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• W2028932222 abstract "K2W6Br14 (I), Rb2W6Br14 (II), and Cs2W6Br14 (III) were formed by reactions of W6Br12 with the corresponding alkali metal bromides in evacuated silica tubes with a temperature gradient of 925 K/915 K. (I) crystallizes in the cubic space group Pn3 (no. 201), a = 13.808 Å, Z = 4, cP88. (II) crystallizes in the monoclinic space group C2/c (no. 15), a = 20.301 Å, b = 15.396 Å, c = 9.720 Å, β = 115.69°, Z = 4, mC88. (III) crystallizes in the trigonal space group P31c (no. 163), a = 10.180 Å, c = 15.125 Å, Z = 2, hP44. The crystal structures are composed of the isolated [(W6Br)Br]2– cluster anions and the alkali metal cations (d(W–W) = 2.635(2) Å, d(W–Bri) = 2.624(4) Å, d(W–Bra) = 2.595(4) Å). The shape of the anions is influenced by the crystal field symmetry, but the mean bond lengths are not changed by the cation size. The packing of the cluster anions corresponds to ccp pattern in (I) and hcp pattern in (II) and (III), respectively. The alkali metal cations in the octahedral holes are coordinated only by the Bra ligands while those in the tetrahedral and trigonal-bipyramidal cavities are surrounded by Bra and Bri ligands. The details will be discussed and compared with other structures. Synthesen und Kristallstrukturen der Clusterverbindungen A2[(W6Br)Br] mit A = K, Rb, Cs K2W6Br14 (I), Rb2W6Br14 (II), und Cs2W6Br14 (III) bilden sich durch die Reaktion von W6Br12 mit Alkalimetallbromiden in evakuierten Quarzampullen im Temperaturgradienten 925 K/915 K. (I) kristallisiert kubisch in der Raumgruppe Pn3 (Nr. 201), a = 13,808 Å, Z = 4, cP88. (II) kristallisiert monoklin in der Raumgruppe C2/c (Nr. 15), a = 20,301 Å, b = 15,396 Å, c = 9,720 Å, β = 115,69°, Z = 4, mC88. (III) kristallisiert trigonal in der Raumgruppe P31c (Nr. 163), a = 10,180 Å, c = 15,125 Å, Z = 2, hP44. Die Kristallstrukturen sind aus isolierten Clusteranionen [(W6Br)Br]2– und den Alkalimetallkationen aufgebaut (d(W–W) = 2,635(2) Å, d(W–Bri) = 2,624(4) Å, d(W–Bra) = 2,595(4) Å). Die Form der Anionen wird durch die Symmetrie der Kristallfelder beeinflußt, jedoch sind die mittleren Bindungslängen nicht von der Größe der Kationen abhängig. Die Packung der Clusteranionen entspricht in (I) einem ccp-Muster, in (II) und (III) einem hcp-Muster. Die Kationen in oktaedrischen Lücken werden nur von den Bra-Liganden koordiniert, während die Kationen in tetraedrischen und trigonal-bipyramidalen Lücken von Bra- und Bri-Liganden umgeben sind. Die Strukturen werden im Detail diskutiert und mit anderen verglichen." @default.
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• W2028932222 date "1998-03-01" @default.
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• W2028932222 title "Syntheses and Crystal Structures of the Cluster Compounds A2[(W6Br8i)Br6a] with A = K, Rb, Cs" @default.
• W2028932222 doi "https://doi.org/10.1002/(sici)1521-3749(199803)624:3<506::aid-zaac506>3.0.co;2-a" @default.
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