Neue Oxocuprate(I). Zur Kenntnis von Rb3Cu5O4 [1]

Klassen, H.; Hoppe, R.

doi:10.1002/zaac.19824940103

Cited by 23 publications

(5 citation statements)

References 12 publications

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“…Reaction of Cu 2 O with 0.6 equiv of Rb 2 O generates Rb 3 Cu 5 O 4 , which has a complicated two-dimensional net structure with linear Cu coordination (30). 133 (31). 134 The remaining bridges are cleaved upon assimilating one further equivalent of Rb 2 O to form the saturated compound Rb 3 CuO 2 , with discrete linear [CuO 2 ] 3ions (32).…”

Section: Framework With Edge-sharing Octahedramentioning

confidence: 99%

“…Two such frameworks actually interpenetrate in the crystal structure, but this does not affect the predictions of dimensional reduction. Reaction of Cu 2 O with 0.6 equiv of Rb 2 O generates Rb 3 Cu 5 O 4 , which has a complicated two-dimensional net structure with linear Cu coordination ( 30 ) . Additional Rb 2 O produces Rb 4 Cu 4 O 4 , a compound containing molecular [Cu 4 O 4 ] 4- squares ( 31 ) .…”

Section: Examining the Scope Of Dimensional Reductionmentioning

confidence: 99%

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Dimensional Reduction: A Practical Formalism for Manipulating Solid Structures

2001

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Conceptually, it is not difficult to imagine reaching into a solid structure and carving out just that portion of the framework we desire. Solid-state reactions incorporating an ionic component into a covalent structure have long been recognized as experimental means for accomplishing just such feats. However, the method does not always succeed, and so, in an effort to extend its use in more logical approaches to solid synthesis, we herein provide an assessment of the scope and limitations of the reaction type. Dimensional reduction is set forth as a general formalism describing how the metal−anion (M−X) framework of a parent compound, MX x , is dismantled upon reaction with an ionic reagent A a X to form a child compound A na MX x + n . The added anions serve to terminate M−X−M bridges, yielding a less tightly connected framework that retains the metal coordination geometry and polyhedron connectivity mode of the original parent structure. In most instances, the connectedness of the ensuing framework can also be predicted, facilitating enumeration of likely structures. A database containing more than 3000 relevant crystal structures has been compiled (available at ) and is employed in evaluating the applicability of dimensional reduction to various systems. Examples are provided and results are tabulated for the deconstruction of parent solids featuring octahedral, tetrahedral, square planar, and linear metal coordination polyhedra linked through corner-, edge-, and face-sharing interactions. The success of dimensional reduction is observed to depend significantly on the choice of the countercation A (with smaller cations typically giving more reliable results), suggesting that this should be considered a variable parameter when targeting a specific child framework. The utility of the method in dismantling cluster-containing frameworks is also discussed.

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Section: Framework With Edge-sharing Octahedramentioning

confidence: 99%

Section: Examining the Scope Of Dimensional Reductionmentioning

confidence: 99%

Dimensional Reduction: A Practical Formalism for Manipulating Solid Structures

2001

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“…1), coordination numbers below the lower limit of six occur only with very strong bases. Most, if not all, of these compounds are extremely moisture sensitive and require special handling (see for example Klassen & Hoppe, 1982)* as is predicted by the valence-matching principle for compounds in which the Lewis base is much stronger than the Lewis acid (Brown, 1981).…”

Section: Prediction Of Coordination Numbersmentioning

confidence: 99%

What factors determine cation coordination numbers?

Brown¹

1988

Acta Crystallogr B Struct Sci

256

166

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Over 14 000 coordination environments of 100 different cations retrieved from the Inorganic Crystal Structure Database have been analyzed. For comparison predicted coordination numbers (PCN's) have been calculated using ionic radius ratios. The observed coordination numbers are generally smaller than or equal to the PCN's and their range, for most cations, can be predicted from a knowledge of the Lewis-base strengths of available anions and the requirement that these strengths be close to the Lewis-acid strength of the cation. The occurrence of smaller coordination numbers is associated with strongly directed bonds (electronic effects) and is found for main-group elements in low oxidation states and for closed-d-shell cations of Groups 11, 12 and 13. An analysis of the results shows that to use ionic radii to predict both coordination numbers and interatomic distances it is necessary to use cation and anion radii that both vary in the same way with the cation coordination number (N). The value found for the oxygen radius is 1.12 + 0.23In(N-2)/~. The average observed coordination number is used to calculate cation Lewis-acid strengths which are shown to correlate with electronegativity.

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“…Hieraus wurde gefolgert, daû die Reaktion zur Bildung von Rb 3 Cu 5 O 4 unter Beteiligung der Wand erfolgen sollte [4]. Hieraus wurde gefolgert, daû die Reaktion zur Bildung von Rb 3 Cu 5 O 4 unter Beteiligung der Wand erfolgen sollte [4].…”

Section: Die Darstellung Von Rb 3 Cu 5 O 4 Aus Den Bina è Renunclassified

“…Die Formeltypen ACuO mit A = Na±Cs [1] und A 3 CuO 2 mit A = Na, K, Rb [2] sind anhand von Einkristalldaten belegt. Rb 3 Cu 5 O 4 [4] ist der einzige an Einkristalldaten belegte Vertreter dieser Zusammensetzung und u È ber weitere Phasen im System A/Cu I /O konnte anhand von Pulverdaten die Isotypie der Oxide A 3 Cu 5 O 4 mit A = K, Rb, Cs belegt und die gemischten Vertreter KRb 2 Cu 5 O 4 und K 2 RbCu 5 O 4 nachgewiesen werden [5]. Rb 3 Cu 5 O 4 [4] ist der einzige an Einkristalldaten belegte Vertreter dieser Zusammensetzung und u È ber weitere Phasen im System A/Cu I /O konnte anhand von Pulverdaten die Isotypie der Oxide A 3 Cu 5 O 4 mit A = K, Rb, Cs belegt und die gemischten Vertreter KRb 2 Cu 5 O 4 und K 2 RbCu 5 O 4 nachgewiesen werden [5].…”

Section: Introductionunclassified

Untersuchungen zur Reaktivität in den Systemen A/Cu/M/O (A = Na-Cs und M = Co, Ni, Cu, Ag); Synthese und Kristallstrukturen von K3Cu5O4 und Cs3Cu5O4

Möller

2001

Z. anorg. allg. Chem.

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Neue Oxocuprate(I). Zur Kenntnis von Rb₃Cu₅O₄ [1]

Cited by 23 publications

References 12 publications

Dimensional Reduction: A Practical Formalism for Manipulating Solid Structures

Dimensional Reduction: A Practical Formalism for Manipulating Solid Structures

What factors determine cation coordination numbers?

Untersuchungen zur Reaktivität in den Systemen A/Cu/M/O (A = Na-Cs und M = Co, Ni, Cu, Ag); Synthese und Kristallstrukturen von K3Cu5O4 und Cs3Cu5O4

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