7,7′,8,8′-Tetra­meth­oxy-4,4′-dimethyl-3,5′-bichromene-2,2′-dione

Fun, H.-K.; Jebas, S.R.; Parveen, M.; Khanam, Z.; Ghalib, R.M.

doi:10.1107/S1600536809018029

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages o1322-o1323

doi:10.1107/S1600536809018029

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7,7′,8,8′-Tetramethoxy-4,4′-dimethyl-3,5′-bichromene-2,2′-dione

Hoong-Kun Fun,^a ^*‡ Samuel Robinson Jebas,^a § Mehtab Parveen,^b Zakia Khanam ^b and Raza Murad Ghalib ^b

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 Universiti Sains Malaysia, Penang, Malaysia, and ^bDepartment of Chemistry, Aligarh Muslim University, Aligarh 202 002 (UP), India
^*Correspondence e-mail: hkfun@usm.my

(Received 5 May 2009; accepted 13 May 2009; online 20 May 2009)

In the title molecule, C₂₄H₂₂O₈, the mean planes of the two coumarin units are inclined to each other at a dihedral angle of 79.93 (3)°. The attached methoxy groups form torsion angles of 7.65 (19) and 78.36 (14)° with respect to one coumarin unit, and angles of 9.01 (16) and 99.08 (11)° with respect to the other coumarin unit. In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds connect pairs of molecules to form dimers, generating R₂²(16) and R₂²(18) rings; the dimers are linked by further weak intermolecular C—H⋯O hydrogen bonds, forming extended chains. Additional stabilization is provided by weak C—H⋯π interactions.

Related literature

For the biological activity of coumarins, see: El-Agrody et al. (2001 ); El-Farargy (1991 ); Emmanuel-Giota et al. (2001 ); Ghate et al. (2005 ); Laakso et al. (1994 ); Nofal et al. (2000 ); Pratibha et al. (1999 ); Shaker (1996 ); Yang et al. (2005 ). For the pharmaceutical properties of coumarin derivatives, see: Kennedy et al. (1997 ). For related literature on natural and synthetic coumarins, see: Carlton et al. (1996 ); Zhou et al. (2000 ). For standard bond-length data, see: Allen et al. (1987 ). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₄H₂₂O₈
M_r = 438.42
Monoclinic, P 2₁ /c
a = 9.4724 (1) Å
b = 23.4766 (3) Å
c = 9.3525 (1) Å
β = 96.254 (1)°
V = 2067.43 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.50 × 0.27 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.949, T_max = 0.985
58385 measured reflections
7006 independent reflections
6023 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.125
S = 1.07
7006 reflections
295 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21A⋯O6ⁱ	0.96	2.55	3.2921 (15)	134
C22—H22A⋯O6ⁱⁱ	0.96	2.52	3.4385 (14)	161
C22—H22B⋯O8ⁱ	0.96	2.56	3.4401 (15)	152
C6—H6A⋯Cg1ⁱⁱⁱ	0.93	2.92	3.6706 (12)	138
C19—H19A⋯Cg2^iv	0.96	2.60	3.5446 (14)	170
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y+2, -z+2; (iii) x+1, y, z; (iv) $[x+1, -y+{\script{1\over 2}}, z-{\script{3\over 2}}]$ . Cg1 is the centroid of the O7/C14–C18 ring and Cg2 is the centroid of the C10–C18 ring.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809018029/lh2822sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809018029/lh2822Isup2.hkl

checkCIF report

Comment top

Coumarins are a large group of naturally occurring oxygen heterocycles representing 2H-1-benzopyran-2-one derivatives. Many natural coumarins are reputed for their wide range of biological activites such as antibacterial (El-Agrody et al., 2001; Pratibha et al., 1999), antifungal (Shaker, 1996; El-Farargy, 1991), antioxidant (Yang et al., 2005), analgesic (Ghate et al., 2005), anti-inflammatory (Emmanuel-Giota et al., 2001) and antitumor (Nofal et al., 2000). Bi and tri-coumarins are a comparatively new group of compounds which are widespread in nature and their biological properties are also well known (Laakso et al., 1994). One of the characteristic pharmacological properties of coumarin derivatives is anticoagulant action (Kennedy et al., 1997). A large number of natural and semisynthetic coumarin and bicoumarin derivatives have been reported to demonstrate chemopreventive (Carlton et al., 1996) and anti-HIV (Zhou et al., 2000) activities. Keeping in view of these biological importance of coumarins and their dimers, we have synthesized the title compound (I) and report herein its crystal structure.

The molecular structure of the title compound is shown in Fig .1. In crystal structure of (I) molecules are linked by weak intermolecular C-H···O hydrogen bonds to form R₂²(16) and R₂²(18) rings (Bernstein et al., (1995). The two coumarin units are essentially planar with the maximum deviation from planarity of 0.0665 (11)Å for atom C9 in the ring (O3/C1–C9) and 0.0419 (12)Å for atom C16 in the ring (O7/C10–C18). The two coumarin units forming a dihedral angle of 79.93 (3)° (O3/C1–C9:O7/C10–C18), indicating that they are inclined to each other. Two of the methoxy units attached to the each coumarin units are twisted from the plane of coumarin unit as indicated by the torsion angles of C19–O1—C4–C5=-7.65 (19)°; C20–O2–C3–C2=78.36 (14)°; C22–O5–C12–C11=9.01 (16)° and C23–O6–C13–C14=99.08 (11)°, respectively. The bond lengths Allen et al. (1987) and bond angles are normal.

The crystal packing is illustrated in Fig. 2. In addition C—H···π interactions help stabilize the crystal structure.

Related literature top

For the biological activity of coumarins, see: El-Agrody et al. (2001); El-Farargy (1991); Emmanuel-Giota et al. (2001); Ghate et al. (2005); Laakso et al. (1994); Nofal et al. (2000); Pratibha et al. (1999); Shaker (1996); Yang et al. (2005). For the pharmaceutical properties of coumarin derivatives, see: Kennedy et al. (1997). For related literature on natural and synthetic coumarins, see: Carlton et al. (1996); Zhou et al. (2000). For standard bond-length data, see: Allen et al. (1987). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995). Cg1 is the centroid of the O7/C14–C18 ring and Cg2 is the centroid of the C10–C18 ring.

Experimental top

A mixture of 7,8-dimethoxy-4-methyl coumarin (2.20 g, 10 mmol) and manganese(III) acetate (0.774 g, 1 mmol) was stirred at room temperature, then 70% perchloric acid (0.8 g, 6 mmol) was added. The reaction mixture was heated under reflux at 114°C with stirring in the atmosphere of nitrogen for 3 h. The reaction mixture was cooled and diluted with 50 ml of benzene. The benzene solution was washed with water and aq. NaHCO₃, dried over anhydrous Na₂SO₄ and left to evaporate. The residue showed two major compounds which were separated by column chromatography followed by preparative thin layer chromatography (Benzene: EtOAc, 9:1) into the title compound (I) (260 mg, 12%).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom numbering scheme.
	Fig. 2. Part of the crystal structure of (I). Dashed lines indicate the hydrogen bonds.

7,7',8,8'-Tetramethoxy-4,4'-dimethyl-3,5'-bichromene-2,2'-dione top

Crystal data top

C₂₄H₂₂O₈	F(000) = 920
M_r = 438.42	D_x = 1.409 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9875 reflections
a = 9.4724 (1) Å	θ = 2.7–33.0°
b = 23.4766 (3) Å	µ = 0.11 mm⁻¹
c = 9.3525 (1) Å	T = 100 K
β = 96.254 (1)°	Plate, colourless
V = 2067.43 (4) Å³	0.50 × 0.27 × 0.14 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7006 independent reflections
Radiation source: fine-focus sealed tube	6023 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 31.7°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→13
T_min = 0.949, T_max = 0.985	k = −34→34
58385 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0593P)² + 0.8142P] where P = (F_o² + 2F_c²)/3
7006 reflections	(Δ/σ)_max < 0.001
295 parameters	Δρ_max = 0.47 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₂₄H₂₂O₈	V = 2067.43 (4) Å³
M_r = 438.42	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.4724 (1) Å	µ = 0.11 mm⁻¹
b = 23.4766 (3) Å	T = 100 K
c = 9.3525 (1) Å	0.50 × 0.27 × 0.14 mm
β = 96.254 (1)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	7006 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	6023 reflections with I > 2σ(I)
T_min = 0.949, T_max = 0.985	R_int = 0.030
58385 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.07	Δρ_max = 0.47 e Å⁻³
7006 reflections	Δρ_min = −0.24 e Å⁻³
295 parameters

Special details top

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.69654 (9)	0.68242 (4)	0.29953 (11)	0.0282 (2)
O2	0.43643 (8)	0.65723 (3)	0.37372 (10)	0.02296 (17)
O3	0.26852 (8)	0.73969 (3)	0.46388 (9)	0.01987 (16)
O4	0.05685 (9)	0.76180 (3)	0.52477 (10)	0.02502 (18)
O5	0.03012 (9)	0.95276 (4)	0.88144 (9)	0.02254 (17)
O6	−0.18774 (8)	0.99197 (3)	0.69969 (9)	0.02027 (16)
O7	−0.22134 (8)	0.96109 (3)	0.42722 (8)	0.01782 (15)
O8	−0.35251 (9)	0.97343 (4)	0.21952 (10)	0.02664 (18)
C1	0.17182 (11)	0.77961 (4)	0.50060 (12)	0.01762 (19)
C2	0.40061 (11)	0.75552 (4)	0.43041 (12)	0.01703 (19)
C3	0.48594 (11)	0.71220 (4)	0.38541 (13)	0.0191 (2)
C4	0.62110 (12)	0.72617 (5)	0.34739 (13)	0.0217 (2)
C5	0.66991 (12)	0.78230 (5)	0.36156 (16)	0.0274 (3)
H5A	0.7607	0.7914	0.3398	0.033*
C6	0.58343 (12)	0.82435 (5)	0.40787 (15)	0.0247 (2)
H6A	0.6174	0.8615	0.4172	0.030*
C7	0.44578 (11)	0.81239 (4)	0.44116 (12)	0.01799 (19)
C8	0.34781 (11)	0.85546 (4)	0.48140 (12)	0.01690 (18)
C9	0.21437 (11)	0.83939 (4)	0.50522 (11)	0.01574 (18)
C10	0.10535 (11)	0.88049 (4)	0.54652 (11)	0.01548 (18)
C11	0.12224 (11)	0.89822 (4)	0.68924 (11)	0.01727 (19)
H11A	0.1996	0.8852	0.7502	0.021*
C12	0.02494 (11)	0.93527 (4)	0.74272 (11)	0.01696 (18)
C13	−0.09034 (11)	0.95541 (4)	0.65136 (11)	0.01643 (18)
C14	−0.10474 (10)	0.93843 (4)	0.50800 (11)	0.01503 (18)
C15	−0.24804 (11)	0.95111 (5)	0.28163 (12)	0.0192 (2)
C16	−0.15038 (12)	0.91360 (5)	0.21998 (12)	0.01956 (19)
H16A	−0.1646	0.9067	0.1215	0.023*
C17	−0.03892 (11)	0.88778 (4)	0.29753 (11)	0.01678 (18)
C18	−0.00961 (10)	0.90076 (4)	0.45039 (11)	0.01475 (17)
C19	0.82791 (13)	0.69680 (6)	0.24429 (17)	0.0318 (3)
H19A	0.8643	0.6639	0.1997	0.048*
H19B	0.8956	0.7094	0.3218	0.048*
H19C	0.8115	0.7267	0.1745	0.048*
C20	0.49521 (14)	0.62163 (6)	0.48972 (18)	0.0333 (3)
H20A	0.4725	0.5826	0.4674	0.050*
H20B	0.4560	0.6322	0.5763	0.050*
H20C	0.5965	0.6262	0.5031	0.050*
C21	0.39362 (12)	0.91653 (5)	0.49091 (15)	0.0257 (2)
H21A	0.3114	0.9406	0.4878	0.039*
H21B	0.4459	0.9254	0.4115	0.039*
H21C	0.4528	0.9227	0.5796	0.039*
C22	0.15479 (13)	0.93845 (5)	0.97486 (12)	0.0238 (2)
H22A	0.1452	0.9520	1.0701	0.036*
H22B	0.2362	0.9559	0.9401	0.036*
H22C	0.1667	0.8978	0.9770	0.036*
C23	−0.29354 (12)	0.96294 (5)	0.77235 (14)	0.0259 (2)
H23A	−0.3698	0.9887	0.7853	0.039*
H23B	−0.2515	0.9498	0.8645	0.039*
H23C	−0.3297	0.9310	0.7156	0.039*
C24	0.04626 (13)	0.84603 (5)	0.22071 (12)	0.0231 (2)
H24A	0.0104	0.8448	0.1207	0.035*
H24B	0.0389	0.8089	0.2622	0.035*
H24C	0.1440	0.8577	0.2301	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0195 (4)	0.0190 (4)	0.0486 (6)	0.0025 (3)	0.0146 (4)	−0.0069 (4)
O2	0.0185 (4)	0.0128 (3)	0.0376 (5)	−0.0003 (3)	0.0030 (3)	−0.0021 (3)
O3	0.0148 (3)	0.0137 (3)	0.0323 (4)	0.0002 (3)	0.0084 (3)	0.0006 (3)
O4	0.0187 (4)	0.0191 (4)	0.0394 (5)	−0.0007 (3)	0.0131 (3)	0.0040 (3)
O5	0.0217 (4)	0.0293 (4)	0.0165 (4)	0.0057 (3)	0.0015 (3)	−0.0044 (3)
O6	0.0202 (4)	0.0194 (3)	0.0224 (4)	0.0060 (3)	0.0074 (3)	−0.0010 (3)
O7	0.0160 (3)	0.0176 (3)	0.0196 (4)	0.0032 (3)	0.0009 (3)	0.0009 (3)
O8	0.0217 (4)	0.0313 (4)	0.0257 (4)	0.0055 (3)	−0.0034 (3)	0.0020 (3)
C1	0.0160 (4)	0.0151 (4)	0.0225 (5)	0.0022 (3)	0.0059 (4)	0.0022 (3)
C2	0.0130 (4)	0.0153 (4)	0.0234 (5)	0.0004 (3)	0.0045 (4)	0.0005 (3)
C3	0.0156 (4)	0.0136 (4)	0.0283 (5)	0.0003 (3)	0.0039 (4)	−0.0018 (4)
C4	0.0172 (5)	0.0167 (4)	0.0326 (6)	0.0026 (3)	0.0078 (4)	−0.0031 (4)
C5	0.0171 (5)	0.0187 (5)	0.0485 (7)	−0.0010 (4)	0.0136 (5)	−0.0040 (5)
C6	0.0175 (5)	0.0156 (4)	0.0428 (7)	−0.0013 (4)	0.0106 (5)	−0.0032 (4)
C7	0.0147 (4)	0.0138 (4)	0.0263 (5)	0.0005 (3)	0.0057 (4)	−0.0005 (3)
C8	0.0151 (4)	0.0137 (4)	0.0220 (5)	0.0010 (3)	0.0030 (4)	−0.0002 (3)
C9	0.0154 (4)	0.0139 (4)	0.0184 (4)	0.0017 (3)	0.0041 (3)	0.0004 (3)
C10	0.0148 (4)	0.0137 (4)	0.0185 (4)	0.0010 (3)	0.0044 (3)	0.0007 (3)
C11	0.0156 (4)	0.0187 (4)	0.0176 (4)	0.0030 (3)	0.0022 (3)	0.0003 (3)
C12	0.0172 (4)	0.0179 (4)	0.0161 (4)	0.0009 (3)	0.0031 (3)	−0.0010 (3)
C13	0.0165 (4)	0.0153 (4)	0.0181 (4)	0.0029 (3)	0.0047 (3)	−0.0006 (3)
C14	0.0132 (4)	0.0143 (4)	0.0176 (4)	0.0009 (3)	0.0019 (3)	0.0012 (3)
C15	0.0184 (5)	0.0194 (4)	0.0194 (5)	−0.0014 (3)	0.0007 (4)	0.0014 (4)
C16	0.0205 (5)	0.0215 (5)	0.0167 (4)	−0.0011 (4)	0.0020 (4)	−0.0004 (4)
C17	0.0181 (4)	0.0156 (4)	0.0173 (4)	−0.0018 (3)	0.0049 (3)	−0.0005 (3)
C18	0.0152 (4)	0.0132 (4)	0.0165 (4)	0.0004 (3)	0.0043 (3)	0.0004 (3)
C19	0.0205 (5)	0.0279 (6)	0.0496 (8)	0.0011 (4)	0.0157 (5)	−0.0096 (5)
C20	0.0235 (6)	0.0236 (5)	0.0527 (8)	0.0009 (4)	0.0034 (5)	0.0119 (5)
C21	0.0184 (5)	0.0143 (4)	0.0451 (7)	−0.0001 (4)	0.0063 (5)	−0.0029 (4)
C22	0.0240 (5)	0.0293 (5)	0.0176 (5)	0.0024 (4)	−0.0006 (4)	−0.0004 (4)
C23	0.0184 (5)	0.0284 (5)	0.0322 (6)	0.0002 (4)	0.0078 (4)	−0.0034 (5)
C24	0.0285 (6)	0.0238 (5)	0.0178 (5)	0.0052 (4)	0.0057 (4)	−0.0028 (4)

Geometric parameters (Å, º) top

O1—C4	1.3548 (13)	C11—C12	1.3988 (14)
O1—C19	1.4386 (15)	C11—H11A	0.9300
O2—C3	1.3733 (12)	C12—C13	1.3939 (14)
O2—C20	1.4332 (16)	C13—C14	1.3911 (14)
O3—C2	1.3736 (12)	C14—C18	1.4107 (13)
O3—C1	1.3798 (12)	C15—C16	1.4421 (15)
O4—C1	1.2106 (13)	C16—C17	1.3569 (15)
O5—C12	1.3565 (13)	C16—H16A	0.9300
O5—C22	1.4305 (14)	C17—C18	1.4586 (14)
O6—C13	1.3723 (12)	C17—C24	1.5015 (15)
O6—C23	1.4419 (14)	C19—H19A	0.9600
O7—C14	1.3755 (12)	C19—H19B	0.9600
O7—C15	1.3777 (13)	C19—H19C	0.9600
O8—C15	1.2108 (13)	C20—H20A	0.9600
C1—C9	1.4594 (14)	C20—H20B	0.9600
C2—C3	1.3924 (14)	C20—H20C	0.9600
C2—C7	1.4023 (14)	C21—H21A	0.9600
C3—C4	1.4043 (15)	C21—H21B	0.9600
C4—C5	1.3980 (15)	C21—H21C	0.9600
C5—C6	1.3822 (15)	C22—H22A	0.9600
C5—H5A	0.9300	C22—H22B	0.9600
C6—C7	1.4016 (15)	C22—H22C	0.9600
C6—H6A	0.9300	C23—H23A	0.9600
C7—C8	1.4496 (14)	C23—H23B	0.9600
C8—C9	1.3605 (14)	C23—H23C	0.9600
C8—C21	1.4977 (14)	C24—H24A	0.9600
C9—C10	1.4945 (14)	C24—H24B	0.9600
C10—C11	1.3906 (14)	C24—H24C	0.9600
C10—C18	1.4168 (14)

C4—O1—C19	116.67 (9)	O8—C15—O7	116.93 (10)
C3—O2—C20	112.74 (10)	O8—C15—C16	126.78 (10)
C2—O3—C1	121.26 (8)	O7—C15—C16	116.26 (9)
C12—O5—C22	117.03 (9)	C17—C16—C15	123.69 (10)
C13—O6—C23	112.73 (8)	C17—C16—H16A	118.2
C14—O7—C15	121.80 (8)	C15—C16—H16A	118.2
O4—C1—O3	116.55 (9)	C16—C17—C18	118.98 (9)
O4—C1—C9	125.29 (9)	C16—C17—C24	117.60 (10)
O3—C1—C9	118.15 (9)	C18—C17—C24	123.41 (9)
O3—C2—C3	116.39 (9)	C14—C18—C10	116.55 (9)
O3—C2—C7	121.30 (9)	C14—C18—C17	116.36 (9)
C3—C2—C7	122.30 (9)	C10—C18—C17	127.08 (9)
O2—C3—C2	120.39 (9)	O1—C19—H19A	109.5
O2—C3—C4	120.81 (9)	O1—C19—H19B	109.5
C2—C3—C4	118.76 (9)	H19A—C19—H19B	109.5
O1—C4—C5	124.40 (10)	O1—C19—H19C	109.5
O1—C4—C3	115.77 (10)	H19A—C19—H19C	109.5
C5—C4—C3	119.82 (10)	H19B—C19—H19C	109.5
C6—C5—C4	120.12 (10)	O2—C20—H20A	109.5
C6—C5—H5A	119.9	O2—C20—H20B	109.5
C4—C5—H5A	119.9	H20A—C20—H20B	109.5
C5—C6—C7	121.60 (10)	O2—C20—H20C	109.5
C5—C6—H6A	119.2	H20A—C20—H20C	109.5
C7—C6—H6A	119.2	H20B—C20—H20C	109.5
C6—C7—C2	117.31 (9)	C8—C21—H21A	109.5
C6—C7—C8	123.73 (9)	C8—C21—H21B	109.5
C2—C7—C8	118.93 (9)	H21A—C21—H21B	109.5
C9—C8—C7	118.78 (9)	C8—C21—H21C	109.5
C9—C8—C21	121.61 (9)	H21A—C21—H21C	109.5
C7—C8—C21	119.58 (9)	H21B—C21—H21C	109.5
C8—C9—C1	121.36 (9)	O5—C22—H22A	109.5
C8—C9—C10	122.93 (9)	O5—C22—H22B	109.5
C1—C9—C10	115.60 (9)	H22A—C22—H22B	109.5
C11—C10—C18	120.57 (9)	O5—C22—H22C	109.5
C11—C10—C9	115.52 (9)	H22A—C22—H22C	109.5
C18—C10—C9	123.91 (9)	H22B—C22—H22C	109.5
C10—C11—C12	121.19 (9)	O6—C23—H23A	109.5
C10—C11—H11A	119.4	O6—C23—H23B	109.5
C12—C11—H11A	119.4	H23A—C23—H23B	109.5
O5—C12—C13	115.33 (9)	O6—C23—H23C	109.5
O5—C12—C11	125.00 (9)	H23A—C23—H23C	109.5
C13—C12—C11	119.63 (9)	H23B—C23—H23C	109.5
O6—C13—C14	119.86 (9)	C17—C24—H24A	109.5
O6—C13—C12	121.34 (9)	C17—C24—H24B	109.5
C14—C13—C12	118.79 (9)	H24A—C24—H24B	109.5
O7—C14—C13	114.02 (8)	C17—C24—H24C	109.5
O7—C14—C18	122.74 (9)	H24A—C24—H24C	109.5
C13—C14—C18	123.23 (9)	H24B—C24—H24C	109.5

C2—O3—C1—O4	178.16 (10)	C8—C9—C10—C18	103.55 (13)
C2—O3—C1—C9	−0.94 (15)	C1—C9—C10—C18	−80.20 (12)
C1—O3—C2—C3	−175.74 (10)	C18—C10—C11—C12	1.57 (15)
C1—O3—C2—C7	4.15 (16)	C9—C10—C11—C12	−178.01 (9)
C20—O2—C3—C2	−103.96 (12)	C22—O5—C12—C13	−173.06 (9)
C20—O2—C3—C4	78.36 (14)	C22—O5—C12—C11	9.01 (16)
O3—C2—C3—O2	1.16 (16)	C10—C11—C12—O5	177.12 (10)
C7—C2—C3—O2	−178.72 (10)	C10—C11—C12—C13	−0.73 (16)
O3—C2—C3—C4	178.89 (10)	C23—O6—C13—C14	99.08 (11)
C7—C2—C3—C4	−1.00 (17)	C23—O6—C13—C12	−81.83 (12)
C19—O1—C4—C5	−7.65 (19)	O5—C12—C13—O6	2.19 (15)
C19—O1—C4—C3	172.97 (11)	C11—C12—C13—O6	−179.76 (9)
O2—C3—C4—O1	0.06 (17)	O5—C12—C13—C14	−178.71 (9)
C2—C3—C4—O1	−177.65 (10)	C11—C12—C13—C14	−0.66 (15)
O2—C3—C4—C5	−179.34 (11)	C15—O7—C14—C13	176.70 (9)
C2—C3—C4—C5	2.94 (18)	C15—O7—C14—C18	−4.07 (14)
O1—C4—C5—C6	178.29 (13)	O6—C13—C14—O7	−0.41 (14)
C3—C4—C5—C6	−2.4 (2)	C12—C13—C14—O7	−179.52 (9)
C4—C5—C6—C7	−0.2 (2)	O6—C13—C14—C18	−179.63 (9)
C5—C6—C7—C2	2.14 (19)	C12—C13—C14—C18	1.25 (15)
C5—C6—C7—C8	−175.98 (12)	C14—O7—C15—O8	−179.20 (9)
O3—C2—C7—C6	178.61 (11)	C14—O7—C15—C16	2.60 (14)
C3—C2—C7—C6	−1.51 (17)	O8—C15—C16—C17	−176.66 (11)
O3—C2—C7—C8	−3.18 (16)	O7—C15—C16—C17	1.34 (16)
C3—C2—C7—C8	176.71 (10)	C15—C16—C17—C18	−3.75 (16)
C6—C7—C8—C9	177.07 (11)	C15—C16—C17—C24	174.94 (10)
C2—C7—C8—C9	−1.03 (16)	O7—C14—C18—C10	−179.60 (9)
C6—C7—C8—C21	−0.87 (18)	C13—C14—C18—C10	−0.43 (14)
C2—C7—C8—C21	−178.97 (11)	O7—C14—C18—C17	1.53 (14)
C7—C8—C9—C1	4.21 (16)	C13—C14—C18—C17	−179.31 (9)
C21—C8—C9—C1	−177.89 (11)	C11—C10—C18—C14	−0.98 (14)
C7—C8—C9—C10	−179.74 (10)	C9—C10—C18—C14	178.57 (9)
C21—C8—C9—C10	−1.85 (17)	C11—C10—C18—C17	177.76 (10)
O4—C1—C9—C8	177.67 (11)	C9—C10—C18—C17	−2.69 (16)
O3—C1—C9—C8	−3.33 (15)	C16—C17—C18—C14	2.26 (14)
O4—C1—C9—C10	1.35 (16)	C24—C17—C18—C14	−176.35 (9)
O3—C1—C9—C10	−179.65 (9)	C16—C17—C18—C10	−176.47 (10)
C8—C9—C10—C11	−76.88 (13)	C24—C17—C18—C10	4.91 (16)
C1—C9—C10—C11	99.37 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21A···O6ⁱ	0.96	2.55	3.2921 (15)	134
C22—H22A···O6ⁱⁱ	0.96	2.52	3.4385 (14)	161
C22—H22B···O8ⁱ	0.96	2.56	3.4401 (15)	152
C6—H6A···Cg1ⁱⁱⁱ	0.93	2.92	3.6706 (12)	138
C19—H19A···Cg2^iv	0.96	2.60	3.5446 (14)	170

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

Experimental details

Crystal data
Chemical formula	C₂₄H₂₂O₈
M_r	438.42
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	9.4724 (1), 23.4766 (3), 9.3525 (1)
β (°)	96.254 (1)
V (Å³)	2067.43 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.50 × 0.27 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.949, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	58385, 7006, 6023
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.740

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.125, 1.07
No. of reflections	7006
No. of parameters	295
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.47, −0.24

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21A···O6ⁱ	0.96	2.55	3.2921 (15)	134
C22—H22A···O6ⁱⁱ	0.96	2.52	3.4385 (14)	161
C22—H22B···O8ⁱ	0.96	2.56	3.4401 (15)	152
C6—H6A···Cg1ⁱⁱⁱ	0.93	2.92	3.6706 (12)	138
C19—H19A···Cg2^iv	0.96	2.60	3.5446 (14)	170

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

Footnotes

‡Thomson Reuters ResearcherID: A-3561-2009.

§Thomson Reuters ResearcherID: A-5473-2009. Permanent address: Department of Physics, Karunya University, Karunya Nagar, Coimbatore 641 114, India.

Acknowledgements

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

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