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.     

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.     

Metal Complexes of New Mixed Oxaaza‐Macrocyclic Ligands. X‐Ray Crystal Structure of L1, L2, [SrL2(H2O)2](ClO4)2 and [BaL2(NCS)2(CH3CN)]·CH3CN

A new mixed oxaaza‐macrocyclic ligand, L¹, has been obtained by direct synthesis between 1,4‐bis‐(2′‐formylphenyl)‐1,4‐dioxabutane and the diamine 2,2′‐ethylenedioxydiethylamine. The dialkylated ligand L², bearing two nitrobenzyl pendant groups, has been prepared and transitional, post‐transitional and Ca²⁺, Sr²⁺, and Ba²⁺ metal complexes have been synthesized in order to elucidate the coordination preferences. The crystal structures of the ligands L¹ and L² and the complexes [SrL²(H₂O)₂](ClO₄)₂ and [BaL²(NCS)₂(CH₃CN)]·CH₃CN have been determined by single crystal X‐ray diffraction. The structures reveal the presence of mononuclear endomacrocyclic complexes where the pendant arms radiate away from the ligand.     

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,Crystal Structure and Properties of Rubidium Dihydrogentricyanomelaminate Semihydrate Rb[H2C6N9] · 1/2 H2O

Rubidium dihydrogentricyanomelaminate semihydrate Rb[H₂C₆N₉] · ¹/₂ H₂O was obtained as colorless rod‐like single crystals from a solution of Rb₃[C₆N₉] · H₂O and 0.1 M HCl after water evaporation at room temperature. According to the X‐ray single‐crystal structure determination (Rb[H₂C₆N₉] · ¹/₂ H₂O: C2/c (no. 15), a = 2007.4(3) pm, b = 512.2(1) pm, c = 2168.0(4) pm, β = 111.66(2)°, Z = 8, R1 = 0.059, 2391 independent reflections, 159 parameters) Rb⁺ and cyclic planar [H₂C₆N₉]^— ions as well as hydrate water molecules occur in the crystal. Rb[H₂C₆N₉] · ¹/₂ H₂O was investigated by FTIR and Raman spectroscopy, TG measurements and temperature‐dependent X‐ray powder diffraction. According to the thermoanalytic investigations, dehydration of Rb[H₂C₆N₉] · ¹/₂ H₂O starts above 60 °C and is finished below 250 °C.     

Photomagnetic Switching of the Complex [Nd(dmf)4(H2O)3(μ‐CN)Fe(CN)5]⋅H2O Analyzed by Single‐Crystal X‐Ray Diffraction

X‐ray vision : Single‐crystal XRD experiments (see picture) reveal the excited‐state structure of the photomagnetic heterobimetallic title complex. The system shows a decrease in all the iron–ligand bond lengths, suggesting that photoexcitation involves a ligand‐to‐metal charge transfer or a change in the superexchange coupling between the metal centers.

     

Synthesis,Crystal Structures,and Vibrational Spectra of Novel Azidopalladates of the Alkali Metals Cs2[Pd(N3)4] and Rb2[Pd(N3)4]·2/3H2O

The transparent dark orange compounds Cs₂[Pd(N₃)₄] and Rb₂[Pd(N₃)₄]·²/₃H₂O are synthesized by reaction of the respective binary alkali metal azides with K₂PdCl₄ in aqueous solutions. According to single‐crystal X‐ray diffraction investigations, the novel ternary azidopalladates(II) crystallize in the monoclinic space group P2₁/c (no. 14) with a = 705.7(2) pm, b = 717.3(2) pm, c = 1125.2(5) pm, β = 104.58(2)°, mP30 for Cs₂[Pd(N₃)₄] and a = 1041.4(1) pm, b = 1292.9(2) pm, c = 1198.7(1) pm, β = 91.93(1)°, mP102 for Rb₂[Pd(N₃)₄]·²/₃H₂O, respectively. Predominant structural features of both compounds are discrete [Pd^II(N₃)₄]^2– anions with palladium in a planar coordination by nitrogen, but differing in point group symmetries., The vibrational spectra of the compounds are analyzed based on the idealized point group C_4h of the spectroscopically relevant unit, [Pd(N₃)₄]^2– taking into account the site symmetry splitting due to the symmetry reduction in the solid phase.     

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.     

Synthesis and Crystal Structure Determination by X‐Ray Powder Diffraction of Nickel Tetrametaphosphimate Octahydrate Ni2(PO2NH)4 · 8 H2O

Ni₂(PO₂NH)₄ · 8 H₂O is isotypic with M₂(PO₂NH)₄ · 8 H₂O (M = Mg, Mn, Co, Zn) and crystallizes in the space group P2₁/c, Z = 2, with a = 641.25(1), b = 1041.42(1), c = 1278.18(2) pm and β = 104.243(1)°. The structure is composed of Ni²⁺ and (PO₂NH)₄^4? ions as well as crystal water molecules. The P₄N₄ rings of the (PO₂NH)₄^4? ions exhibit a slightly distorted chair–2 conformation, which has been described by torsion angles, displacement asymmetry parameters and puckering parameters. The tetrametaphosphimate anions are connected forming layers. These layers are linked solely by hydrogen bonds, forming a three‐dimensional network.     

Synthesis,Single Crystal Structure Determination and Rietveld Refinement of Cadmium Tetrametaphosphimate Octahydrate Cd2(PO2NH)4·8H2O

Cd₂(PO₂NH)₄ · 8H₂O crystallizes in space group P2₁/c (no. 14), Z = 2, with a = 648.5(2), b = 1070.5(2), c = 1328.7(3) pm and β = 103.11(3) °. The structure, isotypic with M₂(PO₂NH)₄ · 8H₂O (M = Mg, Mn, Co, Ni, Zn), is composed of Cd²⁺ and (PO₂NH)₄^4? ions as well as crystal water molecules. The P₄N₄ rings of the (PO₂NH)₄^4? ions exhibit a slightly distorted chair‐2 conformation, which has been described by torsion angles, displacement asymmetry parameters and puckering parameters. The tetrametaphosphimate anions are connected forming layers. These layers are linked solely by hydrogen bonds, forming a three‐dimensional network.     

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.     

The Crystal Structure of Trimethyl Borate by Neutron and X‐ray Powder Diffraction

The crystal structure of one of the simplest organoboron compounds, trimethyl borate does not appear to have been determined hitherto. The compound is of interest for the study of π‐donor ligands and their interaction with the π‐acceptor behavior of trigonal boron and the consequences of such interactions on molecular structure. We used powder neutron (with isotopically labeled material) and X‐ray diffraction to determine the crystal structure of trimethyl borate at 15 K and 200 K (neutron) and 200 K (X‐ray). The material is hexagonal (Z = 2) with a = b = 6.950(8) Å and c = 6.501(3) Å at 15 K. The unit cell volume is 272.00(1) ų. The space group is P6₃/m (SG 176) at 15 K and 200 K. This is the first crystal structure solved on the Neutron Powder Diffractometer (NPDF) at the Lujan Center.     

[Gd(C10H9N2O4)(C10H8N2O4)(H2O)3]2·phen·4H2O的晶体结构和生物活性

在水乙醇混合溶剂中，首次得到了2-羰基丙酸水杨酰腙、1，10-菲啰啉与硝酸钆形成的配合物[Gd(C₁₀H₉N₂O₄)(C₁₀H₈N₂O₄)(H₂O)₃]₂·phen·4H₂O，并测试了其单晶结构。该配合物属三斜晶系，空间群为P-1。每个配合物分子中有两个九配位的钆的结构单元，每个钆离子与两个三齿配体2-羰基丙酸水杨酰腙（分别以负一价和负二价形式）和三个水分子配位。每个钆单元在空间呈扭曲的单帽四方反棱柱。同时还有一个游离的1，10-菲啰啉存在于晶格中，通过氢键与配位水作用。生物活性试验表明该配合物对三种病原菌有一定的抑菌活性。     

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.     

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.     

Design,Synthesis, and X‐Ray Crystal Structure of a Fullerene‐Linked Metal–Organic Framework

Given the unique structural and electronic properties of C₆₀, metal–organic frameworks (MOFs) containing C₆₀ linkers are expected to exhibit interesting characteristics. A new hexakisfullerene derivative possessing two pairs of phenyl pyridine groups attached to two methano‐carbon atoms located at the trans‐1 positions was designed and synthesized. The four pyridyl nitrogen atoms define a perfectly planar rectangle. This new C₆₀ derivative was used to assemble the first fullerene‐linked two‐dimensional MOF by coordination with Cd²⁺.     

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.