Asymmetric Unit Research Articles

Synthesis of a New Dinuclear Ag(I) Complex with Asymmetric Azine Type Ligand: X-ray Structure and Biological Studies

Aspects of the molecular and supramolecular structure of the new dinuclear [Ag(L)(NO3)]2 complex, where L is 2-((E)-(((E)-1-(thiazol-2-yl)ethylidene)hydrazono)methyl)phenol, were discussed. The complex was crystallized in the monoclinic crystal system and P21/n space group. The unit cell parameters are a = 10.3274(2) Å, b = 11.4504(3) Å, c = 12.7137(3) Å and β = 108.2560(10)°. The asymmetric unit comprised one [Ag(L)(NO3)] formula in which the azine and nitrate ligand groups act as NN- and OO-bidentate chelates, respectively. The coordination environment of the Ag(I) is completed by one weak Ag-O bond with another [Ag(L)(NO3)] unit, leading to the dinuclear formula [Ag(L)(NO3)]2. This was clearly revealed by Hirshfeld analysis. Additionally, the Ag…C, O…H and C…C intermolecular interactions played an important role in the molecular packing of the studied complex. The antimicrobial, antioxidant and cytotoxic activities of the [Ag(L)(NO3)]2 complex and the free ligand (L) were discussed. While the [Ag(L)(NO3)]2 complex showed very weak antioxidant activity, the results of the antifungal and cytotoxic activities were promising. The inhibition zone diameters (IZD) and the minimum inhibitory concentration (MIC) values were determined to be 31 mm and 20 μg/mL, respectively, against A. fumigatus, which is compared to 17 mm and 156 μg/mL, respectively, for the positive control Ketoconazole. Generally, the Ag(I) complex has better antimicrobial activities than the free ligand against all microbes except for S. aureus, where the free ligand has higher activity. Additionally, the IC50 value against colon carcinoma (HCT-116 cell line) was determined to be 12.53 ± 0.69 µg/mL, which is compared to 5.35 ± 0.49 µg/mL for cis-platin. Additionally, the Ag(I) complex displays better cytotoxicity than the free ligand (L) (242.92 ± 8.12 µg/mL).

Synthesis, Molecular and Supramolecular Structures of Symmetric Dinuclear Cd(II) Azido Complex with bis-Pyrazolyl s-Triazine Pincer Ligand

A new dinuclear Cd(II)-azido complex of 2,4-bis(3,5-dimethyl-1H-pyrazol-1-yl)-6-methoxy-1,3,5-triazine (PMT) pincer ligand is synthesized. Its single crystal X-ray structure reveals the dinuclear [Cd(PMT)(Cl)(N3)]2 formula. The triclinic crystal parameters are a = 9.323(4) Å, b = 10.936(5) Å, c = 11.312(6) Å, α = 112.637(10)°, β = 104.547(11)° and γ = 105.133(10)° while V = 944.1(8) Å3. Due to symmetry considerations, the asymmetric unit comprises a half [Cd(PMT)(Cl)(N3)]2 formula. The Cd(II) is hexa-coordinated with one tridentate PMT ligand in a pincer fashion mode in addition to one terminal chloride and two azide ions bridging the two Cd(II) centers in double μ(1,1) bridging mode. Unusually, the Cd-N(s-triazine) bond is not the shortest among the Cd-N interactions with the PMT pincer ligand. The supramolecular structure of the dinuclear [Cd(PMT)(Cl)(N3)]2 formula is controlled by a significant amount of Cl…H (16.4%), N…H (25.3%), H…C (9.8%) and H…H (37.2%) interactions based on Hirshfeld surface analysis. Careful inspection of the shape index map reveals the presence of some weak π-π stacking interactions between the s-triazine and pyrazolyl moieties. The percentage of C…C contacts is 1.9% where the C2…C8 (3.462 Å) is the shortest while the centroid–centroid distance is 3.686 Å. Natural charge analysis describes the charge transferences from the ligand groups to the Cd(II), while and atoms in molecules (AIM) give an indication on the properties of the Cd-N and Cd-Cl bonds.

Synthesis, crystal structure and spectroscopic investigations of heteronuclear Co(III)/Cu(II), Co(III)/Cd(II) and Fe(III)/Cd(II) 3D coordination polymers with 4-(2-aminoethyl)pyridine

The cyanide complexes of transition metals with 4-(2-aminoethyl)pyridine (4aepy) of {[Cu(H2O)(µ-4aepy)Cu(µ-4aepy)2Cu(µ-4aepy)Co2(µ-CN)6(CN)6]·3H2O}n (1), (NH4)[Cd(µ-4aepy)2Co(µ-CN)2(CN)4]n (2) and (NH4)[Cd(µ-4aepy)2Fe(µ-CN)2(CN)4]n (3) were synthesized and investigated by vibrational (FT-IR and Raman), powder X-ray diffraction (PXRD), elemental and thermal analysis techniques. The crystal structures of the complexes have been determined by the single crystal X-ray diffraction (SC-XRD) patterns. The crystallographic analysis reveals that complex 1 crystallizes in the monoclinic system, space group P21, whereas; complexes 2 and 3 crystallize in the tetragonal system, space group P42/ncm. The asymmetric unit of heterometallic complex 1 consists of three Cu(II) ions, two Co(III) ions, four 4aepy ligands, twelve cyanide ligands, one aqua ligand and three non-coordinated water molecules. The asymmetric unit of heterometallic complexes 2–3 consists of one Cd(II) ion, one M ion [M = Co(III) in 2 and Fe(III) in 3], two cyanide ligands, half 4aepy ligand and one ammonium ion. Each Cd(II) ion is located at a center of symmetry and is coordinated by two nitrogen atoms by the cyanide ligands and by four nitrogen atoms by the 4aepy ligands. As a result, they show distorted octahedral coordination geometries. In complex 1, the intermolecular O–H⋯N, N–H⋯N, N–H⋯O and C–H⋯N hydrogen bonds and CN⋯π and π⋯π interactions play a crucial role in the architecture of 3D network. The intermolecular CN···π interaction between cyanide ligand and pyridine ring of the 4aepy ligand is the most striking feature of complex 1. Heterometallic complexes 2–3 have 3D coordination polymers.

Crystal structure of a copper–mefenamate complex solvated with diglyme and water

In the copper–mefenamate complex tetrakis[μ-2-(2,3-dimethylanilino)benzoato-κ2 O:O′]bis[aquacopper(II)]–1-methoxy-2-(2-methoxyethoxy)ethane (1/2), [Cu2(C15H14NO2)4(H2O)2]·2C6H14O3, the asymmetric unit comprises a CuII cation coordinated to two mefenamate ligands solvated with a water molecule and a diglyme molecule. The complex adopts a paddlewheel motif and is compared to structural analogues crystallized with dimethylformamide and dimethyl sulfoxide.

Bis[(4-methylphenyl)diphenylphosphane-κP](nitrato-κ2 O,O′)silver(I)

The molecular structure of the title AgI complex, [Ag(NO3)(C19H17P)2] or [Ag{(p-CH3C6H4)(C6H5)2P-κP}2-NO3-κ2 O:O′], is described, where a distorted trigonal–planar coordination environment is exhibited about the central AgI atom; in this description, the two O atoms are assumed to occupy one position in the coordination sphere. The compound crystallized with half a molecule in the asymmetric unit having the AgI atom lying on a twofold axis.

Melt Crystallization of Celecoxib-Carbamazepine Cocrystals with the Synchronized Release of Drugs.

The fixed-dose combination drug products have been increasingly used to treat some complex diseases. A cocrystal containing two therapeutic components, named as a drug-drug cocrystal, is an ideal solid form to formulate as a fixed-dose combination product. The aim of the study is to prepare celecoxib-carbamazepine (CEL-CBZ) cocrystals by melt crystallization to achieve the synchronized release of drugs. The crystal structure of the CEL-CBZ cocrystal was determined from the cocrystals harvested from melt by single crystal X-ray diffraction. The binary phase diagram and crystal growth kinetics of the CEL-CBZ cocrystal from melt were studied to optimize the process parameters of hot-melt extrusion for manufacturing large-scale cocrystals. The intrinsic dissolution rate studies were conducted to compare the dissolution profiles of drugs in the cocrystal and their individual forms. The CEL-CBZ cocrystal crystallized in the triclinic space group with one CEL and one CBZ molecule in the asymmetric unit. The crystallization of CEL-CBZ cocrystals were observed both in the supercooled liquid and glassy state. The formation of drug-drug cocrystals significantly alter the intrinsic dissolution rates of the parent drugs to favor the synchronized release. Melt crystallization is an alternative, efficient and eco-friendly approach for preparing drug-drug cocrystals on a large scale. The synchronized drug release by drug-drug cocrystals can be used to modulate the release profiles of parent drugs in the fixed-dose combination products.

Structural characterization and antimycobacterial evaluation of a benzimidazole analogue of the antituberculosis clinical drug candidate TBA-7371

The crystal structure and in vitro antimycobacterial properties of N-(2-fluoroethyl)-1-[(6-methoxy-5-methylpyrimidin-4-yl)methyl]-1H-benzo[d]imidazole-4-carboxamide (C17H18FN5O2, 1), a previously reported benzimidazole analogue of the 1,4-azaindole-based antituberculosis drug candidate TBA-7371, are reported. The structure determination was achieved using Hirshfeld atom refinement. Compound 1 crystallizes in the triclinic system (space group P\overline{1}) with two molecules in the asymmetric unit (Z′ = 2). The two crystallographically distinct molecules exhibit a similar conformation with the amide groups in a Z conformation, forming an intramolecular Namide—H...Nbenzimidazole hydrogen bond. The most significant supramolecular feature in the solid-state is a relatively short Cbenzimidazole—H...Npyrimidine hydrogen bond. Antimycobacterial testing confirmed in vitro activity against Mycobacterium smegmatis, but no growth inhibtion of Mycobacterium abscessus was found.

Structure and function of the NS5 methyltransferase domain from Usutu virus

Usutu virus (USUV), is a mosquito-borne flavivirus currently spreading outside the African continent producing substantial avian mortality. In contrast, infected humans could exhibit mild neurological symptoms or remain asymptomatic. As in other flaviviruses, the capped USUV genome encodes three structural and seven non-structural (NS) proteins. Among the NS proteins, NS5 plays crucial roles in virus replication, harbouring the capping and methyltransferase (MTase) activities in its N-terminal domain and the RNA-dependent RNA polymerase (RdRP) activity at the C-terminus. In this work, we present the first structural and functional characterization of the USUV MTase domain. The first structure of the USUV MTase has been determined in complex with its natural ligands (S-adenosyl-L-methionine [SAM]) and S-adenosyl-L-homocysteine [SAH]) at 2.2 Å resolution, showing a molecular dimer in the crystal asymmetric unit. One molecule is bound to the methyl donor SAM while the second is bound to the reaction by-product SAH. Both molecules are almost identical and also show a high structural similarity to the MTase domains of other flaviviruses. The structure of the USUV MTase bound to the inhibitor sinefungin at 1.8 Å resolution is also described. Careful comparisons of the interactions in the SAM-binding cavity prompt us to hypothesize about the strength and weakness of the structure-based design of antivirals directed to the SAM/SAH binding site that could be effective to deal with this threat.

2,5,8,11-Tetramethyl-2,5,8,11-tetraazadodecane-2,11-diium bis[hydroxytris(pentafluorophenyl)borate] benzene 2.5-solvate

The title compound of overall stoichiometry, C12H32N4 2+·2C18HBF15O−·2.5C6H6, crystallizes in the triclinic space group P\overline{1} and the stoichiometry of the asymmetric unit consists of two [C12H32N4]2+ dications, two [C18HBF15O]− anions, and 2.5 molecules of benzene as solvate. The dications are both at half occupancy and located on a center of inversion, as is one of the benzene solvate molecules. In the two anions the O—H groups participate in different hydrogen-bonding schemes. In anion A, the OH group participates in a bifurcated 2R 2 2(6) scheme with F atoms on different rings of an adjacent hydroxy[tris(pentafluorophenyl)]borate moiety with an additional N—H...O hydrogen bond with a dication. For anion B, the OH group participates in a single O—H...F R 2 2(6) scheme. In addition, there are both O—H...N and N—H...O hydrogen bonds involving dication D and anion B in an R 2 2(7) motif. There are numerous C—H...π interactions between the dications and all the three benzene solvate molecules. For solvate 3, the C—H...π interactions are on both sides of the benzene ring and link both dications and solvate into a linear chain in the c-axis direction.

Crystal structure of bis{3-(3,5-dichlorophenyl)-5-[6-(1H-pyrazol-1-yl)pyridin-2-yl]-4H-1,2,4-triazol-4-ido}iron(II) methanol disolvate

The asymmetric unit of the title compound, [FeII(C16H9Cl2N6)2]·2CH3OH, consists of half of a charge-neutral complex molecule and a discrete methanol molecule. The planar anionic tridentate ligand 2-[5-(3,5-dichlorophenyl)-4H-1,2,4-triazol-3-ato]-6-(1H-pyrazol-1-yl)pyridine coordinates to the FeII ion through the N atoms of the pyrazole, pyridine and triazole groups, forming a coordination sphere of the central ion that deviates moderately from an octahedral geometry. The average Fe—N bond distance is 1.953 Å, indicating the low-spin state of the FeII ion. The cone-like-shaped molecules, nested into each other, are linked through double weak C—H(pz)...π(ph) interactions into mono-periodic columns, which are further linked through weak C—H...N′/C′ interactions into di-periodic layers. The layers interact through double weak C–H(ph)...Cl bonds with neighbouring molecules. Energy framework analysis at the B3LYP/6–31 G(d,p) theory level reproduces the strong interaction within the layers and the weaker interlayer interactions. Intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, the relative contributions of the contacts to the crystal packing being H...H 26.1%, H...C/C...H 24.4%, H...Cl/Cl...H 18.9% and H...N/N...H 12.1%.

A new (monohydrate) form of 3,5-dicarboxyanilinium nitrate: crystal structure and Hirshfeld surface analysis

The title compound, C8H8NO4 +·NO3 −·H2O, crystallizes in the same space group (P21/c) as the previously reported dihydrate form [Liang & Zhu (2010). Acta Cryst. E66, o667], but with two formula units per asymmetric unit instead of one. In the crystal, the components are linked into a three-dimensional network by classical intermolecular O—H...O and N—H...O hydrogen bonds and π–π stacking interactions. A Hirshfeld surface (HS) analysis indicated that the most important contributions to the crystal packing are from H...O/O...H (52.4%), H...H (13.9%) and C...C (11.2%) for one cation and H...O/O...H (46.3%), H...H (20%) and O...C/C...O (10.6%) for the other.

Structure and Computational Studies of New Sulfonamide Compound: {(4-nitrophenyl)sulfonyl}tryptophan.

Synthesis of sulfonamide through an indirect method that avoids contamination of the product with no need for purification has been carried out using the indirect process. Here, we report the synthesis of a novel sulfonamide compound, ({4-nitrophenyl}sulfonyl)tryptophan (DNSPA) from 4-nitrobenzenesulphonylchloride and L-tryptophan precursors. The slow evaporation method was used to form single crystals of the named compound from methanolic solution. The compound was characterized by X-ray crystallographic analysis and spectroscopic methods (NMR, IR, mass spectrometry, and UV-vis). The sulfonamide N-H NMR signal at 8.07-8.09 ppm and S-N stretching vibration at 931 cm-1 indicate the formation of the target compound. The compound crystallized in the monoclinic crystal system and P21 space group with four molecules of the compound in the asymmetric unit. Molecular aggregation in the crystal structure revealed a 12-molecule aggregate synthon sustained by O-H⋯O hydrogen bonds and stabilised by N-H⋯O intermolecular contacts. Experimental studies were complemented by DFT calculations at the B3LYP/6-311++G(d,p) level of theory. The computed structural and spectroscopic data are in good agreement with those obtained experimentally. The energies of interactions between the units making up the molecule were calculated. Molecular docking studies showed that DNSPA has a binding energy of -6.37 kcal/mol for E. coli DNA gyrase (5MMN) and -6.35 kcal/mol for COVID-19 main protease (6LU7).

OXA-66 structure and oligomerisation of OXAAb enzymes.

The OXA β-lactamases are responsible for hydrolysing β-lactam antibiotics and contribute to the multidrug-resistant phenotype of several major human pathogens. The OXAAb enzymes are intrinsic to Acinetobacter baumannii and can confer resistance to carbapenem antibiotics. Here we determined the structure of the most prevalent OXAAb enzyme, OXA-66. The structure of OXA-66 was solved at a resolution of 2.1 Å and found to be very similar to the structure of OXA-51, the only other OXAAb enzyme that has had its structure solved. Our data contained one molecule per asymmetric unit, and analysis of positions responsible for dimer formation in other OXA enzymes suggest that OXA-66 likely exists as a monomer.

1-Hy-droxy-4-methyl-pyridinium chloride.

The title salt, C6H8NO+·Cl-, contains two cations and two anions in the asymmetric unit. The components are linked by O-H⋯Cl and C-H⋯Cl hydrogen bonds, leading to tetra- (square-planar) or penta-coordinated (square-pyramidal) chloride ions. The title salt is isostructural with its bromide analogue.

A new heteroleptic cuprous polymer constructed by a cyanopyridine ligand exhibiting a supramolecular framework structure and luminescence.

Luminescent cuprous complexes are of great importance among coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous polymer solvate, catena-poly[[[(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)-κ2P,P'](μ-pyridine-3-carbonitrile-κ2N1:N3)copper(I)] hexafluorophosphate dichloromethane trisolvate], {[Cu(C6H4N2)(C39H32OP2)]PF6·3CH2Cl2}n, conventionally abbreviated as {[Cu(3-PyCN)(Xantphos)]PF6·3CH2Cl2}n, where Xantphos and 3-PyCN represent (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane) and pyridine-3-carbonitrile, respectively, has been described. In this polymer solvate, the asymmetric unit consists of three dichloromethane solvent molecules, a hexafluorophosphate anion and a polymeric heteroleptic cuprous complex cation, in which the cuprous centre is in a CuP2N2 tetrahedral coordination and is coordinated by two P atoms from the Xantphos ligand and two N atoms from two 3-PyCN ligands (the pyridyl and cyano N atoms). It is through the connection of the μ2-bridging 3-PyCN ligand that these cuprous centres are linked into a one-dimensional helical chain structure. The chains are further assembled through C-H...π interactions to form a supramolecular metal-organic framework containing solvent-accessible channels. The UV-Vis absorption and photoluminescence properties of this heteroleptic cuprous polymer have been studied on as-synthesized samples. Its luminescence emission should mainly originate from the metal-to-ligand charge transfer excited state.

Synthesis, crystal structure and Hirshfeld analysis of triphenylphosphine–(4-bromophenyl)borane

The title compound, alternatively called (4-bromophenyl)dihydrido(triphenylphosphanyl)boron, C24H21BBrP, crystallizes in the space group P-1 with one symmetry-independent molecule in the asymmetric unit. The B and P atoms both adopt the expected tetrahedral geometry. A possible intramolecular B-Hδ-...δ+H-C dihydrogen bond exists between an arene group on phosphorus and the borane center. In the solid state, the title molecule is connected to its neighbors by intermolecular C-H...π interactions, with the arene rings on the P atom acting as hydrogen-bond donors and the arene ring of the borane acting as the acceptor. Hirshfeld analysis supports the existence of these interactions, as well as weak Br...Br interactions between neighboring molecules.

Hydrogen Bonding in Crystals of Pyrrol-2-yl Chloromethyl Ketone Derivatives and Methyl Pyrrole-2-Carboxylate

The crystal and molecular structure of three derivatives of carbonyl 2-substituted pyrroles was determined by the single crystal X-ray diffraction. There are 2,2-dichloro-1-(1-methyl-1H-pyrrol-2-yl)ethan-1-one (I), 2-chloro-1-(1H-pyrrol-2-yl)ethan-1-one (II) and methyl 1H-pyrrole-2-carboxylate (III). All compounds crystallize with one molecule in the asymmetric unit in P212121 for I and II, and P21/c group for III. Despite the similar structures of the investigated compounds, the hydrogen bonds formed in their crystal structures adopt different H-bond motifs. In structure I, the dimers R12(5) and R21(7) form a chain along the b-axis, while in structures II and III, chain C(5) structural motifs are formed. The single point calculations at a ωB97XD/6-311++G(d,p) level of theory indicate that systems with N-H⋯O bonds have greater interaction energies (are more stable) compared with systems featuring C-H⋯O/Cl bonds. A descriptive Hirshfeld analysis showed that the greatest differences are visible for the H⋯H interactions. These H⋯H interactions predominate in structure III, accounting for 45% of the intermolecular interactions, while in structures I and II, they account for only 25%. Although compounds I-II contain Cl-atoms, the percentage of Cl⋯Cl interactions is rather low. In structure with two Cl-atoms (I), the contribution of the Cl⋯Cl contacts is 8.7% and for II, the contribution accounts for only 0.4% of the interactions.

Synthesis, Spectroscopic and X-Ray Structure Determination of a New Mononuclear Terbium (III) Complex from the Ligand N,N'-1,5-bis(pyridylmethylidene) Carbonohydrazone (H2L)

In the title compound, [Tb(H2L)2(H2O)3].3Cl.4(H2O).(C2H5OH), the Tb3+ is nine-coordinated in a distorted monocapped square antiprismgeometry by four nitrogen atoms, two oxygen atoms from the ligand molecules of the tridentate N,N'-1,5-bis(pyridylmethylidene) carbonohydrazone) (H2L) and three oxygen atoms of coordinating water molecules. The structure of the complex was elucidated by X-ray diffraction analysis. Suitable crystals were grown by slow evaporation of ethanol solution. The compound crystallizes in the triclinic crystal system with a space group of Pī. The asymmetric unit of the compound contains two neutral ligand molecules, oneterbium ion, three coordinated water molecules, five and half uncoordinated water molecules and one uncoordinated ethanol molecule. In the crystal, the complex cations are linked by hydrogen bonds into layers. These layers, chloride anions and non-coordinating water molecules are connected by O—H···O, O—H···N, O—H···Cl, N—H···O, N—H···Cl and C—H···Cl hydrogen bonds into a three-dimensional structure.

Crystal structure of the capsular polysaccharide-synthesis enzyme CapG from Staphylococcus aureus.

Bacterial capsular polysaccharides provide protection against environmental stress and immune evasion from the host immune system, and are therefore considered to be attractive therapeutic targets for the development of anti-infectious reagents. Here, we focused on CapG, one of the key enzymes in the synthesis pathway of capsular polysaccharides type 5 (CP5) from the opportunistic pathogen Staphylococcus aureus. SaCapG catalyses the 2-epimerization of UDP-N-acetyl-D-talosamine (UDP-TalNAc) to UDP-N-acetyl-D-fucosamine (UDP-FucNAc), which is one of the nucleotide-activated precursors for the synthesis of the trisaccharide repeating units of CP5. Here, the cloning, expression and purification of recombinant SaCapG are reported. After extensive efforts, single crystals of SaCapG were successfully obtained which belonged to space group C2 and exhibited unit-cell parameters a = 302.91, b=84.34, c = 145.09 Å, β = 110.65°. The structure was solved by molecular replacement and was refined to 3.2 Å resolution. The asymmetric unit revealed a homohexameric assembly of SaCapG, which was consistent with gel-filtration analysis. Structural comparison with UDP-N-acetyl-D-glucosamine 2-epimerase from Methanocaldococcus jannaschii identified α2, the α2-α3 loop and α10 as a gate-regulated switch controlling substrate entry and/or product release.

Syntheses and structural characterizations of the first coordination polymers assembled from the Ni(cyclam)2+ cation and the benzene-1,3,5-tri-carboxyl-ate linker.

The asymmetric unit of catena-poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-μ2-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ2 O 1:O 3] octa-hydrate], {[Ni(C9H4O6)(C10H24N4)]·8H2O} n (I), consists of a macrocyclic Ni2+ cation, a carboxyl-ate dianion and eight highly disordered water mol-ecules of crystallization. The components of the compound catena-poly[[[(1,4,8,11-tetra-aza-cyclo-tetra-decane-κ4 N 1,N 4,N 8,N 11)nickel(II)]-μ2-5-carb-oxy-benzene-1,3-di-carboxyl-ato-κ2 O 1:O 3] monohydrate], {[Ni(C9H4O6)(C10H24N4)]·H2O} n (II), are two crystallographically unique centrosymmetric macrocyclic dications, a carboxyl-ate dianion and one water mol-ecule of crystallization. In each compound, the metal ion is coordinated in the equatorial plane by the four secondary N atoms of the macrocyclic ligand, which adopts the most energetically stable trans-III conformation, and two mutually trans O atoms of the carboxyl-ate anions in a slightly tetra-gonally distorted trans-NiN4O2 octa-hedral geometry. The crystals of both compounds are composed of parallel coordination polymeric chains running along the [010] direction in I and the [110] and [10] directions in II. The bridging carboxyl-ate anions display different modes of coordination connected with the relative orientation of coordinated O atoms, i.e., remote in I and inter-mediate in II, thus resulting in essentially different distances between the Ni atoms in the chains [11.0657 (4) and 8.9089 (2) Å in I and II, respectively]. As a result of hydrogen-bonding inter-actions, the chains are joined together in sheets oriented parallel to the (10) and (001) planes in I and II, respectively.