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The Formation of 3D Fullerene Packing in Molecular Complexes of C 60 and C 70 with Metal Diethyl Dithiophosphates: [M(dedtp) 2 ]·[C 60(70) ] 3 (M = Ni II , Co II , and V IV O)
Author(s) -
Konarev Dmitri V.,
Zorina Leokadiya V.,
Khasanov Salavat S.,
Lyubovskaya Rimma N.
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201200822
Subject(s) - fullerene , chemistry , van der waals force , fullerene chemistry , endohedral fullerene , crystallography , metal , molecule , vanadium , van der waals radius , computational chemistry , inorganic chemistry , organic chemistry
A series of molecular complexes of fullerenes C 60 and C 70 with metal diethyl dithiophosphates [M(dedtp) 2 ] · [C 60(70) ] 3 ( 1 – 4 ), in which M = Ni II , Co II , and V IV O was obtained as single crystals and structurally characterized. The complexes exhibit unusual three‐dimensional packing of the fullerenes in which each fullerene molecule forms van der Waals contacts with ten fullerene neighbors. Such fullerene packing has been observed for the first time in the molecular complexes of fullerenes. Each metal diethyl dithiophosphate molecule is surrounded by eight fullerenes and forms short van der Waals C ··· C contacts with fullerenes by ethoxy groups only. Central PS 2 MS 2 P fragments of [M(dedtp) 2 ] do not form short van der Waals contacts with fullerenes in 1 – 4 in contrast to previously studied fullerene complexes with metal diethyldithiocarbamates in which effective π–π interactions between the planar NCS 2 MS 2 CN fragments of dithiocarbamates and fullerenes was found. Both [Ni II (dedtp) 2 ] in 1 and 2 and [Co II (dedtp) 2 ] in 3 have square‐planar environments around the metal center with the M–S bonds in the 2.227(1)–2.275(1) Å range, whereas vanadium atoms have a square‐pyramidal environment in [V IV O(dedtp) 2 ] ( 4 ) with one short V–O bond that is 1.597(1) Å long and four longer V–S bonds in the 2.394–2.439(2) Å range.