Crystal structures of fac-tri­chlorido­tris­(tri­methyl­phosphane-κP)rhodium(III) monohydrate and fac-tri­chlorido­tris­(tri­methyl­phosphane-κP)rhodium(III) methanol hemisolvate: rhodium structures that are isotypic with their iridium analogs

The structures of two solvates (water and methanol) of the facial isomer of (Me₃P)₃RhCl₃ are reported and compared with previously published facial (Me₃P)₃IrCl₃ solvates with which they are isostructural and isomorphous.

Abstract

The crystal structures of two solvates of fac-tri­chlorido­tris­(tri­methyl­phosphane-κP)rhodium(III) are reported, i.e. one with water in the crystal lattice, fac-[RhCl₃(Me₃P)₃]·H₂O, and one with methanol in the crystal lattice, fac-[RhCl₃(Me₃P)₃]·0.5CH₃OH. These rhodium compounds exhibit distorted octahedral coordination spheres at the metal and are isotypic with the analogous iridium compounds previously reported by us [Merola et al. (2013 ▸). Polyhedron, 54, 67–73]. Comparison is made between the rhodium and iridium compounds, highlighting their isostructural relationships.

Chemical context  

Phosphane complexes of noble metals, especially those of rhodium and iridium, have proven to be important in catalysis as well as in studying fundamental reactions at metal surfaces. Chlorido compounds of rhodium and iridium with phosphane ligands provide important starting materials for other metal complexes of that family through replacement of the chlorine. For example, we have shown that (Me₃P)₃IrCl₃ can be converted into (Me₃P)₃IrMe₃ through reaction with methyl­magnesiumchloride. This tri­methyl­iridium compound can, in turn, be used to study organometallic reactions at the irid­ium(III) atom (Merola et al., 2013 ▸). Thus, the fundamental study of crystal structures of phosphane–chlorido complexes of iridium and rhodium is important to help understand the structures, the bonding and the stereochemistry of this class of compounds. This paper adds to the body of knowledge of rhodium complexes that complement the already published structures of the analogous iridium compounds. It contributes to the information on crystal structures of L ₃ MCl₃ compounds, comparing the rhodium structures to the iridium structures as well as confirming the nature of solvate formation in both the iridium and rhodium structures.

Structural commentary  

The title complexes fac-tri­chlorido­tris­(tri­methyl­phosphane-κP)rhodium(III) monohydrate, RhP₃Cl₃water, and fac-tri­chlorido­tris­(tri­methyl­phosphane-κP)rhodium(III) methanol hemihydrate, RhP₃Cl₃MeOH, are isotypic with their iridium counterparts (CCDC 896072, 896073; Merola et al., 2013 ▸). Isotypism in rhodium and iridium complexes is not unusual, largely owing to the lanthanide contraction resulting in very similar radii for both second- and third-row transition elements (Cordero et al., 2008 ▸).

Fig. 1 ▸ is a displacement ellipsoid rendering of compound RhP₃Cl₃water and Fig. 2 ▸ is a displacement ellipsoid rendering of compound RhP₃Cl₃MeOH. For compounds RhP₃Cl₃water and RhP₃Cl₃MeOH reported here, the comparison with their iridium analogs can be found in Tables 1 ▸ and 2 ▸ which list the corresponding unit-cell parameters for the rhodium and iridium water solvates (Table 1 ▸) and the rhodium and iridium methanol solvate (Table 2 ▸). The iridium compounds show a very slight lengthening of the unit-cell dimensions compared to rhodium but they are clearly isotypic overall. Table 3 ▸ lists the important bond lengths for RhP₃Cl₃water and IrP₃Cl₃water while Table 4 ▸ lists these for RhP₃Cl₃MeOH and IrP₃Cl₃MeOH. Bond-length comparisons show little significant difference between the rhodium and iridium analogs.

Figure 1.

Displacement ellipsoid (50% probability level) rendering of the fac-tri­chlorido­tris­(tri­methyl­phosphane)rhodium–water compound, RhP₃Cl₃water.

Figure 2.

Displacement ellipsoid (50% probability level) rendering of the fac-tri­chlorido­tris­(tri­methyl­phosphane)rhodium–0.5(methanol) compound, RhP₃Cl₃MeOH.

Table 1. Comparison of unit-cell dimensions (, ) for water solvate complexes RhP₃Cl₃water and IrP₃Cl₃water .

Compound	space group	a	b	c
RhP3Cl3water	Cc	15.8650(12)	9.0396(3)	14.8223(18)	120.820(7)
IrP3Cl3water	Cc	15.8830(10)	9.0590(10)	14.829(2)	120.530(8)

Table 2. Comparison of unit-cell dimensions (, ) for methanol solvate complexes RhP₃Cl₃MeOH and IrP₃Cl₃MeOH .

Compound	space group	a	b	c
RhP3Cl3MeOH	P21/n	16.0993(16)	15.5910(9)	16.4152(14)	115.084(13)
IrP3Cl3MeOH	P21/n	16.144(3)	15.631(4)	16.469(4)	115.400(17)

Table 3. Comparison of significant bond lengths () for RhP₃Cl₃water and IrP₃Cl₃water .

Compound	MP1	MP2	MP3	MCl1	MCl2	MCl3
RhP3Cl3water	2.279(2)	2.295(3)	2.292(2)	2.450(2)	2.444(3)	2.436(3)
IrP3Cl3water	2.2787(18)	2.2880(19)	2.2912(17)	2.4320(19)	2.4469(18)	2.4451(19)

Table 4. Comparison of significant bond lengths () for RhP₃Cl₃MeOH and IrP₃Cl₃MeOH .

Compound	MP1	MP2	MP3	MCl1	MCl2	MCl3
RhP3Cl3MeOH	2.2824(12)	2.2950(13)	2.2995(12)	2.4246(11)	2.4453(12)	2.4364(12)
	2.2860(13)	2.2954(12)	2.2923(11)	2.4372(12)	2.4476(12)	2.4426(12)
IrP3Cl3MeOH	2.2809(16)	2.2847(17)	2.2964(15)	2.4245(16)	2.4368(17)	2.4394(15)
	2.2932(16)	2.2795(17)	2.2869(16)	2.4442(16)	2.4316(17)	2.4405(17)

Supra­molecular features  

It is not surprising that fac-tris­(tri­methyl­phosphane)tri­chloroidium(III) and -rhodium(III) complexes form lattice solvates since the shape of the individual mol­ecules leads to packing with voids in the lattice. Thus, every structure we have determined with the iridium compounds, as well as the ones reported here, contains a solvent. In the case of the water solvate, Fig. 3 ▸ shows the packing diagram for RhP₃Cl₃water looking down the c axis. One can see that the packing involves alternating layers of rhodium mol­ecules and water mol­ecules. The water mol­ecules show close, hydrogen-bonding inter­actions (Table 5 ▸) between the water and the chlorines on one layer of the rhodium compound as well as close C—H⋯O inter­actions between the phosphane methyl groups and the water oxygen. One should not make much of the hydrogen positions on the water since, although they were originally found in difference maps, the O—H bond lengths and the H—O—H angle were restrained with DFIX and DANG commands (Sheldrick, 2015 ▸). Fig. 4 ▸ shows the packing diagram for RhP₃Cl₃MeOH, looking down the c axis, illustrating the O—H⋯Cl hydrogen bonding (Table 6 ▸) and the location of the methanol mol­ecules in a channel in the crystal.

Figure 3.

Packing diagram of the fac-tri­chlorido­tris­(tri­methyl­phosphane)rhodium–water compound, RhP₃Cl₃water, viewed down the c axis, showing the alternating layers of complex and water mol­ecules. Hydrogen atoms except for water H atoms are omitted for clarity.

Table 5. Hydrogen-bond geometry (, ) for RhP₃Cl₃water .

DHA	DH	HA	D A	DHA
O1H1BCl3	0.97	2.57	3.481	157

Figure 4.

Packing diagram of the fac-tri­chlorido­tris­(tri­methyl­phosphane)rhodium–0.5(methanol) compound, RhP₃Cl₃MeOH, viewed down the c axis, showing the methanol-containing channel in the structure. H atoms, except for water H atoms, a omitted for clarity.

Table 6. Hydrogen-bond geometry (, ) for RhP₃Cl₃MeOH .

DHA	DH	HA	D A	DHA
O1H1Cl6i	0.82	2.47	3.184(5)	147

Symmetry code: (i) .

Database survey  

A search of the Cambridge Structural Database (Groom & Allen, 2014 ▸) surprisingly shows very few structurally characterized tri­chlorido­tris­phosphaneiridium or rhodium compounds. In the case of iridium, beside the structures we recently published (CCDC 896072–896076; Merola et al., 2013 ▸), there are only three other P₃IrCl₃ compounds in the database – the mer and fac isomers with P = phenyldi­methyl­phosphane (refcodes CTPIRA01, CTPIRC: Marsh, 1997 ▸; Robertson & Tucker, 1981 ▸) and one entry where P₃ is cis,cis-1,3,5-tris­(di­phenyl­phosphino)cyclo­hexane (refcode LEXFAV; Mayer et al., 1994 ▸). For rhodium, P₃RhCl₃ structur­ally characterized compounds are also rare with one mixed-ligand complex (two tri-n-butyl­phosphane ligands and one tri­methyl­phosphite ligand; refcode CBPMRH; Allen et al., 1970 ▸), a complex with 3 hy­droxy­methyl­phosphane ligands (CCDC 189926; Raghuraman et al., 2002 ▸), a complex with the tripodal ligand, 1,1,1-tris­(di­methyl­phosphinometh­yl)ethane (refcode NAHXID; Suzuki et al., 1996 ▸), a complex with the tridentate ligand, 1,5,9-tris­(2-prop­yl)-1,5,9-triphospha­cyclo­dodecane (refcode NOLPIN; Edwards et al., 1997 ▸), a mer-tris-di­methyl­phenyl­phosphane compound (CCDC 247871; Parsons et al., 2004 ▸) and a mer-tris-di­ethyl­phenyl­phosphane compound (refcode TCPERH; Skapski & Stephens, 1973 ▸). Of those, the only directly comparable structures are the mer isomer complexes of rhodium and iridium with di­methyl­phenyl­phosphane ligands and those two are indeed isostructural with each other.

Synthesis and crystallization  

The rhodium complexes described herein could not be characterized spectroscopically as pure materials, but were isolated as crystals from complex mixtures. In contrast to the iridium complex [IrCOD(PMe₃)₃]Cl (COD = cyclo­octa­diene) (Frazier & Merola, 1992 ▸) which is the starting material for much of our iridium work, attempts to synthesize the analogous rhodium compound met with no success. Reaction between various Rh^I olefin complexes, including COD, especially in di­chloro­methane solvent, led to complex mixtures of Rh(PMe₃)_n compounds in all cases. That these compounds are compounds of Rh is clearly seen in the Rh–P chemical coupling in the complicated ³¹P NMR spectra. Attempts at extracting a pure compound from the complex mixture with various solvents including di­chloro­methane, water, methanol and acetone did not yield clean materials. Following extraction, the solutions were allowed to sit in the open air for several days and, in the case of water and methanol, a few crystals suitable for X-ray crystallography were formed and used for the data collection described in this communication.

Refinement  

Crystal data, data collection and structure refinement details are summarized in Table 7 ▸. The hydrogens on the lattice water mol­ecule in RhP₃Cl₃water were initially assigned based on residual electron density but were then restrained with DFIX and DANG instructions in SHELXL (Sheldrick, 2015 ▸) during refinement.

Table 7. Experimental details.

	RhP3Cl3water	RhP3Cl3MeOH
Crystal data
Chemical formula	[RhCl3(C3H9P)3]H2O	[RhCl3(C3H9P)3]0.5CH4O
M r	455.49	453.50
Crystal system, space group	Monoclinic, C c	Monoclinic, P21/n
Temperature (K)	298	298
a, b, c ()	15.8650(12), 9.0396(3), 14.8223(18)	16.0993(16), 15.5910(9), 16.4152(14)
()	120.820(7)	115.084(13)
V (3)	1825.5(3)	3731.7(5)
Z	4	8
Radiation type	Mo K	Mo K
(mm1)	1.62	1.59
Crystal size (mm)	0.4 0.4 0.3	0.6 0.6 0.3
Data collection
Diffractometer	Siemens P4	Siemens P4
Absorption correction	scan (North et al., 1968 ▸)	scan (North et al., 1968 ▸)
T min, T max	0.762, 0.974	0.807, 0.915
No. of measured, independent and observed [I > 2(I)] reflections	2034, 1784, 1763	5957, 4858, 4171
R int	0.021	0.034
max ()	25.0	22.5
(sin /)max (1)	0.595	0.538
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.023, 0.059, 1.08	0.029, 0.071, 1.08
No. of reflections	1784	4858
No. of parameters	170	328
No. of restraints	5	0
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H-atom parameters constrained
max, min (e 3)	0.47, 0.60	1.03, 0.41
Absolute structure	Classical Flack (1983 ▸) method preferred over Parsons because s.u. lower
Absolute structure parameter	0.06(3)

Computer programs: XSCANS (Siemens, 1996 ▸), SHELXS87 and SHELXS97 (Sheldrick, 2008 ▸), SHELXL2014 (Sheldrick, 2015 ▸) and OLEX2 (Dolomanov et al., 2009 ▸).

Supplementary Material

CCDC references: 1045021, 1045022

Additional supporting information: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Crystal data

[RhCl3(C3H9P)3]·0.5CH4O	F(000) = 1848
Mr = 453.50	Dx = 1.614 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 16.0993 (16) Å	Cell parameters from 50 reflections
b = 15.5910 (9) Å	θ = 3–20°
c = 16.4152 (14) Å	µ = 1.59 mm−1
β = 115.084 (13)°	T = 298 K
V = 3731.7 (5) Å3	Prism, clear light yellow
Z = 8	0.6 × 0.6 × 0.3 mm

Data collection

Siemens P4 diffractometer	4171 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.034
Graphite monochromator	θmax = 22.5°, θmin = 1.9°
sea;ed X–ray tube scans	h = −1→17
Absorption correction: ψ scan (North et al., 1968)	k = −1→16
Tmin = 0.807, Tmax = 0.915	l = −17→16
5957 measured reflections	3 standard reflections every 200 reflections
4858 independent reflections	intensity decay: 0.0(2)

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.071	w = 1/[σ2(Fo2) + (0.0286P)2 + 4.1793P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.003
4858 reflections	Δρmax = 1.03 e Å−3
328 parameters	Δρmin = −0.41 e Å−3
0 restraints	Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00519 (17)

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
Rh1	0.76635 (2)	0.66132 (2)	0.08786 (2)	0.02237 (12)
Cl1	0.82866 (8)	0.79954 (7)	0.07477 (9)	0.0435 (3)
Cl2	0.65651 (8)	0.67764 (8)	−0.06932 (7)	0.0445 (3)
Cl3	0.87487 (8)	0.60045 (8)	0.03606 (8)	0.0449 (3)
P1	0.72796 (9)	0.52126 (7)	0.09374 (8)	0.0361 (3)
P2	0.87465 (8)	0.66934 (7)	0.23406 (8)	0.0308 (3)
P3	0.64873 (8)	0.71971 (7)	0.11404 (8)	0.0314 (3)
C11	0.8230 (4)	0.4462 (3)	0.1382 (4)	0.0583 (15)
H11A	0.8605	0.4524	0.1061	0.087*
H11B	0.7996	0.3887	0.1311	0.087*
H11C	0.8590	0.4577	0.2009	0.087*
C12	0.6631 (5)	0.4911 (4)	0.1567 (5)	0.076 (2)
H12A	0.6949	0.5102	0.2178	0.114*
H12B	0.6565	0.4298	0.1557	0.114*
H12C	0.6035	0.5172	0.1299	0.114*
C13	0.6596 (4)	0.4779 (3)	−0.0171 (4)	0.0614 (16)
H13A	0.6011	0.5060	−0.0426	0.092*
H13B	0.6509	0.4175	−0.0125	0.092*
H13C	0.6907	0.4872	−0.0550	0.092*
C21	0.8719 (4)	0.5969 (4)	0.3203 (3)	0.0588 (15)
H21A	0.8132	0.6008	0.3222	0.088*
H21B	0.9191	0.6127	0.3778	0.088*
H21C	0.8818	0.5391	0.3063	0.088*
C22	0.9893 (3)	0.6550 (4)	0.2430 (4)	0.0567 (15)
H22A	0.9979	0.5962	0.2310	0.085*
H22B	1.0329	0.6699	0.3027	0.085*
H22C	0.9983	0.6914	0.2002	0.085*
C23	0.8810 (4)	0.7718 (3)	0.2882 (4)	0.0536 (14)
H23A	0.8582	0.8160	0.2434	0.080*
H23B	0.9436	0.7839	0.3282	0.080*
H23C	0.8445	0.7699	0.3217	0.080*
C31	0.5349 (3)	0.6773 (4)	0.0457 (4)	0.0572 (15)
H31A	0.5217	0.6830	−0.0169	0.086*
H31B	0.4902	0.7086	0.0580	0.086*
H31C	0.5327	0.6178	0.0597	0.086*
C32	0.6344 (4)	0.8316 (3)	0.0863 (5)	0.071 (2)
H32A	0.6892	0.8621	0.1238	0.107*
H32B	0.5835	0.8537	0.0958	0.107*
H32C	0.6228	0.8391	0.0243	0.107*
C33	0.6502 (4)	0.7160 (4)	0.2248 (3)	0.0554 (15)
H33A	0.6542	0.6574	0.2442	0.083*
H33B	0.5950	0.7413	0.2227	0.083*
H33C	0.7023	0.7473	0.2664	0.083*
Rh2	0.29937 (2)	0.83004 (2)	0.11738 (2)	0.02531 (12)
Cl4	0.44698 (8)	0.89262 (9)	0.14246 (9)	0.0497 (3)
Cl5	0.29238 (9)	0.77329 (8)	−0.02441 (8)	0.0480 (3)
Cl6	0.38403 (10)	0.69898 (8)	0.18403 (9)	0.0534 (4)
P4	0.15796 (9)	0.76893 (8)	0.07421 (9)	0.0412 (3)
P5	0.31781 (8)	0.86191 (7)	0.26057 (7)	0.0309 (3)
P6	0.24255 (8)	0.96155 (7)	0.05702 (7)	0.0277 (3)
C41	0.0844 (4)	0.7767 (4)	−0.0452 (4)	0.0686 (17)
H41A	0.0786	0.8357	−0.0634	0.103*
H41B	0.0250	0.7539	−0.0571	0.103*
H41C	0.1108	0.7445	−0.0782	0.103*
C42	0.0818 (4)	0.8051 (4)	0.1233 (4)	0.0610 (16)
H42A	0.1085	0.7920	0.1864	0.092*
H42B	0.0237	0.7766	0.0943	0.092*
H42C	0.0729	0.8660	0.1152	0.092*
C43	0.1622 (5)	0.6541 (3)	0.0936 (5)	0.0735 (19)
H43A	0.1949	0.6269	0.0635	0.110*
H43B	0.1010	0.6317	0.0706	0.110*
H43C	0.1931	0.6429	0.1570	0.110*
C51	0.2460 (4)	0.9416 (3)	0.2801 (3)	0.0477 (13)
H51A	0.2562	0.9965	0.2596	0.072*
H51B	0.2612	0.9444	0.3432	0.072*
H51C	0.1828	0.9258	0.2477	0.072*
C52	0.4313 (3)	0.9011 (4)	0.3307 (3)	0.0522 (14)
H52A	0.4761	0.8607	0.3302	0.078*
H52B	0.4376	0.9082	0.3911	0.078*
H52C	0.4406	0.9553	0.3080	0.078*
C53	0.3059 (4)	0.7705 (3)	0.3231 (3)	0.0480 (13)
H53A	0.2448	0.7482	0.2937	0.072*
H53B	0.3177	0.7882	0.3830	0.072*
H53C	0.3491	0.7269	0.3256	0.072*
C61	0.2455 (4)	0.9750 (3)	−0.0508 (3)	0.0470 (13)
H61A	0.3062	0.9631	−0.0452	0.071*
H61B	0.2292	1.0329	−0.0711	0.071*
H61C	0.2028	0.9362	−0.0934	0.071*
C62	0.3089 (4)	1.0522 (3)	0.1198 (3)	0.0516 (14)
H62A	0.3124	1.0511	0.1797	0.077*
H62B	0.2798	1.1045	0.0905	0.077*
H62C	0.3696	1.0493	0.1226	0.077*
C63	0.1272 (3)	0.9971 (3)	0.0347 (3)	0.0425 (12)
H63A	0.0832	0.9593	−0.0082	0.064*
H63B	0.1180	1.0543	0.0108	0.064*
H63C	0.1196	0.9965	0.0896	0.064*
O1	0.0306 (5)	1.0413 (3)	0.1833 (4)	0.1076 (18)
H1	0.0327	1.0913	0.1996	0.161*
C2	−0.0030 (4)	0.9903 (4)	0.2311 (4)	0.0705 (17)
H2A	−0.0355	0.9425	0.1946	0.106*
H2B	−0.0439	1.0232	0.2476	0.106*
H2C	0.0471	0.9696	0.2845	0.106*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Rh1	0.0230 (2)	0.02200 (19)	0.02360 (19)	0.00153 (14)	0.01137 (15)	0.00271 (14)
Cl1	0.0405 (7)	0.0301 (6)	0.0631 (8)	−0.0004 (5)	0.0251 (6)	0.0148 (6)
Cl2	0.0390 (7)	0.0641 (8)	0.0261 (6)	0.0069 (6)	0.0096 (5)	0.0060 (5)
Cl3	0.0452 (7)	0.0563 (8)	0.0423 (7)	0.0173 (6)	0.0273 (6)	0.0041 (6)
P1	0.0411 (7)	0.0244 (6)	0.0434 (7)	−0.0039 (5)	0.0186 (6)	−0.0009 (5)
P2	0.0303 (6)	0.0311 (6)	0.0282 (6)	0.0023 (5)	0.0095 (5)	0.0005 (5)
P3	0.0265 (6)	0.0341 (6)	0.0373 (7)	0.0029 (5)	0.0172 (5)	0.0018 (5)
C11	0.065 (4)	0.027 (3)	0.068 (4)	0.011 (3)	0.015 (3)	0.004 (3)
C12	0.102 (5)	0.042 (3)	0.114 (6)	−0.013 (3)	0.076 (5)	0.013 (3)
C13	0.062 (4)	0.043 (3)	0.064 (4)	−0.009 (3)	0.012 (3)	−0.015 (3)
C21	0.078 (4)	0.060 (4)	0.036 (3)	0.002 (3)	0.022 (3)	0.009 (3)
C22	0.025 (3)	0.081 (4)	0.050 (3)	0.010 (3)	0.002 (2)	0.003 (3)
C23	0.057 (3)	0.044 (3)	0.046 (3)	−0.009 (3)	0.008 (3)	−0.018 (3)
C31	0.029 (3)	0.086 (4)	0.054 (3)	−0.004 (3)	0.016 (3)	−0.004 (3)
C32	0.069 (4)	0.042 (3)	0.131 (6)	0.026 (3)	0.070 (4)	0.022 (3)
C33	0.049 (3)	0.081 (4)	0.043 (3)	0.007 (3)	0.027 (3)	−0.010 (3)
Rh2	0.0255 (2)	0.0244 (2)	0.0276 (2)	0.00468 (14)	0.01264 (16)	0.00091 (14)
Cl4	0.0295 (6)	0.0641 (8)	0.0616 (8)	0.0000 (6)	0.0253 (6)	0.0014 (7)
Cl5	0.0720 (9)	0.0401 (7)	0.0366 (7)	0.0102 (6)	0.0275 (6)	−0.0030 (5)
Cl6	0.0707 (9)	0.0416 (7)	0.0518 (8)	0.0308 (7)	0.0297 (7)	0.0140 (6)
P4	0.0372 (7)	0.0310 (7)	0.0511 (8)	−0.0076 (6)	0.0145 (6)	−0.0006 (6)
P5	0.0313 (7)	0.0342 (7)	0.0281 (6)	0.0046 (5)	0.0134 (5)	0.0024 (5)
P6	0.0283 (6)	0.0244 (6)	0.0297 (6)	0.0011 (5)	0.0118 (5)	0.0003 (5)
C41	0.050 (3)	0.068 (4)	0.062 (4)	−0.019 (3)	−0.001 (3)	−0.013 (3)
C42	0.040 (3)	0.071 (4)	0.079 (4)	−0.009 (3)	0.031 (3)	0.004 (3)
C43	0.079 (5)	0.033 (3)	0.101 (5)	−0.013 (3)	0.032 (4)	0.002 (3)
C51	0.061 (3)	0.047 (3)	0.043 (3)	0.016 (3)	0.030 (3)	0.000 (2)
C52	0.045 (3)	0.066 (4)	0.033 (3)	−0.003 (3)	0.004 (2)	0.002 (3)
C53	0.063 (3)	0.044 (3)	0.045 (3)	0.005 (3)	0.031 (3)	0.013 (2)
C61	0.064 (3)	0.039 (3)	0.047 (3)	0.011 (3)	0.032 (3)	0.009 (2)
C62	0.058 (3)	0.030 (3)	0.053 (3)	−0.013 (2)	0.012 (3)	−0.006 (2)
C63	0.035 (3)	0.042 (3)	0.050 (3)	0.011 (2)	0.017 (2)	0.006 (2)
O1	0.145 (5)	0.095 (4)	0.077 (3)	−0.022 (4)	0.040 (3)	−0.020 (3)
C2	0.063 (4)	0.084 (5)	0.063 (4)	−0.003 (4)	0.026 (3)	0.001 (4)

Geometric parameters (Å, º)

Rh1—Cl1	2.4248 (11)	Rh2—P4	2.2857 (13)
Rh1—Cl2	2.4455 (12)	Rh2—P5	2.2952 (12)
Rh1—Cl3	2.4363 (12)	Rh2—P6	2.2922 (11)
Rh1—P1	2.2825 (12)	P4—C41	1.814 (6)
Rh1—P2	2.2951 (12)	P4—C42	1.819 (5)
Rh1—P3	2.2998 (12)	P4—C43	1.815 (5)
P1—C11	1.816 (5)	P5—C51	1.815 (5)
P1—C12	1.816 (5)	P5—C52	1.804 (5)
P1—C13	1.811 (5)	P5—C53	1.812 (5)
P2—C21	1.827 (5)	P6—C61	1.802 (5)
P2—C22	1.803 (5)	P6—C62	1.808 (5)
P2—C23	1.810 (5)	P6—C63	1.820 (4)
P3—C31	1.820 (5)	C41—H41A	0.9600
P3—C32	1.793 (5)	C41—H41B	0.9600
P3—C33	1.810 (5)	C41—H41C	0.9600
C11—H11A	0.9600	C42—H42A	0.9600
C11—H11B	0.9600	C42—H42B	0.9600
C11—H11C	0.9600	C42—H42C	0.9600
C12—H12A	0.9600	C43—H43A	0.9600
C12—H12B	0.9600	C43—H43B	0.9600
C12—H12C	0.9600	C43—H43C	0.9600
C13—H13A	0.9600	C51—H51A	0.9600
C13—H13B	0.9600	C51—H51B	0.9600
C13—H13C	0.9600	C51—H51C	0.9600
C21—H21A	0.9600	C52—H52A	0.9600
C21—H21B	0.9600	C52—H52B	0.9600
C21—H21C	0.9600	C52—H52C	0.9600
C22—H22A	0.9600	C53—H53A	0.9600
C22—H22B	0.9600	C53—H53B	0.9600
C22—H22C	0.9600	C53—H53C	0.9600
C23—H23A	0.9600	C61—H61A	0.9600
C23—H23B	0.9600	C61—H61B	0.9600
C23—H23C	0.9600	C61—H61C	0.9600
C31—H31A	0.9600	C62—H62A	0.9600
C31—H31B	0.9600	C62—H62B	0.9600
C31—H31C	0.9600	C62—H62C	0.9600
C32—H32A	0.9600	C63—H63A	0.9600
C32—H32B	0.9600	C63—H63B	0.9600
C32—H32C	0.9600	C63—H63C	0.9600
C33—H33A	0.9600	O1—H1	0.8200
C33—H33B	0.9600	O1—C2	1.379 (7)
C33—H33C	0.9600	C2—H2A	0.9600
Rh2—Cl4	2.4371 (12)	C2—H2B	0.9600
Rh2—Cl5	2.4477 (12)	C2—H2C	0.9600
Rh2—Cl6	2.4424 (12)
Cl1—Rh1—Cl2	87.44 (4)	P4—Rh2—Cl5	85.19 (5)
Cl1—Rh1—Cl3	86.01 (4)	P4—Rh2—Cl6	94.79 (5)
Cl3—Rh1—Cl2	88.69 (4)	P4—Rh2—P5	95.00 (5)
P1—Rh1—Cl1	169.61 (4)	P4—Rh2—P6	94.38 (4)
P1—Rh1—Cl2	93.24 (5)	P5—Rh2—Cl4	92.68 (5)
P1—Rh1—Cl3	83.64 (5)	P5—Rh2—Cl5	170.38 (4)
P1—Rh1—P2	96.15 (4)	P5—Rh2—Cl6	85.24 (4)
P1—Rh1—P3	96.41 (4)	P6—Rh2—Cl4	84.07 (4)
P2—Rh1—Cl1	83.39 (4)	P6—Rh2—Cl5	93.63 (4)
P2—Rh1—Cl2	170.60 (4)	P6—Rh2—Cl6	170.61 (5)
P2—Rh1—Cl3	92.69 (4)	P6—Rh2—P5	95.95 (4)
P2—Rh1—P3	95.95 (4)	C41—P4—Rh2	114.5 (2)
P3—Rh1—Cl1	93.96 (4)	C41—P4—C42	101.8 (3)
P3—Rh1—Cl2	82.62 (4)	C41—P4—C43	102.4 (3)
P3—Rh1—Cl3	171.30 (4)	C42—P4—Rh2	120.21 (19)
C11—P1—Rh1	115.90 (18)	C43—P4—Rh2	113.5 (2)
C11—P1—C12	101.2 (3)	C43—P4—C42	102.2 (3)
C12—P1—Rh1	120.2 (2)	C51—P5—Rh2	120.87 (17)
C13—P1—Rh1	112.00 (19)	C52—P5—Rh2	112.52 (18)
C13—P1—C11	102.3 (3)	C52—P5—C51	101.8 (3)
C13—P1—C12	103.0 (3)	C52—P5—C53	103.1 (2)
C21—P2—Rh1	121.30 (19)	C53—P5—Rh2	114.25 (18)
C22—P2—Rh1	112.11 (18)	C53—P5—C51	102.1 (2)
C22—P2—C21	102.8 (3)	C61—P6—Rh2	110.90 (16)
C22—P2—C23	103.1 (3)	C61—P6—C62	102.3 (2)
C23—P2—Rh1	114.92 (18)	C61—P6—C63	102.5 (2)
C23—P2—C21	100.4 (3)	C62—P6—Rh2	114.98 (17)
C31—P3—Rh1	115.75 (18)	C62—P6—C63	100.5 (2)
C32—P3—Rh1	111.43 (18)	C63—P6—Rh2	123.06 (16)
C32—P3—C31	102.1 (3)	P4—C41—H41A	109.5
C32—P3—C33	103.4 (3)	P4—C41—H41B	109.5
C33—P3—Rh1	120.93 (18)	P4—C41—H41C	109.5
C33—P3—C31	100.9 (3)	H41A—C41—H41B	109.5
P1—C11—H11A	109.5	H41A—C41—H41C	109.5
P1—C11—H11B	109.5	H41B—C41—H41C	109.5
P1—C11—H11C	109.5	P4—C42—H42A	109.5
H11A—C11—H11B	109.5	P4—C42—H42B	109.5
H11A—C11—H11C	109.5	P4—C42—H42C	109.5
H11B—C11—H11C	109.5	H42A—C42—H42B	109.5
P1—C12—H12A	109.5	H42A—C42—H42C	109.5
P1—C12—H12B	109.5	H42B—C42—H42C	109.5
P1—C12—H12C	109.5	P4—C43—H43A	109.5
H12A—C12—H12B	109.5	P4—C43—H43B	109.5
H12A—C12—H12C	109.5	P4—C43—H43C	109.5
H12B—C12—H12C	109.5	H43A—C43—H43B	109.5
P1—C13—H13A	109.5	H43A—C43—H43C	109.5
P1—C13—H13B	109.5	H43B—C43—H43C	109.5
P1—C13—H13C	109.5	P5—C51—H51A	109.5
H13A—C13—H13B	109.5	P5—C51—H51B	109.5
H13A—C13—H13C	109.5	P5—C51—H51C	109.5
H13B—C13—H13C	109.5	H51A—C51—H51B	109.5
P2—C21—H21A	109.5	H51A—C51—H51C	109.5
P2—C21—H21B	109.5	H51B—C51—H51C	109.5
P2—C21—H21C	109.5	P5—C52—H52A	109.5
H21A—C21—H21B	109.5	P5—C52—H52B	109.5
H21A—C21—H21C	109.5	P5—C52—H52C	109.5
H21B—C21—H21C	109.5	H52A—C52—H52B	109.5
P2—C22—H22A	109.5	H52A—C52—H52C	109.5
P2—C22—H22B	109.5	H52B—C52—H52C	109.5
P2—C22—H22C	109.5	P5—C53—H53A	109.5
H22A—C22—H22B	109.5	P5—C53—H53B	109.5
H22A—C22—H22C	109.5	P5—C53—H53C	109.5
H22B—C22—H22C	109.5	H53A—C53—H53B	109.5
P2—C23—H23A	109.5	H53A—C53—H53C	109.5
P2—C23—H23B	109.5	H53B—C53—H53C	109.5
P2—C23—H23C	109.5	P6—C61—H61A	109.5
H23A—C23—H23B	109.5	P6—C61—H61B	109.5
H23A—C23—H23C	109.5	P6—C61—H61C	109.5
H23B—C23—H23C	109.5	H61A—C61—H61B	109.5
P3—C31—H31A	109.5	H61A—C61—H61C	109.5
P3—C31—H31B	109.5	H61B—C61—H61C	109.5
P3—C31—H31C	109.5	P6—C62—H62A	109.5
H31A—C31—H31B	109.5	P6—C62—H62B	109.5
H31A—C31—H31C	109.5	P6—C62—H62C	109.5
H31B—C31—H31C	109.5	H62A—C62—H62B	109.5
P3—C32—H32A	109.5	H62A—C62—H62C	109.5
P3—C32—H32B	109.5	H62B—C62—H62C	109.5
P3—C32—H32C	109.5	P6—C63—H63A	109.5
H32A—C32—H32B	109.5	P6—C63—H63B	109.5
H32A—C32—H32C	109.5	P6—C63—H63C	109.5
H32B—C32—H32C	109.5	H63A—C63—H63B	109.5
P3—C33—H33A	109.5	H63A—C63—H63C	109.5
P3—C33—H33B	109.5	H63B—C63—H63C	109.5
P3—C33—H33C	109.5	C2—O1—H1	109.5
H33A—C33—H33B	109.5	O1—C2—H2A	109.5
H33A—C33—H33C	109.5	O1—C2—H2B	109.5
H33B—C33—H33C	109.5	O1—C2—H2C	109.5
Cl4—Rh2—Cl5	87.35 (5)	H2A—C2—H2B	109.5
Cl4—Rh2—Cl6	86.57 (5)	H2A—C2—H2C	109.5
Cl6—Rh2—Cl5	85.15 (4)	H2B—C2—H2C	109.5
P4—Rh2—Cl4	172.28 (5)
Cl1—Rh1—P1—C11	36.4 (4)	P3—Rh1—P2—C23	−47.9 (2)
Cl1—Rh1—P1—C12	158.6 (3)	Cl4—Rh2—P5—C51	111.9 (2)
Cl1—Rh1—P1—C13	−80.4 (3)	Cl4—Rh2—P5—C52	−8.4 (2)
Cl1—Rh1—P2—C21	166.5 (2)	Cl4—Rh2—P5—C53	−125.53 (19)
Cl1—Rh1—P2—C22	−71.8 (2)	Cl4—Rh2—P6—C61	72.9 (2)
Cl1—Rh1—P2—C23	45.5 (2)	Cl4—Rh2—P6—C62	−42.6 (2)
Cl1—Rh1—P3—C31	130.6 (2)	Cl4—Rh2—P6—C63	−165.5 (2)
Cl1—Rh1—P3—C32	14.5 (3)	Cl5—Rh2—P4—C41	−38.0 (2)
Cl1—Rh1—P3—C33	−107.1 (2)	Cl5—Rh2—P4—C42	−159.7 (2)
Cl2—Rh1—P1—C11	129.9 (2)	Cl5—Rh2—P4—C43	79.1 (3)
Cl2—Rh1—P1—C12	−108.0 (3)	Cl5—Rh2—P6—C61	−14.1 (2)
Cl2—Rh1—P1—C13	13.1 (2)	Cl5—Rh2—P6—C62	−129.6 (2)
Cl2—Rh1—P3—C31	43.7 (2)	Cl5—Rh2—P6—C63	107.5 (2)
Cl2—Rh1—P3—C32	−72.3 (3)	Cl6—Rh2—P4—C41	−122.7 (2)
Cl2—Rh1—P3—C33	166.0 (2)	Cl6—Rh2—P4—C42	115.6 (2)
Cl3—Rh1—P1—C11	41.5 (2)	Cl6—Rh2—P4—C43	−5.6 (3)
Cl3—Rh1—P1—C12	163.7 (3)	Cl6—Rh2—P5—C51	−161.7 (2)
Cl3—Rh1—P1—C13	−75.3 (2)	Cl6—Rh2—P5—C52	77.9 (2)
Cl3—Rh1—P2—C21	−107.9 (2)	Cl6—Rh2—P5—C53	−39.2 (2)
Cl3—Rh1—P2—C22	13.9 (2)	P4—Rh2—P5—C51	−67.3 (2)
Cl3—Rh1—P2—C23	131.1 (2)	P4—Rh2—P5—C52	172.3 (2)
P1—Rh1—P2—C21	−24.0 (2)	P4—Rh2—P5—C53	55.2 (2)
P1—Rh1—P2—C22	97.7 (2)	P4—Rh2—P6—C61	−99.5 (2)
P1—Rh1—P2—C23	−145.0 (2)	P4—Rh2—P6—C62	145.0 (2)
P1—Rh1—P3—C31	−48.7 (2)	P4—Rh2—P6—C63	22.1 (2)
P1—Rh1—P3—C32	−164.8 (3)	P5—Rh2—P4—C41	151.7 (2)
P1—Rh1—P3—C33	73.5 (2)	P5—Rh2—P4—C42	30.0 (2)
P2—Rh1—P1—C11	−50.5 (2)	P5—Rh2—P4—C43	−91.3 (3)
P2—Rh1—P1—C12	71.7 (3)	P5—Rh2—P6—C61	164.96 (19)
P2—Rh1—P1—C13	−167.3 (2)	P5—Rh2—P6—C62	49.5 (2)
P2—Rh1—P3—C31	−145.7 (2)	P5—Rh2—P6—C63	−73.4 (2)
P2—Rh1—P3—C32	98.3 (3)	P6—Rh2—P4—C41	55.3 (2)
P2—Rh1—P3—C33	−23.4 (2)	P6—Rh2—P4—C42	−66.4 (2)
P3—Rh1—P1—C11	−147.2 (2)	P6—Rh2—P4—C43	172.4 (3)
P3—Rh1—P1—C12	−25.0 (3)	P6—Rh2—P5—C51	27.6 (2)
P3—Rh1—P1—C13	96.0 (2)	P6—Rh2—P5—C52	−92.7 (2)
P3—Rh1—P2—C21	73.1 (2)	P6—Rh2—P5—C53	150.16 (19)
P3—Rh1—P2—C22	−165.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···Cl6i	0.82	2.47	3.184 (5)	147

Symmetry code: (i) −x+1/2, y+1/2, −z+1/2.