Undeca­carbon­yl[(4-methyl­sulfanylphen­yl)di­phenyl­phosphane]triruthenium(0): crystal structure and Hirshfeld surface analysis

Shawkataly, O. bin; Abdelnasir, H.M.H.; Sirat, S.S.; Jotani, M.M.; Tiekink, E.R.T.

doi:10.1107/S2056989018006989

research communications

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ISSN: 2056-9890

Volume 74| Part 6| June 2018| Pages 791-795

https://doi.org/10.1107/S2056989018006989

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Undecacarbonyl[(4-methylsulfanylphenyl)diphenylphosphane]triruthenium(0): crystal structure and Hirshfeld surface analysis

Omar bin Shawkataly,^a ‡ Hafiz Malik Hussien Abdelnasir,^b Siti Syaida Sirat,^a Mukesh M. Jotani ^c and Edward R. T. Tiekink ^d ^*

^aChemical Sciences Programme, School of Distance Education, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia, ^bDepartment of Chemistry, Alzaiem Alazhari University, 1933, Khartoum, Sudan, ^cDepartment of Physics, Bhavan's Sheth R. A. College of Science, Ahmedabad, Gujarat 380001, India, and ^dResearch 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

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 3 May 2018; accepted 8 May 2018; online 15 May 2018)

The title cluster compound, [Ru₃(C₁₉H₁₇PS)(CO)₁₁], comprises a triangle of Ru⁰ atoms, two of which are bonded to four carbonyl ligands. The third metal atom is bound to three carbonyl ligands and the phosphane-P atom of a dissymmetric phosphane ligand, PPh₂(C₆H₄SMe-4); no Ru⋯S interactions are observed. The phosphane occupies an equatorial position and its proximity to an Ru—Ru edge results in the elongation of this bond with respect to the others [2.8933 (2) Å cf. 2.8575 (2) and 2.8594 (3) Å]. In the crystal, phenyl-C—H⋯O(carbonyl) and carbonyl-O⋯O(carbonyl) [2.817 (2) Å] interactions combine to form a supramolecular chain propagating along [111]; the chains pack without directional interactions between them. The carbonyl-O⋯O(carbonyl) and other weak contacts have an influence upon the Hirshfeld surfaces with O⋯H contacts making the greatest contribution, i.e. 37.4% cf. 15.8% for O⋯O and 15.6% for H⋯H contacts.

Keywords: crystal structure; ruthenium; cluster; carbonyl; Hirshfeld surface analysis.

CCDC reference: 1842044

1. Chemical context

Tertiary phosphanes (PR₃) have played a major role in the formation and subsequent chemistry of metal carbonyl clusters, often relating to the promising catalytic activity of the products (Bruce et al., 2005 ; Shawkataly et al., 2013 ; Park et al., 2016 ). In general, the thermal reaction of Ru₃(CO)₁₂ with PR₃ leads to Ru₃(CO)_12 – n(PR₃)_n, n = 1–4, cluster compounds (Bruce et al., 1988 , 1989 ). The steric and electronic effects of PR₃ often results in the lengthening of Ru—Ru bonds in the Ru₃ triangle as compared with the parent compound, Ru₃(CO)₁₂, thereby making the cluser more reactive (Bruce et al., 1989). The PPh₂C₆H₄SMe ligand is of interest because it contains two different potential donor groups, i.e. P and S, which can result in variable substitution patterns. For example, in the Cu₂₂Se₆(SePh)₁₀[PPh₂(C₆H₄SMe)]₈ cluster, only the P atom of the PPh₂C₆H₄SMe ligand is coordinated to the metal centre while the thiomethyl group remains uncoordinated (Fuhr et al., 2002 ). However, the thiomethyl group can further react with other metal atoms to provide opportunities in surface chemistry (Fuhr et al., 2002). The known crystal structures of triruthenium clusters with the PPh₂(C₆H₄SMe) ligand are surprisingly few in number (Shawkataly et al., 2011a ,b ). Herein, the crystal and molecular structures of the title compound, Ru₃(CO)₁₁PPh₂(C₆H₄SMe-4) (I), are described as well as an analysis of the calculated Hirshfeld surface.

2. Structural commentary

The molecular structure of Ru₃(CO)₁₁PPh₂(C₆H₄SMe-4), (I), is shown in Fig. 1. The molecule comprises an Ru₃ triangle with one Ru centre being bound, equatorially, by the phosphane ligand. The Ru—Ru bond lengths in the Ru₃ triangle are not equivalent with the Ru1—Ru2 bond of 2.8933 (2) Å being longer than the Ru1—Ru3 and Ru2—Ru3 bonds of 2.8575 (2) and 2.8594 (3) Å, respectively. This disparity probably reflects the steric hindrance exerted by the phosphane ligand which occupies the region in the vicinity of the Ru1—Ru2 bond. Some general trends in the geometric parameters involving the carbonyl ligands may be discerned, the relatively high errors in some of the parameters notwithstanding. Thus, the Ru—C bond distances involving carbonyl groups lying in the plane of the Ru₃ ring are generally shorter than those occupying positions perpendicular to the plane, with the respective ranges in Ru—C bond lengths being 1.897 (3)–1.930 (3) Å and 1.937 (2)–1.953 (3) Å. While the Ru—C≡O angles are all close to linear, two distinctive ranges in angles are evident. The Ru—C≡O angles involving carbonyl groups lying in the plane of the Ru₃ ring lie in the range 177.3 (2)–178.7 (2)° while the range for the perpendicularly orientated carbonyl groups is 172.1 (2)–174.6 (2)°. The trend for longer Ru—C distances and greater deviations from linearity of the Ru—C≡O angles for the axial carbonyl ligands, which occupy positions trans to other carbonyl ligands, is consistent with some semi-bridging character for these carbonyl ligands. Thus, the closest intramolecular Ru⋯C(carbonyl) contact of 3.233 (3) Å is formed by the C8-carbonyl ligand which exhibits the maximum deviation from linearity, i.e. 172.1 (2)°.

Figure 1
The molecular structure of (I)

showing the atom-labelling scheme and displacement ellipsoids at the 70% probability level.

3. Supramolecular features

The molecular packing of (I) features phenyl-C—H⋯O(carbonyl) interactions occurring about a centre of inversion and leading to centrosymmetric dimers, Table 1. Connections between the dimers leading to a supramolecular chain along [111] are of the type carbonyl-O⋯O(carbonyl), Fig. 2a. The O3⋯O3ⁱ separation is 2.817 (2) Å, a distance less than the sum of the van der Waals radii of oxygen, i.e. 3.04 Å (Bondi, 1964 ); symmetry operation (i): 1 − x, 1 − y, 1 − z. Such intermolecular O⋯O interactions are examples of homoatomic chalcogen bonding which are rarest for the smaller oxygen atoms (Gleiter et al., 2018 ). The chains pack without directional interactions between them according to the criteria assumed in PLATON (Spek, 2009 ). A view of the unit-cell contents is shown in Fig. 2b.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯O8ⁱ	0.95	2.55	3.238 (3)	129
Symmetry code: (i) -x, -y, -z.

Figure 2
Molecular packing in (I)

: (a) The supramolecular chain sustained by C—H⋯O and O⋯O interactions and (b) a view of the unit-cell contents shown in projection down the b axis. The C—H⋯O and O⋯O interactions are shown as orange and blue dashed lines, respectively.

4. Analysis of the Hirshfeld surface

The Hirshfeld surface calculations of (I) were performed in accordance with a recent publication on a related ruthenium cluster compound (Shawkataly et al., 2017 ). Two views of the Hirshfeld surface mapped over d_norm are shown in Fig. 3. A spot near the O8 atom in Fig. 3a, results from the C21—H⋯O8 interaction (Table 1). The presence of a diminutive red spot near the carbonyl-O3 atom in Fig. 3b reflects the significance of the short O3⋯O3 contact mentioned in Supramolecular features. The intense red spots near the methylsulfanylbenzene-C16 and phenyl-H28 atoms indicate the significance of this short interatomic C⋯H/H⋯C contact (Table 2; calculated in CrystalExplorer3.1 (Wolff et al., 2012 ). In addition, interactions involving several carbonyl groups results in short O⋯O and C⋯O/O⋯C contacts (Table 2) and are characterized as faint red spots in Fig. 3. The Hirshfeld surfaces mapped over the electrostatic potential illustrated in Fig. 4 also reflect the involvement of different atoms in the intermolecular interactions through the appearance of blue and red regions around the participating atoms, and correspond to positive and negative electrostatic potential, respectively. As highlighted in Fig. 4a, an intramolecular carbonyl-C4≡O4⋯Cg(C19–C24) contact is evident. Carbonyl⋯π(arene) interactions are known to be important in the structural chemistry of metal carbonyls (Zukerman-Schpector et al., 2011 ). Here, the O4⋯Cg(C19–C24) separation is 3.850 (3) Å and the angle subtended at the O4 atom is 90.1 (2)°, indicating a side-on (parallel) approach between the residues. The environment about a reference molecule, showing short interatomic O⋯O and C⋯H/H⋯C contacts significant in the molecule packing of (I), is illustrated in Fig. 5.

Table 2
Summary of short interatomic contacts (Å) in (I)

Contact	Distance	Symmetry operation
O3⋯O3	2.817 (2)	1 − x, 1 − y, 1 − z
O6⋯O11	2.986 (3)	1 − x, 1 − y, − z
C3⋯O3	3.150 (3)	1 − x, 1 − y, 1 − z
C7⋯O9	3.088 (3)	1 − x, 1 − y, − z
C9⋯O8	3.137 (3)	−x, 1 − y, − z
C17⋯O11	3.196 (3)	1 − x, 1 − y, 1 − z
C30⋯O11	3.122 (3)	1 − x, 1 − y, 1 − z
C16⋯H28	2.59	−1 + x, y, z
O3⋯H17	2.54	1 − x, 1 − y, 1 − z
H18B⋯H20	2.44	−x, −y, 1 − z

Figure 3
Two views of the Hirshfeld surface of (I)

mapped over d_norm in the range −0.106 to +1.524 au.

Figure 4
Two views of the Hirshfeld surface of (I)

mapped over the electrostatic potential in the range ±0.046 au. The red and blue regions represent negative and positive electrostatic potentials, respectively.

Figure 5
A view of the Hirshfeld surface of (I)

mapped over d_norm in the range −0.090 to +1.204 au highlighting O⋯O and C⋯H/H⋯C contacts by sky-blue and red dashed lines, respectively.

The overall two-dimensional fingerprint plot for (I) and those delineated into H⋯H, O⋯H/H⋯O, O⋯O, C⋯H/H⋯C and C⋯O/O⋯C contacts (McKinnon et al., 2007 ) are illustrated in Fig. 6; the percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are summarized in Table 3. In the fingerprint plot delineated into H⋯H contacts, the relatively small, i.e. 15.6%, contribution from these contacts to the Hirshfeld surfaces is due to the presence of the carbonyl groups on the Ru-cluster which leads to an increase in the contribution of O⋯H/H⋯O contacts to the Hirshfeld surface, i.e. 37.4%. The single tip at d_e + d_i ∼2.4 Å in the H⋯H delineated fingerprint plot, which has a broad appearance, arises from a van der Waals contact between the methyl-H18B and phenyl-H20 atoms (Table 2). The two pairs of adjacent peaks at d_e + d_i ∼2.5 and 2.6 Å in the fingerprint plot delineated into O⋯H/H⋯O contacts are the result of the interatomic C—H⋯O interaction discussed above (Table 1) and a short interatomic O⋯H/H⋯O contact (Table 2), respectively. The influence of the significant interatomic O3⋯O3 contact (Fig. 5) and other such short interatomic contacts (Table 3) are viewed as the distribution of points with the rocket-like tip extending from d_e + d_i ∼2.8 Å in the plot delineated into O⋯O contacts. In the fingerprint plot delineated into C⋯O/O⋯C contacts, the short interatomic contacts between carbonyl-C7 and -O9 atoms appear as the pair of thin tips at d_e + d_i ∼3.1 Å superimposed on the parabolic distribution of points characterizing other such short interatomic contacts through the points around d_e = d_i = 1.6 Å. The other dominant short interatomic C⋯H/H⋯C contacts (Table 2) result in the pair of forceps-like tips at d_e + d_i ∼2.6 Å in the respective delineated fingerprint plot. The small contribution from other remaining interatomic contacts summarized in Table 3 have negligible effect on the packing.

Table 3
Percentage contributions of interatomic contacts to the Hirshfeld surface for (I)

Contact	Percentage contribution
H⋯H	15.6
O⋯H/H⋯O	37.4
C⋯H/H⋯C	14.7
O⋯O	15.8
C⋯O/O⋯C	9.0
S⋯H/H⋯S	2.6
S⋯O/O⋯S	2.4
C⋯C	1.6
C⋯S/S⋯C	0.9

Figure 6
The full two-dimensional fingerprint plot for (I)

and those delineated into H⋯H, O⋯H/H⋯O, O⋯O, C⋯H/H⋯C and C⋯O/O⋯C contacts.

5. Database survey

As mentioned in the Chemical context, there are two other Ru₃ clusters in the literature having the same (4-methylsulfanylphenyl)diphenylphosphane ligand as in (I). These are formulated as Ru₃(CO)₉PPh₂(C₆H₄SMe-4)(Ph₂PCH₂PPh₂) (II) (Shawkataly et al., 2011b) and its arsenic analogue, Ru₃(CO)₉PPh₂(C₆H₄SMe-4)(Ph₂AsCH₂AsPh₂) (Shawkataly et al., 2011a), in each of which the bidentate ligand bridges the other two ruthenium atoms in the triangle. The structural motif found in (I), i.e. with an equatorially substituted phosphane ligand, is consistent with the approximately 35 literature precedents with the general formula Ru₃(CO)₁₁PRR′R′′ and several examples where the phosphane ligand is bidentate bridging, i.e. Ru₃(CO)₁₁PR(R′)–R′′–(R′)RPRu₃(CO)₁₁ (Groom et al., 2016 ). There are no crystallographic examples with perpendicular mono-substitution of phosphane ligands in Ru₃(CO)₁₁PRR′R′′.

6. Synthesis and crystallization

All reactions were carried out under an inert atmosphere of oxygen-free nitrogen (OFN) using standard Schlenk techniques. Ru₃(CO)₁₂ was purchased from Aldrich and PPh₂C₆H₄SMe was synthesized as reported previously (Fuhr et al., 2002). Ru₃(CO)₁₁P(C₆H₄SMe-4)Ph₂ (I) was synthesized by dissolving Ru₃(CO)₁₂ (100 mg, 0.0015 mmol) and PPh₂(C₆H₄SMe) (48 mg, 0.0015 mmol) in tetrahydrofuran (25 ml). The reaction mixture was treated dropwise with sodium diphenylketyl solution until the colour of the mixture turned from orange to dark red and then stirred for 30 min. The solvent was evaporated under vacuum and the residue was chromatographed by preparative TLC. Elution with 7:3 n-hexane/dichloromethane mixture gave four bands and the major orange fraction was characterized as (I) (117 mg, 79.6%). Orange crystals were crystallized from solvent diffusion of dichloromethane into a methanol solution of (I). Analysis calculated for C₃₀H₁₇O₁₁PRu₃S: C, 39.18; H, 1.86%. Found: C, 39.60; H, 1.90%. IR (C₆H₁₂): ν(CO) 2097(m), 2059(w), 2046(m), 2015(s), 1989(w) cm⁻¹. ¹H NMR (CDCl₃): δ 7.45–7.23 (m, 14H, Ph, C₆H₄), 2.48 (s, Me). ¹³C NMR (CDCl₃): δ 204.24 (Ru—CO), 135.19–125.37 (Ph), 14.79 (Me). ³¹P NMR (CDCl₃): δ 34.28 (s).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4. The carbon-bound H atoms were placed in calculated positions (C—H = 0.95–0.98 Å) and were included in the refinement in the riding-model approximation, with U_iso(H) set to 1.2–1.5U_eq(C). Owing to poor agreement, four reflections, i.e. (1 7 14), ( $[\overline{10}]$ $[\overline{2}]$ 6), ( $[\overline{3}]$ 12 12) and ( $[\overline{6}]$ 16 10), were omitted from the final cycles of refinement. The maximum and minimum residual electron density peaks of 1.97 and 0.98 e Å⁻³, respectively, were located 0.69 and 0.61 Å from the atoms Ru1 and Ru3, respectively.

Table 4
Experimental details

Crystal data
Chemical formula	[Ru₃(C₁₉H₁₇PS)(CO)₁₁]
M_r	919.67
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	9.6922 (1), 12.7459 (2), 13.6030 (2)
α, β, γ (°)	103.301 (1), 102.938 (1), 91.771 (1)
V (Å³)	1587.83 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.58
Crystal size (mm)	0.32 × 0.30 × 0.14

Data collection
Diffractometer	Bruker SMART APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.448, 0.526
No. of measured, independent and observed [I > 2σ(I)] reflections	56976, 15652, 11725
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.842

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.097, 1.03
No. of reflections	15652
No. of parameters	416
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.97, −0.98
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), ORTEP-3 for Windows (Farrugia, 2012 ), DIAMOND (Brandenburg, 2006 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1842044

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2056989018006989/hb7749sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989018006989/hb7749Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS (Sheldrick, 2008); 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: publCIF (Westrip, 2010).

Undecacarbonyl[(4-methylsulfanylphenyl)diphenylphosphane]triruthenium(0) top

Crystal data top

[Ru₃(C₁₉H₁₇PS)(CO)₁₁]	Z = 2
M_r = 919.67	F(000) = 896
Triclinic, P1	D_x = 1.924 Mg m⁻³
a = 9.6922 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.7459 (2) Å	Cell parameters from 9414 reflections
c = 13.6030 (2) Å	θ = 2.6–36.5°
α = 103.301 (1)°	µ = 1.58 mm⁻¹
β = 102.938 (1)°	T = 100 K
γ = 91.771 (1)°	Block, orange
V = 1587.83 (4) Å³	0.32 × 0.30 × 0.14 mm

Data collection top

Bruker SMART APEXII CCD diffractometer	11725 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
φ and ω scans	θ_max = 36.8°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −16→16
T_min = 0.448, T_max = 0.526	k = −21→21
56976 measured reflections	l = −22→22
15652 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H-atom parameters constrained
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.048P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
15652 reflections	Δρ_max = 1.97 e Å⁻³
416 parameters	Δρ_min = −0.98 e Å⁻³
0 restraints

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Ru1	0.28387 (2)	0.33186 (2)	0.28051 (2)	0.01428 (4)
Ru2	0.40348 (2)	0.29273 (2)	0.09996 (2)	0.01862 (4)
Ru3	0.21842 (2)	0.46106 (2)	0.13284 (2)	0.01626 (4)
S1	0.11319 (7)	0.13142 (5)	0.73844 (5)	0.02529 (12)
P1	0.37139 (6)	0.19229 (4)	0.36008 (4)	0.01376 (10)
O1	−0.00653 (19)	0.21034 (14)	0.16345 (15)	0.0282 (4)
O2	0.1200 (2)	0.45096 (15)	0.43099 (15)	0.0308 (4)
O3	0.55312 (18)	0.47646 (14)	0.40979 (13)	0.0251 (4)
O4	0.6007 (3)	0.11066 (18)	0.10236 (18)	0.0435 (5)
O5	0.1625 (2)	0.11127 (15)	−0.00206 (15)	0.0312 (4)
O6	0.4152 (2)	0.34976 (16)	−0.10467 (15)	0.0309 (4)
O7	0.6584 (2)	0.45662 (17)	0.22391 (15)	0.0319 (4)
O8	−0.0055 (2)	0.29918 (15)	−0.03258 (16)	0.0326 (4)
O9	0.2453 (2)	0.57908 (15)	−0.03402 (14)	0.0288 (4)
O10	−0.0099 (2)	0.57899 (17)	0.22667 (16)	0.0335 (4)
O11	0.4558 (2)	0.62755 (14)	0.27933 (14)	0.0273 (4)
C1	0.1048 (3)	0.25236 (18)	0.20139 (19)	0.0207 (4)
C2	0.1833 (3)	0.40534 (19)	0.37650 (19)	0.0215 (4)
C3	0.4559 (3)	0.42297 (18)	0.35766 (18)	0.0195 (4)
C4	0.5271 (3)	0.1777 (2)	0.1037 (2)	0.0279 (5)
C5	0.2456 (3)	0.1817 (2)	0.03905 (19)	0.0246 (5)
C6	0.4106 (3)	0.3274 (2)	−0.0295 (2)	0.0236 (5)
C7	0.5600 (3)	0.4000 (2)	0.18099 (19)	0.0238 (5)
C8	0.0801 (3)	0.35306 (19)	0.03187 (19)	0.0228 (5)
C9	0.2348 (3)	0.53252 (19)	0.02662 (18)	0.0211 (4)
C10	0.0760 (3)	0.53550 (19)	0.19383 (19)	0.0223 (4)
C11	0.3718 (3)	0.56093 (19)	0.22852 (19)	0.0215 (4)
C12	0.2835 (2)	0.16989 (17)	0.45989 (17)	0.0155 (4)
C13	0.2366 (2)	0.06656 (18)	0.46472 (17)	0.0174 (4)
H13	0.2421	0.0056	0.4108	0.021*
C14	0.1818 (2)	0.05201 (18)	0.54780 (18)	0.0189 (4)
H14	0.1480	−0.0183	0.5491	0.023*
C15	0.1765 (2)	0.14016 (18)	0.62855 (17)	0.0179 (4)
C16	0.2236 (2)	0.24400 (18)	0.62442 (17)	0.0176 (4)
H16	0.2203	0.3048	0.6792	0.021*
C17	0.2748 (2)	0.25804 (17)	0.54035 (17)	0.0166 (4)
H17	0.3045	0.3288	0.5376	0.020*
C18	0.1152 (3)	−0.0110 (2)	0.7356 (2)	0.0276 (5)
H18A	0.0428	−0.0525	0.6756	0.041*
H18B	0.0949	−0.0232	0.7997	0.041*
H18C	0.2090	−0.0346	0.7299	0.041*
C19	0.3634 (2)	0.05642 (16)	0.27629 (16)	0.0153 (4)
C20	0.2408 (2)	0.01554 (18)	0.19821 (19)	0.0216 (4)
H20	0.1635	0.0592	0.1886	0.026*
C21	0.2302 (3)	−0.08793 (19)	0.1345 (2)	0.0268 (5)
H21	0.1462	−0.1145	0.0818	0.032*
C22	0.3416 (3)	−0.15220 (19)	0.1476 (2)	0.0253 (5)
H22	0.3348	−0.2228	0.1037	0.030*
C23	0.4638 (3)	−0.1130 (2)	0.2255 (2)	0.0264 (5)
H23	0.5405	−0.1572	0.2350	0.032*
C24	0.4747 (2)	−0.00928 (18)	0.28960 (19)	0.0214 (4)
H24	0.5585	0.0168	0.3427	0.026*
C25	0.5593 (2)	0.21583 (17)	0.43099 (17)	0.0171 (4)
C26	0.6609 (3)	0.24650 (19)	0.3821 (2)	0.0224 (4)
H26	0.6323	0.2535	0.3126	0.027*
C27	0.8033 (3)	0.2669 (2)	0.4343 (2)	0.0282 (5)
H27	0.8715	0.2876	0.4003	0.034*
C28	0.8460 (3)	0.2571 (2)	0.5359 (2)	0.0288 (5)
H28	0.9431	0.2725	0.5721	0.035*
C29	0.7475 (3)	0.2249 (2)	0.5841 (2)	0.0266 (5)
H29	0.7772	0.2172	0.6533	0.032*
C30	0.6042 (2)	0.20356 (18)	0.53226 (18)	0.0195 (4)
H30	0.5371	0.1806	0.5660	0.023*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ru1	0.01599 (8)	0.01239 (7)	0.01479 (7)	0.00070 (5)	0.00376 (6)	0.00392 (6)
Ru2	0.02282 (9)	0.01803 (8)	0.01699 (8)	0.00456 (7)	0.00739 (7)	0.00527 (6)
Ru3	0.01832 (8)	0.01340 (7)	0.01637 (8)	0.00103 (6)	0.00223 (6)	0.00411 (6)
S1	0.0303 (3)	0.0269 (3)	0.0244 (3)	0.0041 (2)	0.0138 (2)	0.0103 (2)
P1	0.0135 (2)	0.0127 (2)	0.0147 (2)	0.00001 (18)	0.00275 (18)	0.00325 (18)
O1	0.0219 (9)	0.0246 (9)	0.0366 (10)	−0.0025 (7)	0.0012 (8)	0.0107 (8)
O2	0.0334 (10)	0.0308 (10)	0.0317 (10)	0.0124 (8)	0.0161 (8)	0.0052 (8)
O3	0.0263 (9)	0.0226 (8)	0.0236 (9)	−0.0045 (7)	0.0038 (7)	0.0031 (7)
O4	0.0515 (14)	0.0407 (12)	0.0419 (12)	0.0280 (11)	0.0132 (11)	0.0125 (10)
O5	0.0386 (11)	0.0241 (9)	0.0308 (10)	−0.0003 (8)	0.0110 (8)	0.0042 (8)
O6	0.0403 (11)	0.0320 (10)	0.0250 (9)	0.0068 (8)	0.0130 (8)	0.0103 (8)
O7	0.0289 (10)	0.0379 (11)	0.0280 (10)	−0.0020 (8)	0.0092 (8)	0.0046 (8)
O8	0.0327 (10)	0.0215 (9)	0.0355 (10)	−0.0014 (7)	−0.0062 (8)	0.0053 (8)
O9	0.0333 (10)	0.0297 (9)	0.0255 (9)	0.0008 (8)	0.0080 (8)	0.0103 (8)
O10	0.0272 (10)	0.0376 (11)	0.0334 (10)	0.0080 (8)	0.0092 (8)	0.0014 (9)
O11	0.0287 (9)	0.0231 (8)	0.0266 (9)	−0.0030 (7)	0.0032 (7)	0.0032 (7)
C1	0.0237 (11)	0.0159 (9)	0.0239 (11)	0.0033 (8)	0.0049 (9)	0.0080 (8)
C2	0.0216 (11)	0.0206 (10)	0.0238 (11)	0.0024 (8)	0.0051 (9)	0.0087 (9)
C3	0.0240 (11)	0.0162 (9)	0.0196 (10)	0.0013 (8)	0.0064 (8)	0.0059 (8)
C4	0.0329 (14)	0.0297 (13)	0.0233 (12)	0.0088 (11)	0.0091 (10)	0.0081 (10)
C5	0.0319 (13)	0.0226 (11)	0.0215 (11)	0.0054 (10)	0.0099 (10)	0.0060 (9)
C6	0.0249 (12)	0.0235 (11)	0.0237 (11)	0.0037 (9)	0.0092 (9)	0.0051 (9)
C7	0.0284 (12)	0.0250 (11)	0.0203 (10)	0.0060 (9)	0.0094 (9)	0.0061 (9)
C8	0.0252 (12)	0.0165 (10)	0.0257 (11)	0.0008 (8)	0.0013 (9)	0.0081 (9)
C9	0.0211 (11)	0.0197 (10)	0.0212 (10)	0.0018 (8)	0.0038 (8)	0.0033 (8)
C10	0.0222 (11)	0.0212 (10)	0.0219 (11)	−0.0004 (9)	0.0024 (9)	0.0054 (9)
C11	0.0227 (11)	0.0185 (10)	0.0227 (11)	0.0024 (8)	0.0035 (9)	0.0057 (8)
C12	0.0141 (9)	0.0159 (9)	0.0166 (9)	0.0008 (7)	0.0019 (7)	0.0061 (7)
C13	0.0177 (10)	0.0168 (9)	0.0175 (9)	−0.0010 (7)	0.0031 (8)	0.0054 (8)
C14	0.0183 (10)	0.0183 (10)	0.0210 (10)	−0.0005 (8)	0.0039 (8)	0.0075 (8)
C15	0.0154 (10)	0.0205 (10)	0.0197 (10)	0.0025 (8)	0.0050 (8)	0.0079 (8)
C16	0.0163 (10)	0.0185 (9)	0.0180 (9)	0.0022 (8)	0.0044 (8)	0.0039 (8)
C17	0.0151 (9)	0.0167 (9)	0.0183 (9)	0.0012 (7)	0.0038 (7)	0.0050 (8)
C18	0.0314 (13)	0.0298 (13)	0.0268 (12)	0.0003 (10)	0.0104 (10)	0.0143 (10)
C19	0.0157 (9)	0.0127 (8)	0.0167 (9)	−0.0003 (7)	0.0041 (7)	0.0023 (7)
C20	0.0174 (10)	0.0169 (10)	0.0276 (11)	0.0012 (8)	−0.0001 (9)	0.0047 (9)
C21	0.0240 (12)	0.0170 (10)	0.0305 (13)	−0.0020 (9)	−0.0058 (10)	0.0002 (9)
C22	0.0298 (13)	0.0149 (10)	0.0262 (12)	0.0010 (9)	0.0040 (10)	−0.0022 (9)
C23	0.0249 (12)	0.0192 (11)	0.0315 (13)	0.0068 (9)	0.0044 (10)	0.0005 (9)
C24	0.0182 (10)	0.0195 (10)	0.0223 (10)	0.0028 (8)	−0.0002 (8)	0.0012 (8)
C25	0.0146 (9)	0.0146 (9)	0.0200 (10)	0.0002 (7)	0.0018 (8)	0.0024 (8)
C26	0.0195 (11)	0.0222 (11)	0.0271 (11)	0.0001 (8)	0.0064 (9)	0.0087 (9)
C27	0.0156 (11)	0.0257 (12)	0.0424 (15)	−0.0003 (9)	0.0072 (10)	0.0063 (11)
C28	0.0152 (11)	0.0236 (11)	0.0397 (15)	0.0009 (9)	−0.0024 (10)	0.0006 (11)
C29	0.0243 (12)	0.0238 (11)	0.0244 (11)	0.0048 (9)	−0.0031 (9)	−0.0003 (9)
C30	0.0174 (10)	0.0177 (9)	0.0203 (10)	0.0032 (8)	0.0014 (8)	0.0015 (8)

Geometric parameters (Å, º) top

Ru1—C2	1.897 (3)	C13—C14	1.397 (3)
Ru1—C1	1.937 (2)	C13—H13	0.9500
Ru1—C3	1.941 (2)	C14—C15	1.390 (3)
Ru1—P1	2.3714 (5)	C14—H14	0.9500
Ru1—Ru3	2.8575 (2)	C15—C16	1.404 (3)
Ru1—Ru2	2.8933 (2)	C16—C17	1.389 (3)
Ru2—C4	1.924 (3)	C16—H16	0.9500
Ru2—C6	1.927 (2)	C17—H17	0.9500
Ru2—C5	1.946 (3)	C18—H18A	0.9800
Ru2—C7	1.953 (3)	C18—H18B	0.9800
Ru2—Ru3	2.8594 (3)	C18—H18C	0.9800
Ru3—C9	1.908 (2)	C19—C24	1.392 (3)
Ru3—C10	1.930 (3)	C19—C20	1.398 (3)
Ru3—C8	1.942 (2)	C20—C21	1.388 (3)
Ru3—C11	1.944 (2)	C20—H20	0.9500
S1—C15	1.763 (2)	C21—C22	1.380 (4)
S1—C18	1.808 (3)	C21—H21	0.9500
P1—C12	1.826 (2)	C22—C23	1.390 (4)
P1—C19	1.830 (2)	C22—H22	0.9500
P1—C25	1.840 (2)	C23—C24	1.393 (3)
O1—C1	1.142 (3)	C23—H23	0.9500
O2—C2	1.136 (3)	C24—H24	0.9500
O3—C3	1.138 (3)	C25—C30	1.395 (3)
O4—C4	1.130 (3)	C25—C26	1.397 (3)
O5—C5	1.136 (3)	C26—C27	1.389 (3)
O6—C6	1.133 (3)	C26—H26	0.9500
O7—C7	1.134 (3)	C27—C28	1.387 (4)
O8—C8	1.136 (3)	C27—H27	0.9500
O9—C9	1.141 (3)	C28—C29	1.375 (4)
O10—C10	1.132 (3)	C28—H28	0.9500
O11—C11	1.139 (3)	C29—C30	1.397 (3)
C12—C17	1.396 (3)	C29—H29	0.9500
C12—C13	1.401 (3)	C30—H30	0.9500

C2—Ru1—C1	87.40 (10)	O11—C11—Ru3	172.7 (2)
C2—Ru1—C3	90.22 (10)	C17—C12—C13	118.4 (2)
C1—Ru1—C3	174.97 (9)	C17—C12—P1	118.62 (15)
C2—Ru1—P1	101.13 (7)	C13—C12—P1	122.67 (17)
C1—Ru1—P1	95.84 (6)	C14—C13—C12	120.9 (2)
C3—Ru1—P1	88.97 (7)	C14—C13—H13	119.6
C2—Ru1—Ru3	97.52 (7)	C12—C13—H13	119.6
C1—Ru1—Ru3	83.06 (6)	C15—C14—C13	120.2 (2)
C3—Ru1—Ru3	92.87 (6)	C15—C14—H14	119.9
P1—Ru1—Ru3	161.254 (16)	C13—C14—H14	119.9
C2—Ru1—Ru2	156.94 (7)	C14—C15—C16	119.3 (2)
C1—Ru1—Ru2	92.30 (7)	C14—C15—S1	124.25 (17)
C3—Ru1—Ru2	88.15 (7)	C16—C15—S1	116.43 (17)
P1—Ru1—Ru2	101.829 (15)	C17—C16—C15	120.1 (2)
Ru3—Ru1—Ru2	59.628 (6)	C17—C16—H16	119.9
C4—Ru2—C6	102.37 (11)	C15—C16—H16	119.9
C4—Ru2—C5	87.57 (11)	C16—C17—C12	121.1 (2)
C6—Ru2—C5	95.01 (10)	C16—C17—H17	119.4
C4—Ru2—C7	91.05 (11)	C12—C17—H17	119.5
C6—Ru2—C7	93.55 (10)	S1—C18—H18A	109.5
C5—Ru2—C7	171.43 (10)	S1—C18—H18B	109.5
C4—Ru2—Ru3	169.28 (8)	H18A—C18—H18B	109.5
C6—Ru2—Ru3	88.28 (7)	S1—C18—H18C	109.5
C5—Ru2—Ru3	92.72 (7)	H18A—C18—H18C	109.5
C7—Ru2—Ru3	87.07 (7)	H18B—C18—H18C	109.5
C4—Ru2—Ru1	109.84 (8)	C24—C19—C20	118.6 (2)
C6—Ru2—Ru1	147.73 (7)	C24—C19—P1	121.93 (17)
C5—Ru2—Ru1	84.63 (7)	C20—C19—P1	119.49 (17)
C7—Ru2—Ru1	87.89 (7)	C21—C20—C19	121.0 (2)
Ru3—Ru2—Ru1	59.563 (6)	C21—C20—H20	119.5
C9—Ru3—C10	103.41 (10)	C19—C20—H20	119.5
C9—Ru3—C8	89.88 (10)	C22—C21—C20	120.1 (2)
C10—Ru3—C8	93.49 (10)	C22—C21—H21	119.9
C9—Ru3—C11	89.20 (10)	C20—C21—H21	119.9
C10—Ru3—C11	92.35 (10)	C21—C22—C23	119.6 (2)
C8—Ru3—C11	174.14 (10)	C21—C22—H22	120.2
C9—Ru3—Ru1	160.67 (7)	C23—C22—H22	120.2
C10—Ru3—Ru1	95.01 (7)	C22—C23—C24	120.4 (2)
C8—Ru3—Ru1	94.86 (7)	C22—C23—H23	119.8
C11—Ru3—Ru1	84.18 (7)	C24—C23—H23	119.8
C9—Ru3—Ru2	101.48 (7)	C23—C24—C19	120.3 (2)
C10—Ru3—Ru2	154.74 (7)	C23—C24—H24	119.8
C8—Ru3—Ru2	82.25 (7)	C19—C24—H24	119.8
C11—Ru3—Ru2	92.26 (7)	C30—C25—C26	118.7 (2)
Ru1—Ru3—Ru2	60.808 (6)	C30—C25—P1	122.05 (17)
C15—S1—C18	102.86 (11)	C26—C25—P1	119.26 (17)
C12—P1—C19	103.17 (10)	C27—C26—C25	120.7 (2)
C12—P1—C25	102.11 (10)	C27—C26—H26	119.7
C19—P1—C25	102.31 (10)	C25—C26—H26	119.7
C12—P1—Ru1	114.43 (7)	C28—C27—C26	120.1 (2)
C19—P1—Ru1	117.78 (7)	C28—C27—H27	120.0
C25—P1—Ru1	114.99 (7)	C26—C27—H27	120.0
O1—C1—Ru1	172.8 (2)	C29—C28—C27	119.8 (2)
O2—C2—Ru1	177.3 (2)	C29—C28—H28	120.1
O3—C3—Ru1	174.6 (2)	C27—C28—H28	120.1
O4—C4—Ru2	177.3 (2)	C28—C29—C30	120.7 (2)
O5—C5—Ru2	173.0 (2)	C28—C29—H29	119.7
O6—C6—Ru2	178.7 (2)	C30—C29—H29	119.7
O7—C7—Ru2	174.0 (2)	C25—C30—C29	120.1 (2)
O8—C8—Ru3	172.1 (2)	C25—C30—H30	120.0
O9—C9—Ru3	177.3 (2)	C29—C30—H30	120.0
O10—C10—Ru3	177.9 (2)

C19—P1—C12—C17	177.86 (17)	Ru1—P1—C19—C20	−43.3 (2)
C25—P1—C12—C17	71.95 (18)	C24—C19—C20—C21	−0.6 (4)
Ru1—P1—C12—C17	−52.94 (18)	P1—C19—C20—C21	−178.9 (2)
C19—P1—C12—C13	4.2 (2)	C19—C20—C21—C22	0.0 (4)
C25—P1—C12—C13	−101.70 (19)	C20—C21—C22—C23	0.5 (4)
Ru1—P1—C12—C13	133.40 (16)	C21—C22—C23—C24	−0.4 (4)
C17—C12—C13—C14	0.3 (3)	C22—C23—C24—C19	−0.2 (4)
P1—C12—C13—C14	173.99 (17)	C20—C19—C24—C23	0.6 (4)
C12—C13—C14—C15	−1.7 (3)	P1—C19—C24—C23	178.88 (19)
C13—C14—C15—C16	1.5 (3)	C12—P1—C25—C30	6.3 (2)
C13—C14—C15—S1	−178.67 (17)	C19—P1—C25—C30	−100.32 (19)
C18—S1—C15—C14	16.8 (2)	Ru1—P1—C25—C30	130.78 (16)
C18—S1—C15—C16	−163.38 (18)	C12—P1—C25—C26	−174.03 (18)
C14—C15—C16—C17	−0.1 (3)	C19—P1—C25—C26	79.39 (19)
S1—C15—C16—C17	−179.86 (17)	Ru1—P1—C25—C26	−49.5 (2)
C15—C16—C17—C12	−1.3 (3)	C30—C25—C26—C27	−1.5 (3)
C13—C12—C17—C16	1.2 (3)	P1—C25—C26—C27	178.75 (19)
P1—C12—C17—C16	−172.74 (17)	C25—C26—C27—C28	−0.1 (4)
C12—P1—C19—C24	−94.4 (2)	C26—C27—C28—C29	1.3 (4)
C25—P1—C19—C24	11.3 (2)	C27—C28—C29—C30	−1.0 (4)
Ru1—P1—C19—C24	138.48 (17)	C26—C25—C30—C29	1.9 (3)
C12—P1—C19—C20	83.81 (19)	P1—C25—C30—C29	−178.38 (18)
C25—P1—C19—C20	−170.43 (18)	C28—C29—C30—C25	−0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···O8ⁱ	0.95	2.55	3.238 (3)	129

Symmetry code: (i) −x, −y, −z.

Summary of short interatomic contacts (Å) in (I) top

Contact	Distance	Symmetry operation
O3···O3	2.817 (2)	1 - x, 1 - y, 1 - z
O6···O11	2.986 (3)	1 - x, 1 - y, - z
C3···O3	3.150 (3)	1 - x, 1 - y, 1 - z
C7···O9	3.088 (3)	1 - x, 1 - y, - z
C9···O8	3.137 (3)	-x, 1 - y, - z
C17···O11	3.196 (3)	1 - x, 1 - y, 1 - z
C30···O11	3.122 (3)	1 - x, 1 - y, 1 - z
C16···H28	2.59	-1 + x, y, z
O3···H17	2.54	1 - x, 1 - y, 1 - z
H18B···H20	2.44	-x, -y, 1 - z

Percentage contributions of interatomic contacts to the Hirshfeld surface for (I) top

	Percentage contribution
Contact	(I)
H···H	15.6
O···H/H···O	37.4
C···H/H···C	14.7
O···O	15.8
C···O/O···C	9.0
S···H/H···S	2.6
S···O/O···S	2.4
C···C	1.6
C···S/S···C	0.9

Footnotes

‡Additional correspondence author, e-mail: omarsa@usm.my.

Funding information

OBS wishes to thank Universiti Sains Malaysia (USM) for Research University Grant No. 1001/PJJAUH/8011002. SSS thanks the Universiti Teknologi Mara (UiTM) for a PhD scholarship.

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