research communications
[(Z)-N-(3-Fluorophenyl)-O-methylthiocarbamato-κS](triphenylphosphane-κP)gold(I): Hirshfeld surface analysis and computational study
aResearch 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 title phosphanegold(I) thiolate, C26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiolate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P—Au—S = 176.10 (3)°]. The thiolate ligand is orientated so that the methoxy-O atom is directed towards the Au atom, forming an Au⋯O close contact of 2.986 (2) Å. In the crystal, a variety of intermolecular contacts are discerned with fluorobenzene-C—H⋯O(methoxy) and phenyl-C—H⋯F interactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C—H⋯S(thiolate) and phenyl-C—H⋯π(fluorobenzene, phenyl) interactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C⋯H/H⋯C but this is less than the H⋯H contacts, at 44.9%. Other significant contributions to the surface come from H⋯F/F⋯H [8.1%], H⋯S/S⋯H [6.9%] and H⋯O/O⋯H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C—H⋯π(fluorobenzene) and fluorobenzene-C—H⋯C(imine) interactions (−37.2 kcal mol−1), and from the fluorobenzene-C—H⋯F and phenyl-C—H⋯O interactions (−34.9 kcal mol−1), the latter leading to the dimeric aggregate.
Keywords: crystal structure; gold; thiocarbamate; Hirshfeld surface analysis; computational chemistry.
CCDC reference: 2015568
1. Chemical context
In common with many other phosphanegold(I) thiolates (Yeo et al., 2018), molecules of the general formula R3PAu[SC(OR′)=NAr] have proven to exhibit anti-cancer potential (Ooi et al., 2017). Complimenting this activity is anti-bacterial potential against Gram-positive bacteria based on in vitro assays and time-kill profiles (Yeo et al., 2013) but not anti-amoebic effects, i.e. against Acanthamoeba castellanii (Siddiqui et al., 2017). In keeping with suggestions that the incorporation of fluorine atoms into molecules can enhance their pharmaceutical utility (Müller et al., 2007; Meanwell, 2018), it was thought of interest to synthesize fluoro analogues of R3PAu[SC(OR′)=NAr].
Herein, the compound with R = Ph, R′ = Me and Ar = 3-fluorobenzene, (I), is described: synthesis, spectroscopic characterization, determination, analysis of the calculated Hirshfeld surfaces and interaction energies.
2. Structural commentary
The molecular structure of (I), Fig. 1, features a linearly coordinated AuI centre defined by phosphane-P1 [2.2494 (8) Å] and thiolate-S1 [2.3007 (8) Å] atoms. The deviation of the P1—Au—S1 angle of 176.10 (3)° from the ideal 180° is related to the close approach of the O1 atom, i.e. Au⋯O1 = 2.986 (2) Å, as the O1 atom is directed towards the gold atom. The elongation of the C1—S1 bond to 1.762 (3) Å and the shortening of the C1—N1 bond to 1.262 (4) Å with respect to the comparable bonds in the neutral thiocarbamide molecules, i.e. S=C(OMe)N(H)Ar (Ho et al., 2005), i.e. ca 1.66 and 1.34 Å, respectively, are consistent with the formation of thiolate and imine bonds, respectively.
The overall molecular conformation of (I) is as usually found in molecules formulated as R3PAu[SC(OR′)=NAr]. However, a less common form is known whereby the N-bound aryl ring is orientated towards the gold atom rather than the alkoxy-oxygen atom (Kuan et al., 2008). So, rather than an intramolecular Au⋯O contact, an intramolecular Au⋯π contact is formed. The observation of both forms in Ph3PAu[SC(OEt)=NPh], i.e. with Au⋯O (Hall & Tiekink, 1993) or Au⋯π (Yeo et al., 2016), suggests the energy difference between the conformations is relatively small. In related binuclear species, DFT calculations suggest that a Au⋯π interaction is about 6 kcal mol−1 more stable than a Au⋯O contact (Yeo et al., 2015).
3. Supramolecular features
Several directional intermolecular points of contact between molecules are noted in the extended structure of (I); see Table 1 for a listing of the geometric parameters characterizing these. Centrosymmetrically related molecules are connected via pairwise fluorobenzene-C—H⋯O1 and phenyl-C—H⋯F1 contacts Fig. 2(a). The dimeric aggregates are connected into a three-dimensional architecture by phenyl-C—H⋯S1 interactions, with the phenyl-H atom involved in the latter interaction, i.e. H13, also participating in a C—H⋯π(fluorobenzene) interaction and so may be considered bifurcated. The two remaining contacts are of the type phenyl-C—H⋯π(fluorobenzene, phenyl) so the fluorobenzene ring accepts two contacts, one to either side of the ring. A view of the unit-cell contents is shown in Fig. 2(b).
4. Hirshfeld surface analysis
In order to understand further the interactions operating in the molecular packing of (I), the Hirshfeld surfaces mapped over normalized contact distance dnorm (McKinnon et al., 2004) and two-dimensional fingerprint plots (Spackman & McKinnon, 2002) for (I) were generated using Crystal Explorer 17 (Turner et al., 2017) following literature procedures (Tan et al., 2019). The bright-red spots near the fluorobenzene-H3 and methoxy-O1 atoms on the Hirshfeld surface mapped over dnorm in Fig. 3, correspond to the fluorobenzene-C3—H3⋯O1 contacts. These contacts are associated with phenyl-C36—H36⋯F1 contacts, which appear as faint red spots in Fig. 3, being ∼0.24 Å shorter than the respective sums of their van der Waals radii, Table 2. The phenyl-C13—H13⋯S1 interaction is observed as faint red spots on the dnorm surface in Fig. 4(a), where the cooperative phenyl-C13—H13⋯π(C2–C7) interaction is shown as a distinctive orange `pothole' on the shape-index-mapped Hirshfeld surface in Fig. 4(b). Although the phenyl-C22—H22⋯π(C2–C7) interaction was not manifested on the Hirshfeld surface mapped over dnorm, this interaction shows up as blue `bump' and orange `pothole' near the H22 atom and Cg1(C2–C7) centroid, respectively, in Fig. 5(a). Simultaneously, a fluorobenzene-C7—H7⋯C1(imine) contact, Table 2, is observed through faint red spots near atoms C1 and H7 on the dnorm surface in Fig. 5(b). The presence of the phenyl-C24—H24⋯π(C11–C16) contact is evidenced through faint red spots in Fig. 6(a) and the orange `pothole' in Fig. 6(b) on the dnorm and shape-index mapped Hirshfeld surface, respectively. In addition to the C—H⋯π contacts listed in Table 1, weak phenyl-C32—H32⋯π(C11–C16) and phenyl-C15—H15⋯π(C21–C26) contacts, Table 2, are observed as an orange `hollow' on the Hirshfeld surface mapped over shape-index property in Fig. 7.
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The overall two-dimensional fingerprint plot of (I) is shown in Fig. 8(a), and those delineated into H⋯H, H⋯C/C⋯H, H⋯F/F⋯H, H⋯S/S⋯H and H⋯O/O⋯H contacts are shown in Fig. 8(b)–(f), respectively. The percentage contributions for the different interatomic contacts to the Hirshfeld surface are summarized in Table 3. The H⋯H contacts are the most prominent of all contacts and contribute 44.9% to the entire surface. The delineated fingerprint plot in Fig. 8(b) features a beak-shaped peak tipped at de + di ∼2.3 Å. This tip corresponds to a methyl-H8C⋯H33(phenyl) contact and has a distance 0.1 Å shorter than the sum of their van de Waals radii, Table 2. Consistent with the many C—H⋯π interactions evident in the molecular packing, H⋯C/C⋯H contacts contribute 30.8% to the total surface contacts. The H⋯C/C⋯H contacts shows a distinctive feature in the fingerprint plot of Fig. 8(c) with two symmetric spikes at de + di ∼2.4 Å. The tips of pseudo-mirrored sharp spikes at de + di ∼2.4 Å represent the shortest H⋯F/F⋯H contacts (8.1%), Fig. 8(d), and correspond to the phenyl-C36—H36⋯F1 contact in Table 1. While the C—H⋯O1 and C—H⋯S1 interactions are reflected through two sharp-symmetric wings at de + di ∼2.7 and ∼2.5 Å, respectively, Fig. 8(e) and (f), these types of contacts only contribute 6.9 and 3.2%, respectively, to the total interatomic contacts. The accumulated contribution of the remaining six different interatomic contacts is around 6.0% and these do not have a significant influence on the molecular packing.
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5. Computational chemistry
The interaction energies in the crystal of (I) were calculated based on the procedures reported previously (Yusof et al., 2017). Briefly, the corresponding pairwise molecules were subjected to the calculation via the long-range corrected ωB97XD functional combining the D2 version of Grimme's dispersion model (Chai & Head-Gordon, 2008), with Pople's 6-31+G(d,p) basis set (Petersson et al., 1988; Petersson & Al-Laham, 1991) comprising the polarization and diffuse functions being employed for C, H, N, O, F, P and S while the effective core potential LANL2DZ (Hay & Wadt, 1985) was applied for Au. Counterpoise methods (Boys & Bernardi, 1970; Simon et al., 1996) were applied to correct for basis set superposition error (BSSE) in the obtained energies. The BSSE corrected interaction energies (E) are listed in Table 4.
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The greatest stabilization energy arises from the phenyl-C22—H22⋯π(C2–C7) and fluorobenzene-C7—H7⋯C1(imine) interactions (−37.2 kcal mol−1). This is followed by the phenyl-C36—H36⋯F1 and phenyl-C3—H3⋯O1 interactions (−34.9 kcal mol−1), which lead to the dimeric aggregate in Fig. 2(a). The other directional contacts outlined in Supramolecular features contribute minor stabilization energies to the molecular packing (−8.9 + −5.46 kcal mol−1) while the pairwise weak phenyl-C15—H15⋯π(C21–C26) and phenyl-C32—H32⋯π(C11–C16) interactions, which were identified through the Hirshfeld surface analysis, have a greater stabilization energy (−15.6 kcal mol−1).
6. Database survey
There are several literature precedents for (I), i.e. molecules of the general formula Ph3PAu[SC(OMe)=NC6H4Y-3]. Selected geometric parameters for these are given in Table 5. To a first approximation, the molecules adopt similar conformations and each features a short intramolecular Au⋯O interaction. This being stated, the two overlay diagrams in Fig. 9 indicate differences in the relative dispositions of the terminal arene rings, as reflected in the differences in the dihedral angles between the planes through the CNOS and C6 residues, which vary by up to nearly 15°. Finally, there is an isostructural relationship between (I) and the monoclinic form of the Y = Cl compound (Yeo et al., 2016).
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7. Synthesis and crystallization
All chemicals and solvents were used as sourced without further purification. Melting points were determined on a Biobase automatic melting point apparatus MP450 (Jinan, Shandong Province, China). 1H and 13C{1H} NMR spectra were recorded in CDCl3 solution on a Bruker Ascend 400 MHz NMR spectrometer (Billerica, MA, USA) with chemical shifts relative to tetramethylsilane; the 31P{1H} NMR spectrum was recorded in CDCl3 solution on the same instrument but with the recorded relative to 85% aqueous H3PO4 as the external reference. IR spectra were measured on a Bruker Vertex 70v FTIR spectrophotometer (Billerica, MA, USA) from 4000 to 400 cm−1. Elemental analyses were performed on a Leco TruSpec MicroCHN Elemental Analyser (St Joseph, MI, USA).
The thiol precursor, LH, was prepared from the reaction of 3-fluorophenyl isothiocyanate (Sigma–Aldrich, St. Louis, MO, USA; 2.50 mmol, 0.38 g) and MeOH (Merck, Kenilworth, NJ, USA; 100 ml) in the presence of NaOH (Merck, Kenilworth, NJ, USA; 2.50 mmol, 0.10 g) followed by the addition of excess 1 M HCl. The resulting mixture was extracted using chloroform, yielding colourless crystals after 3 weeks standing. Yield: 0.421 g (91%), m.p. 334.0–334.5 K. Analysis calculated for C8H8FNOS: C, 51.88; H, 4.35; N, 7.56%. Found: C, 51.49; H, 4.46; N, 7.42%. IR (cm−1): 3241 (br) ν(N—H), 1438 (s) ν(C—N), 1150 (s) ν(C—O), 1048 (s) ν (C=S). 1H NMR (400 MHz, CDCl3, 298 K): δ 8.88 (s, br, 1H, NH), 7.29–6.87 (m, 4H, aryl-H), 4.15 (s, 3H, OCH3) ppm. 13C{1H} NMR (400 MHz, CDCl3, 298 K): δ 189.4 (Cq), 162.8 (d, aryl-C3, 1JCF = 245.80 Hz), 138.5 (aryl-C1), 130.2 (d, aryl-C5, 3JCF = 9.25 Hz), 116.8 (aryl-C6), 112.2 (d, aryl-C4, 2JCF = 21.25 Hz), 109.1 (aryl-C2), 58.9 (OCH3) ppm.
The Ph3PAuCl precursor was prepared from the reduction of KAuCl4 using sodium sulfite, followed by the addition of a stoichiometric amount of triphenylphosphane. The precipitate was used as isolated.
NaOH (Merck, Kenilworth, NJ, USA; 0.50 mmol, 0.020 g) in water (5 ml) was added to a suspension of Ph3PAuCl (0.50 mmol, 0.247 g) in acetonitrile (20 ml), LH (0.50 mmol, 0.093 g) in acetonitrile (20 ml) was added and the solution was stirred for 3 h. The solution was left for slow evaporation at room temperature, yielding colourless crystals after 2 weeks. Yield: 0.273 g (85%), m.p. 408.0–408.5 K. Analysis calculated for C26H22AuFNOPS: C, 48.53; H, 3.45; N, 2.18%. Found: C, 48.73; H, 3.56; N, 1.97%. IR (cm−1): 1575 (s) ν(C=N), 1122 (s) ν(C—O), 1100 (s) ν(C—S). 1H NMR (400 MHz, CDCl3, 298 K): δ 7.55–7.43 (m, br, 15H, Ph3P), 6.95–6.89 (m, br, 1H, aryl-H5), 6.63–6.61 (m, br, 2H, aryl-H2,6), 6.39–6.36 (m, br, 1H, aryl-H4), 3.90 (s, 3H, OCH3) ppm. 13C{1H} NMR (400 MHz, CDCl3, 298 K): δ 165.4 (Cq), 163.2 (d, aryl-C3, 1JCF = 244.45 Hz), 152.8 (d, aryl-C1, 3JCF = 9.93 Hz), 134.3 (d, 2-PC6H5, 3JCP = 13.86 Hz), 131.7 (d, 4-PC6H5, 4JCP = 2.30 Hz), 129.7 (d, aryl-C5, 3JCF = 9.62 Hz), 129.3 (d, 3-PC6H5, 1JCP = 57.41 Hz), 129.1 (d, 2-PC6H5, 2JCP = 11.64 Hz), 117.8 (d, aryl-C6, 4JCF = 2.57 Hz), 109.3 (d, aryl-C2, 2JCF = 21.95 Hz), 109.1 (d, aryl-C4, 2JCF = 21.27 Hz), 55.5 (OCH3) ppm. 31P{1H} NMR (400 MHz, CDCl3, 298 K): δ 38.8 ppm.
8. Refinement
Crystal data, data collection and structure . The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2–1.5Ueq(C). The maximum and minimum electron density peaks of 1.17 and 1.22 e Å−3, respectively, are located 0.97 and 0.69 Å, respectively, from the Au atom.
details are summarized in Table 6
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Supporting information
CCDC reference: 2015568
https://doi.org/10.1107/S2056989020009469/hb7932sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020009469/hb7932Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2013); cell
CrysAlis PRO (Agilent, 2013); data reduction: CrysAlis PRO (Agilent, 2013); program(s) used to solve structure: SHELXS97 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Au(C8H7FNOS)(C18H15P)] | F(000) = 1248 |
Mr = 643.44 | Dx = 1.793 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9311 (3) Å | Cell parameters from 12325 reflections |
b = 17.2458 (6) Å | θ = 3.9–29.4° |
c = 15.6857 (5) Å | µ = 6.35 mm−1 |
β = 99.361 (3)° | T = 100 K |
V = 2383.80 (14) Å3 | Block, colourless |
Z = 4 | 0.30 × 0.30 × 0.30 mm |
Agilent Technologies SuperNova Dual diffractometer with Atlas detector | 5429 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 5017 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.045 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
ω scan | h = −11→11 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013) | k = −19→22 |
Tmin = 0.252, Tmax = 1.000 | l = −20→20 |
25800 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.023 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.019P)2 + 0.9042P] where P = (Fo2 + 2Fc2)/3 |
5429 reflections | (Δ/σ)max = 0.002 |
290 parameters | Δρmax = 1.17 e Å−3 |
0 restraints | Δρmin = −1.22 e Å−3 |
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 | ||
Au | 0.19089 (2) | 0.29511 (2) | 0.43142 (2) | 0.01422 (5) | |
S1 | 0.25242 (9) | 0.42032 (5) | 0.40015 (4) | 0.02170 (17) | |
P1 | 0.11477 (8) | 0.17558 (4) | 0.46267 (4) | 0.01214 (15) | |
F1 | 0.3783 (2) | 0.74491 (12) | 0.34520 (12) | 0.0342 (5) | |
O1 | 0.3182 (2) | 0.40907 (13) | 0.56743 (11) | 0.0174 (4) | |
N1 | 0.2716 (3) | 0.53368 (14) | 0.52214 (14) | 0.0166 (5) | |
C1 | 0.2802 (3) | 0.46274 (18) | 0.50373 (17) | 0.0166 (6) | |
C2 | 0.2227 (3) | 0.58863 (18) | 0.45714 (17) | 0.0168 (6) | |
C3 | 0.3275 (3) | 0.63954 (18) | 0.43078 (18) | 0.0196 (6) | |
H3 | 0.432629 | 0.635322 | 0.453168 | 0.023* | |
C4 | 0.2749 (4) | 0.69595 (18) | 0.3716 (2) | 0.0220 (7) | |
C5 | 0.1236 (4) | 0.70522 (18) | 0.3365 (2) | 0.0224 (7) | |
H5 | 0.091705 | 0.744606 | 0.295236 | 0.027* | |
C6 | 0.0213 (3) | 0.65520 (19) | 0.36383 (18) | 0.0214 (7) | |
H6 | −0.083664 | 0.660487 | 0.341475 | 0.026* | |
C7 | 0.0685 (3) | 0.59706 (18) | 0.42351 (18) | 0.0200 (6) | |
H7 | −0.003907 | 0.562999 | 0.441510 | 0.024* | |
C8 | 0.3549 (4) | 0.4400 (2) | 0.65366 (18) | 0.0259 (7) | |
H8A | 0.382956 | 0.397437 | 0.694599 | 0.039* | |
H8B | 0.266609 | 0.467333 | 0.668620 | 0.039* | |
H8C | 0.440246 | 0.476108 | 0.656412 | 0.039* | |
C11 | 0.2043 (3) | 0.09645 (17) | 0.41333 (16) | 0.0137 (6) | |
C12 | 0.2005 (3) | 0.09928 (18) | 0.32403 (16) | 0.0157 (6) | |
H12 | 0.154329 | 0.141957 | 0.291578 | 0.019* | |
C13 | 0.2641 (3) | 0.03972 (18) | 0.28306 (18) | 0.0186 (6) | |
H13 | 0.261179 | 0.041530 | 0.222276 | 0.022* | |
C14 | 0.3322 (3) | −0.02258 (18) | 0.32988 (18) | 0.0197 (6) | |
H14 | 0.375062 | −0.063543 | 0.301276 | 0.024* | |
C15 | 0.3376 (3) | −0.02491 (18) | 0.41910 (18) | 0.0198 (6) | |
H15 | 0.384366 | −0.067488 | 0.451488 | 0.024* | |
C16 | 0.2747 (3) | 0.03502 (18) | 0.46069 (17) | 0.0165 (6) | |
H16 | 0.279928 | 0.033867 | 0.521660 | 0.020* | |
C21 | −0.0875 (3) | 0.16265 (17) | 0.42616 (16) | 0.0139 (6) | |
C22 | −0.1844 (3) | 0.22366 (19) | 0.43861 (18) | 0.0190 (6) | |
H22 | −0.144129 | 0.270054 | 0.465862 | 0.023* | |
C23 | −0.3395 (4) | 0.2166 (2) | 0.4112 (2) | 0.0233 (7) | |
H23 | −0.405616 | 0.257836 | 0.420261 | 0.028* | |
C24 | −0.3976 (3) | 0.1491 (2) | 0.37058 (18) | 0.0220 (7) | |
H24 | −0.503754 | 0.144248 | 0.351765 | 0.026* | |
C25 | −0.3024 (3) | 0.08884 (19) | 0.35728 (17) | 0.0197 (6) | |
H25 | −0.343172 | 0.043087 | 0.328736 | 0.024* | |
C26 | −0.1474 (3) | 0.09489 (18) | 0.38545 (16) | 0.0161 (6) | |
H26 | −0.082202 | 0.053035 | 0.377065 | 0.019* | |
C31 | 0.1488 (3) | 0.15679 (17) | 0.57834 (16) | 0.0140 (6) | |
C32 | 0.0449 (3) | 0.11807 (17) | 0.61907 (17) | 0.0177 (6) | |
H32 | −0.047892 | 0.100392 | 0.586516 | 0.021* | |
C33 | 0.0759 (3) | 0.10496 (18) | 0.70764 (17) | 0.0206 (6) | |
H33 | 0.004161 | 0.078454 | 0.735568 | 0.025* | |
C34 | 0.2111 (4) | 0.13046 (19) | 0.75517 (18) | 0.0255 (7) | |
H34 | 0.232732 | 0.121070 | 0.815605 | 0.031* | |
C35 | 0.3144 (4) | 0.1695 (2) | 0.71456 (19) | 0.0274 (8) | |
H35 | 0.407258 | 0.186851 | 0.747336 | 0.033* | |
C36 | 0.2843 (4) | 0.1838 (2) | 0.62661 (19) | 0.0232 (7) | |
H36 | 0.355046 | 0.211765 | 0.599282 | 0.028* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au | 0.01968 (7) | 0.01105 (8) | 0.01111 (7) | −0.00252 (4) | 0.00000 (4) | −0.00008 (4) |
S1 | 0.0393 (5) | 0.0135 (4) | 0.0121 (3) | −0.0044 (3) | 0.0039 (3) | −0.0002 (3) |
P1 | 0.0144 (3) | 0.0121 (4) | 0.0093 (3) | −0.0020 (3) | 0.0002 (3) | −0.0002 (3) |
F1 | 0.0338 (11) | 0.0293 (12) | 0.0403 (11) | −0.0116 (9) | 0.0089 (9) | 0.0050 (9) |
O1 | 0.0231 (11) | 0.0158 (12) | 0.0122 (10) | 0.0007 (8) | −0.0002 (8) | −0.0017 (8) |
N1 | 0.0174 (12) | 0.0141 (14) | 0.0176 (12) | 0.0003 (10) | 0.0005 (9) | −0.0050 (10) |
C1 | 0.0123 (13) | 0.0215 (18) | 0.0161 (14) | −0.0016 (12) | 0.0024 (11) | −0.0005 (12) |
C2 | 0.0187 (14) | 0.0165 (17) | 0.0154 (13) | 0.0013 (12) | 0.0029 (11) | −0.0048 (12) |
C3 | 0.0174 (15) | 0.0193 (18) | 0.0208 (15) | −0.0017 (12) | −0.0001 (12) | −0.0085 (13) |
C4 | 0.0259 (17) | 0.0181 (18) | 0.0239 (16) | −0.0059 (13) | 0.0097 (13) | −0.0038 (13) |
C5 | 0.0287 (18) | 0.0176 (18) | 0.0201 (16) | 0.0058 (13) | 0.0018 (13) | −0.0018 (12) |
C6 | 0.0168 (15) | 0.0229 (19) | 0.0231 (15) | 0.0057 (13) | −0.0009 (12) | −0.0043 (13) |
C7 | 0.0159 (15) | 0.0204 (18) | 0.0238 (15) | −0.0006 (12) | 0.0039 (12) | −0.0021 (13) |
C8 | 0.0304 (18) | 0.032 (2) | 0.0130 (14) | 0.0037 (15) | −0.0039 (12) | −0.0030 (13) |
C11 | 0.0150 (14) | 0.0132 (16) | 0.0121 (12) | −0.0042 (11) | −0.0002 (10) | −0.0028 (11) |
C12 | 0.0176 (14) | 0.0169 (17) | 0.0119 (13) | −0.0014 (12) | 0.0000 (10) | −0.0010 (11) |
C13 | 0.0193 (15) | 0.0225 (18) | 0.0137 (13) | −0.0038 (12) | 0.0022 (11) | −0.0046 (12) |
C14 | 0.0171 (15) | 0.0193 (18) | 0.0233 (15) | −0.0007 (12) | 0.0050 (12) | −0.0091 (13) |
C15 | 0.0202 (15) | 0.0161 (17) | 0.0219 (15) | 0.0021 (12) | −0.0002 (12) | 0.0015 (12) |
C16 | 0.0182 (14) | 0.0179 (17) | 0.0135 (13) | −0.0018 (12) | 0.0026 (11) | −0.0013 (12) |
C21 | 0.0155 (14) | 0.0192 (17) | 0.0068 (12) | −0.0026 (11) | 0.0013 (10) | 0.0020 (11) |
C22 | 0.0192 (15) | 0.0182 (17) | 0.0186 (15) | 0.0017 (12) | −0.0002 (12) | −0.0039 (12) |
C23 | 0.0192 (15) | 0.027 (2) | 0.0227 (15) | 0.0059 (13) | 0.0008 (12) | −0.0003 (14) |
C24 | 0.0157 (15) | 0.034 (2) | 0.0151 (14) | −0.0024 (13) | −0.0010 (11) | 0.0014 (13) |
C25 | 0.0227 (16) | 0.0212 (18) | 0.0141 (14) | −0.0094 (13) | −0.0007 (11) | −0.0019 (12) |
C26 | 0.0174 (14) | 0.0169 (17) | 0.0135 (13) | −0.0018 (12) | 0.0007 (11) | 0.0000 (12) |
C31 | 0.0186 (14) | 0.0114 (16) | 0.0111 (13) | 0.0008 (11) | −0.0006 (10) | −0.0028 (11) |
C32 | 0.0202 (15) | 0.0146 (16) | 0.0175 (14) | 0.0008 (12) | 0.0006 (11) | −0.0005 (12) |
C33 | 0.0312 (17) | 0.0159 (17) | 0.0153 (14) | −0.0003 (13) | 0.0051 (12) | 0.0028 (12) |
C34 | 0.042 (2) | 0.0215 (19) | 0.0117 (14) | 0.0042 (15) | −0.0012 (13) | 0.0003 (13) |
C35 | 0.0310 (18) | 0.031 (2) | 0.0163 (15) | −0.0063 (15) | −0.0088 (13) | −0.0016 (14) |
C36 | 0.0239 (16) | 0.0272 (19) | 0.0181 (15) | −0.0089 (14) | 0.0017 (12) | −0.0048 (14) |
Au—P1 | 2.2494 (8) | C13—H13 | 0.9500 |
Au—S1 | 2.3007 (8) | C14—C15 | 1.393 (4) |
S1—C1 | 1.762 (3) | C14—H14 | 0.9500 |
P1—C11 | 1.817 (3) | C15—C16 | 1.389 (4) |
P1—C21 | 1.818 (3) | C15—H15 | 0.9500 |
P1—C31 | 1.819 (3) | C16—H16 | 0.9500 |
F1—C4 | 1.365 (3) | C21—C26 | 1.396 (4) |
O1—C1 | 1.364 (3) | C21—C22 | 1.396 (4) |
O1—C8 | 1.441 (3) | C22—C23 | 1.387 (4) |
N1—C1 | 1.262 (4) | C22—H22 | 0.9500 |
N1—C2 | 1.408 (4) | C23—C24 | 1.387 (5) |
C2—C3 | 1.394 (4) | C23—H23 | 0.9500 |
C2—C7 | 1.400 (4) | C24—C25 | 1.379 (4) |
C3—C4 | 1.374 (4) | C24—H24 | 0.9500 |
C3—H3 | 0.9500 | C25—C26 | 1.387 (4) |
C4—C5 | 1.382 (4) | C25—H25 | 0.9500 |
C5—C6 | 1.375 (4) | C26—H26 | 0.9500 |
C5—H5 | 0.9500 | C31—C32 | 1.382 (4) |
C6—C7 | 1.390 (4) | C31—C36 | 1.399 (4) |
C6—H6 | 0.9500 | C32—C33 | 1.390 (4) |
C7—H7 | 0.9500 | C32—H32 | 0.9500 |
C8—H8A | 0.9800 | C33—C34 | 1.384 (4) |
C8—H8B | 0.9800 | C33—H33 | 0.9500 |
C8—H8C | 0.9800 | C34—C35 | 1.379 (5) |
C11—C16 | 1.385 (4) | C34—H34 | 0.9500 |
C11—C12 | 1.397 (4) | C35—C36 | 1.384 (4) |
C12—C13 | 1.382 (4) | C35—H35 | 0.9500 |
C12—H12 | 0.9500 | C36—H36 | 0.9500 |
C13—C14 | 1.385 (4) | ||
P1—Au—S1 | 176.10 (3) | C13—C14—C15 | 119.7 (3) |
C1—S1—Au | 101.30 (10) | C13—C14—H14 | 120.1 |
C11—P1—C21 | 104.91 (13) | C15—C14—H14 | 120.1 |
C11—P1—C31 | 106.09 (13) | C16—C15—C14 | 120.0 (3) |
C21—P1—C31 | 106.78 (12) | C16—C15—H15 | 120.0 |
C11—P1—Au | 115.21 (9) | C14—C15—H15 | 120.0 |
C21—P1—Au | 111.34 (10) | C11—C16—C15 | 120.0 (2) |
C31—P1—Au | 111.91 (10) | C11—C16—H16 | 120.0 |
C1—O1—C8 | 115.4 (2) | C15—C16—H16 | 120.0 |
C1—N1—C2 | 120.6 (2) | C26—C21—C22 | 119.7 (3) |
N1—C1—O1 | 120.5 (2) | C26—C21—P1 | 122.3 (2) |
N1—C1—S1 | 127.5 (2) | C22—C21—P1 | 118.1 (2) |
O1—C1—S1 | 112.0 (2) | C23—C22—C21 | 120.1 (3) |
C3—C2—C7 | 119.3 (3) | C23—C22—H22 | 120.0 |
C3—C2—N1 | 119.6 (3) | C21—C22—H22 | 120.0 |
C7—C2—N1 | 120.8 (3) | C22—C23—C24 | 119.7 (3) |
C4—C3—C2 | 118.3 (3) | C22—C23—H23 | 120.1 |
C4—C3—H3 | 120.9 | C24—C23—H23 | 120.1 |
C2—C3—H3 | 120.9 | C25—C24—C23 | 120.5 (3) |
F1—C4—C3 | 118.0 (3) | C25—C24—H24 | 119.7 |
F1—C4—C5 | 118.3 (3) | C23—C24—H24 | 119.7 |
C3—C4—C5 | 123.7 (3) | C24—C25—C26 | 120.2 (3) |
C6—C5—C4 | 117.4 (3) | C24—C25—H25 | 119.9 |
C6—C5—H5 | 121.3 | C26—C25—H25 | 119.9 |
C4—C5—H5 | 121.3 | C25—C26—C21 | 119.8 (3) |
C5—C6—C7 | 121.2 (3) | C25—C26—H26 | 120.1 |
C5—C6—H6 | 119.4 | C21—C26—H26 | 120.1 |
C7—C6—H6 | 119.4 | C32—C31—C36 | 119.9 (2) |
C6—C7—C2 | 120.1 (3) | C32—C31—P1 | 122.1 (2) |
C6—C7—H7 | 120.0 | C36—C31—P1 | 118.0 (2) |
C2—C7—H7 | 120.0 | C31—C32—C33 | 120.1 (3) |
O1—C8—H8A | 109.5 | C31—C32—H32 | 120.0 |
O1—C8—H8B | 109.5 | C33—C32—H32 | 120.0 |
H8A—C8—H8B | 109.5 | C34—C33—C32 | 120.1 (3) |
O1—C8—H8C | 109.5 | C34—C33—H33 | 120.0 |
H8A—C8—H8C | 109.5 | C32—C33—H33 | 120.0 |
H8B—C8—H8C | 109.5 | C35—C34—C33 | 119.8 (3) |
C16—C11—C12 | 120.0 (3) | C35—C34—H34 | 120.1 |
C16—C11—P1 | 122.6 (2) | C33—C34—H34 | 120.1 |
C12—C11—P1 | 117.4 (2) | C34—C35—C36 | 120.8 (3) |
C13—C12—C11 | 119.7 (3) | C34—C35—H35 | 119.6 |
C13—C12—H12 | 120.1 | C36—C35—H35 | 119.6 |
C11—C12—H12 | 120.1 | C35—C36—C31 | 119.4 (3) |
C12—C13—C14 | 120.6 (3) | C35—C36—H36 | 120.3 |
C12—C13—H13 | 119.7 | C31—C36—H36 | 120.3 |
C14—C13—H13 | 119.7 | ||
C2—N1—C1—O1 | −175.8 (2) | P1—C11—C16—C15 | 178.3 (2) |
C2—N1—C1—S1 | 5.8 (4) | C14—C15—C16—C11 | 1.1 (4) |
C8—O1—C1—N1 | −3.5 (4) | C11—P1—C21—C26 | 12.2 (2) |
C8—O1—C1—S1 | 175.15 (19) | C31—P1—C21—C26 | −100.1 (2) |
Au—S1—C1—N1 | −157.0 (2) | Au—P1—C21—C26 | 137.4 (2) |
Au—S1—C1—O1 | 24.52 (19) | C11—P1—C21—C22 | −166.8 (2) |
C1—N1—C2—C3 | −107.2 (3) | C31—P1—C21—C22 | 80.9 (2) |
C1—N1—C2—C7 | 78.0 (4) | Au—P1—C21—C22 | −41.6 (2) |
C7—C2—C3—C4 | −0.7 (4) | C26—C21—C22—C23 | 0.5 (4) |
N1—C2—C3—C4 | −175.6 (3) | P1—C21—C22—C23 | 179.5 (2) |
C2—C3—C4—F1 | −179.1 (2) | C21—C22—C23—C24 | −0.7 (5) |
C2—C3—C4—C5 | 0.0 (4) | C22—C23—C24—C25 | 0.1 (5) |
F1—C4—C5—C6 | 179.8 (3) | C23—C24—C25—C26 | 0.8 (4) |
C3—C4—C5—C6 | 0.7 (5) | C24—C25—C26—C21 | −1.0 (4) |
C4—C5—C6—C7 | −0.8 (4) | C22—C21—C26—C25 | 0.4 (4) |
C5—C6—C7—C2 | 0.1 (4) | P1—C21—C26—C25 | −178.6 (2) |
C3—C2—C7—C6 | 0.6 (4) | C11—P1—C31—C32 | −94.4 (3) |
N1—C2—C7—C6 | 175.5 (3) | C21—P1—C31—C32 | 17.1 (3) |
C21—P1—C11—C16 | −109.9 (2) | Au—P1—C31—C32 | 139.2 (2) |
C31—P1—C11—C16 | 2.9 (3) | C11—P1—C31—C36 | 86.5 (3) |
Au—P1—C11—C16 | 127.3 (2) | C21—P1—C31—C36 | −161.9 (2) |
C21—P1—C11—C12 | 70.2 (2) | Au—P1—C31—C36 | −39.9 (3) |
C31—P1—C11—C12 | −177.0 (2) | C36—C31—C32—C33 | −1.0 (4) |
Au—P1—C11—C12 | −52.6 (2) | P1—C31—C32—C33 | 179.9 (2) |
C16—C11—C12—C13 | 1.5 (4) | C31—C32—C33—C34 | −0.2 (4) |
P1—C11—C12—C13 | −178.7 (2) | C32—C33—C34—C35 | 0.6 (5) |
C11—C12—C13—C14 | −0.3 (4) | C33—C34—C35—C36 | 0.2 (5) |
C12—C13—C14—C15 | −0.5 (4) | C34—C35—C36—C31 | −1.3 (5) |
C13—C14—C15—C16 | 0.1 (4) | C32—C31—C36—C35 | 1.8 (5) |
C12—C11—C16—C15 | −1.9 (4) | P1—C31—C36—C35 | −179.1 (3) |
Cg1 and Cg2 are the centroids of the (C2–C7) and (C11–C16) rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.95 | 2.42 | 3.269 (3) | 148 |
C36—H36···F1i | 0.95 | 2.51 | 3.218 (4) | 131 |
C13—H13···S1ii | 0.95 | 2.83 | 3.519 (3) | 130 |
C13—H13···Cg1ii | 0.95 | 2.74 | 3.500 (3) | 137 |
C22—H22···Cg1iii | 0.95 | 2.63 | 3.397 (3) | 138 |
C24—H24···Cg2iv | 0.95 | 2.80 | 3.552 (3) | 137 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x, −y+1, −z+1; (iv) x−1, y, z. |
Contact | Distance | Symmetry operation |
C3—H3···O1b | 2.31 | -x + 1, -y + 1, -z + 1 |
C36—H36···F1b | 2.43 | -x + 1, -y + 1, -z + 1 |
C13—H13···S1b | 2.74 | -x + 1/2, y - 1/2, -z + 1/2 |
C7—H7···C1 | 2.66 | -x, -y + 1, -z + 1 |
H8C···H33 | 2.31 | -x + 1/2, y + 1/2, -z + 3/2 |
C15—H15···Cg(C21–C26) | 3.23 | -x, -y, -z + 1 |
C32—H32···Cg(C11–C16) | 3.22 | -x, -y, -z + 1 |
Notes: (a) The interatomic distances are calculated in Crystal Explorer 17 (Turner et al., 2017) whereby the X—H bond lengths are adjusted to their neutron values; (b) these interactions correspond to those discussed above in Supramolecular features. |
Contact | Percentage contribution |
H···H | 44.9 |
H···C/C···H | 30.8 |
H···F/F···H | 8.1 |
H···S/S···H | 6.9 |
H···O/O···H | 3.2 |
Others | 6.1 |
Contact | EBSSEint | Symmetry operation |
C22—H22···π(C2–C7) (×2) + | ||
C7—H7···C1 (×2) | -37.2 | -x, -y + 1, -z + 1 |
C36—H36···F1 (×2) + | ||
C3—H3···O1 (×2) | -34.9 | -x + 1, -y + 1, -z + 1 |
C32—H32···π(C11–C16) (×2) + | ||
C15—H15···π(C21–C26) (×2) | -15.6 | -x, -y, -z + 1 |
C13—H13···π(C2–C7) + | ||
C13—H13···S1 | -8.9 | -x + 1/2, y - 1/2, -z + 1/2 |
C24—H24···π(C11–C16) | -5.4 | x - 1, y, z |
Y | Au—S | Au—P | P—Au—S | Au···O | CNOS/C6 | REFCODE | Ref. |
H | 2.3005 (14) | 2.2578 (12) | 177.72 (4) | 3.045 (4) | 87.18 (18) | HADZAN | Hall & Tiekink (1993) |
Ha | 2.3102 (14) | 2.2613 (12) | 175.96 (5) | 3.140 (3) | 78.4 (2) | COCRUI | Kuan et al. (2008) |
Me | 2.2968 (15) | 2.2479 (11) | 175.12 (4) | 2.954 (3) | 74.69 (16) | COCROC | Kuan et al. (2008) |
Clb | 2.2903 (17) | 2.2416 (14) | 174.61 (5) | 2.988 (3) | 75.01 (14) | VUYKOQ | Tadbuppa & Tiekink (2010) |
Clc | 2.3071 (15) | 2.2535 (15) | 175.62 (5) | 3.052 (3) | 73.95 (16) | VUYKOQ01 | Yeo et al. (2016) |
F | 2.3007 (8) | 2.2494 (8) | 176.10 (3) | 2.986 (2) | 78.73 (9) | – | This work |
Notes: (a) chloroform solvate; (b) P1 polymorph; (c) P21/c polymorph. |
Funding information
This research was supported by the Trans-disciplinary Research Grant Scheme (TR002-2014A) provided by the Ministry of Education, Malaysia. Sunway University Sdn Bhd is thanked for financial support of this work through grant No. STR-RCTR-RCCM-001-2019.
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