The Mössbauer effect in tin(<scp>II</scp>) compounds. Part XI. The spectra of cubic trihalogenostannates(<scp>II</scp>)

Barrett, James H.; Bird, S. R. A.; Donaldson, J. D.; Silver, Jack

doi:10.1039/j19710003105

Cited by 91 publications

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“…Similar low Mrssbauer isomer shifts were found by Barrett et al (1971) for the cubic CsSnX3 phases (e.g. +1.33 mm.sec -~ relative to t-tin for CsSnBra) and similar explanations suggested.…”

Section: Miissbauer Spectroscopysupporting

confidence: 59%

The crystal structure of tin(II) iodide

Howie¹,

Moser²,

Trevena³

1972

Acta Crystallogr Sect B

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“…Similar low Mrssbauer isomer shifts were found by Barrett et al (1971) for the cubic CsSnX3 phases (e.g. +1.33 mm.sec -~ relative to t-tin for CsSnBra) and similar explanations suggested.…”

Section: Miissbauer Spectroscopysupporting

confidence: 59%

The crystal structure of tin(II) iodide

Howie¹,

Moser²,

Trevena³

1972

Acta Crystallogr Sect B

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“…'Easily supercooled down to room temperature; reversal to the LT phase very sluggish at room temperature, but ref. 109 states that the reversal is very fast at 80 K. As against this, "traces of water may catalyze the transition to the low phase; completely dry HT-CsSnC13 was stable at room temperature for at least a year and was also found stable down to 77 K" (1 10).…”

Section: Active Lp E= Inactive L P Conversionmentioning

confidence: 99%

The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

Knop¹,

Linden²,

Vincent³

et al. 1989

Can. J. Chem.

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The results of a detailed analysis of typical situations in crystals containing trigonal-pyramidal YEL3' species are used to argue that, per se, the lone electron pair (E, LP) on the Y atom determines neither the crystal structure nor the onentation of the Y EL3' units in the crystal. Considered as a space-filling entity, the LP has practically no effective volume of its own. Whatever space-filling or orienting properties may be associated with the presence of the LP, they are not autonomous; they arise from the intrinsic stereochemical involvement of the LP in the geometry of and the charge distribution in the free YEL3' ion or molecule and hence from the consequences of this geometry for crystal packing. Ab initio (6-31G*) calculations show that the electron density in the region of the LP in an ion is only slightly perturbed by the charge on the counter ion at distances observed in crystals. There is considerable similarity in the electron density distribution in the LP region of Y between free anionic (~0~~~ and free cationic (Me3S+) species. The problem of the so-called stereochemical inertness of the LP in the 14-electron octahedral Y E X~~-ions in crystals is examined in detail. It is concluded that the crystallographic Oh symmetry of the ion in cubic crystals is the result of dynamic averaging of possible orientations of the inherently noncubic YX62-octahedron (cf. the ab initio results for S e~l~~-) .Such averaging also appears to be responsible for the stereochemical "activation" or "inactivation" of the LP in thermally induced crystallographic transitions in the AYX3 halide perovskites and related crystals. To provide a firmer basis for the discussion of the LP, the crystal structures of the five title compounds have been determined. The crystal chemistry of these and related compounds is discussed.Key words: ab initio calculations, Me3S+ and SeC162-; group V trihalides; lone electron pair; trialkylsulfonium salts; VSEPR theory.OSVALD KNOP, ANTHONY LINDEN, BEVERLY R. VINCENT, S. C. CHOI, T. STANLEY CAMERON et RUSSELL J. BOYD. Can. J. Chem. 67, 1984Chem. 67, (1989.En se basant sur les rCsultats d'une analyse dCtaillte de situations typiques dans des cristaux contenant des espkces YEL3', on suggkre que la paire dYClectron libre (E, PL) sur l'atome Y ne dCtermine pas per se la structure cristalline ou I'orientation des unit& Y EL3' dans le cristal. ConsidCrte comme une entitC qui occupe du volume, la PL n'a pratiquement pas de volume effectif intrinskque. Quelles que soient les propriCtCs associCes avec la prCsence de la PL, elles ne sont pas autonomes; elles dCcoulent de l'implication stCrCochimique intrinskque de la PL dans la gComCtrie de et de la distribution de charge dans l'ion ou la molCcule YEL$ libre et ainsi des consCquences de cette gComCtrie sur I'empilement cristallin. Des calculs ab initio (6-3 lG*) dCmontrent que, aux distances observkes dans les cristaux, la densite tlectronique dans la rkgion de la PL d'un ion n'est que ICgkrement perturbCe par la charge du contre-ion. I1 existe une gr...

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“…Die in den meisten Fällen anzutreffende Liganden Verteilung niederer Symmetrie kann mit der Mischung von s-und p-Valenzzuständen erklärt werden [2], Eines dieser seltenen Beispiele mit stereochemisch inaktiven ns 2 -Elektronen ist das schwarze, im kubischen Perowskitgitter kristallisierende CsSnBr3 [3,4], das sich im Gegensatz zu den übrigen Alkali-Zinn(II)-Halogeniden durch intensive Eigenfarbe und elektrische Leitfähigkeit auszeichnet [5,6], Das Sn(II)-Ion ist hier streng oktaedrisch von den Anionen umgeben.…”

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CH₃NH₃SnBr_xI_3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur / CH₃NH₃SnBr_xI_3-x(x = 0-3), a Sn(II)-System with Cubic Perovskite Structure

Weber

1978

Zeitschrift Für Naturforschung B

210

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CH3NH3SnBrxl3-x: (x = 0-3) has the cubic perovskite structure with the unit cell parameters a = 5.89 Å (x = 3), a = 6.01 Å (x = 2) and a = 6.24 A (x = 0) and Z = 1. The compounds show intense colour and conducting property. The 119Sn Mössbauer data are consistent with the high symmetry environment of the Sn(II)-ion. A bonding model, using a “p-resonance-bonding”, can explain the properties of the cubic system. The synthesis is described.

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The Mössbauer effect in tin(II) compounds. Part XI. The spectra of cubic trihalogenostannates(II)

Cited by 91 publications

References 0 publications

The crystal structure of tin(II) iodide

The crystal structure of tin(II) iodide

The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

CH₃NH₃SnBr_xI_3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur / CH₃NH₃SnBr_xI_3-x(x = 0-3), a Sn(II)-System with Cubic Perovskite Structure

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The Mössbauer effect in tin(II) compounds. Part XI. The spectra of cubic trihalogenostannates(II)

Cited by 91 publications

References 0 publications

The crystal structure of tin(II) iodide

The crystal structure of tin(II) iodide

The lone electron pair and crystal packing: observations on pyramidal YEL3ε species, abinitio calculations, and the crystal structures of Me3SOI, Et3SI, (Me3S)2SnCl6, (Me3SO)2SnCl6, and (Et3S)2SnCl6

CH3NH3SnBrxI3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur / CH3NH3SnBrxI3-x(x = 0-3), a Sn(II)-System with Cubic Perovskite Structure

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The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

CH₃NH₃SnBr_xI_3-x (x = 0-3), ein Sn(II)-System mit kubischer Perowskitstruktur / CH₃NH₃SnBr_xI_3-x(x = 0-3), a Sn(II)-System with Cubic Perovskite Structure