Structure and characterization of A 2D cobalt(II) complex [Co(L)2] n (L = 3-nitro-5-(pyridine-4-yl)benzoate)

The self-assembly of unsymmetrical tecton 3-nitro-5-(pyridin-4-yl)benzoic acid (HL)with cobalt chloride under hydrothermal conditions affords a new 2D coordination polymer [Co(L)₂] _n (1, L = 3-nitro-5-(pyridin-4-yl)benzoate), which is characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction analysis, and single crystal X-ray diffraction. Compound 1 is of the triclinic system, space group P-1 with a = 9.7857(12) Å, b = 10.3417(13) Å, c = 10.8463(13) Å, α = 85.155(2)°, β = 74.785(2)°, γ = 88.962(2)°, V = 1055.4(2) ų. The crystal structural analysis of complex 1 shows that the cobalt center is six-coordinated in an octahedral geometry by four O atoms from four different L ligands and two N atoms from two different L ligands; the Co(II) cations are bridged by μ₃-L into an interesting two-dimensional network structure. It should be pointed out that the thermal analysis results indicate that complex 1 is quite stable up to 420°C.     

Cu(I) cloride complexes with 4,5-(2-pyridylethylene)dithio-1,3-dithiol-2-thione and triphenylphosphine

Heteroligand binuclear complexes of CuCl with triphenylphosphine and 5-pyridine-2-yl-5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiine-2-thione (L¹) of the compositions [CuCl(PPh₃)(L¹)]₂ (I) and [CuCiL¹]₂ (II) are synthesized and studied by X-ray diffraction method. Crystals I are monoclinic; space group P2₁/n, a=8.9520(18) Å, b=18.926(4) Å, c=16.841(3) Å, β=94.96(3)°, Z=2. The Cu(I) atom has a quasi-tetrahedral surrounding involving the tetraphenylphosphine P atom, the pyridyl N atom of the molecule L¹, and two bridging Cl atoms. Crystals II are monoclinic; space group P2₁/c, a=9.3520(19) Å, b=8.1490(16) Å, c=18.660(4) A, β = 104.43(3)°, Z = 2. Both L¹ ligands in complex II act as bridges. The Cu(I) atom also has a quasi-tetrahedral surrounding formed by the Cl atoms, the pyridyl N atoms and thiol S atom of one L¹ ligand, and the thione S atom of the second L¹ ligand. Similar binuclear complexes with the bridging function of the L¹ ligand were also detected in a solution of II by the ESI method.     

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.     

Crystal structures of allyltriphenyl-phosphonium halogenocuprates(I)

Alternating-current electrochemical synthesis is used to obtain for the first time halogenocuprates of an allyl derivative of phosphonium of the composition (CH₂=CHCH₂(C₆H₅)₃P)CuX₂ (X = Br (I), Cl (II)). Compound I crystallizes in the space group P2₁, a = 9.6341(3) Å, b = 12.4167(4) Å, c = 9.9618(4) Å, β = 117.484(5)°, Z = 2. Compound II crystallizes in the space group P2₁/n, a = 9.9725(5) Å, b = 15.4586(8) Å, c = 13.7557(5) Å, β = 90.429(4)°, Z = 4. In the structures of I and II quasilinear CuX ₂ ^? anions are held by C-H…X hydrogen bonds inside a framework formed by the stacking of phenyl groups from CH₂=CHCH₂(C₆P₅)₃P⁺ cations. Allyl groups are not involved in coordination with copper(I) atoms.     

Synthesis and crystal structure of diaquadibenzoatobis(nicotinamide)nickel(II)

A coordination compound of nickel(II) benzoate with nicotinamide [Ni(C₆H₅COO)₂(L)₂(H₂O)₂] (I) (L is nicotinic acid amide) is synthesized and studied by IR spectroscopy. Its crystal structure is solved by X-ray crystallography. The crystals of compound I are monoclinic: a = 7.152 Å, b = 18.266 Å, c = 10.341 Å, β = 109.24°, V = 1275.4 ų, Z = 2, space group P2₁/c. Structural units of a crystal of I are centrosymmetric octahedral complex molecules. The coordination environment of the Ni atom contains two O atoms (Ni-O(1) 2.066(2) Å) and two N atoms (Ni-N(1) 2.091(2) Å) of the monodentate-coordinated benzoate anions and nicotinamide molecules, respectively, as well as two O atoms of the H₂O molecules (Ni-O(1w) 2.110(2) Å).     

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.     

Crystal structures of 3-phenylpropenal thiosemicarbazone and its nickel and zinc chelates

3-Phenylpropenal thiosemicarbazone hydrate C₆H₅-HC=CH-CH=N-NH-C(S)-NH₂ · H₂O (HL · H₂O, I) and two chelates [Ni(L)₂] · nCH₃OH (II) and [Zn(L)₂] (III) are studied by X-ray diffraction. The crystals of I are orthorhombic: a = 6.227(1) Å, b = 7.763(2) Å, c = 25.585(5) Å, β = 90°, space group P2₁2₁2₁, Z = 4, R = 0.0426. A nonplanar molecule of I has an E conformation. The crystals of II are triclinic: a = 6.551(2) Å, b = 10.752(3) Å, c = 10.885(3) Å, α = 64.751(5)°, β = 82.753(5)°, γ = 89.857(5)°, space group, Z = 1, R = 0.0661. In a centrosymmetric molecule of II, the central atom coordinates two deprotonated ligands L through the immine nitrogen atom and thioamide sulfur atom at the vertices of a distorted square. The crystals of III are monoclinic: a = 25.342(2) Å, b = 9.150(2) Å, c = 21.340(3) Å, α = 90°, β = 111.84(2)°, γ = 90°, space group C2/c, Z = 8, R = 0.0556. In a molecule of complex III, two deprotonated bidentate ligands L are coordinated by the zinc ion through the immine nitrogen atoms and thioamide sulfur atoms to form a distorted tetrahedron at the central atom. In both II and III, ligand L after coordination by the metal ion changes the E conformation with respect to the N(1)-C(2) bond for the Z conformation. In crystals I-III, molecules are packed to form infinite layers parallel to the planes (001) and (010).     

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.     

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.     

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.     

Synthesis and crystal structure of Mn(II) and Hg(II) compounds and solution studies of Mn(II), Zn(II), Cd(II) and Hg(II) compounds based on piperazinediium pyridine-2,3-dicarboxylate

Novel metal organic frameworks including {(pipzH₂)[Mn(py-2,3-dc)₂]·7.75H₂O}_n, 1, {(pipzH₂)[Zn(py-2,3-dc)₂]·4H₂O}_n, 2, [Cd(py-2,3-dc)(H₂O)₃]_n, 3 and {(pipzH₂)[Hg₄Cl₁₀]}_n, 4, in which pipz is piperazine and py-2,3-dcH₂ is pyridine-2,3-dicarboxylic acid were synthesized applying a proton transfer ion pair i.e. (pipzH₂)(py-2,3-dcH)₂ and corresponding metallic salts and studied by IR, ¹H NMR, ¹³C NMR spectroscopy and single crystal X-ray diffractometry. The space group of compounds 1 and 4 are P2₁/c and C2/c of monoclinic system, respectively. The crystal dimensions are a = 20.108(2) Å, b = 19.910(2) Å, c = 12.997(1) Å, β = 94.354(2)° for 1 and a = 15.940(1) Å, b = 11.2690(9) Å, c = 11.1307(9) Å, β = 90.685(2)° for 4. The crystal structures of 2 and 3 have been reported previously. However, their solution studies are discussed here. The compounds had all polymeric structures. Although Zn^II, Cd^II and Hg^II were elements of the same group, their behavior against the ion pair was essentially different. Various supramolecular interactions mainly hydrogen bonds of the type O-H?O, N-H?O, C-H?O, N-H…Cl and C-H?Cl were observed in the structures. There was an unusual and huge water cluster in the structure of compound 1. The solution states of compounds 1–4 were studied and reported. The protonation constants of pipz and py-2,3-dc, the py-2,3-dc/pipz proton transfer equilibrium constants and stoichiometry and stability of the system with Mn²⁺, Zn²⁺, Cd²⁺ and Hg²⁺ ions in aqueous solution were investigated by potentiometric pH titrations.     

The crystal structures of α,ω-diaminoalkanecadmium(II) tetracyanonickelate(II)-aromatic molecule inclusion compounds. IV. (1,6-Diaminohexane)cadmium(II) tetracyanonickelate(II)-m-toluidine(1/1),-p-toluidine(1/1), and-2,4-xylidine(1/1) clathrates,and the coordination complex bis(p-toluidine) (1,6-diaminohexane)cadmium(II) tetracyanonickelate(II)

The crystal structures of the four title compounds have been analyzed by single crystal X-ray diffraction methods at room temperature. Three with a general formula Cd[NH₂(CH₂)₆NH₂]Ni(CN)₄·G (G=m-toluidine,Im;p-toluidine,Ip; and 2,4-xylidine,Ix) are the inclusion compounds of the respective aromatic molecules in the three-dimensional metal complex host (1,6-diaminohexane)cadmium(II) tetracyanonickelate(II). The remaining one is a coordination complex ofp-toluidine, bis(p-toluidine) (1,6-diaminohexane)cadmium(II) tetracyanonick-elate(II),II, Im, Ix, andII crystallize under similar experimental conditions;Ip is obtained using thep-toluidinemesitylene mixture at higher dilution than that used forII. Im crystallizes in the tri linic space group \(P\bar 1\) , witha=9.725(2),b=7.598(1),c=7.177(1) Å, α=90.44(1), β=98.80(1), γ=95.70(1)^o, andZ=1 (the final conventionalR=0.037 for 3526 reflections);Ip: monoclinic,P2/m,a=9.540(2),b=7.611(1),c=7.120(1) Å, β=100.95(1)^o, andZ=1 (R=0.027 for 1700 reflections);Ix: monoclinic,P2/m,a=9.628(2),b=7.613(1),c=7.122(1) Å, β=100.01(1)^o, andZ=1 (R=0.049 for 2704 reflections);II: monoclinic,P2₁/n,a=12.107(3),b=10.117(2),c=12.471(3) Å, β=113.67(2)^o, andZ=2 (R=0.037 for 2616 reflections). The structures ofIm, Ip andIx are similar to that of theo-toluidine inclusion compound of the same metal complex host. InII atrans pair of thep-toluidine molecules to the cadmium atom in the two-dimensional network formed by thecatena-μ-linkages of ?Cd?NH₂(CH₂)₆NH₂?Cd? and ?NC?Ni?CN?Cd?NC?Ni?CN?intersecting at each Cd atom; two cyanide groups of the tetracyanonickelate(II) moiety have free N-ends.     

Synthesis and molecular and crystal structures of binuclear complexes of Sm(III), Eu(III), Gd(III), Tb(III), and Dy(III) nitrates with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione

Binuclear complexes of Sm(III), Eu(III), Gd(III), Tb(III), and Dy(III) nitrates with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione (C₁₁H₂₀N₄O₂, SC)—[Sm(NO₃)₃(SC)(H₂O)]₂(I), [Eu(NO₃)₃(SC)(H₂O)]₂ (II), [Gd(NO₃)₂(SC)(H₂O)₃)]₂(NO₃)₂ (III), [Tb(NO₃)₃(SC)(H₂O)]₂ (IV), [Dy(NO₃)₃(SC)(H₂O)]₂ (V), are synthesized, and their X-ray diffraction analyses are carried out. The crystals of complexes I–V are monoclinic: space group P2₁/n for III and P2₁/c for I, II, IV, and V. In centrosymmetric coordination complexes II, III, IV, and V, the Ln atoms are coordinated by two O(1) and O(2) atoms of two molecules of the SC ligands bound by a symmetry procedure (1 ? x, ?y, 1 ? z), three bidentate nitrate anions, and a water molecule. The coordination numbers of the metal atoms are equal to 9, and the coordination polyhedra are considerably distorted three-capped trigonal prisms, whose bases include the O(1), O(2), O(12) and O(3), O(7), O(9) atoms. The dihedral angle between the bases of the prism is 18°, and that between the mean planes of the side faces is 55°–71° for I, 17° and 55°–71° for II, 16° and 55°–70° for IV, and 16° and 55°–70° for V. The Sm...Sm distance in complex I is 9.44 Å, Eu...Eu in II is 9.42 Å, Tb...Tb in IV is 9.36Å, and Dy...Dy in V is 9.36Å. The gadolinium atom in complex III is coordinated by two oxygen atoms of two ligand molecules bound by a symmetry procedure (?x, ?y + 1, ?z + 1), two bidentate nitrate anions, and three water molecules. One of the nitro groups in compound III is localized in the external coordination sphere of the metal. The coordination number of gadolinium is 9, and the coordination polyhedron is a significantly distorted three-capped trigonal prism, whose base includes the O(1), O(2), O(7) and O(4), O(5), O(9) atoms. The dihedral angle between the bases of the prism is 22.8°, and that between the mean planes of the side faces is 53°–72°. The Gd...Gd distance in complex III is 9.17 Å.     

Synthesis and structure of lithium and rubidium compounds with 2-(diphenylacetyl)-1,3-indanedione

Complexes RbL (I) and [Li₂(C₂H₅OH)L₂] (II) (L = C₂₃H₁₅O₃) have been synthesized and their crystal structures have been studied. Both compounds have monoclinic crystals with space group P2₁/c and Z = 4; I: a = 11.632(2) Å, b = 15.154(3) Å, c = 11.457(2) Å, β = 104.34(3)°; II: a = 12.982(3)Å, b = 12.083(2) Å, c = 25.317(5) Å β = 100.11(3)°. In the structure of I, dimeric groups [Rb₂O₆] with a shared edge are linked by the ligands to give infinite layers perpendicular to the x axis and cavities that form oblong channels. In the structure of II, Li₂O₇ dimers are formed by vertex sharing. The coordination of one of the lithium atoms (Li(1)) is completed to tetrahedral by the oxygen atom of the ethanol molecule. The structure of II, like that of I, is layered.     

Hydrothermal synthesis, crystal structure, and photoluminescence of Pb(II) and Mn(II) coordination polymers based on imidazo[4,5-f][1,10]phenanthroline

Two new coordination polymers, [Pb(IDPT)₂(NO₃)₂] (I) and [Mn(IDPT)(SO₄)(H₂O)₂] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P2₁/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) Å, β = 100.47(10)°, V = 2424.0(3) ų, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) Å, β = 99.32(10)°, V = 1490.25(14) ų, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via π-π interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.     

Stability and structure in solution of potassium and barium complexes with N,N’-diaryldiaza-18-crown-6: Crystal structure of N,N’-Bis(4-dimethylaminophenyl)diaza-18-crown-6 and its complex with barium perchlorate

It has been shown that N,N’-diaryldiaza-18-crown-6 ethers with p-dimethylamino-and p-methoxy groups in the benzene ring (aryl is 4-Mc₂NC₆H₄) (I) and 4-MeOC₆H₄ (II) form complexes with potassium and barium salts. The influence of these salts on the UV and ¹H NMR spectra of crown ethers I and II has been studied. The stability constants (logβ) of the complexes increase in the series II · Ba(ClO₄)₂ (2.0), I · Ba(ClO₄)₂ (2.3), II · KBr (2.8), I · KBr (3.0). N,N’-bis(4-dimethylphenylamine)diaza-18-crown-6 (L, I) and its complex with barium perchlorate Ba(ClO₄)₂ · L (III) are characterized by X-ray crystallography. The crystals of I are monoclinic: a = 13.778(2) Å, b = 5.9731(9) Å, c = 17.542(3) Å, β = 106.65(1)°, V = 1383.1(4) ų, Z = 2, space group P2₁/n, R = 0.0374 for 990 reflections with I > 2σ(I). The crystals of III are monoclinic: a = 17.275(4) Å, b = 8.017(2) Å, c = 26.935(4) Å, β = 100.47(2)°, V = 3669(1) ų, Z = 4, space group C2/c, R = 0.0320 for 1897 reflections with I > 2σ(I). The molecules of I and III are centrosymmetric. In III, the Ba atom is in the center of substituted diaza-18-crown-6 (DA18C6). The Ba atom is coordinated by all six donor atoms of diaza-18-crown-6 (av. Ba-O, 2.779(3) Å; Ba-N, 3.004(4) Å) and four oxygen atoms of two asymmetrically bound perchlorate groups (Ba-O, 2.832(4) and 3.031(4) Å) arranged below and above the plane of substituted diaza-18-crown-6. The conformations of the macrocycle in free and coordinated L are different.     

Thiourea-halide lattices. Part 1. Crystal structures of (n-C4H9)4N+F−·3(NH2)2CS, (n-C4H9)3(CH3) N+X−·2(NH2)2CS (X = Cl,Br), and (n-C3H7)4N+I−·(NH2)2CS

The title complexes (1, X = F;2, X = C 1; 3, X = Br and isomorphous with2; 4, X = I) have been prepared and characterized by X-ray crystallography. Crystal data, MoKα radiation:1, space groupCc,Z =4,a = 12.017(3),b = 14.263(5),c = 17.210(7) Å,β = 103.06(2)°, andR _F =0.053 for 2044 observed data;2, space groupCc,Z = 4,a = 12.817(3),b = 11.072(2),c = 16.781(5) Å,β =90.74(2)°,R _F = 0.044 for 2249 data;3,a = 12.873(4),b = 11. 119(2),c = 16.957(2) Å,β = 89.11(2)°,R _F = 0.049 for 2059 data;4, space groupP2₁/n,Z = 4,a = 8.858(2),b = 14.358(3),c = 15.379(3) Å,β = 93.88(1)°,R _F = 0.068 for 3119 data. In all four structures each thiourea molecule interacts with adjacent thiourea molecules via N-H ... S hydrogen bonds to give a ribbon-like arrangement, and also forms a pair of ‘chelating’ N-H ... X hydrogen bonds with a halide ion, resulting in an anionic framework (in1–3) or composite ribbon (in4) as a component in the crystal packing. The measured ranges of N... X distances are: 2.819(5)-2.994(7) Å for1, 3.252(3)-3.291(3)Å for 2, 3.353(6)-3.459(6)Å for3, and 3.564(5)-3.680(5) Å for 4.     

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.     

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.     

Synthesis, crystal structures, and biological activity of zinc(II) complexes derived from 4-bromo-2-[(3-diethylaminopropylimino)methyl]phenol

Two new Schiff base zinc(II) complexes, [ZnBr₂L] (I) and [ZnCl₂L] (II), where L is 4-bromo-2-[(3-diethylaminopropylimino)methyl]phenol, were synthesized and characterized by physico-chemical methods and single crystal X-ray diffraction. The crystal of I is monoclinic: space group P2₁/n a = 7.250 (2), b = 16.136 (3), c = 15.802 (3) Å, β = 90.027 (3)°, V = 1848.6 (7) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/n, a = 7.177 (3), b = 15.970 (4), c = 15.689 (3), β = 91.674 (3)°, V = 1797.5 (9) ų, Z = 4. The Zn atom in each complex is four-coordinated by one phenolate O and one imine N atoms of the Schiff base ligand and two halide atoms, forming a tetrahedral coordination. The urease inhibitory activities of the complexes were evaluated.