research communications
1-Chloro-4-[2-(4-chlorophenyl)ethyl]benzene and its bromo analogue:
Hirshfeld surface analysis and computational chemistryaDepartment 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
The crystal and molecular structures of C14H12Cl2, (I), and C14H12Br2, (II), are described. The of (I) comprises two independent molecules, A and B, each disposed about a centre of inversion. Each molecule approximates mirror symmetry [the Cb—Cb—Ce—Ce 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).
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 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) − x, − y, 1 − z].
of (I)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.
3. Supramolecular features
In the crystal of (I), the main point of contact between the independent molecules comprising the 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 (iii) − x, − y, −z], Fig. 3(a). The topology of the layer is flat and connections between the layers that stack along [10] are weaker end-on Cl1B⋯Cl1Biv contacts [3.4322 (7) Å and C1B—Cl1B⋯Cl1Biv = 155.19 (5)° for (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).
|
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 (i) 1 + x, y, 1 + z; Fig. 4].
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 dnorm 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.
In the crystal of (II), the bright-red spots near the bromine atoms on the Hirshfeld surfaces mapped over dnorm 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.
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.
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.
|
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 de + di ∼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 de + di ∼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 de + di ∼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 de + di ∼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 de + di ∼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 de + di ∼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 de + di ∼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.
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 (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) (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.
|
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 (Eele), green (Edisp) and blue (Etot) 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.
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 Ce—Ce (e = ethylene) bonds are long in these compounds with the exception being the pentabromo derivative, C6Br5CH2CH2C6Br5 (Köppen et al., 2007).
|
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 . The carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.99 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C). In the of (II), owing to poor agreement the (111) reflection was omitted from the final cycles of refinement.
details are summarized in Table 7
|
Supporting information
https://doi.org/10.1107/S2056989019004742/hb7814sup1.cif
contains datablocks I, II, global. DOI: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
For both structures, data collection: APEX2 (Bruker, 2008); cell
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).C14H12Cl2 | F(000) = 1040 |
Mr = 251.14 | Dx = 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 |
Bruker model? CCD area detector diffractometer | 3090 independent reflections |
Radiation source: fine-focus sealed tube | 2627 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 28.4°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −35→34 |
Tmin = 0.623, Tmax = 0.746 | k = −11→12 |
12061 measured reflections | l = −13→13 |
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(Fo2) + (0.046P)2 + 1.4907P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max = 0.001 |
3090 reflections | Δρmax = 0.31 e Å−3 |
145 parameters | Δρmin = −0.27 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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. |
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 |
C14H12Br2 | F(000) = 664 |
Mr = 340.06 | Dx = 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 |
Bruker model? CCD area detector diffractometer | 3065 independent reflections |
Radiation source: fine-focus sealed tube | 2520 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
φ and ω scans | θmax = 28.4°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −14→14 |
Tmin = 0.546, Tmax = 0.746 | k = −10→9 |
11908 measured reflections | l = −20→20 |
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(Fo2) + (0.0289P)2 + 0.0779P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max = 0.001 |
3065 reflections | Δρmax = 0.45 e Å−3 |
145 parameters | Δρmin = −0.40 e Å−3 |
0 restraints |
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. Owing to poor agreement, the (1 1 1) reflection was omitted from the final cycles of refinement. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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) |
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. |
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. |
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 |
Contact | Eele | Epol | Edis | Erep | Etot |
(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 |
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-ClC6H4a | 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.
References
Bestiuc, I., Buruiana, T., Idriceanu, S., Popescu, V. & Caraculacu, A. (1985). Rev. Chim. 36, 621–623. CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Galán, E., Perrin, M. L., Lutz, M., van der Zant, H. S. J., Grozema, F. C. & Eelkema, R. (2016). Org. Biomol. Chem. 14, 2439–2443. PubMed Google Scholar
Gans, J. & Shalloway, D. (2001). J. Mol. Graphics Modell. 19, 557–559. Web of Science CrossRef CAS Google Scholar
Golden, J. H. (1961). J. Chem. Soc. pp. 1604–1610. CrossRef Google Scholar
Hu, Y.-L., Li, F., Gu, G.-L. & Lu, M. (2011). Catal. Lett. 141, 467–473. CrossRef CAS Google Scholar
Kahr, B., Mitchell, C. A., Chance, J. M., Clark, R. V., Gantzel, P., Baldridge, K. K. & Siegel, J. S. (1995). J. Am. Chem. Soc. 117, 4479–4482. CSD CrossRef CAS Web of Science Google Scholar
Köppen, R., Emmerling, F. & Becker, R. (2007). Acta Cryst. E63, o585–o586. Web of Science CSD CrossRef IUCr Journals Google Scholar
Krafczyk, R., Thönnessen, H., Jones, P. G. & Schmutzler, R. (1997). J. Fluor. Chem. 83, 159–166. CSD CrossRef CAS Google Scholar
Liu, J. & Li, B. (2007). Synth. Commun. 37, 3273–3278. CrossRef CAS Google Scholar
Otsubo, T., Ogura, F., Yamaguchi, H., Higuchi, H. & Misumi, S. (1980). Synth. Commun. 10, 595–601. CrossRef CAS Google Scholar
Parnes, Z. N., Romanova, V. S. & Vol'pin, M. E. (1989). Zh. Org. Khim. 25, 1075–1079. CAS Google Scholar
Remizov, A. B., Kamalova, D. I. & Stolov, A. A. (2005). Russ. J. Phys. Chem. A, 79(Suppl. 1), 76–80. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. 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
Sisido, K., Takeda, Y. & Kinugawa, Z. (1961). J. Am. Chem. Soc. 83, 538–541. CrossRef Web of Science Google Scholar
Tan, S. L., Jotani, M. M. & Tiekink, E. R. T. (2019). Acta Cryst. E75, 308–318. Web of Science CrossRef IUCr Journals Google Scholar
Turner, M. J., Mckinnon, J. J., Wolff, S. K., Grimwood, D. J., Spackman, P. R., Jayatilaka, D. & Spackman, M. A. (2017). Crystal Explorer 17. The University of Western Australia. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.