Paddlewheel dirhodium complexes bridged by para-substituted benzoates

The dirhodium complex bis­(benzonitrile)tetra­kis[μ-4-(diethyl­amino)benzoato-κ²O:O′]dirhodium(II)(Rh—Rh) benzonitrile disolvate, [Rh₂(C₁₁H₁₄NO₂)₄(C₇H₅N)₂]·2C₇H₅N, lies about an inversion centre. The dirhodium complex (methanol)tetra­kis(μ-4-nitro­benzoato-κ²O:O′)(pyridine)dirhodium(II)(Rh—Rh) dichloro­methane solvate, [Rh₂(C₇H₄NO₄)₄(C₅H₅N)(CH₄O)]·CH₂Cl₂, lies in a general position in the unit cell, but the complexes dimerize around an inversion centre via O—H...O hydrogen bonding of the axial MeOH to a carboxyl­ate O atom. In the latter crystal structure, π–π stacking inter­actions between the bridging 4-nitro­benzoate ligands and the axial pyridine ligand are observed between adjacent mol­ecules.

S1. Comment

Paddlewheel dimetal complexes have been attracted much attention in recent years, because they are useful modules to make assembled frameworks. Among such paddlewheel complexes, metal–metal single-bonded dirhodium(II) complexes are interesting examples that change their highest occupied molecular orbitals (HOMOs) depending on their bridging and axial ligands (Kawamura et al., 1989, 1998). For example, the HOMOs of such compounds with carboxylate bridges are π* orbitals, but amidate-bridged ones have a δ* HOMO. We have studied assembled structures with paddlewheel dirhodium cationic radicals constructed by π–π stacking interactions between odd electron densities on the bridging ligands (Kawamura et al., 1993, 2000) or by connection with axial linker ligands (Yang et al., 2000, 2001, 2006; Takazaki et al., 2003; Fuma et al., 2004). Substituted benzoates are interesting bridging ligands, the donor ability and stacking pattern of which are changed with their substituents. In this paper, we report the crystal structures of two novel dirhodium complexes with p-substituted benzoate bridges, [Rh₂(O₂CC₆H₄NEt₂)₄(PhCN)₂]·2PhCN, (I), and [Rh₂(O₂CC₆H₄NO₂)₄(MeOH)(py)]·CH₂Cl₂, (II).

In the structure of (I), the rhodium complex lies on a crystallographic inversion centre, there is also one benzonitrile solvent molecule in the asymmetric unit. The O—Rh—Rh—O torsion angles are close to 0°. In one of the two independent bridging ligands, four of the six phenyl C atoms, the N atom and one ethyl group are disordered over two sets of sites, labelled A and B. In both disordered sites, the phenyl groups are slightly tilted from the CO₂ plane (Table 2). The C₂N moiety of the amino group does not deviate much from the C₆H₄ plane. The ethyl groups of the diethylamino substituent point toward opposite sides of the phenyl ring for the A site and towards the same side for the B site. For the other bridging ligand, the C₂N, C₆H₄ and CO₂ moieties are nearly coplanar and the ethyl groups of the amino substituent point towards the same side of the phenyl ring. The near-planarity of the diethylaminobenzoate group suggests that it has a significant quinoid character. This is also reflected in the bond-length pattern of the ligand [average distances are: C2—C3 and C2—C7 1.390 (2) Å; C3—C4 and C6—C7 1.378 (2) Å; C4—C5 and C5—C6 1.408 (2) Å]. The axial positions are occupied by benzonitrile molecules, with almost straight Rh1—Rh1—N3 and the slightly bent Rh1—N3—C23 angles. The Rh—Rh distance of 2.3920 (9) Å is very close to the values observed for dirhodium complexes bridged by benzoate or its derivatives and axially bonded by N-donors [2.3882 (4)–2.4037 (4) Å; Castro et al., 2002; Cotton & Thompson, 1984; Cotton et al., 2002; Hikichi et al., 2003; Mehmet & Tocher, 1991]. In the crystal structure of (I), π–π stacking interactions are not observed.

In the structure of (II), there is one independent molecule in the asymmetric unit with a disordered dichloromethane molecule. The Rh₂O₈ skeleton is in a nearly complete eclipsed conformation, as was found for (I). The bridging nitrobenzoate ligands are almost planar: dihedral angles between the O₂C and phenyl groups and between the phenyl and NO₂ groups for each ligand are close to 0° (Table 5). The axial sites are occupied by one MeOH and one pyridine ligand. Only two dirhodium compounds with an N and an O atom at the axial positions have been reported to date (Cogne et al., 1987, 1989). The pyridine ring is slightly tilted from the plane of the nearer carboxylate groups, with a torsion angle between them of ca 15°. The Rh—Rh distance [2.3936 (10) Å] is very similar to that of (I).

In the crystal structure of (II), the MeOH ligand donates an H atom to an O atom of the bridging carboxylate [O2ⁱ; Fig. 3 and Table 4; symmetry code: (ii) Should this be (i)? 1 - x, 1 - y, 1 - z]. This type of hydrogen bonding has also been observed in some paddlewheel complexes with axial alcohol ligands (Rao et al., 1983; Noinville et al., 1993; Agterberg et al., 1997). Strong π–π stacking interactions between p-nitrobenzoate and pyridine are observed between the complex molecules at (x, y, z) and (1 - x, 1 - y, -z), and between those at (x, y, z) and (2 - x, 1 - y, 1 - z) (Fig. 3). In the former pair, representative short contacts are as follows: N2···C32ⁱⁱ 3.177 (6), C11···C29ⁱⁱ 3.252 (7), O7···C33ⁱⁱ 3.320 (6), C12···C31ⁱⁱ 3.342 (7) and C13···C31ⁱⁱ 3.394 (8) Å [symmetry code: (ii) 1 - x, 1 - y, -z]. In the latter pair, very similar contacts are observed: N4···C30ⁱⁱⁱ 3.172 (7), C25···C33ⁱⁱⁱ 3.270 (7), O16···C30ⁱⁱⁱ 3.230 (5), C27···C31ⁱⁱⁱ 3.386 (7) and C26···C31ⁱⁱⁱ 3.403 (8) Å [symmetry code: (iii) 2 - x, 1 - y, 1 - z]. These interactions result in the nitrobenzoate ligands sandwiching the pyridine.

S2. Experimental

Tetrakis(µ-acetato)bis(methanol)dirhodium was prepared according to the literature procedure of Rempel et al. (1972). p-Diethylaminobenzoic acid and p-nitrobenzoic acid were used as received. Both complexes were prepared by a modification of the procedure reported by Doyle et al. (1990) for tetrakis(µ-acetamidato)dirhodium.

For the preparation of compound (I), [Rh₂(O₂CMe)₄(MeOH)₂] (0.327 g, 0.65 mmol) and p-diethylaminobenzoic acid (2.95 g, 1.53 mmol) dissolved in chlorobenzene (90 ml) were placed in a 200 ml round-bottomed flask. A Soxhlet apparatus, in which sodium carboxylate (3 g) and molecular sieves (1 g) were mixed in a filter, was placed on the flask. The solution was refluxed under an Ar atmosphere for 3 d. The resulting green precipitate was filtered off, dissolved in CH₂Cl₂–PhCN (1:1 v/v), washed with saturated aqueous NaHCO₃ and water, and dried over MgSO₄. Diffusion of ethanol into the solution gave a reddish–purple precipitate. Recrystallization from PhCN by slow diffusion of ethanol gave red crystals of (I).

For the preparation of compound (II), [Rh₂(O₂CMe)₄(MeOH)₂] (1.019 g, 2.01 mmol) and p-nitrobenzoic acid (6.00 g, 35.9 mm mol) were reacted in a similar method to (I). The resulting green precipitate was filtered off and dissolved in PhCN–hexane (1:1 v/v). The solution was washed with saturated aqueous NaHCO₃ and water, and dried over MgSO₄. Diffusion of hexane gave a red precipitate. This was dissolved in CH₂Cl₂ and pyridine was added until the colour of the solution changed to orange. The solid obtained by the evaporation of this solution to dryness was recrystallized from CH₂Cl₂ by slow diffusion of MeOH. Two types of crystals were obtained in an almost 1:1 ratio; one was (II) and the other was poor quality crystals of [Rh₂(O₂CC₆H₄NO₂)₂(py)₂].

S3. Refinement

For compound (I), one diethylaminophenyl group is disordered over two sites. Atoms C15A–C18A/C21A/C22A/N2A constitute one group and atoms C15B–C18B/C21B/C22B/N2B form the other, sharing atoms C13, C14, C19 and C20. The occupancies of sets A and B were refined and converged to 0.530 (1) and 0.470 (1), respectively. For compound (II), the solvated dichloromethane molecule is disordered over two sites, Cl1/Cl2/C35 and Cl3/Cl4/C36. The occupancies were refined and converged to 0.672 (3) and 0.328 (3), respectively. The positional parameters of the O-bound H atom in (I) [Should this be (II)?] were refined [Final O—H = ?], with U_iso(H) = 1.5U_eq(O). All other H atoms were placed in idealized positions and treated as riding atoms, with C—H distances in the range 0.93–0.98 Å and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C).

Computing details

For both compounds, data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and TEXSAN.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The crystal packing of (II). For the sake of clarity, H atoms except H1 have been omitted. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) 1 - x, 1 - y, -z; (iii) 2 - x, 1 - y, 1 - z.]

(I) bis(benzonitrile)tetrakis[µ-p-(diethylamino)benzoato- κ²O,O']dirhodium(II)(Rh—Rh) benzonitrile disolvate

Crystal data

[Rh2(C11H14NO2)4(C7H5N)2]·2C7H5N	Z = 1
Mr = 1387.23	F(000) = 718
TriclinicP1	Dx = 1.368 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 10.049 (4) Å	Cell parameters from 3948 reflections
b = 12.752 (6) Å	θ = 3.1–27.5°
c = 13.479 (6) Å	µ = 0.55 mm^−1
α = 98.641 (6)°	T = 296 K
β = 90.781 (6)°	Block, dark-red
γ = 99.424 (6)°	0.20 × 0.10 × 0.10 mm
V = 1683.3 (13) Å^3

Data collection

Rigaku/MSC Mercury CCD area-detector diffractometer	5661 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 14.62 pixels mm^-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −10→13
13963 measured reflections	k = −14→16
7660 independent reflections	l = −16→17

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0391P)^2] where P = (Fo^2 + 2Fc^2)/3
7660 reflections	(Δ/σ)max = 0.016
475 parameters	Δρmax = 0.52 e Å^−3
0 restraints	Δρmin = −0.71 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rh1	0.552152 (11)	0.421492 (9)	0.485928 (7)	0.02236 (3)
O1	0.73006 (9)	0.51287 (7)	0.54496 (6)	0.0303 (3)
O2	0.62944 (9)	0.66036 (7)	0.57133 (6)	0.0299 (3)
C1	0.73019 (14)	0.61217 (11)	0.57619 (8)	0.0251 (4)
C2	0.85701 (14)	0.67764 (11)	0.62264 (9)	0.0271 (4)
C3	0.97393 (14)	0.63500 (11)	0.63393 (9)	0.0308 (4)
H1	0.9753	0.5637	0.6069	0.037*
C4	1.08789 (15)	0.69553 (12)	0.68399 (9)	0.0355 (5)
H2	1.1636	0.6637	0.6914	0.043*
C5	1.09239 (15)	0.80456 (12)	0.72428 (9)	0.0347 (5)
C6	0.97561 (15)	0.84857 (12)	0.70855 (10)	0.0379 (5)
H3	0.9755	0.9212	0.7310	0.045*
C7	0.86136 (14)	0.78590 (11)	0.66046 (9)	0.0333 (4)
H4	0.7849	0.8169	0.6531	0.040*
N1	1.20521 (12)	0.86475 (10)	0.77475 (9)	0.0448 (4)
C8	1.20818 (17)	0.97993 (13)	0.81210 (12)	0.0588 (6)
H5	1.1692	1.0121	0.7603	0.071*
H6	1.3015	1.0148	0.8239	0.071*
C9	1.1340 (2)	1.00218 (17)	0.90689 (13)	0.0874 (8)
H7	1.0413	0.9682	0.8961	0.131*
H8	1.1386	1.0784	0.9253	0.131*
H9	1.1748	0.9741	0.9598	0.131*
C10	1.31034 (16)	0.81547 (15)	0.81423 (11)	0.0604 (6)
H10	1.3915	0.8689	0.8283	0.072*
H11	1.3306	0.7585	0.7634	0.072*
C11	1.2724 (2)	0.76896 (18)	0.90915 (12)	0.1005 (9)
H12	1.2620	0.8261	0.9621	0.151*
H13	1.3422	0.7320	0.9284	0.151*
H14	1.1889	0.7194	0.8970	0.151*
O3	0.50002 (9)	0.39384 (7)	0.62665 (6)	0.0285 (3)
O4	0.39815 (9)	0.54064 (7)	0.65149 (6)	0.0296 (3)
C12	0.43364 (13)	0.45797 (11)	0.67920 (9)	0.0270 (4)
C13	0.39445 (14)	0.43526 (11)	0.77973 (9)	0.0320 (4)
C14	0.45205 (16)	0.36432 (12)	0.82801 (10)	0.0399 (5)
H15	0.5248	0.3372	0.7982	0.048*	0.5339 (11)
H16	0.5072	0.3204	0.7938	0.048*	0.4661 (11)
C15A	0.4100 (3)	0.3302 (2)	0.91768 (17)	0.0361 (9)	0.5339 (11)
H17	0.4492	0.2793	0.9450	0.043*	0.5339 (11)
C16A	0.3041 (3)	0.3773 (2)	0.96514 (19)	0.0398 (9)	0.5339 (11)
C17A	0.2421 (3)	0.4450 (2)	0.91452 (18)	0.0435 (9)	0.5339 (11)
H18	0.1702	0.4739	0.9439	0.052*	0.5339 (11)
C18A	0.2823 (3)	0.4708 (2)	0.82403 (17)	0.0339 (8)	0.5339 (11)
H19	0.2342	0.5127	0.7913	0.041*	0.5339 (11)
N2A	0.2619 (3)	0.3531 (2)	1.05754 (16)	0.0475 (8)	0.5339 (11)
C19	0.3612 (2)	0.31944 (15)	1.12892 (11)	0.0650 (7)
H20	0.4541	0.3394	1.1110	0.078*	0.5339 (11)
H21	0.3508	0.3496	1.1983	0.078*	0.5339 (11)
H22	0.4576	0.3296	1.1191	0.078*	0.4661 (11)
H23	0.3512	0.3403	1.2003	0.078*	0.4661 (11)
C20	0.3171 (2)	0.20260 (16)	1.11041 (15)	0.0956 (9)
H24	0.2213	0.1866	1.1175	0.143*
H25	0.3622	0.1702	1.1580	0.143*
H26	0.3389	0.1745	1.0436	0.143*
C21A	0.1352 (3)	0.3818 (3)	1.0990 (2)	0.0533 (11)	0.5339 (11)
H27	0.0688	0.3756	1.0446	0.064*	0.5339 (11)
H28	0.1001	0.3315	1.1435	0.064*	0.5339 (11)
C22A	0.1556 (4)	0.4916 (3)	1.1547 (2)	0.0847 (16)	0.5339 (11)
H29	0.2162	0.4966	1.2115	0.127*	0.5339 (11)
H30	0.0705	0.5088	1.1774	0.127*	0.5339 (11)
H31	0.1933	0.5413	1.1115	0.127*	0.5339 (11)
N3	0.63450 (11)	0.26902 (9)	0.45682 (7)	0.0289 (3)
C23	0.65322 (14)	0.18222 (11)	0.44693 (9)	0.0293 (4)
C24	0.67660 (15)	0.07296 (11)	0.43877 (9)	0.0331 (4)
C25	0.58005 (17)	−0.01020 (12)	0.39092 (11)	0.0453 (5)
H32	0.5033	0.0049	0.3603	0.054*
C26	0.59831 (18)	−0.11516 (13)	0.38887 (12)	0.0548 (6)
H33	0.5334	−0.1714	0.3576	0.066*
C27	0.71266 (18)	−0.13652 (13)	0.43313 (12)	0.0563 (6)
H34	0.7250	−0.2074	0.4317	0.068*
C28	0.80813 (19)	−0.05491 (13)	0.47898 (12)	0.0576 (6)
H35	0.8850	−0.0707	0.5088	0.069*
C29	0.79253 (16)	0.05088 (12)	0.48190 (11)	0.0439 (5)
H36	0.8588	0.1064	0.5123	0.053*
N4	0.6152 (2)	0.10310 (16)	0.83623 (12)	0.1085 (9)
C30	0.7048 (2)	0.15151 (17)	0.80061 (13)	0.0774 (8)
C31	0.81370 (19)	0.21005 (15)	0.75547 (12)	0.0598 (6)
C32	0.79204 (19)	0.27358 (14)	0.68501 (11)	0.0564 (6)
H37	0.7041	0.2805	0.6682	0.068*
C33	0.89628 (19)	0.32648 (15)	0.63942 (13)	0.0634 (7)
H38	0.8792	0.3681	0.5912	0.076*
C34	1.0263 (2)	0.31881 (17)	0.66409 (15)	0.0834 (8)
H39	1.0980	0.3555	0.6335	0.100*
C35	1.0497 (2)	0.25543 (18)	0.73555 (16)	0.0952 (9)
H40	1.1381	0.2503	0.7529	0.114*
C36	0.9460 (2)	0.20057 (17)	0.78068 (15)	0.0834 (8)
H41	0.9630	0.1574	0.8276	0.100*
C15B	0.4265 (3)	0.3597 (2)	0.9275 (2)	0.0338 (10)	0.4661 (11)
H42	0.4729	0.3159	0.9593	0.041*	0.4661 (11)
C16B	0.3402 (3)	0.4130 (3)	0.9840 (2)	0.0349 (10)	0.4661 (11)
C17B	0.2857 (3)	0.4890 (3)	0.9367 (2)	0.0386 (10)	0.4661 (11)
H43	0.2271	0.5297	0.9708	0.046*	0.4661 (11)
C18B	0.3196 (3)	0.5029 (3)	0.8395 (2)	0.0356 (10)	0.4661 (11)
H44	0.2916	0.5593	0.8128	0.043*	0.4661 (11)
N2B	0.3119 (3)	0.4045 (2)	1.08063 (17)	0.0440 (9)	0.4661 (11)
C21B	0.2207 (4)	0.4668 (4)	1.1357 (2)	0.0716 (16)	0.4661 (11)
H45	0.2393	0.5399	1.1212	0.086*	0.4661 (11)
H46	0.2383	0.4695	1.2071	0.086*	0.4661 (11)
C22B	0.0685 (5)	0.4204 (4)	1.1101 (3)	0.105 (2)	0.4661 (11)
H47	0.0534	0.4051	1.0386	0.158*	0.4661 (11)
H48	0.0143	0.4722	1.1378	0.158*	0.4661 (11)
H49	0.0441	0.3554	1.1383	0.158*	0.4661 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.02241 (5)	0.02235 (5)	0.02284 (4)	0.00427 (4)	0.00088 (4)	0.00454 (4)
O1	0.0243 (5)	0.0277 (5)	0.0378 (5)	0.0056 (4)	−0.0043 (4)	0.0011 (4)
O2	0.0252 (5)	0.0266 (5)	0.0369 (5)	0.0035 (4)	−0.0029 (4)	0.0031 (4)
C1	0.0263 (7)	0.0303 (7)	0.0208 (6)	0.0028 (6)	0.0032 (5)	0.0121 (5)
C2	0.0231 (7)	0.0326 (8)	0.0254 (6)	0.0003 (6)	−0.0001 (6)	0.0082 (6)
C3	0.0285 (8)	0.0309 (8)	0.0326 (7)	0.0017 (7)	0.0023 (6)	0.0070 (6)
C4	0.0240 (8)	0.0456 (9)	0.0384 (7)	0.0041 (7)	−0.0019 (6)	0.0138 (7)
C5	0.0311 (8)	0.0433 (9)	0.0278 (6)	−0.0010 (7)	−0.0003 (6)	0.0079 (6)
C6	0.0340 (9)	0.0349 (8)	0.0403 (8)	−0.0005 (7)	−0.0049 (7)	−0.0007 (7)
C7	0.0271 (8)	0.0359 (8)	0.0379 (7)	0.0058 (7)	−0.0012 (6)	0.0087 (6)
N1	0.0305 (7)	0.0505 (8)	0.0468 (7)	−0.0048 (6)	−0.0131 (6)	0.0007 (6)
C8	0.0395 (10)	0.0640 (12)	0.0629 (10)	−0.0083 (9)	−0.0090 (9)	−0.0029 (9)
C9	0.0949 (16)	0.1037 (16)	0.0595 (11)	0.0295 (13)	−0.0153 (11)	−0.0124 (11)
C10	0.0347 (9)	0.0768 (13)	0.0610 (10)	0.0047 (9)	−0.0219 (8)	−0.0096 (9)
C11	0.1241 (16)	0.1501 (19)	0.0428 (10)	0.0803 (13)	−0.0129 (11)	0.0031 (11)
O3	0.0336 (5)	0.0292 (5)	0.0261 (4)	0.0107 (4)	0.0068 (4)	0.0089 (4)
O4	0.0349 (5)	0.0336 (5)	0.0241 (4)	0.0113 (4)	0.0080 (4)	0.0100 (4)
C12	0.0212 (7)	0.0323 (8)	0.0268 (6)	0.0005 (6)	0.0016 (6)	0.0071 (6)
C13	0.0334 (8)	0.0367 (8)	0.0286 (6)	0.0099 (7)	0.0073 (6)	0.0087 (6)
C14	0.0416 (9)	0.0519 (9)	0.0322 (7)	0.0222 (7)	0.0103 (6)	0.0094 (7)
C15A	0.0499 (17)	0.0332 (15)	0.0307 (12)	0.0169 (13)	0.0175 (12)	0.0107 (11)
C16A	0.0431 (17)	0.0496 (18)	0.0298 (13)	0.0114 (14)	0.0000 (12)	0.0121 (12)
C17A	0.0442 (17)	0.0597 (19)	0.0333 (13)	0.0252 (14)	0.0177 (12)	0.0094 (13)
C18A	0.0284 (15)	0.0482 (16)	0.0310 (12)	0.0146 (13)	0.0029 (11)	0.0165 (12)
N2A	0.0528 (16)	0.0617 (16)	0.0360 (11)	0.0198 (13)	0.0207 (11)	0.0203 (11)
C19	0.0783 (13)	0.0830 (13)	0.0395 (8)	0.0236 (11)	0.0127 (9)	0.0160 (9)
C20	0.0970 (18)	0.0988 (17)	0.0777 (13)	−0.0187 (15)	0.0234 (13)	0.0080 (12)
C21A	0.058 (2)	0.072 (2)	0.0411 (15)	0.0254 (17)	0.0192 (14)	0.0266 (14)
C22A	0.123 (3)	0.082 (3)	0.0554 (19)	0.024 (3)	0.034 (2)	0.0206 (19)
N3	0.0281 (7)	0.0260 (6)	0.0337 (6)	0.0060 (5)	0.0023 (5)	0.0060 (5)
C23	0.0275 (8)	0.0317 (8)	0.0293 (6)	0.0049 (6)	0.0041 (6)	0.0059 (6)
C24	0.0415 (9)	0.0248 (7)	0.0344 (7)	0.0085 (7)	0.0086 (7)	0.0055 (6)
C25	0.0421 (10)	0.0408 (9)	0.0525 (9)	0.0112 (8)	0.0047 (8)	0.0008 (8)
C26	0.0579 (12)	0.0317 (9)	0.0701 (10)	−0.0014 (8)	0.0180 (9)	0.0011 (8)
C27	0.0694 (12)	0.0296 (8)	0.0776 (11)	0.0173 (8)	0.0287 (9)	0.0210 (8)
C28	0.0632 (12)	0.0432 (9)	0.0760 (11)	0.0218 (9)	0.0030 (9)	0.0265 (8)
C29	0.0446 (10)	0.0347 (9)	0.0560 (9)	0.0137 (8)	0.0001 (8)	0.0114 (7)
N4	0.1033 (16)	0.1449 (18)	0.0730 (11)	−0.0077 (14)	−0.0105 (11)	0.0353 (11)
C30	0.0810 (15)	0.0991 (16)	0.0507 (10)	0.0080 (13)	−0.0138 (10)	0.0164 (10)
C31	0.0566 (12)	0.0717 (13)	0.0499 (9)	0.0110 (10)	0.0004 (9)	0.0052 (9)
C32	0.0569 (11)	0.0647 (11)	0.0470 (9)	0.0179 (9)	−0.0052 (8)	−0.0007 (8)
C33	0.0590 (12)	0.0615 (12)	0.0726 (11)	0.0157 (10)	−0.0056 (10)	0.0141 (9)
C34	0.0599 (14)	0.0911 (16)	0.1027 (15)	0.0137 (12)	0.0121 (12)	0.0239 (13)
C35	0.0626 (14)	0.1208 (18)	0.1132 (16)	0.0381 (13)	−0.0062 (13)	0.0297 (14)
C36	0.0853 (16)	0.0913 (15)	0.0850 (13)	0.0277 (13)	−0.0004 (12)	0.0360 (11)
C15B	0.046 (2)	0.0218 (15)	0.0393 (16)	0.0142 (14)	−0.0093 (15)	0.0139 (13)
C16B	0.042 (2)	0.047 (2)	0.0173 (13)	0.0136 (16)	0.0057 (13)	0.0033 (13)
C17B	0.054 (2)	0.0409 (18)	0.0293 (15)	0.0267 (15)	0.0165 (14)	0.0102 (14)
C18B	0.037 (2)	0.0357 (18)	0.0343 (16)	0.0061 (16)	0.0026 (15)	0.0072 (14)
N2B	0.0512 (18)	0.0590 (18)	0.0262 (12)	0.0158 (15)	0.0095 (12)	0.0129 (12)
C21B	0.091 (3)	0.102 (3)	0.0290 (17)	0.031 (3)	0.0257 (19)	0.0138 (19)
C22B	0.077 (3)	0.187 (5)	0.075 (3)	0.058 (3)	0.027 (2)	0.051 (3)

Geometric parameters (Å, º)

Rh1—Rh1^i	2.3920 (9)	C19—C20	1.465 (3)
Rh1—O1	2.0463 (10)	C19—N2B	1.492 (4)
Rh1—O2^i	2.0276 (10)	C19—H20	0.9700
Rh1—O3	2.0407 (12)	C19—H21	0.9700
Rh1—O4^i	2.0318 (12)	C19—H22	0.9700
Rh1—N3	2.2194 (14)	C19—H23	0.9700
O1—C1	1.2728 (16)	C20—H24	0.9600
O2—C1	1.2732 (18)	C20—H25	0.9600
O2—Rh1^i	2.0276 (10)	C20—H26	0.9600
C1—C2	1.4784 (18)	C21A—C22A	1.467 (4)
C2—C3	1.389 (2)	C21A—H27	0.9700
C2—C7	1.391 (2)	C21A—H28	0.9700
C3—C4	1.3767 (18)	C22A—H29	0.9600
C3—H1	0.9300	C22A—H30	0.9600
C4—C5	1.408 (2)	C22A—H31	0.9600
C4—H2	0.9300	N3—C23	1.1415 (19)
C5—N1	1.3691 (18)	C23—C24	1.439 (2)
C5—C6	1.408 (2)	C24—C29	1.383 (2)
C6—C7	1.3786 (19)	C24—C25	1.3865 (19)
C6—H3	0.9300	C25—C26	1.377 (2)
C7—H4	0.9300	C25—H32	0.9300
N1—C10	1.448 (2)	C26—C27	1.372 (3)
N1—C8	1.475 (2)	C26—H33	0.9300
C8—C9	1.501 (2)	C27—C28	1.360 (2)
C8—H5	0.9700	C27—H34	0.9300
C8—H6	0.9700	C28—C29	1.378 (2)
C9—H7	0.9600	C28—H35	0.9300
C9—H8	0.9600	C29—H36	0.9300
C9—H9	0.9600	N4—C30	1.158 (3)
C10—C11	1.517 (3)	C30—C31	1.419 (3)
C10—H10	0.9700	C31—C32	1.374 (3)
C10—H11	0.9700	C31—C36	1.397 (3)
C11—H12	0.9600	C32—C33	1.357 (3)
C11—H13	0.9600	C32—H37	0.9300
C11—H14	0.9600	C33—C34	1.366 (3)
O3—C12	1.2778 (16)	C33—H38	0.9300
O4—C12	1.2712 (18)	C34—C35	1.388 (3)
O4—Rh1^i	2.0318 (11)	C34—H39	0.9300
C12—C13	1.4731 (19)	C35—C36	1.361 (3)
C13—C14	1.384 (2)	C35—H40	0.9300
C13—C18A	1.391 (3)	C36—H41	0.9300
C13—C18B	1.407 (4)	C15B—C16B	1.359 (5)
C14—C15B	1.377 (3)	C15B—H42	0.9300
C14—C15A	1.393 (3)	C16B—N2B	1.354 (4)
C14—H15	0.9300	C16B—C17B	1.412 (5)
C14—H16	0.9300	C17B—C18B	1.388 (4)
C15A—C16A	1.420 (4)	C17B—H43	0.9300
C15A—H17	0.9300	C18B—H44	0.9300
C16A—N2A	1.383 (3)	N2B—C21B	1.449 (5)
C16A—C17A	1.393 (4)	C21B—C22B	1.561 (6)
C17A—C18A	1.360 (4)	C21B—H45	0.9700
C17A—H18	0.9300	C21B—H46	0.9700
C18A—H19	0.9300	C22B—H47	0.9600
N2A—C21A	1.476 (4)	C22B—H48	0.9600
N2A—C19	1.531 (3)	C22B—H49	0.9600
Rh1^i—Rh1—O1	89.16 (4)	C20—C19—N2B	129.38 (18)
Rh1^i—Rh1—O2^i	87.17 (4)	C20—C19—N2A	99.70 (16)
Rh1^i—Rh1—O3	88.20 (3)	C20—C19—H20	111.8
Rh1^i—Rh1—O4^i	88.11 (3)	N2B—C19—H20	94.1
Rh1^i—Rh1—N3	175.93 (3)	N2A—C19—H20	111.8
O1—Rh1—O2^i	176.33 (4)	C20—C19—H21	111.8
O1—Rh1—O3	89.53 (4)	N2B—C19—H21	97.9
O1—Rh1—O4^i	89.30 (4)	N2A—C19—H21	111.8
O1—Rh1—N3	94.87 (5)	H20—C19—H21	109.6
O2^i—Rh1—O3	90.51 (4)	C20—C19—H22	104.9
O2^i—Rh1—O4^i	90.44 (4)	N2B—C19—H22	104.9
O2^i—Rh1—N3	88.80 (5)	N2A—C19—H22	122.3
O3—Rh1—O4^i	176.14 (4)	H21—C19—H22	105.9
O3—Rh1—N3	91.29 (4)	C20—C19—H23	104.9
O4^i—Rh1—N3	92.47 (4)	N2B—C19—H23	104.9
C1—O1—Rh1	117.60 (9)	N2A—C19—H23	116.9
C1—O2—Rh1^i	120.65 (8)	H20—C19—H23	110.9
O1—C1—O2	125.39 (11)	H22—C19—H23	105.8
O1—C1—C2	117.84 (13)	C19—C20—H24	109.5
O2—C1—C2	116.77 (12)	C19—C20—H25	109.5
C3—C2—C7	117.15 (12)	H24—C20—H25	109.5
C3—C2—C1	122.76 (12)	C19—C20—H26	109.5
C7—C2—C1	120.06 (13)	H24—C20—H26	109.5
C4—C3—C2	121.76 (13)	H25—C20—H26	109.5
C4—C3—H1	119.1	C22A—C21A—N2A	111.8 (3)
C2—C3—H1	119.1	C22A—C21A—H27	109.3
C3—C4—C5	121.48 (14)	N2A—C21A—H27	109.3
C3—C4—H2	119.3	C22A—C21A—H28	109.3
C5—C4—H2	119.3	N2A—C21A—H28	109.3
N1—C5—C6	121.94 (13)	H27—C21A—H28	107.9
N1—C5—C4	121.62 (14)	C23—N3—Rh1	166.99 (11)
C6—C5—C4	116.44 (12)	N3—C23—C24	177.70 (13)
C7—C6—C5	121.14 (14)	C29—C24—C25	120.24 (14)
C7—C6—H3	119.4	C29—C24—C23	120.02 (12)
C5—C6—H3	119.4	C25—C24—C23	119.69 (14)
C6—C7—C2	121.94 (14)	C26—C25—C24	119.69 (16)
C6—C7—H4	119.0	C26—C25—H32	120.2
C2—C7—H4	119.0	C24—C25—H32	120.2
C5—N1—C10	121.85 (14)	C27—C26—C25	119.73 (14)
C5—N1—C8	120.05 (14)	C27—C26—H33	120.1
C10—N1—C8	116.48 (12)	C25—C26—H33	120.1
N1—C8—C9	114.46 (15)	C28—C27—C26	120.58 (16)
N1—C8—H5	108.6	C28—C27—H34	119.7
C9—C8—H5	108.6	C26—C27—H34	119.7
N1—C8—H6	108.6	C27—C28—C29	120.88 (17)
C9—C8—H6	108.6	C27—C28—H35	119.6
H5—C8—H6	107.6	C29—C28—H35	119.6
C8—C9—H7	109.5	C28—C29—C24	118.86 (14)
C8—C9—H8	109.5	C28—C29—H36	120.6
H7—C9—H8	109.5	C24—C29—H36	120.6
C8—C9—H9	109.5	N4—C30—C31	179.1 (2)
H7—C9—H9	109.5	C32—C31—C36	119.02 (18)
H8—C9—H9	109.5	C32—C31—C30	121.49 (18)
N1—C10—C11	113.23 (15)	C36—C31—C30	119.46 (19)
N1—C10—H10	108.9	C33—C32—C31	121.34 (18)
C11—C10—H10	108.9	C33—C32—H37	119.3
N1—C10—H11	108.9	C31—C32—H37	119.3
C11—C10—H11	108.9	C32—C33—C34	120.26 (19)
H10—C10—H11	107.7	C32—C33—H38	119.9
C10—C11—H12	109.5	C34—C33—H38	119.9
C10—C11—H13	109.5	C33—C34—C35	119.0 (2)
H12—C11—H13	109.5	C33—C34—H39	120.5
C10—C11—H14	109.5	C35—C34—H39	120.5
H12—C11—H14	109.5	C36—C35—C34	121.3 (2)
H13—C11—H14	109.5	C36—C35—H40	119.3
C12—O3—Rh1	118.97 (9)	C34—C35—H40	119.3
C12—O4—Rh1^i	119.68 (8)	C35—C36—C31	119.0 (2)
O4—C12—O3	125.02 (12)	C35—C36—H41	120.5
O4—C12—C13	116.87 (12)	C31—C36—H41	120.5
O3—C12—C13	118.11 (13)	C16B—C15B—C14	126.4 (3)
C14—C13—C18A	115.90 (16)	C16B—C15B—H42	116.8
C14—C13—C18B	116.21 (17)	C14—C15B—H42	116.8
C14—C13—C12	122.34 (13)	N2B—C16B—C15B	125.9 (3)
C18A—C13—C12	120.99 (16)	N2B—C16B—C17B	119.3 (3)
C18B—C13—C12	119.96 (18)	C15B—C16B—C17B	114.6 (3)
C15B—C14—C13	119.02 (19)	C18B—C17B—C16B	120.2 (3)
C13—C14—C15A	125.33 (18)	C18B—C17B—H43	119.9
C13—C14—H15	117.3	C16B—C17B—H43	119.9
C15A—C14—H15	117.3	C17B—C18B—C13	122.6 (3)
C15B—C14—H16	120.5	C17B—C18B—H44	118.7
C13—C14—H16	120.5	C13—C18B—H44	118.7
C15A—C14—H16	112.1	C16B—N2B—C21B	122.0 (3)
C14—C15A—C16A	116.5 (2)	C16B—N2B—C19	119.6 (3)
C14—C15A—H17	121.8	C21B—N2B—C19	117.9 (2)
C16A—C15A—H17	121.8	N2B—C21B—C22B	113.6 (3)
N2A—C16A—C17A	121.6 (3)	N2B—C21B—H45	108.8
N2A—C16A—C15A	120.2 (3)	C22B—C21B—H45	108.8
C17A—C16A—C15A	118.1 (2)	N2B—C21B—H46	108.9
C18A—C17A—C16A	122.8 (3)	C22B—C21B—H46	108.9
C18A—C17A—H18	118.6	H45—C21B—H46	107.7
C16A—C17A—H18	118.6	C21B—C22B—H47	109.5
C17A—C18A—C13	121.0 (3)	C21B—C22B—H48	109.5
C17A—C18A—H19	119.5	H47—C22B—H48	109.5
C13—C18A—H19	119.5	C21B—C22B—H49	109.5
C16A—N2A—C21A	121.5 (3)	H47—C22B—H49	109.5
C16A—N2A—C19	119.5 (2)	H48—C22B—H49	109.5
C21A—N2A—C19	117.6 (2)
O1—Rh1—Rh1^i—O2	−0.15 (4)	C14—C15A—C16A—N2A	−176.0 (2)
O3—Rh1—Rh1^i—O4	−1.13 (3)	C14—C15A—C16A—C17A	6.1 (3)
O4^i—Rh1—O1—C1	89.17 (9)	N2A—C16A—C17A—C18A	179.5 (2)
O3—Rh1—O1—C1	−87.15 (9)	C15A—C16A—C17A—C18A	−2.6 (4)
N3—Rh1—O1—C1	−178.41 (9)	C16A—C17A—C18A—C13	−4.0 (4)
Rh1^i—Rh1—O1—C1	1.06 (8)	C14—C13—C18A—C17A	6.4 (3)
Rh1—O1—C1—O2	−2.01 (16)	C12—C13—C18A—C17A	176.57 (19)
Rh1—O1—C1—C2	177.59 (8)	C17A—C16A—N2A—C21A	10.9 (4)
Rh1^i—O2—C1—O1	1.89 (16)	C15A—C16A—N2A—C21A	−167.0 (2)
Rh1^i—O2—C1—C2	−177.72 (8)	C17A—C16A—N2A—C19	−155.2 (2)
O1—C1—C2—C3	−0.51 (18)	C15A—C16A—N2A—C19	27.0 (3)
O2—C1—C2—C3	179.13 (12)	C16A—N2A—C19—C20	−100.5 (2)
O1—C1—C2—C7	−178.23 (11)	C21A—N2A—C19—C20	92.9 (2)
O2—C1—C2—C7	1.41 (17)	C16A—N2A—C21A—C22A	−86.5 (3)
C7—C2—C3—C4	2.65 (19)	C19—N2A—C21A—C22A	79.8 (3)
C1—C2—C3—C4	−175.13 (12)	O2^i—Rh1—N3—C23	−36.5 (4)
C2—C3—C4—C5	−1.5 (2)	O4^i—Rh1—N3—C23	−126.9 (4)
C3—C4—C5—N1	179.51 (13)	O3—Rh1—N3—C23	53.9 (4)
C3—C4—C5—C6	−1.4 (2)	O1—Rh1—N3—C23	143.6 (4)
N1—C5—C6—C7	−177.84 (13)	C29—C24—C25—C26	1.8 (2)
C4—C5—C6—C7	3.1 (2)	C23—C24—C25—C26	−175.74 (14)
C5—C6—C7—C2	−2.0 (2)	C24—C25—C26—C27	−0.8 (2)
C3—C2—C7—C6	−0.9 (2)	C25—C26—C27—C28	0.0 (3)
C1—C2—C7—C6	176.90 (12)	C26—C27—C28—C29	−0.1 (3)
C6—C5—N1—C10	163.30 (14)	C27—C28—C29—C24	1.1 (2)
C4—C5—N1—C10	−17.7 (2)	C25—C24—C29—C28	−1.9 (2)
C6—C5—N1—C8	−1.7 (2)	C23—C24—C29—C28	175.59 (14)
C4—C5—N1—C8	177.37 (13)	C36—C31—C32—C33	0.3 (3)
C5—N1—C8—C9	78.16 (19)	C30—C31—C32—C33	−177.67 (17)
C10—N1—C8—C9	−87.58 (18)	C31—C32—C33—C34	−1.0 (3)
C5—N1—C10—C11	−75.91 (18)	C32—C33—C34—C35	0.6 (3)
C8—N1—C10—C11	89.55 (17)	C33—C34—C35—C36	0.4 (3)
O2^i—Rh1—O3—C12	−85.58 (9)	C34—C35—C36—C31	−1.1 (3)
O1—Rh1—O3—C12	90.76 (9)	C32—C31—C36—C35	0.7 (3)
N3—Rh1—O3—C12	−174.38 (9)	C30—C31—C36—C35	178.76 (18)
Rh1^i—Rh1—O3—C12	1.58 (8)	C13—C14—C15B—C16B	5.4 (4)
Rh1^i—O4—C12—O3	−0.13 (16)	C14—C15B—C16B—N2B	177.2 (3)
Rh1^i—O4—C12—C13	179.94 (8)	C14—C15B—C16B—C17B	−7.9 (4)
Rh1—O3—C12—O4	−1.23 (16)	N2B—C16B—C17B—C18B	176.4 (3)
Rh1—O3—C12—C13	178.70 (8)	C15B—C16B—C17B—C18B	1.2 (4)
O4—C12—C13—C14	−164.63 (12)	C16B—C17B—C18B—C13	7.8 (5)
O3—C12—C13—C14	15.44 (18)	C14—C13—C18B—C17B	−10.2 (4)
O4—C12—C13—C18A	25.9 (2)	C12—C13—C18B—C17B	−176.6 (2)
O3—C12—C13—C18A	−154.05 (16)	C15B—C16B—N2B—C21B	178.4 (3)
O4—C12—C13—C18B	0.9 (2)	C17B—C16B—N2B—C21B	3.7 (5)
O3—C12—C13—C18B	−179.06 (17)	C15B—C16B—N2B—C19	−9.5 (5)
C18B—C13—C14—C15B	3.8 (3)	C17B—C16B—N2B—C19	175.9 (2)
C12—C13—C14—C15B	169.83 (18)	C20—C19—N2B—C16B	−70.6 (4)
C18A—C13—C14—C15A	−2.7 (2)	C20—C19—N2B—C21B	101.9 (3)
C12—C13—C14—C15A	−172.64 (16)	C16B—N2B—C21B—C22B	78.9 (4)
C13—C14—C15A—C16A	−3.6 (3)	C19—N2B—C21B—C22B	−93.4 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

(II) (methanol)tetrakis(µ-p-nitrobenzoato- κ²O,O')(pyridine)dirhodium(II)(Rh—Rh) dichloromethane solvate, [Rh₂(C₇H₄NO₄)₄(C₂H₄O)(C₅H₅N)]·CH₂Cl₂

Crystal data

[Rh2(C7H4NO4)4(C2H4O)(C5H5N)]·CH2Cl2	Z = 2
Mr = 1066.34	F(000) = 1064
TriclinicP1	Dx = 1.806 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71070 Å
a = 12.750 (6) Å	Cell parameters from 5195 reflections
b = 13.290 (4) Å	θ = 3.0–27.5°
c = 14.773 (5) Å	µ = 1.06 mm^−1
α = 96.55 (3)°	T = 113 K
β = 109.42 (1)°	Block, dark-red
γ = 118.43 (1)°	0.30 × 0.10 × 0.10 mm
V = 1961.0 (13) Å^3

Data collection

Rigaku/MSC Mercury CCD area-detector diffractometer	6931 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
Detector resolution: 14.62 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ω scans	h = −16→16
16189 measured reflections	k = −17→13
8932 independent reflections	l = −12→19

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0533P)^2 + 2.6928P] where P = (Fo^2 + 2Fc^2)/3
8932 reflections	(Δ/σ)max = 0.001
577 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −1.05 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rh1	0.65481 (3)	0.45721 (2)	0.28436 (2)	0.01313 (9)
Rh2	0.48824 (3)	0.39051 (2)	0.34454 (2)	0.01327 (9)
O1	0.6812 (3)	0.6242 (2)	0.3173 (2)	0.0196 (6)
O2	0.5260 (3)	0.5609 (2)	0.3755 (2)	0.0220 (6)
O3	0.8234 (3)	1.2025 (3)	0.4742 (3)	0.0353 (8)
O4	0.6737 (3)	1.1383 (3)	0.5294 (2)	0.0309 (7)
O5	0.7915 (3)	0.5082 (2)	0.4296 (2)	0.0183 (6)
O6	0.6337 (3)	0.4434 (3)	0.4852 (2)	0.0206 (6)
O7	1.2647 (3)	0.7855 (3)	0.9301 (2)	0.0316 (7)
O8	1.1089 (3)	0.7131 (3)	0.9790 (2)	0.0321 (7)
O9	0.6176 (3)	0.2860 (2)	0.2560 (2)	0.0195 (6)
O10	0.4603 (3)	0.2251 (2)	0.3126 (2)	0.0230 (6)
O11	0.4497 (4)	−0.3047 (3)	0.1239 (3)	0.0368 (8)
O12	0.3019 (3)	−0.3563 (3)	0.1814 (3)	0.0318 (8)
O13	0.5075 (3)	0.4038 (2)	0.1432 (2)	0.0180 (6)
O14	0.3514 (3)	0.3426 (3)	0.2010 (2)	0.0246 (6)
O15	0.0097 (3)	0.1383 (3)	−0.3450 (2)	0.0351 (8)
O16	−0.1368 (3)	0.0902 (3)	−0.2881 (2)	0.0289 (7)
O17	0.3274 (3)	0.3247 (3)	0.4007 (2)	0.0180 (6)
H1	0.331 (5)	0.349 (4)	0.444 (4)	0.027*
N1	0.7357 (4)	1.1217 (3)	0.4882 (3)	0.0237 (8)
N2	1.1473 (4)	0.7256 (3)	0.9124 (3)	0.0236 (8)
N3	0.3914 (4)	−0.2804 (3)	0.1650 (3)	0.0225 (8)
N4	−0.0212 (3)	0.1375 (3)	−0.2746 (3)	0.0211 (7)
N5	0.8072 (3)	0.5171 (3)	0.2266 (2)	0.0126 (6)
C1	0.6140 (4)	0.6407 (3)	0.3568 (3)	0.0167 (8)
C2	0.6431 (4)	0.7659 (3)	0.3880 (3)	0.0168 (8)
C3	0.7495 (4)	0.8627 (3)	0.3828 (3)	0.0200 (8)
H2	0.8020	0.8485	0.3569	0.024*
C4	0.7802 (4)	0.9790 (4)	0.4147 (3)	0.0237 (9)
H3	0.8527	1.0449	0.4107	0.028*
C5	0.7026 (4)	0.9971 (3)	0.4527 (3)	0.0173 (8)
C6	0.5973 (4)	0.9037 (4)	0.4603 (3)	0.0205 (8)
H4	0.5466	0.9189	0.4877	0.025*
C7	0.5674 (4)	0.7876 (4)	0.4270 (3)	0.0191 (8)
H5	0.4945	0.7219	0.4309	0.023*
C8	0.7537 (4)	0.4958 (3)	0.4991 (3)	0.0152 (8)
C9	0.8570 (4)	0.5497 (3)	0.6067 (3)	0.0172 (8)
C10	0.9918 (4)	0.6106 (3)	0.6299 (3)	0.0168 (8)
H6	1.0180	0.6128	0.5766	0.020*
C11	1.0873 (4)	0.6678 (3)	0.7296 (3)	0.0195 (8)
H7	1.1791	0.7092	0.7458	0.023*
C12	1.0463 (4)	0.6636 (3)	0.8059 (3)	0.0197 (8)
C13	0.9121 (4)	0.6013 (3)	0.7851 (3)	0.0187 (8)
H8	0.8862	0.5984	0.8386	0.022*
C14	0.8179 (4)	0.5440 (3)	0.6848 (3)	0.0187 (8)
H9	0.7260	0.5004	0.6688	0.022*
C15	0.5283 (4)	0.2072 (3)	0.2751 (3)	0.0172 (8)
C16	0.4987 (4)	0.0815 (3)	0.2501 (3)	0.0179 (8)
C17	0.5565 (5)	0.0485 (4)	0.1980 (4)	0.0283 (10)
H10	0.6191	0.1071	0.1804	0.034*
C18	0.5228 (5)	−0.0700 (4)	0.1717 (4)	0.0280 (10)
H11	0.5632	−0.0929	0.1374	0.034*
C19	0.4299 (4)	−0.1541 (3)	0.1961 (3)	0.0195 (8)
C20	0.3714 (4)	−0.1232 (4)	0.2477 (3)	0.0217 (9)
H12	0.3077	−0.1826	0.2640	0.026*
C21	0.4067 (4)	−0.0047 (3)	0.2753 (3)	0.0209 (9)
H13	0.3680	0.0180	0.3116	0.025*
C22	0.3891 (4)	0.3558 (3)	0.1317 (3)	0.0169 (8)
C23	0.2829 (4)	0.3072 (3)	0.0256 (3)	0.0177 (8)
C24	0.3151 (4)	0.3186 (3)	−0.0560 (3)	0.0183 (8)
H14	0.4057	0.3637	−0.0436	0.022*
C25	0.2158 (4)	0.2645 (3)	−0.1543 (3)	0.0181 (8)
H15	0.2368	0.2724	−0.2102	0.022*
C26	0.0846 (4)	0.1982 (3)	−0.1699 (3)	0.0181 (8)
C27	0.0493 (4)	0.1890 (4)	−0.0914 (3)	0.0218 (9)
H16	−0.0416	0.1462	−0.1045	0.026*
C28	0.1493 (4)	0.2436 (4)	0.0072 (3)	0.0219 (9)
H17	0.1272	0.2378	0.0626	0.026*
C29	0.9372 (4)	0.5897 (3)	0.2916 (3)	0.0158 (8)
H18	0.9626	0.6144	0.3624	0.019*
C30	1.0343 (4)	0.6290 (3)	0.2587 (3)	0.0198 (8)
H19	1.1255	0.6799	0.3060	0.024*
C31	0.9966 (4)	0.5929 (4)	0.1540 (3)	0.0231 (9)
H20	1.0615	0.6193	0.1290	0.028*
C32	0.8629 (4)	0.5181 (3)	0.0884 (3)	0.0187 (8)
H21	0.8345	0.4920	0.0172	0.022*
C33	0.7709 (4)	0.4814 (3)	0.1266 (3)	0.0172 (8)
H22	0.6790	0.4294	0.0809	0.021*
C34	0.2082 (5)	0.2092 (4)	0.3509 (4)	0.0328 (11)
H23	0.1619	0.2007	0.2799	0.049*
H24	0.1512	0.1997	0.3847	0.049*
H25	0.2285	0.1468	0.3536	0.049*
Cl1	0.8365 (3)	0.0287 (2)	0.1603 (2)	0.0666 (9)	0.672 (3)
Cl2	0.7855 (3)	−0.0314 (2)	−0.0540 (2)	0.0672 (8)	0.672 (3)
C35	0.7184 (10)	−0.0394 (8)	0.0300 (10)	0.069 (3)	0.672 (3)
H26	0.6537	−0.1257	0.0177	0.083*	0.672 (3)
H27	0.6688	0.0005	0.0162	0.083*	0.672 (3)
Cl3	0.8996 (6)	0.0533 (5)	0.0948 (5)	0.075 (2)	0.328 (3)
Cl4	0.6120 (7)	−0.1059 (5)	−0.0202 (4)	0.0692 (18)	0.328 (3)
C36	0.754 (2)	−0.0111 (19)	−0.0202 (16)	0.046 (5)*	0.328 (3)
H28	0.7489	0.0558	−0.0401	0.055*	0.328 (3)
H29	0.7629	−0.0538	−0.0735	0.055*	0.328 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01197 (17)	0.01514 (15)	0.01285 (17)	0.00688 (13)	0.00705 (13)	0.00426 (12)
Rh2	0.01196 (16)	0.01534 (15)	0.01294 (16)	0.00685 (13)	0.00706 (13)	0.00429 (12)
O1	0.0211 (15)	0.0187 (13)	0.0275 (16)	0.0116 (12)	0.0180 (14)	0.0086 (12)
O2	0.0287 (17)	0.0204 (14)	0.0328 (17)	0.0160 (13)	0.0248 (15)	0.0143 (13)
O3	0.038 (2)	0.0186 (15)	0.045 (2)	0.0106 (15)	0.0219 (18)	0.0076 (14)
O4	0.0260 (18)	0.0267 (16)	0.0365 (19)	0.0163 (14)	0.0113 (16)	−0.0016 (14)
O5	0.0109 (14)	0.0258 (14)	0.0125 (14)	0.0060 (12)	0.0056 (12)	0.0057 (11)
O6	0.0157 (15)	0.0312 (15)	0.0162 (15)	0.0117 (13)	0.0094 (13)	0.0106 (12)
O7	0.0174 (17)	0.0325 (17)	0.0234 (17)	0.0049 (14)	0.0015 (14)	0.0030 (14)
O8	0.036 (2)	0.0429 (19)	0.0140 (16)	0.0205 (16)	0.0106 (15)	0.0062 (14)
O9	0.0206 (15)	0.0181 (13)	0.0279 (16)	0.0114 (12)	0.0174 (14)	0.0100 (12)
O10	0.0225 (16)	0.0151 (13)	0.0356 (18)	0.0077 (12)	0.0216 (15)	0.0068 (12)
O11	0.042 (2)	0.0254 (16)	0.047 (2)	0.0192 (16)	0.0256 (19)	0.0030 (15)
O12	0.0347 (19)	0.0203 (15)	0.038 (2)	0.0119 (14)	0.0178 (17)	0.0118 (14)
O13	0.0138 (14)	0.0243 (14)	0.0155 (14)	0.0097 (12)	0.0071 (12)	0.0074 (12)
O14	0.0126 (15)	0.0380 (17)	0.0138 (15)	0.0090 (13)	0.0048 (13)	0.0041 (13)
O15	0.0231 (18)	0.057 (2)	0.0162 (17)	0.0184 (16)	0.0076 (15)	0.0021 (15)
O16	0.0121 (15)	0.0347 (17)	0.0247 (17)	0.0072 (13)	0.0034 (13)	0.0007 (14)
O17	0.0170 (15)	0.0198 (14)	0.0184 (16)	0.0084 (12)	0.0119 (13)	0.0048 (12)
N1	0.0210 (19)	0.0224 (17)	0.0209 (19)	0.0115 (16)	0.0043 (16)	0.0022 (15)
N2	0.028 (2)	0.0216 (17)	0.0162 (18)	0.0125 (16)	0.0069 (16)	0.0043 (14)
N3	0.0205 (19)	0.0176 (16)	0.0223 (19)	0.0090 (15)	0.0055 (16)	0.0025 (14)
N4	0.0195 (19)	0.0218 (17)	0.0193 (19)	0.0108 (15)	0.0076 (16)	0.0040 (15)
N5	0.0120 (16)	0.0128 (14)	0.0135 (16)	0.0069 (13)	0.0058 (14)	0.0054 (12)
C1	0.017 (2)	0.0229 (19)	0.015 (2)	0.0125 (17)	0.0084 (17)	0.0078 (16)
C2	0.015 (2)	0.0225 (19)	0.0124 (19)	0.0104 (17)	0.0050 (16)	0.0062 (16)
C3	0.019 (2)	0.0194 (19)	0.024 (2)	0.0111 (17)	0.0125 (18)	0.0031 (17)
C4	0.021 (2)	0.021 (2)	0.024 (2)	0.0088 (18)	0.0107 (19)	0.0044 (17)
C5	0.019 (2)	0.0169 (18)	0.0117 (19)	0.0103 (16)	0.0030 (16)	0.0002 (15)
C6	0.020 (2)	0.027 (2)	0.018 (2)	0.0165 (18)	0.0076 (18)	0.0062 (17)
C7	0.015 (2)	0.0212 (19)	0.020 (2)	0.0099 (17)	0.0077 (17)	0.0073 (17)
C8	0.015 (2)	0.0140 (17)	0.019 (2)	0.0084 (16)	0.0086 (17)	0.0069 (15)
C9	0.018 (2)	0.0160 (18)	0.019 (2)	0.0084 (16)	0.0093 (18)	0.0086 (16)
C10	0.018 (2)	0.0194 (18)	0.017 (2)	0.0111 (17)	0.0100 (17)	0.0090 (16)
C11	0.017 (2)	0.0193 (19)	0.021 (2)	0.0082 (17)	0.0084 (18)	0.0089 (17)
C12	0.023 (2)	0.0161 (18)	0.017 (2)	0.0107 (17)	0.0058 (18)	0.0045 (16)
C13	0.022 (2)	0.0230 (19)	0.017 (2)	0.0132 (18)	0.0132 (18)	0.0067 (16)
C14	0.015 (2)	0.0189 (19)	0.023 (2)	0.0081 (16)	0.0094 (18)	0.0101 (17)
C15	0.016 (2)	0.0178 (18)	0.015 (2)	0.0067 (16)	0.0079 (17)	0.0043 (15)
C16	0.018 (2)	0.0190 (18)	0.021 (2)	0.0107 (17)	0.0116 (18)	0.0064 (16)
C17	0.031 (3)	0.021 (2)	0.040 (3)	0.013 (2)	0.026 (2)	0.0102 (19)
C18	0.030 (3)	0.020 (2)	0.039 (3)	0.0124 (19)	0.023 (2)	0.0047 (19)
C19	0.017 (2)	0.0150 (18)	0.020 (2)	0.0060 (16)	0.0048 (17)	0.0039 (16)
C20	0.016 (2)	0.0186 (19)	0.023 (2)	0.0042 (17)	0.0093 (18)	0.0054 (17)
C21	0.021 (2)	0.0204 (19)	0.025 (2)	0.0110 (18)	0.0156 (19)	0.0075 (17)
C22	0.018 (2)	0.0185 (18)	0.015 (2)	0.0096 (17)	0.0091 (17)	0.0053 (15)
C23	0.016 (2)	0.0200 (18)	0.017 (2)	0.0098 (17)	0.0084 (17)	0.0044 (16)
C24	0.016 (2)	0.0217 (19)	0.018 (2)	0.0095 (17)	0.0094 (17)	0.0087 (16)
C25	0.019 (2)	0.0202 (19)	0.015 (2)	0.0101 (17)	0.0087 (17)	0.0053 (16)
C26	0.014 (2)	0.0170 (18)	0.016 (2)	0.0061 (16)	0.0039 (17)	0.0020 (15)
C27	0.015 (2)	0.028 (2)	0.021 (2)	0.0100 (18)	0.0096 (18)	0.0076 (18)
C28	0.021 (2)	0.031 (2)	0.018 (2)	0.0138 (19)	0.0122 (19)	0.0095 (18)
C29	0.016 (2)	0.0156 (17)	0.0131 (19)	0.0082 (16)	0.0048 (16)	0.0038 (15)
C30	0.016 (2)	0.0190 (19)	0.024 (2)	0.0098 (17)	0.0084 (18)	0.0072 (17)
C31	0.024 (2)	0.024 (2)	0.031 (3)	0.0151 (19)	0.019 (2)	0.0120 (19)
C32	0.023 (2)	0.0212 (19)	0.018 (2)	0.0128 (17)	0.0126 (18)	0.0078 (16)
C33	0.018 (2)	0.0180 (18)	0.018 (2)	0.0114 (16)	0.0079 (17)	0.0055 (16)
C34	0.024 (3)	0.024 (2)	0.040 (3)	0.004 (2)	0.016 (2)	0.010 (2)
Cl1	0.0632 (17)	0.0462 (13)	0.090 (2)	0.0339 (12)	0.0299 (15)	0.0151 (13)
Cl2	0.0725 (19)	0.0584 (15)	0.082 (2)	0.0366 (14)	0.0384 (17)	0.0419 (14)
C35	0.025 (5)	0.029 (4)	0.116 (10)	0.003 (4)	0.018 (6)	−0.002 (5)
Cl3	0.071 (4)	0.049 (3)	0.096 (5)	0.033 (3)	0.028 (4)	0.019 (3)
Cl4	0.085 (5)	0.058 (3)	0.061 (4)	0.037 (3)	0.032 (3)	0.020 (3)

Geometric parameters (Å, º)

Rh1—Rh2	2.3937 (10)	C10—H6	0.9500
Rh1—O1	2.051 (3)	C11—C12	1.387 (6)
Rh1—O5	2.039 (3)	C11—H7	0.9500
Rh1—O9	2.050 (3)	C12—C13	1.397 (6)
Rh1—O13	2.042 (3)	C13—C14	1.380 (6)
Rh1—N5	2.218 (3)	C13—H8	0.9500
Rh2—O2	2.037 (3)	C14—H9	0.9500
Rh2—O6	2.028 (3)	C15—C16	1.495 (5)
Rh2—O10	2.022 (3)	C16—C21	1.392 (5)
Rh2—O14	2.030 (3)	C16—C17	1.393 (5)
Rh2—O17	2.291 (3)	C17—C18	1.385 (6)
O1—C1	1.268 (4)	C17—H10	0.9500
O2—C1	1.264 (4)	C18—C19	1.377 (6)
O3—N1	1.227 (5)	C18—H11	0.9500
O4—N1	1.224 (5)	C19—C20	1.380 (6)
O5—C8	1.267 (4)	C20—C21	1.381 (5)
O6—C8	1.270 (5)	C20—H12	0.9500
O7—N2	1.225 (5)	C21—H13	0.9500
O8—N2	1.231 (5)	C22—C23	1.494 (5)
O9—C15	1.272 (4)	C23—C28	1.399 (6)
O10—C15	1.265 (5)	C23—C24	1.399 (5)
O11—N3	1.230 (5)	C24—C25	1.380 (5)
O12—N3	1.234 (4)	C24—H14	0.9500
O13—C22	1.266 (5)	C25—C26	1.386 (5)
O14—C22	1.264 (5)	C25—H15	0.9500
O15—N4	1.227 (4)	C26—C27	1.375 (5)
O16—N4	1.225 (4)	C27—C28	1.385 (6)
O17—C34	1.409 (5)	C27—H16	0.9500
O17—H1	0.65 (5)	C28—H17	0.9500
N1—C5	1.479 (5)	C29—C30	1.372 (6)
N2—C12	1.469 (5)	C29—H18	0.9500
N3—C19	1.469 (5)	C30—C31	1.403 (6)
N4—C26	1.467 (5)	C30—H19	0.9500
N5—C33	1.341 (5)	C31—C32	1.378 (6)
N5—C29	1.344 (5)	C31—H20	0.9500
C1—C2	1.497 (5)	C32—C33	1.375 (5)
C2—C3	1.390 (5)	C32—H21	0.9500
C2—C7	1.394 (5)	C33—H22	0.9500
C3—C4	1.377 (5)	C34—H23	0.9800
C3—H2	0.9500	C34—H24	0.9800
C4—C5	1.385 (6)	C34—H25	0.9800
C4—H3	0.9500	Cl1—C35	1.780 (12)
C5—C6	1.378 (6)	Cl2—C35	1.713 (12)
C6—C7	1.383 (5)	C35—H26	0.9900
C6—H4	0.9500	C35—H27	0.9900
C7—H5	0.9500	Cl3—C36	1.77 (2)
C8—C9	1.491 (5)	Cl4—C36	1.64 (2)
C9—C10	1.396 (5)	C36—H28	0.9900
C9—C14	1.398 (5)	C36—H29	0.9900
C10—C11	1.379 (6)
N2···C32^i	3.177 (6)	N4···C30^ii	3.172 (7)
C11···C29^i	3.252 (7)	O16···C30^ii	3.230 (5)
O7···C33^i	3.320 (6)	C25···C33^ii	3.270 (7)
O8···C32^i	3.340 (7)	O15···C29^ii	3.289 (6)
C12···C31^i	3.342 (7)	C25···N5^ii	3.310 (6)
C11···N5^i	3.347 (7)	N4···C29^ii	3.323 (5)
C13···C31^i	3.394 (8)	C27···C31^ii	3.386 (7)
C10···C29^i	3.399 (7)	C26···C31^ii	3.403 (8)
N2···C33^i	3.430 (7)	C26···C30^ii	3.459 (7)
C12···C30^i	3.433 (6)	C24···C33^ii	3.464 (6)
C12···C32^i	3.454 (7)	C26···C32^ii	3.484 (6)
C13···C30^i	3.477 (7)	C27···C32^ii	3.491 (6)
O7···C32^i	3.493 (5)	O15···C30^ii	3.568 (7)
C11···C30^i	3.536 (6)	C26···C29^ii	3.581 (6)
N2···C31^i	3.564 (5)
O5—Rh1—O13	175.59 (10)	C10—C11—H7	120.7
O5—Rh1—O9	90.76 (12)	C12—C11—H7	120.7
O13—Rh1—O9	89.73 (12)	C11—C12—C13	122.2 (4)
O5—Rh1—O1	88.89 (12)	C11—C12—N2	119.0 (4)
O13—Rh1—O1	90.28 (12)	C13—C12—N2	118.8 (4)
O9—Rh1—O1	175.46 (10)	C14—C13—C12	118.3 (4)
O5—Rh1—N5	92.70 (12)	C14—C13—H8	120.8
O13—Rh1—N5	91.66 (12)	C12—C13—H8	120.8
O9—Rh1—N5	91.74 (10)	C13—C14—C9	120.4 (4)
O1—Rh1—N5	92.80 (10)	C13—C14—H9	119.8
O5—Rh1—Rh2	87.95 (8)	C9—C14—H9	119.8
O13—Rh1—Rh2	87.69 (8)	O10—C15—O9	125.8 (3)
O9—Rh1—Rh2	87.86 (8)	O10—C15—C16	116.4 (3)
O1—Rh1—Rh2	87.61 (8)	O9—C15—C16	117.8 (3)
N5—Rh1—Rh2	179.23 (9)	C21—C16—C17	119.9 (4)
O10—Rh2—O6	90.41 (12)	C21—C16—C15	118.9 (3)
O10—Rh2—O14	90.05 (13)	C17—C16—C15	121.1 (3)
O6—Rh2—O14	176.52 (11)	C18—C17—C16	120.0 (4)
O10—Rh2—O2	176.70 (11)	C18—C17—H10	120.0
O6—Rh2—O2	88.83 (12)	C16—C17—H10	120.0
O14—Rh2—O2	90.52 (13)	C19—C18—C17	119.1 (4)
O10—Rh2—O17	91.18 (10)	C19—C18—H11	120.5
O6—Rh2—O17	92.37 (11)	C17—C18—H11	120.5
O14—Rh2—O17	91.07 (12)	C18—C19—C20	121.9 (4)
O2—Rh2—O17	92.06 (10)	C18—C19—N3	118.7 (4)
O10—Rh2—Rh1	88.33 (8)	C20—C19—N3	119.4 (3)
O6—Rh2—Rh1	88.05 (8)	C19—C20—C21	119.0 (4)
O14—Rh2—Rh1	88.51 (9)	C19—C20—H12	120.5
O2—Rh2—Rh1	88.43 (8)	C21—C20—H12	120.5
O17—Rh2—Rh1	179.36 (8)	C20—C21—C16	120.2 (4)
C1—O1—Rh1	119.2 (2)	C20—C21—H13	119.9
C1—O2—Rh2	119.1 (2)	C16—C21—H13	119.9
C8—O5—Rh1	119.0 (3)	O14—C22—O13	126.5 (4)
C8—O6—Rh2	119.4 (2)	O14—C22—C23	116.6 (3)
C15—O9—Rh1	118.4 (2)	O13—C22—C23	117.0 (3)
C15—O10—Rh2	119.5 (2)	C28—C23—C24	119.7 (4)
C22—O13—Rh1	118.7 (2)	C28—C23—C22	119.5 (3)
C22—O14—Rh2	118.5 (3)	C24—C23—C22	120.7 (4)
C34—O17—Rh2	122.0 (3)	C25—C24—C23	120.2 (4)
C34—O17—H1	109 (5)	C25—C24—H14	119.9
Rh2—O17—H1	128 (5)	C23—C24—H14	119.9
O4—N1—O3	123.8 (4)	C24—C25—C26	118.5 (4)
O4—N1—C5	118.1 (3)	C24—C25—H15	120.7
O3—N1—C5	118.1 (4)	C26—C25—H15	120.7
O7—N2—O8	123.6 (4)	C27—C26—C25	122.8 (4)
O7—N2—C12	118.5 (3)	C27—C26—N4	118.6 (4)
O8—N2—C12	117.9 (4)	C25—C26—N4	118.6 (4)
O11—N3—O12	123.6 (3)	C26—C27—C28	118.5 (4)
O11—N3—C19	118.3 (3)	C26—C27—H16	120.8
O12—N3—C19	118.1 (3)	C28—C27—H16	120.8
O16—N4—O15	122.7 (4)	C27—C28—C23	120.2 (4)
O16—N4—C26	118.5 (3)	C27—C28—H17	119.9
O15—N4—C26	118.8 (3)	C23—C28—H17	119.9
C33—N5—C29	119.2 (3)	N5—C29—C30	122.0 (4)
C33—N5—Rh1	120.5 (3)	N5—C29—H18	119.0
C29—N5—Rh1	120.3 (3)	C30—C29—H18	119.0
O2—C1—O1	125.6 (4)	C29—C30—C31	119.0 (4)
O2—C1—C2	116.2 (3)	C29—C30—H19	120.5
O1—C1—C2	118.1 (3)	C31—C30—H19	120.5
C3—C2—C7	119.2 (4)	C32—C31—C30	118.4 (4)
C3—C2—C1	120.4 (3)	C32—C31—H20	120.8
C7—C2—C1	120.3 (3)	C30—C31—H20	120.8
C4—C3—C2	121.0 (4)	C33—C32—C31	119.7 (4)
C4—C3—H2	119.5	C33—C32—H21	120.2
C2—C3—H2	119.5	C31—C32—H21	120.2
C3—C4—C5	118.2 (4)	N5—C33—C32	121.8 (4)
C3—C4—H3	120.9	N5—C33—H22	119.1
C5—C4—H3	120.9	C32—C33—H22	119.1
C6—C5—C4	122.5 (4)	O17—C34—H23	109.5
C6—C5—N1	118.8 (4)	O17—C34—H24	109.5
C4—C5—N1	118.6 (4)	H23—C34—H24	109.5
C5—C6—C7	118.4 (4)	O17—C34—H25	109.5
C5—C6—H4	120.8	H23—C34—H25	109.5
C7—C6—H4	120.8	H24—C34—H25	109.5
C6—C7—C2	120.6 (4)	Cl2—C35—Cl1	114.6 (6)
C6—C7—H5	119.7	Cl2—C35—H26	108.6
C2—C7—H5	119.7	Cl1—C35—H26	108.6
O5—C8—O6	125.2 (4)	Cl2—C35—H27	108.6
O5—C8—C9	118.4 (3)	Cl1—C35—H27	108.6
O6—C8—C9	116.3 (3)	H26—C35—H27	107.6
C10—C9—C14	120.0 (4)	Cl4—C36—Cl3	117.2 (14)
C10—C9—C8	120.6 (3)	Cl4—C36—H28	108.0
C14—C9—C8	119.3 (3)	Cl3—C36—H28	108.0
C11—C10—C9	120.4 (4)	Cl4—C36—H29	108.0
C11—C10—H6	119.8	Cl3—C36—H29	108.0
C9—C10—H6	119.8	H28—C36—H29	107.2
C10—C11—C12	118.6 (4)
O5—Rh1—Rh2—O10	−91.09 (12)	N1—C5—C6—C7	−179.9 (3)
O13—Rh1—Rh2—O10	89.57 (12)	C5—C6—C7—C2	0.8 (6)
O9—Rh1—Rh2—O10	−0.25 (12)	C3—C2—C7—C6	0.1 (6)
O1—Rh1—Rh2—O10	179.94 (12)	C1—C2—C7—C6	177.1 (4)
O5—Rh1—Rh2—O6	−0.61 (10)	Rh1—O5—C8—O6	6.7 (5)
O13—Rh1—Rh2—O6	−179.96 (11)	Rh1—O5—C8—C9	−171.2 (2)
O9—Rh1—Rh2—O6	90.22 (12)	Rh2—O6—C8—O5	−7.5 (5)
O1—Rh1—Rh2—O6	−89.59 (12)	Rh2—O6—C8—C9	170.4 (2)
O5—Rh1—Rh2—O14	178.82 (11)	O5—C8—C9—C10	−1.0 (5)
O13—Rh1—Rh2—O14	−0.52 (11)	O6—C8—C9—C10	−179.1 (3)
O9—Rh1—Rh2—O14	−90.34 (13)	O5—C8—C9—C14	175.8 (3)
O1—Rh1—Rh2—O14	89.85 (12)	O6—C8—C9—C14	−2.3 (5)
O5—Rh1—Rh2—O2	88.26 (12)	C14—C9—C10—C11	−1.5 (5)
O13—Rh1—Rh2—O2	−91.08 (12)	C8—C9—C10—C11	175.4 (3)
O9—Rh1—Rh2—O2	179.10 (12)	C9—C10—C11—C12	−0.2 (5)
O1—Rh1—Rh2—O2	−0.71 (11)	C10—C11—C12—C13	1.5 (6)
O5—Rh1—O1—C1	−86.1 (3)	C10—C11—C12—N2	−179.2 (3)
O13—Rh1—O1—C1	89.5 (3)	O7—N2—C12—C11	4.5 (5)
N5—Rh1—O1—C1	−178.8 (3)	O8—N2—C12—C11	−174.6 (4)
Rh2—Rh1—O1—C1	1.8 (3)	O7—N2—C12—C13	−176.2 (4)
O6—Rh2—O2—C1	87.9 (3)	O8—N2—C12—C13	4.7 (5)
O14—Rh2—O2—C1	−88.7 (3)	C11—C12—C13—C14	−1.1 (6)
O17—Rh2—O2—C1	−179.8 (3)	N2—C12—C13—C14	179.6 (3)
Rh1—Rh2—O2—C1	−0.2 (3)	C12—C13—C14—C9	−0.6 (5)
O9—Rh1—O5—C8	−90.4 (3)	C10—C9—C14—C13	1.9 (5)
O1—Rh1—O5—C8	85.1 (3)	C8—C9—C14—C13	−175.0 (3)
N5—Rh1—O5—C8	177.9 (3)	Rh2—O10—C15—O9	1.2 (6)
Rh2—Rh1—O5—C8	−2.5 (3)	Rh2—O10—C15—C16	−177.9 (3)
O10—Rh2—O6—C8	92.3 (3)	Rh1—O9—C15—O10	−1.5 (5)
O2—Rh2—O6—C8	−84.5 (3)	Rh1—O9—C15—C16	177.6 (3)
O17—Rh2—O6—C8	−176.5 (3)	O10—C15—C16—C21	−4.3 (6)
Rh1—Rh2—O6—C8	4.0 (3)	O9—C15—C16—C21	176.5 (4)
O5—Rh1—O9—C15	88.8 (3)	O10—C15—C16—C17	172.6 (4)
O13—Rh1—O9—C15	−86.8 (3)	O9—C15—C16—C17	−6.6 (6)
N5—Rh1—O9—C15	−178.4 (3)	C21—C16—C17—C18	−0.3 (7)
Rh2—Rh1—O9—C15	0.9 (3)	C15—C16—C17—C18	−177.1 (4)
O6—Rh2—O10—C15	−88.4 (3)	C16—C17—C18—C19	1.3 (7)
O14—Rh2—O10—C15	88.2 (3)	C17—C18—C19—C20	−1.3 (7)
O17—Rh2—O10—C15	179.3 (3)	C17—C18—C19—N3	178.0 (4)
Rh1—Rh2—O10—C15	−0.3 (3)	O11—N3—C19—C18	4.4 (6)
O9—Rh1—O13—C22	86.4 (3)	O12—N3—C19—C18	−175.4 (4)
O1—Rh1—O13—C22	−89.0 (3)	O11—N3—C19—C20	−176.3 (4)
N5—Rh1—O13—C22	178.2 (3)	O12—N3—C19—C20	4.0 (6)
Rh2—Rh1—O13—C22	−1.4 (3)	C18—C19—C20—C21	0.3 (7)
O10—Rh2—O14—C22	−85.7 (3)	N3—C19—C20—C21	−179.0 (4)
O2—Rh2—O14—C22	91.1 (3)	C19—C20—C21—C16	0.8 (6)
O17—Rh2—O14—C22	−176.9 (3)	C17—C16—C21—C20	−0.8 (7)
Rh1—Rh2—O14—C22	2.6 (3)	C15—C16—C21—C20	176.1 (4)
O10—Rh2—O17—C34	−40.0 (3)	Rh2—O14—C22—O13	−4.8 (5)
O6—Rh2—O17—C34	−130.5 (3)	Rh2—O14—C22—C23	173.6 (2)
O14—Rh2—O17—C34	50.1 (3)	Rh1—O13—C22—O14	4.2 (5)
O2—Rh2—O17—C34	140.6 (3)	Rh1—O13—C22—C23	−174.2 (2)
O5—Rh1—N5—C33	165.0 (3)	O14—C22—C23—C28	−4.3 (5)
O13—Rh1—N5—C33	−15.7 (3)	O13—C22—C23—C28	174.3 (3)
O9—Rh1—N5—C33	74.1 (3)	O14—C22—C23—C24	179.3 (3)
O1—Rh1—N5—C33	−106.0 (3)	O13—C22—C23—C24	−2.0 (5)
O5—Rh1—N5—C29	−15.0 (3)	C28—C23—C24—C25	−1.9 (6)
O13—Rh1—N5—C29	164.4 (3)	C22—C23—C24—C25	174.5 (3)
O9—Rh1—N5—C29	−105.8 (3)	C23—C24—C25—C26	−0.6 (6)
O1—Rh1—N5—C29	74.0 (3)	C24—C25—C26—C27	3.2 (6)
Rh2—O2—C1—O1	1.8 (5)	C24—C25—C26—N4	−178.2 (3)
Rh2—O2—C1—C2	−175.9 (2)	O16—N4—C26—C27	6.5 (5)
Rh1—O1—C1—O2	−2.6 (5)	O15—N4—C26—C27	−174.9 (4)
Rh1—O1—C1—C2	175.0 (2)	O16—N4—C26—C25	−172.2 (3)
O2—C1—C2—C3	171.6 (4)	O15—N4—C26—C25	6.4 (5)
O1—C1—C2—C3	−6.3 (6)	C25—C26—C27—C28	−3.1 (6)
O2—C1—C2—C7	−5.3 (5)	N4—C26—C27—C28	178.3 (3)
O1—C1—C2—C7	176.8 (4)	C26—C27—C28—C23	0.5 (6)
C7—C2—C3—C4	−0.7 (6)	C24—C23—C28—C27	2.0 (6)
C1—C2—C3—C4	−177.7 (4)	C22—C23—C28—C27	−174.5 (4)
C2—C3—C4—C5	0.4 (6)	C33—N5—C29—C30	0.3 (5)
C3—C4—C5—C6	0.5 (6)	Rh1—N5—C29—C30	−179.7 (3)
C3—C4—C5—N1	179.3 (4)	N5—C29—C30—C31	0.3 (5)
O4—N1—C5—C6	4.9 (5)	C29—C30—C31—C32	−0.6 (5)
O3—N1—C5—C6	−174.8 (4)	C30—C31—C32—C33	0.2 (6)
O4—N1—C5—C4	−174.0 (4)	C29—N5—C33—C32	−0.8 (5)
O3—N1—C5—C4	6.3 (6)	Rh1—N5—C33—C32	179.3 (3)
C4—C5—C6—C7	−1.0 (6)	C31—C32—C33—N5	0.5 (6)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O17—H1···O2^iii	0.65 (5)	2.42 (5)	2.963 (4)	143 (6)

Symmetry code: (iii) −x+1, −y+1, −z+1.