Mixed crystals in the system Cu2MnGexSn1−xS4: Phase analytical investigations and inspection of tetrahedra volumes

Cu₂MnGeS₄ crystallizes orthorhombic in a wurtzite superstructure type while Cu₂MnSnS₄ crystallizes in a tetragonal sphalerite superstructure type. Lattice constants and thermal analyses of the solid solution series Cu₂MnGe_xSn_1−xS₄ are presented. A two-phase region is found from Cu₂MnGe_0.3Sn_0.7S₄ to Cu₂MnGe_0.5Sn_0.5S₄. The cell volume of the mixed crystals increases with increasing Sn content. The melting points increase smoothly with increasing Ge content to x=0.5 and then steeply for higher Ge contents. The single crystal X-ray structure analysis of Cu₂MnGe_0.55Sn_0.45S₄ is presented. The refinement converges to R=0.0270 and wR₂=0.0586, Z is 2. The volumes of the tetrahedra [MS₄] (M=Cu, Mn, Ge, Sn) are calculated. From these volumes the differences in size of the tetrahedra are derived and compared with the corresponding differences in the end members of the solid solution series. It turns out that the resulting structure type in these materials depends on the volume differences of the constituting tetrahedra [MS₄].     

Electrical,magnetic, and EPR studies of the quaternary chalcogenides Cu2AIIBIVX4 prepared by iodine transport

Electrical, magnetic, and electron paramagnetic resonance (EPR) measurements have been made on crystals and powders of several quaternary chalcogenides of the type Cu₂A^IIB^IVX₄, where A^II = Zn, Mn, Fe, or Co, B^IV = Si, Ge, or Sn, and X = S or Se. The electrical properties of these compounds are extrinsic, but their magnetic properties do not appear to be affected by impurities. The magnetic moments of the Cu₂MnBX₄ compounds decrease with increasing covalency of the MnX bond, and those of Cu₂FeGeS₄ and Cu₂CoGeS₄ reflect an orbital contribution to the moment. Both the Weiss constants and magnetic ordering temperatures in these compounds show an evolution from antiferromagnetism to ferromagnetism with increasing separation between the moments. Magnetic measurements on single crystals of Cu₂MnGeS₄, Cu₂CoGeS₄, and Cu₂FeGeS₄ indicate that only the latter is anisotropic. EPR measurements on crystals and powders of Cu₂ZnGeS₄ doped nominally with 0.1% Mn reveal that Mn²⁺ experiences an axial distortion and that the bond ionicity is the same as in ZnS.     

On Aliovalent Substitution on the Li Site in LiMPO4: an ­X‐ray Diffraction Study of the Systems LiMPO4–M1.5PO4 (= LixM1.5–x/2PO4; M = Ni,Co, Fe,Mn)

In this paper we report on the possibility of Li substitution by M²⁺ to various high degrees in LiMPO₄ olivine‐type compounds (M = Ni, Co, Fe, Mn), depending on the kind of transition metal M. The experimental studies were carried through by reacting stoichiometric amounts of LiM^IIPO₄ and M^II_1.5PO₄ (= M^II₃(PO₄)₂) to form compounds of composition Li_xM^II_1.5–x/2PO₄ (0 ≤ x ≤ 1). A complete solid solution over the whole range of x was found for M = Ni (together with a second order structural transition from orthorhombic to monoclinic for decreasing x), whereas far smaller degrees of dopability of the Li site were found for LiCoPO₄ and LiFePO₄ (up to compositions of approx. (Li_0.8Co_0.1)CoPO₄ and approx. (Li_0.9Fe_0.05)FeO₄. In addition, the nearly stoichiometric monoclinically distorted olivine‐type compounds with compositions (Li_0.42–0.47Co_0.29–0.265)CoPO₄ and (Li_0.14–0.16Fe_0.43–0.42)FePO₄ could be identified and are described in this article.     

Doping studies of the magnetic cobaltocuprate CoSr2Y2−xCexCu2O9±δ

A structural, magnetic and electronic study of the cobaltocuprate CoSr₂Y_2−xCe_xCu₂O_9±δ (x=0.5-0.8) has been performed. All materials crystallise in the orthorhombic Cmcm symmetry space group in which chains of corner linked CoO₄ tetrahedra run parallel to the 1 1 0 direction. An antiferromagnetic transition is observed for x=0.5-0.8; T_M increases with x. A change in the dimensionality of the magnetic order occurs at x=0.8 as the interchain distance increases to a critical value. There is charge transfer between the cuprate planes and cobaltate layer as Ce doping increases, so that Co³⁺ is partially oxidised to Co⁴⁺ with a concomitant reduction in the valence of Cu. Superconductivity is not observed in any of the samples and a crossover from Mott to Efros and Shklovskii variable range hopping behaviour is evidenced as x increases from 0.5 to 0.8.     

KSbO(Ge0.32Si0.68)O4, a KTP isomorph

A structural model of potassium antimony germanate/silicate (0.32/0.68), KSbO(Ge_0.32Si_0.68)O₄, has been determined at room temperature. KSbO(Ge_0.32Si_0.68)O₄ belongs to the KTiOPO₄ (KTP) isomorphic family and is composed of SbO₆ octahedra (site symmetry and 2) arranged in helical chains bridged by (Ge/Si)O₄ tetrahedra. Germanium and silicon have a similar distribution in the crystallographically independent tetrahedra (site symmetry 2). The structure contains large cavities occupied by the K atom. Two partially occupied potassium positions have been identified 1.273 (8) Å apart, with an indication of a third potassium position between them. At room temperature, KSbO(Ge_0.32Si_0.68)O₄ crystallizes in the paraelectric phase of space group Pnan. This phase is found at elevated temperatures for almost all KTiOPO₄ isomorphic compounds and KSbO(Ge_0.32Si_0.68)O₄ is the second isomorph that is paraelectric at room temperature.     

Festkörperreaktionen in Chalkogenidsystemen. V. Verteilungsgleichgewichte zweiwertiger Übergangsmetalle in Chromthiospinell-Mischkristallen

The solid-state equilibria of the chromium thiospinel solid solutions M_xM′_1?xCr₂S₄ (M,M′ = Mn, Co, Zn, Cd), with excess binary sulfides MS and M′S or M_1?xM′_xS mixed crystals, are investigated. At 600°C the following equilibrium compositions are found: Mn_0.38Co_0.62Cr₂S₄, Mn_0.36Zn_0.64Cr₂S₄, Mn_0.64Cd_0.36Cr₂S₄, Co_0.33Zn_0.67Cr₂S₄, Co_0.68Cd_0.32Cr₂S₄, and Zn_0.75Cd_0.25Cr₂S₄. The results show that metals with small crystal radii and high tetrahedral site preference energy are preferentially incorporated into the tetrahedral sites of chromium thiospinels. With increasing temperature the composition of the quaternary spinels approach M_0.5M′_0.5Cr₂S₄. From the temperature dependence of the equilibrium constants the reaction enthalpies could be determined. The binary sulfides MS and M′S are incompletely miscible excepting the system $\text{ZnS}\text{CdS}$. At 600°C the following miscibility gaps are found: Mn_yZn_1?yS: y = 0.43 – ≈ 1.0, Mn_yCd_1?yS: y = 0.50 – >0.9, Co_yMn_1?yS: y = <0.1 – ≈ 1.0, Co_yZn_t?yS: y = 0.1 – ≈ 1.0, and Co_yCd_1?yS: y = 0.1 – ≈ 1.0. With increasing temperature the miscibility gaps, especially of the systems with CoS, get smaller. The spinel solid solutions and the $\text{ZnS}\text{CdS}$ mixed crystals obey Vegard's rule.     

Crystal structure of the thortveitite‐related M phase, (MnxZn1–x)2V2O7 (0.75 < x < 0.913): a combined synchrotron powder and single‐crystal X‐ray study

The determination of the crystal structure of the M phase, (Mn_xZn_1–x)₂V₂O₇ (0.75 < x < 0.913), in the pseudobinary Mn₂V₂O₇–Zn₂V₂O₇ system for x ≃ 0.8 shows that the previously published triclinic unit‐cell parameters for this thortveitite‐related phase do not describe a true lattice for this phase. Instead, single‐crystal X‐ray data and Rietveld refinement of synchrotron X‐ray powder data show that the M phase has a different triclinic structure in the space group P with Z = 2. As prior work has suggested, the crystal structure can be described as a distorted version of the thortveitite crystal structure of β‐Mn₂V₂O₇. A twofold superstructure in diffraction patterns of crystals of the M phase used for single‐crystal X‐ray diffraction work arises from twinning by reticular pseudomerohedry. This superstructure can be described as a commensurate modulation of a pseudo‐monoclinic basis structure closely related to the crystal structure of β‐Mn₂V₂O₇. In comparison with the distortions introduced when β‐Mn₂V₂O₇ transforms at low temperature to α‐Mn₂V₂O₇, the distortions which give rise to the M phase from the β‐Mn₂V₂O₇ prototype are noticeably less pronounced.     

Developing Intense Blue and Magenta Colors in α‐LiZnBO3: The Role of 3d‐Metal Substitution and Coordination

We describe the synthesis, crystal structures, and optical absorption spectra/colors of 3d‐transition‐metal‐substituted α‐LiZnBO₃ derivatives: α‐LiZn_1?xM^II_xBO₃ (M^II=Co^II (0<x<0.50), Ni^II (0<x≤0.05), Cu^II (0<x≤0.10)) and α‐Li_1+xZn_1?2xM^III_xBO₃ (M^III=Mn^III (0<x≤0.10), Fe^III (0<x≤0.25)). The crystal structure of the host α‐LiZnBO₃, which is both disordered and distorted with respect to Li and Zn occupancies and coordination geometries, is largely retained in the derivatives, which gives rise to unique colors (blue for Co^II, magenta for Ni^II, violet for Cu^II) that could be of significance for the development of new, inexpensive, and environmentally friendly pigment materials, particularly in the case of the blue pigments. Accordingly, this work identifies distorted tetrahedral MO₄ (M=Co, Ni, Cu) structural units, with a long M?O bond that results in trigonal bipyramidal geometry, as new chromophores for blue, magenta, and violet colors in a α‐LiZnBO₃ host. From the L*a*b* color coordinates, we found that Co‐substituted compounds have an intense blue color that is stronger than that of CoAl₂O₄ and YIn_0.90Mn_0.10O₃. The near‐infrared (NIR) reflectance spectral studies indicate that these compounds exhibit a moderate IR reflectivity that could be significant for applications as “cool pigments”.     

(CuI)P4Se4: An Adduct of Polymeric P4Se4 with CuI

Pure yellow (CuI)P₄Se₄ was prepared by reaction of stoichiometric amounts of CuI, red P, and gray Se in evacuated silica ampoules. The crystal structure was determined from single crystals at room temperature. (CuI)P₄Se₄ crystallizes in the orthorhombic system, space group Cmca with a = 14.770 (1) Å, b = 12.029 (1) Å, c = 12.449 (1) Å, V = 2211.9(6) ų, and Z = 8. The structure refinement converged to R = 0.0190 (wR = 0.0272) for 1020 independent reflections and 51 parameters. A prominent feature of the crystal structure are neutral polymeric P₄Se₄ strands which are connected by copper iodide. These strands consist of norbornane analogous P₄Se₃ cages which are linked by selenium bridges. The polymers are achiral since a mirror plane exists perpendicular to the strands. The single polymers are connected by [Cu₂I₂] units to form layers. These layers are stacked along the b axis and are connected by van der Waals-interactions only. Raman spectra of (CuI)P₄Se₄ differ significantly from Raman spectra of (CuI)₃P₄Se₄ and catena-(P₄Se₄)_x.     

Synthesis and study of cesium-containing phosphates with a β-tridymite structure

Complex phosphates CsMg_{1 ? x} M _x PO₄ (M = Mn, Co, Cu, Zn), containing cesium and metals in the oxidation state +2, have been synthesized, and their structure and thermal behavior have been studied. Continuous solid solutions (0 ?? x ?? 1) of the ??-tridymite structure type are formed in the CsMg_{1 ? x} Mn _x PO₄, CsMg_{1 ? x} Co _x PO₄, and CsMg_{1 ? x} Zn _x PO₄ systems, whereas limited solid solutions (0 ?? x ?? 0.4) are formed in the CsMg_{1 ? x} Cu _x PO₄ system. Based on DTA data, phase transitions have been revealed in the cobalt-, copper-, and zinc-containing phosphates, and the orthorhombic or monoclinic crystal system has been identified. Unit cell parameters of the solid solutions have been calculated. Thermal expansion of the CsMPO₄ phosphates has been studied.     

An interpretation of the polarized crystal spectra of Mn(II) and Co(II) in D2h symmetry

Crystals of TMAM_xM′_1?xCl₃ · 2H₂O where TMA = (CH₃)₃NH⁺ and M = Mn²⁺, M′ = Co²⁺ are strikingly pleochroic. The polarized spectra of these highly colored orthorhombic salts are reported and transition assignments are made based on D_2h symmetry. Peaks in the Mn(II) spectra are explained as electric dipole transitions while peaks in the Co(II) spectra are explained as magnetic dipole transitions.     

Synthesis and characterization of complexes of the first transition series cations with 2,2′-biimidazole and 2,2′-biimidazolate

Mononuclear [M(hfacac)₂(H₂biim)] complexes, where M = Mn^II, Fe^II, Co^II, Ni^II, Cu^II or Zn^II, hfacac = hexafluoroacetylacetonate, H₂biim = 2,2-biimidazole; dinuclear K₂[M₂(acac)₄(-biim)] (M = Cu^II or Zn^II) and tetranuclear K₂[M₄(acac)₈( ₄-biim)] (M = Co^II or Ni^II) complexes have been prepared and characterized by chemical analysis, conductance measurements, i.r., electronic and e.p.r. spectroscopies and by magnetic susceptibility measurements (in the 2–300 K range). Mn^II, Fe^II and Co^II are in a high spin state. The e.p.r. spectra of Cu^II and Mn^II compounds have been recorded.     

Ammonothermal Synthesis and Crystal Growth of the Chain-type Oxonitridosilicate Ca1+xY1–xSiN3–xOx (x > 0)

The oxonitridosilicate Ca_1+xY_1–xSiN_3–xO_x (x > 0) was synthesized in custom-built high-temperature autoclaves starting from CaH₂, intermetallic YSi and NaN₃ using supercritical ammonia as solvent at a maximum pressure of 140 MPa and temperature of 1070 K. In situ formed NaNH₂ acts as ammonobasic mineralizer and increases the solubility of the other starting materials. Air and moisture sensitive rod-shaped single crystals of the title compound with length of up to 200 μm were obtained. The crystal structure was solved and refined by single-crystal X-ray diffraction. The results are supported by powder X-ray diffraction, energy dispersive X-ray spectroscopy and lattice energy (MAPLE) calculations. Ca_1+xY_1–xSiN_3–xO_x (x > 0) is isostructural to Ca₂PN₃ and Eu₂SiN₃ and crystallizes in the orthorhombic space group Cmce (no. 64) with a = 5.331(2), b = 10.341(4), c = 11.248(4) Å and Z = 8 (R₁ = 0.0257, wR₂ = 0.0447) and contains infinite zweier single chains running along [100] which are built up from corner sharing Si(N,O)₄ tetrahedra.     

Crystal structure refinement of manganese thiogermanate Mn2GeS4

The crystal structure of Mn₂GeS₄ was solved by X-ray diffraction, on a single crystal. It has the olivine type, orthorhombic Pnma, with a = 12.776, b = 7.441, c = 6.033Å; R = 0.038 for 956 independent reflections.     

Postsynthetic Metal and Ligand Exchange in MFU‐4l: A Screening Approach toward Functional Metal–Organic Frameworks Comprising Single‐Site Active Centers

The isomorphous partial substitution of Zn²⁺ ions in the secondary building unit (SBU) of MFU‐4l leads to frameworks with the general formula [M_xZn_(5–x)Cl₄(BTDD)₃], in which x≈2, M=Mn^II, Fe^II, Co^II, Ni^II, or Cu^II, and BTDD=bis(1,2,3‐triazolato‐[4,5‐b],[4′,5′‐i])dibenzo‐[1,4]‐dioxin. Subsequent exchange of chloride ligands by nitrite, nitrate, triflate, azide, isocyanate, formate, acetate, or fluoride leads to a variety of MFU‐4l derivatives, which have been characterized by using XRPD, EDX, IR, UV/Vis‐NIR, TGA, and gas sorption measurements. Several MFU‐4l derivatives show high catalytic activity in a liquid‐phase oxidation of ethylbenzene to acetophenone with air under mild conditions, among which Co‐ and Cu derivatives with chloride side‐ligands are the most active catalysts. Upon thermal treatment, several side‐ligands can be transformed selectively into reactive intermediates without destroying the framework. Thus, at 300 °C, Co^II‐azide units in the SBU of Co‐MFU‐4l are converted into Co^II‐isocyanate under continuous CO gas flow, involving the formation of a nitrene intermediate. The reaction of Cu^II‐fluoride units with H₂ at 240 °C leads to Cu^I and proceeds through the heterolytic cleavage of the H₂ molecule.     

Structural study by X-ray diffraction, magnetic susceptibility and Mössbauer spectroscopy of the Na2Mn2(1 − x)Cd2xFe(PO4)3 (0 ≤ x ≤ 1) solid solution

Na₂Mn_{2(1 − x)}Cd_2xFe(PO₄)₃ (0 ≤ x ≤ 1) phosphates were prepared by solid state reaction and characterized by powder X-ray diffraction, magnetic susceptibility and Mössbauer spectroscopy. The X-ray diffraction patterns indicated the formation of a continuous solid solution which crystallizes in the alluaudite structural type characterized by the general formula X(2)X(1)M(1)M(2)₂(PO₄)₃. The cation distribution, deduced from a structure refinement of the x = 0, 0.5 and 1 compositions, is ordered in the X(2) sites and disordered in the remaining X(1), M(1) and M(2) sites. The magnetic susceptibility study revealed an antiferromagnetic behaviour of the studied compounds. The ⁵⁷Fe Mössbauer spectroscopy confirmed the structural results and proved the exclusive presence of Fe³⁺ ions.     

The new high-pressure borate Co7B24O42(OH)2·2 H2O—Formation of edge-sharing BO4 tetrahedra in a hydrated borate

The new borate hydrate Co₇B₂₄O₄₂(OH)₂·2 H₂O was synthesized under high-pressure/high-temperature conditions of 6 GPa and 880 °C in a Walker-type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pbam (Z=2) with the lattice parameters a=819.0(2), b=2016.9(4), c=769.9(2) pm, V=1.2717(4) nm³, R₁=0.0758, wR₂=0.0836 (all data). The new structure type of Co₇B₂₄O₄₂(OH)₂·2 H₂O is built up from corner-sharing BO₄ tetrahedra forming corrugated layers, that are interconnected among each other by two edge-sharing BO₄ tetrahedra (B₂O₆ units) forming Z-shaped channels. Interestingly, the here presented structure of Co₇B₂₄O₄₂(OH)₂·2 H₂O is closely related to the structures of M₆B₂₂O₃₉·H₂O (M=Fe, Co), which exhibit BO₄ tetrahedra in an intermediate state on the way to edge-sharing BO₄ tetrahedra.     

Geometric parameterization of the YBaCo4O7 structure type: Implications for stability of the hexagonal form and oxygen uptake

We explore the stability of the hexagonal form of MBaCo₄O₇ cobaltites in terms of geometric characteristics of the crystal structure and Global Instability Index (GII) based on the bond-valence considerations. Mismatch between an M^3+/2+ and the three-dimensional network of CoO₄ tetrahedra, whether expressed using an M ionic radii or GII, is shown to essentially determine both the temperature of structural transition to an orthorhombic modification and oxygen storage properties. A number of M cations not reported in the literature are identified to be suitable for the octahedral sites in an MBaCo₄O₇ structure.     

Hydrothermal Synthesis and Crystal Structure of a Novel 3-D Porous Lanthanum Sulfate

A new lanthanum compound with three-dimensional channels, La₂(H₂O)(SO₄)₃ has been synthesized hydrothermally by using 1,2-dizminiopnopane as a structure-directing agent (SDA). The colorless block crystals were characterized by IR, TGA, ICP and XRD. The structure was determined by single-crystal diffraction. The title compound crystallizes in the orthorhombic, P2₁2₁2₁(No. 19) with cell parameters, a = 17.095(3) ?, b = 17.331(3) ?, c = 6.8633(12) ?, V = 1659.0(8) ?³, Z = 4, R = 0.0545, wR = 0.1246. The open framework of title compound is built up by LaO₁₀, LaO₉ polyhedra and SO₄ tetrahedra, connected to form interesting eight-membered ring channels along crystallographic a axis.