Syntheses,crystal structures and fluorescent properties of four one-dimensional lanthanide coordination polymers with 3-cyanobenzoato

The hydrothermal reactions of Nd(ClO₄)₃·6H₂O, Gd(ClO₄)₃·6H₂O, Dy(ClO₄)₃·6H₂O, Er(ClO₄)₃·6H₂O with 1,3-dicyanobenzene, give rise to four one-dimensional rare earth-based coordination polymers: [M(3-CNC₆H₄COO)₃(H₂O)₂] _n (where M?=?Nd (1), Gd (2), Dy (3), Er (4), 3-CNC₆H₄COO?=?3-cyanobenzoato), respectively. Their solid-state structures have been characterized by X-ray single-crystal diffraction studies. The results show that 1,3-dicyanobenzene hydrolyzed to give 3-cyanobenzoato under hydrothermal condition, and the four complexes are isomorphous. Crystal data for 1: triclinic, space group P-1, a?=?9.4063(19), b?=?11.485(2), c?=?12.616(3)?Å, α?=?66.38(3), β?=?74.01(3), γ?=?86.96(3)°, V?=?1197.9(4)?ų, Z?=?1, D _c?=?1.704?Mg?m^?3; for 2: triclinic, space group P-1, a?=?9.3712(19), b?=?11.446(2), c?=?12.627(3)?Å, α?=?65.86(3), β?=?73.89(3), γ?=?86.84(3)°, V?=?1184.8(4)?ų, Z?=?1, D _c?=?1.759?Mg?m^?3; for 3: triclinic, space group P-1, a?=?9.3425(19), b?=?11.432(2), c?=?12.703(3)?Å, α?=?65.28(3), β?=?73.80(3), γ?=?86.86(3)°, V?=?1180.6(4)?ų, Z?=?1, D _c?=?1.780?Mg?m^?3; for 4: triclinic, space group P-1, a?=?9.3425(19), b?=?11.432(2), c?=?12.703(3)?Å, α?=?65.28(3), β?=?73.80(3), γ?=?86.86(3)°, V?=?1180.6(4)?ų, Z?=?1, D _c?=?1.7794?Mg?m^?3. The fluorescence emission spectra of compounds 1 to 4 are also reported.     

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.     

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.     

Synthesis,crystal structures and fluorescence of cadmium(II) coordination polymers with derivatives of pyrazine-1,4-dioxide and thiocyanate as mixed-bridging ligands

Two Cd(II) coordination polymers have been synthesized with derivatives of pyrazine-1,4-dioxide and thiocyanate anion as bridging ligands and structurally determined by X-ray crystallography. Complex 1, [Cd(μ_1,3-SCN^?)₂(μ_1,6-L1)] _n (L1?=?2,5-dimethylpyrazine-1,4-dioxide), belongs to the triclinic, space group P 1 with a?=?5.7627(18)?Å, b?=?7.182(2)?Å, c?=?7.509(2)?Å, α?=?74.042(3)°, β?=?84.766(4)°, γ?=?88.162(4)°; complex 2, [Cd₂(μ_1,3-SCN^?)₄(μ₄-L2)] _n (L2?=?2,3,5,6-tetramethylpyrazine-1,4-dioxide), crystallizes in a monoclinic system with space group C2/m with a?=?10.194(4)?Å, b?=?13.491(6)?Å, c?=?8.140(3)?Å, β?=?120.372(4)°. Complex 1 shows a two-dimensional sheet structure, and in a direction the Cd(II) ions were coordinated by μ_1,3-SCN^? forming the one-dimensional chain and the L1 bridging ligand made the chains connect in the c direction leading to formation of a two-dimensional sheet on the ac plane. For 2 the one-dimensional chains in the a axis were constructed by coordination of μ_1,3-SCN^? bridging ligands with the Cd(II) ions, and in b and c directions the chains were joined by L2 bridging ligands leading to a three-dimensional structure. In 2 L2 displays a μ₄-bridging coordination mode. Both complexes exhibit strong fluorescence emission.     

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.     

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.     

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.     

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.     

An open-framework cobalt molybdate possessing {Mo2O7} building block: hydrothermal synthesis and structural characterization of [CoMo2O7(4,4′-bipy)1.5]

The hydrothermal reaction of Co(COO)₂?·?4H₂O, MoO₃, H₃PO₄ and 4,4′-bipyridine yields bipyridine-ligated cobalt dimolybdate [CoMo₂O₇(4,4′-bipy)_1.5] (1) (4,4′-bipy?=?4,4′-bipyridine) in the triclinic system with space group of P 1 and cell parameters of a?=?7.1951(8)?Å, b?=?11.1708(17)?Å, c?=?11.4514(11)?Å, α?=?98.545(7)°, β?=?90.315(2)°, γ?=?105.777(5)°, V?=?874.88(19)?ų, and Z?=?2. Its structure consists of Co/Mo/O bimetal oxide layers with {Mo₂O₇} building blocks, linked by the coordination of 4,4′-bipy ligand with Co and Mo atoms, into a 3D porous hybrid framework.     

Syntheses,crystal structures,and fluorescence properties of two isomorphic binuclear compounds incorporating N-acetyl-N-phenylglycinate with N-donor co-ligands

In this study, two new isomorphic binuclear compounds, [Ln(µ-NAP)₄(NAP)₂(phen)₂]?·?H₂O (1) and (2) (Ln?=?Eu, Tb, NAP?=?N-acetyl-N-phenylglycinate; phen?=?1,10-phenanthroline), have been synthesized and characterized by infrared spectroscopy, elemental analysis, and X-ray crystallography. These compounds crystallize in a triclinic form with space group Pī with a?=?11.7519(11), b?=?13.4293(12), c?=?14.0686(13)?Å, V?=?1992.7(3)?ų, and Z?=?1. Single-crystal X-ray structural analysis reveals that 1 is binuclear, assembled into a 3-D supramolecular network with self-complementary double hydrogen-bonding interactions and aromatic π–π interactions. Fluorescence properties of 1 and 2 are also discussed.     

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.     

Hydrothermal synthesis and crystal structure of a new two-dimensional zinc citrate complex

A new two-dimensional compound C₁₂H₁₄O₁₆Zn₃ (1), containing seven-coordinate zinc atoms was prepared by the hydrothermal technique. The compound obtained was characterized by TG-DTA, single crystal X-ray diffraction, elemental analysis and FT-IR analysis. Single-crystal X-ray diffraction analysis shows that compound 1 crystallizes with monoclinic symmetry in the space group P2₁/c, a?=?6.1552(13)?Å, b?=?14.546(3)?Å, c?=?9.581?Å, β?=?102.66(2)°, V?=?836.9(4)?ų, Z?=?2, R1?=?0.0311, wR2?=?0.0830.     

Solid state structures of the chiral heterobimetallic complexes [Cu(dach)2][Pt(CN)4] · 2H2O, [Ni(dach)3][Pt(CN)4] · 2DMF · H2O,and [Pd(dach)2][Pt(CN)4] · H2O (dach = 1 R , 2 R -diaminocyclohexane)

The chiral dinuclear heterometallic complexes [Cu(dach)₂][Pt(CN)₄]?·?2H₂O (1), [Ni(dach)₃][Pt(CN)₄]?·?2DMF?·?H₂O (2), and [Pd(dach)₄][Pt(CN)₄]?·?H₂O (3) (dach?=?1R,2R-cyclohexanediamine) have been prepared and characterized by X-ray diffraction analysis. Crystal data: 1, monoclinic, P2₁, a?=?8.108(3), b?=?15.552(6), c?=?9.914(4)?Å, β?=?110.931(6)°, V?=?1167.6(8)?ų, Z?=?2, R ₁?=?0.0420, wR ₂?=?0.1122; 2, monoclinic, P2₁, a?=?13.264(11), b?=?9.285(7), c?=?16.211(13)?Å, β?=?111.640(9)°, V?=?1856(3)?ų, Z?=?2, R ₁?=?0.0276, wR ₂?=?0.0698; 3, monoclinic, P2₁, a?=?6.887(2), b?=?12.809(4), c?=?12.975(4)?Å, β?=?94.865(4)°, V?=?1140.6(6)?ų, Z?=?2, R ₁?=?0.057, wR ₂?=?0.156. In complex 1, the Pt and Cu atoms are linked by a CN bridge that presents a very bent C=N–Cu angle [136.8(8)°].     

Synthesis and structure of a three-dimensional lanthanide complex [Tm2(C5H3N(COO)2)3(H2O)3)]·H2O

A new three-dimensional complex [Tm₂(C₅H₃N(COO)₂)₃(H₂O)₃)]·H₂O (PDC?=?3,5-pyridinedicarboxylate), has been synthesized and its structure determined by x-ray single crystal diffraction methods. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a?=?14.579(4), b?=?11.193(3), c?=?14.839(5)?Å, β?=?94.009(6)°, U?=?2415.5(13)?ų. Two independent PDC ligands bridge Tm^III ions from different orientations to form a network. Thermogravimetric analyses on compound 1 show its high structural stability to 410°C.     

Synthesis and crystal structure of a trinuclear titanium(IV) β -diketonate complex with a six-membered [Ti–(μ-O)]3 ring

The trinuclear titanium(IV) β-diketonate complex, [Ti₃(μ-O)₃(dppd)₆]?·?(DMF)(0.5EtOH) (1) (H-dppd?=?1,3-diphenylpropane-1,3-dione) has been synthesized and its crystal structure and spectroscopic properties have been studied. Complex 1 crystallizes in monoclinic system with space group C2/c and a?=?20.954(5)?Å, b?=?18.705(4)?Å, c?=?24.617(6)?Å, β?=?111.957(4)°, Z?=?4. The complex consists of a six-membered [Ti–(μ-O)]₃ ring, of which three titanium(IV) ions are linked together by bridging oxygen atoms. Each titanium(IV) possesses an octahedral geometry, with four oxygen atoms from the two β-diketonate ligands and two bridging oxygen atoms.     

Synthesis and structures of two cobalt complexes [NaCoII(NTA)(H2O)] n and NH4[CoIII(IDA)2] · 2H2O

Two cobalt complexes [NaCo^II(nta)(H₂O)] _n (H₃nta?=?nitrilotriacetic acid) (1) and NH₄[Co^III(ida)₂]?·?2H₂O (H₂ida?=?iminodiacetic acid) (2) have been synthesized and characterized by single-crystal X-ray diffraction analysis. Compound 1 crystallizes in the orthorhombic system, space group P2₁2₁2₁ with a?=?7.9770(12)?Å, b?=?9.7613(15)?Å, c?=?12.1945(18)?Å, V?=?949.5(2)?ų, Z?=?4, and R ₁?=?0.0705 for 1597 observed reflections. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c with a?=?5.1801(3)?Å, b?=?11.2073(6)?Å, c?=?12.2891(7)?Å, V?=?707.09(7)?ų, Z?=?2, and R ₁?=?0.0349 for 1143 observed reflections. In compound 1, the Co is coordinated by a nitrogen and five oxygen atoms in a distorted octahedral geometry {CoNO₅}, and the Na is coordinated by one water molecule and four carboxyl oxygen atoms in slightly distorted square pyramidal geometry. The entire structure shows a three-dimensional network. In compound 2, Co atom is equatorially coordinated by two ida ligands in a distorted octahedral geometry {CoN₂O₄}. The discrete [Co(ida)₂]^2? anions are linked by hydrogen bonding to a three-dimensional supramolecular network.     

Bis(2-Amino-5-bromopyrimidinium) Tetrahalometallates: Crystal structures of (2-amino-5-bromopyrimidinium)2 MCl4 (M = Co,Zn)

The reactions of metal(II) chlorides and bromides with 2-amino-5-bromopyrimidine (2-abpm) in neutral and acidic solution were investigated. The reaction with ZnCl₂, ZnBr₂, CoCl₂, CoBr₂ and MnCl₂ in acidic nitromethane solution gave complexes of the formula (2-abpmH)₂MX₄ (1, M?=?Zn, X?=?Cl; 2, M?=?Zn, X?=?Br; 3, M?=?Co, X?=?Cl; 4, M?=?Co, X?=?Br; 5, M?=?Mn, X?=?Cl). Crystals of 1 and 3 suitable for single crystal X-ray diffraction were obtained. Crystal data: For (1): triclinic, P-1, a?=?6.2485(13), b?=?9.0520(14), c?=?15.334(4)?Å, α?=?94.81(2), β?=?95.224(17), γ?=?98.027(17)°, V?=?851.1(3)?ų, Z?=?2, R?=?0.0596 for [|I|?≥?2σ(I)]. For (3): triclinic, P-1, a?=?6.2438(13), b?=?9.0597(15), c?=?15.318(3)?Å, α?=?94.749(18), β?=?95.343(15), γ?=?98.021(17)°, V?=?850.2(3)?ų, Z?=?2, R?=?0.0452 for [|I|?≥?2σ(I) ]. Variable temperature magnetic susceptibility data indicates weak antiferromagnetic interactions in the cobalt and manganese complexes.     

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.