Treatment of the diethyl ester of o-phenylenebis(oxamic acid) (opbaH2Et2, 1) with 5/6 equivalent of MeNH2 in abs. EtOH results in the exclusive formation of the ethyl ester of o-phenylene(N′-methyl oxamide)(oxamic acid) (opooH3EtMe, 2) in ca. 50% yield. Treatment of 2 with four equivalents of [Me4N]OH followed by the addition of Cu(ClO4)2·6H2O gave [Me4N]2[Cu(opooMe)]·H2O (3A) in ca. 80% yield. As 3A appears to be a hygroscopic solid, the related [nBu4N]+ salts [nBu4N]2[M(opooMe)]·H2O (M = Cu (3B), Ni (4)) have been synthesized. By addition of two equivalents of [Cu(pmdta)(NO3)2] to a MeCN solution of 3B the novel asymmetric trinuclear complex [Cu3(opooMe)(pmdta)2](NO3)2 (5) could be obtained in ca. 90% yield. Compounds 2, 3A, 3B, 4 and 5 have been characterized by elemental analysis and NMR/IR spectroscopy. Furthermore, the solid state structures of 3A in the form of [Me4N]2[Cu(opooMe)]·MeOH (3A′), 3B in the form of [nBu4N]2[Cu(opooMe)] (3B′), 4 in the form of [nBu4N]2[Ni(opooMe)]·1.25H2O (4′) and 5 in the form of [Cu3(opooMe)(pmdta)2] (NO3)2·3MeCN (5′), respectively, have been determined by single-crystal X-ray diffraction studies. By controlled cocrystallization, diamagnetically diluted 3B (1%) in the host lattice of 4 (99%) in the form of single crystals have been made available, allowing single crystal EPR studies to extract all components of the g-factor and the tensors of onsite CuA and transferred NA hyperfine interaction. Out of these studies the spin density distribution of the [Cu(opooMe)]2− complex fragment could be determined. The magnetic properties of 5 were studied by susceptibility measurements versus temperature. An intramolecular J parameter of −65 cm−1 has been obtained, unexpectedly, as 5 should possess two different J values due to its two different spacers between the adjacent CuII ions, namely an oxamate (C2NO3) and an oxamidate (C2N2O2) fragment. This unexpected result is explained by a summarizing discussion of the experimentally obtained EPR results (spin density distribution) of 3B, the geometries of the terminal [Cu(pmdta)]2+ fragments of 5 determined by X-ray crystallographic studies and accompanying quantum chemical calculations of the spin density distribution of the mononuclear [Cu(opooMe)]2− and of the magnetic exchange interactions of trinuclear [Cu3(opooMe)(pmdta)2]2+ complex fragments. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

The new borophosphates described here were synthesized under mild hydrothermal conditions (170 oC or 220 oC). Powder and single crystal X-ray diffraction were employed to determine and refine the crystal structures. DTA-TG methods were used to analyze the thermal stability. High temperature powder X-ray diffraction (HT-XRD) was applied to study the thermal behavior of products and identify the intermediate phase during the decomposition. Chemical analyses were performed to quantitatively determine the chemical composition. Magnetic properties of the compounds were investigated. 19F MAS NMR was used to check the number of fluorine positions in the crystal structure. The following compounds were prepared and characterized: (C2H10N2)[BPO4F2](C6H14N2){Zn[ZnB2P4O15(OH)2]¡P(C6H13N2)Cl} (zndabcocl) (C3H12N2){Mn[B2P3O12(OH)]} (DAP-Mn) and (C4H12N2){Mn[B2P3O12(OH)]} (PIP-Mn) (C3H12N2){FeIII6(H2O)4[B4P8O32(OH)8]}(C3H12N2)2{VIII2VIV3B2P8O38H8} (dapvbpo) K3[B5PO10(OH)3](C2H10N2)[BPO4F2] is the first fluorine-substituted borophosphate and the first borophosphate with crystal structure closely related to the pyroxene type structure. Unbranched zweier single chain {[BPO4F2]2?} represents a new type of borophosphate partial structure. zndabcoclrepresents the first organo-templated zincoborophosphate. The structure contains diaza-bicyclo[2.2.2]-octane (DABCO) which acts in its diprotonated form (H2DABCO)2+ as a pure template and in its monoprotonated form (HDABCO)+ as a ligand to Zn-positions at the borders of ribbons to complete structural motif. This compound is also the first example containing a quaternary Zn-tetrahedron (ZnO2NCl), and can formally be described as an adduct of (C6H14N2)Zn[ZnB2P4O15(OH)2] with diaza-bicyclo[2.2.2]octane-hydrochloride. The thermal behavior of zndabcocl has been studied by HT-XRD and DTA-TG in the temperature range 25?600 oC. The new phase occurring during the decomposition has been identified as HT-NH4[ZnBP2O8].DAP-Mnand PIP-Mn contain identical framework interconnections but difference in the shape of resulting channels, which are due to the different shape of organic templates. The crystal structures are built from the same building units: loop-branched single chains are connected via MnO6-octahedra resulting in a 3-D structure with intersecting channel systems running along [100], [011] and [01], respectively. The different shape of the template controls the shape of the channels, especially channels running along [100], resulting in dramatic shape-differences. The linear (H2DAP)2+ ions make the channels more elongated, while the cyclic (H2PIP)2+ ions give rise to more regular shaped channels. The flexibility of frameworks may be due to the more flexible coordination of Mn-atoms (octahedron and square pyramid).(C3H12N2){FeIII6(H2O)4[B4P8O32(OH)8]} is a new borophosphate with 3-D framework structure, a large size of 10-ring channel (778 ¡Ñ 867 pm2) is occupied by organic templates. The magnetic susceptibility measurements show it to exhibit antiferromagnetic susceptibility at low temperature (TN ?l 14K).dapvbpois the first mixed-valency vanadium borophosphate with a new structure type. Its structure can be considered as an ?intergrowth? of puckered vanadium(III) borophosphate layer (VIIIBPO-layer) and planar vanadium(IV) phosphate layers (VIVPO-layer) stacked and interconnected alternately along [001], which results in a new and unusual building motif. The corner sharing trimers of vanadium octahedra are observed for the first time in vanadium borophosphates. K3[B5PO10(OH)3] has a double unit cell of a twin crystal structure having the same chemical formula. The double b-axis solves the disorder problem of two oxygen positions coordinated to phosphorous. It represents a much more reasonable structure determination.

Im Mittelpunkt dieser Arbeit standen die Darstellung und Charakterisierung ternärer Bismutsubchloride unter Einbau von Übergangsmetallen der 8., 9. und 10. Gruppe. Durch Vorlage eines hohen Chloranteils in der Synthese wurde die "chemische Schere" der Oxidation so stark wirksam, dass in den Verbindungen die gewünschten voneinander isolierten Cluster aus Metallatomen vorlagen. Die Verbindungen Bi12PtCl12, Bi12-xRhCl13-x, Bi12-xIrCl13-x (x < 1) und Bi6,67PtCl12 wurden als Pulver und als Kristalle durch Festkörperreaktionen bei 1273 K in Quarzglasampullen hergestellt. Die schwarz glänzenden, würfelförmigen Kristalle sind luftstabil, in verdünnten Mineralsäuren und in organischen Lösungsmitteln beständig. Die Zusammensetzungen wurden mit EDX-Analysen und Röntgenbeugung am Einkristall bestimmt. Zur weiteren Charakterisierung wurden quantenchemische Rechnungen, ramanspektroskopische Untersuchungen, Messungen der magnetischen Suszeptibilität und der elektrischen Leitfähigkeit durchgeführt. Kristalle der Verbindung Bi12PtCl12 täuschen ein rhomboedrisches Kristallsystem vor, die Struktur konnte in der Raumgruppe P 1 als nahezu perfekter Inversionszwilling eines Achsendrillings gelöst werden. Auf den Eckplätzen der pseudorhomboedrischen Elementarzelle befinden sich [PtBi6Cl12]2- -Cluster und in der Mitte ein (Bi6)2+ -Polykation. Dieses (Bi6)2+ -Polykation in Form eines geöffneten Oktaeders bestätigt experimentell Vorhersagen von Kuznetsov et al. Nach den Regeln von Wade ist das Polykation mit 2 x 6 + 4 = 16 Gerüstelektronen als nido-Cluster zu verstehen. Die Schwerpunkte der Anionen und Kationen fügen sich zu einer dem CsCl-Typ analogen Anordnung zusammen. Mit einer vollständigen Besetzung aller Bismutlagen in der Mitte der Elementarzelle kann Bi12PtCl12 eine Schlüsselrolle zugeordnet werden, die sozusagen den Prototyp für diesen Strukturtyp darstellt. Die weiteren Verbindungen stellen unterbesetzte Varianten dar und können von Bi12PtCl12 abgeleitet werden. Im Verlauf der Untersuchungen zu den ternären Subchloriden in den Systemen wurden wenige Kristalle der binären Verbindung Bi7Cl10 erhalten. Die Tatsache, dass es sich um eine neue binäre Phase im recht stark untersuchten Gebiet Bismut-Chlor handelte führte zu einer neuerlichen, systematischen Überprüfung des Systems Bi/Cl. Mittels thermischer Analysen wurde das Zustandsdiagramm Bi/BiCl3 präzisiert. Bi7Cl10 zersetzt sich bereits bei 190 °C peritektoid in Bi6Cl7 und BiCl3 Bi7Cl10(s) = Bi6Cl7(s) + BiCl3(g). Das Zustandsbarogramm des binären Systems wurde über Gesamtdruckmessungen im Membran-Nullmanometer erstmalig bestimmt. Aus den Druckfunktionen der Bismutchloride sowie aus Messungen der Molwärme von Bi6Cl7 wurden die thermodynamischen Standarddaten abgeleitet. Unter Verwendung dieser Daten wurden thermodynamische Modellierungen der Festkörper-Gasphasen-Gleichgewichte durchgeführt, mit deren Hilfe die Synthese von Bi7Cl10 optimiert werden konnte. Die phasenreine Gasphasenabscheidung von Bi7Cl10 ist aufgrund der Kondensation der dominierenden Gasphasenspezies BiCl und BiCl3 im Existenzbereich der Verbindung oberhalb des Zersetzungspunktes (190 °C) nicht möglich. Im Existenzgebiet von Bi7Cl10 kommt der Transport dann wegen der resultierenden Partialdrücke unmittelbar zum Erliegen. Aus Röntgenbeugungsuntersuchungen an Einkristallen geht hervor, dass Bi7Cl10 bei Raumtemperatur in der tetragonalen Raumgruppe I 41/a c d mit a = 28,235(3) und c = 39,950(4) Å kristallisiert (Z = 64). Analog zu Bi6Cl7 = ((Bi9)5+)[(Bi3Cl14)5-] kann Bi7Cl10 unter Verdopplung der Summenformel als ((Bi9)5+)[(Bi5Cl20)5-] formuliert werden. In der Kristallstruktur sind Polykationen (Bi9)5+, welche die Gestalt zweifach überkappter trigonaler Prismen haben, in ein Chlorobismutat(III)-Raumnetzwerk [(Bi5Cl20)5-] eingebettet. Die Polykationen und das Anionennetzwerk sind deutlich voneinander separiert.

In the course of these investigations altogether 18 different compounds have been synthesized and their chemical, structural and physical properties were characterized (XRD, XANES, IR, Raman spectrum, magnetic susceptibility, electrical resistivity, low temperature and TG/DTA). Up to now only nitridonickelates and nitridocuprates were known to exhibit exclusively low oxidation states of the transition metals between 0 and +2. In this work it has been presented that also nitridocobaltates belong to this group. We have proved that “Ca3CoIIIN3” do not exist and the real chemical formula can be regarded as Ca5[CoIN2]2. In the thesis another seven new nitridocobaltates(I) have been described, these add to four already known structures. Among novel phases only Ba9Ca[Co2N3]3 may indicate higher valency state for cobalt with the [Co2N3]5- complexes. The XANES data supporting CoII state by comparison with other compounds possess this oxidation state. The crystal structure of Ba9Ca[Co2N3]3 is related to the perovskite type structure. The remarkable structural features of Sr2[CoN2]0.72[CN2]0.28 ≈ Sr6[CoN2]2[CN2] nitridocobaltates [CoIN2]5- ions partially substituted by carbodiimides [N=C=N]2- ions. Up to now in the crystal structure no indications for a homogeneity range could be observed. Both crystal structures of (Sr6N)[CoN2][CN2]2 and Sr6[CoN2]2[CN2] encompass nitridocobaltate [CoN2]5- and carbodiimide [N=C=N]2- ions. In the structures distorted rocksalt motif based on Sr-N partial structure can be distinguished. Up to now in the system AE-Fe-N-(C) only four crystal structures were reported and in the thesis three new were refined Sr8[FeIIIN3]2[FeIIN2], Sr3[FeN3] and (Sr6N)[FeN2][CN2]2 and their physical properties were characterized. The system AE-Mn-N-(C) via this work was extended by Sr8[MnN3]3 and Sr4[MnN3][CN2]. Up to date the only nitridometalate containing different transition elements is Ba[Ni1-xCuxN]. In this work one more mixed nitridometalate has been described Sr8[MnIIIN3]2[FeIIN2]. The crystal structure of Sr4[MnN3][CN2] revealed some weak diffuse scattering lines. The general formula of Sr4[MnN3][CN2] can be written as Sr4[Mn0.96N2.90][C0.96N2] to emphasize possible homogeneity range. Any explanation of the phenomena and establishment of possible homogeneity range are still a challenge. The structures of Sr8[MIIIN3]2[FeIIN2] (M = Mn, Fe) are related to Sr8[MnIVN3]2[MnIIIN3]. All these compounds are first mixed-valency compounds for respective systems and exhibit close relation to crystal structures of Sr3[MN3] (M = Mn, Fe). From the XANES data alike behaviour of all structures containing Mn was observed. Due to some possible degree of Mn/Fe mixing in the crystal structure of Sr8[MIIIN3]2[FeIIN2] the chemical formula might be written as Sr8[MnN3]2-x[FeN3]x[FeN2]. This needs to be investigate in details. Up to now in the literature the only crystallographic data of nitridometalates contain [NCN]2- ions include two compounds. In this work four novel nitridometalate carbodiimides and cyanamides Sr4[MnN3][CN2], (Sr6N)[MN2][CN2]2 (M = Co, Fe) and Sr6[CoN2]2[CN2] have been synthesized. Predominant magnetic properties in the investigated nitridometalates are connected to some antiferromagnetic M-M interactions supported by AFM ordering. The electrical resistivity often shows at some semi-conducting character of these compounds. XANES spectroscopy provided many useful data about valency states of the transition elements, coordination environment around absorbing atoms and electronic structure. The influence of different parameters on the transition metals K-edges was studied in details. IR and Raman give general data about [NCN]2- ions.

The phase diagram of the Mg-Pd system was redetermined in the range from 50 at. % Mg to 100 at. % Mg. It contains several intermediate phases with some of them being complex metallic alloy phases (CMAs), i.e., characterized by (i) giant unit cells with more than hundred atoms, (ii) inherent disorder, (iii) the presence of a cluster substructure. Phase fields and heterogeneous equilibria of the intermediate phases β- Mg6Pd, γ-Mg57Pd13, δ-Mg56.4Pd13.6, ε-Mg306Pd77, ζ-Mg64Pd17, η-Mg3Pd, θ-Mg5Pd2, ι- Mg2Pd and κ-MgPd were determined. The first five phases are CMAs with Mackay clusters as fundamental structural units. The crystal structure of the most magnesium-rich compound β-Mg6Pd was redetermined. It was found to be more complicated than previously thought due to correlated disorder of only two atom sites in the cubic unit cell. The γ-, ε- and ζ-phases form in a small window of temperature (50 oC) and composition (3 at. %) close to 80 at. % Mg. A new structure type was assigned to Mg3Pd (Cu3P, P63cm). The single phase field of the θ-phase is caused by constitutional vacancies. The new ι-phase crystallizes with NiTi2 structure-type. / Das Phasendiagramm des Systems Mg–Pd wurde im Bereich von 50 bis 100 At.-% Mg neu bestimmt. In diesem Phasendiagramm finden sich mehrere intermediäre Phasen, darunter auch komplexe intermetallische Verbindungen (engl.: complex intermetallic alloys, CMAs). CMAs sind charakterisiert durch (i) große Elementarzellen mit mehr als einhundert Atomen, (ii) intrinsischer Fehlordnung und (iii) dem Vorhandensein einer Cluster- Substruktur. Die Phasenfelder und heterogenen Gleichgewichte der intermediären Phasen β-Mg6Pd, γ- Mg57Pd13, δ-Mg56.4Pd13.6, ε-Mg306Pd77, ζ-Mg64Pd17, η-Mg3Pd, θ-Mg5Pd2, ι-Mg2Pd und κ- MgPd wurden bestimmt. Die ersten fünf der eben genannten Phasen sind CMAs mit Mackay Clustern als fundamentales strukturelles Einheit. Alle übrigen Phasen besitzen einen einfacheren kristallografischen Aufbau. Die Kristallstruktur der Mg-reichsten Verbindung β-Mg6Pd wurde neu bestimmt und ist weitaus sich als komplizierter als bisher angenommen. Die Ausdehnung des Einphasenfeldes von β-Mg6Pd lässt sich jedoch sehr einfach mit korrelierter Fehlordnung von lediglich zwei Atomen in der kubischen Elementarzelle verstehen. Die γ-, ε-, und ζ-Phasen bilden sich in einem schmalen Temperatur- (50 °C) und Zusammensetzungsbereich (3 at. %) nahe 80 at. % Mg. Der Verbindung Mg3Pd (Cu3P, P63cm) wurde ein neuer Strukturtyp zugewiesen. Die Ausdehnung des Einphasenfeldes der θ-Phase lässt sich mit dem Einbau konstitutioneller Leerstellen erklären. Die neue ι-Phase kristallisiert im NiTi2 Strukturtyp.

Consolidating a microscopic understanding of magnetic properties is crucial for a rational design of magnetic materials with tailored characteristics. The interplay of 3d and 4f magnetism in rare-earth transition metal antimonides is an ideal platform to search for such complex behavior. Here the synthesis, crystal growth, structure, and complex magnetic properties are reported of the new compound Pr3Fe3Sb7 as studied by magnetization and electrical transport measurements in static and pulsed magnetic fields up to 56 T, powder neutron diffraction, and Mößbauer spectroscopy. On cooling without external magnetic field, Pr3Fe3Sb7 shows spontaneous magnetization, indicating a symmetry breaking without a compensating domain structure. The Fe substructure exhibits noncollinear ferromagnetic order below the Curie temperature TC ≈ 380 K. Two spin orientations exist, which approximately align along the Fe–Fe bond directions, one parallel to the ab plane and a second one with the moments canting away from the c axis. The Pr substructure orders below 40 K, leading to a spin-reorientation transition (SRT) of the iron substructure. In low fields, the Fe and Pr magnetic moments order antiparallel to each other, which gives rise to a magnetization antiparallel to the external field. At 1.4 K, the magnetization approaches saturation above 40 T. The compound exhibits metallic resistivity along the c axis, with a small anomaly at the SRT.

No description available.

No description available.

The title compounds, C23H25Br2NO2 (1) and C31H29BrN2O4 (2), crystallize in the space group P21/n with two (1-A and 1-B) and one mol­ecules, respectively, in the asymmetric unit of the cell. The mol­ecular conformation of these compounds is stabilized by intra­molecular C—H⋯O hydrogen bonds and C—H⋯N or C—H⋯π inter­actions. The crystal structure of 1 features a relatively strong Br⋯O=C halogen bond, which is not observed in the case of 2. Both crystal structures are characterized by the presence of C—H⋯Br hydrogen bonds and numerous inter­molecular C—H⋯O hydrogen-bonding inter­actions.

The title compound, C20H18O3, crystallizes in the space group P21/c with one mol­ecule in the asymmetric unit of the cell. The fluorene skeleton is nearly planar and the crystal structure is composed of mol­ecular layers extending parallel to the (302) plane. Within a layer, one formyl oxygen atom participates in the formation of a Carene—H...O bond, which is responsible for the formation of an inversion symmetric supra­molecular motif of graph set R22(10). A second oxygen atom is involved in an intra­molecular Carene—H...O hydrogen bond and is further connected with a formyl hydrogen atom of an adjacent mol­ecule. A Hirshfeld surface analysis indicated that the most important contributions to the overall surface are from H...H (46.9%), O...H (27.9%) and C...H (17.8%) inter­actions.