C42H32M11N10S6, triclinio, P\ (no. 2), a = 9.666(1) Â, b = 11.077(2) Â, c = 11.352(2) Â, a = 87.663(2)°, β = 76.871(2)°,γ = 67.682(2)°, V= 1093.6 Â, Z= 1, Rgt(F) = 0.053, wRrerfF) = 0.148, T= 296 K. Source of material Manganese(II) acetate tetrahydrate (0.123 g, 0.5 mmol) and NH4SCN (0.076 g, 1 mmol) were refluxed in anhydrous methanol (10 mL) for 50 min, then were simultaneously added 20 mL methanol solution of freshly distilled salicylaldehyde and ethylenediamine at molar ratio 2 :1 . The mixture was stirred for 5 h, 4,4'bipyridyl sulfide (0.11 g, 0.5 mmol) was added, the pH value was adjusted to 5 with CH3COOH solution, and the mixture was further stirred for 2 h, then filtered. The resulting clear solution was diffused with diethyl ether vapor at room temperature for three weeks, yellow crystals were collected by filtration and dried in air (yield 0.156 g, 37 %). Elemental analysis — found: C, 54.61 %; H, 3.43 %; N, 15.19 %; S, 20.74 %; calculated for C42H32NioS6Mni: C, 54.58 %; H, 3.49 %; N, 15.15 %; S, 20.82 %. IR data are available in the CIF. Discussion The chemistry of complexes with multi-dentate ligands such as 4,4'-bipyridinl sulfide has gained much interest because of their use as models in biological systems, organic reactions, materials [1-4]. 4,4-Bipyridinl sulfide is an excellent rod-like Afunctional ligand and has been extensively employed as the rigid organic building block for the construction of the infinite ID, 2D, 3D polymeric frameworks [5-7]. Manganese is an essential trace element, forming the active sites of a number of metalloproteins [810]. Potential importance of manganese complexes is evidenced by the realization that the active site in photosystem Π (PSII) is a tetranuclear manganese complex [11]. Manganese has a vital role in many enzymatic systems such as superoxide dismutase, peroxidase, dioxygenase and catatase in which mononuclear manganese active centers are present [12]. The title crystal structure consists of manganese complex with isothiocyanato anions and 4,4'-bipyridinl sulfide molecules. The salicylaldehyde and ethylenediamine are not present in the final product. The central Mn(II) ion is coordinated by two isothiocyanato groups and two 4,4'-bipyridinl sulfide molecules in monodentate mode. The Μη(Π) ion adopts a slightly distorted octhedronal coordination in a MnNó mode, among which the two nitrogen atoms are from the coordinated isothiocyanato anions, and the other four nitrogen atoms are from two 4,4 -bipyridyl sulfide molecules, respectively. The nitrogen atoms from the two isothio-cyanato groups occupy the axial positions, and four other nitrogen atoms occupy the equatorial positions. The bond distances of Mnl—N2, Mnl—N3, Mnl—N5 were found to be 2.363(3) Â, 2.287(3) Â, 2.158(3) Â, respectively, in which d(Mn—Nbipyridyi) are longer than <f(Mn—Njsothiocyanato), and the ¿(Μη—N) are comparable with those in corresponding Mn(II) complexes involing 4,4'-bipyridine [11]. The angle ZN5-C21S3 is 178.8(3)°, which means the isothio-cyanato anion is nearly linear. The torsion angles of N2-Mnl-N3-C14, N2'-Mnl-N3C14, N5'-Mn 1-N5-C21, N3-Mnl-N5-C21, and Mnl-N5C21-S3 are -55.7(3)°, 124.3(3)°, 157(100)°, 20.7(15)°, 56(17)°, respectively (symmetry code i: -jc.-y+Ι,-ζ+Ι). All the atoms of the mean pyridinyl ring defined by C1/C2/C3/C4/C5/N1 are almost planar with the average deviation of0.054 Â, and the maximum deviation are -0.096 Â for C4. As to the the other ring C6/C7/C8/C9/C10/N2, all the atoms are almost strictly planar with the average and the maximum deviation from pyridine ring are 0.011 Â and-0.019 Â of C8, respectively. In the molecule of 4,4-bipyridyl sulfide, the dihedral angle between two pyridine rings is 122.2°, and this is comparable with the assembly in the other complex containing 4,4-dipyridne [13]. * Correspondence author (e-mail: fengx@lynu.edu.cn)
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 P2(1)/c with a = 20.245(3), b = 7.2905(9), c = 7.5458(10) angstrom, beta = 94.1920(10)degrees, V = 1110.8(2) angstrom(3), M-r = 267.34, Z = 4, D-c = 1.599 g/cm(3), mu(MoK alpha) = 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.
Reaction of 3,5-pyridine-dicarboxylic acid(3,5-PydcH2) with iron salt in hydrothermal condition results in the formation of a three-dimensional self-assembly network formulated as [C14H14Fe2N2O12]n,and it has been structurally characterized by elemental analysis,IR spectra and X-ray diffraction.It crystallizes in the monoclinic system,space group C2/c with a=9.9633(15),b=12.0942(18),c=7.4297(11) and β=105.822o.The units of Fe2(pydc)2·2H2O are linked into a one-dimensional structure via the chelate carboxylate groups from the 3,5-pyridine-dicarboxylate.The interlayer hydrogen bonding interactions result in a three-dimensional supramolecular architecture.In the complex,the Fe(Ⅲ) ion displays a slightly distorted pentagonal bipyramidal geometry with seven coordination numbers.Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are quasi-reversible in nature.
C6H8CdN2O7, orthorhombic, P2(1)2(1)2(1) (no. 19), a = 5.7479(8) angstrom, b = 10.909(2) angstrom, c = 15.370(2) angstrom, V = 963.7 angstrom(3), Z = 4, R-gt(F) = 0.034, wR(ref)(F-2) = 0.080, T = 296 K.
A dicyanamido-bridged polymeric complex formulated as [NaCu2(dca)2(salpn)2]n (1) (dca = dicyanamide anion, H2salpn = N, N'-bis (salicylaldehyde)propylenediimine Schiff base) has been synthesized and characterized systematically. The complex 1 forms the single end-to-end ([image omitted]-) dicyanamido-bridged one dimensional (1D) infinite chain, and the sodium cations ligated by the dca ion ligands display a 1D zigzag chain array, where the diverse coordination fashions of salpn ligand have been observed. The cyclic voltammogram of 1 demonstrates the Cu(II)/Cu(I) and Cu(I)/ Cu(0) reduction couples. The magnetic susceptibility investigation for 1 indicates the presence of very weak antiferromagnetic coupling between Cu(II) cations through the -O-Na-O- bridge.
通过模板法合成了一个新颍的Mn(Ⅲ)配合物,其混合配体由一无机盐阴离子和水杨醛席夫(schiff)碱组成.分别用元素分析、红外光谱、X-射线单晶衍射等对该配合物进行了结构表征.标题配合物属正交晶系,Pbca空间点群.晶胞参数为:a=12.4478(8),b=13.7536(9),c=18.7800(12)A,V=3215.2(4)A3,Z=8.锰(Ⅲ)离子与schiff碱上的两个氮原子、三个氧原子和一个异硫氰酸根离子上一个氮原子的配位,具有扭曲的八面体六配位环境.两个Mn(Ⅲ)配位体通过氧桥联形成双核结构.两个最近的Mn(Ⅲ)原子之间的距离为3.554 A.
C16H28N2O23Yb2, monoclinic, C12/c1 (no. 15), a = 23.126(6) Å, b = 18.174(4) Å, c = 7.840(2) Å, * = 94.090(3)°, V = 3286.7 Å, Z = 4, Rgt(F) = 0.028, wRref(F ) = 0.070, T = 296 K. Source of material The mixture of 2,6-pyridinedicarboxylic acid (H2pydc, 0.0342 g, 0.2.mmol) and (NH4)2C2O4.·.H2O (0.0584 g, 0.4 mmol) in an aqueous solution (10 mL) of NaOH (0.008 g, 0.2 mmol) was added to the aqueous solution (10 mL) of Yb(NO3)3.·.6H2O (0.190 g, 0.4 mmol), and the pH value was adjusted to 3 with 0.2.M nitric acid solution. After stirring for 10 min in air the mixture was placed into 25 mL Teflon-lined autoclave and heated under autogenous pressure at 160 °C for 72 h. The autoclave was cooled over a period of 12 h at a rate 5 °C/h. After the mixture was slowly cooled to room temperature, colourless crystals were obtained. The products are stable in air and insoluble in water (yield 0.017 g, 37 % based on Yb). IR data are available in the CIF. Discussion Carboxylate ligands play an important role in constructing novel metal-organic frameworks (MOFs) based on lanthanides in coordination chemistry. They usually adopt diverse coordination modes such as terminal monodentate, chelating to one metal center, bridging bidentate in syn-syn, syn-anti, or anti-anti configurations to two metal centers [1-3]. Recently, some studies on diand multi-carboxyl ligands or multi-functional carboxyl-containing ligands incorporating other coordination groups, such as N, S have been reported [4,5]. Among them imidazole dior multicarboxylate have been intensively employed to provide a great variety of topological architectures [6,7]. On the other hand, oxalate ligand has been proven to be a good candidate for pillar ligand due to its various bridging abilities and strong coordination to metals to form 2D and 3D moderately robust networks exhibiting tunable ferroor antiferromagnetic exchanges [8]. In contrast to a large number of lanthanide complexes containing only rigid or flexible multicarboxylate ligands, the rare homogeneous constructions involving nitrogen-heterocyclic carboxylate ions and oxalate ligand always only can be obtained from the in situ reaction, in which the multior dicarboxylic acid were decomposed into C2O4 [9,10]. The asymmetric unit of the title complex consists of two Yb(III) cations, two pydc ligands, one bridging oxalate group, six coordinated water molecules and five lattice water molecules. The Yb(III) is octa-coordinated with two oxygen atoms from the multichelating oxalate ligands, two oxygen atoms from the chelating carboxylate group of bpyc ligand and three oxygen atoms from water molecules, as well as the nitrogen atom from the pyridyl ring, respectively. The Yb(III) exhibits a distorted [YbO8] trigonal dodecahedral coordination polyhedron. The bond lengths of Yb—O range from 2.286(3) to 2.348(3) Å, which are comparable to the distances observed in Yb(III) complexes with similar coordination spheres [11,12]. The oxalate anion acts as tetradentate bridge pillar to connect two adjacent Yb1 and Yb1A ions in a anti-anti mode, and thus affords a dimer unit with the Yb···Yb separation of 6.069 Å. The pydc ligand forms two five-membered Yb/N/C/C/O rings, as the ligands based on the gemdiol or the hemiacetal forms of di-2-pyridincarboxylate or ketone have been observed in numerous ligation modes. Hydrogen-bond interactions are observed: O10–H7W···O2 [2.768(5) Å, 144.8°], O10–H8W···O2 [2.733(5) Å, 158.5°], O9–H6W···O10 [2.801(3) Å, 164.2°], O9–H5W···O12 [2.677(5) Å, 166.7°], O8–H4W · · ·O4 [2.664(4) Å , 168.2°]; O8–H3W · · ·O11 [2.701(5).Å, 179.1°], O7–H2W···O1 [2.741(4) Å, 153.4°], O7–H1W···O11 [2.993(7) Å, 129.1°]. The complex can also be considered as a three-dimensional supramolecular architecture, built via strong intermolecular hydrogen-bond interactions. Z. Kristallogr. NCS 225 (2010) 275-276 / DOI 10.1524/ncrs.2010.0119 275 © by Oldenbourg Wissenschaftsverlag, München
A series of novel self-assembly lanthanide coordination polymers formulated as {[Ce-2(pyda)(2)(mu(4)-SO4)center dot 5H(2)O]center dot 2H(2)O}(n) (1), {[Gd-2(Hpimda)(2)(mu(4)-C2O4)center dot 4H(2)O]center dot 2H(2)O}(n) (2), {[Sm-4(pyda)(2)(mu(4)-C2O4)(4)center dot 8H(2)O]center dot 6H(2)O}(n)} (3), and {[Gd-2(pyda)(mu(4)-C2O4)(2)center dot 4H(2)O]center dot 3H(2)O}n (4), (H(3)pimda = 2-propyl-4,5- imidazole-dicarboxylic acid, H(2)pyda - 2,6-pyridine-dicarboxylic acid) have been synthesized from the reactions of H(3)pimda or H(2)pyda with lanthanide salts in the presence of different anions, and were characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Compound 1 is a 2D hybrid in which Ce3+ ions are doubly linked by a carboxylate group of the pyda(2-) ligand. Complexes 2, 3 and 4 have 3D framework structures fabricated through two alternately arranging hexanuclear Ln(3+) motifs, among which the guest water molecules are trapped in the 1D tunnel. In 3 and 4, the [Ln(2)(pyda)(2)](n) layers also consist of alternate left- and right helical chains. Both complexes 2 and 4 exhibit the robust network based on the hexadimeric subunits as 3,3-connected nodes. The emission spectra of the complexes vary depending on which lanthanide ion is present and the aromatic ligands. In addition, compound 1 exhibits weak but significant ferromagnetic couplings between the Ce(III) ions through carboxylato bridges, while dominant antiferromagnetic interactions were observed in compounds 2, 3 and 4.
Seven new lanthanide-organic coordination polymers incorporating both nitrogen heterocyclic dicarboxylate and various auxiliary ligands, {[Ln(3)(Hpimda)(4)(mu(2)-HCOO).5H(2)O].H(2)O}(n)} Ln = Sm (1), Ln = Eu (2), Ln = Gd (3), Ln = Dy (4), Ln = Ho (5), {[Ce(2)(Hpimda)(2)(mu(4)-C(2)O(4)).8H(2)O].2H(2)O}(n) (6), {[Yb(2)(pyda)(mu(4)-C(2)O(4))(2).4H(2)O].3H(2)O}(n) (7) (H(3)pimda = 1H-2-propyl-4,5-imidazoledicarboxylic acid, H(2)pyda = 2,6-pyridinedicarboxylic acid) have been fabricated successfully and characterized systematically. Complexes 1-5 are isomorphous and isostructural, and are built from two-dimensional (2-D) double-decker networks based on the tetranuclear basic carboxylate as a secondary building unit (SBU). Both polymers 6 and 7 feature a (3,4)-connected 3-D framework consisting of 2-D lanthanide-organic hexagonal grids, which are further interlinked via the mu(4)-oxalate ligand. The results of magnetic determination show the same end-to-end bridging fashion of formate group results in different magnetic properties occurring between lanthanide centers. The luminescence emission spectra of the complexes vary depending on the lanthanide ion present.
A novel dicyanamido-bridged 3D polymeric complex {[Zn-2(bpa)(2)(dca)]dca}(n) (1) (dca = dicyanamide anion, bpa = 1,2-bis(4-pyridyl)ethane) has been synthesized by reacting 1,2-bis(4-pyridyl)ethane with zinc salt in the presence of sodium dicyanamide, and characterized by elemental analysis, IR spectra and X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with a = 18.587(3), b = 20.070(3), c = 8.7957(13) angstrom, beta = 100.611(2)degrees, V = 3225.0(8) angstrom(3), M-r = 539.92, mu = 0.789 mm(-1), F(000) = 1116, Z = 4, rho = 1.112 (g/cm(3)), R = 0.0582 and wR = 0.1762. Complex 1 forms a 3D porous framework through the bpa and dca ligands, and gives 1-D coordination channels encapsulated by the guest dca molecules. Complex 1 also displays strong photo-luminescent properties in the solid state at room temperature.
C16H22CaN4O10, monoclinic, Cl2/c1 (no 15), a = 12 724(2) angstrom, b = 13.030(2) angstrom, c = 11 703(2) angstrom, beta 97.856(2)degrees. V = 1922 1 angstrom(3), Z = 4, R-gt(F) = 0 039, R-w(ref)(F-2) = 0.109, T = 296 K
A family of self-assembly lanthanide-organic coordination polymers with both rigid and flexible ligands formulated as {[Ln(2)(Hpimda)(2)(mu(4)-C2O4)center dot 2H(2)O]center dot 4H(2)O}(n) (Ln = Sm (1), Eu (2), Tb (3), Dy (4), Ho (5), Er (6), H(3)pimda = 2-propyl-1H-imidazole-4,5-dicarboxylic acid) has been synthesized from the reactions of H3pimda with trivalent lanthanide salts in the presence of oxalate as coligand. X-ray diffraction analysis reveals that these complexes are isomorphous and isostructural, and each forms a novel three-dimensional (3D) frameworks structure, in which the metalloligands' two-dimensional (2D) networks were constructed from the lanthanide ion, 2-propyl-imidazole-dicarboxylate as well as oxalate ligands, and the oxalate further acts is a pillar to link the [Ln(Pimda)(oxo)] 2D grids to generate the 3D open frameworks, leaving one-dimensional channels. which are occupied by water clusters displaying an intricate array. The luminescence emission spectra of the complexes vary depending on which lanthanide ion is present. In addition, compounds 3, 4, and 5 exhibited weak but significant ferromagnetic couplings within the two adjacent magnetic centers bridged through oxalato, whereas dominant antiferromagnetic interaction was observed in the erbium compound of 6, respectively.
C6H8CeN2O7, orthorhombic, P2(1)2(1)2(1) (no 19), a = 5 7479(8) angstrom, b = 10 909(2) angstrom, c = 15.370(2) angstrom, V = 963.7 angstrom(3), Z = 4, R-gt(F)= 0045, wR(ref)(F-2) = 0.121, T= 296 K
A three dimensional holmium(III) coordination polymer formulated as [Ho4(pydc)2(4-C2O4)4 center dot 8H2O]center dot 6H2On (H2pydc = 2, 6-pyridine-dicarboxylic acid) has been synthesized via the reaction of 2,6-pyridine-dicarboxylic acid and ammonium oxalate with holmium nitrate, and characterized by elemental analysis, IR spectroscopy and X-ray single crystal diffraction. The complex presents 1D zigzag alternate chain array, and these 1D chains are further linked by oxalate ligand into 3D frameworks. Preliminary magnetic studies reveal the complex having weak but significant ferromagnetic couplings within the two adjacent magnetic centers bridged through oxalato, and the complex displays characteristic metal-centered fluorescence in solid state.
The ultra-fine magnesium oxide powders were obtained via direct precipitation process, during which the industrial pure MgSO4·7H2O( origined from szaibelyite) and (NH4)2C2O4 were emplyed as raw materials. The precursor and the final product Nano-meter MgO powders were characterized by IR, XRD and TEM. It belongs to cubic lattic, in sphere shape, white, stable in air. The diameter of powder is about 25-35 nm and homogenous. The mechanism and factors that influences the quality of final produce, such as reaction concentration, feeding fashion, calcining temperature were investigated.
C64H52N16O18Zn4, monoclinic, C12/cl (no. 15), a = 28.914(2) angstrom, b = 17.122(2) angstrom, c = 15.873(1) angstrom, beta = 123.204(2)degrees, V = 6575.1 angstrom(3), Z = 4, R-gt(F) = 0.115, wR(ref)(F-2) = 0.194, T = 273 K.
C42H32M11N10S6, triclinio, P\ (no. 2), a = 9.666(1) Â, b = 11.077(2) Â, c = 11.352(2) Â, a = 87.663(2)°, β = 76.871(2)°,γ = 67.682(2)°, V= 1093.6 Â, Z= 1, Rgt(F) = 0.053, wRrerfF) = 0.148, T= 296 K. Source of material Manganese(II) acetate tetrahydrate (0.123 g, 0.5 mmol) and NH4SCN (0.076 g, 1 mmol) were refluxed in anhydrous methanol (10 mL) for 50 min, then were simultaneously added 20 mL methanol solution of freshly distilled salicylaldehyde and ethylenediamine at molar ratio 2 :1 . The mixture was stirred for 5 h, 4,4'bipyridyl sulfide (0.11 g, 0.5 mmol) was added, the pH value was adjusted to 5 with CH3COOH solution, and the mixture was further stirred for 2 h, then filtered. The resulting clear solution was diffused with diethyl ether vapor at room temperature for three weeks, yellow crystals were collected by filtration and dried in air (yield 0.156 g, 37 %). Elemental analysis — found: C, 54.61 %; H, 3.43 %; N, 15.19 %; S, 20.74 %; calculated for C42H32NioS6Mni: C, 54.58 %; H, 3.49 %; N, 15.15 %; S, 20.82 %. IR data are available in the CIF. Discussion The chemistry of complexes with multi-dentate ligands such as 4,4'-bipyridinl sulfide has gained much interest because of their use as models in biological systems, organic reactions, materials [1-4]. 4,4-Bipyridinl sulfide is an excellent rod-like Afunctional ligand and has been extensively employed as the rigid organic building block for the construction of the infinite ID, 2D, 3D polymeric frameworks [5-7]. Manganese is an essential trace element, forming the active sites of a number of metalloproteins [810]. Potential importance of manganese complexes is evidenced by the realization that the active site in photosystem Π (PSII) is a tetranuclear manganese complex [11]. Manganese has a vital role in many enzymatic systems such as superoxide dismutase, peroxidase, dioxygenase and catatase in which mononuclear manganese active centers are present [12]. The title crystal structure consists of manganese complex with isothiocyanato anions and 4,4'-bipyridinl sulfide molecules. The salicylaldehyde and ethylenediamine are not present in the final product. The central Mn(II) ion is coordinated by two isothiocyanato groups and two 4,4'-bipyridinl sulfide molecules in monodentate mode. The Μη(Π) ion adopts a slightly distorted octhedronal coordination in a MnNó mode, among which the two nitrogen atoms are from the coordinated isothiocyanato anions, and the other four nitrogen atoms are from two 4,4 -bipyridyl sulfide molecules, respectively. The nitrogen atoms from the two isothio-cyanato groups occupy the axial positions, and four other nitrogen atoms occupy the equatorial positions. The bond distances of Mnl—N2, Mnl—N3, Mnl—N5 were found to be 2.363(3) Â, 2.287(3) Â, 2.158(3) Â, respectively, in which d(Mn—Nbipyridyi) are longer than 2 a(lobs), 2914 N(param}„ fined: 268 Programs: SHELXS-97 [14], SHELXL-97 [15], SHELXTL [16] Table 2. Atomic coordinates and displacement parameters (in Ä). Atom Site χ y ζ l/¡so H(l) 21 -0.7180 0.7548 0.1183 0.096 H(2) 2i -0.4943 0.7772 0.1251 0.084 H(4) 2 i -0.3085 0.5889 -0.1986 0.078 H(5) li -0.5403 0.5806 -0.1974 0.096 H(6) li 0.0858 0.6377 0.2538 0.062 H(7) li 0.0165 0.7128 0.0768 0.064 H(9) li -0.2823 0.5353 0.1448 0.070 H(10) li -0.2054 0.4678 0.3192 0.067 H(11) li 0.3565 0.3541 0.4811 0.066 H(12) li 0.5661 0.1707 0.4078 0.075 H(14) li 0.0933 0.2294 0.3519 0.067 H(15) li 0.2957 0.0437 0.2710 0.080 H(16) 2 i 0.9680 0.1205 0.1059 0.160 H(17) li 0.7574 0.0774 0.1140 0.124 H(19) li 0.8344 -0.1149 0.4085 0.103 H(20) li 1.0475 -0.0659 0.3876 0.122 Table 3. Atomic coordinates and displacement parameters (in À). Atom Site X y ζ Un 1/22 1/33 Un Un í/23 Mn(l) 1« 0 Vi Vi 0.0373(4) 0.0530(4) 0.0460(4) -0.0210(3) -0.0109(3) 0.0064(3) S(l) li 0.6081(1) -0.0642(1) 0.2751(2) 0.0615(7) 0.0729(8) 0.185(2) -0.0236(6) -0.0029(8) -0.0526(9) S(2) li -0.1969(1) 0.7012(1) -0.04363(8) 0.0584(6) 0.0987(8) 0.0494(5) -0.0391(5) -0.0197(4) 0.0196(5) S(3) li 0.3805(2) 0.7010(2) 0.3879(1) 0.0936(9) 0.168(1) 0.0919(9) -0.099(1) -0.0255(7) 0.0272(9) N(l) 2 i -0.6527(4) 0.6654(4) -0.0395(4) 0.076(2) 0.100(3) 0.085(3) -0.048(2) -0.039(2) 0.033(2) N(2) 2 i -0.0547(3) 0.5475(3) 0.3069(2) 0.043(2) 0.055(2) 0.044(2) -0.020(1) -0.011(1) 0.002(1) N(3) 2i 0.2038(3) 0.3118(3) 0.4237(2) 0.046(2) 0.061(2) 0.048(2) -0.022(1) -0.013(1) 0.002(1) N(4) 2 i 1.0309(5) 0.0328(5) 0.2438(6) 0.078(3) 0.136(4) 0.147(5) -0.059(3) -0.030(3) 0.001(4) N(5) li 0.1509(3) 0.6058(3) 0.4658(3) 0.056(2) 0.073(2) 0.068(2) -0.035(2) -0.021(2) 0.013(2) C(l) li -0.6346(5) 0.7218(5) 0.0526(4) 0.053(2) 0.106(4) 0.078(3) -0.028(2) -0.014(2) 0.013(3) C(2) 2i -0.4999(4) 0.7353(4) 0.0580(4) 0.058(2) 0.095(3) 0.060(2) -0.027(2) -0.020(2) -0.001(2) C(3) 2 i -0.3742(4) 0.6860(4) -0.0372(3) 0.053(2) 0.064(2) 0.049(2) -0.024(2) -0.020(2) 0.013(2) C(4) 2 i -0.3909(5) 0.6255(4) -0.1328(3) 0.070(3) 0.078(3) 0.054(2) -0.032(2) -0.024(2) 0.012(2) C(5) li -0.5306(6) 0.6196(5) -0.1303(4) 0.102(4) 0.091(3) 0.075(3) -0.055(3) -0.045(3) 0.019(2) C(6) li 0.0090(4) 0.6182(3) 0.2323(3) 0.047(2) 0.061(2) 0.054(2) -0.025(2) -0.018(2) 0.003(2) C(7) 2i -0.0321(4) 0.6642(3) 0.1255(3) 0.053(2) 0.063(2) 0.051(2) -0.030(2) -0.012(2) 0.009(2) C(8) 2 i -0.1463(4) 0.6371(3) 0.0917(3) 0.044(2) 0.058(2) 0.040(2) -0.018(2) -0.012(1) 0.002(2) C(9) 2 i -0.2086(4) 0.5596(4) 0.1658(3) 0.055(2) 0.077(3) 0.059(2) -0.038(2) -0.023(2) 0.013(2) C(10) 2 i -0.1608(4) 0.5189(4) 0.2703(3) 0.054(2) 0.073(2) 0.053(2) -0.036(2) -0.016(2) 0.011(2) C(ll) 2 i 0.3442(4) 0.2903(4) 0.4385(3) 0.048(2) 0.058(2) 0.060(2) -0.018(2) -0.017(2) -0.006(2) C(12) 2 i 0.4707(4) 0.1807(4) 0.3950(4) 0.046(2) 0.064(2) 0.077(3) -0.017(2) -0.021(2) -0.012(2) C(13) 2 i 0.4549(4) 0.0848(4) 0.3318(4) 0.052(2) 0.058(2) 0.082(3) -0.021(2) -0.008(2) -0.013(2) C(14) 2 i 0.1902(4) 0.2177(4) 0.3624(3) 0.049(2) 0.068(2) 0.058(2) -0.029(2) -0.014(2) -0.000(2) C(15) 2 i 0.3105(4) 0.1054(4) 0.3145(4) 0.059(2) 0.069(3) 0.079(3) -0.032(2) -0.011(2) -0.017(2) C(16) 2 i 0.9415(8) 0.0712(7) 0.1688(7) 0.142(6) 0.161(6) 0.139(5) -0.102(5) -0.045(5) 0.064(5) C(17) 2 i 0.8140(6) 0.0469(5) 0.1728(5) 0.103(4) 0.112(4) 0.123(4) -0.054(3) -0.063(3) 0.054(4) C(18) 2 i 0.7698(4) -0.0229(4) 0.2643(4) 0.051(2) 0.053(2) 0.083(3) -0.012(2) -0.010(2) -0.009(2) C(19) 2 i 0.8591(6) -0.0657(5) 0.3448(4) 0.102(4) 0.088(3) 0.070(3) -0.040(3) -0.015(3) 0.004(2) C(20) li 0.9875(6) -0.0357(6) 0.3311(5) 0.088(4) 0.109(4) 0.109(4) -0.021(3) -0.053(3) 0.000(3) C(21) 2i 0.2466(4) 0.6455(3) 0.4346(3) 0.048(2) 0.064(2) 0.043(2) -0.026(2) -0.017(2) 0.005(2) Acknowledgments. This work was supported by the National Natural Science Foundation of China (grant no.20771054) and the Natural Science Foundation of Henan province (grant no. 0311021200).
C19H22N3NdO16, monoclinic, P12(1)/c(1) (no. 14), a = 11.347(2) angstrom, b = 10.857(2) angstrom, c = 19.514(3) angstrom, beta = 92.927(2)degrees, V = 2400.9 angstrom(3), Z = 4, R-gt(F) = 0.022, wR(ref)(F-2) = 0.05 3, T = 296 K.
Reaction of 2,6-pyridine-dicarboxylic acid and ammonium oxalate with erbium salt results in the formation of a self-assembly network based upon mixed ligands of oxalate and pyridine-dicarboxylate formulated as {[Er4(pydc)2(μ4-C2O4)4]·8H2O·6H2O}n (H2pydc=2,6-pyridine-dicarboxylic acid), in which supramolecular left-handed and right-handed helices are connected via μ4-oxalate anions, and gave the 1D coordination channels constructed via bridging oxalate and pydc ligands. The complex also displayed photo-luminescent properties in the solid state at room temperature.
C32H32Mn2N8O12, orthorhombic, Pccn (no. 56), a = 13.028(2) Å, b = 19.081(3) Å, c = 7.261(1) Å, V = 1805.0 Å, Z = 2, Rgt(F) = 0.029, wRref(F) = 0.075, T = 291 K. Source of material Mn(CH3COO)2 · 4H2O (0.123 g, 0.5 mmol) and 4,4'-bipyridine (0.96 g, 0.5 mmol) were refluxed in anhydrous methanol (10 ml) for 50 min, then, cyanoacetic acid (0.88 g, 1 mmol) was added. The pH value was adjusted to 3 with 0.5 M CH3COOH solution. The mixture was further stirred for 2 h, then filtered. The resulting clear solution was diffused with diethyl ether vapor at room temperature for two weeks. Dark green crystals were obtained, collected by filtration and dried in air (yield, 0.156 g, 37 %). Elemental analysis — found: C, 46.48 %; H, 34.59 %; N, 13.46.%; calculated for C32H32N8O12Mn2: C, 46.27 %; H, 34.88.%; N, 13.49 %. IR data are available in the CIF. Experimental details The positions of the water hydrogen atoms were found from Fourier difference synthesis and refined isotropically. The remaining hydrogen atoms were generated theoretically, and included as fixed contributions without futher refinement. Discussion The chemistry of complexes with multidentate ligands such as 4,4'-bipyridine have gained much interest because of their use as models in biological systems, organic reactions, and as fluorescent materials [1-4]. 4,4'-Bipyridine is an excellent rod-like bifunctional ligand. It has been extensively employed as the rigid organic building block for the construction of the infinite 1D, 2D, 3D atomic arrangements [5-7]. Manganese is an essential trace element, forming the active sites in metalloproteins [8]. Potential importance of manganese complexes is evidenced as active site in photosystem II (PSII) which is a tetranuclear manganese complex [9]. It plays a vital role in many enzymatic systems such as superoxide dismutase, peroxidase, dioxygenase and catalase where mononuclear manganese active centers are present [10]. The title crystal structure consists of manganese complexes with cyanoacetic acid anions, bridged via 4,4'-bipy molecules, with the Mn···Mn separation of 11.558 Å. The Mn(II) ions are coordinated with two cyanoacetic acid, two waters and two 4,4'bipyridine molecules. The Mn(II) ions adopt a distorted octhedral coordination N2O4, maybe due to the Jahn-Teller effect. The two oxygen atoms are from the coordinated water molecules, the other two oxygen atoms are from the cyanoacetic acid anions, and two nitrogen atoms are from two 4,4'-bipyridine molecules, respectively. The nitrogen atoms from the 4,4'-bipy molecules are located in the axial positions, the oxygeon atoms occupy the equatorial positions. The cyanoacetic acid anions display the monodentate coordination fashion, while the 4,4'-bipy molecules adopted a bidentate coordination mode. The bond distances of Mn1—N1, Mn1—O2, Mn1—O3 are 2.256(1) Å, 2.177(1) Å, 2.235(2) Å, respectively, being in the range found for other Mn complexes [11,12]. The N1−Mn1−N1 group and the O2−Mn1− O2 group are linear by symmetry. The torsion angles of O2− Mn1−O2−C6, O3−Mn1−O2−C6, O3−Mn1−O2−C6, and N1− Mn1−O2−C6 are 119(3)°, 22.2(2)°, −157.8(2)°, −66.7(2)°, respectively (symmetry code i: −x,−y,−z). The pyridinyl ring C1− C2−C3−C4−C5−N1 is almost planar with the average deviation from the ring plane is 0.054 Å, and the maximum deviation are /0 081 . Å for N1, and +0.006 Å for C1A, respectively. The three-dimensional supramolecular framework is constructed by hydrogen bonds O−H(W)···O linking the neighboring molecules. Both kinds of hydrogen bonds O3−H1W···O1, [O3− H1W···O1 = 2.679(2) Å, 167(2)°], and O3−H2W···O1, [O3− H2W···O1 = 2.934(2) Å, 146(2)° (symmetry code ii: −x,−y,−z+1 )]; are formed by the oxygen atoms from cyanoacetic acid anions. Several one-dimensional channles along [010] are formed by the 4,4'-bipy molecules and cyanoacetic acid anions. Z. Kristallogr. NCS 224 (2009) 193-194 / DOI 10.1524/ncrs.2009.0086 193 © by Oldenbourg Wissenschaftsverlag, München