Synthesis and Crystal Structures of Octahedral Sn(IV) Complexes Prepared from SnCl<Subscript>2</Subscript>·2H<Subscript>2</Subscript>O and 2-Hydroxyacetophenone (<Emphasis Type="Italic">S</Emphasis>-benzydithiocarbazate) Ligand (H<Subscript>2</Subscript>L)

Abstract  

Two coordination octahedral Sn(IV) complexes [Sn(L)₂] and cis-[SnCl₂(L)(dmso)], where H₂L is 2-hydroxyacetophenone (S-benzydithiocarbazate), were prepared and characterized by elemental analysis, IR, NMR (¹H, ¹³C), ¹¹⁹Sn M?ssbauer spectroscopies and X-ray diffraction techniques to investigate their structural properties. Both crystallize in the Monoclinic system, with parameters: a = 8.1905(3), b = 30.8811(15), c = 12.8959(7) ?, β = 94.465(3)° and Z = 4 for [Sn(L)₂] and a = 8.5247(2), b = 21.5445(7), c = 12.3706(3) ?, β = 96.932(2)° and Z = 4 for cis-[SnCl₂(L)(dmso)]. In both complexes, the Sn(IV) central atom is coordinated in a distorted octahedral geometry with the thiolate ligand (L²⁻) coordinated via O, N and S atoms. The ¹¹⁹Sn M?ssbauer spectroscopy of the complexes were studied and the results revealed that both complexes posses isomer shift (δ) and quadrupole splitting (Δ), which are almost the same.     

Crystal Structure of [Zn(2-Bromobenzoato)<Subscript>2</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> and [Zn(2-Bromobenzoato)<Subscript>2</Subscript>(<Emphasis Type="Italic">N</Emphasis>-Methylnicotinamide)]<Subscript>2</Subscript>

Abstract  

The syntheses and structural characterizations of two novel 2-bromobenzoatozinc(II) complexes—[Zn(2-BrC₆H₄COO)₂] _n (I) and [Zn(2-BrC₆H₄COO)₂(mnad)]₂ (II), where mnad is N-methylnicotinamide are reported. Compound (I) crystallized with a monoclinic lattice (space group P2₁/c) and is polymeric in solid state. Its cell parameters are: a = 7.37220(10) Å, b = 19.9639(3) Å, c = 30.2756(5) Å, β = 94.7510(7)°, V = 4440.59(12) ų, Z = 4. The coordination environments of all zinc atoms are distorted tetrahedra built from four carboxylate oxygen atoms coming from four 2-bromobenzoato ligands. Compound (II) crystallized with a monoclinic lattice (space group P2₁/c) with a = 11.7488(2) Å, b = 20.3683(3) Å, c = 9.30130(10) Å, β = 100.3941(11)°, V = 2189.30(5) ų, Z = 2. This dimeric molecule features a paddle-wheel [Zn₂O₈] cage in solid state; the coordination environment of the central atom is square pyramidal consisting of four carboxylate oxygen atoms and the pyridine N atom of the mnad ligand.     

Synthesis,Structure and DNA-Binding Studies of Oxamido-Bridged Binuclear Copper(II) Complex: [Cu<Subscript>2</Subscript>(heap)](bipy)(ClO<Subscript>4</Subscript>)<Subscript>2</Subscript>

Abstract  

A new μ-oxamido-bridged copper(II)–copper(II) binuclear complex with formula of [Cu₂(heap)](bipy)(ClO₄)₂, where H₂heap and bipy are N,N′-bis(N-hydroxyethylaminopropyl)-oxamide and 4,4′-bipyridine, respectively, has been synthesized and characterized by elemental analyses, molar conductivity measurement, IR and electronic spectra studies, and single-crystal X-ray diffraction. The single-crystal X-ray analysis reveals that the complex has two embedded inversion centers at the mid-points of the C6–C6ⁱ bond of the oxamido group and the C7–C7ⁱⁱ bond of the 4,4′-bipyridine, respectively [symmetry code: (i) 2−x, 1−y, 1−z; (ii) =2−x, −y, 1−z]. Copper(II) atom is in a square-planar coordination geometry. The Cu···Cu separation through the oxamido birdge is 5.1430(8) ?. The bridging ligand (heap²⁻) adopts a bis-tetradentate trans conformation. A one-dimensional hydrogen bonding supramolecular structure parallel to the [2 1 0] direction is found in the crystal. The interaction of the binuclear copper(II) complex with herring sperm DNA (HS-DNA) was investigated by using absorption and emission spectra, electrochemical techniques and viscometry. The results suggest that the binuclear copper(II) complex interacts with HS-DNA by electrostatic interaction with intrinsic binding constant of 1.54 × 10⁴ M⁻¹.     

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.      

Reaction of (<Emphasis Type="Italic">n</Emphasis>-Bu<Subscript>4</Subscript>N)<Subscript>2</Subscript>[Re<Subscript>2</Subscript>Cl<Subscript>8</Subscript>] with a 2-Oxocarboxylic Acid: Crystallographic Characterization of a New Dirhenate(III) Complex

Abstract  

The reaction of tetra-n-butylammonium-octachloridodirhenate(III), (Bu₄N)₂[Re₂Cl₈], with molten 2-oxobutanoic acid Et(CO)CO₂H at 75 °C afforded pale-green tetra-n-butylammonium-hexachlorido-(2-oxobutanoato)-dirhenate(III), (Bu₄N)[Re₂(O₂C(CO)Et)Cl₆]. Slow evaporation of a solution in CHCl₃ yielded shiny, mint-green crystals of the dirhenate complex. The X-ray crystal structure determination (monoclinic, P2₁/n, a = 11.6557(3) ?, b = 20.5382(5) ?, c = 13.9281(3) ?, β = 112.508(1)°, Z = 4) revealed the presence of [Re₂(O₂C(CO)Et)Cl₆]⁻ anions and tetra-n-butylammonium cations. The central [Re₂]⁶⁺ core with a Re≣Re quadruple bond of 2.2263(3) ? length is μ₂-bridged by one 2-oxobutanoato ligand and additionally coordinated by six chlorido ligands. Each dirhenate unit is linked via two Re···Cl contacts to dimeric, centrosymmetric entities of the constitution {[Re₂(O₂C(CO)Et)Cl₆]₂}²⁻. In the crystal, these dimers of dinuclear complexes are separated from each other by the bulky tetra-n-butylammonium cations.     

Structural Studies of (Pyridine)<Subscript>3</Subscript>ZnFe(CO)<Subscript>4</Subscript> and (Pyridine)(Neocuproin)CdFe(CO)<Subscript>4</Subscript>

Abstract  

The structure of the previously reported (py)₃ZnFe(CO)₄ (py = pyridine) has been determined, confirming the monomeric nature of this species. The complex has average Zn–N and Zn–Fe bond lengths of 2.0970(7) and 2.4017(3) ?, and features a coordination geometry about Fe which is intermediate between trigonal bipyramidal and face monocapped tetrahedral. The space group is P2₁/c, with a = 8.22080(10) ?, b = 16.1668(3) ?, c = 15.4669(3) ?, β = 102.5869(11)°, V = 2006.21(6) ?³, D_calc. = 1.558 g/cm³ at 150(1) K. A monomeric cadmium analogue, (pyridine)(neocuproin)CdFe(CO)₄, has also been synthesized, and found to possess a similar geometry, with average Cd–N and Cd–Fe bond lengths of 2.352(2) and 2.5380(5) ?. The space group is P[`1] P\overline{1} with a = 10.8900(2) ?, b = 11.3042(3) ?, c = 15.5488(4) ?, α = 85.1251(10)°, β = 84.3468(14)°, γ = 72.0377(15)°, V = 1808.93(7) ?³, D_calc. = 1.478 g/cm³ at 150(1) K.     

<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 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.      

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.     

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.      

Synthesis and Structural Characterization of <Emphasis Type="Italic">N</Emphasis>-(2-Pyridylmethyl)-3-Methoxysalicylaldiminato Copper(II) Chloride

Abstract  The copper(II) complex [Cu(C₅H₄NCH₂−N=CH–C₆H₃OCH₃–O)Cl], (1) containing a new tridentate Schiff base ligand (LH), which is the 1:1 condensation product of 2-(aminomethyl)pyridine and o-vaniline, has been synthesised and characterized by IR and UV–Vis spectra. Structural investigation shows that 1 crystallizes to a monoclinic system, having space group P2(1)/c, a = 6.9634(7), b = 18.1209(19), c = 10.3448(11) ?, α = 90°, β = 103.97(2)°, γ = 90° and Z = 4. The coordination geometry around the copper atom is slightly distorted square planar, formed by the N₂O donor set of the Schiff base and one Cl atom. The Cu–N(1), Cu–N(2), Cu–O(1) and Cu–Cl bond distances are 2.0114(14), 1.9414(14), 1.9147(12) and 2.2520(5) ?, respectively. Index Abstract  The copper(II) complex [Cu(C₅H₄NCH₂−N=CH–C₆H₃OCH₃–O)Cl], (1) containing a tridentate Schiff base ligand (LH), synthesised and characterized by IR and UV–Vis spectra. The central copper ion possesses a distorted square-planar geometry.      

Synthesis,Crystal Structure and Luminescence Property of a Chiral Magnesium (II) Mixed-ligand Complex [Mg(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(phen)(HBDC)<Subscript>2</Subscript>](phen)

Abstract  

A new mixed-ligand complex of [Mg(H₂O)₂(phen)(HBDC)₂](phen) (phen = 1, 10-phenanthroline, H₂BDC = 1,3-benzene dicarboxylic acid) has been synthesized and its crystal structure determined by single-crystal X-ray diffraction. It is noteworthy that this complex was formed from achiral reactants, and found to crystallize in the chiral space group C2. Structure analysis shows that each Mg(II) ion is coordinated by the two nitrogen atoms of phen, one oxygen atom from each of the two 1,3-HBDC molecules and one oxygen atom from each of the two water molecules, leading to a distorted octahedral geometry. The mixed-ligand complexes are assembled into a two-dimensional supramolecular network through the formation of intermolecular hydrogen bonds. The luminescence property and thermal stability behavior of the complex were also investigated. The complex shows a strong blue luminescence emission. Crystal data: a = 24.5856(16), b = 10.1598(6), c = 7.1460(4) ?, β = 105.226(2)o, V = 1722.30(18)?³, Z = 2, R ₁ = 0.0367, wR ₂ = 0.0833 [I>2σ(I)].     

Synthesis and Characterization of [(1-benzylpyrazole) [<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-bis(2-aminoethyl)-1,2-ethanediamine]copper(II)] Diperchlorate,a Structure with a Sterically Strained,Distorted-Trigonal-Bipyramidal Cation

Abstract  The synthesis, characterization, and molecular structure of the title compound, [(1-benzylpyrazole)[N,N-bis(2-aminoethyl)-1,2-ethanediamine]copper(II)] diperchlorate, [(nbp)(tren)Cu(II)](ClO₄)₂, 2  · 2ClO₄, is reported. The salt crystallized in the monoclinic space group P2₁/n with a = 10.1453(5) ?, b = 17.5250(8) ?, c = 13.6021(6) ?, β = 100.737(19)° and V = 2376.06(19) ?³ with Z = 4. The structure contains copper(II) (nbp)(tren) cations, each with a distorted-trigonal-bipyramidal CuN₅ coordination geometry, separated by perchlorate anions. The cations exhibit steric strain associated primarily with close contacts between the methylene protons of the nbp ligand and one of the amine groups of the tren ligand. The strain has a noticeable effect on the coordination geometry and certain physical properties of the complex. Graphical Abstract  In the title structure, steric strain in the (nbp)(tren)Cu(II) cations, associated with close contacts between protons of the nbp ligand and two of the amine groups of the tren ligand (dashed lines in the figure below) affects certain physical properties of the cation and is consistent with an anomalously long Cu(II)–N(pyrazole) distance (Cu–N41) and an unusually large axial–equatorial angle, N41–Cu–N12.      

Synthesis and Structure of (TMEDA)Cr(I)<Subscript>2</Subscript>(THF) and [(<Emphasis Type="Italic">N,N</Emphasis>-DMEDA)<Subscript>2</Subscript>CrI] I

Abstract  

The complexes (TMEDA)Cr(I)₂(THF) (1) and [(N,N-DMEDA)₂CrI] I (2) were synthesized and spectroscopically characterized (TMEDA = tetramethylethylenediamine, N,N-DMEDA = N,N dimethylethylenediamine). Complex 1 possesses square pyramidal geometry and crystallizes in spacegroup Pbca with crystal cell parameters a = 11.206(2) ?, b = 12.698(3) ?, c = 23.434(5) ?, V = 3,334.6(12) ?³ and Z = 4. Complex 2 also possesses square pyramidal geometry with a non-coordinated iodide counter anion and crystallizes in spacegroup P2₁/n with crystal cell parameters a = 9.4071(13) ?, b = 14.628(2) ?, c = 11.7516(16) ?, β = 98.904(2) ?°, V = 1,597.6(4) ?³ and Z = 4. Complex 2 has previously been incorrectly assigned as an octahedral complex based on spectroscopy.     

Convenient Route to Alkylene Dithiophosphato Ligands: Synthesis and Crystallographic Analysis of [OCH<Subscript>2</Subscript>CMe<Subscript>2</Subscript>CH<Subscript>2</Subscript>OPS<Subscript>2</Subscript>HNEt<Subscript>3</Subscript>]

Abstract  

Triethylammonium salts of O,O′-alkylene dithiophosphato like OGOPS₂HNEt₃, [where, G = –CH₂CMe₂CH₂–(1), –CH₂CEt₂CH₂–(2), –CMe₂CH₂CHMe–(3) and –CMe₂CMe₂–(4)] have been synthesized in quantitative yield by the direct reaction of P₂S₅ with 1,2- and 1,3-substituted glycols in presence of triethylamine, Et₃N, in 1:2:2 molar stoichiometry in toluene. These have been mainly characterized by molecular weight, IR and NMR (¹H, ¹³C and ³¹P) spectroscopic studies. Single crystal X-ray structure analysis of [OCH₂CMe₂CH₂OPS₂HNEt₃] reveals that phosphorus atom is tetrahedrally bonded to two sulfur atoms and two oxygen atoms in the ring and the molecule exists as discrete cation and anion. The structure is stabilized by cation–anion N–H···S hydrogen bonded interactions. Antiparallel pattern of triethylammonium ion is sandwiched within the two-dimensional layers of the ring system.     

Unusual Co-Crystallization of both Monomeric and Dimeric Forms of Cu[PhN(py)quin]Cl<Subscript>2</Subscript>

Abstract  

The aryl functionalized diquinolyl amine MesN(quin)₂ (1) and the pyridyl-quinolyl amine (2,6-iPr₂C₆H₃)N(py)quin (2) have been prepared via palladium catalyzed cross-coupling of substituted anilines with 2-chloroquinoline. The HBF₄ acid salts of (2,6-ⁱPr₂C₆H₃)N(quin)₂ (3) and MesN(py)quin (4), as well as the copper complex [Cu{PhN(py)quin}Cl₂] (5) have been prepared in order to probe the effect that ligand coordination has on its geometry. The molecular structures of each have been determined by X-ray crystallography. The free ligands 1 and 2 crystallize in three-bladed propellar conformations, having smaller degrees of “pitch” between the two heterocycles than either has with the aryl “blade”, allowing for greater heterocycle π-system overlap with the amine lone pair. Acid confinement of similar ligands in 3 and 4 results in forced coplanarity of the two heterocycles, which coordinate the HBF₄ proton in an asymmetric fashion. The copper complex 5 crystallizes with both monomeric and dimeric forms present in the asymmetric unit. Crystal data: (1) Space group P2₁/c, a = 14.058(3), b = 12.202(2), c = 12.831(3) ?, β = 104.61(3)°, V = 2129.8(8) ?³, Z = 4, R = 0.0596, wR₂ = 0.1453. (2) Space group P2₁/c, a = 22.250(4), b = 8.628(2), c = 23.031(5) ?, β = 92.88(3)°, V = 4370(2) ?³, Z = 8, R = 0.0514, wR₂ = 0.1323. (3) Space group Pbca, a = 13.886(3), b = 18.016(4), c = 21.347(4) ?, V = 5340(2) ?³, Z = 8, R = 0.0722, wR₂ = 0.1635. (4) Space group P2₁/c, a = 10.629(2), b = 18.489(4), c = 10.907(2) ?, β = 92.88(3), V = 2140.6(7) ?³, Z = 4, R = 0.0551, wR₂ = 0.1531. (5) Space group \text P[`1]{\text P}\bar{1}, a = 9.706(2), b = 11.325(2), c = 17.322(4) ?, α = 98.28(3), β = 94.85(3), γ = 91.83(3)°, V = 1875.6(7) ?³, Z = 1, R = 0.0481, wR₂ = 0.0946.     

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 and Characterization of <Emphasis Type="Italic">N,N</Emphasis>-di(prop-2-ynyl)-<Emphasis Type="Italic">p</Emphasis>-toluidine

Abstract  

In order to investigate the intramolecular [4 + 2] cycloaddition, we prepared some new tertiary N-(5-substituted-2-furfuryl)-N-prop-2-ynyl-p-toluidines [Hergold-Brundić et al., Acta Cryst C56:e520, 2000; Mance and Jakopčić, Mol Divers 9:229, 2005; Mance, “unpublished results”] by the alkylation of secondary N-(5-substituted-2-furfuryl)-p-toluidines with the propargyl-bromide [Mance and Šindler-Kulyk, Synth Commun 26:923, 1996]. In the course of preparation of N-(5-methoxy-2-furfuryl)-N-prop-2-ynyl-p-toluidine [Mance, “unpublished results”], besides the main product (compound 1) (Scheme 1) we obtained N,N-di(prop-2-ynyl)-p-toluidine (compound 2) as the colourless crystals. The title compound 2, N,N-di(prop-2-ynyl)-p-toluidine, C₁₃H₁₃N, crystallizes in monoclinic C 2/c space group with unit cell parameters: a = 19.5319(9) ?, b = 7.5230(3) ?, c = 15.9000(7) ?, β = 112.554(5)°, V = 2157.64(18) ?³, Z = 8. The crystal structure is dominated by van der Waals forces only. The bond distances around amine N atom correspond to σ dominated bonds (1.467(2), 1.462(2) and 1.419(2) ?). The angles sum around amine N atom is in accord with sp³ hybridization (343°).     

Structural Studies of [Ru(1,8-naphthyridine)<Subscript>4</Subscript>]<Superscript>2+</Superscript> and [Ru(1,5-cyclooctadiene)(1,8-naphthyridine)<Subscript>2</Subscript>]<Superscript>2+</Superscript> as their Tetraphenylborate Salts

Abstract  

The previously reported [Ru(naph)₄]²⁺ complex (naph = 1,8-naphthyridine) has been prepared by a simplified route using [RuCl₂(1,5-COD)] _x (COD = cyclooctadiene) as starting material and isolated as its tetraphenylborate salt. The salt crystallizes in the monoclinic space group P2₁/n with a = 13.6531(3) ?, b = 12.5389(4) ?, c = 20.0349(5) ?, β = 96.5884(15)o, V = 3407.22(16) ?, D _calc = 1.300 at 150(1) K. The dication has crystallographically imposed inversion symmetry. Although the iron analogue has been found to have a coordination number of eight, the ruthenium complex is only six-coordinate, which is achieved by the presence of two monodentate and two bidentate 1,8-naphthyridine ligands. The observation of a higher coordination number for Fe(II) vs. Ru(II) can be explained by the high spin nature of the iron complex. A byproduct complex, [Ru(1,5-COD)(naph)₂][B(C₆H₅)₄]₂, could also be synthesized, isolated pure, and structurally characterized. The organometallic complex possesses an 18 electron configuration by virtue of the dicationic metal center being coordinated by the diene ligand and all four nitrogen lone pairs. This salt crystallizes in the triclinic space group \textP[`1] {\text{P}}\bar{1} with a = 12.9538(3) ?, b = 14.9485(3) ?, c = 17.4291(3) ?, α = 69.0649(11)o, β = 78.3211(9)o, γ = 78.5629(10)o, V = 3057.50(11) ?³, D _calc = 1.293 at 150(1) K.     

Crystal Structure of a New Quinternary Oxide: NaTl<Subscript>3</Subscript>Cu<Subscript>4</Subscript>Te<Subscript>2</Subscript>O<Subscript>12</Subscript>

Abstract  

A new quinternary oxide, NaTl₃Cu₄Te₂O₁₂, has been synthesized and characterized by single crystal X-ray diffraction. The reported material was synthesized by hydrothermal techniques using TlNO₃, CuO, TeO₂, and NaOH as reagents. The material exhibits a two-dimensional layered structure consisting of edge-shared CuO₆ and TeO₆ polyhedra separated by Na⁺ and Tl⁺ cations. NaTl₃Cu₄Te₂O₁₂ crystallizes in space group C2/m with a = 12.9800(17) ?, b = 9.3455(12) ?, c = 5.2335(7) ?, β = 104.276(2)°, V = 615.24(14) ?³, and Z = 2.