Transformation of Ammonium Dicyanamide into Dicyandiamide in the Solid

Ammonium dicyanamide NH4[N(CN)2] was synthesized through aqueous ion exchange. The crystal structure was investigated by single-crystal X-ray diffraction (P21/c, a = 378.67(6) pm, b = 1240.9(3) pm, c = 911.84(14) pm, β = 91.488(18)°, Z = 4). It derives from the CsCl structure type. Medium strong hydrogen bonds between NH4+ and [N(CN)2]- ions are indicative of the observed formation of dicyandiamide H4C2N4 during heating. According to DSC and temperature-dependent X-ray powder diffractometry, this isomerization is exothermic and occurs between 102 and 106°C in the solid. The reaction represents the isolobal analogue to the classical synthesis of urea by heating NH4OCN. While other alkali and alkaline earth dicyanamides undergo trimerization or polymerization of their anions during heating, ammonium dicyanamide thus shows a different reactivity

Trimerization of NaC2N3 to Na3C6N9 in the Solid

Sodium dicyanamide NaC2N3 was found to undergo two phase transitions. According to thermal analysis and temperature-dependent X-ray powder diffractometry, the transition of α-NaC2N3 (1a) to β-NaC2N3 (1b) occurs at 33°C and is displacive. 1a crystallizes in the monoclinic system, space group P21/n (no. 14), with a = 647.7(1), b = 1494.8(3), c = 357.25(7) pm, β = 93.496(1)°, and Z = 4. The structure was solved from powder diffraction data (Cu Kα1, T = 22°C) using direct methods and it was refined by the Rietveld method. The final agreement factors were wRp = 0.072, Rp = 0.053, and RF = 0.074. 1b crystallizes in the orthorhombic system, space group Pbnm (no. 62), with a = 650.15(5), b = 1495.1(2), c = 360.50(3) pm, and Z = 4. The structure was refined by the Rietveld method using the atomic coordinates of 1a as starting values (Mo Kα1, T = 150°C). The final agreement factors were wRp = 0.044, Rp = 0.034, RF = 0.140. The crystal structures of both polymorphs contain sheets of Na+ and N(CN)2- ions which are in 1a nearly and in 1b exactly coplanar. Above 340°C, 1b trimerizes in the solid to Na3C6N9 (2). 2 crystallizes in the monoclinic system, space group P21/n (no. 14), with a = 1104.82(1), b = 2338.06(3), c = 351.616(3) pm, β = 97.9132(9)°, and Z = 4. The structure was solved from synchrotron powder diffraction data (λ = 59.733 pm) using direct methods and it was refined by the Rietveld method. The final agreement factors were wRp = 0.080, Rp = 0.059, and RF = 0.080. The compound contains Na+ and the planar tricyanomelaminate C6N93-. The phase transition from 1b to 2 is reconstructive. It occurs in the solid-state without involvement of other phases or intermediates. The crystal structures of 1b and 2 indicate that there is no preorientation of the N(CN)2- in the solid before their trimerization to C6N93-

Synthesis and Crystal Structure of the New Telluric Acid Adduct (RbCl)3·Te(OH)6

The new telluric acid adduct (RbCl)3 ・ Te(OH)6 was prepared by dissolving RbCl and Te(OH)6 in the molar ratio of 3 : 1 in deionized water at r. t. and slow evaporation of the solvent in air. The crystal structure of the colorless crystals was determined with single-crystal X-ray diffraction (trigonal space group: R3̄c (no. 167), a = 14.4392(8), c = 10.4301(16) Å , Z = 6). In (RbCl)3 ・ Te(OH)6, the rubidium atom is surrounded by five chlorine and four oxygen atoms in form of an irregular tricapped trigonal prism. Each tellurium atom is octahedrally surrounded by six oxygen atoms. The Te(OH)6 octahedra and the RbCl5O4 polyhedra are linked to a dense three-dimensional network which is additionally strengthened by hydrogen bonds

High-temperature synthesis, single-crystal X-ray and neutron powder diffraction, and materials properties of Sr3Ln10Si18Al12O18N36 (Ln = Ce, Pr, Nd)

The novel oxonitridoaluminosilicates (sialons) Sr3Ln10Si18Al12O18N36 (Ln = Ce, Pr, Nd) were obtained by the reaction of the respective lanthanide metals with Si(NH)2, SrCO3, and AlN using a radiofrequency furnace at temperatures between 1550–1650°C. The crystal structures of the isotypic sialons were determined by single-crystal X-ray investigations (Sr3Ce10Si18Al12O18N36: I3m, Z = 2, a = 1338.2(2) pm, R1 = 0.0333; Sr3Pr10Si18Al12O18N36: a = 1334.54(6) pm, R1 = 0.0296; Sr3Nd10Si18Al12O18N36: a = 1332.85(6) pm, R1 = 0.0271) and in the case of Sr3Pr10Si18Al12O18N36 with powder neutron diffraction as well. The three-dimensional sialon network is built up by SiON3, SiN4, and AlON3 tetrahedra. Besides the bridging O and N atoms of the sialon network there are isolated O2− which are tetrahedrally coordinated by Sr and Ln. The crystallographic differentiation of Si/Al and O/N seemed to be possible by a careful evaluation of the single-crystal X-ray diffraction data combined with lattice energy calculations using the MAPLE concept (Madelung Part of Lattice Energy). In the case of Sr3Pr10Si18Al12O18N36 the differentiation of O and N and the proposed ordering was completely confirmed by powder neutron diffraction

Melem (2,5,8-Triamino-tri-s-triazine), an Important Intermediate during Condensation of Melamine Rings to Graphitic Carbon Nitride: Synthesis, Structure Determination by X-ray Powder Diffractometry, Solid-State NMR, and Theoretical Studies

Single-phase melem (2,5,8-triamino-tri-s-triazine) C6N7(NH2)3 was obtained as a crystalline powder by thermal treatment of different less condensed C−N−H compounds (e.g., melamine C3N3(NH2)3, dicyandiamide H4C2N4, ammonium dicyanamide NH4[N(CN)2], or cyanamide H2CN2, respectively) at temperatures up to 450°C in sealed glass ampules. The crystal structure was determined ab initio by X-ray powder diffractometry (Cu Kα1:  P21/c (No. 14), a = 739.92(1) pm, b = 865.28(3) pm, c = 1338.16(4) pm, β = 99.912(2)°, and Z = 4). In the solid, melem consists of nearly planar C6N7(NH2)3 molecules which are arranged into parallel layers with an interplanar distance of 327 pm. Detailed 13C and 15N MAS NMR investigations were performed. The presence of the triamino form instead of other possible tautomers was confirmed by a CPPI (cross-polarization combined with polarization inversion) experiment. Furthermore, the compound was characterized using mass spectrometry, vibrational (IR, Raman), and photoluminescence spectroscopy. The structural and vibrational properties of molecular melem were theoretically studied on both the B3LYP and the MP2 level. A structural optimization in the extended state was performed employing density functional methods utilizing LDA and GGA. A good agreement was found between the observed and calculated structural parameters and also for the vibrational frequencies of melem. According to temperature-dependent X-ray powder diffractometry investigations above 560°C, melem transforms into a graphite-like C−N material

A Theoretical and Experimental Study on the Lewis Acid−Base Adducts (P4E3)·(BX3) (E = S, Se; X = Br, I) and (P4Se3)·(NbCl5)

The Lewis acid−base adducts (P4E3)·(BX3) (E = S, Se; X = Br, I) and (P4Se3)·(NbCl5) have been prepared and characterized by Raman, IR, and solid-state 31P MAS NMR spectroscopy. Hybrid density functional calculations (B3LYP) have been carried out for both the apical and the basal (P4E3)·(BX3) (E = S, Se; X = Br, I) adducts. The thermodynamics of all considered species has been discussed. In accordance with solid-state 31P MAS NMR and vibrational data, the X-ray powder diffraction structures of (P4S3)·(BBr3) [monoclinic, space group P21/m (No. 11), a = 8.8854(1) Å, b = 10.6164(2) Å, c = 6.3682(1) Å, β = 108.912(1)°, V = 568.29(2) Å3, Z = 2] and (P4S3)·(BI3) [orthorhombic, space group Pnma (No. 62), a = 12.5039(5) Å, b = 11.3388(5) Å, c = 8.9298(4) Å, V = 1266.09(9) Å3, Z = 4] indicate the formation of an apical P4S3 complex in the reaction of P4S3 with BX3 (X = Br, I). Basal adducts are formed when P4Se3 is used as the donor species. Vibrational assignment for the normal modes of these adducts has been made on the basis of comparison between theoretically obtained and experimentally observed vibrational data

Synthesis, characterization and reactivity of an imidazolin-2-iminato aluminium dihydride

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.The reaction of bis(2,6-diisopropylphenyl)imidazolin-2-imine (LH, 1) with Me3N·AlH3furnishes {μ-LAlH2}2(2). The marked tendency of2to release its hydride substituents is ascribed to the strong electron-donor character of the imidazolin-2-iminato ligand. This is supported by its reactivity study and DFT calculations. In fact, compound2was further converted with Me3SiOTf, Me2S·BH3, Me2S·BBr3, and BX3(with X = Cl, Br, and I) into {μ-LAl(H)OTf}2(3), {μ-LAl(BH4)2}2(4), and {μ-LAlX2}2(5, X = Br;6, X = Cl;7, X = I), respectively. For all new aluminium complexes the formulation as dimers was evidenced by high resolution mass spectrometry, as well as single-crystal X-ray diffraction analysis. A prominent structural motif of these compounds is the square-planar four-membered Al2N2ring with two bridging bulky imidazolin-2-imino moieties

Kristallstrukturuntersuchungen von Hauptgruppen-Nitriden mittels Pulverbeugung

In this thesis new nitrides and imides were investigated by powder diffraction methods. The crystal structures of a series of nitridophosphates and nitridocarbonates which were available only as powder were solved by direct methods after indexing and extraction of the integrated intensities. By neutron powder diffraction on the one hand hydrogen was localized in an imide, on the other hand the elements nitrogen and oxygen, which are difficult to distinguish by X-ray diffraction, were discerned in oxonitridophosphates and oxonitridosilicates. Thus the importance of the powder diffraction for nitrides could be proved.In der vorliegenden Arbeit wurden neue Nitride und Imide mit Pulverbeugungsmethoden untersucht. Die Kristallstrukturen einer Reihe von Nitridophosphaten und Nitridocarbonaten, die nur als Pulver vorlagen, wurden nach der Indizierung und dem Extrahieren der integrierten Intensitäten mit Direkten Methoden bestimmt. Mit Neutronenbeugung an Pulvern wurde einerseits Wasserstoff in einem Imid lokalisiert, andererseits die mit Röntgenbeugung schwer zu unterscheidenden Elemente N und O in Oxonitrophosphaten und Oxonitridosilicaten unterschieden. Damit konnte die Bedeutung der Pulverbeugung im Bereich der Nitride gezeigt werden

Catalytic difunctionalization of unactivated alkenes with unreactive hexamethyldisilane through regeneration of silylium ions

A metal‐free, intermolecular syn‐addition of hexamethyldisilane across simple alkenes is reported. The catalytic cycle is initiated and propagated by the transfer of a methyl group from the disilane to a silylium‐ion‐like intermediate, corresponding to the (re)generation of the silylium‐ion catalyst. The key feature of the reaction sequence is the cleavage of the Si−Si bond in a 1,3‐silyl shift from silicon to carbon. A central intermediate of the catalysis was structurally characterized by X‐ray diffraction, and the computed reaction mechanism is fully consistent with the experimental findings.TU Berlin, Open-Access-Mittel - 201

Tetrapodal amidoxime ligands I. Coordination isomerism due to self-complementary dimerization of a pyramidal cobalt(III) coordination module

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.A bis-μ-amidoximato-bridged cobalt(III) dimer obtained with a new tetrapodal ligand possesses interesting structural parameters as a consequence of intramolecular hydrogen bonding intentionally built into the complex. Its synthesis and properties are described. The new ligand type combines attributes of two previously described ligand classes: It binds a metal ion in a tetrapodal pentadentate fashion and forms a pseudomacrocycle through hydrogen bonds, characteristic of chelating oxime ligands. Coordination isomerism, which is a consequence of dimer formation, has been analyzed by means of X-ray crystallography and carbon-13 nuclear magnetic resonance spectroscopy