Synthesis and structural refinement of fully dehydrated fully Zn<Superscript>2+</Superscript>-exchanged zeolite Y (FAU), |Zn<Subscript>35.5</Subscript>|[Si<Subscript>121</Subscript>Al<Subscript>71</Subscript>O<Subscript>384</Subscript>]-FAU

The single-crystal structure of |Zn_35.5|[Si₁₂₁Al₇₁O₃₈₄]-FAU per unit cell, a = 24.794(1), dehydrated at 673 K and 1 × 10^?6 Torr, has been determined by single-crystal X-ray diffraction techniques in the space group \( Fd\bar{3}m \) at 294(1) K. The structure was refined using all intensities to the final error indices (using the 930 reflections for which F _o > 4σ(F _o)) R ₁ = 0.0448 (based on F) and wR ₂ = 0.1545 (based on F ²). About 35.5 Zn²⁺ ions per unit cell are found at an unusually large number of crystallographic distinct positions, six. The 0.5 Zn²⁺ ion per unit cell is located at the center of double 6-ring (D6R, site I; Zn(I)-O(3) = 2.642(3) Å and O(3)-Zn(I)-O(3) = 81.23(12) and 98.77(12)°). Two different site-I′ positions (in the sodalite cavities opposite D6Rs) are occupied by 14 and 3 Zn²⁺ ions per unit cell, respectively; these Zn²⁺ ions are recessed 0.67 Å and 1.02 Å, respectively, into the sodalite cavities from their 3-oxygens plane (Zn(I′a)-O(3) = 2.094(3) Å, Zn(I′b)-O(3) = 2.23(5) Å, O(3)-Zn(I′a)-O(3) = 110.32(12)°, and O(3)-Zn(I′b)-O(3) = 100.9(30)°). Site-II′ positions (in the sodalite cavities opposite S6Rs) are occupied by 6 Zn²⁺ ions, each of which extends 0.63 Å into the sodalite cavities from their 3-oxygens plane (Zn(II′)-O(2) = 2.164(3) Å and O(2)-Zn(II′)-O(2) = 112.00(12)°). Twelve Zn²⁺ ions are found at two nonequivalent sites II (in the supercage) with occupancies of 7 and 5 ions, respectively; these Zn²⁺ ions are recessed 0.52 Å and 0.96 Å, respectively, into the supercage from their 3-oxygens plane (Zn(IIa)-O(2) = 2.138(12) Å, Zn(IIb)-O(2) = 2.28(4) Å, O(2)-Zn(IIa)-O(2) = 114.2(10)°, and O(2)-Zn(IIb)-O(2) = 103.7(25)°).     

Lanthanide(III) 1,4-Phenylenediacetate Complexes: The Relation Between the Structure and Thermal Properties

The series of isostructural lanthanide coordination polymers with the empirical formula [Ln₂(PDA)₃(H₂O)]·2H₂O, where PDA = 1,4-phenylenediacetate anion = [C₈H₈(COO)₂]^2?; Ln = La-Lu(III), and Y(III) were produced in the reaction of LnCl₃·nH₂O with ammonium salt of 1,4-phenylenediacetic acid in water solution. The compounds were characterised structurally using powder X-ray diffraction, elemental and thermogravimetric analyses as well as FT-IR spectroscopy. Thermogravimetric analyses show that in the range 60–170 °C the dehydration process occurs. The thermal stability of dehydrated compounds, Ln₂(PDA)₃ increased from about 200–350 °C in the whole series of complexes. Single-crystal X-ray diffraction analysis for the Gd(III) complex revealed that the compound crystallizes in the monoclinic P2₁/c space group with a = 21.863(2) Å, b = 10.035(1) Å, c = 13.854(1) Å, β = 91.53(1)° and V = 3,038.5(4) ų. The complex contains one-dimensional gadolinium-carboxylato chains, which are connected with the –CH₂–C₆H₄–CH₂– spacers of PDA ligand to the three-dimensional metal–organic framework.     

1D Coordination Polymer from Tetraaza Macrocyclic Nickel(II) Complex and 1,2,3,4-Cyclobutanetetracarboxylic Acid

The self assembly of [Ni(L)]Cl₂·2H₂O (L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) and 1,2,3,4-cyclobutanetetracarboxylic acid (H₄cbtc) acid generates a 1D coordination and 2D hydrogen-bonded polymer [Ni(L)(H₂cbtc)₂·3H₂O] _n (1). Complex 1 is characterized by X-ray crystallography, spectroscopy and magnetic susceptibility. Each nickel(II) ion has a distorted octahedral coordination environment with the four secondary amines of the macrocycle in which two carboxylate anions of the H₂cbtc^2? ligand have assembled around each nickel center. The compound crystallizes in the triclinic system P-1 with a = 9.715(3) Å, b = 12.891(5) Å, c = 13.903(6) Å, α = 72.64(2)°, β = 75.70(3)°, γ = 73.27(3)°, V = 1566.6(10) ų, Z = 2. The electronic spectrum of 1 indicates a high-spin octahedral environment. The magnetic behavior of 1 reveals a weak intramolecular antiferromagnetic interaction with J = ?1.23(1) cm^?1.     

[Zn2(H2O)3(2,2′-bipy)2(btc)][Zn(H2O)(2,2′-bipy)(btc)] ·8H2O: a novel zinc–carboxylate complex consisting of independently cationic and anionic chains

A novel zinc complex, [Zn₂(H₂O)₃ (2,2^′-bipy)₂(btc)][Zn(H₂O)(2, 2^′-bipy)(btc)]·8H₂O (1), (H₃btc=1,3,5- benzenetricarboxylic acid, 2,2^′-bipy=2,2^′-bipyridine) has been prepared by hydrothermal reaction of H₃btc, Zn(CH₃CO₂)₂·2H₂O and 2,2^′-bipyridine at 180 °C and characterized by single-crystal X-ray diffraction analysis. Complex 1 consists of independently cationic and anionic chains. The hydrogen bonding interactions between chains extend 1 into a two-dimensional supramolecular architecture.     

Metal–Organic Framework Based on Pyridine-2,3-Dicarboxylate and a Flexible Bis-imidazole Ligand: Synthesis, Structure, and Photoluminescence

A novel metal–organic framework {[Zn(2,3-pydc)(bbi)]·0.5CH₃CN·2H₂O} _n (2,3-pydc = pyridine-2,3-dicarboxylate, bbi = 1,1′-(1,4-butanediyl)bis(imidazole)) (1), was prepared under hydrothermal conditions and characterized by elemental analyses, IR and X-ray diffraction. Crystal data for 1 are monoclinic, space group C2/c, a = 19.685(2) Å, b = 14.332(1) Å, c = 16.930(2) Å, β = 121.205(2)°, U = 4085.3(6) Å³, Z = 4. The results reveal that the Zn(II)-atom is five-coordinated with two O-atoms and three N-atoms forming a distorted trigonal bipyramidal geometry. The Zn(II) atoms are bridged by 2,3-pydc and bbi ligands, leading to a three-dimensional network. The Zn···Zn separations are 8.277 Å [through the 2,3-pydc bridge] and 12.638 Å [through the bbi bridge]. Additionally, 1 shows strong fluorescence in the solid state at room temperature.     

1D Ladder-Like Structure Motif Assembled from Edge-Sharing Rhombic Squares of Sm2Mo2 Based on [Mo(CN)8]4− and Sm3+ Ions as Building Blocks

Novel bimetallic 4d–4f complex, {Cs[Sm(MeOH)₃(DMF)(H₂O)Mo(CN)₈] · H₂O} _n (1) (DMF = N,N′-dimethylformamide) has been synthesized and structurally characterized. The crystal analyses shown that 1 exhibit a one-dimension (1D) infinite chain structure, which adopts a 1D ladder-like structure motif assembled from edge-sharing rhombic squares of Sm₂Mo₂, and that is the first structurally characterized example of a 1D ladder structure based on the [Mo(CN)₈]^4? and Sm³⁺ building blocks. The complex 1 crystallizes in triclinic, space group P-1, with a = 9.905(2), b = 10.333(2), c = 13.562(3) Å, α = 82.00(3)°, β = 86.62(3)°, γ = 65.76(3)°, V = 1253.5(4) Å³ and Z = 2. The magnetic behavior of 1 has also been studied in this paper.     

Assembly and Property Study of a Keggin-Based Inorganic–Organic Supramolecular Compound

By introducing mixed organic ligands (pytz and 4,4′-bipy) into a Keggin POM system, a new Keggin POM-based supramolecular compound, [Cu₃(bipy)₄(pytz)₂(H₂O)₆][HSiMo₁₂O₄₀]₂·8H₂O (1) (pytz = 5-(pyridyl)tetrazolate, bipy = 4,4′-bipy) was hydrothermally synthesized and characterized by routine methods. Crystal structure analysis reveals that the title compound contains both right- and left-helical chains, and these helical chains are further connected together forming an interesting mesh network via sharing the [Cu₃(bipy)₄(pytz)₂(H₂O)₆] subunits. Finally, the 1D pillar-like chains link the mesh nets to construct a 3D supramolecular structure of 1. In addition, compound 1 shows good photocatalytic activity for the degradation of Rhodamine B dye.     

Interligand π,π-stacking interactions giving a bi-layered 2D framework in the crystal of poly-{(N4′-2,4′-bipyridine)-μ-(N,O,O′,O″-iminodiacetato)copper(II) hydrate}, {[Cu(IDA)(2,4′-bipy)]·H2O}n

The stoichiometric reaction of Cu₂CO₃(OH)₂, iminodiacetic acid [H₂IDA=HN(CH₂CO₂H)₂)] and 2,4^′-bipyridine (2,4^′-bipy) in water yields crystalline samples of {[Cu(IDA)(2,4^′-bipy)]·H₂O}_n. The compound was studied by thermal, spectral (FT-IR and reflectance), magnetic (ESR and susceptibility) and X-ray diffraction methods. The structure was solved and refined to a final R₁=0.035. The Cu(II) atom exhibits a type 4 + 1 coordination and 2,4^′-bipy ligand links the metal by its N4-donor. IDA exhibits a mer-tridentate chelating role and uses a syn-anti-bridging carboxylato group to give polymeric chains extending parallel to the c axis, leaving all 2,4^′-bipy ligands towards the same side. Water molecule reinforces the chain stability forming H-bonds with two O(carboxyl) acceptors from adjacent complex units. Both pyridyl rings of 2,4^′-bipy are nearly coplanar (1.0(2)°). Adjacent 2,4^′-bipy ligands of the same complex chain define an open dihedral angle (69°). 2,4^′-bipy ligands belonging to symmetry related chains stack both pyridyl rings at 3.40 Å, thus forming a 2D framework with IDA ligands lying towards both external faces and N-heterocyclic ligands inside. In the crystal N(IDA)-H⋯O(IDA) hydrogen bonds connect up and down adjacent 2D frameworks in a 3D network.     

A Novel Boat-Shaped Rare Earth Complex with a 3-D Interlinked Structure of Pr(III) and 1,2,4,5-Benzenetetracarboxylic Acid

A novel boat-shaped praseodymium (III)-carboxylate polymeric complex [Pr(Hbtec)]_n (H₄btec = 1,2,4,5-benzenetetracarboxylic acid) with 3-D interlinked structure, which contains nine-coordinate rare earth metal centers, simplified as PRCPC, has been synthesized under hydrothermal conditions. The frames interlinked with each other and formed a unique boat-like alignment. PRCPC that was obtained was characterized by differential thermal analysis/thermogravimetry (DTA/TG), single crystal X-ray diffraction, elemental analysis and FTIR spectral analysis. Analysis of the single-crystal X-ray diffraction confirms that PRCPC crystallizes in triclinic symmetry with space group (P ? 1), where a = 7.325(3), b = 8.162(3), c = 8.791(3) Å, α = 65.345(4), β = 86.015(4), γ = 84.203(5)°, V = 475.0(3) Å³, Z = 2, R1 = 0.0201, wR2 = 0.0505. PRCPC exhibits high thermal stability and its supramolecular frame remains stable without any change under heat treatment to 510°C.     

The synthesis and crystal structure of [M{H2B(tz*)2}2(H2O)] (M=Cu,Zn and tz*=3,5-dimethyl-1,2,4-triazole)

New ligand [KH₂B(tz^*)₂] (tz*=3,5-dimethyl-1,2,4-triazolyl) has been synthesized and the reactions of two different metal salts (copper and zinc) with the new ligand in agar gave two similar crystalline polymorphic forms: [Cu{H₂B(tz^*)₂}₂(H₂O)] (1) and [Zn{H₂B(tz^*)₂}₂(H₂O)] (2). A single crystal X-ray study revealed that the compound 1 was the monoclinic system with space group C2/c and a=8.462(3) Å, b=14.039(6) Å, c=19.991(8) Å, β=94.622(7)°, Z=4, R₁=0.0451, wR₂=0.1110. And the compound 2 was the monoclinic system with space group C2/c and a=8.4214(4) Å, b=13.8765(7) Å, c=20.2969(6) Å, β=95.615(2)°, Z=4, R₁=0.0667, wR₂=0.1375. The metal(II) ion in the complex is five-coordinated with four nitrogen atoms which come from triazolyl and one oxygen atom which come from water molecular. In both compounds, the hydrogen atoms of water molecule are connected by hydrogen bonding with N atoms of two adjacent complex molecules to form 2-D planes. The spectroscopic results are consistent with the crystallographic study.     

Synthesis,Crystal Structure of Tetra-Nuclear Macrocyclic Cu(II) Complex Material and Its Application as Catalysts for A3 Coupling Reaction

A novel tetra-nuclear macrocyclic Cu(II) complex has been synthesized by the reaction of cupric acetate monohydrate with N-acetyl-l-phenylalanine and 4,4-bipyridine in water/ethanol (v:v = 1:1) solution, and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the Cu(II) complex belongs to monoclinic, space group P ₂₁ with a = 14.993(3) Å, b = 14.831(3) Å, c = 22.262(4) Å, β = 99.37(3)°, V = 4884.2(16) Å³, Z = 2, D _c  = 1.420 μg m^?3, μ = 0.942 mm^?1, F(000) = 2,160, and final R ₁ = 0.0701, ωR ₂ = 0.1905. The molecules form three dimensional tubular structures by the interaction of hydrogen bonds and π–π interaction. The A³ coupling reaction of phenylacetylene, aldehyde and amine (piperidine) in the presence of Cu(II) complex as an efficient heterogeneous catalyst has been studied. The catalyst displayed high activity and afforded the corresponding propargylamines with excellent yields. The Cu(II) complex catalyst was reused three times without significant loss of its catalytic activity.     

A Flexible Hexacarboxylate-Samarium(III) Metal–Organic Framework: Synthesis, Structure and Spectroscopic Properties

A new flexible triazine-based polycarboxylate metal–organic framework, [Sm₂(TTHA)(H₂O)₄]·9H₂O (I) (TTHA = 1,3,5-triazine-2,4,6-triamine hexaacetate), has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction, elemental analysis and FT-IR spectroscopy. Crystal data for I are monoclinic C2/c, a = 12.6974(13) Å, b = 16.7309(12) Å, c = 14.8076(15) Å, β = 91.452(8)°, V = 3,144.7(5) Å³. Each Sm^III ion is 9-coordinate in a distorted tri-capped trigonal prismatic geometry; but, the principal inorganic building block is {Sm₂O₁₆}, which comprises two of these polyhedra that share an edge. The complex exhibits a three-dimensional open-framework structure of approximately 31 % void volume, which comprises two types of channels oriented in three directions; [0 0 1], [1 1 0] and [?1 1 0]. The network can be simplified into either the cooperite (pts) or anatase (ant) topologies depending on the choice of nodes. The UV–Vis spectra of the compound are dominated by the absorption of the TTHA ligand. Thermogravimetric analysis shows that the loss of channel and coordinated water upon heating occurs in two distinct steps.     

One-pot template synthesis and crystal structure of two new polyaza copper(II) complexes

A new 14-membered hexazamacrocyclic copper(II) complex [Cu(H₂L¹)](ClO₄)₄(L¹=1,8-bis(2-aminoethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) has been prepared by the one-pot reaction of ethylenediamine and formaldehyde in the presence of the Cu(II) ion. The crystal structure of [Cu(H₂L¹)](ClO₄)₄ was determined by X-ray diffraction. It crystallizes in the triclinic space group P−1 with a=12.118(2) Å, b=12.438(2) Å, c=12.466(2) Å, α=102.26(1)°, β=112.82(1)°, γ=111.51(1)°, and Z=2. The coordination geometry around the copper(II) ions is axially elongated octahedral with four nitrogen atoms of the macrocycle [Cu–N 2.012(7) Å for Cu(1) and 2.013(6) Å for Cu(2), average value] and two oxygen atoms of two ClO₄⁻ anions [Cu–O=2.550 Å for Cu(1) and 2.601(6) Å for Cu(2)]. [CuL²](ClO₄)₂(L²=3,7-bis(2-aminoethyl)-1,3,5,7-tetraazabicyclo[3,3,2]decane) with a novel tetraazabicyclic ligand was obtained from the same reaction system as an additional product. Crystal structure of [CuL²](ClO₄)₂: monoclinic space group Cc, a=16.393(3) Å, b=8.8640(18) Å, c= 13.085(3) Å, β=105.01(3)°, and Z=4.     

Microwave Assisted Crystal Growth of a New Organic—Decavanadate Assembly: [V10O27(OH)] · 2(C6N2H14) · (C6N2H13) · (C6N2H12) · 2H2O

Microwave synthesis was used to grow single crystals of a new organic–inorganic supramolecular assembly, [V₁₀O₂₇(OH)] · 2(C₆N₂H₁₄) · (C₆N₂H₁₃) · (C₆N₂H₁₂) · 2H₂O, in a very short time compared to the conventional solution technique. In order to generate crystals suitable for single crystal experiments, an equimolar mixture of reactants and a few hours of microwave heating are required. Although non-merohedral twinning is an inherent problem, the crystal structure can be solved and refined in the orthorhombic space group Pna2 ₁ with a = 20.972(4) Å, b = 10.3380(14) Å, c = 20.432(3) Å, Z = 4, with an excellent result, R(F²) = 0.0431. The assembly is hydrogen bond-assisted and built up of the monoprotonated decavanadate and 1,4-diazabicyclo[2.2.2]octane of various degrees of protonation. The number and location of protons on both the inorganic and organic motifs govern the formation of the extensive hydrogen bonding network, which in turn regulates the assembly architecture.     

Syntheses and Characterizations of Three Cu(II) Complexes with 2,2′-Bipyridine-3,3′-dicarboxylate and <Emphasis Type="Italic">N</Emphasis>-Donor Ancillary Ligands

Abstract  

Three novel inorganic–organic hybrid frameworks of [Cu(BPDC)(2,2′-bipy)] (1), [Cu(BPDC)(BIB)₂ ·H₂O]_n (2) and [Cu(BPDC)(4,4′-bipy)]_n (3) (BPDC²⁻ = 2,2′-bipyridine-3,3′-dicarboxylate; 2,2′-bipy = 2,2′-bipyridine; BIB = 1,2-bis(imidazol-1-ylmethyl)benzene; 4,4′-bipy = 4,4′-bipyridine) were prepared. The three complexes have been characterized by the elemental analyses, IR spectra, TGA and the single crystal X-ray diffraction. Two intramolecular Cu(II) centers of 1 are encircled by two BPDC²⁻ ligands forming an 18-membered ring, which is further assembled into a three-dimensional (3D) supramolecular architecture through the C–H···O hydrogen-bonding interactions. Complex 2 possesses a two-dimensional layer network, while complex 3 is a three-dimensional polymer composed of Cu-BPDC helical chains bridged by 4,4′-bipy. In addition, the electrochemistry of complex 1 was investigated.     

Construction of Two One-Dimensional Coordination Polymers by 5-Chlorosalicylic Acid Plus N-Donor Ligand: Synthesis,Structure and Catalytic Properties

Two novel coordination polymers, namely, [Co(HL5)(4,4′-bpy)_1.5(H₂O)₂]_n·n(HL5) (1) and [Zn(HL5)₂(4,4′-bpy)]_n (2) (H₂L5 = 5-chlorosalicylic acid), have been hydrothermally synthesized through the reaction of 5-chlorosalicylic acid with divalent transition-metal salts in the presence of N-donor ancillary coligand (4,4′-bpy = 4,4′-bipyridine). Polymer 1 exhibits one-dimensional (1D) infinite ladderlike chain, which is extended into a 2D supramolecular network via O–H···O hydrogen-bonding interactions. In polymer 2, 4,4′-bpy acts as a bidentate ligand to bind Zn(II) ions to form a [Zn(4,4′-bpy)]_n infinite zigzag chain structure, which is linked by hydrogen bonds into a 3D suparmolecular assembly. Also, IR spectra, powder X-ray diffraction, fluorescence Properties and thermal decomposition process of polymers were investigated. Moreover, both compounds exhibit catalytic properties on degradation of methyl orange in Fenton-like process.     

Synthesis,Characterization, Crystal Structure and Antimicrobial Evaluation of a Novel –M–X–M–X– Type Infinite Chain 1D Cu(II) Complex with Eflornithine Hydrochloride Hydrate as Ligand

A novel –M–X–M–X– type infinite chain 1D copper(II) complex of Eflornithine, Dichloro-[2-amino-5-ammonio-2-(difluoromethyl)pentanoate]copper(II) hydrate, [Cu(C₆H₁₂F₂N₂O₂)Cl₂]·H₂O 1 has been synthesized and characterized by elemental analysis, spectroscopic techniques (UV/Vis and FT-IR), TGA and X-ray diffraction. Single-crystal X-ray diffraction analysis of the complex 1 showed the structure to be monoclinic with space group Cc, a = 13.1295(15) Å, b = 12.1859(14) Å, c = 8.1927(9) Å, β = 118.359(3) Å, V = 1153.5(2) Å³, Z = 4. The complex exhibits a quadratic planar coordination of the Cu-atom. The Cu(II) centre is coordinated by two chloride atoms, an oxygen atom of the carboxyl- and a nitrogen atom of the amino-group, respectively, forming a quadratic planar geometry. The terminal amino group of the ligand is protonated to form NH₃ ⁺ while the carboxylic moiety is deprotonated to form Zwitterionic eflornithine ligand, with the coordination of the metal at the nitrogen atom of the second amino group. The compound has –M–X–M–X– infinite 1D chain polymeric structure. Two neigbouring Cu(EFL)Cl chain units are bridged by an Cl^? ion, forming a –Cu–Cl–Cu–Cl– linear chain structure along C-axis. The antibacterial activities of the complex on Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa) were investigated and found to be active at higher concentration than the parent ligand.     

Structural characterization and conformational analysis of (aqua)(ethylenediamine-N,N,N′-triacetato)chromium(III) monohydrate complex. Crystal structure of the cis-equatorial isomer of [Cr(ed3a)(H2O)] · H2O

The structure of the cis-equatorial isomer of [Cr(ed3a)(H₂O)] · H₂O (ed3a=ethylenediamine-N,N,N^′-triacetate ion) was determined by X-ray diffraction method. The complex crystallizes in the monoclinic space group P2₁/n, a=7.004(1) Å, b=15.958(2) Å, c=11.046(1) Å, β=97.16(1)°, and Z=4. Conformational analysis of the three possible geometrical isomers, trans(H₂O,N^′), trans(H₂O,N_H), and trans(H₂O,O) of [Cr(ed3a)(H₂O)] moiety, performed using the consistent force field (CFF) program with the recently developed parameters for EDTA-type complexes, yielded structural details and energies of the minimized form for each of the isomers. Calculated energies showed that the cis-eq isomer is the most stable one, with the geometry in a very good agreement with the crystallographic structure. Comparison of the molecular mechanics calculations with those for the analogous [Cr(ed3p)(H₂O)] · H₂O (ed3p=ethylenediamine-N,N,N^′-tripropionate ion) revealed some general patterns for the conformational preference of EDTA-type complexes.