Phase transitions in N(CH3)4HSO4: a novel compound with an incommensurate phase

Speziali, N. L.; Chapuis, G.

doi:10.1107/s0108768191003646

Cited by 14 publications

(5 citation statements)

References 5 publications

(7 reference statements)

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“…at room temperature the hydrogen sulfate anion is disordered by rotation around the S1-O1 bond over two positions (70:30 ratio), at low temperature an ordered structure is obtained. Phase transitions are a well known phenomenon for [HSO 4 ] − salts [28,29]. A similar disorder of the hydrogen sulfate anion is also observed in the structure containing additional acetonitrile solvate molecules even at T = 150 K. In contrast, the [PNP] + cations are well ordered and adopt typical conformations [10].…”

Section: Crystal Structuresmentioning

confidence: 60%

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻

Jenne

Nierstenhöfer

2019

Zeitschrift Für Naturforschung B

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Metathesis reactions of [PNP]Cl ([PNP]+ ≡ bis(triphenyl-λ5-phosphanylidene)ammonium) with Na2[SO4] or K[HSO4] in water yield [PNP]2[SO4] and [PNP][HSO4], respectively, as colorless solids. Reactions under basic conditions lead to a partial decomposition of the weakly coordinating [PNP]+ cation. N-Diphenylphosphine-triphenylphosphazene, triphenylphosphinimine, and benzene were identified as decomposition products by NMR spectroscopy. The compounds [PNP]2[SO4] and [PNP][HSO4] were characterized by multinuclear NMR and vibrational spectroscopy. [PNP][HSO4] could be crystallized from acetonitrile-diethyl ether giving single crystals with and without additional acetonitrile solvate molecules. The [HSO4]− anions form dimers in the solid state in both structures, which are held together by O–H⋯O hydrogen bonds. At T = 127 K the [HSO4]− anions in the crystal structure of solvate free [PNP][HSO4] are ordered, while at T = 300 K and in the structure containing additional acetonitrile solvate molecules a disorder of the [HSO4]− anions over two positions is observed, for the latter even at 150 K.

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Section: Crystal Structuresmentioning

confidence: 60%

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻

Jenne

Nierstenhöfer

2019

Zeitschrift Für Naturforschung B

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“…Although TMPHS is not isostructural with its ammonium analogue, (CH 3 ) 4 NHSO 4 , both high- and low-temperature polymorphs of the latter reveal similar structural features, particularly ion coordination and association of the HSO − anions into a zigzag chain. 46…”

Section: Resultsmentioning

confidence: 99%

“…44 The geometry of hydrogen bonds found in TMPHS, TEPHS and TBPHS, with (S-O⋯H) min = 1.63(3)-1.79(6) Å, (O⋯O) = 2.572(2)-2.65(6) Å, and O-H⋯O = 163(4)-176(3)°indicates the rather moderate strength of these interactions, 40 similar to those in tetraalkylammonium hydrogen sulfates or hydrogen selenates. [45][46][47] On the other hand, the hydrogen bonds present in TEPS monohydrate are somewhat weaker, Fig. 2(c), with (O⋯O) min = 2.781(4) Å, resembling the distance between oxygen atoms in hexagonal ice (ca.…”

Section: Crystal Structures Of the Tetraalkylphosphonium Sulfates And...mentioning

confidence: 99%

“…Although TMPHS is not isostructural with its ammonium analogue, (CH 3 ) 4 -NHSO 4 , both high-and low-temperature polymorphs of the latter reveal similar structural features, particularly ion coordination and association of the HSO − anions into a zigzag chain. 46 Note that the terms "isostructural" and "isomorphous" used in the literature reveal some ambiguity. The first one denotes the systems sharing the same structure (atomic coordination and connectivity), with some degree of variability of the numerical parameters (fractional coordinates of the atoms and a Structures solved from powder data.…”

Section: Crystal Structures Of the Tetraalkylphosphonium Sulfates And...mentioning

confidence: 99%

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Synthesis and structural trends in a series of simple tetraalkylphosphonium salts

Gawraczyński,

Leszczyński,

Cyrański

et al. 2024

CrystEngComm

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“…Secondly, we wished to characterize plausible phase transitions in (I). For example, in tetramethylammonium hydrogensulfate, [N(CH 3 ) 4 ]HSO 4 (Speziali & Chapuis, 1991), three phase transitions were detected. In some cases, phase transitions at elevated temperatures can lead to superprotonic phases in related compounds.…”

Section: Commentmentioning

confidence: 99%

Bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate at 292 and 150 K

Fábry

Krupková

Císařová³

et al. 2003

Acta Crystallogr C

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The title compound, 2C(8)H(20)N(+) x HSO(4)(-) x H(2)PO(4)(-), was crystallized in a desiccator over P(4)O(10) from a water solution of stoichiometric amounts of tetraethylammonium hydroxide and sulfuric and phosphoric acids. The compound is deliquescent. The structure contains two symmetry-independent cations in nearly the same conformation, as well as two symmetry-independent anions, the central atoms of which are equally occupied by P and S. The anions are interconnected by short O...O hydrogen bonds into one-dimensional chains. The distances and angles between some of the methyl or methylene groups and anionic O atoms indicate the presence of C-H...O hydrogen bonds. The structure was determined from data at 292 (2) and 150 (2) K. These room- and low-temperature structures are virtually the same, with the exception of the localization of the H atoms that participate in the symmetry-restricted O...O hydrogen bonds. A differential scanning calorimetry experiment indicated no phase transition below the temperature at which the compound started to decompose (353 K), down to 93 K.

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Phase transitions in N(CH₃)₄HSO₄: a novel compound with an incommensurate phase

Cited by 14 publications

References 5 publications

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻

Synthesis and structural trends in a series of simple tetraalkylphosphonium salts

Bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate at 292 and 150 K

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Phase transitions in N(CH3)4HSO4: a novel compound with an incommensurate phase

Cited by 14 publications

References 5 publications

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]+[HSO4]−

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]+[HSO4]−

Synthesis and structural trends in a series of simple tetraalkylphosphonium salts

Bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate at 292 and 150 K

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Phase transitions in N(CH₃)₄HSO₄: a novel compound with an incommensurate phase

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻

Temperature- and solvate-dependent disorder in the crystal structure of [PNP]⁺[HSO₄]⁻