Charge density in (NH4)2Cr(SO4)2.6H2O at 84 K: a Jahn–Teller distorted complex

Figgis, Brian N.; Kucharski, E. S.; Reynolds, P. A.

doi:10.1107/s0108768190005845

Cited by 20 publications

(6 citation statements)

References 22 publications

(38 reference statements)

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“…For all these compounds the longest CuÐO bond is to O(7), a characteristic of form B. Also given are the CuÐO bond lengths reported for deuterated ammonium copper(II) sulfate at 15 K and ambient pressure (Simmons et al, 1993), as well as the CrÐO bond lengths for the hydrogenous and deuterated forms of the analogous chromium(II) compound (Figgis et al, 1990(Figgis et al, , 1991 measured at ambient pressure and very low temperature. For these latter compounds the longest bond occurs to O(8), which is characteristic of form A.…”

Section: Resultsmentioning

confidence: 99%

Bonding effects and the crystal structures of (NH₄)₂[Cu(H₂O)₆](SO₄)₂ and its H₂ ¹⁸O substituted form at 9.5 K

Figgis

Sobolev

Simmons

et al. 2000

Acta Crystallogr Sect B

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The crystal structures of the Tutton salts (NH 4 ) 2 -[Cu(H 2 O) 6 ](SO 4 ) 2 , diammonium hexaaquacopper disulfate, formed with normal water and isotopically substituted H 2 18 O, have been determined by X-ray diffraction at 9.5 K and are very similar, with CuÐO(7) the longest of the CuÐO bonds of the Jahn±Teller distorted octahedral [Cu(H 2 O) 6 ] 2+ complex. It is known that structural differences accompany deuteration of (NH 4 ) 2 [Cu(H 2 O) 6 ](SO 4 ) 2 , the most dramatic of which is a switch to CuÐO(8) as the longest such bond. The present result suggests that the structural differences are associated with hydrogen-bonding effects rather than with increased mass of the water ligands affecting the Jahn±Teller coupling. The Jahn±Teller distortions and hydrogen-bonding contacts in the compounds are compared with those reported for other Tutton salts at ambient and high pressure.

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Section: Resultsmentioning

confidence: 99%

Bonding effects and the crystal structures of (NH₄)₂[Cu(H₂O)₆](SO₄)₂ and its H₂ ¹⁸O substituted form at 9.5 K

Figgis

Sobolev

Simmons

et al. 2000

Acta Crystallogr Sect B

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“…The DFT calculated data compare well with available experimental data. A summary of available experimental structural data for selected hexaaquametal(II) ions is given in Supporting information Table S1 for [Cu(OH 2 ) 6 ] 2+ [2], Table S2 for [Cr(OH 2 ) 6 ] 2+ [3], [4], [5], [6], [7], [8] and Table S3 for [Ni(OH 2 ) 6 ] 2+ [2]. Selected experimental structural data of [Cu(OH 2 ) 6 ] 2+ , illustrated in Fig.…”

Section: Datamentioning

confidence: 99%

“…3Illustration of Cr─O bond lengths (L1–L6 in Å on x -axis) for experimentally observed octahedral elongated geometries of selected [Cr(OH 2 ) 6 ] 2+ ions. Data from references [3] for S1–S4, [4] for S5, [5] for S6 and S7, [6] for S8 and [7] for S9.…”

Section: Datamentioning

confidence: 99%

Structural and electronic data of three first-row transition octahedral hexaaquametal(II) ions, metal=Cr, Ni or Cu

Conradie

2018

Data in Brief

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Structural and density functional theory calculated data of three octahedral hexaaquametal(II) ions containing different metals (Cr, Ni or Cu) are presented to illustrate different geometries these octahedral hexaaquametal(II) ions can have. The density functional theory optimized geometries exhibit either a regular octahedral geometry, an octahedral elongated or an octahedral compressed geometry. Experimental structures exhibit octahedral or distorted octahedral geometries, the latter includes octahedral elongated, octahedral compressed and orthorhombic distorted geometries.

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“…This is illustrated for a high-spin d 4 (Cr 2þ ) complex in Figure 8.5, in which the driving force of the Jahn-Teller effect is seen to be the energy E JT . Indeed, the Cr(H 2 O) 6 2þ unit in the high-spin solid Tutton salt (NH 4 ) 2 [Cr(H 2 O) 6 ](SO 4 ) 2 80 is tetragonally distorted with a 16% elongation of the axial Cr-O bond lengths relative to the equatorial, 81 and it is reasonable to assume that this structure persists in solution. Clearly, the two remote ligands could be easily exchanged with solvent by either an I a or an I d mechanism, and vibrations of the complex should result in rapid inversion of the axial and equatorial positions on a femtosecond to picosecond timescale.…”

Section: Water Exchange Reactionsmentioning

confidence: 99%

Ligand Substitution Dynamics in Metal Complexes

Swaddle

2010

Physical Inorganic Chemistry

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On the base of our previous studies due to the presence of halides in our complexes there is strong probability for obtaining coordination polymers. Crystal engineering well-defined as the understanding of intermolecular interactions in the context of crystal packing and the utilization of such understanding in the design of new solids with desired physical and chemical properties. Owing to the fact that the small changes in the ligands may play a significant role in the complexes, the organic ligand (1-naphtyl pyridine-2-carboxylate) (L), was synthesized. In order make more steric repulsion around of the complexes resulted in the substitution effect around of the naphtyl moiety was hired in the design. Relocation in the position of functional group was fulfilled our expectations. Three new mercury (II) halide complexes, [Hg(L)2Cl2] (1), [Hg(L)2Br2] (2) and [Hg(L)2I2] (3) were synthesized. All of the compounds were fully characterized using FT-IR, TGA, DSC, mass spectrometry, CHNOS elemental analyses, PXRD, NMR and SCXRD. The results indicate that metal-ligand polymerization controlled by substitution effect. The coordination geometry around the Hg (II) ion is seesaw shape in distorted tetrahedral geometry for compounds (1), (2) and (3) with τ4 of 0.74, 0.76 and 0.78, respectively. Due to the replacement of the functional group (mentioned substitution effect), flexibility of coodinated ligand was decreased. In the previously reported structures, the angle between two planes of aromatic rings in the analogous ligand was 78.37o which changed to the 59.47o, 50.75o and 64.90o for mercury halide series complexes. In present study these angles are 89.09, 89.73 and 88.90 for titled complexes based on new designed ligand. Consequently, this study emphasize that the substitution effect can play the significant role through the flexibility of designed ligand to control the metal-ligand polymerization.

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Charge density in (NH₄)₂Cr(SO₄)₂.6H₂O at 84 K: a Jahn–Teller distorted complex

Abstract: Abstract

Cited by 20 publications

References 22 publications

Bonding effects and the crystal structures of (NH₄)₂[Cu(H₂O)₆](SO₄)₂ and its H₂ ¹⁸O substituted form at 9.5 K

Bonding effects and the crystal structures of (NH₄)₂[Cu(H₂O)₆](SO₄)₂ and its H₂ ¹⁸O substituted form at 9.5 K

Structural and electronic data of three first-row transition octahedral hexaaquametal(II) ions, metal=Cr, Ni or Cu

Ligand Substitution Dynamics in Metal Complexes

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Charge density in (NH4)2Cr(SO4)2.6H2O at 84 K: a Jahn–Teller distorted complex

Abstract: Abstract

Cited by 20 publications

References 22 publications

Bonding effects and the crystal structures of (NH4)2[Cu(H2O)6](SO4)2 and its H2 18O substituted form at 9.5 K

Bonding effects and the crystal structures of (NH4)2[Cu(H2O)6](SO4)2 and its H2 18O substituted form at 9.5 K

Structural and electronic data of three first-row transition octahedral hexaaquametal(II) ions, metal=Cr, Ni or Cu

Ligand Substitution Dynamics in Metal Complexes

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Product

Resources

About

Charge density in (NH₄)₂Cr(SO₄)₂.6H₂O at 84 K: a Jahn–Teller distorted complex

Bonding effects and the crystal structures of (NH₄)₂[Cu(H₂O)₆](SO₄)₂ and its H₂ ¹⁸O substituted form at 9.5 K

Bonding effects and the crystal structures of (NH₄)₂[Cu(H₂O)₆](SO₄)₂ and its H₂ ¹⁸O substituted form at 9.5 K