Chloro­bis­(tri­phenyl­phosphine)­nickel(I) tetra­hydro­furan solvate and an unsolvated trigonal phase of chloro­tris­(tri­phenyl­phosphine)­nickel(I)

In [NiCl(C₁₈H₁₅P)₂]·C₄H₈O, the Ni atom is coordinated by three ligands in a distorted trigonal–planar configuration, with a P—Ni—P angle of 111.52 (2)°. In [NiCl(C₁₈H₁₅P)₃], there are three independent mol­ecules in the asymmetric unit, with each Ni—Cl bond on a crystallographic threefold rotation axis. Each Ni centre is tetrahedrally bound. The Ni atoms in both compounds have a d⁹ configuration and a formal oxidation state of Ni^I. A comparison is made between the form of [NiCl(PPh₃)₃] presented here and that of a known toluene solvate.     

A pseudo‐trigonal bipyramidally ­coordinated Pt atom in dicarbonyl­bis(octacarbonyl‐μ‐di­cyclo­hexyl­phosphidodirhenio)­platinum(II)

In the title compound, [PtRe₄(C₁₂H₂₂P)₂(CO)₁₈] or [(μ‐PCy₂)(CO)₈Re₂]₂Pt(CO)₂ (Cy is cyclohexyl), two phosphido‐bridged dirhenium groups are linked by a Pt(CO)₂ unit and show different bonding patterns for stereochemical reasons. The Re—Re distances are 3.2620 (15) and 3.0739 (15) Å, and the Pt—Re distances are 2.9165 (12), 2.9025 (15) and 2.8548 (13) Å.     

The trans influence in mer‐tri­chloro­nitridobis­(tri­phenyl­arsine)­ruthenium(VI)

The title compound, mer‐[RuCl₃N(C₁₈H₁₅As)₂], is the first structurally characterized example of a nitride complex in which ruthenium is six‐coordinated to monodentate ligands only. The Ru[triple‐bond]N bond length [1.6161 (15) Å] is relatively long, and the trans influence of the nitride ligand is reflected by the difference between the Ru—Cl_trans and Ru—Cl_cis bond lengths [0.1234 (4) Å]. The N—Ru—Cl_trans axis is sited on a twofold axis.     

trans‐Bis(2,2‐diphenyl­ethyl­amine‐κN)bis­(5,5‐diphenyl­hydantoinato‐κN3)copper(II) and its chloro­form disolvate

The crystal structures of the title compounds, [Cu(C₁₅H₁₁N₂O₂)₂(C₁₄H₁₅N)₂] and [Cu(C₁₅H₁₁N₂O₂)₂(C₁₄H₁₅N)₂]·2CHCl₃, respectively, have been determined. The red disolvate complex affords a square‐planar CuN₄ coordination environment in which the Cu^II atom lies on a centre of symmetry. The blue solvent‐free complex affords a distorted square‐pyramidal CuN₄O coordination environment and adjacent mol­ecules form centrosymmetric dimers. A comparison of the different crystal structures focuses on the role of the solvent mol­ecules in supramolecular assemblies of the copper(II) complexes.     

Tris(2,6‐di‐tert‐butyl‐4‐methyl­phenol­ato‐O)(tri­phenyl­phosphine oxide‐O)samarium(III)

In the title complex, [Sm(C₁₅H₂₃O)₃(C₁₈H₁₅OP)], the central metal atom is coordinated by three O atoms of the aryl­oxo ligands and by one O atom of the tri­phenyl­phosphine oxide mol­ecule resulting in a distorted tetrahedral geometry. The Sm—O_Ar distances (Ar is aryl) range from 2.122 (2) to 2.190 (2) Å and the Sm—O_PPh3 bond length is 2.306 (2) Å.     

Bis(iminodiethylenedi­ammonium) di‐μ5‐hydrogen­phosphato‐penta­molybdate(VI) tetra­hydrate

The crystal structure of the title compound, (C₄H₁₅N₃)₂[Mo₅O₁₅(HPO₄)₂]·4H₂O, is made up of [Mo₅O₁₅(HPO₄)₂]⁴⁻ clusters, iminodiethylenediammonium cations and solvent water mol­ecules. The [Mo₅O₁₅(HPO₄)₂]⁴⁻ cluster, with approximate C₂ symmetry, can be considered as a ring formed by five distorted edge‐ and corner‐sharing MoO₆ octa­hedra, capped on both poles by a hydro­phosphate tetra­hedron. There exist N—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds between the organic ammonium groups and the clusters, with inter­atomic N⋯O distances ranging from 2.675 (3) to 2.999 (3) Å, and C⋯O distances ranging from 3.139 (5) to 3.460 (5) Å.     

[N,N‐Bis(2‐hydroxy­ethyl)­di­thio­car­bamato‐S]­bis­(tri­phenyl­phosphine‐P)­copper(I) tri­phenyl­phosphine solvate

In the title compound, [Cu(C₅H₁₀NO₂S₂)(C₁₈H₁₅P)₂]·C₁₈H₁₅P, the Cu atom is in a distorted tetrahedral coordination, with two tri­phenyl­phosphine P atoms and two S atoms from an N,N‐bis(2‐hydroxy­ethyl)­di­thio­carbamate ligand occupying the vertices. The crystal structure is characterized by alternate layers of complex and tri­phenyl­phosphine mol­ecules.     

Azido­[1,1′‐bis­(di­phenyl­phosphino)­ferrocene](penta­methyl­cyclo­penta­dienyl)­rhodium(III) hexa­fluoro­phosphate

In the title compound, azido‐2κN‐bis­[μ‐(1η⁵:2κP)‐di­phenyl­phosphino­cyclo­penta­dienyl][2(η⁵)‐penta­methyl­cyclo­penta­di­enyl]­iron(III)­rhodium(III) hexa­fluoro­phosphate, [{Rh(C₁₀H₁₅)(N₃)}{Fe(μ‐C₁₇H₁₄P)₂}]PF₆ or [FeRh(C₁₀H₁₅)(μ‐C₁₇H₁₄P)₂(N₃)]PF₆, the coordination sphere of Rh^III can be described as pseudo‐tetrahedral, composed of two P atoms from a 1,1′‐bis­(di­phenyl­phosphino)­ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C₅Me₅ (Cp*) ligand. The two cyclo­penta­dienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh⋯Fe distance is 4.340 (2) Å.     

[Bis(3,5‐dimethylpyrazol‐1‐yl‐κN2)dithioacetato‐κS](triphenylphosphine‐κP)copper(I)

In the title compound, [Cu(C₁₂H₁₅N₄S₂)(C₁₈H₁₅P)], the copper(I) center is tetrahedrally coordinated by one S atom and two N atoms from one bis(3,5‐dimethylpyrazol‐1‐yl)dithioacetate ligand and one P atom from a triphenylphosphine ligand. In the crystal structure, adjacent pyrazole rings are involved in weak π–π interactions, thereby forming a one‐dimensional zigzag chain running along the b axis.     

Chloro{2,2′‐[(1S,2S)‐1,2‐di­phenyl‐1,2‐ethanediyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ4O,N,N′,O′}(ethanol‐κO)­manganese(III)

The crystal structure of the title compound, [MnCl(C₂₈H₂₂N₂O₂)(C₂H₆O)], has been determined at 173 (2) K in the non‐centrosymmetric space group P2₁2₁2₁. The asymmetric unit contains two molecular units. An intermolecular O—H⋯Cl hydrogen bond is formed between the OH group of an ethanol mol­ecule coordinated to the Mn atom and the coordinated Cl⁻ anion, and so polymeric chains of Mn‐containing fragments are formed [O—H⋯Cl = 3.1281 (16) and 3.1282 (15) Å]. The Mn atoms have a pseudo‐octahedral coordination sphere, with the four donor atoms of the Schiff base forming an equatorial plane [Mn—O distances are 1.8740 (13), 1.8717 (13), 1.8749 (13) and 1.8823 (13) Å, and Mn—N distances are 1.9868 (15), 1.9910 (14), 1.9828 (15) and 1.9979 (14) Å]. The axial positions are occupied by an ethanol mol­ecule [Mn—O distances of 2.3069 (15) and 2.3130 (15) Å] and a Cl⁻ ligand [Mn—Cl distances of 2.5732 (6) and 2.5509 (6) Å].     

Hydrothermally synthesized Ni(OH)<Subscript>2</Subscript>@Zn(OH)<Subscript>2</Subscript> composite with enhanced electrochemical performance for supercapacitors

Two kinds of electrode materials Ni(OH)₂ and Ni(OH)₂@Zn(OH)₂ composite are fabricated on nickel foam. Electrochemical experiments indicate Ni(OH)₂@Zn(OH)₂ composite deserves further study due to high specific capacitance and good cycle stability, so that it can achieve energy storage and conversion as much as possible. When the hydrothermal time is different, the electrochemical performance of the sample is also different. Accurately, samples can obtain better electrochemical performance at 15 h, and the maximum specific capacitance of Ni(OH)₂@Zn(OH)₂ is 7.87 F cm^?2 compared to Ni(OH)₂ (0.61 F cm^?2) at 5 mA cm^?2. Even at 50 mA cm^?2, specific capacitance is 5.24 F cm^?2 and rate capability is 66.6%. Furthermore, Ni(OH)₂@Zn(OH)₂-15 h loses 19.8% after 1000 cycles, revealing the composite has an outstanding stable cycle. These properties also indicate Ni(OH)₂@Zn(OH)₂-15 h is a promising electrode material.     

cis‐Di­chloro­(di­methyl­aminomethyl­ene)­(tri­phenyl­phosphine)palladium(II) acetone solvate

The synthesis and X‐ray structural analysis of the title compound, [PdCl₂(C₃H₇N)(C₁₈H₁₅P)]·C₃H₆O, are described. The crystal structure contains discrete monomeric mol­ecules of the carbene complex and solvent mol­ecules separated by normal van der Waals distances. The Pd atom is four‐coordinate in an essentially square‐planar environment, with the chlorine ligands mutually cis; Pd—P = 2.2495 (7), Pd—Cl = 2.3508 (7) and 2.3600 (7), Pd—C 1.948 (2) and N—C(carbene) 1.274 (3) Å.     

[Ba(Benzo‐15‐Krone‐5)2](In)2: Darstellung und strukturelle Charakterisierung eines Triiodids (n = 3) und eines Heptaiodids (n = 7)

[Ba(benzo‐15‐crown‐5)₂](I₃)₂ and [Ba(benzo‐15‐crown‐5)₂](I₇)₂ can be obtained in crystalline form by reacting benzo‐15‐crown‐5 (C₁₄H₂₀O₅), barium iodide (BaI₂), and iodine (I₂) in ethan‐ole /dichloromethane. The triiodide consists of a sandwich‐like cation [Ba(benzo‐15‐crown‐5)₂]²⁺ and an isolated symmetrically linear I₃^‐ anion. The unusual I₇^‐ anion in the heptaiodide can be described as a V‐shaped pentaiodide unit, which is connected with a slightly widened iodine molecule to the rare Z‐form of the heptaiodide ion. In the crystal structure, secondary bonding distances lead to almost planar ten‐membered iodine rings, which are connected by common edges to form staircase‐like bands.     

Supramolecular networks of 10‐(2‐hydroxyethyl)acridin‐9(10H)‐one and 10‐(2‐chloroethyl)acridin‐9(10H)‐one

Both 10‐(2‐hydroxyethyl)acridin‐9(10H)‐one, C₁₅H₁₃NO₂, and 10‐(2‐chloroethyl)acridin‐9(10H)‐one, C₁₅H₁₂ClNO, have monoclinic (P2₁/c) symmetry and supramolecular three‐dimensional networks. But the differences in the intermolecular interactions displayed by the hydroxy group and the chlorine substituent lead to stronger intermolecular π‐stacking interactions and hydrogen bonding, and hence a significantly higher melting point for the former.     

Trigonal–planar silver coordination in (3,5‐di­nitro­benzoato)­bis­(tri­phenyl­phosphine)­silver(I)

The three‐coordinate Ag atom in the title compound, [Ag(C₇H₃N₂O₆)(C₁₈H₁₅P)₂], shows trigonal–planar coordination [P—Ag—P = 147.1 (1)° and Σ_Ag = 359.0 (3)°]. Adjacent mol­ecules are linked through the O atoms of adjacent nitro groups [Ag?O = 3.205 (3) and 3.302 (4) Å] into a zigzag chain running parallel to the c axis.     

Supramolecular Structures of Titanium(IV)‐Substituted Wells–Dawson Polyoxotungstates

The novel, dimeric titanium(IV )‐substituted phosphotungstate [(TiP₂W₁₅O₅₅OH)₂]^14? ( 1 ) has been synthesized and characterized by IR and ³¹P NMR spectroscopy, elemental analysis, and single‐crystal Xray diffraction. The polyanion consists of two [P₂W₁₅O₅₆]^12? Wells–Dawson moieties linked through two titanium(IV ) centers. Polyanion 1 is a dilacunary species and represents the first Ti‐containing sandwich‐type structure. The titanium centers are octahedrally coordinated by three oxygen atoms of each P₂W₁₅O₅₆ subunit. The edge‐shared TiO₆ units are symmetrically equivalent and have no terminal ligands. Polyanion 1 shows a chiral distortion within each P₂W₁₅Ti fragment. We also report on the structural characterization of the tetrameric, supramolecular species [{Ti₃P₂W₁₅O_57.5(OH)₃}₄]^24? ( 2 ). Polyanion 2 is composed of four equivalent P₂W₁₅Ti₃ fragments, fused together through terminal Ti? O bonds, leading to a structure with T_d symmetry.     

15N Chemically Induced Dynamic Nuclear Polarization (15N‐CIDNP) Investigations of the Peroxynitrite Decay and Nitration of N‐Acetyl‐L‐tyrosine

During the decay of (¹⁵N)peroxynitrite (O?¹⁵NOO ^? ) in the presence of N‐acetyl‐L ‐tyrosine (Tyrac) in neutral solution and at 268 K, the ¹⁵N‐NMR signals of ¹⁵NO and ¹⁵NO show emission (E) and enhanced absorption (A) as it has already been observed by Butler and co‐workers in the presence of L ‐tyrosine (Tyr). The effects are built up in radical pairs [CO , ¹⁵NO ]^S formed by O? O bond scission of the (¹⁵N)peroxynitrite? CO₂ adduct (O?¹⁵NO? OCO ). In the absence of Tyrac and Tyr, the peroxynitrite decay rate is enhanced, and ¹⁵N‐CIDNP does not occur. This is explained by a chain reaction during the peroxynitrite decay involving N₂O₃ and radicals NO ^. and NO . The interpretation is supported by ¹⁵N‐CIDNP observed with (¹⁵N)peroxynitrite generated in situ during reaction of H₂O₂ with N‐acetyl‐N‐(¹⁵N)nitroso‐dl ‐tryptophan ((¹⁵N)NANT) at 298 K and pH 7.5. In the presence of Na¹⁵NO₂ at pH 7.5 and in acidic solution, ¹⁵N‐CIDNP appears in the nitration products of Tyrac, 1‐(¹⁵N)nitro‐N‐acetyl‐L ‐tyrosine (1‐¹⁵NO₂‐Tyrac) and 3‐(¹⁵N)nitro‐N‐acetyl‐L ‐tyrosine (3‐¹⁵NO₂‐Tyrac). The effects are built up in radical pairs [Tyrac ^. , ¹⁵NO ]^F formed by encounters of independently generated radicals Tyrac ^. and ¹⁵NO . Quantitative ¹⁵N‐CIDNP studies show that nitrogen dioxide dependent reactions are the main if not the only pathways for yielding both nitrate and nitrated products.     

trans‐[1,3‐Bis(2,4‐di­methyl­phenyl)­imidazolidin‐2‐yl­idene]­di­chloro­(tri­phenyl­phosphine‐κP)­palladium(II)

The title complex, [PdCl₂(C₁₉H₂₂N₂)(C₁₈H₁₅P)], shows slightly distorted square‐planar coordination of the palladium(II) metal center. The Pd—C bond distance between the N‐heterocyclic ligand and the metal atom is 2.008 (3) Å. The dihedral angle between the two di­methyl­phenyl ring planes is 33.17 (13)°.     

Tri­benzyl(η5‐penta­methyl­cyclo­penta­dienyl)­hafnium(IV)

The title compound, [Hf(C₇H₇)₃(C₁₀H₁₅)], adopts a monomeric three‐legged piano‐stool structure. One benzyl ligand is disordered between two sites (44:56%) related by a ～30° rotation about an axis defined by the Hf atom and the ipso‐C atom of the benzyl ligand.     

[(8a,9,9a‐η)‐9‐(η5‐Cyclopentadienyl)‐9‐nickelafluorenyl](η5‐pentamethylcyclopentadienyl)nickel(II)

The title compound, [Ni₂(C₅H₅)(C₁₀H₁₅)(C₁₂H₈)] or [Ni(C₁₀H₁₅){Ni(C₅H₅)(C₁₂H₈)}], is a rare example (and the first obtained from nickelafluorenyllithium) of an analogue of nickelocene in which the central Ni atom is coordinated to one pentamethylcyclopentadienyl ring and one nickelafluorenyl ring. Both rings lie almost parallel to one another: the dihedral angle between the planes which include these rings is 4.4 (1)°. Slip parameter analysis indicates that the bonding mode of the central Ni atom to the nickelacyclic ring is between η³ and η⁵. Two‐dimensional layers of molecules are formed by C—H...π interactions.