Synthesis, Structure and Magnetic Properties of Catena-Micron-Oxo-Hemiporphyrazinatoiron(IV), the First Polymeric Micron-Oxo-Bridged Complex of Iron.
Abstract
The crystal and molecular structure of the compound catena-micron-oxo-hemiporphyrazinatoiron(IV), (Fe0N8C26H14n), has been determined from single-crystal, three-dimensional X-ray diffraction counter data. The compound crystalizes as blue-black needles in space group P2/n with Z = 2 and having unit cell dimensions (at 210 K) a = 16.090 (3) angstroms, b = 3.975 (2) angstroms, c = 16.070 (3) and beta = 92.97 (1). The structure was refined by full-matrix least-squares techniques to a conventional R value of 0.054. Distorted hemiporphyrazinatoiron units stack along the b axis and are linked into polymeric, uniformly spaced, linear chains by axially-bound oxygen bridges. The oxygen atoms are disordered into two crystallographically distinct sites lying about a central location which is normal to the C2 axis collinear with the chain. The Fe-0-Fe angles are 158.2 and 170.5, and the Fe-0 bond distances range from 1.973 angstroms to 2.030 angstroms, Mossbauer spectral studies at 4.2 K, room temperature and at 420 K reveal that there are two iron sites in the chain as a result of the disorder of the oxygen atoms, and the spectrum is essentially temperature independent. Magnetic susceptibility studies reveal that the iron ions are antiferromagnetically coupled in an alternating chain with J = -133 per cm, g = 2.3 and an alternation parameter of 0.4.
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 26, 1983
- Accession Number
- ADA132388
Entities
People
- Armin Datz
- Joachim Straehle
- Michael Hanack
- William E. Hatfield
- Wolfgang Hiller
Organizations
- University of North Carolina at Chapel Hill