Tris(1,10-phenanthroline-[kappa]²N,N')cobalt(III) tris­(trifluoro­methane­sulfonate) dihydrate

The title compound, [Co(C₁₂H₈N₂)₃](CF₃SO₃)₃·2H₂O, crystallizes to form infinite chains of complex cations that are connected through offset face-to-face and edge-to-face inter­actions between their phenanthroline ligands. The chains are themselves inter­connected through weak offset face-to-face ligand inter­actions. The three trifluoro­methane­sulfonate anions of the asymmetric unit are connected with one another through the two water mol­ecules by hydrogen bonds. One of the trifluoro­methane­sulfonate anions is described by a disorder over three positions, with occupancies of 0.35, 0.35 and 0.3 in the refined model.

S1. Comment

The tris(1,10-phenanthroline)cobalt(III) complex was first synthesized by Pfeiffer & Werdelmann (1950). It has been used in conjunction with the tris(1,10-phenanthroline)cobalt(II) complex as a redox couple in dye-sensitized solar cells (Nusbaumer, 2004), serving as an alternative to the prolific I^-/I₃^- couple (Grätzel, 2005). Co complexes with various ligands have been used with trifluoromethanesulfonate counter-ions (Wen et al., 2000; Nusbaumer, 2004), where [Co(C₁₂H₈N₂)₃](CF₃SO₃)₃·2H₂O, compound (I), is an example of such a complex.

Compound (I) crystallizes into a racemic triclinic structure with two water molecules per complex cation. Powder X-ray diffraction confirms that the synthesis of (I) yields a stoichiometric compound with only one crystal structure.

The asymmetric unit contains one [Co(phen)₃]³⁺ cation, three trifluoromethanesulfonate anions and two water molecules. The three trifluoromethanesulfonate ions interact with the two water molecules to form a chain, bridged by hydrogen bonds (Fig. 1 and Table 1). The complex cations are not isolated by the anions and water molecules, but rather they interact with one another in motifs that have been described in the literature (Russell et al., 2001). The structure contains four different pairs of cations with a significant van der Waals interaction between ligands (Figs. 2a–2d).

In general, two types of motifs are distinguished, depending on whether the planes of the interacting ligands are parallel (face-to-face) or perpendicular (edge-to-face) to one another. Offset face-to-face (OFF) interactions are clearly present in the motifs shown in Figs. 2(b) and 2(c), and even an edge-to-face (EF) interaction can be recognized in Fig. 2(b). However, the motifs presented in Figs. 2(a) and 2(d) have limited OFF or EF characteristics. This is supported by additional geometric parameters given in Table 2. It should be noted that Russell et al. limited their characterization of OFF ligand interactions to those complex pairs that fulfilled certain geometric criteria. In our context, where all motifs are centrosymmetric, these translate to a plane-to-plane distance in the range 3.2–3.6 Å and a shortest C···C distance between a C atom equivalent to C11 (assuming D₃ symmetry for the complex cation) and any C atom of the second phenanthroline ligand not exceeding 4.0 Å (Russell et al., 2001). As motifs (a) and (d) do not comply with these requirements, they will be considered to be weak interactions compared with (b) and (c).

Further characterization of these motifs was carried out by calculating the energy contributions arising from van der Waals and Coulombic interactions, considering either a complete pair of complex cations or only a pair of ligands forming an OFF or EF motif. This was achieved using the methodology of Russell et al. (2001). The atomic charge distribution of a complex cation was approximated on the basis of the charge distribution of an [Fe(phen)₃]²⁺ cation (Russell et al., 2001), multiplying each partial charge by 1.5 to achieve the correct total charge. Although this procedure does not take into account details such as electronegativity in distributing the additional charge, other approaches (such as adding an equal fractional charge to each atom) only result in minor quantitative deviations. The obtained values for the interactions (Table 3) show that only OFF interaction motifs (b) and (c) contribute significantly to a favorable attractive energy. The total intermolecular energy is positive in all cases, however, owing to the high total charge of the complex cations.

It is interesting to note that motif (a), in which the distance between the two Co atoms is shortest, has the least favorable interaction energy. The close proximity of the cations leads to a strong Coulombic repulsion and only a weak van der Waals attraction between ligands, since their close approach causes them to avoid one another.

The packing of the complex cations can be described as infinite chains along [111] that are formed through the strong interaction motifs (b) and (c), as shown in Fig. 2(e). These chains are interconnected in two directions by the weaker interaction motifs (a) and (d), and form a three-dimensional network similar to a distorted diamond structure. The voids and channels of this network are then filled with the short chains of anions and water molecules. The two ordered trifluoromethanesulfonate anions are located in channels (rings), whereas the disordered trifluoromethanesulfonate group points into a void (cage). This might provide enough freedom to allow a rocking motion of the anion, resulting in the observed disorder. Such anionic and solvent disorder is a common phenomenon found in crystals containing [M(phen)₃]ⁿ⁺ complex cations (Anderson, 1973; Baker et al., 1975; Boys et al., 1984; Deacon et al., 1979; Freire et al., 1998; Goodwin et al., 1984; Koh et al., 1994; Luck et al., 2000).

Related literature

For related literature, see: Anderson (1973); Baker et al. (1975); Boys et al. (1984); Deacon et al. (1979); Freire et al. (1998); Goodwin et al. (1984); Grätzel (2005); Koh et al. (1994); Luck et al. (2000); Nusbaumer (2004); Pfeiffer & Werdelmann (1950); Russell et al. (2001); Wen et al. (2000).

S2. Experimental

Compound (I) was synthesized according to a method described by Nusbaumer (2004). To cobalt(II) chloride hexahydrate (236 mg) in water (10 ml) was added 1,10-phenanthroline hydrate (596 mg) in methanol (2 ml), and the mixture was stirred at room temperature for 30 min. Bromine (0.1 ml) in water (8 ml) was added dropwise, whereupon a red–brown powder precipitated. The temperature was elevated to 318–323 K to complete the oxidation. Immediately after the oxidation step, the counter-ions were exchanged by adding silver trifluoromethanesulfonate (0.567 mg) in methanol (2.5 ml). The Ag halide precipitate was filtered off, leaving an orange solution. Evaporation under reduced pressure led to large orange crystals.

S3. Refinement

All atoms except those of the disordered trifluoromethanesulfonate anion were refined anisotropically. The final model describes the disorder by considering three different orientations of the disordered trifluoromethanesulfonate group (refered to as A, B and C). Restraints were used in order to equalize the C—S bond lengths (of A, B and C) and the C—F, S—O and C···O distances (separately for A and B). Occupancies were constrained to add up to unity and were fixed after convergence to 35% (A), 30% (B) and 35% (C). All H-atom parameters were refined, giving C—H distances in the range 0.88 (3)–0.96 (2).

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2005); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of the crystal structure of (I) at 140 K, showing the atomic labeling and 50% probability displacement ellipsoids. Aromatic H atoms and two sites of the disordered anion have been omitted for clarity. Dashed lines represent hydrogen bonds.
	Fig. 2. (a)–(d) Supramolecular motifs formed by pairs of complex cations in the order of increasing Co···Co distance. The view is perpendicular to the phenanthroline ligand planes participating in an `OFF' interaction. (e) Chains formed from an alternating succession of motifs (b) and (c). The third ligand is shown as a ball and stick model for clarity.

Tris(1,10-phenanthroline-κ²N,N')cobalt(III) tris(trifluoromethanesulfonate) dihydrate

Crystal data

[Co(C12H8N2)3](CF3O3S)3·2H2O	Z = 2
Mr = 1082.78	F(000) = 1096
Triclinic, P1	Dx = 1.738 Mg m^−3
a = 12.4096 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 13.0039 (4) Å	Cell parameters from 9027 reflections
c = 13.4669 (4) Å	θ = 2.7–33.3°
α = 92.764 (1)°	µ = 0.68 mm^−1
β = 107.367 (1)°	T = 140 K
γ = 91.878 (1)°	Triangular, orange
V = 2069.2 (1) Å^3	0.28 × 0.20 × 0.15 mm

Data collection

Bruker SMART 6000 diffractometer	14813 independent reflections
Radiation source: fine-focus sealed tube	13149 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
ω scans	θmax = 33.5°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2002)	h = −18→19
Tmin = 0.77, Tmax = 0.90	k = −19→20
36176 measured reflections	l = −20→19

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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F^2) = 0.107	All H-atom parameters refined
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0536P)^2 + 1.3093P] where P = (Fo^2 + 2Fc^2)/3
14813 reflections	(Δ/σ)max = 0.005
758 parameters	Δρmax = 0.75 e Å^−3
21 restraints	Δρmin = −0.63 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	Occ. (<1)
Co1	0.207589 (14)	0.295187 (13)	0.740936 (13)	0.01400 (4)
N1	0.31395 (9)	0.37027 (9)	0.68838 (8)	0.01688 (19)
N2	0.32690 (9)	0.30877 (8)	0.87328 (8)	0.01570 (18)
N3	0.14688 (9)	0.42076 (9)	0.77994 (8)	0.01643 (19)
N4	0.10192 (9)	0.22723 (9)	0.80048 (9)	0.01689 (19)
N5	0.09296 (9)	0.27995 (9)	0.60603 (9)	0.01682 (19)
N6	0.26006 (10)	0.16664 (9)	0.69638 (9)	0.01743 (19)
C1	0.30038 (12)	0.40487 (12)	0.59405 (11)	0.0220 (3)
H1	0.2296 (17)	0.3872 (15)	0.5424 (15)	0.019 (4)*
C2	0.38513 (13)	0.46582 (13)	0.57235 (11)	0.0243 (3)
H2	0.369 (2)	0.4898 (18)	0.5062 (19)	0.035 (6)*
C3	0.48628 (12)	0.48898 (12)	0.64793 (11)	0.0220 (2)
H3	0.5391 (19)	0.5294 (17)	0.6352 (17)	0.029 (5)*
C4	0.50387 (11)	0.45031 (10)	0.74743 (10)	0.0178 (2)
C5	0.60628 (11)	0.46729 (11)	0.83209 (11)	0.0214 (2)
H4	0.6644 (17)	0.5031 (16)	0.8199 (16)	0.022 (5)*
C6	0.61457 (11)	0.43116 (11)	0.92720 (11)	0.0213 (2)
H5	0.6822 (18)	0.4399 (17)	0.9826 (17)	0.027 (5)*
C7	0.52134 (11)	0.37717 (10)	0.94690 (10)	0.0172 (2)
C8	0.52011 (12)	0.34374 (11)	1.04458 (10)	0.0206 (2)
H6	0.5852 (18)	0.3568 (17)	1.1035 (17)	0.028 (5)*
C9	0.42333 (13)	0.29686 (11)	1.05445 (10)	0.0214 (2)
H7	0.4153 (19)	0.2785 (18)	1.1186 (18)	0.032 (6)*
C10	0.32720 (12)	0.28012 (10)	0.96740 (10)	0.0184 (2)
H8	0.2593 (18)	0.2480 (16)	0.9715 (16)	0.024 (5)*
C11	0.42174 (10)	0.35813 (9)	0.86389 (9)	0.0152 (2)
C12	0.41418 (10)	0.39303 (10)	0.76381 (10)	0.0159 (2)
C13	0.17646 (12)	0.51882 (11)	0.77135 (10)	0.0200 (2)
H9	0.2331 (17)	0.5319 (16)	0.7421 (16)	0.022 (5)*
C14	0.12186 (14)	0.60044 (11)	0.80428 (11)	0.0244 (3)
H10	0.1480 (19)	0.6664 (18)	0.7985 (17)	0.032 (6)*
C15	0.03454 (13)	0.58101 (12)	0.84499 (11)	0.0245 (3)
H11	0.002 (2)	0.6337 (18)	0.8688 (18)	0.034 (6)*
C16	0.00054 (12)	0.47831 (11)	0.85325 (10)	0.0209 (2)
C17	−0.08995 (12)	0.44700 (13)	0.89268 (11)	0.0256 (3)
H12	−0.1340 (19)	0.4972 (18)	0.9100 (17)	0.031 (5)*
C18	−0.11397 (12)	0.34641 (14)	0.90308 (12)	0.0261 (3)
H13	−0.172 (2)	0.3242 (19)	0.9257 (19)	0.037 (6)*
C19	−0.04890 (12)	0.26681 (12)	0.87481 (11)	0.0219 (2)
C20	−0.06533 (13)	0.16089 (13)	0.88639 (13)	0.0274 (3)
H14	−0.120 (2)	0.1386 (18)	0.9163 (18)	0.036 (6)*
C21	0.00211 (14)	0.09213 (12)	0.85603 (13)	0.0267 (3)
H15	−0.008 (2)	0.024 (2)	0.8617 (19)	0.038 (6)*
C22	0.08535 (12)	0.12739 (11)	0.81250 (11)	0.0214 (2)
H16	0.1319 (17)	0.0816 (16)	0.7931 (15)	0.022 (5)*
C23	0.03639 (11)	0.29570 (10)	0.83203 (10)	0.0173 (2)
C24	0.06117 (11)	0.40097 (10)	0.82130 (10)	0.0172 (2)
C25	0.00934 (11)	0.34118 (11)	0.56340 (11)	0.0200 (2)
H17	0.0018 (17)	0.3992 (16)	0.5983 (16)	0.022 (5)*
C26	−0.06853 (12)	0.31526 (12)	0.46494 (11)	0.0237 (3)
H18	−0.124 (2)	0.3606 (18)	0.4380 (18)	0.034 (6)*
C27	−0.05974 (13)	0.22616 (12)	0.40981 (11)	0.0240 (3)
H19	−0.1092 (18)	0.2089 (17)	0.3453 (17)	0.027 (5)*
C28	0.02872 (12)	0.16109 (11)	0.45286 (10)	0.0207 (2)
C29	0.04867 (14)	0.06720 (12)	0.40237 (11)	0.0260 (3)
H20	0.0034 (19)	0.0510 (17)	0.3372 (18)	0.029 (5)*
C30	0.13543 (15)	0.00812 (12)	0.44850 (12)	0.0267 (3)
H21	0.151 (2)	−0.049 (2)	0.415 (2)	0.043 (7)*
C31	0.21172 (13)	0.03825 (11)	0.55007 (11)	0.0218 (2)
C32	0.30569 (14)	−0.01707 (12)	0.60305 (12)	0.0257 (3)
H22	0.323 (2)	−0.075 (2)	0.5756 (19)	0.039 (6)*
C33	0.37377 (13)	0.02118 (12)	0.69901 (12)	0.0247 (3)
H23	0.434 (2)	−0.0125 (18)	0.7371 (18)	0.035 (6)*
C34	0.34901 (12)	0.11353 (11)	0.74413 (11)	0.0207 (2)
H24	0.3917 (17)	0.1396 (16)	0.8055 (16)	0.021 (5)*
C35	0.19334 (11)	0.12998 (10)	0.60041 (10)	0.0178 (2)
C36	0.10198 (11)	0.19125 (10)	0.55168 (10)	0.0176 (2)
S1A	0.21955 (18)	0.26890 (17)	0.2397 (2)	0.0134 (3)*	0.35
C37A	0.2948 (7)	0.1503 (6)	0.2860 (7)	0.0182 (17)*	0.35
O1A	0.3168 (5)	0.3439 (4)	0.2765 (5)	0.0350 (10)*	0.35
O2A	0.1792 (4)	0.2542 (5)	0.1306 (4)	0.0235 (8)*	0.35
O3A	0.1315 (6)	0.2725 (5)	0.2910 (6)	0.0190 (11)*	0.35
F1A	0.2296 (5)	0.0659 (3)	0.2550 (5)	0.0227 (7)*	0.35
F2A	0.3846 (4)	0.1409 (4)	0.2516 (4)	0.0247 (8)*	0.35
F3A	0.3482 (5)	0.1556 (6)	0.3862 (5)	0.0432 (13)*	0.35
S1B	0.2083 (2)	0.2529 (2)	0.2269 (2)	0.0383 (8)*	0.30
C37B	0.3105 (7)	0.1652 (6)	0.3013 (6)	0.040 (2)*	0.30
O1B	0.2855 (6)	0.3524 (5)	0.2575 (5)	0.0461 (15)*	0.30
O2B	0.1732 (6)	0.2289 (6)	0.1227 (5)	0.049 (2)*	0.30
O3B	0.1218 (6)	0.2562 (5)	0.2789 (6)	0.0321 (19)*	0.30
F1B	0.2549 (6)	0.0711 (6)	0.2755 (6)	0.062 (3)*	0.30
F2B	0.4008 (5)	0.1655 (5)	0.2698 (4)	0.0465 (15)*	0.30
F3B	0.3302 (6)	0.1698 (5)	0.4004 (4)	0.0407 (12)*	0.30
S1C	0.23023 (15)	0.27610 (14)	0.25737 (14)	0.0266 (6)*	0.35
C37C	0.2874 (9)	0.1488 (8)	0.2745 (8)	0.037 (3)*	0.35
O1C	0.3103 (5)	0.3553 (4)	0.3056 (4)	0.0423 (12)*	0.35
O2C	0.2002 (5)	0.2802 (5)	0.1448 (5)	0.0494 (17)*	0.35
O3C	0.1485 (4)	0.2738 (5)	0.3105 (4)	0.0308 (15)*	0.35
F1C	0.2079 (4)	0.0725 (4)	0.2369 (4)	0.0451 (17)*	0.35
F2C	0.3699 (4)	0.1339 (3)	0.2285 (3)	0.0328 (11)*	0.35
F3C	0.3235 (4)	0.1380 (3)	0.3814 (3)	0.0314 (8)*	0.35
C38	0.38610 (17)	0.79792 (13)	0.34817 (14)	0.0322 (3)
C39	0.32757 (14)	0.97148 (12)	1.00627 (12)	0.0275 (3)
S2	0.28934 (3)	0.72498 (3)	0.40090 (3)	0.02283 (7)
S3	0.27390 (3)	0.86882 (3)	0.90444 (3)	0.02393 (7)
F4	0.49070 (10)	0.76594 (10)	0.38110 (11)	0.0452 (3)
F5	0.39003 (13)	0.89755 (9)	0.37673 (12)	0.0507 (3)
F6	0.35369 (14)	0.78822 (12)	0.24434 (10)	0.0554 (4)
F7	0.41173 (12)	0.94161 (11)	1.08339 (10)	0.0540 (4)
F8	0.24641 (12)	1.00139 (11)	1.04551 (11)	0.0528 (4)
F9	0.36432 (13)	1.05392 (9)	0.96969 (10)	0.0458 (3)
O4	0.34057 (13)	0.74230 (11)	0.51177 (9)	0.0361 (3)
O5	0.18310 (11)	0.77275 (11)	0.35997 (11)	0.0360 (3)
O6	0.29251 (11)	0.62038 (9)	0.36088 (10)	0.0315 (2)
O7	0.17961 (13)	0.91199 (12)	0.83166 (12)	0.0454 (4)
O8	0.36892 (12)	0.85314 (10)	0.86495 (11)	0.0366 (3)
O9	0.24785 (14)	0.78508 (10)	0.96084 (12)	0.0410 (3)
O10	0.12487 (11)	0.47292 (11)	0.39099 (10)	0.0302 (2)
H25	0.125 (2)	0.421 (2)	0.363 (2)	0.039 (7)*
H26	0.168 (2)	0.508 (2)	0.376 (2)	0.045 (7)*
O11	0.33191 (12)	0.68523 (11)	0.71035 (10)	0.0320 (3)
H27	0.337 (2)	0.698 (2)	0.656 (2)	0.046 (7)*
H28	0.346 (2)	0.738 (2)	0.743 (2)	0.040 (7)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.01305 (8)	0.01605 (8)	0.01317 (8)	0.00044 (5)	0.00425 (6)	0.00176 (5)
N1	0.0147 (4)	0.0215 (5)	0.0151 (4)	0.0008 (4)	0.0049 (4)	0.0040 (4)
N2	0.0159 (4)	0.0167 (5)	0.0148 (4)	0.0009 (4)	0.0048 (4)	0.0022 (3)
N3	0.0159 (4)	0.0172 (5)	0.0153 (4)	0.0006 (4)	0.0033 (4)	0.0013 (4)
N4	0.0158 (4)	0.0186 (5)	0.0165 (5)	−0.0006 (4)	0.0053 (4)	0.0010 (4)
N5	0.0152 (4)	0.0193 (5)	0.0158 (4)	0.0003 (4)	0.0045 (4)	0.0017 (4)
N6	0.0179 (5)	0.0190 (5)	0.0166 (5)	0.0022 (4)	0.0066 (4)	0.0025 (4)
C1	0.0195 (6)	0.0310 (7)	0.0164 (5)	0.0022 (5)	0.0059 (5)	0.0074 (5)
C2	0.0235 (6)	0.0324 (7)	0.0205 (6)	0.0027 (5)	0.0104 (5)	0.0099 (5)
C3	0.0208 (6)	0.0251 (6)	0.0243 (6)	0.0016 (5)	0.0125 (5)	0.0067 (5)
C4	0.0157 (5)	0.0193 (5)	0.0202 (5)	0.0016 (4)	0.0079 (4)	0.0024 (4)
C5	0.0153 (5)	0.0240 (6)	0.0256 (6)	−0.0010 (4)	0.0074 (5)	0.0019 (5)
C6	0.0149 (5)	0.0242 (6)	0.0231 (6)	0.0004 (4)	0.0032 (5)	−0.0002 (5)
C7	0.0163 (5)	0.0173 (5)	0.0169 (5)	0.0030 (4)	0.0033 (4)	0.0011 (4)
C8	0.0217 (6)	0.0214 (6)	0.0162 (5)	0.0035 (5)	0.0014 (4)	0.0019 (4)
C9	0.0260 (6)	0.0230 (6)	0.0145 (5)	0.0023 (5)	0.0043 (5)	0.0038 (4)
C10	0.0205 (6)	0.0192 (6)	0.0164 (5)	0.0006 (4)	0.0067 (4)	0.0036 (4)
C11	0.0154 (5)	0.0153 (5)	0.0152 (5)	0.0019 (4)	0.0048 (4)	0.0018 (4)
C12	0.0148 (5)	0.0183 (5)	0.0154 (5)	0.0020 (4)	0.0054 (4)	0.0028 (4)
C13	0.0214 (6)	0.0183 (6)	0.0182 (5)	−0.0012 (4)	0.0027 (5)	0.0017 (4)
C14	0.0303 (7)	0.0179 (6)	0.0205 (6)	0.0021 (5)	0.0010 (5)	0.0000 (5)
C15	0.0292 (7)	0.0224 (6)	0.0189 (6)	0.0090 (5)	0.0021 (5)	−0.0011 (5)
C16	0.0193 (6)	0.0262 (6)	0.0153 (5)	0.0064 (5)	0.0021 (4)	−0.0006 (4)
C17	0.0200 (6)	0.0363 (8)	0.0206 (6)	0.0083 (5)	0.0062 (5)	−0.0023 (5)
C18	0.0182 (6)	0.0401 (8)	0.0219 (6)	0.0021 (5)	0.0091 (5)	−0.0003 (6)
C19	0.0173 (5)	0.0304 (7)	0.0188 (6)	−0.0012 (5)	0.0070 (4)	0.0012 (5)
C20	0.0242 (7)	0.0329 (8)	0.0283 (7)	−0.0058 (6)	0.0132 (6)	0.0043 (6)
C21	0.0283 (7)	0.0236 (7)	0.0302 (7)	−0.0061 (5)	0.0120 (6)	0.0047 (5)
C22	0.0226 (6)	0.0185 (6)	0.0235 (6)	−0.0022 (5)	0.0079 (5)	0.0019 (5)
C23	0.0150 (5)	0.0213 (6)	0.0156 (5)	0.0000 (4)	0.0048 (4)	0.0006 (4)
C24	0.0156 (5)	0.0208 (6)	0.0142 (5)	0.0014 (4)	0.0029 (4)	0.0003 (4)
C25	0.0174 (5)	0.0229 (6)	0.0192 (6)	0.0024 (4)	0.0044 (4)	0.0028 (5)
C26	0.0180 (6)	0.0310 (7)	0.0198 (6)	0.0012 (5)	0.0017 (5)	0.0052 (5)
C27	0.0215 (6)	0.0310 (7)	0.0165 (6)	−0.0036 (5)	0.0015 (5)	0.0029 (5)
C28	0.0212 (6)	0.0248 (6)	0.0150 (5)	−0.0046 (5)	0.0047 (4)	−0.0003 (4)
C29	0.0320 (7)	0.0277 (7)	0.0173 (6)	−0.0055 (6)	0.0074 (5)	−0.0040 (5)
C30	0.0361 (8)	0.0234 (7)	0.0223 (6)	−0.0030 (6)	0.0126 (6)	−0.0049 (5)
C31	0.0277 (6)	0.0202 (6)	0.0203 (6)	0.0007 (5)	0.0119 (5)	0.0002 (5)
C32	0.0329 (7)	0.0215 (6)	0.0274 (7)	0.0065 (5)	0.0155 (6)	0.0020 (5)
C33	0.0273 (7)	0.0228 (6)	0.0272 (7)	0.0085 (5)	0.0118 (5)	0.0054 (5)
C34	0.0207 (6)	0.0226 (6)	0.0197 (6)	0.0047 (5)	0.0067 (5)	0.0041 (5)
C35	0.0191 (5)	0.0187 (5)	0.0169 (5)	−0.0002 (4)	0.0077 (4)	0.0010 (4)
C36	0.0183 (5)	0.0194 (5)	0.0154 (5)	−0.0014 (4)	0.0058 (4)	0.0008 (4)
C38	0.0434 (9)	0.0256 (7)	0.0339 (8)	0.0007 (6)	0.0209 (7)	0.0033 (6)
C39	0.0317 (7)	0.0246 (7)	0.0253 (7)	−0.0065 (6)	0.0085 (6)	−0.0003 (5)
S2	0.02964 (17)	0.02101 (15)	0.02015 (15)	0.00264 (12)	0.01068 (13)	0.00227 (11)
S3	0.02834 (17)	0.01895 (15)	0.02268 (16)	0.00063 (12)	0.00528 (13)	−0.00077 (12)
F4	0.0371 (6)	0.0398 (6)	0.0657 (8)	−0.0010 (5)	0.0271 (6)	−0.0012 (6)
F5	0.0671 (9)	0.0214 (5)	0.0751 (9)	−0.0024 (5)	0.0393 (8)	0.0031 (5)
F6	0.0775 (10)	0.0646 (9)	0.0323 (6)	−0.0073 (7)	0.0290 (6)	0.0111 (6)
F7	0.0560 (8)	0.0533 (8)	0.0341 (6)	−0.0055 (6)	−0.0138 (5)	0.0027 (5)
F8	0.0586 (8)	0.0501 (7)	0.0577 (8)	−0.0124 (6)	0.0358 (7)	−0.0251 (6)
F9	0.0696 (9)	0.0237 (5)	0.0467 (7)	−0.0157 (5)	0.0239 (6)	−0.0008 (4)
O4	0.0485 (8)	0.0411 (7)	0.0193 (5)	−0.0002 (6)	0.0113 (5)	0.0016 (5)
O5	0.0332 (6)	0.0370 (7)	0.0392 (7)	0.0106 (5)	0.0116 (5)	0.0058 (5)
O6	0.0401 (6)	0.0205 (5)	0.0366 (6)	0.0000 (4)	0.0161 (5)	−0.0013 (4)
O7	0.0393 (7)	0.0430 (8)	0.0394 (7)	0.0120 (6)	−0.0099 (6)	−0.0074 (6)
O8	0.0460 (7)	0.0317 (6)	0.0386 (7)	0.0084 (5)	0.0220 (6)	0.0023 (5)
O9	0.0574 (9)	0.0266 (6)	0.0420 (7)	−0.0145 (6)	0.0217 (7)	−0.0006 (5)
O10	0.0294 (6)	0.0333 (6)	0.0262 (5)	0.0035 (5)	0.0057 (5)	0.0022 (5)
O11	0.0404 (7)	0.0340 (6)	0.0220 (5)	−0.0047 (5)	0.0103 (5)	0.0034 (5)

Geometric parameters (Å, º)

Co1—N1	1.9330 (11)	C25—H17	0.89 (2)
Co1—N3	1.9349 (11)	C26—C27	1.371 (2)
Co1—N4	1.9399 (11)	C26—H18	0.93 (2)
Co1—N5	1.9410 (11)	C27—C28	1.409 (2)
Co1—N2	1.9435 (11)	C27—H19	0.91 (2)
Co1—N6	1.9458 (11)	C28—C36	1.3984 (18)
N1—C1	1.3330 (16)	C28—C29	1.433 (2)
N1—C12	1.3635 (16)	C29—C30	1.355 (2)
N2—C10	1.3373 (16)	C29—H20	0.90 (2)
N2—C11	1.3639 (16)	C30—C31	1.439 (2)
N3—C13	1.3353 (17)	C30—H21	0.91 (3)
N3—C24	1.3629 (17)	C31—C35	1.4023 (19)
N4—C22	1.3330 (18)	C31—C32	1.412 (2)
N4—C23	1.3608 (17)	C32—C33	1.375 (2)
N5—C25	1.3353 (17)	C32—H22	0.88 (3)
N5—C36	1.3618 (17)	C33—C34	1.404 (2)
N6—C34	1.3334 (17)	C33—H23	0.91 (2)
N6—C35	1.3635 (17)	C34—H24	0.88 (2)
C1—C2	1.404 (2)	C35—C36	1.4200 (19)
C1—H1	0.96 (2)	S1A—O2A	1.404 (5)
C2—C3	1.373 (2)	S1A—O3A	1.458 (5)
C2—H2	0.92 (2)	S1A—O1A	1.474 (6)
C3—C4	1.4120 (19)	S1A—C37A	1.866 (7)
C3—H3	0.89 (2)	C37A—F3A	1.312 (10)
C4—C12	1.3965 (18)	C37A—F1A	1.315 (9)
C4—C5	1.4339 (19)	C37A—F2A	1.335 (8)
C5—C6	1.362 (2)	S1B—O2B	1.356 (7)
C5—H4	0.91 (2)	S1B—O3B	1.447 (6)
C6—C7	1.4318 (19)	S1B—O1B	1.546 (6)
C6—H5	0.94 (2)	S1B—C37B	1.834 (8)
C7—C11	1.4025 (17)	C37B—F3B	1.281 (9)
C7—C8	1.4094 (19)	C37B—F2B	1.310 (8)
C8—C9	1.374 (2)	C37B—F1B	1.362 (9)
C8—H6	0.95 (2)	S1C—O1C	1.398 (6)
C9—C10	1.4029 (19)	S1C—O3C	1.405 (5)
C9—H7	0.94 (2)	S1C—O2C	1.453 (6)
C10—H8	0.95 (2)	S1C—C37C	1.820 (9)
C11—C12	1.4204 (17)	C37C—F1C	1.342 (11)
C13—C14	1.401 (2)	C37C—F2C	1.360 (11)
C13—H9	0.92 (2)	C37C—F3C	1.390 (11)
C14—C15	1.374 (2)	C38—F4	1.328 (2)
C14—H10	0.92 (2)	C38—F5	1.329 (2)
C15—C16	1.407 (2)	C38—F6	1.333 (2)
C15—H11	0.90 (2)	C38—S2	1.8290 (18)
C16—C24	1.4013 (18)	C39—F7	1.318 (2)
C16—C17	1.434 (2)	C39—F9	1.3240 (19)
C17—C18	1.355 (2)	C39—F8	1.330 (2)
C17—H12	0.93 (2)	C39—S3	1.8239 (16)
C18—C19	1.438 (2)	S2—O4	1.4408 (13)
C18—H13	0.91 (2)	S2—O5	1.4424 (13)
C19—C23	1.3972 (18)	S2—O6	1.4449 (12)
C19—C20	1.409 (2)	S3—O7	1.4341 (14)
C20—C21	1.373 (2)	S3—O9	1.4389 (14)
C20—H14	0.93 (2)	S3—O8	1.4473 (14)
C21—C22	1.406 (2)	O10—H25	0.75 (3)
C21—H15	0.90 (3)	O10—H26	0.77 (3)
C22—H16	0.92 (2)	O11—H27	0.77 (3)
C23—C24	1.4169 (19)	O11—H28	0.78 (3)
C25—C26	1.4058 (19)
N1—Co1—N3	92.35 (5)	N3—C24—C16	123.35 (13)
N1—Co1—N4	176.25 (5)	N3—C24—C23	115.95 (12)
N3—Co1—N4	84.50 (5)	C16—C24—C23	120.70 (12)
N1—Co1—N5	93.62 (5)	N5—C25—C26	121.27 (13)
N3—Co1—N5	92.63 (5)	N5—C25—H17	119.6 (13)
N4—Co1—N5	88.58 (5)	C26—C25—H17	119.1 (13)
N1—Co1—N2	84.76 (5)	C27—C26—C25	120.47 (14)
N3—Co1—N2	89.11 (5)	C27—C26—H18	121.3 (15)
N4—Co1—N2	93.13 (5)	C25—C26—H18	118.2 (15)
N5—Co1—N2	177.67 (5)	C26—C27—C28	119.15 (13)
N1—Co1—N6	89.26 (5)	C26—C27—H19	121.3 (14)
N3—Co1—N6	176.72 (5)	C28—C27—H19	119.5 (14)
N4—Co1—N6	93.98 (5)	C36—C28—C27	117.13 (13)
N5—Co1—N6	84.42 (5)	C36—C28—C29	118.23 (13)
N2—Co1—N6	93.88 (5)	C27—C28—C29	124.64 (13)
C1—N1—C12	118.41 (12)	C30—C29—C28	121.52 (14)
C1—N1—Co1	129.59 (10)	C30—C29—H20	121.3 (14)
C12—N1—Co1	111.92 (8)	C28—C29—H20	117.1 (14)
C10—N2—C11	118.40 (11)	C29—C30—C31	120.91 (14)
C10—N2—Co1	130.15 (9)	C29—C30—H21	121.6 (16)
C11—N2—Co1	111.43 (8)	C31—C30—H21	117.4 (16)
C13—N3—C24	118.52 (12)	C35—C31—C32	116.91 (13)
C13—N3—Co1	129.69 (10)	C35—C31—C30	118.23 (13)
C24—N3—Co1	111.79 (9)	C32—C31—C30	124.86 (14)
C22—N4—C23	118.42 (12)	C33—C32—C31	119.24 (13)
C22—N4—Co1	129.79 (10)	C33—C32—H22	118.8 (16)
C23—N4—Co1	111.79 (9)	C31—C32—H22	121.9 (16)
C25—N5—C36	118.51 (12)	C32—C33—C34	120.19 (14)
C25—N5—Co1	129.52 (10)	C32—C33—H23	122.6 (15)
C36—N5—Co1	111.94 (9)	C34—C33—H23	117.2 (15)
C34—N6—C35	118.26 (12)	N6—C34—C33	121.80 (13)
C34—N6—Co1	129.98 (10)	N6—C34—H24	116.5 (13)
C35—N6—Co1	111.75 (9)	C33—C34—H24	121.7 (13)
N1—C1—C2	121.53 (13)	N6—C35—C31	123.59 (13)
N1—C1—H1	116.7 (12)	N6—C35—C36	115.90 (12)
C2—C1—H1	121.8 (12)	C31—C35—C36	120.51 (12)
C3—C2—C1	120.35 (13)	N5—C36—C28	123.45 (13)
C3—C2—H2	122.2 (15)	N5—C36—C35	115.93 (11)
C1—C2—H2	117.4 (15)	C28—C36—C35	120.60 (12)
C2—C3—C4	119.05 (13)	O2A—S1A—O3A	114.5 (4)
C2—C3—H3	120.6 (14)	O2A—S1A—O1A	113.3 (4)
C4—C3—H3	120.4 (14)	O3A—S1A—O1A	118.3 (4)
C12—C4—C3	117.11 (12)	O2A—S1A—C37A	105.7 (4)
C12—C4—C5	118.48 (12)	O3A—S1A—C37A	104.0 (3)
C3—C4—C5	124.41 (13)	O1A—S1A—C37A	98.2 (4)
C6—C5—C4	120.72 (13)	F3A—C37A—F1A	112.7 (7)
C6—C5—H4	121.7 (13)	F3A—C37A—F2A	98.0 (7)
C4—C5—H4	117.6 (13)	F1A—C37A—F2A	107.9 (6)
C5—C6—C7	121.50 (12)	F3A—C37A—S1A	113.7 (6)
C5—C6—H5	121.4 (13)	F1A—C37A—S1A	112.5 (6)
C7—C6—H5	117.1 (13)	F2A—C37A—S1A	111.0 (5)
C11—C7—C8	116.74 (12)	O2B—S1B—O3B	116.8 (5)
C11—C7—C6	118.12 (12)	O2B—S1B—O1B	113.1 (4)
C8—C7—C6	125.11 (12)	O3B—S1B—O1B	109.7 (4)
C9—C8—C7	119.54 (12)	O2B—S1B—C37B	113.9 (4)
C9—C8—H6	120.8 (13)	O3B—S1B—C37B	104.3 (4)
C7—C8—H6	119.6 (13)	O1B—S1B—C37B	97.0 (4)
C8—C9—C10	120.26 (12)	F3B—C37B—F2B	115.0 (7)
C8—C9—H7	123.3 (14)	F3B—C37B—F1B	100.3 (7)
C10—C9—H7	116.3 (14)	F2B—C37B—F1B	109.1 (7)
N2—C10—C9	121.45 (12)	F3B—C37B—S1B	117.3 (6)
N2—C10—H8	116.2 (13)	F2B—C37B—S1B	110.3 (6)
C9—C10—H8	122.4 (13)	F1B—C37B—S1B	103.3 (6)
N2—C11—C7	123.56 (11)	O1C—S1C—O3C	107.5 (4)
N2—C11—C12	116.03 (11)	O1C—S1C—O2C	109.9 (4)
C7—C11—C12	120.39 (12)	O3C—S1C—O2C	122.3 (3)
N1—C12—C4	123.49 (12)	O1C—S1C—C37C	112.8 (4)
N1—C12—C11	115.81 (11)	O3C—S1C—C37C	103.2 (4)
C4—C12—C11	120.66 (12)	O2C—S1C—C37C	100.9 (4)
N3—C13—C14	121.42 (14)	F1C—C37C—F2C	107.2 (7)
N3—C13—H9	118.3 (13)	F1C—C37C—F3C	104.4 (8)
C14—C13—H9	120.3 (13)	F2C—C37C—F3C	113.3 (8)
C15—C14—C13	120.35 (14)	F1C—C37C—S1C	112.7 (7)
C15—C14—H10	122.4 (14)	F2C—C37C—S1C	113.3 (7)
C13—C14—H10	117.2 (14)	F3C—C37C—S1C	105.8 (6)
C14—C15—C16	119.30 (13)	F4—C38—F5	107.65 (16)
C14—C15—H11	119.8 (15)	F4—C38—F6	107.08 (15)
C16—C15—H11	120.8 (15)	F5—C38—F6	108.00 (15)
C24—C16—C15	117.01 (13)	F4—C38—S2	111.93 (12)
C24—C16—C17	117.80 (14)	F5—C38—S2	110.75 (12)
C15—C16—C17	125.18 (13)	F6—C38—S2	111.24 (14)
C18—C17—C16	121.66 (14)	F7—C39—F9	107.79 (15)
C18—C17—H12	119.6 (14)	F7—C39—F8	108.03 (15)
C16—C17—H12	118.8 (14)	F9—C39—F8	106.88 (15)
C17—C18—C19	120.87 (14)	F7—C39—S3	111.69 (12)
C17—C18—H13	123.5 (15)	F9—C39—S3	111.57 (11)
C19—C18—H13	115.6 (16)	F8—C39—S3	110.67 (12)
C23—C19—C20	117.15 (13)	O4—S2—O5	114.78 (8)
C23—C19—C18	118.16 (14)	O4—S2—O6	114.69 (8)
C20—C19—C18	124.69 (13)	O5—S2—O6	115.13 (8)
C21—C20—C19	119.25 (13)	O4—S2—C38	102.55 (9)
C21—C20—H14	120.9 (15)	O5—S2—C38	103.63 (8)
C19—C20—H14	119.8 (15)	O6—S2—C38	103.75 (8)
C20—C21—C22	120.10 (14)	O7—S3—O9	116.31 (10)
C20—C21—H15	120.5 (16)	O7—S3—O8	113.83 (10)
C22—C21—H15	119.3 (16)	O9—S3—O8	114.47 (9)
N4—C22—C21	121.59 (14)	O7—S3—C39	104.06 (8)
N4—C22—H16	117.9 (13)	O9—S3—C39	102.88 (8)
C21—C22—H16	120.5 (13)	O8—S3—C39	102.97 (8)
N4—C23—C19	123.49 (13)	H25—O10—H26	106 (3)
N4—C23—C24	115.79 (11)	H27—O11—H28	104 (3)
C19—C23—C24	120.70 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H26···O6	0.77 (3)	2.15 (3)	2.913 (2)	170 (3)
O10—H25···O3A	0.75 (3)	2.14 (3)	2.891 (7)	177 (3)
O10—H25···O3B	0.75 (3)	2.38 (3)	3.126 (7)	178 (3)
O10—H25···O3C	0.75 (3)	2.08 (3)	2.817 (6)	170 (3)
O11—H27···O4	0.77 (3)	2.07 (3)	2.841 (2)	175 (3)
O11—H28···O8	0.78 (3)	2.12 (3)	2.870 (2)	162 (3)