Two versatile N,N'-bipyridine-type ligands for preparing organic-inorganic coordination polymers: new cobalt- and nickel-containing framework materials

The Schiff base ligands 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L1, monoclinic, P2(1)/c, a = 3.856(1) A, b = 11.032(2) A, c = 12.738(3) A, beta = 92.21(3) degrees, Z = 2) and 2,5-bis(4-pyridyl)-3,4-diaza-2,4-hexadiene (L2, monoclinic, P2(1)/c, a = 10.885(2) A, b = 4.613(1) A, c = 14.978(3) A, beta = 92.827(4) degrees, Z = 2) were used in the synthesis of four new organic-inorganic coordination polymers, each of them adopting a different structural motif. Synthesis, X-ray structural determinations, and spectroscopic and thermogravimetric analyses are presented. The reaction between Co(NO(3))(2).6H(2)O and L1 afforded a two-dimensional noninterpenetrating brick-wall structure, [Co(C(12)N(4)H(10))(1.5)(NO(3))(2)(H(2)O)(CH(2)Cl(2))(2)](n)() (1, triclinic, P1; a = 10.242(7) A, b = 10.802(7) A, c = 15.100(1) A, alpha = 70.031(1), beta = 75.168(11), gamma = 76.155(11), Z = 2), while Ni(NO(3))(2).6H(2)O combined with L1 yielded an interpenetrating three-dimensional rhombus-grid polymer, [Ni(C(12)N(4)H(10))(2)(NO(3))(2)(OC(4)H(8))(1.66)(H(2)O)(0.33)](n) (2, monoclinic, C2/c; a = 20.815(8) A, b = 23.427(8) A, c = 17.291(6) A, beta = 116.148(6), Z = 8). The reaction of Co(NO(3))(2).6H(2)O and L2 was found to be solvent-sensitive and resulted in the formation of two different noninterpenetrating compounds: [Co(C(14)N(4)H(14))(2)(NO(3))(2)(C(6)H(6))(1.5)](n)() (3, monoclinic, C2/c; a = 22.760(2) A, b = 21.010(3) A, c = 25.521(2) A, beta = 97.151(2), Z = 8), which adopts a two-dimensional square-grid motif formed by propeller-type modules, and [Co(C(14)N(4)H(14))(1.5)(NO(3))(2)(CH(2)Cl(2))(2)](n)() (4, monoclinic, P2(1)/n; a = 14.432(2) A, b = 14.543(8) A, c = 15.448(4) A, beta = 96.968(0), Z = 4), consisting of T-shaped building blocks assembled into a one-dimensional ladder-type structure. These four coordination polymers all exhibit impressive thermal stability. Thermogravimetric studies showed that after complete removal of the solvents, the frameworks are stable to temperatures between 234 degrees C and 260 degrees C.     

Synthesis and characterization of diverse coordination polymers. Linear and zigzag chains involving their structural transformation via intermolecular hydrogen-bonded, interpenetrating ladders polycatenane, and noninterpenetrating square grid from long, rigid N,N'-bidentate ligands: 1,4-bis[(x-pyridyl)ethynyl]benzene (x = 3 and 4)

The long, rigid ligands 1,4-bis[(3-pyridyl)ethynyl]benzene (L1) and 1,4-bis[(4-pyridyl)ethynyl]benzene (L2) were used in the synthesis of 10 new organic-inorganic coordination frameworks, each of them adopting different structural motifs. Synthesis, single-crystal X-ray structure determination, and spectroscopic and thermogravimetric analyses are presented. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] with L1 afforded the following one-dimensional zigzag chain structures: [Cd(C20H12N2)0.5(NO3)(CH3OH)]n (1, monoclinic, C2/c; a = 7.586(1) A, b = 23.222(1) A, c = 13.572(1) A, beta = 92.824(1), Z = 4); [{Cu(C20H12N2)(NO3)2(CH3OH)} x CH3OH]n (2, orthorhombic, P2(1)2(1)2(1); a = 8.589(1) A, b = 15.766(1) A, c = 17.501(1) A, Z = 4); [Co(C20H12N2)2(NO3)2(H2O)2] (5, triclinic, P1; a = 7.493(1) A, b = 8.948(1) A, c = 14.854(1) A, alpha = 100.427(1), beta = 97.324(1), gamma = 110.901(1), Z = 1); [Cu(C20H12N2)(hfac)2]n (4, monoclinic, C2/c, a = 18.828(1) A, b = 14.671(1) A, c = 13.427(1) A, beta = 90.447(1) degrees, Z = 4). Moreover, the minority phase compound formed from Cu(NO3)2 x 3H2O and L1 yielded a metallocyclic chain structure, [Cu(C20H12N2)(NO3)]n (3, triclinic, P; a = 8.728(1) A, b = 10.018(1) A, c = 11.893(1) A, alpha = 109.991(1), beta = 97.109(1), gamma = 115.542(1), Z = 1). In addition to the dinuclear coordination complex 5, all other polymeric structures (1-4) from L1 are composed of interpenetrating 2D and 3D cross-linked zigzag chains via hydrogen-bonding interactions. The reactions between M(NO3)2 x xH2O; M = Cd(II), Cu(II), and Co(II); x = 3-6 and Cu(hfac)2 x H2O [hfac = bis(hexafluoroacetylacetonato)] and L2 were dependent on the nature of the metal center and resulted in the formation of four different interpenetrating and noninterpenetrating compounds (6-10): [Co(C20H12N2)1.5(NO3)2]n (6, triclinic, P; a = 14.172(1) A, b = 15.795(1) A, c = 18.072(1) A, alpha = 115.380(1), beta = 101.319(1), gamma = 93.427(2), Z = 4), which consists of T-shaped building blocks assembled into three-dimensional interpenetrating polycatenated ladders; [Cd(C20H12N2)2(NO3)2]n (7, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), which adopts a two-dimensional noninterpenetrating square-grid motif; [Cu(C20H12N2)(hfac)2]n (8, monoclinic, I2/a; a = 11.371(1) A, b = 20.311(2) A, c = 15.240(2) A, beta = 100.201(2) degrees, Z = 4), composed of three sets of distinct one-dimensional linear chains; [Cu(C20H12N2)(EtOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2EtOH (9, triclinic, P; a = 12.248(2) A, b = 13.711(3) A, c = 18.257(4) A, alpha = 108.078(4) degrees, beta = 97.890(4) degrees, gamma = 103.139(5) degrees, Z = 2) and [Cu(C20H12N2)(MeOH)(NO3)2] [Cu(C20H12N2)1.5(NO3)2] x 2MeOH (10, triclinic, P; a = 12.136(1) A, b = 13.738(2) A, c = 17.563(3) A, alpha = 107.663(3) degrees, beta = 94.805(4) degrees, gamma = 104.021(4) degrees, Z = 2). Both 9 and 10 stack into infinite interpenetrating ladders through bundles of infinite chains and are described in our preliminary communication.     

Coordination polymers assembled from angular dipyridyl ligands and CuII, CdII, CoII salts: crystal structures and properties

Six new metal-organic coordination networks based on linking unit 2,5-bis(4-pyridyl)-1,3,4-thiadiazole (L(1)) or 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (L(3)) and inorganic Cu(II), Cd(II), and Co(II) salts have been prepared and structurally characterized by single-crystal X-ray analysis. Using L(1) to react with three different Cu(II) salts, Cu(OAc)(2).H(2)O, Cu(NO(3))(2).3H(2)O, and CuSO(4).5H(2)O, respectively, two different one-dimensional (1-D) coordination polymers, [[Cu(2)L(1)(mu-OAc)(4)](CHCl(3))(2)](n) (1) [triclinic, space group P1, a = 7.416(3) A, b = 8.207(3) A, c = 14.137(5) A, alpha = 100.333(7) degrees, beta = 105.013(6) degrees, gamma = 94.547(6) degrees, Z = 1] and [[CuL(1)(NO(3))(2)](CHCl(3))(0.5)](n) (2) [monoclinic, space group C2/c, a = 28.070(8) A, b = 9.289(3) A, c = 15.235(4) A, beta = 113.537(5) degrees, Z = 8], and a chiral 3-D open framework, [[CuL(1)(H(2)O)(SO(4))](H(2)O)(2)](n) (3) [orthorhombic, space group P2(1)2(1)2(1), a = 5.509(2) A, b = 10.545(4) A, c = 29.399(11) A, Z = 4], were obtained. Reaction of L(1) and Cd(ClO(4))(2).6H(2)O or Co(ClO(4))(2).6H(2)O, in the presence of NH(4)SCN, yielded another 3-D open framework, [[CdL(1)(NCS)(2)](CH(3)OH)(1.5)](n) (4) [monoclinic, space group C2/c, a = 28.408(10) A, b = 9.997(5) A, c = 7.358(4) A, beta = 99.013(8) degrees, Z = 4], or a 2-D network, [[Co(L(1)())(2)(NCS)(2)](H(2)O)(2.5)](n) (5) [orthorhombic, space group Pnna, a = 22.210(5) A, b = 12.899(3) A, c = 20.232(4) A, Z = 4]. When L(1) was replaced by L(3) to react with Co(ClO(4))(2).6H(2)O and NH(4)SCN, another 2-D coordination polymer, [Co(L(3))(2)(NCS)(2)](n) (6) [monoclinic, space group P2(1)/c, a = 8.120(3) A, b = 9.829(4) A, c = 17.453(6) A, beta = 103.307(6) degrees, Z = 2], was constructed. These results indicate that the nature of the ligands, metal centers, or counteranions plays the critical role in construction of these novel coordination polymers. The interesting porous natures of two 3-D open frameworks 3 and 4 were investigated by TGA and XPRD techniques, and the magnetic properties of the Cu(II) and Co(II) complexes were studied by variable-temperature magnetic susceptibility and magnetization measurements.     

Synthesis and characterization of new coordination polymers generated from oxadiazole-containing organic ligands and inorganic silver(I) salts

The coordination chemistry of the oxadiazole-containing rigid bidentate ligands 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L2) and 2,5-bis(4-aminophenyl)-1,3,4-oxadiazole (L3) with inorganic Ag(I) salts has been investigated. Four new coordination polymers were prepared by solution reactions and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. [[Ag(L2)]SO3CF3]n (1)(triclinic, P1; a = 10.1231(7) A, b = 13.9340-(10) A, c = 13.9284(10) A, alpha = 116.7300(10) degrees, beta = 94.6890(10) degrees, gamma = 108.7540(10) degrees, Z = 4) was obtained by the combination of L2 with AgOTf in a CH2Cl2/CH3OH mixed-solvent system and features a unique one-dimensional elliptical macrocycle-containing chain motif. The approximate dimensions of the rings are ca. 22 x 11 A. [[Ag-(L2)](ClO4)(CH3OH)0.5(H2O)0.5]n (2) (triclinic, P1; a = 8.4894(5) A, b = 13.9092(8) A, c = 14.1596(8) A, alpha = 71.1410(10) degrees, beta = 77.3350(10) degrees, gamma = 81.5370(10) degrees, Z = 4) was generated from the reaction of L2 with AgClO4 in a H2O/CH3OH mixed-solvent system and consists of one-dimensional chains that are linked to each other by weak noncovalent pi-pi interactions into two-dimensional sheets. Uncoordinated ClO4-counterions and guest solvent molecules are located between the layers. [[Ag(L2)]NO3]n (3) was obtained by the combination of L2 with Ag(NO3)2 in a MeOH/H2O mixed-solvent system (triclinic, P1; a = 8.3155(6) A, b = 8.8521(6) A, c = 9.8070(7) A, alpha = 74.8420(10) degrees, beta = 77.2800(10) degrees, gamma = 68.6760(10) degrees, Z = 2). In the solid state, it exhibits an interesting pair of chains associated with C-H...O hydrogen bonds. [[Ag(L3)]SO3CF3]n (4) is generated from L3 and AgSO3CF3 in a CH2Cl2/MeOH mixed-solvent system and crystallizes in the unusual space group Pnnm, with a = 7.9341(4) A, b = 11.5500(5) A, c = 18.1157(8) A, and Z = 4. It adopts a novel three-dimensional structural motif in the solid state with big rhombic channels (ca. 15 x 10 A).     

A New Supramolecular Compound Based on Cd（II）-Schiff-base and Keggin-type [PMo_（12）O_（40）]~3

A new supramolecular compound, {[Cd(L)2]2[PMo12O40NO3]·CH3CN·2H2O}n 1 (L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), based on Cd(II)-Schiff-base and Keggin- type [PMo12O40]3- was synthesized via self-assembly and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a = 12.0128(11), b = 13.6196(13), c = 13.9995(13) , α = 103.868(2), β = 95.225(2), γ = 101.024(2)°, V = 2160.0(3) 3, Z = 1, C34H39N26O45Cd2Mo12P, Mr = 2938.96, Dc = 2.259 g/cm3, μ = 2.276 mm-1, F(000) = 1400, the final R = 0.0565 and wR = 0.1613 for 4973 observed reflections with I 2σ(I). The crystal structure can be described by the packing of Keggin anionic and Metal-Schiff-base cationic layers.     

Self-assembled dinuclear,trinuclear, tetranuclear,pentanuclear, and octanuclear Ni(II) complexes of a series of polytopic diazine based ligands: structural and magnetic properties

The nickel coordination chemistry of a series of polytopic diazine (N-N) based ligands has been examined. Self-assembly reactions lead to examples of dinuclear, trinuclear, tetranuclear, pentanuclear, and octanuclear complexes, all of which exhibit magnetic exchange coupling, with antiferromagnetic and ferromagnetic examples. Structural details are presented for [(L1)(2)Ni(2)(H(2)O)(2)](NO(3))(4).3H(2)O (1), [(L2)(2)Ni(3)(H(2)O)(2)](NO(3))(6).8H(2)O (2), [(L3)(4)Ni(4)(H(2)O)(8)] (NO(3))(4).8H(2)O (3), [(L4)(2)Ni(5)(H(2)O)(10)(NO(3))](NO(3))(7).8H(2)O (4), and [(L5)(4)Ni(8)(H(2)O)(8)](BF(4))(8).16H(2)O (5). Compound 1 crystallizes in the monoclinic system, space group P2(1)/c, with a = 14.937(1) A, b = 18.612(2) A, c = 20.583(2) A, beta = 108.862(2) degrees, Z = 4. Compound 2 crystallizes in the orthorhombic system, space group P2(1)2(1)2, with a = 21.771(4) A, b = 13.700(2) A, c = 20.017(3) A, Z = 4. Compound 3 crystallizes in the tetragonal system, space group P4(3), with a = 12.9483(7) A, c = 33.416(3) A, Z = 4. Compound 4 crystallizes in the triclinic system, space group P(-)1, with a = 12.6677(8) A, b = 18.110(1) A, c = 19.998(1) A, alpha = 100.395(1) degrees, beta = 109.514(1) degrees, gamma = 109.686(1) degrees, Z = 2. Compound 5 crystallizes in the monoclinic system, space group P2(1)/n, with a = 21.153(5) A, b = 35.778(9) A, c = 21.823(5) A, beta = 97.757(6) degrees, Z = 4. The linear trinuclear Ni(II) complex (2) has a cis-N-N single bond bridge, and a water bridge linking the central Ni(II) to each external Ni(II) center in each of two similar trinuclear subunits, and exhibits intramolecular ferromagnetic exchange (J = 5.0 cm(-1)). A novel octanuclear metallacyclic ring structure exists in 5, with trans-N-N single bond bridges linking adjacent Ni(II) centers, leading to quite strong intramolecular antiferromagnetic exchange (J = -30.4 cm(-1)).     

Synthesis and characterization of a novel cadmium-organic framework with trimesic acid and 1,2-bis(4-pyridyl)ethane

The hydrothermal reaction between Cd(NO(3))(2), trimesic acid (H(3)BTC), 1,2-bis(4-pyridyl)ethane (BPE), and triethylamine under mild conditions yielded, after 3 days, a novel three-dimensional metal-organic framework, [Cd(1.5)(BTC)(BPE)(H(2)O)(2)].(H(2)O), which has been characterized structurally using single-crystal and powder X-ray diffraction, elemental analysis, infrared and Raman spectroscopies, thermogravimetry, and differential scanning calorimetry. The structure exhibits a 2-fold interpenetration of identical [Cd(1.5)(BTC)(BPE)(H(2)O)(2)] single frameworks, described as an unusual (9) net. Crystal data: Cd(1.5)C(21)H(21)N(2)O(9), monoclinic, space group C2/c, with a = 10.8264(5) A, b = 17.4563(5) A, c = 24.2605(11) A, beta = 91.978(2) degrees, V = 4582.2(3) A(3), and Z = 8.     

New Cd(II)-, Co(II)-, and Cu(II)-containing coordination polymers synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA)

Four new organic/inorganic coordination polymers, [Cd(C(10)H(8)N(2))(2)(H(2)O)(2)(NO(3))(2)](n)(1), [Co(C(10)H(8)N(2))(H(2)O)NO(3)CH(3)OH](n)(2), [Cu(C(10)H(8)N(2))(CH(3)OH)(NO(3))(2)](n) (3), and [Cu(C(10)H(8)N(2))(hfac)(2)](n)(4), were synthesized by using the rigid ligand 1,2-bis(3-pyridyl)ethyne (3,3'-DPA). Complex 1 crystallizes in space group P2/n: a = 12.462(2) A, b = 9.485(1) A, c = 13.383(2) A, beta = 96.629(2) degrees, V = 1559.6(3) A(3), Z = 4. Complex 2 crystallizes in space group Fddd: a = 9.248(4) A, b = 19.982(7) A, c = 35.093(16) A, V = 6485.0(4) A(3), Z = 8. Complex 3 crystallizes in space group I2/a: a = 18.315(2) A, b = 8.517(1) A, c = 20.494(3) A, beta = 104.042(2) degrees, V = 3101.2(7) A(3), Z = 8. Complex 4 crystallizes in space group P21/c: a = 6.576(1) A, b = 16.189(1) A, c = 11.653(1) A, beta = 91.337(1) degrees, V = 1240.3(2) A(3), Z = 2. The coordination polymers display a variety of structural architectures, ranging from sinusoidal and zigzag chains (1, 3, 4) to two-dimensional channel-type architectures (2). The effects of the orientation of the nitrogen atom in the pyridine rings on the resultant structures are discussed.     

Pentanuclear homoleptic M(5)L(6) (M = Mn(II), Co(II), Zn(II)) complexes formed by strict self-assembly

A series of trigonal bipyramidal pentanuclear complexes involving the alkoxo-diazine ligands poap and p3oap, containing the M(5)[mu-O](6) core is described, which form by a strict self-assembly process. [Co(5)(poap-H)(6)](ClO(4))(4).3H(2)O (1), [Mn(5)(poap-H)(6)](ClO(4))(4).3.5CH(3)OH.H(2)O (2), [Mn(5)(p3oap-H)(6)](ClO(4))(4).CH(3)CH(2)OH.3H(2)O (3), and [Zn(5)(poap-H)(6)](ClO(4))(4).2.5H(2)O (4) are homoleptic pentanuclear complexes, where there is an exact match between the coordination requirements of the five metal ions in the cluster, and the available coordination pockets in the polytopic ligand. [Zn(4)(poap)(poap-H)(3)(H(2)O)(4)] (NO(3))(5).1.5H(2)O (5) is a square [2 x 2] grid with a Zn(4)[mu-O](4) core, and appears to result from the presence of NO(3), which is thought to be a competing ligand in the self-assembly. X-ray structures are reported for 1, 4, and 5. 1 crystallized in the monoclinic system, space group P2(1)/n with a = 13.385(1) A, b = 25.797(2) A, c = 28.513(3) A, beta = 98.704(2) degrees, and Z = 4. 4 crystallized in the triclinic system, space group P1 with a = 13.0897(9) A, b = 18.889(1) A, c = 20.506(2) A, alpha = 87.116(1) degrees, beta = 74.280(2) degrees, gamma = 75.809(2) degrees, and Z = 2. 5 crystallized in the monoclinic system, space group P2(1)/n with a = 14.8222(7) A, b = 21.408(1) A, c = 21.6197(9) A, beta = 90.698(1) degrees, and Z = 4. Compounds 1-3 exhibit intramolecular antiferromagnetic coupling.     

Reactions and reactivity of Co-bpdc coordination polymers (bpdc = 4,4'-biphenyldicarboxylate)

By choosing a suitable metal center, ligand, and solvents, we have revealed several structural transformations involving a polymer precursor. infinity 1[Co(bpdc)(H2O)2].H2O (1) was prepared by reaction of Na2bpdc and Co(NO3)2 in aqueous solution. Immersing 1 in pyridine/water solutions of (2:1) and (8:1) ratios yielded a second one-dimensional structure infinity 1[Co(bpdc)(py)2(H2O)2].2py (2) and a two-dimensional structure infinity 2[Co(bpdc)(py)2].H2O (3), respectively. After heating 1 under N2 to remove all water within the structure, the compound Co(bpdc) (IR) was obtained. When IR was immersed in solutions of pyridine/water (5:4) and in pure pyridine (in air), a third one-dimensional structure of infinity 1[Co(bpdc)(py)2(H2O)2].2py.H2O (4) and 3, respectively, were obtained. Compounds 2-4 easily transformed to 1 when immersed in water. Crystal data for 1: monoclinic, space group C2/c with a = 6.950(1), b = 31.585(6), and c = 6.226(1) A, beta = 95.84(3) degrees, Z = 4. Crystal data for 2: triclinic, space group P1 with a = 9.646(2), b = 10.352(2), and c = 17.031(3) A, alpha = 79.02(3) degrees, beta = 86.88(3) degrees, gamma = 77.16(3) degrees, Z = 2. Crystal data for 3: triclinic, space group P1 with a = 9.137(2), b = 10.480(2), and c = 12.254(2) A, alpha = 102.10(3) degrees, beta = 100.80(3) degrees, gamma = 99.43(3) degrees, Z = 2. Crystal data for 4: orthorhombic, space group Pbcn with a = 13.468(3), b = 16.652 (3), and c = 14.977(3) A, Z = 4.     

Synthesis and characterization of new coordination polymers generated from bent bis(cyanophenyl)oxadiazole ligands and Ag(I) salts

Two new bent bis(cyanophenyl)oxadiazole ligands, 2,5-bis(4-cyanophenyl)-1,3,4-oxadiazole (L7) and 2,5-bis(3-cyanophenyl)-1,3,4-oxadiazole (L8), were synthesized. The coordination chemistry of these ligands with various Ag(I) salts has been investigated. Seven new coordination polymers, namely, {[Ag(L7)(H2O)]ClO4}n) (1) (triclinic, P1, a = 9.342(4) A, b = 9.889(4) A, c = 10.512(4) A, alpha = 68.978(6) degrees, beta = 78.217(6) degrees, gamma = 81.851(7) degrees, Z = 2), {[Ag(L7)]SO3CF3}n (2) (monoclinic, P2(1)/n, a = 7.559(2) A, b = 23.739(6) A, c = 10.426(3) A, beta = 108.071(4) degrees, Z = 4), {[Ag(L8)]BF4 x 0.5(C6H6) x H2O}n (3) (triclinic, P1, a = 7.498(3) A, b = 10.649(4) A, c = 13.673(5) A, alpha = 98.602(5) degrees, beta = 100.004(5) degrees, gamma =110.232(5) degrees, Z = 2), {[Ag(L8)SbF6] x H2O}n (4) (triclinic, P1, a = 8.2621(9) A, b = 10.6127(12) A, c = 13.3685(15) A, alpha = 98.012(2) degrees, beta = 106.259(2) degrees, gamma = 112.362(2) degrees, Z = 2), {[Ag2(L8)2(SO3CF3)] x H2O}n (5) (triclinic, P1, a = 10.713(4) A, b = 13.449(5) A, c = 15.423(5) A, alpha = 65.908(5) degrees, beta = 74.231(5) degrees, gamma = 83.255(5) degrees, Z = 2), {[Ag2(L8)(C6H6)(ClO4)] x ClO4}n (6) (monoclinic, P2(1)/n, a = 6.9681(17) A, b = 20.627(5) A, c = 17.437(4) A, beta = 95.880(4) degrees, Z = 4), and {[Ag2(L8)(H2PO4)2]}n (7) (triclinic, P1, a = 7.956(2) A, b = 9.938(3) A, c = 14.242(4) A, alpha = 106.191(4) degrees, beta = 97.322(4) degrees, gamma = 107.392(4) degrees, Z = 1), were obtained by the combination of L7 and L8 with Ag(I) salts in a benzene/methylene chloride mixed-solvent system and fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. In addition, the luminescence and electrical conductance properties of compounds 1-6 and the host-guest chemistry of compound 3 were investigated.     

Organometallic silver(I) supramolecular complexes generated from multidentate furan-containing symmetric and unsymmetric fulvene ligands and silver(I) salts

One new conjugated symmetric fulvene ligand L1 and two new unsymmetric fulvene ligands L2 and L3 were synthesized. Five new supramolecular complexes, namely Ag2(L1)3(SO3CF3)3 (1) (1, monoclinic, P2(1)/c; a = 12.702(3) A, b = 26.118(7) A, c = 13.998(4) A, beta = 96.063(4) degrees, Z = 4), [Ag(L1)]ClO4 (2) (monoclinic, C2/c; a = 17.363(2) A, b = 13.2794(18) A, c = 13.4884(18) A, beta = 100.292(2) degrees, Z = 8), [Ag(L1)(C6H6)SbF6] x 0.5C6H6 x H2O (3) (monoclinic, P2(1)/c; a = 6.8839(11) A, b = 20.242(3) A, c = 18.934(3) A, beta = 91.994(3) degrees, Z = 4), Ag(L2)(SO3CF3) (4) (triclinic, P1; a = 8.629(3) A, b = 10.915(3) A, c = 11.178(3) A, alpha = 100.978(4) degrees, beta = 91.994(3) degrees, gamma = 105.652(4) degrees, Z = 2), and Ag(L3)(H2O)(SO3CF3) (5) (triclinic, P1; a = 8.914(5) A, b = 10.809(6) A, c = 11.283(6) A, alpha = 69.255(8) degrees, beta = 87.163(9) degrees, gamma = 84.993(8) degrees, Z = 2) were obtained through self-assembly based on these three new fulvene ligands in a benzene/toluene mixed-solvent system. Compounds 1-5 have been fully characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The results indicate that the coordination chemistry of new fulvene ligands is versatile. They can adopt either cis- or trans-conformation to bind soft acid Ag(I) ion through not only the terminal -CN and furan functional groups but also the fulvene carbon atoms into organometallic coordination polymers or discrete complexes. In addition, the luminescent properties of L1-L3 and their Ag(I) complexes were investigated preliminarily in EtOH and solid state.     

Two Cobalt(Ⅱ) Complexes Derived from the Hydrolysis Product of Di-Schiff Base Ligand N,N'-Bis-(1-benzimidazo-2-ylethylidene)-ethane-1,2-diamine: Preparation,Characterization and Crystal Structure of the 6-Coordinate Species [CoL2]X·H2O (X = ClO4-,NO3-)

The reactions of Co(CIO4)2.6H2O and Co(NO3)2·6H2O with the di-Schiff base ligand N,N'-bis-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine (LA) in ethanol have been investigated.The reactions of LA with excess amount of cobalt salts yield the six-coordinate complexes [CoL2](CIO4)2·H2O 1 and [CoL2](NO3)2·H2O 2 as isolatable products (L = N-(1-benzimidazo-2-yl-ethylidene)-ethane-1,2-diamine), where L is a tri-dentate mono-Schiff base ligand, resulting from the hydrolysis of the precursor di-Schiff base LA.Both complexes were characterized by X-ray crystallography.Crystal data for complex 1: monoclinic, space group P21/c, a = 11.9214(10), b = 23.5828(17), c = 14.0387(12)(A), β= 135.219[4]°,C22H30CI2CoN9O9,Mr = 680.37, V = 2780.1(4)(A)3, Z = 4, Dc = 1.625 g/cm3,μ(MoKa) = 0.876 mm-1, F(000) = 1404,the final R = 0.0725 and wR = 0.1530 for 5726 observed reflections (I＞2σ(I)).Crystal data for complex 2: monoclinic, space group P21/c, a = 18.2162(16), b = 10.0610(6), c = 18.593(2)(A),β=130.099(3)°, C22H30CoN10O7, Mr = 605.49, V = 2606.5(4)(A)3, Z = 4, Dc = 1.543 g/cm3,μ(MoKα)= 0.722 mm-1, F(000) = 1260, the final R = 0.0619 and wR = 0.1429 for 5194 observed reflections (I ＞ 2σ(I)).X-ray diffraction analysis reveals that each cobalt atom in the two complexes is chelated by six nitrogen atoms from two tridentate iigands L, exhibiting a slightly distorted octahedral coordination sphere.In both complexes, the strong hydrogen-bonding interactions between the lattice waters and N-H groups of the ligands result in 1D chains which are further connected by ClO4- (or NO3-) groups to form a 3D framework.In complex 2, the strong π-π interactions increase the stability of the structure.     

Synthesis and Structural Characterization of a New Cadmium(Ⅱ) Complex with a Double Betaine

A new flexible double betaine L (L =1,4-bis(pyridinio-4-carboxylato-N-methyl)and its crystal structure was determined by single-crystal X-ray diffraction analysis.Crystallo13.7854(3), b = 14.2820(3), c = 14.9188(4)(。A), β = 116.418(1)°, V = 2630.5(1)(。A)3, Z = 4, Dc = 1.704g/cm3, μ(MoKα) = 0.911 mm-1, F(000) = 1368, the final R = 0.0315 and wR = 0.0768 for 3637observed reflections with I ＞ 2σ(I).In complex 1, L acts as a monodentate ligand to link a Cd(Ⅱ) ion in a novel coordination mode of double betaines.The mononuclear [Cd(H2O)4L(NO3)] units are connected through intermolecular hydrogen bonds and π-π stacking reactions to generate a 3D network.     

Syntheses and Crystal Structures of Cobalt(II) Chloride Complexes of 1,3-Bis(pyridyl-4-ylthio)propan-2-one

1 INTRODUCTION Widespread interest of metal-organic coordination compounds has been stirred by their intriguing struc- tural topologies and promising properties[1]. Al- though structural motifs of coordination compounds are mainly defined by metal ions’ coordination pre- ferences and chemical structures of organic ligands including the molecular angle, length and relative orientation of the donor groups[2], numerous other factors such as solvent systems, concentration, coun- terions and e…     

Synthesis and Structural Characterization of a New Cadmium(II) Complex with a Double Betaine

1 INTRODUCTION The construction of supramolecular aggregates has received much attention due to their intriguing network topologies and potential functions as new classes of materials[1, 2]. Multiple noncovalent interac- tions, such as hydrogen bonds, π-π stacking and host- guest ionic interactions, play important roles in the supramolecular assembly of metal ions and organic ligands[3, 4]. In this context the multidentate ligands with conjugated groups are employed as building blocks in…     

二硝酸根二4′，5′-二氮-9′-(4，5-二(硫乙基)-1，3-二硫杂环戊烯-2-叶立德)-芴合镉的合成、结构及光谱性质

Cd(NO₃)₂·4H₂O与配体4′,5′-二氮-9′-(4，5-二(硫乙基)-1，3-二硫杂环戊烯-2-叶立德)-芴(L)在甲醇和二氯甲烷的混合溶剂中生成配合物Cd(NO₃)₂(L)₂。晶体的空间群是Pbcn(#60)，晶体学参数分别是a=1.578 7(2) nm，b=0.987 96(11) nm，c=2.719 5(3) nm。V=4.241 6(8) nm³，Z=4。2个硝酸根离子各提供1个氧原子，2个配体L各提供2个氮原子，形成了镉的6配位结构。晶体结构显示分子通过平面之间的π-π相互作用沿b轴形成柱状结构，这些柱通过中心原子镉(Ⅱ)的配位连接形成二维层状结构，再通过2个硫乙基上的短距离S…S接触进一步形成了三维结构。对其 ¹H NMR、UV-Vis和荧光光谱进行了研究。     

Synthesis,characterization, and crystal structures of two new divalent metal complexes of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6: a hydrogen-bonded 1D array and a 3D network with a large channel

Reaction of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6 (H(4)L) with copper(II) acetate in 1:1 ethanol/water mixed solvents afforded a new crystal-engineered supramolecular metal phosphonate, Cu(H(2)L) (complex 1). By reaction of the same ligand with cadmium(II) nitrate in a 2:1 (M/L) ratio in methanol, a cadmium(II) complex with a 3D network structure was isolated, Cd(2.75)(L)(H(2)O)(7) x 1.5NO(3) x 7H(2)O x MeOH (complex 2). The copper(II) complex crystallized in the monoclinic space group P2(1)/c, with a =10.125(4), b = 14.103(6), and c = 14.537(6) A, beta = 91.049(8) degrees, V = 2075.4(16) A(3), and Z = 2. The Cu(II) ions in complex 1 are 6-coordinated by two phosphonate oxygen atoms, two nitrogen, and two oxygen atoms from the crown ether ring. Their coordination geometry can be described as Jahn-Teller-distorted octahedral, with elongated Cu-O(crown) distances (2.634(4) and 2.671(4) A for Cu(1) and Cu(2), respectively). The other two crown oxygen atoms remain uncoordinated. Neighboring two Cu(H(2)L) units are further interlinked via a pair of strong hydrogen bonds between uncoordinated phosphonate oxygen atoms, resulting in a one-dimensional supramolecular array along the a axis. The cadmium(II) complex is tetragonal, P4(2)/n (No. 86) with a = 20.8150(9) and c = 18.5846(12) A, V = 8052.0(7) A(3), and Z = 8. Among four cadmium(II) atoms in an asymmetric unit, one is 8-coordinated by four chelating phosphonate groups, the second one is 8-coordinated by 6 coordination atoms from a crown ring and two oxygen atoms from two phosphonate groups, the third Cd(II) atom is octahedrally coordinated by three aqua ligands and three phosphonate oxygen atoms from three phosphonate groups, and the fourth one is 6-coordinated by four aqua ligands and two oxygen atoms from two phosphonate groups in a distorted octahedral geometry. These cadmium atoms are interconnected by bridging phosphonate tetrahedra in such a way as to form large channels along the c direction, in which the lattice water molecules, methanol solvent, and nitrate anions reside. The effect of extent of deprotonation of phosphonic acids on the type of complex formed is also discussed.     

Synthesis and structural characterization of 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O and 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O and [Co(dien)(2)][V(3)O(9)].H(2)O templated by cobalt complexes: cooperative organization of the complexes and the inorganic networks

A 0D vanadium borophosphate [Co(en)(3)](2)[V(3)P(3)BO(19)][H(2)PO(4)].4H(2)O (1) and two 1D vanadium oxides [Co(en)(3)][V(3)O(9)].H(2)O (2) and [Co(dien)(2)][V(3)O(9)].H(2)O (3) have been synthesized hydrothermally from the reaction mixture of V(2)O(5)-H(3)PO(4)-H(3)BO(3)-CoCl(2)-R-H(2)O at 110 degrees C (R: en or dien). The complex cations Co(en)(3)(3+) and Co(dien)(2)(3+) are cooperatively organized in the reaction medium to play a structure-directing role in the formation of the inorganic clusters and chains. The structures are determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The structure of 1 contains isolated [V(3)P(3)BO(19)](5)(-) cluster anions, H(2)PO(4)(-) anions, racemic Co(en)(3)(3+) cations, and H(2)O molecules, which form a complex H-bond network. 2 and 3 both contain chains of corner-sharing VO(4) tetrahedra running along the 2(1) screw axis. The complex cations located in the interchain region interact with the chains through H-bonds. 2 is crystallized in an enantiomorphic space group and only one enantiomer of Co(en)(3)(3+) is involved in the structure. Crystal data: 1, monoclinic, C2/c, a = 32.8492(14) A, b = 11.9601(3) A, c = 22.6001(7) A, beta = 108.9630(8) degrees, Z = 8; 2, orthorhombic, P2(1)2(1)2(1), a = 8.1587(16) A, b = 12.675(3) A, c = 18.046(4) A, Z = 4; 3, monoclinic, P2(1)/c, a = 16.1663(10) A, b = 8.7028(3) A, c = 13.9773(5) A, beta = 103.1340(18) degrees, Z = 4.     

Syntheses, structures, and photoluminescence of a novel class of d10 metal complexes constructed from pyridine-3,4-dicarboxylic acid with different coordination architectures

Two novel d(10) metal coordination polymers [Zn(PDB)](n)() (1) and [Cd(3)(PDB)(2)(OH)(2)(H(2)O)(2)](n)() (2) (H(2)PDB = pyridine-3,4-dicarboxylic acid) have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TG analysis, and single-crystal X-ray diffraction. Crystal data for 1: C(7)H(3)NO(4)Zn, orthorhombic Pna2(1), a = 8.423(17) A, b = 6.574(13) A, c = 12.899(3) A, Z = 4. Crystal data for 2: C(14)H(12)N(2)O(12)Cd(3), monoclinic C2/c, a= 20.130(4) A, b = 6.692(13) A, c = 13.081(3) A, beta = 102.78(3) degrees, Z = 4. Both compounds exhibit novel three-dimensional frameworks. Compound 1 not only possesses a one-dimensional rectangular channel but also contains infinite double-stranded helical chains. Compound 2 has two different types of channels, one being built up from pyridine rings and [CdO(5)N] and [CdO(6)] building units and the other being constructed from pyridine rings and [CdO(5)N] building units. Furthermore, both compounds show strong photoluminescence properties at room temperature.