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Article history:
Received 16 October 2013
Received in revised form
12 November 2013
Accepted 13 November 2013
1. Introduction
The eld of macrocyclic complexes is extremely wide due to the
diverse uses found for that kind of compounds in catalysis [1], selective metal recovery and recycling [2], sensors [3] and therapy
and diagnosis [4]. Among other macrocyclic ligands, cyclens and
cyclams were extensively studied because they are able to accommodate and stabilize a large variety of metal cations in several
oxidation states [5]. Copper(II) complexes based on such ligands
display high thermodynamic stability with respect to metal dissociation as well as interesting electrochemical properties. The
properties of tetra-N-functionalized cyclams are quite different
from those of the unsubstituted parent macrocyclic compounds [6].
Moreover, coordinative pendant arms on the nitrogen atoms allow
the tuning of the properties and the selectivity for particular metal
ions [7]. The establishment of selective synthetic procedures for
tetrazamacrocyclic compounds is thus an important topic. TransN,N0 -disubstituted cyclams may be obtained by reactions of the
bisaminal cyclam 1,4,8,11-tetraazatricyclo[9.3.1.14,8]hexadecane
with electrophiles [8]. Those reactions are highly selective because
the stereochemical conformation imposed by the methylene crossbridges forces trans-nitrogen atoms lone pairs to point out of the
* Corresponding author.
E-mail address: ana.martins@ist.utl.pt (A.M. Martins).
0022-328X/$ e see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.11.015
131
Scheme 1.
4
6a
6b
7a
7b
9
Substituents
MeN(1)
MeN(2)
MeN(3)
MeN(4)
MeO
MeCl
2.094(2)
2.283(3)
2.333(4)
2.108(3)
2.113(2)
2.025(3)
1.992(2)
2.063(3)
2.052(4)
1.995(2)
2.000(3)
2.009(3)
e
2.313(3)
2.295(3)
e
e
2.040(3)
e
2.056(3)
2.065(3)
e
e
2.006(3)
2.670(4)
e
e
2.440(2)
2.395(2)
2.444(3)
e
2.247(1)
2.235(1)
e
e
2.846(3)
NeqeMeNeq
4
6a
6b
7a
7b
9
86.58(7)
120.9(1)
107.9(2)
86.6(1)
86.3(1)
85.6(1)
93.4(1)
93.7(1)
86.8(1)
Compound
DeH/A
d (DeH)
d (H/A)
d (D/A)
^
(DHA)
O(1)eH(1O)/S(1)
O(1)eH(2O)/S(1)
N(2)eH(2N)/S(1)
N(4)eH(4N)/Cl(2)
N(8)eH(8N)/Cl(4)
N(2)eH(2N)/O(5)
N(4)eH(4N)/O(6)
N(2)eH(2N)/Cl(1)
0.959
0.911
0.916
0.889
0.843
0.825
0.783
0.855
2.210
2.315
2.323
2.341
2.593
2.078
2.145
2.445
3.161
3.196
3.231
3.186
3.354
2.892
2.918
3.282
171.73
162.56
171.61
158.70
150.70
168.52
169.42
166.14
6a
6b
7a
7b
9
NeqeMeCleq
NeqeMeCleq
XaxeMeXax
118.6(1)
128.3(2)
e
e
e
120.5(1)
123.8(1)
e
e
e
180.00
159.6(1)
165.0(1)
180.00(8)
180.0
151.27
93.42(7)
The coordination geometry of copper is octahedral. The equatorial plane is dened by the four nitrogen atoms of the cyclam ring
with internal NeCueN angles close to 90 and the axial positions
are occupied by two water molecules. The data obtained for complex 4 are similar to those reported for other octahedral Cu(II)
complexes displaying cyclams and two axial water molecules [17],
in
particular,
[H2{1,5,8,12-tetramethyl-1,8,11-tetraazacyclo
tetradecane}Cu(H2O)2]X (X NO2, Br, Cl, I) [17a]. The two benzyl
substituents are located at opposite sides of the cyclam ring
dening a trans-III conguration that corresponds to the most
stable diastereomer in octahedral cyclam complexes [18].
Hydrogen bonds are established between S(1) and the hydrogen
atoms H(1O), H(2O) and H(2N) with distances of 2.210, 2.315 and
2.323
A, respectively, as shown in Fig. 1b (see Table 2 for details).
Table 2
Hydrogen bond distances (
A) and angles ( ) of the compounds 4, 6, 7 and 9.
Table 1
Selected distances (
A) and angles ( ) of the compounds 4, 6, 7 and 9.
Ligand set
Fig. 1. a) ORTEP diagram of [{H2(PhCH2)2Cyclam}Cu(H2O)2]S, 4, showing thermal ellipsoids at 40% probability level. Half molecule is generated by symmetry. Selected
hydrogen atoms are omitted for clarity; b) Best view of 4 revealing the hydrogen bonds
between S(1) and H(1O), H(2O) and H(2N) atoms (dashed lines).
132
2
JHeH of 19 and 15 Hz for 5 and 6, respectively. The 13C{1H} NMR
spectra are in conformity with the proton data showing six
resonances for the ligand methylene carbons and one set of
aromatic signals.
Crystals of complex 6 suitable for X-ray diffraction were obtained from slow evaporation of an aqueous solution (crystallographic and experimental details are presented in Table 4).
Compound 6 crystallized in the triclinic space group P-1 with two
molecules in the asymmetric unit (6a and 6b). An ORTEP depiction
of the molecular structure of 6a is shown in Fig. 2 and relevant
distances and angles are presented in Table 1.
The coordination geometry around the zinc is trigonal bipyramidal as observed in other pentacoordinated zinc cyclam complexes [19]. The equatorial plane is dened by N(2), N(4) and Cl(1)
atoms. The axial positions are occupied by the other two nitrogen
atoms of the macrocycle with N(1)eZn(1)eN(3) angle of 159.6(1)
in 6a and 165.0(1) in 6b. In general, the distances and angles
determined for 6a and 6b are in agreement with values reported
[20]. The counter-ion is in the proximity of one NH group of the
cyclam ring with which it forms a Cl/H/N bridge (see Table 2 for
details).
The compounds presented in Scheme 2, with general formula
[{H2(MeOCH2)2Cyclam}Cu]X (X SO4, 7, (CH3COO)2, 8, and [CuCl4],
9) were obtained from reactions of 1,4,8,11-tetraazatricyclo
[9.3.1.14,8]hexadecane with the corresponding Cu(II) salts in
methanol. A comparable procedure was reported for the preparation of other copper cyclam derivatives using Cu(ClO4)2$6H2O [9].
Complex 9 is obtained independently of the reaction being performed with one or two equiv. of CuCl2$2H2O.
The role of Cu2 is critical for the outcome of the reactions once
it is only in the presence of copper that the bridging methylene
carbons are activated for nucleophilic attack by methanol.
In the IR spectra of complexes 7e9 the nNeH bands are observed
in the range 3159e2946 cm1. The nS]O bonds in 7 give rise to a
broad band at 1108e1020 cm1 and one sharp band at 620 cm1
and the nC]O bands in 8 show up at 1622 and 1569 cm1.
The magnetic moments of compounds 7e9 are 1.6 MB, 1.7 MB
and 2.1 Bohr magnetons, respectively, in agreement with their
formulations. The EPR spectra are shown in Fig. 3 and the experimental spin Hamiltonian parameters are presented in Table 3.
Fig. 3. First derivative X-band EPR spectra of compounds 7 (top), 8 (middle) and 9
(bottom) recorded at 77 K in ethyleneglycol.
7
8
9
[CuCl4]2a
Scheme 2.
gx, gy
(or gt)
gz
(or gjj)
Az (or Ajj)
104 cm1
gz/Az cm
2.045
2.067
2.013
2.094
2.060
15.3
16.9
21.7
1.9
1.1
2.190
2.187
193.9
200.2
112
109
2.190
200.0
109
2.385
139.0
171
experimental details of data collection and crystal structure determinations are presented in Table 4.
133
bridges the metal centers of the cation and the anion. The angle
O(2)eCu(1)e(Cl3_$1) deviates from linearity with a value of
Table 4
Crystal data and structure renement for complexes 4, 6, 7 and 9.
Compound
7$(CH3OH)2
Empirical formula
Formula weight
Temperature (K)
Wavelength (
A)
Crystal system
Space group
Unit cell dimensions:
a (
A)
b (
A)
c (
A)
a( )
b( )
g( )
Volume (
A3)
Z
Calculated density (g m3)
Absorption coefcient (mm1)
F (000)
Crystal size (mm)
Theta range for data collection ( )
Limiting indices
C24H40CuN4O2S2
544.29
150
0.71073
Monoclinic
P21/c
C24H36Cl2N4Zn
516.86
302
0.71073
Triclinic
P-1
C16H40CuN4O8S
512.14
150
0.71073
Monoclinic
P21/n
C14H32Cl4Cu2N4O2
557.34
150
0.71073
Monoclinic
P21/n
9.8760(4)
9.8668(5)
13.2932(6)
90
94.243(2)
90
1291.8(1)
2
1.399
1.036
578
0.08 0.10 0.20
2.57e29.60
13 h 13, 13 k 13,
18 l 18
23,227/3631 [0.0497]
99.9 (q 29.60)
Full-matrix least squares on F2
3631/0/163
1.087
R1 0.0390, wR2 0.1158
R1 0.0507, wR2 0.1211
Multi-scan
1.182 and 0.609
9.584(1)
12.661(1)
23.035(3)
88.848(4)
82.146(4)
68.358(4)
2572.3(5)
4
1.335
1.181
1088
0.20 0.20 0.20
2.32e25.38
11 h 11, 15 k 15,
27 l 27
80,203/9444 [0.0373]
99.5 (q 25.38)
Full-matrix least squares on F2
9444/0/569
1.047
R1 0.0596, wR2 0.1580
R1 0.0695, wR2 0.1656
Multi-scan
1.669 and 1.390
11.291(1)
13.327(1)
17.455(2)
90
98.260(4)
90
2599.3(4)
4
1.309
0.963
1092
0.30 0.30 0.30
1.93e27.21
14 h 14, 15 k 17,
22 l 22
39,447/5756 [0.0352]
99.1 (q 27.21)
Full-matrix least squares on F2
5756/0/288
1.055
R1 0.0472, wR2 0.1246
R1 0.0648, wR2 0.1326
Multi-scan
0.931 and 0.676
10.026(3)
15.934(2)
14.438(2)
90
95.93(1)
90
2294.2(8)
4
1.613
2.336
1144
0.02 0.06 0.10
1.91e25.77
12 h 12, 19 k 19,
17 l 17
28,985/4365 [0.0695]
99.1 (q 25.77)
Full-matrix least squares on F2
4365/0/244
1.058
R1 0.0409, wR2 0.0815
R1 0.0645, wR2 0.0877
Multi-scan
0.711 and 0.422
conformations of the macrocycle ring as well as in the supramolecular structures adopted by the complexes, as discussed below.
Compound 7 reveals a linear polymeric structure growing in the
b direction as shown in Fig. 4a. The average planes dened by two
consecutive cyclam rings of molecules 7a and 7b dene dihedral
angles of 31.30 , leading to a zigzag arrangement (Fig. 4b). This
supramolecular architecture is maintained by hydrogen bonds between the oxygen atoms of the sulphate anion and NH groups of
the macrocyclic rings (see details in Table 2).
The coordination of copper is octahedral with four nitrogen
atoms of the macrocycle dening the equatorial plane and two
oxygen atoms of sulphate ions at the axial positions (Fig. 4c). The
CueN and CueO bond distances are within the ranges observed for
other compounds [20]. The N-CH2OMe pending arms attached to
the trans-nitrogen atoms of the cyclam ring point in opposite directions in relation to the average [N4] plane resulting in trans-II
conformation of the complex [18].
The supramolecular arrangement in 9 is shown in Fig. 5a and an
ORTEP view of the molecular structure is presented in Fig. 5b. The
complex shows a trans-III conformation with the two N-CH2OMe
pending arms directed to the same side of the average nitrogen
plane of cyclam [18]. The coordination geometry of copper is distorted octahedral in the cation and tetrahedral in the anion. The
equatorial plane of the cation is dened by the four nitrogen atoms
of the cyclam ring and presents very regular CueN bond lengths
and NeCueN angles, in agreement with other copper cyclam
complexes [6b,17a,23]. The two axial positions are occupied by the
oxygen atom of one CH2OMe group and by a chlorine atom that
134
3. Experimental section
3.1. General considerations
H2(PhCH2)2Cyclam, H2(4 t BuPhCH2 )2Cyclam and 1,4,8,11tetraazatricyclo[9.3.1.14,8]hexadecane were prepared according to
described procedures [8,13a]. All other reagents were commercial
grade and used without further purication. NMR spectra were
recorded in a Bruker AVANCE II 400 MHz spectrometer, at 296 K
unless stated otherwise, referenced internally to residual protonsolvent (1H) or solvent (13C) resonances, and reported relative to
tetramethylsilane (0 ppm). 1He13C{1H} HSQC NMR experiments
were performed in order to make all the assignments. Elemental
analyses were obtained from Laboratrio de Anlises do IST. FT-IR
spectra were recorded on a Jasco FT/IR-4100 spectrometer at IST.
135
136
structures were made with Mercury 3.0 [34] or ORTEP-3 [35] for
Windows.
Compounds 6, 7 and 9 crystallized with disordered molecules of
solvent. As all attempts to model the disorder did not lead to
acceptable solutions, the Squeeze/PLATON [36] sequence was
applied.
[7]
Acknowledgements
The authors thank Fundao para a Cincia e a Tecnologia,
Portugal, for funding (PEst-OE/QUI/UI0100/2013, SFRH/BPD/86815/
2012).
Appendix A. Supplementary material
CCDC 965244e965247 contain the supplementary crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
[8]
[9]
[10]
[11]
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