Darstellung und Kristallstruktur von [Co(NH3)6]2P4O13 · 5 H2O

Preparation and Crystal Structure of [Co(NH₃)₆]₂P₄O₁₃ 7·5H₂O Single crystals of [Co(NH₃)₆]P₄O₁₃ · 5 H₂O were obtained by diffusion controlled growth. To this end sodium polytetraphosphate was prepared by column chromatography and allowed to react with [Co(NH₃)₆]Cl₃. The compound [Co(NH₃)₆]₂P₄O₁₃ · 5 H₂O contains the novel isolated polytetraphosphate anion. The expected systematic variation in bond length in the P? O? P bridges of the poly tetraphosphate anion was verified. The conformation of the anion is discussed.     

Synthesis,vibrational spectra,and structure of divalent metal peroxodisulfates

Simple strontium peroxodisulfate SrS₂O₈ · 4H₂O was synthesized by the reaction of solid Sr(OH)₂ · 8H₂O taken in 30% excess with an aqueous solution of (NH₄)₂S₂O₈; simple magnesium peroxodisulfate MgS₂O₈ · 6H₂O was synthesized by the reaction of an aqueous solution of BaS₂O₈ with a stoichiometric amount of MgSO₄ · 7H₂O. Persulfate ammine complexes [M(NH₃)₄]S₂O₈ (M = Zn, Cu) were prepared in concentrated aqueous ammonia from [Zn(NH₃)₄](OH)₂, [Cu(NH₃)₄](OH)₂, and an ammoniac solution of (NH₄)₂S₂O₈. The compounds were characterized by X-ray powder diffraction (pRSA) and vibrational (IR and Raman) spectroscopy. Their stability was studied during storage and in DTA experiments. The [Zn(NH₃)₄]S₂O₈ structure was solved. Its crystals are orthorhombic, a = 10.5512(8) Å, b = 12.8039(12) Å, c = 8.0448(5) Å, V = 1086(15) ų, Z = 4, space group Pna2₁. The compound is built of [Zn(NH₃)₄]²⁺ complex cations and S₂O ₈ ^2? persulfate anions. In a cation, Zn-N bond lengths are within 2.04(2)–2.056(14) Å. In an anion, the lengths of S(1)–O(4), S(2)–O(5), and O(4)–O(5) bridging bonds are, respectively, 1.676(14), 1.672(16), and 1.465(16) Å; the other S–O bond lengths are within 1.409(14)–1.443(12) Å; the S(1)O(4)O(5)S(2) torsion angle is 140.8(7)°.     

Mehrkernige Kobaltkomplexe. II. Herstellung und Struktur von [(tren) (NH3)Co(O2)Co(NH3) (tren)](SCN)4 · 2H2O

Polynuclear Cobalt Complexes. II. Preparation and Structure of [(tren) (NH₃)Co(O₂)Co(NH₃) (tren)](SCN)₄ · 2H₂O The title compound is obtained on oxygenation of [Co(tren)(H₂O)₂]²⁺ in 6M aqueous ammonia or by ligand exchange starting from [(NH₃)₅Co(O₂)Co(NH₃)₅]-(NO₃)₄. An X-ray structure determination was made. The substance forms monoclinic crystals, space group P2₁/c, lattice constants a=10,135, b=8,473, c=19,484 Å, β=108,58°, with two formula units in the cell. The final R is 0,066. The binuclear cation has a center of symmetry, so the Co? O? O? Co unit is planar; the Co? O? O angle is 111,5°. The tertiary nitrogen atoms of both chelate groups are cis to the O₂ bridge, as found in doubly bridged [(tren)Co(O₂,OH)Co(tren)](ClO₄)₃ · 3H₂O. On acidification in solution, the singly bridged cation [(tren) (NH₃)CoO₂Co(NH₃)(tren)]⁴⁺ (a) loses the bound O₂ completely. But unlike the doubly bridged cation b , the rate of dissociation of a is independent of pH (Fig. 5). At higher pH (8–10) bridging a→b (Fig. 2) occurs. Both reactions must have the same rate determining step, the first order rate constants being of the order of 2 · 10^?3 s^?1 (25°, 0,35M KCl).     

Water‐soluble and Halogen‐free Hexaammine Complexes of Metal Ions of Group 9 – Synthesis,Crystal Structures,and Vibrational Spectra

Reaction of [M(NH₃)₆]Cl₃ (M = Co, Rh, Ir) and [Ir(NH₃)₅(OH₂)]Cl₃ with (NH₄)₂C₂O₄ · H₂O in aqueous solution resulted in the isolation of [M(NH₃)₆]₂(C₂O₄)₃ · 4 H₂O and [Ir(NH₃)₅(OH₂)]₂(C₂O₄)₃ · 4 H₂O, respectively. The complexes have been characterized by X‐ray crystallography, IR and UV/VIS spectroscopy. The isomorphous compounds crystallize in the orthorhombic space group Pnnm (No. 58). Four molecules of crystal water are involved in an extended three‐dimensional hydrogen bonding network. The librational modes of the lattice water around 600 cm^–1 allow the characterization of [Ir(NH₃)₆]₂(C₂O₄)₃ · 4 H₂O and [Ir(NH₃)₅(OH₂)]₂(C₂O₄)₃ · 4 H₂O, respectively, by IR spectroscopy. The band around 600 cm^–1 shows a significant frequency shift in the IR spectra of the hexaammine and aquapentaammine complex of iridium(III) and, by that, a distinction is possible.     

Kristallstruktur von Na5P3O10 · 6 H2O

Crystal Structure of Na₅P₃O₁₀ · 6 H₂O Na₅P₃O₁₀ · 6 H₂O crystallizes triclinic in P1 with a = 1 037.0(2), b = 984.8(4), c = 761.5(3) pm; α = 92.24(7)°, β = 94.55(9), γ = 90.87(6)°; Z = 2. The structure has been determined from fourcycle diffractometer data (2 089 independent reflections, R = 0.053). All hydrogen positions have been taken from a weighted difference-fourier-syntheses. Na₅P₃O₁₀ · 6 H₂O forms colorless, plate-like crystals, which are twinned systematically parallel (001) and can be divided mechanically into single-crystalline portions.     

Thermal analysis of some polynuclear coordination compounds as precursors of iron garnets (M3Fe5O12, M=Y3+ or Er3+)

The thermal behaviour of four coordination compounds (NH₄)₆[Y₃Fe₅(C₄O₅H₄)₆(C₄O₅H₃)₆]·12H₂O, (NH₄)₆[Y₃Fe₅(C₆O₇H₁₀)₆(C₆O₇H₉)₆]·8H₂O, (NH₄)₆[Er₃Fe₅(C₄O₅H₄)₆(C₄O₅H₃)₆]·10H₂O and (NH₄)₆[Er₃Fe₅(C₄O₆H₄)₆(C₄O₆H₃)₆]·22H₂O has been studied to evaluate their suitability for garnet synthesis. The thermal decomposition and the phase composition of the resulted decomposition compounds are influenced by the nature of metallic cations (yttrium-iron or erbium-iron) and ligand anions (malate or gluconate).     

Synthesis and Crystal Structure of Two New Molydenum(V) Pyrophosphate Complexes

Two new reduced molybdenum pyrophosphates, Na₂₈[Na₂{(Mo₂O₄)₁₀(P₂O₇)₁₀(HCOO)₁₀}]·108H₂O ( 1 ) and Na₂₂(H₃O)₂[Na₄{(Mo₂O₄)₁₀(P₂O₇)₁₀(CH₃COO)₈(H₂O)₄}]·91H₂O ( 2 ) have been synthesized and characterized by single‐crystal X‐ray diffraction. Red crystals of 1 are triclinic, space group , with a = 17.946(4) Å, b = 18.118(4) Å, c = 21.579(4) Å, α = 114.47(3)°, β = 93.54(3)°, γ = 114.39(3)° and V = 5581.8(19) ų, and orange crystals of 2 are monoclinic, space group P2₁/n, with a = 21.467(4) Å, b = 23.146(5) Å, c = 24.069(5) Å, β = 101.76(3)° and V = 11708(4) ų. They are both constructed by Mo^V dimers ({Mo₂O₄(O_P)₄(HCOO)} in 1 , {Mo₂O₄(O_P)₄(CH₃COO)} and {Mo₂O₄(O_P)₄(H₂O)₂} in 2 ) and pyrophosphoric groups. Their structures can be described as two interconnected nonequivalent wheels which are approximately perpendicular, delimiting a large cavity. The larger wheel contains six Mo^V dimers, while the smaller one has four dimers.     

Einfach und doppelt deprotonierte Maleinsäure in Praseodym‐hydrogenmaleat‐octahydrat,Pr(C4O4H3)3 · 8 H2O,und Praseodym‐maleatchlorid‐tetrahydrat,Pr(C4O4H2)Cl · 4 H2O

Single and Double Deprotonated Maleic Acid in Praseodymium Hydrogenmaleate Octahydrate, Pr(C₄O₄H₃)₃ · 8 H₂O, and Praseodymiummaleatechloride Tetrahydrate, Pr(C₄O₄H₂)Cl · 4 H₂O Single crystals of Pr(C₄O₄H₃)₃ · 8 H₂O grew by slow evaporation of a solution which had been obtained by dissolving Pr(OH)₃ in aqueous maleic acid. The triclinic compound (P1, Z = 2, a = 728.63(3), b = 1040.23(3), c = 1676.05(8) pm, α = 72.108(2)°, β = 87.774(2)°, γ = 70.851(2)°, R_all = 0.0261) contains Pr³⁺ ions in ninefold coordination of oxygen atoms which belong to two monodentate maleate ions and seven H₂O molecules. There is one further non‐coordinating maleate ion and one crystal water molecule in the unit cell. Thermal treatment of Pr(C₄O₄H₃)₃ · 8 H₂O leads first to the anhydrous compound which then decomposes to the respective oxide in two steps upon further heating. Evaporation of a solution of Pr(C₄O₄H₃)₃ · 8 H₂O which contained additional Cl^– ions yielded single crystals of Pr(C₄O₄H₂)Cl · 4 H₂O. In the crystal structure (monoclinic, P2₁/c, Z = 4, a = 866.0(1), b = 1344.3(1), c = 896.9(1) pm, β = 94.48(2)°, R_all = 0.0227), the Pr³⁺ ions are surrounded by nine oxygen atoms. The latter belong to four H₂O molecules and three maleate ions. Two of the latter act as bidentate ligands.     

Chemical preparations and crystal data for eight new condensed phosphates

Chemical preparations and main crystallographic data are reported for eight new condensed phosphates: four new cyclotriphosphates, with a general formula MnM₂^II(P₃O₉)₂ · nH₂O, MnBa₂(P₃O₉)₂ · 6H₂O, MnCa₂(P₃O₉)₂ · 10H₂O, MnCa₂(P₃O₉)₂, MnSr₂(P₃O₉)₂ · 4H₂O and four other cyclotriphosphates Mn(NH₄)₄(P₃O₉)₂ · 6H₂O, CdK₄(P₃O₉)₂, MnK₄(P₃O₉)₂ and NiRb₄(P₃O₉)₂. Seven of them belong to previously investigated structure types.     

Tetraammonium Diglycinyl‐octamolybdate(VI) Dihydrate, (NH4)4[(NH3CH2CO)2(Mo8O28)] · 2 H2O

The reaction of ammonium heptamolybdate with hydrazine sulfate in an aqueous solution of glycine at room temperature yielded colorless crystals of (NH₄)₄[(NH₃CH₂CO)₂(Mo₈O₂₈)] · 2 H₂O. The crystal is monoclinic, space group C2/c (no. 15), a = 17.234 Å, b = 10.6892 Å, c = 18.598 Å, β = 108.280°, V = 3253.2 ų, Z = 4. The crystal structure contains ammonium cations and isolated octamolybdate(4–) anions, [(NH₃CH₂CO)₂(Mo₈O₂₈)]^4–, with two zwitterionic glycine molecules as ligands.     

Structure of [NH3(CH2)4NH3]2P4O12·2H2O

After a short survey of what is the present state of the cyclophosphates associated with the organic molecule NH₂(CH₂)₄NH₂, we report chemical preparation and crystal structure for a new example of such compounds. [NH₃(CH₂)₄NH₃]₂P₄O₁₂.2H₂O is monoclinic (S.G. : P2₁/n), with Z = 2 and the following unit-cell parameters : a = 7.6728(8) Å, b = 18.962(3) Å, c = 7.9789(9) Å β = 111.751(9)°. Bidimensional layer arrangement of P₄O₁₂ rings connected to the water molecules thanks to weak H-bonds run parallel to the ab plane. The organic groupements located between these inorganic planes perform the three-dimensional cohesion by NH····O hydrogen bonds.     

Preparation,Structure, and Second‐order Nonlinear Optical Properties of a Borate‐Carboxylic Acid Compound: NH4B[d‐(+)‐C4H4O5]2·H2O

The organic‐inorganic hybrid nonlinear optical (NLO) material NH₄B(d‐ (+)‐C₄H₄O₅)₂ · H₂O (NBC) was synthesized in a borate‐carboxylic acid system. Its structure was determined by single crystal X‐ray diffraction. It crystallizes in the orthorhombic system, space group Pna2₁ (No. 33), with cell parameters a = 11.484(6) Å, b = 5.354(3) Å, c = 21.079(12) Å, V = 1296.0(12), Z = 4. It exhibits a three‐dimensional pseudo tunnel structure consisting of fundamental building block [B(d‐ (+)‐C₄H₄O₅)₂]^– anions. The small cavities are occupied by the H₂O molecules and NH₄⁺ cations, which stabilize the whole structure by O–H ··· O and N–H ··· O hydrogen bonds. The powder X‐ray diffraction (PXRD) of the crystal was also recorded. Elemental analyses, FT‐IR and FT‐Raman spectra analyses, thermal analysis, and diffuse‐reflectance spectra for the compound are also presented, as are band structures and density of states calculation. Nonlinear optical measurements indicate that the material has second harmonic generation (SHG) properties and is phase‐matchable.     

A series of Mixed-Valent Molybdenum Monophosphates,isotypic with leucophosphite represented by CsMo2P2O10 and K1.5Mo2P2O10 · H2O

The structure of two mixed valent molybdenum phosphates, CsMo₂P₂O₁₀ and K_1.5Mo₂P₂O₁₀ · H₂O has been solved from single crystals by X-ray diffraction in the space group P2₁/c with a = 9.428(1), b = 9.943(2), c = 12.348(2) Å and β = 127.38(1)° for CsMo₂P₂O₁₀ and a = 9.721(2), b = 9.805(3), c = 12.329(3) Å and β = 128.73(2)° for K_1.5Mo₂P₂O₁₀ · H₂O. These compounds isotypic with NH₄Mo₂P₂O₁₀ · H₂O and RbMo₂P₂O₁₀ · (1 ? x)H₂O exhibit the leucophosphite structure. The possibility of cationic non stoichiometry in this structure is also shown by the synthesis of two isotypic compounds A_1.5Mo₂P₂O₁₀ · xH₂O (A = Rb, Tl). In these monophosphates, one site Mo(1) is fully occupied by Mo^V, whereas the other octahedral site Mo(2) exhibits a variable valency Mo^III? Mo^IV to Mo^V. The main difference between these different phosphates deals with the distribution of the A cations inside the tunnels, depending upon their size and their content.     

Double complex salts [Pt(NH3)5Cl][M(C2O4)3] · n H2O (M = Fe, Co, Cr): Synthesis and study

Double complexes [Pt(NH₃)₅Cl][Fe(C₂O₄)₃] · 4H₂O, [Pt(NH₃)₅Cl][Co(C₂O₄)₃] · 2H₂O, and [Pt(NH₃)₅Cl][Cr(C₂O₄)₃] · 4H₂O were synthesized and studied by single-crystal X-ray diffraction, X-ray phase analysis, differential thermal analysis, elemental analysis, and IR spectroscopy. The crystal structures of the compounds were examined from the viewpoint of the close packing of coordination polyhedra. The thermal properties of the synthesized complexes and K₃[M(C₂O₄)₃] salts (M = Fe, Co, Cr) were compared. A procedure for the synthesis of the FePt, CoPt, and CrPt intermetallic compounds through the thermolysis of the obtained complexes was developed. Original Russian Text ? K.V. Yusenko, D.B. Vasil’chenko, A.V. Zadesenets, I.A. Baidina, Yu.V. Shubin, S.V. Korenev, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 10, pp. 1589–1593.     

Contribution to the crystal chemistry of tetrametaphosphates (I)

Crystal structures of K₄P₄O₁₂ · 2H₂O and of two polymorphs of Na₂K₂P₄O₁₂ · 2H₂O are reported. K₄P₄O₁₂ · 2H₂O is triclinic P1 with a = 8.153(4), b = 8.222(4), c = 11.154(8) Å, α = 97.33(5), β = 95.46(5), γ = 88.92(5)°, and Z = 2. R = 0.021 for 2898 reflections. Na₂K₂P₄O₁₂ · 2H₂O has two crystalline forms: a triclinic one ($\text{P}\text{1}$) with a = 11.366(8), b = 7.908(5), c = 7.929(5) Å, α = 90.07(5), β = 106.85(5), γ = 95.66(5)°, and Z = 2, and a tetragonal one (P4₁) with a = 7.928(5), c = 21.66(2), and Z = 4. The crystal structures of the first and second crystalline forms have been solved with final R values of 0.022 for 2505 reflections and 0.036 for 1347 reflections, respectively. Crystal data and chemical preparations are given for Na₂(NH₄)₂P₄O₁₂ · 2H₂O and Na₂Rb₂P₄O₁₂ · 2H₂O, both isotypic with the triclinic form of Na₂K₂P₄O₁₂ · 2H₂O. Unit-cell dimensions are, respectively, a = 11.547(8), b = 8.012(5), c = 8.044(5) Å, α = 89.76(5), β = 106.22(5), and γ = 94.78(5)°, for the ammonium salt, and a = 11.577(8), b = 8.006(5), c = 8.032(5) Å, α = 89.79(5), β = 106.58(5), and γ = 95.19(5)° for the rubidium salt. In addition the crystal structures of the two crystalline forms of Na₄P₄O₁₂ · 4H₂O were reexamined in order to localize the hydrogen atoms and refine their positions.     

Interaction in the Li2Mo3O10-CO(NH2)2-H2O system at 25°C

The solubilities and solid phases in the Li₂Mo₃O₁₀-CO(NH₂)₂-H₂O system at 25°C are studied. A compound of composition Li₂Mo₃O₁₀ · 6CO(NH₂)₂ · 4H₂O and lithium trimolybdate decahydrate Li₂Mo₃O₁₀ · 10H₂O are found to exist. The Li₂Mo₃O₁₀ · 6CO(NH₂)₂ · 4H₂O ray crosses the solubility isotherm, which indicates the congruent solubility of the double compound in water. The density, refractive index, dynamic viscosity, surface tension, electrical conductivity, and pH of saturated solutions of the system are determined. The molar volume, equivalent electrical conductivity, reduced conductivity, and solution ionic strength isotherms are calculated. A strong correlation between all the property isotherms and the solubility is observed.     

IV Dodekaedrische [Mo(CN)8]‐Koordination in den cyanoverbrückten Cobalt‐ und Nickel‐Amminkomplexen MII2(NH3)8[Mo(CN)8] · 1,5 H2O (MII = Co,Ni) und Ni2(NH3)9[Mo(CN)8] · 2 H2O

Crystal Structures of Octacyanomolybdates(IV). IV Dodecahedral [Mo(CN)₈] Coordination of the Cyano‐Bridged Cobalt and Nickel Ammin Complexes M^II₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (M^II = Co, Ni) and Ni₂(NH₃)₉[Mo(CN)₈] · 2 H₂O At single crystals of the hydrated cyano complexes Co₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (a = 910.0(4), b = 1671(2), c = 1501(1) pm, β = 93.76(6)°) and Ni₂(NH₃)₈[Mo(CN)₈] · 1.5 H₂O (a = 899.9(9), b = 1654.7(4), c = 1488(1) pm, β = 94.01°), isostructurally crystallizing in space group P2₁/c, Z = 4, and of trigonal Ni₂(NH₃)₉[Mo(CN)₈] · 2 H₂O (a = 955.1(1), c = 2326.7(7) pm, P3₁, Z = 3), X‐ray structure determinations were performed at 168 resp. 153 K. The [Mo(CN)₈]^4– groups of the three compounds, prepared at about 275 K and easily decomposing, show but slightly distorted dodecahedral coordination (mean distances Mo–C: 216.3, 215.4 and 216.1 pm). Within the monoclinic complexes the anions twodimensionally form cyano bridges to the ammin cations [M(NH₃)₄]²⁺ and are connected with the resulting [MN₆] octahedra (Co–N: 215.1 pm, Ni–N: 209.8 pm) into strongly puckered layers. The trigonal complex exhibits a chain structure, as one [Ni(NH₃)₅]²⁺ cation is only bound as terminal octahedron (Ni–N: 212.0 pm). Details and the influence of hydrogen bridges are discussed.     

Study of the solubility of components in the system Mg(ClO3)2-2NH2C2H4OH · H3C6H5O7-H2O

The solubility of components in the system Mg(ClO₃)₂-2NH₂C₂H₄OH · H₃C₆H₅O₇-H₂O was studied from the complete freezing temperature ?59.4°C to 20.0°C. A polythermal solubility diagram was constructed, in which the crystallization fields were determined for ice, Mg(ClO₃)₂ · 16H₂O, Mg(ClO₃)₂ · 12H₂O, Mg(ClO₃)₂ · 6H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇ · H₂O, 2NH₂C₂H₄OH · H₃C₆H₅O₇, and two new compounds, [(HOC(CH₂COOH)₂COO)₂Mg · 2H₂O] and [HOC(CH₂COO)₂MgCOOH · 2H₂O], which were identified by chemical and physicochemical analysis methods.     

Synthese,Kristallstruktur und Eigenschaften der käfigartigen,sechsbasigen Säure P12S12N8(NH)6 · 14 H2O sowie ihrer Salze Li6[P12S12N14] · 26 H2O, (NH4)6[P12S12N14] · 10 H2O und K6[P12S12N14] · 8 H2O

Syntheses, Crystal Structure, and Properties of the Cage‐like, Hexaacidic P₁₂S₁₂N₈(NH)₆ · 14 H₂O and its Salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O, (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O, and K₆[P₁₂S₁₂N₁₄] · 8 H₂O The cage‐like acid P₁₂S₁₂N₈(NH)₆ · 14 H₂O was obtained by the reaction of KSCN with P₄S₁₀ via the formation of K₆[P₁₂S₁₂N₁₄] · 8 H₂O and subsequent ion exchange reactions in aqueous solution. Starting from the acid the salts Li₆[P₁₂S₁₂N₁₄] · 26 H₂O and (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O were synthesized. According to X‐ray single‐crystal structure analyses the compounds are built up by isosteric P–N cages [P₁₂S₁₂N^[3]₈N^[2]₆]^6–. Each of them is made up of twelve P₃N₃ rings, which exclusively exhibit the boat conformation. The cages have the idealized symmetry 2/m3; P₁₂S₁₂N₈(NH)₆ · 14 H₂O: P1, a = 1119.11(7), b = 1123.61(7), c = 1125.80(6) pm, α = 80.186(4), β = 60.391(4), γ = 60.605(4)°, Z = 1; Li₆[P₁₂S₁₂N₁₄] · 26 H₂O: Fm3, a = 1797.4(1) pm, Z = 4; (NH₄)₆[P₁₂S₁₂N₁₄] · 10 H₂O: P6₃, a = 1153.2(1), c = 2035.6(2) pm, Z = 2; K₆[P₁₂S₁₂N₁₄] · 8 H₂O: R3c, a = 1142.37(5), c = 6009.6(3) pm, Z = 6. In the crystal the cages of the acid are crosslinked via hydrate molecules by hydrogen bonds. The cations in the salts show a high‐mobility and are located between the cages.     

Reactivity of sodium triphosphate crystal hydrates

Kinetics of thermal decomposition of single crystals and polycrystalline samples of Na₅P₃O₁₀·6D₂O and Na₅P₃O₁₀·6H₂O, interaction of fine-crystalline Na₅P₃O₁₀·1.6H₂O with humid gaseous ammonia were studied using TLC, XRDA, IRS, TG, DTA, DSK.