Synthesis and structure of [(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>CSSC(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>[OsBr<Subscript>6</Subscript>]Br<Subscript>2</Subscript> · 3H<Subscript>2</Subscript>O

The complex [(NH₂)₂CSSC(NH₂)₂]₂[OsBr₆]Br₂ · 3H₂O is synthesized by the reaction of K₂OsBr₆ with thiocarbamide in concentrated HBr and characterized using electronic absorption and IR absorption spectroscopy. Its crystal structure is determined by X-ray diffraction. The crystals are orthorhombic, a = 11.730(2) Å, b = 14.052(3) Å, c = 16.994(3) Å, space group Cmcm, and Z = 4. The [OsBr₆]^2? anionic complex has an octahedral structure. The Os-Br distances fall in the range 2.483–2.490 Å. The α,α′-dithiobisformamidinium cation is a product of the oxidation of thiocarbamide. The S-S and C-S distances are 2.016 and 1.784 Å, respectively. The H₂O molecules, Br^?ions, and NH₂ groups of the cation are linked by hydrogen bonds.     

Crystal structure and properties of K<Subscript>2</Subscript>[OsO<Subscript>2</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>] · 2H<Subscript>2</Subscript>O

The synthesis and X-ray diffraction study of the compound K₂[OsO₂(C₂O₄)₂] · 2H₂O are performed. The compound crystallizes in the triclinic crystal system, space group P \(\bar 1\), a = 6.545(1) Å, b = 6.835(2) Å, c = 7.595(2) Å, α = 85.76(2)°, β = 65.33(2)°, γ = 71.14(2)°, and Z = 1. The osmium atom is located at the center of symmetry and has a distorted octahedral coordination formed by oxygen atoms: two oxygen atoms of the osmyl group occupy the apical positions [Os-O, 1.730(2) Å], and four oxygen atoms of the oxalate ions lie in the equatorial plane. The K⁺ cation is surrounded by ten oxygen atoms located at different K-O distances in the range from 2.787(2) to 3.158(2) Å. The assignment of the absorption bands in the IR spectrum of K₂[OsO₂(C₂O₄)₂] · 2H₂O is performed. The electronic absorption spectra of the compound are recorded in different solvents, and the thermal behavior in air is studied.     

X-ray diffraction study of Rb<Subscript>2</Subscript>[(UO<Subscript>2</Subscript>)<Subscript>2</Subscript>(CrO<Subscript>4</Subscript>)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 4H<Subscript>2</Subscript>O

The compound Rb₂[(UO₂)₂(CrO₄)₃(H₂O)₂] · 4H₂O was studied by X-ray diffraction. The crystals are monoclinic, a = 10.695(2) Å, b = 14.684(3) Å, c = 14.125(3) Å, β = 108.396(4)°, sp. gr. P2₁/c, Z = 4, V = 2104.9(7) ų, and R = 0.0491. The main structural units are layers consisting of [(UO₂)₂(CrO₄)₃(H₂O)₂]^2? anions belonging to the crystal-chemical group A ₂ T ₂ ³ B ²M ₂ ¹ (A = UL ₂ ²⁺ , T ³ and B ² are CrO ₄ ^2? , and M ¹ is H₂O) of uranyl complexes. The uranium-containing layered groups are held together by electrostatic interactions with rubidium cations, as well as by hydrogen bonds with the participation of inner- and outer-sphere water molecules.     

Crystal structure of byelorussite-(Ce) NaMnBa<Subscript>2</Subscript>Ce<Subscript>2</Subscript>(TiO)<Subscript>2</Subscript>[Si<Subscript>4</Subscript>O<Subscript>12</Subscript>]<Subscript>2</Subscript>(F,OH) · H<Subscript>2</Subscript>O

The crystal structure of the mineral byelorussite-(Ce) NaMnBa₂Ce₂Ti₂Si₈O₂₆(F,OH) · H₂O belonging to the joaquinite group was solved and refined to R = 0.033 based on 4813 reflections with I > σ2(I). The parameters of the orthorhombic unit cell are a = 22.301(4) Å, b = 10.514(2) Å, c = 9.669(2) Å, V = 2267.1(8) ų, sp. gr. Ama2, and Z = 4. The structure is composed of three-layer sheets, which consist of dimers of edge-sharing Ti octahedra located between isolated four-membered [Si₄O₂] rings. The sheets are linked to each other by Mn 5-vertex polyhedra to form a heteropolyhedral framework. Large cavities in the framework are occupied by Na 6-vertex polyhedra, Ba 11-vertex polyhedra, and REE 9-vertex polyhedra.     

Synthesis and X-ray diffraction study of [UO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>] · 2C<Subscript>12</Subscript>H<Subscript>18</Subscript>O

The compound [UO₂(NO₃)₂(H₂O)₂] · 2C₁₂H₁₈O was synthesized and studied by IR spectroscopy and X-ray diffraction. The structure consists of the neutral island groups [UO₂(NO₃)₂(H₂O)₂], which belong to the crystal-chemical group AB ⁰¹ ₂ M ¹ ₂ (A = UO₂ ²⁺, B ⁰¹ = NO₃⁻, M ¹ = H₂O) of uranyl complexes, and 1-adamantyl methyl ketone molecules. The characteristic features of the association of the complexes [UO₂(NO₃)₂(H₂O)₂] and 1-adamantyl methyl ketone molecules in the crystal structure via hydrogen bonds are considered with the use of Voronoi-Dirichlet polyhedra.     

Crystal and molecular structure of phenanthrolinium peroxodisulfate dihydrate (C<Subscript>12</Subscript>H<Subscript>9</Subscript>N<Subscript>2</Subscript>)<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>8</Subscript> · 2H<Subscript>2</Subscript>O

The crystal structure of (HPhen)₂S₂O₈ · 2H₂O is studied using X-ray diffraction. The crystals are monoclinic, a = 23.716(5) Å, b = 10.220(2) Å, c = 13.103(3) Å, β = 128.03(2)°, V = 2501.6(9) ų, Z = 4, space group C2/c, and R = 0.0745 for 1579 reflections with I > 2σ(I). The crystal is built of S₂O ₈ ^2? centrosymmetric anions, HPhen ⁺ cations, and molecules of crystallization water. Hydrogen bonds link the structural units into chains. Within a chain, stacking interactions are observed between the phenanthroline rings (the interplanar spacing between the rings is 3.8 Å, and the dihedral angle between their planes is 8°). The data of IR spectroscopy confirm the formation of the N(Phen)-H bond.     

Synthesis and crystal structure of Na<Subscript>3</Subscript>(H<Subscript>3</Subscript>O)[UO<Subscript>2</Subscript>(SeO<Subscript>3</Subscript>)<Subscript>2</Subscript>]<Subscript>2</Subscript>· H<Subscript>2</Subscript>O

Single crystals of the compound Na₃(H₃O)[UO₂(SeO₃)₂]₂ · H₂O (I) have been synthesized, and their structure has been investigated using X-ray diffraction. Compound I crystallizes in the triclinic system with the unit cell parameters a = 9.543(6)Å, b = 9.602(7)Å, c = 11.742(8)Å, α = 66.693(16)°, β = 84.10(2)°, γ = 63.686(14)°, space group P \(\bar 1\), Z = 2, and R = 0.0734. The uranium-containing structural units of the crystals are [UO₂(SeO₃)₂]^2? chains, which belong to the crystal-chemical group AB ² B ¹¹ (A = UO ₂ ²⁺ , B ² = SeO ₃ ^2? , B ¹¹ = SeO ₃ ^2? ) of the uranyl complexes. The structures of the compounds containing the [UO₂(SeO₃)₂]^2? anionic complexes are compared.     

Synthesis and crystal structure of [UO<Subscript>2</Subscript>CrO<Subscript>4</Subscript>(C<Subscript>5</Subscript>NH<Subscript>5</Subscript>COO)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)]·2H<Subscript>2</Subscript>O

Crystals of UO₂CrO₄(C₅NH₅COO)₂(H₂O)] · 2H₂O are synthesized and their structure is studied by X-ray diffraction. The compound crystallizes in the triclinic crystal system. The unit cell parameters are as follows: a = 7.0834(10) Å, b = 10.6358(14) Å, c = 12.9539(17) Å, α = 75.096(2)°, β = 74.490(2)°, and γ = 80.657(2)°; V = 904.1(2) ų, space group P \(\bar 1\), Z = 2, and R = 0.026. The structure is built of [UO₂CrO₄(C₅NH₅COO)₂(H₂O)]₂ centrosymmetric dimers, which are linked into a framework by a system of hydrogen bonds involving inner-sphere and outer-sphere water molecules. The coordination number of the U(VI) atom is seven, and the coordination polyhedron is a pentagonal bipyramid with the oxygen atoms of the uranyl group, two chromate groups, two molecules of isonicotinic acid, and a water molecule at the vertices. The crystal chemical formula of the [UO₂CrO₄(C₅NH₅COO)₂(H₂O)]₂ dimer is represented as AB ² M ₃ ¹ , where AB ² M ₃ ¹ , where A = UO ₂ ²⁺ , B ² = CrO ₄ ^2? , and M ¹ = = C₅NH₄COOH and H₂O.     

Non-isothermal crystallization kinetics of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–CaO–SiO<Subscript>2</Subscript> glass containing nucleation agent P<Subscript>2</Subscript>O<Subscript>5</Subscript>/TiO<Subscript>2</Subscript>

Fe₂O₃–CaO–SiO₂ glass ceramics containing nucleation agent P₂O₅/TiO₂ were prepared by sol-gel method. The samples were characterized by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The activation energy and kinetic parameters for crystallization of the samples were calculated by the Johnson-Mehi-Avrami (JMA) model and Augis-Bennett method according to the results of DSC. The results showed that the crystallization mechanism of Fe₂O₃–CaO–SiO₂ glass, whose non-isothermal kinetic parameter n = 2.3, was consistent with surface crystallization of the JMA model. The kinetics model function of Fe₂O₃–CaO–SiO₂ glass, f(α) = 2.3(1–α)[–ln(1–α)]^0.57, was also obtained. The addition of nucleation agent P₂O₅/TiO₂ could reduce the activation energy, which made the crystal growth modes change from onedimensional to three-dimensional.     

Synthesis and crystal structure of [(C<Subscript>7</Subscript>H<Subscript>10</Subscript>N)<Subscript>2</Subscript>]<Superscript>2+</Superscript> [Sb<Subscript>2</Subscript>Cl<Subscript>8</Subscript>]<Superscript>2−1</Superscript>

The reaction of 2,6-dimethylpyridine with SbCl₃ and HCl affords the title compound, the structure of which is ascertained by X-ray diffraction. The unit cell consists of one bridged Sb₂Cl₈²⁻ anion and two 2,6-dimethylpyridinium cations. The trivalent antimony ion is bonded not only directly to chlorine anions, but also is coordinated with chlorine anions by secondary bonds. In the crystal, there exists infinite coordinated chains of [Sb₂Cl₈] _n ²ⁿ⁻ anions running along the a axis, which link 2,6-dimethylpyridinium cations by N-H…Cl hydrogen bonds.     

Crystal structure of the solid solution NH<Subscript>4</Subscript>Al<Subscript>0.62</Subscript>Cr<Subscript>0.38</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 12H<Subscript>2</Subscript>O

The solid solution NH₄Al_0.62Cr_0.38(SO₄)₂ · 12H₂O was studied by X-ray diffraction. The crystal structure was determined in a series of the maximal subgroups Pa3? > R3? > P1? > P1. Reflections forbidden in sp. gr. Pa3? are indicative of symmetry lower than cubic. In the centrosymmetric models under consideration, all sulfate groups are oppositely oriented with respect to each other. In non-centrosymmetric sp. gr. P1, four of the eight sulfate groups have the same orientation, whereas the other four groups are oriented in an opposite direction.     

Crystal structure of a new polar borate Na<Subscript>2</Subscript>Ce<Subscript>2</Subscript>[BO<Subscript>2</Subscript>(OH)][BO<Subscript>3</Subscript>]<Subscript>2</Subscript> · H<Subscript>2</Subscript>O with isolated boron triangles

Crystals of a new polar borate Na₂Ce₂[BO₂(OH)][BO₃]₂ · H₂O were prepared by hydrothermal synthesis. The crystals are orthorhombic, a = 7.2295(7) Å, b = 11.2523(8) Å, c = 5.1285(6) Å, Z = 2, sp. gr. C2mm (Amm2), R = 0.0253. The formula of the compound was derived from the structure determination. The Ce and Na atoms are coordinated by nine and six O atoms, respectively. The Ce position is split, and a small amount of Ce is incorporated into the Na1 site with the isomorphous substitution for Na. The anionic moieties exist as isolated BO₃ and BO₂(OH) triangles. The planes of the BO₂(OH) triangles with mm2 symmetry are parallel to the ab plane. The planes of the BO₃ triangles with m symmetry are perpendicular to the ab plane and are rotated in a diagonal way. The splitting of the Ce positions and the polar arrangement of the BO₂(OH) triangles, water molecules, and Na atoms are observed along the polar a axis. The new structure is most similar to the new borate NaCa₄[BO₃]₃ (sp. gr. Ama2), in which triangles of one type are arranged in a polar fashion along the c axis. Weak nonlinear-optical properties of both polar borates are attributed to the quenching of the second-harmonic generation due to the mutually opposite orientation of two-thirds of B triangles in the unit cell.     

New Diphosphopentamolybdate K<Subscript>5</Subscript>[HP<Subscript>2</Subscript>Mo<Subscript>5</Subscript>O<Subscript>23</Subscript>] · 10H<Subscript>2</Subscript>O: Synthesis,Structure, and Characterization

A new diphosphopentamolybdate(VI) K₅[HP₂Mo₅O₂₃] · 10H₂O has been prepared employing solution method and characterized by single crystal X-ray diffraction, energy dispersive analysis, infrared spectroscopy, thermal stability analysis, cyclic voltammetry analysis, and ultraviolet visible spectroscopy. The compound crystallizes in the orthorhombic sp. gr. Pcab: a = 15.9661(10) Å, b = 19.0832(10) Å, c = 20.0970(9) Å, V = 6123.27(10) Å3, Z = 8. The crystal structure contains the polyanion units [HP₂Mo₅O₂₃]^5– around the potassium cations and lattice water. The [HP₂Mo₅O₂₃]^5– subunits are connected together through K?O?Mo bridges and hydrogen bonds. The crystal shape morphology was simulated using the Bravais–Friedel–Donnay–Harker model.     

Crystal structure of CoUO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 5H<Subscript>2</Subscript>O at 293 K

Single crystals of cobalt uranyl sulfate are grown. The crystal structure is established by X-ray diffraction: the orthorhombic system, sp. gr. Pmc2₁, a = 6.452(2) Å, b = 8.295(2) Å, c = 11.288(3) Å, R₁ = 0.0303, wR₂ = 0.0735 for reflections with I > 2σ(I). The structure of CoUO₂(SO₄)₂ · 5H₂O consists of infinite two-dimensional uncharged [CoUO₂(SO₄)₂H₂O]_2∞ layers, which are linked to each other by hydrogen bonds.     

Molecular Structure of [Cu<Subscript>2</Subscript>(MeCN)<Subscript>2</Subscript>(μ-tpy)<Subscript>2</Subscript>][BPh<Subscript>4</Subscript>]<Subscript>2</Subscript>: A Helical Di-Cuprous Terpyridine Complex

Abstract  The molecular structure of [Cu₂(MeCN)₂(μ-tpy)₂][BPh₄]₂ has been determined. The two terpyridine ligands coordinate to the same Cu(I) center in a bidentate configuration, in which the copper adopted a distorted tetrahedral geometry with the four nitrogen donors. The third ring of each terpyridine ligand forms a bridge with a second Cu(I) center, whose tetrahedral coordination sphere is completed by two acetonitrile ligands. The resulting structure represents a section of a double helix. Crystal data: space group C2/c, a = 27.202(5), b = 12.995(3), c = 23.409(5) ?, β = 123.13(3)°; V = 6930(2) ?³, Z = 4, R = 0.0613, wR ₂ = 0.0946. Graphical Abstract  The molecular structure of [Cu₂(MeCN)₂(μ-tpy)₂][BPh₄]₂ has been determined. The terpyridine ligands coordinate in a bidentate fashion to the same Cu center and monodentate to a second Cu center resulting in a double helical structural motif.      

Synthesis and crystal structure of binuclear molecule Ho<Subscript>2</Subscript>(2-FC<Subscript>6</Subscript>H<Subscript>4</Subscript>COO)<Subscript>6</Subscript>⋅4H<Subscript>2</Subscript>O

The complex Ho₂(2-FC₆H₄COO)₆?4H₂O has been synthesized and structurally characterized by single crystal X-ray diffraction methods. The complex crystallizes in the triclinic system with space group P \(\bar 1\), lattice parameters a = 9.293(8) Å, b = 9.845(8) Å, c = 12.703(11) Å, α = 85.470(14)^°, β = 87.537(12)^°, γ = 62.485(11)^°, V = 1027.5(15) ų, Z = 1, D_calc = 1.998 Mg/m³. The Ho³⁺ ion is in distorted monocapped square-antiprism coordination environment and is coordinated by nine oxygen atoms, seven from five 2-FC₆H₄COO^2? groups, two from two water molecules. Two Ho³⁺ ions are linked together by four bridging carboxylate groups to form a binuclear molecule with inversion center.     

Crystal structure and properties of [OsO<Subscript>2</Subscript>(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>]SO<Subscript>4</Subscript> · H<Subscript>2</Subscript>O

The structure of a single crystal of tetraammindioxoosmium(VI) sulfate [OsO₂(NH₃)₄]SO₄ · H₂O, which is synthesized by the reaction of K₂[OsO₂(OH)₄] with (NH₄)₂SO₄ in an aqueous solution, is investigated using X-ray diffraction analysis. The compound crystallizes in the monoclinic crystal system, space group P2₁/c, a = 13.102(2) Å, b = 6.158(3) Å, c = 11.866(2) Å, β = 98.13(2)°, and Z = 4. The [OsO₂(NH₃)₄]SO₄ · H₂O compound has an island structure. Two crystallographically independent osmium atoms are situated at the centers of symmetry, and their octahedral coordination includes two oxygen atoms and four nitrogen atoms of the ammonia molecules. In both octahedra, the osmyl group is linear. The Os-O distances in the octahedra are identical within the standard deviations [Os(1)-O, 1.762(2) Å; Os(2)-O, 1.769(2) Å]. The Os-N bond lengths vary from 2.082(3) to 2.101(3) Å. The cationic complexes, SO₄ groups, and water molecules are linked via the system of hydrogen bonds. The assignment of the absorption bands in the IR spectrum of the compound synthesized is performed, and its thermal behavior in air is studied.     

Synthesis,Structure and Luminescent Property of a Novel Lanthanide Metal-Organic Coordination Polymer Yb<Subscript>3</Subscript>(BDC)<Subscript>4.5</Subscript>(DMF)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript> · (DMF)<Subscript>2</Subscript>

Abstract  A three-dimensional lanthanide metal-organic coordination polymer Yb₃(BDC)_4.5(DMF)₂(H₂O)₃ · (DMF)₂ has been synthesized by the reaction of the lanthanide metal ion (Yb³⁺) with 1,4-benzenedicarboxylic acid (H₂BDC) under mild condition. The compound crystallizes in the triclinic system, space group PI with unit cell parameters a = 10.7428(9) Å, b = 11.2786(9) Å, c = 26.172(2) Å, α = 85.060(2)°, β = 88.1060(10)°, γ = 62.3670(10)°, V = 2798.9 (4) ų, Z = 2. The crystal structure exhibits one-dimensional channels along the [011] direction. The fluorescent results showed that there were two emission peaks at 375 and 420 nm when the compound was excited by a 235 nm excitation. Graphical Abstract  The preparation, X-ray structure and luminescent property are presented for a new lanthanide metal-organic coordination polymer Yb₃(BDC)_4.5(DMF)₂(H₂O)₃ · (DMF)₂.      

Synthesis and structure of a new hybrid vanadium arsenate: [VO<Subscript>2</Subscript>(phen)]<Subscript>2</Subscript>(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)⋅H<Subscript>3</Subscript>O

A new hybrid vanadium arsenate [VO₂(phen)]₂(H₂AsO₄)H₃O 1 (phen = 1,10-phenanthroline) was synthesized under hydrothermal reaction conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis (TGA), IR and elemental analyses. Crystal data for 1: monoclinic, P2₁/n, a = 9.175(2) Å, b = 18.638(5) Å, c = 14.482(4) Å, = 102.333(3), V = 2419(1) ų, Z = 4. Compound 1 is composed of discrete tricyclic (VO₂)₂(H₂AsO₄) cluster decorated with two phen ligands. The discrete arsenic–vanadium clusters are extended into three-dimensional supramolecular arrays via – stacking interactions of phen groups.     

Pseudosymmetry in Cr(urea)<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>·3NO<Subscript>3</Subscript>

Abstract  

The low temperature crystal structure of the complex, Cr(urea)₄(H₂O)₂·3NO₃ (1), displays intriguing pseudosymmetry that complicates the structure determination. 1 crystallises in the centrosymmetric monoclinic space group P2₁/c with Z = 8 and Z′ = 2; a = 18.3338(4) ?, b = 16.5472(4) ?, c = 13.9252(3) ? and β = 106.3260(10)°, V = 4054.19(16) ?³. The two symmetry independent [Cr(urea)₄(H₂O)₂]³⁺ ions in the asymmetric unit both feature coordinated urea (O=C(NH₂)₂) and lie on general positions. A further six independent nitrate anions complete the structure. The unit cell is primitive but the two Cr³⁺ ions are related by a pseudo translation of ?, ?, 0. The deviation from a truly C-centred cell is clear from an examination of geometry of the urea ligands and the hydrogen bonds which they form. The identification of the space group in this case is described and methods for quantifying the degree of deviation from a C-centred cell discussed.