Preparation, Crystal Structure, and Properties of Barium Pernitride, BaN<sub>2</sub>

Vajenine, Grigori V.; Auffermann, Gudrun; Prots, Yurii; Schnelle, Walter; Kremer, Reinhard K.; Simon, Arndt; Kniep, Rüdiger

doi:10.1021/ic010263+

Cited by 87 publications

(107 citation statements)

References 26 publications

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“…Magnetic susceptibility measurements and electronic structure calculations for BaN 2 already revealed that the compound exhibits Pauli paramagnetism and should be metallic, despite the paramagnetic triplet state of the diazenide ion. 11 Therefore, a test spin-polarized calculation with nonzero magnetic moments artificially placed on the nitrogen atoms of CaN 2 and SrN 2 was performed and converged also back to the metallic state. Both alkaline earth diazenides crystallize in the same structure type, which is isotypic with the corresponding alkaline earth acetylenides (M AE C 2 ), namely, in a tetragonally distorted NaCl-type.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Alkaline Earth Diazenides M_AEN₂(M_AE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

2012

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The alkaline earth diazenides M AE N 2 with M AE = Ca, Sr and Ba were synthesized by a novel synthetic approach, namely, a controlled decomposition of the corresponding azides in a multianvil press at highpressure/high-temperature conditions. The crystal structure of hitherto unknown calcium diazenide (space group I4/mmm (no. 139), a = 3.5747(6) Å, c = 5.9844(9) Å, Z = 2, wR p = 0.078) was solved and refined on the basis of powder X-ray diffraction data as well as that of SrN 2 and BaN 2 . Accordingly, CaN 2 is isotypic with SrN 2 (space group I4/mmm (no. 139), a = 3.8054(2) Å, c = 6.8961(4) Å, Z = 2, wR p = 0.057) and the corresponding alkaline earth acetylenides (M AE C 2 ) crystallizing in a tetragonally distorted NaCl structure type. In accordance with literature data, BaN 2 adopts a more distorted structure in space group C2/c (no. 15) with a = 7.1608(4) Å, b and their remarkable properties (e.g., superconductivity, photoluminescence, magnetism and low compressibility comparable to that of c-BN) 15−24 justify the investigation of the crystalline structure, stability, elasticity and electronic structures of the diazenides. However, except for M = Sr, Ba, Os, Ir, Pd and Pt, no other metal diazenides or pernitrides of formula type MN 2 have been synthesized in crystalline form as yet, but have been predicted by density-functional calculations to form under HP/HT conditions. 24−29 In order to extend the class of nitrogen rich metal diazenides or pernitrides, we have targeted new synthetic approaches for these compounds, and we were successful using controlled decomposition of highly reactive precursors like the corresponding azides. In this contribution, we present our novel synthesis route for the alkaline earth diazenides SrN 2 and BaN 2 . In addition, we report on the synthesis, structural, spectroscopic and electronic characterization of the novel alkaline earth diazenide CaN 2 and compare its structure to the predicted model. 26,29

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Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Alkaline Earth Diazenides M_AEN₂(M_AE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

2012

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“…In a1 922 contribution, Franklin mentioned [15] the doubly deprotonated guanidinate unit [C(NH) 3 ] 2À but without convincing evidence,i np articular without spectroscopic or structural proof.W eh ave finally succeeded in quantitatively synthesizing such an anion in the alkaline-earth metal guanidinate SrC(NH) 3 and determining its crystal structure. Thes tructure was approximately solved, despite the strong scattering power of Sr, from X-ray powder data, significantly improved by DFT calculations,and finally validated by means of highly resolved neutron diffraction ( Figure 1).…”

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Synthesis, Structure, and Properties of SrC(NH)₃, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif

et al. 2015

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Strontium guanidinate, SrC(NH)3 , the first compound with a doubly deprotonated guanidine unit, was synthesized from strontium and guanidine in liquid ammonia and characterized by X-ray and neutron diffraction, IR spectroscopy, and density-functional theory including harmonic phonon calculations. The compound crystallizes in the hexagonal space group P63 /m, constitutes the nitrogen analogue of strontium carbonate, SrCO3 , and its structure follows a layered motif between Sr(2+) ions and complex anions of the type C(NH)3 (2-) ; the anions adopt the peculiar trinacria shape. A comparison of theoretical phonons with experimental IR bands as well as quantum-chemical bonding analyses yield a first insight into bonding and packing of the formerly unknown anion in the crystal.

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“…) in Festkörpern [4] oder Metallkomplexen [5] oder auch der konjugierten Säure H 2 N 2 (Diazen, "Diimin") in Koordinationsverbindungen [6] wurden mit großem Interesse registriert. [7] Der nächste Schritt zum Drei-Elektronen-reduzierten N 2 C 3À (Dinitrid(3À)) wurde bislang nicht intensiv diskutiert, wohl wegen der hohen negativen Ladung zusätzlich zum Radikalcharakter.…”

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N₂^.3−: eine Lücke in der N₂ⁿ⁻‐Reihe gefüllt

Kaim

Sarkar

2009

Angewandte Chemie

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Preparation, Crystal Structure, and Properties of Barium Pernitride, BaN₂

Cited by 87 publications

References 26 publications

Synthesis of Alkaline Earth Diazenides M_AEN₂(M_AE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

Synthesis of Alkaline Earth Diazenides M_AEN₂(M_AE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

Synthesis, Structure, and Properties of SrC(NH)₃, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif

N₂^.3−: eine Lücke in der N₂ⁿ⁻‐Reihe gefüllt

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Preparation, Crystal Structure, and Properties of Barium Pernitride, BaN2

Cited by 87 publications

References 26 publications

Synthesis of Alkaline Earth Diazenides MAEN2(MAE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

Synthesis of Alkaline Earth Diazenides MAEN2(MAE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

Synthesis, Structure, and Properties of SrC(NH)3, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif

N2.3−: eine Lücke in der N2n−‐Reihe gefüllt

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Preparation, Crystal Structure, and Properties of Barium Pernitride, BaN₂

Synthesis of Alkaline Earth Diazenides M_AEN₂(M_AE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

Synthesis of Alkaline Earth Diazenides M_AEN₂(M_AE= Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure

Synthesis, Structure, and Properties of SrC(NH)₃, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif

N₂^.3−: eine Lücke in der N₂ⁿ⁻‐Reihe gefüllt