data reports Bis(4-cobaltoceniumyl-1-ferrocenyl-3-methyltriazolylidene)gold(I) hexafluoridophosphate trifluoromethanesulfonate Structure description

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1 ISSN Bis(4-cobaltoceniumyl-1-ferrocenyl-3-methyl-1,2,3- triazolylidene)gold(i) hexafluoridophosphate trifluoromethanesulfonate (1.2/1.8) Stefan Vanicek, Klaus Wurst, Holger Kopacka and Benno Bildstein* Received 9 April 2018 Accepted 24 April 2018 Edited by J. Simpson, University of Otago, New Zealand Keywords: homoleptic triazolylidene complex; tricationic; push pull system; gold; crystal structure. University of Innsbruck, Faculty of Chemistry and Pharmacy, Innrain 80-82, 6020 Innsbruck, Austria. *Correspondence benno.bildstein@uibk.ac.at The title compound, [AuCo 2 Fe 2 (C 5 H 5 ) 4 (C 13 H 11 N 3 ) 2 ](PF 6 ) 1.2 (CF 3 SO 3 ) 1.8, was synthesized by deprotonation of 4-cobaltoceniumyl-1-ferrocenyl-3-methyl-1,2,3- triazolium hexafluoridophosphate trifluoromethanesulfonate with thallium ethoxide, followed by transmetalation with chlorido(triphenylphosphine)- gold(i), crystallizing as orange prisms. It is a unique example of a homoleptic dimetallocenyl-substituted triazolylidene complex. CCDC reference: Structural data: full structural data are available from iucrdata.iucr.org Structure description The title compound (Figs. 1 and 2) is the first representative of a homoleptic dimetallocenyl substituted triazolylidene complex. As a result of the divergent electronic properties of the metallocene moieties, the ligand scaffold constitutes a push pull system. Structurally, regular ferrocene and cobaltocenium sandwich entities are observed, exhibiting coplanar cyclopentadienyl rings and displaying unexceptional carbon iron [2.016 (4) (14) Å], carbon cobalt [2.014 (6) (5) Å], as well as carbon carbon [1.392 (15)(16) (7)(14) Å] bond distances. The triazolylidene ring also has the anticipated bond lengths similar to its heteroleptic congeners, which have been published recently (Vanicek et al., 2018). The carbene gold distances of (4) and (4) Å are in line with expectations for this class of compounds. Synthesis and crystallization Bis(4-cobaltoceniumyl-1-ferrocenyl-3-methyltriazolylidene)gold(I) hexafluoridophosphate trifluoromethanesulfonate (1/1.2/1.8) was obtained by deprotonating g (0.186 mmol, 1 equiv.) of 4-cobaltoceniumyl-1-ferrocenyl-3-methyltriazolium hexa- 1of3

2 Table 1 Experimental details. Crystal data Chemical formula [AuCo 2 Fe 2 (C 5 H 5 ) 4 (C 13 H 11 N 3 ) 2 ]- (PF 6 ) 1.2 (CF 3 O 3 S) 1.8 M r Crystal system, space group Triclinic, P1 Temperature (K) 173 a, b, c (Å) (6), (7), (7),, ( ) (1), (1), (1) V (Å 3 ) (2) Z 2 Radiation type Mo K (mm 1 ) 4.13 Crystal size (mm) Figure 1 The structure of the title compound, with displacement ellipsoids drawn at the 30% probability level for non-h atoms (the disordered counterions were omitted for clarity). fluoridophosphate trifluoromethanesulfonate (Vanicek et al., 2018) with 0.37 ml of a freshly prepared 0.5 M thallium ethoxide THF solution (0.186 mmol, 1 equiv.) in 35 ml of THF (abs) at 80 C with the exclusion of light and under protection from air by an argon atmosphere. The reaction mixture was allowed to warm to 60 C and g (0.186 mmol, 1 equiv.) of chlorido(triphenylphosphine)gold(i) was added. After warming to room temperature, the reaction was Data collection Diffractometer Bruker D8 QUEST PHOTON 100 Absorption correction Multi-scan (SADABS; Bruker, 2014) T min, T max 0.697, No. of measured, independent and 99685, 9826, 9103 observed [I > 2(I)] reflections R int (sin /) max (Å 1 ) Refinement R[F 2 >2(F 2 )], wr(f 2 ), S 0.032, 0.080, 1.03 No. of reflections 9826 No. of parameters 796 No. of restraints 14 H-atom treatment H-atom parameters constrained max, min (e Å 3 ) 1.15, 0.97 Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXT2014 (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b)Mercury (Macrae et al., 2008), and WinGX (Farrugia 2012). completed overnight. Precipitated thallium chloride was filtered off via syringe filtration, 300 ml of diethyl ether was added and the orange product was allowed to precipitate at 20 C for 2 h. The orange powder was filtered off through a Büchner funnel and washed thoroughly with three portions of diethyl ether. Meanwhile, the oily product was washed out of the funnel with acetone and the solvent was removed on a rotary evaporator. Drying in vacuo provided an orange oily foam, representing a product mixture containing various hetero- and homoleptic triazolylidene complexes from the 1 H, 13 C NMR and mass spectra. Single crystals of the title compound were obtained at 4 C via diffusion crystallization in acetone out of diethyl ether. Figure 2 The arrangement of molecular entities of the tricationic title compound in the unit cell (the counter-ions were omitted for clarity). [Symmetry code: 1 x, 1 y, 1 z.] Refinement Crystal data, data collection and structure refinement details are summarized in Table 1. Specifically, the structure contains a statistical mixture of hexafluoridophosphate and trifluoromethanesulfonate anions with different distributions over three positions. The overall ratio of PF 6 /CF 3 SO 3 is approximately 1.2/1.8, leading to many nearly overlapping positions. The PF 6 anions seem well ordered; however, in one instance they were refined with restrained bond distances. At two of the three positions, the trifluoromethanesulfonate anions show additional positional disorder effects. Most of the C, F 2of3 Vanicek et al. [AuCo 2 Fe 2 (C 5 H 5 ) 4 (C 13 H 11 N 3 ) 2 ](PF 6 ) 1.2 (CF 3 O 3 S) 1.8

3 and O atoms were therefore refined with isotropic displacement parameters. The P and S atoms could be refined anisotropically, except for P2 and S2B with occupancies of 20% and 15% respectively. EADP/EXYZ commands were used to accommodate overlapping O- and F-atom positions in the case of the trifluoromethanesulfonate S2B. Funding information The presented work was supported by the Austrian Science Fund (FWF), P NBL and J References Bruker (2014). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Farrugia, L. J. (2012). J. Appl. Cryst. 45, Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, Sheldrick, G. M. (2015a). Acta Cryst. A71, 3 8. Sheldrick, G. M. (2015b). Acta Cryst. C71, 3 8. Vanicek, S., Podewitz, M., Stubbe, J., Schulze, D., Kopacka, H., Wurst, K., Müller, T., Lippmann, P., Haslinger, S., Schottenberger, H., Liedl, K. R., Ott, I., Sarkar, B. & Bildstein, B. (2018). Chem. Eur. J. 24, Vanicek et al. [AuCo 2 Fe 2 (C 5 H 5 ) 4 (C 13 H 11 N 3 ) 2 ](PF 6 ) 1.2 (CF 3 O 3 S) 1.8 3of3

4 full crystallographic data [ Bis(4-cobaltoceniumyl-1-ferrocenyl-3-methyl-1,2,3-triazolylidene)gold(I) hexafluoridophosphate trifluoromethanesulfonate (1.2/1.8) Stefan Vanicek, Klaus Wurst, Holger Kopacka and Benno Bildstein Bis(4-cobaltoceniumyl-1-ferrocenyl-3-methyl-1,2,3-triazolylidene)gold(I) hexafluoridophosphate triflate (1.2/1.8) Crystal data [AuCo 2 Fe 2 (C 5 H 5 ) 4 (C 13 H 11 N 3 ) 2 ](PF 6 ) 1.2 (CF 3 O 3 S) 1.8 M r = Triclinic, P1 a = (6) Å b = (7) Å c = (7) Å α = (1) β = (1) γ = (1) V = (2) Å 3 Data collection Bruker D8 QUEST PHOTON 100 diffractometer Radiation source: Incoatec Microfocus Multi layered optics monochromator Detector resolution: 10.4 pixels mm -1 φ and ω scans Absorption correction: multi-scan (SADABS; Bruker, 2014) T min = 0.697, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 796 parameters 14 restraints Z = 2 F(000) = 1518 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 9667 reflections θ = µ = 4.13 mm 1 T = 173 K Prism, orange mm measured reflections 9826 independent reflections 9103 reflections with I > 2σ(I) R int = θ max = 25.5, θ min = 2.1 h = k = l = Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0385P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 1.15 e Å 3 Δρ min = 0.97 e Å 3 data-1

5 Special details Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. Refinement. statistical mixture of PF6/triflate anions with different distribution over three positions. The ratio PF6/triflate is around 1.2/1.8, whereas many nearly overlying positions are formed. The PF6 anions seem well ordered, but must be refined in one case with restrained bond distances. At two of the three positions the triflate anions show additional positional disordered effects. Most of the C-, F- and O-atoms were refined with isotropic displacement parameters.the P- and S-atoms could be refined anisotropically, except for P2 and S2B with occupancies of 20% and 15%. EADP/EXYZ orders were used for overlying O- and F-positions at triflate S2B. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Occ. (<1) Au (2) (2) (2) (6) Co (6) (6) (4) (17) Co (5) (6) (3) (15) Fe (8) (7) (6) (2) Fe (7) (5) (4) (17) N (4) (3) (2) (9) N (4) (3) (3) (11) N (4) (3) (3) (11) N (3) (3) (2) (8) N (4) (3) (3) (12) N (4) (3) (3) (11) C (8) (7) (6) (3) H * C (9) (8) (5) (3) H * C (11) (9) (8) (4) H * C (11) (7) (7) (4) H * C (8) (7) (5) (3) H * C (6) (4) (4) (14) H * C (6) (5) (5) (18) H * C (6) (6) (5) (2) H * C (5) (5) (4) (17) H * C (5) (4) (3) (12) C (4) (3) (3) (9) C (4) (3) (3) (10) C (5) (4) (3) (11) C (6) (4) (4) (16) data-2

6 H * C (6) (5) (4) (17) H * C (5) (4) (3) (13) H * C (5) (4) (3) (11) H * C (7) (9) (4) (3) H * C (7) (8) (4) (3) H * C (6) (7) (4) (2) H * C (6) (7) (4) (2) H * C (7) (8) (4) (2) H * C (7) (4) (4) (2) H23A * H23B * H23C * C (7) (6) (4) (2) H * C (7) (5) (3) (18) H * C (7) (5) (4) (17) H * C (6) (5) (4) (17) H * C (6) (5) (4) (19) H * C (4) (3) (3) (10) H * C (5) (4) (3) (12) H * C (5) (4) (3) (13) H * C (5) (4) (3) (12) H * C (4) (3) (3) (10) C (4) (3) (2) (9) C (4) (3) (3) (10) C (4) (4) (3) (10) C (5) (4) (3) (14) H * C (5) (5) (3) (14) H * C (5) (5) (3) (12) data-3

7 H * C (4) (4) (3) (10) H * C (5) (6) (3) (17) H * C (5) (6) (4) (19) H * C (5) (6) (3) (18) H * C (6) (5) (4) (16) H * C (6) (5) (3) (16) H * C (7) (4) (4) (2) H53A * H53B * H53C * P (10) (7) (6) (3) 0.4 F (12) (12) (7) (4)* 0.4 F (8) (7) (5) (19)* 0.4 F (14) (10) (8) (3)* 0.4 F (2) (19) (16) (8)* 0.4 F (12) (11) (8) (4)* 0.4 F (7) (6) (5) (2)* 0.4 S (8) (6) (4) (2) 0.3 O1A (3) (3) (2) (11)* 0.3 O2A (2) (19) (14) (8)* 0.3 O3A (14) (12) (8) (4)* 0.3 C53A (2) (2) (15) (6)* 0.3 F1A (15) (13) (10) (4)* 0.3 F2A (17) (16) (12) (5)* 0.3 F3A (13) (11) (8) (3)* 0.3 S1B (8) (6) (4) (2) 0.3 O1B (10) (9) (6) (3)* 0.3 O2B (17) (14) (11) (5)* 0.3 O3B (17) (15) (10) (5)* 0.3 C53B (2) (18) (13) (5)* 0.3 F1B (16) (14) (11) (5)* 0.3 F2B (2) (19) (16) (7)* 0.3 F3B (13) (12) (8) (4)* 0.3 P (7) (9) (4) (19)* 0.2 F (18) (16) (11) (7)* 0.2 F (2) (2) (12) (7)* 0.2 F (2) (3) (2) (16)* 0.2 F (2) (3) (18) (9)* 0.2 F (4) (3) (3) (17)* 0.2 F (3) (2) (2) (12)* 0.2 S (2) (2) (14) (6) 0.65 data-4

8 O (8) (10) (5) (3) 0.65 O (13) (9) (6) (4) 0.65 O (14) (11) (10) (6) 0.65 C (13) (8) (7) (6) 0.65 F4A (12) (10) (8) (7) 0.65 F5A (8) (6) (4) (3) 0.65 F6A (13) (6) (6) (6) 0.65 S2B (13) (12) (9) (3)* 0.15 O4B (4) (3) (2) (8)* 0.15 O5B (8) (6) (4) (3) 0.15 O6B (12) (10) (8) (7) 0.15 C54B (3) (16) (15) 0.11 (2)* 0.15 F4B (13) (6) (6) (6) 0.15 F5B (18) (16) (11) (7)* 0.15 F6B (2) (3) (2) (16)* 0.15 P (5) (5) (5) (2) 0.6 F (18) (15) (12) (8)* 0.6 F (14) (12) (10) (5)* 0.6 F (2) (19) (15) (11)* 0.6 F (9) (9) (6) (3)* 0.6 F (9) (8) (6) (3)* 0.6 F (10) (9) (7) (3)* 0.6 S (13) (19) (9) (15) 0.4 O (16) (15) (10) (5)* 0.4 O (18) (15) (12) (6)* 0.4 O (2) (19) (14) (7)* 0.4 C (3) (3) (18) (7)* 0.4 F7A (18) (17) (11) (6)* 0.4 F8A (15) (13) (10) (5)* 0.4 F9A (14) (13) (9) (4)* 0.4 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Au (9) (9) (9) (6) (6) (6) Co (3) (4) (4) (3) (3) (3) Co (3) (4) (3) (3) (2) (3) Fe (5) (5) (6) (4) (4) (4) Fe (4) (4) (4) (3) (3) (3) N (2) (19) (2) (16) (17) (16) N (3) (2) (3) (2) (2) (18) N (3) (2) (2) (2) (2) (17) N (2) (18) (2) (15) (16) (15) N (3) (2) (3) (2) (2) (18) N (3) (2) (3) (19) (2) (18) C (6) (6) (6) (5) (5) (5) C (6) (7) (6) (6) (5) (5) C (9) (8) (10) (7) (8) (8) data-5

9 C (8) (5) (10) (5) (7) (6) C (5) (5) (6) (4) (4) (5) C (4) (3) (4) (3) (3) (3) C (3) (4) (5) (3) (3) (4) C (4) (4) (7) (3) (4) (4) C (3) (3) (5) (3) (3) (3) C (3) (2) (3) (2) (2) (2) C (2) (2) (2) (18) (18) (17) C (3) (2) (2) (19) (2) (18) C (3) (2) (3) (2) (2) (19) C (4) (3) (4) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (4) (3) (3) (3) (2) (2) C (3) (3) (3) (2) (2) (2) C (5) (10) (3) (6) (3) (4) C (4) (8) (5) (5) (4) (5) C (4) (7) (4) (4) (3) (4) C (4) (6) (4) (4) (3) (4) C (4) (8) (4) (5) (3) (5) C (5) (3) (4) (3) (4) (3) C (5) (5) (4) (4) (4) (4) C (6) (4) (3) (4) (3) (3) C (4) (4) (3) (3) (3) (3) C (5) (3) (4) (3) (3) (3) C (4) (4) (4) (3) (3) (3) C (3) (2) (2) (19) (19) (18) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (3) (3) (3) (2) (2) (2) C (2) (2) (2) (19) (19) (18) C (2) (2) (2) (17) (17) (17) C (2) (2) (2) (18) (18) (18) C (2) (2) (2) (19) (19) (19) C (3) (3) (3) (2) (2) (2) C (3) (4) (3) (3) (2) (3) C (3) (3) (2) (3) (2) (2) C (2) (3) (2) (2) (18) (19) C (3) (5) (3) (4) (3) (3) C (3) (6) (3) (4) (3) (4) C (3) (6) (3) (4) (2) (3) C (4) (5) (3) (4) (3) (3) C (3) (4) (3) (3) (3) (3) C (6) (3) (4) (3) (4) (3) P (5) (3) (4) (3) (3) (2) S (5) (3) (5) (3) (3) (3) S1B (5) (3) (5) (3) (3) (3) S (17) (13) (14) (12) (11) (10) O (5) (9) (5) (6) (4) (5) data-6

10 O (11) (8) (6) (8) (7) (6) O (8) (6) (15) (5) (10) (7) C (17) (6) (10) (9) (10) (7) F4A (13) (11) (14) (11) (11) (10) F5A (8) (5) (5) (5) (5) (4) F6A (16) (4) (8) (7) (8) (5) O5B (8) (5) (5) (5) (5) (4) O6B (13) (11) (14) (11) (11) (10) F4B (16) (4) (8) (7) (8) (5) P (3) (5) (5) (3) (3) (4) S (11) 0.64 (4) (14) (18) (11) 0.35 (2) Geometric parameters (Å, º) Au1 C (4) C31 C (10) Au1 C (4) C31 C (10) Co1 C (6) C31 H Co1 C (5) C32 C (9) Co1 C (6) C32 H Co1 C (6) C33 C (9) Co1 C (5) C33 H Co1 C (7) C34 C (10) Co1 C (5) C34 H Co1 C (7) C35 H Co1 C (6) C36 C (6) Co1 C (5) C36 C (7) Co2 C (5) C36 H Co2 C (5) C37 C (8) Co2 C (5) C37 H Co2 C (5) C38 C (7) Co2 C (4) C38 H Co2 C (5) C39 C (7) Co2 C (6) C39 H Co2 C (6) C41 C (6) Co2 C (6) C42 C (6) Co2 C (5) C43 C (7) Fe1 C (5) C43 C (7) Fe1 C (7) C44 C (8) Fe1 C (5) C44 H Fe1 C (7) C45 C (8) Fe1 C (8) C45 H Fe1 C (7) C46 C (7) Fe1 C (6) C46 H Fe1 C (8) C47 H Fe1 C (7) C48 C (9) Fe1 C (8) C48 C (9) Fe2 C (4) C48 H Fe2 C (5) C49 C (9) data-7

11 Fe2 C (6) C49 H Fe2 C (5) C50 C (9) Fe2 C (5) C50 H Fe2 C (7) C51 C (8) Fe2 C (4) C51 H Fe2 C (6) C52 H Fe2 C (6) C53 H53A Fe2 C (5) C53 H53B N1 N (6) C53 H53C N1 C (6) P1 F (14) N1 C (7) P1 F (16) N2 N (7) P1 F (12) N3 C (6) P1 F (3) N3 C (7) P1 F (17) N4 N (5) P1 F (19) N4 C (6) S1 O2A 1.39 (3) N4 C (6) S1 O3A (18) N5 N (6) S1 O1A 1.69 (4) N6 C (6) S1 C53A 1.72 (3) N6 C (6) O1A O2A 1.43 (4) C1 C (12) C53A F3A 1.14 (3) C1 C (12) C53A F1A 1.22 (3) C1 H C53A F2A 1.48 (3) C2 C (15) S1B O1B (14) C2 H S1B O2B 1.43 (2) C3 C (15) S1B O3B 1.66 (2) C3 H S1B C53B 1.80 (2) C4 C (13) C53B F3B 1.21 (2) C4 H C53B F1B 1.30 (3) C5 H C53B F2B 1.36 (3) C6 C (8) P2 F (2) C6 C (8) P2 F (2) C6 H P2 F (3) C7 C (11) P2 F (2) C7 H P2 F (3) C8 C (10) P2 F (18) C8 H S2 O (12) C9 C (8) S2 O (8) C9 H S2 O (8) C11 C (6) S2 C (10) C12 C (7) C54 F4A (14) C13 C (7) C54 F6A (14) C13 C (7) C54 F5A (12) C14 C (9) S2B O5B (16) C14 H S2B O6B (17) C15 C (8) S2B O4B 1.66 (5) C15 H S2B C54B 1.69 (2) C16 C (7) C54B F6B (19) data-8

12 C16 H C54B F5B (18) C17 H C54B F4B (18) C18 C (12) P3 F (12) C18 C (11) P3 F (13) C18 H P3 F (3) C19 C (10) P3 F (11) C19 H P3 F (2) C20 C (11) P3 F (16) C20 H S3 O (2) C21 C (9) S3 O (3) C21 H S3 O (2) C22 H S3 C (3) C23 H23A C55 F9A 0.96 (3) C23 H23B C55 F7A 1.50 (4) C23 H23C C55 F8A 1.54 (3) C41 Au1 C (17) C17 C16 H C14 Co1 C (2) Co1 C16 H C14 Co1 C (4) C16 C17 C (4) C15 Co1 C (4) C16 C17 Co (3) C14 Co1 C (3) C13 C17 Co (3) C15 Co1 C (3) C16 C17 H C18 Co1 C (3) C13 C17 H C14 Co1 C (2) Co1 C17 H C15 Co1 C (2) C22 C18 C (6) C18 Co1 C (2) C22 C18 Co (4) C20 Co1 C (3) C19 C18 Co (4) C14 Co1 C (3) C22 C18 H C15 Co1 C (3) C19 C18 H C18 Co1 C (3) Co1 C18 H C20 Co1 C (3) C18 C19 C (8) C17 Co1 C (3) C18 C19 Co (4) C14 Co1 C (2) C20 C19 Co (4) C15 Co1 C (2) C18 C19 H C18 Co1 C (3) C20 C19 H C20 Co1 C (3) Co1 C19 H C17 Co1 C (2) C21 C20 C (6) C21 Co1 C (3) C21 C20 Co (4) C14 Co1 C (3) C19 C20 Co (4) C15 Co1 C (3) C21 C20 H C18 Co1 C (3) C19 C20 H C20 Co1 C (3) Co1 C20 H C17 Co1 C (3) C22 C21 C (8) C21 Co1 C (3) C22 C21 Co (4) C16 Co1 C (3) C20 C21 Co (4) C14 Co1 C (4) C22 C21 H C15 Co1 C (3) C20 C21 H C18 Co1 C (3) Co1 C21 H data-9

13 C20 Co1 C (3) C18 C22 C (7) C17 Co1 C (2) C18 C22 Co (4) C21 Co1 C (4) C21 C22 Co (4) C16 Co1 C (3) C18 C22 H C22 Co1 C (4) C21 C22 H C14 Co1 C (2) Co1 C22 H C15 Co1 C (2) N3 C23 H23A C18 Co1 C (2) N3 C23 H23B C20 Co1 C (3) H23A C23 H23B C17 Co1 C (19) N3 C23 H23C C21 Co1 C (2) H23A C23 H23C C16 Co1 C (2) H23B C23 H23C C22 Co1 C (2) C32 C31 C (6) C19 Co1 C (3) C32 C31 Fe (4) C46 Co2 C (2) C35 C31 Fe (4) C46 Co2 C (2) C32 C31 H C49 Co2 C (3) C35 C31 H C46 Co2 C (2) Fe2 C31 H C49 Co2 C (3) C31 C32 C (6) C50 Co2 C (2) C31 C32 Fe (4) C46 Co2 C (19) C33 C32 Fe (4) C49 Co2 C (2) C31 C32 H C50 Co2 C (2) C33 C32 H C45 Co2 C (2) Fe2 C32 H C46 Co2 C (3) C32 C33 C (6) C49 Co2 C (3) C32 C33 Fe (3) C50 Co2 C (2) C34 C33 Fe (3) C45 Co2 C (3) C32 C33 H C47 Co2 C (2) C34 C33 H C46 Co2 C (2) Fe2 C33 H C49 Co2 C (3) C33 C34 C (6) C50 Co2 C (3) C33 C34 Fe (3) C45 Co2 C (2) C35 C34 Fe (3) C47 Co2 C (2) C33 C34 H C48 Co2 C (3) C35 C34 H C46 Co2 C (2) Fe2 C34 H C49 Co2 C (3) C34 C35 C (6) C50 Co2 C (3) C34 C35 Fe (4) C45 Co2 C (2) C31 C35 Fe (4) C47 Co2 C (2) C34 C35 H C48 Co2 C (3) C31 C35 H C44 Co2 C (2) Fe2 C35 H C46 Co2 C (3) C40 C36 C (4) C49 Co2 C (3) C40 C36 Fe (3) C50 Co2 C (3) C37 C36 Fe (3) C45 Co2 C (3) C40 C36 H C47 Co2 C (2) C37 C36 H C48 Co2 C (3) Fe2 C36 H data-10

14 C44 Co2 C (2) C38 C37 C (4) C51 Co2 C (2) C38 C37 Fe (3) C46 Co2 C (2) C36 C37 Fe (3) C49 Co2 C (2) C38 C37 H C50 Co2 C (3) C36 C37 H C45 Co2 C (2) Fe2 C37 H C47 Co2 C (19) C37 C38 C (4) C48 Co2 C (2) C37 C38 Fe (3) C44 Co2 C (19) C39 C38 Fe (3) C51 Co2 C (2) C37 C38 H C52 Co2 C (2) C39 C38 H C10 Fe1 C (3) Fe2 C38 H C10 Fe1 C (2) C40 C39 C (5) C1 Fe1 C (3) C40 C39 Fe (3) C10 Fe1 C (3) C38 C39 Fe (3) C1 Fe1 C (4) C40 C39 H C6 Fe1 C (3) C38 C39 H C10 Fe1 C (4) Fe2 C39 H C1 Fe1 C (4) C36 C40 C (4) C6 Fe1 C (4) C36 C40 N (4) C5 Fe1 C (4) C39 C40 N (4) C10 Fe1 C (3) C36 C40 Fe (3) C1 Fe1 C (4) C39 C40 Fe (3) C6 Fe1 C (3) N4 C40 Fe (3) C5 Fe1 C (4) N4 C41 C (4) C2 Fe1 C (4) N4 C41 Au (3) C10 Fe1 C (2) C42 C41 Au (3) C1 Fe1 C (4) N6 C42 C (4) C6 Fe1 C (2) N6 C42 C (4) C5 Fe1 C (4) C41 C42 C (4) C2 Fe1 C (4) C47 C43 C (4) C8 Fe1 C (3) C47 C43 C (4) C10 Fe1 C (5) C44 C43 C (5) C1 Fe1 C (4) C47 C43 Co (3) C6 Fe1 C (5) C44 C43 Co (3) C5 Fe1 C (4) C42 C43 Co (3) C2 Fe1 C (4) C45 C44 C (5) C8 Fe1 C (4) C45 C44 Co (3) C7 Fe1 C (4) C43 C44 Co (3) C10 Fe1 C (2) C45 C44 H C1 Fe1 C (4) C43 C44 H C6 Fe1 C (2) Co2 C44 H C5 Fe1 C (3) C46 C45 C (4) C2 Fe1 C (4) C46 C45 Co (3) C8 Fe1 C (3) C44 C45 Co (3) C7 Fe1 C (3) C46 C45 H C3 Fe1 C (4) C44 C45 H C10 Fe1 C (4) Co2 C45 H data-11

15 C1 Fe1 C (4) C45 C46 C (5) C6 Fe1 C (4) C45 C46 Co (3) C5 Fe1 C (4) C47 C46 Co (3) C2 Fe1 C (5) C45 C46 H C8 Fe1 C (4) C47 C46 H C7 Fe1 C (4) Co2 C46 H C3 Fe1 C (4) C46 C47 C (4) C9 Fe1 C (4) C46 C47 Co (3) C40 Fe2 C (2) C43 C47 Co (3) C40 Fe2 C (2) C46 C47 H C33 Fe2 C (3) C43 C47 H C40 Fe2 C (2) Co2 C47 H C33 Fe2 C (3) C52 C48 C (5) C32 Fe2 C (3) C52 C48 Co (3) C40 Fe2 C (19) C49 C48 Co (3) C33 Fe2 C (3) C52 C48 H C32 Fe2 C (3) C49 C48 H C34 Fe2 C (3) Co2 C48 H C40 Fe2 C (2) C50 C49 C (6) C33 Fe2 C (3) C50 C49 Co (3) C32 Fe2 C (3) C48 C49 Co (3) C34 Fe2 C (3) C50 C49 H C39 Fe2 C (3) C48 C49 H C40 Fe2 C (18) Co2 C49 H C33 Fe2 C (2) C49 C50 C (5) C32 Fe2 C (2) C49 C50 Co (3) C34 Fe2 C (2) C51 C50 Co (3) C39 Fe2 C (2) C49 C50 H C31 Fe2 C (2) C51 C50 H C40 Fe2 C (2) Co2 C50 H C33 Fe2 C (3) C50 C51 C (6) C32 Fe2 C (3) C50 C51 Co (4) C34 Fe2 C (3) C52 C51 Co (3) C39 Fe2 C (3) C50 C51 H C31 Fe2 C (3) C52 C51 H C36 Fe2 C (2) Co2 C51 H C40 Fe2 C (19) C48 C52 C (6) C33 Fe2 C (3) C48 C52 Co (4) C32 Fe2 C (3) C51 C52 Co (3) C34 Fe2 C (3) C48 C52 H C39 Fe2 C (2) C51 C52 H C31 Fe2 C (3) Co2 C52 H C36 Fe2 C (2) N6 C53 H53A C35 Fe2 C (3) N6 C53 H53B C40 Fe2 C (18) H53A C53 H53B C33 Fe2 C (2) N6 C53 H53C C32 Fe2 C (2) H53A C53 H53C C34 Fe2 C (2) H53B C53 H53C data-12

16 C39 Fe2 C (2) F2 P1 F (10) C31 Fe2 C (3) F2 P1 F (8) C36 Fe2 C (19) F3 P1 F (9) C35 Fe2 C (3) F2 P1 F (11) C38 Fe2 C (2) F3 P1 F (14) N2 N1 C (4) F6 P1 F (10) N2 N1 C (4) F2 P1 F (7) C11 N1 C (4) F3 P1 F (8) N3 N2 N (4) F6 P1 F (11) N2 N3 C (4) F4 P1 F (11) N2 N3 C (5) F2 P1 F (10) C12 N3 C (5) F3 P1 F (8) N5 N4 C (4) F6 P1 F (7) N5 N4 C (4) F4 P1 F (11) C41 N4 C (4) F5 P1 F (8) N6 N5 N (4) O2A S1 O3A (13) N5 N6 C (4) O2A S1 O1A 54.4 (16) N5 N6 C (5) O3A S1 O1A 84.4 (13) C42 N6 C (5) O2A S1 C53A (14) C5 C1 C (9) O3A S1 C53A (13) C5 C1 Fe (4) O1A S1 C53A 76.2 (16) C2 C1 Fe (5) O2A O1A S (16) C5 C1 H S1 O2A O1A 73.6 (19) C2 C1 H F3A C53A F1A 116 (2) Fe1 C1 H F3A C53A F2A 107 (2) C3 C2 C (10) F1A C53A F2A 98 (2) C3 C2 Fe (5) F3A C53A S (19) C1 C2 Fe (4) F1A C53A S1 122 (2) C3 C2 H F2A C53A S (17) C1 C2 H O1B S1B O2B 97.3 (10) Fe1 C2 H O1B S1B O3B 85.0 (10) C2 C3 C (10) O2B S1B O3B (12) C2 C3 Fe (5) O1B S1B C53B (10) C4 C3 Fe (5) O2B S1B C53B (12) C2 C3 H O3B S1B C53B (10) C4 C3 H F3B C53B F1B 107 (2) Fe1 C3 H F3B C53B F2B 98 (2) C5 C4 C (11) F1B C53B F2B 103 (2) C5 C4 Fe (5) F3B C53B S1B (16) C3 C4 Fe (6) F1B C53B S1B (17) C5 C4 H F2B C53B S1B (19) C3 C4 H F8 P2 F (16) Fe1 C4 H F8 P2 F (18) C4 C5 C (10) F10 P2 F (18) C4 C5 Fe (5) F8 P2 F (15) C1 C5 Fe (5) F10 P2 F (18) C4 C5 H F12 P2 F (18) C1 C5 H F8 P2 F (2) data-13

17 Fe1 C5 H F10 P2 F (2) C10 C6 C (6) F12 P2 F (2) C10 C6 Fe (3) F9 P2 F11 71 (2) C7 C6 Fe (3) F8 P2 F (13) C10 C6 H F10 P2 F (14) C7 C6 H F12 P2 F (17) Fe1 C6 H F9 P2 F (15) C8 C7 C (6) F11 P2 F (18) C8 C7 Fe (4) O6 S2 O (9) C6 C7 Fe (3) O6 S2 O (10) C8 C7 H O4 S2 O (8) C6 C7 H O6 S2 C (8) Fe1 C7 H O4 S2 C (7) C9 C8 C (6) O5 S2 C (6) C9 C8 Fe (4) F4A C54 F6A (12) C7 C8 Fe (4) F4A C54 F5A (12) C9 C8 H F6A C54 F5A (11) C7 C8 H F4A C54 S (8) Fe1 C8 H F6A C54 S (9) C8 C9 C (6) F5A C54 S (7) C8 C9 Fe (4) O5B S2B O6B 86.3 (10) C10 C9 Fe (3) O5B S2B O4B (16) C8 C9 H O6B S2B O4B (18) C10 C9 H O5B S2B C54B 98.0 (12) Fe1 C9 H O6B S2B C54B 92.5 (13) C6 C10 N (5) O4B S2B C54B (19) C6 C10 C (5) F6B C54B F5B 103 (2) N1 C10 C (5) F6B C54B F4B 115 (2) C6 C10 Fe (3) F5B C54B F4B 134 (2) N1 C10 Fe (3) F6B C54B S2B 96.7 (19) C9 C10 Fe (3) F5B C54B S2B (18) N1 C11 C (4) F4B C54B S2B 91.8 (14) N1 C11 Au (3) F16 P3 F (6) C12 C11 Au (3) F16 P3 F (11) N3 C12 C (4) F18 P3 F (11) N3 C12 C (4) F16 P3 F (7) C11 C12 C (4) F18 P3 F (7) C17 C13 C (5) F15 P3 F (10) C17 C13 C (4) F16 P3 F (8) C14 C13 C (4) F18 P3 F (9) C17 C13 Co (3) F15 P3 F (12) C14 C13 Co (3) F17 P3 F (8) C12 C13 Co (3) F16 P3 F (8) C15 C14 C (5) F18 P3 F (7) C15 C14 Co (3) F15 P3 F (11) C13 C14 Co (3) F17 P3 F (7) C15 C14 H F13 P3 F (8) C13 C14 H O8 S3 O (17) data-14

18 Co1 C14 H O8 S3 O7 105 (2) C14 C15 C (5) O9 S3 O (13) C14 C15 Co (3) O8 S3 C (15) C16 C15 Co (3) O9 S3 C (2) C14 C15 H O7 S3 C (14) C16 C15 H F9A C55 F7A 122 (3) Co1 C15 H F9A C55 F8A 132 (3) C15 C16 C (5) F7A C55 F8A 82.6 (18) C15 C16 Co (3) F9A C55 S3 108 (3) C17 C16 Co (3) F7A C55 S (19) C15 C16 H F8A C55 S3 108 (2) C11 N1 N2 N3 0.5 (5) C37 C38 C39 C (6) C10 N1 N2 N (4) Fe2 C38 C39 C (3) N1 N2 N3 C (6) C37 C38 C39 Fe (4) N1 N2 N3 C (5) C37 C36 C40 C (5) C41 N4 N5 N6 0.8 (6) Fe2 C36 C40 C (3) C40 N4 N5 N (4) C37 C36 C40 N (4) N4 N5 N6 C (6) Fe2 C36 C40 N (5) N4 N5 N6 C (6) C37 C36 C40 Fe (3) C5 C1 C2 C3 0.5 (9) C38 C39 C40 C (6) Fe1 C1 C2 C (6) Fe2 C39 C40 C (3) C5 C1 C2 Fe (5) C38 C39 C40 N (4) C1 C2 C3 C4 1.1 (10) Fe2 C39 C40 N (4) Fe1 C2 C3 C (6) C38 C39 C40 Fe (4) C1 C2 C3 Fe (5) N5 N4 C40 C (5) C2 C3 C4 C5 1.2 (10) C41 N4 C40 C (7) Fe1 C3 C4 C (6) N5 N4 C40 C (7) C2 C3 C4 Fe (6) C41 N4 C40 C (5) C3 C4 C5 C1 0.8 (9) N5 N4 C40 Fe (6) Fe1 C4 C5 C (5) C41 N4 C40 Fe (4) C3 C4 C5 Fe (6) N5 N4 C41 C (5) C2 C1 C5 C4 0.2 (8) C40 N4 C41 C (4) Fe1 C1 C5 C (5) N5 N4 C41 Au (4) C2 C1 C5 Fe (5) C40 N4 C41 Au1 5.6 (6) C10 C6 C7 C8 0.9 (7) N5 N6 C42 C (6) Fe1 C6 C7 C (5) C53 N6 C42 C (6) C10 C6 C7 Fe (4) N5 N6 C42 C (5) C6 C7 C8 C9 0.9 (8) C53 N6 C42 C (9) Fe1 C7 C8 C (5) N4 C41 C42 N6 1.4 (5) C6 C7 C8 Fe (4) Au1 C41 C42 N (4) C7 C8 C9 C (7) N4 C41 C42 C (5) Fe1 C8 C9 C (4) Au1 C41 C42 C (8) C7 C8 C9 Fe (5) N6 C42 C43 C (5) C7 C6 C10 N (5) C41 C42 C43 C (8) Fe1 C6 C10 N (5) N6 C42 C43 C (8) C7 C6 C10 C9 0.6 (6) C41 C42 C43 C (5) Fe1 C6 C10 C (4) N6 C42 C43 Co (5) data-15

19 C7 C6 C10 Fe (4) C41 C42 C43 Co (7) N2 N1 C10 C (5) C47 C43 C44 C (6) C11 N1 C10 C (8) C42 C43 C44 C (5) N2 N1 C10 C (7) Co2 C43 C44 C (4) C11 N1 C10 C (5) C47 C43 C44 Co (3) N2 N1 C10 Fe (6) C42 C43 C44 Co (5) C11 N1 C10 Fe (5) C43 C44 C45 C (7) C8 C9 C10 C6 0.0 (6) Co2 C44 C45 C (4) Fe1 C9 C10 C (4) C43 C44 C45 Co (4) C8 C9 C10 N (5) C44 C45 C46 C (6) Fe1 C9 C10 N (5) Co2 C45 C46 C (3) C8 C9 C10 Fe (4) C44 C45 C46 Co (4) N2 N1 C11 C (5) C45 C46 C47 C (6) C10 N1 C11 C (5) Co2 C46 C47 C (3) N2 N1 C11 Au (3) C45 C46 C47 Co (4) C10 N1 C11 Au1 3.1 (7) C44 C43 C47 C (5) N2 N3 C12 C (6) C42 C43 C47 C (4) C23 N3 C12 C (5) Co2 C43 C47 C (3) N2 N3 C12 C (4) C44 C43 C47 Co (4) C23 N3 C12 C (9) C42 C43 C47 Co (5) N1 C11 C12 N3 1.1 (5) C52 C48 C49 C (7) Au1 C11 C12 N (3) Co2 C48 C49 C (4) N1 C11 C12 C (5) C52 C48 C49 Co (4) Au1 C11 C12 C (8) C48 C49 C50 C (7) N3 C12 C13 C (5) Co2 C49 C50 C (4) C11 C12 C13 C (8) C48 C49 C50 Co (4) N3 C12 C13 C (8) C49 C50 C51 C (7) C11 C12 C13 C (6) Co2 C50 C51 C (4) N3 C12 C13 Co (4) C49 C50 C51 Co (4) C11 C12 C13 Co (7) C49 C48 C52 C (7) C17 C13 C14 C (7) Co2 C48 C52 C (4) C12 C13 C14 C (5) C49 C48 C52 Co (4) Co1 C13 C14 C (5) C50 C51 C52 C (6) C17 C13 C14 Co (4) Co2 C51 C52 C (4) C12 C13 C14 Co (5) C50 C51 C52 Co (4) C13 C14 C15 C (7) O3A S1 O1A O2A (17) Co1 C14 C15 C (4) C53A S1 O1A O2A (19) C13 C14 C15 Co (4) O3A S1 O2A O1A 74.0 (18) C14 C15 C16 C (7) C53A S1 O2A O1A 45 (2) Co1 C15 C16 C (4) O2A S1 C53A F3A 54 (2) C14 C15 C16 Co (5) O3A S1 C53A F3A (16) C15 C16 C17 C (6) O1A S1 C53A F3A 91 (2) Co1 C16 C17 C (3) O2A S1 C53A F1A 172 (2) C15 C16 C17 Co (4) O3A S1 C53A F1A 57 (2) C14 C13 C17 C (6) O1A S1 C53A F1A 136 (3) C12 C13 C17 C (5) O2A S1 C53A F2A 60 (2) Co1 C13 C17 C (4) O3A S1 C53A F2A 55.8 (19) C14 C13 C17 Co (4) O1A S1 C53A F2A 23.2 (19) data-16

20 C12 C13 C17 Co (5) O1B S1B C53B F3B 79.9 (17) C22 C18 C19 C (8) O2B S1B C53B F3B 45 (2) Co1 C18 C19 C (5) O3B S1B C53B F3B (14) C22 C18 C19 Co (5) O1B S1B C53B F1B (17) C18 C19 C20 C (9) O2B S1B C53B F1B 77 (2) Co1 C19 C20 C (5) O3B S1B C53B F1B 56 (2) C18 C19 C20 Co (5) O1B S1B C53B F2B 28 (2) C19 C20 C21 C (8) O2B S1B C53B F2B 154 (2) Co1 C20 C21 C (4) O3B S1B C53B F2B 74 (2) C19 C20 C21 Co (5) O6 S2 C54 F4A 62.3 (13) C19 C18 C22 C (8) O4 S2 C54 F4A (10) Co1 C18 C22 C (4) O5 S2 C54 F4A 51.0 (13) C19 C18 C22 Co (5) O6 S2 C54 F6A (11) C20 C21 C22 C (8) O4 S2 C54 F6A 54.6 (10) Co1 C21 C22 C (5) O5 S2 C54 F6A 70.2 (11) C20 C21 C22 Co (5) O6 S2 C54 F5A 53.2 (13) C35 C31 C32 C (7) O4 S2 C54 F5A 68.7 (11) Fe2 C31 C32 C (4) O5 S2 C54 F5A (12) C35 C31 C32 Fe (4) O5B S2B C54B F6B 74.6 (18) C31 C32 C33 C (7) O6B S2B C54B F6B (18) Fe2 C32 C33 C (4) O4B S2B C54B F6B 62 (2) C31 C32 C33 Fe (4) O5B S2B C54B F5B (18) C32 C33 C34 C (7) O6B S2B C54B F5B 92.7 (19) Fe2 C33 C34 C (4) O4B S2B C54B F5B 44 (3) C32 C33 C34 Fe (4) O5B S2B C54B F4B 41.1 (16) C33 C34 C35 C (7) O6B S2B C54B F4B 45.6 (15) Fe2 C34 C35 C (4) O4B S2B C54B F4B (18) C33 C34 C35 Fe (4) O8 S3 C55 F9A 48 (4) C32 C31 C35 C (7) O9 S3 C55 F9A 174 (3) Fe2 C31 C35 C (4) O7 S3 C55 F9A 67 (3) C32 C31 C35 Fe (4) O8 S3 C55 F7A 79 (3) C40 C36 C37 C (6) O9 S3 C55 F7A 59 (2) Fe2 C36 C37 C (4) O7 S3 C55 F7A 165 (2) C40 C36 C37 Fe (3) O8 S3 C55 F8A 164 (2) C36 C37 C38 C (6) O9 S3 C55 F8A 26 (3) Fe2 C37 C38 C (4) O7 S3 C55 F8A 81 (2) C36 C37 C38 Fe (3) data-17