Structure And Polymorphism In M(ethylenediamine)3MoS4 (M = Mn, Co, Ni)

Title:
Structure And Polymorphism In M(ethylenediamine)3MoS4 (M = Mn, Co, Ni)
Authors:
Tian, Hengfeng; Iliff, Hadley A.; Moore, Lee J.; Oertel, Catherine M.
Abstract:
Polymorphism in hybrid inorganic-organic materials has not been explored as extensively as that in organic compounds, yet differences in solid-state structure can significantly affect the physical properties central to application of these materials. A new polymorph of Ni(en)(3)MoS4 (en = ethylenediamine), a hydrodesulfurization catalyst precursor, has been synthesized solvothermally and structurally characterized by single-crystal X-ray diffraction. The new structure (2) assumes the orthorhombic Pcab space group with a = 14.020(5) angstrom, b = 14.821(7) angstrom, and c = 16.230(6) angstrom. The structure of a polymorph that had been found previously (1) was redetermined at 100 K, confirming the orthorhombic Pna2(1) structure with a=15.916(13) angstrom, b = 7.610(3) angstrom, and c = 14.093(6) angstrom. Solvothermal reaction conditions including temperature, solvent water content, and nickel source were important in controlling polymorph formation. Differential scanning calorimetry and solvent-mediated conversion studies were used to compare the stabilities of the two nickel-containing polymorphs. The system was characterized as enantiotropic, with 2 favored at ambient temperature and I favored at 120 degrees C. However, kinetic factors are influential in the intermediate temperature range, and conversion is kinetically hindered under certain conditions. The new structures Co-(en)(3)MoS4 (3) and Mn(en)(3)MoS4 (4) were determined through single-crystal methods to be isostructural to 2. Compounds 1-4 were also characterized by elemental analysis, infrared spectroscopy, variable-temperature magnetic susceptibility measurements, and thermogravimetric analysis.
Citation:
Tian, Hengfeng, Hadley A. Iliff, Lee J. Moore, and Catherine M. Oertel. 2010. "Structure And Polymorphism In M(ethylenediamine)3MoS4 (M = Mn, Co, Ni)." Crystal Growth & Design 10(2): 669-675.
Publisher:
American Chemical Society
DATE ISSUED:
2010-02
Department:
Chemistry
Type:
article
PUBLISHED VERSION:
10.1021/cg901087x
PERMANENT LINK:
http://hdl.handle.net/11282/309976

Full metadata record

DC FieldValue Language
dc.contributor.authorTian, Hengfengen_US
dc.contributor.authorIliff, Hadley A.en_US
dc.contributor.authorMoore, Lee J.en_US
dc.contributor.authorOertel, Catherine M.en_US
dc.date.accessioned2013-12-23T16:22:25Zen
dc.date.available2013-12-23T16:22:25Zen
dc.date.issued2010-02en
dc.identifier.citationTian, Hengfeng, Hadley A. Iliff, Lee J. Moore, and Catherine M. Oertel. 2010. "Structure And Polymorphism In M(ethylenediamine)3MoS4 (M = Mn, Co, Ni)." Crystal Growth & Design 10(2): 669-675.en_US
dc.identifier.issn1528-7483en_US
dc.identifier.urihttp://hdl.handle.net/11282/309976en
dc.description.abstractPolymorphism in hybrid inorganic-organic materials has not been explored as extensively as that in organic compounds, yet differences in solid-state structure can significantly affect the physical properties central to application of these materials. A new polymorph of Ni(en)(3)MoS4 (en = ethylenediamine), a hydrodesulfurization catalyst precursor, has been synthesized solvothermally and structurally characterized by single-crystal X-ray diffraction. The new structure (2) assumes the orthorhombic Pcab space group with a = 14.020(5) angstrom, b = 14.821(7) angstrom, and c = 16.230(6) angstrom. The structure of a polymorph that had been found previously (1) was redetermined at 100 K, confirming the orthorhombic Pna2(1) structure with a=15.916(13) angstrom, b = 7.610(3) angstrom, and c = 14.093(6) angstrom. Solvothermal reaction conditions including temperature, solvent water content, and nickel source were important in controlling polymorph formation. Differential scanning calorimetry and solvent-mediated conversion studies were used to compare the stabilities of the two nickel-containing polymorphs. The system was characterized as enantiotropic, with 2 favored at ambient temperature and I favored at 120 degrees C. However, kinetic factors are influential in the intermediate temperature range, and conversion is kinetically hindered under certain conditions. The new structures Co-(en)(3)MoS4 (3) and Mn(en)(3)MoS4 (4) were determined through single-crystal methods to be isostructural to 2. Compounds 1-4 were also characterized by elemental analysis, infrared spectroscopy, variable-temperature magnetic susceptibility measurements, and thermogravimetric analysis.en_US
dc.language.isoen_USen_US
dc.publisherAmerican Chemical Societyen_US
dc.identifier.doi10.1021/cg901087xen
dc.subject.departmentChemistryen_US
dc.titleStructure And Polymorphism In M(ethylenediamine)3MoS4 (M = Mn, Co, Ni)en_US
dc.typearticleen_US
dc.identifier.journalCrystal Growth & Designen_US
dc.subject.keywordRay-structure characterizationen_US
dc.subject.keywordNonlinear-optical propertiesen_US
dc.subject.keywordMetal-organic frameworken_US
dc.subject.keywordCrystal structureen_US
dc.subject.keywordSulfide catalystsen_US
dc.subject.keywordHydrogen uptakeen_US
dc.subject.keywordTetrathiomolybdatesen_US
dc.subject.keywordComplexesen_US
dc.subject.keywordClusteren_US
dc.subject.keywordMolybdenumen_US
dc.subject.keywordChemistry, multidisciplinaryen_US
dc.subject.keywordCrystallographyen_US
dc.subject.keywordMaterials science, multidisciplinaryen_US
dc.identifier.volume10en_US
dc.identifier.issue2en_US
dc.identifier.startpage669en_US
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