Variable Temperature Powder X-ray Diffraction Research Articles

Polymorphism and Phase Transformation Behavior of Solid Forms of 4-Amino-3,5-dinitrobenzamide

We report the preparation, analysis, and phase transformation behavior of polymorphs and the hydrate of 4-amino-3,5-dinitrobenzamide. The compound crystallizes in four different polymorphic forms, Form I (monoclinic, P21/n), Form II (orthorhombic, Pbca), Form III (monoclinic, P21/c), and Form IV (monoclinic, P21/c). Interestingly, a hydrate (triclinic, P1̅) of the compound is also discovered during the systematic identification of the polymorphs. Analysis of the polymorphs has been investigated using hot stage microscopy, differential scanning calorimetry, in situ variable-temperature powder X-ray diffraction, and single-crystal X-ray diffraction. On heating, all of the solid forms convert into Form I irreversibly, and on further heating, melting is observed. In situ single-crystal X-ray diffraction studies revealed that Form II transforms to Form I above 175 °C via single-crystal-to-single-crystal transformation. The hydrate, on heating, undergoes a double phase transition, first to Form III upon losing water in a single-crystal-to-single-crystal fashion and then to a more stable polymorph Form I on further heating. Thermal analysis leads to the conclusion that Form II appears to be the most stable phase at ambient conditions, whereas Form I is more stable at higher temperature.

Structural disorder and transformation in crystal growth: direct observation of ring-opening isomerization in a metal-organic solid solution.

A rare example is reported in which discrete Ag2 L 2 ring and (AgL)∞ chain motifs [L = N,N'-bis(3-imidazol-1-yl-propyl)-pyromellitic diimide] co-crystallize in the same crystal lattice with varying ratios and degrees of disorder. Crystal structures obtained from representative crystals reveal compatible packing arrangements of the cyclic and polymeric isomers within the crystal lattice, which enables them to co-exist within a crystalline solid solution. A feasible pathway for transformation between the isomers is suggested via facile rotation of the coordinating imidazolyl groups. This chemical system could provide a chance for direct observation of ring-opening isomerization at the crystal surface. Mass spectrometry and (1)H NMR titration show a dynamic equilibrium between cyclic and oligomeric species in solution, and a potential crystallization process is suggested involving alignment of precursors directed by aromatic stacking interactions between pyromellitic diimide units, followed by ring-opening isomerization at the interface between the solid and the solution. Both cyclic and oligomeric species can act as precursors, with interconversion between them being facile due to a low energy barrier for rotation of the imidazole rings. Thermogravimetric analysis and variable-temperature powder X-ray diffraction indicate a transition to a different crystalline phase around 120°C, which is associated with loss of solvent from the crystal lattice.

Synthesis, structure and band gap energy of a series of thermostable alkaline earth metal based metal–organic frameworks

Three new compounds based on alkaline earth element ions and 4,4′-oxy-bis(benzoic acid) (OBA) were synthesized and characterized. Compound 1, [Ca(H2O)(OBA)], consists of a Ca2O10 dimer, which is connected through OBA anions to form the three-dimensional structure. While in compound 2, [Sr(H2O)(OBA)], SrO7 units are connected to form one-dimensional chains, which are in-turn connected by OBA anions to form the three-dimensional architecture. In compound 3, [Ba2O3(OBA)2], BaO8 and BaO9 units are connected to form the 6-membered two-dimensional sheet structure. These two-dimensional layers are pillared by OBA anions to complete the three-dimensional connectivity. Variable temperature powder X-ray diffraction and thermogravimetric analysis studies show that all these structures are thermally stable up to 400 °C. We have measured the optical band gap energies and results show that the values decrease slightly from 1 to 3. This variation in band gap energy may be due to the different architectures, which affect the states of conduction and valence bands of the materials.

Thermoresponsive studies of porous and non-porous borophosphates.

In this work we present the synthesis and structure-property investigation of anhydrous low porosity borophsophates [1] BPO4 and porous (NH4)0.5M1.25(H2O)2)(BP2O8)(H2O)0.5 M = Co (II), Mn (II) and NH4Fe[BP2O8(OH)] phases. Cristobalite-type BPO4 crystallizes in the tetragonal lattice, space group I-4 (No. 82) [2]. Variable-Temperature Powder X-ray diffraction (VT-PXRD) patterns for these material were analysed by the sequential and parametric Rietveld refinement [3] protocols. Both methods were used to determine the temperature dependency of the lattice parameters and linear thermal expansion coefficient. Whereas the lattice parameters were refined freely in the sequential method, the individual cell parameters were described using an empirically derived function in the parametric method. Both refinement protocols reveal significant anisotropy along the a- and c- axis as a function of temperature, with thermal expansion coefficients of 10.6 x10-6 /0C and 2.83 x10-6 /0C, respectively. Structural changes accompanying this thermoresponsive behaviour will be discussed, including the variation of the interatomic distances and P-O-B (inter-polyhedral angle, figure 1) with temperature. The open framework (NH4)0.5M1.25(H2O)2)(BP2O8)(H2O)0.5 M = Co(II) (1a), Mn(II) (1b) and NH4Fe[BP2O8(OH)] (2) phases were synthesized under mild hydrothermal methods at 1800C. The crystal structure of the isostructural (1a) and (1b) phases were refined in the hexagonal lattice, space group P65 (no. 170) and compound (2) in the monoclinic lattice, space group P21/c (no.14). Both (1a) and (1b) phases consists of NH4+ and H2O molecules located within the helical channels running along the [001] direction with compound (2) consisting exclusively of NH4+ molecules located within the helical channels running along the [100] direction. Thermoresponsive investigation conducted by TGA analysis reveal a five, four and three step mass loss process for compounds (1a), (1b) and (2) respectively, with the final step observed at 500-7000C range. Preliminary VT-PXRD results of these compounds will also be presented.

Anisotropic strain and Jahn-Teller effect of chiral complexes and metal oxides

For about a decade, we have systematically investigated thermally-accessible lattice strain and local pseudo Jahn-Teller distortion of [CuL2]3[M(CN)6]2·4H2O (L = (1R, 2R)-cyclohexanediamine; M = Cr, Co, and Fe). In mononuclear Cu(II) complexes, (pseudo) Jahn-Teller effect plays an important role in flexible distortion of crystal structures especially Cu(II) coordination environment. Beside Jahn-Teller distortion, we have dealt with some factors for example, metal substitution as bimetallic assemblies, chirality of ligands, and H/D isotope effect to vary intermolecular interaction and crystal packing. According to the course work using variable temperature PXRD, we have found that anisotropy of crystal strain distortion did not corporate with Jahn-Teller distortion around local coordination environment because of the discrepancy of the crystallographic axes and molecular alignment. In order to elucidate the anisotropic control of lattice strain and Jahn-Teller distortion closely, we have employed transition metal oxide with orthogonal or layered structures to prepare composite materials with the chiral metal complexes for discussion of thermally-accessible PXRD changes and IR shift due to adsorption. At first, we have employed chiral one-dimensional zig-zag Cu-Cr bimetallic assemblies and their oxides prepared by burining. Based on variable temperature XRD patterns, a linear correlation (lnK = a/T + b) of K (=d(T)-d(0)/d(T)) values, where d(T) and d(0) are spacing of lattice plane (d = nλ/(2sinθ)) at T K and 0 K (extrapolated), respectively, and its deviation from ideal correlation indicates degree of anisotropic lattice distortion of the composite materials. For example, we could observe LiMnO2, typical material of lithium ion battery, was enhanced anisotropic lattice strain along the b axis or the (011) plane added by [CuL2(H2O)2](NO3)2 complexes. Which may prevent from breaking down regular crystal structures during charge-discharge of secondary battery.

Structural Transition in the Perovskite-like Bimetallic Azido Coordination Polymers: (NMe4)2[B′·B″(N3)6] (B′ = Cr3+, Fe3+; B″ = Na+, K+)

Through in situ variable-temperature single-crystal X-ray diffraction analysis, a solid–solid structural phase transition induced by the successive displacements of the [NMe4]+ guest and a subsequent abrupt order–disorder transform for both the cationic guest and the cage-like framework was tracked in four perovskite-like bimetallic azido coordination polymers: (NMe4)2[B′·B″(N3)6] (B′ = Cr3+, Fe3+; B″ = Na+, K+). Such structural transition was also confirmed by differential scanning calorimeter measurement, variable-temperature powder X-ray diffraction analysis, and variable-temperature dielectric permittivity measurement, as well as molecular dynamics simulation. Conclusively, these compounds provide a good host–guest model for understanding and modulating the thermal motion behavior of the [NMe4]+ guest in various confined spaces constructed by the perovskite-like azido frameworks.

An Investigation into the Dehydration Behavior of Paroxetine HCl Form I Using a Combination of Thermal and Diffraction Methods: The Identification and Characterization of a New Anhydrous Form

Paroxetine HCl can exist as a nonstoichiometric hydrate (Form II) or as a stoichiometric hemihydrate (Form I); the latter is considered to be the stable form and its structure is well-known. However, little work has been performed to investigate its dehydration behavior; hence, the generation of the anhydrous form via dehydration of Form I was investigated. A combination of thermal (differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)) and diffraction (variable-temperature X-ray powder diffraction (VT-XRPD)) techniques was used. Dehydrated Form I was prepared using ultradry conditions, and the resulting product was compared to dehydrated Form II. DSC indicated that the two dehydrated forms of Forms I and II had distinct melting points. TGA experiments allowed the calculation of the activation energy for the dehydration of Form I, which varies between 86 and 114 kJ/mol. Pawley refinement of the VT-XRPD data suggested that Form I dehydrates to an isostructural anhydrate, since the unit cell parameters of this new form were very similar to those of Form I with only a smaller volume as a consequence of dehydration. Comparison with dehydrated Form II indicated that these two forms represent different crystal entities; hence, a new anhydrous form of paroxetine HCl has been identified.

When long bis(pyrazolates) meet late transition metals: structure, stability and adsorption of metal–organic frameworks featuring large parallel channels

A family of bis(pyrazolato)-based metal-organic frameworks (MOFs) was isolated by reacting 1,4-bis(1H-pyrazol-4-ylethynyl)benzene (H2BPEB) with a number of transition metal ions. Special attention was dedicated to their structural features, their thermal and chemical stability, as well as their spectroscopic and adsorption properties. The rod-like ligands, connecting Zn(II), Ni(II) and Fe(III) nodes, fabricate 3-D networks containing 1-D pervious channels. The combination of thermal analysis and variable-temperature XRPD demonstrated the remarkable thermal robustness of the three materials, which are stable in air up to at least 410 °C, and showed their structural response to increasing temperature. Specific experiments permitted us to test the chemical stability of the three species toward water as well as moderately acidic and basic solutions, the Ni(II) derivative being stable and hydrophobic in all the conditions assayed. The electronic transitions of both the ligand and the MOFs were investigated by solid-state UV-Vis absorption as well as by steady-state and time-resolved fluorescence analysis, which showed that the high fluorescence of the linker is perturbed in the three MOFs, suggesting high sensitivity to environmental changes. N2 adsorption measurements at 77 K allowed to estimate promising Langmuir specific surface areas, peaking at 2378 m2 g−1 in the case of the Ni(II) derivative. The best CO2 and CH4 uptake performances were achieved with the Fe(III)-based MOF. Indeed, adsorption experiments with CO2 revealed that a considerable amount, up to 40% wt, is adsorbed by the Fe(III) derivative under the mild conditions of 298 K and 10 bar.

The influence of hydrogen bonding on the planar arrangement of melamine in crystal structures of its solvates, cocrystals and salts

The hydrogen bonding patterns of melamine as well as mono- and diprotonated melamine have been analysed in five crystal structures of a solvate, a cocrystal and three organic and inorganic salts, namely, melamine DMSO solvate ([mel]·DMSO (1)), melamine theobromine cocrystal ([mel]·[TBR]3 (2)), dimelaminium ethylenediaminetetraacetate ([mel-H]2[EDTA-H2]·2H2O (3)), anhydrous dimelaminium sulfate ([mel-H]2[SO4] (4)), and anhydrous melaminium dinitrate ([mel-H2][NO3]2 (5)). Melamine is a versatile molecular building block (tecton) in cocrystals, solvates and salts. Depending on the degree of protonation and/or other molecules or ions present in the structure, parallels could be drawn to determine whether melamine is arranged in a cross-linked manner, in undulating sheets or in the form of perfectly planar sheets in the structure. Graph set analysis was used to compare the geometry of hydrogen bond interactions of the new structures with those of other structures published in the literature. Solvent drop-assisted solid state reactions (kneading) were performed for “green” synthesis of the compounds. The organic salt 3 has high thermal stability as shown by variable-temperature X-ray powder diffraction, which is presumably related to its extensive hydrogen bond network. Rietveld refinements were carried out on laboratory powder diffraction data to confirm the structures of the compounds obtained from single-crystal data.

Prediction of Polymorphic Transformations of Paracetamol in Solid Dispersions

A novel approach employing variable-temperature X-ray powder diffraction (VTXRPD) was used to exploit its suitability as an off-line predictive tool to study the polymorphic transformations of paracetamol (PMOL) in melt-extruded hydrophilic polymer matrices. Physical mixtures (PMs) and extruded formulations of PMOL with either polyvinyl caprolactam graft copolymer (Soluplus®) or vinylpyrrolidone-vinyl acetate copolymer (Kollidon®) in the solid state were characterized by using differential scanning calorimetry, hot-stage microscopy, and scanning electron microscopy. The experimental findings from VTXRPD showed that the stable Form I (monoclinic) of PMOL transformed to the metastable polymorph Form II (orthorhombic) at temperatures varying from 112°C to 120°C, in both the PMs and extrudates suggesting an effect of both temperature and identity of the polymers. The findings obtained from VTXRD analysis for both the PMs and the extruded formulations were confirmed by in-line near-infrared (NIR) monitoring during the extrusion processing. In the NIR study, PMOL underwent the same pattern of polymorphic transformations as those detected using VTXPRD. The results of this study suggest that VTXRPD can be used to predict the polymorphic transformation of drugs in polymer matrices during extrusion processing and provides a better understanding of extrusion processing parameters.

Bis(pyrazolato)-Based Metal–Organic Frameworks Fabricated with 4,4′-Bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)biphenyl and Late Transition Metals

The reaction between the flexible, bis(pyrazolato)-based ligand 4,4′-bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)biphenyl (H2DMPMB) and late transition metal ions allowed the isolation of the two series of thermally stable metal–organic frameworks [M(DMPMB)] (M = Co, Zn, Cd) and [M2(DMPMB)] (M = Cu, Ag). X-ray powder diffraction (XRPD) structure determinations demonstrated that the anti conformation adopted by the ligand, juxtaposed to its exo-tetradentate coordination mode, induces the formation of a 3-D architecture with nonpervious 1-D channels in the three isomorphous species [M(DMPMB)] and of corrugated 2-D layers in [Cu2(DMPMB)]. Coupling thermogravimetric analyses and variable temperature XRPD highlighted that the five materials are thermally stable at least up to 300 °C, both under nitrogen and in air, the Cd(II) derivative decomposing only at the remarkably high temperature of 500 °C. No thermal event could be detected; all the materials preserve their structural motifs up to decomposition. The adsorption properties of the five compounds were assayed toward N2 at 77 K: while no adsorption was observed for [Cd(DMPMB)], the other species possess estimated BET and Langmuir specific surface areas in the ranges 64(1)–526(3) m2/g and 142(4)–713(27) m2/g, respectively, thus being an example of the interesting phenomenon known as “porosity without pores”. Finally, the luminescence properties of the Zn(II), Cd(II), and Cu(I) derivatives were investigated.

Inorganic–organic hybrid with one-dimensional face-sharing iodoplumbate chain showing novel dielectric anomaly and semiconductor emission

An inorganic–organic hybrid [tetrabutylammonium][PbI3] crystallizes in tetragonal space group I-42d, which inorganic components form one-dimensional (1D) face-sharing iodoplumbate chain. This hybrid shows a novel dielectric anomaly around 125°C. The variable-temperature single crystal and powder X-ray diffraction (PXRD) measurements revealed that the dielectric anomaly arises from the disorder–order transformation of tetrabutylammonium. The hybrid emits orange-red luminescence, ascribed to the semiconductor emission of 1D [PbI3]∞ chain.

Structure and stability of two polymorphs of creatine and its monohydrate

An experimental search for crystalline forms of creatine including a variable temperature X-ray powder diffraction study has produced three polymorphs and a formic acid solvate. The crystal structures of creatine forms I and II were determined from X-ray powder diffraction data plus the creatine formic acid (1 : 1) solvate structure was obtained by single crystal X-ray diffraction methods. Evidence of a third polymorphic form of creatine obtained by rapid desolvation of creatine monohydrate is also presented. The results highlight the role of automated parallel crystallisation, slurry experiments and VT-XRPD as powerful techniques for effective physical form screening. They also highlight the importance of various complementary analytical techniques in structural characterisation and in achieving better understanding of the relationship between various solid-state forms. The structural relationships between various solid-state forms of creatine using the XPac method provided a rationale for the different relative stabilities of forms I and II of creatine with respect to the monohydrate form.

Reversible Dehydration in Polyoxometalate-Based Hybrid Compounds: A Study of Single-Crystal to Single-Crystal Transformations in Keggin-Type Germanotungstates Decorated with Copper(II) Complexes of Tetradentate N-Donor Ligands

Hydrothermal reaction of the Keggin-type [α-GeW11O39]8– anion with copper(II) complexes of the tetradentate N-donor ligands N,N′-dimethyl-N,N′-bis-(pyridine-2-ylmethyl)-1,2-diaminoethane (bpmen) or N,N′-dimethyl-N,N′-bis-(pyridine-2-ylmethyl)-1,3-diaminopropane (bpmpn) results in three new hybrid compounds [Cu(bpmen)(H2O)][GeW12O40{Cu(bpmen)}]·3.5H2O (1), [GeW12O40{Cu(bpmpn)(H2O)}2]·3H2O (2), and [Cu(bpmpn)(H2O)][GeW12O40{Cu(bpmpn)}]·8H2O (3). All compounds have been characterized by elemental analyses and infrared spectroscopy, and their structures have been established by single-crystal X-ray diffraction. Both 1 and 3 contain monodecorated polyanions and additional complex cations, but their layered structures show noticeable differences. For 1, the polyanions are arranged in rows whose stacking generates intralamellar cavities where complex cations and lattice water molecules are hosted, whereas double-layers of hybrid anions pillared by the cations occupying the interlamellar space are observed for 3. In the case of 2, the packing of trans-didecorated clusters generates honeycomb-like metalorganic layers and perpendicular hexagonal channels where Keggin moieties are nested. A combination of thermogravimetric and variable temperature powder X-ray diffraction analyses show that dehydration of 1 and 2 results in thermally stable, crystalline phases. Dehydrations are fully reversible upon exposure to air and proceed via single-crystal to single-crystal transformations implying rupture/formation processes in the copper(II) bonding and consequent geometrical and conformational modifications in the complexes. Transformations have been followed by single-crystal X-ray diffraction, allowing for the structures of the anhydrous phases [GeW12O40{Cu(bpmen)}2] (1a) and [GeW12O40{Cu(bpmpn)}2] (2a) to be determined. Dehydration of 1 into 1a with consequent formation of neutral, didecorated clusters does not result in the collapse of the intralamellar cavities but rather in an open-framework structure with slit-shaped micropores. Structural variations between 1 and 2 and their corresponding anhydrous phases are reflected in the electron paramagnetic resonance spectra.

Unsolvated ruthenium(II) benzene dichloride: The beta polymorph

A novel polymorph of the unsolvated species [Ru2(benzene)2Cl4] (β form in the following) was serendipitously isolated as a polycrystalline powder. Its molecular and crystal structure was unraveled by means of state-of-the-art X-ray powder diffraction structure determination methods applied to laboratory data, and was compared to those of both the α polymorph and the CHCl3 solvate, throwing light on some discrepant results recently appeared in the literature. The thermal behavior of the α and β polymorphs was investigated by coupling thermogravimetric analyses to variable-temperature X-ray powder diffraction experiments. No temperature-stimulated phase transformation could be detected between the two polymorphs, each preserving its structural features up to decomposition, suggesting that kinetic, more than thermodynamic, factors regulate their isolation.

A Solubility Comparison of Neutral and Zwitterionic Polymorphs

Several amphoteric model compounds and drugs, such as isomers of aminobenzoic acids (ortho, meta, and para), N-aryl-2-amino-nicotinic acids (three isomers), amino-salicylic acids (meta and para), clonixin, and niflumic acid, were selected to obtain their zwitterionic and neutral polymorphs with the objective to study their X-ray crystal structures, solubility and dissolution rate, and stability. We were successful in crystallizing neutral and ionic polymorphs for 2- and 3-aminobenzoic acid (ABA), 2-(p-tolylamino)nicotinic acid (TNA), and clonixin (CLX), as well as 4- and 5-aminosalicylic acid (4-ASA as neutral and 5-ASA in ionic form). The neutral and zwitterionic crystalline polymorphs were differentiated by their distinctive powder Xray diffraction (PXRD), Fourier transform infrared, Raman and ss-NMR spectroscopy, and further quantified by Hirshfeld surface analysis. Phase transitions were monitored by differential scanning calorimetry and variable temperature powder X-ray diffraction. The difference in...

Chemical Control of Thermal Expansion in Cation-Exchanged Zeolite A

Variable-temperature powder X-ray diffraction studies have been used to monitor dramatic changes in the thermal expansion properties of zeolites with the LTA topology on changing the pore contents. Detailed structural analysis was performed on dehydrated Li-, Na-, K-, Rb-, and Cs-exchanged zeolite A and a comparison made with their purely siliceous analogue ITQ-29. Mean thermal expansion coefficients were also determined for the hydrated alkali-metal-exchanged forms. Thermal expansion behavior ranging from negative to positive was observed as different monovalent cations were included in the zeolite pores. Cation-induced strain to the zeolite framework has been shown to play a significant role in the thermal expansion mechanism of LTA-zeolites. Atomic-scale mechanisms behind the thermal expansion behavior have been deduced for ITQ-29, dehydrated Ag-A, and dehydrated Na-A systems.

1D and 2D Thiazole-Based Copper(II) Coordination Polymers: Synthesis and Applications in Carbon Dioxide Capture.

The reaction of different copper(II) salts with a class of thiazole-based ligands under solvothermal conditions produces three crystalline 1D/2D coordination polymers: [Cu(κ-N-thiazole)4 (SiF6 )]∞ (1 (1D)), {Cu[μ-(κ-N:κ-COO)-L1 ]2 ⋅(H2 O)}∞ (2 (2D); HL1 =2-aminothiazole-5-carboxylic acid), and {Cu[μ-(κ-N:κ-COO)-L2 ]2 ⋅1.5 (H2 O)}∞ (3 (2D); HL2 =thiazole-5-carboxylic acid). All the materials have been characterized through common solid-state techniques: single-crystal (XRD) and (variable-temperature) powder X-ray diffraction (PXRD), infrared spectroscopy (IR), thermogravimetric analysis combined with mass spectrometry (TGA-MS), and BET surface area and pore-size distribution measurements. Polymer 3 shows a porous structure made of squared channels formed by the ordered stacking of the planar sheets along the a crystallographic axis (inner surface area equal to 15 m2 g-1 , as inferred from N2 adsorption at T=77 K on the pre-activated form), and it has been exploited for CO2 physisorption at ambient temperature (T=303 K) and pressure (p max.=920 torr). A remarkable CO2 uptake equal to 9.0 wt % was recorded under these mild conditions, thereby making the material promising for carbon dioxide capture in post-combustion flue gas, in which the key factor for a successful performance is the high chemical selectivity for CO2 over N2 .

Capsule voided nanospace confinement in a π-stacked supramolecular organic solid

Solid state supramolecular assembly of a novel C3-symmetric tripodal luminescent organic molecule has been explored to understand the molecular aggregation and the different possible interactions between host–host and host–guest pairs. Interesting capsule voided confinement of guest molecules and the helical arrangement via non-covalent interactions have been evidenced by single crystal X-ray diffraction and solid state circular dichroism study, respectively. Visual color change and variable temperature powder X-ray diffraction study supported solid state transitions in the supramolecular architecture.

Coordination frameworks assembled from Cu(II) ions and H₂-1,3-bdpb ligands: X-ray and magneto structural investigations, and catalytic activity in the aerobic oxidation of tetralin.

The syntheses and crystal structures of H2-1,3-bdpb·MeOH, [Cu(II)2(1,3-bdpb)(OCH3)2] (CFA-5) and [Cu(I)Cl(H2-1,3-bdpb)] (H2-1,3-bdpb = 1,3-bis(3,5-dimethyl-1H-pyrazol-4-yl)benzene) are described. The copper(II) containing metal-organic framework (termed Coordination Framework Augsburg University-5, CFA-5) crystallizes in the trigonal crystal system, within the space group R3̄ (no. 148) and the unit cell parameters are as follows: a = 26.839(3), c = 15.8317(16) Å, V = 9876.2(19) Å(3). CFA-5 features a two-fold interpenetrated 3-D microporous framework structure of cross-linked wheel-shaped {Cu(II)(pz)(OMe)}12 fundamental building units, each containing twelve copper(II) ions, μ2-bridging MeO(-) groups and pyrazolate (pz(-)) ligands. Replacing copper(II) acetate by copper(II) chloride in the synthesis leads to compound [Cu(I)Cl(H2-1,3-bdpb)], which crystallizes in the orthorhombic crystal system, within the space group Pnma (no. 62) and the unit cell parameters are as follows: a = 6.1784(8), b = 6.1784(8), c = 6.1784(8) Å, V = 1583.8(4) Å(3). In contrast to the former compound, CuCl(H2-1,3-bdpb) is a non-porous compound consisting of Cu(I)-Cl zigzag chains expanding in the direction [100] and H2-1,3-bdpb ligands. CFA-5 is characterized by elemental and thermogravimetric analyses, variable temperature powder X-ray diffraction and IR-spectroscopy; and its porosity and magnetic properties are described in detail. CFA-5 shows a promising catalytic activity in the heterogeneously catalyzed aerobic oxidation of tetralin, which is compared with other catalytically active metal-organic frameworks.