Syntheses,Crystal Structures,and Antimicrobial Activities of N′-(5-Hydroxy-2-nitrobenzylidene)-4-dimethylaminobenzohydrazide Methanol Solvate and 2-Fluoro-N′-(5-hydroxy-2-nitrobenzylidene)benzohydrazide

Two new hydrazone compounds,N'-(5-hydroxy-2-nitrobenzylidene)-4-dimethyl-aminobenzohydrazide methanol solvate (1) and 2-fluoro-N'-(5-hydroxy-2-nitrobenzylidene)benzo-hydrazide (2),have been synthesized and characterized by elemental analysis,IR spectra,1H NMR,and single-crystal X-ray diffraction.Compound 1 crystallizes in the monoclinic space group P21/c with a=11.571(3),b=12.420(3),c=12.360(2) ?,β=97.495(2)°,V=1761.1(7) 3,Z=4,R=0.0735 and wR=0.1344.Compound 2 crystallizes in the triclinic space group P with a=7.551(3),b=8.254(3),c=11.365(2) ?,α=79.352(2),β=76.154(2),γ=71.624(2)°,V=648.2(4) 3,Z=2,R=0.0393 and wR=0.1008.The hydrazone molecules of the compounds display E configurations with respect to the C=N double bonds.In the crystal structure of 1,the hydrazone molecules are linked by methanol molecules through N-H…O,O-H…N and O-H…O hydrogen bonds,forming chains running along the c axis.In the crystal structure of 2,molecules are linked through N-H…O and O-H…O hydrogen bonds,forming ribbons running along the b axis.The preliminary antimicrobial activities were studied.     

CRYSTAL AND MOLECULAR STRUCTURES OF BIS (CYCLOPENTADIENYL) BIS (2,4,6-TRICHLOROPHENOXY)TITANIUM, Cp_2Ti(OC_6H_2Cl_3-2,4,6)_2 (Ⅰ) AND TETRAKIS(CYCLOPENTADIENYL)BIS (4-CHLOROPHENOXY)-μ-OXO-DIZIRCONIUM,[Cp_2Zr(OC_6H_4Cl-p)]_2O (Ⅱ)

The crystal and molecular structures of (Ⅰ) and (Ⅱ) have been determined from single-crystal, X-ray diffraotion data collected by counter methods. Compound (Ⅰ) crystallizes inthe monoclinic space group C 2/c with a=19.618(11) ?, b=9.356(4) ?, c=15.985(8) ?,β=128.84 (3)°, Z=4. The molecule possesses C_2 point symmetry. Compound (Ⅱ) erystallizesin the monoclinic space group P 2_1/a with a=8.329(2) ?, b=36.509(13) ?, c=10.647(4)?, β=96.04(2)°, Z=4. The oxo-bridge links two [Cp_2Zr(OC_6H_4Cl-p)] units together withthe bond angle Zr-O-Zr of 161.1(9)°. The relatively shorter Zr-O bond lengths show the pre-sence of partial double-bond character. Both Ti and Zr atoms have d° electronic configura-tion in (Ⅰ) and (Ⅱ). The M-O bonds of the two compounds are discussed.     

Switchable Dielectric Materials Based on 2-Methylimidazole

Two novel coordination polymers with molecular structures(2MI)~+[Zn(2MI)Cl_3]~-(1) and(2MI)~+NO_3~-(2) based on ligand 2-methylimidazole(2MI) were synthesized under solution method. Compound 1 crystallizes in the monoclinic system, space group Cc with a=7.489(2), b=13.448(4), c=13.983(4) ?, β=98.402(2)°, Z=4 and V=102.246(2) ?~3. Compound 2 crystallizes in the orthorhombic system, space group pnma with a=14.296(3), b=6.3180(12), c=7.3862(13) ?, β=90°, Z=4 and V=667.1(2) ?~3. Dielectric measurements show compounds 1 and 2 have reversible dielectric anomalous behaviors with variation frequencies at different temperature.     

Syntheses,Structures,Fluorescence and Heterogeneous Catalysis of Coordination Polymers with 4-Benzoimidazol-1-yl-methyl Benzoic Acid and 2,2′-Dipyridine

Two coordination polymers called [Ni(L)_2]_n(1) and [Ni(2,2?-bpy)_22(H_2O)]n (2)(HL = 4-benzoimidazol-1-yl-methyl benzoic acid, 2,2?-bpy = 2,2?-dipyridine) were synthesized by solvothermal reaction simultaneously and characterized by elemental analyses, thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic system, space group P2_1/c with a = 14.673(3), b = 10.773(2), c = 16.566(3) ?, V = 2559.2(8) ?~3, Z = 4 and F(000) = 1160. 2 also crystallizes in monoclinic system, space group C2/c with a = 15.404(3), b = 12.652(3), c = 6.5362(13) ?, V = 1246.2(5) ?~3, Z = 4 and F(000) = 712. The bridging L ligand connects the Ni~Ⅱ cations into a 2D network in complex 1, while 2 shows a 1D structure formed through the two O atoms of SO_4~(2-) ions connecting the molecule. The catalytic properties indicate that complex 1 shows good catalytic activities for the cyanosilylation of 4-chlorobenzaldehyde. In addition, fluorescence property of complex 1 which quenches the excitation intensity in solid state was investigated at room temperature.     

Solid-state Syntheses,Crystal Chemistry and Optical Properties of Two Europium Oxide/sulfide Silicates,Eu_2O(SiO_4) and Eu_5S(SiO_4)_3

Two europium oxide/sulfide silicates, Eu_2O(SiO_4)(1) and Eu5S(SiO 4)3(2), have been synthesized using high-temperature solid-state reactions. 1 crystallizes in the monoclinic space group P21/c with a = 9.1459(7), b = 7.1280(5), c = 6.7655(5) ? and b = 107.611(2)°, belonging to the Gd_2O(SiO_4) structure type; 2 crystallizes in space group P63/m of the hexagonal system with a = 9.786(4) and c = 6.789(3) ?, belonging to the apatite Ca_5Cl(PO_4)_3 structure type. The structure chemistry of related RE_2O(SiO_4) and RE_5S(SiO_4)_3 compounds is also discussed. The optical energy gap of 2 is determined to be 2.05 eV.     

Two New Chlorovanadates: Ba_8Cs_5V_8O_(24)Cl_(13) with [V_8O_(24)] Ring and MgCsV_2O_6Cl with [VO_3]_∞ Chain

Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_(24)Cl_(13)(1) and MgCsV_2O_6Cl(2),were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm(No. 123),with a = 14.801(2),c = 12.341(3) ?,V = 2703.5(8) ?~3,Z = 2,Mr = 3015.56,F(000) = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 2σ(I). 2 crystallizes in a monoclinic space group C2/c(No. 15) with a = 11.128(2),b = 10.540(2),c = 6.9892(14) ?,β = 118.38(3)°,V = 721.2(2) ?~3,Z = 4,M_r = 390.55,F(000) = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm~3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 2σ(I). 1 exhibits a novel 8-membered-ring [V_8O_(24)] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.     

Synthesis,Structure and Polymorphism of a Novel Two-dimensional Cobalt(Ⅱ) Coordination Polymer Constructed from Citrazinate Ligand

The polymeric Co(Ⅱ) complex[Co(Hdhpc)(py)]_n(1)(py = pyridine,H_3dhpc =2,6-dihydroxypyridine-4-carboxyl acid) was prepared and characterized.X-ray diffraction data revealed that the compound crystallizes in dimorphic 1α and 1β forms at room and low temperature,respectively.The former crystallizes in the orthorhombic crystal system,space group Pbcm with a =7.209(1),b = 14.834(3),c = 15.376(3) ?,V= 1644.3(5) ?~3,Z = 4,C_(16)H_(13)CoN_3O_4,M_r = 370.22,D_c= 1.496 g/cm~3,F(000) = 756,μ = 1.068 mm~(-1),R = 0.0633 and wR = 0.1192.While 1β is attributed to the monoclinic space group C2/c with a = 32.102(4),b = 7.022,c = 14.945(2) ?,β = 109.052(5)°,V= 3184.4(6) ?~3,Z= 8,D_c= 1.544 g/cm~3,F(000) = 1512,μ = 1.103 mm~(-1),R = 0.0428 and wR =0.0797.The conformation changes of pyridines between Co-citrazinate planes leading to a reversible single-crystal to single-crystal transformation.The variable temperature magnetic data indicate a weak ferrimagnetism.     

hree Inorganic-organic Composite Polyoxotungstates:Syntheses, Characterization and Structures of [Cu(2,2'-bpy)2]5[α-PW11.5Cu0.5O40]·2H2O,[Co(2,2'-bpy)2(N3)2]4H3[α-PW12O40]·3H2O and [Cu(2,2'-bpy)2(4,4'-bpy)]2[α-GeW12O40]·4H2O

Three new inorganic-organic composite polyoxotungstates [Cu(2,2'- bpy)2]5[α- PW11.5Cu0.5O40]·2H2O 1, [Co(2,2'-bp3)2(N3)2]4H3[α-PW12O40]·3H2O 2 and [Cu(2,2'-bpy)2(4,4'- bpy)]2[α-GeW12O40].4H2O 3 (2,2'-bpy = 2,2'-bipyridine, 4,4'-bpy = 4,4'-bipyridine) have been hydrothermally synthesized and structurally characterized. 1 crystallizes in the orthorhombie space group Pna21 with α = 27.847(3), b = 21.597(2), c = 20.1179(19) A, V = 12099(2) A3, Z = 4, GOF= 1.038, R = 0.0427 and wR = 0.1035; 2 belongs to the triclinic space group P1 with a= 12.31150(10), b = 16.1954(4), c = 19.36290(10) A, α = 99.366(11), β=105.168(8),γ = 111.836(8)°, V = 3309.98(9) A3, Z = 1, GOF = 1.024, R = 0.0739 and wR = 0.2216; and 3 crystallizes in the monoclinic space group P21/n with a = 12.858(4), b = 20.943(6), c = 15.598(5) A, β = 102.338(5)°, V = 4103(2) A3, Z = 2, GOF = 1.026, R = 0.0557 and wR = 0.1316. The common structural features of 1～3 are that their molecular structures all consist of a saturated a-Keggin polyoxoanion and several discrete metal-organic moieties. Intriguingly, 2 and 3 are composed of metal-organic coordination moieties with two mixed ligands.     

Two Co(Ⅱ) Coordination Polymers Based on 3,5-Di(4H-1,2,4-triazole-4-yl)benzoic Acid Ligand: Syntheses,Structures and Magnetic Property

Two Co(Ⅱ) coordination polymers, namely [Co(L)Cl]_n(1) and [Co(L)(CH_3 COO)]_n(2), {HL = 3,5-di(4 H-1,2,4-triazole-4-yl)benzoic acid}, were synthesized under hydrothermal conditions. Compound 1 crystallizes in orthorhombic system, space group Pmma with a = 7.032(5), b = 11.555(8), c = 8.185(5) ?, V = 665.1(7) ?~3, Z = 2, Dc = 1.746 g/cm3~, F(000) = 350, Mr = 349.61, μ = 1.504 mm~(-1), the final R = 0.0568 and w R = 0.1739 for 2312 observed reflections with I 2σ(I). Compound 2 crystallizes in orthorhombic system, space group Pmma with a = 7.7505(17), b = 11.391(3), c = 8.0298(18) ?, V = 708.9(3) ?~3, Z = 2, Dc = 1.748 g/cm~3, F(000) = 378, Mr = 373.20, μ = 1.245 mm-1, the final R = 0.0350 and w R = 0.0873 for 5239 observed reflections with I 2σ(I). Single-crystal X-ray analyses revealed that complexes 1 and 2 exhibit similar 2 D layer structures with uncoordinated carboxyl as dangling arms. The neighboring layers are further connected by these arms, leading to interest 2 D → 3 D polythreading frameworks. Moreover, the magnetic susceptibility study indicates compound 1 exhibits antiferromagnetic behavior.     

Crystal Structures,Luminescent Properties and Hirshfeld Surface Analyses of Zn(Ⅱ) and Cd(Ⅱ) Compounds Based on 1-(2-Carboxyl-phenyl)-3-(pyridin-2-yl)pyrazole

Two compounds,[Zn_2(Hcppp)_2(cppp)_2(H_2O)_2]·2 NO_3·6 H_2O(1) and [Cd(Hcppp)_2Cl_2]· 3H_2O(2)(Hcppp = 1-(2-carboxyl-phenyl)-3-(pyridin-2-yl)pyrazole),are synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group P2_1/c with a = 9.894(2),b = 15.856(3),c = 20.430(4) ?,β = 101.70(3)°,V = 3138.5(11) ?~3,Z = 2,M_r = 1457.94,D_c = 1.543 g/cm~3,F(000) = 1504,R = 0.0278 and wR = 0.0749 for 6157 observed reflections(I 2σ(I)).Compound 2 crystallizes in triclinic system,space group P1 with a = 9.1424(4),b = 11.6427(5),c = 16.1345(7) ?,α = 102.6430(10)°,β = 95.4530(10)°,γ = 104.0060(10)°,V = 1605.94(12) ?~3,Z = 2,M_r = 767.88,D_c = 1.588 g/cm~3,F(000) = 776,R = 0.0307 and wR = 0.0764 for 6275 observed reflections(I 2σ(I)).Compound 1 exhibits a binuclear structure while compound 2 shows a mononuclear structure.In compound 1,two cppp-ligands display the μ_2-kN,N′:k O and two Hcppp ligands show the μ_1-kN,N′ coordination modes.However,two Hcppp ligands connect one Cd(Ⅱ) cation and exhibit the μ_1-kN,N′ binding mode in compound 2.The compounds are both studied using Hirshfeld surface analyses and 2D fingerprint plots.The luminescent properties are also discussed.     

Coordination Modes of Polypyridyl Quinoxaline with Hg(Ⅱ),Pb(Ⅱ),Co(Ⅱ) and Mn(Ⅱ)

The interaction of metal ions(Hg~(2+),Pb~(2+),Co~(2+),Mn~(2+)) with polypyridyl quinoxaline ligand 2,3,6,7,10,ll-hexakis(2-pyridyl)dipyrazino[2,3-f:20,30-h]quinoxaline(HPDQ) was investigated,and four new complexes have been synthesized and characterized.Complex 1 exhibits a 0dimensional dual-core structure,2 is a one-dimensional chain structure based on a dual-core Pb unit,while 3 and 4 show a 0 dimensional single-core structural unit.Complex 1 is of monoclinic system,space group C2/c with a = 19.211(4),b = 23.896(5),c = 12.698(3) ?,β= 120.11(3)°,V= 5043.0(17)?~3,Z = 4,S = 1.053,F(000) = 2976,R~a = 0.0637 and wR~b = 0.1068(I 2σ(I)).Complex 2 adopts triclinic system,space group P1 with a = 10.370(2),b = 12.195(2),c = 21.033(4) ?,α = 80.87(3),β= 81.22(3),γ = 82.38(3)°,V= 2579.3(8) ?~3,Z = 2,S = 1.099,F(000) = 1328,R~a = 0.0609 and wR~b =0.1365(I 2σ(I)).Complex 3 is of monoclinic system,space group Cllc with a = 14.166(3),b =16.621(3),c = 20.248(4) ?,β = 92.18(3)°,V= 4764.0(16) ?~3,Z = 4,S = 1.005,F(000) = 2108,R~a =0.0589 and wR~b = 0.1332(I 2σ(I)).Complex 4 belongs to the monoclinic system,space group C2/c with a = 14.404(3),b = 16.626(3),c = 20.346(4) ?,β = 92.43(3)°,V= 4868.2(17) ?~3,Z = 4,S= 1.068,F(000) = 2108,R~a = 0.0833 and wR~b = 0.1591(I 2σ(I)).Furthermore,the behavior of HPDQ with Hg~(2+),Pb~(2+),Co~(2+) and Mn~(2+) in the solution was also investigated,and the result shows after the metal ions were added respectively,the emission of all solutions shows fluorescence quenching and has a red shift compared with that of the HPDQ ligand.     

Syntheses,Structures and Anticancer Activities of Three 4(3H)-Quinazolinone Cd(Ⅱ) Complexes

The title complexes based on 4(3H)-quinazolinone ligand have been synthesized and characterized by elemental analysis, IR spectrum and single-crystal X-ray diffraction analysis.Complex 1 belongs to the triclinic system, space group P1, with a = 6.5392(3), b = 7.4402(5), c =10.3397(7) ?, α = 83.204(5), β = 75.465(5), γ = 86.075(5)° and V = 483.88(5) ?~3. Complex 2 is of orthorhombic system, space group Pbca, with a = 10.1294(3), b = 7.6747(5), c = 23.8171(15) ? and V = 1849.1(4) ?~3. Complex 3 belongs to the orthorhombic system, space group Pbca, with a =12.7188(2), b = 6.66582(9), c = 25.6987(6) ? and V = 2178.77(5) ?~3. The complex structures are affected by the synthesis conditions.     

Syntheses,Structures and Luminescent Properties of Cd(Ⅱ)/Zn(Ⅱ) Coordination Polymers Based on the Flexible 4-Substituted Bis(1,2,4-triazole) Ligand

Two new cadmium(Ⅱ) and zinc(Ⅱ) coordination polymers, {[Cd(btre)0.5-(mip)(H_2O)_2]·H_2O}n(1) and [Zn(btre)(mip)]n(2), were synthesized at room temperature condition and characterized by IR spectra, elemental analyses, single-crystal and powder X-ray diffractions(btre = 1,2-bis(1,2,4-triazol-4-yl)ethane, H2 mip = 5-methyl-1,3-benzenedicarboxylic acid). Complex 1 belongs to the triclinic system, P1 space group, with a = 8.9830(6), b = 10.0579(6), c = 10.2479(9) ?, α = 98.837(6), β = 115.975(8), γ = 106.370(6)°, V = 756.30(11) ?~3 and Z = 2; complex 2 crystallizes in monoclinic, space group P21/c, with a = 7.0332(3), b = 14.9947(7), c = 15.9689(7) ?, β = 97.1170(10)°, V = 1671.12(13) ?~3 and Z = 4. Compounds 1 and 2 based on the same N/O-donor ligands show different structures. The one-dimensional chains of 1 are further linked by hydrogen bonding and π-π interactions to yield a three-dimensional supramolecular structure. The two-dimensional(6,3) networks of 2 are further extended into a 3D framework via π-π interactions. Thermal stabilities and luminescence of 1 and 2 were investigated.     

Syntheses,Structures and Properties for Zn~Ⅱ Coordination Polymers Based on a Functional 4'-(3-Pyridyl)-3,2':6',3'-terpyridine Ligand

Two new Zn~Ⅱ coordination polymers,namely,[Zn L(o-bdc)]n(1) and [Zn L(mbdc)]_n·n H_2O(2)(L = 4?-(3-pyridyl)-3,2?:6?,3??-terpyridine,H_2(o-bdc) = benzene-1,2-dicarboxylic acid,H_2(m-bdc) = benzene-1,3-dicarboxylic acid),were synthesized by hydrothermal methods. The crystal structures have been determined by single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic C2/c space group,with a = 28.016(2),b = 11.3815(11),c = 19.8071(17) ?,β = 133.961(2)°,V = 4546.2(7) ?3,Z = 8,Mr = 539.83,Dc = 1.577 Mg/m~3,μ = 1.127 mm-1,F(000) = 2208,the final R = 0.0426 and w R = 0.0986 for 2875 observed reflections with I 2σ(I) and displays a 1D coordination chain. While compound 2 crystallizes in monoclinic C2/c space group,with a = 15.6003(14),b = 11.9152(11),c = 26.633(3) ?,β = 94.320(2)°,V = 4936.5(8) ?~3,Z = 4,M_r = 1115.67,Dc = 1.496 Mg/m~3,μ = 1.043 mm~(-1),F(000) = 2272,the final R = 0.0499 and w R = 0.1342 for 2659 observed reflections with I 2σ(I) and shows a classical 3D cds topological network with point symbol of {65.8}. Furthermore,thermal stability and luminescent properties of 1 and 2 have also been investigated.     

Synthesis, Structure and Properties of (n-Bu_4N)_3[Mo_6O_18NNAr(NO_2)_2]

The title compound was synthesized and characterized by means of elemental analysis, IR, DTA-TG and UV. Its single crystal structure was solved by using direct methods. The compound crystallizes in the orthorhombic space group Pmc(?) with lattice parameters: a = 1. 7261(2), b=l. 7537(3), c=2. 4258(3) nm. V=7. 34220 nm3, F(000) = 3648, Z = 4. The structure was refined to conventional discrepancy factors of R=0. 060 for 3176 observed reflections [Ⅰ>3σ/(Ⅰ)]. The anion represents a modification of the well-known [Mo6O19]2- anion, in which a single terminal oxo group is replaced by a 2,4-dinitrophenyl hydrazine ligand while the structure integrity of the hexanuclear framework is maintained.     

Solvothermal Syntheses and Crystal Structures of Two New Nonmetal Borates: C4H10N2·B6O8(OH)2 and (NH3CH2CH2NH3)B5O8(OH)

Two new borate compounds, C4H10N2·B6O8(OH)2 1 and (NH3CH2CH2NH3)B5O8(OH)2, have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, elemental analysis and thermal analysis. Compound 1 crystallizes in the monoclinic system, space group P21/c, with a = 8.3318(17), b = 6.2118(12), c = 12.479(3) (A), β = 108.96(3)°, V = 610.8(2) (A)3, Mr = 313.02, Z = 2, Dc= 1.702 g/cm3, μ = 0.150 mm-1, F(000) = 320, R = 0.0387and wR = 0.0924. Its layered structure is linked by infinite covalently coordinated neutral sheets with 3,20-membered window system, which are built up from alternative B6O8(OH)2 subunits donated by two piperzazine nitrogen donors. 2 crystallizes in monoclinic, space group Cc, with a =6.7207(13), b = 11.481(2), c = 12.564(3) (A),β = 95.25(3)°, V= 965.4(3) (A)3, Mr= 261.18, Z= 4, Dc=1.797 g/cm3, μ = 0.164 mm-1, F(000) = 536, R = 0.0396 and wR = 0.0752. Its oxoborate structure is generated from the sheets of 3,9-membered boron rings bonded diamine molecules through electrostatic and H-bonding interactions to form a two-dimensional layered network.     

Synthesis,Structure and Norbornene Polymerization Catalyzed by o-Benzene Diimine Di-nuclear Palladium(Ⅱ) Complex

The title complex, C20H17N4Pd2Cl3·0.5CH3OH, crystallizes in the triclinic system, space group P1 with a = 9.927(6), b = 11.079(6), c = 11.233(6) ?, α = 73.970(12), β = 85.738(16), γ = 83.300(12)o, V = 1178.1(11)?3, Mr = 648.55, Z = 2, Dc = 1.520 g/cm3, μ = 1.884 mm-1, F(000) = 634, the final R = 0.0460 and wR = 0.1280. This title compound was investigated for the catalytic behavior towards norbornene(NB) vinyl addition polymerization. And the complex exhibits good catalytic activity to catalyze norbornene polymerization using MAO as a cocatalyst.     

Solvothermal Syntheses and Crystal Structures of Two New Nonmetal Borates:C_4H_(10)N_2·B_6O_8(OH)_2 and (NH_3CH_2CH_2NH_3)B_5O_8(OH)

Two new borate compounds,C4H10N2·B6O8(OH)2 1 and (NH3CH2CH2NH3)B5O8-(OH) 2,have been solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction,IR,elemental analysis and thermal analysis. Compound 1 crystallizes in the monoclinic system,space group P21/c,with a=8.3318(17),b=6.2118(12),c=12.479(3) ,β=108.96(3)o,V=610.8(2) 3,Mr=313.02,Z=2,Dc=1.702 g/cm3,μ=0.150 mm-1,F(000)=320,R =0.0387 and wR =0.0924. Its layered structure is linked by infinite covalently coordinated neutral sheets with 3,20-membered window system,which are built up from alternative B6O8(OH)2 subunits donated by two piperzazine nitrogen donors. 2 crystallizes in monoclinic,space group Cc,with a=6.7207(13),b=11.481(2),c=12.564(3) ,β=95.25(3)o,V=965.4(3) 3,Mr=261.18,Z=4,Dc=1.797 g/cm3,μ= 0.164 mm-1,F(000)=536,R=0.0396 and wR=0.0752. Its oxoborate structure is generated from the sheets of 3,9-membered boron rings bonded diamine molecules through electrostatic and H-bonding interactions to form a two-dimensional layered network.     

Syntheses,Structures,and Luminescent Properties of Zinc(Ⅱ) and Silver(Ⅰ) Complexes Based on 1-(4?-Carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole

Two novel coordination compounds, [Zn(CBPP)2(H2O)2]·3H2O(1) and[Ag(CBPP)·2H2O](2)(HCBPP = 1-(4?-carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole), were hydrothermally synthesized and characterized. Compound 1 crystallizes in monoclinic, space group C2 with a = 26.221(4), b = 8.4211(7), c = 14.295(3) ?, β = 114.561(8)o, V = 2705.9(2) ?3, Dc = 1.587 g/cm3, C28H28Cl2N8O9 Zn, Mr = 685.97 F(000) = 1416, μ(Mo Kα) = 0.926 mm-1, Z = 4, R = 0.0287, w R = 0.1076 for 2818 observed reflections(I 2σ(I)), and R = 0.0300, w R = 0.1110 for all data. In 1, each deprotonated CBPP-ligand with a bidentate coordination mode connects two Zn(II) atoms to generate a 1D helical chain along the b axis. The adjacent chains intersect with each other through hinged Zn(II) ions to build up an interesting two-dimensional network. Compound 2 crystallizes in monoclinic, space group P21/n with a = 6.3544(1), b = 11.7195(3), c = 19.3188(4) ?, β = 94.297(2)o, V = 1434.64(5) ?3, Dc = 1.894 g/cm3, C14H13 Ag N4O4, Mr = 409.15 F(000) = 816, μ(Mo Kα) = 11.536 mm-1, Z = 4, R = 0.0456 and w R = 0.1184 for 2402 observed reflections(I 2σ(I)), and R = 0.0517, w R = 0.1275 for all data. In 2, each ligand binds two Ag(I) atoms in a tridentate coordination mode to form an infinite zigzag chain. Their thermal and photoluminescent properties were also investigated.     

Synthesis,Characterization and Luminescent Properties of Two Copper(Ⅰ) Complexes Based on 2,2?-Biquinoline and Phosphorous Ligand

Three new copper(Ⅰ) complexes, namely [Cu(DPEphos)(Biq)]CF_3SO_3(1) and [Cu(PPh_3)_2(Biq)]CF_3SO_3(2) and [Cu(PPh_3)_2(Biq)]ClO_4(3)(DPEphos = bis[2-(diphenylphosp hino)phenyl]ether, PPh_3 = triphenylphosphine and Biq = 2,2?-biquinoline), are synthesized and characterized by IR, ~1H NMR, ~(31) P NMR, fluorescence spectra and terahertz time-domain spectroscopy(THz-TDS). Complex 1 crystallizes in triclinic, space group P1 with a = 12.6997(5), b = 13.2813(5), c = 15.3593(6) ?, α = 80.211(3)°, β = 88.752(3)°, γ = 70.113(3)°, V = 2398.85(15) ?~3, C_(55)H_(41.2)CuF_3N_2O_(4.6)P_2S, Mr = 1018.27, Z = 2, Dc = 1.410 g/cm3, F(000) = 1048, μ = 0.628 mm-1, the final R = 0.0450 and w R = 0.1105 for 9419 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group C2/c with a = 19.9961(7), b = 15.9774(5), c = 17.7908(6) ?, β = 119.758(4)°, V = 4982.8(3) ?~3, C_(56.47)H_(47.88)CuF_3N_2O_(4.47)P_2S, Mr = 1040.54, Z = 4, Dc = 1.387 g/cm~3, F(000) = 2154, μ = 0.606 mm-1, the final R = 0.0430 and w R = 0.1218 for 4897 observed reflections(I 2σ(I)). Complex 3 crystallizes in monoclinic, space group C2/c with a = 19.7534(8), b = 15.0797(5), c = 17.8097(7) ?, β = 116.400(5)°, V = 4751.8(3) ?~3, C_(56)H_(45)ClCuN_3O_4P_2, Mr = 984.88, Z = 4, Dc = 1.377 g/cm~3, F(000) = 2040, μ = 0.635 mm-1, the final R = 0.0731 and w R = 0.2180 for 4670 observed reflections(I 2σ(I)). In the emission spectra, shifts of emission peak are derived from ligand-centered(π-π*) transition.