Selen Bilge

Crystal Structure of 15,21‐Bis(diethoxyphosphinoyl)‐2,5,8‐trioxa‐16,20‐diazatricyclo‐ [20.4.0.09,14] hexacosa‐9,11,13,22,24,26(1)‐hexaene‐Ethylphosphonic Acid‐Water (1/1/1)

The title compound (C 31 H 55 N 2 O 13 P 3 ) crystallizes in the triclinic space group P1 with a=12.676(4) A, b=13.733(3)A, c=14.042(2)A, α=67.94(4)°, β=77.15(4)°, γ=61.95(4)°, V=1996.2(8)A 3 , Z=2, D x =1.259 g.cm -3 . The structure was solved by direct methods and refined by full-matrix least-squares method (R=0.055). The macrocyclic ligand is an 18-membered lariat ether containing two N and three etheral O atoms and two phosphonate side groups. The title compound consists of the macrocyclic ligand, one ethyl phosphonic acid and one water molecule, as a whole. In the macrocyclic ring, the mean N...O distance is 5.481(6) A. The relative macrocyclic inner hole size, estimated as twice the mean distance of the donor atoms from their centroid is approximately 2.29 A.

2,5,8-Trioxa-16,20-diazatricyclo[20.4.0.09,14]hexacosa-9,11,13,15,20,22,24,26-octaene

The title molecule, C 21 H 24 N 2 O 3 , an N 2 O 3 -type crown compound, is a crystallographically centrosymmetric multidentate Schiff base ligand containing two imine N and three ether O atoms. It has a short C=N imine bond length [1.254 (4) A] and a narrow C-NC angle [117.9 (3)°] compared with salicylaldimine and naphthaldimine Schiff bases.

5,6,7,8,9,10,11,12,18,19,21,22-Dodecahydro-8,9:18,19-dibenzo-1,4,7-trioxa-11,16-diazacyclononadeca-10,16-diene

The title compound, C 22 H 26 N 2 O 3 , is a 19-membered Schiff base crown ether ligand containing two imine-N and three etheral-O atoms. In the macrocyclic ring, the mean N...O distance is 6.248(3)A. The relative macrocyclic inner hole size, estimated as twice the mean distance of the donor atoms from their centroid is approximately 2.53 A. The mean C=N imine bond length [1.256(3) A] and C-N=C imine bond angle [117.8 (2)°] are smaller than the corresponding values in salicylaldimine and naphthaldimine Schiff base ligands.

Clathrate and channel inclusion systems co-exist in the crystal structure of a bis-C-pivot macrocycle (Z′ = 2)

15,22-Bis(dimethoxyphosphoryl)-2,5,8-trioxa-16,21-diazatricyclo [21.4.0.09,14] heptacosa-9,11,13,23,25,27(1)-hexaene (1c) crystallises from tetrahydrofuran/methanol (7 : 1) as an inclusion compound with one mole of each of the solvent species. The methanol occupies a clathrate inclusion site within a stacked column of host molecules, while the THF occupies channels which lie between the host columns, which are held rigidly apart by antiparallel N–H⋯OP hydrogen bonds. The marked pseudosymmetry of the crystal structure (Z′ = 2) arises because of the twisting of the host columns about their axes to reduce the channel volumes to fit THF. The phosphorylation reaction of imines used here has the potential to provide a supramolecular synthon of a predictable fixed orientation with respect to such a host molecule.

Syntheses, spectroscopic properties and stereochemistry of bis-C-pivot macrocycles with two dialkyl phosphonate groups.

Bis-C-pivot macrocycles containing dimethyl (1a, 2a) or diethyl phosphonate (1b, 2b) groups have been prepared by adding dimethyl or diethyl phosphite to two -CH=N bonds in corresponding dibenzo-bis-imino crown ethers (1 and 2). Bis-C-pivot macrocycles possess two equivalent stereogenic centres giving rise to diastereoisomers (meso and racemate). The structures were characterized by elemental analysis, FTIR, MS, TGA, DSC and NMR measurements. (1)H, (13)C and (31)P NMR assignments were made for the isolated meso form of compounds 2a and 2b and for the meso and racemic forms of compounds 1a and 1b by analysis of chemical shifts, signal intensities and splitting patterns and the DEPT and 2D HETCOR NMR techniques. Thermal analysis and (1)H NMR showed that the crystallised form of compound 1a contained an equimolar amount of water of crystallisation.

4,4,6,6-tetrachloro-2,2-(propylene-dioxydi-o-phenylenediimino)-2λ5, 4λ5, 6λ5-cyclo triphosphazene

The title compound, C(15)H(16)Cl(4)N(5)O(2)P(3), is a cyclophosphazenic lariat (PNP-pivot) ether with a spiro-cyclic 12-membered macrocyclic ligand containing two ether O and two N atoms; the phosphazene ring is nearly planar. In the macrocyclic ring, there is a four-center (trifurcate) N-H.O/N-H.N hydrogen bond. The relative inner-hole size of the macrocycle is estimated as approximately 0.95 A.

4,4,6,6-Tetrachloro-2,2-(propylenedioxydi-o-phenylenediimino)-2lambda5,4lambda5,6lambda5-cyclotriphosphazene.

The title compound, C(15)H(16)Cl(4)N(5)O(2)P(3), is a cyclophosphazenic lariat (PNP-pivot) ether with a spiro-cyclic 12-membered macrocyclic ligand containing two ether O and two N atoms; the phosphazene ring is nearly planar. In the macrocyclic ring, there is a four-center (trifurcate) N-H.O/N-H.N hydrogen bond. The relative inner-hole size of the macrocycle is estimated as approximately 0.95 A.

4,4,6,6-Tetra­chloro-2,2-(propyl­ene­dioxy­di-o-phenyl­enedi­imino)-2λ5,4λ5,6λ5-cyclotriphosphazene

The title compound, C(15)H(16)Cl(4)N(5)O(2)P(3), is a cyclophosphazenic lariat (PNP-pivot) ether with a spiro-cyclic 12-membered macrocyclic ligand containing two ether O and two N atoms; the phosphazene ring is nearly planar. In the macrocyclic ring, there is a four-center (trifurcate) N-H.O/N-H.N hydrogen bond. The relative inner-hole size of the macrocycle is estimated as approximately 0.95 A.