An organometallic Rh^III complex with a distorted octahedral structure: (acetonitrile-[kappa]N)dimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane-[kappa]³N,N',N'')rhodium(III) tetraphenylborate

In the title compound, [Rh(CH₃)₂(C₂H₃N)(C₉H₂₁N₃)](C₂₄H₂₀B), the geometry around the Rh^III centre is distorted octahedral, with elongated Rh-N bonds trans to the metal-bonded methyl groups. The metal-containing cations are located in channels formed by an anionic supramolecular mesh, in which aromatic [pi]-[pi] interactions between anionic [B(Ph)₄]^- units play a major role.

S1. Comment

Recent years have seen an increasing interest in hard non-π-interacting ligands for organometallic and inorganic coordination compounds, azacrown compounds being one group of interest (Chaudhuri & Wieghardt, 1987; Reichenbach-Klinke & Konig, 2002). In this respect, the Cn^* ligand present in the title compound, (I) [Cn^* is 1,4,7-trimethyl-1,4,7-triazacyclononane, according to the notation suggested by Flood et al. (2000)], represents a six-electron, and thus isoelectronic, alternative to the more conventional ligand systems, such as cyclopentadienyl (Cp and Cp^*; η⁵-C₅R₅, R = H or Me), tris(pyrazolyl)borate and tridentate phosphine ligands. Azacrown ligands are devoid of back-bonding capabilities, commonly yielding highly electron-rich metal centres (Flood, Sowa et al., 1996). \sch

A range of group IX organometallic compounds have been shown to exhibit catalytic activity in a variety of reactions, such as C—H activation and olefin polymerization (for recent reviews, see Shilov & Shul'pin, 1997; Britovsek et al., 1999). In some instances (i.e. polymerization), late-metal compounds might represent robust alternatives to early-metal catalysts, which tend to be highly sensitive towards polar functional groups, air and water. In fact, Cn^*Rh(H₂O)(Me)(OH)⁺, a complex closely related to (I), has been reported to polymerize ethene using water as solvent (Flood et al., 1993).

Compound (I) was synthesized as part of a general study of electron-transfer induced reactions of certain group IX organometallic complexes (Fooladi & Tilset, 1997; Fooladi et al., 2002, and references therein). Oxidation of the trimethyl complex Cn^*RhMe₃, previously reported by Flood, Wang et al. (1996), in acetonitrile solvent resulted in the spontaneous elimination of ethane, yielding a mixture of the two solvento complexes Cn^*Rh(Me)(NCMe)₂²⁺ and (I). The oxidatively induced simultaneous cleavage of two M—C bonds yielding ethane resembles the reactivity of other Rh^III compounds [Cp^*Rh(Me₂SO)Me₂ and Cp^*Rh(PPh₃)Me₂], but contrasts with the reactivity of related Ir compounds [Cp^*Ir(Me₂SO)Me₂ and Cp^*Ir(PPh₃)Me₂], in which bond formation (Ir—Ir bond formation and insertion of Ir into a Cp^* C—H bond) is involved in the primary reactions, presumably due to the relatively different M—C and M—M bond strengths of second- versus third-row metals (Fooladi et al., 2002).

The structure of the Rh^III cation in (I) is shown in Fig. 1. The three N—Rh—N bond angles within the Cn^* ligand exhibit a marked deviation from the ideal value of 90° for octahedral coordination, with values lying between 80.95 (3) and 83.08 (4)°. Also, the acetonitrile and the two Rh-bound methyl ligands are forced slightly towards one another, but less than for the cyclononane ligand. In both cases, the bond angles closely resemble those observed in the corresponding trimethyl analogue Cn^*RhMe₃ [N—Rh—N 80.2 (2) and 80.0 (3)°, Me—Rh—Me 87.6 (3) and 87.2 (5)°; Flood, Wang et al. (1996)]. A noticeable trans influence is reflected in the Rh—N(Cn^*) bond distances, as the two Rh—N bonds trans to the Rh-bound methyl groups are markedly elongated [2.2135 (9) and 2.2258 (9) Å] compared with the Rh—N bond trans to the acetonitrile ligand [2.0942 (8) Å]. This elongation also affects the Cn^* ligand, in that the N—Rh—N angle trans to the two methyl groups is smaller relative to the angles involving the shorter Rh—N bond, as would be expected according to a valence-shell electron-pair repulsion argument: a shorter bond results in more steric congestion close to the metal centre, thus resulting in a wider N—Rh—N bond angle.

To our knowledge, only one other X-ray crystal structure of a rhodium acetonitrile alkyl compound has been reported, namely that of the octahedral compound [Rh(PNP)(Ph)(Me)(NCMe)][BF₄], in which PNP is the tridentate ligand 2,6-bis(diphenylphospanylmethyl)pyridine, (II) (Hahn et al., 1999). The Rh—N bond of the acetonitrile ligand in (II) is slightly longer [2.142 (3) Å] than the corresponding bond in (I). This elongation is presumably due to a stronger trans influence of the methyl group compared with the Cn^* N atom. In (I), the end-on coordinated acetonitrile exhibits a nearly linear arrangement [Rh1—N4—C10 176.31 (11)° and N4—C10—C11 179.08 (15)°], as observed in (II) and other related compounds (Hahn et al., 1999, and references therein). Furthermore, a related tetranuclear Cn^* acetonitrile complex, [{Cn^*Rh(NCMe)Cl₂}₃Ag][OTf] was recently published (OTf is?; Südfeld & Sheldrick, 2000). Unfortunately, the characterization is insufficient for a detailed discussion of the structural properties of the compound.

As far as the crystal packing of (I) is concerned, it should be noted that numerous π–π-stacking interactions between adjacent [B(Ph)₄]^- anions play a major role in the solid-state phase of this complex. These interactions are typically in the range 2.9–3.2 Å, where the distance is between the aromatic H atoms and the C atoms of neighbouring molecules. Furthermore, the [B(Ph)₄]^- anions form a mesh with channels when looking along the b axis in the crystal. The metal-containing cations are confined within these channels (Fig. 2).

S2. Experimental

The synthesis of (I) was carried out according to the procedure previously reported by Fooladi et al. (1997). A solution of HBF₄·Et₂O (51 mg, 0.31 mmol) in acetonitrile (1 ml) was added dropwise to a stirred solution of Cn^*RhMe₃ (100 mg, 0.31 mmol) in acetonitrile-dichloromethane (2:1, 6 ml) at 259 K. The mixture was warmed to ambient temperature and stirred for another 1.5 h, followed by the removal of the solvent in vacuo. The oily residue was washed with benzene (2 ml) in order to remove any remaining Cn^*RhMe₃, dissolved in dichloromethane, filtered through Celite and recrystallized from dichloromethane-ether (Ratio?), to give yellow crystals of (I) (yield 108 mg, 81%). X-ray quality crystals were obtained by slow diffusion of diethyl ether into a solution of (I) in dichloromethane under a nitrogen atmosphere over a period of nine months.

S3. Refinement

All H atoms were placed in calculated geometric positions, with C—H distances in the range 0.95–0.99 Å Is this added text OK?, and refined isotropically riding on their parent atoms.

Computing details

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. A view of the molecular structure of the cation in (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A molecular packing diagram for (I), viewed along the b axis, showing the anionic channel-forming network in which the metal-containing cations are confined.

(acetonitrile-κN)dimethyl(1,4,7-trimethyl-1,4,7-triazacyclononane- κ³N)rhodium(III) tetraphenylborate

Crystal data

[Rh(CH3)2(C2H3N)(C9H21N3)][B(C6H5)4]	F(000) = 1400
Mr = 664.53	Dx = 1.277 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.2560 (3) Å	Cell parameters from 8192 reflections
b = 16.6074 (3) Å	θ = 2.3–40.4°
c = 14.6189 (3) Å	µ = 0.52 mm^−1
β = 92.789 (1)°	T = 150 K
V = 3457.0 (1) Å^3	Block, yellow
Z = 4	0.6 × 0.4 × 0.3 mm

Data collection

Siemens SMART CCD area-detector diffractometer	20545 independent reflections
Radiation source: fine-focus sealed tube	17370 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω scans	θmax = 40.4°, θmin = 2.3°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −25→25
Tmin = 0.73, Tmax = 0.85	k = −29→30
55207 measured reflections	l = −25→26

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H-atom parameters constrained
S = 1.21	w = 1/[σ^2(Fo^2) + (0.02P)^2 + 1.41P] where P = (Fo^2 + 2Fc^2)/3
20545 reflections	(Δ/σ)max = 0.003
388 parameters	Δρmax = 0.74 e Å^−3
0 restraints	Δρmin = −0.64 e Å^−3

Special details

Refinement. Data collection was carried out using a Siemens SMART CCD Area-Detector Diffractometer (Siemens, 1995) and nominally covered over a hemisphere of reciprocal space, by a combination of 5 sets of exposures. Each exposure of 30 s covered 0.6° in ω. Crystal-to-detector distance was 5.00 cm.

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

	x	y	z	Uiso*/Ueq
Rh1	0.296683 (5)	0.087162 (5)	−0.187845 (5)	0.01646 (2)
N1	0.15194 (6)	0.09656 (6)	−0.17165 (6)	0.02086 (14)
N2	0.28258 (6)	0.21633 (5)	−0.22326 (7)	0.02165 (15)
N3	0.25207 (7)	0.07506 (6)	−0.33524 (6)	0.02287 (15)
N4	0.43332 (6)	0.08282 (6)	−0.20910 (7)	0.02301 (15)
B1	0.16728 (7)	0.10662 (6)	0.26848 (7)	0.01664 (15)
C1	0.12077 (8)	0.18382 (7)	−0.18156 (10)	0.0286 (2)
H1A	0.0903	0.1919	−0.2432	0.034*
H1B	0.0739	0.1958	−0.1357	0.034*
C2	0.20277 (8)	0.24153 (7)	−0.16852 (9)	0.0284 (2)
H2A	0.1824	0.2963	−0.1873	0.034*
H2B	0.2234	0.2434	−0.1029	0.034*
C3	0.25902 (9)	0.22485 (7)	−0.32367 (8)	0.0272 (2)
H3A	0.2919	0.2725	−0.3473	0.033*
H3B	0.1906	0.2339	−0.3335	0.033*
C4	0.28693 (9)	0.15086 (8)	−0.37655 (8)	0.0283 (2)
H4A	0.2613	0.1552	−0.4405	0.034*
H4B	0.3562	0.1486	−0.3779	0.034*
C5	0.14697 (8)	0.07107 (8)	−0.34039 (9)	0.0285 (2)
H5A	0.1261	0.0311	−0.3873	0.034*
H5B	0.1212	0.1242	−0.3594	0.034*
C6	0.10885 (7)	0.04775 (7)	−0.24891 (9)	0.0262 (2)
H6A	0.0399	0.0555	−0.2516	0.031*
H6B	0.1216	−0.0100	−0.2372	0.031*
C7	0.11694 (9)	0.06524 (9)	−0.08413 (9)	0.0306 (2)
H7A	0.0481	0.0648	−0.0877	0.046*
H7B	0.1394	0.1000	−0.0335	0.046*
H7C	0.1403	0.0104	−0.0737	0.046*
C8	0.36653 (9)	0.26530 (8)	−0.19760 (10)	0.0320 (2)
H8A	0.3515	0.3225	−0.2057	0.048*
H8B	0.4178	0.2508	−0.2367	0.048*
H8C	0.3859	0.2550	−0.1334	0.048*
C9	0.29219 (12)	0.00559 (9)	−0.38258 (9)	0.0358 (3)
H9A	0.2742	0.0083	−0.4481	0.054*
H9B	0.2683	−0.0444	−0.3569	0.054*
H9C	0.3608	0.0068	−0.3742	0.054*
C10	0.51289 (7)	0.08183 (7)	−0.21665 (10)	0.0271 (2)
C11	0.61376 (8)	0.08169 (8)	−0.22523 (14)	0.0419 (4)
H11A	0.6326	0.1312	−0.2559	0.063*
H11B	0.6317	0.0349	−0.2614	0.063*
H11C	0.6452	0.0789	−0.1642	0.063*
C12	0.30220 (8)	−0.03601 (7)	−0.15738 (8)	0.02548 (19)
H12A	0.2806	−0.0669	−0.2115	0.038*
H12B	0.2616	−0.0475	−0.1068	0.038*
H12C	0.3670	−0.0512	−0.1396	0.038*
C13	0.33397 (9)	0.10531 (9)	−0.05126 (8)	0.0308 (2)
H13A	0.4026	0.1045	−0.0425	0.046*
H13B	0.3071	0.0624	−0.0146	0.046*
H13C	0.3100	0.1576	−0.0318	0.046*
C14	0.15430 (6)	0.00851 (5)	0.25660 (6)	0.01619 (13)
C15	0.14865 (7)	−0.02813 (6)	0.16991 (7)	0.02044 (16)
H15	0.1485	0.0052	0.1171	0.025*
C16	0.14320 (8)	−0.11149 (7)	0.15811 (9)	0.02563 (19)
H16	0.1397	−0.1336	0.0981	0.031*
C17	0.14288 (8)	−0.16235 (6)	0.23353 (10)	0.0272 (2)
H17	0.1372	−0.2190	0.2258	0.033*
C18	0.15112 (8)	−0.12859 (6)	0.32064 (9)	0.0260 (2)
H18	0.1526	−0.1624	0.3731	0.031*
C19	0.15718 (7)	−0.04509 (6)	0.33125 (7)	0.02066 (16)
H19	0.1635	−0.0236	0.3914	0.025*
C20	0.11976 (7)	0.14283 (6)	0.36035 (7)	0.01845 (14)
C21	0.04392 (7)	0.10640 (7)	0.40219 (7)	0.02191 (17)
H21	0.0221	0.0557	0.3799	0.026*
C22	−0.00086 (8)	0.14167 (8)	0.47528 (8)	0.0275 (2)
H22	−0.0512	0.1144	0.5022	0.033*
C23	0.02821 (9)	0.21636 (8)	0.50855 (8)	0.0307 (2)
H23	−0.0022	0.2408	0.5578	0.037*
C24	0.10244 (10)	0.25477 (8)	0.46862 (9)	0.0308 (2)
H24	0.1227	0.3061	0.4904	0.037*
C25	0.14753 (8)	0.21832 (7)	0.39643 (8)	0.02485 (18)
H25	0.1987	0.2455	0.3708	0.030*
C26	0.28173 (7)	0.11834 (6)	0.27288 (7)	0.01767 (14)
C27	0.33537 (8)	0.11065 (7)	0.35563 (8)	0.02511 (19)
H27	0.3037	0.1060	0.4111	0.030*
C28	0.43345 (9)	0.10966 (9)	0.35942 (10)	0.0340 (3)
H28	0.4672	0.1039	0.4167	0.041*
C29	0.48181 (8)	0.11704 (8)	0.27948 (12)	0.0364 (3)
H29	0.5485	0.1169	0.2818	0.044*
C30	0.43137 (9)	0.12456 (8)	0.19647 (11)	0.0321 (3)
H30	0.4636	0.1295	0.1414	0.038*
C31	0.33340 (8)	0.12494 (7)	0.19360 (8)	0.02404 (18)
H31	0.3003	0.1298	0.1359	0.029*
C32	0.11267 (7)	0.15491 (6)	0.18310 (7)	0.01845 (14)
C33	0.02382 (7)	0.12904 (7)	0.14924 (7)	0.02222 (17)
H33	−0.0012	0.0809	0.1734	0.027*
C34	−0.02946 (9)	0.17018 (8)	0.08213 (8)	0.0283 (2)
H34	−0.0892	0.1500	0.0615	0.034*
C35	0.00463 (10)	0.24084 (8)	0.04520 (9)	0.0340 (3)
H35	−0.0310	0.2693	−0.0009	0.041*
C36	0.09157 (12)	0.26887 (8)	0.07701 (10)	0.0373 (3)
H36	0.1157	0.3173	0.0527	0.045*
C37	0.14466 (9)	0.22681 (7)	0.14470 (9)	0.0294 (2)
H37	0.2041	0.2476	0.1652	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01368 (3)	0.01882 (3)	0.01683 (3)	0.00017 (2)	0.00035 (2)	0.00018 (2)
N1	0.0149 (3)	0.0239 (4)	0.0240 (4)	−0.0007 (3)	0.0027 (3)	−0.0003 (3)
N2	0.0199 (3)	0.0189 (3)	0.0259 (4)	−0.0020 (3)	−0.0017 (3)	−0.0003 (3)
N3	0.0257 (4)	0.0249 (4)	0.0179 (3)	−0.0032 (3)	0.0009 (3)	−0.0007 (3)
N4	0.0165 (3)	0.0245 (4)	0.0282 (4)	0.0010 (3)	0.0022 (3)	0.0007 (3)
B1	0.0179 (4)	0.0157 (4)	0.0164 (4)	0.0005 (3)	0.0014 (3)	0.0002 (3)
C1	0.0199 (4)	0.0260 (5)	0.0402 (6)	0.0053 (4)	0.0036 (4)	0.0000 (4)
C2	0.0270 (5)	0.0219 (4)	0.0363 (6)	0.0036 (4)	0.0017 (4)	−0.0051 (4)
C3	0.0297 (5)	0.0243 (5)	0.0271 (5)	−0.0035 (4)	−0.0038 (4)	0.0072 (4)
C4	0.0346 (5)	0.0312 (5)	0.0192 (4)	−0.0042 (4)	0.0015 (4)	0.0044 (4)
C5	0.0268 (5)	0.0315 (5)	0.0262 (5)	−0.0069 (4)	−0.0096 (4)	0.0008 (4)
C6	0.0178 (4)	0.0272 (5)	0.0332 (5)	−0.0056 (3)	−0.0025 (4)	0.0006 (4)
C7	0.0256 (5)	0.0362 (6)	0.0309 (5)	−0.0009 (4)	0.0119 (4)	0.0026 (5)
C8	0.0291 (5)	0.0253 (5)	0.0408 (7)	−0.0095 (4)	−0.0066 (5)	0.0004 (5)
C9	0.0494 (8)	0.0329 (6)	0.0257 (5)	−0.0017 (5)	0.0071 (5)	−0.0074 (4)
C10	0.0173 (4)	0.0221 (4)	0.0421 (6)	0.0001 (3)	0.0035 (4)	−0.0016 (4)
C11	0.0161 (4)	0.0267 (6)	0.0835 (12)	−0.0019 (4)	0.0098 (5)	−0.0054 (6)
C12	0.0241 (4)	0.0249 (5)	0.0276 (5)	0.0036 (4)	0.0031 (4)	0.0049 (4)
C13	0.0308 (5)	0.0424 (7)	0.0187 (4)	−0.0010 (5)	−0.0035 (4)	−0.0023 (4)
C14	0.0150 (3)	0.0152 (3)	0.0184 (3)	0.0007 (2)	0.0015 (3)	0.0004 (3)
C15	0.0230 (4)	0.0185 (4)	0.0197 (4)	0.0022 (3)	−0.0002 (3)	−0.0020 (3)
C16	0.0258 (4)	0.0203 (4)	0.0304 (5)	0.0026 (3)	−0.0027 (4)	−0.0080 (4)
C17	0.0235 (4)	0.0151 (4)	0.0433 (6)	0.0011 (3)	0.0047 (4)	−0.0018 (4)
C18	0.0270 (4)	0.0177 (4)	0.0341 (5)	0.0047 (3)	0.0094 (4)	0.0069 (4)
C19	0.0232 (4)	0.0184 (4)	0.0207 (4)	0.0034 (3)	0.0042 (3)	0.0036 (3)
C20	0.0197 (3)	0.0185 (4)	0.0173 (4)	0.0037 (3)	0.0012 (3)	−0.0004 (3)
C21	0.0212 (4)	0.0244 (4)	0.0204 (4)	0.0037 (3)	0.0037 (3)	0.0005 (3)
C22	0.0266 (5)	0.0348 (6)	0.0216 (4)	0.0098 (4)	0.0070 (4)	0.0025 (4)
C23	0.0366 (6)	0.0355 (6)	0.0201 (4)	0.0176 (5)	0.0031 (4)	−0.0035 (4)
C24	0.0395 (6)	0.0245 (5)	0.0281 (5)	0.0098 (4)	−0.0011 (4)	−0.0087 (4)
C25	0.0290 (5)	0.0193 (4)	0.0263 (5)	0.0030 (3)	0.0023 (4)	−0.0040 (3)
C26	0.0195 (3)	0.0149 (3)	0.0187 (4)	−0.0012 (3)	0.0019 (3)	−0.0023 (3)
C27	0.0245 (4)	0.0283 (5)	0.0222 (4)	0.0038 (4)	−0.0028 (3)	−0.0064 (4)
C28	0.0247 (5)	0.0337 (6)	0.0425 (7)	0.0052 (4)	−0.0106 (5)	−0.0152 (5)
C29	0.0188 (4)	0.0264 (5)	0.0639 (9)	−0.0028 (4)	0.0025 (5)	−0.0124 (6)
C30	0.0255 (5)	0.0244 (5)	0.0478 (7)	−0.0031 (4)	0.0164 (5)	−0.0004 (5)
C31	0.0244 (4)	0.0226 (4)	0.0257 (5)	−0.0012 (3)	0.0077 (3)	0.0008 (3)
C32	0.0219 (4)	0.0155 (3)	0.0180 (4)	0.0017 (3)	0.0014 (3)	0.0006 (3)
C33	0.0205 (4)	0.0246 (4)	0.0215 (4)	0.0028 (3)	0.0000 (3)	0.0028 (3)
C34	0.0274 (5)	0.0346 (6)	0.0226 (5)	0.0103 (4)	−0.0025 (4)	−0.0001 (4)
C35	0.0436 (7)	0.0328 (6)	0.0252 (5)	0.0169 (5)	−0.0013 (5)	0.0066 (4)
C36	0.0505 (8)	0.0236 (5)	0.0378 (7)	0.0046 (5)	0.0012 (6)	0.0138 (5)
C37	0.0348 (5)	0.0191 (4)	0.0338 (6)	−0.0020 (4)	−0.0019 (4)	0.0066 (4)

Geometric parameters (Å, º)

Rh1—N1	2.0942 (8)	C12—H12B	0.9800
Rh1—N2	2.2135 (9)	C12—H12C	0.9800
Rh1—N3	2.2258 (9)	C13—H13A	0.9800
Rh1—N4	1.9888 (9)	C13—H13B	0.9800
Rh1—C12	2.0941 (11)	C13—H13C	0.9800
Rh1—C13	2.0633 (12)	C14—C15	1.4046 (14)
N1—C7	1.4895 (15)	C14—C19	1.4073 (13)
N1—C6	1.4976 (15)	C15—C16	1.3968 (15)
N1—C1	1.5205 (15)	C15—H15	0.9500
N2—C8	1.4802 (14)	C16—C17	1.3891 (18)
N2—C2	1.4828 (15)	C16—H16	0.9500
N2—C3	1.4965 (15)	C17—C18	1.3912 (19)
N3—C9	1.4750 (17)	C17—H17	0.9500
N3—C4	1.4918 (15)	C18—C19	1.3975 (15)
N3—C5	1.4980 (15)	C18—H18	0.9500
N4—C10	1.1451 (13)	C19—H19	0.9500
B1—C26	1.6414 (14)	C20—C21	1.4048 (15)
B1—C20	1.6472 (14)	C20—C25	1.4093 (15)
B1—C32	1.6470 (14)	C21—C22	1.3995 (15)
B1—C14	1.6480 (14)	C21—H21	0.9500
C1—C2	1.5165 (17)	C22—C23	1.388 (2)
C1—H1A	0.9900	C22—H22	0.9500
C1—H1B	0.9900	C23—C24	1.388 (2)
C2—H2A	0.9900	C23—H23	0.9500
C2—H2B	0.9900	C24—C25	1.3998 (16)
C3—C4	1.5152 (19)	C24—H24	0.9500
C3—H3A	0.9900	C25—H25	0.9500
C3—H3B	0.9900	C26—C27	1.4051 (15)
C4—H4A	0.9900	C26—C31	1.4074 (14)
C4—H4B	0.9900	C27—C28	1.3967 (17)
C5—C6	1.5181 (18)	C27—H27	0.9500
C5—H5A	0.9900	C28—C29	1.391 (2)
C5—H5B	0.9900	C28—H28	0.9500
C6—H6A	0.9900	C29—C30	1.386 (2)
C6—H6B	0.9900	C29—H29	0.9500
C7—H7A	0.9800	C30—C31	1.3953 (17)
C7—H7B	0.9800	C30—H30	0.9500
C7—H7C	0.9800	C31—H31	0.9500
C8—H8A	0.9800	C32—C33	1.4046 (15)
C8—H8B	0.9800	C32—C37	1.4049 (15)
C8—H8C	0.9800	C33—C34	1.3906 (15)
C9—H9A	0.9800	C33—H33	0.9500
C9—H9B	0.9800	C34—C35	1.389 (2)
C9—H9C	0.9800	C34—H34	0.9500
C10—C11	1.4495 (16)	C35—C36	1.383 (2)
C11—H11A	0.9800	C35—H35	0.9500
C11—H11B	0.9800	C36—C37	1.4026 (18)
C11—H11C	0.9800	C36—H36	0.9500
C12—H12A	0.9800	C37—H37	0.9500
N1—Rh1—N2	82.84 (3)	H9B—C9—H9C	109.5
N1—Rh1—N3	83.08 (4)	N4—C10—C11	179.08 (15)
N2—Rh1—N3	80.95 (3)	C10—C11—H11A	109.5
N4—Rh1—C12	88.33 (4)	C10—C11—H11B	109.5
N4—Rh1—C13	87.04 (5)	H11A—C11—H11B	109.5
N4—Rh1—N1	176.69 (4)	C10—C11—H11C	109.5
C13—Rh1—N1	95.08 (5)	H11A—C11—H11C	109.5
C12—Rh1—C13	86.08 (5)	H11B—C11—H11C	109.5
N1—Rh1—C12	94.35 (4)	Rh1—C12—H12A	109.5
N4—Rh1—N2	94.42 (4)	Rh1—C12—H12B	109.5
C13—Rh1—N2	95.80 (5)	H12A—C12—H12B	109.5
C12—Rh1—N2	176.74 (4)	Rh1—C12—H12C	109.5
N4—Rh1—N3	94.67 (4)	H12A—C12—H12C	109.5
C13—Rh1—N3	176.42 (5)	H12B—C12—H12C	109.5
C12—Rh1—N3	97.11 (4)	Rh1—C13—H13A	109.5
C7—N1—C6	108.45 (9)	Rh1—C13—H13B	109.5
C7—N1—C1	107.83 (9)	H13A—C13—H13B	109.5
C6—N1—C1	109.68 (9)	Rh1—C13—H13C	109.5
C7—N1—Rh1	116.37 (7)	H13A—C13—H13C	109.5
C6—N1—Rh1	104.16 (6)	H13B—C13—H13C	109.5
C1—N1—Rh1	110.20 (6)	C15—C14—C19	115.08 (9)
C8—N2—C2	109.89 (10)	C15—C14—B1	121.64 (8)
C8—N2—C3	109.68 (9)	C19—C14—B1	123.01 (9)
C2—N2—C3	111.17 (9)	C16—C15—C14	122.76 (10)
C8—N2—Rh1	114.21 (7)	C16—C15—H15	118.6
C2—N2—Rh1	102.17 (7)	C14—C15—H15	118.6
C3—N2—Rh1	109.55 (7)	C17—C16—C15	120.46 (11)
C9—N3—C4	109.00 (10)	C17—C16—H16	119.8
C9—N3—C5	110.58 (10)	C15—C16—H16	119.8
C4—N3—C5	111.66 (9)	C16—C17—C18	118.57 (10)
C9—N3—Rh1	115.20 (8)	C16—C17—H17	120.7
C4—N3—Rh1	103.33 (7)	C18—C17—H17	120.7
C5—N3—Rh1	106.90 (7)	C17—C18—C19	120.23 (10)
Rh1—N4—C10	176.31 (11)	C17—C18—H18	119.9
C26—B1—C20	111.85 (8)	C19—C18—H18	119.9
C26—B1—C32	113.84 (8)	C18—C19—C14	122.84 (10)
C20—B1—C32	104.02 (7)	C18—C19—H19	118.6
C26—B1—C14	103.16 (7)	C14—C19—H19	118.6
C20—B1—C14	113.48 (8)	C21—C20—C25	115.36 (9)
C32—B1—C14	110.80 (8)	C21—C20—B1	123.61 (9)
C2—C1—N1	111.74 (9)	C25—C20—B1	120.71 (9)
C2—C1—H1A	109.3	C22—C21—C20	122.78 (11)
N1—C1—H1A	109.3	C22—C21—H21	118.6
C2—C1—H1B	109.3	C20—C21—H21	118.6
N1—C1—H1B	109.3	C23—C22—C21	120.13 (11)
H1A—C1—H1B	107.9	C23—C22—H22	119.9
N2—C2—C1	111.14 (9)	C21—C22—H22	119.9
N2—C2—H2A	109.4	C22—C23—C24	118.94 (10)
C1—C2—H2A	109.4	C22—C23—H23	120.5
N2—C2—H2B	109.4	C24—C23—H23	120.5
C1—C2—H2B	109.4	C23—C24—C25	120.38 (11)
H2A—C2—H2B	108.0	C23—C24—H24	119.8
N2—C3—C4	111.82 (9)	C25—C24—H24	119.8
N2—C3—H3A	109.3	C24—C25—C20	122.40 (11)
C4—C3—H3A	109.3	C24—C25—H25	118.8
N2—C3—H3B	109.3	C20—C25—H25	118.8
C4—C3—H3B	109.3	C27—C26—C31	115.55 (10)
H3A—C3—H3B	107.9	C27—C26—B1	121.41 (9)
N3—C4—C3	112.14 (9)	C31—C26—B1	122.42 (9)
N3—C4—H4A	109.2	C28—C27—C26	122.48 (12)
C3—C4—H4A	109.2	C28—C27—H27	118.8
N3—C4—H4B	109.2	C26—C27—H27	118.8
C3—C4—H4B	109.2	C29—C28—C27	120.12 (12)
H4A—C4—H4B	107.9	C29—C28—H28	119.9
N3—C5—C6	111.54 (9)	C27—C28—H28	119.9
N3—C5—H5A	109.3	C30—C29—C28	119.11 (11)
C6—C5—H5A	109.3	C30—C29—H29	120.4
N3—C5—H5B	109.3	C28—C29—H29	120.4
C6—C5—H5B	109.3	C29—C30—C31	120.18 (12)
H5A—C5—H5B	108.0	C29—C30—H30	119.9
N1—C6—C5	112.02 (9)	C31—C30—H30	119.9
N1—C6—H6A	109.2	C30—C31—C26	122.55 (11)
C5—C6—H6A	109.2	C30—C31—H31	118.7
N1—C6—H6B	109.2	C26—C31—H31	118.7
C5—C6—H6B	109.2	C33—C32—C37	115.08 (10)
H6A—C6—H6B	107.9	C33—C32—B1	120.20 (9)
N1—C7—H7A	109.5	C37—C32—B1	124.47 (9)
N1—C7—H7B	109.5	C34—C33—C32	123.41 (11)
H7A—C7—H7B	109.5	C34—C33—H33	118.3
N1—C7—H7C	109.5	C32—C33—H33	118.3
H7A—C7—H7C	109.5	C33—C34—C35	119.98 (12)
H7B—C7—H7C	109.5	C33—C34—H34	120.0
N2—C8—H8A	109.5	C35—C34—H34	120.0
N2—C8—H8B	109.5	C36—C35—C34	118.58 (11)
H8A—C8—H8B	109.5	C36—C35—H35	120.7
N2—C8—H8C	109.5	C34—C35—H35	120.7
H8A—C8—H8C	109.5	C35—C36—C37	120.90 (12)
H8B—C8—H8C	109.5	C35—C36—H36	119.5
N3—C9—H9A	109.5	C37—C36—H36	119.5
N3—C9—H9B	109.5	C32—C37—C36	122.05 (12)
H9A—C9—H9B	109.5	C32—C37—H37	119.0
N3—C9—H9C	109.5	C36—C37—H37	119.0
H9A—C9—H9C	109.5