Single-crystal and high-resolution X-ray diffraction studies and Raman spectrum of a phosphorus(V) chloride complex containing a single bromide ion, P3Cl14Br

Gates, Peter N.; Knachel, Howard C.; Finch, Arthur; Fratini, Albert; Fitch, Andrew N.; Nardone, Ottavio; Otto, James C.; Snider, Daniel A.

doi:10.1039/dt9950002719

Cited by 6 publications

(5 citation statements)

References 12 publications

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“…The broad agreement between these estimates (eqs 46 and 47) and those stemming from the more rigorous calculations we have made suggest that the ionic models used in the LATEN calculations (despite the probable proximity of the ionic−covalent borderline) are likely to be valid and that the predominant contribution to the bonding in the [PCl 4 ] 2 [PCl 6 ]X salts is strongly ionic. This conclusion appears to be borne out by spectroscopic evidence …”

Section: Resultsmentioning

confidence: 83%

“…Both powder and simple crystal X-ray 20 structural data are available for the corresponding bromide salt, and lattice energy calculations can be used to compare the structures from the two sources. The total lattice potential energy of bis(tetrachlorophosphorus) hexachlorophosphate bromide is found to be (with U ELEC = 912 kJ mol -1 , U R = 174 kJ mol -1 , U dd = 254 kJ mol -1 , and U qd = 20 kJ mol -1 ) for the process based on unpublished powder data ( a = 8.7472 Å, c = 12.3281 Å, space group I 4/ m ) while taking the value (with U ELEC = 908 kJ mol -1 , U R = 172 kJ mol -1 , U dd = 256 kJ mol -1 , and U qd = 21 kJ mol -1 ) based on the published Knachel et al single crystal data ( a = 8.739 Å, c = 12.320 Å, space group I 4).…”

Section: Calculationsmentioning

confidence: 99%

“…The solid state structure of bis(tetrachlorophosphonium) hexachlorophosphate bromide, [PCl 4 ] 2 [PCl 6 ]Br, empirical formula P 3 Cl 14 Br, has, on the other hand, been solved by both single-crystal X-ray diffraction techniques and by Rietveld refinement of high-resolution powder X-ray diffraction data …”

Section: Introductionmentioning

confidence: 99%

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Ionic Isomerism. 3. Estimation of Enthalpies of Formation of the Gaseous Tetrachlorophosphonium Ion, Δ_fH°(PCl₄⁺,g), and of the Gaseous Hexachlorophosphate Ion, Δ_fH°(PCl₆^-,g). Lattice Enthalpy Calculations for Bis(tetrachlorophosphonium) Hexachlorophosphate Halides, [PCl₄]₂[PCl₆]X, Where X = Cl or Br. Bond Enthalpies of Phosphorus(V) Chloro Compounds

Jenkins¹,

Sharman²,

Finch³

et al. 1996

Inorg. Chem.

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Recent structural and synthetic work on phosphorus−halo compounds over the past 3 years has provided a means of estimating associated thermochemical data. The lattice energy of Me4NPCl6 and the stability criteria for the existence of CsPCl6 as the only stable alkali metal hexachlorophosphate at ambient temperature are used to predict values for Δf H°(PCl6 -,g) while, in parallel, the rigorous calculation of the lattice potential energy of normal PCl5 (phase II, PCl5 as [PCl4 +][PCl6 -]) provides a functional thermodynamic relationship between Δf H°(PCl6 -,g) and Δf H°(PCl4 +,g) and hence enables estimation of Δf H°(PCl4 +,g). The total lattice potential energies of the [PCl4]2[PCl6]X (X = Cl (phase III, PCl5) and Br) salts are computed using a rigorous computational procedure designed to model lattices possessing complex anions and cations. These calculations lead to values of 1038 ± 5 kJ mol-1 for the lattice potential energy of [PCl4]2[PCl6]Cl and 1013 ± 5 kJ mol-1 for [PCl4]2[PCl6]Br and to estimates for the enthalpies of formation of the gaseous complex ions, Δf H°(PCl4 +,g) and Δf H°(PCl6 -,g) of 384 ± 10 kJ mol-1 and −813 ± 10 kJ mol-1, respectively. The above values differ from our previous estimates, which were based on speculative structures. Bond enthalpy estimates are made for phosphorus(V) chloro compounds. A brief consideration of the recent Glasser extension of the Kapustinskii equation is made with respect to these salts.

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Section: Resultsmentioning

confidence: 83%

Section: Calculationsmentioning

confidence: 99%

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Ionic Isomerism. 3. Estimation of Enthalpies of Formation of the Gaseous Tetrachlorophosphonium Ion, Δ_fH°(PCl₄⁺,g), and of the Gaseous Hexachlorophosphate Ion, Δ_fH°(PCl₆^-,g). Lattice Enthalpy Calculations for Bis(tetrachlorophosphonium) Hexachlorophosphate Halides, [PCl₄]₂[PCl₆]X, Where X = Cl or Br. Bond Enthalpies of Phosphorus(V) Chloro Compounds

Jenkins¹,

Sharman²,

Finch³

et al. 1996

Inorg. Chem.

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“…With the exception of bismuth, examples of tetrahalopnicogen(V) cations are known for all remaining group 15 elements. While only the fluoro- , and chlorocations are known for nitrogen, all the tetraphosphonium(V) cations have been synthesized and are the most fully characterized series of tetrahalopnicogen cations, with crystal structure determinations for PCl 4 + , − PBr 4 + , , and PI 4 + , 31 P NMR spectroscopic studies for PCl 4 + and PBr 4 + , − and vibrational studies for PCl 4 + , ,,− PBr 4 + , ,,− and PI 4 + . The PF 4 + cation has only been characterized in the solid state by Raman spectroscopy. , Several SbCl 4 + salts have been characterized by X-ray crystallography − and vibrational spectroscopy. , We recently reported a full characterization in solution by 121,123 Sb NMR spectroscopy and in the solid state of the previously unknown SbBr 4 + and known SbCl 4 + cations as their Sb(OTeF 5 ) 6 - salts .…”

Section: Introductionmentioning

confidence: 99%

Tetrachloro- and Tetrabromoarsonium(V) Cations: Raman and ⁷⁵As, ¹⁹F NMR Spectroscopic Characterization and X-ray Crystal Structures of [AsCl₄][As(OTeF₅)₆] and [AsBr₄][AsF(OTeF₅)₅]

et al. 2000

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The salts [AsX4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5] (X = Cl, Br) have been prepared by oxidation of AsX3 with XOTeF5 in the presence of the OTeF5 acceptors As(OTeF5)5 and AsF(OTeF5)4. The mixed salts [AsCl4][Sb(OTeF5)6-nCl(n-2)] and [AsCl4][Sb(OTeF5)6-nCl(n)] (n > or = 2) have also been prepared. The AsBr4+ cation has been fully structurally characterized for the first time in SO2ClF solution by 75As NMR spectroscopy and in the solid state by a single-crystal X-ray diffraction study of [AsBr4][AsF(OTeFs)5]: P1, a = 9.778(4) A, b = 17.731(7) A, c = 18.870(8) A, alpha = 103.53(4)degrees, beta = 103.53(4) degrees, gamma = 105.10(4) degrees, V = 2915(2) A3, Z = 4, and R1 = 0.0368 at -183 degrees C. The crystal structure determination and solution 75As NMR study of the related [AsCl4][As(OTeF5)6] salt have also been carried out: [AsCl4][As(OTeF5)6], R3, a = 9.8741(14) A, c = 55.301(11) A, V= 4669(1) A3, Z = 6, and R1 = 0.0438 at -123 degrees C; and R3, a = 19.688(3) A, c = 55.264(11) A, V= 18552(5) A3, Z = 24, and R1 = 0.1341 at -183 degrees C. The crystal structure of the As(OTeF5)6- salt reveals weaker interactions between the anion and cation than in the previously known AsF6- salt. The AsF(OTeF5)5- anion is reported for the first time and is also weakly coordinating with respect to the AsBr4+ cation. Both cations are undistorted tetrahedra with bond lengths of 2.041(5)-2.056(3) A for AsCl4+ and 2.225(2)-2.236(2) A for AsBr4+. The Raman spectra are consistent with undistorted AsX4+ tetrahedra and have been assigned under Td point symmetry. The 35Cl/37Cl isotope shifts have been observed and assigned for AsCl4+, and the geometrical parameters and vibrational frequencies of all known and presently unknown PnX4+ (Pn = P, As, Sb, Bi; X = F, Cl, Br, I) cations have been calculated using density functional theory methods.

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“…It is well recognized that joint powder and single-crystal diffraction techniques constitute a very powerful tool to achieve a high level of accuracy in crystal structure determinations. [42][43][44][45][46][47][48] It is therefore desirable to apply such approach when the expected changes in the crystallographic structure are hardly detectable.…”

Section: A Rt Scd Experimentsmentioning

confidence: 99%

Crystal structure and structural phase transitions in the GdBaCo2O5.0cobaltite

et al. 2011

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We present an accurate investigation of the prototypical rare-earth cobaltite GdBaCo 2 O 5.0 by complementary synchrotron powder and conventional source single-crystal x-ray diffraction experiments. The correct space group (Pmmm) and the accurate crystallographic structure of this compound at room temperature (RT) have been determined. By increasing T a second-order structural-phase transition to a tetragonal structure with space group P4/mmm at T ≈ 331 K is found. Close to the Néel temperature (T N ≈ 350 K), anomalies appear in the trend of the lattice constants, suggesting that the structural phase transition is incipient at T N . A possible mechanism for this complex behavior is suggested.

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Single-crystal and high-resolution X-ray diffraction studies and Raman spectrum of a phosphorus(V) chloride complex containing a single bromide ion, P3Cl14Br

Cited by 6 publications

References 12 publications

Tetrachloro- and Tetrabromoarsonium(V) Cations: Raman and ⁷⁵As, ¹⁹F NMR Spectroscopic Characterization and X-ray Crystal Structures of [AsCl₄][As(OTeF₅)₆] and [AsBr₄][AsF(OTeF₅)₅]

Crystal structure and structural phase transitions in the GdBaCo2O5.0cobaltite

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Single-crystal and high-resolution X-ray diffraction studies and Raman spectrum of a phosphorus(V) chloride complex containing a single bromide ion, P3Cl14Br

Cited by 6 publications

References 12 publications

Tetrachloro- and Tetrabromoarsonium(V) Cations: Raman and 75As, 19F NMR Spectroscopic Characterization and X-ray Crystal Structures of [AsCl4][As(OTeF5)6] and [AsBr4][AsF(OTeF5)5]

Crystal structure and structural phase transitions in the GdBaCo2O5.0cobaltite

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Tetrachloro- and Tetrabromoarsonium(V) Cations: Raman and ⁷⁵As, ¹⁹F NMR Spectroscopic Characterization and X-ray Crystal Structures of [AsCl₄][As(OTeF₅)₆] and [AsBr₄][AsF(OTeF₅)₅]