Synthesis and Crystal Structure of La(NO<Subscript>2</Subscript>)(SO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>O)

Abstract Single crystals of new open-framework lanthanide sulphate nitrite La(NO₂)(SO₄)(H₂O) has been synthesized, in the presence of 2,6-diformyl-4-chlorophenol. His structure has been determined by X-ray diffraction data: the complex crystallizes in the tetragonal system, space group P4₃, with a = 7.0028(2) (?), b = 7.0028(2) (?), c = 11.8341(4) ?, V = 580.34(3) ?³, Z = 4, D _c = 3.582 Mg m⁻³. The three-dimensional (3D) framework of this compound is built up by the linkages of lanthanide atoms and the oxygen atoms of the sulphate and nitrite groups. The lanthanum atom is 9-fold coordinated. The structure is unfamiliar in lanthanide chemistry and this compound represents the first example of nitrite lanthanide sulphate complex. Graphical Abstract An unfamiliar structure in lanthanide chemistry represented by the first example of nitrite lanthanide sulphate complex is described.      

Synthesis and Structure of [Fe<Subscript>3</Subscript>O(O<Subscript>2</Subscript>CCH<Subscript>2</Subscript>OMe)<Subscript>6</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>][FeCl<Subscript>4</Subscript>]

Abstract  The structure of [Fe₃O(O₂CCH₂OMe)₆(H₂O)₃][FeCl₄] · 2.5H₂O has been determined. The three iron atoms and the μ₃-oxo are coplanar. Each carboxylic ligand is bidentate and links two iron atoms in the cluster. The clusters are linked by intra-trimer hydrogen bonding to form a zigzag motif that forms sheets via hydrogen bonding involving disordered waters of hydration. The [FeCl₄]⁻ anion is intercalated between the hydrogen-bonded sheets. Crystal data: space group P2₁/n, a = 10.276(2), b = 22.793(5), c = 17.091(3) ?, β = 96.66(3)°, V = 3976(1) ?³, Z = 4, R = 0.0837, wR ₂ = 0.1836. Graphical Abstract  The structure of [Fe₃O(O₂CCH₂OMe)₆(H₂O)₃][FeCl₄] · 2.5H₂O has been determined in which the clusters are linked by intra-trimer hydrogen bonding to form a zigzag motif that forms sheets via hydrogen bonding involving disordered waters of hydration.      

Crystal Structures of Energetic Compounds. I. Safe Small-Scale Preparation and X-Ray Structure Determination of the High-Energy Cobalt(III) Complex [Co(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>N<Subscript>3</Subscript>](N<Subscript>3</Subscript>)<Subscript>2</Subscript>

Abstract  Well-formed dark red single-crystals of the potentially explosive cobalt(III) azido complex [Co(NH₃)₅N₃](N₃)₂ (nitrogen content: 72.59%) have been grown using a safe small-scale preparation from [Co(NH₃)₅N₃]Cl₂ and sodium azide. The complex crystallizes in the orthorhombic system, space group Pnma with unit cell parameters a = 12.921(3) ?, b = 10.346(2) ?, c = 8.0315(16) ?, V = 1,073.7(4) ?³ and Z = 4. Five NH₃ ligands and the azide anion surround the Co³⁺ ion in a nearly perfect octahedral geometry. Two azide anions are non-coordinating, and no water of crystallization is present in the crystal structure. Graphical Abstract  Well-formed dark red single-crystals of the potentially explosive cobalt(III) azido complex [Co(NH₃)₅N₃](N₃)₂ (nitrogen content: 72.59%) have been grown using a safe small-scale preparation from [Co(NH₃)₅N₃]Cl₂ and sodium azide. Five NH₃ ligands and the azide anion surround the Co³⁺ ion in a nearly perfect octahedral geometry. Two azide anions are non-coordinating, and no water of crystallization is present in the crystal structure.      

Synthesis and Structure of Ba<Subscript>5</Subscript>(V<Subscript>2</Subscript>O<Subscript>7</Subscript>)<Subscript>2</Subscript>Cl<Subscript>2</Subscript>

Abstract  A new barium chlorovanadate, Ba₅(V₂O₇)₂Cl₂, was isolated by a high-temperature (850 °C) reaction employing a CsCl/RbCl flux. The structure was determined by single crystal X-ray diffraction methods. This compound crystallizes in an orthorhombic crystal system, Pmmn (No. 59), with a = 11.558(2) ?, b = 15.164(3) ?, c = 10.023(2) ?, Z = 4 and V = 1756.7(6) ?³. The structure of Ba₅(V₂O₇)₂Cl₂ was determined by full-matrix, least-squares methods with R ₁ = 0.0398, wR ₂ = 0.1069 and GOF = 1.048 for all data. This new structure can be described as a composite lattice made up of mixed covalent and ionic moities. The extended framework is orchestrated by stacked [Ba(V₂O₇)Cl]³⁻ slabs that are interconnected by Ba²⁺ cations through Ba–O bonds to the [V₂O₇] units. The Ba²⁺ and Cl^- ions form BN-type “[BaCl]” sheets with pseudo-hexagonal windows that are centered by [V₂O₇]⁴⁻ pyrovanadate units. Graphical Abstract  The structure of a new chlorovanadate, Ba₅(V₂O₇)₂Cl₂, exhibits an interesting BN-type salt lattice that consists of an extended [BaCl] sheet containing pseudo-hexagonal windows that are centered by [V₂O₇] pyrovanadate units.      

Crystal and Molecular Structure of Dichloro(ethylenediamine)gold(III) Nitrate: [Au(NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>CH<Subscript>2</Subscript>NH<Subscript>2</Subscript>)Cl<Subscript>2</Subscript>]NO<Subscript>3</Subscript>

Abstract  The gold(III) atom in [Au(NH₂CH₂CH₂NH₂)Cl₂]NO₃ is chelated by the ethylenediamine (en) ligand and the approximately square planar geometry is completed by two chloride atoms. Weak Au···O and Au···Cl contacts are noted above and below the square plane leading to a tetragonally distorted octahedron for the gold(III) center. Extensive charge-assisted hydrogen bonding of the type N–H···O leads to the formation of a 2-D array and layers are consolidated into a 3-D network via C–H···O and C–H···Cl contacts. The compound crystallizes in the orthorhombic space group Pbca with a = 10.3380(11) ?, b = 8.2105(7) ?, c = 19.625(2) ?, and Z = 8. Index Abstract  Square planar complex cations form additional Au···O and Au···Cl interactions to form a tetragonally distorted octahedron for gold. The ionic components are connected into a 2-D array via charge-assisted N–H···O hydrogen bonding interactions.      

The orthorhombic polymorph of diammonium trichromate(VI) decaoxide, <Emphasis Type="Italic">α</Emphasis>–(NH<Subscript>4</Subscript>)<Subscript>2</Subscript>Cr<Subscript>3</Subscript>O<Subscript>10</Subscript>

Synthesis and crystal structure of a trichromium(VI) decaoxide compound, α–(NH₄)₂Cr₃O₁₀, is reported. The crystal structure has been determined from three dimensional X-ray data collected at low temperature, 173 K. The structure is isomorphous with its Rb and Cs trichromate analogues, orthorhombic, space group Pbca, with a = 11.2558(3), b = 9.3193(3), c = 18.9819(5) ? and Z = 8. The title compound is composed of discrete [Cr₃O₁₀]^2– chains held together by the counter ion charge and a hydrogen bonding network. The different conformations adopted by trichromate anion within its ammonium, alkali and organic salts are discussed.     

[Cd<Subscript>5</Subscript>(OH)(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>][CH<Subscript>3</Subscript>CO<Subscript>2</Subscript>]<Subscript>9</Subscript>, a cadmium hydroxy-acetate compound with a layered network

[Cd₅(OH)(H₂O)₃][CH₃CO₂]₉ crystallizes in the triclinic system, with the space group P , a = 10.897(3) Å, b = 11.035(5) Å, c = 16.061(12) Å, = 96.83(7), = 95.31(8), = 118.22(6) and z = 2. Its structure has been determined using 9497 unique single crystal data. The final refinements let the agreement factors R₁ and wR₂(F²) converge to reach the respective values of 0.0548 and 0.0986. R₁ = 0.0338 for the 7264 unique data with I > 2(I). [Cd₅(OH)(H₂O)₃][CH₃CO₂]₉ is a cadmium hydroxide acetate compound with a bi-dimensional structure in which hydrogen bonds insure cohesion between layers stacked along the [1 10] direction. The inorganic network is built up of layers constituted of CdO₆ octahedra and CdO₇ pentagonal bi-pyramids sharing edge or corner.     

Hydrothermal Synthesis and Structure of Fe<Subscript>6.36</Subscript>Mn<Subscript>0.64</Subscript>(PO<Subscript>3</Subscript>(OH))<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Abstract  

Single crystals of iron and manganese phosphate Fe_6.36Mn_0.64(PO₃(OH))₄(PO₄)₂ was synthesized by hydrothermal method. The compound crystallizes in the Fe₇(PO₄)₆ structure type and is isotypic with the solid solution \textM_{7 - \textx} \textM_\textx^￠ ( \textHPO₄ )₄ ( \textPO₄ )₂ {\text{M}}_{{7 - {\text{x}}}} {\text{M}}_{\text{x}}^{\prime} \left( {{\text{HPO}}_{4} } \right)_{4} \left( {{\text{PO}}_{4} } \right)_{2} where M is Fe, Co, Mg, Mn. The compound is triclinic, P-1, a = 6.571(5), b = 7.993(3), c = 9.547(2) Ǻ, α = 103.97(1)°, β = 109.29(2)°, γ = 101.57(3)°. The structure is based on a three-dimensional framework of distorted edge-sharing MO₆ and MO₅ polyhedra, forming infinite chains, which are interlinked by corner-sharing with PO₄ tetrahedra. The formula unit is centrosymmetric, with all atoms in general positions except for one Fe atom, which has site symmetry −1.     

[KCl<Subscript>3</Subscript>{H<Subscript>2</Subscript>dabco}]: A Unique 3-D Charge-Assisted Hydrogen-Bonded Hybrid Network of Anionic KCl<Subscript>3</Subscript> Chains and Organic Cations

Abstract  The 3-D hybrid network [KCl₃{H₂dabco}] resulted from the assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O. The compound crystallizes in the trigonal space group R-3c with a = b = 16.0437(2) Å, and c = 22.3094(2) Å. The structure consists in polymeric chains of anionic {KCl₃}²⁻ linked to {H₂dabco}²⁺ units by hydrogen bonds. Each organic cation establishes such charge-assisted H···Cl interactions with two inorganic arrays leading to a 3-D network. Index Abstract  Assemblage of KCl and [{H₂dabco}Cl₂] (1,4-diazabicyclo[2.2.2]octane) in H₂O resulted in a 3-D hybrid network of inorganic {KCl₃}²⁻ chains H-bonded to bridging organic cations.      

<Emphasis Type="Italic">Trans-</Emphasis>dichlorodioxobis(triphenylphosphate)molybdenum(VI), MoO<Subscript>2</Subscript>Cl<Subscript>2</Subscript>[OP(OPh)<Subscript>3</Subscript>]<Subscript>2</Subscript>

Abstract  The molecular structure of trans-dichlorodioxobis(triphenylphosphate) molybdenum(VI), MoO₂Cl₂[OP(OPh)₃]₂ has been determined. Crystal data: Monoclinic, Pn, a = 11.767(2), b = 10.341(2), c = 15.682(3) ?, β = 92.27(3)°, V = 1906.8(7) ?⁻³, Z = 2. Trans-dichlorodioxobis(triphenylphosphate)molybdenum(VI) was obtained by the reaction of molybdenum oxide, HCl and triphenylphosphate and was characterized by elemental analysis, IR, and ¹H-NMR spectroscopy. Index Abstract   Trans-dichlorodioxobis(triphenylphosphate)molybdenum(VI), MoO₂Cl₂[OP(OPh)₃]₂ V. Huch¹, R. Kumar², S. Mathur¹, R. Ratnani² The immediate environment around Mo is distorted octahedral with two cis-oxygen atoms and two trans-chlorine atoms along with two triphenylphosphate moieties.      

Synthesis and Crystal Structure of a Polymorph of the DMF Solvate of the Dicoppertetracarboxylate Paddlewheel Complex Cu<Subscript>2</Subscript>(p-aminobenzoate)<Subscript>4</Subscript>(DMF)<Subscript>2</Subscript>

Abstract  Reaction between p-aminobenzoic acid (HpABA) and Cu(NO₃)₂ · 2.5H₂O in basic MeOH/DMF affords green crystals of the dicopper paddlewheel complex, Cu₂(pABA)₄(DMF)₂ · 2DMF, 1, identified by single crystal X-ray crystallography: triclinic P-1, with a = 10.3728(2) ?, b = 10.617(2) ?, c = 11.128(2) ?, α = 81.705(3)°, β = 79.984(2)°, γ = 65.965(2)° and Z = 2. The crystal structure of 1 reveals that it is the second polymorph of Cu₂(pABA)₄(DMF)₂ · 2DMF and experiments on the stability of 1 indicate that it can be converted to Form I through desolvation followed by exposure to DMF. Graphical Abstract  Crystal structure of a polymorphic discrete dicoppertetracarboxylate is investigated for the conversion between the two forms influenced by hydrogen bonds.      

Synthesis and Crystal Structure of New Indium Iodate (K<Subscript>0.6</Subscript>Na<Subscript>0.4</Subscript>Ba)In[IO<Subscript>3</Subscript>]<Subscript>6</Subscript>

Crystals of new indium iodate (K_0.6Na_0.4Ba)In[IO₃]₆ were prepared by the hydrothermal synthesis. The unit-cell parameters are a = 11.3984(3) Å, с = 11.3817(3) Å, sp. gr. R3?. The chemical formula of the compound was derived from the structure determination and refinement with anisotropic displacement parameters to R = 0.0284. In the structure the InO₆ octahedra share vertices with six umbrella-like [IO₃]–groups typical of iodates and form isolated 3?-symmetric charged \(\rm{In[IO_{3}]_6^{3-}}\) clusters. Large Ba, K, and Na cations occupy a common site on a threefold axis due to the isomorphous substitution and compensate the charge of the clusters. The new structure extends the family of the recently discovered alkali-metal and barium iodates containing Ti and Zr atoms in octahedral sites. The iodate K₂Ge[IO₃]₆ containing Ge atoms in the centers of octahedra is the parent compound of this structural family.     

Expanded Prussian Blue Analogue Based on Octahedral {Nb<Subscript>6</Subscript>} Clusters and {K<Subscript>2</Subscript>} Dimers as Nodes

Abstract  The preparation, structures, and characterization of two new compounds containing octahedral niobium cyanochloride clusters as building units and (Et₄N)⁺ as cation are reported. The reaction between Nb₆Cl₁₄ · 8H₂O, KCN and (Et₄N)Cl led to the formation of (Et₄N)₄[Nb₆Cl₁₂(CN)₆] · 2.67H₂O (1) which crystallizes in triclinic P-1 space group (No. 2) with a = 12.552(2), b = 12.818(2), c = 12.919(2) ?, α = 105.157(3)°, β = 104.188(3)°, γ = 117.390(2)°, V = 1611.7(5) ?³ and Z = 1. 1 has a 2D hydrogen-bonded layer structure based on [Nb₆Cl₁₂(CN)₆]⁴⁻ units connected through hydrogen bonding between cyanide ligands and solvent water molecules. In the presence of large excess of K⁺ ions, similar reaction leads to formation of K₂(Et₄N)₂[Nb₆Cl₁₂(CN)₆] (2) which crystallizes in the tetragonal I4/m space group (No. 87) with a = b = 10.9597(3), c = 19.178(1) ?, V = 2303.6(2) ?³ and Z = 2. Its 3D structure is based on [Nb₆Cl₁₂]²⁺ and [K₂]²⁺ nodes bridged by cyanide ligands to form an expanded Prussian blue type framework with (Et₄N)⁺ acting as charge compensating ions. Index Abstract  An expanded Prussian blue type 3D framework based on hexanuclear {Nb₆} and dinuclear {K₂} units which are bridged by cyanide linker was synthesized and characterized. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Synthesis of <Emphasis Type="Italic">E</Emphasis> Isomer and Crystal Structures of <Emphasis Type="Italic">E</Emphasis> and <Emphasis Type="Italic">Z</Emphasis> Isomers of 3-(2,5-Dimethoxyphenyl)-2-(4-methoxyphenyl)acrylonitrile

Abstract Details of the synthesis of the E isomer of 3-(2,5-dimethoxyphenyl)-2-(4-methoxyphenyl)acrylonitrile, and the X-ray crystal structures of both the E and Z isomers of this compound are presented. The E isomer crystallizes in the P2₁/c space group with cell parameters, a = 8.5659(17) ?, b = 16.399(3) ?, c = 11.224(2) ?, α = 90°, β = 95.27(3)°, γ = 90°and Z = 4. The Z isomer crystallizes in the Pca2₁ space group with cell parameters, a = 4.1223(8) ?, b = 19.113(4) ?, c = 19.453(4) ?, α = 90°, β = 90°, γ = 90° and Z = 4. Index Abstract Synthesis of E isomer and X-ray crystal structure determination of both E and Z isomers of 3-(2,5-dimethoxyphenyl)-2-(4-methoxyphenyl)acrylonitrile are presented.      

Growth and crystal structure of binary molybdate CsFe(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>

CsFe(MoO₄)₂ single crystals have been grown by solution-melt crystallization with a charge-to-solvent ratio of 1: 3 (with Cs₂Mo₃O₁₀ used as a solvent). The crystal structure of this compound has been refined by X-ray diffraction (X8 APEX automatic diffractometer, MoK _α radiation, 356 F(hkl), R = 0.0178). The trigonal unit cell has the following parameters: a = b = 5.6051(2) Å, c = 8.0118(4) Å, V = 217.985(15) ų, Z = 1, ρ_calc = 3.875 g/cm³, and sp. gr. P \(\bar 3\) m1. The structure is composed of alternating layers of FeO₆ octahedra (with MoO₄ tetrahedra attached by sharing vertices) and CsO₁₂ icosahedra.     

Dimer Formation in 4-Benzyl-5-Methoxymethyl-3-Methyl-1<Emphasis Type="Italic">H</Emphasis>-Pyrrole-2-Carboxylic Acid Benzyl Ester

Abstract A new substituted pyrrole, a precursor of meso-free-porphyrins, has been synthesised and characterised by single-crystal X-ray diffraction: monoclinic, P2₁/c with a = 14.607(9) ?, b = 5.136(2) ?, c = 25.832(17) ?, β = 108.14(5)°, Mr = 349.41, V = 1841.6(18) ?³, Z = 4. The molecules are assembled in centrosymmetric dimers via strong N–H...O hydrogen bonds. The dimers are gathered into chains via C–H...π intermolecular interactions. Graphical abstract The molecules in 4-benzyl-5-methoxymethyl-3-methyl-1H-pyrrole-2-carboxylic acid benzyl ester are joined in dimmers by strong hydrogen bonds. The dimmers are aggregated in chains running along the b axis through C-H...?€ intermoleculear interactions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The Influence of Cation Substitution on the Kinetics of Phase Transitions in Crystals of (K,NH<Subscript>4</Subscript>)<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> Solid Solutions

The structure of (K_0.967(NH₄)_0.033)₃H(SO₄)₂ crystals, belonging to the K₃H(SO₄)₂–(NH₄)₃H(SO₄)₂–H₂O salt system, has been investigated by X-ray structural analysis. The room-temperature characteristics of the atomic structure of these crystals are found to be as follows: sp. gr. C2/c, Z = 4, a = 14.7025(4) Å, b = 5.6859(2) Å, c = 9.7885(3) Å, and R/wR = 0.021/0.030%. The thermal and optical properties of (K,NH₄)₃H(SO₄)₂ and K₃H(SO₄)₂ single crystals have been investigated and compared in a temperature range of 295–500 K.     

Synthesis and crystal structure of anhydrous copper suberate: [Cu<Subscript>2</Subscript>(OOC-(CH<Subscript>2</Subscript>)<Subscript>6</Subscript> -COO)<Subscript>2</Subscript>]

The title compound [Cu₂(OOC-(CH₂)₆-COO)₂] was synthesized and its crystal structure has been determined by single crystal X-ray diffraction methods. The complex crystallizes in the triclinic space group P-1 with a=5.1077(5) ?, b=8.362(2) ?, c=11.378(2) ?, α=93.773(6)°, β=97.587(9)°, γ=90.493(’9)° and D _cal=1.629 mg/m³ for Z=1.  The structure is polymeric and consists of discrete anhydrous centrosymmetric binuclear units [Cu₂(OOC-(CH₂)₆-COO)₂]. The two copper(II) centres bridged by the suberate groups in a syn-syn conformation, are in pentacoordinated distorted square-pyramidal coordination environment, with an intramolecular Cu–Cu distance of 2.5793(10) ?. Each binuclear unit, related to the next through μ_oxo bridges with a Cuμ_oxo–Cuμ_oxo separation of 3.2326(10)?, defines infinite chains of one-edge sharing CuO₅ square pyramid.     

Synthesis and crystal structure of bis(malonato)tetra (aqua)barium(II)cobalt(II): [BaCo(C<Subscript>3</Subscript>H<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>]

The title compound [BaCo(C₃H₂O₄)₂(H₂O)₄] was synthesized and its crystal structure was determined. The compound is orthorhombic, space group Pccn with a = 18.974(3) Å, b = 6.783(2) Å, c = 9.394(4) Å. The structure is polymeric and consists of edge-sharing BaO₈ polyhedra and CoO₆ octahedra linked together by the malonate groups. The geometry around the Ba(II) centres is a slightly distorted square-antiprism with Ba–O distances ranging from 2.789(4) to 2.843(4) Å. Around the Co(II) centres, the coordination forms a distorted octahedron with Co–O bonds between 2.040(3) and 2.238(4) Å.     

Crystal Structure of a Rearranged Cage Compound, 3-Hydroxy-4-aza-8-oxoheptacyclo [9.4.1.0<Superscript>2,10</Superscript>.0<Superscript>3,14</Superscript>.0<Superscript>4,9</Superscript>.0<Superscript>9,13</Superscript>.0<Superscript>12,15</Superscript>]tetradecane

Abstract  Polycyclic hydrocarbon compounds exhibit a wide variety of biological activities, ranging from antiviral to Parkinson’s disease. Several structures such as the adamantanes have reached clinical status and are used therapeutically to treat, amongst others, neurodegenerative disorders such as Alzheimer’s. Polycyclics have also been utilised as carrier molecules to facilitate entry of drugs into the brain. The synthesis, molecular and crystal structure of a new polycyclic compound, 3-hydroxy-4-aza-8-oxoheptacyclo[9.4.1.0^2,10.0^3,14.0^4,9.0^9,13.0^12,15]tetradecane, are reported. NMR spectroscopy was applied for structure elucidation of the novel compound and a rearrangement mechanism is proposed for its formation. This compound crystallises in the orthorhombic system, space group Pbca (no. 61). The unit cell parameters are: a = 12.3763 (7), b = 11.6597 (6), c = 15.0539 (8) ?, V = 2172.3 (2) ?³ , and Z = 8 molecules in the unit cell. The reported structure was confirmed by X-ray analysis, which showed that the title molecules associate into centrosymmetric dimers via N–H···O hydrogen bonding. Index Abstract  The synthesis and structure of a new polycyclic compound, 3-hydroxy-4-aza-8-oxoheptacyclo[9.4.1.0^2,10.0^3,14.0^4,9.0^9,13.0^12,15]tetradecane, are reported in this article.