Tetracoordinated phosphorus atoms in derivatives of cyclophosphazenes are pentavalent and are potentially chiral. Chirality does not seem to have been investigated nor discussed for any literature examples of crystal structures of those cyclophosphazene compounds which are expected to be chiral. In cyclotriphosphazatriene compounds with ansa-substituted macrocyclic rings the two phosphorus atoms attached to the macrocycle are chiral, although the cis-ansa cyclotriphosphazatriene-macrocycle 1 is the meso form. Reaction of 1 with the di-secondary amine, piperazine, provides a convenient way to investigate the chiral configurational properties of cyclophosphazene compounds. It is found by X-ray crystallography that there are two configurational isomers (one meso and one racemate) of the singly bridged di(cyclophosphazene-macrocyclic) piperazine derivative 6i, and that there are two configurational isomers (both meso) of the doubly bridged di(cyclophosphazene-macrocyclic) piperazine derivative 8i; in 8i one meso form has a center of symmetry and the other a plane of symmetry. The chiral configurational properties of each stage of the reaction scheme for formation of 6i and 8i from 1 have been confirmed by P-31 NMR spectroscopy and the results are consistent with inversion of configuration at phosphorus at each step of the reaction of >P(OR)Cl groups with HNR'R" to form >P(OR)(NR'R") derivatives: viz. reaction of 1 with piperazine gives the monosubstituted compound 4i, which exists as a racemate with the macrocyclic ring in the trans-configuration; reaction of compound 4i with 1 gives the two configurational forms (meso and racemate) of the singly bridged derivative 6i with the macrocyclic rings in the trans-trans configuration; reaction of 6i with piperazine gives the monosubstituted singly bridged derivative 7i. which exists as two racemic mixtures with the macrocyclic rings in cis-trans configurations; and intramolecular condensation of 7i gives the two configurational forms of the doubly bridged derivative 8i with each of the macrocyclic rings in the cis-cis configuration. In this work the configurational properties of derivatives of cyclotriphosphazatriene rings with two (one N3P3 unit) or four (two N3P3 units) chiral centers have been rationalized. It is found that the chiral structures of cyclotriphosphazatriene derivatives may be represented by 2D molecular diagrams, as long as the Fischer rules for chiral carbon compounds are followed for phosphorus compounds.