Crystal structure analyses of bis(triphenyl- phosphoranyliden)ammonium bis(pentafluoroethyl) argentate, [Ph3P=N=PPh3][Ag(C2F5)2] and bis[bis(triphenylphosphoranyliden)ammonium] tetrachloro-diargentate, [Ph3P=N=PPh3]2[ClAg(μ-Cl)2AgCl]

Bis(triphenylphosphoranyliden)ammonium bis(pentafluoroethyl)argentate, [Ph₃P=N= PPh₃][Ag(C₂F₅)₂] (1) and bis[bis(triphenylphosphoranyliden)ammonium]tetrachloro-diargentate, [Ph₃P=N=PPh₃]₂[ClAg(μ-Cl)₂AgCl] (2) were crystallized from the reaction mixture of pentafluoroethylsilver(I) and bis(triphenylphosphoranyliden)ammonium chlo-ride. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 17.083(2) Å, b = 11.600(2) Å, c = 19.833(2) Å, β = 109.66(1)°, V = 3700.8(7) ų, Z = 4. 2 crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 19.540(1) Å, b = 15.926(1) Å, c = 20.160(1) Å, V = 6273.6(3) ų, Z = 8.     

Synthesis and crystal structure of an infinite double- stranded chain manganese(II) coordination polymer bridged through 1,2-bis(imidazol-1-yl)ethane ligand

The manganese complex [Mn(bim)₂(NCO)₂]_n (1) (bim = 1,2-bis(imidazol-1-yl)ethane) has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in the monoclinic space group C2/c, a = 9.896(3) Å, b = 15.383(4) Å, c = 13.949(4) Å, β = 98.966(5)^∘, V = 2097.5(9) ų, Z = 4. The coordination geometry of Mn(II) atom is distorted octahedral; it is coordinated equatorially by four nitrogen atoms from the imidazole rings of four symmetry-related bim ligands, and axially by two nitrogen atoms from two symmetry-related cyanate anions. The structure is polymeric, with 18-membered spiro-fused rings and each 18-membered ring involving two inversion-related bim molecules.     

Caged phosphite complexes of copper(I) halides

The coordination chemistry of the caged phosphites 4-2,6,7-trioxa-1-phosphabicyclo [2.2.2]octane (MeCage) and 4-nitro-t2,6,7-trioxa-1t-phosphabicyclo[2.2.2]octane (NO₂Caget) with copper(I) halides is reported. Reactions of CuX = CuCl, CuBr, and CuI with the phosphite ligands afford complexes of the type [CuX(MeCage)]₄, [CuX(NO₂Cage)]₄, [CuX(MeCage)₂]₂, [CuX(NO₂Cage)₂]₂, and [CuX(MeCage)₃]. Recrystallization of [CuBr(NO₂Cage)₂]₂ in MeCN produced [CuBr(NO₂Cage)(NCMe)]₂. Three X-ray crystal structures are reported: [CuCl(MeCage)]₄ (I – 4, a = 13.4292(5) Å, b = 13.4292(5) Å, c = 9.4641(5) Å, V = 1706.79(13) ų, Z = 2), [CuBr(MeCage)₂]₂ (I4₁/a, a = 19.5751(17) Å, b = 19.5751(17) Å, c = 16.4513(15) Å, V = 6303.9(10) ų, Z = 8), and [CuBr(NO₂Cage)(NCMe)]₂ (P2₁/c, a = 9.0506(4) Å, b = 15.2428(7) Å, c = 8.8673(4) Å, = 109.7640(10), V = 1151.24(9) ų, Z = 2).     

Synthesis and crystal structure of a macrocyclic azidotetraamine copper(II) complex

The complex [Cu(L)N₃](H₂O)(ClO₄) (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18, 0^7.12]docosane) has been prepared and characterized by X-ray crystallography. 1 crystallizes in the monoclinic space group P2₁/c, with a = 8.907(5), b = 20.036(3), c = 14.773(2) Å, = 103.78(2)°, V = 2560.6(15) ų, and Z = 4. The coordination geometry around the Cu(II) ion is a distorted square-pyramidal with four nitrogen atoms of the macrocycle and one nitrogen atom of the axial azido group.     

8-Thiatheophylline nitrato silver (I): Spectroscopic characterization and crystal structure

A new metal-theophylline derivative was synthesized from AgNO₃ and 8-thiatheophylline. The thermal stability of the Ag(C₆H₆N₄O₂S)(NO₃) complex was studied by TG and DSC techniques. The silver coordination has been discussed from IR,¹H-NMR and¹³C-NMR spectra. The crystal structure was established by X-ray diffraction. Ag(TTH)(NO₃) crystallizes in space groupP2₁2₁2₁ witha=6.198(1),b=12.576(2),c=13.422(2) Å andZ=4. The structure was refined toR=0.032. This complex reveals interesting features in the coordination mode of the TTH ligand. The sulfur atom and the carbonyl groups are not involved in the coordination. Silver tetrahedral coordination occurs through N7 and N9 of two different TTH ligands (Ag-N7=2.422(3) Å; Ag-N9=2.356(2) Å) and through two oxygen atoms of two different nitrato groups (Ag-O=2.435(4) and 2.518(4) Å) giving a polymeric structure.     

A novel four-coordinate zinc(II) complex of the di-N-hydroxypropylated tetraaza macrocycle

The compound [Zn(L²)Cl]ClO₄·H₂O (1) (L² = 2,13,-bis(3-hydroxypropyl)-5,16-di-methyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) has been synthesized and structurally characterized. 1 crystallizes in the monoclinic system, space group P2₁/c with a = 8.932(2), b = 16.189(2), c = 22.492(4) Å = 95.34(2)° V = 3238.3(11) ų; and Z = 4. The zinc atom is placed in a highly distorted tetrahedral environment bonding with three nitrogen atoms of the macrocycle and one chlorine atom.     

Synthesis, properties, and X-ray structure of [Cu(dpa)Cl2] (dpa = di-(2-picolyl)amine)

The mono(dpa)copper(II) complex [Cu(dpa)Cl₂] (1) (dpa = di-(2-picolyl)amine) has been synthesized and structurally characterized. It crystallizes in the monoclinic system P2₁/n with a = 8.155(1), b = 12.560(1), c = 12.817(2) Å, = 91.64(2)°, V = 1312.3(2) ų, Z = 4. The copper atom is coordinated by three nitrogen atoms from the dpa ligand and two chlorides in a distorted square-pyramidal environment. Cyclic voltammetric data show that 1 undergoes the reversible one-electron oxidation to the Cu(III) and the reversible one-electron reduction to the Cu(I) state.     

Synthesis and crystal structure of a silver(I) complex with dithioether ligand

The reaction of the dithioether ligand, 2,3-bis(5-methyl-1,3,4-thiadiazole-2-thiomethyl) quinoxaline (L) with AgBF₄, leads to the formation of a novel complex {[AgL](BF₄)}_∞ 1, which has been characterized by single-crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 20.316(7) ?, b = 12.401(4) ?, c = 18.039(6) ?, β = 108.404(6)° and V = 4312(3) ?³. The crystal structure of the complex consists of 1D {[AgL]⁺}_∞ cation chain and BF₄ ⁻ anions. In 1, the coordination geometry of Ag^I center can be best described as trigonal planar coordinated by three N from two distinct L ligands. The ligand is polydentate with one end adopting a bidentate conformation to chelate an Ag^I atom and the other end monodentate to bridge another Ag^I resulting in an infinite chain along b axis. There exist Ag⋯N weak coordination, π–π stacking and F⋯S weak interactions in the complex, and these weak interactions link the 1D complex into 3D supramolecular structure and further stabilize the crystal structure in the solid state.     

Synthesis and structural characterization of a novel polymeric gadolinium(III)–copper(II) complex of iminodiacetic acid

A novel polymeric Gd₂Cu₃ complex of iminodiacetic acid (H₂L¹=NH{CH₂COOH}₂), namely, Gd₂Cu₃(L¹)₆, 1, has been synthesized and structurally characterized. In the title complex, the Gd³⁺ ion is nine-coordinated by six O atoms from three bidentate chelating carboxylate groups and three O atoms from three anti-anti bridging carboxylic groups of six L¹ ligands; the Cu²⁺ ion is six-coordinated by four O and two N atoms from two chelating L¹ ligands. Each pair of Gd(III) atoms is bridged by three L¹ ligands, each of which also chelates with one copper(II) ion, thus forming a Gd₂Cu₃ cluster unit. Such cluster units are cross-linked by flexible L¹ ligands into a three-dimensional coordination framework. The title complex crystallizes in the trigonal space group P-3c1 (No. 165) with a = b = 13.433(4), c = 14.770(6) Å; V = 2308(1) ų; D_calca = 1.859 g cm^–3; Z = 2.     

[Ag{NCC(O)CN}<Subscript>2</Subscript>]<Subscript>n</Subscript> [SbF<Subscript>6</Subscript>]<Subscript>n</Subscript>, the first metal complex of carbonyl cyanide

The first metal complex of carbonyl cyanide [Ag{NCC(O)CN}₂]_n [SbF₆]_n was synthesized and characterized by X-ray crystallography. The silver(I) centers are bridged by the cyanide groups of the carbonyl cyanides giving a two-dimensional layer structure. The SbF₆⁻ anions are embedded in the cationic framework to neutralize the charge with only very weak contacts to the Ag⁺. The compound crystallizes in the monoclinic space group C2/c with a = 11.8737(13) Å, b = 10.2497(13) Å, c = 10.5883(13) Å, β = 90.183(3)^∘.     

Synthesis of homoleptic lanthanide amides and the crystal structure of [Li(THF)4][Y(NPh2)4]

Anhydrous LnCl₃ reacted with three equivalents of LiNPh₂ in THF to give the unexpected homoleptic lanthanide amides [Li(THF)₄][Ln(NPh₂)₄] (Ln = Sm (1), Y (2)) in high yield. The crystal structure of complex 2 has been determined by X-ray diffraction methods. It crystallizes in the orthorhombic space group Pbcn with a = 17.522(3) Å, b = 16.321(3) Å, c = 19.947(3) Å, V = 5704.4(17) ų, and D _calc = 1.231 mg/m³ for Z = 4. Complex 2 is composed of discrete [Li(THF)₄]⁺ cations and [Y(NPh₂)₄]^– anions, both of which have crystallographically imposed two-fold symmetry. To achieve steric saturation of the metal center, there are interactions between the yttrium atom and one -carbon atom of each amide ligand. The yttrium and lithium atoms both exhibit distorted tetrahedral coordination geometry.     

Synthesis and crystal structure of an unsymmetric dysprosium(III) cryptate

Synthesis, crystal and molecular structure of [Dy(H₃L)(NO₃)(H₂O)](ClO₄)₂ H₂O are reported. The complex crystallizes in the orthorhombic system, space group Pbca with lattice parameters a = 16.8036(3) Å, b = 20.9756(3) Å, c = 25.1113(4) Å, and D _calc = 1.797 Mg m^–3 for Z = 8. The coordination number of dysprosium(III) is 9, and its coordination geometry is a distorted monocapped square antiprisms. In the cryptate, a water molecule acts as a guest molecule encapsulated in the cryptate.     

Synthesis and Structure of a Silver(I) Complex {[Ag5(L)2(NO3)4](NO3)(CHCl3)2}n [L?=?2,3-bis(pyrimidine-2-thiomethyl)quinoxaline]

Abstract  The reaction of the dithioether ligand, 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline (L) with AgNO₃, leads to the formation of a novel complex {[Ag₅(L)₂(NO₃)₄](NO₃)(CHCl₃)₂}n 1, which has been characterized by single-crystal X-ray diffraction analysis: monoclinic, space group C2/c, with a = 34.741(7), b = 9.930(2), c = 17.004(4) ?, β = 106.497(6)° and V = 5625(2) ?³.Complex 1 consists of 2D {[Ag₅(L)₂(NO₃)₄]⁺}n cations, uncoordinated anions and CHCl₃ solvent molecules. In 1, there exist three crystallographic independent Ag^I centers, which adopt different coordination geometries. There exist π–π stacking interactions in the complex and these weak interactions further stabilize the crystal structure in the solid state. The coordination feature of the ligand has been investigated by DFT calculations. Index Abstract  Synthesis and Structure of a Silver(I) Complex {[Ag₅(L)₂(NO₃)₄](NO₃)(CHCl₃)₂}_n [L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline] Chao-Yan Zhang, Qian Gao, Ya-Bo Xie*, and Jian-Bo Feng The crystal structure of complex {[Ag₅(L)₂(NO₃)₄](NO₃)(CHCl₃)₂}n (L = 2,3-bis(pyrimidine-2-thiomethyl)quinoxaline) consists of 2D {[Ag₅(L)₂(NO₃)₄]⁺}n cations, uncoordinated anions and CHCl₃ solvent molecules. There exist three crystallographic independent Ag^I centers, which adopt different coordination geometries. The coordination feature of the ligand has been investigated by DFT calculations.      

Crystal structure of aquo (hydroxo) (ethylenediaminetetraacetato) sodium(I) tin(IV), NaSn(OH)(edta)(H2O)

NaSn(OH)(edta)(H₂O) is monoclinic, space groupP2₁/c, witha=9.747(3)Å,b=9.121(3)Å,c=16.430(6)Å, =98.69(4)°, ų, andZ=4. The coordination environment of Sn(IV) is a capped octahedron. Sn–O distances range from 1.990(6)Å to 2.351(7)Å. Na(I) is five coordinated to three different edta molecules. Na–O distances range from 2.283(9)Å to 2.414(7)Å. The edta ligand presents the E, G/R conformation. The crystal structure is composed of sheets parallel to (001): inside a sheet Sn(OH)(edta) molecules are connected to each other by the Na(I) interactions.     

Crystal structures of 2-pyrazinecarboxylato silver(I) and ammine 2,3-pyrazinecarboxylato disilver(I)

X-ray analysis has shown that the complexes of silver(I) with the anionic forms of 2-pyrazinecarboxylic and 2,3-pyrazinedicarboxylic acids are three-dimensional network polymers. Ag(C₅H₃O₂N₂) (1) crystallizes in space groupPna2₁ witha=7.028(2),b=11.510(3),c=6.949(2) Å andZ=4. Silver tetrahedral coordination occurs through three ligands: the first one acts as a bidentate chelator (Ag–O=2.539(4), Ag–N=2.334(4)Å), the second one involves one N pyrazine atom (Ag–N=2.196(4)Å) and the third one bonds through one O-carboxylato atom (Ag–O=2.323(4)Å). The dinuclear complex Ag₂(C₆H₂O₄N₂)(NH₃) (2) crystallizes in space groupP2₁/c witha=7.775(2),b=16.455(2),c=7.174(1) Å, -115.21(1)° andZ =4. Each of the two silver atoms shows a trigonal environment. The first silver atom involves two O carboxylic atoms (Ag–O=2.312(4), 2.374(4)Å) and one N pyrazine atom (Ag–N=2.277(3)Å) belonging to three different ligands. The second one involves one O carboxylic atom (Ag–O=2.364(3)Å) and one N pyrazine atom (Ag–N=2.304(4)Å) from the same chelating ligand and one N ammine atom (Ag–N=2.158(5)Å).     

Silver (I) coordination by 1-(t-butyl)-2-benzoylaziridine

The reaction between AgNO₃ and 1-(t-butyl)-2-benzoylaziridine (tBBA) leads to the formation of bis-(1-(t-butyl)-2-benzoylaziridine) nitrato silver (I) which is a new metal aziridine derivative. The crystal structure was established by X-ray diffraction. [Ag(tBBA)₂(NO₃)] crystallizes in space groupC222₁ witha=11.877(6),b=13.560(4),c=16.923(4)Å andZ=4. The silver atom is six-coordinated by two N atoms of two aziridine rings (Ag-N=2.39(1)Å), two O atoms of two benzoyl groups (Ag-O=2.60(1)Å) and two O atoms of the nitrato group (Ag-O=2,60(1) Å). The coordination around the silver atom defines a very distorted octahedron with the C2 symmetry. The twofold axis passes through one O and the N nitrato atoms, and the silver atom. The nitrato group and tBBA act as bidentate ligands. These results are in contrast with our previous studies on aziridine zinc (II) complexation where the zinc atom is not coordinated by the benzoyl group.     

Hydrogen-bonded coordination network in crystal structures of [Cu(3-PM)4Cl2] and [Cu(4-PM)4Cl]Cl, (PM = pyridylmethanol)

The crystal and molecular structures of [Cu(3-PM)₄Cl₂] (1) and [Cu(4-PM)₄Cl]Cl (2) have been determinated by X-ray crystallography. Complex 1 crystallizes in the triclinic system, space group P–1, with lattice parameters a = 7.972(2) Å, b = 8.293(2) Å, c = 10.707(2) Å, = 105.73(3)°, = 90.04(3)°, = 110.38(3)°, and Z = 1 at 100 K. The coordination geometry of each Cu atom is approximately octahedral formed by four nitrogen atoms of pyridine rings of 3-pyridylmethanol molecules in the equatorial plane and two chlorine atoms occupying the axial positions. The O—HsO, C—HsCl, and O—HsCl intermolecular hydrogen bonds and s stacking link the molecules in 3-D hydrogen-bonded coordination network. Complex 2 crystallizes in the tetragonal system, space group P4/n, with lattice parameters a = 10.464(1) Å, c = 11.339(2) Å, and Z = 2 at 217 K and a = 10.352(1) Å, c = 11.201(2) Å, and Z = 2 at 293 K. The coordination geometry of Cu atom in the [Cu(4-PM)₄Cl]⁺ ion is approximately square pyramidal formed by four nitrogen atoms of pyridine rings of 4-pyridylmethanol molecules in equatorial plane and one chlorine atom in axial position. The O—HsCl and C—HsCl intermolecular hydrogen bonds link the molecules in 2-D hydrogen-bonded coordination network.     

Synthesis and characterization of copper(II) tetraaza macrocyclic complex with 2- benzimidazolepropionate ligand

A mononuclear complex [Cu(L)(bip)₂] (1) (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo [14,4,0^1.18, 0^7.12]docosane; bip = 2-benzimidazolepropionate) has been synthesized and structurally characterized by X-ray crystal structure analysis. The crystals are monoclinic P2 ₁/n with a = 10.2990(2), b = 15.9400(3), c = 11.991(14) Å, = 101.92(7)°, V = 1926(2) ų, Z = 2. The copper(II) coordination geometry exhibits an axially elongated octahedron with four nitrogen atoms from the macrocycle and two oxygen atoms from the bip ligands. The cyclic voltammogram of 1gives 2 one-electron waves corresponding to Cu^II/Cu^III and Cu^II/Cu^I processes.     

Synthesis and crystal structure of macrocyclic nickel(II) complex bridged by chromate

A novel compound catena-(-CrO₄-O,O)[Ni(L¹)Ni(L²)] 3H₂O (1) (L¹ = 3,5,10,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane and L² = 2,5,9,12-tetramethyl-1,4,8,11-tetraazacyclotetradecane) has been synthesized for the first time and structurally characterized. 1 crystallizes in the triclinic space group P with a = 9.623(1), b = 10.084(1), c = 12.723 (3) Å, = 66.74(2), = 75.20(1), = 72.02(1)°, V = 1066.2(3) ų, and Z = 2. The coordination environment around the Ni(II) ions is an axially elongated octahedron with the secondary amines of the isomeric ligands and two oxygen atoms of [CrO₄]^2–.     

Preparation and characterization of a bidentate carboxylate-bridged dinuclear cadmium(II) complex with bis(2-pyridylmethyl)amino-3-propionic acid

The carboxylate-bridged dinuclear complex [Cd(-pmpa)(H₂O)](ClO₄)·H₂O (1) (Hpmpa = bis(2-pyridylmethyl)amino-3-propionic acid) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the monoclinic system P2 ₁/n with a = 7.9678(6) Å, b = 17.5103(9) Å, c = 14.3147(9) Å, = 94.1030(10)°, V = 1992.0(2) ų, Z = 4. The carboxylate group of the pmpa ligand adopts a bidentate bridging coordination mode, and the ligand acts as -bridge linking two cadmium(II) ions to form a dinuclear complex. Each cadmium atom is seven-coordinate, with a distorted pentagonal bipyramidal geometry. The cyclic voltammogram of 1 undergoes irreversible one-electron oxidation to the Cd(III) and reversible one-electron reduction to the Cd(I).