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  • Chemistry  (18)
  • Cesium copper(II) fluoride, CsCu2F5  (1)
  • Cyano-elpasolites  (1)
  • IR Spectra
  • Wiley-Blackwell  (18)
  • 1990-1994  (11)
  • 1980-1984  (7)
  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Refinement of the 12L Structure of the Hexagonal-rhombohedral Elpasolite Rb2LiFeF6The single crystal structure determination of the hexagonal Elpasolite Rb2LiFeF6 confirmed (R = 2.4%) the compound to be isotypic to the hexagonal-rhombohedral 12 layer structure of the Cs2NaCrF6 type. The compound crystallizes with a = 588.0(3), c = 2879.0(8) pm (a = 1017.9 pm, α = 33.57°) in space group R3m. The fluorine distances of the two iron atoms differing in distortion of their octahedral coordination are 191.9(3) and 193.6(3) pm, resp. By face-sharing with FeF6 octahedra at one side and edge-sharing at the other, the LiF6 octahedra are strongly deformed, Li—F = 200.8/223.1(13), Li—Fe = 281.0(18) pm. Both rubidium atoms are 12 coordinated, average distance Rb—F = 297.7 pm. The relations of hexagonal-rhombohedral lattice constants to those of a pseudomonoclinic cell, as claimed for some Elpasolites, are pointed out.
    Notes: Die Einkristallstrukturbestimmung an dem hexagonalen Elpasolith Rb2LiFeF6 bestätigte (R = 2,4%) die Isotypie mit der hexagonal-rhomboedrischen 12-Schichtenstruktur des Cs2NaCrF6-Typs. Die Verbindung kristallisiert mit a = 588,0(3), c = 2879,0(8) pm (a = 1017,9 pm, α = 33,57°) in der Raumgruppe R≙m. Die Fluorabstände der beiden mit unterschiedlichem Verzerrungsgrad oktaedrisch koordinierten Eisenatome betragen Fe—F = 191,9(3) bzw. 193,6(3) pm. Durch die Flächenverknüpfung mit FeF6-Oktaedern auf der einen, Eckenverknüpfung auf der anderen Seite sind die LiF6-Oktaeder stark deformiert, Li—F = 200,8/223,1(13), Li—Fe = 281,0(18) pm. Die beiden Rubidiumatome sind 12fach koordiniert, Mittelwert Rb—F = 297,7 pm. Auf die Beziehungen hexagonal-rhomboedrischer Gitterkonstanten zu denen einer pseudomonoklinen Zelle, wie sie für manche Elpasolithe angegeben wurde, wird hingewiesen.
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  • 2
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: X-Ray Studies on Titanium(III) Fluoro Compounds with Pyrochlore-related StructuresThe cubic compounds (a/pm) CsMIITiIIIF6, MII = Mg (1041.6), Ni (1043.9), Zn (1049.8), Co (1051.7), V (1052.6), Fe (1055.3), Mn (1064.9) and CsM0,5ITi1,5IIIF6, MI = K (1074.6), Rb (1080.6) were prepared. They crystallize in the modified pyrochlore structure of the RbNiCrF6 type, which is confirmed once more at single crystals of an oxide fluoride phase CsTi2X6 (X6 between O2F4 and O3F3): Space group Fd3m, a = 1028.8 pm, R = 2.6% (126 independent reflections). Further compounds CsM0,5ITi1,5IIIF6 according to their powder diagrams are orthorhombic (MI = NH4: a = 764.1, b = 767.5, c = 1087.5 pm) or monoclinic (Na: a = 737.0, b = 758.0, c = 1061.8 pm, β = 91.1°, Li: a = 1466, b = 1479, c = 1041 pm, β = 93.3°) with related, but not exactly know structures.
    Notes: Die kubischen verbindungen (a/pm) CsMIITiIIIF6, MII = Mg(1041,6), Ni(1043,9), Zn(1049,8), Co(1051,7), V(1052,6), Fe(1055,3), Mn(1064,9) und CsM0,5ITi1,5IIIF6, MI = K(1074,6), Rb(1080,6) wurden dargestellt. Sie kristallisieren in der modifizierten Pyrochlorstruktur des RbNiCrF6-Types, der an Einkristallen einer Oxidfluoridphase CsTi2X6 (X6 zwischen O2F4 und O3F3) erneut bestätigt wird: Raumgruppe Fd3m, a = 1028,8 pm, R = 2,6% (126 symmetrieunabhängige Reflexe). Weitere Verbindungen CsM0,5ITi1,5IIIF6 sind nach Pulveraufnahmen orthorhombisch (MI = NH4: a = 764,1, b = 767,5, c = 1087,5 pm) bzw. monoklin (Na: a = 737,0, b = 758,0, c = 1061,8 pm, β = 91,1°, Li: a = 1466, b = 1479, c = 1041 pm,β = 93,3°), mit verwandten, aber nicht genauer bekannten Strukturen.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 505 (1983), S. 153-160 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Lattice Constants and Ionic Radii of Pyrochlores CsMIIMIIIF6From observed lattice constants a0 of 30 cubic pyrochlores CsMIIMIIIF6 (MII = Mg, Ni, Cu, Zn, Co, Mn; MIII = Ga, Cr, Fe, V, Ti) balanced values ac were calculated, which deviate in average less than 0.1% from the observed ones. Radii rc of the M(II) and M(III) ions are evaluated from the balanced values ac by means of an empiric equation; they reproduce the lattice constants a0 equally well. By analogy derived radii rII and rIII from additional pyrochlores CsMIIMIIIF6 are given and discussed in comparison with tabulated radii and observed M—F distances.
    Notes: Aus den beobachteten Gitterkonstanten a0 von 30 kubischen Pyrochloren CsMIIMIIIF6 (MII = Mg, Ni, Cu, Zn, Co, Mn; MIII = Ga, Cr, Fe, V, Ti) werden Ausgleichswerte ac gebildet, die im Mittel weniger als 0,1% von den Beobachtungsgrößen abweichen. Aus den Ausgleichswerten ac werden mit Hilfe einer empirischen Beziehung Radien rc für die M(II)- und M(III)-Ionen abgeleitet, mit denen die Gitterkonstanten a0 mit entsprechender Genauigkeit reproduzierbar sind. Analog aus weiteren Pyrochloren CsMIIMIIIF6 ermittelte Radien rII und rIII werden mitgeteilt und im Vergleich mit tabellierten Radien und beobachteten M—F-Abständen diskutiert.
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  • 4
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Crystal Structure of a High Temperature Modification of Barium-Zinc-Iron(III) Fluoride BaZnFeF7A metastable high temperature form of BaZnFeF7 prepared at 750°C crystallizes monoclinically (a = 560.3(1), b = 997,1(3), c = 958.4(4) pm, β = 92.80(4)°, Z = 4) in the same space group P21/c as the low temperature form. The X-ray structure determination (RG = 5.2— for 2426 independent reflections) showed analogy in the coordination behaviour of Zn2+ and Fe3+ cations, which occupy in an ordered way groups of two edgesharing octahedra, at each of which one ligand remains unbridged (mean distances Zn—F = 204.7 pm, Fe—F = 194.6 pm). The linking of double octahedra via corners to form a threedimensional framework involves strongly bent fluorine bridges (average Zn—F—Fe = 126.5°). Related structures are discussed.
    Notes: Eine bei 750°C in Einkristallen dargestellte metastabile Hochtemperatur-form von BaZnFeF7 kristallisiert monoklin (a = 560,3(1), b = 997,1(3), c = 958,4(4) pm, β = 92,80(4)°, Z = 4) in derselben Raumgruppe P21/c, wie die Tieftemperaturform. Die röntgenographische Strukturbestimmung (RG = 5,2 -  für 2 426 unabhängige Reflexe) ergab koordinationschemisch analoges Verhalten für Zn2+- und Fe3+-Kationen, die geordnet kantenverknüpfte Gruppen von zwei Oktaedern besetzen, an denen je ein Ligand unverbrückt bleibt (mittlere Abstände Zn—F = 204,7 pm, Fe—F = 194,6 pm). Die Eckenverknüpfung der Doppeloktaeder zu einer Raumnetzstruktur verläuft über stark gewinkelte Fluorbrücken (Mittel Zn—F—Fe = 126,5°). Verwandte Strukturen werden diskutiert.
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  • 5
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Jahn-Teller Effect and Crystal Structure Distortion of the Copper Fluoroperovskites NaCuF3 and RbCuF3The crystal structures of triclinic NaCuF3 (a = 539.1, b = 555.2, c = 792.8 pm, α = 90.66, β = 92.05, γ = 86.95°; P1, Z = 4) and of tetragonal RbCuF3, isotypic with KCuF3, (a = 602.3, c = 791.2 pm; I4/mcm, Z = 4), were determined by x-ray methods and refined to wR = 0.038 (2113 reflections) resp. 0.039 (257 reflections). The structures derive from orthorhombic (GdFeO)3 and cubic perovskite type, resp., by Jahn-Teller distortion. The CuF64- octahedra, differently elongated in the two compounds (average NaCuF3: Cu—F = 188.9/197.3/225.6(2) pm; RbCuF3: 188.3/197.8/237.6(3) pm), show the same pattern of antiferrodistortive ordering, but there are bent bridges Cu—F—Cu = 144.2…148.0(1)° in NaCuF3. Structural relations to the prototypes mentioned and to comparably Jahn-Teller distorted copper fluoro compounds are discussed.
    Notes: Die Kristallstrukturen des triklinen NaCuF3 (a = 539,1, b = 555,2, c = 792,8 pm, α = 90,66, β = 92,05, γ = 86,95°; P1, Z = 4) und des tetragonalen, mit KCuF3 isotypen RbCuF3 (a = 602,3, c = 791,2 pm; I4/mcm, Z = 4) wurden röntgenographisch bestimmt und auf wR = 0,038 (2113 Reflexe) bzw. 0,039 (257 Reflexe) verfeinert. Die Strukturen leiten sich vom orthorhombischen (GdFeO3-) bzw. kubischen Perowskit-Typ durch Jahn-Teller-Verzerrung ab. Die in beiden Verbindungen unterschiedlich gestreckten CuF64--Oktaeder (Mittelwert NaCuF3: Cu—F = 188,9/197,3/225,6(2) pm; RbCuF3: 188,3/197,8/237,6(3) pm) sind nach demselben Muster antiferrodistortiv geordnet, jedoch unter Winkelung Cu—F—Cu = 144,2…148,0(1)° in NaCuF3. Strukturelle Beziehungen zu den genannten Prototypen und zu vergleichbar Jahn-Teller-verzerrten Kupfer-Fluorverbindungen werden diskutiert.
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  • 6
    ISSN: 0044-2313
    Keywords: Cyano-elpasolites ; bis(-tetramethylammonium) alkali hexacyanometallates ; preparation ; crystal structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Tetragonal Cyano-Elpasolites: The Crystal Structures of [N(CH3)4]2KMn(CN)6 and [N(CH3)4]2RbCo(CN)6The tetragonal bis(-tetramethylammonium)-alkali-hexacyanometallates [N(CH3)4]2KMn(CN)6 (a = 884.8(2), c = 1222.2(6) pm) and [N(CH3)4]2RbCo(CN)6 (a = 884.7(1), c = 1233.1(2) pm) were prepared in the form of single crystals and their structures determined by X-ray methods (wR = 0.050 and 0.047 for 486 and 463 independent reflections, respectively; space group 14/m, Z = 2). The average distances in the resulting elpasolite structure, which is but slightly tetragonally distorted by small ferro-rotative displacements of the [M(CN6]3-) octahedra (Mn—C = 201.8, C—N = 115.6, K—N = 307.1 pm resp. Co—C = 190.7, C—N = 114.8, Rb—N = 320.1 pm), seem a bit enlarged if compared to related cyano complexes. Reasons for this are discussed using a tolerance factor concept for cyanoepasolites.
    Notes: Die tetragonalen Bis(-tetramethylammonium)-Alkali-Hexacyanometallate [N(CH3)4]2KMn(CN)6 (a = 884.8(2), c = 1222,2(6) pm) und [N(CH3)4]2RbCo(CN)6 (a = 884,7(1), c = 1233,1(2) pm) wurden in Form von Einkristallen dargestellt und röntgenographisch ihre Strukturen bestimmt (wR = 0,050 bzw. 0,047 für 486 bzw. 463 unabhängige Reflexe; Raumgruppe 14/m, Z = 2). Die mittleren Abstände in der resultierenden Elpasolithstruktur, die durch geringe ferrorotative Drehung der [M(CN)6]3--Oktaeder nur wenig tetragonal verzerrt ist (Mn—C = 201,8, C—N = 115,6, K—N = 307,1 pm bzw. Co—C = 190,7, C—N = 114,8, Rb—N = 320,1 pm), erscheinen leicht vergrößert im Vergleich zu Werten die in verwandten Cyanokomplexen beobachtet wurden. Gründe dafür werden im Rahmen einer Toleranzfaktorbetrachtung für Cyano-Elpasolithe diskutiert.
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  • 7
    ISSN: 0044-2313
    Keywords: Copper weberites, Na2CuGaF7, Na2CuInF7 ; crystal structure ; magnetic investigation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Kupferweberite: Kristallstruktur und magnetische Untersuchung von Na2CuGaF7 und Na2CuInF7Die Kristallstruktur von zwei neuen Kupferweberiten Na2CuGaF7 und Na2CuInF7 wurde bestimmt. Na2CuGaF7: monokline Raumgruppe C2/c; a = 1232,5(5), b = 731,8(1), c = 1278,0(5) pm, β = 109,29(2)°, Z = 8. Na2CuInF7: orthorhombische Raumgruppe Pmnb; a = 731,8(1) pm, b = 1060,2(2) pm, c = 771,2(1) pm Z = 4. Die Strukturen wurden verfeinert mit 1175 Reflexen bis zu R = 0,043 (wR = 0,035) für Na2CuGaF7 und mit 1917 Reflexen bis zu R = 0,034 (wR = 0,025) für Na2CuInF7. Die Strukturen bestehen aus [CuF5]n3n--Ketten, die im Na2CuInF7 parallel zur a-Achse orientiert sind und in zwei alternierenden Richtungen im Na2CuGaF7. Die Natriumatome besitzen entweder siebenfache oder achtfache Koordination. Obwohl starke antiferromagnetische Wechselwirkungen innerhalb der Ketten beobachtet werden, gibt es keine Hinweise auf eine dreidimensionale Ordnung.
    Notes: The crystal structures of two new copper weberites Na2CuGaF7 and Na2CuInF7 have been determined. Na2CuGaF7 has the monoclinic space group C2/c: a = 1232.5(5) pm, b = 731.8(1) pm, c = 1278.0(5) pm, β = 109.29(2)° and Z = 8. Na2CuInF7 crystallizes in the orthorhombic space group Pmnb: a = 731.8(1) pm, b = 1060.2(2) pm, c = 771.2(1) pm and Z = 4. The structures have been refined from 1175 reflections to R = 0.043 (wR = 0.035) for Na2CuGaF7, and from 1917 reflections to R = 0.034 (wR = 0.025) for Na2CuInF7. The structures consist of [CuF5]n3n- chains which are parallel the a-axis in Na2CuInF7 and oriented in two alternating directions in Na2CuGaF7. Sodium atoms exhibit either seven-fold or eight-fold coordination. Although strong antiferromagnetic interactions are observed inside the chains, there is no evidence for three-dimensional ordering.
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  • 8
    ISSN: 0044-2313
    Keywords: Weberite ; crystal structure ; nickel aluminium fluoride ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Crystal Structure of Na2NiAlF7  -  a Contribution to the Problem of the True Space Group of Orthorhombic WeberitesThe X-ray single crystal structure determination of the orthorhombic weberite Na2NiAlF7 (a = 707.4(2), b = 1003.8(2), c = 731.5(1) pm; Z = 4) was performed in space group Imma, after all reflections hk0 with h(k) = 2n + 1 could be eliminated, as they proved simulated by Renninger effect and/or λ/2 reflections. The alternative space groups Imm2 resp. I212121 of former weberite structure determinations thus became obsolete. The refinement using 880 independent reflections ended at wR = 0.0232. The resulting average distances within the framework of octahedra are Ni—F = 197.3, Al—F = 180.4 pm.
    Notes: Die Röntgen-Einkristallstrukturbestimmung des orthorhombischen Weberits Na2NiAlF7 (a = 707,4(2), b = 1003,8(2), c = 731,5(1) pm; Z = 4) wurde in der Raumgruppe Imma vorgenommen, nachdem alle Reflexe hk0 mit h(k) = 2n + 1 eliminiert werden konnten, weil sie sich durch Renninger-Effekt und/oder λ/2-Reflexe als vorgetäuscht erwiesen. Damit wurden die alternativen Raumgruppen Imm2 bzw. I212121 früherer Weberit-Strukturbestimmungen obsolet. Die Verfeinerung mit 880 unabhängigen Reflexen schloß ab mit wR = 0,0232. Die resultierenden Mittelwerte für die Abstände im Oktaedernetz betragen Ni—F = 197,3 pm, Al—F = 180,4 pm.
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  • 9
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: X-Ray Single Crystal Structure Determinations of the Potassium Copper(II) Fluorides K2CuF4 and K3Cu2F7With single crystals of the tetragonal compounds K2CuF4 (a = 414.7(2), c = 1273(3) pm) and K3Cu2F7 (a = 415.6(3), c = 2052(3) pm), showing no superstructure reflections, crystal structure determinations were based on space group I4/mmm of the K2NiF4 and Sr3Ti2O7 type, resp. The shape of F0-Fourier maxima at the positions of linking fluorine atoms within the layers of octahedra suggested disorder of bridging ligands caused by multidomain structure, which could be refined assuming half occupation of higherfold positions. The results confirmed the Jahn-Teller-distortions of octahedra being elongated with a significant orthorhombic component: Cu—F = 190.9(7)/193.9(2)/223.8(7) pm in K2CuF4 (RW = 0.020) and 190.0(7)/194.7/225.6(7) pm in K3Cu2F7 (RW = 0.023). In the acentric octahedra of the latter compound the intermediate distance is averaged from the splitted lengths 192.7(4)/196.8(1) pm of axes along the c direction.
    Notes: Von Einkristallen der tetragonalen Verbindungen K2CuF4 (a = 414,7(2), c = 1273(3) pm) und K3Cu2F7 (a = 415,6(3), c = 2052(3) pm), die röntgenographisch keine Überstrukturreflexe zeigten, wurden die Kristallstrukturen unter Zugrundelegung der Raumgruppe I4/mmm des K2NiF4- bzw. Sr3Ti2O7-Typs bestimmt. Aus den Formen der F0-Fouriermaxima an den Stellen der die Oktaeder zu Schichten verknüpfenden Fluoratome wurde auf Fehlordnung der Brükkenliganden geschlossen, die von einer Multidomänenstruktur herrührt und unter Annahme halbbesetzter höherzähliger Punktlagen verfeinert werden kann. Das Ergebnis bestätigte die Jahn-Teller-Verzerrung zu gestreckten Oktaedern mit signifikanter orthorhombischer Komponente: Cu—F = 190,9(7)/193,9(2)/223,8(7) pm in K2CuF4 (RW = 0,020) und 190,0(7)/194,7/225,6(7) pm in K3Cu2F7 (RW = 0,023). In den azentrischen Oktaedern der letztgenannten Verbindung setzt sich der mittlere Abstand aus entlang der c-Richtung aufgespaltenen Achslängen von 192,7(4)/196,8(1) pm zusammen.
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  • 10
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Relations of Distances and Coordination in the Layer Structures of the Ternary Fluorides K2MF4 and K3M2F7 (MII = Mg, Mn, Co=Zn)Results of X-ray single crystal structure refinements of the compounds K2MF4 (M = Mg, Mn, Co, Ni) and K3M2F7 (M = Mn, Co, Ni), all crystallizing in the tetragonal space group I4/mmm of the K2NiF4 and Sr3Ti2O7 type, resp., are reported. The distances obtained are discussed, including data of the compounds with M = Cu, Zn. The influence of the KF9 coordination is made responsible for the fact, that the octahedral MF6 dimensions are much the same as in the corresponding perovskites KMF3. The shortest K—F distance of this KF9 group, occuring in both layer structure types, decreases against lattice widening from 263.4 pm (K2MgF4) to 258.0 pm (K2MnF4). The charge ratio calculated from the KF9 coordination for the unlike bonded anions leads to a better balanced charge distribution in the K2MF4 type, as is obtained by applying Pauling's rules.
    Notes: Ergebnisse röntgenographischer Einkristallstrukturverfeinerungen an den im K2NiF4- bzw. Sr3Ti2O7-Typ kristallisierenden Verbindungen K2MF4 (M = Mg, Mn, Co, Ni) und K3M2F7 (M = Mn, Co, Ni), die alle der tetragonalen Raumgruppe I4/mmm angehören, werden mitgeteilt. Die resultierenden Abstandsdaten werden unter Einbeziehung der Verbindungen mit M = Cu, Zn diskutiert. Die weitgehend den zugehörigen Perowskiten KMF3 entsprechenden Abstandsverhältnisse in den MF6-Oktaedern werden dem Einfluß der KF9-Koordination zugeschrieben, deren kürzester Abstand K—F in beiden Schichtstrukturtypen entgegen der Gitteraufweitung von 263,4 pm (K2MgF4) auf 258,0 pm (K2MnF4) abnimmt. Das aus der KF9-Koordination berechnete Ladungsverhältnis der ungleich gebundenen Anionen führt zu einer ausgeglicheneren Ladungsbilanz für den K2MF4-Typ, als die Anwendung der Paulingschen Regeln.
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