Dimeric Molecules in the Crystals of a Calcium(II) Complex with Pyridine-2,6-Dicarboxylate and Water Ligands

The crystals of bis[ w -pyridine-2,6-dicarboxylato-O,N,O')]bis[trisaqua-calcium(II)] di(pyridine-2,6-dicarboxylic acid) contain dimeric molecules composed of two calcium(II) ions and two ligand molecules. Calcium ions are bridged by two bidentate oxygen atoms each donated by one carboxylic group of the ligand [Ca―N 2.467(2)Å], a monodentate oxygen atom of the second carboxylate group of the ligand [Ca―N 2.484(2)Å] and three oxygen atoms donated by the water molecules [mean Ca―O 2.388(2)Å]. The coordination polyhedron is a distorted pentagonal bipyramid. Acid molecules were found to be located in the space between dimers and involved in an extended network of hydrogen bonds.     

Crystal structures of two Ca(II) complexes with imidazole-4,5-dicarboxylate and water ligands

The structure of compound I: poly-diaqua(μ-imidazole-4,5-dicarboxylato-N,O; -O′; -O′′, -O′′′) calcium(II) monohydrate [Ca(C₅H₂N₂O₄)(H₂O)₂·H₂O] is built of molecular sheets in which imidazole-4,5-dicarboxylate ligands bridge the metal ions using both carboxylate groups, each bidentate. Ca(II) is coordinated by six oxygen atoms and one hetero-ring nitrogen atom distributed at the apices of a capped tetragonal bipyramid. The basal plane of the pyramid is formed by two carboxylate oxygen atoms [d(Ca–O2?=?2.374(1)?Å, d(Ca–O4)?=?2.412(1)?Å] and two water oxygen atoms [d(Ca–O5)?=?2.384(1)?Å, d(Ca–O6)?=?2.455(1)?Å], the capped position is occupied by the carboxylate oxygen atom O3 [d(Ca–O3)?=?2.325(1)?Å], the hetero-ring nitrogen atom [d(Ca–N2)?=?2.523(1)?Å] and the carboxylate oxygen atom O4 [d(Ca–O2)?= 2.412(1)?Å] form the apices of the prism. The solvation water molecule plays a significant role in a framework of hydrogen bonds responsible for the stability of the crystal. The structure of compound II: trans-tetraquadi(H-imidazole-4,5-dicarboxylato-N,O) calcium(II) monohydrate, [Ca(C₅H₃N₂O₄)₂(H₂O)₄·H₂O] consists of monomers in which the Ca(II) ion is located on a centre of symmetry. The coordination around the Ca(II) is a strongly deformed pentagonal bipyramidal with the imidazole-4,5-dicarboxylate (4,5-IDA) ligands in the trans arrangement forming a dihedral angle of 68.3°. An imidazole-ring nitrogen atom [d(Ca–N)?=?2.632(2)?Å] and one carboxylate O atom [d(Ca–O)?=?2.531(2)?Å] from each ligand coordinate to the metal ion. The coordination is completed by four water oxygen atoms [d(Ca–O)?=?2.393(2)?Å] and [d(Ca–O)?=?2.367(2)?Å]. The coordinated water molecules act as hydrogen bond donors and acceptors to the unbonded carboxylate oxygen atoms in adjacent monomers giving rise to a three-dimensional molecular network.     

Crystal structure of a calcium(II) complex with pyrazine-2,3-dicarboxylate,nitrate and water ligands

The structure of catena-[tris(aquo-O)(nitrato-O,O′)(µ-hydrogen pyrazine-2,3-dicarboxylato-O,N–O′,N′)calcium(II)][tetra(aquo-O)(μ-hydrogen pyrazine-2,3-dicarboxylato-O,N–O′,N′) calcium(I)] nitrate, {Ca[H(2,3-PZDC)](H₃O)₃(NO₃)}{Ca[H(2,3-PZDC)](H₂O)₄}⁺ (NO₃)^?, is composed of molecular ribbons in which calcium atoms are bridged by both N,O-bonding moieties of singly deprotonated ligand molecules. The hydrogen atom donated by one carboxylic group is linked by a short intramolecular hydrogen bond of 2.37 Å to an oxygen atom of the second carboxylic group of the same ligand. Two crystallographically independent Ca(II) ions exhibit different coordination modes. One is coordinated by two bonding moieties of the bridging ligand molecules, three water oxygen atoms and two oxygen atoms of a nitrate ligand. The other calcium ion is chelated by two bonding moieties donated by the bridging ligand molecules and four water oxygen atoms, forming a positively charged assembly with a nitrate anion located nearby. The coordination polyhedron of the first calcium ion is a strongly deformed bicapped pentagonal bipyramid with nine-coordinated atoms; the second calcium ion is also in a strongly deformed pentagonal bipyramid with one apex on one side of the equatorial plane and two apices on the other. Coordinated water oxygen atoms act as donors in a hydrogen-bond network.     

The Crystal and Molecular Structure of a New Calcium(II) Complex with Pyridine-2,6-DiCarboxylate,Water and Nitrate Ligands

Crystals of {catena-[μ-aqua-O]bis[μ-pyridine-2,6-dicarboxylato-O,N-O']} {[monoaqua-nitrato, O-calcium(II)] [diaqua-calcium(II)]} contain dimeric units composed of two calcium(II) ions and two ligand molecules, in which the calcium ions are bridged by two bidentate oxygen atoms, each donated by one carboxylic group of the ligand. The Ca(II) ion is also coordinated by one oxygen atom of the second carboxylate group and the hetero-ring nitrogen atom belonging to the same ligand molecule. The dimers form molecular chains through protons situated at the symmetry centers halfway between the non-bridging carboxylate oxygen atoms. In addition, both calcium ions in the dimer are bridged to calcium ions in adjacent dimers - each by a pair water oxygen molecules giving rise to two-dimensional molecular sheets. Coordination of the Ca ion in the dimer is completed either by two water oxygen atoms or by one water oxygen atom and an oxygen atom donated by a nitrate group. The molecular sheets are held together by an extended system of hydrogen bonds.     

Three-dimensional polymeric molecular pattern in the structure of a Ca(II) complex with pyrazine-2,3,5,6-tetracarboxylate and water ligands

Triclinic unit cell [space group P 1] of the calcium(II) complex with pyrazine-2,3,5,6-tetracarboxylate (2,3,5,6-PZTC) and water ligands [poly-bis(μ-aqua)di(μ-pyrazine-2,3,5,6-tetracarboxylate)tetracalcium(II)] contains four Ca(II) ions in two symmetry independent sites, two 2,3,5,6-PZTC ligands with their geometrical centers at the inversion centers at 0, 1/2, 1/2 and 0, 1/2, 0 and two coordinated water molecules. Metal ions are bridged by the ligand molecules via their N,O bonding moieties and carboxylate oxygen atoms as well as coordinated water oxygen atoms producing a densely packed three-dimensional molecular pattern. The Ca1 ion coordinates eight atoms at the corners of a distorted bicapped tetragonal bipyramid. The coordination number of the Ca2 ion is seven in a strongly distorted pentagonal bipyramid. The pyrazine ring planes of the ligands are parallel to each other forming molecular sheets stacked normal to the a axis. They are interconnected by carboxylate oxygen atoms coordinating calcium ions located between the adjacent sheets.     

The Crystal Structures of Two Calcium(II) Complexes with Pyrazine- 2,6-Dicarboxylate and Water Ligands

The structure of catena-{bis[(μ-aqua)(diaqua)(pyrazine-2,6-dicarboxylato-O,N-μ-O')](calcium(II)} consists of dimeric units composed of two calcium(II) ions, two ligand molecules and six water molecules. The calcium ions are bridged by two bidentate oxygen atoms, each donated by one carboxylic group of the ligand. The Ca(II) ion is also coordinated by one oxygen atom of the second carboxylate group and the hetero-ring nitrogen atom belonging to the same ligand molecule. Both calcium ions in a dimer are bridged to the Ca(II) ions in adjacent dimers by a pair of water molecules forming infinite molecular ribbons. In addition, each Ca(II) ion is coordinated by three water molecules; one of them is used for bridging the adjacent dimer. The coordination polyhedron around the Ca(II) ion is a pentagonal bipyramid with two apices above and one apex below the equatorial plane. The same molecular pattern is observed in the structure of catena-{bis[(μ-aqua)(diaqua)(pyrazine-2,6-dicarboxylato-O,N-μ-O')](calcium(II)} dihydrate which, in addition, contains two solvation water molecules per unit cell. In both compounds the molecular ribbons are held together by extended systems of hydrogen bonds.     

MOLECULAR RIBBONS COMPOSED OF CALCIUM(II) IONS BRIDGED BY CARBOXYLATE AND WATER OXYGEN ATOMS IN THE CRYSTALS OF Ca(II) COMPLEX WITH 5-METHYLPYRAZINE-2-CARBOXYLATE LIGANDS

Abstract

Crystals of monoaquo(μ-5-methylpyrazine-2-carboxylato-N,O,O′), (5-methylpyrazine-2-carboxyato-N,O)di(μ-aquo-O,O)calcium(II) contain molecular ribbons in which two adjacent calcium(II) ions are bridged by two bidentate oxygen atoms donated by two ligand molecules on one side and bidentate oxygen atoms of two water molecules on the other. The coordination polyhedron around the Ca(II) ion is a pentagonal bipyramid. The vertices of its pentagonal base are composed of two bridging water oxygen atoms, two carboxylate oxygen atoms of two ligand molecules and a nitrogen atom belonging to one of the bridging ligands. A coordinated water molecule constitutes the apex of the pyramid on one side of the base, while the N, O bonding moiety of a second ligand molecule makes two apices on the other side of the base. The ribbons are held together by a system of hydrogen bonds.     

Molecular chains in the structure of a Zinc(Ii) Complex with Pyrazine-2,6-Dicarboxylate and Water Ligands

Crystals of catena-[diaqua-(μ-pyrazine-2,6-dicarboxylato-N,O,O′-μ-N′)]zinc(II) contain molecular chains in which the Zn(II) ions are bridged by pyrazine-2,6-dicarboxylate ligands via two symmetry-related oxygen atoms, each donated by a different carboxylic group [Zn–O(1) and O(1) ^I : 2.182(2)?Å] and the hetero-ring nitrogen atom [Zn–N(1): 2.049(3)?Å] situated between them on one side and the second hetero-ring nitrogen atom [Zn–N(2) ^II 2.118(3)?Å] from the adjacent ligand on the other. The Zn(II) ion and four coordinating atoms are coplanar. Two symmetry related water molecules [Zn–O3 and O: 2.116(2)?Å] situated above and below this plane complete the coordination around the Zn(II) ion to six atoms forming a distorted octahedron.     

POLYMERIC MOLECULAR PATTERN IN THE CRYSTALS OF A CALCIUM(II) COMPLEX WITH PYRIDINE-3,4-DICARBOXYLATE AND WATER LIGANDS

Abstract

Crystals of triaquamono (μ-pyridine-3,4-dicarboxylato-O,O′,O,O′)(aqua-O)calcium(II) contain molecular ribbons in which two adjacent calcium ions are bridged via oxygen atoms donated by the carboxylate group attached to carbon atom “3” in the pyridine ring. Both oxygen atoms are bidentate, each being coordinated to two caloium ions. In addition, every second pair of calcium(II) ions is bridged by a water oxygen atom. The coordination polyhedron around the calcium(II) ion is pentagonal bipyramidal; its equatorial plane is composed of two bridging oxygen atoms each belonging to the carboxylate group of the adjacent ligands, the bridging water oxygen atom and two coordinated water molecules. Another coordinated water oxygen atom constitutes the apex of the pyramid on one side of the pentagon, while two bridging carboxylate oxygen atoms donated by the same carboxylate group make two apices on the other side of the pentagon. The pyridine hetero-ring nitrogen atom does not participate in coordination to the central ion. Both oxygen atoms of the carboxylate group attached to the carbon atom in position “4” of the pyridine ring are not directly coordinated to the calcium(II) ion and act only as acceptors in the hydrogen bond system.     

Catenated polymeric molecular patterns in structures of two calcium(II) complexes with pyridine-2,3-dicarboxylate (quinolinic) and water ligands

The structure of triclinic catena-tetraquo(μ-pyridine-2,3-dicarboxylato-N,O; O′)calcium(II) is composed of two symmetry independent Ca(II) ions and two independent ligand molecules. Each Ca(II) is coordinated by a N,O-bonding moiety of a ligand, four water oxygens, and a carboxylate oxygen donated by an adjacent bridging ligand. The resulting molecular ribbons are propagating in the [010] crystal direction. Both Ca(II) ions are eight coordinate forming a capped pentagonal bipyramidal with strongly distorted pentagonal equatorial planes. Hydrogen bonds between carboxylate oxygens and coordinated waters are responsible for the stability of the structure. The orthorhombic structure of catena-trisaquo[(μ-2, 3-dicarboxypyridin-1-ium-O,O′; O′′) (H pyridine-2,3-dicarboxylato-N,O)]calcium(II) is composed of molecular ribbons in which the bridging of Ca(II) ions occurs through a ligand using one bidentate carboxylate. The other carboxylate of this ligand donates only one O atom to Ca(II), the second remaining inactive. A proton is attached to the hetero-nitrogen. Each Ca(II) is also chelated by a N,O-bonding moiety of a second ligand, which does not bridge and its second carboxylate remains protonated. Three water oxygen atoms complete the coordination around the Ca(II) ion to eight. The resulting coordination polyhedron is a capped pentagonal bipyramid with a strongly distorted equatorial plane. Hydrogen bonds in which coordinated waters act as donors are responsible for the stability of the structure.     

Two-dimensional molecular pattern in the structure of a calcium(II) complex with pyrazine-2,3-dicarboxylate and water ligands

The structure of di(aquo-O)(pyrazine-2,3-dicarboxylato-N,O; -O′,O′′) calcium(II) hydrate [Ca(2,3-PZDC)(H₂O)₂·;H₂O] contains molecular sheets in which Ca(II) ions are bridged by the carboxylate groups of the ligand molecules. Two bridging paths are evident. In the first, an N,O-bonding moiety formed by a hetero-ring nitrogen atom and the carboxylate oxygen atom nearest to it and both oxygen atoms of the second carboxylic group are active. The second path is formed by the other oxygen atom from the carboxylic group involved in the N,O-bonding moiety and an oxygen atom from the second carboxylic group. The latter atom is bidentate. A two-dimensional molecular pattern is formed. Each Ca(II) ion is also coordinated by two water oxygen atoms, making the number of coordinated atoms eight. The coordination polyhedron is a distorted pentagonal bipyramid with an oxygen atom at the apex on one side of the equatorial plane and two oxygen atoms forming the apices on the other side.     

The Crystal Structures of Two Polymorphic Forms of a Calcium(II) Complex with Pyridine-2,6-Dicarboxylate,Water and Nitrate Ligands

The calcium (II) complex: catena-mono(μ-pyridine-2,6-dicarboxylato-O:O:N;O') (diaqua-O)mono (nitrato-O:O)calcium(II) exists in two polymorphic forms. Each contains molecular ribbons in which adjacent Ca(II) ions are bridged by monodentate oxygen atoms donated by one carboxylate group of the pyridine-2,6-carboxylate ligand. Apart from this bridging oxygen atom, the Ca(II) ion is coordinated by two carboxylate oxygen atoms contributed by a different carboxylate group of the ligand molecule, the heteroring nitrogen atom, two water oxygen atoms and two oxygen atoms of a nitrate group giving rise to a distorted pentagonal bipyramid as a coordination polyhedron. The structures of the polymorphic modifications differ in the way in which the nitrate ligands are oriented with respect to the equatorial planes of the adjacent Ca(II) coordination polyhedra: the trans mode in the α-form; the cis mode in the β-form. In both forms, hydrogen bonds operate between the carboxylate oxygen atoms, water oxygen atoms and nitrate oxygen atoms.     

Molecular Topology in Crystals of a Potassium(I) Complex with [Z-5-(2-Chlorobenzylidene)-4-Oxoimidazolin-2-YL]-3-Amino-Propanoate

In a complex with [ Z -5-(2-chlorobenzylidene)-4-oxoimidazolin-2-yl]-3-amino-propanoate acid (APAC), potassium ion adopts distorted square-bipyramidal (4 + 2) coordination. All donor atoms are oxygens; four of them originate from carboxylate groups of APAC, while the remaining ones are water oxygens. The equatorial plane of coordination polyhedron is composed of two carboxylate oxygens (with K-O distances of 2.769 and 2.806 Å) and two water oxygens (with K-O distances of 2.722 and 2.749 Å). Two axial K-O bonds (2.663 and 2.664 Å), involving the remaining carboxylate O atoms, complete the sixfold coordination of the K atom. Coordination polyhedra are condensed in two ways. The distance between two potassium pairs are significantly different, 4.224 and 3.801 Å. APAC molecules are held together by a network of hydrogen bonds and create a gap along the [ab] plane with molecular ribbons of potassium ions and water molecules inside. Due to the potassium alignment of aliphatic chains in two neighbouring, crystalgraphically independent APAC molecules, small cavities are created, which form small channels along the b axis with the remaining water molecule.     

Crystal structure and triboluminescence of the [Eu(TTA)2(NO3)(TPPO)2] complex

The crystal structure of [Eu(TTA)₂(NO₃)(TPPO)₂] (I) (TTA = thenoyltrifluoroacetone, TPPO = triphenylphosphine oxide) possessing intense triboluminescence was established by X-ray crystallography. The crystals are triclinic, noncentrocymmetrical: a = 11.047(3) Å, b = 11.794(3) Å, c = 12.537(3) Å; α = 102.635 (4)°, β = 102.088(4)°,γ = 117.765(3)°; space group P1, Z = 1. The central Eu(III) atom coordinates two oxygen atoms of two TPPO molecules at distances of 2.271 Å and 2.282 Å, two oxygen atoms of the nitrate group at distances of 2.478 Å and 2.481 Å, four oxygen atoms of two TTA ions at distances of 2.365 Å, 2.381 Å, and 2.363 Å, 2.371 Å (coordination number is 8). The coordination polyhedron of the Eu(III) atom is a distorted dodecahedron. Possible reasons for spectral differences in the Stark structure of photo-and triboluminescence of I are discussed.     

TRANSITION METAL COMPLEXES WITH HYDRAZIDES AND HYDRAZONES. PART 81. X-RAY CRYSTAL STRUCTURE OF A CATENA-POLYBROMO (ACETONE-1-NAPHTHOYLHYDRAZONE) COPPER(II)-COPPER(I) COMPLEX

Abstract

The title compound [Cu₃Br₄C₂₈H₂₈N₄O₂] is a type of polymeric three-centre octahedral-trigonal planar coordination complex. The copper(II) atom located at a centre of symmetry is six-coordinate with two bidentate (N3, O1) ligands of acetone-1-naphthoylhydrazone forming the equatorial plane and two bromine ions in axial positions (Cul-Brl = 2.946(1)Å). The ligands are in trans positions. The Cu(I) atoms are in trigonal planar coordination by two bridging Br^? ions (Cu2-Br2 = 2.412(1)Å, Cu2-Br2? = 2.407(2)Å) which connect two Cu(I) atoms and a third bromine ion shared with the octahedral Cu(II) ion (Cu2-Br1 = 2.304(1)Å). The arrangement forms an infinite chain along the b axis.     

Crystal structure of barium (cyclohexane-1,2-diaminetetraacetato)cobaltate(III) nonahydrate Ba[Co(Cdta)]2 · 9H2O

The crystal structure of Ba[Co(Cdta)]₂ · 9H₂O has been determined by X-ray diffraction. The crystals are monoclinic, a = 15.9415(10) Å, b = 7.8449(6) Å, c = 32.230(2) Å, β = 100.387(8)°, Z = 4, space group C2/c)). The cyclohexane-1,2-diaminetetraacetate ion forms the octahedral [Co(Cdta)]^? complex through two donor nitrogen atoms and four oxygen atoms and is also connected to two barium atoms through oxygens. The Ba atoms are on a twofold axis. Its nearest environment comprises five O atoms of water molecules, one also being located on a twofold axis, and four O atoms of the four neighboring complex ions. This gives infinite layers parallel to the ab plane. All water molecules form hydrogen bonds within one layer.     

The First Calcium(II) Complex with the Saccharinate Ligand: Synthesis,Crystal Structure,Spectral and Thermal Characterization of Trans—diaquabis[(2—hydroxyethyl)pyridinium]bis(saccharinato)calcium(II) Disaccharinate, [Ca(sac)2(H2O)2(Hpyet)2](sac)2

A new calcium(II) complex of the saccharinate ligand (sac) with 2—hydroxyethylpyridinium (Hpyet) was synthesized and characterized by elemental analysis, FT—IR spectroscopy, thermal analysis and single crystal X—ray diffractometry. The [Ca(sac)₂(H₂O)₂(Hpyet)₂](sac)₂ complex crystallizes in the triclinic space group (P1¯) with the cell dimensions a = 7.4360(7)Å, b = 12.5263(12)Å, c = 12.8329(13)Å, α = 82.534(8)°, β = 75.202(8)° and γ = 89.662(8)° (293 K). The title complex consists of a complex cation and two sac anions. In the complex cation, the calcium(II) ion is six—coordinate, bonding to two aqua ligands, two Hpyet ligands andtwo sac ligands located in the trans positions. Two of the sac ions are coordinated to the calcium(II) ion through the carbonyl O atom, while the other two remain outside the coordination sphere as the counter—ions. Thermal decomposition of the complex in air results in elimination of aqua, Hpyet, and sac ions, respectively.     

Synthesis, crystal structure, and luminescent properties of a silver(I) perrhenate complex with phenazine

The silver complex with phenazine [Ag(Phz)₂(H₂O)]ReO₄ (Phz is C₁₂H₈N₂) has been synthesized, and its crystal structure has been determined. The crystals are triclinic: space group $P\bar 1$ , a = 9.587(1) Å, b = 10.875(1) Å, c = 11.668(1) Å, α = 104.98(1)°, β = 103.87(1)°, γ = 92.94(1)°, V = 1132.6(2) ų, Z = 2, ρ_calc = 2.160 g/cm³. The structure is composed of the [Ag(Phz)₂(H₂O)]⁺ silver cationic complexes and ReO ₄ ^? anions. The Ag⁺ ion is coordinated by two nitrogen atoms of independent phenazine molecules and the water oxygen atoms and has a T-shaped coordination (Ag-N_av 2.223 Å, Ag-O_w 2.498(8) Å). Phenazine, being an electron-donor ligand, forms columns due to π-π stacking interaction between the aromatic groups. The water molecules form hydrogen bonds with the oxygen atoms of water molecules of neighboring complexes and with oxygen atoms of the ReO ₄ ^? anions.     

X-Ray Diffraction Study on Manganese(II) Complexes with Thiophene-2-Carboxylate and Furan-3-Carboxylate Ligands

Abstract

Mn(II) cations in the crystals of trisaquobis(μ-thiophen-2-carboxylato-O,O′)(thiophen-2-carboxylato-O)manganese(II) monohydrate are bridged by oxygen atoms donated by bidentate carboxylic groups of two thiophen-2-carboxylate ligands. In addition, each Mn(II) ion is coordinated by an oxygen atom of a monodentate carboxylic group of this ligand and three oxygen atoms of water molecules. The coordination around the Mn(II) cation is octahedral. The bridging of the ligands results in molecular ribbons propagating in the c-direction of the crystal held together by C?H…O hydrogen bonds. The crystal structure of diaquobis(μ-furan-3-carboxylato-O,O′)di(μ-furan-3-carboxylato-O,O)(μ-aqua-O)manganese(II) consists of dinuclear structural units. In each molecule Mn(II) cations are O,O′ bridged by oxygen atoms of bidentate carboxylic groups of two furan-3-carboxylate ligands and have a water located between the Mn cations. The units are O,O′ bridged to Mn(II) ions located in adjacent units by bidentate oxygen atoms, forming molecular ribbons extending in the c-direction. Octahedral coordination around each Mn(II) ion is completed by two water molecules. The octahedra around two adjacent metal ions in the unit share a common apex - the bridging oxygen atom of the water molecule. The ribbons are held together by C?H…O hydrogen bonds between furan ring oxygen atoms and the carbon atoms of adjacent furan rings.     

Synthesis and Crystal Structures of Nickel(II) and Copper(II) Complexes of Meso-3,6,6,9-Tetramethyl-4,8-Diazaundecane-2,10-Dione Dioxime

The nickel(II) and copper(II) complexes of meso-3,6,6,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime (meso-HM-PAO) have an intramolecular hydrogen bond between cis oxime groups. [Cu(meso-HM-PAO-H)(H₂O)](NCS) crystallizes in space group P2₁/n with a = 7.692(1), b = 12.028(2), c=20.235(3) Å, β=93.03(1)°, Z = 4 and Dc=1.46 g/cm³. The final R value for this complex was 0.034 for 2223 observed reflections with I ≥ 2.5σ (I). The Cu(II) coordination is a distorted square pyramid. The Cu(II) ion is five-coorinated with the diazadioxime N atoms equatorial and water O atom axial. The Cu(II) is 0.12 Å from the equatorial plane towards the hydrate. The equatorial Cu-N distances span a narrow range, 1.953(3)-1.999(3) Å. The axial Cu-O distance is 2.314(3) Å. The thiocyanate group is almost linear. The intramolecular O ?O hydrogen bond length is 2.479(4) Å. [Ni(meso-HM-PAO-H)](ClO₄) crystallizes in space group P2₁/c with a = 14.774(3), b = 12.752(3), c = 20.035(4) Å, β = 92.94(3)°, Z = 8 and Dc = 1.51 g/cm³. The final R value for the complex was 0.053 for 4794 observed reflections with F ≥ 4σ (F). The coordination about Ni(II) is a slightly distorted square plane. The Ni(II) ion is 0.0673(7) Å from the best plane of the four donor nitrogen atoms away from the perchlorate ion. The Ni-N distances span a narrow range 1.863(4)-1.927(4) Å. There are two molecules per asymmetrical unit resulting in eight molecules being packed in an unit cell; they are bound together by van der Waals interactions. The O-H ?O bonds of these complexes give characteristic infrared absorptions as well as chemical shift of the ¹H NMR signal (Ni complex).