Hydrothermal synthesis and characterizations of a novel modular europium(III) coordination polymer bridged by biphenyl-2,2′-dicarboxylate dianions and 1,10-phenanthroline

A novel europium(III) coordination polymer, [Eu₂(bpdc)₃(phen)₂(H₂O)₂] _n ·nH₂O (1) (bpdc?= biphenyl-2,2′-dicarboxylate; phen?=?1,10-phenanthroline), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction methods. Complex 1 is monoclinic, space group C2/c, with a?=?24.3862(6), b?=?12.0792(3), c?=?22.9120(5)?Å, α?=?90.00, β?=?115.160(1), γ?=?90.00°, V?=?6108.8(3)?ų, Z?=?4, final R ₁?=?0.0605 and wR ₂?=?0.1760. Each Eu(III) ion is coordinated by six oxygen atoms from three carboxylate groups of three different bpdc anions, an oxygen atom from one coordinated water molecule and two nitrogen atoms from one phen ligand to complete a deformed monocapped square antiprism. Each pair of bpdc anions acts as a tetradentate ligand to connect two adjacent Eu(III) ions through chelating carboxylate groups, resulting in a centrosymmetric binuclear unit. Each binuclear unit links two adjacent binuclear units through two terminal bpdc anions to produce a one-directional zigzag chain. Two different kinds of hydrogen-bonding interactions link the chains and the lattice water molecules to form a hydrogen-bonding network.     

Hydrothermal synthesis,structures and characterization of two new copper(II) triphosphonate compounds

Two copper(II) triphosphonate compounds, Cu[(APTPH₄)(phen)(H₂O)]?·?2.16H₂O (1) and [Cu(APTPH₄)(2,2′-bipy)(H₂O)]?·?2.63H₂O (2), have been prepared by a low temperature hydrothermal reaction from 1-aminopropane-1,1,3-triphosphonic acid (APTPH₆), CuO and a second ligand, phen?=?1,10-phenanthroline, or 2,2′-bipy?=?2,2′-bipyridyl. These two compounds were characterized by single crystal X-ray diffraction, elemental analysis, IR and TG. Crystal data for 1: Monoclinic, space group P2₁ /c, a?=?14.4830(7)?Å, b?=?9.1721(5)?Å, c?=?16.7403(8)?Å, β?=?90.101(2)°. For compound 2: Triclinic, space group P 1, a?=?7.1215(7)?Å, b?=?10.460(2)?Å, c?=?14.671(2)?Å, α?=?82.983(2)°, β?=?83.882(2)°, γ?=?80.617(2)°. In both compounds, each Cu²⁺ ion is five-coordinate with two oxygen atoms from the triphosphonate, two nitrogen atoms from the second ligand and one water molecule, to form a distorted square-pyramidal geometry. Both complexes have 3D supramolecular structures constructed by hydrogen bonds and π–π stacking interactions.     

Syntheses,crystal structures and magnetic study of two binuclear manganese(II) complexes with aromatic N-oxide as bridging ligand

Two new binuclear complexes, [Mn₂(μ-dmpo)₂(SCN)₄(H₂O)₂] (1) (where dmpo?=?3,5-dimethylpyridine N-oxide), [Mn₂(μ-po)₂(H₂O)₆I₂]I₂ (2) (where po?=?pyridine N-oxide), have been synthesized and their crystal structures determined by X-ray crystallography. Complexes 1 and 2 crystallize in monoclinic, space group P2₁/c, with unit cell dimensions a?=?8.8836(18)?Å, b?=?15.450(3)?Å, c?=?15.484(3)?Å, β?=?91.020(3)° for 1, and a?=?8.8352(13)?Å, b?=?17.927(3)?Å, c?=?8.3338(12)?Å, β?=?103.765(2)° for 2. In each binuclear complex two Mn(II) were bridged by two 3,5-dimethylpyridine N-oxides or by two pyridine N-oxides and the distances between the bridged Mn(II) ions are 3.599?Å for 1 and 3.552?Å for 2. Variable temperature (4–300?K) magnetic measurements were performed for 1 and the susceptibility data were fitted by using a binuclear Mn(II) magnetic coupling formula producing the 2J?=??2.17?cm^?1.     

Hydrothermal synthesis,crystal structure and third-order non-linear optical property of a copper chloride cluster

A novel one-dimensional chain coordination polymer [[CuCl₂]₂(phen)₂]_∞ (1) and a three-dimensional coordination polymer [[CuCl] (phen)₂](CuCl₂) (2) were synthesized from simple hydrothermal reactions and the structures were characterized with elemental analysis, FT-IR spectrum and X-ray diffraction. Compound 1 crystallized in the monoclinic space group Cc with a?=?9.874(2), b?=?17.871(4), and c?=?13.440(3)?Å, α?=?90.00°, β?=?106.59(3)°, γ?=?90.00°, R ₁?=?0.0463, wR ₂?=?0.0819. Compound 2 crystallized in the monoclinic space group P2/c with a?=?14.4084(13), b?=?12.6280(11) and c?=?13.3560(12)?Å, α?=?90.00°, β?=?111.490(2)°, γ?=?90.00°, R ₁?=?0.0771, wR ₂?=?0.1439. In the packing structure, π–π stacking interactions are the most significant factors controlling the novel supramolecular sheets for the title compound. Moreover, the third-order non-linear optical property of the two compounds were also investigated and they show reverse saturable absorption and self-focusing performance.     

A 1D coordination polymer {Pb[C6H4(COO)2][phen]} n with strong blue fluorescent emission

The hydrothermal reaction of 1,3-dicyanobenzene, 1,10-phenanthroline (phen) and Pb(CH₃COO)₂ yields a new 1D coordination polymer, {Pb[C₆H₄(COO)₂][phen]} _n . The 1,3-benzenecarboxylate anion found in the final product was generated in situ during the synthesis by hydrolysis of 1,3-dicyanobenzene. X-ray diffraction shows that complex 1 crystallizes in the triclinic system, space group P 1, a?=?7.5442(2)?Å, b?=?9.7962(3)?Å, c?=?13.1505(4)?Å, α?=?69.739(2)?Å, β?=?80.597(2)?Å, γ?=?71.377(2)?Å, v?=?862.48(4)?ų, Z?=?2, D _c?=?2.124 Mg?m^?3. Complex 1 emits strong blue fluorescent light (λem(max)?=?482.4?nm) when excited by UV light in the solid state at room temperature.     

Hydrothermal synthesis,characterization, and luminescence of two new arsenic–vanadium compounds with a γ-[As8V14O42(H2O)]4− anion

Two new compounds, [Zn(phen)₃]₂[γ-As₈V₁₄O₄₂(H₂O)]?·?4H₂O (1) and [Cd(phen)₃]₂[γ-As₈V₁₄O₄₂(H₂O)]?·?2H₂O (2) (phen?=?1,10′-phenanthroline), have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, infrared spectrum, and thermogravimetric analysis. Compound 1 crystallizes in the triclinic space group P 1 with a?=?11.429(4)?Å, b?=?15.760(5)?Å, c?=?15.952(5)?Å, α?=?108.825(5)°, β?=?92.194(5)°, γ?=?104.155(5)°, V?=?2615.6(15)?ų, Z?=?1; 2 crystallizes in the triclinic space group P 1 with a?=?11.450(4)?Å, b?=?15.629(6)?Å, c?=?16.302(6)?Å, α?=?109.177(5)°, β?=?92.628(5)°, γ?=?104.251(4)°, V?=?2644.8(17)?ų, Z?=?1. Single-crystal structural analysis shows that both 1 and 2 consist of a new type of [γ-As₈V₁₄O₄₂(H₂O)]^4? cluster anion.     

A novel inorganic-organic hybrid based on a Wells–Dawson polyanion containing two types of organic fragments

A new inorganic-organic hybrid, [Zn(phen)₂(ppy)][{Zn(phen)₂}{Zn(phen)₂(H₂O)}{P₂W₁₈O₆₂}]?·?2H₂O (phen?=?1,10′-phenanthroline, ppy?=?2-(5-phenylpyridin-2-yl)pyridine) (1), by using pre-prepared Wells–Dawson salt α-K₆P₂W₁₈O₆₂?·?15H₂O as precursor, has been synthesized under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray diffraction, elemental analyses, IR spectrum and cyclic voltammetry. Yellow crystals crystallized in the monoclinic space group P2 (1)/c with a?=?16.2450(11)?Å, b?=?17.0918(11)?Å, c?=?43.640(3)?Å, β?=?92.0060(10)°, V?=?12109.4(14)?ų, Z?=?4. The title compound represents a novel zero-dimensional structure based on bisupporting Wells–Dawson POM: one terminal oxygen atom located in the “belt” site and another located in the “cap” site of the same hemisphere of the polyanion are coordinated by Zn²⁺ cations. Compound 1 also contains the isolated secondary metal complex [Zn(phen)₂(ppy)]²⁺ with two different organic ligands phen and ppy.     

Synthesis and structures of three triphosphonate compounds containing d10 transition metal ions

Three new triphosphonate compounds, [Zn(APTPH₄)(2,2′-bipy)(H₂O)]?·?2H₂O (1), [Cd(APTPH₄)(2,2′-bipy)(H₂O)]?·?2H₂O (2), and [Zn(APTPH₄)(phen)₂]?·?phen?·?4H₂O (3) (APTPH₆?=?1-aminopropane-1,1,3-triphosphonic acid, 2,2′-bipy?=?2,2′-bipyridine, phen?=?1,10-phenanthroline), are synthesized by a low-temperature hydrothermal method. Compounds 1 and 2 are isomorphous, both one-dimensional (1D) coordination polymers expanded into three-dimensional (3D) supramolecular structures by hydrogen bonds and π–π stacking interactions. Compound 3 is a molecular complex and forms a 3D network through an S-shaped water hexamer. Crystal data for 1: Triclinic, space group P 1, a?=?6.6814(5)?Å, b?=?10.0929(7)?Å, c?=?15.438(2)?Å, α?=?81.544(2)°, β?=?79.066(2)°, γ?=?82.278(2)°, Z?=?2; for 2: Triclinic, space group P 1, a?=?6.9380(8)?Å, b?= 10.043(2)?Å, c?=?15.681(2)?Å, α?=?81.357(2)°, β?=?78.510(2)°, γ?=?81.902(2)°, Z?=?2; Crystal data for 3: Triclinic, space group P 1, a?=?12.540(2)?Å, b?=?12.596(2)?Å, c?=?14.997(2)?Å, α?=?100.795(2)°, β?=?113.328(2)°, γ?=?101.358(2)°, Z?=?2.     

A dimeric luminescent lanthanide complex [Eu(PAA)2(phen)(NO3)]2: hydrothermal synthesis,crystal structure and fluorescence

A lanthanide coordination complex [Eu(PAA)₂(phen)(NO₃)]₂ (PAA?=?phenylacetic acid, phen?=?1,10-phenanthroline) has been synthesized by the hydrothermal method. Single crystal X-ray diffractions show that it forms a dimeric molecular structure. The title complex crystallizes in the triclinic system, space group P 1, with lattice parameters a?=?8.9473(8)?Å, b?=?13.3659(12)?Å, c?=?13.4745(12)?Å, α?=?60.7590(10)°, β?=?89.5100(10)°, γ?=?71.9850(10)°, V?=?1317.3(2)?ų, D _c?= 1.675?Mg?m^?3, Z?=?1, F(000)?=?660, GOF?=?1.003, R ₁?=?0.0206, wR ₂?=?0.0575. The fluorescence excitation and emission spectra have been investigated.     

Synthesis and crystal structure of a novel luminescent cadmium complex

A novel cadmium complex Cd(IPA)₂(phen)₂ (IPAH?=?isophthanic acid, phen?=?1,10-phenanthroline) was synthesized by hydrothermal methods and characterized structurally by X-ray diffraction. The complex possesses a monomeric molecular structure. Cd(IPA)₂(phen)₂ is orthorhombic, space group Aba2, with a?=?14.670(7), b?=?22.876(8), c?=?9.473(6)?Å, V?=?3179(3)?ų, D _c?=?1.573?Mg?m^?3, Z?=?4, F(000)?=?1520, GOF?=?1.027, R1?=?0.0299, wR2?=?0.0617. Photophysical properties (fluorescence excitation and emission spectra) are reported.     

A cyanide-containing cobalt(III) complex [Co(phen)2(CN)2][Co(phen)(CN)4]·4.5H2O: hydrothermal synthesis,crystal structure and spectroscopic properties

A cyanide-containing cobalt(III) complex, [Co(phen)₂(CN)₂][Co(phen)(CN)₄]?·?4.5H₂O (1: phen?=?1,10-phenanthroline) has been synthesized by hydrothermal techniques and characterized by elemental analyses, IR spectroscopy, UV–vis spectroscopy and single-crystal X-ray diffraction methods. The complex is triclinic, space group P 1 , with a?=?11.0047(16), b?=?12.9587(19), c?=?15.076(2)?Å, α?=?100.060(2), β?=?102.061(2), γ?=?91.803(2)°, V?=?2065.0(5)?ų, Z?=?2, and R ₁ [I?>?2σ(I)]?=?0.0481. The molecular unit of 1 consists of a cation/anion pair with interstitial water molecules in the crystal lattice. The combination of coordinative, hydrogen bonding and π–π stacking interactions results in the stabilization of a supramolecular solid-state architecture.     

Synthesis and crystal structure of a Cu(II) complex with mixed malonate/1,10-phenanthroline ligands

A Cu(II) complex with mixed ligands, [Cu₃(mal)₃(phen)₃(H₂O)₂]?·?11H₂O (mal?=?malonate, phen?=?1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, UV, electron paramagnetic resonance (EPR) and luminescence spectra and single-crystal X-ray diffraction. The complex crystallizes in the monoclinic system, space group Cc with a?=?13.1631(10)?Å, b?=?20.1089(10)?Å, c?=?20.1267(13)?Å, β?=?103.500(3)°, V?=?5180.2(6)?ų, Z?=?4, and R ₁?=?0.0476 for 7993 observed reflections. In the complex, one Cu is coordinated by a mal dianion and a phen molecule, exhibiting N₂O₂ square-planar geometry, while the other two Cu atoms are coordinated, respectively, by a mal dianion, a phen and water molecules, exhibiting N₂O₃ square pyramidal coordination geometry.     

Synthesis,crystal structures and magnetism of lanthanide(III) binuclear complexes [Ln2(μ1 ,3-CH3CO2)2(SCN−)4L2(H2O)6] (Ln = Gd(III) and Eu(III), L = 4-methylpyridine N-oxide)

Two lanthanide(III) binuclear complexes have been synthesized with acetate as bridging ligand and 4-methylpyridine N-oxide (L), SCN^? and H₂O as terminal ligands and structurally determined by X-ray crystallography. Both crystals [Gd₂(μ_1,3-CH₃CO₂)₂(SCN^?)₄(L)₂(H₂O₆) (1) and [Eu₂(μ_1,3-CH₃CO₂)₂(SCN^?)₄(L)₂(H₂O)₆] (2) belong to monoclinic with space group P2₁/n. The relevant cell parameters are as follows: a?=?9.0034(12)?Å, b?=?15.998(2)?Å, c?=?12.1277(17)?Å, β?=?100.625(2)° for complex 1; and a?=?9.0168(18)?Å, b?=?15.990(3)?Å, c?=?12.142(2)?Å, β?=?100.734(3)° for complex 2; The two lanthanide(III) ions are bridged by two acetate anions forming a binuclear unit, in which L, SCN^? and H₂O as unidentate terminal ligands take part in the coordination. The variable-temperature magnetic susceptibility of 1 was measured in the 4–300?K range; fitting for the susceptibility data reveals that there is no magnetic interaction between the bridged Gd(III) ions.     

Synthesis of novel copper compounds containing isonicotinic acid and/or 2,6-pyridinedicarboxylic acid: third-order nonlinear optical properties

Two novel compounds, [Cu₂(pydc)₂(inta)₂(H₂O)₂]·3H₂O 1 (pydc?=?2,6-pyridinedicarboxylic acid, inta?= isonicotinic acid) and [Cu(pydc)₂][Cu(H₂O)₅]·2H₂O 2, have been synthesized in aqueous solution and characterized by single-crystal X-ray diffraction, elemental analyses and IR spectra. Compound 1 exhibits reverse saturable absorption and self-defocusing. X-ray structural analysis reveals that Compounds 1 and 2 both possess π–π stacking and hydrogen-bonding interactions forming three-dimensional (3D) networks. Crystal data for 1: a?=?7.2345(14), b?=?12.219(2), c?=?17.069(3)?Å, α?=?90.44(3), β?=?91.82(3), γ?=?93.56(3)°, Z?=?1, R1?=?0.0435, wR2?=?0.1216. Crystal data for 2: a?=?8.3708(17), b?=?27.386(6), c?=?9.6170(19)?Å, α?=?90.00, β?=?98.14(3), γ?=?90.00°, Z?=?3, R1?=?0.0742, wR2?=?0.2160.     

Syntheses,structural determination,and binding studies of nine-coordinate mononuclear (mnH)2[DyIII(Httha)]·3H2O and (enH2)3[DyIII(ttha)]2·9H2O

Two dysprosium coordination compounds, (mnH)₂[Dy^III(Httha)]·3H₂O (1) (H₆ttha?=?triethylenetetramine-N,N,N′,N″,N′′′,N′′′-hexaacetic acid and mn?=?methylamine) and (enH₂)₃[Dy^III(ttha)]₂·9H₂O (2) (en?=?ethylenediamine), were synthesized through direct heating and characterized by elemental analysis, FT-IR, thermal analysis, and single-crystal X-ray diffraction. X-ray diffraction analysis displays that 1 is a mononuclear nine-coordinate complex with a pseudo-monocapped square antiprismatic conformation (MCSAP) crystallizing in the monoclinic crystal system with P2(1)/c space group. The crystal data are as follows: a?=?16.1363(19)?Å, b?=?13.9336(11)?Å, c?=?13.6619(14)?Å, β?=?102.2490(10)°, and V?=?3001.8(5)?ų. There are two kinds of methylamine cation in 1. They connect [Dy^III(Httha)]^2?and crystal waters through hydrogen bonds, leading to formation of a 2-D ladder-like layer structure. The polymeric 2 also is a nine-coordinate structure with a pseudo-MCSAP crystallizing in the monoclinic crystal system with P2/c space group. The cell dimensions are: a?=?17.7801(16)?Å, b?=?9.7035(10)?Å, c?=?22.096(2)?Å, β?=?118.874(2)°, and V?=?3338.3(6)?ų. In 2 there are also two types of ethylenediamine cations. One connects three adjacent [Dy^III(ttha)]^3? complex anions through hydrogen bonds and the other is symmetrical forming hydrogen bonds with two neighboring [Dy^III(ttha)]^3? complex anions. These hydrogen bonds result in formation of a 2-D ladder-like layer structure as well.     

Synthesis,structure and characterization of copper(II) and zinc(II) complexes based on 3-carboxyl-1,2,4-triazole

Two complexes [CuL₂(H₂O)₂] (1) and [ZnL₂(H₂O)₂] (2) (L?=?3-carboxyl-1,2,4-triazole (L)) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the monoclinic space group P ₂(1)/n, a?=?8.632(8)?Å, b?=?9.153(8)?Å, c?=?6.991(7)?Å, β?=?94.279(12)°, Z?=?2, R ₁?=?0.0296, wR ₂?=?0.0918. Compound 2 also crystallizes in the monoclinic space group P ₂(1)/n, a?=?4.937(3)?Å, b?=?18.107(10)?Å, c?=?6.344(4)?Å, β?=?106.839(7)°, Z?=?2, R ₁?=?0.0230, wR ₂?=?0.0556. Extensive intermolecular hydrogen bonds assemble 1 and 2 into three-dimensional (3D) supramolecular architectures, with eight-member H-bonded synthons. Compounds 1 and 2 were also characterized by element analysis, FT–IR, luminescence and EPR studies.     

Hydrothermal synthesis and crystal structure of a metal–organic compound with unique pseudo-hexagonal water channels: [CuII(phen)(sal)]·0.5H2O (phen=1,10-phenanthroline,sal=salicylic acid)

This article presents a metal–organic compound [Cu^II(phen)(sal)]?·?0.5H₂O (1) with intriguing structural motif of 3D hexagonal water channels. Furthermore, IR, element analysis, and TGA were employed to characterize it. The TG-DTA showed that this structure is stable to 300°C. Compound 1 belongs to the hexagonal system, space group R-3, a?=?33.337(5)?Å, b?=?33.337(5)?Å, c?=?9.4599(19)?Å, γ?=?120°, V?=?9105(3)?ų, Z?=?18.     

Syntheses,crystal structures,and antimicrobial activities of nickel(II) and cadmium(II) complexes with 4-methylsulfonyl cinnamate and diamines

Two metal complexes, [Ni^II(mscinn)₂(pda)₂] (1) and [Cd^II(mscinn)₂(dmeda)₂·2H₂O] (2) (mscinn?=?4-methylsulfonyl cinnamate, pda?=?propane-1,3-diamine, dmeda?=?N′,N′-dimethylethane-1,2-diamine), were synthesized by reacting 4-methylsulfonyl cinnamate with the diamines and metal salts. Their structures were determined by single-crystal X-ray diffraction analysis. Crystal parameters of 1: C₂₆H₃₈N₄NiO₈S₂, M?=?657.43, monoclinic, P2₁/c, a?=?16.6123(8)?Å, b?=?8.5956(4)?Å, c?=?11.2047(5)?Å, β?=?107.423(1)°, V?=?1526.54(12)?ų, Z?=?2, D _calcd?=?1.430?g?cm^?3, F(000)?=?692, μ?=?0.825?mm^?1, R ₁?=?0.0257, wR ₂?=?0.0669. Crystal data of 2: C₂₈H₄₂CdN₄O₈S_2?·?2(H₂O), M?=?775.24, monoclinic, P2₁/c, a?=?9.8278(4)?Å, b?=?11.6611(5)?Å, c?=?15.3972(7)?Å, β?=?96.195(1)°, V?=?1754.26(13)?ų, Z?=?2, D _calcd?=?1.468?g?cm^?3, F(000)?=?804, μ?=?0.798?mm^?1, R ₁?=?0.0299, wR ₂?=?0.0770. Antimicrobial activities for 1 and 2 against Escherichia coli, Pseudomonas putida, Bacillus subtilis, and Bacillus cereus had better antibacterial activity than their parent carboxylic acid against Gram-positive bacteria (B. subtilis and B. cereus). The cadmium complex of the cinnamate displayed high inhibitory activity with an MIC value of 5?µg?mL^?1 against P. putida, while the nickel complex also exhibited good inhibitory potency with an MIC value of 5?µg?mL^?1 against B. subtilis.     

Metal–oxo cluster-supported transition metal complexes: hydrothermal synthesis and characterization of [{Cu(phen)2}2SiW12O40]

A new neutral α-Keggin polyoxometalate, [{Cu(phen)₂}₂SiW₁₂O₄₀] (1) (phen?=?1,10-phenanthroline) was hydrothermally synthesized and characterized by IR, TG and single-crystal X-ray diffraction. The compound is monoclinic, space group P2₁/c with a?=?26.065(5), b?=?11.867(2), c?=?23.385(5)?Å, β?=?113.78(3)°, V?=?6619?ų, Z?=?4. X-ray analysis showed that both [Cu(phen)₂]²⁺ units are supported on the α-Keggin polyoxoanion [SiW₁₂O₄₀]^4? via the surface bridging and terminal oxygen atoms of two non-adjacent WO6 octahedra; these show unusual coordination environments. One Cu ion displays distorted trigonal bipyramidal geometry and the other square pyramidal. The unusual coexistence of complexes with different geometries is most likely caused by steric effects involving surface oxygen atoms of the heteropolytungstate and phen, which prevent the presence of a sixth coordinating atom. Weak π–π stacking interactions between phen groups give a 1D chain-like structure and hydrogen bonds are responsible for extended 2D and 3D motifs in the crystal.