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 ...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.展开更多
A new 3D Cd(II) coordination polymer, [Cd(Hpidc)]n(1, H3 pidc = 2-(pyrid-2-yl)-1H-imidazole-4,5-dicarboxy acid), has been prepared and characterized by elemental analysis, IR spectra, PXRD, and single-crystal X-ray di...A new 3D Cd(II) coordination polymer, [Cd(Hpidc)]n(1, H3 pidc = 2-(pyrid-2-yl)-1H-imidazole-4,5-dicarboxy acid), has been prepared and characterized by elemental analysis, IR spectra, PXRD, and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group Fdd2 with a = 22.833(9), b = 25.536(9), c = 7.437(3) A, V = 4336(3) A3, Z = 16, Dc = 2.105 Mg·m-3, μ = 2.025 mm-1, F(000) = 2656, and the final R = 0.0261 and w R = 0.0636. The structure determination reveals that 1 exhibits a rare 3D 3-connected lig net with a point symbol of(82·10). In addition, the solid state properties such as thermogravimetric analysis and luminescence of 1 were also studied.展开更多
A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex 2 ∞ [Co- ...A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex 2 ∞ [Co- (phen)(μ-L)3/3]?H2O (H2L = pyrazine-2,3-dicarboxylic acid) has been hydrothermally synthesized, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group P21/n with a = 11.480(2), b = 11.885(2), c = 12.939(3) ?, β = 110.55(3)°, V = 1653.1(6) ?3, Mr = 423.25, Dc = 0.425 g/cm3, Z = 4, R = 0.0361 and wR = 0.1011. The title complex consists of 2D 2 ∞ [Co(phen)(μ-L)3/3] layers and crystal water molecules. Each Co atom is octahedrally coordinated by three N atoms and three O atoms to form 2D 2 ∞ [Co(phen)(μ-L)3/3] polymeric layers. Furthermore, such 2D layers are stacked into 3D supramolecular frameworks via Van der Waals’ intermolecular forces, strong and weak hydrogen-bond interactions. The coordination phen and crystal water molecules are resided into cavities of the frameworks.展开更多
The coordination polymer, [Mn3(bpta)2(bip)2], (H3bpta = biphenyl-3,3',5-tricar- boxylic acid, bip = 2,6-bis(imidazole-1-yl)pyridine), has been synthesized under hydrothermal con- ditions and characterized by ...The coordination polymer, [Mn3(bpta)2(bip)2], (H3bpta = biphenyl-3,3',5-tricar- boxylic acid, bip = 2,6-bis(imidazole-1-yl)pyridine), has been synthesized under hydrothermal con- ditions and characterized by elemental analysis, FT-IR, XRD, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.919(3), b = 9.780(2), c = 20.352(7) A, V = 2344.4(10) A3, Z= 2, C52H32Mn3N10012, Mr = 1153.70, Dc = 1.634 g/cm3, p(MoKa) = 0.876 mm-1, F(000) = 1170, the finalR = 0.0605 and wR = 0.1177. The complex forms a 2D layer with trinuclear Mn(II) units and further assembles into a 3D supramolecular network structure through C-H..'O hydrogen bonding and C-H...π interactions. Moreover, the negative J value indicates the presence of antiferromagnetic coupling between the Mn(II) ions within a trinuclear unit.展开更多
The title Mn(Ⅱ) coordination polymer,poly{[heptaaqua-(μ4-bi-phenyl-3,3?,5,5?-tetracarboxylate)-bimanganese(Ⅱ)] pentahydrate},[Mn_2(bpta)(H_2O)_7]_n·5n H_2O(I),is crystallized from a mixture of bi...The title Mn(Ⅱ) coordination polymer,poly{[heptaaqua-(μ4-bi-phenyl-3,3?,5,5?-tetracarboxylate)-bimanganese(Ⅱ)] pentahydrate},[Mn_2(bpta)(H_2O)_7]_n·5n H_2O(I),is crystallized from a mixture of biphenyl-3,3?,5,5?-tetracarboxylic acid(H_4bpta) and MnCl_2·4H_2O in waterethanol under room temperature. Its asymmetric unit consists of one and two halves of crystallographically independent Mn(Ⅱ) cations,one fully deprotonated H4 bpta ligand,seven coordinated water molecules and five solvent water as guest molecules. In I,each Mn(Ⅱ) atom is octahedrally coordinated by six oxygen atoms from bpta^(4-) anions and coordinated water molecules. In the Mn(Ⅱ) cations,one half Mn(Ⅱ) ion of them located at a 2-fold axis generating a trinuclear [Mn_3(H_2O)_2(RCOO)_2] linker by μ1,1-O(water) and μ1,3-O,O?(carboxylate) bridges and another half Mn(Ⅱ) ion with an inversion is a mononuclear linker. These neighbouring trinuclear and mononuclear Mn(Ⅱ) cations are linked together by biphenyl-3,3?,5,5?-tetracarboxylates to form a three-dimensional framework with a(42.84) topology of a(4,4)-connected net,in which the positions of the trinuclear [Mn_3(H_2O)_2(R-COO)_2] linker as a 4-connector linking four bpta^(4-) ligands in I reproduce an eagle-shaped arrangement. The polymeric structure exhibits a water channel with an accessible void of 797.1 ?~3,amounting to 15.7% of the total unit-cell volume. Each of the cavities in the network is occupied by solvent water molecules.展开更多
A three-dimensional coordination polymer [Mn2(μ1.3-N3)4(μ-PP)2]n (PP = 3-(pyrazin-2-yloxy)-pyridine) has been synthesized with 3-(pyrazin-2-yloxy)-pyridine and azide anion as mixed bridge ligand, and its c...A three-dimensional coordination polymer [Mn2(μ1.3-N3)4(μ-PP)2]n (PP = 3-(pyrazin-2-yloxy)-pyridine) has been synthesized with 3-(pyrazin-2-yloxy)-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data: triclinic system, space group P1, with a = 6.794(4), b = 9.885(6), c = 9.947(6) A, α = 64.170(6), β= 84.190(8), γ= 85.319(8)°, V = 597.7(6)A^3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm^3, F(000) = 314 and μ = 1.117 mm^-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn(Ⅱ) ions connect into a two-dimensional sheet on the ab plane, then 3-(pyrazin-2-yloxy)-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along展开更多
Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)tereph...Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3^(10).5.6~4)4(3^(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.展开更多
One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxyli...One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(Hbtc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.展开更多
The coordination polymer of [Mn(m-CPOAH)2(H2O)2]n (m-CPOAH– = 3-carboxyl- phenoxyacetate) has been synthesized and characterized by elemental analyses, IR, TG and single- crystal X-ray diffraction. The title complex ...The coordination polymer of [Mn(m-CPOAH)2(H2O)2]n (m-CPOAH– = 3-carboxyl- phenoxyacetate) has been synthesized and characterized by elemental analyses, IR, TG and single- crystal X-ray diffraction. The title complex crystallizes in the triclinic system, space group P1 with a = 4.7013(9), b = 5.6822(11), c = 17.758(4) ?, α = 87.39(3), β = 85.39(3), γ = 85.76(3)o, V = 471.18(17) ?3, Z = 1, Mr = 481.26, Dc = 1.696 g/cm3, μ = 0.770 mm-1, F(000) = 247, R = 0.0385 and wR = 0.1015. The Mn(II) atom assumes a distorted octahedral geometry, involving four carboxyl oxygen atoms from different m-CPOAH– ligands and two coordinated water molecules. The Mn(II) atoms are linked by the m-CPOAH– ligand to form a one-dimensional chain structure along the a axis. The shortest Mn…Mn separation within the polymer is 7.401(4) ?. A three- dimensional supramolecular network is constructed by O–H…O hydrogen bonding interactions.展开更多
The coordination polymer,[Mn3(L) 2(adip) 3]·2H2O(L = 2-(4-fluorophenyl) -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid) ,has been synthesized under hydro-thermal conditions and character...The coordination polymer,[Mn3(L) 2(adip) 3]·2H2O(L = 2-(4-fluorophenyl) -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid) ,has been synthesized under hydro-thermal conditions and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1^- with a = 8.4085(11) ,b = 11.1273(14) ,c = 14.5758(18) ,α = 78.528(2) ,β = 75.425(2) ,γ = 78.143(2) °,V = 1276.0(3) A^3,Z = 1,C56H50F2Mn3N8O14,Mr = 1261.86,Dc = 1.642 g/cm^3,F(000) = 647,μ(MoKa) = 0.819 mm^-1,R = 0.0446 and wR = 0.1008. The backbones of the two types of adip dianions link the neighboring trinuclear Mn(Ⅱ) clusters to yield a two-dimensional layer structure. The large conjugated L ligands are located on both sides of the two-dimensional layers. Additionally,the O-H···O,O-H···N and N-H···O hydrogen bonds further stabilize the structure.展开更多
A novel two-dimensional coordination polymer [Ba2(phen)4(tp)2]n (phen = 1,10- phenanthroline, tp = terephthalic acid) has been synthesized with tp as bridge ligands and structurally determined by X-ray crystallo...A novel two-dimensional coordination polymer [Ba2(phen)4(tp)2]n (phen = 1,10- phenanthroline, tp = terephthalic acid) has been synthesized with tp as bridge ligands and structurally determined by X-ray crystallography. The crystal belongs to the monoclinic system, space group C2/c, with a = 18.877(4), b = 18.489(4), c = 15.658(3) A, β = 103.61(3)°, V= 5311.5(19)A^3, C32H20O4N4Ba, Mr = 661.86, Z= 8, F(000) = 2624,μ= 1.542 mm^-1, Dc= 1.655 g/cm^3, the final R = 0.0228 and wR = 0.0554 for 6063 observed reflections (I 〉 2σ(I)). The structural analysis shows that each tp ligand bridges barium atoms to form a two-dimensional infinite layer. There are aromatic π-π stacking interactions between neighboring layers, and aromatic π-π interactions further extend such layers into a three-dimensional supramolecular framework.展开更多
A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structur...A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603(7), b = 8.6907(4), c = 8.4745(3)A, β = 101.1110(11)°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25(9)A3, Z = 4, Dc = 2.628 g/cm^3, F(000) = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead(II) cation, one(5-chloro-quinolin-8-yloxy)acetate(L) ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit(SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1)A. The fluorescence emission peak of complex 1 appears near 407 nm.展开更多
A new coordination polymer [Ni(L)(m-bix)(H2O)]n (1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis(imidazol-1-ylmethyl)-benzene) has been synthesized by the hydrothermal method and characterized by IR, element...A new coordination polymer [Ni(L)(m-bix)(H2O)]n (1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis(imidazol-1-ylmethyl)-benzene) has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638(3), b = 10.2319(3), c = 13.2463(4) ?, α = 80.1710(10), β = 83.671(2), γ = 70.3790(10)o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85(6) ?3, Dc = 1.746 g/cm3, F(000) = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ(I). In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric (TG) and differential thermal analysis (DTA).展开更多
The title compound [Cu(HSSA)(py)3H2O]n (H3SSA = 5-sulfosalicylic acid, py = pyridine) I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemen...The title compound [Cu(HSSA)(py)3H2O]n (H3SSA = 5-sulfosalicylic acid, py = pyridine) I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemental analyses, thermogravimetric analyses, IR and UV-visible spectroscopy. The crystal belongs to the monoclinic system, space group P21/c with a = 9.4564(10), b = 18.2679(19), c = 15.7284(12) A,β= 126.045(4)°, V= 2196.9(4)A^3, Z= 4, Dc = 1.618 g/cm^3, Mr = 535.02,μ = 1.141 mm^-1, F(000) = 1100, 2(MoKα) = 0.71073 A, the final R = 0.0429 and wR = 0.1044 for all observed reflections. In the structure, every two Cu(II) atoms are bridged by a bivalent 5-sulfosalicylic anion to form a 1D chain-like coordination polymer. Lattice waters between chains link them to form 2D layers which are further linked by C-H…O hydrogen bonds to form a three-dimensional supramolecular network.展开更多
A new 1D chain copper coordination polymer [CuE(H2L)2(C10HsN2)(HEO)2]n'3n(H20) with 2,3-pyridinedi carboxylic acid (H2L) and 2,2'-bipyridine (2,2'-bipy) as ligands has been synthesized in the mixed etha...A new 1D chain copper coordination polymer [CuE(H2L)2(C10HsN2)(HEO)2]n'3n(H20) with 2,3-pyridinedi carboxylic acid (H2L) and 2,2'-bipyridine (2,2'-bipy) as ligands has been synthesized in the mixed ethanol and water solvents. Crystal data for this complex are as follows: monoclinic, space group P2Jc, a = 7.7713(7), b = 27.478(3), c = 13.2621(13)/1,, fl = 100.6940(10), V= 2782.8(5) A3, Dc = 1.722 g/cm3, Z = 4, p = 1.61 mm-1, F(000) = 1472, the final R = 0.0363 and wR = 0.0933. In the crystal structure, the whole molecule consists of two cooper ions, two H2L, one 2,2"-bipy molecule and six water molecules. Each central copper ion is coordinated with three oxygen atoms from two H2L and one water molecule, two nitrogen atoms from one 2,2'-bipy molecule and two H2L, giving a distorted tetragonal pyramidal geometry. Thermal stability properties of the complex were investigated.展开更多
A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2...A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2-aminoethanesulfonic acid with a 1:2 mole ratio and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Crystal structural analysis reveals it crystallizes in monoclinic, space group P21/c with a=8.672(4), b=6.523(3), c=9.134(5) , β=115.441(5)°, V=466.6(4) 3, Mr=313.65, Z=2, Dc=2.232 Mg·m-3, F(000) =320, μ(MoKα)=3.091 mm-1, the final R=0.0358 and wR=0.0919 for 2026 observed reflections with Ⅰ 〉 2σ(Ⅰ). In the structure, each zinc(Ⅱ) ion is coordinated in a slightly distorted octahedron, and each μ3-TAU– acts as a bridge to bond three neighboring Zn(Ⅱ) ions to form an infinite 2D network structure.展开更多
A three-dimensional cobalt coordination polymer [Co(IMPAA)2]n(1, HIMPAA =(2E)-3-[4-(1H-imidazol-1-ylmethyl)phenyl]acrylic acid) was synthesized with ozagrel and structurally characterized by element analysis, ...A three-dimensional cobalt coordination polymer [Co(IMPAA)2]n(1, HIMPAA =(2E)-3-[4-(1H-imidazol-1-ylmethyl)phenyl]acrylic acid) was synthesized with ozagrel and structurally characterized by element analysis, IR, PXRD, TGA and X-ray diffraction. Complex 1 is of monoclinic system, space group P21 with a = 5.136(4), b = 25.577(19), c = 8.174(6) A, V = 1078.6(14) A3, Mr = 513.41, Z = 2, Dc = 1.581 g/cm3, F(000) = 686, μ = 0.840 mm-1, S = 1.119, Rint = 0.0637 and w R = 0.1456. In complex 1, four IMPAA- and four Co(II) ions form a S-shaped 52-membered macrocycle [Co4(IMPAA)4]4+. Two carboxlate oxygen atoms link the macrocycles to form a one-dimensional chain. IMPAA- ligands bridge one-dimensional chains to yield a novel three-dimensional metal-organic framework(MOFs). The complex is stable up to 350 ℃.展开更多
Two new cadmium(II)-thiocyanato coordination polymers with 4,4'-dimethyl-2,2'-bipyridine(4,4'-dm-2,2'-bpy) and 4,4'-dimethoxy-2,2'-bipyridine(4,4'-dmo-2,2'-bpy) as chelating ligands were synthesized and ...Two new cadmium(II)-thiocyanato coordination polymers with 4,4'-dimethyl-2,2'-bipyridine(4,4'-dm-2,2'-bpy) and 4,4'-dimethoxy-2,2'-bipyridine(4,4'-dmo-2,2'-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy and X-ray crystallography. Thermal properties were also studied as well. These complexes have formed as [Cd(4,4'-dm-2,2'-bpy)(NCS)2]n(1) and [Cd(4,4'-dmo-2,2'-bpy)(NCS)2]n(2). The coordination numbers of CdII in 1 and 2 are six(Cd N4S2). Direction of bridging of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.展开更多
The hydrothermal reaction of Cd(OAc)2·2H2O, 4,4'-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid (H4L) yields a three-dimensional (3D) coordination porous framework [Cd2LI(4,4'-bpy)1.5(H2O)2]n·2...The hydrothermal reaction of Cd(OAc)2·2H2O, 4,4'-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid (H4L) yields a three-dimensional (3D) coordination porous framework [Cd2LI(4,4'-bpy)1.5(H2O)2]n·2nH2O, which was characterized by single-crystal X-ray diffraction (MoKα radiation, λ = 0.71073), elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951(3), b = 11.6618(12), c = 20.046(2) A, β = 114.863(2)o, V = 5504.4(10)A^3, Z = 8, Dc = 1.900 g/cm^3, Mr = 787.30, μ = 1.615 mm^-1, F(000) = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4'-bpy ligands. The 4,4'-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I (e,a,a,e) conformation and acts as a pentadentate ligand to connect five Cd(Ⅱ) atoms via the carboxylate groups in different coordination modes.展开更多
A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]?H2O}n (4-CPOA2– = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elem...A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]?H2O}n (4-CPOA2– = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The complex C19H22N2O10Cu crystallizes in triclinic system, space group P1 with a = 7.672(2), b = 18.490(4), c = 13.271(3) ?, α = 72.81(3), β = 84.64(3), γ = 87.28(3)o, V = 1026.3(4) ?3, Z = 2, Mr = 501.94, Dc = 1.624 g/cm3, μ = 1.126 mm–1, F(000) = 518, the final R = 0.0580 and wR = 0.1310 for 3364 observed reflections with I > 2σ(I). Each Cu(II) ion is coordinated with two different carboxyl O atoms from two 4-carboxyphenoxyacetate groups, two N atoms from two 3-PyOH ligands and two water molecules, residing in a distorted octahedral environment. Adjacent Cu(II) atoms are linked by bi-monodentate 4-CPOA2– groups into an one-dimensional chain along the b axis. A three-dimensional supramolecular network is constructed by O–H…O hydrogen bonds.展开更多
基金This work was supported by the National Natural Science Foundation of China (No. 20231020)
文摘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.
基金Supported by the NSRF of Hubei Provincial Education Office of China(Q20141201)the SRASF of Yichang of Hubei Province(A13-302a-02)
文摘A new 3D Cd(II) coordination polymer, [Cd(Hpidc)]n(1, H3 pidc = 2-(pyrid-2-yl)-1H-imidazole-4,5-dicarboxy acid), has been prepared and characterized by elemental analysis, IR spectra, PXRD, and single-crystal X-ray diffraction. Compound 1 crystallizes in orthorhombic, space group Fdd2 with a = 22.833(9), b = 25.536(9), c = 7.437(3) A, V = 4336(3) A3, Z = 16, Dc = 2.105 Mg·m-3, μ = 2.025 mm-1, F(000) = 2656, and the final R = 0.0261 and w R = 0.0636. The structure determination reveals that 1 exhibits a rare 3D 3-connected lig net with a point symbol of(82·10). In addition, the solid state properties such as thermogravimetric analysis and luminescence of 1 were also studied.
基金This work was supported by the Science and Technology Bureau of Jinhua City (No 2003-01-179)
文摘A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex 2 ∞ [Co- (phen)(μ-L)3/3]?H2O (H2L = pyrazine-2,3-dicarboxylic acid) has been hydrothermally synthesized, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group P21/n with a = 11.480(2), b = 11.885(2), c = 12.939(3) ?, β = 110.55(3)°, V = 1653.1(6) ?3, Mr = 423.25, Dc = 0.425 g/cm3, Z = 4, R = 0.0361 and wR = 0.1011. The title complex consists of 2D 2 ∞ [Co(phen)(μ-L)3/3] layers and crystal water molecules. Each Co atom is octahedrally coordinated by three N atoms and three O atoms to form 2D 2 ∞ [Co(phen)(μ-L)3/3] polymeric layers. Furthermore, such 2D layers are stacked into 3D supramolecular frameworks via Van der Waals’ intermolecular forces, strong and weak hydrogen-bond interactions. The coordination phen and crystal water molecules are resided into cavities of the frameworks.
基金conducted in the framework of a project sponsored by the National Natural Science Foundation of China(No.21071100)Liaoning Baiqianwan Talents Program and the LNET(LJQ2011038)
文摘The coordination polymer, [Mn3(bpta)2(bip)2], (H3bpta = biphenyl-3,3',5-tricar- boxylic acid, bip = 2,6-bis(imidazole-1-yl)pyridine), has been synthesized under hydrothermal con- ditions and characterized by elemental analysis, FT-IR, XRD, TGA and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 14.919(3), b = 9.780(2), c = 20.352(7) A, V = 2344.4(10) A3, Z= 2, C52H32Mn3N10012, Mr = 1153.70, Dc = 1.634 g/cm3, p(MoKa) = 0.876 mm-1, F(000) = 1170, the finalR = 0.0605 and wR = 0.1177. The complex forms a 2D layer with trinuclear Mn(II) units and further assembles into a 3D supramolecular network structure through C-H..'O hydrogen bonding and C-H...π interactions. Moreover, the negative J value indicates the presence of antiferromagnetic coupling between the Mn(II) ions within a trinuclear unit.
基金supported by the National Natural Science Foundation of China(No.21571118)
文摘The title Mn(Ⅱ) coordination polymer,poly{[heptaaqua-(μ4-bi-phenyl-3,3?,5,5?-tetracarboxylate)-bimanganese(Ⅱ)] pentahydrate},[Mn_2(bpta)(H_2O)_7]_n·5n H_2O(I),is crystallized from a mixture of biphenyl-3,3?,5,5?-tetracarboxylic acid(H_4bpta) and MnCl_2·4H_2O in waterethanol under room temperature. Its asymmetric unit consists of one and two halves of crystallographically independent Mn(Ⅱ) cations,one fully deprotonated H4 bpta ligand,seven coordinated water molecules and five solvent water as guest molecules. In I,each Mn(Ⅱ) atom is octahedrally coordinated by six oxygen atoms from bpta^(4-) anions and coordinated water molecules. In the Mn(Ⅱ) cations,one half Mn(Ⅱ) ion of them located at a 2-fold axis generating a trinuclear [Mn_3(H_2O)_2(RCOO)_2] linker by μ1,1-O(water) and μ1,3-O,O?(carboxylate) bridges and another half Mn(Ⅱ) ion with an inversion is a mononuclear linker. These neighbouring trinuclear and mononuclear Mn(Ⅱ) cations are linked together by biphenyl-3,3?,5,5?-tetracarboxylates to form a three-dimensional framework with a(42.84) topology of a(4,4)-connected net,in which the positions of the trinuclear [Mn_3(H_2O)_2(R-COO)_2] linker as a 4-connector linking four bpta^(4-) ligands in I reproduce an eagle-shaped arrangement. The polymeric structure exhibits a water channel with an accessible void of 797.1 ?~3,amounting to 15.7% of the total unit-cell volume. Each of the cavities in the network is occupied by solvent water molecules.
基金Supported by the National Natural Science Foundation of China (No. 20271043)Natural Science Foundation of Shandong Province (Y2007B26)
文摘A three-dimensional coordination polymer [Mn2(μ1.3-N3)4(μ-PP)2]n (PP = 3-(pyrazin-2-yloxy)-pyridine) has been synthesized with 3-(pyrazin-2-yloxy)-pyridine and azide anion as mixed bridge ligand, and its crystal structure was determined by X-ray crystallography. The crystal data: triclinic system, space group P1, with a = 6.794(4), b = 9.885(6), c = 9.947(6) A, α = 64.170(6), β= 84.190(8), γ= 85.319(8)°, V = 597.7(6)A^3, Z = 1, C18H14Mn2N18O2, Mr = 624.35, Dc = 1.735 g/cm^3, F(000) = 314 and μ = 1.117 mm^-1. In the crystal, the azide anion acts as a bridge ligand and makes adjacent Mn(Ⅱ) ions connect into a two-dimensional sheet on the ab plane, then 3-(pyrazin-2-yloxy)-pyridine serves as a bidentate bridge ligand to connect neighboring sheets along
基金Supported by Guangdong Province Higher Vocational Colleges&Schools Pearl River Scholar Funded Scheme(2015)the Natural Science Foundation of Guangdong Province(No.2016A030313761)+3 种基金Science and Technology Planning Project of Guangzhou(No.201510010170)the Pearl River Scholar Foundation of Guangdong Industry Polytechnic(No.RC2015-001)the Opening Foundation of MOE Key Laboratory of Bioinorganic and Synthetic Chemistry School of Chemistry Sun Yat-Sen University(2016)National Natural Science Foundation of China(No.11272093)
文摘Two coordination polymers, namely {[Mn(HL_1)(phen)]·4H_2O}_n(1) and [Co_2(HL_2)_2(H_2O)_2]_n(2) have been constructed hydrothermally using H_3L_1 and H_3L_2(H_3L_1 = 2-(5-carboxypyridin-2-yl)terephthalic acid, H_3L_2 = 2-(4-carboxypyridin-3-yl)terephthalic acid), phen, MnCl_2×4H_2O and CoCl_2×6H_2O. The products were isolated as stable crystalline solids and were characterized by IR spectroscopy, elemental, thermogravimetric(TGA), powder(PXRD) and single-crystal X-ray diffraction analyses. Compound 1 features a 3D framework structure, which was topologically classified as a trinodal 4,6,6-connected net with the unique topology defined by the point symbol of(3^(10).5.6~4)4(3^(10).6.7~4)2(5.6~2.8~2.9). Compound 2 possesses a 2D metal-organic layer, which was topologically classified as a binodal 4,4-connected layer defined by the point symbol of(4~3.6~2.8). The layers are further extended into a 3D supramolecular framework via hydrogen bonds. The magnetic properties for both compounds were also investigated, indicating antiferromagnetic interactions between the adjacent metal ions.
基金Supported by the Natural Science Foundation of Guangxi Province(No.2017GXNSFAA198268)the Foundation of Guangxi Key Laboratory of Electrochemical and Magneto-chemical Functional Materials(EMFM20161102)the National Natural Science Foundation of China(No.61765005)
文摘One new coordination polymer, [Mn(Hbtc)(bpy)(HO)]1, was synthesized by the reaction of manganese(Ⅱ) salt under pH-controlled hydrothermal conditions with unsymmetrical polycarboxylic acid of 1,2,4-benzenetricarboxylic acid(Hbtc) and 2,2?-bipyridine(bpy). The structure of complex 1 was characterized by single-crystal X-ray diffraction, IR spectra, powder X-ray analysis, thermal gravimetric analysis(TGA), UV-Vis spectrometry, photoluminescence and magnetic susceptibility. Complex 1 is a one-dimensional(1D) polymeric single-chain structure. Photoluminescence property is quite similar to the bpy ligand. Magnetic susceptibility measurement indicates that 1 shows a weak ferromagnetic coupling between the Mn~Ⅱ ions.
基金This work was supported by the National Natural Science Foundation of China (No. 20101003), and the Scientific Fund of Remarkable Teachers of Heilongjiang Province (No. 1054G036)
文摘The coordination polymer of [Mn(m-CPOAH)2(H2O)2]n (m-CPOAH– = 3-carboxyl- phenoxyacetate) has been synthesized and characterized by elemental analyses, IR, TG and single- crystal X-ray diffraction. The title complex crystallizes in the triclinic system, space group P1 with a = 4.7013(9), b = 5.6822(11), c = 17.758(4) ?, α = 87.39(3), β = 85.39(3), γ = 85.76(3)o, V = 471.18(17) ?3, Z = 1, Mr = 481.26, Dc = 1.696 g/cm3, μ = 0.770 mm-1, F(000) = 247, R = 0.0385 and wR = 0.1015. The Mn(II) atom assumes a distorted octahedral geometry, involving four carboxyl oxygen atoms from different m-CPOAH– ligands and two coordinated water molecules. The Mn(II) atoms are linked by the m-CPOAH– ligand to form a one-dimensional chain structure along the a axis. The shortest Mn…Mn separation within the polymer is 7.401(4) ?. A three- dimensional supramolecular network is constructed by O–H…O hydrogen bonding interactions.
基金Supported by the Institute Foundation of Siping City (No.2009011)
文摘The coordination polymer,[Mn3(L) 2(adip) 3]·2H2O(L = 2-(4-fluorophenyl) -1H-imidazo[4,5-f] [1,10]phenanthroline and H2adip = adipic acid) ,has been synthesized under hydro-thermal conditions and characterized by elemental analysis,IR and single-crystal X-ray diffraction. It crystallizes in triclinic,space group P1^- with a = 8.4085(11) ,b = 11.1273(14) ,c = 14.5758(18) ,α = 78.528(2) ,β = 75.425(2) ,γ = 78.143(2) °,V = 1276.0(3) A^3,Z = 1,C56H50F2Mn3N8O14,Mr = 1261.86,Dc = 1.642 g/cm^3,F(000) = 647,μ(MoKa) = 0.819 mm^-1,R = 0.0446 and wR = 0.1008. The backbones of the two types of adip dianions link the neighboring trinuclear Mn(Ⅱ) clusters to yield a two-dimensional layer structure. The large conjugated L ligands are located on both sides of the two-dimensional layers. Additionally,the O-H···O,O-H···N and N-H···O hydrogen bonds further stabilize the structure.
基金supported by the grants from Program for New Century Excellent Talents in University (NCET-04-0987)Specialized Research Fund for the Doctoral Program of Higher Education (No 200507550033)
文摘A novel two-dimensional coordination polymer [Ba2(phen)4(tp)2]n (phen = 1,10- phenanthroline, tp = terephthalic acid) has been synthesized with tp as bridge ligands and structurally determined by X-ray crystallography. The crystal belongs to the monoclinic system, space group C2/c, with a = 18.877(4), b = 18.489(4), c = 15.658(3) A, β = 103.61(3)°, V= 5311.5(19)A^3, C32H20O4N4Ba, Mr = 661.86, Z= 8, F(000) = 2624,μ= 1.542 mm^-1, Dc= 1.655 g/cm^3, the final R = 0.0228 and wR = 0.0554 for 6063 observed reflections (I 〉 2σ(I)). The structural analysis shows that each tp ligand bridges barium atoms to form a two-dimensional infinite layer. There are aromatic π-π stacking interactions between neighboring layers, and aromatic π-π interactions further extend such layers into a three-dimensional supramolecular framework.
基金Supported by Key Laboratory of Organic Synthesis of Jiangsu Province(KJS1308)
文摘A novel two-dimensional lead(II) coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand(5-chloro-quinolin-8-yloxy)acetic acid(HL) with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603(7), b = 8.6907(4), c = 8.4745(3)A, β = 101.1110(11)°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25(9)A3, Z = 4, Dc = 2.628 g/cm^3, F(000) = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead(II) cation, one(5-chloro-quinolin-8-yloxy)acetate(L) ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit(SBU) and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079(1)A. The fluorescence emission peak of complex 1 appears near 407 nm.
基金supported by the International Technology Cooperation Project of Science and Technology Department of Henan Province(No.124300510050)
文摘A new coordination polymer [Ni(L)(m-bix)(H2O)]n (1, H2L = 5-iodo-isophthalic acid, m-bix=1,3-bis(imidazol-1-ylmethyl)-benzene) has been synthesized by the hydrothermal method and characterized by IR, elemental analysis, powder XRD and single-crystal X-ray analysis. The crystal is of triclinic, space group Pī with a = 9.1638(3), b = 10.2319(3), c = 13.2463(4) ?, α = 80.1710(10), β = 83.671(2), γ = 70.3790(10)o,C22H19NiIN4O5, Mr = 605.02, V = 1150.85(6) ?3, Dc = 1.746 g/cm3, F(000) = 600, μ = 2.225 mm-1, S = 1.045 and Z = 2. The final R = 0.0388 and wR = 0.1257 for 5089 observed reflections with I 〉 2σ(I). In the title complex, the M and P layers are arranged alternately to give a double-layer structure by the symmetry related hydrogen bonds, and these double-layers are further joined together to achieve a 2D supramolecular architecture through I···π interaction involving iodine atoms and imidazole rings. The thermal stability of the title complex was studied by thermal gravimetric (TG) and differential thermal analysis (DTA).
基金supported by the Project for Innovation Team of Liaoning Province (No. 2007T052)Liaoning Provincial Key Laboratory (No. 2008S104)Startup Project of Doctor of Liaoning University
文摘The title compound [Cu(HSSA)(py)3H2O]n (H3SSA = 5-sulfosalicylic acid, py = pyridine) I has been synthesized and structurally determined by single-crystal X-ray diffraction. I was further characterized by elemental analyses, thermogravimetric analyses, IR and UV-visible spectroscopy. The crystal belongs to the monoclinic system, space group P21/c with a = 9.4564(10), b = 18.2679(19), c = 15.7284(12) A,β= 126.045(4)°, V= 2196.9(4)A^3, Z= 4, Dc = 1.618 g/cm^3, Mr = 535.02,μ = 1.141 mm^-1, F(000) = 1100, 2(MoKα) = 0.71073 A, the final R = 0.0429 and wR = 0.1044 for all observed reflections. In the structure, every two Cu(II) atoms are bridged by a bivalent 5-sulfosalicylic anion to form a 1D chain-like coordination polymer. Lattice waters between chains link them to form 2D layers which are further linked by C-H…O hydrogen bonds to form a three-dimensional supramolecular network.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)+1 种基金Science and Technology Plan of Hunan Province(2012GK3031,2012WK3029)the Construct Program of the Key Discipline in Hunan Province
文摘A new 1D chain copper coordination polymer [CuE(H2L)2(C10HsN2)(HEO)2]n'3n(H20) with 2,3-pyridinedi carboxylic acid (H2L) and 2,2'-bipyridine (2,2'-bipy) as ligands has been synthesized in the mixed ethanol and water solvents. Crystal data for this complex are as follows: monoclinic, space group P2Jc, a = 7.7713(7), b = 27.478(3), c = 13.2621(13)/1,, fl = 100.6940(10), V= 2782.8(5) A3, Dc = 1.722 g/cm3, Z = 4, p = 1.61 mm-1, F(000) = 1472, the final R = 0.0363 and wR = 0.0933. In the crystal structure, the whole molecule consists of two cooper ions, two H2L, one 2,2"-bipy molecule and six water molecules. Each central copper ion is coordinated with three oxygen atoms from two H2L and one water molecule, two nitrogen atoms from one 2,2'-bipy molecule and two H2L, giving a distorted tetragonal pyramidal geometry. Thermal stability properties of the complex were investigated.
基金Supported by the foundation for Dr of Jianggangshan University (JZ10044)the NSF of Guangxi Province (No. 0832090)the NSF of the Education Committee of Guangxi Province (No. 201012MS203)
文摘A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2-aminoethanesulfonic acid with a 1:2 mole ratio and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Crystal structural analysis reveals it crystallizes in monoclinic, space group P21/c with a=8.672(4), b=6.523(3), c=9.134(5) , β=115.441(5)°, V=466.6(4) 3, Mr=313.65, Z=2, Dc=2.232 Mg·m-3, F(000) =320, μ(MoKα)=3.091 mm-1, the final R=0.0358 and wR=0.0919 for 2026 observed reflections with Ⅰ 〉 2σ(Ⅰ). In the structure, each zinc(Ⅱ) ion is coordinated in a slightly distorted octahedron, and each μ3-TAU– acts as a bridge to bond three neighboring Zn(Ⅱ) ions to form an infinite 2D network structure.
基金supported by the National Natural Foundation of China(No.31060213)the Research Foundation of Educational Department of Jiangxi Province(No.GJJ13261)
文摘A three-dimensional cobalt coordination polymer [Co(IMPAA)2]n(1, HIMPAA =(2E)-3-[4-(1H-imidazol-1-ylmethyl)phenyl]acrylic acid) was synthesized with ozagrel and structurally characterized by element analysis, IR, PXRD, TGA and X-ray diffraction. Complex 1 is of monoclinic system, space group P21 with a = 5.136(4), b = 25.577(19), c = 8.174(6) A, V = 1078.6(14) A3, Mr = 513.41, Z = 2, Dc = 1.581 g/cm3, F(000) = 686, μ = 0.840 mm-1, S = 1.119, Rint = 0.0637 and w R = 0.1456. In complex 1, four IMPAA- and four Co(II) ions form a S-shaped 52-membered macrocycle [Co4(IMPAA)4]4+. Two carboxlate oxygen atoms link the macrocycles to form a one-dimensional chain. IMPAA- ligands bridge one-dimensional chains to yield a novel three-dimensional metal-organic framework(MOFs). The complex is stable up to 350 ℃.
基金supported by Islamic Azad University Maku Branch
文摘Two new cadmium(II)-thiocyanato coordination polymers with 4,4'-dimethyl-2,2'-bipyridine(4,4'-dm-2,2'-bpy) and 4,4'-dimethoxy-2,2'-bipyridine(4,4'-dmo-2,2'-bpy) as chelating ligands were synthesized and characterized by elemental analysis, IR and 1H NMR spectroscopy and X-ray crystallography. Thermal properties were also studied as well. These complexes have formed as [Cd(4,4'-dm-2,2'-bpy)(NCS)2]n(1) and [Cd(4,4'-dmo-2,2'-bpy)(NCS)2]n(2). The coordination numbers of CdII in 1 and 2 are six(Cd N4S2). Direction of bridging of thiocyanato anions in 1 and 2 created one- and two-dimensional coordination polymers, respectively. The supramolecular features in these complexes were guided and controlled by weak directional intermolecular interactions.
基金Supported by the National Natural Science Foundation of China (No. 20901018)the Natural Science Foundation of Guangdong Province (No. 9451009101003177)
文摘The hydrothermal reaction of Cd(OAc)2·2H2O, 4,4'-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid (H4L) yields a three-dimensional (3D) coordination porous framework [Cd2LI(4,4'-bpy)1.5(H2O)2]n·2nH2O, which was characterized by single-crystal X-ray diffraction (MoKα radiation, λ = 0.71073), elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951(3), b = 11.6618(12), c = 20.046(2) A, β = 114.863(2)o, V = 5504.4(10)A^3, Z = 8, Dc = 1.900 g/cm^3, Mr = 787.30, μ = 1.615 mm^-1, F(000) = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4'-bpy ligands. The 4,4'-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I (e,a,a,e) conformation and acts as a pentadentate ligand to connect five Cd(Ⅱ) atoms via the carboxylate groups in different coordination modes.
基金This work was supported by the National Natural Science Foundation of China (No. 20101003), Natural Science Foundation of Heilongjiang Province (No. B0007) and Outstanding Teacher Foundation of Heilongjiang Province (1054G036)
文摘A novel one-dimensional copper(II) coordination polymer of {[Cu(4-CPOA)(3- PyOH)2(H2O)2]?H2O}n (4-CPOA2– = 4-carboxyphenoxyacetate dianion, 3-PyOH = 3-hydroxypyri- dine) has been synthesized and characterized by elemental analyses, IR spectra and single-crystal X-ray diffraction. The complex C19H22N2O10Cu crystallizes in triclinic system, space group P1 with a = 7.672(2), b = 18.490(4), c = 13.271(3) ?, α = 72.81(3), β = 84.64(3), γ = 87.28(3)o, V = 1026.3(4) ?3, Z = 2, Mr = 501.94, Dc = 1.624 g/cm3, μ = 1.126 mm–1, F(000) = 518, the final R = 0.0580 and wR = 0.1310 for 3364 observed reflections with I > 2σ(I). Each Cu(II) ion is coordinated with two different carboxyl O atoms from two 4-carboxyphenoxyacetate groups, two N atoms from two 3-PyOH ligands and two water molecules, residing in a distorted octahedral environment. Adjacent Cu(II) atoms are linked by bi-monodentate 4-CPOA2– groups into an one-dimensional chain along the b axis. A three-dimensional supramolecular network is constructed by O–H…O hydrogen bonds.