Synthesis, crystal structure and Hirshfeld surface analysis of 4′-cyano-[1,1′-biphen­yl]-4-yl 3-(benz­yloxy)benzoate

Harish Kumar, M.; Vinduvahini, M.; Devarajegowda, H.C.; Srinivasa, H.T.; Palakshamurthy, B.S.

doi:10.1107/S2056989024008570

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ISSN: 2056-9890

Volume 80| Part 10| October 2024| Pages 1010-1013

https://doi.org/10.1107/S2056989024008570

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Synthesis, crystal structure and Hirshfeld surface analysis of 4′-cyano-[1,1′-biphenyl]-4-yl 3-(benzyloxy)benzoate

M. Harish Kumar,^a M. Vinduvahini,^b H. C. Devarajegowda,^a H. T. Srinivasa ^c and B. S. Palakshamurthy ^d ^*

^aDepartment of Physics, Yuvaraja's College, University of Mysore, Mysore, 570005, Karnaataka, India, ^bDepartment of Physics, Maharani's Science College for Women(Autonomous) Mysore, Karnataka, 750005, India, ^cRaman Research Institute, C. V. Raman, Avenue, Sadashivanagar, Bangalore, Karnataka, India, and ^dDepartment of PG Studies and Research in Physics, Albert Einstein Block, UCS, Tumkur University, Tumkur, Karnataka 572103, India
^*Correspondence e-mail: palaksha.bspm@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 13 August 2024; accepted 29 August 2024; online 12 September 2024)

In the title compound, C₂₇H₁₉O₃N, the dihedral angle between the aromatic rings of the biphenyl unit is 38.14 (2)° and the C—O—C—C torsion angle in the benzyloxy benzene fragment is 179.1 (2)°. In the crystal, the molecules are linked by weak C—H⋯O interactions forming S(9) chains propagating along [010]. The most important contributions to the Hirshfeld surface arise from H⋯H (32.4%) and C⋯H/H⋯C (37.0%) contacts.

Keywords: crystal structure; Hirshfeld surface; 4′-cyano-[1,1′-biphenyl]; (benzyloxy)benzoate.

CCDC reference: 2380701

1. Chemical context

Cyanobiphenyl-substituted derivatives can act as biological inhibitors and potential agents for the treatment of Alzheimer's disease (Godyń et al., 2021 ) as well as antibacterial and antimalarial drugs (Malani et al., 2013 ). Benzyloxy derivatives exhibit anti-bacterial, anti-platelet and anti-malarial activities (Kaushik et al., 2018 ; de Candia et al., 2015 ; Mohebi et al., 2022 ) and related pyrimidinylphenylamine derivatives are most active towards the inhibition of HIV-1 (Rai et al., 2013 ). The cyanobiphenyl and (benzyloxy)benzoate groups exhibit distinct structural geometries and these derivatives play significant roles in the construction of organic liquid crystal materials (Srinivasa et al., 2015 ), which have been investigated for their display technology applications, such as optoelectronic materials, sensor materials, light-emitting diodes, and photovoltaic solar cells (Goodby et al., 2022 ; Srinivasa et al., 2024 ). As part of our studies of this family of materials, we now present the synthesis, structure and Hirshfeld surface analysis of the title compound, C₂₇H₁₉NO₃ (I).

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1. The aromatic rings in the molecule are designated as A (C2–C7), B (C8–C13), C (C15–C20) and D (C22–C27) and the dihedral angles between the rings A/B = 38.14 (2), A/C = 8.29 (3) and A/D = 50.66 (2)°, whereas B/C, B/D and C/D are 46.43 (4), 83.95 (2) and 44.01 (2)°, respectively. The torsion angle associated with the phenyl benzoate group (C11—O1—C14—C15) is −177.8 (2)° and that for the benzyloxy group (C22—C21—O3—C17) is 179.1 (2)°. Otherwise, the bond distances and angles may be regarded as normal.

Figure 1
The molecular structure of (I)

with displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

The crystal structure features a weak C3—H3⋯O1 interaction (Table 1), which forms an S(9) chain propagating along the [010] direction as shown in Fig. 2. Furthermore, the packing is consolidated by three weak C—H⋯π interactions as shown in Fig. 3. In addition there exists an aromatic π–π stacking interaction between the C2–C7 and C15–C20 rings with a centroid–centroid distance of 3.9282 (19) Å (Fig. 4).

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C22–C27 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.52	3.395 (4)	158
CH—H4⋯Cg2ⁱ	0.93	2.97	3.805 (3)	151
C9—H9⋯Cg4ⁱⁱ	0.93	2.90	3.579 (3)	131
C12—H12⋯Cg4ⁱⁱⁱ	0.93	2.77	3.485 (13)	135
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z]$ ; (iii) $[-x+2, y+{\script{1\over 2}}, -z]$ .

Figure 2
The crystal structure of (I)

with a weak C—H ⋯ O interaction forming an S(9) chain running along the [010] direction.

Figure 3
The molecular packing of (I)

with C—H⋯π interactions depicted by dashed lines.

Figure 4
The molecular packing of (I)

with π–π interactions depicted by pale green coloured dashed lines.

4. Hirshfeld surface analysis

CrystalExplorer17.5 (Turner et al., 2017 ) was used to perform a Hirshfeld surface analysis to further quantify the various intermolecular interactions. Fig. 5 illustrates the Hirshfeld surface mapped over d_norm with red spots corresponding to short contacts. The fingerprint plots (Fig. 6) indicate that the major contributions to the crystal structure are from H⋯H (36.2%), C⋯H/H⋯C (33.8%), O⋯H/H⋯O (12.1.6%), N⋯H/H⋯N (10.1.8%) and C⋯C (5.0%) contacts. The characteristic spikes in the O⋯H/H⋯O plot indicate the existence of the C—H⋯O hydrogen bond listed in Table 1.

Figure 5
Hirshfeld surface representation for (I)

plotted over d_norm.

Figure 6
The full two-dimensional fingerprint plots for the title compound, showing all interactions and delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, N⋯H/H⋯N and C⋯C interactions.

5. Database survey

A search of the Cambridge Structural Database (CSD, version 5.42, update of November 2020; Groom et al., 2016 ) for molecules containing the 4′-cyano-[1,1′-biphenyl] fragment resulted in two matches with CSD refcodes PIFZEN and PIFZIR (Jakubowski et al., 2023 ). In these structures, the dihedral angle between the 4-cyanophenoxy ring and the neighbouring ring are 31.71 (2) and 38.95 (3)°, respectively, compared to 38.14 (2)° for (I). For molecules containing the (benzyloxy)benzoate fragment, a search resulted in thirteen matches: in all of these, the torsion angle of the linking C—O—C—C unit indicates a conformation close to anti.

6. Synthesis and crystallization

A mixture of 3-(benzyloxy)benzoic acid (1 eq., 0.228 g) and 4′-hydroxy-[1,1′-biphenyl]-4-carbonitrile (1 eq., 0.195 g), dicyclohexylcarbodiimide (1.2 eq.) and a catalytic amount of dimethylaminopyrimidine were stirred in dry dichloromethane at room temperature overnight. After completion of the reaction, the product mass was subjected to column chromatography with silica gel and chloroform as eluent. The crude product was recrystallized from chloroform solution to yield colourless blocks of (I). Melting point = 398 K, analysis (%) calculated for C₂₇H₁₉NO₃, C 79.98, H 4.72, N 3.45; found C 78.01; H 4.76, N 3.48. ¹H NMR (500 MHz, CDCl₃, δ/ppm): 7.82 (m, 4H, Ar-H), 7.65 (m, 4H, Ar-H), 7.44 (m, 4H, Ar-H), 7.23 (m, 5H, Ar-H), 5.24 (s, 2H, Ar—CH₂—O—).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All the H-atoms were positioned with idealized geometry and refined using a riding model with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₇H₁₉NO₃
M_r	405.43
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	270
a, b, c (Å)	9.4289 (10), 9.6739 (9), 11.4872 (11)
β (°)	97.668 (4)
V (Å³)	1038.43 (18)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.42 × 0.38 × 0.24

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.966, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	27994, 3639, 3308
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.080, 1.08
No. of reflections	3639
No. of parameters	280
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.16
Absolute structure	Flack x determined using 1347 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.0 (5)
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ) and Mercury (Macrae et al., 2020 ).

Supporting information

CCDC reference: 2380701

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008570/hb8105sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024008570/hb8105Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024008570/hb8105Isup3.cml

checkCIF report

Computing details top

4'-Cyano-[1,1'-biphenyl]-4-yl 3-(benzyloxy)benzoate top

Crystal data top

C₂₇H₁₉NO₃	Rod
M_r = 405.43	D_x = 1.297 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 9.4289 (10) Å	Cell parameters from 3639 reflections
b = 9.6739 (9) Å	θ = 3.5–25.1°
c = 11.4872 (11) Å	µ = 0.09 mm⁻¹
β = 97.668 (4)°	T = 270 K
V = 1038.43 (18) Å³	Block, colourless
Z = 2	0.42 × 0.38 × 0.24 mm
F(000) = 424

Data collection top

Bruker SMART APEXII CCD diffractometer	3639 independent reflections
Radiation source: fine-focus sealed tube	3308 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
Detector resolution: 1.09 pixels mm^-1	θ_max = 25.0°, θ_min = 3.6°
φ and Ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −11→11
T_min = 0.966, T_max = 0.981	l = −13→13
27994 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.080	w = 1/[σ²(F_o²) + (0.0339P)² + 0.1198P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
3639 reflections	Δρ_max = 0.11 e Å⁻³
280 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint	Absolute structure: Flack x determined using 1347 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
0.012 constraints	Absolute structure parameter: 0.0 (5)
Primary atom site location: structure-invariant direct methods

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	0.7334 (2)	0.77894 (19)	0.21126 (16)	0.0509 (5)
O3	0.8888 (2)	0.5498 (2)	−0.24091 (16)	0.0555 (6)
O2	0.7452 (3)	0.5514 (2)	0.17589 (19)	0.0695 (7)
C11	0.6854 (3)	0.7566 (3)	0.3203 (2)	0.0430 (7)
C13	0.7200 (3)	0.7988 (3)	0.5258 (2)	0.0443 (7)
H13	0.775740	0.834123	0.592030	0.053*
C21	0.8166 (3)	0.4201 (3)	−0.2372 (2)	0.0484 (7)
H21A	0.715024	0.435077	−0.236419	0.058*
H21B	0.853943	0.369863	−0.166652	0.058*
C10	0.5549 (3)	0.6967 (3)	0.3284 (2)	0.0506 (7)
H10	0.498693	0.663636	0.261571	0.061*
C16	0.8197 (3)	0.6095 (3)	−0.0507 (2)	0.0414 (6)
H16	0.783496	0.521562	−0.040255	0.050*
C8	0.5898 (3)	0.7372 (3)	0.5372 (2)	0.0384 (6)
C22	0.8404 (3)	0.3390 (3)	−0.3434 (2)	0.0401 (6)
C12	0.7683 (3)	0.8085 (3)	0.4174 (2)	0.0450 (7)
H12	0.855882	0.849784	0.410635	0.054*
C20	0.8662 (3)	0.8422 (3)	0.0195 (2)	0.0488 (7)
H20	0.860968	0.910130	0.076078	0.059*
C27	0.8103 (3)	0.3941 (3)	−0.4553 (3)	0.0481 (7)
H27	0.775214	0.483768	−0.465142	0.058*
C17	0.8782 (3)	0.6410 (3)	−0.1512 (2)	0.0421 (6)
C9	0.5083 (3)	0.6864 (3)	0.4366 (2)	0.0470 (7)
H9	0.420768	0.644553	0.442524	0.056*
C15	0.8154 (3)	0.7109 (3)	0.0354 (2)	0.0391 (6)
C6	0.5598 (3)	0.8325 (3)	0.7351 (2)	0.0461 (7)
H6	0.611277	0.910110	0.717919	0.055*
C5	0.5377 (3)	0.7261 (3)	0.6536 (2)	0.0393 (6)
C2	0.4316 (3)	0.7098 (3)	0.8675 (2)	0.0493 (7)
C4	0.4646 (3)	0.6095 (3)	0.6828 (2)	0.0496 (7)
H4	0.451143	0.536161	0.630193	0.060*
C19	0.9250 (3)	0.8715 (3)	−0.0818 (3)	0.0550 (8)
H19	0.959121	0.959983	−0.093327	0.066*
C23	0.8922 (3)	0.2051 (3)	−0.3313 (3)	0.0475 (7)
H23	0.911977	0.166328	−0.256862	0.057*
N1	0.3247 (4)	0.6894 (4)	1.0630 (3)	0.0907 (11)
C7	0.5067 (3)	0.8251 (3)	0.8410 (2)	0.0506 (7)
H7	0.521498	0.897631	0.894393	0.061*
C3	0.4113 (3)	0.6006 (3)	0.7889 (3)	0.0552 (8)
H3	0.362120	0.521913	0.807373	0.066*
C14	0.7605 (3)	0.6679 (3)	0.1449 (3)	0.0450 (7)
C18	0.9338 (3)	0.7717 (3)	−0.1657 (2)	0.0515 (8)
H18	0.976819	0.791722	−0.232010	0.062*
C26	0.8322 (3)	0.3164 (3)	−0.5526 (3)	0.0549 (8)
H26	0.811223	0.353879	−0.627419	0.066*
C25	0.8848 (3)	0.1843 (3)	−0.5389 (3)	0.0588 (8)
H25	0.900050	0.132486	−0.604287	0.071*
C1	0.3728 (4)	0.6998 (4)	0.9774 (3)	0.0635 (9)
C24	0.9147 (3)	0.1288 (3)	−0.4283 (3)	0.0561 (8)
H24	0.950410	0.039321	−0.418934	0.067*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0725 (14)	0.0391 (10)	0.0449 (11)	0.0014 (10)	0.0219 (10)	−0.0050 (9)
O3	0.0780 (15)	0.0486 (12)	0.0448 (11)	−0.0129 (11)	0.0262 (10)	−0.0078 (9)
O2	0.112 (2)	0.0427 (12)	0.0623 (14)	−0.0043 (13)	0.0450 (13)	−0.0047 (11)
C11	0.0543 (17)	0.0372 (15)	0.0398 (15)	0.0058 (13)	0.0142 (13)	−0.0018 (12)
C13	0.0456 (16)	0.0440 (15)	0.0421 (15)	−0.0021 (13)	0.0016 (12)	−0.0031 (12)
C21	0.0514 (17)	0.0455 (16)	0.0506 (17)	−0.0032 (13)	0.0152 (14)	−0.0025 (14)
C10	0.0530 (17)	0.0555 (18)	0.0437 (16)	−0.0063 (15)	0.0079 (13)	−0.0136 (14)
C16	0.0458 (15)	0.0361 (14)	0.0431 (15)	−0.0021 (12)	0.0085 (12)	0.0004 (12)
C8	0.0385 (14)	0.0334 (14)	0.0435 (15)	0.0041 (11)	0.0066 (11)	−0.0026 (11)
C22	0.0382 (14)	0.0404 (15)	0.0432 (16)	−0.0017 (12)	0.0103 (12)	−0.0023 (12)
C12	0.0445 (15)	0.0408 (15)	0.0508 (17)	−0.0009 (13)	0.0110 (13)	−0.0008 (13)
C20	0.0572 (17)	0.0453 (17)	0.0435 (16)	−0.0077 (14)	0.0050 (13)	−0.0047 (13)
C27	0.0515 (17)	0.0429 (16)	0.0514 (18)	0.0016 (13)	0.0130 (14)	−0.0007 (13)
C17	0.0487 (15)	0.0428 (15)	0.0350 (15)	−0.0007 (13)	0.0060 (12)	−0.0027 (12)
C9	0.0429 (15)	0.0548 (17)	0.0445 (16)	−0.0065 (14)	0.0102 (12)	−0.0083 (14)
C15	0.0385 (14)	0.0403 (15)	0.0386 (14)	0.0012 (12)	0.0048 (11)	−0.0003 (12)
C6	0.0544 (17)	0.0361 (15)	0.0479 (17)	0.0009 (13)	0.0068 (13)	−0.0029 (13)
C5	0.0402 (14)	0.0386 (14)	0.0387 (14)	0.0057 (12)	0.0033 (11)	−0.0012 (12)
C2	0.0559 (18)	0.0544 (18)	0.0377 (15)	0.0068 (15)	0.0067 (13)	−0.0004 (15)
C4	0.0586 (18)	0.0489 (17)	0.0427 (16)	−0.0082 (14)	0.0119 (13)	−0.0097 (13)
C19	0.071 (2)	0.0476 (17)	0.0465 (17)	−0.0191 (16)	0.0078 (15)	−0.0018 (14)
C23	0.0473 (16)	0.0450 (16)	0.0511 (16)	−0.0004 (14)	0.0091 (13)	0.0027 (14)
N1	0.114 (3)	0.112 (3)	0.0516 (18)	0.004 (2)	0.0303 (18)	−0.0054 (19)
C7	0.0602 (18)	0.0490 (17)	0.0418 (16)	0.0078 (15)	0.0039 (14)	−0.0123 (13)
C3	0.063 (2)	0.0538 (17)	0.0510 (17)	−0.0105 (16)	0.0151 (15)	−0.0012 (14)
C14	0.0506 (16)	0.0398 (15)	0.0465 (16)	−0.0002 (13)	0.0131 (13)	−0.0048 (13)
C18	0.0608 (19)	0.0557 (17)	0.0390 (16)	−0.0142 (15)	0.0105 (14)	0.0036 (15)
C26	0.0610 (19)	0.062 (2)	0.0428 (17)	−0.0149 (16)	0.0112 (14)	−0.0030 (15)
C25	0.061 (2)	0.056 (2)	0.063 (2)	−0.0137 (17)	0.0226 (16)	−0.0223 (17)
C1	0.074 (2)	0.070 (2)	0.0475 (19)	0.0047 (19)	0.0114 (16)	−0.0063 (18)
C24	0.0561 (19)	0.0386 (16)	0.076 (2)	−0.0020 (14)	0.0166 (16)	−0.0101 (16)

Geometric parameters (Å, º) top

O1—C14	1.361 (3)	C27—H27	0.9300
O1—C11	1.405 (3)	C17—C18	1.387 (4)
O3—C17	1.370 (3)	C9—H9	0.9300
O3—C21	1.431 (3)	C15—C14	1.482 (4)
O2—C14	1.197 (3)	C6—C7	1.378 (4)
C11—C12	1.369 (4)	C6—C5	1.388 (4)
C11—C10	1.374 (4)	C6—H6	0.9300
C13—C12	1.386 (4)	C5—C4	1.386 (4)
C13—C8	1.386 (4)	C2—C7	1.377 (4)
C13—H13	0.9300	C2—C3	1.386 (4)
C21—C22	1.492 (4)	C2—C1	1.448 (4)
C21—H21A	0.9700	C4—C3	1.381 (4)
C21—H21B	0.9700	C4—H4	0.9300
C10—C9	1.376 (4)	C19—C18	1.374 (4)
C10—H10	0.9300	C19—H19	0.9300
C16—C17	1.379 (4)	C23—C24	1.376 (4)
C16—C15	1.398 (4)	C23—H23	0.9300
C16—H16	0.9300	N1—C1	1.141 (4)
C8—C9	1.389 (4)	C7—H7	0.9300
C8—C5	1.488 (3)	C3—H3	0.9300
C22—C27	1.385 (4)	C18—H18	0.9300
C22—C23	1.385 (4)	C26—C25	1.372 (5)
C12—H12	0.9300	C26—H26	0.9300
C20—C15	1.378 (4)	C25—C24	1.373 (4)
C20—C19	1.384 (4)	C25—H25	0.9300
C20—H20	0.9300	C24—H24	0.9300
C27—C26	1.385 (4)

C14—O1—C11	119.0 (2)	C20—C15—C14	122.5 (2)
C17—O3—C21	117.4 (2)	C16—C15—C14	116.8 (2)
C12—C11—C10	121.2 (2)	C7—C6—C5	121.2 (3)
C12—C11—O1	117.0 (3)	C7—C6—H6	119.4
C10—C11—O1	121.6 (2)	C5—C6—H6	119.4
C12—C13—C8	121.0 (3)	C4—C5—C6	118.3 (2)
C12—C13—H13	119.5	C4—C5—C8	120.7 (2)
C8—C13—H13	119.5	C6—C5—C8	121.0 (2)
O3—C21—C22	108.2 (2)	C7—C2—C3	120.3 (3)
O3—C21—H21A	110.1	C7—C2—C1	120.9 (3)
C22—C21—H21A	110.1	C3—C2—C1	118.8 (3)
O3—C21—H21B	110.1	C3—C4—C5	121.1 (3)
C22—C21—H21B	110.1	C3—C4—H4	119.5
H21A—C21—H21B	108.4	C5—C4—H4	119.5
C11—C10—C9	119.2 (3)	C18—C19—C20	120.9 (3)
C11—C10—H10	120.4	C18—C19—H19	119.5
C9—C10—H10	120.4	C20—C19—H19	119.5
C17—C16—C15	119.4 (2)	C24—C23—C22	120.7 (3)
C17—C16—H16	120.3	C24—C23—H23	119.6
C15—C16—H16	120.3	C22—C23—H23	119.6
C13—C8—C9	118.2 (2)	C2—C7—C6	119.7 (3)
C13—C8—C5	121.2 (2)	C2—C7—H7	120.2
C9—C8—C5	120.6 (2)	C6—C7—H7	120.2
C27—C22—C23	118.6 (3)	C4—C3—C2	119.5 (3)
C27—C22—C21	121.5 (3)	C4—C3—H3	120.3
C23—C22—C21	119.9 (3)	C2—C3—H3	120.3
C11—C12—C13	119.1 (3)	O2—C14—O1	122.5 (3)
C11—C12—H12	120.4	O2—C14—C15	125.9 (3)
C13—C12—H12	120.4	O1—C14—C15	111.5 (2)
C15—C20—C19	119.1 (3)	C19—C18—C17	119.8 (3)
C15—C20—H20	120.5	C19—C18—H18	120.1
C19—C20—H20	120.5	C17—C18—H18	120.1
C22—C27—C26	120.4 (3)	C25—C26—C27	120.3 (3)
C22—C27—H27	119.8	C25—C26—H26	119.9
C26—C27—H27	119.8	C27—C26—H26	119.9
O3—C17—C16	124.4 (2)	C26—C25—C24	119.8 (3)
O3—C17—C18	115.5 (2)	C26—C25—H25	120.1
C16—C17—C18	120.1 (2)	C24—C25—H25	120.1
C10—C9—C8	121.2 (3)	N1—C1—C2	178.4 (4)
C10—C9—H9	119.4	C25—C24—C23	120.3 (3)
C8—C9—H9	119.4	C25—C24—H24	119.9
C20—C15—C16	120.6 (2)	C23—C24—H24	119.9

C14—O1—C11—C12	120.6 (3)	C9—C8—C5—C4	37.8 (4)
C14—O1—C11—C10	−65.3 (4)	C13—C8—C5—C6	38.2 (4)
C17—O3—C21—C22	179.1 (2)	C9—C8—C5—C6	−141.5 (3)
C12—C11—C10—C9	−1.4 (4)	C6—C5—C4—C3	1.8 (4)
O1—C11—C10—C9	−175.3 (3)	C8—C5—C4—C3	−177.6 (3)
C12—C13—C8—C9	−0.5 (4)	C15—C20—C19—C18	−0.3 (5)
C12—C13—C8—C5	179.8 (2)	C27—C22—C23—C24	0.7 (4)
O3—C21—C22—C27	−52.9 (3)	C21—C22—C23—C24	180.0 (3)
O3—C21—C22—C23	127.8 (3)	C3—C2—C7—C6	1.0 (5)
C10—C11—C12—C13	0.8 (4)	C1—C2—C7—C6	−179.1 (3)
O1—C11—C12—C13	174.9 (2)	C5—C6—C7—C2	0.7 (4)
C8—C13—C12—C11	0.2 (4)	C5—C4—C3—C2	−0.2 (4)
C23—C22—C27—C26	−0.2 (4)	C7—C2—C3—C4	−1.2 (5)
C21—C22—C27—C26	−179.5 (3)	C1—C2—C3—C4	178.9 (3)
C21—O3—C17—C16	9.1 (4)	C11—O1—C14—O2	0.0 (4)
C21—O3—C17—C18	−172.0 (3)	C11—O1—C14—C15	−177.8 (2)
C15—C16—C17—O3	179.6 (3)	C20—C15—C14—O2	−162.2 (3)
C15—C16—C17—C18	0.8 (4)	C16—C15—C14—O2	14.9 (4)
C11—C10—C9—C8	1.0 (4)	C20—C15—C14—O1	15.5 (4)
C13—C8—C9—C10	−0.1 (4)	C16—C15—C14—O1	−167.4 (2)
C5—C8—C9—C10	179.6 (3)	C20—C19—C18—C17	2.4 (5)
C19—C20—C15—C16	−1.6 (4)	O3—C17—C18—C19	178.4 (3)
C19—C20—C15—C14	175.4 (3)	C16—C17—C18—C19	−2.7 (4)
C17—C16—C15—C20	1.3 (4)	C22—C27—C26—C25	−0.4 (4)
C17—C16—C15—C14	−175.9 (2)	C27—C26—C25—C24	0.5 (4)
C7—C6—C5—C4	−2.0 (4)	C26—C25—C24—C23	0.0 (4)
C7—C6—C5—C8	177.3 (3)	C22—C23—C24—C25	−0.6 (4)
C13—C8—C5—C4	−142.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C22–C27 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.93	2.52	3.395 (4)	158
CH—H4···Cg2ⁱ	0.93	2.97	3.805 (3)	151
C9—H9···Cg4ⁱⁱ	0.93	2.90	3.579 (3)	131
C12—H12···Cg4ⁱⁱⁱ	0.93	2.77	3.485 (13)	135

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

Acknowledgements

HM extends his gratitude to Kishore and Shivakumar, C. SSCU, IISc for their help in collecting SCXRD data.

Funding information

BSPM thanks the Vision Group on Science and Technology, Government of Karnataka, for the award of a major project under the CISEE scheme (reference No. VGST/ CISEE/GRD-319/2014–15) to carry out this work at the Department of PG Studies and Research in Physics, Albert Einstein Block, UCS, Tumkur University.

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