research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

Crystal structure of [(1,2,3,4,11,12-η)-anthracene]tris­­(tri­methyl­stann­yl)cobalt(III)

aDepartment of Chemistry, 120 Trustee Road, University of Rochester, Rochester, NY 14627, USA, and bDepartment of Chemistry, 207 Pleasant Street SE, University of Minnesota, Minneapolis, MN 55455, USA
*Correspondence e-mail: brennessel@chem.rochester.edu

Edited by R. F. Baggio, Comisión Nacional de Energía Atómica, Argentina (Received 17 September 2014; accepted 1 October 2014; online 8 October 2014)

The asymmetric unit of the title structure, [Co(η6-C14H10){Sn(CH3)3}3], contains two independent mol­ecules. Each anthracene ligand is η6-coordinating to a CoIII cation and is nearly planar [fold angles of 5.4 (3) and 9.7 (3)°], as would be expected for its behaving almost entirely as a donor to a high-oxidation-state metal center. The slight fold in each anthracene ligand gives rise to slightly longer Co—C bond lengths to the ring junction carbon atoms than to the other four. Each CoIII cation is further coordinated by three Sn(CH3)3 ligands, giving each mol­ecule a three-legged piano-stool geometry. In each of the two independent mol­ecules, the trio of SnMe3 ligands are modeled as disordered over two positions, rotated by approximately 30%, such that the C atoms nearly overlap. In one mol­ecule, the disorder ratio refined to 0.9365 (8):0.0635 (8), while that for the other refined to 0.9686 (8):0.0314 (8). The mol­ecules are well separated, and thus no significant inter­molecular inter­actions are observed. The compound is of inter­est as the first structure report of an η6-anthracene cobalt(III) complex.

1. Chemical context

Oxidation derivatives of unstable low-valent species often provide indirect support for their formulations. For example, thermally unstable alkyl isocyanide complexes of formally M(−II) that were proposed to be `K2[M(CNtBu)4],' M = Fe (Brennessel et al., 2007[Brennessel, W. W., Jilek, R. E. & Ellis, J. E. (2007). Angew. Chem. Int. Ed. 46, 6132-6136.]), Ru (Corella et al., 1992[Corella, J. A. II, Thompson, R. L. & Cooper, N. J. (1992). Angew. Chem. Int. Ed. Engl. 31, 83-84.]), were reacted at low temperature in situ with SnPh3Cl to afford isolable and readily characterizable derivatives, trans-M(SnPh3)2(CNtBu)4. Similarly, it was planned to derivatize the formally Co(−I) anion [Co(C10H8)2], C10H8 = naphthalene, which is the analog of the well-characterized and isolable anthracene cobaltate [Co(C14H10)2] (C14H10 = anthracene; Brennessel et al., 2002[Brennessel, W. W., Ellis, J. E., Pomije, M. K., Sussman, V. J., Urnezius, E. & Young, V. G. Jr (2002). J. Am. Chem. Soc. 124, 10258-10259.]). To date, the only established instance of [Co(C10H8)2] is as part of the highly specific triple salt [K(18-crown-6)]3[Co(C10H8)(C2H4)2]2[Co(C10H8)2] (Brennes­sel et al., 2006[Brennessel, W. W., Young, V. G. Jr & Ellis, J. E. (2006). Angew. Chem. Int. Ed. 45, 7268-7271.]). But before applying this procedure to the naphthalene system, we chose to first apply it to the well-behaved anthracene system to test the feasibility of the deriv­atization. Thus, one equivalent of SnMe3Cl was added in situ to a THF solution of [K(THF)x][Co(C14H10)2] (Brennessel et al., 2002[Brennessel, W. W., Ellis, J. E., Pomije, M. K., Sussman, V. J., Urnezius, E. & Young, V. G. Jr (2002). J. Am. Chem. Soc. 124, 10258-10259.]), which produced an intense violet, pentane-soluble species. Rather than being the expected `[Co(C14H10)2(SnMe3)]' formally Co(I) species, however, after further investigation it was determined to be the title compound, [Co(η6-C14H10)(SnMe3)3] (I)[link], based on single-crystal X-ray diffraction.

[Scheme 1]

Similar reactions using SnPh3 and Sn(cyclo­hex­yl)3 produced only intra­ctable mixtures. Filtration of the reaction mixture left a very reactive dark-gray filter cake, which appeared to be from the deposition of Co metal. A tentative balanced equation has been proposed based on the initial evidence (see equation below). No yield was obtained, but if the equation holds, a qu­anti­tative yield would only be 33.3% based on cobalt. Single crystals were grown from a saturated pentane solution in a 243 K freezer and NMR experiments (see Synthesis and crystallization) were performed on the single crystals, which corroborated the structure analysis from diffraction data.

[Scheme 2]

2. Structural Commentary

The structure contains two independent mol­ecules of (I)[link] (Fig. 1[link]) that are metrically very similar. Each mol­ecule contains one anthracene and three SnMe3 ligands in a three-legged-piano-stool geometry. In each of the two independent mol­ecules, the trio of tin ligands are disordered with a 30° rotation of the set, although the minor component of the disorder is very small (<10% by mass in both cases). The anthracene ligands in both mol­ecules are coordinated in an η6 mode and are nearly planar, with only the slightest bends at the imaginary lines joining atoms C1 and C4 [5.4 (3)°] and C24 and C27 [9.7 (3)°]. The Co—C distances to the ring junction carbon atoms are slightly longer by 0.17 Å than those to the metal-coordinating non-ring junction atoms (Table 1[link]). This has been referred to as a `flat-slipped' coordination mode, and is likely due to an anti­bonding component of the anthracene HOMO at the ring-junction carbon atoms (Zhu et al., 2006[Zhu, G., Janak, K. E., Figueroa, J. S. & Parkin, G. (2006). J. Am. Chem. Soc. 128, 5452-5461.]). Thus the anthracene ligand is displaced slightly from the symmetric coordination mode found in η6-benzene metal complexes, in order to maximize the bonding overlaps with the four non-ring-junction carbon atoms. Because the metal is formally d6 CoIII, the π-donation from the anthracene ligand is likely the most important contribution to its bonding.

Table 1
Comparison of (I)[link] with free anthracene and selected `flat-slipped' structures (Å, °)

The numbering is according to Fig. 2[link]. For (I)[link] and the molybdenum complex, only one of the two independent mol­ecules for each is listed because they are metrically similar.

Feature (I) Anthracenea [(Cp")Ru(An)][PF6]b MoAn(PMe3)3c
M—C1 2.101 (5)   2.207 (4) 2.297 (3)
M—C2 2.102 (5)   2.217 (4) 2.261 (3)
M—C3 2.098 (5)   2.223 (4) 2.285 (3)
M—C4 2.132 (5)   2.210 (4) 2.268 (3)
M—C11 2.273 (5)   2.289 (4) 2.405 (3)
M—C21 2.274 (5)   2.283 (4) 2.424 (3)
         
Increase (avg.) 0.165   0.072 0.137
         
C1—C2 1.387 (7) 1.3675 (9) 1.399 (6) 1.407 (6)
C2—C3 1.423 (8) 1.4264 (10) 1.415 (7) 1.419 (7)
C3—C4 1.393 (9) 1.3674 (9) 1.398 (7) 1.408 (7)
C1—C11 1.438 (7) 1.4297 (8) 1.431 (6) 1.434 (6)
C4—C12 1.436 (7) 1.4295 (8) 1.441 (6) 1.452 (6)
C11—C12 1.449 (7) 1.4384 (8) 1.449 (5) 1.455 (6)
         
Fold angle 5.4 (3)   4.4 5.4
Notes: (a) unpublished structure determined locally; (b) Konovalov et al. (2011[Konovalov, A. I., Karslyan, E. E., Perekalin, D. S., Nelyubina, Y. V., Petrovskii, P. V. & Kudinov, A. R. (2011). Mendeleev Commun. 21, 163-164.]), Cp′′ = C5Me4(CH2OMe), An = anthracene; (c) Zhu et al. (2006[Zhu, G., Janak, K. E., Figueroa, J. S. & Parkin, G. (2006). J. Am. Chem. Soc. 128, 5452-5461.]).
[Figure 1]
Figure 1
The two independent mol­ecules of (I)[link], showing the atom numbering. The minor components of the disorder are shown with dashed lines and boundary ellipsoids. The two orientations of the SnMe3 ligand set fit in essentially the same volume because the methyl groups are overlapped. Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms have been omitted.

3. Database Survey

Structures of η6-coordinated anthracene transition metal complexes are few [Cambridge Structural Database, Version 5.35, update No. 3, May 2014; Groom & Allen, 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. Engl. 53, 662-671.]], but range from Ti (Seaburg et al., 1998[Seaburg, J. K., Fischer, P. J., Young, V. G. Jr & Ellis, J. E. (1998). Angew. Chem. Int. Ed. 37, 155-158.]) to Co (this work). Although one ligand in the titanium complex, [Ti(dmpe)(η4-C14H10)(η6-C14H10)] [dmpe = 1,2-bis(dimethylphosphino), is considered η6-coordinating based on Ti—C bond lengths, the fold angle between the plane consisting of non-ring-junction metal-coordinating carbon atoms and the rest of the ligand is nearly 20°, very likely placing it on the cusp of an η4 coordination mode. However, both [Cr(C14H10)(CO)3] (Hanic & Mills, 1968[Hanic, F. & Mills, O. S. (1968). J. Organomet. Chem. 11, 151-158.]) and [Mo(C14H10)(PMe3)3] (Zhu et al., 2006[Zhu, G., Janak, K. E., Figueroa, J. S. & Parkin, G. (2006). J. Am. Chem. Soc. 128, 5452-5461.]) have nearly planar anthracene ligands (6.6 and 5.5–5.8°, respectively). The small fold angles and the M—C(ring junction) bond lengths that are slightly longer than the M—C(non-ring junction) ones exemplify the `flat-slipped' coordination mode (Table 1[link]). For these cases of early transition metals, the π-donation of anthracene is supplemented by δ-backbonding to the anthracene LUMO; however, the C—C bond lengths are not all that different from those seen in normal-valent late transition metal complexes, and all are elongated relative to those in free anthracene (Table 1[link]).

In the structures of later transition metal compounds, the η6 `flat-slipped' coordination mode is found in normal- or slightly sub-valent metal complexes, and the fold angle appears to be sensitive to oxidation state. In structures with RuII coordination centers (Garcia et al., 2010[Garcia, M. H., Valente, A., Florindo, P., Morais, T. S., Piedade, M. F. M., Duarte, M. T., Moreno, V., Avilés, F. X. & Loreno, J. (2010). Inorg. Chim. Acta, 363, 3765-3775.]; Konovalov et al., 2011[Konovalov, A. I., Karslyan, E. E., Perekalin, D. S., Nelyubina, Y. V., Petrovskii, P. V. & Kudinov, A. R. (2011). Mendeleev Commun. 21, 163-164.]) the fold angles are 3.1 and 4.4°, respectively. As the oxidation state decreases, as in the cases of FeI (Schnöckelborg et al., 2012[Schnöckelborg, E.-M., Khusniyarov, M. M., de Bruin, B., Hartl, F., Langer, T., Eul, M., Schulz, S., Pöttgen, R. & Wolf, W. (2012). Inorg. Chem. 51, 6719-6730.]; Hatanaka et al., 2012[Hatanaka, T., Ohki, Y., Kamachi, T., Nakayama, T., Yoshizawa, K., Katada, M. & Tatsumi, K. (2012). Chem. Asian J. 7, 1231-1242.]) and RhI (Woolf et al., 2011[Woolf, A., Chaplin, A. B., McGrady, J. E., Alibadi, M. A. M., Rees, N., Draper, S., Murphy, F. & Weller, A. S. (2011). Eur. J. Inorg. Chem. pp. 1614-1625.]), the fold angles increase slightly to 15.8, 9.1, 9.2, and 13.8°, respectively. Although fold angles may be subject to a variety of additional effects, including packing and sterics, in general the trend is that these angles increase with greater electron-acceptor behavior. This has been examined for the series Cp*Fe(C14H10)(−/0/+) and Cp*Fe(C10H8)(−/0/+), Cp* = C5Me5, by a combination of X-ray crystallography and DFT methods (Schnöckelborg et al., 2012[Schnöckelborg, E.-M., Khusniyarov, M. M., de Bruin, B., Hartl, F., Langer, T., Eul, M., Schulz, S., Pöttgen, R. & Wolf, W. (2012). Inorg. Chem. 51, 6719-6730.]). In low oxidation states, the fold angles are significant and the ring-junction carbon atoms are bent away from the metal, thus making the coordination η4. Whereas the folds become almost non-existent (<10°) for normal valent oxidation states and the coordination is η6, consistent with what is observed in (I)[link], a formally CoIII, d6 metal atom.

The 1H NMR data trends are in agreement with those reported for the isoelectronic species, [RuCp(η6-C14H10)](PF6) (McNair & Mann, 1986[McNair, A. M. & Mann, K. R. (1986). Inorg. Chem. 25, 2519-2527.]) and [OsCp(η6-C14H10)](PF6) (Freedman et al., 1997[Freedman, D. A., Gill, T. P., Blough, A. M., Koefod, R. S. & Mann, K. R. (1997). Inorg. Chem. 36, 95-102.]), and for the cationic cobalt complex [(η4-C4Me4)Co(η6-C14H10)](PF6) (Mutseneck et al., 2007[Mutseneck, E. V., Loginov, D. A., Pronin, A. A., Petrovskii, P. V. & Kudinov, A. R. (2007). Russ. Chem. Bull. 56, 1927-1929.]). The most upfield anthracene 1H NMR resonances of δ = 5.98 (I)[link], 6.33 (Ru), 6.62 (Os), and 6.65 (Co cation) p.p.m. demonstrate that the ligand is behaving almost entirely as a donor. The slightly upfield shifts from those of free anthracene may be due to a synergistic effect caused by the donation from the other ligands present, especially three SnMe3 anions, for which the shift is most pronounced.

To date, the analogous reaction using naphthalene instead of anthracene has not been performed.

4. Synthesis and crystallization

A clear blue solution of CoBr2 (0.500 g, 2.29 mmol) in THF (60 ml, 195 K) was added to a deep-blue solution of K[C14H10] (6.86 mmol) in THF (60 ml, 195 K). To the resulting deep pinkish-red solution was added SnMe3Cl (0.455 g, 2.29 mmol) in THF (20 ml, 195 K), which dulled the color. After slow warming to room temperature, the solution was filtered to remove KBr and KCl. The solvent was removed under vacuum, and the product was extracted into pentane (25 ml) and filtered to give an intense violet solution. After the filtrate was cooled to and kept at 273 K for one h, the violet supernatant was carefully transferred to another vessel and placed in a freezer (243 K) for two days, during which time big purple–black crystals of the title complex formed. No attempts to establish the yield or obtain bulk elemental analyses were carried out. However, the product was characterized using the single crystals in solution by NMR and in the solid state by single-crystal X-ray diffraction. 1H NMR (300 MHz, CDCl3, 293 K, δ, p.p.m.): 8.32 (s, 2H, H9,10), 7.90 (m, 2H, H5,8 or H6,7), 7.48 (m, 2H, H5,8 or H6,7), 7.27 (CDCl3), 6.79 (m, 2H, H1,4 or H2,3), 5.98 (m, 2H, H1,4 or H2,3), 0.01 [s, 27H, 2J(1H119Sn) = 20.6 Hz, CH3], 13C{1H} NMR (75.5 MHz, CDCl3, 293 K, δ, p.p.m.): 127.8 (An), 127.4 (An), 126.9 (An), 93.3 (An), 86.3 (An), 77.2 (t, CDCl3), −2.9 (CH3). Quaternary carbon resonances were not resolved.

5. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2[link]. In each of the two independent mol­ecules, the trio of SnMe3 ligands are modeled as disordered over two positions, such that the carbon atoms nearly overlap. In the mol­ecule containing Co1 the disorder ratio refined to 0.9366 (8):0.0634 (8). That for the other mol­ecule refined to 0.9685 (8):0.0315 (8). Despite the small fraction of the minor components, when the disorders are not modeled, the R1 residual increases from 0.0375 to 0.0538. For each disorder model, analogous bond lengths and angles were heavily restrained to be similar. Anisotropic displacement parameters for pairs of near-isopositional carbon atoms were constrained to be equivalent.

Table 2
Experimental details

Crystal data
Chemical formula [CoSn3(CH3)9(C14H10)]
Mr 728.52
Crystal system, space group Triclinic, P[\overline{1}]
Temperature (K) 173
a, b, c (Å) 12.9784 (18), 13.0834 (18), 16.734 (2)
α, β, γ (°) 72.754 (2), 75.891 (2), 89.551 (2)
V3) 2625.5 (6)
Z 4
Radiation type Mo Kα
μ (mm−1) 3.45
Crystal size (mm) 0.28 × 0.24 × 0.06
 
Data collection
Diffractometer Siemens SMART CCD platform
Absorption correction Multi-scan (SADABS; Sheldrick, 2012[Sheldrick, G. M. (2012). SADABS. University of Göttingen, Germany.])
Tmin, Tmax 0.493, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections 30588, 11891, 9564
Rint 0.032
(sin θ/λ)max−1) 0.650
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.086, 1.08
No. of reflections 11891
No. of parameters 639
No. of restraints 42
H-atom treatment H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3) 1.93, −0.79
Computer programs: SMART and SAINT (Bruker, 2003[Bruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97, SHELXL2014 and SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]).

The rather large residual peak in the difference map (1.93 electrons per Å3, located 1.74 Å from atom C4) has no chemical meaning. It (and other similar smaller peaks) is likely due to a very minor twin component whose twin law is [[\overline{1}] 0 0 / 0 [\overline{1}] 0 / −0.623 −0.754 1], a 180 degree rotation about [001] (Parsons et al., 2003[Parsons, S., Gould, B., Cooper, R. & Farrugia, L. (2003). ROTAX. University of Edinburgh, Scotland.]).

H-atom positions of cobalt-coordinating carbon atoms were refined freely, but with relative displacement parameters. All other H atoms were placed geometrically and treated as riding atoms: sp2, C—H = 0.95 Å, with Uiso(H) = 1.2Ueq(C), and methyl, C—H = 0.98 Å with Uiso(H) = 1.5Ueq(C).

[Figure 2]
Figure 2
Anthracene numbering scheme for comparisons in Table 1[link].

Supporting information


Chemical context top

Oxidation derivatives of unstable low-valent species often provide indirect support for their formulations. For example, thermally unstable alkyl isocyanide complexes of formally Fe(—II) that were proposed to be `K2[M(CNtBu)4],' M = Fe (Brennessel et al., 2007), Ru (Corella et al., 1992), were reacted at low temperature in situ with SnPh3Cl to afford isolable and readily characterizable derivatives, trans-M(SnPh3)2(CNtBu)4. Similarly, it was planned to derivatize the formally Co(—I) anion [Co(C10H8)2]-, C10H8 = naphthalene, which is the analog of the well characterized and isolable anthracene cobaltate [Co(C14H10)2]- (C14H10 = anthracene; Brennessel et al., 2002). To date, the only established instance of [Co(C10H8)2]- is as part of the highly specific triple salt [K(18-crown-6)]3[Co(C10H8)(C2H4)2]2[Co(C10H8)2] (Brennessel et al., 2006). But before applying this procedure to the naphthalene system, we chose to first apply it to the well-behaved anthracene system to test the feasibility of the derivatization. Thus, one equivalent of SnMe3Cl was added in situ to a THF solution of [K(THF)x][Co(C14H10)2] (Brennessel et al., 2002), which produced an intense violet, pentane-soluble species. Rather than being the expected `[Co(C14H10)2(SnMe3)]' formally Co(I) species, however, after further investigation it was determined to be the title compound, [Co(η6-C14H10)(SnMe3)3] (I), based on single-crystal X-ray diffraction. Similar reactions using SnPh3 and Sn(cyclo­hexyl)3 produced only intra­cta­ble mixtures. Filtration of the reaction mixture left a very reactive dark-gray filter cake, which appeared to be from the deposition of Co metal. A tentative balanced equation has been proposed based on the initial evidence (see below). No yield was obtained, but if the equation holds, a qu­anti­tative yield would only be 33.3% based on cobalt. Single crystals were grown from a saturated pentane solution in a 243 K freezer and NMR experiments (see Synthesis and crystallization) were performed on the single crystals, which corroborated the crystallography.

Structural Commentary top

The structure contains two independent molecules of (I) (Fig. 1) that are metrically very similar. Each molecule contains one anthracene and three SnMe3 ligands in a three-legged-piano-stool geometry. In each of the two independent molecules, the trio of tin ligands are disordered with a 30° rotation of the set, although the minor component of the disorder is very small (< 10% by mass in both cases). The anthracene ligands in both molecules are coordinated η6 and are nearly planar, with only the slightest bends at the imaginary lines joining atoms C1 and C4 [5.4 (3)°] and C24 and C27 [9.7 (3)°]. The Co—C distances to the ring junction carbon atoms are slightly longer by 0.17 Å than those to the metal-coordinated non-ring junction atoms (Table 1). This has been referred to as a `flat-slipped' coordination mode, and is likely due to an anti­bonding component of the anthracene HOMO at the ring-junction carbon atoms (Zhu et al., 2006). Thus the anthracene ligand is displaced slightly from the symmetric coordination mode found in η6-benzene metal complexes, in order to maximize the bonding overlaps with the four non-ring-junction carbon atoms. Because the metal is formally d6 CoIII, the π-donation from the anthracene ligand is likely the most important contribution to its bonding.

Database Survey top

Structures of η6-coordinated anthracene transition metal complexes are few [Cambridge Structural Database, Version 5.35, update No. 3, May 2014; Groom & Allen, 2014], but range from Ti (Seaburg et al., 1998) to Co (this work). Although one ligand in the titanium complex, [Ti(dmpe)(η4-C14H10)(η6-C14H10)], is considered η6-coordinating based on Ti—C bond lengths, the fold angle between the plane consisting of non-ring-junction metal-coordinated carbon atoms and the rest of the ligand is nearly 20°, very likely placing it on the cusp of η4. However, both [Cr(C14H10)(CO)3] (Hanic & Mills, 1968) and [Mo(C14H10)(PMe3)3] (Zhu et al., 2006) have nearly planar anthracene ligands (6.6 and 5.5–5.8°, respectively). The small fold angles and the M—C(ring junction) bond lengths that are slightly longer than the M—C(non-ring junction) ones exemplify the `flat-slipped' coordination mode (Table 1). For these cases of early transition metals, the π-donation of anthracene is supplemented by δ-backbonding to the anthracene LUMO; however, the C—C bond lengths are not all that different from those seen in normal-valent late transition metal complexes, and all are elongated relative to those in free anthracene (Table 1).

In later transition metal structures, the η6 `flat-slipped' coordination mode is found in normal- or slightly sub-valent metal complexes, and the fold angle appears to be sensitive to oxidation state. In structures with RuII metal centers (Garcia et al., 2010; Konovalov et al., 2011) the fold angles are 3.1 and 4.4°, respectively. As the oxidation state decreases, as in the cases of FeI (Schnöckelborg et al., 2012; Hatanaka et al., 2012) and RhI (Woolf et al., 2011), the fold angles increase slightly to 15.8, 9.1, 9.2, and 13.8°, respectively. Although fold angles may be subject to a variety of additional effects, including packing and sterics, in general the trend is that these angles increase with greater electron-acceptor behavior. This has been examined for the series Cp*Fe(C14H10)(-/0/+) and Cp*Fe(C10H8)(-/0/+), Cp* = C5Me5, by a combination of X-ray crystallography and DFT methods (Schnöckelborg et al., 2012). In low oxidation states, the fold angles are significant and the ring-junction carbon atoms are bent away from the metal, thus making the coordination η4. Whereas the folds become almost non-existent (<10°) for normal valent oxidation states and the coordination is η6, consistent with what is observed in (I), a formally CoIII, d6 metal center.

The 1H NMR data trends are in agreement with those reported for the isoelectronic species, [RuCp(η6-C14H10)](PF6) (McNair & Mann, 1986) and [OsCp(η6-C14H10)](PF6) (Freedman et al., 1997), and for the cationic cobalt complex [(η-C4Me4)Co(η-C14H10)](PF6) (Mutseneck et al., 2007). The most upfield anthracene 1H NMR resonances of δ = 5.98 (I), 6.33 (Ru), 6.62 (Os), and 6.65 (Co cation) p.p.m. demonstrate that the ligand is behaving almost entirely as a donor. The slightly upfield shifts from those of free anthracene may be due to a synergistic effect caused by the donation from the other ligands present, especially three SnMe3- anions, for which the shift is most pronounced.

To date, the analogous reaction using naphthalene instead of anthracene has not been performed.

Synthesis and crystallization top

A clear blue solution of CoBr2 (0.500 g, 2.29 mmol) in THF (60 ml, 195 K) was added to a deep-blue solution of K[C14H10] (6.86 mmol) in THF (60 ml, 195 K). To the resulting deep pinkish-red solution was added SnMe3Cl (0.455 g, 2.29 mmol) in THF (20 ml, 195 K), which dulled the color. After slow warming to room temperature, the solution was filtered to remove KBr and KCl. The solvent was removed under vacuum, and the product was extracted into pentane (25 ml) and filtered to give an intense violet solution. After the filtrate was cooled to and kept at 273 K for one hour, the violet supernatant was carefully transferred to another vessel and placed in a freezer (243 K) for two days, during which time big purple–black crystals of the title complex formed. No attempts to establish the yield or obtain bulk elemental analyses were carried out. However, the product was characterized using the single crystals in solution by NMR and in the solid state by single-crystal X-ray diffraction. 1H NMR (300 MHz, CDCl3, 293 K, δ, p.p.m.): 8.32 (s, 2H, H9,10), 7.90 (m, 2H, H5,8 or H6,7), 7.48 (m, 2H, H5,8 or H6,7), 7.27 (CDCl3), 6.79 (m, 2H, H1,4 or H2,3), 5.98 (m, 2H, H1,4 or H2,3), 0.01 (s, 27H, 2J(1H119Sn) = 20.6 Hz, CHH3), 13C{1H} NMR (75.5 MHz, CDCl3, 293 K, δ, p.p.m.): 127.8 (An), 127.4 (An), 126.9 (An), 93.3 (An), 86.3 (An), 77.2 (t, CDCl3), -2.9 (CH3). Quaternary carbon resonances were not resolved.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. In each of the two independent molecules, the trio of SnMe3 ligands are modeled as disordered over two positions, such that the carbon atoms nearly overlap. In the molecule containing Co1 the disorder ratio refined to 0.9366 (8):0.0634 (8). That for the other molecule refined to 0.9685 (8):0.0315 (8). Despite the small mass of the minor components, when the disorders are not modeled, the R1 residual increases from 0.0375 to 0.0538. For each disorder model, analogous bond lengths and angles were heavily restrained to be similar. Anisotropic displacement parameters for pairs of near-isopositional carbon atoms were constrained to be equivalent.

The rather large residual peak in the difference map (1.93 electrons per Å3, located 1.74 Å from atom C4) has no chemical meaning. It (and other similar smaller peaks) is likely due to a very minor twin component whose twin law is [1 0 0 / 0 1 0 / -0.623 -0.754 1], a 180 degree rotation about [001] (Parsons et al., 2003).

H-atom positions of cobalt-coordinated carbon atoms were refined freely, but with relative thermal parameters. All other H atoms were placed geometrically and treated as riding atoms: sp2, C—H = 0.95 Å, with Uiso(H) = 1.2Ueq(C), and methyl, C—H = 0.98 Å with Uiso(H) = 1.5Ueq(C).

Related literature top

For related literature, see: Groom & Allen (2014); Brennessel et al. (2002, 2006, 2007); Corella, Thompson & Cooper (1992); Freedman et al. (1997); Garcia et al. (2010); Hanic & Mills (1968); Hatanaka et al. (2012); Konovalov et al. (2011); McNair & Mann (1986); Mutseneck et al. (2007); Parsons et al. (2003); Schnöckelborg et al. (2012); Seaburg et al. (1998); Woolf et al. (2011); Zhu et al. (2006).

Computing details top

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: SHELXL2014 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
The two independent molecules of (I), showing the atom numbering. The minor components of the disorder are shown with dashed lines and boundary ellipsoids. The two orientations of the SnMe3 ligand set fit in essentially the same volume because the methyl groups are overlapped. Displacement ellipsoids are drawn at the 50% probability level and hydrogen atoms have been omitted.

Anthracene numbering scheme for comparisons in Table 1.
[(1,2,3,4,11,12-η)-Anthracene]tris(trimethylstannyl)cobalt(III) top
Crystal data top
[CoSn3(C14H10)(CH3)9]Z = 4
Mr = 728.52F(000) = 1408
Triclinic, P1Dx = 1.843 Mg m3
a = 12.9784 (18) ÅMo Kα radiation, λ = 0.71073 Å
b = 13.0834 (18) ÅCell parameters from 3885 reflections
c = 16.734 (2) ŵ = 3.45 mm1
α = 72.754 (2)°T = 173 K
β = 75.891 (2)°Plate, dark purple
γ = 89.551 (2)°0.28 × 0.24 × 0.06 mm
V = 2625.5 (6) Å3
Data collection top
Siemens SMART CCD platform
diffractometer
9564 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tubeRint = 0.032
ω scansθmax = 27.5°, θmin = 1.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2012)
h = 1616
Tmin = 0.493, Tmax = 0.746k = 1616
30588 measured reflectionsl = 2121
11891 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.038Hydrogen site location: mixed
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.032P)2 + 4.7781P]
where P = (Fo2 + 2Fc2)/3
11891 reflections(Δ/σ)max = 0.001
639 parametersΔρmax = 1.93 e Å3
42 restraintsΔρmin = 0.79 e Å3
Crystal data top
[CoSn3(C14H10)(CH3)9]γ = 89.551 (2)°
Mr = 728.52V = 2625.5 (6) Å3
Triclinic, P1Z = 4
a = 12.9784 (18) ÅMo Kα radiation
b = 13.0834 (18) ŵ = 3.45 mm1
c = 16.734 (2) ÅT = 173 K
α = 72.754 (2)°0.28 × 0.24 × 0.06 mm
β = 75.891 (2)°
Data collection top
Siemens SMART CCD platform
diffractometer
11891 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2012)
9564 reflections with I > 2σ(I)
Tmin = 0.493, Tmax = 0.746Rint = 0.032
30588 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.03842 restraints
wR(F2) = 0.086H atoms treated by a mixture of independent and constrained refinement
S = 1.08Δρmax = 1.93 e Å3
11891 reflectionsΔρmin = 0.79 e Å3
639 parameters
Special details top

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. The largest residual peak of 1.93 electrons per Å3, located 1.74 Å from atom C4, has no chemical meaning. It (and other smaller peaks that likewise having no chemical meaning) is likely due to a very minor twin component whose twin law is [-1 0 0 / 0 - 1 0 / -0.623 - 0.754 1], a 180 degree rotation about [001] (Parsons, 2003).

In each of the two independent molecules, the trio of SnMe3 ligands are modeled as disordered over two positions, such that the carbon atoms nearly overlap. In the molecule containing Co1 the disorder ratio refined to 0.9366 (8):0.0634 (8). That for the other molecule refined to 0.9686 (8):0.0314 (8). Despite the small mass of the minor components, when the disorders are not modeled, the R1 residual increases from 0.0375 to 0.0538.

For each disorder model, analogous bond lengths and angles were heavily restrained to be similar. Anisotropic displacement parameters for pairs of near-isopositional carbon atoms were constrained to be equivalent.

H atom positions of cobalt-coordinated carbon atoms were refined freely, but with relative thermal parameters as described below. All other H atoms were placed geometrically and treated as riding atoms: sp2, C—H = 0.95 Å, with Uiso(H) = 1.2Ueq(C), and methyl, C—H = 0.98 Å with Uiso(H) = 1.5Ueq(C).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Co10.37703 (4)0.13516 (5)0.21652 (4)0.02862 (14)
C10.3223 (4)0.0682 (4)0.1335 (4)0.0415 (12)
H10.362 (4)0.067 (4)0.077 (4)0.050*
C20.2640 (4)0.1551 (5)0.1430 (4)0.0461 (13)
H20.260 (5)0.209 (5)0.097 (4)0.055*
C30.2146 (4)0.1582 (5)0.2279 (4)0.0517 (15)
H30.184 (5)0.217 (5)0.238 (4)0.062*
C40.2238 (4)0.0760 (5)0.3005 (4)0.0450 (13)
H40.196 (4)0.083 (4)0.359 (4)0.054*
C50.3347 (6)0.2885 (5)0.4240 (4)0.0660 (18)
H50.30250.28710.48110.079*
C60.3857 (6)0.3749 (5)0.4118 (5)0.0712 (19)
H60.38910.43280.46110.085*
C70.4344 (4)0.3834 (4)0.3286 (4)0.0463 (13)
H70.46930.44550.32190.056*
C80.4293 (4)0.2988 (4)0.2581 (4)0.0458 (13)
H80.46110.30310.20180.055*
C90.3733 (4)0.1173 (4)0.1964 (3)0.0354 (10)
H90.40480.12100.13980.042*
C100.2779 (4)0.1078 (5)0.3626 (4)0.0506 (14)
H100.24510.10560.41940.061*
C110.3238 (3)0.0242 (4)0.2056 (3)0.0351 (11)
C120.2743 (4)0.0195 (4)0.2919 (4)0.0418 (12)
C130.3286 (4)0.1992 (4)0.3520 (3)0.0453 (13)
C140.3777 (4)0.2042 (4)0.2670 (3)0.0383 (11)
Sn10.55882 (2)0.16207 (3)0.10994 (2)0.03084 (9)0.9365 (8)
C150.7078 (6)0.2100 (7)0.1306 (7)0.0558 (16)0.9365 (8)
H15A0.71290.16890.18870.084*0.9365 (8)
H15B0.71000.28680.12490.084*0.9365 (8)
H15C0.76760.19600.08750.084*0.9365 (8)
C160.6052 (8)0.0186 (5)0.0754 (4)0.0454 (15)0.9365 (8)
H16A0.67830.03050.03900.068*0.9365 (8)
H16B0.55710.00150.04350.068*0.9365 (8)
H16C0.60110.04120.12800.068*0.9365 (8)
C170.5498 (5)0.2734 (5)0.0128 (4)0.0489 (14)0.9365 (8)
H17A0.61210.26870.05810.073*0.9365 (8)
H17B0.54830.34660.00860.073*0.9365 (8)
H17C0.48480.25530.02720.073*0.9365 (8)
Sn20.47432 (3)0.10385 (3)0.33620 (2)0.03731 (10)0.9365 (8)
C180.5817 (5)0.2171 (6)0.3523 (6)0.0574 (18)0.9365 (8)
H18A0.61020.18240.40210.086*0.9365 (8)
H18B0.54320.27880.36200.086*0.9365 (8)
H18C0.64050.24140.30010.086*0.9365 (8)
C190.3608 (8)0.0671 (7)0.4623 (4)0.068 (2)0.9365 (8)
H19A0.34800.01090.48790.102*0.9365 (8)
H19B0.29360.09870.45550.102*0.9365 (8)
H19C0.38970.09680.50030.102*0.9365 (8)
C200.5637 (5)0.0349 (5)0.3326 (5)0.0568 (18)0.9365 (8)
H20A0.63400.02310.34140.085*0.9365 (8)
H20B0.57210.04670.27620.085*0.9365 (8)
H20C0.52560.09800.37840.085*0.9365 (8)
Sn30.39786 (3)0.33197 (3)0.20495 (2)0.03421 (9)0.9365 (8)
C210.5464 (5)0.4278 (4)0.1656 (4)0.0454 (15)0.9365 (8)
H21A0.53200.50260.16090.068*0.9365 (8)
H21B0.58720.42320.10930.068*0.9365 (8)
H21C0.58760.40100.20850.068*0.9365 (8)
C220.3205 (5)0.4202 (5)0.1061 (5)0.0527 (17)0.9365 (8)
H22A0.24600.39270.12170.079*0.9365 (8)
H22B0.35710.41100.05030.079*0.9365 (8)
H22C0.32370.49650.10180.079*0.9365 (8)
C230.3121 (5)0.3570 (5)0.3242 (4)0.0522 (16)0.9365 (8)
H23A0.35520.33740.36640.078*0.9365 (8)
H23B0.24500.31230.34690.078*0.9365 (8)
H23C0.29700.43270.31370.078*0.9365 (8)
Sn1'0.5647 (4)0.0882 (5)0.1893 (4)0.0500 (18)0.0635 (8)
C15'0.697 (7)0.210 (8)0.135 (7)0.0558 (16)0.0635 (8)
H15D0.69060.25790.17090.084*0.0635 (8)
H15E0.76420.17490.13420.084*0.0635 (8)
H15F0.69560.25100.07620.084*0.0635 (8)
C16'0.604 (12)0.001 (6)0.097 (4)0.0454 (15)0.0635 (8)
H16D0.59010.04180.04190.068*0.0635 (8)
H16E0.67930.01540.08750.068*0.0635 (8)
H16F0.55990.06850.11910.068*0.0635 (8)
C17'0.601 (7)0.021 (6)0.303 (3)0.0522 (16)0.0635 (8)
H17D0.58640.01180.34990.078*0.0635 (8)
H17E0.55750.08820.32090.078*0.0635 (8)
H17F0.67690.03510.28930.078*0.0635 (8)
Sn2'0.3993 (5)0.1957 (6)0.3414 (4)0.065 (2)0.0635 (8)
C18'0.554 (4)0.231 (8)0.356 (9)0.0574 (18)0.0635 (8)
H18D0.60120.17470.34630.086*0.0635 (8)
H18E0.58500.30030.31390.086*0.0635 (8)
H18F0.54770.23530.41470.086*0.0635 (8)
C19'0.349 (9)0.056 (5)0.455 (4)0.068 (2)0.0635 (8)
H19D0.38990.00460.44610.102*0.0635 (8)
H19E0.36070.07240.50580.102*0.0635 (8)
H19F0.27280.03700.46490.102*0.0635 (8)
C20'0.307 (5)0.326 (4)0.364 (5)0.0489 (14)0.0635 (8)
H20D0.23450.31510.35870.073*0.0635 (8)
H20E0.30290.32900.42290.073*0.0635 (8)
H20F0.34020.39390.32210.073*0.0635 (8)
Sn3'0.4487 (5)0.3255 (5)0.1205 (4)0.0535 (18)0.0635 (8)
C21'0.542 (6)0.450 (5)0.137 (5)0.0454 (15)0.0635 (8)
H21D0.51460.45610.19520.068*0.0635 (8)
H21E0.61650.43200.12900.068*0.0635 (8)
H21F0.53730.51840.09390.068*0.0635 (8)
C22'0.299 (4)0.400 (6)0.119 (6)0.0527 (17)0.0635 (8)
H22D0.26470.40460.17730.079*0.0635 (8)
H22E0.31200.47290.07820.079*0.0635 (8)
H22F0.25150.35760.10210.079*0.0635 (8)
C23'0.516 (6)0.320 (6)0.009 (2)0.0568 (18)0.0635 (8)
H23D0.47690.26460.02010.085*0.0635 (8)
H23E0.51200.38990.05030.085*0.0635 (8)
H23F0.59120.30350.01520.085*0.0635 (8)
Co20.00682 (4)0.36883 (5)0.78274 (4)0.02670 (13)
C240.0921 (4)0.4357 (4)0.8698 (3)0.0363 (11)
H240.090 (4)0.437 (4)0.922 (3)0.044*
C250.1491 (4)0.3499 (4)0.8624 (4)0.0395 (11)
H250.181 (4)0.292 (4)0.914 (4)0.047*
C260.1519 (4)0.3471 (5)0.7790 (4)0.0429 (12)
H260.192 (4)0.291 (4)0.778 (3)0.051*
C270.1030 (4)0.4293 (4)0.7063 (3)0.0384 (11)
H270.103 (4)0.422 (4)0.652 (4)0.046*
C280.0525 (5)0.8050 (5)0.5773 (4)0.0524 (14)
H280.04340.80710.52220.063*
C290.0933 (5)0.8922 (5)0.5886 (4)0.0621 (17)
H290.11270.95570.54080.074*
C300.1081 (5)0.8923 (5)0.6696 (4)0.0637 (17)
H300.13930.95470.67480.076*
C310.0788 (4)0.8054 (4)0.7391 (4)0.0461 (13)
H310.08880.80700.79310.055*
C320.0046 (4)0.6209 (4)0.8032 (3)0.0381 (11)
H320.00160.62220.85830.046*
C330.0198 (4)0.6166 (4)0.6414 (3)0.0436 (12)
H330.02430.61510.58590.052*
C340.0510 (4)0.5279 (4)0.7965 (3)0.0347 (10)
C350.0569 (4)0.5249 (4)0.7129 (3)0.0358 (11)
C360.0227 (4)0.7085 (4)0.6489 (3)0.0390 (11)
C370.0323 (4)0.7102 (4)0.7325 (3)0.0379 (11)
Sn40.12611 (2)0.33492 (3)0.88667 (2)0.02952 (8)0.9686 (8)
C380.2862 (4)0.2827 (5)0.8632 (4)0.0469 (14)0.9686 (8)
H38A0.31190.27060.91550.070*0.9686 (8)
H38B0.33310.33810.81540.070*0.9686 (8)
H38C0.28620.21590.84820.070*0.9686 (8)
C390.1534 (4)0.4762 (5)0.9231 (4)0.0424 (14)0.9686 (8)
H39A0.20240.46090.96080.064*0.9686 (8)
H39B0.08560.49570.95400.064*0.9686 (8)
H39C0.18460.53570.87110.064*0.9686 (8)
C400.0413 (5)0.2233 (5)1.0099 (4)0.0519 (15)0.9686 (8)
H40A0.08010.22141.05370.078*0.9686 (8)
H40B0.03570.15151.00380.078*0.9686 (8)
H40C0.03030.24671.02780.078*0.9686 (8)
Sn50.17472 (2)0.40061 (3)0.65953 (2)0.03177 (9)0.9686 (8)
C410.2885 (5)0.2841 (5)0.6367 (4)0.0550 (17)0.9686 (8)
H41A0.34710.31870.58640.083*0.9686 (8)
H41B0.25320.22550.62590.083*0.9686 (8)
H41C0.31660.25550.68770.083*0.9686 (8)
C420.1347 (5)0.4509 (6)0.5354 (4)0.0554 (17)0.9686 (8)
H42A0.18880.42920.49260.083*0.9686 (8)
H42B0.13220.52910.51650.083*0.9686 (8)
H42C0.06500.41720.54130.083*0.9686 (8)
C430.2710 (5)0.5340 (5)0.6633 (4)0.0466 (14)0.9686 (8)
H43A0.33670.54730.61690.070*0.9686 (8)
H43B0.28870.51620.71930.070*0.9686 (8)
H43C0.23080.59840.65550.070*0.9686 (8)
Sn60.01690 (3)0.17235 (3)0.79114 (2)0.03626 (9)0.9686 (8)
C440.1420 (5)0.0721 (5)0.8241 (5)0.0539 (16)0.9686 (8)
H44A0.12510.00080.82430.081*0.9686 (8)
H44B0.14830.07060.88160.081*0.9686 (8)
H44C0.20950.10100.78140.081*0.9686 (8)
C450.1180 (5)0.0839 (5)0.8929 (5)0.0530 (16)0.9686 (8)
H45A0.11930.00830.89480.080*0.9686 (8)
H45B0.18410.11400.88130.080*0.9686 (8)
H45C0.11160.08940.94870.080*0.9686 (8)
C460.0068 (5)0.1551 (5)0.6712 (4)0.0544 (16)0.9686 (8)
H46A0.02680.07990.67980.082*0.9686 (8)
H46B0.05940.17800.62550.082*0.9686 (8)
H46C0.06360.19980.65440.082*0.9686 (8)
Sn4'0.1818 (9)0.4147 (9)0.8092 (8)0.053 (4)0.0314 (8)
C38'0.295 (8)0.293 (7)0.830 (8)0.0469 (14)0.0314 (8)
H38D0.29970.25350.78760.070*0.0314 (8)
H38E0.36490.32750.82180.070*0.0314 (8)
H38F0.27110.24370.88830.070*0.0314 (8)
C39'0.191 (11)0.485 (8)0.910 (5)0.0424 (14)0.0314 (8)
H39D0.14230.54300.90860.064*0.0314 (8)
H39E0.16990.42990.96620.064*0.0314 (8)
H39F0.26370.51370.89970.064*0.0314 (8)
C40'0.264 (10)0.540 (6)0.693 (4)0.0466 (14)0.0314 (8)
H40D0.21680.59800.67970.070*0.0314 (8)
H40E0.32840.56770.70210.070*0.0314 (8)
H40F0.28330.50990.64440.070*0.0314 (8)
Sn5'0.1087 (11)0.3209 (11)0.6522 (7)0.061 (4)0.0314 (8)
C41'0.279 (2)0.305 (11)0.619 (11)0.0550 (17)0.0314 (8)
H41D0.29740.24800.66540.083*0.0314 (8)
H41E0.29940.28720.56490.083*0.0314 (8)
H41F0.31630.37300.61240.083*0.0314 (8)
C42'0.096 (12)0.450 (7)0.539 (6)0.0554 (17)0.0314 (8)
H42D0.02120.46720.54480.083*0.0314 (8)
H42E0.13870.51410.53460.083*0.0314 (8)
H42F0.12180.42830.48710.083*0.0314 (8)
C43'0.040 (11)0.176 (6)0.641 (9)0.0544 (16)0.0314 (8)
H43D0.03750.17650.65490.082*0.0314 (8)
H43E0.06670.17290.58160.082*0.0314 (8)
H43F0.06100.11280.68110.082*0.0314 (8)
Sn6'0.0243 (11)0.1762 (9)0.8696 (8)0.067 (5)0.0314 (8)
C44'0.152 (7)0.078 (9)0.838 (9)0.0539 (16)0.0314 (8)
H44D0.22010.11430.83200.081*0.0314 (8)
H44E0.14200.00890.88340.081*0.0314 (8)
H44F0.15170.06520.78270.081*0.0314 (8)
C45'0.111 (6)0.074 (9)0.877 (9)0.0530 (16)0.0314 (8)
H45D0.17670.10880.89120.080*0.0314 (8)
H45E0.10330.06130.82070.080*0.0314 (8)
H45F0.11300.00510.92140.080*0.0314 (8)
C46'0.012 (11)0.178 (11)1.001 (3)0.0519 (15)0.0314 (8)
H46D0.04540.22221.01790.078*0.0314 (8)
H46E0.00300.10451.04070.078*0.0314 (8)
H46F0.07960.20771.00440.078*0.0314 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0235 (3)0.0335 (3)0.0337 (3)0.0020 (2)0.0095 (2)0.0155 (3)
C10.033 (3)0.057 (3)0.048 (3)0.001 (2)0.018 (2)0.030 (3)
C20.033 (3)0.054 (3)0.068 (4)0.009 (2)0.032 (3)0.026 (3)
C30.022 (2)0.061 (4)0.084 (5)0.006 (2)0.014 (3)0.040 (4)
C40.031 (3)0.050 (3)0.054 (3)0.006 (2)0.000 (2)0.025 (3)
C50.094 (5)0.048 (4)0.042 (3)0.011 (3)0.000 (3)0.006 (3)
C60.090 (5)0.048 (4)0.061 (4)0.007 (3)0.009 (4)0.002 (3)
C70.044 (3)0.045 (3)0.048 (3)0.001 (2)0.004 (2)0.018 (3)
C80.040 (3)0.050 (3)0.051 (3)0.003 (2)0.008 (2)0.023 (3)
C90.032 (2)0.044 (3)0.035 (3)0.000 (2)0.0075 (19)0.019 (2)
C100.050 (3)0.051 (3)0.044 (3)0.017 (3)0.008 (2)0.020 (3)
C110.026 (2)0.041 (3)0.045 (3)0.0019 (19)0.011 (2)0.021 (2)
C120.029 (2)0.048 (3)0.051 (3)0.007 (2)0.001 (2)0.026 (3)
C130.045 (3)0.043 (3)0.042 (3)0.012 (2)0.001 (2)0.012 (2)
C140.033 (2)0.043 (3)0.042 (3)0.006 (2)0.008 (2)0.018 (2)
Sn10.02348 (16)0.03726 (19)0.03407 (19)0.00299 (13)0.00831 (13)0.01343 (15)
C150.030 (3)0.064 (4)0.082 (5)0.002 (3)0.017 (3)0.034 (3)
C160.037 (3)0.055 (4)0.048 (4)0.011 (3)0.006 (3)0.026 (3)
C170.041 (3)0.058 (4)0.040 (3)0.004 (3)0.008 (2)0.006 (3)
Sn20.0451 (2)0.0371 (2)0.0365 (2)0.00380 (15)0.02069 (16)0.01288 (16)
C180.064 (4)0.062 (4)0.063 (4)0.003 (3)0.039 (4)0.027 (3)
C190.092 (5)0.076 (5)0.038 (3)0.007 (4)0.020 (3)0.015 (3)
C200.065 (5)0.054 (4)0.066 (4)0.024 (3)0.039 (4)0.021 (3)
Sn30.03129 (18)0.03110 (18)0.0436 (2)0.00540 (13)0.01187 (15)0.01455 (15)
C210.040 (3)0.035 (3)0.059 (4)0.004 (2)0.018 (3)0.005 (3)
C220.047 (3)0.047 (4)0.064 (4)0.015 (3)0.020 (3)0.012 (3)
C230.055 (4)0.050 (4)0.055 (4)0.013 (3)0.009 (3)0.026 (3)
Sn1'0.037 (3)0.061 (4)0.059 (4)0.003 (3)0.013 (3)0.027 (3)
C15'0.030 (3)0.064 (4)0.082 (5)0.002 (3)0.017 (3)0.034 (3)
C16'0.037 (3)0.055 (4)0.048 (4)0.011 (3)0.006 (3)0.026 (3)
C17'0.055 (4)0.050 (4)0.055 (4)0.013 (3)0.009 (3)0.026 (3)
Sn2'0.066 (4)0.084 (5)0.051 (4)0.022 (4)0.011 (3)0.034 (4)
C18'0.064 (4)0.062 (4)0.063 (4)0.003 (3)0.039 (4)0.027 (3)
C19'0.092 (5)0.076 (5)0.038 (3)0.007 (4)0.020 (3)0.015 (3)
C20'0.041 (3)0.058 (4)0.040 (3)0.004 (3)0.008 (2)0.006 (3)
Sn3'0.046 (4)0.060 (4)0.054 (4)0.008 (3)0.017 (3)0.012 (3)
C21'0.040 (3)0.035 (3)0.059 (4)0.004 (2)0.018 (3)0.005 (3)
C22'0.047 (3)0.047 (4)0.064 (4)0.015 (3)0.020 (3)0.012 (3)
C23'0.065 (5)0.054 (4)0.066 (4)0.024 (3)0.039 (4)0.021 (3)
Co20.0242 (3)0.0307 (3)0.0301 (3)0.0025 (2)0.0111 (2)0.0132 (3)
C240.032 (2)0.047 (3)0.036 (3)0.015 (2)0.010 (2)0.021 (2)
C250.021 (2)0.042 (3)0.051 (3)0.0059 (19)0.005 (2)0.010 (2)
C260.027 (2)0.052 (3)0.061 (4)0.003 (2)0.024 (2)0.024 (3)
C270.040 (3)0.044 (3)0.044 (3)0.011 (2)0.027 (2)0.019 (2)
C280.067 (4)0.047 (3)0.039 (3)0.005 (3)0.004 (3)0.014 (3)
C290.073 (4)0.047 (4)0.051 (4)0.001 (3)0.000 (3)0.006 (3)
C300.067 (4)0.049 (4)0.071 (4)0.011 (3)0.004 (3)0.023 (3)
C310.040 (3)0.049 (3)0.058 (3)0.004 (2)0.012 (2)0.030 (3)
C320.034 (2)0.056 (3)0.035 (3)0.007 (2)0.012 (2)0.026 (2)
C330.059 (3)0.044 (3)0.034 (3)0.011 (2)0.020 (2)0.015 (2)
C340.029 (2)0.045 (3)0.034 (3)0.009 (2)0.0116 (19)0.016 (2)
C350.037 (3)0.040 (3)0.041 (3)0.011 (2)0.022 (2)0.020 (2)
C360.041 (3)0.043 (3)0.037 (3)0.012 (2)0.011 (2)0.016 (2)
C370.036 (3)0.037 (3)0.051 (3)0.013 (2)0.022 (2)0.021 (2)
Sn40.02549 (16)0.03679 (18)0.03028 (17)0.00225 (12)0.01220 (12)0.01196 (14)
C380.033 (3)0.059 (4)0.059 (4)0.011 (2)0.022 (3)0.024 (3)
C390.038 (3)0.054 (3)0.050 (3)0.004 (2)0.020 (2)0.029 (3)
C400.048 (3)0.064 (4)0.036 (3)0.004 (3)0.014 (2)0.000 (3)
Sn50.02953 (17)0.03985 (19)0.02961 (17)0.00062 (13)0.00817 (13)0.01540 (14)
C410.049 (3)0.059 (4)0.059 (4)0.014 (3)0.006 (3)0.027 (3)
C420.052 (4)0.089 (5)0.032 (3)0.002 (3)0.017 (3)0.023 (3)
C430.043 (3)0.051 (3)0.045 (3)0.012 (2)0.013 (3)0.012 (3)
Sn60.03465 (18)0.03089 (18)0.0499 (2)0.00055 (13)0.01780 (15)0.01638 (16)
C440.060 (4)0.035 (3)0.076 (5)0.014 (3)0.031 (3)0.019 (3)
C450.042 (3)0.046 (3)0.070 (4)0.009 (2)0.021 (3)0.009 (3)
C460.060 (4)0.055 (4)0.066 (4)0.004 (3)0.029 (3)0.036 (3)
Sn4'0.038 (6)0.074 (9)0.062 (9)0.009 (6)0.026 (6)0.032 (7)
C38'0.033 (3)0.059 (4)0.059 (4)0.011 (2)0.022 (3)0.024 (3)
C39'0.038 (3)0.054 (3)0.050 (3)0.004 (2)0.020 (2)0.029 (3)
C40'0.043 (3)0.051 (3)0.045 (3)0.012 (2)0.013 (3)0.012 (3)
Sn5'0.059 (8)0.082 (10)0.064 (9)0.016 (7)0.026 (7)0.046 (8)
C41'0.049 (3)0.059 (4)0.059 (4)0.014 (3)0.006 (3)0.027 (3)
C42'0.052 (4)0.089 (5)0.032 (3)0.002 (3)0.017 (3)0.023 (3)
C43'0.060 (4)0.055 (4)0.066 (4)0.004 (3)0.029 (3)0.036 (3)
Sn6'0.067 (9)0.053 (9)0.072 (10)0.000 (7)0.021 (8)0.005 (7)
C44'0.060 (4)0.035 (3)0.076 (5)0.014 (3)0.031 (3)0.019 (3)
C45'0.042 (3)0.046 (3)0.070 (4)0.009 (2)0.021 (3)0.009 (3)
C46'0.048 (3)0.064 (4)0.036 (3)0.004 (3)0.014 (2)0.000 (3)
Geometric parameters (Å, º) top
Co1—C32.098 (5)Co2—C242.088 (5)
Co1—C12.101 (5)Co2—C262.100 (5)
Co1—C22.102 (5)Co2—C252.104 (5)
Co1—C42.132 (5)Co2—C272.136 (5)
Co1—C112.273 (5)Co2—C342.264 (5)
Co1—C122.274 (5)Co2—C352.291 (5)
Co1—Sn1'2.474 (5)Co2—Sn5'2.512 (11)
Co1—Sn2'2.521 (5)Co2—Sn4'2.526 (10)
Co1—Sn32.5359 (8)Co2—Sn62.5366 (8)
Co1—Sn12.5418 (7)Co2—Sn42.5423 (7)
Co1—Sn22.5518 (7)Co2—Sn52.5471 (7)
Co1—Sn3'2.566 (6)Co2—Sn6'2.549 (12)
C1—C21.387 (7)C24—C251.400 (7)
C1—C111.438 (7)C24—C341.435 (7)
C1—H10.97 (5)C24—H240.89 (5)
C2—C31.423 (8)C25—C261.416 (8)
C2—H20.88 (6)C25—H250.96 (5)
C3—C41.393 (9)C26—C271.377 (8)
C3—H30.91 (6)C26—H260.91 (6)
C4—C121.436 (7)C27—C351.435 (7)
C4—H40.99 (6)C27—H270.94 (5)
C5—C61.348 (9)C28—C291.343 (8)
C5—C131.425 (8)C28—C361.437 (7)
C5—H50.9500C28—H280.9500
C6—C71.418 (8)C29—C301.417 (9)
C6—H60.9500C29—H290.9500
C7—C81.373 (8)C30—C311.340 (8)
C7—H70.9500C30—H300.9500
C8—C141.431 (7)C31—C371.434 (7)
C8—H80.9500C31—H310.9500
C9—C141.388 (7)C32—C371.382 (7)
C9—C111.403 (7)C32—C341.406 (7)
C9—H90.9500C32—H320.9500
C10—C131.397 (8)C33—C361.378 (7)
C10—C121.398 (8)C33—C351.407 (7)
C10—H100.9500C33—H330.9500
C11—C121.449 (7)C34—C351.432 (6)
C13—C141.431 (7)C36—C371.440 (7)
Sn1—C162.162 (5)Sn4—C382.163 (5)
Sn1—C172.167 (6)Sn4—C392.167 (5)
Sn1—C152.174 (6)Sn4—C402.175 (5)
C15—H15A0.9800C38—H38A0.9800
C15—H15B0.9800C38—H38B0.9800
C15—H15C0.9800C38—H38C0.9800
C16—H16A0.9800C39—H39A0.9800
C16—H16B0.9800C39—H39B0.9800
C16—H16C0.9800C39—H39C0.9800
C17—H17A0.9800C40—H40A0.9800
C17—H17B0.9800C40—H40B0.9800
C17—H17C0.9800C40—H40C0.9800
Sn2—C202.155 (6)Sn5—C412.164 (6)
Sn2—C182.159 (6)Sn5—C422.174 (5)
Sn2—C192.179 (7)Sn5—C432.179 (5)
C18—H18A0.9800C41—H41A0.9800
C18—H18B0.9800C41—H41B0.9800
C18—H18C0.9800C41—H41C0.9800
C19—H19A0.9800C42—H42A0.9800
C19—H19B0.9800C42—H42B0.9800
C19—H19C0.9800C42—H42C0.9800
C20—H20A0.9800C43—H43A0.9800
C20—H20B0.9800C43—H43B0.9800
C20—H20C0.9800C43—H43C0.9800
Sn3—C232.151 (6)Sn6—C442.152 (6)
Sn3—C212.157 (5)Sn6—C452.172 (6)
Sn3—C222.176 (6)Sn6—C462.177 (6)
C21—H21A0.9800C44—H44A0.9800
C21—H21B0.9800C44—H44B0.9800
C21—H21C0.9800C44—H44C0.9800
C22—H22A0.9800C45—H45A0.9800
C22—H22B0.9800C45—H45B0.9800
C22—H22C0.9800C45—H45C0.9800
C23—H23A0.9800C46—H46A0.9800
C23—H23B0.9800C46—H46B0.9800
C23—H23C0.9800C46—H46C0.9800
Sn1'—C16'2.162 (7)Sn4'—C38'2.163 (6)
Sn1'—C17'2.167 (7)Sn4'—C39'2.167 (6)
Sn1'—C15'2.174 (7)Sn4'—C40'2.175 (7)
C15'—H15D0.9800C38'—H38D0.9800
C15'—H15E0.9800C38'—H38E0.9800
C15'—H15F0.9800C38'—H38F0.9800
C16'—H16D0.9800C39'—H39D0.9800
C16'—H16E0.9800C39'—H39E0.9800
C16'—H16F0.9800C39'—H39F0.9800
C17'—H17D0.9800C40'—H40D0.9800
C17'—H17E0.9800C40'—H40E0.9800
C17'—H17F0.9800C40'—H40F0.9800
Sn2'—C20'2.155 (7)Sn5'—C41'2.164 (7)
Sn2'—C18'2.159 (7)Sn5'—C42'2.174 (7)
Sn2'—C19'2.179 (8)Sn5'—C43'2.179 (7)
C18'—H18D0.9800C41'—H41D0.9800
C18'—H18E0.9800C41'—H41E0.9800
C18'—H18F0.9800C41'—H41F0.9800
C19'—H19D0.9800C42'—H42D0.9800
C19'—H19E0.9800C42'—H42E0.9800
C19'—H19F0.9800C42'—H42F0.9800
C20'—H20D0.9800C43'—H43D0.9800
C20'—H20E0.9800C43'—H43E0.9800
C20'—H20F0.9800C43'—H43F0.9800
Sn3'—C23'2.151 (7)Sn6'—C44'2.152 (7)
Sn3'—C21'2.157 (6)Sn6'—C45'2.172 (7)
Sn3'—C22'2.176 (7)Sn6'—C46'2.177 (7)
C21'—H21D0.9800C44'—H44D0.9800
C21'—H21E0.9800C44'—H44E0.9800
C21'—H21F0.9800C44'—H44F0.9800
C22'—H22D0.9800C45'—H45D0.9800
C22'—H22E0.9800C45'—H45E0.9800
C22'—H22F0.9800C45'—H45F0.9800
C23'—H23D0.9800C46'—H46D0.9800
C23'—H23E0.9800C46'—H46E0.9800
C23'—H23F0.9800C46'—H46F0.9800
C3—Co1—C170.3 (2)C24—Co2—C2670.8 (2)
C3—Co1—C239.6 (2)C24—Co2—C2539.0 (2)
C1—Co1—C238.5 (2)C26—Co2—C2539.4 (2)
C3—Co1—C438.4 (2)C24—Co2—C2783.0 (2)
C1—Co1—C483.1 (2)C26—Co2—C2737.9 (2)
C2—Co1—C470.8 (2)C25—Co2—C2769.9 (2)
C3—Co1—C1180.9 (2)C24—Co2—C3438.24 (18)
C1—Co1—C1138.1 (2)C26—Co2—C3481.00 (19)
C2—Co1—C1168.7 (2)C25—Co2—C3468.77 (19)
C4—Co1—C1168.30 (19)C27—Co2—C3467.99 (18)
C3—Co1—C1268.4 (2)C24—Co2—C3568.27 (19)
C1—Co1—C1268.8 (2)C26—Co2—C3567.7 (2)
C2—Co1—C1281.8 (2)C25—Co2—C3580.68 (19)
C4—Co1—C1237.86 (19)C27—Co2—C3537.62 (17)
C11—Co1—C1237.15 (17)C34—Co2—C3536.63 (16)
C3—Co1—Sn1'170.6 (2)C24—Co2—Sn5'166.4 (3)
C1—Co1—Sn1'100.5 (2)C26—Co2—Sn5'102.3 (3)
C2—Co1—Sn1'132.9 (2)C25—Co2—Sn5'139.3 (3)
C4—Co1—Sn1'141.2 (2)C27—Co2—Sn5'84.6 (3)
C11—Co1—Sn1'90.71 (18)C34—Co2—Sn5'130.5 (3)
C12—Co1—Sn1'107.26 (19)C35—Co2—Sn5'98.4 (3)
C3—Co1—Sn2'98.8 (2)C24—Co2—Sn4'97.6 (3)
C1—Co1—Sn2'165.9 (2)C26—Co2—Sn4'168.4 (3)
C2—Co1—Sn2'135.2 (2)C25—Co2—Sn4'130.4 (3)
C4—Co1—Sn2'82.8 (2)C27—Co2—Sn4'142.9 (3)
C11—Co1—Sn2'133.4 (2)C34—Co2—Sn4'89.6 (3)
C12—Co1—Sn2'99.2 (2)C35—Co2—Sn4'108.3 (3)
Sn1'—Co1—Sn2'90.02 (19)Sn5'—Co2—Sn4'89.0 (3)
C3—Co1—Sn386.04 (17)C24—Co2—Sn6127.92 (15)
C1—Co1—Sn3127.76 (16)C26—Co2—Sn685.08 (15)
C2—Co1—Sn395.20 (16)C25—Co2—Sn694.87 (14)
C4—Co1—Sn3106.55 (15)C27—Co2—Sn6105.56 (14)
C11—Co1—Sn3163.89 (13)C34—Co2—Sn6163.54 (12)
C12—Co1—Sn3143.26 (13)C35—Co2—Sn6142.22 (12)
C3—Co1—Sn1144.16 (19)C24—Co2—Sn485.28 (14)
C1—Co1—Sn186.74 (15)C26—Co2—Sn4141.95 (16)
C2—Co1—Sn1106.42 (17)C25—Co2—Sn4104.72 (15)
C4—Co1—Sn1166.18 (15)C27—Co2—Sn4166.36 (14)
C11—Co1—Sn197.96 (12)C34—Co2—Sn498.44 (12)
C12—Co1—Sn1129.04 (13)C35—Co2—Sn4130.42 (12)
Sn3—Co1—Sn187.09 (2)Sn6—Co2—Sn487.15 (2)
C3—Co1—Sn2126.82 (19)C24—Co2—Sn5145.11 (15)
C1—Co1—Sn2146.16 (16)C26—Co2—Sn5128.37 (16)
C2—Co1—Sn2166.12 (17)C25—Co2—Sn5167.34 (15)
C4—Co1—Sn295.78 (17)C27—Co2—Sn597.77 (15)
C11—Co1—Sn2110.27 (13)C34—Co2—Sn5109.82 (12)
C12—Co1—Sn289.63 (14)C35—Co2—Sn591.08 (13)
Sn3—Co1—Sn285.14 (2)Sn6—Co2—Sn585.73 (2)
Sn1—Co1—Sn287.46 (2)Sn4—Co2—Sn587.95 (2)
C3—Co1—Sn3'97.4 (2)C24—Co2—Sn6'105.7 (4)
C1—Co1—Sn3'103.7 (2)C26—Co2—Sn6'96.5 (3)
C2—Co1—Sn3'84.7 (2)C25—Co2—Sn6'85.8 (4)
C4—Co1—Sn3'130.8 (2)C27—Co2—Sn6'129.0 (3)
C11—Co1—Sn3'140.25 (19)C34—Co2—Sn6'142.7 (3)
C12—Co1—Sn3'165.27 (19)C35—Co2—Sn6'164.1 (3)
Sn1'—Co1—Sn3'86.31 (18)Sn5'—Co2—Sn6'86.5 (3)
Sn2'—Co1—Sn3'86.25 (19)Sn4'—Co2—Sn6'86.8 (3)
C2—C1—C11122.2 (5)C25—C24—C34121.2 (5)
C2—C1—Co170.8 (3)C25—C24—Co271.1 (3)
C11—C1—Co177.4 (3)C34—C24—Co277.5 (3)
C2—C1—H1121 (3)C25—C24—H24119 (3)
C11—C1—H1117 (3)C34—C24—H24119 (3)
Co1—C1—H1126 (3)Co2—C24—H24131 (3)
C1—C2—C3118.6 (6)C24—C25—C26118.9 (5)
C1—C2—Co170.7 (3)C24—C25—Co269.9 (3)
C3—C2—Co170.0 (3)C26—C25—Co270.1 (3)
C1—C2—H2121 (4)C24—C25—H25119 (3)
C3—C2—H2120 (4)C26—C25—H25121 (3)
Co1—C2—H2129 (4)Co2—C25—H25128 (3)
C4—C3—C2121.1 (5)C27—C26—C25120.7 (5)
C4—C3—Co172.1 (3)C27—C26—Co272.5 (3)
C2—C3—Co170.4 (3)C25—C26—Co270.5 (3)
C4—C3—H3116 (4)C27—C26—H26124 (4)
C2—C3—H3122 (4)C25—C26—H26115 (4)
Co1—C3—H3123 (4)Co2—C26—H26134 (4)
C3—C4—C12120.9 (5)C26—C27—C35121.3 (5)
C3—C4—Co169.5 (3)C26—C27—Co269.6 (3)
C12—C4—Co176.5 (3)C35—C27—Co277.1 (3)
C3—C4—H4120 (3)C26—C27—H27118 (3)
C12—C4—H4119 (3)C35—C27—H27120 (3)
Co1—C4—H4126 (3)Co2—C27—H27127 (3)
C6—C5—C13120.6 (6)C29—C28—C36119.7 (6)
C6—C5—H5119.7C29—C28—H28120.1
C13—C5—H5119.7C36—C28—H28120.1
C5—C6—C7122.9 (6)C28—C29—C30121.8 (6)
C5—C6—H6118.5C28—C29—H29119.1
C7—C6—H6118.5C30—C29—H29119.1
C8—C7—C6117.7 (5)C31—C30—C29120.8 (6)
C8—C7—H7121.1C31—C30—H30119.6
C6—C7—H7121.1C29—C30—H30119.6
C7—C8—C14122.0 (5)C30—C31—C37120.4 (6)
C7—C8—H8119.0C30—C31—H31119.8
C14—C8—H8119.0C37—C31—H31119.8
C14—C9—C11122.3 (4)C37—C32—C34122.3 (4)
C14—C9—H9118.9C37—C32—H32118.8
C11—C9—H9118.9C34—C32—H32118.8
C13—C10—C12121.6 (5)C36—C33—C35122.4 (5)
C13—C10—H10119.2C36—C33—H33118.8
C12—C10—H10119.2C35—C33—H33118.8
C9—C11—C1123.0 (5)C32—C34—C35118.6 (4)
C9—C11—C12118.8 (5)C32—C34—C24122.9 (4)
C1—C11—C12118.2 (4)C35—C34—C24118.5 (4)
C9—C11—Co1135.6 (3)C32—C34—Co2135.6 (3)
C1—C11—Co164.4 (3)C35—C34—Co272.7 (3)
C12—C11—Co171.5 (3)C24—C34—Co264.2 (3)
C10—C12—C4123.1 (5)C33—C35—C34118.6 (4)
C10—C12—C11118.7 (5)C33—C35—C27123.0 (4)
C4—C12—C11118.2 (5)C34—C35—C27118.4 (5)
C10—C12—Co1135.5 (4)C33—C35—Co2138.5 (4)
C4—C12—Co165.7 (3)C34—C35—Co270.6 (3)
C11—C12—Co171.4 (3)C27—C35—Co265.3 (3)
C10—C13—C5121.9 (5)C33—C36—C28122.4 (5)
C10—C13—C14119.9 (5)C33—C36—C37119.1 (5)
C5—C13—C14118.2 (5)C28—C36—C37118.5 (5)
C9—C14—C8122.6 (5)C32—C37—C31122.5 (5)
C9—C14—C13118.8 (5)C32—C37—C36119.0 (4)
C8—C14—C13118.6 (5)C31—C37—C36118.5 (5)
C16—Sn1—C17102.3 (2)C38—Sn4—C3999.8 (2)
C16—Sn1—C1599.3 (2)C38—Sn4—C40105.0 (2)
C17—Sn1—C15104.9 (3)C39—Sn4—C40101.9 (2)
C16—Sn1—Co1112.4 (2)C38—Sn4—Co2126.31 (15)
C17—Sn1—Co1109.18 (16)C39—Sn4—Co2112.00 (15)
C15—Sn1—Co1126.0 (3)C40—Sn4—Co2109.04 (16)
Sn1—C15—H15A109.5Sn4—C38—H38A109.5
Sn1—C15—H15B109.5Sn4—C38—H38B109.5
H15A—C15—H15B109.5H38A—C38—H38B109.5
Sn1—C15—H15C109.5Sn4—C38—H38C109.5
H15A—C15—H15C109.5H38A—C38—H38C109.5
H15B—C15—H15C109.5H38B—C38—H38C109.5
Sn1—C16—H16A109.5Sn4—C39—H39A109.5
Sn1—C16—H16B109.5Sn4—C39—H39B109.5
H16A—C16—H16B109.5H39A—C39—H39B109.5
Sn1—C16—H16C109.5Sn4—C39—H39C109.5
H16A—C16—H16C109.5H39A—C39—H39C109.5
H16B—C16—H16C109.5H39B—C39—H39C109.5
Sn1—C17—H17A109.5Sn4—C40—H40A109.5
Sn1—C17—H17B109.5Sn4—C40—H40B109.5
H17A—C17—H17B109.5H40A—C40—H40B109.5
Sn1—C17—H17C109.5Sn4—C40—H40C109.5
H17A—C17—H17C109.5H40A—C40—H40C109.5
H17B—C17—H17C109.5H40B—C40—H40C109.5
C20—Sn2—C18105.1 (3)C41—Sn5—C4299.8 (3)
C20—Sn2—C19108.1 (3)C41—Sn5—C43104.2 (3)
C18—Sn2—C1998.7 (3)C42—Sn5—C43106.4 (2)
C20—Sn2—Co1106.28 (18)C41—Sn5—Co2126.63 (18)
C18—Sn2—Co1127.0 (2)C42—Sn5—Co2110.42 (16)
C19—Sn2—Co1110.5 (3)C43—Sn5—Co2107.81 (16)
Sn2—C18—H18A109.5Sn5—C41—H41A109.5
Sn2—C18—H18B109.5Sn5—C41—H41B109.5
H18A—C18—H18B109.5H41A—C41—H41B109.5
Sn2—C18—H18C109.5Sn5—C41—H41C109.5
H18A—C18—H18C109.5H41A—C41—H41C109.5
H18B—C18—H18C109.5H41B—C41—H41C109.5
Sn2—C19—H19A109.5Sn5—C42—H42A109.5
Sn2—C19—H19B109.5Sn5—C42—H42B109.5
H19A—C19—H19B109.5H42A—C42—H42B109.5
Sn2—C19—H19C109.5Sn5—C42—H42C109.5
H19A—C19—H19C109.5H42A—C42—H42C109.5
H19B—C19—H19C109.5H42B—C42—H42C109.5
Sn2—C20—H20A109.5Sn5—C43—H43A109.5
Sn2—C20—H20B109.5Sn5—C43—H43B109.5
H20A—C20—H20B109.5H43A—C43—H43B109.5
Sn2—C20—H20C109.5Sn5—C43—H43C109.5
H20A—C20—H20C109.5H43A—C43—H43C109.5
H20B—C20—H20C109.5H43B—C43—H43C109.5
C23—Sn3—C21105.8 (3)C44—Sn6—C4599.8 (3)
C23—Sn3—C22106.6 (3)C44—Sn6—C46107.4 (2)
C21—Sn3—C22100.4 (2)C45—Sn6—C46106.1 (2)
C23—Sn3—Co1109.53 (18)C44—Sn6—Co2126.20 (17)
C21—Sn3—Co1125.91 (17)C45—Sn6—Co2107.62 (18)
C22—Sn3—Co1106.98 (19)C46—Sn6—Co2108.02 (17)
Sn3—C21—H21A109.5Sn6—C44—H44A109.5
Sn3—C21—H21B109.5Sn6—C44—H44B109.5
H21A—C21—H21B109.5H44A—C44—H44B109.5
Sn3—C21—H21C109.5Sn6—C44—H44C109.5
H21A—C21—H21C109.5H44A—C44—H44C109.5
H21B—C21—H21C109.5H44B—C44—H44C109.5
Sn3—C22—H22A109.5Sn6—C45—H45A109.5
Sn3—C22—H22B109.5Sn6—C45—H45B109.5
H22A—C22—H22B109.5H45A—C45—H45B109.5
Sn3—C22—H22C109.5Sn6—C45—H45C109.5
H22A—C22—H22C109.5H45A—C45—H45C109.5
H22B—C22—H22C109.5H45B—C45—H45C109.5
Sn3—C23—H23A109.5Sn6—C46—H46A109.5
Sn3—C23—H23B109.5Sn6—C46—H46B109.5
H23A—C23—H23B109.5H46A—C46—H46B109.5
Sn3—C23—H23C109.5Sn6—C46—H46C109.5
H23A—C23—H23C109.5H46A—C46—H46C109.5
H23B—C23—H23C109.5H46B—C46—H46C109.5
C16'—Sn1'—C17'102.3 (5)C38'—Sn4'—C39'99.8 (4)
C16'—Sn1'—C15'99.3 (4)C38'—Sn4'—C40'105.0 (5)
C17'—Sn1'—C15'104.9 (5)C39'—Sn4'—C40'101.9 (5)
C16'—Sn1'—Co1113 (4)C38'—Sn4'—Co2120 (4)
C17'—Sn1'—Co1113 (2)C39'—Sn4'—Co2122 (4)
C15'—Sn1'—Co1122 (3)C40'—Sn4'—Co2106 (4)
Sn1'—C15'—H15D109.5Sn4'—C38'—H38D109.5
Sn1'—C15'—H15E109.5Sn4'—C38'—H38E109.5
H15D—C15'—H15E109.5H38D—C38'—H38E109.5
Sn1'—C15'—H15F109.5Sn4'—C38'—H38F109.5
H15D—C15'—H15F109.5H38D—C38'—H38F109.5
H15E—C15'—H15F109.5H38E—C38'—H38F109.5
Sn1'—C16'—H16D109.5Sn4'—C39'—H39D109.5
Sn1'—C16'—H16E109.5Sn4'—C39'—H39E109.5
H16D—C16'—H16E109.5H39D—C39'—H39E109.5
Sn1'—C16'—H16F109.5Sn4'—C39'—H39F109.5
H16D—C16'—H16F109.5H39D—C39'—H39F109.5
H16E—C16'—H16F109.5H39E—C39'—H39F109.5
Sn1'—C17'—H17D109.5Sn4'—C40'—H40D109.5
Sn1'—C17'—H17E109.5Sn4'—C40'—H40E109.5
H17D—C17'—H17E109.5H40D—C40'—H40E109.5
Sn1'—C17'—H17F109.5Sn4'—C40'—H40F109.5
H17D—C17'—H17F109.5H40D—C40'—H40F109.5
H17E—C17'—H17F109.5H40E—C40'—H40F109.5
C20'—Sn2'—C18'105.1 (5)C41'—Sn5'—C42'99.8 (5)
C20'—Sn2'—C19'108.1 (5)C41'—Sn5'—C43'104.2 (5)
C18'—Sn2'—C19'98.7 (5)C42'—Sn5'—C43'106.4 (5)
C20'—Sn2'—Co1116 (2)C41'—Sn5'—Co2125 (5)
C18'—Sn2'—Co1122 (3)C42'—Sn5'—Co2107 (4)
C19'—Sn2'—Co1105 (3)C43'—Sn5'—Co2112 (4)
Sn2'—C18'—H18D109.5Sn5'—C41'—H41D109.5
Sn2'—C18'—H18E109.5Sn5'—C41'—H41E109.5
H18D—C18'—H18E109.5H41D—C41'—H41E109.5
Sn2'—C18'—H18F109.5Sn5'—C41'—H41F109.5
H18D—C18'—H18F109.5H41D—C41'—H41F109.5
H18E—C18'—H18F109.5H41E—C41'—H41F109.5
Sn2'—C19'—H19D109.5Sn5'—C42'—H42D109.5
Sn2'—C19'—H19E109.5Sn5'—C42'—H42E109.5
H19D—C19'—H19E109.5H42D—C42'—H42E109.5
Sn2'—C19'—H19F109.5Sn5'—C42'—H42F109.5
H19D—C19'—H19F109.5H42D—C42'—H42F109.5
H19E—C19'—H19F109.5H42E—C42'—H42F109.5
Sn2'—C20'—H20D109.5Sn5'—C43'—H43D109.5
Sn2'—C20'—H20E109.5Sn5'—C43'—H43E109.5
H20D—C20'—H20E109.5H43D—C43'—H43E109.5
Sn2'—C20'—H20F109.5Sn5'—C43'—H43F109.5
H20D—C20'—H20F109.5H43D—C43'—H43F109.5
H20E—C20'—H20F109.5H43E—C43'—H43F109.5
C23'—Sn3'—C21'105.8 (5)C44'—Sn6'—C45'99.8 (5)
C23'—Sn3'—C22'106.6 (5)C44'—Sn6'—C46'107.4 (5)
C21'—Sn3'—C22'100.4 (4)C45'—Sn6'—C46'106.1 (5)
C23'—Sn3'—Co1108 (2)C44'—Sn6'—Co2126 (4)
C21'—Sn3'—Co1133 (2)C45'—Sn6'—Co2110 (4)
C22'—Sn3'—Co199 (2)C46'—Sn6'—Co2106 (4)
Sn3'—C21'—H21D109.5Sn6'—C44'—H44D109.5
Sn3'—C21'—H21E109.5Sn6'—C44'—H44E109.5
H21D—C21'—H21E109.5H44D—C44'—H44E109.5
Sn3'—C21'—H21F109.5Sn6'—C44'—H44F109.5
H21D—C21'—H21F109.5H44D—C44'—H44F109.5
H21E—C21'—H21F109.5H44E—C44'—H44F109.5
Sn3'—C22'—H22D109.5Sn6'—C45'—H45D109.5
Sn3'—C22'—H22E109.5Sn6'—C45'—H45E109.5
H22D—C22'—H22E109.5H45D—C45'—H45E109.5
Sn3'—C22'—H22F109.5Sn6'—C45'—H45F109.5
H22D—C22'—H22F109.5H45D—C45'—H45F109.5
H22E—C22'—H22F109.5H45E—C45'—H45F109.5
Sn3'—C23'—H23D109.5Sn6'—C46'—H46D109.5
Sn3'—C23'—H23E109.5Sn6'—C46'—H46E109.5
H23D—C23'—H23E109.5H46D—C46'—H46E109.5
Sn3'—C23'—H23F109.5Sn6'—C46'—H46F109.5
H23D—C23'—H23F109.5H46D—C46'—H46F109.5
H23E—C23'—H23F109.5H46E—C46'—H46F109.5
C11—C1—C2—C37.7 (7)C34—C24—C25—C269.7 (7)
Co1—C1—C2—C352.9 (4)Co2—C24—C25—C2652.0 (4)
C11—C1—C2—Co160.6 (4)C34—C24—C25—Co261.7 (4)
C1—C2—C3—C40.2 (7)C24—C25—C26—C272.5 (7)
Co1—C2—C3—C453.4 (4)Co2—C25—C26—C2754.4 (4)
C1—C2—C3—Co153.2 (4)C24—C25—C26—Co251.8 (4)
C2—C3—C4—C126.4 (8)C25—C26—C27—C356.2 (7)
Co1—C3—C4—C1259.0 (4)Co2—C26—C27—C3559.6 (4)
C2—C3—C4—Co152.6 (4)C25—C26—C27—Co253.5 (4)
C13—C5—C6—C70.8 (11)C36—C28—C29—C300.0 (10)
C5—C6—C7—C80.5 (10)C28—C29—C30—C312.0 (10)
C6—C7—C8—C140.4 (8)C29—C30—C31—C370.5 (9)
C14—C9—C11—C1177.3 (4)C37—C32—C34—C352.0 (7)
C14—C9—C11—C121.0 (7)C37—C32—C34—C24178.3 (4)
C14—C9—C11—Co191.4 (6)C37—C32—C34—Co296.2 (6)
C2—C1—C11—C9173.3 (4)C25—C24—C34—C32172.2 (4)
Co1—C1—C11—C9129.3 (4)Co2—C24—C34—C32129.2 (4)
C2—C1—C11—C128.4 (7)C25—C24—C34—C358.1 (7)
Co1—C1—C11—C1249.0 (4)Co2—C24—C34—C3550.4 (4)
C2—C1—C11—Co157.4 (4)C25—C24—C34—Co258.6 (4)
C13—C10—C12—C4179.4 (5)C36—C33—C35—C340.6 (8)
C13—C10—C12—C110.6 (8)C36—C33—C35—C27178.9 (5)
C13—C10—C12—Co191.6 (7)C36—C33—C35—Co292.0 (6)
C3—C4—C12—C10174.6 (5)C32—C34—C35—C332.4 (7)
Co1—C4—C12—C10129.7 (5)C24—C34—C35—C33177.9 (4)
C3—C4—C12—C115.5 (7)Co2—C34—C35—C33135.4 (4)
Co1—C4—C12—C1150.2 (4)C32—C34—C35—C27179.1 (4)
C3—C4—C12—Co155.6 (4)C24—C34—C35—C270.5 (6)
C9—C11—C12—C100.2 (7)Co2—C34—C35—C2746.1 (4)
C1—C11—C12—C10178.2 (4)C32—C34—C35—Co2133.0 (4)
Co1—C11—C12—C10132.3 (5)C24—C34—C35—Co246.7 (4)
C9—C11—C12—C4179.9 (4)C26—C27—C35—C33170.7 (5)
C1—C11—C12—C41.7 (6)Co2—C27—C35—C33133.2 (5)
Co1—C11—C12—C447.6 (4)C26—C27—C35—C347.6 (7)
C9—C11—C12—Co1132.5 (4)Co2—C27—C35—C3448.5 (4)
C1—C11—C12—Co145.9 (4)C26—C27—C35—Co256.1 (4)
C12—C10—C13—C5178.5 (5)C35—C33—C36—C28174.8 (5)
C12—C10—C13—C140.5 (8)C35—C33—C36—C371.7 (8)
C6—C5—C13—C10178.9 (6)C29—C28—C36—C33179.8 (6)
C6—C5—C13—C140.2 (9)C29—C28—C36—C373.3 (8)
C11—C9—C14—C8179.0 (4)C34—C32—C37—C31179.4 (5)
C11—C9—C14—C131.0 (7)C34—C32—C37—C360.2 (7)
C7—C8—C14—C9179.1 (5)C30—C31—C37—C32176.3 (5)
C7—C8—C14—C131.0 (7)C30—C31—C37—C362.9 (8)
C10—C13—C14—C90.3 (7)C33—C36—C37—C322.1 (7)
C5—C13—C14—C9179.4 (5)C28—C36—C37—C32174.5 (5)
C10—C13—C14—C8179.8 (5)C33—C36—C37—C31178.7 (5)
C5—C13—C14—C80.7 (7)C28—C36—C37—C314.7 (7)
Comparison of (I) with free anthracene and selected `flat-slipped' structures (Å, °). top
The numbering is according to Fig. 2. For (I) and the molybdenum complex, only one of the two independent molecules for each is listed because they are metrically similar.
Feature(I)Anthracenea[(Cp")Ru(An)][PF6]bMoAn(PMe3)3c
M—C12.101 (5)2.207 (4)2.297 (3)
M—C22.102 (5)2.217 (4)2.261 (3)
M—C32.098 (5)2.223 (4)2.285 (3)
M—C42.132 (5)2.210 (4)2.268 (3)
M—C112.273 (5)2.289 (4)2.405 (3)
M—C212.274 (5)2.283 (4)2.424 (3)
Increase (avg.)0.1650.0720.137
C1—C21.387 (7)1.3675 (9)1.399 (6)1.407 (6)
C2—C31.423 (8)1.4264 (10)1.415 (7)1.419 (7)
C3—C41.393 (9)1.3674 (9)1.398 (7)1.408 (7)
C1—C111.438 (7)1.4297 (8)1.431 (6)1.434 (6)
C4—C121.436 (7)1.4295 (8)1.441 (6)1.452 (6)
C11—C121.449 (7)1.4384 (8)1.449 (5)1.455 (6)
Fold angle5.4 (3)4.45.4
Notes: (a) unpublished structure determined locally; (b) Konovalov et al. (2011), Cp'' = C5Me4(CH2OMe); (c) Zhu et al. (2006).

Experimental details

Crystal data
Chemical formula[CoSn3(C14H10)(CH3)9]
Mr728.52
Crystal system, space groupTriclinic, P1
Temperature (K)173
a, b, c (Å)12.9784 (18), 13.0834 (18), 16.734 (2)
α, β, γ (°)72.754 (2), 75.891 (2), 89.551 (2)
V3)2625.5 (6)
Z4
Radiation typeMo Kα
µ (mm1)3.45
Crystal size (mm)0.28 × 0.24 × 0.06
Data collection
DiffractometerSiemens SMART CCD platform
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2012)
Tmin, Tmax0.493, 0.746
No. of measured, independent and
observed [I > 2σ(I)] reflections
30588, 11891, 9564
Rint0.032
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.038, 0.086, 1.08
No. of reflections11891
No. of parameters639
No. of restraints42
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)1.93, 0.79

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

 

Acknowledgements

This research has been supported by the US National Science Foundation and the donors of the Petroleum Research Fund, administered by the American Chemical Society. The authors thank Benjamin D. Hamilton for preliminary work performed on the structure.

References

First citationBrennessel, W. W., Ellis, J. E., Pomije, M. K., Sussman, V. J., Urnezius, E. & Young, V. G. Jr (2002). J. Am. Chem. Soc. 124, 10258–10259.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationBrennessel, W. W., Jilek, R. E. & Ellis, J. E. (2007). Angew. Chem. Int. Ed. 46, 6132–6136.  Web of Science CSD CrossRef CAS Google Scholar
First citationBrennessel, W. W., Young, V. G. Jr & Ellis, J. E. (2006). Angew. Chem. Int. Ed. 45, 7268–7271.  Web of Science CSD CrossRef CAS Google Scholar
First citationBruker (2003). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationCorella, J. A. II, Thompson, R. L. & Cooper, N. J. (1992). Angew. Chem. Int. Ed. Engl. 31, 83–84.  CrossRef Web of Science Google Scholar
First citationFreedman, D. A., Gill, T. P., Blough, A. M., Koefod, R. S. & Mann, K. R. (1997). Inorg. Chem. 36, 95–102.  CrossRef CAS Web of Science Google Scholar
First citationGarcia, M. H., Valente, A., Florindo, P., Morais, T. S., Piedade, M. F. M., Duarte, M. T., Moreno, V., Avilés, F. X. & Loreno, J. (2010). Inorg. Chim. Acta, 363, 3765–3775.  Web of Science CSD CrossRef CAS Google Scholar
First citationGroom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. Engl. 53, 662–671.  Web of Science CrossRef CAS PubMed Google Scholar
First citationHanic, F. & Mills, O. S. (1968). J. Organomet. Chem. 11, 151–158.  CSD CrossRef CAS Web of Science Google Scholar
First citationHatanaka, T., Ohki, Y., Kamachi, T., Nakayama, T., Yoshizawa, K., Katada, M. & Tatsumi, K. (2012). Chem. Asian J. 7, 1231–1242.  Web of Science CSD CrossRef CAS PubMed Google Scholar
First citationKonovalov, A. I., Karslyan, E. E., Perekalin, D. S., Nelyubina, Y. V., Petrovskii, P. V. & Kudinov, A. R. (2011). Mendeleev Commun. 21, 163–164.  Web of Science CSD CrossRef CAS Google Scholar
First citationMcNair, A. M. & Mann, K. R. (1986). Inorg. Chem. 25, 2519–2527.  CrossRef CAS Web of Science Google Scholar
First citationMutseneck, E. V., Loginov, D. A., Pronin, A. A., Petrovskii, P. V. & Kudinov, A. R. (2007). Russ. Chem. Bull. 56, 1927–1929.  Web of Science CrossRef CAS Google Scholar
First citationParsons, S., Gould, B., Cooper, R. & Farrugia, L. (2003). ROTAX. University of Edinburgh, Scotland.  Google Scholar
First citationSchnöckelborg, E.-M., Khusniyarov, M. M., de Bruin, B., Hartl, F., Langer, T., Eul, M., Schulz, S., Pöttgen, R. & Wolf, W. (2012). Inorg. Chem. 51, 6719–6730.  Web of Science PubMed Google Scholar
First citationSeaburg, J. K., Fischer, P. J., Young, V. G. Jr & Ellis, J. E. (1998). Angew. Chem. Int. Ed. 37, 155–158.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2012). SADABS. University of Göttingen, Germany.  Google Scholar
First citationWoolf, A., Chaplin, A. B., McGrady, J. E., Alibadi, M. A. M., Rees, N., Draper, S., Murphy, F. & Weller, A. S. (2011). Eur. J. Inorg. Chem. pp. 1614–1625.  Web of Science CSD CrossRef Google Scholar
First citationZhu, G., Janak, K. E., Figueroa, J. S. & Parkin, G. (2006). J. Am. Chem. Soc. 128, 5452–5461.  Web of Science CSD CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds