Coordination Polymers of the Macrocyclic Nickel(II) and Copper(II) Complexes with Isomeric Benzenedicarboxylates: The Case of Spatial Complementarity between the Bis-Macrocyclic Complexes and <i>o</i>-Phthalate

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In the asymmetric unit of the title compound, trans-diaqua(1,4,8,11-tetraazacyclotetradecane-κ4 N 1,N 4,N 8,N 11)zinc(II) trans-bis(hydrogen 4-phosphonatobiphenyl-4′-carboxylato-κO)(1,4,8,11-tetraazacyclotetradecane-κ4 N 1,N 4,N 8,N 11)zinc(II), [Zn(C10H24N4)(H2O)2][Zn(C13H9O5P)2(C10H24N4)], both Zn atoms lie on crystallographic inversion centres and the atoms of the macrocycle in the cation are disordered over two sets of sites. In both macrocyclic units, the metal ions possess a tetragonally elongated ZnN4O2 octahedral environment formed by the four secondary N atoms of the macrocyclic ligand in the equatorial plane and the two trans O atoms of the water molecules or anions in the axial positions, with the macrocyclic ligands adopting the most energetically favourable trans-III conformation. The average Zn—N bond lengths in both macrocyclic units do not differ significantly [2.112 (12) Å for the anion and 2.101 (3) Å for the cation] and are shorter than the average axial Zn—O bond lengths [2.189 (4) Å for phosphonate and 2.295 (4) Å for aqua ligands]. In the crystal, the complex cations and anions are connected via hydrogen-bonding interactions between the N—H groups of the macrocycles, the O—H groups of coordinated water molecules and the P—O—H groups of the acids as proton donors, and the O atoms of the phosphonate and carboxylate groups as acceptors, resulting in the formation of layers lying parallel to the (110) plane.

Section: Structural Commentarymentioning

confidence: 93%

Synthesis and crystal structure of diaqua(1,4,8,11-tetraazacyclotetradecane)zinc(II) bis(hydrogen 4-phosphonatobiphenyl-4′-carboxylato)(1,4,8,11-tetraazacyclotetradecane)zinc(II)

Tsymbal¹,

Andriichuk²,

Lozan³

et al. 2022

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“…The five-membered chelate rings are present in gauche (bite angles ca 85.5 ) and the six-membered in chair (bite angles ca 94.5 ) conformations (Table 1). The geometric parameters observed are characteristic of high-spin d 8 nickel(II) complexes with macrocyclic 14-membered tetraamine ligands (Lampeka & Tsymbal, 2004;Tsymbal et al, 2021). The axial Ni-N(CN) bond lengths are somewhat longer than the Ni-N(amine) ones, resulting in a slight tetragonal distortion of the trans-NiN 4 N 2 coordination polyhedron.…”

Section: Structural Commentarymentioning

confidence: 93%

Crystal structure of [{[Ni(C₁₀H₂₄N₄)][Ni(CN)₄]}·2H₂O]_n, a one-dimensional coordination polymer formed from the [Ni(cyclam)]²⁺cation and the [Ni(CN)₄]^2–anion

Tsymbal¹,

Andriichuk²,

Shova³

et al. 2021

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The asymmetric unit of the title compound, catena-poly[[[(1,4,8,11-tetraazacyclotetradecane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-μ-cyanido-κ2 N:C-[bis(cyanido-κC)nickel(II)]-μ-cyanido-κ2 C:N] dihydrate], {[Ni2(CN)4(C10H24N4)]·2H2O] n or [{[Ni(C10H24N4)][Ni(CN)4]}·2H2O] n , consists of a pair of crystallographically non-equivalent macrocyclic cations and anions. The nickel(II) ions (all with site symmetry \overline{1}) are coordinated by the four secondary N atoms of the macrocyclic ligands, which adopt the most energetically stable trans-III conformation, and the mutually trans N atoms of the tetracyanonickelate anion in a slightly tetragonally distorted NiN6 octahedral coordination geometry. The [Ni(CN)4)]2– anion exhibits a bridging function, resulting in the formation of parallel polymeric chains running along the [1\overline{1}0] direction. The water molecules of crystallization play a pivotal role in the three-dimensional supramolecular organization of the crystal. Acting as acceptors, they form N—H...Ow (w = water) hydrogen bonds with the secondary amino groups of the macrocycles, forming layers oriented parallel to the (001) plane. At the same time, as donors, they interact with the non-coordinated cyano groups of the anion via Ow—H...Nc (c = cyanide) hydrogen bonds, giving two-dimensional layers oriented parallel to the (100) plane and thus generating a three-dimensional network.

“…At the same time, open-chain aliphatic tetraamines like L (L = 1,4,8,11-tetraazaundecane, C 7 H 20 N 4 ), which is the closest structural and electronic analogue of cyclam, are practically unexploited in this respect and only one work dealing with the crystal structures of MOFs formed by the [Ni(L)] 2+ cation with tris(4carboxylatobenzyl)amine has been reported to date (Jiang et al, 2012). Besides, the [M(L)] synthons (M = Cu II , Ni II ) are convenient precursors for the one-pot template preparation of corresponding metal complexes of 14-membered azacyclam macrocycles (azacyclam = 1,4,8,11,13-pentaazacyclotetradecane) (Rosokha et al, 1993;Gerbeleu et al, 1999) and some complexes of this type functionalized at the N 13 position of the macrocyclic backbone have been structurally characterized by our group (Andriichuk et al, 2019;Tsymbal et al, 2010Tsymbal et al, , 2021. Herein, we report the syntheses and crystal structure of the product of the reaction of CuCl 2 , L and the isophthalate anion (ip 2À ) as its sodium salt, namely, trans-diaqua (1,4,8,11-…”

Section: Chemical Contextmentioning

confidence: 99%

Synthesis and crystal structure of trans-diaqua(1,4,8,11-tetraazaundecane)copper(II) isophthalate monohydrate

Tsymbal¹,

Arion²,

Lampeka³

2022

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In the title hydrated molecular salt, [Cu(C7H20N4)(H2O)2](C8H4O4)·H2O, the metal ion is coordinated by the two primary and two secondary N atoms of the amine ligand and the mutually trans O atoms of the water molecules in a tetragonally distorted octahedral geometry. The average equatorial Cu—N bond lengths (2.013 and 2.026 Å for Cu—Nprim and Cu—Nsec, respectively) are substantially shorter than the average axial Cu—O bond length (2.518 Å). The tetraamine ligand adopts its energetically favored conformation with its five- and six-membered chelate rings in gauche and chair conformations, respectively. In the crystal, the N—H donor groups of the tetraamine, the acceptor carboxylate groups of the isophthalate dianion and both the coordinated water molecules and the water molecule of crystallization are involved in numerous N—H...O and O—H...O hydrogen bonds, resulting in the formation of electroneutral layers oriented parallel to the ac plane.