NaMn6(P2O7)2(P3O10) and KCd6(P2O7)2(P3O10)

The crystal structures of two new diphosphates, sodium hexamanganese bis­(diphosphate) triphosphate, NaMn₆(P₂O₇)₂(P₃O₁₀), and potassium hexacadmium bis­(diphosphate) triphosphate, KCd₆(P₂O₇)₂(P₃O₁₀), confirm the rigidity of the M₆(P₂O₇)₂(P₃O₁₀) matrix (M is Mn or Cd) and the relatively fixed dimensions of the tunnels extending in the a direction of the unit cell. The compounds are isomorphous; the P₂O₇^4? anion and the alkali metal cations lie on mirror planes. Bond‐valence analysis of the bonding details of the atoms found within the tunnels permits a prediction of the conductivity.     

Preparation,Crystal Structure and Vibrational Spectra of Ca2P2O6·2H2O and [Ca(H2O)3(H2P2O6)]·0.5(C12H24O6)·H2O

The calcium salts Ca₂P₂O₆ · 2H₂O ( 1 ) and [Ca(H₂O)₃(H₂P₂O₆)] · 0.5(C₁₂H₂₄O₆) · H₂O ( 2 ) were prepared and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic space group Pbca and compound 2 in the monoclinic space group P2₁/n. The crystal structure of compound 1 consists of chains of edge‐sharing [CaO₇] polyhedra linked by hypodiphosphate(IV) anions to form a three‐dimensional network. The crystal structure of compound 2 consists of alternated layers of crown ether and water molecules and respective ionic units. Within the layers of ionic units the Ca²⁺ cations are octahedrally coordinated by three monodentate dihydrogenhypodiphosphate(IV) anions and three water molecules. The IR/Raman spectra of the title compounds were recorded and interpreted, especially with respect to the [P₂O₆]^4– and [H₂P₂O₆]^2– groups. The phase purity of 2 was verified by powder diffraction measurements.     

Low temperature heat capacity Study of Fe(PO3)3 and Fe2P2O7

The heat capacities of two iron phosphates, Fe(PO₃)₃ and Fe₂P₂O₇, have been measured over the temperature range from (2 to 300) K using the heat capacity option of a Quantum Design Physical Property Measurement System (PPMS). A phase transition related to magnetic ordering has been found in the heat capacity at T = 8.76 K for Fe(PO₃)₃ and T = 18.96 K for Fe₂P₂O₇, which are comparable with literature values from magnetic measurements. By fitting the experimental heat capacity values, the thermodynamic functions, magnetic heat capacities, and magnetic entropies have been determined. Additionally, theoretical fits at low temperatures suggest that Fe₂P₂O₇ has an anisotropic antiferromagnetic contribution to the heat capacity and a large linear term likely caused by oxygen vacancies. Further data fitting in a series over widened temperature regions found that this linear term exists only below 15 K and disappears gradually from (15 to 17) K.     

Syntheses and Crystal Structures of the Cyclotriphosphate Hydrates Nd(P3O9)·3H2O,Nd(P3O9)·4.5H2O,RE(P3O9)·5H2O (RE = Pr,Nd), and Na3RE(P3O9)2·6H2O (RE = Pr,Nd)

Several rare‐earth cyclotriphosphate hydrates were obtained from mixtures of sodium cyclotriphosphates and the respective rare‐earth chlorides. Nd(P₃O₉) · 3H₂O [P$\bar{6}$ , Z = 3, a = 677.90(9), c = 608.67(9) pm, R₁ = 0.016, wR₂ = 0.038, 312 data, 36 parameters] was obtained by a solid state reaction and is isotypic with respective rare‐earth phosphate hydrates, while all the others adopt new structure types. Nd(P₃O₉) · 4.5H₂O [C2/c, Z = 8, a = 1644.6(3), b = 756.11(15), c = 1856.1(4) pm, β = 97.25(3)°, R₁ = 0.032, wR₂ = 0.081, 1763 data, 194 parameters], Nd(P₃O₉) · 5H₂O [P2₁/c, Z = 4, a = 773.75(15), b = 1149.1(2), c = 1394.9(3) pm, β = 106.07(3)°, R₁ = 0.042, wR₂ = 0.082, 1338 data, 194 parameters], Pr(P₃O₉) · 5H₂O [P$\bar{1}$ , Z = 2, a = 745.64(15), b = 889.07(18), c = 934.55(19) pm, α = 79.00(3), β = 80.25(3), γ = 66.48(3), R₁ = 0.059, wR2 = 0.089, 1468 data, 193 parameters], Na₃Nd(P₃O₉)₂ · 6H₂O [P2₁/n, Z = 4, a = 1059.78(18), b = 1207.25(15), c = 1645.7(4) pm, β = 99.742(17), R₁ = 0.047, wR₂ = 0.119, 1109 data, 351 parameters] and Na₃Pr(P₃O₉)₂ · 6H₂O [P2₁/n, Z = 4, a = 1061.42(16), b = 1209.0(2), c = 1635.5(3) pm, β = 99.841(13), R₁ = 0.035, wR₂ = 0.062, 1323 data, 350 parameters] were obtained by careful crystallization at room temperature. A thorough structure discussion is given. The infrared spectrum of Nd(P₃O₉) · 4.5H₂O is also reported.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Identification of a new family of phosphate compounds,AIBII6(P2O7)2P3O10: structures of KMn6(P2O7)2P3O10 and AgMn6(P2O7)2P3O10

Two members of a new family of inorganic phosphates of general formula A^IB^II₆(P₂O₇)₂P₃O₁₀; KMn₆(P₂O₇)₂P₃O₁₀ (a=5.405(2), b=26.918(11), c=6.660(5), β=107.31(3)°, V=925.1(9) Å³, space group P2₁/m, Z=2, D_calc=3.481 Mg m⁻³, R=0.0377 for 2235 observed reflections) and AgMn₆(P₂O₇)₂P₃O₁₀ (a=5.424(7), b=26.97(4), c=6.627(9), β=106.81(7)°, V=928(2) Å³, space group P2₁/m, Z=2, D_calc=3.716 Mg m⁻³, R=0.0594 for 1577 observed reflections) have been synthesized and identified by single crystal X-ray diffraction. The isostructural complexes present an interesting comparison of silver and potassium bonding.     

Kristallstrukturen des Sr(BrO3)2 · H2O,Ba(BrO3)2 · H2O,Ba(IO3)2 · H2O,Pb(CIO3)2 · H2O und Pb(BrO3)2 · H2O

Crystal Structure of Sr(BrO₃)₂ · H₂O, Ba(BrO₃)₂ · H₂O, Ba(IO₃)₂ · H₂O, Pb(ClO₃)₂ · H₂O, and Pb(BrO₃)₂ · H₂O The crystall structures of the isostructural halates Sr(BrO₃)₂ · H₂O, Ba(BrO₃)₂ · H₂O, Ba(IO₃)₂ · H₂O, Pb(ClO₃)₂ · H₂O, and Pb(BrO₃)₂ · H₂O were determined using X-ray single crystal data (monoclinic space group C2/c? C, Z = 4), The mean bond lengths and bond angles of the halate ions in the Ba(ClO₃)₂ · 1 H₂O-type compounds, which correspond to those of other halates, are Cl? O, 149.0, Br? O, 165.9, I? O, 180.2 pm, ClO₃^?, 106.4, BrO₃^?, 104.0, and IO₃^?, 99.6°. The structure data obtained are discussed in terms of possible orientational disorder of the water molecules, strengths of the hydrogen bonds, influence of the lead ions on the structure, and site group distortion of the halate ions.     

KZn(HP2O7)·2H2O and KMn(HP2O7)·2H2O: acid pyrophosphate metallates(II) with layer structures

The crystal structures of the isomorphous title compounds, namely potassium zinc hydrogen pyrophosphate dihydrate and potassium manganese hydrogen pyrophosphate dihydrate, consist of acidic pyrophosphate–metallate(II) layers joined by K⁺ ions and hydrogen‐bridging bonds. The Zn²⁺/Mn²⁺ ions are octahedrally surrounded by four pyrophosphate O atoms and by two water mol­ecules. The (HP₂O₇)^3? anions exhibit eclipsed conformations. The metal ions and water O atoms lie on mirror planes, as does the central O atom of the (HP₂O₇)^3? anion.     

配合物Nd(C7H7N2O2)3(H2O)3的合成及其晶体结构

用水热法合成了3,5-二氨基苯甲酸与Nd(Ⅲ)的配合物Nd(C7H7N2O2)3(H2O)3(1),其结构经IR,元素分析和X-射线单晶衍射仪表征。1为单核结构,属六方晶系,R3空间群,晶胞参数:a=1.887 29(18)nm,b=1.887 29(18)nm,c=0.603 53(12)nm,β=90,°γ=120°,V=1.861 7(4)nm3,Z=3,μ=2.154 mm-1,Dc=1.744 g.cm-3,R1=0.014 3,wR2=0.033 2。1中Nd(Ⅲ)与来自3个3,5-二氨基苯甲酸的6个氧原子及3个配位水的氧原子进行配位,形成9配位化合物。     

Zoledronate complexes. III. Two zoledronate complexes with alkaline earth metals: [Mg(C5H9N2O7P2)2(H2O)2] and [Ca(C5H8N2O7P2)(H2O)]n

Diaquabis[dihydrogen 1‐hydroxy‐2‐(imidazol‐3‐ium‐1‐yl)ethylidene‐1,1‐diphosphonato‐κ²O,O′]magnesium(II), [Mg(C₅H₉N₂O₇P₂)₂(H₂O)₂], consists of isolated dimeric units built up around an inversion centre and tightly interconnected by hydrogen bonding. The Mg^II cation resides at the symmetry centre, surrounded in a rather regular octahedral geometry by two chelating zwitterionic zoledronate(1−) [or dihydrogen 1‐hydroxy‐2‐(imidazol‐3‐ium‐1‐yl)ethylidene‐1,1‐diphosphonate] anions and two water molecules, in a pattern already found in a few reported isologues where the anion is bound to transition metals (Co, Zn and Ni). catena‐Poly[[aquacalcium(II)]‐μ₃‐[hydrogen 1‐hydroxy‐2‐(imidazol‐3‐ium‐1‐yl)ethylidene‐1,1‐diphosphonato]‐κ⁵O:O,O′:O′,O′′], [Ca(C₅H₈N₂O₇P₂)(H₂O)]_n, consists instead of a Ca^II cation in a general position, a zwitterionic zoledronate(2−) anion and a coordinated water molecule. The geometry around the Ca^II atom, provided by six bisphosphonate O atoms and one water ligand, is that of a pentagonal bipyramid with the Ca^II atom displaced by 0.19 Å out of the equatorial plane. These Ca^II coordination polyhedra are `threaded' by the 2₁ axis so that successive polyhedra share edges of their pentagonal basal planes. This results in a strongly coupled rhomboidal Ca₂–O₂ chain which runs along [010]. These chains are in turn linked by an apical O atom from a –PO₃ group in a neighbouring chain. This O‐atom, shared between chains, generates strong covalently bonded planar arrays parallel to (100). Finally, these sheets are linked by hydrogen bonds into a three‐dimensional structure. Owing to the extreme affinity of zoledronic acid for bone tissue, in general, and with calcium as one of the major constituents of bone, it is expected that this structure will be useful in modelling some of the biologically interesting processes in which the drug takes part.     

Open-framework Borophosphate:(NH4)0.5FeⅡ0.5FeⅢ0.5·(H2O)2 BP2O8·0.5 H2O

An open-framework ammonium ferricborophosphate compound was synthesized by mild hydrothermal condition at 110°C. The crystal structure has been determined by single-crystal X-ray diffraction analysis: hexagonal, P6522, a = 9.452(2)A, c = 15.698(5)A,α = 90°,γ = 120°,Z= 6, Mr = 310.58, V = 1214.0(5)A3, Dc = 2.549 g/cm3, μ= 2.311mm-1, F(000) = 930. The chiral tetrahedral-tetrahedral helical ribbons are linked by the mixed valance FeII/FeIIIO6 coordinated octahedra. The ammonium ions are located inside the free loop of helical ribbons close to the inner wall of the helical channels{[BP2O8]3-}, effecting on balancing charge and stabilizing helical ribbons.     

Synthesis and Structural Characterization of Two Molybdenum~phosphate Cluster Compounds: (C_(14)N_(14)H_(63) )Na(H_2Mo_6P_4O_(31))_2·8H_2Oand(C_(14)N_(14)H_(63))Na(H_2Mo_6P_4O_(31) )_2·5H_2O

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Crystal structure and heat capacity of the mixed-valence trinuclear iron monoiodoacetate complex, [Fe(III)2Fe(II)O(O2CCH2I)6(H2O)3][Fe(III)3O(O2CCH2I)6(H2O)3]I

The crystal structure of a trinuclear iron monoiodoacetate complex was determined. Although it has been incorrectly characterized as [Fe₃O(O₂CCH₂I)₆(H₂O)₃], the correct chemical formula turned out to be [Fe(III)₂Fe(II)O(O₂CCH₂I)₆(H₂O)₃]-[Fe(III)₃O(O₂CCH₂I)₆(H₂O)₃]I (1). The two kinds of Fe₃O molecules (Fe(III)₂Fe(II)O and Fe(III)₃O) are crystallographically indistinguishable. All the Fe atoms are crystallographically equivalent because of a crystallographic threefold symmetry. Heat capacities of 1 seem to exhibit no thermal anomaly in the temperature range 5.5–309 K, although the valence detrapping phenomenon has been observed in this temperature range. This fact indicates that the valence-detrapping phenomenon in 1 occurs without any phase transition, leading 1 to a glassy state, probably because the crystal of 1 is just like a solid solution of distorted mixed-valence Fe(III)₂Fe(II)O molecules and permanently undistorted Fe(III)₃O molecules which may act as an inhibitor for a cooperative valence-trapping.