THE PHENOMENON OF CONGLOMERATE CRYSTALLIZATION. PART 47. COUNTERION CONTROL OF THE CRYSTALLIZATION PATHWAY. PART 8. THE CRYSTALLIZATION BEHAVIOR OF [trans-Co(3, 2, 3-tet)(NO2)2] CLO4 (I), trans-Co(3, 2, 3-tet)(NO2)2] BR · 3H2O (II) AND [trans-Co(3, 2, 3-tet)(NO2)2]I (III)

Abstract

[trans-Co(3,2,3-tet)(NO2)2]ClO4 (I, CoClO8H6C8H22, crystallizes, at 22°C, from a deionized water solution in space group P21/n (a variant of No. 14), with lattice constants: a=10.782(3), b=9.198(3), c=17.031(5) Å, β=105.30(2)°; V=1629.14 Å3 and d(calc; MW=424.69, Z=4)=1.731 g-cm−3. A total of 3217 data were collected over the range of 4° ≤ 2θ ≤ 50°; of these, 2393 (independent and with I ≥ (2.5σ(I)) were used in the structural analysis. Data were corrected for absorption (μ=12.70 cm−1) and the transmission coefficients ranged from 0.9163 to 0.9965. The final R(F) and Rw(F) residuals were, respectively 0.043 and 0.045. The cations exist in the lattice as enantiomeric pairs and the conformation of the central, five-membered ring for the molecule described here is δ(N2-C4-C5-N3=+49.0°). The secondary nitrogens are both R(or S). The ClO4 − anion forms O…H bonds with a hydrogen of each of the two terminal -NH2 groups, thus rendering those hydrogens different and the terminal nitrogens chiral. In the cation we used as the asymmetric unit, they are both R. [trans-Co(3,2,3-tet)(NO2)2]Br · 3H2O (II), BrCoO7N6C8H28, crystallizes at 22°C, from a deionized water solution in space group P212121 (No. 19) with lattice constants: a=18.352(10), b=14.757(8), c=6.497(2) Å; V=1759.46 Å and d(calc; MW=459.19, Z=4)=1.733 g-cm−3. A total of 2917 data were collected over the range of 4° ≤ 2θ ≤ 60°; of these, 2175 (independent and with I ≥ 2.5σ(I)) were used in the structural analysis. Data were corrected for absorption (μ=32.918 cm−1) and the transmission coefficients ranged from 0.3266 to 0.4783. The final R(F) and Rw(F) residuals were, respectively 0.056 and 0.061. The cations exist in the lattice pure enantiomers and the conformation of the central ring for the molecule described here is δ(N2-C4-C5-N3=47.9°). The chiral, secondary nitrogens are both R. [trans-Co(3,2,3-tet)(NO2)2]I (III), ICoO4N6C8H22, crystallizes in total darkness, at 22°C, from a deionized water solution in space group P21 or P21/m with lattice constants: a=6.451(6)(3), b=15.253(18), c=7.859(9) Å, β=97.58(8)°; V=766.59 Å3 and d/(calc; MW=452.138, Z=2)=1.959 g-cm−3. A total of 1720 data were collected over the range of 4° ≤ 2θ ≤ 60°; of these, 292 (independent and with I ≥ 2.5σ(I)) were used in the structural analysis. Data were corrected for absorption (μ=31.306 cm−1) and the transmission coefficients ranged from 0.1983 to 0.5039. The quality of the crystal was so poor that only 17% of the collected data had I ≥ 2.5σ(I); therefore, data processing was abandoned.