7-Meth­oxy-1-(4-nitro­benzo­yl)naph­thalen-2-yl 4-nitro­benzoate

Muto, T.; Hijikata, D.; Okamoto, A.; Oike, H.; Yonezawa, N.

doi:10.1107/S1600536811027619

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2040

doi:10.1107/S1600536811027619

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7-Methoxy-1-(4-nitrobenzoyl)naphthalen-2-yl 4-nitrobenzoate

Toyokazu Muto,^a Daichi Hijikata,^a Akiko Okamoto,^a ^* Hideaki Oike ^a and Noriyuki Yonezawa ^a

^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 9 July 2011; accepted 10 July 2011; online 16 July 2011)

In the title compound, C₂₅H₁₆N₂O₈, the dihedral angle between the naphthalene ring system and the benzene ring of the nitrophenyl ketone unit is 82.64 (7)°. The bridging ester O—C(=O)—C plane makes dihedral angles of 42.12 (8) and 11.47 (9)°, respectively, with the naphthalene ring system and the benzene ring of the nitrophenyl ester unit. In the crystal, two types of weak intermolecular C—H⋯O interactions are observed.

Related literature

For electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009 ). For the structures of closely related compounds, see: Muto et al. (2010 ); Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa (2008 ); Mitsui, Nakaema, Noguchi & Yonezawa (2008 ); Mitsui et al. (2009 ); Nagasawa et al. (2010 ); Watanabe et al. (2010 ).

Experimental

Crystal data

C₂₅H₁₆N₂O₈
M_r = 472.40
Triclinic, $[P \overline 1]$
a = 7.30691 (15) Å
b = 10.2555 (2) Å
c = 14.7645 (3) Å
α = 84.750 (1)°
β = 86.278 (1)°
γ = 74.079 (1)°
V = 1058.57 (4) Å³
Z = 2
Cu Kα radiation
μ = 0.95 mm⁻¹
T = 193 K
0.60 × 0.20 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.599, T_max = 0.911
19272 measured reflections
3818 independent reflections
2769 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.124
S = 1.09
3818 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O7ⁱ	0.95	2.58	3.211 (3)	124
C23—H23⋯O4ⁱⁱ	0.95	2.55	3.435 (2)	154
Symmetry codes: (i) x, y, z+1; (ii) -x+3, -y, -z.

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811027619/is2749sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811027619/is2749Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811027619/is2749Isup3.cml

checkCIF report

Comment top

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). Recently, we have reported the crystal structures of several 1,8-diaroylated naphthalene homologues exemplified by 1,8-bis(4-methylbenzoyl)-2,7-dimethoxynaphthalene (Muto et al., 2010). The aroyl groups at the 1,8-positions of the naphthalene rings in these compounds are twistedly connected in an almost perpendicular fashion, but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene rings. The crystal structures of 1-monoaroylated naphthalene compounds such as 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe et al., 2010) also exhibit essentially the same non-coplanar structure as the 1,8-diaroylated naphthalenes. Furthermore, the crystal structures of several 1-monoaroylated naphthalene derivatives have revealed. For example, (2-hydroxy-7-methoxynaphthalen-1-yl)(4-methylphenyl)methanone (Nagasawa et al., 2010) and (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui, Nakaema, Noguchi & Yonezawa, 2008) prepared by regioselective demethylation form intramolecular hydrogen bond between the carbonyl group and the adjacent hydroxy one. Besides, (4-chlorobenzoyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone (Mitsui et al., 2009) has similar non-coplanar configuration to 1-(4-chlorobenzoyl)-2,7-dimethoxynaphthalene (Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa, 2008). As a part of our continuous studies on the molecular structures of this kind of homologous molecules, the crystal structure of the title compound, 1-monoaroylated naphthalene bearing 4-nitrobenzoyloxy group at 2-position is discussed in this report.

The molecular structure of the title compound is displayed in Fig. 1. The benzene ring of nitrophenyl ketone moiety (C12–C17) is out of the plane of the naphthalene ring. The dihedral angle between the best planes of the benzene ring (C12–C17) and the naphthalene ring system (C1–C10) is 82.64 (7)° [C2–C1–C11–O1 torsion angle = -79.8 (2)°]. However, the carbonyl group (C11═O1) and the benzene ring (C12–C17) have almost coplanar configuration [O1–C11–C12–C17 torsion angle = 5.0 (2)°]. Besides, the dihedral angle between the benzene ring (C12–C17) and the nitro group plane (O4/N1/O5) is 29.35 (9)°. On the other hand, the benzene ring of nitrophenyl ester moiety (C19–C24) makes a rather small dihedral angle with naphthalene ring system (C1–C10) than that with the benzene ring of nitrophenyl ketone moiety (C12–C17), i.e., 31.38 (7)°. Moreover, the dihedral angles of the benzene ring (C19–C24) and the naphthalene ring system (C1–C10) with the ester plane (O2—C18(═ O6)—C19) are 11.47 (9)° and 42.12 (8)°, respectively. The nitro group plane (O7/N2/O8) makes a small dihedral angle of 6.47 (10)° with the benzene ring (C19–C24). In the crystal structure, the molecular packing of the title compound is stabilized mainly by van der Waals interactions. The crystal packing is additionally stabilized by intermolecular C—H···O interaction between the oxygen atom (O7) of the nitro group in nitrophenyl ester and one hydrogen atom (H6) of the naphthalene ring of the adjacent molecule (C6—H6···O7ⁱ; Fig. 2 and Table 1). Moreover, there is also intermolecular C—H···O interaction between the oxygen atom (O4) of the nitro group in nitrophenyl ketone and one hydrogen atom (H23) of the nitrophenyl ester of the adjacent molecule (C23—H23···O4ⁱⁱ; Fig. 3 and Table 1).

Related literature top

For electrophilic aromatic substitution of naphthalene derivatives, see: Okamoto & Yonezawa (2009). For the structures of closely related compounds, see: Muto et al. (2010); Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa (2008); Mitsui, Nakaema, Noguchi & Yonezawa (2008); Mitsui et al. (2009); Nagasawa et al. (2010); Watanabe et al. (2010).

Experimental top

To a 100 ml flask, 4-nitrobenzoyl chloride (17 mmol, 3.173 g), aluminium chloride (18.7 mmol, 2.495 g) and methylene chloride (21 ml) were placed and stirred at 273 K. To the reaction mixture thus obtained, 2,7-dimethoxynaphthalene (8.5 mmol, 1.599 g) was added. After the reaction mixture was stirred at 273 K for 60 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 silica-gel chromatography from CHCl₃. Yellow platelet single crystals suitable for X-ray diffraction were obtained by crystallization from ethanol (10 mg, 0.2% yield).

¹H NMR δ (300 MHz, CDCl₃); 3.75 (3H, s), 6.91 (1H, d, J = 2.4 Hz), 7.24 (1H, dd, J = 2.4, 9.0 Hz), 7.34 (1H, d, J = 8.4 Hz), 7.89 (1H, d, J = 9.0 Hz), 7.98 (2H, d, J = 9.0 Hz), 8.00 (2H, d, J = 8.4 Hz), 8.04 (1H, d, J = 9.0 Hz), 8.21 (2H, d, J = 8.4 Hz), 8.22 (2H, d, J = 9.3 Hz) p.p.m..

¹³C NMR δ (75 MHz, CDCl₃); 55.32, 103.27, 118.37, 119.57, 123.65, 123.93, 125.45, 127.27, 130.14, 130.39, 131.00, 132.03, 132.54, 133.55, 141.98, 146.62, 150.55, 150.96, 159.37, 162.57, 194.18 p.p.m..

IR (KBr); 1746, 1679, 1619, 1525, 1349, 1234, 1208 cm^-1

HRMS (m/z); [M + H]+ Calcd for C₂₅H₁₇N₂O₈, 473.0985; found, 473.0977.

m.p. = 452.0–454.0 K

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

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids at 50% probability.
	Fig. 2. A partial packing diagram of the title compound, showing intermolecular C6—H6···O7ⁱ interactions [symmetry code: (i) x, y, 1 + z].
	Fig. 3. A partial packing diagram of the title compound, showing intermolecular C23—H23···O4ⁱⁱ interactions [symmetry code: (ii) 3 - x, -y, -z].

7-Methoxy-1-(4-nitrobenzoyl)naphthalen-2-yl 4-nitrobenzoate top

Crystal data top

C₂₅H₁₆N₂O₈	Z = 2
M_r = 472.40	F(000) = 488
Triclinic, P1	D_x = 1.482 Mg m⁻³
Hall symbol: -P 1	Melting point = 452.0–454.0 K
a = 7.30691 (15) Å	Cu Kα radiation, λ = 1.54187 Å
b = 10.2555 (2) Å	Cell parameters from 13543 reflections
c = 14.7645 (3) Å	θ = 3.0–68.2°
α = 84.750 (1)°	µ = 0.95 mm⁻¹
β = 86.278 (1)°	T = 193 K
γ = 74.079 (1)°	Platelet, yellow
V = 1058.57 (4) Å³	0.60 × 0.20 × 0.10 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3818 independent reflections
Radiation source: rotating anode	2769 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 10.00 pixels mm^-1	θ_max = 68.2°, θ_min = 3.0°
ω scans	h = −8→8
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −12→12
T_min = 0.599, T_max = 0.911	l = −17→17
19272 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)] = 0.041	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.066P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
3818 reflections	Δρ_max = 0.25 e Å⁻³
319 parameters	Δρ_min = −0.22 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: 0.0109 (9)

Crystal data top

C₂₅H₁₆N₂O₈	γ = 74.079 (1)°
M_r = 472.40	V = 1058.57 (4) Å³
Triclinic, P1	Z = 2
a = 7.30691 (15) Å	Cu Kα radiation
b = 10.2555 (2) Å	µ = 0.95 mm⁻¹
c = 14.7645 (3) Å	T = 193 K
α = 84.750 (1)°	0.60 × 0.20 × 0.10 mm
β = 86.278 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3818 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	2769 reflections with I > 2σ(I)
T_min = 0.599, T_max = 0.911	R_int = 0.046
19272 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 1.09	Δρ_max = 0.25 e Å⁻³
3818 reflections	Δρ_min = −0.22 e Å⁻³
319 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	0.72939 (15)	0.14056 (11)	0.14376 (8)	0.0481 (3)
O2	0.81352 (16)	0.41705 (10)	0.13883 (8)	0.0441 (3)
O3	0.7430 (2)	−0.05991 (14)	0.52467 (9)	0.0626 (4)
O4	1.72999 (17)	−0.14620 (12)	0.21963 (9)	0.0572 (4)
O5	1.69619 (17)	−0.13852 (12)	0.07413 (10)	0.0550 (4)
O6	0.57830 (17)	0.61275 (11)	0.12164 (8)	0.0497 (3)
O7	0.8971 (2)	0.37502 (16)	−0.32155 (10)	0.0792 (5)
O8	0.7462 (2)	0.58713 (17)	−0.34326 (9)	0.0801 (5)
N1	1.6332 (2)	−0.11728 (13)	0.15166 (11)	0.0460 (4)
N2	0.8126 (2)	0.48522 (19)	−0.29361 (11)	0.0587 (4)
C1	0.7879 (2)	0.26316 (16)	0.26282 (11)	0.0383 (4)
C2	0.7743 (2)	0.39621 (16)	0.23280 (12)	0.0416 (4)
C3	0.7412 (2)	0.50013 (18)	0.29209 (13)	0.0498 (5)
H3	0.7355	0.5910	0.2698	0.060*
C4	0.7176 (3)	0.46701 (19)	0.38256 (14)	0.0525 (5)
H4	0.6969	0.5362	0.4237	0.063*
C5	0.7230 (2)	0.33340 (18)	0.41736 (12)	0.0468 (4)
C6	0.6962 (3)	0.2986 (2)	0.51139 (13)	0.0568 (5)
H6	0.6712	0.3676	0.5528	0.068*
C7	0.7053 (3)	0.1694 (2)	0.54338 (13)	0.0595 (5)
H7	0.6882	0.1487	0.6069	0.071*
C8	0.7402 (3)	0.0650 (2)	0.48347 (12)	0.0500 (5)
C9	0.7681 (2)	0.09310 (17)	0.39186 (12)	0.0437 (4)
H9	0.7933	0.0223	0.3518	0.052*
C10	0.7594 (2)	0.22823 (17)	0.35694 (12)	0.0415 (4)
C11	0.8441 (2)	0.15771 (15)	0.19458 (11)	0.0380 (4)
C12	1.0499 (2)	0.07968 (15)	0.18749 (11)	0.0372 (4)
C13	1.1798 (2)	0.09503 (16)	0.24817 (11)	0.0420 (4)
H13	1.1372	0.1520	0.2968	0.050*
C14	1.3706 (2)	0.02737 (16)	0.23747 (11)	0.0432 (4)
H14	1.4597	0.0351	0.2793	0.052*
C15	1.4283 (2)	−0.05105 (15)	0.16524 (12)	0.0403 (4)
C16	1.3033 (2)	−0.06977 (17)	0.10467 (12)	0.0468 (4)
H16	1.3475	−0.1255	0.0555	0.056*
C17	1.1129 (2)	−0.00550 (16)	0.11758 (12)	0.0444 (4)
H17	1.0236	−0.0196	0.0782	0.053*
C18	0.6997 (2)	0.52340 (16)	0.08865 (12)	0.0412 (4)
C19	0.7424 (2)	0.51149 (16)	−0.01015 (12)	0.0405 (4)
C20	0.6551 (2)	0.62210 (17)	−0.06911 (13)	0.0449 (4)
H20	0.5785	0.7031	−0.0451	0.054*
C21	0.6792 (2)	0.61456 (17)	−0.16166 (13)	0.0468 (5)
H21	0.6210	0.6898	−0.2022	0.056*
C22	0.7898 (2)	0.49528 (18)	−0.19427 (12)	0.0451 (4)
C23	0.8803 (2)	0.38428 (18)	−0.13809 (13)	0.0475 (5)
H23	0.9570	0.3038	−0.1627	0.057*
C24	0.8563 (2)	0.39339 (17)	−0.04519 (12)	0.0448 (4)
H24	0.9177	0.3187	−0.0050	0.054*
C25	0.7807 (3)	−0.1711 (2)	0.46867 (14)	0.0637 (6)
H25A	0.7773	−0.2542	0.5064	0.076*
H25B	0.9069	−0.1831	0.4383	0.076*
H25C	0.6838	−0.1525	0.4228	0.076*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0423 (7)	0.0422 (7)	0.0595 (8)	−0.0068 (6)	−0.0133 (6)	−0.0083 (6)
O2	0.0433 (7)	0.0352 (6)	0.0505 (7)	−0.0052 (5)	−0.0038 (5)	−0.0019 (5)
O3	0.0694 (9)	0.0699 (9)	0.0509 (8)	−0.0263 (7)	−0.0071 (7)	0.0083 (7)
O4	0.0444 (8)	0.0506 (8)	0.0703 (9)	−0.0003 (6)	−0.0121 (7)	−0.0036 (6)
O5	0.0492 (8)	0.0476 (7)	0.0659 (9)	−0.0096 (6)	0.0103 (7)	−0.0117 (6)
O6	0.0436 (7)	0.0381 (7)	0.0632 (8)	−0.0028 (6)	−0.0013 (6)	−0.0088 (6)
O7	0.0857 (11)	0.0800 (11)	0.0672 (10)	−0.0038 (9)	−0.0163 (8)	−0.0293 (8)
O8	0.0850 (11)	0.0858 (11)	0.0592 (9)	−0.0083 (9)	−0.0114 (8)	0.0088 (8)
N1	0.0425 (9)	0.0341 (8)	0.0600 (10)	−0.0082 (6)	0.0006 (8)	−0.0052 (7)
N2	0.0486 (10)	0.0684 (11)	0.0592 (11)	−0.0123 (9)	−0.0103 (8)	−0.0101 (9)
C1	0.0298 (9)	0.0371 (9)	0.0473 (10)	−0.0061 (7)	−0.0052 (7)	−0.0066 (7)
C2	0.0346 (9)	0.0393 (9)	0.0489 (10)	−0.0053 (7)	−0.0041 (8)	−0.0060 (8)
C3	0.0452 (11)	0.0389 (9)	0.0642 (13)	−0.0061 (8)	−0.0076 (9)	−0.0110 (9)
C4	0.0468 (11)	0.0499 (11)	0.0606 (12)	−0.0070 (9)	−0.0056 (9)	−0.0201 (9)
C5	0.0356 (10)	0.0528 (11)	0.0512 (11)	−0.0068 (8)	−0.0050 (8)	−0.0136 (9)
C6	0.0481 (12)	0.0726 (14)	0.0499 (12)	−0.0116 (10)	−0.0045 (9)	−0.0192 (10)
C7	0.0546 (12)	0.0812 (15)	0.0444 (11)	−0.0202 (11)	−0.0055 (9)	−0.0062 (10)
C8	0.0419 (10)	0.0619 (12)	0.0476 (11)	−0.0170 (9)	−0.0075 (8)	0.0016 (9)
C9	0.0359 (9)	0.0471 (10)	0.0474 (10)	−0.0090 (8)	−0.0056 (8)	−0.0044 (8)
C10	0.0301 (9)	0.0464 (10)	0.0474 (10)	−0.0072 (7)	−0.0059 (7)	−0.0071 (8)
C11	0.0381 (9)	0.0345 (8)	0.0422 (9)	−0.0109 (7)	−0.0078 (8)	0.0011 (7)
C12	0.0389 (9)	0.0312 (8)	0.0406 (9)	−0.0081 (7)	−0.0048 (7)	−0.0011 (7)
C13	0.0379 (10)	0.0419 (9)	0.0453 (10)	−0.0071 (8)	−0.0027 (7)	−0.0087 (8)
C14	0.0394 (10)	0.0422 (9)	0.0481 (11)	−0.0091 (8)	−0.0085 (8)	−0.0056 (8)
C15	0.0357 (9)	0.0307 (8)	0.0516 (10)	−0.0049 (7)	−0.0012 (8)	−0.0014 (7)
C16	0.0460 (11)	0.0414 (10)	0.0502 (11)	−0.0044 (8)	−0.0004 (8)	−0.0133 (8)
C17	0.0422 (10)	0.0423 (9)	0.0481 (10)	−0.0068 (8)	−0.0097 (8)	−0.0089 (8)
C18	0.0361 (9)	0.0309 (8)	0.0582 (11)	−0.0109 (7)	−0.0063 (8)	−0.0021 (8)
C19	0.0351 (9)	0.0337 (9)	0.0539 (11)	−0.0102 (7)	−0.0041 (8)	−0.0053 (8)
C20	0.0400 (10)	0.0338 (9)	0.0597 (12)	−0.0070 (7)	−0.0057 (8)	−0.0042 (8)
C21	0.0402 (10)	0.0423 (10)	0.0576 (12)	−0.0104 (8)	−0.0098 (8)	0.0016 (8)
C22	0.0377 (10)	0.0490 (10)	0.0500 (11)	−0.0123 (8)	−0.0063 (8)	−0.0062 (8)
C23	0.0409 (10)	0.0419 (10)	0.0596 (12)	−0.0079 (8)	−0.0043 (8)	−0.0112 (8)
C24	0.0398 (10)	0.0364 (9)	0.0566 (11)	−0.0070 (7)	−0.0071 (8)	−0.0018 (8)
C25	0.0671 (14)	0.0584 (13)	0.0665 (14)	−0.0216 (11)	−0.0093 (11)	0.0094 (10)

Geometric parameters (Å, º) top

O1—C11	1.2181 (17)	C9—C10	1.420 (2)
O2—C18	1.3654 (19)	C9—H9	0.9500
O2—C2	1.407 (2)	C11—C12	1.499 (2)
O3—C8	1.362 (2)	C12—C17	1.387 (2)
O3—C25	1.425 (2)	C12—C13	1.395 (2)
O4—N1	1.2319 (17)	C13—C14	1.382 (2)
O5—N1	1.2214 (18)	C13—H13	0.9500
O6—C18	1.2016 (19)	C14—C15	1.369 (2)
O7—N2	1.224 (2)	C14—H14	0.9500
O8—N2	1.222 (2)	C15—C16	1.380 (2)
N1—C15	1.474 (2)	C16—C17	1.375 (2)
N2—C22	1.475 (2)	C16—H16	0.9500
C1—C2	1.374 (2)	C17—H17	0.9500
C1—C10	1.419 (2)	C18—C19	1.481 (2)
C1—C11	1.502 (2)	C19—C24	1.390 (2)
C2—C3	1.401 (2)	C19—C20	1.395 (2)
C3—C4	1.360 (3)	C20—C21	1.373 (2)
C3—H3	0.9500	C20—H20	0.9500
C4—C5	1.410 (2)	C21—C22	1.377 (2)
C4—H4	0.9500	C21—H21	0.9500
C5—C6	1.416 (2)	C22—C23	1.381 (2)
C5—C10	1.420 (2)	C23—C24	1.380 (2)
C6—C7	1.351 (3)	C23—H23	0.9500
C6—H6	0.9500	C24—H24	0.9500
C7—C8	1.410 (3)	C25—H25A	0.9800
C7—H7	0.9500	C25—H25B	0.9800
C8—C9	1.371 (2)	C25—H25C	0.9800

C18—O2—C2	120.25 (13)	C13—C12—C11	121.03 (15)
C8—O3—C25	117.74 (14)	C14—C13—C12	120.00 (16)
O5—N1—O4	124.40 (15)	C14—C13—H13	120.0
O5—N1—C15	118.15 (15)	C12—C13—H13	120.0
O4—N1—C15	117.45 (15)	C15—C14—C13	118.59 (15)
O8—N2—O7	123.76 (19)	C15—C14—H14	120.7
O8—N2—C22	118.23 (17)	C13—C14—H14	120.7
O7—N2—C22	118.01 (17)	C14—C15—C16	122.86 (16)
C2—C1—C10	119.72 (15)	C14—C15—N1	118.25 (15)
C2—C1—C11	118.15 (15)	C16—C15—N1	118.89 (16)
C10—C1—C11	122.03 (14)	C17—C16—C15	118.09 (16)
C1—C2—C3	122.62 (17)	C17—C16—H16	121.0
C1—C2—O2	114.39 (14)	C15—C16—H16	121.0
C3—C2—O2	122.75 (15)	C16—C17—C12	120.77 (15)
C4—C3—C2	117.97 (17)	C16—C17—H17	119.6
C4—C3—H3	121.0	C12—C17—H17	119.6
C2—C3—H3	121.0	O6—C18—O2	123.46 (17)
C3—C4—C5	122.17 (17)	O6—C18—C19	125.18 (15)
C3—C4—H4	118.9	O2—C18—C19	111.34 (15)
C5—C4—H4	118.9	C24—C19—C20	119.88 (17)
C4—C5—C6	122.42 (17)	C24—C19—C18	122.59 (15)
C4—C5—C10	119.49 (17)	C20—C19—C18	117.44 (15)
C6—C5—C10	118.08 (16)	C21—C20—C19	120.39 (16)
C7—C6—C5	121.38 (18)	C21—C20—H20	119.8
C7—C6—H6	119.3	C19—C20—H20	119.8
C5—C6—H6	119.3	C20—C21—C22	118.35 (16)
C6—C7—C8	120.66 (18)	C20—C21—H21	120.8
C6—C7—H7	119.7	C22—C21—H21	120.8
C8—C7—H7	119.7	C21—C22—C23	122.92 (17)
O3—C8—C9	125.24 (17)	C21—C22—N2	118.69 (16)
O3—C8—C7	114.50 (17)	C23—C22—N2	118.39 (16)
C9—C8—C7	120.26 (17)	C24—C23—C22	118.21 (17)
C8—C9—C10	119.91 (17)	C24—C23—H23	120.9
C8—C9—H9	120.0	C22—C23—H23	120.9
C10—C9—H9	120.0	C23—C24—C19	120.22 (16)
C1—C10—C9	122.34 (15)	C23—C24—H24	119.9
C1—C10—C5	117.96 (15)	C19—C24—H24	119.9
C9—C10—C5	119.70 (16)	O3—C25—H25A	109.5
O1—C11—C12	121.01 (15)	O3—C25—H25B	109.5
O1—C11—C1	121.49 (14)	H25A—C25—H25B	109.5
C12—C11—C1	117.41 (13)	O3—C25—H25C	109.5
C17—C12—C13	119.59 (15)	H25A—C25—H25C	109.5
C17—C12—C11	119.35 (14)	H25B—C25—H25C	109.5

C10—C1—C2—C3	2.9 (2)	O1—C11—C12—C13	−177.25 (14)
C11—C1—C2—C3	−173.59 (14)	C1—C11—C12—C13	6.3 (2)
C10—C1—C2—O2	177.35 (13)	C17—C12—C13—C14	1.1 (2)
C11—C1—C2—O2	0.9 (2)	C11—C12—C13—C14	−176.67 (14)
C18—O2—C2—C1	135.88 (14)	C12—C13—C14—C15	1.7 (2)
C18—O2—C2—C3	−49.7 (2)	C13—C14—C15—C16	−2.6 (2)
C1—C2—C3—C4	−1.5 (3)	C13—C14—C15—N1	176.96 (14)
O2—C2—C3—C4	−175.56 (15)	O5—N1—C15—C14	−150.67 (15)
C2—C3—C4—C5	−0.9 (3)	O4—N1—C15—C14	28.6 (2)
C3—C4—C5—C6	−179.22 (16)	O5—N1—C15—C16	28.9 (2)
C3—C4—C5—C10	1.8 (3)	O4—N1—C15—C16	−151.83 (15)
C4—C5—C6—C7	−178.77 (17)	C14—C15—C16—C17	0.6 (3)
C10—C5—C6—C7	0.2 (3)	N1—C15—C16—C17	−179.02 (14)
C5—C6—C7—C8	−0.7 (3)	C15—C16—C17—C12	2.4 (3)
C25—O3—C8—C9	0.9 (3)	C13—C12—C17—C16	−3.2 (2)
C25—O3—C8—C7	−178.95 (16)	C11—C12—C17—C16	174.59 (14)
C6—C7—C8—O3	−179.10 (17)	C2—O2—C18—O6	9.5 (2)
C6—C7—C8—C9	1.0 (3)	C2—O2—C18—C19	−168.93 (12)
O3—C8—C9—C10	179.26 (16)	O6—C18—C19—C24	−166.57 (15)
C7—C8—C9—C10	−0.9 (3)	O2—C18—C19—C24	11.9 (2)
C2—C1—C10—C9	178.82 (14)	O6—C18—C19—C20	10.0 (2)
C11—C1—C10—C9	−4.9 (2)	O2—C18—C19—C20	−171.59 (13)
C2—C1—C10—C5	−1.8 (2)	C24—C19—C20—C21	0.7 (2)
C11—C1—C10—C5	174.53 (13)	C18—C19—C20—C21	−175.95 (14)
C8—C9—C10—C1	179.79 (14)	C19—C20—C21—C22	0.5 (2)
C8—C9—C10—C5	0.4 (2)	C20—C21—C22—C23	−1.3 (3)
C4—C5—C10—C1	−0.5 (2)	C20—C21—C22—N2	178.58 (14)
C6—C5—C10—C1	−179.47 (14)	O8—N2—C22—C21	6.3 (2)
C4—C5—C10—C9	178.94 (15)	O7—N2—C22—C21	−173.67 (15)
C6—C5—C10—C9	−0.1 (2)	O8—N2—C22—C23	−173.82 (16)
C2—C1—C11—O1	−79.86 (19)	O7—N2—C22—C23	6.2 (2)
C10—C1—C11—O1	103.77 (18)	C21—C22—C23—C24	0.8 (3)
C2—C1—C11—C12	96.63 (17)	N2—C22—C23—C24	−179.08 (15)
C10—C1—C11—C12	−79.75 (18)	C22—C23—C24—C19	0.5 (2)
O1—C11—C12—C17	5.0 (2)	C20—C19—C24—C23	−1.2 (2)
C1—C11—C12—C17	−171.52 (14)	C18—C19—C24—C23	175.27 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O7ⁱ	0.95	2.58	3.211 (3)	124
C23—H23···O4ⁱⁱ	0.95	2.55	3.435 (2)	154

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

Experimental details

Crystal data
Chemical formula	C₂₅H₁₆N₂O₈
M_r	472.40
Crystal system, space group	Triclinic, P1
Temperature (K)	193
a, b, c (Å)	7.30691 (15), 10.2555 (2), 14.7645 (3)
α, β, γ (°)	84.750 (1), 86.278 (1), 74.079 (1)
V (Å³)	1058.57 (4)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.60 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.599, 0.911
No. of measured, independent and observed [I > 2σ(I)] reflections	19272, 3818, 2769
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.124, 1.09
No. of reflections	3818
No. of parameters	319
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.22

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2004), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O7ⁱ	0.95	2.58	3.211 (3)	124
C23—H23···O4ⁱⁱ	0.95	2.55	3.435 (2)	154

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

Acknowledgements

The authors express their gratitude to Masters Yuichi Kato and Atsushi Nagasawa, Department of Organic and Polymer Materials Chemistry, Graduate School, Tokyo University of Agriculture & Technology, and Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture & Technology, for technical advice.

References

Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381–388. 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
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Mitsui, R., Nakaema, K., Noguchi, K., Okamoto, A. & Yonezawa, N. (2008). Acta Cryst. E64, o1278. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mitsui, R., Nakaema, K., Noguchi, K. & Yonezawa, N. (2008). Acta Cryst. E64, o2497. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mitsui, R., Noguchi, K. & Yonezawa, N. (2009). Acta Cryst. E65, o543. Web of Science CSD CrossRef IUCr Journals Google Scholar
Muto, T., Kato, Y., Nagasawa, A., Okamoto, A. & Yonezawa, N. (2010). Acta Cryst. E66, o2752. Web of Science CSD CrossRef IUCr Journals Google Scholar
Nagasawa, A., Mitsui, R., Okamoto, A. & Yonezawa, N. (2010). Acta Cryst. E66, o2820–o2821. Web of Science CSD CrossRef IUCr Journals Google Scholar
Okamoto, A. & Yonezawa, N. (2009). Chem. Lett. 38, 914–915. Web of Science CrossRef CAS Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2004). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals 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