1,8-Bis(4-chloro­benzo­yl)-7-meth­oxy­naphthalen-2-ol ethanol monosolvate

Mitsui, R.; Nagasawa, A.; Noguchi, K.; Okamoto, A.; Yonezawa, N.

doi:10.1107/S1600536810024074

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1790

doi:10.1107/S1600536810024074

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1,8-Bis(4-chlorobenzoyl)-7-methoxynaphthalen-2-ol ethanol monosolvate

Ryosuke Mitsui,^a Atsushi Nagasawa,^a Keiichi Noguchi,^b Akiko Okamoto ^a and Noriyuki Yonezawa ^a ^*

^aDepartment of Organic and Polymer Materials Chemistry, Tokyo University of Agriculture & Technology, 2-24-16 Naka-machi, Koganei, Tokyo 184-8588, Japan, and ^bInstrumentation Analysis Center, Tokyo University of Agriculture & Technology, 2-24-16 Naka-machi, Koganei, Tokyo 184-8588, Japan
^*Correspondence e-mail: yonezawa@cc.tuat.ac.jp

(Received 8 June 2010; accepted 21 June 2010; online 26 June 2010)

In the title compound, C₂₅H₁₆Cl₂O₄·C₂H₆O, the two 4-chlorobenzoyl groups are in syn orientations with respect to the naphthalene ring system and are approximately parallel to each other: the dihedral angle between the benzene rings is 11.43 (16)°. The conformation around each of the carbonyl C—(C=O)—C groups forms a larger angle to the plane of the naphthalene ring system than that to the benzene ring; the angles of the C=O bond vector with the naphthalene ring system and the benzene ring are 55.4 (3) versus 13.5 (3)° and 52.2 (3) versus 17.9 (3)°. An intramolecular O—H⋯O=C hydrogen bond generates a six-membered ring. In the crystal structure, intermolecular O—H⋯O hydrogen bonds including the ethanol solvent molecule are observed. A C—H⋯O interaction also occurs. The ethyl group of the ethanol molecule is disordered over two positions with site occupancies of 0.63 and 0.37. The crystal studied was an inversion twin.

Related literature

For the structures of closely related compounds, see: Mitsui et al. (2008 ); Nakaema et al. (2007 ).

Experimental

Crystal data

C₂₅H₁₆Cl₂O₄·C₂H₆O
M_r = 497.35
Tetragonal, $[I \overline 4]$
a = 25.2992 (5) Å
c = 7.3068 (2) Å
V = 4676.71 (18) Å³
Z = 8
Cu Kα radiation
μ = 2.81 mm⁻¹
T = 193 K
0.60 × 0.10 × 0.10 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ) T_min = 0.283, T_max = 0.766
43771 measured reflections
4272 independent reflections
3676 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.146
S = 1.11
4272 reflections
322 parameters
50 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ), 1951 Friedel pairs
Flack parameter: 0.425 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4O⋯O2	0.82	2.21	2.900 (4)	141
O4—H4O⋯O5ⁱ	0.82	2.32	2.919 (5)	131
O5—H5O⋯O4ⁱⁱ	0.90 (1)	1.83 (1)	2.636 (4)	147 (2)
C21—H21⋯O2ⁱⁱⁱ	0.95	2.58	3.374 (5)	141
Symmetry codes: (i) x, y, z+1; (ii) $[y-{\script{1\over 2}}, -x+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) x, y, z-1.

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/S1600536810024074/is2562sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810024074/is2562Isup2.hkl

checkCIF report

Comment top

Recently, we reported the crystal structures of aroylated 2,7-dimethoxynaphthalenes, 1,8-bis(4-chlorobenzoyl)-2,7-dimethoxynaphthalene, (I) (Nakaema et al., 2007) and (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (Mitsui et al., 2008). As a part of our ongoing studies on the synthesis and crystal structure analysis of aroylated naphthalene derivatives, we prepared and analysed the structure of crystal of 1,8-bis(4-chlorobenzoyl)-2-hydroxy-7-methoxynaphthalene, (II). The title compound was prepared by electrophilic aromatic aroylation reaction of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone with 4-chlorobenzoyl chloride.

An ORTEPIII (Burnett & Johnson, 1996) plot of (II) is shown in Fig. 1. In analogous aroylated naphthalenes, for example compound (I) shown in Fig. 2, has two methoxy groups on the naphthalene ring, and the two 4-chlorobenzoyl groups that are in an anti orientation against the naphthalene ring system. In contrast, compound (II) has one hydroxy group instead of methoxy group, and the conformation of 4-chlorobenzoyl groups in compound (II) are in a syn orientation. The two benzene rings are nearly parallel, the dihedral angle between the benzene rings are 11.43 (16)°. The conformation around the central carbonyl C—(C═O)—C group is such that the C═O bond vector forms a larger angle to the plane of the naphthalene ring system [C1/C2/C3/C4/C5/C10 ring and C5/C6/C7/C8/C9/C10 ring] than that to the plane of the benzene ring [C12/C13/C14/C15/C16/C17 ring and C19/C20/C21/C22/C23/C24 ring], viz. 55.4 (3)° versus 13.5 (3)° and 52.2 (3)° versus 17.9 (3)°, respectively. The intramolecular O—H···O═C hydrogen bond generates a six-membered ring (Figs. 1 and 4, Table 1).

In the crystal structure, Cl1 and Cl2 interact with each other [Cl1···Cl2 = 3.4305 (14) Å] and the 4-chlorobenzoyl groups interact with the carbonyl groups (H21···O1 = 2.64 Å, H21···O2 = 2.58 Å) along the c axis (Fig. 3 and Table 1). The hydroxy groups in the compound (II) and the ethanol molecule act as a hydrogen-bond donor [H5O···O4 = 1.833 (11) Å, H4O···O5 = 2.32 Å], and these intermolecular O—H···O hydrogen bonds connecting the compound (II) and the ethanol molecule contribute to the stabilization of the molecular conformation and crystal structure (Fig. 4 and Table 1).

Related literature top

For the structures of closely related compounds, see: Mitsui et al. (2008); Nakaema et al. (2007).

Experimental top

To a solution of (4-chlorophenyl)(2-hydroxy-7-methoxynaphthalen-1-yl)methanone (62 mg, 0.20 mmol) in dichloromethane (0.1 ml) was added 4-chlorobenzoyl chloride (77 mg, 0.44 mmol) and titanium tetrachloride (250 mg, 1.32 mmol). The reaction mixture was heated at reflux for 3 h, then poured into H₂O (10 ml), and the aqueous layer was extracted with CHCl₃ (3 × 10 ml). The combined organic layers were washed with saturated NaHCO₃ (3 × 30 ml) and brine (3 × 30 ml), and dried over MgSO₄ overnight. The solvent was removed in vacuo and the crude material was purified by column chromatography (silica gel, 1:1 EtOAc:hexane) to give the title compound (yield 73 mg, 81%). Single crystals suitable for X-ray diffraction analysis were obtained from EtOH as yellow platelet (m.p. 505.5–506.5 K).

Spectroscopic Data: ¹H NMR (300 MHz, CDCl₃) δ 9.34 (s, 1H), 7.94–7.86 (m, 2H), 7.33 (d, 2H), 7.20–7.10 (m, 6H), 6.91 (d, 2H), 3.60 (s, 3H); ¹³C NMR (75 MHz, CDCl₃) δ 196.8, 195.1, 159.5, 157.6, 139.7, 138.4, 136.8, 136.3, 135.0, 133.7, 132.6, 131.9, 130.5, 128.5, 127.7, 124.6, 121.3, 117.3, 110.6, 56.0; IR (KBr): 1643, 1612, 1587, 1510, 1278, 1089, 831; HRMS (m/z): [M + H]⁺ calcd for C₂₅H₁₇O₄Cl₂, 451.0504; found, 451.0520. Anal. Calcd for C₂₅H₁₆O₄Cl₂: C 66.53, H 3.57. Found: C 66.31, H 3.76.

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 asymmetric unit of compound (II), showing 30% probability displacement ellipsoids. Only major parts of the disordered atoms are shown. The intramolecular O—H···O═C hydrogen bond is shown as a dashed line.
	Fig. 2. The asymmetric unit of compound (I), showing 30% probability displacement ellipsoids.
	Fig. 3. Partial crystal packing diagram of compound (II), viewed down the b axis. Intermolecular C—H···O hydrogen bonds and Cl···Cl and H···O interactions are shown as dashed lines.
	Fig. 4. Partial crystal packing diagram of compound (II), viewed down the c axis. The intramolecular O—H···O═C hydrogen bond and the intermolecular O—H···O hydrogen bonds are shown as dashed lines.

1,8-Bis(4-chlorobenzoyl)-7-methoxynaphthalen-2-ol ethanol monosolvate top

Crystal data top

C₂₅H₁₆Cl₂O₄·C₂H₆O	D_x = 1.413 Mg m⁻³
M_r = 497.35	Melting point = 505.5–506.5 K
Tetragonal, I4	Cu Kα radiation, λ = 1.54187 Å
Hall symbol: I -4	Cell parameters from 34431 reflections
a = 25.2992 (5) Å	θ = 3.5–68.2°
c = 7.3068 (2) Å	µ = 2.81 mm⁻¹
V = 4676.71 (18) Å³	T = 193 K
Z = 8	Platelet, yellow
F(000) = 2064	0.60 × 0.10 × 0.10 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	4272 independent reflections
Radiation source: rotating anode	3676 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 10.00 pixels mm^-1	θ_max = 68.2°, θ_min = 3.5°
ω scans	h = −30→30
Absorption correction: numerical (NUMABS; Higashi, 1999)	k = −29→30
T_min = 0.283, T_max = 0.766	l = −8→8
43771 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.050	w = 1/[σ²(F_o²) + (0.0883P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.146	(Δ/σ)_max = 0.001
S = 1.11	Δρ_max = 0.41 e Å⁻³
4272 reflections	Δρ_min = −0.24 e Å⁻³
322 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
50 restraints	Extinction coefficient: 0.00147 (14)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1951 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.425 (17)

Crystal data top

C₂₅H₁₆Cl₂O₄·C₂H₆O	Z = 8
M_r = 497.35	Cu Kα radiation
Tetragonal, I4	µ = 2.81 mm⁻¹
a = 25.2992 (5) Å	T = 193 K
c = 7.3068 (2) Å	0.60 × 0.10 × 0.10 mm
V = 4676.71 (18) Å³

Data collection top

Rigaku R-AXIS RAPID diffractometer	4272 independent reflections
Absorption correction: numerical (NUMABS; Higashi, 1999)	3676 reflections with I > 2σ(I)
T_min = 0.283, T_max = 0.766	R_int = 0.059
43771 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.146	Δρ_max = 0.41 e Å⁻³
S = 1.11	Δρ_min = −0.24 e Å⁻³
4272 reflections	Absolute structure: Flack (1983), 1951 Friedel pairs
322 parameters	Absolute structure parameter: 0.425 (17)
50 restraints

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	Occ. (<1)
Cl1	0.05719 (3)	0.03898 (3)	0.17865 (14)	0.0621 (3)
Cl2	−0.02496 (4)	0.16783 (4)	0.08841 (16)	0.0770 (3)
O1	0.11592 (9)	0.21618 (9)	0.8263 (4)	0.0551 (6)
O2	0.04808 (10)	0.31611 (10)	0.8034 (4)	0.0612 (6)
O3	0.23047 (8)	0.17133 (9)	0.6041 (4)	0.0598 (6)
O4	0.07574 (10)	0.41241 (9)	0.6105 (4)	0.0678 (7)
H4O	0.0566	0.3955	0.6795	0.081*
C1	0.17824 (11)	0.24765 (13)	0.6109 (5)	0.0479 (7)
C2	0.22785 (13)	0.22437 (13)	0.5843 (5)	0.0522 (8)
C3	0.27296 (13)	0.25544 (15)	0.5449 (5)	0.0566 (9)
H3	0.3063	0.2393	0.5240	0.068*
C4	0.26750 (14)	0.30881 (15)	0.5375 (5)	0.0584 (9)
H4	0.2979	0.3298	0.5153	0.070*
C5	0.21886 (14)	0.33392 (14)	0.5614 (5)	0.0545 (8)
C6	0.21545 (15)	0.39011 (14)	0.5502 (5)	0.0612 (9)
H6	0.2467	0.4099	0.5287	0.073*
C7	0.16923 (16)	0.41585 (14)	0.5690 (6)	0.0645 (10)
H7	0.1681	0.4533	0.5609	0.077*
C8	0.12273 (14)	0.38691 (13)	0.6008 (5)	0.0560 (8)
C9	0.12359 (12)	0.33224 (12)	0.6194 (5)	0.0506 (8)
C10	0.17206 (12)	0.30356 (13)	0.5983 (5)	0.0489 (7)
C11	0.13535 (12)	0.21062 (13)	0.6754 (5)	0.0488 (7)
C12	0.11815 (12)	0.16695 (12)	0.5514 (5)	0.0464 (7)
C13	0.13067 (13)	0.16708 (13)	0.3672 (5)	0.0521 (8)
H13	0.1527	0.1942	0.3194	0.063*
C14	0.11142 (14)	0.12794 (14)	0.2511 (5)	0.0548 (8)
H14	0.1190	0.1288	0.1238	0.066*
C15	0.08117 (12)	0.08796 (12)	0.3244 (5)	0.0501 (7)
C16	0.06922 (13)	0.08626 (13)	0.5068 (5)	0.0535 (8)
H16	0.0488	0.0579	0.5545	0.064*
C17	0.08686 (12)	0.12576 (13)	0.6207 (5)	0.0527 (8)
H17	0.0778	0.1252	0.7469	0.063*
C18	0.07059 (13)	0.30794 (12)	0.6591 (5)	0.0513 (8)
C19	0.04529 (13)	0.27497 (13)	0.5116 (5)	0.0510 (8)
C20	0.06054 (14)	0.27961 (14)	0.3330 (6)	0.0572 (8)
H20	0.0868	0.3047	0.3000	0.069*
C21	0.03752 (15)	0.24741 (15)	0.1975 (6)	0.0625 (9)
H21	0.0478	0.2503	0.0729	0.075*
C22	−0.00009 (14)	0.21190 (14)	0.2508 (6)	0.0588 (9)
C23	−0.01677 (14)	0.20716 (14)	0.4298 (6)	0.0610 (9)
H23	−0.0430	0.1820	0.4622	0.073*
C24	0.00536 (13)	0.23966 (13)	0.5612 (6)	0.0560 (8)
H24	−0.0065	0.2380	0.6844	0.067*
C25	0.28018 (15)	0.14558 (17)	0.5787 (7)	0.0720 (11)
H25A	0.2756	0.1073	0.5930	0.086*
H25B	0.3054	0.1585	0.6700	0.086*
H25C	0.2936	0.1532	0.4556	0.086*
C26	0.10138 (18)	0.4338 (3)	0.0813 (9)	0.1041 (17)
H26A	0.1190	0.4317	0.2004	0.125*	0.63
H26B	0.1041	0.4700	0.0339	0.125*	0.63
H26C	0.1183	0.4093	−0.0045	0.125*	0.63
H26D	0.1226	0.4626	0.1330	0.125*	0.37
H26E	0.1193	0.4193	−0.0264	0.125*	0.37
H26F	0.0969	0.4059	0.1731	0.125*	0.37
C27A	0.0461 (3)	0.4197 (4)	0.1019 (11)	0.092 (2)	0.63
H27A	0.0445	0.3839	0.1557	0.111*	0.63
H27B	0.0302	0.4443	0.1919	0.111*	0.63
C27B	0.0485 (4)	0.4546 (5)	0.028 (2)	0.092 (4)	0.37
H27C	0.0313	0.4689	0.1394	0.110*	0.37
H27D	0.0539	0.4845	−0.0571	0.110*	0.37
O5	0.01506 (14)	0.42004 (17)	−0.0507 (6)	0.1179 (14)
H5O	−0.0194 (3)	0.4263 (11)	−0.026 (3)	0.141*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0672 (5)	0.0567 (5)	0.0624 (6)	−0.0070 (4)	−0.0069 (4)	−0.0074 (4)
Cl2	0.0848 (6)	0.0637 (5)	0.0826 (7)	0.0000 (4)	−0.0310 (6)	−0.0117 (5)
O1	0.0530 (12)	0.0687 (14)	0.0436 (13)	−0.0058 (10)	0.0053 (11)	−0.0048 (11)
O2	0.0612 (14)	0.0643 (14)	0.0580 (16)	−0.0030 (11)	0.0122 (13)	−0.0105 (13)
O3	0.0514 (12)	0.0651 (14)	0.0630 (16)	0.0046 (10)	0.0009 (12)	−0.0015 (12)
O4	0.0671 (15)	0.0577 (14)	0.0787 (19)	−0.0015 (11)	0.0040 (14)	0.0011 (13)
C1	0.0464 (15)	0.0612 (18)	0.0363 (17)	−0.0059 (13)	0.0009 (13)	−0.0056 (14)
C2	0.0526 (18)	0.063 (2)	0.0414 (18)	−0.0029 (14)	−0.0019 (15)	−0.0039 (16)
C3	0.0462 (17)	0.078 (2)	0.0453 (19)	−0.0041 (15)	0.0027 (15)	−0.0040 (17)
C4	0.055 (2)	0.077 (2)	0.0428 (19)	−0.0147 (17)	−0.0010 (16)	−0.0027 (17)
C5	0.0551 (18)	0.066 (2)	0.0423 (18)	−0.0132 (15)	0.0018 (15)	−0.0058 (16)
C6	0.069 (2)	0.063 (2)	0.052 (2)	−0.0227 (17)	0.0005 (18)	−0.0029 (17)
C7	0.074 (2)	0.0544 (19)	0.065 (2)	−0.0153 (17)	0.002 (2)	−0.0025 (18)
C8	0.0626 (19)	0.0550 (18)	0.051 (2)	−0.0080 (15)	0.0049 (17)	−0.0070 (16)
C9	0.0531 (17)	0.0539 (17)	0.0447 (18)	−0.0067 (13)	0.0020 (15)	−0.0040 (15)
C10	0.0501 (17)	0.0591 (18)	0.0374 (17)	−0.0100 (13)	−0.0018 (14)	−0.0068 (14)
C11	0.0437 (15)	0.0582 (18)	0.0446 (18)	−0.0023 (13)	0.0004 (15)	−0.0016 (16)
C12	0.0424 (15)	0.0536 (17)	0.0431 (18)	0.0012 (12)	−0.0031 (14)	−0.0002 (14)
C13	0.0530 (17)	0.0567 (18)	0.047 (2)	−0.0071 (13)	0.0036 (15)	0.0008 (15)
C14	0.0595 (19)	0.062 (2)	0.0432 (18)	−0.0040 (16)	0.0029 (15)	−0.0015 (16)
C15	0.0479 (16)	0.0499 (16)	0.0527 (19)	−0.0020 (13)	−0.0034 (15)	−0.0039 (16)
C16	0.0545 (18)	0.0499 (18)	0.056 (2)	−0.0046 (14)	0.0048 (15)	0.0036 (15)
C17	0.0553 (17)	0.0524 (17)	0.050 (2)	0.0004 (14)	0.0052 (15)	0.0027 (15)
C18	0.0519 (17)	0.0506 (17)	0.051 (2)	−0.0009 (13)	0.0021 (16)	−0.0004 (15)
C19	0.0485 (17)	0.0518 (18)	0.053 (2)	0.0015 (14)	−0.0018 (15)	−0.0007 (15)
C20	0.0587 (19)	0.0565 (19)	0.056 (2)	−0.0049 (15)	−0.0040 (17)	0.0011 (17)
C21	0.071 (2)	0.066 (2)	0.050 (2)	0.0013 (17)	−0.0074 (18)	−0.0045 (18)
C22	0.058 (2)	0.0518 (19)	0.066 (2)	0.0023 (15)	−0.0163 (17)	−0.0054 (17)
C23	0.0553 (19)	0.0515 (18)	0.076 (3)	−0.0047 (14)	−0.0056 (19)	−0.0023 (18)
C24	0.0534 (18)	0.0540 (18)	0.061 (2)	−0.0039 (14)	0.0014 (16)	0.0005 (17)
C25	0.068 (2)	0.080 (3)	0.067 (3)	0.0053 (18)	0.006 (2)	−0.002 (2)
C26	0.078 (3)	0.140 (5)	0.095 (4)	0.015 (3)	−0.018 (3)	−0.023 (4)
C27A	0.104 (5)	0.093 (5)	0.080 (6)	0.009 (4)	−0.002 (4)	−0.002 (4)
C27B	0.080 (7)	0.095 (9)	0.102 (11)	−0.004 (6)	0.001 (7)	−0.012 (8)
O5	0.0704 (19)	0.158 (3)	0.125 (4)	0.016 (2)	−0.007 (2)	−0.054 (3)

Geometric parameters (Å, º) top

Cl1—C15	1.743 (3)	C16—C17	1.375 (5)
Cl2—C22	1.746 (4)	C16—H16	0.9500
O1—C11	1.215 (4)	C17—H17	0.9500
O2—C18	1.216 (4)	C18—C19	1.506 (5)
O3—C2	1.351 (4)	C19—C20	1.366 (6)
O3—C25	1.428 (4)	C19—C24	1.396 (5)
O4—C8	1.354 (4)	C20—C21	1.408 (5)
O4—H4O	0.8200	C20—H20	0.9500
C1—C2	1.400 (5)	C21—C22	1.365 (5)
C1—C10	1.426 (5)	C21—H21	0.9500
C1—C11	1.509 (4)	C22—C23	1.379 (6)
C2—C3	1.415 (5)	C23—C24	1.383 (5)
C3—C4	1.358 (5)	C23—H23	0.9500
C3—H3	0.9500	C24—H24	0.9500
C4—C5	1.396 (5)	C25—H25A	0.9800
C4—H4	0.9500	C25—H25B	0.9800
C5—C6	1.427 (5)	C25—H25C	0.9800
C5—C10	1.437 (4)	C26—C27A	1.451 (7)
C6—C7	1.345 (6)	C26—C27B	1.488 (8)
C6—H6	0.9500	C26—H26A	0.9800
C7—C8	1.405 (5)	C26—H26B	0.9800
C7—H7	0.9500	C26—H26C	0.9800
C8—C9	1.390 (5)	C26—H26D	0.9800
C9—C10	1.433 (5)	C26—H26E	0.9800
C9—C18	1.503 (4)	C26—H26F	0.9800
C11—C12	1.494 (5)	C27A—O5	1.364 (7)
C12—C13	1.382 (5)	C27A—H27A	0.9900
C12—C17	1.403 (4)	C27A—H27B	0.9900
C13—C14	1.392 (5)	C27B—O5	1.347 (8)
C13—H13	0.9500	C27B—H27C	0.9900
C14—C15	1.377 (5)	C27B—H27D	0.9900
C14—H14	0.9500	O5—H5O	0.904 (10)
C15—C16	1.367 (5)

C2—O3—C25	118.8 (3)	O2—C18—C9	121.0 (3)
C8—O4—H4O	107.7	O2—C18—C19	121.1 (3)
C2—C1—C10	120.4 (3)	C9—C18—C19	117.9 (3)
C2—C1—C11	115.3 (3)	C20—C19—C24	120.5 (3)
C10—C1—C11	123.9 (3)	C20—C19—C18	121.1 (3)
O3—C2—C1	116.5 (3)	C24—C19—C18	118.4 (3)
O3—C2—C3	122.3 (3)	C19—C20—C21	120.3 (3)
C1—C2—C3	121.2 (3)	C19—C20—H20	119.8
C4—C3—C2	118.6 (3)	C21—C20—H20	119.8
C4—C3—H3	120.7	C22—C21—C20	117.9 (4)
C2—C3—H3	120.7	C22—C21—H21	121.0
C3—C4—C5	122.5 (3)	C20—C21—H21	121.0
C3—C4—H4	118.8	C21—C22—C23	122.7 (3)
C5—C4—H4	118.8	C21—C22—Cl2	118.5 (3)
C4—C5—C6	120.0 (3)	C23—C22—Cl2	118.6 (3)
C4—C5—C10	120.4 (3)	C22—C23—C24	118.9 (3)
C6—C5—C10	119.6 (3)	C22—C23—H23	120.6
C7—C6—C5	121.9 (3)	C24—C23—H23	120.6
C7—C6—H6	119.0	C23—C24—C19	119.5 (4)
C5—C6—H6	119.0	C23—C24—H24	120.2
C6—C7—C8	119.5 (3)	C19—C24—H24	120.2
C6—C7—H7	120.2	O3—C25—H25A	109.5
C8—C7—H7	120.2	O3—C25—H25B	109.5
O4—C8—C9	118.9 (3)	H25A—C25—H25B	109.5
O4—C8—C7	119.7 (3)	O3—C25—H25C	109.5
C9—C8—C7	121.4 (3)	H25A—C25—H25C	109.5
C8—C9—C10	120.4 (3)	H25B—C25—H25C	109.5
C8—C9—C18	114.3 (3)	C27A—C26—H26A	109.5
C10—C9—C18	125.2 (3)	C27A—C26—H26B	109.5
C1—C10—C9	126.1 (3)	H26A—C26—H26B	109.5
C1—C10—C5	116.9 (3)	C27A—C26—H26C	109.5
C9—C10—C5	117.0 (3)	H26A—C26—H26C	109.5
O1—C11—C12	121.2 (3)	H26B—C26—H26C	109.5
O1—C11—C1	120.2 (3)	C27B—C26—H26D	109.3
C12—C11—C1	118.6 (3)	C27B—C26—H26E	109.9
C13—C12—C17	118.8 (3)	H26D—C26—H26E	109.5
C13—C12—C11	121.5 (3)	C27B—C26—H26F	109.2
C17—C12—C11	119.6 (3)	H26D—C26—H26F	109.5
C12—C13—C14	120.8 (3)	H26E—C26—H26F	109.5
C12—C13—H13	119.6	O5—C27A—C26	117.9 (6)
C14—C13—H13	119.6	O5—C27A—H27A	107.8
C15—C14—C13	118.7 (3)	C26—C27A—H27A	107.8
C15—C14—H14	120.7	O5—C27A—H27B	107.8
C13—C14—H14	120.7	C26—C27A—H27B	107.8
C16—C15—C14	121.7 (3)	H27A—C27A—H27B	107.2
C16—C15—Cl1	119.8 (3)	O5—C27B—C26	116.6 (8)
C14—C15—Cl1	118.5 (3)	O5—C27B—H27C	108.1
C15—C16—C17	119.7 (3)	C26—C27B—H27C	108.1
C15—C16—H16	120.2	O5—C27B—H27D	108.1
C17—C16—H16	120.2	C26—C27B—H27D	108.1
C16—C17—C12	120.3 (3)	H27C—C27B—H27D	107.3
C16—C17—H17	119.9	C27B—O5—H5O	114.2 (14)
C12—C17—H17	119.9	C27A—O5—H5O	113.4 (14)

C25—O3—C2—C1	−179.9 (3)	O1—C11—C12—C13	165.1 (3)
C25—O3—C2—C3	−2.0 (5)	C1—C11—C12—C13	−15.8 (5)
C10—C1—C2—O3	178.1 (3)	O1—C11—C12—C17	−12.4 (5)
C11—C1—C2—O3	5.4 (5)	C1—C11—C12—C17	166.7 (3)
C10—C1—C2—C3	0.1 (5)	C17—C12—C13—C14	1.8 (5)
C11—C1—C2—C3	−172.5 (3)	C11—C12—C13—C14	−175.7 (3)
O3—C2—C3—C4	−176.3 (3)	C12—C13—C14—C15	−2.3 (5)
C1—C2—C3—C4	1.6 (5)	C13—C14—C15—C16	0.8 (5)
C2—C3—C4—C5	−2.2 (5)	C13—C14—C15—Cl1	−179.9 (3)
C3—C4—C5—C6	−179.3 (4)	C14—C15—C16—C17	1.1 (5)
C3—C4—C5—C10	1.1 (5)	Cl1—C15—C16—C17	−178.1 (2)
C4—C5—C6—C7	178.8 (4)	C15—C16—C17—C12	−1.6 (5)
C10—C5—C6—C7	−1.6 (6)	C13—C12—C17—C16	0.2 (5)
C5—C6—C7—C8	0.0 (6)	C11—C12—C17—C16	177.8 (3)
C6—C7—C8—O4	−176.6 (4)	C8—C9—C18—O2	−67.1 (4)
C6—C7—C8—C9	2.2 (6)	C10—C9—C18—O2	113.8 (4)
O4—C8—C9—C10	176.0 (3)	C8—C9—C18—C19	110.5 (4)
C7—C8—C9—C10	−2.8 (6)	C10—C9—C18—C19	−68.6 (5)
O4—C8—C9—C18	−3.2 (5)	O2—C18—C19—C20	157.9 (4)
C7—C8—C9—C18	178.1 (4)	C9—C18—C19—C20	−19.7 (5)
C2—C1—C10—C9	178.9 (3)	O2—C18—C19—C24	−21.6 (5)
C11—C1—C10—C9	−9.1 (5)	C9—C18—C19—C24	160.9 (3)
C2—C1—C10—C5	−1.2 (5)	C24—C19—C20—C21	−2.3 (5)
C11—C1—C10—C5	170.8 (3)	C18—C19—C20—C21	178.2 (3)
C8—C9—C10—C1	−178.9 (3)	C19—C20—C21—C22	0.0 (5)
C18—C9—C10—C1	0.2 (6)	C20—C21—C22—C23	1.2 (6)
C8—C9—C10—C5	1.2 (5)	C20—C21—C22—Cl2	−174.6 (3)
C18—C9—C10—C5	−179.8 (3)	C21—C22—C23—C24	0.0 (6)
C4—C5—C10—C1	0.6 (5)	Cl2—C22—C23—C24	175.8 (3)
C6—C5—C10—C1	−179.0 (3)	C22—C23—C24—C19	−2.4 (5)
C4—C5—C10—C9	−179.4 (3)	C20—C19—C24—C23	3.5 (5)
C6—C5—C10—C9	0.9 (5)	C18—C19—C24—C23	−177.0 (3)
C2—C1—C11—O1	114.4 (4)	C27B—C26—C27A—O5	49.3 (9)
C10—C1—C11—O1	−58.0 (5)	C27A—C26—C27B—O5	−49.3 (9)
C2—C1—C11—C12	−64.7 (4)	C26—C27B—O5—C27A	48.9 (9)
C10—C1—C11—C12	122.9 (3)	C26—C27A—O5—C27B	−51.4 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4O···O2	0.82	2.21	2.900 (4)	141
O4—H4O···O5ⁱ	0.82	2.32	2.919 (5)	131
O5—H5O···O4ⁱⁱ	0.90 (1)	1.83 (1)	2.636 (4)	147 (2)
C21—H21···O2ⁱⁱⁱ	0.95	2.58	3.374 (5)	141

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

Experimental details

Crystal data
Chemical formula	C₂₅H₁₆Cl₂O₄·C₂H₆O
M_r	497.35
Crystal system, space group	Tetragonal, I4
Temperature (K)	193
a, c (Å)	25.2992 (5), 7.3068 (2)
V (Å³)	4676.71 (18)
Z	8
Radiation type	Cu Kα
µ (mm⁻¹)	2.81
Crystal size (mm)	0.60 × 0.10 × 0.10

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.283, 0.766
No. of measured, independent and observed [I > 2σ(I)] reflections	43771, 4272, 3676
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.146, 1.11
No. of reflections	4272
No. of parameters	322
No. of restraints	50
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.24
Absolute structure	Flack (1983), 1951 Friedel pairs
Absolute structure parameter	0.425 (17)

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
O4—H4O···O2	0.82	2.21	2.900 (4)	141
O4—H4O···O5ⁱ	0.82	2.32	2.919 (5)	131
O5—H5O···O4ⁱⁱ	0.904 (11)	1.833 (11)	2.636 (4)	147 (2)
C21—H21···O2ⁱⁱⁱ	0.95	2.58	3.374 (5)	141

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

Acknowledgements

This work was partially supported by the Mukai Science and Technology Foundation, Tokyo, Japan.

References

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