Synthesis,structures and magnetic properties of three copper(II) complexes of 2-(1<Emphasis Type="Italic">H</Emphasis>-pyrazol-3-yl) pyridine

Three Cu(II) complexes: [Cu₂(μ-L)₂(HCOO)₂(H₂O)₂] (1), [Cu₂(μ-L)₂(NO₃)₂] (2), and [Cu₄(μ-L)₆(CH₃COO)₂]·2H₂O (3) constructed from 2-(1H-pyrazol-3-yl) pyridine (HL) were synthesized and structurally characterized by X-ray single-crystal diffraction. The X-ray analyses revealed that all three complexes feature a di-ligand-bridged Cu₂ unit, which is nearly planar. Each deprotonated ligand chelates one copper atom by means of N,N(pyridine-pyrazole) pocket and simultaneously bridges the other one by the N,N(pyrazole) groups. The remaining coordination sites of the Cu(II) centers are either occupied by different anionic coligands to balance the charge, or bridged by another L to develop a tetranuclear structure. Magnetic investigations reveal that the distortion of the Cu(II) coordination geometry (as described by the τ values) and the coplanarity of the Cu–(N=N)₂–Cu unit have cooperative effects on the antiferromagnetic strength of these systems.     

Hydrothermal synthesis and crystal structure of a composite complex constructed from Keggin-type tungstoborate and copper

A novel composite complex constructed from Keggin-type tungstoborate and copper, [Cu(En)₂(H₂O)][Cu(En)₂]₂H₃[BW_11.75Cu_0.25O₄₀] · 3.75H₂O (I), where En is ethylenediamine, has been synthesized hydrothermally and characterized by elemental analysis, IR, XPS, TGA, and single-crystal X-ray diffraction. The crystal structure of I consists of one Keggin polyoxoanion [BW_11.75Cu_0.25O₄₀]^6?, one cation [Cu(En)₂(H₂O)]⁺, two cations [Cu(En)₂]⁺, three protons, and 3.75 lattice water molecules. Compound I crystallizes in the orthorhombic, space group Pbca, a = 21.5438(18), b = 20.6591(18), c = 26.052(2) Å, V = 11595.2(17) ų, Z = 8, ρ = 3.968 g/cm³, F(000) = 12322, μ = 24.476 mm^?1, R = 0.0306 and wR = 0.0666.     

Structural study and magnetic properties of copper(II) thiophene-2-carboxylate with 4-pyridinemethanol and isonicotinamide

The synthesis and characterization of [Cu(5-Me-2-tpc)₂(4-pyme)₂] (I), [Cu(3-Me-2-tpc)₂(4-pyme)₂] (II), [Cu(2-tpc)₂(4-pyme)₂] (III), [Cu(2-tpc)₂(isonia)₂(2-tpcH)] (IV), [Cu(5-Me-2-tpc)₂(isonia)₂(5-Me-2-tpcH)] (V), [Cu₂(2-tpc)₄(4-pyme)₂] (VI), [Cu₂(3-Me-2-tpc)₄(isonia)₂] (VII) (where 2-tpc is 2-thiophenecarboxylate, 3-Me-2-tpc is 3-methyl-2-thiophenecarboxylate, 5-Me-2-tpc is 5-methyl-2-thiophenecarboxylate and 4-pyme is 4-pyridinemethanol and isonia is isonicotinamide) are reported. The complexes under study were characterized by electronic, IR and EPR spectroscopy, magnetic susceptibility over the temperature range and X-ray structure analysis. Structural studies revealed a distorted tetragonal-bipyramidal environment around the copper ion for monomeric complexes I–V. The structure of dimeric complexes VI and VII consists of units of the known paddle-wheel dicopper(II) tetracarboxylates, which are made up of four thiophene-2-carboxylate ions thus bridging the two copper atoms. The complex molecules of all compounds are connected through H-bonds into supramolecular chains or frameworks. The spectral and magnetic properties are discussed with regard to X-ray data.     

X-ray study of rhodium(III) sulfates

Compounds with compositions [Rh(H₂O)₆]₂(SO₄)₃·4H₂O (I), (H₃O)[Rh(H₂O)₆](SO₄)₂ (II), [Rh(H₂O)₅OH](SO₄)·0.5H₂O (III), and [Rh(H₂O)₆]₂(SO₄)·(H₂SO₄) _x ·5H₂O (IV) have been studied. The crystal structures of II, III, and IV were determined. All compounds crystallized in the monoclinic crystal system. Crystal data for II: a = 7.279(2) Å, b = 10.512(7) Å, c = 15.806(3) Å, β = 96.71(3)°, space group P2₁/n, Z = 2, d _calc = 2.334 g/cm³; III: a = 20.433(4) Å, b = 7.820(2) c = 11.215(2) Å, β = 114.14(1)°, space group C2/c, Z = 8, d _calc = 2.559 g/cm³; IV: a = 6.2250(4 Å), b = 27.0270(12) Å, c = 7.2674(5) Å, β = 97.04(3)°, space group P2₁/c, Z = 4, d _calc = 2.143 g/cm³. The compounds were studied by IR spectroscopy and powder X-ray diffraction. All of the isolated crystalline phases are sparingly soluble in ethanol and well soluble in water.     

<Emphasis Type="Italic">trans</Emphasis>-Tetraaqua(dibromo)nickel(II) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane dibromide: Synthesis and crystal structure

A new complex, trans-tetraaqua(dibromo)nickel(II) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane dibromide, [NiBr₂(H₂O)₄][H₂(Crypt-222)]Br₂ (I), was synthesized and its crystal sructure was studied by X-ray diffraction analysis: space group P2₁/c, a = 13.573, b = 8.328, c = 14.523 Å, β = 111.08°, Z = 2. Structure I was solved by a direct method and refined by full-matrix least-squares method in anisotropic approximation to R = 0.067 on 2684 independent reflections (CAD-4 autodiffractometer, λMoKα). The octahedral complex molecule [NiBr₂(H₂O)₄] and the [H₂(Crypt-222)]²⁺ dication (with two protonated N atoms) are located around the inversion center; the latter is statistically disordered. The dication contains trifurcate hydrogen bonds N-H(…O)₃. Crystal I also contains intermolecular hydrogen bonds O(w)-H…Br^?, which join the complex molecules [NiBr₂(H₂O)₄] and the Br^? anions into infinite “thick” layers parallel to the plane yz.     

The effect of the substituents in the malonate anion and the solvent molecules on the structures of novel coordination polymers [Li2VO(R2mal)2]n

Reactions of vanadyl sulfate (VOSO₄?3H₂O) with dimethylmalonic (H₂Me₂mal = = C₃H₆(CO₂H)₂), cyclobutane-1,1-dicarboxylic (H₂cbdc = C₄H₆(CO₂H)₂), or butylmalonic acid (H₂Bumal = C₄H₁₀(CO₂H)₂) and Li₂CO₃ in a ratio of 1: 2: 2 afforded novel coordination polymers of similar compositions ([Li₂(VO)(Me₂mal)₂]_n (1), [Li₂(VO)(Me₂mal)₂(EtOH)-(H₂O)]_n (2), [Li₄(VO)₂(cbdc)₄(H₂O)₇]_n (3), and [Li₂(VO)(Bumal)₂(H₂O)_5.5]_n (4)) but different structures. The crystal structures of the compounds containing the Me₂mal^2– and Bumal^2– anions depend on the solvent nature.     

Deca(hydroxo)-23-aqua-hexa(lanthanum(III)) iodide octahydrate and deca(hydroxo)-23-aqua-hexa(neodymium(III)) iodide octahydrate: Syntheses and structures

New hexanuclear complexes of lanthanum and neodymium iodides, [La₆(H₂O)₂₃(OH)₁₀]I₈ · 8H₂O (I) and [Nd₆(H₂O)₂₃(OH)₁₀]I₈ · 8H₂O (II), are synthesized and studied by X-ray diffraction analysis. The isostructural crystals of complexes I and II are orthorhombic: a = 13.197(4) Å, b = 15.152(3) Å, c = 15.302(4) Å and a = 13.060(4) Å, b = 14.967(5) Å, c = 15.098(4) Å, respectively; Z = 2, space group Pnnm. The lanthanum (neodymium) atoms coordinate the aqua and hydroxo ligands and enter the composition of the Ln₆ -containing complex cations. The coordination polyhedron (ignoring the central oxygen atom) of each atom of the complexing agent is somewhat distorted square antiprism with the aqua and hydroxo ligands being in the vertices. Four bridging ligands link this atom of the complexing agent with the four adjacent atoms.     

Different structural types of copper(II) furan- and thiophencarboxylates: X-ray structural,EPR, spectral and magnetic analyses

Synthesis and characterization of eight new complexes of various structural types are reported. With 5-nitro-2-furancarboxylic acid (5-NO₂-2-fucH), two monomeric complexes, [Cu(5-NO₂-2-fuc)₂(H₂O)₂] (II) and [Cu(5-NO₂-2-fuc)₂(H₂O)₄] (III), as well as a dimeric complex with ethylnicotinate (Etnic), [Cu(5-NO₂-2-fuc)₂(Etnic)₂]₂ (V), were prepared. With other acids: 2,5-dimethyl-3-furancarboxylic acid (2,5-Me₂-3-fucH), 2-thiophencarboxylic acid (2-tpcH), 3-methyl-2-thiophencarboxylic acid (3-Me-2-tpcH) or 5-methyl-2-thiophencarboxylic acid (5-Me-2-tpcH), only dimeric complexes [Cu(2,5-Me₂-3-fuc)₂(H₂O)]₂ (I), [Cu(2,5-Me₂-3-fuc)₂(Etnic)]₂ (IV), [Cu(2-tpc)₂(Etnic)]₂ (VI), [Cu(3-Me-2-tpc)₂(Etnic)]2 (VII) and Cu(5-Me-2-tpc)₂(Etnic)]₂ (VIII) have been synthesised. Characterizations of the complexes were based on elemental analysis and infrared, electronic, EPR and magnetic measurements. Moreover, complexes III, V, VII and VIII were also studied by X-ray structural analysis. Two structural types of dimeric complexes were observed differing in the number of carboxylate bridges. Most of the dinuclear complexes exhibit the common “paddle-wheel” structural motif while the molecular structure of V contains two pentacoordinated copper(II) ions bridged by two carboxylate groups of two 5-nitro-2-furancarboxylate ligands resulting in the intramolecular copper-copper distance of 4.4960(8) Å. Magnetic properties (monomeric EPR signal and isotropic exhchange constant (J of approximately 0 cm^?1) of V confirmed a very weak magnetic interaction between copper centres.     

Self assembly of three new copper coordination polymers based on N-[(3-pyridine)-sulfonyl]aspartate: Synthesis and structure

Three new copper coordination polymers [Cu(L) · 6H₂O] _n (I), [Cu₂(L)₂] _n (II), and [Cu(HL)₂] _n (III), where H₂L is N-[(3-pyridine)-sulfonyl]aspartate, have been synthesized and characterized by singlecrystal X-ray diffraction (CIF files CCDC nos. 1435871 (I), 1435872 (II), 1435873 III), elemental analysis and IR spectra. Moreover, the variable-temperature magnetic susceptibility had been studied for complex I. A structural comparison of these polymers suggests that different reaction temperatures play important role in the construction of resulting architectures for I–III.     

Thermal properties of solid complexes with biologically important heterocyclic ligands

Thermogravimetry (TG), derivative thermogravimetry (DTG) and infrared (IR) spectroscopy have been applied to the investigation of the thermal behaviour and structure of the compounds [Cu(2-Clbz)₂(nia)₂(H₂O)₂] (I), [Cu(2-Clbz)₂(nia)₂]·H₂O (II), [Cu(2-Brbz)₂(nia)₂]·2H₂O (III), [Cu(2-Brbz)₂(nia)₂(H₂O)] (IV), where 2-Clbz and 2-Brbz?=?2-chloro- and 2-bromobenzoate anions, nia?=?nicotinamide, H₂O?=?water molecules. Thermal decomposition of all studied compounds proceeds in three steps. Heating the compounds first results in a release of non-coordinated and/or coordinated water molecules. The final product of thermal decomposition was CuO. The thermal stability of the complexes can be ordered in the sequence: I<IV<III<II. Nicotinamide is coordinated to Cu(II) through the nitrogen atom of the heterocyclic ring. IR data suggest the unidentate coordination of benzoate anions to Cu(II) in complexes I, IV and bidentate coordination in complexes II and III.     

Four novel metal–organic frameworks based on 3,4,7,8-tetramethyl-1,10-phenanthroline: Syntheses,structures, and thermal properties

Four novel metal–organic frameworks, [Cu(Tmp)₂(H₂O)] · NO₃ (I) (Tmp = 3,4,7,8-tetramethyl-1,10-phenanthroline), [Mn(Tmp)₂(H₂O)₂] · 2NO₃ · H₂O (II), [Pb(Tmp)(CH₃COO)₂] · 3H₂O (III) and [Zn(Tmp)₂(H₂O)₂] · 2NO₃ · 2H₂O (IV), have been synthesized and characterized by single crystal X-ray diffraction (CIF files CCDC nos. 88362–88365 for I–IV, respectively), IR spectroscopy, elemental analysis and thermogravimetric analysis. Both I and II complexes are crystallized in monoclinic system with space groups C2/c, P2₁/c, respectively, while III and IV complexes are crystallized in triclinic system with space groups \(P\overline 1 \). Generally, these crystal structures are stabilized by O–H···O hydrogen bonds and π–π interactions between the phenanthroline rings of neighboring molecules. Thermogravimetric analyses of compounds I–IV display considerable thermal stability.     

Bis(citrato)germanates of bivalent 3<Emphasis Type="Italic">d</Emphasis> metals (Fe,Co, Ni,Cu, Zn): Crystal and molecular structure of [Fe(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>][Ge(HCit)<Subscript>2</Subscript>] · 4H<Subscript>2</Subscript>O

In continuation of a systematic study of bis(citrate)germanates, we synthesized a number of heterometallic germanium(IV) and 3d metal complexes based in citric acid (H₄Cit) with the molecular formula [M(H₂O)₆][Ge(HCit)₂] · nH₂O, where M = Fe, n = 4 (I); Co, n = 2 (II); Ni, n = 2 (III); Cu, n = 1 (IV); Zn, n = 3 (V). The complexes were characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The X-ray diffraction analysis of compound I was performed. Crystals are monoclinic, a = 10.091(4) Å, b = 11.126(4) Å, c = 10.996(4) Å, β = 100.966(6)°, V = 1212.1(8) ų, Z = 4, space group P2₁/n, R1 = 0.0561 for 2266 reflections with I > 2σ(I). Compound I is composed of centrosymmetric octahedral complexes-[Ge(HCit)₂]^2? anions and [Fe(H₂O)₆]²⁺ cations—and crystallization water molecules. Structural units in compound I are combined by a hydrogen bond system.     

SOD mimetic activity of salicylatocopper complexes

Investigation of salicylatocopper complexes in the presence of a nitrogen donor ligand is a growing research area due to the interesting mimetic activities of such complexes. Here, three X-salicylatocopper (where X = 3-methyl, or 4-methoxy) complexes with three different N-donor ligands, [Cu(μ-menia)(3-Mesal)₂(menia)(H₂O)]₂ (I), Cu(3-Mesal)₂(denia)₂(H₂O)₂ (II), Cu(4-MeOsal)₂(2-pyme)₂ (III), are presented (where 3-Mesal = 3-methysalicylate, 4-MeOsal = 4-methoxysalicylate, menia = N-methylnicotinamide, 2-pyme = 2-pyridylmethanol). The complexes were characterized by elemental analysis, IR and UV-VIS spectrophotometry. Cyclic voltammetry and the superoxide dismutase activity of the prepared complexes in solution were measured and the complexes were characterized by means of the inhibition concentration IC₅₀. In addition, the superoxide dismutase (SOD) activity of these complexes was compared with those of the parent ligand copper acetate, native SOD enzyme, and the related copper complexes containing non-steroidal anti-inflammatory drugs. The resulting SOD activity was correlated to the composition, structure and redox stability of the prepared complexes. The best value of the inhibition concentration was found for complex I (IC₅₀ = 2.24 µM), which classifies this complex into a group of good superoxide scavengers.     

Synthesis and crystal structure of triaqua[0.25(bromo)1.75(nitrato-O)]copper(II) 18-crown-6 hydrate (solvate)

A complex triaqua[0.25(bromo)1.75(nitrato-O)]copper(II) 18-crown-6 hydrate (solvate), [CuBr_0.25(NO₃)_1.75(H₂O)₃] · 18-crown-6 · 5H₂O, is synthesized, and its crystal structure is studied by X-ray diffraction analysis (space group Cmc2₁, a = 13.705, b = 14.583, c = 13.174 Å, Z = 4; direct method, full-matrix least-squares refinement in the anisotropic approximation to R = 0.069 for 2547 independent reflections; CAD-4 automated diffractometer, λMoK _α radiation). The mixed complex molecule is a randomly disordered mixture of [Cu(NO₃)₂(H₂O)₃] and [CuBr(NO₃)(H₂O)₃] molecules with site occupancies of 0.875 and 0.125, respectively. The mixed complex molecule and 18-crown-6 molecule lie on the m plane. In the main complex molecule [Cu(NO₃)₂(H₂O)₃], the coordination polyhedron of the Cu²⁺ cation is a slightly distorted square pyramid. The 18-crown-6 molecule has the conformation of a crown with the approximate symmetry D _3d .     

4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]-hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates: Synthesis and crystal structures

Two complex salts, i.e., 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane tetrachloromanganese(II) and tetrachlorozinc(II) hydrates, [H₂(Crypt-222)][MnCl₄] · 1.5H₂O (I) and [H₂(Crypt-222)][ZnCl₄] · 2H₂O (II) were synthesized and their crystal structures were studied by X-ray diffraction. Crystals I and II are trigonal (space group R \(\bar 3\) c, Z = 12); I: a = 11.033, c = 77.775 Å; II: a = 11.046, c = 77.555 Å (the structures were solved by the direct method and refined by the full-matrix least-squares method in anisotropic approximation to R = 0.056 (I) and 0.065 (II) for all 2634 (I) and 2636 (II) independent reflections; CAD-4 automated diffractometer, λMoK _α). The [MnCl₄]^2? or [ZnCl₄]^2? anion in structures I or II and the 2.2.2-cryptand dication (with two protonated N atoms) lie on crystal axis 3. The dication contains trifurcate hydrogen bonds N⁺-H(…O)₃. The bond lengths and bond angles in tetrahedral anions [MnCl₄]^2? or [ZnCl₄]^2? are disproportional, probably, due to the Jahn-Teller effect. The molecules of water of crystallization in crystals I, II are disordered over two positions.     

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.     

Copper(II) complex with 3-(2-hydroxy-3-sulfo-5-nitrophenylhydrazo)pentane-2,4-dione: Synthesis and structure

The copper(II) complex with 3-(2-hydroxy-3-sulfo-5-nitrophenylhydrazo)pentane-2,4-dione (H₃L) is studied, and its crystal structure is studied by X-ray diffraction analysis. The crystals of [Cu(H₂O)₂]₂(μ-L)₂[Cu(H₂O)₄] (I) are triclinic (space group P \(\bar 1\)) at 100 K, a = 7.085(3), b = 10.373(5), c = 12.265(6) Å, α = 0.842(5)°, β = 104.996(6)°, γ = 99.156(6)°, Z = 1). The C=O and NH groups of hydrazone and the OH and SO₃H groups from the aromatic moiety of the molecule are involved in coordination with the copper(II) atom. In the centrosymmetric trinuclear molecule the central Cu(2) atom has the coordination number six, and the terminal Cu(1) atoms have the coordination number five. The thermal properties of complex I are studied. The complex formation of copper(II) with the H₃L ligand in an aqueous solution at temperatures 298 ± 0.5, 308 ± 0.5, and 318 ± 0.5 K is studied by potentiometric titration. The standard thermodynamic functions of the complex formation are determined.     

Synthesis,structures, and magnetic properties of two closely-related manganese(II) coordination polymers

The reactions of Mn²⁺ ion with 4-nitrobenzene-1,2-bicarboxylic acid in the presence of bipyridyl-type coligands gave two new manganese(II) coordination polymers, [Mn₂(Nbdc)₂(Bipyp)(H₂O)₄] _n (I) and [Mn₂(Nbdc)₂(Bipye)(H₂O)₄] _n (II) (H₂Nbdc = 4-nitrobenzene-1,2-bicarboxylic acid, Bipyp = 1,3-bi(4-pyridyl)propane, and Bipye = 1,2-bi(4-pyridyl)ethane). Both two complexes contain uniform carboxyl-bridged manganese chains with the composition of [Mn₂(Nbdc)₂(H₂O)₄] _n , which are interlinked by interchain Bipyp/Bipye spacers to afford two closely-related layers (CIF files CCDC nos. 1008182 (I) and 1008183 (II)). Magnetic studies for two compounds show the presence of similar antiferromagnetic couplings between the adjacent Mn²⁺ ions through the carboxyl bridges, the best fittings to the experimental magnetic susceptibilities gave J =–0.20 cm^–1 and g = 1.96 for I, and J =–0.24 cm^–1 and g = 1.98 for II. Similar magnetic parameters and thermal behaviors further verify that two compounds possess closely-related structures.     

Two copper complexes with imidazole ligands: Syntheses,crystal structures and fluorescence

Two copper (imidazole) complexes, namely, [Cu(im)₆]Cl₂ · 4H₂O (1), and [Cu(im)₆]Cl₂ · 2H₂O (2) (im-imidazole) have been synthesized by hydrothermal method. Single-crystal X-ray analysis revealed that the complex 1 belongs to triclinic system, space group P \(\bar 1\) with a = 8.8097(18) Å, b = 9.0812(18) Å, c = 10.586(2) Å; α = 75.08(3)°, β = 83.14(2)°, γ = 61.84(3)°; R ₁ = 0.0562, wR ₂ = 0.1607. In compound 1, [Cu(im)₆]²⁺ cation and counter anions Cl^? alternatively array in an ABAB fashion via N-H...Cl hydrogen bonding. Compound 2 falls into monoclinic system, space group P2₁/n with a = 8.073(2) Å, b = 13.239(2) Å, c = 15.0810(10) Å; β = 97.940(10)°; R ₁ = 0.0434, wR ₂ = 0.1243. The equatorial ligands are involved into a complex hydrogen bond network that involves the chloride anions and uncoordinated water molecules. We report there synthesis, crystal structure, thermal stability, IR spectrum and fluorescent property.     

Ruthenium(II,III,III) μ<Subscript>3</Subscript>-oxotrifluoroacetate with dimethyl sulfoxide: Synthesis,structure, and DTF quantum-chemical calculations

The reaction of [Ru ₃ ^III (μ₃-O)(μ-O₂CCF₃)₆(H₂O)₃](O₂CCF₃) in methanol gives two solvates, [Ru₃O(O₂CCF₃)₆(DMSO)₃] · 1/2H₂O (I) and [Ru₃O(O₂CCF₃)₆(DMSO)₃] · H₂O (II), of a novel trinuclear mixedvalence Ru(II,III,III) trifluoroacetate complex, where two DMSO molecules are coordinated to the Ru atoms through the O atom, while the third DMSO molecule is coordinated through the S atom. According to the X-ray diffraction data, the complex can crystallize in two crystal systems: triclinic (I) (space group P \(\overline 1 \)) and monoclinic (II) (space group P2₁/m). The unit cell parameters for I are: a = 9.354, b = 11.005, c = 20.846 Å, α = 99.10, β = 96.38, γ = 92.17, Z = 2; R = 7.27%; for I are: a = 9.186, b = 17.044, c = 13.091 Å, β = 101.10, Z = 2; R = 14.18%.