Synthesis and Crystal Structure Determination of a Guanidine Adduct of Sodium Guanidinate, NaCN3H4(CN3H5)2

Hoepfner, Veronika; Englert, U.; Dronskowski, Richard

doi:10.5560/znb.2011.66b0975

Cited by 6 publications

(4 citation statements)

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“…Regarding such one-dimensional fragments, chains are an important structural motif when it comes to assembling complex molecular crystal structures. In the field of guanidine chemistry, one may think of the closely related and recently synthesized sodium guanidinate adduct NaCN 3 H 4 (CN 3 H 5 ) 2 39 which contains guanidine tubes wrapped around linear chains of sodium cations; of course, many other cases of chemical interest are pertinent.…”

Section: ■ Theory and Methodsmentioning

confidence: 99%

Hydrogen-Bonding Networks from First-Principles: Exploring the Guanidine Crystal

2012

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Hydrogen bonding is among the most important interactions in molecular crystals, and examples are abundant. As a consequence of such interactions, many molecules crystallize in complex but intriguing structures, in contrast to the relatively simple packing principles of metallic or ionic solids. In this work, we present a computational approach based on plane-wave density-functional theory (DFT) and supercell techniques, aiming to understand and quantify hydrogen-bonded networks in the solid state and in two-, one-, and zero-dimensional fragments derived from the molecular crystal. With such methodology at hand, we investigate guanidine, a fitting example of a molecular crystal and an important compound for inorganic and organic chemistry alike. On the basis of our computations, we discuss the initially proposed layered structure of guanidine and identify both stabilizing and destabilizing cooperative interactions in the three crystalline dimensions.

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Section: ■ Theory and Methodsmentioning

confidence: 99%

Hydrogen-Bonding Networks from First-Principles: Exploring the Guanidine Crystal

2012

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“…The C-N bond lengths reported here match the respective C-N distances found in NaCN 3 H 4 (CN 3 H 5 ) 2 , NaCN 3 H 4 and KCN 3 H 4 (d(C-N1) ≈ 1.40 Å and d(C-N2) ≈ 1.34 Å). [2,3] Hence, the bond lengths in the CN 3 H 4 -anion are almost independent from the cation, as expected for a complex anion. It is noteworthy, however, that the C-N1 bond in CsCN 3 H 4 (d(C-N1) = 1.37 Å) is found to be shorter than usual in this class of compounds, so this points towards an artefact which presumably goes back to absorption problems.…”

Section: Resultsmentioning

confidence: 62%

“…[1] Shortly after this study, three more representatives, namely NaCN 3 H 4 (CN 3 H 5 ) 2 , NaCN 3 H 4 , and KCN 3 H 4 , were synthesized and structurally characterized from single-crystal X-ray diffraction (SC-XRD). [2,3] The very first crystal structure of RbCN 3 H 4 was solved from powder X-ray diffraction (P-XRD) data collected at 10 K and revealed the positions of the Rb, C, and N atoms. Due to the limitations of the diffraction method, the positions of the hydrogen atoms could not be experimentally resolved but were derived from GGA-PBE density-functional theory calculations.…”

Section: Introductionmentioning

confidence: 99%

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

Hoepfner

Jacobs

Sawinski

et al. 2013

Zeitschrift anorg allge chemie

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Abstract. Rubidium guanidinate, RbCN 3 H 4 , is the first example of a new class of compounds containing the unsubstituted guanidinate anion CN 3 H 4 -. While the first crystal-structure determination was based on powder X-ray diffraction, neutron powder and single-crystal X-ray diffraction have now been utilized to improve the previous structural model, in particular with respect to experimentally localizing the hydrogen positions, which were so far derived from density-functional

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“…A straightforward approach to synthesizing guanidinates involves the deprotonation of guanidine, which can be performed by strong bases like alkali metal hydrides or amides (Table S1) [16–24] . This method allowed achieving the double‐deprotonated guanidinates with the chemical formula MC(NH) 3 (M=Ca, Ba, Sr, Eu, Yb) [17,20,24,25] .…”

Section: Experiments Reagents Pressure (Gpa)mentioning

confidence: 99%

Stabilization of Guanidinate Anions [CN₃]⁵⁻ in Calcite‐Type SbCN₃

Brüning,

Jena,

Bykova

et al. 2023

Angew Chem Int Ed

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The stabilization of nitrogen‐rich phases presents a significant chemical challenge due to the inherent stability of the dinitrogen molecule. This stabilization can be achieved by utilizing strong covalent bonds in complex anions with carbon, such as cyanide CN‐ and NCN2‐ carbodiimide, while more nitrogen‐rich carbonitrides are hitherto unknown. Following a rational chemical design approach, we synthesized antimony guanidinate SbCN3 at pressures of 32‐38 GPa using various synthetic routes in laser‐heated diamond anvil cells. SbCN3, which is isostructural to calcite CaCO3, can be recovered under ambient conditions. Its structure contains the previously elusive guanidinate anion [CN3]5‐, marking a fundamental milestone in nitridocarbonate chemistry. The crystal structure of SbCN3 was solved and refined from synchrotron single‐crystal X‐ray diffraction data and was fully corroborated by theoretical calculations, which also predict that SbCN3 has a direct band gap with the value 2.20 eV. This study opens a straightforward route to the entire new family of inorganic nitridocarbonates.

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Synthesis and Crystal Structure Determination of a Guanidine Adduct of Sodium Guanidinate, NaCN3H4(CN3H5)2

Cited by 6 publications

References 0 publications

Hydrogen-Bonding Networks from First-Principles: Exploring the Guanidine Crystal

Hydrogen-Bonding Networks from First-Principles: Exploring the Guanidine Crystal

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

Stabilization of Guanidinate Anions [CN₃]⁵⁻ in Calcite‐Type SbCN₃

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Synthesis and Crystal Structure Determination of a Guanidine Adduct of Sodium Guanidinate, NaCN3H4(CN3H5)2

Cited by 6 publications

References 0 publications

Hydrogen-Bonding Networks from First-Principles: Exploring the Guanidine Crystal

Hydrogen-Bonding Networks from First-Principles: Exploring the Guanidine Crystal

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

Stabilization of Guanidinate Anions [CN3]5− in Calcite‐Type SbCN3

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Product

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

Stabilization of Guanidinate Anions [CN₃]⁵⁻ in Calcite‐Type SbCN₃