Hydrothermal Synthesis and Crystal Structures of Na2Be3(SeO3)4·H2O and Cs2[Mg(H2O)6]3(SeO3)4

The selenites, Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄, were synthesized under hydrothermal conditions. The crystal structures of Na₂Be₃(SeO₃)₄ · H₂O and Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ were determined by single‐crystal X‐ray diffractions. Na₂Be₃(SeO₃)₄ · H₂O crystallizes in the triclinic space group P1 (no. 2) with unit cell parameters a = 4.8493(9), b = 12.013(2), c = 12.077(2) Å, and Z = 2, whereas Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ crystallizes in the monoclinic space group C2/m (no. 12) with lattice cell parameters a = 12.596(6), b = 7.297(4), c = 16.914(8) Å, and Z = 2. Na₂Be₃(SeO₃)₄ · H₂O features a three‐dimensional open framework structure formed by BeO₄ tetrahedra and SeO₃ trigonal pyramids. Na cations and H₂O molecules are located in different tunnels. Cs₂[Mg(H₂O)₆]₃(SeO₃)₄ has a structure composed of isolated [Mg(H₂O)₆] octahedra and SeO₃ trigonal pyramids interacted by hydrogen bonds, and Cs cations are resided in‐between. Both compounds were characterized by thermogravimetric analysis and FT‐IR spectroscopy.     

Synthesis and Crystal Structure of In(OH)(SeO3)

In(OH)(SeO₃), prepared by a hydrothermal reaction, crystallizes in a new structure type containing cis InO₄(OH)₂ octahedra. These groups share both corners (via OH) and edges (via O) to result in a layered motif containing octahedral 8‐ring holes that resembles a single layer of the hollandite structure. The selenium atoms [as pyramidal (SeO₃)^2? selenite groups] decorate the 8‐ring holes and crosslink the sheets, leading to a three‐dimensional structure. Crystal data: In(OH)(SeO₃), M_r = 258.79, triclinic, (No. 2), a = 5.6523 (2) Å, b = 7.9598 (3) Å, c = 8.0911 (3) Å, α = 87.925 (2)°, β = 79.679 (2)°, γ = 83.201 (3)°, V = 355.58 (2) ų, Z = 4, R (F) = 0.023, wR (F²) = 0.054.     

(Ba6O)(ReN3)2: Synthesis,Crystal Structure and Physical Properties

The reaction of a mixture of barium and rhenium (3:1) at 850 °C under flowing nitrogen yielded the nitride‐oxide (Ba₆O)(ReN₃)₂ (R (No. 148); a = 8.1178(2) Å, c = 17.5651(4) Å; V = 1002.43(5) Å³; Z = 6). According to a structure refinement on X‐ray powder diffraction data, this compound is isostructural to a recently described nitride‐oxide of osmium of analogous composition. The structure consists of sheets of trigonal ReN₃ units and trigonal antiprismatic Ba₆O groups. The Ba–O distance of 2.73 Å is close to the sum of the respective ionic radii. The trigonal ReN₃^5– nitride anion displays a Re–N bond length of 1.94 Å, and is planar within the limits of experimental error. The constitution of the anion was confirmed by IR and Raman spectroscopy. The nitride‐oxide is stable up to 1000 °C, semiconducting (σ = 4.57 × 10^–3 Ω^–1 · cm^–1 at RT), and paramagnetic down to 25 K. A Curie–Weiss analysis resulted in a magnetic moment of μ = 0.68 μ_B per rhenium atom.     

钴、镍-氨基三乙酸配位聚合物Na[M(nta)]·H2O(M=Co,Ni)的水热合成、结构与磁性

由有机配体同金属离子作用构建的配位聚合物具有与无机微孔晶体类似的空旷骨架结构,并在非线性光学材料、磁性材料、超导材料及催化等诸多方面具有潜在的应用前景[1～4].在配位聚合物的合成中,配体的种类不仅直接影响到聚合物的合成,而且还涉及到聚合物的结构维数[5～7].目前,用来构建这些配合物的有机配体大多数都带有相同的可配位基团,较少应用具有两种以上的配位基团的有机配体.本文采用同时含有氮和氧两种配位原子的多齿配体氨基三乙酸[8～12],在水热条件下分别以Co2+和Ni2+作为组装基元,通过自组装合成了具有三维骨架结构的Na[M(nta)]·H2O [M=Co(1),Ni(2)]配位聚合物,并进行了结构与磁性研究.     

Syntheses and Characterization of 1,4‐Phenylenebisphosphonates,A[HO3PC6H4PO3H2] (A = Li,K, Rb,Cs, Tl,Ag and NH4) and Crystal Structure of 1,4‐Phenylenebisphosphonic Acid

Seven 1,4‐phenylenebisphosphonates of monovalent ions, A(HO₃PC₆H₄PO₃H₂) (A = Li, K, Rb, Cs, Tl, Ag and NH₄), were synthesized and characterized by single‐crystal X‐ray diffraction, spectroscopic and thermal methods. These compounds and the reported sodium analogue have four structure types. The sodium compound, one‐dimensional lithium compound and pillared‐layered cesium compounds have different structure types, whereas the potassium, rubidium, thallium, ammonium and silver compounds have a pillared ladder‐like structure. They undergo initial thermal decomposition in the range of 120–270 °C. Moreover, the single crystal X‐ray structure of 1,4‐phenylenebisphosphonic acid was determined.     

Synthesis and Crystal Structures of the First Quaternary Tantalum Thiogermanates,ATaGeS5 (A = K,Rb, Cs)

The new quaternary thiogermanates, ATaGeS₅ (A = K, Rb, Cs) were prepared with the use of halide fluxes and the crystal structures of the compounds were determined by single‐crystal X‐ray diffraction methods. The compounds are isostructural and crystallize in space group P\bar{1} of the triclinic system with two formula units in a cell of dimensions: a = 6.937(1) Å, b = 6.950(2) Å, c = 8.844(3) Å, α = 71.07(2)°, β = 78.56(2)°, γ = 75.75(2)°, V = 387.6(2) Å³ for KTaGeS₅; a = 6.996(3) Å, b = 7.033(3) Å, c = 8.985(4) Å, α = 70.33(3)°, β = 78.12(4)°, γ = 75.63(4)°, V = 399.6(3) Å³ for RbTaGeS₅; a = 7.012(4) Å, b = 7.202(3) Å, c = 9.267(5) Å, α = 68.55(3)°, β = 77.27(4)°, γ = 74.75(4)°, V = 416.2(4) Å³ for CsTaGeS₅. The structures of ATaGeS₅ (A = K, Rb, Cs) are comprised of anionic infinite two‐dimensional {}_\infty^2 [TaGeS₅^–] layers separated from one another by alkali metal cations (A⁺). Each layer is made up of tantalum centered sulfur octahedra and pairs of edge‐sharing germanium centered sulfur tetrahedra. The classical charge valence of these compounds should be represented by [A⁺][(Ta⁵⁺)(Ge⁴⁺)(S^2–)₅]. UV/Vis diffuse reflectance measurements indicate that they are semiconductors with optical bandgaps of ca. 2.0 eV.     

Crystal Structure,Synthesis, and Properties of tri‐Calcium di‐Citrate tetra‐Hydrate [Ca3(C6H5O7)2(H2O)2]·2H2O

From hydrothermal synthesis needle‐shaped crystals of [Ca₃(C₆H₅O₇)₂(H₂O)₂] · 2H₂O were obtained. The crystal structure was determined by single‐crystal X‐ray experiments and confirmed by powder data (P$\bar{1}$ (no. 2) a = 5.9466(4), b = 10.2247(8), c = 16.6496(13) Å, α = 72.213(7)°, β = 79.718(7)°, γ = 89.791(6)°, V = 947.06(13) Å³, Z = 2, R1 = 0.0426, wR2 = 0.1037). The structure was obtained from pseudo merohedrically polysynthetic twinned crystals using a combined data collection approach and refinement processes. The observed three‐dimensional network is dominated by eightfold coordinated Ca²⁺ cations linked by citrate anions and hydrogen bonds between two non‐coordinating crystal water molecules and two coordinating water molecules.     

Synthesis,Band and Crystal Structures,and Optical Properties of the Ternary Compound Mg2Te3O8

The new spiroffite Mg₂Te₃O₈ ( 1 ) was prepared by hydrothemal methods and structurally characterized by single‐crystal X‐ray diffraction analysis. Compound 1 crystallizes in the space group C2/c of the monoclinic system with two formula units in a cell: a = 12.6030(7), b = 5.2254(3), c = 11.6331(7) Å, β = 98.6960(10)°, V = 757.30(8) ų. The structure features a 3D open‐framework with spiroffite topology that has large tunnels approximately 3.2 × 5.5 Å. The optical properties and thermal stability of 1 were characterized by UV and IR spectroscopy as well as TG. Calculations of the electronic band structure along with the density of states (DOS) indicate that the present compound is a semiconductor with an indirect band gap, and that the optical absorption is mainly originated from the charge transitions from O‐2p state to Te‐5p and Te‐5s states.     

Metal‐Organic Niccolite: Synthesis,Structures, Phase Transition,and Magnetic Properties of [CH3NH2(CH2)2NH2CH3][M2(HCOO)6] (M=divalent Mn,Fe, Co,Ni, Cu and Zn)

We report the synthesis, crystal structures, thermal and magnetic characterizations of a family of metal‐organic frameworks adopting the niccolite (NiAs) structure, [dmenH₂²⁺][M₂(HCOO)₆²⁻] (dmen=N,N′‐dimethylethylenediamine; M=divalent Mn, 1Mn ; Fe, 2Fe ; Co, 3Co ; Ni, 4Ni ; Cu, 5Cu ; and Zn, 6Zn ). The compounds could be synthesized by either a diffusion method or directly mixing reactants in methanol or methanol–water mixed solvents. The five members, 1Mn , 2Fe , 3Co , 4Ni , and 6Zn are isostructural and crystallize in the trigonal space group P 1c, while 5Cu crystallizes in C2/c. In the structures, the octahedrally coordinated metal ions are connected by anti–anti formate bridges, thus forming the anionic NiAs‐type frameworks of [M₂(HCOO)₆²⁻], with dmenH₂²⁺ located in the cavities of the frameworks. Owing to the Jahn–Teller effect of the Cu²⁺ ion, the 3D framework of 5Cu consists of zigzag Cu‐formate chains with Cu OCHO Cu connections through short basal Cu O bonds, further linked by the long axial Cu O bonds. 6Zn exhibits a phase transition probably as a result of the order–disorder transition of the dmenH₂²⁺ cation around 300 K, confirmed by differential scanning calorimetry and single crystal X‐ray diffraction patterns under different temperatures. Magnetic investigation reveals that the four magnetic members, 1Mn , 2Fe , 3Co , and 4Ni , display spin‐canted antiferromagnetism, with a Néel temperature of 8.6 K, 19.8 K, 16.4 K, and 33.7 K, respectively. The Mn, Fe, and Ni members show spin‐flop transitions below 50 kOe. 2Fe possesses a large hysteresis loop with a large coercive field of 10.8 kOe. The Cu member, 5Cu , shows overall antiferromagnetism (both inter‐ and intra‐chains) with low‐dimensional characteristics.     

Crystal Structures,Dimorphism and Lithium Mobility of Li7MO6 (M = Bi,Ru, Os)

Li₇MO₆ (M = Bi, Ru, Os) have been synthesized by solid state reaction of Li₂O with Bi₂O₃, or MO₂ (M = Ru, Os) and characterized using powder X‐ray diffraction, differential scanning calorimetry, magnetic susceptibility (for M = Ru, Os), ionic conductivity and ⁶Li solid state NMR (for M = Bi) measurements. All three compounds exhibit a temperature induced triclinic – rhombohedral phase transition. Structures of the new low temperature triclinic phases have been refined by the Rietveld method from powder X‐ray data using atomic parameters of Li₇TaO₆ as a starting model ( Li₇BiO₆ : triclinic, , a = 5.5071(1), b = 6.0425(1), c = 5.5231(1) Å, α = 116.912(1), β = 120.867(1), γ = 62.234(1)°, V = 133.96(1) ų, Z = 1, T = 230 K; Li₇RuO₆ : triclinic, , a = 5.3654(1), b = 5.8584(1), c = 5.3496(1) Å, α = 117.182(1), β = 119.117(1), γ = 62.632(1)°, V = 124.43(1) ų, Z = 1, T = 295 K; Li₇OsO₆ : triclinic, , a = 5.3786(1), b = 5.8725(1), c = 5.3591(1) Å, α = 117.193(1), β = 119.277(1), γ = 62.700(1)°, V = 125.15(1) ų, Z = 1, T = 295 K). Upon cooling, Li₇RuO₆ and Li₇OsO₆ undergo a magnetic transition at 12 and 13 K, respectively, from the paramagnetic to the antiferromagnetic state. The higher ionic conductivity of Li₇BiO₆ at T < 300 °C, as compared to Li₇RuO₆ and Li₇OsO₆, can be ascribed to the undergoing of the triclinic – rhombohedral transition at a much lower temperature. At T > 300 °C, the ionic conductivity of all three compounds increases sharply due to the melting of the lithium sublattice; for Li₇RuO₆ and Li₇OsO₆ the latter effect is superimposed by the phase transitions to the rhombohedral modifications.     

Synthesis,Crystal Structure,and Properties of the Sodium Molybdate Fluoride Na3MoO4F

The compound Na₃MoO₄F was synthesized by high temperature solution methods. Single‐crystal X‐ray diffraction analysis reveals that Na₃MoO₄F crystallizes in the orthorhombic space group Pnma (No. 62) with lattice constants a = 5.588(2) Å, b = 7.515(3) Å, c = 12.876(5) Å, and Z = 4. The crystal structure consists of isolated MoO₄ groups and [FNa₃]_∞ chains, which are connected by Na–O bonds to form a three‐dimensional framework. A detailed structure comparison between Na₃MoO₄F and NaMoO₃F was carried out. IR spectroscopy and bond valence sum analysis of Na₃MoO₄F indicate that the structure is reasonable. In addition, the electronic structure was investigated by the first‐principles method.     

Further Example of Diphosphates: Synthesis and Characterization of K2Li2P2O7

By the application of cation substitution, a new mixed‐alkali metal diphosphate, K₂Li₂P₂O₇, was successfully synthesized through high temperature solution method for the first time. The single‐crystal X‐ray structural analysis shows that it crystallizes in the monoclinic space group C2/c (no. 15), with lattice constants a = 9.814(3) Å, b = 5.5163(15) Å, c = 13.538(4) Å, Z = 4, and β = 110.47(2)°. Its open cage‐like _∞³[Li₂(P₂O₇)]^2– framework is built up from alternating arrangement of Li₂O₆ and P₂O₇ dimers that form eight and twelve‐membered‐ring channels along the [010] direction, and the K atoms are entrapped in the larger twelve‐membered‐ring channels. Detailed structure comparisons in the N₄P₂O₇ (N = mixed alkali metals) family are discussed. In addition, the structural validity was verified through the IR spectrum. Thermal analyses and UV/Vis/NIR diffuse reflectance spectrum are also performed on the reported compound.     

The Low and High Temperature Crystal Structures of [Mg(H2O)6]XBr3 Double Salts (X = Rb,Cs

The crystal structures of the alkali double salts [Mg(H₂O)₆]XBr₃ (X = Rb⁺, Cs⁺) were analyzed in dependence on temperature from laboratory and synchrotron X‐ray powder diffraction data. At room temperature, both compounds are isostructural to [Mg(H₂O)₆](NH₄)Br₃ (C2/c; Z = 4; a = 9.64128(6) Å, b = 9.86531(5) Å, c = 13.78613(9) Å, β = 90.0875(5)° for [Mg(H₂O)₆]RbBr₃; a = 9.82304(7) Å, b = 9.98043(6) Å, c = 14.0100(1) Å, β = 90.1430(4)° for [Mg(H₂O)₆]CsBr₃). At a temperature of T = 358 K, [Mg(H₂O)₆]RbBr₃ undergoes a reversible phase transition towards a cubic perovskite type of structure with the [Mg(H₂O)₆]²⁺ octahedron in the cuboctahedral cavity exhibiting 4‐fold disorder ( ; a = 6.94198(1) Å at T = 458 K). In case of [Mg(H₂O)₆]CsBr₃ the lattice parameters in dependence on temperature show a distinct kink at T = 340 K, but no symmetry breaking phase transition occurs before decomposition starts. The dominant role of hydrogen bonding with respect to the stability of the crystal structures is discussed.     

Syntheses and Structures of Na2Mg3(OH)2(SO4)3·4H2O and K2Mg3(OH)2(SO4)3·2H2O

The crystal structures of Na₂Mg₃(OH)₂(SO₄)₃ · 4H₂O and K₂Mg₃(OH)₂(SO₄)₃ · 2H₂O, were determined from conventional laboratory X‐ray powder diffraction data. Synthesis and crystal growth were made by mixing alkali metal sulfate, magnesium sulfate hydrate, and magnesium oxide with small amounts of water followed by heating at 150 °C. The compounds crystallize in space group Cmc2₁ (No. 36) with lattice parameters of a = 19.7351(3), b = 7.2228(2), c = 10.0285(2) Å for the sodium and a = 17.9427(2), b = 7.5184(1), c = 9.7945(1) Å for the potassium sample. The crystal structure consists of a linked MgO₆–SO₄ layered network, where the space between the layers is filled with either potassium (K⁺) or Na⁺‐2H₂O units. The potassium‐bearing structure is isostructural to K₂Co₃(OH)₂(SO₄)₃ · 2(H₂O). The sodium compound has a similar crystal structure, where the bigger potassium ion is replaced by sodium ions and twice as many water molecules. Geometry optimization of the hydrogen positions were made with an empirical energy code.     

Synthesis,Crystal Structure,Bonding, and Properties of (Ba6O)(OsN3)2

The new barium nitridoosmate oxide (Ba₆O)(OsN₃)₂ was prepared by reacting elemental barium and osmium (3:1) in nitrogen at 815–830 °C. The crystal structure of (Ba₆O)(OsN₃)₂ as determined by laboratory powder X‐ray diffraction ( , No 148: a=b=8.112(1) Å, c=17.390(1) Å, V=991.0(1) ų, Z=3), consists of sheets of trigonal OsN₃ units and trigonal‐antiprismatic Ba₆O groups, and is structurally related to the “313 nitrides” AE₃MN₃ (AE=Ca, Sr, Ba, M=V–Co, Ga). Density functional calculations, using a hybrid functional, likewise indicate the existence of oxygen in the Ba₆ polyhedra. The oxidation state 4+ of osmium is confirmed, both by the calculations and by XPS measurements. The bonding properties of the OsN₃^5? units are analyzed and compared to the Raman spectrum. The compound is paramagnetic from room temperature down to T=10 K. Between room temperature and 100 K it obeys the Curie–Weiss law (μ=1.68 μ_B). (Ba₆O)(OsN₃)₂ is semiconducting with a good electronic conductivity at room temperature (8.74×10^?2 Ω^?1 cm^?1). Below 142 K the temperature dependence of the conductivity resembles that of a variable‐range hopping mechanism.     

Synthesis,Characterization, and X‐ray Structures of Ru3(CO)9(dotpm)(L) Complexes [L = PPh3, P(C6H4Cl‐p)3, and PPh2(C6H4Br‐p)]

The reaction of Ru₃(CO)₁₀(dotpm) ( 1 ) [dotpm = (bis(di‐ortho‐tolylphosphanyl)methane)] and one equivalent of L [L = PPh₃, P(C₆H₄Cl‐p)₃ and PPh₂(C₆H₄Br‐p)] in refluxing n‐hexane afforded a series of derivatives [Ru₃(CO)₉(dotpm)L] ( 2 – 4 ), respectively, in ca. 67–70 % yield. Complexes 2 – 4 were characterized by elemental analysis (CHN), IR, ¹H NMR, ¹³C{¹H} NMR and ³¹P{¹H} NMR spectroscopy. The molecular structures of 2 , 3 , and 4 were established by single‐crystal X‐ray diffraction. The bidentate dotpm and monodentate phosphine ligands occupy equatorial positions with respect to the Ru triangle. The effect of substitution resulted in significant differences in the Ru–Ru and Ru–P bond lengths.     

Synthesis,Crystal and Electronic Structure of Layered AMSb Compounds (A = Rb,Cs; M = Zn,Cd)

Synthesis, crystal structure, thermal stability, and electronic band structure of four new metal antimonides AMSb (A = Rb, Cs; M = Zn, Cd) are reported. CsZnSb and RbZnSb crystallize in the hexagonal ZrBeSi structure type, in a P6₃/mmc space group (no. 194, Z = 2) and unit cell dimensions of a = 4.5588(2)/4.5466(4) Å and c = 11.9246(6)/11.0999(10) Å. CsCdSb and RbCdSb crystallize in the tetragonal PbFCl structure type in a P4/nmm space group (no. 129; Z = 2) and unit cell parameters of a = 4.8884(5)/4.8227(3) Å and c = 8.8897(9)/8.5492(7) Å. All four compounds are air- and water-sensitive and are shown through DSC measurements to decompose between 975 K and 1060 K. Analysis of the calculated electronic band structure shows that the Zn-containing antimonides are topologically trivial narrow bandgap semiconductors, whereas Cd-containing compounds exhibit a band inversion along Γ-Z direction.     

Three Inter‐Alkali Metal Acetylides: KNaC2, KRbC2, and NaRbC2: Syntheses,Crystal Structures,and Structural Systematics

Three alkali metal acetylides, namely KNaC₂, KRbC₂, and NaRbC₂, were synthesized and characterized by means of X‐ray powder diffraction. KNaC₂ and KRbC₂ crystallize as a variant of the anti‐PbCl₂‐type structure (Pnma, Z = 4), whereas NaRbC₂ crystallizes as a variant of the anti‐PbFCl‐type structure (Pmmn, Z = 2). Based on a simple systematic approach developed by Sabrowsky et al. for inter‐alkali metal chalcogenides all known inter‐alkali metal acetylides can be classified into two classes: variants of the anti‐PbCl₂ type structure and variants of the anti‐PbFCl type structure. Acetylides with Q(ABC₂) ≤ 1.45 crystallize in the anti‐PbCl₂‐type structure, whereas for Q(ABC₂) > 1.45 the anti‐PbFCl‐type structure is found (Q(ABC₂) = V_m(A₂C₂)/V_m(B₂C₂) with V_m(A₂C₂) > V_m(B₂C₂); V_m: molar volume, A, B = alkali metals).     

Synthesis and Characterization of a Two‐Dimensional Zinc Phosphite,Zn3(tren)(HPO3)3·xH2O (x ≈ 0.5; tren = tris(2‐aminoethyl)amine)

A new zinc phosphite with the formula Zn₃(tren)(HPO₃)₃·xH₂O (x≈0.5) has been synthesized under hydrothermal conditions and characterized by FTIR, elemental analysis, powder X‐ray diffraction, single‐crystal X‐ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the triclinic system, space group (No.2), a = 10.1188(9) Å, b = 10.4194(9) Å, c = 10.5176(9) Å, α = 60.763(2)°, β = 70.6150(10)°, γ = 80.725(2)°, V = 912.77(14) ų, Z = 2. The structure consists of double crankshaft chains, which are linked by Zn‐O‐P bonds to form 8‐ and 12‐membered channels along the [100] direction. The claw‐like Zn‐centered complexes of Zn(N₄C₆H₁₈) as the supported templates, hang into the 12‐MR channels through Zn‐O‐P linkages with framework.