Influence of meridional N3-ligands on supramolecular assembling and redox behavior of carboxylatocopper(II) complexes

Article abstract of DOI:10.1016/j.inoche.2011.08.005

Mononuclear phenylglyoxylato- and 4-R-benzoatocopper(II) complexes with two different 1,3-bis(2-arylimino)isoindoline ligands (aryl = pyridyl, or benzimidazolyl) have been synthesized and characterized. Coordination mode of the carboxylate ligands is very

Full text of DOI:10.1016/j.inoche.2011.08.005

Inorganic Chemistry Communications 14 (2011) 1767–1772
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/inoche
Influence of meridional N3-ligands on supramolecular assembling and redox behavior
of carboxylatocopper(II) complexes
a
b
József S. Pap a, Vanda Bányai a, Dávid S. Szilvási a, József Kaizer a, , Gábor Speier , Michel Giorgi
⁎
a
Department of Chemistry, University of Pannonia, 8200 Veszprém, Hungary
b
Aix-Marseille Université, FR1739, Spectropole, Campus St. Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille cedex 20, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Mononuclear phenylglyoxylato- and 4-R-benzoatocopper(II) complexes with two different 1,3-bis(2-arylimino)
isoindoline ligands (aryl=pyridyl, or benzimidazolyl) have been synthesized and characterized. Coordination
mode of the carboxylate ligands is very similar (monodentate) in each case, while redox behavior of the copper
center is dependent on the aryl- and 4-R-substituents. The supramolecular assembly in the solid state via hydro-
gen bonds and π-stacking between the ligands can be influenced by the aryl-group and carboxylate ligand.
© 2011 Elsevier B.V. All rights reserved.
Received 23 June 2011
Accepted 13 August 2011
Available online 27 August 2011
Keywords:
Copper(II)
Isoindoline
Carboxylate
Redox chemistry
Supramolecular assembly
Mixed-ligand copper complexes with carboxylate ligands are
of perpetual interest due to their interesting structural properties
[1,2], therapeutic potential [3] or biomimetic activities [3–5]. O-
Benzoylsalicylato- and salicylatocopper(II) complexes with the rigid,
meridional N3-ligand 1,3-bis(2-pyridylimino)isoindoline (HL1, Scheme 1)
[6] have been structurally characterized as products from the oxygenation
of the corresponding flavonolato- and methylchromonatocopper(II)
complexes [6,7]. These compounds served as functional models for
the copper-containing 2,4-flavonol dioxygenase enzyme [8]. Aceta-
tocopper(II) complexes with other tridentate isoindoline derivatives
were also studied as selective peroxylation catalysts for olefins [9].
An interesting, common feature of the structurally characterized
complexes is that the carboxylate is coordinated to the copper exclu-
sively as a monodentate ligand in spite that the isoindoline-based
ligands allow other bidentate ligands such as flavonol and methyl-
chromone to occupy one quasi-equatorial and one apical position
in a square-pyramidal geometry, or another isoindoline [10] to form
hexacoordinate, bis-chelate copper(II) complexes. The aim of the
present work was to apply the two different isoindolines, 1,3-bis(2-pyr-
idylimino)isoindoline (HL1) [11] and 1,3-bis(2-benzimidazolylimino)
isoindoline (HL2) [11], and the carboxylate ligands shown in Scheme 1
in order to possibly alter the carboxylate coordination mode by elec-
tronic and steric effects. As it will be shown the binding mode does
not change significantly for a wide spectrum of ligand combinations,
instead systematic change in the supramolecular assembling of the
mononuclear complexes is experienced along with changes in the
Cu2+/Cu+ redox potential and reversibility.
The complexes were synthesized according to the procedure in
Scheme 2 [12]. Crystallization of the solid products from DMF provid-
ed single crystals of 1, 2·2DMF and 4·DMF that were suitable for
X-ray crystallography [13–15]. Structure of 1 is shown in Fig. 1a.
The Cu(II) center adopts distorted SPY-5 geometry, the basal square
plane is constituted of three nitrogens of L1 (N1, N3 and N5) and
one carboxylate oxygen (O1) of pga. The copper atom is out of the
N1,N3,N5 plane by 0.128 Å. The steric hindrance of the two pyridyl
arms on L1 pushes the O1 atom out from the fourth equatorial posi-
tion leading to distortion of the geometry toward TBPY-5 (the τ-
value is 0.21 [16]). The apical position is occupied by a water mole-
cule. The distance of the pga O2 atom from the Cu(II) center
(2.993 Å) excludes bonding interaction thus the carboxylate is coor-
dinated to the metal as a monodentate ligand. The Δ=184 cm−1 en-
ergy difference between the νas and νs vibration modes of the
carboxylate group that were observed in the FTIR spectrum of 1
(Fig. S1, FTIR data: ref. [12]) also indicates monodentate coordination
mode in agreement with the X-ray structural information.
The presence of water ligand, carboxylate and carbonyl oxygen
atoms and exocyclic imine nitrogens on L1 may lead to H-bonding
interactions. These interactions are observed in the crystal struc-
ture of 1 and indicated with dashed lines in Fig. 1b. For clarity,
the pattern of the intermolecular H-bonds is depicted for one of
the two individual molecules in the unit cell. Each mononuclear
complex is bound to three adjacent ones by four intermolecular
⁎
Corresponding author. Tel.: +36 88 624 720; fax: +36 88 624 469.
E-mail address: kaizer@almos.vein.hu (J. Kaizer).
1387-7003/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.inoche.2011.08.005

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J.S. Pap et al. / Inorganic Chemistry Communications 14 (2011) 1767–1772
Scheme 1. Structure of the applied ligands.
H-bonds of two types: O2′…H2w−O4 and N4′…H1w−O4. Based
on the distances and angles (caption of Fig. 1) these two interac-
tions are close in energy and belong to the medium-strength cate-
gory [17]. The interactions assist in building of a double-chain
network of 1 that is further supported by “intra-chain” π-stacking
between the A and C, or C′ (Scheme 1) heterocyclic moieties of L1.
The geometrical parameters describing the π-stacking are listed in
Table 1 (X is the distance between the centroids of the stacked ar-
omatic rings, d is the perpendicular distance between their mean
planes, δ is the offset between the centers measured along one of
the planes, α is the angle between the line connecting centroids
(X) and the normal to the plane of the aromatic system (d), and
β is the dihedral angle between the planes in a stack, according to Scheme
S1). Somewhat similar interactions were reported for the [Cu(4′-MeL1
(H2O)2]+ complex (4′-MeL1=1,3-bis{2-(4-methylpyridyl)imino}isoin-
dolinate) with TPBY-5 geometry [18]. In the case of 1 a further, sheet-
like arrangement of the “double-chains” is observed as shown in Fig. 1c.
The chains are anchored by π–π interactions between the benzene rings
of the pga ligands (for parameters see Table 1) that lead to a highly orga-
nized supramolecular assembly.
0.293 Å. The O2 atom of the pga ligand is found at 2.616 Å from the
Cu(II) center that does not support significant bonding interaction.
The Δ=νas(CO2)−νs(CO2) value from FTIR data (Fig. S2) is smaller
(171 cm−1) than in the case of 1 in accordance with the smaller
observed Cu−O2 distance.
The presence of NH functions on L2 of 2 and the absence of water
ligand lead to changes in the intermolecular interactions in compari-
son with 1. The N4 and N7 atoms form almost linear H-bonds with
two O-atoms (O4 and O5) of DMF molecules (Fig. 2a). Between two
2.2DMF assemblies offset π-stacking forces make contact due to inter-
actions of A and C or C′ rings of the two L2 moieties (Table 1). These
pairs of two independent molecules along with the H-bonded DMF
molecules are positioned across a center of pseudosymmetry at the
center of the unit cell or at the half of axis a (Fig. 2b). Such interac-
tions were shown to imprint chiral information on supramolecular di-
mers of Pd complexes with β-pinene containing isoindolines [19].
Furthermore, there are short intermolecular contacts between methyl
H-atoms (H34A) of DMF molecules and a neighboring carboxylic O2
atom of a dimeric assembly that render a chain of dimers together
(Fig. 2c), where the L2 ligands in antiparallel conformation are strong-
ly slipped (δ=2.54 Å) therefore only weak (if any) stacking can be
presumed (Table 1).
In comparison, in single crystals of 2 from DMF the complex
adopts a significantly distorted SP-4 geometry with an N3O donor
set (Fig. 2a) where the Cu atom is out of the N1,N3,N5 plane by
Complex 4 crystallizes from DMF with one solvent per complex
molecule that is H-bonded to the N7 atom of the L2 ligand via H7
(Fig. 3a). The Cu(II) center is four-coordinate, surrounded by a N3O
donor set. The geometry is distorted square-planar where the O1
points out of the plane due to strong steric hindrance of the L2 ligand
(H-atoms on C21 and C15). To show that the distortion of the SPY-4
geometry is dominantly governed by the steric hindrance of the
two in-plane H-atoms a brief structural analysis was done with car-
boxylate complexes that contain L1 [6], 4'-Me-L1 [9], L2, or 1,3-bis
(2-thiazolylimino)isoindolinate (L3) [9]. Ligands L1, L2 and L3 have
in-plane H⋯H distances that span a range between 3.33 and 4.85 Å
(Table S1). A negative relationship was found between the distance
of the quasi-equatorial carboxylate O atom from the line of the two
in-plane H-atoms and the H⋯H distance (Fig. S3), e.g. the least dis-
torted SPY-4 geometries were found with L3, where the H···H dis-
tance is the longest. The Cu atom in 4 is above the N1,N3,N5 plane
by 0.361 Å. The Cu1−O2 distance (2.614 Å) is indicative of mono-
dentate coordination of the benzoate ligand. Note that the Δ=
ν
as(CO2)−νs(CO2) value from FTIR (Fig. S2) is 162 cm−1, unusu-
ally small for a monodentate carboxylate ligand. However, the
4·DMF assemblies form H-bonded dimers in which the N4–H4A⋯O2′
interactions are relatively strong, based on their distance and linearity
(Fig. 3a, caption). This interaction can be accounted for the small differ-
ence in ν(CO2). The L2 moieties are arranged antiparallel in the
Scheme 2. Synthesis and numbering of the mixed-ligand complexes.

J.S. Pap et al. / Inorganic Chemistry Communications 14 (2011) 1767–1772
1769
Fig. 1. (a) Molecular structure of 1 showing 30% probability thermal ellipsoids; (b) packing and double-chain assembling pattern of 1 (Cu atoms and those involved in H-bonds are
plotted as spheres, Cu: orange, N: blue, O: red, H: white, H-bonds are indicated with dotted lines); (c) sheet-like arrangement of the chains (C atoms of π-stacked benzene rings are
drawn as black spheres) Selected bond distances (Å) and angles (°): Cu1–O1 1.986(3), Cu1–N1 1.901(4), Cu1–N3 2.023(4), Cu1–N5 2.029(4), Cu1–O4 2.399(3), O4–H1W 0.8499,
O4–H2W 0.846. N1–Cu1–O1 155.58(15), O1–Cu1–O4 97.23(13), N3–Cu1–N5 172.68(16), O1–Cu1–N3 91.95(14). Distances (Å) and angles (°) of H-bonds: O2(⋯H2W)–O4 2.931,
162.95; O4(⋯H1W)–N4 2.921, 171.63.
supramolecular dimers and there is only weak offset π-stacking interac-
tions between the A and D rings (Scheme 1) with parameters given in
Table 1. Therefore the major forces that tether the dimers of
4·DMF assemblies are the H-bonds. A further offset π-stacking be-
tween these dimers results in a supramolecular chain with units of
antiparallel conformation (Fig. 3b). In this assembly the A and D or
B and C rings of adjacent dimers are stacked (Table 1).
The various ligands were selected to affect first of all the coordina-
tion mode of the carboxylate moiety by a quantifiable electronic ef-
fect, or an additional donor group in pgaH. As it became clear from
the structural data, the presence of a α-carbonyl group in the pga
complexes left the structure of the first coordination sphere unaffect-
ed compared to the corresponding benzoate complex. Instead, the
various combinations of N3 and carboxylate ligands have led to supra-
molecular assemblies based on the systematically modified mononu-
clear complexes. Analysis of FTIR data was used to elucidate the effect
of the 4-R substituents on geometry. The energy difference between
the νas and νs vibration modes of the carboxylate group was calculat-
ed for complexes 4–10 and plotted against the Hammett σ-constant
for the R-groups (Fig. 5b). Although the σ spans from −0.83 to

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J.S. Pap et al. / Inorganic Chemistry Communications 14 (2011) 1767–1772
0.75, the values of Δν(CO2) scatter around ~156 cm−1 indicating that
no change in mono-/bidentate binding took place. Redox transitions
are, in turn, strongly dependent on the ligands according to cyclic vol-
tammetry (CV) measurements. The reduction and oxidation current
peak potentials (Epc and Epa) are listed in Table 2 and four typical
CV spectra are shown in Fig. 4 in DMF.
Table 1
Geometrical parameters describing the intermolecular π-stacking of the aromatic frag-
ments for 1, 2·2DMF and 4·DMF.
1
2·2DMF
4·DMF
L1
pga
3.70
3.67
3.35
3.38
1.57
1.43
L2
L2
X (Å)
d (Å)
δ (Å)
α (°)
β (°)
3.65
3.68
4.29
3.34
3.46
1.54
2.53
65.2
53.8
0.8
3.67
3.97
3.52
3.66
1.04
1.54
73.6
67.2
4.1
The L1-containing complexes (1 and 3) show a quasi-irreversible
transition (ipa b|ipc|) that is associated with the Cu2+/Cu+ couple.
The corresponding complexes with L2 ligand on the other hand are
reduced irreversibly that is already apparent from the non-Nernstian
peak shape of the reduction waves. Also, the re-oxidation wave is pre-
sent at similar potentials for 2 and 4–10 (roughly −0.690 V) albeit
the reduction potential is sensitive to the identity of the carboxylate
3.95
3.51
3.52
1.00
1.79
74.1
63.0
8.1
64.9
67.1
0
9.1
Fig. 2. (a) Molecular structure of 2·2DMF showing 30% probability thermal ellipsoids; (b) packing of 2·2DMF (π-stacked molecules at the center of the unit cell are drawn with spheres,
Cu: orange, N: blue, O: red, H: white, C: black); (c) chain-like arrangement of 2·2DMF (atoms involved in H-bonds or close contacts are plotted as spheres, H-bonds and close contacts are
drawn with dotted lines). Selected bond distances (Å) and angles (°): Cu1–O1 2.015(2), Cu1–N1 1.934(3), Cu1–N3 1.941(2), Cu1–N6 1.953(2). N1–Cu1–O1 151.61(10), N1–Cu1–N6 90.58
(10), O1–Cu1–N3 93.80(10). Distances (Å) and angles (°) of H-bonds: N4–(H4A⋯)O5 2.705, 163.46; N7–(H7⋯)O4 2.743, 169.58.

J.S. Pap et al. / Inorganic Chemistry Communications 14 (2011) 1767–1772
1771
Fig. 3. (a) Molecular structure of 4·DMF showing 30% probability thermal ellipsoids and its dimeric assembling (H-bonds are indicated with dotted lines); (b) packing and chain
arrangement of π-stacked 4·DMF assemblies (atoms participating in H-bonds are plotted as spheres). Selected bond distances (Å) and angles (°): Cu1–O1 1.988(3), Cu1–N1 1.931
(3), Cu1–N3 1.954(3), Cu1–N6 1.946(3). N1–Cu1–O1 156.07(12), N1–Cu1–N6 97.23(13), O1–Cu1–N3 92.43(12). Distances (Å) and angles (°) of H-bonds: N4–(H4A···)O2′ 2.754,
177.92; N7–(H7⋯)O3 2.718, 170.28.
ligand. Therefore we believe that the oxidized species should be the
same in each case, from which the pga, or 4-R-ba ligands are absent.
Despite the irreversible transition for the L2-containing complexes
the 4-R sensitive reduction potential carries valuable information. As
electron-pushing substituents are introduced, the transition shifts to
the more negative potentials and accordingly, electron-withdrawing
substituents result in easier oxidation. This potential shift is linearly
dependent on the σ-values as Fig. 5a illustrates (the slope of the fitted
line is 169.4 19.9 mV/σ-unit, R=0.96). In conclusion, the studied li-
gand combinations exclude chelate coordination for a carboxylate. In
exchange, the relative rigidity of the first coordination sphere allows
not only the formation of versatile supramolecular assemblies, but
also, the redox properties of the Cu center can be fine-tuned by clearly
electronic effects of the ligands.
Table 2
Electrochemical data for the isoindoline complexes in DMF vs. the ferrocene internal
standard (unity of potential values is V).
Complex
Epc
Epa
1
2
3
4
5
6
7
8
9
−1.050
−0.980
−1.158
−1.355
−1.450
−1.420
−1.385
−1.293
−1.245
−1.180
−0.862
−0.675
−1.030
−0.690a
10
a
10 mV, average value of the Epa potentials for 4–10.

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J.S. Pap et al. / Inorganic Chemistry Communications 14 (2011) 1767–1772
[6] (a) É. Balogh-Hergovich, J. Kaizer, G. Speier, G. Huttner, A. Jacobi, Inorg. Chem. 39
(2000) 4224;
(b) J. Kaizer, J. Pap, G. Speier, L. Párkányi, Z. Krist.- New Cryst. Str. 219 (2004) 141.
[7] (a) J. Kaizer, J. Pap, G. Speier, M. Reglier, M. Giorgi, Transit. Met. Chem. 29 (2004)
630;
(b) J.S. Pap, J. Kaizer, G. Speier, Coord. Chem. Rev. 254 (2010) 781.
[8] R.A. Steiner, K.H. Kalk, B.W. Dijkstra, Proc. Natl. Acad. Sci. U. S. A. 99 (2002) 16625.
[9] M.B. Meder, L.H. Gade, Eur. J. Inorg. Chem. (2004) 2716.
[10] J.S. Pap, B. Kripli, V. Bányai, M. Giorgi, L. Korecz, T. Gajda, D. Árus, J. Kaizer, G. Speier,
Inorg. Chim. Acta (2011), doi:10.1016/j.ica.2011.06.001.
[11] (a) J. Kaizer, B. Kripli, G. Speier, L. Párkányi, Polyhedron 28 (2009) 933;
(b) W.O. Siegl, J. Org. Chem. 42 (1977) 1872.
[12] General procedure for 1–10: to a stirred solution of CuII(ClO4)2·6H2O (0.185 g,
0.5 mmol) in acetonitrile (30 mL) HLn (0.150 g for n=1, or 0.188 g for n=2,
0.5 mmol) was added and the mixture was stirred for 30 min at room tempera-
ture. Triethylamine (0.5 mmol, 70 μL) was added dropwise, followed by the addi-
tion of the corresponding carboxylic acid (2.0 mmol) and another 0.5 mmol of
triethylamine. Stirring at room temperature for 3 h yielded the corresponding
products as solid precipitates that were filtered off, washed with acetonitrile
and vacuum-dried. 1: Yield: 0.21 g (80%). Anal. Calcd (Found) for
C
26H19CuN5O4: C, 59.0 (59.2); H, 3.6 (3.7); N, 13.2 (13.4). FTIR (KBr, cm−1
)
3420 ν(H2O), 1615 ν(C=O), 1580 νas(CO2), 1529 ν(C=N), 1396 νs(CO2). UV–
vis (DMF) [λmax, nm (logε)] 681 (1.98), 448 (4.27), 423 (4.35), 403 (4.19), 352
(4.10), 336 (4.27), 321 (4.25), 311 (4.27). Single crystals suitable for structural
analysis were obtained from DMF upon standing. 2: Yield: 0.25 g (85%). Anal.
Calcd (Found) for C30H19CuN7O3: C, 61.2 (61.1); H, 3.3 (3.2); N, 16.6 (16.8).
FTIR (KBr, cm−1) 1618 ν(C=O), 1559 νas(CO2), 1525 ν(C=N), 1388 νs(CO2).
UV–vis (DMF) [λmax, nm (logε)] 670 (1.96), 480 (4.15), 449 (4.32), 424 (4.28),
383 (4.10), 364 (4.32), 349 (4.29), 294 (4.16). Single crystals suitable for struc-
tural analysis were obtained from DMF upon standing. 3: Yield: 0.23 g (92%).
Anal. Calcd (Found) for C25H19CuN5O3: C, 59.9 (60.2); H, 3.8 (3.8); N, 14.0
(14.1). FTIR (KBr, cm−1) 3394 ν(H2O), 1577 νas(CO2), 1529 ν(C=N), 1392 νs
(CO2). UV–vis (DMF) [λmax, nm (logε)] 641 (1.96), 448 (4.27), 423 (4.35), 403
(4.19), 352 (4.10), 336 (4.27), 321 (4.25), 311 (4.27). 4: Yield: 0.22 g (78%).
Anal. Calcd (Found) for C29H19CuN7O2: C, 62.1 (61.9); H, 3.4 (3.5); N, 17.5
(17.7). FTIR (KBr, cm−1) 1554 νas(CO2), 1511 ν(C=N), 1392 νs(CO2). UV–vis
(DMF) [λmax, nm (logε)] 590 (2.06), 480 (4.15), 449 (4.32), 424 (4.28), 383
(4.10), 364 (4.32), 349 (4.29), 294 (4.16). Single crystals suitable for structural
analysis were obtained from DMF upon standing. 5: Yield: 0.26 g (87%). Anal.
Calcd (Found) for C31H24CuN8O2: C, 61.6 (61.4); H, 4.0 (3.9); N, 18.6 (18.8).
FTIR (KBr, cm−1) 2894 ν(CH3), 1555 νas(CO2), 1505 ν(C=N), 1389 νs(CO2). 6:
Yield: 0.21 g (71%). Anal. Calcd (Found) for C30H21CuN7O3: C, 61.0 (60.5); H, 3.6
Fig. 4. Cyclic voltammograms of complexes 1–4 in DMF (c=1 mM, 0.1 M TBAP, Pt aux-
iliary electrode, GCE working el., Ag/AgCl ref. el., 100 mVs−1 scan rate, plotted vs. the
redox potential of the Fc+/Fc internal standard).
(3.7); N, 16.6 (16.8). FTIR (KBr, cm−1
ν(C=N), 1393 νs(CO2). 7: Yield: 0.20 g (70%). Anal. Calcd (Found) for
30H21CuN7O2: C, 62.7 (62.6); H, 3.7 (3.9); N, 17.1 (17.0). FTIR (KBr, cm−1
2969 ν(CH3), 1551 as(CO2), 1506 ν(C=N), 1392 νs(CO2). 8: Yield: 0.26 g
) 2950 ν(CH3), 1548 νas(CO2), 1505
C
)
ν
(87%). Anal. Calcd (Found) for C29H18ClCuN7O2: C, 58.5 (58.9); H, 3.1 (3.2); N,
16.5 (16.4). FTIR (KBr, cm−1) 1550 νas(CO2), 1508 ν(C=N), 1399 νs(CO2). 9:
Yield: 0.20 g (69%). Anal. Calcd (Found) for C30H18CuN8O2: C, 61.5 (61.2); H, 3.1
Fig. 5. (a) Dependence of the anodic peak potential for complexes 4–10 vs. the Hammett σ
with respect to the 4-R substitution on the benzoate ligand; (b) change in the Δν(CO2) vs.
the Hammett σ.
(3.2); N, 19.1 (18.7). FTIR (KBr, cm−1
)
2233 (C≡N), 1552
ν(C=N), 1398 νs(CO2). 10: Yield: 0.25 g (82%). Anal. Calcd (Found) for
29H18CuN8O4: C, 57.5 (57.3); H, 3.0 (3.1); N, 18.5 (18.6). FTIR (KBr, cm−1
1555 νas(CO2), 1506 ν(C=N), 1407 νs(CO2), 1345 ν(NO2).
νas(CO2), 1507
C
)
Acknowledgements
[13] The intensity data were collected with Bruker–Nonius Kappa CCD diffractometer
using Mo Kα radiation (λ=0.71073 Å) at 203(2) K for 1 and 2·2DMF and at
293(2) K for 4·DMF. Crystallographic data and details of the structure determina-
tions are found in Table 1. SHELX-97 [14] was used for structure solution and full
matrix least squares refinement on F2. The structures were solved by direct and
difmap methods (SIR92) [15]. Summary of crystal structure details of 1, 2·2DMF
Financial support of the Hungarian National Research Fund (OTKA
PD75360, OTKA K67871 and OTKA K75783) and COST is gratefully
acknowledged.
and 4·DMF, respectively: chemical formula:
C26H19Cu1N5O4, C36H33Cu1N9O5,
C
32H26Cu1N8O3; formula weight: 529, 735.25, 634.15; space group: triclinic P-1,
Appendix A. Supplementary material
monoclinic P21/c, monoclinic P2/n; a (Å): 7.3155(5), 17.4399(2), 12.0436(3); b
(Å): 12.1916(7), 7.4101(1), 19.3649(4); c (Å): 12.998(1), 27.4511(5), 12.3094
(3); α (°): 87.143(2), 90, 90; β (°): 82.728(2), 107.985(1), 89.976(1); γ (°):
76.259(6), 90, 90; V (Å3): 1116.79(13), 3374.20(9), 2870.1(2); Z: 2, 4, 4; Dcalc
(Mg m−3): 1.573, 1.447, 1.467; temp. (K): 203(2), 203(2), 293(2); unique reflec-
tions: 4139, 8053, 7137; dataN2σ/parameters/restraints: 3184/325/2, 5587/
464/0, 4008/397/0; R1 [F2N2σ(F2)] and wR2 (F2): 0.0635 and 0.1192, 0.0526
and 0.1234, 0.0598 and 0.1360, where R1=Σ||Fo|−|Fc||/Σ|Fo|.wR2=[Σw(Fo2 −
Files CCDC 831064–831066 (1, 2·2DMF and 4·DMF) contain the
supplementary crystallographic information for this paper. These
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supplementary data to this article can be found online at doi:10.
1016/j.inoche.2011.08.005.
Fc2)2/Σw(Fo2)2]1/2
,
w=1/σ2(Fo)2 +(AP)2 +BP (P=[Fo2 +2Fc2]/3; A=0,
0.0767 and 0.0645, B=2.8639, 1.5110 and 3.4907 for 1, 2·2DMF and 4·DMF, re-
spectively); goodness of fit: 1.131, 1.128, 1.040. Crystal structures have been de-
posited at the Cambridge Crystallographic Data Centre (Deposition no. CCDC
831064 (1), CCDC 831065 (2·2DMF) and CCDC 831066 (4·DMF)).
[14] G.M. Sheldrick, Acta Crystallogr. A64 (2008) 112.
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