Synthesis and crystal structure of methyl 3-(3-hy­droxy-3-phenyl­prop-2-eno­yl)benzoate

Zharinova, I.S.; Bilyalova, A.A.; Bezzubov, S.I.

doi:10.1107/S2056989018007259

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Volume 74| Part 6| June 2018| Pages 816-819

https://doi.org/10.1107/S2056989018007259

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Synthesis and crystal structure of methyl 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate

Irina S. Zharinova,^a Alfiya A. Bilyalova ^a and Stanislav I. Bezzubov ^b ^*

^aDepartment of Chemistry, Lomonosov Moscow State University, Lenin's Hills 1/3, Moscow 119991, Russian Federation, and ^bKurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskiy pr. 31, Moscow 119991, Russian Federation
^*Correspondence e-mail: bezzubov@igic.ras.ru

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 April 2018; accepted 14 May 2018; online 18 May 2018)

The title compound, C₁₇H₁₄O₄, was synthesized under mild conditions and characterized by various analytical techniques. Combined NMR and X-ray diffraction data show that the substance exists exclusively in the enol tautomeric form. An intramolecular ⋯O=C—C=C—OH⋯ hydrogen bond is present in the molecular structure. The analysis of the difference density map disclosed two adjacent positions of a disordered hydrogen atom taking part in this hydrogen bond, indicating the presence of two enol tautomers in the crystal. The enol molecules are assembled through numerous C—H⋯π and π–π as well as weak C(aryl)—H⋯O interactions, thus forming a dense crystal packing. The obtained substance was also studied by UV–Vis spectroscopy and cyclic voltammetry.

Keywords: crystal structure; β-diketone; hydrogen bond; tautomerism.

CCDC reference: 1838743

1. Chemical context

The high complexing ability via O-donor atoms and excellent optical properties of aromatic β-diketones make them practically irreplaceable in the creation of efficient emitters [as lanthanide or iridium(III) complexes] for application in OLEDs (organic light-emitting diodes; Eliseeva & Bünzli, 2010 ; Bünzli, 2015 ). In addition, β-diketone-based Ir^III complexes have attracted particular attention as promising photosensitizers in dye-sensitized solar cells (Baranoff et al., 2010 ). Surprisingly, aromatic β-diketones functionalized by anchoring COOH groups have not been considered as a possible alternative to traditional anchoring 4,4′-dicarboxy-2,2′-bipyridine groups.

Herein we report on the crystal structure as well as optical and electrochemical properties of a non-symmetric aromatic β-diketone with formula C₁₇H₁₄O₄, bearing a carboxymethyl group.

2. Structural commentary

A ¹H NMR study of the prepared β-diketone showed that it appears exclusively as an enol tautomer in solution (CDCl₃). Single-crystal X-ray diffraction analysis also confirmed unambiguously that the compound exists in the enol form in the solid state (Fig. 1a). In the molecular structure, an intramolecular resonance-assisted hydrogen bond (for related structures, see: Gilli et al., 2004 ) connects the two oxygen atoms of the keto–enol moiety with the O3⋯O4 distance as short as 2.4358 (10) Å (Table 1). The hydrogen atom involved in this interaction is disordered over two sites (H21 and H22) with almost equal occupancies. The virtual H⋯H distance of 0.625 (1) Å is a result of the simultaneous presence of two enol forms, O3—H⋯O4 and O3⋯H—O4, respectively, in an approximate 1:1 ratio in the crystal. The title molecule is almost planar with a variation of the dihedral angles between phenyl rings and the keto–enol plane between 5.65 (4) and 11.05 (4)°.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C3–C8 and C12–C17 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H21⋯O4	0.92 (7)	1.54 (7)	2.4358 (10)	162 (4)
O4—H22⋯O3	0.94 (6)	1.55 (6)	2.4358 (10)	156 (3)
C16—H16⋯O3ⁱ	0.956 (14)	2.417 (14)	3.0837 (12)	126.6 (11)
C5—H5⋯Cg2ⁱⁱ	0.990 (14)	2.740 (15)	3.525 (13)	135.0 (8)
C14—H14⋯Cg1ⁱⁱⁱ	0.990 (14)	2.758 (15)	3.968 (12)	127.2 (8)
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 1
(a) Molecular structure of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate. Displacement ellipsoids are shown at the 50% probability level; (b) difference-density map in the plane of the hydrogen-bonded ring. This map was computed after least-squares refinement without the hydrogen atoms H21 and H22 involved in the hydrogen bond. Contours are drawn at 0.04 e Å⁻³ intervals.

3. Supramolecular features

The enol molecules are assembled in a `head-to-tail' manner by several C—H⋯π [range 2.740 (15)–2.758 (15) Å] interactions (Table 1]) involving the phenyl H atoms and the centroids of the phenyl rings of adjacent molecules as well as by π–π contacts [range 3.422 (14)–3.531 (15) Å]. The resultant stacks are grafted together by weak C—H⋯O interactions (Desiraju & Steiner, 2001 ) between the aryl rings and the oxygen atoms of the keto–enol fragment with a C⋯O distance of 3.0837 (12) Å, forming a network structure (Table 1; Figs. 2 and 3).

Figure 2
Crystal packing of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate.

Figure 3
Intermolecular C—H⋯O hydrogen bonding in the crystal structure of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate.

4. Database survey

Although there have been numerous reports on crystal structures of various symmetric and non-symmetric β-diketones in the Cambridge Structural Database (Version 5.38, February 2018; Groom et al., 2016 ), only a few examples of aromatic β-diketones functionalized by COOH groups (or COOR) are well documented (Langer et al., 2006 ; Ishikawa & Ugai, 2013 ; Hui et al., 2010 ). In their molecular structures, the intramolecular resonance-assisted hydrogen bonds exhibit quite short O⋯O distances (2.39–2.55 Å; Bertolasi et al., 1991 ). The hydrogen atom located between these O atoms is either ordered or disordered by symmetry as in dibenzoylmethane and other symmetrical β-diketones (see, for example: Thomas et al., 2009 ; Andrews et al., 2014 ) or with unequal occupancies in the vast majority of non-symmetric enols (see, for instance: Aromí et al., 2002 , Soldatov et al., 2003 ). In some cases, crystals contain two different enol molecules (O—H⋯O and O⋯H—O) with ordered H atoms (Mohamed et al., 2015 ; Zheng et al., 2009 ; Bertolasi et al., 1991).

5. Synthesis and crystallization

There are some synthetic difficulties encountered in preparation of carboxylated β-diketones according to the common Claisen condensation. Fortunately, the desired compounds can be obtained under mild conditions via an MgBr₂·Et₂O-assisted acylation of ketones by benzotriazole amides of the corresponding diesters (Lim et al., 2007 ). The title compound was prepared as follows:

To a suspension of MgBr₂·Et₂O (0.73 g, 2.8 mmol) in dry CH₂Cl₂ (16 ml), acetophenone (0.35 ml, 3.0 mmol) was added and the mixture was sonicated for a minute. N,N-Diisopropylethylamine (0.52 ml, 3.0 mmol) was added to the mixture and it was sonicated for a minute. The resulted suspension was added quickly to a solution of the methyl ester of isophtalic acid benzotriazole amide (1.15 g, 4.0 mmol) in dry CH₂Cl₂ (16 ml) and the mixture was stirred at 293 K for 34 h. The reaction mixture was treated by a 2 M HCl solution (40 ml) and stirred vigorously for 1 h. The organic layer was separated and the aqueous layer extracted with CH₂Cl₂ (3 × 20 ml). The combined organic extracts were washed with water (1 × 20 ml) and brine (1 × 20 ml) and filtrated through paper followed by evaporation of the solvent. The resulting oil was crystallized from CH₃OH solution at 255 K to give a light-yellow powder, which was purified by column chromatography (SiO₂, CHCl₃/hexane 1/3 v/v) and dried in vacuo. Yield 457 mg (54%). Single crystals suitable for X-ray analysis were grown by slow evaporation of the solvent from a solution of the substance in chloroform.

Analysis: calculated for C₁₇H₁₄O₄: C, 72.33; H, 5.00. Found: C, 72.28; H, 5.04.

¹H NMR (CDCl₃, ppm, 400 MHz): δ 3.99 (s, 3H, CH₃), 6.92 (s, 1H, C–H), 7.51 (t, J = 7.5 Hz, 2H, Ar–H), 7.57–7.62 (m, 2H, Ar–H), 8.02 (d, J = 7.4 Hz, 2H, Ar–H), 8.22 (t, J = 7.8 Hz, 2H, Ar–H), 8.63 (s, 1H, Ar–H). See supplementary Fig. S1.

¹³C NMR (CDCl₃, ppm, 100 MHz): δ 51.97, 92.81, 126.85, 127.78, 128.29, 128.50, 130.29, 130.96, 132.27, 132.74, 134.82, 135.45, 165.88, 183.99, 185.71. See supplementary Fig. S2.

UV–Vis (CH₂Cl₂): λ_max = 344 nm (∊_max = 32000 cm⁻¹ M⁻¹). See supplementary Fig. S3.

Redox potentials (Ar-saturated CH₃CN with 0.01 M (n-Bu₄N)ClO₄ at scan rate of 25 mV s⁻¹, ferrocene as external standard): E_ox1 = 1.15, E_ox2 = 1.53 V vs standard hydrogen electrode. See supplementary Fig. S4.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All hydrogen atoms were located from a difference-density map and refined freely. The disordered hydrogen atoms H21 and H22 were clearly discernible from a difference-density map (Fig. 1b). Their occupancies refined to a ratio of 0.44 (7):0.56 (7) and with U_iso(H) = 1.5U_eq(O).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₇H₁₄O₄
M_r	282.28
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	7.8085 (10), 10.5171 (14), 17.124 (2)
β (°)	102.711 (2)
V (Å³)	1371.8 (3)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.40 × 0.40

Data collection
Diffractometer	Bruker SMART APEXII
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
No. of measured, independent and observed [I > 2σ(I)] reflections	16222, 4006, 3488
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.114, 1.03
No. of reflections	4006
No. of parameters	249
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXL2014/7 (Sheldrick, 2015 ), SHELXTL (Sheldrick, 2008 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1838743

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018007259/wm5445sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018007259/wm5445Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018007259/wm5445Isup3.mol

^1^H-NMR spectrum of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate. DOI: https://doi.org/10.1107/S2056989018007259/wm5445sup4.tif

^13^C-NMR spectrum of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate. DOI: https://doi.org/10.1107/S2056989018007259/wm5445sup5.tif

UV-Vis spectrum of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate in CH2Cl2 at 298 K. DOI: https://doi.org/10.1107/S2056989018007259/wm5445sup6.tif

Polarographic curves of 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate (CH3CN, 298 K). DOI: https://doi.org/10.1107/S2056989018007259/wm5445sup7.tif

Supporting information file. DOI: https://doi.org/10.1107/S2056989018007259/wm5445Isup8.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014/7 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

Methyl 3-(3-hydroxy-3-phenylprop-2-enoyl)benzoate top

Crystal data top

C₁₇H₁₄O₄	F(000) = 592
M_r = 282.28	D_x = 1.367 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.8085 (10) Å	Cell parameters from 7383 reflections
b = 10.5171 (14) Å	θ = 2.3–30.6°
c = 17.124 (2) Å	µ = 0.10 mm⁻¹
β = 102.711 (2)°	T = 150 K
V = 1371.8 (3) Å³	Block, colorless
Z = 4	0.40 × 0.40 × 0.40 mm

Data collection top

Bruker SMART APEXII diffractometer	3488 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.019
ω scans	θ_max = 30.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −10→10
	k = −14→14
16222 measured reflections	l = −24→23
4006 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Only H-atom coordinates refined
wR(F²) = 0.114	w = 1/[σ²(F_o²) + (0.0663P)² + 0.2977P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
4006 reflections	Δρ_max = 0.37 e Å⁻³
249 parameters	Δρ_min = −0.22 e Å⁻³

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	Occ. (<1)
O1	−0.02289 (10)	0.46985 (7)	0.30296 (4)	0.02697 (17)
O2	−0.12474 (11)	0.26937 (7)	0.28859 (4)	0.03277 (19)
O3	0.38132 (11)	0.60581 (7)	0.53783 (4)	0.02964 (17)
H21	0.453 (8)	0.656 (5)	0.576 (4)	0.044*	0.44 (7)
O4	0.57483 (11)	0.70032 (7)	0.65449 (4)	0.02985 (18)
H22	0.514 (6)	0.679 (3)	0.602 (3)	0.045*	0.56 (7)
C1	−0.10630 (15)	0.49402 (11)	0.22003 (6)	0.0300 (2)
C2	−0.04506 (12)	0.35314 (9)	0.32993 (5)	0.02290 (19)
C3	0.03831 (11)	0.33830 (9)	0.41682 (5)	0.02148 (18)
C4	−0.00756 (13)	0.23323 (10)	0.45741 (6)	0.0255 (2)
C5	0.06741 (13)	0.21642 (10)	0.53842 (6)	0.0272 (2)
C6	0.18868 (12)	0.30374 (9)	0.57898 (6)	0.02360 (19)
C7	0.23487 (11)	0.40975 (8)	0.53865 (5)	0.01984 (17)
C8	0.15825 (12)	0.42696 (9)	0.45750 (5)	0.02100 (18)
C9	0.35890 (12)	0.50819 (8)	0.57990 (5)	0.02039 (18)
C10	0.44676 (12)	0.49939 (8)	0.66080 (5)	0.02051 (18)
C11	0.55464 (12)	0.59996 (8)	0.69575 (5)	0.02053 (18)
C12	0.65178 (12)	0.60014 (8)	0.78042 (5)	0.01982 (17)
C13	0.66742 (13)	0.49140 (9)	0.82826 (6)	0.02281 (19)
C14	0.76486 (13)	0.49531 (10)	0.90678 (6)	0.0260 (2)
C15	0.84439 (13)	0.60801 (10)	0.93823 (6)	0.0264 (2)
C16	0.82857 (13)	0.71666 (10)	0.89115 (6)	0.0266 (2)
C17	0.73336 (13)	0.71309 (9)	0.81247 (6)	0.02385 (19)
H1	−0.232 (2)	0.4767 (14)	0.2115 (9)	0.039 (4)*
H2	−0.085 (2)	0.5860 (16)	0.2101 (9)	0.049 (4)*
H3	−0.0581 (19)	0.4386 (14)	0.1844 (8)	0.036 (3)*
H4	−0.0921 (19)	0.1711 (14)	0.4287 (8)	0.036 (3)*
H5	0.0327 (18)	0.1435 (14)	0.5681 (8)	0.036 (3)*
H6	0.2389 (17)	0.2880 (12)	0.6355 (8)	0.028 (3)*
H8	0.1889 (17)	0.4998 (13)	0.4304 (8)	0.030 (3)*
H10	0.4322 (18)	0.4265 (13)	0.6917 (8)	0.028 (3)*
H13	0.6130 (18)	0.4132 (13)	0.8092 (8)	0.031 (3)*
H14	0.7750 (18)	0.4169 (13)	0.9395 (8)	0.034 (3)*
H15	0.9105 (19)	0.6135 (14)	0.9943 (9)	0.038 (4)*
H16	0.8836 (18)	0.7951 (13)	0.9107 (8)	0.034 (3)*
H17	0.7219 (18)	0.7909 (13)	0.7788 (8)	0.035 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0310 (4)	0.0272 (4)	0.0201 (3)	−0.0005 (3)	−0.0001 (3)	−0.0007 (3)
O2	0.0381 (4)	0.0291 (4)	0.0263 (4)	−0.0026 (3)	−0.0033 (3)	−0.0062 (3)
O3	0.0382 (4)	0.0254 (4)	0.0218 (3)	−0.0056 (3)	−0.0012 (3)	0.0055 (3)
O4	0.0421 (4)	0.0227 (3)	0.0224 (3)	−0.0083 (3)	0.0019 (3)	0.0034 (3)
C1	0.0315 (5)	0.0358 (5)	0.0202 (4)	0.0036 (4)	0.0003 (4)	0.0018 (4)
C2	0.0208 (4)	0.0251 (4)	0.0221 (4)	0.0024 (3)	0.0032 (3)	−0.0035 (3)
C3	0.0194 (4)	0.0241 (4)	0.0205 (4)	0.0027 (3)	0.0035 (3)	−0.0031 (3)
C4	0.0227 (4)	0.0266 (5)	0.0265 (5)	−0.0031 (3)	0.0039 (3)	−0.0033 (4)
C5	0.0270 (5)	0.0273 (5)	0.0269 (5)	−0.0045 (4)	0.0055 (4)	0.0016 (4)
C6	0.0236 (4)	0.0259 (4)	0.0207 (4)	0.0000 (3)	0.0037 (3)	0.0010 (3)
C7	0.0186 (4)	0.0211 (4)	0.0193 (4)	0.0018 (3)	0.0030 (3)	−0.0015 (3)
C8	0.0206 (4)	0.0222 (4)	0.0197 (4)	0.0018 (3)	0.0033 (3)	−0.0010 (3)
C9	0.0204 (4)	0.0204 (4)	0.0200 (4)	0.0017 (3)	0.0035 (3)	−0.0004 (3)
C10	0.0234 (4)	0.0192 (4)	0.0182 (4)	−0.0011 (3)	0.0029 (3)	0.0000 (3)
C11	0.0227 (4)	0.0196 (4)	0.0194 (4)	0.0003 (3)	0.0049 (3)	−0.0007 (3)
C12	0.0209 (4)	0.0198 (4)	0.0188 (4)	−0.0013 (3)	0.0044 (3)	−0.0025 (3)
C13	0.0240 (4)	0.0201 (4)	0.0229 (4)	−0.0024 (3)	0.0022 (3)	−0.0004 (3)
C14	0.0256 (5)	0.0274 (5)	0.0234 (4)	−0.0011 (3)	0.0018 (4)	0.0027 (3)
C15	0.0248 (4)	0.0320 (5)	0.0208 (4)	−0.0019 (4)	0.0015 (3)	−0.0037 (4)
C16	0.0283 (5)	0.0259 (5)	0.0250 (4)	−0.0056 (4)	0.0044 (4)	−0.0074 (4)
C17	0.0283 (4)	0.0202 (4)	0.0233 (4)	−0.0031 (3)	0.0062 (3)	−0.0028 (3)

Geometric parameters (Å, º) top

O1—C2	1.3361 (12)	C7—C8	1.3985 (12)
O1—C1	1.4486 (12)	C7—C9	1.4858 (13)
O2—C2	1.2127 (12)	C8—H8	0.953 (13)
O3—C9	1.2881 (11)	C9—C10	1.4072 (12)
O3—H21	0.92 (7)	C10—C11	1.4017 (12)
O4—C11	1.2989 (11)	C10—H10	0.952 (13)
O4—H22	0.94 (6)	C11—C12	1.4811 (12)
C1—H1	0.980 (15)	C12—C13	1.3963 (13)
C1—H2	1.003 (17)	C12—C17	1.4015 (12)
C1—H3	0.977 (14)	C13—C14	1.3922 (13)
C2—C3	1.4952 (12)	C13—H13	0.950 (14)
C3—C4	1.3936 (14)	C14—C15	1.3904 (14)
C3—C8	1.3945 (13)	C14—H14	0.990 (14)
C4—C5	1.3932 (14)	C15—C16	1.3882 (14)
C4—H4	0.981 (15)	C15—H15	0.986 (15)
C5—C6	1.3903 (14)	C16—C17	1.3887 (13)
C5—H5	0.990 (14)	C16—H16	0.956 (14)
C6—C7	1.3999 (13)	C17—H17	0.993 (14)
C6—H6	0.975 (13)

C2—O1—C1	115.82 (8)	C7—C8—H8	119.3 (8)
C9—O3—H21	101 (3)	O3—C9—C10	120.41 (8)
C11—O4—H22	103 (2)	O3—C9—C7	116.37 (8)
O1—C1—H1	109.5 (9)	C10—C9—C7	123.21 (8)
O1—C1—H2	106.3 (9)	C11—C10—C9	119.19 (8)
H1—C1—H2	110.7 (13)	C11—C10—H10	120.3 (8)
O1—C1—H3	110.8 (8)	C9—C10—H10	120.5 (8)
H1—C1—H3	108.0 (12)	O4—C11—C10	120.96 (8)
H2—C1—H3	111.5 (12)	O4—C11—C12	115.73 (8)
O2—C2—O1	123.67 (9)	C10—C11—C12	123.31 (8)
O2—C2—C3	124.07 (9)	C13—C12—C17	119.40 (8)
O1—C2—C3	112.25 (8)	C13—C12—C11	122.22 (8)
C4—C3—C8	119.94 (8)	C17—C12—C11	118.37 (8)
C4—C3—C2	118.40 (8)	C14—C13—C12	120.07 (8)
C8—C3—C2	121.65 (8)	C14—C13—H13	117.7 (8)
C5—C4—C3	119.97 (9)	C12—C13—H13	122.2 (8)
C5—C4—H4	120.3 (8)	C15—C14—C13	120.12 (9)
C3—C4—H4	119.8 (8)	C15—C14—H14	121.2 (8)
C6—C5—C4	120.29 (9)	C13—C14—H14	118.7 (8)
C6—C5—H5	119.2 (8)	C16—C15—C14	120.11 (9)
C4—C5—H5	120.4 (8)	C16—C15—H15	118.5 (8)
C5—C6—C7	120.05 (9)	C14—C15—H15	121.4 (8)
C5—C6—H6	117.7 (8)	C15—C16—C17	120.09 (9)
C7—C6—H6	122.2 (8)	C15—C16—H16	122.1 (8)
C8—C7—C6	119.53 (8)	C17—C16—H16	117.8 (8)
C8—C7—C9	118.28 (8)	C16—C17—C12	120.20 (9)
C6—C7—C9	122.15 (8)	C16—C17—H17	120.1 (8)
C3—C8—C7	120.22 (9)	C12—C17—H17	119.7 (8)
C3—C8—H8	120.5 (8)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C3–C8 and C12–C17 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
O3—H21···O4	0.92 (7)	1.54 (7)	2.4358 (10)	162 (4)
O4—H22···O3	0.94 (6)	1.55 (6)	2.4358 (10)	156 (3)
C16—H16···O3ⁱ	0.956 (14)	2.417 (14)	3.0837 (12)	126.6 (11)
C5—H5···Cg2ⁱⁱ	0.990 (14)	2.740 (15)	3.525 (13)	135.0 (8)
C14—H14···Cg1ⁱⁱⁱ	0.990 (14)	2.758 (15)	3.968 (12)	127.2 (8)

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

Acknowledgements

X-ray diffraction studies were performed at the Centre of Shared Equipment of IGIC RAS.

Funding information

Funding for this research was provided by: Russian Science Foundation (grant No. 17-73-10084).

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