Synthesis, Characterization, and Chemical Bonding Analysis of the Lithium Alkaline‐earth Metal Gallide Nitrides Li2(Ca3N)2[Ga4] and Li2(Sr3N)2[Ga4]

Pathak, Manisha; Stoiber, Dominik; Bobnar, Matej; Ovchinnikov, Alexander; Ormeci, Alim; Niewa, Rainer; Höhn, Peter

doi:10.1002/zaac.201700296

Cited by 7 publications

(2 citation statements)

References 55 publications

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“…This allows the consideration of the respective [Cl2Na6] framework in northupite as an antipyrochlo or an inverse pyrochlore, by analogy with antiperovskites or inverse perovskites [31]. Si ilar antipyrochlore frameworks formed by N-centered metal octahedra are known in kaline earth metal nitrides [32,33] and by O-centered (OTi6) octahedra in Ti2[Ti3O]2(P [34].…”

Section: Structural Relationsmentioning

confidence: 99%

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

et al. 2023

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The crystal structure of manganotychite has been refined using the holotype specimen from the Alluaiv Mountain, Lovozero massif, Kola peninsula, Russia. The mineral is cubic, Fd3¯, a = 14.0015(3) Å, V = 2744.88(18) Å3, Z = 8, R1 = 0.020 for 388 independently observed reflections. Manganotychite is isotypic to tychite and ferrotychite. Its crystal structure is based upon a three-dimensional infinite framework formed by condensation of MnO6 octahedra and CO3 groups by sharing common O atoms. The sulfate groups and Na+ cations reside in the cavities of the octahedral-triangular metal-carbonate framework. In terms of symmetry and basic construction of the octahedral-triangular framework, the crystal structure of manganotychite is identical to that of northupite, Na3Mg(CO3)2Cl. The transition northupite → tychite can be described as a result of the multiatomic 2Cl− → (SO4)2− substitution, where both chlorine and sulfate ions are the extra-framework constituents. However, the positions occupied by sulfate groups and chlorine ions correspond to different octahedral cavities within the skeletons of Na atoms. The crystal structure of northupite can be considered as an interpenetration of two frameworks: anionic [Mg(CO3)2]2− octahedral-triangular framework and cationic [ClNa3]2− framework with the antipyrochlore topology. Both manganotychite and northupite structure types can be described as a modification of the crystal structure of diamond (or the dia net) via the following steps: (i) replacement of a vertex of the dia net by an M4 tetrahedron (no symmetry reduction); (ii) attachment of (CO3) triangles to the triangular faces of the M4 tetrahedra (accompanied by the Fd3¯m → Fd3¯ symmetry reduction); (iii) filling voids of the resulting framework by Na+ cations (no symmetry reduction); and (iv) filling voids of the Na skeleton by either sulfate groups (in tychite-type structures) or chlorine atoms (in northupite). As a result, the information-based structural complexity of manganotychite and northupite exceeds that of the dia net.

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Section: Structural Relationsmentioning

confidence: 99%

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

et al. 2023

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“…The single crystal growth of nitrides is often challenging due to the large dissociation energy of the N 2 molecule, the reactivity of the starting materials and enhanced vapor pressures, but the high temperature centrifugation aided filtration (HTCAF) technique [18,19] using Li as a flux provides a powerful tool to produce large single crystals of a large variety of phases even in complex systems such as nitridometalates (e. g. Li 2 Sr[(Li 1−x Fe I x )N] 2 [20], LiSr 2 [Co I N 2 ] [21]) or nitride metalides like LiSr 3 Ga 2 N [22].…”

Section: Introductionmentioning

confidence: 99%

Li$_2$Sr[MnN]$_2$: a magnetically ordered, metallic nitride

Hirschberger,

Ballé,

Haas

et al. 2021

Preprint

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Li2Sr [MnN]2 single crystals were successfully grown out of Li rich flux. The crystal structure was determined by single crystal X-ray diffraction and revealed almost linear −N−Mn−N−Mn− chains as central structural motif. Tetragonal columns of this air and moisture sensitive nitridomanganate were employed for electrical transport, heat capacity, and anisotropic magnetization measurements. Both the electronic and magnetic properties are most remarkable, in particular the linear increase of the magnetic susceptibility with temperature that is reminiscent of underdoped cuprate and Fe-based superconductors. Clear indications for antiferromagnetic ordering at TN = 290 K were obtained. Metallic transport behavior is experimentally observed in accordance with electronic band structure calculations.

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Sr₄N[CN₂][C₂N]: The First Carbodiimide Acetonitriletriide

et al. 2019

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The acetonitriletriide anion C 2 N 3-, the fully deprotonated form of acetonitrile, is stabilized in a pure alkaline earth metal environment in Sr 4 N[CN 2 ][C 2 N]. The heterogeneous reaction of graphite and elemental nitrogen (from decomposed NaN 3 ) with Sr 2 N at 1020 K yields for the first time a phase that contains the two triatomic anions acetonitriletriide C 2 N 3and carbodiimide CN 2 2side by side. Further synthetic routes were likewise successfully tested, including a sodium free approach [a]

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Synthesis, Characterization, and Chemical Bonding Analysis of the Lithium Alkaline‐earth Metal Gallide Nitrides Li₂(Ca₃N)₂[Ga₄] and Li₂(Sr₃N)₂[Ga₄]

Cited by 7 publications

References 55 publications

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

Li$_2$Sr[MnN]$_2$: a magnetically ordered, metallic nitride

Sr₄N[CN₂][C₂N]: The First Carbodiimide Acetonitriletriide

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Synthesis, Characterization, and Chemical Bonding Analysis of the Lithium Alkaline‐earth Metal Gallide Nitrides Li2(Ca3N)2[Ga4] and Li2(Sr3N)2[Ga4]

Cited by 7 publications

References 55 publications

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

The Crystal Structure of Manganotychite, Na6Mn2(CO3)4(SO4), and Structural Relations in the Northupite Group

Li$_2$Sr[MnN]$_2$: a magnetically ordered, metallic nitride

Sr4N[CN2][C2N]: The First Carbodiimide Acetonitriletriide

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Synthesis, Characterization, and Chemical Bonding Analysis of the Lithium Alkaline‐earth Metal Gallide Nitrides Li₂(Ca₃N)₂[Ga₄] and Li₂(Sr₃N)₂[Ga₄]

Sr₄N[CN₂][C₂N]: The First Carbodiimide Acetonitriletriide