4-Hy­droxy­methyl-10-meth­oxy-17,22-dioxapenta­cyclo­[21.2.2.213,16.13,7.011,30]triaconta-1(25),3,5,7(30),8,10,13,15,23,26,28-undeca­ene-2,12-dione acetone monosolvate

Hijikata, D.; Sasagawa, K.; Yoshiwaka, S.; Okamoto, A.; Yonezawa, N.

doi:10.1107/S1600536812033521

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 8| August 2012| Pages o2598-o2599

https://doi.org/10.1107/S1600536812033521

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4-Hydroxymethyl-10-methoxy-17,22-dioxapentacyclo[21.2.2.2^13,16.1^3,7.0^11,30]triaconta-1(25),3,5,7(30),8,10,13,15,23,26,28-undecaene-2,12-dione acetone monosolvate

Daichi Hijikata,^a Kosuke Sasagawa,^a Sayaka Yoshiwaka,^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: aokamoto@cc.tuat.ac.jp

(Received 19 July 2012; accepted 25 July 2012; online 28 July 2012)

In the title compound, C₃₀H₂₆O₆·C₃H₆O, the syn-oriented benzoyl groups are nearly parallel to each other; the dihedral angle between their benzene rings is 15.9 (1)°. They form dihedral angles of 72.5 (1) and 84.3 (1)° with the naphthalene system. In the crystal, molecules are linked into a three-dimensional architecture by C—H⋯O and C—H⋯π interactions.

Related literature

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009 ); Okamoto et al. (2011 ). For applications of related molecules, see; Okamoto et al. (2012 ). For the structures of closely related compounds, see: Hijikata et al. (2010 ); Mitsui et al. (2010 ); Sasagawa et al. (2011 ); Watanabe et al. (2010 ).

Experimental

Crystal data

C₃₀H₂₆O₆·C₃H₆O
M_r = 540.59
Orthorhombic, P b c a
a = 15.4948 (3) Å
b = 16.1272 (3) Å
c = 22.4430 (4) Å
V = 5608.23 (18) Å³
Z = 8
Cu Kα radiation
μ = 0.73 mm⁻¹
T = 193 K
0.50 × 0.45 × 0.40 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.712, T_max = 0.759
99441 measured reflections
5132 independent reflections
4829 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.098
S = 1.05
5132 reflections
366 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C12–C17 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O2ⁱ	0.95	2.47	3.3241 (15)	150
C6—H6⋯O1ⁱⁱ	0.95	2.38	3.3245 (16)	172
C7—H7⋯O3ⁱⁱ	0.95	2.59	3.3910 (17)	143
C14—H14⋯O5ⁱⁱⁱ	0.95	2.40	3.3328 (15)	169
C21—H21⋯O1S^iv	0.95	2.54	3.482 (2)	172
C2S—H2S2⋯Cg^v	0.98	2.86	3.830 (2)	171
Symmetry codes: (i) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+2, -y+1, -z; (iv) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ ; (v) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, z]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812033521/ld2069sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812033521/ld2069Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812033521/ld2069Isup3.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; Okamoto, Mitsui et al., 2011). As one of applications, the authors have integrated the resulting molecular unit to poly(ether ketone)backbone via nucleophilic aromatic substitution polycondensation (Okamoto et al., 2012). Furthermore we have also reported the crystal structures of several 1,8-diaroylated naphthalene analogues exemplified by (2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorobenzoyl)dimethanone (Watanabe et al., 2010) and [8-(4-butoxybenzoyl)-2,7-dimethoxynaphthalen-1-yl](4-butoxyphenyl)methanone (Sasagawa et al., 2011). These molecules have essentially same non-coplanarly features. The aroyl groups at the 1,8-positions of the naphthalene rings in these molecules are twisted in almost perpendicular fashion, but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene rings. On the other hand, 1,8-bis(4-chlorobenzoyl)-7-methoxynaphthalene-2-ol ethanol monosolvate (Mitsui et al., 2010) and 2,7-dimethoxy-1,8-bis(4-phenoxybenzoyl)naphthalene (Hijikata et al., 2010) have apparently different spatial organizations. The aroyl groups attached to the naphthalene ring are oriented in the same directions. 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 containing a 1,8-diaroylenenaphthalene moiety is discussed in this article.

The crystal packing is stabilized by intermolecular C—H···O hydrogen bonding between the oxygen atom (O2) of the carbonyl group of the adjacent molecule and one hydrogen atom (H3) on the naphthalene ring along the a axis (C3—H3···O2ⁱ= 2.47 Å; Table 1). Furthermore, two intermolecular C—H···O interactions, between the oxygen atom (O3) of the methoxy group and one hydrogen atom (H7) on the naphthalene ring, and between the oxygen atom (O1) of the carbonyl group and one hydrogen atom (H6) on the naphthalene ring, are observed along the c axis (C7—H7···O3ⁱⁱ= 2.59 Å, C6—H6···O1ⁱⁱ= 2.38 Å; Table 1). Moreover, the title compounds and acetones are linked by two C—H···O interactions and C—H···π interaction forming a three-dimensional architecture. The C—H···O interactions (C14—H14···O5ⁱⁱⁱ= 2.40 Å, C21—H21···O1S^iV= 2.54 Å; Fig. 2 and Table 1) and the C—H···π interaction (C2S^v—H2S2^v···Cg= 2.86 Å; Fig. 2 and Table 1) also contribute to the stabilization of the molecular conformation and crystal structure.

Related literature top

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009); Okamoto et al. (2011). For applications of related molecules, see; Okamoto et al. (2012). For the structures of closely related compounds, see: Hijikata et al. (2010); Mitsui et al. (2010); Sasagawa et al. (2011); Watanabe et al. (2010).

Experimental top

The title compound was prepared by S_N2 reaction of 1,8-bis(4-hydroxybenzoyl)-2,7-dimethoxynaphthalene (1.0 mmol, 428 mg) with 1,4-dibromobutane (1.0 mmol, 215 mg) in N,N-dimethylacetamide (DMAc; 25.0 ml) with potassium carbonate (5.0 mmol, 691 mg). [The precursor, 1,8-bis(4-hydroxybenzoyl)-2,7-dimethoxynaphthalene, was obtained via S_NAr reaction of 1,8-bis(4-fluorobenzoyl)-2,7-dimethoxynaphthalene with sodium hydroxide.] After the reaction, the mixture was stirred at 333 K for 48 h, it was poured into water and extracted with CHCl₃. The combined extracts were washed with 2M aqueous NaOH followed with brine. The organic layers were dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give the crude product, which was purified by column chromatography (silica gel, CHCl₃; isolated yield 47%). The pure product was crystallized from acetone to yield single crystals.

¹H NMR δ (300 MHz, CDCl₃): 1.78–1.93(4H, m),3.72(6H, s), 4.10–4.27(4H, m) 6.31(2H, dd, J=8.5, 2.4 Hz), 6.63(2H, dd, J=8.9, 2.4 Hz), 6.88(2H, dd, J=8.5, 2.0 Hz), 7.20(2H, d, J=8.9 Hz), 7.87(2H, dd, J=8.9, 2.0 Hz), 7.92(2H, d, J=8.9 Hz) p.p.m.

¹³C NMR δ (75 MHz, CDCl₃): 22.49, 56.59, 66.80, 111.15, 113.77, 115.45, 121.81, 125.10, 128.81, 129.93, 131.24, 131.69, 133.82, 156.01, 160.90, 193.86 p.p.m.

IR (KBr): 1668 (C=O), 1600, 1509, 1460 (Ar, naphthalene), 1263 (=C—O—C) cm^-1.

HRMS (m/z): [M + H]⁺ calcd for C₃₀H₂₇O₆, 483.1808 found, 483.1836.

m.p. 537.5–538.8 K

Structure description top

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009); Okamoto et al. (2011). For applications of related molecules, see; Okamoto et al. (2012). For the structures of closely related compounds, see: Hijikata et al. (2010); Mitsui et al. (2010); Sasagawa et al. (2011); 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: Il Milione (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 50% probability displacement ellipsoids
	Fig. 2. The dimeric associates of title compound. The C—H···O and C—H···π interactions are shown as dashed lines.

4-Hydroxymethyl-10-methoxy-17,22- dioxapentacyclo[21.2.2.2^13,16.1^3,7.0^11,30]triaconta- 1(25),3,5,7(30),8,10,13,15,23,26,28-undecaene-2,12-dione acetone monosolvate top

Crystal data top

C₃₀H₂₆O₆·C₃H₆O	D_x = 1.280 Mg m⁻³
M_r = 540.59	Melting point = 537.5–538.8 K
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 92773 reflections
a = 15.4948 (3) Å	θ = 3.4–68.3°
b = 16.1272 (3) Å	µ = 0.73 mm⁻¹
c = 22.4430 (4) Å	T = 193 K
V = 5608.23 (18) Å³	Block, colorless
Z = 8	0.50 × 0.45 × 0.40 mm
F(000) = 2288

Data collection top

Rigaku R-AXIS RAPID diffractometer	5132 independent reflections
Radiation source: rotating anode	4829 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 10.000 pixels mm^-1	θ_max = 68.3°, θ_min = 3.9°
ω scans	h = −18→18
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −19→19
T_min = 0.712, T_max = 0.759	l = −27→27
99441 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) = 0.098	w = 1/[σ²(F_o²) + (0.0495P)² + 1.7635P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
5132 reflections	Δρ_max = 0.20 e Å⁻³
366 parameters	Δρ_min = −0.19 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/6(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00160 (9)

Crystal data top

C₃₀H₂₆O₆·C₃H₆O	V = 5608.23 (18) Å³
M_r = 540.59	Z = 8
Orthorhombic, Pbca	Cu Kα radiation
a = 15.4948 (3) Å	µ = 0.73 mm⁻¹
b = 16.1272 (3) Å	T = 193 K
c = 22.4430 (4) Å	0.50 × 0.45 × 0.40 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	5132 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	4829 reflections with I > 2σ(I)
T_min = 0.712, T_max = 0.759	R_int = 0.021
99441 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.05	Δρ_max = 0.20 e Å⁻³
5132 reflections	Δρ_min = −0.19 e Å⁻³
366 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	1.07047 (5)	0.27102 (5)	0.20944 (4)	0.0347 (2)
O2	1.19956 (5)	0.17013 (6)	0.14801 (4)	0.0365 (2)
O3	0.85352 (6)	0.25079 (6)	0.23241 (4)	0.0408 (2)
O4	1.19863 (7)	−0.01523 (6)	0.13445 (5)	0.0546 (3)
O5	0.89572 (6)	0.42949 (5)	−0.01715 (4)	0.0411 (2)
O6	1.01931 (7)	0.19019 (6)	−0.10484 (4)	0.0521 (3)
O1S	0.72978 (11)	0.11706 (9)	0.09895 (8)	0.0950 (5)
C1	0.96632 (7)	0.16581 (7)	0.20049 (5)	0.0284 (2)
C2	0.88697 (8)	0.17239 (7)	0.22823 (5)	0.0324 (3)
C3	0.84625 (8)	0.10363 (8)	0.25505 (5)	0.0378 (3)
H3	0.7913	0.1093	0.2734	0.045*
C4	0.88732 (9)	0.02911 (8)	0.25413 (6)	0.0392 (3)
H4	0.8608	−0.0171	0.2729	0.047*
C5	0.96831 (8)	0.01832 (8)	0.22606 (5)	0.0351 (3)
C6	1.00846 (10)	−0.06012 (8)	0.22537 (6)	0.0434 (3)
H6	0.9814	−0.1052	0.2452	0.052*
C7	1.08489 (10)	−0.07290 (8)	0.19709 (7)	0.0463 (3)
H7	1.1115	−0.1260	0.1978	0.056*
C8	1.12400 (9)	−0.00658 (8)	0.16673 (6)	0.0400 (3)
C9	1.08822 (8)	0.07214 (7)	0.16682 (5)	0.0315 (3)
C10	1.00922 (8)	0.08721 (7)	0.19760 (5)	0.0295 (3)
C11	1.00809 (7)	0.24613 (7)	0.18132 (5)	0.0274 (2)
C12	0.97305 (7)	0.29312 (7)	0.13029 (5)	0.0276 (2)
C13	1.01308 (8)	0.36739 (7)	0.11391 (5)	0.0319 (3)
H13	1.0598	0.3879	0.1371	0.038*
C14	0.98588 (8)	0.41120 (7)	0.06475 (6)	0.0349 (3)
H14	1.0139	0.4614	0.0539	0.042*
C15	0.91706 (8)	0.38176 (7)	0.03089 (5)	0.0328 (3)
C16	0.87467 (8)	0.30933 (8)	0.04747 (6)	0.0341 (3)
H16	0.8264	0.2902	0.0253	0.041*
C17	0.90344 (8)	0.26532 (7)	0.09658 (5)	0.0312 (3)
H17	0.8752	0.2153	0.1074	0.037*
C18	1.13496 (7)	0.13598 (7)	0.12938 (5)	0.0293 (2)
C19	1.10244 (7)	0.15208 (7)	0.06846 (5)	0.0299 (3)
C20	1.13965 (8)	0.21529 (7)	0.03479 (6)	0.0334 (3)
H20	1.1838	0.2483	0.0520	0.040*
C21	1.11380 (8)	0.23109 (8)	−0.02314 (6)	0.0385 (3)
H21	1.1399	0.2744	−0.0455	0.046*
C22	1.04891 (9)	0.18246 (8)	−0.04813 (6)	0.0394 (3)
C23	1.01050 (9)	0.11965 (8)	−0.01486 (6)	0.0414 (3)
H23	0.9659	0.0870	−0.0320	0.050*
C24	1.03688 (8)	0.10465 (7)	0.04282 (6)	0.0361 (3)
H24	1.0103	0.0617	0.0652	0.043*
C25	0.76197 (9)	0.25914 (10)	0.22669 (7)	0.0496 (4)
H25A	0.7472	0.3177	0.2212	0.060*
H25B	0.7339	0.2382	0.2628	0.060*
H25C	0.7421	0.2272	0.1922	0.060*
C26	1.22703 (12)	−0.09660 (10)	0.12000 (10)	0.0656 (5)
H26A	1.1788	−0.1284	0.1034	0.079*
H26B	1.2482	−0.1241	0.1561	0.079*
H26C	1.2737	−0.0934	0.0906	0.079*
C27	0.84853 (8)	0.39230 (9)	−0.06580 (6)	0.0410 (3)
H27A	0.8372	0.4352	−0.0964	0.049*
H27B	0.7921	0.3725	−0.0508	0.049*
C28	0.89555 (9)	0.32062 (9)	−0.09454 (6)	0.0409 (3)
H28A	0.8645	0.3045	−0.1313	0.049*
H28B	0.8942	0.2726	−0.0671	0.049*
C29	0.98906 (9)	0.33975 (9)	−0.11025 (6)	0.0435 (3)
H29A	0.9906	0.3864	−0.1389	0.052*
H29B	1.0199	0.3574	−0.0738	0.052*
C30	1.03545 (11)	0.26622 (10)	−0.13715 (6)	0.0531 (4)
H30A	1.0165	0.2592	−0.1790	0.064*
H30B	1.0983	0.2774	−0.1374	0.064*
C1S	0.73688 (11)	0.04533 (11)	0.11251 (9)	0.0641 (4)
C2S	0.68285 (14)	0.00854 (15)	0.16044 (10)	0.0800 (6)
H2S1	0.7202	−0.0168	0.1906	0.096*
H2S2	0.6450	−0.0339	0.1434	0.096*
H2S3	0.6477	0.0520	0.1789	0.096*
C3S	0.80147 (16)	−0.00945 (16)	0.08399 (14)	0.1037 (8)
H3S1	0.8474	−0.0222	0.1125	0.124*
H3S2	0.8262	0.0186	0.0492	0.124*
H3S3	0.7735	−0.0610	0.0713	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0305 (4)	0.0346 (4)	0.0390 (5)	−0.0018 (3)	−0.0044 (4)	−0.0020 (3)
O2	0.0293 (4)	0.0451 (5)	0.0350 (5)	−0.0036 (4)	−0.0012 (4)	−0.0012 (4)
O3	0.0337 (5)	0.0391 (5)	0.0494 (5)	−0.0001 (4)	0.0108 (4)	−0.0077 (4)
O4	0.0438 (6)	0.0353 (5)	0.0847 (8)	0.0101 (4)	0.0133 (5)	−0.0011 (5)
O5	0.0472 (5)	0.0364 (5)	0.0398 (5)	−0.0068 (4)	−0.0094 (4)	0.0096 (4)
O6	0.0694 (7)	0.0524 (6)	0.0345 (5)	0.0088 (5)	−0.0144 (5)	−0.0026 (4)
O1S	0.0980 (11)	0.0695 (9)	0.1174 (13)	0.0063 (8)	−0.0003 (10)	0.0117 (9)
C1	0.0308 (6)	0.0314 (6)	0.0229 (5)	−0.0028 (5)	−0.0010 (4)	0.0000 (4)
C2	0.0335 (6)	0.0363 (6)	0.0273 (6)	−0.0032 (5)	0.0012 (5)	−0.0037 (5)
C3	0.0359 (6)	0.0472 (7)	0.0304 (6)	−0.0097 (5)	0.0056 (5)	−0.0015 (5)
C4	0.0458 (7)	0.0416 (7)	0.0302 (6)	−0.0135 (6)	0.0016 (5)	0.0064 (5)
C5	0.0420 (7)	0.0343 (6)	0.0291 (6)	−0.0062 (5)	−0.0040 (5)	0.0051 (5)
C6	0.0535 (8)	0.0325 (6)	0.0441 (7)	−0.0062 (6)	−0.0064 (6)	0.0118 (6)
C7	0.0508 (8)	0.0294 (6)	0.0585 (9)	0.0048 (6)	−0.0075 (7)	0.0076 (6)
C8	0.0361 (7)	0.0342 (6)	0.0497 (8)	0.0037 (5)	−0.0038 (6)	0.0016 (6)
C9	0.0319 (6)	0.0304 (6)	0.0322 (6)	0.0010 (5)	−0.0044 (5)	0.0022 (5)
C10	0.0328 (6)	0.0309 (6)	0.0247 (5)	−0.0023 (5)	−0.0048 (4)	0.0025 (4)
C11	0.0263 (5)	0.0274 (5)	0.0284 (6)	0.0015 (4)	0.0039 (4)	−0.0052 (4)
C12	0.0285 (6)	0.0261 (5)	0.0282 (6)	0.0000 (4)	0.0038 (4)	−0.0022 (4)
C13	0.0323 (6)	0.0307 (6)	0.0326 (6)	−0.0056 (5)	−0.0011 (5)	−0.0026 (5)
C14	0.0393 (7)	0.0287 (6)	0.0367 (6)	−0.0078 (5)	0.0006 (5)	0.0019 (5)
C15	0.0347 (6)	0.0316 (6)	0.0319 (6)	0.0003 (5)	0.0008 (5)	0.0027 (5)
C16	0.0314 (6)	0.0364 (6)	0.0345 (6)	−0.0063 (5)	−0.0037 (5)	0.0005 (5)
C17	0.0328 (6)	0.0285 (6)	0.0325 (6)	−0.0056 (5)	0.0030 (5)	0.0006 (5)
C18	0.0260 (5)	0.0284 (6)	0.0334 (6)	0.0047 (4)	0.0024 (5)	−0.0027 (5)
C19	0.0274 (6)	0.0290 (6)	0.0334 (6)	0.0048 (4)	0.0003 (5)	−0.0021 (5)
C20	0.0288 (6)	0.0340 (6)	0.0373 (6)	0.0015 (5)	−0.0015 (5)	0.0003 (5)
C21	0.0378 (7)	0.0398 (7)	0.0377 (7)	0.0046 (5)	0.0009 (5)	0.0068 (5)
C22	0.0444 (7)	0.0412 (7)	0.0327 (6)	0.0116 (6)	−0.0060 (5)	−0.0047 (5)
C23	0.0449 (7)	0.0357 (7)	0.0436 (7)	0.0001 (6)	−0.0114 (6)	−0.0072 (5)
C24	0.0368 (6)	0.0306 (6)	0.0410 (7)	0.0003 (5)	−0.0035 (5)	−0.0012 (5)
C25	0.0373 (7)	0.0528 (8)	0.0588 (9)	0.0057 (6)	0.0047 (6)	0.0065 (7)
C26	0.0530 (9)	0.0409 (8)	0.1029 (14)	0.0106 (7)	0.0068 (9)	−0.0143 (9)
C27	0.0364 (7)	0.0479 (7)	0.0387 (7)	−0.0037 (6)	−0.0100 (5)	0.0098 (6)
C28	0.0409 (7)	0.0469 (7)	0.0350 (7)	−0.0063 (6)	−0.0092 (5)	0.0073 (6)
C29	0.0406 (7)	0.0512 (8)	0.0388 (7)	−0.0013 (6)	−0.0050 (6)	0.0134 (6)
C30	0.0586 (9)	0.0698 (10)	0.0309 (7)	0.0094 (8)	−0.0038 (6)	0.0079 (7)
C1S	0.0513 (9)	0.0580 (10)	0.0830 (12)	−0.0041 (8)	−0.0127 (9)	−0.0068 (9)
C2S	0.0652 (12)	0.0906 (14)	0.0844 (14)	−0.0182 (10)	−0.0137 (10)	0.0009 (11)
C3S	0.0761 (15)	0.0973 (17)	0.138 (2)	0.0054 (13)	0.0116 (15)	−0.0289 (16)

Geometric parameters (Å, º) top

O1—C11	1.2222 (14)	C17—H17	0.9500
O2—C18	1.2166 (14)	C18—C19	1.4800 (16)
O3—C2	1.3697 (15)	C19—C20	1.3939 (17)
O3—C25	1.4306 (16)	C19—C24	1.3959 (17)
O4—C8	1.3717 (17)	C20—C21	1.3841 (18)
O4—C26	1.4215 (17)	C20—H20	0.9500
O5—C15	1.3654 (15)	C21—C22	1.3930 (19)
O5—C27	1.4445 (16)	C21—H21	0.9500
O6—C22	1.3586 (16)	C22—C23	1.392 (2)
O6—C30	1.4463 (19)	C23—C24	1.3787 (18)
O1S—C1S	1.201 (2)	C23—H23	0.9500
C1—C2	1.3822 (16)	C24—H24	0.9500
C1—C10	1.4328 (16)	C25—H25A	0.9800
C1—C11	1.5107 (15)	C25—H25B	0.9800
C2—C3	1.4109 (17)	C25—H25C	0.9800
C3—C4	1.3600 (19)	C26—H26A	0.9800
C3—H3	0.9500	C26—H26B	0.9800
C4—C5	1.4149 (19)	C26—H26C	0.9800
C4—H4	0.9500	C27—C28	1.511 (2)
C5—C6	1.4098 (19)	C27—H27A	0.9900
C5—C10	1.4297 (16)	C27—H27B	0.9900
C6—C7	1.359 (2)	C28—C29	1.5227 (19)
C6—H6	0.9500	C28—H28A	0.9900
C7—C8	1.4057 (19)	C28—H28B	0.9900
C7—H7	0.9500	C29—C30	1.512 (2)
C8—C9	1.3852 (17)	C29—H29A	0.9900
C9—C10	1.4266 (17)	C29—H29B	0.9900
C9—C18	1.5134 (16)	C30—H30A	0.9900
C11—C12	1.4766 (16)	C30—H30B	0.9900
C12—C17	1.3917 (16)	C1S—C3S	1.481 (3)
C12—C13	1.3980 (16)	C1S—C2S	1.487 (3)
C13—C14	1.3764 (17)	C2S—H2S1	0.9800
C13—H13	0.9500	C2S—H2S2	0.9800
C14—C15	1.3927 (17)	C2S—H2S3	0.9800
C14—H14	0.9500	C3S—H3S1	0.9800
C15—C16	1.3908 (17)	C3S—H3S2	0.9800
C16—C17	1.3846 (17)	C3S—H3S3	0.9800
C16—H16	0.9500

C2—O3—C25	117.13 (10)	C19—C20—H20	119.2
C8—O4—C26	118.39 (12)	C20—C21—C22	118.91 (12)
C15—O5—C27	119.04 (10)	C20—C21—H21	120.5
C22—O6—C30	119.28 (11)	C22—C21—H21	120.5
C2—C1—C10	120.07 (10)	O6—C22—C23	115.15 (12)
C2—C1—C11	116.33 (10)	O6—C22—C21	124.69 (13)
C10—C1—C11	123.16 (10)	C23—C22—C21	120.15 (12)
O3—C2—C1	116.00 (10)	C24—C23—C22	120.31 (12)
O3—C2—C3	121.81 (11)	C24—C23—H23	119.8
C1—C2—C3	121.98 (11)	C22—C23—H23	119.8
C4—C3—C2	118.61 (12)	C23—C24—C19	120.44 (12)
C4—C3—H3	120.7	C23—C24—H24	119.8
C2—C3—H3	120.7	C19—C24—H24	119.8
C3—C4—C5	122.04 (11)	O3—C25—H25A	109.5
C3—C4—H4	119.0	O3—C25—H25B	109.5
C5—C4—H4	119.0	H25A—C25—H25B	109.5
C6—C5—C4	120.45 (12)	O3—C25—H25C	109.5
C6—C5—C10	119.78 (12)	H25A—C25—H25C	109.5
C4—C5—C10	119.77 (11)	H25B—C25—H25C	109.5
C7—C6—C5	121.72 (12)	O4—C26—H26A	109.5
C7—C6—H6	119.1	O4—C26—H26B	109.5
C5—C6—H6	119.1	H26A—C26—H26B	109.5
C6—C7—C8	119.11 (12)	O4—C26—H26C	109.5
C6—C7—H7	120.4	H26A—C26—H26C	109.5
C8—C7—H7	120.4	H26B—C26—H26C	109.5
O4—C8—C9	115.56 (11)	O5—C27—C28	113.35 (10)
O4—C8—C7	122.82 (12)	O5—C27—H27A	108.9
C9—C8—C7	121.61 (13)	C28—C27—H27A	108.9
C8—C9—C10	120.01 (11)	O5—C27—H27B	108.9
C8—C9—C18	115.55 (11)	C28—C27—H27B	108.9
C10—C9—C18	124.31 (10)	H27A—C27—H27B	107.7
C9—C10—C5	117.68 (11)	C27—C28—C29	113.75 (11)
C9—C10—C1	124.80 (10)	C27—C28—H28A	108.8
C5—C10—C1	117.49 (11)	C29—C28—H28A	108.8
O1—C11—C12	121.52 (10)	C27—C28—H28B	108.8
O1—C11—C1	118.25 (10)	C29—C28—H28B	108.8
C12—C11—C1	120.23 (10)	H28A—C28—H28B	107.7
C17—C12—C13	118.49 (11)	C30—C29—C28	112.69 (13)
C17—C12—C11	122.76 (10)	C30—C29—H29A	109.1
C13—C12—C11	118.72 (10)	C28—C29—H29A	109.1
C14—C13—C12	120.98 (11)	C30—C29—H29B	109.1
C14—C13—H13	119.5	C28—C29—H29B	109.1
C12—C13—H13	119.5	H29A—C29—H29B	107.8
C13—C14—C15	119.79 (11)	O6—C30—C29	112.49 (12)
C13—C14—H14	120.1	O6—C30—H30A	109.1
C15—C14—H14	120.1	C29—C30—H30A	109.1
O5—C15—C16	124.78 (11)	O6—C30—H30B	109.1
O5—C15—C14	115.09 (10)	C29—C30—H30B	109.1
C16—C15—C14	120.13 (11)	H30A—C30—H30B	107.8
C17—C16—C15	119.44 (11)	O1S—C1S—C3S	121.8 (2)
C17—C16—H16	120.3	O1S—C1S—C2S	121.1 (2)
C15—C16—H16	120.3	C3S—C1S—C2S	117.1 (2)
C16—C17—C12	121.13 (11)	C1S—C2S—H2S1	109.5
C16—C17—H17	119.4	C1S—C2S—H2S2	109.5
C12—C17—H17	119.4	H2S1—C2S—H2S2	109.5
O2—C18—C19	121.20 (11)	C1S—C2S—H2S3	109.5
O2—C18—C9	120.73 (10)	H2S1—C2S—H2S3	109.5
C19—C18—C9	117.99 (10)	H2S2—C2S—H2S3	109.5
C20—C19—C24	118.57 (11)	C1S—C3S—H3S1	109.5
C20—C19—C18	119.23 (11)	H3S1—C3S—H3S2	109.5
C24—C19—C18	122.18 (11)	H3S1—C3S—H3S3	109.5
C21—C20—C19	121.61 (12)	H3S2—C3S—H3S3	109.5
C21—C20—H20	119.2

C25—O3—C2—C1	144.21 (12)	O1—C11—C12—C13	0.48 (16)
C25—O3—C2—C3	−40.90 (17)	C1—C11—C12—C13	179.74 (10)
C10—C1—C2—O3	175.75 (10)	C17—C12—C13—C14	−1.57 (17)
C11—C1—C2—O3	3.16 (15)	C11—C12—C13—C14	176.45 (11)
C10—C1—C2—C3	0.87 (17)	C12—C13—C14—C15	0.49 (18)
C11—C1—C2—C3	−171.72 (11)	C27—O5—C15—C16	−22.73 (18)
O3—C2—C3—C4	−173.61 (11)	C27—O5—C15—C14	158.29 (11)
C1—C2—C3—C4	0.97 (18)	C13—C14—C15—O5	−179.49 (11)
C2—C3—C4—C5	−1.43 (19)	C13—C14—C15—C16	1.47 (19)
C3—C4—C5—C6	−179.21 (12)	O5—C15—C16—C17	178.76 (12)
C3—C4—C5—C10	0.05 (19)	C14—C15—C16—C17	−2.30 (19)
C4—C5—C6—C7	177.84 (13)	C15—C16—C17—C12	1.20 (18)
C10—C5—C6—C7	−1.4 (2)	C13—C12—C17—C16	0.71 (17)
C5—C6—C7—C8	−1.3 (2)	C11—C12—C17—C16	−177.22 (11)
C26—O4—C8—C9	−164.56 (14)	C8—C9—C18—O2	−80.03 (15)
C26—O4—C8—C7	14.4 (2)	C10—C9—C18—O2	104.23 (14)
C6—C7—C8—O4	−176.42 (13)	C8—C9—C18—C19	96.73 (13)
C6—C7—C8—C9	2.5 (2)	C10—C9—C18—C19	−79.01 (14)
O4—C8—C9—C10	178.17 (11)	O2—C18—C19—C20	−8.52 (16)
C7—C8—C9—C10	−0.8 (2)	C9—C18—C19—C20	174.74 (10)
O4—C8—C9—C18	2.23 (17)	O2—C18—C19—C24	169.87 (11)
C7—C8—C9—C18	−176.74 (12)	C9—C18—C19—C24	−6.87 (16)
C8—C9—C10—C5	−1.91 (17)	C24—C19—C20—C21	−0.75 (18)
C18—C9—C10—C5	173.65 (11)	C18—C19—C20—C21	177.70 (11)
C8—C9—C10—C1	−179.77 (11)	C19—C20—C21—C22	0.07 (18)
C18—C9—C10—C1	−4.20 (18)	C30—O6—C22—C23	162.23 (12)
C6—C5—C10—C9	3.00 (17)	C30—O6—C22—C21	−18.9 (2)
C4—C5—C10—C9	−176.27 (11)	C20—C21—C22—O6	−178.25 (12)
C6—C5—C10—C1	−178.99 (11)	C20—C21—C22—C23	0.59 (19)
C4—C5—C10—C1	1.75 (16)	O6—C22—C23—C24	178.38 (12)
C2—C1—C10—C9	175.67 (11)	C21—C22—C23—C24	−0.6 (2)
C11—C1—C10—C9	−12.26 (17)	C22—C23—C24—C19	−0.13 (19)
C2—C1—C10—C5	−2.18 (16)	C20—C19—C24—C23	0.77 (18)
C11—C1—C10—C5	169.88 (10)	C18—C19—C24—C23	−177.63 (11)
C2—C1—C11—O1	107.36 (12)	C15—O5—C27—C28	−59.83 (15)
C10—C1—C11—O1	−64.98 (14)	O5—C27—C28—C29	−49.10 (15)
C2—C1—C11—C12	−71.92 (13)	C27—C28—C29—C30	178.19 (11)
C10—C1—C11—C12	115.74 (12)	C22—O6—C30—C29	−65.93 (17)
O1—C11—C12—C17	178.41 (11)	C28—C29—C30—O6	−45.27 (16)
C1—C11—C12—C17	−2.33 (16)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C12–C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.95	2.47	3.3241 (15)	150
C6—H6···O1ⁱⁱ	0.95	2.38	3.3245 (16)	172
C7—H7···O3ⁱⁱ	0.95	2.59	3.3910 (17)	143
C14—H14···O5ⁱⁱⁱ	0.95	2.40	3.3328 (15)	169
C21—H21···O1S^iv	0.95	2.54	3.482 (2)	172
C2S—H2S2···Cg^v	0.98	2.86	3.830 (2)	171

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

Experimental details

Crystal data
Chemical formula	C₃₀H₂₆O₆·C₃H₆O
M_r	540.59
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	193
a, b, c (Å)	15.4948 (3), 16.1272 (3), 22.4430 (4)
V (Å³)	5608.23 (18)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.50 × 0.45 × 0.40

Data collection
Diffractometer	Rigaku R-AXIS RAPID
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.712, 0.759
No. of measured, independent and observed [I > 2σ(I)] reflections	99441, 5132, 4829
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.098, 1.05
No. of reflections	5132
No. of parameters	366
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.19

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

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C12–C17 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O2ⁱ	0.95	2.47	3.3241 (15)	150
C6—H6···O1ⁱⁱ	0.95	2.38	3.3245 (16)	172
C7—H7···O3ⁱⁱ	0.95	2.59	3.3910 (17)	143
C14—H14···O5ⁱⁱⁱ	0.95	2.40	3.3328 (15)	169
C21—H21···O1S^iv	0.95	2.54	3.482 (2)	172
C2S—H2S2···Cg^v	0.98	2.86	3.830 (2)	171

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

Acknowledgements

The authors would express their gratitude to Master Toyokazu Muto, Department of Organic and Polymer Materials Chemistry, Graduate School, Tokyo University of Agriculture and Technology, and Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, for their technical advice. This work was partially supported by the Ogasawara Foundation for the Promotion of Science & Engineering, Tokyo, Japan.

References

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
Higashi, T. (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Hijikata, 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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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 (2010). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
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Volume 68| Part 8| August 2012| Pages o2598-o2599

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

4-Hy­dr­oxy­methyl-10-meth­­oxy-17,22-dioxa­penta­cyclo­[21.2.2.213,16.13,7.011,30]triaconta-1(25),3,5,7(30),8,10,13,15,23,26,28-undeca­ene-2,12-dione acetone monosolvate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-Hydroxymethyl-10-methoxy-17,22-dioxapentacyclo[21.2.2.2^13,16.1^3,7.0^11,30]triaconta-1(25),3,5,7(30),8,10,13,15,23,26,28-undecaene-2,12-dione acetone monosolvate