Trimethyl 4,4′,4′′-(ethene-1,1,2-tri­yl)tribenzoate

Lesley, M.J.G.; Ozhan, K.; Sung, H.H.-Y.; Williams, I.D.

doi:10.1107/S2414314620004174

organic compounds

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ISSN: 2414-3146

Volume 5| Part 3| March 2020| x200417

https://doi.org/10.1107/S2414314620004174

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Trimethyl 4,4′,4′′-(ethene-1,1,2-triyl)tribenzoate

Melvin J. G. Lesley,^a ^* Koray Ozhan,^a ‡ Herman H.-Y. Sung ^b and Ian D. Williams ^b

^aDepartment of Chemistry, Southern Connecticut State University, 501 Crescent, Street, New Haven, CT, 06515-1355, USA, and ^bDepartment of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong
^*Correspondence e-mail: lesleym1@southernct.edu

Edited by M. Zeller, Purdue University, USA (Received 21 February 2020; accepted 26 March 2020; online 31 March 2020)

The title compound, C₂₆H₂₂O₆, is formed as the major product from the reaction between syn-1,2-bis(pinacolatoboron)-1,2-bis(4-methylcarboxyphenyl)ethene and excess methyl 4-iodobenzoate in basic DMSO using a palladium catalyst at 80°C via Suzuki coupling followed by protodeboronation. Crystals were grown by slow evaporation of a hexanes solution at room temperature.

Keywords: crystal structure; protodeboronation; Suzuki coupling.

CCDC reference: 1984328

Structure description

Protodeboronation is a well-known side reaction resulting in the replacement of boryl groups with hydrogen (Lee & Cheon, 2016 ). Initial studies of reductive deboronation have been reported for alkene (Brown & Murray, 1959 , 1986 ) and alkyne (Brown & Zweifel, 1961 ; Zweifel et al., 1971 ) derivatives under acidic conditions as an alternative method to the hydrogenation of π-bonds. More recent studies have focused on the beneficial outcomes of protodeboronation for the control of regioselectivity in reactions with arylboronic acid or arylboronate ester derivatives and heteroatomic ring structures utilizing both acidic (Beckett et al., 1993 ; Kuivila & Nahabedian, 1961 ; Nahabedian & Kuivila, 1961 ) and basic (Lozada et al., 2014 ) reaction conditions. Protodeboronation has also been reported for reactions involving metal catalysis employing copper (Liu et al., 2014 ), gold (Barker et al., 2015 ) and palladium (Lai et al., 2006 ; Brown & Armstrong, 1996 ). The palladium-catalyzed Suzuki coupling reaction (Lennox & Lloyd-Jones, 2014 ; Suzuki, 2011 ; Miyaura & Suzuki, 1995 ) commonly employs basic conditions in hygroscopic solvents such as DMSO and DMF in addition to water for the dissolution of the base. These reactions are therefore prone to protodeboronation especially when elevated temperatures are employed. The title compound, (I), was the major product isolated in the attempted synthesis of 1,1′,2,2′-tetrakis(4-methylcarboxyphenyl)ethene via the Pd-catalyzed double Suzuki coupling reaction (Ishiyama et al., 1993 ; Ishiyama, Yamamoto et al., 1996 ) between syn-1,2-bis(pinacolatoboron)-1,2-bis(4-methylcarboxyphenyl)ethene (Ishiyama, Matsuda et al., 1996 ) and methyl 4-iodobenzoate. The molecular structure of (I) is shown in Fig. 1.

Figure 1
A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 40% probability level.

The title compound (I) contains four molecules in the unit cell. The three methyl 4-carboxyphenyl rings 1 (C11–C16), 2 (C21–C26), and 3 (C31–C36) form dihedral angles of 23.37 (6), 65.95 (4), and 33.72 (7)°, respectively, with the plane including the alkene vector (C10/C11) made up from the atoms C1, C10, C11, C21 and C31. The angles between the methoxy groups and the phenyl rings were calculated and indicate the groups are close to coplanar with angles of 6.3 (1)° for the mean planes defined by (C11–C16) and (C17, O2, C18); 12.5 (1)° for the mean planes defined by (C21–C26) and (C27, O4, C28); and 6.7 (2)° for the mean planes defined by (C31–C36) and (C37, O6, C38). The bond lengths and angles conform to typical value ranges (Allen et al., 1987 ). There are a number of short C—O⋯H—C intermolecular interactions (Table 1) observed in the crystal packing as shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10⋯O5ⁱ	0.95	2.51	3.4082 (18)	159
C18—H18B⋯O4ⁱⁱ	0.98	2.72	3.5520 (19)	144
C28—H28C⋯O6ⁱⁱⁱ	0.98	2.85	3.769 (2)	156
C38—H38A⋯O1^iv	0.98	2.79	3.275 (2)	111
C38—H38B⋯O3^v	0.98	2.57	3.339 (2)	135
C38—H38C⋯O2^vi	0.98	2.66	3.595 (2)	159
Symmetry codes: (i) -x, -y+1, -z; (ii) $[-x+3, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (v) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vi) -x+1, -y+1, -z.

Figure 2
A view of the packing diagram showing short C—O⋯H—C intermolecular interactions.

Synthesis and crystallization

A 100-ml Schlenk flask was equipped with a magnetic stir bar and charged with syn-1,2-bis(pinacolatoboron)-1,2-bis(4-methylcarboxyphenyl)ethene (3.710 g, 6.77 mmol), methyl 4-iodobenzoate (3.723 g, 14.2 mmol), Pd₂(dba)₃ (0.155 g, 2.5 mol%), and P(o-tolyl)₃ (0.108 g, 5.25 mol%). The reaction flask was evacuated for a period of 30 minutes and placed under a dry N₂ (g) atmosphere. An aqueous solution of degassed K₂CO₃ (2.42 ml, 7 M, 2.5 equiv.) was added via syringe followed by the addition of degassed DME (50 ml). A condenser was attached and the reaction was heated to reflux under an N₂ atmosphere for 24 h. The reaction mixture was cooled to room temperature and water and diethyl ether were added. The orange ether layer was isolated and dried in vacuo. Recrystallization from ether/hexanes gave a white precipitate that was isolated by filtration and washed with hexane (2 × 10 ml) yielding a white solid (2.345 g, 81%; m.p. 397 K). The hexane layers were combined and slow evaporation in air gave a crop of colorless crystals of (I). Analytical data for C₂₆H₂₂O₆; calculated (found): %C: 72.55 (71.28); %H: 5.15 (5.16); HRMS (EI: m + 1⁺) calculated (found): 431.142 (431.149); ¹H NMR (300 MHz, CDCl₃): 8.01 (d, J = 7.8 Hz, 2H, Ar—H), 7.99 (d, J = 7.8 Hz, 2H, Ar—H), 7.81 (d, J = 6.3 Hz, 2H, Ar—H), 7.36 (d, J = 7.8 Hz, 2H, Ar—H), 7.25 (d, J = 7.8 Hz, 2H, Ar—H), 7.12 (s, 1H, =CH), 7.07 (d, J = 6.3 Hz, 2H, Ar—H), 3.94 (s, 3H, OCH₃), 3.93 (s, 3H, OCH₃), 3.88 (s, 3H, OCH₃); ¹³C{¹H} (75 MHz, CDCl₃): 166.71(1 C, C=O), 166.70 (1 C, C=O), 166.64 (1 C, C=O), 146.6 (1 C, C₄—Ar), 144.1 (1 C, C₄—Ar), 143.0 (1 C, C₄—Ar), 141.0 (1 C, Ph(Ph)—C=), 130.4 (2 C, Ar—C—H), 130.1 (2 C, Ar—C—H), 129.8 (1 C, C₁—Ar), 129.7 (overlapped 2 C, Ar—C—H and 1 C, =CH), 129.6 (1 C, C₁—Ar), 129.5 (2 C, Ar—C–-H) 129.4 (2 C, Ar—C—H), 128.8 (1 C, C₁—Ar), 127.6 (2 C, Ar—C—H), 52.22 (1 C, OCH₃), 52.18 (1 C, OCH₃), 52.08 (1 C, OCH₃).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂₆H₂₂O₆
M_r	430.43
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.1631 (6), 19.253 (2), 18.0743 (19)
β (°)	96.830 (1)
V (Å³)	2129.5 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.4 × 0.12 × 0.06

Data collection
Diffractometer	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.964, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	19788, 5132, 4358
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.125, 1.02
No. of reflections	5132
No. of parameters	292
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.23
Computer programs: SMART and SAINT (Bruker, 2006 ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1984328

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314620004174/zl4040sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620004174/zl4040Isup2.hkl

checkCIF report

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Trimethyl 4,4',4''-(ethene-1,1,2-triyl)tribenzoate top

Crystal data top

C₂₆H₂₂O₆	F(000) = 904
M_r = 430.43	D_x = 1.343 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.1631 (6) Å	Cell parameters from 6842 reflections
b = 19.253 (2) Å	θ = 2.3–28.2°
c = 18.0743 (19) Å	µ = 0.10 mm⁻¹
β = 96.830 (1)°	T = 100 K
V = 2129.5 (4) Å³	Needle, colourless
Z = 4	0.4 × 0.12 × 0.06 mm

Data collection top

Bruker SMART APEX CCD area detector diffractometer	4358 reflections with I > 2σ(I)
ω and φ scans	R_int = 0.021
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 28.3°, θ_min = 1.6°
T_min = 0.964, T_max = 1.00	h = −8→7
19788 measured reflections	k = −25→25
5132 independent reflections	l = −24→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.048	H-atom parameters constrained
wR(F²) = 0.125	w = 1/[σ²(F_o²) + (0.0603P)² + 1.2194P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
5132 reflections	Δρ_max = 0.42 e Å⁻³
292 parameters	Δρ_min = −0.23 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.

Refinement. Hydrogen atoms were placed geometrically and treated with riding constraints and thermal parameters derived from the C atoms to which they were attached. All –CH and CH₂ groups had H—U_iso fixed at 1.2 times the C atom. Methyls were idealized as freely rotating CH₃ groups with H—U_iso fixed at 1.5 times that of the C atom.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	1.4240 (2)	0.76631 (7)	0.24887 (7)	0.0368 (3)
O2	1.39707 (17)	0.77704 (6)	0.12488 (6)	0.0271 (2)
O3	0.73744 (19)	0.41585 (6)	0.52402 (6)	0.0316 (3)
O4	1.06230 (17)	0.40164 (6)	0.48215 (6)	0.0276 (2)
O5	−0.37892 (18)	0.37535 (6)	0.03473 (6)	0.0307 (3)
O6	−0.20613 (18)	0.28543 (6)	0.09445 (6)	0.0286 (3)
C1	0.5152 (2)	0.52320 (7)	0.18403 (8)	0.0195 (3)
C10	0.5799 (2)	0.57397 (7)	0.14079 (8)	0.0209 (3)
H10	0.4962	0.5785	0.0934	0.025*
C11	0.7611 (2)	0.62360 (7)	0.15587 (8)	0.0204 (3)
C12	0.8586 (2)	0.64214 (8)	0.22724 (8)	0.0251 (3)
H12	0.7998	0.6249	0.2699	0.030*
C13	1.0391 (2)	0.68521 (8)	0.23623 (9)	0.0260 (3)
H13	1.1035	0.6972	0.2849	0.031*
C14	1.1273 (2)	0.71115 (7)	0.17448 (8)	0.0219 (3)
C15	1.0257 (2)	0.69628 (7)	0.10334 (8)	0.0216 (3)
H15	1.0810	0.7155	0.0609	0.026*
C16	0.8438 (2)	0.65346 (7)	0.09441 (8)	0.0215 (3)
H16	0.7739	0.6442	0.0457	0.026*
C17	1.3300 (2)	0.75414 (8)	0.18812 (9)	0.0236 (3)
C18	1.5992 (2)	0.81570 (8)	0.13491 (10)	0.0286 (3)
H18A	1.5806	0.8571	0.1650	0.043*
H18B	1.6390	0.8297	0.0862	0.043*
H18C	1.7152	0.7865	0.1604	0.043*
C21	0.6187 (2)	0.50418 (7)	0.26047 (8)	0.0189 (3)
C22	0.4967 (2)	0.51013 (7)	0.32031 (8)	0.0201 (3)
H22	0.3573	0.5318	0.3132	0.024*
C23	0.5766 (2)	0.48481 (7)	0.39003 (8)	0.0204 (3)
H23	0.4915	0.4888	0.4303	0.024*
C24	0.7814 (2)	0.45347 (7)	0.40100 (8)	0.0189 (3)
C25	0.9079 (2)	0.44951 (8)	0.34232 (8)	0.0212 (3)
H25	1.0498	0.4296	0.3501	0.025*
C26	0.8270 (2)	0.47469 (8)	0.27240 (8)	0.0220 (3)
H26	0.9139	0.4718	0.2325	0.026*
C27	0.8533 (2)	0.42235 (7)	0.47540 (8)	0.0216 (3)
C28	1.1394 (3)	0.36749 (9)	0.55144 (9)	0.0318 (4)
H28A	1.0950	0.3944	0.5932	0.048*
H28B	1.2992	0.3642	0.5564	0.048*
H28C	1.0765	0.3208	0.5518	0.048*
C31	0.3270 (2)	0.47814 (7)	0.15514 (8)	0.0188 (3)
C32	0.3224 (2)	0.40802 (8)	0.17503 (8)	0.0207 (3)
H32	0.4409	0.3891	0.2072	0.025*
C33	0.1488 (2)	0.36576 (7)	0.14883 (8)	0.0216 (3)
H33	0.1491	0.3181	0.1626	0.026*
C34	−0.0268 (2)	0.39329 (7)	0.10213 (8)	0.0200 (3)
C35	−0.0243 (2)	0.46303 (8)	0.08209 (8)	0.0210 (3)
H35	−0.1436	0.4820	0.0504	0.025*
C36	0.1507 (2)	0.50481 (7)	0.10801 (8)	0.0205 (3)
H36	0.1510	0.5523	0.0936	0.025*
C37	−0.2229 (2)	0.35197 (8)	0.07316 (8)	0.0220 (3)
C38	−0.3997 (3)	0.24411 (9)	0.07264 (10)	0.0312 (4)
H38A	−0.5224	0.2627	0.0964	0.047*
H38B	−0.3724	0.1959	0.0884	0.047*
H38C	−0.4353	0.2458	0.0184	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0355 (6)	0.0451 (7)	0.0285 (6)	−0.0181 (5)	−0.0013 (5)	−0.0022 (5)
O2	0.0243 (5)	0.0288 (6)	0.0287 (6)	−0.0083 (4)	0.0056 (4)	−0.0029 (4)
O3	0.0357 (6)	0.0374 (6)	0.0231 (6)	0.0127 (5)	0.0088 (5)	0.0084 (5)
O4	0.0238 (5)	0.0371 (6)	0.0208 (5)	0.0077 (4)	−0.0018 (4)	0.0055 (4)
O5	0.0261 (6)	0.0356 (6)	0.0282 (6)	−0.0044 (5)	−0.0060 (5)	0.0026 (5)
O6	0.0270 (5)	0.0254 (5)	0.0320 (6)	−0.0065 (4)	−0.0029 (4)	−0.0014 (4)
C1	0.0184 (6)	0.0222 (7)	0.0178 (7)	0.0020 (5)	0.0010 (5)	−0.0010 (5)
C10	0.0200 (6)	0.0237 (7)	0.0184 (7)	0.0007 (5)	0.0000 (5)	−0.0005 (5)
C11	0.0176 (6)	0.0192 (7)	0.0241 (7)	0.0010 (5)	0.0015 (5)	0.0003 (5)
C12	0.0288 (7)	0.0271 (7)	0.0197 (7)	−0.0048 (6)	0.0042 (6)	0.0022 (6)
C13	0.0277 (7)	0.0282 (8)	0.0208 (7)	−0.0037 (6)	−0.0022 (6)	−0.0006 (6)
C14	0.0203 (6)	0.0190 (6)	0.0265 (7)	−0.0008 (5)	0.0026 (5)	−0.0009 (5)
C15	0.0229 (7)	0.0206 (7)	0.0220 (7)	0.0003 (5)	0.0050 (5)	0.0021 (5)
C16	0.0235 (7)	0.0211 (7)	0.0192 (7)	0.0016 (5)	−0.0011 (5)	−0.0009 (5)
C17	0.0241 (7)	0.0210 (7)	0.0254 (7)	−0.0014 (5)	0.0014 (6)	−0.0018 (6)
C18	0.0229 (7)	0.0262 (8)	0.0373 (9)	−0.0079 (6)	0.0067 (6)	−0.0047 (6)
C21	0.0191 (6)	0.0191 (6)	0.0180 (6)	−0.0007 (5)	0.0006 (5)	0.0005 (5)
C22	0.0171 (6)	0.0222 (7)	0.0206 (7)	0.0028 (5)	0.0007 (5)	0.0004 (5)
C23	0.0209 (6)	0.0223 (7)	0.0187 (7)	0.0017 (5)	0.0050 (5)	−0.0003 (5)
C24	0.0200 (6)	0.0184 (6)	0.0176 (6)	0.0005 (5)	−0.0002 (5)	−0.0001 (5)
C25	0.0166 (6)	0.0258 (7)	0.0206 (7)	0.0033 (5)	0.0006 (5)	0.0005 (5)
C26	0.0199 (6)	0.0282 (7)	0.0187 (7)	0.0026 (5)	0.0051 (5)	0.0009 (6)
C27	0.0248 (7)	0.0203 (7)	0.0192 (7)	0.0038 (5)	0.0004 (5)	0.0000 (5)
C28	0.0354 (8)	0.0336 (8)	0.0243 (8)	0.0096 (7)	−0.0056 (6)	0.0061 (6)
C31	0.0180 (6)	0.0218 (7)	0.0168 (6)	−0.0008 (5)	0.0035 (5)	−0.0014 (5)
C32	0.0192 (6)	0.0233 (7)	0.0190 (7)	0.0028 (5)	−0.0010 (5)	0.0023 (5)
C33	0.0255 (7)	0.0187 (6)	0.0207 (7)	−0.0003 (5)	0.0034 (5)	0.0010 (5)
C34	0.0199 (6)	0.0247 (7)	0.0155 (6)	−0.0028 (5)	0.0032 (5)	−0.0031 (5)
C35	0.0197 (6)	0.0270 (7)	0.0160 (6)	0.0022 (5)	0.0004 (5)	0.0028 (5)
C36	0.0226 (7)	0.0201 (6)	0.0189 (7)	0.0013 (5)	0.0028 (5)	0.0037 (5)
C37	0.0241 (7)	0.0259 (7)	0.0163 (7)	−0.0018 (6)	0.0038 (5)	−0.0025 (5)
C38	0.0295 (8)	0.0297 (8)	0.0331 (9)	−0.0109 (6)	−0.0017 (7)	−0.0055 (7)

Geometric parameters (Å, º) top

O1—C17	1.2021 (19)	C21—C22	1.3934 (19)
O2—C17	1.3356 (19)	C21—C26	1.3967 (19)
O2—C18	1.4439 (17)	C22—H22	0.9500
O3—C27	1.2030 (18)	C22—C23	1.3857 (19)
O4—C27	1.3400 (17)	C23—H23	0.9500
O4—C28	1.4439 (18)	C23—C24	1.3921 (19)
O5—C37	1.2046 (18)	C24—C25	1.391 (2)
O6—C37	1.3380 (19)	C24—C27	1.4905 (19)
O6—C38	1.4491 (17)	C25—H25	0.9500
C1—C10	1.341 (2)	C25—C26	1.390 (2)
C1—C21	1.4968 (19)	C26—H26	0.9500
C1—C31	1.4922 (19)	C28—H28A	0.9800
C10—H10	0.9500	C28—H28B	0.9800
C10—C11	1.4704 (19)	C28—H28C	0.9800
C11—C12	1.403 (2)	C31—C32	1.398 (2)
C11—C16	1.399 (2)	C31—C36	1.3963 (19)
C12—H12	0.9500	C32—H32	0.9500
C12—C13	1.382 (2)	C32—C33	1.382 (2)
C13—H13	0.9500	C33—H33	0.9500
C13—C14	1.391 (2)	C33—C34	1.396 (2)
C14—C15	1.391 (2)	C34—C35	1.391 (2)
C14—C17	1.495 (2)	C34—C37	1.4891 (19)
C15—H15	0.9500	C35—H35	0.9500
C15—C16	1.386 (2)	C35—C36	1.382 (2)
C16—H16	0.9500	C36—H36	0.9500
C18—H18A	0.9800	C38—H38A	0.9800
C18—H18B	0.9800	C38—H38B	0.9800
C18—H18C	0.9800	C38—H38C	0.9800

C17—O2—C18	114.39 (12)	C23—C24—C27	118.03 (12)
C27—O4—C28	115.36 (12)	C25—C24—C23	119.75 (13)
C37—O6—C38	114.49 (12)	C25—C24—C27	122.17 (12)
C10—C1—C21	126.32 (13)	C24—C25—H25	120.0
C10—C1—C31	119.49 (13)	C26—C25—C24	120.08 (13)
C31—C1—C21	114.16 (12)	C26—C25—H25	120.0
C1—C10—H10	115.2	C21—C26—H26	119.8
C1—C10—C11	129.60 (13)	C25—C26—C21	120.40 (13)
C11—C10—H10	115.2	C25—C26—H26	119.8
C12—C11—C10	124.65 (13)	O3—C27—O4	123.37 (13)
C16—C11—C10	117.39 (13)	O3—C27—C24	124.22 (13)
C16—C11—C12	117.95 (13)	O4—C27—C24	112.41 (12)
C11—C12—H12	119.6	O4—C28—H28A	109.5
C13—C12—C11	120.77 (14)	O4—C28—H28B	109.5
C13—C12—H12	119.6	O4—C28—H28C	109.5
C12—C13—H13	119.8	H28A—C28—H28B	109.5
C12—C13—C14	120.47 (14)	H28A—C28—H28C	109.5
C14—C13—H13	119.8	H28B—C28—H28C	109.5
C13—C14—C15	119.48 (13)	C32—C31—C1	120.65 (12)
C13—C14—C17	117.72 (13)	C36—C31—C1	121.06 (13)
C15—C14—C17	122.80 (13)	C36—C31—C32	118.29 (12)
C14—C15—H15	120.0	C31—C32—H32	119.4
C16—C15—C14	119.93 (13)	C33—C32—C31	121.24 (13)
C16—C15—H15	120.0	C33—C32—H32	119.4
C11—C16—H16	119.4	C32—C33—H33	120.1
C15—C16—C11	121.20 (13)	C32—C33—C34	119.78 (13)
C15—C16—H16	119.4	C34—C33—H33	120.1
O1—C17—O2	123.56 (14)	C33—C34—C37	123.26 (13)
O1—C17—C14	124.15 (14)	C35—C34—C33	119.49 (13)
O2—C17—C14	112.30 (12)	C35—C34—C37	117.24 (13)
O2—C18—H18A	109.5	C34—C35—H35	119.8
O2—C18—H18B	109.5	C36—C35—C34	120.39 (13)
O2—C18—H18C	109.5	C36—C35—H35	119.8
H18A—C18—H18B	109.5	C31—C36—H36	119.6
H18A—C18—H18C	109.5	C35—C36—C31	120.81 (13)
H18B—C18—H18C	109.5	C35—C36—H36	119.6
C22—C21—C1	119.09 (12)	O5—C37—O6	123.55 (13)
C22—C21—C26	118.98 (13)	O5—C37—C34	124.19 (14)
C26—C21—C1	121.67 (12)	O6—C37—C34	112.26 (12)
C21—C22—H22	119.6	O6—C38—H38A	109.5
C23—C22—C21	120.73 (13)	O6—C38—H38B	109.5
C23—C22—H22	119.6	O6—C38—H38C	109.5
C22—C23—H23	120.0	H38A—C38—H38B	109.5
C22—C23—C24	119.99 (13)	H38A—C38—H38C	109.5
C24—C23—H23	120.0	H38B—C38—H38C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10···O5ⁱ	0.95	2.51	3.4082 (18)	159
C18—H18B···O4ⁱⁱ	0.98	2.72	3.5520 (19)	144
C28—H28C···O6ⁱⁱⁱ	0.98	2.85	3.769 (2)	156
C38—H38A···O1^iv	0.98	2.79	3.275 (2)	111
C38—H38B···O3^v	0.98	2.57	3.339 (2)	135
C38—H38C···O2^vi	0.98	2.66	3.595 (2)	159

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

Footnotes

‡Current address: Institute of Marine Sciences, Department of Oceanography, Middle East Technical University, Erdemli, Mersin, Turkey.

Acknowledgements

MJGL thanks IDW and HKUST for hosting a sabbatical leave used to complete this work.

Funding information

Funding for this research was provided by: CSU Faculty Research Grant (grant to MJGL); CSU Faculty Travel Grant (grant to MJGL).

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