Bis­[tris(2,2'-bi­pyridine-[kappa]²N,N')­ruthenium(II)] hexa­cyano­ferrate(III) chloride octahydrate

In the title compound, [Ru^II(C₁₀H₈N₂)₃]₂[Fe^III(CN)₆]Cl·8H₂O, the [Ru(bpy)₃]²⁺ (bpy is 2,2'-bi­pyridine) cations and water mol­ecules afford intriguing microporous honeycomb layers, while the [Fe(CN)₆]^3- anions and the remainder of the water mol­ecules form anionic sheets based on extensive hydrogen-bonding networks. The cationic and anionic layers alternate along the c axis. The Fe atom in [Fe(CN)₆]^3- lies on an inversion centre and the axial cyano ligands are hydrogen bonded to the water mol­ecules encapsulated within the micropores [N...O = 2.788 (5) Å], giving an unusual interpenetration between the cationic and anionic layers. On the other hand, the in-plane cyano ligands are relatively weakly hydrogen bonded to the water mol­ecules [N...O = 2.855 (7) and 2.881 (8) Å] within the anionic sheets.

S1. Comment

We previously discovered that amidate-bridged cis-diammineplatinum(II) dimers [Pt₂(NH₃)₄(µ-amidato)₂]²⁺ (amidate is acetamidate, α-pyrrolidinonate, α-pyridonate etc.) serve as efficient homogeneous catalysts in the photoreduction of water into molecular hydrogen (Sakai & Matsumoto, 1990; Sakai et al., 1993). Since then, efforts have also been made to develop `photomolecular devices evolving molecular hydrogen from water'. With this aim, a well known photosystem consisting of [Ru(bpy)₃]²⁺ (bpy is 2,2'-bipyridine) and methylviologen (usually N,N'-dimethyl-4,4'-bipyridinium dichloride; Borgarello et al., 1981) has been employed to evaluate the catalytic activity of various platinum complexes. In this context, we started five years ago to explore the chemistry of double salts containing [Ru(bpy)₃]²⁺ and the platinum complexes. Our aim has been to develop water-insoluble crystals involving both photosensitizers and H₂-evolving catalysts. Visible-light-induced water splitting into H₂ and O₂ might be promoted under dispersion of such hybrid crystals in water. As part of such studies, we report here the crystal structure of the title compound, [Ru^II(bpy)₃]₂[Fe^III(CN)₆]Cl^.8H₂O, (I).

Up to now, several crystal structures of double salts having the same composition type with different metal/halide combinations have been reported, namely [M₁^II(bpy)₃]₂[M₂^III(CN)₆]X·8H₂O [M₁/M₂/X = Ru/Co/Cl (refcode HIGZAY; Tamura et al., 1996), Os/Cr/Cl (refcode HIRDOB; Otsuka et al., 1999; corrected as HIRDOB01; Marsh & Spek, 2001), Ru/Cr/Br (HIRDUH01; Otsuka et al., 2001) and Ru/Cr/Cl (HIRFAP01; Otsuka et al., 2001)], where 'refcodes' are assigned by the November 2002 release of the Cambridge Structural Database (Allen, 2002). All of these structures were described in space group C2. However, it was later pointed out that the structure of HIRDOB should be more properly described in C2/c (Marsh & Spek, 2001; see also Marsh et al., 1995). In addition, the structures of HIGZAY, HIRDUH01 and HIRFAP01 may also be more properly described in C2/c. As reported for the above-mentioned analogs, the authors initially decided to choose space group C2 for (I), since a chloride and a water O atom can be described as independent atoms without suffering from any disorder problem. However, at the suggestion of the co-editor of this paper, the validity of space-group selection has been re-examined. As a result, the final reliability factors in C2/c and C2 have been confirmed to be essentially similar, suggesting that the positional and displacement parameters independently determined for the Cl and O atoms in C2 can be considered as artifacts. Thus space group C2/c has been judged to be valid in the present case.

The asymmetric unit of (I) consists of an [Ru^II(bpy)₃]²⁺ cation, one-half of an [Fe^III(CN)₆]³⁻ anion, one-half of a chloride anion and four water molecules (Fig. 1). Atom Fe1 is located at an inversion center. Atoms Cl1 and O1 are assumed to occupy the same site, each having an occupancy of 50%. Atom O2 is located on a twofold axis. Compound (I) possesses an intriguing layered structure (similar to that previously reported for HIGZAY, HIRDOB01, HIRDUH01 and HIRFAP01), in which the layers consisting of the [Ru^II(bpy)₃]²⁺ cations and water molecules, and the layers consisting of the [Fe^III(CN)₆]³⁻ anions and water molecules alternate along the c axis (Figs. 2–4). More interestingly, each cationic layer can be understood as a honeycomb layer in which a water molecule (O2) is encapsulated within each microporous cavity (Fig. 2). An important feature is that the layer within 0 < z < 1/2, shown in Fig. 2, is made up of the Δ isomers, while the layer within 1/2 < z < 1 only involves the Λ isomers. The structural features of the hexagons are listed in Table 1. Mean-plane calculations reveal that the hexagons containing the Ru1 centers have a planar geometry, where the r.m.s. deviation of the six atoms from the plane of the hexagon is 0.108 Å. When the cavity is viewed along the c axis (Fig. 2), it is considered to be elliptical (ca 3.8 × 2.8 Å in inner diameter, where the van der Waals components of the H atoms are suppressed by assuming a radius of 1.2 Å). The intercationic interactions are stabilized by hydrophobic interactions between the aromatic hydrocarbon moieties, where the shortest C···C distance is ca 3.6 Å and no π–π stacking interactions are achieved between the bpy ligands.

The [Fe^III(CN)₆]³⁻ anions and the rest of the water molecules form two-dimensional sheets based on extensive hydrogen-bonding networks (Figs. 3 and 4, and Table 2). Interestingly, all the components, excluding the axial cyano ligands (C33 and N9), lie in a thin slab of depth 0.0310 (4) Å, one-half of which corresponds to the shift of atom O4 from the plane z=0. Another important feature is that two neighbouring anionic sheets are connected to one another through hydrogen bonds formed between the N(cyano) atoms (N9) and the water molecules (O2) encapsulated within the micropores [N9···O2 = 2.788 (5) Å]. Thus interpenetration occurs via the formation of a one-dimensional hydrogen-bonding network along the c axis (Fig. 5).

The Fe^III ion adopts a nearly regular octahedral geometry, even though the in-plane Fe—C distances [Fe1—C32 = 1.937 (6) Å and Fe1—C31 = 1.942 (6) Å] appear slightly shorter than the axial distance [Fe1—C33 = 1.951 (5) Å], where the in-plane Fe(CN)₄ plane is assumed to be parallel to the ab plane. In addition, the so-called tetragonality (T=0.994) is close to unity. The most remarkable feature is that the hydrogen bonds formed between the in-plane cyano ligands and the neighbouring water molecules [N7···O3 = 2.855 (7) Å and N8···O4 = 2.881 (8) Å] are much weaker than those for the axial cyano ligands, revealing that the in-plane Fe—C bonds possess higher flexibility toward changes in the bond length, which? may be induced upon the photochemical process discussed below.

It was previously reported that the ³MLCT (MLCT is metal-to-ligand charge transfer) excited state of [Ru^II(bpy)₃]²⁺ in (I) is very rapidly quenched, even at 77 K, based on the electron transfer (ET) quenching, affording [Ru^III(bpy)₃]³⁺ and [Fe^II(CN)₆]⁴⁻ (Iguro et al., 1994). This outcome is attributed to the fact that the reorganization energy required for the process is small as a result of the small number of water molecules involved in (I) (Iguro et al., 1994). On the other hand, it was previously reported that the Ru—N distances in [Ru^II(bpy)₃](PF₆)₂ [2.053 (2) Å, 105 K] are virtually indistinguishable from those in [Ru^III(bpy)₃](PF₆)₃ [2.057 (3) Å, 105 K] (Biner et al., 1992). Moreover, the Fe^III—C(CN) and Fe^III···N(CN) distances observed in (I) [the Fe^III—C(CN) distances are given in Table 1; Fe1···N7 = 3.084 (5) Å, Fe1···N8 = 3.089 (5) Å and Fe1···N9 = 3.094 (5) Å] are similar to those reported for [Fe^II(CN)₆]⁴⁻, for example Fe^II—C(CN) = 1.922 (8)–1.935 (5) Å and Fe^II···N(CN) = 3.108–3.125 Å for Li₄[Fe^II(CN)₆].hexamethylenetetramine·5H₂O (Meyer & Pickardt, 1988). These ? indicate that the change in the molecular volume upon ET quenching is relatively small in ?either Ru- or Fe-complex ion. Consequently, it is considered that a relatively small reorganization energy is required to drive the ET quenching process, regardless of whether it is undertaken in solution or in the crystal. What can be deduced from the crystal structure of (I) is that the in-plane Fe—C bonds can afford either elongation or shortening upon the ET quenching process, as a result of the loose hydrogen-bonding character of the in-plane cyano ligands. This study implies that such structural features may be relevant to the relatively rapid ET quenching character previously reported for the title double salt (Iguro et al., 1994).

S2. Experimental

It is often believed that double salts are almost insoluble in water and that their crystals should be grown using the so-called diffusion methods. Indeed, a crystalline sample of (I) was previously prepared by a diffusion method (Iguro et al., 1994). Crystals of all the double salts cited above have similarly been reported to have been grown by diffusion methods (Tamura et al., 1996; Otsuka et al., 1999, 2001). However, we found that (I) can be merely recrystallized from hot water in a conventional manner as follows. [Ru(bpy)₃]Cl₂^.6H₂O was prepared as previously reported (Fujita & Kobayashi, 1972), except that acetone instead of benzene was used to extract the unreacted bpy. To a solution of [Ru(bpy)₃]Cl₂^.6H₂O in a minimum amount of water was added a solution of K₃[Fe(CN)₆] in a minimum amount of water. The brown precipitate deposited was collected by filtration and recrystallized from hot water as follows. An aqueous saturated solution of (I) was prepared at 343 K and filtered while it was hot. Gradual cooling to room temperature resulted in the growth of good quality red–brown needles of (I). Compound (I) is quite stable in air at room temperature. Analysis calculated for Ru₂FeClO₈N₁₈C₆₆H₆₄: C 51.57, H 4.02, N 16.42%; found: C 51.78, H 4.21, N 16.47%. Water content determined by thermogravimetric analysis: H₂O 9.42% (calculated); 9.63% (found). The powder X-ray diffractometry of (I) (Cu Kα) displayed a pattern consistent with that simulated in TEXSAN (Molecular Structure Corporation, 2001) based on the crystal structure of (I). The temperature dependence of magnetic susceptibility of (I) revealed that the effective magnetic moment gradually decreases upon cooling (µ_eff = 2.4 µ_B at 300 K; µ_eff = 1.8 µ_B at 2 K), which result is indicative of a weak antiferromagnetic character of the material (J values remain undetermined). The X-ray diffraction data were collected using a single-crystal that was cut from a well formed needle with a length of a few millimeters.

S3. Refinement

Atoms Cl1 and O1 were assumed to be disordered at the same site, each with 50% occupancy, where all the positional and displacement parameters were constrained to be equal. All H atoms, except those of the water molecules, were placed in idealized positions (C—H=0.93 Å) and included in the refinement as riding, with U_iso(H) equal to 1.2U_eq(C). The water H atoms were not introduced. The highest peak was 0.45 Å from atom O3, while the deepest hole was 0.54 Å from atom Fe1.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: KENX (Sakai, 2002); software used to prepare material for publication: SHELXL97, TEXSAN, KENX and ORTEP (Johnson, 1976).

Figures

	Fig. 1. The structure of (I) in the asymmetric unit, showing the atom-labelling scheme. Atoms Cl1 and O1 occupy the same site, each with 50% occupancy. Displacement ellipsoids are shown at the 50% probability level. Dashed lines denote hydrogen bonds.
	Fig. 2. A view along the c axis within a layer defined by 0 < z < 1/2, showing a cationic honeycomb sheet consisting of Δ-[Ru^II(bpy)3]^2+ cations and water molecules (O2). Anionic components and water molecules, shown in Fig. 3, have been omitted for clarity. H atoms have also been omitted for clarity.
	Fig. 3. A view along the c axis within a layer defined by −0.15 < z < 0.15, showing the hydrogen-bonding network consisting of [Fe^III(CN)6]^3− and water molecules (O1/O3—O5), leading to the formation of an anionic two-dimensional layer. Dashed lines denote hydrogen bonds. Sites where atoms Cl1 and O1 are disordered are marked with asterisks.
	Fig. 4. The crystal packing of (I), viewed along the b axis. H atoms have been omitted for clarity.
	Fig. 5. A view of the one-dimensional hydrogen-bonding network, given by the alternating stack of [Fe^III(CN)6]^3− and water molecules, giving rise to the interpenetration through the honeycomb layers consisting of the cations. Dashed lines denote hydrogen bonds.

Bis[tris(2,2'-bipyridine-κ²N,N')ruthenium(II)] hexacyanoferrate(III) chloride octahydrate

Crystal data

[Ru(C10H8N2)3]2[Fe(CN)6]Cl·8H2O	F(000) = 3124
Mr = 1530.79	? # Insert any comments here.
Monoclinic, C2/c	Dx = 1.509 Mg m^−3
Hall symbol: -C 2yc	Mo Kα radiation, λ = 0.71073 Å
a = 22.2498 (17) Å	Cell parameters from 4404 reflections
b = 13.6859 (10) Å	θ = 2.0–27.1°
c = 22.1298 (16) Å	µ = 0.76 mm^−1
β = 90.459 (1)°	T = 296 K
V = 6738.5 (9) Å^3	Needle, brown
Z = 4	0.15 × 0.15 × 0.12 mm

Data collection

Bruker SMART APEX CCD-detector diffractometer	7417 independent reflections
Radiation source: fine-focus sealed tube	4798 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 8.366 pixels mm^-1	θmax = 27.1°, θmin = 2.5°
ω scans	h = −28→28
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −14→17
Tmin = 0.785, Tmax = 0.913	l = −28→24
20872 measured reflections

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.133	H-atom parameters constrained
S = 1.15	w = 1/[σ^2(Fo^2) + (0.0284P)^2 + 26.0458P] where P = (Fo^2 + 2Fc^2)/3
7417 reflections	(Δ/σ)max < 0.001
435 parameters	Δρmax = 0.53 e Å^−3
0 restraints	Δρmin = −0.36 e Å^−3

Special details

Experimental. The first 50 frames were rescanned at the end of data collection to evaluate any possible decay phenomenon. Since it was judged to be negligible, no decay correction was applied to the data.

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.

Mean-plane data from final SHELXL refinement run:-

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

0.0026 (0.0000) x + 0.0000 (0.0000) y + 22.1291 (0.0017) z = 16.5981 (0.0013)

* −0.1080 (0.0004) Ru1 * 0.1067 (0.0004) Ru1_$2 * 0.1080 (0.0004) Ru1_$3 * −0.1067 (0.0004) Ru1_$4 * −0.1080 (0.0004) Ru1_$5 * 0.1080 (0.0004) Ru1_$6

Rms deviation of fitted atoms = 0.1076

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	0.334623 (19)	0.02540 (3)	0.74514 (2)	0.03378 (13)
Fe1	0.0000	0.0000	1.0000	0.0299 (3)
Cl1	0.32915 (14)	−0.00723 (19)	0.98742 (15)	0.0856 (9)	0.50
O1	0.32915 (14)	−0.00723 (19)	0.98742 (15)	0.0856 (9)	0.50
O2	0.0000	0.0810 (4)	0.7500	0.0627 (18)
O3	0.1912 (2)	0.2967 (4)	1.0051 (2)	0.0908 (17)
O4	0.2382 (2)	−0.1521 (4)	1.0155 (2)	0.0921 (18)
O5	0.4367 (2)	−0.1353 (4)	1.0037 (3)	0.1003 (18)
N1	0.39792 (18)	−0.0467 (3)	0.69342 (19)	0.0370 (11)
N2	0.34225 (19)	−0.1051 (3)	0.79015 (19)	0.0358 (10)
N3	0.26384 (18)	−0.0249 (3)	0.69305 (18)	0.0356 (10)
N4	0.26218 (19)	0.0748 (3)	0.79408 (18)	0.0351 (10)
N5	0.39634 (18)	0.0960 (3)	0.80044 (19)	0.0374 (11)
N6	0.34359 (19)	0.1561 (3)	0.70100 (19)	0.0362 (11)
N7	0.0887 (3)	0.1727 (4)	0.9927 (2)	0.0613 (15)
N8	0.1090 (3)	−0.1390 (5)	1.0092 (2)	0.0726 (18)
N9	−0.0004 (2)	−0.0166 (4)	0.8606 (2)	0.0539 (13)
C1	0.4205 (2)	−0.0155 (4)	0.6404 (3)	0.0469 (14)
H1	0.4130	0.0483	0.6282	0.056*
C2	0.4547 (3)	−0.0760 (5)	0.6035 (3)	0.0547 (17)
H2	0.4681	−0.0536	0.5663	0.066*
C3	0.4683 (3)	−0.1680 (5)	0.6223 (3)	0.0556 (17)
H3	0.4916	−0.2087	0.5984	0.067*
C4	0.4471 (3)	−0.2003 (4)	0.6772 (3)	0.0523 (16)
H4	0.4565	−0.2628	0.6909	0.063*
C5	0.4113 (2)	−0.1386 (4)	0.7121 (3)	0.0408 (14)
C6	0.3835 (2)	−0.1691 (4)	0.7685 (2)	0.0390 (13)
C7	0.3979 (3)	−0.2544 (4)	0.7988 (3)	0.0499 (16)
H7	0.4260	−0.2970	0.7827	0.060*
C8	0.3705 (3)	−0.2765 (5)	0.8530 (3)	0.0570 (18)
H8	0.3798	−0.3335	0.8739	0.068*
C9	0.3292 (3)	−0.2116 (5)	0.8747 (3)	0.0587 (18)
H9	0.3103	−0.2241	0.9113	0.070*
C10	0.3154 (3)	−0.1287 (4)	0.8432 (3)	0.0495 (16)
H10	0.2864	−0.0867	0.8586	0.059*
C11	0.2670 (3)	−0.0718 (4)	0.6399 (3)	0.0485 (15)
H11	0.3047	−0.0882	0.6252	0.058*
C12	0.2170 (3)	−0.0967 (5)	0.6059 (3)	0.0565 (18)
H12	0.2213	−0.1297	0.5695	0.068*
C13	0.1611 (3)	−0.0727 (4)	0.6262 (3)	0.0514 (16)
H13	0.1269	−0.0870	0.6034	0.062*
C14	0.1568 (2)	−0.0265 (4)	0.6813 (3)	0.0465 (14)
H14	0.1192	−0.0106	0.6966	0.056*
C15	0.2079 (2)	−0.0038 (4)	0.7140 (2)	0.0356 (13)
C16	0.2074 (2)	0.0488 (4)	0.7715 (2)	0.0348 (12)
C17	0.1550 (3)	0.0679 (4)	0.8037 (3)	0.0472 (15)
H17	0.1179	0.0484	0.7882	0.057*
C18	0.1584 (3)	0.1158 (5)	0.8584 (3)	0.0581 (18)
H18	0.1238	0.1287	0.8802	0.070*
C19	0.2130 (3)	0.1439 (5)	0.8798 (3)	0.0599 (18)
H19	0.2161	0.1767	0.9165	0.072*
C20	0.2636 (3)	0.1236 (5)	0.8471 (3)	0.0535 (17)
H20	0.3006	0.1444	0.8621	0.064*
C21	0.4175 (3)	0.0648 (5)	0.8542 (3)	0.0472 (15)
H21	0.4092	0.0012	0.8663	0.057*
C22	0.4511 (3)	0.1236 (5)	0.8918 (3)	0.0514 (16)
H22	0.4642	0.0996	0.9290	0.062*
C23	0.4653 (3)	0.2159 (5)	0.8755 (3)	0.0536 (17)
H23	0.4879	0.2559	0.9010	0.064*
C24	0.4451 (3)	0.2491 (4)	0.8194 (3)	0.0472 (15)
H24	0.4550	0.3117	0.8066	0.057*
C25	0.4106 (2)	0.1895 (4)	0.7828 (2)	0.0376 (13)
C26	0.3843 (2)	0.2204 (4)	0.7253 (2)	0.0370 (13)
C27	0.3985 (3)	0.3064 (4)	0.6969 (3)	0.0484 (15)
H27	0.4258	0.3492	0.7147	0.058*
C28	0.3722 (3)	0.3294 (5)	0.6418 (3)	0.0570 (17)
H28	0.3819	0.3871	0.6220	0.068*
C29	0.3314 (3)	0.2649 (5)	0.6170 (3)	0.0566 (17)
H29	0.3133	0.2779	0.5799	0.068*
C30	0.3179 (3)	0.1818 (4)	0.6480 (3)	0.0489 (15)
H30	0.2891	0.1402	0.6314	0.059*
C31	0.0554 (3)	0.1094 (4)	0.9954 (2)	0.0404 (14)
C32	0.0681 (3)	−0.0878 (4)	1.0061 (2)	0.0437 (14)
C33	0.0000 (2)	−0.0103 (4)	0.9121 (2)	0.0371 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ru1	0.0299 (2)	0.0350 (2)	0.0364 (2)	−0.0021 (2)	−0.00003 (17)	−0.0020 (2)
Fe1	0.0298 (5)	0.0339 (6)	0.0261 (5)	0.0013 (4)	0.0004 (4)	0.0016 (4)
Cl1	0.087 (2)	0.0515 (17)	0.118 (2)	−0.0022 (14)	0.0131 (18)	−0.0088 (15)
O1	0.087 (2)	0.0515 (17)	0.118 (2)	−0.0022 (14)	0.0131 (18)	−0.0088 (15)
O2	0.098 (5)	0.041 (4)	0.049 (4)	0.000	0.013 (4)	0.000
O3	0.087 (4)	0.096 (4)	0.089 (4)	−0.046 (3)	−0.004 (3)	−0.005 (3)
O4	0.059 (3)	0.138 (5)	0.079 (4)	0.017 (3)	0.003 (3)	0.023 (3)
O5	0.080 (4)	0.118 (5)	0.103 (4)	−0.014 (3)	−0.005 (3)	−0.013 (4)
N1	0.031 (2)	0.043 (3)	0.036 (3)	−0.002 (2)	0.002 (2)	0.002 (2)
N2	0.035 (3)	0.038 (3)	0.034 (3)	−0.006 (2)	0.005 (2)	−0.003 (2)
N3	0.034 (2)	0.037 (2)	0.036 (2)	−0.003 (2)	0.0018 (19)	−0.007 (2)
N4	0.036 (3)	0.041 (3)	0.028 (2)	0.002 (2)	−0.002 (2)	−0.008 (2)
N5	0.031 (2)	0.046 (3)	0.035 (3)	0.000 (2)	−0.006 (2)	−0.001 (2)
N6	0.035 (3)	0.038 (3)	0.036 (3)	0.000 (2)	−0.004 (2)	−0.001 (2)
N7	0.067 (4)	0.063 (4)	0.053 (4)	−0.026 (3)	0.002 (3)	−0.003 (3)
N8	0.070 (4)	0.101 (5)	0.047 (3)	0.050 (4)	−0.006 (3)	0.000 (3)
N9	0.064 (3)	0.064 (3)	0.033 (3)	0.003 (3)	0.001 (2)	0.003 (3)
C1	0.042 (3)	0.050 (4)	0.049 (4)	−0.004 (3)	0.005 (3)	0.008 (3)
C2	0.047 (4)	0.081 (5)	0.036 (3)	−0.003 (3)	0.015 (3)	−0.001 (3)
C3	0.057 (4)	0.063 (5)	0.046 (4)	0.006 (3)	0.020 (3)	−0.009 (3)
C4	0.050 (4)	0.047 (4)	0.061 (4)	0.007 (3)	0.009 (3)	−0.008 (3)
C5	0.035 (3)	0.041 (3)	0.046 (4)	−0.001 (3)	0.000 (3)	−0.002 (3)
C6	0.040 (3)	0.043 (3)	0.034 (3)	−0.004 (3)	−0.002 (3)	−0.001 (3)
C7	0.058 (4)	0.043 (4)	0.049 (4)	0.008 (3)	0.000 (3)	−0.003 (3)
C8	0.087 (5)	0.040 (4)	0.044 (4)	−0.003 (4)	−0.001 (4)	0.009 (3)
C9	0.077 (5)	0.061 (5)	0.039 (4)	−0.008 (4)	0.013 (3)	0.009 (3)
C10	0.057 (4)	0.048 (4)	0.044 (4)	−0.008 (3)	0.012 (3)	0.003 (3)
C11	0.042 (3)	0.059 (4)	0.045 (4)	−0.007 (3)	0.008 (3)	−0.017 (3)
C12	0.059 (4)	0.069 (5)	0.041 (4)	−0.015 (4)	0.003 (3)	−0.024 (3)
C13	0.047 (4)	0.059 (4)	0.048 (4)	−0.009 (3)	−0.005 (3)	−0.009 (3)
C14	0.034 (3)	0.058 (4)	0.048 (4)	−0.002 (3)	0.002 (3)	−0.006 (3)
C15	0.034 (3)	0.033 (3)	0.040 (3)	0.000 (2)	−0.001 (2)	−0.001 (2)
C16	0.034 (3)	0.035 (3)	0.036 (3)	0.001 (2)	−0.002 (2)	−0.001 (2)
C17	0.039 (3)	0.058 (4)	0.045 (4)	0.002 (3)	0.000 (3)	−0.005 (3)
C18	0.051 (4)	0.076 (5)	0.048 (4)	0.014 (4)	0.011 (3)	−0.017 (3)
C19	0.065 (5)	0.071 (5)	0.043 (4)	0.014 (4)	0.007 (3)	−0.026 (3)
C20	0.044 (4)	0.067 (4)	0.049 (4)	0.005 (3)	−0.009 (3)	−0.018 (3)
C21	0.047 (4)	0.053 (4)	0.042 (4)	−0.005 (3)	−0.006 (3)	0.003 (3)
C22	0.047 (4)	0.072 (5)	0.035 (3)	0.001 (3)	−0.009 (3)	−0.008 (3)
C23	0.045 (4)	0.061 (4)	0.055 (4)	−0.007 (3)	−0.006 (3)	−0.020 (3)
C24	0.046 (4)	0.043 (4)	0.053 (4)	−0.009 (3)	−0.007 (3)	−0.003 (3)
C25	0.030 (3)	0.041 (3)	0.043 (3)	0.001 (2)	0.003 (3)	−0.001 (3)
C26	0.032 (3)	0.036 (3)	0.043 (3)	−0.001 (2)	0.001 (3)	−0.005 (3)
C27	0.050 (4)	0.045 (4)	0.050 (4)	−0.009 (3)	−0.002 (3)	0.001 (3)
C28	0.065 (5)	0.047 (4)	0.058 (4)	−0.007 (3)	0.004 (4)	0.011 (3)
C29	0.063 (4)	0.060 (4)	0.047 (4)	0.001 (4)	−0.009 (3)	0.021 (3)
C30	0.044 (4)	0.053 (4)	0.050 (4)	−0.009 (3)	−0.011 (3)	0.005 (3)
C31	0.047 (4)	0.052 (4)	0.022 (3)	−0.004 (3)	0.004 (3)	0.000 (3)
C32	0.042 (3)	0.055 (4)	0.034 (3)	0.007 (3)	0.000 (3)	0.000 (3)
C33	0.040 (3)	0.041 (3)	0.030 (3)	0.000 (2)	0.000 (2)	0.001 (2)

Geometric parameters (Å, º)

Ru1—N6	2.049 (4)	C15—C16	1.463 (7)
Ru1—N2	2.051 (4)	C16—C17	1.396 (7)
Ru1—N3	2.062 (4)	C17—C18	1.378 (8)
Ru1—N4	2.063 (4)	C18—C19	1.355 (8)
Ru1—N5	2.071 (4)	C19—C20	1.373 (8)
Ru1—N1	2.072 (4)	C21—C22	1.375 (8)
Fe1—C32	1.937 (6)	C22—C23	1.352 (8)
Fe1—C31	1.942 (6)	C23—C24	1.393 (8)
Fe1—C33	1.951 (5)	C24—C25	1.379 (7)
Ru1—Ru1^i	7.3606 (10)	C25—C26	1.459 (7)
Ru1—Ru1^ii	7.8145 (6)	C26—C27	1.372 (7)
N1—C1	1.349 (7)	C27—C28	1.384 (8)
N1—C5	1.356 (7)	C28—C29	1.378 (8)
N2—C6	1.359 (7)	C29—C30	1.361 (8)
N2—C10	1.361 (7)	C1—H1	0.9300
N3—C11	1.343 (6)	C2—H2	0.9300
N3—C15	1.361 (6)	C3—H3	0.9300
N4—C20	1.350 (7)	C4—H4	0.9300
N4—C16	1.361 (6)	C7—H7	0.9300
N5—C21	1.346 (7)	C8—H8	0.9300
N5—C25	1.375 (7)	C9—H9	0.9300
N6—C30	1.349 (7)	C10—H10	0.9300
N6—C26	1.371 (6)	C11—H11	0.9300
N7—C31	1.142 (7)	C12—H12	0.9300
N8—C32	1.151 (7)	C13—H13	0.9300
N9—C33	1.143 (6)	C14—H14	0.9300
C1—C2	1.393 (8)	C17—H17	0.9300
C2—C3	1.358 (8)	C18—H18	0.9300
C3—C4	1.380 (8)	C19—H19	0.9300
C4—C5	1.398 (8)	C20—H20	0.9300
C5—C6	1.457 (7)	C21—H21	0.9300
C6—C7	1.382 (8)	C22—H22	0.9300
C7—C8	1.383 (8)	C23—H23	0.9300
C8—C9	1.368 (9)	C24—H24	0.9300
C9—C10	1.366 (8)	C27—H27	0.9300
C11—C12	1.381 (8)	C28—H28	0.9300
C12—C13	1.366 (8)	C29—H29	0.9300
C13—C14	1.378 (8)	C30—H30	0.9300
C14—C15	1.379 (7)
Cl1···O4	2.904 (6)	N7···O3	2.855 (7)
Cl1···O5	2.986 (7)	N8···O4	2.881 (8)
O1···O4	2.904 (6)	O3···O3^iii	2.922 (12)
O1···O5	2.986 (7)	O5···N8^iv	3.265 (9)
N9···O2	2.788 (5)
N6—Ru1—N2	169.66 (17)	C12—C11—H11	118.4
N2—Ru1—N1	78.43 (17)	C13—C12—C11	119.6 (6)
N3—Ru1—N4	78.84 (16)	C13—C12—H12	120.2
N6—Ru1—N5	78.90 (17)	C11—C12—H12	120.2
N6—Ru1—N3	95.84 (17)	C12—C13—C14	118.1 (6)
N2—Ru1—N3	92.34 (17)	C12—C13—H13	121.0
N6—Ru1—N4	92.49 (17)	C14—C13—H13	121.0
N2—Ru1—N4	95.31 (17)	C13—C14—C15	120.3 (5)
N2—Ru1—N5	93.88 (17)	C13—C14—H14	119.8
N3—Ru1—N5	170.24 (17)	C15—C14—H14	119.8
N4—Ru1—N5	93.08 (16)	N3—C15—C14	121.8 (5)
N6—Ru1—N1	94.79 (17)	N3—C15—C16	114.5 (4)
N3—Ru1—N1	92.97 (16)	C14—C15—C16	123.7 (5)
N4—Ru1—N1	169.57 (17)	N4—C16—C17	120.9 (5)
N5—Ru1—N1	95.65 (17)	N4—C16—C15	115.7 (4)
C32—Fe1—C33	91.1 (2)	C17—C16—C15	123.3 (5)
C32—Fe1—C31	89.2 (2)	C18—C17—C16	119.7 (6)
C31—Fe1—C33	89.9 (2)	C18—C17—H17	120.2
C32—Fe1—C31^v	90.8 (2)	C16—C17—H17	120.2
C32—Fe1—C33^v	88.9 (2)	C19—C18—C17	119.1 (6)
C31—Fe1—C33^v	90.1 (2)	C19—C18—H18	120.5
Ru1^i—Ru1—Ru1^ii	118.757 (6)	C17—C18—H18	120.5
Ru1^vi—Ru1—Ru1^ii	122.251 (12)	C18—C19—C20	119.6 (6)
C1—N1—C5	118.5 (5)	C18—C19—H19	120.2
C6—N2—C10	117.0 (5)	C20—C19—H19	120.2
C11—N3—C15	117.0 (5)	N4—C20—C19	123.0 (6)
C20—N4—C16	117.6 (5)	N4—C20—H20	118.5
C21—N5—C25	117.8 (5)	C19—C20—H20	118.5
C30—N6—C26	116.7 (5)	N5—C21—C22	122.3 (6)
N1—C1—C2	122.0 (6)	N5—C21—H21	118.8
N1—C1—H1	119.0	C22—C21—H21	118.8
C2—C1—H1	119.0	C23—C22—C21	120.8 (6)
C3—C2—C1	119.5 (6)	C23—C22—H22	119.6
C3—C2—H2	120.3	C21—C22—H22	119.6
C1—C2—H2	120.3	C22—C23—C24	118.0 (6)
C2—C3—C4	119.3 (6)	C22—C23—H23	121.0
C2—C3—H3	120.3	C24—C23—H23	121.0
C4—C3—H3	120.3	C25—C24—C23	120.3 (6)
C3—C4—C5	119.5 (6)	C25—C24—H24	119.9
C3—C4—H4	120.2	C23—C24—H24	119.9
C5—C4—H4	120.2	N5—C25—C24	120.8 (5)
N1—C5—C4	121.0 (5)	N5—C25—C26	115.2 (5)
N1—C5—C6	115.7 (5)	C24—C25—C26	123.9 (5)
C4—C5—C6	123.2 (5)	N6—C26—C27	121.6 (5)
N2—C6—C7	121.8 (5)	N6—C26—C25	114.5 (5)
N2—C6—C5	114.1 (5)	C27—C26—C25	123.8 (5)
C7—C6—C5	124.0 (5)	C26—C27—C28	120.2 (6)
C6—C7—C8	120.3 (6)	C26—C27—H27	119.9
C6—C7—H7	119.8	C28—C27—H27	119.9
C8—C7—H7	119.9	C29—C28—C27	118.5 (6)
C9—C8—C7	117.7 (6)	C29—C28—H28	120.8
C9—C8—H8	121.2	C27—C28—H28	120.8
C7—C8—H8	121.2	C30—C29—C28	118.8 (6)
C10—C9—C8	120.6 (6)	C30—C29—H29	120.6
C10—C9—H9	119.7	C28—C29—H29	120.6
C8—C9—H9	119.7	N6—C30—C29	124.2 (6)
N2—C10—C9	122.6 (6)	N6—C30—H30	117.9
N2—C10—H10	118.7	C29—C30—H30	117.9
C9—C10—H10	118.7	N7—C31—Fe1	179.0 (6)
N3—C11—C12	123.2 (5)	N8—C32—Fe1	179.0 (6)
N3—C11—H11	118.4	N9—C33—Fe1	179.5 (6)
C5—N1—C1—C2	2.8 (8)	N3—C15—C16—N4	4.1 (7)
N1—C1—C2—C3	−3.0 (9)	C14—C15—C16—N4	−172.8 (5)
C1—C2—C3—C4	1.0 (10)	N3—C15—C16—C17	−172.9 (5)
C2—C3—C4—C5	1.0 (10)	C14—C15—C16—C17	10.2 (8)
C1—N1—C5—C4	−0.7 (8)	N4—C16—C17—C18	1.5 (9)
C1—N1—C5—C6	−177.6 (5)	C15—C16—C17—C18	178.4 (5)
C3—C4—C5—N1	−1.2 (9)	C16—C17—C18—C19	0.2 (10)
C3—C4—C5—C6	175.5 (6)	C17—C18—C19—C20	−0.5 (10)
C10—N2—C6—C7	−0.2 (8)	C16—N4—C20—C19	2.9 (9)
C10—N2—C6—C5	−179.0 (5)	C18—C19—C20—N4	−1.1 (10)
N1—C5—C6—N2	7.8 (7)	C25—N5—C21—C22	1.6 (8)
C4—C5—C6—N2	−169.1 (5)	N5—C21—C22—C23	−1.3 (9)
N1—C5—C6—C7	−171.0 (5)	C21—C22—C23—C24	−0.3 (9)
C4—C5—C6—C7	12.1 (9)	C22—C23—C24—C25	1.5 (9)
N2—C6—C7—C8	−0.5 (9)	C21—N5—C25—C24	−0.3 (8)
C5—C6—C7—C8	178.2 (6)	C21—N5—C25—C26	−177.7 (5)
C6—C7—C8—C9	0.2 (9)	C23—C24—C25—N5	−1.2 (8)
C7—C8—C9—C10	0.7 (10)	C23—C24—C25—C26	175.9 (5)
C6—N2—C10—C9	1.2 (8)	C30—N6—C26—C27	−0.4 (8)
C8—C9—C10—N2	−1.5 (10)	C30—N6—C26—C25	179.7 (5)
C15—N3—C11—C12	1.4 (9)	N5—C25—C26—N6	7.6 (7)
N3—C11—C12—C13	0.6 (10)	C24—C25—C26—N6	−169.7 (5)
C11—C12—C13—C14	−2.0 (10)	N5—C25—C26—C27	−172.3 (5)
C12—C13—C14—C15	1.4 (9)	C24—C25—C26—C27	10.4 (9)
C11—N3—C15—C14	−2.0 (8)	N6—C26—C27—C28	−1.0 (9)
C11—N3—C15—C16	−179.0 (5)	C25—C26—C27—C28	178.9 (5)
C13—C14—C15—N3	0.6 (9)	C26—C27—C28—C29	0.8 (9)
C13—C14—C15—C16	177.3 (5)	C27—C28—C29—C30	0.8 (10)
C20—N4—C16—C17	−3.0 (8)	C26—N6—C30—C29	2.1 (9)
C20—N4—C16—C15	179.9 (5)	C28—C29—C30—N6	−2.4 (10)

Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+1/2, −y+1/2, −z+2; (iv) −x+1/2, −y−1/2, −z+2; (v) −x, −y, −z+2; (vi) −x+1/2, y−1/2, −z+3/2.