Structures and stabilization due to stacking of ternarycopper(II) complexes containing an aromatic aminoacid(AA) and an aromatic diamine (DA), Cu(AA)(DA), have beeninvestigated by potentiometric, spectroscopic, andX-ray diffraction methods. For the systems with AA =
para-X-substituted
L-phenylalanine(
L-XPhe; X = H,NO
2, OH, NH
2) and DA = 2,2'-bipyridine (bpy)or 1,10-phenanthroline (phen), the difference absorptionspectrain the region 320-400 nm exhibited a peak assignable to the chargetransfer interaction between the aromaticrings of DA and
L-XPhe, the intensity being in the orderNH
2 > OH > H
NO
2 with respect to X.The stabilityconstants of Cu(AA)(DA) determined for AA =
DL-XPhe (X = F, Cl, Br) and
L-XPhe (X =NH
2, NO
2, I) at 25
C and
I = 0.1 M (KNO
3) indicated thatstabilization of Cu(
L-XPhe)(DA) relative toCu(
L-Ala)(en) (Ala = alanine;en = ethylenediamine) is in the order Br > OH > Cl
NH
2 > NO
2 H
F. The structures of[Cu(
L-NH
2Phe)(bpy)]NO
3·H
2O (
1),[Cu(
L-Tyr)(phen)]ClO
4·2.5H
2O(
2),[Cu(
L-Phe)(phen)]Cl·3H
2O(
3), and [Cu(
L-Phe)(bpy)]ClO
4·H
2O (
4), isolatedas crystals, were determined by the X-ray diffraction method:
1, orthorhombic,
P2
12
12
1,
a= 10.292(1) Å,
b = 13.576(4) Å,
c= 14.407(1) Å,
V = 2012.9 Å
3,
Z = 4,
R = 0.037,
Rw= 0.038;
2, orthorhombic,
P2
12
12
1,
a= 18.20(2) Å,
b = 32.63(1) Å,
c= 8.14(1) Å,
V = 4833 Å
3,
Z = 4,
R = 0.111,
Rw= 0.087;
3, monoclinic,
P2
1,
a = 11.738(2) Å,
b = 16.301(1) Å,
c = 11.795(1) Å,
= 102.01(1)
,
V = 2207.4Å
3,
Z = 2,
R = 0.045,
Rw = 0.035;
4, monoclinic,
P2
1,
a = 9.954(2) Å,
b = 24.179(3) Å,
c = 9.780(2) Å,
=107.32(1)
,
V = 2257.1 Å
3,
Z = 4,
R = 0.065,
Rw= 0.060. All of the complexes have a similardistortedsquare-pyramidal structure around the central Cu(II) ion.While
1 and
2 have a structure involvingaromatic ringstacking in the solid state,
4 has a structure without itand
3 has both types of structures in the unitcell.