SYNTHESIS AND STRUCTURAL SYSTEMATICS OF NITROGEN BASE ADDUCTS OF GROUP-2 SALTS .5. SOME COMPLEXES WITH 3-AZAPENTANE-1,5-DIAMINE

Syntheses and room-temperature single-crystal X-ray structural charact erizations are recorded for an array of adducts of H2N(CN2)(2)NH(CH2)( 2)NH2, 'dien', with salts of Group 2 elements, MX(2).n(dien). [Mg(dien )(2)]Cl-2 (1) is monoclinic, P2(1)/c, a 11.326(6), b 10.928(5), c 12.6 36(6) Angstrom, beta 92.74(4)degrees, Z = 4 f.u.; R was 0.047 for N-o 1726 independent 'observed' (I > 3 sigma(I)) diffractometer reflection s. [Mg(dien)(2)]Br-2 (2) is monoclinic, P2(1)/c, a 9.541(7), b 14.55(1 ), c 11.894(8) Angstrom, beta 100.42(5)degrees, Z=4 f.u., R 0.054 for N-o 1778. [Mg(dien)(2)]I-2 (3) is isomorphous, a 9.969(2), b 14.907(2) , c 12.300(3) Angstrom, beta 100.02(2)degrees, R 0.039 for N-o 3180. I n all three complexes, the two tridentate ligands are disposed mer in a six-coordinate MgN6 environment, the trans Mg-N(central) distances b eing somewhat shorter (2.161(4)-2.181(9) Angstrom) than Mg-N(distal) ( 2.215(8)-2.249(4) Angstrom). [Ba(dien)(3)] Cl-2 (4a) is orthorhombic, Pnaa, a 19.309(2), b 13.545(2), c 8.872(2) Angstrom, Z=4 f.u., R 0.055 for N-o 1070; the methanol disolvate (4b) is monoclinic, P2(1)/c, a 1 6.807(8), b 8.764(5), c 19.493(4) Angstrom, beta 102.39(3)degrees, Z=4 f.u., R 0.11 for N-o 2613. A family of derivative structures (5)-(8), [M(dien)(3)] X(2), M, X = Sr, Br (5), Sr, I (6), Ba, Br (7), Ba, I (8 ), have cells of half the volume (a approximate to 13.8, b approximate to 9, c approximate to 9.8 Angstrom), probable space group P2(1)2(1)2 , R 0.050, 0.061, 0.034, 0.037 for N-o 549, 914, 1044, 1801 respective ly, with the cations disposed about crystallographic 2 axes with one d isordered ligand. [Ba(dien)(3)] (ClO4)(2) (9) is rhombohedral, R(3) ov er barc$, a 10.240(2), c 45.19(1) Angstrom (hexagonal setting), Z = 6 f.u., R 0.054 for N-o 508. Like (4)-(8), the barium environment is nin e-coordinate with the three tridentate ligands here disposed about a 3 axis through the metal.