The effective shapes and sizes of Cu2+ and Mn3+ ions in oxides and fluorides
Abstract
Structural data, retrieved from the Inorganic Crystal Structure Database, have been used to study the effective shape and sizes of six coordinated Cu2+ and Mn3+ ions in oxides and fluorides. The distortions of the coordination octahedra for these two metal ions, essentially due to the structural implications of the Jahn-Teller effect, are assumed to be interpretable in terms of a nonspherical (ellipsoidal) effective shape of the metal ions. For octahedra with approximate tetragonal D4h symmetry (rotational ellipsoid) a reasonable one-parameter correlation function is shown to be 2/r42 + 1/r22 = 3/r02, where r4 is the ionic size perpendicular to and r2 the size along the rotation axis. The single parameter r0 to be determined, estimated to 0.66(1) Å for Cu2+ and 0.59(1) Å for Mn3+, represents the size of the spherical case. From the correlation function, possible estimates of the effective sizes for square planar four coordination (and linear two coordination) can be obtained by extrapolation, giving 0.54 Å and 0.48 Å for four coordinated Cu2+ and Mn3+, respectively. According to the correlation function the radii decrease with the square root of the coordination number.
For ions with effective ellipsoidal shapes like Cu2+ and Mn3+, it is shown that i.a. not only the use of average bond distances but also the previously used linear relation between average distances and distortion-parameters are strongly dependent on the degree of non-sphericity. A modified linear relation, between average bond distance and distortion, with improved linear correlation is suggested. As an alternative, the root harmonic mean square (rhms) value, 1/[unk], that gives an estimate of the parameter r0, is suggested to be used for judging the relevance of an observed bond length distribution (R1,…,R6 and ri estimated Ri – rligand) for six-coordinated ions.
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Artikel in diesem Heft
- The effective shapes and sizes of Cu2+ and Mn3+ ions in oxides and fluorides
- Determination of cation distributions by anomalous dispersion
- The NaAlSiO4 nepheline-carnegieite solid-state transformation
- Dielectric, pyroelectric, piezoelectric and optical investigation of the phase transition sequence in BaZnGeO4
- Anisotropy of anomalous scattering in X-ray diffraction. ‘Forbidden’ axial reflections in tetragonal space groups
- Growth and dissolution morphology of Ge crystals formed in GeI2-GeI4 vapor mixtures
- Ab initio direct phasing of proteins: the limits
- Rutile type derivatives
- Zn3Pt9B4, Ga2,7Ir9B5 und Ga3Pt9B4, Zink- und Gallium-Übergangsmetallboride mit neuen Kanalstrukturen
- Bestimmung der Strukturen von Ba(OH)Cl, Ba(OD)Cl und Ba(OD)Br durch Röntgeneinkristall- und Neutronenpulver-Messungen
- Kristallzüchtung und Einkristallstrukturverfeinerungen der Rhodium(III)-phosphate RhPO4 und RhP3O9
- Crystal and molecular structure of bis(3-cyano-2,4 pentanedionato)-bis(N,N-dimethylethylenediamine)copper(II). An unusual conformation and co-ordination of a β-dione
- Electro-optic and electrostrictive properties of the complex thiosulphates (NH4)9[Cu(S2O3)4]Br2, (NH4)9[Cu(S2O3)4]I2, and (NH4)9[Ag(S2O3)4]Br2
- Structures of the trans and cis isomers of 3,5-dioxo-3,5-diisopropoxy-1,3,5-thiadiphosphorinane
- Crystal structure of rubidium pentanitrato-scandate(III), Rb2Sc(NO3)5
- Crystal structure of tetrabarium bis(dinitridoborate) monoxide, Ba4(BN2)2O
- Crystal structure of lithium tetracalcium tris(dinitridoborate), LiCa4(BN2)3
- Crystal structure of 9-cis-5,9-bis(desmethyl)-9-methoxy-5-trifluoromethyl-β-ionylideneacetic acid ethyl ester, C17H23F3O3
- Crystal structure of 9-cis-5,9-bis(desmethyl)-5,9-bis(trifluoromethyl)-retinonitrile, C20H21F6N
- Crystal structure of bis(tetraphenylphosphonium) tetrakis(o-chlorothiophenolato)nickelate(II), [(C6H5)4P]2[Ni(SC6H4Cl)4]
- Crystal structure of trichlor-[2,5-di-tert-butyl-3-trimethylsilylpyrrolyl]-titanium(IV), C15H28Cl3NSiTi
- Crystal structure of 2-chloro-4-chloromethyl-6,7-dimethylquinoline, C12H11Cl2N
- Crystal structure of 1,10-phenanthrolinedichlorodiphenyltin, C24H18Cl2N2Sn
- Crystal structure of methyl 2-N-(diphenylmethylene)-2-propargylpent-4-ynoate, C22H19NO2
- Crystal structure of 5-tert-butyl-2-(2-methoxy-5-tert-butyl-phenyl)benzofuran, C23H28O2
- Crystal structure of bis{2-[dimethyl(2,3-dimethyl-2-butyl)silyloxy]-5-(2-methylpropyl)-phenyl}ethyne, C19H21OSi
- Crystal structure of 6-phenyl-1,2,3-triazine-9-carboxylic acid methyl ester, N3CCHC(C6H5)CO2(CH3)
Artikel in diesem Heft
- The effective shapes and sizes of Cu2+ and Mn3+ ions in oxides and fluorides
- Determination of cation distributions by anomalous dispersion
- The NaAlSiO4 nepheline-carnegieite solid-state transformation
- Dielectric, pyroelectric, piezoelectric and optical investigation of the phase transition sequence in BaZnGeO4
- Anisotropy of anomalous scattering in X-ray diffraction. ‘Forbidden’ axial reflections in tetragonal space groups
- Growth and dissolution morphology of Ge crystals formed in GeI2-GeI4 vapor mixtures
- Ab initio direct phasing of proteins: the limits
- Rutile type derivatives
- Zn3Pt9B4, Ga2,7Ir9B5 und Ga3Pt9B4, Zink- und Gallium-Übergangsmetallboride mit neuen Kanalstrukturen
- Bestimmung der Strukturen von Ba(OH)Cl, Ba(OD)Cl und Ba(OD)Br durch Röntgeneinkristall- und Neutronenpulver-Messungen
- Kristallzüchtung und Einkristallstrukturverfeinerungen der Rhodium(III)-phosphate RhPO4 und RhP3O9
- Crystal and molecular structure of bis(3-cyano-2,4 pentanedionato)-bis(N,N-dimethylethylenediamine)copper(II). An unusual conformation and co-ordination of a β-dione
- Electro-optic and electrostrictive properties of the complex thiosulphates (NH4)9[Cu(S2O3)4]Br2, (NH4)9[Cu(S2O3)4]I2, and (NH4)9[Ag(S2O3)4]Br2
- Structures of the trans and cis isomers of 3,5-dioxo-3,5-diisopropoxy-1,3,5-thiadiphosphorinane
- Crystal structure of rubidium pentanitrato-scandate(III), Rb2Sc(NO3)5
- Crystal structure of tetrabarium bis(dinitridoborate) monoxide, Ba4(BN2)2O
- Crystal structure of lithium tetracalcium tris(dinitridoborate), LiCa4(BN2)3
- Crystal structure of 9-cis-5,9-bis(desmethyl)-9-methoxy-5-trifluoromethyl-β-ionylideneacetic acid ethyl ester, C17H23F3O3
- Crystal structure of 9-cis-5,9-bis(desmethyl)-5,9-bis(trifluoromethyl)-retinonitrile, C20H21F6N
- Crystal structure of bis(tetraphenylphosphonium) tetrakis(o-chlorothiophenolato)nickelate(II), [(C6H5)4P]2[Ni(SC6H4Cl)4]
- Crystal structure of trichlor-[2,5-di-tert-butyl-3-trimethylsilylpyrrolyl]-titanium(IV), C15H28Cl3NSiTi
- Crystal structure of 2-chloro-4-chloromethyl-6,7-dimethylquinoline, C12H11Cl2N
- Crystal structure of 1,10-phenanthrolinedichlorodiphenyltin, C24H18Cl2N2Sn
- Crystal structure of methyl 2-N-(diphenylmethylene)-2-propargylpent-4-ynoate, C22H19NO2
- Crystal structure of 5-tert-butyl-2-(2-methoxy-5-tert-butyl-phenyl)benzofuran, C23H28O2
- Crystal structure of bis{2-[dimethyl(2,3-dimethyl-2-butyl)silyloxy]-5-(2-methylpropyl)-phenyl}ethyne, C19H21OSi
- Crystal structure of 6-phenyl-1,2,3-triazine-9-carboxylic acid methyl ester, N3CCHC(C6H5)CO2(CH3)
