Tris-(tetraethylammonium) hexacyanoferrate (III): Stability of its hydrates and X-ray structure of the pentahydrate

Ouahab, Lahcène; Bouherour, Soraya; Auffrédic, Jean-Paul; Grandjean, Daniel

doi:10.1016/0022-4596(89)90233-8

Cited by 7 publications

(8 citation statements)

References 5 publications

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“…van der Waals interactions between the cetyl chains of CDA favor close packing and interdigitation of the extended nonpolar alkyl tails of neighboring surfactant molecules. The interdigitated bilayer structure in the crystal is a common morphology of surfactants in their crystalline forms, as reported earlier for CTAB and SDS. , The formation of [Fe(CN) 6 ] 3- layers in the crystal is promoted by the (CDA) + surfactants, as shown by comparison with the structure of (Et 4 N) 3 [Fe(CN) 6 ] that displays no bilayer structure …”

supporting

confidence: 73%

“…21,22 The formation of [Fe(CN) 6 ] 3layers in the crystal is promoted by the (CDA) + surfactants, as shown by comparison with the structure of (Et 4 N) 3 [Fe(CN) 6 ] that displays no bilayer structure. 23 In summary, we have shown that 1 forms RMs in chloroform. These RMs can incorporate anionic metal complexes with hydrogen bonding to the ligands as exemplified by the [Fe(CN) 6 ] 3anion.…”

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confidence: 63%

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Amide−Ligand Hydrogen Bonding in Reverse Micelles

et al. 2005

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One approach to modeling the second coordination shell of metalloproteins is to pair amide-containing counterions with metal complexes to form hydrogen bonds in the solid state. In a more general approach, we have designed a surfactant counterion that can sustain hydrogen bonding interactions with metal complexes in solution. The surfactant is cationic and incorporates an amide as part of its headgroup to form hydrogen. The surfactant forms hydrogen bonding reverse micelles that accommodate anionic metal complexes in their polar core. In reverse micelles containing an iron(III) hexacyanide complex, spectroscopic evidence suggests that the anion is confined to the polar core region in solution. Single-crystal X-ray diffraction data on the surfactant ferricyanide system reveals a layered structure with interdigitated alkyl chains and an extensive network of hydrogen bonds that link amide groups to the cyanide ligands and to neighboring headgroups.

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confidence: 73%

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confidence: 63%

Amide−Ligand Hydrogen Bonding in Reverse Micelles

et al. 2005

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“…Octahedral A 4 [Mn II (CN) 6 ] ( n =1, m =4; A=Na, K) is low spin ( S =1/2) [15,19] as expected for possessing the strong field C‐bonded CN − ligand [20] . Formation of A 4 [Mn II (CN) 6 ] (A=tetraalkylammonium), akin to the known A 4 [Fe II (CN) 6 ], [21] solely led to the formation of A 2 [Mn II (CN) 4 ], the first tetrahedral percyanometallate of a transition metal, Figure 1a [22] . Due to the strong field nature of the CN − ligand, all previously characterized percyanometallates [4 (square planar) and 6 coordinate] are low spin.…”

Section: Compounds Of Ammniin(cn)m+2n Compositionmentioning

confidence: 99%

“…Cs 2 Mn II [Mn II (CN) 6 ] was cubic, Figure 3a, but Rb 2 Mn II [Mn II -(CN) 6 ], Figure 3b, like K 2 Mn II [Mn II (CN) 6 ] was monoclinic. [14] At- 2À showing thermal ellipsoids (50 %) (Mn is maroon, C black, and N light blue) (a), [22,23] and two interpenetrating diamondoid Mn(CN) 2 lattices in magenta and cyan (b). [25,26] tempts to make Na 2 Mn II [Mn II (CN) 6 ] led to monoclinic Na 2 Mn II -[Mn II (CN) 6 ] • 2H 2 O, Figure 3c, which upon dehydration formed rhombohedral Na 2 Mn II [Mn II (CN) 6 ], Figure 3d.…”

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Cation Adaptive Structures Based on Manganese Cyanide Prussian Blue Analogues: Application of Powder Diffraction Data to Solve Complex, Unprecedented Stoichiometries and New Structure Types

Miller

Stephens

2023

Chemistry A European J

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A Mn(II) salt and A+CN‐ under anaerobic conditions react to form extended structured compounds of AmMnIIn(CN)m+2n stoichiometry, e.g. AMnII3(CN)7, A2MnII3(CN)8, A2MnII5(CN)12, A3MnII5(CN)13, and A2MnII[MnII(CN)6] (A represents alkali and tetraalkylammonium cations). Cs2MnII[MnII(CN)6] has the typical Prussian blue face centered cubic unit cell. However, the other alkali salts are monoclinic or rhombohedral. This is in accord with smaller alkali cation radii creating void space that is minimized by increasing the van der Waals stabilization energy by reducing ∠Mn–N≡C. This is attributed to the non‐rigidity of the framework structure due the significant ionic character associated with the high‐spin MnII sites. For larger tetraalkylammonium cations, the high‐spin Mn sites lack sufficient electrostatic A+•••NC stabilization and only form unexpected 4‐ and 5‐coordinated Mn sites within a flexible, extended framework around the cation; hence, the size, shape, and charge of the cation dictate the unprecedented stoichiometry and unpredictable cation adaptive structures. Antiferromagnetic coupling between adjacent MnII sites leads to ferrimagnetic ordering, but in some cases antiferromagnetic coupling of ferrimagnetic layers are compensated and synthetic antiferromagnets are observed. The magnetic ordering temperatures for ferrimagnetic A2MnII[MnII(CN)6] with both octahedral high‐ and low‐spin MnII sites increase with decreasing ∠Mn–N≡C. The extended structured materials were obtained by powder diffraction.

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