Bis­[tris­(ethyl­enedi­amine)­cobalt(III)] di­chloro­bis­[μ-(1-hydroxy­ethyl­idene)­di­phospho­nato(4–)]­di­ruthenium(II,­III)­(Ru–Ru) chloride trihydrate

In the title compound, [Co(C₂H₈N₂)₃]₂[Ru₂(C₂H₄O₇P₂)₂Cl₂]Cl·3H₂O, the building unit contains two crystallographically independent dinuclear [Ru₂(hedp)₂Cl₂]⁵⁻ anions, where hedp [viz. (1-hydroxy­ethyl­idene)­di­phospho­nate] serves as a bis-chelating bridging ligand, two types of [Co(en)₃]³⁺ cations, one uncoordinated Cl⁻ anion and five water mol­ecules of crystallization. The [Ru₂(hedp)₂Cl₂]⁵⁻ anions are connected to one another, forming one-dimensional chains along the a axis. The [Co(en)₃]³⁺ cations are located between these chains and lie across inversion centres. An extensive series of hydrogen bonds lead to the formation of a three-dimensional supramol­ecular network structure, with channels generated along the [100] direction. The uncoordinated water mol­ecules and Cl⁻ anions reside in these channels.

S1. Comment

Metal phosphonates are organic–inorganic hybrid materials that are important because of their potential applications in ion exchange, sensors, catalysis and molecular recognition (Clearfield et al., 1998; Cao et al., 1992; Zheng et al., 2000; Katz et al., 1991; Alberti et al., 1996). Although a number of new compounds have been reported, examples of ruthenium phosphonate compounds are extremely limited (Yi et al., 2003; Macann et al., 1993). In a previous paper, we described the synthesis of a ruthenium–hedp compound, (NH₄)₃Ru₂(hedp)₂·2H₂O [hedp is 1-hydroxyethylidenediphosphonate, CH₃C(OH)(PO₃)₂], which exhibits a novel two-dimensional structure. We present here the synthesis and structure of a new ruthenium phosphonate compound, namely [(Co(en)₃)]₂[Ru₂(hedp)₂Cl₂]Cl·5H₂O, (I).

Compound 1 has a three-dimensional open-network structure, composed of [Ru₂(hedp)₂Cl₂]⁵⁻ anions and [Co(en)₃]³⁺ cations. As shown in Fig. 1, there are two crystallographically independent Ru atoms, each having a distorted octahedral environment, with the four basal positions occupied by phosphonate O atoms from two equivalent hedp ligands (O3, O6, O2A and O4A for atom Ru1,and O9, O12, O8A and O13A for atom Ru2). The Ru—O bond distances range from 2.000 (3) to 2.047 (3) Å and the O—Ru—O bond angles from 88.40 (13) to 88.42 (9)°. One axial position of each Ru octahedron is occupied by a Cl⁻ anion and the other site is filled by the equivalent Ru atom. The Ru1—Cl1 and Ru2—Cl2 bond distances are 2.600 (8) and 2.553 (13) Å, respectively. Each hedp serves as a bis-chelating bridging ligand, linking the two equivalent Ru atoms via four phosphonate O atoms, thus forming [Ru₂(hedp)₂Cl₂]⁵⁻ dimers. The remaining two phosphonated O atoms are pendent. The Ru1—Ru1A and Ru2—Ru2A bond distances are 2.359 (8) and 2.379 (8) Å, respectively. These values are in agreement with those reported for (NH₄)₃Ru₂(hedp)₂·2H₂O. Inversion centers are located at the mid-points of the Ru1—Ru1A and Ru2—Ru2A bonds.

The diruthenium units, Ru1₂ and Ru2₂, are each linked to their equivalents via O···O hydrogen bonds [O7—H7E···O5ⁱ = 2.717 (5) Å for Ru1₂, and O14—H14D···O11ⁱⁱ = 2.679 (5) Å for Ru2₂; symmetry codes: (i) −x,1 − y,2 − z; (ii) 1 − x,-y,1 − z], forming two types of chains along the a axis (Fig. 2). The chains are separated by [Co(en)₃]³⁺ cations, with extensive intermolecular hydrogen bonding [N3—H3c···O2ⁱⁱⁱ = 3.006 (5) Å, N6—H6C···O6^iv = 3.040 (5) Å, N6—H6C···O2ⁱⁱⁱ = 2.875 Å, N8—H8C···O3^v = 2.905 (6) Å, N9—H9C···O7^v = 2.978 (5) Å, N9—H9C···O^v = 3.052 (5) Å and N11—H11C···O1^v = 2.955 (5) Å for Ru1₂, and N1—H1C···O11ⁱⁱⁱ = 3.001 (6) Å and N10—H10···O8^vi = 2.967 (5) Å for Ru2₂; symmetry codes: (iii) 1 − x,1 − y,1 − z; (iv) x,y,-1 + z; (v) 1 − x,1 − y,2 − z; (vi) 2 − x,1 − y,1 − z]. Consequently, a three-dimensional supramolecular open-network structure is constructed, with channels generated along the [100] direction (Fig. 3). The uncoordinated water molecules and chloride anions reside within these channels. Although each [Co(en)₃]³⁺ ion is chiral, the overall structure of (I) is not chiral because each [Co(en)₃]³⁺ is centrosymmetrically related to its equivalent.

S2. Experimental

Compound (NH₄)₃[Ru₂{CH₃C(OH)(PO₃)₂}²]·2H₂O was synthesized according to the literature (Yi et al., 2003). A mixture of (NH₄)₃[Ru₂(hedp)₂]·2H₂O (0.0634 g, 0.089 mmol), Co(en)₃Cl₃·3H₂O (2.0231 g, 5.1 mmol) and water (10 ml) was stirred at 343 K? for 5 h. The filtration was kept at room temperature for 30 d. Brown column-like single crystals were collected as monophasic material. Analysis calculated for (I): C 15.29, N 13.37%; found: C 14.61, N 12.32%. IR (KBr, cm⁻¹): 3.507 (s, br), 3440 (s, br), 3212 (s, br), 2362 (w), 1612 (m), 1579 (s), 1463 (s), 1365 (m), 1326 (m), 1155 (s), 1057 (s), 963 (s), 903 (s), 815 (m), 776 (w), 583 (s), 487 (s), 439 (m).

S3. Refinement

All H atoms were positioned geometrically and refined as riding, with U_iso values of 1.2 to 1.5 times U_eq of the parent atom, and C—H distances of 0.96 and 0.97 Å, N—H distances of 0.90 Å, and O—H distances of 0.8200–1.1654 Å.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SMART; data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I), with the atomic labeling scheme. H atoms have been omitted for clarity. Atoms labeled with the suffix A are at the symmetry postion (1 − x, 1 − y, 2 − z).
	Fig. 2. One chain of diruthenium phosphonate in (I), along the [100] direction. All H atoms, water molecules and hydrogen bonds, except N—H···O and O—H···O bonds, have been omitted for clarity.
	Fig. 3. The bc plane of diruthenium phosphonate in (I). All H atoms, water molecules and hydrogen bonds, except N—H···O bonds, have been omitted for clarity.

Bis[tris(ethylenediamine)cobalt(III)] dichlorobis[µ-(1- hydroxyethylidene)diphosphonato(4-)]diruthenium(II,III)(Ru—Ru) chloride trihydrate

Crystal data

[Co(C2H8N2)3]2[Ru2Cl2(C2H4O7P2)2]Cl·3H2O	Z = 2
Mr = 1245.01	F(000) = 1262
Triclinic, P1	Dx = 1.669 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.5166 (16) Å	Cell parameters from 1000 reflections
b = 15.297 (2) Å	θ = 2.3–19.8°
c = 15.497 (2) Å	µ = 1.61 mm^−1
α = 90.788 (3)°	T = 293 K
β = 91.362 (4)°	Prism, brown
γ = 96.273 (3)°	0.3 × 0.2 × 0.2 mm
V = 2477.2 (6) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	8573 independent reflections
Radiation source: sealed tube	6430 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
ϕ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −12→6
Tmin = 0.69, Tmax = 0.72	k = −18→18
12440 measured reflections	l = −17→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.109	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.06P)^2] where P = (Fo^2 + 2Fc^2)/3
8573 reflections	(Δ/σ)max = 0.001
559 parameters	Δρmax = 0.39 e Å^−3
0 restraints	Δρmin = −0.37 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 F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² 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 (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru1	0.49084 (4)	0.49713 (3)	1.07563 (2)	0.04397 (11)
Ru2	0.97359 (4)	−0.07757 (3)	0.49578 (2)	0.04410 (12)
Co1	0.43294 (6)	0.76962 (4)	0.24969 (4)	0.04687 (17)
Co2	0.82572 (6)	0.75827 (4)	0.76128 (4)	0.04562 (16)
P1	0.30511 (12)	0.36186 (8)	0.98100 (8)	0.0440 (3)
P2	0.25596 (12)	0.55337 (8)	0.98565 (8)	0.0453 (3)
P3	0.82749 (12)	0.01841 (8)	0.36461 (8)	0.0451 (3)
P4	0.75459 (12)	0.01992 (8)	0.55309 (8)	0.0453 (3)
Cl1	0.47227 (12)	0.49354 (8)	1.24256 (7)	0.0475 (3)
Cl2	0.92162 (12)	−0.24439 (8)	0.48579 (8)	0.0494 (3)
Cl3	0.61973 (12)	−0.03218 (8)	0.85186 (8)	0.0496 (3)
C1	0.1789 (5)	0.7799 (3)	0.2730 (3)	0.0514 (12)
H1A	0.1002	0.8025	0.2545	0.062*
H1B	0.1816	0.7806	0.3356	0.062*
C2	0.1746 (5)	0.6795 (3)	0.2393 (4)	0.0521 (12)
H2A	0.1153	0.6401	0.2714	0.063*
H2B	0.1536	0.6734	0.1781	0.063*
C3	0.5849 (5)	0.6821 (3)	0.3583 (3)	0.0520 (12)
H3A	0.6710	0.6680	0.3712	0.062*
H3B	0.5256	0.6321	0.3738	0.062*
C4	0.5595 (5)	0.7607 (3)	0.4104 (3)	0.0476 (11)
H4A	0.5492	0.7457	0.4706	0.057*
H4B	0.6294	0.8073	0.4062	0.057*
C5	0.6007 (5)	0.8719 (3)	0.1428 (3)	0.0485 (11)
H5A	0.6707	0.8355	0.1449	0.058*
H5B	0.6334	0.9298	0.1231	0.058*
C6	0.4946 (5)	0.8307 (3)	0.0811 (3)	0.0467 (11)
H6A	0.5303	0.8143	0.0269	0.056*
H6B	0.4332	0.8723	0.0694	0.056*
C7	0.5999 (5)	0.7807 (3)	0.6684 (3)	0.0474 (11)
H7A	0.5385	0.7568	0.6242	0.057*
H7B	0.6049	0.8443	0.6673	0.057*
C8	0.5581 (5)	0.7482 (3)	0.7558 (3)	0.0468 (11)
H8A	0.4854	0.7772	0.7739	0.056*
H8B	0.5325	0.6854	0.7528	0.056*
C9	0.9128 (5)	0.5892 (3)	0.7509 (3)	0.0509 (12)
H9A	0.8876	0.5302	0.7283	0.061*
H9B	0.9763	0.5870	0.7970	0.061*
C10	0.9602 (5)	0.6511 (3)	0.6809 (3)	0.0521 (12)
H10A	1.0424	0.6347	0.6634	0.063*
H10B	0.9019	0.6401	0.6315	0.063*
C11	0.9183 (5)	0.8691 (3)	0.8963 (3)	0.0519 (12)
H11A	0.9838	0.8842	0.9408	0.062*
H11B	0.8365	0.8808	0.9188	0.062*
C12	0.9476 (5)	0.9232 (3)	0.8174 (3)	0.0474 (11)
H12A	0.9352	0.9843	0.8282	0.057*
H12B	1.0351	0.9201	0.8003	0.057*
C13	0.1837 (5)	0.4374 (3)	0.9749 (3)	0.0442 (11)
C14	0.1113 (5)	0.4237 (3)	0.8875 (3)	0.0467 (11)
H14A	0.0475	0.4639	0.8834	0.070*
H14B	0.0708	0.3644	0.8830	0.070*
H14C	0.1704	0.4343	0.8416	0.070*
C15	0.7018 (4)	0.0301 (3)	0.4396 (3)	0.0430 (10)
C16	0.6551 (5)	0.1227 (3)	0.4294 (3)	0.0478 (11)
H16A	0.5885	0.1295	0.4695	0.072*
H16B	0.6226	0.1285	0.3716	0.072*
H16C	0.7253	0.1672	0.4409	0.072*
N1	0.2825 (4)	0.8367 (3)	0.2442 (3)	0.0503 (10)
H1C	0.2956	0.8851	0.2783	0.060*
H1D	0.2676	0.8534	0.1897	0.060*
N2	0.3138 (4)	0.6654 (3)	0.2594 (3)	0.0485 (9)
H2C	0.3367	0.6237	0.2231	0.058*
H2D	0.3195	0.6451	0.3134	0.058*
N3	0.5711 (4)	0.6977 (3)	0.2672 (2)	0.0470 (9)
H3C	0.5537	0.6462	0.2382	0.056*
H3D	0.6443	0.7254	0.2473	0.056*
N4	0.4446 (4)	0.7874 (3)	0.3747 (3)	0.0498 (10)
H4C	0.4412	0.8447	0.3873	0.060*
H4D	0.3772	0.7565	0.3988	0.060*
N5	0.5462 (4)	0.8788 (3)	0.2299 (3)	0.0478 (9)
H5C	0.5014	0.9257	0.2328	0.057*
H5D	0.6094	0.8857	0.2704	0.057*
N6	0.4293 (4)	0.7490 (3)	0.1252 (2)	0.0474 (9)
H6C	0.4703	0.7020	0.1128	0.057*
H6D	0.3477	0.7379	0.1057	0.057*
N7	0.7272 (4)	0.7517 (3)	0.6517 (2)	0.0448 (9)
H7C	0.7681	0.7868	0.6126	0.054*
H7D	0.7182	0.6962	0.6306	0.054*
N8	0.6632 (4)	0.7671 (3)	0.8173 (3)	0.0473 (9)
H8C	0.6545	0.7288	0.8608	0.057*
H8D	0.6622	0.8217	0.8395	0.057*
N9	0.8032 (4)	0.6311 (2)	0.7792 (3)	0.0460 (9)
H9C	0.7915	0.6207	0.8356	0.055*
H9D	0.7327	0.6073	0.7498	0.055*
N10	0.9752 (4)	0.7415 (3)	0.6970 (3)	0.0489 (10)
H10C	0.9770	0.7717	0.6476	0.059*
H10D	1.0473	0.7580	0.7283	0.059*
N11	0.9146 (4)	0.7781 (2)	0.8728 (2)	0.0469 (9)
H11C	0.8734	0.7447	0.9130	0.056*
H11D	0.9947	0.7630	0.8695	0.056*
N12	0.8596 (4)	0.8853 (2)	0.7524 (2)	0.0459 (9)
H12C	0.8913	0.8984	0.7001	0.055*
H12D	0.7855	0.9092	0.7566	0.055*
O1	0.2443 (3)	0.2700 (2)	0.9768 (2)	0.0467 (8)
O2	0.4029 (3)	0.3828 (2)	0.9087 (2)	0.0465 (8)
O3	0.3770 (3)	0.3822 (2)	1.0689 (2)	0.0446 (7)
O4	0.3540 (3)	0.5671 (2)	0.9129 (2)	0.0456 (7)
O5	0.1528 (3)	0.6123 (2)	0.9793 (2)	0.0455 (7)
O6	0.3296 (3)	0.5609 (2)	1.0742 (2)	0.0472 (8)
O7	0.1046 (3)	0.4190 (2)	1.0471 (2)	0.0451 (7)
H7E	0.0295	0.4107	1.0306	0.054*
O8	0.9355 (3)	0.0916 (2)	0.3890 (2)	0.0459 (7)
O9	0.8769 (3)	−0.0708 (2)	0.3834 (2)	0.0454 (7)
O10	0.7762 (3)	0.0220 (2)	0.2755 (2)	0.0473 (8)
O11	0.6505 (3)	0.0295 (2)	0.6139 (2)	0.0469 (8)
O12	0.8075 (3)	−0.0695 (2)	0.5574 (2)	0.0463 (7)
O13	0.8665 (3)	0.0922 (2)	0.5673 (2)	0.0452 (7)
O14	0.5989 (3)	−0.0386 (2)	0.4190 (2)	0.0489 (8)
H14D	0.5318	−0.0167	0.4117	0.059*
O1W	0.6641 (3)	0.1073 (2)	0.1513 (2)	0.0517 (8)
H1WA	0.7161	0.0799	0.1804	0.062*
H1WB	0.5880	0.0906	0.1659	0.062*
O2W	0.2669 (11)	0.5831 (8)	0.7125 (8)	0.046 (3)	0.25
H2WB	0.2091	0.5466	0.6891	0.055*	0.25
H2WD	0.3367	0.5815	0.6863	0.055*	0.25
O3W	0.1810 (12)	0.7250 (8)	0.8344 (7)	0.043 (3)	0.25
H3WD	0.1987	0.6843	0.8004	0.052*	0.25
H3WC	0.2499	0.7518	0.8558	0.052*	0.25
O4W	0.8691 (13)	0.8099 (10)	0.2777 (9)	0.057 (4)	0.25
H4WA	0.8847	0.8338	0.2294	0.068*	0.25
H4WC	0.8789	0.8486	0.3179	0.068*	0.25
O5W	0.1730 (12)	0.7850 (8)	0.0536 (8)	0.046 (3)	0.25
H5WB	0.0947	0.7691	0.0412	0.055*	0.25
H5WC	0.1880	0.8405	0.0493	0.055*	0.25
O6W	0.0679 (12)	0.1600 (7)	0.8929 (8)	0.043 (3)	0.25
H6WA	0.0627	0.1107	0.9178	0.064*	0.25
H6WC	0.0948	0.1542	0.8420	0.064*	0.25
O7W	0.9456 (13)	0.5207 (9)	0.4205 (9)	0.054 (3)	0.25
H7WB	1.0045	0.4880	0.4119	0.065*	0.25
H7WD	0.8916	0.5023	0.4578	0.065*	0.25
O8W	0.3120 (12)	0.6189 (9)	0.4856 (8)	0.049 (3)	0.25
H8WD	0.3923	0.6233	0.4784	0.059*	0.25
H8WA	0.3051	0.5983	0.5576	0.059*	0.25
O9W	0.6361 (13)	0.5715 (8)	0.5703 (7)	0.045 (3)	0.25
H9WA	0.6254	0.5584	0.5169	0.054*	0.25
H9WD	0.5868	0.5365	0.5998	0.054*	0.25

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0434 (2)	0.0438 (2)	0.0446 (2)	0.00423 (17)	0.00133 (16)	0.00031 (16)
Ru2	0.0435 (2)	0.0444 (2)	0.0443 (2)	0.00456 (17)	0.00169 (16)	0.00038 (16)
Co1	0.0457 (4)	0.0463 (4)	0.0484 (4)	0.0043 (3)	0.0015 (3)	−0.0008 (3)
Co2	0.0456 (4)	0.0456 (4)	0.0458 (4)	0.0047 (3)	0.0022 (3)	0.0035 (3)
P1	0.0417 (6)	0.0447 (7)	0.0452 (7)	0.0037 (5)	−0.0001 (5)	0.0007 (5)
P2	0.0443 (7)	0.0451 (7)	0.0465 (7)	0.0049 (5)	−0.0004 (5)	0.0017 (5)
P3	0.0447 (7)	0.0458 (7)	0.0446 (7)	0.0046 (5)	0.0003 (5)	0.0001 (5)
P4	0.0439 (7)	0.0471 (7)	0.0449 (7)	0.0049 (5)	0.0020 (5)	0.0011 (5)
Cl1	0.0505 (7)	0.0455 (6)	0.0461 (6)	0.0033 (5)	0.0022 (5)	0.0008 (5)
Cl2	0.0512 (7)	0.0481 (6)	0.0488 (6)	0.0052 (5)	0.0002 (5)	−0.0006 (5)
Cl3	0.0492 (7)	0.0473 (6)	0.0527 (7)	0.0070 (5)	0.0005 (5)	0.0006 (5)
C1	0.051 (3)	0.043 (3)	0.059 (3)	0.001 (2)	0.001 (2)	0.001 (2)
C2	0.048 (3)	0.046 (3)	0.062 (3)	0.003 (2)	−0.003 (2)	−0.003 (2)
C3	0.051 (3)	0.048 (3)	0.057 (3)	0.005 (2)	0.002 (2)	−0.003 (2)
C4	0.050 (3)	0.051 (3)	0.042 (3)	0.005 (2)	0.000 (2)	−0.005 (2)
C5	0.047 (3)	0.050 (3)	0.049 (3)	0.008 (2)	0.001 (2)	0.001 (2)
C6	0.050 (3)	0.045 (3)	0.046 (3)	0.007 (2)	0.007 (2)	0.002 (2)
C7	0.048 (3)	0.046 (3)	0.047 (3)	−0.001 (2)	0.006 (2)	0.001 (2)
C8	0.044 (3)	0.051 (3)	0.045 (3)	0.006 (2)	0.001 (2)	−0.004 (2)
C9	0.057 (3)	0.046 (3)	0.052 (3)	0.014 (2)	−0.003 (2)	0.004 (2)
C10	0.052 (3)	0.050 (3)	0.053 (3)	0.005 (2)	−0.002 (2)	−0.002 (2)
C11	0.049 (3)	0.053 (3)	0.052 (3)	−0.003 (2)	0.005 (2)	0.004 (2)
C12	0.043 (3)	0.053 (3)	0.046 (3)	0.005 (2)	0.007 (2)	0.003 (2)
C13	0.053 (3)	0.039 (2)	0.041 (2)	0.009 (2)	0.001 (2)	−0.0041 (19)
C14	0.045 (3)	0.041 (2)	0.053 (3)	0.002 (2)	0.000 (2)	0.003 (2)
C15	0.036 (2)	0.057 (3)	0.036 (2)	0.002 (2)	−0.0003 (19)	0.004 (2)
C16	0.050 (3)	0.047 (3)	0.046 (3)	0.004 (2)	0.000 (2)	0.006 (2)
N1	0.053 (2)	0.047 (2)	0.051 (2)	0.0044 (19)	−0.0012 (19)	−0.0022 (18)
N2	0.046 (2)	0.043 (2)	0.057 (2)	0.0014 (18)	0.0031 (19)	−0.0007 (18)
N3	0.049 (2)	0.046 (2)	0.046 (2)	0.0059 (18)	0.0014 (18)	−0.0022 (17)
N4	0.051 (2)	0.043 (2)	0.055 (2)	0.0026 (19)	0.0055 (19)	−0.0003 (18)
N5	0.045 (2)	0.047 (2)	0.050 (2)	0.0020 (18)	0.0009 (18)	−0.0029 (18)
N6	0.047 (2)	0.050 (2)	0.045 (2)	0.0066 (19)	−0.0025 (18)	−0.0020 (18)
N7	0.044 (2)	0.044 (2)	0.047 (2)	0.0068 (18)	−0.0020 (18)	0.0005 (17)
N8	0.047 (2)	0.048 (2)	0.048 (2)	0.0071 (18)	0.0059 (18)	0.0006 (18)
N9	0.047 (2)	0.046 (2)	0.045 (2)	0.0047 (18)	0.0017 (18)	0.0024 (17)
N10	0.047 (2)	0.050 (2)	0.050 (2)	0.0068 (19)	0.0003 (19)	0.0007 (18)
N11	0.049 (2)	0.044 (2)	0.048 (2)	0.0074 (18)	−0.0055 (18)	0.0029 (17)
N12	0.052 (2)	0.040 (2)	0.046 (2)	0.0016 (18)	0.0061 (18)	0.0015 (17)
O1	0.0466 (18)	0.0440 (18)	0.0499 (19)	0.0062 (15)	0.0034 (15)	−0.0032 (14)
O2	0.054 (2)	0.0412 (17)	0.0435 (18)	0.0020 (15)	−0.0003 (15)	−0.0031 (14)
O3	0.0446 (18)	0.0442 (18)	0.0449 (17)	0.0044 (14)	−0.0007 (14)	0.0019 (14)
O4	0.0464 (18)	0.0426 (17)	0.0485 (18)	0.0072 (14)	0.0015 (15)	0.0037 (14)
O5	0.0451 (18)	0.0478 (18)	0.0432 (17)	0.0027 (15)	0.0025 (14)	0.0044 (14)
O6	0.0450 (18)	0.0492 (18)	0.0482 (18)	0.0083 (15)	0.0033 (15)	0.0020 (14)
O7	0.0399 (17)	0.0479 (18)	0.0477 (18)	0.0059 (14)	0.0003 (14)	0.0013 (14)
O8	0.0458 (18)	0.0473 (18)	0.0451 (18)	0.0076 (15)	0.0009 (15)	−0.0005 (14)
O9	0.0469 (18)	0.0459 (18)	0.0435 (17)	0.0049 (15)	0.0013 (14)	−0.0021 (14)
O10	0.0499 (19)	0.0469 (18)	0.0448 (18)	0.0044 (15)	−0.0017 (15)	0.0001 (14)
O11	0.0429 (18)	0.0476 (18)	0.0494 (19)	0.0003 (15)	0.0058 (15)	−0.0010 (14)
O12	0.0411 (18)	0.0512 (19)	0.0464 (18)	0.0054 (15)	−0.0007 (14)	−0.0027 (14)
O13	0.0415 (17)	0.0465 (18)	0.0485 (18)	0.0093 (14)	0.0019 (14)	−0.0018 (14)
O14	0.0431 (18)	0.0529 (19)	0.0499 (19)	0.0031 (15)	−0.0040 (15)	−0.0027 (15)
O1W	0.053 (2)	0.053 (2)	0.0496 (19)	0.0105 (16)	0.0005 (16)	0.0014 (15)
O2W	0.031 (6)	0.053 (8)	0.054 (8)	0.010 (6)	0.009 (6)	0.008 (6)
O3W	0.053 (8)	0.045 (7)	0.030 (6)	0.002 (6)	−0.013 (5)	0.013 (5)
O4W	0.046 (8)	0.072 (9)	0.057 (8)	0.032 (7)	−0.002 (6)	0.011 (7)
O5W	0.043 (7)	0.041 (7)	0.053 (8)	0.003 (6)	0.013 (6)	0.006 (6)
O6W	0.050 (7)	0.031 (6)	0.045 (7)	−0.008 (5)	−0.013 (6)	0.007 (5)
O7W	0.055 (8)	0.051 (8)	0.059 (8)	0.016 (7)	0.010 (7)	0.013 (6)
O8W	0.036 (7)	0.062 (8)	0.053 (8)	0.015 (6)	0.017 (6)	0.008 (6)
O9W	0.061 (8)	0.044 (7)	0.032 (6)	0.012 (6)	0.002 (6)	0.006 (5)

Geometric parameters (Å, º)

Ru1—O4^i	2.000 (3)	C9—H9A	0.9700
Ru1—O3	2.015 (3)	C9—H9B	0.9700
Ru1—O6	2.047 (3)	C10—N10	1.393 (6)
Ru1—O2^i	2.051 (3)	C10—H10A	0.9700
Ru1—Ru1^i	2.3587 (8)	C10—H10B	0.9700
Ru1—Cl1	2.5997 (13)	C11—N11	1.430 (6)
Ru2—O13^ii	1.997 (3)	C11—C12	1.505 (7)
Ru2—O9	2.005 (3)	C11—H11A	0.9700
Ru2—O12	2.025 (3)	C11—H11B	0.9700
Ru2—O8^ii	2.031 (3)	C12—N12	1.425 (6)
Ru2—Ru2^ii	2.3785 (8)	C12—H12A	0.9700
Ru2—Cl2	2.5525 (13)	C12—H12B	0.9700
Co1—N2	1.927 (4)	C13—O7	1.422 (6)
Co1—N3	1.932 (4)	C13—C14	1.539 (6)
Co1—N6	1.949 (4)	C14—H14A	0.9600
Co1—N4	1.951 (4)	C14—H14B	0.9600
Co1—N5	1.975 (4)	C14—H14C	0.9600
Co1—N1	1.979 (4)	C15—O14	1.450 (5)
Co2—N10	1.920 (4)	C15—C16	1.558 (6)
Co2—N12	1.945 (4)	C16—H16A	0.9600
Co2—N11	1.949 (4)	C16—H16B	0.9600
Co2—N8	1.952 (4)	C16—H16C	0.9600
Co2—N9	1.958 (4)	N1—H1C	0.9000
Co2—N7	1.964 (4)	N1—H1D	0.9000
P1—O1	1.479 (3)	N2—H2C	0.9000
P1—O2	1.552 (4)	N2—H2D	0.9000
P1—O3	1.554 (3)	N3—H3C	0.9000
P1—C13	1.815 (5)	N3—H3D	0.9000
P2—O5	1.487 (3)	N4—H4C	0.9000
P2—O4	1.547 (4)	N4—H4D	0.9000
P2—O6	1.556 (3)	N5—H5C	0.9000
P2—C13	1.855 (5)	N5—H5D	0.9000
P3—O10	1.475 (3)	N6—H6C	0.9000
P3—O9	1.541 (3)	N6—H6D	0.9000
P3—O8	1.542 (3)	N7—H7C	0.9000
P3—C15	1.803 (5)	N7—H7D	0.9000
P4—O11	1.479 (3)	N8—H8C	0.9000
P4—O12	1.533 (3)	N8—H8D	0.9000
P4—O13	1.534 (3)	N9—H9C	0.9000
P4—C15	1.845 (4)	N9—H9D	0.9000
C1—N1	1.403 (6)	N10—H10C	0.9000
C1—C2	1.611 (7)	N10—H10D	0.9000
C1—H1A	0.9700	N11—H11C	0.9000
C1—H1B	0.9700	N11—H11D	0.9000
C2—N2	1.528 (6)	N12—H12C	0.9000
C2—H2A	0.9700	N12—H12D	0.9000
C2—H2B	0.9700	O2—Ru1^i	2.051 (3)
C3—N3	1.442 (6)	O4—Ru1^i	2.000 (3)
C3—C4	1.491 (6)	O7—H7E	0.8200
C3—H3A	0.9700	O8—Ru2^ii	2.031 (3)
C3—H3B	0.9701	O13—Ru2^ii	1.997 (3)
C4—N4	1.420 (6)	O14—H14D	0.8200
C4—H4A	0.9700	O1W—H1WA	0.8498
C4—H4B	0.9700	O1W—H1WB	0.8500
C5—N5	1.485 (6)	O2W—H2WB	0.8499
C5—C6	1.528 (7)	O2W—H2WD	0.8500
C5—H5A	0.9700	O3W—H3WD	0.8499
C5—H5B	0.9700	O3W—H3WC	0.8501
C6—N6	1.537 (6)	O4W—H4WA	0.8501
C6—H6A	0.9700	O4W—H4WC	0.8496
C6—H6B	0.9700	O5W—H5WB	0.8500
C7—N7	1.482 (6)	O5W—H5WC	0.8501
C7—C8	1.507 (7)	O6W—H6WA	0.8501
C7—H7A	0.9700	O6W—H6WC	0.8501
C7—H7B	0.9700	O7W—H7WB	0.8500
C8—N8	1.444 (6)	O7W—H7WD	0.8501
C8—H8A	0.9700	O8W—H8WD	0.8500
C8—H8B	0.9700	O8W—H8WA	1.1654
C9—N9	1.452 (6)	O9W—H9WA	0.8499
C9—C10	1.508 (7)	O9W—H9WD	0.8500
O4^i—Ru1—O3	90.69 (13)	C10—C9—H9B	111.7
O4^i—Ru1—O6	175.38 (13)	H9A—C9—H9B	109.5
O3—Ru1—O6	88.41 (13)	N10—C10—C9	119.8 (4)
O4^i—Ru1—O2^i	92.24 (13)	N10—C10—H10A	107.4
O3—Ru1—O2^i	174.93 (13)	C9—C10—H10A	107.4
O6—Ru1—O2^i	88.34 (13)	N10—C10—H10B	107.4
O4^i—Ru1—Ru1^i	91.52 (9)	C9—C10—H10B	107.4
O3—Ru1—Ru1^i	92.61 (9)	H10A—C10—H10B	106.9
O6—Ru1—Ru1^i	93.05 (9)	N11—C11—C12	108.6 (4)
O2^i—Ru1—Ru1^i	91.45 (9)	N11—C11—H11A	110.0
O4^i—Ru1—Cl1	88.69 (10)	C12—C11—H11A	110.0
O3—Ru1—Cl1	88.33 (9)	N11—C11—H11B	110.0
O6—Ru1—Cl1	86.75 (9)	C12—C11—H11B	110.0
O2^i—Ru1—Cl1	87.60 (9)	H11A—C11—H11B	108.3
Ru1^i—Ru1—Cl1	179.04 (4)	N12—C12—C11	104.9 (4)
O13^ii—Ru2—O9	90.48 (13)	N12—C12—H12A	110.8
O13^ii—Ru2—O12	176.82 (12)	C11—C12—H12A	110.8
O9—Ru2—O12	88.42 (13)	N12—C12—H12B	110.8
O13^ii—Ru2—O8^ii	91.02 (13)	C11—C12—H12B	110.8
O9—Ru2—O8^ii	176.38 (13)	H12A—C12—H12B	108.8
O12—Ru2—O8^ii	89.92 (13)	O7—C13—C14	113.5 (4)
O13^ii—Ru2—Ru2^ii	91.29 (9)	O7—C13—P1	106.0 (3)
O9—Ru2—Ru2^ii	92.48 (9)	C14—C13—P1	108.8 (3)
O12—Ru2—Ru2^ii	91.74 (9)	O7—C13—P2	107.8 (3)
O8^ii—Ru2—Ru2^ii	90.78 (9)	C14—C13—P2	109.4 (3)
O13^ii—Ru2—Cl2	87.55 (10)	P1—C13—P2	111.3 (3)
O9—Ru2—Cl2	87.80 (9)	C13—C14—H14A	109.5
O12—Ru2—Cl2	89.42 (10)	C13—C14—H14B	109.5
O8^ii—Ru2—Cl2	88.97 (9)	H14A—C14—H14B	109.5
Ru2^ii—Ru2—Cl2	178.81 (4)	C13—C14—H14C	109.5
N2—Co1—N3	88.64 (17)	H14A—C14—H14C	109.5
N2—Co1—N6	88.29 (17)	H14B—C14—H14C	109.5
N3—Co1—N6	92.25 (16)	O14—C15—C16	110.7 (4)
N2—Co1—N4	92.12 (18)	O14—C15—P3	107.3 (3)
N3—Co1—N4	84.89 (16)	C16—C15—P3	109.1 (3)
N6—Co1—N4	177.09 (18)	O14—C15—P4	109.2 (3)
N2—Co1—N5	174.68 (17)	C16—C15—P4	107.8 (3)
N3—Co1—N5	94.83 (18)	P3—C15—P4	112.8 (2)
N6—Co1—N5	87.54 (17)	C15—C16—H16A	109.5
N4—Co1—N5	92.21 (17)	C15—C16—H16B	109.5
N2—Co1—N1	87.05 (17)	H16A—C16—H16B	109.5
N3—Co1—N1	173.20 (17)	C15—C16—H16C	109.5
N6—Co1—N1	92.88 (17)	H16A—C16—H16C	109.5
N4—Co1—N1	90.01 (17)	H16B—C16—H16C	109.5
N5—Co1—N1	89.85 (17)	C1—N1—Co1	106.2 (3)
N10—Co2—N12	91.33 (17)	C1—N1—H1C	110.5
N10—Co2—N11	95.94 (18)	Co1—N1—H1C	110.5
N12—Co2—N11	83.70 (16)	C1—N1—H1D	110.5
N10—Co2—N8	173.79 (17)	Co1—N1—H1D	110.5
N12—Co2—N8	92.16 (17)	H1C—N1—H1D	108.7
N11—Co2—N8	89.55 (17)	C2—N2—Co1	114.2 (3)
N10—Co2—N9	87.89 (17)	C2—N2—H2C	108.7
N12—Co2—N9	174.68 (17)	Co1—N2—H2C	108.7
N11—Co2—N9	91.15 (16)	C2—N2—H2D	108.7
N8—Co2—N9	89.10 (17)	Co1—N2—H2D	108.7
N10—Co2—N7	88.38 (17)	H2C—N2—H2D	107.6
N12—Co2—N7	90.73 (16)	C3—N3—Co1	108.5 (3)
N11—Co2—N7	173.01 (16)	C3—N3—H3C	110.0
N8—Co2—N7	86.44 (17)	Co1—N3—H3C	110.0
N9—Co2—N7	94.51 (16)	C3—N3—H3D	110.0
O1—P1—O2	112.85 (18)	Co1—N3—H3D	110.0
O1—P1—O3	111.01 (18)	H3C—N3—H3D	108.4
O2—P1—O3	107.50 (18)	C4—N4—Co1	111.9 (3)
O1—P1—C13	110.1 (2)	C4—N4—H4C	109.2
O2—P1—C13	109.4 (2)	Co1—N4—H4C	109.2
O3—P1—C13	105.71 (19)	C4—N4—H4D	109.2
O5—P2—O4	113.25 (18)	Co1—N4—H4D	109.2
O5—P2—O6	113.20 (18)	H4C—N4—H4D	107.9
O4—P2—O6	108.69 (19)	C5—N5—Co1	107.9 (3)
O5—P2—C13	109.1 (2)	C5—N5—H5C	110.1
O4—P2—C13	106.1 (2)	Co1—N5—H5C	110.1
O6—P2—C13	106.1 (2)	C5—N5—H5D	110.1
O10—P3—O9	111.89 (18)	Co1—N5—H5D	110.1
O10—P3—O8	114.68 (19)	H5C—N5—H5D	108.4
O9—P3—O8	107.95 (18)	C6—N6—Co1	109.3 (3)
O10—P3—C15	109.6 (2)	C6—N6—H6C	109.8
O9—P3—C15	106.4 (2)	Co1—N6—H6C	109.8
O8—P3—C15	105.9 (2)	C6—N6—H6D	109.8
O11—P4—O12	113.73 (19)	Co1—N6—H6D	109.8
O11—P4—O13	111.75 (18)	H6C—N6—H6D	108.3
O12—P4—O13	108.25 (18)	C7—N7—Co2	108.0 (3)
O11—P4—C15	112.2 (2)	C7—N7—H7C	110.1
O12—P4—C15	105.2 (2)	Co2—N7—H7C	110.1
O13—P4—C15	105.2 (2)	C7—N7—H7D	110.1
N1—C1—C2	115.0 (4)	Co2—N7—H7D	110.1
N1—C1—H1A	108.5	H7C—N7—H7D	108.4
C2—C1—H1A	108.5	C8—N8—Co2	110.2 (3)
N1—C1—H1B	108.5	C8—N8—H8C	109.6
C2—C1—H1B	108.5	Co2—N8—H8C	109.6
H1A—C1—H1B	107.5	C8—N8—H8D	109.6
N2—C2—C1	98.7 (4)	Co2—N8—H8D	109.6
N2—C2—H2A	112.0	H8C—N8—H8D	108.1
C1—C2—H2A	112.0	C9—N9—Co2	111.9 (3)
N2—C2—H2B	112.0	C9—N9—H9C	109.2
C1—C2—H2B	112.0	Co2—N9—H9C	109.2
H2A—C2—H2B	109.7	C9—N9—H9D	109.2
N3—C3—C4	111.1 (4)	Co2—N9—H9D	109.2
N3—C3—H3A	109.4	H9C—N9—H9D	107.9
C4—C3—H3A	109.5	C10—N10—Co2	102.4 (3)
N3—C3—H3B	109.3	C10—N10—H10C	111.3
C4—C3—H3B	109.5	Co2—N10—H10C	111.3
H3A—C3—H3B	107.9	C10—N10—H10D	111.3
N4—C4—C3	105.4 (4)	Co2—N10—H10D	111.3
N4—C4—H4A	110.7	H10C—N10—H10D	109.2
C3—C4—H4A	110.7	C11—N11—Co2	108.8 (3)
N4—C4—H4B	110.7	C11—N11—H11C	109.9
C3—C4—H4B	110.7	Co2—N11—H11C	109.9
H4A—C4—H4B	108.8	C11—N11—H11D	109.9
N5—C5—C6	108.2 (4)	Co2—N11—H11D	109.9
N5—C5—H5A	110.1	H11C—N11—H11D	108.3
C6—C5—H5A	110.1	C12—N12—Co2	112.6 (3)
N5—C5—H5B	110.1	C12—N12—H12C	109.1
C6—C5—H5B	110.1	Co2—N12—H12C	109.1
H5A—C5—H5B	108.4	C12—N12—H12D	109.1
C5—C6—N6	107.1 (4)	Co2—N12—H12D	109.1
C5—C6—H6A	110.3	H12C—N12—H12D	107.8
N6—C6—H6A	110.3	P1—O2—Ru1^i	113.53 (17)
C5—C6—H6B	110.3	P1—O3—Ru1	115.21 (18)
N6—C6—H6B	110.3	P2—O4—Ru1^i	116.35 (18)
H6A—C6—H6B	108.5	P2—O6—Ru1	113.17 (18)
N7—C7—C8	108.5 (4)	C13—O7—H7E	109.5
N7—C7—H7A	110.0	P3—O8—Ru2^ii	115.45 (19)
C8—C7—H7A	110.0	P3—O9—Ru2	115.69 (17)
N7—C7—H7B	110.0	P4—O12—Ru2	115.50 (19)
C8—C7—H7B	110.0	P4—O13—Ru2^ii	116.70 (18)
H7A—C7—H7B	108.4	C15—O14—H14D	109.5
N8—C8—C7	109.1 (4)	H1WA—O1W—H1WB	109.5
N8—C8—H8A	109.9	H2WB—O2W—H2WD	109.8
C7—C8—H8A	109.9	H3WD—O3W—H3WC	109.5
N8—C8—H8B	109.9	H4WA—O4W—H4WC	109.8
C7—C8—H8B	109.9	H5WB—O5W—H5WC	109.5
H8A—C8—H8B	108.3	H6WA—O6W—H6WC	109.5
N9—C9—C10	100.3 (4)	H7WB—O7W—H7WD	115.1
N9—C9—H9A	111.7	H8WD—O8W—H8WA	101.7
C10—C9—H9A	111.7	H9WA—O9W—H9WD	109.8
N9—C9—H9B	111.7

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WD···O2W	0.85	2.23	3.081 (18)	174
O1W—H1WA···O10	0.85	1.86	2.663 (4)	157
N7—H7D···O9W	0.90	2.19	3.062 (13)	162
N6—H6D···O5W	0.90	2.19	2.999 (14)	150
N1—H1C···O11^iii	0.90	2.13	3.001 (5)	162
N4—H4C···O11^iii	0.90	2.24	3.079 (5)	154
N5—H5C···Cl3^iii	0.90	2.54	3.320 (4)	146
N6—H6C···O2^iii	0.90	1.99	2.872 (5)	167
O2W—H2WB···O7W^iii	0.85	2.46	3.268 (19)	159
O4W—H4WA···O6W^iii	0.85	1.97	2.773 (19)	157
O6W—H6WC···O4W^iii	0.85	1.98	2.773 (19)	156
N2—H2C···O6^iv	0.90	2.48	3.282 (5)	148
N3—H3C···Cl1^iv	0.90	2.40	3.197 (4)	148
N7—H7C···O12^v	0.90	2.37	3.161 (5)	147
N8—H8D···Cl3^v	0.90	2.33	3.193 (4)	160
N10—H10C···Cl2^v	0.90	2.56	3.323 (4)	143
O4W—H4WC···O9^v	0.85	1.59	2.429 (15)	169
N8—H8C···O3^i	0.90	2.03	2.906 (5)	164
N9—H9C···O7^i	0.90	2.22	2.978 (5)	141
N11—H11C···O1^i	0.90	2.13	2.955 (5)	151
N9—H9D···Cl1^i	0.90	2.52	3.297 (4)	146
O9W—H9WD···Cl1^i	0.85	2.57	3.270 (12)	140
N12—H12C···O8^vi	0.90	2.30	3.106 (5)	148
N11—H11D···O3W^vii	0.90	2.18	3.071 (14)	169
N10—H10D···O3W^vii	0.90	2.24	3.032 (12)	147
N12—H12D···Cl3^v	0.90	2.54	3.341 (4)	149
O7—H7E···O5^viii	0.82	1.91	2.717 (5)	167
O14—H14D···O11^ix	0.82	1.94	2.679 (5)	150
O1W—H1WB···Cl3^ix	0.85	2.28	3.078 (4)	157

Symmetry codes: (i) −x+1, −y+1, −z+2; (iii) −x+1, −y+1, −z+1; (iv) x, y, z−1; (v) x, y+1, z; (vi) −x+2, −y+1, −z+1; (vii) x+1, y, z; (viii) −x, −y+1, −z+2; (ix) −x+1, −y, −z+1.