Chlorido(dimethyl 2,2′-bi­pyridine-4,4′-di­carboxyl­ate-κ²N,N′)(η⁵-penta­methyl­cyclo­penta­dien­yl)rhodium(III) chloride 1-hy­droxy­pyrrolidine-2,5-dione disolvate

The title complex, [Rh(C₁₀H₁₅)Cl(C₁₄H₁₂N₂O₄)]Cl·2C₄H₅NO₃, has been synthesized by a substitution reaction of the precursor [bis­(2,5-dioxopyrrolidin-1-yl) 2,2′-bi­pyridine-4,4′-di­­carboxyl­ate]chlorido(penta­methyl­cyclo­penta­dien­yl)rhodium(III) chloride with NaOCH₃. The Rh^III cation is located in an RhC₅N₂Cl eight-coordinated environment. In the crystal, 1-hy­droxy­pyrrolidine-2,5-dione (NHS) solvent mol­ecules form strong hydrogen bonds with the Cl⁻ counter-anions in the lattice and weak hydrogen bonds with the penta­methyl­cyclo­penta­dienyl (Cp*) ligands. Hydrogen bonding between the Cp* ligands, the NHS solvent mol­ecules and the Cl⁻ counter-anions form links in a V-shaped chain of Rh^III com­plex cations along the c axis. Weak hydrogen bonds between the dimethyl 2,2′-bi­pyridine-4,4′-di­carboxyl­ate lig­ands and the Cl⁻ counter-anions connect the components into a supra­molecular three-dimensional net­work. The synthetic route to the dimethyl 2,2′-bi­pyridine-4,4′-di­carboxyl­ate-containing rhodium complex from the [bis­(2,5-dioxopyrroli­din-1-yl) 2,2′-bi­pyridine-4,4′-di­carboxyl­ate]rho­dium(III) pre­cursor may be applied to link Rh catalysts to the surface of electrodes.

S1. Comment

The regioselective reduction of nicotinamide adenine dinucleotide (NAD⁺) to NADH, catalyzed by highly water-soluble rhodium complexes, has been studied extensively (Ruppert et al., 1988; Steckhan et al., 1991). Using rhodium complexes, regeneration of NADH was achieved by electrochemical, chemical and indirect electrochemical methods (Chenault et al., 1987; Adlercreutz, 1996). The key redox chemicals were [Cp*(bpy)Rh^III(H₂O)]²⁺ and [Cp*(bpy)Rh^IIIH]⁺ species, where Cp* and bpy are pentamethylcyclopentadienyl and 2,2'-bipyridine, respectively. Currently, the complexes [Cp*Rh^III(bpy)(H₂O)](PF₆)₂ and [Cp*Rh^III(6,6'-Me₂bpy)(H₂O)](CF₃SO₃)₂, where 6,6'-Me₂bpy is 6,6'-dimethyl-2,2'-bipyridine, were characterized fully by X-ray crystallography (Ogo et al., 2005). These water-bound Rh^III complexes originate from the corresponding chloride-coordinated rhodium species, where the chloride ions can easily dissociate from the metal centre to form complexes with Lewis bases such as H₂O. Interestingly, although a chloride-coordinated rhodium complex with arylazoimidazole and Cp* has been reported (Govindaswamy et al., 2007), reports of chloride-coordinated rhodium complexes with Cp* and bipyridine ligands are rare.

The regeneration of NADH using Rh^III complexes has often been utilized in the biotransformation of organic substrates by various enzymes. Recently, it was also reported that spatial separation between enzymes and Rh metal complex mediators should be implemented to ensure long-term stability of the electro-enzymatic transformation (Hildebrand & Lütz, 2009). Unfortunately, not much effort was made to covalently immobilize the mediators to generate reagent-free bioelectrocatalytic devices, partially because of the absence of available precursor mediators with linker units and relevant chemistry (Poizat et al., 2010).

1-Hydroxypyrrolidine-2,5-dione (NHS) is commonly used to activate the acid group in organic chemistry (Cheng et al., 2007; Jones et al., 2003). Once the NHS-tethered rhodium(III) complexes are available and the concept of linking rhodium(III) catalysts on the electrode using the NHS-tethered rhodium precursor is proved, biotransformation of organic substrates utilizing the regeneration of NADH by Rh^III complexes may be widely used.

We report here the crystal structure of [Rh^IIICp*Cl(bpyCOOMe)]Cl.2NHS, (I) (see Scheme), where bpyCOOMe is dimethyl 2,2'-bipyridine-4,4'-dicarboxylate, showing the various intermolecular hydrogen-bonding interactions between the NHS solvent molecules, then Cl^- counter-anions and the bpyCOOMe ligands in the crystal lattice. (I) was synthesized by treating two equivalents of NaOMe with [bis(2,5-dioxopyrrolidin-1-yl) 2,2'-bipyridine-4,4'-dicarboxylate]chlorido(η⁵-pentamethylcyclopentadienyl)rhodium(III) chloride, (II) (see Scheme).

Complex (I) contains NHS solvent molecules and [Rh^IIICp*Cl(bpyCOOMe)]Cl (Fig. 1). The Rh^III atom is coordinated by Cp*, bpyCOOMe and Cl ligands, with another Cl^- anion present in the lattice to balance the charge. The Rh—C(Cp*) bond lengths of the nearly flat Cp* ligand are in the range 2.136 (5)–2.175 (5) Å. The Rh—Cl distance in (I) is 2.3823 (14) Å and this relatively long distance indicates that the Cl atom can easily dissociate from the metal ion. The dihedral angle between the plande of the pyridine rings in the bpyCOOMe ligand is 179.0 (4)°, which shows the near planarity of the bipyridine system. The Rh—N distances are shorter than in a previously reported complex, which indicates that the acidity of the rhodium centre of (I) is greater than that in the reported complex (Ogo et al., 2005). The N—Rh—N angle involving the bipyridine N atoms is 76.9 (15)°, which is comparable to previously reported values of 77.1 (2) and 75.6 (1)° (Ogo et al., 2005).

The hydrogen-bonding interactions between the methyl groups of the Cp* ligand and the carbonyl (C═O) and hydroxy (OH) groups of the NHS solvent molecules are depicted in Fig. 2. The NHS donor atoms are O4S and O6S and the Cp*–carbonyl and Cp*–hydroxy C—H···O hydrogen-bond distances (Table 1 and Fig. 2) indicate a weak interaction.

The NHS solvent molecules present in the crystal lattice form O—H···Cl interactions with the Cl^- counter-anion. Considering that the reported distance of the van der Waals radii for H and neutral Cl atoms is 2.95 Å (Aullon et al., 1998), the hydrogen-bonding interaction is very strong. The two methylene groups of NHS are also engaged in weak C—H···O interactions with carbonyl atoms O5S and O1S, forming R₂²(8) and R₂²(9) rings. The hydrogen-bonding interactions between the NHS solvent molecules the Cl^- counter-anion form a chain along the c axis due to c-glide symmetry (Fig. 3). Previously, NHS and its derivatives were reported to form weak hydrogen-bond interactions, e.g. O—H···O, N—H···O and C—H···O (Stefanowicz et al., 2007).

The weak C20—H20···Cl2ⁱ and C22—H22C···Cl1ⁱⁱ hydrogen bonds (Table 2) between the bpyCOOMe ligand and the Cl^- counter-anion connect the components into a supramolecular three-dimensional network along the b axis. Of these two interactions, that involcing the aromatic ring (C20—H20···Cl2ⁱ) is an intermediate contact (Balamurugan et al., 2004; Rinta et al., 2012) and the other is a weak C—H···Cl contact. Additionally, intermolecular C—H···π interactions of bpyCOOMe with a methyl group of Cp* and with a pyridine C—H group stabilize the crystal packing in (I). The hydrogen bonding between the Cp* ligands, NHS solvent molecules and Cl^- counter-anions forms the links in a V-shaped chain of Rh complexes along the c axis. The two sides of the chain are constructed by [Rh^IIICp*Cl(bpyCOOMe)]⁺; the solvent molecules and counter-anions extend the chain along the c axis through C—H···O, O—H···Cl and C—H···O(carbonyl) hydrogen bonds (Fig. 4).

To ensure the long-term stability of the electro-enzymatic transformation and reagent-free bioelectrocatalytic devices in the regeneration of NADH, Rh^III complexes or mediators should be separated from the enzymes. The isolation of (I) from the [bis(2,5-dioxopyrrolidin-1-yl) 2,2'-bipyridine-4,4'-dicarboxylate]rhodium(III) precursor by treatment with NaOCH₃, indicates that a similar synthetic route can be utilized to link the Rh catalyst on the surface of electrodes with NaO(CH₂)_nR units (Walcarius et al., 2011).

Related literature

For related literature, see: Adlercreutz (1996); Aullon et al. (1998); Balamurugan et al. (2004); Chenault & Whitesides (1987); Cheng et al. (2007); Govindaswamy et al. (2007); Hildebrand & Lütz (2009); Jones (2003); Ogo et al. (2005); Poizat et al. (2010); Rinta et al. (2012); Ruppert et al. (1988); Steckhan et al. (1991); Stefanowicz et al. (2007); Walcarius et al. (2011).

S2. Experimental

For the preparation of [bis(2,5-dioxopyrrolidin-1-yl) 2,2'-bipyridine-4,4'-dicarboxylate]chlorido(η⁵-pentamethylcyclopentadienyl)rhodium(III) chloride, (II), {Cp*Rh(µ-Cl)Cl}₂ (0.028 g, 0.045 mmol) was added to a solution of bis(2,5-dioxopyrrolidin-1-yl)-2,2'-bipyridine-4,4'-dicarboxylic acid (0.040 g, 0.091 mmol) in methanol (5 ml) under an N₂ atmosphere. The colour of the reaction mixture slowly turned to yellow–orange from red–brown. After 3 h of additional stirring at room temperature, the volume was reduced to 2 ml and upon addition of diethyl ether (10 ml) a yellow–orange precipitate of (II) was obtained (yield: 0.055 g, 82%). ¹H NMR: (CD₃OD): δ 9.22 (d, 2H), 9.10 (s, 2H), 8.32 (d, 2H), 2.95 (s, 8H), 1.71 (s, 15H).

For the synthesis of the title compound, (I), NaOMe (14.0 mg, 0.268 mmol) was added to a solution of (II) (0.100 g, 0.134 mmol) in MeOH (5 ml) and the resulting mixture stirred for 2 h under an N₂ atmosphere. The volume of the resulting orange–yellow solution was reduced to 2 ml and precipitated with diethyl ether; crystals were collected from a methanol and diethyl ether diffusion system (yield: 0.082 g, 76%). ¹H NMR (CD₃OD): δ 9.20 (d, 2H), 9.08 (s, 2H), 8.36 (d, 2H), 4.09 (s, 6H), 2.64 (s, 8H), 1.77 (s, 15H). MS–ESI: m/z 545.10 [Cp*(bpyCOOMe)RhCl]⁺.

S3. Refinement

The hydroxy H atoms were located in a difference electron-density map and were refined using O—H distance restraints of 0.84 (2) Å [Uiso(H) = 1.5Ueq(O)]. Distance restraints were also applied to the N···H distances to harmonize the two N—O—H angles (applied s.u. = 0.02 Å). All other H atoms were introduced at their calculated positions and were then refined as riding, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic, and C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. Two reflections affected by the beam stop and with (I_o-I_c)/ΣW > 10 were excluded from the refinement.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (I) with H atoms omitted, showing the atom-numbering scheme and displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The molecular structure of (I) showing the hydrogen-bond interactions (dashed lines). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 3. The interactions between the NHS solvent molecules and the Cl^- anion in (I), viewed along the c axis (c-glide symmetry), shown without [Cp^*(bpyCOOMe)Rh^IIICl]. [Symmetry codes: (i) x, -y+1/2, z-1/2; (ii) x, -y+1/2, z+1/2; (iii) x, y, z+1.]
	Fig. 4. A partial view of the crystal packing diagram of (I), showing the V-shaped chain along the c axis.

Chlorido(dimethyl 2,2'-bipyridine-4,4'-dicarboxylate-κ²N,N')(η⁵-pentamethylcyclopentadienyl)rhodium(III) chloride 1-hydroxypyrrolidine-2,5-dione disolvate

Crystal data

[Rh(C10H15)Cl(C14H12N2O4)]Cl·2C4H5NO3	F(000) = 1664
Mr = 811.47	Dx = 1.557 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3791 reflections
a = 8.6511 (7) Å	θ = 2.4–23.9°
b = 33.613 (3) Å	µ = 0.71 mm^−1
c = 11.9147 (9) Å	T = 200 K
β = 92.723 (2)°	Block, yellow
V = 3460.8 (5) Å^3	0.19 × 0.15 × 0.09 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	6273 independent reflections
Radiation source: fine-focus sealed tube	3649 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.096
ϕ and ω scans	θmax = 25.3°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→9
Tmin = 0.77, Tmax = 1.00	k = −35→40
20576 measured reflections	l = −14→14

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.089	H atoms treated by a mixture of independent and constrained refinement
S = 0.85	w = 1/[σ^2(Fo^2) + (0.0114P)^2] where P = (Fo^2 + 2Fc^2)/3
6273 reflections	(Δ/σ)max = 0.001
457 parameters	Δρmax = 0.71 e Å^−3
4 restraints	Δρmin = −0.60 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
Rh1	0.78349 (5)	0.106934 (13)	0.86490 (3)	0.03094 (13)
Cl1	0.65184 (15)	0.04482 (4)	0.87279 (11)	0.0403 (4)
C1	0.8345 (6)	0.16191 (16)	0.7846 (5)	0.0387 (14)
C2	0.7246 (6)	0.13983 (16)	0.7138 (4)	0.0346 (14)
C3	0.5889 (6)	0.13536 (16)	0.7747 (5)	0.0421 (15)
C4	0.6148 (6)	0.15318 (17)	0.8824 (4)	0.0410 (15)
C5	0.7669 (6)	0.17015 (16)	0.8858 (4)	0.0408 (15)
C6	0.9905 (6)	0.17563 (18)	0.7510 (5)	0.065 (2)
H6A	0.9802	0.2013	0.7122	0.098*
H6B	1.0341	0.1560	0.7007	0.098*
H6C	1.0593	0.1786	0.8182	0.098*
C7	0.7411 (7)	0.12702 (18)	0.5939 (4)	0.0598 (19)
H7A	0.7050	0.0995	0.5846	0.090*
H7B	0.8501	0.1287	0.5754	0.090*
H7C	0.6790	0.1445	0.5438	0.090*
C8	0.4440 (6)	0.11496 (18)	0.7324 (5)	0.068 (2)
H8A	0.3751	0.1343	0.6943	0.101*
H8B	0.3920	0.1032	0.7958	0.101*
H8C	0.4699	0.0940	0.6795	0.101*
C9	0.4956 (6)	0.15783 (19)	0.9695 (5)	0.070 (2)
H9A	0.4288	0.1343	0.9688	0.105*
H9B	0.4326	0.1815	0.9524	0.105*
H9C	0.5476	0.1608	1.0439	0.105*
C10	0.8395 (7)	0.19398 (17)	0.9791 (5)	0.0610 (19)
H10A	0.9474	0.1856	0.9925	0.092*
H10B	0.7828	0.1898	1.0474	0.092*
H10C	0.8363	0.2222	0.9590	0.092*
N1	0.9787 (4)	0.07340 (12)	0.8253 (3)	0.0322 (11)
N2	0.8838 (4)	0.09196 (12)	1.0242 (3)	0.0299 (10)
C11	1.0219 (6)	0.06564 (16)	0.7213 (4)	0.0375 (14)
H11	0.9670	0.0781	0.6600	0.045*
C12	1.1414 (6)	0.04056 (16)	0.6988 (4)	0.0383 (14)
H12	1.1698	0.0364	0.6236	0.046*
C13	1.2202 (5)	0.02143 (15)	0.7866 (4)	0.0297 (13)
C14	1.1786 (5)	0.02899 (15)	0.8956 (4)	0.0281 (12)
H14	1.2316	0.0162	0.9573	0.034*
C15	1.0587 (5)	0.05538 (15)	0.9137 (4)	0.0283 (12)
C16	1.0030 (5)	0.06593 (15)	1.0247 (4)	0.0253 (12)
C17	1.0669 (5)	0.05041 (15)	1.1242 (4)	0.0297 (13)
H17	1.1486	0.0316	1.1224	0.036*
C18	1.0120 (5)	0.06233 (15)	1.2262 (4)	0.0278 (12)
C19	0.8927 (5)	0.08931 (15)	1.2246 (4)	0.0323 (13)
H19	0.8524	0.0982	1.2929	0.039*
C20	0.8315 (5)	0.10344 (15)	1.1226 (4)	0.0308 (12)
H20	0.7489	0.1221	1.1228	0.037*
C21	1.3446 (6)	−0.00814 (17)	0.7605 (5)	0.0360 (14)
O1	1.3874 (4)	−0.01352 (13)	0.6688 (3)	0.0542 (12)
O2	1.3914 (4)	−0.02777 (10)	0.8519 (3)	0.0364 (9)
C22	1.5114 (6)	−0.05696 (17)	0.8359 (5)	0.0504 (16)
H22A	1.4693	−0.0789	0.7897	0.076*
H22B	1.5492	−0.0673	0.9091	0.076*
H22C	1.5971	−0.0445	0.7981	0.076*
C23	1.0749 (6)	0.04641 (16)	1.3366 (4)	0.0316 (13)
O3	1.0268 (4)	0.05493 (11)	1.4253 (3)	0.0440 (10)
O4	1.1866 (4)	0.02016 (11)	1.3192 (3)	0.0381 (9)
C24	1.2627 (6)	0.00215 (17)	1.4178 (4)	0.0511 (17)
H24A	1.3196	0.0226	1.4613	0.077*
H24B	1.3349	−0.0184	1.3943	0.077*
H24C	1.1849	−0.0099	1.4643	0.077*
N3S	0.1944 (5)	0.35082 (15)	0.8207 (4)	0.0456 (13)
C29	0.1335 (6)	0.33124 (19)	0.7271 (5)	0.0477 (17)
C30	0.0106 (6)	0.30341 (18)	0.7693 (5)	0.0505 (17)
H30A	0.0324	0.2756	0.7482	0.061*
H30B	−0.0932	0.3109	0.7375	0.061*
C31	0.0189 (6)	0.30825 (18)	0.8965 (5)	0.0517 (17)
H31A	−0.0836	0.3158	0.9235	0.062*
H31B	0.0522	0.2831	0.9334	0.062*
C32	0.1343 (6)	0.34034 (19)	0.9220 (5)	0.0462 (16)
O2S	0.3018 (5)	0.38108 (13)	0.8126 (4)	0.0628 (13)
O3S	0.1762 (5)	0.35474 (13)	1.0108 (3)	0.0636 (13)
O1S	0.1724 (4)	0.33561 (15)	0.6320 (3)	0.0763 (15)
O6S	0.6317 (5)	0.25143 (14)	0.8206 (4)	0.0542 (11)
O5S	0.3085 (4)	0.24794 (13)	0.8166 (3)	0.0623 (13)
N4S	0.5362 (5)	0.24186 (13)	0.7278 (4)	0.0408 (12)
C28	0.3778 (7)	0.24062 (18)	0.7347 (5)	0.0467 (16)
O4S	0.7295 (5)	0.22848 (12)	0.6100 (4)	0.0660 (13)
C25	0.5955 (7)	0.22991 (17)	0.6276 (5)	0.0451 (16)
C27	0.3160 (6)	0.22997 (18)	0.6198 (4)	0.0518 (17)
H27A	0.2590	0.2527	0.5849	0.062*
H27B	0.2449	0.2070	0.6228	0.062*
C26	0.4568 (7)	0.21946 (19)	0.5524 (4)	0.0576 (18)
H26A	0.4570	0.1908	0.5336	0.069*
H26B	0.4565	0.2350	0.4818	0.069*
Cl2	0.60900 (15)	0.33924 (4)	0.80009 (12)	0.0464 (4)
H2S	0.381 (4)	0.3683 (14)	0.794 (7)	0.16 (4)*
H6S	0.629 (7)	0.2769 (5)	0.816 (5)	0.09 (3)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.0344 (2)	0.0325 (3)	0.0258 (2)	0.0026 (2)	−0.00025 (17)	0.0021 (2)
Cl1	0.0466 (9)	0.0358 (9)	0.0380 (8)	−0.0042 (7)	−0.0034 (7)	0.0010 (7)
C1	0.038 (3)	0.032 (4)	0.046 (4)	0.000 (3)	0.003 (3)	0.005 (3)
C2	0.042 (3)	0.033 (4)	0.028 (3)	0.006 (3)	0.001 (3)	0.008 (3)
C3	0.040 (4)	0.036 (4)	0.049 (4)	−0.001 (3)	−0.011 (3)	0.018 (3)
C4	0.045 (4)	0.048 (4)	0.031 (3)	0.023 (3)	0.002 (3)	0.009 (3)
C5	0.055 (4)	0.031 (4)	0.036 (4)	0.007 (3)	−0.007 (3)	0.003 (3)
C6	0.054 (4)	0.056 (5)	0.087 (5)	−0.005 (3)	0.008 (4)	0.021 (4)
C7	0.086 (5)	0.057 (5)	0.036 (4)	0.011 (4)	−0.002 (3)	0.000 (3)
C8	0.049 (4)	0.070 (5)	0.080 (5)	−0.014 (4)	−0.032 (3)	0.032 (4)
C9	0.069 (5)	0.078 (6)	0.065 (5)	0.039 (4)	0.022 (4)	0.021 (4)
C10	0.085 (5)	0.043 (4)	0.052 (4)	0.013 (4)	−0.022 (4)	−0.009 (3)
N1	0.038 (3)	0.035 (3)	0.024 (2)	−0.003 (2)	−0.002 (2)	0.001 (2)
N2	0.035 (3)	0.030 (3)	0.024 (2)	0.003 (2)	0.000 (2)	−0.001 (2)
C11	0.041 (3)	0.050 (4)	0.020 (3)	0.003 (3)	−0.002 (3)	0.003 (3)
C12	0.044 (4)	0.046 (4)	0.025 (3)	0.006 (3)	0.003 (3)	−0.003 (3)
C13	0.031 (3)	0.032 (3)	0.026 (3)	0.001 (2)	0.004 (2)	−0.001 (3)
C14	0.029 (3)	0.032 (3)	0.023 (3)	0.001 (2)	−0.002 (2)	0.005 (2)
C15	0.026 (3)	0.035 (4)	0.024 (3)	−0.007 (2)	−0.001 (2)	0.001 (3)
C16	0.031 (3)	0.027 (3)	0.018 (3)	−0.001 (2)	0.000 (2)	−0.001 (2)
C17	0.031 (3)	0.035 (4)	0.024 (3)	0.001 (2)	0.003 (2)	0.000 (3)
C18	0.028 (3)	0.030 (3)	0.025 (3)	−0.007 (2)	−0.005 (2)	−0.001 (2)
C19	0.037 (3)	0.038 (4)	0.023 (3)	−0.001 (3)	0.007 (2)	−0.006 (3)
C20	0.032 (3)	0.031 (3)	0.030 (3)	0.000 (3)	0.005 (2)	0.002 (3)
C21	0.031 (3)	0.047 (4)	0.030 (3)	−0.004 (3)	0.001 (3)	−0.002 (3)
O1	0.050 (3)	0.087 (4)	0.026 (2)	0.020 (2)	0.0094 (19)	−0.006 (2)
O2	0.038 (2)	0.036 (2)	0.036 (2)	0.0096 (18)	0.0063 (17)	−0.0004 (19)
C22	0.045 (4)	0.048 (4)	0.058 (4)	0.010 (3)	0.005 (3)	0.003 (3)
C23	0.031 (3)	0.034 (4)	0.030 (3)	−0.001 (3)	0.003 (3)	−0.003 (3)
O3	0.049 (2)	0.062 (3)	0.022 (2)	0.010 (2)	0.0039 (18)	0.001 (2)
O4	0.043 (2)	0.046 (3)	0.025 (2)	0.0123 (19)	−0.0002 (17)	0.0041 (18)
C24	0.044 (4)	0.076 (5)	0.033 (3)	0.019 (3)	0.000 (3)	0.005 (3)
N3S	0.030 (3)	0.050 (4)	0.057 (3)	−0.001 (2)	0.003 (3)	0.002 (3)
C29	0.031 (4)	0.068 (5)	0.044 (4)	0.015 (3)	0.002 (3)	0.003 (4)
C30	0.041 (4)	0.057 (5)	0.053 (4)	−0.003 (3)	−0.003 (3)	−0.007 (3)
C31	0.044 (4)	0.062 (5)	0.049 (4)	−0.010 (3)	−0.001 (3)	0.010 (3)
C32	0.040 (4)	0.056 (5)	0.043 (4)	0.009 (3)	0.001 (3)	0.012 (4)
O2S	0.046 (3)	0.052 (3)	0.090 (4)	−0.003 (2)	0.008 (3)	0.013 (3)
O3S	0.068 (3)	0.073 (4)	0.048 (3)	−0.007 (2)	−0.012 (2)	−0.002 (3)
O1S	0.063 (3)	0.121 (5)	0.046 (3)	−0.002 (3)	0.016 (2)	0.001 (3)
O6S	0.054 (3)	0.048 (3)	0.059 (3)	0.006 (2)	−0.018 (2)	−0.002 (3)
O5S	0.050 (3)	0.090 (4)	0.047 (3)	−0.002 (2)	0.008 (2)	−0.012 (3)
N4S	0.040 (3)	0.043 (3)	0.038 (3)	0.004 (2)	−0.006 (2)	−0.001 (2)
C28	0.046 (4)	0.056 (5)	0.037 (4)	0.003 (3)	−0.005 (3)	−0.004 (3)
O4S	0.054 (3)	0.058 (3)	0.088 (4)	0.008 (2)	0.028 (3)	0.017 (3)
C25	0.050 (4)	0.034 (4)	0.053 (4)	0.000 (3)	0.014 (4)	0.016 (3)
C27	0.053 (4)	0.067 (5)	0.035 (4)	0.003 (3)	−0.003 (3)	−0.005 (3)
C26	0.074 (5)	0.067 (5)	0.032 (4)	0.021 (4)	0.000 (3)	0.000 (3)
Cl2	0.0411 (9)	0.0464 (10)	0.0519 (9)	−0.0014 (7)	0.0046 (7)	0.0091 (8)

Geometric parameters (Å, º)

Rh1—N1	2.102 (4)	C16—C17	1.386 (6)
Rh1—N2	2.110 (4)	C17—C18	1.385 (6)
Rh1—C1	2.136 (5)	C17—H17	0.9500
Rh1—C5	2.145 (5)	C18—C19	1.373 (6)
Rh1—C4	2.149 (5)	C18—C23	1.498 (6)
Rh1—C2	2.153 (5)	C19—C20	1.386 (6)
Rh1—C3	2.175 (5)	C19—H19	0.9500
Rh1—Cl1	2.3823 (14)	C20—H20	0.9500
C1—C5	1.393 (7)	C21—O1	1.184 (5)
C1—C2	1.446 (7)	C21—O2	1.321 (6)
C1—C6	1.499 (7)	O2—C22	1.448 (5)
C2—C3	1.417 (7)	C22—H22A	0.9800
C2—C7	1.505 (7)	C22—H22B	0.9800
C3—C4	1.425 (7)	C22—H22C	0.9800
C3—C8	1.495 (7)	C23—O3	1.190 (5)
C4—C5	1.433 (7)	C23—O4	1.332 (6)
C4—C9	1.505 (7)	O4—C24	1.451 (5)
C5—C10	1.485 (7)	C24—H24A	0.9800
C6—H6A	0.9800	C24—H24B	0.9800
C6—H6B	0.9800	C24—H24C	0.9800
C6—H6C	0.9800	N3S—C29	1.378 (7)
C7—H7A	0.9800	N3S—C32	1.382 (7)
C7—H7B	0.9800	N3S—O2S	1.384 (6)
C7—H7C	0.9800	C29—O1S	1.206 (6)
C8—H8A	0.9800	C29—C30	1.520 (7)
C8—H8B	0.9800	C30—C31	1.523 (7)
C8—H8C	0.9800	C30—H30A	0.9900
C9—H9A	0.9800	C30—H30B	0.9900
C9—H9B	0.9800	C31—C32	1.491 (7)
C9—H9C	0.9800	C31—H31A	0.9900
C10—H10A	0.9800	C31—H31B	0.9900
C10—H10B	0.9800	C32—O3S	1.204 (6)
C10—H10C	0.9800	O2S—H2S	0.851 (16)
N1—C11	1.337 (6)	O6S—N4S	1.386 (5)
N1—C15	1.373 (5)	O6S—H6S	0.859 (16)
N2—C20	1.334 (5)	O5S—C28	1.195 (6)
N2—C16	1.353 (5)	N4S—C28	1.378 (6)
C11—C12	1.371 (6)	N4S—C25	1.381 (7)
C11—H11	0.9500	C28—C27	1.490 (7)
C12—C13	1.380 (6)	O4S—C25	1.189 (6)
C12—H12	0.9500	C25—C26	1.505 (7)
C13—C14	1.387 (6)	C27—C26	1.532 (7)
C13—C21	1.508 (7)	C27—H27A	0.9900
C14—C15	1.390 (6)	C27—H27B	0.9900
C14—H14	0.9500	C26—H26A	0.9900
C15—C16	1.472 (6)	C26—H26B	0.9900
N1—Rh1—N2	76.91 (15)	N1—C11—C12	123.2 (5)
N1—Rh1—C1	100.26 (18)	N1—C11—H11	118.4
N2—Rh1—C1	121.61 (18)	C12—C11—H11	118.4
N1—Rh1—C5	128.03 (19)	C11—C12—C13	119.2 (5)
N2—Rh1—C5	99.14 (18)	C11—C12—H12	120.4
C1—Rh1—C5	37.96 (19)	C13—C12—H12	120.4
N1—Rh1—C4	165.01 (19)	C12—C13—C14	119.0 (5)
N2—Rh1—C4	109.71 (18)	C12—C13—C21	118.8 (5)
C1—Rh1—C4	64.8 (2)	C14—C13—C21	122.2 (5)
C5—Rh1—C4	38.99 (19)	C13—C14—C15	119.4 (4)
N1—Rh1—C2	104.38 (18)	C13—C14—H14	120.3
N2—Rh1—C2	160.99 (18)	C15—C14—H14	120.3
C1—Rh1—C2	39.40 (18)	N1—C15—C14	121.1 (4)
C5—Rh1—C2	64.8 (2)	N1—C15—C16	114.1 (4)
C4—Rh1—C2	64.85 (19)	C14—C15—C16	124.8 (4)
N1—Rh1—C3	137.37 (19)	N2—C16—C17	121.4 (4)
N2—Rh1—C3	145.58 (19)	N2—C16—C15	115.7 (4)
C1—Rh1—C3	64.55 (19)	C17—C16—C15	122.9 (4)
C5—Rh1—C3	64.4 (2)	C18—C17—C16	120.2 (5)
C4—Rh1—C3	38.47 (19)	C18—C17—H17	119.9
C2—Rh1—C3	38.22 (18)	C16—C17—H17	119.9
N1—Rh1—Cl1	85.96 (12)	C19—C18—C17	117.9 (5)
N2—Rh1—Cl1	86.12 (11)	C19—C18—C23	119.3 (5)
C1—Rh1—Cl1	152.25 (15)	C17—C18—C23	122.8 (5)
C5—Rh1—Cl1	145.98 (16)	C18—C19—C20	119.6 (5)
C4—Rh1—Cl1	107.57 (17)	C18—C19—H19	120.2
C2—Rh1—Cl1	112.86 (15)	C20—C19—H19	120.2
C3—Rh1—Cl1	92.53 (15)	N2—C20—C19	122.7 (5)
C5—C1—C2	108.4 (5)	N2—C20—H20	118.7
C5—C1—C6	126.2 (5)	C19—C20—H20	118.7
C2—C1—C6	125.3 (5)	O1—C21—O2	126.0 (5)
C5—C1—Rh1	71.4 (3)	O1—C21—C13	123.3 (5)
C2—C1—Rh1	70.9 (3)	O2—C21—C13	110.6 (4)
C6—C1—Rh1	126.4 (4)	C21—O2—C22	115.1 (4)
C3—C2—C1	107.1 (5)	O2—C22—H22A	109.5
C3—C2—C7	125.0 (5)	O2—C22—H22B	109.5
C1—C2—C7	127.7 (5)	H22A—C22—H22B	109.5
C3—C2—Rh1	71.7 (3)	O2—C22—H22C	109.5
C1—C2—Rh1	69.7 (3)	H22A—C22—H22C	109.5
C7—C2—Rh1	128.1 (4)	H22B—C22—H22C	109.5
C2—C3—C4	108.5 (5)	O3—C23—O4	125.8 (5)
C2—C3—C8	125.3 (5)	O3—C23—C18	124.5 (5)
C4—C3—C8	126.1 (5)	O4—C23—C18	109.6 (4)
C2—C3—Rh1	70.1 (3)	C23—O4—C24	117.1 (4)
C4—C3—Rh1	69.8 (3)	O4—C24—H24A	109.5
C8—C3—Rh1	125.6 (4)	O4—C24—H24B	109.5
C3—C4—C5	107.3 (5)	H24A—C24—H24B	109.5
C3—C4—C9	125.5 (5)	O4—C24—H24C	109.5
C5—C4—C9	126.7 (5)	H24A—C24—H24C	109.5
C3—C4—Rh1	71.7 (3)	H24B—C24—H24C	109.5
C5—C4—Rh1	70.4 (3)	C29—N3S—C32	116.1 (5)
C9—C4—Rh1	129.3 (4)	C29—N3S—O2S	121.8 (5)
C1—C5—C4	108.6 (5)	C32—N3S—O2S	122.0 (5)
C1—C5—C10	125.1 (5)	O1S—C29—N3S	126.1 (6)
C4—C5—C10	126.2 (5)	O1S—C29—C30	128.1 (6)
C1—C5—Rh1	70.7 (3)	N3S—C29—C30	105.8 (5)
C4—C5—Rh1	70.7 (3)	C29—C30—C31	105.2 (5)
C10—C5—Rh1	126.4 (4)	C29—C30—H30A	110.7
C1—C6—H6A	109.5	C31—C30—H30A	110.7
C1—C6—H6B	109.5	C29—C30—H30B	110.7
H6A—C6—H6B	109.5	C31—C30—H30B	110.7
C1—C6—H6C	109.5	H30A—C30—H30B	108.8
H6A—C6—H6C	109.5	C32—C31—C30	106.2 (5)
H6B—C6—H6C	109.5	C32—C31—H31A	110.5
C2—C7—H7A	109.5	C30—C31—H31A	110.5
C2—C7—H7B	109.5	C32—C31—H31B	110.5
H7A—C7—H7B	109.5	C30—C31—H31B	110.5
C2—C7—H7C	109.5	H31A—C31—H31B	108.7
H7A—C7—H7C	109.5	O3S—C32—N3S	123.7 (6)
H7B—C7—H7C	109.5	O3S—C32—C31	129.8 (6)
C3—C8—H8A	109.5	N3S—C32—C31	106.4 (5)
C3—C8—H8B	109.5	N3S—O2S—H2S	102 (4)
H8A—C8—H8B	109.5	N4S—O6S—H6S	100 (3)
C3—C8—H8C	109.5	C28—N4S—C25	117.0 (5)
H8A—C8—H8C	109.5	C28—N4S—O6S	121.1 (5)
H8B—C8—H8C	109.5	C25—N4S—O6S	121.7 (5)
C4—C9—H9A	109.5	O5S—C28—N4S	125.5 (5)
C4—C9—H9B	109.5	O5S—C28—C27	128.9 (6)
H9A—C9—H9B	109.5	N4S—C28—C27	105.5 (5)
C4—C9—H9C	109.5	O4S—C25—N4S	124.7 (6)
H9A—C9—H9C	109.5	O4S—C25—C26	129.9 (6)
H9B—C9—H9C	109.5	N4S—C25—C26	105.3 (5)
C5—C10—H10A	109.5	C28—C27—C26	106.1 (5)
C5—C10—H10B	109.5	C28—C27—H27A	110.5
H10A—C10—H10B	109.5	C26—C27—H27A	110.5
C5—C10—H10C	109.5	C28—C27—H27B	110.5
H10A—C10—H10C	109.5	C26—C27—H27B	110.5
H10B—C10—H10C	109.5	H27A—C27—H27B	108.7
C11—N1—C15	118.2 (4)	C25—C26—C27	105.4 (5)
C11—N1—Rh1	125.1 (3)	C25—C26—H26A	110.7
C15—N1—Rh1	116.5 (3)	C27—C26—H26A	110.7
C20—N2—C16	118.3 (4)	C25—C26—H26B	110.7
C20—N2—Rh1	125.4 (3)	C27—C26—H26B	110.7
C16—N2—Rh1	116.1 (3)	H26A—C26—H26B	108.8
N1—C15—C16—C17	179.0 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C30—H30A···O5S	0.99	2.65	3.209 (7)	116
C10—H10C···O6S	0.98	2.56	3.195 (7)	123
C6—H6A···O4S	0.98	2.60	3.274 (7)	126
C22—H22C···O4^i	0.98	2.52	3.497 (6)	172
O6S—H6S···Cl2	0.86 (2)	2.11 (2)	2.967 (5)	176 (5)
O2S—H2S···Cl2	0.85 (2)	2.20 (3)	3.016 (5)	162 (7)
C22—H22C···Cl1^ii	0.98	3.16	3.650 (6)	113
C20—H20···Cl2^iii	0.95	2.80	3.504 (5)	131

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