The open-chain bis-imino podans (1 and 2) and C-bis-pivot podands (5 and 6), bis-imino crown ethers (3 and 4) and C-bispivot lariat ethers (7 and 8) have been synthesized. The crystal structure of (7) has been determined which contains two moles of water molecules. Compound (7) crystallizes in the triclinic space group PĪ with a = 10.418(2), b = 12.914(2), c = 13.075(3) Å, α = 63.6(2), β = 75.5(2), γ = 78.8(2)°, V = 1518.0(5) Å3, Z = 2 and Dcalc = 1.266 g cm-3. The relative macrocyclic inner hole size, estimated as twice the mean distance of the donor atoms from their centroid is approximately 2.18 Å. In the new C-bis-pivot podands (5 and 6) and C-bis-pivot lariat ether (7), the phosphorus atoms are bonded to carbon atoms directly, and both of the phosphite groups are partially hydrolized. The sailent features of IR, 1H, 13C-, 31P-NMR, HETCOR and MS spectral data of the compounds have been discussed. © 2002 Elsevier Science B.V. All rights reserved.