Triosmium and triruthenium clusters containing morpholine ligand: X-ray structure of Os<Subscript>3</Subscript>(CO)<Subscript>10</Subscript>(μ-η<Superscript>2</Superscript>-NC<Subscript>4</Subscript>H<Subscript>6</Subscript>O)(μ-H)

Treatment of the labile cluster Os₃(CO)₁₀(CH₃CN)₂ with morpholine in benzene at 60^°C afforded Os₃(CO)₁₀(μ-η²-NC₄H₆O)(μ-H) (1). Decarbonylation of 1 at 128^°C gave Os₃(CO)₉(μ₃-η²-NC₄H₆O)(μ-H) (2), which reacts with PPh₃ at ambient temperature to give an addition product Os₃(CO)₉(μ-η²-NC₄H₆O)(PPh₃)(μ-H) (3). Compound 1 reacted with PPh₃ at 98^°C to give the substitution product 4 which is an isomer of 3. The reaction of Ru₃(CO)₁₂ with morpholine in the presence of Me₃NO in refluxing benzene at 80^°C afforded Ru₃(CO)₉(μ₃-η²-NC₄H₆O)(μ-H) (5). Compounds 1– 5 have been characterized by elemental analysis, infrared, ¹H NMR, and mass spectroscopic data. The molecular structure of 1 has been determined by single crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group P2/c with a = 29.598(8) Å, b = 9.202(2) Å, c = 14.496(4) Å, β = 93.19(3)^°, Z = 8, and V = 3942(2) ų. Compound 1 consists of an isosceles triangle of osmium atoms with one elongated Os–Os edge, which is bridged by the hydride and the morpholine ligand.     

Aquanitrilotris(methylenephosphonato)dirubidium [Rb<Subscript>2</Subscript>(H<Subscript>2</Subscript>O){μ<Superscript>12</Superscript>-NH(CH<Subscript>2</Subscript>PO<Subscript>3</Subscript>H)<Subscript>3</Subscript>}]: Synthesis and structure

Aquanitrilotris(methylenephosphonato)dirubidium is a 3D coordination polymer with a layer structure. Space group \(P\bar 1\), Z = 2; a = 8.0380(3) Å, b = 9.0522(4) Å, and c = 10.7837(4) Å; α = 113.252(4)°, β = 105.391(3)°, and γ = 96.182(3)°. Rb atoms populate two symmetrically inequivalent positions with c.n. = 8 and 10; significant difference in O–Rb–O angles in the coordination polyhedra is indicative of the ionic type of Rb–O bonds. In the crystal packing, molecules are connected by not only coordination bonds but hydrogen bonds as well.     

Synthesis and Crystal Structures of Three Pyrazine-2-carboxylate Containing Isostructural Complexes: M(2-pyrazine-carboxylate)<Subscript>3</Subscript> (M = Co<Superscript>+3</Superscript>, Cr<Superscript>+3</Superscript>, and Rh<Superscript>+3</Superscript>)

Abstract Three new isostructural coordination complexes, M(pca)₃, where M = Co (1), Cr (2), or Rh (3) and 2-pyrazine-carboxylate (pca), have been synthesized solvothermally and characterized by single crystal X-ray diffraction and powder X-ray diffraction. In structures 1-3, the pca ligand chelates to the metal centers in a tris-chelating arrangement through proximal nitrogen and oxygen donor atoms. Structures 1-3 are monoclinic and crystallize in the space group C2/C. In structure 1, a = 28.066(13) ?, b = 8.036(4) ?, c = 13.577(6) ?, and β = 90.2(10)°. In structure 2 a = 28.318(3) ?, b = 8.089(4) ?, c = 13.792(12) ?, and β = 90.256(2)°. In structure 3, a = 28.679(4) ?, b = 8.051(13) ?, c=13.847(2) ?, and β = 90.585(2)°. Graphical Abstract Three new isostructural coordination complexes, M(pca)₃, where M = Co, Cr, or Rh and 2-pyrazine-carboxylate (pca), have been synthesized solvothermally and characterized by single crystal X-ray diffraction and powder X-ray diffraction.      

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,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.      

α-Diimine Chelation at a Triosmium Cluster: Synthesis and X-ray Structure of 1,1-Os<Subscript>3</Subscript>(CO)<Subscript>9</Subscript>(μ-CO)(1,10-phen)

Abstract The α-diimine ligand 1,10-phenanthroline (phen) reacts with the activated cluster 1,2-Os₃(CO)₁₀(MeCN)₂ to afford the carbonyl-bridged cluster 1,1-Os₃(CO)₉(μ-CO)(phen), which has been characterized by IR and NMR spectroscopies and X-ray diffraction analysis. Replacement of the 1,5-cyclooctadiene (cod) ligand in 1,1-Os₃(CO)₁₀(cod) by phen proceeds sluggishly over a 24 h period, showing less than 5% conversion to 1,1-Os₃(CO)₉(μ-CO)(phen). Graphical abstract α-Diimine Chelation at a Triosmium Cluster: Synthesis and X-ray Structure of 1,1-Os ₃ (CO) ₉ (μ-CO)(1,10-phen) Bhaskar Poola, Xiaoping Wang, and Michael G. Richmond The reaction between the triosmium cluster 1,2-Os3(CO)10(MeCN)2 and 1,10-phenanthroline yields 1,1-Os3(CO)9(μ-CO)(phen) at room temperature. The presence of a bridging carbonyl group in the product cluster has been observed by IR spectroscopy and confirmed by X-ray crystallography.      

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.     

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.     

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.     

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.     

Molecular structure of [(<Superscript>t</Superscript>Bu)<Subscript>2</Subscript>Al(μ-OC<Subscript>6</Subscript>H<Subscript>4</Subscript>-2-Me)]<Subscript>2</Subscript>

The molecular structure of [(^tBu)₂Al(-OC₆H₅-2-Me)]₂ has been determined. Both the ortho-tolyl methyl groups are oriented towards Al(2). The intramolecular steric interaction between the ortho-methyl groups and the tert-butyl ligands results in the geometry about the bridging oxygen being significantly distorted while the geometries about the aluminum centers show a distortion from tetrahedral that is less than the sterically less hindered [(^tBu)₂Al(-OPh)]₂. Crystal data: group C2/c, a = 13.733(3) Å, b = 15.135(3) Å, c = 15.420(3) Å, = 104.24(3), V = 3106(1) ų, Z = 4, R = 0. 0612, wR₂ = 0.1787.     

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 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.     

Optical and nonlinear laser properties of the χ<Superscript>(3)</Superscript>-active monoclinic α-KY(WO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

Monoclinic α-KRE(WO₄)₂ crystals are grown. Their structure is described in two crystallographic settings. The principal refractive indices are determined and the coefficients and characteristic wavelengths are used for calculating refractive indices by the Selmeyer formulas. The data on the anisotropic parametric Raman generation in these crystals under the picosecond pumping are discussed.     

Crystal Structure and Physical Characterisation of [Zn<Subscript>2</Subscript>(Benzoato)<Subscript>4</Subscript>(Caffeine)<Subscript>2</Subscript>]·2 Caffeine

Abstract  

The crystal structure of [Zn₂(benzoato)₄(caffeine)₂]·(caffeine)₂ was determined by direct method and Fourier technique. The structure was refined by full-matrix least-squares method to a weighted R factor of 0.0582. The structure consists of centrosymmetric dimeric units where the two zinc(II) atoms are coordinated by four bridging benzoates in a syn–syn arrangement and two caffeine ligands at the apices of a bicapped square prism. Remaining two caffeines are bound only by hydrogen bonds. The Zn–Zn distance is 2.961(1) ?. The Zn(II) atoms are displaced by 0.365 ? from the basal plane containing four oxygen atoms towards the apical caffeine molecules. The dimeric structure of the complex is consistent with spectrum and thermal data. The structural data are compared with those found in similar [Zn₂(RCOO)₄(NL)₂] complexes.     

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.     

Solvothermal Syntheses and Crystal Structures of Two Thiostannates(IV) [M(tepa)]<Subscript>2</Subscript>(<Emphasis Type="Italic">μ</Emphasis>-Sn<Subscript>2</Subscript>S<Subscript>6</Subscript>) (M = Fe<Superscript>2+</Superscript> and Co<Superscript>2+</Superscript>)

Abstract  

Two new thiostannates [M(tepa)]₂(μ-Sn₂S₆) (tepa = tetraethylenepentamine, M = Fe²⁺ 1 and Co²⁺ 2) were prepared by solvothermal method. Compounds 1 and 2 are isostructural. Both the compounds crystallize in the tetragonal system, space group I41/a (no. 88) with the crystal parameters of 1: a = 25.683(2) ?, b = 25.683(2) ?, c = 9.9860(9) ?, V = 6,586.7(11) ?³, Z = 8, and 2: a = 25.742(3) ?, b = 25.742(3) ?, c = 9.8977(12) ?, V = 6,558.5(14) ?³, Z = 8. The Sn₂S₆ ⁴⁻ anion acts as a bidentate bridging ligand connecting two transition metal complex cations by trans terminal S atoms to form neutral centrosymmetric [M(tepa)]₂(μ-Sn₂S₆) moieties.     

One Novel Three-dimensional Network Constructed from [Mn(4,4′-bip)<Subscript>2</Subscript>(OH<Subscript>2</Subscript>)<Subscript>4</Subscript>]<Superscript>2+</Superscript> Cations and DBA<Superscript>2−</Superscript> Anions via Hydrogen-bonding and π–π Interactions

Abstract One new mononuclear manganese complex of [Mn(4,4′-bip)₂(OH₂)₄](DBA) · 4H₂O (1) (4,4′-bipyridine, 4,4′-bip; H₂DBA, benzene-1,3-dicarboxylic acid) has been obtained from the hydrothermal reaction of MnCl₂ · 4H₂O, 4,4′-bipyridine and H₂DBA in the solvent of H₂O at 140 °C for 3 days, characterized by X-ray analysis, spectroscopic methods, and thermal analysis. Packing diagram shows that the three-dimensional network was formed via hydrogen bonds and strong π–π interactions. Graphical abstract One Novel Three-dimensional Network Constructed from [Mn(4,4′-bip) ₂ (OH ₂ ) ₄ ] ²⁺ Cations and DBA ²⁻ Anions via Hydrogen-bonding and π–π Interactions Ying Liu, Bao Zhang, Jian-min Dou, Da-qi Wang, Da-cheng Li, Lei Zhou One new mononuclear manganese complex of [Mn(4,4’-bip)₂(OH₂)₄](DBA) · 4H₂O (1) (4,4’-bipyridine, 4,4’-bip; H₂DBA, benzene-1, 3-dicarboxylic acid) has been obtained and haracterized by X-ray analysis, spectroscopic methods, and thermal analysis. Packing diagram shows that the three-dimensional network was formed via hydrogen bonds and strong π-π interactions.      

Crystal Structure and Vibrational Spectra of Erbium Trisodium Bis(Cyclotriphosphate) Nonahydrate,ErNa<Subscript>3</Subscript>(P<Subscript>3</Subscript>O<Subscript>9</Subscript>)<Subscript>2</Subscript> · 9H<Subscript>2</Subscript>O

Abstract The cyclotriphosphate salt, ErNa₃(P₃O₉)₂ · 9H₂O, has been characterized by single-crystal X-ray diffraction [hexagonal, space group , with unit cell parameters of a = b = 30.8451(14), c = 12.8063(8) ?; Z = 18]. The structure consists of alternating layers of [P₃O₉]³⁻ groups, ErO₈ dodecahedra, Na(1)O₆ and Na(2)O₇ polyhedra linked together by water molecules. The P₃O₉ rings are grouped along the c-axis in a P₃O₉–ErO₈ arrangement thereby producing broad, hexagonal channels of diameter of 6.65 ? with a side dimension of 3.907 ?. The absence of coincidences for the majority of the IR and Raman bands observed for the cyclotriphosphate salt is in accord with the centrosymmetric structure of the material. The vibrational spectra have been interpreted on the basis of factor group effects. Graphical abstract We report the crystal structure and vibrational spectra of erbium trisodium bis(cyclotriphosphate)nanohydrate salt ErNa ₃ (P ₃ O ₉ ) ₂ · 9H ₂ O H. Assaaoudi, M. Ijjaali, A. Ennaciri, I. S. Butler* and J. A. Kozinski Crystal structure and vibrational spectra of erbium trisodium bis(cyclotriphosphate) nonahydrate,ErNa₃(P₃O₉)₂ · 9H₂O. Projection of the coordination polyhedra of ErNa₃(P₃O₉)₂ · 9H₂O down the c axis     

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.