Crystal structure and Hirshfeld surface analysis of 3,4-di­hydro-2H-anthra[1,2-b][1,4]dioxepine-8,13-dione

Zazouli, S.; Chigr, M.; Jouaiti, A.; Kyritsakas, N.; Ketatni, E.M.

doi:10.1107/S2056989020003965

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 76| Part 4| April 2020| Pages 576-580

https://doi.org/10.1107/S2056989020003965

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Crystal structure and Hirshfeld surface analysis of 3,4-dihydro-2H-anthra[1,2-b][1,4]dioxepine-8,13-dione

Sofia Zazouli,^a ^* Mohammed Chigr,^b Ahmed Jouaiti,^a Nathalie Kyritsakas ^c and El Mostafa Ketatni ^b

^aLaboratory of Sustainable Development, Sultan Moulay Slimane University, Faculty of Sciences and Technologies, BP 523, 23000 Beni-Mellal, Morocco, ^bLaboratory of Organic and Analytical Chemistry, University Sultan Moulay Slimane, Faculty of Science and Technology, PO Box 523, Beni-Mellal, Morocco, and ^cMolecular Tectonics Laboratory, Université de Strasbourg, CNRS, CMC UMR 7140, F-67000 Strasbourg, France
^*Correspondence e-mail: szazouli@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 5 March 2020; accepted 18 March 2020; online 27 March 2020)

The title compound, C₁₇H₁₂O₄, was synthesized from the dye alizarin. The dihedral angle between the mean plane of the anthraquinone ring system (r.m.s. deviation = 0.039 Å) and the dioxepine ring is 16.29 (8)°. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds, forming sheets lying parallel to the ab plane. The sheets are connected through π–π and C=O⋯π interactions to generate a three-dimensional supramolecular network. Hirshfeld surface analysis was used to investigate intermolecular interactions in the solid-state: the most important contributions are from H⋯H (43.0%), H⋯O/O⋯H (27%), H⋯C/C⋯H (13.8%) and C⋯C (12.4%) contacts.

Keywords: crystal structure; anthraquinone; dioxepine; Schiff base; Hirshfeld surface analysis.

CCDC reference: 1991271

1. Chemical context

Anthraquinone derivatives, which are extracted from the seeds of the Rubiaceae family of shrubs, include alizarin (1,2-dihydroxyanthraquinone; C₁₄H₈O₄) and other polycyclic aromatic hydrocarbons. The colour of anthraquinone-based compounds can be modified by the type and position of the substituents attached to the anthraquinone nucleus (Nakagawa et al. 2017 ; Cheuk et al., 2015 ; Tonin et al., 2017 ). Besides their application as pigments or dyes in textile, photographic, cosmetic and other industries (Wang et al., 2011 ), anthraquinone derivatives have been used for centuries for medical applications, for example, as laxatives (Oshio et al., 1985 ), antioxidants (Yen et al., 2000 ), antimicrobial (Xiang et al., 2008 ; Yadav et al., 2010 ) and anitiviral (Alves et al., 2004 ) agents. Their redox properties and cytotoxicity have been investigated recently (Okumura et al., 2019 ). Anthraquinone derivatives exhibit various applications in supramolecular and electro-analytical chemistry (Czupryniak et al., 2012 ).

As part of our studies in this area, the synthesis and structure of the title compound, (I), are described along with a detailed analysis of its supramolecular associations through an analysis of the Hirshfeld surfaces.

2. Structural commentary

Compound (I) crystallizes in space group P2₁/n with one molecule in the asymmetric unit: it consists of three fused six-membered rings and one seven-membered ring as shown in Fig. 1. The fused-ring system is close to planar with an r.m.s. deviation for all non-hydrogen atoms of 0.039 Å (the dihedral angle between the aromatic rings of the anthraquinone unit and the central ring range from 1.5 to 1.9°). The dioxepine ring is inclined to the mean plane of the anthraquinone ring system by 16.29 (8)°.

Figure 1
The molecular structure of (I)

with displacement ellipsoids drawn at the 50% probability level.

A puckering analysis of the seven-membered ring yielded the parameters q2 = 0.896 (2) Å, φ₂ = 113.50 (12)°, q₃ = 0.358 (2) Å, and φ₃ = 217.8 (3)°. These metrics indicate that the ring adopts a screw boat conformation. The C—O and C=O bond lengths lie within the ranges 1.355 (2)–1.457 (2) Å and 1.216 (2)–1.226 (2) Å, respectively, confirming their single and double-bond character.

3. Supramolecular features

In the extended structure of (I), C15—H15B⋯O1 hydrogen bonds form inversion dimers with an R₂²(14) ring motif. Adjacent dimers are linked by C15—H15A⋯O3 contacts, thereby generating corrugated chains of molecules (Fig. 2a). A C17—H17B⋯O2 hydrogen bond links the chains together (Table 1; Fig. 2b and 2c), forming sheets propagating in the ab plane. These sheets are supported by extensive π–π contacts between adjacent rings, with centroid-to-centroid distances Cg1⋯Cg2 = 3.599 (2) and Cg2⋯Cg3 = 3.683 (2) Å [Cg1, Cg2 and Cg3 are the centroids of the rings C1–C4/C13–C14, C4–C6/C11–C13 and C6–C11, respectively] and weak C12=O1⋯π [oxygen–centroid distance = 3.734 (2) Å] interactions (Fig. 3), linking the slabs to form a three-dimensional supramolecular network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C15—H15B⋯O1ⁱ	0.99	2.43	3.248 (2)	139
C15—H15A⋯O3ⁱⁱ	0.99	2.48	3.461 (3)	171
C17—H17A⋯O4ⁱⁱⁱ	0.99	2.59	3.580 (3)	174
Symmetry codes: (i) -x, -y+1, -z+1; (ii) x+1, y, z; (iii) x-1, y, z.

Figure 2
(a) Inversion dimers with R₂²(14) ring motifs; (b) and (c) packing diagrams of the title compound, viewed along the a and b axes, respectively. Dotted lines indicate C—H⋯O hydrogen bonds.

Figure 3
Partial crystal packing for (I)

showing the C—H⋯O hydrogen bonds and the offset π–π (purple) and C=O⋯π (green) interactions between inversion-related molecules.

4. Database survey

A search in the Cambridge Structural Database (CSD, Version 5.40, updated to February 2020; Groom et al., 2016 ) revealed 55 alizarin-ring motifs incorporated in more complex molecules or bearing functional groups. These include several compounds with a different substituent in place of the dioxepine in the title compound, viz. 1-hydroxy-2-methoxy-6-methyl (BOTXUE; Ismail et al., 2009 ), 1,2-dimethoxy (refcode: KIBHUZ; Kar et al., 2007 ) and 3-hydroxy-1,2-dimethoxy (BOVVEO; Xu et al., 2009 ). In these compounds, the anthraquinone ring system are almost planar, the dihedral angle between the benzene rings for BOTXUE, KIBHUZ and BOVVEO being 3.49, 2.83 and 1.12°, respectively. The methoxy groups in position 1 (C14) in KIBHUZ and BOVVEO are almost perpendicular to the anthraquinone ring plane. The other compound belongs to the same class of alizarins with different substituents.

5. Hirshfeld surface analysis

The nature of the intermolecular interactions in (I) have been examined with CrystalExplorer17.5 (Turner et al., 2017 ), using Hirshfeld surface analysis (Spackman & Jayatilaka, 2009 ) mapped over d_norm, with a fixed colour scale of −0.1779 to 1.3612 a.u (see Fig. S1a in the supporting information) and two-dimensional fingerprint plots (McKinnon et al., 2007 ). The intense red spots on the surface are due to the C—H⋯O hydrogen bonds (Fig. 4). Fig. S2 (supporting information) shows the molecular electrostatic potential surface generated using TONTO with a STO-3G basis set in the range −0.050 to 0.050 a.u. within the Hartree–Fock level of theory. Molecular sites evidenced in red correspond to positive potential energy and in blue to negative potential energy (Spackman et al., 2008 ).

Figure 4
Views of the Hirshfeld surface for (I)

mapped over (a) d_norm showing the C—H⋯O contacts as green dashed lines and short C⋯H/H⋯C contacts as cyan dashed lines; and (b) shape-index highlighting the π–π stacking (black lines).

As illustrated in Fig. 5, the overall fingerprint plot for (I) and those delineated into H⋯H, H⋯O/O⋯H, C⋯H/H⋯C and C⋯C show characteristic pseudo-symmetric wings in the d_e and d_i diagonal axes. The most important interaction is H⋯H, contributing 43% to the overall crystal packing, which is reflected in Fig. 5b as widely scattered points of high density due to the large hydrogen content of the molecule, with small split tips at d_e ≃ d_i ≃ 1.2 Å. The contribution from the O⋯H/H⋯O contacts (27%) [note that the O⋯H interactions make a larger contribution (14.6%) than the H⋯O interactions (12.4%)], corresponding to C—H⋯O interactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond interaction, d_e + d_i ≃ 2.35 Å (Fig. 5c). The significant contribution from C⋯H/H⋯C contacts (13.8%) to the Hirshfeld surface of (I) reflect the short C⋯H/H⋯C contacts, and the distribution of points has characteristic wings, Fig. 5d, with d_e + d_i ≃2.55 Å. The distribution of points in the d_e = d_i ≃ 1.75 Å range in the fingerprint plot delineated into C⋯C contacts indicates the existence of weak π–π stacking interactions between the central anthracene ring and the C6–C11 and C1–C4/C13–C14 rings (Fig. 4b and 5e). Aromatic π–π interactions are indicated by adjacent red and blue triangles in the shape-index map (Fig. S1b)and also by the flat region around these rings in the Hirshfeld surfaces mapped over curvedness in Fig. S1c.

Figure 5
The full two-dimensional fingerprint plots for (I)

showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯C/C⋯H, (e) C⋯C and (f) O⋯C/C⋯O interactions.

The contribution of 3.2% from C⋯O/O⋯C contacts is due to the presence of short interatomic C=O⋯π contacts, and is apparent as the pair of parabolic tips at d_e + d_i ≃ 3.2 Å in Fig. 5f.

6. Synthesis and crystallization

Under argon, alizarin (0.50 g, 2.0 mmol) was treated with 1,3-dibromo-propane (0.42 g, 2.0 mmol) in dimethylformamide (30 ml) in the presence of anhydrous potassium carbonate (1.0 g, 7.2 mmol) with stirring and heated to 393 K for 24 h. The reaction mixture was evaporated to dryness under vacuum and the resulting crude product was acidified with 12 N hydrochloric acid, extracted with chloroform (3 × 30 ml) and then chromatographed on a silica gel column with dichloromethane/petroleum ether (1/1) as eluent, which yielded 200 mg (35%) of 1,2-propylenedioxyanthraquinone as a yellow compound (Fig. 6). Colourless needles were obtained by slow evaporation of a dichloromethane/petroleum ether (1:1) solution.

Figure 6
Synthesis pathway leading to the formation of the title compound.

¹H NMR (CDCl₃, 500 MHz): δ (ppm): 8.21 (m, 2H), 7.95 (d, J = 8.5 Hz, 1H), 7.72 (m, 2H), 7.26 (d, J = 8.5 Hz, 1H), 4.48 (t, J = 6 Hz, 2H), 4.43 (t, J = 6 Hz, 2H), 2.34 (qt, J = 6 Hz, 2H); ¹³C NMR (CDCl₃, 126 MHz): δ (ppm): 182.9, 182.5, 157.3, 151.3, 135.2, 133.9, 133.4, 132.6, 129.6, 127.1, 126.5, 126.0, 125.9, 123.3, 70.5, 70.2, 30.0. Analysis calculated for C₁₇H₁₂O₄: C, 72.85%; H, 4.32%; found: C, 72.82%; H, 4.29%.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms were placed in calculated positions and refined in the riding model: C—H = 0.95–0.99 Å with U_iso(H) = 1.2U_eq(C). The reflection (011), affected by the beam-stop, was removed during refinement.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₂O₄
M_r	280.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	4.2951 (2), 16.7714 (9), 18.0537 (11)
β (°)	95.941 (2)
V (Å³)	1293.51 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.12 × 0.10 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.988, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	19692, 3436, 2309
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.697

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.149, 1.03
No. of reflections	3436
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg et al., 2012 ), PLATON (Spek, 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1991271

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989020003965/hb7899sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020003965/hb7899Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989020003965/hb7899Isup3.cml

Supplementary figures: Hirshfeld surface analysis. DOI: https://doi.org/10.1107/S2056989020003965/hb7899sup4.docx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg et al., 2012); software used to prepare material for publication: PLATON (Spek, 2020) and publCIF (Westrip, 2010).

3,4-Dihydro-2H-anthra[1,2-b][1,4]dioxepine-8,13-dione top

Crystal data top

C₁₇H₁₂O₄	F(000) = 584
M_r = 280.27	D_x = 1.439 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.2951 (2) Å	Cell parameters from 3436 reflections
b = 16.7714 (9) Å	θ = 2.4–29.7°
c = 18.0537 (11) Å	µ = 0.10 mm⁻¹
β = 95.941 (2)°	T = 173 K
V = 1293.51 (12) Å³	Prism, colorless
Z = 4	0.12 × 0.10 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	2309 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.044
Absorption correction: multi-scan (SADABS; Bruker, 2012)	θ_max = 29.7°, θ_min = 2.4°
T_min = 0.988, T_max = 0.990	h = −5→4
19692 measured reflections	k = −23→23
3436 independent reflections	l = −24→25

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.055	H-atom parameters constrained
wR(F²) = 0.149	w = 1/[σ²(F_o²) + (0.0548P)² + 0.8849P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
3436 reflections	Δρ_max = 0.41 e Å⁻³
190 parameters	Δρ_min = −0.32 e Å⁻³
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	−0.2635 (5)	0.49906 (10)	0.64736 (8)	0.0546 (5)
O2	0.1717 (4)	0.34277 (9)	0.89646 (7)	0.0449 (4)
O3	0.0471 (3)	0.40325 (8)	0.56747 (6)	0.0293 (3)
O4	0.4204 (4)	0.25897 (8)	0.56830 (7)	0.0356 (3)
C1	0.3367 (5)	0.29496 (11)	0.63141 (10)	0.0274 (4)
C2	0.4523 (5)	0.26018 (11)	0.69817 (11)	0.0321 (4)
H2	0.590316	0.215932	0.697909	0.038*
C3	0.3704 (5)	0.28874 (11)	0.76486 (10)	0.0302 (4)
H3	0.451085	0.264092	0.810209	0.036*
C4	0.1701 (4)	0.35347 (10)	0.76600 (9)	0.0244 (4)
C5	0.0822 (5)	0.37964 (11)	0.83960 (10)	0.0285 (4)
C6	−0.1143 (5)	0.45162 (10)	0.84226 (9)	0.0269 (4)
C7	−0.1904 (5)	0.47948 (12)	0.91105 (10)	0.0351 (5)
H7	−0.121046	0.451264	0.955331	0.042*
C8	−0.3662 (6)	0.54788 (13)	0.91472 (11)	0.0407 (5)
H8	−0.413992	0.567394	0.961621	0.049*
C9	−0.4731 (5)	0.58819 (12)	0.85004 (11)	0.0377 (5)
H9	−0.595642	0.635045	0.852781	0.045*
C10	−0.4023 (5)	0.56056 (11)	0.78134 (11)	0.0308 (4)
H10	−0.478159	0.588130	0.737151	0.037*
C11	−0.2198 (4)	0.49227 (10)	0.77718 (9)	0.0248 (4)
C12	−0.1467 (5)	0.46397 (10)	0.70231 (9)	0.0271 (4)
C13	0.0595 (4)	0.39292 (10)	0.69919 (9)	0.0227 (4)
C14	0.1495 (4)	0.36425 (10)	0.63107 (9)	0.0238 (4)
C15	0.2543 (5)	0.40456 (12)	0.50847 (10)	0.0331 (4)
H15A	0.474823	0.405280	0.530766	0.040*
H15B	0.216063	0.453607	0.478396	0.040*
C16	0.1997 (6)	0.33217 (13)	0.45871 (11)	0.0389 (5)
H16A	0.001584	0.338786	0.426047	0.047*
H16B	0.372274	0.327239	0.426649	0.047*
C17	0.1829 (6)	0.25735 (13)	0.50493 (11)	0.0384 (5)
H17A	−0.026930	0.253140	0.522692	0.046*
H17B	0.214839	0.210027	0.473818	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0835 (14)	0.0550 (10)	0.0254 (7)	0.0370 (9)	0.0062 (8)	0.0053 (6)
O2	0.0590 (12)	0.0499 (9)	0.0257 (7)	0.0106 (8)	0.0036 (7)	0.0110 (6)
O3	0.0301 (8)	0.0378 (7)	0.0201 (6)	0.0062 (6)	0.0029 (5)	0.0009 (5)
O4	0.0345 (9)	0.0386 (8)	0.0346 (7)	0.0062 (6)	0.0078 (6)	−0.0075 (6)
C1	0.0248 (10)	0.0272 (9)	0.0307 (9)	−0.0022 (7)	0.0053 (7)	−0.0040 (7)
C2	0.0296 (11)	0.0267 (9)	0.0394 (10)	0.0036 (7)	0.0010 (8)	0.0015 (7)
C3	0.0297 (11)	0.0283 (9)	0.0313 (9)	0.0005 (7)	−0.0030 (8)	0.0054 (7)
C4	0.0245 (10)	0.0230 (8)	0.0252 (8)	−0.0033 (7)	0.0002 (7)	0.0022 (6)
C5	0.0314 (11)	0.0298 (9)	0.0237 (8)	−0.0042 (7)	0.0002 (7)	0.0022 (7)
C6	0.0309 (11)	0.0278 (8)	0.0220 (8)	−0.0070 (7)	0.0025 (7)	−0.0014 (6)
C7	0.0445 (14)	0.0376 (10)	0.0238 (9)	−0.0053 (9)	0.0064 (8)	−0.0010 (7)
C8	0.0538 (16)	0.0407 (11)	0.0295 (10)	−0.0035 (10)	0.0143 (9)	−0.0078 (8)
C9	0.0429 (14)	0.0317 (10)	0.0402 (11)	0.0007 (9)	0.0126 (9)	−0.0054 (8)
C10	0.0342 (12)	0.0264 (9)	0.0322 (9)	−0.0008 (7)	0.0054 (8)	−0.0002 (7)
C11	0.0274 (10)	0.0233 (8)	0.0239 (8)	−0.0051 (7)	0.0027 (7)	−0.0011 (6)
C12	0.0304 (11)	0.0274 (9)	0.0234 (8)	0.0015 (7)	0.0015 (7)	0.0006 (6)
C13	0.0233 (10)	0.0213 (8)	0.0231 (8)	−0.0039 (6)	0.0010 (6)	0.0006 (6)
C14	0.0218 (10)	0.0255 (8)	0.0236 (8)	−0.0033 (7)	0.0005 (7)	−0.0003 (6)
C15	0.0353 (12)	0.0407 (11)	0.0246 (9)	0.0002 (8)	0.0085 (8)	0.0014 (7)
C16	0.0396 (14)	0.0525 (12)	0.0256 (9)	0.0027 (10)	0.0080 (8)	−0.0079 (8)
C17	0.0376 (13)	0.0428 (11)	0.0357 (10)	−0.0027 (9)	0.0078 (9)	−0.0145 (8)

Geometric parameters (Å, º) top

O1—C12	1.216 (2)	C7—H7	0.9500
O2—C5	1.226 (2)	C8—C9	1.386 (3)
O3—C14	1.355 (2)	C8—H8	0.9500
O3—C15	1.457 (2)	C9—C10	1.387 (3)
O4—C1	1.370 (2)	C9—H9	0.9500
O4—C17	1.452 (3)	C10—C11	1.394 (3)
C1—C2	1.384 (3)	C10—H10	0.9500
C1—C14	1.413 (3)	C11—C12	1.496 (2)
C2—C3	1.375 (3)	C12—C13	1.489 (2)
C2—H2	0.9500	C13—C14	1.411 (2)
C3—C4	1.387 (3)	C15—C16	1.514 (3)
C3—H3	0.9500	C15—H15A	0.9900
C4—C13	1.414 (2)	C15—H15B	0.9900
C4—C5	1.485 (2)	C16—C17	1.513 (3)
C5—C6	1.477 (3)	C16—H16A	0.9900
C6—C11	1.393 (2)	C16—H16B	0.9900
C6—C7	1.397 (2)	C17—H17A	0.9900
C7—C8	1.379 (3)	C17—H17B	0.9900

C14—O3—C15	117.23 (15)	C11—C10—H10	120.0
C1—O4—C17	116.12 (16)	C6—C11—C10	119.49 (16)
O4—C1—C2	115.92 (17)	C6—C11—C12	121.76 (16)
O4—C1—C14	123.85 (16)	C10—C11—C12	118.75 (15)
C2—C1—C14	120.22 (16)	O1—C12—C13	123.57 (16)
C3—C2—C1	120.95 (18)	O1—C12—C11	118.43 (17)
C3—C2—H2	119.5	C13—C12—C11	117.99 (14)
C1—C2—H2	119.5	C14—C13—C4	119.06 (16)
C2—C3—C4	120.08 (17)	C14—C13—C12	121.55 (15)
C2—C3—H3	120.0	C4—C13—C12	119.39 (15)
C4—C3—H3	120.0	O3—C14—C13	118.68 (15)
C3—C4—C13	120.52 (16)	O3—C14—C1	122.38 (15)
C3—C4—C5	117.40 (15)	C13—C14—C1	118.92 (15)
C13—C4—C5	122.07 (16)	O3—C15—C16	110.66 (16)
O2—C5—C6	121.06 (17)	O3—C15—H15A	109.5
O2—C5—C4	120.92 (18)	C16—C15—H15A	109.5
C6—C5—C4	118.02 (15)	O3—C15—H15B	109.5
C11—C6—C7	120.04 (18)	C16—C15—H15B	109.5
C11—C6—C5	120.65 (16)	H15A—C15—H15B	108.1
C7—C6—C5	119.31 (16)	C17—C16—C15	110.55 (16)
C8—C7—C6	120.04 (18)	C17—C16—H16A	109.5
C8—C7—H7	120.0	C15—C16—H16A	109.5
C6—C7—H7	120.0	C17—C16—H16B	109.5
C7—C8—C9	120.06 (18)	C15—C16—H16B	109.5
C7—C8—H8	120.0	H16A—C16—H16B	108.1
C9—C8—H8	120.0	O4—C17—C16	110.46 (18)
C8—C9—C10	120.42 (19)	O4—C17—H17A	109.6
C8—C9—H9	119.8	C16—C17—H17A	109.6
C10—C9—H9	119.8	O4—C17—H17B	109.6
C9—C10—C11	119.94 (18)	C16—C17—H17B	109.6
C9—C10—H10	120.0	H17A—C17—H17B	108.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C15—H15B···O1ⁱ	0.99	2.43	3.248 (2)	139
C15—H15A···O3ⁱⁱ	0.99	2.48	3.461 (3)	171
C17—H17A···O4ⁱⁱⁱ	0.99	2.59	3.580 (3)	174

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

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