Molybdenum(VI) network polymers based on anion–π interaction and hydrogen bonding: Synthesis, crystal structures and oxidation catalytic application

A crystallographic investigation of anion–π interactions and hydrogen bonds on the preferred structural motifs of molybdenum(VI) complexes has been carried out. Two molybdenum(VI) network polymers MoO₂F₄·(Hinca)₂ (1) and MoO₂F₃(H₂O)·(Hinpa) (2), where inca = isonicotinamide and inpa = isonipecotamide, have been synthesized, crystallographically characterized and successfully applied to alcohol oxidation reaction. Complex 1 crystallizes in the monoclinic space C2/c: a = 16.832(3) Å, b = 8.8189(15) Å, c = 12.568(2) Å, β = 118.929(3)°, V = 1560.1(5) Å³, Z = 4. Complex 2 crystallizes in the triclinic space P-1: a = 5.459(2) Å, b = 9.189(4) Å, c = 12.204(5) Å, α = 71.341(6)°, β = 81.712(7)°, γ = 77.705(7)°, V = 564.8(4) Å³, Z = 2. Complex 1 consists of hydrogen bonding and anion–π interactions, both of which are considered as important factors for controlling the geometric features and packing characteristics of the crystal structure. The geometry of the sandwich complex of [MoO₂F₄]²⁻ with two pyridine rings indicates that the anion–π interaction is an additive and provides a base for the design and synthesis of new complexes. For complex 2, the anions and the protonated inpa ligands form a 2D supramolecular network by four different types of hydrogen contacts (N–HF, N–HO, O–HF and O–HO). The catalytic ability of complexes 1 and 2 has also been evaluated by applying them to the oxidation of benzyl alcohol with TBHP as oxidant.     

Crystal chemistry of three new monodimensional fluorometalates templated with ethylenediamine

Three new monodimensional hybrid metal (Ti, In, Al) fluorides are synthesized with ethylenediamine (en) as a templating agent in solvothermal conditions assisted by microwave heating. All structures involve inorganic chains built up from TiO₂F₄ octahedra connected by two opposite O²⁻ vertices in [H₂en]·(TiOF₄) (I), from InF₆(H₂O) pentagonal bipyramids linked by F–F edges in [H₂en]·(InF₄(H₂O))₂·H₂O (II) and from (Al₇F₃₀)⁹⁻ polyanions sharing two opposite AlF₆ octahedra in [H₂en]₃·(Al₆F₂₄) (III). I is tetragonal, P4/ncc, a = 12.761(3) Å, c = 8.041(3) Å; II is orthorhombic, F2dd, a = 6.904(5) Å, b = 16.559(5) Å, c = 19.777(4) Å and III is monoclinic, P2₁/n, a = 9.387(2) Å, b = 6.710(2) Å, c = 21.513(6) Å, β = 97.18(3)°.     

Flux synthesis of (3,4)-connected zinc phosphites with different framework topologies

Two three-dimensional open-framework zinc phosphites, H₂aem·Zn₃(HPO₃)₄·0.5H₂O (1) and H₂apm·Zn₃(HPO₃)₄ (2), have been synthesized by a phosphorous acid flux method, where aem=4-(2-aminoethyl)morpholine and apm=4-(3-aminopropyl)morpholine. Compound 1 crystallizes in the monoclinic system, P2₁/c, a=9.5852(7) Å, b=20.3941(8) Å, c=10.5339(8) Å, β=94.125(9)°, V=2053.8(2) Å³, Z=4, R₁=0.0319, wR₂=0.0628. Compound 2 crystallizes in the monoclinic system, P2₁/n, a=8.589(2) Å, b=14.020(3) Å, c=16.606(3) Å, β=97.190(8)°, V=1983.9(7) Å³, Z=4, R₁=0.0692, wR₂=0.1479. Both compounds are based on (3,4)-connected networks with 8- and 12-ring channels, which are constructed from Zn₃(HPO₃)₄ clusters as the same secondary building units. These inorganic clusters are spatially organized by different structure-directing agents into different three-dimensional frameworks.     

Novel M(II)–Hg(II) coordination polymers generated from metal-containing building blocks M(2-pyrazinecarboxylate)2 · (H2O)2 (M=Cu, Ni, Co) and HgCl2

A new class of M(II)–Hg(II) (M=Cu(II), Co(II), Ni(II)) mixed-metal coordination polymers, Cu(2-pyrazinecarboxylate)₂HgCl₂ (4), [Co(2-pyrazinecarboxylate)₂(HgCl₂)₂] · 0.61H₂O (5) and [Ni(2-pyrazinecarboxylate)₂(HgCl₂)₂] · 0.77H₂O (6), have been prepared by self assembly of metal-containing building blocks, M(2-pyrazinecarboxylate)₂ · (H₂O)₂(M=Cu(II), Co(II), Ni(II)), with HgCl₂. Compounds 4–6 were characterized fully by IR, elemental analysis and single crystal X-ray diffraction. Compound 4 crystallized in the monoclinic space group C2/c, with a=17.916(5) Å, b=7.223(2) Å, c=13.335(4) Å, β=128.726(3)°, V=1346.2(6) ų, Z=4. It contains alternating Hg(II) and Cu(II) metal centers that are cross-linked by 2-pyrazinecarboxylate spacers and chlorine co-ligands to generate a unique three-dimensional Hg(II)–Cu(II) mixed metal framework. Compound 5 crystallized in the triclinic space group P , with a=6.3879(7) Å, b=6.6626(8) Å, c=13.2286(15) Å, α=96.339(2)°, β=91.590(2)°, γ=113.462(2)°, V=511.71(10) ų, Z=1. Compound 6 also crystallized in the triclinic space group P , with a=6.3543(8) Å, b=6.6194(8) Å, c=13.2801(16) Å, α=96.449(2)°, β=92.263(2)°, γ=113.541(2)°, V=506.67(11) ų, Z=1. Compounds 5 and 6 are isostructural and in the solid state the Hg(II)M(II)Hg(II) units are connected by Hg₂Cl₂ linkages to produce a novel M(II)–Hg(II) (M=Co(II), Ni(II)) zigzag mixed-metal chain, in which a new type of M–M′–M′–M array was observed. The metal containing building blocks, M(2-pyrazinecarboxylate)₂ · (H₂O)₂ (M=Cu(II), Co(II), Ni(II)), exhibit different connectivities to HgCl₂ depending on the metal cation contained within them.     

Comparative evolved gas analytical and structural study on trans-diammine-bis(nitrito)-palladium(II) and platinum(II) by TG/DTA–MS, TG–FTIR, and single crystal X-ray diffraction

Detailed study on identification and thermal decomposition of solid title compounds 1 and 2 crystallized from the used aqueous ammonia solutions of Pd(NH₃)₂(NO₂)₂ and Pt(NH₃)₂(NO₂)₂, has been carried out. Beyond the composition of complexes 1 and 2, their trans square planar configuration have already been recognized by reference IR spectra and powder XRD patterns, nevertheless their exact molecular and crystal structure as of trans-Pd(NH₃)₂(NO₂)₂ (1, Pd-NN) and trans-Pt(NH₃)₂(NO₂)₂ (2, Pt-NN) has been determined by single crystal X-ray diffraction (R = 0.0515 and 0.0341), respectively. Despite their compositional and configuration analogy, they crystallize in different crystal systems and space groups. The crystals of 1 (Pd-NN) are triclinic (space group No. 2, P-1, a = 5.003(1) Å, b = 5.419(1) Å, c = 6.317(1) Å, α = 91.34(2)°, β = 111.890(10)°, γ = 100.380(10)°), while those of 2 (Pt-NN) are monoclinic (space group No. 5, C2, a = 7.4235(16) Å, b = 9.130(2) Å, c = 4.4847(10) Å, β = 99.405(7)°).The pyrolytic processes of 1 and 2 (which might be sensitive to shock and heat) have been followed by simultaneous thermogravimetric and differential thermal analysis (TG/DTA), while the evolved gaseous species have been traced in situ by online coupled TG/DTA–EGA–MS and TG–EGA–FTIR instruments in He and air. Pd and Pt powders, forming as final solid products in single step, are captured and checked by TG and XRD. Whilst the unified evolved gas analyses report evolution of N₂, H₂O, NH₃, N₂O, NO, and NO₂ gases as gaseous product components in the exothermic decomposition of both trans-Pd(NH₃)₂(NO₂)₂ (1) and trans-Pt(NH₃)₂(NO₂)₂ (2) starting from ca. 230 and 220 °C, in sealed crucibles with a pinhole on the top, respectively.     

Formation of helix-containing rods in a hybrid inorganic–organic material

The novel aluminum ethylenediphosphonate fluoride, [HN(CH₂CH₂NH₃)₃][Al₂(O₃PCH₂CH₂PO₃)₂F₂]·H₂O (1) (monoclinic, P2₁/n, a=12.145(4) Å, b=9.265(3) Å, c=20.422(6) Å, β=104.952(4)°, Z=3, R₁=0.092, wR₂=0.196) has been synthesized by solvothermal methods in the presence of tris(2-aminoethyl)amine and its structure determined using single microcrystal X-ray diffraction data. Compound 1 is a one-dimensional extended chain structure composed of well-separated anionic [Al₂(O₃PCH₂CH₂PO₃)₂F₂]⁴⁻ rods containing helical chains of corner-shared cis-AlO₄F₂ octahedra at their core. The charge-compensating tris(2-aminoethyl)ammonium cations separate the anionic [Al₂(O₃PCH₂CH₂PO₃)₂F₂]⁴⁻ rods that contain either left- or right-handed helical chains. The incorporation of the organic components into this hybrid material has aided the adoption of one-dimensionality by the compound and defined the pitch of the helical AlO₄F chain.     

Crystal structure and IR spectrum of 1-O-α- -glucopyranosyl- -mannitol–ethanol (2/1)

1-O-α- -Glucopyranosyl- -mannitol–ethanol (2/1), (C₁₂H₂₄O₁₁)₂–C₂H₅OH, crystallizes in the monoclinic space group P2₁ with unit cell dimensions a=11.4230(8) Å, b=9.525(4) Å, c=15.854(2) Å, β=102.751(7)° and V=1682.4(7) ų, Z=2, D_x=1.45 Mg m⁻³, λ (Mo-K_α)=0.71069 Å, μ=0.128 mm⁻¹, F(000)=788 and T=293(2) K. The structure was solved by direct methods and refined by least-squares calculations on F² to R₁=0.0371[I>2σ(I)], and 0.0930 (all data, 3542 independent reflections, R_int=0.021). There are two molecules of glucopyranosylmannitol (GPM) and one ethanol molecule in the asymmetric unit, and the glucopyranosyl ring adopts a chair conformation in both GPM molecules. Bond lengths and angles accord well with the mean values of related structures. The conformation along the mannitol side chain for one of the GPM molecules was the same as for the known polymorphs of -mannitol, while the conformation of the other molecule was different, indicating different conformational arrangements in the terminal carbon atoms of the mannitol side chains of the two GPM molecules. The structure in 1-O-α- -glucopyranosyl- -mannitol–ethanol (2/1) is held together by a very complex hydrogen bonding system, which consists of an infinte chain propagating along the b-axis and a discontinuous chain, which binds the ethanol molecule to the structure. The FTIR spectra for anhydrous GPM, GPM dihydrate and GPM–ethanol (2/1) were recorded. Both IR and X-ray results indicate the extensive hydrogen bonding in crystalline state.     

Strontium–copper selenite–chlorides: Synthesis and structural investigation

Two new complex selenite–chlorides of strontium and copper Sr₂Cu(SeO₃)₂Cl₂ (I) and SrCu₂(SeO₃)₂Cl₂ (II) were obtained and characterized by X-ray diffraction technique, DTA and IR spectroscopy. Both compounds crystallize in the monoclinic system I: Sp. gr. P2₁/n, a=5.22996(3) Å, b=6.50528(4) Å, c=12.34518(7) Å, β=91.3643(2)°, Z=2; II: Sp. gr. P2₁, a=7.1630(14) Å, b=7.2070(14) Å, c=8.0430(16) Å, β=95.92(3)°, Z=2. Comparison of the crystal structure of (I) with the structures of Sr₂M(SeO₃)₂Cl₂ (M=Co, Ni) was performed. The substitution of strontium atom in the structure of (I) by Cu²⁺ ion with a 3d⁹ Jahn–Teller distorted surrounding leads to the lowering of the structure symmetry and to the appearance of the noncentrosymmetric structure of (II). The noncentrosymmetric character of the structure of (II) was confirmed by SHG signal (1.2 units relative to an α-quartz powder sample).     

The O–H···O, O–H···N and C–H···O hydrogen bonds in 1,4-dimethylpiperazine mono-betaine monohydrate

1,4-Dimethylpiperazine mono-betaine (1-carboxymethyl-1,4-dimethylpiperazinium inner salt, MBPZ) crystallizes as monohydrate. The crystals are orthorhombic, space group Pccn. Two MBPZ molecules and two water molecules form a cyclic oligomer, (MBPZ·H₂O)₂. The O–H···O and O–H···N hydrogen bonds are of 2.769(1) and 2.902(1) Å, respectively. The dimers interact with the neighboring molecules through the C–H···O hydrogen bonds of 3.234(1) Å. The piperazine ring assumes a chair conformation with the N(4)–CH₃ and N⁺(1)–CH₂COO⁻ groups in the equatorial position and the N⁺(1)–CH₃ group in the axial one. The FTIR spectrum is compared with that calculated by the B3LYP/6-31G(d,p) level of theory.     

Ba2(VO2)(PO4)(HPO4)·H2O, a New Barium Vanadium(V) Phosphate Hydrate Containing Trigonal Bipyramidal VO5Groups

The hydrothermal synthesis, single crystal structure, and some physical properties of Ba₂(VO₂)(PO₄)(HPO₄)·H₂O, a new barium vanadium(V) phosphate hydrate, are reported. This phase is built up from one-dimensional chains of unusual VO₅trigonal bipyramids and (H)PO₄tetrahedra, fused together via V–O–P linkages. These anionic chains propagate along the polar [010] direction. 11-Coordinate barium cations and water molecules occupy the interchain regions and link the chains together. Structural data for this phase and other known barium vanadium phosphates are briefly compared. Crystal data: Ba₂(VO₂)(PO₄)(HPO₄)·H₂O,M_r=566.57, monoclinic, space groupP2₁(No. 4),a=5.0772(5) Å,b=8.724(2) Å,c=10.806(1) Å,β=90.795(8)°,V=478.6(1) ų,Z=2,R=2.65%,R_w=2.89% [147 parameters, 1893 observed reflections withI>3σ(I)].     

A 3D porous indium(III) coordination polymer involving in-situ ligand synthesis

The hydrothermal reaction of In³⁺ and 1,2,4-benzenetricarboxylic acid with the presence of piperazine leads to the generation of a novel 3D porous coordination polymer, [H₃O][In₂(btc)(bdc)(OH)₂]·5.5H₂O (1), (btc=1,2,4-benzenetricarboxylate, bdc=1,4-benzenedicarboxylate). Compound 1 crystallizes in orthorhombic space group Pbca with a=16.216(7) Å, b=13.437(6) Å, c=31.277(14) Å, and Z=8. It is interesting to find that the in-situ decarboxylation reaction of 1,2,4-benzenetricarboxylate (btc) partially transformed into 1,4-benzenedicarboxylate (bdc) occurs. The 16 indium(III) centers were linked by four btc, four bdc and two μ₂-OH ligands to form a box-girder. The adjacent box-girders are further connected by the bdc and btc ligands to generate a novel porous metal–organic framework containing nanotubular open channel with a cross-section of approximately 11.5×11.3 Å². The micropores are occupied by lattice water molecules, and the solvent-accessible volume of the unit cell was estimated to be 3658.6 Å³, which is approximately 53.7% of the unit-cell volume (6815.4 Å³).     

New Layered Materials in the K–In–Ge–As System: K8In8Ge5As17and K5In5Ge5As14

Exploratory synthesis in the K–In–Ge–As system has yielded the unusual layered compounds K₈In₈Ge₅As₁₇(1) and K₅In₅Ge₅As₁₄(2), both of which contain In–Ge–As layers with interleaved potassium ions, Ge–Ge bonds, InAs₄tetrahedra, As–As bonds, and rows of Ge₂As₆dimers. Compound 1 has As₃groups, while compound 2 has infinite As ribbons on both faces of each layer. Unlike compound 1, compound 2 has substitutional defects where indium partially occupies each of the three independent germanium sites in the ratio of 1:5 for In:Ge. This partial occupancy makes 2 an electron-precise compound. The Ge(In)–Ge(In) bond of 2 is longer than the Ge–Ge bond of 1, and this bond lengthening effect was confirmed by performing DFT-MO calculations on the model compounds H₃Ge–GeH₃and H₃Ge–InH⁻₃. Possible implications of electron imprecise formulas determined by X-ray crystal structure determinations are discussed. Compound 1: space groupP2₁/cwitha=18.394 (8) Å,b=19.087 (7) Å,c=25.360 (3) Å,β=105.71 (2)°,V=8571 (4) ų, andD_calcd=4.45g/cm³forZ=4. Refinement on 4455 reflections yieldedR(R_w)=6.8%(7.8%). Compound 2: space groupC2/mwitha=40.00 (1) Å,b=3.925 (2) Å,c=10.299 (3),β=99.97 (2)°,V=1592 (1) ų, andD_calcd= 4.55g/cm³forZ=8. Refinement on 1206 reflections yieldedR(R_w)=5.6% (5.7%).     

(C6H16N2)Zn3(HPO3)4H2O: a new layered zinc phosphite templated by diprotonated trans-1,4-diaminocyclohexane

Employing trans-1,4-diaminocyclohexane (trans-1,4-DACH) as a template, a new two-dimensional layered zinc phosphite (C₆H₁₆N₂)Zn₃(HPO₃)₄H₂O (1) has been prepared hydrothermally. Single-crystal X-ray diffraction analysis shows that it crystallizes in the monoclinic space group P2₁/n with a=10.458(2) Å, b=14.720(3) Å, c=13.079(3) Å, β=97.93(3)°, V=1994.1(7) ų, Z=4, R₁=0.0349 (I>2σ(I)) and wR₂=0.0605 (all data). The inorganic layer is built up by alternation of ZnO₄ tetrahedra and HPO₃ pseudo pyramids forming a 4.6.8-net. The sheet is featured by a series of capped six-membered rings. The diprotonated trans-1,4-DACH molecules reside in the interlayer region and interact with the inorganic network through H-bonds.     

Molecular structure of the unusual complex of 1-piperidineacetic acid with 2,4,6-trinitrophenol studied by X-ray, FTIR and H, C and C CP MAS NMR

Crystals containing three kinds of molecules 1-piperidiniumacetate (II), 1-piperidiniumacetic acid (III) and 2,4,6-trinitrophenolate (picrate, TNP⁻), belong to the monoclinic system, space group P2₁/c and Z=4, a=12.831(3), b=26.093(5), c=7.157(1) Å, β=101.18(3)°, R=0.0758. The zwitterion molecule (II) is a double acceptor of protons from two molecules of 1-piperidiniumacetic acid (III) (N–HO, 2.735(5) Å and O–HO, 2.472(5) Å), and a donor of proton to the picrate molecule (N–HO, 2.747(5) Å). These three molecules, which have three donor centers and several acceptor groups, form hydrogen-bonded chains parallel to the z axis. The oxygen atoms inactive in these hydrogen bonds, are engaged in the C–HO short contacts, which can be treated as weak hydrogen bonds, and join the chains into a three-dimensional network. The presence of protonated 1-piperidineacetic acid (III) and its zwitterion (II) in the crystal has been confirmed by ¹³C CP MAS NMR and solid state FTIR spectra.     

Tetrameric O–HO hydrogen-bond systems accompanied by C–HO hydrogen-bonds in the crystal of 1,4-bis(hydroxymethyl)triptycene: an X-ray study

The crystal structure of the title compound was determined (crystal data at 143 K: triclinic, space group P−1, Z=4, a=9.538(2) Å, b=11.638(2) Å, c=14.473(2) Å, α=88.647(3)°, β=89.875(3)°, γ=83.835(3)°, V=1596.9(4) ų). In the crystal there exist two kinds of tetrameric O–HO hydrogen-bond (H-bond) systems that are quite similar to each other. The oxygen atoms accept also intermolecular C–HO H-bonds. The two types of the H-bonds connect the molecules to an infinite two-dimensional supramolecular unit, the stacking of which is aided by an intermolecular C–Hπ H-bond. A phase transition with ΔH_t=4.4±0.1 kJ/mol was found at around 420 K.     

Neutron diffraction study of the β′ and γ phases of LiFeO2

The β, β′, γ and α phases of LiFeO₂, synthesized as powders, were annealed at different temperatures and characterized by X-ray measurements. The β′ and γ modifications were also studied by time-of-flight neutron diffraction (ISIS Facility, UK). The structure of the β′ phase was refined in the monoclinic C2/c space group (a=8.566(1), b=11.574(2), c=5.1970(5) Å, β=146.064(5)°) to wR_p=0.071–0.080 (data from four counter banks). Fe and Li atoms are ordered over two of the four independent sites, and partially disordered over the other two. The ordered Li has a distorted tetrahedral coordination. The γ structure was refined at RT (a=4.047(1), c=8.746(2) Å) and at 570 °C (a=4.082(3), c=8.822(6) Å) in the I4₁/amd symmetry, showing full order with Li in octahedral coordination at RT, and in a split-atom configuration at high temperature. On annealing, the β′ polymorph was found to transform to γ at 550 °C, thus suggesting that it is a metastable phase. Electrostatics is discussed as the driving force for the α→β′→γ ordering process of LiFeO₂.     

The crystal structure, vibrational spectra, and thermal behavior of dilithium piperazinium(2+) selenate tetrahydrate and dilithium N,N′-dimethylpiperazinium(2+) selenate tetrahydrate

The crystal structure of dilithium piperazinium(2+) selenate tetrahydrate has been solved; this substance crystallizes in the triclinic space group , a=7.931(2) Å, b=7.974(2) Å, c=7.991(2) Å, α=106.99(2)°, β=101.83(2)°, γ=119.28(2)° Z=1, R=0.0280 for 1489 observed reflections. A similar compound, dilithium N,N′-dimethylpiperazinium(2+) selenate tetrahydrate crystallizes in a monoclinic system with space group P2₁/c and lattice parameters a=7.338(1) Å, b=8.792(2) Å, c=12.856(1) Å, β=92.04(2)°, Z=2, R=0.0334 for 1462 observed reflections. Both structures are centrosymmetric with center of symmetry in the center of eight membered ring formed with two SeO₄ tetrahedra and two LiO₄ tetrahedra connected through tops. The two remaining oxygens on each Li atom come from water molecules. The FTIR and FT Raman spectra of both natural and N,O-deuterated substances have been measured and studied. The thermoanalytical properties were studied using TG, DTG and DTA methods in the temperature range 293–873 K for piperazinium derivative and in the range 293–523 K for dimethylpiperazinium derivative. DSC measurements were carried out in the temperature range 95–343 K. No phase transition was found in this temperature region for either of the compounds.     

Hydrothermal Synthesis and Crystal Structure of [(CH3NH3)1.03K2.97]Sb12S20·1.34H2O

A novel thioantimonate(III) [(CH₃NH₃)_1.03K_2.97]Sb₁₂S₂₀·1.34H₂O was synthesized hydrothermally. It crystallizes in space groupP , witha=11.9939(7) Å,b=12.8790(8) Å,c=14.9695(9) Å,α=100.033(1)°,β=99.691(1)°,γ=108.582(1)°,V=2095.3(2) ų, andZ=2. The structure is determined from single crystal X-ray diffraction data collected at room temperature and refined toR(F)=0.037. In the crystal structure, each Sb(III) atoms has short bonds (2.37–2.58 Å) to three S atoms. The pyramidal [SbS₃] groups share common S atoms forming two types of centrosymmetric [Sb₁₂S₂₀] rings with the same topology. These rings are interconnected by weaker Sb–S bonds (2.92–3.29 Å) into 2-dimensional layers. Adjacent layers are parallel with K⁺and CH₃NH⁺₃ions and H₂O molecules located between them. Variation of bond valence sums calculated for the Sb(III) cations is found to be correlated with the coordination geometry. This is interpreted as due to the stereochemical activity of their lone electron pairs.     

The Phase Relations in the System In2O3–TiO2–MgO at 1100 and 1350°C

The phase relations in the system In₂O₃–TiO₂–MgO at 1100 and 1350°C are determined by a classical quenching method. In this system, there are four pseudobinary compounds, In₂TiO₅, MgTi₂O₅ (pseudobrookite type), MgTiO₃ (ilmenite type), and Mg₂TiO₄ (spinel type) at 1100°C. At 1350°C, in addition to these compounds there exist a spinel-type solid solution Mg_2−xIn_2xTi_1−xO₄ (0≤x≤1) and a compound In₆Ti₆MgO₂₂ with lattice constants a=5.9236(7) Å, b=3.3862(4) Å, c=6.3609(7) Å, β=108.15(1)°, and q=0.369, which is isostructural with the monoclinic In₃Ti₂FeO₁₀ in the system In₂O₃–TiO₂–MgO. The relation between the lattice constants of the spinel phase and the composition nearly satisfies Vegard's law. In₆Ti₆MgO₂₂ extends a solid solution range to In₂₀Ti₁₇Mg₃O₆₇ with lattice constants of a=5.9230(5) Å, b=3.3823(3) Å, c=6.3698(6) Å, β=108.10(5)°, and q=0.360. The distributions of constituent cations in the solid solutions are discussed in terms of their ionic radius and site preference effect.     

A two-dimensional bimetallic oxide constructed from ζ-octamolybdate clusters and Ag(I)-tpyprz cationic polymer components (tpyprz = tetra-2-pyridylpyrazine)

The hydrothermal reaction of Na₂MoO₄, Ag(CH₃CO₂), tetra-2-pyridylpyrazine (tpyprz), HF and water at 170 °C for 48 h yields [ Ag₄(tpyprz)₂(H₂O) Mo₈O₂₆] (1) as colorless plates. The structure of 1 is a two-dimensional network, constructed from Ag₄(tpyprz)₂(H₂O) ⁴ⁿ⁺_n chains linked through ζ- clusters. The chains exhibit three distinct Ag(I) environments: a four coordinate AgN₄ site, a three coordinate AgN₂O_aqua site, and four coordinate AgN₃O_oxo site which links to the molybdate cluster. Each cluster is connected by bridging oxo-groups to two silver/tpyprz chains to form the network architecture. Crystal data: C₂₄H₁₇Ag₂Mo₄N₆O_13.5, fw 1204.94, orthorhombic Pccn, a=20.8234(9) Å, b=14.5076(6) Å, c=20.3537(9) Å, V=6148.9(5) Å³, Z=8, D_calc=2.603 g cm⁻³.