Structural systematics of rare earth complexes. XIV - Hydrated 1 : 1 adducts of lanthanoid(III) nitrates with 2,2 :: 6 :,2 ''-terpyridine

Room-temperature single-crystal X-ray structure determinations are recorded for (hydrated) lanthanoid(III) nitrate/2,2':6',2 "-terpyridine ('tpy') (1 : 1) complexes; all are of the form Ln(NO3)(3)/tpy/H2O(1 : 1 :x), [(tpy)Ln( O2NO)(2)(OH2)(y)](NO3)(.z H2O), and form two series of compounds. For Ln = La(-)Gd, the complexes are [(tpy)Ln(O2NO)(2)(OH2)(3)](NO3), the lanthanoid atom being ten-coordinate; crystals are triclinic, <P(1)over bar>, a approx imate to 11.8, b approximate to 11.3, c approximate to 8.9 Angstrom, alpha approximate to 75, beta approximate to 69, gamma approximate to 89 degrees, Z = 2 f.u., conventional R on \F\ 0.045, 0.062 for N-o 4513, 2710 independ ent 'observed' (I > 3 sigma(I)) diffractometer reflections for Ln = La, Gd respectively. For Ln = Tb(-)Lu, a different form is found: monoclinic, P 2( 1)/c, a approximate to 8.8, b approximate to 11.5, c approximate to 23.8 An gstrom, beta approximate to 111 degrees, Z = 4, R 0.055, 0.037, 0.056 for N -o 2427, 3079, 1857 for Ln = Tb, Lu, Y respectively, the form of the comple x being [(tpy)Ln(O2NO)(2)(OH2)(2)](NO3).2H(2)O, with nine-coordinate lantha noid. Crystallization of the Ln = La adduct from methanol yields an adduct of La(NO3)(3)/tpy/MeOH (1 : 1 : 2) [(tpy)La(O2NO)(3)(HOMe)(2)] stoichiometr y with 11-coordinate lanthanum. Crystals are triclinic, <P(1)over bar>, a 1 2.361(2), b 12.244(3), c 7.753(2) Angstrom, alpha 96.56(2), beta 103.22(2), gamma 91.16(2)degrees, Z = 2, R 0.037 for N-o 6597.