[1,3-Bis(2-ethoxy­phenyl)imidazolidin-2-yl­idene]bromo­(cyclo­octa-1,5-diene)­rhodium(I)

The title complex, [RhBr(C₈H₁₂)(C₁₉H₂₂N₂O₂)], has a distorted square-planar geometry. There are two mol­ecules, A and B, in the asymmetric unit. The Rh-C bond distance between the N-heterocyclic ligand and the metal atom is 2.039 (2) Å in mol­ecule A and 2.042 (2) Å in mol­ecule B. The angle between the carbene heterocycle and the coordination plane is 87.56 (12)° in mol­ecule A and 87.03 (11)° in mol­ecule B. It is shown that the average Rh-C(COD) (COD is cyclo­octa­diene) distance is linearly dependent on the Rh-C(imidazolidine) distance in this type of compound. This can be ascribed to the steric hindrance produced by the packing. The crystal structure contains intra­molecular C-H...O and inter­molecular C-H...Br inter­actions.

S1. Comment

N-Heterocyclic carbenes (NHCs) based on the imidazole ring system are a novel class of ligands in organometallic chemistry (Weskamp et al., 2000) which tend to coordinate very strongly to the metal centre. Side chains containing hemilabile functionalities should trigger the chemistry at the metal centre and, at the same time, enhance the stability of the catalyst (Bourissou et al., 2000; Hermann, 2002a). For example, NHC complexes with methoxyethyl substituents have been used as catalysts in cyclopropanation reactions (Çetinkaya et al., 1997). The objective of the present work was to seek a metal carbene complex, L_nM—CN(Ar)CH₂CH₂N(Ar), in which the Ar group has an o-ethoxy functionality, so that the carbene ligand has potential as a bidentate chelating or bridging ligand. We describe here the crystal structure of the title compound, (II).

The structures of the two independent molecules, A and B, of (II) have very similar molecular dimensions (Fig. 1 and Table 1). In the following discussion, parameters for molecule B are quoted in square brackets. The two molecules are separated by van der Waals interactions and one weak hydrogen bond. Atom C43 of the ethoxyphenyl group forms a hydrogen bond with the Br1 ligand. Similarly, atom C16 of the ethoxyphenyl group forms a C—H···Br contact with the Br2 ligand (Table 2). This arrangement results in the formation of infinite chains running along the a axis in the crystal (Fig. 2).

Complex (II) has a distorted square-planar geometry (Fig. 1 and Table 1), the metal centre being coordinated to the centres of the two alkene bonds of the 1,5-cyclooctadiene ligand, to the non-substituted C atom of the imidazolidine ring, and to one Br atom. The angle between the carbene heterocycle and the coordination plane (Br1/C4/C11) is 87.56 (12)° [87.03 (11)° for Br2/C31/C38]. This value is somewhat smaller than in similar complexes (Hermann, 2002a). The Rh—C_COD distances range from 2.123 (2) to 2.274 (3) Å [2.132 (2) to 2.274 (2) Å]. The bond distances Rh1—C4 and Rh1—C11 are shorter than Rh1—C7 and Rh1—C8. This is not unexpected, due to the trans influence of the chelating ligand.

Comparing the average Rh—C(COD) bond length, 2.204 (2) Å [2.198 (2) Å], and the Rh—C(imidazolidine) bond length, 2.039 (2) Å [2.042 (2) Å], with literature values, it is observed that Rh—C(COD) increases with increasing Rh—C(imidazolidine) distance [2.159 (5) and 2.015 (5) Å; Günay et al., 2005]. This suggests that the bond lengths involving the Rh atom are more affected by steric hindrance of the packing than by electronic effects. In the COD moiety, the C4═C11 [C31═C38] double-bonds are longer than those opposite, C7═C8 [C34═C35]. In molecule A, the ethoxyphenyl group (O1/C12–C19) attached to the imidazolidine ring shows positional disorder.

Although the imidazolidine ring is planar [maximum deviation −0.012 (3) Å for atom C1], the imidazolidine ring in B is close to a very shallow envelope conformation, with atom C30 displaced by −0.052 (3) Å from the plane. The imidazole ring makes dihedral angles of 52.8 (3) (A), 62.8 (7) (B) and 78.08 (14)° with the ethoxyphenyl ring planes [68.24 (13) and 72.22 (13)°], respectively.

The metal–carbon bond distance between Rh and the NHC ligand of 2.039 (2) Å [2.042 (2) Å] is longer than in other rhodium NHC complexes [2.015 (5) Å; Günay et al., 2005], mainly due to the presence of a Br ligand instead of a Cl ligand. The N1—C1 and N2—C1 bond distances are 1.354 (3) and 1.358 (3) Å, respectively [N3—C28 and N4—C28, 1.348 (3) and 1.361 (3) Å, respectively]. These are significantly shorter than the other N—C_carbene bond distances in these complexes. For instance N1—C2 is 1.514 (3) Å [N3—C29, 1.503 (3) Å], possibly indicative of a greater partial double-bond character due to partial electron donation by N to the carbene C donor (Hermann, 2002b; Fröhlich et al., 1997).

Theoretical studies also indicate that the stability of these carbenes is due to electron donation from the N-atom lone pairs into the formally vacant p(π) orbital of the carbene C atom (McGuinness et al., 1998). The Br—Rh—C_carbene angle of 87.89 (6)° [86.98 (6)°] is somewhat smaller than for similar compounds (Herrmann, 2002b; Danopoulos et al., 2002).

The O atoms of the o-ethoxy substituents of the phenyl ring do not interact with the Rh atoms. Instead, there are four intramolecular C—H···O interactions (Table 2). The interactions involving the imidazolidine ring form a six-membered closed ring, which is fused with both the imidazolidine ring and the phenyl rings. These intramolecular interactions strongly influence the orientation of the ethoxyphenyl rings, resulting in a tilting of these rings towards to the imidazolidine rings.

S2. Experimental

All reactions were conducted under argon using standard Schlenk Cannula techniques. The solvents were purified using the system described by Pangborn et al. (1996). The imidazolinium salt (Günay, 2004) and [Rh(OMe)(COD)]₂ (Uson et al., 1985) were synthesized according to the published procedures. ¹H and ¹³C NMR spectra were recorded on a Bruker DPX-400 MHz s pectrometer. Elemental analyses were performed using a CHNS-932 (LECO) in the TUBITAK (Scientific and Technical Research Council of Turkey) Microlaboratory and melting points were determined using an electrothermal melting point detection apparatus.

A 50 ml Schlenk tube was charged with compound (I) (0.196 g, 0.5 mmol), [Rh(OMe)(η⁴-COD)]₂ (0.121 g, 0.25 mmol) and toluene (5 ml). The solution was heated under reflux for 4 h. Upon cooling to room temperature, hexane (10 ml) was added to the mixture. The resulting solid was filtered off and then recrystallized in CH₂Cl₂–Et₂O (Ratio?). Yield: 0.242 g. (80%), m.p. 493–495 K. Analysis calculated for RhBrC₂₇H₃₄N₂O₂: C 53.92, H 5.70, N 4.66%; found: C 53.87, H 5.62, N 4.45%. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 1.42 [s, 6H, 2-(OCH₂CH₃)C₆H₄], 1.43 (m, COD-CH), 1.63 (m, COD-CH₂), 3.79 (m, COD-CH), 3.76–3.81 (m, 2H, NCH₂CH₂N), 4.00–4.07 [m, 2H, 2-(OCH₂CH₃)C₆H₄], 4.10–4.16 [m, 2H, 2-(OCH₂CH₃)C₆H₄], 4.41–4.54 (m, 2H, NCH₂CH₂N), 4.66 (d, J = 2.80 Hz, COD-CH), 6.93 [dd, 2H, J = 7.20 and 1.20 Hz, 2-(OCH₂CH₃)C₆H₄], 7.08–7.12 [tt, 2H, J = 6.8, 1.6 and 1.2 Hz, 2-(OCH₂CH₃)C₆H₄], 7.30–7.34 [tt, 2H, J = 6.0, 2.0 and 1.6 Hz, 2-(OCH₂CH₃)C₆H₄], 8.50 [dd, 2H, J = 6.0 and 1.60 Hz, 2-(OCH₂CH₃)C₆H₄]; ¹³C NMR (CDCl₃, δ, p.p.m.): 15.1 [2-(OCH₂CH₃)C₆H₄], 28.7 (COD-CH), 32.2 (COD-CH₂), 51.2 (NCH₂CH₂N), 63.8 [2-(OCH₂CH₃)C₆H₄], 68.3 [2-(OCH₂CH₃)C₆H₄], 97.1 (COD-CH), 111.6 [2-(OCH₂CH₃)C₆H₄], 120.8 [2-(OCH₂CH₃)C₆H₄], 128.7 [2-(OCH₂CH₃)C₆H₄], 130.3 [2-(OCH₂CH₃)C₆H₄], 132.6 [2-(OCH₂CH₃)C₆H₄], 154.4 [2-(OCH₂CH₃)C₆H₄], 213.95 (d, J = 45.8 Hz, C_carb Rh).

S3. Refinement

H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.96, 0.97, 0.98 and 0.93 Å for CH₃, CH₂, CH and CH(ar), respectively. The displacement parameters of the H atoms were constrained as U_iso(H) = 1.2U_eq (1.5U_eq for methyl) of the parent atom. In molecule A, the ethoxyphenyl group (O1/C12–C19) shows positional disorder and the refined site-occupancy factors of the disordered parts, O1A/C12A–C19A and O1B/C12B–C19B, are 73 (6) and 27 (6)%, respectively. The disordered atoms were refined using the following restraints: SIMU, DELU, FLAT and SAME (SHELXL97; Sheldrick, 1997).

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. The two molecules of (II), with 50% probability displacement ellipsoids and atom-numbering scheme. H atoms have been omitted for clarity.
	Fig. 2. A projection of (II) approximately along b, showing the one-dimensional polymer built via intermolecular C—H···Br interactions.

[1,3-Bis(2-ethoxyphenyl)imidazolidin-2-ylidene]bromo(1,5- cyclooctadiene)rhodium(I)

Crystal data

[RhBr(C19H22N2O2)(C8H12)]	F(000) = 2448
Mr = 601.38	Dx = 1.471 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 75141 reflections
a = 19.7510 (6) Å	θ = 1.3–27.3°
b = 17.6450 (6) Å	µ = 2.12 mm^−1
c = 17.1978 (7) Å	T = 100 K
β = 114.982 (3)°	Prism, yellow
V = 5432.8 (3) Å^3	0.45 × 0.32 × 0.20 mm
Z = 8

Data collection

Stoe IPDS 2 diffractometer	10685 independent reflections
Radiation source: sealed X-ray tube	9007 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.088
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.6°
ω scans	h = −24→24
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −21→21
Tmin = 0.488, Tmax = 0.683	l = −21→21
76907 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.062	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0324P)^2 + 2.0889P] where P = (Fo^2 + 2Fc^2)/3
10685 reflections	(Δ/σ)max = 0.003
680 parameters	Δρmax = 0.75 e Å^−3
278 restraints	Δρmin = −0.87 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	0.833810 (10)	0.845952 (10)	0.653460 (11)	0.01627 (5)
Br1	0.769931 (13)	0.731330 (15)	0.686647 (16)	0.02359 (6)
O1A	0.9526 (2)	0.7780 (2)	0.4509 (3)	0.0347 (8)	0.730 (6)
O1B	0.9772 (5)	0.8010 (6)	0.4901 (8)	0.037 (2)	0.270 (6)
O2	0.75068 (10)	0.94111 (10)	0.39219 (12)	0.0283 (4)
N1	0.84716 (12)	0.75353 (12)	0.50789 (13)	0.0219 (4)
N2	0.73958 (11)	0.81001 (12)	0.46829 (13)	0.0213 (4)
C1	0.80718 (13)	0.79991 (13)	0.53540 (15)	0.0171 (5)
C2	0.80751 (18)	0.73080 (17)	0.41445 (17)	0.0337 (6)
H2A	0.8017	0.6763	0.4081	0.040*
H2B	0.8339	0.7489	0.3817	0.040*
C3	0.73192 (17)	0.77053 (16)	0.38723 (17)	0.0315 (6)
H3A	0.7234	0.8066	0.3415	0.038*
H3B	0.6913	0.7342	0.3683	0.038*
C4	0.86134 (13)	0.95384 (14)	0.61366 (16)	0.0207 (5)
H4	0.8423	0.9599	0.5514	0.025*
C5	0.84467 (15)	1.02179 (16)	0.65983 (19)	0.0306 (6)
H5A	0.8914	1.0421	0.7019	0.037*
H5B	0.8202	1.0613	0.6182	0.037*
C6	0.79487 (19)	0.99985 (18)	0.7049 (2)	0.0439 (8)
H6A	0.7430	1.0011	0.6634	0.053*
H6B	0.8011	1.0372	0.7488	0.053*
C7	0.81243 (18)	0.92061 (18)	0.74671 (19)	0.0370 (7)
H7	0.7741	0.9011	0.7636	0.044*
C8	0.88077 (18)	0.88964 (19)	0.79059 (17)	0.0405 (8)
H8	0.8828	0.8515	0.8330	0.049*
C9	0.95486 (19)	0.9301 (2)	0.8119 (2)	0.0500 (9)
H9A	0.9913	0.9130	0.8674	0.060*
H9B	0.9480	0.9842	0.8157	0.060*
C10	0.98582 (15)	0.91503 (18)	0.7424 (2)	0.0426 (8)
H10A	1.0186	0.9565	0.7440	0.051*
H10B	1.0155	0.8691	0.7576	0.051*
C11	0.92536 (13)	0.90691 (14)	0.65048 (18)	0.0247 (5)
H11	0.9435	0.8873	0.6094	0.030*
C12A	0.9191 (4)	0.7279 (4)	0.5585 (5)	0.0202 (12)	0.730 (6)
C13A	0.9370 (5)	0.6945 (5)	0.6394 (6)	0.0227 (13)	0.730 (6)
H13A	0.8995	0.6857	0.6575	0.027*	0.730 (6)
C14A	1.0108 (5)	0.6746 (4)	0.6926 (5)	0.0284 (15)	0.730 (6)
H14A	1.0230	0.6526	0.7460	0.034*	0.730 (6)
C15A	1.0653 (4)	0.6884 (4)	0.6635 (4)	0.0298 (15)	0.730 (6)
H15A	1.1145	0.6753	0.6982	0.036*	0.730 (6)
C16A	1.0487 (3)	0.7216 (3)	0.5834 (4)	0.0292 (12)	0.730 (6)
H16A	1.0866	0.7299	0.5659	0.035*	0.730 (6)
C17A	0.9745 (3)	0.7423 (3)	0.5291 (3)	0.0256 (11)	0.730 (6)
C18A	1.0065 (3)	0.7978 (3)	0.4174 (4)	0.0495 (12)	0.730 (6)
H18A	0.9812	0.8035	0.3556	0.059*	0.730 (6)
H18B	1.0429	0.7573	0.4299	0.059*	0.730 (6)
C19A	1.0465 (3)	0.8714 (4)	0.4574 (4)	0.0602 (16)	0.730 (6)
H19A	1.0102	0.9098	0.4516	0.072*	0.730 (6)
H19B	1.0764	0.8875	0.4286	0.072*	0.730 (6)
H19C	1.0780	0.8633	0.5171	0.072*	0.730 (6)
C12B	0.9269 (10)	0.7314 (12)	0.5732 (14)	0.020 (2)	0.270 (6)
C13B	0.9348 (14)	0.6866 (15)	0.6446 (16)	0.020 (2)	0.270 (6)
H13B	0.8930	0.6743	0.6537	0.024*	0.270 (6)
C14B	1.0054 (13)	0.6606 (13)	0.7015 (14)	0.019 (2)	0.270 (6)
H14B	1.0112	0.6311	0.7487	0.023*	0.270 (6)
C15B	1.0663 (12)	0.6802 (10)	0.6855 (10)	0.021 (3)	0.270 (6)
H15B	1.1134	0.6631	0.7230	0.025*	0.270 (6)
C16B	1.0600 (8)	0.7242 (9)	0.6158 (9)	0.021 (2)	0.270 (6)
H16B	1.1024	0.7359	0.6077	0.026*	0.270 (6)
C17B	0.9897 (8)	0.7513 (8)	0.5574 (8)	0.019 (2)	0.270 (6)
C18B	1.0386 (7)	0.8258 (9)	0.4715 (10)	0.046 (3)	0.270 (6)
H18C	1.0550	0.7842	0.4466	0.055*	0.270 (6)
H18D	1.0803	0.8409	0.5243	0.055*	0.270 (6)
C19B	1.0148 (9)	0.8910 (9)	0.4105 (11)	0.061 (4)	0.270 (6)
H19D	0.9706	0.8775	0.3606	0.073*	0.270 (6)
H19E	1.0540	0.9035	0.3937	0.073*	0.270 (6)
H19F	1.0044	0.9340	0.4379	0.073*	0.270 (6)
C20	0.69229 (13)	0.87390 (14)	0.46637 (15)	0.0216 (5)
C21	0.64216 (14)	0.86874 (17)	0.50407 (17)	0.0284 (6)
H21	0.6370	0.8237	0.5291	0.034*
C22	0.59951 (15)	0.93315 (19)	0.50349 (18)	0.0355 (7)
H22	0.5659	0.9305	0.5284	0.043*
C23	0.60732 (16)	1.00125 (18)	0.46560 (19)	0.0370 (7)
H23	0.5790	1.0431	0.4662	0.044*
C24	0.65694 (15)	1.00734 (16)	0.42696 (18)	0.0300 (6)
H24	0.6617	1.0525	0.4019	0.036*
C25	0.69965 (13)	0.94281 (15)	0.42708 (16)	0.0229 (5)
C26	0.77306 (17)	1.01308 (18)	0.3670 (2)	0.0374 (7)
H26A	0.7902	1.0486	0.4145	0.045*
H26B	0.7313	1.0355	0.3191	0.045*
C27	0.83558 (19)	0.9941 (2)	0.3416 (3)	0.0561 (10)
H27A	0.8755	0.9700	0.3889	0.084*
H27B	0.8537	1.0398	0.3267	0.084*
H27C	0.8173	0.9605	0.2932	0.084*
Rh2	0.301662 (9)	0.710167 (10)	0.533440 (11)	0.01546 (5)
Br2	0.246080 (14)	0.784945 (15)	0.620368 (17)	0.02694 (6)
O3	0.54336 (9)	0.61880 (10)	0.68834 (12)	0.0264 (4)
O4	0.32904 (9)	0.45013 (10)	0.56687 (12)	0.0254 (4)
N3	0.42080 (10)	0.65817 (11)	0.70627 (13)	0.0186 (4)
N4	0.32686 (10)	0.57942 (11)	0.65814 (13)	0.0180 (4)
C28	0.35418 (12)	0.64467 (13)	0.64015 (15)	0.0161 (4)
C29	0.44153 (13)	0.60028 (14)	0.77669 (15)	0.0211 (5)
H29A	0.4419	0.6224	0.8285	0.025*
H29B	0.4902	0.5784	0.7896	0.025*
C30	0.37891 (13)	0.54015 (14)	0.73836 (15)	0.0216 (5)
H30A	0.3977	0.4932	0.7257	0.026*
H30B	0.3551	0.5299	0.7764	0.026*
C31	0.32044 (14)	0.62843 (14)	0.45040 (15)	0.0214 (5)
H31	0.3333	0.5775	0.4750	0.026*
C32	0.26000 (15)	0.62995 (17)	0.35706 (17)	0.0301 (6)
H32A	0.2811	0.6510	0.3200	0.036*
H32B	0.2439	0.5786	0.3382	0.036*
C33	0.19198 (15)	0.67778 (18)	0.34913 (18)	0.0344 (7)
H33A	0.1576	0.6455	0.3609	0.041*
H33B	0.1664	0.6955	0.2904	0.041*
C34	0.21143 (14)	0.74694 (16)	0.40974 (16)	0.0270 (6)
H34	0.1682	0.7691	0.4153	0.032*
C35	0.27005 (15)	0.79769 (15)	0.42681 (17)	0.0277 (6)
H35	0.2610	0.8487	0.4430	0.033*
C36	0.32249 (17)	0.79488 (17)	0.3820 (2)	0.0356 (7)
H36A	0.3364	0.8461	0.3740	0.043*
H36B	0.2967	0.7719	0.3258	0.043*
C37	0.39304 (16)	0.74919 (17)	0.4345 (2)	0.0340 (6)
H37A	0.4296	0.7828	0.4757	0.041*
H37B	0.4140	0.7306	0.3963	0.041*
C38	0.38018 (14)	0.68135 (15)	0.48317 (16)	0.0231 (5)
H38	0.4266	0.6596	0.5261	0.028*
C39	0.47003 (12)	0.71812 (14)	0.70488 (15)	0.0190 (5)
C40	0.45372 (13)	0.79549 (14)	0.70906 (16)	0.0220 (5)
H40	0.4109	0.8090	0.7156	0.026*
C41	0.50149 (14)	0.85253 (15)	0.70344 (17)	0.0258 (5)
H41	0.4905	0.9035	0.7060	0.031*
C42	0.56542 (14)	0.83116 (15)	0.69404 (17)	0.0264 (6)
H42	0.5975	0.8683	0.6906	0.032*
C43	0.58247 (13)	0.75355 (15)	0.68967 (16)	0.0239 (5)
H43	0.6255	0.7403	0.6834	0.029*
C44	0.53466 (13)	0.69656 (14)	0.69473 (15)	0.0210 (5)
C45	0.60682 (14)	0.59161 (16)	0.67623 (19)	0.0286 (6)
H45A	0.6522	0.5986	0.7282	0.034*
H45B	0.6117	0.6192	0.6301	0.034*
C46	0.59390 (17)	0.50688 (18)	0.6538 (2)	0.0415 (8)
H46A	0.5892	0.4802	0.7000	0.062*
H46B	0.6355	0.4869	0.6453	0.062*
H46C	0.5490	0.5007	0.6022	0.062*
C47	0.25859 (13)	0.54487 (14)	0.59865 (15)	0.0193 (5)
C48	0.19130 (14)	0.57818 (14)	0.58723 (16)	0.0230 (5)
H48	0.1907	0.6207	0.6189	0.028*
C49	0.12464 (14)	0.54692 (16)	0.52760 (18)	0.0286 (6)
H49	0.0791	0.5679	0.5203	0.034*
C50	0.12633 (15)	0.48333 (16)	0.47832 (19)	0.0312 (6)
H50	0.0816	0.4635	0.4382	0.037*
C51	0.19347 (14)	0.44959 (15)	0.48847 (18)	0.0279 (6)
H51	0.1939	0.4082	0.4552	0.033*
C52	0.26010 (13)	0.47970 (14)	0.55017 (16)	0.0217 (5)
C53	0.33277 (15)	0.38751 (15)	0.51195 (17)	0.0264 (5)
H53A	0.3164	0.4048	0.4532	0.032*
H53B	0.3008	0.3461	0.5127	0.032*
C54	0.41287 (16)	0.36183 (17)	0.54742 (19)	0.0345 (6)
H54A	0.4440	0.4035	0.5470	0.052*
H54B	0.4176	0.3214	0.5127	0.052*
H54C	0.4281	0.3442	0.6052	0.052*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01514 (9)	0.01814 (10)	0.01528 (9)	−0.00431 (7)	0.00617 (7)	−0.00146 (7)
Br1	0.02167 (12)	0.02910 (14)	0.02176 (12)	−0.00818 (10)	0.01087 (10)	−0.00173 (10)
O1A	0.0286 (17)	0.047 (2)	0.035 (2)	−0.0043 (14)	0.0202 (15)	0.0068 (15)
O1B	0.028 (4)	0.044 (4)	0.047 (5)	0.003 (3)	0.024 (3)	0.014 (4)
O2	0.0308 (10)	0.0246 (10)	0.0308 (10)	0.0024 (8)	0.0142 (8)	0.0046 (8)
N1	0.0291 (11)	0.0203 (11)	0.0214 (11)	0.0044 (9)	0.0157 (9)	0.0019 (8)
N2	0.0237 (10)	0.0216 (11)	0.0146 (10)	0.0032 (8)	0.0042 (8)	−0.0025 (8)
C1	0.0187 (11)	0.0127 (11)	0.0220 (12)	−0.0012 (9)	0.0107 (9)	0.0036 (9)
C2	0.0535 (18)	0.0283 (15)	0.0213 (13)	0.0126 (13)	0.0178 (13)	0.0014 (11)
C3	0.0466 (17)	0.0254 (14)	0.0187 (13)	0.0073 (12)	0.0100 (12)	−0.0010 (10)
C4	0.0197 (11)	0.0184 (12)	0.0231 (12)	−0.0032 (9)	0.0084 (10)	0.0014 (9)
C5	0.0278 (14)	0.0234 (14)	0.0351 (15)	0.0009 (11)	0.0079 (12)	−0.0051 (11)
C6	0.0493 (19)	0.0368 (18)	0.052 (2)	−0.0034 (14)	0.0281 (16)	−0.0183 (15)
C7	0.0464 (18)	0.0406 (17)	0.0324 (15)	−0.0142 (14)	0.0247 (14)	−0.0170 (13)
C8	0.0546 (19)	0.0502 (19)	0.0139 (12)	−0.0303 (16)	0.0117 (13)	−0.0101 (12)
C9	0.0450 (19)	0.050 (2)	0.0314 (17)	−0.0208 (16)	−0.0065 (14)	0.0037 (15)
C10	0.0164 (13)	0.0362 (17)	0.057 (2)	−0.0065 (12)	−0.0023 (13)	0.0059 (15)
C11	0.0177 (11)	0.0200 (13)	0.0383 (15)	−0.0032 (10)	0.0136 (11)	0.0011 (11)
C12A	0.022 (2)	0.0142 (19)	0.026 (3)	0.0005 (17)	0.011 (2)	−0.0025 (18)
C13A	0.0215 (18)	0.019 (3)	0.030 (2)	0.0004 (18)	0.0128 (17)	−0.003 (2)
C14A	0.029 (2)	0.022 (3)	0.030 (3)	0.005 (2)	0.0081 (18)	0.002 (2)
C15A	0.0231 (18)	0.027 (3)	0.038 (3)	0.0062 (18)	0.012 (2)	−0.001 (2)
C16A	0.024 (2)	0.031 (2)	0.039 (3)	0.0008 (17)	0.019 (2)	−0.004 (2)
C17A	0.027 (2)	0.021 (2)	0.031 (3)	0.0023 (17)	0.014 (2)	−0.002 (2)
C18A	0.040 (2)	0.070 (3)	0.053 (3)	−0.006 (2)	0.034 (2)	0.012 (2)
C19A	0.033 (3)	0.060 (4)	0.082 (4)	−0.005 (2)	0.020 (3)	0.033 (3)
C12B	0.017 (4)	0.016 (4)	0.028 (4)	0.004 (3)	0.011 (3)	0.000 (4)
C13B	0.022 (4)	0.016 (4)	0.024 (4)	−0.002 (4)	0.013 (3)	0.005 (4)
C14B	0.020 (3)	0.017 (5)	0.028 (4)	0.000 (4)	0.017 (3)	0.002 (4)
C15B	0.022 (4)	0.019 (4)	0.026 (5)	0.004 (3)	0.014 (4)	0.003 (4)
C16B	0.016 (4)	0.025 (4)	0.031 (5)	0.004 (3)	0.017 (4)	0.002 (4)
C17B	0.022 (4)	0.016 (4)	0.026 (5)	0.001 (3)	0.016 (4)	0.001 (4)
C18B	0.032 (5)	0.055 (6)	0.062 (6)	−0.004 (4)	0.030 (4)	0.016 (5)
C19B	0.044 (7)	0.077 (8)	0.076 (8)	−0.006 (6)	0.040 (6)	0.028 (6)
C20	0.0183 (11)	0.0234 (13)	0.0161 (11)	0.0017 (10)	0.0004 (9)	−0.0019 (9)
C21	0.0193 (12)	0.0357 (15)	0.0238 (13)	−0.0012 (11)	0.0029 (10)	0.0018 (11)
C22	0.0195 (13)	0.056 (2)	0.0285 (14)	0.0076 (12)	0.0075 (11)	−0.0011 (13)
C23	0.0287 (15)	0.0423 (18)	0.0311 (15)	0.0180 (13)	0.0042 (12)	−0.0014 (13)
C24	0.0304 (14)	0.0242 (14)	0.0264 (14)	0.0081 (11)	0.0034 (11)	0.0019 (11)
C25	0.0208 (12)	0.0235 (13)	0.0179 (12)	0.0031 (10)	0.0018 (10)	−0.0012 (10)
C26	0.0360 (16)	0.0329 (16)	0.0362 (16)	−0.0035 (13)	0.0083 (13)	0.0125 (13)
C27	0.0403 (19)	0.075 (3)	0.056 (2)	−0.0037 (17)	0.0231 (17)	0.025 (2)
Rh2	0.01330 (9)	0.01446 (9)	0.01711 (9)	0.00249 (7)	0.00495 (7)	0.00109 (7)
Br2	0.02309 (12)	0.02640 (14)	0.03186 (14)	0.00492 (10)	0.01211 (11)	−0.00284 (11)
O3	0.0192 (8)	0.0224 (9)	0.0407 (11)	0.0000 (7)	0.0157 (8)	−0.0028 (8)
O4	0.0208 (9)	0.0227 (9)	0.0297 (10)	−0.0003 (7)	0.0079 (7)	−0.0072 (7)
N3	0.0120 (9)	0.0208 (10)	0.0197 (10)	0.0013 (8)	0.0035 (8)	0.0031 (8)
N4	0.0150 (9)	0.0159 (10)	0.0193 (10)	0.0001 (8)	0.0035 (8)	0.0028 (8)
C28	0.0137 (10)	0.0158 (11)	0.0199 (11)	0.0015 (9)	0.0081 (9)	−0.0026 (9)
C29	0.0177 (11)	0.0241 (13)	0.0192 (12)	0.0023 (10)	0.0056 (9)	0.0027 (10)
C30	0.0195 (11)	0.0198 (12)	0.0208 (12)	0.0025 (10)	0.0040 (10)	0.0057 (10)
C31	0.0259 (12)	0.0195 (12)	0.0194 (12)	0.0068 (10)	0.0102 (10)	−0.0012 (9)
C32	0.0309 (14)	0.0313 (15)	0.0224 (13)	0.0004 (12)	0.0057 (11)	−0.0065 (11)
C33	0.0245 (13)	0.0394 (17)	0.0277 (15)	0.0043 (12)	−0.0005 (11)	−0.0029 (12)
C34	0.0197 (12)	0.0317 (15)	0.0204 (12)	0.0131 (11)	−0.0005 (10)	0.0073 (11)
C35	0.0357 (14)	0.0193 (13)	0.0254 (13)	0.0093 (11)	0.0104 (11)	0.0105 (10)
C36	0.0479 (17)	0.0286 (15)	0.0354 (16)	−0.0004 (13)	0.0227 (14)	0.0105 (12)
C37	0.0367 (15)	0.0354 (17)	0.0372 (16)	−0.0049 (13)	0.0228 (13)	0.0014 (13)
C38	0.0223 (12)	0.0277 (13)	0.0235 (13)	0.0044 (10)	0.0139 (10)	0.0008 (10)
C39	0.0127 (10)	0.0236 (13)	0.0171 (11)	−0.0015 (9)	0.0029 (9)	0.0003 (9)
C40	0.0141 (11)	0.0241 (13)	0.0234 (12)	0.0013 (9)	0.0035 (9)	0.0006 (10)
C41	0.0223 (12)	0.0213 (13)	0.0281 (13)	−0.0017 (10)	0.0050 (10)	0.0006 (10)
C42	0.0200 (12)	0.0279 (14)	0.0257 (13)	−0.0090 (10)	0.0042 (10)	−0.0002 (11)
C43	0.0144 (11)	0.0320 (15)	0.0240 (13)	−0.0033 (10)	0.0069 (10)	−0.0008 (11)
C44	0.0156 (11)	0.0242 (13)	0.0198 (12)	0.0003 (9)	0.0041 (9)	−0.0004 (10)
C45	0.0178 (12)	0.0352 (15)	0.0364 (15)	0.0010 (11)	0.0150 (11)	−0.0081 (12)
C46	0.0314 (15)	0.0393 (18)	0.055 (2)	0.0012 (13)	0.0201 (15)	−0.0149 (15)
C47	0.0184 (11)	0.0166 (12)	0.0198 (12)	−0.0033 (9)	0.0052 (9)	0.0018 (9)
C48	0.0227 (12)	0.0198 (13)	0.0236 (13)	0.0012 (10)	0.0070 (10)	0.0015 (10)
C49	0.0185 (12)	0.0268 (14)	0.0330 (15)	0.0014 (10)	0.0038 (11)	0.0039 (11)
C50	0.0198 (12)	0.0272 (14)	0.0353 (15)	−0.0042 (11)	0.0007 (11)	0.0001 (12)
C51	0.0251 (13)	0.0199 (13)	0.0311 (14)	−0.0030 (10)	0.0046 (11)	−0.0023 (11)
C52	0.0206 (12)	0.0177 (12)	0.0231 (12)	−0.0009 (10)	0.0056 (10)	0.0024 (10)
C53	0.0289 (13)	0.0214 (13)	0.0274 (13)	−0.0014 (10)	0.0103 (11)	−0.0059 (10)
C54	0.0323 (15)	0.0346 (16)	0.0348 (15)	0.0053 (12)	0.0125 (12)	−0.0083 (12)

Geometric parameters (Å, º)

Rh1—Br1	2.5722 (3)	C23—H23	0.9300
Rh1—C1	2.039 (2)	C24—C25	1.417 (4)
Rh1—C4	2.168 (2)	C24—H24	0.9300
Rh1—C7	2.249 (3)	C26—C27	1.511 (5)
Rh1—C8	2.274 (3)	C26—H26A	0.9700
Rh1—C11	2.123 (2)	C26—H26B	0.9700
O1A—C17A	1.379 (6)	C27—H27A	0.9600
O1A—C18A	1.452 (5)	C27—H27B	0.9600
O1B—C17B	1.389 (17)	C27—H27C	0.9600
O1B—C18B	1.447 (14)	Rh2—Br2	2.5627 (3)
O2—C25	1.374 (3)	Rh2—C28	2.042 (2)
O2—C26	1.469 (3)	Rh2—C31	2.169 (2)
N1—C1	1.354 (3)	Rh2—C34	2.218 (2)
N1—C12A	1.391 (8)	Rh2—C35	2.274 (2)
N1—C2	1.514 (3)	Rh2—C38	2.132 (2)
N1—C12B	1.55 (2)	O3—C44	1.393 (3)
N2—C1	1.358 (3)	O3—C45	1.437 (3)
N2—C20	1.455 (3)	O4—C52	1.370 (3)
N2—C3	1.508 (3)	O4—C53	1.475 (3)
C2—C3	1.533 (4)	N3—C28	1.348 (3)
C2—H2A	0.9700	N3—C39	1.444 (3)
C2—H2B	0.9700	N3—C29	1.503 (3)
C3—H3A	0.9700	N4—C28	1.361 (3)
C3—H3B	0.9700	N4—C47	1.439 (3)
C4—C11	1.418 (3)	N4—C30	1.497 (3)
C4—C5	1.548 (4)	C29—C30	1.549 (3)
C4—H4	0.9800	C29—H29A	0.9700
C5—C6	1.537 (4)	C29—H29B	0.9700
C5—H5A	0.9700	C30—H30A	0.9700
C5—H5B	0.9700	C30—H30B	0.9700
C6—C7	1.543 (5)	C31—C38	1.421 (4)
C6—H6A	0.9700	C31—C32	1.544 (3)
C6—H6B	0.9700	C31—H31	0.9800
C7—C8	1.353 (5)	C32—C33	1.543 (4)
C7—H7	0.9800	C32—H32A	0.9700
C8—C9	1.527 (4)	C32—H32B	0.9700
C8—H8	0.9800	C33—C34	1.544 (4)
C9—C10	1.578 (5)	C33—H33A	0.9700
C9—H9A	0.9700	C33—H33B	0.9700
C9—H9B	0.9700	C34—C35	1.393 (4)
C10—C11	1.533 (4)	C34—H34	0.9800
C10—H10A	0.9700	C35—C36	1.531 (4)
C10—H10B	0.9700	C35—H35	0.9800
C11—H11	0.9800	C36—C37	1.531 (4)
C12A—C17A	1.409 (6)	C36—H36A	0.9700
C12A—C13A	1.412 (6)	C36—H36B	0.9700
C13A—C14A	1.400 (6)	C37—C38	1.542 (4)
C13A—H13A	0.9300	C37—H37A	0.9700
C14A—C15A	1.387 (7)	C37—H37B	0.9700
C14A—H14A	0.9300	C38—H38	0.9800
C15A—C16A	1.402 (7)	C39—C40	1.411 (4)
C15A—H15A	0.9300	C39—C44	1.412 (3)
C16A—C17A	1.412 (6)	C40—C41	1.411 (4)
C16A—H16A	0.9300	C40—H40	0.9300
C18A—C19A	1.525 (8)	C41—C42	1.391 (4)
C18A—H18A	0.9700	C41—H41	0.9300
C18A—H18B	0.9700	C42—C43	1.420 (4)
C19A—H19A	0.9600	C42—H42	0.9300
C19A—H19B	0.9600	C43—C44	1.407 (4)
C19A—H19C	0.9600	C43—H43	0.9300
C12B—C13B	1.413 (14)	C45—C46	1.538 (4)
C12B—C17B	1.421 (14)	C45—H45A	0.9700
C13B—C14B	1.400 (14)	C45—H45B	0.9700
C13B—H13B	0.9300	C46—H46A	0.9600
C14B—C15B	1.387 (14)	C46—H46B	0.9600
C14B—H14B	0.9300	C46—H46C	0.9600
C15B—C16B	1.389 (13)	C47—C48	1.389 (3)
C15B—H15B	0.9300	C47—C52	1.428 (3)
C16B—C17B	1.409 (13)	C48—C49	1.396 (4)
C16B—H16B	0.9300	C48—H48	0.9300
C18B—C19B	1.494 (14)	C49—C50	1.415 (4)
C18B—H18C	0.9700	C49—H49	0.9300
C18B—H18D	0.9700	C50—C51	1.396 (4)
C19B—H19D	0.9600	C50—H50	0.9300
C19B—H19E	0.9600	C51—C52	1.400 (3)
C19B—H19F	0.9600	C51—H51	0.9300
C20—C21	1.397 (4)	C53—C54	1.505 (4)
C20—C25	1.428 (4)	C53—H53A	0.9700
C21—C22	1.412 (4)	C53—H53B	0.9700
C21—H21	0.9300	C54—H54A	0.9600
C22—C23	1.406 (5)	C54—H54B	0.9600
C22—H22	0.9300	C54—H54C	0.9600
C23—C24	1.401 (4)
C1—Rh1—C4	91.67 (9)	C25—C24—H24	120.9
C1—Rh1—C7	153.69 (11)	O2—C25—C24	124.3 (2)
C11—Rh1—C7	97.98 (11)	O2—C25—C20	115.3 (2)
C4—Rh1—C7	81.86 (10)	C24—C25—C20	120.4 (2)
C1—Rh1—C8	171.40 (11)	O2—C26—C27	106.2 (3)
C1—Rh1—C11	92.41 (10)	O2—C26—H26A	110.5
C11—Rh1—C8	82.81 (11)	C27—C26—H26A	110.5
C4—Rh1—C8	89.02 (10)	O2—C26—H26B	110.5
C7—Rh1—C8	34.80 (12)	C27—C26—H26B	110.5
C1—Rh1—Br1	87.89 (6)	H26A—C26—H26B	108.7
C11—Rh1—Br1	154.99 (7)	C26—C27—H27A	109.5
C4—Rh1—Br1	166.45 (6)	C26—C27—H27B	109.5
C7—Rh1—Br1	92.58 (8)	H27A—C27—H27B	109.5
C8—Rh1—Br1	93.43 (8)	C26—C27—H27C	109.5
C17A—O1A—C18A	121.0 (4)	H27A—C27—H27C	109.5
C17B—O1B—C18B	120.2 (10)	H27B—C27—H27C	109.5
C25—O2—C26	118.5 (2)	C28—Rh2—C31	92.99 (9)
C1—N1—C12A	124.7 (4)	C38—Rh2—C31	38.59 (10)
C1—N2—C20	120.79 (19)	C28—Rh2—C34	157.62 (10)
C2—N1—C12A	120.8 (4)	C38—Rh2—C34	96.22 (10)
C11—Rh1—C4	38.56 (9)	C31—Rh2—C34	81.64 (10)
C1—N1—C2	114.5 (2)	C28—Rh2—C35	166.22 (10)
C1—N1—C12B	117.6 (8)	C28—Rh2—C38	92.81 (9)
C1—N2—C3	113.8 (2)	C38—Rh2—C35	80.44 (10)
C2—N1—C12B	127.9 (8)	C31—Rh2—C35	89.18 (10)
C20—N2—C3	121.60 (19)	C34—Rh2—C35	36.11 (10)
N1—C1—N2	106.9 (2)	C28—Rh2—Br2	86.98 (6)
N1—C1—Rh1	130.22 (17)	C38—Rh2—Br2	157.48 (7)
N2—C1—Rh1	122.79 (17)	C31—Rh2—Br2	163.94 (7)
N1—C2—C3	101.7 (2)	C34—Rh2—Br2	92.31 (7)
N1—C2—H2A	111.4	C35—Rh2—Br2	94.67 (7)
C3—C2—H2A	111.4	C44—O3—C45	119.0 (2)
N1—C2—H2B	111.4	C52—O4—C53	117.69 (19)
C3—C2—H2B	111.4	C28—N3—C39	122.66 (19)
H2A—C2—H2B	109.3	C28—N3—C29	113.35 (19)
N2—C3—C2	103.0 (2)	C28—N4—C47	122.61 (19)
N2—C3—H3A	111.2	C28—N4—C30	114.64 (18)
C2—C3—H3A	111.2	C39—N3—C29	123.72 (18)
N2—C3—H3B	111.2	C47—N4—C30	122.11 (19)
C2—C3—H3B	111.2	N3—C28—N4	107.3 (2)
H3A—C3—H3B	109.1	N3—C28—Rh2	127.04 (17)
C11—C4—C5	124.5 (2)	N4—C28—Rh2	125.67 (16)
C11—C4—Rh1	68.99 (14)	N3—C29—C30	103.05 (18)
C5—C4—Rh1	112.46 (17)	N3—C29—H29A	111.2
C11—C4—H4	114.2	C30—C29—H29A	111.2
C5—C4—H4	114.2	N3—C29—H29B	111.2
Rh1—C4—H4	114.2	C30—C29—H29B	111.2
C6—C5—C4	112.6 (2)	H29A—C29—H29B	109.1
C6—C5—H5A	109.1	N4—C30—C29	100.90 (18)
C4—C5—H5A	109.1	N4—C30—H30A	111.6
C6—C5—H5B	109.1	C29—C30—H30A	111.6
C4—C5—H5B	109.1	N4—C30—H30B	111.6
H5A—C5—H5B	107.8	C29—C30—H30B	111.6
C5—C6—C7	113.4 (3)	H30A—C30—H30B	109.4
C5—C6—H6A	108.9	C38—C31—C32	123.3 (2)
C7—C6—H6A	108.9	C38—C31—Rh2	69.28 (14)
C5—C6—H6B	108.9	C32—C31—Rh2	113.63 (16)
C7—C6—H6B	108.9	C38—C31—H31	114.2
H6A—C6—H6B	107.7	C32—C31—H31	114.2
C8—C7—C6	126.9 (3)	Rh2—C31—H31	114.2
C8—C7—Rh1	73.60 (18)	C33—C32—C31	111.3 (2)
C6—C7—Rh1	105.77 (19)	C33—C32—H32A	109.4
C8—C7—H7	114.0	C31—C32—H32A	109.4
C6—C7—H7	114.0	C33—C32—H32B	109.4
Rh1—C7—H7	114.0	C31—C32—H32B	109.4
C7—C8—C9	125.0 (3)	H32A—C32—H32B	108.0
C7—C8—Rh1	71.60 (16)	C32—C33—C34	114.4 (2)
C9—C8—Rh1	109.7 (2)	C32—C33—H33A	108.7
C7—C8—H8	114.2	C34—C33—H33A	108.7
C9—C8—H8	114.2	C32—C33—H33B	108.7
Rh1—C8—H8	114.2	C34—C33—H33B	108.7
C8—C9—C10	112.2 (2)	H33A—C33—H33B	107.6
C8—C9—H9A	109.2	C35—C34—C33	126.7 (3)
C10—C9—H9A	109.2	C35—C34—Rh2	74.12 (14)
C8—C9—H9B	109.2	C33—C34—Rh2	106.63 (16)
C10—C9—H9B	109.2	C35—C34—H34	113.8
H9A—C9—H9B	107.9	C33—C34—H34	113.8
C11—C10—C9	114.5 (2)	Rh2—C34—H34	113.8
C11—C10—H10A	108.6	C34—C35—C36	123.5 (3)
C9—C10—H10A	108.6	C34—C35—Rh2	69.77 (14)
C11—C10—H10B	108.6	C36—C35—Rh2	111.74 (17)
C9—C10—H10B	108.6	C34—C35—H35	114.5
H10A—C10—H10B	107.6	C36—C35—H35	114.5
C4—C11—C10	124.4 (2)	Rh2—C35—H35	114.5
C4—C11—Rh1	72.45 (14)	C35—C36—C37	111.1 (2)
C10—C11—Rh1	108.85 (19)	C35—C36—H36A	109.4
C4—C11—H11	114.4	C37—C36—H36A	109.4
C10—C11—H11	114.4	C35—C36—H36B	109.4
Rh1—C11—H11	114.4	C37—C36—H36B	109.4
N1—C12A—C17A	117.4 (5)	H36A—C36—H36B	108.0
N1—C12A—C13A	121.1 (6)	C36—C37—C38	114.3 (2)
C17A—C12A—C13A	121.3 (5)	C36—C37—H37A	108.7
C14A—C13A—C12A	120.4 (6)	C38—C37—H37A	108.7
C14A—C13A—H13A	119.8	C36—C37—H37B	108.7
C12A—C13A—H13A	119.8	C38—C37—H37B	108.7
C15A—C14A—C13A	118.2 (5)	H37A—C37—H37B	107.6
C15A—C14A—H14A	120.9	C31—C38—C37	126.5 (2)
C13A—C14A—H14A	120.9	C31—C38—Rh2	72.14 (14)
C14A—C15A—C16A	122.2 (5)	C37—C38—Rh2	110.46 (17)
C14A—C15A—H15A	118.9	C31—C38—H38	113.4
C16A—C15A—H15A	118.9	C37—C38—H38	113.4
C15A—C16A—C17A	120.3 (5)	Rh2—C38—H38	113.4
C15A—C16A—H16A	119.9	C40—C39—C44	120.3 (2)
C17A—C16A—H16A	119.9	C40—C39—N3	122.6 (2)
O1A—C17A—C12A	117.4 (5)	C44—C39—N3	117.1 (2)
O1A—C17A—C16A	125.0 (5)	C41—C40—C39	120.9 (2)
C12A—C17A—C16A	117.6 (5)	C41—C40—H40	119.6
O1A—C18A—C19A	110.7 (4)	C39—C40—H40	119.6
O1A—C18A—H18A	109.5	C42—C41—C40	118.7 (2)
C19A—C18A—H18A	109.5	C42—C41—H41	120.6
O1A—C18A—H18B	109.5	C40—C41—H41	120.6
C19A—C18A—H18B	109.5	C41—C42—C43	121.0 (2)
H18A—C18A—H18B	108.1	C41—C42—H42	119.5
C18A—C19A—H19A	109.5	C43—C42—H42	119.5
C18A—C19A—H19B	109.5	C44—C43—C42	120.4 (2)
H19A—C19A—H19B	109.5	C44—C43—H43	119.8
C18A—C19A—H19C	109.5	C42—C43—H43	119.8
H19A—C19A—H19C	109.5	O3—C44—C43	126.2 (2)
H19B—C19A—H19C	109.5	O3—C44—C39	115.0 (2)
C13B—C12B—C17B	121.3 (15)	C43—C44—C39	118.7 (2)
C13B—C12B—N1	118.4 (16)	O3—C45—C46	107.3 (2)
C17B—C12B—N1	120.2 (15)	O3—C45—H45A	110.2
C14B—C13B—C12B	120.2 (16)	C46—C45—H45A	110.2
C14B—C13B—H13B	119.9	O3—C45—H45B	110.2
C12B—C13B—H13B	119.9	C46—C45—H45B	110.2
C15B—C14B—C13B	118.1 (14)	H45A—C45—H45B	108.5
C15B—C14B—H14B	121.0	C45—C46—H46A	109.5
C13B—C14B—H14B	121.0	C45—C46—H46B	109.5
C14B—C15B—C16B	122.7 (14)	H46A—C46—H46B	109.5
C14B—C15B—H15B	118.6	C45—C46—H46C	109.5
C16B—C15B—H15B	118.6	H46A—C46—H46C	109.5
C15B—C16B—C17B	120.6 (12)	H46B—C46—H46C	109.5
C15B—C16B—H16B	119.7	C48—C47—C52	120.8 (2)
C17B—C16B—H16B	119.7	C48—C47—N4	118.3 (2)
O1B—C17B—C16B	125.8 (12)	C52—C47—N4	120.8 (2)
O1B—C17B—C12B	116.9 (13)	C47—C48—C49	119.1 (2)
C16B—C17B—C12B	117.1 (12)	C47—C48—H48	120.5
O1B—C18B—C19B	110.0 (10)	C49—C48—H48	120.5
O1B—C18B—H18C	109.7	C48—C49—C50	120.0 (2)
C19B—C18B—H18C	109.7	C48—C49—H49	120.0
O1B—C18B—H18D	109.7	C50—C49—H49	120.0
C19B—C18B—H18D	109.7	C51—C50—C49	121.7 (2)
H18C—C18B—H18D	108.2	C51—C50—H50	119.2
C18B—C19B—H19D	109.5	C49—C50—H50	119.2
C18B—C19B—H19E	109.5	C50—C51—C52	118.2 (3)
H19D—C19B—H19E	109.5	C50—C51—H51	120.9
C18B—C19B—H19F	109.5	C52—C51—H51	120.9
H19D—C19B—H19F	109.5	O4—C52—C51	123.2 (2)
H19E—C19B—H19F	109.5	O4—C52—C47	116.6 (2)
C21—C20—C25	120.6 (2)	C51—C52—C47	120.2 (2)
C21—C20—N2	120.9 (2)	O4—C53—C54	107.1 (2)
C25—C20—N2	118.5 (2)	O4—C53—H53A	110.3
C20—C21—C22	118.8 (3)	C54—C53—H53A	110.3
C20—C21—H21	120.6	O4—C53—H53B	110.3
C22—C21—H21	120.6	C54—C53—H53B	110.3
C23—C22—C21	120.6 (3)	H53A—C53—H53B	108.5
C23—C22—H22	119.7	C53—C54—H54A	109.5
C21—C22—H22	119.7	C53—C54—H54B	109.5
C24—C23—C22	121.4 (3)	H54A—C54—H54B	109.5
C24—C23—H23	119.3	C53—C54—H54C	109.5
C22—C23—H23	119.3	H54A—C54—H54C	109.5
C23—C24—C25	118.2 (3)	H54B—C54—H54C	109.5
C23—C24—H24	120.9
C12A—N1—C1—N2	−178.3 (4)	C22—C23—C24—C25	−0.2 (4)
C2—N1—C1—N2	2.2 (3)	C26—O2—C25—C24	11.6 (4)
C12B—N1—C1—N2	−179.0 (9)	C26—O2—C25—C20	−167.4 (2)
C12A—N1—C1—Rh1	−1.0 (5)	C23—C24—C25—O2	−179.4 (2)
C2—N1—C1—Rh1	179.64 (18)	C23—C24—C25—C20	−0.5 (4)
C12B—N1—C1—Rh1	−1.6 (9)	C21—C20—C25—O2	180.0 (2)
C20—N2—C1—N1	−160.5 (2)	N2—C20—C25—O2	1.6 (3)
C3—N2—C1—N1	−2.1 (3)	C21—C20—C25—C24	1.0 (4)
C20—N2—C1—Rh1	21.9 (3)	N2—C20—C25—C24	−177.4 (2)
C3—N2—C1—Rh1	−179.69 (17)	C25—O2—C26—C27	173.2 (2)
C11—Rh1—C1—N1	62.0 (2)	C39—N3—C28—N4	172.7 (2)
C4—Rh1—C1—N1	100.6 (2)	C29—N3—C28—N4	−1.5 (3)
C7—Rh1—C1—N1	175.5 (2)	C39—N3—C28—Rh2	−8.6 (3)
Br1—Rh1—C1—N1	−92.9 (2)	C29—N3—C28—Rh2	177.22 (16)
C11—Rh1—C1—N2	−120.9 (2)	C47—N4—C28—N3	−175.7 (2)
C4—Rh1—C1—N2	−82.4 (2)	C30—N4—C28—N3	−4.7 (3)
C7—Rh1—C1—N2	−7.5 (3)	C47—N4—C28—Rh2	5.6 (3)
Br1—Rh1—C1—N2	84.08 (19)	C30—N4—C28—Rh2	176.53 (16)
C1—N1—C2—C3	−1.5 (3)	C38—Rh2—C28—N3	70.7 (2)
C12A—N1—C2—C3	179.0 (4)	C31—Rh2—C28—N3	109.3 (2)
C12B—N1—C2—C3	179.8 (10)	C34—Rh2—C28—N3	−175.5 (2)
C1—N2—C3—C2	1.1 (3)	C35—Rh2—C28—N3	10.6 (5)
C20—N2—C3—C2	159.3 (2)	Br2—Rh2—C28—N3	−86.74 (19)
N1—C2—C3—N2	0.2 (3)	C38—Rh2—C28—N4	−110.8 (2)
C1—Rh1—C4—C11	−91.77 (16)	C31—Rh2—C28—N4	−72.2 (2)
C7—Rh1—C4—C11	113.85 (17)	C34—Rh2—C28—N4	3.0 (4)
C8—Rh1—C4—C11	79.66 (17)	C35—Rh2—C28—N4	−170.9 (3)
Br1—Rh1—C4—C11	−179.7 (2)	Br2—Rh2—C28—N4	91.76 (19)
C1—Rh1—C4—C5	148.40 (17)	C28—N3—C29—C30	6.6 (3)
C11—Rh1—C4—C5	−119.8 (2)	C39—N3—C29—C30	−167.6 (2)
C7—Rh1—C4—C5	−5.98 (18)	C28—N4—C30—C29	8.4 (3)
C8—Rh1—C4—C5	−40.17 (19)	C47—N4—C30—C29	179.4 (2)
Br1—Rh1—C4—C5	60.5 (4)	N3—C29—C30—N4	−8.2 (2)
C11—C4—C5—C6	−93.8 (3)	C28—Rh2—C31—C38	−90.75 (15)
Rh1—C4—C5—C6	−14.6 (3)	C34—Rh2—C31—C38	111.08 (16)
C4—C5—C6—C7	37.8 (3)	C35—Rh2—C31—C38	75.63 (16)
C5—C6—C7—C8	40.7 (4)	Br2—Rh2—C31—C38	179.78 (19)
C5—C6—C7—Rh1	−40.4 (3)	C28—Rh2—C31—C32	150.89 (19)
C1—Rh1—C7—C8	−177.2 (2)	C38—Rh2—C31—C32	−118.4 (3)
C11—Rh1—C7—C8	−64.96 (19)	C34—Rh2—C31—C32	−7.27 (19)
C4—Rh1—C7—C8	−100.11 (19)	C35—Rh2—C31—C32	−42.7 (2)
Br1—Rh1—C7—C8	92.31 (18)	Br2—Rh2—C31—C32	61.4 (3)
C1—Rh1—C7—C6	−52.6 (3)	C38—C31—C32—C33	−91.6 (3)
C11—Rh1—C7—C6	59.6 (2)	Rh2—C31—C32—C33	−11.7 (3)
C4—Rh1—C7—C6	24.5 (2)	C31—C32—C33—C34	34.3 (4)
C8—Rh1—C7—C6	124.6 (3)	C32—C33—C34—C35	43.5 (4)
Br1—Rh1—C7—C6	−143.09 (19)	C32—C33—C34—Rh2	−38.8 (3)
C6—C7—C8—C9	3.9 (5)	C28—Rh2—C34—C35	−177.6 (2)
Rh1—C7—C8—C9	101.6 (3)	C38—Rh2—C34—C35	−64.36 (17)
C6—C7—C8—Rh1	−97.6 (3)	C31—Rh2—C34—C35	−100.19 (17)
C11—Rh1—C8—C7	115.26 (19)	Br2—Rh2—C34—C35	94.76 (16)
C4—Rh1—C8—C7	77.08 (19)	C28—Rh2—C34—C33	−53.3 (3)
Br1—Rh1—C8—C7	−89.58 (18)	C38—Rh2—C34—C33	60.0 (2)
C11—Rh1—C8—C9	−6.3 (2)	C31—Rh2—C34—C33	24.12 (19)
C4—Rh1—C8—C9	−44.5 (2)	C35—Rh2—C34—C33	124.3 (3)
C7—Rh1—C8—C9	−121.6 (3)	Br2—Rh2—C34—C33	−140.93 (18)
Br1—Rh1—C8—C9	148.9 (2)	C33—C34—C35—C36	4.1 (4)
C7—C8—C9—C10	−93.3 (4)	Rh2—C34—C35—C36	103.3 (2)
Rh1—C8—C9—C10	−12.4 (3)	C33—C34—C35—Rh2	−99.2 (2)
C8—C9—C10—C11	34.1 (4)	C28—Rh2—C35—C34	176.1 (3)
C5—C4—C11—C10	2.3 (4)	C38—Rh2—C35—C34	114.65 (17)
Rh1—C4—C11—C10	−101.2 (3)	C31—Rh2—C35—C34	76.87 (17)
C5—C4—C11—Rh1	103.5 (2)	Br2—Rh2—C35—C34	−87.51 (16)
C9—C10—C11—C4	42.6 (4)	C28—Rh2—C35—C36	57.0 (5)
C9—C10—C11—Rh1	−38.6 (3)	C38—Rh2—C35—C36	−4.4 (2)
C1—Rh1—C11—C4	89.66 (16)	C31—Rh2—C35—C36	−42.2 (2)
C7—Rh1—C11—C4	−66.10 (17)	C34—Rh2—C35—C36	−119.1 (3)
C8—Rh1—C11—C4	−97.51 (17)	Br2—Rh2—C35—C36	153.40 (19)
Br1—Rh1—C11—C4	179.83 (13)	C34—C35—C36—C37	−94.1 (3)
C1—Rh1—C11—C10	−149.10 (19)	Rh2—C35—C36—C37	−14.6 (3)
C4—Rh1—C11—C10	121.2 (3)	C35—C36—C37—C38	34.8 (4)
C7—Rh1—C11—C10	55.1 (2)	C32—C31—C38—C37	2.7 (4)
C8—Rh1—C11—C10	23.7 (2)	Rh2—C31—C38—C37	−102.6 (3)
Br1—Rh1—C11—C10	−58.9 (3)	C32—C31—C38—Rh2	105.3 (2)
C1—N1—C12A—C17A	−124.3 (4)	C36—C37—C38—C31	43.8 (4)
C2—N1—C12A—C17A	55.1 (6)	C36—C37—C38—Rh2	−38.7 (3)
C12B—N1—C12A—C17A	−120 (9)	C28—Rh2—C38—C31	91.28 (15)
C1—N1—C12A—C13A	50.6 (5)	C34—Rh2—C38—C31	−68.22 (16)
C2—N1—C12A—C13A	−130.0 (4)	C35—Rh2—C38—C31	−100.82 (16)
C12B—N1—C12A—C13A	55 (9)	Br2—Rh2—C38—C31	−179.84 (13)
N1—C12A—C13A—C14A	−174.9 (6)	C28—Rh2—C38—C37	−145.61 (19)
C17A—C12A—C13A—C14A	−0.2 (2)	C31—Rh2—C38—C37	123.1 (3)
C12A—C13A—C14A—C15A	−0.1 (2)	C34—Rh2—C38—C37	54.9 (2)
C13A—C14A—C15A—C16A	0.1 (4)	C35—Rh2—C38—C37	22.30 (18)
C14A—C15A—C16A—C17A	0.1 (6)	Br2—Rh2—C38—C37	−56.7 (3)
C18A—O1A—C17A—C12A	177.4 (5)	C28—N3—C39—C40	70.3 (3)
C18A—O1A—C17A—C16A	−0.2 (7)	C29—N3—C39—C40	−116.1 (3)
N1—C12A—C17A—O1A	−2.5 (7)	C28—N3—C39—C44	−106.6 (3)
C13A—C12A—C17A—O1A	−177.4 (4)	C29—N3—C39—C44	67.0 (3)
N1—C12A—C17A—C16A	175.3 (5)	C44—C39—C40—C41	−0.2 (4)
C13A—C12A—C17A—C16A	0.4 (4)	N3—C39—C40—C41	−177.0 (2)
C15A—C16A—C17A—O1A	177.2 (5)	C39—C40—C41—C42	−0.3 (4)
C15A—C16A—C17A—C12A	−0.4 (5)	C40—C41—C42—C43	0.3 (4)
C17A—O1A—C18A—C19A	−81.2 (6)	C41—C42—C43—C44	0.1 (4)
C1—N1—C12B—C13B	65.8 (10)	C45—O3—C44—C43	0.7 (4)
C12A—N1—C12B—C13B	−110 (9)	C45—O3—C44—C39	178.8 (2)
C2—N1—C12B—C13B	−115.6 (9)	C42—C43—C44—O3	177.6 (2)
C1—N1—C12B—C17B	−118.9 (11)	C42—C43—C44—C39	−0.5 (4)
C12A—N1—C12B—C17B	65 (8)	C40—C39—C44—O3	−177.8 (2)
C2—N1—C12B—C17B	59.7 (16)	N3—C39—C44—O3	−0.8 (3)
C17B—C12B—C13B—C14B	−0.1 (3)	C40—C39—C44—C43	0.6 (4)
N1—C12B—C13B—C14B	175.2 (15)	N3—C39—C44—C43	177.5 (2)
C12B—C13B—C14B—C15B	0.0 (3)	C44—O3—C45—C46	−169.1 (2)
C13B—C14B—C15B—C16B	0.1 (6)	C28—N4—C47—C48	−74.5 (3)
C14B—C15B—C16B—C17B	0.0 (8)	C30—N4—C47—C48	115.2 (3)
C18B—O1B—C17B—C16B	4.2 (19)	C28—N4—C47—C52	103.1 (3)
C18B—O1B—C17B—C12B	178.2 (13)	C30—N4—C47—C52	−67.2 (3)
C15B—C16B—C17B—O1B	173.9 (14)	C52—C47—C48—C49	0.2 (4)
C15B—C16B—C17B—C12B	−0.1 (8)	N4—C47—C48—C49	177.8 (2)
C13B—C12B—C17B—O1B	−174.4 (12)	C47—C48—C49—C50	−1.5 (4)
N1—C12B—C17B—O1B	10.4 (16)	C48—C49—C50—C51	1.0 (4)
C13B—C12B—C17B—C16B	0.1 (6)	C49—C50—C51—C52	0.9 (4)
N1—C12B—C17B—C16B	−175.0 (15)	C53—O4—C52—C51	5.1 (4)
C17B—O1B—C18B—C19B	−167.5 (14)	C53—O4—C52—C47	−174.2 (2)
C1—N2—C20—C21	−87.6 (3)	C50—C51—C52—O4	178.6 (2)
C3—N2—C20—C21	115.6 (3)	C50—C51—C52—C47	−2.2 (4)
C1—N2—C20—C25	90.7 (3)	C48—C47—C52—O4	−179.0 (2)
C3—N2—C20—C25	−66.0 (3)	N4—C47—C52—O4	3.4 (3)
C25—C20—C21—C22	−0.7 (4)	C48—C47—C52—C51	1.7 (4)
N2—C20—C21—C22	177.6 (2)	N4—C47—C52—C51	−175.8 (2)
C20—C21—C22—C23	0.0 (4)	C52—O4—C53—C54	−175.9 (2)
C21—C22—C23—C24	0.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1A	0.97	2.20	2.795 (6)	118
C3—H3A···O2	0.97	2.51	3.030 (4)	114
C16B—H16B···Br2^i	0.93	2.88	3.798 (2)	167
C29—H29B···O3	0.97	2.49	3.007 (4)	113
C30—H30A···O4	0.97	2.60	3.121 (3)	114
C43—H43···Br1	0.93	2.83	3.745 (3)	167

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