Synthesis and Crystal Structure of a Novel Ternary Ni(II) Complex with 2-Hydroxyl-1,10- phenanthroline and 2-Hydroxynicotinic Acid as Ligands

A novel ternary complex of [NiL1L2·2H2O]·NO3·H2O （L1 = 2-hydroxyl-1,10-phenanthroline （HOphen）, L2 = 2-hydroxynicotinic acid （H2nicO）） was synthesized, and its crystal structure was determined by X-ray diffraction and further characterized by infrared and elementary analysis. The title complex （C18H18NiN4O10, Mr = 509.07） belongs to the triclinic system, space group P1^- with a = 712490（7）, b = 11.0164（10）, c = 13.3864（13）A, α = 91.6040（10）,β= 98.8620（10）, γ= 107.1140（10）°, V= 1006.43（17）A^3, Z = 2, Dc = 1.680 g/cm^3,μ= 1.032 mm^-1, F（000） = 524, the final R = 0.0461 and wR= 0.1238. In the complex, the Ni（H） ion is six-coordinated to assume a distorted octahedral geometry, and a 3D supramolecular network comes into being via weak intermolecular interactions of X-O--.H （X = N, O）.

Synthesis and Crystal Structure of an Unusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate (phenH)_2[La(NO_3)_5(phen)]·CH_3OH

Lanthanum complex （phenH）2[La（NO3）5（phen）]·CH3OH （1, phen=phenanthroline） was synthesized and characterized by single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/c with a=20.3040（3）, b=10.7091（1）, c=19.0771（2）, β=102.090（1）°, V=4056.07（8）3, Z=4, Dc=1.676 g/cm3, μ= 1.142 mm-1, F（000）=2056, the final R=0.0346 and wR=0.0793 for 9981 （Rint=0.0358） independent reflections. The mononuclear complex 1 consists of four parts： two phenH＋ cations formed by the protonation of phen, one complex anion [La（NO3）5（phen）]2-, and one solvent methanol molecule. The complex anion contains one phen and five nitrate ligands which both chelate the center La（III） ion, adopting a distorted twelve-coordinated icosahedral geometry. The cations, anion and solvent molecule are linked together by hydrogen bonds. One of the protonated phenanthrolines （phenH＋） acting as cation connects to the anion via N–H…O hydrogen bond directly, and the other one links to the anion through an intermediate solvent CH3OH via N–H…O and O–H…O hydrogen bonds. By the plentiful additional weak C–H…O intermolecular hydrogen bonds, the compound molecules construct a two-dimensional layer structure.

Hydrothermal Syntheses and Crystal Structures of Three Lanthanide(Ⅲ)Complexes Based on Carboxyl Derivatives of 1,10-Phenanthroline

Three lanthanide（III） complexes [Ln（4-NCP）（1,4-BDC）]n·xn H2O（Ln = Pr（1）, Sm（2）, Nd（3）. 4-HNCP = 2-（4-carboxyphenyl）imidazo（4,5-f）（1,10）phenanthroline, 1,4-H2 BDC = benzene-1,4-dicarboxylic acid） have been hydrothermally synthesized and characterized via elemental analysis, infrared spectrometry and single-crystal X-ray diffraction. Structural analyses revealed that complexes 1~3 possess similar porous three-dimensional frameworks with the point symbol {4^（12）·6~3}. Meanwhile, complexes 1~3 exhibit excellent thermal stabilities and complex 2 exhibits characteristic luminescent property.

A Novel Potassium Complex Based on the Taurine-salicylaldehyde Schiff Base:Synthesis,Crystal Structure and Spectroscopy

A novel two-dimensional self-assembly network formulated as [K（TSSB）]n （TSSB= taurine-salicylaldehyde Schiff base） has been synthesized via the reaction of salicylaldehyde with taurine at the presence of potassium hydroxide in water-methanol solution,and was structurally characterized by elemental analysis,IR,UV-VIS spectra and X-ray diffraction.It crystallizes in the monoclinic system,space group P21/c with a=20.245（3）,b=7.2905（9）,c=7.5458（10）,β= 94.1920（10）o,V=1110.8（2）3,Mr=267.34,Z=4,Dc=1.599 g/cm3,μ（MoKα）=0.663 mm-1 and F（000）=552.The units of K[TSSB] are linked into a one-dimensional double chain structure via the sulfonic groups from the taurine-salicylaldelyde Schiff base,and such chains are further extended through O-K-O bond interactions resulting in a two-dimensional supramolecular architecture.In the complex,the K（I） ion displays a slightly distorted dodecahedral geometry with an eight-coordination number.

Preparation, Crystal Structure and Thermal Decomposition Process of Dysprosium Benzoate Complex with 1,10-Phenanthroline

A dinuclear dysprosium（III） complex with benzoic acid and 1,10-phenanthroline, [Dy（BA）3phen]2 （BA = benzoate, PHEN = 1,10-phenanthroline） （C66H46Dy2NaO12, Mr = 1412.07） was synthesized and characterized by elemental analysis, UV, IR, X-ray diffraction, molar conductance and TG-DTG techniques. It crystallizes in triclinic, space group P1 with a = 10.773（2）, b = 11.933（3）, c = 12.417（5） A, α= 105.226（3）,β= 93.470（3）, γ= 113.475（2）°, V= 1388.0（7）, Z = 1, Dc = 1.689 g/cm3, μ（MoKa） = 2.742 mm-1 and F（000） = 698. R = 0.0210, wR = 0.0538. In the crystal, each Dy（III） ion is eight-coordinated by one bidentate chelating carboxylate group, four bidentate bridging carboxylate groups and one 1,10-phenanthroline molecule. The thermal decomposition process of [Dy（BA）3phen]2 has been determined by thermal analysis.

Synthesis and Crystal Structure of the Copper(Ⅱ) Complex with 1,10-Phenanthroline-5,6-dione

The complex Cu(phon)(NO3)2(CH3CN) (phon = 1,10-phenanthroline-5,6-dione) has been synthesized and characterized by elemental analysis, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex crystallizes in orthorhombic system, space group P212121 with a = 8.353(1), b = 11.299(2), c = 17.764(2)(A), V = 1676.5(4) (A)3, Z = 4, C14H9CuN5O8, Mr = 438.8, Dc = 1.739 g/cm3, F(000) = 884 and ((MoK() = 1.361 mm-1. The final R and wR factors for the observed reflections with I > 2((I) are 0.0353 and 0.0855, respectively. R = 0.0432 and wR = 0.0899 for all data. The structure of the title complex consists of a neutral mononuclear entity. The central Cu (Ⅱ) atom is five-coordinated by two nitrogen donors of one ligand, two unidentate NO3- ions and one CH3CN molecule. The coordination geometry of Cu (Ⅱ) can be considered as a distorted trigonal bipyramidal configuration. The complex ability of the NO3- ion has more effect than that of the ClO4- ion on the structure of the complex.

Synthesis and Crystal Structure of a New Ternary Complex of Nickel(II) with L-Aspartic Acid and 1,10-Phenanthroline

A new ternary complex of nickel(II) with L-aspartate (L-Asp) and 1, 10-phenan- throline(Phen), [Ni3(L-Asp)(Phen)5(H2O)3](ClO4)4?4.75H2O, has been synthesized in a mixed sol- vent of H2OC2H5OH at the pH value of 3. It crystallizes in triclinic, space group P1 with a = 11.861(2), b = 18.384(4), c = 19.746(3) ?, α = 107.68(1), β = 105.94(1), γ = 103.41(2)°, V = 3703.6(11) ?3, Mr = 1745.66, Z = 2, Dc =1.565 g/cm3, μ = 0.989 mm-1, F(000) = 1791, R = 0.0643 and wR = 0.1611. The complex contains two cations, binuclear [Ni2(L-Asp)(Phen)3(H2O)]2+ and mononu- clear [Ni(Phen)2(H2O)2]2+. All the nickel ions in the complex are six-coordinated with a distorted octahedral geometry, but the coordination environments for them are different. There exist hydrogen bonds and π-π stacking interactions in the complex.

Synthesis and Crystal Structure of the Copper(II) Complex with Tris-(1,10-phenanthroline-5,6-dione)

The title complex [CuL3]（ClO4）2·2H2O·2CH3CN （L = 1,10-phenanthroline-5,6-dione） has been synthesized and characterized by elemental analysis, conductivity, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex （C40H28Cl2CuN8O16, Mr = 1011.14） crystallizes in orthorhombic system, space group P212121 with a=13.983（1）, b=14.310（1）, c= 20\^890（2） , V = 4179.7（6） 3, Z = 4, Dc = 1.607 g/cm3, F（000） = 2026,μ（MoKα） = 0.736 mm-1. The final R and wR factors are 0.0446 and 0.1212 respectively with 8545 independent reflections. The title complex is composed of a discrete [CuL3]2+ cation, uncoordinated ClO4- anions, H2O and CH3CN molecules. The central Cu（II） atom is six-coordinated by six nitrogen donors of three ligands. The coordination geometry of Cu（II） could be considered as an approximately ideal octahedral configuration with little static Jahn-Teller distortion （the longest and shortest Cu-N bonds are 2.102 vs 2.139  with the mean length of 2.122 ）, which is very rare for a six-coordinated Cu（II） complex.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex with Tridentate Schiff Base and Azido Bridge

A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.

Syntheses and Crystal Structures of Complexes [Cu(C_(14)H_8N_3O_4Br)](C_4H_9NO) and [Ni(C_(14)H_9N_2O_3Br)](C_4H_9NO)

The title compounds, Cu（L1）（C4H8NHO） and Ni（L2）（C4H8NHO） （H2L1 = 5-bromosalicylaldehyde-p-nitrobenzoylhydrazone, H2L2 = 5-bromosalicylaldehyde-p-hydroxybenzoylhydrazone）, have been obtained and characterized by single-crystal X-ray diffraction. Complex 1 belongs to the triclinic system, space group P1 with a = 8.6960（2）, b = 9.957（2）, c = 11.878（2）A, α = 73.36（3）, β = 78.25（3）, γ = 82.64（3）°, V = 962.1（3） A^3, Mr= 512.81, Z = 2, F（000） = 514, Dc = 1.770 g/cm^3,μ（MoKα） = 3.251, R = 0.0337 and wR = 0.0846. Complex 2 is of monoclinic, space group P21/c with a = 13.313（2）, b = 8.2096（1）, c = 21.890（3） A,β = 125.737（3）°, V = 1941.9（4） A^3, Mr= 478.97, Z = 4, F（000） = 968, Dc = 1.638 g/cm^3,μ（MoKα） = 3.085, R = 0.0356 and wR = 0.0817. The ligands form a satisfactory N2O2 square plane around the metal centers in two compounds. Different patterns of hydrogen bonds are observed owing to the presence of different substituents on aromatic ring of the acylhydrazone Schiff bases. In complex 1, square-planar copper（Ⅱ） complexes are linked by intermolecular hydrogen bonds leading to zigzag infinite chains. In complex 2, the metal complexes are linked via hydrogen bonds to form corrugated sheets in a staggered fashion; 3D channels along the b axis are constructed through other non-covalent interactions between the neighboring layers.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex [Cu(C_(12)H_(17)N_2O)(NCS)]_2 with Tridentate Schiff Base Ligand N-(Salicylidene)-3-dimethylaminopropylamine

A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.

Syntheses, Crystal Structures and Antibacterial Activities of Copper(Ⅱ) and Zinc(Ⅱ) Complexes Based on (E)-4-fluoro-2-((3-morpholinopropylimino)methyl)phenol

Two Schiff base complexes [Cu（L）2] （1） and [Zn（L）2]·3H2O（2） of （E）-4-fluoro-2-（（3-morpholino propylimino）methyl）phenol （HL） have been synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Crystal data for 1： triclinic, space group Pī with a=4.8000（10）, b=11.109（2）, c=13.921（3）,α=66.55（3）,β=80.35（3）,γ=81.09（3）°, V=668.2（2）3 , Z=1, Dc=1.477g/cm 3 , F（000）=311, and the final R=0.0744 and wR=0.1601 for 2301 observed reflections with I 〉 2σ（I）. And those for 2： monoclinic, space group P21 /c with a=14.789（3）, b=11.713（2）, c=18.846（4）,β=107.85（3）°, V=3107.4（11）3 , Z=4, D c=1.389 g/cm 3 , F（000）=1368, and the final R=0.0749 and wR=0.1348 for 5423 observed reflections with I 〉 2σ（I）. Both 1 and 2 are four-coordinated complexes, with a square-planar geometry of copper（Ⅱ） in 1 and a slightly distorted tetrahedral geometry of zinc（Ⅱ） in 2. An asymmetric unit consists of only one half of a Cu ion and one L ligand in 1, while an asymmetric unit is composed of one Zn ion, two L ligands and three water molecules in 2. Non-classical C-H···O and C-H F hydrogen bonds play important roles in the formation of a 1D chain of 1, but O-H O and O-H N hydrogen bonds play dominant roles in the self-assembly of a 3D network of 2. The antibacterial activities of 1 and 2 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli and E. cloacae have been evaluated by MTT method.

Synthesis, Crystal Structure, Thermal Behavior and Photoluminescent Property of Complex [Zn(L)(SO_4)]·0.5H_2O

Complex [Zn（L）（SO4）]0.5H20 （L = 2-（2-chloro-6-fluorophenyl）-lH-imidazo[4,5- J][1,10]phenanthroline） has been synthesized under hydrothermal conditions. The compound was characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 9.9916（7）, b = 12.3834（9）, c = 29.259（2） A, fl = 97.7720（10）°, V = 3587.0（4） A^3, Z = 2, C76H41CI4F4NI60952Zn2, Mr = 1734.91, Dc = 1.606 g/cm^3, F（000） = 1754, p（MoKa） = 0.959 mm-1, R = 0.0492 and wR = 0.1385. The asymmetric unit of 1 contains one Zn（lI） atom, two L ligands, one sulfate anion and half a water molecule. Each Zn（lI） atom is five-coordinated by four nitrogen atoms from two different L ligands and one sulfate oxygen atom in a tetragonal pyramidal coordination environment. The N-H＇＂O hydrogen bonds link the discrete structure of 1 into a 2D supramolecular architecture. The photoluminescent property of 1 has also been studied in the solid state at room temperature.

Synthesis and Crystal Structure of an Ion-pair Supramolecular Associate 2,9-Diformyl-1,10-phenanthrolinebis-(2,6-dimethylanil)cobalt(Ⅱ) Perchlorate

2,9-Diformyl-l, 10-phenanthrolinebis（2,6-dimethylanil）cobalt（Ⅱ） perchlorate was synthesized and demonstrated to be [COL2][ClO4]2 by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group C2/c with a = 22.294（4）, b = 15.122（3）, c = 20.640（4） A, β = 119.618（4）°, V = 6048.9（19） A^3, C63H52Cl2CoN9O9, Mr= 1208.97, F（000） = 2504, De= 1.328g/cm^3, Z = 4, μ= 0.436, the final R = 0.0712 and wR = 0.1718 for 1734 observed reflections （I 〉 2σ（I））. In its solid state the helical polymeric chains are supramolecularly associated through intermolecular and interionic hydrogen bonding interactions.

Synthesis and Crystal Structure of a New Complex [CuL(Phen)]·NO_3

A new mononuclear copper（Ⅱ） complex [CuL（Phen）]-NO3 （L - 2-{2-[（3,5-dibro- mosalicylidene）amino]ethyl }- 1 H- 1,3-benzimidazole, Phen = 1,10-phenanthroline） has been synthesized and its crystal structure was determined by X-ray diffraction method. It crystallizes in monoclinic, space group C2/c with a = 24.966（7）, b = 15.673（4）, c = 16.600（5） A,β = 123.981（4）°, C28H20Br2CuN604, Mr = 727.86, V = 5386（2） A^3, Z = 8, Dc = 1.795 g/cm^3,μ（MoKα = 3.826 mm^-1, F（000） = 2888, the final R = 0.0508 and wR = 0.1024 for 5440 independent reflections with Rint = 0.1134. The title compound is composed of [CuL（Phen）]＋ cation and NO3^- anion. The coordination geometry around copper atom is a highly distorted trigonal bipyramid consisting of one benzimidazole nitrogen atom, one phenolato oxygen atom and one phenanthroline nitrogen atom on the equatorial plane together with one imine nitrogen atom and one phenanthroline nitrogen atom occupying the axial positions. The hydrogen bonding and π-π stacking interactions link the copper complex molecules into a 3-D supramolecular structure.

Synthesis and Crystal Structure of trans(N)-(1,10-Phenanthroline)-bis (DL-Al aninato)-Cobalt( Ⅲ ) Chloridetrihydrate

The title compound was synthesized by the reaction of cis-[Co(phen)2Cl2]Cl·3H2O with DL-alanine at pH = 8, and isolated using a column chromatographic method. Its crystal structure was determined. The crystal structure belongs to mono-clinic system, space group P21/c, with a = 0. 9549(6) nm, b=2.3746(8) nm, c= 1.0782(4) nm, β=114.13(3)°? Z = 4, Dc= 1. 50 g/cm3. The final refinement converged to R = 0. 047 for 3246 independent observed reflections. In the octahedral coordination sphere formed by the cobalt atom and the coordinate atoms, N, O of DL-alan-inato ligands are in the configuration of trans-N ,N form.

Synthesis and Crystal Structure of[Copper(1,10-phenanthroline)_2(pyridine)]perchlorates

The complex [Cu(phen)2py](ClO4)2 was obtained by the reaction of 1,10-phenanthroline with Cu(ClO4)2·6H2O in water and by recrystallization from pyridine. A single-crystal X-ray study shows that the complex is a square pyramidal arrangement of five nitrogen atoms from the two 1,10-phenanthroline ligands and one pyridine ligand, respectively. The compound is orthorhombic, C29H21N5Cl2O8Cu, Mr = 701.958, with space group Pbcn, a = 29.9593(3), b = 16.1240(3), c = 11.9183(6) ?, V = 5757.3(3) ?3, Z = 8, Dc = 1.409g/cm3, μ =1.121 mm-1, F(000) = 2465, R = 0.0539, Rw = 0.1380 for 4293 reflections with I >2σ(I). The bond lengths of Cu(1)－N(1), Cu(1)－N(2), Cu(1)－N(3) and Cu(1)－N(4) are 2.223(3), 2.017(3), 2.013(3) and 2.038(3) ?, respectively. The distance from copper to pyridine N(5) is 2.012(3) ?. The angles N(2)－Cu(1)－N(3) and N(4)－Cu(1)－N(5) are 176.1(1) ° and 160.9(1)°, respectively. The angles between axial position nitrogen atom N (1) and four square position nitrogen atoms N(2), N(3), N(4), N(5) are 79.3(1), 98.3(1), 90.7(1), 108.4(1)°, respectively.

Synthesis Crystal Structureof Quaternary Mixed AnionComplex of Lanthanides[Ln(CCl_3COO)_2 (CH_3COO)(phen) (H_2O)]_2

Three new quaternary mixed anion complexes of lanthanides were prepared from thewater-ethanol solution under slightacidity condition and characterizedby elemental analysis, IR, UVspectrum and single crystal X-raydiffraction analysis. The crystal ofLa(CCl3COO)2 (CH3COO) (phen)(H2O)·DMF]2 belongs to tricliniccrystal system, space group P1with a=1 .2510 (4) nm, b=1.3460(5) nm, c=1.0343 (3)nm, α=102.47(3)°, β=102.34(2)°, γ=113.82 (2)°, μ(MoKa) = 20.47 cm-1, Z= 1, Dc=1. 800 g·cm-3, F (000) =780. 00. The acetate tends to coordinate with the center ion as abridge and trichloroacetate has fourkinds of coordination modes, somany coordination modes were observed in their co-ligand system.