Mixed-Ligand Complexes of Copper(II) with a-Hydroxycarboxylic Acids

and 1,10-Phenanthroline
R. Carballo*, B. Covelo
Vigo/Spain, Universidad de Vigo, Departamento de Qumica Inorganica

S. Balboa, A. Castineiras
Santiago de Compostela/Spain, Universidad de Santiago de Compostela, Departamento de Qumica Inorganica

J. Niclos
Granada/Spain, Universidad de Granada, Departamento de Qumica Inorganica
Received November 20th, 2000.

Dedicated to Professor Kurt Dehnicke on the Occasion of his 70th Birthday

Abstract. Eight new two-ligand complexes of copper(II) with
1,10-phenanthroline and one of four different a-hydroxycarboxylic acids (glycolic, lactic, mandelic and benzylic) were
prepared. The complexes of general formula [Cu(HL)2(phen)] nH2O (HL = monodeprotonated acid) (14) were
characterized by elemental analysis, IR, electronic and EPR
spectroscopy, magnetic measurements and thermo-gravimetric analysis. The complexes of general formulae
[Cu(HL)(phen)2](HL) H2L nSolv [1 a (HL = HGLYO,
n = 1, Solv = MeCN) and 3 a (HL = HMANO, n = 0)] and
[Cu(L)(phen)(OH2)] nH2O [2 a (L = LACO2, n = 4) and
4 a (L = BENO2, n = 2)] were characterized by X-ray diffractometry. In all these latter a pentacoordinated copper

atom has a basically square pyramidal coordination polyhedron, the distortion of which towards a trigonal bipyramidal
configuration has been evaluated in terms of the parameter s.
In 1 a and 3 a there are three forms of a-hydroxycarboxylic
acid: a monodentate monoanion, a monoanionic counterion,
and a neutral molecule lying in the outer coordination
sphere; in 2 a and 4 a the a-hydroxycarboxylic acid is a bidentate dianion coordinating through carboxyl and hydroxyl
oxygens.
Keywords: Mixed-ligand complexes; Copper(II) complexes;
Phenanthroline complexes; glycolic acid; lactic acid: mandelic acid; benzylic acid; crystal structures

Gemischtliganden-Komplexe von Kupfer(II) mit a-Hydroxycarbonsauren

und 1,10-Phenanthrolin
Inhaltsubersicht. Acht neue Zweiligand-Komplexe von Kupfer(II) mit 1,10-Phenanthrolin und einer von vier a-Hydroxycarbonsauren (Glykol-, Milch-, Mandel-, Benzilsaure)
wurden dargestellt. Die Komplexe mit der allgemeinen Formel [Cu(HL)2(phen)] nH2O (HL = monodeprotonierte
Saure) (14) wurden elementaranalytisch, durch IR-, UV/
Vis- und EPR-Spektroskopie, magnetische Messungen
sowie thermogravimetrisch charakterisiert. Die Komplexe
[Cu(HL)(phen)2](HL) H2L nSolvens [1 a (HL = HGLYO,
n = 1, Solvens = MeCN) und 3 a (HL = HMNO, n = 0] und
[Cu(L)(phen)(OH2)] nH2O [2 a (L = LACO2, n = 4) und

4 a (L = BENO2, n = 2)] wurden rontgenographisch charakterisiert. In allen letztgenannten Komplexen bildet das funffach koordinierte Kupferatom ein im wesentlichen quadratisch-pyramidales Koordinationspolyeder, die Verzerrung zu
einer trigonal-bipyramidalen Konfiguration wird uber den
Parameter s definiert. In 1 a und 3 a liegen die a-Hydroxycarbonsaure in drei Formen vor: als einzahniges Monoanion,
als monoanionisches Gegenion und als neutrales Molekul in
der aueren Koordinationssphare; in 2 a und 4 a ist die
a-Hydroxycarbonlsaure ein zweizahniges Dianion, das uber
die Carboxyl- und Hydroxyl-Sauerstoffatome koordiniert.

Introduction
* Prof. Dr. R. Carballo,
Departamento de Qumica Inorganica,
Facultad de Ciencias Qumica,
Universidad de Vigo,
E-36200 Vigo/Spain,
Fax: +3 49 86 81 23 82
E-mail: rcrial@uvigo.es
948

WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001

Of the many types of compound being explored in the

search for new anti-cancer drugs, we note here the following three:
1. Complexes of copper(II) with salicylate or similar
ligands [1].
2. Metal complexes of 1,10-phenanthroline [1, 2].
Flat chelating ligands such as 1,10-phenanthroline can
00442313/01/627948954 $ 17.50+.50/0

Z. Anorg. Allg. Chem. 2001, 627, 948954

Mixed-Ligand Complexes of Copper(II) with a-Hydroxycarboxylic Acids and 1,10-Phenanthroline

be intercalated in base pairs in the DNA helix with

sufficient overlap between their own rings and those
of the DNA bases for stacking interactions to be
formed.
3. Cisplatin analogues [3]. Two cisplatin analogues
currently undergoing clinical trials, nedaplatin (254-S)
and lobaplatin (D-19466), are aminocomplexes of platinum(II) with biological a-hydroxy-carboxylic acids:
glycolate in the case of nedaplatin, lactate in that of
lobaplatin.
With a view to the possible advantages of combining characteristics of each of these classes of compound, in the work described here we synthesized and
characterized the structures of a series of mixed-ligand
complexes of copper(II) with 1,10-phenanthroline and
one of four a-hydroxycarboxylic acids of different
bulkiness: glycolic acid (H2GLYO), lactic acid
(H2LACO), mandelic acid (H2MANO) and benzylic
acid (H2BENO) (Scheme 1).

Scheme 1

Results and Discussion

Reaction of the a-hydroxycarboxylic acids and 1,10phenanthroline in ethanol with basic salts of copper(II) (hydroxy-carbonate for 13, acetate for 4) afforded powdery blue solids with analytical data corresponding to the general formula [Cu(HL)2(phen)]
nH2O, where HL = HGLYO (1), HLACO (2),
HMANO (3) or HBENO (4). These compounds are
stable in air, have melting points in the range 150
230 C, and in general are very poorly soluble in both
polar and apolar solvents.
The IR spectra of 14 show one or more generally
medium-intensity bands in the 30003500 cm1 region
corresponding to OH stretching vibrations of ligands
and water of crystallization. A strong band around
1600 cm1 is attributable to masym(OCO) and the band
between 1330 and 1390 cm1 to msym(OCO), although
identification of the latter is hampered by the presence of phenanthroline bands in this region. The values of 215290 cm1 for Dm = masym(OCO) msym(OCO)
are typical of monodentate carboxylato groups [4]. A
weak band around 400 cm1 is attributed to m(CuO),
and the band between 280 and 300 cm1 is tentatively
identified as due to m(CuN) [5].
The electronic spectra obtained by diffuse reflectance
show an asymmetric broad band attributable to d-d
Z. Anorg. Allg. Chem. 2001, 627, 948954

Table 1 UV-Vis, EPR and magnetic moments data for the

complexes 14
Complex

UV-Vis data/cm1

g||

g^

leff/
B. M.

lcalc/
B. M.

26110
24100
26740
27700
28500

14790

2.29

2.06

1.13

1.85

14000
14000
15500

2.29
2.23
2.24

2.06
2.05
2.06

1.82
1.44
1.95

1.85
1.83
1.84

2
3
4

transitions centred in the range 1400015500 cm1, as

expected for octahedral copper(II) complexes with
tetragonal distortion [6]. Charge transfer bands appear
at 24000 and 28500 cm1.
The magnetic moments of compounds 1 and 3 fall
markedly as temperature rises; at room temperature
leff is only 1.44 B. M. for 3 and only 1.13 B. M. for 1
(Table 1). Such low values suggest the possibility of
antiferromagnetic coupling between metal centres [7,
8]. By contrast, the magnetic moment of 2 shows no
marked temperature dependence, and at room temperature the values of leff of both 2 (1.82 B.M.) and 4
1.95 B.M. are typical of copper(II) species with no
CuCu interaction [9, 10].
The EPR spectra for polycrystalline samples at
room temperature are typical of the axial symmetry.
The axial spectra with g|| > g^ indicate that the symmetry at the site of copper is approximately C4v and the
unpaired electron occupies a 3d(x2y2) orbital. The values of 2.292.24 (Table 1) suggests CuII in an octahedral environment with tetragonal distortion [7, 11].
Using the EPR g values the magnetic moments for uncoupled species were calculated {lcalc = gav[S(S + 1)]1/2}
and compared with the observed values (Table 1): the
magnetic moment of 4 is large compared with the expected value. Assuming that the experimental errors
are not large, this could indicate ferromagnetic interactions; 1 and 3 have low magnetic moments, suggesting antiferromagnetic coupling; and the magnetic moment of 2 is normal and do not indicate whether the
coupling, if there is any, is ferromagnetic or antiferromagnetic.
Compounds 14 behave quite similarly upon thermogravimetric analysis (Table 2), being stable up to
150200 (except for loss of water of crystallization)
and thereafter undergoing weight losses which in the
case of 4 clearly correspond to loss of the anionic ligand followed by loss of phen (in the other compounds the order of these processes is not so clear).
Note that the loss of water by 2 between 100 and
150 C is less than what corresponds to its formula,
and that 4 shows no loss of water; it is perhaps possible that the water of crystallization is so weakly bound
in the lattice that it is largely lost during stabilization
of the balance.
Single crystals suitable for X-ray diffractometry
were obtained by slow evaporation of the mother li949

R. Carballo, B. Covelo, S. Balboa, A. Castineiras, J. Niclos

Table 2

Thermogravimetric Analysis for the complex 14

Compound

Temp. range/C

Weight loss/%

corresponding to

RT-190
190300
300440

stable
64.64
stable

HGLYO + phen

RT-100
100150
150200
200360

stable
6.47
stable
49.51

RT-160
160300
300410

stable
55.41
stable

RT-150
150320
320560

stable
62.92
22.13

1.77 water
HLACO + phen
HMANO + phen

HBENO
phen

quor of 2 (giving [Cu(LACO)(phen)(OH2)] 4 H2O,

2 a); recrystallization of 4 from CH3CN/H2O (giving
[Cu(BENO)(phen)(OH2)] 2 H2O, 4 a); and slow
evaporation of the mother liquors of 1 and 3 to obtain
oils that were then crystallized from CH3CN
and EtOH, respectively, as [Cu(HGLYO)(phen)2](HGLYO) H2GLYO CH3CN (1 a) and [Cu(HMANO)(phen)2](HMANO) H2MANO (3 a).

n = 2)]. Table 3 lists the chief bond lengths and bond

angles. Figs. 14 show the structures of [Cu(HGLYO)(phen)2]+, [Cu(LACO)(phen)(OH2)][Cu(HMANO)(phen)2]+ and [Cu(BENO)(phen)(OH2)], respectively,
together with the atom-numbering schemes used.
Notwithstanding the above binary classification, the
detailed behaviours of the a-hydroxycarboxylic acids
in these complexes are very diverse, apparently without the similarities and differences being explicable in
terms of their different bulks. In 1 a and 3 a there are
three different types of a-hydroxycarboxylic acid molecule, one acting as a monodentate monoanion, one
as a monoanionic counterion, and one as a neutral
molecule lying in the outer coordination sphere. A
combination of these behaviours by lactic acid has
been observed in complexes of copper(II) and zinc(II)
with diamines other than phen [12, 13]. However, in
the lactate derivative prepared in this work (2 a), and
in 4 a, the a-hydroxycarboxylic acids behave only as
bidentate dianions, as in complexes of lactic [3, 14],
mandelic [15], and benzylic [1620] acids with other
metals.

Molecular structures
On the basis of the behaviour of their a-hydroxycarboxylic acids, compounds 1 a4 a may be classified
in two groups: those of general formula [Cu(HL)(phen)2](HL) H2L nSolv [1 a (HL = HGLYO, n = 1,
Solv = MeCN) and 3 a (HL = HMANO, n = 0)]; and
those of general formula [Cu(L)(phen)(OH2)] nH2O
[2 a (L = LACO2, n = 4) and 4 a (L = BENO2,
and angles/ for the comTable 3 Selected bond lengths/A
plexes 1 a4 a
Compound

1a

2a

3a

4a

Cu1O1
Cu1O11
Cu1O13
Cu1N1
Cu1N2
Cu1N3
Cu1N4
Cu1O12

1.994(4)

2.012(5)
2.036(5)
2.206(5)
2.005(5)
2.929(4)

2.299(4)
1.947(4)
1.904(4)
2.019(4)
2.021(5)

3.913(5)

2.018(4)

1.992(4)
2.069(4)
2.177(4)
2.006(4)
2.582(5)

2.281(7)
1.983(7)
1.904(7)
2.003(9)
2.039(8)

3.926(7)

90.35(18)
154.41(18)
97.94(17)
93.64(18)

81.32(19)
100.48(18)
176.01(19)
107.33(17)
95.11(19)
78.8(2)

100.19(17)
96.91(17)
94.38(18)
91.06(18)
96.06(16)
164.47(18)
92.59(18)

97.56(18)
172.02(18)
81.73(19)

91.90(17)
153.51(16)
104.15(15)
93.98(16)

81.14(17)
97.18(16)
173.88(17)
102.08(14)
94.28(16)
79.75(16)

O1Cu1O11
O1Cu1O13
O1Cu1N1
O1Cu1N2
O11Cu1O13
O11Cu1N1
O11Cu1N2
O11Cu1N3
O11Cu1N4
O13Cu1N1
O13Cu1N2
N1Cu1N2
N1Cu1N3
N1Cu1N4
N2Cu1N3
N2Cu1N4
N3Cu1N4
s

950

0.36

0.13

0.34

Fig. 1 Structure of the cationic complex [Cu(HGLYO)(phen)2]+.

100.1(3)
103.8(3)
83.3(3)
98.2(3)
84.9(3)
94.9(4)
161.0(3)

172.8(4)
95.8(4)
82.0(4)

0.20

Fig. 2 Molecular structure of the complex [Cu(LACO)(phen)(H2O)].

Z. Anorg. Allg. Chem. 2001, 627, 948954

Mixed-Ligand Complexes of Copper(II) with a-Hydroxycarboxylic Acids and 1,10-Phenanthroline

Table 4
1 a4 a

Intermolecular hydrogen bonds for the complex

DH A

d(DH)/A

d(H A)/A

d(D A)/A

< (DHA)/

0.82
0.82
0.82
0.82
0.82

2.31
2.42
2.50
2.21
2.37

2.905(6)
3.178(7)
2.938(7)
2.938(7)
3.124(7)

130.2
154.7
114.5
148.1
154.0

Compound 1 a
O13H13A O16 1
O13H13A O14 1
O14H14A O16 2
O16H16A O14 3
O16H16A O15 3

Symmetry transformations: 1) 1 + x, y 1/2, z + 1/2; 2) x, y + 1/2, z + 1/2;

3) x, y + 1/2, z 1/2
Compound 2 a

Fig. 3 Structure of the cationic complex [Cu(HMANO)(phen)2]+.

O13 O2
O1 O12 1
O2 O4
O2 O5
O3 O12 2
O3 O5
O3 O11 1
O4 O4 3
O4 O13 4
O5 O5 5

2.731(7)
2.753(6)
2.778(8)
2.800(8)
2.742(6)
2.751(8)
2.860(6)
2.708(12)
2.804(7)
2.827(11)

Symmetry transformations: 1) x+, y, z + 1; 2) x + 1, y, z; 3) x + 2, y + 1, z;

4) x + 1, y + 1, z; 5) x + 1, y + 1, z + 1
Compound 3 a
O13H13A O12
O17H17A O14 1

0.82
0.82

2.10
1.71

2.596(6)
2.507(6)

118.3
162.5

Symmetry transformations: 1) x 1, y, z + 1
Compound 4 a
O1 O13 1
O1 O2
O11 O3
O12 O3 2
O2 O3

2.614(9)
2.961(13)
2.822(12)
2.860(12)
2.848(16)

Symmetry transformations: 1) x, y, z + 1; 2) x, y, z + 2

Fig. 4 Molecular structure of the complex [Cu(BENO)(phen)(H2O)].

Compounds 1 a and 3 a are composed of a cationic

complex [Cu(HL)(phen)2]+ and, in the outer coordination sphere, a counterion HL and a nondeprotonated neutral molecule of H2L; 1 a also contains solvating acetonitrile. The copper atom is coordinated to
the four 1,10-phenanthroline nitrogens and to one of
the carboxylato oxygens of the monodentate, monodeprotonated acid; these CuN and CuO distances are
within the normal range for this kind of copper(II)
complex [8, 10, 21]. O12 is too far from the metal
, respectively} to be complet{2.929(4) and 2.582(5) A
ing a distorted octahedral coordination polyhedron,
but as in similar cases [8, 22] may be considered to
contribute to a coordination sphere of (4 + 1 + 1*)
type, although in 3 a there is some Cu1O12 signifi,
cant interaction {bond lengts: C1O11 = 1.248(7) A
in contrast to 1.279(7) and
C1O12 = 1.233(7) A
respectively in 1 a}. The five strongly coor1.230(7) A
Z. Anorg. Allg. Chem. 2001, 627, 948954

dinated atoms basically form a square pyramid with

one of the phenanthroline nitrogens (N3) at the apex
from the copper atom, but there is
about 2.20 A
marked distortion towards the trigonal bipyramid in
both 1 a and 3 a, and the overall degree of distortion,
evaluated using Addison et al.'s parameter s [23], is almost the same in both (Table 3). The distortion shows
up most in the angles between adjacent atoms in the
base, which deviate markedly from 90 (Table 3).
Also, the four atoms defining the base of the pyramid
from the least-squares plane they delie 0.210.25 A
from this
fine, and the copper atom lies about 0.20 A
plane. The crystal lattice is stabilized by hydrogen
bonds involving the hydroxyl and carboxy groups of
the various species derived from the a-hydroxycarboxylic acid; the parameters of the main hydrogen
bonds are listed in Table 4.
In compounds 2 a and 4 a the asymmetric unit is
composed of the neutral complex [Cu(L)(phen)(OH2)] and water of crystallization. In these compounds, too, the copper atom is pentacoordinated, but
the donors are now the two nitrogen atoms of the single phenanthroline ligand, two oxygens belonging to a
dideprotonated bidentate a-hydroxycarboxylato ligand (which like the phenanthroline forms a fivemembered chelate ring), and the oxygen of the coordinated water molecule. In both complexes the coordi951

R. Carballo, B. Covelo, S. Balboa, A. Castineiras, J. Niclos

ing point apparatus and are uncorrected. IR spectra in KBr
discs (4000400 cm1) or polyethylene-sandwiched Nujol
mulls (500100 cm1) were recorded on a Bruker IFS66v
spectrophotometer. A Shimadzu UV-3101PC spectrophotometer was used to obtain electronic spectra in the region
900350 nm. Magnetic susceptibility measurements were
made at room temperature using a Johnson Matthey Magnetic Susceptibility Balance (for 4), or at variable temperature with a DSM-10 magnetometer (for 13). The X-band
(9300 MHz) EPR spectra were obtained at room temperature with a Bruker ESP 300E spectrometer. Thermogravimetric analyses were performed on a Shimadzu TGA-DGT50H instrument coupled to an IR-TF Nicolet Magma 550
spectrophotometer.
General Procedure for Preparation of the Complexes

Fig. 5 Molecular packing of [Cu(LACO)(phen)(H2O)]

4 H2O showing the stacking interactions between the phenanthroline rings.

nation polyhedron is a square pyramid with the coordinated water molecule at its apex, with slightly more
distortion towards the trigonal bipyramid in 4 a
(s = 0.20) than in 2 a (s = 0.13). As in 1 a and 3 a, the
copper atom lies above the least-squares plane defined by the four atoms forming the base of the pyra away in 2 a, 0.226 A
in 4 a. The CuN
mid: 0.196 A
distances are longer than the CuO(hydroxycarboxylato) distances, and similar to the basal CuN distances in 1 a and 3 a. The deprotonation of the lactato
and benzylato hydroxyls leads to the CuO(hydroxyl)
distance being shorter than the CuO(carboxylato)
distance (Table 3), whereas in complexes in which a
lactato ligand is bidentate but monoanionic the reverse is the case [24, 25]. In the two complexes there
are stacking interactions between the phenanthroline
rings of neighbouring molecules, with an inter-ring dis (2 a) and 3.45 A
(4 a) (Fig. 5).
tances between 3.65 A
This stacking distance is similar both to those observed in other copper(II)-phenanthroline complexes
with this kind of coordination geometry [26], and to
the inter-base stacking distance in the DNA helix [27],
suggesting that complexes of this kind may indeed be
able to intercalate in DNA base pairs. Finally, in both
2 a and 4 a the presence of water of crystallization
gives rise to a network of hydrogen bonds, the O O
distances of which are listed in Table 4.
Experimental Section
General. Chemicals were purchased from commercial
sources and used without further purification. Elemental
analyses (C, N, H) were performed in a Carlo Erba 1108 microanalyser. Melting points were measured in a Buchi melt952

Complexes of H2GLYO, H2LACO or H2MANO. A suspension of CuCO3 Cu(OH)2 (2.26 mmol) and of the appropriate a-hydroxy-carboxylic acid (9.10 mmol) in 35 mL of
EtOH was refluxed for 4 h at 75 C. 1,10-Phenanthroline
(4.52 mmol) was added, and refluxing was continued for 2 h,
after which the mixture was stirred for several days. The
blue solids formed were filtered out, washed with ethanol,
and dried over CaCl2.
Complexes of H2BENO. A solution of 1,10-phenanthroline
(0.22 mmol) in 5 mL of ethanol was slowly added to a
solution of H2BENO (0.44 mmol) and Cu(AcO)2 H2O
(0.22 mmol) in 10 mL of the same solvent, and the mixture
was stirred at room temperature for 2 days. The blue precipitate formed was isolated, washed with ethanol, and dried
over CaCl2.
[Cu(HGLYO)2(phen)] (1) Yield: 55%. M.p.: 230 C.
C16H14N2O6Cu (393.01): calcd. C 48.8, H 3.6, N 7.1; found
C 49.6, H 4.1, N 7.2%.
IR (KBr) m (cm1): 3396, 3084 (OH), 1614 (CC), 1604
masym(OCO), 1386 msym(OCO), 1518, 1428 (CC, CN), 1077
(CO), 1061 (ring breathing), 725 c(CH), 405 (CuO), 289
(CuN).
The recrystalization in hot CH3CN of the blue oil obtained after the slow evaporation of the mother liquor of 1,
allowed the isolation of single crystals with the composition
[Cu(HGLYO)(phen)2](HGLYO) H2GLYO CH3CN (1 a).
[Cu(HLACO)2(phen)] 4 H2O (2) Yield: 80%. M.p.: 186 C.
C18H26N2O10Cu (493.08): calcd. C 43.8, H 5.3, N 5.7; found
C 43.1, H 4.9, N 5.6%.
IR (KBr) m (cm1): 3430 (OH), 1610 (CC), 1605 masym(OCO),
1384 msym(OCO), 1518, 1429 (CC, CN), 1094 (CO), 1056
(ring breathing), 725 c(CH), 398 (CuO), 293 (CuN).
Single crystals of formula [Cu(LACO)(phen)(OH2)]
4 H2O (2 a) were obtained by slow evaporation at room temperature of the filtrate of 2.
[Cu(HMANO)2(phen)] (3) Yield: 79%. M.p.: 180 C.
C28H12N2O6Cu (534.99): calcd. C 61.6, H 4.1, N 5.1; found
C 61.2, H 4.3, N 5.2%.
IR (KBr) m (cm1): 3449, 3086 (OH), 1637 (CC), 1603
masym(OCO), 1341 msym(OCO), 1520, 1430 (CC, CN), 1091
(CO), 1059 (ring breathing), 724 c(CH), 405 (CuO), 298
(CuN).
The recrystalization in EtOH at 0 C of the green oil resulting from the slow evaporation of the mother liquor yield
Z. Anorg. Allg. Chem. 2001, 627, 948954

Mixed-Ligand Complexes of Copper(II) with a-Hydroxycarboxylic Acids and 1,10-Phenanthroline

Table 5

Crystal data and structure refinement for the complex 1 a4 a

Compound

1a

2a

3a

4a

Empirical formula
Colour, Habit
Crystal size/mm

Radiation/k, A
Crystal system
Space group

C12H29CuN5O9
blue, prism
0.35 0.25 0.25
CuKa, (1.54104)
monoclinic
P21/c (No. 14)

C15H22CuN2O8
blue, prism
0.40 0.08 0.08
CuKa, (1.54104)
triclinic
P1 (No. 2)

C48H38CuN4O9
green, prism
0.23 0.22 0.14
MoKa, (0.71073)
triclinic
P1 (No. 2)

C26H24CuN2O6
green, prism
0.17 0.10 0.10
MoKa, (0.71073)
monoclinic
C2 (No. 5)

Unit cell dimensions

a/A

b/A

c/A
a/
b/
c/
3
Volume/A
Z
Formula weight
Density (calc.) Mg/m3
Absorption coeff. mm1
F(000)
h range/
Absorption corr.
Max./Min. transm.
Reflex. colleted
Data/parameters
Final R [I > 2r(I)]
R indices (all data)
Goodness-of-Fit
3
Largest diff. peak/hole/eA

14.3513(16)
19.8339(13)
10.7041(8)
90.000
98.901(8)
90.000
3010.1(4)
4
691.14
1.525
1.590
1428
3.1265.87
w-scans
0.919/0.817
10896
5236/421
R = 0.058, wR = 0.137
R = 0.233, wR = 0.197
0.921
0.568/0.522

7.284(4)
11.737(10)
12.116(7)
65.77(6)
84.25(6)
75.38(6)
914.0(10)
2
421.89
1.553
2.103
438
4.0075.92
w-scans
0.890/0.782
4000
3808/254
R = 0.086, wR = 0.229
R = 0.127, wR = 0.251
1.009
0.782/1.444

11.4281(12)
12.9686(14)
16.1101(7)
86.408(2)
69.914(2)
67.345(2)
2062.7(4)
2
878.36
1.414
0.594
910
1.7128.03
empirical
0.922/0.875
13801
9581/553
R = 0.072, wR = 0.164
R = 0.190, wR = 0.207
0.857
0.738/0.747

19.957(9)
11.558(6)
10.787(5)
90.00
106.22(1)
90.00
2389(2)
4
524.01
1.457
0.959
1084
1.9728.07
empirical
0.910/0.854
6638
4198/317
R = 0.077, wR = 0.156
R = 0.159, wR = 0.186
0.876
0.728/0.810

the green single crystals of formula [Cu(HMANO)(phen)2](HMANO) H2MANO (3 a).

[Cu(HBENO)2(phen)] H2O (4) Yield: 61%. M.p.: 150 C.
C40H32N2O7Cu (716.25): calcd. C 67.1, H 4.5, N 3.9; found
C 67.3, H 4.3, N 4.2%.
IR (KBr) m (cm1): 3375, 3060 (OH), 1651 (CC), 1625
masym(OCO), 1336 msym(OCO), 1489, 1428 (CC, CN), 1090
(CO), 1053 (ring breathing), 731 c(CH), 427 (CuO), 306
(CuN).
The slow evaporation at room temperature of the disolution of 4 in a hot CH3CN/H2O (1 : 1) mixture yield the green
single crystals of composition [Cu(BENO)(phen)(OH2)]
2 H2O (4 a).
X-ray Crystallography
Data collection and refinement parameters are summarised
in Table 5. The diffraction data were collected on either an
Enraf-Nonius CAD4 diffractometer (complexes 1 a and 2 a)
or a Bruker SMART CCD instrument (complexes 3 a and
4 a) at 293 K using monochromated radiation. A semi-empirical absortion correction (w-scans [28]) was applied for 1 a
and 2 a. For 3 a and 4 a the data were corrected for absorption using the SADABS program of the SAINT software
package [29]. The structures were solved by direct methods
and subsequent difference Fourier techniques (SHELXS)
[30] and refined on F 2 using SHELXL [31]. Hydrogen atoms
were included in the refinement in calculated positions riding on their carrier atoms. Neutral atom scattering factors
and anomalous dispersion corrections were taken from International Tables for X-ray Crystallography [32]. Geometrical
calculations and illustrations were performed or generated
with the SHELXL97 [31], PLATON [33] packages. Crystallographic data for the structures reported in this paper (exZ. Anorg. Allg. Chem. 2001, 627, 948954

cluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre as supplementary
publications CCDC-153009 [Cu(HGLYO)(phen)2](HGLYO)
H2GLYO CH3CN (1 a), CCDC-153010 [Cu(LACO)(phen)(OH2)] 4 H2O (2 a), CCDC-153011 [Cu(HMANO)(phen)2](HMANO) H2MANO (3 a) and CCDC-153012 [Cu(BENO)(phen)(OH2)] 2 H2O (4 a). Copies of the data can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CD2 1EZ, UK (Fax, +44-12 23/3 36-0 33;
E-mail, deposit@ccdc.cam.ac.uk).
Acknowledgements. We thank the DGESIC (Spain) for
financial support (Project PB98-0605-C03).

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Z. Anorg. Allg. Chem. 2001, 627, 948954