Synthesis and structure of 4-bromo-2-chloro­phenyl 4′-meth­oxy-[1,1′-biphen­yl]-4-carboxyl­ate featuring short halogen⋯oxygen contacts

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

doi:10.1107/S2056989025002658

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Volume 81| Part 5| May 2025|

https://doi.org/10.1107/S2056989025002658

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Synthesis and structure of 4-bromo-2-chlorophenyl 4′-methoxy-[1,1′-biphenyl]-4-carboxylate featuring short halogen⋯oxygen contacts

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

^aDepartment of PG Studies and Research in Physics, Albert Einstein Block, UCS, Tumkur University, Tumkur, Karnataka-572103, India, ^bDepartment of Physics, Government First Grade College, Chikkballapur, Karnataka-562101, India, ^cDepartment of Physics, Yuvaraja's College, University of Mysore, Mysore-, 570005, Karnataka, India, and ^dRaman Research Institute, C. V. Raman, Avenue, Sadashivanagar, Bangalore-560080, Karnataka, India
^*Correspondence e-mail: harishkagalipur@gmail.com

Edited by W. T. A. Harrison, University of Aberdeen, United Kingdom (Received 3 March 2025; accepted 24 March 2025; online 4 April 2025)

In the title compound, C₂₀H₁₄BrClO₃, the dihedral angles between the aromatic ring of the 4-bromo-2-chlorophenyl and the immediate neighbour and second aromatic ring of the biphenyl moiety are 80.59 (2) and 75.42 (2)°, respectively. The dihedral angle between the rings within the biphenyl moiety is 24.57 (4)°. The torsion angle associated with the ester group linking the biphenyl ring and the 4-bromo-2-chlorophenyl group is −166.6 (2)°. The extended structure features short halogen⋯oxygen contacts [Cl⋯O = 2.991 (3), Br⋯O = 3.139 (2) Å], forming molecular sheets lying parallel to (101). The Hirshfeld surface analysis reveals that the major contributions to the intermolecular interactions are from C⋯H/H⋯C (32.2%), H⋯H/H⋯H (26.3%), Br⋯H/H⋯Br (10.7%), O⋯H/H⋯O (10.4%) and Cl⋯H/H⋯Cl (7.5%) contacts.

Keywords: crystal structure; biphenyl; Hirshfeld surface.

CCDC reference: 2433444

1. Chemical context

Biphenyl derivates exhibit medicinal properties such as antihypertensive (Sharma et al., 2010 ), anti-diabetic (Sachan et al., 2009 ), anti-bacterial (Trivedi et al., 2009 ), antifungal (Zhao et al., 2017 ) and anticancer (Mukherjee et al., 2016 ) effects. The drug obtained from the piperidine derivative of biphenyl-4-carboxylate selectively kills the bacterial persisters that are resistant to antibiotic treatments (Kim et al., 2011 ). Some biphenyl-carboxylic acid derivatives act as antiresorptive drugs (Van't Hof et al., 2004 ; Idris et al., 2009 ) by stopping or slowing down bone loss in osteoporosis. It is found that biphenyl compounds substituted with a heterocyclic ring can act as anti-tyrosinase agents (Kwong et al., 2017 ) that reduce the activity of tyrosinase enzyme. Biphenyl-4-carboxylic acid derivatives inhibit tubulin polymerization to act as anticancer agents (Mahale et al., 2014 ). 4-Bromo-2-chlorophenyl-based compounds exhibit significant in vitro inhibitory effects on plasmodium falciparum against malaria parasites (Vallone et al., 2018 , Kos et al., 2022 ). The presence of a halogen atom in the phenyl moiety of 4-bromo-2-chlorophenyl derivatives is found to induce antimicrobial properties in the compounds (Radwan et al., 2014 ).

As part of our studies in this area, we now present the synthesis and crystal structure of the title compound, C₂₀H₁₄BrClO₃ (I).

2. Structural commentary

The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the aromatic ring (C1–C6) of the 4-bromo-2-chlorophenyl group and the C8–C13 and C14–C19 rings of the methoxy-biphenyl-carboxylate moiety are 80.59 (2) and 75.42 (2)°, respectively. The dihedral angle between the aromatic rings in the biphenyl moiety (C8–C13 and C14–C19) is 24.57 (4)°. The torsion angle in the ester group (C1—O1—C7—C8) linking the 4-bromo-2-chlorophenyl group with the biphenyl moiety is −166.6 (2)°.

Figure 1
The molecular structure of (I) showing displacement ellipsoids drawn at the 50% probability level.

3. Supramolecular features

The crystal packing features short C2—Cl1⋯O3 and C4—Br1⋯O2 interactions with a Cl1⋯O3 distance of 2.991 (3) Å and a Br1⋯O2 distance of 3.139 (2) Å, forming molecular sheets propagating in the (101) plane, as shown in Fig. 2. The van der Waals separations of Cl and O atoms and Br and O atoms are 3.27 and 3.37 Å, respectively. Two weak C—H⋯π interactions also occur (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯Cg3ⁱ	0.93	2.65	3.459 (3)	147
C10—H10⋯Cg3ⁱⁱ	0.93	2.85	3.577 (3)	136
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[-x, y+{\script{3\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 2
The packing of (I) with dashed lines indicating Cl⋯O and Br⋯O contacts.

4. Hirshfeld surface analysis

A Hirshfeld surface analysis for (I) was performed to quantify and visualize the intermolecular interaction present in the molecules using Crystal-Explorer17 (Turner et al., 2017 ). The Hirshfeld surface (Spackman & Jayatilaka, 2009 ) mapped over normalised contact distance d_norm (Fig. 3) shows the presence of red spots on the iso-surface that correspond to the existence of the short halogen⋯oxygen type interactions noted above. The two-dimensional fingerprint plots (McKinnon et al., 2007 ) are shown in Fig. 4. The major contributions for the intermolecular interactions are from C⋯H/H⋯C (32.2%), H⋯H (26.3%), Br⋯H/H⋯Br (10.7%), O⋯H/H⋯O (10.4%) and Cl⋯H/H⋯Cl (7.5%). The sharp spikes in the fingerprint plots for Cl⋯O and Br⋯O contacts (Fig. 5) confirm the existence of the directional halogen⋯oxygen interactions.

Figure 3
The Hirshfeld surface of (I) mapped over d_norm with red spots corresponding to Cl⋯O and Br⋯O short contacts.

Figure 4
The two-dimensional fingerprint plots of the major contributors to intermolecular interactions in (I).

Figure 5
Fingerprints plots for the Cl⋯O/O⋯Cl and Br⋯O/O⋯Br contacts in (I).

5. Database survey

A search of the Cambridge Structural Database (CSD version 2.0.4, December 2019; Groom et al., 2016 ) for molecules containing a [1,1′-biphenyl]-4-carboxylate fragment resulted in more than thirty matches, but six compounds were identified with a substitution at the oxygen atom of the ester group similar to the title compound. In five of the compounds, namely CSD refcodes PUGZUP (Chen et al., 2020 ), ESEMAT (Wang et al., 2021 ), FIRYIR(Royal et al., 2019 ), JOCVAB (Chen et al., 2019 ) and JOCVEF (Chen et al., 2019), the dihedral angles between the aromatic rings of the biphenyl carboxylic acid range between 29.42 (2) and 38.39 (3)° whereas in NEKPAK (Wang et al., 2017 ), the dihedral angle is 12.42 (2)°. The conformations of the ester groups (C—O—C—C), which link the biphenyl ring and the functional group in the above compounds and (I), are all anti.

6. Synthesis and crystallization

A mixture of 4-bromo-2-chlorophenol (0.208 g, 1.00 mmol) and 4′-methoxy-[1,1′-biphenyl]-4-carboxylic acid (0.228 g, 1.00 mmol) was suspended in anhydrous chloroform (10 ml). To this were added N,N-dicyclohexylcarbodiimide (0.206 g, 1.00 mmol) and 4-N,N-dimethylamino pyridine (5 mg) and the mixture was stirred overnight at room temperature. The N,N-dicyclohexyl urea formed was filtered off and the filtrate diluted with chloroform (25 ml). This solution was washed successively with 5% aqueous acetic acid solution (2 × 25 ml) and water (2 × 25 ml) and dried over sodium sulfate. The residue obtained on removal of the solvent was chromatographed on silica gel using chloroform as the eluent. Removal of solvent from the eluate afforded a white material, which was recrystallized from the mixed solvents of chloroform and petroleum ether to yield colourless prisms of (I). Yield 78%. Elemental analysis calculated: C, 57.51; H, 3.38; Br, 19.13; Cl, 8.49; O, 11.49% found is C, 57.56; H, 3.39; Br, 19.15; Cl, 8.53%, m.p. 338–340 K.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. All H atoms were positioned with idealized geometry and refined using a riding model with C—H = 0.93–0.96 Å and U_iso(H) = 1.2U_eq(C) or 1.5U_eq(methyl C).

Table 2
Experimental details

Crystal data
Chemical formula	C₂₀H₁₄BrClO₃
M_r	417.67
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	296
a, b, c (Å)	8.8347 (4), 9.4124 (5), 20.5526 (11)
V (Å³)	1709.07 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	2.58
Crystal size (mm)	0.40 × 0.35 × 0.29

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.371, 0.475
No. of measured, independent and observed [I > 2σ(I)] reflections	28805, 4264, 4012
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.04
No. of reflections	4264
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.23
Absolute structure	Flack parameter
Absolute structure parameter	0.011 (8)
Computer programs: APEX2 and SAINT (Bruker, 2017 ), SHELXL2018/3 and SHELXL2019/2 (Sheldrick, 2015b ), SHELXT2018/2 (Sheldrick, 2015a ) and Mercury (Macrae et al., 2020 ).

Supporting information

CCDC reference: 2433444

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002658/hb8126sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025002658/hb8126Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989025002658/hb8126Isup3.cml

checkCIF report

Computing details top

4-Bromo-2-chlorophenyl 4'-methoxy-[1,1'-biphenyl]-4-carboxylate top

Crystal data top

C₂₀H₁₄BrClO₃	prism
M_r = 417.67	D_x = 1.623 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.8347 (4) Å	Cell parameters from 4264 reflections
b = 9.4124 (5) Å	θ = 2.5–28.5°
c = 20.5526 (11) Å	µ = 2.58 mm⁻¹
V = 1709.07 (15) Å³	T = 296 K
Z = 4	Prism, colourless
F(000) = 840	0.40 × 0.35 × 0.29 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	4264 independent reflections
Radiation source: fine-focus sealed tube	4012 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
Detector resolution: 1.02 pixels mm^-1	θ_max = 28.4°, θ_min = 2.0°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	k = −12→11
T_min = 0.371, T_max = 0.475	l = −27→27
28805 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)] = 0.023	H-atom parameters constrained
wR(F²) = 0.054	w = 1/[σ²(F_o²) + (0.0209P)² + 0.2511P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.005
4264 reflections	Δρ_max = 0.27 e Å⁻³
228 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Absolute structure: Flack parameter
0 constraints	Absolute structure parameter: 0.011 (8)
Primary atom site location: dual

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.

Refinement. Refined as a 2-component inversion twin.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.36294 (3)	0.65415 (3)	1.07977 (2)	0.02179 (8)
Cl1	0.27206 (8)	0.77586 (8)	0.82023 (3)	0.02310 (15)
O1	0.5178 (2)	0.5732 (2)	0.79614 (9)	0.0205 (4)
O2	0.6829 (2)	0.7562 (2)	0.79511 (9)	0.0237 (4)
O3	0.5585 (2)	0.6213 (2)	0.28240 (9)	0.0200 (4)
C1	0.4892 (3)	0.5971 (3)	0.86220 (13)	0.0170 (5)
C2	0.3733 (3)	0.6880 (3)	0.87978 (12)	0.0162 (5)
C3	0.3367 (3)	0.7066 (3)	0.94475 (13)	0.0179 (5)
H3	0.260073	0.768730	0.957100	0.021*
C4	0.4174 (3)	0.6301 (3)	0.99101 (12)	0.0163 (5)
C5	0.5330 (3)	0.5395 (3)	0.97413 (13)	0.0192 (6)
H5	0.586627	0.490548	1.005954	0.023*
C6	0.5685 (3)	0.5224 (3)	0.90840 (13)	0.0200 (6)
H6	0.645518	0.460749	0.895960	0.024*
C7	0.6090 (3)	0.6712 (3)	0.76569 (12)	0.0173 (5)
C8	0.6024 (3)	0.6556 (3)	0.69402 (12)	0.0162 (5)
C9	0.7052 (3)	0.7323 (3)	0.65671 (13)	0.0193 (5)
H9	0.776532	0.789750	0.677077	0.023*
C10	0.7022 (3)	0.7237 (3)	0.58936 (13)	0.0199 (5)
H10	0.772926	0.773917	0.565012	0.024*
C11	0.5936 (3)	0.6401 (3)	0.55758 (12)	0.0137 (5)
C12	0.4918 (3)	0.5638 (3)	0.59588 (12)	0.0181 (6)
H12	0.419557	0.507014	0.575668	0.022*
C13	0.4953 (3)	0.5702 (3)	0.66334 (13)	0.0171 (5)
H13	0.426611	0.517802	0.687867	0.021*
C14	0.5846 (3)	0.6327 (3)	0.48544 (12)	0.0137 (5)
C15	0.6389 (3)	0.7435 (3)	0.44582 (12)	0.0163 (5)
H15	0.682792	0.822772	0.465137	0.020*
C16	0.6283 (3)	0.7369 (3)	0.37886 (12)	0.0172 (5)
H16	0.664628	0.811468	0.353630	0.021*
C17	0.5634 (3)	0.6189 (3)	0.34898 (12)	0.0160 (5)
C18	0.5083 (3)	0.5085 (3)	0.38685 (12)	0.0163 (5)
H18	0.464090	0.429602	0.367308	0.020*
C19	0.5197 (3)	0.5164 (3)	0.45424 (13)	0.0158 (5)
H19	0.482771	0.441679	0.479239	0.019*
C20	0.4945 (4)	0.5005 (3)	0.25032 (13)	0.0238 (6)
H20A	0.509264	0.509222	0.204215	0.036*
H20B	0.388077	0.495699	0.259587	0.036*
H20C	0.543054	0.415659	0.265624	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.03127 (14)	0.02241 (13)	0.01170 (11)	−0.00941 (12)	0.00389 (11)	−0.00150 (11)
Cl1	0.0232 (3)	0.0267 (3)	0.0194 (3)	0.0006 (3)	−0.0048 (3)	0.0066 (3)
O1	0.0279 (10)	0.0228 (10)	0.0107 (9)	−0.0050 (8)	0.0038 (8)	0.0002 (8)
O2	0.0236 (10)	0.0321 (11)	0.0153 (9)	−0.0082 (9)	0.0012 (8)	−0.0034 (8)
O3	0.0248 (10)	0.0231 (11)	0.0120 (9)	−0.0039 (8)	−0.0019 (8)	0.0016 (7)
C1	0.0160 (12)	0.0222 (13)	0.0128 (12)	−0.0036 (11)	0.0030 (10)	−0.0014 (10)
C2	0.0160 (11)	0.0177 (13)	0.0147 (11)	−0.0027 (10)	−0.0046 (10)	0.0035 (9)
C3	0.0180 (13)	0.0174 (12)	0.0182 (12)	−0.0007 (10)	0.0023 (10)	−0.0003 (10)
C4	0.0190 (12)	0.0196 (14)	0.0104 (11)	−0.0076 (11)	0.0023 (9)	0.0008 (10)
C5	0.0181 (13)	0.0243 (14)	0.0152 (13)	−0.0012 (12)	−0.0015 (10)	0.0057 (11)
C6	0.0173 (12)	0.0231 (14)	0.0197 (14)	0.0030 (11)	0.0033 (11)	0.0010 (11)
C7	0.0150 (12)	0.0210 (13)	0.0160 (11)	−0.0002 (11)	0.0021 (10)	0.0002 (10)
C8	0.0161 (12)	0.0191 (12)	0.0134 (11)	0.0003 (11)	0.0015 (9)	−0.0029 (11)
C9	0.0179 (12)	0.0258 (14)	0.0142 (12)	−0.0077 (12)	0.0001 (10)	−0.0041 (11)
C10	0.0192 (12)	0.0250 (13)	0.0157 (14)	−0.0067 (11)	0.0034 (11)	0.0000 (11)
C11	0.0143 (11)	0.0141 (12)	0.0127 (11)	0.0015 (10)	−0.0003 (9)	−0.0010 (10)
C12	0.0163 (12)	0.0204 (13)	0.0177 (13)	−0.0028 (11)	−0.0014 (10)	−0.0020 (10)
C13	0.0163 (12)	0.0193 (13)	0.0158 (13)	−0.0041 (11)	0.0031 (10)	0.0017 (10)
C14	0.0124 (11)	0.0160 (13)	0.0128 (11)	0.0036 (10)	−0.0008 (9)	0.0011 (10)
C15	0.0167 (11)	0.0144 (12)	0.0179 (12)	0.0008 (11)	−0.0014 (11)	−0.0019 (9)
C16	0.0173 (11)	0.0176 (12)	0.0168 (12)	−0.0012 (12)	0.0004 (11)	0.0045 (9)
C17	0.0151 (12)	0.0214 (14)	0.0114 (12)	0.0030 (10)	−0.0002 (10)	−0.0008 (9)
C18	0.0177 (12)	0.0152 (13)	0.0162 (13)	−0.0005 (10)	−0.0037 (10)	−0.0018 (10)
C19	0.0161 (12)	0.0160 (13)	0.0154 (12)	0.0010 (11)	−0.0004 (10)	0.0029 (10)
C20	0.0287 (14)	0.0283 (16)	0.0143 (13)	−0.0021 (13)	−0.0031 (11)	−0.0035 (11)

Geometric parameters (Å, º) top

Br1—C4	1.900 (2)	C10—C11	1.402 (4)
Cl1—C2	1.727 (3)	C10—H10	0.9300
O1—C7	1.375 (3)	C11—C12	1.395 (4)
O1—C1	1.399 (3)	C11—C14	1.487 (3)
O2—C7	1.196 (3)	C12—C13	1.388 (4)
O3—C17	1.369 (3)	C12—H12	0.9300
O3—C20	1.431 (3)	C13—H13	0.9300
C1—C6	1.374 (4)	C14—C19	1.392 (4)
C1—C2	1.382 (4)	C14—C15	1.408 (3)
C2—C3	1.385 (4)	C15—C16	1.381 (3)
C3—C4	1.389 (4)	C15—H15	0.9300
C3—H3	0.9300	C16—C17	1.392 (4)
C4—C5	1.375 (4)	C16—H16	0.9300
C5—C6	1.396 (4)	C17—C18	1.387 (4)
C5—H5	0.9300	C18—C19	1.391 (3)
C6—H6	0.9300	C18—H18	0.9300
C7—C8	1.482 (3)	C19—H19	0.9300
C8—C9	1.391 (4)	C20—H20A	0.9600
C8—C13	1.393 (4)	C20—H20B	0.9600
C9—C10	1.387 (4)	C20—H20C	0.9600
C9—H9	0.9300

C7—O1—C1	116.1 (2)	C11—C10—H10	119.6
C17—O3—C20	117.4 (2)	C12—C11—C10	117.9 (2)
C6—C1—C2	120.9 (2)	C12—C11—C14	120.3 (2)
C6—C1—O1	119.7 (2)	C10—C11—C14	121.9 (2)
C2—C1—O1	119.1 (2)	C13—C12—C11	121.8 (2)
C6—C1—O1	119.7 (2)	C13—C12—H12	119.1
C2—C1—O1	119.1 (2)	C11—C12—H12	119.1
C1—C2—C3	120.2 (2)	C12—C13—C8	119.5 (2)
C1—C2—Cl1	119.6 (2)	C12—C13—H13	120.3
C3—C2—Cl1	120.1 (2)	C8—C13—H13	120.3
C2—C3—C4	118.3 (2)	C19—C14—C15	117.2 (2)
C2—C3—H3	120.8	C19—C14—C11	121.3 (2)
C4—C3—H3	120.8	C15—C14—C11	121.6 (2)
C5—C4—C3	122.0 (2)	C16—C15—C14	121.3 (2)
C5—C4—Br1	120.3 (2)	C16—C15—H15	119.3
C3—C4—Br1	117.7 (2)	C14—C15—H15	119.3
C4—C5—C6	118.9 (3)	C15—C16—C17	120.2 (2)
C4—C5—H5	120.6	C15—C16—H16	119.9
C6—C5—H5	120.6	C17—C16—H16	119.9
C1—C6—C5	119.7 (3)	O3—C17—C18	124.2 (2)
C1—C6—H6	120.2	O3—C17—C16	116.1 (2)
C5—C6—H6	120.2	C18—C17—C16	119.6 (2)
O2—C7—O1	122.5 (2)	C17—C18—C19	119.6 (2)
O2—C7—O1	122.5 (2)	C17—C18—H18	120.2
O2—C7—C8	126.2 (2)	C19—C18—H18	120.2
O1—C7—C8	111.3 (2)	C18—C19—C14	122.1 (3)
O1—C7—C8	111.3 (2)	C18—C19—H19	119.0
C9—C8—C13	119.6 (2)	C14—C19—H19	119.0
C9—C8—C7	118.1 (2)	O3—C20—H20A	109.5
C13—C8—C7	122.3 (2)	O3—C20—H20B	109.5
C10—C9—C8	120.5 (2)	H20A—C20—H20B	109.5
C10—C9—H9	119.8	O3—C20—H20C	109.5
C8—C9—H9	119.8	H20A—C20—H20C	109.5
C9—C10—C11	120.7 (2)	H20B—C20—H20C	109.5
C9—C10—H10	119.6

O1—O1—C1—C6	0.0 (6)	O2—C7—C8—C13	−169.1 (3)
C7—O1—C1—C6	−100.4 (3)	O1—C7—C8—C13	11.1 (4)
O1—O1—C1—C2	0.0 (6)	O1—C7—C8—C13	11.1 (4)
C7—O1—C1—C2	84.4 (3)	C13—C8—C9—C10	−0.3 (4)
C7—O1—C1—O1	0 (34)	C7—C8—C9—C10	−178.8 (3)
C6—C1—C2—C3	0.9 (4)	C8—C9—C10—C11	1.4 (4)
O1—C1—C2—C3	176.0 (2)	C9—C10—C11—C12	−1.5 (4)
O1—C1—C2—C3	176.0 (2)	C9—C10—C11—C14	178.0 (2)
C6—C1—C2—Cl1	−178.0 (2)	C10—C11—C12—C13	0.6 (4)
O1—C1—C2—Cl1	−2.8 (3)	C14—C11—C12—C13	−178.9 (2)
O1—C1—C2—Cl1	−2.8 (3)	C11—C12—C13—C8	0.4 (4)
C1—C2—C3—C4	−1.1 (4)	C9—C8—C13—C12	−0.6 (4)
Cl1—C2—C3—C4	177.7 (2)	C7—C8—C13—C12	177.8 (2)
C2—C3—C4—C5	1.2 (4)	C12—C11—C14—C19	−24.4 (4)
C2—C3—C4—Br1	−178.8 (2)	C10—C11—C14—C19	156.1 (3)
C3—C4—C5—C6	−1.1 (4)	C12—C11—C14—C15	154.5 (3)
Br1—C4—C5—C6	178.9 (2)	C10—C11—C14—C15	−25.0 (4)
C2—C1—C6—C5	−0.7 (4)	C19—C14—C15—C16	−0.1 (4)
O1—C1—C6—C5	−175.8 (2)	C11—C14—C15—C16	−179.1 (3)
O1—C1—C6—C5	−175.8 (2)	C14—C15—C16—C17	−0.2 (4)
C4—C5—C6—C1	0.8 (4)	C20—O3—C17—C18	−1.1 (4)
O1—O1—C7—O2	0.0 (5)	C20—O3—C17—C16	179.1 (2)
C1—O1—C7—O2	13.6 (4)	C15—C16—C17—O3	−179.7 (3)
C1—O1—C7—O1	0 (67)	C15—C16—C17—C18	0.5 (4)
O1—O1—C7—C8	0.0 (4)	O3—C17—C18—C19	179.7 (3)
C1—O1—C7—C8	−166.6 (2)	C16—C17—C18—C19	−0.5 (4)
O2—C7—C8—C9	9.3 (4)	C17—C18—C19—C14	0.2 (4)
O1—C7—C8—C9	−170.5 (2)	C15—C14—C19—C18	0.1 (4)
O1—C7—C8—C9	−170.5 (2)	C11—C14—C19—C18	179.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C14–C19 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cg3ⁱ	0.93	2.65	3.459 (3)	147
C10—H10···Cg3ⁱⁱ	0.93	2.85	3.577 (3)	136

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

top

Parameter	SCXRD	DFT
Br1—C4	1.900 (2)	1.9148
Cl1—C2	1.727 (3)	1.7468
O1—C7	1.375 (3)	1.3831
O1—C1	1.399 (3)	1.3848
O2—C7	1.196 (3)	1.2025
O3—C17	1.369 (3)	1.3619
C7—O1—C1	116.1 (2)	117.908
C17—O3—C20	117.4 (2)	118.693
C6—C1—C2	120.9 (2)	119.670
C6—C1—O1	119.7 (2)	119.844
O2—C7—O1	122.5 (2)	122.388
O2—C7—C8	126.2 (2)	126.007
C1—O1—C7—C8	-166.6 (2	-179.143
C7—O1—C1—C6	-100.4 (3)	-88.445
O1—C1—C2—Cl1	-2.8 (3)	-3.598

Acknowledgements

The authors acknowledge the Raman Research Institute, Bangalore, and Center of Innovative Science, Engineering and Education (CISEE), UCS, Tumkur University, for constant support in extending the laboratory facilities. MH is thankful to BSPM's lab for use of their computing facilities at the Department of PG Studies and Research in Physics, Albert Einstein Block, UCS, Tumkur University, Tumkur.

Funding information

Funding for this research was provided by: Vision Group of Science and Technology (award No. GRD319 to Palakshamrthy BS).

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