Antimycobacterial activity of mixed-ligand copper quinolone complexes

New mixed-ligand Cu^II, complexes: [Cu(cf)(phen)Cl)](BF₄) · 4H₂O (3), [Cu(cf)(bipy)(Cl)](BF₄) · 2H₂O (4) and [Cu(cf)(dafone)(Cl)](BF₄) · 2H₂O (5) (cf = ciprofloxacin, phen = 1,10-phenanthroline, bipy = 2,2-bipyridine and dafone = 4,5-diazafluoren-9-one) have been isolated and characterized by elemental analyses, i.r., u.v.–vis. spectra, magnetic susceptibility and cyclic voltammetry. Complex (4) crystallizes in the monoclinic space group P2₁/n with a = 13.8919(13) Å, b = 14.5718(13) Å, c = 14.0725(13) Å, = 95.150(2)°, V=2837.2(5) ų. All complexes possess square-pyramidal geometry. The antimycobacterial activity of ciprofloxacin and complexes (3–5) has been evaluated against Mycobacterium smegmatis, which shows clear enhancement in the antitubercular activity upon copper complexation with N—N donors.     

Mixed Complex Salt [Cu4(SCN2H4)7(NO3)](NO3)(SO4) · 3.3H2O: Synthesis and X-Ray Diffraction Analysis

The complex salt [Cu₄(SCN₂H₄)₇(NO₃)](NO₃)(SO₄) · 3.3H₂O was synthesized via reaction of aqueous solutions of thiourea with copper nitrate at 80°C and studied using X-ray diffraction analysis. The conditions and reasons for the partial oxidation of thiourea to sulfate ions were established. The crystals are monoclinic: a = 12.6072(7) Å, b = 15.4265(8) Å, c = 22.108(1) Å, = 120.133(6)°, space group P2₁/c, Z = 4. The crystal structure consists of [Cu₄(SCN₂H₄)₇(NO₃)]³⁺ complex cations, SO₄ ^2–, and NO₃ ^– anions, and molecules of the water of crystallization. Three types of coordination of the Cu atom were distinguished in the structure: trigonal (Cu–S 2.213–2.279 Å), tetrahedral (Cu–S 2.315–2.459 Å), and trigonal–pyramidal (3+1) (Cu–S 2.26–2.288, Cu–O 2.68 Å). The NO₃ ligand was found to be orientationally disordered.     

Diaqua[N,N-di(2-carboxyethyl)-o-anisidinato]copper(II) Dihydrate [Cu(o-Andp)(H2O)2] · 2H2O: Synthesis and Crystal Structure

Crystals of [Cu(o-Andp)(H₂O)₂] · 2H₂O (where o-Andp^2–is -anisidine-N,N-di-3-propionate) were synthesized and studied using X-ray diffraction analysis. The crystals are triclinic: a= 12.063(1) Å, b= 12.483(3) Å, c= 13.586(2) Å, = 91.29(1)°, = 111.67(1)°, = 104.00(1)°, V= 1830.5(5) ų, space group P , Z= 2, and R= 0.0528 for 5965 reflections with I2(I). The two crystallographically independent complexes are isostructural. The tetragonal–bipyramidal coordination of copper(III) involves three O atoms, the N atom of the tetradentate ligand o-Andp^2–, and two O atoms from water. The aminodipropionate group of the ligand (average Cu–O 1.939 Å and Cu–N 2.051 Å) and one of the coordinated water molecules (Cu–O(w) 1.991 Å) lie in the equatorial plane. The second water molecule (Cu–O(w) 2.32 Å) and the methoxy O atom of o-Andp^2–(Cu–O 2.37 Å) are in the apical positions of the bipyramid.     

Synthesis, Structure, and 31P NMR of Sulfur/Oxygen-Bridged Incomplete Cubane-Type Molybdenum and Tungsten Clusters with Triphenylphosphine Ligands

Sulfur/oxygen-bridged incomplete cubane-type triphenylphosphine molybdenum and tungsten-clusters [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·3THF (1A), [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (2A), [Mo₃OS₃Cl₄(H₂O)₂(PPh₃)₃]·2THF (1B), and [W₃S₄Cl₄(H₂O)₂(PPh₃)₃]·2THF (1C) were prepared from the corresponding aqua clusters and PPh₃ in THF/MeOH. On recrystallization from THF, procedures with and without addition of hexane to the solution gave 1A and 2A, respectively, while the procedures gave no effect on the formation of 1B and 1C. Crystallographic results obtained are as follows: 1A: monoclinic, P2₁/n, a=17.141(4) Å, b=22.579(5) Å, c=19.069(4) Å, =96.18(2)°, V=7337(3) ų, Z=4, R(R _w)=0.078(0.102); 1C: monoclinic, P2 ₁/c, a=12.635(1) Å, b=20.216(4) Å, c=27.815(3) Å, =96.16(1)°, V=7062(2) ų, Z=4, R(R _w)=0.071(0.083). If the phenyl groups are ignored, the molecule [Mo₃S₄Cl₄(H₂O)₂(PPh₃)₃] in 2A has idealized CS symmetry with the mirror plane perpendicular to the plane determined by the metal atoms, while the molecule in 1A does not have the symmetry. The tungsten compound 1C is isomorphous with the molybdenum compound 2A. ³¹P NMR spectra of 1A, 2A, and 1C were obtained and compared with similar clusters with dmpe (1,2-bis(dimethylphosphino)ethane) ligands.     

Synthesis and Structure of Catena-[Bis(2-Methylimidazole)(μ-Phthalato)cobaltate(II)]

A new coordination compound [Co(Pht)(2-MeIm)₂] (I), where Pht^2–is the deprotonated radical of o-phthalic acid (H₂Pht) and 2-MeIm is 2-methylimidazole, was synthesized. Its structure was established using X-ray diffraction analysis. The crystal is orthorhombic: space group Pca2₁, a= 15.350(3), b= 7.957(2), c= 13.997(3) Å, (calcd.) = 1.505 g/cm³, and Z= 4. The tetrahedral coordination of the Co(II) atom includes two N atoms of two 2-methylimidazole molecules and two oxygen atoms of two carboxyl groups from different acid radicals. The Co–N distances are equal to 2.022(2) and 2.031(2) Å, while the Co–O distances are 1.972(2) and 2.000(2) Å. The carboxyl groups of the Pht^2–radical and the aromatic nucleus form angles of 47.2° and 35.9°, whereas the angle formed by the carboxyl groups themselves is 50.3°. Compound Iis a polymer, which is confirmed by the 1,6-bridging function of the o-phthalic acid radical. The Co···Co distance in a chain is equal to 7.367 Å. Separate chains are united in the crystal into a framework via N–H···O hydrogen bonds.     

Crystal structure of K3SbS4·4 1/2 H2O

Summary The crystal structure of K₃SbS₄·4 1/2 H₂O, monoclinic, P2₁/c-C ₅ ^2h ,a=12.732(3),b=7.720(2),c=13.928(4) Å, =90.19(1)°,V=1369.0(5) ų,Z=4, has been determined from X-ray single crystal data and refined by least-squares methods toR=0.031 for 3 024 reflections. The structure is built up from KS_{4 – 5}(H₂O)_{3 – 5} polyhedra and SbS₄ tetrahedra (Sb-S=2.327 Å) which are three-dimensionally linked. The water molecules are bonded to two or three K⁺ ions and form exclusively O-H ... S-type hydrogen bonds. One of the five crystallographically different water molecule sites is due to space limitations only half occupied.

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Die Kristallstruktur von K₃SbS₄·4 1/2 H₂O

Zusammenfassung Die Kristallstruktur von K₃SbS₄·4 1/2 H₂O, monoklin, P2₁/c-C ₅ ^2h ,a=12.732(3),b=7.720(2),c=13.928(4) Å, =90.19(1)°,V=1369.0(5) ų,Z=4, wurde mit Röntgen-Einkristalldaten bestimmt und für 3 024 Reflexe aufR=0.031 verfeinert. Die Kristallstruktur ist aus dreidimensional verknüpften KS_{4 – 5}(H₂O)_{3 – 5}-Polyedern und SbS₄-Tetraedern (Sb-S=2.327 Å) aufgebaut. Die Wassermoleküle sind an zwei bis drei Kaliumionen gebunden und bilden ausschließlich Wasserstoffbrücken des Typs O-H...S aus. Eine der fünf kristallographisch verschiedenen H₂O-Lagen ist aus Platzmangel nur zur Hälfte besetzt.

     

The crystal structure of bis(1,4-dithioniumdicyclo-[2,2,2]-octane) μ-oxo-bis[tetracyanooxorhenate(V)]tetrahydrate

Summary The structure of [S(CH₂CH₂)₃S]₂[Re₂O₃(CN)₈]·4H₂O has been determined from three-dimensional x-ray diffraction data. The blue crystals are monoclinic, space group P2₁/c, with cell dimensionsa=9.431(2),b=10.879(2),c=16.217(3)Å, =110.84(2)°,Z=2 andD _m=2.11 gcm^–3. Anisotropic refinement by least-squares methods of 2483 observed reflections converged toR=0.050.The centrosymmetric binuclear anion has a linear O=Re–O–Re=O grouping with an eclipsed configuration for the cyano ligands. Bond distances: Re–O (terminal)=1.69(1), Re–O (bridging)=1.921(1) and Re–C_av=2.12(2)Å. Each Re atom is displaced by 0.11(2)Å towards the terminal oxygen atom giving a slight square-pyramidal distortion of the octahedral environment. The ring-constrained cation has C–S_av=1.82(2)Å with averaged bond angles C–S–C=101(1) and S–C–C=113(1)°.     

The crystal structure of Fe(SeO2OH)(SeO4)·H2O

Summary The crystal structure of the hydrothermally synthesized compound Fe(SeO₂OH) (SeO₄) · H₂O was determined by single crystal diffraction methods:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, space group P2₁/c,R=0.029,R _w=0.027 for 2430 independent reflections (sin /0.76 Å^–1). Isolated FeO₅(H₂O)-octahedra share five corners with [SeO₂OH] and [SeO₄] groups to form sheets parallel to (100). These sheets are interconnected via hydrogen bonds only.

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Die Kristallstruktur von Fe(SeO₂OH)(SeO₄)·H₂O

Zusammenfassung Die Kristallstruktur der hydrothermal dargestellten Verbindung Fe(SeO₂OH) (SeO₄)·H₂O wurde mittels Einkristallbeugungsmethoden bestimmt:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, Raumgruppe P2₁/c,R=0.029,R _w=0.027 für 2 430 unabhängige Reflexe (sin / 0.76 Å^–1). Isolierte FeO₅(H₂O)-Oktaeder teilen fünf Ecken mit [SeO₂OH]- und [SeO₄]-Gruppen, wobei sie Schichten parallel (100) bilden. Diese Schichten sind nur über Wasserstoffbrücken miteinander verbunden.

     

Crystal structure and spectra of the Ni(II) complex of pyridine-2,6-dithio-carbomethylamide

The crystal structure of the paramagnetic bis(pyridine-2,6-dithiocarbomethylamide) nickel(II) nitrate (NiPDTA) is described: C₁₈H₂₂N₆S₄·(NO₃)₂·(H₂O)_1,5, monoclinic, C2/c,Z=4,a=14.705 (3) Å,b=23.254 (8) Å,c=8.383 (3) A, =98.18 (2)°,d _x=1.55 gcm^–3,d _m=1.53 gcm^–3. The structure was solved withPatterson and differenceFourier techniques and refined to a residual ofR=0.053. The nickel is surrounded by a square bipyramidal coordination of four thioamide sulfur atoms and two pyridine nitrogen atoms. Vibrational and electronic band positions for this compound are discussed.

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Kristallstruktur und Spektren des Pyridin-2,6-dithiocarbomethylamid Nickel(II)-Komplexes

Zusammenfassung Die Kristallstruktur des paramagnetischen bis(Pyridin-2,6-dithiocarbomethylamid) Nickel(II)-nitrats (NiPDTA) wurde bestimmt. C₁₈H₂₂N₆S₄Ni·(NO₃)₂·(H₂O)_1,5, monoklin, C2/c,Z=4,a=14,705 (3) Å,b=23,254 (8) Å,c=8,383 (3) A, =98,18 (2)°,d _x=1,55gcm^–3,d _m=1,53gcm^–3. Das Phasenproblem wurde mittelsPatterson-und Differenz-Fourier-Synthese bestimmt und die Struktur bis zu einem kristallographischenR-Faktor vonR=0.053 verfeinert. Das Nickel-Atom ist von vier Thioamid-Schwefelatomen und zwei Pyridin-Stickstoffatomen in quadratisch-bipyramidaler Anordnung umgeben. Schwingungsspektren und Anregungsspektren des Komplexes werden diskutiert.

     

Crystal Structure of Calcium [Aqua(Nitrilotriacetatocobaltate(II)] Tetrahydrate,Ca[Co(Nta)(H2O)]2· 4H2O

Crystals of Ca[Co^II(Nta)]₂· 6H₂O (I), where Nta^3–is a nitrilotriacetate ion, were synthesized and studied using X-ray diffraction analysis. They were found to be monoclinic: a= 6.991(1), b= 10.031(1), c= 16.238(3) Å, = 98.50(1)°, V= 1126.2(3) ų, space group P2₁/n, Z= 2, R ₁= 0.0241, wR ₂= 0.0636, GOOF = 1.050 (for 3132 reflections with I> 2(I)). Structure Iis composed of {[Co(Nta)(H₂O)]^–}₁anion chains united by Ca²⁺cations into a three-dimensional framework. The coordination polyhedra of Co and Ca atoms are distorted octahedra. The Co(II) atom environment includes atoms N(1), O(1), O(3), and O(5) of one Nta^3–ligand, a carbonyl O(2)" atom of the neighboring anion fragment, and an O(w1) atom of the water molecule. The shortest bond is formed by the Co atom with the bridging O(2)" atom in trans-position relative to atom N(1). The Co–O(2)" distance (2.029 Å) is noticeably shorter than the other bond lengths, Co–O(Nta) (2.069–2.103 Å), Co–O(w1), and Co–N(1) (2.155 and 2.177 Å, respectively). Cations Ca²⁺are located in the inversion centers and involve in their coordination atoms O(4), O(6), O(w2), and the oxygen atoms symmetrically bond to them and arranged at 2.271(1), 2.420(1), and 2.351(2) Å, respectively. The structural formula of the title compound is {Ca(H₂O)₂[Co(Nta)(H₂O)]₂}₃· 2H₂O.     

Crystal structures of Co3(SeO3)3·H2O and Ni3(SeO3)3·H2O,two new isotypic compounds

Summary The crystal structures of the new, hydrothermally synthesized, isotypic compounds Co₃(SeO₃)₃·H₂O and Ni₃(SeO₃)₃·H₂O were determined by direct and Fourier methods and refined toR _w=0.023, 0.032 using single crystal X-ray data up to sin/=0.81 Å^–1 [space group P ,a=8.102 (2), 7.986 (3) Å;b=8.219 (2), 8.133 (3) Å;c=8.572 (2), 8.422 (3) Å, =69.15 (1), 69.50 (1)°; =62.88 (1), 62.50 (1)°; =67.23 (1), 67.64 (1)°;Z=2]. The structures are built up from [Me ₅(SeO₃)₆·2H₂O]^2– sheets containing three crystallographically different types of octahedrally coordinatedMe ²⁺ and trigonal pyramidal coordinated Se⁴⁺ atoms, respectively. These sheets are linked only by a fourth type ofMe ^2+[6] atom. All coordination polyhedra deviate significantly from their ideal shapes, bond lengths within the extremly distortedMe(4)O₆ polyhedra range from 1.983 (2) Å to 2.403 (2) Å in Co₃(SeO₃)₃·H₂O and from 1.987 (4) Å to 2.301 (3) Å in the Ni compound, O-Se-O bond angles were found between 92.8 (2)° and 104.9 (1)°. Hydrogen bond lengths are 2.802 (3)Å and 2.600 (4)Å in the Co compound, and 2.762 (6) Å and 2.561 (6) Å in Ni₃(SeO₃)₃·H₂O. The latter is one of the shortest known hydrogen bonds donated by a water molecule.

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Die Kristallstrukturen von Co₃(SeO₃)₃·H₂O und Ni₃(SeO₃)₃·H₂O, zwei neue isotype Verbindungen

Zusammenfassung Die Kristallstrukturen der neuen, hydrothermal synthetisierten, isotypen Verbindungen Co₃(SeO₃)₃·H₂O und Ni₃(SeO₃)₃·H₂O wurden mit direkten und Fourier-Methoden bestimmt und unter Verwendung von Einkristallröntgendaten bis sin/=0.81 Å^–1 aufR _w-Werte von 0.023, 0.032 verfeinert [Raumgruppe P ,a=8.102 (2), 7.986 (3) Å;b=8.219 (2), 8.133 (3) Å;c=8.572 (2), 8.422 (3) Å, =69.15 (1), 69.50 (1)°; =62.88 (1), 62.50 (1)°; =67.23 (1), 67.64 (1)°;Z=2]. Die Strukturen werden von [Me ₅(SeO₃)₆·2H₂O]^2– Schichten aufgebaut, die je drei kristallographisch unterschiedliche Arten von oktaedrisch koordiniertenMe ²⁺ und trigonal pyramidal koordinierten Se⁴⁺ Atomen enthalten. Diese Schichten sind nur durch eine vierte Art vonMe ^2+[6] Atomen verknüpft. Alle Koordinationspolyeder weichen deutlich von ihren Idealformen ab, Bindungslängen in den extrem verzerrtenMe(4)O₆ Polyedern variieren zwischen 1.983 (2) Å und 2.403 (2) Å in Co₃(SeO₃)₃·H₂O und zwischen 1.987 (4) Å und 2.301 (3) Å in der Ni-Verbindung, O-Se-O-Bindungswinkel liegen zwischen 92.8 (2)° und 104.9 (1)°. Wasserstoffbrückenlängen sind 2.802 (3) Å und 2.600 (4) Å in der Co-Verbindung, und 2.762 (6) Å und 2.561 (6) Å in Ni₃(SeO₃)₃·H₂O. Letztere ist eine der kürzesten bekannten Wasserstoffbrücken eines Wassermoleküls.

     

Crystal and molecular structures of heteroligand bis(hexafluoroacetylacetonato)copper(II) complexes with 3-imidazoline nitroxyl radicals,Cu(C5HF6O2)2:L=1:1 (L1=C13H18N3O,L2=C8H15N2O)

Crystal structures were determined for two new derivatives of heteroligand complexes of Cu(C₅HF₆O₂)₂ with nitroxyl radicals derived from 3-imidazoline: Cu(C₅HF₆O₂)₂(C₁₃H₁₈N₃O) (I) and Cu(C₅HF₆O₂)₂(C₈H₁₅N₂O) (II). The unit cell parameters for I are as follows: a=10.555(3), b=15.505(5), c=18.509(6) Å, V = 3029(1) ų, Z=4, d_calc=1.57 g/cm³, space group P2₁2₁2₁. The unit cell parameters for II are as follows: a=16.018(3), b=15.886(3), c=19.665(4) Å, V = 5004(1)ų, Z=8, d_calc=1.68 g/cm³, d_exp=1.68 g/cm³, space group P2₁2₁2₁. The structure of I is molecular. The coordination of the copper ion is a trigonal bipyramid formed by two oxygen atoms of the (hfac) ions and the nitrogen atom of the imidazoline heterocycle in the equatorial plane [Cu–O, 1.91(7), 2.242(7) Å, Cu–N, 2.010(7) Å] and the other oxygen atoms of the (hfac) anion in the axial positions [Cu–O, 1.940(6), 1.963(6) Å]. Complex II is polymeric. The two crystallographically independent Cu(hfac)₂ fragments are linked in a chain by means of two L² ligands. The coordination of the copper ions is a square bipyramid, whose equatorial plane is formed by the oxygen atoms of the (hfac) anion [Cu–O, 1.89(1)–2.03(1) Å]. The axial positions are occupied by nitrogen atoms [Cu–N, 2.52(1), 2.40(1) Å] and an oxygen atom of the NO fragment [Cu–O, 2.96(1), 2.67(1) Å] of different L² ligands. The ...Cu(hfac)₂–L²–Cu(hfac)₂–L₂... chains in the unit cell are located at two levels (x1/4 and 3/4).Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 2, pp. 126–133, March–April, 1993.     

The structure of binuclear molybdenum(VI) oxocomplexes with dianionic tridentate Schiff bases

Summary The new Mo^VI complex [Mo(O) (-O) (SAE)]₂ was prepared and characterized by means of spectroscopic (i.r.,¹Hn.m.r.) and crystallographic measurements. Crystals of the [Mo(C₉H₈NO₂)(H₂O)]₂, M=582.3, orthorhombic, space group Pbca,a=13.108(4),b=8.982(2),c=16.842(4) Å, v=1982.9 ų, z=4, D_m=1.93(2), D_c=1.95 g cm^–3, MoK =0.71069 Å, =1.3 mm^–1, F(000)=1152, T=295K, R=0.035 for 2413 reflections.The crystal structure consists of [Mo(O)(-O)(L)]₂, in dimeric units. The coordination geometry around each molybdenum atom is distorted octahedral with Mo–O (terminal) and Mo–O (bridge) distances of 1.694(3) and 1.760(3) Å, respectively, and with the angle O(1)–Mo–O(2) of 105.6(1)^o, typical for manycis-dioxocomplexes of Mo^VI. The asymmetric bridge is characterized by the following parameters: Mo–O(2)ⁱ and Mo–Moⁱ distances equal 2.408(3) and 3.319(3) Å, respectively, and the Mo–O(2)–Moⁱ and O(2)–Mo–O(2)ⁱ angles equal 104.5(1)^o and 75.5(1)^o, respectively.The i. r. and Raman spectra of molybdenum complexes with an asymmetric double oxygen bridge display a strong absorption the 800–850 cm^–1 range.     

An approach to the structure and spectra of copper barbiturate trihydrate

In the neutral title complex [Cu(C₄N₂H₃)₂(H₂O)₃] or [Cu(BBR)₂(H₂O)₃] (BBR^– = Barbiturate), the Cu^II ion, in the slightly distorted square-pyramidal geometry, is coordinated by two O atoms of the two monodentate barbiturates and three O atoms of three water ligands. The average bond length of Cu—O (BBR^–) is 1.981(5) Å and the average bond length of Cu—O (H₂O) at the basal sites is 1.94(5) Å, i.e. much shorter than that of Cu—O (H₂O) [2.175(11) Å]. The crystal structure is characterized by an extensive network of hydrogen bonds in which each [Cu(BBR)₂(H₂O)₃] entity links to six adjacent [Cu(BBR)₂(H₂O)₃] by O(C=O) ··· H—O(H₂O) bonds. Tautomerism in the coordination process for BBR^– was found from the crystal structure and i.r. spectral analysis. The interaction of Cu^II and BBR^– in aqueous solution was also investigated by electronic spectra and electrochemical method. It was observed that the copper ion could not only form the [Cu(BBR)₂(H₂O)₃] complex in aqueous but also catalyze the decomposition of BBR^– at pH 1.1.     

Two-Dimensional Supramolecular from the Self-Assembly of Dissymmetrical Oxamidato-Bridged Heterometallic Trinuclear Building Blocks: Synthesis, Crystal Structure, and Magnetic Properties

Two heterometallic trinuclear complexes {[Cu(oxbp)]₂Co(H₂O)₂}1.5DMF0.5H₂O (complex 1) and {[Cu(oxbm)]₂Co(H₂O)₂}2DMF (complex 2) were obtained from the self-organization of two new dissymmetrical oxamidato-bridged copper(II) building blocks [Cu(oxbp)]^– and [Cu(oxbm)]^–[H₃oxbp=N-benzoato-N'-(3-aminopropyl)oxamido, H₃oxbm=N-benzoato-N'-(2-amino-2-methylethyl)oxamido, DMF=dimethylformamide]. The crystal structure of complex 1 has been determined. Complex 1 crystallize in triclinic system, space group P-1, a=8.0609(16) Å, b=10.661(2) Å, c=22.279(5) Å, =85.32(3), =86.64(3), =70.90(3), and Z=1. The crystal structure of complex 1 consists of neutral trinuclear complex units, and hydrogen bond involved DMF and water molecules. Through the hydrogen bonds, weak coordination and CuCu weak interactions, complex 1 features a 2-D supramolecular structure. Magnetic susceptibility measurements (5–100 K) indicate that the central Co(II) and terminal copper metal ions are antiferromagnetically coupled with J=–28.09 and J=–29.70 cm^–1 for complex 1 and 2, respectively.     

Crystal structure of anhydrous alum RbFe3+(SeO4)2

Summary The compound RbFe(SeO₄)₂ was prepared hydrothermally by reaction of Rb₂CO₃ and FeC₂O₄·2H₂O with H₂O and H₂SeO₄ at 490 K. Single crystal X-ray methods revealed isotypy with KAl(SO₄)₂. RbFe(SeO₄)₂ crystallizes in space group P321;Z=1;a=5.005(1)Å,c=8.548(2) Å,V=185.4 ų; 781 unique data up to 80 °2;R,R _w =0.045, 0.042. The structure is best described as sheets of [Fe(SeO₄)₂]^– parallel (001), interconnected by Rb⁺. FeO₆ trigonal prims and SeO₄ tetrahedra have bond lengths of 1.99 Å and 1.63 Å, respectively. The Rb atom is [6 + 6] coordinated with Rb-O distances of 3.04 Å and 3.48 Å.

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Die Kristallstruktur des wasserfreien Alauns RbFe³⁺(SeO₄)₂

Zusammenfassung Die Verbindung RbFe(SeO₄)₂ wurde hydrothermal dargestellt durch Reaktion von Rb₂CO₃ und FeC₂O₄·2H₂O mit H₂O und H₂SeO₄ bei 490K. Einkristallröntgenmethoden belegten die Isotypie mit KAl(SO₄)₂ RbFe(SeO₄)₂ kristallisiert in der Raumgruppe P321;Z=1;a=5.005(1) Å,c=8.548(2) Å,V=185.4 ų; 781 unabhängige Daten bis 80 °2;R,R _w =0.045, 0.042. Die Struktur läßt sich am besten als Schichten von [Fe(SeO₄)₂]^– parallel (001) beschreiben, die durch Rb⁺ verbunden sind. FeO₆ trigonale Prismen und SeO₄ Tetraeder weisen Bindungslängen von 1.99 Å bzw. 1.63 Å auf. Das Rb-Atom ist [6+6] koordiniert mit Rb-O Abständen von 3.04 Å und 3.48 Å.

     

Crystal Structure of Diaqua(1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane)(perchlorato-O)strontium Perchlorate Hydrate

The aqua complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with strontium perchlorate of the composition [Sr(ClO₄)L(H₂O)₂]⁺ · ClO₄ ^– · H₂O (I) was synthesized and studied using X-ray diffraction analysis: space group P2₁/c, a = 16.195 Å, b = 11.382 Å, c = 16.646 Å, = 117.01°, Z = 4. The structure was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.069 for 4278 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains complex cation [Sr(ClO₄)L(H₂O)₂]⁺ of the host–guest type. The Sr²⁺ cation (coordination number 9) is coordinated to all six O atoms of the L podand, O atom of a disordered ClO₄ ^– ligand, and two O atoms of two water molecules. The coordination polyhedron of Sr²⁺ is irregular; in a rough approximation, it can be described as a face-centered cube. The crystal structure of I contains an infinite three-dimensional network of the O–H···O hydrogen bonds joining the complex cations, ClO₄ ^– anions, and molecules of crystallization water.     

The crystal structure of tetraphenylphosphonium tetracyanohydroxooxorhenium(V)

Summary The crystal structure of (PPh₄)₂[ReO(OH)(CN)₄]·5H₂O has been determined from three-dimensional x-ray diffraction data. The light brown crystals are monoclinic, space group P2₁/n, with cell dimensionsa=16.753(2),b=19.928(2),c=15.338(2) Å and =101,894(1)°,z=4, D_m=1.45(1) g cm^–3. The anisotropic refinement of the 6088 observed reflections converged to R=0.077.The [ReO(OH)(CN)₄]^2– ion has a distorted octahedral geometry. Bond distances: Re =1.70(1), Re–OH=1.90(1) and ReC_av=2.12(2) Å. The Re atom is displaced by 0.08 Å out of the plane formed by the four carbon atoms towards the terminal oxo ligand.     

Copper(II) Complexes with N-(3-Hydroximino-2-methylbutan-2-yl)methylamine (HL): Synthesis and Properties. Crystal and Molecular Structures of [Cu(HL)Cl2] and [Cu(HL)(H2O)2SO4]n

Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl₂(I), Cu(HL)(SO₄) · 2H₂O (II), and Cu(HL)(NO₃)₂(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C₆H₁₄Cl₂CuN₂O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) ų, space group P2₁/c, _calcd = 1.679 g/cm³, Z = 4 for R ₁ = 0.0250; for II(C₆H₁₈CuN₂O₇S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) ų, space group P2₁/c, _calcd = 1.753 g/cm³, Z = 4 for R ₁ = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H₂O) + 2O(SO₄)). Complexes I–IIIare characterized by IR and EPR spectroscopy.     

Structure of Cu(II) complexes of pyridine-2,6-dithiocarbomethylamide

The crystal structure of the paramagnetic pyridine-2,6-dithiocarbomethyl-amide—copper(II) chloride (CuPDTA-Cl₂) is described: C₉H₁₁N₃S₂CuCl₂·H₂O, monoclinic, P2₁/n,a=9.163 (2),b=8.925 (5),c=17.590 (9) Å, =102.08 (1)°,Z=4,d _x =1.784g cm^–3. The structure was refined to a residual ofR=0.059, The copper is coordinated in a square—pyramidal arrangement by the pyridine nitrogen, the two thioamide sulfur atoms and the two chloride ions. The shortest Cu—Cu distance in the crystal is 5.02 Å, leading to only very weak antiferromagnetism. Spectroscopic and magnetic data are given for additional members of the CuPDTA-X [X=Cl₂, Br₂, I₂, (NO₃)₂, (SCN)₂,Py] complex type, which suggest a large degree of structural resemblance with the CuPDTA-Cl₂ complex.

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Struktur von Kupfer(II)-Komplexen des Pyridin-2,6-dithiocarbomethylamids

Zusammenfassung Die Kristallstruktur des paramagnetischen Pyridin-2,6-dithiocarbomethyl-amid Kupfer(II)-chlorids wurde bestimmt: C₉H₁₁N₃S₂CuCl₂·H₂O, monoklin, P2₁/n,a=9,163 (2),b=8,925 (5),c=17,590 (9) Å, =102,08 (1)°,Z=4,d _x =1,784g cm^–3. Die Struktur wurde bis zu einemR-Faktor vonR=0,059 verfeinert. Das Kupfer-Zentralatom zeigt quadratisch-pyramidale Koordination durch den Pyridin-Stickstoff, die beiden Thioamid Schwefelatome sowie zwei Chloridionen. Der kürzeste Cu—Cu-Abstand im Kristall beträgt 5,02 Å, was zu einem nur sehr schwachen Antiferromagnetismus führt. Spektroskopische und magnetische Größen werden für weitere Derivate vom CuPDTA-X Typ [X=Cl₂, Br₂, I₂, (NO₃)₂, (SCN)₂, Pyridin] angegeben, und im Sinne einer großen strukturellen Ähnlichkeit mit dem CuPDTA-Cl₂ interpretiert.