The phenomenon of conglomerate crystallization part 51. The crystallization behavior of nickel dinitro amine complexes. Trans-[Ni(3,2,3-tet) (NO 2) 2]·H 2O ( I), mer-[Ni(N5-Me-1,5,9-triazanonane) (NO 2) 2 ( II), cis-[Ni(tren) (NO 2) 2]·H 2O ( III) and cis-[Ni(edda) (H 2O) 2]·H 2O ( IV) and control of the bonding mode of the nitrite ligand by the choice of the amine

Abstract

Trans-[Ni(3,2,3-tet)(NO 2) 2]·H 2)O ( I) (3,2,3-tet=1,5,8,12-tetraazadodecane), NiO 5N 6C 8H 24, crystallizes at 5°C, from a deionized water solution, as a racemate, space group P2 1/ n (No. 14) with lattice constants: a=13.694(4), b=6.826(3), c=16.470(4) Å, β=108.80(2)° V=1485.80 Å 3 and D cale=1.533 g cm −4 (MW=343.01, Z=4 ). A total of 2699 data was collected over the range of 4⩽2 φ⩽50°: of these, 1613 (independent and with I⩾2.5 σ( l)) were used in the structural analysis. Data were corrected for absorption ( μ=13.2 cm −1) and the relative transmission coefficients ranged from 0.5452 to 0.7094. The final R( F) and ( R w( F) residuals were, respectively 0.041 and 0.049. The molecule contains two trans, N-bound -NO 2 ligands with the tetraamine nitrogens occupying the basal plane. Mer-[Ni(N5-Me-1,5,9-triazanonane)(NO 2) 2] ( II), NiO 4N 5C 7H 19, crystallizes at 5°C, from a deionized water solution in space group P2 1/ m (No. 11) with lattice constants: a=7.250(4), b=22.749(8), c=11.068(7) A ̊ , β=104.00(5)°; V=1486.68 A ̊ 2 and D cale =1.983 g cm −3 MW=295.95, Z=6 ). A total of 4547 data was collected over the range of 4⩽2 φ⩽60°; of these 2820 (independent and with 1⩾2.5 σ( I) were used in the structural analysis. Data were corrected for absorption ( μ=11.02 cm −1) and the transmission coefficients ranged from 0.5108 to 0.7810. The final refinement of the structure are R( F)=0.040 and R w( F)=0.045. The lattice contains one molecule at a general position and another one at a mirror plane. The -NO 2 ligands occupy three mer positions, one N-bound and the second is a bidentate (O,O)-bound ligand. The N-methyl amine occupies the other three mer positions of the octahedron. Cis-[Ni(tren)(NO 2) 2]·2H 2O ( III) (tren=tris-[2-ethylamine) amine] NiO 6N 6C 6H 20, crystallizes at 5°C, from a deionized water solution, as a racemate, space group Cc (No.9) with lattice constants: a=9.848(6), b=11.739(5), c=12.283(6) A ̊ , β=97.47(4)°, V=1407.89 A ̊ 3 and D cale =1.567 g cm −3 ( MW=330.95, Z=4 ). A total of 2205 data was collected over the range of 4⩽2 φ⩽60°; of these, 1292 were unique and of those 896 (independent and with 1 2 .5σ(I) ) were used in th structural analysis. The absorption coefficient is 14.10 cm −1 and the relative transmission coefficients ranged from 0.5645 to 0.7632. The final R( F) and R w( F) residuals were, respectively 0.044 and 0.051. The molecule contains two cis, N-bound-NO 2 ligands with the tetraamine nitrogens occupying the other four octahedral sites. There are two lattice waters of crystallization. Cis-[Ni(edda)(H 2O) 2]·H 2O ( IV) (edda= N, N′-ethylenediaminediacetate) NiO 5 N 2 C 6 H 108 crystallizes at 5°C, from a deionized water solution, as a racemate, space group C2/ c (No. 15) with lattice constants: a=20.286(2), b=7.7696(7), c=14.056(1) A ̊ , β=94.327(8)°, V=2209.1 A ̊ 3 and D cale =1.725 g cm −3 ( MW=286.91, Z=8 ), A total of 3557 data was collected over the range of 4⩽2 φ⩽44°: of these, 2635 (independent and with I⩾1.0 σ( I)) were used in the structural analysis. Data were corrected for absorption ( μ=17.85 cm −1) and the relative transmission coefficients ranged from 0.8864 to 0.9993. The final R( F) and R w( F) residuals were, respectively 0.025 and 0.031. The molecule contains two cis water ligands and a cis-α bonded edda tetradentate ligand, with amino nitrogens trans to the water ligands, while the carboxylato oxygens are located in the trans-axial positions.