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.     

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,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.      

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 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.     

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.     

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.     

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.     

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 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.     

Synthesis and Crystal Structure of a Novel Double-Chain Coordination Polymer [Zn<Subscript>2</Subscript>(bipy)<Subscript>2</Subscript>(btec)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]<Subscript>n</Subscript> (bipy = 2,2′-bipyridine; btec = 1,2,4,5-benzenetetracarboxylate)

Abstract  A novel aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. Compound 1 belongs to the triclinic crystal system, space group P-1; a = 7.7449(6) ?, b = 8.9286(8) ?, c = 10.7422(8) ?, α = 80.95(1)°, β = 70.21(1)°, γ = 78.14(1)°, V = 680.93(10) ?³, Z = 2. The coordination geometry of Zn(II) atom is distorted trigonal bipyramidal with two nitrogen atoms of one 2,2′-bipy group, two oxygen atoms from two different btec ligands, and one water. The 16-membered rings are alternately arranged forming an infinite 1-D double-chain structure. A 3-D network was constructed by interlayer C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state. Graphical Abstract  A 1-D double-chain aromatic polycarboxylate polymer, [Zn₂(bipy)₂(btec)(H₂O)₂]_n (1), has been synthesized and structurally characterized by the single crystal X-ray diffraction. A 3-D network was constructed by intermolecular C···H–O, O···H–O hydrogen bonds and π–π stacking interactions. Compound 1 exhibits fluorescence at room temperature in the solid state.      

Hydrogen Atoms Location in Os<Subscript>3</Subscript>(μ-H)(CO)<Subscript>9</Subscript>(μ<Subscript>3</Subscript>, η<Superscript>2</Superscript>-C<Subscript>2</Subscript>H) from Accurate X-Ray Data at 100 K

Abstract  

The structure of the complex Os₃(μ-H)(CO)₉(μ₃, η²-C₂H) has been determined using X-ray data collected at low temperature (100 K); all hydrogen atoms have been located. The asymmetric unit is formed by two molecules joined through hydrogen bonds involving the hydrogen atoms of C₂H moiety and the oxygen atoms of carbonyl groups. The complex crystallizes in the monoclinic space group P2₁/c with a = 12.94040(2), b = 15.4705(2), c = 16.0164(2) ?, β = 106.0860(10)°, and V = 3,080.85(7) ?³, Z = 8. A molecule is formed by a triangular Os₃ cluster, with metal atoms bearing terminal CO groups. The acetylenic residual is formally π-bonded to two Os atoms in a perpendicular mode and σ-linked to the third Os atom. A bridging hydride atom completes the coordination.     

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.     

Crystal Structure and Characterization of [Ni(RPOEt)<Subscript>2</Subscript>(C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH)<Subscript>2</Subscript>](ClO<Subscript>4</Subscript>)<Subscript>2</Subscript> [RPOEt = bis{(diphenylphosphinyl)methyl}ethyl phosphinate]

Abstract  

The compound [Ni(RPOEt)₂(C₂H₅OH)₂](ClO₄)₂ (1) [RPOEt = bis{(diphenylphosphinyl)methyl}ethyl phosphinate] has been prepared in the form of single crystals and characterized by elemental and thermal analyses, IR spectroscopy and by a single crystal X-ray diffraction study. The complex crystallizes in the triclinic P[`1] P\bar{1} space group with a = 9.8773(5), b = 13.741(1), c = 14.287(1) ?, α = 64.313(9), β = 70.280(5), γ = 89.973(7)o, V = 1620.5(2) ?³, and Z = 1. The nickel(II) atom in 1, situated at the centre of symmetry, is coordinated by four oxygen atoms from two RPOEt ligands and two oxygen atoms from two ethanol molecules in a slightly distorted octahedral environment. The third phosphoryl-oxygen atom from the phosphinate ligand is hydrogen bonded to the oxygen atom of the ethanol molecule coordinated to nickel(II). The complex [Ni(RPOEt)₂(C₂H₅OH)₂]²⁺ cations are linked by the C–H···O hydrogen bonds into one-dimensional chains and by the composite π···π and C–H···π phenyl interactions into a final three-dimensional structure.     

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.     

Synthesis and Crystal Structures of the Coordination Polymers Pb(PYTAC)<Subscript>2</Subscript> and Pb<Subscript>2</Subscript>(PYTAC)<Subscript>3</Subscript>(NO<Subscript>3</Subscript>) (PYTAC = 2-(pyridin-4-yl)thiazole-5-carboxylate)

Abstract  

Two lead coordination compounds, Pb(PYTAC)₂ (1), and Pb(PYTAC)₂(NO₃) (2), were grown as single crystals via hydrothermal synthesis (PYTAC = 2-(4-pyridyl) thiazole-4-carboxylate). Both compounds have been identified via single crystal X-ray diffraction. Coordination polymer 1 crystallizes in a triclinic space group P-1 (a = 5.5097(4) ?, b = 7.2822(5) ?, c = 11.3134(8) ?, α = 103.5580(10)°, β = 99.4330(10)°, γ = 97.1050(10)°), and forms 2-D layers parallel to the crystallographic (ac) plane. Coordination polymer 2 crystallizes in a triclinic space group P-1 (a = 9.8102(5) ?, b = 10.5972(6) ?, c = 14.8076(8) ?, α = 91.9350(10)°, β = 100.8050(10)°, γ = 103.1350(10)°), and forms an infinite 1-D chains along the a axis.     

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 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 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.