2',4'-Di­hydroxy-3-methoxy-[alpha],[beta]-di­hydro­chalcone and 2',4-di­hydroxy-[alpha],[beta]-di­hydro­chalcone: supramolecular structures formed by O-H...O, C-H...O and stacking interactions

The crystal structures of 2',4'-di­hydroxy-3-methoxy-[alpha],[beta]-di­hydro­chalcone, C₁₆H₁₆O₄, and 2',4-di­hydroxy-[alpha],[beta]-di­hydro­chalcone, C₁₅H₁₄O₃, have been determined. In both compounds, the structure consists of two nearly planar six-membered aromatic rings connected by a propanal chain, which is bent in the methoxy compound and almost straight in the other compound. In the crystal structures, the molecular units of both compounds are linked by O-H...O hydrogen bonds to form infinite one-dimensional chains. Hydro­gen bonds and C-H...O contacts in the crystal structures were studied by topological analysis of charge density based on Hartree-Fock calculations. Almost all of the investigated C-H...O contacts should be characterized as weak hydrogen bonds.

S1. Comment

Chalcones are the biogenetic precursors of the flavonoids in higher plants. Dihydrochalcones, together with chalcones, are often isolated from various plants (Achenbach et al., 1988; Masaoud et al., 1995; Thuy et al., 1998; Sinz et al., 1999). These compounds display a wide variety of pharmacological effects, including antibacterial, antiviral, antimutagenic, antimitotic, anti-inflammatory, antiulcerative and hepatoprotective (Batt et al., 1993; Sogawa et al., 1994; Arty et al. 2000). Since some chalcones inhibit various enzymes involved in the generation of reactive oxygen species (5-lipoxygenase, 12-lipoxygenase, cyclooxygenase etc.), the majority of their pharmacological properties are supposed to be related to their antioxidative effect (Sogawa et al., 1993; Forejtníková et al., 2005). The biological effects are often connected with electron distribution around the molecule and capability of entering into the intermolecular interactions under formation of supramolecular complexes with biomacromolecules. The crystal structures described here were studied as model systems in the course of theoretical characterization of intermolecular O—H···O and C—H···O interactions.

The structures of 2',4'-dihydroxy-3-methoxydihydrochalcone, (I) (Fig. 1 and Table 1), and 2',4-dihydroxydihydrochalcone, (II) (Fig. 2 and Table 3), are similar to that of 2',4'-dihydroxy-4,6'-dimethoxy-α,β-dihydrochalcone (De Matheus et al., 1991). They consist of two nearly planar six-membered aromaric rings (A and B), with maximum deviations from the A(I), B(I), A(II) and B(II) planes of 0.0056 (15), 0.0085 (15), 0.0089 (13) and 0.0095 (13) Å, respectively. The interplanar angle between rings A and B in (I) is 43.66 (5)°, the interplanar A/B angle in (II) is 67.40 (4). The atoms connected to rings A and B are slightly displaced out of the corresponding planes (the deviations from the planes are summarized in Table 5). Rings A and B are connected by a propanal chain, which is bent in (I) [the C1'–C9–C8–C7 and C9–C8–C7–C1 torsion angles are 100.23 (18) and −168.33 (14)°; see Table 1] and almost straight in (II) [the C1'–C9–C8–C7 and C9–C8–C7–C1 torsion angles are 171.12 (11) and −172.51 (11)°; see Table 3].

In the crystal structures of (I) and (II), the molecules are involved in extensive networks of O—H···O and C—H···O hydrogen bonds [Fig. 2 and Table 2 for (I), and Fig. 4 and Table 4 for (II)]. The two shortest intra- and intermolecular O—H···O bonds in (I) [O13···O10 = 2.5499 (16) Å and O14···O10ⁱ = 2.7005 (16) Å; symmetry code: (i) 1 + x, 3/2 − y, 1/2 + z] connect molecules into linear chains in the (201) direction; the two shortest bonds in (II) [O13···O10 = 2.5482 (13) Å and O11···O13^v = 2.8147 (13) Å; symmetry code: (v) x − 1, y, z − 1] form linear chains in the (101) direction.

In order to characterize individual hydrogen bonds, a topological analysis in the framework of the Bader (2003) `atoms in molecules' (AIM) theory was applied. According to this theory, the bond is characterized by the charge density and the Laplacian of charge density in its bond critical point (BCP). The BCP is extremum at the electron density surface with one positive and two negative eigenvalues of the matrix of second derivatives of ρ(r_c). BCPs belonging to the particular intermolecular contact were found and charge density and the Laplacian of the charge density at BCP were calculated as descibed in the Experimental section (Tables 2 and 4). The largest values of NABLA²ρ(r_c) were obtained for intramolecular O—H···H hydrogen bonds forming the stable six-membered ring C. Intermolecular O—H···O hydrogen bonds are somewhat weakened. However, all C—H···O contacts summarized in Tables 2 and 4 should be classified as weak hydrogen bonds (Desiraju & Steiner, 1999) because the calculated values of ρ(r_c) and NABLA²ρ(r_c) fall within the ranges specified in the literature [0.013–0.236 e Å⁻³ for ρ(r_c) and 0.58–3.35 e Å⁻⁵ for NABLA²ρ(r_c); Koch & Popelier, 1995]. The only exception from the determined set is represented by the C7—H7A···O13 shortened contact, which should be characterized rather by the van der Waals concept. It is evident from this study that C—H motives from aromatic fragments are capable of forming stronger attractive hydrogen bonds than their standard aliphatic counterparts.

In the crystal structure of (I), the molecular packing is such that stacking interactions between rings B of adjacent molecules are optimized (Fig. 2). If CgB is the centroid of ring B and CgB^x is that of ring B^x [symmetry code: (x) −x, 1 − y, 1 − z], the CgB···CgB^x distance is 3.577 Å and the distance of CgB from the plane through the Bx ring atoms is 3.357 Å.

S2. Experimental

Dihydrochalcones (I) and (II) were prepared by hydrogenation of the appropriate chalcones over 10% palladium on activated carbon as a catalyst (Davis & Chen, 1993). The catalyst was added to a solution of 2',4-dihydroxychalcone (2 g) in ethylacetate (5 ml); the mixture was hydrogenated at normal pressure and room temperature for 30 min, after which the catalyst was removed by filtration and the solution was evaporated to dryness, with 98% yield of the crude product (I). A similar procedure was used for the preparation of (II) from 2',4'-dihydroxy-3-O-methylchalcone, where hydrogenation took 60 min and we obtained crude (II) in 89% yield. Colorless crystals of (I) and (II) were prepared by recrystallization from methanol at room temperature under normal pressure.

S3. Refinement

H atoms attached to C atoms were positioned geometrically, with C—H = 0.95–0.99 Å, and with U_iso(H) values equal to 1.2U_eq(C) [1.5U_eq(C) for methyl atoms]. The parameters of H atoms attached to O atoms were refined with the O···H distances restrained to 0.95 (1) Å. The electron density and Laplacian of electron density in BCP were calculated for X-ray geometry with optimized positions of the H atoms. Geometry optimizations by AM1 method and calculations of wavefunctions at basis RHF/6–31G** were performed using the GAUSSIAN98 package (Frisch et al., 1998). Topological analyses based on the theory of Bader et al. (1982a,b) were carried out using the EXTREME program in the AIMPAC program package (Biegler-König et al., 1982).

Computing details

For both compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2004); cell refinement: CrysAlis RED (Oxford Diffraction, 2004); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Johnson & Burnett, 1996); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).

Figures

	Fig. 1. : A view of (I). Displacement parameters for non-H atoms are drawn at the 50% probability level.
	Fig. 2. : Part of the crystal structure of (I), showing the formation of linear chains of hydrogen-bonded molecules of dihydrochalcone (I) and stacking interaction between coplanar B rings of adjacent molecular units of (I). [Symmetry codes: (i) 1 + x, 3/2 − y, 1/2 + z; (ix) x − 1, 3/2 − y, z − 1/2; (x) −x, 1 − y, 1 − z.]
	Fig. 3. : A view of (II). Displacement parameters for non-H atoms are drawn at the 50% probability level.
	Fig. 4. : Part of the crystal structure of (II), showing the formation of linear chains of hydrogen-bonded molecules of dihydrochalcone (II). [Symmetry codes: (v) x − 1, y, z − 1; (viii) x + 1, y, z + 1.]

(I) 2',4'-Dihydroxy-3-methoxy-α,β-dihydrochalcone

Crystal data

C16H16O4	F(000) = 576
Mr = 272.29	Dx = 1.376 Mg m^−3
Monoclinic, P21/c	Melting point: 345(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.3074 (9) Å	Cell parameters from 3635 reflections
b = 22.968 (3) Å	θ = 2.7–27.9°
c = 7.8343 (9) Å	µ = 0.10 mm^−1
β = 91.972 (10)°	T = 120 K
V = 1314.1 (3) Å^3	Prism, colorless
Z = 4	0.50 × 0.30 × 0.20 mm

Data collection

Kuma KM-4-Plus CCD diffractometer	1831 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Enhance (Oxford Diffraction) monochromator	θmax = 25.0°, θmin = 3.2°
Detector resolution: 16.3 pixels mm^-1	h = −8→8
ω scans	k = −27→25
8679 measured reflections	l = −9→9
2312 independent reflections

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0425P)^2 + 0.1P] where P = (Fo^2 + 2Fc^2)/3
2312 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.14 e Å^−3
2 restraints	Δρmin = −0.19 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
C1	0.1660 (2)	0.54966 (7)	0.3504 (2)	0.0203 (4)
C2	0.2396 (2)	0.52637 (7)	0.5017 (2)	0.0203 (4)
H2	0.2745	0.5514	0.5938	0.024*
C3	0.2619 (2)	0.46678 (7)	0.5179 (2)	0.0207 (4)
C4	0.2164 (2)	0.43058 (7)	0.3830 (2)	0.0242 (4)
H4	0.2341	0.3897	0.3936	0.029*
C5	0.1449 (2)	0.45374 (7)	0.2322 (2)	0.0242 (4)
H5	0.1128	0.4287	0.1394	0.029*
C6	0.1201 (2)	0.51301 (7)	0.2158 (2)	0.0223 (4)
H6	0.0713	0.5287	0.1116	0.027*
C7	0.1401 (2)	0.61439 (7)	0.3362 (2)	0.0231 (4)
H7A	0.1740	0.6327	0.4471	0.028*
H7B	0.0093	0.6229	0.3102	0.028*
C8	0.2561 (2)	0.64090 (7)	0.1967 (2)	0.0219 (4)
H8A	0.3831	0.6261	0.2086	0.026*
H8B	0.2055	0.6292	0.0829	0.026*
C9	0.2564 (2)	0.70598 (7)	0.2108 (2)	0.0205 (4)
O10	0.11676 (15)	0.73279 (5)	0.15537 (15)	0.0270 (3)
O11	0.32662 (16)	0.44010 (5)	0.66464 (14)	0.0278 (3)
C12	0.3764 (2)	0.47654 (8)	0.8054 (2)	0.0304 (5)
H12A	0.2710	0.5004	0.8354	0.046*
H12B	0.4778	0.5019	0.7744	0.046*
H12C	0.4145	0.4524	0.9034	0.046*
O13	0.25727 (16)	0.82960 (5)	0.25059 (15)	0.0250 (3)
O14	0.84219 (16)	0.83051 (5)	0.50919 (15)	0.0277 (3)
C1'	0.4084 (2)	0.73696 (7)	0.2910 (2)	0.0189 (4)
C2'	0.4043 (2)	0.79840 (7)	0.30483 (19)	0.0192 (4)
C3'	0.5509 (2)	0.82838 (7)	0.37653 (19)	0.0198 (4)
H3'	0.5469	0.8697	0.3829	0.024*
C4'	0.7038 (2)	0.79889 (7)	0.4393 (2)	0.0208 (4)
C5'	0.7118 (2)	0.73834 (7)	0.4289 (2)	0.0228 (4)
H5'	0.8166	0.7180	0.4720	0.027*
C6'	0.5671 (2)	0.70863 (7)	0.3558 (2)	0.0222 (4)
H6'	0.5738	0.6674	0.3485	0.027*
H13	0.172 (2)	0.8023 (7)	0.206 (3)	0.054 (7)*
H14	0.935 (2)	0.8065 (8)	0.561 (3)	0.060 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0184 (9)	0.0205 (9)	0.0223 (9)	−0.0005 (7)	0.0032 (7)	0.0006 (7)
C2	0.0201 (9)	0.0201 (9)	0.0209 (9)	−0.0014 (7)	0.0012 (7)	−0.0022 (7)
C3	0.0167 (9)	0.0221 (9)	0.0234 (9)	0.0017 (7)	0.0028 (7)	0.0046 (7)
C4	0.0265 (10)	0.0166 (9)	0.0300 (10)	0.0009 (7)	0.0059 (8)	0.0005 (8)
C5	0.0259 (10)	0.0232 (9)	0.0236 (9)	−0.0019 (7)	0.0019 (7)	−0.0063 (8)
C6	0.0227 (10)	0.0239 (9)	0.0203 (9)	0.0000 (7)	−0.0003 (7)	0.0007 (7)
C7	0.0281 (10)	0.0199 (9)	0.0214 (9)	0.0016 (7)	0.0005 (7)	−0.0011 (7)
C8	0.0211 (9)	0.0188 (9)	0.0256 (9)	−0.0026 (7)	−0.0014 (7)	−0.0018 (7)
C9	0.0220 (9)	0.0206 (9)	0.0188 (9)	−0.0001 (7)	0.0011 (7)	0.0023 (7)
O10	0.0238 (7)	0.0212 (6)	0.0354 (7)	−0.0011 (5)	−0.0084 (5)	0.0014 (5)
O11	0.0338 (7)	0.0251 (7)	0.0243 (7)	0.0056 (5)	−0.0018 (5)	0.0045 (5)
C12	0.0329 (11)	0.0379 (11)	0.0202 (9)	0.0090 (8)	−0.0022 (8)	0.0024 (8)
O13	0.0230 (7)	0.0187 (6)	0.0328 (7)	0.0023 (5)	−0.0080 (5)	0.0019 (5)
O14	0.0250 (7)	0.0200 (6)	0.0371 (7)	−0.0032 (5)	−0.0122 (6)	0.0024 (6)
C1'	0.0206 (9)	0.0168 (8)	0.0191 (8)	−0.0013 (7)	0.0004 (7)	0.0009 (7)
C2'	0.0210 (9)	0.0198 (9)	0.0167 (8)	0.0025 (7)	0.0002 (7)	0.0038 (7)
C3'	0.0253 (9)	0.0149 (8)	0.0191 (8)	−0.0004 (7)	0.0010 (7)	0.0009 (7)
C4'	0.0233 (9)	0.0210 (9)	0.0181 (8)	−0.0020 (7)	−0.0011 (7)	0.0019 (7)
C5'	0.0209 (9)	0.0217 (9)	0.0255 (9)	0.0035 (7)	−0.0041 (7)	0.0027 (7)
C6'	0.0261 (10)	0.0159 (8)	0.0244 (9)	0.0005 (7)	−0.0008 (7)	0.0004 (7)

Geometric parameters (Å, º)

C1—C6	1.382 (2)	C9—C1'	1.444 (2)
C1—C2	1.391 (2)	O11—C12	1.4216 (19)
C1—C7	1.502 (2)	C12—H12A	0.9800
C2—C3	1.384 (2)	C12—H12B	0.9800
C2—H2	0.9500	C12—H12C	0.9800
C3—O11	1.3724 (18)	O13—C2'	1.3481 (19)
C3—C4	1.376 (2)	O13—H13	0.942 (10)
C4—C5	1.382 (2)	O14—C4'	1.3462 (18)
C4—H4	0.9500	O14—H14	0.953 (10)
C5—C6	1.379 (2)	C1'—C6'	1.409 (2)
C5—H5	0.9500	C1'—C2'	1.416 (2)
C6—H6	0.9500	C2'—C3'	1.377 (2)
C7—C8	1.532 (2)	C3'—C4'	1.382 (2)
C7—H7A	0.9900	C3'—H3'	0.9500
C7—H7B	0.9900	C4'—C5'	1.395 (2)
C8—C9	1.499 (2)	C5'—C6'	1.367 (2)
C8—H8A	0.9900	C5'—H5'	0.9500
C8—H8B	0.9900	C6'—H6'	0.9500
C9—O10	1.2566 (19)
C6—C1—C2	119.52 (15)	O10—C9—C1'	120.82 (15)
C6—C1—C7	121.28 (14)	O10—C9—C8	117.63 (15)
C2—C1—C7	119.20 (14)	C1'—C9—C8	121.51 (14)
C3—C2—C1	119.95 (15)	C3—O11—C12	117.30 (13)
C3—C2—H2	120.0	O11—C12—H12A	109.5
C1—C2—H2	120.0	O11—C12—H12B	109.5
O11—C3—C4	116.15 (14)	H12A—C12—H12B	109.5
O11—C3—C2	123.67 (15)	O11—C12—H12C	109.5
C4—C3—C2	120.17 (15)	H12A—C12—H12C	109.5
C3—C4—C5	119.87 (15)	H12B—C12—H12C	109.5
C3—C4—H4	120.1	C2'—O13—H13	105.7 (13)
C5—C4—H4	120.1	C4'—O14—H14	112.0 (13)
C6—C5—C4	120.31 (16)	C6'—C1'—C2'	116.87 (14)
C6—C5—H5	119.8	C6'—C1'—C9	122.70 (14)
C4—C5—H5	119.8	C2'—C1'—C9	120.42 (15)
C5—C6—C1	120.16 (15)	O13—C2'—C3'	117.59 (14)
C5—C6—H6	119.9	O13—C2'—C1'	121.63 (14)
C1—C6—H6	119.9	C3'—C2'—C1'	120.78 (15)
C1—C7—C8	112.01 (14)	C2'—C3'—C4'	120.53 (15)
C1—C7—H7A	109.2	C2'—C3'—H3'	119.7
C8—C7—H7A	109.2	C4'—C3'—H3'	119.7
C1—C7—H7B	109.2	O14—C4'—C3'	117.84 (14)
C8—C7—H7B	109.2	O14—C4'—C5'	121.97 (15)
H7A—C7—H7B	107.9	C3'—C4'—C5'	120.19 (15)
C9—C8—C7	110.07 (14)	C6'—C5'—C4'	119.27 (15)
C9—C8—H8A	109.6	C6'—C5'—H5'	120.4
C7—C8—H8A	109.6	C4'—C5'—H5'	120.4
C9—C8—H8B	109.6	C5'—C6'—C1'	122.37 (15)
C7—C8—H8B	109.6	C5'—C6'—H6'	118.8
H8A—C8—H8B	108.2	C1'—C6'—H6'	118.8
C6'—C1'—C9—C8	2.0 (2)	C9—C8—C7—C1	−168.34 (14)
C1'—C9—C8—C7	100.22 (18)	C8—C7—C1—C2	117.24 (16)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O10	0.94 (1)	1.69 (1)	2.5499 (16)	150 (2)
O14—H14···O10^i	0.95 (1)	1.75 (1)	2.7005 (16)	176 (2)
C5—H5···O14^ii	0.95	2.56	3.407 (2)	148
C7—H7A···O13^iii	0.99	2.58	3.569 (2)	174
C6′—H6′···O11^iv	0.95	2.58	3.508 (2)	167

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

(II) 2',4-dihydroxy-α,β-dihydrochalcone

Crystal data

C15H14O3	F(000) = 512
Mr = 242.26	Dx = 1.334 Mg m^−3
Monoclinic, P21/c	Melting point: 379(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.2802 (17) Å	Cell parameters from 2425 reflections
b = 9.4904 (10) Å	θ = 3.0–27.2°
c = 11.5764 (15) Å	µ = 0.09 mm^−1
β = 116.637 (16)°	T = 120 K
V = 1206.0 (3) Å^3	Prism, colorless
Z = 4	0.50 × 0.30 × 0.20 mm

Data collection

Kuma KM-4-Plus CCD diffractometer	1741 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.026
Enhance (Oxford Diffraction) monochromator	θmax = 25.0°, θmin = 4.3°
Detector resolution: 16.3 pixels mm^-1	h = −12→14
ω scans	k = −11→10
6218 measured reflections	l = −13→10
2114 independent reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.1P] where P = (Fo^2 + 2Fc^2)/3
2114 reflections	(Δ/σ)max = 0.005
171 parameters	Δρmax = 0.15 e Å^−3
2 restraints	Δρmin = −0.19 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
O10	0.78172 (8)	0.43899 (10)	0.60548 (8)	0.0275 (2)
O11	0.22486 (8)	0.35771 (10)	−0.15126 (8)	0.0288 (2)
O13	0.99964 (8)	0.49546 (9)	0.76922 (8)	0.0247 (2)
C1'	0.90248 (10)	0.59536 (13)	0.55426 (11)	0.0197 (3)
C2'	1.00198 (11)	0.58447 (13)	0.67790 (11)	0.0203 (3)
C3'	1.10635 (11)	0.66363 (13)	0.71034 (12)	0.0230 (3)
H3'	1.1721	0.6572	0.7947	0.028*
C4'	1.11456 (11)	0.75170 (14)	0.62005 (12)	0.0242 (3)
H4'	1.1866	0.8053	0.6423	0.029*
C5'	1.01886 (11)	0.76301 (14)	0.49699 (12)	0.0248 (3)
H5'	1.0253	0.8237	0.4351	0.030*
C6'	0.91404 (11)	0.68553 (13)	0.46499 (11)	0.0225 (3)
H6'	0.8485	0.6937	0.3806	0.027*
C1	0.49098 (11)	0.40206 (14)	0.22942 (12)	0.0243 (3)
C2	0.37348 (11)	0.45009 (14)	0.19292 (12)	0.0260 (3)
H2	0.3541	0.4918	0.2560	0.031*
C3	0.28365 (11)	0.43861 (14)	0.06658 (12)	0.0248 (3)
H3	0.2038	0.4726	0.0436	0.030*
C4	0.31081 (11)	0.37743 (13)	−0.02581 (11)	0.0224 (3)
C5	0.42794 (11)	0.33129 (14)	0.00762 (12)	0.0260 (3)
H5	0.4475	0.2914	−0.0561	0.031*
C6	0.51657 (11)	0.34336 (14)	0.13405 (12)	0.0264 (3)
H6	0.5967	0.3109	0.1564	0.032*
C7	0.58792 (11)	0.41114 (15)	0.36806 (12)	0.0279 (3)
H7A	0.6262	0.3174	0.3955	0.033*
H7B	0.5489	0.4361	0.4238	0.033*
C8	0.68672 (10)	0.51917 (14)	0.38822 (11)	0.0223 (3)
H8A	0.7185	0.5019	0.3246	0.027*
H8B	0.6505	0.6147	0.3722	0.027*
C9	0.79060 (11)	0.51355 (13)	0.52236 (11)	0.0207 (3)
H11	0.1489 (10)	0.3910 (18)	−0.1633 (15)	0.055 (5)*
H13	0.9210 (10)	0.4544 (18)	0.7301 (15)	0.066 (6)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O10	0.0232 (5)	0.0349 (6)	0.0226 (5)	−0.0039 (4)	0.0086 (4)	0.0040 (4)
O11	0.0231 (5)	0.0369 (6)	0.0203 (5)	0.0009 (4)	0.0042 (4)	0.0005 (4)
O13	0.0219 (5)	0.0310 (5)	0.0183 (5)	−0.0030 (4)	0.0063 (4)	0.0032 (4)
C1'	0.0189 (6)	0.0214 (7)	0.0194 (6)	0.0020 (5)	0.0091 (5)	−0.0025 (5)
C2'	0.0222 (7)	0.0205 (7)	0.0193 (6)	0.0023 (5)	0.0104 (5)	−0.0011 (5)
C3'	0.0202 (6)	0.0253 (7)	0.0203 (6)	0.0004 (5)	0.0062 (5)	−0.0034 (5)
C4'	0.0218 (7)	0.0229 (7)	0.0295 (7)	−0.0027 (5)	0.0129 (6)	−0.0042 (6)
C5'	0.0283 (7)	0.0238 (7)	0.0245 (7)	−0.0005 (5)	0.0139 (6)	0.0013 (5)
C6'	0.0228 (7)	0.0245 (7)	0.0186 (6)	0.0027 (5)	0.0080 (5)	−0.0010 (5)
C1	0.0195 (7)	0.0268 (7)	0.0240 (7)	−0.0044 (5)	0.0074 (5)	0.0013 (6)
C2	0.0242 (7)	0.0281 (8)	0.0254 (7)	−0.0022 (5)	0.0109 (6)	−0.0037 (6)
C3	0.0182 (6)	0.0247 (7)	0.0286 (7)	0.0019 (5)	0.0080 (5)	0.0008 (6)
C4	0.0214 (7)	0.0218 (7)	0.0194 (6)	−0.0028 (5)	0.0050 (5)	0.0026 (5)
C5	0.0249 (7)	0.0296 (8)	0.0257 (7)	0.0006 (5)	0.0132 (6)	0.0008 (6)
C6	0.0163 (6)	0.0326 (8)	0.0286 (7)	0.0002 (5)	0.0085 (5)	0.0024 (6)
C7	0.0222 (7)	0.0356 (8)	0.0233 (7)	−0.0036 (6)	0.0080 (6)	0.0017 (6)
C8	0.0186 (7)	0.0255 (7)	0.0209 (6)	0.0008 (5)	0.0072 (5)	0.0001 (5)
C9	0.0199 (7)	0.0224 (7)	0.0200 (6)	0.0028 (5)	0.0091 (5)	−0.0013 (5)

Geometric parameters (Å, º)

O10—C9	1.2380 (14)	C1—C6	1.3925 (17)
O11—C4	1.3725 (15)	C1—C7	1.5124 (18)
O11—H11	0.935 (9)	C2—C3	1.3860 (18)
O13—C2'	1.3635 (14)	C2—H2	0.9500
O13—H13	0.947 (9)	C3—C4	1.3829 (17)
C1'—C6'	1.3972 (17)	C3—H3	0.9500
C1'—C2'	1.4087 (17)	C4—C5	1.3825 (18)
C1'—C9	1.4737 (17)	C5—C6	1.3825 (18)
C2'—C3'	1.3843 (17)	C5—H5	0.9500
C3'—C4'	1.3769 (18)	C6—H6	0.9500
C3'—H3'	0.9500	C7—C8	1.5243 (17)
C4'—C5'	1.3859 (18)	C7—H7A	0.9900
C4'—H4'	0.9500	C7—H7B	0.9900
C5'—C6'	1.3810 (18)	C8—C9	1.5051 (17)
C5'—H5'	0.9500	C8—H8A	0.9900
C6'—H6'	0.9500	C8—H8B	0.9900
C1—C2	1.3862 (18)
C4—O11—H11	110.8 (10)	C4—C3—H3	120.2
C2'—O13—H13	104.8 (11)	C2—C3—H3	120.2
C6'—C1'—C2'	117.84 (11)	O11—C4—C5	117.58 (11)
C6'—C1'—C9	121.99 (11)	O11—C4—C3	122.54 (11)
C2'—C1'—C9	120.16 (11)	C5—C4—C3	119.87 (11)
O13—C2'—C3'	117.69 (11)	C4—C5—C6	119.77 (12)
O13—C2'—C1'	121.54 (11)	C4—C5—H5	120.1
C3'—C2'—C1'	120.77 (11)	C6—C5—H5	120.1
C4'—C3'—C2'	119.83 (11)	C5—C6—C1	121.47 (12)
C4'—C3'—H3'	120.1	C5—C6—H6	119.3
C2'—C3'—H3'	120.1	C1—C6—H6	119.3
C3'—C4'—C5'	120.69 (12)	C1—C7—C8	113.24 (11)
C3'—C4'—H4'	119.7	C1—C7—H7A	108.9
C5'—C4'—H4'	119.7	C8—C7—H7A	108.9
C6'—C5'—C4'	119.56 (12)	C1—C7—H7B	108.9
C6'—C5'—H5'	120.2	C8—C7—H7B	108.9
C4'—C5'—H5'	120.2	H7A—C7—H7B	107.7
C5'—C6'—C1'	121.28 (11)	C9—C8—C7	112.48 (10)
C5'—C6'—H6'	119.4	C9—C8—H8A	109.1
C1'—C6'—H6'	119.4	C7—C8—H8A	109.1
C2—C1—C6	117.64 (11)	C9—C8—H8B	109.1
C2—C1—C7	121.42 (12)	C7—C8—H8B	109.1
C6—C1—C7	120.94 (11)	H8A—C8—H8B	107.8
C3—C2—C1	121.54 (12)	O10—C9—C1'	120.23 (10)
C3—C2—H2	119.2	O10—C9—C8	119.53 (11)
C1—C2—H2	119.2	C1'—C9—C8	120.24 (11)
C4—C3—C2	119.68 (12)
C6'—C1'—C9—C8	3.37 (18)	C9—C8—C7—C1	−172.51 (11)
C1'—C9—C8—C7	171.12 (11)	C8—C7—C1—C2	−109.99 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O10	0.95 (1)	1.68 (1)	2.5482 (13)	151 (2)
O11—H11···O13^i	0.94 (1)	1.92 (1)	2.8147 (13)	161 (2)
C6′—H6′···O11^ii	0.95	2.44	3.2731 (16)	146
C5′—H5′···O13^iii	0.95	2.49	3.4212 (16)	167

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