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The determined space group of C2/c for Dy 3N@C80·Ni(OEP)·2C6H6, which is different from those of the analogous compounds (C2/m) for M3N@C80 (I, M, Sc, Gd, refs 3 and 16, and the doubling of the c parameter indicate that the reason of a mirror disorder of the C80 cage reported in refs 3 and 16 was simply a nonperfect crystallization. This resulted in an irregular translation along the c axis and, consequently, in averaging of two mirrored orientations of the C80 cage, whereas the M(OEP) units (oriented more symmetrically relative the crystallographic axes) appeared to be not disordered. However, in a more recent report on CeSc2N@C80 (ref 14, the determined space group (C2/c) and c parameter were almost identical to our case, confirming the more perfect crystallization for Dy3N@C 80·
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80 cage for both cases.
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32
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33845991379
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Dy-to-ring center distances are 1.941, 1.927, and 1.936 Å, smaller than those for the case of Gd3 reported in ref 16.
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Dy-to-ring center distances are 1.941, 1.927, and 1.936 Å, smaller than those for the case of Gd3 reported in ref 16.
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33845972857
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Because the carbon cage atoms involved in interactions with Dy atoms are somewhat pushed outward from the cage, there is an additional small disorder for these atoms (because of the disorder of Dy atoms, thus explaining some irregularities (or distortions) for thermal ellipsoids of a few carbon atoms of the C80 cage
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80 cage.
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0035828670
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Krause, M.; Kuzmany, H.; Georgi, P.; Dunsch, L.; Vietze, K.; Seifert, G. J. Chem. Phys. 2001, 115, 6596-6605.
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Seifert, G.6
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33846029357
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This is contrary to the case of M-N antisymmetric stretching mode, which is defined only by the M-N force constant since displacements of the metal atoms in this vibration are negligible. Hence, νas,M-N frequencies of different M3N@C80 (I) can be compared directly
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80 (I) can be compared directly.
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