Synthesis and structures of nickel(II) and copper(II) compounds of 5,5,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradecane and the 13-ethyl-5,5,7-trimethyl-homologue

Reduction by NaBH₄ of the imine functions of (5,7,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradec-4-ene)-nickel(II) and -copper(II), and of their 13-ethyl-5,7,7-trimethyl-homologues, yield the nitro-substituted cyclic tetraamine cations (5,5,7,13-tetramethyl-13-nitro-1,4,8,11-tetraazacyclotetradecane)-nickel(II) and -copper(II), [M(neh)]²⁺, and (13-ethyl-5,5,7-trimethyl-homologues, [M(nph)]²⁺, respectively. The nickel(II) cations form square–planar, singlet ground, state salts with poorly coordinating anions and octahedral, triplet ground state, compounds with additional ligands, trans-β-[Ni(neh)A₂], A⁻ = Cl⁻, NCS⁻ and trans-β-[Ni(neh)A₂](ClO₄)₂, X = NH₃, MeCN, all with nitrogen configuration III, 1R,4R,8S,11S = β. With oxalate the chain-polymeric compound catena-trans-β-[Ni(neh)(μ-C₂O₄)]_n · 3n(H₂O) is formed. Folded macrocycle compounds cis-α-[Ni(neh)(C₅H₇O₂)]ClO₄ and cis-α-[{Ni(neh)}₂(C₂O₄)](ClO₄)₂ are formed with the chelates acetylacetonate and oxalate, with configuration 1R,4R,8R,11R = α. These react with HClO₄ to form metastable α-[Ni(neh)](ClO₄)₂ with retention of configuration. The copper(II) cations form crimson salts with poorly coordinating anions and compounds of the type β-[Cu(neh)A]ClO₄ of varying shades of blue with coordinating anions. Structures of singlet ground state square–planar nickel(II) compounds β-[Ni(neh)](ClO₄)₂ · H₂O, β-[Ni(neh)](ClO₄)₂, β-[Ni(neh)]₂[ZnCl₃(OH₂)]₂[ZnCl₄] · H₂O and α-[Ni(neh)](ClO₄)₂, the triplet ground state chain-polymeric compound catena-trans-β-[Ni(neh)(μ-C₂O₄)]_n · 3n(H₂O) and of square–pyramidal β-[Cu(nph)Cl]ClO₄ are reported.     

Nickel(II) compounds of a tri-amine mono-imine macrocycle: Preparations and structures of (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradec-4-ene)nickel(II) compounds

Reduction of one imine function of (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene)nickel(II) with 1 molar proportion of NaBH₄ produces as the major product the tri-amine-mono-imine macrocyclic cation (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradec-4-ene)nickel(II), Ni(tm)]²⁺. Pairs of isomeric singlet ground state perchlorate and tetrachlorozincate salts of [Ni(tm)]²⁺ were prepared and the structures determined for the 1RS,8SR,11SR,12RS (labeled as β) and 1RS,8RS,11RS,12SR (labeled as α) tetrachlorozincate salts. Triplet ground state trans-β-[Ni(tm)(NCS)₂] and catena-trans-{β-Ni(tm)-NC-Ni(CN)₂-CN-}_n·2nH₂O have the macrocycle in planar coordination and α-[{Ni(tm)}₂(C₂O₄)](ClO₄)₂ has the macrocycle folded. With pentane-2,4-dione the compounds [β-Ni(tm)]·[α-Ni(tm)(acac)](ClO₄)₃ and [Ni(teta)]·[α-Ni(tm)(acac)](ClO₄)₃ (teta = C-meso-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) with both square-planar and octahedral Ni(II) cations were prepared and the latter was structurally characterized. Isomerisation in solution of metastable α-[Ni(tm)]²⁺ to stable β-[Ni(tm)]²⁺ is extremely slow, even in base.     

Nickel(II) complexes of the macrocyclic ligand 5-nitromethyl-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene containing a pendant nitro group

The reaction of MeNO2 in the presence of Et3N with the nickel(II) complex of C-meso-5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene gives the nickel(II) complex of the 5-nitromethyl derivative containing a pendant nitro group. The complex is octahedral with the nitro group coordinated to nickel(II) via the aci-nitro tautomer. Although the complex contains one water molecule, six-coordination occurs by interaction with a neighbouring CH NO2- group in a polymeric structure. Recrystallisation from aqueous ammonia gives a blue paramagnetic complex with lattice ammonia. Addition of HClO4 to the blue paramagnetic hydrate gives the orange-brown diperchlorate salt with a pendant nitro group. This salt displays a planar octahedral equilibrium in aqueous solution, NiL+2H2O NiL(H2O)2, with K=0.28 at 40degC. The thermodynamic parameters for this equilibrium are DeltaH=-59+2kJmol-1and DeltaS=-200+5JK-1mol-1. The nitro group can be reduced with Zn/HCl to give the amino derivative. The configurations of the complexes are considered and the spectroscopic results discussed. This revised version was published online in June 2006 with corrections to the Cover Date.     

Oxamato-bridged trinuclear Ni(II)Cu(II)Ni(II) complexes with irregular spin state structures and a binuclear Ni(II)Cu(II) complex with an unusual supramolecular structure: crystal structure and magnetic properties

Four oxamato-bridged heterotrinuclear Ni(II)Cu(II)Ni(II) complexes of formula ([Ni(bispictn)](2)Cu(pba))(ClO(4))(2).2.5H(2)O (1), ([Ni(bispictn)](2)Cu(pbaOH))(ClO(4))(2).H(2)O (2), ([Ni(cth)](2)Cu(pba))(ClO(4))(2) (3), and ([Ni(cth)](2)Cu(opba))(ClO(4))(2).H(2)O (4) and a binuclear Ni(II)Cu(II) complex of formula [Cu(opba)Ni(cth)].CH(3)OH (5) have been synthesized and characterized by means of elemental analysis, IR, ESR, and electronic spectra, where pba = 1,3-propylenebis(oxamato), pbaOH = 2-hydroxyl-1,3-propylenebis(oxamato), opba = o-phenylenebis(oxamato), bispictn = N,N'-bis(2-pyridylmethyl)-1,3-propanediamine, and cth = rac-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane. The crystal structures of 1, 3, and 5 have been determined. The structures of complexes 1 and 3 consist of trinuclear cations and perchlorate anions, and that of 5 consists of neutral binuclear molecules which are connected by hydrogen bonds and pi-pi interactions to produce a unique supramolecular "double" sheet. In the three complexes, the copper atom in a square-planar or axially elongated octahedral environment and the nickel atom in a distorted octahedral environment are bridged by the oxamato groups, with Cu.Ni separations between 5.29 and 5.33 A. The magnetic properties of all five complexes have been investigated. The chi(M)T versus T plots for 1-4 exhibit the minimum characteristic of antiferromagnetically coupled NiCuNi species with an irregular spin state structure and a spin-quartet ground state. The chi(M)T versus T plot for 5 is typical of an antiferromagnetically coupled NiCu pair with a spin-doublet ground state. The Ni(II)-Cu(II) isotropic interaction parameters for the five complexes were evaluated and are between 102 and 108 cm(-)(1) (H = -JS(Cu).S(Ni)).     

Preparation and characterization of nickel(II), copper(II) and palladium(II) complexes with 5,14-dihydro-7,16-diethyl-dipyrazo[b,i][1,4,8,11]tetraazacyclotetradecine

A novel macrocycle, 5,14-dihydro-7,16-diethyldipyrazo[b,i][1,4,8,11]tetraazacyclotetradecine, has been synthesized from 1,2-diaminopyrazine and 2-ethyl-3-ethoxyacrolein. The absorption bands appearing in the energy range greater than 20000 cm^?1 were attributable to the π → π transitions. The bands in the range of the 20100–23300 cm^?1 show more bathochromic shift and greater intensity than those observed for corresponding 5,14-dihydro-7,16-diethyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine and/or 5,14-dihydro-7,16-diethyl-(Z)-dipyrido[b,i][1,4,8,11]tetraazacyclotetradecine. The nickel(II), copper(II) and palladium(II) complexes of 5,14-dihydro-7,16-diethyldipyrazo[b,i][1,4,8,11]tetraazacyclotetradecine have been synthesized using a metal template reaction. In ¹H and ¹³C nmr spectra, the signals of annulene skeleton for metal-free ligand and its complexes were found to observe in the lower field than those of the dibenzoanalogue.     

Synthesis, characterization, crystal structure and antimicrobial activities of new transN,N-substituted macrocyclic dioxocyclam and their copper(II) and nickel(II) complexes

New trans-disubstituted macrocyclic ligands, 1,8-[N,N-bis(3-formyl-12-hydroxy-5-methyl)benzyl]-5,12-dioxo-1,4,8,11-tetraazacyclotetradecane (L¹), 1,8-[N,N-bis(3-formyl-12-hydroxy-5-bromo)benzyl]-5,12-dioxo-1,4,8,11-tetraazacyclotetradecane (L²), N,N-bis[1,8-dibenzoyl]-5,12-dioxo-1,4,8,11-tetraazacyclotetradecane (L³), N,N-bis[1,8-(2-nitrobenzoyl)]-5,12-dioxo-1,4,8,11-tetraazacyclotetradecane (L⁴), and N,N-bis[1,8-(4-nitrobenzoyl)]-5,12-dioxo-1,4,8,11-tetraazacyclotetradecane (L⁵) were synthesized. The ligands were characterized by elemental analysis, FT IR, ¹H NMR and mass spectrometry studies. The crystal structure of L¹ is also reported. The copper(II) and nickel(II) complexes of these ligands were prepared and characterized by elemental analysis, FT IR, UV-Vis and mass spectral studies. The cyclic voltammogram of the complexes of ligand L^1-3 show one-electron quasi-reversible reduction wave in the region −0.65 to −1.13 V, whereas that of L⁴ and L⁵ show two quasi-reversible reduction peaks. Nickel(II) complexes show one electron quasi-reversible oxidation wave at a positive potential in the range +0.95 to +1.06 V. The ESR spectra of the mononuclear copper(II) complexes show four lines, characteristic of square-planar geometry with nuclear hyperfine spin 3/2. All copper(II) complexes show a normal room temperature magnetic moment value μ_eff 1.70-1.73 BM which is close to the spin only value of 1.73 BM. Kinetic studies on the oxidation of pyrocatechol to o-quinone using the copper(II) complexes as catalysts and hydrolysis of 4-nitrophenylphosphate using the copper(II) and nickel(II) complexes as catalysts were carried out. The ligands and their complexes were also screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and human pathogenic fungi.     

"Swollen" Macrocycles: Palladium(II)-Directed Template Syntheses of Pendant-Arm 14-, 16-, and 18-Membered Macrocycles

The bis(diamine)palladium(II) cations (diamine = ethane-1,2-diamine, propane-1,3-diamine, or butane-1,4-diamine) all undergo condensation reactions with formaldehyde and nitroethane to produce macromonocycles where each pair of cis-disposed primary amines has been converted to a -NH-CH(2)-C(CH(3))(NO(2))-CH(2)-NH- strap. The 14-membered-ring macrocycle has been previously prepared by condensation around copper(II) and nickel(II), but this does not permit synthesis of the larger ring macrocycles. The macrocyclic complex (6,13-dimethyl-6, 13-dinitro-1,4,8,11-tetraazacyclotetradecane)palladium(II) perchlorate crystallizes in the triclinic space group P&onemacr;, a = 8.105(3) ?, b = 8.370(2) ?, c = 9.437(4) ?, alpha = 69.04(3) degrees, beta = 68.60(3), gamma = 71.53(3) degrees. Complexes of the 16- and 18-membered macrocycles (3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)palladium(II) perchlorate and (3,12-dimethyl-3,12-dinitro-1,5,10,14-tetraaazacyclooctadecane)palladium(II) perchlorate crystallize in the monoclinic space group P2(1)/c, with a = 8.391(2) ?, b = 12.816(3) ?, c = 23.925(9) ?, and beta = 93.18(2) degrees, and the triclinic space group P&onemacr;, with a = 7.746(5) ?, b = 9.912(5) ?, c = 18.96(2) ?, alpha = 91.76(6) degrees, beta = 101.73(7) degrees, and gamma = 112.83(5) degrees respectively. The larger macrocycles are "swollen" by incorporating longer methylene chains, "swelling" leading to an increase in Pd-N distance and in tetrahedral distortion, with the dominant geometric isomer apparently changing with macrocycle size from anti-disposed nitro pendants (14-membered) to the syn isomer (16-, 18-membered). An irreversible Pd(II/IV) oxidation occurs at ca +1 V (vs Ag/AgCl), varying slightly with ring size, with a multi-electron nitro group reduction observed near -0.8 V in each case. Electronic spectra also vary slightly with ring size.     

A perchlorate-selective membrane electrode based on a Cu(II) complex of the ligand 1,4,8,11-tetra(n-octyl)-1,4,8,11-tetraazacyclotetradecane

The new cyclic polyazacycloalkane 1.4,8,11-tetra(n-octyl)-1,4,8,11-tetraazacyclotetradecane (L1) was synthesised and the copper(II) complex [Cu(L1)]2+ characterised. Different electrodes were prepared using the [Cu(L1)]2+ complex as ionophore, PVC as plastic matrix and o-nitrophenyl octyl ether (NPOE), bis(2-ethylhexyl) sebacate (BEHS) or dibutyl phthalate (DBP) as plasticizers. The electrode containing DBP showed a Nernstian response over a wide pH range and a fast response time (ca. 3 s) whereas NPOE and BEHS gave near-Nernstian slopes. Selectivity coefficients for the different anions with respect to perchlorate were calculated. The response of the electrodes basically followed the Hofmeister sequence, suggesting that interaction of the ionophore with the anions is via electrostatic forces rather than due to anion coordination to the axial sites of the square-planar [Cu(L1)]2+ complex.     

Copper(II) and nickel(II) complexes of mono-oxocyclam(5-oxo-1,4,8,11-tetraazacyclotetradecane). Synthetic and potentiometric studies

Summary The macrocyclic mono-oxotetraamine, 5-oxo-1,4,8,11-tetraazacyclotetradecane (mono-oxocyclam=LH) has been prepared by reaction of methyl acrylate with 2,3,2-tetra(1,9-diamino-3,7-diazanonane). The protonation constants of the ligand are log K₁=9.40, log K₂=6.65 and log K₃=2.87 at 25 °C (I=0.1 mol dm^–3 NaClO₄). Detailed potentiometric studies of the interaction of the base with copper(II) and nickel(II) have been carried out. In the pH range 2.5–7.0 two complexes, [CuLH]²⁺ and [CuL]⁺, form; the deprotonated complex being 100% abundant at pH 7. For nickel(II), only [NiL]⁺ forms (log _11–1 = 3.90), the yellow low spin nickel complex reaching its maximum concentration above pH 6. The [CuL][ClO₄] · H₂O and [NiL][ClO₄] 0.5 H₂O complexes have been characterised in the solid state. The nickel(II) complex is square planar with a d-d band at 22625 cm^–1.     

Synthesis and characterization of macrocyclic ligands containing benzene and/or pyridine rings and their nickel(II), copper(II) and zinc(II) complexes

Macrocycles, 7,16-diethyl-5,6,7,8,9,14,15,16,17,18-decahydrodibenzo[b,i][1,4,8,11]tetraazacyclotetradecine ( 2B ), 7,16-diethyl-5,6,7,8,9,14,15,16,17,18-decahydro-(E)dipyrido[b,i][1,4,8,11]tetraazacyclotetradecine ( 2E ) and 7,16-diethyl-5,6,7,8,9,14,15,16,17,18-decahydro-(Z)-dipyrido[b,i][1,4,8,11]tetraazacyclotetradecine ( 2Z ), have been synthesized by hydrogenation of 7,16-diethyl-5,14-dihydrodibenzo[b,i][1,4,8,11]tetraazacyclotetradecine and 7,16-diethyl-5,14-dihydro-(E)- or -(Z)-dipyrido[b,i][1,4,8,11]tetraazacyclotetradecine. In each case, two isomers were produced with differing orientations of the ethyl groups relative to the macrocyclic plane. The isomers were separated by repeated recrystallization. Carbon-13 nmr spectra for the metal-free ligands were used to distinguish between the two isomers. The nickel(II), copper(II) and zinc(II) complexes of the two isomers of 2B were prepared and their spectroscopic data were determined. The ligand-field bands in the 15000–30000 cm^?1 region for the nickel(II) and copper(II) complexes are consistent with square-planar configurations. A strong band appearing at ca. 3200 cm^?1 in the infrared spectra was assigned to the N-H stretching mode which shifted to lower frequency upon metal coordination.     

Macrocyclic ligands with potential axial interactions. The preparation of copper(II), nickel(II) and cobalt(III) complexes of 7,14-o-hydroxyphenyl-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene

Summary The new macrocyclic ligand 7,14-o-hydroxyphenyl-5,12-dimethyl-1,4,8,11-tetraazacyclotetradeca-4,11-diene (1=L) has been prepared and complexes with copper(II), nickel(II) and cobalt(III) characterised. The nickel(II) complex is a yellow square-planar species, while the purple-red copper(II) complex is probably tetragonal in both the solid state and solution. The complexes appear to have an N-meso arrangement of the chiral nitrogen centres with the HOC₆H₄ groups occupying equatorial sites so that axial interactions with the metal do not occur. A variety oftrans-[CoLX₂]ClO₄ complexes (X=Cl, Br, NO₂, or N₃) have been characterised.     

The Structure of Nickel(Ii) and Copper(Ii) Complexes with 1,4,8,11-Tetraazacyclotetradecanein Aqueous Solution as Studied by the X-Ray Diffraction Method

The structure of 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes with nickel(II) and copper(II) ions in aqueous solution has been determined by the x-ray diffraction method at 25°C. The [Ni-(cyclam)]²⁺ complex has a square-planar structure with four nitrogen atoms of the cyclam, and the Ni-N bond length has been determined to be 198 pm. Upon the addition of ammonia, the color of the nickel(II)-cyclam solution turns to deep purple and the [Ni(NH₃)₂(cyclam)]²⁺ complex is formed. The complex has a regular octahedral structure with an additional two NH₃ molecules along the axis vertical of the cyclam plane, and the Ni-N (NH₃ and cyclam) bond lengths are 209 pm. The copper(II)-cyclam complex in the aqueous solution is a distorted octahedron with two water molecules along the elongated axis. The axial Cu—O and equatorial Cu—N bond lengths are 277 and 210 pm, respectively.     

Kinetics and mechanism of complex formation of nickel(II) with tetra-N-alkylated cyclam in N,N-dimethylformamide (DMF): comparative study on the reactivity and solvent exchange of the species Ni(DMF)6(2+) and Ni(DMF)5Cl+

13C NMR was used to study the rate of DMF exchange in the nickel(II) cation Ni(DMF)6(2+) and in the monochloro species Ni(DMF)5Cl+ with 13C-labeled DMF in the temperature range of 193-395 K in DMF (DMF = N,N-dimethylformamide). The kinetic parameters for solvent exchange are kex = (3.7 +/- 0.4) x 10(3) s-1, delta H++ = 59.3 +/- 5 kJ mol-1, and delta S++ = +22.3 +/- 14 J mol-1 K-1 for Ni(DMF)6(2+) and kex = (5.3 +/- 1) x 10(5) s-1, delta H++ = 42.4 +/- 4 kJ mol-1, and delta S++ = +6.7 +/- 15 J mol-1 K-1 for Ni(DMF)5Cl+. Multiwavelength stopped-flow spectrophotometry was used to study the kinetics of complex formation of the cation Ni(DMF)6(2+) and of the 100-fold more labile cation Ni(DMF)5Cl+ with TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and TEC (1,4,8,11-tetraethyl-1,4,8,11-tetraazacyclotetradecane) in DMF at 298 K and I = 0.6 M (tetra-n-butylammoniumperchlorate). Equilibrium constants K for the addition of the nucleophiles DMF, Cl-, and Br- to the complexes Ni(TMC)2+ and Ni(TEC)2+ were determined by spectrophotometric titration. Formation of the complexes Ni(TMC)2+ and Ni(TEC)2+ was found to occur in two stages. In the initial stage, fast, second-order nickel incorporation with rate constants k1(TMC) = 99 +/- 5 M-1 s-1 and k1 (TEC) = 235 +/- 12 M-1 s-1 leads to the intermediates Ni(TMC)int2+ and Ni(TEC)int2+, which have N4-coordinated nickel. In the second stage, these intermediates rearrange slowly to form the stereochemically most stable configuration. First-order rate constants for the one-step rearrangement of Ni(TMC)int2+ and the two-step rearrangment of Ni(TEC)int2+ are presented. Because of the rapid formation of Ni(DMF)5Cl+, the reactions of Ni(DMF)6(2+) with TMC and TEC are accelerated upon the addition of tetra-n-butylammoniumchloride (TBACl) and lead to the complexes Ni(TMC)Cl+ and Ni(TEC)Cl+, respectively. For initial concentrations such that [TBACl]o/[nickel]o > or = 20, intermediate formation is 230 times (TMC) and 47 times (TEC) faster than in the absence of chloride. The mechanism of complex formation is discussed.     

Preparation and characterization of copper(II) and nickel(II) complexes with novel tetraaza-macrocyclic schiff bases

Novel tetraaza-macrocycles with N-substituted carbamoyl groups were prepared by the reaction of 5,7,12,14-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,5,7,12-tetraene with isocyanates (RNCO, R = Ch₃ and C₆H₅). Their copper(II) and nickel(II) complexes were characterized by magnetic susceptibilities, electronic absorption spectra, and electrochemical properties. The complexing abilities and extractabilities of the ligands for the metal ions were investigated.     

Diaquabis(1,3‐propanediamine‐κ2N,N′)nickel(II) bis(sulfanilate)

The title compound, [Ni(C₃H₁₀N₂)₂(H₂O)₂](C₆H₆NO₃S)₂, contains alternating layers of sulfanilate anions and di­aqua­bis(1,3‐propane­di­amine)­nickel(II) cations. The Ni atom lies on an inversion centre and is hexacoordinated by the 1,3‐propane­di­amine ligands, which function as N,N′‐bidentate ligands, and the water mol­ecules, which are in a trans arrangement. The sulfanilate anions are arranged in layers, with the sulfonate and amine groups directed towards opposite sides of the layer. The structure is stabilized by a network of hydrogen bonding between the O and N atoms of the sulfanilate anions, the water mol­ecules, and the N atoms of the 1,3‐propane­di­amine ligands.     

Oxidation of (7,16-diethyl-5,6,7,8,9,14,15,16,17,18-decahydrodibenzo[b,i][1,4,8,11]tetraazacyclotetradecine)nickel(II) complexes

The oxidation reaction of two isomers of (7,16-diethyl-5,6,7,8,9,14,15,16,17,18-decahydrodibenzo[b,i]-[1,4,8,11]tetraazacyclotetradecine)nickel(II) diperchlorate and/or dichloride (NiL¹X₂ (X = ClO₄, Cl)) in methanol in air under atmospheric pressure leads to the production of (7,16-diethyl-5,6,7,8,9-pentahydrodibenzo-[b,i][1,4,8,11]tetraazacyclotetradecinato)nickel(II) complexes (NiL²X). Proton and ¹³C nmr spectra suggest that NiL²X is formed by partial oxidation from a macrocyclic skeleton of NiL¹X₂. The dehydrogenation of NiL¹X₂ does not occur at symmetric positions such as d- and k-positions of the macrocyclic skeleton but at unsymmetrical positions such as d- and f-positions. Treatment of NiL¹X₂ and/or NiL²X in a methanol solution with an excess of bases in air gives (7,16-diethyldibenzo[b,t][1,4,8,11]tetraazacyclotetradecinato)nickel(II) (NiL³).     

Structure of two azide salts of a copper(II) macrocycle and magnetic properties of Cu(14ane)Cu(N3)4

Synthesis of azide complexes with the copper(II) macrocycle complex Cu(14ane)(2+) (where 14ane = 1,4,8,11-tetraazacyclothetradecane) has yielded two compounds. Cu(14ane)Cu(N(3))(4) contains micro(1,3)-azido bridged chains of Cu(14ane)(2+) cations and Cu(N(3))(4)(2)(-) anions. Magnetic studies reveal the presence of ferromagnetic interactions within the chains with J/k = 0.635(4) K. [Cu(14ane)N(3)]BF(4) contains [Cu(14ane)N(3)]+ cations with elongated square pyramidal geometry. The BF(4)(-) anions are weakly coordinated in the sixth coordination site of the cations.     

Structure Studies on New Types of Macrocyclic Compounds Part V．Crystal Structure of Nickel（II） Complex of 5，12－Diphenyl－7，14－dimethyl－1，4，8，11－tetraazacyclotetradecane－N＇，N－diacetic Acid

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The structures of some (hexamethyl-1,5,9,13-tetraazacyclohexadecadiene)copper(II) compounds

The structure of the crystalline azamacrocyclic product formed by reaction of bis(propane-1,3-diamine)copper(II) perchlorate with acetone has been determined as N-rac-(6,8,8,14,16,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,13-diene)copper(II) · N-meso-(6,8,8,14,14,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,16(1)-diene)copper(II) perchlorate, with the cis, 5,16(1)-diene, and trans, 5,13-diene, isomeric cations co-crystallised. The structures of three compounds crystallised from solutions of this mixture have been determined. N-rac-(6,8,8,14,14,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,16(1)-diene)copper(II) tetrachlorozincate has an irregular flattened tetrahedral coordination geometry with trans-N-Cu-N angles of 139.27(8)° and 155.94(8)°. (Hexamethyl-1,5,9,13-tetraazacyclohexadecadiene)(thiocyanato-N)copper(II) perchlorate has twofold symmetrical square-pyramidal cations. A (μ-cyano)-tetracyanonickelate(II) compound has two (hexamethyl-1,5,9,13-tetraazacyclohexadecadiene)copper(II) cations each with a single axially coordinated tetracyanonickelate(II) group. The compounds, except for the tetrachlorozincate(II) salt, show disorder in the location of the imine functions and axial methyl substituents, attributed to co-crystallisation of enantiomers for the N-rac-trans isomer and/or of rotated arrangements of the N-meso-cis isomer. For the thiocyanato and tetracyanonickelato compounds this disorder precluded unambiguous assignment of configuration.     

Catenation control in the two-dimensional coordination polymers based on tritopic carboxylate linkers and azamacrocyclic nickel(II) complexes

Four new coordination polymer frameworks, namely [(NiL(1))(3)(BTB)(2)]·6H(2)O, [(NiL(2))(3)(BTB)(2)]·6H(2)O, [(NiL(3))(3)(BTB)(2)]·6H(2)O and [(NiL(2))(3)(BTC)(2)]·10.25H(2)O (L(1) = 1,4,8,11-tetraazacyclotetradecane, L(2) = 3-methyl-1,3,5,8,12-pentaazacyclotetradecane, L(3) = 3,10-dimethyl-1,3,5,8,10,12-hexaazacyclotetradecane, BTC(3-) = benzene-1,3,5-tricarboxylate, BTB(3-) = 4,4',4'-benzene-1,3,5-triyl-tribenzoate) were prepared in water-N,N-dimethylformamide solutions. The molecular and crystal structures of these compounds are compared to the related coordination polymers formed by nickel(II) macrocyclic cations to examine the effect of carboxylate linker size on the framework architecture. Luminescent properties of the complexes based on the BTB(3-) bridging ligand are also discussed.