An aryl cyclohexyl nonanoid, an antiproliferative compound, has been extracted from spice from M. myristica using gradient solvent elution. In the crystal, intermolecular hydroxy O—H⋯Ocarbonyl hydrogen-bonding interactions generate large 36-membered centrosymmetric cyclic dimers, which are then extended into one-dimensional ribbons along [1
1].
Keywords: crystal structure, aryl cyclohexyl nonanoid, M. malabarica, antiproliferative activity, atom disorder and refinement, hydrogen bonding
Abstract
The title compound, C21H26O5, an aryl cyclohexyl nonanoid {systematic name: 3,5-dihydroxy-2-[9-(4-hydroxyphenyl)nonanoyl]cyclohexa-2,4-dien-1-one}, extracted from the spice plant Myristica malabarica comprises two ring components, a 4-hydroxyphenyl moiety and a 3,5-dihydroxycyclohexa-2,4-dienone moiety linked by a nonanoyl chain. The molecule has an extended essentially planar conformation stabilized by an intramolecular hydroxy O—H⋯Ocarbonyl hydrogen bond, giving a dihedral angle between the two ring systems of 6.37 (15)°. The C, O and H atoms associated with one of the hydroxy groups of the cyclohexadienone component are disordered over two sets of sites with site occupancies of 0.6972 and 0.3028. In the crystal, hydroxy O—H⋯O hydrogen bonds to carbonyl O-atom acceptors form large centrosymmetric R 2 2(36) cyclic dimers, which are further extended into supramolecular one-dimensional ribbon structures along [1-11].
Chemical context
The fruit rind of M. malabarica (family: Myristicaceae) is popularly known as Rampatri in Mumbai, India. It is used as an exotic spice in various Indian cuisines and also as a phytomedicine for the treatment of various kinds of ailments (Forrest & Heacock, 1972 ▸, and references therein). Its major pharmacological activities are credited with hepatoprotective (Morita et al., 2003 ▸), anti-carcinogenic (Patro et al., 2010 ▸; Maity et al., 2012 ▸), anti-leishmanial (Sen et al., 2007 ▸), anti-ulceral (Banerjee et al., 2007 ▸; Banerjee et al., 2008 ▸), antiproliferative (Manna et al., 2012 ▸, 2015 ▸, 2016 ▸; Tyagi et al., 2014 ▸), anti-inflammatory (Maity et al., 2012 ▸), anti-quorum sensing (Chong et al., 2011 ▸) and anti-thrombotic (Olajide et al., 1999 ▸; Patro et al., 2005 ▸, 2010 ▸) properties and it is found as a constituent in many ayurvedic preparations such as Pasupasi. Previous phytochemical investigations of the fruit rind of M. malabarica revealed the presence of four novel diaryl nonanoids named as malabaricones A–D (Purushothaman et al., 1977 ▸) and aryl tetradecanoid (Bauri et al., 2016 ▸). In addition, a lignan malabaricanol A and an isoflavone have been isolated from the heart wood of this plant (Purushothaman et al., 1974 ▸; Talukdar et al., 2000 ▸). A detailed phytochemical investigation of a methanol extract of the fruit rind of M. malabarica has been carried out. We have isolated a new type of molecule named as an aryl cyclohexyl nonanoid, the title compound C21H26O5, as a very minor constituent in addition to the reported compounds malabaricones A–D and aryl tetradecanoid. This molecule has exhibited anti-proliferative activity against various cancer cell lines such as A431, U937, MOLT-3, A549 and A2780 by using MTT and western blotting assay (unpublished result). Therefore, based on experimental results, it may be inferred that this fruit rind of M. malabarica may be used as a health promoter, a natural remedy which can be prescribed as a botanical dietary supplement to patients who are suffering from these kinds of health problems. The structure of the title compound is reported herein.
Structural commentary
The title compound comprises three molecular components, a 4-hydroxyphenyl ring, a 3,5-dihydroxcyclohexa-2,5-dienone ring and a bridging nonanoyl moiety (Fig. 1 ▸). The cyclohexadienone ring has a puckered conformation. There is an intramolecular O3—H⋯O4carbonyl bond enclosing an S(6) ring motif, which aids in stabilizing the essentially planar overall molecular conformation [inter-ring dihedral angle = 6.37 (15)° and r.m.s. deviation of fitted atoms = 0.2549 Å]. The C, O and H atoms associated with the second hydroxy group of the cyclohexadienone component are disordered over two sets of sites (C4, O2, H2A and (C4′, O2′, H2B) with a site-occupancy factor of 0.6972:0.3028.
Figure 1.
The molecular structure of the title compound, showing the atom labeling and displacement ellipsoids drawn at the 50% probability level. The disordered hydroxy group (C4—O2—H2A and C2′—O2′—H2B) is also shown, together with the intramolecular O—H⋯O hydrogen bond.
Supramolecular features
In the crystal, the molecules are linked by hydroxy O5—H⋯O1ii hydrogen bonds to carbonyl O-atom acceptors (Table 1 ▸), forming a primary large centrosymmetric 
(36) cyclic dimer (Fig. 2 ▸). These dimers are, in turn, linked through the disordered C4 hydroxy group [O2—H⋯O5i and O2′—H′⋯O5i], extending the structure into a one-dimensional ribbon along [11] (Fig. 3 ▸). No inter-ring π–π interactions are present in the structure (minimum ring-centroid separation = 5.66 Å).
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| O2—H2A⋯O5i | 0.83 | 2.18 | 3.004 (7) | 174 |
| O2′—H2B⋯O5i | 0.82 | 1.86 | 2.565 (16) | 143 |
| O3—H3O⋯O4 | 0.86 | 1.64 | 2.440 (3) | 153 |
| O5—H5O⋯O1ii | 0.83 | 1.86 | 2.687 (3) | 172 |
Symmetry codes: (i) 
; (ii) 
.
Figure 2.
Centrosymmetric dimer formation in the crystal packing of the title compound, with intermolecular hydrogen bonds shown as dashed lines.
Figure 3.
A view of the crystal packing in the unit cell, showing dimer extension into one-dimensional ribbons extending along [11]. Blue- and orange-coloured dashed lines indicate the intra- and intermolecular O—H⋯O hydrogen bonding. Only H atoms involved in hydrogen bonds are shown.
Database survey
A search of the Cambridge Structural Database (CSD, Version 5.37, updates November, 2015; Groom et al., 2016 ▸) has registered two hits for the compounds found in M. malabarica: malabaricone-A (Bauri et al., 2006a ▸) and malabaricone-C monohydrate (Bauri et al., 2006b ▸), but no other examples were found resembling the title compound.
Synthesis and crystallization
The compound has been isolated as a very minor constituent from a methanol extraction of the fruit rind of M. malabarica by using CC/SiO2 with gradient solvent elution with a binary mixture of solvent methanol and chloroform. Suitable crystals for X-ray data collection were obtained after recrystallization (×3) from hexane:ethyl acetate (4:1), by slow evaporation at room temperature. The NMR spectroscopic analysis of the crystallized product has been interpreted as follows. 1H NMR data (acetone-d 6, 200 MHz): 8.80 (s, brs-OH, 1H), 6.89 (dd, 1H, J = 8.2 Hz, H-2′′ & H-6′′, 2 × Ar-H), 6.59 (dd, 2H, J = 8.2 Hz, H-3′′ & H-5′′, 2 × Ar-H), 4.20–4.15 (m, 1H, H-6), 2.90 (dd, 2H, J = 7.0 Hz, H-2′), 2.61–2.43 (dd, 2H, J = 2.20 Hz each, H-4), 2.39 (dd, 2H, J = 7.0 Hz, H-9) 1.67–1.40 (m, 4H, H-3′ & H-8′), 1.19 (s, 8H, 4 × –CH2 H-4′ H-5′, H-6′ & H-7′). 13C NMR data (50 MHz,acetone-d 6): 205.69 (C-1′, >C=O), 198 (C-1, >C=O), 194 (C-3 & C-5, >C=C—OH), 156.20 (C-4′′, Ar—C—OH), 129.94 (C-2′′ & C-6′′, 2 × Ar—C—H), 116.6 (C-3′ & C-5′, Ar—C—H), 134.12 (C-6, >C=C<), 113.60 (C-2, >C=C<), 47.58 (C-2′, –CH2—CO–), 42.13 (C-9′, Ar—CH2), 40.57 (C-3′, –CH2—CH2), 35.56 (C-4′, –CH2—CH2–), 32.37 (C-6′, –CH2—CH2), 30.19 (C-3′, –CH2—CH2–), 25.40 (C-5′, –CH2).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H atoms were positioned with idealized geometry using a riding model with aromatic C—H = 0.93 Å (aromatic) or 0.97 Å (methylene). The H atoms of the OH groups were located in a difference map and were refined as riding on their parent O atoms. All H atoms were refined with isotropic displacement parameters set at 1.2 U
eq of the parent atom. The atoms C4 and O2 are disordered and were refined using a split model with site-occupancy factors 0.6972:0.3028. The corresponding bond distances in the disordered groups were restrained to be equal. The reflections 0 14 and 0 0 7 had poor disagreement with their calculated values and were omitted from the refinement.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C21H26O5 |
| M r | 358.42 |
| Crystal system, space group | Triclinic, P
|
| Temperature (K) | 293 |
| a, b, c (Å) | 5.6630 (8), 8.707 (1), 20.152 (3) |
| α, β, γ (°) | 81.69 (1), 86.48 (1), 88.48 (1) |
| V (Å3) | 981.2 (2) |
| Z | 2 |
| Radiation type | Mo Kα |
| μ (mm−1) | 0.09 |
| Crystal size (mm) | 0.48 × 0.48 × 0.20 |
| Data collection | |
| Diffractometer | Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector |
| Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▸) |
| T min, T max | 0.960, 0.983 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6013, 3552, 2638 |
| R int | 0.013 |
| (sin θ/λ)max (Å−1) | 0.602 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.071, 0.178, 1.10 |
| No. of reflections | 3552 |
| No. of parameters | 254 |
| No. of restraints | 3 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.36, −0.20 |
Supplementary Material
Crystal structure: contains datablock(s) I, 1R. DOI: 10.1107/S2056989016013797/zs2367sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016013797/zs2367Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016013797/zs2367Isup3.cml
CCDC reference: 1501296
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors thank Professor Dr Hartmut Fuess, FG Strukturforschung, Material und Geowissenschaften, Technische Universität Darmstadt, Petersenstrasse 23, 64287 Darmstadt, and Professor Kingston, Department of Chemistry, M/C 0212, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061, USA, for their kind co-operation to record X-ray diffraction data of the crystal, to provide diffractometer time and to carry out an antiproliferative bioassay against a cancer cell line.
supplementary crystallographic information
Crystal data
| C21H26O5 | Z = 2 |
| Mr = 358.42 | F(000) = 384 |
| Triclinic, P1 | Dx = 1.213 Mg m−3 |
| a = 5.6630 (8) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 8.707 (1) Å | Cell parameters from 2139 reflections |
| c = 20.152 (3) Å | θ = 2.9–27.7° |
| α = 81.69 (1)° | µ = 0.09 mm−1 |
| β = 86.48 (1)° | T = 293 K |
| γ = 88.48 (1)° | Prism, yellow |
| V = 981.2 (2) Å3 | 0.48 × 0.48 × 0.20 mm |
Data collection
| Oxford Diffraction Xcalibur diffractometer with Sapphire CCD detector | 2638 reflections with I > 2σ(I) |
| Radiation source: Enhance (Mo) X-ray source | Rint = 0.013 |
| Rotation method data acquisition using ω scans | θmax = 25.4°, θmin = 2.9° |
| Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | h = −6→6 |
| Tmin = 0.960, Tmax = 0.983 | k = −10→10 |
| 6013 measured reflections | l = −21→24 |
| 3552 independent reflections |
Refinement
| Refinement on F2 | 3 restraints |
| Least-squares matrix: full | Hydrogen site location: mixed |
| R[F2 > 2σ(F2)] = 0.071 | H-atom parameters constrained |
| wR(F2) = 0.178 | w = 1/[σ2(Fo2) + (0.0517P)2 + 0.9321P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.10 | (Δ/σ)max < 0.001 |
| 3552 reflections | Δρmax = 0.36 e Å−3 |
| 254 parameters | Δρmin = −0.20 e Å−3 |
Special details
| Experimental. Absorption correction: CrysAlis RED (Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
| Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| O1 | −0.0508 (4) | −0.0225 (3) | 0.83338 (11) | 0.0664 (7) | |
| O2 | 0.1863 (14) | −0.3525 (8) | 1.0267 (3) | 0.0655 (19) | 0.6972 |
| H2A | 0.2365 | −0.2936 | 1.0510 | 0.079* | 0.6972 |
| O2' | 0.254 (4) | −0.310 (2) | 1.0277 (7) | 0.069 (5) | 0.3028 |
| H2B | 0.2933 | −0.2259 | 1.0380 | 0.083* | 0.3028 |
| O3 | 0.6549 (4) | −0.3272 (3) | 0.82020 (11) | 0.0658 (7) | |
| H3O | 0.6550 | −0.2796 | 0.7798 | 0.079* | |
| O4 | 0.5334 (4) | −0.1694 (3) | 0.71742 (10) | 0.0673 (7) | |
| O5 | −0.5995 (4) | 0.8647 (2) | 0.10839 (10) | 0.0617 (6) | |
| H5O | −0.7128 | 0.9054 | 0.1283 | 0.074* | |
| C1 | 0.3066 (5) | −0.1679 (3) | 0.81894 (13) | 0.0427 (6) | |
| C2 | 0.1065 (5) | −0.1099 (3) | 0.85825 (14) | 0.0481 (7) | |
| C3 | 0.0917 (6) | −0.1598 (4) | 0.93293 (15) | 0.0742 (11) | |
| H3 | 0.0167 | −0.0988 | 0.9625 | 0.089* | |
| C4 | 0.2009 (10) | −0.3083 (6) | 0.9562 (2) | 0.0636 (14) | 0.6972 |
| C4' | 0.3050 (18) | −0.2280 (11) | 0.9622 (4) | 0.046 (2) | 0.3028 |
| C5 | 0.4429 (6) | −0.3327 (4) | 0.92481 (15) | 0.0605 (9) | |
| H5A | 0.5567 | −0.2819 | 0.9480 | 0.073* | |
| H5B | 0.4808 | −0.4430 | 0.9313 | 0.073* | |
| C6 | 0.4698 (5) | −0.2731 (3) | 0.85166 (14) | 0.0470 (7) | |
| C7 | 0.3503 (5) | −0.1185 (3) | 0.74718 (14) | 0.0467 (7) | |
| C8 | 0.1815 (5) | −0.0110 (3) | 0.70682 (14) | 0.0501 (7) | |
| H8A | 0.1566 | 0.0819 | 0.7279 | 0.060* | |
| H8B | 0.0303 | −0.0616 | 0.7084 | 0.060* | |
| C9 | 0.2634 (6) | 0.0367 (4) | 0.63382 (14) | 0.0566 (8) | |
| H9A | 0.3025 | −0.0553 | 0.6131 | 0.068* | |
| H9B | 0.4049 | 0.0981 | 0.6314 | 0.068* | |
| C10 | 0.0701 (6) | 0.1314 (4) | 0.59556 (15) | 0.0598 (8) | |
| H10A | −0.0672 | 0.0670 | 0.5959 | 0.072* | |
| H10B | 0.0231 | 0.2186 | 0.6187 | 0.072* | |
| C11 | 0.1480 (6) | 0.1921 (4) | 0.52332 (15) | 0.0627 (9) | |
| H11A | 0.2042 | 0.1053 | 0.5010 | 0.075* | |
| H11B | 0.2796 | 0.2612 | 0.5232 | 0.075* | |
| C12 | −0.0481 (6) | 0.2792 (4) | 0.48314 (15) | 0.0614 (9) | |
| H12A | −0.1808 | 0.2108 | 0.4836 | 0.074* | |
| H12B | −0.1027 | 0.3672 | 0.5048 | 0.074* | |
| C13 | 0.0332 (6) | 0.3360 (4) | 0.41130 (15) | 0.0599 (8) | |
| H13A | 0.0865 | 0.2474 | 0.3899 | 0.072* | |
| H13B | 0.1679 | 0.4026 | 0.4113 | 0.072* | |
| C14 | −0.1574 (6) | 0.4262 (3) | 0.36914 (14) | 0.0528 (7) | |
| H14A | −0.2963 | 0.3627 | 0.3705 | 0.063* | |
| H14B | −0.2036 | 0.5197 | 0.3880 | 0.063* | |
| C15 | −0.0638 (5) | 0.4693 (4) | 0.29700 (15) | 0.0553 (8) | |
| H15A | −0.0314 | 0.3738 | 0.2783 | 0.066* | |
| H15B | 0.0863 | 0.5201 | 0.2975 | 0.066* | |
| C16 | −0.2175 (5) | 0.5731 (3) | 0.24928 (14) | 0.0433 (6) | |
| C17 | −0.4281 (5) | 0.6465 (3) | 0.26883 (14) | 0.0486 (7) | |
| H17 | −0.4819 | 0.6297 | 0.3138 | 0.058* | |
| C18 | −0.5602 (5) | 0.7439 (3) | 0.22330 (14) | 0.0492 (7) | |
| H18 | −0.7001 | 0.7906 | 0.2376 | 0.059* | |
| C19 | −0.4795 (5) | 0.7697 (3) | 0.15660 (14) | 0.0458 (7) | |
| C20 | −0.2681 (5) | 0.6987 (3) | 0.13615 (14) | 0.0528 (8) | |
| H20 | −0.2128 | 0.7169 | 0.0913 | 0.063* | |
| C21 | −0.1409 (5) | 0.6019 (3) | 0.18188 (14) | 0.0502 (7) | |
| H21 | −0.0015 | 0.5550 | 0.1673 | 0.060* |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0639 (14) | 0.0742 (15) | 0.0563 (13) | 0.0366 (12) | −0.0044 (10) | 0.0007 (11) |
| O2 | 0.082 (5) | 0.068 (4) | 0.043 (2) | 0.013 (3) | 0.005 (2) | −0.001 (2) |
| O2' | 0.107 (13) | 0.067 (9) | 0.032 (5) | −0.021 (6) | −0.013 (5) | 0.004 (5) |
| O3 | 0.0579 (13) | 0.0792 (15) | 0.0541 (12) | 0.0328 (12) | 0.0045 (10) | 0.0024 (11) |
| O4 | 0.0666 (15) | 0.0829 (16) | 0.0474 (12) | 0.0210 (12) | 0.0073 (10) | −0.0015 (11) |
| O5 | 0.0625 (14) | 0.0668 (14) | 0.0496 (12) | 0.0272 (11) | −0.0018 (10) | 0.0066 (10) |
| C1 | 0.0426 (15) | 0.0434 (15) | 0.0404 (14) | 0.0073 (12) | −0.0031 (11) | −0.0018 (11) |
| C2 | 0.0477 (16) | 0.0482 (16) | 0.0463 (16) | 0.0125 (13) | −0.0043 (13) | −0.0017 (13) |
| C3 | 0.073 (2) | 0.099 (3) | 0.0426 (17) | 0.044 (2) | 0.0076 (16) | 0.0028 (17) |
| C4 | 0.078 (4) | 0.070 (3) | 0.036 (2) | 0.032 (3) | 0.010 (2) | 0.006 (2) |
| C4' | 0.068 (7) | 0.040 (5) | 0.030 (5) | −0.002 (5) | −0.007 (4) | −0.005 (4) |
| C5 | 0.062 (2) | 0.068 (2) | 0.0464 (17) | 0.0210 (16) | −0.0074 (14) | 0.0038 (15) |
| C6 | 0.0430 (16) | 0.0492 (16) | 0.0470 (16) | 0.0106 (13) | −0.0005 (12) | −0.0041 (13) |
| C7 | 0.0523 (17) | 0.0438 (15) | 0.0437 (15) | 0.0036 (13) | −0.0044 (13) | −0.0053 (12) |
| C8 | 0.0565 (18) | 0.0486 (16) | 0.0429 (15) | 0.0030 (14) | −0.0080 (13) | 0.0019 (12) |
| C9 | 0.071 (2) | 0.0545 (18) | 0.0433 (16) | 0.0027 (15) | −0.0105 (14) | 0.0005 (13) |
| C10 | 0.078 (2) | 0.0532 (18) | 0.0467 (17) | 0.0009 (16) | −0.0139 (15) | 0.0031 (14) |
| C11 | 0.081 (2) | 0.0580 (19) | 0.0471 (17) | 0.0033 (17) | −0.0151 (16) | 0.0034 (14) |
| C12 | 0.081 (2) | 0.0522 (18) | 0.0492 (17) | 0.0053 (16) | −0.0117 (16) | 0.0014 (14) |
| C13 | 0.074 (2) | 0.0544 (18) | 0.0488 (17) | 0.0063 (16) | −0.0148 (15) | 0.0037 (14) |
| C14 | 0.0605 (19) | 0.0465 (16) | 0.0492 (17) | 0.0035 (14) | −0.0075 (14) | 0.0018 (13) |
| C15 | 0.0510 (18) | 0.0560 (18) | 0.0542 (18) | 0.0050 (14) | −0.0073 (14) | 0.0082 (14) |
| C16 | 0.0428 (15) | 0.0400 (14) | 0.0455 (15) | 0.0013 (12) | −0.0052 (12) | 0.0001 (12) |
| C17 | 0.0486 (17) | 0.0539 (17) | 0.0400 (15) | 0.0034 (13) | 0.0017 (12) | 0.0012 (13) |
| C18 | 0.0437 (16) | 0.0503 (17) | 0.0518 (17) | 0.0084 (13) | 0.0025 (13) | −0.0048 (13) |
| C19 | 0.0462 (16) | 0.0431 (15) | 0.0461 (15) | 0.0081 (13) | −0.0040 (12) | −0.0003 (12) |
| C20 | 0.0544 (18) | 0.0581 (18) | 0.0424 (15) | 0.0147 (15) | 0.0031 (13) | −0.0009 (13) |
| C21 | 0.0461 (17) | 0.0520 (17) | 0.0504 (16) | 0.0140 (13) | 0.0004 (13) | −0.0039 (13) |
Geometric parameters (Å, º)
| O1—C2 | 1.238 (3) | C10—C11 | 1.518 (4) |
| O2—C4 | 1.415 (7) | C10—H10A | 0.9700 |
| O2—H2A | 0.8256 | C10—H10B | 0.9700 |
| O2'—H2B | 0.8247 | C11—C12 | 1.534 (4) |
| O3—C6 | 1.305 (3) | C11—H11A | 0.9700 |
| O3—H3O | 0.8588 | C11—H11B | 0.9700 |
| O4—C7 | 1.268 (3) | C12—C13 | 1.509 (4) |
| O5—C19 | 1.382 (3) | C12—H12A | 0.9700 |
| O5—H5O | 0.8342 | C12—H12B | 0.9700 |
| C1—C6 | 1.408 (4) | C13—C14 | 1.543 (4) |
| C1—C7 | 1.456 (4) | C13—H13A | 0.9700 |
| C1—C2 | 1.463 (4) | C13—H13B | 0.9700 |
| C2—C3 | 1.503 (4) | C14—C15 | 1.514 (4) |
| C3—C4 | 1.446 (5) | C14—H14A | 0.9700 |
| C3—C4' | 1.452 (10) | C14—H14B | 0.9700 |
| C3—H3 | 0.9300 | C15—C16 | 1.519 (4) |
| C4—C5 | 1.497 (5) | C15—H15A | 0.9700 |
| C4'—C5 | 1.449 (9) | C15—H15B | 0.9700 |
| C5—C6 | 1.490 (4) | C16—C21 | 1.390 (4) |
| C5—H5A | 0.9700 | C16—C17 | 1.400 (4) |
| C5—H5B | 0.9700 | C17—C18 | 1.395 (4) |
| C7—C8 | 1.510 (4) | C17—H17 | 0.9300 |
| C8—C9 | 1.517 (4) | C18—C19 | 1.382 (4) |
| C8—H8A | 0.9700 | C18—H18 | 0.9300 |
| C8—H8B | 0.9700 | C19—C20 | 1.400 (4) |
| C9—C10 | 1.531 (4) | C20—C21 | 1.379 (4) |
| C9—H9A | 0.9700 | C20—H20 | 0.9300 |
| C9—H9B | 0.9700 | C21—H21 | 0.9300 |
| C4—O2—H2A | 119.3 | C10—C11—C12 | 113.8 (3) |
| C6—O3—H3O | 105.4 | C10—C11—H11A | 108.8 |
| C19—O5—H5O | 107.1 | C12—C11—H11A | 108.8 |
| C6—C1—C7 | 117.7 (2) | C10—C11—H11B | 108.8 |
| C6—C1—C2 | 119.2 (2) | C12—C11—H11B | 108.8 |
| C7—C1—C2 | 123.1 (2) | H11A—C11—H11B | 107.7 |
| O1—C2—C1 | 123.6 (3) | C13—C12—C11 | 112.6 (3) |
| O1—C2—C3 | 118.4 (3) | C13—C12—H12A | 109.1 |
| C1—C2—C3 | 118.0 (2) | C11—C12—H12A | 109.1 |
| C4—C3—C2 | 116.1 (3) | C13—C12—H12B | 109.1 |
| C4'—C3—C2 | 116.5 (4) | C11—C12—H12B | 109.1 |
| C4—C3—H3 | 122.0 | H12A—C12—H12B | 107.8 |
| C2—C3—H3 | 122.0 | C12—C13—C14 | 114.5 (3) |
| O2—C4—C3 | 115.1 (5) | C12—C13—H13A | 108.6 |
| O2—C4—C5 | 113.0 (5) | C14—C13—H13A | 108.6 |
| C3—C4—C5 | 114.4 (4) | C12—C13—H13B | 108.6 |
| C5—C4'—C3 | 117.1 (6) | C14—C13—H13B | 108.6 |
| C4'—C5—C6 | 112.4 (4) | H13A—C13—H13B | 107.6 |
| C6—C5—C4 | 114.3 (3) | C15—C14—C13 | 110.4 (3) |
| C6—C5—H5A | 108.7 | C15—C14—H14A | 109.6 |
| C4—C5—H5A | 108.7 | C13—C14—H14A | 109.6 |
| C6—C5—H5B | 108.7 | C15—C14—H14B | 109.6 |
| C4—C5—H5B | 108.7 | C13—C14—H14B | 109.6 |
| H5A—C5—H5B | 107.6 | H14A—C14—H14B | 108.1 |
| O3—C6—C1 | 122.7 (3) | C14—C15—C16 | 118.1 (3) |
| O3—C6—C5 | 114.7 (2) | C14—C15—H15A | 107.8 |
| C1—C6—C5 | 122.6 (2) | C16—C15—H15A | 107.8 |
| O4—C7—C1 | 119.1 (2) | C14—C15—H15B | 107.8 |
| O4—C7—C8 | 119.0 (2) | C16—C15—H15B | 107.8 |
| C1—C7—C8 | 122.0 (2) | H15A—C15—H15B | 107.1 |
| C7—C8—C9 | 114.7 (3) | C21—C16—C17 | 117.4 (2) |
| C7—C8—H8A | 108.6 | C21—C16—C15 | 118.1 (3) |
| C9—C8—H8A | 108.6 | C17—C16—C15 | 124.5 (3) |
| C7—C8—H8B | 108.6 | C18—C17—C16 | 122.4 (3) |
| C9—C8—H8B | 108.6 | C18—C17—H17 | 118.8 |
| H8A—C8—H8B | 107.6 | C16—C17—H17 | 118.8 |
| C8—C9—C10 | 110.7 (3) | C19—C18—C17 | 118.8 (3) |
| C8—C9—H9A | 109.5 | C19—C18—H18 | 120.6 |
| C10—C9—H9A | 109.5 | C17—C18—H18 | 120.6 |
| C8—C9—H9B | 109.5 | O5—C19—C18 | 122.4 (2) |
| C10—C9—H9B | 109.5 | O5—C19—C20 | 117.9 (2) |
| H9A—C9—H9B | 108.1 | C18—C19—C20 | 119.7 (2) |
| C11—C10—C9 | 113.2 (3) | C21—C20—C19 | 120.6 (3) |
| C11—C10—H10A | 108.9 | C21—C20—H20 | 119.7 |
| C9—C10—H10A | 108.9 | C19—C20—H20 | 119.7 |
| C11—C10—H10B | 108.9 | C20—C21—C16 | 121.2 (3) |
| C9—C10—H10B | 108.9 | C20—C21—H21 | 119.4 |
| H10A—C10—H10B | 107.8 | C16—C21—H21 | 119.4 |
| C6—C1—C2—O1 | −176.9 (3) | C6—C1—C7—C8 | 177.6 (3) |
| C7—C1—C2—O1 | 5.0 (5) | C2—C1—C7—C8 | −4.3 (4) |
| C6—C1—C2—C3 | 3.0 (4) | O4—C7—C8—C9 | −5.2 (4) |
| C7—C1—C2—C3 | −175.1 (3) | C1—C7—C8—C9 | 176.1 (3) |
| O1—C2—C3—C4 | 152.2 (4) | C7—C8—C9—C10 | 174.2 (3) |
| C1—C2—C3—C4 | −27.6 (5) | C8—C9—C10—C11 | 176.0 (3) |
| O1—C2—C3—C4' | −164.8 (5) | C9—C10—C11—C12 | 176.6 (3) |
| C1—C2—C3—C4' | 15.4 (7) | C10—C11—C12—C13 | −179.1 (3) |
| C2—C3—C4—O2 | 179.6 (5) | C11—C12—C13—C14 | −179.2 (3) |
| C2—C3—C4—C5 | 46.1 (6) | C12—C13—C14—C15 | −176.4 (3) |
| C2—C3—C4'—C5 | −40.0 (10) | C13—C14—C15—C16 | −173.8 (3) |
| C3—C4'—C5—C6 | 43.6 (9) | C14—C15—C16—C21 | −174.6 (3) |
| O2—C4—C5—C6 | −174.4 (5) | C14—C15—C16—C17 | 7.6 (5) |
| C3—C4—C5—C6 | −39.9 (6) | C21—C16—C17—C18 | 0.6 (4) |
| C7—C1—C6—O3 | −0.4 (4) | C15—C16—C17—C18 | 178.4 (3) |
| C2—C1—C6—O3 | −178.6 (3) | C16—C17—C18—C19 | −0.4 (5) |
| C7—C1—C6—C5 | −179.6 (3) | C17—C18—C19—O5 | −179.9 (3) |
| C2—C1—C6—C5 | 2.2 (5) | C17—C18—C19—C20 | −0.2 (4) |
| C4'—C5—C6—O3 | 155.7 (5) | O5—C19—C20—C21 | −179.6 (3) |
| C4—C5—C6—O3 | −163.2 (4) | C18—C19—C20—C21 | 0.7 (5) |
| C4'—C5—C6—C1 | −25.0 (6) | C19—C20—C21—C16 | −0.5 (5) |
| C4—C5—C6—C1 | 16.1 (5) | C17—C16—C21—C20 | −0.1 (4) |
| C6—C1—C7—O4 | −1.1 (4) | C15—C16—C21—C20 | −178.1 (3) |
| C2—C1—C7—O4 | 177.0 (3) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2A···O5i | 0.83 | 2.18 | 3.004 (7) | 174 |
| O2′—H2B···O5i | 0.82 | 1.86 | 2.565 (16) | 143 |
| O3—H3O···O4 | 0.86 | 1.64 | 2.440 (3) | 153 |
| O5—H5O···O1ii | 0.83 | 1.86 | 2.687 (3) | 172 |
Symmetry codes: (i) x+1, y−1, z+1; (ii) −x−1, −y+1, −z+1.
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Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Supplementary Materials
Crystal structure: contains datablock(s) I, 1R. DOI: 10.1107/S2056989016013797/zs2367sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016013797/zs2367Isup2.hkl
Supporting information file. DOI: 10.1107/S2056989016013797/zs2367Isup3.cml
CCDC reference: 1501296
Additional supporting information: crystallographic information; 3D view; checkCIF report