Methyl 4-(2,7-dimeth­oxy-1-naphtho­yl)benzoate

Hijikata, D.; Nakaema, K.; Watanabe, S.; Okamoto, A.; Yonezawa, N.

doi:10.1107/S160053681000382X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o554

doi:10.1107/S160053681000382X

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Methyl 4-(2,7-dimethoxy-1-naphthoyl)benzoate

Daichi Hijikata,^a Kosuke Nakaema,^a Shoji Watanabe,^a Akiko Okamoto ^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: yonezawa@cc.tuat.ac.jp

(Received 18 January 2010; accepted 31 January 2010; online 6 February 2010)

In the title compound, C₂₁H₁₈O₅, the dihedral angle between the naphthalene ring system and the benzene ring is 86.65 (6)°. The bridging carbonyl C—C(=O)—C plane makes dihedral angles of 83.57 (7) and 20.21 (8)°, respectively, with the naphthalene ring system and the benzene ring. The ester O—C=O plane and the benzene ring are almost coplanar, making a dihedral angle of 3.81 (18)°. The two methoxy groups lie essentially in the naphthalene ring plane [C—O—C—C torsion angles = 2.1 (2) and −1.44 (19)°]. In the crystal structure, a centrosymmetric dimer is formed through C—H⋯O bonds connecting the 7-methoxy group and the carbonyl O atom of the ester group. The dimers are further linked by C—H⋯O hydrogen bonds between the methoxycarbonyl group and the bridging carbonyl O atom.

Related literature

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

Experimental

Crystal data

C₂₁H₁₈O₅
M_r = 350.35
Triclinic, $[P \overline 1]$
a = 7.7714 (2) Å
b = 9.5195 (3) Å
c = 12.2737 (4) Å
α = 97.525 (2)°
β = 97.919 (2)°
γ = 106.630 (2)°
V = 847.73 (5) Å³
Z = 2
Cu Kα radiation
μ = 0.81 mm⁻¹
T = 193 K
0.40 × 0.20 × 0.05 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.816, T_max = 0.960
15482 measured reflections
3066 independent reflections
2571 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.117
S = 1.08
3066 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19B⋯O2ⁱ	0.98	2.57	3.461 (2)	152
C21—H21A⋯O1ⁱⁱ	0.98	2.49	3.4446 (19)	163
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x-1, y-1, 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 global, I. DOI: 10.1107/S160053681000382X/is2518sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681000382X/is2518Isup2.hkl

checkCIF report

Comment top

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). The aroyl groups at 1,8-positions of the naphthalene rings in these compounds are twisted almost perpendicularly but a little tiltedly toward exo sides against the naphthalene ring.

Recently, we have reported the X-ray crystal structures of several 1,8-diaroylated naphthalene homologues exemplified by bis(4-bromobenzoyl)(2,7-dimethoxynaphthalene-1,8-diyl)dimethanone (Watanabe et al., 2010). Furthermore, we have also clarified the crystal structures of 1-monoaroylated naphthalenes. 1-(4-Chlorobenzoyl)-2,7-dimethoxynaphthalene (Mitsui, Nakaema, Noguchi, Okamoto & Yonezawa, 2008) and (4-chlorobenzoyl)(2-ethoxy-7-methoxynaphthalen-1-yl)methanone (Mitsui et al., 2009) have essentially same non-coplanar structure as 1,8-diaroylated naphthalenes, and (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone has substantially coplanar structure by intramolecular hydrogen bonding (Mitsui, Nakaema, Noguchi & Yonezawa, 2008). As a part of the course of our continuous study on the molecular structures of this kind of homologous molecules, the X-ray crystal structure of title compound, 1-monoaroylnaphthalene bearing ester group, is discussed in this report.

An ORTEPIII (Burnett & Johnson, 1996) plot of (I) is displayed in Fig. 1. In the molecule of (I), the interplanar angle between the benzene ring (C12—C17) and the naphthalene ring (C1—C10) is 86.65 (6)°. The dihedral angle between the ketonic C=O plane and the naphthalene ring is 83.57 (7)° [C10—C1—C11—O1 torsion angle = 84.41 (18)°]. The dihedral angle between the ketonic C=O plane and the benzene ring is 20.21 (8)° [C17—C12—C11—O1 torsion angle = 19.9 (2)°]. The torsion angle between the ketonic carbonyl group and benzene ring [C17—C12—C11—O1 torsion angle = 19.9 (2)°] is larger than that between the carbonyl moiety of ester group and the benzene ring [C14—C15—C20—O2 torsion angle = -4.0 (2)°]. Two methoxy groups lie essentially on the naphthalene ring plane. The methyl group on O4, which is a part of methoxy group adjacent to the aroyl group, is oriented to the exo site of the molecule and that on O5 is directed to endo site. In the crystal packing, molecules are aligned forming dimeric pairs. Each pair has two intermolecular C—H···O bonds therein: equivalent hydrogen bonds between a H atom of 7-methoxy group (H19B) and the O atom of carbonyl moiety in ester group (O2). There is another type of hydrogen bond between dimeric pairs: hydrogen bonds between a H atom of the methyl moiety in ester group (H21A) and the O atom of ketonic carbonyl group (O1) (Fig. 2 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: Mitsui, Nakaema, Noguchi et al. (2008); Mitsui, Nakaema, Noguchi & Yonezawa (2008); Mitsui et al. (2009); Watanabe et al. (2010).

Experimental top

The title compound was prepared by regioselective electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene with 4-(bromomethyl)benzoyl chloride followed by transformation of bromomethyl group. Single crystals suitable for X-ray diffraction were obtained by recrystallization from ethanol.

Spectroscopic Data: ¹H NMR (300 MHz, CDCl₃): δ 3.73 (3H, s), 3.76 (3H, s), 3.94 (3H, s), 6.83 (1H, s), 7.01 (1H, d, J = 9.0 Hz), 7.14 (1H, d, J = 9.0 Hz), 7.71 (1H, d, J = 9.0 Hz), 7.87–7.90 (3H, m), 8.07 (2H, d, J = 8.1 Hz); ¹³C NMR (75.0 MHz, CDCl₃): δ 52.4, 55.2, 56.2, 101.9, 110.1, 117.2, 121.0, 124.4, 129.2, 129.7, 129.8, 131.6, 133.0, 133.9, 141.6, 155.4, 159.1, 166.4, 197.5; IR (KBr): 1674, 1625, 1511; m.p. = 154.6–157.1 °C; Anal. Calcd for C₂₁H₁₈O₅: C 71.99, H 5.18%. Found: C 72.05, H 5.25%.

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 (I), showing the atom-labeling scheme and 50% probability displacement ellipsoids.
	Fig. 2. A partial crystal packing diagram of compound (I). The intermolecular C—H···O interactions are shown as dashed lines.

Methyl 4-(2,7-dimethoxy-1-naphthoyl)benzoate top

Crystal data top

C₂₁H₁₈O₅	Z = 2
M_r = 350.35	F(000) = 368
Triclinic, P1	D_x = 1.373 Mg m⁻³
Hall symbol: -P 1	Melting point = 427.6–430.1 K
a = 7.7714 (2) Å	Cu Kα radiation, λ = 1.54187 Å
b = 9.5195 (3) Å	Cell parameters from 10631 reflections
c = 12.2737 (4) Å	θ = 3.7–68.2°
α = 97.525 (2)°	µ = 0.81 mm⁻¹
β = 97.919 (2)°	T = 193 K
γ = 106.630 (2)°	Block, yellow
V = 847.73 (5) Å³	0.40 × 0.20 × 0.05 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	3066 independent reflections
Radiation source: rotating anode	2571 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
Detector resolution: 10.00 pixels mm^-1	θ_max = 68.2°, θ_min = 3.7°
ω scans	h = −9→9
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −11→11
T_min = 0.816, T_max = 0.960	l = −14→14
15482 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.117	w = 1/[σ²(F_o²) + (0.0674P)² + 0.1365P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3066 reflections	Δρ_max = 0.24 e Å⁻³
239 parameters	Δρ_min = −0.20 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: 0.0056 (9)

Crystal data top

C₂₁H₁₈O₅	γ = 106.630 (2)°
M_r = 350.35	V = 847.73 (5) Å³
Triclinic, P1	Z = 2
a = 7.7714 (2) Å	Cu Kα radiation
b = 9.5195 (3) Å	µ = 0.81 mm⁻¹
c = 12.2737 (4) Å	T = 193 K
α = 97.525 (2)°	0.40 × 0.20 × 0.05 mm
β = 97.919 (2)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3066 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	2571 reflections with I > 2σ(I)
T_min = 0.816, T_max = 0.960	R_int = 0.029
15482 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.08	Δρ_max = 0.24 e Å⁻³
3066 reflections	Δρ_min = −0.20 e Å⁻³
239 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	1.18952 (13)	0.98013 (12)	0.33288 (8)	0.0454 (3)
O2	0.76893 (17)	0.46407 (13)	0.65183 (9)	0.0570 (3)
O3	0.59054 (13)	0.32936 (11)	0.49174 (8)	0.0423 (3)
O4	0.76938 (14)	1.00486 (13)	0.26247 (8)	0.0470 (3)
O5	1.29922 (14)	0.59184 (12)	0.00036 (9)	0.0479 (3)
C1	0.94439 (17)	0.87694 (14)	0.17801 (11)	0.0320 (3)
C2	0.80587 (18)	0.93926 (15)	0.16515 (12)	0.0363 (3)
C3	0.7095 (2)	0.93512 (17)	0.05840 (12)	0.0420 (4)
H3	0.6144	0.9794	0.0502	0.050*
C4	0.7548 (2)	0.86624 (17)	−0.03362 (12)	0.0431 (4)
H4	0.6898	0.8635	−0.1058	0.052*
C5	0.89479 (18)	0.79937 (15)	−0.02438 (11)	0.0351 (3)
C6	0.9413 (2)	0.72579 (16)	−0.11830 (12)	0.0426 (4)
H6	0.8780	0.7228	−0.1910	0.051*
C7	1.0735 (2)	0.65969 (16)	−0.10717 (12)	0.0439 (4)
H7	1.1012	0.6098	−0.1715	0.053*
C8	1.17077 (19)	0.66469 (15)	0.00021 (12)	0.0375 (3)
C9	1.13305 (18)	0.73542 (15)	0.09430 (11)	0.0342 (3)
H9	1.1997	0.7383	0.1659	0.041*
C10	0.99256 (17)	0.80497 (14)	0.08386 (11)	0.0326 (3)
C11	1.04313 (18)	0.88600 (15)	0.29455 (11)	0.0334 (3)
C12	0.95508 (17)	0.77299 (15)	0.36010 (11)	0.0328 (3)
C13	1.00721 (19)	0.79937 (16)	0.47627 (11)	0.0370 (3)
H13	1.0970	0.8899	0.5134	0.044*
C14	0.92869 (19)	0.69435 (16)	0.53730 (11)	0.0391 (3)
H14	0.9634	0.7133	0.6164	0.047*
C15	0.79879 (18)	0.56076 (16)	0.48323 (11)	0.0352 (3)
C16	0.74621 (19)	0.53386 (16)	0.36727 (11)	0.0370 (3)
H16	0.6573	0.4429	0.3301	0.044*
C17	0.82356 (18)	0.63965 (15)	0.30640 (11)	0.0358 (3)
H17	0.7869	0.6214	0.2274	0.043*
C18	0.6225 (2)	1.0673 (2)	0.25460 (15)	0.0519 (4)
H18A	0.6111	1.1086	0.3297	0.062*
H18B	0.5085	0.9895	0.2185	0.062*
H18C	0.6472	1.1467	0.2101	0.062*
C19	1.4033 (2)	0.59325 (18)	0.10659 (13)	0.0460 (4)
H19A	1.4865	0.5344	0.0961	0.055*
H19B	1.3203	0.5502	0.1553	0.055*
H19C	1.4742	0.6961	0.1411	0.055*
C20	0.72025 (19)	0.44915 (16)	0.55271 (11)	0.0381 (3)
C21	0.5110 (2)	0.21403 (17)	0.55273 (13)	0.0466 (4)
H21A	0.4122	0.1347	0.5020	0.056*
H21B	0.4621	0.2568	0.6138	0.056*
H21C	0.6051	0.1726	0.5835	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0398 (6)	0.0492 (6)	0.0360 (5)	0.0012 (5)	0.0004 (4)	0.0041 (5)
O2	0.0752 (8)	0.0539 (7)	0.0302 (6)	0.0028 (6)	0.0075 (5)	0.0079 (5)
O3	0.0465 (6)	0.0410 (6)	0.0352 (5)	0.0071 (4)	0.0065 (4)	0.0075 (4)
O4	0.0489 (6)	0.0594 (7)	0.0394 (6)	0.0285 (5)	0.0095 (5)	0.0043 (5)
O5	0.0547 (6)	0.0520 (6)	0.0406 (6)	0.0230 (5)	0.0140 (5)	0.0008 (5)
C1	0.0331 (7)	0.0312 (7)	0.0297 (7)	0.0068 (5)	0.0052 (5)	0.0061 (5)
C2	0.0357 (7)	0.0351 (7)	0.0363 (7)	0.0084 (6)	0.0066 (6)	0.0063 (6)
C3	0.0391 (8)	0.0460 (8)	0.0414 (8)	0.0157 (6)	0.0006 (6)	0.0116 (7)
C4	0.0450 (8)	0.0437 (8)	0.0349 (7)	0.0074 (6)	−0.0021 (6)	0.0113 (6)
C5	0.0393 (7)	0.0317 (7)	0.0285 (7)	0.0033 (6)	0.0031 (5)	0.0059 (5)
C6	0.0530 (9)	0.0391 (8)	0.0283 (7)	0.0047 (7)	0.0041 (6)	0.0054 (6)
C7	0.0572 (9)	0.0394 (8)	0.0313 (7)	0.0098 (7)	0.0117 (6)	0.0017 (6)
C8	0.0407 (7)	0.0325 (7)	0.0374 (7)	0.0077 (6)	0.0112 (6)	0.0035 (6)
C9	0.0383 (7)	0.0328 (7)	0.0292 (7)	0.0077 (6)	0.0065 (5)	0.0048 (5)
C10	0.0355 (7)	0.0289 (7)	0.0290 (7)	0.0030 (5)	0.0055 (5)	0.0058 (5)
C11	0.0361 (7)	0.0349 (7)	0.0290 (7)	0.0130 (6)	0.0059 (5)	0.0006 (5)
C12	0.0338 (7)	0.0366 (7)	0.0287 (7)	0.0139 (6)	0.0047 (5)	0.0028 (5)
C13	0.0401 (7)	0.0375 (7)	0.0290 (7)	0.0096 (6)	0.0020 (5)	0.0005 (6)
C14	0.0452 (8)	0.0445 (8)	0.0251 (6)	0.0127 (6)	0.0039 (5)	0.0027 (6)
C15	0.0388 (7)	0.0392 (8)	0.0304 (7)	0.0164 (6)	0.0073 (5)	0.0057 (6)
C16	0.0414 (7)	0.0345 (7)	0.0317 (7)	0.0099 (6)	0.0024 (6)	0.0023 (6)
C17	0.0414 (7)	0.0387 (8)	0.0254 (6)	0.0129 (6)	0.0020 (5)	0.0027 (6)
C18	0.0459 (9)	0.0587 (10)	0.0587 (10)	0.0274 (8)	0.0132 (7)	0.0078 (8)
C19	0.0449 (8)	0.0487 (9)	0.0463 (9)	0.0180 (7)	0.0103 (6)	0.0051 (7)
C20	0.0428 (8)	0.0407 (8)	0.0310 (7)	0.0140 (6)	0.0078 (6)	0.0041 (6)
C21	0.0498 (9)	0.0439 (9)	0.0462 (9)	0.0121 (7)	0.0118 (7)	0.0109 (7)

Geometric parameters (Å, º) top

O1—C11	1.2154 (16)	C9—C10	1.4298 (19)
O2—C20	1.2002 (17)	C9—H9	0.9500
O3—C20	1.3368 (17)	C11—C12	1.4933 (18)
O3—C21	1.4499 (17)	C12—C17	1.3939 (19)
O4—C2	1.3772 (17)	C12—C13	1.3960 (18)
O4—C18	1.4277 (18)	C13—C14	1.381 (2)
O5—C8	1.3687 (17)	C13—H13	0.9500
O5—C19	1.4327 (18)	C14—C15	1.391 (2)
C1—C2	1.3708 (19)	C14—H14	0.9500
C1—C10	1.4154 (19)	C15—C16	1.3937 (19)
C1—C11	1.5065 (18)	C15—C20	1.496 (2)
C2—C3	1.407 (2)	C16—C17	1.3813 (19)
C3—C4	1.370 (2)	C16—H16	0.9500
C3—H3	0.9500	C17—H17	0.9500
C4—C5	1.408 (2)	C18—H18A	0.9800
C4—H4	0.9500	C18—H18B	0.9800
C5—C6	1.413 (2)	C18—H18C	0.9800
C5—C10	1.4231 (18)	C19—H19A	0.9800
C6—C7	1.351 (2)	C19—H19B	0.9800
C6—H6	0.9500	C19—H19C	0.9800
C7—C8	1.414 (2)	C21—H21A	0.9800
C7—H7	0.9500	C21—H21B	0.9800
C8—C9	1.3695 (19)	C21—H21C	0.9800

C20—O3—C21	115.70 (11)	C13—C12—C11	119.85 (12)
C2—O4—C18	118.25 (12)	C14—C13—C12	120.21 (13)
C8—O5—C19	117.18 (11)	C14—C13—H13	119.9
C2—C1—C10	120.65 (12)	C12—C13—H13	119.9
C2—C1—C11	118.48 (12)	C13—C14—C15	120.17 (12)
C10—C1—C11	120.86 (12)	C13—C14—H14	119.9
C1—C2—O4	115.70 (12)	C15—C14—H14	119.9
C1—C2—C3	121.08 (14)	C14—C15—C16	119.85 (13)
O4—C2—C3	123.22 (13)	C14—C15—C20	118.23 (12)
C4—C3—C2	118.99 (14)	C16—C15—C20	121.91 (12)
C4—C3—H3	120.5	C17—C16—C15	119.91 (13)
C2—C3—H3	120.5	C17—C16—H16	120.0
C3—C4—C5	121.91 (13)	C15—C16—H16	120.0
C3—C4—H4	119.0	C16—C17—C12	120.43 (12)
C5—C4—H4	119.0	C16—C17—H17	119.8
C4—C5—C6	122.64 (13)	C12—C17—H17	119.8
C4—C5—C10	118.76 (13)	O4—C18—H18A	109.5
C6—C5—C10	118.61 (13)	O4—C18—H18B	109.5
C7—C6—C5	121.56 (13)	H18A—C18—H18B	109.5
C7—C6—H6	119.2	O4—C18—H18C	109.5
C5—C6—H6	119.2	H18A—C18—H18C	109.5
C6—C7—C8	120.04 (14)	H18B—C18—H18C	109.5
C6—C7—H7	120.0	O5—C19—H19A	109.5
C8—C7—H7	120.0	O5—C19—H19B	109.5
O5—C8—C9	124.51 (13)	H19A—C19—H19B	109.5
O5—C8—C7	114.37 (12)	O5—C19—H19C	109.5
C9—C8—C7	121.10 (14)	H19A—C19—H19C	109.5
C8—C9—C10	119.48 (13)	H19B—C19—H19C	109.5
C8—C9—H9	120.3	O2—C20—O3	123.51 (13)
C10—C9—H9	120.3	O2—C20—C15	124.10 (13)
C1—C10—C5	118.60 (13)	O3—C20—C15	112.39 (11)
C1—C10—C9	122.18 (12)	O3—C21—H21A	109.5
C5—C10—C9	119.20 (12)	O3—C21—H21B	109.5
O1—C11—C12	121.49 (12)	H21A—C21—H21B	109.5
O1—C11—C1	121.30 (12)	O3—C21—H21C	109.5
C12—C11—C1	117.20 (11)	H21A—C21—H21C	109.5
C17—C12—C13	119.41 (12)	H21B—C21—H21C	109.5
C17—C12—C11	120.72 (11)

C10—C1—C2—O4	179.30 (11)	C6—C5—C10—C9	−0.47 (18)
C11—C1—C2—O4	−0.32 (18)	C8—C9—C10—C1	178.58 (11)
C10—C1—C2—C3	−0.8 (2)	C8—C9—C10—C5	−0.08 (18)
C11—C1—C2—C3	179.60 (12)	C2—C1—C11—O1	−98.98 (16)
C18—O4—C2—C1	−177.96 (12)	C10—C1—C11—O1	81.40 (17)
C18—O4—C2—C3	2.1 (2)	C2—C1—C11—C12	82.03 (15)
C1—C2—C3—C4	0.6 (2)	C10—C1—C11—C12	−97.59 (14)
O4—C2—C3—C4	−179.50 (13)	O1—C11—C12—C17	−158.78 (14)
C2—C3—C4—C5	0.1 (2)	C1—C11—C12—C17	20.22 (18)
C3—C4—C5—C6	178.96 (13)	O1—C11—C12—C13	19.9 (2)
C3—C4—C5—C10	−0.5 (2)	C1—C11—C12—C13	−161.07 (12)
C4—C5—C6—C7	−178.55 (13)	C17—C12—C13—C14	−0.2 (2)
C10—C5—C6—C7	0.9 (2)	C11—C12—C13—C14	−178.91 (12)
C5—C6—C7—C8	−0.8 (2)	C12—C13—C14—C15	0.8 (2)
C19—O5—C8—C9	−1.44 (19)	C13—C14—C15—C16	−0.8 (2)
C19—O5—C8—C7	179.73 (12)	C13—C14—C15—C20	178.81 (13)
C6—C7—C8—O5	179.11 (12)	C14—C15—C16—C17	0.2 (2)
C6—C7—C8—C9	0.2 (2)	C20—C15—C16—C17	−179.44 (13)
O5—C8—C9—C10	−178.55 (11)	C15—C16—C17—C12	0.5 (2)
C7—C8—C9—C10	0.2 (2)	C13—C12—C17—C16	−0.5 (2)
C2—C1—C10—C5	0.31 (19)	C11—C12—C17—C16	178.25 (12)
C11—C1—C10—C5	179.92 (11)	C21—O3—C20—O2	−0.9 (2)
C2—C1—C10—C9	−178.35 (12)	C21—O3—C20—C15	178.40 (12)
C11—C1—C10—C9	1.26 (19)	C14—C15—C20—O2	−4.0 (2)
C4—C5—C10—C1	0.33 (18)	C16—C15—C20—O2	175.62 (15)
C6—C5—C10—C1	−179.18 (11)	C14—C15—C20—O3	176.73 (12)
C4—C5—C10—C9	179.04 (11)	C16—C15—C20—O3	−3.64 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19B···O2ⁱ	0.98	2.57	3.461 (2)	152
C21—H21A···O1ⁱⁱ	0.98	2.49	3.4446 (19)	163

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

Experimental details

Crystal data
Chemical formula	C₂₁H₁₈O₅
M_r	350.35
Crystal system, space group	Triclinic, P1
Temperature (K)	193
a, b, c (Å)	7.7714 (2), 9.5195 (3), 12.2737 (4)
α, β, γ (°)	97.525 (2), 97.919 (2), 106.630 (2)
V (Å³)	847.73 (5)
Z	2
Radiation type	Cu Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.40 × 0.20 × 0.05

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.816, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	15482, 3066, 2571
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.117, 1.08
No. of reflections	3066
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.20

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
C19—H19B···O2ⁱ	0.98	2.57	3.461 (2)	152
C21—H21A···O1ⁱⁱ	0.98	2.49	3.4446 (19)	163

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

Acknowledgements

The authors would express their gratitude to Professor Keiichi Noguchi for technical advice. This work was partially supported by the Iketani Science and Technology Foundation, Tokyo, Japan.

References

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