Poly[[hexa-μ-cyanido-manganese(II)iron(III)] pentahydrate]

Abstract

Key indicators: single-crystal X-ray study; T = 90 K; mean (Mn-O) = 0.012 Å; Hatom completeness 1%; disorder in main residue; R factor = 0.047; wR factor = 0.136; data-to-parameter ratio = 13.2.The structure of the title compound, Mn II [Fe III (CN) 6 ] 2/3 Á-5H 2 O, features a face-centered cubic -Mn-NC-Fe-framework with both Mn and Fe having site symmetry m3m. Since one-third of the [Fe(CN) 6 ] 3À units are missing for a given formula in order to maintain charge neutrality, each Mn atom around such a vacancy is coordinated not only by the N atoms of the CN groups but also by the O atoms of the ligand water molecules. In addition to ligand water molecules, two types of non-coordinated water molecules, so-called zeolitic water molecules, exist in the interstitial sites of the -Mn-NC-Feframework. The positions of the O atoms of the zeolitic water molecules are fixed by the linkage via hydrogen bonds between ligand water and zeolitic water molecules. The structure is related to a recently reported rubidium manganese hexacyanoferrate. Site occupancy factors for Fe, C, N are 0.67; for two O atoms the value is 0.83 and for one O atom is 0.17. (1997, 2000, 2004, 2005); Sato et al. (1996);Tokoro et al. (2003Tokoro et al. ( , 2004Zeigler et al. (1999). Related literature ExperimentalCrystal data Mn[Fe(CN)

Guest-host interaction ofK0.34Co[Fe(CN)6]Kim1, Kato2, Takata3 et al. 2009Phys. Rev. B16190View full textAdd to dashboardCite

“…1͑b͒ at z = 3.6. Our structural analysis indicates that the off-axis water coexists with the ligand water, making a sharp contrast with the result reported by Matsuda et al 10 Consistently with our analysis, Takeda et al 17 performed a magic angle spinning ͑MAS͒ deutron NMR ͓ 2 D-MAS NMR ͑Ref. 18͔͒ for Na 0.40 Co͓Na͑CN͒ 6 ͔ 0.79 · zD 2 O and found three signals, whose isotropic shifts are 2 ppm ͑49%͒, −13 ppm ͑20%͒, and −39 ppm ͑31%͒ at 364 K. The water site at 2 ppm, which negligibly interacts with magnetic ions, should be ascribed to the zeolite water ͑41%͒ while the isotropic shift of −39 ppm is ascribed to the coordination bond of the ligand water ͑25%͒.…”

“…We, therefore, think that formation of the hydrogen bonding between the zeolite and the off-axis waters is the reason for the existence of the lowsymmetry off-axis site. A similar argument is performed by Matsuda et al 10 It is interesting that a distorted dodecahedron ͑3O 1 +3O 2 + 12O 4 ͒ appears within the void if we link the O 1 -O 4 and O 2 -O 4 hydrogen bonds. Such a dodecahedron would be configured with the aid of the interaction between O 4 and the neighboring Co atom ͑vide infra͒, and should not be regarded as an isolated cluster.…”

“…Herren et al 9 determined the oxygen positions, i.e., zeolite site ͑8c and 32f͒ and the ligand site ͑24c͒ in Fm3m model, for Fe III ͓Fe II ͑CN͒ 6 ͔ 3/4 · 3.5H 2 O by means of the neutron powder structural analysis. Matsuda et al, 10 however, proposed off-axis site ͑96i͒ instead of ligand site for Mn II ͓Fe III ͑CN͒ 6 ͔ 2/3 ·5H 2 O by means of the single-crystal x-ray structural analysis. Thus, even the position of the guest waters within the host lattice is still controversial.…”

Desorption-erasure of the Spin State Transition in Prussian-blue Type Cyanide

“…The residual waters (zeolite water) form clusters and are weakly bound within the nano pores. [3][4][5][6] A significant feature of the cyano-bridged compound is the tenability of the guest concentration by heat treatment, 4) humidity, 7) electrochemical process, 8) and so on. Especially, the valence state of the transition metal can be tuned by the Na concentration (x), 8) analogously to the case of the chemical hole-doping in the transition metal oxides.…”

“…Hereafter, we will call the absorption band ''Co II band''. The Co II band is dipole-forbidden within a center-symmetric (O h ) ligand field, e.g., in the coordination of Co(CN) 6 . In an actual Co-Fe cyanide, however, part of the CN group is replaced by the ligand water, making the band dipole-allowed via the strong hybridization between the Coe g orbital and the CN orbital.…”