The phenomenon of conglomerate crystallization. Part 50. The crystallization behavior of [trans-co(en)_2(no_2)_2]cio_4(I), meso-[co-trans-me-(n-me-ethylenediamine)_2-trans-(no_2)_2](II), k[trans-co(#beta#-alaninato)_2(no_2)_2](III) and the isolation

摘要

[trans-co(en)_2(no_2)_2]cio_4(I), crystallizes, at22degC, from a deionized water solution, as a racemate, in spacegroup P1 (no.2), with lattice constants: a=6.581(2)A,b=8.274(1)A, c=12.660(3)A, #alpha#=77.28(2)deg,#beta#=76.58(2)deg, #lambde#=75.20(2)deg; V=638.71;A~3 andd(calc;MW-=370.59, z=2)=1.927gcm~-3. A total of 2233 datawere collected over the range of 4deg <-2#theta#<-50deg; of these,1961(independent and with I>-3#sigma#(I)) were used in thestructural analysis. Data were corrected for absorption(#mu#=15.989cm~-1) and the relative transmission coefficientsranged from 1.6797 to 0.9874. The final R(F) residuals were,respectively, 0.0738 and 0.0763. Two half cations are located atinversion centers; the anions are in general positions.meso-[co-trans-me-(n-me-ethylenediamine)_2-trans-(no_2)_2](II) [(n-meen)=n-methylethylenediami-ne] crystallizes at22degC, from a deionized water solution in space grouppbca(no.61) with alttice constants: a=16.882(5)A, b=11.999(3)A,c=15.017(5)A; V=3039.72A~3 and d (calc; MW =398.64,z=8)=1.742gcm~-3. A total of 5281 data were collected over therange of 4deg <-2#theta#<-50deg; of these , 1779(independent andwith ) I>-2.5#sigma#(I) were used in the structural analysis. Datawere corrected for absorption(#mu#=13.501cm~-1) and thetransmission coefficients ranged from 0.7956 to 0.9947. The finalrefinement of the structure (anisotropic thermal parameters for thehvavy atoms; idealized hydrogens for the cation) are R(F)=0.045and R_w(F)=0.052. The –no_2 ligands are trans to one another inthe axial direction while the N-methyl groups are trans to oneanother across the basal plane. The cations are located in generalpositions and the torsional angles of the en rings are #delta#(n1-c1-c2-n2=52.0deg) and #delta#(n3-c1-c3-c4-c4=51.0deg), incontrast with those of (I) which are of opposite helical chirality.This compound is one of two trans –co(III)x_2 cations of whichwe are aware that, while sitting at a general position of the spacegroup, has two ethylenediamine rings of the same helical chirality.k[trans-co(#beta#-alaninato)_2(no_2)_2](III) obtained afterseveral batches of crystals of (iv) had separated from the motherliquor (see syntheses). (III) crystallizes at 22degC, in space groupc_c(no.9) with lattice constants: a=12.385(6)A, b=13.109(5)A,c=8.290(5)A, #beta#=115.19deg, V=1217.97A~3 andd(calc;MW-=366.22, z=4)=1.997gcm~-3. A total of 1238datawere collected over the range of 4deg <-2#theta#<-50deg; of these,1016 (independent and with I>-2.5#sigma#(I) ) were used in thestructural analysis. Data were corrected forabsorption(#mu#=17.90cm~-1) and the transmission coefficientsranged from 0.5322 to 0.6627. The final R(F) and R_W(F)residuals were, respectively 0.022. Solution of the structure, usingthe first batch of crystals, proved that the compound isolated wasthe (H_5O_2)~+ derivative (see below and Discussion). A alterbatch of crystals contained (III). We have previously observed theprecipitation of hydronium salts, trapped by amine carboxylatosalts of cobalt (see Discussion). The anions consist of two six –membered rings formed by the metal and two (o,n)-bound #beta#-alaninato ligands; and , both have chair conformations.(H_5O_2) [trans-co(#beta#-alaninato)_2(no_2)_2](IV) is thesubstance that first crystalized from an aqueous solution of (III)(see Experimental). It crystallizes, at 22degC, in space groupc_c(no.9)or c2/c (no.15) with lattice constants: a=12.389(39)A,b=13.120(11)A, c=8.299(9)A, #beta#=115.09(19)deg,V=1221.72A~3 and d(calc;MW-=364.15, z=4)=1.980gcm~-3. Anincomplete data set of 1592 reflections was collected over therange 4deg <-2#theta#<-50deg because the crystal decomposes inair due to rapid loss of water of crystallization, as shown bydifferential scanning calorimetry. 956 data were independent withI>-2.5#sigma#(I) and were used in the structural analysis. Datawere not corrected for absorption because of decomposition of thecrystal. The final R(F) and R_w(F) residuals were, respectively,0.1