research communications
A triclinic polymorph of tricyclohexylphosphane sulfide:
and Hirshfeld surface analysisaResearch Centre for Crystalline Materials, School of Science and Technology, Sunway University, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia, bDepartment of Chemistry, Lancaster University, Lancaster LA1 4YB, United Kingdom, and cDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India
*Correspondence e-mail: edwardt@sunway.edu.my
The title compound, (C6H11)3PS (systematic name: tricyclohexyl-λ5-phosphanethione), is a triclinic (P-1, Z′ = 1) polymorph of the previously reported orthorhombic form (Pnma, Z′ = 1/2) [Kerr et al. (1977). Can. J. Chem. 55, 3081–3085; Reibenspies et al. (1996). Z. Kristallogr. 211, 400]. While conformational differences exist between the non-symmetric molecule in the triclinic polymorph, cf. the mirror-symmetric molecule in the orthorhombic form, these differences are not chemically significant. The major feature of the molecular packing in the triclinic polymorph is the formation of linear chains along the a axis sustained by methine-C—H⋯S(thione) interactions. The chains pack with no directional interactions between them. The analysis of the Hirshfeld surface for both polymorphs indicates a high degree of similarity, being dominated by H⋯H (ca 90%) and S⋯H/H⋯S contacts.
CCDC reference: 1536014
1. Chemical context
Recent interest in the chemistry of phosphanegold(I) dithiocarbamate compounds stems from their potential as anti-cancer agents (de Vos et al. 2004; Ronconi et al. 2005; Gandin et al. 2010; Jamaludin et al. 2013; Keter et al. 2014; Altaf et al. 2015). In keeping with the increasing interest in gold compounds as potential anti-microbial agents to meet the challenges of microbes developing resistance to available chemotherapies (Glišić & Djuran, 2014) and in recognition of the potential of metal dithiocarbamates as anti-microbial agents (Hogarth, 2012), the anti-bacterial properties of phosphanegold(I) dithiocarbamates have also been explored in recent times (Sim et al., 2014; Chen et al., 2016). For example, the `all-ethyl' compound, Et3PAu(S2CNEt2), exhibits broad-range activity against Gram-positive and Gram-negative bacteria and was shown to be bactericidal against methicillin-resistant Staphylococcus aureus (MRSA) (Chen et al., 2016). As an extension of these studies, investigations into the anti-microbial potential of related bis(phosphane)copper(I) dithiocarbamates and their silver(I) analogues were undertaken, again revealing interesting results and dependency of activity upon phosphane- and dithiocarbamate-bound substituents (Jamaludin et al., 2016). During further investigations in this field, the title compound, Cy3P=S (I), was isolated as a decomposition product from a long-term (months) recrystallization of an acetone solution containing (Cy3P)2Ag(S2CNEt2). The crystal and molecular structures of (I) are reported herein and the results compared with those of a previously determined orthorhombic polymorph, (II) (Kerr et al., 1977; Reibenspies et al., 1996). Further, a detailed comparison of the Hirshfeld surfaces for (I) and (II) is presented.
2. Structural commentary
The molecular structure of (I), Fig. 1, features a tetrahedrally coordinated PV centre defined by a thione-S and three α-carbon atoms of the cyclohexyl substituents. The P1—C bond lengths span an experimentally distinct range of 1.8350 (14) to 1.8468 (15) Å, Table 1. The distortions from the ideal tetrahedral geometry are relatively minor with the widest angles generally involving the thione-S atom. The cyclohexyl rings, each with a chair conformation, adopt orientations so that the methine-H atom is directed towards the thione-S atom in the cases of the C1- and C13-rings, i.e. are syn, with that of the C7-ring being anti.
As mentioned above, the structure of (I) has been reported previously in an orthorhombic form in two separate determinations (Kerr et al., 1977; Reibenspies et al., 1996). Data from the more recent determination, measured at 163 K (Reibenspies et al., 1996), are included in Table 1. The major difference in (II) is that the molecule lies on a crystallographic mirror plane; the 2 × syn plus 1 × anti-conformation of the methine-H atoms with respect to the thione-S atom persists. In (II), the P—C bond lengths are equal within experimental error. However, differences are apparent in the bond angles subtended at the PV centre whereby the angles in (II) span a wider range, i.e. 8.5°, cf. 6.3 ° in (I). Also, the widest angle at the P1 atom in (II) is subtended by the symmetry-related cyclohexyl rings.
An overlay diagram for (I) and (II) is shown in Fig. 2, which highlights the coincidence of the cyclohexyl ring associated with the methine-H atom having the anti-disposition with respect to the thione-S atom. Clearly, there are conformational differences apparent between the cyclohexyl rings related across the pseudo- and crystallographic mirror planes in (I) and (II), respectively.
3. Supramolecular features
The only directional supramolecular interactions in the crystal of (I) identified in PLATON (Spek, 2009) are methine-C—H7⋯S(thione) contacts, i.e. involving the anti-disposed thione-S and methine-H atoms, Table 2. These lead to a linear chain aligned along the a axis as illustrated in Fig. 3a. The chains pack with no directional interactions between them, Fig. 3b.
In the original report of polymorph (II), it was stated `There are no unusual inter-molecular contacts' (Kerr et al., 1977); no comment on the molecular packing was made in the redetermination (Reibenspies et al., 1996). As seen from Fig. 4, supramolecular zigzag chains are evident in the molecular packing of (II), but these are sustained by weak methylene-C—H⋯S(thione) interactions [H⋯Si = 3.027 (2) Å, C⋯Si = 3.938 (2) Å with the angle at H = 159° for (i) 1 + x, y, z] formed on either side of the mirror plane, so the sulfur atom forms two such contacts, and propagate along the a axis.
A more detailed analysis of the molecular packing in (I) and (II) is given in Hirshfeld surface analysis.
4. Hirshfeld surface analysis
In order to gain more insight into the molecular packing found in (I) and (II), the structures were subjected to a Hirshfeld surface analysis which was performed as described in a recent publication (Jotani et al., 2016).
The different shapes of Hirshfeld surfaces mapped over electrostatic potential in Fig. 5 are indicative of the different molecular conformations adopted by the cyclohexane rings in (I) and (II). A pair of bright-red spots appearing on the Hirshfeld surface mapped over dnorm near methine-H7 and thione-S1 for (I), Fig. 6, on the extremities of the molecule represent the donor and acceptor of the C—H⋯S interaction, Table 2. They are viewed as the respective blue (positive) and red (negative) regions on the Hirshfeld surface mapped over electrostatic potential, Fig. 5. The absence of characteristic spots on the dnorm-mapped Hirshfeld surfaces in the orthorhombic polymorph (II) (not shown) indicates no similar interactions within the sum of the van der Waals radii; see below. The immediate environments about reference molecules of (I) and (II) within the dnorm-mapped Hirshfeld surfaces showing intermolecular C—H⋯S interactions are displayed in Fig. 7a and b, respectively. In the crystal of (II), the zigzag chain of weak intermolecular methylene-C—H⋯S(thione) contacts on either side of the crystallographic mirror plane is viewed as the pair of red dashed lines in Fig. 7b (see above).
The overall two-dimensional fingerprint plots for (I) and (II), and those delineated into H⋯H and S⋯H/H⋯S contacts (McKinnon et al., 2007) are illustrated in Fig. 8. It is interesting to note that in both polymorphs only sulfur and hydrogen atoms lie on the periphery of the Hirshfeld surfaces and contribute to interatomic contacts such as they are; the percentage contributions are as quantified in Table 3. The different relative orientations of the cyclohexane rings in the two forms are also evident through the distinct distribution of points in their respective two-dimensional fingerprint plots, Fig. 8a. In particular for (II), Fig. 8a, the top region, corresponding to donor interactions is stunted with respect to the lower, acceptor region. For (I), a pair of small peaks at de + di < 2.4 Å in the fingerprint plot delineated into H⋯H contacts, Fig. 8b, show the contribution from short interatomic H⋯H contacts in the molecular packing, Table 4. This contrasts the situation for (II), where the pair of peaks occur at de + di > 2.4 Å, i.e. at separations greater than the sum of van der Waals radii. The relative strength of the intermolecular C—H⋯S interactions in (I) and (II) are characterized from the fingerprint plots delineated into S⋯H/H⋯S contacts, Fig. 8c, through the pair of spikes at de + di ∼ 2.7 Å and de + di ∼ 3.1 Å, respectively. The asymmetric distribution of points in the fingerprint plot delineated into S⋯H/H⋯S contacts for (II) in Fig. 8c is the result of the orientation of the cyclohexane rings with respect to the crystallographic mirror plane. The upper region, corresponding to donor H⋯S contacts, contributes 4.7% to the surface cf. 6.5% in the lower region, corresponding to S⋯H acceptor contacts.
|
|
The similarity in the molecular packing of (I) and (II) is reflected in the similarity in the physiochemical data collated in Table 5 and calculated in Crystal Explorer (Wolff et al., 2012) and PLATON (Spek, 2009). While it is noted the values are very close for (I) and (II) (Table 5), the volume of the molecule in (I) is slightly greater than that in (II), as is the surface area. However, the molecule in (II) is marginally more globular and reflecting the lack of directional interactions between molecules, allowing a closer approach, the density is greater than in (I). Nevertheless, the packing efficiency is marginally greater in (I), probably reflecting the lack of symmetry in the molecule cf. (I).
|
5. Database survey
There are a number of triorganophosphane sulfide structures in the crystallographic literature (Groom et al., 2016) with those conforming to the general formula R3P=S being summarized here. Thus, structures have been described with fractional atomic coordinates, for example with R = Me (Tasker et al., 2005), iPr (Staples & Segal, 2001), tBu (Steinberger et al., 2001), Ph (Foces-Foces & Llamas-Saiz, 1998; monoclinic polymorph), Ph (Ziemer et al., 2000; triclinic polymorph), 2-tolyl (Cameron & Dahlèn, 1975), 3-tolyl (Cameron et al., 1978), 4-FPh (Barnes et al., 2007), 2-(Me2NCH2)3Ph (Rotar et al., 2010), 2,4,6-Me3Ph (Garland et al., 2013) and 2,4,6-(OMe)3Ph (Finnen et al., 1994). Selected geometric data for these structures along with those for (I) and (II) are collected in Table 6. The R = Me and iPr molecules have crystallographic mirror symmetry as for (II) whereas the R = tBu compound has crystallographically imposed threefold symmetry. Two polymorphs have been found for R = Ph, and each of these features two independent molecules in the asymmetric unit.
|
The longest P=S bond length, i.e. 1.9748 (13) Å, is found in sterically encumbered (2,4,6-Me3Ph)3P=S (Garland et al., 2013). That steric effects are not the only factors influencing the magnitude of the P=S bond length is realized in the structure of Me3P=S, with small, electron-donating groups, which has the second longest P=S bond length across the series. The comments on the lack of definitive trends in the S—P—C and C—P—C bond angles made above for (I) and (II) hold true across the series although, generally, the former are wider than the latter. Interestingly, in the threefold symmetric tBu3P=S structure, all angles are about 109°.
6. Synthesis and crystallization
The title compound (I) is an unexpected product from the in situ reaction of (Cy3P)2AgCl with Na[S2CNEt2] in a 2:1 ratio. The preparation was as follows: Cy3P (Sigma–Aldrich; 0.6 mmol, 0.196 g) dissolved in acetone (20 ml) was added to an acetone solution (20 ml) of AgCl (Sigma–Aldrich; 0.3 mmol, 0.05 g) at room temperature. Then, Na[S2CNEt2] (BDH, 0.3 mmol, 0.08 g) in acetone (20 ml) was added to the reaction mixture followed by stirring for 4 h. The resulting mixture was filtered, covered to exclude light and left for evaporation at room temperature. Colourless crystals were obtained after four months. Yield: 0.132 g (55%), m.p.: 437–440 K. IR (cm−1): ν(P=S) 624 (s).
7. Refinement
Crystal data, data collection and structure . Carbon-bound H atoms were placed in calculated positions (C—H = 0.99–1.00 Å) and were included in the in the riding-model approximation, with Uiso(H) set to 1.2Ueq(C).
details are summarized in Table 7
|
Supporting information
CCDC reference: 1536014
https://doi.org/10.1107/S205698901700353X/hb7665sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901700353X/hb7665Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S205698901700353X/hb7665Isup3.cml
Data collection: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); cell
CrysAlis PRO (Rigaku Oxford Diffraction, 2015); data reduction: CrysAlis PRO (Rigaku Oxford Diffraction, 2015); 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).C18H33PS | Z = 2 |
Mr = 312.47 | F(000) = 344 |
Triclinic, P1 | Dx = 1.170 Mg m−3 |
a = 6.6400 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.8089 (9) Å | Cell parameters from 4800 reflections |
c = 12.8818 (10) Å | θ = 3.7–29.5° |
α = 103.430 (7)° | µ = 0.26 mm−1 |
β = 98.467 (7)° | T = 100 K |
γ = 91.912 (7)° | Prism, colourless |
V = 887.26 (12) Å3 | 0.40 × 0.20 × 0.17 mm |
Agilent SuperNova, Dual, Mo at zero, AtlasS2 diffractometer | 4208 independent reflections |
Radiation source: micro-focus sealed X-ray tube, SuperNova (Mo) X-ray Source | 3739 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.022 |
ω scans | θmax = 29.7°, θmin = 2.8° |
Absorption correction: multi-scan (CrysAlis PRO; Rigaku Oxford Diffraction, 2015) | h = −8→9 |
Tmin = 0.926, Tmax = 1.000 | k = −13→12 |
8658 measured reflections | l = −16→17 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0433P)2 + 0.4808P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
4208 reflections | Δρmax = 0.47 e Å−3 |
181 parameters | Δρmin = −0.35 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 | ||
S1 | 0.28983 (5) | 0.28303 (4) | 0.60522 (3) | 0.02266 (11) | |
P1 | 0.58024 (5) | 0.29616 (3) | 0.66467 (3) | 0.01328 (10) | |
C1 | 0.6361 (2) | 0.17062 (13) | 0.73806 (11) | 0.0155 (3) | |
H1 | 0.5711 | 0.0898 | 0.6877 | 0.019* | |
C2 | 0.8619 (2) | 0.14502 (14) | 0.76697 (12) | 0.0176 (3) | |
H2A | 0.9269 | 0.1300 | 0.7012 | 0.021* | |
H2B | 0.9347 | 0.2205 | 0.8197 | 0.021* | |
C3 | 0.8780 (2) | 0.02835 (15) | 0.81546 (12) | 0.0215 (3) | |
H3A | 0.8173 | −0.0484 | 0.7599 | 0.026* | |
H3B | 1.0238 | 0.0157 | 0.8371 | 0.026* | |
C4 | 0.7689 (2) | 0.04367 (15) | 0.91382 (12) | 0.0215 (3) | |
H4A | 0.8396 | 0.1143 | 0.9727 | 0.026* | |
H4B | 0.7751 | −0.0355 | 0.9400 | 0.026* | |
C5 | 0.5457 (2) | 0.07171 (15) | 0.88609 (12) | 0.0210 (3) | |
H5A | 0.4708 | −0.0033 | 0.8337 | 0.025* | |
H5B | 0.4820 | 0.0873 | 0.9524 | 0.025* | |
C6 | 0.5286 (2) | 0.18808 (14) | 0.83768 (12) | 0.0183 (3) | |
H6A | 0.5910 | 0.2649 | 0.8927 | 0.022* | |
H6B | 0.3828 | 0.2012 | 0.8168 | 0.022* | |
C7 | 0.7413 (2) | 0.27103 (13) | 0.55847 (11) | 0.0151 (3) | |
H7 | 0.8872 | 0.2799 | 0.5940 | 0.018* | |
C8 | 0.7119 (2) | 0.37069 (14) | 0.49033 (12) | 0.0209 (3) | |
H8A | 0.5663 | 0.3672 | 0.4581 | 0.025* | |
H8B | 0.7496 | 0.4570 | 0.5376 | 0.025* | |
C9 | 0.8424 (3) | 0.34686 (15) | 0.40031 (12) | 0.0252 (3) | |
H9A | 0.8170 | 0.4105 | 0.3565 | 0.030* | |
H9B | 0.9886 | 0.3571 | 0.4325 | 0.030* | |
C10 | 0.7926 (3) | 0.21275 (15) | 0.32763 (12) | 0.0254 (3) | |
H10A | 0.8810 | 0.1984 | 0.2710 | 0.030* | |
H10B | 0.6488 | 0.2042 | 0.2915 | 0.030* | |
C11 | 0.8260 (2) | 0.11291 (14) | 0.39418 (12) | 0.0203 (3) | |
H11A | 0.7889 | 0.0267 | 0.3465 | 0.024* | |
H11B | 0.9721 | 0.1172 | 0.4257 | 0.024* | |
C12 | 0.6967 (2) | 0.13517 (14) | 0.48499 (11) | 0.0178 (3) | |
H12A | 0.7261 | 0.0720 | 0.5290 | 0.021* | |
H12B | 0.5503 | 0.1224 | 0.4532 | 0.021* | |
C13 | 0.6633 (2) | 0.45629 (13) | 0.75178 (11) | 0.0155 (3) | |
H13 | 0.6674 | 0.5136 | 0.7012 | 0.019* | |
C14 | 0.5091 (2) | 0.51104 (15) | 0.82558 (12) | 0.0202 (3) | |
H14A | 0.3716 | 0.5046 | 0.7820 | 0.024* | |
H14B | 0.5027 | 0.4609 | 0.8804 | 0.024* | |
C15 | 0.5722 (2) | 0.65042 (15) | 0.88193 (12) | 0.0219 (3) | |
H15A | 0.5689 | 0.7014 | 0.8271 | 0.026* | |
H15B | 0.4736 | 0.6838 | 0.9304 | 0.026* | |
C16 | 0.7857 (2) | 0.66490 (14) | 0.94750 (12) | 0.0205 (3) | |
H16A | 0.7863 | 0.6202 | 1.0064 | 0.025* | |
H16B | 0.8246 | 0.7563 | 0.9807 | 0.025* | |
C17 | 0.9411 (2) | 0.60985 (15) | 0.87601 (13) | 0.0242 (3) | |
H17A | 1.0768 | 0.6154 | 0.9212 | 0.029* | |
H17B | 0.9516 | 0.6609 | 0.8222 | 0.029* | |
C18 | 0.8796 (2) | 0.47037 (14) | 0.81713 (12) | 0.0200 (3) | |
H18A | 0.8846 | 0.4175 | 0.8706 | 0.024* | |
H18B | 0.9779 | 0.4392 | 0.7678 | 0.024* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.01585 (19) | 0.0258 (2) | 0.0254 (2) | 0.00077 (14) | 0.00114 (14) | 0.00571 (15) |
P1 | 0.01333 (18) | 0.01384 (18) | 0.01275 (17) | 0.00045 (12) | 0.00201 (12) | 0.00351 (13) |
C1 | 0.0171 (7) | 0.0152 (7) | 0.0156 (6) | 0.0008 (5) | 0.0049 (5) | 0.0050 (5) |
C2 | 0.0175 (7) | 0.0190 (7) | 0.0197 (7) | 0.0038 (5) | 0.0062 (5) | 0.0090 (6) |
C3 | 0.0237 (8) | 0.0200 (8) | 0.0248 (8) | 0.0066 (6) | 0.0081 (6) | 0.0101 (6) |
C4 | 0.0263 (8) | 0.0204 (8) | 0.0222 (7) | 0.0040 (6) | 0.0074 (6) | 0.0116 (6) |
C5 | 0.0240 (8) | 0.0209 (8) | 0.0217 (7) | 0.0008 (6) | 0.0083 (6) | 0.0095 (6) |
C6 | 0.0197 (7) | 0.0197 (7) | 0.0189 (7) | 0.0034 (5) | 0.0074 (5) | 0.0084 (6) |
C7 | 0.0200 (7) | 0.0129 (7) | 0.0130 (6) | 0.0013 (5) | 0.0047 (5) | 0.0026 (5) |
C8 | 0.0334 (8) | 0.0140 (7) | 0.0174 (7) | 0.0034 (6) | 0.0080 (6) | 0.0054 (5) |
C9 | 0.0427 (10) | 0.0172 (8) | 0.0207 (7) | 0.0040 (6) | 0.0140 (7) | 0.0089 (6) |
C10 | 0.0429 (10) | 0.0208 (8) | 0.0152 (7) | 0.0069 (7) | 0.0094 (6) | 0.0061 (6) |
C11 | 0.0293 (8) | 0.0151 (7) | 0.0169 (7) | 0.0029 (6) | 0.0066 (6) | 0.0026 (5) |
C12 | 0.0249 (7) | 0.0129 (7) | 0.0165 (7) | 0.0009 (5) | 0.0058 (5) | 0.0039 (5) |
C13 | 0.0162 (7) | 0.0158 (7) | 0.0146 (6) | 0.0008 (5) | 0.0029 (5) | 0.0034 (5) |
C14 | 0.0166 (7) | 0.0219 (8) | 0.0194 (7) | 0.0024 (5) | 0.0032 (5) | −0.0006 (6) |
C15 | 0.0252 (8) | 0.0205 (8) | 0.0185 (7) | 0.0075 (6) | 0.0025 (6) | 0.0012 (6) |
C16 | 0.0250 (8) | 0.0150 (7) | 0.0194 (7) | −0.0003 (5) | 0.0024 (6) | 0.0004 (5) |
C17 | 0.0205 (8) | 0.0203 (8) | 0.0282 (8) | −0.0052 (6) | 0.0047 (6) | −0.0011 (6) |
C18 | 0.0164 (7) | 0.0177 (7) | 0.0233 (7) | −0.0001 (5) | 0.0028 (6) | 0.0003 (6) |
S1—P1 | 1.9548 (5) | C9—H9A | 0.9900 |
P1—C1 | 1.8435 (14) | C9—H9B | 0.9900 |
P1—C7 | 1.8350 (14) | C10—C11 | 1.529 (2) |
P1—C13 | 1.8468 (15) | C10—H10A | 0.9900 |
C1—C6 | 1.5356 (18) | C10—H10B | 0.9900 |
C1—C2 | 1.5408 (19) | C11—C12 | 1.5302 (19) |
C1—H1 | 1.0000 | C11—H11A | 0.9900 |
C2—C3 | 1.532 (2) | C11—H11B | 0.9900 |
C2—H2A | 0.9900 | C12—H12A | 0.9900 |
C2—H2B | 0.9900 | C12—H12B | 0.9900 |
C3—C4 | 1.530 (2) | C13—C18 | 1.5376 (19) |
C3—H3A | 0.9900 | C13—C14 | 1.5391 (19) |
C3—H3B | 0.9900 | C13—H13 | 1.0000 |
C4—C5 | 1.530 (2) | C14—C15 | 1.527 (2) |
C4—H4A | 0.9900 | C14—H14A | 0.9900 |
C4—H4B | 0.9900 | C14—H14B | 0.9900 |
C5—C6 | 1.529 (2) | C15—C16 | 1.523 (2) |
C5—H5A | 0.9900 | C15—H15A | 0.9900 |
C5—H5B | 0.9900 | C15—H15B | 0.9900 |
C6—H6A | 0.9900 | C16—C17 | 1.527 (2) |
C6—H6B | 0.9900 | C16—H16A | 0.9900 |
C7—C8 | 1.540 (2) | C16—H16B | 0.9900 |
C7—C12 | 1.5437 (19) | C17—C18 | 1.533 (2) |
C7—H7 | 1.0000 | C17—H17A | 0.9900 |
C8—C9 | 1.528 (2) | C17—H17B | 0.9900 |
C8—H8A | 0.9900 | C18—H18A | 0.9900 |
C8—H8B | 0.9900 | C18—H18B | 0.9900 |
C9—C10 | 1.528 (2) | ||
C7—P1—C1 | 105.82 (6) | C10—C9—H9B | 109.5 |
C7—P1—C13 | 105.70 (6) | C8—C9—H9B | 109.5 |
C1—P1—C13 | 111.43 (6) | H9A—C9—H9B | 108.1 |
C7—P1—S1 | 112.11 (5) | C9—C10—C11 | 110.38 (12) |
C1—P1—S1 | 109.99 (5) | C9—C10—H10A | 109.6 |
C13—P1—S1 | 111.60 (5) | C11—C10—H10A | 109.6 |
C6—C1—C2 | 110.75 (11) | C9—C10—H10B | 109.6 |
C6—C1—P1 | 111.78 (10) | C11—C10—H10B | 109.6 |
C2—C1—P1 | 117.32 (10) | H10A—C10—H10B | 108.1 |
C6—C1—H1 | 105.3 | C12—C11—C10 | 110.93 (12) |
C2—C1—H1 | 105.3 | C12—C11—H11A | 109.5 |
P1—C1—H1 | 105.3 | C10—C11—H11A | 109.5 |
C3—C2—C1 | 110.13 (12) | C12—C11—H11B | 109.5 |
C3—C2—H2A | 109.6 | C10—C11—H11B | 109.5 |
C1—C2—H2A | 109.6 | H11A—C11—H11B | 108.0 |
C3—C2—H2B | 109.6 | C11—C12—C7 | 111.43 (12) |
C1—C2—H2B | 109.6 | C11—C12—H12A | 109.3 |
H2A—C2—H2B | 108.1 | C7—C12—H12A | 109.3 |
C4—C3—C2 | 111.72 (12) | C11—C12—H12B | 109.3 |
C4—C3—H3A | 109.3 | C7—C12—H12B | 109.3 |
C2—C3—H3A | 109.3 | H12A—C12—H12B | 108.0 |
C4—C3—H3B | 109.3 | C18—C13—C14 | 110.45 (11) |
C2—C3—H3B | 109.3 | C18—C13—P1 | 115.68 (10) |
H3A—C3—H3B | 107.9 | C14—C13—P1 | 113.42 (10) |
C3—C4—C5 | 111.30 (12) | C18—C13—H13 | 105.4 |
C3—C4—H4A | 109.4 | C14—C13—H13 | 105.4 |
C5—C4—H4A | 109.4 | P1—C13—H13 | 105.4 |
C3—C4—H4B | 109.4 | C15—C14—C13 | 110.25 (12) |
C5—C4—H4B | 109.4 | C15—C14—H14A | 109.6 |
H4A—C4—H4B | 108.0 | C13—C14—H14A | 109.6 |
C6—C5—C4 | 111.10 (12) | C15—C14—H14B | 109.6 |
C6—C5—H5A | 109.4 | C13—C14—H14B | 109.6 |
C4—C5—H5A | 109.4 | H14A—C14—H14B | 108.1 |
C6—C5—H5B | 109.4 | C16—C15—C14 | 111.29 (12) |
C4—C5—H5B | 109.4 | C16—C15—H15A | 109.4 |
H5A—C5—H5B | 108.0 | C14—C15—H15A | 109.4 |
C5—C6—C1 | 111.04 (12) | C16—C15—H15B | 109.4 |
C5—C6—H6A | 109.4 | C14—C15—H15B | 109.4 |
C1—C6—H6A | 109.4 | H15A—C15—H15B | 108.0 |
C5—C6—H6B | 109.4 | C15—C16—C17 | 110.86 (12) |
C1—C6—H6B | 109.4 | C15—C16—H16A | 109.5 |
H6A—C6—H6B | 108.0 | C17—C16—H16A | 109.5 |
C8—C7—C12 | 110.18 (11) | C15—C16—H16B | 109.5 |
C8—C7—P1 | 111.69 (10) | C17—C16—H16B | 109.5 |
C12—C7—P1 | 110.46 (10) | H16A—C16—H16B | 108.1 |
C8—C7—H7 | 108.1 | C16—C17—C18 | 111.30 (12) |
C12—C7—H7 | 108.1 | C16—C17—H17A | 109.4 |
P1—C7—H7 | 108.1 | C18—C17—H17A | 109.4 |
C9—C8—C7 | 111.28 (12) | C16—C17—H17B | 109.4 |
C9—C8—H8A | 109.4 | C18—C17—H17B | 109.4 |
C7—C8—H8A | 109.4 | H17A—C17—H17B | 108.0 |
C9—C8—H8B | 109.4 | C17—C18—C13 | 111.07 (12) |
C7—C8—H8B | 109.4 | C17—C18—H18A | 109.4 |
H8A—C8—H8B | 108.0 | C13—C18—H18A | 109.4 |
C10—C9—C8 | 110.78 (13) | C17—C18—H18B | 109.4 |
C10—C9—H9A | 109.5 | C13—C18—H18B | 109.4 |
C8—C9—H9A | 109.5 | H18A—C18—H18B | 108.0 |
C7—P1—C1—C6 | 173.93 (10) | P1—C7—C8—C9 | −178.51 (10) |
C13—P1—C1—C6 | 59.51 (11) | C7—C8—C9—C10 | 57.32 (17) |
S1—P1—C1—C6 | −64.79 (10) | C8—C9—C10—C11 | −57.82 (18) |
C7—P1—C1—C2 | 44.45 (12) | C9—C10—C11—C12 | 57.32 (17) |
C13—P1—C1—C2 | −69.97 (12) | C10—C11—C12—C7 | −56.28 (16) |
S1—P1—C1—C2 | 165.73 (9) | C8—C7—C12—C11 | 54.86 (16) |
C6—C1—C2—C3 | 56.61 (16) | P1—C7—C12—C11 | 178.74 (10) |
P1—C1—C2—C3 | −173.43 (10) | C7—P1—C13—C18 | −67.43 (12) |
C1—C2—C3—C4 | −56.03 (16) | C1—P1—C13—C18 | 47.06 (12) |
C2—C3—C4—C5 | 55.46 (17) | S1—P1—C13—C18 | 170.45 (9) |
C3—C4—C5—C6 | −54.99 (17) | C7—P1—C13—C14 | 163.46 (10) |
C4—C5—C6—C1 | 55.98 (16) | C1—P1—C13—C14 | −82.05 (11) |
C2—C1—C6—C5 | −57.02 (16) | S1—P1—C13—C14 | 41.34 (11) |
P1—C1—C6—C5 | 170.15 (10) | C18—C13—C14—C15 | 56.93 (16) |
C1—P1—C7—C8 | −179.57 (10) | P1—C13—C14—C15 | −171.34 (10) |
C13—P1—C7—C8 | −61.26 (11) | C13—C14—C15—C16 | −57.70 (16) |
S1—P1—C7—C8 | 60.53 (11) | C14—C15—C16—C17 | 56.93 (17) |
C1—P1—C7—C12 | 57.43 (11) | C15—C16—C17—C18 | −55.49 (18) |
C13—P1—C7—C12 | 175.73 (9) | C16—C17—C18—C13 | 55.34 (17) |
S1—P1—C7—C12 | −62.47 (10) | C14—C13—C18—C17 | −55.97 (16) |
C12—C7—C8—C9 | −55.35 (16) | P1—C13—C18—C17 | 173.48 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
C7—H7···S1i | 1.00 | 2.65 | 3.5961 (14) | 157 |
Symmetry code: (i) x+1, y, z. |
Parameter | triclinic polymorph | orthorhombic polymorpha |
P1═S1 | 1.9548 (5) | 1.9612 (11) |
P1—C1 | 1.8435 (14) | 1.842 (3) |
P1—C7 | 1.8350 (14) | 1.836 (2) |
P1—C13 | 1.8468 (15) | 1.836 (2) |
S1—P1—C1 | 109.99 (5) | 112.16 (11) |
S1—P1—C7 | 112.11 (5) | 110.15 (7) |
S1—P1—C13 | 111.60 (5) | 110.15 (7) |
C1—P1—C7 | 105.82 (6) | 105.22 (9) |
C1—P1—C13 | 105.70 (6) | 105.22 (9) |
C7—P1—C13 | 111.43 (6) | 113.80 (10) |
Notes: (a) the molecule has crystallographic mirror symmetry with the S1, P1 and C1 atoms lying on the plane. |
Contact | % contribution in (I) | % contribution in (II) |
H···H | 89.8 | 88.8 |
S···H/H···S | 10.2 | 11.2 |
Contact | distance | symmetry operation |
H6A···H15B | 2.32 | 1 - x, 1 - y, 2 - z |
H10B···H15A | 2.37 | 1 - x, 1 - y, 1 - z |
Property | (I) | (II) |
Volume, V (Å3) | 436.83 | 430.96 |
Surface area, A (Å2) | 351.03 | 345.83 |
A:V (Å-1) | 0.804 | 0.802 |
Globularity, G | 0.793 | 0.798 |
Asphericity, Ω | 0.051 | 0.046 |
Density (g cm-3) | 1.170 | 1.186 |
Packing index (%) | 68.6 | 68.4 |
R | P═S | S—P—C | C—P—C | Reference |
Mea | 1.9664 (7) | 112.88 (6)–113.22 (8) | 105.33 (8)–106.53 (8) | Tasker et al., 2005 |
iPra | 1.926 (3) | 110.08 (19)–112.3 (2) | 103.88 (19)–116.3 (4) | Staples et al., 2001 |
tBub | 1.9627 (15) | 109.29 (14) | 109.65 (19) | Steinberger et al., 2001 |
Phc,d | 1.9554 (7) | 112.16 (6)–113.47 (6) | 103.70 (8)–107.76 (8) | Foces-Foces & Llamas-Saiz, 1998 |
1.9547 (7) | 112.28 (7)–113.67 (6) | 103.12 (8)–107.53 (9) | ||
Phd,e | 1.9544 (9) | 112.47 (7)–113.99 (7) | 103.43 (8)–106.83 (8) | Ziemer et al., 2000 |
1.9529 (8) | 111.97 (7)–113.19 (7) | 103.61 (8)–107.38 (8) | ||
2-tolyld | 1.953 (6) | 110.7 (3)–114.2 (3) | 101.4 (3)–110.6 (4) | Cameron & Dahlèn, 1975 |
1.942 (5) | 111.6 (2)–114.3 (2) | 104.9 (3)–107.9 (3) | ||
3-tolyl | 1.937 (4) | 112.1 (8)–112.6 (4) | 105.5 (7)–108.2 (10) | Cameron et al., 1978 |
4-FPh | 1.9540 (9) | 113.27 (8)–113.59 (8) | 104.97 (10)–105.92 (10) | Barnes et al., 2007 |
2,4,6-Me3Ph | 1.9748 (13) | 107.32 (11)–109.49 (12) | 108.90 (16)–112.45 (15) | Garland et al., 2013 |
2,4,6-(OMe)3Ph | 1.9619 (12) | 109.22 (11)–116.15 (11) | 100.77 (14)–110.58 (14) | Finnen et al., 1994 |
2-(Me2NCH2)3Ph | 1.9622 (17) | 110.66 (8)–116.15 (10) | 103.51 (13)–106.33 (11) | Rotar et al., 2010 |
Cya,f | 1.9612 (11) | 110.15 (7)–112.16 (11) | 105.22 (9)–113.80 (10) | Reibenspies et al., 1996 |
Cye | 1.9548 (5) | 109.99 (5)–112.11 (5) | 105.70 (6)–111.43 (6) | this work |
Notes: (a) The molecule has crystallographic mirror symmetry with the S1, P1 and C1 atoms lying on the plane; (b) the molecule has crystallographic threefold symmetry with the S1 and P1 atoms lying on the axis; (c) monoclinic polymorph; (d) two independent molecules in the asymmetric unit; (e) triclinic polymorph; (f) orthorhombic polymorph. |
Footnotes
‡Additional correspondence author, e-mail: mmjotani@rediffmail.com.
Acknowledgements
The authors are grateful to Sunway University (INT-RRO-2017–096) for supporting this research.
References
Altaf, M., Monim-ul-Mehboob, M., Seliman, A. A. A., Sohail, M., Wazeer, M. I. M., Isab, A. A., Li, L., Dhuna, V., Bhatia, G. & Dhuna, K. (2015). Eur. J. Med. Chem. 95, 464–472. Web of Science CSD CrossRef CAS PubMed Google Scholar
Barnes, N. A., Godfrey, S. M., Halton, R. T. A., Khan, R. Z., Jackson, S. L. & Pritchard, R. G. (2007). Polyhedron, 26, 4294–4302. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Cameron, T. S. & Dahlèn, B. (1975). J. Chem. Soc. Perkin Trans. 2, pp. 1737–1751. CSD CrossRef Web of Science Google Scholar
Cameron, T. S., Howlett, K. D. & Miller, K. (1978). Acta Cryst. B34, 1639–1644. CSD CrossRef CAS IUCr Journals Web of Science Google Scholar
Chen, B.-J., Jamaludin, N. S., Khoo, C.-H., See, T.-H., Sim, J.-H., Cheah, Y.-K., Halim, S. N. A., Seng, H.-L. & Tiekink, E. R. T. (2016). J. Inorg. Biochem. 163, 68–80. Web of Science CrossRef CAS PubMed Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Finnen, D. C. & Pinkerton, A. A. (1994). Phosphorus Sulfur Silicon Relat. Elem. 90, 11–19. CSD CrossRef CAS Web of Science Google Scholar
Foces-Foces, C. & Llamas-Saiz, A. L. (1998). Acta Cryst. (1998). C54, IUC9800013. Google Scholar
Gandin, V., Fernandes, A. P., Rigobello, M. P., Dani, B., Sorrentino, F., Tisato, F., Björnstedt, M., Bindoli, A., Sturaro, A., Rella, R. & Marzano, C. (2010). Biochem. Pharmacol. 79, 90–101. Web of Science CrossRef PubMed CAS Google Scholar
Gans, J. & Shalloway, D. (2001). J. Mol. Graphics Modell. 19, 557–559. Web of Science CrossRef CAS Google Scholar
Garland, J., Slawin, A. M. Z. & Woollins, J. D. (2013). Private communication (refcode ZIVRAZ). CCDC, Cambridge, England. Google Scholar
Glišić, B. Đ. & Djuran, M. I. (2014). Dalton Trans. 43, 5950–5969. Web of Science PubMed Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals Google Scholar
Hogarth, G. (2012). Mini Rev. Med. Chem. 12, 1202–1215. CrossRef CAS PubMed Google Scholar
Jamaludin, N. S., Goh, Z.-J., Cheah, Y. K., Ang, K.-P., Sim, J. H., Khoo, C. H., Fairuz, Z. A., Halim, S. N. A., Ng, S. W., Seng, H.-L. & Tiekink, E. R. T. (2013). Eur. J. Med. Chem. 67, 127–141. Web of Science CSD CrossRef CAS PubMed Google Scholar
Jamaludin, N. S., Halim, S. N. A., Khoo, C.-H., Chen, B.-J., See, T.-H., Sim, J.-H., Cheah, Y.-K., Seng, H.-L. & Tiekink, E. R. T. (2016). Z. Kristallogr. 231, 341–349. CAS Google Scholar
Jotani, M. M., Poplaukhin, P., Arman, H. D. & Tiekink, E. R. T. (2016). Acta Cryst. E72, 1085–1092. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kerr, K. A., Boorman, P. M., Misener, B. S. & van Roode, J. H. G. (1977). Can. J. Chem. 55, 3081–3085. CSD CrossRef CAS Web of Science Google Scholar
Keter, F. K., Guzei, I. A., Nell, M., van Zyl, W. E. & Darkwa, J. (2014). Inorg. Chem. 53, 2058–2067. Web of Science CSD CrossRef CAS PubMed Google Scholar
McKinnon, J. J., Jayatilaka, D. & Spackman, M. A. (2007). Chem. Commun. pp. 3814–3816. Web of Science CrossRef Google Scholar
Reibenspies, J. H., Draper, J. D., Struck, G. & Darensbourg, D. J. (1996). Z. Kristallogr. 211, 400. Google Scholar
Rigaku Oxford Diffraction (2015). CrysAlis PRO. Agilent Technologies Inc., Santa Clara, CA, USA. Google Scholar
Ronconi, L., Giovagnini, L., Marzano, C., Bettìo, F., Graziani, R., Pilloni, G. & Fregona, D. (2005). Inorg. Chem. 44, 1867–1881. Web of Science CrossRef PubMed CAS Google Scholar
Rotar, A., Covaci, A., Pop, A. & Silvestru, A. (2010). Rev. Roum. Chim. 55, 823–829. CAS 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
Sim, J.-H., Jamaludin, N. S., Khoo, C.-H., Cheah, Y.-K., Halim, S. N. A., Seng, H.-L. & Tiekink, E. R. T. (2014). Gold Bull. 47, 225–236. Web of Science CrossRef CAS Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Staples, R. J. & Segal, B. M. (2001). Acta Cryst. E57, o432–o433. Web of Science CSD CrossRef IUCr Journals Google Scholar
Steinberger, H.-U., Ziemer, B. & Meisel, M. (2001). Acta Cryst. C57, 835–837. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Tasker, P., Coventry, D., Parsons, S. & Messenger, D. (2005). Private communication (refcode METPHS01). CCDC, Cambridge, England. Google Scholar
Vos, D. de, Ho, S. Y. & Tiekink, E. R. T. (2004). Bioinorg. Chem. Appl. 2, 141–154. Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wolff, S. K., Grimwood, D. J., McKinnon, J. J., Turner, M. J., Jayatilaka, D. & Spackman, M. A. (2012). Crystal Explorer. The University of Western Australia. Google Scholar
Ziemer, B., Rabis, A. & Steinberger, H.-U. (2000). Acta Cryst. C56, e58–e59. Web of Science CSD 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.