research communications
A monoclinic polymorph of [(Z)-N-(3-chlorophenyl)-O-methylthiocarbamato-κS](triphenylphosphane-κP)gold(I): and Hirshfeld surface analysis
aResearch Centre for Crystalline Materials, Faculty of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia
*Correspondence e-mail: edwardt@sunway.edu.my
The title compound, [Au(C8H7ClNOS)(C18H15P)], is a monoclinic (P21/n, Z′ = 1; form β) polymorph of the previously reported triclinic form (P-1, Z′ = 1; form α) [Tadbuppa & Tiekink (2010). Acta Cryst. E66, m664]. The molecular structures of both forms feature an almost linear gold(I) coordination geometry [P—Au—S = 175.62 (5)° in the title polymorph], being coordinated by thiolate S and phosphane P atoms, a Z conformation about the C=N bond and an intramolecular Au⋯O contact. The major conformational difference relates to the relative orientations of the residues about the Au—S bond: the P—Au—S—C torsion angles are −8.4 (7) and 106.2 (7)° in forms α and β, respectively. The molecular packing of form β features centrosymmetric aggregates sustained by aryl-C—H⋯O interactions, which are connected into a three-dimensional network by aryl-C—H⋯π contacts. The Hirshfeld analysis of forms α and β shows many similarities with the notable exception of the influence of C—H⋯O interactions in form β.
Keywords: crystal structure; polymorph; gold; thiocarbamate; Hirshfeld surface analysis.
CCDC reference: 1489737
1. Chemical context
Interest in the chemistry of phosphanegold(I) N-aryl-O-alkylthiocarbamates, i.e. compounds of general formula R3PAu[SC(OR′)=NR′′] (R, R′ = alkyl, aryl; R′′ = aryl) continues owing to their recently disclosed exciting biological activities. Thus, various triphenylphosphane derivatives display excellent cytotoxicity profiles against HT-29 colon cancer cells, a particularly virulent form of cancer, and mechanistic studies have shown these to induce both intrinsic and extrinsic pathways of cell death leading to apoptosis (Yeo, Ooi et al., 2013; Ooi et al., 2015). Further, species with R′′ = p-tolyl have proven to exhibit impressive in vitro potency against Gram-positive bacteria (Yeo, Sim et al., 2013). It was during another synthesis of the title compound, (I), for further biological studies, that crystals of a new polymorph were isolated from its methanol solution. This is called form β to distinguish it from the earlier triclinic form, form α (Tadbuppa & Tiekink, 2010). Herein, the crystal and molecular structures of form β of (I) are described along with a comparison with the parameters characterizing form α. Further, a Hirshfeld surface analysis of both polymorphic forms of (I) is presented.
2. Structural commentary
The molecular structure of the new monoclinic form of (I), form β, is shown in Fig. 1, and selected geometric parameters are collected in Table 1. The gold(I) atom is coordinated in an approximately linear configuration by phosphane-P and thiolate-S atoms. Confirmation of the `thiolate' assignment is readily seen in the relatively long C1—S1 bond length and the significant π-character in the C1—N1 bond when the geometric parameters are compared with structures of related thiocarbamide molecules (Ho et al., 2005; Kuan et al., 2007); the of the thiocarbamide precursor in (I) is not available for comparison. As is invariably observed in this class of compound, the Au—S bond length is longer than the Au—P bond. The small deviation from ideal linearity for the P—Au—S bond is related to the close approach of the oxygen atom to the gold(I) atom, i.e. 3.052 (3) Å. The pattern of bond angles about the quaternary carbon atom, C1, follow the expected trends with the widest angle involving the sulfur and doubly bonded nitrogen atom and with the narrowest angle involving the single-bonded atoms. The conformation about the formal C1=N1 bond, Table 1, is Z.
Form β crystallizes in the monoclinic P21/n with Z′ = 1. The earlier polymorph, by contrast, crystallizes in triclinic P, also with Z′ = 1. A comparison of the key geometric parameters is given in Table 1. From these data, it is clear that there is experimental inequivalence in the bond lengths involving the gold(I) atoms, with the Au—S and Au—P bond lengths in form β being marginally longer. The intramolecular Au⋯O separation in form β is also longer than the comparable separation in form α, and this is correlated with a smaller deviation from a linear geometry about the gold(I) atom in β. By contrast, the bond angles are, by and large, equivalent within experimental error. A significant conformational difference is evident in the molecular structures of forms α and β of (I). As seen from the overlay diagram shown in Fig. 2, this difference occurs as a result of a twist about the Au—S bond as seen in the values of the P1—Au—S1—C1 torsion angles of −8.4 (7) and 106.2 (7)° in forms α and β, respectively.
3. Supramolecular features
Supramolecular dimers feature in the molecular packing of form β of (I), which are sustained by N-aryl-C—H⋯O(methoxy) interactions, Fig. 3a and Table 2. The dimers are connected into a three-dimensional architecture by a network of C—H⋯π interactions, Fig. 3b and Table 2. Within this arrangement, centrosymmetrically related Ph3P ligands align to form a so-called six-fold phenyl embrace (6PE) (Dance & Scudder, 1995) featuring edge-to-face phenyl-C—H⋯π(phenyl) interactions, Fig. 3c. While the interactions are too long to be considered as significant in terms of the criteria in PLATON (Spek, 2009), there are a number of such interactions, i.e. 2 × [3.22, 3.26 and 3.29 Å], that serve to reinforce the 6PE embrace with one pair of rings accepting two interactions each. In form α of (I), the most prominent feature of the molecular packing is the formation of supramolecular chains mediated by C—H⋯π interactions (Tadbuppa & Tiekink, 2010). Further analysis of the molecular packing in polymorphic (I) is given in the following Section.
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4. Analysis of the Hirshfeld surfaces
The non-covalent interactions present in the pair of polymorphs of (I), i.e. forms α and β, were studied through Hirshfeld surface analysis by mapping on the normalized contact distance (dnorm) upon computation of the inner (di) and outer (de) distances of the Hirshfeld surface to the nearest nucleus (Spackman & Jayatilaka, 2009; McKinnon et al., 2007). All computation as well as generation of two-dimensional fingerprint plots were performed using Crystal Explorer 3.1 (Wolff et al., 2012). Distances involving hydrogen atoms were normalized by default to the standard neutron-diffraction bond lengths.
As evident from Fig. 4 and Table 3, forms α and β of (I) exhibit relatively similar percentage contributions of the indicated intermolecular interactions to their Hirshfeld surfaces. However, the specific contributions to their interaction profiles are distinct as evidenced from the overall and decomposed two-dimensional fingerprint plots shown in Fig. 5. As mentioned above in Supramolecular features, C—H⋯π interactions feature in both structures. To a first approximation the decomposed fingerprint plots look similar, as seen from Fig. 5b. However, relatively shorter contacts are found in form β cf. form α, i.e. 2.62 vs 2.68 Å. The clear distinction between the two forms is readily noted from the decomposed fingerprint plots for the O⋯H/H⋯O contacts with very distinct spikes evident for form β, Fig. 5c, correlating with the C—H⋯O interactions leading to dimer formation. While beyond the sum of their respective van der Waals radii (Spek, 2009), Cl⋯H/H⋯Cl interactions make contributions to the Hirshfeld surfaces of both forms α and β, with the contacts, again, being shorter in form β, i.e. 2.76 vs 3.00 Å, leading to more the distinct forceps in Fig. 5d.
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In general, the observation of generally shorter contacts in form β may indicate greater crystal-packing efficiency (Lloyd et al., 2005). Table 4 collates various molecular/crystal structure descriptors for the polymorphic forms. Immediately evident is that the calculated unit-cell densities are identical but the crystal-packing efficiency (KPI; Spek, 2009) for form β is marginally greater. Computation on the area-to-volume ratio between forms α and β revealed very little difference as did the globularity (G) and asphericity (Ω) indices. All these indicators suggest that the polymorphs arise as a result of a simple interplay between molecular conformation and crystal-packing effects.
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5. Database survey
The most closely related structure to (I) in the crystallographic literature (Groom et al., 2016), is the R′ = OEt analogue, i.e. (II), (Tadbuppa & Tiekink, 2009). Key geometric parameters for this structure are also included in Table 1. Non-systematic variations in parameters are noted, e.g. the Au—S bond length in (II) is intermediate between those found in the polymorphic forms of (I), and the Au—P bond length is the longest of the three structures. However, differences are small and probably can be ascribed to the influences of crystal-packing effects.
As indicated in the Chemical context, biological considerations motivate ongoing investigations into the chemistry of phosphanegold(I) N-aryl-O-alkylthiocarbamates. This notwithstanding, the relative ease of growing crystals have prompted several crystal engineering studies. Thus, correlations between Au⋯Au (aurophilic) and solid-state luminescence responses have been made for the series of compounds, R3PAu[SC(OMe)=NC6H4NO2-p] (R = Et, Cy and Ph), and bidentate phosphane analogues, Ph2P–(CH2)n–PPh2 for n = 1–4 and when the bridge is Fc (ferrocenyl) (Ho et al., 2006). In another study, the influence of R and Y substituents upon the molecular packing of compounds of the general formula [(Ph2P(CH2)4PPh2){AuSC(OR′)=NC6H4Y-p}2] for R′ = Me, Et or iPr and Y = H, NO2 or Me was undertaken (Ho & Tiekink, 2007). Besides the anticipated linear P—Au—S configuration, a common feature of all the analysed structures until then was the presence of intramolecular Au⋯O interactions, as illustrated in Fig. 1. This changed in another systematic study, this time of R3PAu[SC(OMe)=NR′′], for R = Ph, o-tol, m-tol or p-tol, and R′' = Ph, o-tol, m-tol, p-tol or C6H4NO2-p, where it proved possible to induce a conformational change in the molecule so that an intramolecular Au⋯π interaction formed rather than Au⋯O (Kuan et al., 2008); Au⋯π interactions are well documented in the crystallographic literature (Tiekink & Zukerman-Schpector, 2009; Caracelli et al., 2013). For example, having R = R′′ = p-tol simultaneously activated the gold atom, making it amenable to form an Au⋯π interaction with the comparatively electron-rich aryl ring. Recently, bipodal forms of the thiocarbamide ligands were prepared and complexed with phosphanegold(I) species yielding binuclear molecules also with intramolecular Au⋯π interactions (Yeo et al., 2015). Computational chemistry showed the Au⋯π interactions to be more favourable, by ca 12 kcal mol−1, than the putative Au⋯O interaction (Yeo et al., 2015).
Such interplay between substituents in crystal engineering endeavours, along with the observation that biological activities are acutely sensitive to substitution patterns, ensures this area of research will continue to attract significant attention.
6. Synthesis and crystallization
All chemicals and solvents were used as purchased without purification. All reactions were carried out under ambient conditions. Melting points were determined on a Biobase auto melting point apparatus MP300. IR spectra were obtained on a Perkin Elmer Spectrum 400 FT Mid-IR/Far-IR spectrophotometer from 4000 to 400 cm−1; abbreviation: s, strong.
Preparation of (I): NaOH (Merck; 0.25 mmol, 0.01 g) in MeOH (Merck; 1 ml) was added to a suspension of Ph3PAuCl (0.25 mmol, 0.12 g) in MeOH (Merck; 15 ml), followed by addition of the thiocarbamide, MeOC(=S)N(H)C6H4Cl3 (0.25 mmol, 0.05 g), prepared following literature precedents (Ho et al., 2005), in MeOH (15 ml). The resulting mixture was stirred for 2 h at 323 K. The solution mixture was left for slow evaporation at room temperature, yielding colourless prisms of the title compound after 3 weeks. Yield: 0.134 g (81%). M.p. 431–433 K. IR (cm−1): 1434 (s) ν(C=N), 1180 (s) ν(C—O), 1098 (s) ν(C—S).
7. 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 residual electron density peaks of 2.04 and 1.06 e Å−3, respectively, were located 1.01 and 0.77 Å from the Au atom.
details are summarized in Table 5
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Supporting information
CCDC reference: 1489737
https://doi.org/10.1107/S2056989016010781/hb7598sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016010781/hb7598Isup2.hkl
Data collection: CrysAlis PRO (Agilent, 2010); cell
CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012), QMol (Gans & Shalloway, 2001) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Au(C8H7ClNOS)(C18H15P)] | F(000) = 1280 |
Mr = 659.89 | Dx = 1.805 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0078 (4) Å | Cell parameters from 5344 reflections |
b = 17.4732 (7) Å | θ = 2.3–27.5° |
c = 15.5641 (7) Å | µ = 6.34 mm−1 |
β = 97.595 (4)° | T = 100 K |
V = 2428.22 (18) Å3 | Prism, colourless |
Z = 4 | 0.10 × 0.05 × 0.03 mm |
Agilent SuperNova Dual Source diffractometer with an Atlas detector | 5613 independent reflections |
Radiation source: SuperNova (Mo) X-ray Source | 4470 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.065 |
Detector resolution: 10.4041 pixels mm-1 | θmax = 27.6°, θmin = 2.3° |
ω scan | h = −11→9 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010) | k = −22→22 |
Tmin = 0.570, Tmax = 0.833 | l = −17→20 |
18211 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.040 | H-atom parameters constrained |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0282P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
5613 reflections | Δρmax = 2.04 e Å−3 |
290 parameters | Δρmin = −1.06 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 | 0.19155 (2) | 0.79563 (2) | 0.43242 (2) | 0.02135 (8) | |
Cl1 | 0.35621 (18) | 1.26890 (8) | 0.33228 (10) | 0.0342 (4) | |
P1 | 0.11209 (17) | 0.67786 (8) | 0.46382 (9) | 0.0209 (3) | |
S1 | 0.25415 (18) | 0.91846 (8) | 0.39637 (9) | 0.0263 (3) | |
O1 | 0.3390 (4) | 0.9118 (2) | 0.5632 (2) | 0.0231 (8) | |
N1 | 0.2776 (5) | 1.0330 (2) | 0.5172 (3) | 0.0238 (10) | |
C1 | 0.2894 (6) | 0.9623 (3) | 0.4991 (3) | 0.0206 (11) | |
C2 | 0.2162 (7) | 1.0859 (3) | 0.4530 (4) | 0.0240 (12) | |
C3 | 0.3063 (6) | 1.1426 (3) | 0.4247 (3) | 0.0222 (12) | |
H3 | 0.4107 | 1.1438 | 0.4442 | 0.027* | |
C4 | 0.2408 (7) | 1.1975 (3) | 0.3675 (4) | 0.0237 (12) | |
C5 | 0.0901 (7) | 1.1990 (3) | 0.3373 (4) | 0.0231 (12) | |
H5 | 0.0489 | 1.2371 | 0.2975 | 0.028* | |
C6 | 0.0000 (7) | 1.1425 (3) | 0.3670 (4) | 0.0270 (13) | |
H6 | −0.1046 | 1.1423 | 0.3478 | 0.032* | |
C7 | 0.0618 (6) | 1.0863 (3) | 0.4249 (4) | 0.0262 (13) | |
H7 | −0.0007 | 1.0484 | 0.4452 | 0.031* | |
C8 | 0.3796 (7) | 0.9450 (3) | 0.6480 (3) | 0.0294 (13) | |
H8A | 0.4077 | 0.9042 | 0.6903 | 0.044* | |
H8B | 0.2941 | 0.9735 | 0.6647 | 0.044* | |
H8C | 0.4645 | 0.9798 | 0.6466 | 0.044* | |
C11 | −0.0850 (6) | 0.6656 (3) | 0.4249 (3) | 0.0208 (12) | |
C12 | −0.1829 (7) | 0.7251 (3) | 0.4386 (4) | 0.0258 (13) | |
H12 | −0.1448 | 0.7711 | 0.4657 | 0.031* | |
C13 | −0.3350 (7) | 0.7173 (3) | 0.4127 (4) | 0.0316 (14) | |
H13 | −0.4014 | 0.7575 | 0.4228 | 0.038* | |
C14 | −0.3908 (7) | 0.6504 (3) | 0.3719 (4) | 0.0301 (14) | |
H14 | −0.4953 | 0.6451 | 0.3544 | 0.036* | |
C15 | −0.2952 (7) | 0.5923 (3) | 0.3569 (4) | 0.0289 (13) | |
H15 | −0.3340 | 0.5474 | 0.3277 | 0.035* | |
C16 | −0.1436 (6) | 0.5982 (3) | 0.3838 (3) | 0.0252 (12) | |
H16 | −0.0788 | 0.5569 | 0.3747 | 0.030* | |
C21 | 0.2049 (5) | 0.6011 (3) | 0.4174 (3) | 0.0157 (11) | |
C22 | 0.2091 (6) | 0.6018 (3) | 0.3269 (3) | 0.0222 (12) | |
H22 | 0.1637 | 0.6431 | 0.2935 | 0.027* | |
C23 | 0.2778 (6) | 0.5437 (3) | 0.2856 (4) | 0.0261 (13) | |
H23 | 0.2804 | 0.5458 | 0.2248 | 0.031* | |
C24 | 0.3423 (6) | 0.4830 (3) | 0.3338 (4) | 0.0251 (12) | |
H24 | 0.3879 | 0.4427 | 0.3057 | 0.030* | |
C25 | 0.3412 (6) | 0.4803 (3) | 0.4227 (4) | 0.0258 (13) | |
H25 | 0.3868 | 0.4386 | 0.4554 | 0.031* | |
C26 | 0.2729 (6) | 0.5389 (3) | 0.4639 (4) | 0.0243 (12) | |
H26 | 0.2725 | 0.5366 | 0.5248 | 0.029* | |
C31 | 0.1333 (6) | 0.6589 (3) | 0.5800 (3) | 0.0197 (11) | |
C32 | 0.0283 (6) | 0.6151 (3) | 0.6158 (3) | 0.0233 (12) | |
H32 | −0.0569 | 0.5951 | 0.5804 | 0.028* | |
C33 | 0.0503 (7) | 0.6009 (3) | 0.7051 (4) | 0.0274 (13) | |
H33 | −0.0207 | 0.5709 | 0.7303 | 0.033* | |
C34 | 0.1734 (7) | 0.6299 (3) | 0.7572 (4) | 0.0293 (14) | |
H34 | 0.1883 | 0.6192 | 0.8176 | 0.035* | |
C35 | 0.2751 (7) | 0.6748 (3) | 0.7201 (4) | 0.0318 (14) | |
H35 | 0.3587 | 0.6961 | 0.7557 | 0.038* | |
C36 | 0.2558 (7) | 0.6890 (3) | 0.6314 (4) | 0.0286 (13) | |
H36 | 0.3265 | 0.7192 | 0.6063 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Au | 0.02540 (14) | 0.01827 (12) | 0.02023 (13) | −0.00202 (8) | 0.00242 (9) | −0.00004 (8) |
Cl1 | 0.0355 (9) | 0.0266 (7) | 0.0414 (9) | −0.0078 (6) | 0.0081 (7) | 0.0040 (6) |
P1 | 0.0232 (8) | 0.0201 (7) | 0.0192 (7) | 0.0002 (6) | 0.0027 (6) | 0.0008 (5) |
S1 | 0.0387 (9) | 0.0204 (7) | 0.0198 (7) | −0.0048 (6) | 0.0033 (6) | 0.0002 (5) |
O1 | 0.025 (2) | 0.022 (2) | 0.022 (2) | 0.0015 (16) | 0.0009 (16) | −0.0001 (15) |
N1 | 0.023 (3) | 0.021 (2) | 0.027 (3) | −0.0022 (19) | 0.003 (2) | −0.0017 (19) |
C1 | 0.018 (3) | 0.024 (3) | 0.020 (3) | −0.002 (2) | 0.004 (2) | 0.000 (2) |
C2 | 0.031 (3) | 0.014 (3) | 0.026 (3) | −0.001 (2) | 0.004 (2) | −0.003 (2) |
C3 | 0.020 (3) | 0.022 (3) | 0.025 (3) | 0.002 (2) | 0.004 (2) | −0.005 (2) |
C4 | 0.026 (3) | 0.020 (3) | 0.026 (3) | 0.000 (2) | 0.007 (2) | −0.001 (2) |
C5 | 0.031 (3) | 0.020 (3) | 0.019 (3) | 0.006 (2) | 0.005 (2) | 0.000 (2) |
C6 | 0.026 (3) | 0.026 (3) | 0.028 (3) | 0.002 (2) | −0.002 (2) | −0.003 (2) |
C7 | 0.024 (3) | 0.023 (3) | 0.033 (3) | −0.005 (2) | 0.006 (3) | 0.000 (2) |
C8 | 0.033 (4) | 0.030 (3) | 0.023 (3) | 0.001 (3) | −0.001 (3) | −0.003 (2) |
C11 | 0.023 (3) | 0.022 (3) | 0.016 (3) | −0.002 (2) | 0.001 (2) | 0.002 (2) |
C12 | 0.029 (3) | 0.023 (3) | 0.025 (3) | 0.002 (2) | 0.006 (3) | −0.002 (2) |
C13 | 0.030 (4) | 0.034 (3) | 0.032 (3) | 0.009 (3) | 0.005 (3) | 0.000 (3) |
C14 | 0.019 (3) | 0.046 (4) | 0.023 (3) | −0.006 (3) | −0.004 (2) | 0.004 (3) |
C15 | 0.029 (3) | 0.033 (3) | 0.023 (3) | −0.005 (3) | 0.000 (2) | −0.003 (2) |
C16 | 0.024 (3) | 0.024 (3) | 0.026 (3) | 0.001 (2) | 0.000 (2) | 0.004 (2) |
C21 | 0.007 (3) | 0.019 (3) | 0.019 (3) | −0.009 (2) | −0.005 (2) | 0.006 (2) |
C22 | 0.022 (3) | 0.021 (3) | 0.023 (3) | −0.003 (2) | 0.001 (2) | −0.003 (2) |
C23 | 0.028 (3) | 0.031 (3) | 0.020 (3) | −0.005 (3) | 0.004 (2) | −0.002 (2) |
C24 | 0.025 (3) | 0.018 (3) | 0.032 (3) | 0.002 (2) | 0.006 (2) | −0.006 (2) |
C25 | 0.027 (3) | 0.019 (3) | 0.030 (3) | 0.002 (2) | 0.001 (3) | 0.007 (2) |
C26 | 0.027 (3) | 0.024 (3) | 0.022 (3) | −0.001 (2) | 0.002 (2) | −0.002 (2) |
C31 | 0.020 (3) | 0.016 (3) | 0.023 (3) | −0.002 (2) | 0.005 (2) | −0.005 (2) |
C32 | 0.027 (3) | 0.015 (3) | 0.026 (3) | −0.002 (2) | −0.003 (2) | 0.000 (2) |
C33 | 0.031 (3) | 0.026 (3) | 0.026 (3) | −0.001 (3) | 0.005 (3) | 0.002 (2) |
C34 | 0.039 (4) | 0.026 (3) | 0.021 (3) | 0.001 (3) | 0.000 (3) | 0.003 (2) |
C35 | 0.030 (4) | 0.040 (3) | 0.024 (3) | −0.013 (3) | −0.004 (3) | −0.002 (3) |
C36 | 0.031 (4) | 0.033 (3) | 0.023 (3) | −0.004 (3) | 0.006 (3) | 0.001 (2) |
Au—P1 | 2.2535 (14) | C13—H13 | 0.9500 |
Au—S1 | 2.3070 (14) | C14—C15 | 1.372 (8) |
Cl1—C4 | 1.756 (6) | C14—H14 | 0.9500 |
P1—C21 | 1.783 (5) | C15—C16 | 1.378 (8) |
P1—C11 | 1.811 (6) | C15—H15 | 0.9500 |
P1—C31 | 1.824 (5) | C16—H16 | 0.9500 |
S1—C1 | 1.764 (5) | C21—C26 | 1.402 (7) |
O1—C1 | 1.362 (6) | C21—C22 | 1.413 (7) |
O1—C8 | 1.443 (6) | C22—C23 | 1.390 (7) |
N1—C1 | 1.274 (6) | C22—H22 | 0.9500 |
N1—C2 | 1.418 (7) | C23—C24 | 1.383 (7) |
C2—C3 | 1.389 (8) | C23—H23 | 0.9500 |
C2—C7 | 1.402 (8) | C24—C25 | 1.386 (8) |
C3—C4 | 1.387 (7) | C24—H24 | 0.9500 |
C3—H3 | 0.9500 | C25—C26 | 1.394 (7) |
C4—C5 | 1.378 (8) | C25—H25 | 0.9500 |
C5—C6 | 1.395 (8) | C26—H26 | 0.9500 |
C5—H5 | 0.9500 | C31—C36 | 1.379 (7) |
C6—C7 | 1.398 (7) | C31—C32 | 1.389 (7) |
C6—H6 | 0.9500 | C32—C33 | 1.399 (7) |
C7—H7 | 0.9500 | C32—H32 | 0.9500 |
C8—H8A | 0.9800 | C33—C34 | 1.380 (8) |
C8—H8B | 0.9800 | C33—H33 | 0.9500 |
C8—H8C | 0.9800 | C34—C35 | 1.389 (8) |
C11—C12 | 1.398 (8) | C34—H34 | 0.9500 |
C11—C16 | 1.409 (7) | C35—C36 | 1.391 (8) |
C12—C13 | 1.383 (8) | C35—H35 | 0.9500 |
C12—H12 | 0.9500 | C36—H36 | 0.9500 |
C13—C14 | 1.391 (8) | ||
P1—Au—S1 | 175.62 (5) | C15—C14—C13 | 120.2 (6) |
C21—P1—C11 | 105.5 (2) | C15—C14—H14 | 119.9 |
C21—P1—C31 | 105.8 (2) | C13—C14—H14 | 119.9 |
C11—P1—C31 | 106.2 (2) | C14—C15—C16 | 120.8 (5) |
C21—P1—Au | 114.80 (17) | C14—C15—H15 | 119.6 |
C11—P1—Au | 111.17 (17) | C16—C15—H15 | 119.6 |
C31—P1—Au | 112.75 (17) | C15—C16—C11 | 119.8 (5) |
C1—S1—Au | 101.78 (18) | C15—C16—H16 | 120.1 |
C1—O1—C8 | 115.4 (4) | C11—C16—H16 | 120.1 |
C1—N1—C2 | 120.8 (5) | C26—C21—C22 | 117.0 (5) |
N1—C1—O1 | 119.7 (5) | C26—C21—P1 | 124.8 (4) |
N1—C1—S1 | 127.7 (4) | C22—C21—P1 | 118.2 (4) |
O1—C1—S1 | 112.6 (4) | C23—C22—C21 | 121.8 (5) |
C3—C2—C7 | 119.6 (5) | C23—C22—H22 | 119.1 |
C3—C2—N1 | 119.9 (5) | C21—C22—H22 | 119.1 |
C7—C2—N1 | 120.1 (5) | C24—C23—C22 | 119.4 (5) |
C4—C3—C2 | 118.8 (5) | C24—C23—H23 | 120.3 |
C4—C3—H3 | 120.6 | C22—C23—H23 | 120.3 |
C2—C3—H3 | 120.6 | C23—C24—C25 | 120.6 (5) |
C5—C4—C3 | 123.2 (5) | C23—C24—H24 | 119.7 |
C5—C4—Cl1 | 118.5 (4) | C25—C24—H24 | 119.7 |
C3—C4—Cl1 | 118.2 (4) | C24—C25—C26 | 119.8 (5) |
C4—C5—C6 | 117.6 (5) | C24—C25—H25 | 120.1 |
C4—C5—H5 | 121.2 | C26—C25—H25 | 120.1 |
C6—C5—H5 | 121.2 | C25—C26—C21 | 121.5 (5) |
C5—C6—C7 | 120.8 (5) | C25—C26—H26 | 119.3 |
C5—C6—H6 | 119.6 | C21—C26—H26 | 119.3 |
C7—C6—H6 | 119.6 | C36—C31—C32 | 120.8 (5) |
C6—C7—C2 | 119.9 (5) | C36—C31—P1 | 118.4 (4) |
C6—C7—H7 | 120.0 | C32—C31—P1 | 120.7 (4) |
C2—C7—H7 | 120.0 | C31—C32—C33 | 118.8 (5) |
O1—C8—H8A | 109.5 | C31—C32—H32 | 120.6 |
O1—C8—H8B | 109.5 | C33—C32—H32 | 120.6 |
H8A—C8—H8B | 109.5 | C34—C33—C32 | 121.0 (5) |
O1—C8—H8C | 109.5 | C34—C33—H33 | 119.5 |
H8A—C8—H8C | 109.5 | C32—C33—H33 | 119.5 |
H8B—C8—H8C | 109.5 | C33—C34—C35 | 119.1 (5) |
C12—C11—C16 | 119.0 (5) | C33—C34—H34 | 120.5 |
C12—C11—P1 | 118.1 (4) | C35—C34—H34 | 120.5 |
C16—C11—P1 | 122.9 (4) | C34—C35—C36 | 120.7 (5) |
C13—C12—C11 | 120.2 (5) | C34—C35—H35 | 119.7 |
C13—C12—H12 | 119.9 | C36—C35—H35 | 119.7 |
C11—C12—H12 | 119.9 | C31—C36—C35 | 119.5 (5) |
C12—C13—C14 | 120.0 (6) | C31—C36—H36 | 120.2 |
C12—C13—H13 | 120.0 | C35—C36—H36 | 120.2 |
C14—C13—H13 | 120.0 | ||
C2—N1—C1—O1 | −175.5 (5) | C12—C11—C16—C15 | 0.8 (8) |
C2—N1—C1—S1 | 6.8 (8) | P1—C11—C16—C15 | 179.0 (4) |
C8—O1—C1—N1 | −2.1 (7) | C11—P1—C21—C26 | −110.0 (5) |
C8—O1—C1—S1 | 176.0 (4) | C31—P1—C21—C26 | 2.3 (5) |
Au—S1—C1—N1 | −153.4 (5) | Au—P1—C21—C26 | 127.3 (4) |
Au—S1—C1—O1 | 28.7 (4) | C11—P1—C21—C22 | 69.0 (4) |
C1—N1—C2—C3 | −113.5 (6) | C31—P1—C21—C22 | −178.7 (4) |
C1—N1—C2—C7 | 73.4 (7) | Au—P1—C21—C22 | −53.7 (4) |
C7—C2—C3—C4 | −1.4 (8) | C26—C21—C22—C23 | −0.2 (7) |
N1—C2—C3—C4 | −174.6 (5) | P1—C21—C22—C23 | −179.3 (4) |
C2—C3—C4—C5 | 0.3 (8) | C21—C22—C23—C24 | 0.8 (8) |
C2—C3—C4—Cl1 | −180.0 (4) | C22—C23—C24—C25 | −1.1 (8) |
C3—C4—C5—C6 | 0.7 (8) | C23—C24—C25—C26 | 0.7 (8) |
Cl1—C4—C5—C6 | −179.0 (4) | C24—C25—C26—C21 | −0.1 (8) |
C4—C5—C6—C7 | −0.6 (8) | C22—C21—C26—C25 | −0.2 (8) |
C5—C6—C7—C2 | −0.6 (8) | P1—C21—C26—C25 | 178.8 (4) |
C3—C2—C7—C6 | 1.6 (8) | C21—P1—C31—C36 | 90.7 (5) |
N1—C2—C7—C6 | 174.7 (5) | C11—P1—C31—C36 | −157.5 (4) |
C21—P1—C11—C12 | −169.0 (4) | Au—P1—C31—C36 | −35.5 (5) |
C31—P1—C11—C12 | 79.0 (5) | C21—P1—C31—C32 | −89.3 (5) |
Au—P1—C11—C12 | −44.0 (5) | C11—P1—C31—C32 | 22.4 (5) |
C21—P1—C11—C16 | 12.7 (5) | Au—P1—C31—C32 | 144.4 (4) |
C31—P1—C11—C16 | −99.3 (5) | C36—C31—C32—C33 | −1.1 (8) |
Au—P1—C11—C16 | 137.7 (4) | P1—C31—C32—C33 | 179.0 (4) |
C16—C11—C12—C13 | 0.6 (8) | C31—C32—C33—C34 | 0.2 (8) |
P1—C11—C12—C13 | −177.7 (4) | C32—C33—C34—C35 | 1.1 (9) |
C11—C12—C13—C14 | −0.8 (9) | C33—C34—C35—C36 | −1.7 (9) |
C12—C13—C14—C15 | −0.3 (9) | C32—C31—C36—C35 | 0.6 (9) |
C13—C14—C15—C16 | 1.7 (9) | P1—C31—C36—C35 | −179.5 (5) |
C14—C15—C16—C11 | −1.9 (8) | C34—C35—C36—C31 | 0.8 (9) |
Hydrogen-bond geometry (Å, °) for (I), Form β, Cg1, Cg3 and Cg4 are the centroids of the C2–C7, C21–C26 and C31–C36 rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1i | 0.95 | 2.47 | 3.315 (7) | 148 |
C5—H5···Cg4ii | 0.95 | 2.85 | 3.492 (6) | 126 |
C12—H12···Cg1ii | 0.95 | 2.64 | 3.450 (6) | 143 |
C14—H14···Cg3iii | 0.95 | 2.80 | 3.570 (6) | 139 |
C23—H23···Cg1iv | 0.95 | 2.65 | 3.435 (6) | 140 |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x, −y+2, −z+1; (iii) x−1, y, z; (iv) −x+1/2, y−1/2, −z+1/2. |
Parameter | (I): form α | (I): form β | (II) |
Au—S1 | 2.2902 (13) | 2.3070 (14) | 2.3041 (9) |
Au—P1 | 2.2416 (11) | 2.2535 (14) | 2.2588 (8) |
C1—S1 | 1.760 (5) | 1.764 (5) | 1.759 (4) |
C1—O1 | 1.355 (6) | 1.362 (6) | 1.356 (4) |
C1—N1 | 1.241 (6) | 1.274 (6) | 1.265 (4) |
Au···O1 | 2.988 (3) | 3.052 (3) | 2.967 (3) |
S1—Au—P1 | 174.61 (4) | 175.62 (5) | 175.86 (3) |
Au—S1—C1 | 102.46 (16) | 101.78 (18) | 103.15 (12) |
C1—O1—C8 | 116.8 (4) | 115.4 (4) | 117.8 (3) |
C1—N1—C2 | 120.4 (4) | 120.8 (5) | 119.6 (3) |
S1—C1—O1 | 113.0 (3) | 112.6 (4) | 111.9 (2) |
S1—C1—N1 | 126.6 (4) | 127.7 (4) | 127.7 (3) |
O1—C1—N1 | 120.4 (4) | 119.7 (5) | 120.3 (3) |
Notes: (a) Tadbuppa & Tiekink (2010); (b) Tadbuppa & Tiekink (2009). |
Contact | % Contribution form α | % Contribution form β |
Au···Cl | 0.2 | 0.6 |
Au···C | 0.3 | 0.2 |
Au···H | 4.2 | 2.8 |
Cl···C | 2.7 | 0.3 |
Cl···H | 7.6 | 9.8 |
Cl···S | 0.0 | 0.2 |
S···C | 0.1 | 0.0 |
S···H | 6.6 | 6.3 |
O···H | 2.5 | 3.2 |
N···H | 1.9 | 1.7 |
N···C | 0.0 | 0.3 |
C···C | 0.4 | 0.8 |
C···H | 27.8 | 30.6 |
H···H | 45.6 | 43.2 |
Total | 99.9 | 100 |
Parameter | Form α | Form β |
Volume, V (Å3) | 596.42 | 596.78 |
Surface area, A (Å2) | 518.92 | 511.11 |
A:V (Å-1) | 0.87 | 0.86 |
Globularity, G | 0.660 | 0.671 |
Asphericity, Ω | 0.165 | 0.172 |
Density (g cm-1) | 1.805 | 1.805 |
Packing index (%) | 66.9 | 67.4 |
Acknowledgements
Intensity data were provided by the University of Malaya Crystallographic Laboratory.
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