Volume 55, Issue 11

1 -Iodo-2,6-bis(4-methoxy-phenyl)benzene (BipapI) was prepared in a Grignard reaction from 4-bromo-anisol and 2,6-dibrom o-1 -iodo-benzene in tetrahydrofuran (61% yield). Treatment of BipapI with Az-butyllithium in hexane/diethylether gave the corresponding terphenyl-lithium compound BipapLi which crystallized as the dietherate in 83% yield. The structure of BipapLi • (OE 2 ) 2 has been determined by single crystal X-ray methods. The molecule is a monomer in the lattice, and the lithium atom is three-coordinate. Preparation of BipapLi in the presence of PbCl 2 in diethylether gave a green solution, from which yellow crystalline (n -Bu)(Bipap) 2 Pbl was isolated in 73% yield. In the crystal this triorganolead(IV) iodide is monomeric and has tetrahedrally four-coordinate lead atoms.

The reaction of equivalent quantities of (triphenylphosphine)gold chloride and silver fluoride in CH 2 Cl 2 /MeOH gives tris[(triphenylphosphine)gold(I)]oxonium dihydrogentrifluoride in good yield. This product is formed through the action of water in the reaction medium. Crystals of {[(Ph 3 P)Au) 3 O} - [H 2 F 3 ] - 1.5 CH 2 CI 2 (monoclinic, space group P2 1 /c, Z = 4) contain the cations as hexanuclear dimers with short intra- and intermolecular Au-Au contacts. The structural details are similar to those of related salts with different anions. The [H 2 F 3 P anion is V-shaped with one symmetrical and one unsymmetrical F-H-F hydrogen bond and is best described as an addition compound of an HF molecule and a [F-H-F] - anion. The results indicate a high affinity of H 2 O/OH - for (phosphine)gold fluorides and - by the same token - prove that tri(gold)oxonium cations are stable to anhydrous HF and F - anions. By contrast, hydrochloric acid is known to degrade {[(R 3 P)Au] 3 O} + affording (R 3 P)AuCl and water.

The crystal and molecular structures of the phosphinomethyl-substituted lithium cyclopentadienides [Li(tmeda)][R 2 PCMe 2 C 5 H 4 ], R = Ph (1), Me (2) (tmeda = N,N,N',N'-tetramethylethylenediamine) were determined as their tmeda adducts on the basis of low temperature single crystal X-ray diffraction. (Crystal data: 1: monoclinic, space group P2 1 /n, a = 8.511(5), b = 11.936(2), c = 24.20(1) Å, β = 90.02(3)°, Z = 4.2: monoclinic, space group P2 1 /n, a = 10.887(2), b = 13.326(2), c = 13.131(2) Å, β= 92.872(6)°, Z = 4). In both compounds lithium has a slightly distorted 17 coordination to the cyclopentadienide (Cp) ring. There are no interactions between lithium and the phosphine donors in the solid state as the phosphinomethyl substituents are oriented to the other side of the Cp ring for steric reasons. The isopropene-substituted lithium cyclopentadienide, which is formed as a by-product in the synthesis of phosphinomethyl cyclopentadienides containing a CMe 2 bridge, was also structurally characterized as its tmeda adduct [Li(tmeda)][H 2 C=CMeC 5 H 4 ] (3). (Crystal data: monoclinic, P2 1 /c, a = 8.00(2), b = 16.701(2), c = 11.942(6) Å, β= 112.68(7)°, Z = 4). As in 1 and 2, lithium is η 5 -coordinated to the Cp ring, and there is no interaction of the functional group (isopropene) with lithium.

The absolute configuration of the conformationally flexible six membered ring system 2-methyl- and 2,6-dimethyl-l,4-cyclohexanedione monoethylene acetal was determined by comparison of measured and calculated CD spectra. The rotational strengths were calculated by means of the CNDO/S-method assuming R at the stereogenic center. The results were compared with the predictions made by the octant rule. The enantiomerically pure material was synthesized via the corresponding SAMP- and RAMP-hydrazones.

N,N′-Tetramethyl-N″-p-chlorobenzoylphosphoryltriamide (I), N,N′-tetramethyl-N″-o-fluorobenzoylphosphoryltriamide (II) and their sodium salts were synthesized and characterized by means of IR and 1 H , 31 P NMR spectroscopy. The structures of both compounds were determined by X-ray diffraction (I triclinic, space group P1̄ with a = 12.073(2), b = 12.869(3), c = 12.854(4) Å, α = 56.93(2), β = 62.45(2), γ = 66.34(2)° V = 1453.7(6)Å 3 , ρ(caled.) = 1.324 mg/cm 3 , Z = 4 and R = 0.0545, wR2 = 0.1425; II monoclinic, space group P2(1)/n with a = 10.051(2), b = 13.093(2), c = 10.856(2) Å, β = 108.36(2)°, V = 1355.9(4) Å 3 , ρ(caled.) = 1.339 mg/cm 3 , Z = 4 and R = 0.0533, wR2 = 0.1263). In both structures the molecules are associated into dimers via hydrogen bonds formed by the phosphorylic oxygen atoms and hydrogen atoms of amide groups. In I the unit cell consists of two independent molecules connected into non-symmetric dimers, in II of centrosymmetric dimer molecules.

Crystals of nicinquinium chloride and bromide incorporate water molecules due to the im­ balance of hydrogen bond donors and acceptors. The resulting intermolecular hydrogen bond system indicates a better proton accepting ability of chloride ions than bromide ions. The chlo­ ride anions accept four hydrogen bonds in an almost tetrahedral arrangement whereas only two are formed with the bromide anions. As a consequence in the crystal structure of the chloride a three dimensional network of hydrogen bonds is formed, while in that of the bromide only chains of hydrogen bonded species exist. Both cations retain the absolute configuration of all asymmetric carbon atoms as compared with the absolute configuration of the parent cinchonine.

The ternary indides ScPtln, TbPtln, and HoPtln were synthesized by reaction of the elements in an arc-melting furnace and subsequent annealing for four weeks. ScPtln and HoPtln are reported here for the first time. The three indides crystallize with the hexagonal ZrNiAl structure, a ternary ordered version of the Fe 2 P type, space group P6̄2m. Single crystal X-ray data yielded a = 754.6(1), c = 348.31(8) pm, wR2 = 0.0390, 177 F 2 values for ScPtln, a = 759.3(1), c = 387.6(1) pm, wR2 = 0.0576, 183 F2 values for TbPtln, and a = 758.13(1), c = 381.62(1) pm, wR2 = 0.0530, 239 F2 values for HoPtln with 14 variable parameters for each refinement. Striking structural motifs of these intermetallics are short Pt-In distances (270 - 286 pm) within the three-dimensional [Ptln] polyanions which are composed of Pt(2)In 6 trigonal prisms and trigonal planar P t(l)In 3 units. The platinum-indium substructure of ScPtln is discussed in comparison with the various platinum-indium networks in the structures of Ptln 2 , Pt 3 In 7 , SrPtln, Sr2Pt 3 ln 4 , SrPtIn 2 , LaPtIn 3 , and PtIn 7 Fi 3 .

The first aryl derivatives of c/oso-hexahydrohexaborate are formed by reaction of [B 6 H 6 ] 2- with 1-bromo-4-nitrobenzene and 2-bromo-5-nitrotoluene in acetonitrile at 80 °C. Cs 2 [B 6 H 5 - (1,4-C 6 H 4 (NO 2 ))] and Cs 2 [B 6 H 5 (C 6 H 3 -1-(CH 3 )-5-(NO 2 ))] can be isolated by ion exchange chromatography on diethylaminoethyl (DEAE) cellulose. Further treatment with /V-chlorosuccinimide yields the perhalogenated derivative (CH 2 Py 2 )[B 6 Cl 5 (1,4-Ph(NO 2 ))]CH 3 CN which has been characterized by X-ray diffraction analysis (orthorhombic, space group P2( 2,2t, a = 9.810(4), b - 14.412(3), c - 18.586(9) A, Z = 4). The 11 B NMR spectra of all compounds are consistent with a monosubstituted B 6 -cluster. The IR and Raman spectra exhibit characteristic BB, BH, CH, CC and NO vibrations, respectively.

The tetrapodal pentaamine 2,6-C 5 H 3 N[CMe(CH 2 NH 2 ) 2 ] 2 (pyN 4 , 1) readily reacts with four equivalents of 2-hydroxyphenyl-substituted carbonyl compounds, such as (i) 2-hydroxybenzaldehyde, (ii) 2,4-dihydroxybenzaldehyde, (iii) 3,5-di-rm-butyl-2-hydroxybenzaldehyde, and (iv) 2-hydroxyacetophenone, to give the corresponding Schiff base derivatives with N N 4O .1 donor sets (i: 2; ii: 3, iii: 4; iv: 5). With ligand 5, two transition metal complexes (M = Ni 11 (6), Cu 11 (7)) have been isolated, which are dinuclear and contain square-planar M(N 2 O 2 ) units, linked by a pyridine-derived spacer whose nitrogen atom is uncoordinated. The reaction of 1 with ferrocenecarbaldehyde affords, under neutral conditions and irrespective of an excess of the aldehyde present, the bis(aminal) 8 as the major product, in which the two 1,3-propylenediamine subunits of 1 have condensed with two carbaldehyde moieties to give two 1,3-diazacyclohexane rings. All compounds have been characterised by IR spectroscopy and elemental analysis, as well as 1 H and 13 C NMR spectroscopy (except paramagnetic 7). The crystal structures of compounds 2, 6, 7, and 8 have been determined.

Lipophilically wrapped polyion-aggregates of alkali salts are fascinating examples of selforganisation, which stimulate the design of novel ligands. Phenylene-1,4-bis(4-nitrophenylsulfonamide),. selected and structurally characterized, can be deprotonated by [NaH] ∞ in THF to its dianion. Recrystallisation from methanol solution however, does not yield the polyion aggregate expected, but a disodium(tetramethanol-dihydrate) salt, for which a structure determination proves an intriguing three-dimensional network of Na ⊕ ···O contacts to sulfonamide as well as nitro substituents and the small solvent molecules methanol as well as water. Ligand comparison between polyioncluster-forming tetraphenylimidodiphosphate and the title phenylene- 1,4-bis(4-nitrophenylsulfonamide) allows to specify the ligand properties necessary for the self-aggregation of alkali salts.

Di(arylsulfonyl)amides are presented as novel anionic ligands for polycation aggregates. Starting from the structures of Ag ⊕ and Na ⊕ salts registered in the Cambridge Structural Database, the largest alkali cation Cs ⊕ with high coordination number has been selected and in extreme low gradient crystallisation single crystals of both cesium-di(benzenesulfonyl)amide and cesium-di(4-toluenesulfonyl)amide were grown. Their structure determinations revealed that both polymeric salts contain cation layers (Cs ⊕ ) ∝ : The one lipophilically wrapped by di(benzenesulfonyl)amide ligands exhibits hexagonal (Cs ⊕ )6 subunits, whereas the methylsubstituted di(4-toluenesulfonyl)amide ligands of the other one are interspersed within (Cs ⊕ )^ layers. The resulting lipophilically wrapped sheets with Cs ⊕ cations of ten- and twelve-fold coordination to disulfonyl O and C centers vary in their overall thickness of 1.77 nm and 1.39 nm because the toluene substituents in the thinner one are tilted. The remarkable effects caused by the 4-methyl substitution of the phenyl rings determine the structures of the parent di(arylsulfonyl)amines as well: Contrary to the polymeric phenyl substituted derivative, the toluene homologue crystallizes in dimers. The single crystals grown of the closely related di(arylsulfonyl)amides with or without para methyl substituents and their poly(Cs ⊕ ) aggregates without any solvent inclusion show hitherto unknown structural motifs and, therefore, further improve our knowledge of alkali salt self-organisation phenomena in crystals.

[Cu 4 (L) 2 (O 2 CMe) 2 ] H 2 O (L = 1,3-bis(5-bromo-2-hydroxybenzylidene)propan-2-ol) was synthesized and its crystal structure determined. (C 38 H 34 N 4 O 10 Br 4 Cu 4 )·H 2 O, monoclinic, space group P2 1 /c, a = 21.072(5), b = 9.673(2), c = 21.934(4) Å, β = 109.73(2)°, V = 4208(2) Å 3 , Z = 4. The crystal structure consists of two independent binuclear copper(II) complexes and the non-coordinating water molecule in the asymetric unit. The Cu(II) ions are in a square-planar geometry and coordinated by donor atoms of the ligand (NO 3 ). The average Cu···Cu distance and average Cu-O-Cu angle are 3.491(2) Å and 132.0(1)°, respectively. Temperature-dependent magnetic susceptibility measurements of the complex show an intramolecular anti ferromagnetic coupling in the dimeric Cu(II) core. The fitting parameters are -2J = 174.4 cm -1 , g = 1.98.

Template reaction of L-3-acetyl-1-phenyl-5-isopropyl-4,5-dihydro-1,2,4-triazin-6-one (lb) with 1,3-diaminopropane and nickel acetate gave the corresponding chiral complex 4 in high yield. X-ray structure determination showed that the nickel complex is square planar, and the ligand N,N’-bis[(l-phenyl-5-isopropyl-4,5-dihydro-6-oxo-1,2,4-triazin-3-yl)ethylid-ene]- propane-1,3-diamine is of tetra-aza type where the imine nitrogens and the ring HN(4) nitrogens are the coordinating sites. MS-FAB and NMR spectral data are in agreement with the X-ray structure.

X-ray crystal structure data for the substituted 5-(2,3-dihydro-7-benzofuryl)-2-methylpyrazolo[ 4,3-d]pyrimidin-7-one (3) reveal that the two bicyclic heteroaryl systems show no coplanarity along their joint C (5) - C (11) axis with an interplanar angle of 9.6°. Nonetheless, the spatial interatomic distance for O(17)-N(6), determined as 2.73 A, allows the formation of a relatively weak intramolecular hydrogen bond between the pyrimidinone N(6)-H and the O(17) lone pair of the dihydrobenzofuryl moiety.

A series of (bis-2,3-naphthalenediyl)orthoborate salts of Cinchona alkaloids has been synthesized and characterized. The interactions between ions in the salts have been studied by means of circular dichroism spectroscopy and X-ray crystal structure determination. The CD spectra of the dihydroquinidine salt show that in non-polar solvents it exists as a tightly held ion pair. The crystal structure of the cinchonidine salt proves the existence of ions in the solid state. The protonation takes place at the quinuclidine nitrogen atom. The hydrogen bonds connect cation and anion into one recognizable unit. Additional hydrogen bonds (with hydroxy group as a hydrogen donor and quinoline nitrogen atom as an acceptor) form infinite chains of cations along the [001] direction. There are cavities in the crystal structure that are partially filled by solvent molecules (acetone).

The X-ray crystal structure determination of 4-(4'-fluorophenyl)hexahydro-1H,3H-pyrido[ 1,2-c]pyrimidine-1,3-dione (5) and 4-(4'-chlorophenyl)hexahydro-1H,3H-pyrido [1,2-c]- pyrimidine-1,3-dione (8) is reported. The crystal structures show the formation of centrosymmetric dimers via intermolecular N-H···O hydrogen bonds. The saturated ring adopts a slightly distorted sofa conformation both in 5 and in 8. In either compound the planar phenyl ring is twisted with respect to the pyrimidine-1,3-dione fragment.

Reaction of [MI 2 (CO)(NCMe)(η 2 -EtC 2 Et) 2 ] (M = Mo,W) with one equivalent of 2,2' -bipyridine (bipy) in CH 2 C 12 at room temperature gives either the neutral complex, [MoI 2 (CO)(bipy)- (η 2 -EtC2Et)] (1) or the cationic complex, [WI(CO)(bipy)(η 2 -EtC 2 Et) 2 ]I (2). The neutral molybdenum complex 1, has been crystallographically characterised, and has a pseudo-octahedral geometry with the iodo-ligand trans to the 3-hexyne, and with the bipy, carbon monoxide and other iodo-ligand occupying the equatorial face. 13 C NMR studies show the 3-hexyne is donating four electrons to the molybdenum in 1.

Reaction of tetramethylcyclopentenone and cyclopentadienyl anion gave the title pentafulvalene derivative. Its deprotonation with sodium or potassium hydride proceeded selectively at one of the methyl groups. The resulting 3,4-dihydro-1,3,4-trimethyl(2-methylene)pentafulvalenide ion was converted to the corresponding ferrocene which was obtained as two diasteroisomers in the ratio of 1/1.