Sixfold Coordination Research Articles

The role of calcium phosphates and silicates in the storage and transport of phosphorus at the upper-to-lower mantle transition: An experimental study to 25 GPa in a model peridotitic bulk composition

Calcium (Ca) phosphates are major hosts for phosphorus, halogens and incompatible trace elements in the Earth’s crust and mantle and, by supplying almost all phosphorus to the biosphere, are indispensable for sustaining life on Earth. To better understand the role of Ca-phosphates in the deep silicate Earth portion of the global phosphorus cycle at depths of the transition zone, we performed experiments in the P-T range of 15–25 GPa and 1600–2000 °C using a moderately fertile peridotite doped with 3 % synthetic β-Ca3(PO4)2 and 1 % of a trace element mix containing a range of HFSE, LILE, REEs, Cl and Br. Tuite is stable to at least 25 GPa at which pressure its upper T-stability limit is between 1700 and 1750 °C. At 15 GPa, by comparison, the upper T-stability limit is located between 1750 and 1800 °C, indicating a negative slope of the tuite-out reaction(s). Thus, tuite is stable to at least 700-km depth with a maximum T-stability close to or slightly above the average current mantle adiabat (ACMA) at 20–25 GPa and significantly above the ACMA at 15 GPa. Beyond the P-T stability limit of majoritic garnet, tuite is the principal subsolidus phosphorus carrier in the uppermost lower mantle. Beyond the P-T stability limit of tuite, phosphorus is likely to either (i) enter a Ca3(PO4)2 polymorph with an even higher density, (ii) form an entirely new phosphate phase or (iii) be accommodated in lower mantle silicates in six-fold coordination. Within the P-T range of our experiments, the phases encountered show the following trend of phosphorus contents:Pmelt>Pmajoritic garnet > Polivine ≅ Pringwoodite > Pdavemaoite ≅ Pwadsleyite > Pclinoenstatite ≅ Pbridgmanite ≅ Pferropericlase. Even when coexisting with tuite, bridgmanite and ferropericlase show phosphorus contents < 100 µg/g, and davemaoite has phosphorus contents that do not exceed 390 µg/g, testifying to the very limited phosphorus storage capacity of the lower mantle. Model calculations based on the phosphorus contents of ocean island basalts (OIBs) compared with those of mid ocean ridge basalts (MORBs) indicate that the OIB source is significantly richer in phosphorus than the MORB source and, for a wide range of OIB phosphorus contents, is likely to contain modal apatite. The relative importance of Ca-phosphates and silicates as phosphorus carriers in the peridotitic upper and uppermost lower mantle is strongly dependent upon pressure and the bulk phosphorus content. With increasing P, phosphorus is progressively transferred from Ca-phosphates to silicates with an ensuing decrease in the modal amount of the Ca-phosphates. Dependent upon the bulk phosphorus content, this may cause the Ca-phosphates to disappear before the upper-to-lower mantle boundary is reached, leaving majoritic garnet as the major phosphorus host. Breakdown of garnet will subsequently cause tuite to re-appear in the uppermost lower mantle and to resume its role of the principal subsolidus phosphorus carrier. For sufficiently high bulk phosphorus contents, tuite will remain stable throughout the transition zone, thereby maintaining phosphorus saturation in the coexisting silicates, and will eventually be joined by the tuite newly generated by garnet breakdown.

Solidification process of ABO3-type perovskites: Kinetic two-phase growth method with optimized potential

The functional properties of ABO3-type perovskite materials have garnered extensive attention, yet their solidification properties have remained challenging to investigate due to high-temperature environments and characterization limitations. In this study, molecular dynamics simulations are employed to comprehensively explore the melting, quenching, and crystal growth processes of SrTiO3 (STO) structural evolution. Through iterative fitting and optimization of ion effective charge, a set of potential functions capable of accurately simulating the high-temperature melting of STO are derived. The melting point obtained for STO (2403 K) using the two-phase coexistence method closely corresponds to the empirical value (2333 K), affirming the precision of the optimized potential. Quenching the molten STO yields an amorphous structure characterized primarily by Ti-O six-fold coordination, which increased by 13.09% when reduced to 300 K at a cooling rate of 0.1 K/ps. Notably, the results for different cooling rates revealed that slower cooling rates and lower temperatures yielded more ordered amorphous structures. To circumvent the formation of amorphous states during crystal growth of perovskite materials, we have developed a kinetic two-phase growth (KTPG) method. This approach regulates the cooling rate within a solid-liquid two-phase system, maintaining constant low supercooling at the interface to mimic STO crystal growth kinetics. Cooling at 0.01 K/ps to 1760 K leads to a notable transformation, with the percentage of Ti-O six-fold coordination reaching 90%. This signifies substantial progress in achieving crystal growth through this method, highlighting its efficacy in facilitating crystal formation from the melt phase.

Molecular insight into the initial hydration of tricalcium aluminate

Portland cement (PC) is ubiquitously used in construction for centuries, yet the elucidation of its early-age hydration remains a challenge. Understanding the initial hydration progress of tricalcium aluminate (C3A) at molecular scale is thus crucial for tackling this challenge as it exhibits a proclivity for early-stage hydration and plays a pivotal role in structural build-up of cement colloids. Herein, we implement a series of ab-initio calculations to probe the intricate molecular interactions of C3A during its initial hydration process. The C3A surface exhibits remarkable chemical activity in promoting water dissociation, which in turn facilitates the gradual desorption of Ca ions through a metal-proton exchange reaction. The dissolution pathways and free energies of these Ca ions follow the ligand-exchange mechanism with multiple sequential reactions to form the ultimate products where Ca ions adopt fivefold or sixfold coordination. Finally, these Ca complexes reprecipitate on the remaining Al-rich layer through the interface-coupled dissolution-reprecipitation mechanism, demonstrating dynamically stable inner-sphere adsorption states. The above results are helpful in unmasking the early-age hydration of PC and advancing the rational design of cement-based materials through the bottom-up approach.

Dense and high flexural strength cordierite ceramics doped with Li2O

High-strength cordierite ceramics with Li2O were fabricated by non-pressure sintering. The results showed that the addition of Li2O significantly reduced the sintering temperature and expanded the sintering range. Additionally, the mechanical strength of the samples clearly increased after Li2O doping. In particular, the sample with 0.5 wt% Li2O sintered at 1250 °C showed the best properties, with a flexural strength of 178.6 MPa and a thermal expansion coefficient of 2.1 × 10−6 °C−1. Its flexural strength is much higher than samples without Li2O and the cordierite ceramics prepared by non-pressure sintering reported in the literature. The high density of the sample (2.52 g cm−3) is the main reason for its excellent mechanical properties. Furthermore, first-principles calculations verify that Li+ dopants insert at the vacant channel of α-cordierite crystal with six-fold coordination, which may reduce the anisotropy of the thermal expansion coefficient of α-cordierite, thus improving the strength of ceramics.

Crystal structure and synchrotron X-ray powder reference pattern for the porous pillared cyanonickelate, Ni(3-amino-4,4′-bipyridine)[Ni(CN)4

The structure of Ni(3-amino-4,4′-bipyridine)[Ni(CN)4] (or known as Ni-BpyNH2) in powder form was determined using synchrotron X-ray diffraction and refined using the Rietveld refinement technique (R = 8.8%). The orthorhombic (Cmca) cell parameters were determined to be a = 14.7218(3) Å, b = 22.6615(3) Å, c = 12.3833(3) Å, V = 4131.29(9) Å3, and Z = 8. Ni-BpyNH2 forms a 3-D network, with a 2-D Ni(CN)4 net connecting to each other via the BpyNH2 ligands. There are two independent Ni sites on the net. The 2-D nets are connected to each other via the bonding of the pyridine “N” atom to Ni2. The Ni2 site is of six-fold coordination to N with relatively long Ni2–N distances (average of 2.118 Å) as compared to the four-fold coordinated Ni1–C distances (average of 1.850 Å). The Ni(CN)4 net is arranged in a wave-like fashion. The functional group, –NH2, is disordered and was found to be in the m-position relative to the N atom of the pyridine ring. Instead of having a unique position, N has ¼ site occupancy in each of the four m-positions. The powder reference diffraction pattern for Ni-BpyNH2 was prepared and submitted to the Powder Diffraction File (PDF) at the International Centre of Diffraction Data (ICDD).

Antimony Doped Hybrid Zinc Halide Crystals with Tunable Light Emission and Long‐Term Stability

AbstractAs a class of emerging photoluminescent materials, hybrid halide crystals have drawn research attention for their potential application in the fields of light‐emitting, security, and waveguide. Nevertheless, hybrid halide crystals containing antimony with long‐term stability and tunable light emission are still increasingly in demand. In this work, serial new hybrid halide crystals (BZA)2ZnCl4·2H2O:xSb3+ (x = 0–0.2, x represents the reaction ratio) and (BZA)2SbCl5 are synthesized (BZA = 2,4‐diamino‐6‐phenyl‐1,3,5‐triazine). In (BZA)2ZnCl4·2H2O:xSb3+ crystals, Sb3+ cations replace partial Zn2+ cations to form [SbCl4]− tetrahedron. Red light emission caused by the substitution of Sb3+ for Zn2+ enhances as the doping rate increases, resulting in the tunable emission from light blue to pink and finally to dark red. There are two kinds of Sb3+ in (BZA)2SbCl5 crystal. Sb(1) has a sixfold coordination with Cl to form a [Sb(1)Cl5]∞ 1D zigzag chain. Sb(2) atom adopts a fivefold coordination with Cl and is separated from each other by BZA+ cations. (BZA)2SbCl5 crystal shows bright orange‐yellow light emission with a photoluminescence quantum yield of 45%. Moreover, the organic–inorganic hybrid metal halide crystals containing antimony have excellent long‐term stability, with phase and luminescence keeping nearly unchanged after more than six months in ambient air.

Structure and chemical durability improvement of alkali silicate glass by zirconium dioxide and erbium oxide addition

Glass structure tailoring of alkali silicate glasses by addition of ZrO2 and Er2O3 is found to enhance the chemical durability of glasses. ZrO2 (x ranged between 5 mol% to 15 mol%) and Er2O3 (y ranged between 0.5 mol% to 1.5 mol%) were used to replace SiO2 and Na2O, respectively, in the glasses with the nominal composition of 10Li2O-(15-y)Na2O-10CaO-(65-x)SiO2-xZrO2-y Er2O3. The samples were prepared by conventional melt quenching technique. The structures of produced glasses were examined by X-ray absorption spectroscopy (XAS) and Raman spectroscopy. XAS spectra demonstrated that the oxidation numbers of Zr and Er ions were +4 and +3, respectively. The chemical environment around both cations was six-fold coordination. In addition, Raman spectra demonstrated that the Zr4+ ions formed the Q4(Zr) structure, which caused the reduction of non-bridging oxygen. In case of the Er3+ ions, the formation of the Si-O-Er bonds was explained from the Raman study. The chemical durability of glass was determined from Na+ ions leaching values. In pH 7 solution, the leached Na+ ions reduced from 25.67% to 21.43% and from 22.50% to 20.49% as a function of concentration of ZrO2 (x = 5 mol% to 15 mol%) and Er2O3 (y = 0.5 mol% to 1.5 mol%), respectively. As the results, the chemical durability of the ZrO2-containing and Er2O3-containing glasses were significantly improved due to charge compensated mechanism and enhancing network rigidity by increasing cation field strength. Moreover, the micro-hardness (580 HV to 837 HV) and density (2.54 g⸳cm-3 to 2.82 g⸳cm-3) also displayed an increased tendency with larger concentration of ZrO2 and Er2O3.

An X-ray and Neutron Scattering Study of Aqueous MgCl2 Solution in the Gigapascal Pressure Range

The structure of electrolyte solutions under pressure at a molecular level is a crucial issue in the fundamental science of understanding the nature of ion solvation and association and application fields, such as geological processes on the Earth, pressure-induced protein denaturation, and supercritical water technology. We report the structure of an aqueous 2 m (=mol kg−1) MgCl2 solution at pressures from 0.1 MPa to 4 GPa and temperatures from 300 to 500 K revealed by X-ray- and neutron-scattering measurements. The scattering data are analyzed by empirical potential structure refinement (EPSR) modeling to derive the pair distribution functions, coordination number distributions, angle distributions, and spatial density functions (3D structure) as a function of pressure and temperature. Mg2+ forms rigid solvation shells extended to the third shell; the first solvation shell of six-fold octahedral coordination with about six water molecules at 0 GPa transforms into about five water molecules and one Cl− due to the formation of the contact ion pairs in the GPa pressure range. The Cl− solvation shows a substantial pressure dependence; the coordination number of a water oxygen atom around Cl− increases from 8 at 0.1 MPa/300 K to 10 at 4 GPa/500 K. The solvent water transforms the tetrahedral network structure at 0.1 MPa/300 K to a densely packed structure in the GPa pressure range; the number of water oxygen atoms around a central water molecule gradually increases from 4.6 at 0.1 MPa/298 K to 8.4 at 4 GPa/500 K.

First-principles investigations of the crystal and electronic structures, dynamical and mechanical stabilities, Born effective charges and dielectric permittivities of a novel tetragonal zirconia

In this paper, a novel tetragonal ZrO2 phase has been predicted from first-principles calculations. The detailed crystal structural analysis shows that the tetragonal ZrO2 has a space group I41/amd (D4h19, No. 141) with 4 formula units per unit cell and 16 symmetry operations as well as six-fold cation coordination. The Zr atoms occupy 4a Wyckoff positions (0, 1/2, 1/4) and (1/2, 1/2, 1/2) and the O atoms occupy 8e Wyckoff positions (0, 0, z+1/8), (0, 1/2, z+3/8), (1/2, 0, -z+5/8) and (1/2, 1/2, -z+3/8) with z = 0.0761. The electronic structures, dynamical and mechanical stabilities investigations show the tetragonal ZrO2 is dynamical and mechanical stable as well as with a large direct band gap of 3.9015eV at Γ point. The phonon dispersion is divided into two regions: the low frequency part (0–8.6240 THz) and the high frequency part (10.3453–18.4034 THz) with a separation gap of 1.7213 THz. The magnitudes of Born effective charges are greater than the nominal chemical valences of +4 and −2 for Zr and O ions, respectively, reflecting a strong dynamic charge transfer from Zr to O atoms and thus a p-d hybridized Zr–O ionic bond. A diagonal and anisotropic static dielectric permittivity εij0 is obtained between ab-plane ε110=ε220=17.80 and along c axis ε330=14.77.

Comparison of Empirical Zn2+ Models in Protein–DNA Complexes

Zinc ions are the second most abundant ions found in humans. Their role in proteins can be merely structural but also catalytic, owing to their transition metal character. Modelling their geometric–coordination versatility by empirical force fields is, thus, a challenging task. In this work, we evaluated three popular models, specifically designed to represent zinc ions with regard to their capability of preserving structural integrity. To this end, we performed molecular dynamics simulations of two zinc-containing protein–DNA complexes, which differed in their zinc coordination, i.e., four cysteines or two cysteines and two histidines. The most flexible non-bonded 12-6-4 Lennard–Jones-type model shows a preference for six-fold coordination of the Zn2+-ions in contradiction to the crystal structure. The cationic dummy atom model favours tetrahedral geometry, whereas the bonded extended zinc AMBER force field model, by construction, best preserves the initial geometry of a regular or slightly distorted tetrahedron. Our data renders the extended zinc AMBER force field the best model for structural zinc ions in a given geometry. In more complicated cases, though, more flexible models may be advantageous.

Molecularly Designed Ion-Imprinted Nanoparticles for Real-Time Sensing of Cu(II) Ions Using Quartz Crystal Microbalance.

A molecularly designed imprinting method was combined with a gravimetric nanosensor for the real-time detection Cu(II) ions in aqueous solutions without using expensive laboratory devices. Thus, 1:1 and 2:1 mol-ratio-dependent coordination modes between Cu(II), N-methacyloly-L histidine methyl ester (MAH) functional monomer complexes, and their four-fold and six-fold coordinations were calculated by means of density functional theory molecular modeling. Cu(II)-MIP1 and Cu(II)-MIP2 nanoparticles were synthesized in the size range of 80-100 nm and characterized by SEM, AFM and FTIR. Cu(II)-MIP nanoparticles were then conducted to a quartz crystal microbalance sensor for the real-time detection of Cu(II) ions in aqueous solutions. The effects of initial Cu(II) concentration, selectivity, and imprinting efficiency were investigated for the optimization of the nanosensor. Linearity of 99% was obtained in the Cu(II) ion linear concentration range of 0.15-1.57 µM with high sensitivity. The LOD was obtained as 40.7 nM for Cu(II)-MIP2 nanoparticles. The selectivity and the imprinting efficiency of the QCM nanosensor were obtained significantly in the presence of competitive ion samples (Co(II), Ni(II), Zn(II), and Fe(II)). The results are promising for sensing Cu(II) ions as environmental toxicants in water by combining molecularly designed ion-imprinted nanoparticles and a gravimetric sensor.

Columbite supergroup of minerals: nomenclature and classification

AbstractThe columbite supergroup is established. It includes five mineral groups (ixiolite, wolframite, samarskite, columbite and wodginite) and one ungrouped species (lithiotantite). The criteria for a mineral to belong to the columbite supergroup are: the general stoichiometry MO2; the crystal structure based on the hexagonal close packing (hcp) of anions (or close to it); the six-fold coordination number of M-type cations (augmented to eight-fold in the case of slight distortion of hcp); and the presence of zig-zag chains of edge-sharing M-centred polyhedra. The ixiolite-type structure is considered as an aristotype with the space group Pbcn, the smallest unit cell volume, and the basic vectors a0, b0 and c0. Based on the multiplying of the ixiolite-type unit cell the following derivatives are distinguished: ixiolite type [ixiolite-group minerals; a = a0,b = b0 and c = c0; space group Pbcn; the members are ixiolite-(Mn2+), ixiolite-(Fe2+), scrutinyite, seifertite and srilankite]; wolframite type [wolframite-group minerals, ordered analogues of the ixiolite type with a = a0,b = b0 and c = c0; P2/c; the members are ferberite, hübnerite, huanzalaite, sanmartinite, heftetjernite, nioboheftetjernite, rossovskyite and riesite]; samarskite type [samarskite-group minerals; a = 2a0, b = b0 and c = c0; P2/c; the members are samarskite-(Y), ekebergite and shakhdaraite-(Y)]; columbite type [columbite-group minerals; a = 3a0,b = b0 and c = c0; Pbcn; the members are columbite-(Fe), columbite-(Mn), columbite-(Mg), tantalite-(Fe), tantalite-(Mn), tantalite-(Mg), fersmite, euxenite-(Y), tanteuxenite-(Y) and uranopolycrase]; and wodginite type [wodginite-group minerals; a = 2a0,b = 2b0 and c = c0; C2/c; the members are wodginite, ferrowodginite, titanowodginite, ferrotitanowodginite, tantalowodginite, lithiowodginite and achalaite]. Samarskite-(Yb), ishikawaite and calciosamarskite are insufficiently studied, tentatively considered as possible members of the samarskite supergroup. Qitianlingite, yttrocolumbite-(Y), yttrotantalite-(Y) and yttrocrasite-(Y) are questionable and need further studies. Polycrase-(Y) is discredited as identical to euxenite-(Y). Ixiolite has been renamed as ixiolite-(Mn2+), with the end-member formula (Ta2/3Mn2+1/3)O2. Ta- and Nb-dominant analogues of ixiolite with different schemes of charge balancing have the end-member formulae (M15+0.5M23+0.5)O2, M15+2/3M22+1/3)O2, M15+0.75M2+0.25)O2 or M15+0.8□0.2)O2 and the root name ‘ixiolite’ (for M1 = Ta) or ‘nioboixiolite’ (for M1 = Nb).

Newly detected shock-induced high-pressure phases formed in amphibolite clasts of the suevite breccia (Ries impact crater, Germany): Liebermannite, kokchetavite, and other ultrahigh-pressure phases

Amphibolite clasts in the suevite of the Ries impact crater contain shock-induced melt veins (SMVs) with high-pressure phases such as majoritic garnet, jadeitic clinopyroxene and others. In addition, heat conduction from hot SMVs into adjacent rock portions locally produced further high P–T melt pools. These melts were preferentially generated in rock domains, where the SMVs cross older (‘pre-Ries’) veinlets with analcime or prehnite and larger grains of sericitized plagioclase. Melting of such chemically different local bulk systems (Na-, Ca-, Ca-Na- and K-Na-rich) was facilitated by low solidus temperatures of the original secondary OH-bearing phases. From the resulting shock-induced melts, liebermannite, kokchetavite, jadeite, nonstoichiometric and albitic jadeite, grossular, vuagnatite, lawsonite + coesite, and clinozoisite crystallized during pressure release. Vuagnatite is now proven to be a genuine high-pressure phase. Its ubiquitous distance of 20–35 μm from the hot shock veins suggests a temperature sensitivity typical for an OH-bearing phase. In local Na-rich melts albitic jadeite appears instead of the assemblage jadeite + SiO2. Liebermannite, a dense polymorph of K-feldspar was identified by Raman spectroscopy. After stishovite, liebermannite constitutes the second known high-pressure phase in the Ries that contains silicon exclusively in six-fold coordination. The KAlSi3O8-polymorph kokchetavite was formed in alkali-rich melt glasses. Pressure and temperature values in the range of about 8–11 GPa and ~ 800–1100 °C were estimated from the chemical compositions of locally occurring majoritic garnets (Si = 3.21–3.32 and 3.06–3.10 apfu), respectively, and the presence of fine-grained aggregates of lawsonite and coesite. Generally, the neighboring areas of the veins are characterized by a sequence of variable high-pressure phases documenting strongly falling P–T conditions with increasing distance from the vein. These novel features enlighten the dynamic event during passage of a shock wave.

Cation speciation, compactness, and structure‐property correlations in manganese aluminosilicate glasses

AbstractWe report on the elastic properties of xMnO‐Al2O3‐(6‐x)SiO2 manganese aluminosilicate glasses, in which pronounced exchange coupling and antiferromagnetic interaction occurs among the paramagnetic Mn2+ ions. X‐ray absorption reveals a Mn‐O bond length of ∼2.1 Å, and a distance of ∼3 Å between Mn2+ ions in sixfold coordination, further corroborated by electron paramagnetic resonance and dynamic photoluminescence spectroscopy. This indicates the presence of edge‐sharing MnO6 units, in resemblance to edge‐sharing MnO8 in the crystalline Spessartine garnet Mn3Al2[SiO4]3. We argue that these cluster species have a profound effect on material stiffness: the compact structure of manganese aluminosilicate glasses enables a Young's modulus in the 100 GPa range and a Poisson's ratio of about 0.3. This exceeds the compositional trend with cation field strength observed for other aluminosilicate glasses.

Density Functional‐Based Tight‐Binding Simulations of Pristine and Aluminum‐Modified Silica

Using self-consistent density functional tight-binding simulations it is shown that Aluminum (Al) content in amorphous silica (a-SiO2) changes its ideal microscopic structure in a manner compatible to densification. Similar to the structure of pressure-densified a-SiO2, the Al-modified a-SiO2 comprises a network of Silicon (Si)-centered tetrahedra as well as unquenchable pentahedra and, to a smaller extent, hexahedra coordination defects. Al itself acts not only as a network former, with fourfold coordination, but also as a center for fivefold and sixfold coordination defects. Al content promotes densification since it shifts the potential energy minima at densities larger than in their pristine counterpart. Calculations uncover that Young's modulus (Y) and static dielectric constants (ε0) can be effectively doubled through densification. Oxygen starvation promotes network polymerization, which further increases Y and ε0. However, the small rings formation through Si─Si bonding and presence of undercoordinated Si introduce electronic states in the electronic band gap. The results provide guidance for the bottom-up design of amorphous silica with tunable microscopic structure and properties desirable for advancing electronic applications.

Vibrational properties of SrVO2H with large spin-phonon coupling

The antiferromagnetic transition metal oxyhydride ${\mathrm{SrVO}}_{2}\mathrm{H}$ is distinguished by its stoichiometric composition and an ordered arrangement of H atoms. The tetragonal structure is related to the cubic perovskite and consists of alternating layers of ${\mathrm{VO}}_{2}$ and SrH. ${d}^{2}$ V(III) attains a sixfold coordination by four O and two H atoms. The latter are arranged in a trans fashion, which produces H--V--H chains along the tetragonal axis. Here, we investigate the vibrational properties of ${\mathrm{SrVO}}_{2}\mathrm{H}$ by inelastic neutron scattering and infrared spectroscopy combined with phonon calculations based on density functional theory. The H-based vibrational modes divide into a degenerate bending motion perpendicular to the H--V--H chain direction and a highly dispersed stretching motion along the H--V--H chain direction. The bending motion, with a vibrational frequency of approximately 800 ${\mathrm{cm}}^{\ensuremath{-}1}$, is split into two components separated by about 50 ${\mathrm{cm}}^{\ensuremath{-}1}$, owing to the doubled unit cell from the antiferromagnetic structure. Interestingly, spin-phonon coupling stiffens the H-based modes by $50\ensuremath{-}100\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ although super-exchange coupling via H is very small. Frequency shifts of the same order of magnitude also occur for V--O modes. It is inferred that ${\mathrm{SrVO}}_{2}\mathrm{H}$ displays the hitherto largest recognized coupling between magnetism and phonons in a material.

Effects of Transition Metal Ions on the Colour of Blue-Green Beryl

This study reports the effects of transition metal ions on the colour of blue-green beryl. Industrial cameras were used to measure colour in the CIELAB colour space. X-ray fluorescence (XRF), X-ray diffraction (XRD), infrared spectroscopy (IR), and ultraviolet-visible (UV–vis) spectroscopy were used for characterization. The d–d transition of Fe3+ with sixfold coordination, the O2−→Fe3+ charge transfer, and the charge transition of binuclear metal M–M complexes formed by [Fe2(OH)4]2+ in the channel caused a yellow tone, whereas the charge transfer of Fe2+/Fe3+ with sixfold coordination caused a blue-green tone. The chroma of blue-green beryl was negatively correlated with the ratio of Cs+Mn to Fe contents. The lightness of blue-green beryl was negatively correlated with the total content of transition metal ions.

Structural Variations across Wolframite Solid Solutions, (Fe,Mn)WO4

The crystal structure of four samples from natural wolframite solid solutions, (Fe,Mn)WO4, was obtained with synchrotron high-resolution powder X-ray diffraction (HRPXRD) data, Rietveld refinements, space group P2/c, and Z = 2. Wolframite solid solutions extend from ferberite (FeWO4) to hübnerite (MnWO4). The W and (Mn,Fe) cations are in six-fold coordination. This study shows that the unit-cell parameters, a, b, c, and β angle, vary linearly with the unit-cell volume, V, across the wolframite series. The average &lt;Mn,Fe–O&gt; distance increases linearly because of larger Mn2+ (0.83 Å) replacing smaller Fe2+ (0.78 Å) cations, whereas the average &lt;W–O&gt; distance increases slightly because of the higher effective charge of the smaller Fe2+ cation. The distortions of the two types of polyhedra across the series are discussed.

(μ-2,2',2'',2'''-{[Pyrazine-2,3,5,6-tetra-yltetra-kis(methyl-ene)]tetra-kis(sulfanedi-yl)}tetra-acetato)bis-[aqua-nickel(II)] hepta-hydrate.

Reaction of the ligand 2,2',2'',2'''-{[pyrazine-2,3,5,6-tetra-yltetra-kis-(methyl-ene)]tetra-kis-(sulfanedi-yl)}tetra-acetic acid (H4L1), with NiCl2 leads to the formation of a binuclear complex, (μ-2,2',2'',2'''-{[pyrazine-2,3,5,6-tetra-yltetra-kis-(methyl-ene)]tetra-kis-(sulfanedi-yl)}tetra-acetato-κ5 O,S,N 1,S',O':κ5 O'',S'',N 4,S''',O''')bis[aqua-nickel(II)] hepta-hydrate, {[Ni2(C16H16N2O8S4)(H2O)2]·7H2O} (I). It crystallizes with two half mol-ecules in the asymmetric unit. The complete mol-ecules are generated by inversion symmetry, with the center of the pyrazine rings being located at crystallographic centres of inversion. The ligand coordinates two NiII ions in a bis-penta-dentate manner and the sixfold coordination sphere of each nickel(II) atom (NiS2O3N) is completed by a water mol-ecule. The complex crystallized as a hepta-hydrate. The binuclear complexes are linked by Owater-H⋯Ocarbon-yl hydrogen bonds, forming layers parallel to the (101) plane. This layered structure is additionally stabilized by weak C-H⋯O hydrogen bonds. Further O-H⋯O hydrogen bonds involving binuclear complexes and solvent water mol-ecules, together with weak C-H⋯S hydrogen bonds, link the layers to form a supra-molecular framework.

Three metal(II) complexes constructed using the 2-(1H-benzo[d]imidazol-2-yl)quinoline ligand

Abstract 2-(1H-benzo[d]imidazol-2-yl)quinoline (BQ) as ligand and three coordination compounds of formula {Zn(BQ)Cl2} (1), {Pb(BQ)Cl2} n (2) and {[Cu(BQ)2(OC(O)CH3)]OC(O)CH3 · CH3COOH} (3) have been synthesized and fully characterized. The complexes crystallize in triclinic space group P 1 ‾ $P&amp;#x203e;{1}$ . In complexes 1 and 2, the coordination geometry is a distorted tetrahedral environment around the zinc center and a distorted sixfold coordination geometry around the lead center, respectively. In complex 3 the central Cu(II) center is in a trigonal bipyramidal coordination geometry. The Cu(II) ion is surrounded by two bidentate 2-(2′-quinolyl)benzimidazole (BQ) ligands and one coordinated acetate molecule. One further acetate anion associated by a strong hydrogen bond with a molecule of acetic acid balances the charge of the compound.