
C13	0.58214 (6)	0.03741 (13)	0.07495 (13)	0.0410 (3)
H13	0.5494	0.0187	0.0143	0.049*
C14	0.64361 (6)	0.43699 (15)	−0.04805 (14)	0.0458 (3)
H14A	0.6698	0.4913	0.0121	0.055*
H14B	0.6252	0.4930	−0.1193	0.055*
C15	0.67573 (7)	0.32734 (18)	−0.10160 (18)	0.0615 (4)
H15A	0.6952	0.2756	−0.0297	0.074*
H15B	0.7041	0.3631	−0.1535	0.074*
H15C	0.6488	0.2717	−0.1567	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0325 (5)	0.0357 (5)	0.0403 (5)	−0.0042 (3)	0.0003 (3)	−0.0047 (4)
O2	0.0451 (5)	0.0403 (5)	0.0458 (5)	−0.0028 (4)	0.0167 (4)	0.0027 (4)
O3	0.1189 (12)	0.1059 (12)	0.0720 (9)	0.0757 (10)	0.0100 (8)	−0.0127 (8)
O4	0.0517 (7)	0.0739 (9)	0.1132 (11)	0.0221 (6)	−0.0077 (7)	0.0084 (8)
N1	0.0580 (8)	0.0581 (8)	0.0623 (8)	0.0231 (6)	0.0198 (7)	0.0154 (7)
C1	0.0301 (6)	0.0293 (6)	0.0306 (6)	−0.0002 (4)	−0.0027 (5)	0.0010 (4)
C2	0.0338 (6)	0.0353 (7)	0.0338 (6)	−0.0014 (5)	−0.0004 (5)	0.0012 (5)
C3	0.0414 (7)	0.0351 (7)	0.0418 (7)	−0.0071 (5)	0.0024 (5)	0.0071 (5)
C4	0.0463 (7)	0.0276 (6)	0.0427 (7)	−0.0031 (5)	−0.0033 (6)	0.0033 (5)
C5	0.0370 (9)	0.0294 (9)	0.0349 (8)	0.000	−0.0050 (7)	0.000
C6	0.0304 (8)	0.0282 (8)	0.0300 (8)	0.000	−0.0047 (6)	0.000
C7	0.0327 (6)	0.0323 (6)	0.0266 (5)	−0.0025 (5)	0.0024 (4)	−0.0004 (5)
C8	0.0334 (6)	0.0291 (6)	0.0354 (6)	−0.0036 (5)	0.0058 (5)	−0.0004 (5)
C9	0.0364 (6)	0.0340 (7)	0.0393 (6)	−0.0015 (5)	0.0024 (5)	−0.0027 (5)
C10	0.0346 (7)	0.0444 (8)	0.0447 (7)	0.0002 (5)	0.0017 (5)	0.0042 (6)
C11	0.0394 (7)	0.0388 (7)	0.0507 (7)	0.0082 (5)	0.0140 (6)	0.0090 (6)
C12	0.0502 (8)	0.0351 (7)	0.0528 (8)	0.0026 (6)	0.0129 (6)	−0.0074 (6)
C13	0.0385 (7)	0.0377 (7)	0.0464 (7)	−0.0029 (5)	0.0036 (5)	−0.0085 (6)
C14	0.0384 (7)	0.0536 (8)	0.0463 (7)	−0.0059 (6)	0.0094 (6)	0.0084 (6)
C15	0.0469 (8)	0.0731 (11)	0.0686 (10)	0.0035 (7)	0.0238 (7)	0.0044 (8)

Geometric parameters (Å, º) top

O1—C7	1.2181 (14)	C7—C8	1.4970 (16)
O2—C2	1.3546 (15)	C8—C13	1.3903 (17)
O2—C14	1.4298 (15)	C8—C9	1.3904 (17)
O3—N1	1.224 (2)	C9—C10	1.3813 (18)
O4—N1	1.2188 (19)	C9—H9	0.9500
N1—C11	1.4698 (17)	C10—C11	1.385 (2)
C1—C2	1.3872 (17)	C10—H10	0.9500
C1—C6	1.4278 (14)	C11—C12	1.381 (2)
C1—C7	1.4997 (17)	C12—C13	1.3809 (19)
C2—C3	1.4116 (19)	C12—H12	0.9500
C3—C4	1.3584 (19)	C13—H13	0.9500
C3—H3	0.9500	C14—C15	1.500 (2)
C4—C5	1.4105 (15)	C14—H14A	0.9900
C4—H4	0.9500	C14—H14B	0.9900
C5—C4ⁱ	1.4105 (15)	C15—H15A	0.9800
C5—C6	1.433 (2)	C15—H15B	0.9800
C6—C1ⁱ	1.4278 (14)	C15—H15C	0.9800

C2—O2—C14	120.70 (11)	C10—C9—C8	120.65 (12)
O4—N1—O3	123.69 (14)	C10—C9—H9	119.7
O4—N1—C11	118.84 (14)	C8—C9—H9	119.7
O3—N1—C11	117.46 (15)	C9—C10—C11	118.03 (12)
C2—C1—C6	120.28 (12)	C9—C10—H10	121.0
C2—C1—C7	116.77 (10)	C11—C10—H10	121.0
C6—C1—C7	122.12 (11)	C12—C11—C10	122.71 (12)
O2—C2—C1	115.43 (11)	C12—C11—N1	118.54 (13)
O2—C2—C3	123.23 (11)	C10—C11—N1	118.75 (13)
C1—C2—C3	121.22 (12)	C11—C12—C13	118.37 (12)
C4—C3—C2	119.13 (12)	C11—C12—H12	120.8
C4—C3—H3	120.4	C13—C12—H12	120.8
C2—C3—H3	120.4	C12—C13—C8	120.41 (12)
C3—C4—C5	122.13 (12)	C12—C13—H13	119.8
C3—C4—H4	118.9	C8—C13—H13	119.8
C5—C4—H4	118.9	O2—C14—C15	105.65 (12)
C4ⁱ—C5—C4	121.13 (16)	O2—C14—H14A	110.6
C4ⁱ—C5—C6	119.43 (8)	C15—C14—H14A	110.6
C4—C5—C6	119.43 (8)	O2—C14—H14B	110.6
C1—C6—C1ⁱ	124.45 (15)	C15—C14—H14B	110.6
C1—C6—C5	117.77 (7)	H14A—C14—H14B	108.7
C1ⁱ—C6—C5	117.77 (7)	C14—C15—H15A	109.5
O1—C7—C1	120.12 (10)	C14—C15—H15B	109.5
O1—C7—C8	119.87 (11)	H15A—C15—H15B	109.5
C1—C7—C8	120.00 (9)	C14—C15—H15C	109.5
C13—C8—C9	119.81 (12)	H15A—C15—H15C	109.5
C13—C8—C7	118.22 (11)	H15B—C15—H15C	109.5
C9—C8—C7	121.96 (11)

C14—O2—C2—C1	−173.03 (10)	C2—C1—C7—C8	58.11 (14)
C14—O2—C2—C3	10.93 (18)	C6—C1—C7—C8	−132.34 (10)
C6—C1—C2—O2	−176.93 (8)	O1—C7—C8—C13	26.83 (17)
C7—C1—C2—O2	−7.18 (14)	C1—C7—C8—C13	−151.79 (11)
C6—C1—C2—C3	−0.81 (16)	O1—C7—C8—C9	−151.86 (12)
C7—C1—C2—C3	168.94 (11)	C1—C7—C8—C9	29.52 (17)
O2—C2—C3—C4	174.63 (11)	C13—C8—C9—C10	−1.34 (19)
C1—C2—C3—C4	−1.18 (18)	C7—C8—C9—C10	177.33 (11)
C2—C3—C4—C5	1.68 (18)	C8—C9—C10—C11	1.42 (19)
C3—C4—C5—C4ⁱ	179.81 (13)	C9—C10—C11—C12	−0.4 (2)
C3—C4—C5—C6	−0.19 (13)	C9—C10—C11—N1	178.57 (12)
C2—C1—C6—C1ⁱ	−177.76 (11)	O4—N1—C11—C12	−175.30 (14)
C7—C1—C6—C1ⁱ	13.05 (7)	O3—N1—C11—C12	3.6 (2)
C2—C1—C6—C5	2.24 (11)	O4—N1—C11—C10	5.7 (2)
C7—C1—C6—C5	−166.95 (7)	O3—N1—C11—C10	−175.35 (14)
C4ⁱ—C5—C6—C1	178.24 (8)	C10—C11—C12—C13	−0.8 (2)
C4—C5—C6—C1	−1.76 (8)	N1—C11—C12—C13	−179.72 (12)
C4ⁱ—C5—C6—C1ⁱ	−1.76 (8)	C11—C12—C13—C8	0.9 (2)
C4—C5—C6—C1ⁱ	178.24 (8)	C9—C8—C13—C12	0.2 (2)
C2—C1—C7—O1	−120.50 (12)	C7—C8—C13—C12	−178.56 (12)
C6—C1—C7—O1	49.05 (15)	C2—O2—C14—C15	169.06 (11)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the six-membered C1–C6 and C1^v–C4^v/C5/C6 rings, respectively. [Symmetry code: (v) -x+1, y, -z+1/2.]

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱⁱ	0.95	2.50	3.2129 (17)	132
C10—H10···O3ⁱⁱⁱ	0.95	2.59	3.360 (2)	138
C14—H14B···Cg1^iv	0.99	2.81	3.6284 (15)	140
C14—H14B···Cg2^v	0.99	2.81	3.6284 (15)	140

Symmetry codes: (ii) −x+1, −y, −z; (iii) −x+3/2, y+1/2, −z+1/2; (iv) x, −y, z−1/2; (v) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the six-membered C1–C6 and C1^v–C4^v/C5/C6 rings, respectively. [Symmetry code: (v) -x+1, y, -z+1/2.]

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1ⁱ	0.95	2.50	3.2129 (17)	132
C10—H10···O3ⁱⁱ	0.95	2.59	3.360 (2)	138
C14—H14B···Cg1ⁱⁱⁱ	0.99	2.81	3.6284 (15)	140
C14—H14B···Cg2^iv	0.99	2.81	3.6284 (15)	140

Symmetry codes: (i) −x+1, −y, −z; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x, −y, z−1/2; (iv) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₈H₂₂N₂O₈
M_r	514.48
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	193
a, b, c (Å)	23.5359 (16), 10.2522 (5), 10.3605 (11)
β (°)	97.257 (14)
V (Å³)	2479.9 (3)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.86
Crystal size (mm)	0.50 × 0.40 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.674, 0.847
No. of measured, independent and observed [I > 2σ(I)] reflections	21420, 2272, 2118
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.02
No. of reflections	2272
No. of parameters	175
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.26

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku, 2010), SIR2004 (Burla et al., 2007), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Acknowledgements

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

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bulman Page, P. C., Bartlett, C. J., Chan, Y., Day, D., Parker, P., Buckley, B. R., Rassias, G. A., Slawin, A. M. Z., Allin, S. M. & Lacour, J. (2012). J. Org. Chem. 77, 6128–6138. Web of Science CSD CrossRef CAS PubMed Google Scholar
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G., Siliqi, D. & Spagna, R. (2007). J. Appl. Cryst. 40, 609–613. Web of Science CrossRef CAS IUCr Journals Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory. Tennessee, USA. Google Scholar
Cohen, S., Thirumalaikumar, M., Pogodin, S. & Agranat, I. (2004). Struct. Chem. 15, 339–346. Web of Science CSD CrossRef CAS Google Scholar
Hatano, S., Horino, T., Tokita, A., Oshima, T. & Abe, J. (2013). J. Am. Chem. Soc. 135, 3164–3172. Web of Science CSD CrossRef CAS PubMed Google Scholar
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Isogai, A., Tsumuki, T., Murohashi, S., Okamoto, A. & Yonezawa, N. (2013). Acta Cryst. E69, o71. CSD CrossRef IUCr Journals Google Scholar
Jayalakshmi, V., Wood, T., Basu, R., Du, J., Blackburn, T., Rosenblatt, C., Crudden, C. M. & Lemieux, R. P. (2012). J. Mater. Chem. 22, 15255–15261. Web of Science CrossRef CAS Google Scholar
Jing, L.-H., Qin, D.-B., He, L., Gu, S.-J., Zhang, H.-X. & Lei, G. (2005). Acta Cryst. E61, o3595–o3596. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Kano, T., Tokuda, O. & Maruoka, K. (2006). Tetrahedron Lett. 47, 7423–7426. Web of Science CrossRef CAS Google Scholar
Nakaema, K., Watanabe, S., Okamoto, A., Noguchi, K. & Yonezawa, N. (2008). Acta Cryst. E64, o807. Web of Science CSD CrossRef IUCr Journals Google Scholar
Okamoto, A., Mitsui, R., Oike, H. & Yonezawa, N. (2011). Chem. Lett. 40, 1283–1284. Web of Science CrossRef CAS Google Scholar
Okamoto, A. & Yonezawa, N. (2009). Chem. Lett. 38, 914–915. Web of Science CrossRef CAS Google Scholar
Park, J. K., Lee, K. H., Park, J. S., Seo, J. H., Kim, Y. K. & Yoon, S. S. (2010). Mol. Cryst. Liq. Cryst. 531, 55–64. CAS Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Vaghi, L., Benincori, T., Cirilli, R., Alberico, E., Mussini, P., Romana, P., Marco, P. T., Rizzo, S. & Sannicolo, F. (2013). Eur. J. Org. Chem. pp. 8174–8184. Web of Science CSD CrossRef Google Scholar
Wang, Y., McGonigal, P. R., Herle, B., Basora, M. & Echavarren, A. (2014). J. Am. Chem. Soc. 136, 801–809. Web of Science CrossRef CAS PubMed Google Scholar
Watanabe, S., Nakaema, K., Nishijima, T., Okamoto, A. & Yonezawa, N. (2010). Acta Cryst. E66, o615. Web of Science CSD CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages 138-141

doi:10.1107/S1600536814018674

Open

access