MACROBICYCLIC D-METAL TRIS-DIOXIMATES OBTAINED BY CROSS-LINKING WITH P-BLOCK ELEMENTS .8. PREPARATION, CRYSTAL AND MOLECULAR-STRUCTURES AND MOSSBAUER (FE-57) PARAMETERS OF MACROBICYCLIC N-BUTYL AND PHENYLBORON-CONTAINING IRON(II) TRIS-DIOXIMATES

The structure of two clathrochelate complexes with glyoxime FeGm3(Bn-C4H9)2 (I, monoclinic, a = 8,256 (7), b = 23.98 (2), c = 19.76 (2) angstrom, beta = 90.06 (2)degrees, V = 3911 (5) angstrom3, space group Pn, Z = 8) and difurylglyoxime FeFd3(BC6H5)2.1/4 CHCl3 (II, monoclinic, a = 27.385 (5), b = 9.753 (2), c = 17.047 (3) angstrom, beta = 107.17 (3)degrees, V = 4350 (1) angstrom3, space group P2(1)/c, Z = 4) were solved. The coordination polyhedrons of encapsulated by the clathrochelate ligands central iron atoms are intermediate between trigonal prism and trigonal antiprism. Distortion angle in I (approximately 10.9-degrees) is the smallest of the values known for complexes of this type. The distortion angle value for II (approximately 26.5-degrees) is much lower than predicted from Mossbauer (Fe-57) data. The Fe-N bond length (1.91-1.92 angstrom) and bite angles (38.6 and 39.2-degrees respectively) are typical of macrobicyclic tris-dioximates. The differences between the calculated and experimentally observed Mossbauer (Fe-57) parameters and molecular structure requliarities of synthesized compounds are discussed.