catena-Poly[[[tetrakis([mu]-acetato-[kappa]²O:O')dirhodium(II)]-[mu]-[1,3-bis(dimethylamino)propan-2-ol-[kappa]²N:N']] tetrahydrofuran hemisolvate]

In the structure of the title compound, {[Rh₂(C₂H₃O₂)₄(C₇H₁₈N₂O)]·0.5C₄H₈O}_n or {[Rh₂(O₂CMe)₄(Hbdmap)]·0.5C₄H₈O}_n, where Hbdmap is 1,3-bis­(dimethyl­amino)propan-2-ol, each Hbdmap ligand is coordinated to two [Rh₂(O₂CMe)₄] units by two N atoms, resulting in a polymeric chain structure. The observed coordination mode of the Hbdmap mol­ecule is unprecedented.

S1. Comment

A vast amount of interest has been devoted to the dirhodium(II) carboxylates since 1960 with respect to their structure, reactivity and electronic properties. X-ray diffraction studies have revealed dimeric `lantern' or `paddlewheel' structures, which also possess a metal–metal bond. The interest in dirhodium(II) carboxylates has been maintained in recent years especially by their potential practical applications as antitumor agents and as catalysts in organic synthesis. The ability of dirhodium(II) carboxylates to form [Rh₂(O₂CR)₄L_n] (n = 1 or 2) complexes with the ligands (L) in axial positions is well established (Boyar & Robinson, 1983; Cotton et al., 1999). The largest class of such compounds are diadducts with discrete structure. Additionally, polymeric structures comprising axial ligands with two binding sites are also known (Cotton et al., 1999, and references therein; Kim et al., 2001). It is known that dirhodium(II) carboxylates interact with DNA, this possibly being the reason for their cytotoxic effect. Moreover, it is proposed that they can interact, through vacant axial positions, with adenine (at N7) but not with N9-substituted guanine and N1-substituted cytosine, this selectivity being due to intramolecular interligand interactions associated with the octahedral coordination environment about the Rh atom (Aoki & Yamazaki, 1984; Aoki & Salam, 2001, 2002). It is also reported that they can react, through equatorial positions, with guanine as well as adenine by displacing carboxylate ligands (Chifotides & Dunbar, 2005).

1,3-Bis(dimethylamino)-2-propanol (Hbdmap) has two amino groups and one hydroxyl group which can be deprotonated readily. Several complexes with deprotonated bdmap⁻ or zwitterionic Hbdmap (see first scheme below) as a ligand for metal ions have been isolated and structurally characterized. By far the highest in number of complexes with this ligand are copper(II) complexes (Wang et al., 1992, 1993; Wang, 1996; El Fallah et al., 2004) but the complexes with Zr (Fleeting et al., 1999), B (Huskens et al., 1998), Ga (Sun et al., 1999), Si (Lo et al., 2004), Bi (Breeze et al., 1996), Y (Guillon et al., 2000), Zn (Demsar et al., 2002) and Li (Henderson et al., 1995) are also known. Additionally, several heterometallic complexes that contain two different metal ions in the structure are also known. The reason for extensive work in the field is also possible interesting magnetic properties of the products or isolation of precursors for preparation of superconductors (Wang, 1998; Wang et al., 1994, 1995). However, no structure was found where the Hbdmap molecule is bonded as a ligand to a dimetal carboxylate core.

The molecular structure of (I) (Figs. 1 and 2) consists of a zigzag chain of dirhodium(II,II)–tetraacetate bridged by the Hbdmap molecule as a ligand. The chains run along the b axis with van der Waals interactions between the chains. The disordered tetrahydrofuran (THF) molecules occupy the vacancies in the structure. It is interesting to note that in the reaction of dicopper(II) acetate with Hbdmap a tetranuclear complex, [Cu₄(OAc)₆(bdmap)₂(H₂O)₆]_n, was isolated (Wang et al., 1992). Obviously, after coordination of anionic bdmap⁻ in this reaction, the dicopper–dicarboxylate core was converted to a polynuclear structure, where bdmap⁻ acts as a tridentate ligand. In our reaction between dirhodium(II,II) acetate and Hbdmap, the isolated product is structurally completely different. The basic dirhodium dicarboxylate core remains intact, with an Rh···Rh distance of 2.4085 (5) Å, but Hbdmap is coordinated only in axial positions, through its terminal N atoms, to form a polymeric structure. A unique role of the Hbdmap hydroxy group was observed in this structure – it is not involved in coordination but it participates in intramolecular O—H···O hydrogen bonding involving the O atom from the Hbdmap ligand and an O atom from the dirhodium–dicarboxylate core (Table 2 and Fig. 1). The coordination of the Hbdmap molecule in the title compound represents, to the best of our knowledge, a new coordination mode of this ligand.

S2. Experimental

The reaction was carried out under nitrogen atmosphere by using standard Schlenk line techniques. In a Schlenk flask, Rh₂(O₂CCH₃)₄ (52.4 mg) was suspended in THF (4.0 ml) and Hbdmap (17.0 mg) was added. The green suspension was stirred for 24 h. The resulting pink solution was filtered to remove traces of undissolved Rh₂(O₂CCH₃)₄. Pink crystals formed during slow evaporation of the solvent in vacuo.

S3. Refinement

All H atoms were positioned geometrically, fixing the C—H bond lengths at 0.98, 0.99 and 1.00 Å for CH₃, CH₂ and CH groups, respectively and constrained to ride on their parent atom with U_iso(H) = 1.2U_eq(C) [or 1.5U_eq(C) for methyl]. The H atom attached to the O atom was constrained to ride on their parent atom with O—H = 0.84 Å and U_iso(H) = 1.5U_eq(O). The solvent THF molecule is disordered at two sets of positions, which are related by a center of symmetry. The occupancy factor for each of O10, C20, C30 and C50 from the THF solvent molecule was set to 0.5 in the refinement.

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the title compound, showing the atom-numbering scheme. Non-hydroxy H atoms and solvent THF molecules have been omitted for clarity. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the intramolecular hydrogen bond. [Symmetry codes: (i) −x + 1, y + 1/2, −z + 3/2; (ii) −x + 1, y − 1/2, −z + 3/2.]
	Fig. 2. The disordered THF molecules and polymeric chains in the structure of (I), viewed along the a axis.

catena-Poly-[tetrakis(µ-acetato-O,O')- µ-1,3-bis(dimethylamino)-2-propanol-N,N'-dirhodium(II) tetrahydrofuran hemisolvate]

Crystal data

[Rh2(C2H3O2)4(C7H18N2O)]·C4H8O	F(000) = 1264
Mr = 624.28	Dx = 1.706 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5556 reflections
a = 8.4443 (2) Å	θ = 2.6–27.5°
b = 18.0873 (4) Å	µ = 1.41 mm^−1
c = 15.9154 (3) Å	T = 150 K
β = 90.3330 (9)°	Block, pink
V = 2430.79 (9) Å^3	0.10 × 0.05 × 0.05 mm
Z = 4

Data collection

Nonius KappaCCD area-detector diffractometer	5542 independent reflections
Radiation source: fine-focus sealed tube	4012 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.037
Detector resolution: 0.055 pixels mm^-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −10→10
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −23→23
Tmin = 0.872, Tmax = 0.933	l = −20→20
10601 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.078	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0172P)^2 + 4.6899P] where P = (Fo^2 + 2Fc^2)/3
5542 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.70 e Å^−3
4 restraints	Δρmin = −0.56 e Å^−3

Special details

Experimental. 203 frames in 5 sets of ω scans at fixed χ = 55°. Rotation/frame = 1.7 °. Crystal-detector distance = 35 mm. Measuring time = 420 s/°.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Rh1	0.28446 (3)	0.375565 (18)	0.826721 (17)	0.02483 (9)
Rh2	0.30434 (3)	0.245496 (18)	0.796142 (17)	0.02492 (9)
N1	0.2494 (4)	0.50027 (19)	0.85537 (18)	0.0293 (7)
N2	0.6730 (4)	0.62051 (18)	0.72995 (19)	0.0296 (7)
O1	0.5075 (3)	0.36781 (15)	0.87917 (15)	0.0300 (6)
O2	0.5235 (3)	0.24621 (16)	0.85069 (16)	0.0311 (6)
O3	0.3800 (3)	0.39636 (16)	0.71136 (15)	0.0303 (6)
O4	0.4013 (3)	0.27488 (16)	0.68345 (15)	0.0295 (6)
O5	0.0651 (3)	0.37459 (16)	0.77431 (16)	0.0326 (6)
O6	0.0817 (3)	0.25249 (16)	0.74585 (15)	0.0306 (6)
O7	0.1886 (3)	0.34630 (16)	0.93859 (15)	0.0322 (6)
O8	0.2052 (3)	0.22439 (16)	0.90993 (15)	0.0304 (6)
O9	0.6747 (4)	0.50686 (19)	0.8801 (2)	0.0501 (8)
H9	0.6640	0.4616	0.8906	0.075*
C1	0.5771 (5)	0.3056 (2)	0.8814 (2)	0.0297 (9)
C2	0.4164 (4)	0.3423 (3)	0.6649 (2)	0.0308 (9)
C3	0.0113 (4)	0.3139 (3)	0.7460 (2)	0.0307 (9)
C4	0.1682 (4)	0.2788 (2)	0.9567 (2)	0.0280 (9)
C5	0.7361 (5)	0.3020 (3)	0.9251 (3)	0.0430 (11)
H5A	0.7208	0.3033	0.9861	0.065*
H5B	0.8009	0.3442	0.9079	0.065*
H5C	0.7898	0.2559	0.9097	0.065*
C6	0.4848 (5)	0.3593 (3)	0.5792 (2)	0.0371 (10)
H6A	0.6000	0.3529	0.5810	0.056*
H6B	0.4594	0.4104	0.5638	0.056*
H6C	0.4391	0.3255	0.5375	0.056*
C7	−0.1545 (5)	0.3169 (3)	0.7082 (3)	0.0445 (12)
H7A	−0.1479	0.3305	0.6487	0.067*
H7B	−0.2175	0.3539	0.7381	0.067*
H7C	−0.2049	0.2683	0.7134	0.067*
C8	0.0971 (5)	0.2613 (2)	1.0399 (2)	0.0337 (10)
H8A	0.0360	0.2154	1.0357	0.051*
H8B	0.0271	0.3018	1.0570	0.051*
H8C	0.1816	0.2552	1.0819	0.051*
C9	0.1167 (5)	0.5069 (3)	0.9147 (3)	0.0444 (11)
H9A	0.1440	0.4816	0.9673	0.067*
H9B	0.0218	0.4841	0.8902	0.067*
H9C	0.0960	0.5592	0.9261	0.067*
C10	0.2062 (5)	0.5398 (3)	0.7775 (2)	0.0380 (10)
H10A	0.1114	0.5172	0.7527	0.057*
H10B	0.2939	0.5367	0.7376	0.057*
H10C	0.1847	0.5918	0.7905	0.057*
C11	0.3933 (5)	0.5335 (2)	0.8937 (3)	0.0377 (10)
H11A	0.4200	0.5061	0.9457	0.045*
H11B	0.3697	0.5852	0.9097	0.045*
C12	0.5381 (5)	0.5330 (2)	0.8355 (3)	0.0369 (10)
H12	0.5165	0.4999	0.7864	0.044*
C13	0.5733 (5)	0.6109 (2)	0.8041 (3)	0.0381 (10)
H13A	0.4706	0.6353	0.7923	0.046*
H13B	0.6238	0.6384	0.8509	0.046*
C14	0.6023 (6)	0.5855 (3)	0.6543 (3)	0.0485 (12)
H14A	0.5984	0.5318	0.6622	0.073*
H14B	0.6670	0.5972	0.6051	0.073*
H14C	0.4947	0.6045	0.6457	0.073*
C15	0.8329 (6)	0.5896 (3)	0.7415 (3)	0.0526 (13)
H15A	0.8778	0.6072	0.7947	0.079*
H15B	0.9005	0.6054	0.6950	0.079*
H15C	0.8268	0.5355	0.7424	0.079*
O10	−0.1093 (10)	0.4286 (6)	0.5369 (5)	0.083 (3)	0.50
C20	0.049 (3)	0.4515 (15)	0.550 (2)	0.094 (8)	0.50
H20A	0.1230	0.4163	0.5238	0.113*	0.50
H20B	0.0726	0.4538	0.6113	0.113*	0.50
C30	0.064 (2)	0.5262 (10)	0.5116 (10)	0.091 (5)	0.50
H30A	0.1707	0.5328	0.4867	0.109*	0.50
H30B	0.0470	0.5656	0.5539	0.109*	0.50
C40	−0.062 (3)	0.5279 (14)	0.4447 (16)	0.083 (8)	0.50
H40A	−0.1317	0.5717	0.4516	0.099*	0.50
H40B	−0.0151	0.5292	0.3880	0.099*	0.50
C50	−0.1532 (18)	0.4582 (9)	0.4577 (7)	0.081 (4)	0.50
H50A	−0.2683	0.4685	0.4563	0.097*	0.50
H50B	−0.1286	0.4224	0.4126	0.097*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.02437 (15)	0.03204 (18)	0.01808 (14)	0.00239 (13)	0.00026 (11)	−0.00009 (13)
Rh2	0.02366 (15)	0.03252 (19)	0.01858 (15)	−0.00020 (13)	0.00001 (11)	−0.00178 (13)
N1	0.0297 (17)	0.035 (2)	0.0231 (15)	0.0034 (15)	0.0036 (13)	0.0004 (15)
N2	0.0319 (18)	0.032 (2)	0.0245 (16)	0.0014 (15)	0.0021 (13)	0.0034 (14)
O1	0.0289 (14)	0.0339 (17)	0.0272 (13)	−0.0009 (13)	−0.0041 (11)	0.0010 (12)
O2	0.0275 (14)	0.0332 (17)	0.0325 (14)	0.0033 (13)	−0.0031 (11)	−0.0006 (13)
O3	0.0345 (15)	0.0363 (17)	0.0201 (13)	0.0023 (12)	0.0045 (11)	0.0032 (12)
O4	0.0327 (15)	0.0348 (17)	0.0211 (13)	−0.0001 (12)	0.0034 (11)	−0.0043 (12)
O5	0.0260 (14)	0.0418 (18)	0.0299 (14)	0.0054 (13)	−0.0004 (11)	0.0004 (13)
O6	0.0248 (14)	0.0423 (18)	0.0246 (13)	−0.0039 (13)	−0.0023 (11)	−0.0034 (13)
O7	0.0385 (16)	0.0386 (18)	0.0194 (13)	0.0039 (13)	0.0038 (11)	−0.0004 (12)
O8	0.0361 (16)	0.0342 (17)	0.0208 (13)	−0.0004 (12)	0.0020 (11)	0.0004 (12)
O9	0.0487 (19)	0.049 (2)	0.0521 (19)	−0.0019 (16)	−0.0110 (15)	0.0146 (17)
C1	0.026 (2)	0.037 (3)	0.026 (2)	−0.0003 (18)	−0.0021 (16)	0.0008 (18)
C2	0.025 (2)	0.043 (3)	0.0246 (19)	−0.0004 (18)	−0.0012 (16)	0.0020 (19)
C3	0.022 (2)	0.052 (3)	0.0183 (19)	0.0009 (19)	0.0023 (15)	0.0031 (18)
C4	0.026 (2)	0.036 (3)	0.0226 (19)	0.0002 (17)	−0.0021 (16)	0.0048 (17)
C5	0.034 (2)	0.049 (3)	0.046 (3)	0.002 (2)	−0.014 (2)	0.000 (2)
C6	0.040 (2)	0.048 (3)	0.0236 (19)	0.000 (2)	0.0041 (17)	0.0015 (19)
C7	0.026 (2)	0.072 (4)	0.035 (2)	0.002 (2)	−0.0040 (18)	0.000 (2)
C8	0.042 (2)	0.038 (3)	0.0211 (19)	0.001 (2)	0.0051 (17)	0.0023 (17)
C9	0.047 (3)	0.043 (3)	0.043 (2)	0.009 (2)	0.016 (2)	0.001 (2)
C10	0.041 (2)	0.038 (3)	0.034 (2)	0.006 (2)	0.0046 (19)	0.0042 (19)
C11	0.045 (3)	0.034 (3)	0.034 (2)	−0.002 (2)	−0.0029 (19)	−0.0028 (19)
C12	0.038 (2)	0.039 (3)	0.034 (2)	0.001 (2)	−0.0004 (18)	0.0026 (19)
C13	0.045 (3)	0.037 (3)	0.032 (2)	0.001 (2)	0.0026 (19)	0.0014 (19)
C14	0.073 (3)	0.039 (3)	0.033 (2)	−0.007 (2)	0.000 (2)	−0.001 (2)
C15	0.046 (3)	0.043 (3)	0.069 (3)	0.011 (2)	0.006 (3)	0.009 (3)
O10	0.074 (6)	0.119 (8)	0.057 (5)	−0.001 (5)	−0.002 (4)	0.040 (5)
C20	0.107 (19)	0.052 (12)	0.123 (19)	−0.014 (10)	−0.022 (14)	0.004 (11)
C30	0.108 (15)	0.094 (14)	0.070 (11)	−0.014 (10)	−0.006 (10)	−0.017 (10)
C40	0.108 (17)	0.088 (19)	0.051 (10)	0.001 (11)	−0.018 (10)	0.035 (12)
C50	0.080 (10)	0.117 (13)	0.045 (7)	−0.014 (9)	−0.010 (6)	0.016 (8)

Geometric parameters (Å, º)

Rh1—O1	2.060 (3)	C7—H7A	0.9800
Rh1—O3	2.045 (2)	C7—H7B	0.9800
Rh1—O5	2.028 (3)	C7—H7C	0.9800
Rh1—O7	2.030 (3)	C8—H8A	0.9800
Rh1—N1	2.321 (3)	C8—H8B	0.9800
Rh1—Rh2	2.4085 (5)	C8—H8C	0.9800
Rh2—O2	2.040 (3)	C9—H9A	0.9800
Rh2—O4	2.046 (2)	C9—H9B	0.9800
Rh2—O6	2.043 (3)	C9—H9C	0.9800
Rh2—O8	2.036 (2)	C10—H10A	0.9800
Rh2—N2^i	2.307 (3)	C10—H10B	0.9800
N1—C9	1.475 (5)	C10—H10C	0.9800
N1—C10	1.475 (5)	C11—C12	1.538 (6)
N1—C11	1.483 (5)	C11—H11A	0.9900
N2—C13	1.464 (5)	C11—H11B	0.9900
N2—C14	1.482 (5)	C12—C13	1.526 (6)
N2—C15	1.472 (5)	C12—H12	1.0000
N2—Rh2^ii	2.307 (3)	C13—H13A	0.9900
O1—C1	1.269 (5)	C13—H13B	0.9900
O2—C1	1.263 (5)	C14—H14A	0.9800
O3—C2	1.265 (5)	C14—H14B	0.9800
O4—C2	1.261 (5)	C14—H14C	0.9800
O5—C3	1.270 (5)	C15—H15A	0.9800
O6—C3	1.260 (5)	C15—H15B	0.9800
O7—C4	1.266 (5)	C15—H15C	0.9800
O8—C4	1.275 (5)	O10—C20	1.412 (19)
O9—C12	1.431 (5)	O10—C50	1.417 (12)
O9—H9	0.8400	C20—C30	1.493 (18)
C1—C5	1.510 (5)	C20—H20A	0.9900
C2—C6	1.515 (5)	C20—H20B	0.9900
C3—C7	1.521 (5)	C30—C40	1.51 (3)
C4—C8	1.491 (5)	C30—H30A	0.9900
C5—H5A	0.9800	C30—H30B	0.9900
C5—H5B	0.9800	C40—C50	1.491 (17)
C5—H5C	0.9800	C40—H40A	0.9900
C6—H6A	0.9800	C40—H40B	0.9900
C6—H6B	0.9800	C50—H50A	0.9900
C6—H6C	0.9800	C50—H50B	0.9900
O5—Rh1—O7	89.46 (11)	H7A—C7—H7B	109.5
O5—Rh1—O3	89.81 (10)	C3—C7—H7C	109.5
O7—Rh1—O3	175.43 (12)	H7A—C7—H7C	109.5
O5—Rh1—O1	175.58 (12)	H7B—C7—H7C	109.5
O7—Rh1—O1	89.71 (10)	C4—C8—H8A	109.5
O3—Rh1—O1	90.67 (10)	C4—C8—H8B	109.5
O5—Rh1—N1	88.40 (11)	H8A—C8—H8B	109.5
O7—Rh1—N1	91.67 (11)	C4—C8—H8C	109.5
O3—Rh1—N1	92.82 (11)	H8A—C8—H8C	109.5
O1—Rh1—N1	95.96 (11)	H8B—C8—H8C	109.5
O5—Rh1—Rh2	88.45 (8)	N1—C9—H9A	109.5
O7—Rh1—Rh2	87.20 (8)	N1—C9—H9B	109.5
O3—Rh1—Rh2	88.27 (8)	H9A—C9—H9B	109.5
O1—Rh1—Rh2	87.18 (8)	N1—C9—H9C	109.5
N1—Rh1—Rh2	176.66 (8)	H9A—C9—H9C	109.5
O8—Rh2—O2	89.96 (10)	H9B—C9—H9C	109.5
O8—Rh2—O6	88.74 (10)	N1—C10—H10A	109.5
O2—Rh2—O6	175.57 (11)	N1—C10—H10B	109.5
O8—Rh2—O4	175.75 (11)	H10A—C10—H10B	109.5
O2—Rh2—O4	90.26 (10)	N1—C10—H10C	109.5
O6—Rh2—O4	90.72 (10)	H10A—C10—H10C	109.5
O8—Rh2—N2^i	90.65 (11)	H10B—C10—H10C	109.5
O2—Rh2—N2^i	90.38 (11)	N1—C11—C12	113.7 (3)
O6—Rh2—N2^i	93.87 (11)	N1—C11—H11A	108.8
O4—Rh2—N2^i	93.59 (11)	C12—C11—H11A	108.8
O8—Rh2—Rh1	88.51 (8)	N1—C11—H11B	108.8
O2—Rh2—Rh1	88.39 (8)	C12—C11—H11B	108.8
O6—Rh2—Rh1	87.34 (8)	H11A—C11—H11B	107.7
O4—Rh2—Rh1	87.26 (8)	O9—C12—C13	108.0 (4)
N2^i—Rh2—Rh1	178.51 (8)	O9—C12—C11	110.2 (3)
C10—N1—C9	108.3 (3)	C13—C12—C11	110.4 (4)
C10—N1—C11	110.3 (3)	O9—C12—H12	109.4
C9—N1—C11	109.1 (3)	C13—C12—H12	109.4
C10—N1—Rh1	109.7 (2)	C11—C12—H12	109.4
C9—N1—Rh1	107.6 (3)	N2—C13—C12	119.2 (4)
C11—N1—Rh1	111.7 (2)	N2—C13—H13A	107.5
C13—N2—C15	112.7 (3)	C12—C13—H13A	107.5
C13—N2—C14	111.9 (3)	N2—C13—H13B	107.5
C15—N2—C14	107.7 (4)	C12—C13—H13B	107.5
C13—N2—Rh2^ii	108.1 (2)	H13A—C13—H13B	107.0
C15—N2—Rh2^ii	108.5 (3)	N2—C14—H14A	109.5
C14—N2—Rh2^ii	107.8 (2)	N2—C14—H14B	109.5
C1—O1—Rh1	119.6 (2)	H14A—C14—H14B	109.5
C1—O2—Rh2	119.5 (2)	N2—C14—H14C	109.5
C2—O3—Rh1	118.8 (3)	H14A—C14—H14C	109.5
C2—O4—Rh2	119.9 (2)	H14B—C14—H14C	109.5
C3—O5—Rh1	118.5 (3)	N2—C15—H15A	109.5
C3—O6—Rh2	119.2 (3)	N2—C15—H15B	109.5
C4—O7—Rh1	120.5 (2)	H15A—C15—H15B	109.5
C4—O8—Rh2	118.6 (3)	N2—C15—H15C	109.5
C12—O9—H9	109.5	H15A—C15—H15C	109.5
O2—C1—O1	125.3 (3)	H15B—C15—H15C	109.5
O2—C1—C5	117.2 (4)	C20—O10—C50	105.4 (16)
O1—C1—C5	117.5 (4)	O10—C20—C30	106.8 (19)
O4—C2—O3	125.8 (3)	O10—C20—H20A	110.4
O4—C2—C6	116.5 (4)	C30—C20—H20A	110.4
O3—C2—C6	117.6 (4)	O10—C20—H20B	110.4
O6—C3—O5	126.5 (4)	C30—C20—H20B	110.4
O6—C3—C7	117.7 (4)	H20A—C20—H20B	108.6
O5—C3—C7	115.8 (4)	C20—C30—C40	104.2 (17)
O7—C4—O8	125.2 (3)	C20—C30—H30A	110.9
O7—C4—C8	117.6 (4)	C40—C30—H30A	110.9
O8—C4—C8	117.1 (4)	C20—C30—H30B	110.9
C1—C5—H5A	109.5	C40—C30—H30B	110.9
C1—C5—H5B	109.5	H30A—C30—H30B	108.9
H5A—C5—H5B	109.5	C50—C40—C30	104.4 (14)
C1—C5—H5C	109.5	C50—C40—H40A	110.9
H5A—C5—H5C	109.5	C30—C40—H40A	110.9
H5B—C5—H5C	109.5	C50—C40—H40B	110.9
C2—C6—H6A	109.5	C30—C40—H40B	110.9
C2—C6—H6B	109.5	H40A—C40—H40B	108.9
H6A—C6—H6B	109.5	O10—C50—C40	108.2 (14)
C2—C6—H6C	109.5	O10—C50—H50A	110.1
H6A—C6—H6C	109.5	C40—C50—H50A	110.1
H6B—C6—H6C	109.5	O10—C50—H50B	110.1
C3—C7—H7A	109.5	C40—C50—H50B	110.1
C3—C7—H7B	109.5	H50A—C50—H50B	108.4
O5—Rh1—Rh2—O8	−89.10 (10)	N1—Rh1—O5—C3	−178.2 (3)
O7—Rh1—Rh2—O8	0.44 (11)	Rh2—Rh1—O5—C3	0.7 (3)
O3—Rh1—Rh2—O8	−178.96 (10)	O8—Rh2—O6—C3	88.6 (3)
O1—Rh1—Rh2—O8	90.29 (10)	O4—Rh2—O6—C3	−87.2 (3)
O5—Rh1—Rh2—O2	−179.10 (10)	N2^i—Rh2—O6—C3	179.1 (3)
O7—Rh1—Rh2—O2	−89.56 (10)	Rh1—Rh2—O6—C3	0.0 (3)
O3—Rh1—Rh2—O2	91.04 (10)	O5—Rh1—O7—C4	87.7 (3)
O1—Rh1—Rh2—O2	0.29 (10)	O1—Rh1—O7—C4	−88.0 (3)
O5—Rh1—Rh2—O6	−0.29 (10)	N1—Rh1—O7—C4	176.0 (3)
O7—Rh1—Rh2—O6	89.25 (10)	Rh2—Rh1—O7—C4	−0.8 (3)
O3—Rh1—Rh2—O6	−90.15 (10)	O2—Rh2—O8—C4	88.2 (3)
O1—Rh1—Rh2—O6	179.10 (10)	O6—Rh2—O8—C4	−87.6 (3)
O5—Rh1—Rh2—O4	90.56 (10)	N2^i—Rh2—O8—C4	178.5 (3)
O7—Rh1—Rh2—O4	−179.90 (10)	Rh1—Rh2—O8—C4	−0.2 (3)
O3—Rh1—Rh2—O4	0.70 (10)	Rh2—O2—C1—O1	−2.5 (5)
O1—Rh1—Rh2—O4	−90.05 (10)	Rh2—O2—C1—C5	176.8 (3)
O5—Rh1—N1—C10	−54.0 (2)	Rh1—O1—C1—O2	2.9 (5)
O7—Rh1—N1—C10	−143.4 (2)	Rh1—O1—C1—C5	−176.4 (3)
O3—Rh1—N1—C10	35.7 (2)	Rh2—O4—C2—O3	1.9 (5)
O1—Rh1—N1—C10	126.7 (2)	Rh2—O4—C2—C6	−178.2 (2)
O5—Rh1—N1—C9	63.6 (3)	Rh1—O3—C2—O4	−1.0 (5)
O7—Rh1—N1—C9	−25.8 (3)	Rh1—O3—C2—C6	179.1 (3)
O3—Rh1—N1—C9	153.3 (3)	Rh2—O6—C3—O5	0.5 (5)
O1—Rh1—N1—C9	−115.7 (3)	Rh2—O6—C3—C7	−179.9 (2)
O5—Rh1—N1—C11	−176.6 (2)	Rh1—O5—C3—O6	−0.9 (5)
O7—Rh1—N1—C11	93.9 (2)	Rh1—O5—C3—C7	179.5 (2)
O3—Rh1—N1—C11	−86.9 (2)	Rh1—O7—C4—O8	0.9 (5)
O1—Rh1—N1—C11	4.1 (2)	Rh1—O7—C4—C8	−180.0 (2)
O7—Rh1—O1—C1	85.6 (3)	Rh2—O8—C4—O7	−0.4 (5)
O3—Rh1—O1—C1	−89.8 (3)	Rh2—O8—C4—C8	−179.5 (2)
N1—Rh1—O1—C1	177.3 (3)	C10—N1—C11—C12	−58.5 (4)
Rh2—Rh1—O1—C1	−1.6 (3)	C9—N1—C11—C12	−177.3 (4)
O8—Rh2—O2—C1	−87.6 (3)	Rh1—N1—C11—C12	63.8 (4)
O4—Rh2—O2—C1	88.1 (3)	N1—C11—C12—O9	−133.1 (4)
N2^i—Rh2—O2—C1	−178.3 (3)	N1—C11—C12—C13	107.6 (4)
Rh1—Rh2—O2—C1	0.9 (3)	C15—N2—C13—C12	−60.2 (5)
O5—Rh1—O3—C2	−88.6 (3)	C14—N2—C13—C12	61.3 (5)
O1—Rh1—O3—C2	87.0 (3)	Rh2^ii—N2—C13—C12	179.8 (3)
N1—Rh1—O3—C2	−177.0 (3)	O9—C12—C13—N2	77.6 (5)
Rh2—Rh1—O3—C2	−0.2 (3)	C11—C12—C13—N2	−161.8 (4)
O2—Rh2—O4—C2	−89.9 (3)	C50—O10—C20—C30	34 (3)
O6—Rh2—O4—C2	85.8 (3)	O10—C20—C30—C40	−25 (4)
N2^i—Rh2—O4—C2	179.7 (3)	C20—C30—C40—C50	7 (4)
Rh1—Rh2—O4—C2	−1.5 (3)	C20—O10—C50—C40	−29.7 (16)
O7—Rh1—O5—C3	−86.6 (3)	C30—C40—C50—O10	13 (2)
O3—Rh1—O5—C3	88.9 (3)

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···O1	0.84	2.16	2.884 (4)	145