The phenol-based macrocyclic ligands (L
2,3)
2- and (L
2,4)
2-, derived from the [2:1:1] condensation of 2,6-diformyl-4-methylphenol, ethylenediamine, and 1,3-trimethylenediamine or 1,4-tetramethylenediamine, have a salen-likemetal-binding site (salen =
N,
N'-ethylenedisalicylideneaminate) and a saltn- or salbn-like metal-binding site (saltn=
N,
N'-trimethylenedisalicylideneaminate, salbn =
N,
N'-tetramethylenedisalicylideneaminate) sharing the phenolicm
oieties. They form the (
![](/images/entities/mgr.gif)
-phenoxo)
2Co
IIM
II complexes [CoMn(L
2,3)(AcO)]ClO
4·DMF (
1), [CoMn(L
2,4)(AcO)]ClO
4 (
2), [CoCo(L
2,3)(AcO)]ClO
4 (
3), [CoCo(L
2,4)(AcO)]ClO
4 (
4), [CoZn(L
2,3)(AcO)]ClO
4 (
5), and [CoZn(L
2,4)(AcO)]ClO
4 (
6). Complex
1 crystallizes in the monoclinic space group
P2
1/
c, with
a = 10.027(3) Å,
b = 11.713(3)Å,
c = 26.821(9) Å,
![](/images/gifchars/beta2.gif)
= 93.85(2)
![](/images/entities/deg.gif)
,
V = 3142(1) Å
3, and
Z = 4. The Co and Mn ions are bridged by the twophenolic oxygens of the macrocycle and an acetate group in the syn-syn mode. The Co
II in the salen site is oflow-spin and assumes a square-pyramidal geometry with an acetate oxygen at the axial site. The Mn
II has a cissix-coordinate geometry with respect to the acetate oxygen and the DMF oxygen. The Mn is displaced 0.955 Åfrom the basal N
2O
2 least-squares plane. [CoMn(L
2,4)(AcO)]ClO
4·DMF (
2') crystallizes in the monoclinic spacegroup
P2
1/
c, with
a = 10.166(5) Å,
b = 11.934(4) Å,
c = 27.380(8) Å,
![](/images/gifchars/beta2.gif)
= 93.97(3)
![](/images/entities/deg.gif)
,
V = 3313(1) Å
3, and
Z= 4. It has a dinuclear core similar to that of
1, with square-pyramidal Co
II in the salen site and cis six-coordinateMn
II in the salbn site. Complex
3 crystallizes in the triclinic space group
P![](/images/entities/onemacr.gif)
,
a = 12.118(3) Å,
b = 12.156(2) Å,
c = 9.977(1) Å,
![](/images/gifchars/alpha.gif)
= 112.49(1)
![](/images/entities/deg.gif)
,
![](/images/gifchars/beta2.gif)
= 99.22(2)
![](/images/entities/deg.gif)
,
![](/images/gifchars/gamma.gif)
= 77.63(2)
![](/images/entities/deg.gif)
,
V = 1321.1(5) Å
3, and Z = 2. Both Co
II ionsin the salen and saltn sites assume a square-pyramidal geometry with a bridging acetate group in the syn-synmode. The displacement of the Co in the saltn site, from the basal N
2O
2 least-squares plane toward the apicalacetate oxygen, is 0.53 Å. Complex
5 is found to be isostructural with
3. The complexes
1,
2,
4,
5, and
6 arereversibly oxygenated in DMF at 0
![](/images/entities/deg.gif)
C to afford a
![](/images/entities/mgr.gif)
-peroxo dimer complex [{Co
IIIM
II(L)(AcO)}
2(O
22-)]
2+. Complex
3 also forms such a
![](/images/entities/mgr.gif)
-peroxo dimer complex but is irreversibly oxidized through an intramolecular-type
![](/images/entities/mgr.gif)
-peroxocomplex [Co
IIICo
III(L
2,3)(AcO)(O
22-)]
+.