(Imidazole)(3,3′-trimethylenedinitrilo bis (2-butanone oximate)) copper(II) perchlorate: Synthesis and crystal structure of a five-coordinate copper-protein model complex

The synthesis and crystal structure of the novel pentacoordinated complex [Cu(DOHPN)(IMI-DAZOLE)] (ClO4), (DOHPN=(3,3′-trimethylenedinitrilo bis 2-butanone oxime) are reported. The X-ray crystal structure (space groupP2₁/n, a=11.349(2) Å,b=14.241(3) Å,c= 12.635(3) Å; α=90°, β=100.21 (3)°, γ=90°) shows that the copper(II) ion occupies a distorted square-pyramidal geometry with the imidazole ligand occupying the axial position. The copper(II)-(N)imidazole distance is 2.125(3) Å and the copper(II)-tetraaza plane distance is 0.385/Å. The tetraaza ligand DOHPN adopts a “butterfly-like” geometry with a dihedral angle of 149.69°. The title complex is the first structurally characterized compound of the series [Cu(DOHPN)(axial ligand)]ⁿ⁺ where the axial ligand is a neutral N-heterocycle with known biological relevance. A comparison of the structural parameters with those observed when the axial ligand is H₂O or NCS^? (N-bonded) gives the following series with increasing metal-ligand interaction: H₂O>IMIDAZOLE>NCS^? (N-bonded).     

Synthesis and crystal structure of charge-transfer salt (BEDT-TTF) [Pt(mnt)2]

The synthesis and crystal structure of the title organic charge-transfer salt (BEDT-TTF)[Pt(mnt)₂] (BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene; mnt = cis-3,4-dimercapto-2-butenedinitrile) is described. The salt crystallizes in the P1 space group with a = 6.728(2) Å, b = 7.371(2) Å, c = 13.596(4) Å, = 97.904(5)°, = 90.114(5)°, and =108.147(5)°. The stoichiometry between BEDT-TTF and [Pt(mnt)₂] is 1:1. The bond length of the central C=C bond in a BEDT-TTF ion is 1.398 (16) Å, indicating an oxidation state of +1 in BEDT-TTF ion. The structure consists of layers of BEDT-TTF and Pt(mnt)₂ along the c axis. Within each layer, both BEDT-TTF and Pt(mnt)₂ ions form segregated stacks. The stacking is not in a face-to-face manner, but instead, is through a side-by-side arrangement along the a axis, with closest SS contacts of 3.461(3) Å between neighboring BEDT-TTF ions. The structure is consistent with the semiconducting behavior found in the solid.     

Ether cleavage of [2.2.2]cryptand: synthesis and X-ray crystal structure of [NH(CH2CH2I)3][I5]

Treatment of [2.2.2]cryptand1 in toluene with HI(g) has resulted in the formation of a twophase liquid clathrate solution from which the complex [NH(CH₂CH₂I)₃][I₅]2 has been isolated and crystallographically characterized. Crystal data for2: triclinic, space group $P\bar 1$ ,a=9.301(3) Å,b=10.419(3) Å,c=11.078(3) Å, α=90.20(2)^o, β=103.28(2)^o γ=96.50(2)^o,D _c =3.57g/cm³,Z=2,R _f =0.054,R _w =0.054. The salt is a product of an ether cleavage of the macrobicycle. The crystal structure of2 contains [NH(CH₂CH₂I)₃]⁺ ions and zigzag chains of [I₅]^? ions which self-assemble to form alternating layers, of cations and anions.     

Crystal and molecular structure of [Rh(μ-SBut)(CO)(PPh3)]2

Reaction of [Rh(CO)₂Cl]₂ with Bu ^t SLi followed by refluxing with PPh₃ yields [Rh(-SBu ^t )(CO)(PPh₃)]₂(1). The structure of (1) has been determined by X-ray crystallography. Empirical formula: Rh₂P₂S₂C₄₆H₄₈O₂,M=964.78, triclinic, P¯1,a=11.408(9),b=13.241(8),c=15.830(3) Å,=93.67(3),=93.12(5),=110.8(6)°,Z=2,D _calc=1.44 g cm^–3,R=0.048 (R _w =0.062) for 5939 observed reflections. In the solid state, the compound exhibitscis geometry with respect to the phosphine and CO ligands. The geometry about the two metals is essentially square planar, with a dihedral angle of 103.2°, and a butterfly angle of 102.3°. Compound (1) is stereochemically rigid on the NMR time scale from –80 to +80°C.     

1,4-Di-[2-phenyl-1-diazenyl]perhydro-1,4-diazepine: X-ray crystal structure

1,4-Di-[2-phenyl-1-diazenyl]perhydro-1,4-diazepine (1) has been synthesized by reaction of benzenediazonium chloride with homopiperazine (perhydro-1,4-diazepine). The crystal structure of 1 has been determined by single crystal X-ray diffraction analysis. The bis-triazene (1) adopts an extended conformation which precludes any close intramolecular interaction of the phenyl rings. The heterocyclic seven-membered ring adopts a chair conformation, with the triazene side chains occupying alternate axial and equatorial positions consistent with cis-geometry. Internal torsion angles of the seven-membered ring have been measured. The crystal packing is determined by short contacts between C=H groups of phenyl rings and nitrogens of triazene moieties and by van der Waals interactions, with no evidence for intermolecular – interactions. This work establishes the structure of the product of diazonium coupling with homopiperazine as 1,4-di[(E)-2-phenyl-1-diazenyl]perhydro-1,4-diazepine. Crystal data: 1 C₁₇H₂₀N₆, monoclinic, space group P2₁/n, a = 9.1838(5) Å, b = 12.1095(6) Å, c = 15.0081(8) Å, = 101.320(2), V = 1636.6(2) Å,³ for Z = 4.     

Crystal structure of [Pb(cis-anti-cis-dicyclohexyl-18-crown-6)(OH2)2][ClO4]2

[Pb(cis-anti-cis-dicyclohexyl-18-crown-6)(OH₂)₂][ClO₄]₂ was crystallized using a slightly modified literature method for the separation of dicyclohexyl-18-crown-6 isomers. It crystallizes in the monoclinic space groupP2₁/n witha=8.415(5),b=20.993(9),c=8.973(5) Å, β=111.56(6)^o, andD _calc=1.84 g/cm³ for Z=2. The Pb²⁺ ion resides on a crystallographic center of inversion and is coordinated to the six crown ether donors and two axial water molecules in a hexagonal bipyramidal geometry. The Pb-O(etheric) distances range from 2.694(4) to 2.743(4) Å while the Pb?OH₂ distance is 2.522(6) Å.     

Synthesis and crystal structure of 2-propyl-5-phenyl-1, 4-dioxo-1,2,3,4,5,6,7,8-octahydro-[1,4,2]diazaphosphorino [1,2-a][1,3,2]benzodiazaphosphorine 3-oxide

The synthesis and structure characterization of 2-propyl-5-phenyl-1,4-dioxo-1,2,3,4,5, 6,7,8-octahydro-[1,4,2]diazaphosphorino[1,2-a][1,3,2]benzodiazaphosphorine 3-oxide are described. The title compound has been designed to incorporate proximate carbonyl and phosphoryl groups in a heterocycle fused to benzophosphadiamide heterocycle. Crystal data: C₁₉H₂₀N₃O₃P, Monoclinic, space group P2(1)/c, with a = 9.7585(9) Å, b = 21.4319(19) Å, c = 17.7900(16) Å, β = 100.823(2)°, Z = 8, V = 3654.5(6) ų. The crystal structure shows that the proximate carbonyl and phosphoryl groups are not coplanar, and the [1,4,2]diazaphosphorino moiety prefers the boat conformation.     

Crystal structure of cis-[Rh(biq)2Cl2]Cl·3H2O: Solid-state characterization and crystal packing analysis

The title compound, cis-[Rh(biq)₂Cl₂]Cl·3H₂O (biq = 2,2′-biquinoline) crystallized in the monoclinic space group P2 ₁ /n with a = 11.231(2) Å, b = 20.895(4) Å, c = 14.081(3) Å, β = 94.76(3)°, V = 3293.0(11) ų, D _c = 1.565 g cm⁻³, μ = 0.806 mm⁻¹, F(000) = 1576 and Z = 4. It contains a monomeric [Rh(biq)₂Cl₂]⁺ cation, a chloride ion and three molecules of H₂O. The rhodium(III) ion is hexa coordinated forming a distorted octahedral arrangement. The mean Rh(III)–N distance for the four Rh(III)–N bonds is 2.0625 Å. The two chloride atoms are bonded in a cis configuration [Rh(III)–Cl bond distances are 2.329(3) and 2.341(4) Å]. The structure shows a curling stacks of cationic complexes interacting via offset-face-to-face (OFF) π–π aryl interaction motif. Water molecules and chloride ions are hydrogen bonded (H₂O···H–OH and Cl···H–OH) and links the curling stacks by hydrogen bonding via Rh–Cl···H–OH interactions.     

Crystal and molecular structure of a new biguanide metal complex, [Cu(AMNH)2]Cl2

The crystal structure of C₆H₁₆N₈O₂·CuCl₂, a biguanide metal complex, has been determined by X-ray diffraction data using MoK radiation. The compound crystallizes in the monoclinic space groupP2₁/a, witha=11.074(4),b=12.061(4),c=5.312(3)Å and=102.8(1)°.The structure was solved by direct methods and refined by full-matrix least-squares to a finalR value 0.037 with 1245 unique reflections. The complex molecule is centrosymmetric, with the Cu atom (0.5,0.5,0.5) on a crystallographic center of symmetry. The complex molecule is rhombic planar with a trans configuration.     

Synthesis and crystal structure of bis[2-[N-(2-chlorophenyl)formimidayl]-1-naphtholato]-(6Cl)copper(II)

The title compound, bis[2-[N-(2-chlorophenyl)formimidayl]-1-naphtholato]-(6Cl) copper(II), [Cu(C₁₇H₁₁NOCl)₂] (1) was synthesized and its crystal structure was determined. The Compound 1 is monoclinic, space group P2 ₁/c with a = 9.146(3) Å, b = 18.724(3) Å, c = 16.230(2) Å, β = 96.46(1)°, V = 2761.8(11) ų, Z = 4, D _c = 1.503 g cm^?3, μ(Mo Kα) = 1.020 mm^?1, R = 0.0606 for 2361 reflections [I > 2σ(I)]. In the title compound, the Cu atom is coordinated by an N₂O₂ donor set from the imine-phenol ligand in a slightly distorted square planar coordination geometry, with the two phenolate O atoms being deprotonated. The Cu–O bond lengths are 1.878(4) and 1.889(4) Å, the Cu–N bond lengths are 1.980(5) and 1.985(5) Å. The angles O1–Cu–N1 and O2–Cu–N2 are 90.96(19) and 90.72(19)°, respectively.     

Synthesis and crystal structure of 4,5-dibromo[2.1.1]triblattene

Reaction of 4-bromopentacyclo[7.3.0.0^2,7.0^3,11.0^6,10]dodec-11-ene (1) with Br₂—CCl₄ afforded 4,4,5-tribromopentacyclo[7.3.0.0^2,7.0^3,11.0^6,10]dodecane (2) in 89–94% yield. Subsequent treatment of 2 with KOt-Bu-t-BuOH resulted in competitive elimination of the elements of HBr and of Br₂ with concomitant formation of 4,5-dibromopentacyclo[7.3.0.0^2,7.0^3,11.0^6,10]dodec-11-ene (3, 76%) and 1 (17%), respectively. The structure of 3 was established unequivocally via application of X-ray crystallographic methods. Crystal data for 3: monoclinic, C2/c, a = 9.895(1), b = 9.0963(7), c = 12.471(1) Å, = 106.875(8)°, z = 4.     

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.     

Ionic liquid mediated preparation and X-ray crystal structure of [1-methylimidazolium]2[cis-MoO2(salicylato-O1,O2)2]

The complex salt, [1-MeimH]₂[cis-MoO₂(sal)₂], 1, (1-Meim=1-methylimidazole, sal=o-C₆H₄(C^–) (COC^–)) has been prepared by reacting Mo(CO)₆ with molten 1-methyl imidazolium salicylate [1-MeimH][salH], and the structure of 1 has been determined by single crystal X-ray crystallography: triclinic, P¯1,a=9.220(2),b=9.469(3),c=15.368(4)Å, =105.04(4),=99.48(3), =109.48(3)°,Z=2,D _calc=1.60 g/cm. 2809 reflections withI>2.5(I) gave a final values ofR=0.031 andR _w =0.041.     

Structure of a styrylbenzoselenazole platinum(II) complex: [NEt4][Pt(nsbse)Br3]

Tetraethylammonium tribromo[2-(2-chloro-5-nitrostyryl)benzoselenazole] platinate (II), [(C₂H₅)₄N][PtBr₃(C₁₅H₉ClN₂O₂Se)], is monoclinic, in space groupP2₁/c, witha=9.496(2),b=20.321(7),c=15.166(3)Å,=100.18(1)°,V=2880(2)ų,M _r =928.72,Z=4,D _x =2.141 g cm^–3, (MoK)=0.71073 Å,=104.1 cm^–1,F(000)=1752,T=298 K. The structure was solved by direct methods and refined toR=0.032 for 2626 unique observed reflections withI>3(I). The [Pt(nsbse)Br₃)] unit has square-planar geometry about the Pt atom, with the nsbse coordinated to the Pt through the N of the selenazole ring. The ligand molecule is non-planar, with a dihedral angle of 61.6(2)° between the benzoselenazole and phenyl rings. The dihedral angles between the PtBr₃ plane and the benzoselenazole and phenyl planes are 105.2(1) and 80.7(1)°, respectively.     

Synthesis and crystal structure of a terephthalato-bridged copper(II) complex [Cu2(tpt)(bpy)2(H2O)4] [Cu2(tpt)3 (bpy)2(H2O)2]

A terephthalato-bridged copper(II) complex [Cu₂(tpt)(bpy)₂(H₂O)₄][Cu₂(tpt)₃(bpy)₂ (H₂O)₂] (1) (tpt = terephthalate, bpy =; 2,2'-bipyridine) was synthesized by the reaction of Cu(ClO₄)₂ 6H₂O and terephthalic acid in the presence of 2,2'-bipyridine in H₂O solution. Crystal structure of 1 was determined by X-ray diffraction analysis in the triclinic space group P , with a = 10.7327(10) Å, b = 11.1658(11) Å, c = 17.3768(16) Å, = 108.063(2), = 91.064(2), = 116.721(2), V = 1737.5(3) ų, and Z = 2. Both the anion and the countercation in 1 are copper(II) complexes linked by terephthalate bridges in the bis(monodentate) (syn–anti) mode. The anion and the countercation are also linked by two hydrogen bonds between coordinating water molecules and terephthalate ligand.     

Synthesis,redox properties,and X-ray diffraction structure of the platinum catecholate complex Pt(1,5-COD)(1,2-O2C6H4)

The new compound Pt(1,5-COD)(1,2-O₂C₆H₄)(1) (where COD=cyclooctadiene) has been prepared from the reaction between Pt(1,5-COD)Cl₂ and the disodium salt of catechol. Pt(1,5-COD)(1,2-O₂C₆H₄) has been isolated and structurally characterized by X-ray diffraction analysis, which confirms the monomeric nature of this compound and the chelating mode adopted by the ancillary 1,5-COD and catecholate ligands. Pt(1,5-COD)(1,2-O₂C₆H₄) crystallized in the monoclinic space groupP2₁/n,a=10.208(1) Å,b=10.3829(8) Å,c=11.473(2) Å, =103.817(9)°,V=1180.9(2) ų,Z=4,d _calc=2.314 g·cm^–3;R=0.0307,R _w =0.0445 for 1216 observed reflections withI>3(I). Cyclic voltammetric studies on1 reveal an irreversible oxidation (E _p ^a =0.78 V) and an irreversible reduction (E _p ^c =–1.99 V) in CH₂Cl₂ solution. The nature of the HOMO and LUMO in Pt(1,5-COD)(1,2-O₂C₆H₄) was examined by using the model compound Pt(ethylene)₂(1,2-O₂C₆H₄), with the results discussed relative to compound1.     

Room temperature ligand fragmentation in the reaction between PhCCo3(CO)9 and Ph2PN(Me)N(Me)PPh2. X-ray diffraction structure of PhCCo3(CO)8[Ph2PP(O)Ph2]

The cobalt cluster PhCCo₃(CO)₉ reacts with the bis(phosphanyl)hydrazine ligand bis(diphenylphosphino)dimethylhydrazine (dppdmh) in CH₂Cl₂ with added Me₃NO to give the monosubstituted cluster PhCCo₃(CO)₈[Ph₂PP(O)PPh₂] as the major isolable product. The solid-state structure of this new cluster was unequivocally established by X-ray diffraction analysis, which has confirmed the presence of a noncoordinated (O)PPh₂ moiety. PhCCo₃(CO)₈[Ph₂PP(O)Ph₂] crystallizes in the triclinic space group P , a = 12.036(2), b = 12.037(2), c = 15.124(3) Å, = 84.82(1)°, = 89.44(2)°, = 60.09(1)°, V = 1890.0(6) ų, Z = 2, and d_calc = 1.540 g/cm³.     

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 structure of [CpFe(CO){(Ph2P)2NlNMe2}] [I]-CH2Cl2

C₃₂H₃₁FeIN₂OP₂-[CH₂Cl₂],1, monoclinicP2₁/c,a=14.134(3),b=9.496(3),c=26.272(6) Å,=90.92(2)°,Z=4,D _c=1.49 g cm^–3,R=0.044,R _w=0.048, GOF=0.84. Interaction of the hydrazinophosphine Me₂NN(PPh₂)₂ with cyclopentdienyliron dicarbonyl iodide in THF yields compound1 as the sole phosphorous containing species (by³¹P{¹H} NMR). The structure of1 was inferred on the basis of spectroscopic data and solubility characteristics and confirmed via X-ray diffraction.