The reaction of molybdenum(VI) oxide with oxalic acid and RCl where R=NH
4 (
1) and (C
6H
5)
4P (
2), results in the formation of molybdenum(VI) oxalate complexes of the general formula R
2Mo
2O
5(C
...2O
4)
2(H
2O)
2. As determined by X-ray structure analysis both salts are built up of the dimeric anions containing Mo
2O
5 core. Molybdenum atoms exhibit distorted octahedral coordination. Whereas in the ammonium salt the MoOMo bridge is linear, the one in the corresponding tetraphenylphosphonium salt is angular with an angle of 162.42(15)° at the oxygen atom. This angular structure of
2 is also caused by additional strong intramolecular hydrogen bonds (2.719(4) and 2.661(4) Å) between coordinated water molecules and oxalato-oxygens. Both complexes were characterized by chemical analysis, thermogravimetry, UV and IR spectroscopy as well as by conductivity measurements.
(PyH)
2MoOCl
5 reacts with methanol and pyridine or 4-methylpyridine to give neutral oxomolybdenum(V) and oxomolybdenum(V,VI) clusters built of Mo
2O
4
2+
units, i.e. tetranuclear Mo
4O
8(OCH
3)
2Cl
...2Py
4·2Py (Py=pyridine (C
5H
5N)) (
i), Mo
4O
8(OCH
3)
2Cl
2(4-MePy)
4·2(4-MePy) (4-MePy=4-methylpyridine (C
6H
7N)) (
ii), Mo
4O
8(OCH
3)
4(4-MePy)
4 (
iii), hexanuclear Mo
6O
12(OCH
3)
6Py
4 (
iv) and decanuclear Mo
10O
26Py
8·7Py (
v). It was shown by the X-ray structure analysis that
i and
iii contain the same Mo
4O
4(μ
2-O)
2(μ
3-O)
2(μ
2-OCH
3)
2
2+ core to which different peripheral ligands are attached. The structure of
ii is analogous to that of
i, based on the similarity of infrared and far infrared spectra. Molecules of
iv were shown to contain a planar arrangement of six molybdenum atoms linked together by oxo and methoxo bridging groups. The X-ray structure analysis of
v revealed the presence of molybdenum(V) and molybdenum(VI) atoms. Neutral, decanuclear molecules of
v are built of four Mo
2O
4
2+
units which are connected with two molybdenum(VI) centres.
The title compound, Ta6Br12(H2O)6(Br0.4Cl1.6)·8H2O, crystallizes in space group P. The structure contains two crystallographically independent Ta6Br12(H2O)62+ cluster cations forming distinct layers ...parallel to the ab plane. The compound is isoconfigurational with the double salts Ta6Br12(H2O)6X2·trans‐Ta6Br12(OH)4(H2O)2·18H2O (X = Cl, Br).
Indazolium (OC‐6‐11)‐tetrachlorobis(indazole) ruthenate(III), HInd (OC‐6‐11)‐RuCl4ind2, exhibits excellent results in different tumor models in vitro and in vivo. Substitution reactions of this ...ruthenium(III) complex are of special interest for a deeper understanding of its interactions with biologically occurring targets and its mode of action. The indazolium complex salt can be transformed to the neutral, meridionally configurated trisindazole complex (OC‐6‐21)‐RuCl3ind3 in solvents like tetrahydrofuran. The X‐ray crystal structure of this complex could be solved (monoclinic space group P2(1)/n, a = 12.441(3), b = 10.415(3), c = 21.635(4) Å, β = 105.02(1)°). In spite of the paramagnetic RuIII atom most of the coordinated indazole protons could be assigned with the help of two‐dimensional NMR experiments. Additionally, a reduced reaction product of HInd (OC‐6‐11)‐RuCl4ind2 in the physiological solubilizer 2‐pyrrolidone could be isolated and the X‐ray crystal structure of this RuII complex, (OC‐6‐12)‐RuCl2ind4, crystallized with two 2‐pyrrolidones, could be solved (monoclinic space group P2(1)/n, a = 12.139(2), b = 10.426(2), c = 14.426(3) Å, β = 100.06(3)°).
RuCl3ind3 und RuCl2ind4: Zwei neue aus der tumorhemmenden RuIII‐Verbindung HInd (OC‐6‐11)‐RuCl4ind2 erhaltene Rutheniumkomplexe (ind = Indazol)
Indazolium (OC‐6‐11)‐Tetrachlorobis(indazol)ruthenat(III), HInd (OC‐6‐11)‐RuCl4ind2, zeigt ausgezeichnete Ergebnisse in unterschiedlichen Tumormodellen in vitro und in vivo. Substitutionsreaktionen dieses Ruthenium(III)‐Komplexes sind zum besseren Verständnis seines Wirkmechanismus, insbesondere der Wechselwirkung mit biologisch relevanten Molekülen, von großem Interesse. Das Indazolium Komplexsalz kann in Lösungsmitteln wie Tetrahydrofuran in den meridional konfigurierten Trisindazolkomplex (OC‐6‐21)‐RuCl3ind3 überführt werden. Die Kristallstruktur dieses RuIII‐Komplexes konnte gelöst werden (monokline Raumgruppe, P2(1)/n, a = 12.441(3), b = 10.415(3), c = 21.635(4) Å, β = 105.02(1)°). Trotz des paramagnetischen RuIII‐Atoms konnten die Protonen des koordinierten Indazols mit Hilfe zweidimensionaler NMR‐Experimente größtenteils zugeordnet werden. Darüber hinaus konnte ein reduziertes Reaktionsprodukt von HInd (OC‐6‐11)‐RuCl4ind2 im physiologischen Lösevermittler 2‐Pyrrolidon isoliert und die Kristallstruktur dieses RuII‐Komplexes, (OC‐6‐12)‐RuCl2ind4, kristallisiert mit zwei Molekülen 2‐Pyrrolidon, gelöst werden (monokline Raumgruppe, P2(1)/n, a = 12.139(2), b = 10.426(2), c = 14.426(3) Å, β = 100.06(3)°).
In the crystal structure of the title complex, Co(C6H8N3S)3, the CoIII atom is octahedrally coordinated by three monodeprotonated bidentate 3,5‐dimethyl‐1H‐pyrazole‐1‐thiocarboxamide ligands with ...two thiocarboxamide N atoms in axial positions. The asymmetric unit contains two molecules (A and B) and these molecules are arranged in chains in an alternating fashion connected by N—H⋯S interactions.
In the title compound, C13H13N5O4·H2O (4,5′‐cyclowyosine·H2O), the cyclization forces a syn arrangement of the aglycon with respect to the sugar moiety. The ribofuranose part of the molecule ...displays a β‐d configuration with an envelope C1′‐endo pucker. The molecules are arranged in columns along the short a axis and are linked to water molecules through O—H⋯O and O—H⋯N hydrogen bonds.
