Synthetic, X-ray Structure, Electron Paramagnetic Resonance, and Magnetic Studies of the Manganese(II) Complex of 1-Thia-4,7-diazacyclononane ([9]aneN2S)

Abstract
Reaction of manganese(II) perchlorate hexahydrate with a methanol solution of 1-thia-4,7-diazacyclononane ([9]aneN2S) resulted in the isolation of the manganese(II) complex [Mn([9]aneN2S)2](ClO4)2. The X-ray structure of this complex is reported: crystal system orthorhombic, space group Pbam, No. 55, a = 7.937(2) Å, b = 8.811(2) Å, c = 15.531(3) Å, Z = 2, R = 0.0579. The complex is high spin (S = 5/2) with an effective magnetic moment (μeff) 5.82 μB at 298 K and 5.65 μB at 4.2 K. Computer simulation of the Q-band EPR spectrum of [Mn([9]aneN2S)2](ClO4)2 yields g = 1.99 ± 0.01, |D| = 0.19 ± 0.005 cm-1, and E/D = 0.04 ± 0.02. For the analogous hexaamine complex [Mn([9]aneN3)2](ClO4)2 ([9]aneN3 = 1,4,7-triazacyclononane) analysis of the EPR spectra produced the following values: g = 1.98 ± 0.01, |D| = 0.09 ± 0.003 cm-1, and E/D = 0.1 ± 0.01. The spin Hamiltonian parameters for [Mn([9]aneN2S)2](ClO4)2 derived from the EPR spectra produced a good fit to the magnetic susceptibility data.

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