A 1,2,4-diazaphospholane complex of rhodium

The crystal structure of a prospective olefin catalyst, namely {2-[1-acetyl-5-(2-hydroxy­phenyl)-4-phenyl-1,2,4-di­aza­phospholan-3-yl]­phenyl acetate-κP}chloro­(η⁴-cyclo­octa-1,5-diene)rhodium(I) di­chloro­methane solvate, [RhCl(C₈H₁₂)(C₂₄H₂₃N₂O₄P)]·CH₂Cl₂, has been determined at 173 K. The five-membered heterocycle of the phosphine ligand is in a slightly distorted twist conformation. An intramolecular N1—H1...Cl1 hydrogen bond contributes to the adopted conformation and may additionally participate in secondary interactions with substrates during catalysis.

S1. Comment

Rhodium complexes utilizing chiral phosphine ligands, such as 1,2-bis[(2R,5R)-2,5-dimethylphospholano]benzene [(R,R)—Me-DuPHOS], have become important compounds in catalyzing highly enantioselective asymmetric hydrogenation reactions (Burk et al., 1999). In this study, the title complex, (I), of rhodium coordinated by 1,2,4-diazaphospholane, which is a structural analog of DuPHOS, has been successfully synthesized and structurally characterized. Diazaphospholane-based phosphine ligands are a potentially attractive class of ligand in catalyst development, because these compounds are readily synthesized and easily varied (Landis et al., 2001). \sch

Compound (I) is a rhodium(I) complex where the metal center is formally in a square-planar coordination environment. The ligands about Rh consist of a multiply substituted 1,2,4-diazaphospholane, Cl⁻ and cycloocta-1,5-diene (COD). While the Rh—Cl1 and Rh—P distances are typical, statistically significant differences are observed between the corresponding Rh-olefin [Rh-centroid(C═C)] bonds of COD in (I) (Table 1). The Rh-olefin distance trans to P [2.108 (2) Å] is 0.104 Å longer than the Rh-olefin separation trans to Cl [2.004 (2) Å]. In 85 compounds containing 161 relevant bonds reported to the Cambridge Structural Database (CSD, Version?; Allen, 2002), the corresponding values for Rh-olefin bonds trans to P average 2.12 (3) Å. When the trans ligand is Cl⁻, however, the average Rh-olefin distance is 1.99 (2) Å for 40 compounds containing 48 relevant bonds. The disparity observed between the Rh-olefin bonds is due to the differing trans influence effects of P, a strong σ donor, compared with Cl⁻, a weak π and σ donor (Miessler & Tarr, 1999). Additionally, the C1═C2 distance is 0.03 Å shorter than the C5═C6 distance (Table 1). However, these distances fall in the expected range for coordinated olefins.

The conformation of the five-membered heterocycle P/C9/N1/N2/C10 in (I) was characterized according to Cremer & Pople (1975). Typically, the most stable spatial arrangement of five-membered rings such as cyclopentane is either the twist or the energetically similar envelope conformation, and the most favorable combination of steric, electronic and non-bonding interactions determine the adopted conformation (March, 1992). The generalized puckering coordinates q₂ [0.472 (2) Å] and ϕ₂ [56.6 (3)°] suggest that the spatial arrangement of the ring atoms in (I) is essentially the twist form ³T₂, with a very minor contribution of the envelope ³E form, where atom N1 acts as the `flap' atom of the envelope.

The twist conformation of the ring in (I) is stabilized by an intramolecular N1—H1···Cl1 hydrogen-bonding interaction (Table 2). The corresponding values for 105 compounds with 130 similar hydrogen bonds reported to the CSD average 3.24 (9) Å and 162 (7)°. Therefore, the distance observed in (I) is indicative of a relatively strong hydrogen bond. The observed N1—H1···Cl1 hydrogen bond may also play a role in the future development of this class of catalysts, due to possible participation in `secondary interactions'. Such interactions have been proposed or are believed to be potentially important in increasing enantioselectivity by forming non-bonding contacts with the reacting substrates (Sawamura & Ito, 1992). Steric interactions also contribute to the conformation adopted by (I), as the majority of the bulky ring substituents occupy pseudo-equatorial positions. Additionally, ester atoms O1, O2, C23 and C24 are nearly perpendicular to the phenyl ring (atoms C17—C22), to mitigate steric repulsion between atoms O2 and H21.

In the lattice of (I), there are intermolecular hydrogen-bonding interactions between symmetry-related molecules. These O4—H4···O3(-x, 1 − y, 2 − z) interactions result in the formation of dimers of rhodium complexes (Table 2). The corresponding values for 67 compounds with 74 similar hydrogen bonds in structures reported to the CSD averag 2.68 (6) Å and 168 (7)°, and compare reasonably well with the O···O hydrogen bond in (I).

S2. Experimental

A CH₂Cl₂ solution of the multiply substituted 1,2,4-diazaphospholane ligand was treated with 0.5 equivalents of [RhCl(cycloocta-1,5-diene)]₂ in CH₂Cl₂ at room temperature. The mixture was stirred for 1 h and dried in vacuo to yield the yellow title solid, (I), in quantitative yield. Crystals suitable for X-ray structure determination were obtained by slow crystallization from CH₂Cl₂ and hexanes (Ratio?) at room temperature. Spectroscopic analysis: ¹H NMR (CDCl₃, δ, p.p.m.): 1.6 (m, 4H, CH₂), 1.94 (b, 1H), 2.07 (s, 3H, CH₃), 2.15 (b, 1H), 2.34 (b, 2H), 2.57 (s, 3H, CH₃), 2.72 (b, 1H), 3.02 (b, 1H), 5.34 (b, 2H), 6.32 (b, 2H), 6.39 (d, 1H, J = 8 Hz), 6.7 (m 2H), 7.0 (m, 2H), 7.07–7.25 (m, 6H), 7.35 (m, 2H), 8.25 (d, 1H), 8.95 (b, 1H); ³¹P{¹H} NMR (CDCl₃, δ, p.p.m.): 67.4 (d, J_Rh—P = 157.4 Hz).

S3. Refinement

Hydroxyl and methyl H atoms were constrained to an ideal geometry, with U_iso(H) = 1.5U_eq(O,C) and allowed to rotate freely about their C—O or C—C bonds, respectively. All other H atoms except H1 were constrained and allowed to ride on their C atoms, with U_iso(H) = 1.2U_eq(C). Atom H1 bonded to N1 was positioned from inspection of difference maps and refined subject to a DFIX restraint of 0.90 (2) Å, with U_iso(H) = 1.2U_eq(N). A residual peak of electron density (0.80 e Å⁻³) was located in a chemically unreasonable position in the vicinity of the Rh atom and considered to be noise.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); 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 (I). Displacement ellipsoids are drawn at the 30% probability level and all H atoms except for H1 and H4 have been omitted for clarity.

{2-[1-acetyl-5-(2-hydroxyphenyl)-4-phenyl-1,2,4-diazaphospholan-3-yl]phenyl acetate-κP}chloro(cycloocta-1,5-diene-κ⁴C¹,C²,C⁵,C⁶)rhodium(I) dichloromethane solvate

Crystal data

[Rh(C8H12)(C24H23N2O4P)Cl]·CH2Cl2	Z = 2
Mr = 765.88	F(000) = 784
Triclinic, P1	Dx = 1.539 Mg m^−3
a = 11.6420 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.8755 (5) Å	Cell parameters from 5120 reflections
c = 12.7087 (6) Å	θ = 2.0–25.0°
α = 102.261 (10)°	µ = 0.85 mm^−1
β = 103.03 (1)°	T = 173 K
γ = 95.789 (10)°	Needle, orange
V = 1652.21 (17) Å^3	0.45 × 0.15 × 0.08 mm

Data collection

Bruker SMART1000 CCD area-detector diffractometer	6453 independent reflections
Radiation source: fine-focus sealed tube	5873 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω scans	θmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −14→13
Tmin = 0.702, Tmax = 0.935	k = −14→14
13910 measured reflections	l = 0→15

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0486P)^2 + 0.8831P] where P = (Fo^2 + 2Fc^2)/3
6453 reflections	(Δ/σ)max < 0.001
403 parameters	Δρmax = 0.80 e Å^−3
1 restraint	Δρmin = −0.45 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
Rh	0.275305 (15)	0.173446 (15)	0.961962 (14)	0.02008 (8)
P	0.16239 (5)	0.25500 (5)	0.83422 (5)	0.01927 (13)
Cl1	0.45876 (5)	0.26706 (6)	0.94431 (6)	0.03173 (15)
Cl2	0.25111 (8)	0.90356 (8)	0.64874 (8)	0.0566 (2)
Cl3	0.47067 (10)	1.04469 (13)	0.65436 (11)	0.0907 (4)
O1	0.29847 (16)	0.25175 (16)	0.51988 (15)	0.0311 (4)
O2	0.3692 (2)	0.4348 (2)	0.5184 (2)	0.0597 (7)
O3	0.14376 (16)	0.63148 (15)	0.84877 (16)	0.0300 (4)
O4	0.00898 (15)	0.37233 (15)	1.02488 (14)	0.0259 (4)
H4	−0.0373	0.3767	1.0671	0.039*
N1	0.31141 (18)	0.40651 (18)	0.78875 (17)	0.0232 (4)
H1	0.3696 (17)	0.391 (2)	0.8413 (16)	0.028*
N2	0.23813 (17)	0.47493 (17)	0.84293 (16)	0.0215 (4)
C1	0.3652 (2)	0.1696 (2)	1.1325 (2)	0.0293 (6)
H1A	0.4401	0.2274	1.1659	0.035*
C2	0.3799 (2)	0.0694 (2)	1.0649 (2)	0.0297 (6)
H2	0.4632	0.0675	1.0568	0.036*
C3	0.3096 (3)	−0.0493 (2)	1.0522 (2)	0.0349 (6)
H3A	0.2834	−0.0505	1.1209	0.042*
H3B	0.3618	−0.1094	1.0423	0.042*
C4	0.2000 (3)	−0.0788 (2)	0.9524 (2)	0.0328 (6)
H4A	0.2237	−0.1162	0.8849	0.039*
H4B	0.1397	−0.1359	0.9652	0.039*
C5	0.1440 (2)	0.0262 (2)	0.9320 (2)	0.0254 (5)
H5	0.0846	0.0107	0.8582	0.030*
C6	0.1220 (2)	0.1149 (2)	1.0126 (2)	0.0231 (5)
H6	0.0503	0.1506	0.9854	0.028*
C7	0.1487 (2)	0.1174 (2)	1.1362 (2)	0.0280 (5)
H7A	0.1387	0.0363	1.1446	0.034*
H7B	0.0901	0.1579	1.1688	0.034*
C8	0.2755 (2)	0.1788 (2)	1.2013 (2)	0.0306 (6)
H8A	0.2728	0.2623	1.2313	0.037*
H8B	0.3023	0.1443	1.2654	0.037*
C9	0.2338 (2)	0.2956 (2)	0.72495 (19)	0.0229 (5)
H9	0.2853	0.2364	0.7044	0.027*
C10	0.1602 (2)	0.41415 (19)	0.89699 (19)	0.0201 (5)
H10	0.0773	0.4317	0.8738	0.024*
C11	0.0109 (2)	0.1831 (2)	0.76125 (19)	0.0238 (5)
C12	0.0016 (2)	0.0844 (2)	0.6755 (2)	0.0299 (6)
H12	0.0718	0.0579	0.6602	0.036*
C13	−0.1097 (3)	0.0251 (2)	0.6127 (2)	0.0379 (7)
H13	−0.1157	−0.0417	0.5541	0.046*
C14	−0.2119 (3)	0.0629 (3)	0.6352 (2)	0.0390 (7)
H14	−0.2881	0.0225	0.5919	0.047*
C15	−0.2034 (2)	0.1595 (3)	0.7206 (2)	0.0350 (6)
H15	−0.2738	0.1851	0.7361	0.042*
C16	−0.0925 (2)	0.2195 (2)	0.7839 (2)	0.0277 (5)
H16	−0.0872	0.2856	0.8430	0.033*
C17	0.1522 (2)	0.3105 (2)	0.6195 (2)	0.0236 (5)
C18	0.0421 (2)	0.3493 (2)	0.6149 (2)	0.0277 (5)
H18	0.0168	0.3700	0.6815	0.033*
C19	−0.0306 (3)	0.3585 (2)	0.5161 (2)	0.0324 (6)
H19	−0.1053	0.3846	0.5152	0.039*
C20	0.0052 (3)	0.3295 (3)	0.4179 (2)	0.0365 (6)
H20	−0.0457	0.3335	0.3494	0.044*
C21	0.1143 (3)	0.2950 (2)	0.4208 (2)	0.0345 (6)
H21	0.1403	0.2765	0.3543	0.041*
C22	0.1869 (2)	0.2873 (2)	0.5207 (2)	0.0270 (5)
C23	0.3848 (3)	0.3366 (3)	0.5149 (2)	0.0394 (7)
C24	0.4964 (3)	0.2877 (3)	0.5041 (3)	0.0549 (9)
H24A	0.5480	0.3419	0.4798	0.082*
H24B	0.4756	0.2124	0.4492	0.082*
H24C	0.5385	0.2768	0.5764	0.082*
C25	0.2201 (2)	0.5778 (2)	0.8182 (2)	0.0232 (5)
C26	0.2995 (2)	0.6241 (2)	0.7537 (2)	0.0332 (6)
H26A	0.2807	0.7003	0.7434	0.050*
H26B	0.2863	0.5698	0.6808	0.050*
H26C	0.3832	0.6326	0.7948	0.050*
C27	0.2024 (2)	0.44839 (19)	1.02271 (19)	0.0217 (5)
C28	0.3175 (2)	0.5021 (2)	1.0798 (2)	0.0326 (6)
H28	0.3736	0.5188	1.0392	0.039*
C29	0.3520 (3)	0.5318 (3)	1.1953 (2)	0.0417 (7)
H29	0.4318	0.5670	1.2331	0.050*
C30	0.2706 (3)	0.5103 (3)	1.2551 (2)	0.0385 (7)
H30	0.2940	0.5312	1.3342	0.046*
C31	0.1542 (2)	0.4579 (2)	1.1997 (2)	0.0293 (6)
H31	0.0978	0.4439	1.2408	0.035*
C32	0.1207 (2)	0.4262 (2)	1.0843 (2)	0.0222 (5)
C33	0.3886 (3)	0.9835 (3)	0.7328 (3)	0.0543 (9)
H33A	0.3740	1.0462	0.7910	0.065*
H33B	0.4351	0.9313	0.7702	0.065*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh	0.02073 (11)	0.01997 (11)	0.02029 (11)	0.00314 (7)	0.00422 (7)	0.00757 (7)
P	0.0213 (3)	0.0184 (3)	0.0181 (3)	0.0022 (2)	0.0041 (2)	0.0058 (2)
Cl1	0.0223 (3)	0.0366 (3)	0.0400 (4)	0.0030 (3)	0.0067 (3)	0.0194 (3)
Cl2	0.0517 (5)	0.0661 (6)	0.0541 (5)	0.0065 (4)	0.0065 (4)	0.0277 (4)
Cl3	0.0603 (7)	0.1134 (10)	0.0835 (8)	−0.0229 (6)	0.0200 (6)	0.0069 (7)
O1	0.0345 (10)	0.0339 (10)	0.0267 (9)	0.0056 (8)	0.0138 (8)	0.0050 (8)
O2	0.0591 (15)	0.0464 (14)	0.0784 (18)	−0.0038 (12)	0.0293 (14)	0.0185 (13)
O3	0.0350 (10)	0.0235 (9)	0.0383 (10)	0.0078 (8)	0.0173 (8)	0.0118 (8)
O4	0.0255 (9)	0.0287 (9)	0.0238 (9)	0.0000 (7)	0.0103 (7)	0.0049 (7)
N1	0.0226 (10)	0.0243 (10)	0.0252 (11)	0.0052 (8)	0.0089 (8)	0.0079 (8)
N2	0.0240 (10)	0.0211 (10)	0.0222 (10)	0.0031 (8)	0.0096 (8)	0.0072 (8)
C1	0.0227 (12)	0.0409 (15)	0.0234 (13)	0.0020 (11)	−0.0011 (10)	0.0147 (11)
C2	0.0248 (13)	0.0401 (15)	0.0315 (14)	0.0140 (11)	0.0076 (11)	0.0199 (12)
C3	0.0379 (15)	0.0338 (15)	0.0447 (16)	0.0174 (12)	0.0170 (13)	0.0219 (13)
C4	0.0464 (16)	0.0209 (12)	0.0354 (15)	0.0072 (11)	0.0154 (12)	0.0100 (11)
C5	0.0298 (13)	0.0216 (12)	0.0240 (12)	−0.0010 (10)	0.0059 (10)	0.0075 (10)
C6	0.0235 (12)	0.0238 (12)	0.0235 (12)	0.0007 (9)	0.0065 (10)	0.0096 (10)
C7	0.0288 (13)	0.0334 (14)	0.0242 (13)	0.0052 (11)	0.0087 (10)	0.0094 (11)
C8	0.0337 (14)	0.0370 (14)	0.0210 (12)	0.0059 (11)	0.0051 (11)	0.0085 (11)
C9	0.0284 (12)	0.0228 (12)	0.0212 (12)	0.0076 (10)	0.0101 (10)	0.0075 (9)
C10	0.0214 (11)	0.0191 (11)	0.0218 (12)	0.0029 (9)	0.0083 (9)	0.0061 (9)
C11	0.0291 (13)	0.0217 (12)	0.0194 (11)	0.0012 (10)	0.0005 (9)	0.0101 (9)
C12	0.0373 (15)	0.0238 (12)	0.0267 (13)	0.0019 (11)	0.0036 (11)	0.0083 (10)
C13	0.0528 (18)	0.0276 (14)	0.0247 (14)	−0.0053 (13)	−0.0010 (12)	0.0046 (11)
C14	0.0344 (15)	0.0428 (16)	0.0303 (15)	−0.0127 (13)	−0.0070 (12)	0.0137 (13)
C15	0.0278 (14)	0.0428 (16)	0.0336 (15)	−0.0008 (12)	0.0021 (11)	0.0167 (12)
C16	0.0284 (13)	0.0302 (13)	0.0231 (12)	0.0005 (10)	0.0028 (10)	0.0094 (10)
C17	0.0310 (13)	0.0193 (11)	0.0213 (12)	0.0024 (10)	0.0069 (10)	0.0068 (9)
C18	0.0362 (14)	0.0264 (13)	0.0244 (13)	0.0068 (11)	0.0111 (11)	0.0098 (10)
C19	0.0347 (14)	0.0319 (14)	0.0352 (15)	0.0095 (11)	0.0083 (12)	0.0166 (12)
C20	0.0413 (16)	0.0417 (16)	0.0246 (13)	0.0032 (13)	0.0001 (12)	0.0138 (12)
C21	0.0462 (17)	0.0355 (15)	0.0226 (13)	0.0033 (12)	0.0108 (12)	0.0080 (11)
C22	0.0321 (13)	0.0234 (12)	0.0253 (13)	0.0017 (10)	0.0079 (10)	0.0063 (10)
C23	0.0397 (16)	0.0468 (18)	0.0279 (14)	−0.0021 (13)	0.0104 (12)	0.0037 (13)
C24	0.0373 (18)	0.072 (2)	0.0475 (19)	0.0001 (16)	0.0139 (15)	−0.0020 (17)
C25	0.0255 (12)	0.0213 (12)	0.0224 (12)	0.0002 (10)	0.0054 (10)	0.0066 (9)
C26	0.0353 (15)	0.0294 (14)	0.0440 (16)	0.0055 (11)	0.0187 (13)	0.0189 (12)
C27	0.0272 (12)	0.0174 (11)	0.0211 (12)	0.0039 (9)	0.0069 (10)	0.0049 (9)
C28	0.0325 (14)	0.0354 (14)	0.0278 (13)	−0.0021 (11)	0.0109 (11)	0.0029 (11)
C29	0.0338 (15)	0.0527 (18)	0.0270 (14)	−0.0090 (13)	0.0005 (12)	−0.0001 (13)
C30	0.0450 (17)	0.0438 (16)	0.0201 (13)	−0.0019 (13)	0.0060 (12)	0.0002 (12)
C31	0.0360 (14)	0.0304 (13)	0.0238 (13)	0.0032 (11)	0.0121 (11)	0.0075 (10)
C32	0.0264 (12)	0.0168 (11)	0.0246 (12)	0.0056 (9)	0.0071 (10)	0.0058 (9)
C33	0.060 (2)	0.055 (2)	0.0416 (18)	0.0155 (17)	−0.0002 (16)	0.0102 (16)

Geometric parameters (Å, º)

Rh—C5	2.111 (2)	C10—C27	1.513 (3)
Rh—C6	2.130 (2)	C10—H10	1.0000
Rh—C1	2.197 (2)	C11—C16	1.387 (4)
Rh—C2	2.235 (2)	C11—C12	1.396 (3)
Rh—P	2.2943 (6)	C12—C13	1.387 (4)
Rh—Cl1	2.3856 (7)	C12—H12	0.9500
P—C11	1.823 (2)	C13—C14	1.381 (4)
P—C9	1.891 (2)	C13—H13	0.9500
P—C10	1.894 (2)	C14—C15	1.379 (4)
Cl2—C33	1.759 (4)	C14—H14	0.9500
Cl3—C33	1.741 (4)	C15—C16	1.387 (4)
O1—C23	1.372 (4)	C15—H15	0.9500
O1—C22	1.408 (3)	C16—H16	0.9500
O2—C23	1.191 (4)	C17—C22	1.385 (3)
O3—C25	1.230 (3)	C17—C18	1.399 (4)
O4—C32	1.361 (3)	C18—C19	1.379 (4)
O4—H4	0.8400	C18—H18	0.9500
N1—N2	1.425 (3)	C19—C20	1.389 (4)
N1—C9	1.478 (3)	C19—H19	0.9500
N1—H1	0.90 (2)	C20—C21	1.369 (4)
N2—C25	1.349 (3)	C20—H20	0.9500
N2—C10	1.475 (3)	C21—C22	1.384 (4)
C1—C2	1.362 (4)	C21—H21	0.9500
C1—C8	1.504 (4)	C23—C24	1.497 (4)
C1—H1A	1.0000	C24—H24A	0.9800
C2—C3	1.514 (4)	C24—H24B	0.9800
C2—H2	1.0000	C24—H24C	0.9800
C3—C4	1.533 (4)	C25—C26	1.504 (3)
C3—H3A	0.9900	C26—H26A	0.9800
C3—H3B	0.9900	C26—H26B	0.9800
C4—C5	1.507 (3)	C26—H26C	0.9800
C4—H4A	0.9900	C27—C28	1.385 (4)
C4—H4B	0.9900	C27—C32	1.400 (3)
C5—C6	1.392 (3)	C28—C29	1.387 (4)
C5—H5	1.0000	C28—H28	0.9500
C6—C7	1.524 (3)	C29—C30	1.379 (4)
C6—H6	1.0000	C29—H29	0.9500
C7—C8	1.539 (4)	C30—C31	1.390 (4)
C7—H7A	0.9900	C30—H30	0.9500
C7—H7B	0.9900	C31—C32	1.387 (4)
C8—H8A	0.9900	C31—H31	0.9500
C8—H8B	0.9900	C33—H33A	0.9900
C9—C17	1.514 (3)	C33—H33B	0.9900
C9—H9	1.0000
C5—Rh—C6	38.30 (9)	N2—C10—P	102.59 (14)
C5—Rh—C1	96.54 (10)	C27—C10—P	113.63 (16)
C6—Rh—C1	81.77 (9)	N2—C10—H10	109.2
C5—Rh—C2	80.65 (10)	C27—C10—H10	109.2
C6—Rh—C2	88.77 (9)	P—C10—H10	109.2
C1—Rh—C2	35.79 (10)	C16—C11—C12	119.2 (2)
C5—Rh—P	94.10 (7)	C16—C11—P	125.22 (19)
C6—Rh—P	91.45 (7)	C12—C11—P	115.59 (19)
C1—Rh—P	152.83 (8)	C13—C12—C11	120.2 (3)
C2—Rh—P	171.17 (7)	C13—C12—H12	119.9
C5—Rh—Cl1	152.42 (7)	C11—C12—H12	119.9
C6—Rh—Cl1	167.60 (7)	C14—C13—C12	120.0 (3)
C1—Rh—Cl1	89.06 (7)	C14—C13—H13	120.0
C2—Rh—Cl1	88.63 (7)	C12—C13—H13	120.0
P—Rh—Cl1	92.97 (2)	C15—C14—C13	120.0 (3)
C11—P—C9	106.33 (11)	C15—C14—H14	120.0
C11—P—C10	109.41 (11)	C13—C14—H14	120.0
C9—P—C10	90.90 (10)	C14—C15—C16	120.4 (3)
C11—P—Rh	119.06 (8)	C14—C15—H15	119.8
C9—P—Rh	116.79 (8)	C16—C15—H15	119.8
C10—P—Rh	110.70 (8)	C15—C16—C11	120.1 (3)
C23—O1—C22	114.8 (2)	C15—C16—H16	119.9
C32—O4—H4	109.5	C11—C16—H16	119.9
N2—N1—C9	106.00 (18)	C22—C17—C18	116.5 (2)
N2—N1—H1	108.3 (18)	C22—C17—C9	119.7 (2)
C9—N1—H1	108.6 (18)	C18—C17—C9	123.8 (2)
C25—N2—N1	118.78 (19)	C19—C18—C17	121.6 (2)
C25—N2—C10	122.50 (19)	C19—C18—H18	119.2
N1—N2—C10	116.35 (18)	C17—C18—H18	119.2
C2—C1—C8	125.3 (2)	C18—C19—C20	120.0 (3)
C2—C1—Rh	73.63 (15)	C18—C19—H19	120.0
C8—C1—Rh	108.41 (16)	C20—C19—H19	120.0
C2—C1—H1A	114.0	C21—C20—C19	119.5 (2)
C8—C1—H1A	114.0	C21—C20—H20	120.3
Rh—C1—H1A	114.0	C19—C20—H20	120.3
C1—C2—C3	123.9 (2)	C20—C21—C22	119.8 (2)
C1—C2—Rh	70.58 (14)	C20—C21—H21	120.1
C3—C2—Rh	111.47 (17)	C22—C21—H21	120.1
C1—C2—H2	114.3	C21—C22—C17	122.4 (2)
C3—C2—H2	114.3	C21—C22—O1	117.9 (2)
Rh—C2—H2	114.3	C17—C22—O1	119.6 (2)
C2—C3—C4	111.8 (2)	O2—C23—O1	122.7 (3)
C2—C3—H3A	109.3	O2—C23—C24	126.5 (3)
C4—C3—H3A	109.3	O1—C23—C24	110.7 (3)
C2—C3—H3B	109.3	C23—C24—H24A	109.5
C4—C3—H3B	109.3	C23—C24—H24B	109.5
H3A—C3—H3B	107.9	H24A—C24—H24B	109.5
C5—C4—C3	113.4 (2)	C23—C24—H24C	109.5
C5—C4—H4A	108.9	H24A—C24—H24C	109.5
C3—C4—H4A	108.9	H24B—C24—H24C	109.5
C5—C4—H4B	108.9	O3—C25—N2	121.4 (2)
C3—C4—H4B	108.9	O3—C25—C26	121.9 (2)
H4A—C4—H4B	107.7	N2—C25—C26	116.7 (2)
C6—C5—C4	126.2 (2)	C25—C26—H26A	109.5
C6—C5—Rh	71.59 (14)	C25—C26—H26B	109.5
C4—C5—Rh	111.16 (17)	H26A—C26—H26B	109.5
C6—C5—H5	113.4	C25—C26—H26C	109.5
C4—C5—H5	113.4	H26A—C26—H26C	109.5
Rh—C5—H5	113.4	H26B—C26—H26C	109.5
C5—C6—C7	124.0 (2)	C28—C27—C32	118.5 (2)
C5—C6—Rh	70.10 (14)	C28—C27—C10	123.2 (2)
C7—C6—Rh	113.14 (16)	C32—C27—C10	118.3 (2)
C5—C6—H6	114.0	C27—C28—C29	121.1 (2)
C7—C6—H6	114.0	C27—C28—H28	119.4
Rh—C6—H6	114.0	C29—C28—H28	119.4
C6—C7—C8	113.2 (2)	C30—C29—C28	120.0 (3)
C6—C7—H7A	108.9	C30—C29—H29	120.0
C8—C7—H7A	108.9	C28—C29—H29	120.0
C6—C7—H7B	108.9	C29—C30—C31	120.0 (2)
C8—C7—H7B	108.9	C29—C30—H30	120.0
H7A—C7—H7B	107.7	C31—C30—H30	120.0
C1—C8—C7	113.6 (2)	C32—C31—C30	119.9 (2)
C1—C8—H8A	108.8	C32—C31—H31	120.1
C7—C8—H8A	108.8	C30—C31—H31	120.1
C1—C8—H8B	108.8	O4—C32—C31	122.9 (2)
C7—C8—H8B	108.8	O4—C32—C27	116.5 (2)
H8A—C8—H8B	107.7	C31—C32—C27	120.6 (2)
N1—C9—C17	111.29 (19)	Cl3—C33—Cl2	111.29 (19)
N1—C9—P	101.19 (15)	Cl3—C33—H33A	109.4
C17—C9—P	117.69 (17)	Cl2—C33—H33A	109.4
N1—C9—H9	108.7	Cl3—C33—H33B	109.4
C17—C9—H9	108.7	Cl2—C33—H33B	109.4
P—C9—H9	108.7	H33A—C33—H33B	108.0
N2—C10—C27	112.88 (19)
C5—Rh—P—C11	3.21 (12)	C10—P—C9—N1	35.10 (15)
C6—Rh—P—C11	−35.05 (12)	Rh—P—C9—N1	−78.73 (15)
C1—Rh—P—C11	−109.72 (18)	C11—P—C9—C17	24.2 (2)
Cl1—Rh—P—C11	156.54 (10)	C10—P—C9—C17	−86.35 (19)
C5—Rh—P—C9	−126.64 (11)	Rh—P—C9—C17	159.82 (15)
C6—Rh—P—C9	−164.90 (11)	C25—N2—C10—C27	−90.4 (3)
C1—Rh—P—C9	120.42 (17)	N1—N2—C10—C27	107.3 (2)
Cl1—Rh—P—C9	26.69 (9)	C25—N2—C10—P	146.94 (19)
C5—Rh—P—C10	131.26 (10)	N1—N2—C10—P	−15.4 (2)
C6—Rh—P—C10	93.00 (10)	C11—P—C10—N2	−120.18 (15)
C1—Rh—P—C10	18.32 (17)	C9—P—C10—N2	−12.51 (16)
Cl1—Rh—P—C10	−75.41 (8)	Rh—P—C10—N2	106.69 (13)
C9—N1—N2—C25	−118.3 (2)	C11—P—C10—C27	117.64 (17)
C9—N1—N2—C10	44.7 (2)	C9—P—C10—C27	−134.69 (18)
C5—Rh—C1—C2	63.97 (16)	Rh—P—C10—C27	−15.49 (18)
C6—Rh—C1—C2	99.42 (16)	C9—P—C11—C16	−121.6 (2)
P—Rh—C1—C2	176.37 (13)	C10—P—C11—C16	−24.7 (2)
Cl1—Rh—C1—C2	−88.96 (15)	Rh—P—C11—C16	104.0 (2)
C5—Rh—C1—C8	−58.45 (19)	C9—P—C11—C12	57.8 (2)
C6—Rh—C1—C8	−23.01 (18)	C10—P—C11—C12	154.69 (18)
C2—Rh—C1—C8	−122.4 (3)	Rh—P—C11—C12	−76.66 (19)
P—Rh—C1—C8	53.9 (3)	C16—C11—C12—C13	1.2 (4)
Cl1—Rh—C1—C8	148.62 (18)	P—C11—C12—C13	−178.2 (2)
C8—C1—C2—C3	−2.1 (4)	C11—C12—C13—C14	−0.4 (4)
Rh—C1—C2—C3	−103.3 (2)	C12—C13—C14—C15	−0.4 (4)
C8—C1—C2—Rh	101.3 (2)	C13—C14—C15—C16	0.4 (4)
C5—Rh—C2—C1	−115.21 (17)	C14—C15—C16—C11	0.4 (4)
C6—Rh—C2—C1	−77.58 (16)	C12—C11—C16—C15	−1.2 (4)
Cl1—Rh—C2—C1	90.30 (15)	P—C11—C16—C15	178.15 (19)
C5—Rh—C2—C3	4.61 (18)	N1—C9—C17—C22	93.3 (3)
C6—Rh—C2—C3	42.24 (19)	P—C9—C17—C22	−150.64 (19)
C1—Rh—C2—C3	119.8 (3)	N1—C9—C17—C18	−85.3 (3)
Cl1—Rh—C2—C3	−149.89 (18)	P—C9—C17—C18	30.8 (3)
C1—C2—C3—C4	94.5 (3)	C22—C17—C18—C19	3.2 (4)
Rh—C2—C3—C4	14.0 (3)	C9—C17—C18—C19	−178.2 (2)
C2—C3—C4—C5	−34.0 (3)	C17—C18—C19—C20	−0.4 (4)
C3—C4—C5—C6	−44.2 (4)	C18—C19—C20—C21	−1.8 (4)
C3—C4—C5—Rh	37.9 (3)	C19—C20—C21—C22	1.2 (4)
C1—Rh—C5—C6	67.82 (16)	C20—C21—C22—C17	1.7 (4)
C2—Rh—C5—C6	99.99 (15)	C20—C21—C22—O1	−179.9 (2)
P—Rh—C5—C6	−87.15 (14)	C18—C17—C22—C21	−3.8 (4)
Cl1—Rh—C5—C6	168.42 (12)	C9—C17—C22—C21	177.5 (2)
C6—Rh—C5—C4	−122.6 (2)	C18—C17—C22—O1	177.8 (2)
C1—Rh—C5—C4	−54.78 (19)	C9—C17—C22—O1	−0.8 (3)
C2—Rh—C5—C4	−22.60 (18)	C23—O1—C22—C21	77.8 (3)
P—Rh—C5—C4	150.25 (17)	C23—O1—C22—C17	−103.8 (3)
Cl1—Rh—C5—C4	45.8 (3)	C22—O1—C23—O2	4.8 (4)
C4—C5—C6—C7	−1.9 (4)	C22—O1—C23—C24	−175.0 (2)
Rh—C5—C6—C7	−105.1 (2)	N1—N2—C25—O3	168.6 (2)
C4—C5—C6—Rh	103.2 (3)	C10—N2—C25—O3	6.7 (4)
C1—Rh—C6—C5	−111.64 (16)	N1—N2—C25—C26	−12.6 (3)
C2—Rh—C6—C5	−76.40 (15)	C10—N2—C25—C26	−174.5 (2)
P—Rh—C6—C5	94.78 (14)	N2—C10—C27—C28	−18.1 (3)
Cl1—Rh—C6—C5	−154.4 (3)	P—C10—C27—C28	98.1 (2)
C5—Rh—C6—C7	119.5 (2)	N2—C10—C27—C32	160.9 (2)
C1—Rh—C6—C7	7.88 (18)	P—C10—C27—C32	−82.8 (2)
C2—Rh—C6—C7	43.13 (18)	C32—C27—C28—C29	1.0 (4)
P—Rh—C6—C7	−145.70 (17)	C10—C27—C28—C29	−180.0 (3)
Cl1—Rh—C6—C7	−34.8 (4)	C27—C28—C29—C30	−1.4 (5)
C5—C6—C7—C8	89.7 (3)	C28—C29—C30—C31	0.5 (5)
Rh—C6—C7—C8	8.8 (3)	C29—C30—C31—C32	0.8 (4)
C2—C1—C8—C7	−48.0 (3)	C30—C31—C32—O4	178.5 (2)
Rh—C1—C8—C7	34.6 (3)	C30—C31—C32—C27	−1.2 (4)
C6—C7—C8—C1	−29.5 (3)	C28—C27—C32—O4	−179.4 (2)
N2—N1—C9—C17	77.0 (2)	C10—C27—C32—O4	1.5 (3)
N2—N1—C9—P	−48.85 (18)	C28—C27—C32—C31	0.3 (4)
C11—P—C9—N1	145.63 (15)	C10—C27—C32—C31	−178.8 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3^i	0.84	1.82	2.654 (2)	173
N1—H1···Cl1	0.90 (2)	2.34 (2)	3.167 (2)	152 (2)

Symmetry code: (i) −x, −y+1, −z+2.