[Ga6Se14]10− : A 1900 pm Long, Hexameric Anion

Deiseroth, H. J.; Fu‐Son, Han

doi:10.1002/anie.198109621

Cited by 20 publications

(9 citation statements)

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“…[14,15] Nearly all of the known compounds fulfil electronically precise ionic formulations if assumed to contain Ge . Silicon and germanium clearly prefer to be tetravalent, but lower oxidation states are possible.…”

Section: Introductionmentioning

confidence: 99%

Strontium Selenogermanate(III) and Barium Selenogermanate(II,IV): Synthesis, Crystal Structures, and Chemical Bonding

Johrendt

Tampier

2000

Chem. Eur. J.

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The new selenogermanates Sr2Ge2Se5 and Ba2Ge2Se5 were synthesized by heating stoichiometric mixtures of binary selenides and the corresponding elements to 750 degrees C. The crystal structures were determined by single-crystal X-ray methods. Both compounds adopt previously unknown structure types. Sr2Ge2Se5 (P2(1)/n, a = 8.445(2) A, b = 12.302 A, c = 9.179 A, beta = 93.75(3) degrees, Z = 4) contains [Ge4Se10]8- ions with homonuclear Ge-Ge bonds (dGe-Ge = 2.432 A), which may be described as two ethane-like Se3Ge-GeSeSe2/2 fragments sharing two selenium atoms. Ba2Ge2Se5 (Pnma, a = 12.594(3) A, b = 9.174(2) A, c = 9.160(2) A, Z = 4) contains [Ge2Se5]4- anions built up by two edge-sharing GeSe4 tetrahedra, in which one terminal Se atom is replaced by a lone pair from the divalent germanium atom. The alkaline earth cations are arranged between the complex anions, each coordinated by eight or nine selenium atoms. Ba2Ge2Se5 is a mixed-valence compound with GeII and GeIV coexisting within the same anion. Sr2Ge2Se5 contains exclusively GeIII. These compounds possess electronic formulations that correspond to (Sr2+)2(Ge3+)2(Se2-)5 and (Ba2+)2- Ge2+Ge4+(Se2-)5. Calculations of the electron localization function (ELF) reveal clearly both the lone pair on GeII in Ba2Ge2Se5 and the covalent Ge-Ge bond in Sr2Ge2Se5. Analysis of the ELF topologies shows that the GeIII-Se and GeIV-Se covalent bonds are almost identical, whereas the GeII-Se interactions are weaker and more ionic in character.

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Section: Introductionmentioning

confidence: 99%

Strontium Selenogermanate(III) and Barium Selenogermanate(II,IV): Synthesis, Crystal Structures, and Chemical Bonding

Johrendt

Tampier

2000

Chem. Eur. J.

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“…Related structures containing one-dimensional [GaS 2 ] À chains were described by Vaqueiro (2006a,b). A fragment of a gallium selenide chain, [Ga 6 Se 14 ] 10À , was reported by Deiseroth & Fu-Son (1981).…”

Section: Related Literaturementioning

confidence: 99%

“…The compound reported here is isostructural to piperazinium gallium selenide, {(C 4 H 11 N 2 )[GaSe 2 ]} n (Bu, Zheng, Wang et al, 2004), which contains [GaSe 2 ]chains. A gallium selenide containing six-gallium atom fragments, [Ga 6 Se 14 ] 10-, of this type of one-dimensional chains has also been reported (Deiseroth & Fu-Son, 1981). Recently some solvothermally prepared gallium sulfides, [C 10 N 4 H 26 ] 0.5 [GaS 2 ] and [M(en) 3 ] 0.5 [GaS 2 ] (M = Mn, Co, Ni), which contain [GaS 2 ]chains separated by monoprotonated 1,4-bis(3-aminopropyl)piperazine or [M(en) 3 ] 2+ complexes respectively, have also been described (Vaqueiro, 2006ab).…”

Section: Sup-1mentioning

confidence: 99%

catena-Poly[piperazinium di-μ-sulfido-gallium]

Vaqueiro¹,

Romero²

2007

Acta Cryst E

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“…It is also, naturally, directly related to the value of the angle. At k = 0, in (BeCl2)" the crystal orbital of SS4 is Be-Be antibonding (4), while in (BeMe2)" it is bonding (10). Therefore, SS4 contributes to the destruction of the Be-Be bond in (BeCl2)" and to its buildup in (BeMe2)".…”

Section: (Becl2)" Chainmentioning

confidence: 99%

Structure and stability of one-dimensional (MX2)n polymers. A band structure analysis

Canadell¹,

Eisenstein²

1983

Inorg. Chem.

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Band structure calculations are used to analyze the structures of one-dimensional (BeCl2)" and (BeMe2)" polymers. The distortion away from the ideal tetrahedral angle at the beryllium atom, 98.2°in (BeCl2)" and 114°in (BeMe2)", is related to the existence of a lone pair on the bridging group or atom available for bonding with the Be centers. The analysis accounts correctly for the structures of other one-dimensional polymers such as (SiS2)", (SiSe2)", and fibrous (Si02)". The stability of these polymers is discussed in terms of the number of valence electrons per unit cell. It is demonstrated that 32 electrons per unit cell is the optimal number, which is in good agreement with the experimental evidence. New one-dimensional (MX2)" polymers are proposed on the basis of this 32-electron rule.In this paper we present a theoretical analysis of edgesharing tetrahedral (MX2)" periodic systems ( = main group metal, X = halide, alkyl, alkoxide, hydride) by means of band structure calculations. Our purpose is a better understanding of the structures and stabilities of these systems.One-dimensional polymeric chains of MX2 are commonly found for M = Be1-5 and Mg6"8 with various bridging X's. The best known examples are (BeCl2)"* and (BeMe2)".2 The simplest compound (BeH2)"3 has been synthesized, although its structure could not be determined. With M = Be, X can also be an alkoxy group48 or a dissimilar pair (H, alkyl).* Grignard reagents are believed to be polymeric.8 (MgMe2)"6 and (MgEt2)",7 which are also related to Grignard reagents, are well-characterized polymers.The basic motif of these polymers is an edge-sharing tetrahedron as shown in 1. A similar arrangement is known for the silicon derivatives9 (SiS2)", (SiSe2)", and fibrous (Si02)".A small-size polymer made of gallium and selenium (Ga6Se14)10™ has been recently characterized.10 An interesting pattern emerges from the examination of the geometrical parameters of 1. Although M is said to be tetrahedrally coordinated, the angle at the M center, ZXMX, departs noticeably from the usual value of 109.47°. In (Be-Cl2)" the /ClBeCl angle is 98.2°1 while in (BeMe2)" the

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[Ga₆Se₁₄]¹⁰⁻ : A 1900 pm Long, Hexameric Anion

Cited by 20 publications

References 3 publications

Strontium Selenogermanate(III) and Barium Selenogermanate(II,IV): Synthesis, Crystal Structures, and Chemical Bonding

Strontium Selenogermanate(III) and Barium Selenogermanate(II,IV): Synthesis, Crystal Structures, and Chemical Bonding

catena-Poly[piperazinium di-μ-sulfido-gallium]

Structure and stability of one-dimensional (MX2)n polymers. A band structure analysis

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