RbCN3H4 and CsCN3H4: A Neutron Powder and Single‐­Crystal X‐ray Diffraction Study

Hoepfner, Veronika; Jacobs, Philipp; Sawinski, Peter Klaus; Houben, Andreas; Reim, Johannes; Dronskowski, Richard

doi:10.1002/zaac.201300164

Cited by 17 publications

(17 citation statements)

References 9 publications

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“…In the gas phase, the most stable conformation was calculated as the syn-conformation [35], adopted in the solid state in KCN3H4, RbCN3H4, and CsCN3H4 [27,28,41]. The energetically less favorable anti-conformation is adopted in LiCN3H4 and NaCN3H4, owing presumably to improved packing and hydrogen-bonding [28,29].…”

Section: Refinement and Crystalmentioning

confidence: 99%

“…To obtain a sensible structural model, the U iso of the C and N atoms of each guanidinate unit were constrained. Also, the C-N distances, N-C-N angles, and CN 3 torsion angles were restrained to established values for the guanidinate unit as obtained from neutron-diffraction measurements [31,41]. Finally, a secondary phase of EuO [50] was added in the refinement, reaching a weight-percentage of 1.3(2) wt %.…”

Section: Powder X-ray Diffractionmentioning

confidence: 99%

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Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

et al. 2017

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Abstract:We report the first magnetically coupled guanidinate, α-Eu(CN 3 H 4 ) 2 (monoclinic, P2 1 , a = 5.8494(3) Å, b = 14.0007(8) Å, c = 8.4887(4) Å, β = 91.075(6) • , V = 695.07(6) Å 3 , Z = 4). Its synthesis, polymorphism, crystal structure, and properties are complemented and supported by density-functional theory (DFT) calculations. The α-, β-and γ-polymorphs of Eu(CN 3 H 4 ) 2 differ in powder XRD, while the γ-phase transforms into the β-form over time. In α-Eu(CN 3 H 4 ) 2 , Eu is octahedrally coordinated and sits in one-dimensional chains; the guanidinate anions show a hydrogen-bonding network. The different guanidinate anions are theoretically predicted to adopt syn-, anti-and all-trans-conformations. Magnetic measurements evidence ferromagnetic interactions, presumably along the Eu chains. Finally, EuC(NH) 3 (isostructural to SrC(NH) 3 and YbC(NH) 3 , hexagonal, P6 3 /m, a = 5.1634(7) Å, c = 7.1993(9) Å, V = 166.23(4) Å 3 , Z = 2) is introduced as a possible ferromagnet.

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Section: Refinement and Crystalmentioning

confidence: 99%

Section: Powder X-ray Diffractionmentioning

confidence: 99%

Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

et al. 2017

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“…The first successful characterization of rubidium guanidinate, RbCN 3 H 4 was achieved in 2011 through a solid‐state reaction using RbH and guanidine 16. All other alkali guanidinates were subsequently synthesized as single crystals in liquid ammonia 17–19. To do so, guanidine and the alkali metals were used as starting materials through in situ formation of alkali amides as strong bases.…”

Section: Introductionmentioning

confidence: 99%

The First Structurally Characterized Salts of Deprotonated Urea: M(CN₂H₃O) with M = Na, K, Rb, and Cs

Sawinski

Dronskowski

2014

Zeitschrift anorg allge chemie

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The ureates of the alkali metals Na – Cs were synthesized from urea and the metals in liquid ammonia at temperatures below 50 °C. The crystal structures were determined using single‐crystal X‐ray diffraction. NaCN2H3O crystallizes in the monoclinic system [P21/c, Z = 16, a = 17.529(1) Å, b = 6.4784(5) Å, c = 10.8211(9) Å, β = 96.938(1)°]. All other ureates are orthorhombic, with KCN2H3O and RbCN2H3O being isotypic [Pbca, Z = 8, KCN2H3O: a = 7.102(4) Å, b = 7.221(4) Å, c = 13.533(8) Å; RbCN2H3O: a = 7.1973(8) Å, b = 7.3531(8) Å, c = 13.921(2) Å]. CsCN2H3O adopts a smaller unit cell [P212121, Z = 4, a = 6.3520(3) Å, b = 7.1645(4) Å, c = 9.0911(5) Å]. The ureates of K, Rb, and Cs contain hydrogen‐bond networks, the imino nitrogen atom acting as the hydrogen‐bond acceptor in CsCN2H3O. In KCN2H3O and RbCN2H3O, however, the carbonyl oxygen atom accepts the hydrogen bonds.

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“…In many of these studies, the primary focus has not necessarily been on the determination of hydrogen parameters specifically, but on structures containing hydrogen, while the focus here is on hydrogen atom determination. However, amongst many examples of previous work that offer an indication of the wide scope of this, are studies of potassium hydrogen selenates [2], pure organic molecules [3], hydrated salts [4], clathrates [5], organometallic complexes [6] including joint neutron powder / single crystal X-ray studies [7], in situ studies [8] and hydrides for energy applications [9].…”

Section: Introductionmentioning

confidence: 99%

Neutron powder diffraction – new opportunities in hydrogen location in molecular and materials structure

Wilson¹,

Henry²,

Schmidtmann³

et al. 2014

Crystallography Reviews

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The potential of neutron powder diffraction in the location of hydrogen atoms in molecular materials and inorganic-molecular complexes is reviewed. Advances in instrumentation and data collection techniques that have made this field accessible are reviewed, along with a wide range of applications carried out by our collaboration investigating functional materials, hydrogen-containing minerals and molecular compounds. Some of the limitations in this area, particularly for molecular systems, are also addressed. IntroductionHydrogen is a key element whose functionality in inorganic material systems stretches from geochemical materials (e.g. clay minerals, cements), through key inorganic compounds (e.g. catalysts, co-ordination complexes and hydroxides/hydrates) and materials (e.g. polymers, hydrogen storage media, proton conductors/fuel cell components) to supramolecular and framework systems (e.g aluminosilicates, solvates and clathrates). The role of hydrogen in the structures (and hence derived applications) of these materials is thus of the utmost importance but one that, until recently, experimental methods generally failed to address, or could only do so in selected cases at great expense and considerable effort.Determination of the position of hydrogen in a material, whether it be a naturally occurring hydrate/hydroxide, a cement, a hydride/hydrogen storage material, a solvate or an organometallic compound has traditionally been difficult, time-consuming, expensive and imprecise, even where possible. However, knowledge of the distribution of hydrogen is central to understanding behaviours such as polymorphism, hydrogen bonding and three-dimensional structure definition, proton diffusion 2 pathways and levels of uptake in hydrogen storage materials, physical properties ranging from ferroelectricity to the elastic properties of polymers, and reaction mechanisms. Therefore the implementation and application of methodology that allows routine hydrogen position definition from readily available material (i.e. small easily synthesised quantities and in polycrystalline/small single crystal (≤50µm) form)is both of widespread application and key importance.In the work described here, development of the application of powder neutron diffraction methods in an optimised fashion to such materials is shown to have the capability to reveal structural information in a range of hydrogen-containing materials. A range of recent studies will be summarized, to illustrate the potential of this new capability. The powerful complementary use of both X-ray and computational methods with neutron powder diffraction in these studies will also be highlighted. The aim in this Review is not to provide a detailed account of the different materials studied, but to highlight the power of the methods of approach we have been systematically developing to access more accurate and different chemistry. It draws on a range of examples from our own collaborative work, which has recently focused on this theme [1].In this review, we have deli...

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RbCN₃H₄ and CsCN₃H₄: A Neutron Powder and Single‐Crystal X‐ray Diffraction Study

Cited by 17 publications

References 9 publications

Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

The First Structurally Characterized Salts of Deprotonated Urea: M(CN₂H₃O) with M = Na, K, Rb, and Cs

Neutron powder diffraction – new opportunities in hydrogen location in molecular and materials structure

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RbCN3H4 and CsCN3H4: A Neutron Powder and Single‐­Crystal X‐ray Diffraction Study

Cited by 17 publications

References 9 publications

Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

Synthesis, Crystal Structure, Polymorphism, and Magnetism of Eu(CN3H4)2 and First Evidence of EuC(NH)3

The First Structurally Characterized Salts of Deprotonated Urea: M(CN2H3O) with M = Na, K, Rb, and Cs

Neutron powder diffraction – new opportunities in hydrogen location in molecular and materials structure

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Product

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RbCN₃H₄ and CsCN₃H₄: A Neutron Powder and Single‐Crystal X‐ray Diffraction Study

The First Structurally Characterized Salts of Deprotonated Urea: M(CN₂H₃O) with M = Na, K, Rb, and Cs