3,3′-[o-Phenyl­enebis­(methyl­eneoxy)]­bis(6-chloro­flavone) and 3,3′-propyl­ene­dioxy­bis­[6-chloro-2-(2-furyl)-4H-1-benzopyran-4-one]

The title compound 3,3′-[o-phenyl­enebis­(methyl­eneoxy)]­bis(6-chloro­flavone), C₃₈H₂₄Cl₂O₆, (I), crystallizes in the monoclinic space group C2/c, with the molecules lying across twofold rotation axes so that there is half a mol­ecule in the asymmetric unit, while the other title compound, 3,3′-propyl­ene­dioxy­bis­[6-chloro-2-(2-furyl)-4H-1-benzopyran-4-one], C₂₉H₁₈Cl₂O₈, (II), crystallizes in monoclinic space group P2₁/n with one mol­ecule in the asymmetric unit. In both compounds, the benzopyran moiety is nearly planar, with dihedral angles between the two fused rings of 1.43 (8)° in (I), and 2.54 (7) and 3.00 (6)° with respect to the benzopyran moieties in the two halves of (II). The furan rings are twisted by 8.3 (1) and 8.4 (1)° in the two halves of (II). In both compounds, the molecular structure is stabilized by intramolecular C—H...O hydrogen bonds, while the crystal packing is stabilized by C—H...Cl and C—H...O intermolecular hydrogen bonds in (I) and (II), respectively.

S1. Comment

Flavonoids exhibit antidiabetic (Hii & Howell, 1985; Basnet et al., 1993; Ragunathan & Sulochana, 1994) and aldose reductase inhibitory activities (Varma & Kinoshita, 1976; Okuda et al., 1984; Aida et al., 1990). Flavone derivatives are known to have a coronary dilatory effect (Itz & Potzsch, 1963) and capillary resistance activity (Gabor, 1981). Chromanone derivatives dilate the heart and are used to treat angina pectoris (Hasegaida, 1967). Against this background and in order to obtain detailed information about the molecular conformations of the title compounds in the solid state, X-ray structure determinations of (I) and (II) were carried out and the results are presented here.

Figs. 1 and 2 show ORTEP and ZORTEP plots of the molecules of (I) and (II), respectively, with atom-numbering schemes. The asymmetric unit of the xylene derivative, (I), consists of a half molecule, while that of the propane derivative, (II), comprises one whole molecule. In (I), a phenyl ring is substituted to the flavone moiety, whereas in (II), a furan ring is substituted. Four C and two O atoms form a linear coupling chain between the two flavone moieties in (I), while in (II), this coupling chain consists of three C and two O atoms.

In compound (I), the C8—O2 bond length (Table 1) agrees with the value of 1.385 (3) Å reported by Bruno et al. (2001). In compound (II), the C8—O2 and C24—O7 bond lengths agree with the literature values [1.364 (2) Å in Shuib et al. (1999) and 1.352 (3) Å in Thinagar et al. (2000)]. The angle C3—C8—C7 in (I) agrees with the literature value [122.1 (3)° in Ozbey et al. (1999)], while C7—C8—-C3 and C19—C24—C23 in (II) are comparable with the reported value [121.4 (4)° in Letcher et al. (1992)].

The pyran rings are planar in both compounds and contrast with the normal half-chair conformation, as reported in Alex et al. (1993). The hetero atoms, viz. O2 in the ring and the oxo substituent O1 at position 4, cause slight varaiations in the geometric parameters within the ring. The values of the bond angles within the heterocyclic ring are in the range 113.3 (2)–122.6 (2)° in (I) and in the ranges 114.5 (2)–122.8 (2) and 114.4 (2)–123.0 (2)° in the two halves of (II) (Table 1). Similar variations in the geometric parameters of the the pyran ring of the benzopyran system have been reported previously (Rybarczyk-Pirek et al., 2002).

The torsion angle C1—C9—C10—C11 shows a +synclinal (+sc) orientation of the phenyl ring with respect to the 4-chromanone moiety (C1–C8/O2/C9/O1) in (I), while torsion angles C1—C9—C10—C13 and C17—C25—C26—C29 indicate +synperiplanar (+sp) orientations of the two furan rings with respect to the 4-chromanone moieties (O1/O2/C1–C9 and O6/O7/C17–C25, respectively) in (II). The torsion angle O3—C16—C17—C18 in (I) is +anticlinal (+ac), while O4—C14—C15—C16 and O5—C16—C15—C14 in (II) are +synclinal.

The benzopyran systems of (I) and (II) are not strictly planar and the dihedral angle formed by the benzene and pyran planes is 1.43 (8)° in (I), and 2.54 (7) and 3.00 (6)° in the two halves of (II). The dihedral angle between the best planes of the 4-chromanone moiety (C1–C8/O2/C9/O1) and the phenyl ring is 53.5 (1)° in (I). In (II), the furan rings are not quite coplanar with flavone moieties C1–C8/O2/O3/C9–C13 and C17–C24/O7/O8/C25–C29, the corresponding dihedral angles being 6.88 (6) and 6.77 (6)°, respectively. The dihedral angles formed by the O3/C10–C13 and O8/C26–C29 furan rings with the O1/O2/C1–C9 and O6/O7/C17–C25 4-chromanone moieties are 9.22 (6) and 9.41 (6)°, respectively. The oxo and oxy atoms lie practically in the benzopyran plane in (I) and the two halves of (II).

In addition to van der Waals interactions, an intermolecular C—H···Cl hydrogen bond stabilizes the crystal packing of (I). The H18···Cl1 (2.88 Å) contact is significantly shorter than the sum of van der Waals radii (2.95 Å; Bondi, 1964; Taylor & Kennard, 1982). The molecular packing is stabilized by one intramolecular C—H···O hydrogen bond. In (II), the molecular structure is stabilized by two intramolecular C—H···O hydrogen bonds, while the crystal packing is stabilized by two intermolecular C—H···O hydrogen bonds. The hydrogen-bond geometry for (I) and (II) are given in Tables 2 and 4, respectively.

S2. Experimental

A suspension of 6-chloro-3-hydroxy-2-(2-furyl)-4-oxo-4H-1-benzopyran (1 g, 0.0038 mol), 1,ω-dibromoalkane (0.0019m ol) [bis(1,1'-dibromoethylbenzene for (I) and 1,3-dibromopropane for (II)], tetra-n-butylammonium iodide (1 g) and freshly ignited K₂CO₃ (1 g) were refluxed in dry acetone (30 ml) for 4 h. The colour of the reaction mixture changed from yellow to colourless. The reaction mixture, after filtration and distillation of acetone, was poured into cold water, giving a mixture of monochromone and bischromone. This was then crystallized from acetone to obtain the pure bischromone compounds.

S3. Refinement

In both compounds, all the H atoms were fixed geometrically and allowed to ride on the corresponding non-H atoms, with C—H distances of 0.93 and 0.97 Å, and U_iso = 1.2U_eq of the attached C atoms for non-methyl H atoms.

Computing details

Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994) for (I); SMART (Siemens, 1996) for (II). Cell refinement: CAD-4 EXPRESS for (I); SAINT (Siemens, 1996) for (II). Data reduction: XCAD4 (Harms & Wocadlo, 1996) for (I); SAINT for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997). Program(s) used to refine structure: SHELXL97 (Sheldrick, 1997) for (I); SHELXL97(Sheldrick, 1997) for (II). Molecular graphics: ORTEPII (Johnson, 1976) for (I); ZORTEP (Zsolnai, 1997) for (II). For both compounds, software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. ORTEPII (Johnson, 1976) plot of the molecular structure of (I), showing 35% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. ZORTEP (Zsolnai, 1997) plot of the molecular structure of (II), showing 35% probability displacement ellipsoids and the atom-numbering scheme.

(I) 3,3'-[o-Phenylenebis(methyleneoxy)]bis(6-chloro-2-phenylflavanone)

Crystal data

C38H24Cl2O6	F(000) = 1336
Mr = 647.47	Dx = 1.382 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 13.236 (1) Å	Cell parameters from 25 reflections
b = 10.799 (4) Å	θ = 1.2–28°
c = 21.775 (4) Å	µ = 0.26 mm^−1
β = 91.393 (3)°	T = 293 K
V = 3111.5 (13) Å^3	Block, colourless
Z = 4	0.47 × 0.43 × 0.40 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.024
Radiation source: fine-focus sealed tube	θmax = 30.4°, θmin = 2.4°
Graphite monochromator	h = 0→18
Non–profiled w/2θ scans	k = 0→15
4781 measured reflections	l = −31→31
4612 independent reflections	3 standard reflections every 100 reflections
1928 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.230	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1073P)^2 + 1.2599P] where P = (Fo^2 + 2Fc^2)/3
4612 reflections	(Δ/σ)max < 0.001
208 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.45 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	−0.00142 (10)	0.19640 (16)	0.02509 (5)	0.1133 (6)
O1	0.31016 (18)	−0.0226 (2)	−0.08577 (10)	0.0645 (7)
O2	0.14304 (14)	0.1378 (2)	−0.22423 (8)	0.0434 (5)
O3	0.37549 (15)	−0.03714 (19)	−0.20629 (9)	0.0472 (5)
C1	0.2884 (2)	0.0245 (3)	−0.19096 (12)	0.0381 (6)
C2	0.2607 (2)	0.0279 (3)	−0.12679 (13)	0.0434 (7)
C3	0.1672 (2)	0.0969 (3)	−0.11629 (13)	0.0423 (7)
C4	0.1304 (3)	0.1116 (3)	−0.05660 (14)	0.0576 (9)
H4	0.1642	0.0759	−0.0231	0.069*
C5	0.0444 (3)	0.1791 (4)	−0.04859 (15)	0.0622 (10)
C6	−0.0083 (3)	0.2306 (4)	−0.09685 (16)	0.0616 (10)
H6	−0.0667	0.2759	−0.0899	0.074*
C7	0.0250 (2)	0.2153 (3)	−0.15547 (15)	0.0520 (8)
H7	−0.0108	0.2490	−0.1888	0.062*
C8	0.1128 (2)	0.1488 (3)	−0.16410 (13)	0.0409 (7)
C9	0.2309 (2)	0.0754 (3)	−0.23602 (12)	0.0383 (6)
C10	0.2516 (2)	0.0731 (3)	−0.30218 (13)	0.0400 (7)
C11	0.2684 (3)	−0.0377 (3)	−0.33210 (15)	0.0543 (8)
H11	0.2658	−0.1116	−0.3102	0.065*
C12	0.2890 (3)	−0.0404 (4)	−0.39440 (16)	0.0618 (10)
H12	0.2992	−0.1156	−0.4141	0.074*
C13	0.2943 (3)	0.0683 (4)	−0.42649 (15)	0.0641 (10)
H13	0.3093	0.0670	−0.4680	0.077*
C14	0.2776 (3)	0.1794 (4)	−0.39761 (15)	0.0605 (9)
H14	0.2812	0.2530	−0.4196	0.073*
C15	0.2554 (2)	0.1817 (3)	−0.33566 (14)	0.0505 (8)
H15	0.2431	0.2570	−0.3165	0.061*
C16	0.4669 (2)	0.0283 (4)	−0.18564 (14)	0.0544 (9)
H16A	0.5249	−0.0253	−0.1909	0.065*
H16B	0.4623	0.0465	−0.1422	0.065*
C17	0.4833 (2)	0.1466 (3)	−0.21990 (13)	0.0450 (7)
C18	0.4660 (3)	0.2595 (4)	−0.1916 (2)	0.0765 (12)
H18	0.4425	0.2606	−0.1517	0.092*
C19	0.4828 (3)	0.3696 (4)	−0.2213 (3)	0.106 (2)
H19	0.4703	0.4442	−0.2016	0.127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1048 (10)	0.1815 (15)	0.0554 (6)	0.0481 (9)	0.0362 (6)	−0.0058 (7)
O1	0.0578 (14)	0.0859 (18)	0.0501 (12)	0.0237 (13)	0.0090 (11)	0.0225 (13)
O2	0.0404 (11)	0.0515 (13)	0.0385 (10)	0.0121 (9)	0.0033 (8)	0.0000 (9)
O3	0.0376 (11)	0.0517 (13)	0.0526 (12)	0.0093 (9)	0.0108 (9)	0.0076 (10)
C1	0.0348 (14)	0.0382 (15)	0.0418 (14)	0.0043 (12)	0.0105 (11)	0.0044 (13)
C2	0.0412 (15)	0.0476 (17)	0.0419 (15)	0.0053 (14)	0.0091 (12)	0.0108 (14)
C3	0.0399 (15)	0.0466 (17)	0.0408 (15)	0.0046 (13)	0.0092 (12)	0.0037 (13)
C4	0.0557 (19)	0.077 (2)	0.0407 (16)	0.0133 (18)	0.0089 (14)	0.0066 (16)
C5	0.055 (2)	0.090 (3)	0.0429 (16)	0.0126 (19)	0.0191 (15)	−0.0083 (18)
C6	0.0446 (17)	0.079 (3)	0.061 (2)	0.0148 (18)	0.0088 (16)	−0.0146 (19)
C7	0.0388 (16)	0.065 (2)	0.0527 (17)	0.0122 (15)	0.0012 (13)	−0.0048 (16)
C8	0.0373 (14)	0.0471 (17)	0.0387 (14)	0.0031 (13)	0.0073 (12)	−0.0050 (13)
C9	0.0388 (15)	0.0386 (16)	0.0377 (14)	0.0008 (12)	0.0076 (11)	−0.0035 (12)
C10	0.0337 (14)	0.0456 (17)	0.0409 (15)	0.0029 (13)	0.0058 (11)	−0.0027 (13)
C11	0.064 (2)	0.050 (2)	0.0491 (17)	0.0044 (16)	0.0040 (15)	−0.0030 (15)
C12	0.071 (2)	0.067 (2)	0.0477 (18)	0.0068 (19)	0.0062 (16)	−0.0168 (18)
C13	0.062 (2)	0.093 (3)	0.0377 (16)	0.003 (2)	0.0101 (15)	−0.0132 (19)
C14	0.069 (2)	0.071 (2)	0.0426 (16)	0.0014 (19)	0.0150 (16)	0.0064 (17)
C15	0.059 (2)	0.0499 (19)	0.0430 (15)	0.0062 (15)	0.0118 (14)	−0.0027 (14)
C16	0.0338 (15)	0.082 (2)	0.0474 (17)	0.0106 (16)	0.0050 (13)	0.0131 (17)
C17	0.0331 (15)	0.0540 (19)	0.0478 (16)	0.0036 (13)	−0.0037 (12)	−0.0059 (14)
C18	0.050 (2)	0.086 (3)	0.094 (3)	0.006 (2)	0.001 (2)	−0.036 (3)
C19	0.052 (3)	0.056 (2)	0.210 (8)	0.001 (2)	−0.002 (3)	−0.033 (3)

Geometric parameters (Å, º)

Cl1—C5	1.739 (3)	C10—C15	1.382 (4)
O1—C2	1.223 (4)	C11—C12	1.391 (4)
O2—C9	1.373 (3)	C11—H11	0.9300
O2—C8	1.383 (3)	C12—C13	1.369 (5)
O3—C1	1.379 (3)	C12—H12	0.9300
O3—C16	1.463 (4)	C13—C14	1.375 (5)
C1—C9	1.345 (4)	C13—H13	0.9300
C1—C2	1.454 (4)	C14—C15	1.388 (4)
C2—C3	1.468 (4)	C14—H14	0.9300
C3—C8	1.371 (4)	C15—H15	0.9300
C3—C4	1.408 (4)	C16—C17	1.498 (5)
C4—C5	1.367 (5)	C16—H16A	0.9700
C4—H4	0.9300	C16—H16B	0.9700
C5—C6	1.365 (5)	C17—C18	1.387 (5)
C6—C7	1.370 (4)	C17—C17^i	1.394 (6)
C6—H6	0.9300	C18—C19	1.375 (7)
C7—C8	1.384 (4)	C18—H18	0.9300
C7—H7	0.9300	C19—C19^i	1.340 (11)
C9—C10	1.473 (4)	C19—H19	0.9300
C10—C11	1.384 (4)
C9—O2—C8	119.0 (2)	C15—C10—C9	120.8 (3)
C1—O3—C16	112.5 (2)	C10—C11—C12	121.0 (3)
C9—C1—O3	118.9 (2)	C10—C11—H11	119.5
C9—C1—C2	122.6 (2)	C12—C11—H11	119.5
O3—C1—C2	118.5 (2)	C13—C12—C11	119.6 (3)
O1—C2—C1	123.2 (3)	C13—C12—H12	120.2
O1—C2—C3	123.4 (3)	C11—C12—H12	120.2
C1—C2—C3	113.3 (2)	C12—C13—C14	120.3 (3)
C8—C3—C4	117.9 (3)	C12—C13—H13	119.9
C8—C3—C2	121.2 (2)	C14—C13—H13	119.9
C4—C3—C2	120.9 (3)	C13—C14—C15	120.1 (3)
C5—C4—C3	119.1 (3)	C13—C14—H14	120.0
C5—C4—H4	120.5	C15—C14—H14	120.0
C3—C4—H4	120.5	C10—C15—C14	120.6 (3)
C6—C5—C4	122.0 (3)	C10—C15—H15	119.7
C6—C5—Cl1	118.9 (3)	C14—C15—H15	119.7
C4—C5—Cl1	119.0 (3)	O3—C16—C17	112.8 (2)
C5—C6—C7	119.9 (3)	O3—C16—H16A	109.0
C5—C6—H6	120.0	C17—C16—H16A	109.0
C7—C6—H6	120.0	O3—C16—H16B	109.0
C6—C7—C8	118.6 (3)	C17—C16—H16B	109.0
C6—C7—H7	120.7	H16A—C16—H16B	107.8
C8—C7—H7	120.7	C18—C17—C17^i	118.5 (2)
C3—C8—C7	122.4 (3)	C18—C17—C16	120.0 (3)
C3—C8—O2	121.7 (2)	C17^i—C17—C16	121.43 (17)
C7—C8—O2	115.9 (3)	C19—C18—C17	121.4 (4)
C1—C9—O2	122.1 (2)	C19—C18—H18	119.3
C1—C9—C10	126.2 (2)	C17—C18—H18	119.3
O2—C9—C10	111.7 (2)	C19^i—C19—C18	120.1 (3)
C11—C10—C15	118.5 (3)	C19^i—C19—H19	120.0
C11—C10—C9	120.7 (3)	C18—C19—H19	120.0
C16—O3—C1—C9	111.1 (3)	O3—C1—C9—O2	179.8 (3)
C16—O3—C1—C2	−71.0 (3)	C2—C1—C9—O2	2.0 (4)
C9—C1—C2—O1	176.8 (3)	O3—C1—C9—C10	−0.3 (4)
O3—C1—C2—O1	−1.0 (5)	C2—C1—C9—C10	−178.1 (3)
C9—C1—C2—C3	−2.7 (4)	C8—O2—C9—C1	0.2 (4)
O3—C1—C2—C3	179.5 (3)	C8—O2—C9—C10	−179.7 (2)
O1—C2—C3—C8	−178.1 (3)	C1—C9—C10—C11	54.1 (4)
C1—C2—C3—C8	1.4 (4)	O2—C9—C10—C11	−126.0 (3)
O1—C2—C3—C4	1.8 (5)	C1—C9—C10—C15	−125.4 (3)
C1—C2—C3—C4	−178.7 (3)	O2—C9—C10—C15	54.4 (4)
C8—C3—C4—C5	−1.7 (5)	C15—C10—C11—C12	0.2 (5)
C2—C3—C4—C5	178.4 (3)	C9—C10—C11—C12	−179.3 (3)
C3—C4—C5—C6	1.4 (6)	C10—C11—C12—C13	0.9 (5)
C3—C4—C5—Cl1	179.6 (3)	C11—C12—C13—C14	−1.1 (5)
C4—C5—C6—C7	−0.1 (6)	C12—C13—C14—C15	0.1 (5)
Cl1—C5—C6—C7	−178.3 (3)	C11—C10—C15—C14	−1.3 (5)
C5—C6—C7—C8	−0.9 (6)	C9—C10—C15—C14	178.3 (3)
C4—C3—C8—C7	0.7 (5)	C13—C14—C15—C10	1.1 (5)
C2—C3—C8—C7	−179.4 (3)	C1—O3—C16—C17	−68.8 (3)
C4—C3—C8—O2	−179.4 (3)	O3—C16—C17—C18	106.2 (3)
C2—C3—C8—O2	0.5 (5)	O3—C16—C17—C17^i	−74.4 (4)
C6—C7—C8—C3	0.6 (5)	C17^i—C17—C18—C19	−1.1 (6)
C6—C7—C8—O2	−179.3 (3)	C16—C17—C18—C19	178.3 (4)
C9—O2—C8—C3	−1.4 (4)	C17—C18—C19—C19^i	−0.4 (8)
C9—O2—C8—C7	178.5 (3)

Symmetry code: (i) −x+1, y, −z−1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16B···O1	0.97	2.50	3.091 (4)	119
C18—H18···Cl1^ii	0.93	2.88	3.676 (5)	144

Symmetry code: (ii) −x+1/2, −y+1/2, −z.

(II) 3,3'-Propylenedioxybis[6-chloro-2-(2-furyl)flavanone]

Crystal data

C29H18Cl2O8	F(000) = 1160
Mr = 565.33	Dx = 1.605 Mg m^−3 Dm = 0.44 Mg m^−3 Dm measured by not measured
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 15.0485 (2) Å	Cell parameters from 10418 reflections
b = 7.6144 (1) Å	θ = 1.5–28.6°
c = 20.7890 (2) Å	µ = 0.34 mm^−1
β = 100.784 (1)°	T = 293 K
V = 2340.04 (5) Å^3	Prism, colourless
Z = 4	0.44 × 0.18 × 0.16 mm

Data collection

Siemens SMART CCD area-detector diffractometer	5813 independent reflections
Radiation source: fine-focus sealed tube	3529 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
ω scans	θmax = 28.6°, θmin = 1.5°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −19→20
Tmin = 0.867, Tmax = 0.948	k = −5→10
15953 measured reflections	l = −27→27

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 0.92
5813 reflections	(Δ/σ)max = 0.001
352 parameters	Δρmax = 0.56 e Å^−3
0 restraints	Δρmin = −0.46 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.27684 (5)	−0.04043 (10)	0.21880 (3)	0.0623 (2)
Cl2	1.24467 (4)	−0.00895 (9)	0.80900 (3)	0.05341 (19)
O1	0.58386 (10)	0.1925 (2)	0.36368 (8)	0.0539 (5)
O2	0.40531 (9)	0.17555 (19)	0.48759 (7)	0.0383 (4)
O3	0.43745 (11)	0.2454 (2)	0.60864 (8)	0.0464 (4)
O4	0.63782 (10)	0.2882 (2)	0.49802 (8)	0.0517 (4)
O5	0.87566 (11)	0.2711 (2)	0.52660 (7)	0.0511 (4)
O6	0.93334 (10)	0.1953 (2)	0.66247 (8)	0.0496 (4)
O7	1.10726 (9)	0.15019 (19)	0.53612 (7)	0.0371 (3)
O8	1.07277 (10)	0.2062 (2)	0.41415 (7)	0.0442 (4)
C1	0.55250 (14)	0.2439 (3)	0.46873 (10)	0.0362 (5)
C2	0.52998 (14)	0.1930 (3)	0.40109 (11)	0.0379 (5)
C3	0.43593 (13)	0.1378 (3)	0.37958 (10)	0.0342 (5)
C4	0.40346 (14)	0.0872 (3)	0.31524 (11)	0.0386 (5)
H4	0.4401	0.0961	0.2840	0.046*
C5	0.31786 (15)	0.0248 (3)	0.29843 (11)	0.0388 (5)
C6	0.26120 (15)	0.0098 (3)	0.34375 (12)	0.0437 (5)
H6	0.2032	−0.0359	0.3314	0.052*
C7	0.29164 (14)	0.0628 (3)	0.40650 (11)	0.0407 (5)
H7	0.2542	0.0562	0.4373	0.049*
C8	0.37853 (14)	0.1265 (3)	0.42403 (10)	0.0349 (5)
C9	0.49042 (14)	0.2362 (3)	0.50820 (10)	0.0353 (5)
C10	0.50583 (15)	0.2853 (3)	0.57608 (11)	0.0373 (5)
C11	0.46442 (18)	0.3079 (3)	0.67028 (12)	0.0519 (6)
H11	0.4309	0.2979	0.7034	0.062*
C12	0.54377 (19)	0.3842 (3)	0.67724 (12)	0.0547 (6)
H12	0.5752	0.4376	0.7149	0.066*
C13	0.57200 (17)	0.3697 (3)	0.61688 (12)	0.0503 (6)
H13	0.6261	0.4106	0.6070	0.060*
C14	0.69328 (15)	0.3888 (3)	0.46276 (11)	0.0415 (5)
H14A	0.6563	0.4700	0.4332	0.050*
H14B	0.7243	0.3117	0.4371	0.050*
C15	0.76059 (14)	0.4878 (3)	0.51150 (12)	0.0431 (5)
H15A	0.7969	0.5592	0.4877	0.052*
H15B	0.7277	0.5673	0.5350	0.052*
C16	0.82270 (14)	0.3816 (3)	0.56027 (11)	0.0420 (5)
H16A	0.8620	0.4583	0.5902	0.050*
H16B	0.7881	0.3104	0.5855	0.050*
C17	0.96155 (14)	0.2291 (3)	0.55547 (11)	0.0365 (5)
C18	0.98638 (13)	0.1895 (3)	0.62451 (10)	0.0348 (5)
C19	1.08064 (13)	0.1373 (3)	0.64575 (10)	0.0320 (4)
C20	1.11493 (14)	0.1006 (3)	0.71098 (10)	0.0346 (5)
H20	1.0797	0.1185	0.7427	0.042*
C21	1.20114 (15)	0.0376 (3)	0.72805 (11)	0.0376 (5)
C22	1.25475 (15)	0.0088 (3)	0.68169 (11)	0.0428 (5)
H22	1.3125	−0.0382	0.6942	0.051*
C23	1.22273 (14)	0.0493 (3)	0.61799 (11)	0.0414 (5)
H23	1.2588	0.0342	0.5866	0.050*
C24	1.13578 (13)	0.1132 (3)	0.60052 (10)	0.0332 (4)
C25	1.02245 (14)	0.2120 (3)	0.51543 (10)	0.0337 (4)
C26	1.00571 (14)	0.2517 (3)	0.44661 (10)	0.0360 (5)
C27	1.04502 (18)	0.2598 (3)	0.35162 (11)	0.0478 (6)
H27	1.0779	0.2441	0.3184	0.057*
C28	0.96548 (18)	0.3368 (3)	0.34377 (12)	0.0525 (6)
H28	0.9332	0.3850	0.3053	0.063*
C29	0.93907 (17)	0.3318 (3)	0.40518 (12)	0.0523 (6)
H29	0.8856	0.3757	0.4151	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0464 (4)	0.0846 (5)	0.0546 (4)	−0.0084 (3)	0.0060 (3)	−0.0173 (3)
Cl2	0.0417 (4)	0.0711 (4)	0.0449 (3)	0.0082 (3)	0.0017 (3)	0.0048 (3)
O1	0.0330 (9)	0.0806 (12)	0.0529 (10)	−0.0091 (8)	0.0205 (8)	−0.0126 (9)
O2	0.0268 (8)	0.0478 (8)	0.0425 (8)	−0.0001 (6)	0.0122 (7)	−0.0011 (7)
O3	0.0387 (9)	0.0593 (10)	0.0447 (9)	0.0021 (7)	0.0166 (7)	0.0036 (8)
O4	0.0291 (9)	0.0803 (12)	0.0455 (9)	−0.0118 (8)	0.0063 (7)	0.0130 (8)
O5	0.0342 (9)	0.0762 (11)	0.0425 (9)	0.0174 (8)	0.0063 (7)	−0.0075 (8)
O6	0.0303 (8)	0.0762 (11)	0.0459 (9)	0.0090 (8)	0.0163 (7)	0.0083 (8)
O7	0.0260 (8)	0.0490 (9)	0.0378 (8)	0.0025 (6)	0.0100 (6)	0.0008 (7)
O8	0.0385 (9)	0.0560 (9)	0.0413 (9)	0.0020 (7)	0.0154 (7)	−0.0011 (7)
C1	0.0244 (11)	0.0425 (11)	0.0425 (12)	−0.0007 (9)	0.0079 (9)	0.0049 (9)
C2	0.0284 (11)	0.0426 (12)	0.0450 (12)	0.0021 (9)	0.0131 (10)	0.0014 (9)
C3	0.0256 (11)	0.0320 (10)	0.0468 (12)	0.0029 (8)	0.0115 (9)	0.0014 (9)
C4	0.0325 (12)	0.0392 (11)	0.0459 (12)	0.0029 (9)	0.0125 (10)	−0.0009 (10)
C5	0.0314 (12)	0.0372 (11)	0.0477 (12)	0.0020 (9)	0.0076 (10)	−0.0025 (9)
C6	0.0290 (12)	0.0426 (12)	0.0596 (15)	−0.0020 (9)	0.0086 (11)	0.0027 (11)
C7	0.0272 (11)	0.0479 (12)	0.0497 (13)	0.0002 (9)	0.0137 (10)	0.0037 (10)
C8	0.0279 (11)	0.0337 (10)	0.0443 (12)	0.0044 (8)	0.0103 (9)	0.0017 (9)
C9	0.0289 (11)	0.0351 (11)	0.0433 (12)	0.0040 (8)	0.0098 (9)	0.0056 (9)
C10	0.0338 (12)	0.0393 (11)	0.0412 (12)	0.0070 (9)	0.0130 (10)	0.0086 (9)
C11	0.0523 (16)	0.0675 (16)	0.0394 (13)	0.0093 (13)	0.0177 (12)	0.0026 (11)
C12	0.0570 (17)	0.0635 (16)	0.0432 (13)	0.0026 (13)	0.0086 (12)	−0.0020 (12)
C13	0.0430 (14)	0.0595 (15)	0.0500 (14)	−0.0062 (12)	0.0125 (12)	0.0010 (12)
C14	0.0297 (11)	0.0487 (12)	0.0466 (12)	−0.0018 (10)	0.0084 (10)	0.0108 (10)
C15	0.0338 (12)	0.0406 (12)	0.0553 (13)	0.0037 (9)	0.0096 (11)	0.0036 (10)
C16	0.0286 (11)	0.0477 (12)	0.0502 (13)	0.0025 (9)	0.0084 (10)	−0.0067 (10)
C17	0.0272 (11)	0.0415 (11)	0.0416 (11)	0.0032 (9)	0.0080 (9)	−0.0024 (9)
C18	0.0250 (10)	0.0415 (11)	0.0394 (11)	0.0022 (8)	0.0097 (9)	0.0016 (9)
C19	0.0241 (10)	0.0331 (10)	0.0394 (11)	−0.0028 (8)	0.0075 (8)	−0.0011 (8)
C20	0.0285 (11)	0.0361 (11)	0.0406 (11)	−0.0004 (8)	0.0099 (9)	0.0011 (9)
C21	0.0314 (11)	0.0391 (11)	0.0413 (11)	−0.0006 (9)	0.0041 (9)	0.0005 (9)
C22	0.0262 (12)	0.0494 (13)	0.0518 (13)	0.0072 (9)	0.0052 (10)	−0.0028 (11)
C23	0.0289 (12)	0.0524 (13)	0.0451 (12)	0.0040 (10)	0.0129 (10)	−0.0040 (10)
C24	0.0245 (10)	0.0378 (11)	0.0374 (11)	−0.0021 (8)	0.0063 (8)	−0.0024 (9)
C25	0.0272 (11)	0.0353 (10)	0.0389 (11)	0.0010 (8)	0.0072 (8)	−0.0025 (9)
C26	0.0335 (12)	0.0363 (11)	0.0410 (12)	−0.0018 (9)	0.0140 (10)	−0.0045 (9)
C27	0.0516 (15)	0.0574 (14)	0.0377 (12)	−0.0058 (12)	0.0164 (11)	−0.0028 (11)
C28	0.0550 (16)	0.0640 (16)	0.0384 (13)	0.0038 (13)	0.0083 (11)	0.0016 (11)
C29	0.0448 (15)	0.0716 (17)	0.0418 (13)	0.0150 (12)	0.0113 (11)	0.0024 (12)

Geometric parameters (Å, º)

Cl1—C5	1.728 (2)	C11—H11	0.9300
Cl2—C21	1.724 (2)	C12—C13	1.402 (3)
O1—C2	1.224 (2)	C12—H12	0.9300
O2—C9	1.353 (2)	C13—H13	0.9300
O2—C8	1.360 (3)	C14—C15	1.495 (3)
O3—C11	1.356 (3)	C14—H14A	0.9700
O3—C10	1.368 (2)	C14—H14B	0.9700
O4—C1	1.357 (3)	C15—C16	1.484 (3)
O4—C14	1.432 (2)	C15—H15A	0.9700
O5—C17	1.357 (3)	C15—H15B	0.9700
O5—C16	1.429 (2)	C16—H16A	0.9700
O6—C18	1.224 (2)	C16—H16B	0.9700
O7—C25	1.353 (2)	C17—C25	1.355 (3)
O7—C24	1.357 (2)	C17—C18	1.446 (3)
O8—C27	1.352 (3)	C18—C19	1.460 (3)
O8—C26	1.360 (2)	C19—C24	1.378 (2)
C1—C9	1.355 (2)	C19—C20	1.386 (3)
C1—C2	1.437 (3)	C20—C21	1.366 (3)
C2—C3	1.464 (3)	C20—H20	0.9300
C3—C8	1.381 (2)	C21—C22	1.385 (3)
C3—C4	1.390 (3)	C22—C23	1.357 (3)
C4—C5	1.356 (3)	C22—H22	0.9300
C4—H4	0.9300	C23—C24	1.380 (3)
C5—C6	1.389 (3)	C23—H23	0.9300
C6—C7	1.361 (3)	C25—C26	1.438 (3)
C6—H6	0.9300	C26—C29	1.340 (3)
C7—C8	1.378 (3)	C27—C28	1.315 (3)
C7—H7	0.9300	C27—H27	0.9300
C9—C10	1.436 (3)	C28—C29	1.407 (3)
C10—C13	1.345 (3)	C28—H28	0.9300
C11—C12	1.312 (4)	C29—H29	0.9300
C9—O2—C8	119.5 (2)	C16—C15—C14	116.63 (19)
C11—O3—C10	105.66 (19)	C16—C15—H15A	108.1
C1—O4—C14	119.79 (17)	C14—C15—H15A	108.1
C17—O5—C16	119.62 (17)	C16—C15—H15B	108.1
C25—O7—C24	119.4 (2)	C14—C15—H15B	108.1
C27—O8—C26	106.03 (18)	H15A—C15—H15B	107.3
C9—C1—O4	116.14 (19)	O5—C16—C15	108.91 (18)
C9—C1—C2	121.2 (2)	O5—C16—H16A	109.9
O4—C1—C2	122.45 (17)	C15—C16—H16A	109.9
O1—C2—C1	124.0 (2)	O5—C16—H16B	109.9
O1—C2—C3	121.5 (2)	C15—C16—H16B	109.9
C1—C2—C3	114.5 (2)	H16A—C16—H16B	108.3
C8—C3—C4	118.38 (19)	C25—C17—O5	116.65 (19)
C8—C3—C2	120.3 (2)	C25—C17—C18	120.7 (2)
C4—C3—C2	121.28 (17)	O5—C17—C18	122.41 (17)
C5—C4—C3	119.41 (19)	O6—C18—C17	123.7 (2)
C5—C4—H4	120.3	O6—C18—C19	121.93 (19)
C3—C4—H4	120.3	C17—C18—C19	114.4 (2)
C4—C5—C6	121.9 (2)	C24—C19—C20	118.64 (19)
C4—C5—Cl1	119.96 (16)	C24—C19—C18	120.3 (2)
C6—C5—Cl1	118.15 (18)	C20—C19—C18	120.91 (16)
C7—C6—C5	119.1 (2)	C21—C20—C19	119.12 (18)
C7—C6—H6	120.4	C21—C20—H20	120.4
C5—C6—H6	120.4	C19—C20—H20	120.4
C6—C7—C8	119.37 (19)	C20—C21—C22	121.5 (2)
C6—C7—H7	120.3	C20—C21—Cl2	119.64 (16)
C8—C7—H7	120.3	C22—C21—Cl2	118.82 (17)
O2—C8—C7	116.59 (17)	C23—C22—C21	119.7 (2)
O2—C8—C3	121.6 (2)	C23—C22—H22	120.1
C7—C8—C3	121.8 (2)	C21—C22—H22	120.1
O2—C9—C1	122.8 (2)	C22—C23—C24	118.89 (18)
O2—C9—C10	111.67 (16)	C22—C23—H23	120.6
C1—C9—C10	125.5 (2)	C24—C23—H23	120.6
C13—C10—O3	109.33 (19)	O7—C24—C19	121.7 (2)
C13—C10—C9	135.13 (19)	O7—C24—C23	116.25 (17)
O3—C10—C9	115.5 (2)	C19—C24—C23	122.0 (2)
C12—C11—O3	111.42 (19)	O7—C25—C17	123.0 (2)
C12—C11—H11	124.3	O7—C25—C26	111.64 (16)
O3—C11—H11	124.3	C17—C25—C26	125.3 (2)
C11—C12—C13	106.8 (2)	C29—C26—O8	109.42 (18)
C11—C12—H12	126.6	C29—C26—C25	134.89 (19)
C13—C12—H12	126.6	O8—C26—C25	115.62 (19)
C10—C13—C12	106.8 (2)	C28—C27—O8	111.35 (19)
C10—C13—H13	126.6	C28—C27—H27	124.3
C12—C13—H13	126.6	O8—C27—H27	124.3
O4—C14—C15	107.98 (18)	C27—C28—C29	106.3 (2)
O4—C14—H14A	110.1	C27—C28—H28	126.9
C15—C14—H14A	110.1	C29—C28—H28	126.9
O4—C14—H14B	110.1	C26—C29—C28	106.9 (2)
C15—C14—H14B	110.1	C26—C29—H29	126.5
H14A—C14—H14B	108.4	C28—C29—H29	126.5
C14—O4—C1—C9	−146.3 (2)	C17—O5—C16—C15	147.85 (19)
C14—O4—C1—C2	38.9 (3)	C14—C15—C16—O5	61.4 (2)
C9—C1—C2—O1	−177.9 (2)	C16—O5—C17—C25	−145.39 (19)
O4—C1—C2—O1	−3.3 (3)	C16—O5—C17—C18	39.8 (3)
C9—C1—C2—C3	1.3 (3)	C25—C17—C18—O6	−176.8 (2)
O4—C1—C2—C3	175.84 (18)	O5—C17—C18—O6	−2.2 (3)
O1—C2—C3—C8	174.9 (2)	C25—C17—C18—C19	1.9 (3)
C1—C2—C3—C8	−4.3 (3)	O5—C17—C18—C19	176.56 (18)
O1—C2—C3—C4	−1.8 (3)	O6—C18—C19—C24	172.7 (2)
C1—C2—C3—C4	179.05 (18)	C17—C18—C19—C24	−6.0 (3)
C8—C3—C4—C5	−1.5 (3)	O6—C18—C19—C20	−3.3 (3)
C2—C3—C4—C5	175.20 (19)	C17—C18—C19—C20	177.99 (18)
C3—C4—C5—C6	0.0 (3)	C24—C19—C20—C21	−1.7 (3)
C3—C4—C5—Cl1	−179.44 (16)	C18—C19—C20—C21	174.38 (19)
C4—C5—C6—C7	1.5 (3)	C19—C20—C21—C22	−0.4 (3)
Cl1—C5—C6—C7	−179.04 (17)	C19—C20—C21—Cl2	−179.92 (15)
C5—C6—C7—C8	−1.4 (3)	C20—C21—C22—C23	2.3 (3)
C9—O2—C8—C7	178.83 (18)	Cl2—C21—C22—C23	−178.11 (18)
C9—O2—C8—C3	−0.4 (3)	C21—C22—C23—C24	−2.2 (3)
C6—C7—C8—O2	−179.30 (19)	C25—O7—C24—C19	−0.2 (3)
C6—C7—C8—C3	−0.1 (3)	C25—O7—C24—C23	179.48 (18)
C4—C3—C8—O2	−179.24 (18)	C20—C19—C24—O7	−178.55 (18)
C2—C3—C8—O2	4.0 (3)	C18—C19—C24—O7	5.4 (3)
C4—C3—C8—C7	1.6 (3)	C20—C19—C24—C23	1.8 (3)
C2—C3—C8—C7	−175.2 (2)	C18—C19—C24—C23	−174.24 (19)
C8—O2—C9—C1	−2.9 (3)	C22—C23—C24—O7	−179.54 (19)
C8—O2—C9—C10	178.65 (17)	C22—C23—C24—C19	0.1 (3)
O4—C1—C9—O2	−172.61 (18)	C24—O7—C25—C17	−4.3 (3)
C2—C1—C9—O2	2.3 (3)	C24—O7—C25—C26	177.19 (17)
O4—C1—C9—C10	5.7 (3)	O5—C17—C25—O7	−171.74 (18)
C2—C1—C9—C10	−179.43 (19)	C18—C17—C25—O7	3.2 (3)
C11—O3—C10—C13	−0.1 (2)	O5—C17—C25—C26	6.6 (3)
C11—O3—C10—C9	−177.91 (18)	C18—C17—C25—C26	−178.46 (19)
O2—C9—C10—C13	−170.4 (2)	C27—O8—C26—C29	−0.4 (2)
C1—C9—C10—C13	11.2 (4)	C27—O8—C26—C25	−177.95 (18)
O2—C9—C10—O3	6.7 (3)	O7—C25—C26—C29	−171.0 (3)
C1—C9—C10—O3	−171.7 (2)	C17—C25—C26—C29	10.5 (4)
C10—O3—C11—C12	0.6 (3)	O7—C25—C26—O8	5.7 (3)
O3—C11—C12—C13	−0.8 (3)	C17—C25—C26—O8	−172.78 (19)
O3—C10—C13—C12	−0.4 (3)	C26—O8—C27—C28	0.6 (3)
C9—C10—C13—C12	176.8 (2)	O8—C27—C28—C29	−0.6 (3)
C11—C12—C13—C10	0.7 (3)	O8—C26—C29—C28	0.0 (3)
C1—O4—C14—C15	153.75 (19)	C25—C26—C29—C28	176.9 (2)
O4—C14—C15—C16	59.9 (2)	C27—C28—C29—C26	0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O4	0.93	2.49	2.896 (3)	107
C29—H29···O5	0.93	2.48	2.898 (3)	107
C6—H6···O6^i	0.93	2.41	3.299 (3)	160
C22—H22···O1^ii	0.93	2.44	3.161 (3)	134

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