trans-Diaceto­nitrilebis­(di-2-pyridyl sulfide-N,N')ruthenium(II) bis­(tetra­fluoro­borate) monohydrate

The title complex, [Ru(C₁₀H₈N₂S)₂(CH₃CN)₂](BF₄)₂·H₂O, is the product of the solvolysis of [Ru(dps-N,N)₂(dps-N,S)](PF₆)₂ (dps is di-2-pyridyl sulfide) in the presence of HBF₄ in acetone-aceto­nitrile at room temperature. There are two independent cations, with the Ru atoms on inversion centres; each Ru atom has an octahedral geometry with the dps mol­ecules behaving as N,N'-bidentate ligands and assuming a trans arrangement.

S1. Comment

Following our interest in the chemistry of the flexible non-planar bipyridine-like ligands (Tresoldi et al., 1991, 1992) we were particularly interested to know how they would modify the chemical and physical properties of the ruthenium complexes (Bruno et al., 1995; Tresoldi et al., 1996). Recently taking advantage of the steric hindrance of the cis-Ru(N,N-dps)₂-core and steric demanding nature of dps we were able to introduce into the above centre a N,S-coordinated dps ligand and provide the possibility for pairs of chemically distinct coordination modes being present in [Ru(N,N-dps)₂(N,S-dps)][PF₆]₂ (Scopelliti et al., 2001). In this work the solvolysis of the last complex in the presence of an excess of HBF₄ has led to the title complex (I).

It is the first example of a ruthenium complex in which two dps ligands adopt the trans arrangement.

The IR spectrum contains the characteristic bands of the dps ligands at 1589 (s), 1561 (ms), 783 (versus), 774 (versus), 752 (ms) and 723 (s). The ¹H-NMR spectrum in CD₃(CO)₂ show a single ABMX system with signals at d 8.90, assigned to the proton H6 in ortho position with respect to the N atom, 7.82, assigned to the proton H5 in the meta position, 8.34, assigned to the proton H4 in the para position and 8.00, assigned to the proton H3 in the ortho position with respect to the S atom, while the ¹³C NMR show signals at d 146.87 (C6), 125.13 (C5), 143.18 (C4), 126.82 (C3) and 154.57 (C2). These data are in agreement with the presence of a trans isomer which has four equivalent pyridine rings. A cis isomer should have only two equivalent pyridyl rings.

Di-2-pyridyl sulfide and its derivatives are flexible ligands that can adopt several possible conformations and dynamic interconvertion depending on their chemical condition (protonated or unprotonated free molecule, chelating or bridging ligand) and on the physical state (Nicoló et al., 1996; and references therein).

The crystal packing of the title compound (I) shows two complex cations placed on two crystallographic independent inversion centres, in the 1:2 ratio with the tetrafluoroborate anions for charge balance. Then both molecules have the imposed C_i symmetry and appear equal within the experimental errors. The dps ligand adopts the twisted N,N inside `butterfly-like' arrangement and the resulting six-membered chelate rings show the usual boat conformation, as evidenced by the puckering analysis (Cremer & Pople, 1975) on Ru1,N1,C5,S1,C6,N2 [Ru2,N4,C17,S2,C18,N5] ring: θ=88.4 (2) [88.9 (2)]°, ϕ=2.4 (2) [-0.2 (2)]°, Q_T=0.897 (2) [0.898 (2)] Å and Δ_S(Ru)=0.025 (1) [0.001 (1)], respectively. The C and N atoms lie on a plane from which the Ru and S atoms deviate 0.8148 (1) [0.8055 (1)] and 0.743 (1) [0.754 (1)]Å on the same side, respectively. The geometry of the trans-arrangement of the two chelating dps is very similar to that one found in the square-planar palladium cation [Pd(dps)₂]²⁺ (Bruno et al., 1995) showing shorter metal-nitrogen bond lengths as expected by the different metal atom size. The geometry about the ruthenium(II) ion is distorted octahedral (Fig.1), with the coordination polyhedron defined by four N atoms of the two opposite chelating dps rings on the equatorial plane and the two acetonitrile N atoms along the axial direction. The Ru—N_py bonds are equivalent [av. 2.091 (3) Å] but significantly longer than the axial Ru—N_ac due to the different electronic and steric properties of the two ligand types and the larger hindrance on the equatorial plane. In fact the dps chelating bite (average N_py—Ru—N_py and N_py^···N_py are 88.5 (1)° and 2.918 (5) Å, respectively) is very similar in the cis-[Ru(dps)₂Cl₂] (Bruno et al., 1995) [88.5 (1)° and 2.893 (4) Å] and in one N,N-chelate ligand in [Ru(dps)₃]²⁺ (Scopelliti et al., 2001) [89.5 (2)° and 2.918 (7) Å]. The main distortion from the regular coordination geometry is due to the hindering effect of the S atom on the axial acetonitrile ligand on the same side with respect to the equatorial plane, increasing the N_py—Ru—N_ac up to the mean value of 93.5 (1) and 94.5 (1)° in the Ru1 and Ru2 cations, respectively.

In order to understand the structural modifications of the ligand induced by the dps coordination to the metal centre ab initio calculations [HF/6–31+G(d,p) method] were carried out on the free ligand by using GAUSSIAN98 (Frisch et al., 1998). The most important variations concern pyridyl-N atoms: the calculated N—C distances 1.318 and 1.321 Å in each ring are shorter than the experimental mean value 1.350 (5) Å while the N^···N computed separation of 3.41 Å is significantly longer, mainly due to the N,N-coordination of dps. The calculated C—S bond lengths are slightly longer than the experimental mean value of 1.764 (4) Å], while the C—S—C computed bond angle of 101.5° is very close to the observed average 102.3 (2)°.

S2. Experimental

[Ru(N,N-dps)₂(N,S-dps)][PF₆]₂^.H₂O was prepared according to the method of Scopelliti et al. (2001). All other chemicals were reagent grade. An acetone-acetonitrile (1:1) solution (5 ml) of Ru(N,N-dps)₂(N,S-dps)][PF₆]₂^.H₂O (48.68 mg, 0.05 mmol) was introduced into a test-tube and 0.1 ml of an aqueous solution of HBF₄ (7.65M) added. Di-isopropyl ether (8 ml) was layered on top of the reaction mixture and the test tube was closed with parafilm. After 20 d colourless crystals were isolated and found to be suitable for X-ray structure investigation. The analysis of C₂₄H₂₄B₂F₈N₆ORuS₂ gave C 38.37 versus 38.40, H 3.22 versus 3.35, N 11.19 versus 11.10 and S 8.53 versus 8.50% for the calculated and found composition, respectively.

Reflection intensities were evaluated by profile fitting of a 96-steps peak scan among 2θ shells procedure (Diamond, 1969). H atoms were located in idealized positions and allowed to ride on their parent C atoms with isotropic displacement parameters related to the refined values of their corresponding parent atoms. In the last refinement cycles the water-H atoms were fixed in the idealized positions located by HYDROGEN (Nardelli, 1999). Both [BF₄]^- anions appear to be affected by the usual rotational disorder and one tetrahedral moiety was split in two orientations.

Computing details

Data collection: XSCANS (Bruker,1999); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS90 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XPW (SHELXTL; Siemens, 1996); software used to prepare material for publication: PARST97 (Nardelli, 1995) and SHELXL97.

Figures

Fig. 1. View of one ruthenium complex showing the atomic numbering scheme of the independent fragment. Displacement ellipsoids are drawn at the 30% probability level while H atoms are of arbitrary size. The unlabelled atoms represent the centrosymmetric (1 - x, 1 - y, -z) portion of the complex, with the anions and water molecule omitted for clarity.

trans-bis(acetonitrile)-bis(di-2-pyridylsulfide-N,N')-ruthenium(ii) bis(tetrafluoroborate) monohydrate

Crystal data

[Ru(C2H3N)2(C10H8N2S)2].2(BF4).H2O	Z = 2
Mr = 751.30	F(000) = 752
Triclinic, P1	Dx = 1.627 Mg m^−3
a = 10.0709 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.6595 (8) Å	Cell parameters from 37 reflections
c = 13.547 (1) Å	θ = 8.2–16.0°
α = 77.016 (7)°	µ = 0.73 mm^−1
β = 75.004 (6)°	T = 298 K
γ = 68.225 (6)°	Prysmatic, pale yellow
V = 1533.3 (2) Å^3	0.36 × 0.30 × 0.25 mm

Data collection

Siemens P4 diffractometer	4761 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 26.0°, θmin = 1.6°
2θ/ω scans	h = −11→1
Absorption correction: numerical by seven indexed faces (XPREPW in SHELXTL; Siemens, 1996)	k = −14→14
Tmin = 0.689, Tmax = 0.826	l = −16→16
7496 measured reflections	3 standard reflections every 197 reflections
5922 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0413P)^2 + 0.9658P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.051
5922 reflections	Δρmax = 0.53 e Å^−3
440 parameters	Δρmin = −0.39 e Å^−3
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0028 (5)

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.

One BF₄^- anion appeared to be affected by rotational disorder and it was splitted into two positions (0.53/0.47 occup.).

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ru1	0.5000	0.5000	0.0000	0.03497 (10)
N1	0.5978 (3)	0.3215 (2)	0.02163 (17)	0.0426 (5)
C1	0.5364 (4)	0.2561 (3)	−0.0051 (2)	0.0516 (7)
H1	0.4501	0.2926	−0.0299	0.062*
C2	0.5949 (5)	0.1389 (3)	0.0026 (3)	0.0697 (10)
H2	0.5488	0.0969	−0.0158	0.084*
C3	0.7239 (6)	0.0842 (3)	0.0382 (3)	0.0857 (13)
H3	0.7676	0.0049	0.0421	0.103*
C4	0.7862 (5)	0.1480 (3)	0.0676 (3)	0.0745 (11)
H4	0.8726	0.1124	0.0923	0.089*
C5	0.7203 (3)	0.2664 (3)	0.0604 (2)	0.0519 (7)
S1	0.80545 (9)	0.34311 (8)	0.10157 (7)	0.0585 (2)
C6	0.6585 (3)	0.4328 (3)	0.1807 (2)	0.0484 (7)
C7	0.6782 (4)	0.4332 (3)	0.2783 (3)	0.0649 (9)
H7	0.7629	0.3841	0.3011	0.078*
C8	0.5719 (5)	0.5065 (4)	0.3405 (3)	0.0741 (11)
H8	0.5844	0.5096	0.4054	0.089*
C9	0.4464 (4)	0.5756 (3)	0.3060 (2)	0.0643 (9)
H9	0.3721	0.6254	0.3475	0.077*
C10	0.4319 (4)	0.5702 (3)	0.2092 (2)	0.0504 (7)
H10	0.3456	0.6162	0.1872	0.060*
N2	0.5367 (3)	0.5013 (2)	0.14480 (17)	0.0421 (5)
N3	0.6882 (3)	0.5266 (2)	−0.07705 (17)	0.0415 (5)
C11	0.7904 (3)	0.5444 (3)	−0.1224 (2)	0.0483 (7)
C12	0.9247 (4)	0.5660 (4)	−0.1778 (3)	0.0775 (11)
H12A	1.0048	0.4950	−0.1768	0.116*
H12B	0.9415	0.6186	−0.1452	0.116*
H12C	0.9162	0.5987	−0.2480	0.116*
Ru2	0.5000	0.0000	0.5000	0.03769 (10)
N4	0.3750 (2)	0.17193 (19)	0.51251 (19)	0.0443 (5)
C13	0.3093 (3)	0.2031 (3)	0.6071 (3)	0.0534 (7)
H13	0.3202	0.1464	0.6644	0.064*
C14	0.2278 (4)	0.3138 (3)	0.6228 (3)	0.0679 (9)
H14	0.1876	0.3315	0.6895	0.081*
C15	0.2058 (4)	0.3979 (3)	0.5401 (4)	0.0739 (11)
H15	0.1504	0.4735	0.5493	0.089*
C16	0.2673 (4)	0.3687 (3)	0.4426 (3)	0.0638 (9)
H16	0.2525	0.4243	0.3849	0.077*
C17	0.3515 (3)	0.2558 (3)	0.4313 (2)	0.0494 (7)
S2	0.43334 (10)	0.22457 (7)	0.30422 (6)	0.0581 (2)
C18	0.3829 (3)	0.1060 (3)	0.3008 (2)	0.0467 (7)
C19	0.3218 (3)	0.1116 (3)	0.2182 (2)	0.0565 (8)
H19	0.3059	0.1769	0.1688	0.068*
C20	0.2852 (4)	0.0209 (3)	0.2099 (3)	0.0624 (9)
H20	0.2468	0.0227	0.1538	0.075*
C21	0.3057 (3)	−0.0731 (3)	0.2857 (3)	0.0591 (8)
H21	0.2797	−0.1353	0.2825	0.071*
C22	0.3655 (3)	−0.0734 (3)	0.3665 (2)	0.0496 (7)
H22	0.3774	−0.1365	0.4182	0.060*
N5	0.4077 (2)	0.0133 (2)	0.37408 (17)	0.0432 (5)
N6	0.6772 (3)	0.0372 (2)	0.41339 (18)	0.0444 (5)
C23	0.7854 (3)	0.0495 (3)	0.3741 (2)	0.0500 (7)
C24	0.9247 (4)	0.0654 (4)	0.3237 (3)	0.0745 (11)
H24A	0.9084	0.1344	0.2746	0.112*
H24B	0.9858	0.0009	0.2887	0.112*
H24C	0.9715	0.0715	0.3745	0.112*
B1	0.0766 (5)	0.7393 (4)	0.5048 (3)	0.0661 (11)
F1	−0.0135 (5)	0.8416 (3)	0.4887 (4)	0.197 (2)
F2	0.0894 (4)	0.6796 (3)	0.4248 (2)	0.1297 (11)
F3	0.2127 (3)	0.7381 (3)	0.5038 (2)	0.1249 (11)
F4	0.0336 (3)	0.6803 (3)	0.5939 (2)	0.1212 (10)
B2	0.1943 (6)	0.2454 (4)	0.9234 (4)	0.0747 (12)
F5	0.3217 (14)	0.1845 (13)	0.8897 (15)	0.202 (7)	0.55 (2)
F6	0.2077 (16)	0.3463 (8)	0.8939 (13)	0.179 (6)	0.55 (2)
F7	0.1507 (17)	0.2074 (14)	1.0198 (9)	0.205 (8)	0.55 (2)
F8	0.1033 (18)	0.2267 (18)	0.8888 (11)	0.166 (5)	0.55 (2)
F5A	0.3007 (18)	0.1719 (10)	0.8596 (9)	0.120 (5)	0.45 (2)
F7A	0.208 (3)	0.1899 (12)	1.0168 (12)	0.165 (8)	0.45 (2)
F6A	0.1953 (13)	0.3471 (12)	0.9400 (18)	0.174 (8)	0.45 (2)
F8A	0.0579 (13)	0.2803 (10)	0.8852 (8)	0.088 (3)	0.45 (2)
O	0.9078 (5)	0.2009 (5)	0.7862 (3)	0.163 (2)
H0A	0.9179	0.2317	0.7215	0.080*
H0B	0.9564	0.2240	0.8135	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.03699 (17)	0.04050 (18)	0.03119 (16)	−0.01942 (13)	−0.00549 (12)	−0.00249 (12)
N1	0.0471 (13)	0.0449 (13)	0.0358 (12)	−0.0205 (11)	−0.0031 (10)	−0.0028 (10)
C1	0.0625 (19)	0.0530 (18)	0.0444 (16)	−0.0317 (15)	0.0029 (14)	−0.0107 (13)
C2	0.093 (3)	0.056 (2)	0.063 (2)	−0.038 (2)	0.007 (2)	−0.0178 (17)
C3	0.118 (4)	0.046 (2)	0.078 (3)	−0.012 (2)	−0.013 (3)	−0.0128 (19)
C4	0.087 (3)	0.054 (2)	0.066 (2)	0.0001 (19)	−0.022 (2)	−0.0096 (17)
C5	0.0556 (18)	0.0513 (17)	0.0416 (16)	−0.0131 (14)	−0.0074 (13)	−0.0031 (13)
S1	0.0474 (4)	0.0689 (5)	0.0579 (5)	−0.0153 (4)	−0.0194 (4)	−0.0030 (4)
C6	0.0551 (18)	0.0586 (18)	0.0404 (15)	−0.0302 (15)	−0.0152 (13)	0.0020 (13)
C7	0.074 (2)	0.086 (3)	0.0491 (19)	−0.041 (2)	−0.0248 (17)	0.0007 (18)
C8	0.095 (3)	0.109 (3)	0.0407 (18)	−0.057 (3)	−0.0163 (19)	−0.0110 (19)
C9	0.082 (2)	0.082 (2)	0.0418 (17)	−0.045 (2)	0.0027 (17)	−0.0197 (16)
C10	0.0575 (18)	0.0567 (18)	0.0418 (16)	−0.0283 (15)	−0.0029 (13)	−0.0081 (13)
N2	0.0474 (13)	0.0508 (13)	0.0354 (12)	−0.0269 (11)	−0.0068 (10)	−0.0035 (10)
N3	0.0429 (13)	0.0481 (13)	0.0373 (12)	−0.0215 (11)	−0.0076 (10)	−0.0028 (10)
C11	0.0430 (16)	0.0508 (17)	0.0498 (17)	−0.0196 (14)	−0.0076 (14)	0.0009 (13)
C12	0.0457 (19)	0.087 (3)	0.089 (3)	−0.0318 (19)	0.0035 (18)	0.006 (2)
Ru2	0.03723 (17)	0.03944 (18)	0.03546 (17)	−0.01596 (13)	−0.01024 (13)	0.00574 (12)
N4	0.0431 (13)	0.0423 (13)	0.0479 (14)	−0.0170 (10)	−0.0128 (11)	0.0020 (10)
C13	0.0521 (18)	0.0529 (18)	0.0535 (18)	−0.0164 (14)	−0.0110 (14)	−0.0056 (14)
C14	0.066 (2)	0.063 (2)	0.076 (2)	−0.0145 (17)	−0.0143 (19)	−0.0222 (19)
C15	0.075 (2)	0.0477 (19)	0.103 (3)	−0.0145 (17)	−0.028 (2)	−0.017 (2)
C16	0.072 (2)	0.0428 (17)	0.084 (3)	−0.0246 (16)	−0.034 (2)	0.0086 (17)
C17	0.0482 (16)	0.0452 (16)	0.0589 (18)	−0.0223 (13)	−0.0204 (14)	0.0079 (13)
S2	0.0660 (5)	0.0575 (5)	0.0493 (4)	−0.0301 (4)	−0.0166 (4)	0.0184 (4)
C18	0.0401 (15)	0.0548 (17)	0.0377 (14)	−0.0133 (13)	−0.0072 (12)	0.0035 (12)
C19	0.0505 (18)	0.070 (2)	0.0380 (16)	−0.0109 (16)	−0.0113 (13)	−0.0001 (14)
C20	0.0544 (19)	0.083 (2)	0.0460 (18)	−0.0114 (18)	−0.0148 (15)	−0.0162 (17)
C21	0.0520 (18)	0.070 (2)	0.062 (2)	−0.0203 (16)	−0.0140 (16)	−0.0189 (17)
C22	0.0474 (16)	0.0520 (17)	0.0515 (17)	−0.0197 (14)	−0.0126 (13)	−0.0026 (13)
N5	0.0401 (12)	0.0495 (13)	0.0389 (12)	−0.0172 (10)	−0.0104 (10)	0.0027 (10)
N6	0.0411 (13)	0.0467 (13)	0.0430 (13)	−0.0170 (11)	−0.0085 (11)	0.0032 (10)
C23	0.0447 (17)	0.0520 (17)	0.0493 (17)	−0.0175 (14)	−0.0123 (14)	0.0067 (13)
C24	0.0491 (19)	0.092 (3)	0.075 (2)	−0.0329 (19)	−0.0046 (17)	0.012 (2)
B1	0.075 (3)	0.065 (3)	0.062 (3)	−0.030 (2)	−0.026 (2)	0.012 (2)
F1	0.228 (5)	0.083 (2)	0.251 (5)	0.019 (2)	−0.137 (4)	0.016 (3)
F2	0.139 (3)	0.183 (3)	0.094 (2)	−0.073 (2)	−0.0276 (19)	−0.034 (2)
F3	0.114 (2)	0.187 (3)	0.103 (2)	−0.093 (2)	−0.0193 (18)	−0.006 (2)
F4	0.132 (2)	0.152 (3)	0.0819 (18)	−0.080 (2)	−0.0105 (17)	0.0233 (18)
B2	0.089 (3)	0.075 (3)	0.068 (3)	−0.026 (3)	−0.036 (3)	−0.004 (2)
F5	0.097 (6)	0.235 (12)	0.312 (18)	−0.032 (6)	−0.003 (8)	−0.195 (13)
F6	0.266 (13)	0.079 (6)	0.229 (12)	−0.088 (7)	−0.133 (9)	0.062 (7)
F7	0.196 (10)	0.192 (11)	0.074 (6)	0.074 (8)	−0.008 (6)	0.020 (5)
F8	0.153 (10)	0.199 (14)	0.198 (9)	−0.073 (9)	−0.117 (8)	−0.005 (9)
F5A	0.164 (11)	0.093 (6)	0.084 (6)	−0.034 (5)	0.002 (5)	−0.021 (5)
F7A	0.31 (2)	0.106 (7)	0.115 (10)	−0.059 (11)	−0.158 (13)	0.033 (6)
F6A	0.104 (7)	0.126 (9)	0.35 (2)	−0.005 (6)	−0.104 (9)	−0.132 (13)
F8A	0.081 (5)	0.115 (7)	0.079 (5)	−0.027 (4)	−0.035 (4)	−0.020 (4)
O	0.172 (4)	0.290 (6)	0.095 (3)	−0.152 (4)	−0.033 (3)	−0.020 (3)

Geometric parameters (Å, º)

Ru1—N3	2.022 (2)	C14—C15	1.363 (5)
Ru1—N1	2.088 (2)	C14—H14	0.9300
Ru1—N2	2.092 (2)	C15—C16	1.374 (5)
N1—C5	1.348 (4)	C15—H15	0.9300
N1—C1	1.353 (4)	C16—C17	1.385 (5)
C1—C2	1.369 (5)	C16—H16	0.9300
C1—H1	0.9300	C17—S2	1.768 (3)
C2—C3	1.380 (6)	S2—C18	1.767 (3)
C2—H2	0.9300	C18—N5	1.346 (3)
C3—C4	1.361 (6)	C18—C19	1.387 (4)
C3—H3	0.9300	C19—C20	1.364 (5)
C4—C5	1.387 (5)	C19—H19	0.9300
C4—H4	0.9300	C20—C21	1.376 (5)
C5—S1	1.761 (3)	C20—H20	0.9300
S1—C6	1.763 (3)	C21—C22	1.378 (4)
C6—N2	1.351 (4)	C21—H21	0.9300
C6—C7	1.389 (4)	C22—N5	1.347 (4)
C7—C8	1.365 (5)	C22—H22	0.9300
C7—H7	0.9300	N6—C23	1.133 (4)
C8—C9	1.373 (5)	C23—C24	1.458 (4)
C8—H8	0.9300	C24—H24A	0.9600
C9—C10	1.375 (4)	C24—H24B	0.9600
C9—H9	0.9300	C24—H24C	0.9600
C10—N2	1.348 (4)	B1—F1	1.285 (5)
C10—H10	0.9300	B1—F4	1.329 (5)
N3—C11	1.127 (4)	B1—F3	1.362 (5)
C11—C12	1.457 (4)	B1—F2	1.410 (5)
C12—H12A	0.9600	B2—F8	1.245 (13)
C12—H12B	0.9600	B2—F5	1.253 (14)
C12—H12C	0.9600	B2—F6	1.296 (10)
Ru2—N6	2.018 (2)	B2—F7	1.307 (14)
Ru2—N4	2.091 (2)	B2—F7A	1.317 (13)
Ru2—N5	2.093 (2)	B2—F6A	1.360 (12)
N4—C17	1.348 (4)	B2—F5A	1.380 (14)
N4—C13	1.353 (4)	B2—F8A	1.472 (13)
C13—C14	1.369 (4)	O—H0A	0.872
C13—H13	0.9300	O—H0B	0.843
N3—Ru1—N3^i	180.000 (1)	C17—N4—C13	116.5 (3)
N3—Ru1—N1^i	86.79 (9)	C17—N4—Ru2	124.2 (2)
N3—Ru1—N1	93.21 (9)	C13—N4—Ru2	119.30 (19)
N1^i—Ru1—N1	180.00 (13)	N4—C13—C14	123.3 (3)
N3—Ru1—N2^i	86.25 (9)	N4—C13—H13	118.3
N1—Ru1—N2^i	91.71 (9)	C14—C13—H13	118.3
N3—Ru1—N2	93.75 (9)	C15—C14—C13	119.6 (4)
N1—Ru1—N2	88.29 (9)	C15—C14—H14	120.2
N2^i—Ru1—N2	180.0	C13—C14—H14	120.2
C5—N1—C1	117.2 (3)	C14—C15—C16	118.7 (3)
C5—N1—Ru1	124.0 (2)	C14—C15—H15	120.7
C1—N1—Ru1	118.8 (2)	C16—C15—H15	120.7
N1—C1—C2	123.2 (3)	C15—C16—C17	119.4 (3)
N1—C1—H1	118.4	C15—C16—H16	120.3
C2—C1—H1	118.4	C17—C16—H16	120.3
C1—C2—C3	118.7 (4)	N4—C17—C16	122.6 (3)
C1—C2—H2	120.6	N4—C17—S2	120.1 (2)
C3—C2—H2	120.6	C16—C17—S2	117.3 (3)
C4—C3—C2	119.1 (4)	C18—S2—C17	102.4 (1)
C4—C3—H3	120.5	N5—C18—C19	122.2 (3)
C2—C3—H3	120.5	N5—C18—S2	120.7 (2)
C3—C4—C5	119.7 (4)	C19—C18—S2	117.1 (2)
C3—C4—H4	120.1	C20—C19—C18	119.6 (3)
C5—C4—H4	120.1	C20—C19—H19	120.2
N1—C5—C4	121.9 (3)	C18—C19—H19	120.2
N1—C5—S1	120.8 (2)	C19—C20—C21	119.1 (3)
C4—C5—S1	117.3 (3)	C19—C20—H20	120.5
C5—S1—C6	102.3 (1)	C21—C20—H20	120.5
N2—C6—C7	122.5 (3)	C20—C21—C22	118.7 (3)
N2—C6—S1	120.7 (2)	C20—C21—H21	120.7
C7—C6—S1	116.6 (3)	C22—C21—H21	120.7
C8—C7—C6	119.2 (3)	N5—C22—C21	123.2 (3)
C8—C7—H7	120.4	N5—C22—H22	118.4
C6—C7—H7	120.4	C21—C22—H22	118.4
C7—C8—C9	119.0 (3)	C18—N5—C22	117.2 (3)
C7—C8—H8	120.5	C18—N5—Ru2	123.7 (2)
C9—C8—H8	120.5	C22—N5—Ru2	119.00 (19)
C8—C9—C10	119.1 (3)	C23—N6—Ru2	171.5 (2)
C8—C9—H9	120.4	N6—C23—C24	179.9 (4)
C10—C9—H9	120.4	C23—C24—H24A	109.5
N2—C10—C9	123.2 (3)	C23—C24—H24B	109.5
N2—C10—H10	118.4	H24A—C24—H24B	109.5
C9—C10—H10	118.4	C23—C24—H24C	109.5
C10—N2—C6	116.8 (2)	H24A—C24—H24C	109.5
C10—N2—Ru1	119.4 (2)	H24B—C24—H24C	109.5
C6—N2—Ru1	123.8 (2)	F1—B1—F4	112.9 (5)
C11—N3—Ru1	177.5 (2)	F1—B1—F3	112.6 (4)
N3—C11—C12	178.0 (3)	F4—B1—F3	107.7 (3)
C11—C12—H12A	109.5	F1—B1—F2	108.5 (4)
C11—C12—H12B	109.5	F4—B1—F2	107.9 (4)
H12A—C12—H12B	109.5	F3—B1—F2	107.0 (4)
C11—C12—H12C	109.5	F8—B2—F5	111.4 (9)
H12A—C12—H12C	109.5	F8—B2—F6	116.5 (9)
H12B—C12—H12C	109.5	F5—B2—F6	99.6 (11)
N6^ii—Ru2—N6	180.0	F8—B2—F7	96.0 (12)
N6^ii—Ru2—N4	85.99 (9)	F5—B2—F7	110.9 (10)
N6—Ru2—N4	94.01 (9)	F6—B2—F7	122.9 (12)
N6—Ru2—N4^ii	85.99 (9)	F7A—B2—F6A	96.8 (11)
N4—Ru2—N4^ii	180.00 (14)	F7A—B2—F5A	103.5 (10)
N6—Ru2—N5^ii	85.12 (9)	F6A—B2—F5A	126.3 (12)
N6—Ru2—N5	94.88 (9)	F7A—B2—F8A	122.5 (12)
N4—Ru2—N5	88.61 (9)	F6A—B2—F8A	102.3 (7)
N4^ii—Ru2—N5	91.39 (9)	F5A—B2—F8A	107.2 (8)
N5^ii—Ru2—N5	180.000 (1)	H0A—O—H0B	106.3
N3—Ru1—N1—C5	50.6 (2)	N6^ii—Ru2—N4—C17	−125.6 (2)
N3^i—Ru1—N1—C5	−129.4 (2)	N6—Ru2—N4—C17	54.4 (2)
N2^i—Ru1—N1—C5	137.0 (2)	N5^ii—Ru2—N4—C17	139.6 (2)
N2—Ru1—N1—C5	−43.0 (2)	N5—Ru2—N4—C17	−40.4 (2)
N3—Ru1—N1—C1	−128.9 (2)	N6^ii—Ru2—N4—C13	52.8 (2)
N3^i—Ru1—N1—C1	51.1 (2)	N6—Ru2—N4—C13	−127.2 (2)
N2^i—Ru1—N1—C1	−42.6 (2)	N5^ii—Ru2—N4—C13	−42.0 (2)
N2—Ru1—N1—C1	137.4 (2)	N5—Ru2—N4—C13	138.0 (2)
C5—N1—C1—C2	−2.1 (4)	C17—N4—C13—C14	−2.7 (5)
Ru1—N1—C1—C2	177.6 (2)	Ru2—N4—C13—C14	178.8 (3)
N1—C1—C2—C3	−0.7 (5)	N4—C13—C14—C15	2.3 (5)
C1—C2—C3—C4	2.0 (6)	C13—C14—C15—C16	−0.3 (6)
C2—C3—C4—C5	−0.6 (6)	C14—C15—C16—C17	−1.1 (5)
C1—N1—C5—C4	3.6 (4)	C13—N4—C17—C16	1.2 (4)
Ru1—N1—C5—C4	−176.0 (3)	Ru2—N4—C17—C16	179.6 (2)
C1—N1—C5—S1	−177.9 (2)	C13—N4—C17—S2	179.5 (2)
Ru1—N1—C5—S1	2.5 (3)	Ru2—N4—C17—S2	−2.0 (3)
C3—C4—C5—N1	−2.3 (6)	C15—C16—C17—N4	0.7 (5)
C3—C4—C5—S1	179.1 (3)	C15—C16—C17—S2	−177.7 (3)
N1—C5—S1—C6	49.1 (3)	N4—C17—S2—C18	51.9 (3)
C4—C5—S1—C6	−132.2 (3)	C16—C17—S2—C18	−129.7 (3)
C5—S1—C6—N2	−53.4 (3)	C17—S2—C18—N5	−52.0 (3)
C5—S1—C6—C7	129.7 (3)	C17—S2—C18—C19	129.9 (2)
N2—C6—C7—C8	−1.0 (5)	N5—C18—C19—C20	−0.1 (5)
S1—C6—C7—C8	175.8 (3)	S2—C18—C19—C20	177.9 (2)
C6—C7—C8—C9	1.9 (6)	C18—C19—C20—C21	2.0 (5)
C7—C8—C9—C10	−0.8 (5)	C19—C20—C21—C22	−1.3 (5)
C8—C9—C10—N2	−1.2 (5)	C20—C21—C22—N5	−1.3 (5)
C9—C10—N2—C6	2.1 (4)	C19—C18—N5—C22	−2.4 (4)
C9—C10—N2—Ru1	179.4 (2)	S2—C18—N5—C22	179.7 (2)
C7—C6—N2—C10	−1.0 (4)	C19—C18—N5—Ru2	179.8 (2)
S1—C6—N2—C10	−177.7 (2)	S2—C18—N5—Ru2	1.9 (3)
C7—C6—N2—Ru1	−178.2 (2)	C21—C22—N5—C18	3.1 (4)
S1—C6—N2—Ru1	5.2 (3)	C21—C22—N5—Ru2	−179.0 (2)
N3—Ru1—N2—C10	128.5 (2)	N6^ii—Ru2—N5—C18	126.5 (2)
N3^i—Ru1—N2—C10	−51.5 (2)	N6—Ru2—N5—C18	−53.5 (2)
N1^i—Ru1—N2—C10	41.6 (2)	N4—Ru2—N5—C18	40.4 (2)
N1—Ru1—N2—C10	−138.4 (2)	N4^ii—Ru2—N5—C18	−139.6 (2)
N3—Ru1—N2—C6	−54.5 (2)	N6^ii—Ru2—N5—C22	−51.3 (2)
N3^i—Ru1—N2—C6	125.5 (2)	N6—Ru2—N5—C22	128.7 (2)
N1^i—Ru1—N2—C6	−141.4 (2)	N4—Ru2—N5—C22	−137.4 (2)
N1—Ru1—N2—C6	38.6 (2)	N4^ii—Ru2—N5—C22	42.6 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C19—H19···F7A^iii	0.93	2.45	3.05 (1)	122
C20—H20···F7A^iii	0.93	2.46	3.05 (1)	121
C12—H12C···F4^iv	0.96	2.38	3.205 (5)	144
C12—H12A···F6^iv	0.96	2.45	3.34 (1)	154
O—H0A···F2^v	0.87	2.05	2.917 (5)	171
O—H0B···F8^vi	0.84	2.02	2.83 (1)	162
O—H0B···F8A^vi	0.84	1.96	2.81 (1)	176

Symmetry codes: (iii) x, y, z−1; (iv) x+1, y, z−1; (v) −x+1, −y+1, −z+1; (vi) x+1, y, z.