Anomalous Stoichiometry and Antiferromagnetic Ordering for the Extended Hydroxymanganese(II) Cubes/Hexacyanometalate‐Based 3D‐Structured [MnII4(OH)4][MnII(CN)6](OH2)6⋅H2O. Issue 7 (8th January 2019)

• Record Type: Journal Article
• Authors: Lapidus, Saul H.; Stephens, Peter W.; Kareis, Christopher M.; VanNatta, Peter E.; Miller, Joel S.
• Is Part Of: Chemistry. Volume 25:Issue 7(2019)
• Page Start: 1752
• Page End: 1757
• Publication Date: 2019-01-08
• Subjects: antiferromagnet -- crystal structure -- magnetic properties -- Mn; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201804935
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The reaction of Mn II (O2 CMe)2 and NaCN or LiCN in water forms a light green insoluble material. Structural solution and Rietveld refinement of high‐resolution synchrotron powder diffraction data for this unprecedented, complicated compound of previously unknown composition revealed a new alkali‐free ordered structural motif with [Mn II 4 (μ3 ‐OH)4 ] 4+ cubes and octahedral [Mn II (CN)6 ] 4− ions interconnected in 3D by Mn II ‐N≡C‐Mn II linkages. The composition is {[Mn II (OH2 )3 ][Mn II (OH2 )]3 }(μ3 ‐OH)4 ][Mn II (μ‐CN)2 (CN)4 ]⋅ H2 O=[Mn II 4 (μ3 ‐OH)4 (OH2 )6 ][Mn II (μ‐CN)2 (CN)4 ]⋅ H2 O, which is further simplified to [Mn4 (OH)4 ][Mn(CN)6 ](OH2 )7 (1 ).1 has four high‐spin ( S =5/2) Mn II sites that are antiferromagnetically coupled within the cube and are antiferromagnetically coupled to six low‐spin ( S =1/2) octahedral [Mn II (CN)6 ] 4− ions. Above 40 K the magnetic susceptibility, χ ( T ), can be fitted to the Curie–Weiss expression, χ ∝( T − θ ) −1, with θ =−13.4 K, indicative of significant antiferromagnetic coupling and1 orders as an antiferromagnet at T c =7.8 K. Abstract : Structural solution and Rietveld refinement of high‐resolution diffraction data for an unprecedented, complicated compound of previously unknown composition revealed a new alkali‐free ordered structural motif with [Mn II 4 (μ3 ‐OH)4 ] 4+ cubes and octahedral [Mn II (CN)6 ] 4− ions interconnected in 3D.