ABSTRACT
Two subsets of data, corresponding to different crystalline modifications of the title compound, 5-oxatricyclo[5.1.0.0(1,3)]octane-4-one (C(7)H(8)O(2)), have been obtained from the same experiment. Both structures were successfully solved and refined. The packing of identical layers of molecules is different for monoclinic and orthorhombic forms.
ABSTRACT
Perspirocyclopropanated bicyclopropylidene (6) was prepared in three steps from 7-cyclopropylidenedispiro[2.0.2.1]heptane (4) (24% overall) or, more efficiently, through dehalogenative coupling of 7,7-dibromo[3]triangulane (15) (82%). This type of reductive dimerization turned out to be successful for the synthesis of (E)- and (Z)-bis(spiropentylidene) 14 (67%) and even of the "third-generation" spirocyclopropanated bicyclopropylidene 17 (17% overall from 15). Whereas the parent bicyclopropylidene 1 dimerized at 180 degrees C to yield [4]rotane, dimerization of 6 at 130 degrees C under 10 kbar pressure occured only with opening of one three-membered ring to yield the polyspirocyclopropanated (cyclopropylidene)cyclopentane derivative 19 (34% yield), and at the elevated temperature the polyspirocyclopropanated 2-cyclopropylidene[3.2.2]propellane derivative 20 (25 % yield). Perspirocyclopropanated bicyclopropylidene 6 and the "third-generation" bicyclopropylidene 17 gave addition of bromine, hydrogen bromide, and various dihalocarbenes without rearrangement. The functionally substituted branched [7]triangulane 28 and branched dichloro-C2v-[15]triangulane 32 were used to prepare the perspirocyclopropanated [3]rotane (D3h-[10]triangulane) 49 (six steps from 6, 1.4% overall yield) and the C2v-[15]triangulane 51 (two steps from 17, 41% overall). Upon catalytic hydrogenation, the perspirocyclopropanated bicyclopropylidene 6 yielded 7,7'-bis(dispiro[2.0.2.]-heptyl) (52) and, under more forcing conditions, 1,1'-bis(2,2,3,3-tetramethylcyclopropyl) (53). The bromofluorocarbene adduct 33 of 17 reacted with butyllithium to give the unexpected polyspirocyclopropanated 1,4-di-n-butyl-2-cyclopropylidenebicyclo[2.2.0]hexane derivative 37 as the main product (55% yield) along with the expected "third-generation" perspirocyclopropanated dicyclopropylidenemethane 38 (21% yield). Mechanistic aspects of this and the other unusual reactions are discussed. The structures of all new unusual hydrocarbons were proven by X-ray crystal structure analyses, and the most interesting structural and crystal packing features are presented.
ABSTRACT
The central three-membered ring in the title compound, trans-1,1',1"-cyclopropane-1,2,3-triyltris(cyclopropanol), C(12)H(18)O(3), shows pronounced asymmetry of the bond lengths, which is induced by the different orientations of the substituents. A network of hydrogen bonds links the molecules into sheets.
ABSTRACT
The crystal structure of poly[copper(II)-di-mu-hypophosphito-mu-urea], [Cu(H2PO2)2(CH4N2O)]n, has been determined at 293, 100 and 15 K. The geometry of the hypophosphite anion is very close to ideal, with point symmetry mm2. Each Cu atom lies on an inversion centre and is coordinated to six O atoms from four hypophosphite anions and two urea molecules, forming a tetragonal bipyramid. The unique urea molecule lies on a twofold axis. Each hypophosphite anion in the structure is coordinated to two Cu atoms. The hypophosphite anions, urea molecules and Cu(II) cations form polymeric ribbons. The Cu(II) cations in the ribbon are linked together by two hypophosphite anions and a urea molecule, which is coordinated to Cu via an O atom. The ribbons are linked to each other by N-H...O hydrogen bonds and form polymeric layers.
