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.     

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.     

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 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.     

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.     

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.     

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 Ethylenediammonium bis iodate tetra iodic Acid: [C<Subscript>2</Subscript>H<Subscript>10</Subscript>N<Subscript>2</Subscript>] (IO<Subscript>3</Subscript>)<Subscript>2</Subscript>·4HIO<Subscript>3</Subscript>

Abstract  

The synthesis and crystal structure are presented for the ethylenediammonium bis iodate tetra iodic acid. An X-ray investigation has shown that this compound crystallizes in a centrosymmetric monoclinic system, space group P2₁/c with the lattice parameters: a = 7.2536(2) ?, b = 18.5351(5) ?, c = 7.5685(2) ?, β = 107.937(1)°, V = 968.10(3) ?³. The structure was solved from 5281 independent reflections with R ₁ = 0.0229 and wR ₂ = 0.0428, and refined with 156 parameters. The structure is built up of [(CH₂)₂(NH₃)₂]²⁺ cations connected to the one-dimensional [HIO₃]_n chains and to the [H₂I₄O₁₂]²⁻ clusters by a weak N–H···O hydrogen bonds.     

Solvothermal Syntheses and Crystal Structures of Rare Earth Thioantimonates [Y(en)<Subscript>4</Subscript>]SbS<Subscript>4</Subscript>·0.5en and [Tm(en)<Subscript>4</Subscript>]SbS<Subscript>4</Subscript>·0.5en

Abstract  

Two rare earth metal thioantimonates [RE(en)₄]SbS₄·0.5en (RE = Y(1), Tm(2); en = ethylenediamine) were synthesized under mild solvothermal conditions. Compounds 1 and 2 are isostructural, and both crystallize in monoclinic space group P2₁/n. Crystallographic data for 1: a = 11.0894(19), b = 12.905(2), c = 16.000(3) ?, β = 91.792(4), V = 2288.7(7) ?³, Z = 4. For 2: a = 11.0870(14), b = 12.8977(16), c = 15.986(2) ?, β = 91.879(3), V = 2284.7(5) ?³, Z = 4. The four-en coordinated rare earth complex cation [RE(en)₄]³⁺ formed in situ balances the charge of the [SbS₄]³⁻ anion in the crystal structure. The RE³⁺ ion is in an eight-coordinated environment involving eight N atoms of four en ligands forming a bicapped trigonal prism. Hydrogen bonds link [RE(en)₄]³⁺, [SbS₄]³⁻ and en species into a three-dimensional structure. The structure determination of 1 and 2 implies that the ionic radii of rare earth metal ions play an important role on the structures of the rare earth metal thioantimonates.     

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.      

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.     

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.     

Synthesis and Crystal Structure of [Na(H<Subscript>2</Subscript>O)<Subscript>1.5</Subscript>][Na(H<Subscript>2</Subscript>O)<Subscript>3.5</Subscript>] X<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O (X = 4′-Methoxy-7-Hydroxyisoflavone-3′-Sulfonate)

Abstract  

Water-soluble derivative of formononetin, [Na(H₂O)_1.5][Na(H₂O)_3.5] X₂·2H₂O(X = 4′-methoxy-7-hydroxyisoflavone-3′-sulfonate) was synthesized by sulfonation reaction. It was characterized by IR, ¹H NMR and single-crystal X-ray diffraction analysis. Single-crystal X-ray diffraction analysis showed that the title compound crystallized in a triclinic space group P-1 with cell parameters a = 6.9642(15) ?, b = 13.343(3) ?, c = 20.634(5) ?, α = 107.115(3)˚, β = 93.121(4)˚, γ = 91.911(3)˚, V = 1827.3(7) ?⁻³, D _c  = 1.575 Mg m ⁻³, Z = 2. There are two conformers of 4′-methoxy-7-hydroxyisoflavone-3′-sulfonate anions, two kinds of sodium cations, five coordinated water molecules and two lattice water molecules in the crystal structure. The sodium atoms coordinated with the oxygen atoms from water molecules, hydroxyl groups and sulfo-groups to form a Na–O coordinated network. Aromatic π···π stacking interactions and hydrogen bonding existed in the crystal structure of title compound, which together with coordinated interactions and electrostatic interactions between sodium cations and anions sulfonates C₁₆H₁₀O₄SO₃ ⁻ lead to the moieties into a three-dimensional network.     

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.     

Crystal and molecular structures of [Co(<Emphasis Type="Italic">D</Emphasis>H)(<Emphasis Type="Italic">o-phen</Emphasis>)<Subscript>2</Subscript>][BF<Subscript>4</Subscript>]<Subscript>2</Subscript> · 2H<Subscript>2</Subscript>O

The crystal structure of a new mixed-ligand complex [Co(DH)(o-phen)₂][BF₄]₂ · 2H₂O is determined by X-ray diffraction. The crystal is monoclinic, a = 12.2081(11) Å, b = 14.3474(9) Å, c = 17.7393(16) Å, β = 104.95(1)°, and space group P2₁/c. The coordination octahedron of Co³⁺ is formed by two nitrogen atoms of the dimethylglyoxime molecule and four nitrogen atoms of o-phenanthroline molecules. The dimethylglyoxime molecule is singly deprotonated and acts as DH^?. The mean Co-N distances for dioxime and o-phenanthroline are 1.911 and 1.964 Å, respectively. The key role in the formation of the crystal structure is played by [BF₄]^? outer-sphere anions and crystallization water molecules, which form an extended hydrogen-bond system.     

Synthesis,Crystal Structure and Spectral Properties of [Fe<Subscript>3</Subscript>(2,2′-bipy)<Subscript>6</Subscript>(ox)<Subscript>3</Subscript>]·12.25H<Subscript>2</Subscript>O Complex

A novel iron (II) complex of formula [Fe₃(2,2′-bipy)₆(ox)₃]·12.25H₂O (2,2′-bipy = 2,2′-bipyridine, ox = oxalate) has been prepared and structurally characterized by X-ray crystallography. In the complex, the metal atoms are six-coordinated in distorted octahedral environment. In the complex [Fe(ox)₃]^4? anions and water molecules are linked together into 1D chain structure by hydrogen interaction. The red crystal of the complex is monoclinic, space group P2₁/c, with a = 22.932(6) Å, b = 13.715(4) Å, c = 22.493(6) Å, β = 93.177(5)°, and V = 7063(3) Å³ with Z = 4.     

Na<Subscript>3</Subscript>Tb<Subscript>3</Subscript>[Si<Subscript>6</Subscript>O<Subscript>18</Subscript>] · H<Subscript>2</Subscript>O,a synthetic analogue of microporous mineral gerenite

Crystals of a new silicate, Na₃Tb₃[Si₆O₁₈] · H₂O, space group \(P\bar 1\), are obtained under hydrothermal conditions. The formula of the compound is determined in the course of structure solution. The silicate is a synthetic analogue of the gerenite mineral (Ca_1.21Na_0.57)(Y_2.24Dy_0.68)Si₆O₁₈ · 2H₂O, whose structure contains six-membered rings formed by SiO₄ tetrahedra. The [Si₆O₁₈] rings are connected by TbO₆ octahedra into a mixed microporous framework with voids filled by Na atoms and water molecules. The new silicate differs from gerenite by the occupation of the Ca position by Na atoms and population of the pores sandwiched between six-membered rings. By virtue of conditions of hydrothermal synthesis in the absence of Ca and excess of Na in the system, an additional Na position appears in the void. It is populated statistically, and in gerenite it was occupied by water molecules only. In the new structure, the position of water is split into two statistically populated positions. The inclusion of Na atoms in additional positions in framework pores and their high thermal vibrations are indicative of ion-exchange properties of the structure. Possible paths of ion exchange are discussed.     

Synthesis and Crystal Structure of 2D Supramolecular Compound [Co(phth)(phen) (H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]·H<Subscript>2</Subscript>O

Abstract  

A 2D supramolecular compound [Co(phth)(phen) (H₂O)₃]·H₂O has been synthysized by the reactions of Co(NO₃)₂·6H₂O, 1, 10-phenanthroline(phen) and phthalate acid(H₂phth) in NaOH solution with pH 7.0.The complex has been characterized by elemental analysis, IR, and single-crystal X-ray diffraction analysis which shows it belongs the monoclinic space group P2(1)/n, a = 7.571(2) ?, b = 13.737(3) ?, c = 20.015(4) ?, β = 95.56(1)°. V = 2071.9(8) ?³, Mr = 475.31, Dc = 1.524 g/cm⁻³, Z = 4, F(000) = 980, μ(MoKa) = 0.879 mm⁻¹. The final R1 and wR2 are 0.0348 and 0.0711, respectively. The cobalt(II) ion is six-coordinated in a distorted octahedron to form a unit. Every unit is connected by hydrogen bonds forming 1D chain and 2D supramolecular network by π–π stacking interaction between adjoining chains.     

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.     

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.