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An Unusual (10,3)‐a Racemic Twofold Interpenetrating Network Assembled from Isolable Tris(cyclopentadienyl)manganate and Cesocene Building Blocks
Author(s) -
Kheradmandan Sohrab,
Schmalle Helmut W.,
Jacobsen Heiko,
Blacque Olivier,
Fox Thomas,
Berke Heinz,
Gross Mathias,
Decurtins Silvio
Publication year - 2002
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20020603)8:11<2526::aid-chem2526>3.0.co;2-i
Subject(s) - orthorhombic crystal system , chemistry , crown ether , crystallography , density functional theory , crystal structure , stereochemistry , computational chemistry , ion , organic chemistry
The syntheses and X‐ray crystal structures of [([18]crown‐6) 2 Cs] + [Cp 3 Mn] − ( 1 ), [([18]crown‐6) 2 Cs] + [Cp′ 3 Mn] − ( 2 ), [CsCp′] ( 3 ), [(CsCp′) 2 ([18]crown‐6)] ( 4 ), and Cs[MnCp 3 ] ( 5 ), and the synthesis of Cs[MnCp′ 3 ] ( 6 ) are reported (Cp′=C 5 H 4 Me). The anions [Cp 3 Mn] − ( 1 − ) and [Cp′ 3 Mn] − ( 2 − ) are characterized by η 2 coordination of all three Cp or Cp′ rings. Measurements of the magnetic susceptibilities χ M resulted in values of μ eff =6.20 μ B (300 K), μ eff =6.33 μ B (301 K), and μ eff =5.83 μ B (300 K) for 1, 2 , and 5 , respectively, which are indicative of high‐spin d 5 ‐ Mn 2+ centers. Density functional calculations illustrate that the coordination mode of 1 − is characteristic for its sextet electronic ground state. Compound 3 forms infinite chains of cesocene‐type sandwiches in the solid state, which are broken up into small subunits by the addition of crown ether to form 4 . Compound 5 is a rare example of a (10,3)‐a racemic interpenetrating network that crystallizes in the orthorhombic space group Pbca.