Ryszard Kubiak

X-ray analysis of phthalocyanines formed in the reaction of AuCu and AuSn alloys with 1,2-dicyanobenzene

Abstract X-ray investigations of the reactions of copper, tin and their alloys with gold, with 1,2-dicyanobenzene at 210 °C have been performed. It was found that under the conditions used, gold does not take part in the reaction with 1,2-dicyanobenzene, but separates from the alloys. Copper and tin phthalocyanines are formed as the main products of the above reactions. The crystal structure of tin phthalocyanine (SnPC) has been determined. SnPc crystallizes in the triclinic system ( a=12.048(3) A , b=12.630(3) A , c=8.671(3) A , a=95.85(5)°, β=95.10(5)°, γ=68.25(5)°), space group P 1 , Z=2. The refined structure with anisotropic temperature factors gave R=0.041. The Sn atom is coordinated by four isoindole N atoms, the average SnN distance being 2.267(6) A. The SnPc molecule is not planar. The Sn atom is 1.1286 A out of the plane of the four coordinating N atoms.

Synthesis, structural investigations and magnetic properties of dipyridinated manganese phthalocyanine, MnPc(py)2

Abstract The MnPc(py)2 complex was obtained in the reaction of MnPc with purified and dry pyridine under non-oxidation conditions. It crystallises in the centrosymmetric space group P21/c of the monoclinic system with two molecules per unit cell. The Mn2+ cation is coordinated by four N-isoindole atoms of phthalocyaninato(2−) macrocycle and axially by two nitrogen atoms of pyridine molecules into a tetragonal bipyramid. The MnPc(py)2 crystals are moderately stable under air, but in pyridine solution the MnPc(py)2 complex undergoes oxidation by O2 yieldings the binuclear manganese(III) μ-oxo complex (MnPcpy)2O as evidenced by the UV–Vis spectroscopy. The magnetic susceptibility measurement performed on solid sample of MnPc(py)2 shows the Curie–Weiss behaviour in the temperature region of 300–15 K. The calculated magnetic moment μeff indicates three unpaired electrons (S=3/2), thus the ground state configuration of Mn ion is (a1g)2(eg)2(b2g)1, and the MnPc(py)2 complex is the intermediate spin complex. Below 5.5 K (TN) the magnetic susceptibility sharply decreases due to the cooperative intermolecular antiferromagnetic interactions.

Crystal and molecular structures of metal-free phthalocyanines, 1,2-dicyanobenzene tetramers. II: α form

Abstract Phthalocyanine (C32H16N8) is formed besides tin phthalocyanine in the reaction of AuSn4 with 1,2-dicyanobenzene at 210 °C and crystallizes in the monoclinic system (space group, P21/c). The unit-cell parameters are a = 14.803(3) A , b = 4.729(2) A , c = 19.870(4) A , β = 122.02(2)° and Z = 2. The refined structure with anisotropic temperature factors for carbon and nitrogen atoms and isotropic for hydrogen atoms gave R = 0.0487. The crystal structure data for metal-free phthalocyanines are discussed and compared with metal phthalocyanines. The phthalocyanine molecule is planar; the average derivation of the atoms from the phthalocyanine plane is 0.0257.

Crystal structure of a novel bismuth phthalocyanine-bismuth iodide complex

Abstract A new phthalocyaninato complex of bismuth with formula [(BiPc) 4 (Bi 4 I 16 )] was obtained in the reaction of bismuth with 1,2-dicyanobenzene in iodine vapour. The crystal and molecular structure of the complex was determined by single crystal X-ray diffraction. The unit cell consists of four discrete (BiPc) + cations and (Bi 4 I 16 ) 4− anions. The (Bi 4 I 16 ) 4− complex anion is formed by four edge-sharing BiI 6 octahedra. The arrangement of molecules in the crystalline structure of the complex is mainly determined by ionic attraction between the (BiPc) + and (Bi 4 I 16 ) 4− moieties, i.e. each (Bi 4 I 16 ) 4− complex anion is encapsulated between four (BiPc) + cations. The structure is additionally stabilised by a set of distinct acceptor-donor intermolecular forces. The exceptionally short covalent BiN isoindole bonds are a pronounced feature of the (BiPc) + cations. To our knowledge the [(BiPc) 4 (Bi 4 I 16 )] compound is the only example of a metallophthalocyaninato complex in which the metal atoms are not exclusively incorporated into macrocyclic Pc molecules, but occupy independent sites in the common crystalline lattice.

SYNTHESIS AND X-RAY CHARACTERIZATION OF THE IODINE-DOPED METALLODIPHTHALOCYANINE UPC2I5/3

Abstract Partially oxidized by iodine, uranium(IV) diphthalocyanine, U(C32H16N8)2I5/3, (UPc2I5/3), was obtained by the direct reaction of pure powder uranium with 1,2-dicyanobenzene under a stream of iodine. The compound crystallizes in a space group D4h2−P4/mcc of the tetragonal system with one molecule in a unit. The two heavy atoms (U and I) are disordered in the crystal. The crystal is composed of partially oxidized UPc2 units, which form a pseudo monodimensional stack along the [001] direction. The stacks are surrounded by disordered chains of iodine, identified as I3− ions by Raman spectroscopy. The EPR measurements (g=2.0014) confirm that phthalocyaninato ligand is partially oxidized.

BISMUTH TRIPLE-DECKER PHTHALOCYANINE : SYNTHESIS AND STRUCTURE

Abstract Triclinic crystals of bismuth(III) triple-decker phthalocyanine, Bi2Pc3, Pc=C32H16N82−, were grown directly by the reaction of Bi2Se3 with 1,2-dicyanobenzene at 220°C. The Bi2Pc3 molecule is centrosymmetric with the bismuth atoms located closer to the peripheral phthalocyaninato(2−) rings than to the central ring. Each bismuth(III) ion is connected by four N-isoindole atoms to the peripheral and by four N-isoindole to the central Pc ring with average distances of 2.333 and 2.747 A, respectively. This indicates a stronger connection of Bi(III) to the peripheral saucer-shaped macrocyclic rings than to the central rings. The neighbouring phthalocyaninato(2−) moieties in the Bi2Pc3 molecule are separated by a distance of 3.101(5) A. The central Pc ring is rotated by 36.4° with respect to the peripheral ones. Differences in Bi–N bond lengths are a result of interaction of the bismuth ion with peripheral and central rings as well as the repulsion forces between two bismuth ions in the same Bi2Pc3 molecule, which are separated by a distance of 3.839(2) A. The crystal packing is characterized by a distance of 3.56 A between Pc rings of neighbouring Bi2Pc3 molecules.

INDATE(III) PHTHALOCYANINES : SYNTHESIS, SPECTROSCOPY AND CRYSTAL STRUCTURE OF IODOPHTHALOCYANINATO(2-) INDATE(III)

Abstract A new complex of iodophthalocyaninato(2-) indate(III) has been synthesized in crystalline form by the reaction of indium powder with 1,2-dicyanobenzene under a stream of iodine at about 200°C. It crystallizes in the monoclinic system, space group P21/n with Z=4 in a unit cell of dimensions a=12.797(3), b=10.776(2), c=19.475 A and β=98.05(3)° (V=2659.1 A3). The structure was solved by Patterson and Fourier difference methods and refined by full-matrix least-squares techniques to R=0.0380, wR (on F2)=0.0702 and S=1.058 for 3303 independent reflections and 379 refined parameters. The indium atom coordinates four Niso atoms of the saucer-shaped phthalocyaninato(2-) ligand and apically on iodine atom in a tetragonal pyramidal arrangement. The indium atom is located out of the plane towards the iodine atom by 0.737(3) A. The In–I distance is 2.672(1) A, the In–Niso distances range from 2.124(6) to 2.133(7) A. The phthalocyaninato ligand is severely distorted from planarity (convex distortion). The characteristic frequencies observed in IR and Raman spectroscopy have been assigned and discussed in relation to other metallophthalocyanines.

On polymorphic and non-polymorphic conversions of phthalocyanines

Abstract The X-ray and IR spectra of metal-free phthalocyanine show that the x-form of H 2 Pc is β-Pc. X-ray measurements of the β-form of MgPc reveal that alteration to the so-called α-form of MgPc occurs in air. Continued cycling of the sample between vacuum and air demonstrated the reversibility of this process. It has been concluded, that, in general, α-forms of M(II)Pc are not pure phthalocyanines, but are complexes of M(II)Pc with N 2 and O 2 molecules.

Crystal and molecular structure of dithallium phthalocyanine at 300 K

Abstract A new complex of dithallium phthalocyanine (C 32 H 16 N 8 Tl 2 ) in crystalline form has been synthesized. The crystal at room temperature is orthorhombic, space group Cmca , with lattice parameters a = 25.173(4) A , b = 7.353(2) A and c = 13.765(3) A , V = 2547.9(7) A 3 , Z = 4, M = 921.3 , D 0 (flotation) = 2.397 g cm −3 , D c = 2.402 g cm −3 . The refined crystal structure with anisotropic temperature factors for Tl, C and N atoms and isotropic for H atoms gave R = 0.043, wR = 0.040 and S = 1.75. The structure consists of discrete dithallium phthalocyanine molecules. The thallium atoms are displaced above and below the phthalocyanine skeleton plane. The deviation of the Tl atoms with the above plane is ± 1.844 A . Details of the molecular structure are compared and discussed with regard to other metallophthalocyanines.

A simple, novel method for the preparation of metallophthalocyanines

Abstract New metallophthalocyanines (MePc) in the crystalline form were synthesized by the direct reaction between the 1,2-dicyanobenzene and filings of the metallic elements or intermetallic alloys. The reaction took place at about 480 K in vacuum over a few days. Some remarks on the reaction mechanism of the MePc formation are made. It is assumed that under the experimental conditions used the 1,2-dicyanobenzene liquid undergoes a catalytic tetramerization. The catalytic atom of the metal is simultaneously coordinated by the forming tetramer.