Protonated Melonate Ca[HC6N7(NCN)3]·7H2O – Synthesis,Crystal Structure,and Thermal Properties

Calcium hydrogenmelonate heptahydrate Ca[HC₆N₇(NCN)₃] · 7H₂O was obtained by metathesis reaction in aqueous solution. The structure of the molecular salt was elucidated by single‐crystal X‐ray diffraction. The crystal structure consists of alternating layers of planar monopronated melonate ions, Ca²⁺ and crystal water molecules. The anions of adjacent layers are staggered so that no π–π stacking occurs. The melonate entities are interconnected by hydrogen bonds within and between the layers. Ca[HC₆N₇(NCN)₃] · 7H₂O was investigated by solid‐state NMR and FTIR spectroscopy, TG and DTA measurements.     

Synthesis and Crystal Structure of the Palladium(IV) Polyoxomolybdate,K0.75Na3.75[PdMo6O24H3.5]·17H2O

The first example of a heteropolyoxomolybdate containing palladium(IV) was isolated and characterized by X‐ray crystallography. The palladium(IV) hexamolybdate, K_0.75Na_3.75[PdMo₆O₂₄H_3.5]·17H₂O, was isolated from an aqueous solution at pH 4.5 in the space group P\bar{1} , a 10.790(2), b 12.244(3), c 14.086(3) Å, α 113.77(1), β 90.41(1),γ 107.86(1)°, and the structure was determined using X‐ray diffraction methods, refining to a residual of 0.0301 for 5334 reflections. A formal “[PdMo₆O₂₄H₃]^5–” subunit exhibits the basic Anderson structure, with two [PdMo₆O₂₄H₃]^5– cluster anions in the structure bridged by a hydrogen atom (formally an H⁺) situated on a center of symmetry to give a “[Pd₂Mo₁₂O₄₈H₇]^9–” dimeric anion. The palladium(IV) atom occupies a slightly distorted octahedral environment, with Pd–O distances ranging from 1.968 to 2.009 Å.     

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.     

Monodentate Coordination of 4,4′‐Bipyridine Leading to a Supramolecular Network – Synthesis and Crystal Structure of [H2bpp][{Cu(Hbpy)2}{α‐HP2W18O62}]·4H2O

The new supramolecular compound [H₂bpp][{Cu(Hbpy)₂}{α‐HP₂W₁₈O₆₂}]·4H₂O ( 1 ) (bpy = 4,4′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane) was synthesized hydrothermally and characterized byelemental analysis, IR spectroscopy, thermogravimetric analysis and single‐crystal X‐ray diffraction. In compound 1 , the cationic fragment [Cu(Hbpy)₂]⁺ connects to the Dawson anion through a coordinating Cu←O bond, and the copper atom is coordinated by another polyoxoanion through a weak covalent bond with a Cu1–O26 distance of 2.879(2) Å, forming a polymeric chain. The bpy ligand in [Cu(Hbpy)₂]⁺ adopts a monodentate coordination mode, the other nitrogen atom of the bpy ligand is protonated. The protonated Hbpy⁺ acts as hydrogen‐bond donor and constructs a two‐dimensional double‐sheet supramolecular network involving the one‐dimensional chains through the hydrogen bonds. The H₂bpp²⁺ ion connects twoα‐HP₂W₁₈O₆₂^6– clusters from two supramolecular networks through hydrogen bonds and creates a three‐dimensional supramolecular architecture. The thermal decomposition of 1 happens over a wide temperature range (450–800 °C), which indicates that it might include complicated oxidation–reduction processes.     

Synthesis,Crystal Structure,Thermal and Explosive Properties of [Cd(SCZ)3(H2O)](PA)2·3H2O (SCZ = Semicarbazide,PA = Picrate)

The heptacoordinate transition metal coordination compound [Cd(SCZ)₃(H₂O)](PA)₂ · 3H₂O ( 1 ) with the ligand semicarbazide (SCZ) and the counteranion picrate (PA) was synthesized and characterized by elemental analysis and FTIR spectroscopy. Single‐crystal X‐ray diffraction analysis revealed that 1 crystallizes in the monoclinic space group P21/c. The Cd²⁺ ion is heptacoordinated by three SCZ groups and a water molecule. SCZ presents typical bidentate coordination modes. The thermal decomposition mechanism of 1 was studied by differential scanning calorimetry (DSC), which revealed that complex 1 exhibits three small endothermic and two large exothermic processes. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa‐Doyle's method, respectively. The heat of combustion was measured by oxygen bomb calorimetry. The enthalpy of formation, the critical temperature of thermal explosion, the entropy of activation (ΔS^≠), the enthalpy of activation (ΔH^≠), and the free energy of activation (ΔG^≠) were also calculated. Sensitivity tests revealed that 1 is insensitive to mechanical stimuli.     

New Borate‐citrate: Synthesis,Structure, and Properties of Sr[B(C6H5O7)2](H2O)4·3H2O

Single crystals of Sr[B(C₆H₅O₇)₂](H₂O)₄ · 3H₂O, a new borate‐citrate material, were grown with sizes up to 8 × 6 × 2 mm by slow evaporation of water at room temperature. The structure of Sr[B(C₆H₅O₇)₂](H₂O)₄ · 3H₂O was determined by single‐crystal X‐ray diffraction. It crystallizes in the monoclinic space group P2₁/c, with a = 11.363(3) Å, b = 18.829(4) Å, c = 11.976(3) Å, β = 110.736(3)°, and Z = 4. The SrO₈ dodecahedra, BO₄ tetrahedra and citrate groups are linked together to form chains. The compound was characterized by IR and UV/Vis/NIR transmittance spectroscopy as well as thermal analysis.     

Synthesis,Crystal Structure Determination from X‐Ray Powder Diffractometry and Vibrational Spectroscopic Properties of Mg[N(CN)2]2 · 4 H2O

Magnesium dicyanamide tetrahydrate Mg[N(CN)₂]₂ · 4 H₂O was synthesized by aqueous ion exchange starting from Na[N(CN)₂] and Mg(NO₃)₂ · 6 H₂O. The crystal structure was solved and refined on the basis of powder X‐ray diffraction data (P2₁/c, Z = 2, a = 737.50(2), b = 732.17(1), c = 971.67(2) pm, β = 98.074(1)°, wR_p = 0.059, R_p = 0.046, R_F = 0.075). In the crystal there are neutral complexes [Mg[N(CN)₂]₂(H₂O)₄] which are only connected via hydrogen bonds. Above 40 °C the tetrahydrate decomposes into anhydrous Mg[N(CN)₂]₂.     

Synthesis,Crystal and Electronic Structure of the Nitridoaluminosilicate Ca5[Si2Al2N8]

Ca₅[Si₂Al₂N₈] was synthesized from elementary aluminum and silicon with phase‐pure tricalcium dinitride at 1280 K under dry argon in a sealed niobium ampoule. Ca₃N₂ was freshly prepared from distilled calcium metal in a dry nitrogen atmosphere. The compound crystallizes in form of transparent yellow distorted octahedra. In air and under moisture Ca₅[Si₂Al₂N₈] undergoes hydrolysis. The structure was determined from a single crystal to be orthorhombic (space group Pbcn – no. 60, a = 925.5, b = 614.0 and c = 1557.8 pm). The nitridoaluminate and ‐silicate substructures are separated into planes of edge and corner‐shared aluminate tetrahedra, which are linked by edge‐sharing double tetrahedral pillars of the silicate. The structure was confirmed by electrostatic and quantum mechanical analysis.     

Synthesis,Crystal Structure and Magnetic Behaviour of {[Co(dimb)2(H2O)2]·(NO3)2·(H2O)2}n

The title complex {[Co(dimb)₂(H₂O)₂]·(NO₃)₂·(H₂O)₂}_n ( 1 ) (dimb = 1,3‐di(imidazol‐1‐ylmethyl)‐5‐methylbenzene) has been hydrothermally synthesized by the reaction of dimb with Co(NO₃)₂·6H₂O in aqueous solution. The cobalt(II) atoms are linked by bridging dimb ligands to form 2D corrugated and wavy networks containing Co₄(dimb)₄ macrocyclic motifs. Two neighboring independent layers interlinked each other in a parallel fashion to construct three‐dimensional structure by O–H···O, N–H···O and C–H···O hydrogen bonds. Magnetic measurement shows the weak antiferromagnetic interaction with a one‐dimensional chain model in the range of 5–300 K, with J of –0.68 cm⁻¹.     

(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.     

Ein anionischer Oxohydroxo‐Komplex mit Bismut(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O

An Anionic Oxohydroxo Complex with Bismuth(III): Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O Colourless, plate‐like, air sensitive crystals of Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O are obtained by reaction of Bi₂O₃ or Bi(NO₃)₃ · 5H₂O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi₂O₂(OH)₆]^4— with bismuth in an ψ¹‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na₃BiO₃.     

A New Energetic Complex [Co(2,4,3‐tpt)2(H2O)2]·2NO3: Synthesis,Structure, and Catalytic Thermal Decomposition for Ammonium Perchlorate

The energetic complex, [Co(2,4,3‐tpt)₂(H₂O)₂] · 2NO₃ ( 1 ) [2,4,3‐tpt = 3‐(2‐pyridyl)‐ 4‐(4'‐pyridyl)‐5‐(3′‐pyridyl)‐1H‐1,2,4‐triazole], was synthesized and characterized by single‐crystal X‐ray diffraction, thermogravimetric analyses, elemental analysis, X‐ray powder diffraction, and IR spectroscopy. The title complex is a 0D motif with a unit of [Co(2,4,3‐tpt)₂(H₂O)₂]²⁺, whereas NO₃^– ions not only act as counter anions to balance the charge of the Co^II cations, but also provide hydrogen bond interactions, which make the 0D motif into a 1D chain. Furthermore, the thermal decomposition of ammonium perchlorate (AP) with complex 1 was explored by differential scanning calorimetry (DSC) over the temperature range from 50–500 °C. AP is completely decomposed in a shorter time in the presence of complex 1 , and the decomposition heat of the mixture is 2.143 kJ g^–1, significantly higher than pure AP. By Kissinger's method, the ratio of E_a/ln(A) is 11.87 for the mixture, which indicates that complex 1 shows good catalytic activity toward AP decomposition.     

Synthesis,Crystal Structure and Characterization of a new Protonated Magnesium Borophosphate: (H3O)Mg(H2O)2[BP2O8]·H2O

A new protonated borophosphate (H₃O)Mg(H₂O)₂[BP₂O₈]·H₂O ( 1 ) was synthesized under mild hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, FTIR spectroscopy and TG‐DTA. The compound crystallizes in the hexagonal system, space group P6(1)22 (No 178), a = 9.4462(7) Å, c = 15.759(2) Å, V = 1217.8(2) Å³, and Z = 6. There exist infinite helical $^1_\infty$ {[BP₂O₈]^3–} ribbons built up from corner‐sharing PO₄ and BO₄ tetrahedra, which are connected by MgO₄(H₂O)₂ leading to an infinite three‐dimensional open‐framework. The H₃O⁺ ions are located at the free thread of the helical ribbons, whereas crystallized water occupy the channels of the helical ribbons. The dehydration of the compound occurs at a higher temperature which is presumably due to the anisotropic hydrogen bonds in the crystal structure. The luminescent properties of the compound were studied.     

Crystal and Molecular Structure of [2,6‐(Me2NCH2)2C6H3]2SnF2, an Intramolecularly Coordinated Diorganotin Difluoride

Single‐crystal X‐ray diffraction analysis of [2,6‐(Me₂NCH₂)₂C₆H₃]₂SnF₂ reveals that only one of the two dimethylaminomethyl groups of each pincer‐type ligands [2,6‐(CH₂NMe₂)₂C₆H₃]^? is coordinated to the tin atom at Sn‐N distances of 2.576(2) and 2.470(2) Å, inducing chirality of the latter. The tin atom exhibits a distorted octahedral trans(C,C)cis(N,N)cis(F,F) configuration. Extensive intra‐ and intermolecular C‐H···F hydrogen bonding is observed with the latter giving rise to formation of polymeric chains.     

Synthesis and Characterization of the New Lacunar Zincophosphate [C6H10N2][ZnP2O8H2]·0.6H2O

The new zincophosphate of chemical formula [C₆H₁₀N₂][ZnP₂O₈H₂] · 0.6H₂O was hydrothermally synthesized with p‐phenylenediamine as structure‐directing agent. The title compound crystallizes in the trigonal symmetry (proposed space group P3m1), where inorganic zincophosphate chains form layers due to the half occupancy of the unique crystallographic zinc site. The layers are separated from each other by p‐phenylenediammonium dications with hydrogen bonding scheme involving the ammonium protons that reveals a pillar‐like 3D structure aspect. The compound was characterized by powder X‐ray diffraction, multinuclear solid‐state NMR, scanning electron microscopy, chemical analysis, and thermogravimetric analysis.     

Synthesis and Characterization of the Mixed‐Linker Copper(II) Coordination Polymer [Cu(HO3PC6H4SO3)(C10N2H8)]·H2O

A new copper(II) phosphonatobenzenesulfonate incorporating 4,4′‐bipyridine (4,4′‐bipy) as auxiliary ligand has been discovered through systematic high‐throughput (HT) screening of the system Cu(NO₃)₂·3H₂O/H₂O₃PC₆H₄SO₃H/4,4′‐bipy using different solvents. The hydrothermal synthesis of [Cu(HO₃PC₆H₄SO₃)(C₁₀H₈N₂)]·H₂O ( 1 ) was further optimized by screening various copper(II) salts. The crystal structure of 1 was determined by single‐crystal X‐ray diffraction and unveiled the presence of isolated sixfold coordinated Jahn–Teller‐distorted Cu²⁺ ions. The isolated CuN₂O₄ octahedra are interconnected by phosphonate and sulfonate groups to form chains along the c‐axis. The organic groups, namely phenyl rings and 4,4′‐bipy molecules cross‐link the chains into a three‐dimensional framework. Water molecules are found in the narrow voids in the structure which are held by weak hydrogen bonds. Upon dehydration, the structure of 1 undergoes a phase transition, which was confirmed by TG measurements and temperature dependent X‐ray powder diffraction. The new structure of 1‐h was refined with Rietveld methods. Detailed inspection of the structure revealed the directional switching of the Jahn–Teller distortion upon de/rehydration. Weak ferro‐/ferrimagnetic interactions were observed by magnetic investigations of 1 , which switch to antiferromagnetic below 3.5 K. Compounds 1 and 1‐h are further characterized by thermogravimetric and elemental analysis as well as IR spectroscopy.     

Solvothermal Synthesis,Crystal Structure and Properties of the First Organic‐templated Holmium Sulfate [C2N2H10]3[Ho2(SO4)6·2H2O]

The first organic amine‐templated holmium sulfate [C₂N₂H₁₀]₃[Ho₂(SO₄)₆·2H₂O] ( 1 ) has been synthesized solvothermally and has been structurally characterized by single‐crystal X‐ray diffraction studies, IR spectroscopic, thermogravimetric (TG) and inductivity coupled plasma (ICP) measurements. Crystal analyses of compound 1 showed a novel inorganic layer constructed from the zigzag and helical [–Ho–O–S–O–]_n chains, both of the chains are connected by μ‐2 SO₄^2– groups to form 10‐membered rings. The solvent plays an important role during the formation of 1 .     

Structural and Vibrational Studies of Sr2[W(CN)8]·10H2O

The crystal structure of distrontium octacyanotungstate decahydrate, Sr₂[W(CN)₈] · 10H₂O, was solved using X‐ray single crystal diffraction. The tungsten atom lies on a two fold axis. Eight cyanide anions create tetragonal antiprismatic coordination sphere of tungsten atom. The two edge‐sharing tetragonal antiprisms of [Sr(NC)₃(OH₂)₅], create a dimer, [Sr₂(CN)₆(H₂O)₆(μ‐H₂O)₂], which lies on the inversion center. One symmetry independent water molecule is located in a void of 40 Å³. Vibrational (FT‐IR and FT‐Raman spectroscopic) behavior of main structural units is discussed. It was spectroscopically confirmed that the geometry of [W(CN)₈]^4– anion is slightly distorted from that corresponding to “free” anion. The number of observed bands is significantly lower than that expected for C₂ point group.     

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.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.