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1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN Chlorido(chlorodiphenylphosphine-jP)- (diphenylpiperidinophosphine-jp)- (g 5 -pentamethylcyclopentadienyl)- ruthenium(ii) Florian Jantscher, a Karl Kirchner a and Kurt Mereiter b * a Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163, A-1060 Vienna, Austria, and b Institute of Chemical Technologies and Analytics, Vienna University of Technology, Getreidemarkt 9/164SC, A-1060 Vienna, Austria Correspondence kurt.mereiter@tuwien.ac.at Received 12 July 2009; accepted 14 July 2009 Experimental Crystal data [Ru(C 10 H 15 )Cl(C 12 H 10 ClP)- (C 17 H 20 NP)] M r = Monoclinic, P2 1 =c a = (12) Å b = (6) Å c = (15) Å Data collection Bruker SMART APEX CCD diffractometer Absorption correction: multi-scan (SADABS; Bruker, 2003) T min = 0.61, T max = 0.76 Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections = (1) V = (4) Å 3 Z =4 Mo K radiation = 0.72 mm 1 T = 173 K mm measured reflections independent reflections 8628 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 1.10 e Å 3 min = 0.97 e Å 3 Key indicators: single-crystal X-ray study; T = 173 K; mean (C C) = Å; R factor = 0.033; wr factor = 0.083; data-to-parameter ratio = Table 1 Selected bond lengths (Å). The title compound, [Ru(C 10 H 15 )Cl(C 12 H 10 ClP)(C 17 H 20 NP)], is a half-sandwich complex of Ru II with the chlorodiphenylphosphine ligand formed from the diphenylpiperidinophosphine and chlorine of the precursor complex [Ru( 5 -C 5 Me 5 )( 1 P Ph 2 PNC 5 H 10 )Cl 2 ] by an unexpected reaction with NaBH 4. The complex has a three-legged piano-stool geometry, with Ru P bond lengths of (5) Å for the chlorophosphine and (5) Å for the aminophosphine. Related literature For general background to the reaction of half-sandwich ruthenium aminophosphine complexes with diynes, see: Pavlik et al. (2006). For the unexpected formation and the crystal structure of a related Ru chlorodiphenylphosphine complex, see: Torres-Lubia et al. (1999). For the unexpected formation of another Mn chlorodiphenylphosphine complex, see: Liu et al. (1995). For the preparation of [Ru(Cp*)Cl 2 ] 2, see: Oshima et al. (1984). Ru C (2) Ru C (2) Ru C (2) Ru C (2) Ru C (2) Ru Cl (5) Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT, SADABS and XPREP (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL. Financial support by the FWF Austrian Science Fund (project No. P16600-N11) is gratefully acknowledged. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: GK2223). References Bruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Liu, S.-T., Huo, D.-R., Lin, T.-C., Cheng, M.-C. & Peng, S.-M. (1995). Organometallics, 14, Oshima, N., Suzuki, H. & Moro-oka, Y. (1984). Chem. Lett. 13, Pavlik, S., Jantscher, F., Dazinger, G., Mereiter, K. & Kirchner, K. (2006). Eur. J. Inorg. Chem. pp Sheldrick, G. M. (2008). Acta Cryst. A64, Torres-Lubia, R., Rosales-Hoz, M. J., Arif, A. M., Ernst, R. D. & Paz-Sandoval, M. A. (1999). J. Organomet. Chem. 585, doi: /s Jantscher et al. m941

2 supporting information [doi: /s ] Chlorido(chlorodiphenylphosphine-κP)(diphenylpiperidinophosphine-κP)(η 5 - pentamethylcyclopentadienyl)ruthenium(ii) Florian Jantscher, Karl Kirchner and Kurt Mereiter S1. Comment We found that halfsandwich ruthenium aminophosphine complexes [Ru(Cp )(κ 1 P Ph 2 PNRR ) 2 (CH 3 CN) 2 ] + (Cp is either Cp = cyclopentadienyl or Cp* = pentamethylcyclopentadienyl; Ph = phenyl; NRR = NH n Pr, NEt 2, or NC 5 H 10 = piperidin-1-yl) react with diynes to afford novel η 3 -phosphaallyl-η 2 -vinylamine complexes and may transform under certain conditions to aminocarbenes (Pavlik et al., 2006). In continuation of this work we were interested to react [Ru(Cp*)(κ 1 P Ph 2 PNC 5 H 10 )Cl 2 ], a Ru(III) complex, with NaBH 4 in order to obtain a hydrido or borohydride complex. After workup of the reaction, NMR spectra indicated that another unknown Ru complex must have formed which was studied subsequently with X-ray diffraction and is reported here. The title compound, (I), turned out to contain, in addition to an intact piperidinodiphenylphosphine (Ph 2 PNC 5 H 10 ), a chlorodiphenylphosphine as the second phosphine ligand of a half-sandwich complex with a three-legged piano-stool structure (Fig. 1). It is a Ru II complex with the chemical formula [Ru(Cp*)(κ 1 P Ph 2 PCl)(κ 1 P Ph 2 PNC 5 H 10 )Cl] that bears similarities to [Ru(Cp*)(κ 1 P Ph 2 PCl) 2 Cl] (Torres-Lubia et al., 1999) with respect to stereochemistry of the complex, but also with respect to its formation. In case of [Ru(Cp*)(κ 1 P Ph 2 PCl) 2 Cl] the chlorophosphine was not directly introduced but formed from [Ru(Cp*)(κ 1 P Ph 2 PH) 2 Cl] (Ph 2 PH = hydridodiphenylphosphine) in CDCl 3 as the solvent in the presence of the strong base DBN (1,5-diazabicyclo[4.3.0]non-5-ene) by a stepwise chlorine/hydride exchange between the solvent and the two hydridophosphines. In a related way the title compound must have formed from [Ru(Cp*)(κ 1 P Ph 2 PNC 5 H 10 )Cl 2 ] and NaBH 4. However, there were no chlorinated solvents present in our reaction and the chlorine of the generated chlorophosphine must originate from the starting complex. It can be speculated that the formation of the title compound involves the intermediary formation of a hydridodiphenylphosphine, which by a hydride/chloride substitution leads to the chlorodiphenylphosphine of the title compound obtained in a poor yield of only 9%. A related and also unexpected transformation of a thiol-substituted hydridodiphenylphosphine into a thiol-substituted chlorodiphenylphosphine was observed in the reaction with Mn(CO) 5 Br in chloroform (Liu et al., 1995). Bond lengths and angles in the title compound (see Table 1 and supplementary materials) are similar to those of [Ru(Cp*)(κ 1 P Ph 2 PCl) 2 Cl] (Torres-Lubia et al., 1999), which has <Ru C> = (20) Å (2.245 (21) Å for (I)), Ru P = (2) and (2) Å, Ru Cl = (2) Å, and P Cl = (3) Å. Both Ru complexes adopt related conformations and have in common that the Ru-bonded and the P-bonded Cl lie on opposite sides. In both complexes the phosphine ligands adopt orientations that lead to a stabilization by intramolecular π-π-stacking between the two adjacent phenyl rings (Fig. 1) with a shortest contact distance of C(12) C(28) = (3) Å in the title compound (ring-ring centroid distance (2) Å, ring-ring inclination angle ). Moreover, it is remarkable that the title compound shows eight intramolecular C H Cl/N interactions (seven to Cl, one to N), but only one intermolecular C H Cl interaction (see supplementary materials). sup-1

3 S2. Experimental The synthesis of [Ru(Cp*)(κ 1 P-PPh 2 NC 5 H 10 )(κ 1 P-PPh 2 Cl)Cl], (I), was carried out as follows: A solution of [Ru(Cp*)Cl 2 ] 2 (322 mg, 0.52 mmol) (Oshima et al., 1984) in THF (10 ml) in THF (10 ml) was treated with Ph 2 PNC 5 H 10 (300 mg, 1.2 mmol) and the solution was stirred for 1 h at room temperature. After that NaBH 4 (150 mg, 4.0 mmol) was added and the mixture was stirred for 12 h. After evaporation of the solvent an oily residue was obtained from which the product was extracted with pentane (2 x 10 ml). The volume of the solution was then reduced to about 0.5 ml whereupon red crystals of the title compound were obtained. Yield: 42 mg (9%). 1 H NMR (C 6 D 6, 293 K, δ, p.p.m.): [m, 20H, Ph], [m, 4H, CH 2 ], 1.40 [s, 15H, Cp*], [m, 4H, CH 2 ], [m, 2H, CH 2 ]. 13 C{ 1 H} NMR (C 6 D 6, 293 K, δ, p.p.m.): [Ph], 93.2 [Cp*], [CH 2 ], 26.2 [CH 2 ], 24.6 [CH 2 ], 8.9 [Cp*]. 31 P{ 1 H} NMR (acetone-d 6, 293 K, δ, p.p.m.): 93.1 [d, J HP = 37.2 Hz, PPh 2 Cl], 36.0 [d, J HP = 38.5 Hz, PPh 2 N]. Crystals for X-ray diffraction were obtained by cooling a pentane solution to -20 C. S3. Refinement All H atoms were placed in calculated positions, with C H = Å, and were thereafter treated as riding, with U iso (H) values of 1.5U eq (C) for methyl groups and 1.2U eq (C) for others. Figure 1 Perspective view of the title compound with the atom numbering scheme. Displacement ellipsoids are at the 30% probability level. Chlorido(chlorodiphenylphosphine-κP)(diphenylpiperidinophosphine- κp)(η 5 - pentamethylcyclopentadienyl)ruthenium(ii) Crystal data [Ru(C 10 H 15 )Cl(C 12 H 10 ClP)(C 17 H 20 NP)] M r = Monoclinic, P2 1 /c Hall symbol: -P 2ybc a = (12) Å b = (6) Å sup-2

4 c = (15) Å β = (1) V = (4) Å 3 Z = 4 F(000) = 1576 D x = Mg m 3 Mo Kα radiation, λ = Å Data collection Bruker SMART APEX CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: multi-scan (SADABS; Bruker, 2003) T min = 0.61, T max = 0.76 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 411 parameters 0 restraints Primary atom site location: structure-invariant direct methods Cell parameters from 8233 reflections θ = µ = 0.72 mm 1 T = 173 K Block, orange mm measured reflections independent reflections 8628 reflections with I > 2σ(I) R int = θ max = 30.0, θ min = 2.4 h = k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0326P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 1.10 e Å 3 Δρ min = 0.97 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. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wr and goodness of fit S are based on F 2, conventional R-factors R are based on F, with F set to zero for negative F 2. The threshold expression of F 2 > σ(f 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Ru (8) (17) (6) (4) Cl (3) (6) (2) (10) Cl (4) (8) (3) (16) P (3) (5) (2) (9) P (3) (6) (2) (11) N (9) (18) (7) (3) C (12) (2) (9) (4) C (11) (2) (9) (4) C (12) (2) (10) (4) C (13) (3) (10) (5) sup-3

5 C (11) (3) (10) (4) C (14) (3) (11) (6) H6A * H6B * H6C * C (13) (3) (10) (5) H7A * H7B * H7C * C (15) (3) (13) (6) H8A * H8B * H8C * C (18) (3) (12) (7) H9A * H9B * H9C * C (13) (4) (13) (7) H10A * H10B * H10C * C (11) (2) (8) (4) C (12) (2) (9) (4) H * C (14) (3) (10) (5) H * C (15) (3) (11) (6) H * C (14) (3) (11) (6) H * C (12) (3) (10) (5) H * C (10) (2) (9) (4) C (11) (2) (11) (4) H * C (13) (3) (13) (6) H * C (14) (3) (16) (7) H * C (14) (3) (15) (7) H * C (13) (3) (12) (5) H * C (13) (2) (9) (4) H23A * H23B * C (14) (3) (10) (5) H24A * sup-4

6 H24B * C (15) (3) (10) (5) H25A * H25B * C (13) (3) (10) (5) H26A * H26B * C (11) (2) (9) (4) H27A * H27B * C (12) (3) (9) (5) C (15) (3) (11) (6) H * C (19) (4) (13) (8) H * C (2) (4) (13) (9) H * C (18) (4) (12) (9) H * C (15) (3) (11) (6) H * C (12) (2) (9) (4) C (13) (3) (10) (5) H * C (15) (3) (12) (5) H * C (15) (3) (11) (6) H * C (15) (3) (10) (6) H * C (14) (3) (9) (5) H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Ru (7) (8) (7) (5) (5) (5) Cl (2) (2) (2) (18) (18) (18) Cl (3) (4) (3) (3) (3) (3) P (2) (2) (2) (16) (16) (17) P (2) (3) (2) (19) (17) (19) N (7) (8) (7) (6) (6) (6) C (9) (11) (9) (8) (7) (8) C (9) (10) (9) (7) (7) (8) C (10) (10) (10) (8) (8) (8) C (11) (12) (10) (9) (8) (9) C (9) (12) (10) (8) (7) (9) C (13) (15) (11) (11) (9) (11) sup-5

7 C (11) (13) (10) (10) (8) (9) C (13) (11) (15) (9) (11) (10) C (18) (15) (14) (13) (13) (12) C (10) (2) (14) (11) (10) (14) C (9) (10) (8) (7) (7) (7) C (10) (10) (9) (8) (7) (8) C (13) (12) (10) (10) (9) (9) C (14) (16) (11) (12) (10) (10) C (11) (17) (12) (11) (9) (11) C (10) (13) (10) (9) (8) (9) C (8) (9) (10) (7) (7) (8) C (9) (10) (11) (8) (8) (9) C (11) (12) (16) (9) (11) (11) C (12) (12) (2) (9) (13) (13) C (12) (13) (2) (10) (12) (14) C (10) (12) (13) (9) (9) (10) C (10) (10) (9) (8) (8) (8) C (12) (13) (10) (10) (9) (9) C (14) (13) (10) (11) (10) (9) C (12) (13) (11) (10) (9) (10) C (9) (11) (9) (8) (7) (8) C (10) (14) (9) (9) (7) (9) C (13) (16) (11) (11) (10) (11) C (19) (2) (14) (16) (13) (14) C (2) (2) (14) (19) (14) (15) C (16) (3) (13) (17) (11) (14) C (13) (18) (12) (12) (10) (12) C (10) (11) (9) (8) (7) (8) C (11) (12) (11) (9) (9) (9) C (12) (14) (13) (10) (10) (11) C (14) (14) (12) (11) (11) (10) C (15) (15) (10) (12) (10) (10) C (12) (13) (9) (10) (8) (9) Geometric parameters (Å, º) Ru C (2) C15 H Ru C (2) C16 H Ru C (2) C17 C (3) Ru C (2) C17 C (3) Ru C (2) C18 C (3) Ru P (5) C18 H Ru P (5) C19 C (4) Ru Cl (5) C19 H P1 N (16) C20 C (4) P1 C (2) C20 H P1 C (2) C21 C (4) P2 Cl (8) C21 H sup-6

8 P2 C (2) C22 H P2 C (2) C23 C (3) N1 C (2) C23 H23A N1 C (2) C23 H23B C1 C (3) C24 C (3) C1 C (3) C24 H24A C1 C (3) C24 H24B C2 C (3) C25 C (4) C2 C (3) C25 H25A C3 C (3) C25 H25B C3 C (3) C26 C (3) C4 C (3) C26 H26A C4 C (3) C26 H26B C5 C (3) C27 H27A C6 H6A C27 H27B C6 H6B C28 C (3) C6 H6C C28 C (4) C7 H7A C29 C (4) C7 H7B C29 H C7 H7C C30 C (5) C8 H8A C30 H C8 H8B C31 C (5) C8 H8C C31 H C9 H9A C32 C (4) C9 H9B C32 H C9 H9C C33 H C10 H10A C34 C (3) C10 H10B C34 C (3) C10 H10C C35 C (3) C11 C (3) C35 H C11 C (3) C36 C (4) C12 C (3) C36 H C12 H C37 C (4) C13 C (4) C37 H C13 H C38 C (3) C14 C (4) C38 H C14 H C39 H C15 C (3) P1 Ru P (2) C16 C11 P (17) P1 Ru Cl (2) C12 C11 P (15) P2 Ru Cl (2) C13 C12 C (2) N1 P1 C (8) C13 C12 H N1 P1 C (8) C11 C12 H C11 P1 C (9) C14 C13 C (2) Cl2 P2 C (8) C14 C13 H Cl2 P2 C (8) C12 C13 H C28 P2 C (9) C13 C14 C (2) sup-7

9 C3 Ru C (8) C13 C14 H C3 Ru C (8) C15 C14 H C4 Ru C (9) C14 C15 C (2) C3 Ru C (8) C14 C15 H C4 Ru C (8) C16 C15 H C5 Ru C (8) C15 C16 C (2) C3 Ru P (6) C15 C16 H C4 Ru P (6) C11 C16 H C5 Ru P (6) C22 C17 C (2) C1 Ru P (6) C22 C17 P (17) C3 Ru C (8) C18 C17 P (16) C4 Ru C (8) C17 C18 C (2) C5 Ru C (7) C17 C18 H C1 Ru C (7) C19 C18 H P2 Ru C (6) C20 C19 C (3) C3 Ru P (6) C20 C19 H C4 Ru P (6) C18 C19 H C5 Ru P (5) C19 C20 C (2) C1 Ru P (6) C19 C20 H C2 Ru P (5) C21 C20 H C3 Ru Cl (6) C20 C21 C (2) C4 Ru Cl (6) C20 C21 H C5 Ru Cl (6) C22 C21 H C1 Ru Cl (6) C21 C22 C (2) C2 Ru Cl (6) C21 C22 H N1 P1 Ru (6) C17 C22 H C17 P1 Ru (6) N1 C23 C (17) C11 P1 Ru (6) N1 C23 H23A C34 P2 Ru (7) C24 C23 H23A C28 P2 Ru (7) N1 C23 H23B Cl2 P2 Ru (3) C24 C23 H23B C2 C1 C (19) H23A C23 H23B C2 C1 C (2) C23 C24 C (19) C5 C1 C (2) C23 C24 H24A C2 C1 Ru (11) C25 C24 H24A C5 C1 Ru (11) C23 C24 H24B C6 C1 Ru (16) C25 C24 H24B C1 C2 C (18) H24A C24 H24B C1 C2 C (2) C26 C25 C (19) C3 C2 C (2) C26 C25 H25A C1 C2 Ru (11) C24 C25 H25A C3 C2 Ru (11) C26 C25 H25B C7 C2 Ru (14) C24 C25 H25B C4 C3 C (19) H25A C25 H25B C4 C3 C (2) C25 C26 C (19) C2 C3 C (2) C25 C26 H26A C4 C3 Ru (12) C27 C26 H26A C2 C3 Ru (11) C25 C26 H26B sup-8

10 C8 C3 Ru (16) C27 C26 H26B C5 C4 C (19) H26A C26 H26B C5 C4 C (2) N1 C27 C (17) C3 C4 C (2) N1 C27 H27A C5 C4 Ru (12) C26 C27 H27A C3 C4 Ru (11) N1 C27 H27B C9 C4 Ru (16) C26 C27 H27B C4 C5 C (18) H27A C27 H27B C4 C5 C (2) C33 C28 C (2) C1 C5 C (2) C33 C28 P (2) C4 C5 Ru (11) C29 C28 P (17) C1 C5 Ru (11) C28 C29 C (3) C10 C5 Ru (16) C28 C29 H C1 C6 H6A C30 C29 H C1 C6 H6B C31 C30 C (3) H6A C6 H6B C31 C30 H C1 C6 H6C C29 C30 H H6A C6 H6C C32 C31 C (3) H6B C6 H6C C32 C31 H C2 C7 H7A C30 C31 H C2 C7 H7B C31 C32 C (3) H7A C7 H7B C31 C32 H C2 C7 H7C C33 C32 H H7A C7 H7C C28 C33 C (3) H7B C7 H7C C28 C33 H C3 C8 H8A C32 C33 H C3 C8 H8B C35 C34 C (2) H8A C8 H8B C35 C34 P (16) C3 C8 H8C C39 C34 P (17) H8A C8 H8C C34 C35 C (2) H8B C8 H8C C34 C35 H C4 C9 H9A C36 C35 H C4 C9 H9B C37 C36 C (2) H9A C9 H9B C37 C36 H C4 C9 H9C C35 C36 H H9A C9 H9C C38 C37 C (2) H9B C9 H9C C38 C37 H C5 C10 H10A C36 C37 H C5 C10 H10B C37 C38 C (2) H10A C10 H10B C37 C38 H C5 C10 H10C C39 C38 H H10A C10 H10C C38 C39 C (2) H10B C10 H10C C38 C39 H C16 C11 C (19) C34 C39 H C3 Ru P1 N (9) C2 C3 C4 C (2) C4 Ru P1 N (11) C8 C3 C4 C9 1.7 (3) C5 Ru P1 N (16) Ru C3 C4 C (2) sup-9

11 C1 Ru P1 N (9) C2 C3 C4 Ru (13) P2 Ru P1 N (6) C8 C3 C4 Ru (2) C2 Ru P1 N (8) C3 Ru C4 C (18) Cl1 Ru P1 N (6) C1 Ru C4 C (12) C3 Ru P1 C (9) P2 Ru C4 C (12) C4 Ru P1 C (12) C2 Ru C4 C (13) C5 Ru P1 C (16) P1 Ru C4 C (11) C1 Ru P1 C (10) Cl1 Ru C4 C (14) P2 Ru P1 C (7) C5 Ru C4 C (18) C2 Ru P1 C (9) C1 Ru C4 C (14) Cl1 Ru P1 C (7) P2 Ru C4 C (12) C3 Ru P1 C (10) C2 Ru C4 C (12) C4 Ru P1 C (12) P1 Ru C4 C (17) C5 Ru P1 C (16) Cl1 Ru C4 C (11) C1 Ru P1 C (10) C3 Ru C4 C (3) P2 Ru P1 C (8) C5 Ru C4 C (3) C2 Ru P1 C (10) C1 Ru C4 C (3) Cl1 Ru P1 C (8) P2 Ru C4 C9 1.7 (2) C3 Ru P2 C (10) C2 Ru C4 C (3) C4 Ru P2 C (10) P1 Ru C4 C (2) C5 Ru P2 C (11) Cl1 Ru C4 C (3) C1 Ru P2 C (14) C3 C4 C5 C1 1.4 (2) C2 Ru P2 C (13) C9 C4 C5 C (2) P1 Ru P2 C (8) Ru C4 C5 C (14) Cl1 Ru P2 C (8) C3 C4 C5 C (2) C3 Ru P2 C (11) C9 C4 C5 C (4) C4 Ru P2 C (11) Ru C4 C5 C (2) C5 Ru P2 C (11) C3 C4 C5 Ru (14) C1 Ru P2 C (14) C9 C4 C5 Ru (2) C2 Ru P2 C (13) C2 C1 C5 C4 1.7 (2) P1 Ru P2 C (10) C6 C1 C5 C (2) Cl1 Ru P2 C (10) Ru C1 C5 C (14) C3 Ru P2 Cl (7) C2 C1 C5 C (2) C4 Ru P2 Cl (7) C6 C1 C5 C (3) C5 Ru P2 Cl (7) Ru C1 C5 C (2) C1 Ru P2 Cl (11) C2 C1 C5 Ru (14) C2 Ru P2 Cl (10) C6 C1 C5 Ru (2) P1 Ru P2 Cl (3) C3 Ru C5 C (12) Cl1 Ru P2 Cl (3) C1 Ru C5 C (18) C17 P1 N1 C (15) P2 Ru C5 C (12) C11 P1 N1 C (16) C2 Ru C5 C (13) Ru P1 N1 C (16) P1 Ru C5 C (17) C17 P1 N1 C (16) Cl1 Ru C5 C (12) C11 P1 N1 C (16) C3 Ru C5 C (13) Ru P1 N1 C (12) C4 Ru C5 C (18) C3 Ru C1 C (12) P2 Ru C5 C (11) C4 Ru C1 C (14) C2 Ru C5 C (12) C5 Ru C1 C (19) P1 Ru C5 C (2) sup-10

12 P2 Ru C1 C (12) Cl1 Ru C5 C (12) P1 Ru C1 C (13) C3 Ru C5 C (3) Cl1 Ru C1 C (12) C4 Ru C5 C (3) C3 Ru C1 C (14) C1 Ru C5 C (3) C4 Ru C1 C (13) P2 Ru C5 C (3) P2 Ru C1 C (19) C2 Ru C5 C (3) C2 Ru C1 C (19) P1 Ru C5 C (2) P1 Ru C1 C (11) Cl1 Ru C5 C (2) Cl1 Ru C1 C (12) N1 P1 C11 C (18) C3 Ru C1 C (2) C17 P1 C11 C (2) C4 Ru C1 C (2) Ru P1 C11 C (16) C5 Ru C1 C (2) N1 P1 C11 C (16) P2 Ru C1 C (19) C17 P1 C11 C (15) C2 Ru C1 C (3) Ru P1 C11 C (17) P1 Ru C1 C (2) C16 C11 C12 C (3) Cl1 Ru C1 C (19) P1 C11 C12 C (16) C5 C1 C2 C3 4.2 (2) C11 C12 C13 C (3) C6 C1 C2 C (2) C12 C13 C14 C (3) Ru C1 C2 C (14) C13 C14 C15 C (4) C5 C1 C2 C (19) C14 C15 C16 C (4) C6 C1 C2 C7 8.4 (3) C12 C11 C16 C (3) Ru C1 C2 C (2) P1 C11 C16 C (17) C5 C1 C2 Ru (13) N1 P1 C17 C (17) C6 C1 C2 Ru (2) C11 P1 C17 C (18) C3 Ru C2 C (18) Ru P1 C17 C (17) C4 Ru C2 C (14) N1 P1 C17 C (18) C5 Ru C2 C (13) C11 P1 C17 C (17) P2 Ru C2 C (13) Ru P1 C17 C (16) P1 Ru C2 C (12) C22 C17 C18 C (3) Cl1 Ru C2 C (14) P1 C17 C18 C (17) C4 Ru C2 C (12) C17 C18 C19 C (3) C5 Ru C2 C (13) C18 C19 C20 C (4) C1 Ru C2 C (18) C19 C20 C21 C (4) P2 Ru C2 C (17) C20 C21 C22 C (4) P1 Ru C2 C (11) C18 C17 C22 C (3) Cl1 Ru C2 C (10) P1 C17 C22 C (18) C3 Ru C2 C (3) C27 N1 C23 C (2) C4 Ru C2 C (3) P1 N1 C23 C (15) C5 Ru C2 C (3) N1 C23 C24 C (3) C1 Ru C2 C (3) C23 C24 C25 C (3) P2 Ru C2 C (2) C24 C25 C26 C (3) P1 Ru C2 C (2) C23 N1 C27 C (2) Cl1 Ru C2 C (2) P1 N1 C27 C (15) C1 C2 C3 C4 5.0 (2) C25 C26 C27 N (3) C7 C2 C3 C (19) C34 P2 C28 C (2) Ru C2 C3 C (14) Cl2 P2 C28 C (2) C1 C2 C3 C (2) Ru P2 C28 C (19) C7 C2 C3 C8 0.5 (3) C34 P2 C28 C (19) sup-11

13 Ru C2 C3 C (2) Cl2 P2 C28 C (16) C1 C2 C3 Ru (14) Ru P2 C28 C (19) C7 C2 C3 Ru (2) C33 C28 C29 C (4) C5 Ru C3 C (13) P2 C28 C29 C (2) C1 Ru C3 C (14) C28 C29 C30 C (4) P2 Ru C3 C (13) C29 C30 C31 C (5) C2 Ru C3 C (18) C30 C31 C32 C (5) P1 Ru C3 C (12) C29 C28 C33 C (3) Cl1 Ru C3 C (18) P2 C28 C33 C (19) C4 Ru C3 C (18) C31 C32 C33 C (4) C5 Ru C3 C (13) C28 P2 C34 C (19) C1 Ru C3 C (11) Cl2 P2 C34 C (17) P2 Ru C3 C (10) Ru P2 C34 C (2) P1 Ru C3 C (11) C28 P2 C34 C (2) Cl1 Ru C3 C (18) Cl2 P2 C34 C (19) C4 Ru C3 C (3) Ru P2 C34 C (16) C5 Ru C3 C (2) C39 C34 C35 C (4) C1 Ru C3 C (2) P2 C34 C35 C (19) P2 Ru C3 C (2) C34 C35 C36 C (4) C2 Ru C3 C (3) C35 C36 C37 C (4) P1 Ru C3 C (2) C36 C37 C38 C (4) Cl1 Ru C3 C (16) C37 C38 C39 C (4) C2 C3 C4 C5 3.9 (2) C35 C34 C39 C (3) C8 C3 C4 C (2) P2 C34 C39 C (18) Ru C3 C4 C (15) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A C6 H6B Cl (2) 131 C12 H12 Cl (2) 154 C18 H18 N (3) 107 C22 H22 Cl (2) 135 C23 H23A Cl (2) 130 C29 H29 Cl (3) 125 C33 H33 Cl (3) 113 C37 H37 Cl1 i (2) 159 C39 H39 Cl (2) 115 Symmetry code: (i) x+1, y+1/2, z+1/2. sup-12