(Nitrito-κO)(nitro-κN)(nitrosyl-κN)bis­(tri­phenylphosphane-κP)rhodium(III)

Albert, D.R.; Gau, M.; Rajaseelan, E.

doi:10.1107/S241431462500598X

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 7| July 2025| x250598

https://doi.org/10.1107/S241431462500598X

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(Nitrito-κO)(nitro-κN)(nitrosyl-κN)bis(triphenylphosphane-κP)rhodium(III)

Daniel R. Albert,^a Michael Gau ^b and Edward Rajaseelan ^a ^*

^aDepartment of Chemistry, Millersville University, Millersville, PA 17551, USA, and ^bDepartment of Chemistry, University of Pennsylvania, Philadelphia, PA 19104, USA
^*Correspondence e-mail: [email protected]

Edited by S. Bernès, Benemérita Universidad Autónoma de Puebla, México (Received 4 June 2025; accepted 2 July 2025; online 8 July 2025)

The structure of the title compound, [Rh(NO)(NO₂)₂(C₁₈H₁₅P)₂] or [Rh(NO)(NO₂)(ONO)(PPh₃)₂], has been determined by single-crystal X-ray diffraction. A previous report of the title compound showed it crystallized in a monoclinic space group [Rajaseelan et al. (1999 ). J. PA. Acad. Sci. 73, 63–66; refcode SASTOW in the CSD]. However, it was unable to be refined because of severe disorder. In this study, two distinct crystals of the title compound were found showing the compound to be polymorphic. One of the crystals was unable to be resolved but was found to be in a monoclinic space group, as in the previously reported study. The other crystal was able to be refined and crystallizes in the triclinic space group P1. The refined structure consists of two discrete monomeric molecules per unit cell. The molecular geometry around rhodium is that of a distorted square pyramid, with nitrogen of the nitro ligand, oxygen of the nitrito ligand and phosphorus atoms of the phosphane ligands lying in the basal plane and the nitrogen atom of the bent nitrosyl occupying the apical position. The nitrosyl ligand exhibits positional disorder whereas the nitro and nitrito ligands show disorder across coordination sites with the disorder modelled in a 0.91:0.09 ratio. Both intramolecular C—H ⋯O (nitro and nitrito) and intermolecular C—H ⋯N (nitrito) interactions are observed. There are no hydrogen-bonding interactions with the N or O atoms of the nitrosyl ligand.

Keywords: crystal structure; rhodium; nitrito; nitrosyl; nitro.

CCDC reference: 2469479

Structure description

Nitrosyl is a versatile ligand and synthetic, structural, chemical reactivity, and spectroscopic studies of transition metal nitrosyl complexes are of interest due to the role of NO in biochemical systems and in coordination chemistry (Machura, 2005 ; Daniel & Gourlaouen, 2019 ). Nitrite coordinates to transition metals in different bonding modes. The different MNO₂ isomers are characterized by distinct infrared bands, ¹⁵N-NMR chemical shifts, and crystal structures of these linkages (Feltham, 1989 ). Synthesis and structures of many rhodium nitrosyl and nitrite complexes have been reported (English et al., 1987 ; Cheung et al., 2007 ; Gaviglio et al., 2009 ; Singh et al., 2011 ; Vorobyeva et al., 2022 ). The title compound has previously been reported and characterized with the bonding modes of the NO_x groups confirmed by the infrared spectra, ¹⁵N labelling studies, and multinuclear NMR spectra (Rajaseelan et al., 1999).

The title complex, [Rh(NO)(NO₂)(ONO)(PPh₃)₂], consists of two well-separated monomeric structural units per unit cell. There is no crystallographically imposed twofold axis on the molecule and the NO_x ligands are disordered and refined with a ratio of 0.91:0.09 as shown in Fig. 1. The coordination sphere around rhodium, formed by nitrosyl, nitro, nitrito, and two triphenylphosphane ligands, results in a distorted square-pyramidal environment as shown in Fig. 2. The square pyramidal shape is supported by τ₅ parameters (Addison et al., 1984 ) of both the main (τ₅ = 0.078) and disordered (τ₅ = 0.062) structures that are close to zero. The nitrogen atom of the nitrosyl ligand which coordinates in a bent fashion, occupies the apical position. The Rh1—N1 [Rh1—N1*] distance is 1.938 (3) [1.93 (3)] Å and the Rh1—N1—O1 [Rh1—N1*—O1*] bond angle is 126.1 (2) [111 (2)]°. The two phosphane ligands occupy the sterically favoured trans positions in the basal plane. The Rh1—P1 and Rh1—P2 bond lengths are 2.4001 (6) and 2.3978 (6) Å, respectively, and the P2—Rh1—P1 bond angle is 173.609 (19)°. The nitrito (–ONO) ligand is in the endo-conformation with a Rh1—O2 [Rh1—O5*] bond length of 2.1105 (19) [2.09 (2)] Å, and a O2—N2—O3 [O5*—N3*—O4] bond angle of 114.1 (3) [116 (2)]°. The nitrogen atom of the nitro (–NO₂) group occupies the other position on the basal plane and is trans to the oxygen of the nitrito (–ONO) ligand. The Rh1—N3 [Rh1—N2*] bond length is 2.019 (2) [2.03 (3)] Å and the O5—N3—O4 [O2*—N2*—O3*] bond angle is 120.3 (2) [118 (3)]°, as expected for an sp² hybridized nitrogen atom.

Figure 1
Molecular structure of the title compound shown with displacement ellipsoids at the 50% probability level.

Figure 2
A perspective view of the main component (91%) title compound displaying the distorted square-pyramidal coordination around Rh1 with the nitrosyl ligand in the apical position.

It has been proposed and supported by molecular orbital calculations that the nitrosyl group bends in the direction of the strongest π-acceptor ligand coordinating in the basal plane (Hoffmann et al., 1974 ; Ibers & Mingos, 1971 ; Pierpont & Eisenberg, 1972 ). In Rh(NO)Cl₂(PPh₃)₂ the nitrosyl ligand lies in the P—Rh—P plane (Goldberg et al., 1975 ). The NO₂⁻ ligand is a better π-acceptor than PPh₃ (Comas-Vilà & Salvador, 2024 ) and in the title complex the nitrosyl ligand lies approximately in the O(nitrito)—Rh—N(nitro) plane. This is clearly indicated in Fig. 3 (major component) and Fig. 4 (minor disordered component). The dihedral angle formed by the Rh1/N1/O1 and the O2/Rh1/N3 planes is 25.3 (6)°, and similarly, the dihedral angle between the Rh1/N1*/O1* and N2*/Rh/O5* planes is 7 (6)°.

Figure 3
A perspective view of the main component (91%) of the title compound showing the bent nitrosyl ligand oriented along the N—Rh—O plane.

Figure 4
A perspective view of the minor disordered component (9%) of the title compound showing the bent nitrosyl ligand oriented along the N—Rh—O plane.

The packing diagram for the title compound is shown in Fig. 5. Both intermolecular and intramolecular non-classical hydrogen-bonding interactions are observed. All of the C—H⋯O hydrogen bonding interactions with the phenyl moieties and nitro and nitrito ligands are intramolecular. Whereas all of the C—H⋯N hydrogen-bonding interactions between the phenyl moieties and the nitrito ligand are intermolecular. No hydrogen-bonding interactions are observed with the nitrosyl ligand. All hydrogen-bonding interactions are summarized in Table 1 and shown as dotted green lines in Fig. 5.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O5	0.95	2.27	3.200 (3)	166
C2—H2⋯O5*	0.95	2.40	3.213 (19)	144
C18—H18⋯O4	0.95	2.34	3.130 (3)	140
C21—H21⋯N2ⁱ	0.95	2.44	3.328 (4)	155
C32—H32⋯O2	0.95	2.40	3.118 (3)	132
C32—H32⋯O2*	0.95	2.36	3.24 (2)	154
C33—H33⋯N3*ⁱⁱ	0.95	2.38	3.21 (2)	145
Symmetry codes: (i) ; (ii) .

Figure 5
Crystal packing of the title compound viewed along the b-axis direction. Non-classical hydrogen-bonding interactions are shown as dotted green lines.

Synthesis and crystallization

The tile compound was synthesized by the previously reported procedure (Rajaseelan et al., 1999). It was crystallized by slow diffusion of pentane into a CH₂Cl₂ solution. The complex was polymorphic with two distinct crystals recovered. Both crystals were dark green with one of them forming irregular shaped blocks and the other forming needle-like crystals. Both types of crystals had identical infrared spectra showing the presence of the nitrosyl, nitro, and nitrito ligands. The irregular shaped block crystal crystallizes in the monoclinic crystal system with large amount of disorder in the NO_x groups, and its crystal structure did not refine in a satisfactory manner. Hence, the structural set-up of the irregular shaped block crystals remains an open question. The disorder in the NO_x groups for the needle-like crystals, which solved in the triclinic P $[\overline{1}]$ space group, was very minimal and refined well. The structure of the needle-like crystals is reported in this article.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The nitrosyl ligand exhibits positional disorder whereas the nitro and nitrito ligands show disorder across coordination sites with the disorder modelled in a 0.91:0.09 ratio. All nitro and nitrito N—O bond lengths involving disordered parts were restrained to 1.25 (2) Å. In addition, for the minor part of the nitro ligand, the O—N—O bond angle was restrained to ∼120°, with an O⋯O bond distance restrained to 2.15 (4) Å. For the disordered nitrosyl ligand, the N—O bond length in the minor part was restrained to 1.15 (2) Å. The U_ij components of all disordered atoms closer to each other than 2.0 Å were restrained to be similar, within a standard deviation of 0.002 A² (Sheldrick, 2015b ).

Table 2
Experimental details

Crystal data
Chemical formula	[Rh(NO)(NO₂)₂(C₁₈H₁₅P)₂]
M_r	749.48
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	10.2732 (2), 10.3317 (2), 18.1514 (4)
α, β, γ (°)	90.118 (2), 105.089 (2), 118.323 (2)
V (Å³)	1619.50 (6)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	5.60
Crystal size (mm)	0.17 × 0.1 × 0.03

Data collection
Diffractometer	Rigaku XtaLAB Synergy-S
Absorption correction	Multi-scan (SCALE3 ABSPACK; Oxford Diffraction, 2005 $[Oxford Diffraction (2005). SCALE3 ABSPACK. Oxford Diffraction Ltd: Abingdon, UK.]$ )
T_min, T_max	0.850, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	38997, 6535, 6126
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.082, 1.08
No. of reflections	6535
No. of parameters	487
No. of restraints	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −1.04
Computer programs: CrysAlis PRO (Rigaku OD, 2025 ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2469479

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S241431462500598X/bh4097sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462500598X/bh4097Isup2.hkl

checkCIF report

Computing details top

(Nitrito-κO)(nitro-κN)(nitrosyl-κN)bis(triphenylphosphane-κP)rhodium(III) top

Crystal data top

[Rh(NO)(NO₂)₂(C₁₈H₁₅P)₂]	Z = 2
M_r = 749.48	F(000) = 764
Triclinic, P1	D_x = 1.537 Mg m⁻³
a = 10.2732 (2) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.3317 (2) Å	Cell parameters from 26769 reflections
c = 18.1514 (4) Å	θ = 4.9–74.4°
α = 90.118 (2)°	µ = 5.60 mm⁻¹
β = 105.089 (2)°	T = 100 K
γ = 118.323 (2)°	Needle, green
V = 1619.50 (6) Å³	0.17 × 0.1 × 0.03 mm

Data collection top

Rigaku XtaLAB Synergy-S diffractometer	6126 reflections with I > 2σ(I)
Detector resolution: 10.0000 pixels mm^-1	R_int = 0.047
ω scans	θ_max = 74.5°, θ_min = 4.9°
Absorption correction: multi-scan (SCALE3 ABSPACK; Oxford Diffraction, 2005)	h = −12→12
T_min = 0.850, T_max = 1.000	k = −12→12
38997 measured reflections	l = −22→20
6535 independent reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0475P)² + 1.2428P] where P = (F_o² + 2F_c²)/3
6535 reflections	(Δ/σ)_max = 0.002
487 parameters	Δρ_max = 0.50 e Å⁻³
160 restraints	Δρ_min = −1.04 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Rh1	0.69455 (2)	0.72063 (2)	0.73984 (2)	0.01782 (7)
P1	0.78304 (6)	0.84065 (6)	0.63584 (3)	0.01877 (12)
P2	0.63593 (6)	0.61376 (6)	0.85208 (3)	0.01834 (12)
O1	0.3977 (2)	0.5606 (3)	0.63816 (14)	0.0403 (5)	0.91
O1*	0.441 (3)	0.510 (3)	0.6490 (16)	0.037 (2)	0.09
O2	0.8146 (2)	0.6017 (3)	0.74115 (12)	0.0306 (4)	0.91
O2*	0.892 (3)	0.580 (2)	0.7594 (12)	0.0315 (18)	0.09
O3	0.9814 (4)	0.8223 (4)	0.7943 (3)	0.0385 (8)	0.91
O3*	1.002 (5)	0.808 (4)	0.800 (3)	0.036 (2)	0.09
O4	0.6922 (2)	0.94890 (19)	0.81800 (10)	0.0277 (3)
O5	0.4959 (2)	0.8559 (2)	0.71591 (12)	0.0309 (4)	0.91
O5*	0.528 (2)	0.788 (2)	0.7215 (11)	0.0250 (12)	0.09
N1	0.5063 (4)	0.5562 (3)	0.67278 (15)	0.0296 (5)	0.91
N1*	0.566 (3)	0.533 (3)	0.6720 (15)	0.0333 (15)	0.09
N2	0.9564 (3)	0.6945 (3)	0.77560 (15)	0.0357 (5)	0.91
N2*	0.882 (3)	0.691 (3)	0.7696 (16)	0.0344 (12)	0.09
N3	0.6127 (3)	0.8576 (3)	0.75739 (13)	0.0231 (4)	0.91
N3*	0.567 (2)	0.900 (2)	0.7675 (11)	0.0261 (11)	0.09
C1	0.6388 (3)	0.8054 (3)	0.54337 (13)	0.0227 (5)
C2	0.5094 (3)	0.8184 (3)	0.54348 (15)	0.0286 (5)
H2	0.494092	0.836812	0.590960	0.034*
C3	0.4032 (3)	0.8042 (3)	0.47396 (16)	0.0344 (6)
H3	0.315916	0.813992	0.474200	0.041*
C4	0.4236 (3)	0.7758 (3)	0.40436 (16)	0.0341 (6)
H4	0.350085	0.765054	0.357057	0.041*
C5	0.5524 (3)	0.7632 (3)	0.40421 (15)	0.0345 (6)
H5	0.567554	0.744994	0.356622	0.041*
C6	0.6591 (3)	0.7771 (3)	0.47329 (14)	0.0300 (5)
H6	0.746170	0.767166	0.472777	0.036*
C7	0.9129 (3)	0.7841 (3)	0.61338 (13)	0.0217 (4)
C8	0.8534 (3)	0.6345 (3)	0.58525 (13)	0.0242 (5)
H8	0.745487	0.566960	0.573356	0.029*
C9	0.9521 (3)	0.5854 (3)	0.57487 (14)	0.0273 (5)
H9	0.911444	0.484159	0.555225	0.033*
C10	1.1108 (3)	0.6832 (3)	0.59298 (14)	0.0278 (5)
H10	1.178146	0.648121	0.586676	0.033*
C11	1.1700 (3)	0.8316 (3)	0.62018 (14)	0.0274 (5)
H11	1.277986	0.898430	0.631972	0.033*
C12	1.0721 (3)	0.8828 (3)	0.63025 (14)	0.0235 (5)
H12	1.112988	0.984776	0.648581	0.028*
C13	0.8930 (3)	1.0430 (3)	0.65558 (13)	0.0210 (4)
C14	0.9389 (3)	1.1237 (3)	0.59653 (14)	0.0244 (5)
H14	0.913317	1.073008	0.546782	0.029*
C15	1.0216 (3)	1.2776 (3)	0.61078 (14)	0.0278 (5)
H15	1.056194	1.332126	0.571264	0.033*
C16	1.0544 (3)	1.3525 (3)	0.68239 (15)	0.0286 (5)
H16	1.107521	1.458101	0.691253	0.034*
C17	1.0093 (3)	1.2730 (3)	0.74093 (14)	0.0284 (5)
H17	1.032255	1.324186	0.790112	0.034*
C18	0.9313 (3)	1.1197 (3)	0.72809 (14)	0.0239 (5)
H18	0.903358	1.065904	0.768954	0.029*
C19	0.5170 (3)	0.6706 (3)	0.88654 (14)	0.0221 (5)
C20	0.3787 (3)	0.6470 (3)	0.83388 (15)	0.0268 (5)
H20	0.345315	0.594367	0.783672	0.032*
C21	0.2902 (3)	0.6998 (3)	0.85440 (17)	0.0335 (6)
H21	0.195776	0.682420	0.818574	0.040*
C22	0.3393 (3)	0.7781 (3)	0.92717 (18)	0.0348 (6)
H22	0.279499	0.816250	0.940739	0.042*
C23	0.4751 (3)	0.8010 (3)	0.98034 (17)	0.0332 (6)
H23	0.507462	0.853773	1.030425	0.040*
C24	0.5645 (3)	0.7466 (3)	0.96031 (14)	0.0257 (5)
H24	0.657231	0.761405	0.996838	0.031*
C25	0.8054 (3)	0.6635 (2)	0.93392 (13)	0.0203 (4)
C26	0.9306 (3)	0.8090 (3)	0.94934 (14)	0.0238 (5)
H26	0.927203	0.879629	0.916565	0.029*
C27	1.0593 (3)	0.8494 (3)	1.01262 (14)	0.0268 (5)
H27	1.143967	0.948024	1.023111	0.032*
C28	1.0653 (3)	0.7469 (3)	1.06066 (14)	0.0277 (5)
H28	1.154064	0.775106	1.103662	0.033*
C29	0.9420 (3)	0.6037 (3)	1.04595 (14)	0.0275 (5)
H29	0.946168	0.533630	1.078950	0.033*
C30	0.8113 (3)	0.5615 (3)	0.98281 (14)	0.0240 (5)
H30	0.726371	0.463211	0.973195	0.029*
C31	0.5316 (3)	0.4110 (3)	0.83444 (13)	0.0235 (5)
C32	0.6032 (3)	0.3373 (3)	0.81272 (15)	0.0295 (5)
H32	0.704272	0.393404	0.807580	0.035*
C33	0.5282 (3)	0.1835 (3)	0.79864 (15)	0.0335 (6)
H33	0.578905	0.134618	0.785066	0.040*
C34	0.3792 (4)	0.1007 (3)	0.80434 (16)	0.0383 (7)
H34	0.327126	−0.004743	0.793955	0.046*
C35	0.3069 (3)	0.1723 (3)	0.82517 (19)	0.0418 (7)
H35	0.204757	0.115570	0.828892	0.050*
C36	0.3824 (3)	0.3269 (3)	0.84077 (17)	0.0344 (6)
H36	0.332296	0.375031	0.855739	0.041*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Rh1	0.01562 (9)	0.02078 (10)	0.01968 (10)	0.01061 (7)	0.00593 (6)	0.00453 (6)
P1	0.0167 (3)	0.0223 (3)	0.0190 (3)	0.0107 (2)	0.0056 (2)	0.0042 (2)
P2	0.0156 (2)	0.0197 (3)	0.0202 (3)	0.0090 (2)	0.0054 (2)	0.0039 (2)
O1	0.0245 (10)	0.0361 (11)	0.0473 (12)	0.0111 (9)	−0.0014 (9)	−0.0047 (9)
O1*	0.027 (3)	0.032 (3)	0.041 (3)	0.010 (2)	0.000 (2)	−0.001 (3)
O2	0.0353 (9)	0.0436 (10)	0.0324 (9)	0.0301 (8)	0.0188 (8)	0.0158 (8)
O2*	0.033 (2)	0.047 (3)	0.032 (2)	0.030 (2)	0.017 (2)	0.018 (2)
O3	0.0268 (13)	0.0532 (13)	0.0279 (12)	0.0135 (10)	0.0084 (11)	0.0120 (11)
O3*	0.030 (3)	0.052 (3)	0.030 (2)	0.022 (2)	0.014 (2)	0.014 (2)
O4	0.0267 (8)	0.0257 (8)	0.0293 (8)	0.0107 (6)	0.0105 (6)	0.0010 (6)
O5	0.0298 (9)	0.0396 (10)	0.0313 (10)	0.0251 (8)	0.0056 (8)	0.0050 (8)
O5*	0.0251 (16)	0.0279 (16)	0.0267 (16)	0.0153 (15)	0.0102 (15)	0.0065 (16)
N1	0.0246 (12)	0.0271 (12)	0.0309 (12)	0.0104 (10)	0.0036 (10)	−0.0012 (9)
N1*	0.025 (2)	0.030 (2)	0.035 (2)	0.0098 (19)	0.0020 (19)	−0.0011 (19)
N2	0.0334 (10)	0.0534 (12)	0.0322 (10)	0.0274 (9)	0.0157 (9)	0.0175 (9)
N2*	0.0332 (15)	0.0499 (15)	0.0320 (15)	0.0263 (15)	0.0161 (14)	0.0159 (14)
N3	0.0231 (9)	0.0251 (9)	0.0259 (9)	0.0139 (8)	0.0105 (7)	0.0075 (7)
N3*	0.0257 (14)	0.0276 (14)	0.0276 (14)	0.0138 (13)	0.0103 (13)	0.0051 (13)
C1	0.0208 (11)	0.0220 (11)	0.0231 (11)	0.0105 (9)	0.0033 (9)	0.0044 (9)
C2	0.0213 (11)	0.0357 (13)	0.0294 (13)	0.0148 (10)	0.0067 (10)	0.0072 (10)
C3	0.0210 (12)	0.0413 (15)	0.0368 (14)	0.0143 (11)	0.0040 (10)	0.0096 (12)
C4	0.0289 (13)	0.0321 (14)	0.0281 (13)	0.0109 (11)	−0.0035 (10)	0.0059 (11)
C5	0.0428 (15)	0.0361 (14)	0.0221 (12)	0.0207 (12)	0.0033 (11)	0.0028 (10)
C6	0.0340 (13)	0.0376 (14)	0.0227 (12)	0.0218 (11)	0.0066 (10)	0.0069 (10)
C7	0.0219 (11)	0.0269 (11)	0.0204 (11)	0.0143 (9)	0.0082 (9)	0.0056 (9)
C8	0.0262 (12)	0.0279 (12)	0.0223 (11)	0.0149 (10)	0.0097 (9)	0.0070 (9)
C9	0.0335 (13)	0.0295 (12)	0.0250 (12)	0.0192 (11)	0.0106 (10)	0.0048 (10)
C10	0.0322 (13)	0.0388 (14)	0.0259 (12)	0.0252 (11)	0.0138 (10)	0.0103 (10)
C11	0.0222 (11)	0.0372 (14)	0.0271 (12)	0.0164 (10)	0.0103 (9)	0.0080 (10)
C12	0.0205 (11)	0.0266 (12)	0.0254 (12)	0.0124 (9)	0.0080 (9)	0.0060 (9)
C13	0.0162 (10)	0.0246 (11)	0.0235 (11)	0.0115 (9)	0.0048 (8)	0.0039 (9)
C14	0.0250 (11)	0.0276 (12)	0.0221 (11)	0.0145 (10)	0.0061 (9)	0.0057 (9)
C15	0.0265 (12)	0.0295 (13)	0.0256 (12)	0.0126 (10)	0.0073 (10)	0.0109 (10)
C16	0.0221 (11)	0.0250 (12)	0.0317 (13)	0.0089 (10)	0.0025 (10)	0.0056 (10)
C17	0.0250 (12)	0.0282 (12)	0.0240 (12)	0.0087 (10)	0.0040 (9)	−0.0013 (10)
C18	0.0200 (11)	0.0284 (12)	0.0214 (11)	0.0101 (9)	0.0067 (9)	0.0050 (9)
C19	0.0185 (10)	0.0210 (11)	0.0292 (12)	0.0094 (9)	0.0117 (9)	0.0080 (9)
C20	0.0214 (11)	0.0295 (12)	0.0334 (13)	0.0137 (10)	0.0120 (10)	0.0109 (10)
C21	0.0236 (12)	0.0357 (14)	0.0488 (16)	0.0173 (11)	0.0174 (11)	0.0170 (12)
C22	0.0347 (14)	0.0368 (14)	0.0514 (17)	0.0243 (12)	0.0278 (13)	0.0187 (12)
C23	0.0392 (15)	0.0328 (13)	0.0374 (14)	0.0195 (12)	0.0226 (12)	0.0080 (11)
C24	0.0251 (11)	0.0278 (12)	0.0289 (12)	0.0133 (10)	0.0146 (10)	0.0084 (10)
C25	0.0168 (10)	0.0222 (11)	0.0216 (11)	0.0091 (9)	0.0060 (8)	0.0024 (9)
C26	0.0217 (11)	0.0230 (11)	0.0281 (12)	0.0106 (9)	0.0102 (9)	0.0055 (9)
C27	0.0193 (11)	0.0245 (12)	0.0298 (13)	0.0068 (9)	0.0048 (9)	−0.0039 (9)
C28	0.0229 (11)	0.0349 (13)	0.0243 (12)	0.0161 (10)	0.0016 (9)	−0.0017 (10)
C29	0.0293 (12)	0.0299 (13)	0.0238 (12)	0.0159 (10)	0.0060 (10)	0.0055 (10)
C30	0.0229 (11)	0.0247 (11)	0.0230 (11)	0.0110 (9)	0.0060 (9)	0.0043 (9)
C31	0.0219 (11)	0.0220 (11)	0.0217 (11)	0.0092 (9)	0.0022 (9)	0.0056 (9)
C32	0.0362 (13)	0.0291 (13)	0.0257 (12)	0.0178 (11)	0.0098 (10)	0.0049 (10)
C33	0.0481 (16)	0.0293 (13)	0.0227 (12)	0.0217 (12)	0.0044 (11)	0.0034 (10)
C34	0.0445 (16)	0.0205 (12)	0.0318 (14)	0.0115 (11)	−0.0078 (12)	0.0019 (10)
C35	0.0249 (13)	0.0285 (14)	0.0553 (18)	0.0066 (11)	−0.0010 (12)	0.0124 (13)
C36	0.0215 (12)	0.0274 (13)	0.0493 (17)	0.0103 (10)	0.0061 (11)	0.0087 (11)

Geometric parameters (Å, º) top

Rh1—P1	2.4001 (6)	C12—H12	0.9500
Rh1—P2	2.3978 (6)	C13—C14	1.400 (3)
Rh1—O2	2.1105 (19)	C13—C18	1.395 (3)
Rh1—O5*	2.09 (2)	C14—H14	0.9500
Rh1—N1	1.938 (3)	C14—C15	1.385 (4)
Rh1—N1*	1.93 (3)	C15—H15	0.9500
Rh1—N2*	2.03 (3)	C15—C16	1.387 (4)
Rh1—N3	2.019 (2)	C16—H16	0.9500
P1—C1	1.827 (2)	C16—C17	1.385 (4)
P1—C7	1.819 (2)	C17—H17	0.9500
P1—C13	1.822 (2)	C17—C18	1.379 (4)
P2—C19	1.819 (2)	C18—H18	0.9500
P2—C25	1.818 (2)	C19—C20	1.398 (3)
P2—C31	1.825 (2)	C19—C24	1.393 (3)
O1—N1	1.152 (4)	C20—H20	0.9500
O1—N1	1.147 (10)	C20—C21	1.381 (4)
O2—N2	1.277 (4)	C21—H21	0.9500
O2—N2	1.216 (18)	C21—C22	1.384 (4)
O3—N2	1.248 (5)	C22—H22	0.9500
O3—N2	1.23 (2)	C22—C23	1.384 (4)
O4—N3	1.251 (3)	C23—H23	0.9500
O4—N3*	1.230 (16)	C23—C24	1.399 (3)
O5—N3	1.231 (3)	C24—H24	0.9500
O5—N3	1.259 (18)	C25—C26	1.403 (3)
C1—C2	1.397 (3)	C25—C30	1.392 (3)
C1—C6	1.394 (3)	C26—H26	0.9500
C2—H2	0.9500	C26—C27	1.388 (3)
C2—C3	1.391 (4)	C27—H27	0.9500
C3—H3	0.9500	C27—C28	1.387 (4)
C3—C4	1.386 (4)	C28—H28	0.9500
C4—H4	0.9500	C28—C29	1.381 (4)
C4—C5	1.391 (4)	C29—H29	0.9500
C5—H5	0.9500	C29—C30	1.395 (3)
C5—C6	1.388 (4)	C30—H30	0.9500
C6—H6	0.9500	C31—C32	1.399 (4)
C7—C8	1.401 (3)	C31—C36	1.394 (4)
C7—C12	1.401 (3)	C32—H32	0.9500
C8—H8	0.9500	C32—C33	1.385 (4)
C8—C9	1.381 (3)	C33—H33	0.9500
C9—H9	0.9500	C33—C34	1.388 (4)
C9—C10	1.394 (4)	C34—H34	0.9500
C10—H10	0.9500	C34—C35	1.381 (5)
C10—C11	1.385 (4)	C35—H35	0.9500
C11—H11	0.9500	C35—C36	1.393 (4)
C11—C12	1.388 (3)	C36—H36	0.9500

P2—Rh1—P1	173.609 (19)	C7—C12—H12	120.0
O2—Rh1—P1	90.54 (5)	C11—C12—C7	120.0 (2)
O2—Rh1—P2	86.46 (5)	C11—C12—H12	120.0
O5*—Rh1—P1	91.4 (5)	C14—C13—P1	119.40 (18)
O5*—Rh1—P2	93.0 (5)	C18—C13—P1	121.50 (18)
N1—Rh1—P1	94.47 (8)	C18—C13—C14	119.1 (2)
N1—Rh1—P2	91.22 (8)	C13—C14—H14	120.1
N1—Rh1—O2	90.83 (10)	C15—C14—C13	119.9 (2)
N1—Rh1—N3	99.52 (10)	C15—C14—H14	120.1
N1*—Rh1—P1	90.3 (8)	C14—C15—H15	119.8
N1*—Rh1—P2	93.8 (8)	C14—C15—C16	120.4 (2)
N1—Rh1—O5	96.8 (9)	C16—C15—H15	119.8
N1—Rh1—N2	93.3 (11)	C15—C16—H16	120.1
N2*—Rh1—P1	88.1 (8)	C17—C16—C15	119.8 (2)
N2*—Rh1—P2	86.8 (8)	C17—C16—H16	120.1
N2—Rh1—O5	169.9 (9)	C16—C17—H17	119.9
N3—Rh1—P1	92.49 (6)	C18—C17—C16	120.2 (2)
N3—Rh1—P2	89.44 (6)	C18—C17—H17	119.9
N3—Rh1—O2	168.95 (9)	C13—C18—H18	119.7
C1—P1—Rh1	118.18 (8)	C17—C18—C13	120.5 (2)
C7—P1—Rh1	109.77 (8)	C17—C18—H18	119.7
C7—P1—C1	104.60 (11)	C20—C19—P2	117.62 (19)
C7—P1—C13	105.26 (11)	C24—C19—P2	122.60 (18)
C13—P1—Rh1	115.08 (8)	C24—C19—C20	119.6 (2)
C13—P1—C1	102.70 (10)	C19—C20—H20	119.8
C19—P2—Rh1	112.01 (8)	C21—C20—C19	120.4 (3)
C19—P2—C31	106.84 (11)	C21—C20—H20	119.8
C25—P2—Rh1	114.11 (8)	C20—C21—H21	120.0
C25—P2—C19	105.75 (11)	C20—C21—C22	120.0 (3)
C25—P2—C31	105.04 (10)	C22—C21—H21	120.0
C31—P2—Rh1	112.48 (8)	C21—C22—H22	119.8
N2—O2—Rh1	105.34 (19)	C21—C22—C23	120.4 (2)
N3—O5—Rh1	113.5 (16)	C23—C22—H22	119.8
O1—N1—Rh1	126.1 (2)	C22—C23—H23	120.0
O1—N1—Rh1	111 (2)	C22—C23—C24	120.0 (3)
O3—N2—O2	114.1 (3)	C24—C23—H23	120.0
O2—N2—Rh1	130 (2)	C19—C24—C23	119.6 (2)
O2—N2—O3*	118 (3)	C19—C24—H24	120.2
O3—N2—Rh1	111 (2)	C23—C24—H24	120.2
O4—N3—Rh1	113.23 (16)	C26—C25—P2	119.17 (18)
O5—N3—Rh1	126.50 (19)	C30—C25—P2	121.30 (18)
O5—N3—O4	120.3 (2)	C30—C25—C26	119.5 (2)
O4—N3—O5	116 (2)	C25—C26—H26	120.1
C2—C1—P1	118.11 (19)	C27—C26—C25	119.8 (2)
C6—C1—P1	122.31 (18)	C27—C26—H26	120.1
C6—C1—C2	119.4 (2)	C26—C27—H27	119.8
C1—C2—H2	120.0	C28—C27—C26	120.5 (2)
C3—C2—C1	119.9 (2)	C28—C27—H27	119.8
C3—C2—H2	120.0	C27—C28—H28	120.0
C2—C3—H3	119.7	C29—C28—C27	120.0 (2)
C4—C3—C2	120.5 (3)	C29—C28—H28	120.0
C4—C3—H3	119.7	C28—C29—H29	119.9
C3—C4—H4	120.2	C28—C29—C30	120.3 (2)
C3—C4—C5	119.6 (2)	C30—C29—H29	119.9
C5—C4—H4	120.2	C25—C30—C29	120.0 (2)
C4—C5—H5	119.8	C25—C30—H30	120.0
C6—C5—C4	120.3 (3)	C29—C30—H30	120.0
C6—C5—H5	119.8	C32—C31—P2	118.68 (19)
C1—C6—H6	119.9	C36—C31—P2	122.5 (2)
C5—C6—C1	120.2 (2)	C36—C31—C32	118.9 (2)
C5—C6—H6	119.9	C31—C32—H32	119.7
C8—C7—P1	118.47 (18)	C33—C32—C31	120.7 (3)
C8—C7—C12	119.6 (2)	C33—C32—H32	119.7
C12—C7—P1	121.65 (18)	C32—C33—H33	120.0
C7—C8—H8	120.1	C32—C33—C34	120.1 (3)
C9—C8—C7	119.7 (2)	C34—C33—H33	120.0
C9—C8—H8	120.1	C33—C34—H34	120.1
C8—C9—H9	119.7	C35—C34—C33	119.7 (3)
C8—C9—C10	120.6 (2)	C35—C34—H34	120.1
C10—C9—H9	119.7	C34—C35—H35	119.7
C9—C10—H10	120.1	C34—C35—C36	120.6 (3)
C11—C10—C9	119.9 (2)	C36—C35—H35	119.7
C11—C10—H10	120.1	C31—C36—H36	120.0
C10—C11—H11	119.9	C35—C36—C31	120.1 (3)
C10—C11—C12	120.2 (2)	C35—C36—H36	120.0
C12—C11—H11	119.9

Rh1—P1—C1—C2	48.7 (2)	C9—C10—C11—C12	0.7 (4)
Rh1—P1—C1—C6	−135.99 (19)	C10—C11—C12—C7	0.4 (4)
Rh1—P1—C7—C8	64.22 (19)	C12—C7—C8—C9	0.4 (4)
Rh1—P1—C7—C12	−109.70 (19)	C13—P1—C1—C2	−79.2 (2)
Rh1—P1—C13—C14	−174.86 (16)	C13—P1—C1—C6	96.1 (2)
Rh1—P1—C13—C18	4.5 (2)	C13—P1—C7—C8	−171.37 (18)
Rh1—P2—C19—C20	54.1 (2)	C13—P1—C7—C12	14.7 (2)
Rh1—P2—C19—C24	−120.50 (19)	C13—C14—C15—C16	−2.4 (4)
Rh1—P2—C25—C26	39.3 (2)	C14—C13—C18—C17	1.9 (3)
Rh1—P2—C25—C30	−142.69 (17)	C14—C15—C16—C17	2.5 (4)
Rh1—P2—C31—C32	61.4 (2)	C15—C16—C17—C18	−0.4 (4)
Rh1—P2—C31—C36	−117.7 (2)	C16—C17—C18—C13	−1.8 (4)
Rh1—O2—N2—O3	−2.7 (4)	C18—C13—C14—C15	0.2 (3)
Rh1—O5—N3—O4	−4 (3)	C19—P2—C25—C26	−84.2 (2)
P1—C1—C2—C3	174.9 (2)	C19—P2—C25—C30	93.8 (2)
P1—C1—C6—C5	−174.6 (2)	C19—P2—C31—C32	−175.35 (19)
P1—C7—C8—C9	−173.66 (18)	C19—P2—C31—C36	5.6 (2)
P1—C7—C12—C11	172.88 (18)	C19—C20—C21—C22	0.7 (4)
P1—C13—C14—C15	179.58 (18)	C20—C19—C24—C23	−1.3 (4)
P1—C13—C18—C17	−177.46 (19)	C20—C21—C22—C23	−1.5 (4)
P2—C19—C20—C21	−174.10 (19)	C21—C22—C23—C24	0.8 (4)
P2—C19—C24—C23	173.17 (19)	C22—C23—C24—C19	0.6 (4)
P2—C25—C26—C27	178.60 (18)	C24—C19—C20—C21	0.6 (4)
P2—C25—C30—C29	−178.92 (18)	C25—P2—C19—C20	178.94 (18)
P2—C31—C32—C33	−179.91 (19)	C25—P2—C19—C24	4.4 (2)
P2—C31—C36—C35	178.7 (2)	C25—P2—C31—C32	−63.3 (2)
C1—P1—C7—C8	−63.5 (2)	C25—P2—C31—C36	117.6 (2)
C1—P1—C7—C12	122.6 (2)	C25—C26—C27—C28	0.1 (4)
C1—P1—C13—C14	−45.1 (2)	C26—C25—C30—C29	−0.9 (4)
C1—P1—C13—C18	134.26 (19)	C26—C27—C28—C29	−0.5 (4)
C1—C2—C3—C4	0.6 (4)	C27—C28—C29—C30	0.1 (4)
C2—C1—C6—C5	0.6 (4)	C28—C29—C30—C25	0.6 (4)
C2—C3—C4—C5	−0.7 (4)	C30—C25—C26—C27	0.6 (3)
C3—C4—C5—C6	0.8 (4)	C31—P2—C19—C20	−69.5 (2)
C4—C5—C6—C1	−0.7 (4)	C31—P2—C19—C24	115.9 (2)
C6—C1—C2—C3	−0.6 (4)	C31—P2—C25—C26	162.96 (19)
C7—P1—C1—C2	171.12 (19)	C31—P2—C25—C30	−19.0 (2)
C7—P1—C1—C6	−13.6 (2)	C31—C32—C33—C34	1.4 (4)
C7—P1—C13—C14	64.2 (2)	C32—C31—C36—C35	−0.4 (4)
C7—P1—C13—C18	−116.51 (19)	C32—C33—C34—C35	−0.9 (4)
C7—C8—C9—C10	0.7 (4)	C33—C34—C35—C36	−0.2 (4)
C8—C7—C12—C11	−1.0 (4)	C34—C35—C36—C31	0.9 (4)
C8—C9—C10—C11	−1.3 (4)	C36—C31—C32—C33	−0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O5	0.95	2.27	3.200 (3)	166
C2—H2···O5*	0.95	2.40	3.213 (19)	144
C18—H18···O4	0.95	2.34	3.130 (3)	140
C21—H21···N2ⁱ	0.95	2.44	3.328 (4)	155
C32—H32···O2	0.95	2.40	3.118 (3)	132
C32—H32···O2*	0.95	2.36	3.24 (2)	154
C33—H33···N3*ⁱⁱ	0.95	2.38	3.21 (2)	145

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

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