Crystal structure of trirubidium diphosphidogallate, Rb<sub>3</sub>GaP<sub>2</sub>

Somer, M.; Peters, Karl; Thiery, D.; Schnering, H. G. Von

doi:10.1524/zkri.1990.192.3-4.271

Cited by 11 publications

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“…The Al atoms are coordinated in a trigonal planar manner by phosphorus atoms, leading to dimers of edge‐sharing triangles. In the case of related gallium compounds, only ternary alkali metal phosphidogallates with trigonal planar GaP 3 triangles are reported (Na 6 GaP 3 , K 2 GaP 2 , Rb 3 GaP 2 , Cs 6 Ga 2 P 4 ), and Li 3 GaP 2 represents the first ternary alkali metal‐based phosphidogallate with gallium in a tetrahedral coordination environment. Further, in quaternary mixed‐alkali metal phosphidogallates, such GaP 4 tetrahedra already exist, for example, in K 2 NaGaP 2 and Cs 2 NaGaP 2 .…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Restle

Dums

Raudaschl‐Sieber

et al. 2020

Chemistry A European J

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Thel ithium phosphidoaluminate Li 9 AlP 4 represents apromising new compound with ahigh lithium ion mobility. This triggered the searchf or new members in the familyo f lithium phosphidotrielates, and the novel compounds Li 3 AlP 2 and Li 3 GaP 2 ,o btained directly from the elements via ball milling ands ubsequenta nnealing, are reported here. It was unexpectedly found through band structure calculations that Li 3 AlP 2 and Li 3 GaP 2 are directb and gap semiconductors with band gaps of 3.1 and 2.8 eV,r espectively.R ietveld anal-yses revealt hat both compounds crystallize isotypically in the orthorhombic space group Cmce (no. 64) with lattice parameters of a = 11.5138(2), b = 11.7634(2)a nd c = 5.8202(1) for Li 3 AlP 2 ,a nd a = 11.5839(2), b = 11.7809(2) and c = 5.8129(2) for Li 3 GaP 2 .T he crystal structures feature TrP 4 (Tr = Al, Ga) corner-and edge-sharing tetrahedra, forming two-dimensional 1 2 TrP 2 3À ½ layers. The lithium atoms are located between and inside these layers. The crystal structures were confirmed by MAS-NMR spectroscopy.Li 2 SiP 2 . [8,11] Interestingly,t he phases Li 8 SiP 4 ,L i 5 SiP 3 (= Li 10 Si 2 P 6 ), Li 2 SiP 2 ,a nd LiSi 2 P 3 are connected by af ormal reduction of the formula by units of Li 3 P. [11] Al ower Li 3 Pc ontent leads to a higherc onnectivity of the tetrahedra.Compared to the related sulfide-basedl ithium ion conductors, [3,6,7,12] the anionic substructure of phosphido-based conductorsc arry one additional charge( formal "P 3À "v ersus a formal "S 2À "), and thus the Li content that is required for chargeb alance is higher.R ecently,w ee xpanded this concept of highly charged tetrahedra to lithium phosphidoaluminates by replacing the centralg roup 14 metal by aluminium. [13] Li 9 AlP 4 contains highly charged[TrP 4 ] 9À tetrahedra andreaches high ionic conductivities of % 3.0 mS cm at room temperature. Besides this first report of astructurally characterized lithium phosphidoaluminate, another compound of the composition Li 3 AlP 2 was mentioned already in 1952 and described with an orthorhombic distorted CaF 2 -type structure, in which the phosphorus atoms form ad istorted cubic close packing, althoughw ithoutr eliable crystallographic data. [14] Twoy ears later,t he corresponding gallium compound Li 3 GaP 2 was also postulated. [15] Despite the poorly characterized structure model, quantum-chemical calculations of Li 3 AlP 2 and Li 3 GaP 2 were performed, anticipating the model of vertex-sharing AlP 4 tetrahedra. [16][17][18] As forl ithium phosphidotetrelates, lithium phosphidoaluminates can also be connected on al ine in a Gibbs composition triangle (Finetti diagram). Li 3 AlP 2 is located on the line in the phase system Li-Al-P connecting Li 3 Pa nd AlP ( Figure S7, Supporting Information) by reducing Li 9 AlP 4 by two units of Li 3 P( Li 3 AlP 2 = Li 9 AlP 4 À2 Li 3 P). Assuming ac harge balanced valence compound, the degree of connectivity of the AlP 4 tetrahedra in Li 3 AlP 2 mustb eh igher, and isolated tetrahedra as observed in Li 9 AlP 4 cannot occur.Here...

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Restle

Dums

Raudaschl‐Sieber

et al. 2020

Chemistry A European J

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“…As), [5,6] and Cs 6 GaSb 3 [7] ( Figure 1a). Phases with the heavier alkali metals like Cs 6 Ga 2 P 4 , [8] Rb 3 GaP 2 , [9] and Cs 3 GaAs 2 [10] contain isolated dimeric anions [Ga…”

Section: Introductionmentioning

confidence: 99%

“…Phases with the highly charged [ TrPn 3 ] 6– anions consequently have a high alkali metal content for charge compensation, such as in Na 6 Ga Pn 3 ( Pn = P, As), K 6 In Pn 3 ( Pn = P, As),, and Cs 6 GaSb 3 (Figure a). Phases with the heavier alkali metals like Cs 6 Ga 2 P 4 , Rb 3 GaP 2 , and Cs 3 GaAs 2 contain isolated dimeric anions [Ga 2 Pn 4 ] 6– , which share two Pn atoms in an almost planar Ga 2 Pn 2 butterfly‐type ring structure with two Ga‐ Pn exo bonds (Figure b). The Ga‐containing ternary K 20 Ga 6 As 12.66 and K 20 Ga 6 Sb 12.66 as well as quaternary phases RbNa 8 Ga 3 P 6 and RbNa 8 Ga 3 As 6 comprise cyclic trimers [Ga 3 Pn 6 ] 9– ( Pn = P, As and Sb) in which three monomers formally share two Pn atoms each.…”

Section: Introductionmentioning

confidence: 99%

K₁₀Ga₃Bi_6.65 – The First Compound in the Ternary A‐Ga‐Bi System Comprising Cyclic Tris‐meta Borate‐Analogous [Ga₃Bi₆]^9– Units and Bi₂ Dumbbells

Boyko

Hlukhyy

Fässler

2020

Zeitschrift anorg allge chemie

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K10Ga3Bi6.65 is the first representative in the ternary system A‐Ga‐Bi (A = alkali metal). It contains [Ga3Bi6]9– anions with planar triangular‐coordinated Ga atoms as the main structural feature, accompanied by isolated Bi–Bi dumbbells. Alkali metal cations are counterbalancing the charges and fill the space between the anionic units. According to the Zintl‐Klemm concept charge balance is reached if an almost equal ratio of single and double‐bonded Bi2 dumbbells are present according to (K+)10[Ga3Bi6]9–([Bi‐Bi]4–)1/6([Bi=Bi]2–)1/6.

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Crystal structure of caesium potassium di-μ-phosphido-bis(phosphidogallate), Cs_5.31K_0.69(Ga₂P₄)

Somer¹,

Peters²,

Thiery³

et al. 1991

Zeitschrift für Kristallographie

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Crystal structure of trirubidium diphosphidogallate, Rb₃GaP₂

Cited by 11 publications

References 0 publications

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

K₁₀Ga₃Bi_6.65 – The First Compound in the Ternary A‐Ga‐Bi System Comprising Cyclic Tris‐meta Borate‐Analogous [Ga₃Bi₆]^9– Units and Bi₂ Dumbbells

Crystal structure of caesium potassium di-μ-phosphido-bis(phosphidogallate), Cs_5.31K_0.69(Ga₂P₄)

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Crystal structure of trirubidium diphosphidogallate, Rb3GaP2

Cited by 11 publications

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Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li3AlP2 and Li3GaP2

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li3AlP2 and Li3GaP2

K10Ga3Bi6.65 – The First Compound in the Ternary A‐Ga‐Bi System Comprising Cyclic Tris‐meta Borate‐Analogous [Ga3Bi6]9– Units and Bi2 Dumbbells

Crystal structure of caesium potassium di-μ-phosphido-bis(phosphidogallate), Cs5.31K0.69(Ga2P4)

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Crystal structure of trirubidium diphosphidogallate, Rb₃GaP₂

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

Synthesis, Structure, Solid‐State NMR Spectroscopy, and Electronic Structures of the Phosphidotrielates Li₃AlP₂ and Li₃GaP₂

K₁₀Ga₃Bi_6.65 – The First Compound in the Ternary A‐Ga‐Bi System Comprising Cyclic Tris‐meta Borate‐Analogous [Ga₃Bi₆]^9– Units and Bi₂ Dumbbells

Crystal structure of caesium potassium di-μ-phosphido-bis(phosphidogallate), Cs_5.31K_0.69(Ga₂P₄)