(η⁶-Benzene)(carbonato-κ²O,O′)[di­cyclohex­yl(naphthalen-1-ylmeth­yl)phosphane-κP]ruthenium(II) chloro­form tris­olvate

The title compound, [Ru(CO₃)(η⁶-C₆H₆){(C₆H₁₁)₂P(CH₂C₁₀H₇)}]·3CHCl₃, was synthesized by carbonation of [RuCl₂(η⁶-C₆H₆){(C₆H₁₁)₂P(CH₂C₁₀H₇)}] with NaHCO₃ in methanol at room temperature. The Ru^II atom is surrounded by a benzene ligand, a chelating carbonate group and a phosphane ligand in a piano-stool configuration. The crystal packing is consolidated by C—H...O and C—H...Cl hydrogen-bonding inter­actions between adjacent metal complexes and between the complexes and the solvent mol­ecules. The asymmetric unit contains one metal complex and three chloro­form solvent mol­ecules of which only one was modelled. The estimated diffraction contributions of the other two strongly disordered chloro­form solvent mol­ecules were substracted from the observed diffraction data using the SQUEEZE procedure in PLATON [Spek (2009). Acta Cryst. D65, 148–155].

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.007 Å
Some non-H atoms missing
• R factor = 0.041
• wR factor = 0.110
• Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level A
CHEMW03_ALERT_2_A ALERT: The ratio of given/expected molecular weight as
            calculated from the _atom_site* data lies outside
            the range 0.90 <> 1.10
           From the CIF: _cell_formula_units_Z                    8
           From the CIF: _chemical_formula_weight           935.74
           TEST: Calculate formula weight from _atom_site_*
           atom     mass    num     sum
           C        12.01   31.00  372.34
           H         1.01   38.00   38.30
           O        16.00    3.00   48.00
           P        30.97    1.00   30.97
           Cl       35.45    3.00  106.36
           Ru      101.07    1.00  101.07
           Calculated formula weight              697.04

Author Response: The two omitted disordered chloroform molecules are considered in the molecular formula and therefore also for the molecular weight.

PLAT051_ALERT_1_A Mu(calc) and Mu(CIF) Ratio Differs from 1.0 by .      40.26 %

Author Response: The two omitted disordered chloroform molecules are considered in the formula, but not in the model.

Alert level B
            Crystal system given = orthorhombic
PLAT019_ALERT_1_B  _diffrn_measured_fraction_theta_full/_max < 1.0      0.978 Why ?

Alert level C
PLAT041_ALERT_1_C Calc. and Reported SumFormula    Strings  Differ     Please Check
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...     Please Check
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C2     --  C3      ..        5.7 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C11    --  C12     ..        5.8 su
PLAT241_ALERT_2_C High      Ueq as Compared to Neighbors for .....         C2 Check
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors of         C31 Check
PLAT410_ALERT_2_C Short Intra H...H Contact  H8A    ..  H17     ..       1.95 Ang.
PLAT906_ALERT_3_C Large K value in the Analysis of Variance ......      2.372 Check
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595         25 Why ?

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C33 H40 Cl9 O3 P1 Ru1
            Atom count from the _atom_site data:  C31 H38 Cl3 O3 P1 Ru1
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G ALERT: Large difference may be due to a
            symmetry error - see SYMMG tests
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C33 H40 Cl9 O3 P Ru
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        264.00    248.00   16.00
           H        320.00    304.00   16.00
           Cl        72.00     24.00   48.00
           O         24.00     24.00    0.00
           P          8.00      8.00    0.00
           Ru         8.00      8.00    0.00
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT044_ALERT_1_G Calculated and Reported Density Dx  Differ by ..     0.3988 Check
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size ....       0.64 mm
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       8.47 Why ?
PLAT606_ALERT_4_G VERY LARGE Solvent Accessible VOID(S) in Structure        ! Info
PLAT869_ALERT_4_G ALERTS Related to the use of SQUEEZE Suppressed           ! Info
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          73 %
PLAT961_ALERT_5_G Dataset Contains no Negative Intensities .......     Please Check

   2 ALERT level A = Most likely a serious problem - resolve or explain
   1 ALERT level B = A potentially serious problem, consider carefully
   9 ALERT level C = Check. Ensure it is not caused by an omission or oversight
  11 ALERT level G = General information/check it is not something unexpected

   8 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

---

S1. Comment

The title compound was prepared in a two step synthesis: In the presence of 60 bar hydrogen, the benzene ruthenium dichloride dimer and the dicyclohexyl(1-naphthoyl)phosphane ligand react to give the [RuCl₂(η⁶-C₆H₆){(C₆H₁₁)₂PCH₂C₁₀H₇)}] complex in 80% yield. Here, the carbonyl group of the ligand is reduced to a methylen unit (Gowrisankar et al., 2014). In the second step the reduced complex was carbonated at room temperature in methanol with 10 equivalent of NaHCO₃ to yield the title compound, [Ru(CO₃)(η⁶-C₆H₆){(C₆H₁₁)₂PCH₂C₁₀H₇)}], as a chloroform solvate after recrystallization from a CHCl₃/heptane mixture. Related carbonatophosphane ruthenium complexes are known from the literature (Allen et al., 2009; Blosser et al., 2004; Davies et al., 2013; Dell'Amico et al., 2000; Demerseman et al., 2006; Drake et al., 2013).

The asymmetric unit contains one complex and one chloroform solvent molecule (Fig. 1). Contributions of two further strongly disordered solvent molecules (chloroform) were removed from the diffraction data with the SQUEEZE option in PLATON (Spek, 2009). The Ru^II atom is surrounded by a benzene ligand, a chelating carbonate group and a phosphane ligand (C₆H₁₁)₂P(CH₂C₁₀H₇) in a piano-stool geometry. The phosphane ligand is linked through its P atom with a Ru—P bond length of 2.3705 (8) Å; both cyclohexyl rings at the P atom adopt a chair conformation. The molecular structure shows a planar arrangement of the Ru(CO₃) fragment (mean deviation of the best plane defined by Ru1, O1, C1, O2, O3 is 0.036 Å). As expected, the exocyclic C—O bond in the Ru(CO₃) unit is with 1.242 (4) Å significantly shorter than the two endocyclic C—O bonds (C1—O1 = 1.326 (4) and C1—O2 = 1.309 (4) Å). The complex molecules as well as complex and solvent molecules are linked by C—H···Cl and C—H···O hydrogen bonds (Fig. 2).

The ³¹P-NMR spectrum of the title complex shows a singulett at 42.5 p.p.m., whereas the reduced complex [RuCl₂(η⁶-C₆H₆){(C₆H₁₁)₂PCH₂C₁₀H₇)}] exhibits an upfield shift to 39.1 p.p.m..

Related literature

For crystal structures of related carbonatophosphane ruthenium(II) complexes, see: Allen et al. (2009); Blosser et al. (2004); Davies et al. (2013); Dell'Amico et al. (2000); Demerseman et al. (2006); Drake et al. (2013). The starting complex [RuCl₂(η⁶-C₆H₆)(C₆H₁₁)₂PCH₂C₁₀H₇)] was described by Gowrisankar et al. (2014).

S2. Experimental

At room temperature, a mixture consisting of [RuCl₂(η⁶-C₆H₆){(C₆H₁₁)₂P(1-methylnaphthyl)}] (20 mg, 0.034 mmol), NaHCO₃(63 mg, 0.34 mmol) and methanol (5 ml) was stirred under argon in a Schlenk tube. The orange suspension changed to a yellow solution. The reaction was completed within 10 min and the solution was filtered over celite. The solvent was removed in vacuo and 18 mg (94%) of a yellow solid was obtained. Crystals suitable for X-ray analysis were grown from a CHCl₃/heptane mixture at 245 K. ¹H NMR (300 MHz, CDCl₃) δ 8.18 (d, J = 8.6 Hz, 1H, naphthyl), 7.88–7.75 (m, 2H, naphthyl), 7.63–7.30 (m, 3H, naphthyl), 7.33 (m, 1H, naphthyl), 5.07 (s, 6H, benzene), 3.55 (d, J = 10.2 Hz, 2H, CH₂), 2.14–1.95 (m, 4H, Cy), 1.95–1.79 (m, 4H, Cy), 1.79–1.65 (m, 4H, Cy), 1.67–1.47 (m, 2H, Cy), 1.32–1.01 (m, 8H, Cy). ³¹P{¹H} NMR (121 MHz, CDCl₃): δ 42.5.

S3. Refinement

H atoms were placed in idealized positions with d(C—H) = 0.95 - 1.00 Å (CH), 0.99 Å (CH₂) and refined using a riding model with U_iso(H) fixed at 1.2U_eq(C). Contributions of further disordered solvent molecules were removed from the diffraction data with PLATON / SQUEEZE (Spek, 2009). SQUEEZE estimated the electron count in the void volume of 1149 ų to be 501; two voids are given. The highest peak in the final difference Fourier map is located 0.86 Å from Ru1 and the deepest hole 0.75 Å from Cl3.

Computing details

Data collection: APEX2 (Bruker, 2012); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound with atoms at the 30% probability level for the displacement ellipsoids. Hydrogen atoms are omitted for clarity.
	Fig. 2. A packing diagram of the title compound showing hydrogen bonds as dashed lines.

(η⁶-Benzene)(carbonato-κ²O,O')[dicyclohexyl(naphthalen-1-ylmethyl)phosphane-κP]ruthenium(II) chloroform trisolvate

Crystal data

[Ru(CO3)(C6H6)(C23H31P)]·3CHCl3	Dx = 1.563 Mg m^−3
Mr = 935.74	Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, Pbca	Cell parameters from 9902 reflections
a = 22.1730 (4) Å	θ = 3.7–66.2°
b = 15.1385 (3) Å	µ = 9.40 mm^−1
c = 23.6954 (5) Å	T = 150 K
V = 7953.7 (3) Å^3	Needle, yellow
Z = 8	0.64 × 0.08 × 0.05 mm
F(000) = 3792

Data collection

Bruker Kappa APEXII DUO diffractometer	6998 independent reflections
Radiation source: microfocus	5815 reflections with I > 2σ(I)
Multilayer monochromator	Rint = 0.062
Detector resolution: 8.3333 pixels mm^-1	θmax = 66.6°, θmin = 3.7°
ω and φ scans	h = −26→25
Absorption correction: multi-scan (SADABS; Bruker, 2008)	k = −17→17
Tmin = 0.065, Tmax = 0.651	l = −28→27
68879 measured reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.110	w = 1/[σ^2(Fo^2) + (0.050P)^2 + 8.4698P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
6998 reflections	Δρmax = 1.17 e Å^−3
352 parameters	Δρmin = −0.79 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C31	0.03361 (18)	0.8411 (3)	0.0554 (2)	0.0638 (12)
H31	0.0732	0.8184	0.0695	0.077*
Cl1	0.00779 (7)	0.92264 (10)	0.10140 (6)	0.0870 (4)
Cl2	0.04409 (5)	0.88587 (10)	−0.01171 (6)	0.0783 (4)
Cl3	−0.01875 (5)	0.75354 (8)	0.05459 (7)	0.0812 (4)
C1	0.18339 (13)	−0.1129 (2)	0.06775 (15)	0.0346 (7)
C2	0.1466 (2)	0.1023 (3)	−0.0075 (2)	0.0668 (14)
H2	0.1235	0.0740	−0.0361	0.080*
C3	0.12336 (17)	0.1126 (3)	0.0464 (2)	0.0598 (12)
H3	0.0836	0.0931	0.0544	0.072*
C4	0.15773 (19)	0.1512 (2)	0.0888 (2)	0.0572 (11)
H4	0.1424	0.1537	0.1262	0.069*
C5	0.21390 (18)	0.1860 (2)	0.07708 (19)	0.0509 (9)
H5	0.2362	0.2152	0.1057	0.061*
C6	0.23753 (16)	0.1778 (2)	0.02288 (19)	0.0489 (9)
H6	0.2761	0.2022	0.0150	0.059*
C7	0.2066 (2)	0.1351 (3)	−0.01994 (19)	0.0580 (11)
H7	0.2241	0.1276	−0.0562	0.070*
C8	0.31201 (14)	−0.1025 (2)	0.11038 (15)	0.0371 (7)
H8A	0.2770	−0.1058	0.1362	0.045*
H8B	0.3036	−0.1438	0.0789	0.045*
C9	0.36532 (14)	−0.1397 (2)	0.14218 (16)	0.0387 (8)
C10	0.41559 (16)	−0.1674 (3)	0.1131 (2)	0.0533 (10)
H10	0.4172	−0.1610	0.0733	0.064*
C11	0.46469 (19)	−0.2052 (3)	0.1421 (3)	0.0810 (18)
H11	0.4989	−0.2247	0.1215	0.097*
C12	0.4639 (2)	−0.2142 (4)	0.1988 (3)	0.0815 (17)
H12	0.4980	−0.2387	0.2174	0.098*
C13	0.4139 (2)	−0.1880 (3)	0.2304 (2)	0.0621 (12)
C14	0.4120 (3)	−0.1993 (4)	0.2895 (2)	0.0862 (18)
H14	0.4468	−0.2210	0.3084	0.103*
C15	0.3619 (4)	−0.1801 (4)	0.3205 (3)	0.101 (2)
H15	0.3615	−0.1887	0.3602	0.121*
C16	0.3109 (3)	−0.1471 (4)	0.2924 (2)	0.0869 (17)
H16	0.2757	−0.1337	0.3136	0.104*
C17	0.3106 (2)	−0.1339 (3)	0.23569 (19)	0.0598 (11)
H17	0.2751	−0.1120	0.2182	0.072*
C18	0.36244 (16)	−0.1520 (2)	0.20162 (17)	0.0443 (8)
C19	0.34391 (14)	0.0887 (2)	0.13099 (14)	0.0356 (7)
H19	0.3404	0.1482	0.1129	0.043*
C20	0.30672 (17)	0.0935 (2)	0.18484 (16)	0.0461 (8)
H20A	0.3111	0.0376	0.2062	0.055*
H20B	0.2636	0.1010	0.1752	0.055*
C21	0.3276 (2)	0.1705 (3)	0.22123 (19)	0.0596 (11)
H21A	0.3037	0.1721	0.2565	0.072*
H21B	0.3208	0.2267	0.2008	0.072*
C22	0.3943 (2)	0.1608 (4)	0.2353 (2)	0.0681 (13)
H22A	0.4077	0.2126	0.2575	0.082*
H22B	0.4003	0.1074	0.2587	0.082*
C23	0.43187 (18)	0.1536 (3)	0.18300 (19)	0.0576 (11)
H23A	0.4746	0.1445	0.1937	0.069*
H23B	0.4292	0.2096	0.1615	0.069*
C24	0.41101 (15)	0.0771 (2)	0.14555 (17)	0.0450 (8)
H24A	0.4170	0.0204	0.1656	0.054*
H24B	0.4352	0.0758	0.1104	0.054*
C25	0.36856 (15)	0.0046 (2)	0.02310 (15)	0.0390 (7)
H25	0.4062	−0.0206	0.0399	0.047*
C26	0.38481 (18)	0.0969 (3)	−0.00015 (18)	0.0537 (10)
H26A	0.3488	0.1236	−0.0180	0.064*
H26B	0.3975	0.1357	0.0313	0.064*
C27	0.4356 (2)	0.0903 (4)	−0.0434 (2)	0.0668 (13)
H27A	0.4448	0.1499	−0.0584	0.080*
H27B	0.4724	0.0674	−0.0248	0.080*
C28	0.4183 (2)	0.0297 (4)	−0.0917 (2)	0.0828 (17)
H28A	0.3843	0.0559	−0.1129	0.099*
H28B	0.4529	0.0236	−0.1178	0.099*
C29	0.4004 (2)	−0.0598 (4)	−0.0700 (2)	0.0771 (16)
H29A	0.4363	−0.0890	−0.0536	0.092*
H29B	0.3865	−0.0963	−0.1022	0.092*
C30	0.35006 (18)	−0.0565 (3)	−0.02506 (18)	0.0586 (11)
H30A	0.3123	−0.0347	−0.0424	0.070*
H30B	0.3426	−0.1166	−0.0102	0.070*
O1	0.18027 (9)	−0.05130 (14)	0.10738 (10)	0.0363 (5)
O2	0.20684 (9)	−0.08313 (15)	0.02076 (10)	0.0365 (5)
O3	0.16578 (10)	−0.19007 (15)	0.07473 (12)	0.0455 (6)
P1	0.31196 (3)	0.00947 (5)	0.08005 (4)	0.03076 (17)
Ru1	0.21220 (2)	0.04581 (2)	0.05258 (2)	0.03286 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C31	0.040 (2)	0.064 (3)	0.088 (3)	−0.0052 (19)	−0.009 (2)	0.016 (2)
Cl1	0.0890 (9)	0.0875 (9)	0.0845 (9)	−0.0228 (7)	0.0002 (7)	−0.0021 (7)
Cl2	0.0510 (6)	0.1074 (10)	0.0766 (8)	−0.0010 (6)	0.0000 (5)	0.0143 (7)
Cl3	0.0556 (6)	0.0563 (6)	0.1317 (12)	−0.0060 (5)	−0.0115 (7)	0.0108 (7)
C1	0.0250 (14)	0.0301 (17)	0.049 (2)	0.0032 (12)	−0.0052 (13)	0.0029 (14)
C2	0.068 (3)	0.038 (2)	0.094 (4)	0.0077 (19)	−0.050 (3)	0.008 (2)
C3	0.0327 (18)	0.037 (2)	0.110 (4)	0.0105 (15)	−0.002 (2)	0.016 (2)
C4	0.059 (2)	0.0327 (19)	0.080 (3)	0.0206 (17)	0.011 (2)	0.0012 (19)
C5	0.063 (2)	0.0221 (16)	0.068 (3)	0.0063 (15)	−0.007 (2)	−0.0026 (16)
C6	0.0422 (18)	0.0268 (17)	0.078 (3)	0.0011 (14)	−0.0052 (19)	0.0159 (17)
C7	0.083 (3)	0.039 (2)	0.052 (2)	0.0145 (19)	−0.008 (2)	0.0156 (18)
C8	0.0340 (16)	0.0285 (15)	0.049 (2)	−0.0033 (13)	−0.0107 (14)	0.0073 (14)
C9	0.0334 (16)	0.0254 (15)	0.057 (2)	−0.0059 (12)	−0.0077 (15)	0.0074 (14)
C10	0.043 (2)	0.0402 (19)	0.076 (3)	0.0020 (16)	0.0048 (19)	0.0169 (19)
C11	0.038 (2)	0.050 (2)	0.154 (6)	0.0098 (18)	0.013 (3)	0.039 (3)
C12	0.046 (2)	0.074 (3)	0.125 (5)	0.000 (2)	−0.032 (3)	0.047 (3)
C13	0.064 (3)	0.046 (2)	0.077 (3)	−0.0015 (19)	−0.033 (2)	0.009 (2)
C14	0.121 (5)	0.062 (3)	0.075 (4)	0.013 (3)	−0.055 (4)	0.006 (3)
C15	0.181 (7)	0.065 (3)	0.058 (3)	0.030 (4)	−0.031 (4)	0.002 (3)
C16	0.138 (5)	0.065 (3)	0.058 (3)	0.028 (3)	0.009 (3)	0.008 (2)
C17	0.075 (3)	0.046 (2)	0.059 (3)	0.012 (2)	−0.005 (2)	0.0082 (19)
C18	0.0495 (19)	0.0279 (16)	0.055 (2)	−0.0054 (14)	−0.0157 (17)	0.0057 (15)
C19	0.0371 (16)	0.0287 (15)	0.0411 (18)	−0.0097 (13)	−0.0055 (14)	0.0017 (14)
C20	0.0454 (18)	0.044 (2)	0.049 (2)	−0.0112 (16)	−0.0032 (16)	−0.0035 (17)
C21	0.066 (3)	0.061 (3)	0.053 (2)	−0.015 (2)	0.003 (2)	−0.016 (2)
C22	0.069 (3)	0.077 (3)	0.057 (3)	−0.029 (2)	−0.015 (2)	−0.012 (2)
C23	0.052 (2)	0.054 (2)	0.066 (3)	−0.0213 (18)	−0.019 (2)	0.003 (2)
C24	0.0366 (17)	0.0430 (19)	0.056 (2)	−0.0071 (15)	−0.0097 (16)	0.0043 (16)
C25	0.0353 (16)	0.0423 (18)	0.0395 (18)	0.0049 (14)	−0.0014 (14)	0.0034 (15)
C26	0.053 (2)	0.054 (2)	0.054 (2)	0.0086 (18)	0.0118 (18)	0.0227 (19)
C27	0.061 (3)	0.077 (3)	0.062 (3)	0.016 (2)	0.020 (2)	0.025 (2)
C28	0.064 (3)	0.118 (5)	0.067 (3)	0.037 (3)	0.020 (2)	0.025 (3)
C29	0.056 (3)	0.108 (4)	0.067 (3)	0.024 (3)	0.001 (2)	−0.030 (3)
C30	0.048 (2)	0.081 (3)	0.047 (2)	0.014 (2)	−0.0018 (18)	−0.016 (2)
O1	0.0323 (11)	0.0287 (11)	0.0479 (14)	−0.0004 (8)	0.0041 (10)	0.0046 (10)
O2	0.0351 (11)	0.0357 (12)	0.0387 (13)	0.0009 (9)	−0.0075 (9)	−0.0021 (10)
O3	0.0351 (11)	0.0276 (12)	0.0739 (18)	−0.0011 (9)	−0.0048 (12)	0.0023 (12)
P1	0.0283 (4)	0.0257 (4)	0.0383 (4)	−0.0019 (3)	−0.0040 (3)	0.0038 (3)
Ru1	0.02876 (14)	0.02455 (14)	0.04527 (16)	0.00038 (8)	−0.00458 (10)	0.00306 (10)

Geometric parameters (Å, º)

C31—Cl2	1.744 (5)	C16—C17	1.359 (7)
C31—Cl1	1.743 (5)	C16—H16	0.9500
C31—Cl3	1.762 (4)	C17—C18	1.431 (6)
C31—H31	1.0000	C17—H17	0.9500
C1—O3	1.242 (4)	C19—C20	1.521 (5)
C1—O2	1.309 (4)	C19—C24	1.537 (4)
C1—O1	1.326 (4)	C19—P1	1.844 (3)
C1—Ru1	2.513 (3)	C19—H19	1.0000
C2—C3	1.386 (7)	C20—C21	1.522 (5)
C2—C7	1.451 (7)	C20—H20A	0.9900
C2—Ru1	2.209 (4)	C20—H20B	0.9900
C2—H2	0.9500	C21—C22	1.524 (6)
C3—C4	1.390 (7)	C21—H21A	0.9900
C3—Ru1	2.219 (4)	C21—H21B	0.9900
C3—H3	0.9500	C22—C23	1.497 (6)
C4—C5	1.380 (6)	C22—H22A	0.9900
C4—Ru1	2.177 (4)	C22—H22B	0.9900
C4—H4	0.9500	C23—C24	1.531 (5)
C5—C6	1.393 (6)	C23—H23A	0.9900
C5—Ru1	2.200 (4)	C23—H23B	0.9900
C5—H5	0.9500	C24—H24A	0.9900
C6—C7	1.384 (6)	C24—H24B	0.9900
C6—Ru1	2.192 (3)	C25—C30	1.525 (5)
C6—H6	0.9500	C25—C26	1.545 (5)
C7—Ru1	2.190 (4)	C25—P1	1.844 (3)
C7—H7	0.9500	C25—H25	1.0000
C8—C9	1.511 (4)	C26—C27	1.526 (5)
C8—P1	1.841 (3)	C26—H26A	0.9900
C8—H8A	0.9900	C26—H26B	0.9900
C8—H8B	0.9900	C27—C28	1.516 (8)
C9—C10	1.376 (5)	C27—H27A	0.9900
C9—C18	1.422 (5)	C27—H27B	0.9900
C10—C11	1.409 (6)	C28—C29	1.502 (8)
C10—H10	0.9500	C28—H28A	0.9900
C11—C12	1.349 (8)	C28—H28B	0.9900
C11—H11	0.9500	C29—C30	1.544 (6)
C12—C13	1.397 (8)	C29—H29A	0.9900
C12—H12	0.9500	C29—H29B	0.9900
C13—C14	1.412 (8)	C30—H30A	0.9900
C13—C18	1.437 (5)	C30—H30B	0.9900
C14—C15	1.363 (9)	O1—Ru1	2.085 (2)
C14—H14	0.9500	O2—Ru1	2.096 (2)
C15—C16	1.404 (9)	P1—Ru1	2.3705 (8)
C15—H15	0.9500
Cl2—C31—Cl1	109.8 (3)	C23—C22—H22B	109.3
Cl2—C31—Cl3	111.7 (3)	C21—C22—H22B	109.3
Cl1—C31—Cl3	108.8 (2)	H22A—C22—H22B	108.0
Cl2—C31—H31	108.8	C22—C23—C24	111.5 (3)
Cl1—C31—H31	108.8	C22—C23—H23A	109.3
Cl3—C31—H31	108.8	C24—C23—H23A	109.3
O3—C1—O2	124.2 (3)	C22—C23—H23B	109.3
O3—C1—O1	123.4 (3)	C24—C23—H23B	109.3
O2—C1—O1	112.4 (3)	H23A—C23—H23B	108.0
O3—C1—Ru1	176.4 (2)	C23—C24—C19	109.6 (3)
O2—C1—Ru1	56.47 (15)	C23—C24—H24A	109.8
O1—C1—Ru1	56.03 (15)	C19—C24—H24A	109.8
C3—C2—C7	119.3 (4)	C23—C24—H24B	109.8
C3—C2—Ru1	72.2 (2)	C19—C24—H24B	109.8
C7—C2—Ru1	70.1 (2)	H24A—C24—H24B	108.2
C3—C2—H2	120.4	C30—C25—C26	110.1 (3)
C7—C2—H2	120.4	C30—C25—P1	112.9 (3)
Ru1—C2—H2	129.8	C26—C25—P1	112.5 (3)
C2—C3—C4	120.7 (4)	C30—C25—H25	107.0
C2—C3—Ru1	71.3 (2)	C26—C25—H25	107.0
C4—C3—Ru1	69.9 (2)	P1—C25—H25	107.0
C2—C3—H3	119.7	C27—C26—C25	110.6 (3)
C4—C3—H3	119.7	C27—C26—H26A	109.5
Ru1—C3—H3	132.0	C25—C26—H26A	109.5
C5—C4—C3	120.7 (4)	C27—C26—H26B	109.5
C5—C4—Ru1	72.5 (2)	C25—C26—H26B	109.5
C3—C4—Ru1	73.2 (2)	H26A—C26—H26B	108.1
C5—C4—H4	119.7	C28—C27—C26	111.1 (4)
C3—C4—H4	119.7	C28—C27—H27A	109.4
Ru1—C4—H4	126.5	C26—C27—H27A	109.4
C4—C5—C6	119.4 (4)	C28—C27—H27B	109.4
C4—C5—Ru1	70.7 (2)	C26—C27—H27B	109.4
C6—C5—Ru1	71.2 (2)	H27A—C27—H27B	108.0
C4—C5—H5	120.3	C29—C28—C27	110.8 (4)
C6—C5—H5	120.3	C29—C28—H28A	109.5
Ru1—C5—H5	130.3	C27—C28—H28A	109.5
C7—C6—C5	122.1 (4)	C29—C28—H28B	109.5
C7—C6—Ru1	71.5 (2)	C27—C28—H28B	109.5
C5—C6—Ru1	71.9 (2)	H28A—C28—H28B	108.1
C7—C6—H6	119.0	C28—C29—C30	113.4 (4)
C5—C6—H6	119.0	C28—C29—H29A	108.9
Ru1—C6—H6	130.4	C30—C29—H29A	108.9
C6—C7—C2	117.8 (4)	C28—C29—H29B	108.9
C6—C7—Ru1	71.6 (2)	C30—C29—H29B	108.9
C2—C7—Ru1	71.4 (2)	H29A—C29—H29B	107.7
C6—C7—H7	121.1	C25—C30—C29	110.0 (4)
C2—C7—H7	121.1	C25—C30—H30A	109.7
Ru1—C7—H7	127.8	C29—C30—H30A	109.7
C9—C8—P1	122.6 (2)	C25—C30—H30B	109.7
C9—C8—H8A	106.7	C29—C30—H30B	109.7
P1—C8—H8A	106.7	H30A—C30—H30B	108.2
C9—C8—H8B	106.7	C1—O1—Ru1	92.15 (19)
P1—C8—H8B	106.7	C1—O2—Ru1	92.16 (19)
H8A—C8—H8B	106.6	C8—P1—C19	110.09 (15)
C10—C9—C18	119.5 (3)	C8—P1—C25	104.37 (16)
C10—C9—C8	119.9 (4)	C19—P1—C25	104.11 (15)
C18—C9—C8	120.5 (3)	C8—P1—Ru1	108.75 (10)
C9—C10—C11	120.4 (5)	C19—P1—Ru1	112.78 (11)
C9—C10—H10	119.8	C25—P1—Ru1	116.32 (11)
C11—C10—H10	119.8	O1—Ru1—O2	63.14 (9)
C12—C11—C10	121.1 (5)	O1—Ru1—C4	94.77 (13)
C12—C11—H11	119.4	O2—Ru1—C4	142.45 (13)
C10—C11—H11	119.4	O1—Ru1—C7	154.77 (14)
C11—C12—C13	121.0 (4)	O2—Ru1—C7	106.83 (13)
C11—C12—H12	119.5	C4—Ru1—C7	79.91 (17)
C13—C12—H12	119.5	O1—Ru1—C6	158.39 (14)
C12—C13—C14	121.5 (5)	O2—Ru1—C6	138.42 (14)
C12—C13—C18	118.9 (4)	C4—Ru1—C6	66.45 (16)
C14—C13—C18	119.6 (5)	C7—Ru1—C6	36.83 (16)
C15—C14—C13	122.2 (5)	O1—Ru1—C5	121.43 (13)
C15—C14—H14	118.9	O2—Ru1—C5	173.76 (13)
C13—C14—H14	118.9	C4—Ru1—C5	36.75 (15)
C14—C15—C16	118.5 (5)	C7—Ru1—C5	67.20 (16)
C14—C15—H15	120.7	C6—Ru1—C5	36.98 (16)
C16—C15—H15	120.7	O1—Ru1—C2	116.80 (15)
C17—C16—C15	121.6 (6)	O2—Ru1—C2	95.23 (13)
C17—C16—H16	119.2	C4—Ru1—C2	66.72 (19)
C15—C16—H16	119.2	C7—Ru1—C2	38.51 (18)
C16—C17—C18	121.7 (5)	C6—Ru1—C2	66.96 (15)
C16—C17—H17	119.1	C5—Ru1—C2	78.94 (16)
C18—C17—H17	119.1	O1—Ru1—C3	93.51 (13)
C9—C18—C17	124.7 (3)	O2—Ru1—C3	110.50 (13)
C9—C18—C13	119.0 (4)	C4—Ru1—C3	36.84 (18)
C17—C18—C13	116.3 (4)	C7—Ru1—C3	67.43 (18)
C20—C19—C24	110.0 (3)	C6—Ru1—C3	77.92 (14)
C20—C19—P1	111.8 (2)	C5—Ru1—C3	66.00 (15)
C24—C19—P1	116.4 (2)	C2—Ru1—C3	36.48 (18)
C20—C19—H19	106.0	O1—Ru1—P1	88.99 (6)
C24—C19—H19	106.0	O2—Ru1—P1	86.30 (6)
P1—C19—H19	106.0	C4—Ru1—P1	125.43 (13)
C19—C20—C21	110.3 (3)	C7—Ru1—P1	114.30 (13)
C19—C20—H20A	109.6	C6—Ru1—P1	93.47 (9)
C21—C20—H20A	109.6	C5—Ru1—P1	97.78 (11)
C19—C20—H20B	109.6	C2—Ru1—P1	151.84 (15)
C21—C20—H20B	109.6	C3—Ru1—P1	162.24 (13)
H20A—C20—H20B	108.1	O1—Ru1—C1	31.82 (10)
C20—C21—C22	110.2 (4)	O2—Ru1—C1	31.38 (10)
C20—C21—H21A	109.6	C4—Ru1—C1	120.25 (14)
C22—C21—H21A	109.6	C7—Ru1—C1	133.50 (15)
C20—C21—H21B	109.6	C6—Ru1—C1	169.46 (15)
C22—C21—H21B	109.6	C5—Ru1—C1	152.76 (14)
H21A—C21—H21B	108.1	C2—Ru1—C1	107.16 (13)
C23—C22—C21	111.5 (4)	C3—Ru1—C1	102.69 (12)
C23—C22—H22A	109.3	P1—Ru1—C1	88.63 (7)
C21—C22—H22A	109.3

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O3^i	0.95	2.51	3.179 (5)	127
C29—H29A···Cl3^ii	0.99	2.68	3.457 (6)	135
C31—H31···O3^iii	1.00	2.06	3.004 (5)	156

Symmetry codes: (i) −x+1/2, y+1/2, z; (ii) x+1/2, −y+1/2, −z; (iii) x, y+1, z.