Na8TiAs4, eine neue Zintl-Phase mit idealen isolierten TiAs4-Tetraedern / Na8TiAs4, a New Zintl-Compound with Ideal Isolated TiAs4-Tetrahedra

Stuhrmann, J.; Adam, Arnold; Schuster, Hans‐Uwe

doi:10.1515/znb-1993-0707

Cited by 11 publications

(4 citation statements)

References 3 publications

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“…Hence, the removal of 1/2 of the Zn atoms yields the ∞ 1 [ZnSb 2 ] 4− chains, seen in Ba 2 ZnSb 2 ; further reduction in dimensionality occurs when another 1/2 of the Zn atoms are taken away, which generates the structure of the hypothetical compound “Ba 4 ZnSb 4 ” (Ba 4 SiAs 4 type) . Such a compound with isolated [ZnSb 4 ] 10− units is two-electron deficient and, therefore, does not exist; however, similar structures, but with twice as many cations and electron-precise formulations, are known for Na 8 SnSb 4 and Na 8 TiAs 4 . Based on the above, one could argue that the described transformations of the [ZnSb] substructure (via empting the Zn-tetrahedral sites) will favor small lattice distortions and/or the “addition” of more cations.…”

Section: Resultsmentioning

confidence: 99%

“…61 Such a compound with isolated [ZnSb 4 ] 10units is two-electron deficient and, therefore, does not exist; however, similar structures, but with twice as many cations and electron-precise formulations, are known for Na 8 SnSb 4 62 and Na 8 TiAs 4 . 63 Based on the above, one could argue that the described transformations of the [ZnSb] substructure (via empting the Zn-tetrahedral sites) will favor small lattice distortions and/or the "addition" of more cations. This could also lead to better packing efficiency and maximizing the Madelung energy through stronger cation-anion interactions.…”

Section: Resultsmentioning

confidence: 99%

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Isolated _∞¹[ZnPn₂]⁴⁻ Chains in the Zintl Phases Ba₂ZnPn₂ (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Saparov

Bobev

2010

Inorg. Chem.

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Reported are the synthesis of three new Zintl phases, Ba2ZnAs2 (I), Ba2ZnSb2 (II), Ba2ZnBi2 (III) and their structural characterization by single-crystal X-ray diffraction. They are isoelectronic and isotypic and crystallize in the orthorhombic space group Ibam, with four formula units per cell (Pearson symbol oI20; K2SiP2 type). Lattice parameters are as follows: a = 13.399(9)/14.133(3)/14.325(6); b = 6.878(5)/7.1919(15)/7.280(3); and c = 6.541(4)/6.9597(15)/7.089(3) A for I/II/III, respectively. The structure can be viewed as polyanionic chains, infinity1[ZnPn2]4- (Pn = As, Sb, Bi), running parallel to the c-axis, with Ba2+ cations separating them. The chains are made of edge-shared ZnPn4 tetrahedra, which are isosteric with the infinity1[SiS4/2] chains in SiS2. This and some other structural parallels with known Zintl phases have been discussed. The experimental results have been complemented by tight-binding linear muffin-tin orbital electronic structure calculations.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Isolated _∞¹[ZnPn₂]⁴⁻ Chains in the Zintl Phases Ba₂ZnPn₂ (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Saparov

Bobev

2010

Inorg. Chem.

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“…In some of them the four-membered ring made of the two shared arsenic atoms and the two niobium centers is planar, flat dimers (Figure a), while in others this ring is bent around the shared arsenic edge, bent dimers (Figure b). Dimers of the first type involving transition metal have been characterized before, for example [Hf 2 As 6 ] 10- in Na 5 HfAs 3 with d 0 hafnium(IV) 4b 1 ORTEP drawing (95% probability thermal ellipsoids) of (a) the “flat” and (b) the “bent” dimers in K 38 Nb 7 As 24 .…”

Section: Resultsmentioning

confidence: 99%

“…“Admitted” initially were transition-metal phases that were isostructural with known main-group Zintl phases . These included, for example, Na 8 TiAs 4 and Na 5 HfAs 3 isostructural with A 8 SnSb 4 (A = Na, K) and Na 5 SnAs 3 , respectively . Next came all electronically balanced compounds that contain transition-metal ions with d 0 or d 10 closed-shell configurations.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of K₃₈Nb₇As₂₄ and Cs₉Nb₂As₆: The First Mixed-Valence Transition-Metal Zintl Phases

Gascoin

Sevov

2002

Inorg. Chem.

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The two title compounds were prepared by direct reactions of the corresponding elements at high temperature, and their structures were determined from single-crystal X-ray diffraction data. The structure of K(38)Nb(7)As(24) (orthorhombic; Cmcm; Z = 4; a = 10.4974(6), b = 23.915(2), c = 36.046(2) A) comprises isolated tetrahedra of NbAs(4) and two types of dimers of edge-sharing tetrahedra: dimers containing only Nb(V), [Nb(V)2As(6)](8-), and mixed-valence dimers with both Nb(IV) and Nb(V), [Nb(IV)Nb(V)As(6)](9-). The structure of Cs(9)Nb(2)As(6) (orthorhombic; Pbca; Z = 8; a = 17.5848(7), b = 16.940(2), c = 18.183(4) A) contains only the latter dimers. Magnetic measurements showed Curie-Weiss paramagnetic behavior for both compounds consistent with one unpaired electron/mixed-valence dimer. Cs(9)Nb(2)As(6) exhibits also an antiferromagnetic transition at about 36 K. The two compounds are the first mixed-valence (of class III) transition-metal Zintl phases.

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Cubane with a Handle: [{In3As4Nb}−As]7− in Cs7NbIn3As5

Gascoin¹,

Sevov²

2002

Angew. Chem.

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Compared to the large number of main group Zintl compounds there are only a few that contain transition metals. [1] This is not surprising since the traditional definition of Zintl phases automatically excludes transition metals. However, many such compounds with transition metals can qualify for Zintl phases when a broader definition is used. The latter includes compounds of transition metals with filled or empty d shells, that is the late transition metals of the Ni, Cu, and Zn groups, [2] and the early transition elements of the Ti, V, and Cr groups at maximum formal oxidation states. [3] There are only two Zintl compounds containing a transition metal with partially filled d shell, both based on manganese, (AE) 14 MnPn 11 (AE alkaline-earth metal, Pn pnictogen) and Sr 21 Mn 4 Sb 18 . [4] Perhaps only they should be called true ™transition metal Zintl phases∫ although the name is contradictory in itself. All but two of the d 0 compounds contain isolated tetrahedra [MPn 4 ] nÀ (M Nb, Ta, W, Ti). [5] The two exceptions are Na 5 HfAs 3 with dimers of edge-sharing tetrahedra of [Hf 2 As 6 ] 10À and Rb 5 TaAs 4 Tl 2 with [TaAs 4 ] tetrahedra, where two Tl atoms bridge opposite edges, (m-Tl)-[As 2 TaAs 2 ](m-Tl) 5À . [6] Here we report a new d 0 transition metal Zintl phase, Cs 7 NbIn 3 As 4 , which contains an unprecedented anion, [{In 3 As 4 Nb}ÀAs] 7À , a cubane made of three indium, four arsenic, and one niobium atom and a ™handle∫ composed of an arsenic atom that is multiply bonded to the niobium corner.The title compound was initially made in an attempt to synthesize the recently reported Cs 5 In 3 As 4 at temperatures higher than the original 500 8C. [7] The reaction was carried out in niobium containers at 800 8C, at which temperature the arsenic apparently attacked the container and formed the quaternary compound Cs 7 NbIn 3 As 4 . Later it was synthesized in high yield using the corresponding elements in stoichiometric ratio at the same temperature. [8] The overall structure of Cs 7 NbIn 3 As 5 is quite simple and unremarkable, [9] an ionic assembly of isolated anions of [NbIn 3 As 5 ] 7À immersed in a ™sea∫ of cesium cations that screen them from each other (inter-anion d min 5.009(4) ä). What is remarkable is the structure and bonding of the anion (Figure 1). Its geometry can be viewed in a few different ways. The more obvious approach is to recognize the cubane shape made of one Nb, three In, and four As atoms, [NbIn 3 As 4 ], and its ™handle∫ of a fifth arsenic atom attached to the niobium [*] Prof.

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Na₈TiAs₄, eine neue Zintl-Phase mit idealen isolierten TiAs₄-Tetraedern / Na₈TiAs₄, a New Zintl-Compound with Ideal Isolated TiAs₄-Tetrahedra

Abstract: The new cubic compound Na8TiAs4, a = 1376.7(1) pm, space group Fd 3 m, is isostructural to Na8SnSb4 [1]. The structure is characterized by ideal isolated TiAs4 tetrahedra. The compound is in agreement with the Zintl concept.

Cited by 11 publications

References 3 publications

Isolated _∞¹[ZnPn₂]⁴⁻ Chains in the Zintl Phases Ba₂ZnPn₂ (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Isolated _∞¹[ZnPn₂]⁴⁻ Chains in the Zintl Phases Ba₂ZnPn₂ (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Synthesis and Characterization of K₃₈Nb₇As₂₄ and Cs₉Nb₂As₆: The First Mixed-Valence Transition-Metal Zintl Phases

Cubane with a Handle: [{In3As4Nb}−As]7− in Cs7NbIn3As5

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Na8TiAs4, eine neue Zintl-Phase mit idealen isolierten TiAs4-Tetraedern / Na8TiAs4, a New Zintl-Compound with Ideal Isolated TiAs4-Tetrahedra

Abstract: The new cubic compound Na8TiAs4, a = 1376.7(1) pm, space group Fd 3 m, is isostructural to Na8SnSb4 [1]. The structure is characterized by ideal isolated TiAs4 tetrahedra. The compound is in agreement with the Zintl concept.

Cited by 11 publications

References 3 publications

Isolated ∞1[ZnPn2]4− Chains in the Zintl Phases Ba2ZnPn2 (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Isolated ∞1[ZnPn2]4− Chains in the Zintl Phases Ba2ZnPn2 (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Synthesis and Characterization of K38Nb7As24 and Cs9Nb2As6: The First Mixed-Valence Transition-Metal Zintl Phases

Cubane with a Handle: [{In3As4Nb}−As]7− in Cs7NbIn3As5

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Na₈TiAs₄, eine neue Zintl-Phase mit idealen isolierten TiAs₄-Tetraedern / Na₈TiAs₄, a New Zintl-Compound with Ideal Isolated TiAs₄-Tetrahedra

Isolated _∞¹[ZnPn₂]⁴⁻ Chains in the Zintl Phases Ba₂ZnPn₂ (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Isolated _∞¹[ZnPn₂]⁴⁻ Chains in the Zintl Phases Ba₂ZnPn₂ (Pn = As, Sb, Bi)—Synthesis, Structure, and Bonding

Synthesis and Characterization of K₃₈Nb₇As₂₄ and Cs₉Nb₂As₆: The First Mixed-Valence Transition-Metal Zintl Phases