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Acta Crystallographica Section E: Crystallographic Communications logoLink to Acta Crystallographica Section E: Crystallographic Communications
. 2019 Mar 20;75(Pt 4):460–464. doi: 10.1107/S2056989019003499

Crystal structure and Hirshfeld surface analysis of dimethyl (1R*,3aS*,3a1 R*,6aS*,9R*,9aS*)-3a1,5,6,9a-tetra­hydro-1H,4H,9H-1,3a:6a,9-di­epoxy­phenalene-2,3-di­carboxyl­ate

Kseniia A Alekseeva a, Pavel V Raspertov a, Sevim Türktekin Çelikesir b, Mehmet Akkurt b, Flavien A A Toze c,*, Elena A Sorokina a
PMCID: PMC6509682  PMID: 31161057

In the title di­epoxy­phenalene derivative, two di­hydro­furan and two tetra­hydro­furan rings, as well as one cyclo­hexane ring, are fused together with two methyl carboxyl­ate groups in positions 2- and 3-. In the crystal, two pairs of C—H⋯O hydrogen bonds link the mol­ecules to form inversion dimers, enclosing two Inline graphic(6) ring motifs.

Keywords: crystal structure, di­epoxy­phenalene, fused hexa­cyclic system, C—H⋯O hydrogen bonds, Hirshfeld surface analysis

Abstract

The title di­epoxy­phenalene derivative, C17H18O6, comprises a fused cyclic system containing four five-membered rings (two di­hydro­furan and two tetra­hydro­furan) and one six-membered ring (cyclo­hexa­ne). The five-membered di­hydro­furan and tetra­hydro­furan rings adopt envelope conformations, and the six-membered cyclo­hexane ring adopts a distorted chair conformation. Two methyl carboxyl­ate groups occupy adjacent positions (2- and 3-) on a tetra­hydro­furan ring. In the crystal, two pairs of C—H⋯O hydrogen bonds link the mol­ecules to form inversion dimers, enclosing two R 2 2(6) ring motifs, that stack along the a-axis direction and are arranged in layers parallel to the bc plane.

Chemical context  

Reactions totally depending on thermodynamic and kinetic control are infrequently found in the field of organic synthesis, at the same time such transformations are very perspective and attractive from a practical point of view since they allow the direction of the reaction to be changed radically by varying only one of the reaction parameters (usually the catalyst or temperature).

The first example of kinetic/thermodynamic control in the course of the Diels–Alder reaction was reported in 1948 (Woodward & Baer, 1948 ▸). Since then, the reversibility of the [4 + 2] cyclo­addition was observed many times for examples of a broad range of dienes and dienophiles, including alkynes and furans (Boutelle & Northrop, 2011 ▸; Taffin et al., 2010 ▸; White et al., 2000 ▸; Marchand et al., 1998 ▸; Manoharan & Venuvanalingam, 1997 ▸; Bott et al., 1996 ▸; Bartlett & Wu, 1985 ▸). From this diversity of diene/dienophile combinations, tandem and domino reactions of the [4 + 2] cyclo­addition based on acetyl­enic dienophiles are more inter­esting for the total synthesis of natural or bioactive products (Sears & Boger, 2016 ▸; Parvatkar et al., 2014 ▸; Winkler, 1996 ▸). However, the range of bis-dienes suitable for such tandem transformations is very limited and, currently, there are only a few published examples of full kinetic/thermodynamic control in the course of the tandem intra­molecular [4 + 2] cyclo­addition (reactions leading to either kinetically or thermodynamically controlled products, depending on temperature; Marchionni et al., 1996 ▸; Oh et al., 2010 ▸; Criado et al., 2010 ▸; Paquette et al., 1978 ▸; Visnick & Battiste, 1985 ▸).

The present paper describes the uncommon thermal rearrangement of the ‘pincer-adduct’ (1) into the ‘domino-adduct’ (2) [the terminology and the mechanism of the reaction are given in references Borisova, Nikitina et al. (2018 ▸) and Borisova, Kvyatkovskaya et al. (2018 ▸); for references of works related to the present paper, see also Lautens & Fillion (1998 ▸), Lautens & Fillion (1997 ▸) and Domingo et al. (2000 ▸)]. The transformation proceeds through the reversible retro-Diels–Alder reaction of the kinetically controlled ‘pincer-adduct’ (1), followed by the repeated intra­molecular [4 + 2] cyclo­addition in an inter­mediate, leading to the formation of the thermodynamically controlled ’domino-adduct’ (2) in an almost qu­anti­tative yield.graphic file with name e-75-00460-scheme1.jpg

Structural commentary  

The mol­ecule structure of compound (2) is illustrated in Fig. 1 ▸. It is made up from a fused cyclic system containing four five-membered rings (two di­hydro­furan and two tetra­hydro­furan) in the usual envelope conformations and a six-membered cyclo­hexane ring in a distorted chair conformation. The puckering parameters of the five-membered di­hydro­furan (A = O1/C1/C2/C5/C6 and B = O2/C1/C6/C7/C10) and tetra­hydro­furan (C = O1/C2–C5 and D = O2/C7–C10) rings are Q(2) = 0.5230 (18) Å and φ(2) = 178.1 (2)° for ring A, Q(2) = 0.5492 (17) Å and φ(2) = 182.3 (2)° for B, Q(2) = 0.5230 (18) Å and φ(2) = 1.0 (2)° for C, and Q(2) = 0.5303 (17) Å and φ(2) = 358.9 (2)° for D. The puckering parameters of the six-membered cyclo­hexane ring (C1/C2/C10–C13) are Q T = 0.518 (2) Å, θ = 6.9 (2)° and φ = 178.2 (18)°. In positions 2- and 3-, i.e. on atoms C8 and C9 (Fig. 1 ▸), there are methyl carboxyl­ate substituents whose mean planes are inclined to the mean plane through atoms C7–C10 by 7.38 (13) and 70.65 (14)° for groups O3/O4/C14/C15 and O5/O6/C16/C17, respectively.

Figure 1.

Figure 1

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The mol­ecular structure of compound (2), with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Supra­molecular features and Hirshfeld surface analysis  

In the crystal, two pairs of C—H⋯O hydrogen bonds link the mol­ecules forming inversion dimers, enclosing two Inline graphic(6) ring motifs. The dimers stack along the a-axis direction and are arranged in layers parallel to the bc plane (Table 1 ▸ and Fig. 2 ▸). C—H⋯π and π–π inter­actions are not observed, but H⋯H contacts (Tables 2 ▸ and 3 ▸) dominate in the packing, as detailed in the next section.

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C5—H5⋯O2i 1.00 2.58 3.330 (2) 132
C7—H7⋯O1i 1.00 2.52 3.351 (2) 140
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Symmetry code: (i) Inline graphic.

Figure 2.

Figure 2

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A viewed along the b axis of the crystal packing of compound (2), emphasizing the formation of C—H⋯O hydrogen-bonded dimers. Hydrogen bonds are shown as dashed lines (Table 1 ▸).

Table 2. Summary of short inter­atomic contacts (Å) in the crystal of compound (2).

Contact Distance Symmetry operation
H7⋯O1 2.52 1 − x, 1 − y, 1 − z
H13B⋯H17B 2.49 x, Inline graphic − y, −Inline graphic + z
H15C⋯H12A 2.53 1 − x, −Inline graphic + y, Inline graphic − z
H15A⋯H3 2.56 −x, 1 − y, 1 − z
H6⋯H15B 2.57 x, Inline graphic − y, −Inline graphic + z
H17A⋯O5 2.90 −x, 1 − y, 2 − z
H15B⋯H6 2.57 x, Inline graphic − y, Inline graphic + z
H5⋯H17C 2.48 x, y, −1 + z
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Table 3. Percentage contributions of inter­atomic contacts to the Hirshfeld surface of compound (2).

Contact Percentage contribution
H⋯H 54.6
O⋯H/H⋯O 36.2
C⋯H/H⋯C 8.0
O⋯O 1.1
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Hirshfeld surface analysis and two-dimensional fingerprint plots  

Hirshfeld surface and fingerprint plots were generated using CrystalExplorer (McKinnon et al., 2007 ▸). Hirshfeld surfaces enable the visualization of inter­molecular inter­actions by different colours and colour intensity, representing short or long contacts and indicating the relative strength of the inter­actions. Fig. 3 ▸ shows the Hirshfeld surface of the title compound mapped over d norm, where it is evident from the bright-red spots appearing near the O atoms that these atoms play a significant role in the mol­ecular packing. The red spots represent closer contacts and negative d norm values on the surface, corresponding to the C—H⋯O inter­actions.

Figure 3.

Figure 3

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Hirshfeld surface of compound (2) mapped over d norm.

The bright-red spots indicate their roles as the respective donors and/or acceptors; they also appear as blue and red regions corresponding to positive and negative potentials on the Hirshfeld surface mapped over electrostatic potential (Fig. 4 ▸; Spackman et al., 2008 ▸; Jayatilaka et al., 2005 ▸). The blue regions indicate the positive electrostatic potential (hydrogen-bond donors), while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape index of the Hirshfeld surface is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π inter­actions. Fig. 5 ▸ clearly suggest that no π–π inter­actions are present in the title compound.

Figure 4.

Figure 4

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View of the three-dimensional Hirshfeld surface of compound (2) plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. Hydrogen-bond donors and acceptors are shown as blue and red regions around the atoms corresponding to positive and negative potentials, respectively.

Figure 5.

Figure 5

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Hirshfeld surface of compound (2) plotted over shape index.

The percentage contributions of various contacts to the total Hirshfeld surface are given in Table 3 ▸ and are also shown as two-dimensional (2D) fingerprint plots in Fig. 6 ▸. The H⋯H inter­actions appear in the middle of the scattered points in the 2D fingerprint plots with an overall contribution to the Hirshfeld surface of 54.6% (Fig. 6 ▸ b). The contribution from the O⋯H/H⋯O contacts, corresponding to C—H⋯O inter­actions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bonding inter­action (36.2%, Fig. 6 ▸ c and Tables 2 ▸ and 3 ▸). The small percentage contributions from the remaining inter­atomic contacts are summarized in Table 3 ▸ and indicated by their fingerprint plots for C⋯H/H⋯C (Fig. 6 ▸ d) and O⋯O (Fig. 6 ▸ e). The large number of H⋯H and O⋯H/H⋯O inter­actions suggest that van der Waals inter­actions and hydrogen bonding play the major roles in the crystal packing (Hathwar et al., 2015 ▸).

Figure 6.

Figure 6

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The 2D fingerprint plots of compound (2), showing (a) all inter­actions, and delineated into (b) H⋯H, (c) O⋯H/H⋯O, (d) C⋯H/H⋯C and (e) O⋯O inter­actions [d e and d i represent the distances from a point on the Hirshfeld surface to the nearest atoms outside (external) and inside (inter­nal) the surface, respectively].

Database survey  

A search of the Cambridge Structural Database (CSD, Version 5.40, February 2019; Groom et al., 2016 ▸) for the di­epoxy­phenalene skeleton gave only 2 hits, viz. 9b-acetyl-9a-meth­oxy­carbonyl-1,3a:6a,9-diep­oxy-4,5,6,9-tetra­hydro­phena­lene (CSD refcode RUSGOB; Lautens & Fillion, 1997 ▸) and 9a-benzene­sulfonyl-1,3a:6a,9-diep­oxy-9b-meth­oxy­carbonyl-4,5,6,9-tetra­hydro­phenalene (RUSHAO; Lautens & Fillion, 1997 ▸). A search for the di­epoxy­benzo[de]iso­quinoline skelton gave 8 hits, three of which are very similar to compounds (1) and (2), viz. 2-benzyl-6a,9b-bis­(tri­fluoro­meth­yl)-2,3,6a,9b-tetra­hydro-1H,6H,7H-3a,6:7,9a-di­epoxy­benzo[de]iso­quinoline (CSD refcode HENLAQ; Borisova, Nikitina et al., 2018 ▸), 2-benzyl-4,5-bis­(tri­fluoro­meth­yl)-2,3,6a,9b-tetra­hydro-1H,6H,7H-3a,6:7,9a-di­epoxy­benzo[de]iso­quinoline (HENLEU; Borisova, Nikitina et al., 2018 ▸) and dimethyl (3aS,6R,6aS,7S)-2-(2,2,2-tri­fluoro­acet­yl)-2,3-di­hydro-1H,6H,7H-3a,6:7,9a-di­epoxy­benzo[de]iso­quinoline-3a1,6a-di­carboxyl­ate (LIRKAB; Atioğlu et al., 2018 ▸).

In the crystal of HENLAQ, inversion-related mol­ecules are linked into dimers by pairs of C—H⋯O hydrogen bonds, and the dimers lie in layers parallel to (100). C—H⋯π inter­actions are also observed, together with intra­molecular F⋯F contacts. The asymmetric unit of HENLEU contains two independent mol­ecules. In the crystal, mol­ecules are linked by C—H⋯O and C—H⋯F hydrogen bonds, forming columns along [010]. Likewise, C—H⋯π inter­actions and F⋯F intra­molecular contacts are also present. In the crystal structure of LIRKAB, inter­molecular C—H⋯O inter­actions involving the O atoms of the carbonyl groups, the oxygen bridgehead atoms and the meth­oxy O atoms, as well as C—H⋯F hydrogen bonds, define the crystal packing. These packing features lead to the formation of a supra­molecular three-dimensional structure. C—H⋯π and π–π inter­actions are not observed, but H⋯H inter­actions dominate in the packing. This situation is similar to that in the crystal of the title compound.

Synthesis and crystallization  

The synthesis of the title compound (2) is illustrated in the Scheme. Compound (1) (0.89 g, 2.81 mmol) was dissolved in dry o-Me2C6H4 (15 ml) and then heated under reflux for 4 h at ∼413 K (thin-layer chromatography monitoring). The reaction mixture was cooled and the solvent removed under reduced pressure. The residue was purified by recrystallization from an EtOAc/hexane mixture (1:1 v/v) to give compound (2) as large colourless prismatic crystals [0.82 g, 2.61 mmol, 93%; m.p. 410.4–411.8 K (hexa­ne/EtOAc)]. 1H NMR (400 MHz, CDCl3): δ 6.43 (1H, dd, J = 1.8 and J = 5.6 Hz, H-8), 6.27 (1H, d, J = 5.6 Hz, H-9), 5.09 (1H, s, H-1), 4.88 (1H, d, J = 1.8 Hz, H-9), 3.78 (3H, s, CO2Me), 3.73 (3H, s, CO2Me), 2.23–2.17 (3H, m, H-4A, H-6A and H-9a), 2.00–1.88 (4H, m, H-4B, H-6B, H-5A and H-9b) 1.71–1.68 (1H, m, H-5B). 13C NMR (100 MHz, CDCl3): δ 164.7 (CO2Me), 162.6 (CO2Me), 150.6 (C-3), 143.8 (C-2), 140.8 (C-7), 138.5 (C-8), 89.3 (C-3a), 85.8 (C-6a), 81.3 (C-1), 80.5 (C-9), 52.2 (C-9a), 52.0 (2 × CO2 Me), 49.8 (C-9b), 26.7 (C-9), 25.0 (C-6), 17.2 (C-5). IR νmax/cm−1 (KBr): 1709, 1628, 1284, 1261. HRMS (ESI–TOF): calculated for C17H18O6 [M + H]+ 318.1103; found 318.1125.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 4 ▸. All H atoms were fixed and allowed to ride on the parent atoms, with C—H = 0.95–1.00 Å, and with U iso(H) = 1.5U eq(C) for methyl H atoms and 1.2U eq(C) for other H atoms.

Table 4. Experimental details.

Crystal data
Chemical formula C17H18O6
M r 318.31
Crystal system, space group Monoclinic, P21/c
Temperature (K) 100
a, b, c (Å) 9.3903 (19), 14.157 (3), 11.520 (2)
β (°) 99.032 (3)
V (Å3) 1512.5 (5)
Z 4
Radiation type Synchrotron, λ = 0.96990 Å
μ (mm−1) 0.23
Crystal size (mm) 0.35 × 0.15 × 0.10
 
Data collection
Diffractometer MAR CCD
Absorption correction Multi-scan (SCALA; Evans, 2006 ▸)
T min, T max 0.918, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections 17699, 3216, 2464
R int 0.151
(sin θ/λ)max (Å−1) 0.641
 
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S 0.067, 0.192, 1.11
No. of reflections 3216
No. of parameters 211
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.50, −0.41
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Computer programs: Automar (Doyle, 2011 ▸), iMosflm (Battye et al., 2011 ▸), SHELXS97 (Sheldrick, 2008 ▸), SHELXL2018 (Sheldrick, 2015 ▸), ORTEP-3 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) 2, Global. DOI: 10.1107/S2056989019003499/rz5253sup1.cif

e-75-00460-sup1.cif (612.2KB, cif)

CCDC reference: 1902671

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

C17H18O6 F(000) = 672
Mr = 318.31 Dx = 1.398 Mg m−3
Monoclinic, P21/c Synchrotron radiation, λ = 0.96990 Å
a = 9.3903 (19) Å Cell parameters from 500 reflections
b = 14.157 (3) Å θ = 3.5–35.0°
c = 11.520 (2) Å µ = 0.23 mm−1
β = 99.032 (3)° T = 100 K
V = 1512.5 (5) Å3 Prism, colourless
Z = 4 0.35 × 0.15 × 0.10 mm
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Data collection

MAR CCD diffractometer 2464 reflections with I > 2σ(I)
/f scan Rint = 0.151
Absorption correction: multi-scan (Scala; Evans, 2006) θmax = 38.5°, θmin = 3.6°
Tmin = 0.918, Tmax = 0.975 h = −11→12
17699 measured reflections k = −17→14
3216 independent reflections l = −14→14
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Refinement

Refinement on F2 Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.067 w = 1/[σ2(Fo2) + (0.0746P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.192 (Δ/σ)max < 0.001
S = 1.11 Δρmax = 0.50 e Å−3
3216 reflections Δρmin = −0.40 e Å−3
211 parameters Extinction correction: SHELXL2018 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints Extinction coefficient: 0.038 (4)
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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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
C1 0.20277 (19) 0.59385 (13) 0.59498 (15) 0.0155 (5)
H1 0.106665 0.591973 0.621979 0.019*
C2 0.21999 (18) 0.67977 (14) 0.51388 (16) 0.0177 (5)
C3 0.0861 (2) 0.67729 (14) 0.41833 (16) 0.0195 (5)
H3 0.006228 0.719276 0.409799 0.023*
C4 0.1054 (2) 0.60374 (14) 0.34962 (16) 0.0214 (5)
H4 0.041452 0.582144 0.282721 0.026*
C5 0.25131 (19) 0.56171 (14) 0.40095 (15) 0.0173 (5)
H5 0.299224 0.523974 0.344653 0.021*
C6 0.22826 (19) 0.50832 (14) 0.51569 (15) 0.0163 (5)
H6 0.144221 0.464107 0.502585 0.020*
C7 0.36433 (19) 0.46304 (13) 0.58988 (15) 0.0157 (5)
H7 0.419362 0.418266 0.546483 0.019*
C8 0.31304 (18) 0.42263 (13) 0.69973 (15) 0.0156 (5)
C9 0.29437 (19) 0.49717 (13) 0.76792 (16) 0.0160 (5)
C10 0.33216 (18) 0.58488 (13) 0.69840 (15) 0.0141 (5)
C11 0.3755 (2) 0.67670 (13) 0.76102 (16) 0.0194 (5)
H11A 0.465992 0.667147 0.816594 0.023*
H11B 0.299650 0.695990 0.806996 0.023*
C12 0.3976 (2) 0.75571 (15) 0.67394 (17) 0.0198 (5)
H12A 0.481612 0.739906 0.635317 0.024*
H12B 0.419398 0.815491 0.717708 0.024*
C13 0.2644 (2) 0.77010 (14) 0.57926 (17) 0.0202 (5)
H13A 0.183317 0.793440 0.616846 0.024*
H13B 0.286127 0.818677 0.522740 0.024*
C14 0.27146 (19) 0.32255 (14) 0.71005 (16) 0.0159 (5)
C15 0.1868 (2) 0.20708 (15) 0.83169 (18) 0.0268 (5)
H15A 0.104113 0.188440 0.773336 0.040*
H15B 0.162026 0.200255 0.910798 0.040*
H15C 0.269400 0.166559 0.823982 0.040*
C16 0.22323 (19) 0.50325 (14) 0.87480 (16) 0.0163 (5)
C17 0.2451 (3) 0.46966 (17) 1.07828 (17) 0.0322 (6)
H17A 0.179303 0.415658 1.075185 0.048*
H17B 0.191531 0.528174 1.085776 0.048*
H17C 0.321654 0.463002 1.146134 0.048*
O1 0.32913 (13) 0.64562 (9) 0.44759 (10) 0.0165 (4)
O2 0.44470 (13) 0.54506 (9) 0.64055 (10) 0.0160 (4)
O3 0.27815 (14) 0.26386 (10) 0.63425 (11) 0.0211 (4)
O4 0.22345 (14) 0.30455 (10) 0.81243 (11) 0.0216 (4)
O5 0.10290 (15) 0.53573 (11) 0.87145 (11) 0.0287 (4)
O6 0.30886 (14) 0.47284 (10) 0.97057 (11) 0.0231 (4)
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
C1 0.0115 (9) 0.0231 (12) 0.0132 (9) 0.0005 (7) 0.0054 (7) 0.0011 (8)
C2 0.0127 (9) 0.0273 (12) 0.0140 (9) 0.0018 (8) 0.0053 (7) 0.0002 (8)
C3 0.0177 (10) 0.0258 (12) 0.0155 (9) 0.0009 (8) 0.0043 (7) 0.0040 (8)
C4 0.0182 (10) 0.0328 (13) 0.0131 (9) −0.0008 (8) 0.0028 (7) 0.0055 (8)
C5 0.0180 (10) 0.0214 (11) 0.0133 (9) −0.0026 (8) 0.0051 (7) −0.0039 (8)
C6 0.0135 (9) 0.0236 (12) 0.0129 (9) −0.0010 (8) 0.0054 (7) −0.0002 (8)
C7 0.0148 (9) 0.0193 (11) 0.0140 (9) 0.0003 (7) 0.0057 (7) −0.0032 (8)
C8 0.0126 (9) 0.0216 (12) 0.0134 (9) 0.0003 (8) 0.0047 (7) 0.0015 (8)
C9 0.0129 (9) 0.0236 (12) 0.0120 (9) −0.0001 (8) 0.0037 (7) 0.0020 (8)
C10 0.0125 (9) 0.0199 (11) 0.0112 (9) 0.0025 (7) 0.0055 (7) −0.0007 (7)
C11 0.0164 (10) 0.0270 (12) 0.0156 (9) −0.0019 (8) 0.0055 (7) −0.0015 (8)
C12 0.0195 (10) 0.0208 (12) 0.0197 (10) −0.0042 (8) 0.0051 (7) −0.0025 (8)
C13 0.0213 (10) 0.0221 (12) 0.0186 (10) 0.0012 (8) 0.0072 (7) −0.0008 (8)
C14 0.0119 (9) 0.0220 (12) 0.0143 (9) 0.0026 (7) 0.0032 (7) 0.0010 (8)
C15 0.0328 (12) 0.0273 (13) 0.0219 (10) −0.0056 (10) 0.0088 (9) 0.0049 (9)
C16 0.0183 (10) 0.0167 (11) 0.0146 (9) −0.0027 (7) 0.0048 (7) −0.0013 (7)
C17 0.0488 (15) 0.0368 (14) 0.0141 (10) 0.0058 (11) 0.0148 (9) 0.0028 (10)
O1 0.0154 (7) 0.0210 (8) 0.0148 (7) −0.0006 (5) 0.0070 (5) −0.0011 (6)
O2 0.0128 (7) 0.0214 (8) 0.0151 (7) −0.0006 (5) 0.0060 (5) −0.0033 (5)
O3 0.0236 (8) 0.0228 (9) 0.0177 (7) 0.0006 (6) 0.0057 (6) −0.0018 (6)
O4 0.0282 (8) 0.0212 (8) 0.0175 (7) −0.0017 (6) 0.0099 (6) 0.0028 (6)
O5 0.0204 (8) 0.0479 (11) 0.0198 (8) 0.0063 (7) 0.0094 (6) −0.0001 (7)
O6 0.0283 (8) 0.0319 (9) 0.0100 (7) 0.0043 (6) 0.0054 (6) 0.0023 (6)
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Geometric parameters (Å, º)

C1—C2 1.558 (3) C10—O2 1.449 (2)
C1—C6 1.558 (3) C10—C11 1.511 (2)
C1—C10 1.568 (2) C11—C12 1.538 (3)
C1—H1 1.0000 C11—H11A 0.9900
C2—O1 1.454 (2) C11—H11B 0.9900
C2—C13 1.509 (3) C12—C13 1.539 (3)
C2—C3 1.536 (3) C12—H12A 0.9900
C3—C4 1.337 (3) C12—H12B 0.9900
C3—H3 0.9500 C13—H13A 0.9900
C4—C5 1.525 (3) C13—H13B 0.9900
C4—H4 0.9500 C14—O3 1.214 (2)
C5—O1 1.453 (2) C14—O4 1.351 (2)
C5—C6 1.567 (2) C15—O4 1.448 (2)
C5—H5 1.0000 C15—H15A 0.9800
C6—C7 1.559 (3) C15—H15B 0.9800
C6—H6 1.0000 C15—H15C 0.9800
C7—O2 1.456 (2) C16—O5 1.215 (2)
C7—C8 1.534 (2) C16—O6 1.331 (2)
C7—H7 1.0000 C17—O6 1.461 (2)
C8—C9 1.343 (3) C17—H17A 0.9800
C8—C14 1.479 (3) C17—H17B 0.9800
C9—C16 1.493 (2) C17—H17C 0.9800
C9—C10 1.549 (3)
C2—C1—C6 102.44 (14) C11—C10—C9 120.61 (15)
C2—C1—C10 112.21 (14) O2—C10—C1 102.48 (13)
C6—C1—C10 102.16 (13) C11—C10—C1 114.30 (14)
C2—C1—H1 113.0 C9—C10—C1 104.17 (14)
C6—C1—H1 113.0 C10—C11—C12 111.59 (15)
C10—C1—H1 113.0 C10—C11—H11A 109.3
O1—C2—C13 112.43 (15) C12—C11—H11A 109.3
O1—C2—C3 100.43 (13) C10—C11—H11B 109.3
C13—C2—C3 120.53 (16) C12—C11—H11B 109.3
O1—C2—C1 101.74 (14) H11A—C11—H11B 108.0
C13—C2—C1 114.14 (15) C11—C12—C13 112.36 (15)
C3—C2—C1 105.17 (14) C11—C12—H12A 109.1
C4—C3—C2 105.69 (16) C13—C12—H12A 109.1
C4—C3—H3 127.2 C11—C12—H12B 109.1
C2—C3—H3 127.2 C13—C12—H12B 109.1
C3—C4—C5 105.73 (17) H12A—C12—H12B 107.9
C3—C4—H4 127.1 C2—C13—C12 111.82 (16)
C5—C4—H4 127.1 C2—C13—H13A 109.3
O1—C5—C4 101.15 (15) C12—C13—H13A 109.3
O1—C5—C6 102.15 (13) C2—C13—H13B 109.3
C4—C5—C6 106.29 (14) C12—C13—H13B 109.3
O1—C5—H5 115.2 H13A—C13—H13B 107.9
C4—C5—H5 115.2 O3—C14—O4 124.10 (17)
C6—C5—H5 115.2 O3—C14—C8 123.61 (16)
C1—C6—C7 100.74 (13) O4—C14—C8 112.28 (15)
C1—C6—C5 100.02 (14) O4—C15—H15A 109.5
C7—C6—C5 116.80 (14) O4—C15—H15B 109.5
C1—C6—H6 112.6 H15A—C15—H15B 109.5
C7—C6—H6 112.6 O4—C15—H15C 109.5
C5—C6—H6 112.6 H15A—C15—H15C 109.5
O2—C7—C8 100.19 (13) H15B—C15—H15C 109.5
O2—C7—C6 102.74 (14) O5—C16—O6 125.93 (17)
C8—C7—C6 105.62 (13) O5—C16—C9 122.01 (16)
O2—C7—H7 115.5 O6—C16—C9 112.01 (15)
C8—C7—H7 115.5 O6—C17—H17A 109.5
C6—C7—H7 115.5 O6—C17—H17B 109.5
C9—C8—C14 130.17 (16) H17A—C17—H17B 109.5
C9—C8—C7 106.03 (16) O6—C17—H17C 109.5
C14—C8—C7 123.00 (15) H17A—C17—H17C 109.5
C8—C9—C16 130.09 (17) H17B—C17—H17C 109.5
C8—C9—C10 105.42 (15) C5—O1—C2 96.38 (13)
C16—C9—C10 123.29 (15) C10—O2—C7 97.18 (12)
O2—C10—C11 113.16 (14) C14—O4—C15 115.69 (15)
O2—C10—C9 99.72 (14) C16—O6—C17 116.06 (15)
C6—C1—C2—O1 −33.60 (15) C16—C9—C10—C1 −96.67 (18)
C10—C1—C2—O1 75.25 (16) C2—C1—C10—O2 −76.85 (16)
C6—C1—C2—C13 −154.94 (14) C6—C1—C10—O2 32.17 (16)
C10—C1—C2—C13 −46.10 (19) C2—C1—C10—C11 45.96 (19)
C6—C1—C2—C3 70.76 (16) C6—C1—C10—C11 154.98 (14)
C10—C1—C2—C3 179.61 (14) C2—C1—C10—C9 179.61 (14)
O1—C2—C3—C4 33.34 (19) C6—C1—C10—C9 −71.37 (16)
C13—C2—C3—C4 157.33 (17) O2—C10—C11—C12 66.21 (19)
C1—C2—C3—C4 −71.98 (18) C9—C10—C11—C12 −176.00 (15)
C2—C3—C4—C5 −0.86 (19) C1—C10—C11—C12 −50.6 (2)
C3—C4—C5—O1 −31.98 (18) C10—C11—C12—C13 55.1 (2)
C3—C4—C5—C6 74.35 (19) O1—C2—C13—C12 −64.1 (2)
C2—C1—C6—C7 118.41 (14) C3—C2—C13—C12 177.84 (15)
C10—C1—C6—C7 2.08 (16) C1—C2—C13—C12 51.2 (2)
C2—C1—C6—C5 −1.57 (15) C11—C12—C13—C2 −55.4 (2)
C10—C1—C6—C5 −117.90 (14) C9—C8—C14—O3 170.32 (18)
O1—C5—C6—C1 36.44 (15) C7—C8—C14—O3 2.1 (3)
C4—C5—C6—C1 −69.17 (17) C9—C8—C14—O4 −8.8 (3)
O1—C5—C6—C7 −71.09 (18) C7—C8—C14—O4 −177.03 (14)
C4—C5—C6—C7 −176.70 (16) C8—C9—C16—O5 −102.8 (2)
C1—C6—C7—O2 −35.69 (15) C10—C9—C16—O5 62.9 (3)
C5—C6—C7—O2 71.42 (17) C8—C9—C16—O6 79.6 (2)
C1—C6—C7—C8 68.87 (17) C10—C9—C16—O6 −114.78 (19)
C5—C6—C7—C8 175.98 (15) C4—C5—O1—C2 51.11 (15)
O2—C7—C8—C9 31.95 (17) C6—C5—O1—C2 −58.46 (15)
C6—C7—C8—C9 −74.48 (17) C13—C2—O1—C5 179.32 (15)
O2—C7—C8—C14 −157.37 (15) C3—C2—O1—C5 −51.27 (15)
C6—C7—C8—C14 96.20 (19) C1—C2—O1—C5 56.79 (14)
C14—C8—C9—C16 −1.3 (3) C11—C10—O2—C7 −178.39 (14)
C7—C8—C9—C16 168.50 (18) C9—C10—O2—C7 52.18 (14)
C14—C8—C9—C10 −168.84 (17) C1—C10—O2—C7 −54.81 (15)
C7—C8—C9—C10 0.92 (17) C8—C7—O2—C10 −51.89 (15)
C8—C9—C10—O2 −33.65 (17) C6—C7—O2—C10 56.83 (14)
C16—C9—C10—O2 157.70 (15) O3—C14—O4—C15 3.6 (3)
C8—C9—C10—C11 −158.04 (16) C8—C14—O4—C15 −177.27 (15)
C16—C9—C10—C11 33.3 (2) O5—C16—O6—C17 6.7 (3)
C8—C9—C10—C1 71.98 (16) C9—C16—O6—C17 −175.75 (15)
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Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A
C5—H5···O2i 1.00 2.58 3.330 (2) 132
C7—H7···O1i 1.00 2.52 3.351 (2) 140
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Symmetry code: (i) −x+1, −y+1, −z+1.

Funding Statement

This work was funded by Russian Science Foundation grant 18–13-00456.

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) 2, Global. DOI: 10.1107/S2056989019003499/rz5253sup1.cif

e-75-00460-sup1.cif (612.2KB, cif)

CCDC reference: 1902671

Additional supporting information: crystallographic information; 3D view; checkCIF report

Articles from Acta Crystallographica Section E: Crystallographic Communications are provided here courtesy of International Union of Crystallography

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