research communications
2-[(4-Chlorophenyl)sulfanyl]-2-methoxy-1-phenylethan-1-one:
and Hirshfeld surface analysisaDepartamento de Física, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, bDepartamento de Química, Universidade Federal de São Carlos, 13565-905 São Carlos, SP, Brazil, cInstituto de Química, Universidade de São Paulo, 05508-000 São Paulo, SP, Brazil, dDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and eResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: julio@power.ufscar.br
The title compound, C15H13ClO2S, comprises (4-chlorophenyl)sulfanyl, benzaldehyde and methoxy residues linked at a chiral methine-C atom (the crystal is racemic). A twist in the methine-C—C(carbonyl) bond [O—C—C—O torsion angle = 19.3 (7)°] leads to a dihedral angle of 22.2 (5)° between the benzaldehyde and methine+methoxy residues. The chlorobenzene ring is folded to lie over the O atoms, with the dihedral angle between the benzene rings being 42.9 (2)°. In the crystal, the carbonyl-O atom accepts two C—H⋯O interactions with methyl- and methine-C—H atoms being the donors. The result is an helical supramolecular chain aligned along the c axis; chains pack with no directional interactions between them. An analysis of the Hirshfeld surface points to the important contributions of weak H⋯H and C⋯C contacts to the molecular packing.
Keywords: crystal structure; sulfanyl; phenylethanone; Hirshfeld surface analysis; NCI plots.
CCDC reference: 1838590
1. Chemical context
As part of our ongoing studies on the conformational and electronic characteristics of some β-thiocarbonyl, β-bis-thiocarbonyl and β-thio-β-oxacarbonyl compounds, e.g. N,N-diethyl-2-[(4′-substituted)phenylthio]acetamides (Vinhato et al., 2013), 1-methyl-3-phenylsulfonyl-2-piperidones (Zukerman-Schpector et al., 2008), 3,3-bis[(4′-substituted) phenylsulfanyl]-1-methyl-2-piperidones (Olivato et al., 2013), 2-alkylthio-2-alkylsulfinyl-acetophenones and 2-alkylthio-2-phenylsulfonyl-acetophenones, 2-alkylsulfinyl-2-alkylsulfonyl-acetophenones (Distefano et al., 1996), 2-methoxy-2-[(4′-substituted) phenylsulfanyl]-acetophenones (Zukerman-Schpector et al., 2015; Caracelli et al., 2015) and 2-methoxy-2-(phenylselanyl)-(4′-substituted)acetophenones (Traesel et al., 2018), utilizing infrared spectroscopy, computational chemistry and X-ray diffraction methods, the title compound (I) was synthesized and characterized. The primary motivation behind this work is the search for selenium/sulfur-containing compounds with anti-inflammatory activity that could be selective COX-2 inhibitors (Cerqueira et al., 2015, 2017). Molecular have also been conducted in order to understand the mechanism of inhibition (Baptistini, 2015). Herein, the crystal and molecular structures of (I) are described along with an analysis of the calculated Hirshfeld surfaces and non-covalent interaction plots for selected interactions.
2. Structural commentary
The molecular structure of (I) sees (4-chlorophenyl)sulfanyl, phenylethanone and methoxy groups linked at the chiral methine-C8 atom, Fig. 1. In the arbitrarily chosen asymmetric molecule, C8 has an R configuration, but crystal symmetry generates a The base of the molecule is defined by the phenylethanone [r.m.s. deviation of the eight non-hydrogen atoms = 0.0134 Å] and methoxy groups. These residues are not co-planar, with the dihedral angle between the two planes being 22.2 (5)° owing to the twist about the C8—C9 bond as seen in the value of the O1—C8—C9—O2 torsion angle of 19.3 (7)°. The 4-chlorophenyl group is orientated so that the ring lies over the oxygen atoms with the dihedral angle between the benzene rings being 42.9 (2)°.
3. Supramolecular features
The molecular packing of (I) features C—H⋯O interactions where the donors are methyl-C7 and methine-C8 H atoms, and the acceptor is the carbonyl-O2 atom, Table 1. These interactions combine to sustain a supramolecular chain along [001] with an helical topology as it is propagated by 21 symmetry, Fig. 2a. Chains assemble into the three-dimensional architecture without directional interactions between them, Fig. 2b.
4. Hirshfeld surface analysis
The Hirshfeld surface calculations for (I) were performed as per a recent study (Zukerman-Schpector et al., 2017) and serve to provide additional information on the molecular packing, in particular the weaker interactions between molecules. In addition to bright-red spots near the methyl-H7A and methine-H8 atoms, a pair near the carbonyl-O2 atom arise as a result of the C—H⋯O interactions leading to the supramolecular chain discussed above, Table 1. The presence of diminutive and faint-red spots on the Hirshfeld surfaces illustrated in Fig. 3 indicate the influence of short interatomic contacts on the molecular packing in the crystal, Table 2. Thus, the C⋯C and C⋯H/H⋯C contacts involving chlorobenzene-C6, carbonyl-C9 and methyl-H7C atoms are viewed as the pair of diminutive and faint-red spots near these atoms in Fig. 3, whereas similar features near the methyl-H7B, phenyl-C14 and -H14 atoms represent H7B⋯H14 and C⋯H/H⋯C contacts. Views of the Hirshfeld surfaces mapped over electrostatic potential are shown in Fig. 4 and also indicate the donors and acceptors of the C—H⋯O interactions through the appearance of intense-blue and -red regions around the participating atoms. Fig. 5 illustrates the environment around a reference molecule within the dnorm-mapped Hirshfeld surface and highlight the intermolecular C—H⋯O interactions and short interatomic H⋯H, C⋯H/H⋯C and C⋯C contacts.
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The non-symmetric molecular geometry in (I) results in an asymmetric distribution of points in its overall two-dimensional fingerprint plot shown in Fig. 6 and also in those delineated into H⋯H, C⋯H/H⋯C, Cl⋯H/H⋯Cl, O⋯H/H⋯O and C⋯C contacts (McKinnon et al., 2007), also illustrated in Fig. 6. The major percentage contributions to the Hirshfeld surface are from (in descending order) H⋯H, C⋯H/H⋯C, Cl⋯H/H⋯Cl, O⋯H/H⋯O and S⋯H/H⋯S contacts along with a small, i.e. 0.6%, contribution from C⋯C contacts as summarized in Table 3. These interactions result in distinctive features in their respective delineated fingerprint plots. The short interatomic H⋯H and C⋯H/H⋯C contacts are characterized as a pair of beak-shape tips at de + di ∼ 2.1 Å and the pair of parabolic distributions of points at around de + di < 2.8 Å in their respective delineated fingerprint plots. The short interatomic C⋯H/H⋯C contacts in the crystal, Table 2, appear as a pair of thin tips at de + di ∼ 2.7 Å attached to the aforementioned parabolic distribution. The interatomic Cl⋯H/H⋯Cl contacts, making the next most significant contribution to the Hirshfeld surface, i.e. 12.8%, are at van der Waals separations. The C—H⋯O contacts, involving the carbonyl-O2 with methyl-C7 H and methine-C8 H atoms, Table 1, are evident as a pair of spikes with tips at de + di ∼ 2.3 Å. The vase-shaped distribution of points beginning at de + di ∼ 3.3 Å in the fingerprint plot delineated into C⋯C contacts results from the contacts highlighted in Fig. 5 and Table 2. The small contribution from other remaining interatomic contacts summarized in Table 3 have a negligible influence upon the molecular packing.
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5. Non-covalent interaction plots
Non-covalent interaction plots are a convenient means by which the nature of a specified intermolecular interaction may be assessed in terms of it being attractive or otherwise (Johnson et al., 2010; Contreras-García et al., 2011). If a specified interaction is attractive, the isosurface will be blue in appearance whereas a repulsive interaction will result in a red isosurface. On the other hand, a weakly attractive interaction will appear green. The isosurfaces for the interactions between the methyl-C7 and methine-C H atoms and the carbonyl-O2 atom are shown in Fig. 7a, clearly indicating their weakly attractive nature. Similarly, the interactions between the chlorobenzene-C6 and methyl-H7C atoms, Fig. 7b, and between the methyl-H7B and phenyl-H14 atoms, Fig. 7c, are weakly attractive.
6. Database survey
There are two closely related literature precedents for (I), namely the S-bound 4-methoxybenzene [(II); Caracelli et al., 2015] and 4-tolyl [(III); Zukerman-Schpector et al., 2015] derivatives. The three compounds crystallize in the same Pca21 and present similar unit-cell dimensions. An overlay diagram for (I)–(III) is shown in Fig. 8 from which it can be noted there is a high degree of concordance for (I) and (III). The molecule in (II) is coincident with (I) and (III) except for the relative disposition of the S-bound methoxybenzene ring. This difference arises as a result of a twist about the C8—S1 bond as seen in the C4—S1—C8—C9 torsion angles of 57.3 (5), 46.6 (3) and 57.9 (3)° for (I)–(III), respectively. Despite this difference, the angles between the S-bound benzene rings and the phenyl rings in (I)–(III) are relatively constant at 42.9 (2), 40.11 (16) and 44.03 (16)°, respectively.
7. Synthesis and crystallization
The 4′-chlorophenyl disulfide precursor was prepared as previously described (Ali & McDermott, 2002) through the oxidation of 4′-chlorothiophenol by bromine. A solution of 2-methoxy acetophenone (0.70 ml, 5.08 mmol, Sigma–Aldrich) in THF (15 ml), was added dropwise to a cooled (195 K) solution of diisopropylamine (0.78 ml, 5.59 mmol) and n-butyllithium (3.76 ml, 5.08 mmol) in THF (25 ml). After 30 min., a solution of 4′-chlorophenyl disulfide (1.61 g, 5.08 mmol) with hexamethylphosphoramide (HMPA) (0.90 ml, ca 5.08 mmol) dissolved in THF (15 ml) was added dropwise to the enolate solution (Zoretic & Soja, 1976). After stirring for 3 h, water (50 ml) was added at room temperature and extraction with diethyl ether was performed. The organic layer was then treated with a of ammonium chloride until neutral pH and dried over anhydrous magnesium sulfate. A brown oil was obtained after evaporation of solvent. Purification through flash with n-hexane was used in order to remove the non-polar reactant (disulfide), then with dry acetone to give a mixture of both acetophenones (product and reactant). Crystallization was performed by vapour diffusion of n-hexane into a chloroform solution held at 283 K to give pure product (0.4 g, yield = 60%). Irregular colourless crystals for X-ray diffraction of (I) were obtained by the same pathway. M.p. 358.2–358.8 K. 1H NMR (CDCl3, 500 MHz, δ ppm): 3.67 (s, 3H), 5.86 (s, 1H), 7.24–7.29 (m, 4H), 7.44–7.47 (m, 2H), 7.57–7.60 (m, 1H), 7.93–7.95 (m, 2H). 13C NMR (CDCl3, 125 MHz, δ p.p.m.): 190.20, 135.60, 135.25, 134.23, 133.55, 129.22, 128.84, 128.59, 89.37, 56.13. Microanalysis calculated for C15H13ClO2S (%): C 61.53, H 4.48. Found (%): C 61.47, H 4.55. High-resolution MS [M+, M2+] calculated: 292.0325, 294.0295; found: 292.0324, 294.0296.
8. details
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.93–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C).
details are summarized in Table 4Supporting information
CCDC reference: 1838590
https://doi.org/10.1107/S2056989018006072/hb7746sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006072/hb7746Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989018006072/hb7746Isup3.cml
Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SIR2014 (Burla et al., 2015); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: MarvinSketch (ChemAxon, 2010) and publCIF (Westrip, 2010).C15H13ClO2S | Dx = 1.380 Mg m−3 |
Mr = 292.76 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 1839 reflections |
a = 17.964 (3) Å | θ = 2.5–23.7° |
b = 8.0234 (15) Å | µ = 0.41 mm−1 |
c = 9.7761 (19) Å | T = 293 K |
V = 1409.0 (5) Å3 | Irregular, colourless |
Z = 4 | 0.42 × 0.21 × 0.12 mm |
F(000) = 608 |
Bruker APEXII CCD diffractometer | 1505 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.049 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 25.0°, θmin = 2.3° |
Tmin = 0.365, Tmax = 0.745 | h = −20→21 |
5010 measured reflections | k = −7→9 |
2081 independent reflections | l = −11→8 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.048 | w = 1/[σ2(Fo2) + (0.043P)2 + 0.3264P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.116 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.28 e Å−3 |
2081 reflections | Δρmin = −0.18 e Å−3 |
173 parameters | Absolute structure: Flack x determined using 465 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
1 restraint | Absolute structure parameter: 0.06 (9) |
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 | ||
Cl1 | 0.36121 (11) | 0.3177 (3) | 1.0687 (2) | 0.0916 (7) | |
S1 | 0.41934 (10) | 0.2492 (2) | 0.4390 (2) | 0.0646 (5) | |
O1 | 0.5511 (2) | 0.0919 (5) | 0.4909 (4) | 0.0616 (11) | |
O2 | 0.4654 (2) | −0.1253 (5) | 0.6070 (4) | 0.0685 (12) | |
C1 | 0.3786 (4) | 0.2943 (8) | 0.8946 (7) | 0.0571 (17) | |
C2 | 0.3254 (4) | 0.2193 (8) | 0.8147 (9) | 0.069 (2) | |
H2 | 0.2812 | 0.1806 | 0.8527 | 0.083* | |
C3 | 0.3396 (4) | 0.2028 (8) | 0.6744 (8) | 0.0644 (18) | |
H3 | 0.3048 | 0.1506 | 0.6186 | 0.077* | |
C4 | 0.4045 (3) | 0.2632 (7) | 0.6186 (7) | 0.0529 (15) | |
C5 | 0.4565 (4) | 0.3385 (7) | 0.7019 (7) | 0.0579 (16) | |
H5 | 0.5005 | 0.3793 | 0.6647 | 0.069* | |
C6 | 0.4432 (4) | 0.3534 (8) | 0.8404 (7) | 0.0593 (18) | |
H6 | 0.4784 | 0.4038 | 0.8967 | 0.071* | |
C7 | 0.6003 (4) | 0.1950 (9) | 0.4167 (9) | 0.081 (2) | |
H7A | 0.6078 | 0.1492 | 0.3271 | 0.121* | |
H7B | 0.6472 | 0.2011 | 0.4637 | 0.121* | |
H7C | 0.5794 | 0.3047 | 0.4090 | 0.121* | |
C8 | 0.4828 (3) | 0.0677 (6) | 0.4279 (7) | 0.0504 (14) | |
H8 | 0.4915 | 0.0421 | 0.3312 | 0.060* | |
C9 | 0.4447 (3) | −0.0804 (7) | 0.4942 (6) | 0.0493 (14) | |
C10 | 0.3836 (3) | −0.1693 (7) | 0.4225 (7) | 0.0465 (13) | |
C11 | 0.3538 (3) | −0.3095 (7) | 0.4869 (7) | 0.0577 (16) | |
H11 | 0.3719 | −0.3431 | 0.5716 | 0.069* | |
C12 | 0.2974 (3) | −0.3981 (7) | 0.4246 (9) | 0.0690 (18) | |
H12 | 0.2784 | −0.4924 | 0.4674 | 0.083* | |
C13 | 0.2691 (4) | −0.3500 (9) | 0.3017 (9) | 0.073 (2) | |
H13 | 0.2306 | −0.4097 | 0.2613 | 0.087* | |
C14 | 0.2984 (4) | −0.2114 (9) | 0.2377 (8) | 0.075 (2) | |
H14 | 0.2794 | −0.1774 | 0.1537 | 0.090* | |
C15 | 0.3559 (3) | −0.1224 (8) | 0.2978 (7) | 0.0621 (17) | |
H15 | 0.3758 | −0.0303 | 0.2531 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.1147 (15) | 0.1100 (15) | 0.0501 (11) | 0.0357 (11) | 0.0107 (12) | −0.0064 (10) |
S1 | 0.0977 (11) | 0.0519 (8) | 0.0441 (8) | 0.0100 (8) | −0.0060 (11) | 0.0053 (8) |
O1 | 0.072 (3) | 0.068 (3) | 0.045 (3) | −0.012 (2) | −0.002 (2) | 0.001 (2) |
O2 | 0.103 (3) | 0.066 (3) | 0.037 (3) | −0.010 (2) | −0.008 (3) | 0.009 (2) |
C1 | 0.074 (4) | 0.054 (4) | 0.042 (4) | 0.022 (3) | 0.005 (4) | −0.003 (3) |
C2 | 0.075 (5) | 0.061 (4) | 0.071 (5) | 0.002 (3) | 0.014 (4) | −0.002 (4) |
C3 | 0.073 (4) | 0.054 (4) | 0.066 (5) | 0.000 (3) | −0.005 (4) | −0.006 (3) |
C4 | 0.074 (4) | 0.036 (3) | 0.048 (4) | 0.009 (3) | −0.003 (4) | 0.001 (3) |
C5 | 0.068 (4) | 0.051 (4) | 0.055 (4) | 0.005 (3) | 0.001 (4) | −0.004 (3) |
C6 | 0.068 (4) | 0.058 (4) | 0.052 (4) | 0.014 (3) | −0.010 (3) | −0.015 (3) |
C7 | 0.087 (5) | 0.092 (5) | 0.063 (6) | −0.026 (4) | 0.004 (5) | −0.004 (5) |
C8 | 0.068 (3) | 0.049 (3) | 0.034 (3) | 0.001 (3) | 0.003 (3) | 0.003 (3) |
C9 | 0.075 (4) | 0.046 (3) | 0.028 (3) | 0.009 (3) | 0.009 (3) | 0.002 (3) |
C10 | 0.061 (3) | 0.044 (3) | 0.035 (3) | 0.006 (3) | 0.006 (3) | −0.002 (3) |
C11 | 0.067 (4) | 0.056 (4) | 0.050 (4) | 0.005 (3) | 0.004 (3) | 0.008 (3) |
C12 | 0.073 (4) | 0.053 (4) | 0.081 (6) | −0.007 (3) | 0.012 (5) | 0.005 (4) |
C13 | 0.073 (5) | 0.076 (5) | 0.069 (5) | −0.011 (3) | 0.002 (4) | −0.011 (4) |
C14 | 0.088 (5) | 0.092 (5) | 0.046 (5) | −0.003 (4) | −0.010 (4) | −0.006 (4) |
C15 | 0.082 (4) | 0.059 (4) | 0.046 (4) | −0.013 (3) | −0.003 (4) | 0.001 (3) |
Cl1—C1 | 1.741 (7) | C7—H7B | 0.9600 |
S1—C4 | 1.780 (7) | C7—H7C | 0.9600 |
S1—C8 | 1.853 (5) | C8—C9 | 1.517 (7) |
O1—C8 | 1.386 (6) | C8—H8 | 0.9800 |
O1—C7 | 1.412 (8) | C9—C10 | 1.485 (8) |
O2—C9 | 1.219 (7) | C10—C15 | 1.370 (9) |
C1—C6 | 1.362 (9) | C10—C11 | 1.395 (8) |
C1—C2 | 1.372 (10) | C11—C12 | 1.379 (9) |
C2—C3 | 1.401 (10) | C11—H11 | 0.9300 |
C2—H2 | 0.9300 | C12—C13 | 1.360 (11) |
C3—C4 | 1.376 (9) | C12—H12 | 0.9300 |
C3—H3 | 0.9300 | C13—C14 | 1.380 (9) |
C4—C5 | 1.378 (8) | C13—H13 | 0.9300 |
C5—C6 | 1.381 (9) | C14—C15 | 1.387 (8) |
C5—H5 | 0.9300 | C14—H14 | 0.9300 |
C6—H6 | 0.9300 | C15—H15 | 0.9300 |
C7—H7A | 0.9600 | ||
C4—S1—C8 | 101.5 (3) | O1—C8—S1 | 114.1 (4) |
C8—O1—C7 | 114.1 (5) | C9—C8—S1 | 108.2 (4) |
C6—C1—C2 | 121.6 (7) | O1—C8—H8 | 108.6 |
C6—C1—Cl1 | 119.7 (6) | C9—C8—H8 | 108.6 |
C2—C1—Cl1 | 118.6 (6) | S1—C8—H8 | 108.6 |
C1—C2—C3 | 118.2 (7) | O2—C9—C10 | 120.7 (5) |
C1—C2—H2 | 120.9 | O2—C9—C8 | 118.8 (5) |
C3—C2—H2 | 120.9 | C10—C9—C8 | 120.6 (5) |
C4—C3—C2 | 120.6 (6) | C15—C10—C11 | 118.9 (6) |
C4—C3—H3 | 119.7 | C15—C10—C9 | 123.8 (5) |
C2—C3—H3 | 119.7 | C11—C10—C9 | 117.3 (5) |
C3—C4—C5 | 119.6 (7) | C12—C11—C10 | 119.9 (7) |
C3—C4—S1 | 119.7 (5) | C12—C11—H11 | 120.0 |
C5—C4—S1 | 120.6 (5) | C10—C11—H11 | 120.0 |
C4—C5—C6 | 120.0 (6) | C13—C12—C11 | 121.2 (6) |
C4—C5—H5 | 120.0 | C13—C12—H12 | 119.4 |
C6—C5—H5 | 120.0 | C11—C12—H12 | 119.4 |
C1—C6—C5 | 119.9 (6) | C12—C13—C14 | 119.1 (7) |
C1—C6—H6 | 120.1 | C12—C13—H13 | 120.5 |
C5—C6—H6 | 120.1 | C14—C13—H13 | 120.5 |
O1—C7—H7A | 109.5 | C13—C14—C15 | 120.5 (7) |
O1—C7—H7B | 109.5 | C13—C14—H14 | 119.8 |
H7A—C7—H7B | 109.5 | C15—C14—H14 | 119.8 |
O1—C7—H7C | 109.5 | C10—C15—C14 | 120.4 (6) |
H7A—C7—H7C | 109.5 | C10—C15—H15 | 119.8 |
H7B—C7—H7C | 109.5 | C14—C15—H15 | 119.8 |
O1—C8—C9 | 108.6 (5) | ||
C6—C1—C2—C3 | 0.8 (9) | O1—C8—C9—O2 | 19.3 (7) |
Cl1—C1—C2—C3 | 179.3 (5) | S1—C8—C9—O2 | −105.1 (5) |
C1—C2—C3—C4 | −1.2 (9) | O1—C8—C9—C10 | −160.4 (5) |
C2—C3—C4—C5 | 0.9 (9) | S1—C8—C9—C10 | 75.2 (6) |
C2—C3—C4—S1 | −177.2 (5) | O2—C9—C10—C15 | 177.7 (6) |
C8—S1—C4—C3 | −101.5 (5) | C8—C9—C10—C15 | −2.5 (8) |
C8—S1—C4—C5 | 80.5 (5) | O2—C9—C10—C11 | −2.9 (8) |
C3—C4—C5—C6 | −0.2 (8) | C8—C9—C10—C11 | 176.9 (5) |
S1—C4—C5—C6 | 177.9 (5) | C15—C10—C11—C12 | 0.0 (9) |
C2—C1—C6—C5 | 0.0 (9) | C9—C10—C11—C12 | −179.4 (5) |
Cl1—C1—C6—C5 | −178.5 (5) | C10—C11—C12—C13 | −1.0 (9) |
C4—C5—C6—C1 | −0.3 (9) | C11—C12—C13—C14 | 1.0 (10) |
C7—O1—C8—C9 | 163.9 (5) | C12—C13—C14—C15 | 0.1 (10) |
C7—O1—C8—S1 | −75.3 (6) | C11—C10—C15—C14 | 1.0 (10) |
C4—S1—C8—O1 | −63.7 (4) | C9—C10—C15—C14 | −179.6 (5) |
C4—S1—C8—C9 | 57.3 (5) | C13—C14—C15—C10 | −1.1 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7A···O2i | 0.96 | 2.53 | 3.297 (9) | 137 |
C8—H8···O2i | 0.98 | 2.42 | 3.305 (8) | 150 |
Symmetry code: (i) −x+1, −y, z−1/2. |
Contact | Distance | Symmetry operation |
H7B···H14 | 2.10 | 1 - x, - y, 1/2 + z |
H7B···C14 | 2.76 | 1 - x, - y, 1/2 + z |
H7C···C6 | 2.73 | 1 - x, 1 - y, 1/2 + z |
C6···C9 | 3.33 | 1 - x, - y, 1/2 + z |
Contact | Percentage contribution |
H···H | 39.3 |
C···H/H···C | 23.2 |
Cl···H/H···Cl | 12.8 |
O···H/H···O | 11.0 |
S···H/H···S | 4.4 |
Cl···S/S···Cl | 2.1 |
Cl···O/O···Cl | 2.1 |
C···O/O···C | 1.5 |
C···Cl/Cl···C | 1.5 |
C···S/S···C | 1.2 |
C···C | 0.6 |
Footnotes
‡Additional correspondence author, e-mail: edwardt@sunway.edu.my.
Funding information
The Brazilian agency the São Paulo Research Foundation (FAPESP) is thanked for financial support of this research, the Coordination for the Improvement of Higher Education Personnel for a scholarship (CAPES 3300201191P0 to HJT) and the National Council for Scientific and Technological Development for fellowships (CNPq: 308480/2016–3 to IC; 303207/2017–5 to JZ-S; 301180/2013–0 to PRO). Funding for this research was provided by the Conselho Nacional de Desenvolvimento Científico e Tecnológico (awards No. 457255/2014–5 and 301180/2013–0).
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