1-Chloro-4-[2-(4-chloro­phen­yl)eth­yl]benzene and its bromo analogue: crystal structure, Hirshfeld surface analysis and computational chemistry

Jotani, M.M.; Lee, S.M.; Lo, K.M.; Tiekink, E.R.T.

doi:10.1107/S2056989019004742

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ISSN: 2056-9890

Volume 75| Part 5| May 2019| Pages 624-631

https://doi.org/10.1107/S2056989019004742

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1-Chloro-4-[2-(4-chlorophenyl)ethyl]benzene and its bromo analogue: crystal structure, Hirshfeld surface analysis and computational chemistry

Mukesh M. Jotani,^a ‡ See Mun Lee,^b Kong Mun Lo ^b and Edward R. T. Tiekink ^b ^*

^aDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and ^bResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
^*Correspondence e-mail: edwardt@sunway.edu.my

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 2 April 2019; accepted 8 April 2019; online 12 April 2019)

The crystal and molecular structures of C₁₄H₁₂Cl₂, (I), and C₁₄H₁₂Br₂, (II), are described. The asymmetric unit of (I) comprises two independent molecules, A and B, each disposed about a centre of inversion. Each molecule approximates mirror symmetry [the C_b—C_b—C_e—C_e torsion angles = −83.46 (19) and 95.17 (17)° for A, and −83.7 (2) and 94.75 (19)° for B; b = benzene and e = ethylene]. By contrast, the molecule in (II) is twisted, as seen in the dihedral angle of 59.29 (11)° between the benzene rings cf. 0° in (I). The molecular packing of (I) features benzene-C—H⋯π(benzene) and Cl⋯Cl contacts that lead to an open three-dimensional (3D) architecture that enables twofold 3D–3D interpenetration. The presence of benzene-C—H⋯π(benzene) and Br⋯Br contacts in the crystal of (II) consolidate the 3D architecture. The analysis of the calculated Hirshfeld surfaces confirm the influence of the benzene-C—H⋯π(benzene) and X⋯X contacts on the molecular packing and show that, to a first approximation, H⋯H, C⋯H/H⋯C and C⋯X/X⋯C contacts dominate the packing, each contributing about 30% to the overall surface in each of (I) and (II). The analysis also clearly differentiates between the A and B molecules of (I).

Keywords: crystal structure; 1,2-bis(phenyl)ethane; Hirshfeld surface analysis; interaction energies.

CCDC references: 1908484; 1908483

1. Chemical context

The synthesis and physical characterization of the title compound, 1-chloro-4-[2-(4-chlorophenyl)ethyl]benzene, C₁₄H₁₂Cl₂, (I), has been reported by several research groups over the years (Otsubo et al., 1980 ; Bestiuc et al., 1985 ; Parnes et al., 1989 ; Hu et al., 2011 ; Liu & Li, 2007 ). In the same way, the bromo analogue of (I), 1-bromo-4-[2-(4-bromophenyl)ethyl]benzene, C₁₄H₁₂Br₂, (II), has been described previously (Golden, 1961 ; Otsubo et al., 1980; Remizov et al., 2005 ; Liu & Li, 2007). Despite this interest, crystallographic characterization is lacking. Recently, compounds (I) and (II) became available as minor side-products during the synthesis of the respective tri(4-halobenzyl)tin hydroxide from the reaction of tri(4-halobenzyl)tin halide and sodium hydroxide. Herein, the crystal and molecular structures of (I) and (II) are described. The structures are not isostructural and in order to gain further insight into the molecular packing, the structures were subjected to an analysis of their Hirshfeld surfaces along with some computational chemistry.

2. Structural commentary

The two independent molecules comprising the asymmetric unit of (I) are shown in Fig. 1(a) and (b); each is disposed about a centre of inversion. The molecules present very similar features and, from inversion symmetry, comprise parallel benzene rings. The C3A—C4A—C7A—C7Aⁱ and C5A—C4A—C7A—C7Aⁱ torsion angles of −83.46 (19) and 95.17 (17)° highlight deviations from mirror symmetry in the molecule [symmetry operation: (i) 1 − x, 1 − y, 1 − z]. These values are equal within experimental error and are very close to the equivalent angles for the second independent molecule of −83.7 (2) and 94.75 (19)°, respectively [symmetry operation: (ii) $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z].

Figure 1
The molecular structures of (a) the Cl1A-containing molecule of (I)

, (b) the Cl1B-containing molecule of (I)

and (c) the molecule of (II)

showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level. Unlabelled atoms in (a) and (b) are related by the symmetry operations 1 − x, 1 − y, 1 − z and $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, 1 − z, respectively.

The molecule of (II) is shown in Fig. 1(c) and does not feature the molecular symmetry of (I). The difference in the conformation in (II), cf. (I), is seen immediately in the magnitude of the dihedral angle formed between the benzene rings of 59.29 (11)°, indicating an inclined disposition. The central torsion angle, i.e. C4—C7—C8—C9 of 172.1 (2)°, deviates from the 180° angles observed for the two independent molecules in (I). The twist in the molecule of (II) is reflected in the four torsion angles C3—C4—C7—C8 [46.6 (3)°], C5—C4—C7—C8 [−134.8 (2)°], C7—C8—C9—C14 [16.4 (3)°] and C7—C8—C9—C10 [−163.7 (2)°].

The conformational differences between the molecules in (I) and (II) are highlighted in the overlay diagram shown in Fig. 2.

Figure 2
Overlap diagram of the (a) Cl1A-molecule in (I)

(red image), (b) Cl1B-molecule in (I)

(green) and (c) the molecule in (II)

(blue). Molecules have been overlapped so that the C1-benzene rings are coincident.

3. Supramolecular features

In the crystal of (I), the main point of contact between the independent molecules comprising the asymmetric unit are of the type benzene-C—H⋯π(benzene), Table 1. The result is the formation of a supramolecular chain along the a-axis direction. Chains are connected into a supramolecular layer via end-on Cl1A⋯Cl1Aⁱⁱⁱ contacts [3.3184 (7) Å and C1—C11A⋯Cl1Aⁱⁱⁱ = 164.61 (5)° for symmetry operation (iii) $[{1\over 2}]$ − x, $[{3\over 2}]$ − y, −z], Fig. 3(a). The topology of the layer is flat and connections between the layers that stack along [1 $[\overline{1}]$ 0] are weaker end-on Cl1B⋯Cl1B^iv contacts [3.4322 (7) Å and C1B—Cl1B⋯Cl1B^iv = 155.19 (5)° for symmetry operation (iv) 1 − x, 2 − y, 2 − z], which lead to a three-dimensional (3-D) architecture. As seen from Fig, 3(b), there are large voids defined by the aforementioned contacts which enables twofold, 3D–3D interpenetration, Fig. 3(c).

Table 1
Hydrogen-bond geometry (Å, °) for (I)

Cg1 is the centroid of the (C1A–C6A) ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5B—H5B⋯Cg1	0.93	2.62	3.4866 (15)	155

Figure 3
Molecular packing in (I)

: (a) a view of the supramolecular layer parallel to [1 $[\overline{1}]$ 0] sustained by C—H⋯π and Cl⋯Cl contacts shown as purple and orange dashed lines, respectively, (b) a view of half of the unit-cell contents shown in projection down the c axis and (c) an image highlighting the twofold interpenetration in space-filling mode.

The 3-D architecture of (II) is supported by benzene-C—H⋯π(benzene) and Br⋯Br contacts. Globally, molecules assemble in the ac plane and are connected to layers along [010] by benzene-C—H⋯π(benzene) contacts, Table 2. Further, lateral interactions are Br1⋯Br2ⁱ [3.5242 (4) Å, C1—Br⋯Br2ⁱ = 144.67 (7)° and C12ⁱ—Br2ⁱ⋯Br1 = 154.39 (7)° for symmetry operation (i) 1 + x, y, 1 + z; Fig. 4].

Table 2
Hydrogen-bond geometry (Å, °) for (II)

Cg1 and Cg2 are the centroids of the (C1–C6) and (C9–C14) rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯Cg2ⁱ	0.95	2.69	3.442 (2)	136
C6—H6⋯Cg1ⁱⁱ	0.95	2.91	3.704 (2)	141
C13—H13⋯Cg2ⁱⁱⁱ	0.95	2.87	3.569 (2)	131
Symmetry codes: (i) -x, -y+1, -z+1; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 4
Molecular packing in (II)

: a view of the unit-cell contents shown in projection down the a axis, highlighting C—H⋯π and Br⋯Br contacts as purple and orange dashed lines, respectively.

4. Hirshfeld surface analysis

The Hirshfeld surface calculations for (I) and (II) were performed in accord with established procedures (Tan et al., 2019 ) with the aid of Crystal Explorer (Turner et al., 2017 ) to determine the influence of weak intermolecular interactions upon the molecular packing in the absence of conventional hydrogen bonds.

In the crystal of (I), with two independent molecules, labelled A and B, disposed about a centre of inversion the presence of faint-red spots near the benzene-C2A, C3A and H5B atoms in the images of Hirshfeld surfaces mapped over d_norm in Fig. 5 represent C—H⋯π contacts, Tables 1 and 3. The diminutive red spot viewed near the benzene-C5B atom in Fig. 5(b) indicates the effect of a short interatomic C5B⋯H2B contact, Table 3. Also, the presence of diminutive red spots near the terminal chlorine atoms of both independent molecules in Fig. 5 are due to the formation of short interatomic Cl⋯Cl contacts, Table 3.

Table 3
Summary of short interatomic contacts (Å) in (I)^a

Contact	Distance	Symmetry operation
(I)
H6B⋯H72A	2.35	x, y, z
H5B⋯C2A	2.75	x, y, z
H5B⋯C3A	2.72	x, y, z
H2B⋯C5B	2.67	x, 2 − y, $[{1\over 2}]$ + z
C11A⋯Cl1A	3.3184 (7)	$[{1\over 2}]$ − x, $[{3\over 2}]$ − y, −z
Cl1B⋯Cl1B	3.4322 (7)	1 − x, 2 − y, 2 − z
(II)
H8B⋯H8B	2.21	−x, 2 − y, 1 − z
H3⋯C13	2.74	−x, 1 − y, 1 − z
H3⋯C14	2.72	−x, 1 − y, 1 − z
H6⋯C1	2.82	1 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H6⋯C2	2.62	1 − x, $[{1\over 2}]$ + y, $[{3\over 2}]$ − z
H11⋯C6	2.80	−x, 2 − y, 1 − z
Br1⋯Br2	3.5242 (4)	1 + x, y, 1 + z
Notes: (a) The interatomic distances are calculated in Crystal Explorer (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values.

Figure 5
Views of the Hirshfeld surfaces for (I)

mapped over d_norm for (a) molecule A [in the range −0.103 to +1.259 arbitrary units] and (b) molecule B [−0.072 to +1.234 arbitrary units] highlighting the short interatomic C⋯H/H⋯C and H⋯H contacts through black and red dashed lines, respectively.

In the crystal of (II), the bright-red spots near the bromine atoms on the Hirshfeld surfaces mapped over d_norm in Fig. 6 indicate interatomic Br⋯Br contacts, Table 3, whereas those near the benzene-C2 and H6 atoms in Fig. 6(b) indicate short interatomic C—H⋯π interactions, Table 3. The presence of faint-red spots near the benzene-C13, C14 and H3 atoms in Fig. 6(a) also reflect the presence of C—H⋯π contacts, Table 3.

Figure 6
Views of the Hirshfeld surfaces for (II)

mapped over d_norm [in the range −0.104 to +1.172 arbitrary units] highlighting the short interatomic C⋯H/H⋯C contacts through black dashed lines.

From the views of Hirshfeld surfaces mapped over the calculated electrostatic potentials in Figs. 7(a) and (b) for the independent molecules of (I) highlight the small deviations from putative mirror symmetry through the slight differences in the blue and red regions around the atoms of their surfaces corresponding, respectively, to positive and negative potentials. For (II), Fig.7(c), the donors and acceptors of the C—H⋯π interactions are viewed as blue bumps and light-red concave regions. Further, the donors and acceptors of the C—H⋯π contacts for each of (I) and (II) are also illustrated through black dotted lines on the Hirshfeld surfaces mapped with shape-index properties in Fig. 8.

Figure 7
Views of the Hirshfeld surfaces mapped over the calculated electrostatic potential for (a) (I)

, molecule A [−0.032 to +0.035 a.u.], (b) (I)

, molecule B in [−0.033 to +0.044 a.u.] range and (c) (II)

[−0.022 to +0.039 a.u.]. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 8
Views of the Hirshfeld surfaces mapped with the shape index property for (a) (I)

, molecule B, (b)–(d) (II)

, highlighting intermolecular C—H⋯π interactions through black dotted lines.

The overall two-dimensional fingerprint plot for the independent molecules A and B as well as entire (I) are shown in Fig. 9(a), and those delineated into H⋯H, C⋯H/H⋯C, Cl⋯H/H⋯Cl and Cl⋯Cl contacts are illustrated in Fig. 9(b)–(e), respectively. The quantitative summary of percentage contributions from the different interatomic contacts to the respective Hirshfeld surfaces of A, B and (I) are presented in Table 4.

Table 4
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II)

Contact	Percentage contribution
	(I) - molecule A	(I) - molecule B	(I)	(II)
H⋯H	30.8	35.1	31.4	30.6
C⋯H/H⋯C	32.5	27.0	28.4	32.7
X⋯H/H⋯X	30.5	33.3	34.2	30.4
X⋯X	3.9	2.2	3.4	4.9
C⋯C	1.3	1.3	1.4	0.0
C⋯X/X⋯C	1.1	1.1	1.2	1.4

Figure 9
(a) The full two-dimensional fingerprint plot for molecule A of (I)

, molecule B of (I)

, and overall (I)

, and (b)–(e) those delineated into H⋯H, C⋯H/H⋯C, Cl⋯H/H⋯Cl and Cl⋯Cl contacts.

Some qualitative differences in the fingerprint plots are evident for molecules A and B, confirming their distinct packing interactions. The complementary pair of forceps-like tips at d_e + d_i ∼2.3 Å in the fingerprint plots delineated into H⋯H contacts for A and B in Fig. 9(b) represent the short interatomic H⋯H contact, Table 3, which merge to form a pair of tips in the overall plot for (I). The fingerprint plots delineated into C⋯H/H⋯C contacts for molecules A and B in Fig. 9(c) exhibit the clearest distinction between the interatomic contacts formed by the molecules through the asymmetric distribution of points. The complementary distribution of points in the acceptor and donor regions of the plots for A and B, respectively, with the peaks at d_e + d_i ∼2.7 Å, are due to the formation of short interatomic C⋯H/H⋯C contacts between the benzene-C2A, C3A and H5B atoms, Table 3. Similar short interatomic contacts between benzene-C5B and H2B atoms of B results in forceps-like tips at d_e + d_i ∼2.7 Å in the acceptor region of the plot whereas it is merged within the tip of previously mentioned contact in the donor region. However, the respective plot for an overall structure is symmetric owing to the merging of the asymmetric distribution of points. The significant and quite similar contributions from Cl⋯H/H⋯Cl contacts to the Hirshfeld surfaces of A, B and overall (I), Fig. 9(d), have very little influence on the molecular packing due to their interatomic distances being equal to or greater than the sum of their van der Waals radii. The linear distribution of points beginning from d_e + d_i ∼3.3 and 3.4 Å, Fig. 9(e), in the Cl⋯Cl delineated plots for A and B, respectively, indicate the presence of Cl⋯Cl interactions. The small contribution from C⋯C contacts to the Hirshfeld surface of (I) has a negligible effect on the packing.

Comparable fingerprint plots for (II) are shown in Fig. 10 and percentage contributions are collected in Table 4. The short interatomic H⋯H contact between symmetry-related ethylene-H8B atoms is viewed as a single peak at d_e + d_i ∼2.2 Å in Fig. 10(b). In Fig. 10(c), delineated into C⋯H/H⋯C contacts, Table 3, the forceps-like tips at d_e + d_i ∼2.6 Å reflect the significant C—H⋯π contacts in the molecular packing. The contribution of Br⋯H/H⋯Br contacts to the Hirshfeld surface of (II), Fig. 10(d), have very little influence on the packing due to their interatomic distances being around the sum of their van der Waals radii. The short interatomic Br⋯Br contacts in (II) are viewed as a thin, linear distribution of points initiating from d_e + d_i ∼3.5 Å, Fig. 10(e). As for (I), the small contribution from C⋯C contacts to the Hirshfeld surface of (II) has a negligible effect in the crystal.

Figure 10
(a) The full two-dimensional fingerprint plot for (II)

, and (b)–(e) those delineated into H⋯H, C⋯H/H⋯C, Br⋯Br and Br⋯H/H⋯Br contacts.

5. Computational chemistry

The pairwise interaction energies between the molecules in the crystals of (I) and (II) were calculated by summing up four energy components, being electrostatic (E_ele), polarization (E_pol), dispersion (E_dis) and exchange-repulsion (E_rep) (Turner et al., 2017). These energies were obtained by using the wave functions calculated at the B3LYP/6-31G(d,p) level theory for (I) and the HF/STO-3G level theory for (II). The individual energy components as well as total interaction energy relative to reference molecule within molecular clusters out to 3.8 Å. The nature and strength of the energies for the key identified intermolecular interactions are quantitatively summarized in Table 5. Dispersive components are dominant as conventional hydrogen bonding is not possible.

Table 5
Summary of interaction energies (kJ mol⁻¹) calculated for (I) and (II)

Contact	E_ele	E_pol	E_dis	E_rep	E_tot
(I)
Cl1A⋯Cl1A	−0.9	0.0	−3.3	7.6	0.9
Cl1B⋯Cl1B	−0.9	−0.1	−3.4	5.8	−0.4
C5—H5⋯Cg(C1A–C6A)	−8.5	−1.5	−33.5	26.1	−23.1
C5⋯H2B	−3.7	−0.8	−18.2	12.9	−12.3
(II)
Br1⋯Br2	−2.2	−0.1	−4.9	8.4	0.1
C3—H3⋯Cg(C9–C14)	−14.6	−4.7	−62.4	38.3	−43.2
C6—H6⋯Cg(C1–C6)	−5.6	−1.5	−25.1	15.5	−16.7
C13—H13⋯Cg(C9–C14)	−8.9	−1.9	−30.9	14.2	−25.9
H11⋯C6	−5.0	−3.2	−50.6	24.7	−32.7
H8B⋯H8B	−5.0	−3.2	−50.6	24.7	−32.7

The significant contributions from the C—H⋯π interaction and short interatomic C⋯H/H⋯C contacts in the crystal of (I) are evident from Table 5. Also notable, are the negligible energies associated with the Cl⋯Cl contacts due to the dominance of repulsive contributions. With respect to (II), it is evident from the comparison of the dispersive component as well as total energies for the different interactions that the strength of interactions in the crystal depend upon distance between the respective molecules. The short Br⋯Br contacts in (II) also have very small interaction energies.

The magnitudes of intermolecular energies are represented graphically in the energy frameworks of Fig. 11. Here, the supramolecular architecture of each crystal is viewed through the cylinders joining the centroids of molecular pairs. The red (E_ele), green (E_disp) and blue (E_tot) colour scheme represent the specified energy components. The radii of the cylinders are proportional to the magnitude of interaction energies which are adjusted with a cut-off value of 2 kJ mol⁻¹ within 4 × 4 × 4 unit cells. The energy frameworks constructed for the clusters about the independent molecules A and B of (I) as well as that for (II) also indicate the distinct mode of supramolecular association around the molecules in the molecular packing. The small effect of the electrostatic components and the significant influence of the dispersive components are clearly evident from the energy frameworks shown in Fig. 11.

Figure 11
A comparison of the energy frameworks composed of (a) electrostatic potential force, (b) dispersion force and (c) total energy for cluster about a reference molecule of A and B of (I)

, and for (II)

. The energy frameworks were adjusted to the same scale factor of 80 with a cut-off value of 2 kJ mol⁻¹ within 4 × 4 × 4 unit cells.

6. Database survey

There are only four halo-substituted 1,2-bis(phenyl)ethylene derivatives in the literature. The key structural parameters for these are summarized in Table 6. Only one literature structure is not disposed about a centre of inversion, namely the non-symmetric, mixed-halo structure (4-Br,2,6-F₂C₆H₂)CH₂CH₂C₆H₄Br-4 (Galán et al., 2016 ). Generally, the central C_e—C_e (e = ethylene) bonds are long in these compounds with the exception being the pentabromo derivative, C₆Br₅CH₂CH₂C₆Br₅ (Köppen et al., 2007 ).

Table 6
Geometric data (Å, °) for halo-substituted 1,2-bis(phenyl)ethane structures

Ring 1	Ring 2	Symmetry	CH₂—CH₂	dihedral angle C₆/C₆	Reference
2-BrC₆H₄	2-BrC₆H₄	$[\overline{1}]$	1.540 (7)	0	Kahr et al. (1995 )
C₆F₅	C₆F₅	$[\overline{1}]$	1.542 (3)	0	Krafczyk et al. (1997 )
C₆Br₅	C₆Br₅	$[\overline{1}]$	1.495 (13)	0	Köppen et al. (2007)
4-Br,2,6-F₂C₆H₂	4-BrC₆H₄	–	1.522 (10)	1.67 (16)	Galán et al. (2016)
4-ClC₆H₄^a	4-ClC₆H₄	$[\overline{1}]$	1.530 (2)	0	This work
		$[\overline{1}]$	1.530 (3)	0
4-BrC₆H₄	4-BrC₆H₄	–	1.516 (3)	59.29 (11)	This work
Notes: (a) Two independent molecules comprise the asymmetric unit.

7. Synthesis and crystallization

Tri(4-chlorobenzyl)tin chloride was prepared by direct synthesis using tin powder (Merck) and 4-chlorobenzyl chloride (Sigma–Aldrich) in water (Sisido et al., 1961 ). Tri(4-chlorobenzyl)tin chloride (5.3 g, 10 mmol) was dissolved in 95% ethanol (150 ml) and to this was added dropwise 10% sodium hydroxide solution (4 ml). The resulting solution was heated for 1 h. After cooling, the white tri(4-chlorobenzyl)tin hydroxide was filtered off and the filtrate was evaporated slowly to obtain a colourless crystalline solid which was identified crystallographically as (I). Yield: 0.28 g (0.11%). The bromo analogue was similarly obtained as a side-product from the base hydrolysis of tri(4-bromobenzyl)tin bromide. Tri(4-bromobenzyltin) bromide was prepared from the reaction of tin powder (Sigma–Aldrich) and 4-bromobenzyl bromide (Merck) in water (Sisido et al., 1961). Tri(4-bromobenzyl)tin bromide (7.0 g, 10 mmol) was dissolved in 95% ethanol (150 ml) and to this was added 10% sodium hydroxide solution (4 ml). The resulting precipitation was heated for 1 h. After cooling, the yellow tri(4-bromobenzyl)tin hydroxide was filtered off and the filtrate was evaporated slowly to obtain a yellow crystalline solid which was identified crystallographically as (II). Yield: 0.25 g (0.07%)

8. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 7. The carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.99 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2U_eq(C). In the refinement of (II), owing to poor agreement the (111) reflection was omitted from the final cycles of refinement.

Table 7
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₁₄H₁₂Cl₂	C₁₄H₁₂Br₂
M_r	251.14	340.06
Crystal system, space group	Monoclinic, C2/c	Monoclinic, P2₁/c
Temperature (K)	296	100
a, b, c (Å)	26.6755 (19), 9.3259 (7), 10.0405 (8)	10.8761 (2), 7.5157 (1), 15.6131 (3)
β (°)	99.560 (4)	106.177 (1)
V (Å³)	2463.1 (3)	1225.71 (4)
Z	8	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.50	6.58
Crystal size (mm)	0.30 × 0.20 × 0.10	0.20 × 0.11 × 0.07

Data collection
Diffractometer	Bruker SMART APEX CCD area detector	Bruker SMART APEX CCD area detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996 )	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.623, 0.746	0.546, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	12061, 3090, 2627	11908, 3065, 2520
R_int	0.026	0.035
(sin θ/λ)_max (Å⁻¹)	0.669	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.090, 1.04	0.026, 0.058, 1.03
No. of reflections	3090	3065
No. of parameters	145	145
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.27	0.45, −0.41
Computer programs: APEX2 (Bruker, 2008 ), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ), QMol (Gans & Shalloway, 2001 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC references: 1908484; 1908483

Crystal structure: contains datablocks I, II, global. DOI: https://doi.org/10.1107/S2056989019004742/hb7814sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004742/hb7814Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019004742/hb7814IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989019004742/hb7814Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989019004742/hb7814IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), DIAMOND (Brandenburg, 2006) and QMol (Gans & Shalloway, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

1-Chloro-4-[2-(4-chlorophenyl)ethyl]benzene (I) top

Crystal data top

C₁₄H₁₂Cl₂	F(000) = 1040
M_r = 251.14	D_x = 1.354 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 26.6755 (19) Å	Cell parameters from 4470 reflections
b = 9.3259 (7) Å	θ = 3.1–28.3°
c = 10.0405 (8) Å	µ = 0.50 mm⁻¹
β = 99.560 (4)°	T = 296 K
V = 2463.1 (3) Å³	Prism, colourless
Z = 8	0.30 × 0.20 × 0.10 mm

Data collection top

Bruker model? CCD area detector diffractometer	3090 independent reflections
Radiation source: fine-focus sealed tube	2627 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
φ and ω scans	θ_max = 28.4°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −35→34
T_min = 0.623, T_max = 0.746	k = −11→12
12061 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.090	w = 1/[σ²(F_o²) + (0.046P)² + 1.4907P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3090 reflections	Δρ_max = 0.31 e Å⁻³
145 parameters	Δρ_min = −0.27 e Å⁻³
0 restraints

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
Cl1A	0.30558 (2)	0.69571 (4)	0.08421 (3)	0.02990 (11)
C1A	0.35616 (5)	0.64904 (15)	0.20984 (13)	0.0213 (3)
C2A	0.39856 (5)	0.73741 (15)	0.23346 (13)	0.0227 (3)
H2A	0.400392	0.819329	0.181667	0.027*
C3A	0.43825 (5)	0.70121 (14)	0.33594 (13)	0.0224 (3)
H3A	0.466935	0.759394	0.351988	0.027*
C4A	0.43591 (5)	0.57952 (14)	0.41510 (13)	0.0202 (3)
C5A	0.39306 (5)	0.49193 (14)	0.38683 (13)	0.0224 (3)
H5A	0.391223	0.409246	0.437578	0.027*
C6A	0.35314 (5)	0.52569 (15)	0.28454 (13)	0.0237 (3)
H6A	0.324808	0.466334	0.266505	0.028*
C7A	0.47884 (5)	0.54105 (15)	0.52636 (13)	0.0236 (3)
H7A1	0.465754	0.482765	0.592893	0.028*
H7A2	0.492801	0.628077	0.570743	0.028*
Cl1B	0.44971 (2)	0.90465 (4)	0.91449 (4)	0.03360 (12)
C1B	0.39561 (5)	0.87925 (14)	0.79317 (14)	0.0229 (3)
C2B	0.34836 (6)	0.90808 (15)	0.82606 (14)	0.0271 (3)
H2B	0.345284	0.938736	0.912478	0.033*
C3B	0.30571 (5)	0.89060 (15)	0.72836 (15)	0.0274 (3)
H3B	0.273843	0.910620	0.749858	0.033*
C4B	0.30929 (5)	0.84387 (14)	0.59888 (13)	0.0223 (3)
C5B	0.35742 (5)	0.81356 (15)	0.56992 (14)	0.0254 (3)
H5B	0.360595	0.780451	0.484341	0.031*
C6B	0.40064 (5)	0.83161 (15)	0.66564 (14)	0.0258 (3)
H6B	0.432599	0.811998	0.644554	0.031*
C7B	0.26239 (5)	0.82320 (15)	0.49401 (15)	0.0272 (3)
H7B1	0.271471	0.832325	0.404772	0.033*
H7B2	0.238029	0.898025	0.504017	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1A	0.02150 (17)	0.0400 (2)	0.02582 (18)	0.00466 (13)	−0.00301 (12)	0.00464 (14)
C1A	0.0173 (6)	0.0266 (7)	0.0191 (6)	0.0037 (5)	0.0005 (5)	−0.0009 (5)
C2A	0.0226 (6)	0.0237 (6)	0.0222 (6)	0.0005 (5)	0.0051 (5)	0.0011 (5)
C3A	0.0186 (6)	0.0257 (6)	0.0230 (6)	−0.0014 (5)	0.0041 (5)	−0.0029 (5)
C4A	0.0175 (6)	0.0246 (6)	0.0186 (6)	0.0046 (5)	0.0031 (5)	−0.0031 (5)
C5A	0.0230 (6)	0.0206 (6)	0.0236 (6)	0.0016 (5)	0.0035 (5)	0.0009 (5)
C6A	0.0199 (6)	0.0247 (7)	0.0258 (7)	−0.0028 (5)	0.0017 (5)	−0.0024 (5)
C7A	0.0199 (6)	0.0292 (7)	0.0207 (6)	0.0045 (5)	0.0003 (5)	−0.0019 (5)
Cl1B	0.02872 (19)	0.0322 (2)	0.0356 (2)	−0.00182 (13)	−0.00707 (15)	−0.00290 (14)
C1B	0.0223 (6)	0.0199 (6)	0.0251 (6)	−0.0016 (5)	0.0001 (5)	0.0008 (5)
C2B	0.0296 (7)	0.0296 (7)	0.0233 (7)	−0.0023 (5)	0.0076 (6)	−0.0057 (5)
C3B	0.0214 (6)	0.0308 (7)	0.0313 (7)	−0.0006 (5)	0.0084 (5)	−0.0031 (6)
C4B	0.0211 (6)	0.0203 (6)	0.0250 (6)	−0.0005 (5)	0.0024 (5)	0.0028 (5)
C5B	0.0279 (7)	0.0278 (7)	0.0215 (6)	0.0031 (5)	0.0067 (5)	−0.0011 (5)
C6B	0.0216 (6)	0.0280 (7)	0.0286 (7)	0.0041 (5)	0.0069 (5)	0.0002 (5)
C7B	0.0251 (7)	0.0269 (7)	0.0276 (7)	−0.0002 (5)	−0.0011 (6)	0.0033 (6)

Geometric parameters (Å, º) top

Cl1A—C1A	1.7424 (13)	Cl1B—C1B	1.7432 (13)
C1A—C6A	1.3829 (19)	C1B—C2B	1.381 (2)
C1A—C2A	1.3877 (18)	C1B—C6B	1.383 (2)
C2A—C3A	1.3899 (18)	C2B—C3B	1.383 (2)
C2A—H2A	0.9300	C2B—H2B	0.9300
C3A—C4A	1.3928 (19)	C3B—C4B	1.3895 (19)
C3A—H3A	0.9300	C3B—H3B	0.9300
C4A—C5A	1.3952 (18)	C4B—C5B	1.3917 (18)
C4A—C7A	1.5043 (17)	C4B—C7B	1.5079 (18)
C5A—C6A	1.3873 (18)	C5B—C6B	1.3832 (19)
C5A—H5A	0.9300	C5B—H5B	0.9300
C6A—H6A	0.9300	C6B—H6B	0.9300
C7A—C7Aⁱ	1.530 (2)	C7B—C7Bⁱⁱ	1.530 (3)
C7A—H7A1	0.9700	C7B—H7B1	0.9700
C7A—H7A2	0.9700	C7B—H7B2	0.9700

C6A—C1A—C2A	121.37 (12)	C2B—C1B—C6B	121.11 (12)
C6A—C1A—Cl1A	119.51 (10)	C2B—C1B—Cl1B	119.26 (11)
C2A—C1A—Cl1A	119.12 (10)	C6B—C1B—Cl1B	119.63 (10)
C1A—C2A—C3A	118.77 (12)	C3B—C2B—C1B	118.90 (13)
C1A—C2A—H2A	120.6	C3B—C2B—H2B	120.6
C3A—C2A—H2A	120.6	C1B—C2B—H2B	120.6
C2A—C3A—C4A	121.30 (12)	C2B—C3B—C4B	121.62 (13)
C2A—C3A—H3A	119.4	C2B—C3B—H3B	119.2
C4A—C3A—H3A	119.4	C4B—C3B—H3B	119.2
C3A—C4A—C5A	118.28 (12)	C3B—C4B—C5B	117.94 (12)
C3A—C4A—C7A	121.15 (12)	C3B—C4B—C7B	121.02 (12)
C5A—C4A—C7A	120.55 (12)	C5B—C4B—C7B	121.03 (12)
C6A—C5A—C4A	121.33 (12)	C6B—C5B—C4B	121.43 (13)
C6A—C5A—H5A	119.3	C6B—C5B—H5B	119.3
C4A—C5A—H5A	119.3	C4B—C5B—H5B	119.3
C5A—C6A—C1A	118.92 (12)	C5B—C6B—C1B	118.99 (12)
C5A—C6A—H6A	120.5	C5B—C6B—H6B	120.5
C1A—C6A—H6A	120.5	C1B—C6B—H6B	120.5
C4A—C7A—C7Aⁱ	112.14 (13)	C4B—C7B—C7Bⁱⁱ	112.23 (14)
C4A—C7A—H7A1	109.2	C4B—C7B—H7B1	109.2
C7Aⁱ—C7A—H7A1	109.2	C7Bⁱⁱ—C7B—H7B1	109.2
C4A—C7A—H7A2	109.2	C4B—C7B—H7B2	109.2
C7Aⁱ—C7A—H7A2	109.2	C7Bⁱⁱ—C7B—H7B2	109.2
H7A1—C7A—H7A2	107.9	H7B1—C7B—H7B2	107.9

C6A—C1A—C2A—C3A	−0.98 (19)	C6B—C1B—C2B—C3B	−1.0 (2)
Cl1A—C1A—C2A—C3A	178.52 (10)	Cl1B—C1B—C2B—C3B	178.62 (11)
C1A—C2A—C3A—C4A	−0.5 (2)	C1B—C2B—C3B—C4B	0.5 (2)
C2A—C3A—C4A—C5A	1.63 (19)	C2B—C3B—C4B—C5B	0.5 (2)
C2A—C3A—C4A—C7A	−179.71 (12)	C2B—C3B—C4B—C7B	179.08 (13)
C3A—C4A—C5A—C6A	−1.28 (19)	C3B—C4B—C5B—C6B	−1.2 (2)
C7A—C4A—C5A—C6A	−179.95 (12)	C7B—C4B—C5B—C6B	−179.72 (13)
C4A—C5A—C6A—C1A	−0.2 (2)	C4B—C5B—C6B—C1B	0.8 (2)
C2A—C1A—C6A—C5A	1.3 (2)	C2B—C1B—C6B—C5B	0.3 (2)
Cl1A—C1A—C6A—C5A	−178.18 (10)	Cl1B—C1B—C6B—C5B	−179.24 (11)
C3A—C4A—C7A—C7Aⁱ	−83.46 (19)	C3B—C4B—C7B—C7Bⁱⁱ	−83.7 (2)
C5A—C4A—C7A—C7Aⁱ	95.17 (17)	C5B—C4B—C7B—C7Bⁱⁱ	94.75 (19)

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

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the (C1A–C6A) ring.

D—H···A	D—H	H···A	D···A	D—H···A
C5B—H5B···Cg1	0.93	2.62	3.4866 (15)	155

1-Bromo-4-[2-(4-chlorophenyl)ethyl]benzene (II) top

Crystal data top

C₁₄H₁₂Br₂	F(000) = 664
M_r = 340.06	D_x = 1.843 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.8761 (2) Å	Cell parameters from 3449 reflections
b = 7.5157 (1) Å	θ = 2.9–28.3°
c = 15.6131 (3) Å	µ = 6.58 mm⁻¹
β = 106.177 (1)°	T = 100 K
V = 1225.71 (4) Å³	Prism, colourless
Z = 4	0.20 × 0.11 × 0.07 mm

Data collection top

Bruker model? CCD area detector diffractometer	3065 independent reflections
Radiation source: fine-focus sealed tube	2520 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
φ and ω scans	θ_max = 28.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.546, T_max = 0.746	k = −10→9
11908 measured reflections	l = −20→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H-atom parameters constrained
wR(F²) = 0.058	w = 1/[σ²(F_o²) + (0.0289P)² + 0.0779P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
3065 reflections	Δρ_max = 0.45 e Å⁻³
145 parameters	Δρ_min = −0.40 e Å⁻³
0 restraints

Special details top

Refinement. Owing to poor agreement, the (1 1 1) reflection was omitted from the final cycles of refinement.

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

	x	y	z	U_iso*/U_eq
Br1	0.50841 (2)	0.84764 (3)	0.90903 (2)	0.02370 (8)
Br2	−0.25048 (2)	0.70383 (3)	0.09773 (2)	0.02253 (8)
C1	0.4150 (2)	0.8055 (3)	0.78827 (15)	0.0159 (5)
C2	0.3013 (2)	0.7135 (3)	0.77050 (15)	0.0161 (4)
H2	0.269796	0.672242	0.817887	0.019*
C3	0.2335 (2)	0.6817 (3)	0.68274 (15)	0.0177 (5)
H3	0.155194	0.617644	0.670292	0.021*
C4	0.2778 (2)	0.7417 (3)	0.61232 (15)	0.0167 (5)
C5	0.3933 (2)	0.8356 (3)	0.63289 (16)	0.0187 (5)
H5	0.425069	0.878319	0.585874	0.022*
C6	0.4624 (2)	0.8674 (3)	0.72041 (15)	0.0173 (5)
H6	0.541066	0.930801	0.733576	0.021*
C7	0.2051 (2)	0.7034 (4)	0.51691 (16)	0.0255 (6)
H7A	0.218424	0.577129	0.503799	0.031*
H7B	0.241041	0.777365	0.477256	0.031*
C8	0.0625 (2)	0.7386 (3)	0.49531 (15)	0.0212 (5)
H8A	0.025232	0.652822	0.529264	0.025*
H8B	0.049949	0.859257	0.516862	0.025*
C9	−0.0116 (2)	0.7260 (3)	0.39829 (14)	0.0147 (4)
C10	−0.1344 (2)	0.7992 (3)	0.36922 (15)	0.0167 (5)
H10	−0.170004	0.854105	0.411688	0.020*
C11	−0.2056 (2)	0.7945 (3)	0.28122 (15)	0.0172 (5)
H11	−0.288380	0.846752	0.263034	0.021*
C12	−0.1540 (2)	0.7119 (3)	0.21965 (15)	0.0161 (4)
C13	−0.0336 (2)	0.6354 (3)	0.24522 (15)	0.0172 (5)
H13	0.000460	0.578442	0.202509	0.021*
C14	0.0369 (2)	0.6430 (3)	0.33433 (15)	0.0154 (4)
H14	0.119669	0.590830	0.352166	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02109 (13)	0.02960 (15)	0.01712 (13)	−0.00317 (9)	−0.00014 (9)	−0.00484 (9)
Br2	0.01971 (13)	0.03068 (15)	0.01471 (12)	−0.00164 (9)	0.00065 (9)	0.00265 (9)
C1	0.0149 (11)	0.0157 (12)	0.0151 (11)	0.0040 (8)	0.0009 (9)	−0.0027 (8)
C2	0.0160 (11)	0.0163 (11)	0.0175 (11)	0.0019 (8)	0.0073 (9)	0.0018 (9)
C3	0.0136 (11)	0.0205 (12)	0.0185 (12)	−0.0004 (8)	0.0036 (9)	−0.0009 (9)
C4	0.0146 (11)	0.0200 (12)	0.0152 (11)	0.0023 (8)	0.0036 (9)	−0.0006 (9)
C5	0.0146 (11)	0.0216 (12)	0.0214 (12)	0.0015 (9)	0.0076 (9)	0.0038 (9)
C6	0.0106 (10)	0.0172 (12)	0.0243 (12)	−0.0004 (8)	0.0053 (9)	−0.0012 (9)
C7	0.0160 (12)	0.0436 (16)	0.0171 (12)	0.0027 (10)	0.0050 (10)	−0.0026 (11)
C8	0.0166 (12)	0.0281 (13)	0.0172 (12)	0.0018 (10)	0.0021 (9)	−0.0023 (10)
C9	0.0169 (11)	0.0132 (11)	0.0146 (11)	−0.0018 (8)	0.0054 (9)	0.0007 (8)
C10	0.0173 (11)	0.0152 (12)	0.0195 (12)	−0.0002 (8)	0.0082 (9)	0.0003 (9)
C11	0.0129 (10)	0.0172 (12)	0.0211 (12)	0.0006 (8)	0.0039 (9)	0.0026 (9)
C12	0.0160 (11)	0.0175 (12)	0.0133 (10)	−0.0038 (8)	0.0015 (9)	0.0025 (9)
C13	0.0189 (11)	0.0165 (12)	0.0174 (11)	−0.0011 (9)	0.0070 (9)	−0.0003 (9)
C14	0.0129 (11)	0.0160 (11)	0.0176 (11)	−0.0012 (8)	0.0048 (9)	0.0015 (9)

Geometric parameters (Å, º) top

Br1—C1	1.902 (2)	C7—H7B	0.9900
Br2—C12	1.901 (2)	C8—C9	1.507 (3)
C1—C2	1.376 (3)	C8—H8A	0.9900
C1—C6	1.382 (3)	C8—H8B	0.9900
C2—C3	1.384 (3)	C9—C10	1.399 (3)
C2—H2	0.9500	C9—C14	1.399 (3)
C3—C4	1.393 (3)	C10—C11	1.377 (3)
C3—H3	0.9500	C10—H10	0.9500
C4—C5	1.398 (3)	C11—C12	1.388 (3)
C4—C7	1.507 (3)	C11—H11	0.9500
C5—C6	1.385 (3)	C12—C13	1.384 (3)
C5—H5	0.9500	C13—C14	1.390 (3)
C6—H6	0.9500	C13—H13	0.9500
C7—C8	1.516 (3)	C14—H14	0.9500
C7—H7A	0.9900

C2—C1—C6	121.4 (2)	C9—C8—C7	116.1 (2)
C2—C1—Br1	119.02 (17)	C9—C8—H8A	108.3
C6—C1—Br1	119.57 (17)	C7—C8—H8A	108.3
C1—C2—C3	119.2 (2)	C9—C8—H8B	108.3
C1—C2—H2	120.4	C7—C8—H8B	108.3
C3—C2—H2	120.4	H8A—C8—H8B	107.4
C2—C3—C4	121.3 (2)	C10—C9—C14	117.4 (2)
C2—C3—H3	119.4	C10—C9—C8	119.73 (19)
C4—C3—H3	119.4	C14—C9—C8	122.9 (2)
C3—C4—C5	117.9 (2)	C11—C10—C9	122.3 (2)
C3—C4—C7	121.1 (2)	C11—C10—H10	118.8
C5—C4—C7	120.9 (2)	C9—C10—H10	118.8
C6—C5—C4	121.3 (2)	C10—C11—C12	118.6 (2)
C6—C5—H5	119.3	C10—C11—H11	120.7
C4—C5—H5	119.3	C12—C11—H11	120.7
C1—C6—C5	118.8 (2)	C13—C12—C11	121.3 (2)
C1—C6—H6	120.6	C13—C12—Br2	119.32 (17)
C5—C6—H6	120.6	C11—C12—Br2	119.41 (17)
C4—C7—C8	114.2 (2)	C12—C13—C14	119.0 (2)
C4—C7—H7A	108.7	C12—C13—H13	120.5
C8—C7—H7A	108.7	C14—C13—H13	120.5
C4—C7—H7B	108.7	C13—C14—C9	121.4 (2)
C8—C7—H7B	108.7	C13—C14—H14	119.3
H7A—C7—H7B	107.6	C9—C14—H14	119.3

C6—C1—C2—C3	0.3 (3)	C7—C8—C9—C10	−163.7 (2)
Br1—C1—C2—C3	−179.64 (16)	C7—C8—C9—C14	16.4 (3)
C1—C2—C3—C4	−0.3 (3)	C14—C9—C10—C11	−1.3 (3)
C2—C3—C4—C5	0.0 (3)	C8—C9—C10—C11	178.8 (2)
C2—C3—C4—C7	178.7 (2)	C9—C10—C11—C12	0.9 (3)
C3—C4—C5—C6	0.4 (3)	C10—C11—C12—C13	0.0 (3)
C7—C4—C5—C6	−178.3 (2)	C10—C11—C12—Br2	−179.99 (16)
C2—C1—C6—C5	0.0 (3)	C11—C12—C13—C14	−0.5 (3)
Br1—C1—C6—C5	179.96 (16)	Br2—C12—C13—C14	179.49 (16)
C4—C5—C6—C1	−0.4 (3)	C12—C13—C14—C9	0.1 (3)
C3—C4—C7—C8	46.6 (3)	C10—C9—C14—C13	0.7 (3)
C5—C4—C7—C8	−134.8 (2)	C8—C9—C14—C13	−179.4 (2)
C4—C7—C8—C9	172.1 (2)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the (C1–C6) and (C9–C14) rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg2ⁱ	0.95	2.69	3.442 (2)	136
C6—H6···Cg1ⁱⁱ	0.95	2.91	3.704 (2)	141
C13—H13···Cg2ⁱⁱⁱ	0.95	2.87	3.569 (2)	131

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

Summary of short interatomic contacts (Å) in (I)^a top

Contact	Distance	Symmetry operation
(I)
H6B···H72A	2.35	x, y, z
H5B···C2A	2.75	x, y, z
H5B···C3A	2.72	x, y, z
H2B···C5B	2.67	x, 2 - y, 1/2 + z
C11A···Cl1A	3.3184 (7)	1/2 - x, 3/2 - y, -z
Cl1B···Cl1B	3.4322 (7)	1 - x, 2 - y, 2 - z
(II)
H8B···H8B	2.21	-x, 2 - y, 1 - z
H3···C13	2.74	-x, 1 - y, 1 - z
H3···C14	2.72	-x, 1 - y, 1 - z
H6···C1	2.82	1 - x, 1/2 + y, 3/2 - z
H6···C2	2.62	1 - x, 1/2 + y, 3/2 - z
H11···C6	2.80	-x, 2 - y, 1 - z
Br1···Br2	3.5242 (4)	1 + x, y, 1 + z

Notes: (a) The interatomic distances are calculated in Crystal Explorer (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values.

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) and (II) top

Contact	Percentage contribution
	(I) - molecule A	(I) - molecule B	(I)	(II)
H···H	30.8	35.1	31.4	30.6
C···H/H···C	32.5	27.0	28.4	32.7
X···H/H···X	30.5	33.3	34.2	30.4
X···X	3.9	2.2	3.4	4.9
C···C	1.3	1.3	1.4	0.0
C···X/X···C	1.1	1.1	1.2	1.4

Summary of interaction energies (kJ mol^-1) calculated for (I) and (II) top

Contact	E_ele	E_pol	E_dis	E_rep	E_tot
(I)
Cl1A···Cl1A	-0.9	0.0	-3.3	7.6	0.9
Cl1B···Cl1B	-0.9	-0.1	-3.4	5.8	-0.4
C5—H5···Cg(C1A–C6A)	-8.5	-1.5	-33.5	26.1	-23.1
C5···H2B	-3.7	-0.8	-18.2	12.9	-12.3
(II)
Br1···Br2	-2.2	-0.1	-4.9	8.4	0.1
C3—H3···Cg(C9–C14)	-14.6	-4.7	-62.4	38.3	-43.2
C6—H6···Cg(C1–C6)	-5.6	-1.5	-25.1	15.5	-16.7
C13—H13···Cg(C9–C14)	-8.9	-1.9	-30.9	14.2	-25.9
H11···C6	-5.0	-3.2	-50.6	24.7	-32.7
H8B···H8B	-5.0	-3.2	-50.6	24.7	-32.7

Geometric data (Å, °) for halo-substituted 1,2-bis(phenyl)ethane structures top

Ring 1	Ring 2	Symmetry	CH₂—CH₂	dihedral angle C₆/C₆	Reference
2-BrC₆H₄	2-BrC₆H₄	1	1.540 (7)	0	Kahr et al. (1995)
C₆F₅	C₆F₅	1	1.542 (3)	0	Krafczyk et al. (1997)
C₆Br₅	C₆Br₅	1	1.495 (13)	0	Köppen et al. (2007)
4-Br,2,6-F₂C₆H₂	4-BrC₆H₄	–	1.522 (10)	1.67 (16)	Galán et al. (2016)
4-ClC₆H₄^a	4-ClC₆H₄	1	1.530 (2)	0	This work
		1	1.530 (3)	0
4-BrC₆H₄	4-BrC₆H₄	–	1.516 (3)	59.29 (11)	This work

Notes: (a) Two independent molecules comprise the asymmetric unit.

Footnotes

‡Additional correspondence author, e-mail: mmjotani@rediffmail.com.

Acknowledgements

Sunway University Sdn Bhd is thanked for support.

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