(2,2'-Bi-pyridine)-chlorido-[diethyl (2,2':6',2''-terpyridin-4-yl)phospho-nate]ruthenium(II) hexa-fluorido-phosphate aceto-nitrile/water solvate.

The cationic complex in the title compound, [RuCl(C10H8N2)(C19H20N3O3P)]PF6·0.83CH3CN·0.17H2O, is a water-oxidation precatalyst functionalized for TiO2 attachment via terpyridine phospho-nate. The The Ru(II) atom in the complex has a distorted octa-hedral geometry due to the restricted bite angle [159.50 (18)°] of the terpyridyl ligand. The dihedral angle between the least-squares planes of the terpyridyl and bipyridyl moieties is 86.04 (14)°. The mean Ru-N bond length for bi-pyridine is 2.064 (5) Å, with the bond opposite to Ru-Cl being 0.068 Å shorter. For the substituted terpyridine, the mean Ru-N distance involving the outer N atoms trans to each other is 2.057 (6) Å, whereas the bond length involving the central N atom is 1.944 (5) Å. The Ru-Cl distance is 2.4073 (15) Å. The P atom of the phospho-nate group lies in the same plane as its adjacent pyridyl ring, with the ordinary character of the bond between P and Ctpy [1.801 (6) Å] allowing for free rotation of the terpyridine substituent around the P-Ctpy axis. The aceto-nitrile solvent mol-ecule was refined to be disordered with two water mol-ecules; occupancies for the acetontrile and water mol-ecules were 0.831 (9) and 0.169 (9), respectively. Also disordered was the PF6 (-) counter-ion (over three positions) and one of the eth-oxy substituents (with two positions). The crystal structure shows significant intra- and inter-molecular H⋯X contacts, especially some involving the Cl(-) ligand.

Related literature

For a related crystal stpan class="Chemical">run>cture, see: pan class="Chemical">Zakeeruddin et al. (1997 ▶). For the stpan class="Chemical">ructures of terpyrid­yl/bipyridyl RuII-chlorido compounds relevant to the comparative discussion, see: Chen et al. (2011 ▶, 2013 ▶); Jude et al. (2008 ▶, 2009 ▶, 2013 ▶). For literature used in the synthetic preparations, see: Evans et al. (1973 ▶); Jakubikova et al. (2009 ▶); Zakeeruddin et al. (1997 ▶). For the catalytic properties of related complexes, see: Chen et al. (2009 ▶); Concepcion et al. (2008 ▶); Masaoka & Sakai (2009 ▶); Tseng et al. (2008 ▶); Wasylenko et al. (2010 ▶); Yagi et al. (2011 ▶).

Experimental

Crystal data

[pan class="Chemical">Run>Cl(C10pan class="Species">H8N2)(C19pan class="Chemical">H20N3O3P)]PF6·0.83C2H3N·0.17H2O

M = 847.23

Monoclinic,

a = 8.6367 (14) Å

b = 31.515 (5) Å

c = 12.696 (2) Å

β = 100.155 (2)°

V = 3401.5 (9) Å3

Z = 4

Mo Kα radiation

μ = 0.71 mm−1

T = 120 K

0.28 × 0.20 × 0.08 mm

Data collection

Bpan class="Chemical">run>ker D8 with Apan class="Chemical">PEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bn class="Chemical">pan class="Chemical">ruker, 2007 ▶) T min = 0.826, T max = 0.945

24414 measured reflections

6233 independent reflections

5056 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.062

wR(F 2) = 0.141

S = 1.14

6233 reflections

574 parameters

394 restraints

pan class="Disease">H atomsn> treated by a mixture of independent and constrained refinement

Δρmax = 0.94 e Å−3

Δρmin = −1.20 e Å−3

Data collection: Apan class="Chemical">Pn>EX2 (Bpan class="Chemical">ruker, 2007 ▶); cell refinement: SAINT-pan class="Chemical">Plus (Bruker, 2007 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶) and SHELXLE (Hübschle et al., 2011 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal stpan class="Chemical">run>cture: contains datablock(s) I, New_Global_pan class="Chemical">Publ_Block. DOI: 10.1107/S1600536813022940/zl2555sup1.cif

Stpan class="Chemical">run>cture factors: contains datablock(s) I. DOI: 10.1107/S1600536813022940/zl2555Isup2.hkl

Additional supn class="Chemical">plementary materials: crystallographic information; 3D view; checkCIF report

[RuCl(C10H8N2)(C19H20N3O3P)]PF6·0.83C2H3N·0.17H2O	F(000) = 1710.6
Mr = 847.23	Dx = 1.655 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 8.6367 (14) Å	Cell parameters from 4889 reflections
b = 31.515 (5) Å	θ = 5.0–49.1°
c = 12.696 (2) Å	µ = 0.71 mm−1
β = 100.155 (2)°	T = 120 K
V = 3401.5 (9) Å3	Block, red
Z = 4	0.28 × 0.20 × 0.08 mm

Bruker D8 with APEXII CCD diffractometer	6233 independent reflections
Radiation source: fine-focus sealed tube	5056 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 25.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
Tmin = 0.826, Tmax = 0.945	k = −37→38
24414 measured reflections	l = −15→15

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.062	Hydrogen site location: mixed
wR(F2) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0274P)2 + 23.9905P] where P = (Fo2 + 2Fc2)/3
6233 reflections	(Δ/σ)max = 0.003
574 parameters	Δρmax = 0.94 e Å−3
394 restraints	Δρmin = −1.20 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	Occ. (<1)
Ru1	0.11155 (5)	0.19185 (2)	0.07673 (4)	0.01776 (14)
Cl1	−0.03875 (17)	0.21030 (4)	−0.09533 (11)	0.0228 (3)
P1	0.1827 (2)	0.39059 (5)	0.20621 (14)	0.0343 (4)
O1	0.3502 (6)	0.40325 (15)	0.2183 (5)	0.0492 (14)
N1	0.3155 (5)	0.20702 (15)	0.0232 (4)	0.0188 (10)
N2	0.1283 (5)	0.25162 (14)	0.1148 (4)	0.0180 (10)
N3	−0.0819 (5)	0.19850 (14)	0.1500 (4)	0.0200 (10)
N4	0.2321 (6)	0.16840 (15)	0.2163 (4)	0.0205 (11)
N5	0.1106 (5)	0.12661 (15)	0.0439 (4)	0.0208 (11)
C1	0.4122 (7)	0.18137 (19)	−0.0200 (5)	0.0251 (14)
H1	0.3820	0.1526	−0.0336	0.030*
C2	0.5521 (7)	0.1947 (2)	−0.0452 (5)	0.0243 (13)
H2	0.6182	0.1753	−0.0737	0.029*
C3	0.5956 (7)	0.2366 (2)	−0.0285 (5)	0.0286 (14)
H3	0.6914	0.2465	−0.0465	0.034*
C4	0.4985 (7)	0.2640 (2)	0.0146 (5)	0.0249 (13)
H4	0.5263	0.2930	0.0260	0.030*
C5	0.3599 (7)	0.24847 (18)	0.0409 (5)	0.0208 (12)
C6	0.2522 (7)	0.27427 (18)	0.0923 (5)	0.0215 (13)
C7	0.2689 (7)	0.31671 (19)	0.1202 (5)	0.0249 (13)
H7	0.3569	0.3325	0.1065	0.030*
C8	0.1540 (7)	0.33567 (18)	0.1686 (5)	0.0238 (13)
C9	0.0274 (7)	0.31249 (18)	0.1888 (5)	0.0235 (13)
H9	−0.0523	0.3257	0.2201	0.028*
C10	0.0168 (7)	0.26958 (18)	0.1630 (4)	0.0196 (12)
C11	−0.1020 (7)	0.23929 (17)	0.1854 (4)	0.0194 (12)
C12	−0.2213 (7)	0.24910 (19)	0.2401 (5)	0.0257 (14)
H12	−0.2356	0.2775	0.2613	0.031*
C13	−0.3200 (7)	0.2175 (2)	0.2640 (5)	0.0296 (15)
H13	−0.4013	0.2239	0.3031	0.036*
C14	−0.2997 (7)	0.1765 (2)	0.2308 (5)	0.0284 (14)
H14	−0.3662	0.1543	0.2468	0.034*
C15	−0.1808 (7)	0.16847 (18)	0.1738 (5)	0.0220 (13)
H15	−0.1682	0.1403	0.1502	0.026*
O2	0.0733 (6)	0.41696 (14)	0.1220 (4)	0.0476 (14)
C16	0.1522 (13)	0.4448 (3)	0.0503 (7)	0.073 (3)
H16A	0.2530	0.4319	0.0401	0.088*
H16B	0.0839	0.4476	−0.0207	0.088*
C17	0.1817 (14)	0.4879 (2)	0.1013 (8)	0.077 (3)
H17A	0.2051	0.5083	0.0480	0.116*
H17B	0.2712	0.4863	0.1605	0.116*
H17C	0.0880	0.4972	0.1287	0.116*
O3	0.068 (3)	0.3923 (10)	0.288 (2)	0.0376 (17)	0.207 (13)
C18	0.000 (4)	0.4298 (10)	0.338 (3)	0.043 (3)	0.207 (13)
H18A	−0.0050	0.4550	0.2911	0.051*	0.207 (13)
H18B	−0.1066	0.4232	0.3514	0.051*	0.207 (13)
C19	0.111 (6)	0.4375 (16)	0.442 (3)	0.079 (17)	0.207 (13)
H19A	0.2185	0.4403	0.4279	0.119*	0.207 (13)
H19B	0.1057	0.4135	0.4902	0.119*	0.207 (13)
H19C	0.0805	0.4636	0.4747	0.119*	0.207 (13)
O3B	0.1198 (10)	0.3933 (2)	0.3123 (5)	0.0376 (17)	0.793 (13)
C18B	0.1154 (12)	0.4349 (3)	0.3644 (8)	0.040 (2)	0.793 (13)
H18C	0.0701	0.4565	0.3112	0.048*	0.793 (13)
H18D	0.2232	0.4438	0.3968	0.048*	0.793 (13)
C19B	0.0162 (14)	0.4307 (3)	0.4489 (8)	0.050 (3)	0.793 (13)
H19D	0.0083	0.4583	0.4831	0.075*	0.793 (13)
H19E	0.0643	0.4101	0.5027	0.075*	0.793 (13)
H19F	−0.0891	0.4209	0.4164	0.075*	0.793 (13)
C20	0.2890 (7)	0.19166 (19)	0.3034 (5)	0.0260 (13)
H20	0.2796	0.2217	0.2986	0.031*
C21	0.3592 (8)	0.1744 (2)	0.3978 (5)	0.0298 (15)
H21	0.3961	0.1921	0.4575	0.036*
C22	0.3761 (9)	0.1312 (2)	0.4060 (6)	0.0406 (18)
H22	0.4244	0.1185	0.4714	0.049*
C23	0.3218 (9)	0.1067 (2)	0.3179 (5)	0.0382 (17)
H23	0.3341	0.0768	0.3217	0.046*
C24	0.2493 (7)	0.12545 (18)	0.2234 (5)	0.0253 (14)
C25	0.1897 (7)	0.10225 (18)	0.1243 (5)	0.0245 (13)
C26	0.2106 (8)	0.05900 (19)	0.1113 (5)	0.0324 (15)
H26	0.2660	0.0423	0.1680	0.039*
C27	0.1489 (8)	0.0409 (2)	0.0138 (5)	0.0320 (15)
H27	0.1618	0.0113	0.0029	0.038*
C28	0.0690 (7)	0.0655 (2)	−0.0675 (5)	0.0317 (15)
H28	0.0270	0.0533	−0.1350	0.038*
C29	0.0510 (7)	0.10805 (19)	−0.0493 (5)	0.0270 (14)
H29	−0.0059	0.1250	−0.1050	0.032*
P2	0.7996 (7)	0.04256 (16)	0.2491 (4)	0.0514 (14)	0.726 (14)
F1	0.9091 (15)	0.0792 (2)	0.3042 (7)	0.102 (4)	0.726 (14)
F2	0.7768 (19)	0.0239 (2)	0.3607 (7)	0.124 (5)	0.726 (14)
F3	0.6949 (13)	0.0053 (3)	0.1890 (9)	0.092 (3)	0.726 (14)
F4	0.8227 (9)	0.0618 (2)	0.1346 (5)	0.048 (2)	0.726 (14)
F5	0.6492 (13)	0.0715 (3)	0.2426 (9)	0.092 (3)	0.726 (14)
F6	0.9482 (10)	0.0134 (2)	0.2475 (7)	0.083 (3)	0.726 (14)
P2B	0.755 (2)	0.0482 (6)	0.2461 (15)	0.109 (6)	0.274 (14)
F1B	0.800 (4)	0.0835 (7)	0.3349 (18)	0.118 (8)	0.274 (14)
F2B	0.637 (4)	0.0278 (7)	0.313 (2)	0.130 (9)	0.274 (14)
F3B	0.712 (4)	0.0119 (8)	0.159 (2)	0.136 (9)	0.274 (14)
F4B	0.872 (3)	0.0681 (8)	0.177 (3)	0.134 (10)	0.274 (14)
F5B	0.620 (3)	0.0777 (8)	0.185 (2)	0.110 (8)	0.274 (14)
F6B	0.895 (3)	0.0194 (8)	0.307 (3)	0.181 (10)	0.274 (14)
N6	0.6748 (10)	0.3516 (3)	0.1400 (10)	0.072 (3)	0.831 (9)
C30	0.6579 (11)	0.3871 (3)	0.1224 (10)	0.056 (3)	0.831 (9)
C31	0.6410 (14)	0.4298 (3)	0.1053 (12)	0.081 (4)	0.831 (9)
H31A	0.5756	0.4417	0.1537	0.121*	0.831 (9)
H31B	0.5906	0.4350	0.0310	0.121*	0.831 (9)
H31C	0.7447	0.4434	0.1188	0.121*	0.831 (9)
O4	0.680 (3)	0.3472 (7)	0.254 (2)	0.055 (11)	0.169 (9)
H4A	0.679 (6)	0.3723 (8)	0.271 (6)	0.066*	0.169 (9)
H4B	0.592 (4)	0.3385 (13)	0.228 (7)	0.066*	0.169 (9)
O5	0.505 (5)	0.3723 (8)	−0.026 (2)	0.101 (19)	0.169 (9)
H5A	0.462 (8)	0.3767 (17)	−0.088 (2)	0.122*	0.169 (9)
H5B	0.541 (9)	0.3941 (10)	0.004 (3)	0.122*	0.169 (9)

	U11	U22	U33	U12	U13	U23
Ru1	0.0167 (2)	0.0161 (2)	0.0199 (2)	0.00053 (19)	0.00165 (17)	−0.00016 (19)
Cl1	0.0219 (7)	0.0231 (7)	0.0227 (7)	0.0017 (6)	0.0021 (6)	0.0014 (6)
P1	0.0517 (12)	0.0200 (8)	0.0308 (10)	−0.0051 (8)	0.0062 (8)	−0.0059 (7)
O1	0.050 (3)	0.027 (3)	0.070 (4)	−0.012 (2)	0.010 (3)	−0.014 (2)
N1	0.017 (2)	0.023 (2)	0.016 (2)	0.0008 (19)	0.001 (2)	−0.004 (2)
N2	0.018 (2)	0.019 (2)	0.017 (2)	0.0009 (19)	0.001 (2)	0.0020 (19)
N3	0.019 (2)	0.020 (2)	0.020 (2)	0.001 (2)	0.000 (2)	0.000 (2)
N4	0.020 (3)	0.022 (3)	0.020 (3)	0.001 (2)	0.003 (2)	0.004 (2)
N5	0.017 (2)	0.020 (2)	0.026 (3)	0.0003 (19)	0.003 (2)	0.002 (2)
C1	0.024 (3)	0.027 (3)	0.022 (3)	0.005 (3)	−0.001 (3)	0.000 (3)
C2	0.020 (3)	0.033 (3)	0.019 (3)	0.006 (3)	0.004 (2)	0.004 (3)
C3	0.022 (3)	0.037 (4)	0.026 (3)	−0.002 (3)	0.004 (3)	0.006 (3)
C4	0.020 (3)	0.030 (3)	0.024 (3)	−0.004 (3)	0.004 (3)	0.001 (3)
C5	0.017 (3)	0.026 (3)	0.018 (3)	0.002 (2)	−0.001 (2)	0.000 (2)
C6	0.022 (3)	0.023 (3)	0.020 (3)	0.001 (2)	0.003 (2)	0.003 (2)
C7	0.025 (3)	0.027 (3)	0.023 (3)	−0.004 (3)	0.004 (3)	−0.002 (3)
C8	0.033 (3)	0.018 (3)	0.018 (3)	−0.001 (3)	0.001 (3)	−0.001 (2)
C9	0.027 (3)	0.024 (3)	0.018 (3)	0.004 (3)	0.001 (2)	−0.002 (2)
C10	0.017 (3)	0.022 (3)	0.019 (3)	0.006 (2)	0.003 (2)	0.004 (2)
C11	0.019 (3)	0.020 (3)	0.018 (3)	0.002 (2)	0.001 (2)	0.001 (2)
C12	0.024 (3)	0.024 (3)	0.027 (3)	0.006 (3)	−0.001 (3)	−0.004 (3)
C13	0.022 (3)	0.034 (4)	0.034 (4)	−0.001 (3)	0.009 (3)	0.001 (3)
C14	0.019 (3)	0.034 (3)	0.032 (4)	0.000 (3)	0.004 (3)	0.008 (3)
C15	0.020 (3)	0.022 (3)	0.023 (3)	0.002 (2)	0.002 (3)	0.002 (2)
O2	0.067 (4)	0.022 (2)	0.046 (3)	−0.004 (2)	−0.009 (3)	0.000 (2)
C16	0.128 (9)	0.042 (5)	0.041 (5)	−0.012 (5)	−0.011 (5)	0.016 (4)
C17	0.117 (9)	0.032 (4)	0.078 (7)	−0.020 (5)	0.003 (6)	−0.004 (4)
O3	0.055 (4)	0.026 (2)	0.033 (3)	0.002 (3)	0.010 (3)	−0.011 (3)
C18	0.058 (7)	0.028 (6)	0.041 (6)	−0.001 (6)	0.009 (6)	−0.007 (6)
C19	0.08 (2)	0.08 (2)	0.08 (2)	−0.021 (18)	0.018 (18)	−0.008 (18)
O3B	0.055 (4)	0.026 (2)	0.033 (3)	0.002 (3)	0.010 (3)	−0.011 (3)
C18B	0.056 (5)	0.024 (4)	0.042 (4)	−0.008 (4)	0.016 (4)	−0.011 (3)
C19B	0.060 (7)	0.038 (5)	0.056 (6)	−0.006 (5)	0.024 (5)	−0.020 (5)
C20	0.025 (3)	0.022 (3)	0.029 (3)	0.003 (3)	−0.002 (3)	−0.002 (3)
C21	0.032 (4)	0.033 (3)	0.021 (3)	0.001 (3)	−0.003 (3)	−0.002 (3)
C22	0.051 (5)	0.034 (4)	0.030 (4)	0.005 (3)	−0.010 (3)	−0.001 (3)
C23	0.055 (5)	0.022 (3)	0.034 (4)	0.008 (3)	−0.002 (3)	0.009 (3)
C24	0.027 (3)	0.018 (3)	0.031 (4)	0.000 (2)	0.006 (3)	0.000 (3)
C25	0.015 (3)	0.024 (3)	0.034 (4)	0.001 (2)	0.005 (3)	0.001 (3)
C26	0.042 (4)	0.018 (3)	0.036 (4)	0.003 (3)	0.002 (3)	0.005 (3)
C27	0.040 (4)	0.019 (3)	0.037 (4)	0.003 (3)	0.007 (3)	0.000 (3)
C28	0.026 (3)	0.032 (4)	0.035 (4)	−0.002 (3)	−0.001 (3)	−0.010 (3)
C29	0.026 (3)	0.029 (3)	0.024 (3)	0.003 (3)	−0.003 (3)	0.002 (3)
P2	0.078 (3)	0.023 (2)	0.057 (2)	0.0126 (18)	0.022 (2)	0.0061 (15)
F1	0.167 (9)	0.049 (4)	0.071 (6)	0.001 (5)	−0.027 (6)	−0.013 (4)
F2	0.274 (15)	0.048 (4)	0.075 (5)	0.056 (7)	0.102 (7)	0.021 (4)
F3	0.134 (7)	0.044 (4)	0.115 (7)	−0.035 (5)	0.067 (6)	−0.008 (5)
F4	0.058 (4)	0.037 (4)	0.051 (4)	−0.003 (3)	0.011 (3)	0.008 (3)
F5	0.115 (7)	0.067 (5)	0.111 (9)	0.039 (5)	0.068 (6)	0.021 (5)
F6	0.121 (6)	0.051 (4)	0.081 (6)	0.038 (4)	0.028 (5)	0.014 (4)
P2B	0.141 (13)	0.029 (7)	0.187 (13)	0.024 (7)	0.109 (9)	0.014 (6)
F1B	0.16 (2)	0.069 (12)	0.123 (15)	0.005 (13)	0.016 (14)	0.037 (9)
F2B	0.19 (2)	0.071 (15)	0.16 (2)	−0.012 (14)	0.121 (17)	−0.003 (13)
F3B	0.22 (2)	0.050 (12)	0.184 (18)	−0.037 (12)	0.161 (15)	−0.002 (12)
F4B	0.148 (18)	0.079 (17)	0.20 (2)	−0.031 (14)	0.093 (18)	0.013 (16)
F5B	0.124 (15)	0.061 (13)	0.14 (2)	−0.022 (11)	0.025 (14)	−0.010 (13)
F6B	0.199 (19)	0.119 (18)	0.25 (2)	0.077 (17)	0.098 (18)	0.061 (17)
N6	0.040 (5)	0.039 (5)	0.137 (11)	0.003 (4)	0.014 (6)	0.004 (6)
C30	0.041 (6)	0.039 (6)	0.091 (9)	−0.003 (4)	0.021 (5)	−0.014 (5)
C31	0.080 (9)	0.023 (5)	0.150 (13)	−0.007 (5)	0.052 (9)	−0.011 (6)
O4	0.06 (2)	0.05 (2)	0.06 (2)	0.023 (17)	0.039 (19)	0.027 (17)
O5	0.18 (5)	0.04 (2)	0.08 (3)	−0.01 (3)	0.00 (3)	0.00 (2)

Ru1—N2	1.944 (5)	O3—C18	1.509 (17)
Ru1—N4	2.030 (5)	C18—C19	1.502 (18)
Ru1—N1	2.053 (5)	C18—H18A	0.9900
Ru1—N3	2.061 (5)	C18—H18B	0.9900
Ru1—N5	2.098 (5)	C19—H19A	0.9800
Ru1—Cl1	2.4073 (15)	C19—H19B	0.9800
P1—O1	1.483 (5)	C19—H19C	0.9800
P1—O2	1.540 (5)	O3B—C18B	1.472 (9)
P1—O3B	1.541 (6)	C18B—C19B	1.491 (11)
P1—O3	1.554 (17)	C18B—H18C	0.9900
P1—C8	1.801 (6)	C18B—H18D	0.9900
N1—C1	1.347 (8)	C19B—H19D	0.9800
N1—C5	1.369 (7)	C19B—H19E	0.9800
N2—C10	1.353 (7)	C19B—H19F	0.9800
N2—C6	1.358 (7)	C20—C21	1.358 (8)
N3—C15	1.345 (7)	C20—H20	0.9500
N3—C11	1.383 (7)	C21—C22	1.371 (9)
N4—C20	1.345 (7)	C21—H21	0.9500
N4—C24	1.363 (7)	C22—C23	1.372 (9)
N5—C29	1.340 (8)	C22—H22	0.9500
N5—C25	1.361 (7)	C23—C24	1.383 (9)
C1—C2	1.369 (8)	C23—H23	0.9500
C1—H1	0.9500	C24—C25	1.468 (9)
C2—C3	1.378 (9)	C25—C26	1.389 (8)
C2—H2	0.9500	C26—C27	1.382 (9)
C3—C4	1.381 (9)	C26—H26	0.9500
C3—H3	0.9500	C27—C28	1.376 (9)
C4—C5	1.387 (8)	C27—H27	0.9500
C4—H4	0.9500	C28—C29	1.375 (9)
C5—C6	1.472 (8)	C28—H28	0.9500
C6—C7	1.385 (8)	C29—H29	0.9500
C7—C8	1.391 (9)	P2—F1	1.575 (8)
C7—H7	0.9500	P2—F5	1.577 (8)
C8—C9	1.376 (9)	P2—F2	1.578 (8)
C9—C10	1.391 (8)	P2—F6	1.581 (8)
C9—H9	0.9500	P2—F3	1.592 (8)
C10—C11	1.465 (8)	P2—F4	1.620 (7)
C11—C12	1.375 (8)	P2B—F2B	1.577 (16)
C12—C13	1.379 (9)	P2B—F1B	1.582 (16)
C12—H12	0.9500	P2B—F5B	1.583 (16)
C13—C14	1.380 (9)	P2B—F3B	1.586 (17)
C13—H13	0.9500	P2B—F4B	1.586 (16)
C14—C15	1.379 (9)	P2B—F6B	1.597 (16)
C14—H14	0.9500	N6—C30	1.144 (12)
C15—H15	0.9500	C30—C31	1.369 (13)
O2—C16	1.511 (9)	C31—H31A	0.9800
C16—C17	1.507 (10)	C31—H31B	0.9800
C16—H16A	0.9900	C31—H31C	0.9800
C16—H16B	0.9900	O4—H4A	0.8200 (11)
C17—H17A	0.9800	O4—H4B	0.8200 (11)
C17—H17B	0.9800	O5—H5A	0.8200 (11)
C17—H17C	0.9800	O5—H5B	0.8200 (11)
N2—Ru1—N4	97.55 (19)	H17B—C17—H17C	109.5
N2—Ru1—N1	79.99 (19)	C18—O3—P1	131 (3)
N4—Ru1—N1	92.05 (19)	C19—C18—O3	105 (2)
N2—Ru1—N3	79.62 (19)	C19—C18—H18A	110.7
N4—Ru1—N3	88.54 (19)	O3—C18—H18A	110.7
N1—Ru1—N3	159.50 (18)	C19—C18—H18B	110.7
N2—Ru1—N5	175.42 (19)	O3—C18—H18B	110.7
N4—Ru1—N5	78.45 (19)	H18A—C18—H18B	108.8
N1—Ru1—N5	97.82 (18)	C18—C19—H19A	109.5
N3—Ru1—N5	102.37 (18)	C18—C19—H19B	109.5
N2—Ru1—Cl1	89.79 (14)	H19A—C19—H19B	109.5
N4—Ru1—Cl1	172.62 (14)	C18—C19—H19C	109.5
N1—Ru1—Cl1	90.03 (13)	H19A—C19—H19C	109.5
N3—Ru1—Cl1	92.00 (13)	H19B—C19—H19C	109.5
N5—Ru1—Cl1	94.25 (13)	C18B—O3B—P1	118.9 (6)
O1—P1—O2	113.2 (3)	O3B—C18B—C19B	107.9 (7)
O1—P1—O3B	112.5 (4)	O3B—C18B—H18C	110.1
O2—P1—O3B	108.0 (4)	C19B—C18B—H18C	110.1
O1—P1—O3	130.2 (12)	O3B—C18B—H18D	110.1
O2—P1—O3	93.4 (13)	C19B—C18B—H18D	110.1
O1—P1—C8	111.8 (3)	H18C—C18B—H18D	108.4
O2—P1—C8	107.2 (3)	C18B—C19B—H19D	109.5
O3B—P1—C8	103.4 (4)	C18B—C19B—H19E	109.5
O3—P1—C8	97.8 (11)	H19D—C19B—H19E	109.5
C1—N1—C5	117.6 (5)	C18B—C19B—H19F	109.5
C1—N1—Ru1	128.7 (4)	H19D—C19B—H19F	109.5
C5—N1—Ru1	113.6 (4)	H19E—C19B—H19F	109.5
C10—N2—C6	121.7 (5)	N4—C20—C21	123.3 (6)
C10—N2—Ru1	119.4 (4)	N4—C20—H20	118.4
C6—N2—Ru1	118.9 (4)	C21—C20—H20	118.4
C15—N3—C11	117.4 (5)	C20—C21—C22	119.4 (6)
C15—N3—Ru1	128.9 (4)	C20—C21—H21	120.3
C11—N3—Ru1	113.5 (4)	C22—C21—H21	120.3
C20—N4—C24	117.8 (5)	C21—C22—C23	118.6 (6)
C20—N4—Ru1	125.2 (4)	C21—C22—H22	120.7
C24—N4—Ru1	116.9 (4)	C23—C22—H22	120.7
C29—N5—C25	118.7 (5)	C22—C23—C24	120.3 (6)
C29—N5—Ru1	126.2 (4)	C22—C23—H23	119.8
C25—N5—Ru1	114.8 (4)	C24—C23—H23	119.8
N1—C1—C2	123.2 (6)	N4—C24—C23	120.6 (6)
N1—C1—H1	118.4	N4—C24—C25	114.9 (5)
C2—C1—H1	118.4	C23—C24—C25	124.6 (5)
C1—C2—C3	119.0 (6)	N5—C25—C26	121.5 (6)
C1—C2—H2	120.5	N5—C25—C24	114.6 (5)
C3—C2—H2	120.5	C26—C25—C24	123.9 (6)
C2—C3—C4	119.4 (6)	C27—C26—C25	118.4 (6)
C2—C3—H3	120.3	C27—C26—H26	120.8
C4—C3—H3	120.3	C25—C26—H26	120.8
C3—C4—C5	119.0 (6)	C28—C27—C26	120.1 (6)
C3—C4—H4	120.5	C28—C27—H27	119.9
C5—C4—H4	120.5	C26—C27—H27	119.9
N1—C5—C4	121.7 (5)	C29—C28—C27	118.7 (6)
N1—C5—C6	114.8 (5)	C29—C28—H28	120.6
C4—C5—C6	123.5 (5)	C27—C28—H28	120.6
N2—C6—C7	120.3 (5)	N5—C29—C28	122.5 (6)
N2—C6—C5	112.7 (5)	N5—C29—H29	118.8
C7—C6—C5	127.0 (5)	C28—C29—H29	118.8
C6—C7—C8	118.5 (6)	F1—P2—F5	91.4 (5)
C6—C7—H7	120.7	F1—P2—F2	92.0 (5)
C8—C7—H7	120.7	F5—P2—F2	91.8 (5)
C9—C8—C7	120.4 (5)	F1—P2—F6	90.3 (5)
C9—C8—P1	122.5 (5)	F5—P2—F6	176.3 (6)
C7—C8—P1	117.1 (5)	F2—P2—F6	91.4 (5)
C8—C9—C10	119.6 (6)	F1—P2—F3	177.0 (7)
C8—C9—H9	120.2	F5—P2—F3	90.5 (6)
C10—C9—H9	120.2	F2—P2—F3	90.3 (6)
N2—C10—C9	119.4 (5)	F6—P2—F3	87.7 (5)
N2—C10—C11	113.2 (5)	F1—P2—F4	88.0 (5)
C9—C10—C11	127.4 (5)	F5—P2—F4	88.1 (4)
C12—C11—N3	121.4 (5)	F2—P2—F4	179.9 (7)
C12—C11—C10	124.3 (5)	F6—P2—F4	88.7 (4)
N3—C11—C10	114.2 (5)	F3—P2—F4	89.7 (5)
C11—C12—C13	119.7 (6)	F2B—P2B—F1B	90.1 (10)
C11—C12—H12	120.1	F2B—P2B—F5B	90.6 (11)
C13—C12—H12	120.1	F1B—P2B—F5B	90.1 (10)
C12—C13—C14	119.5 (6)	F2B—P2B—F3B	89.1 (10)
C12—C13—H13	120.3	F1B—P2B—F3B	178.5 (13)
C14—C13—H13	120.3	F5B—P2B—F3B	91.3 (11)
C15—C14—C13	118.5 (6)	F2B—P2B—F4B	178.7 (14)
C15—C14—H14	120.7	F1B—P2B—F4B	91.1 (11)
C13—C14—H14	120.7	F5B—P2B—F4B	89.1 (11)
N3—C15—C14	123.4 (6)	F3B—P2B—F4B	89.7 (11)
N3—C15—H15	118.3	F2B—P2B—F6B	91.0 (11)
C14—C15—H15	118.3	F1B—P2B—F6B	89.3 (11)
C16—O2—P1	116.5 (5)	F5B—P2B—F6B	178.3 (14)
C17—C16—O2	109.0 (7)	F3B—P2B—F6B	89.4 (10)
C17—C16—H16A	109.9	F4B—P2B—F6B	89.3 (11)
O2—C16—H16A	109.9	N6—C30—C31	177.7 (14)
C17—C16—H16B	109.9	C30—C31—H31A	109.5
O2—C16—H16B	109.9	C30—C31—H31B	109.5
H16A—C16—H16B	108.3	H31A—C31—H31B	109.5
C16—C17—H17A	109.5	C30—C31—H31C	109.5
C16—C17—H17B	109.5	H31A—C31—H31C	109.5
H17A—C17—H17B	109.5	H31B—C31—H31C	109.5
C16—C17—H17C	109.5	H4A—O4—H4B	112.0 (2)
H17A—C17—H17C	109.5	H5A—O5—H5B	112.0 (2)
C5—N1—C1—C2	1.0 (8)	C10—C11—C12—C13	−175.1 (6)
Ru1—N1—C1—C2	−174.8 (4)	C11—C12—C13—C14	−1.3 (9)
N1—C1—C2—C3	−1.7 (9)	C12—C13—C14—C15	−0.3 (9)
C1—C2—C3—C4	1.0 (9)	C11—N3—C15—C14	0.2 (8)
C2—C3—C4—C5	0.5 (9)	Ru1—N3—C15—C14	174.8 (4)
C1—N1—C5—C4	0.6 (8)	C13—C14—C15—N3	0.9 (9)
Ru1—N1—C5—C4	177.0 (4)	O1—P1—O2—C16	11.7 (6)
C1—N1—C5—C6	−177.6 (5)	O3B—P1—O2—C16	137.0 (6)
Ru1—N1—C5—C6	−1.2 (6)	O3—P1—O2—C16	148.6 (12)
C3—C4—C5—N1	−1.3 (9)	C8—P1—O2—C16	−112.2 (5)
C3—C4—C5—C6	176.7 (5)	P1—O2—C16—C17	−90.4 (8)
C10—N2—C6—C7	1.1 (8)	O1—P1—O3—C18	67 (4)
Ru1—N2—C6—C7	−178.8 (4)	O2—P1—O3—C18	−58 (3)
C10—N2—C6—C5	179.4 (5)	O3B—P1—O3—C18	85 (5)
Ru1—N2—C6—C5	−0.5 (6)	C8—P1—O3—C18	−166 (3)
N1—C5—C6—N2	1.1 (7)	P1—O3—C18—C19	−93 (4)
C4—C5—C6—N2	−177.0 (5)	O1—P1—O3B—C18B	62.8 (8)
N1—C5—C6—C7	179.3 (6)	O2—P1—O3B—C18B	−62.9 (8)
C4—C5—C6—C7	1.2 (9)	O3—P1—O3B—C18B	−102 (4)
N2—C6—C7—C8	−1.9 (9)	C8—P1—O3B—C18B	−176.3 (7)
C5—C6—C7—C8	−179.9 (5)	P1—O3B—C18B—C19B	166.6 (9)
C6—C7—C8—C9	0.4 (9)	C24—N4—C20—C21	−1.4 (9)
C6—C7—C8—P1	178.7 (4)	Ru1—N4—C20—C21	175.1 (5)
O1—P1—C8—C9	156.3 (5)	N4—C20—C21—C22	1.0 (10)
O2—P1—C8—C9	−79.0 (6)	C20—C21—C22—C23	0.3 (11)
O3B—P1—C8—C9	35.0 (6)	C21—C22—C23—C24	−1.1 (12)
O3—P1—C8—C9	17.0 (14)	C20—N4—C24—C23	0.6 (9)
O1—P1—C8—C7	−21.9 (6)	Ru1—N4—C24—C23	−176.2 (5)
O2—P1—C8—C7	102.8 (5)	C20—N4—C24—C25	−177.8 (5)
O3B—P1—C8—C7	−143.2 (5)	Ru1—N4—C24—C25	5.3 (7)
O3—P1—C8—C7	−161.1 (14)	C22—C23—C24—N4	0.6 (11)
C7—C8—C9—C10	1.7 (9)	C22—C23—C24—C25	178.9 (7)
P1—C8—C9—C10	−176.4 (4)	C29—N5—C25—C26	0.5 (9)
C6—N2—C10—C9	1.0 (8)	Ru1—N5—C25—C26	−174.6 (5)
Ru1—N2—C10—C9	−179.0 (4)	C29—N5—C25—C24	−179.5 (5)
C6—N2—C10—C11	−176.9 (5)	Ru1—N5—C25—C24	5.4 (6)
Ru1—N2—C10—C11	3.0 (6)	N4—C24—C25—N5	−7.0 (8)
C8—C9—C10—N2	−2.4 (8)	C23—C24—C25—N5	174.6 (6)
C8—C9—C10—C11	175.2 (5)	N4—C24—C25—C26	172.9 (6)
C15—N3—C11—C12	−1.8 (8)	C23—C24—C25—C26	−5.4 (10)
Ru1—N3—C11—C12	−177.2 (4)	N5—C25—C26—C27	0.1 (10)
C15—N3—C11—C10	175.9 (5)	C24—C25—C26—C27	−179.9 (6)
Ru1—N3—C11—C10	0.5 (6)	C25—C26—C27—C28	0.0 (10)
N2—C10—C11—C12	175.5 (5)	C26—C27—C28—C29	−0.5 (10)
C9—C10—C11—C12	−2.3 (9)	C25—N5—C29—C28	−1.1 (9)
N2—C10—C11—N3	−2.2 (7)	Ru1—N5—C29—C28	173.4 (5)
C9—C10—C11—N3	−179.9 (5)	C27—C28—C29—N5	1.2 (10)
N3—C11—C12—C13	2.4 (9)

Table 1

Selected bond lengths (Å)

Ru1—N2	1.944 (5)
Ru1—N4	2.030 (5)
Ru1—N1	2.053 (5)
Ru1—N3	2.061 (5)
Ru1—N5	2.098 (5)
Ru1—Cl1	2.4073 (15)
P1—O1	1.483 (5)
P1—O2	1.540 (5)
P1—O3B	1.541 (6)
P1—O3	1.554 (17)
P1—C8	1.801 (6)