Die Kristallstruktur von TlFeSe2 und TlFeS2

TlFeSe₂ is monoclinic, space groupC2/m–C _2h ³ ,a=11.973 Å,b=5.490 Å,c=7.110 Å, =118.2°,Z=4.TlFeS₂ is isotypic witha=11.636 Å,b=5.304 Å,c=6.799 Å, =116.7°.The crystal structure of TlFeSe₂ has been determined from single crystal diffractometer data. Isotypy of the sulfide has been confirmed from powder diffraction data. The crystal structure containing infinite linear chains of edgesharing FeX ₄-tetrahedra, and its relationship to the thio- and selenoferrates of the alkali metals are discussed. The mineral raguinite is very probably isotypic to synthetic TlFeS₂.

     

Zur Kenntnis von Cr2H2(As2O7)(As4O12)

The crystal structure of Cr₂H₂(As₂O₇)(As₄O₁₂) has been determined by X-ray methods using single crystal diffractometer data (1,152 reflections,R=0.054, orthorhombic,Pmmn,a=1317.7 (7),b=1124.9 (6),c=494.3 (4) pm,Z=2). The crystal structure contains both diarsenate(V) and the hitherto unknown cyclo-tetraarsenate(V)-anions. The magnetic susceptibility follows theCurie-Weiss law (=3.86±0.01 _B/Cr³⁺, =–31 K).

     

Natural product chemistry,part 100: The structure of carissone,C15H24O2

Summary C₁₅H₂₄O₂,M=236.2, monoclinic, P 2₁,a=7.229(7),b=14.925 (9),c=6.235 (9) Å, =92.40 (9)°,V=672.1 ų,T=–133 °C,Z=2,D _x=1.17 g cm^–3. The X-ray diffraction analysis of this sesquiterpenoid fromCarissa opaca confirmed the previously proposed constitution of the isolate and, furthermore, allowed precise NMR assignment.

---

Naturstoffchemie, 100. Mitt.: Die Struktur des Carissons, C₁₅H₂₄O₂

Zusammenfassung C₁₅H₂₄O₂,M=236.2, monoklin, P 2₁,a=7.229 (7),b=14.925 (9),c=6.235 (9) Å, =92.40 (9)°,V=672.1 ų,T=–133 °C,Z=2,D _x=1.17 g cm^–3. Die Röntgenstrukturanalyse dieses Sesquiterpenoids ausCarissa opaca bestätigte die bereits vorgeschlagene Struktur und erlaubte ferner eine genaue NMR-Zuordnung.

     

Complexes of dioxouranium(VI) with zwitter-ionic forms of Bi- and tetra-dentateSchiff bases

Potentially bi- and tetra-dentateSchiff bases derived from salicylaldehyde react with hydrated uranyl salts to give complexes: UO₂H₂ LX ₂, UO₂H₂ LX ₂ and UO₂(HL)₂ X ₂ [H₂ L=N,N-propane-1,3-diylbis(salicylideneimine), H₂ L=N,N-ethylenebis(salicylideneimine) and HL=N-phenylsalicylideneimine;X ^–=Cl^–, Br^–, I^–, NO₃ ^–, ClO₄ ^–, and NCS^–]. Because of marked spectral similrities with the structurally known Ca(H₂ L) (NO₃)₂, theSchiff bases are coordinated through the negatively charged phenolic oxygen atoms and not the nitrogen atoms of the azomethine groups which carry the protons transferred from phenolic groups on coordination. Halide, nitrate, perchlorate and thiocyanate groups are covalently bonded to the uranyl ion, resulting a 6-coordinated uranium ion in the halo and thiocyanato complexes and 8-coordinated in nitrato and perchlorato complexes.

---

Komplexe von Dioxouranyl(VI) mit zwitterionischen Formen von zwei- und vierzähnigen Schiff-Basen

Zusammenfassung Von Salizylaldehyd abgeleitete zwei- und vierzähnigeSchiff-Basen reagieren mit hydratisierten Uranylsalzen zu Komplexen folgenden Typs: UO₂H₂ LX ₂, UO₂H₂ LX ₂ und UO₂(HL)₂ X ₂ [H₂ L=N,N-Propan-1,3-diylbis(salicylidenimin), H₂ L=N,N-Ethylen-bis(salicylidenimin) und HL=N-Phenylsalicylidenimin;X ^–=Cl^–, Br^–, I^–, NO₃ ^–, ClO₄ ^– und NCS^–]. Auf Grund eindeutiger spektraler Ähnlichkeiten mit dem bekannten Ca(H₂ L) (NO₃)₂ wird auf Koordination über die negativ geladenen phenolischen Sauerstoffatome (und nicht über die Azomethin-Stickstoffe) geschlossen. Die AnionenX ^– sind kovalent an das Uranyl-Ion gebunden; damit ergibt sich ein hexakoordiniertes Uranyl-Ion für die Halogen- und Thiocyanat-Komplexe und Oktakoordination für die Nitrat- und Perchlorat-Komplexe.

     

PbCu3(OH)(NO3)(SeO3)3·1/2H2O und Pb2Cu3O2(NO3)2(SeO3)2: Synthese und Kristallstrukturuntersuchung

Crystals of PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O [a=7.761(3)Å,b=9.478(4)Å,c=9.514(4)Å, =66.94(2)°, =69.83(2)°, =81.83(2)°, space group P ,Z=2] and Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ [a=5.884(2)Å,b=12.186(3)Å,c=19.371(4)Å, space group Cmc2₁,Z=4] were synthesized under hydrothermal conditions. Their crystal structures were refined with three-dimensional X-ray data toR _w=0.033 resp. 0.055. In PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O the Cu atoms are [4+1] and [4+2] coordinated and via SeO₃ groups a three-dimensional atomic arrangement is built up. In Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ there are sheets, which are connected only via Pb-O bonds ranging from 2.98 Å to 3.16 Å.

     

Crystal Structures of Ammonium and Cesium Pentadecafluorotetraantimonates(III)

Antimony(III) fluoride complexes with compositions (NH₄)₃Sb₄F₁₅(I) and Cs₃Sb₄F₁₅(II) are structurally characterized. Crystals Iare triclinic: a= 8.317(3) Å, b= 10.419(6) Å, c= 10.826(3) Å, = 63.71(4)°, = 73.24(3)°, = 77.42(5)°, Z= 2, _calcd= 3.42 g/cm³, _exp= 3.45 g/cm³, space group P , R= 0.051; crystals IIare monoclinic: a= 8.079(2) Å, b= 29.116(8) Å, c= 8.162(2) Å, = 117.08(2)°, Z= 4, _calcd= 4.549 g/cm³, _exp= 4.50 g/cm³, space group P2₁/c, R= 0.036. Structure Iis composed of SbF₄E and SbF₅E polyhedra combined into tetranuclear chains; crystals IIconsist of SbF₄E polyhedra, two of which form a dimer Sb₂F₇E₂, while the other two are isolated (E is the antimony lone electron pair).     

Kristallstruktur von Trisilber(I)amidosulfat-3-Ammoniak-2-Wasser,Ag3SO3N · 3NH3 · 2H2O

An X-ray crystal structure analysis of colourless Ag₃SO₃N · 3NH₃ · 2H₂O was carried out at room temperature:M=504.79, orthorhombic, P2₁2₁2₁,a=6.275 (1) Å,b=11.826 (2) Å,c=14.299 (12) Å,V=1061.10 ų,Z=4,d _x=3.160 Mgm^–3,F(000)=940, Mo K, =0.71069 Å (graphite monochromator), =5.60 mm^–1,R=4.71%,R _w=4.96% (982 reflections, 120 parameters). The structure consists of Ag ribbons; each Ag atom is linearly co-ordinated to two N atoms with distances corresponding to covalent Ag-N bonds; no Ag-O coordination is observed; the N atom of the SO₃N group is surrounded by three Ag atoms; compared to amidosulfuric acid, the SO₃N group shows significant deformation.

     

Synthesis and physico-chemical studies of some polynuclear mixed carboxylate complexes of nickel(II)

A number of polynuclear mixed carboxylates of nickel(II) with the general composition [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (whereR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ and C₂₁H₄₃ andn=1 or 2) have been synthesized by the transacylation reactions of anhydrous nickel acetate with higher carboxylic acids in refluxing toluene. On recrystallization from benzene-alcohol mixtures, mono-alcoholate complexes, Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (whereR=CH₃ and C₂H₅) have been isolated. All these derivatives have been characterized by the molecular weight determinations, infra-red and electronic reflectance spectra and magnetic susceptibility measurements.

---

Synthese und Eigenschaften einiger gemischter Carboxylat-Komplexe von Nickel(II)

Zusammenfassung Komplexe des Typs [Ni(OOCCH₃)_2–n (OOCR) _n ] _x (mitR=C₁₃H₂₇, C₁₅H₃₁, C₁₇H₃₅ und C₂₁H₄₃,n=1 oder 2) wurden aus wasserfreiem Nickelacetat mit höheren Carbonsäuren in siedendem Toluol erhalten. Bei der Kristallisation aus Benzol-Alkohol-Mischungen wurden Monoalkoholate Ni(OOCCH₃)_2–n (OOCR) _n ·ROH (mitR=CH₃ und C₂H₅) isoliert. Die Charakterisierung der Komplexe erfolgte mittels Molekulargewichtsbestimmung, Infrarot- und Elektronenspektren und der Messung der magnetischen Susceptibilität.

     

Structure and magnetic properties of the ferromagnetically coupled nickel dimer [Ni(terpy)(NCO)(H2O)]2(PF6)2

Summary The crystal structure of the dimeric [{Ni(C₁₅H₁₁N₃)(NCO)(H₂O)}₂](PF₆)₂ has been determined by x-ray diffraction methods. Crystal data are as follows: P 1,a=11.904(4) Å,b=10.392(4) Å,c=8.531(3) Å, =111.87(2)^o, =90.61(3)^o, =107.37(5)^o, U=926.7(4) ų, Z=2, D_m=1.77(2), D_x=1.78 g. cm^–3, (Mo-K)=12.1 cm^–1, F(000)=494. Least-squares refinement of 1230 reflections with I1.5(1) gave a final R =0.035 (R=0.038). The structure is formed by cationic [{Ni(C₁₅H₁₁N₃)(NCO)(H₂O)}₂]²⁺ and anionic PF ₆ ^– units, linked through hydrogen bonds between the water molecule and the hexafluorophosphate ion. The resulting coordination geometry around each nickel(II) ion is ferragonally elongated octahedral. The N-bridging cyanate groups occupy simultaneously an equatorial position in the coordination sphere of one of the nickel atoms and an axial position in the other. The remaining axial positions are occupied by the water molecules. Powder susceptibility data, between 2.0 and 300 K, show the existence of ferromagnetic exchange between nickel centres. The magnetic parameters are J/K=6.6K, D/K =–17.6 K, zJ/K=0.57 and g-2.21.     

Die Kristallstruktur von Dikalium-trikobalt(II)-dihydroxid-trisulfat-dihydrat,K2Co3(OH)2(SO4)3·2H2O

Crystals of K₂Co₃(OH)₂(SO₄)₃·2H₂O were synthesized under hydrothermal conditions. The crystal structure [a=17.945 (4) Å,b=7.557 (2) Å,c=9.760 (3) Å, space group Cmc2₁,Z=4] was determined by direct methods and refined with single crystal X-ray data. The H atoms were located byFourier syntheses. Their structural parameters were refined, too. The finalR-values areR=0.025 andR _w =0.028 (w=1/) for 612 reflections withF ₀>3 (F ₀). Both Co(II) atoms are octahedral six coordinated and form zigzag chains running parallel [001]. These chains are connected via sulfate groups to built up sheets parallel (100). The KO₉ polyhedron and one of the four hydrogen bonds link these sheets.

     

Synthesis of some schiff bases of 3-aroyl-6-aryl-4-hydroxy-2H-pyran-2-ones

Summary The reaction of 3-aroyl-6-aryl-4-hydroxy-2H-pyran-2-ones (Ar=p-tolyl, 1,1-biphenyl-4-yl or thienyl) with aniline and substitutedo-phenylenediamine (R=H, CH₃ or Cl) yields a series of new Schiff bases2a–f in 51–72% yield. Bromination of1a gave the 5-bromo derivative1c, while the compounds1a,1b,2b,2e, and2f were converted into 2,6-diaryl-4H-pyran-4-ones3a–c. All products have been fully characterized.

---

Synthese von Schiff'schen Basen von 3-Aroyl-6-aryl-4-hydroxy-2H-pyran-2-onen

Zusammenfassung Die Reaktion von 3-Aroyl-6-aryl-4-hydroxy-2H-pyran-2-onen (Ar=p-Tolyl, 1,1-Biphenyl-4-yl oder Thienyl) mit Anilin und substituierteno-Phenylendiaminen liefert neue Schiff'sche Basen2a–f/bd in 51–72% Ausbeute. Bromierung von1a gab das 5-Bromderivate1c, während die Verbindungen1a,1b,2b,2e und2f in 2,6-Diaryl-4H-pyran-4-onen3a–c übergeführt wurden. Alle Produkte wurden voll charakterisiert.

     

Zur Mannich-Reaktion von Dihydro-6-methyl-2(1H)-pyrimidinonen

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone reagieren mit Formaldehyd und sekundären bzw. primären Aminen zu 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinonen bzw. Hexahydro-2(1H)-pyrido[4,3-d]Pyrimidinonen. Mit Succindialdehyd bzw. Glutardialdehyd und primären Aminen entstehen 5,7-Äthanohexahydro-2(1H)-pyrido[4,3-d]pyrimidinone bzw. Tetrahydro-6,8-propano-6H-pyrimido[1,6-c]pyrimidin-1(2H)-one. Die 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinone geben mit Phenolen Tetrahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-one, mit cycl. -Dicarbonylverbindungen Hexahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2,5(3H, 6H)-dione bzw. Tetrahydrospiro(2H,5H-pyrano[3,2-c][1]benzopyran-2,4(1H)-pyrimidin)-2(3H),5-dione bzw. mit Malonestern -(Tetrahydro-4,4-dimethyl-2-oxo-6-pyrimidyl)-äthylmalonester.Zusammenfassung Dihydro-4.4.6-trimethyl-2(1H)-pyrimidinones react with formaldehyde and sec. and prim. amines resp. to 6-dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones and hexahydro-2(1H)-pyrido[4.3-d]pyrimidinones, resp. succindialdehyde and glutaraldehyde with primary amines give 5.7-ethanohexahydro-2(1H)-pyrido[4.3-d]pyrimidinones and tetrahydro6.8-propano-6H-pyrimido[1.6-c]pyrimidin-1(2H)-ones, resp. 6-Dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones react with phenols to tetrahydrospiro([1]benzopyran-2.4(1H)-pyrimidin)-2(3H)-ones, with cyclic -dicarbonyl compounds to hexahydrospiro([1]benzopyran-2.4 (1H)-pyrimidin)-2,5 (3H), 6H)-diones and tetrahydrospiro(2H,5H-pyrano[3.2-c][1]benzopyran-2.4(1H)-pyrimidin)-2(3H),5-diones, resp., with malonates -(tetrahydro-4.4-dimethyl-2-oxopyrimidyl-6)-ethylmalonates.

---

Mannich reaction with dihydro-6-methyl-2(1H)-pyrimidinones

---

Herrn Prof. Dr.F. Kuffner zum 65. Geburtstag gewidmet.     

Reactions of 2H-3,4-dihydro-1,4-benzoxazin-6(8aH)-ones with 2,4,6-trimethylbenzonitrile oxide,III

Summary Regio-, stereo- and siteselectivity of the cycloadditions of trimethylbenzonitrile oxide with 2H-3,4-Dihydro-1,4-benzoxazin-6(8aH)-ones have been investigated. The structures of the obtained products were elucidated by means of homonuclear NOE difference spectroscopy and HMQC and HMBC spectra. The structure of 6-Benzyl-9a-methoxy-3-mesityl-9b-methyl-7,8,9a,9b-tetrahydro-3aH-1,2-oxazolo-[4,5-h]1,4-benzoxazin-4(6H)-on5 was elucidated from a single crystal X-ray structure analysis at ambient temperature: C₂₇H₃₀N₂O₄, M=446.55g/mol, monoclinic, P2₁/c,a=10.372 (34) Å,b=11.908 (21) Å,c=20.040 (34) Å, =97.16 (17)°,V=2455.8 (1.9)ų,Z=4,d _c=1.208g/cm³, =0.08mm^–1,R=0.0546.Dedicated to Prof. Ott with best wishes for his 70^th birthday     

Preparation,spectroscopic and structural analysis of uranium-arabinose complexes

The reaction betweenL-arabinose and hydrated uranyl salts has been investigated in aqueous solution and the solid complexes of the type UO₂(L-arabinose)X ₂ · 2 H₂O, whereX=Cl^–, Br^–, and NO ₃ ^– , have been isolated and characterized. Due to the marked similarities with those of the structurally known Ca(L-arabinose)X ₂ · 4 H₂O and Mg(L-arabinose)X ₂ · 4 H₂O (X=Cl^– or Br^–) compounds, the UO ₂ ²⁺ ion binds obviously to twoL-arabinose moieties, through O1, O5 of the first and O3, O4 of the second molecule resulting into a six-coordinated geometry around the uranium ion with no direct U-X (X=Cl^–, Br^– or NO ₃ ^– ) interaction. The intermolecular hydrogen bonding network of the freeL-arabinose is rearranged upon uranium interaction. The -anomer configuration is predominant in the freeL-arabinose, whereas the -anomer conformation is preferred in the uranium complexes.

---

Darstellung, spektroskopische und Strukturanalyse von Uran-Arabinose Komplexen

Zusammenfassung Es wurde die Reaktion zwischenL-Arabinose und hydratisierten Uranylsalzen in wäßriger Lösung untersucht und kristalline Komplexe des Typs UO₂(L-Arabinose)X ₂ · 2 H₂O mitX=Cl^–, Br^– und NO ₃ ^– isoliert und charakterisiert. Wie aus markanten Ähnlichkeiten der Komplexe mit den bekannten Verbindungen Ca(L-Arabinose)X ₂ · 4 H₂O und Mg(L-Arabinose)X ₂ · 4 H₂O (X=Cl^– oder Br^–) abzuleiten ist, bindet das UO ₂ ²⁺ -Ion mit zweiL-Arabinose Einheiten, wobei sich durch die O1,O5-Koordination des ersten und die O3,O4-Koordination des zweiten Moleküls eine sechs-koordinierte Geometrie um das Uranylion [ohne direkte U-X (X=Cl^–, Br^– oder NO ₃ ^– ) Wechselwirkung] ausbildet. Die intermolekularen Wasserstoffbrücken zeigen nach der Wechselwirkung mit dem Uranylion eine Umgruppierung. In der freienL-Arabinose ist das -Anomere vorherrschend, in den Urankomplexen hingegen das -Anomere.

     

Coordination compounds of N-(2-aminophenyl)- and N-(3-aminophenyl)pyridine-2′-carboxamide with cobalt(II) and cobalt(III). The nature of amide deprotonation induced by cobalt(III) in acidicpH

New complexes of the general formulae CoL ₂ X·nH₂O (X=Cl, Br, I, NCS, NO₃ andn=0, 1, 2 or 3), Co₂ L ₂ X ₃·EtOH (X=Cl, Br, I, NCS), Co(DH)X ₂ (X=NCS, NO₃) and Co(DH)₂ X ₂ (X=NCS, I) have been prepared, whereLH=N-(2-aminophenyl)pyridine-2-carboxamide andDH=N-(3-aminophenyl)pyridine-2-carboxamide. The compounds were characterized by X-ray powder patterns, conductivity measurements, thermogravimetric analysis, magnetic properties as well as by IR, ligand field and¹H-NMR spectroscopy. In the presence of oxygen,LH undergoes a cobalt(III) ion promoted amide hydrogen ionization in thepH region 4–6.

---

Koordinationsverbindungen von N-(2-aminophenyl)- und N-(3-aminophenyl)pyridin-2-carboxamid mit Cobalt(II) und Cobalt(III). Die Natur der Deprotonierung von Amiden induziert von Cobalt(III) in saurem Medium

Zusammenfassung Neue Komplexe der allgemeinen Formeln CoL ₂ X·nH₂O (X=Cl, Br, I, NCS, NO₃ undn=0, 1, 2, 3), Co₂ L ₂ X ₃·EtOH (X=Cl, Br, I, NCS), Co(DH)X ₂ (X=NCS, NO₃) und Co(DH)₂ X ₂ (X=NCS, I) wurden dargestellt mit LH=N-(2-aminophenyl)pyridin-2-carboxamid undDH=N-(3-aminophenyl)pyridin-2-carboxamid. Die Verbindungen wurden mittels Röntgenstrukturanalyse, Leitfähigkeitsmessungen, thermogravimetrischen Analysen, magnetischen Eigenschaften sowie mit IR-, Ligandenfeld- und¹H-NMR-Spektroskopie charakterisiert. In Gegenwart von Sauerstoff unterliegtLH einer Cobalt(III)ion-induzierten Amidwasserstoffionisierung impH-Bereich 4–6.

     

Hydrothermal Syntheses and Structural Characterization of One-Dimensional [Cu4Br2I3(C12H8N2)2] n and Molecular Cu3Br3(C12H8N2)2

The hydrothermal reactions of CuBr₂, CuX (X=Br, I), and phen (phen=1,10-phenanthroline, C₁₂H₈N₂) have lead to the syntheses of two novel complexes of one-dimensional [Cu₄Br₂I₃(phen)₂] _n 1 and trinuclear discrete cluster Cu₃Br₃(phen)₂ 2. Both compounds were characterized by singe-crystal X-ray diffraction. Crystal data for 1. Monoclinic, space group P2 ₁/c with a=14.054(3) Å, b=13.700(3) Å, c=15.920(3) Å, =114.16(3)°, Z=2; 2. Monoclinic, space group C2/c with a=10.040(2) Å, b=14.516(3) Å, c=16.319(3) Å, =94.29(3)°, Z=6.     

Coordination chemistry of alkali and alkaline earth cations: Crystal structure of rubidium (benzo-15-crown-5)2NO3·H2O

The complex Rb(B15C5)₂NO₃·H₂O is monoclinic,P2_1/c,a=12.695(3),b=19.471(3),c=12.991(2)Å, =99.60(2)^o,V=3166 ų,D _c =1.473 g/cm³ (163 K),D _c =1.434 g/cm³ (298 K),D _o =1.44 g/cm³ (298 K),T=163K,Z=4, MoK=0.71069 Å, 2(4^o–53^o), =16.43 cm^–1,F(000)=1424. FinalR for the 4588 observed reflections (F>3) is 0.062. All ten oxygens of the two benzo-crowns are shown to coordinate to the rubidium ion (Rb...O,2.92 to 3.07 Å) forming a charge-separated sandwich. The nearest nitrate oxygen is displaced 6.51 Å from the rubidium ion and is hydrogen bonded to a water molecule. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82028 (28 pages)     

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.

---

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.

     

Kristallstruktur von Trimethylisocyanursäure, (CH3NCO)3, und von Trichlorisocyanursäure-1/2-Ethylenchlorid, (ClNCO)3·1/2C2H4Cl2

X-ray crystal structure analyses of (CH₃NCO)₃ (M) and (ClNCO)₃·1/2C₂H₄Cl₂ (C) were carried out at room temperature (MoK, graphite monochromator, =0.71069 Å): 1.M=171.16, monochlinic, P2₁/c,a=14.848 (1) Å,b=13.400 (2) Å,c=8.149 (1) Å, =100.87 (1)°,V=1 592.3 ų,Z=8,F(000)=720,d _x =1.428 Mgm^–3, =76m^–1,R=6.51%,R _w =7.01% (964 reflections, 218 parameters). 2.M=281.89, monochlinic, P 2₁/c,a=9.416 (3) Å,b=5.728 (1) Å,c=18.199 (8) Å, =98.64 (2)°,V=970.4 Å₃,Z=4,F(000)=556,d _x =1.929 Mgm^–3, =1.11 mm^–1,R=3.96%,R _w =3.44% (605 reflections, 132 parameters). The ring systems together with the C atoms of the methyl groups in (M) and with the Cl atoms in (C) are planar and have D_3h-symmetry. Bond lengths and bond angles are discussed with regard to¹⁴N-NQR,³⁵Cl-NQR and vibrational spectroscopic data.

     

Komplexverbindungen von Germaniumsäure mit ÄDTE und ÄDTE-Analogen, 2. Mitt.: 1,2-Diaminopropan-N,N,N′,N′-tetraessigsäure; N-2-Hydroxyäthyl-1,2-diaminoäthan-N,N′,N′-triessigsäure

Zusammenfassung Feste 11-Komplexverbindungen von Germaniumsäure mit 1,2-Diaminopropan-N,N,N,N-tetraessigsäure und N-2-Hydroxyäthyl-1,2-diaminoäthan-N,N,N-triessigsäure werden dargestellt. Auf Grund von TG-, DTG-, DTA- sowie IR-spektroskopischen Untersuchungen wird ein Strukturvorschlag für die erhaltenen Verbindungen (GeY·2 H₂O, GeY, GeZ·H₂O, GeZ, GeX·H₂O, GeX ^*** abgeleitet.In wäßriger Lösung erweist sich GeZ·H₂O als einbasige Säure, H[Ge(OH)Z], mit einer DissoziationskonstanteK _c =3,15·10^–3 (pK _c =2,50±0,03) für 25° C, Ionenstärke 0,1m.Es werden die Stabilitätskonstanten der Komplexverbindungen H[Ge(OH)Z], [Ge(OH)Z]^– und GeX·H₂O in wäßriger Lösung bestimmt: (25° C, Ionenstärke 0,1 m).Mit 3 Abbildungen1. Mitt.:N. Konopik undP. Mészáros, Mh. Chem.99, 902 (1968).Auszugsweise vorgetragen auf der Jahrestagung des Vereines Österreichischer Chemiker am 5. Oktober 1967 in Wien. Vgl. Allgem. u. Prakt. Chemie18, 268 (1967).