Crystal structure and Hirshfeld surface analysis and energy frameworks of 1-(2,4-di­methyl­phen­yl)-4-(4-meth­oxy­phen­yl)naphthalene

Mohamooda Sumaya, U.; KarunaKaran, J.; Biruntha, K.; MohanaKrishnan, A.K.; Usha, G.

doi:10.1107/S2056989018008332

research communications

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 74| Part 7| July 2018| Pages 939-943

https://doi.org/10.1107/S2056989018008332

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Crystal structure and Hirshfeld surface analysis and energy frameworks of 1-(2,4-dimethylphenyl)-4-(4-methoxyphenyl)naphthalene

U. Mohamooda Sumaya,^a J. KarunaKaran,^b K. Biruntha,^a A. K. MohanaKrishnan ^b and G. Usha ^c ^*

^aDepartment of Physics, Bharathi Women's College (A), Chennai-108, Tamilnadu, India, ^bDepartment of Organic Chemistry, University of Madras, Chennai-25, Tamilnadu, India, and ^cPG and Research Department of Physics, Queen Mary's College (A), Chennai-4, Tamilnadu, India
^*Correspondence e-mail: guqmc@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 May 2018; accepted 6 June 2018; online 8 June 2018)

In the title compound, C₂₅H₂₂O, the two rings of the naphthalene system are inclined to each other by 3.06 (15)°. The mean plane of the naphthalene ring system makes a dihedral angle of 65.24 (12)° with the dimethylphenyl ring and 55.82 (12)° with the methoxyphenyl ring. The dimethylphenyl ring is inclined to the methoxyphenyl ring by 59.28 (14)°. In the crystal, adjacent molecules are linked via C—H⋯π interactions, forming chains along [100]. Using Hirshfeld surface and two-dimensional fingerprint plots, the presence of short intermolecular interactions in the crystal structure were analysed. The intermolecular interaction energies were also calculated and their distribution over the crystal structure was visualized graphically using energy frameworks.

Keywords: crystal structure; naphthalene; C—H⋯π interactions; Hirshfeld surface analysis; two-dimensional fingerprint plots; energy frameworks..

CCDC reference: 1841351

1. Chemical context

Naphthalene and its derivatives are known for their wide range of applications in the field of pharmaceuticals. They are also used in the manufacturing of colorants, surface-active agents, resins, disinfectants and insecticides. These derivatives play a vital role in the control of microbial infection (Rokade & Sayyed, 2009 ) and in the chemical defence against biological enemies (Wright et al., 2000 ). Compounds with a naphthalene moiety have been shown to exhibit significant anti-TB activity (Upadhayaya et al., 2010 ).

2. Structural commentary

The molecular structure of the title compound is illustrated in Fig. 1. The benzene ring (C9–C14) of the naphthalene moiety is substituted by a dimethylphenyl ring (C2–C4/C6–C8) and a methoxyphenyl ring (C19–C24) para to each other. The naphthalene ring system is slightly bent with the two aryl rings being inclined to each other by 3.06 (15)°. Its mean plane makes dihedral angles of 65.24 (12)° with the dimethylphenyl ring (C2–C4/C6–C8) and 55.82 (12)° with methoxyphenyl ring (C19–C24). The latter two rings are inclined to each other by 59.28 (14)°. The methoxy group (C22/O1/C25) lies out of the plane of the benzene ring (C19–C24) to which it is attached by 11.3 (3)°. The bond lengths and bond angles are similar to those reported for 1,4-diphenylnaphthalene, which crystallized with two independent molecules in the asymmetric unit (Lima et al., 2012 ).

Figure 1
The molecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at 50% probability level.

3. Supramolecular features

In the crystal, there is only one significant intermolecular interaction present, viz. a C—H⋯π interaction linking adjacent molecules to form chains propagating along the a-axis direction (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C13–C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C25—H25C⋯Cgⁱ	0.96	2.78	3.597 (5)	144
Symmetry code: (i) x-1, y, z.

Figure 2
The crystal packing of the title compound, viewed along the b axis. The C—H⋯π interactions (see Table 1

) are shown as dashed lines, and only the H atom H25C (grey ball) has been included.

4. Database survey

A search of the Cambridge Structural Database (Version 5.39, last update February 2018; Groom et al., 2016 ) for the aromatic skeleton of the title compound yielded ten hits. They include 1,4-diphenylnaphthalene itself, which crystallized with two independent molecules in the asymmetric unit (CSD refcode ZAXJEP: Lima et al., 2012). There are also a number of copper(II) complexes (LAYQOU: Chen et al., 2017 ; BOSHIC: Cai et al., 2014 ; PUBSOV: Lin et al., 2009 ) of the tetracarboxylic acid derivative, 5,5′-(naphthalene-1,4-diyl)diisophthalic acid, all of which are metal–organic frameworks.

5. Analysis of the Hirshfeld surfaces, interaction energies and energy frameworks

The Hirshfeld surfaces and two-dimensional fingerprint plots were generated in order to explore and quantify the weak intermolecular interactions using the program CrystalExplorer 17.5 (Turner et al., 2017 ). The electrostatic potentials were calculated using TONTO, integrated in the program CrystalExplorer (Spackman et al., 2008 ; Jayatilaka et al., 2005 ). The Hirshfeld surfaces of the title compound were mapped over d_norm, electrostatic potential, curvedness and shape index (Fig. 3a–3d); depending upon the closeness to the adjacent molecules, the colour patches are mapped differently on the Hirshfeld surface (Fig. 3e). Two-dimensional fingerprint plots showing the result of all intermolecular contacts (McKinnon et al., 2007 ) are presented in Fig. 4a; d_i (x axis) and d_e (y axis) are the closest internal and external distance from a given point on the Hirshfeld surface. The fingerprint plot of H⋯H contacts, which represent the largest contribution to the Hirshfeld surface (64.6%), are shown as a distinct pattern with a minimum value of d_e = d_i ≃ 1.2 Å (Fig. 4b). The C⋯H/H⋯C interactions appear as the next largest region of the fingerprint plot, highly concentrated at the edges, having almost the same d_e + d_i ≃ 2.7 Å (Fig. 4c), with on overall contribution of 27.1%. The O⋯H/H⋯O interactions on the fingerprint plot, which contribute 5.2% of the total Hirshfeld surfaces, with d_e + d_i ≃ 2.8 Å (Fig. 4d) are shown as two symmetrical wings. The C⋯C contacts, which are the measure of π–π stacking interactions, occupy 3.1% of the Hirshfeld surfaces and appear as a unique triangle at about d_e = d_i ≃ 1.8 Å (Fig. 4e). These weak interactions mostly contribute to the packing of the title compound.

Figure 3
Hirshfeld surfaces mapped over (a) d_norm, (b) electrostatic potential, (c) shape index and (d) curvedness and (e) fragment patches.

Figure 4
Two-dimensional fingerprint plot for the title compound showing the contributions of individual types of interactions: (a) all intermolecular contacts, (b) H⋯H contacts, (c) C⋯H/H⋯C contacts, (d) H⋯O/O⋯H contacts, (e) C⋯C contacts. The outline of the full fingerprint is shown in grey. Surfaces to the right highlight the relevant surface patches associated with the specific contacts with d_norm mapped.

The interaction energies between the molecules are obtained using monomer wavefunctions at the B3LYP/6-31G(p,d) level. The total interaction energy, which is the sum of scaled components, was calculated for a 3.8 Å radius cluster of molecules around the selected molecule (Fig. 5a). The scale factors used in the CE-B3LYP benchmarked energy model (Mackenzie et al., 2017 ) are given in Table 2. The energies calculated by the energy model reveals that the dispersion energy contributes significantly to the interactions in the crystal (Table 3).

Table 2
Scale factors for the benchmarked energy model

Energy model	k_elec	k_pol	k_{energy-dispersive}	k_rep
CE-B3LYP⋯B3LYP/6–31G(d,p) electron densities	1.057	0.740	0.871	0.618

Table 3
Interaction energies (kJ mol⁻¹)

R is the distance between molecular centroids (mean atomic position) in Å and N is the number of molecules at that distance.

Colour	N	symop	R	E_elec	E_pol	E_{energy-dispersive}	E_rep	E_total
Red	2	x, y, z	15.38	−2.2	−0.6	−11.2	6.2	−8.6
Orange	1	−x, −y, −z	15.99	−4.3	−0.8	−11.5	4.2	−12.5
Yellow	1	−x, −y, −z	7.45	−6.2	−1.3	−39.2	19.3	−29.7
Lime	2	x, y, z	9.17	−10.0	−1.8	−44.0	26.8	−33.6
Green	2	x, y, z	10.46	−0.1	−0.1	−6.6	1.5	−5.0
Aquamarine	1	−x, −y, −z	6.86	−6.8	−0.9	−39.9	18.7	−31.0
Cyan	1	−x, −y, −z	10.11	−0.3	−0.4	−19.8	6.7	−13.7
Blue	1	−x, −y, −z	5.37	−3.3	−1.9	−69.2	32.2	−45.2
Violet	1	−x, −y, −z	9.31	−6.5	−0.8	−36.0	20.7	−26.0
Orchid	2	x, y, z	14.01	0.1	0.0	−2.0	0.0	−1.7
Magenta	1	−x, −y, −z	11.61	−3.3	−1.0	−41.6	20.4	−27.9

Figure 5
(a) Interaction between the selected molecule and the molecules present in a 3.8 Å cluster around it, (b) Coulombic energy, (c) dispersion energy and (d) total energy.

The energy framework calculations were performed for a cluster of molecules present in 2 × 2 × 2 unit cells using the CE-B3LYP energy model. Energies between molecular pairs are represented as cylinders joining the centroids of pairs of molecules with the cylinder radius proportional to the magnitude of the interaction energy. Energy frameworks were constructed for E_elec as red cylinders, E_dis as green and E_tot as blue (Fig. 5b–5d) and these cylinders represent the relative strength of molecular packing in different directions. Thus the supramolecular architecture of the crystal structure is visualized uniquely by energy frameworks.

6. Synthesis and crystallization

A reaction scheme for the synthesis of the title compound is illustrated in Fig. 6. To a solution of m-xylyl-p-anisyl tethered benzo[c]furan (0.16 g, 0.49 mmol) in dry xylenes (15 ml) was added tetrathiafulvalene (TTF) (0.10 g, 0.49 mmol) and the mixture was refluxed until the consumption of benzo[c]furan was complete; monitored by the disappearance of the fluorescent colour after 6 h. After the removal of xylenes in vacuo, the crude adduct was dissolved in dry CH₂Cl₂ (15 ml) and then kept at 273 K. To this, triflic acid (0.02 g, 0.13 mmol) was added and the mixture stirred at room temperature for 10 min. After completion of the reaction (monitored by TLC), it was poured into ice–water (20 ml) and then extracted with CH₂Cl₂ (2 × 10 ml). The organic layers were combined and washed with aq. NaHCO₃ (2 × 10 ml) and then dried (Na₂SO₄). Removal of the solvent followed by column chromatographic purification (silica gel, 5% ethyl acetate in hexane) afforded the title compound as a yellow solid (0.20 g, 79%). Yellow block-like crystals of the title compound, suitable for X-ray diffraction analysis, were obtained by slow evaporation of a solution in CHCl₃ (m.p. 351–353 K).

Figure 6
Reaction scheme.

7. Refinement

Crystal data collection and structure refinement details are summarized in Table 4. All H atoms were positioned geometrically and refined using a riding model: C—H = 0.93–0.96 Å with U_iso(H) = 1.5 U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.

Table 4
Experimental details

Crystal data
Chemical formula	C₂₅H₂₂O
M_r	338.42
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.1670 (9), 10.4566 (10), 11.2499 (11)
α, β, γ (°)	64.707 (4), 71.312 (4), 77.032 (4)
V (Å³)	918.75 (16)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.07
Crystal size (mm)	0.15 × 0.10 × 0.10

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.900, 0.945
No. of measured, independent and observed [I > 2σ(I)] reflections	19120, 3828, 1777
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.193, 1.00
No. of reflections	3828
No. of parameters	238
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.19
Computer programs: APEX2, SAINT and XPREP (Bruker, 2012), SHELXT2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and Mercury (Macrae et al., 2008 ).

Supporting information

CCDC reference: 1841351

Crystal structure: contains datablocks I, Global. DOI: https://doi.org/10.1107/S2056989018008332/su5445sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018008332/su5445Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989018008332/su5445Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 and SAINT (Bruker, 2012); data reduction: SAINT and XPREP (Bruker, 2012); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

1-(2,4-Dimethylphenyl)-4-(4-methoxyphenyl)naphthalene top

Crystal data top

C₂₅H₂₂O	Z = 2
M_r = 338.42	F(000) = 360
Triclinic, P1	D_x = 1.223 Mg m⁻³
a = 9.1670 (9) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4566 (10) Å	Cell parameters from 19154 reflections
c = 11.2499 (11) Å	θ = 2.3–22.7°
α = 64.707 (4)°	µ = 0.07 mm⁻¹
β = 71.312 (4)°	T = 296 K
γ = 77.032 (4)°	Block, yellow
V = 918.75 (16) Å³	0.15 × 0.10 × 0.10 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	1777 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.060
ω and φ scan	θ_max = 26.6°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→11
T_min = 0.900, T_max = 0.945	k = −13→13
19120 measured reflections	l = −14→14
3828 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.193	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0922P)² + 0.0768P] where P = (F_o² + 2F_c²)/3
3828 reflections	(Δ/σ)_max < 0.001
238 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.19 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
C1	0.7907 (4)	0.8345 (4)	0.2984 (3)	0.0771 (10)
H1A	0.7017	0.8047	0.2937	0.116*
H1B	0.7750	0.9350	0.2771	0.116*
H1C	0.8053	0.7849	0.3885	0.116*
C2	0.9307 (3)	0.8015 (3)	0.1987 (3)	0.0509 (7)
C3	1.0610 (3)	0.8748 (3)	0.1542 (3)	0.0578 (8)
H3	1.0583	0.9411	0.1898	0.069*
C4	1.1927 (3)	0.8530 (3)	0.0602 (3)	0.0573 (8)
C5	1.3309 (4)	0.9324 (4)	0.0196 (4)	0.0863 (11)
H5A	1.4237	0.8679	0.0169	0.129*
H5B	1.3205	0.9724	0.0848	0.129*
H5C	1.3365	1.0071	−0.0686	0.129*
C6	1.1935 (3)	0.7571 (3)	0.0065 (3)	0.0598 (8)
H6	1.2803	0.7415	−0.0585	0.072*
C7	1.0668 (3)	0.6835 (3)	0.0480 (3)	0.0541 (7)
H7	1.0699	0.6198	0.0093	0.065*
C8	0.9353 (3)	0.7015 (3)	0.1453 (3)	0.0446 (7)
C9	0.8049 (3)	0.6158 (3)	0.1869 (3)	0.0437 (6)
C10	0.7284 (3)	0.6328 (3)	0.0942 (3)	0.0537 (7)
H10	0.7534	0.7037	0.0079	0.064*
C11	0.6138 (3)	0.5472 (3)	0.1247 (3)	0.0527 (7)
H11	0.5648	0.5633	0.0581	0.063*
C12	0.5716 (3)	0.4408 (3)	0.2488 (3)	0.0426 (6)
C13	0.6437 (3)	0.4220 (3)	0.3514 (2)	0.0393 (6)
C14	0.7621 (3)	0.5075 (3)	0.3195 (2)	0.0403 (6)
C15	0.8360 (3)	0.4807 (3)	0.4219 (3)	0.0507 (7)
H15	0.9173	0.5323	0.4017	0.061*
C16	0.7907 (3)	0.3810 (3)	0.5493 (3)	0.0602 (8)
H16	0.8414	0.3649	0.6147	0.072*
C17	0.6690 (3)	0.3029 (3)	0.5823 (3)	0.0612 (8)
H17	0.6361	0.2374	0.6706	0.073*
C18	0.5983 (3)	0.3221 (3)	0.4860 (3)	0.0518 (7)
H18	0.5180	0.2682	0.5092	0.062*
C19	0.4540 (3)	0.3483 (3)	0.2743 (2)	0.0432 (6)
C20	0.3108 (3)	0.4064 (3)	0.2491 (3)	0.0504 (7)
H20	0.2877	0.5046	0.2182	0.060*
C21	0.2007 (3)	0.3235 (3)	0.2682 (3)	0.0525 (7)
H21	0.1051	0.3658	0.2507	0.063*
C22	0.2331 (3)	0.1787 (3)	0.3130 (3)	0.0510 (7)
C23	0.3750 (3)	0.1177 (3)	0.3379 (3)	0.0601 (8)
H23	0.3977	0.0195	0.3676	0.072*
C24	0.4841 (3)	0.2011 (3)	0.3193 (3)	0.0543 (7)
H24	0.5794	0.1581	0.3371	0.065*
C25	−0.0236 (4)	0.1430 (4)	0.3343 (4)	0.0834 (11)
H25A	−0.0854	0.0667	0.3644	0.125*
H25B	−0.0284	0.2070	0.2437	0.125*
H25C	−0.0624	0.1932	0.3942	0.125*
O1	0.1324 (2)	0.0867 (2)	0.3352 (2)	0.0742 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.076 (2)	0.079 (2)	0.081 (2)	−0.0173 (19)	−0.0011 (18)	−0.044 (2)
C2	0.0503 (17)	0.0521 (17)	0.0505 (17)	−0.0106 (14)	−0.0132 (14)	−0.0171 (14)
C3	0.068 (2)	0.0485 (17)	0.0622 (19)	−0.0158 (15)	−0.0235 (16)	−0.0169 (15)
C4	0.0534 (18)	0.0526 (18)	0.0532 (18)	−0.0149 (15)	−0.0173 (15)	−0.0013 (15)
C5	0.069 (2)	0.091 (3)	0.088 (3)	−0.040 (2)	−0.0228 (19)	−0.007 (2)
C6	0.0523 (18)	0.0585 (19)	0.0533 (18)	−0.0127 (15)	−0.0040 (14)	−0.0106 (16)
C7	0.0547 (17)	0.0528 (18)	0.0498 (17)	−0.0128 (14)	−0.0061 (14)	−0.0169 (14)
C8	0.0491 (16)	0.0419 (15)	0.0427 (15)	−0.0124 (13)	−0.0133 (13)	−0.0113 (13)
C9	0.0458 (15)	0.0475 (16)	0.0415 (15)	−0.0104 (13)	−0.0101 (12)	−0.0186 (13)
C10	0.0621 (18)	0.0550 (18)	0.0421 (16)	−0.0192 (15)	−0.0150 (14)	−0.0093 (14)
C11	0.0593 (18)	0.0571 (18)	0.0424 (17)	−0.0159 (15)	−0.0180 (14)	−0.0113 (14)
C12	0.0412 (15)	0.0454 (15)	0.0438 (16)	−0.0070 (12)	−0.0088 (12)	−0.0197 (13)
C13	0.0393 (14)	0.0416 (15)	0.0365 (15)	−0.0044 (12)	−0.0067 (11)	−0.0165 (12)
C14	0.0404 (14)	0.0416 (15)	0.0408 (15)	−0.0055 (12)	−0.0091 (12)	−0.0178 (13)
C15	0.0515 (16)	0.0574 (18)	0.0482 (17)	−0.0131 (14)	−0.0149 (14)	−0.0197 (15)
C16	0.069 (2)	0.070 (2)	0.0467 (18)	−0.0158 (17)	−0.0230 (15)	−0.0174 (16)
C17	0.073 (2)	0.067 (2)	0.0392 (17)	−0.0215 (17)	−0.0110 (15)	−0.0115 (15)
C18	0.0526 (17)	0.0563 (18)	0.0454 (17)	−0.0149 (14)	−0.0063 (13)	−0.0185 (15)
C19	0.0435 (15)	0.0456 (16)	0.0436 (15)	−0.0065 (13)	−0.0088 (12)	−0.0206 (13)
C20	0.0522 (17)	0.0465 (16)	0.0551 (17)	−0.0068 (14)	−0.0183 (13)	−0.0179 (14)
C21	0.0458 (16)	0.0576 (19)	0.0610 (18)	−0.0057 (14)	−0.0174 (13)	−0.0261 (15)
C22	0.0521 (18)	0.0548 (19)	0.0544 (18)	−0.0148 (15)	−0.0075 (14)	−0.0285 (15)
C23	0.060 (2)	0.0463 (17)	0.076 (2)	−0.0056 (16)	−0.0136 (16)	−0.0280 (16)
C24	0.0451 (16)	0.0518 (18)	0.0666 (19)	−0.0019 (14)	−0.0130 (14)	−0.0256 (15)
C25	0.060 (2)	0.102 (3)	0.108 (3)	−0.029 (2)	−0.0172 (19)	−0.051 (2)
O1	0.0641 (14)	0.0687 (14)	0.1023 (18)	−0.0233 (12)	−0.0140 (12)	−0.0415 (13)

Geometric parameters (Å, º) top

C1—C2	1.495 (4)	C13—C18	1.413 (3)
C1—H1A	0.9600	C13—C14	1.421 (3)
C1—H1B	0.9600	C14—C15	1.416 (3)
C1—H1C	0.9600	C15—C16	1.360 (4)
C2—C8	1.399 (4)	C15—H15	0.9300
C2—C3	1.401 (3)	C16—C17	1.390 (3)
C3—C4	1.375 (4)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.357 (4)
C4—C6	1.373 (4)	C17—H17	0.9300
C4—C5	1.510 (4)	C18—H18	0.9300
C5—H5A	0.9600	C19—C20	1.380 (4)
C5—H5B	0.9600	C19—C24	1.391 (4)
C5—H5C	0.9600	C20—C21	1.383 (3)
C6—C7	1.381 (3)	C20—H20	0.9300
C6—H6	0.9300	C21—C22	1.370 (4)
C7—C8	1.385 (3)	C21—H21	0.9300
C7—H7	0.9300	C22—O1	1.373 (3)
C8—C9	1.488 (3)	C22—C23	1.373 (4)
C9—C10	1.366 (3)	C23—C24	1.381 (3)
C9—C14	1.430 (3)	C23—H23	0.9300
C10—C11	1.397 (3)	C24—H24	0.9300
C10—H10	0.9300	C25—O1	1.420 (4)
C11—C12	1.363 (4)	C25—H25A	0.9600
C11—H11	0.9300	C25—H25B	0.9600
C12—C13	1.430 (3)	C25—H25C	0.9600
C12—C19	1.488 (3)

C2—C1—H1A	109.5	C18—C13—C12	121.9 (2)
C2—C1—H1B	109.5	C14—C13—C12	119.8 (2)
H1A—C1—H1B	109.5	C15—C14—C13	118.0 (2)
C2—C1—H1C	109.5	C15—C14—C9	121.8 (2)
H1A—C1—H1C	109.5	C13—C14—C9	120.2 (2)
H1B—C1—H1C	109.5	C16—C15—C14	121.4 (3)
C8—C2—C3	118.4 (2)	C16—C15—H15	119.3
C8—C2—C1	122.1 (2)	C14—C15—H15	119.3
C3—C2—C1	119.5 (3)	C15—C16—C17	120.4 (3)
C4—C3—C2	122.9 (3)	C15—C16—H16	119.8
C4—C3—H3	118.5	C17—C16—H16	119.8
C2—C3—H3	118.5	C18—C17—C16	120.1 (3)
C6—C4—C3	117.8 (3)	C18—C17—H17	120.0
C6—C4—C5	121.9 (3)	C16—C17—H17	120.0
C3—C4—C5	120.3 (3)	C17—C18—C13	121.6 (3)
C4—C5—H5A	109.5	C17—C18—H18	119.2
C4—C5—H5B	109.5	C13—C18—H18	119.2
H5A—C5—H5B	109.5	C20—C19—C24	117.0 (2)
C4—C5—H5C	109.5	C20—C19—C12	120.9 (2)
H5A—C5—H5C	109.5	C24—C19—C12	122.1 (2)
H5B—C5—H5C	109.5	C19—C20—C21	122.2 (3)
C4—C6—C7	120.7 (3)	C19—C20—H20	118.9
C4—C6—H6	119.7	C21—C20—H20	118.9
C7—C6—H6	119.7	C22—C21—C20	119.7 (3)
C6—C7—C8	122.1 (3)	C22—C21—H21	120.2
C6—C7—H7	119.0	C20—C21—H21	120.2
C8—C7—H7	119.0	C21—C22—O1	124.4 (3)
C7—C8—C2	118.1 (2)	C21—C22—C23	119.5 (3)
C7—C8—C9	118.8 (2)	O1—C22—C23	116.0 (3)
C2—C8—C9	123.1 (2)	C22—C23—C24	120.5 (3)
C10—C9—C14	117.6 (2)	C22—C23—H23	119.8
C10—C9—C8	120.0 (2)	C24—C23—H23	119.8
C14—C9—C8	122.3 (2)	C23—C24—C19	121.2 (3)
C9—C10—C11	122.3 (3)	C23—C24—H24	119.4
C9—C10—H10	118.9	C19—C24—H24	119.4
C11—C10—H10	118.9	O1—C25—H25A	109.5
C12—C11—C10	122.1 (3)	O1—C25—H25B	109.5
C12—C11—H11	119.0	H25A—C25—H25B	109.5
C10—C11—H11	119.0	O1—C25—H25C	109.5
C11—C12—C13	118.0 (2)	H25A—C25—H25C	109.5
C11—C12—C19	120.0 (2)	H25B—C25—H25C	109.5
C13—C12—C19	122.0 (2)	C22—O1—C25	117.3 (2)
C18—C13—C14	118.4 (2)

C8—C2—C3—C4	0.2 (4)	C12—C13—C14—C9	2.4 (3)
C1—C2—C3—C4	−178.4 (3)	C10—C9—C14—C15	179.2 (2)
C2—C3—C4—C6	1.4 (4)	C8—C9—C14—C15	3.5 (4)
C2—C3—C4—C5	−178.2 (3)	C10—C9—C14—C13	0.0 (3)
C3—C4—C6—C7	−1.2 (4)	C8—C9—C14—C13	−175.7 (2)
C5—C4—C6—C7	178.4 (3)	C13—C14—C15—C16	−3.2 (4)
C4—C6—C7—C8	−0.7 (4)	C9—C14—C15—C16	177.6 (2)
C6—C7—C8—C2	2.3 (4)	C14—C15—C16—C17	−0.3 (4)
C6—C7—C8—C9	−178.6 (2)	C15—C16—C17—C18	2.4 (4)
C3—C2—C8—C7	−2.0 (4)	C16—C17—C18—C13	−0.9 (4)
C1—C2—C8—C7	176.6 (3)	C14—C13—C18—C17	−2.6 (4)
C3—C2—C8—C9	178.9 (2)	C12—C13—C18—C17	178.8 (3)
C1—C2—C8—C9	−2.5 (4)	C11—C12—C19—C20	−53.8 (3)
C7—C8—C9—C10	−63.5 (3)	C13—C12—C19—C20	126.4 (3)
C2—C8—C9—C10	115.5 (3)	C11—C12—C19—C24	123.9 (3)
C7—C8—C9—C14	112.1 (3)	C13—C12—C19—C24	−56.0 (3)
C2—C8—C9—C14	−68.9 (3)	C24—C19—C20—C21	0.5 (4)
C14—C9—C10—C11	−1.1 (4)	C12—C19—C20—C21	178.2 (2)
C8—C9—C10—C11	174.7 (2)	C19—C20—C21—C22	−0.3 (4)
C9—C10—C11—C12	−0.3 (4)	C20—C21—C22—O1	−179.9 (2)
C10—C11—C12—C13	2.7 (4)	C20—C21—C22—C23	−0.2 (4)
C10—C11—C12—C19	−177.2 (2)	C21—C22—C23—C24	0.6 (4)
C11—C12—C13—C18	174.9 (2)	O1—C22—C23—C24	−179.7 (2)
C19—C12—C13—C18	−5.2 (3)	C22—C23—C24—C19	−0.4 (4)
C11—C12—C13—C14	−3.7 (3)	C20—C19—C24—C23	−0.1 (4)
C19—C12—C13—C14	176.2 (2)	C12—C19—C24—C23	−177.8 (2)
C18—C13—C14—C15	4.5 (3)	C21—C22—O1—C25	−11.4 (4)
C12—C13—C14—C15	−176.8 (2)	C23—C22—O1—C25	168.9 (3)
C18—C13—C14—C9	−176.2 (2)

Hydrogen-bond geometry (Å, º) top

Cg is the centroid of the C13–C18 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C25—H25C···Cgⁱ	0.96	2.78	3.597 (5)	144

Symmetry code: (i) x−1, y, z.

Scale factors for the benchmarked energy model top

Energy model	k_elec	k_pol	k_disp	k_rep
CE-B3LYP···B3LYP/6-31G(d,p) electron densities	1.057	0.740	0.871	0.618

Interaction energies (KJ mol^-1) top

R is the distance between molecular centroids (mean atomic position) in Å.

Colour	N	symop	R	E_elec	E_pol	E_disp	E_rep	E_total
Red	2	x, y, z	15.38	-2.2	-0.6	-11.2	6.2	-8.6
Orange	1	-x, -y, -z	15.99	-4.3	-0.8	-11.5	4.2	-12.5
Yellow	1	-x, -y, -z	7.45	-6.2	-1.3	-39.2	19.3	-29.7
Lime	2	x, y, z	9.17	-10.0	-1.8	-44.0	26.8	-33.6
Green	2	x, y, z	10.46	-0.1	-0.1	-6.6	1.5	-5.0
Aquamarine	1	-x, -y, -z	6.86	-6.8	-0.9	-39.9	18.7	-31.0
Cyan	1	-x, -y, -z	10.11	-0.3	-0.4	-19.8	6.7	-13.7
Blue	1	-x, -y, -z	5.37	-3.3	-1.9	-69.2	32.2	-45.2
Violet	1	-x, -y, -z	9.31	-6.5	-0.8	-36.0	20.7	-26.0
Orchid	2	x, y, z	14.01	0.1	0.0	-2.0	0.0	-1.7
Magenta	1	-x, -y, -z	11.61	-3.3	-1.0	-41.6	20.4	-27.9

Acknowledgements

The authors thank the Central Instrumentation Facility (DST–FIST), Queen Mary's College (A), Chennai-4, for the computing facilities and the SAIF, IIT, Madras, for the X-ray data collection facility.

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