(E)-1,3-Bis(anthracen-9-yl)prop-2-en-1-one: crystal structure and DFT study

Zainuri, D.A.; Razak, I.A.; Arshad, S.

doi:10.1107/S2056989018003791

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ISSN: 2056-9890

Volume 74| Part 4| April 2018| Pages 492-496

https://doi.org/10.1107/S2056989018003791

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(E)-1,3-Bis(anthracen-9-yl)prop-2-en-1-one: crystal structure and DFT study

Dian Alwani Zainuri,^a Ibrahim Abdul Razak ^a and Suhana Arshad ^a ^*

^aX-ray Crystallography Unit, School of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
^*Correspondence e-mail: suhanaarshad@usm.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 12 February 2018; accepted 5 March 2018; online 9 March 2018)

The title compound, C₃₁H₂₀O, was synthesized using a Claisen–Schmidt condensation. The enone group adopts an s-trans conformation and the anthracene ring systems are twisted at angles of 85.21 (19) and 83.98 (19)° from the enone plane. In the crystal, molecules are connected into chains along [100] via weak C—H⋯π interactions. The observed band gap of 3.03 eV is in excellent agreement with that (3.07 eV) calculated using density functional theory (DFT) at the B3LYP/6–311++G(d,p) level. The Hirshfeld surface analysis indicates a high percentage of C⋯H/H⋯C (41.2%) contacts in the crystal.

Keywords: crystal structure; chalcone; absorption spectra; HOMO–LUMO; Hirshfeld surface.

CCDC reference: 1817217

1. Chemical context

Anthrancene and its derivatives constitute a very well-known class with interesting photophysical properties and they are used extensively in the design of luminescent chemosensors and switches (Montalti et al., 2000 ). A chalcone molecule with a π-conjugated system provides a large charge-transfer axis with appropriate substituent groups on the terminal aromatic rings. Strong intermolecular charge transfer (ICT) will give rise to second harmonic generation (SHG) efficiency and this may enhance the non-linear optical (NLO) properties (D'silva et al., 2011 ). Furthermore, π-conjugated molecular materials with fused rings are the focus of considerable interest in the emerging area of organic electronics, since the combination of good charge-carrier mobility and high stability may lead to potential optoelectronic applications (Wu et al., 2010 ). As part of our work in this area, we now report the synthesis and combined experimental and theoretical studies of the title compound, (I).

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1 (for the optimized structure, see Fig. S1 in the Supporting information). The structure consists of two anthracene rings (Anth A and Anth B) . Anth A is formed by the aromatic rings labeled as Cg1(C1–C6), Cg2(C1/C6–C8/C13/C14) and Cg3(C8–C13). Anth B consists of Cg4(C18/C19/C24–C26/C31, Cg5(C19–C24) and Cg6(C26–C31).

Figure 1
The molecular structure of (I)

showing 50% displacement ellipsoids.

The C—C distances in the central ring of the anthracene units show little variation compared to the other rings (Anth A: C20—C21, C22—C23, C27—C28 and C29—C30; Anth B: C2—C3, C4—C5, C9—C10 and C11—C12), which are much shorter. These observations are consistent with an electronic structure for the anthracene units where a central ring displaying aromatic delocalization is flanked by two isolated diene units (Glidewell & Lloyd, 1984 ). Both theoretical and experimental structures exist in an E configuration with respect to the C16=C17 double bond [experimental = 1.291 (2) Å and DFT (see below) = 1.34 Å].

The enone moiety (O1/C15–C17) shows an s-trans configuration with the O1—C15—C16—C17 torsion angle being −179.19 (19) and 179.64° in the experimental and calculated structures, respectively. Additionally, the enone moiety [O1/C15–C17, maximum deviation of 0.0039 (18) Å at C16] forms dihedral angles of 85.21 (19) and 83.98 (19)° with the Anth A [C1–C14, maximum deviation of 0.103 (2) Å at C11] and Anth B [C18–C31, maximum deviation of 0.016 (3) Å at C27] groups, respectively. The large dihedral-angle deviation indicates that the possibility for electronic effects between the anthracene units through the enone moiety has decreased (Jung et al., 2008 ). This is in contrast with the molecular structure of (E)-1-(anthracen-9-yl)-3-(2-chloro-6-fluorophenyl)prop-2-en-1-one (Abdullah et al. 2016 ), which shows the enone moiety locked in an s-cis configuration because of the intramolecular hydrogen bond. Furthermore, the bulkiness of the anthracene ring gives rise to a highly twisted structure at both terminal rings. Compound (I) is twisted at the C17—C18 and C14—C15 bonds with C16—C17—C18—C19 and C1—C14—C15—C16 torsion angles of 84.0 (2) and 93.65 (19)°, respectively (see Fig. S2 in the Supporting information). The corresponding torsion angles for the DFT study are 48.01 and 94.05°, respectively. We propose that the torsion-angle difference of about 35.9° between the experimental and DFT studies are the result of the formation of intermolecular C—H⋯π interactions involving the anthracene units. The observed intermolecular interactions in the crystal packing are the main cause of the angle difference when this interaction is not taken into consideration during the optimization process.

3. Supramolecular features

In the crystal of (I), C—H⋯π interactions are mainly responsible for the packing. Two C—H⋯π interactions (Fig. 2 and Table 1) occur between anthracene rings (Anth A and Anth B), connecting the molecules into infinite zigzag chains propagating along the [100] direction.

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 and Cg6 are the centroids of the C18/C19/C24–C26/C31 and C26–C31 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯Cg4ⁱ	0.93	2.75	3.511 (2)	140
C7—H7A⋯Cg6ⁱ	0.93	2.91	3.672 (2)	140
Symmetry code: (i) x-1, y, z.

Figure 2
The weak C—H⋯π interactions in the crystal of (I)

4. Theoretical chemistry study

The optimization of the molecular geometries leading to energy minima was achieved using DFT [with Becke's non-local three parameter exchange and the Lee–Yang–Parr correlation functional (B3LYP)] with the 6-311++G (d,p) basis set as implemented in Gaussian09 program package (Frisch et al., 2009 ). The selected bond lengths and angles of the optimized structure in comparison to the experimental values are presented in Table S2 in the Supporting information and the optimized structure is presented in Figure S1. Agreement between experimental and calculated geometrical data is generally good and any deviations may be ascribed to the fact that the optimization is performed in an isolated condition, whereas the crystal environment affects the molecular geometry (Ramya et al., 2015 ).

5. Absorption spectrum and frontier molecular orbitals

The longest wavelength absorption maxima for (I) is observed in the UV region at 383 nm as shown in Fig. 3. The TD–DFT calculation at the B3LYP/6-311G++(d,p) level shows that this feature is due to an electronic transition from the highest occupied molecular orbital (HOMO) to the lowest unoccupied molecular orbital (LUMO). In the ground state (HOMO), the charge densities are mainly delocalized over the anthracene rings and the enone moiety, while in the LUMO state, the charge densities are accumulated on the Anth A and enone moiety (see Fig. S3 in the Supporting information). The calculated λ_max of 390 nm is shifted from the experimental value, which may be attributed to solvent effects, compared to the gas-phase calculation.

Figure 3
UV–Vis absorption spectra of (I)

The HOMO–LUMO energy gap (Fig. S3) relates to the chemical activity of the molecule (Kosar & Albayrak, 2011 ). The predicted energy gap of 3.07 eV shows excellent agreement with the estimated experimental energy gap of 3.03 eV. These optical band-gap values indicate the potential suitability of this compound for optoelectronic applications, as previously reported by Prabhu et al. (2016 ). Additionally, Nietfeld et al. (2011 ) compared the structural, electrochemical and optical properties of fused-ring and non-fused ring compounds, indicating that fused rings have lower band gaps than other structures.

6. Hirshfeld Surface analysis

Fig. 4 shows the Hirshfeld surface mapped over d_norm. As expected, the d_norm surfaces reveal the C—H⋯π intermolecular interaction as a large depression (bright-red spot). The presence of this C—H⋯π interaction is also indicated through the combination of pale-orange and bright-red spots that are present on the Hirshfeld surfaces mapped over d_e (Fig. 5a) and shape-index (Fig. 5b).

Figure 4
View of the Hirshfeld surfaces mapped over d_norm for (I)

Figure 5
View of the Hirshfeld surfaces for (I)

mapped over (a) d_e and (b) shape-index with the pale-orange spot within the red circles showing the presence of the C—H⋯π interactions.

The two-dimensional fingerprint plots shown in Fig. 6 illustrate the difference between the intermolecular interaction patterns and the major intermolecular contacts associated with the title compound. The H⋯H contacts (Fig. 6b) appear to be the major contributor to the Hirshfeld surface and are seen as one distinct spike with a minimum value for d_e + d_i that is less than the sum of the van der Waals radii (2.4 Å). The intermolecular C—H⋯π interactions are characterized by the short interatomic C⋯H/H⋯C (41.2%) contacts and their presence is indicated by the distribution of points around a pair of wings at d_e + d_i ∼2.6 Å (Fig. 6c).

Figure 6
Fingerprint plots of interactions, listing the percentage of contacts (a) full two-dimensional fingerprint plots, and (b) H⋯H and (c) C⋯H/H⋯C contributions to the total Hirshfeld surface. The outline of the full fingerprint plots is shown in grey.

7. Database survey

A survey of the Cambridge Structural Database (CSD, Version 5.38, last update Nov 2016; Groom et al., 2016 ) revealed fused-ring substituted chalcones similar to the title compound. There are four compounds which have an anthracene-ketone subtituent on the chalcone: 9-anthryl styryl ketone and 9,10-anthryl bis(styryl ketone) (Harlow et al., 1975 ), (2E)-1-(anthracen-9-yl)-3-[4-(propan-2-yl)phenyl]prop-2-en-1-one (Girisha et al., 2016 ) and (E)-1-(anthracen-9-yl)-3-(2-chloro-6-fluorophenyl) prop-2-en-1-one (Abdullah et al., 2016). Jung et al. (2008) reported two ferrocenyl chalcones containing an anthracenyl subtituent, 9-(2-ferrocenylethenylcarbonyl)anthracene and 1-(9-anthracenyl)-3-ferrocenyl-2-propen-1-one. Other related compounds include, 1-(anthracen-9-yl)-2-methylprop-2-en-1-one (Agrahari et al., 2015 ) and 9-anthroylacetone (Cicogna et al., 2004 ).

8. Synthesis and crystallization

A mixture of 9-acetylanthracene (0.5 mmol) and 9-anthracenecarboxaldehyde (0.5 mmol) was dissolved in methanol (20 ml). A catalytic amount of NaOH (5 ml, 20%) was added to the solution dropwise with vigorous stirring. The reaction mixture was stirred for about 5-6 h at room temperature. After stirring, the contents of the flask were poured into ice-cold water (50 ml). The resultant crude products were filtered, washed successively with distilled water and recrystallized from acetone solution as yellow blocks. The single crystal (Fig. S4) used for data collection was obtained by the slow-evaporation technique using acetone as the solvent.

9. Refinement

Crystal data collection and structure refinement details are summarized in Table 2. All H atoms were positioned geometrically (C—H =0.93 Å) and refined using riding model with U_iso(H)=1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	C₃₁H₂₀O
M_r	408.47
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.8310 (17), 10.7521 (18), 11.3029 (19)
α, β, γ (°)	67.146 (2), 73.586 (2), 78.768 (2)
V (Å³)	1051.2 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.45 × 0.38 × 0.26

Data collection
Diffractometer	Bruker SMART APEXII DUO CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
No. of measured, independent and observed [I > 2σ(I)] reflections	42832, 6216, 2792
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.709

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.187, 1.00
No. of reflections	6216
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.15
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXL2013 (Sheldrick, 2015 ), SHELXTL (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Supporting information

CCDC reference: 1817217

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989018003791/hb7739sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018003791/hb7739Isup2.hkl

Supplemetary figures and table. DOI: https://doi.org/10.1107/S2056989018003791/hb7739sup3.pdf

Supporting information file. DOI: https://doi.org/10.1107/S2056989018003791/hb7739Isup4.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

(E)-1,3-Bis(anthracen-9-yl)prop-2-en-1-one top

Crystal data top

C₃₁H₂₀O	Z = 2
M_r = 408.47	F(000) = 428
Triclinic, P1	D_x = 1.290 Mg m⁻³
a = 9.8310 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7521 (18) Å	Cell parameters from 3766 reflections
c = 11.3029 (19) Å	θ = 2.3–22.1°
α = 67.146 (2)°	µ = 0.08 mm⁻¹
β = 73.586 (2)°	T = 296 K
γ = 78.768 (2)°	Block, yellow
V = 1051.2 (3) Å³	0.45 × 0.38 × 0.26 mm

Data collection top

Bruker SMART APEXII DUO CCD area-detector diffractometer	2792 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
φ and ω scans	θ_max = 30.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −13→13
	k = −15→15
42832 measured reflections	l = −15→15
6216 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.057	H-atom parameters constrained
wR(F²) = 0.187	w = 1/[σ²(F_o²) + (0.0746P)² + 0.1037P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
6216 reflections	Δρ_max = 0.20 e Å⁻³
289 parameters	Δρ_min = −0.15 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
O1	0.44003 (14)	0.39564 (13)	0.83904 (17)	0.0974 (5)
C1	0.18125 (17)	0.58896 (16)	0.72383 (17)	0.0557 (4)
C2	0.2456 (2)	0.55577 (19)	0.6096 (2)	0.0745 (5)
H2A	0.3398	0.5184	0.5977	0.089*
C3	0.1725 (3)	0.5774 (2)	0.5176 (2)	0.0895 (6)
H3A	0.2174	0.5560	0.4428	0.107*
C4	0.0287 (3)	0.6321 (2)	0.5335 (2)	0.0848 (6)
H4A	−0.0202	0.6472	0.4690	0.102*
C5	−0.0372 (2)	0.66204 (17)	0.6411 (2)	0.0702 (5)
H5A	−0.1325	0.6962	0.6513	0.084*
C6	0.03472 (17)	0.64307 (16)	0.74020 (18)	0.0564 (4)
C7	−0.03088 (16)	0.67773 (16)	0.84986 (18)	0.0589 (4)
H7A	−0.1270	0.7093	0.8621	0.071*
C8	0.04251 (16)	0.66686 (15)	0.94246 (17)	0.0551 (4)
C9	−0.0227 (2)	0.70868 (18)	1.05166 (19)	0.0707 (5)
H9A	−0.1189	0.7397	1.0651	0.085*
C10	0.0525 (3)	0.7042 (2)	1.1362 (2)	0.0834 (6)
H10A	0.0083	0.7335	1.2065	0.100*
C11	0.1973 (2)	0.6556 (2)	1.1191 (2)	0.0776 (5)
H11A	0.2487	0.6544	1.1772	0.093*
C12	0.26246 (19)	0.61070 (18)	1.01937 (18)	0.0659 (5)
H12A	0.3577	0.5762	1.0115	0.079*
C13	0.18947 (16)	0.61474 (15)	0.92571 (16)	0.0529 (4)
C14	0.25475 (16)	0.57424 (15)	0.81840 (16)	0.0528 (4)
C15	0.40796 (17)	0.51694 (18)	0.80046 (18)	0.0633 (5)
C16	0.51726 (17)	0.61184 (17)	0.73382 (18)	0.0666 (5)
H16A	0.6119	0.5756	0.7213	0.080*
C17	0.49221 (16)	0.74227 (16)	0.69108 (16)	0.0564 (4)
H17A	0.3972	0.7775	0.7032	0.068*
C18	0.59990 (15)	0.84051 (15)	0.62495 (16)	0.0510 (4)
C19	0.65765 (16)	0.87661 (16)	0.48951 (17)	0.0547 (4)
C20	0.6174 (2)	0.82323 (19)	0.40902 (19)	0.0701 (5)
H20A	0.5499	0.7606	0.4473	0.084*
C21	0.6744 (2)	0.8611 (2)	0.2788 (2)	0.0881 (6)
H21A	0.6459	0.8247	0.2282	0.106*
C22	0.7768 (3)	0.9552 (2)	0.2183 (2)	0.0955 (7)
H22A	0.8155	0.9807	0.1280	0.115*
C23	0.8190 (2)	1.0082 (2)	0.2896 (2)	0.0830 (6)
H23A	0.8875	1.0697	0.2480	0.100*
C24	0.76171 (18)	0.97267 (17)	0.42761 (18)	0.0634 (5)
C25	0.80165 (19)	1.02850 (18)	0.5019 (2)	0.0720 (5)
H25A	0.8687	1.0914	0.4605	0.086*
C26	0.74538 (19)	0.99421 (17)	0.6362 (2)	0.0658 (5)
C27	0.7864 (3)	1.0506 (2)	0.7140 (3)	0.0899 (7)
H27A	0.8524	1.1146	0.6740	0.108*
C28	0.7316 (3)	1.0133 (2)	0.8443 (3)	0.0980 (7)
H28A	0.7605	1.0513	0.8933	0.118*
C29	0.6313 (2)	0.9178 (2)	0.9075 (2)	0.0841 (6)
H29A	0.5946	0.8925	0.9981	0.101*
C30	0.58805 (19)	0.86234 (18)	0.83782 (19)	0.0676 (5)
H30A	0.5211	0.7994	0.8812	0.081*
C31	0.64201 (16)	0.89751 (15)	0.70003 (17)	0.0555 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0731 (9)	0.0536 (8)	0.1465 (14)	−0.0020 (6)	−0.0287 (9)	−0.0149 (8)
C1	0.0544 (9)	0.0476 (9)	0.0641 (11)	−0.0107 (7)	−0.0152 (8)	−0.0149 (8)
C2	0.0757 (12)	0.0749 (13)	0.0775 (13)	−0.0077 (10)	−0.0177 (10)	−0.0317 (11)
C3	0.1108 (18)	0.0908 (16)	0.0807 (15)	−0.0134 (13)	−0.0278 (13)	−0.0390 (12)
C4	0.1070 (17)	0.0767 (14)	0.0872 (16)	−0.0140 (12)	−0.0502 (14)	−0.0245 (12)
C5	0.0702 (11)	0.0582 (11)	0.0882 (14)	−0.0115 (8)	−0.0370 (11)	−0.0167 (10)
C6	0.0543 (9)	0.0445 (9)	0.0702 (11)	−0.0120 (7)	−0.0225 (8)	−0.0109 (8)
C7	0.0435 (8)	0.0515 (9)	0.0758 (12)	−0.0082 (7)	−0.0146 (8)	−0.0140 (8)
C8	0.0526 (9)	0.0454 (9)	0.0602 (10)	−0.0105 (7)	−0.0106 (8)	−0.0099 (7)
C9	0.0670 (11)	0.0653 (12)	0.0684 (12)	−0.0033 (9)	−0.0078 (10)	−0.0186 (9)
C10	0.1013 (16)	0.0763 (14)	0.0656 (13)	−0.0026 (12)	−0.0139 (12)	−0.0242 (10)
C11	0.0948 (15)	0.0772 (13)	0.0635 (12)	−0.0098 (11)	−0.0296 (11)	−0.0190 (10)
C12	0.0628 (10)	0.0655 (11)	0.0650 (12)	−0.0092 (8)	−0.0222 (9)	−0.0118 (9)
C13	0.0485 (8)	0.0464 (9)	0.0583 (10)	−0.0116 (7)	−0.0135 (7)	−0.0086 (7)
C14	0.0454 (8)	0.0484 (9)	0.0593 (10)	−0.0095 (6)	−0.0121 (7)	−0.0111 (8)
C15	0.0544 (9)	0.0546 (10)	0.0756 (12)	−0.0044 (8)	−0.0167 (8)	−0.0166 (9)
C16	0.0412 (8)	0.0584 (11)	0.0867 (13)	0.0004 (7)	−0.0092 (8)	−0.0175 (9)
C17	0.0419 (8)	0.0567 (10)	0.0652 (11)	−0.0010 (7)	−0.0133 (7)	−0.0171 (8)
C18	0.0399 (7)	0.0478 (9)	0.0582 (10)	0.0023 (6)	−0.0125 (7)	−0.0134 (7)
C19	0.0481 (8)	0.0498 (9)	0.0575 (10)	0.0041 (7)	−0.0113 (7)	−0.0144 (8)
C20	0.0672 (11)	0.0724 (12)	0.0659 (12)	0.0017 (9)	−0.0162 (9)	−0.0228 (10)
C21	0.0967 (16)	0.0941 (16)	0.0701 (14)	0.0103 (13)	−0.0219 (12)	−0.0325 (12)
C22	0.1056 (18)	0.0903 (16)	0.0582 (13)	0.0117 (13)	−0.0007 (12)	−0.0146 (12)
C23	0.0759 (13)	0.0669 (13)	0.0733 (14)	−0.0007 (10)	0.0034 (11)	−0.0072 (11)
C24	0.0568 (10)	0.0500 (10)	0.0634 (11)	0.0030 (8)	−0.0074 (8)	−0.0071 (8)
C25	0.0629 (11)	0.0528 (10)	0.0829 (14)	−0.0129 (8)	−0.0105 (10)	−0.0064 (10)
C26	0.0638 (10)	0.0507 (10)	0.0796 (13)	−0.0066 (8)	−0.0209 (10)	−0.0160 (9)
C27	0.1027 (16)	0.0627 (13)	0.1131 (19)	−0.0197 (11)	−0.0405 (15)	−0.0240 (13)
C28	0.126 (2)	0.0814 (15)	0.109 (2)	−0.0107 (14)	−0.0510 (17)	−0.0402 (14)
C29	0.0993 (16)	0.0847 (15)	0.0747 (14)	0.0017 (12)	−0.0278 (12)	−0.0343 (12)
C30	0.0658 (11)	0.0691 (12)	0.0658 (12)	−0.0019 (9)	−0.0154 (9)	−0.0235 (9)
C31	0.0509 (9)	0.0493 (9)	0.0624 (11)	0.0010 (7)	−0.0161 (8)	−0.0162 (8)

Geometric parameters (Å, º) top

O1—C15	1.2109 (19)	C16—H16A	0.9300
C1—C14	1.397 (2)	C17—C18	1.473 (2)
C1—C2	1.416 (3)	C17—H17A	0.9300
C1—C6	1.433 (2)	C18—C19	1.396 (2)
C2—C3	1.349 (3)	C18—C31	1.403 (2)
C2—H2A	0.9300	C19—C20	1.418 (3)
C3—C4	1.411 (3)	C19—C24	1.431 (2)
C3—H3A	0.9300	C20—C21	1.343 (3)
C4—C5	1.333 (3)	C20—H20A	0.9300
C4—H4A	0.9300	C21—C22	1.406 (3)
C5—C6	1.418 (2)	C21—H21A	0.9300
C5—H5A	0.9300	C22—C23	1.335 (3)
C6—C7	1.380 (2)	C22—H22A	0.9300
C7—C8	1.389 (2)	C23—C24	1.422 (3)
C7—H7A	0.9300	C23—H23A	0.9300
C8—C9	1.417 (2)	C24—C25	1.374 (3)
C8—C13	1.432 (2)	C25—C26	1.385 (3)
C9—C10	1.346 (3)	C25—H25A	0.9300
C9—H9A	0.9300	C26—C27	1.419 (3)
C10—C11	1.404 (3)	C26—C31	1.431 (2)
C10—H10A	0.9300	C27—C28	1.340 (3)
C11—C12	1.344 (3)	C27—H27A	0.9300
C11—H11A	0.9300	C28—C29	1.401 (3)
C12—C13	1.421 (2)	C28—H28A	0.9300
C12—H12A	0.9300	C29—C30	1.345 (3)
C13—C14	1.391 (2)	C29—H29A	0.9300
C14—C15	1.501 (2)	C30—C31	1.416 (2)
C15—C16	1.461 (2)	C30—H30A	0.9300
C16—C17	1.291 (2)

C14—C1—C2	123.06 (16)	C15—C16—H16A	117.6
C14—C1—C6	119.19 (16)	C16—C17—C18	126.16 (14)
C2—C1—C6	117.74 (16)	C16—C17—H17A	116.9
C3—C2—C1	121.13 (19)	C18—C17—H17A	116.9
C3—C2—H2A	119.4	C19—C18—C31	120.92 (15)
C1—C2—H2A	119.4	C19—C18—C17	120.16 (15)
C2—C3—C4	120.9 (2)	C31—C18—C17	118.92 (15)
C2—C3—H3A	119.6	C18—C19—C20	123.09 (16)
C4—C3—H3A	119.6	C18—C19—C24	119.04 (16)
C5—C4—C3	120.04 (19)	C20—C19—C24	117.87 (16)
C5—C4—H4A	120.0	C21—C20—C19	121.5 (2)
C3—C4—H4A	120.0	C21—C20—H20A	119.3
C4—C5—C6	121.60 (19)	C19—C20—H20A	119.3
C4—C5—H5A	119.2	C20—C21—C22	120.5 (2)
C6—C5—H5A	119.2	C20—C21—H21A	119.7
C7—C6—C5	122.16 (16)	C22—C21—H21A	119.7
C7—C6—C1	119.23 (15)	C23—C22—C21	120.5 (2)
C5—C6—C1	118.59 (18)	C23—C22—H22A	119.8
C6—C7—C8	121.90 (15)	C21—C22—H22A	119.8
C6—C7—H7A	119.0	C22—C23—C24	121.5 (2)
C8—C7—H7A	119.0	C22—C23—H23A	119.2
C7—C8—C9	122.02 (16)	C24—C23—H23A	119.2
C7—C8—C13	119.12 (16)	C25—C24—C23	122.26 (19)
C9—C8—C13	118.85 (16)	C25—C24—C19	119.60 (17)
C10—C9—C8	121.02 (18)	C23—C24—C19	118.14 (19)
C10—C9—H9A	119.5	C24—C25—C26	122.21 (17)
C8—C9—H9A	119.5	C24—C25—H25A	118.9
C9—C10—C11	120.5 (2)	C26—C25—H25A	118.9
C9—C10—H10A	119.8	C25—C26—C27	122.71 (19)
C11—C10—H10A	119.8	C25—C26—C31	118.98 (17)
C12—C11—C10	120.56 (19)	C27—C26—C31	118.31 (19)
C12—C11—H11A	119.7	C28—C27—C26	121.1 (2)
C10—C11—H11A	119.7	C28—C27—H27A	119.4
C11—C12—C13	121.64 (18)	C26—C27—H27A	119.4
C11—C12—H12A	119.2	C27—C28—C29	120.8 (2)
C13—C12—H12A	119.2	C27—C28—H28A	119.6
C14—C13—C12	123.25 (15)	C29—C28—H28A	119.6
C14—C13—C8	119.31 (15)	C30—C29—C28	120.3 (2)
C12—C13—C8	117.42 (16)	C30—C29—H29A	119.9
C13—C14—C1	121.16 (15)	C28—C29—H29A	119.9
C13—C14—C15	120.13 (15)	C29—C30—C31	121.57 (19)
C1—C14—C15	118.69 (15)	C29—C30—H30A	119.2
O1—C15—C16	120.98 (16)	C31—C30—H30A	119.2
O1—C15—C14	120.98 (15)	C18—C31—C30	122.86 (15)
C16—C15—C14	118.03 (14)	C18—C31—C26	119.26 (16)
C17—C16—C15	124.87 (15)	C30—C31—C26	117.88 (16)
C17—C16—H16A	117.6

C14—C1—C2—C3	−176.92 (17)	C14—C15—C16—C17	1.4 (3)
C6—C1—C2—C3	1.6 (3)	C15—C16—C17—C18	179.28 (17)
C1—C2—C3—C4	−0.9 (3)	C16—C17—C18—C19	84.0 (2)
C2—C3—C4—C5	−0.6 (3)	C16—C17—C18—C31	−96.6 (2)
C3—C4—C5—C6	1.4 (3)	C31—C18—C19—C20	−179.19 (14)
C4—C5—C6—C7	177.88 (16)	C17—C18—C19—C20	0.3 (2)
C4—C5—C6—C1	−0.7 (3)	C31—C18—C19—C24	0.3 (2)
C14—C1—C6—C7	−0.8 (2)	C17—C18—C19—C24	179.77 (14)
C2—C1—C6—C7	−179.38 (14)	C18—C19—C20—C21	179.48 (16)
C14—C1—C6—C5	177.76 (14)	C24—C19—C20—C21	0.0 (3)
C2—C1—C6—C5	−0.8 (2)	C19—C20—C21—C22	0.2 (3)
C5—C6—C7—C8	−175.90 (14)	C20—C21—C22—C23	0.1 (3)
C1—C6—C7—C8	2.6 (2)	C21—C22—C23—C24	−0.5 (3)
C6—C7—C8—C9	176.81 (14)	C22—C23—C24—C25	−178.53 (18)
C6—C7—C8—C13	−1.7 (2)	C22—C23—C24—C19	0.7 (3)
C7—C8—C9—C10	−176.32 (16)	C18—C19—C24—C25	−0.7 (2)
C13—C8—C9—C10	2.2 (3)	C20—C19—C24—C25	178.85 (15)
C8—C9—C10—C11	−1.1 (3)	C18—C19—C24—C23	−179.92 (15)
C9—C10—C11—C12	−1.1 (3)	C20—C19—C24—C23	−0.4 (2)
C10—C11—C12—C13	2.1 (3)	C23—C24—C25—C26	179.77 (16)
C11—C12—C13—C14	177.40 (16)	C19—C24—C25—C26	0.6 (3)
C11—C12—C13—C8	−0.9 (2)	C24—C25—C26—C27	179.65 (17)
C7—C8—C13—C14	−1.0 (2)	C24—C25—C26—C31	−0.1 (3)
C9—C8—C13—C14	−179.59 (14)	C25—C26—C27—C28	−178.81 (19)
C7—C8—C13—C12	177.34 (14)	C31—C26—C27—C28	0.9 (3)
C9—C8—C13—C12	−1.2 (2)	C26—C27—C28—C29	−0.3 (4)
C12—C13—C14—C1	−175.44 (14)	C27—C28—C29—C30	−0.3 (3)
C8—C13—C14—C1	2.8 (2)	C28—C29—C30—C31	0.4 (3)
C12—C13—C14—C15	2.9 (2)	C19—C18—C31—C30	−178.97 (14)
C8—C13—C14—C15	−178.87 (14)	C17—C18—C31—C30	1.6 (2)
C2—C1—C14—C13	176.59 (14)	C19—C18—C31—C26	0.2 (2)
C6—C1—C14—C13	−1.9 (2)	C17—C18—C31—C26	−179.29 (14)
C2—C1—C14—C15	−1.8 (2)	C29—C30—C31—C18	179.39 (16)
C6—C1—C14—C15	179.75 (14)	C29—C30—C31—C26	0.2 (3)
C13—C14—C15—O1	95.9 (2)	C25—C26—C31—C18	−0.3 (2)
C1—C14—C15—O1	−85.7 (2)	C27—C26—C31—C18	179.96 (15)
C13—C14—C15—C16	−84.7 (2)	C25—C26—C31—C30	178.88 (15)
C1—C14—C15—C16	93.65 (19)	C27—C26—C31—C30	−0.9 (2)
O1—C15—C16—C17	−179.19 (19)

Hydrogen-bond geometry (Å, º) top

Cg4 and Cg6 are the centroids of the C18/C19/C24–C26/C31 and C26–C31 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5A···Cg4ⁱ	0.93	2.75	3.511 (2)	140
C7—H7A···Cg6ⁱ	0.93	2.91	3.672 (2)	140

Symmetry code: (i) x−1, y, z.

Comparison of experimental and calculated molecular geometry parameters (Å, °) top

Parameters	Exp	DFT
C15—O1	1.21 (19)	1.22
C1—C14	1.40 (2)	1.40
C1—C2	1.42 (3)	1.42
C2—C3	1.35 (3)	1.35
C3—C4	1.41 (3)	1.41
C4—C5	1.33 (3)	1.33
C5—C6	1.42 (2)	1.42
C6—C7	1.380 (2)	1.38
C7—C8	1.39 (2)	1.39
C8—C9	1.42 (2)	1.42
C9—C10	1.35 (3)	1.35
C10—C11	1.40 (3)	1.40
C11—C12	1.34 (3)	1.34
C12—C13	1.42 (2)	1.42
C13—C14	1.39 (2)	1.39
C14—C15	1.50 (2)	1.52
C15—C16	1.46 (2)	1.48
C16—C17	1.29 (2)	1.35
C17—C18	1.47 (2)	1.47
C18—C19	1.40 (2)	1.40
C19—C20	1.42 (3)	1.42
C20—C21	1.34 (3)	1.34
C21—C22	1.41 (3)	1.41
C22—C23	1.34 (3)	1.34
C23—C24	1.42 (3)	1.42
C24—C25	1.37 (3)	1.37
C25—C26	1.39 (3)	1.38
C26—C27	1.42 (3)	1.42
C27—C28	1.34 (3)	1.34
C28—C29	1.40 (3)	1.40
C29—C30	1.35 (3)	1.35
C30—C31	1.42 (2)	1.42
C31—C18	1.40 (2)	1.40
C14—C15—C16	118.03 (14)	119.35
O1—C15—C14	120.98 (15)	120.25
O1—C15—C16	120.98 (16)	120.40
C15—C16—C17	124.87 (15)	123.93
C16—C17—C18	126.16 (14)	127.15

Funding information

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and the Fundamental Research Grant Scheme (FRGS) No. 203/PFIZIK/6711572 and for Short Term Grant Scheme (304/PFIZIK/6313336) to conduct this work. DAZ thanks the Malaysian Government for the My Brain15 scholarship.

References

Abdullah, A. A., Hassan, N. H. H., Arshad, S., Khalib, N. C. & Razak, I. A. (2016). Acta Cryst. E72, 648–651. Web of Science CSD CrossRef IUCr Journals Google Scholar
Agrahari, A., Wagers, P. O., Schildcrout, S. M., Masnovi, J. & Youngs, W. J. (2015). Acta Cryst. E71, 357–359. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cicogna, F., Ingrosso, G., Lodato, F., Marchetti, F. & Zandomeneghi, M. (2004). Tetrahedron, 60, 11959–11968. Web of Science CSD CrossRef CAS Google Scholar
D'silva, E. D., Podagatlapalli, G. K., Rao, S. V., Rao, D. N. & Dharmaprakash, S. M. (2011). Cryst. Growth Des. 11, 5362–5369. CAS Google Scholar
Frisch, M. J., et al. (2009). Gaussian 09. Gaussian, Inc., Wallingford CT, USA. Google Scholar
Girisha, M., Yathirajan, H. S., Jasinski, J. P. & Glidewell, C. (2016). Acta Cryst. E72, 1153–1158. Web of Science CSD CrossRef IUCr Journals Google Scholar
Glidewell, C. & Lloyd, D. (1984). Tetrahedron, 40, 4455–4472. CrossRef CAS Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Harlow, R. L., Loghry, R. A., Williams, H. J. & Simonsen, S. H. (1975). Acta Cryst. B31, 1344–1350. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Jung, Y., Son, K., Oh, Y. E. & Noh, D. (2008). Polyhedron, 27, 861–867. Web of Science CSD CrossRef CAS Google Scholar
Kosar, B. & Albayrak, C. (2011). Spectrochim. Acta A Mol. Biomol. Spectrosc. 78, 160–167. Web of Science CrossRef Google Scholar
Montalti, M., Prodi, L. & Zaccheroni, N. (2000). J. Fluoresence, 10, 71–76. Web of Science CrossRef CAS Google Scholar
Nietfeld, J. P., Schwiderski, R. L., Gonnella, T. P. & Rasmussen, S. C. (2011). J. Org. Chem. 76, 6383–6388. Web of Science CSD CrossRef CAS Google Scholar
Prabhu, A. N., Upadhyaya, V., Jayarama, A. & Bhat, K. B. (2016). Mol. Cryst. Liq. Cryst. 637, 76–86. Web of Science CrossRef CAS Google Scholar
Ramya, T., Gunasekaran, S. & Ramkumaar, G. R. (2015). Spectrochim. Acta A Mol. Biomol. Spectrosc. 149, 132–142. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wu, W., Liu, Y. & Zhu, D. (2010). Chem. Soc. Rev. 39, 1489–1502. Web of Science CrossRef CAS Google Scholar