Publication details
Two complexes crystallizing from the aqueous system Ni2+-tacn-[Ni(CN)(4)](2)-(tacn=1,4,7-triazacyclononane)
| Authors | |
|---|---|
| Year of publication | 2008 |
| Type | Article in Periodical |
| Magazine / Source | Journal of coordination chemistry |
| MU Faculty or unit | |
| Citation | |
| web | https://doi.org/10.1080/00958970802056586 |
| Doi | http://dx.doi.org/10.1080/00958970802056586 |
| Keywords | Tetracyanonickellate; Nickel; Crystal structure; 1.4.7-Triazacyclononane; Zero-field splitting |
| Description | Two new complexes [Ni(tacn)(2)][Ni(CN)(4)](H2O)-H-2 (1) and Ni(tacn)Ni(CN)(4)center dot H2O (2) (tacn = 1,4,7-triazacyclononane) have been synthesized from water and characterized by chemical analysis and infrared spectroscopy. Single-crystal X-ray structure analysis of 1 revealed an ionic structure built up of [Ni(tacn)(2)](2+) and [Ni(CN)(4)](2-) complex ions without coordinated water. While cationic Ni(II) atom is octahedrally coordinated by two tridentate tacn ligands with Ni-N bonds from 2.101(3)-2.118(3)angstrom, the anionic Ni(II) atom is square planar with Ni-C bonds from 1.866(4) to 1.880(3)angstrom. An extended hydrogen bonding system connects complex cations, complex anions and water yielding hydrogen-bonded layers. Magnetic study of 1 revealed a decrease of the effective magnetic moment from 2.90 (300 K) to 2.43 mu(B) at 1.8 K due to zero-field splitting. Fitting of the susceptibility data yielded g = 2.05, D/hc = 3.82 cm(-1) and E/hc = 0.23 cm(-1). IR spectral data indicate the presence of bridging cyano ligands in the structure of 2. |