Synthesis and Structural Characterization of Cu（pic）2[CO（NH2）2]2 and （picH2）2[Cu（pic）2（SCN）2]

1 INTRODUCTION The picolinic acid (picH), also called pyridine- 2-carboxylic acid, has a broad spectrum of physio- logical effects on the activity functions of both ani- mal and plant organisms. It is attributed increasing interest due to its ability to …     

Crystal structure of (C2H7N4O)2[(UO2)2)(OH)2(C2O4)(CHO2)2]

An X-ray diffraction study of the single crystals of (C₂H₇N₄O)₂[(UO₂)₂(OH)₂(C₂O₄)(CHO₂)₂] was carried out. The compound crystallizes in the triclinic system, space group $P\bar 1$ , Z = 2, a = 5.5621(8) Å, b = 8.1489(10) Å, c = 11.8757(16) Å, α = 88.866(7)°, β = 82.204(6)°, γ = 87.378(6)°, V = 532.7(1) ų, ρ_calcd = 2.988 g/cm³. The main structural units in the crystal are the [(UO₂)₂(OH)₂(C₂O₄)(CHO₂)₂)]^2? chains corresponding to the crystal chemical group A₂M ₂ ² K⁰²M ₂ ¹ (A = UO ₂ ²⁺ , M² = OH^?, K⁰² = C₂O ₄ ^2? , M¹ = CHO ₂ ^? ) of uranyl complexes. The chains are united into a three-dimensional framework through the electrostatic interaction and hydrogen bonds involving uranyl, oxalate, and hydroxyl groups, formate ions, and 1-carbamoylguanidinium cations.     

Rhodium-catalyzed dehydrocoupling of the sterically encumbered phosphine-borane adduct tBu(2)PH.BH(3): synthesis of the linear dimers tBu(2)PH-BH(2)-tBu(2)P-BH(3) and tBu(2)PH-BH(2)-tBu(2)P-BH(2)Cl

The dehydrocoupling of the sterically hindered phosphine-borane adduct tBu(2)PH.BH(3) above 140 degrees C is catalyzed by the rhodium complexes [Rh(1,5-cod)(2)][OTf] or Rh(6)(CO)(16) to give the four-membered chain tBu(2)PH-BH(2)-tBu(2)P-BH(3) (1), which was isolated in 60% yield and characterized by multinuclear NMR spectroscopy, mass spectrometry, and elemental analysis. Thermolysis of 1 in the temperature range 175-180 degrees C led to partial decomposition and the formation of tBu(2)PH.BH(3). When the dehydrocoupling of tBu(2)PH.BH(3) was performed in the presence of [[Rh(mu-Cl)(1,5-cod)](2)] or RhCl(3) hydrate, the chlorinated compound tBu(2)PH-BH(2)-tBu(2)P-BH(2)Cl (2) was formed which could not be obtained free of 1. The molecular structures of tBu(2)PH.BH(3), tBu(2)PH-BH(2)-tBu(2)P-BH(3) (1), and tBu(2)PH-BH(2)-tBu(2)P-BH(2)Cl (2) together with 1 were determined by single-crystal X-ray diffraction studies.     

Synthesis,Crystal Structure and Properties of [Mn(hdpa)2(N(CN)2)2] and [Co(hdpa)2(N(CN)2)2] (hdpa = 2, 2'‐Dipyridylamine)

Two new transition metal(II) complexes [M(hdpa)₂(N(CN)₂)₂] (M = Mn ( 1 ), Co ( 2 ); hdpa = 2, 2'‐dipyridylamine) have been prepared and characterized structurally and magnetically. Both compounds crystallize in the monoclinic space group C2/c. 1 and 2 are isotypic with the unit cell parameters a = 8.634(9), b = 13.541(14), c = 21.99(2) Å, β = 94.806(18)°, and V = 2562(5) ų for 1 , a = 8.617(3) Å, b = 13.629(5)Å, c = 21.598(8)Å, β = 94.593(6)°, and V = 2528.4(15)ų for 2 , and Z = 4 for both. According to X‐ray crystallographic studies, each metal(II) ion was six‐coordinated with four nitrogen atoms from two bidentate hdpa ligand and two nitrogen atoms from two N(CN)^— anions to form slightly distorted octahedrons. Adjacent complex molecules are connected by hydrogen bonds or π···π interactions to form three‐dimensional network. The IR and UV spectroscopy were measured and the magnetic behaviors were investigated.     

The bivalent metal hypophosphites Sr(H2PO2)2, Pb(H2PO2)2 and Ba(H2PO2)2

The structures of isomorphous monoclinic strontium and lead bis­(di­hydrogenphosphate), Sr(H₂PO₂)₂ and Pb(H₂PO₂)₂, and orthorhombic barium bis­(di­hydrogen­phos­phate), Ba(H₂PO₂)₂, consist of layers of hypophosphite anions and metal cations exhibiting square antiprismatic coordination by O atoms. The Sr and Pb atoms are located on sites with point symmetry 2, and the Ba atoms are on sites with point symmetry 222. Within the layers, each anion bridges four metal cations.     

Infinite Three-Dimensional Coordination Polymers: Synthesis and Structures of [Cd (4,4'-bpy)2 (H2O)2]n (pic)2n, [Zn (4,4'-bpy)2 (H2O)2 ]n-(pic)2n (H2O)2n, and [Zn (4,4'-bpy)2 (H2O)2]n (4,4'-bpy)n (H2O)n (pic)2n

Recently, a new research realm in crystal engineering of supramolecular architecturesassembled by means of coordinate covalent bonding', hydrogen bonding', or other weakintermolecular interactions= has been rapidly expanding in order to rationally developnew classes of functional materials with cavities or pores. These types of compoundsmay exhibit interesting topological structures and the clathrations of the cavity structuresmay have many potential properties such as catalysis', electrical co…     

Synthesis,Characterization and Crystal Structure of (PhCH2)2Sn(S2CENt2) and (PhCH2)2Sn(S2CNC4H8)2

Two new dibenzyltin bisditiocarbamates(PhCH2)2 Sn(S2CNEt2)2(1) and (PhCH2)2 Sn(S2CNC4H8)2(2) were synthesized by the reaction of dibenzyltin dichloride with dithiocarbamates and characterized by elemental analysis ,IR,^1H NMR and MS spectra.The crystal structures were determined by X-ray single crystal diffraction analysis.In both complexes,the tin atom is six-coordinated in a distorted octahedral configuration.In the crystals of 1,the molecular packing in unit cell reveals that the two adjacent molecules are symmetrically linked to each other in dimers by two Sn S interactions of 0.3816nm.In the crystals of 2,the molecules are packed in the unit cell in one-dimensional chain structure linked by weaker intermolecular S S conmtacts.     

(CF3)2PAsH2 und (CF3)2AsAsH2

(CF₃)₂PAsH₂ and (CF₃)₂AsAsH₂ (CF₃)₂PAsH₂ is obtained in yields between 30 and 60% according to eq. (1) (CF₃)₂AsAsH₂ is formed by the analogous reaction with (CF₃)₂AsI, but is not sufficiently stable to be isolated. Both compounds are decomposed according to eq. (2) (CF₃)₂PAsH₂ can be studied in solution below ?40°C; it is characterized by molar mass determination and by its n.m.r. spectra (¹H, ¹⁹F, ³¹P). Reactions with polar [HBr, (CH₃)₂AsH, (CH₃)₂PN(CH₃)₂] and nonpolar [Br₂, As₂(CH₃)₄] reagents proceed by cleavage of the P? As bond.     

Polydentate N(2)S(2)O and N(2)S(2)O(2) Ligands as Alcoholic Derivatives of (N,N'-Bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II) and (N,N'-Bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctane)nickel(II)

The synthesis, structural characterization, spectroscopic, and electrochemical properties of N(2)S(2)-ligated Ni(II) complexes, (N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), and (N,N'-bis(2-mercapto-2-methylpropane)1,5-diazacyclooctane)nickel(II), (bme-daco)Ni(II), derivatized at S with alcohol-containing alkyl functionalities, are described. Reaction of (bme-daco)Ni(II) with 2-iodoethanol afforded isomers, (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-O,N,N',S,S')halonickel(II) iodide (halo = chloro or iodo), 1, and (N,N'-bis(5-hydroxy-3-thiapentyl)-1,5-diazacyclooctane-N,N',S,S')nickel(II) iodide, 2, which differ in the utilization of binding sites in a potentially hexadentate N(2)S(2)O(2) ligand. Blue complex 1 contains nickel in an octahedral environment of N(2)S(2)OX donors; X is best modeled as Cl. It crystallizes in the monoclinic space group P2(1)/n with a = 12.580(6) ?, b = 12.291(6) ?, c = 13.090(7) ?, beta = 97.36(4) degrees, and Z = 4. In contrast, red complex 2 binds only the N(2)S(2) donor set forming a square planar nickel complex, leaving both -CH(2)CH(2)OH arms dangling; the iodide ions serve strictly as counterions. 2 crystallizes in the orthorhombic space group Pca2(1) with a = 15.822(2) ?, b = 13.171(2) ?, c = 10.0390(10) ?, and Z = 4. Reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol affords another octahedral Ni species with a N(2)S(2)OBr donor set, ((5-hydroxy-3,7-dithianonadiyl)-1,5-diazacyclooctane-O,N,N',S,S')bromonickel(II) bromide, 3. Complex 3 crystallizes in the orthorhombic space group Pca2(1) with a = 15.202(5) ?, b = 7.735(2) ?, c = 15.443(4) ?, and Z = 4. Complex 4.2CH(3)CN was synthesized from the reaction of (bme-daco)Ni(II) with 1,3-dibromo-2-propanol. It crystallizes in the monoclinic space group P2/c with a = 20.348(5) ?, b = 6.5120(1) ?, c = 20.548(5) ?, and Z = 4.     

Ni(II), Pd(II), Cu(II) And Zn(II) complexes with N-(2-Pyridyl)Carbonylaniline (L), Syntheses and X-Ray Crystal structures of [Cu(L)2(H2O)2](No3)2, [Cu(L)2(H2O)2](Clo4)2 and [Zn(L)2(H2O)2](Clo4)2

Reaction of the N-(2-pyridyl)carbonylaniline ligand (L) with Cu(NO₃)₂, Cu(ClO₄)₂, Zn(ClO₄)₂, Ni(NO₃)₂ and PdCl₂ gives complexes with stoichiometry [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, [Zn(L)₂(H₂O)₂] (ClO₄)_2, [Ni(L)₂(H₂O)Cl](NO₃) and PdLCl₂. The new complexes were characterized by elemental analyses and infrared spectra. The crystal structures of [Cu(L)₂(H₂O)₂](NO₃)₂, [Cu(L)₂(H₂O)₂](ClO₄)₂, and [Zn(L)₂(H₂O)₂](ClO₄)₂ were determined by X-ray crystallography. The cation complexes [M(L)₂(H₂O)₂] contain copper(II) and zinc(II) with distorted octahedral geometry with two N-(2-pyridyl)carbonylaniline (L) ligands occupying the equatorial sites. The hexa-coordinated metal atoms are bonded to two pyridinic nitrogens, two carbonyl oxygens and two water molecules occupying the axial sites. Both the coordinated water molecules and uncoordinated amide NH groups of the N-(2-pyridyl)carbonylaniline (L) ligands are involved in hydrogen bonding, resulting in infinite hydrogen-bonded chains running in one and two-dimensions.     

Diverse evolution of [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 2, 3) metalloligands in CH(2)Cl(2)

The nucleophilicity of the [Pt(2)S(2)] core in [[Ph(2)P(CH(2))(n)PPh(2)]Pt(mu-S)(2)Pt[Ph(2)P(CH(2))(n)PPh(2)]] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH(2)Cl(2) solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged [Pt(2)S(2)] central ring. The reaction of 1 and 2 with CH(2)Cl(2) has been followed by means of (31)P, (1)H, and (13)C NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt[Ph(2)P(CH(2))(n)PPh(2)](S(2)CH(2))], n = 3 (7), 2 (8), and [Pt[Ph(2)P(CH(2))(n)PPh(2)]Cl(2)], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the [Pt(2)S(2)] ring. Only in the case of 1, the reaction proceeds further yielding [Pt(2)(dppp)(2)[mu-(SCH(2)SCH(2)S)-S,S']]Cl(2) (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH(2) groups that participate in the expansion of the (SCH(2)S)(2-) ligand in 7 to afford the bridging (SCH(2)SCH(2)S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged [(dppp)Pt(mu-S)(2)Pt(dppp)] core capped by a CH(2)SCH(2) fragment.