Azide Anion Research Articles

A Molecular Precursor to Phosphaethyne and Its Application in Synthesis of the Aromatic 1,2,3,4-Phosphatriazolate Anion.

Dibenzo-7-phosphanorbornadiene Ph3PC(H)PA (1, A = C14H10, anthracene) is reported here as a molecular precursor to phosphaethyne (HC≡P), produced together with anthracene and triphenylphosphine. HCP generated by thermolysis of 1 has been observed by molecular beam mass spectrometry, laser-induced fluorescence, microwave spectroscopy, and nuclear magnetic resonance (NMR) spectroscopy. In toluene, fragmentation of 1 has been found to proceed with activation parameters of ΔH(⧧) = 25.5 kcal/mol and ΔS(⧧) = -2.43 eu and is accompanied by formation of an orange insoluble precipitate. Results from computational studies of the mechanism of HCP generation are in good agreement with experimental data. This high-temperature method of HCP generation has pointed to new reaction chemistry with azide anion to produce the 1,2,3,4-phosphatriazolate anion, HCPN3(-), for which structural data have been obtained in a single-crystal X-ray diffraction study. Negative-ion photoelectron spectroscopy has shown the adiabatic detachment energy for this anion to be 3.555(10) eV. The aromaticity of HCPN3(-) has been assessed using nucleus-independent chemical shift, quantum theory of atoms in molecules, and natural bond orbital methods.

Preparation of a Novel Nano-scale Lead (II) Zig-Zag Metal–Organic Coordination Polymer with Ultrasonic Assistance: Synthesis, Crystal Structure, Thermal Properties, and NBO Analysis of [Pb(μ-2-pinh)N3 H2O

A novel nano-cauliflower-shaped lead(II) metal–organic coordination polymer, [Pb(μ-2-pinh)N3 H2O]n (1), was synthesized using an ultrasonic method. The nanostructure was characterized by scanning electron microscopy (SEM), X-ray powder diffraction, IR spectroscopy, elemental analysis, and thermal analysis. The compound was structurally characterized by single-crystal X-ray diffraction. The coordination compound takes the form of a zig-zag one-dimensional polymer in solid state. The coordination number of the lead(II) ions is six (PbN4O2) with three nitrogen atoms and one oxygen atom from two linker organic ligands, as well as one oxygen from coordinated water and one nitrogen atom from terminal coordinated azide anion. It has a stereo-chemically active lone electron pair, and the coordination sphere is hemidirected. The zig-zag 1D chains interact with neighbouring chains through weak interactions, creating a 3D supramolecular metal–organic framework. Lead oxide nanoparticles were obtained by thermolysis of the new nano coordination compound at 180 °C with oleic acid as a surfactant. The morphology and size were further studied using SEM. Natural bond orbital analyses demonstrate the electronic properties of the lead centre and other atoms.

ChemInform Abstract: Synthesis of Enantiopure 1,2‐Azido and 1,2‐Amino Alcohols via Regio‐ and Stereoselective Ring‐Opening of Enantiopure Epoxides by Sodium Azide in Hot Water.

AbstractThe ring‐opening of enantiopure aryl epoxides by azide anion takes place preferentially at the internal position to produce 2‐azido ethanols with high regio‐ and enantioselectivity.

Expedient Route To Access Rare Deoxy Amino l-Sugar Building Blocks for the Assembly of Bacterial Glycoconjugates.

Bacterial glycoproteins and oligosaccharides contain several rare deoxy amino l-sugars which are virtually absent in the human cells. This structural difference between the bacterial and host cell surface glycans can be exploited for the development of carbohydrate based vaccines and target specific drugs. However, the unusual deoxy amino l-sugars present in the bacterial glycoconjugates are not available from natural sources. Thus, procurement of orthogonally protected rare l-sugar building blocks through efficient chemical synthesis is a crucial step toward the synthesis of structurally well-defined and homogeneous complex glycans. Herein, we report a general and expedient methodology to access a variety of unusual deoxy amino l-sugars starting from readily available l-rhamnose and l-fucose via highly regioselective, one-pot double serial and double parallel displacements of the corresponding 2,4-bistriflates using azide and nitrite anions as nucleophiles. Alternatively, regioselective monotriflation at O2, O3, and O4 of l-rhamnose/l-fucose allowed selective inversions at respective positions leading to diverse rare sugars. The orthogonally protected deoxy amino l-sugar building blocks could be stereoselectively assembled to obtain biologically relevant bacterial O-glycans, as exemplified by the first total synthesis of the amino linker-attached, conjugation-ready tetrasaccharide of O-PS of Yersinia enterocolitica O:50 strain 3229 and the trisaccharide of Pseudomonas chlororaphis subsp. aureofaciens strain M71.

Bis{bis-(azido-κN)bis-[bis-(pyridin-2-yl-κN)amine]cobalt(III)} sulfate dihydrate.

The search for new mol-ecular materials with inter-esting magnetic properties, using the pseudohalide azide ion and di-2-pyridyl-amine (dpa, C10H9N3) as a chelating ligand, led to the synthesis and structure determination of the title compound, [Co(N3)2(dpa)2]2SO4·2H2O. The crystal structure comprises discrete [Co(dpa)2(N3)2](+) cations, sulfate anions, as well as H2O solvent mol-ecules. The Co(III) cations display a slightly distorted octa-hedral coordination sphere defined by two N atoms from azide anions and four N atoms from the pyridyl rings of two dpa ligands. In the crystal, extensive C-H⋯O, N-H⋯O, and O-H⋯O inter-actions result in supra-molecular sheets that lie parallel to the ab plane. The sheets are further linked through O-H⋯N inter-actions between the water mol-ecules of one sheet and azide anions of another sheet, forming a supra-molecular framework.

Azide Binding Controlled by Steric Interactions in Second Sphere. Synthesis, Crystal Structure, and Magnetic Properties of [Ni(II)2(L)(μ(1,1)-N3)][ClO4] (L = Macrocyclic N6S2 Ligand).

The dinuclear Ni(II) complex [Ni2(L(2))][ClO4]2 (3) supported by the 28-membered hexaaza-dithiophenolate macrocycle (L(2))(2-) binds the N3(-) ion specifically end-on yielding [Ni2(L(2))(μ(1,1)-N3)][ClO4] (7) or [Ni2(L(2))(μ(1,1)-N3)][BPh4] (8), while the previously reported complex [Ni2L(1)(μ(1,3)-N3)][ClO4] (2) of the 24-membered macrocycle (L(1))(2-) coordinates it in the end-to-end fashion. A comparison of the X-ray structures of 2, 3, and 7 reveals the form-selective binding of complex 3 to be a consequence of its preorganized, channel-like binding pocket, which accommodates the azide anion via repulsive CH···π interactions in the end-on mode. In contrast to [Ni2L(1)(μ(1,3)-N3)][ClO4] (2), which features a S = 0 ground state, [Ni2(L(2))(μ(1,1)-N3)][BPh4] (8) has a S = 2 ground state that is attained by competing antiferromagnetic and ferromagnetic exchange interactions via the thiolato and azido bridges with a value for the magnetic exchange coupling constant J of 13 cm(-1) (H = -2JS1S2). These results are further substantiated by density functional theory calculations. The stability of the azido-bridged complex determined by isothermal titration calorimetry in MeCN/MeOH 1/1 v/v (log K11 = 4.88(4) at I = 0.1 M) lies in between those of the fluorido- (log K11 = 6.84(7)) and chlorido-bridged complexes (log K11 = 3.52(5)). These values were found to compare favorably well with the equilibrium constants derived at lower ionic strength (I = 0.01 M) by absorption spectrophotometry (log K11 = 5.20(1), 7.77(9), and 4.13(3) for N3(-), F(-), and Cl(-) respectively).

Synthesis, characterization and non-linear optical properties of two mononuclear Cu(II) complexes of 2,6-bis(1-butylbenzimidazol-2-yl)pyridine

Two copper(II) complexes, [Cu(L)(N3)2]·MeOH and [Cu(L)(NCS)2]·MeOH, were prepared and characterized by spectroscopic, analytical, and quantum chemical studies, where L is 2,6-bis(1-butylbenzimidazol-2-yl)pyridine. X-ray quality crystals of [Cu(L)(N3)2]·MeOH were obtained by slow evaporation of MeOH solution of the complex. Molecular structure of [Cu(L)(N3)2]·MeOH was determined by X-ray crystallography. The asymmetric unit contains one [Cu(L)(N3)2] and one MeOH molecule. Cu(II) in [Cu(L)(N3)2]·MeOH is five-coordinate, bonded to five nitrogens (three from L and two from two azide anions). Coordination geometry around Cu(II) center is distorted square-pyramidal with τ value of 0.065. Optimized geometries, IR spectra, and non-linear optical properties of the complexes were obtained by computational studies based on density functional theory (DFT) with M062X method. NLO properties of these complexes were investigated computationally and both complexes exhibit better NLO properties than urea.

Structural snapshots in the copper(ii) induced azide-nitrile cycloaddition: effects of peripheral ligand substituents on the formation of unsupported μ1,1-azido vs.μ1,4-tetrazolato bridged complexes.

The azido ligand is widely used in coordination chemistry both as a ligand and as a metal-bound reactant. Its role as a bridge for magnetic exchange coupling has attracted a lot of attention in polynuclear metal complexes. However, only a very limited number of complexes are known in which a single azide anion, particularly in the μ1,1-mode, is the only unsupported connection between two metal centers. We present here a series of copper(ii)-azido complexes with amine anchored, triazole-based tripodal ligands containing varying substituents. In the mononuclear copper-azido complexes there is only a negligible effect of these substituents on the structure of the metal complexes. However, the substituents seem to play a decisive role in the type and formation of the dinuclear complexes. Using the tripodal ligand TBTA with flexible benzyl substituents resulted in a rare example of an unsupported and solely μ1,1-azido-bridged dinuclear complex. The use of the TDTA ligand with 2,6-diisopropylphenyl moieties as rigid and sterically demanding substituents resulted in the formation of a scarce example of a solely μ1,4-tetrazolato-bridged dinuclear complex by in situ cycloaddition between the azide and solvent nitrile. This observation of a reaction of unactivated aliphatic nitrile with the azide anion at room temperature is very unusual. The isolation and characterization (by means of X-ray diffraction) of intermediates allows for mechanistic insights into the cycloaddition reaction. The isolated bridges in both dinuclear complexes render them ideal model compounds for the investigation of the magnetic exchange mediated by these ligands usually employed in polynuclear complexes and frameworks together with additional bridging ligands. Magnetic measurements and broken-symmetry DFT calculations were used to shed light on the magnetic exchange revealing weak and moderate antiferromagnetic exchange for the azide and tetrazolate, respectively.

The vibrational spectroscopy of the coordinated azide anion; a theoretical study.

The vibrational behaviour of the azide anion in a variety of environments has been examined by DFT methods. The frequency is sensitive to polar, dipolar and quadrupolar fields. The frequency is also dependent on the metal to which it is bonded and thus to the details of that bonding. Several azides within one molecule can be strongly vibrationally coupled, a coupling which carries with it a transfer of spectral activity. It is suggested that whilst absolute vibrational frequencies carry little immediately accessible information, a combination of infrared and Raman data for the antisymmetric stretch region might give limited structural insights.

Structural and magnetic modulations of copper(II) azido complexes: unexpected in situ reactions of mono-N-donor pyridine-based co-ligands.

Low-temperature hydrothermal reactions of copper salts with NaN3 and structurally related pyridine-based ligands, 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, 4-benzylpyridine, and quinoline (L(4)), respectively, led to the formation of four new magnetic complexes, [Cu3(L(1))2(N3)6]n (), [Cu3(L(2))2(N3)6]n (), [Cu(L(3))2(N3)2] (), and [Cu(L(4))(N3)2]n (). In these complexes, L(1), L(2), and L(3) are pyridine, 3-azidomethylpyridine, and 4-benzoylpyridine, being generated in situ by the decomposition, azido substitution, and oxidation reaction of the 1-(4-pyridyl)pyridinium, 3-chloromethylpyridine, and 4-benzylpyridine, respectively. and have similar structures being composed of double end-on azido-bridging planar [Cu3(L)2(N3)6] trinuclear units, which are further linked into a two-dimensional layer by the end-to-end azido bridges of themselves, along with their weak end-on coordination. It is interesting that the only slight differences of geometrical parameters in and have led to distinct magnetic interactions between the trinuclear units, where the former is antiferromagnetic but the latter is ferromagnetic, whereas has a mono-nuclear core structure, which is further extended to a one-dimensional (1D) chain by weakly coordinated end-on azido bridges. consists of unique 1D chains with double end-on azido bridge bonding distorted five-coordinated Cu(ii) centers, and exhibits ferromagnetic intrachain interactions. In the structures of these complexes there also exist weak inter-layer or inter-chain hydrogen bonds, which should also be responsible for some magnetic behavior at low temperature. In addition, primary structural and magnetic comparisons and discussions have also been performed by combining other reported azido-Cu(ii) systems with related pyridyl-based co-ligands. These results show that the selection of synthesis conditions and slight decoration of co-ligands (or geometric differences of them) have important influences on the structures and magnetic properties of resulting metal azido complexes.

An ‘OFF–ON’ fluorescent chemosensor based on rhodamine 6G-2-chloronicotinaldehyde for the detection of Al3+ ions: Part II

A novel, optical rhodamine-2-chloronicotinaldehyde-type chemosensor (R6CN) was designed, synthesized and characterized as a reversible switch. R6CN displayed high selectivity toward Al3+ from various metal ions, including Al3+, Li+, Na+, K+, Cs+, Mg2+, Ca2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, Ag+, Cd2+, Hg2+, Pb2+ and the resultant complex [R6CN-Al3+]. The ring-opening mechanism of the rhodamine spirolactam was induced by Al3+ binding, and the 1:1 stoichiometric structure between R6CN and Al3+ was adequately supported by the Job-plot evaluation, optical titration, FT-IR and 1H NMR results. Theoretical calculations and modeling simulations were performed using Material Studio 4.3 suite (VAMP), and the results supported the formation of a 1:1 complex between R6CN and Al3+. The fluorescence quantum yield of R6CN-Al3+ (Φf=92.33%) was very high compared to that of the bare ligand. The detection limit for Al3+ was 4.28×10−9M, and a significant color change from almost colorless to pale-pink occurred in the presence of Al3+. In turn, the R6CN-Al3+ complex acted as a selective chemosensor toward N3− among various anions, including F−, Cl−, Br−, I−, NO3−, CH3COO−, ClO4−, CN−, SCN−, HSO4−, HPO4− and PF6−, in acetonitrile media. Moreover, the R6CN-Al3+ complex also exhibited a high selectivity and sensitivity toward the azide anion upon the addition of Al3+, and the color reversed back to colorless when the two ions were present together in solution. At last, R6CN was productively applied to the PEGDMA polymer to sense Al3+ ions, which was analyzed using FT-IR, fluorescence confocal laser scanning microscopy (CLSM) and scanning electron microscopy (SEM) images.

Reaction between Azidyl Radicals and Alkynes: A Straightforward Approach to NH-1,2,3-Triazoles.

Reaction between nitrogen-centered radicals and unsaturated C-C bonds is an effective synthetic strategy for the construction of nitrogen-containing molecules. Although the reactions between nitrogen-centered radicals and alkenes have been studied extensively, their counterpart reactions with alkynes are extremely rare. Herein, the first example of reactions between azidyl radicals and alkynes is described. This reaction initiated an efficient cascade reaction involving inter-/intramolecular radical homolytic addition toward a C-C triple bond and a hydrogen-atom transfer step to offer a straightforward approach to NH-1,2,3-triazoles under mild reaction conditions. Both the internal and terminal alkynes work well for this transformation and some heterocyclic substituents on alkynes are compatible. This mechanistically distinct strategy overcomes the inherent limitations associated with azide anion chemistry and represents a rare example of reactions between a nitrogen-centered radicals and alkynes.

Nickel(II) complexes of N2S2 donor set ligand and halide/pseudohalides: Synthesis, crystal structure, DNA and bovine/human serum albumin interaction

A series of neutral hexacoordinated nickel(II) complexes of formula [Ni II(L)X2] (where L =3,4-bis(2-pyridylmethylthio)toluene with tetradentate N2S2 donor set and X = chloride (1), azide (2), cyanate (3) and isothiocyanate anion (4)) have been synthesized and isolated in pure form. The complexes were characterized by physicochemical and spectroscopic methods along with detailed structural characterization of 1,2 and 3 by single crystal X-ray diffraction analyses. The structural study showed that the nickel(II) ion has a distorted octahedral geometry being chelated by the tetradentate N2S2 ligand and bound to cis- located choride or pseudohalide anions. In dimethylformamide solution the complexes showed quasi-reversible Ni II/NiIII redox couples in cyclic voltammograms with E1/2 values of + 0.723, + 0.749, + 0.768 and + 0.868 V for 1, 2, 3 and 4, respectively. The study of interaction of the complexes with calf thymus DNA, bovine serum albumin (BSA) and human serum albumin (HSA) using spectroscopic and physicochemical tools clearly indicates that the complexes interact with DNA via groove binding mode. Four new neutral distorted octahedral nickel(II) complexes of general formula, [NiII(L)X2] have been synthesized and structurally characterized. The spectroscopic and physicochemical studies of interaction of the complexes with calf thymus DNA, BSA and HSA have also been included.

Crystal structures of μ-oxalato-bis-[azido-(hista-mine)-copper(II)] and μ-oxalato-bis-[(dicyan-amido)(hista-mine)-copper(II)

The title compounds, μ-oxalato-κ(4) O (1),O (2):O (1'),O (2')-bis-[[4-(2-amino-eth-yl)-1H-imid-azole-κ(2) N (3),N (4)](azido-κN (1))copper(II)], [Cu2(C2O4)(N3)2(C5H9N3)2], (I), and μ-ox-al-ato-κ(4) O (1),O (2):O (1'),O (2')-bis-[[4-(2-amino-eth-yl)-1H-imidazole-κ(2) N (3),N (4)](dicyanamido-κN (1))copper(II)], [Cu2(C2O4)(C2N3)2(C5H9N3)2], (II), are two oxalate-bridged dinuclear copper complexes. Each Cu(II) ion adopts a five-coordinate square-pyramidal coordination sphere where the basal N2O2 plane is formed by two O atoms of the oxalate ligand and two N atoms of a bidentate chelating histamine mol-ecule. The apical coordination site in compound (I) is occupied by a monodentate azide anion through one of its terminal N atoms. The apical coordination site in compound (II) is occupied by a monodentate dicyanamide anion through one of its terminal N atoms. The mol-ecules in both structures are centrosymmetric. In the crystals of compounds (I) and (II), the dinuclear complexes are linked through N-H⋯X and C-H⋯X (X = N, O) hydrogen bonds where the donors are provided by the histamine ligand and the acceptor atoms are provided by the azide, dicyanamide, and oxalate ligands. In compound (I), the coordinatively unsaturated copper ions inter-act with the histamine ligand via a C-H⋯Cu inter-action. The coordinatively unsaturated copper ions in compound (II) inter-act via a weak N⋯Cu inter-action with the dicyanamide ligand of a neighboring mol-ecule. The side chain of the histamine ligand is disordered over three sets of sites in (II).

Structure and magnetic properties of a copper(II) coordination polymer based on azide, pyridine and homophthalic acid.

The azide anion is a short bridging ligand that has been used extensively to construct magnetic coordination polymers, and fundamental magneto-structural correlations have been substantiated by theoretical calculations. The copper(II) coordination polymer poly[bis(μ-azido-κ(2)N(1):N(1))(μ4-homophthalato-κ(4)O:O':O'':O''')bis(pyridine-κN)dicopper(II)], [Cu2(C9H6O4)(N3)2(C5H5N)2]n, was synthesized from homophthalic acid (2-carboxyphenylacetic acid), pyridine and azide (N3(-)) by a hydrothermal reaction. Single-crystal structure analysis indicated that it features a one-dimensional chain structure which is comprised of (μ1,1-N3(-))(μ-syn-syn-COO(-))2- and (μ1,1-N3(-))2-bridged tetranuclear Cu(II) units. Magnetic measurements revealed that the compound exhibits dominant antiferromagnetic behaviour.

Synthesis, Structure, and Properties of Dicopper Complex With Imidazole-Containing Polyamine Ligand

A new dicopper complex [Cu2(L)(N3)2](ClO4)2·4H2O (1) with imidazole-containing macrocyclic polyamine ligand was synthesized, and characterized by elemental analysis, FT-IR, UV-Vis, TGA, single-crystal X-ray diffraction, and PXRD. Complex 1 crystallizes in monoclinic, space group P21/c. The coordination geometry around Cu(II) atom is five-coordinated distorted trigonal-bipyramid, and the imidazole-pendants and the azide anions are located on the different sides of the macrocyclic ligand.

Accommodative Behavior of Non-porous Molecular crystal at Solid-Gas and Solid-Liquid Interface.

Molecular crystals demonstrate drastically different behavior in solid and liquid state, mainly due to their difference in structural frameworks. Therefore, designing of unique structured molecular compound which can work at both these interfaces has been a challenge. Here, we present remarkable ‘molecular’ property by non-porous molecular solid crystal, dinuclear copper complex (C6H5CH(X)NH2)2CuCl2, to reversibly ‘adsorb’ HCl gas at solid-gas interface as well as ‘accommodate’ azide anion at solid-liquid interface with crystal to crystal transformation. The latter process is driven by molecular recognition, self-assembly, and anchimeric assistance. The observed transformations are feasible due to breathing of inner and outer coordination sphere around metal center resulting in change in metal polyhedra for ‘accommodating’ guest molecule. These transformations cause changes in optical, magnetic, and/or ferroelectric property offering diversity in ‘sensing’ application. With the proposed underlying principles in these exceptional reversible and cyclic transformations, we prepared a series of compounds, can facilitate designing of novel multifunctional molecular materials.

Azide anions inhibit GH-18 endochitinase and GH-20 Exo β-N-acetylglucosaminidase from the marine bacterium Vibrio harveyi.

Vibrio harveyi is a bioluminescent marine bacterium that utilizes chitin as its sole source of energy. In the course of chitin degradation, the bacterium primarily secretes an endochitinase A (VhChiA) to hydrolyze chitin, generating chitooligosaccharide fragments that are readily transported into the cell and broken down to GlcNAc monomers by an exo β-N-acetylglucosaminidase (VhGlcNAcase). Here we report that sodium salts, especially sodium azide, inhibit two classes of these chitin-degrading enzymes (VhChiA and VhGlcNAcase) with distinct modes of action. Kinetic analysis of the enzymatic hydrolysis of pNP-glycoside substrates reveals that sodium azide inhibition of VhChiA has a mixed-type mode, but that it inhibits VhGlcNAcase competitively. We propose that azide anions inhibit chitinase activity by acting as strong nucleophiles that attack Cγ of the catalytic Glu or Cβ of the neighbouring Asp residues. Azide anions may bind not only to the catalytic centre, but also to the other subsites in the substrate-binding cleft of VhChiA. In contrast, azide anions may merely occupy the small-binding pocket of VhGlcNAcase, thereby blocking the accessibility of its active site by short-chain substrates.

Two new CuI compounds with zwitterionic tetrazolate ligand: In situ synthesis, crystal structures, luminescence and photocatalytic properties

Two 2D new Cu(I) coordination polymers, namely [Cu2(mpTZ)2Br2]·H2O (1), and [Cu2(mpTZ)2N3]ClO4 (2) (mpTZ=N-methyl-4-pyridinium tetrazolate) have been synthesized under solvothermal conditions, in which the mpTZ ligands and CuI ions were obtained through in situ [2+3] cycloaddition reaction and reduction reaction of CuII salts, respectively. Both compounds have been structural characterized by single crystal X-ray diffraction, FT-IR, PXRD and EA. Compound 1 exhibits a 2D neutral coordination network, in which the CuI ions are bridged by η3−1, 2, 4-tetrazolate into 2D sheet. In compound 2, the CuI ions are linked by azide (in µ3−1, 1, 3 bridging mode) and tetrazolate (in η3−1, 2, 3 bridging mode) anions into 2D positively charged sheet, extended along the bc plane. Both compounds 1 and 2 exhibit intense bluish green luminescence in the solid state. Photocatalytic performances of the two compounds for the degradation of methylene blue (MB) under visible light were also investigated and the MB degradation in the presence of 1 was nearly complete (99%) after 150min.

Delicate structural regulation and stepwise phase transformation of Cu(II) coordination assemblies directed by inorganic counterion

Assembly of 3-(2-pyridyl)-4-(4-pyridyl)-5-(3-pyridyl)-1,2,4-triazole (L243) with Cu(NO3)2 or Cu(ClO4)2 affords a mononuclear complex [Cu(L243)2(H2O)2](NO3)2 (1) or a 1D linear coordination polymer {[Cu(L243)2(H2O)](ClO4)2(CH3OH)}n (3). Incorporating NaN3 into such assembled systems under similar conditions will produce two distinct 2D layered networks with the formulas {[Cu(L243)(N3)](NO3)(H2O)2}n (2) or {[Cu(L243)(N3)](ClO4)(H2O)}n (4), both of which contain dual inorganic-anions as the counterparts (NO3−/N3− for 2 and ClO4−/N3− for 4). Further, with a subtle change of reaction condition for 2 or 4, a 1D linear array [Cu(L243)(N3)2]n (5) is obtained with only N3− equilibrating the positive charges. Significantly, stepwise structural transformations between such crystalline phases can also be achieved by the direction of azide anion.