The crystal structure of a homocoupled compound with absolute configuration 3aR,3′aR,7aS,7′aS was determined. The molecule contains two similar moieties composed of two fused rings. Its supramolecular structure is controlled mainly by C—H⋯O interactions.
Keywords: crystal structure; absolute configuration; homocoupling reaction; palladium-catalyzed; 1,3-benzodioxolyl
Abstract
The absolute configuration, i.e. (3aR,3′aR,7aS,7′aS), of the title compound, C18H26O4, synthesized via a palladium-catalyzed homocoupling reaction, was determined on the basis of the synthetic pathway and was confirmed by X-ray diffraction. The homocoupled molecule is formed by two chemically identical moieties built up from two five- and six-membered fused rings. The supramolecular assembly is controlled mainly by C—H⋯O interactions that lead to the formation of hydrogen-bonded chains of molecules along the [001] direction, while weak dipolar interactions and van der Waals forces hold the chains together in the crystal structure.
Chemical context
Over the last few years, we have focused our efforts on the synthesis of vinylsulfimines as precursors in γ-lactamization reactions to generate asymmetric pyrrolidone derivatives which are of interest in medicinal chemistry (Silveira et al., 2012 ▸, 2014 ▸; Silveira & Marino, 2013 ▸; Pereira et al., 2015 ▸). Encouraged by our previous experience in functionalizing halo-cyclohexadiendiols (Heguaburu et al., 2008 ▸; Labora et al., 2010 ▸; Heguaburu et al., 2010 ▸; Labora et al., 2008 ▸), we synthesized a vinylic sulfide (molecule 3 in Fig. 1 ▸) from protected iodo-cyclohexenediol (molecule 1 in Fig. 1 ▸). This latter compound was obtained firstly by regioselective reduction of iodocyclohexadienediol derived from the biotransformation of iodobenzene (González et al., 1997 ▸). The obtained compound was treated with lithium isopropylthiolate in the presence of 5% of Pd (PPh3)4 as catalyst to obtain the vinyl sulfide in 85% yield. Surprisingly, one of the attempts to perform this reaction proceeded to afford traces of the homocoupled product (molecule 2 in Fig. 1 ▸). Considering this finding, we decided to prepare this new compound via a palladium-catalyzed homocoupling reaction of the vinylic iodide (molecule 1 in Fig. 1 ▸), mediated by indium, according to the Lee protocol (Lee et al., 2005 ▸). Herein, we report this new synthetic method and the crystal structure of the title compound.
Figure 1.
Synthetic pathway showing the formation of the homocoupled compound C18H26O4.
Structural commentary
The absolute configuration of the title compound (Fig. 2 ▸) was determined to be 3aR,3′aR,7aS,7′aS by considering the synthetic pathway and confirmed by X-ray diffraction on the basis of the anomalous dispersion of light atoms only. The molecule is built up from two chemically identical moieties (called A and B), each one composed of two fused rings and connected through the C4A—C4B bond. The six-membered rings (C3AA/AB, C7AA/AB, C7A/B, C6A/B, C5A/B, C4A/B) adopt an envelope conformation with atoms C7A/B (located para to C4A/B) as the flap [puckering parameters are Q = 0.403 (2) Å, θ = 49.2 (3)°, φ = 108.2 (4)° and Q = 0.490 (2) Å, θ = 58.5 (2)°, φ = 114.9 (3)°, respectively]. The five-membered rings (O1A/B, C2A/B, O3A/B, C3AA/AB, C7AA/AB) adopt a twisted conformation [puckering parameters Q(2) = 0.3285 (17) Å, φ(2) = 115.6 (3)° and Q(2) = 0.3268 (18) Å, φ(2) = 101.4 (3)°, respectively]). In fragment A, the flap of the envelope is oriented away from the five-membered ring while in fragment B, both C7 and the five-membered ring are on the same side of the plane of the envelope, making them conformationally different. The dihedral angle between the least-square planes through the six-membered rings is 43.15 (9)° while the dihedral angles between the five and six-membered rings are 69.31 (10) and 76.95 (10)° in A and B, respectively, leaving the two five-membered rings on opposite sides of the C4A—C4B bond and almost in the same plane, normal to the bisector plane of both six-membered rings.
Figure 2.
The molecular structure of the title compound, showing anisotropic displacement ellipsoids drawn at the 50% probability level.
Supramolecular features
In the crystal, weak C22A—H22F⋯O3B i [symmetry code: (i) x, y, z − 1] interactions link the molecules in chains running along [001], see Fig. 3 ▸ and Table 1 ▸. In the [100] and [010] directions, only weak dipolar interactions or van der Waals forces act between neighboring chains to stabilize the three-dimensional array of the crystal structure.
Figure 3.
The crystal structure of the title compound, showing the C—H⋯O hydrogen-bonding interactions (dotted lines) along the [001] direction.
Table 1. Hydrogen-bond geometry (Å, °).
| D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A |
|---|---|---|---|---|
| C22A—H22F⋯O3B i | 0.96 | 2.56 | 3.510 (3) | 171 |
Symmetry code: (i) 
.
Database survey
A search of the Cambridge Structural Database (CSD Version 5.36 with one update; Groom et al., 2016 ▸) using as a criterion the existence of molecular structures composed of two similar fragments of fused five and six-membered rings gave no results. However, a search for similar systems considering only the six-membered ring resulted in four hits, viz. two different crystal structures for (5,5′-diphenyl-1,1′-bi(cyclohex-1-en-1-yl)-4,4′-diyl)dimethanol in space groups P1 and P
, (S,S)-2,2′-bis(diphenylphosphinoyl)bi(cyclohex-1-ene) and (3S,6R)-3-isopropyl-2-[(3R,6S)-6-isopropyl-3-methyl-1-cyclohexenyl]-6-methylcyclohexene; none of which is composed of fused rings. These results demonstrate the rarity of this sort of molecule. While there are no reports about such systems, the structure of (3aS,4S,5R,7aR)-2,2,7-trimethyl-3a,4,5,7a-tetrahydro-1,3-benzodioxole-4,5-diol was published recently (Macías et al., 2015 ▸). In this case, the conformation of the fused rings keeps a level of similarity with the structural assembly of the title compound.
Synthesis and crystallization
A mixture of the vinylic iodide (molecule 1 in Fig. 1 ▸.) (140 mg, 0.5 mmol), Pd(PPh3)4 (10% wt., 14.4 mg, 0.025 mmol), indium (28.7 mg, 0.25 mmol), and lithium chloride (31.8 mg, 0.75 mmol) in dry THF (2 mL) was stirred at reflux for 4 h under a nitrogen atmosphere. The reaction mixture was quenched with NaHCO3 (sat. aq.). The aqueous layer was extracted with ethyl acetate (3 × 20 mL), and the combined organic phases were washed with brine, dried with Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexanes/ethyl acetate 95:5) to give the desired homocoupled product (43.5 mg, 57%).
Crystals suitable for X-ray crystallographic analysis were obtained by dissolving the title compound in the minimum volume of ethyl acetate, adding hexanes until the solution became slightly turbid, and slowly evaporating the solvent at room temperature. 1H NMR (400 MHz, CDCl3) δ: 6.16 (t, J = 4.2 Hz, 2H), 4.72 (d, J = 5.6 Hz, 2H), 4.33–4.29 (m, 2H), 2.36–2.27 (m, 2H), 2.09–2.00 (m, 2H), 1.87–1.71 (m, 4H), 1.40 (s, 6H); 1.39 (s, 6H). All spectroscopic and analytical data were in full agreement with the literature (Boyd et al., 2011 ▸).
Refinement
Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. H atoms bonded to C were placed in calculated positions (C—H = 0.93–0.98 Å) and included as riding contributions with isotropic displacement parameters set to 1.2–1.5 times the U eq of the parent atom.
Table 2. Experimental details.
| Crystal data | |
| Chemical formula | C18H26O4 |
| M r | 306.39 |
| Crystal system, space group | Monoclinic, P21 |
| Temperature (K) | 298 |
| a, b, c (Å) | 6.2927 (7), 17.9903 (19), 7.2991 (8) |
| β (°) | 95.216 (4) |
| V (Å3) | 822.89 (16) |
| Z | 2 |
| Radiation type | Cu Kα |
| μ (mm−1) | 0.69 |
| Crystal size (mm) | 0.40 × 0.35 × 0.30 |
| Data collection | |
| Diffractometer | Bruker D8 Venture/Photon 100 CMOS |
| Absorption correction | Multi-scan (SADABS; Bruker, 2013 ▸) |
| T min, T max | 0.687, 0.754 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 27011, 3232, 3135 |
| R int | 0.026 |
| (sin θ/λ)max (Å−1) | 0.618 |
| Refinement | |
| R[F 2 > 2σ(F 2)], wR(F 2), S | 0.027, 0.071, 1.08 |
| No. of reflections | 3232 |
| No. of parameters | 204 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.13, −0.10 |
| Absolute structure | Flack x determined using 1475 quotients [(I +)−(I −)]/[(I +)+(I −)] (Parsons et al., 2013 ▸) |
| Absolute structure parameter | 0.04 (4) |
Supplementary Material
Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016019927/rz5201sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016019927/rz5201Isup2.hkl
CCDC reference: 1522804
Additional supporting information: crystallographic information; 3D view; checkCIF report
Acknowledgments
The authors wish to thank CAPES/UDELAR (project No. 049/2013) for financial support. GPS and GDV acknowledge CAPES Science Without Borders – Special Visiting Researcher grant No. 096–2013. The authors also wish to thank ANII (EQC_2012_07), CSIC and the Facultad de Química for funds to purchase the diffractometer.
supplementary crystallographic information
Crystal data
| C18H26O4 | F(000) = 332 |
| Mr = 306.39 | Dx = 1.237 Mg m−3 |
| Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
| a = 6.2927 (7) Å | Cell parameters from 9685 reflections |
| b = 17.9903 (19) Å | θ = 4.9–72.4° |
| c = 7.2991 (8) Å | µ = 0.69 mm−1 |
| β = 95.216 (4)° | T = 298 K |
| V = 822.89 (16) Å3 | Parallelepiped, yellow |
| Z = 2 | 0.40 × 0.35 × 0.30 mm |
Data collection
| Bruker D8 Venture/Photon 100 CMOS diffractometer | 3232 independent reflections |
| Radiation source: Cu Incoatec microsource | 3135 reflections with I > 2σ(I) |
| Detector resolution: 10.4167 pixels mm-1 | Rint = 0.026 |
| φ and ω scans | θmax = 72.4°, θmin = 4.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 2013) | h = −7→7 |
| Tmin = 0.687, Tmax = 0.754 | k = −21→22 |
| 27011 measured reflections | l = −9→9 |
Refinement
| Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.0389P)2 + 0.0652P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.071 | (Δ/σ)max < 0.001 |
| S = 1.08 | Δρmax = 0.13 e Å−3 |
| 3232 reflections | Δρmin = −0.10 e Å−3 |
| 204 parameters | Extinction correction: SHELXL, Fc* = kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 1 restraint | Extinction coefficient: 0.0184 (15) |
| Primary atom site location: structure-invariant direct methods | Absolute structure: Flack x determined using 1475 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
| Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.04 (4) |
Special details
| 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 | ||
| C7A | 0.6166 (3) | 1.13949 (11) | 0.8000 (3) | 0.0486 (4) | |
| H7AA | 0.5916 | 1.1910 | 0.7652 | 0.058* | |
| H7AB | 0.6639 | 1.1382 | 0.9302 | 0.058* | |
| C6B | 0.5034 (4) | 0.77162 (12) | 0.6693 (3) | 0.0621 (6) | |
| H6BA | 0.5554 | 0.7523 | 0.5577 | 0.074* | |
| H6BB | 0.3603 | 0.7526 | 0.6774 | 0.074* | |
| C2A | 0.8127 (3) | 1.05458 (10) | 0.4052 (2) | 0.0451 (4) | |
| C7B | 0.6472 (4) | 0.74545 (11) | 0.8343 (3) | 0.0553 (5) | |
| H7BA | 0.5835 | 0.7580 | 0.9464 | 0.066* | |
| H7BB | 0.6625 | 0.6919 | 0.8297 | 0.066* | |
| C22A | 0.6299 (3) | 1.01769 (13) | 0.2920 (3) | 0.0580 (5) | |
| H22D | 0.5609 | 1.0532 | 0.2084 | 0.087* | |
| H22E | 0.5291 | 0.9991 | 0.3719 | 0.087* | |
| H22F | 0.6832 | 0.9773 | 0.2235 | 0.087* | |
| C2B | 1.0094 (3) | 0.83055 (10) | 1.1168 (3) | 0.0480 (4) | |
| C21A | 0.9882 (4) | 1.07986 (15) | 0.2908 (3) | 0.0674 (6) | |
| H21D | 1.0446 | 1.0377 | 0.2306 | 0.101* | |
| H21E | 1.1000 | 1.1030 | 0.3691 | 0.101* | |
| H21F | 0.9314 | 1.1149 | 0.2000 | 0.101* | |
| C21B | 1.2355 (4) | 0.85972 (14) | 1.1342 (4) | 0.0659 (6) | |
| H21A | 1.2803 | 0.8687 | 1.0139 | 0.099* | |
| H21B | 1.3284 | 0.8237 | 1.1970 | 0.099* | |
| H21C | 1.2417 | 0.9053 | 1.2029 | 0.099* | |
| C22B | 0.9298 (5) | 0.81210 (16) | 1.2994 (3) | 0.0716 (7) | |
| H22A | 0.7901 | 0.7905 | 1.2800 | 0.107* | |
| H22B | 0.9231 | 0.8567 | 1.3710 | 0.107* | |
| H22C | 1.0254 | 0.7774 | 1.3637 | 0.107* | |
| C6A | 0.4092 (3) | 1.09664 (11) | 0.7669 (3) | 0.0548 (5) | |
| H6AA | 0.3159 | 1.1102 | 0.8602 | 0.066* | |
| H6AB | 0.3389 | 1.1105 | 0.6481 | 0.066* | |
| C5B | 0.4969 (3) | 0.85505 (11) | 0.6607 (3) | 0.0491 (4) | |
| H5B | 0.3814 | 0.8774 | 0.5935 | 0.059* | |
| C5A | 0.4430 (3) | 1.01436 (10) | 0.7714 (3) | 0.0452 (4) | |
| H5A | 0.3277 | 0.9845 | 0.7940 | 0.054* | |
| C4B | 0.6466 (3) | 0.89895 (9) | 0.7434 (2) | 0.0363 (3) | |
| C4A | 0.6263 (2) | 0.98093 (9) | 0.7455 (2) | 0.0354 (4) | |
| C3AB | 0.8491 (3) | 0.86610 (9) | 0.8348 (2) | 0.0370 (4) | |
| H3AB | 0.9718 | 0.8867 | 0.7785 | 0.044* | |
| O3B | 0.8671 (2) | 0.88358 (7) | 1.02685 (17) | 0.0462 (3) | |
| C3AA | 0.8247 (2) | 1.02504 (9) | 0.7153 (2) | 0.0355 (3) | |
| H3AA | 0.9338 | 1.0159 | 0.8173 | 0.043* | |
| O3A | 0.90773 (18) | 1.00550 (6) | 0.54514 (17) | 0.0426 (3) | |
| C7AB | 0.8628 (3) | 0.78135 (10) | 0.8361 (2) | 0.0452 (4) | |
| H7B | 0.9330 | 0.7645 | 0.7290 | 0.054* | |
| O1B | 0.9974 (3) | 0.76615 (7) | 1.0002 (2) | 0.0601 (4) | |
| C7AA | 0.7894 (3) | 1.10842 (9) | 0.6933 (3) | 0.0423 (4) | |
| H7A | 0.9235 | 1.1349 | 0.7263 | 0.051* | |
| O1A | 0.7303 (3) | 1.11563 (8) | 0.50051 (18) | 0.0580 (4) |
Atomic displacement parameters (Å2)
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C7A | 0.0564 (11) | 0.0367 (9) | 0.0508 (10) | 0.0081 (8) | −0.0048 (8) | −0.0077 (8) |
| C6B | 0.0703 (14) | 0.0432 (11) | 0.0720 (14) | −0.0180 (10) | 0.0032 (11) | −0.0097 (10) |
| C2A | 0.0536 (10) | 0.0381 (9) | 0.0439 (9) | 0.0048 (8) | 0.0056 (8) | 0.0063 (7) |
| C7B | 0.0742 (13) | 0.0309 (9) | 0.0634 (12) | −0.0063 (8) | 0.0210 (10) | 0.0003 (8) |
| C22A | 0.0607 (11) | 0.0618 (13) | 0.0506 (11) | 0.0013 (10) | −0.0001 (9) | −0.0027 (9) |
| C2B | 0.0613 (11) | 0.0383 (9) | 0.0438 (9) | 0.0127 (8) | 0.0026 (8) | 0.0052 (7) |
| C21A | 0.0667 (14) | 0.0740 (15) | 0.0628 (13) | −0.0058 (11) | 0.0129 (10) | 0.0236 (11) |
| C21B | 0.0605 (13) | 0.0570 (13) | 0.0785 (15) | 0.0122 (10) | −0.0026 (11) | 0.0089 (11) |
| C22B | 0.0899 (17) | 0.0771 (17) | 0.0488 (12) | 0.0198 (14) | 0.0117 (11) | 0.0137 (11) |
| C6A | 0.0462 (10) | 0.0513 (12) | 0.0652 (12) | 0.0139 (8) | −0.0034 (8) | −0.0090 (9) |
| C5B | 0.0524 (10) | 0.0445 (10) | 0.0495 (10) | −0.0073 (8) | −0.0002 (8) | 0.0003 (8) |
| C5A | 0.0372 (8) | 0.0459 (10) | 0.0521 (10) | −0.0014 (7) | 0.0022 (7) | −0.0023 (8) |
| C4B | 0.0419 (8) | 0.0333 (8) | 0.0342 (8) | −0.0025 (6) | 0.0060 (6) | 0.0024 (6) |
| C4A | 0.0371 (8) | 0.0348 (8) | 0.0334 (8) | −0.0008 (6) | −0.0019 (6) | 0.0006 (6) |
| C3AB | 0.0435 (8) | 0.0295 (8) | 0.0386 (8) | 0.0007 (6) | 0.0074 (6) | 0.0005 (6) |
| O3B | 0.0590 (7) | 0.0379 (6) | 0.0405 (6) | 0.0146 (6) | −0.0024 (5) | −0.0036 (5) |
| C3AA | 0.0347 (7) | 0.0317 (8) | 0.0391 (8) | 0.0016 (6) | −0.0025 (6) | 0.0019 (6) |
| O3A | 0.0453 (6) | 0.0363 (6) | 0.0472 (6) | 0.0065 (5) | 0.0097 (5) | 0.0063 (5) |
| C7AB | 0.0606 (11) | 0.0331 (9) | 0.0433 (9) | 0.0062 (8) | 0.0133 (8) | −0.0010 (7) |
| O1B | 0.0851 (9) | 0.0355 (7) | 0.0581 (8) | 0.0181 (7) | −0.0034 (7) | 0.0022 (6) |
| C7AA | 0.0477 (9) | 0.0297 (8) | 0.0481 (9) | −0.0021 (7) | −0.0038 (7) | 0.0010 (7) |
| O1A | 0.0899 (10) | 0.0370 (7) | 0.0464 (7) | 0.0179 (7) | 0.0028 (7) | 0.0078 (5) |
Geometric parameters (Å, º)
| C7A—C7AA | 1.502 (3) | C21B—H21B | 0.9600 |
| C7A—C6A | 1.516 (3) | C21B—H21C | 0.9600 |
| C7A—H7AA | 0.9700 | C22B—H22A | 0.9600 |
| C7A—H7AB | 0.9700 | C22B—H22B | 0.9600 |
| C6B—C5B | 1.503 (3) | C22B—H22C | 0.9600 |
| C6B—C7B | 1.514 (3) | C6A—C5A | 1.495 (3) |
| C6B—H6BA | 0.9700 | C6A—H6AA | 0.9700 |
| C6B—H6BB | 0.9700 | C6A—H6AB | 0.9700 |
| C2A—O1A | 1.423 (2) | C5B—C4B | 1.331 (3) |
| C2A—O3A | 1.439 (2) | C5B—H5B | 0.9300 |
| C2A—C22A | 1.508 (3) | C5A—C4A | 1.329 (2) |
| C2A—C21A | 1.514 (3) | C5A—H5A | 0.9300 |
| C7B—C7AB | 1.501 (3) | C4B—C4A | 1.481 (2) |
| C7B—H7BA | 0.9700 | C4B—C3AB | 1.505 (2) |
| C7B—H7BB | 0.9700 | C4A—C3AA | 1.512 (2) |
| C22A—H22D | 0.9600 | C3AB—O3B | 1.431 (2) |
| C22A—H22E | 0.9600 | C3AB—C7AB | 1.527 (2) |
| C22A—H22F | 0.9600 | C3AB—H3AB | 0.9800 |
| C2B—O3B | 1.427 (2) | C3AA—O3A | 1.434 (2) |
| C2B—O1B | 1.435 (2) | C3AA—C7AA | 1.523 (2) |
| C2B—C22B | 1.502 (3) | C3AA—H3AA | 0.9800 |
| C2B—C21B | 1.511 (3) | C7AB—O1B | 1.430 (2) |
| C21A—H21D | 0.9600 | C7AB—H7B | 0.9800 |
| C21A—H21E | 0.9600 | C7AA—O1A | 1.428 (2) |
| C21A—H21F | 0.9600 | C7AA—H7A | 0.9800 |
| C21B—H21A | 0.9600 | ||
| C7AA—C7A—C6A | 112.42 (16) | H22A—C22B—H22B | 109.5 |
| C7AA—C7A—H7AA | 109.1 | C2B—C22B—H22C | 109.5 |
| C6A—C7A—H7AA | 109.1 | H22A—C22B—H22C | 109.5 |
| C7AA—C7A—H7AB | 109.1 | H22B—C22B—H22C | 109.5 |
| C6A—C7A—H7AB | 109.1 | C5A—C6A—C7A | 112.39 (15) |
| H7AA—C7A—H7AB | 107.9 | C5A—C6A—H6AA | 109.1 |
| C5B—C6B—C7B | 110.85 (17) | C7A—C6A—H6AA | 109.1 |
| C5B—C6B—H6BA | 109.5 | C5A—C6A—H6AB | 109.1 |
| C7B—C6B—H6BA | 109.5 | C7A—C6A—H6AB | 109.1 |
| C5B—C6B—H6BB | 109.5 | H6AA—C6A—H6AB | 107.9 |
| C7B—C6B—H6BB | 109.5 | C4B—C5B—C6B | 123.93 (18) |
| H6BA—C6B—H6BB | 108.1 | C4B—C5B—H5B | 118.0 |
| O1A—C2A—O3A | 105.85 (14) | C6B—C5B—H5B | 118.0 |
| O1A—C2A—C22A | 108.30 (16) | C4A—C5A—C6A | 124.64 (17) |
| O3A—C2A—C22A | 111.49 (15) | C4A—C5A—H5A | 117.7 |
| O1A—C2A—C21A | 110.76 (17) | C6A—C5A—H5A | 117.7 |
| O3A—C2A—C21A | 107.39 (16) | C5B—C4B—C4A | 122.49 (16) |
| C22A—C2A—C21A | 112.85 (18) | C5B—C4B—C3AB | 120.26 (16) |
| C7AB—C7B—C6B | 110.32 (16) | C4A—C4B—C3AB | 117.22 (14) |
| C7AB—C7B—H7BA | 109.6 | C5A—C4A—C4B | 121.95 (15) |
| C6B—C7B—H7BA | 109.6 | C5A—C4A—C3AA | 121.45 (15) |
| C7AB—C7B—H7BB | 109.6 | C4B—C4A—C3AA | 116.60 (14) |
| C6B—C7B—H7BB | 109.6 | O3B—C3AB—C4B | 109.67 (13) |
| H7BA—C7B—H7BB | 108.1 | O3B—C3AB—C7AB | 102.38 (13) |
| C2A—C22A—H22D | 109.5 | C4B—C3AB—C7AB | 116.09 (15) |
| C2A—C22A—H22E | 109.5 | O3B—C3AB—H3AB | 109.5 |
| H22D—C22A—H22E | 109.5 | C4B—C3AB—H3AB | 109.5 |
| C2A—C22A—H22F | 109.5 | C7AB—C3AB—H3AB | 109.5 |
| H22D—C22A—H22F | 109.5 | C2B—O3B—C3AB | 107.11 (13) |
| H22E—C22A—H22F | 109.5 | O3A—C3AA—C4A | 111.61 (13) |
| O3B—C2B—O1B | 105.65 (14) | O3A—C3AA—C7AA | 102.20 (13) |
| O3B—C2B—C22B | 108.06 (17) | C4A—C3AA—C7AA | 114.69 (14) |
| O1B—C2B—C22B | 110.10 (19) | O3A—C3AA—H3AA | 109.4 |
| O3B—C2B—C21B | 110.69 (17) | C4A—C3AA—H3AA | 109.4 |
| O1B—C2B—C21B | 109.18 (18) | C7AA—C3AA—H3AA | 109.4 |
| C22B—C2B—C21B | 112.9 (2) | C3AA—O3A—C2A | 107.67 (12) |
| C2A—C21A—H21D | 109.5 | O1B—C7AB—C7B | 113.01 (16) |
| C2A—C21A—H21E | 109.5 | O1B—C7AB—C3AB | 102.98 (15) |
| H21D—C21A—H21E | 109.5 | C7B—C7AB—C3AB | 112.28 (15) |
| C2A—C21A—H21F | 109.5 | O1B—C7AB—H7B | 109.5 |
| H21D—C21A—H21F | 109.5 | C7B—C7AB—H7B | 109.5 |
| H21E—C21A—H21F | 109.5 | C3AB—C7AB—H7B | 109.5 |
| C2B—C21B—H21A | 109.5 | C7AB—O1B—C2B | 109.73 (13) |
| C2B—C21B—H21B | 109.5 | O1A—C7AA—C7A | 109.95 (15) |
| H21A—C21B—H21B | 109.5 | O1A—C7AA—C3AA | 102.46 (14) |
| C2B—C21B—H21C | 109.5 | C7A—C7AA—C3AA | 114.67 (15) |
| H21A—C21B—H21C | 109.5 | O1A—C7AA—H7A | 109.8 |
| H21B—C21B—H21C | 109.5 | C7A—C7AA—H7A | 109.8 |
| C2B—C22B—H22A | 109.5 | C3AA—C7AA—H7A | 109.8 |
| C2B—C22B—H22B | 109.5 | C2A—O1A—C7AA | 109.73 (13) |
| C5B—C6B—C7B—C7AB | −52.6 (2) | C7AA—C3AA—O3A—C2A | −31.87 (16) |
| C7AA—C7A—C6A—C5A | 44.4 (2) | O1A—C2A—O3A—C3AA | 17.72 (18) |
| C7B—C6B—C5B—C4B | 21.4 (3) | C22A—C2A—O3A—C3AA | −99.84 (17) |
| C7A—C6A—C5A—C4A | −21.2 (3) | C21A—C2A—O3A—C3AA | 136.07 (17) |
| C6B—C5B—C4B—C4A | −174.59 (18) | C6B—C7B—C7AB—O1B | 172.70 (16) |
| C6B—C5B—C4B—C3AB | 7.3 (3) | C6B—C7B—C7AB—C3AB | 56.7 (2) |
| C6A—C5A—C4A—C4B | −177.19 (17) | O3B—C3AB—C7AB—O1B | −31.08 (16) |
| C6A—C5A—C4A—C3AA | 2.4 (3) | C4B—C3AB—C7AB—O1B | −150.49 (15) |
| C5B—C4B—C4A—C5A | 41.2 (3) | O3B—C3AB—C7AB—C7B | 90.79 (17) |
| C3AB—C4B—C4A—C5A | −140.59 (17) | C4B—C3AB—C7AB—C7B | −28.6 (2) |
| C5B—C4B—C4A—C3AA | −138.43 (17) | C7B—C7AB—O1B—C2B | −104.65 (19) |
| C3AB—C4B—C4A—C3AA | 39.8 (2) | C3AB—C7AB—O1B—C2B | 16.7 (2) |
| C5B—C4B—C3AB—O3B | −119.03 (18) | O3B—C2B—O1B—C7AB | 4.1 (2) |
| C4A—C4B—C3AB—O3B | 62.73 (18) | C22B—C2B—O1B—C7AB | 120.57 (19) |
| C5B—C4B—C3AB—C7AB | −3.7 (2) | C21B—C2B—O1B—C7AB | −114.94 (18) |
| C4A—C4B—C3AB—C7AB | 178.09 (14) | C6A—C7A—C7AA—O1A | 63.7 (2) |
| O1B—C2B—O3B—C3AB | −25.2 (2) | C6A—C7A—C7AA—C3AA | −51.0 (2) |
| C22B—C2B—O3B—C3AB | −143.02 (19) | O3A—C3AA—C7AA—O1A | 33.75 (16) |
| C21B—C2B—O3B—C3AB | 92.87 (19) | C4A—C3AA—C7AA—O1A | −87.19 (17) |
| C4B—C3AB—O3B—C2B | 158.69 (15) | O3A—C3AA—C7AA—C7A | 152.83 (14) |
| C7AB—C3AB—O3B—C2B | 34.88 (17) | C4A—C3AA—C7AA—C7A | 31.9 (2) |
| C5A—C4A—C3AA—O3A | −122.95 (16) | O3A—C2A—O1A—C7AA | 5.2 (2) |
| C4B—C4A—C3AA—O3A | 56.69 (18) | C22A—C2A—O1A—C7AA | 124.91 (17) |
| C5A—C4A—C3AA—C7AA | −7.3 (2) | C21A—C2A—O1A—C7AA | −110.85 (19) |
| C4B—C4A—C3AA—C7AA | 172.30 (14) | C7A—C7AA—O1A—C2A | −146.62 (16) |
| C4A—C3AA—O3A—C2A | 91.17 (15) | C3AA—C7AA—O1A—C2A | −24.27 (19) |
Hydrogen-bond geometry (Å, º)
| D—H···A | D—H | H···A | D···A | D—H···A |
| C22A—H22F···O3Bi | 0.96 | 2.56 | 3.510 (3) | 171 |
Symmetry code: (i) x, y, z−1.
References
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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. DOI: 10.1107/S2056989016019927/rz5201sup1.cif
Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989016019927/rz5201Isup2.hkl
CCDC reference: 1522804
Additional supporting information: crystallographic information; 3D view; checkCIF report