Large magnetic anisotropy of a decorated spin-chain system K2Co3(MoO4)3(OH)2.

The magnetic structure of K2Co3(MoO4)3(OH)2 is studied in detail. The material has a half-sawtooth one-dimensional (1-D) structure containing two unique Co2+ ions, one in the chain backbone and one on the apex of the sawtooth creating a series of isosceles triangles along the b-axis. These triangles can be a source of magnetic frustration. The ability to grow large single crystals enables detailed magnetic measurements with the crystals oriented in a magnetic field along the respective axes. It has a Curie-Weiss temperature θCW of 5.3(2) K with an effective magnetic moment of 4.8(3)µB/Co. The material is highly anisotropic with a sharp antiferromagnetic ordering transition at 7 K with a metamagnetic transition at 2 kOe. Neutron diffraction was used to determine the magnetic structure and revealed a magnetic structure with canted spins along the backbone of the chain while spins along the sawtooth caps maintained a colinear orientation, arranging antiferromagnetically relative to the backbone spins. The parallel chains arrange antiferromagnetically relative to each other along the c-axis and ferromagnetically along the a-axis.

Enhanced radioluminescence of yttrium pyrosilicate nanoparticles via rare earth multiplex doping.

A series of multi-doped yttrium pyrosilicate (YPS) nanoparticles were synthesized using a high temperature multi-composite reactor, and used to explore the radioluminescent properties that have potential for biological applications. The luminescent activators explored in this work were cerium, terbium, and europium. A series of mono-doped YPS nanoparticles were synthesized that have optical and X-ray luminescent properties that span the entire visible spectrum. Energy transfer experiments were investiagted to increase the photo- and X-ray luminescence of terbium and europium. Cerium was used as a sensitizer for terbium where X-ray luminescence was enhanced. Similar results were also obtained using cerium as a sensitizer and terbium as an energy bridge for europium. By leveraging different energy transfer mechanisms X-ray luminescence can be enhanced for YPS nanoparticles.

X-ray excited luminescence spectroscopy and imaging with NaGdF4:Eu and Tb.

X-ray excited optical luminescence from nanophosphors can be used to selectively generate light in tissue for imaging and stimulating light-responsive materials and cells. Herein, we synthesized X-ray scintillating NaGdF4:Eu and Tb nanophosphors via co-precipitate and hydrothermal methods, encapsulated with silica, functionalized with biotin, and characterized by X-ray excited optical luminescence spectroscopy and imaging. The nanophosphors synthesized by co-precipitate method were ∼90 and ∼106 nm in diameter, respectively, with hydrothermally synthesized particles showing the highest luminescence intensity. More importantly, we investigated the effect of thermal annealing/calcination on the X-ray excited luminescence spectra and intensity. At above 1000 °C, the luminescence intensity increased, but particles fused together. Coating with a 15 nm thick silica shell prevented particle fusion and enabled silane-based chemical functionalization, although luminescence decreased largely due to the increased mass of non-luminescent material. We observed an increase in luminesce intensity with temperature until at 400 °C. At above 600 °C, NaGdF4:Eu@SiO2 converts to NaGd9Si6O26:Eu, an X-ray scintillator brighter than annealed NPs at 400 °C and dimmer than NPs synthesized using the hydrothermal method. The particles generate light through tissue and can be selectively excited using a focused X-ray source for imaging and light generation applications. The particles also act as MRI contrast agents for multi-modal localization.

Development of dispersible radioluminescent silicate nanoparticles through a sacrificial layer approach.

X-rays offer low tissue attenuation with high penetration depth when used in medical applications and when coupled with radioluminescent nanoparticles, offer novel theranostic opportunities. In this role, the ideal scintillator requires a high degree of crystallinity for an application relevant radioluminescence, yet a key challenge is the irreversible aggregation of the particles at most crystallization temperatures. In this communication, a high temperature multi-composite reactor (HTMcR) process was successfully developed to recrystallize monodisperse scintillating particulates by employing a core-multishell architecture. The core-shell morphology of the particles consisted of a silica core over-coated with a rare earth (Re = Y3+, Lu3+, Ce3+) oxide shell. This core-shell assembly was then encapsulated within a poly(divinylbenzene) shell which was converted to glassy carbon during the annealing & crystallization of the silica/rare earth oxide core-shell particle. This glassy carbon acted as a delamination layer and prevented the irreversible aggregation of the particles during the high temperature crystallization step. A subsequent low temperature annealing step in an air environment removed the glassy carbon and resulted in radioluminescent nanoparticles. Two monodisperse nanoparticle systems were synthesized using the HTMcR process including cerium doped Y2Si2O7 and Lu2Si2O7 with radioluminescence peaks at 427 and 399 nm, respectively. These particles may be employed as an in vivo light source for a noninvasive X-ray excited optogenetics.

Chemistry of Metal Silicates and Germanates: The Largest Metal Polygermanate, K11Mn21Ge32O86(OH)9(H2O), with a 76 Å Periodic Lattice.

An examination of manganese silicates and germanates revealed unusual structural motifs and extremely different chemistries, with identical hydrothermal reactions forming K2Mn2Si3O9 versus K11Mn21Ge32O86(OH)9(H2O). The germanate is exceptional in both its c-axis length (exceeding 76 Å) and unit cell volume (nearly 18000 Å3), the largest known polygermanate structure to our knowledge.

Single crystal neutron and magnetic measurements of Rb2Mn3(VO4)2CO3 and K2Co3(VO4)2CO3 with mixed honeycomb and triangular magnetic lattices.

Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I, Rb2Mn3(VO4)2CO3, crystallizes in the trigonal crystal system in the space group P3[combining macron]1c, and compound II, K2Co3(VO4)2CO3, crystallizes in the hexagonal space group P63/m. Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO6 octahedra and MO5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c-axis through tetrahedral [VO4] groups. The MO5 units are connected with each other by carbonate groups in the ab-plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO6-honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO5 triangular lattice ordered below 2.3 K in a colinear 'up-up-down' fashion, followed by a planar 'Y' type magnetic structure. K2Co3(VO4)2CO3 (II) exhibits a canted antiferromagnetic ordering below TN = 8 K. The Curie-Weiss fit (200-350 K) gives a Curie-Weiss temperature of -42 K suggesting a dominant antiferromagnetic coupling in the Co2+ magnetic sublattices.

Alkali Transition-Metal Molybdates: A Stepwise Approach to Geometrically Frustrated Systems.

Materials with triangular arrangements of transition metal ions are of great interest for their complex magnetism resulting from geometric frustration. This paper describes the stepwise formation of kagome lattices of open shell transition-metal ions from half-delta chains to delta/sawtooth chains, and finally kagome nets. The systems can be viewed as a testbed for magnetic studies since a variety of spin states can be introduced across the same structure type, and progress through increasing levels of structural complexity and dimensionality. The synthetic and structural development of this continuum is studied here in well-formed single crystals of A2 M3 (MoO4 )3 (OH)2 (A=K, Rb; M=Mn, Co), CsM2 (MoO4 )2 (OH) (M=Mn, Fe, Co, Zn), and KM3 (MoO4 )2 O(OH) (M=Mn).

Observation of a Large Magnetic Anisotropy and a Field-Induced Magnetic State in SrCo(VO4)(OH): A Structure with a Quasi One-Dimensional Magnetic Chain.

A new member of the descloizite family, a cobalt vanadate, SrCo(VO4)(OH), has been synthesized as large single crystals using high-temperature and high-pressure hydrothermal methods. SrCo(VO4)(OH) crystallizes in the orthorhombic crystal system in space group P212121 with the following unit cell parameters: a = 6.0157(2) Å, b = 7.645(2) Å, c = 9.291(3) Å, V = 427.29(2) Å3, and Z = 4. It contains one-dimensional Co-O-Co chains of edge-sharing CoO6 octahedra along the a-axis connected to each other via VO4 tetrahedra along the b-axis forming a three-dimensional structure. The magnetic susceptibility of SrCo(VO4)(OH) indicates an antiferromagnetic transition at 10 K as well as unusually large spin orbit coupling. Single-crystal magnetic measurements in all three main crystallographic directions displayed a significant anisotropy in both temperature- and field-dependent data. Single-crystal neutron diffraction at 4 K was used to characterize the magnetically ordered state. The Co2+ magnetic spins are arranged in a staggered configuration along the chain direction, with a canting angle that follows the tipping of the CoO6 octahedra. The net magnetization along the chain direction, resulting in ferromagnetic coupling of the a-axis spin components in each chain, is compensated by an antiferromagnetic interaction between nearest neighbor chains. A metamagnetic transition appears in the isothermal magnetization data at 2 K along the chain direction, which seems to correspond to a co-alignment of the spin directions of the nearest neighbor chain. We propose a phenomenological spin Hamiltonian that describes the canted spin configuration of the ground state and the metamagnetic transition in SrCo(VO4)(OH).

One-Pot Absolute Stereochemical Identification of Alcohols via Guanidinium Sulfate Crystallization.

A novel technique for the absolute stereochemical determination of alcohols has been developed that uses crystallization of guanidinium salts of organosulfates. The simple one-pot, two-step process leverages facile formation of guandinium organosulfate single crystals for the straightforward determination of the absolute stereochemistry of enantiopure alcohols by means of X-ray crystallography. The strong hydrogen bonding network drives the stability of the crystal lattice and allows for a diverse range of organic alcohol substrates to be analyzed.

Hydrothermal synthesis and structural characterization of several complex rare earth tantalates: Ln2TaO5(OH) (Ln = La, Pr) and Ln3Ta2O9(OH) (Ln = Pr, Nd).

Reactions are reported of early rare earth oxides, RE2O3 (RE = La, Pr, Nd) with Ta2O5 under hydrothermal conditions (650 °C, 1.5 kbar) in concentrated aqueous hydroxide (20-30 M KOH) as a mineralizer. Under various stoichiometries several members of two new structure types were isolated, Ln2TaO5(OH) (Ln = La, Pr) and Ln3Ta2O9(OH) (Ln = Pr, Nd). The analogous niobate La2NbO5(OH) was also obtained. Both structure types were characterized by single crystal X-ray diffraction and contain pentavalent tantalatum oxide octahedra and complex rare earth oxide frameworks. The Ln2TaO5(OH) structure type contains Ln-O8 and Ln-O9 building blocks and TaO6 octahedra in a 3-D framework. It contains a 3-D rare earth oxide framework formed by from zig-zag chains of rare earth oxides linking sheets of rare earth oxides. The tantalates form edge-shared Ta2O10 dimers occupying gaps in the rare earth oxide frameworks. The structure of Ln3Ta2O9(OH) contains two types of 2-D rare earth oxide slabs built of seven and eight coordinate rare earth metals. The tantalate units form 2-D slabs through a multiple corner-sharing scheme of TaO6 octahedra. The Ln3Ta2O9(OH) structure type has an interesting close structural relationship to the previously reported rare earth titanate La5Ti4O15(OH), which is discussed. The presence of hydroxide in the lattice is confirmed by IR spectroscopy and the H atom locations are assigned unambiguously using bond valence sums.

Magnetic Ground State Crossover in a Series of Glaserite Systems with Triangular Magnetic Lattices.

The magnetic properties are reported for three members of the glaserite series of compounds, Na2BaM(VO4)2, M = Mn, Mn0.6Co0.4, and Co. Large single crystals are grown using a high-temperature hydrothermal synthesis method. This structure type exhibits a triangular magnetic lattice in which M2+O6 octahedra are interconnected with nonmagnetic (VO4)3- groups. All the structures crystallize at room temperature with rigid trigonal symmetry (space group P3̅ m1); however, at lower temperatures both Na2BaMn(VO4)2 and Na2BaMn0.6Co0.4(VO4)2 undergo a structural transition to lower symmetry (monoclinic, C2/ c). The bulk magnetic measurements indicate that Mn- and Co-structures are antiferromagnetic and ferromagnetic, respectively. Na2BaMn0.6Co0.4(VO4)2 does not show any long-range ordering down to 0.5 K, although a broad heat capacity anomaly near 1.2 K suggests short-range magnetic order or freezing into a spin-glass-like state related to the chemical disorder and resulting competing magnetic interactions. The magnetic structures of Na2BaMn(VO4)2 and Na2BaCo(VO4)2 were determined using neutron powder diffraction. At zero magnetic field, Na2BaMn(VO4)2 possesses an antiferromagnetic structure with the moments ordered in a Néel-type arrangement and aligned along the C4 axis of the octahedra. Under applied magnetic field at 0.3 K, the evolution of the magnetic structure toward a fully polarized state is observed. Na2BaCo(VO4)2 represents a ferromagnetic (FM) magnetic structure with Co moments aligned parallel to the c-axis direction. The relationships between these structures and magnetic properties are discussed.

Organic Fluorophore Coated Polycrystalline Ceramic LSO:Ce Scintillators for X-ray Bioimaging.

The current effort demonstrates that lutetium oxyorthosilicate doped with 1-10% cerium (Lu2SiO5:Ce, LSO:Ce) radioluminescent particles can be coated with a single dye or multiple dyes and generate an effective energy transfer between the core and dye(s) when excited via X-rays. LSO:Ce particles were surface modified with an alkyne modified naphthalimide (6-piperidin-1-yl-2-prop-2-yn-1-yl-1 H-benzo[ de]isoquinoline-1,3-(2 H)-dione, AlNap) and alkyne modified rhodamine B ( N-(6-diethylamino)-9-{2-[(prop-2-yn-1-yloxy)carbonyl]phenyl}-3 H-xanthen-3-ylidene)- N-ethylethanaminium, AlRhod) derivatives to tune the X-ray excited optical luminescence from blue to green to red using Förster Resonance Energy Transfer (FRET). As X-rays penetrate tissue much more effectively than UV/visible light, the fluorophore modified phosphors may have applications as bioimaging agents. To that end, the phosphors were incubated with rat cortical neurons and imaged after 24 h. The LSO:Ce surface modified with AlNap was able to be successfully imaged in vitro with a low-output X-ray tube. To use the LSO:Ce fluorophore modified particles as imaging agents, they must not induce cytotoxicity. Neither LSO:Ce nor LSO:Ce modified with AlNap showed any cytotoxicity toward normal human dermal fibroblast cells or mouse cortical neurons, respectively.

Single Crystals of Cubic Rare-Earth Pyrochlore Germanates: RE2Ge2O7 (RE = Yb and Lu) Grown by a High-Temperature Hydrothermal Technique.

Large single crystals of Yb2Ge2O7 in the cubic Fd3̅ m space group, are synthesized and characterized from a high-temperature hydrothermal method (650°C/200 MPa in 1 M KF). The cubic phase displays spin frustration and possibly nonclassical quantum-spin behavior at low temperature. This is the first report of single crystals of this important phase of size and quality suitable for single-crystal neutron diffraction.

High temperature hydrothermal synthesis of rare-earth titanates: synthesis and structure of RE5Ti4O15(OH) (RE = La, Er), Sm3TiO5(OH)3, RE5Ti2O11(OH) (RE = Tm-Lu) and Ce2Ti4O11.

Reactions of rare-earth oxides with TiO2 were performed in high temperature (650-700 °C) hydrothermal fluids. Two different mineralizer fluids were examined, 20 M KOH and 30 M CsF, and their respective products analyzed. When concentrated KOH fluids were used, single crystals of a variety of new OH- containing species were isolated and structurally characterized: RE5Ti4O15(OH) (RE = La, Er) I, Sm3TiO5(OH)3II and RE5Ti2O11(OH) (RE = Tm-Lu) III. La5Ti4O15(OH) I crystallizes in the orthorhombic space group Pnnm with unit cell dimensions of a = 30.5152(12) Å, b = 5.5832(2) Å, c = 7.7590(3) Å and V = 1321.92(9) Å3, Z = 4. Sm3TiO5(OH)3II crystallizes in the monoclinic space group P21/m with unit cell parameters of a = 5.6066(2) Å, b = 10.4622(4) Å, c = 6.1258(2) Å and ß = 104.7390(10)°, V = 347.50(2) Å3, Z = 2. Lu5Ti2O11(OH) III crystallizes in the monoclinic space group C2/m with unit cell dimensions of a = 12.1252(9) Å, b = 5.8243(4) Å, c = 7.0407(5) Å, ß = 106.939(3)° and V = 475.65(6) Å3, Z = 2. When concentrated fluoride solutions are used, mostly RE2Ti2O7 type compounds were isolated in either cubic or monoclinic phases. In the case of cerium, Ce2Ti4O11IV was isolated that crystallizes in the monoclinic space group C2/c with unit cell parameters of a = 13.6875(7) Å, b = 5.0955(3) Å, c = 12.8592(7) Å, ß = 108.964(2)° and V = 848.18(8) Å3, Z = 4. The synthesis, structural characterization, and supporting characterization are reported for all compounds. The work highlights the complementary nature of hydroxide and fluoride fluids in studying the reactivity of refractory oxides.

Two halide-containing cesium manganese vanadates: synthesis, characterization, and magnetic properties.

Two new halide-containing cesium manganese vanadates have been synthesized by a high-temperature (580 °C) hydrothermal synthetic method from aqueous brine solutions. One compound, Cs3Mn(VO3)4Cl, (1) was prepared using a mixed cesium hydroxide/chloride mineralizer, and crystallizes in the polar noncentrosymmetric space group Cmm2, with a = 16.7820(8) Å, b = 8.4765(4) Å, c = 5.7867(3) Å. This structure is built from sinusoidal zig-zag (VO3)n chains that run along the b-axis and are coordinated to Mn2+ containing (MnO4Cl) square-pyramidal units that are linked together to form layers. The cesium cations reside between the layers, but also coordinate to the chloride ion, forming a cesium chloride chain that also propagates along the b-axis. The other compound, Cs2Mn(VO3)3F, (2) crystallizes in space group Pbca with a = 7.4286(2) Å, b = 15.0175(5) Å, c = 19.6957(7) Å, and was prepared using a cesium fluoride mineralizer. The structure is comprised of corner sharing octahedral Mn2+ chains, with trans fluoride ligands acting as bridging units, whose ends are capped by (VO3)n vanadate chains to form slabs. The cesium atoms reside between the manganese vanadate layers, and also play an integral part in the structure, forming a cesium fluoride chain that runs along the b-axis. Both compounds were characterized by single-crystal X-ray diffraction, powder X-ray diffraction, and single-crystal Raman spectroscopy. Additionally, the magnetic properties of 2 were investigated. Above 50 K, it displays behavior typical of a low dimensional system with antiferromagnetic interactions, as to be expected for linear chains of manganese(ii) within the crystal structure.

A Cesium Rare-Earth Silicate Cs3 RESi6 O15 (RE=Dy-Lu, Y, In): The Parent of an Unusual Structural Class Featuring a Remarkable 57†ŠUnit Cell Axis.

The structure of Cs3 RESi6 O15 , where RE=Dy-Lu, Y, In, is unusual in that it contains octahedrally coordinated rare-earth ions; their relative orientation dictates the structure, as they rotate about the c-axis supported by the cyclic Si6 O15 framework. The repeat unit of the rotation is eight units generating a very long (ca. 57 Å) unit cell axis. This unusual repeat unit is created by the structural flexibility of the hexasilicate ring, which is in turn affected by the size of the rare earth ion as well as the size of alkali ion residing within the silicate layers. Previous work showed for the smaller Sc3+ ion, the rotation of the octahedra is not sufficient to achieve closure at an integral repeat unit and an incommensurate structure results. The products are prepared as large, high quality single crystals using a high-temperature (650 °C) hydrothermal method with CsOH and F- mineralizers. The presence of fluoride is essential to the formation of the product.

Investigation of a Structural Phase Transition and Magnetic Structure of Na2BaFe(VO4)2: A Triangular Magnetic Lattice with a Ferromagnetic Ground State.

The structural and magnetic properties of a glaserite-type Na2BaFe(VO4)2 compound, featuring a triangular magnetic lattice of Fe2+ (S = 2), are reported. Temperature dependent X-ray single crystal studies indicate that at room temperature the system adopts a trigonal P3̅m1 structure and undergoes a structural phase transition to a C2/c monoclinic phase slightly below room temperature (Ts = 288 K). This structural transition involves a tilting of Fe-O-V bond angles and strongly influences the magnetic correlation within the Fe triangular lattice. The magnetic susceptibility measurements reveal a ferromagnetic transition near 7 K. Single crystal neutron diffraction confirms the structural distortion and the ferromagnetic spin ordering in Na2BaFe(VO4)2. The magnetic structure of the ordered state is modeled in the magnetic space group C2'/c' that implies a ferromagnetic order of the a and c moment components and antiferromagnetic arrangement for the b components. Overall, the Fe magnetic moments form ferromagnetic layers that are stacked along the c-axis, where the spins point along one of the (111) facets of the FeO6 octahedron.

Crystal chemistry and the role of ionic radius in rare earth tetrasilicates: Ba2RE2Si4O12F2 (RE = Er3+-Lu3+) and Ba2RE2Si4O13 (RE = La3+-Ho3+).

Structural variations across a series of barium rare earth (RE) tetrasilicates are studied. Two different formulas are observed, namely those of a new cyclo-silicate fluoride, BaRE2Si4O12F2 (RE = Er3+-Lu3+) and new compounds in the Ba2RE2Si4O13 (RE = La3+-Ho3+) family, covering the whole range of ionic radii for the rare earth ions. The Ba2RE2Si4O13 series is further subdivided into two polymorphs, also showing a dependence on rare earth ionic radius (space group P{\overline 1} for La3+-Nd3+, and space group C2/c for Sm3+-Ho3+). Two of the structure types identified are based on dinuclear rare earth units that differ in their crystal chemistries, particularly with respect to the role of fluorine as a structural director. The broad study of rare earth ions provides greater insight into understanding structural variations within silicate frameworks and the nature of f-block incorporation in oxyanion frameworks. The single crystals are grown from high-temperature (ca 953 K) hydrothermal fluids, demonstrating the versatility of the technique to access new phases containing recalcitrant rare earth oxides, enabling the study of structural trends.

One-Pot Hydrothermal Synthesis of TbIII13(GeO4)6O7(OH) and K2TbIVGe2O7: Preparation of a Stable Terbium(4+) Complex.

Two terbium germanates have been synthesized via high-temperature and high-pressure hydrothermal synthesis with 20 M KOH as a mineralizer using Tb4O7 as a starting material. Tb13(GeO4)6O7(OH) crystallizes in trigonal space group R3̅, is built up of isolated GeO4 units, and contains a complex arrangement of terbium oxide polyhedra. K2TbGe2O7 is a terbium(4+) pyrogermanate that is isostructural with K2ZrGe2O7 and displays a rare stable Tb4+ oxidation state in the solid state.

Three Unique Barium Manganese Vanadates from High-Temperature Hydrothermal Brines.

Three new barium manganese vanadates, all containing hexagonal barium chloride layers interpenetrated by [V2O7]4- groups, were synthesized using a high-temperature (580 °C) hydrothermal method. Two of the compounds were prepared from a mixed BaCl2/Ba(OH)2 mineralizer, and the third compound was prepared from BaCl2 mineralizer. An interesting structural similarity exists between two of the compounds, Ba2Mn(V2O7)(OH)Cl and Ba4Mn2(V2O7)(VO4)2O(OH)Cl. These two compounds crystallize in the orthorhombic space group Pnma, Z = 4, and are structurally related by a nearly doubled a axis. The first structure, Ba2Mn(V2O7)(OH)Cl (I) (a = 15.097(3) Å, b = 6.1087(12) Å, c = 9.5599(19) Å), consists of octahedral manganese(II) edge-sharing chains linked by pyrovanadate [V2O7] groups, generating a three-dimensional structure. Compound II, Ba4Mn2(V2O7)(VO4)2O(OH)Cl (a = 29.0814(11) Å, b = 6.2089(2) Å, c = 9.5219(4) Å), is composed of manganese(III) edge-sharing chains that are coordinated to one another through pyrovanadate groups in a nearly identical way as in I, forming a zigzag layer. A key difference in II is that these layers are capped on either end by two monomeric [VO4] groups that directly replace one [V2O7] group in I. The third compound, Ba5Mn3(V2O7)3(OH,Cl)Cl3 (III), crystallizes in the trigonal space group R32 (a = 9.7757(4) Å, c = 22.4987(10) Å) and is composed of manganese(II) trimeric units, [Mn3O12(OH,Cl)], coordinated to one another through pyrovanadate [V2O7] groups to form a three-dimensional structure. The unusual manganese trimers are built of three square pyramids all linked by a central (OH/Cl) atom. The key factor directing the formation of the different structures appears to be the identity and concentration of the halide brine mineralizer fluid. The ability of such brines to induce the formation of interpenetrated salt lattices in the present study is suggestive of a versatile realm of descriptive synthetic inorganic chemistry.