Etude cristallochimique d'hydrates intermédiaires de la série des aluns. Cas du dihydrate CsTlIII(SO4)2.2H2O

Manoli, Jean‐Marie; Herpin, Paulette; Dereigne, A.

doi:10.1107/s0567740872003231

Cited by 6 publications

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“…The anomalously large disorder parameter corresponds to a wider than normal distribution of the Tl-O distances, probably the result of a dynamic distortion caused by a weak pseudo-Jahn-Teller effect. Only one signal appears in each type of NMR spectra ( 205 Tl, 13 C, and 1 H NMR) of the complex in solution, showing that the two CH 3 groups of the dimethyl sulfoxide ligands are equivalent on the current NMR time scale.…”

Section: Discussionmentioning

confidence: 94%

“…In an acetonitrile-d 3 solution of hexakis(dimethyl sulfoxide)thallium(III) perchlorate, a 13 C NMR signal was detected at 39.5 ppm, while the corresponding chemical shift is 41.31 ppm in neat dimethyl sulfoxide. It is clear that the two CH 3 groups of the dimethyl sulfoxide ligands in the thallium(III) complex are equivalent on the actual NMR time scale.…”

Section: Resultsmentioning

confidence: 99%

“…9,10 The compound [Tl(H 2 O) 6 ](ClO 4 ) 3 contains octahedrally hexahydrated thallium(III) ions. 10 Disorder in the crystal structure prevented the precise determination of the Tl-O bond distance, but octahedral six-coordination, sometimes severely distorted, is also found in the compounds thallium(III) oxide (Tl 2 O 3 ; mean Tl-O distance 2.27 Å), 11 RbTl(SO 4 ) 2 (2.23 Å), 12 CsTl(SO 4 ) 2 ‚2H 2 O (2.24 Å), 13 Tl(H 2 O) 3 (CF 3 SO 3 ) 3 (2.21 Å), 14 and TlOHSO 4 ‚2.5H 2 O (2.24 Å). 15 In a plot of the observed hydration number versus Shannon's effective radius for trivalent metal ions, thallium(III) is found to have metal-oxygen bond distances similar to those of the smaller octahydrated lanthanide-(III) ions and the yttrium(III) ion.…”

Section: Introductionmentioning

confidence: 99%

“…In acidic aqueous solution, the thallium(III) ion coordinates six water oxygen atoms with d (Tl−O) of 2.235(5) and 2.21(2) Å, as determined by means of LAXS and EXAFS, respectively. , The compound [Tl(H 2 O) 6 ](ClO 4 ) 3 contains octahedrally hexahydrated thallium(III) ions . Disorder in the crystal structure prevented the precise determination of the Tl−O bond distance, but octahedral six-coordination, sometimes severely distorted, is also found in the compounds thallium(III) oxide (Tl 2 O 3 ; mean Tl−O distance 2.27 Å), RbTl(SO 4 ) 2 (2.23 Å), CsTl(SO 4 ) 2 ·2H 2 O (2.24 Å), Tl(H 2 O) 3 (CF 3 SO 3 ) 3 (2.21 Å), and TlOHSO 4 ·2.5H 2 O (2.24 Å) . In a plot of the observed hydration number versus Shannon's effective radius for trivalent metal ions, thallium(III) is found to have metal−oxygen bond distances similar to those of the smaller octahydrated lanthanide(III) ions and the yttrium(III) ion. , Also, thallium(III) has a larger radius than scandium(III), which has a mean Sc−O bond distance of 2.075(3) Å in the crystal structure of [Sc(dmso) 6 ]I 3 , of 2.09 Å in octahedral six-coordinated [Sc(H 2 O) 6 ] 3+ hydrates, and of 2.16 Å in pentagonal-bipyramidal seven-coordinated hydrates .…”

Section: Introductionmentioning

confidence: 99%

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Structure of the Dimethyl Sulfoxide Solvated Thallium(III) Ion in Solution and in the Solid State

Molla-Abbassi

Kritikos

et al. 2001

Inorg. Chem.

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The structure and vibrational spectra of the dimethyl sulfoxide solvated thallium(III) ion have been studied in a dimethyl sulfoxide solution and in the solid state. X-ray crystallography shows a trigonal unit cell, space group R(-)3 (No. 148), for the [Tl(dmso)(6)](ClO(4))(3) compound with Z = 3, a = b = 11.9764(13) [11.8995(9)] A, c = 20.802(2) [20.467(2)] A, and V = 2584.0(5) [2509.9(4)] A(3) at 295 [150] K. The crystal structure comprises a highly symmetric hexakis(dimethyl sulfoxide)thallium(III) ion, with thallium in a (-)3 symmetry site and a Tl-O bond distance of 2.224(3) A at 295 K. The octahedral TlO(6) kernel is compressed along the threefold axis with an O-Tl-O bond angle of 96.20(11) degrees. The Tl-O-S bond angle of 120.7(2) degrees corresponds to a Tl.S distance of 3.292(2) A. One perchlorate ion centered on the (-)3 axis was described by a statistically disordered model. A low-temperature EXAFS study (10 K) resulted in the Tl-O and Tl.S distances of 2.221(4) and 3.282(6) A, respectively, consistent with a Tl-O-S bond angle of 120(1) degrees. The low Debye-Waller factors confirm a regular coordination without the disorder of the dimethyl sulfoxide ligands, which would have resulted from the alternative choice of space group R3 for the crystal structure. Raman and infrared spectra have been recorded and assigned, with the bands at 435 and 447 cm(-)(1) corresponding to the vibrational frequency of the symmetric and asymmetric Tl-O stretching modes, respectively. EXAFS data of a 0.5 mol dm(-3)thallium(III) trifluoromethanesulfonate in a dimethyl sulfoxide solution were consistent with that of a hexasolvated ion with mean Tl-O and Tl.S distances of 2.22(1) and 3.33(2) A, respectively, which correspond to a mean Tl-O-S bond angle of 124(2) degrees. The anomalously large disorder parameter for the Tl-O distances is consistent with a weak pseudo-Jahn-Teller effect. The (205)Tl, (13)C, and (1)H NMR spectra of the complex in solution show single signals at 1886, 39.5, and 2.3 ppm, respectively.

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Section: Discussionmentioning

confidence: 94%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure of the Dimethyl Sulfoxide Solvated Thallium(III) Ion in Solution and in the Solid State

Molla-Abbassi

Kritikos

et al. 2001

Inorg. Chem.

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“…2.21 Å. 12, 14 The mean Tl-O bond distances for other octahedrally oxygen-coordinated thallium() complexes in the solid state are Cs[Tl(OH 2 ) 2 (SO 4 ) 2 ] (2.24 Å), 40 Tl I 2 Tl III OH(SO 4 ) 2 (2.24 Å), 41 TlOHSO 4 ؒ2.5 H 2 O (2.22 Å) 42 and Tl 2 O 3 (2.27 Å). 43 The mean Tl-O-S bond angle in 2, 132.9Њ, is smaller than the corresponding Hg-O-S angle in 1, 137.1Њ.…”

Section: Crystal Structure Ofmentioning

confidence: 99%

Structure and bonding of bisaquamercury(ii) and trisaquathallium(iii) trifluoromethanesulfonate

Molla-Abbassi

Mink

Persson

et al. 2002

J. Chem. Soc., Dalton Trans.

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The structure and bonding in bisaquamercury() trifluoromethanesulfonate, [Hg(OH 2 ) 2 (CF 3 SO 3 ) 2 ] ∞ , and trisaquathallium() trifluoromethanesulfonate, [Tl(OH 2 ) 3 (CF 3 SO 3 ) 3 ], have been studied by means of single-crystal X-ray diffraction, EXAFS and vibrational spectroscopy. The crystal structure of bisaquamercury() trifluoromethanesulfonate shows an unusual connectivity pattern. The mercury() ion strongly binds two water molecules axially with the Hg-O bond distance 2.11 Å, and four oxygen atoms from four trifluoromethanesulfonate ions complete a tetragonally compressed octahedral coordination geometry, at the mean Hg-O distance 2.53 Å. Two trifluoromethanesulfonate ions form double bridges between the bisaquamercury() entities giving rise to infinite >Hg(OH 2 ) 2 <(CF 3 SO 3 ) 2 >Hg(OH 2 ) 2 < chains. The parallel chains are held together in layers by relatively strong hydrogen bonds with O(-H) ؒ ؒ ؒ O distances in the range 2.688(9)-2.735(9) Å. The O-D stretching vibrational frequencies of the hydrogen bonds in the partly deuterated compound occur in a broad band at about 2400 cm Ϫ1 , bandwidth ca. 170 cm Ϫ1 . The layers are connected only via van der Waals interactions between the protruding CF 3 groups, consistent with the fragile sheet-like structure of the crystalline compound. Trisaquathallium() trifluoromethanesulfonate crystallises as molecular complexes where each thallium() ion binds three water molecules and three oxygen atoms from trifluoromethanesulfonate ions, with Tl-O bond distances in the range 2.18-2.24 Å. A hydrogen bond network between the water molecules and trifluoromethanesulfonate ions with O(-H) ؒ ؒ ؒ O distances in the range 2.65(1)-2.80(1) Å holds the structure together. Raman and infrared spectra have been recorded and analysed. The changes in force constants and vibrational frequencies have been correlated with bond lengths for the S-O bond in the coordinated trifluoromethanesulfonate ion and for the Hg-O and Tl-O bonds, also including the hexaaquaions in the comparisons.

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b3503, IV.3.2.1 Sulfates with H2O

Pies¹,

Weiß²

Landolt-Börnstein - Group III Condensed Matter

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Etude cristallochimique d'hydrates intermédiaires de la série des aluns. Cas du dihydrate CsTlIII(SO4)2.2H2O

Cited by 6 publications

References 1 publication

Structure of the Dimethyl Sulfoxide Solvated Thallium(III) Ion in Solution and in the Solid State

Structure of the Dimethyl Sulfoxide Solvated Thallium(III) Ion in Solution and in the Solid State

Structure and bonding of bisaquamercury(ii) and trisaquathallium(iii) trifluoromethanesulfonate

b3503, IV.3.2.1 Sulfates with H2O

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