Bis(triethylammonium) Bis(2-mercaptobenzoato-O,S)dioxomolybdate(VI)

Abstract

Anorg. Allg. Chem. 608, 100-114. CommentThe synthesis of the title compound, (I), was undertaken as part of our current research (Carrillo, Gouzerh & Jeannin, 1985;Bustos et al. 1991; Carrillo, Robert © 1995 , 1992; Debenjak, Bustos, Carrillo, Robert & Gouzerh, 1992a,b;Li-Kao, Bustos, Carrillo, Robert & Gouzerh, 1993). The purpose was to obtain a new precursor for the preparation of molybdenum complexes containing organo-dinitrogen ligands, for use as models of the postulated intermediates in the convertion of coordinated dinitrogen into ammonia (Henderson, Leigh & Picket, 1983;Leigh, 1992).The complex is dianionic in nature ( Fig. 1) and shows monomeric units composed of two mercaptobenzoate ligands coordinated to a cis-Mo02 core through atoms S1, $2, 03 and 05. The coordination sphere around the Mo vt ion is best described as a slightly distorted octahedron, where the basal plane is defined by Mo---O1 The apical sites are occupied by atoms S1 and $2 of the organic anion, 5 ° away from the vertical due to the strain imposed by the close chelate structure. The anion presents a non-crystallographic twofold axis which bisects the Ol~Mo---O2 and O3~Mo---05 angles. These structural characteristics are similar• cc,'~ c20 Fig. 1. View of the title molecule showing the atom-labelling scheme. Displacement ellipsoids are shown at the 40% probability level. H atoms are omitted for clarity, except for those involved in strong hydrogen bonds.to those found in closely related compounds, mainly in (NHn)2[MoO2{O2CC(S)Ph2}2].2H20 (Palanca et al., 1990). The structure is completed by two Et3NH ÷ cations, the geometry of which posed some problems in the early stages of refinement. A soft similarity restraint applied to the C---C and CmN bond lengths was enough to stabilize the convergence. The resulting geometry was fairly regular, showing a strong coupling to the anion through two rather short hydrogen-bonded contacts ( Fig. 1) (04...H1AmN1, estimated length/angle 1.86/~d175°; O6.--H2A~N2, estimated length/angle 1.80/~/171°), leading to somewhat independent neutral units connected to one another only through coulombian interactions (Fig. 2). ExperimentalThe title compound was prepared by reaction of 10 mmol 1.478 (9) CI0---CI 1 i.376 (9) N I---C!51.479(9) CI 1---C12 1.371 (10) N2--C211.477 (7) C12----C13 1.394 (9) N2---C231.481 (7) CI 3------CIA 1.403 (8) N2---C251.485 (8) C15---C16 1.505 (10) O3---CI 1.250 (7) C17---C18 1.514 (10) O4----CI 1.254 (7) Ci9---C20 1.502 (10) O5---C81.270 (7) C21----C22 1.506 (10) O6---C81.251 (7) C23----C24 1.505 (10) C 1----C21.499 (8) C25---C26 1.507 (10) The structure was solved through a combination of direct methods and difference Fourier synthesis using the

Biologically relevant O,S-donor compounds. Synthesis, molybdenum complexation and xanthine oxidase inhibition

“…around the Mo centers of both molecules A and B are comparable to values found for the related MoO 2 compounds [37][38][39][40][41]. Analysis of selected bond lengths and angles given in Table4…”

“…A search in the Cambridge Structural Database 35 revealed only five Mo(VI) dioxo compounds with two additional bidentate O,S-ligands and a similar core geometry (KELXII, LIMSEF, MIJCEN, MPTHMO, XAWDUV). [37][38][39][40][41] With the exception of the long Mo2-S4 distance (see Table 4), all other bond distances Mo2-S3, 2.4630(10) A ˚, is of the same order of magnitude as those reported for other thio complexes, 37-42 the Mo2-S4 bond distance, 2.7376(9) A ˚, is significantly longer. This bond elongation can be attributed to the strong trans effect of a terminal oxygen trans to a thiolate sulfur atom, as found for Mo=O24 and Mo-S4 (O21-Mo-S4, 165.34(9) • ).…”

Mercury(II) Complexes Containing the [Hg(L)2]2–, [Hg(L)(HL)]−, and [Hg(HL)2] Units [H2L = 3-(2-Chlorophenyl)-2-sulfanylpropenoic Acid]. Structural and Spectroscopic Effects of the Different Degrees of Ligand Protonation

“…The two chelate HgSCCO rings, which in this case make an angle between planes of 75.5(1)°, have a different planarity [HgS(1)C(12)C(11)O(11) (rms: 0.148) and HgS(2)C(22)C(21)O(21) (rms: 0.077)] and the angles with the corresponding Cl–C 6 H 4 plane are also different: 59.6(2)° in L 2– and 25.2(2)° in HL – . In the crystal, the triethylammonium cation, which has unremarkable parameters, is hydrogen bonded to the O atom of the carboxylate group through an N–H···O hydrogen bond [N(1)–H(1)···O(11): 0.91, 1.81. 2.718(7) Å, 177.8°], but this bond does not support the association, which is supported by an O–H···O hydrogen bond [O(22)–H(22)···O(12)#1: 0.82, 1.79, 2.597(6) Å, 169.4°; #1 = – x + 1/2, y + 1/2, – z + 1/2] between the COOH group of an [Hg(L)(HL)] anion and the COO – group of a neighbor.…”

(p-Cymene)thioglycollatoruthenium(II) dimer; a complex with an ambi-basic S,O-donor ligand

“…Mn(I)] oxidation states [3,4], as S-or O-bonded only or more commonly as S,O-bidentate chelating [1,2,[5][6][7]. Higher aggregates are possible through bridging via the S atom, or by it acting as a doubly monodentate ligand to two separate metal atoms [1][2][3][4][5].…”