Two crystal polymorphs of a flavonoid from Melicope ellyrana

The crystal structure determinations of two crystalline components of the hexane extract of the fruit of the indigenous Australian tree Melicope ellyrana have shown them to be polymorphs of the same compound, namely the flavonoid 4',5-di­hydroxy-3,3',8-tri­methoxy-7-(3-methyl­but-2-enyl­oxy)­flavone [systematic name: 5-hydroxy-2-(4-hydroxy-3-methoxy­phenyl)-3,8-di­methoxy-7-(3-methyl­but-2-enyl­oxy)-4H-1-benzo­pyran-4-one], C₂₃H₂₄O₈. The two polymorphs, one monoclinic (polymorph A) and the other triclinic (polymorph B), show significant conformational differences, particularly in the enyl­oxy side chain, while only one (polymorph A) shows intermolecular hydrogen bonding.

S1. Comment

Investigation of the hexane extract of the fruit of the indigenous Australian tree Melicope ellyrana (formerly Euodia ellyrana F. Meull) (Hartley, 1981) resulted in the isolation of three flavonoids, namely 4',5-dihydroxy-3,3',8-trimethoxy-7-(3-methylbut-2-enyloxy)flavone, (I), pachypodol (4',5-dihydroxy-3,3',7-trimethoxyflavone), (II), and tenatin (4',5-dihydroxy-3,3',7,8-tetramethoxyflavone), (III). Although compound (I) has previously been isolated from Boronia coerulescens (Ashan et al., 1994), and other prenylated flavones similar to (I) have been reported, i.e. from M. triphylla (Higa et al., 1987) and M. micrococca (Nasim, 1999), this represents the first report and cystallographic characterization of (I) from M. ellyrana.

Two morphologically different crystalline forms of (I) obtained from n-hexane (monoclinic polymorph A) and ethyl acetate (triclinic polymorph B) extracts allowed, in the first instance (because of the minute quantities of the available sample involved), determination of the identity of both polymorphs as the title compound and, in the second instance, confirmation of the existence of two significantly different molecular conformations (Figs. 1 and 2). Triclinic form B has a more compact molecular form than is found for monoclinic form A due mainly to the more convoluted enyloxy side chain (comparative molecular volumes of 506 and 526 ų, respectively). This is reflected particularly in the C7—O7—C71—C72 and O7—C71—C72—C73 torsion angles of 81.9 (4) and 107.4 (5)°, respectively, in form B, and -174.6 (3) and 143.5 (4)° in polymorph A. In addition, the benzene ring substituent at C2, although essentially coplanar with the parent ring, is rotated about the C2—C12 bond vector such that the meta-substituted methoxy groups in the two polymorphs are ca 180° apart. Intramolecular C—H···O(methoxy) and C—H···O(ether) interactions are significant in maintaining the coplanarity of the two ring systems [C22–H22···O3 2.888 (5) Å and C62–H62···O1 2.627 (4) Å for form A; C22–H22···O1 2.664 (5) Å and C62–H62···O3 2.858 (5) Å for form B]. Relatively minor conformational differences are found in the methoxy substituents at C3, C8 and C52, while in each, there are intramolecular hydrogen-bonding interactions involving the hydroxyl group at C5 and the adjacent ketone O atom at C4 [O5—H5···O4: 2.600 (4) Å in form A and 2.586 (4) Å in form B], and the hydroxyl group at C42 and the adjacent methoxy O atom at C52 [O42—H42···O52: 2.692 (4) Å in form A and 2.657 (4) Å in form B].

A major difference between polymorphs A and B lies in the packing; in A, a single intermolecular hydrogen-bond interaction is found between the H atom of the hydroxyl group at C42 and a ketone O atom of a glide-related neighbour [O42—H42···O4ⁱ 2.784 (4) Å; symmetry code: (i) 1/2 + x, 1/2 - y, 1/2 + z]. This completes a three-centred hydrogen-bond association about H42, with a relatively long H42···O4ⁱ separation of 1.87 Å.

Related literature

For related literature, see: Hartley (1981); Higa et al. (1987); Nasim (1999).

S2. Experimental

Fresh fruit from Melicope ellyrana (1.5 kg) was extracted with n-hexane (4.5 l) for 72 h at room temperature and the extract concentrated by rotary evaporation. The extract (20 g) was subjected to GFC (please give full form of abbreviation) separation using methanol (monitored at λ = 254 nm), the eluent yielding 23 separate fractions. Two of these fractions gave crystals of the title compound in morphologically different and visually identifiable forms; one monoclinic (polymorph A) and the other triclinic (polymorph B).

S3. Refinement

With the exception of those H atoms involved in hydrogen-bonding interactions, H atoms were included at calculated positions and were constrained in the refinement (C—H = 0.94–0.96 Å).

[Author, there is a C72—H72 distance of 1.10 Å for form A in the CIF. Is this correct or should it be 0.95 Å ?]

Computing details

For both compounds, data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1999a); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1999b); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON for Windows (Spek, 1999); software used to prepare material for publication: TEXSAN for Windows.

Figures

	Fig. 1. The molecular configuration and atom-numbering scheme for the monoclinic polymorph A. Atoms are shown as 40% probability ellipsoids.
	Fig. 2. The molecular configuration and atom-numbering scheme for the triclinic polymorph B. Atoms are shown as 40% probability ellipsoids.

(I) 4',5-dihydroxy-3,3',8-trimethoxy-7-(3-methylbut-2-enyloxy)flavone

Crystal data

C23H24O8	F(000) = 904
Mr = 428.42	Dx = 1.352 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
a = 14.238 (4) Å	Cell parameters from 25 reflections
b = 11.053 (5) Å	θ = 20.1–27.2°
c = 14.426 (5) Å	µ = 0.10 mm^−1
β = 111.979 (18)°	T = 293 K
V = 2105.3 (13) Å^3	Prism, yellow
Z = 4	0.40 × 0.30 × 0.30 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.026
Radiation source: Rigaku rotating anode	θmax = 25.0°, θmin = 2.5°
Graphite monochromator	h = 0→16
ω–2θ scans	k = 0→13
3865 measured reflections	l = −17→15
3709 independent reflections	3 standard reflections every 150 reflections
1532 reflections with I > 2σ(I)	intensity decay: 0.3%

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.180	H-atom parameters constrained
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0873P)^2 + 0.3178P] where P = (Fo^2 + 2Fc^2)/3
3709 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.27 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
O1	0.89228 (17)	0.3923 (2)	0.44099 (16)	0.0475 (6)
O3	0.65547 (19)	0.4142 (2)	0.4787 (2)	0.0654 (8)
O4	0.63618 (19)	0.5967 (2)	0.34305 (19)	0.0594 (7)
O5	0.7059 (2)	0.7113 (3)	0.2249 (2)	0.0714 (8)
O7	1.02792 (19)	0.5804 (2)	0.22994 (18)	0.0616 (7)
O8	1.04877 (19)	0.4269 (2)	0.38221 (19)	0.0624 (8)
O42	0.9373 (2)	−0.0175 (3)	0.7492 (2)	0.0760 (9)
O52	1.0576 (2)	0.0509 (3)	0.6524 (2)	0.0752 (9)
C2	0.8175 (3)	0.3697 (3)	0.4759 (3)	0.0477 (9)
C3	0.7317 (3)	0.4379 (3)	0.4447 (3)	0.0495 (9)
C4A	0.7954 (3)	0.5524 (3)	0.3357 (3)	0.0489 (9)
C4	0.7154 (3)	0.5336 (3)	0.3729 (3)	0.0484 (9)
C5	0.7887 (3)	0.6385 (4)	0.2618 (3)	0.0536 (10)
C6	0.8642 (3)	0.6486 (4)	0.2244 (3)	0.0554 (10)
C7	0.9503 (3)	0.5759 (3)	0.2630 (3)	0.0519 (10)
C8	0.9599 (3)	0.4918 (3)	0.3375 (3)	0.0468 (9)
C8A	0.8814 (3)	0.4793 (3)	0.3710 (2)	0.0444 (9)
C12	0.8455 (3)	0.2667 (3)	0.5461 (3)	0.0469 (9)
C22	0.7850 (3)	0.2239 (4)	0.5956 (3)	0.0625 (11)
C31	0.6522 (4)	0.4982 (5)	0.5538 (4)	0.1048 (19)
C32	0.8165 (3)	0.1295 (4)	0.6624 (3)	0.0679 (12)
C42	0.9089 (3)	0.0741 (4)	0.6817 (3)	0.0569 (10)
C52	0.9685 (3)	0.1134 (4)	0.6302 (3)	0.0520 (10)
C62	0.9375 (3)	0.2080 (3)	0.5650 (3)	0.0509 (9)
C71	1.0187 (3)	0.6635 (4)	0.1501 (3)	0.0693 (12)
C72	1.1069 (3)	0.6438 (4)	0.1204 (3)	0.0686 (12)
C73	1.1036 (3)	0.6505 (4)	0.0282 (3)	0.0666 (12)
C81	1.0535 (4)	0.3132 (5)	0.3396 (4)	0.0952 (16)
C521	1.1204 (3)	0.0803 (4)	0.5997 (3)	0.0686 (12)
C731	1.1957 (4)	0.6311 (5)	0.0036 (4)	0.0990 (17)
C732	1.0096 (4)	0.6792 (5)	−0.0598 (3)	0.0966 (17)
H5	0.6594	0.6862	0.2617	0.050*
H6	0.8579	0.7052	0.1726	0.065*
H22	0.7210	0.2600	0.5832	0.074*
H32	0.7746	0.1024	0.6960	0.081*
H42	1.0031	−0.0544	0.7624	0.095*
H62	0.9800	0.2343	0.5313	0.061*
H72	1.1810	0.6280	0.1803	0.067*
H311	0.7099	0.4858	0.6140	0.126*
H312	0.6531	0.5788	0.5315	0.126*
H313	0.5924	0.4853	0.5670	0.126*
H521	1.1882	0.0574	0.6384	0.083*
H522	1.0978	0.0386	0.5378	0.083*
H523	1.1176	0.1651	0.5880	0.083*
H711	0.9572	0.6473	0.0941	0.082*
H712	1.0177	0.7441	0.1711	0.082*
H731	1.2529	0.6182	0.0635	0.120*
H732	1.1860	0.5628	−0.0388	0.120*
H733	1.2070	0.7009	−0.0295	0.120*
H734	0.9559	0.6968	−0.0379	0.116*
H735	1.0215	0.7470	−0.0942	0.116*
H736	0.9913	0.6114	−0.1037	0.116*
H811	0.9887	0.2748	0.3194	0.114*
H812	1.0701	0.3244	0.2819	0.114*
H813	1.1027	0.2640	0.3863	0.114*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0472 (14)	0.0515 (15)	0.0442 (14)	0.0005 (12)	0.0176 (12)	0.0019 (12)
O3	0.0568 (17)	0.0674 (19)	0.079 (2)	0.0027 (14)	0.0330 (16)	0.0053 (16)
O4	0.0522 (16)	0.0613 (18)	0.0632 (17)	0.0122 (14)	0.0198 (13)	−0.0006 (14)
O5	0.0658 (18)	0.073 (2)	0.076 (2)	0.0184 (16)	0.0272 (15)	0.0218 (16)
O7	0.0651 (17)	0.0697 (19)	0.0549 (16)	0.0028 (14)	0.0283 (14)	0.0099 (14)
O8	0.0576 (17)	0.0646 (19)	0.0631 (17)	0.0017 (14)	0.0203 (14)	0.0002 (15)
O42	0.0738 (19)	0.080 (2)	0.086 (2)	0.0101 (16)	0.0432 (17)	0.0337 (18)
O52	0.0747 (19)	0.086 (2)	0.082 (2)	0.0232 (17)	0.0489 (17)	0.0338 (17)
C2	0.050 (2)	0.049 (2)	0.044 (2)	−0.0103 (19)	0.0175 (18)	−0.0087 (18)
C3	0.047 (2)	0.052 (2)	0.052 (2)	−0.0048 (19)	0.0209 (19)	−0.0040 (19)
C4A	0.052 (2)	0.047 (2)	0.044 (2)	−0.0002 (19)	0.0127 (18)	−0.0074 (18)
C4	0.048 (2)	0.048 (2)	0.042 (2)	0.0025 (19)	0.0094 (18)	−0.0100 (18)
C5	0.055 (2)	0.051 (2)	0.049 (2)	0.005 (2)	0.012 (2)	−0.002 (2)
C6	0.060 (3)	0.056 (3)	0.046 (2)	0.003 (2)	0.016 (2)	0.006 (2)
C7	0.056 (2)	0.055 (2)	0.044 (2)	−0.006 (2)	0.0170 (19)	−0.0034 (19)
C8	0.047 (2)	0.045 (2)	0.043 (2)	0.0048 (18)	0.0107 (18)	−0.0021 (18)
C8A	0.048 (2)	0.045 (2)	0.037 (2)	−0.0020 (17)	0.0128 (18)	−0.0027 (17)
C12	0.050 (2)	0.047 (2)	0.046 (2)	−0.0045 (18)	0.0196 (18)	−0.0044 (18)
C22	0.051 (2)	0.067 (3)	0.072 (3)	0.002 (2)	0.026 (2)	0.012 (2)
C31	0.144 (5)	0.091 (4)	0.119 (4)	0.020 (3)	0.095 (4)	0.001 (3)
C32	0.059 (3)	0.076 (3)	0.079 (3)	−0.001 (2)	0.037 (2)	0.017 (3)
C42	0.056 (3)	0.061 (3)	0.054 (2)	−0.005 (2)	0.022 (2)	0.015 (2)
C52	0.055 (2)	0.054 (2)	0.050 (2)	0.0052 (19)	0.024 (2)	0.006 (2)
C62	0.057 (2)	0.051 (2)	0.051 (2)	0.0008 (19)	0.0272 (19)	0.0051 (19)
C71	0.082 (3)	0.069 (3)	0.064 (3)	−0.002 (2)	0.036 (2)	0.010 (2)
C72	0.068 (3)	0.075 (3)	0.071 (3)	−0.001 (2)	0.035 (2)	0.016 (2)
C73	0.084 (3)	0.052 (3)	0.078 (3)	−0.005 (2)	0.047 (3)	0.003 (2)
C81	0.099 (4)	0.082 (4)	0.090 (4)	0.030 (3)	0.018 (3)	−0.009 (3)
C521	0.069 (3)	0.079 (3)	0.069 (3)	0.021 (2)	0.038 (2)	0.018 (2)
C731	0.109 (4)	0.092 (4)	0.126 (4)	0.008 (3)	0.077 (4)	0.018 (3)
C732	0.103 (4)	0.131 (5)	0.065 (3)	−0.013 (3)	0.041 (3)	−0.001 (3)

Geometric parameters (Å, º)

O1—C8A	1.360 (4)	C22—H22	0.95
O1—C2	1.361 (4)	C31—H311	0.96
O3—C3	1.373 (4)	C31—H312	0.95
O3—C31	1.441 (5)	C31—H313	0.95
O4—C4	1.257 (4)	C32—C42	1.381 (5)
O5—C5	1.361 (4)	C32—H32	0.95
O5—H5	1.03	C42—C52	1.389 (5)
O7—C7	1.359 (4)	C52—C62	1.365 (5)
O7—C71	1.441 (5)	C62—H62	0.95
O8—C8	1.387 (4)	C71—C72	1.486 (6)
O8—C81	1.411 (5)	C71—H711	0.96
O42—C42	1.358 (4)	C71—H712	0.94
O42—H42	0.97	C72—C73	1.315 (5)
O52—C52	1.373 (4)	C72—H72	1.10
O52—C521	1.412 (4)	C73—C732	1.493 (6)
C2—C3	1.360 (5)	C73—C731	1.496 (6)
C2—C12	1.476 (5)	C81—H811	0.96
C3—C4	1.438 (5)	C81—H812	0.96
C4A—C8A	1.394 (5)	C81—H813	0.94
C4A—C5	1.406 (5)	C521—H522	0.95
C4A—C4	1.444 (5)	C521—H523	0.95
C5—C6	1.374 (5)	C521—H521	0.95
C6—C7	1.396 (5)	C731—H731	0.95
C6—H6	0.95	C731—H732	0.95
C7—C8	1.389 (5)	C731—H733	0.95
C8—C8A	1.381 (5)	C732—H734	0.95
C12—C22	1.391 (5)	C732—H735	0.95
C12—C62	1.394 (5)	C732—H736	0.95
C22—C32	1.376 (6)
C8A—O1—C2	121.1 (3)	C22—C32—H32	120
C3—O3—C31	113.5 (3)	C42—C32—H32	119
C5—O5—H5	106	O42—C42—C32	118.7 (3)
C7—O7—C71	117.5 (3)	O42—C42—C52	122.6 (4)
C8—O8—C81	116.3 (3)	C32—C42—C52	118.7 (4)
C42—O42—H42	117	C62—C52—O52	125.3 (3)
C52—O52—C521	118.4 (3)	C62—C52—C42	120.2 (3)
C3—C2—O1	120.4 (3)	O52—C52—C42	114.5 (3)
C3—C2—C12	129.3 (3)	C52—C62—C12	122.0 (3)
O1—C2—C12	110.4 (3)	C52—C62—H62	119
C2—C3—O3	120.5 (3)	C12—C62—H62	119
C2—C3—C4	122.0 (3)	O7—C71—C72	107.6 (3)
O3—C3—C4	117.5 (3)	O7—C71—H711	110
C8A—C4A—C5	118.1 (3)	C72—C71—H711	109
C8A—C4A—C4	119.2 (3)	O7—C71—H712	111
C5—C4A—C4	122.7 (3)	C72—C71—H712	110
O4—C4—C3	122.5 (3)	H711—C71—H712	109
O4—C4—C4A	121.6 (3)	C73—C72—C71	124.7 (4)
C3—C4—C4A	115.9 (3)	C73—C72—H72	118
O5—C5—C6	119.3 (3)	C71—C72—H72	118
O5—C5—C4A	119.9 (3)	C72—C73—C732	123.5 (4)
C6—C5—C4A	120.8 (4)	C72—C73—C731	121.9 (4)
C5—C6—C7	119.7 (4)	C732—C73—C731	114.5 (4)
C5—C6—H6	120	O8—C81—H811	109
C7—C6—H6	120	O8—C81—H812	109
O7—C7—C8	116.0 (3)	H811—C81—H812	109
O7—C7—C6	123.2 (3)	O8—C81—H813	110
C8—C7—C6	120.7 (3)	H811—C81—H813	110
C8A—C8—O8	120.2 (3)	H812—C81—H813	110
C8A—C8—C7	118.7 (3)	O52—C521—H522	110
O8—C8—C7	121.0 (3)	O52—C521—H523	109
O1—C8A—C8	116.6 (3)	H522—C521—H523	110
O1—C8A—C4A	121.5 (3)	O52—C521—H521	109
C8—C8A—C4A	121.9 (3)	H522—C521—H521	110
C22—C12—C62	117.2 (3)	H523—C521—H521	109
C22—C12—C2	123.7 (3)	C73—C731—H731	110
C62—C12—C2	119.1 (3)	C73—C731—H732	110
C32—C22—C12	121.0 (4)	H731—C731—H732	110
C32—C22—H22	119	C73—C731—H733	109
C12—C22—H22	120	H731—C731—H733	109
O3—C31—H311	109	H732—C731—H733	109
O3—C31—H312	110	C73—C732—H734	110
H311—C31—H312	109	C73—C732—H735	110
O3—C31—H313	110	H734—C732—H735	110
H311—C31—H313	109	C73—C732—H736	110
H312—C31—H313	110	H734—C732—H736	109
C22—C32—C42	120.9 (4)	H735—C732—H736	109
C8A—O1—C2—C3	−3.0 (5)	C2—O1—C8A—C4A	3.0 (5)
C8A—O1—C2—C12	176.5 (3)	O8—C8—C8A—O1	−6.8 (5)
O1—C2—C3—O3	179.1 (3)	C7—C8—C8A—O1	177.3 (3)
C12—C2—C3—O3	−0.4 (6)	O8—C8—C8A—C4A	172.9 (3)
O1—C2—C3—C4	1.4 (5)	C7—C8—C8A—C4A	−3.1 (5)
C12—C2—C3—C4	−178.0 (3)	C5—C4A—C8A—O1	−178.6 (3)
C31—O3—C3—C2	103.4 (4)	C4—C4A—C8A—O1	−1.2 (5)
C31—O3—C3—C4	−78.8 (4)	C5—C4A—C8A—C8	1.8 (5)
C2—C3—C4—O4	179.6 (3)	C4—C4A—C8A—C8	179.2 (3)
O3—C3—C4—O4	1.8 (5)	C3—C2—C12—C22	−1.9 (6)
C2—C3—C4—C4A	0.2 (5)	O1—C2—C12—C22	178.6 (3)
O3—C3—C4—C4A	−177.5 (3)	C3—C2—C12—C62	178.3 (4)
C8A—C4A—C4—O4	−179.7 (3)	O1—C2—C12—C62	−1.2 (4)
C5—C4A—C4—O4	−2.4 (5)	C62—C12—C22—C32	1.7 (6)
C8A—C4A—C4—C3	−0.3 (5)	C2—C12—C22—C32	−178.1 (4)
C5—C4A—C4—C3	176.9 (3)	C12—C22—C32—C42	−0.4 (7)
C8A—C4A—C5—O5	179.7 (3)	C22—C32—C42—O42	179.1 (4)
C4—C4A—C5—O5	2.4 (5)	C22—C32—C42—C52	−1.7 (6)
C8A—C4A—C5—C6	1.1 (5)	C521—O52—C52—C62	−4.2 (6)
C4—C4A—C5—C6	−176.2 (3)	C521—O52—C52—C42	176.7 (4)
O5—C5—C6—C7	178.9 (3)	O42—C42—C52—C62	−178.3 (4)
C4A—C5—C6—C7	−2.5 (6)	C32—C42—C52—C62	2.6 (6)
C71—O7—C7—C8	177.8 (3)	O42—C42—C52—O52	0.8 (6)
C71—O7—C7—C6	−1.1 (5)	C32—C42—C52—O52	−178.3 (4)
C5—C6—C7—O7	179.9 (3)	O52—C52—C62—C12	179.7 (4)
C5—C6—C7—C8	1.1 (6)	C42—C52—C62—C12	−1.2 (6)
C81—O8—C8—C8A	91.3 (4)	C22—C12—C62—C52	−0.9 (6)
C81—O8—C8—C7	−92.8 (4)	C2—C12—C62—C52	179.0 (4)
O7—C7—C8—C8A	−177.2 (3)	C7—O7—C71—C72	−174.6 (3)
C6—C7—C8—C8A	1.7 (5)	O7—C71—C72—C73	143.5 (4)
O7—C7—C8—O8	6.8 (5)	C71—C72—C73—C732	0.0 (7)
C6—C7—C8—O8	−174.3 (3)	C71—C72—C73—C731	179.3 (4)
C2—O1—C8A—C8	−177.4 (3)

(II) 4',5-dihydroxy-3,3',8-trimethoxy-7-(3-methylbut-2-enyloxy)flavone

Crystal data

C23H24O8	Z = 2
Mr = 428.44	F(000) = 452
Triclinic, P1	Dx = 1.405 Mg m^−3
a = 12.291 (5) Å	Mo Kα radiation, λ = 0.71069 Å
b = 13.075 (5) Å	Cell parameters from 17 reflections
c = 7.099 (3) Å	θ = 20.1–25.6°
α = 93.85 (5)°	µ = 0.11 mm^−1
β = 104.33 (4)°	T = 293 K
γ = 111.52 (3)°	Prism, yellow
V = 1012.3 (7) Å^3	0.45 × 0.10 × 0.10 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.097
Radiation source: Rigaku rotating anode	θmax = 25.0°, θmin = 3.0°
Graphite monochromator	h = 0→14
ω–2θ scans	k = −15→14
3754 measured reflections	l = −8→8
3571 independent reflections	3 standard reflections every 150 reflections
1609 reflections with I > 2σ(I)	intensity decay: 3.5%

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.199	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.1P)^2] where P = (Fo^2 + 2Fc^2)/3
3571 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.28 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
O1	0.4223 (2)	0.03091 (19)	0.7148 (4)	0.0405 (7)
O3	0.7498 (2)	0.1101 (2)	0.9082 (4)	0.0460 (7)
O4	0.7320 (2)	0.3132 (2)	0.9353 (4)	0.0531 (8)
O5	0.6002 (2)	0.4297 (2)	0.9128 (5)	0.0577 (8)
O7	0.1660 (2)	0.2245 (2)	0.6717 (4)	0.0467 (7)
O8	0.1964 (2)	0.0345 (2)	0.5843 (4)	0.0483 (7)
O42	0.4692 (3)	−0.4288 (2)	0.6347 (5)	0.0616 (9)
O52	0.6955 (3)	−0.2726 (2)	0.7537 (5)	0.0559 (8)
C2	0.5336 (3)	0.0236 (3)	0.7676 (5)	0.0371 (9)
C3	0.6379 (3)	0.1166 (3)	0.8400 (5)	0.0346 (9)
C4	0.6353 (4)	0.2267 (3)	0.8677 (5)	0.0382 (9)
C4A	0.5172 (3)	0.2307 (3)	0.8167 (5)	0.0361 (9)
C5	0.4999 (4)	0.3315 (3)	0.8430 (6)	0.0410 (10)
C6	0.3852 (4)	0.3316 (3)	0.7983 (6)	0.0424 (10)
C7	0.2830 (3)	0.2322 (3)	0.7211 (5)	0.0384 (9)
C8	0.2965 (3)	0.1307 (3)	0.6872 (5)	0.0369 (9)
C8A	0.4119 (3)	0.1318 (3)	0.7402 (5)	0.0350 (9)
C12	0.5197 (3)	−0.0950 (3)	0.7339 (5)	0.0353 (9)
C22	0.4030 (3)	−0.1796 (3)	0.6737 (6)	0.0424 (10)
C31	0.8331 (4)	0.1554 (4)	0.7951 (7)	0.0624 (13)
C32	0.3868 (4)	−0.2908 (3)	0.6400 (6)	0.0499 (11)
C42	0.4867 (4)	−0.3177 (3)	0.6693 (6)	0.0424 (10)
C52	0.6040 (4)	−0.2347 (3)	0.7301 (6)	0.0420 (10)
C62	0.6202 (3)	−0.1242 (3)	0.7626 (5)	0.0396 (9)
C71	0.1444 (4)	0.3265 (3)	0.6974 (6)	0.0497 (11)
C72	0.1579 (4)	0.3862 (3)	0.5292 (7)	0.0504 (11)
C73	0.0691 (4)	0.3937 (3)	0.3880 (6)	0.0501 (11)
C81	0.1175 (4)	−0.0233 (4)	0.6933 (7)	0.0676 (13)
C521	0.8180 (4)	−0.1927 (4)	0.8194 (6)	0.0570 (12)
C731	−0.0636 (5)	0.3422 (4)	0.3712 (8)	0.0762 (15)
C732	0.0984 (5)	0.4556 (4)	0.2252 (9)	0.0855 (17)
H5	0.6798	0.4180	0.9669	0.074*
H6	0.3753	0.3997	0.8201	0.051*
H22	0.3345	−0.1597	0.6543	0.074*
H32	0.3066	−0.3482	0.5970	0.060*
H42	0.5612	−0.4226	0.6715	0.074*
H62	0.7001	−0.0660	0.8039	0.074*
H72	0.2389	0.4232	0.5219	0.060*
H311	0.8065	0.1069	0.6721	0.075*
H312	0.8352	0.2268	0.7721	0.075*
H313	0.9127	0.1625	0.8660	0.075*
H521	0.8320	−0.1507	0.9438	0.069*
H522	0.8319	−0.1441	0.7264	0.069*
H523	0.8722	−0.2300	0.8322	0.069*
H711	0.0638	0.3076	0.7069	0.060*
H712	0.2018	0.3740	0.8155	0.060*
H731	−0.0774	0.3711	0.4854	0.092*
H732	−0.1089	0.3589	0.2574	0.092*
H733	−0.0894	0.2634	0.3605	0.092*
H734	0.1521	0.5311	0.2795	0.102*
H735	0.1365	0.4217	0.1551	0.102*
H736	0.0250	0.4535	0.1374	0.102*
H811	0.0568	−0.0910	0.6129	0.081*
H812	0.0791	0.0220	0.7334	0.081*
H813	0.1637	−0.0397	0.8068	0.081*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0455 (16)	0.0295 (14)	0.0486 (17)	0.0178 (12)	0.0134 (13)	0.0045 (11)
O3	0.0405 (17)	0.0400 (15)	0.0576 (18)	0.0171 (13)	0.0129 (14)	0.0083 (13)
O4	0.0471 (18)	0.0360 (16)	0.070 (2)	0.0123 (14)	0.0148 (15)	0.0026 (14)
O5	0.0502 (18)	0.0312 (15)	0.085 (2)	0.0139 (14)	0.0147 (16)	0.0004 (14)
O7	0.0493 (18)	0.0366 (15)	0.0578 (18)	0.0232 (13)	0.0123 (14)	0.0078 (13)
O8	0.0484 (17)	0.0378 (15)	0.0549 (19)	0.0151 (14)	0.0135 (14)	0.0008 (13)
O42	0.0596 (19)	0.0307 (15)	0.100 (2)	0.0220 (14)	0.0271 (17)	0.0084 (15)
O52	0.0527 (19)	0.0421 (16)	0.085 (2)	0.0285 (15)	0.0265 (16)	0.0091 (15)
C2	0.045 (2)	0.037 (2)	0.035 (2)	0.022 (2)	0.0130 (18)	0.0085 (17)
C3	0.037 (2)	0.035 (2)	0.032 (2)	0.0155 (19)	0.0095 (17)	0.0051 (17)
C4	0.050 (2)	0.033 (2)	0.033 (2)	0.016 (2)	0.0149 (18)	0.0083 (17)
C4A	0.041 (2)	0.031 (2)	0.040 (2)	0.0145 (18)	0.0165 (18)	0.0092 (17)
C5	0.046 (3)	0.032 (2)	0.041 (2)	0.0120 (19)	0.0116 (19)	0.0056 (17)
C6	0.054 (3)	0.029 (2)	0.046 (2)	0.021 (2)	0.015 (2)	0.0046 (18)
C7	0.043 (2)	0.038 (2)	0.038 (2)	0.0206 (19)	0.0100 (18)	0.0097 (17)
C8	0.046 (2)	0.027 (2)	0.036 (2)	0.0131 (18)	0.0114 (18)	0.0042 (16)
C8A	0.049 (2)	0.029 (2)	0.034 (2)	0.0203 (19)	0.0164 (18)	0.0061 (16)
C12	0.044 (2)	0.033 (2)	0.034 (2)	0.0171 (18)	0.0170 (18)	0.0115 (16)
C22	0.044 (2)	0.038 (2)	0.049 (3)	0.021 (2)	0.0109 (19)	0.0088 (18)
C31	0.051 (3)	0.059 (3)	0.084 (4)	0.022 (2)	0.032 (3)	0.010 (3)
C32	0.047 (3)	0.036 (2)	0.066 (3)	0.015 (2)	0.017 (2)	0.009 (2)
C42	0.053 (3)	0.029 (2)	0.051 (3)	0.020 (2)	0.017 (2)	0.0087 (18)
C52	0.048 (2)	0.042 (2)	0.047 (2)	0.025 (2)	0.020 (2)	0.0127 (19)
C62	0.040 (2)	0.038 (2)	0.043 (2)	0.0159 (18)	0.0160 (18)	0.0092 (18)
C71	0.056 (3)	0.045 (2)	0.064 (3)	0.034 (2)	0.023 (2)	0.011 (2)
C72	0.048 (3)	0.042 (2)	0.068 (3)	0.021 (2)	0.023 (2)	0.012 (2)
C73	0.056 (3)	0.038 (2)	0.058 (3)	0.024 (2)	0.012 (2)	0.005 (2)
C81	0.066 (3)	0.049 (3)	0.074 (3)	0.009 (2)	0.019 (3)	0.011 (2)
C521	0.058 (3)	0.066 (3)	0.060 (3)	0.038 (3)	0.020 (2)	0.007 (2)
C731	0.067 (3)	0.079 (4)	0.076 (4)	0.036 (3)	0.001 (3)	0.007 (3)
C732	0.114 (5)	0.068 (4)	0.085 (4)	0.044 (3)	0.032 (3)	0.030 (3)

Geometric parameters (Å, º)

O1—C2	1.367 (4)	C22—H22	0.95
O1—C8A	1.376 (4)	C31—H311	0.95
O3—C3	1.377 (4)	C31—H312	0.95
O3—C31	1.439 (5)	C31—H313	0.95
O4—C4	1.257 (4)	C32—C42	1.369 (5)
O5—C5	1.366 (4)	C32—H32	0.95
O5—H5	1.03	C42—C52	1.388 (5)
O7—C7	1.358 (4)	C52—C62	1.378 (5)
O7—C71	1.460 (4)	C62—H62	0.95
O8—C8	1.388 (4)	C71—C72	1.480 (6)
O8—C81	1.422 (5)	C71—H711	0.95
O42—C42	1.383 (4)	C71—H712	0.95
O42—H42	1.07	C72—C73	1.325 (5)
O52—C52	1.366 (5)	C72—H72	0.95
O52—C521	1.417 (5)	C73—C731	1.489 (7)
C2—C3	1.354 (5)	C73—C732	1.496 (6)
C2—C12	1.492 (5)	C81—H811	0.95
C3—C4	1.452 (5)	C81—H812	0.95
C4—C4A	1.429 (5)	C81—H813	0.95
C4A—C8A	1.404 (5)	C521—H521	0.95
C4A—C5	1.418 (5)	C521—H522	0.95
C5—C6	1.367 (5)	C521—H523	0.95
C6—C7	1.390 (5)	C731—H731	0.95
C6—H6	0.95	C731—H732	0.95
C7—C8	1.408 (5)	C731—H733	0.95
C8—C8A	1.369 (5)	C732—H734	0.95
C12—C22	1.390 (5)	C732—H735	0.95
C12—C62	1.396 (5)	C732—H736	0.95
C22—C32	1.389 (5)
C2—O1—C8A	121.5 (3)	C42—C32—H32	120
C3—O3—C31	114.7 (3)	C22—C32—H32	120
C5—O5—H5	113	C32—C42—O42	119.2 (4)
C7—O7—C71	118.7 (3)	C32—C42—C52	120.5 (3)
C8—O8—C81	116.5 (3)	O42—C42—C52	120.3 (3)
C42—O42—H42	102	O52—C52—C62	125.6 (4)
C52—O52—C521	118.0 (3)	O52—C52—C42	114.7 (3)
C3—C2—O1	120.7 (3)	C62—C52—C42	119.8 (4)
C3—C2—C12	128.3 (3)	C52—C62—C12	120.7 (4)
O1—C2—C12	111.0 (3)	C52—C62—H62	121
C2—C3—O3	121.3 (3)	C12—C62—H62	118
C2—C3—C4	121.4 (3)	O7—C71—C72	111.3 (3)
O3—C3—C4	117.0 (3)	O7—C71—H711	109
O4—C4—C4A	122.1 (3)	C72—C71—H711	109
O4—C4—C3	121.6 (4)	O7—C71—H712	109
C4A—C4—C3	116.3 (3)	C72—C71—H712	109
C8A—C4A—C5	117.2 (3)	H711—C71—H712	109
C8A—C4A—C4	120.0 (3)	C73—C72—C71	127.0 (4)
C5—C4A—C4	122.8 (3)	C73—C72—H72	117
O5—C5—C6	120.0 (3)	C71—C72—H72	117
O5—C5—C4A	118.9 (3)	C72—C73—C731	125.3 (4)
C6—C5—C4A	121.1 (3)	C72—C73—C732	120.2 (4)
C5—C6—C7	120.1 (3)	C731—C73—C732	114.5 (4)
C5—C6—H6	120	O8—C81—H811	110
C7—C6—H6	120	O8—C81—H812	110
O7—C7—C6	124.1 (3)	H811—C81—H812	109
O7—C7—C8	115.4 (3)	O8—C81—H813	110
C6—C7—C8	120.5 (4)	H811—C81—H813	109
C8A—C8—O8	120.8 (3)	H812—C81—H813	109
C8A—C8—C7	118.4 (3)	O52—C521—H521	109
O8—C8—C7	120.4 (3)	O52—C521—H522	110
C8—C8A—O1	117.4 (3)	H521—C521—H522	110
C8—C8A—C4A	122.5 (3)	O52—C521—H523	109
O1—C8A—C4A	120.1 (3)	H521—C521—H523	110
C22—C12—C62	118.6 (3)	H522—C521—H523	110
C22—C12—C2	119.3 (3)	C73—C731—H731	110
C62—C12—C2	122.1 (3)	C73—C731—H732	110
C32—C22—C12	120.7 (4)	H731—C731—H732	109
C32—C22—H22	121	C73—C731—H733	110
C12—C22—H22	119	H731—C731—H733	109
O3—C31—H311	110	H732—C731—H733	109
O3—C31—H312	110	C73—C732—H734	110
H311—C31—H312	109	C73—C732—H735	110
O3—C31—H313	110	H734—C732—H735	110
H311—C31—H313	109	C73—C732—H736	109
H312—C31—H313	110	H734—C732—H736	109
C42—C32—C22	119.8 (4)	H735—C732—H736	110