Synthesis, structural, and thermal analyses of copper(II) and oxido-vanadium(IV) complexes of 4-bromo-2-(((5-chloro-2-hydroxyphenyl)imino) methyl)phenol

Article abstract of DOI:10.1080/00958972.2013.815343

Reaction of 4-bromo-2-(((5-chloro-2-hydroxyphenyl)imino)methyl)phenol (H2L) with Cu(OAc)2·4H2O or VOSO4·3H2O and 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) in a 1: 1: 1 mol ratio led to [CuL(phen)] and [VOL(bipy)] which have distorted square pyr

Full text of DOI:10.1080/00958972.2013.815343

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Synthesis, structural and thermal analyses of copper(II)
and vanadium(IV) complexes of 4-bromo-2-(((5-
chloro-2-hydroxyphenyl)imino)methyl)phenol
a
b
c
d e
REZA TAKJOO , JOEL T. MAGUE , ALIREZA AKBARI & S. YOUSEF EBRAHIMIPOUR
a
Department of Chemistry, School of Sciences , Ferdowsi University of Mashhad , Mashhad
1775-1436, Iran
9
b
Department of Chemistry , Tulane University , New Orleans , LA 70118 , USA
Department of Chemistry , Payame Noor University (PNU) , 19395-4697, Tehran , Iran
Department of Chemistry , Payame Noor University (PNU) , 19395-4697, Tehran , Iran
Department of Chemistry , University of Jiroft , Jiroft , Iran
c
d
e
Accepted author version posted online: 14 Jun 2013.
To cite this article: REZA TAKJOO , JOEL T. MAGUE , ALIREZA AKBARI & S. YOUSEF EBRAHIMIPOUR (2013):
Synthesis, structural and thermal analyses of copper(II) and vanadium(IV) complexes of 4-bromo-2-(((5-chloro-2-
hydroxyphenyl)imino)methyl)phenol, Journal of Coordination Chemistry, DOI:10.1080/00958972.2013.815343
To link to this article: http://dx.doi.org/10.1080/00958972.2013.815343
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Synthesis, structural and thermal analyses of copper(II) and vanadium(IV)
complexes of 4-bromo-2-(((5-chloro-2-hydroxyphenyl)imino)methyl)phenol
a
b
c
d
REZA TAKJOO* , JOEL T. MAGUE , ALIREZA AKBARI and S. YOUSEF EBRAHIMIPOUR
a
Department of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Mashhad 91775-1436, Iran
b
Department of Chemistry, Tulane University, New Orleans, LA 70118, USA
c
Department of Chemistry, Payame Noor University (PNU), 19395-4697 Tehran, Iran
d
Department of Chemistry, Payame Noor University (PNU), 19395-4697 Tehran, Iran; Department of Chemistry,
University of Jiroft, Jiroft, Iran
Reaction of 4-bromo-2-(((5-chloro-2-hydroxyphenyl)imino)methyl)phenol (H L) with
2
Cu(OAc) ·4H O or VOSO ·3H O and 2,2’-bipyridine (bipy) or 1,10-phenanthroline (phen) in a
2
2
4
2
1
:1:1 mol ratio led to [CuL(phen)] and [VOL(bipy)] which have distorted square pyramidal and
octahedral geometries, respectively. The compounds were characterized by elemental analyses,
FT-IR, UV-Vis, TGA and X-ray diffraction. Their thermolyses have three stages: phen or bipy
removal, separation of H L minus chloride and bromide of H L and complete thermal
2
2
decomposition to the metal oxide.
Keywords: Vanadium complex; Copper complex; TGA; Spectroscopy; Crystal structures
1
. Introduction
Salicylidene compounds containing ONO donors have special potential in biochemistry [1, 2].
The biological effects of metal complexes of these compounds are more pronounced than that of
their ligands [3, 4]. One of the main reasons for attention to these types of ligands is that in many
metalloproteins the central element is surrounded by asymmetric ligands and the targeted
synthesis of these complexes can help us design appropriate mimics for the study of enzymes
[
5, 6]. As the salicylidene used in this work showed antimicrobial properties, it is expected that
its metal complexes demonstrate significant biological properties too [1]. In particular,
complexes of vanadium and copper are interesting because they play significant roles in many
biological processes [7].
Several reports have shown bioactivities of copper complexes with CuL L formulas
1
2
where L and L are ONO Schiff base and NN donor, respectively [8, 9]. These compounds are
1
2
mimics for copper(II) protein species. The biological activity of these compounds depends on
*Corresponding author. Emails: rezatakjoo@yahoo.com; r.takjoo@um.ac.ir
1

non-covalent interactions between aromatic units [10]. Many complexes show anti-tumor and
anti-microbial properties [11, 12]. Heterocyclic copper(II) complexes are associated with, or
intercalated through, the DNA surface and assist in hydrolytic or oxidative cleavage of DNA
[
13, 14]. The oxido vanadium(IV) complexes with ONO donors and heterocycles have
significant impact on biochemistry processes such as DNA cleavage [15]. Vanadium(IV)
complexes are good candidates for insulin mimics [16]. Based on the physico-chemical
investigations on oxide vanadium complexes, these compounds are good models for protein
studies [17, 18]. High absorption and low toxicity of these compounds make them suitable
materials for bio-applications [19].
Herein, we report synthesis, spectroscopy, TGA and X-ray structural studies of two new
complexes of the Schiff base 4-bromo-2-(((5-chloro-2-hydroxyphenyl)imino)methyl)phenol
(
H L) (scheme 1) with Cu(II) and V(IV), [CuL(phen)] and [VOL(bipy)].
2
Scheme 1. General structures of the free ligand tautomers (H L).
2
2
2
. Experimental
.1. Materials and instrumentation
All chemicals and solvents were analytical reagent grade and used as received. 5-Bromo-2-
hydroxybenzaldehyde and 2-amino-4-chlorophenol were purchased from Merck Company. H L
2
was prepared according to our previous work [20]. Microanalyses for C, H and N were
determined on a Thermo Finnigan Flash Elemental Analyzer 1112EA. IR spectra were measured
-1
as KBr pellets on a FT-IR 8400-SHIMADZU spectrophotometer (400-4000 cm ). Molar
2

-3
conductivities of 10 M solutions of the complexes in DMSO were determined by a Metrohm
12 Conductometer at 25 °C. Electronic spectra of the compounds in DMSO (ca. 25 °C) were
run on SHIMADZU model 2550 UV–Vis spectrophotometer (260-800 nm).
Thermogravimetric analyses (TGA and DTG) were carried out in an oxygen atmosphere
10 mL/min) with a heating rate of 10 °C/min using a TGA-50 SHIMADZU thermal analyzer
7
a
(
from 20-1000 °C. X-ray diffraction data were measured by a Bruker Smart APEX CCD
diffractometer.
2
.2. Preparation of 4-bromo-2-(((5-chloro-2-hydroxyphenyl)imino)methyl)phenol (H L)
2
A solution of 2-amino-4-chlorophenol (0.2 mmol, 0.03 g) in 5 mL of ethanol was added to an
equimolar quantity of 2-hydroxy-5-bromobenzaldehyde in 5 mL of ethanol with vigorous
stirring. After 30 min of refluxing, cooling the solution resulted in formation of a red precipitate,
which was separated by filtration, washed with cold ethanol and dried in a desiccator over
anhydrous CaCl . Red. Yield: 0.54 g, 82%. m.p.: 199 °C. Anal. Calc. for C H BrClNO
2
2
13
9
-1
(
326.57 g mol ): C, 47.81; H, 2.87; N, 4.29. Found: C, 47.78; H, 2.80; N, 4.24%. FT-IR (KBr)
-
1
cm : ν(OH) 3448wb, ν(N-H) 3130sb, ν(C=N) 1627s, ν(C=C ) 1581s, ν(C-O) 1319m, ν(C-Cl)
ring
-1
-1
6
78s, ν(C-Br) 585s. UV/Vis (DMSO) λmax, nm (log(ε), L mol cm ): 286(4.03), 368(4.14),
4
38(3.67).
2
.3.
Preparation
of
(1,10-phenanthroline)[4-bromo-2-((5-chloro-2-
hydroxyphenylimino)methyl)phenol]copper(II) [CuL(phen)] (1)
Cu(OAc) ·4H O (0.1 mmol, 0.02 g) was added to a solution of H L (0.1 mmol, 0.03 g) and
2
2
2
NaOH (0.2 mmol, 0.01 g) in 6 mL of boiling methanol, and the mixture was refluxed in a water
bath for 30 min. 1,10-Phenanthroline (0.1 mmol, 0.02 g) was added to the resulting dark-green
solution which was further refluxed for ca. 3 h. After cooling, the solution was filtered and left to
stand overnight. Black crystals suitable for crystallography separated after four days and were
dried in a vacuum desiccator over CaCl . Yield: 0.045 g, 78%. m.p.: >300 °C. Molar
2
-
3
-1
2
-1
conductivity (1.0×10
M, DMSO): 2.90
Ω
cm
mol . Anal. Calc. for
-1
C H BrClCuN O ·0.50H O (577.31 g mol ): C, 52.01; H, 2.79; N, 7.28. Found: C, 52.17; H,
25
15
3
2
2
-1
2
.80; N, 7.24%. FT-IR (KBr) cm : ν(C=N) 1612s, ν(C=C ) 1520s, ν(C-O) 1296m, ρ(py )
ring
ring
3

-1
-1
1
4
018m, ν(C-Cl) 709m, ν(C-Br) 656w. UV/Vis (DMSO) λmax, nm (log(ε), L mol cm ): 272(4.5),
48(4.37), 474(4.32), 654(2.28).
2
.4. Preparation of (2,2'-bipyridine)[4-bromo-2-((5-chloro-2-hydroxyphenylimino)methyl)
phenol] oxidovanadium(IV) [VOL(bipy)] (2)
VOSO ·3H O (0.1 mmol, 0.02 g) was added to a solution of H L (0.1 mmol, 0.03 g) in 6 mL of
4
2
2
hot methanol and the solution was refluxed for 1 h on a water bath. 2,2'-Bipyridine (0.1 mmol,
.02 g) was added to the resulting brown solution and reflux was continued for 3 h. After one
0
day, suitable single crystals appeared upon slow evaporation of the solvent. The product was
isolated, washed with cold ethanol and dried in a vacuum desiccator over CaCl . Parallelepiped.
2
-
3
-1
2
Red. Yield: 0.039 g, 67%. m.p.: 236 °C. Molar conductivity (1.0×10 M, DMSO): 21.5 Ω cm
-1
-1
mol . Anal. Calc. for C H BrClN O V (579.72 g mol ): C, 49.72; H, 3.30; N, 7.25. Found: C,
2
4
19
3
4
-1
4
9.68; H, 3.22; N, 7.31%. FT-IR (KBr) cm : ν(C=N) 1597s, ν(C=C ) 1512s, ν(C-O) 1288m,
ring
ν(V=O) 948s, ρ(py ) 905m, ν(C-Cl) 702m, ν(C-Br) 648w. UV/Vis (DMSO) λmax, nm (logε,
ring
-1
-1
L mol cm ): 276(4.5), 444(4.1), 658(2.1).
2
.5. X-ray Crystal structure determination
Crystals of 1 and 2 were mounted on a Cryoloop™ with Paratone™ oil and placed in the cold
nitrogen stream provided by the low temperature attachment to the diffractometer. Full spheres
of intensity data were collected using 3 sets of 400 frames, each of width 0.5° in ω, collected at φ
=
0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω =
-
30.00 and 210.00° (1) or 3 sets of 606 frames each of width 0.3° in ω collected at φ = 0, 120 and
2
2
40° (2). The raw intensity data were converted to F values with SAINT [21] with the same
software executing a global refinement of unit cell parameters. Absorption corrections and
merging of symmetry equivalent reflections were carried out with SADABS [22] and the
structures solved by Patterson (1) and direct methods (2) using SHELXS [23]. The structures
were refined by full-matrix, least-squares procedures (SHELXL [23]) and all other calculations
were carried out with SHELXTL [24]. Crystal data are provided in table 1.
4

3
3
. Results and discussion
.1. General aspects
Reactions of the ligand and metal salts in an equimolar ratio resulted in the metal complexes in
good yield. The complexes were stable at room temperature and also soluble in DMSO and
DMF, but only partially soluble in other organic solvents such as methanol, acetone, acetonitrile
-3
and chloroform. The C, H, N elemental analysis data and the low molar solution (1.0×10 M)
conductances of the complexes in DMSO are in conformity with the proposed formulas. Our
attempts to prepare crystals of [CuL(bipy)] and [VOL(phen)] compounds were unsuccessful.
3
.2. Characterization
The υ(OH) due to the presence of water (for 1) or methanol (for 2) in the lattice occurs at 3417
-1
-1
and 3232 cm , respectively. The band at 3070 cm is attributed to the NH…O stretch,
confirming the presence of the keto form in the solid (scheme 1) [25]. In solution, the ligand
exists in the enol tautomeric form, and by loss of its enolic proton in complexation is a dianionic
-1
-1
ligand. The band at 1627 cm is assigned to the azomethine of H L and shifts to 1612 cm and
2
-1
1
597 cm in [CuL(phen)] and [VOL(bipy)], respectively [26]. This variation in frequency
supports the coordination of the azomethine nitrogen. By coordination, the C-O vibration of the
-1
-1
-1
ligand at 1319 cm shifts to 1296 cm and 1288 cm , respectively, for 1 and 2 [27]. This
-1
reduction supports coordination of the ligand oxygen to the metal. Bands at 1018 cm in 1 and
-1
9
05 cm in 2 are attributed to the breathing vibration of pyridine [28]. The v(V=O) of the
-1
vanadyl is at 948 cm [29].
The high energy portion of the electronic spectrum of 1 consists of bands at 272, 448 and
74 nm while that of 2 shows bands at 276 and 444 nm. The bands at ca. 270 nm are attributed
4
to a π→π* transition of the azomethine in the complexes while those at 444 nm and 448 nm for 1
and 2, respectively, are attributed to the LMCT charge transfer band which is evidence for
coordination of pyridyl nitrogen to copper(II) and oxidovanadium(IV) [30]. Finally, peaks at
6
54 nm in 1 and 658 nm in 2 are attributed to d-d transitions.
3
.3. Crystallographic description of complexes
The asymmetric unit of 1 consists of two crystallographically independent molecules of the
complex plus two lattice waters while that of 2 is a single molecule. In 1 there are two
5

asymmetric units per unit cell while in 2 there are four. Perspective views of one isomer each
vide infra) of the two independent molecules of 1 are presented in figures 1 and 2 while the
(
unique molecule of 2 is presented in figure 3. Pertinent bond distances and angles are shown in
tables 2 and 3, respectively.
The metal ion in both independent molecules of 1 adopts a slightly distorted square
pyramidal coordination in which the Schiff base occupies basal positions and phen spans basal
and axial positions with the axial Cu-N distance significantly longer than the basal Cu-N3 and
Cu-N2 distances as expected. With this geometry, an unsymmetrical ligand coordinating in the
basal plane can do so in two different ways, as shown figure 4. Since the peripheries of these two
isomers are quite similar, they could easily co-crystallize in the same sites in the unit cell. Were
this to occur, the majority of the atoms of both isomers would occupy essentially the same
positions with the only ones not doing so being the halides and the –CH=N-. The result would be
an apparent disorder in Cl and Br substituents as well as in the azomethine portion, and this is
clearly seen in the difference Fourier maps. This phenomenon has been observed in very similar
tetradentate Schiff-base ligands and it is also found in Mn(III) and Fe(III) complexes [31].
However, there are some cases with a single isomer [32]. This may be caused by the size of the
substituents on phenyl rings or also reaction conditions, but there are insufficient systematic
studies to suggest a pattern of causative factors. The data in tables 2 and 3 indicate that the only
notable difference between the coordination spheres of copper in the two independent molecules
is in the N-Cu-O angle in the 6-membere chelate ring. However, because of the disorder,
significance should not be placed on this difference and detailed discussions of the full geometry
of the coordination sphere of copper are inappropriate. The Schiff base in 1 is twisted such that
the dihedral angles between the phenoxy rings are, respectively, 7.1(1)° and 13.5(4)° for
molecule 1 and molecule 2. There is a π-stacking interaction between the pyridine ring
containing N3 in molecule 1 with that containing N6 in molecule 2 (distance between ring
centroids = 3.498(3) Å, interplanar spacing =3.356(2) Å, interplanar angle = 4.42°).
Additionally, the pyridine ring containing N3 in molecule 1 participates in a π-stacking
interaction with its centrosymmetrically-related counterpart at –x, 1-y, -z (distance between ring
centroids = 3.521(2) Å, interplanar spacing = 3.311(2) Å) while that containing N5 shows π-
stacking with its centrosymmetrically-related counterpart at –x, 2-y, 1-z (distance between ring
6

centroids = 3.803(4) Å, interplanar spacing = 3.350(2) Å). These interactions are depicted by
dotted lines in figure 5.
As is evident from table 3, the vanadium in 2 adopts a distorted octahedral geometry with
the distortions mainly resulting from the geometrical constraints of the ligands. Unlike 1 and
related compounds [20], 2 has one molecule in the asymmetric unit and appears to be a single
isomer. The twist of the Schiff base in 2, measured as for 1, is 5.2(2)° while bipy shows a slight
twist of 4.9(2)° between the pyridine rings. The vanadium is 0.359(2) Å out of the plane defined
by O2, N3, O3 and N2 towards O1 while this plane makes an angle of 87.20(7)° with that
defined by V1, N2, C18, C19 and N3.
3
.4. Thermogravimetric analysis
TGA and DTG curves of 1 and 2 are shown in Supplementary Material, from which 1 is seen to
undergo three thermal decomposition stages and 2 shows only two.
The first combined mass loss for 1 is attributed to removal of 1,10-phenanthroline at 334-
4
05 °C with a mass loss of 35.23% (calc. mass loss = 35.21%). The second DTG peak, having a
maximum at 428 °C, corresponds to a weight decrease of about 29.93% (calc. mass loss =
0.08%), which is consistent with removal of the chloride and bromide of the Schiff base. In the
3
last step at 437-632 °C (maximum at 534 °C), it loses 23.46% (calc. mass loss = 22.08%) of its
mass by decomposition of the remaining ligand, leaving CuO as the final residue. In 2 the TGA
curve shows a mass loss of 28.52% (calc. mass loss = 28.47%) at 271 °C, which is in agreement
with the loss of bipy. In the other step, the Schiff base is removed at 327 °C with a 53.95% (calc.
mass loss = 53.60%) decrease in mass. The 28.75% mass of the remaining residue indicates it to
be V O (calc. value for V O = 29.0%).
2
5
2
5
4
. Conclusion
Preparation
hydroxyphenylimino)methyl)phenol copper(II) [CuL(phen)] and (2,2′-bipyridine)(4-bromo-2-
(5-chloro-2-hydroxyphenylimino)methyl)phenol oxidovanadium(IV) [VOL(bipy)] involving a
dinegative tridentate ONO donor in the form of H L are reported. The [CuL(phen)] and
and
characterization
of
(1,10-phenanthroline)(4-bromo-2-((5-chloro-2-
(
2
[
VOL(bipy)] complexes are structurally characterized as five- and six-coordinate species with
distorted square pyramidal and octahedral geometries, respectively. On the basis of the spectral
7

and X-ray structure analysis H L is doubly deprotonated and coordinated to Cu and V as a
2
dianionic tridentate ligand via the ONO donors. The coordination spheres of the complexes are
completed by phen in [CuL(phen)] and an oxygen atom and a bipy in [VOL(bipy)]. The TGA
results, showing stepwise removal of the ligands to finally yield metal oxide, are fully consistent
with the structural results.
Supplementary data
CCDC 880833 and CCDC 880832 contain the supplementary crystallographic data for
[
CuL(phen)] and [VOL(bipy)], respectively. These data can be obtained free of charge via
http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: (+44) 1223-336-033; or E-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgements
The authors are thankful to the Chemistry Department and Tulane Crystallography Laboratory of
Tulane University for their support. R. Takjoo and A. Akbari acknowledge the Ferdowsi
University of Mashhad and Payame Noor University (PNU) for financial assistance.
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31] (a) M.A. Yampolskaya, S.G. Shova, N. V. Gerbeleu, Yu. A. Simonov, V.K. Belskii, A.A.
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Űlküseven. Polyhedron, 30, 515 (2011).
[
1
0

Table 1. Crystal data for 1 and 2.
Complex
1
2
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
Space group
Unit cell dimensions
a (Å)
C H BrClCuN O ·0.50H O
C H BrClN O V
2
5
15
3
2
2
24 19
3
4
577.31
100(2)
0.71073
Triclinic
Pī
579.72
100(2)
0.71073
Monoclinic
P2 /n
1
12.6593(13)
14.8471(16)
15.306(3)
114.423(2)
92.575(2)
114.961(1)
2289.3(5)
4
9.562(4)
15.221(7)
15.925(7)
b (Å)
c (Å)
α (°)
β (°)
99.612(6)
γ°
3
Volume (Å )
2285.4(18)
4
Z
3
Density (calculated, Mg/m )
1.675
1.685
2.337
1164
-
1
Absorption coefficient (mm )
2.847
F(000)
1152
3
Crystal size (mm )
0.23 × 0.16 × 0.16
2.05 to 28.28
40081
0.20 × 0.07 × 0.03
1.86 to 28.50
19511
θ range for data collection (°)
Reflns. total
Independent reflections
Rint
11139
5370
0.0794
0.0515
Completeness (%) (θmax
)
99.2 (27.50°)
99.5 (27.00°)
Absorption correction
Semi-empirical
from equivalents
Semi-empirical
from equivalents
Max. and min. transmission
Refinement
0.6587 and 0.5277
0.9332 and 0.7143
Full-matrix least-squares on F
5370 / 0 / 308
2
2
Full-matrix least-squares on F
11139 / 20 / 639
1.029
Data / restraints / parameters
2
Goodness-of-fit on F
1.062
Final R indices [I > 2σ(I)]
R1 = 0.0714,
wR2 = 0.1974
R1 = 0.0510,
wR2 = 0.1230
R indices (all data)
R1 = 0.0931,
R1 = 0.0642,
wR2 = 0.2084
wR2 = 0.1309
-
3
Largest diff. peak and hole (e.Å )
1.470 and -1.608
1.820 and -0.837
1
1

Table 2. Bond distances (Å) and angles (°) for 1.
Molecule 1
1.934(5)
Molecule 2
Cu(1)-O(1)
Cu(1)-O(2)
Cu(1)-N(1)
Cu(1)-N(2)
Cu(1)-N(3)
Cu(2)-O(3)
Cu(2)-O(4)
Cu(2)-N(4)
Cu(2)-N(5)
Cu(2)-N(6)
1.917(5)
1.933(5)
1.985(7)
2.013(4)
2.308(4)
1.946(4)
1.972(6)
2.005(4)
2.297(4)
O(1)-Cu(1)-O(2)
O(1)-Cu(1)-N(1)
O(2)-Cu(1)-N(1)
O(1)-Cu(1)-N(2)
O(2)-Cu(1)-N(2)
N(1)-Cu(1)-N(2)
O(1)-Cu(1)-N(3)
O(2)-Cu(1)-N(3)
N(1)-Cu(1)-N(3)
N(2)-Cu(1)-N(3)
165.61(19)
99.6(2)
O(3)-Cu(2)-O(4)
O(3)-Cu(2)-N(4)
O(4)-Cu(2)-N(4)
O(3)-Cu(2)-N(5)
O(4)-Cu(2)-N(5)
N(4)-Cu(2)-N(5)
O(3)-Cu(2)-N(6)
O(4)-Cu(2)-N(6)
N(4)-Cu(2)-N(6)
N(5)-Cu(2)-N(6)
164.5(2)
104.1(2)
74.7(2)
78.4(2)
91.69(19)
89.29(17)
167.4(2)
92.90(16)
101.35(16)
106.7(2)
78.12(15)
90.42(19)
90.4(2)
165.1(2)
91.04(18)
104.27(16)
105.6(2)
76.90(15)
1
2

Table 3. Bond distances (Å) and angles (°) for 2.
V(1)-O(1)
V(1)-O(2)
V(1)-O(3)
1.611(3)
1.947(3)
1.994(3)
V(1)-N(1)
V(1)-N(3)
V(1)-N(2)
2.080(3)
2.135(3)
2.314(3)
O(1)-V(1)-O(2)
O(1)-V(1)-O(3)
O(2)-V(1)-O(3)
O(1)-V(1)-N(1)
O(2)-V(1)-N(1)
O(3)-V(1)-N(1)
O(1)-V(1)-N(3)
O(2)-V(1)-N(3)
100.18(13)
100.73(13)
158.03(11)
103.57(12)
88.65(11)
80.00(11)
96.60(12)
94.52(11)
O(3)-V(1)-N(3)
N(1)-V(1)-N(3)
O(1)-V(1)-N(2)
O(2)-V(1)-N(2)
O(3)-V(1)-N(2)
N(1)-V(1)-N(2)
N(3)-V(1)-N(2)
89.68(11)
158.70(12)
169.28(12)
81.07(11)
79.64(11)
87.07(11)
72.68(11)
1
3

Figure 1. Perspective view of molecule 1 for 1. Displacement ellipsoids are drawn at the 50%
level and hydrogens are shown as spheres of arbitrary radius. Only one component of the
disorder is shown.
1
4

Figure 2. Perspective view of molecule 2 for 1. Displacement ellipsoids are drawn at the 50%
level and hydrogens are shown as spheres of arbitrary radius. Only one component of the
disorder is shown.
1
5

Figure 3. Perspective view of 2. Displacement ellipsoids are drawn at the 50% level and
hydrogens are shown as spheres of arbitrary radius.
1
6

Figure 4. Two different ways of coordination of the unsymmetrical ligand in the basal plane to
copper(II).
1
7

Figure 5. Illustration of the π-π stacking interactions in 1 with hydrogens omitted for clarity.
1
8