NiII Cation Research Articles

Synthesis, crystal structure and thermal properties of catena-poly[[bis-(4-methyl-pyridine)-nickel(II)]-di-μ-thio-cyanato], which shows an alternating all-trans and cis-cis-trans-coordination of the NiS2Np 2Nt 2 octa-hedra (p = 4-methyl-pyridine, t = thio-cyanate).

The title compound, [Ni(NCS)2(C6H7N)2] n , was prepared by the reaction of Ni(NCS)2 with 4-methyl-pyridine in water. Its asymmetric unit consists of two crystallographically independent NiII cations, of which one is located on a twofold rotational axis whereas the second occupies a center of inversion, two independent thio-cyanate anions and two independent 4-methyl-pyridine co-ligands in general positions. Each NiII cation is octa-hedrally coordinated by two 4-methyl-pyridine coligands as well as two N- and two S-bonded thio-cyanate anions. One of the cations shows an all-trans, the other a cis-cis-trans configuration. The metal centers are linked by pairs of μ-1,3-bridging thio-cyanate anions into [101] chains. X-ray powder diffraction shows that a pure crystalline phase has been obtained and thermogravimetry coupled to differential thermoanalysis reveals that the title compound loses half of the 4-methyl-pyridine coligands and transforms into Ni(NCS)2(C6H7N). Nearly pure samples of this compound can be obtained by thermal annealing and a Rietveld refinement demonstrated that it is isotypic to its recently reported Cd analog [Neumann et al., (2020 ▸). CrystEngComm. 22, 184-194] In its crystal structure, the metal cations are linked by one μ-1,3(N,S)- and one μ-1,3,3(N,S,S)-bridging thio-cyanate anion into single chains that condense via the μ-1,3,3(N,S,S)-bridging anionic ligands into double chains.

New sterically hindered disubstituted imine derivatives of (thia)calix[4]arenes bearing bulky tert-butyl groups at the lower rim: synthesis, structures, and complexation ability toward CoII and NiII cations in solution

New sterically hindered disubstituted imine derivatives of (thia)calix[4]arenes bearing bulky tert-butyl groups at the lower rim: synthesis, structures, and complexation ability toward CoII and NiII cations in solution

Poly[di-aqua-[μ-1,4-bis-(pyridin-4-ylmeth-yl)pip-era-zine][μ-4-(carboxyl-atoeth-yl)benzoato]nickel(II)

The title compound, [Ni(C10H8O4)(C16H20N4)(H2O)2]n, contains NiII cations octa-hedrally surrounded within an [O4N2] coordination set. The cations are linked by 4-(carb-oxy-eth-yl)benzoate (ceb) and 1,4-bis-(pyridin-4-ylmeth-yl)piperazine (bpmp) ligands into tri-periodic diamondoid (dia) networks. The fivefold inter-penetrated dia networks are held into the crystal structure by means of O-H⋯O hydrogen bonding between bound water mol-ecules and unligated carboxyl-ate O atoms of the ceb ligands.

Synthesis, crystal structure and Hirshfeld surface analysis of bis-[4-(2-amino-eth-yl)morpholine-κ2 N,N']di-aqua-nickel(II) dichloride.

The title coordination compound, [Ni(C6H14N2O)2(H2O)2]Cl2, was synthesized by mixing 4-(2-amino-eth-yl)morpholine and nickel chloride in double-distilled water. The asymmetric unit comprises one half of an NiII cation (located on an inversion centre), one 4-(2-amino-eth-yl)morpholine ligand, one coordinated water mol-ecule and one chloride ion outside the metal coordination sphere. The nickel ion is in a octa-hedral environment of the N4O2 type, coordinating four N atoms from two 4-(2-amino-eth-yl)morpholine ligands and two trans-located O atoms from two water mol-ecules. The morpholine ligand was found disordered over two positions with a site occupancy ratio of 0.708 (8):0.292 (8). The crystal structure is consolidated by N-H⋯Cl, N-H⋯O, C-H⋯Cl and C-H⋯O hydrogen bonds. Hirshfeld surface analysis confirms that van der Waals inter-actions are prevalent in the crystal packing of the synthesized complex.

Synthesis, crystal structure and properties of catena-poly[[[bis-(3-methyl-pyridine-κN)nickel(II)]-di-μ-1,3-thio-cyanato] aceto-nitrile monosolvate

In the crystal structure of the title compound, {[Ni(NCS)2(C6H7N)2]·CH3CN} n , the NiII cation is octa-hedrally coordinated by two N-bonding and two S-bonding thio-cyanate anions, as well as two 3-methyl-pyridine coligands, with the thio-cyanate S atoms and the 3-methyl-pyridine N atoms in cis-positions. The metal cations are linked by pairs of thio-cyanate anions into chains that, because of the cis-cis-trans coordination, are corrugated. These chains are arranged in such a way that channels are formed in which disordered aceto-nitrile solvate mol-ecules are located. This overall structural motif is very similar to that observed in Ni(NCS)2[4-(boc-amino)-pyridine]2·CH3CN reported in the literature. At room temperature, the title compound loses its solvent mol-ecules within a few hours, leading to a crystalline phase that is structurally related to that of the pristine material. If the ansolvate is stored in an aceto-nitrile atmosphere, the solvate is formed again. Single-crystal X-ray analysis at room-temperature proves that the crystals decompose immediately, presumably because of the loss of solvent mol-ecules, and from the reciprocal space plots it is obvious that this reaction, in contrast to that in Ni(NCS)2[4-(boc-amino)-pyridine]2·CH3CN, does not proceed via a topotactic reaction.

Syntheses and crystal structures of the ethanol, acetonitrile and diethyl ether Werner clathrates bis-(iso-thio-cyanato-κN)tetra-kis-(3-methyl-pyridine-κN)nickel(II).

The reaction of nickel(II)thio-cyanate with 3-methyl-pyridine (3-picoline; C6H7N) in different solvents leads to the formation of crystals of bis-(iso-thio-cyanato-κN)tetra-kis-(3-methyl-pyridine-κN)nickel(II) as the ethanol disolvate, [Ni(NCS)2(C6H7N)4]·2C2H5OH (1), the acetonitrile disolvate, [Ni(NCS)2(C6H7N)4]·2CH3CN (2), and the diethyl ether monosolvate, [Ni(NCS)2(C6H7N)4]·C4H10O (3). The crystal structures of these compounds consist of NiII cations coordinated by two N-bonded thio-cyanate anions and four 3-methyl-pyridine ligands to generate NiN6 octa-hedra with the thio-cyanate groups in a trans orientation. In compounds 1 and 2 these complexes are located on centers of inversion, whereas in compound 3, they occupy general positions. In the crystal structures, the complexes are packed in such a way that cavities are formed in which the solvent mol-ecules are located. Compounds 1 and 2 are isotypic, which is not the case for compound 3. In compounds 1 and 2 the solvate mol-ecules are disordered, whereas they are fully ordered in compound 3. Disorder is also observed for one of the 3-methyl-pyridine ligands in compound 2. Powder X-ray diffraction and IR measurements show that at room temperature all compounds decompose almost immediately into the same phase, as a result of the loss of the solvent mol-ecules.

Varying Structure‐Directing Anions in Uranyl Ion Complexes with Ni(2,2′ : 6′,2′′‐terpyridine‐4′‐carboxylate)2

Abstract2,2′ : 6′,2“‐Terpyridine‐4′‐carboxylic acid (tpycH) reacts with uranyl cations under solvo‐hydrothermal conditions to give [UO2(tpyc)2] ⋅ 2H2O (1), a monoperiodic polymer different from that previously reported. In the additional presence of NiII cations, the Ni(tpyc)2 “expanded ligand” is formed and the structure of its complexes with the uranyl cation depends on the additional anions present. [(UO2)2F4(H2O)2Ni(tpyc)2] ⋅ 2H2O (2) and [UO2(mds)(H2O)Ni(tpyc)2] (3), where mds2− is methanedisulfonate, are monoperiodic polymers in which the fluoride anions are bridging and the mds2− anions chelating. [(UO2)4(NO3)2(H2O)4Ni5(tpyc)10](CF3SO3)4(NO3)2 ⋅ 7H2O (4) crystallizes as a wide and nearly planar monoperiodic ribbon. [(UO2)2(NO3)2(chdc)Ni(tpyc)2] ⋅ chdcH2 ⋅ 2CH3CN (5), where chdc2− is trans‐1,4‐cyclohexanedicarboxylate, is a monoperiodic chain including both bridging Ni(tpyc)2 and chdc2− ligands, the chains being further assembled into layers through hydrogen bonding to bridging chdcH2 molecules. Finally, [UO2Ni2(tpyc)4](I3)2 (6) crystallizes as a diperiodic network with sql topology. These results point to the possibility of modulating the structure of cationic uranyl ion complexes with Ni(tpyc)2 through addition of a wide range of bonding or non‐bonding anions.

Contrasting Networks and Entanglements in Uranyl Ion Complexes with Adipic and trans,trans-Muconic Acids.

Adipic (hexane-1,6-dicarboxylic, adpH2) and trans,trans-muconic (trans,trans-hexa-2,4-diene-1,6-dicarboxylic, mucH2) acids have been reacted with uranyl cations under solvo-hydrothermal conditions, yielding nine homo- or heterometallic complexes displaying in their crystal structure the effects of the different flexibility of the ligands. The complexes [PPh4]2[(UO2)2(adp)3] (1) and [Ni(bipy)3][(UO2)2(muc)3]·5H2O (2), where bipy is 2,2'-bipyridine, crystallize as diperiodic networks with the hcb topology, the layers being strongly puckered or quasiplanar, respectively. Whereas [(UO2)2(adp)3Ni(cyclam)]·2H2O (3), where cyclam is 1,4,8,11-tetraazacyclotetradecane, crystallizes as a diperiodic network, [(UO2)2(muc)3Ni(cyclam)]·2H2O (4) is a triperiodic framework in which the NiII cations are introduced as pillars within a uranyl-muc2- framework with the mog topology. [UO2(adp)(HCOO)2Cu(R,S-Me6cyclam)]·2H2O (5), where R,S-Me6cyclam is 7(R),14(S)-5,5,7,12,12,14-hexamethylcyclam, is a diperiodic assembly with the sql topology, and it crystallizes together with [H2NMe2]2[(UO2)2(adp)3] (6), a highly corrugated hcb network with a square-wave profile, which displays 3-fold parallel interpenetration. In contrast, [(UO2)3(muc)2(O)2Cu(R,S-Me6cyclam)] (7) is a diperiodic assembly containing hexanuclear, μ3-oxido-bridged secondary building units which are the nodes of a network with the hxl topology. The two related complexes [PPh3Me]2[(UO2)2(adp)3]·4H2O (8) and [PPh3Me]2[(UO2)2(muc)3]·H2O (9) crystallize as hcb networks, but their different shapes, undulated or quasiplanar, respectively, result in different entanglements, 2-fold parallel interpenetration in 8 and 2-fold inclined 2D → 3D polycatenation in 9.

Synthesis and crystal structure of bis-[μ-N,N-bis-(2-amino-eth-yl)ethane-1,2-di-amine]-bis-[N,N-bis-(2-amino-eth-yl)ethane-1,2-di-amine]-μ4-oxido-hexa-μ3-oxido-octa-μ2-oxido-tetra-oxido-tetra-nickel(II)hexa-tantalum(V) nona-deca-hydrate.

Reaction of K8{Ta6O19}·16H2O with [Ni(tren)(H2O)Cl]Cl·H2O in different solvents led to the formation of single crystals of the title compound, [Ni4Ta6O19(C6H18N4)4]·19H2O or {[Ni2(κ4-tren)(μ-κ3-tren)]2Ta6O19}·19H2O (tren is N,N-bis-(2-amino-eth-yl)-1,2-ethanediamine, C6H18N4). In its crystal structure, one Lindqvist-type anion {Ta6O19}8- (point group symmetry ) is connected to two NiII cations, with both of them coordinated by one tren ligand into discrete units. Both NiII cations are sixfold coordinated by O atoms of the anion and N atoms of the organic ligand, resulting in slightly distorted [NiON5] octa-hedra for one and [NiO3N3] octa-hedra for the other cation. These clusters are linked by inter-molecular O-H⋯O and N-H⋯O hydrogen bonding involving water mol-ecules into layers parallel to the bc plane. Some of these water mol-ecules are positionally disordered and were refined using a split model. Powder X-ray diffraction revealed that a pure crystalline phase was obtained but that on storage at room-temperature this compound decomposed because of the loss of crystal water mol-ecules.

A new [δ-Mo8O26]4−-based NiⅡ-coordination polymer constructed from a pyridinum ligand as a full spectrum responsive photocatalyst and its electrocatalytic properties

A new octamolybdate-based NiⅡ-coordination polymer [NiII(Bipbc)(δ-Mo8O26)0.5(H2O)3] (1) (Bipbc = 4,4′-bis[(4-carboxypyridino)methyl]biphenyl) was synthesized by hydrothermal reaction of the [Mo7O24]6− precursor with NiⅡ cations in the presence of H2BipbcCl2 ligand and structurally characterized. Compound 1 shows a 1-D chain, which consists of the [Ni2(Bipbc)2]4+ rings and [δ-Mo8O26]4− clusters. These 1-D chains are linked by H-bonds to form a 2-D supramolecular network. The photocatalytic activities of 1 on the degradation of methylene blue (MB) under full spectrum, visible and even near-infrared (NIR) light irradiation were tested, the degradation rates within 120 min are about 95.08%, 83.52%, 73.91%, respectively. Furthermore, the electrocatalytic properties of 1 were measured. 1 shows excellent electrocatalytic activities toward the reduction of H2O2, KBrO3 and the oxidation of ascorbic acid (AA).

2,5-Thiophenedicarboxylate: An Interpenetration-Inducing Ligand in Uranyl Chemistry.

Seven uranyl ion complexes have been crystallized under solvo-hydrothermal conditions from 2,5-thiophenedicarboxylic acid (tdcH2) and diverse additional, structure-directing species. [UO2(tdc)(DMF)] (1) is a two-stranded monoperiodic coordination polymer, while [PPh3Me][UO2(tdc)(HCOO)] (2) is a simple chain with terminal formate coligands. Although it is also monoperiodic, [C(NH2)3][H2NMe2]2[(UO2)3(tdc)4(HCOO)] (3) displays an alternation of tetra- and hexanuclear rings. Two-stranded subunits are bridged by oxo-coordinated NiII cations to form a diperiodic network in [UO2(tdc)2Ni(cyclam)] (4), but a homometallic sql diperiodic assembly is built in [Cu(R,S-Me6cyclam)(H2O)][UO2(tdc)2]·H2O (5), to which the counterion is hydrogen bonded only. Diperiodic networks with the hcb topology are formed in both [Zn(phen)3][(UO2)2(tdc)3]·2H2O·3CH3CN (6) and [PPh4]2[(UO2)2(tdc)3]·2H2O (7). The slightly undulating layers in 6 are crossed by oblique columns of weakly interacting counterions in polythreading-like fashion. In contrast, the larger curvature in 7 allows for three-fold, parallel 2D interpenetration to occur. These results are compared with previously reported cases of interpenetration and polycatenation in the uranyl-tdc2- system.

Stepwise Introduction of Flexibility into Aromatic Dicarboxylates Forming Uranyl Ion Coordination Polymers: a Comparison of 2‐Carboxyphenylacetate and 1,2‐Phenylenediacetate

Abstract2‐Carboxyphenylacetate (cpa2−) and 1,2‐phenylenediacetate (1,2‐pda2−) have been reacted with uranyl cations under solvo‐hydrothermal conditions to generate six homo‐ or heterometallic complexes. Both [UO2(cpa)] (1) and [UO2(cpa)(phen)] (2), where phen is 1,10‐phenanthroline, crystallize as monoperiodic coordination polymers. [Ni(bipy)3][(UO2)2(cpa)3]⋅2.5H2O (3), is a diperiodic network with the hcb topology, in which the hexagonal cells distort to accommodate the counterions. [UO2(cpa)2Ni(R,S‐Me6cyclam)] (4) crystallizes as a heterometallic diperiodic network in which uranyl dicarboxylate chains are assembled by bridging NiII cations. While [dmaepH2][(UO2)2(1,2‐pda)3]⋅3H2O (5), where dmaep is 1,4‐bis(2′‐dimethylaminoethyl)piperazine, is a diperiodic hcb network, [QH]2[(UO2)2(1,2‐pda)3]⋅3CH3CN (6), where Q is quinuclidine, is the first example of a triperiodic framework in the uranyl–phenylenediacetate family, its topological type being bto. The complex involving the related ligand 1,4‐phenylenediacetate (1,4‐pda2–), [QH]2[(UO2)2(1,4‐pda)3]⋅2CH3CN (7), is a daisy‐chain‐like monoperiodic polymer. These and previously reported results are discussed in terms of ligand flexibility and ability to form large chelate rings.

Helical water-soluble NiII complexes with pyridoxal ligand derivatives: Structural evaluation and interaction with biomacromolecules

This article deals with the synthesis of Schiff-based bis-azomethine-based ligands derived from pyridoxal and aliphatic dihydrazides and the synthesis of nickel(II) complexes C1–C4. The synthesized complexes had their structures elucidated by monocrystal X-ray diffraction and were characterized by vibrational and absorption spectroscopy. The synthesized ligands have characteristics that allow the formation of self-assembly processes, thus, the flexibility or rigidity of the coordination of organic molecules added to the orbitals of the NiII cation leads to the formation of helical complexes with double helix and a dinucler nickel(II) complex. Moreover, compounds was their interactions with CT-DNA and HSA absorption and emission analysis and molecular docking calculations.

Crystal structure of bis-(tetra-methyl-thio-urea-κS)bis-(thio-cyanato-κN)nickel(II).

In the course of our investigations regarding transition-metal thio-cyanates with thio-urea derivatives, the title compound, [Ni(NCS)2(C5H12N2S)2], was obtained. The asymmetric unit consists of one thio-cyanate anion and one tetra-methyl-thio-urea mol-ecule on general positions, as well as one NiII cation that is located on a twofold rotational axis. In this compound, discrete complexes are formed in which the NiII cations are surrounded by two trans-N-bonding thio-cyanate anions as well as two trans-S-bonding tetra-methyl-thio-urea mol-ecules within a distorted square-planar coordination geometry. The discrete complexes are linked by pairs of weak C-H⋯S hydrogen bonds between the thio-cyanate S and one of the tetra-methyl-thio-urea methyl hydrogen atoms into chains along the crystallographic a- and c-axis directions, which are combined into layers parallel to the ac plane. X-ray powder diffraction proves that a pure crystalline phase was obtained and measurements using thermogravimetry and differential thermoanalysis reveal that the compound decomposes at about 408 K, where all tetra-methyl-thio-urea mol-ecules are lost.

Flexible RuII Schiff Base Complexes: G-Quadruplex DNA Binding and Photo-Induced Cancer Cell Death.

A series of new RuII Schiff base complexes built on the salphen moiety has been prepared. This includes four flexible monometallic RuII compounds and six rigid bimetallic analogues that contain NiII , PdII or PtII cations into the salphen complexation site. Steady state luminescence titrations illustrated the capacity of the compounds to photoprobe G-quadruplex (G4) DNA. Moreover, the vast array of the Schiff base structural changes allowed to extensively assess the influence of the ligand surface, flexibility and charge on the interaction of the compounds with G4 DNA. This was achieved thanks to circular dichroism melting assays and bio-layer interferometry studies that pointed up high affinities along with good selectivities of RuII Schiff base complexes for G4 DNA. In cellulo studies were carried out with the most promising compounds. Cellular uptake with location of the compounds in the nucleus as well as in the nucleolus was observed. Cell viability experiments were performed with U2OS osteosarcoma cells in the dark and under light irradiation which allowed the measurements of IC50 values and photoindexes. They showed the substantial role played by light irradiation in the activity of the drugs in addition to the low cytotoxicity of the molecules in the dark. Altogether, the reported results emphasize the promising properties of RuII Schiff base complexes as a new class of candidates for developing potential G4 DNA targeting diagnostic or therapeutic compounds.

Uranyl Tricarballylate Triperiodic and Nanotubular Species. Counterion Control of Nanotube Diameter.

Tricarballylic acid (propane-1,2,3-tricarboxylic acid, H3 tca) was reacted with uranyl nitrate hexahydrate under solvo-hydrothermal conditions and in the presence of different additional cations, yielding four complexes which have been crystallographically characterized. [(UO2)2Ba(tca)2(H2O)4] (1), isomorphous to the PbII analogue previously reported, crystallizes as a triperiodic framework in which diperiodic uranyl-tca3- subunits with the hcb (honeycomb) topology are linked by carboxylate-bound BaII cations. Triperiodic polymerization is also found in [(UO2)2(tca)2Ni(cyclam)] (2) and [(UO2)2(tca)2Cu(R,S-Me6cyclam)] (3), but here the diperiodic uranyl-tca3- subunits have the sql (square lattice) topology, and the frameworks formed through bridging by NiII or CuII cations have different topologies, tcs in 2 and xww in 3. [Co(en)3][UO2(tca)]3·2H2O (4) crystallizes as a monoperiodic coordination polymer with the hcb topology and a nanotubular geometry. In contrast to the square-section nanotubules previously found in [NH4][(UO2)2Pb(tca)2(NO3)(bipy)] (bipy = 2,2'-bipyridine), those in 4 have a hexagonal section with a width of ∼7 Å. The structure-directing role of the hydrogen bonded counterions in these nanotubular species, either NH4+ located within the nanotubule cavity or [Co(en)3]3+ located outside, is discussed. Emission spectra in the solid state display the usual vibronic fine structure for 1 and 4, while uranyl emission is quenched in 3.

A 2D coordination polymer assembled from a nickel(II) tetraazamacrocyclic cation and 4,4'-(dimethylsilanediyl)diphthalate(3-) linker.

The preformed nickel(II) complex of the 14-membered macrocyclic ligand 1,4,8,11-tetraazacyclotetradecane (cyclam, L), when treated with 4,4'-(dimethylsilanediyl)diphthalic acid (H4A) in a DMF/H2O mixture (4:1 v/v) under heating, leads to [Ni(L)]3(HA)2·3DMF (I·DMF). Redissolution of this compound in a DMF/H2O/MeOH mixture (4:1:30 v/v/v) with mild acidification under gentle heating results in the formation of a similar compound but containing water and methanol molecules of crystallization, [Ni(L)]3(HA)2·5H2O·2MeOH (II·H2O). At lower temperature and concentration of reactants and longer reaction time, single crystals of composition {[{Ni(L)}3(HA)2]·4CH3OH}n (II·MeOH) were isolated. Single-crystal X-ray diffraction analysis of this compound, which, according to PXRD is isostructural with II·H2O but different from I·DMF, revealed its two-dimensional (2D) polymeric structure, i.e. poly[[bis{μ3-4-[(4-carboxy-3-carboxylatophenyl)dimethylsilyl]benzene-1,2-dicarboxylato-κ3O1:O2:O3'}tris(1,4,8,11-tetraazacyclotetradecane-κ4N)trinickel(II)] methanol tetrasolvate], {[Ni3(C18H13O8Si)2(C10H24N4)3]·4CH3OH}n. It is built up of the monoprotonated tricarboxylate HA3- ligand coordinated in a monodentate manner in the axial positions of two crystallographically independent NiII cations, one of which is located on a crystallographic inversion centre. Both metal ions adopt a slightly tetragonally elongated trans-N4O2 octahedral geometry. The compound has a lamellar structure with polymeric layers oriented parallel to the (10-2) plane, which are in turn linked via hydrogen bonds involving protonated carboxylic acid groups of the ligand. Bulk compounds I·DMF and II·H2O were characterized by FT-IR and diffuse reflectance spectroscopy and thermogravimetry, which provide evidence of their structural differences.

Formation of Oligo-Nuclear Carboxylate Nickel(II) Complexes with Nitrogen-Containing Ligands. Quantum-Chemical Simulation

Using the DFT method PBE0/6-31G(d, p) and taking into account the solvent, the formation of bi- and pentahedral Ni(II) complexes with carboxylate and N-containing ligands in the gas phase was studied, and ΔG° of their formation from simple compounds was estimated. The functional role of bridging groups and hydrogen bonds in the formation of polynuclear structures was revealed. A model of self-organization of penta-nuclear coordination compounds [NiII5(O2CR)8L2n(μ-OH)2]0 from binuclear complex [NiII2(O2CR)4Ln(μ-H2O)]0 was proposed, into the structure of which mononuclear NiII cations are embedding and promote proton transfer from bridging aqua ligands.

Crystal structure of (15,20-bis-(2,3,4,5,6-penta-fluoro-phen-yl)-5,10-{(4-methyl-pyridine-3,5-di-yl)bis-[(sulfanediyl-methyl-ene)[1,1'-biphen-yl]-4',2-di-yl]}porphyrinato)nickel(II) di-chloro-methane x-solvate (x > 1/2).

The title compound, [Ni(C64H33F10N5S2)]·xCH2Cl2, consists of discrete NiII porphyrin complexes, in which the five-coordinate NiII cations are in a distorted square-pyramidal coordination geometry. The four porphyrin nitro-gen atoms are located in the basal plane of the pyramid, whereas the pyridine N atom is in the apical position. The porphyrin plane is strongly distorted and the NiII cation is located above this plane by 0.241 (3) Å and shifted in the direction of the coordinating pyridine nitro-gen atom. The pyridine ring is not perpendicular to the N4 plane of the porphyrin moiety, as observed for related compounds. In the crystal, the complexes are linked via weak C-H⋯F hydrogen bonds into zigzag chains propagating in the [001] direction. Within this arrangement cavities are formed, in which highly disordered di-chloro-methane solvate mol-ecules are located. No reasonable structural model could be found to describe this disorder and therefore the contribution of the solvent to the electron density was removed using the SQUEEZE option in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18].

Crystal structure of 210,220-bis-(2,6-di-chloro-phen-yl)-4,7,12,15-tetra-oxa-2(5,15)-nickel(II)porpyhrina-1,3(1,2)-dibenzena-cyclo-hepta-deca-phane-9-yne di-chloro-methane monosolvate.

The asymmetric unit of the title compound, [Ni(C52H34Cl4N4O4)]·CH2Cl2, consists of two discrete complexes, which show significant differences in the conformation of the side chain. Each NiII cation is coordinated by four nitro-gen atoms of a porphyrin mol-ecule within a square-planar coordination environment. Weak intra-molecular C-H⋯Cl and C-H⋯O inter-actions stabilize the mol-ecular conformation. In the crystal structure, discrete complexes are linked by C-H⋯Cl hydrogen-bonding inter-actions. In addition, the two unique di-chloro-methane solvate mol-ecules (one being disordered) are hydrogen-bonded to the Cl atoms of the chloro-phenyl groups of the porphyrin mol-ecules, thus stabilizing the three-dimensional arrangement. The crystal exhibits pseudo-ortho-rhom-bic metrics, but structure refinements clearly show that the crystal system is monoclinic and that the crystal is twinned by pseudo-merohedry.