Tetra­kis[2-(2-pyridyl)pyridinium] tetra-[mu]₃-iodo-hexa-[mu]₂-iodo-dodeca­iodo­hexa­bismuthate and bis­[tris­(2,2'-bipyridine)ruthenium(II)] di-[mu]₄-iodo-octa-[mu]₂-iodo-dodeca­iodo­hexa­bismuthate

Crystals of the title compounds were grown solvothermally in an ethanol-water solvent mixture using ruthenium triiodide, 2,2'-bipyridine and bismuth triiodide as starting materials. Tetra­kis[2-(2-pyridyl)pyridinium] tetra-[mu]₃-iodo-hexa-[mu]₂-iodo-dodeca­iodo­hexa­bismuthate, (C₁₀H₉N₂)₄[Bi₆I₂₂], crystallizes in the triclinic space group P and is the major reaction product. The asymmetric unit of this compound consists of half a centrosymmetric [Bi₆I₂₂]^4- anion and two independent 2,2'-bipyridinium cations. The minor product of the reaction is bis­[tris­(2,2'-bipyridine)ruthenium(II)] di-[mu]₄-iodo-octa-[mu]₂-iodo-dodeca­iodo­hexa­bismuthate, [Ru(C₁₀H₈N₂)₃]₂[Bi₆I₂₂], which also crystallizes in the triclinic space group P. For this compound, the asymmetric unit consists of one full [Ru(2,2'-bipyridine)₃]²⁺ cation and half a centrosymmetric [Bi₆I₂₂]^4- anion. Although both compounds contain a centrosymmetric [Bi₆I₂₂]^4- anion, the polyhedral arrangement of the distorted BiI₆ octa­hedra in the two compounds is quite different, and the anion of the latter compound has not previously been observed in iodo­bismuthate chemistry.

S1. Comment

The chemistry of main group halometallate materials has been of interest to chemists and materials scientists for some time, due to their promising physical characteristics and their interesting structural diversity. With respect to the physical properties, behaviors such as semiconductivity, luminescence and second-order non-linear optical activity have been observed in this family of materials (Papavassiliou et al., 1995; Zhu et al., 2003; Mitzi & Brock, 2001; Mousdis et al., 1998). The main group halometallate materials display extensive structural diversity, as the anionic inorganic component ranges from discrete clusters (zero-dimensional) to polymeric structures (one-, two- or three-dimensional) depending on the main group metal and on the specific synthetic conditions employed. To date, main group halometallate materials based on Cu^I (Yu et al., 2003), Sn^II (Xu & Mitzi, 2003), Sb^III (Mousdis et al., 1998), Te^IV (Ryan & Xu, 2004), Pb^II (Zhu et al., 2003) and Bi^III (Mousdis et al., 1998; Eickmeier et al., 1999; Lindsjo et al., 2005) have been synthesized and structurally characterized.

We have been interested in the synthesis of new main group halometallate materials containing Bi^III and have been successful in the synthesis of many new iodobismuthate(III) materials having either organic or inorganic cations for charge balance (Goforth et al., 2004; Goforth, Gardinier et al., 2005; Goforth, Peterson et al., 2005). Many halobismuthate compounds have been synthesized by us and others, and most of these compounds contain either discrete anions (of varying sizes) or one-dimensional polymeric anions. In either case, the anion is generally composed of connected BiI₆ polyhedra, which are corner-, edge- or face-sharing. The number of connected polyhedra, and the mode of connectivity and the spatial arrangement of these polyhedra, may vary within a given metal halide system, e.g. iodobismuthates, such that one can envision a large number of possible halometallate anion structures. In fact, certain synthetic conditions, such as cation size and geometry, solvent system and reagent stoichiometry, may be adjusted to affect the identity of the iodobismuthate anion (Eickmeier et al., 1999; Goforth, Peterson et al., 2005; Krautscheid, 1994).

While the vast majority of iodobismuthate materials known to date have contained an organic cation for charge balance, our group has recently demonstrated that a d-metal coordination cation is a viable charge-balancing species for iodobismuthate anions and that the use of such cations may lead to new iodobismuthate anions (Goforth, Gardinier et al., 2005; Goforth, 2005). Here, we report the synthesis and single-crystal X-ray structures of two co-crystallizing iodobismuthate compounds, one of which has a coordination cation for charge balance while the other has an organic counter-cation. Both compounds contain [Bi₆I₂₂]^4- anions. However, the polyhedral arrangements of the six BiI₆ octahedra in the two compounds differ.

The title compounds, [H(2,2'-bipy)]₄[Bi₆I₂₂] {[H(2,2'-bipy)]⁺ is protonated 2,2'-bipyridine}, (I), and [Ru(2,2'-bipy)₃]₂[Bi₆I₂₂], (II), were synthesized solvothermally from RuI₃, 2,2'-bipyridyl and BiI₃ in aqueous ethanol (50% v/v) using a 1:3:3 molar ratio. Crystals of (I) were isolated as the major phase, and crystals of both (I) and (II) were characterized by single-crystal X-ray diffraction. The structure of (II) reveals that the compound contains a novel [Bi₆I₂₂]^4- anion that has not previously been reported in iodobismuthate chemistry, and this anion is discussed in detail following the structure description of (I). Relevant bond distances and angles for the two compounds are presented in Tables 1 and 2. [Please clarify, as no values are flagged in the CIF for publication. Do you wish to add tables?]

Compund (I) crystallizes in the triclinic space group P1 and contains two crystallographically independent 2,2'-bipyridinium cations and a [Bi₆I₂₂]^4- iodobismuthate anion in its asymmetric unit. For the structure solution, the 2,2'-bipyridinium cations were refined isotropically, due to disorder. Anisotropic refinement of the cations resulted in unreasonable ellipsoids for these atoms, most probably due to unresolved disorder in the form of the N atoms oriented in the opposite direction. N-atom positions were assigned based on the magnitude of the U_iso parameter, but are uncertain due to the disorder and probably represent only the major orientation. The position of the H atoms was not calculated or located. However, the H atom is necessary to maintain charge neutrality for the compound. The atoms of the [Bi₆I₂₂]^4- anion were refined anisotropically. The centrosymmetric anion consists of six BiI₆ octahedra, which are connected such that two sets of three trans edge-sharing octahedra share five cis edges (Fig. 1). The arrangement of the six BiI₆ octahedra in (I) is a known arrangement of the [Bi₆I₂₂]^4- anion. For example, the [Bi₆I₂₂]^4- anions of [(THF)₆Na]₄[Bi₆I₂₂] (THF is tetrahydrofuran; Krautscheid, 1994), [EtMe₂PhN]₄[Bi₆I₂₂] (Eickmeier et al., 1999) and [H₂TMDP]₂[Bi₆I₂₂] {H₂TMDP]²⁺ is 1,3-bis(4-piperidinium)propane; Goforth, Peterson et al., 2005} have the same polyhedral connectivity as the anion of (I), and the bond distances and angles of the anion of (I) are comparable with those determined for these compounds. The average terminal Bi—I distance in (I) is 2.8793 Å, the average Bi—µ₂-I distance is 3.1491 Å and the average Bi—µ₃-I distance is 3.3177 Å. The cis I—Bi—I angles in (I) range from 82.350 (13) to 100.270 (17)° and the trans I—Bi—I angles range from 163.460 (16) to 176.741 (16)°.

When the structure of compound (I) is viewed along [001] (Fig. 2), stacks of [H2,2'-bipy]⁺ cations and rows of [Bi₆I₂₂]^4- anions are observed. Weak I···I bonding interactions between [Bi₆I₂₂]^4- anions of neighboring rows are also observed [I3···I9ⁱ = 3.739 (1) Å and I8···I8ⁱⁱ = 3.732 (1) Å; symmetry codes: (i) x - 1, y + 1, z; (ii) -x, 1 - y, 1 - z; van der Waals radius of I = 1.98 Å, I···I = 3.96 Å; Bondi, 1964], and when these interactions are taken into account, the structure may be viewed as an array of weakly bonded inorganic chains, with organic cations situated above and below the chains.

Compound (II) crystallizes in the triclinic space group P1 and contains the well known tris-chelate cation [Ru(2,2'-bipy)₃]²⁺ and a novel arrangement of the [Bi₆I₂₂]^4- anion (Fig. 3). The bond distances and angles of the cation are normal [2.044 (6)–2.067 (6) Å; Biner et al., 1992]. Due to the crystallographic inversion symmetry in the crystal, both the Λ- and Δ- enantiomers of the cation are present in the structure.

The centrosymmetric [Bi₆I₂₂]^4- anion of (II) consists of a central Bi₄I₁₆ core (containing atoms Bi1 and Bi2), with two BiI₃ units (containing atom Bi3) connected to the core by three relatively long Bi—I bonds [3.3268 (6), 3.4311 (6) and 3.5484 (5) Å; Fig. 3). Alternatively, the BiI₃ units can be considered as part of very distorted Bi(3)I₆ octahedra, each of which shares two cis edges with the Bi₄I₁₆ cluster core. The bond lengths and angles of the Bi₄I₁₆ core are within the normal ranges and are comparable with those found in previously reported [Bi₄I₁₆]^4- anions (Goforth, Gardinier et al., 2005). The average terminal Bi—I distance is 2.897 Å and the average Bi—µ₂-I distance is 3.166 Å.

Considering the pendant BiI₃ units of the anion, an unusual bonding feature of the anion of compound (II) is the presence of an essentially µ₄-bridging iodide ligand. However, the average Bi—µ₄-I distance of 3.397 Å is within the reported ranges for Bi—µ₃-I distances in related compounds (Feldmann, 2003), further supporting the description of the anion as a Bi₄I₁₆ core with two pendant BiI₃ groups. In fact, many of the larger known discrete iodobismuthate anions may be considered to be based on Bi₄I₁₆ cores, either joined with one or more pendant BiI₃ units {as in [Bi₅I₁₉]^4- (Krautscheid, 1994), or the typical arrangement of [Bi₆I₂₂]^4- (Eickmeier et al., 1999; Pohl et al., 1994; Goforth, Peterson et al., 2005; Krautscheid et al., 1994)}, or connected to another such core through a single edge {as in [Bi₈I₃₀]^6- (Feldmann, 2003)}. The cis I—Bi—I angles of the anion of (II) range from 78.39 (1) to 103.69 (2)° and the trans I—Bi—I angles from 159.65 (2) to 177.02 (2)°, where the largest deviations from the ideal octahedral angles are observed in the Bi3 polyhedron.

A [100] view of the crystal packing in compound (II) is shown in Fig. 4, where it can be seen that the discrete anions are arranged in layers which are interleaved by layers of the cations. As in compound (I), the discrete anions in (II) are close enough to one another in space that certain I atoms of neighboring anions are closer than the sum of their van der Waals radii (see above), thus leading to the formation of very weak I···I bonding interactions [I10···I3ⁱ = 3.834 (1) Å and I11···I7ⁱⁱ = 3.957 (1) Å; symmetry codes: (i) 1 - x, 1 - y, -z; (ii) -x, 1 - y, z - 1]. When the I···I interactions are taken into consideration, the anionic component of the structure may be viewed as an array of weakly bonded two-dimensional sheets, which lie in the ac plane (Fig. 5). These pseudo-two-dimenional sheets may have an interesting consequence in terms of dimensionality-dependent optical properties, i.e. quantum confinement behavior, in that they serve to extend the dimensionality of the discrete anionic component (Ryan & Xu, 2004). Experiments aimed at isolating the phase-pure compound for optical measurements are in progress.

While it is reasonable to believe that compounds (I) and (II) contain anions of different polyhedral arrangements because they crystallize with different cations, it is also of interest to note that we have prepared another iodobismuthate compound, [Ru(2,2'-bipy)₃]₂[Bi₄I₁₆] (Goforth, Gardinier et al., 2005), which contains the same [Ru(2,2'-bipy)₃]²⁺ cation as compound (II). However, [Ru(2,2'-bipy)₃]₂[Bi₄I₁₆] was synthesized from [Ru(2,2'-bipy)₃]I₂ tetrahydrate and BiI₃, rather than from RuI₃, BiI₃, and 2,2'-bipyridine. Thus, it may be concluded that several reaction conditions, including choice of starting materials and nature of the counter-cation, simultaneously affect the identity of the iodobismuthate anion formed. The anion of [Ru(2,2'-bipy)₃]₂[Bi₄I₁₆] is the same as the Bi₄I₁₆ core in the [Bi₆I₂₂]^4- anion of compound (II).

S2. Experimental

BiI₃ (175 mg, 0.3 mmol; Alfa Aesar, 99.999%), 2,2'-bipyridine (54 mg, 0.3 mmol; Acros, 99+%) and RuI₃ (48 mg, 0.1 mmol; Aldrich, reagent grade) were placed in a 15 ml glass pressure vessel (Ace glass) and covered with aqueous ethanol (10 ml, 50% v/v). The reaction vessel was subsequently sealed with a threaded Teflon plug (with a back seal FETFE O-ring; Ace glass) and heated at rate of 0.1 K min^-1 to 433 K, where the temperature was held for 5 d. At the end of this period, the vessel was cooled at a rate of 0.1 K min^-1 to 353 K and this temperature was maintained for 6 h, afer which the reaction vessel was cooled to room temperature at a rate of 0.1 K min^-1. Red–orange blocks of (I), red–orange prisms of (II) and red–orange polycrystalline material were isolated from the reaction. Suitable red–orange crystals were selected for the structure determinations of (I) and (II).

S3. Refinement

For compound (I), all atoms of the anion were refined with anisotropic displacement parameters. H atoms bonded to C atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). No N-bound H atoms were located or calculated. The highest residual electron-density map peak is located 0.57 Å from C13 and the lowest hole is located 2.88 Å from I5.

For compound (II), all non-H atoms of the structure were refined with anisotropic displacement parameters. H atoms were placed in geometrically idealized positions and included as riding atoms, with C—H = 0.95 Å and U_iso(H) = 1.2U_eq(C). The highest residual electron-density map peak is located 0.93 Å from Bi3 and the lowest hole is located 0.54 Å from I4.

Computing details

For both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A plot of the [Bi6I22]^4- anion of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The cation was refined isotropically and is not shown.
	Fig. 2. An [001] view of the crystal packing in (I). I···I interactions less than or equal to the sum of the van der Waals radii are indicated as two-tone bonds. Bi atoms are shown as light-grey spheres, I atoms as large black spheres, C atoms as dark-grey spheres and N atoms as small black spheres. H atoms are not shown.
	Fig. 3. A plot of the components of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. In order to assist the distinction of the Bi4I16 cluster core from the pendant BiI3 units, two of the three long bonds are drawn as dashed lines. The third, Bi3—I1, is drawn as a solid line.
	Fig. 4. A [100] view of the crystal packing in (II). Bi polyhedra are shown in grey, I atoms as small black spheres and [Ru(2,2'-bipy)3]^2+ cations as large black spheres.
	Fig. 5. An [010] view of a single pseudo-two-dimensional anionic layer in (II). I···I interactions less than or equal to the sum of the van der Waals radii are indicated as two-tone bonds. Bi atoms are shown as light-grey spheres and I atoms as black spheres.

(I) Tetrakis[2-(2-pyridyl)pyridinium] tetra-µ₃-iodo-hexa-µ₂-iodo-dodecaiodohexabismuthate

Crystal data

(C10H9N2)4[Bi6I22]	Z = 1
Mr = 4674.45	F(000) = 1996
TriclinicP1	Dx = 3.748 Mg m^−3 Dm = 0 Mg m^−3 Dm measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.3334 (6) Å	Cell parameters from 8486 reflections
b = 12.9913 (7) Å	θ = 2.3–27.7°
c = 15.7999 (9) Å	µ = 20.93 mm^−1
α = 78.778 (1)°	T = 150 K
β = 79.520 (1)°	Block, orange
γ = 66.023 (1)°	0.12 × 0.11 × 0.08 mm
V = 2071.2 (2) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	9709 independent reflections
Radiation source: fine-focus sealed tube	8250 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.039
ω scans	θmax = 27.7°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −14→14
Tmin = 0.501, Tmax = 1.000	k = −17→16
27864 measured reflections	l = −20→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0369P)^2 + 1.7243P] where P = (Fo^2 + 2Fc^2)/3
9709 reflections	(Δ/σ)max = 0.001
223 parameters	Δρmax = 1.83 e Å^−3
0 restraints	Δρmin = −2.90 e Å^−3

Special details

Experimental. Crystal red at room temperature, orange at 150 K.

Geometry. I3 I9 3.7390 (7) 1_465 ? I8 I8 3.7317 (10) 2_566 ?

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. Ellipsoids of 2,2'-bipy atoms strongly elongated, indicating disorder of these species. Disorder unresolved and these atoms refined isotropically. Due to the disorder the assignment of N atom positions also uncertain. No N-bound proton located or calculated. Owing to these difficulties, only the general location of the 2,2'-bipy groups is reliable.

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
Bi1	0.19109 (3)	0.17040 (2)	0.190490 (18)	0.01939 (7)
Bi2	0.62188 (3)	−0.06638 (2)	0.244952 (17)	0.01877 (7)
Bi3	0.28086 (2)	0.11827 (2)	0.473134 (17)	0.01844 (7)
I1	0.28566 (6)	0.25786 (5)	0.02151 (3)	0.03366 (13)
I2	0.01213 (5)	0.09132 (4)	0.14214 (3)	0.02739 (12)
I3	0.00622 (5)	0.39492 (4)	0.22357 (4)	0.03144 (13)
I4	0.73211 (5)	0.01627 (4)	0.08179 (3)	0.02918 (12)
I5	0.41292 (5)	−0.08997 (4)	0.17011 (4)	0.02722 (12)
I6	0.41409 (4)	0.19590 (4)	0.28983 (3)	0.02060 (10)
I7	0.09823 (5)	0.06735 (4)	0.39344 (3)	0.02522 (11)
I8	0.10872 (5)	0.34867 (4)	0.49082 (4)	0.03088 (12)
I9	0.79429 (5)	−0.30062 (4)	0.24246 (3)	0.02700 (12)
I10	0.49434 (4)	−0.14591 (4)	0.44488 (3)	0.02090 (10)
I11	0.18747 (5)	0.02127 (4)	0.64927 (3)	0.02305 (11)
C1	0.1220 (12)	0.5950 (10)	0.0593 (8)	0.068 (3)*
H1	0.0780	0.5523	0.0464	0.082*
C2	0.0639 (11)	0.7007 (9)	0.0590 (7)	0.057 (3)*
H2	−0.0238	0.7356	0.0465	0.069*
C3	0.1188 (10)	0.7637 (9)	0.0750 (7)	0.051 (3)*
H3	0.0712	0.8431	0.0748	0.061*
C4	0.2607 (10)	0.7101 (9)	0.0942 (7)	0.051 (3)*
H4	0.3053	0.7537	0.1047	0.061*
C5	0.3173 (8)	0.5967 (7)	0.0952 (5)	0.0280 (17)*
C6	0.4523 (8)	0.5254 (7)	0.1134 (5)	0.0279 (17)*
C7	0.5290 (8)	0.5714 (7)	0.1336 (5)	0.0287 (17)*
H7	0.4979	0.6510	0.1347	0.034*
C8	0.6522 (8)	0.5024 (7)	0.1526 (6)	0.0335 (19)*
H8	0.7081	0.5331	0.1668	0.040*
C9	0.6937 (9)	0.3858 (8)	0.1508 (6)	0.038 (2)*
H9	0.7781	0.3354	0.1647	0.045*
C10	0.6111 (9)	0.3459 (8)	0.1287 (6)	0.039 (2)*
H10	0.6405	0.2667	0.1264	0.047*
C11	0.7215 (12)	0.4664 (10)	0.4173 (8)	0.064 (3)*
H11	0.7782	0.4956	0.4323	0.076*
C12	0.7590 (14)	0.3534 (12)	0.4160 (9)	0.083 (4)*
H12	0.8434	0.3035	0.4301	0.100*
C13	0.6861 (15)	0.3128 (14)	0.3969 (10)	0.092 (5)*
H13	0.7167	0.2329	0.3974	0.110*
C14	0.5621 (10)	0.3803 (8)	0.3748 (7)	0.046 (2)*
H14	0.5094	0.3471	0.3596	0.055*
C15	0.5180 (8)	0.4915 (7)	0.3753 (6)	0.0349 (19)*
C16	0.3853 (8)	0.5605 (7)	0.3534 (6)	0.035 (2)*
C17	0.3095 (8)	0.5126 (7)	0.3360 (5)	0.0275 (17)*
H17	0.3416	0.4326	0.3371	0.033*
C18	0.1876 (10)	0.5778 (9)	0.3168 (7)	0.047 (2)*
H18	0.1353	0.5421	0.3046	0.057*
C19	0.1387 (11)	0.6885 (9)	0.3144 (7)	0.057 (3)*
H19	0.0522	0.7321	0.3013	0.068*
C20	0.2115 (12)	0.7386 (11)	0.3304 (8)	0.065 (3)*
H20	0.1751	0.8190	0.3282	0.078*
N1	0.2474 (7)	0.5410 (6)	0.0781 (5)	0.0417 (18)*
N2	0.4892 (7)	0.4133 (6)	0.1099 (5)	0.0403 (18)*
N3	0.5952 (8)	0.5402 (7)	0.3956 (5)	0.048 (2)*
N4	0.3409 (10)	0.6788 (9)	0.3508 (7)	0.069 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.01891 (14)	0.01941 (14)	0.01990 (14)	−0.00701 (11)	−0.00221 (11)	−0.00359 (11)
Bi2	0.01805 (14)	0.01862 (14)	0.01875 (14)	−0.00573 (11)	−0.00083 (10)	−0.00465 (10)
Bi3	0.01800 (14)	0.01872 (14)	0.01782 (14)	−0.00593 (11)	−0.00155 (10)	−0.00371 (10)
I1	0.0460 (3)	0.0380 (3)	0.0234 (3)	−0.0261 (3)	0.0051 (2)	−0.0050 (2)
I2	0.0282 (3)	0.0342 (3)	0.0263 (3)	−0.0180 (2)	−0.0037 (2)	−0.0047 (2)
I3	0.0276 (3)	0.0222 (3)	0.0388 (3)	−0.0032 (2)	−0.0012 (2)	−0.0078 (2)
I4	0.0370 (3)	0.0328 (3)	0.0222 (3)	−0.0202 (2)	0.0012 (2)	−0.0027 (2)
I5	0.0215 (2)	0.0238 (2)	0.0384 (3)	−0.0059 (2)	−0.0076 (2)	−0.0115 (2)
I6	0.0205 (2)	0.0206 (2)	0.0211 (2)	−0.00879 (19)	−0.00040 (18)	−0.00368 (18)
I7	0.0260 (3)	0.0334 (3)	0.0218 (2)	−0.0173 (2)	−0.0046 (2)	−0.0014 (2)
I8	0.0332 (3)	0.0207 (2)	0.0298 (3)	−0.0011 (2)	−0.0014 (2)	−0.0058 (2)
I9	0.0275 (3)	0.0199 (2)	0.0279 (3)	−0.0029 (2)	−0.0020 (2)	−0.0055 (2)
I10	0.0205 (2)	0.0212 (2)	0.0223 (2)	−0.00905 (19)	−0.00158 (18)	−0.00452 (19)
I11	0.0245 (2)	0.0289 (3)	0.0193 (2)	−0.0146 (2)	−0.00204 (19)	−0.00182 (19)

Geometric parameters (Å, º)

Bi1—I2	2.8837 (5)	C6—C7	1.347 (11)
Bi1—I1	2.8871 (6)	C6—N2	1.351 (10)
Bi1—I3	2.8981 (6)	C7—C8	1.369 (11)
Bi1—I5	3.3292 (6)	C7—H7	0.9500
Bi1—I6	3.3596 (5)	C8—C9	1.395 (12)
Bi1—I7	3.3806 (6)	C8—H8	0.9500
Bi2—I4	2.8637 (6)	C9—C10	1.362 (12)
Bi2—I9	2.8750 (5)	C9—H9	0.9500
Bi2—I5	2.9750 (6)	C10—N2	1.352 (11)
Bi2—I11^i	3.2449 (5)	C10—H10	0.9500
Bi2—I10	3.3790 (6)	C11—C12	1.356 (17)
Bi2—I6	3.3868 (5)	C11—N3	1.422 (14)
Bi3—I8	2.8679 (6)	C11—H11	0.9500
Bi3—I7	2.9484 (5)	C12—C13	1.248 (18)
Bi3—I11	3.0166 (5)	C12—H12	0.9500
Bi3—I6	3.1929 (5)	C13—C14	1.386 (17)
Bi3—I10^i	3.2285 (5)	C13—H13	0.9500
Bi3—I10	3.3595 (5)	C14—C15	1.325 (13)
I10—Bi3^i	3.2285 (5)	C14—H14	0.9500
I11—Bi2^i	3.2449 (5)	C15—N3	1.377 (11)
C1—C2	1.258 (15)	C15—C16	1.470 (13)
C1—N1	1.365 (13)	C16—C17	1.337 (11)
C1—H1	0.9500	C16—N4	1.404 (13)
C2—C3	1.293 (14)	C17—C18	1.349 (12)
C2—H2	0.9500	C17—H17	0.9500
C3—C4	1.533 (14)	C18—C19	1.310 (14)
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.346 (12)	C19—C20	1.321 (15)
C4—H4	0.9500	C19—H19	0.9500
C5—N1	1.357 (10)	C20—N4	1.417 (14)
C5—C6	1.479 (11)	C20—H20	0.9500
I2—Bi1—I1	100.270 (17)	C3—C2—H2	118.7
I2—Bi1—I3	97.672 (17)	C2—C3—C4	119.9 (10)
I1—Bi1—I3	92.085 (18)	C2—C3—H3	120.0
I2—Bi1—I5	85.835 (15)	C4—C3—H3	120.0
I1—Bi1—I5	91.187 (17)	C5—C4—C3	114.8 (9)
I3—Bi1—I5	174.704 (17)	C5—C4—H4	122.6
I2—Bi1—I6	163.460 (16)	C3—C4—H4	122.6
I1—Bi1—I6	93.196 (16)	C4—C5—N1	118.9 (8)
I3—Bi1—I6	91.341 (15)	C4—C5—C6	125.1 (8)
I5—Bi1—I6	84.316 (13)	N1—C5—C6	116.0 (7)
I2—Bi1—I7	83.376 (15)	C7—C6—N2	124.1 (8)
I1—Bi1—I7	176.143 (17)	C7—C6—C5	120.9 (7)
I3—Bi1—I7	88.652 (16)	N2—C6—C5	115.0 (7)
I5—Bi1—I7	87.811 (15)	C6—C7—C8	119.3 (8)
I6—Bi1—I7	83.000 (13)	C6—C7—H7	120.3
I4—Bi2—I9	95.744 (17)	C8—C7—H7	120.3
I4—Bi2—I5	94.576 (17)	C7—C8—C9	118.5 (8)
I9—Bi2—I5	94.454 (16)	C7—C8—H8	120.7
I4—Bi2—I11^i	91.960 (15)	C9—C8—H8	120.7
I9—Bi2—I11^i	91.532 (15)	C10—C9—C8	118.7 (9)
I5—Bi2—I11^i	170.651 (16)	C10—C9—H9	120.7
I4—Bi2—I10	175.012 (16)	C8—C9—H9	120.7
I9—Bi2—I10	87.448 (15)	N2—C10—C9	123.3 (9)
I5—Bi2—I10	88.983 (15)	N2—C10—H10	118.4
I11^i—Bi2—I10	84.109 (14)	C9—C10—H10	118.4
I4—Bi2—I6	94.168 (15)	C12—C11—N3	118.4 (12)
I9—Bi2—I6	168.984 (16)	C12—C11—H11	120.8
I5—Bi2—I6	89.528 (14)	N3—C11—H11	120.8
I11^i—Bi2—I6	83.327 (14)	C13—C12—C11	122.1 (15)
I10—Bi2—I6	82.350 (13)	C13—C12—H12	118.9
I8—Bi3—I7	94.847 (17)	C11—C12—H12	118.9
I8—Bi3—I11	94.685 (16)	C12—C13—C14	122.3 (15)
I7—Bi3—I11	89.936 (15)	C12—C13—H13	118.9
I8—Bi3—I6	91.418 (16)	C14—C13—H13	118.9
I7—Bi3—I6	93.227 (15)	C15—C14—C13	119.2 (11)
I11—Bi3—I6	172.868 (15)	C15—C14—H14	120.4
I8—Bi3—I10^i	91.706 (16)	C13—C14—H14	120.4
I7—Bi3—I10^i	173.374 (16)	C14—C15—N3	120.6 (9)
I11—Bi3—I10^i	90.508 (14)	C14—C15—C16	117.9 (9)
I6—Bi3—I10^i	85.618 (14)	N3—C15—C16	121.5 (8)
I8—Bi3—I10	176.741 (16)	C17—C16—N4	121.1 (8)
I7—Bi3—I10	86.680 (15)	C17—C16—C15	121.3 (8)
I11—Bi3—I10	88.189 (14)	N4—C16—C15	117.6 (9)
I6—Bi3—I10	85.617 (13)	C16—C17—C18	120.1 (8)
I10^i—Bi3—I10	86.726 (14)	C16—C17—H17	119.9
Bi2—I5—Bi1	96.952 (15)	C18—C17—H17	119.9
Bi3—I6—Bi1	89.655 (13)	C19—C18—C17	122.4 (10)
Bi3—I6—Bi2	97.402 (14)	C19—C18—H18	118.8
Bi1—I6—Bi2	88.927 (13)	C17—C18—H18	118.8
Bi3—I7—Bi1	93.539 (15)	C18—C19—C20	119.0 (12)
Bi3^i—I10—Bi3	93.275 (14)	C18—C19—H19	120.5
Bi3^i—I10—Bi2	89.164 (13)	C20—C19—H19	120.5
Bi3—I10—Bi2	94.416 (13)	C19—C20—N4	123.4 (12)
Bi3—I11—Bi2^i	95.550 (15)	C19—C20—H20	118.3
C2—C1—N1	120.7 (12)	N4—C20—H20	118.3
C2—C1—H1	119.7	C5—N1—C1	123.0 (8)
N1—C1—H1	119.7	C6—N2—C10	116.1 (8)
C1—C2—C3	122.6 (12)	C15—N3—C11	117.5 (8)
C1—C2—H2	118.7	C16—N4—C20	114.0 (10)
I4—Bi2—I5—Bi1	−90.026 (18)	I6—Bi3—I10—Bi2	−3.564 (12)
I9—Bi2—I5—Bi1	173.835 (16)	I10^i—Bi3—I10—Bi2	−89.414 (14)
I10—Bi2—I5—Bi1	86.475 (15)	I9—Bi2—I10—Bi3^i	85.996 (15)
I6—Bi2—I5—Bi1	4.118 (15)	I5—Bi2—I10—Bi3^i	−179.500 (13)
I2—Bi1—I5—Bi2	−170.866 (18)	I11^i—Bi2—I10—Bi3^i	−5.809 (13)
I1—Bi1—I5—Bi2	88.922 (18)	I6—Bi2—I10—Bi3^i	−89.840 (13)
I6—Bi1—I5—Bi2	−4.172 (15)	I9—Bi2—I10—Bi3	179.216 (15)
I7—Bi1—I5—Bi2	−87.351 (16)	I5—Bi2—I10—Bi3	−86.280 (14)
I8—Bi3—I6—Bi1	−88.906 (15)	I11^i—Bi2—I10—Bi3	87.411 (14)
I7—Bi3—I6—Bi1	6.031 (14)	I6—Bi2—I10—Bi3	3.380 (12)
I10^i—Bi3—I6—Bi1	179.492 (13)	I8—Bi3—I11—Bi2^i	−85.247 (17)
I10—Bi3—I6—Bi1	92.448 (13)	I7—Bi3—I11—Bi2^i	179.894 (14)
I8—Bi3—I6—Bi2	−177.779 (15)	I10^i—Bi3—I11—Bi2^i	6.506 (14)
I7—Bi3—I6—Bi2	−82.842 (16)	I10—Bi3—I11—Bi2^i	93.214 (14)
I10^i—Bi3—I6—Bi2	90.619 (14)	C1—C2—C3—C4	0.7 (18)
I10—Bi3—I6—Bi2	3.575 (12)	C2—C3—C4—C5	−1.8 (15)
I2—Bi1—I6—Bi3	−40.04 (6)	C3—C4—C5—N1	1.2 (13)
I1—Bi1—I6—Bi3	175.352 (15)	C3—C4—C5—C6	−179.1 (8)
I3—Bi1—I6—Bi3	83.188 (16)	C4—C5—C6—C7	2.2 (14)
I5—Bi1—I6—Bi3	−93.772 (14)	N1—C5—C6—C7	−178.1 (8)
I7—Bi1—I6—Bi3	−5.289 (13)	C4—C5—C6—N2	−179.2 (9)
I2—Bi1—I6—Bi2	57.37 (6)	N1—C5—C6—N2	0.5 (11)
I1—Bi1—I6—Bi2	−87.239 (16)	N2—C6—C7—C8	−0.4 (13)
I3—Bi1—I6—Bi2	−179.402 (15)	C5—C6—C7—C8	178.0 (8)
I5—Bi1—I6—Bi2	3.637 (13)	C6—C7—C8—C9	−0.4 (13)
I7—Bi1—I6—Bi2	92.121 (14)	C7—C8—C9—C10	1.2 (13)
I4—Bi2—I6—Bi3	−179.985 (15)	C8—C9—C10—N2	−1.2 (14)
I9—Bi2—I6—Bi3	−25.89 (9)	C13—C14—C15—N3	1.4 (16)
I5—Bi2—I6—Bi3	85.461 (16)	C13—C14—C15—C16	−178.8 (11)
I11^i—Bi2—I6—Bi3	−88.496 (15)	C14—C15—C16—C17	2.0 (14)
I10—Bi2—I6—Bi3	−3.576 (12)	N3—C15—C16—C17	−178.2 (8)
I4—Bi2—I6—Bi1	90.503 (15)	C14—C15—C16—N4	−177.6 (8)
I9—Bi2—I6—Bi1	−115.40 (8)	N3—C15—C16—N4	2.2 (14)
I5—Bi2—I6—Bi1	−4.051 (15)	N4—C16—C17—C18	−1.0 (14)
I11^i—Bi2—I6—Bi1	−178.008 (13)	C15—C16—C17—C18	179.4 (9)
I10—Bi2—I6—Bi1	−93.089 (13)	C16—C17—C18—C19	0.0 (16)
I8—Bi3—I7—Bi1	85.695 (17)	C17—C18—C19—C20	0.7 (18)
I11—Bi3—I7—Bi1	−179.609 (14)	C18—C19—C20—N4	−0.3 (19)
I6—Bi3—I7—Bi1	−6.005 (14)	C4—C5—N1—C1	0.3 (14)
I10—Bi3—I7—Bi1	−91.419 (14)	C6—C5—N1—C1	−179.4 (9)
I2—Bi1—I7—Bi3	176.338 (16)	C2—C1—N1—C5	−1.5 (17)
I3—Bi1—I7—Bi3	−85.778 (17)	C7—C6—N2—C10	0.4 (13)
I5—Bi1—I7—Bi3	90.279 (15)	C5—C6—N2—C10	−178.1 (7)
I6—Bi1—I7—Bi3	5.740 (14)	C9—C10—N2—C6	0.5 (13)
I7—Bi3—I10—Bi3^i	179.346 (16)	C14—C15—N3—C11	−1.2 (14)
I11—Bi3—I10—Bi3^i	−90.614 (14)	C16—C15—N3—C11	179.1 (9)
I6—Bi3—I10—Bi3^i	85.849 (14)	C12—C11—N3—C15	0.6 (16)
I10^i—Bi3—I10—Bi3^i	0.0	C17—C16—N4—C20	1.3 (15)
I7—Bi3—I10—Bi2	89.932 (15)	C15—C16—N4—C20	−179.1 (9)
I11—Bi3—I10—Bi2	179.973 (14)	C19—C20—N4—C16	−0.6 (17)

Symmetry code: (i) −x+1, −y, −z+1.

(II) Bis[tris(2,2'-bipyridine)ruthenium(II)] di-µ₄-iodo-octa-µ₂-iodo-dodecaiodohexabismuthate

Crystal data

[Ru(C10H8N2)3][Bi6I22]	Z = 1
Mr = 5184.92	F(000) = 2244
TriclinicP1	Dx = 3.459 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 12.7346 (7) Å	Cell parameters from 6398 reflections
b = 13.6135 (7) Å	θ = 2.3–26.4°
c = 14.5978 (8) Å	µ = 17.72 mm^−1
α = 91.380 (1)°	T = 150 K
β = 100.077 (1)°	Block, red
γ = 92.010 (1)°	0.18 × 0.14 × 0.10 mm
V = 2489.0 (2) Å^3

Data collection

Bruker SMART APEX CCD area-detector diffractometer	10135 independent reflections
Radiation source: fine-focus sealed tube	8993 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 26.4°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→15
Tmin = 0.686, Tmax = 1.000	k = −17→16
23253 measured reflections	l = −18→18

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-atom parameters constrained
wR(F^2) = 0.070	w = 1/[σ^2(Fo^2) + (0.0252P)^2 + 2.3445P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max = 0.001
10135 reflections	Δρmax = 1.41 e Å^−3
461 parameters	Δρmin = −1.37 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.000139 (15)

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
Bi1	0.41886 (2)	0.30390 (2)	0.291703 (19)	0.01988 (7)
Bi2	0.30928 (2)	0.50057 (2)	0.529847 (18)	0.01762 (7)
Bi3	0.20117 (2)	0.58442 (2)	0.200418 (19)	0.02028 (7)
I1	0.21144 (4)	0.34315 (4)	0.16333 (4)	0.02646 (12)
I2	0.38479 (4)	0.08969 (4)	0.27127 (4)	0.02917 (12)
I3	0.54385 (4)	0.34293 (4)	0.14993 (4)	0.03105 (13)
I4	0.28655 (4)	0.28758 (4)	0.47181 (3)	0.02503 (12)
I5	0.63497 (4)	0.27280 (4)	0.43249 (4)	0.02656 (12)
I6	0.44314 (4)	0.53729 (3)	0.35133 (3)	0.01839 (10)
I7	0.20787 (4)	0.47348 (4)	0.68771 (3)	0.02542 (12)
I8	0.11192 (4)	0.53220 (4)	0.40310 (3)	0.02387 (11)
I9	0.23948 (4)	0.79036 (4)	0.26637 (3)	0.02690 (12)
I10	0.26680 (4)	0.61919 (4)	0.02466 (4)	0.03173 (13)
I11	−0.02140 (4)	0.58406 (4)	0.12845 (4)	0.03035 (13)
Ru1	0.20609 (4)	0.05816 (4)	0.79301 (4)	0.01556 (12)
C1	0.3029 (6)	−0.0056 (6)	0.6255 (5)	0.0227 (16)
H1	0.2554	−0.0616	0.6214	0.027*
C2	0.3613 (6)	0.0065 (5)	0.5566 (5)	0.0218 (16)
H2	0.3512	−0.0379	0.5043	0.026*
C3	0.4358 (6)	0.0845 (6)	0.5637 (5)	0.0268 (18)
H3	0.4792	0.0935	0.5176	0.032*
C4	0.4447 (6)	0.1482 (5)	0.6392 (5)	0.0225 (16)
H4	0.4963	0.2012	0.6466	0.027*
C5	0.3788 (6)	0.1359 (5)	0.7051 (5)	0.0180 (15)
C6	0.3731 (5)	0.2081 (5)	0.7818 (5)	0.0164 (15)
C7	0.4423 (6)	0.2891 (6)	0.8040 (5)	0.0246 (17)
H7	0.5002	0.2994	0.7717	0.029*
C8	0.4269 (6)	0.3540 (5)	0.8722 (5)	0.0255 (17)
H8	0.4744	0.4096	0.8884	0.031*
C9	0.3416 (6)	0.3385 (6)	0.9178 (5)	0.0277 (18)
H9	0.3284	0.3842	0.9643	0.033*
C10	0.2757 (6)	0.2554 (5)	0.8945 (5)	0.0226 (16)
H10	0.2178	0.2440	0.9266	0.027*
C11	0.0882 (6)	0.1942 (5)	0.6516 (5)	0.0237 (17)
H11	0.1430	0.2417	0.6758	0.028*
C12	0.0097 (6)	0.2200 (6)	0.5803 (5)	0.0269 (18)
H12	0.0109	0.2837	0.5552	0.032*
C13	−0.0705 (7)	0.1518 (6)	0.5459 (6)	0.033 (2)
H13	−0.1271	0.1685	0.4980	0.039*
C14	−0.0678 (6)	0.0596 (6)	0.5815 (5)	0.0298 (19)
H14	−0.1225	0.0117	0.5580	0.036*
C15	0.0147 (6)	0.0363 (6)	0.6519 (5)	0.0223 (16)
C16	0.0316 (6)	−0.0632 (5)	0.6874 (5)	0.0205 (16)
C17	−0.0355 (7)	−0.1456 (6)	0.6585 (5)	0.0295 (19)
H17	−0.1015	−0.1384	0.6178	0.035*
C18	−0.0062 (7)	−0.2370 (6)	0.6888 (6)	0.034 (2)
H18	−0.0515	−0.2932	0.6690	0.041*
C19	0.0893 (7)	−0.2465 (6)	0.7481 (6)	0.0315 (19)
H19	0.1123	−0.3092	0.7687	0.038*
C20	0.1500 (6)	−0.1628 (6)	0.7763 (5)	0.0270 (18)
H20	0.2152	−0.1693	0.8183	0.032*
C21	0.3924 (6)	−0.0538 (5)	0.8959 (6)	0.0261 (18)
H21	0.4221	−0.0500	0.8407	0.031*
C22	0.4429 (7)	−0.1084 (6)	0.9676 (6)	0.034 (2)
H22	0.5065	−0.1409	0.9624	0.041*
C23	0.3990 (7)	−0.1146 (6)	1.0468 (6)	0.039 (2)
H23	0.4310	−0.1535	1.0965	0.047*
C24	0.3096 (7)	−0.0651 (6)	1.0543 (6)	0.0315 (19)
H24	0.2795	−0.0691	1.1093	0.038*
C25	0.2628 (6)	−0.0091 (5)	0.9818 (5)	0.0196 (16)
C26	0.1662 (6)	0.0470 (5)	0.9831 (5)	0.0206 (16)
C27	0.1273 (6)	0.0703 (6)	1.0624 (5)	0.0291 (19)
H27	0.1612	0.0480	1.1210	0.035*
C28	0.0384 (7)	0.1263 (6)	1.0562 (6)	0.0308 (19)
H28	0.0121	0.1450	1.1109	0.037*
C29	−0.0125 (6)	0.1553 (5)	0.9697 (6)	0.0285 (18)
H29	−0.0752	0.1921	0.9636	0.034*
C30	0.0307 (6)	0.1291 (5)	0.8933 (6)	0.0240 (17)
H30	−0.0039	0.1486	0.8339	0.029*
N1	0.3084 (5)	0.0570 (4)	0.6992 (4)	0.0205 (13)
N2	0.2911 (5)	0.1899 (4)	0.8276 (4)	0.0178 (13)
N3	0.0911 (5)	0.1042 (4)	0.6889 (4)	0.0195 (13)
N4	0.1244 (5)	−0.0727 (4)	0.7491 (4)	0.0189 (13)
N5	0.3024 (5)	−0.0053 (4)	0.9007 (4)	0.0204 (13)
N6	0.1194 (5)	0.0774 (4)	0.8978 (4)	0.0193 (13)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Bi1	0.02196 (15)	0.01732 (14)	0.02009 (14)	0.00007 (11)	0.00342 (12)	−0.00202 (11)
Bi2	0.01565 (14)	0.01760 (14)	0.01942 (14)	0.00009 (11)	0.00257 (11)	0.00111 (11)
Bi3	0.01814 (15)	0.02053 (15)	0.02202 (15)	0.00111 (11)	0.00282 (11)	0.00236 (11)
I1	0.0247 (3)	0.0225 (3)	0.0294 (3)	−0.0004 (2)	−0.0025 (2)	−0.0003 (2)
I2	0.0346 (3)	0.0179 (3)	0.0320 (3)	0.0009 (2)	−0.0016 (2)	−0.0039 (2)
I3	0.0359 (3)	0.0328 (3)	0.0262 (3)	−0.0044 (2)	0.0124 (2)	−0.0049 (2)
I4	0.0271 (3)	0.0193 (3)	0.0286 (3)	0.0006 (2)	0.0045 (2)	0.0004 (2)
I5	0.0265 (3)	0.0175 (2)	0.0325 (3)	0.0019 (2)	−0.0036 (2)	−0.0004 (2)
I6	0.0168 (2)	0.0180 (2)	0.0203 (2)	−0.00018 (19)	0.00311 (19)	0.00111 (19)
I7	0.0242 (3)	0.0304 (3)	0.0227 (2)	−0.0009 (2)	0.0072 (2)	0.0024 (2)
I8	0.0193 (2)	0.0277 (3)	0.0242 (3)	0.0050 (2)	0.0013 (2)	0.0047 (2)
I9	0.0310 (3)	0.0226 (3)	0.0266 (3)	−0.0001 (2)	0.0040 (2)	−0.0002 (2)
I10	0.0333 (3)	0.0358 (3)	0.0286 (3)	−0.0047 (2)	0.0140 (2)	−0.0010 (2)
I11	0.0184 (3)	0.0398 (3)	0.0321 (3)	−0.0002 (2)	0.0019 (2)	0.0051 (2)
Ru1	0.0153 (3)	0.0144 (3)	0.0171 (3)	−0.0004 (2)	0.0035 (2)	−0.0001 (2)
C1	0.020 (4)	0.025 (4)	0.025 (4)	0.002 (3)	0.007 (3)	0.001 (3)
C2	0.031 (4)	0.014 (4)	0.022 (4)	0.007 (3)	0.007 (3)	0.000 (3)
C3	0.024 (4)	0.027 (4)	0.033 (4)	0.011 (3)	0.012 (4)	0.008 (4)
C4	0.016 (4)	0.020 (4)	0.033 (4)	0.004 (3)	0.007 (3)	0.004 (3)
C5	0.018 (4)	0.013 (3)	0.023 (4)	0.002 (3)	0.003 (3)	0.003 (3)
C6	0.012 (3)	0.019 (4)	0.016 (3)	0.004 (3)	−0.005 (3)	0.008 (3)
C7	0.015 (4)	0.031 (4)	0.029 (4)	−0.002 (3)	0.006 (3)	0.008 (4)
C8	0.024 (4)	0.019 (4)	0.028 (4)	−0.004 (3)	−0.009 (3)	0.002 (3)
C9	0.033 (5)	0.019 (4)	0.029 (4)	0.001 (3)	0.000 (4)	−0.011 (3)
C10	0.028 (4)	0.023 (4)	0.016 (4)	0.000 (3)	0.004 (3)	0.000 (3)
C11	0.027 (4)	0.019 (4)	0.023 (4)	0.003 (3)	0.000 (3)	−0.001 (3)
C12	0.028 (4)	0.031 (5)	0.023 (4)	0.004 (4)	0.008 (3)	0.000 (3)
C13	0.030 (5)	0.041 (5)	0.024 (4)	0.013 (4)	−0.003 (4)	0.000 (4)
C14	0.024 (4)	0.037 (5)	0.027 (4)	0.002 (4)	0.000 (3)	−0.006 (4)
C15	0.016 (4)	0.037 (5)	0.013 (3)	0.001 (3)	0.003 (3)	−0.004 (3)
C16	0.020 (4)	0.028 (4)	0.014 (3)	−0.006 (3)	0.006 (3)	−0.007 (3)
C17	0.029 (4)	0.032 (5)	0.026 (4)	−0.006 (4)	0.004 (4)	−0.009 (4)
C18	0.046 (6)	0.028 (5)	0.029 (4)	−0.020 (4)	0.011 (4)	−0.005 (4)
C19	0.044 (5)	0.017 (4)	0.036 (5)	−0.003 (4)	0.016 (4)	0.002 (3)
C20	0.029 (4)	0.024 (4)	0.030 (4)	0.001 (3)	0.010 (4)	−0.002 (3)
C21	0.023 (4)	0.019 (4)	0.033 (4)	−0.002 (3)	−0.002 (3)	−0.010 (3)
C22	0.027 (5)	0.019 (4)	0.049 (5)	0.007 (3)	−0.011 (4)	−0.007 (4)
C23	0.043 (6)	0.027 (5)	0.039 (5)	−0.005 (4)	−0.013 (4)	0.010 (4)
C24	0.036 (5)	0.028 (4)	0.025 (4)	−0.009 (4)	−0.008 (4)	−0.001 (4)
C25	0.024 (4)	0.019 (4)	0.012 (3)	−0.009 (3)	−0.003 (3)	−0.001 (3)
C26	0.025 (4)	0.014 (4)	0.022 (4)	−0.006 (3)	0.005 (3)	0.001 (3)
C27	0.031 (5)	0.028 (4)	0.027 (4)	−0.013 (4)	0.004 (4)	−0.001 (4)
C28	0.038 (5)	0.023 (4)	0.033 (5)	−0.013 (4)	0.014 (4)	−0.006 (4)
C29	0.025 (4)	0.019 (4)	0.043 (5)	−0.003 (3)	0.015 (4)	−0.008 (4)
C30	0.024 (4)	0.015 (4)	0.034 (4)	0.002 (3)	0.006 (3)	0.000 (3)
N1	0.015 (3)	0.025 (3)	0.022 (3)	0.002 (3)	0.003 (3)	0.006 (3)
N2	0.020 (3)	0.013 (3)	0.021 (3)	0.005 (2)	0.003 (3)	0.003 (2)
N3	0.022 (3)	0.019 (3)	0.019 (3)	0.004 (3)	0.007 (3)	0.003 (3)
N4	0.028 (3)	0.017 (3)	0.014 (3)	−0.001 (3)	0.009 (3)	−0.002 (2)
N5	0.020 (3)	0.013 (3)	0.026 (3)	−0.004 (3)	0.001 (3)	−0.001 (3)
N6	0.020 (3)	0.012 (3)	0.026 (3)	−0.004 (2)	0.007 (3)	−0.005 (3)

Geometric parameters (Å, º)

Bi1—I3	2.8715 (6)	C10—N2	1.350 (9)
Bi1—I2	2.9335 (6)	C10—H10	0.9500
Bi1—I1	3.0315 (6)	C11—N3	1.352 (9)
Bi1—I5	3.1813 (6)	C11—C12	1.372 (10)
Bi1—I6	3.2637 (5)	C11—H11	0.9500
Bi1—I4	3.3695 (6)	C12—C13	1.374 (11)
Bi2—I7	2.8571 (5)	C12—H12	0.9500
Bi2—I8	2.9004 (6)	C13—C14	1.369 (11)
Bi2—I4	2.9909 (6)	C13—H13	0.9500
Bi2—I5^i	3.1548 (6)	C14—C15	1.387 (10)
Bi2—I6^i	3.3850 (6)	C14—H14	0.9500
Bi2—I6	3.3918 (5)	C15—N3	1.349 (9)
Bi3—I11	2.8450 (6)	C15—C16	1.471 (11)
Bi3—I10	2.8786 (6)	C16—N4	1.367 (9)
Bi3—I9	2.9384 (6)	C16—C17	1.396 (10)
Bi3—I1	3.3268 (6)	C17—C18	1.374 (12)
Bi3—I8	3.4311 (6)	C17—H17	0.9500
Bi3—I6	3.5484 (5)	C18—C19	1.375 (12)
I5—Bi2^i	3.1548 (6)	C18—H18	0.9500
I6—Bi2^i	3.3850 (5)	C19—C20	1.369 (10)
Ru1—N3	2.044 (6)	C19—H19	0.9500
Ru1—N5	2.047 (6)	C20—N4	1.332 (9)
Ru1—N1	2.048 (6)	C20—H20	0.9500
Ru1—N6	2.054 (6)	C21—N5	1.354 (9)
Ru1—N4	2.061 (6)	C21—C22	1.377 (11)
Ru1—N2	2.067 (6)	C21—H21	0.9500
C1—N1	1.347 (9)	C22—C23	1.373 (12)
C1—C2	1.362 (10)	C22—H22	0.9500
C1—H1	0.9500	C23—C24	1.362 (12)
C2—C3	1.389 (10)	C23—H23	0.9500
C2—H2	0.9500	C24—C25	1.381 (10)
C3—C4	1.373 (10)	C24—H24	0.9500
C3—H3	0.9500	C25—N5	1.367 (9)
C4—C5	1.391 (10)	C25—C26	1.473 (10)
C4—H4	0.9500	C26—N6	1.363 (9)
C5—N1	1.366 (9)	C26—C27	1.372 (10)
C5—C6	1.485 (10)	C27—C28	1.378 (11)
C6—N2	1.354 (9)	C27—H27	0.9500
C6—C7	1.384 (10)	C28—C29	1.388 (11)
C7—C8	1.359 (11)	C28—H28	0.9500
C7—H7	0.9500	C29—C30	1.373 (10)
C8—C9	1.383 (11)	C29—H29	0.9500
C8—H8	0.9500	C30—N6	1.344 (9)
C9—C10	1.385 (10)	C30—H30	0.9500
C9—H9	0.9500
I3—Bi1—I2	101.416 (17)	C8—C7—H7	120.2
I3—Bi1—I1	92.679 (17)	C6—C7—H7	120.2
I2—Bi1—I1	93.372 (16)	C7—C8—C9	119.5 (7)
I3—Bi1—I5	88.424 (17)	C7—C8—H8	120.3
I2—Bi1—I5	89.118 (15)	C9—C8—H8	120.3
I1—Bi1—I5	177.022 (16)	C8—C9—C10	118.9 (7)
I3—Bi1—I6	88.703 (15)	C8—C9—H9	120.6
I2—Bi1—I6	169.475 (16)	C10—C9—H9	120.6
I1—Bi1—I6	88.991 (14)	N2—C10—C9	122.0 (7)
I5—Bi1—I6	88.269 (14)	N2—C10—H10	119.0
I3—Bi1—I4	172.149 (16)	C9—C10—H10	119.0
I2—Bi1—I4	85.859 (15)	N3—C11—C12	123.1 (7)
I1—Bi1—I4	89.804 (15)	N3—C11—H11	118.5
I5—Bi1—I4	88.746 (15)	C12—C11—H11	118.5
I6—Bi1—I4	83.892 (13)	C11—C12—C13	118.6 (8)
I7—Bi2—I8	94.395 (16)	C11—C12—H12	120.7
I7—Bi2—I4	93.795 (16)	C13—C12—H12	120.7
I8—Bi2—I4	88.622 (16)	C14—C13—C12	119.2 (7)
I7—Bi2—I5^i	96.159 (16)	C14—C13—H13	120.4
I8—Bi2—I5^i	93.814 (15)	C12—C13—H13	120.4
I4—Bi2—I5^i	169.536 (17)	C13—C14—C15	119.9 (8)
I7—Bi2—I6^i	94.164 (15)	C13—C14—H14	120.0
I8—Bi2—I6^i	171.336 (15)	C15—C14—H14	120.0
I4—Bi2—I6^i	89.471 (14)	N3—C15—C14	121.1 (7)
I5^i—Bi2—I6^i	86.602 (14)	N3—C15—C16	114.6 (6)
I7—Bi2—I6	176.570 (16)	C14—C15—C16	124.1 (7)
I8—Bi2—I6	88.683 (14)	N4—C16—C17	120.1 (7)
I4—Bi2—I6	87.784 (14)	N4—C16—C15	114.8 (6)
I5^i—Bi2—I6	82.106 (14)	C17—C16—C15	125.0 (7)
I6^i—Bi2—I6	82.798 (13)	C18—C17—C16	120.1 (8)
I11—Bi3—I10	95.152 (18)	C18—C17—H17	120.0
I11—Bi3—I9	100.273 (18)	C16—C17—H17	120.0
I10—Bi3—I9	93.966 (17)	C17—C18—C19	119.5 (7)
I11—Bi3—I1	92.663 (16)	C17—C18—H18	120.3
I10—Bi3—I1	90.128 (16)	C19—C18—H18	120.3
I9—Bi3—I1	166.008 (17)	C20—C19—C18	117.7 (8)
I11—Bi3—I8	82.427 (15)	C20—C19—H19	121.1
I10—Bi3—I8	176.493 (17)	C18—C19—H19	121.1
I9—Bi3—I8	88.974 (15)	N4—C20—C19	124.7 (8)
I1—Bi3—I8	87.457 (14)	N4—C20—H20	117.6
I11—Bi3—I6	159.653 (16)	C19—C20—H20	117.6
I10—Bi3—I6	103.687 (16)	N5—C21—C22	122.9 (8)
I9—Bi3—I6	86.192 (14)	N5—C21—H21	118.6
I1—Bi3—I6	79.838 (13)	C22—C21—H21	118.6
I8—Bi3—I6	78.392 (13)	C23—C22—C21	118.3 (8)
Bi1—I1—Bi3	99.941 (15)	C23—C22—H22	120.9
Bi2—I4—Bi1	96.877 (15)	C21—C22—H22	120.9
Bi2^i—I5—Bi1	94.705 (15)	C24—C23—C22	120.1 (8)
Bi1—I6—Bi2^i	88.990 (13)	C24—C23—H23	119.9
Bi1—I6—Bi2	91.440 (13)	C22—C23—H23	119.9
Bi2^i—I6—Bi2	97.202 (13)	C23—C24—C25	119.9 (8)
Bi1—I6—Bi3	91.229 (13)	C23—C24—H24	120.1
Bi2^i—I6—Bi3	172.104 (16)	C25—C24—H24	120.1
Bi2—I6—Bi3	90.684 (13)	N5—C25—C24	121.0 (7)
Bi2—I8—Bi3	102.174 (16)	N5—C25—C26	114.9 (6)
N3—Ru1—N5	170.4 (2)	C24—C25—C26	124.1 (7)
N3—Ru1—N1	88.0 (2)	N6—C26—C27	122.0 (7)
N5—Ru1—N1	98.1 (2)	N6—C26—C25	114.0 (6)
N3—Ru1—N6	95.8 (2)	C27—C26—C25	124.0 (7)
N5—Ru1—N6	79.3 (2)	C26—C27—C28	119.3 (8)
N1—Ru1—N6	170.7 (2)	C26—C27—H27	120.4
N3—Ru1—N4	78.8 (2)	C28—C27—H27	120.4
N5—Ru1—N4	93.0 (2)	C27—C28—C29	119.6 (8)
N1—Ru1—N4	97.2 (2)	C27—C28—H28	120.2
N6—Ru1—N4	91.8 (2)	C29—C28—H28	120.2
N3—Ru1—N2	99.3 (2)	C30—C29—C28	117.9 (8)
N5—Ru1—N2	89.1 (2)	C30—C29—H29	121.1
N1—Ru1—N2	78.9 (2)	C28—C29—H29	121.1
N6—Ru1—N2	92.1 (2)	N6—C30—C29	123.6 (8)
N4—Ru1—N2	175.9 (2)	N6—C30—H30	118.2
N1—C1—C2	124.0 (7)	C29—C30—H30	118.2
N1—C1—H1	118.0	C1—N1—C5	117.2 (6)
C2—C1—H1	118.0	C1—N1—Ru1	126.3 (5)
C1—C2—C3	119.2 (7)	C5—N1—Ru1	115.8 (5)
C1—C2—H2	120.4	C10—N2—C6	118.1 (6)
C3—C2—H2	120.4	C10—N2—Ru1	125.9 (5)
C4—C3—C2	118.0 (7)	C6—N2—Ru1	115.8 (5)
C4—C3—H3	121.0	C15—N3—C11	117.9 (6)
C2—C3—H3	121.0	C15—N3—Ru1	116.2 (5)
C3—C4—C5	120.7 (7)	C11—N3—Ru1	125.8 (5)
C3—C4—H4	119.7	C20—N4—C16	117.8 (6)
C5—C4—H4	119.7	C20—N4—Ru1	127.6 (5)
N1—C5—C4	120.9 (7)	C16—N4—Ru1	114.6 (5)
N1—C5—C6	114.8 (6)	C21—N5—C25	117.8 (6)
C4—C5—C6	124.2 (6)	C21—N5—Ru1	126.6 (5)
N2—C6—C7	121.9 (7)	C25—N5—Ru1	115.0 (5)
N2—C6—C5	114.1 (6)	C30—N6—C26	117.5 (6)
C7—C6—C5	124.0 (6)	C30—N6—Ru1	126.2 (5)
C8—C7—C6	119.6 (7)	C26—N6—Ru1	115.5 (5)
I3—Bi1—I1—Bi3	−88.346 (17)	N5—C25—C26—N6	12.5 (9)
I2—Bi1—I1—Bi3	170.044 (16)	C24—C25—C26—N6	−165.1 (7)
I6—Bi1—I1—Bi3	0.308 (15)	N5—C25—C26—C27	−165.5 (7)
I4—Bi1—I1—Bi3	84.203 (15)	C25—C26—C27—C28	177.6 (7)
I11—Bi3—I1—Bi1	−161.238 (17)	C2—C1—N1—Ru1	168.5 (6)
I10—Bi3—I1—Bi1	103.598 (18)	C6—C5—N1—C1	173.7 (6)
I9—Bi3—I1—Bi1	−3.56 (7)	C4—C5—N1—Ru1	−173.4 (5)
I8—Bi3—I1—Bi1	−78.946 (16)	C6—C5—N1—Ru1	2.7 (8)
I6—Bi3—I1—Bi1	−0.288 (14)	N3—Ru1—N1—C1	−69.0 (6)
I7—Bi2—I4—Bi1	−176.382 (15)	N5—Ru1—N1—C1	103.6 (6)
I8—Bi2—I4—Bi1	89.303 (16)	N4—Ru1—N1—C1	9.4 (6)
I5^i—Bi2—I4—Bi1	−14.35 (10)	N2—Ru1—N1—C1	−169.0 (6)
I6^i—Bi2—I4—Bi1	−82.245 (15)	N3—Ru1—N1—C5	101.0 (5)
I6—Bi2—I4—Bi1	0.568 (14)	N5—Ru1—N1—C5	−86.4 (5)
I2—Bi1—I4—Bi2	177.005 (17)	N4—Ru1—N1—C5	179.5 (5)
I1—Bi1—I4—Bi2	−89.600 (16)	N2—Ru1—N1—C5	1.1 (5)
I5—Bi1—I4—Bi2	87.799 (16)	C9—C10—N2—Ru1	175.1 (5)
I6—Bi1—I4—Bi2	−0.593 (14)	C5—C6—N2—C10	−175.8 (6)
I3—Bi1—I5—Bi2^i	79.297 (17)	C7—C6—N2—Ru1	−174.2 (5)
I2—Bi1—I5—Bi2^i	−179.256 (16)	C5—C6—N2—Ru1	7.9 (7)
I6—Bi1—I5—Bi2^i	−9.453 (15)	N3—Ru1—N2—C10	92.9 (6)
I4—Bi1—I5—Bi2^i	−93.379 (15)	N5—Ru1—N2—C10	−82.6 (6)
I3—Bi1—I6—Bi2^i	−79.686 (16)	N1—Ru1—N2—C10	178.9 (6)
I2—Bi1—I6—Bi2^i	84.47 (9)	N6—Ru1—N2—C10	−3.3 (6)
I1—Bi1—I6—Bi2^i	−172.390 (14)	N3—Ru1—N2—C6	−91.1 (5)
I5—Bi1—I6—Bi2^i	8.776 (14)	N5—Ru1—N2—C6	93.4 (5)
I4—Bi1—I6—Bi2^i	97.700 (14)	N1—Ru1—N2—C6	−5.1 (5)
I3—Bi1—I6—Bi2	−176.866 (16)	N6—Ru1—N2—C6	172.7 (5)
I2—Bi1—I6—Bi2	−12.71 (9)	C16—C15—N3—C11	171.9 (6)
I1—Bi1—I6—Bi2	90.430 (15)	C14—C15—N3—Ru1	179.4 (5)
I5—Bi1—I6—Bi2	−88.404 (14)	C16—C15—N3—Ru1	−4.9 (7)
I4—Bi1—I6—Bi2	0.520 (12)	C12—C11—N3—Ru1	178.6 (5)
I3—Bi1—I6—Bi3	92.419 (16)	N1—Ru1—N3—C15	105.4 (5)
I2—Bi1—I6—Bi3	−103.42 (9)	N6—Ru1—N3—C15	−83.2 (5)
I1—Bi1—I6—Bi3	−0.285 (14)	N4—Ru1—N3—C15	7.6 (5)
I5—Bi1—I6—Bi3	−179.119 (14)	N2—Ru1—N3—C15	−176.2 (5)
I4—Bi1—I6—Bi3	−90.195 (13)	N1—Ru1—N3—C11	−71.2 (6)
I8—Bi2—I6—Bi1	−89.254 (15)	N6—Ru1—N3—C11	100.3 (6)
I4—Bi2—I6—Bi1	−0.582 (14)	N4—Ru1—N3—C11	−169.0 (6)
I5^i—Bi2—I6—Bi1	176.711 (14)	N2—Ru1—N3—C11	7.2 (6)
I6^i—Bi2—I6—Bi1	89.164 (13)	C19—C20—N4—Ru1	176.4 (6)
I8—Bi2—I6—Bi2^i	−178.418 (16)	C15—C16—N4—C20	−173.0 (6)
I4—Bi2—I6—Bi2^i	−89.747 (15)	C17—C16—N4—Ru1	−174.7 (5)
I5^i—Bi2—I6—Bi2^i	87.547 (14)	C15—C16—N4—Ru1	9.1 (7)
I6^i—Bi2—I6—Bi2^i	0.0	N3—Ru1—N4—C20	173.4 (6)
I8—Bi2—I6—Bi3	1.992 (14)	N5—Ru1—N4—C20	−11.7 (6)
I4—Bi2—I6—Bi3	90.664 (14)	N1—Ru1—N4—C20	86.9 (6)
I5^i—Bi2—I6—Bi3	−92.042 (13)	N6—Ru1—N4—C20	−91.1 (6)
I6^i—Bi2—I6—Bi3	−179.589 (17)	N3—Ru1—N4—C16	−9.0 (5)
I11—Bi3—I6—Bi1	69.93 (5)	N5—Ru1—N4—C16	165.9 (5)
I10—Bi3—I6—Bi1	−87.369 (16)	N1—Ru1—N4—C16	−95.5 (5)
I9—Bi3—I6—Bi1	179.471 (14)	N6—Ru1—N4—C16	86.5 (5)
I1—Bi3—I6—Bi1	0.264 (13)	C22—C21—N5—Ru1	−168.8 (6)
I8—Bi3—I6—Bi1	89.737 (13)	C26—C25—N5—C21	178.7 (6)
I11—Bi3—I6—Bi2	−21.53 (5)	C24—C25—N5—Ru1	168.2 (5)
I10—Bi3—I6—Bi2	−178.824 (15)	C26—C25—N5—Ru1	−9.5 (7)
I9—Bi3—I6—Bi2	88.015 (14)	N1—Ru1—N5—C21	−14.6 (6)
I1—Bi3—I6—Bi2	−91.192 (13)	N6—Ru1—N5—C21	174.4 (6)
I7—Bi2—I8—Bi3	176.376 (16)	N4—Ru1—N5—C21	83.2 (6)
I4—Bi2—I8—Bi3	−89.923 (16)	N2—Ru1—N5—C21	−93.3 (6)
I5^i—Bi2—I8—Bi3	79.890 (16)	N1—Ru1—N5—C25	174.4 (5)
I6—Bi2—I8—Bi3	−2.108 (15)	N6—Ru1—N5—C25	3.5 (5)
I11—Bi3—I8—Bi2	175.228 (19)	N4—Ru1—N5—C25	−87.8 (5)
I9—Bi3—I8—Bi2	−84.267 (17)	N2—Ru1—N5—C25	95.7 (5)
I1—Bi3—I8—Bi2	82.200 (16)	C29—C30—N6—Ru1	−167.1 (6)
I6—Bi3—I8—Bi2	2.056 (14)	C25—C26—N6—C30	180.0 (6)
C3—C4—C5—C6	−171.7 (7)	C27—C26—N6—Ru1	168.5 (5)
N1—C5—C6—N2	−6.9 (9)	C25—C26—N6—Ru1	−9.5 (7)
C4—C5—C6—N2	169.0 (7)	N3—Ru1—N6—C30	−15.2 (6)
N1—C5—C6—C7	175.2 (7)	N5—Ru1—N6—C30	173.1 (6)
C5—C6—C7—C8	176.3 (7)	N4—Ru1—N6—C30	−94.1 (6)
C13—C14—C15—C16	−172.7 (7)	N2—Ru1—N6—C30	84.4 (6)
N3—C15—C16—N4	−2.9 (9)	N3—Ru1—N6—C26	175.3 (5)
C14—C15—C16—N4	172.7 (7)	N5—Ru1—N6—C26	3.6 (5)
N3—C15—C16—C17	−178.8 (7)	N4—Ru1—N6—C26	96.3 (5)
C15—C16—C17—C18	173.0 (7)	N2—Ru1—N6—C26	−85.1 (5)
C23—C24—C25—C26	180.0 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.