Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid)

The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

Molecular Replacement Studies of Cucurmosin from Cucurbita Moschata:Structure Homology with Trichosanthin

High diffraction quality crystals of cucurmosin, a type I ribosome inactivating protein isolated from the sarcocarp of Cucurbita moschata (pumpkin), have been grown under newly optimised conditions. With in-house rotating anode X-ray source, these crystals diffract to 1.65 ?resolution which is much higher than that of the previously reported crystals that diffracted only to 3 ?resolution. The crystals belong to space group P212121 with cell parameters a = 41.5, b = 58.4 and c = 99.3 . Molecular replacement studies indicate that the cucurmosin structure is homologous to trichosanthin. The initial structural model has been obtained and the model fitting/ refinement is in progress.

Syntheses, Structures and Magnetic Properties of Two Co(II) Coordination Polymers with 2,5-Pyridine Dicarboxylic Acid

The hydro(solvo)thermal reactions of cobalt powder or its chloride with 2,5- pyridine dicarboxylic acid (H2PYDC) yielded two new complexes: [Co(II)2(PYDC)2(H2O)2- (H2O)4]n 1 and {Co(II)[NH2(CH3)2]2(PYDC)2}n 2. It is observed that the reactive solvents result in different connectivity modes of ligand and diverse dimensional extension of crystal structures. The correlation between structure and magnetic property will be discussed in this paper. Crystal data for 1: space group P1, a = 7.0419(17), b = 8.937(2), c = 9.6182(19) ?, α = 91.532(4), β = 99.869(10), γ = 107.889(11)o, V = 565.5(2) ?3, Z = 1, Dc = 1.845 g/cm3, μ = 1.56 mm-1, F(000) = 322 , R = 0.0505 and wR = 0.1580; and those for 2: space group C2/c, a = 14.9075(6), b = 8.2523(3), c = 16.9643(2) ?, β = 100.982(2)o, V = 2048.75(11) ?3, Z = 4, Dc = 1.560 g/cm3, μ = 0.892 mm-1, F(000) = 996, R = 0.0443 and wR = 0.1134.

Synthesis and Crystal Structure of a Co(II) Coordination Polymer Derived from a Flexible Bipyridyl Derivative Ligand

The self-assembly of a flexible bipyridyl ligand 2,2?-bis(4-pyridylmethyle- neoxy)-1,1?-biphenylene (4,4?-bpp) with cobalt(II) center gave rise to a one-dimensional chain complex [Co(μ-4,4?-bpp)2(SCN)2?H2O]n 1 which has been characterized by single-crystal X-ray diffraction. The polymer crystallizes in monoclinic, space group C2/c with unit cell parameters: a = 13.1888(13), b = 24.230(2), c = 15.4218(17) ?, β = 93.291(6)o, V = 4920.1(8) ?3, Z = 4, C50H42CoN6O5S2, Mr = 929.95, Dc = 1.255 g/cm3, F(000) = 1932 and μ(MoKα) = 0.484 mm-1. The final R and wR are 0.0691 and 0.1670 for 3746 observed reflections with I > 2σ(I). 1 possesses an infinite 1-D polymeric chain structure consisting of the repeated basic square units Co2(μ-4,4?-bpp)2, where the Co(II) center acts as the joint of the square ring. The Co(II) center is coordinated in a slightly distorted octahedral geometry with four nitrogen atoms from four different 4,4?-bpp ligands in the equatorial plane and two trans thiocyanate ligands occupying the axial positions, preventing the formation of an extended framework.

Synthesis and Structures of Two New Molybdophosphates

A one dimension solid and a two dimension solid consisting of polyoxoanions bridged by {CoO 3N 2} and {CoO 4} groups respectively have been synthesized by the hydrothermal method and structurally characterized by X Ray crystallography. Each structure has the [(PO 4) 4Mo 6O 15 ] 12- cluster that is commonly observed in many molybdophosphates. In compound 1, [(PO 4) 4Mo 6O 15 ] 12- clusters are linked by {CoO 3N 2} groups to form a chain like structure, and the chains are hydrogen bonded into a network. Compound 2 is a layer structure with channnels constructed from [(PO 4) 4Mo 6O 15 ] 12- clusters and {CoO 4} groups, the organic molecules and the lattice water molecules are distributed disorderly in the interlamellar region and form strong hydrogen bonds with inorganic framework. The IR and the fluorescent spectra were investigated and discussed.

Synthesis and Crystal Structure of Ni(Ⅱ) Complex with N-Salicylaldehyde-N'-phenoxyacetylhydrazine Ligand

The title complex NiL(py)3, where H2L = N-salicylaldehyde-N-phenoxyacetyl hydrazine, was prepared and characterized by X-ray diffraction. The single crystal of the title compound, Ni(C15H12N2O3)(C5H5N)3, is of monoclinic, space group P21/c with a = 11.900(1), b = 9.6855(7), c = 23.658(2) , b = 92.357(2)? V = 2724.5(4) 3, Z = 4, F(000) = 1176, Dc = 1.376 g/cm3, ?= 0.753 mm-1, R = 0.0332 and wR = 0.0820. The coordination polyhedron around the nickel atom is an elongated octahedron. The basal plane consists of one phenol oxygen, one amine carbonyl oxygen and one hydrazine nitrogen atoms from the ligand L2- and one nitrogen atom from one coordinated pyridine ligand, while the axial sites are occupied by two nitrogen atoms of two coordinated pyridine ligands.

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

Hydrothermal Assembly and Structural Characterization of an Octamolybdate Supported Copper (Ⅰ) Tetramer: [Cu_2(1,10-phen)_2(4,4′-bpy)]_2[Mo_8O_(26)]·4H_2O

A hydrothermal reaction of copper acetate with ammonium molybdate, 4,4-bpy (4,4-bipyridine) and 1,10-phen (1,10-phenanthroline) led to the formation of brown crystals of [Cu2(1,10-phen)2(4,4-bpy)]2 [Mo8O26]4H2O 1. Single-crystal X-ray analysis has revealed that 1 (C68H56N12O30Cu4Mo8) crystallizes in the triclinic system, space group P with a = 11.270(3), b = 13.113(6), c = 13.906(3) ? = 103.33(4), b = 98.54(2), g = 101.29(2)? V = 1920.1(1) ?3, Mr = 2542.93, Z = 1, Dc = 2.199 g/cm3, m = 2.435 mm-1, F(000) = 1240, the final R = 0.0445, wR = 0.1082 and S = 1.021 for 5052 observed reflections with I >2s(I). It consists of copper (Ⅰ) tetramer units and -[Mo8O26]4- anions, which are further attached into a three-dimensional framework through hydrogen bonding and - stacking interactions.

Synthesis and Crystal Structure of New Supramolecular Adducts of[PtCl_6]^(2-) with Cucurbit [7] uril:[(H_3O)_2 [PtCl_6]_3 [C_(42)H_(42)N_(28)O_ (14)_2·H_2O

A novel supramolecular adduct 3(C 42H 42N 28O 14) 2·H 2O (1) was synthesized by mixing 2- and cucurbit uril in solution of hydrochloric acid. The crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to orthorhombic system and space group F dd2 with cell dimensions: a=4.705 33 (5) nm, b=7.153 80 (6) nm, c= 1.894 61 (2) nm, Z=16, V=63.7744 (11) nm3, D c= 1.534 g/cm3, μ=3.007 mm -1, F(000)=29 120, R 1= 0.070 7, wR 2=0.169 2. In crystal, the cucurb uril molecules form two zig-zag chains.

Crystal Structure of cis-Dichlorobis-(1,10-phenanthroline) Manganese(Ⅱ)

MnCl2 (C12,H8N2)2, Mr= 486. 26, monoclinic, P21,/c, a= 9. 461 (5),b= 15. 20(1), c= 14. 514(2) A, β=98. 82(3)°, V=2062(2) A3, Z=4, Dc= 1. 57g/cm3. λ(MoKα) = 0. 71073 A, μ(MoKα) = 0. 895 mm-l, F (000) = 988, T= 296K. Final R= 0. 043, Rw= 0. 053 for 2569 observed reflections. The Mn atom is co-ordinated by two Cl anions and four N of two phenanthroline (phen) molecules, forming a distorted octahedron. Two Mn--Cl bond lengths are 2. 437(2) and 2. 449(2) A,respectively. The Mn--N bond lengths vary from 2. 290(3) to 2. 367 (4) A。 The dihedral angle between two phen best planes is 90. 4°.

Synthesis and Characterization of a Two-dimensional Cadmium(II) Compound Involving Covalent and Hydrogen Bonds

A two-dimensional hydrogen-bonded cadmium(II) compound [Cd(dapm)2- (CH3COO)2(H2O)2] (dapm = diaminodiphenylmethane) has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group C2/c with a = 27.572(3), b = 5.5064(5), c = 23.310(2) , = 124.785(1)o, C15H19Cdo.5ON2O3, Mr =331.52, V = 2906.6(5) ?, Z = 4, Dc = 1.515 g/cm3, F(000) = 1368 and = 0.801 mm-1. The final R = 0.0403 and wR = 0.1014 for 1795 observed reflections with I≥4(I). The centrosymmetric Cd(II) is six- coordinated in a distorted octahedral geometry, and the dapm in a trans mode acts as a monoden- tate ligand. The intermolecular hydrogen bonds among coordinated aqua molecules with coordi- nated acetate oxygen atoms and uncoordinated dapm nitrogen atoms form a two-dimensional supramolecular framework.

STUDIES ON RARE EARTH METAL COMPLEXES OF AMINO ACIDS. THE SYNTHESIS AND CRYSTAL STRUCTURE OF TE-TRAKIS ( ALANINE ) OCTAAQUODILANTHANIDE HEXAPER-CHLORATE [Ln_2(Ala)_4(H_2O)_8]*(ClO_4)_6(Ln = Er^(3+)and Eu^(3+),Ala=CH_3CH(^+NH_3)COO^-)

Complex [Er2(Ala)4(H2O)8]·(ClO4)6, 1, Mr = 1431. 8, mono-clinic, space group C2/c with cell parameters a= 18. 21(1), 6 = 14. 67(2), c=17. 19(3)(?), β=101. 60(8)°, V = 4495(4)(?)3, Dc=2.11g/cm3, Do = 2. 09g/cm3, Z = 4, F (000) = 2808, μ= 42. 30cm-1; Complex [Eu2(Ala)4(H2O)8]·(ClO4)6, 2, Mr = 1401.4, monoclinic, space group C2/c, a = 18. 16(4) , b = 14.52(2), c=17. 35(1)(?), β=102. 3(1)°, Z = 4, V= 4468(11)(?)3. The structure of complex 1 is refined by full-matrix least - squares method with 3348 observed reflections (I≥3σ (I)) to R = 0. 048 and Rw= 0.060. The two erbium ions in the dimeric complex cation [Er2(Ala)4(H2O)8]]6+ are connected by four bridging carboxylato groups, each pair of the carboxylato groups is coplanar with the two Er(III) ions and the dihedral angle between the two planes is 91. 42*. Each Er3+ion is coordinated by four carboxylato oxygen atoms and four water oxygen atoms, assuming a square antiprism arrangment. The alanine exists in the form of CH3CH (+NH3) COO- , and the

One-dimensional Zigzag Chain Coordination Polymer [Zn(μ-phth)(imi)_2]_∞ Bridged by ο-Phthalato

The reaction of zinc carbonate with o-phthalic acid and imidazole in an aqueous-alcohol solution led to the formation of colorless crystals of [Zn(-phth)(imi)2]∞. Single-crystal X-ray analysis has revealed that the complex crystallizes in a monoclinic system, space group Pn with a = 8.394(2), b = 9.976(3), c = 9.959(3) ? ?= 104.409(4)? V = 807.6(4) ?, Z = 2, C14H12N4O4Zn, Mr = 365.65, Dc = 1.504 g/cm3, ?= 1.544 mm-1, F(000) = 372, the final R = 0.0466 and wR = 0.1171 for 1834 reflections with I >2(I). The complex displays a zigzag infinite chain structure in which each zinc (Ⅱ) center is coordinated by two oxygen atoms and two nitrogen atoms to generate a ZnN2O2 distorted tetrahedral geometry. The neighboring zinc atoms are bridged by the o-phthalate ligand. Each chain is linked by hydrogen bonds with its neighbors to form a three-dimensional coordination polymer.

Syntheses,Structures and Characterizations of Two New Vanadium(V) Complexes:[PyH][V^VO_2(C_(14)H_9N_2O_3Br)] and [V^VO(C_(14)H_9N_2O_3Br)(OCH_3)]

The new oxovanadium(V)complex,[PyH][VO2(L)]1(salicyladehyde 5-bromo salicyloylhydrazone is abbreviated as H2L;Hpy is protonated pyridine)was obtained from a refluxed solution of VOSO4 and H2L in acetonitrile-methanol-pyridine.Similarly,another new complex,[VO(L)(OCH3)]2 was synthesized by refluxing VOSO4 and H2L in methanol-pyridine.Crystal data for 1:C19H15N3O5BrV,Mr=496.2,monoclinic,P21/n,a=7.1885(3),b=9.2718(3),c=28.803(1)A,β=96.185(1)°,Z=4and V=1908.6(1)A^3;for 2:C15H12N2O5BrV,Mr=431.1,monoclinic ,P21/n,a=12.202(2),b=8.045(2),c=16.604(3)A,β=101.29(3)°,Z=4 and V=1598.4(2)A^3.The structures of 1 and 2 have been determined by X-ray analyses and reveal that the coordination environments of V atoms in both complexes are of square-based pyramid.Three of the four based donor atoms are from the tridentate“ONO”donor ligand while the fourth is one terminal oxygen atom with the V(1)-O(3)distance 1.646(4)Afor 1 and one-OCH3 group with the V(1)-O(3) distance 1.753(3)Afor 2.The V(1)-O(4) terminals occupy the axial sites in both cases.The complexes are also characterized by IR and ^1HNMR spectroscopies.

Synthesis and Crystal Structure of 1-D Chain Copper(Ⅱ) Complex: [Cu(L)Cl_2]_n (L=2,5-Di-2-pyridyl-1,3,4-oxodiazole)

The title complex, [Cu(L)Cl2]n (L = 2,5-di-2-pyridyl-1,3,4-oxodiazole) 1, has been obtained from the reaction of 3,6-di-2-pyridyl-1,2,4,5-tetrazine (bptz) and CuCl2?H2O in a mixture solvent of CH3CN and CH2Cl2 (L is generated from the metal-assisted hydrolysis reaction of bptz) and structurally characterized. It crystallizes in space group C2/c of monoclinic system with cell parameters: a = 9.812(2), b = 12.679(3), c = 11.111(2) ? b = 103.92(3)? V = 1341.6(5) 3, Z = 4, Dc = 1.776 g/cm3, Mr = 358.66, F(000) = 716, ?= 2.024 mm1 and S = 1.004. The final R = 0.0346 and wR = 0.0938 for 1011 observed reflections with I > 2(I). The Cu(Ⅱ) ion is six-coordinated by four N atoms of two L ligands and two Cl ions in a distorted octahedral geometry. The ligand L acts as a bis-bidentate ligand to bridge the Cu(Ⅱ) ions, resulting in an infinite chain structure.

Syntheses and Structures of Lanthanide Complexes with Isonicotinate

The crystal structures of two coordination polymers [Ln(IN)3(H2O)2]n (Ln = Nd 1, Gd 2; IN = isonicotinate) were determined by single-crystal X-ray diffraction and further chara- cterized by IR, elemental analysis and thermogravimetric analysis. Crystal data for 1: monoclinic, space group P21/c, a = 9.6636(5), b = 19.7532(10), c = 11.6183(6) ?, β = 112.032(1)°, V = 2055.83(18) ?3, Z = 4, Dc = 1.766 g/cm3, F(000) = 1076, μ = 2.575 mm–1 and R = 0.0493; Crystal data for 2: monoclinic, space group C2/c, a = 20.251(2), b = 11.6199(11), c = 9.8240(9) ?, β = 115.505(3)°, V = 2086.4(3) ?3, Z = 4, Dc = 1.781 g/cm3, F(000) = 1092, μ = 3.228 mm–1 and R = 0.0695. In the title compounds, the center atoms Ln(III) are in a distorted square antiprismatic geometry and linked by bridging isonicotinate to form an infinite chain. The intermolecular hydro- gen bonds lead to the formation of three-dimensional supramolecular structures.

Synthesis and Structural Characterization of {[Mn(phen)_2(OAc)(H_2O)]ClO_4}_2H_2O

The crystal structure of the title compound {[Mn(phen)2(OAc)(H2O)]ClO4}2H2O (phen = 1,10-phenanthroline) has been synthesized and determined by X-ray diffraction. The crystal is of triclinic, space group P?with a = 12.7955(4), b = 15.0544(4), c = 16.2183(4) , ?= 64.479(1), b =67.526(1), g = 83.582(1), C52H40Cl2Mn2N8O15, Mr = 1197.70, V = 2600.1(1) ?, Dc = 1.530 g/cm3, F(000) = 1224, = 0.666 cm-1 and Z = 2. The final refinement gave R = 0.0691 and wR = 0.1821 for 6131 observed reflections with I > 2s(I). The cell of the complex contains two uniform mono-manganese molecules [Mn(phen)2(OAc)(H2O)]ClO4 and a solvate water molecule. Four nitrogen atoms from two chelating phenanthroline ligands and one oxygen atom from acetate ligate to the MnⅡ ion, forming a distorted octahedral geometry together with one coordinated water molecule. One ClO4- anion and one water molecule exist outside the cation [Mn(phen)2(OAc)- (H2O)]+ as a counter ion and solvate molecule, respectively.

Solvothermal Synthesis and Structure Characterization of a 3D Hydrogen-bonded Copper Compound [Cu(H_2dhpmc)_2]·2H_2O

The solvothermal reaction of H3dhpmc (H3dhpmc = 2, 4-dihydroxypyrimidine- 5-carboxylic acid), CuCl2稨2O and NaVO3 results in the formation of a discrete mononuclear Cu(Ⅱ) complex [Cu(H2dhpmc)2]?H2O. It crystallizes in monoclinic system, space group P21/c with a = 5.0497(9), b = 10.0196(6), c = 13.715(2) ? b = 96.237(1)? V = 689.8(2) 3, Z = 2, Dc = 1.973 g/cm3, ?= 1.654 mm-1, F(000) = 414, R = 0.0736 and wR = 0.1351. Each Cu(Ⅱ) is coordinated to four oxygen atoms of two 2, 4-dihydroxypyrimidine-5-carboxylic acid ligands in the equatorial position and two oxygen atoms of two water molecules in the axial position to form an axially elongated octahedral geometry. The title complex is further linked into a three-dimensional structure through the weak interactions of hydrogen bonds between the oxygen atoms and the nitrogen atoms.

Structure of High Temperature Phase α-Ba_3Y(BO_3)_3 Crystal

The high temperature phase a-Ba3Y(BO3)3 was synthesized by Czochralski method, and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the trigonal system, space group 3R with a = 13.028(2), c = 9.4992(2) ? V = 1396.1(5) ?, Ba3YB3O9, Mr = 677.36, Z = 6, Dc = 4.834 g/cm3, l(MoKa) = 0.71073 ? m = 18.721 mm-1, F(000) = 1764, the final R = 0.0718 and wR = 0.1640 for 1199 observed reflections with I > 2s(I). In this structure two alternate nonequivalent Y atoms form one-dimensional chains bridged by the Ba atoms with BO3 triangles which link Y(1) and Y(2), respectively. The Ba atom is surrounded by nine O atoms belonging to six BO3 triangles.

Synthesis and Structure of a New Polymorph Ba_2CuSi_2O_7

A new phase of dibarium copper disilicate, b-Ba2CuSi2O7, was obtained by the solid-state reaction. Crystal data: Mr = 506.4, tetragonal, P421m, a = 8.284(2), c = 5.313(3) ? V = 364.6(4) ?, Z = 2, Dc = 4.61 g/cm3, l(MoKa) = 0.71703 ? ?= 13.91 mm-1, F(000) = 450 and T = 293(2) K; the final R = 0.0343, wR = 0.0382 and S = 1.02 for 512 observed reflections (I > 3s(I)) refined by 34 variables. The compound was characterized by a layered structure composed of CuO4 tetrahedra and Si2O7 anions with the Ba cations filling the cavities between the layers. The building blocks of the present structure are similar to those in the a-Ba2CuSi2O7, but the linkage of CuO4 tetrahedra and Si2O7 anions is significantly different. In particular, the double-tetrahedral anions of Si2O76- form an orthogonal arrangement in the present structure, in contrast to the parallel arrangement reported in the a-Ba2CuSi2O7.