Di-μ-methano­lato-bis­[(η⁴-tetra­fluoro­benzobarrelene)rhodium(I)]

The versatile synthetic precursor methano­late-bridged title rhodium complex, [Rh₂(CH₃O)₂(C₁₂H₆F₄)₂] or [Rh(μ-OCH₃)(tfbb)]₂ [tfbb = tetra­fluoro­benzobarrelene or 3,4,5,6-tetra­fluoro­tricyclo­[6.2.2.0^2,7]dodeca-2(7),3,5,9,11-penta­ene], has been structurally characterized. The asymmetric unit contains half a mol­ecule that can be expanded via a twofold axis. The title compound has been shown to be a dinuclear rhodium complex where each metal centre is coordinated by two O atoms from two bridging methano­late groups and by the olefinic bonds of a tfbb ligand. Comparison of the bite angles of tfbb, norbornadiene (nbd) and cyclo­octa­diene (cod) olefins in their η⁴-coordination to rhodium reveals similarities between the tfbb and nbd ligands, which are much more rigid than cod. The short distance found between the distorted square-planar metal centres [2.8351 (4) Å] has been related to the syn conformation of the folded core `RhORhO' ring.

S1. Comment

Facile access to rhodium complexes bearing the tetrafluorobenzobarrelene (tfbb) diolefin has promoted the development of a rich rhodium organometallic chemistry within the last few years (Esteruelas & Oro, 1999). In particular, the basicity of the title complex, [Rh(µ-OMe)(tfbb)]₂ (Usón et al., 1985), has allowed entry into a broad spectrum of neutral or cationic polynuclear complexes. Furthermore, replacing tfbb with the well known diolefin cycloocta-1,5-diene (cod) often has remarkable consequences for the structures and nuclearity of the complexes (Mena et al., 2011).

In the present study, [Rh(µ-OMe)(tfbb)]₂, (I), has been shown to be a dinuclear Rh complex formed by two crystallographically related Rh(tfbb) fragments symmetrically bridged by a pair of µ-methanolate ligands. Rhodium exhibits a slightly distorted square-planar coordination involving two O atoms and the olefinic bonds of the tfbb ligands to which they are bonded in an η²-C═C fashion. The Rh—C bond lengths are in the range 2.084 (2)–2.111 (2) Å. The main indication of the slight deviation from the ideal square-planar arrangement is the fact that the Rh^I centre lies 0.0721 (2) Å out of the least-squares plane formed by the two O atoms and the mid-points of the C1═C2 and C4═C5 olefinic bonds (denoted Ct1 and Ct2, respectively); this displacement of the Rh^I centre is in the opposite direction to that of the symmetry-related Rh^I centre in the dimer. Moreover, a dihedral angle of 86.21 (8)° is found between this coordination plane [formed by O1, O1ⁱ, Ct1 and Ct2; symmetry code: (i) x, -y+1/2, -z+1/2] and the plane defined by olefinic atoms C1, C2, C4 and C5. This value indicates that the tfbb ligand does not coordinate perpendicular to the metal coordination plane, but is hardly twisted towards the inner part of the molecule. [Author: this sentence above does not make sense - please remove or clarify]

The coordination of the tfbb ligands to the metal centre in (I) is similar to that found in the [Rh(µ₂-NH₂)(tfbb)]₃ trimer (Mena et al., 2011), as indicated by the mean Rh—Ct distances of 1.978 (3) and 2.001 (3) Å (Ct being the centroid of a C═C bond) found in the methanolate dimer, (I), and in the amido trimer, respectively. The Ct1—Rh1—Ct2 bite angle in the dimer [71.4 (1)°] is very close to that found in the trimer [mean value = 70.8 (2)°] and remains well within the narrow range observed in the Cambridge Structural Database (CSD, Version 5.32; Allen, 2002) for Rh–tfbb complexes (66.9–73.0°), showing the relative rigidity of this diolefin. Interestingly, an analysis of the coordination of tfbb, norbornadiene (nbd) and cod diolefins with rhodium reveals that the bite angle is similar and it varies in a comparable narrow range in Rh–tfbb and Rh–nbd complexes (bite angles between 65.8 and 73.8° are found in the latter), while for the cod ligand it is larger and much more flexible, as indicated by the higher observed values and by a wider distribution of bite angles, ranging from 75.5 to 91.9°.

The four-membered `RhORhO' ring shows a folded conformation: the dihedral angle (θ) between the coordination planes defined by O—Rh—O<sup>i</sup> and O—Rh<sup>i</sup>—O<sup>i</sup> is 120.79 (5)°. Accordingly, a short intermetallic separation of 2.8350 (4) Å was observed. This value, shorter than that observed in the related [Rh(µ-OMe)(cod)]<sub>2</sub> complex (3.231 Å; Tanaka et al., 1983), is in the lower limit of the range (2.785–3.33 Å) reported for dinuclear rhodium compounds bridged by two O atoms (CSD; Allen, 2002). In fact, an analysis of 13 dinuclear square-planar rhodium(I) complexes of the type `Rh₂(µ-OZ)₂' [Z = ?] having two substituted oxide bridges and nondisordered dinuclear `RhORhO' central cores revealed a clear correlation (Fig. 2) between the intermetallic distance (d) and the four-membered ring folding (θ). Notably, the obtained total distribution is clearly bimodal, with a narrow distribution at θ >172° (zone I) and a broader one with 117 < θ < 137° (zone II).

The first group of structures [zone I] comprises µ-hydroxo [Rh(µ-OH)(L)]₂ (L = substituted phosphine; Okazaki et al., 2009; Brune et al., 1988; Gevert et al., 1996), and alkoxide-bridged [Rh(µ-OMe)(cod)]₂ (Tanaka et al., 1983) and [Rh(µ-diphenylphenoxy)(CO)]₂ (Chebi et al., 1990) complexes. Two molecular structures were found where crystallographically independent atoms formed nearly planar rings with an anti configuration, while in three structures the `RhORhO' ring lies across an inversion centre. In this case, the symmetry constrains the four atoms to be coplanar (θ = 180°) and the complexes also exhibit an anti configuration. Intermetallic distances longer than 3.23 Å, well over the reported attracting interaction distances, are observed within this group.

The second group (zone II) corresponds to geometries formed by crystallographically independent atoms or by atoms related by a twofold rotation axis in [Rh(µ-OH)(cod)]₂ (Selent & Ramm, 1995) or dibenzocyclotetraene (Singh & Sharp, 2008), in [{Rh(µ-OEt)(cod)}₂] (Ramm & Selent, 1996) or [{Rh(µ-OSiZ)(L)}₂] with Z = methyl or phenyl groups and L = cod, norbornadiene or carbonyl ligands (Marciniec et al., 1996; Krzyzanowski et al., 1996; Vizi-Orosz et al., 1994). A linear correlation exists between d and θ (Fig. 2) for all these complexes with syn configurations in the folded rings.

The molecular parameters for (I) lie in zone II, where the shortest intermetallic distances for `Rh₂(µ-OZ)₂' (between 2.78 and 2.95 Å) can be found. It is noteworthy that this classification cannot be easily related to the bridging group or the rhodium ligands: [Rh(µ-OH)(cod)]₂ exhibits a folded ring with a syn configuration (Selent & Ramm, 1995), while [Rh(µ-OMe)(cod)]₂ and [Rh(µ-OH)(triphenylphosphine)]₂ exhibit planar rings with anti configurations (Tanaka et al., 1983; Brune et al., 1988). However, for dinuclear complexes exhibiting syn conformations, bulky siloxo-derivative bridging groups tend to occupy axial positions, while complexes with ethanolate- and hydroxide-bridging ligands exhibit a syn–e conformation, very close to the geometry observed in compound (I).

Concerning the crystal packing of (I), the hydrogen-bonding network [H1···O1ⁱⁱ = 2.57 (3) Å, C1···O1ⁱⁱ = 3.424 (3) Å, C1—H1···Oⁱⁱ = 158 (3)°; symmetry code: (ii) -x+1/2, y-1/2, -z+1/2] displayed in Fig. 3 shows a helical arrangement of molecules.

Furthermore, molecules of neighbouring helices are connected through short contacts between F atoms (CF···FC interactions). F-atom characteristics (high electronegativity, low polarizability and small size) distinguish it from Cl, Br and I, and therefore its ability to form C—H···F, F···F and C—F···π interactions has been argued (Reichenbächer et al., 2005). The intermolecular distance between F atoms in (I) is 2.850 (4) Å and, according to the similar values of the C—F···F angles [150.5 (2) and 151.9 (2)°], this contact corresponds to a type-I halogen–halogen interaction (Sakurai et al., 1963; Desiraju & Parthasarathy, 1989). These values also agree with those reported for other CF···FC type-I interactions with distances between 2.659 and 2.899 Å (Hibbs et al., 2004; Chopra et al., 2006; Hathwar & Guru Row, 2011). These previous experimental and theoretical charge-density analyses show that, according to their topological characteristics (charge density, Laplacian and energy densities), these interactions correspond to weak closed-shell interactions. Therefore, they may contribute, albeit weakly, to the packing stability.

Related literature

For related literature, see: Allen (2002); Brune et al. (1988); Chebi et al. (1990); Chopra et al. (2006); Desiraju & Parthasarathy (1989); Esteruelas & Oro (1999); Gevert et al. (1996); Hathwar & Guru Row (2011); Hibbs et al. (2004); Krzyzanowski et al. (1996); Marciniec et al. (1996); Mena et al. (2011); Okazaki et al. (2009); Ramm & Selent (1996); Reichenbächer et al. (2005); Sakurai et al. (1963); Selent & Ramm (1995); Singh & Sharp (2008); Tanaka et al. (1983); Usón et al. (1985); Vizi-Orosz, Ugo, Psaro, Sironi, Moret, Zucchi, Ghelfi & Palyi (1994).

S2. Experimental

The synthesis of the title complex is well known and quite accessible (Usón et al., 1985).

S3. Refinement

All H atoms (except those of the methyl group) were included in the model in observed positions and freely refined. Final C—H distances vary from 0.87 (3) to 0.95 (3) Å. The H atoms of the methyl group have been included in idealized positions and constrained to ride on their parent atoms, with a C—H distance of 0.98 Å and with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: APEX2 (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures

	Fig. 1. A view of the molecular structure of [Rh(µ-OMe)(tfbb)]2, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) x, -y+1/2, -z+1/2.]
	Fig. 2. A graph showing the relationship between the Rh···Rh intermetallic distance (d) versus central core folding (θ). Planar-anti, folded-syn-a and folded-syn-e core `RhORhO' ring compounds are represented by triangles, circles and squares, respectively. Compound (I) is identified by a star. The dashed line shows the linear fit of folded-syn compounds.
	Fig. 3. The hydrogen-bonding network in (I), viewed along the c axis. Dark dotted lines represent hydrogen-bond interactions along a helix (two helices are represented in blue and red in the electronic version of the paper). Short F···F contacts between the helices are depicted in grey (green) dotted lines.

(I)

Crystal data

[Rh2(CH3O)2(C12H6F4)2]	F(000) = 1408
Mr = 720.22	Dx = 2.131 Mg m^−3
Orthorhombic, Pnna	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2bc	Cell parameters from 1665 reflections
a = 25.7648 (17) Å	θ = 1.6–30.5°
b = 10.8166 (7) Å	µ = 1.56 mm^−1
c = 8.0542 (5) Å	T = 100 K
V = 2244.6 (2) Å^3	Prism, yellow
Z = 4	0.18 × 0.04 × 0.04 mm

Data collection

Bruker APEX DUO system diffractometer	3241 independent reflections
Radiation source: fine-focus sealed tube	2700 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω rotations with narrow frames scans	θmax = 30.5°, θmin = 1.6°
Absorption correction: numerical (absorption corrections based on face indexing, using APEX2; Bruker, 2008)	h = −36→25
Tmin = 0.900, Tmax = 1.000	k = −15→15
18639 measured reflections	l = −11→11

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.069	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ^2(Fo^2) + (0.030P)^2 + 2.9733P] where P = (Fo^2 + 2Fc^2)/3
3241 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.78 e Å^−3
0 restraints	Δρmin = −0.48 e Å^−3
0 constraints

Special details

Geometry. Ct1 and Ct2 are the centroids of the C1=C2 and C4=C5 bonds, respectively.

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

	x	y	z	Uiso*/Ueq
Rh1	0.186170 (7)	0.128786 (16)	0.18310 (2)	0.01614 (7)
C1	0.17620 (9)	−0.0619 (2)	0.2294 (3)	0.0172 (5)
C2	0.13232 (9)	0.0046 (2)	0.2804 (3)	0.0180 (5)
C3	0.09150 (9)	0.0183 (2)	0.1437 (3)	0.0192 (5)
C4	0.12506 (9)	0.0905 (2)	0.0193 (3)	0.0188 (5)
C5	0.16925 (9)	0.0258 (2)	−0.0319 (3)	0.0189 (5)
C6	0.17376 (9)	−0.1031 (2)	0.0466 (3)	0.0173 (5)
C7	0.12316 (9)	−0.1718 (2)	0.0178 (3)	0.0189 (5)
C8	0.11702 (10)	−0.2853 (2)	−0.0563 (3)	0.0215 (5)
C9	0.06843 (11)	−0.3375 (2)	−0.0750 (3)	0.0246 (5)
C10	0.02536 (10)	−0.2756 (3)	−0.0170 (4)	0.0260 (6)
C11	0.03088 (10)	−0.1618 (2)	0.0580 (4)	0.0228 (5)
C12	0.07936 (9)	−0.1079 (2)	0.0737 (3)	0.0192 (5)
F1	0.15846 (6)	−0.34857 (14)	−0.1154 (2)	0.0264 (3)
F2	0.06287 (7)	−0.44752 (16)	−0.1494 (2)	0.0351 (4)
F3	−0.02232 (6)	−0.32576 (17)	−0.0346 (2)	0.0369 (4)
F4	−0.01184 (6)	−0.10354 (15)	0.1168 (2)	0.0297 (4)
O1	0.21743 (6)	0.29470 (16)	0.1036 (2)	0.0203 (4)
C13	0.20877 (12)	0.3451 (3)	−0.0538 (4)	0.0342 (7)
H13A	0.2345	0.3124	−0.1319	0.051*
H13B	0.2119	0.4353	−0.0482	0.051*
H13C	0.1739	0.3228	−0.0917	0.051*
H1	0.1994 (12)	−0.095 (3)	0.301 (4)	0.017 (7)*
H3	0.0644 (12)	0.060 (3)	0.178 (3)	0.019 (7)*
H5	0.1874 (11)	0.048 (3)	−0.123 (4)	0.021 (8)*
H4	0.1122 (10)	0.162 (2)	−0.035 (3)	0.009 (6)*
H6	0.2011 (12)	−0.142 (3)	0.012 (4)	0.018 (7)*
H2	0.1230 (11)	0.020 (3)	0.390 (4)	0.023 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Rh1	0.01252 (9)	0.01531 (10)	0.02061 (10)	−0.00020 (7)	−0.00073 (7)	0.00046 (7)
C1	0.0144 (10)	0.0153 (10)	0.0220 (12)	0.0005 (8)	−0.0024 (9)	0.0021 (9)
C2	0.0155 (10)	0.0166 (11)	0.0219 (12)	−0.0023 (9)	−0.0006 (10)	0.0022 (9)
C3	0.0124 (10)	0.0178 (11)	0.0274 (13)	0.0019 (9)	−0.0009 (9)	0.0005 (10)
C4	0.0166 (11)	0.0172 (11)	0.0225 (12)	−0.0006 (9)	−0.0049 (9)	0.0025 (9)
C5	0.0173 (11)	0.0191 (11)	0.0203 (12)	−0.0033 (9)	−0.0015 (9)	0.0006 (10)
C6	0.0169 (10)	0.0128 (10)	0.0222 (12)	0.0003 (8)	−0.0007 (9)	−0.0002 (9)
C7	0.0179 (11)	0.0173 (11)	0.0215 (12)	−0.0013 (9)	−0.0029 (9)	0.0038 (9)
C8	0.0252 (12)	0.0195 (11)	0.0200 (12)	0.0011 (10)	−0.0029 (10)	0.0033 (10)
C9	0.0317 (14)	0.0180 (11)	0.0242 (13)	−0.0053 (10)	−0.0078 (11)	0.0013 (10)
C10	0.0235 (12)	0.0268 (13)	0.0278 (14)	−0.0101 (11)	−0.0084 (11)	0.0049 (11)
C11	0.0175 (11)	0.0228 (12)	0.0279 (13)	−0.0023 (10)	−0.0038 (10)	0.0063 (11)
C12	0.0160 (10)	0.0183 (11)	0.0235 (12)	−0.0014 (9)	−0.0035 (9)	0.0043 (10)
F1	0.0326 (9)	0.0186 (7)	0.0280 (8)	0.0035 (6)	0.0002 (7)	−0.0027 (6)
F2	0.0444 (10)	0.0237 (8)	0.0372 (10)	−0.0100 (8)	−0.0081 (8)	−0.0055 (7)
F3	0.0256 (8)	0.0356 (9)	0.0495 (11)	−0.0155 (7)	−0.0089 (8)	0.0024 (9)
F4	0.0143 (7)	0.0322 (9)	0.0428 (10)	−0.0020 (6)	−0.0012 (7)	0.0033 (8)
O1	0.0184 (8)	0.0195 (8)	0.0230 (9)	−0.0012 (7)	0.0032 (7)	0.0010 (7)
C13	0.0341 (16)	0.0325 (15)	0.0362 (17)	−0.0007 (12)	0.0008 (13)	0.0010 (13)

Geometric parameters (Å, º)

Rh1—Ct1	1.977 (2)	C5—C6	1.535 (3)
Rh1—Ct2	1.980 (2)	C5—H5	0.90 (3)
Rh1—O1	2.0687 (17)	C6—C7	1.519 (3)
Rh1—O1^i	2.0700 (18)	C6—H6	0.87 (3)
Rh1—C1	2.111 (2)	C7—C8	1.374 (3)
Rh1—C2	2.084 (2)	C7—C12	1.398 (3)
Rh1—C4	2.096 (2)	C8—F1	1.354 (3)
Rh1—C5	2.105 (3)	C8—C9	1.381 (4)
Rh1—Rh1^i	2.8351 (4)	C9—F2	1.340 (3)
C1—C2	1.401 (3)	C9—C10	1.378 (4)
C1—C6	1.540 (4)	C10—F3	1.350 (3)
C1—H1	0.90 (3)	C10—C11	1.379 (4)
C2—C3	1.529 (4)	C11—F4	1.354 (3)
C2—H2	0.93 (3)	C11—C12	1.384 (3)
C3—C12	1.510 (3)	O1—C13	1.398 (4)
C3—C4	1.537 (4)	C13—H13A	0.9800
C3—H3	0.88 (3)	C13—H13B	0.9800
C4—C5	1.399 (3)	C13—H13C	0.9800
C4—H4	0.95 (3)
O1—Rh1—O1^i	76.03 (9)	C5—C4—Rh1	70.90 (14)
O1—Rh1—Ct1	178.16 (9)	C3—C4—Rh1	96.47 (16)
O1—Rh1—Ct2	107.10 (9)	C5—C4—H4	123.9 (16)
O1^i—Rh1—Ct1	105.28 (9)	C3—C4—H4	121.1 (16)
O1^i—Rh1—Ct2	172.35 (9)	Rh1—C4—H4	113.1 (16)
Ct1—Rh1—Ct2	71.4 (1)	C4—C5—C6	113.2 (2)
O1—Rh1—C2	159.19 (8)	C4—C5—Rh1	70.20 (15)
O1^i—Rh1—C2	101.82 (9)	C6—C5—Rh1	97.25 (16)
O1—Rh1—C4	105.61 (8)	C4—C5—H5	122 (2)
O1^i—Rh1—C4	153.36 (9)	C6—C5—H5	122 (2)
C2—Rh1—C4	66.98 (10)	Rh1—C5—H5	115 (2)
O1—Rh1—C5	106.57 (9)	C7—C6—C5	108.48 (19)
O1^i—Rh1—C5	167.17 (8)	C7—C6—C1	108.8 (2)
C2—Rh1—C5	80.23 (10)	C5—C6—C1	97.70 (19)
C4—Rh1—C5	38.90 (10)	C7—C6—H6	114.3 (19)
O1—Rh1—C1	161.69 (8)	C5—C6—H6	112 (2)
O1^i—Rh1—C1	106.94 (9)	C1—C6—H6	115 (2)
C2—Rh1—C1	39.02 (9)	C8—C7—C12	119.2 (2)
C4—Rh1—C1	80.02 (10)	C8—C7—C6	127.1 (2)
C5—Rh1—C1	66.62 (10)	C12—C7—C6	113.7 (2)
O1—Rh1—Rh1^i	46.78 (5)	F1—C8—C7	120.9 (2)
O1^i—Rh1—Rh1^i	46.74 (5)	F1—C8—C9	118.0 (2)
C2—Rh1—Rh1^i	116.96 (7)	C7—C8—C9	121.1 (2)
C4—Rh1—Rh1^i	114.97 (7)	F2—C9—C10	119.8 (2)
C5—Rh1—Rh1^i	143.35 (7)	F2—C9—C8	120.6 (3)
C1—Rh1—Rh1^i	146.75 (7)	C10—C9—C8	119.6 (2)
C2—C1—C6	113.3 (2)	F3—C10—C9	120.1 (2)
C2—C1—Rh1	69.43 (14)	F3—C10—C11	119.9 (3)
C6—C1—Rh1	96.83 (15)	C9—C10—C11	119.9 (2)
C2—C1—H1	123.6 (19)	F4—C11—C10	119.0 (2)
C6—C1—H1	121.3 (19)	F4—C11—C12	120.4 (2)
Rh1—C1—H1	115 (2)	C10—C11—C12	120.6 (3)
C1—C2—C3	113.2 (2)	C11—C12—C7	119.4 (2)
C1—C2—Rh1	71.55 (14)	C11—C12—C3	127.0 (2)
C3—C2—Rh1	97.19 (16)	C7—C12—C3	113.6 (2)
C1—C2—H2	125.5 (19)	Rh1—O1—C13	123.83 (17)
C3—C2—H2	119.2 (18)	C13—O1—Rh1	123.83 (17)
Rh1—C2—H2	114.1 (19)	C13—O1—Rh1^i	122.34 (17)
C12—C3—C2	108.9 (2)	Rh1—O1—Rh1^i	86.47 (7)
C12—C3—C4	109.4 (2)	O1—C13—H13A	109.5
C2—C3—C4	97.55 (19)	O1—C13—H13B	109.5
C12—C3—H3	115 (2)	H13A—C13—H13B	109.5
C2—C3—H3	111.7 (19)	O1—C13—H13C	109.5
C4—C3—H3	113 (2)	H13A—C13—H13C	109.5
C5—C4—C3	113.3 (2)	H13B—C13—H13C	109.5
O1—Rh1—C1—C2	−175.3 (2)	C4—Rh1—C5—C6	−112.1 (2)
O1^i—Rh1—C1—C2	87.95 (15)	C1—Rh1—C5—C6	−8.53 (14)
C4—Rh1—C1—C2	−65.58 (16)	Rh1^i—Rh1—C5—C6	−169.49 (9)
C5—Rh1—C1—C2	−103.87 (17)	C4—C5—C6—C7	52.2 (3)
Rh1^i—Rh1—C1—C2	55.3 (2)	Rh1—C5—C6—C7	123.74 (18)
O1—Rh1—C1—C6	−63.0 (3)	C4—C5—C6—C1	−60.7 (2)
O1^i—Rh1—C1—C6	−159.67 (13)	Rh1—C5—C6—C1	10.87 (17)
C2—Rh1—C1—C6	112.4 (2)	C2—C1—C6—C7	−52.9 (3)
C4—Rh1—C1—C6	46.80 (15)	Rh1—C1—C6—C7	−123.40 (16)
C5—Rh1—C1—C6	8.50 (13)	C2—C1—C6—C5	59.7 (2)
Rh1^i—Rh1—C1—C6	167.69 (9)	Rh1—C1—C6—C5	−10.82 (17)
C6—C1—C2—C3	1.4 (3)	C5—C6—C7—C8	124.9 (3)
Rh1—C1—C2—C3	90.03 (19)	C1—C6—C7—C8	−129.9 (3)
C6—C1—C2—Rh1	−88.66 (18)	C5—C6—C7—C12	−54.5 (3)
O1—Rh1—C2—C1	175.9 (2)	C1—C6—C7—C12	50.8 (3)
O1^i—Rh1—C2—C1	−102.39 (15)	C12—C7—C8—F1	178.5 (2)
C4—Rh1—C2—C1	103.01 (17)	C6—C7—C8—F1	−0.8 (4)
C5—Rh1—C2—C1	64.72 (16)	C12—C7—C8—C9	−0.6 (4)
Rh1^i—Rh1—C2—C1	−149.62 (13)	C6—C7—C8—C9	−179.9 (2)
O1—Rh1—C2—C3	63.8 (3)	F1—C8—C9—F2	0.1 (4)
O1^i—Rh1—C2—C3	145.51 (14)	C7—C8—C9—F2	179.1 (2)
C4—Rh1—C2—C3	−9.09 (15)	F1—C8—C9—C10	−179.8 (2)
C5—Rh1—C2—C3	−47.38 (16)	C7—C8—C9—C10	−0.7 (4)
C1—Rh1—C2—C3	−112.1 (2)	F2—C9—C10—F3	0.2 (4)
Rh1^i—Rh1—C2—C3	98.28 (15)	C8—C9—C10—F3	−180.0 (2)
C1—C2—C3—C12	52.1 (3)	F2—C9—C10—C11	−179.3 (2)
Rh1—C2—C3—C12	125.10 (18)	C8—C9—C10—C11	0.6 (4)
C1—C2—C3—C4	−61.4 (2)	F3—C10—C11—F4	1.7 (4)
Rh1—C2—C3—C4	11.54 (18)	C9—C10—C11—F4	−178.8 (2)
C12—C3—C4—C5	−52.6 (3)	F3—C10—C11—C12	−178.6 (2)
C2—C3—C4—C5	60.5 (3)	C9—C10—C11—C12	0.9 (4)
C12—C3—C4—Rh1	−124.60 (17)	F4—C11—C12—C7	177.5 (2)
C2—C3—C4—Rh1	−11.46 (18)	C10—C11—C12—C7	−2.1 (4)
O1—Rh1—C4—C5	97.18 (15)	F4—C11—C12—C3	−3.9 (4)
O1^i—Rh1—C4—C5	−172.93 (16)	C10—C11—C12—C3	176.4 (3)
C2—Rh1—C4—C5	−103.46 (16)	C8—C7—C12—C11	2.0 (4)
C1—Rh1—C4—C5	−64.94 (15)	C6—C7—C12—C11	−178.6 (2)
Rh1^i—Rh1—C4—C5	146.33 (13)	C8—C7—C12—C3	−176.8 (2)
O1—Rh1—C4—C3	−150.32 (14)	C6—C7—C12—C3	2.6 (3)
O1^i—Rh1—C4—C3	−60.4 (2)	C2—C3—C12—C11	126.6 (3)
C2—Rh1—C4—C3	9.03 (14)	C4—C3—C12—C11	−127.8 (3)
C5—Rh1—C4—C3	112.5 (2)	C2—C3—C12—C7	−54.7 (3)
C1—Rh1—C4—C3	47.56 (15)	C4—C3—C12—C7	50.8 (3)
Rh1^i—Rh1—C4—C3	−101.18 (14)	O1^i—Rh1—O1—C13	−169.8 (2)
C3—C4—C5—C6	0.6 (3)	C2—Rh1—O1—C13	−83.3 (3)
Rh1—C4—C5—C6	89.50 (19)	C4—Rh1—O1—C13	−17.3 (2)
C3—C4—C5—Rh1	−88.88 (19)	C5—Rh1—O1—C13	23.2 (2)
O1—Rh1—C5—C4	−94.50 (15)	C1—Rh1—O1—C13	88.4 (3)
O1^i—Rh1—C5—C4	165.6 (3)	Rh1^i—Rh1—O1—C13	−127.1 (2)
C2—Rh1—C5—C4	65.27 (15)	O1^i—Rh1—O1—Rh1^i	−42.68 (8)
C1—Rh1—C5—C4	103.60 (16)	C2—Rh1—O1—Rh1^i	43.8 (3)
Rh1^i—Rh1—C5—C4	−57.35 (19)	C4—Rh1—O1—Rh1^i	109.81 (9)
O1—Rh1—C5—C6	153.36 (13)	C5—Rh1—O1—Rh1^i	150.35 (8)
O1^i—Rh1—C5—C6	53.5 (4)	C1—Rh1—O1—Rh1^i	−144.4 (3)
C2—Rh1—C5—C6	−46.87 (15)

Symmetry code: (i) x, −y+1/2, −z+1/2.