Copper complex of glycine Schiff base: In situ ligand synthesis, structure,

spectral, and thermal properties

Agata Trzesowska-Kruszynska

Department of X-Ray Crystallography and Crystal Chemistry, Institute of General and Ecological Chemistry, Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland
a r t i c l e i n f o
Article history:
Received 25 October 2011
Received in revised form 18 January 2012
Accepted 1 March 2012
Available online 14 March 2012
Keywords:
Glycine Schiff base
In situ ligand synthesis
Copper complex
TD-DFT calculations
Solvent effect
a b s t r a c t
The novel glycine Schiff base copper complex, [Cu(C
7
H
6
NO
3
)
2
(H
2
O)]0.5H
2
O, has been prepared by the
in situ ligand synthesis method. The compound has been characterised by solid state IR and UVVis spec-
troscopy, TGA and single crystal X-ray diffraction studies. The spin-allowed electronic transitions have
been calculated with the time-dependent DFT method for an isolated complex molecule. The electronic
structure calculations have been carried out for the Schiff base molecule in the gas and liquid phase at the
MP2 and DFT levels of theory.
2012 Elsevier B.V. All rights reserved.
1. Introduction
The Schiff bases, compounds of antibacterial, antifungal and
anticancer properties, can be obtained in good yields and high pur-
ity, through the straightforward condensation reaction between an
amine and a carbonyl compound. Synthesis of a particular class of
Schiff bases, those derived from amino acids, requires some special
conditions due to the zwitterionic effect.
A Cambridge Structural Database (CSD) [1] search revealed only
a few crystal structures of pure organic ligands containing amino
acid moieties, but the number of complex structures is higher.
The method of in situ Schiff base synthesis, during coordination
reaction, has been utilised to obtain these compounds, because
the pure ligand undergoes rapid hydrolysis in aqueous media
[24]. The metal ion stabilises the rigid structure of the unstable
ligand, which results in a planar alignment of ligand atoms. pH
and ionic strength of reaction mixture, and in consequence the
usage of dissociating metal salt, inuence the formation of the
Schiff base coordination compounds [5,6]. Such coordination
systems serve as model compounds to examine the intermediate
products in many metabolic reactions of amino acids catalysed
by enzymes. In this context, the synthesis of Schiff base complexes
derived from amino acids and studies of the interactions between
amino acid residue groups and metal ions have crucial importance.
Hence, the solid-state characterisation of a new Schiff base Cu(II)
coordination compound obtained from glycine and furaldehyde,
as well as the results of quantum mechanical calculations, are
reported here. The ligand was synthesised in situ during coordina-
tion reaction. The reagents were chosen due to their important
biological properties and technical applications. The interactions
of copper(II) with amino acid derivatives and peptide derivatives
are of a considerable interest due to the role of such metal ions
in the enzymes [79]. Furaldehyde Schiff bases were found to show
the selectivity towards anions and can act as anion-sensitive mem-
brane electrodes [10], they also possess the nitrication inhibitory
properties [11]. The interaction of the 2-furaldehyde derivative,
namely the 5-(hydroxymethyl)-2-furaldehyde, with amino acids
has been the subject of study since this aldehyde is present in
many foods in high concentrations as a common product of the
Maillard reaction [12]. The Schiff bases of 5-nitro-2-furaldehyde
and sulphonamides show antibacterial activity [13].
2. Experimental
2.1. Synthesis
Furan-2-carbaldehyde (2 mmol) mixed with methanol (20 cm
3
)
was added to an aqueous solution (10 cm
3
) of 2 mmol of glycine.
The reaction mixture was stirred for 15 min and then the copper(II)
acetate monohydrate (1 mmol) dissolved in 5 cm
3
of water was
added dropwise. Next, the solution was stirred for 1.5 h. The result-
ing solution was left to stand at room temperature. After 1 day, the
blue crystalline product of aqua-bis-(N-2-furfurylidene-glycinato-
O,N)-copper(II) hemihydrate (1) (Scheme 1) was obtained, ltered
and dried in air. The obtained complex compound is stable in air.
0022-2860/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2012.03.003

Tel.: +48 42 631 31 37; fax: +48 42 631 31 03.

E-mail address: agata.trzesowska@p.lodz.pl
Journal of Molecular Structure 1017 (2012) 7278
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Journal of Molecular Structure
j our nal homepage: www. el sevi er . com/ l ocat e/ mol st r uc
Attempts to obtain and isolate the pure ligand, N
0
-(2-furfurylid-
ene)glycine, in absence of metal salt during the condensation reac-
tion were unsuccessful. A hot solution of furan-2-carbaldehyde
(5 mmol) in methanol (30 ml) was mixed with a hot aqueous solu-
tion (20 cm
3
) of glycine (5 mmol). The mixture was reuxed for
2 h. The solution was then reduced by evaporation to half-volume
and allowed to cool. After 1 day, the colourless crystals of glycine
were formed. An increase of the reaction time to 8 h has not led
to formation of the Schiff base. Similar reactions performed for
p-dimethylaminobenzaldehyde instead of furan-2-carbaldehyde
or aspartic acid instead of glycine also led, after the process, to
uncreated substrates (on the basis of XRPD and elemental analyses
of formed crystals). The introducing of copper(II) acetate
monohydrate into system consisted of p-dimethylaminobenzalde-
hyde and glycine results in the formation of copper(II) glycinate,
acetic acid and the quantitative crystallisation of unreacted
p-dimethylaminobenzaldehyde.
2.2. X-ray crystallography
The crystal of 1 was mounted on a KM-4-CCD automatic diffrac-
tometer equipped with CCD detector, and used for data collection.
X-ray intensity data were collected with graphite monochromated
Mo Ka radiation (k = 0.71073 ), with x scan mode. The crystal
used for data collection did not change its appearance. Lorentz,
polarisation and numerical absorption [14] corrections were
applied. The structure was solved by direct methods and
subsequently completed by difference Fourier recycling. All the
non-hydrogen atoms were rened anisotropically using full-
matrix, least-squares technique on F
2
. The hydrogen atoms were
found form the difference Fourier syntheses and treated as riding
on their parent non-hydrogen atoms and assigned isotropic dis-
placement parameters equal to 1.5 (water molecules) or 1.2 (other
atoms) times the value of equivalent displacement parameters of
the parent atoms. The geometry of hydrogen atoms attached to
carbon atoms was idealised after each cycle of least-squares rene-
ment. SHELXS97, SHELXL97 and SHELXTL [15] programs were used
for all the calculations. Details concerning crystal data and rene-
ment are summarised in Table 1, selected bond lengths and bond
angles are given in Table S1 of Supplementary material.
2.3. Theoretical calculations
The gas phase and solution geometry optimisation was
performed at the B3LYP [16,17] and at the second-order Mller
Plesset (MP2) [18] level of theory using the 6-31++G(d,p) basis
set and the GAUSSIAN03 [19] program package. The starting
geometrical parameters were employed from crystal structure
data. Basis set superposition error (BSSE) corrections were carried
out using the counterpoise (CP) method of Boys and Bernardi [20].
The solvent effect was treated using the polarizable continuum
model [21,22], for methanol as a solvent. The Gibbs free energy
for systems in the solution and the gas phase were obtained by
computation of vibrational frequencies for the geometrically
optimised molecules. The singlet excited-states, starting from
the ground-state geometry optimised in the gas phase, were
calculated with the time-dependent DFT method (TD-DFT method
[2325]). Molecular orbitals were plotted using the GaussView
program [26].
2.4. Spectroscopic measurements
The IR spectrum (4004000 cm
1
) was recorded on a Jasco FT/
IR-6200 spectrophotometer, with samples prepared as KBr disks.
The UVVis spectrum was recorded on a Jasco V-660 spectropho-
tometer, in transmission mode, for the solid-state sample pressed
between two quartz plates.
Thermal analysis was carried out in a TG/DTA-SETSYS-16/18
thermoanalyser coupled with a ThermoStar (Balzers) mass spec-
trometer. The sample (10.85 mg) was heated in corundum cruci-
bles up to 1000 C, at the heating rate 10 C min
1
in air. The
products of decomposition were calculated from TG curves. The
temperature ranges were determined by means of thermoanalyser
Data Processing Module [27]. A coupled TG-MS system was used to
analyse the principal volatile thermal decomposition and fragmen-
tation products.
3. Results and discussion
3.1. The description of the structure
The complex 1 forms a homo organo-ligand compound with
two Schiff base anions in the inner coordination sphere, which
may be attributed to the smaller steric hindrance of N-substituent
of the imine in 1 (Fig. 1), in comparison to other known copper(II)
N-arylidene-a-amino acid coordination compounds creating the
polymeric, binuclear or mixed ligand structures [1]. The donor
atoms of ligands exist in the trans-planar geometry with the
d
NN
/d
NO
ratio equal to 1.4. Each of the ve-membered metal-
containing rings can be considered planar, and both ring systems
are close to co-planarity in the range of the experimental error.
O
N O
O
O
N
Cu
O
O
OH
2
0.5H
2
O
Scheme 1. The structural formula of 1.
Table 1
Crystal data and renement for 1.
Empirical formula C
28
H
30
Cu
2
N
4
O
15
(1)
Formula weight 789.64
Crystal system Monoclinic
Space group C2/c
Unit cell dimensions
a () 13.5407 (11)
b () 9.7865 (3)
c () 23.1474 (15)
b () 105.601 (7)
Volume (
3
) 2954.4 (3)
Z 4
Absorption coefcient (mm
1
) 1.525
F (000) 1616
Theta range for data collection () 1.8325.00
Index ranges 16 6 h 6 16
11 6 k 6 11
27 6 l 6 27
Goodness-of-t on F
2
1.083
Final R indices [I > 2r(I)] R
1
= 0.0265, wR
2
= 0.0815
R indices (all data) R
1
= 0.0287, wR
2
= 0.0831
Largest difference peak and hole (e
3
) 0.351 and 0.307
A. Trzesowska-Kruszynska / Journal of Molecular Structure 1017 (2012) 7278 73
The angle between two ligand weighted least squares planes is
4.05 (8). The Cu ion displays square pyramidal CuN
2
O
3
coordina-
tion geometry with the water molecule located at the pyramid
apex. The complex molecule of 1 possesses internal non-crystallo-
graphic symmetry, i.e. the twofold axis going through the copper
cation and oxygen atom of water molecule.
The complex molecules of 1 are assembled via p p stacking
interactions and hydrogen bonds (Table S2 of Supplementary
material) to the 3D supramolecular network. The two complex
molecules (second one generated by x + 1/2, y 1/2, z + 1/2
symmetry operation) associated to pairs by CAH O hydrogen
bond and p p stacking interaction between the furan rings are
assembled by uncoordinated water molecules into piles along crys-
tallographic [001] axis. In this arrangement, the shortest Cu Cu
i
(symmetry code: (i) x, y, z + 1/2) distance is 4.253 (3) . The
neighbouring piles, in turn, form supramolecular layers extending
along crystallographic (100) plane due to the presence of weak
CAH O hydrogen bonds between the 5-membered heterocyclic
rings. The presence of local non-crystallographic symmetry within
the complex molecule causes the pseudosymmetry in hydrogen
bonding schemes, i.e. the organic ligand containing N1 atom forms
hydrogen bonds analogous (in environment and geometry) to this
one containing N11 atom (e.g. C6AH6 O13
iii
is analogous to
16AH16 O3
v
, C7AH7 O2
iv
is analogous to C17AH17 O12
vi
etc., symmetry codes as in Table S2 of Supplementary material).
An interesting feature of the structure of 1 is the presence of
C@O p interactions [2830]. In one of the above-mentioned
arrangements of interacting organic ligands [in which the mole-
cules are related by a 2-fold rotation axis with indices [010] at
(0, y, 1/4)] the uncoordinated O atom of the carbonyl group is sit-
uated almost above the furan ring centroid at a distance of 3.359
(3) , with an angle between the ring plane and the vector linking
the ring centroid and the O12 atom of 90 (Fig. 2). All atoms of the
furan ring are closer than 3.6 to the O12 atom and the carbonyl
group is located parallel to the ring plane. This allows existence of
the interaction of the lone pair of the O12 atom with the electron-
decient furan ring. The results of quantum mechanical calcula-
tions imply that this interaction is bonding in character although
the geometrical parameters are not common, that is, the O p dis-
tance does not full the criterion [31,32] of being shorter than the
sum of the O and C van der Waals radii (3.22 [33]). The
MP2/6-31++G(d,p) calculations have been performed for model
system consisting of the furan ring interacting with the glycine
molecule in the zwitterionic form (Fig. 3). Basis set superposition
error (BSSE) corrected interaction enthalpy of formation of this
interaction is equal to 2 kcal/mol. The calculations indicate that
the observed weak lone pairp type interaction is bonding in char-
acter and it is not a merely tolerated short contact. This type of
Fig. 1. The molecular structure of 1 showing the atom numbering scheme. The
displacement ellipsoids are drawn at 50% probability level and H atoms are shown
as spheres of arbitrary radii.
Fig. 2. The C@O p interactions in 1. Hydrogen atoms have been omitted for
clarity.
Fig. 3. MP2/6-31++G(d,p) optimised geometry of glycine-furan pair for electron
lone pairp type interaction.
74 A. Trzesowska-Kruszynska / Journal of Molecular Structure 1017 (2012) 7278
interaction has also been observed for catena-((l
3
-N-(o-hydroxy-
benzyl)glycinato-N,O,O,O
0
,O
00
)-(l
2
-N-(o-hydroxybenzyl)-glycinato-
N,O,O,O
0
)-aqua-di-copper(II) monohydrate) [34].
The bond lengths (Table S1 of Supplementary material) in the
complex molecule are consistent with those in (N-salicylidenegly-
cinato-N,O,O
0
)-copper(II) derivatives, and also uncoordinated ami-
no acid Schiff bases except for the C@N distance. The C@N bond is
shortened in 1, in comparison to free Schiff bases. A search of the
CSD [1] yielded eight structures of the uncoordinated a-amino acid
Schiff bases derived from aromatic aldehydes, from which seven
compounds exist in the zwitterionic form. The average C@N bond
length from 9 hits is 1.302 (2) , and this distance is slightly longer
than this observed in 1. An analogous search carried out for (N-sal-
icylideneglycinato-N,O,O
0
)-copper(II) derivatives gave 36 com-
pounds, with a mean C@N distance of 1.280 (3) , which is very
close to that in 1. This shortening (compared with free Schiff bases)
observed in 1 is caused by redistribution of p-electron density
within the imine bond and the coordination bond. In the free Schiff
base the imine nitrogen atom is protonated (and consequently pos-
itively charged) and acts as a hydrogen bond donor, what causes
the lengthening of the imine bond.
It must be outlined that the changes in the orientation of
N-substituents occur during the formation of coordination com-
pounds. In the (N-salicylideneglycinato-N,O,O
0
)-copper(II) deriva-
tives, as in 1, all groups containing donor atoms are co-planar,
what is in opposition to the similar structurally characterised pure
ligands, in which the COO group is always twisted out of the plane
of C(aryl)-C@N moiety with the C@N-C-C(OO) torsion angle in the
range of 90160 [1]. Additionally, in these free ligands, except of
one (N-o-vanillylidene-L-histidine [35]), the side chain of the chiral
amino acid and carboxylic group are located on the opposite sides
of the C(aryl)AC@N moiety plane. The complexation does not
change the conformation of N-vanillylidenehistidine [36], which
is the double zwitterionic amino acid Schiff base (Fig. 4). Such
alignment of the negatively charged oxygen atom in a linear posi-
tion in the free Schiff base has been explained by the steric
hindrance and the possibility of forming hydrogen bonds. There
is only one more example of an amino acid Schiff base and its coor-
dination compounds, which crystal structures have been deter-
mined. In the N-(2-hydroxy-1-naphthylidene)threonine [37] and
its mixed ligand copper coordination compound [38] the N-substi-
tuent has different spatial orientation (Fig. 4). The quaternary car-
bon atom exhibits a tetrahedral geometry and the carboxylate and
hydroxyethyl groups are situated on the opposite side of the mol-
ecule. The conguration of the chiral centre and in consequence
the placement of the above mentioned groups is opposite in the
coordination compound in comparison to the free ligand (the car-
boxylate group is located above the arbitrary chosen naphthylid-
ene plane, whereas the carboxylic group is beyond this plane).
The existence of a chiral carbon atom seems to be crucial to
obtain the amino acid Schiff base in the crystalline form. There
are many crystal structures of N-salicylideneglycinato-N,O,O
0
)-
copper(II) derivatives but only few structurally characterised a-
amino acid Schiff bases derived from aromatic aldehydes. In
general there are few reports with structural proof on the forma-
tion of imines of glycine esters however the imines of glycine alkyl
esters have been used successfully in numerous syntheses of a-
aminoacids [39,40] and a,b-diamino esters [41]. The presence of
metal ion in the solution allows the creation of the stable ve-
membered ring, this molecular fragment becomes less labile, the
carbonyl group locates itself in the molecule plane and in conse-
quence the electron density is more localised on the double imine
bond, and in consequence increases this bond stability.
Since the molecular geometry of furylidene-glycine is unknown,
the calculations have been carried out for this exible molecule in
the gas and liquid phase at the MP2 and DFT levels to establish its
electronic structure. The three possible geometries of the com-
pound in both zwitterionic and uncharged form have been used
as starting models (Fig. S1 of Supplementary material). The ini-
tial geometrical parameters were established on the basis of the
known solid-state geometry of uncoordinated a-amino acid Schiff
bases derived from aromatic aldehydes and by modifying the
dihedral angles C@NACAC, NACACAOH and C(furan)AC@NAC
(Table 2). The Gibbs free energy values (Table 3), calculated at both
MP2 and DFT levels of theory, suggest that the uncharged tauto-
meric form of furylidene-glycine is the stable one in the gas phase.
In this minimum energy structure the O atom of the furan ring, the
imine N atom and the O atom of hydroxyl group are located on the
same side, the H atom of the hydroxyl group is located in the posi-
tion allowing formation of an intramolecular hydrogen bond with
the imine N atom. During the geometry optimisation process of the
zwitterionic form, the H atom initially attached to the imine N
atom migrated to the carboxylate group, forming the uncharged
tautomer regardless of the starting geometry. According to these
results, it can be stated that the zwitterionic form does not exist
in the gas phase. Since solvent has an effect on the tautomeric
equilibrium, the energy of each form was calculated using the
self-consistent reaction eld (SCRF) approach, with methanol as a
solvent to obtain a more realistic simulation of experimental con-
ditions. In opposition to the gas phase, the DFT calculations show
that the methanol molecules assist in stabilising the zwitterionic
form, what results from the charged solute polar solvent interac-
tions. In the case of the MP2 optimisation, taking the solvent into
account leads to obtain the lowest energy value for the uncharged
tautomeric form. As for solvent-free calculations, the most stable
geometry is this one with carboxylic/carboxylate group twisted
out of the C(furan)AC@NAC moiety plane. The differences between
the energy values of molecules possessing similar geometries in
b
a
Fig. 4. Superimposition of the N-(2-hydroxy-1-naphthylidene)threonine [36] with
its copper coordination compound geometry [37] (a) and (N-o-vanillylidene-L-
histidine [34] with its uranium coordination compound geometry [35] (b).
A. Trzesowska-Kruszynska / Journal of Molecular Structure 1017 (2012) 7278 75
the gas and liquid phase are small, ranging from 13 to 18 kcal/mol.
The results of calculations of the molecule geometry in the pres-
ence of solution are not conclusive and may indicate the equilib-
rium between both forms existing in solution, but taking into
consideration the fact that the known a-amino acid Schiff bases
exist in the solid state as a locally charged molecules, the zwitter-
ionic form is more probable and the equilibriumis probably shifted
towards it.
3.2. Spectroscopic studies
The IR spectrum of the complex (Table S3 of Supplementary
material contains characteristic bands of the stretching and bend-
ing vibrations of the C@C, C@N and CH groups. The OAH stretching
vibrations of water appears as a broad split absorption band
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1
7
4
.
2

0
.
6

6
1
.
2
1
.
2

0
.
3
U
n
c
h
a
r
g
e
d
f
o
r
m
2
1
7
5
.
6
1
2
1
.
5

0
.
6

2
4
.
8
1
8
0
1
7
8
.
3
1
7
5
.
6
1
1
5
.
1

0
.
6

3
9
.
6
1
8
0

1
7
9
.
6
U
n
c
h
a
r
g
e
d
f
o
r
m
3
1
0
3
.
6
1
2
1
.
8

0
.
6

1
7
.
8
1
8
0
1
7
8
.
5
1
0
3
.
6
a

0
.
6
a
1
8
0
a
Z
w
i
t
t
e
r
i
o
n
i
c
f
o
r
m
1
1
7
5
.
6

1
8
0
.
0

1
.
2
0
1
7
5
.
6
1
7
6
.
7

1
.
2
0
.
5
Z
w
i
t
t
e
r
i
o
n
i
c
f
o
r
m
2
1
7
5
.
6
1
7
4
.
6

1
8
0

1
7
9
.
6
1
7
5
.
6
1
2
1
.
1

1
8
0

1
7
8
.
7
Z
w
i
t
t
e
r
i
o
n
i
c
f
o
r
m
3
1
0
3
.
6
1
2
4
.
1

1
8
0

1
7
8
.
9
1
0
3
.
6
1
1
6
.
7

1
8
0

1
7
7
.
9
a

a
n
e
n
e
r
g
y
m
i
n
i
m
u
m
c
o
u
l
d
n
o
t
b
e
f
o
u
n
d
.
a

C
@
N

C
d
i
h
e
d
r
a
l
a
n
g
l
e
.
b

N
A
C
A
C
A
O
(
H
)
d
i
h
e
d
r
a
l
a
n
g
l
e
.
c

C
f
u
r
a
n
A
C
@
N
A
C
d
i
h
e
d
r
a
l
a
n
g
l
e
.
Table 3
Gibbs free energies obtained at 298 K and 1 atm (1 a.u. = 627.5095 kcal/mol).
Tautomers DFT without solvent MP2 without solvent
Uncharged form 1 551.282200 549.727063
Uncharged form 2 551.288186 549.730654
Uncharged form 3 551.288178 549.730654
Zwitterionic form 1 551.289035 549.730877
Zwitterionic form 2 551.291123 549.731763
Zwitterionic form 3 551.291120 549.731764
DFT with solvent MP2 with solvent
Uncharged form 1 a 549.755508
Uncharged form 2 551.317260 549.756850
Uncharged form 3 551.317420 a
Zwitterionic form 1 551.318823 549.755061
Zwitterionic form 2 551.316355 549.752728
Zwitterionic form 3 551.319359 549.752691
a an energy minimum could not be found.
Fig. 5. The experimental (solid line) and calculated (dashed line) electronic
absorption spectra of 1.
76 A. Trzesowska-Kruszynska / Journal of Molecular Structure 1017 (2012) 7278
centred at 3265 cm
1
. The vibration mode corresponding to the
strong absorption band at 1575 cm
1
with a pronounced shoulder
at 1679 cm
1
is complex. It is typical for C@C and C@N stretching
vibrations, and also can be attributed to the asymmetric stretching
vibrations of carboxylate ion. The symmetric stretching vibrations,
m(COO

) are observed at 1393 cm

1
. As for glycine, for 1 the CAN
stretching vibrations appear as a weak intensity band at
958 cm
1
. The single bands at 560 and 480 cm
1
correspond to
the vibrations of CuAO and CuAN bonds, respectively.
The UV/Vis spectrum was recorded for the solid-state sample,
thus no solvent effects were involved. The spectrum of 1 exhibits
four principal absorption bands. The strong bands located at 230
and 250 nm with a shoulder at 330 nm can be attributed to
p ?p

transitions. The broad band centred at 620 nm can be con-

sidered as a d ?d transition band [42,43].
The TD-DFT calculations were performed for an isolated
complex molecule to verify the nature of transitions. The experi-
mental spectrum was measured for the compound in the solid
state, but due to methodological reasons, the calculations were
carried out for the isolated molecule. The experimental and calcu-
lated electronic spectra are compared in Fig. 5. Each calculated
excited state was represented by the Lorentzian function with
the scale parameter of 10. Generally, in the computed UVVis spec-
trum the bands are red shifted. The transitions observed in the
solid-state spectra have increased energy in comparison to those
observed in the calculated TD-DFT spectrum of the isolated mole-
cule, due to structural differences between the optimised and
experimental geometrical parameters. Apart from minor variation
in the bond lengths (mainly the C-H bonds are elongated), the
greatest difference is observed for value of the angle formed be-
tween two ligand planes, which is 4.05 for crystal structure and
49.3 for the optimised structure.
The calculated ground state a- and b-spin molecular orbital en-
ergy level diagram is presented in Fig. 6. The a-spin HOMO orbital
is the spatial counterpart of the b-spin LUMO orbital. The aHOMO-
3, aLUMO and aLUMO + 1 orbitals have spatial distribution similar
to those of the bHOMO-2, bLUMO + 1 and bLUMO + 2 orbitals,
respectively. The major contributions to the change in the electron
density associated with electronic transitions have b-spin orbitals.
The frontier orbitals and bHOMO-1 and bLUMO + 1 are predomi-
nantly Cu d orbitals with small contribution from p ligand orbitals
(Fig. S2 of Supplementary material). The bHOMO-2 and bHOMO-
3 are more delocalised. Energetically lower, the bHOMO-4 and
bHOMO-8 are p-bonding orbitals, localised on the furan rings.
The bHOMO-6 and bHOMO-7 are mainly carboxylate group-based
orbitals.
Experimental and theoretical data are summarised in Table 4.
According to the results of TDDFT calculations, the lower energy
Fig. 6. The selected a- and b-spin molecular orbital energy level diagram of 1 and contours of frontier molecular orbitals. Orbitals with similar spatial distribution are
connected by dashed lines.
Table 4
Experimental and selected calculated UVVis absorption bands, oscillator strengths and the major contributions of 1 calculated by TD-DFT
method.
Wavelength (nm) computed
(experimental)
Oscillator
strength
Character The most important orbital excitation
a-Spin orbital b-Spin orbital
681 (620) 0.005 d ? d HOMO2 ?LUMO + 2
HOMO1 ?LUMO + 2
665 0.003 d ?d HOMO3 ?LUMO + 2
p (Furan) ?d HOMO8 ?LUMO + 2
d ?d HOMO2 ?LUMO + 2
428 (440) 0.007 d ?d HOMO ?LUMO + 1
315 (330) 0.153 p (Furan) ?d HOMO4 ?LUMO + 1
d ?d HOMO3 ?LUMO
307 0.095 p (Furan) ?d HOMO4 ?LUMO + 1
295 0.194 p (CO) ?d/p

(Furan)
HOMO7 ?LUMO
265 (250) 0.019 p (Furan) ?d HOMO8 ?LUMO + 2
p (CO) ?d HOMO6 ?LUMO + 1
249 (230) 0.036 p (Furan) d/p

(Furan)
HOMO8 ?LUMO
A. Trzesowska-Kruszynska / Journal of Molecular Structure 1017 (2012) 7278 77
absorption bands arise from the transitions between a- and b-spin
orbitals and can be attributed to transitions of d ?d character, ad-
mixed with p ?d ligand-to-metal charge-transfer transition
(LMCT) due to participation of p-bonding orbitals of the furan ring.
These transitions are mainly associated with transitions to the
vacant bLUMO + 2. The higher energy absorption bands are related
with the p ?d and p ?p

ligand-to-metal, ligandligand charge-

transfer and interligand transitions.
3.3. Thermal stability
The complex compound 1 is stable up to 70 C in the air atmo-
sphere and its decomposition is a multi-stage process. The initial
step of the thermal decomposition occurs within the temperature
range of 70220 C. The DTA (140 C, 210 C) and DTG (minima
at 140 C, 190 C) curves indicate that there are two sub-processes.
This rst endothermic step is attributed to the removal of water
molecules. The mass spectrum of the thermal decomposition
shows the ion current signals m/z = 17 and 18 which correspond
to the molecular mass of OH
+
, H
2
O
+
, respectively. According to
the detected gaseous products, in the second stage the decomposi-
tion of the organic ligand and removal of the water molecules
begin simultaneously. The succeeding stage is exothermic. This
step of the decomposition is characterised by strong, narrow peaks
on the DTA curve (320 C) and three minima on the DTG curves
(270 C, 305 C and 340 C) and the biggest mass loss. The main
volatile products of decomposition and fragmentation processes
include C
+
, O
+
, CO

2
, CO
2
H
+
, OH
+
, H
2
O
+
, C
2
H

2
, CH
2
O
+
, C
2
H
6
O
+
and
C
3
H

3
. During heating over 400 C the compound decomposition
nishes with forming the copper(II) oxide as a nal product.
4. Conclusions
The mononuclear Cu(II) complex has been prepared with the
bidentate glycine Schiff base ligand obtained in situ from the fur-
an-2-carbaldehyde and glycine. The complex molecule possesses
rather unusual ligand coordination. The results of structural analy-
sis and quantummechanical calculations indicate the existence of
weak C@O p interactions governing the crystal structure.
Although the attempts to obtain and isolate the pure ligand,
N
0
-(2-furfurylidene)glycine, were unsuccessful, the results of MP2
and DFT calculations suggest that if such amino acid Schiff base
exist, it will form the zwitterion in the solid-state. According to
the analysis of the known structural data, the existence of a chiral
centre seems to be crucial to obtain the amino acid Schiff base in
the crystalline form.
Acknowledgments
This work was nanced by funds allocated by the Ministry of
Science and Higher Education to the Institute of General and
Ecological Chemistry, Technical University of Lodz, Poland (Grant
No. IP 2010 043770). The GAUSSIAN03 calculations were carried
out in the Academic Computer Centre CYFRONET of the AGH Uni-
versity of Science and Technology in Cracow, Poland (Grant No.
MNiSW/SGI3700/Pdzka/040/2008).
Appendix A. Supplementary material
CCDC-848630 (1) contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
at www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cam-
bridge Crystallographic Data Centre (CCDC), 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 (0)1223 336033; email: depos-
it@ccdc.cam.ac.uk). Supplementary data associated with this
article can be found, in the online version, at http://dx.doi.org/
10.1016/j.molstruc.2012.03.003.
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