High-pressure and environment effects in selenourea and its labile crystal field around molecules

Roszak, Kinga; Katrusiak, Andrzej

doi:10.1107/s205252062100398x

Cited by 5 publications

(6 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Two crystal structures determined at 100 K (Luo & Dauter, 2017) and 173 K (Rutherford & Calvo, 1969) are both consistent with phase (i.e. space group P3 1 , Z 0 = 9) (Roszak & Katrusiak, 2021;Rutherford & Calvo, 1969). Our differential scanning calorimetry (DSC) measurements revealed a first-order phase transition at 381.0 K and a new solid selenourea phase stable below the melting point at 473 K (Fig.…”

Section: Introductionsupporting

confidence: 68%

“…The 100 K/0.1 MPa points were determined by Luo & Dauter (2017). The molecular volume of phase (the open circle) is also indicated for its lowest limit of pressure range at 0.21 GPa (Roszak & Katrusiak, 2021). Where not indicated, the estimated standard deviations are smaller than the plotted symbols.…”

Section: Figurementioning

confidence: 99%

“…Selenourea is an important metabolite and chemical agent (Hariharan & Dharmaraj, 2020;Koketsu & Ishihara, 2006;Zheng et al, 2002). Its polymorph , which is stable under normal conditions, is unique due to the complex structure comprising nine independent molecules (Z 0 = 9) in the asymmetric unit (Roszak & Katrusiak, 2021;Luo & Dauter, 2017;Rutherford & Calvo, 1969). The recently revealed polymorph , stable above 0.21 GPa, contains two independent molecules (Z 0 = 2).…”

Section: Introductionmentioning

confidence: 99%

“…The recently revealed polymorph , stable above 0.21 GPa, contains two independent molecules (Z 0 = 2). The recrystallization under high pressure also induces a partial stochastic hydration in phase ; the recrystallization from the aqueous solution above 0.21 GPa favors the formation of duotritohydrate 3SeC(NH 2 ) 2 Á2H 2 O, unknown under normal conditions (Roszak & Katrusiak, 2021). Meanwhile, relatively little is known about the thermal behavior of SeC(NH 2 ) 2 .…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Competition of interactions and a new high-temperature phase of selenourea

Roszak

Katrusiak

2023

Acta Crystallogr Sect B

Self Cite

View full text Add to dashboard Cite

The aggregation of molecules is usually associated with a specific type of interaction, which can be altered by thermodynamic conditions. Under normal conditions, the crystal structure of selenourea, SeC(NH2)2, phase α is trigonal, space group P31, Z = 27. Its large number of independent molecules (Z α′ = 9) can be associated with the formation of an NH...N hydrogen bond substituting one of 36 independent NH...Se hydrogen bonds, which prevail among intermolecular interactions. Phase α approximates the trigonal structure with a threefold smaller unit cell (Z = 9), which in turn approximates another still threefold smaller unit cell (Z = 3). The temperature-induced transformations of selenourea have been characterized by calorimetry and by performing 21 single-crystal X-ray diffraction structural determinations as a function of temperature. At 381.0 K, phase α undergoes a first-order displacive transition to phase γ, with space group P3121 and Z reduced to 9, when the NH...N bond is broken and an NH...Se bond is formed in its place. Previously, an analogous competition was observed between NH...N and NH...O hydrogen bonds in high-pressure phase III of urea. The lattice vectors along the (001) plane in low- and high-temperature phases of selenourea are related by a similarity rule, while the lattice dimensions along direction c are not affected. This similarity rule also applies to the structures of phase γ and hypothetical phase δ (Z = 3). The thermally controlled transition between enantiomorphic phases of selenourea contrasts with its high-pressure transition at 0.21 GPa to a centrosymmetric phase β, where both the NH...Se and NH...N bonds are present. The compression and heating reduce the number of independent molecules from Z′ = 9 in phase α, to Z′ = 2 in phase β and to Z′ = 1.5 in phase γ.

show abstract

Section: Introductionsupporting

confidence: 68%

Section: Figurementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Competition of interactions and a new high-temperature phase of selenourea

Roszak

Katrusiak

2023

Acta Crystallogr Sect B

Self Cite

View full text Add to dashboard Cite

show abstract

“…Moreover, the recrystallizations of the pure molten dlmenthol yielded polymorph below 0.40 GPa and polymorph above 0.40 GPa. Because no other compounds except dl- menthol were present in the DAC chamber, this series of experiments showed that no solvent effects, such as stochastic sorption, take place (Roszak & Katrusiak, 2021;Olejniczak et al, 2022a).…”

Section: Resultsmentioning

confidence: 85%

Low-density preference of the ambient and high-pressure polymorphs of DL-menthol

Roszak¹,

Katrusiak²

2023

Int Union Crystallogr J

Self Cite

View full text Add to dashboard Cite

Lower-density polymorphs of DL-menthol were nucleated and crystallized in their high-pressure stability regions. Up to 0.30 GPa, the triclinic DL-menthol polymorph α, which is stable at atmospheric pressure, is less dense than a new β polymorph, which becomes stable above 0.40 GPa, but is less dense than the α polymorph at this pressure. The compression of polymorph α to at least 3.37 GPa is monotonic, with no signs of phase transitions. However, recrystallizations of DL-menthol above 0.40 GPa yield the β polymorph, which is less compressible and becomes less dense than α-DL-menthol. At 0.10 MPa, the melting point of the β polymorph is 14°C, much lower compared with those of α-DL-menthol (42–43°C) and L-menthol (36–38°C). The structures of both DL-menthol polymorphs α and β are very similar with respect to the lattice dimensions, the aggregation of OH...O molecules bonded into C i symmetric chains, the presence of three symmetry-independent molecules (Z′ = 3), their sequence ABCC′B′A′, the disorder of the hydroxyl protons and the parallel arrangement of the chains. However, the different symmetries relating the chains constitute a high kinetic barrier for the solid–solid transition between polymorphs α and β, hence their crystallizations below or above 0.40 GPa, respectively, are required. In the structure of polymorph α, the directional OH...O bonds are shorter and the voids are larger compared with those in polymorph β, which leads to the reverse density relation of the polymorphs in their stability regions. This low-density preference reduces the Gibbs free-energy difference between the polymorphs: when polymorph α is compressed to above 0.40 GPa, the work component pΔV counteracts the transition to the less dense polymorph β, and on reducing the pressure of polymorph β to below 0.40 GPa, its transition to the less dense polymorph α is also hampered by the work contribution.

show abstract

Impact of environmental effect on industrial structure of resource-based cities in western China

Qiu

Zhang

2022

Environ Sci Pollut Res

View full text Add to dashboard Cite

High-pressure and environment effects in selenourea and its labile crystal field around molecules

Cited by 5 publications

References 36 publications

Competition of interactions and a new high-temperature phase of selenourea

Competition of interactions and a new high-temperature phase of selenourea

Low-density preference of the ambient and high-pressure polymorphs of DL-menthol

Impact of environmental effect on industrial structure of resource-based cities in western China

Contact Info

Product

Resources

About