Hexa(isothiocyanato)chromates(III) of Some Yttrium Group Lanthanide(III) and Europium Complexes with Nicotinic Acid: Synthesis and Crystal Structures

Double ionic complexes [M(C₅H₅NCOO)₃(H₂O)₂][Cr(NCS)₆] · nH₂O, where M = Eu (I), n = 1.15; Dy (II), Er (III), n = 1.5; M = Yb (IV), n = 2, have been synthesized by the reaction between M(NO₃)₃, M = Eu, Dy, Er, Yb, K₃[Cr(NCS)₆], and nicotinic acid (C₅H₅NCOO) in an aqueous solution and studied by chemical analysis, IR spectroscopy, and X-ray diffraction. Crystals of complexes I–IV are monoclinic, space group P2₁/n, Z = 4; a = 9.5358(2) Å, b = 25.4871(5) Å, c = 15.4303(4) Å, β = 105.513(1)°, V = 3613.6(1) ų, ρ_calcd = 1.799 g/cm³ for I, a = 9.5901(5) Å, b = 25.8599(15) Å, c = 15.6316(9) Å, β = 106.829(2)°, V = 3710.6(4) ų, ρ_calcd = 1.782 g/cm³ for II, a = 9.5640(3) Å, b = 25.8936(11) Å, c = 15.6498(7) Å, β = 106.895(2)°, V = 3708.3(3) ų, ρ_calcd = 1.791 g/cm³ for III, and a = 9.5049(2) Å, b = 25.6378(4) Å, c = 15.5120(3) Å, β = 106.934(1)°, V = 3616.1(1) ų, ρ_calcd = 1.864 g/cm³ for IV.     

Synthesis and study of tetraamminecobalt hydrogen hexamolybdometalates(III)

Tetraamminecobalt hydrogen hexamolybdoferrate [Co(NH₃)₄] · H[FeMo₆O₁₈(OH)₆] · 6H₂O (I) and tetraamminecobalt hydrogen hexamolybdogallate(III) [Co(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 6H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, and X-ray diffraction. Crystals of I and II are monoclinic; a = 16.21 Å, b = 5.43 Å, c = 12.32 Å, β = 119.63°, V = 1092.11 ų, ρ_calcd = 2.21 g/cm³, and Z = 1 for I; a = 16.24 Å, b = 5.59 Å, c = 12.29 Å, β = 119.79°, V = 1064.05 ų, ρ_calcd = 2.15 g/cm³, and Z = 1 for II. Compounds I and II were used as catalysts for soft oxidation of natural gas.     

Preparation and study of hydrogen hexamolybdometallates(III) with the hexamminecadmium cation

Hydrogen hexamolybdogallate and hexamolybdoaluminate with the hexamminecadmium cation [Cd(NH₃)₆] · H[GaMo₆O₁₈(OH)₆] · 6H₂O (I) and [Cd(NH₃)₆] · H[AlMo₆O₁₈(OH)₆] · 6H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetric analysis, powder X-ray diffraction, and IR spectroscopy. The crystals are monoclinic; I: a = 10.82 Å, b = 3.69 Å, c = 11.99 Å, β = 91.06°, V= 469.72 ų, ρ_calcd = 2.34 g/cm³, Z = 2; II: a = 10.81 Å, b = 3.67 Å, c =11.98 Å, β = 91.08°, V = 469.78 ų, ρ_calcd = 2.38 g/cm³, Z = 2.     

Tetramminenickel hydrogen hexamolybdometalates(III)

Tetramminenickel hydrogen hexamolybdoaluminate and hexamolybdogallate(III) of compositions [Ni(NH₃)₄] · H[AlMo₆O₁₈(OH)₆] · 10H₂O (I) and [Ni(NH₃)₄] · H[GaMo₆O₁₈(OH)₆] · 10H₂O (II) were synthesized and characterized by mass spectrometry, thermogravimetry, X-ray powder diffraction, and IR spectroscopy. Their crystals are triclinic. For compound I, a= 17.30 Å, b= 14.69 Å, c= 10.45 Å, α = 129.07, β = 65.91°, γ = 138.01°, V = 1338.7l ų, ρ_calcd = 2.75g/cm³, Z = 2; for compound II, a = 17.38 Å, b= 14.75 Å, c= 10.51 Å, α = 131.38°, β= 65.96°, γ = 138.09, V = 1338.15 ų, ρ_calcd = 2.68 g/cm³, Z = 2.     

Preparation and physicochemical study of sodium hexamolybdometallates(III)

Sodium hexamolybdocobaltate(III) Na₃[CoMo₆O₁₈(OH)₆] · 8H₂O (I) and sodium hexamolybdochromate Na₃[CrMo₆O₁₈(OH)₆] · 8H₂O (II) were synthesized and studied by mass spectrometry, thermogravimetry, powder X-ray diffraction, and IR spectroscopy. The crystals are monoclinic. For compound a = 10.31 Å, b = 10.31 Å, c = 17.55 Å, β = 100.93°, V = 1834.77 ų, ρ_calcd = 3.04 g/cm³, Z = 3; for compound II: a = 10.33 Å, b = 10.33 Å, c = 17.59 Å, β = 100.98°, V = 1835.09 Å3, ρ_calcd = 3.01 g/cm³, Z = 3.     

Acid Co(II) and Ni(II) trifluoroacetate complexes: Synthesis and crystal structure

Anhydrous and partially hydrated acid trinuclear trifluoroacetates of divalent transition metals of the composition [M₃(CF₃COO)₆(CF₃COOH)₆)](CF₃COOH) and [M₃(CF₃COO)₆(CF₃COOH)₂(H₂O)₄)](CF₃COOH)₂, respectively, where M = Co (I, III) Ni (II, IV), were synthesized and studied by X-ray diffraction. Complexes I and II were obtained by crystallization from solutions of M(CF₃COO)₂ · 4H₂O in trifluoroacetic anhydride; complexes III and IV were synthesized under the same conditions with the use of 99% trifluoroacetic acid as a solvent. Crystals I are triclinic: space group $P\bar 1$ , a = 13.199(6) Å, b = 14.649(6) Å, c = 15.818(6) Å, α = 90.04(4)°, β = 114.32(4)°, γ = 108.55(4)°, V = 2611.3(19) ų, Z = 2, R = 0.0480. Crystals II are trigonal: space group $R\bar 3$ , a = 13.307(2) Å, c = 53.13(1) Å, V = 8148(2) ų, Z = 6, R = 0.1112. Crystals III are triclinic: space group $P\bar 1$ , a = 9.001(8) Å, b = 10.379(9) Å, c = 12.119(9) Å, α = 83.67(5)°, β = 72.33(5)°, γ = 83.44(5)°, V = 1068.3(15) ų, Z = 1 Å, R = 0.1031. Crystals IV are triclinic: space group $P\bar 1$ , a = 9.121(18) Å, b = 10.379(2) Å, c = 12.109(2) Å, α = 84.59(3)°, β = 72.20(3)°, γ = 82.80(3)°, V = 1080.94(40) ų, Z = 1, R = 0.0334.     

Structural investigation of ethylenediaminium tetrachloroaurates(III)

The (EnH₂)[AuCl₄]₂·2H₂O (I) and (EnH₂)₂[AuCl₄]Cl₃ (II) (EnH ₂ ²⁺ is diprotonated ethylenediamine) complexes are produced and characterized by elemental and thermogravimetric analysis, X-ray diffraction, IR and Raman spectroscopy. For I, the crystals are monoclinic, crystallize in the space group P2₁/c: a = 7.5870(2) Å, b = 9.5665(2) Å, c = 11.4706(3) Å, β = 107.0480(10)°, V = 795.97(3) ų, Z = 4. For II, the crystals are orthorhombic, crystallize in the space group Pnma: a = 12.7088(3) Å, b = 17.7435(5) Å, c = 7.4992(2) Å, V = 1691.06(8) ų, Z = 8.     

Coordination molecular compounds of cadmium(II) iodide with dimethylpyridines

The reactions of CdI₂ with dimethylpyridines (Me₂Py is C₇H₉N) afford complexes CdI₂(2,3-Me₂Py)₂] (I), [CdI₂(2,6-Me₂Py) (II), and CdI₂(3,5-Me₂Py)₂ (III). The structures of compounds I and II are determined. The crystals of complex I are orthorhombic, space group Pbca, a = 7.930(1) Å, b = 15.537(1) Å, c = 29.943(1) Å, V = 3689.1(5) ų, ρ_calcd = 2.090 g/cm³, Z = 8. The crystals of complex II are monoclinic, space group C2/c, a = 14.784(1), b = 11.991(1), c = 17.711(1) Å, β = 90.39(1)°, V = 1081.1(2) ų, ρ_calcd = 2.908 g/cm³, Z = 4. The structure of compound I is built of discrete neutral complexes [CdI₂(2,3-Me₂Py)₂]. The Cd polyhedron is a distorted tetrahedron (Cd-I 2.289–2.295, Cd-N 2.708–2.734 Å, angles N(I)CdN(I) 103.1°-114.8°). Polymer chains [CdI₂(2,6-Me₂Py)]_∞ extended along the direction [100] are observed due to the bridging iodine atoms in structure II. The Cd polyhedron is a trigonal bipyramid containing iodine atoms at the axial vertices (Cd-I_aks 3.040 Å) and two iodine atoms and the nitrogen atom of the Me₂Py ligand in the equatorial plane Me₂Py (Cd-I_eq 2.840 Å, Cd-N 2.309 Å). The compounds in the solid state are photoluminescent.     

Coordination compounds of cobalt(II) and cadmium(II) with 2-amino-4-methylpyrimidine: Synthesis, crystal structure, and luminescent properties

The coordination compounds [CoL₂Cl₂] (I) and [CdL₂(H₂O)₂(NO₃)₂] (II) have been synthesized by the reaction of CoCl₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O with L = 2-amino-4-methylpyrimidine (Ampym, C₅H₇N₃), and their structures have been solved. The crystals of complex I are triclinic, space group $P\bar 1$ , a = 5.627(1) Å, b = 11.191(1) Å, c = 12.445(1) Å, α = 81.00(1)°, β = 77.21(1)°, γ = 76.18(1)°, V = 737.7(2) ų, ρ_calcd = 1.567 g/cm³, Z = 2. The crystals of complex II are monoclinic, space group P2₁/c, a = 10.390(1) Å, b = 11.982(1) Å, c = 7.624(1) Å, β = 102.61(1)°, V = 926.1(2) ų, ρ_calcd = 1.760 g/cm³, Z = 2. Discrete [CoL₂Cl₂] moieties are realized in the structure of complex I. The cobalt atom is tetrahedrally coordinated to the two nitrogen atoms of crystallographically nonequivalent ligands L and two chlorine atoms (Co(1)-N_avg, 2.051(4)Å; Co(1)-Cl(1), 2.241(1) Å; Co(1)-Cl(2), 2.263 Å; bond angles at the cobalt atom lie within a range of 102.1°–118.6°). The complexes are linked into supramolecular zigzag chains by N-H...N(Cl) hydrogen bonds. In the structure of complex II, the Cd²⁺ ion (at the inversion center) is coordinated in pairs to the nitrogen atoms of ligand L and the O(NO₃) and O(H₂O) oxygen atoms. The coordination of the Cd²⁺ ion is distorted octahedral (Cd(1)-N(1), 2.341Å; Cd(1)-O(1), 2.340(4) Å; Cd(1)-O(4), 2.327(3) Å; bond angles at the cadmium atom lie within a range of 79.1°–100.9°). N-H...N hydrogen bonds link the complexes into supramolecular chains. These chains are linked into a supramolecular framework by the O-H...O hydrogen bonds between water molecules and NO₃ groups.     

Cadmium(II) iodide molecular coordination compounds with 4-methylpyridine and 4-methylquinoline

The coordination compounds [CdI₂(4-MePy)₂] (I) and [CdI₂(4-MeQuin)₂] (II) where Quin is quinoline have been synthesized, and their structure has been solved. Crystals of complex I are monoclinic, space group C2/c, a = 13.353(1) Å, b = 16.653(1) Å, c = 14.380 (1) Å, β = 103.17(1)°, V = 3113.5(4) ų, ρ_calcd = 2.425 g/cm³, Z = 8. Crystals of complex II are monoclinic, space group P2₁/c, a = 10.647(1) Å, b = 25.264(1) Å, c = 8.610(1) Å, β = 113.73(1)°, V = 2120.1(3) ų, ρ_calcd = 2.044 g/cm³, Z = 4. Polymer [CdI₂(4-MePy)₂]_∞ chains running in the direction [001] are formed in the structure of complex I. Each of the two crystallographically nonequivalent Cd(1) and Cd(2) atoms are octahedrally surrounded by the four iodine and two nitrogen atoms of the 4-MePy ligand. The Cd(1)?Cd(2) distance in a chain is 4.33 Å. The structure of complex II is built of [CdI₂(4-MeQuin)₂] discrete neutral clusters. The two iodine and two nitrogen atoms of the 4-MeQuin ligand participate in the coordination of the Cd²⁺ ion. The cadmium coordination polyhedron is a distorted tetrahedron (Cd-I_avg, 2.72 Å; Cd-N_avg, 2.30 Å; angles N(I)CdN(I), 98.3–121.8°). The minimum and maximum values correspond to the ICdI angle and NCdN angle, respectively. Complex I is photoluminescent in the solid state at room temperature.     

Synthesis and study of hydrogen hexamolybdonickelate and hydrogen hexamolybdozincate with the cobaltammine cation

[Co(NH₃)₆] · H₂[NiMo₆O₁₈(OH)₆] · 6H₂O (I) and [Co(NH₃)₆] · H₂[ZnMo₆O₁₈(OH)₆] · 6H₂O (II) have been synthesized and studied by mass spectroscopy, thermogravimetry, and X-ray powder diffraction. The crystals of compounds I and II are monoclinic, Z = 1; for compound I: a = 16.10 Å, b = 5.58 Å, c = 12.22 Å, β = 117.86°, V = 1045.14 ų, and ρ_calcd = 2.26 g/cm³; for compound II: a = 16.12 Å, b = 5.52 Å, c = 12.12 Å, β = 117.90°, V = 1043.21 ų, and ρ_calcd = 2.21 g/cm³.     

Heteroligand zinc(II) and copper(II) complexes with naphthylacetic acid and monoethanolamine: Syntheses and crystal structures

New heteroligand Cu(II) and Zn(II) complexes with the α-naphthylacetic acid anion (NAA) and monoethanolamine (MEA), [M(NAA)₂(MEA)₂] (M = Cu²⁺, (I), Zn²⁺ (II)), are synthesized. The crystal structures of the obtained complexes are determined by X-ray diffraction analysis (CIF files CCDC 984097 (I) and 930946 (II)). The crystals are monoclinic, for I: a = 18.8140(9) Å, b = 4.82500(14) Å, c = 16.0360(7) Å, β = 115.135(6)°, V = 1317.87(11) ų, space group P2₁/c, Z = 2; for II: a = 32.9760(14) Å, b = 5.0911(3) Å, c = 15.7994(10) Å, β = 94.418(5)°, V = 2644.6(3) ų, space group C2/c, Z = 4. In the structure of complex I, the Cu²⁺ ion arranged in the symmetry center is coordinated at the vertices of the distorted octahedron by the oxygen atoms of two NAA molecules (Cu-O(2) 2.019(4) Å) and two MEA molecules. The latter is the bidentate-chelating ligand and coordinates the metal through the O and N atoms to form the five-membered metallocycle (Cu-O(3) 2.457(5), Cu-N(1) 1.986(5) Å). In complex II, the Zn atom (on axis 2) is coordinated at the vertices of the distorted tetrahedron by the oxygen atoms of two NAA molecules (Zn-O(2) 1.976(4) Å) and the nitrogen atoms of two MEA molecules (Zn-N 2.034(6) Å). The character of the interaction of coordinated NAA and MEA ligands and methods for packing complexes I and II are considered on the basis of the structural data.     

A complex of cadmium(II) iodide with 4-cyanopyridine: Synthesis,crystal structure,and luminescent properties

The complex [CdI₂(4-CNPy)₂] (I) was obtained by a reaction of CdI₂ with 4-cyanopyridine (4-CNPy, C₆H₄N₂) and structurally characterized (CIF file CCDC no. 983377). The crystals of complex I are monoclinic, space group C2, a = 24.698(5) Å, b = 4.127(1) Å, c = 7.597(2) Å, β = 96.05(1)°, V = 770.0(3) ų, ρ_calcd = 2.477 g/cm³, Z = 2. In structure I, iodine atoms serve to unite complex molecules into the polymer chains [CdI₂(4-CNPy)₂]_∞ along the direction [010]. The Cd(1) atom lying on a twofold axis has a slightly distorted octahedral environment made up of four bridging iodine atoms and two nitrogen atoms of two ligands 4-CNPy (Cd-I_av, 2.947(2) and Cd-N(1), 2.410(6) Å). Within each chain, cadmium atoms are spaced apart at 4.13 Å. Complex I exhibits photoluminescence.     

Synthesis and crystal structures of binuclear complexes of cobalt(II) and cadmium(II) diisobutyldithiophosphinates with hexamethylenetetramine

Heteroligand complexes [Co₂(HMTA)(iso-Bu₂PS₂)₄] (I) (μ_eff = 4.67 μB) and [Cd₂(HMTA)(iso-Bu₂PS₂)₄] (II) have been synthesized. Single crystals of compounds I and II have been obtained. The crystals are monoclinic: a = 32.622(2) Å, b = 9.4891(6) Å, c = 21.7570(13) Å, β = 125.774(1)^o, V = 5464.3(6) Å,³, Z = 4, ρ_calcd = 1.331 g/cm³ for I; a = 34.6092(7) Å, b = 9.5595(2) Å, c = 22.3473(5) Å, β = 127.144(1)^o, V = 5893.5(2) Å, Z = 4, ρ_calcd = 1.355 g/cm³ for II; space group for both complexes C2/c. Structures I and II are based on discrete binuclear molecules. The coordination polyhedra of the Co and Cd atoms are distorted tetragonal pyramids NS₄, with the bases formed by four S atoms of two bidentate chelating ligand iso-Bu₂PS ₂ ^? and the axial vertices occupied by N atoms of bidentate bridging HMTA ligand. The character of interaction of the molecules in structures I and II is considered.     

Syntheses, crystal structure, and fluorescent properties of a lanthanide complex

A new complex [Dy₂(Pht)₂(HPht)₂(Phen)₂(H₂O)₄] (I), where Pht^2? = dianion of o-phthalic acid; HPht^? = mono-anion of o-phthalic acid; Phen = 1,10-phenanthroline, has been synthesized and the crystal structure was determined by X-ray crystallography. The I crystallizes in the triclinic system, space group $P\bar 1$ with lattice parameters a =10.1126(3) Å, b =10.7029(3) Å, c = 11.9360(3) Å, α = 90.2260(10)°, β = 99.5340(10)°, γ = 100.9810(10)°, V = 1249.87(6) ų, Z = 2, ρ_calcd = 1.881 mg m^?3. The photophysical property of I has been studied with excitation and emission spectra.     

Synthesis of Cu(II) and Mn(III) Complexes Involving Derivatives of Pyridine

Two complexes with derivatives of pyridine as ligands were synthesized and characterized. From the reaction of 2-pyridinecarboxaldehyde oxime with Cu(OAc)₂ · H₂O afforded the complex C₂₀H₃₀N₆O₁₂Cu₃ (I), and the use of 3-hydroxy-2-pyridinecarboxylic acid with anhydrous MnCl₂ · 4H₂O led to the formation of another complex C₁₂H₁₄N₂OCl₂Mn (II). They were characterized by X-ray diffraction (CIF files CCDC nos. 568718 (I) and 1568880 (II)), NMR, IR and elemental analysis. For I: terigonal, space group R\(\bar 3\)/H, a = 42.548(3), c = 10.2774(9) Å, V = 16113(2) ų, Z = 18, ρ_calcd = 1.367 Mg/m³, the final R factor was R₁ = 0.0945, 6662 for reflections were observed with I > 2σ(I), wR = 0.162 for all data. For II: triclinic, Pī, a = 5.6174(9), b = 7.7259(13), c = 9.7160(16) Å, α = 70.444(3)°, β = 88.009(3)°, γ = 89.818(3)°, V = 397.09(11) ų, Z = 1, ρ_calcd = 1.840 Mg/m³, the final R factor was R₁ = 0.0281, 4280 for reflections were observed with I > 2σ(I), wR = 0.0775 for all data.     

Synthesis and study of hexaamminecadmium hydrogen hexamolybdocobaltate(III) and hexamolybdochromate(III)

Hexaamminecadmium hydrogen hexamolybdocobaltate(III) and hydrogen hexamolybdochromate(III) of compositions [Cd(NH₃)₆] · H[CoMo₆O₁₈(OH)₆] · 6H₂O (I) and [Cd(NH₃)₆] · H[CrMo₆O₁₈(OH)₆] · 6H₂O (II), respectively, were synthesized and studied by mass spectroscopy, thermo-gravimetry, X-ray powder diffraction, and IR spectroscopy. Crystals of I and II are monoclinic. For I: a = 10.79 Å, b = 3.70 Å, c = 11.95 Å, β = 91.05°, V = 470.12 ų, ρ_calc = 2.37 g/cm³, Z = 2; and for II: a = 10.80 Å, b = 3.68 Å, c = 11.97 Å, β = 91.07°, V = 468.98 ų, ρ_calc = 2.36 g/cm³, Z = 2.     

Synthesis and structure of diethylenetriammonium tetrachloroaurates(III)

The (DienH₃)[AuCl₄]₃ · H₂O (I) and (DienH₃)₂[AuCl₄]Cl₅ (II) compounds were obtained by the reaction of HAuCl₄ with diethylenetriamine trihydrochloride (DienH₃Cl₃) in hydrochloric acid. The compounds were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. Crystals of I and II are monoclinic with space group P2₁/n. For I, a = 12.2314(3) Å, b = 14.6077(5) Å, c = 13.2680(5) Å, β = 106.7350(10)°, V = 2270.22(13) ų, Z = 8. For II, a = 6.62990(10) Å, b = 17.9026(5) Å, c = 10.3661(3) Å, β = 101.9230(10)°, V = 1203.83(5) ų, Z = 2. Both structures are ionic. The gold atoms in I and II have a 4 + 2 coordination environment. The Au-Cl bond lengths are within 2.276–2.294 Å, and the axial Au…Cl contacts are within 3.315–3.405 Å. The diethylenetriammonium cation in I and II has different conformations.     

Coordination polymers of silver with piperazine and uncoordinated anions: Syntheses and crystal structures of [Ag(C4H10N2)]CH3SO3 and [Ag(C4H10N2)]PO2F2

The coordination polymers [Ag(C₄H₁₀N₂)]CH₃SO₃ (I) and [Ag(C₄H₁₀N₂)]PO₂F₂ (II) (C₄H₁₀N₂ is piperazine (Ppz)) are synthesized, and their structures are determined. The crystals of I are monoclinic, space group P2₁/c, a = 6.280(1) Å, b = 11.781(1) Å, c = 12.112(1) Å, β = 97.21(1)°, V = 889.0(2) ų, ρ_calcd = 2.160 g/cm³, and Z = 4. The crystals of II are orthorhombic, space group Cmca, a = 13.039(1) Å, b = 10.450(1) Å, c = 12.837(1) Å, V = 1749.1(3) ų, ρ_calcd = 2.240 g/cm³, and Z = 8. Structure I contains cationic polymer chains [Ag(Ppz)] _∞ ⁺ . The silver atom bound to two nitrogen atoms of two Ppz ligands has an almost linear coordination mode (Ag-N_average 2.197 Å, angle NAgN 161.2(1)°). The structure includes supramolecular layers due to weak interactions Ag…O(CH₃SO₃). Structure II is built of zigzag polymer chains [Ag(Ppz)]⁺ and tetrahedral cations PO₂F ₂ ^? . The Ag⁺ ion has a linear coordination mode (Ag-N 2.220(3) Å, and the NAgN angle is 164.3(2)°). The tetrahedral anions PO₂F ₂ ^? having weak contacts with the silver ions (Ag…O 2.630(3)Å) join the [Ag(Ppz)] _∞ ⁺ chains into wavy layers.     

Co(III) complexes with optically active bis(menthane), pinano-para-menthane, carano-para-menthane, and bis(carane) propylenediaminodioximes

Novel optical ligands bis(menthane) (H₂L¹), pinano-para-menthane (H₂L²), and carano-para-menthane (H₂L³) propylenediaminodioximes are obtained. Diamagentic Co(III) complexes of the composition Co(HL¹)Cl₂ (I), Co(HL²)Cl₂ (II), Co(HL³)Cl₂ (III), and Co(HL⁴)Cl₂ · H₂O(IV) are synthesized by reactions of CoCl₂ with H₂L¹, H₂L², H₂L³ and bis(carane) propylenediaminodioxime (H₂L⁴) in ethanol in air. The crystal and molecular structures of compound I is determined by X-ray diffraction analysis. The crystals are monoclinic with the unit cell parameters a = 7.8385(3) Å, b = 11.4074(6) Å, c = 14.9509(6) Å, β = 104.278(2)°, V = 1295.57(10) ų, Z = 2, ρ(calcd) = 1.367 g/cm³, F(000) = 564, M = 533.41, space group P2₁. The crystal structure of complex I consists of individual mononuclear molecules. The Co³⁺ ion coordinates four N atoms of tetradentate cycle-forming anionic ligand and two Cl atoms. The coordination polyhedron of Cl₂N₄ is a distorted octahedron. The ¹³C and ¹H NMR spectra of the complexes synthesized confirm coordination of four N atoms of a ligand.