Crystal structure, Hirshfeld surface and frontier mol­ecular orbital analysis of 9-(3-bromo-4-hy­droxy-5-meth­oxy­phen­yl)-3,3,6,6-tetra­methyl-3,4,5,6,7,9-hexa­hydro-1H-xanthene-1,8(2H)-dione

Suresh Babu, N.; Sughanya, V.; Praveenkumar, D.; Sundararajan, M.L.

doi:10.1107/S2056989021010690

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ISSN: 2056-9890

Volume 77| Part 11| November 2021| Pages 1170-1174

https://doi.org/10.1107/S2056989021010690

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Crystal structure, Hirshfeld surface and frontier molecular orbital analysis of 9-(3-bromo-4-hydroxy-5-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione

N. Suresh Babu,^a ^* V. Sughanya,^b D. Praveenkumar ^c and M. L. Sundararajan ^d

^aDepartment of Chemistry, Government College of Engineering-Sengipatti, Thanjavur-613 402, Tamil Nadu, India, ^bDepartment of Chemistry, Periyar Government Arts College, Cuddalore-607 001, Tamil Nadu, India, ^cDepartment of Chemistry, Swami Vivekananda Arts and Science College, Orathur-605 601, Tamil Nadu, India, and ^dDepartment of Chemistry, Annamalai University, Annamalai Nagar-608 002, Tamil Nadu, India
^*Correspondence e-mail: babusuresh1982@gmail.com

Edited by A. Briceno, Venezuelan Institute of Scientific Research, Venezuela (Received 24 September 2021; accepted 15 October 2021; online 29 October 2021)

In the fused ring system of the title compound, C₂₄H₂₇BrO₅, the mean plane and maximum deviations of the central pyran ring are 0.0384 (2) and 0.0733 (2) Å, respectively. The cyclohexenone rings both adopt envelope conformations with the tetra-substituted C atoms as flap atoms, whereas the central pyran ring adopts a flattened boat conformation. The central pyran and phenyl substituent rings are almost perpendicular to each other, making a dihedral angle of 89.71 (2)°. In the crystal, pairs of molecules are linked via O—H⋯O hydrogen bonds, forming inversion dimers with an R²₂(20) ring motif. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (50.6%), O⋯H/H⋯O (22.9%) and C⋯H/H⋯C (11.1%) contacts. Quantum chemical calculations for the frontier molecular orbitals were undertaken to determine the chemical reactivity of the title compound.

Keywords: crystal structure; dimedone; xanthene; xanthenedione; pyran ring.

CCDC reference: 2064558

1. Chemical context

Xanthene is known as the parent compound of naturally occurring substances with various biological properties including antibacterial (Dimmock et al., 1988 ), antiviral (Naidu et al., 2012 ), antitumor (Al-Omran et al., 2014 ) and anti-inflammatory activities (Dimmock et al., 1988 ; Cottam et al., 1996 ). It is present in organic compounds that are widely used as synthetic dyes (Hilderbrand et al., 2007 ), in fluorescent materials used for visualization of biomolecules (Knight et al., 1989 ), and in laser technologies (Pohlers et al., 1997 ). Ehretianone, a quinonoid xanthene, was reported to possess anti-snake venom activity (Selvanayagam et al., 1996 ; Poupelin et al., 1978 ). Xanthenes whose structures resemble those of 1,4-dihydropyridines can function as calcium channel blockers (Reddy et al., 2010 ; Rathore et al., 2009 ).

2. Structural commentary

The title compound (I) (Fig. 1) crystallizes in the triclinic space group P $[\overline{1}]$ with Z = 2. The central pyran ring B (O1/C1/C8–C10/C17) is almost planar with a mean deviation from the mean plane of 0.0384 (2) Å and a maximum deviation of 0.0733 (3) Å for C9. Atoms C9 and O1 are displaced out of the mean plane in the the same direction so the ring may also be described as having a highly flattened boat conformation. Both cyclohexenone rings, A (C10–C13/C16/C17) and C (C1–C3/C6–C8), adopt envelope conformations with atoms C13 and C3 as the flaps being situated out of the plane of the ring with deviations of 0.3281 (2) and 0.325 (2) Å, respectively. Rings A, B and C show total puckering amplitudes Q(T) of 0.4645 (2), 0.1070 (2) and 0.4607 (16) Å, respectively. The puckering parameters (Cremer & Pople, 1975 ) are φ = 179.52 (8)° and θ = 57.55 (2)° for A, φ = 178.99 (2)° and θ = 68.92 (2)° for B, φ = 304.73 (12)° and θ = 125.47 (2)° for C. The planar phenyl substituent and the central pyran ring form a dihedral angle of 89.71 (2)°. In the pyran ring, C1—C8 and C10—C17 are double bonds, as indicated by the bond lengths [C1—C8 = 1.344 (3) Å and C10—C17 = 1.336 (3) Å]. The angles and bond lengths (Allen et al., 1987 ; Li et al., 2019 ) are within normal ranges. The observed carbonyl bond lengths [C11—O3 = 1.216 (3) and C7—O2 = 1.227 (2) Å] are also normal.

Figure 1
A view of the structure of (I)

, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, molecules are linked by pairs of O4—H4⋯O2 hydrogen bonds (Table 1), forming inversion dimers with an $[R_{2}^{2}]$ (20) ring motif, parallel to the (001) plane (Fig. 2). The molecules are further linked by C6—H6B⋯O2, C16—H16A⋯Br1 and O4—H4⋯O5 hydrogen bonds, forming ribbons (Fig. 3). Overall, the O—H⋯O and C—H⋯O interactions yield a three-dimensional supramolecular network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6B⋯O2ⁱ	0.97	2.60	3.377 (3)	137
C16—H16A⋯Br1ⁱⁱ	0.97	2.94	3.736 (2)	140
O4—H4⋯O2ⁱⁱⁱ	0.82	2.04	2.768 (2)	148
O4—H4⋯O5	0.82	2.28	2.701 (2)	113
Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2
A view of the structure of (I)

showing the O—H⋯O hydrogen bonds, forming a centrosymmetric dimer with an $[R_{2}^{2}]$ (20) ring motif.

Figure 3
Packing view for (I)

, showing the formation of O—H⋯O hydrogen bonds between molecules in the unit cell.

To quantify the intermolecular contacts in the crystal, Hirshfeld surfaces (Spackman & Jayatilaka, 2009 ) and two-dimensional fingerprint plots were generated using Crystal Explorer 17.5 (Turner et al., 2017 ). The Hirshfeld surfaces mapped over d_norm in the range −0.5451 to 1.6834 a.u. (Fig. 4) show the intermolecular contacts as red-coloured spots, which indicate the closer contacts of C—H⋯O and O—H⋯O hydrogen bonds. The bright-red spots indicate their roles as donors and/or acceptors in hydrogen bonding; they also appear as red and blue regions corresponding to negative and positive potentials on the Hirshfeld surface mapped over electrostatic potential (Spackman et al., 2008 ) shown in Fig. 5. Here the red regions indicate negative electrostatic potential (hydrogen-bond acceptors), while the blue regions indicate positive electrostatic potential (hydrogen-bond donors). The 2D fingerprint plots are illustrated in Fig. 6. The H⋯H contacts comprise 50.6% of the total interactions. Besides these contacts, O⋯H/H⋯O (22.9%), C⋯H/H⋯C (11.1%) and Br⋯H/H⋯Br (11.6%) interactions make a significant contribution to the total Hirshfeld surface. The percentage contributions of the Br⋯O/O⋯Br, O⋯O and C⋯C contacts are 1.8, 0.7 and 0.1%, respectively.

Figure 4
View of the three-dimensional Hirshfeld surface of (I)

plotted over d_norm in the range −0.5451 to 1.6834 a.u. The two O—H⋯O hydrogen bonds forming the dimer are depicted as dashed lines.

Figure 5
View of the three-dimensional Hirshfeld surface of (I)

plotted over electrostatic potential energy in the range −0.0500 to 0.0500 a.u. using the STO-3 G basis set at the Hartree–Fock level of theory. The hydrogen-bond donors and acceptors are viewed as blue and red regions, respectively, around atoms, corresponding to positive and negative potentials.

Figure 6
The percentage contributions of close contacts of (I)

. The d_i and d_e values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface.

4. Frontier molecular orbital analysis

The chemical reactivity of the title compound was studied by frontier molecular orbital analysis. For the calculation, the starting structural geometry was taken from the refined experimental structure obtained from X-ray diffraction data. The energy levels for the compound were computed using the DFT-B3LYP/6-311G++(d,p) level of theory as implemented in Gaussian09W (Frisch et al., 2013 ). The calculated frontier molecular orbitals, HOMO, HOMO−1, LUMO and LUMO+1, are shown in Fig. 7. The energies of HOMO, HOMO−1, LUMO and LUMO+1 were calculated to be −5.8915, −6.2499, −1.9353 and −1.0419 eV, respectively, and the energies required to excite one electron from HOMO to LUMO and from HOMO−1 to LUMO+1 are 3.9562 and 5.2080 eV, respectively. The chemical potential, chemical hardness, chemical softness and electrophilicity index of the title molecule are listed in Table 2. Parr et al. (1999 ) have proposed the electrophilicity index as a quantitative measure of the energy lowering due to the maximal electron flow between donor and acceptor orbitals. The electrophilicity index value of 3.8711 eV shows the global electrophilic nature of the molecule. Based on the wide band gap and its chemical hardness value of 1.9781 eV, the title molecule seems to be hard.

Table 2
The global reactivity descriptors (eV) of the title compound

Frontier molecular orbitals	Energy
E_HOMO	−5.8915
E_LUMO	−1.9353
E_HOMO−1	−6.2499
E_LUMO+1	−1.0419
(E_HOMO − E_LUMO) gap	3.9562
(E_HOMO−1 − E_LUMO+1) gap	5.2080
Chemical potential (μ)	3.9134
Chemical hardness (η)	1.9781
Chemical softness (S)	0.5055
Electrophilicity index (ω)	3.8711

Figure 7
The frontier molecular orbitals of (I)

5. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.42, update May 2021; Groom et al., 2016 ) for the xanthene-1,8(2H)-dione unit resulted in 30 hits. They include the following analogues: 2,4-dinitrophenyl (LERZEP; Sureshbabu & Sughanya, 2013 ), 4-hydroxy-3,5-dimethoxyphenyl (YAVTAS; Sughanya & Sureshbabu, 2012a ), 2,4-difluorophenyl (VITWEC; Fun et al., 2011 ), pyridine-2-yl (YIDRIP; Purushothaman & Thiruvenkatam, 2018 ). In the title compound, the dihedral angle between the phenyl and pyran rings is 89.71 (2)°, similar to the values observed for LERZEP, the 2,4-dinitrophenyl analogue, YAVTAS, the 4-hydroxy-3,5-dimethoxyphenyl analogue, and VITWEC, the 2,4-difluorophenyl analogue, for which the dihedral angles are 85.88 (2), 86.32 (2) and 87.55 (4)°, respectively.

6. Synthesis and crystallization

Compound (I) was prepared in two stages (Vanag & Stankevich, 1960 ). A mixture of 5,5-dimethyl cyclohexane-1,3-dione (1.12 g, 8 mmol), 3-bromo-4-hydroxy-5-methoxybenzaldehyde (0.92 g, 4 mmol) and 20 ml of ethanol were heated to 343 K for about 10 minutes. The reaction mixture was allowed to cool to 298–301 K and the resulting intermediate compound, 2,2′-[(3-bromo-4-hydroxy-5-methoxyphenyl)methylene]bis(3-hydroxy-5,5-dimethylcyclohex-2-en-1-one) was filtered and dried (m.p. 491 K, 3.4 mmol, yield: 85%) (Sughanya & Sureshbabu, 2012b ). In the second stage, about 0.50 g (1.04 mmol) of this intermediate were dissolved in 20 ml of ethanol. The content was refluxed together with 5 drops of concentrated hydrochloric acid for 20 minutes with the reaction being monitored by TLC. After completion of the reaction, the reaction mixture was poured into 100 ml of ice-cold water and stirred well. The solid separated was filtered and dried. Yellow single crystals suitable for X-ray diffraction were obtained from 90% ethanol (m.p. 495 K, 0.455 g, 0.96 mmol, yield 92%). IR (KBr): cm⁻¹ 3360, 2953, 2865, 1667, 1622, 1584, 1497, 1278, 1234, 1046, 1003. ¹H NMR (500 MHz, CDCl₃): 1.04 (s, 6H), 1.12 (s, 6H), 2.24 (dd, J = 6 Hz, 4H), 2.47 (dd, J = 6 Hz, 4H), 3.91 (s, 3H), 4.65 (s, 1H), 5.88 (s, 1H), 6.76 (s, 1H), 7.02 (s,1H). ¹³C NMR (125 MHz, CDCl₃): 27.36, 29.21,31.30, 32.23, 40.84, 50.75, 56.32, 107.63, 111.92, 115.26, 123.25, 137.24, 146.56, 162.40, 196.56. ESI–MS: m/z: 475.06 [M + H].

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms were fixed geometrically and treated as riding atoms, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C-methyl).

Table 3
Experimental details

Crystal data
Chemical formula	C₂₄H₂₇BrO₅
M_r	475.36
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	9.851 (3), 10.763 (3), 12.313 (3)
α, β, γ (°)	82.38 (1), 66.900 (9), 73.484 (10)
V (Å³)	1150.9 (5)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.82
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker Kappa APEX3 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.550, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	47600, 4052, 3694
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.072, 1.08
No. of reflections	4052
No. of parameters	276
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.50
Computer programs: APEX3, SAINT-Plus and XPREP (Bruker, 2016), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 2064558

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2056989021010690/zn2010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021010690/zn2010Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989021010690/zn2010Isup3.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: APEX3 and SAINT-Plus (Bruker, 2016); data reduction: SAINT-Plus and XPREP (Bruker, 2016); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL2018 (Sheldrick, 2015a) and publCIF (Westrip, 2010).

9-(3-Bromo-4-hydroxy-5-methoxyphenyl)-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione top

Crystal data top

C₂₄H₂₇BrO₅	F(000) = 492
M_r = 475.36	D_x = 1.372 Mg m⁻³
Triclinic, P1	Melting point: 495 K
a = 9.851 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.763 (3) Å	Cell parameters from 9325 reflections
c = 12.313 (3) Å	θ = 2.6–30.0°
α = 82.38 (1)°	µ = 1.82 mm⁻¹
β = 66.900 (9)°	T = 296 K
γ = 73.484 (10)°	BLOCK, yellow
V = 1150.9 (5) Å³	0.30 × 0.25 × 0.20 mm
Z = 2

Data collection top

Bruker Kappa APEX3 CMOS diffractometer	4052 independent reflections
Radiation source: fine-focus sealed tube	3694 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω and φ scan	θ_max = 25.0°, θ_min = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2016)	h = −11→11
T_min = 0.550, T_max = 0.746	k = −12→12
47600 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.072	w = 1/[σ²(F_o²) + (0.0296P)² + 0.6561P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
4052 reflections	Δρ_max = 0.32 e Å⁻³
276 parameters	Δρ_min = −0.50 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
Br1	0.49132 (3)	0.69406 (2)	0.62363 (2)	0.05292 (10)
C1	0.5946 (2)	0.11911 (17)	0.64639 (15)	0.0319 (4)
C2	0.4569 (2)	0.0735 (2)	0.66746 (17)	0.0412 (5)
H2A	0.484623	−0.020439	0.666673	0.049*
H2B	0.420396	0.105743	0.603872	0.049*
C3	0.3280 (2)	0.1192 (2)	0.78588 (18)	0.0423 (5)
C4	0.2057 (3)	0.0452 (3)	0.8150 (2)	0.0676 (7)
H4A	0.250419	−0.046032	0.819885	0.101*
H4B	0.125530	0.073181	0.889224	0.101*
H4C	0.164507	0.062167	0.754031	0.101*
C5	0.2564 (3)	0.2644 (2)	0.7781 (3)	0.0617 (7)
H5A	0.332860	0.310996	0.759881	0.092*
H5B	0.215134	0.281231	0.717207	0.092*
H5C	0.176157	0.292245	0.852400	0.092*
C6	0.3982 (3)	0.0887 (2)	0.88067 (18)	0.0516 (6)
H6A	0.320679	0.124356	0.954643	0.062*
H6B	0.427417	−0.004661	0.891856	0.062*
C7	0.5345 (2)	0.13965 (17)	0.85383 (16)	0.0366 (4)
C8	0.6339 (2)	0.15206 (16)	0.72946 (15)	0.0313 (4)
C9	0.7704 (2)	0.20575 (17)	0.70112 (16)	0.0322 (4)
C10	0.8672 (2)	0.19047 (17)	0.57072 (16)	0.0322 (4)
C11	1.0196 (2)	0.2146 (2)	0.52605 (19)	0.0439 (5)
C12	1.1113 (2)	0.2068 (2)	0.3948 (2)	0.0495 (5)
H12A	1.180310	0.121046	0.378089	0.059*
H12B	1.172975	0.268803	0.372815	0.059*
C13	1.0158 (2)	0.2333 (2)	0.31752 (18)	0.0428 (5)
C14	0.9298 (3)	0.3771 (2)	0.3217 (2)	0.0617 (7)
H14A	1.001793	0.429336	0.291989	0.093*
H14B	0.869236	0.392418	0.273983	0.093*
H14C	0.864478	0.399531	0.401812	0.093*
C15	1.1185 (3)	0.1973 (3)	0.1891 (2)	0.0627 (7)
H15A	1.189481	0.250422	0.158058	0.094*
H15B	1.173617	0.107698	0.186491	0.094*
H15C	1.056780	0.211083	0.142489	0.094*
C16	0.9043 (2)	0.14713 (19)	0.36435 (16)	0.0378 (4)
H16A	0.831875	0.172240	0.325133	0.045*
H16B	0.960435	0.057845	0.345098	0.045*
C17	0.8192 (2)	0.15590 (17)	0.49441 (15)	0.0313 (4)
C18	0.7174 (2)	0.34791 (17)	0.73598 (16)	0.0318 (4)
C19	0.7345 (2)	0.38397 (18)	0.83369 (16)	0.0342 (4)
H19	0.786711	0.322584	0.873846	0.041*
C20	0.6744 (2)	0.51052 (18)	0.87108 (16)	0.0346 (4)
C21	0.7625 (3)	0.4676 (3)	1.0299 (2)	0.0604 (7)
H21A	0.759056	0.510392	1.094887	0.091*
H21B	0.716974	0.395977	1.059224	0.091*
H21C	0.866680	0.436440	0.977932	0.091*
C22	0.5972 (2)	0.60496 (17)	0.81104 (16)	0.0341 (4)
C23	0.5878 (2)	0.56797 (18)	0.71128 (16)	0.0334 (4)
C24	0.6451 (2)	0.44079 (18)	0.67421 (16)	0.0345 (4)
H24	0.634765	0.418239	0.608017	0.041*
O1	0.68252 (15)	0.12340 (13)	0.52771 (10)	0.0355 (3)
O2	0.56680 (19)	0.16747 (15)	0.93260 (12)	0.0493 (4)
O3	1.0717 (2)	0.2361 (2)	0.59419 (16)	0.0743 (6)
O4	0.53332 (19)	0.72988 (13)	0.84657 (13)	0.0476 (4)
H4	0.531593	0.735147	0.912952	0.071*
O5	0.68156 (19)	0.55546 (14)	0.96789 (13)	0.0489 (4)
H9	0.829 (2)	0.156 (2)	0.7488 (18)	0.035 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.06708 (17)	0.03847 (13)	0.05825 (15)	0.00106 (10)	−0.03853 (12)	−0.00177 (9)
C1	0.0423 (10)	0.0251 (9)	0.0255 (9)	−0.0070 (8)	−0.0102 (8)	−0.0021 (7)
C2	0.0519 (12)	0.0401 (11)	0.0348 (10)	−0.0190 (9)	−0.0126 (9)	−0.0071 (8)
C3	0.0471 (12)	0.0427 (11)	0.0369 (10)	−0.0158 (9)	−0.0104 (9)	−0.0078 (9)
C4	0.0628 (16)	0.0841 (19)	0.0579 (15)	−0.0401 (15)	−0.0067 (13)	−0.0113 (14)
C5	0.0558 (14)	0.0518 (14)	0.0809 (18)	−0.0008 (11)	−0.0323 (13)	−0.0200 (13)
C6	0.0582 (14)	0.0608 (14)	0.0293 (10)	−0.0206 (11)	−0.0070 (10)	0.0027 (10)
C7	0.0520 (12)	0.0273 (9)	0.0273 (9)	−0.0037 (8)	−0.0157 (9)	−0.0007 (7)
C8	0.0428 (10)	0.0230 (8)	0.0262 (9)	−0.0039 (7)	−0.0138 (8)	−0.0010 (7)
C9	0.0409 (10)	0.0287 (9)	0.0294 (9)	−0.0032 (8)	−0.0191 (8)	−0.0027 (7)
C10	0.0371 (10)	0.0267 (9)	0.0319 (9)	−0.0021 (7)	−0.0153 (8)	−0.0036 (7)
C11	0.0407 (11)	0.0464 (12)	0.0470 (12)	−0.0073 (9)	−0.0206 (10)	−0.0034 (9)
C12	0.0385 (11)	0.0577 (14)	0.0491 (12)	−0.0127 (10)	−0.0115 (10)	−0.0049 (10)
C13	0.0417 (11)	0.0446 (11)	0.0349 (10)	−0.0099 (9)	−0.0080 (9)	0.0006 (9)
C14	0.0723 (17)	0.0451 (13)	0.0584 (15)	−0.0140 (12)	−0.0192 (13)	0.0114 (11)
C15	0.0563 (14)	0.0825 (18)	0.0388 (12)	−0.0235 (13)	−0.0026 (11)	−0.0026 (12)
C16	0.0416 (11)	0.0396 (10)	0.0286 (9)	−0.0056 (8)	−0.0115 (8)	−0.0050 (8)
C17	0.0345 (10)	0.0265 (9)	0.0300 (9)	−0.0038 (7)	−0.0116 (8)	−0.0017 (7)
C18	0.0361 (10)	0.0308 (9)	0.0305 (9)	−0.0077 (8)	−0.0138 (8)	−0.0049 (7)
C19	0.0412 (10)	0.0338 (10)	0.0328 (9)	−0.0091 (8)	−0.0194 (8)	−0.0009 (8)
C20	0.0432 (11)	0.0373 (10)	0.0287 (9)	−0.0155 (8)	−0.0140 (8)	−0.0050 (8)
C21	0.0862 (18)	0.0673 (16)	0.0484 (13)	−0.0213 (14)	−0.0426 (13)	−0.0100 (11)
C22	0.0376 (10)	0.0295 (9)	0.0347 (10)	−0.0097 (8)	−0.0104 (8)	−0.0060 (8)
C23	0.0361 (10)	0.0318 (9)	0.0346 (10)	−0.0061 (8)	−0.0175 (8)	−0.0001 (8)
C24	0.0415 (10)	0.0345 (10)	0.0317 (9)	−0.0076 (8)	−0.0178 (8)	−0.0062 (8)
O1	0.0420 (7)	0.0434 (7)	0.0240 (6)	−0.0152 (6)	−0.0112 (5)	−0.0044 (5)
O2	0.0715 (10)	0.0505 (9)	0.0272 (7)	−0.0142 (8)	−0.0204 (7)	−0.0024 (6)
O3	0.0588 (11)	0.1243 (17)	0.0587 (11)	−0.0374 (11)	−0.0297 (9)	−0.0097 (11)
O4	0.0675 (10)	0.0325 (7)	0.0435 (8)	−0.0032 (7)	−0.0248 (8)	−0.0116 (6)
O5	0.0739 (10)	0.0411 (8)	0.0421 (8)	−0.0138 (7)	−0.0303 (8)	−0.0103 (6)

Geometric parameters (Å, º) top

Br1—C23	1.8954 (19)	C12—H12A	0.9700
C1—C8	1.344 (3)	C12—H12B	0.9700
C1—O1	1.378 (2)	C13—C16	1.530 (3)
C1—C2	1.489 (3)	C13—C14	1.535 (3)
C2—C3	1.537 (3)	C13—C15	1.536 (3)
C2—H2A	0.9700	C14—H14A	0.9600
C2—H2B	0.9700	C14—H14B	0.9600
C3—C5	1.529 (3)	C14—H14C	0.9600
C3—C4	1.530 (3)	C15—H15A	0.9600
C3—C6	1.534 (3)	C15—H15B	0.9600
C4—H4A	0.9600	C15—H15C	0.9600
C4—H4B	0.9600	C16—C17	1.489 (3)
C4—H4C	0.9600	C16—H16A	0.9700
C5—H5A	0.9600	C16—H16B	0.9700
C5—H5B	0.9600	C17—O1	1.378 (2)
C5—H5C	0.9600	C18—C24	1.380 (3)
C6—C7	1.494 (3)	C18—C19	1.395 (2)
C6—H6A	0.9700	C19—C20	1.383 (3)
C6—H6B	0.9700	C19—H19	0.9300
C7—O2	1.227 (2)	C20—O5	1.378 (2)
C7—C8	1.471 (3)	C20—C22	1.400 (3)
C8—C9	1.511 (3)	C21—O5	1.403 (3)
C9—C10	1.515 (3)	C21—H21A	0.9600
C9—C18	1.530 (2)	C21—H21B	0.9600
C9—H9	0.98 (2)	C21—H21C	0.9600
C10—C17	1.336 (3)	C22—O4	1.362 (2)
C10—C11	1.470 (3)	C22—C23	1.384 (3)
C11—O3	1.216 (3)	C23—C24	1.387 (3)
C11—C12	1.510 (3)	C24—H24	0.9300
C12—C13	1.533 (3)	O4—H4	0.8200

C8—C1—O1	122.25 (17)	H12A—C12—H12B	107.6
C8—C1—C2	126.24 (17)	C16—C13—C12	107.75 (17)
O1—C1—C2	111.51 (15)	C16—C13—C14	110.89 (18)
C1—C2—C3	112.21 (16)	C12—C13—C14	110.14 (19)
C1—C2—H2A	109.2	C16—C13—C15	108.20 (18)
C3—C2—H2A	109.2	C12—C13—C15	110.44 (19)
C1—C2—H2B	109.2	C14—C13—C15	109.39 (19)
C3—C2—H2B	109.2	C13—C14—H14A	109.5
H2A—C2—H2B	107.9	C13—C14—H14B	109.5
C5—C3—C4	109.3 (2)	H14A—C14—H14B	109.5
C5—C3—C6	111.04 (18)	C13—C14—H14C	109.5
C4—C3—C6	109.72 (19)	H14A—C14—H14C	109.5
C5—C3—C2	109.94 (19)	H14B—C14—H14C	109.5
C4—C3—C2	109.43 (17)	C13—C15—H15A	109.5
C6—C3—C2	107.36 (18)	C13—C15—H15B	109.5
C3—C4—H4A	109.5	H15A—C15—H15B	109.5
C3—C4—H4B	109.5	C13—C15—H15C	109.5
H4A—C4—H4B	109.5	H15A—C15—H15C	109.5
C3—C4—H4C	109.5	H15B—C15—H15C	109.5
H4A—C4—H4C	109.5	C17—C16—C13	112.68 (16)
H4B—C4—H4C	109.5	C17—C16—H16A	109.1
C3—C5—H5A	109.5	C13—C16—H16A	109.1
C3—C5—H5B	109.5	C17—C16—H16B	109.1
H5A—C5—H5B	109.5	C13—C16—H16B	109.1
C3—C5—H5C	109.5	H16A—C16—H16B	107.8
H5A—C5—H5C	109.5	C10—C17—O1	123.42 (16)
H5B—C5—H5C	109.5	C10—C17—C16	125.17 (18)
C7—C6—C3	115.04 (17)	O1—C17—C16	111.41 (15)
C7—C6—H6A	108.5	C24—C18—C19	119.37 (17)
C3—C6—H6A	108.5	C24—C18—C9	119.97 (16)
C7—C6—H6B	108.5	C19—C18—C9	120.58 (16)
C3—C6—H6B	108.5	C20—C19—C18	120.33 (17)
H6A—C6—H6B	107.5	C20—C19—H19	119.8
O2—C7—C8	119.91 (19)	C18—C19—H19	119.8
O2—C7—C6	121.64 (18)	O5—C20—C19	124.98 (18)
C8—C7—C6	118.42 (17)	O5—C20—C22	114.18 (16)
C1—C8—C7	117.75 (18)	C19—C20—C22	120.84 (17)
C1—C8—C9	123.31 (16)	O5—C21—H21A	109.5
C7—C8—C9	118.90 (16)	O5—C21—H21B	109.5
C8—C9—C10	109.09 (15)	H21A—C21—H21B	109.5
C8—C9—C18	110.02 (15)	O5—C21—H21C	109.5
C10—C9—C18	111.38 (15)	H21A—C21—H21C	109.5
C8—C9—H9	107.8 (12)	H21B—C21—H21C	109.5
C10—C9—H9	110.4 (11)	O4—C22—C23	119.68 (17)
C18—C9—H9	108.0 (12)	O4—C22—C20	122.66 (17)
C17—C10—C11	118.59 (17)	C23—C22—C20	117.67 (16)
C17—C10—C9	122.45 (17)	C22—C23—C24	121.99 (17)
C11—C10—C9	118.96 (16)	C22—C23—Br1	119.16 (14)
O3—C11—C10	120.3 (2)	C24—C23—Br1	118.84 (14)
O3—C11—C12	121.2 (2)	C18—C24—C23	119.71 (16)
C10—C11—C12	118.47 (18)	C18—C24—H24	120.1
C11—C12—C13	114.73 (18)	C23—C24—H24	120.1
C11—C12—H12A	108.6	C1—O1—C17	118.39 (14)
C13—C12—H12A	108.6	C22—O4—H4	109.5
C11—C12—H12B	108.6	C20—O5—C21	117.51 (16)
C13—C12—H12B	108.6

C8—C1—C2—C3	24.0 (3)	C12—C13—C16—C17	49.6 (2)
O1—C1—C2—C3	−156.46 (16)	C14—C13—C16—C17	−71.0 (2)
C1—C2—C3—C5	72.5 (2)	C15—C13—C16—C17	169.04 (18)
C1—C2—C3—C4	−167.4 (2)	C11—C10—C17—O1	175.94 (16)
C1—C2—C3—C6	−48.4 (2)	C9—C10—C17—O1	−4.1 (3)
C5—C3—C6—C7	−67.4 (2)	C11—C10—C17—C16	−4.0 (3)
C4—C3—C6—C7	171.63 (19)	C9—C10—C17—C16	175.98 (17)
C2—C3—C6—C7	52.8 (2)	C13—C16—C17—C10	−24.5 (3)
C3—C6—C7—O2	151.79 (19)	C13—C16—C17—O1	155.55 (16)
C3—C6—C7—C8	−30.3 (3)	C8—C9—C18—C24	−68.8 (2)
O1—C1—C8—C7	−177.95 (16)	C10—C9—C18—C24	52.3 (2)
C2—C1—C8—C7	1.5 (3)	C8—C9—C18—C19	107.97 (19)
O1—C1—C8—C9	4.6 (3)	C10—C9—C18—C19	−130.94 (18)
C2—C1—C8—C9	−175.96 (17)	C24—C18—C19—C20	2.5 (3)
O2—C7—C8—C1	179.28 (17)	C9—C18—C19—C20	−174.21 (17)
C6—C7—C8—C1	1.3 (3)	C18—C19—C20—O5	178.32 (18)
O2—C7—C8—C9	−3.1 (3)	C18—C19—C20—C22	−0.9 (3)
C6—C7—C8—C9	178.92 (17)	O5—C20—C22—O4	−0.8 (3)
C1—C8—C9—C10	−10.9 (2)	C19—C20—C22—O4	178.46 (18)
C7—C8—C9—C10	171.59 (15)	O5—C20—C22—C23	178.72 (17)
C1—C8—C9—C18	111.52 (19)	C19—C20—C22—C23	−2.0 (3)
C7—C8—C9—C18	−65.9 (2)	O4—C22—C23—C24	−177.13 (18)
C8—C9—C10—C17	10.7 (2)	C20—C22—C23—C24	3.3 (3)
C18—C9—C10—C17	−111.0 (2)	O4—C22—C23—Br1	2.0 (3)
C8—C9—C10—C11	−169.39 (16)	C20—C22—C23—Br1	−177.59 (14)
C18—C9—C10—C11	69.0 (2)	C19—C18—C24—C23	−1.3 (3)
C17—C10—C11—O3	−174.2 (2)	C9—C18—C24—C23	175.50 (17)
C9—C10—C11—O3	5.9 (3)	C22—C23—C24—C18	−1.7 (3)
C17—C10—C11—C12	3.5 (3)	Br1—C23—C24—C18	179.19 (14)
C9—C10—C11—C12	−176.41 (18)	C8—C1—O1—C17	3.6 (2)
O3—C11—C12—C13	−156.7 (2)	C2—C1—O1—C17	−175.94 (15)
C10—C11—C12—C13	25.6 (3)	C10—C17—O1—C1	−3.8 (3)
C11—C12—C13—C16	−50.9 (2)	C16—C17—O1—C1	176.09 (15)
C11—C12—C13—C14	70.2 (2)	C19—C20—O5—C21	3.2 (3)
C11—C12—C13—C15	−168.9 (2)	C22—C20—O5—C21	−177.50 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6B···O2ⁱ	0.97	2.60	3.377 (3)	137
C16—H16A···Br1ⁱⁱ	0.97	2.94	3.736 (2)	140
O4—H4···O2ⁱⁱⁱ	0.82	2.04	2.768 (2)	148
O4—H4···O5	0.82	2.28	2.701 (2)	113

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

The global reactivity descriptors (eV) of the title compound top

Frontier molecular orbitals	Energy
E_HOMO	-5.8915
E_LUMO	-1.9353
E_HOMO-1	-6.2499
E_LUMO+1	-1.0419
(E_HOMO - E_LUMO) gap	3.9562
(E_HOMO-1 - E_LUMO+1) gap	5.2080
Chemical potential (µ)	3.9134
Chemical hardness (η)	1.9781
Chemical softness (S)	0.5055
Electrophilicity index (ω)	3.8711

The frontier molecular orbital energies of the title compound top

Orbitals	a.u	eV
V₁₃₀	-0.00040	-0.01088
V₁₂₉	-0.00433	-0.11782
V₁₂₈	-0.00548	-0.14911
V₁₂₇	-0.00823	-0.22394
V₁₂₆	-0.01615	-0.43945
V₁₂₅	-0.03829	-1.04190
V₁₂₄	-0.07112	1.93524
O₁₂₃	-0.21651	-5.89145
O₁₂₂	-0.22968	-6.24982
O₁₂₁	-0.24696	-6.72002
O₁₂₀	-0.25386	-6.90778
O₁₁₉	-0.25681	-6.98805
O₁₁₈	-0.28020	-7.62452
O₁₁₇	-0.28631	-7.79078
O₁₁₆	-0.29688	-8.07840
O₁₁₅	-0.33387	-9.08493
O₁₁₄	-0.33908	-9.22670

* O- Occupied orbital V- Vacant orbital a.u-atomic unit eV-Electron Volt

Acknowledgements

The authors thank Dr Sudhadevi Antharjanam and the SAIF, IIT Madras, for the data collection.

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