Copper(ii) complexes of two new pyridylAliphatic amine ligands: Synthetic, structural, EPR, and magnetic studies

Article abstract of DOI:10.1071/CH12145

Two new polyamine ligands, L¹ and L², incorporating pyridyl and aliphatic amine donor sites have been prepared and their reaction with copper(ii) yields the mono- and binuclear complexes [Cu(L ¹)](ClO₄)²

Full text of DOI:10.1071/CH12145

RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem. 2012, 65, 926–930
Full Paper
http://dx.doi.org/10.1071/CH12145
Copper(II) Complexes of Two New Pyridyl Aliphatic Amine
]
Ligands: Synthetic, Structural, EPR, and Magnetic Studies*
A
A
A
A
E
Young Hoon Lee, Hari Kristopo, Arim Woo, Mi Seon Won,
B
C
D
Shinya Hayami, Pierre Thue´ry, Ok-Sang Jung, Hong In Lee,
Bok Jo Kim, Leonard F. Lindoy, and Yang Kim
F
G
A H
,
A
Department of Chemistry and Advanced Materials, Kosin University, 194, Wachi-Ro,
Yeongdo-gu, Busan 606-701, South Korea.
B
Department of Chemistry, Graduate School of Science and Technology, Kumamoto
University, 2-39-1 Kurokami, Kumamoto 860-8555, Japan.
C
CEA, IRAMIS, UMR 3299 CEA/CNRS, SIS2M, LCCEf, Baˆt.125, 91191 Gif-sur-Yvette,
France.
D
E
Department of Chemistry and Chemistry Institute of Functional Materials,
Pusan National University, Pusan 609-735, South Korea.
Department of Chemistry, Kyungpook National University, 702-701, Daegu,
South Korea.
F
Department of Biomedical Laboratory Science, College of Health, Kyungwoon
University, Gumi-si, Gyeongsangbuk-do, 730-739, South Korea.
G
School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.
Corresponding author. Email: ykim@kosin.ac.kr
H
Two new polyamine ligands, L1 and L2, incorporating pyridyl and aliphatic amine donor sites have been prepared and their
reaction with copper(II) yields the mono- and binuclear complexes [Cu(L1)](ClO4)2 (1) and [Cl2Cu(L2)CuCl(H2O)]ClO4
(2), respectively. The X-ray structure of 1 confirms that the five nitrogen donors of L1 are bound to the central copper ion to
give a distorted square pyramidal coordination sphere. In 2, L2 acts as a bridging ligand with its N3-donor coordination
domains separated by a m-xylylene spacer group. An unusual feature of this latter complex is that symmetrical L2 gives rise
to non-equivalent coordination behaviour at the individual copper sites; while both sites display five-coordination with
distorted square pyramidal arrangements, they differ in having N3Cl2- and N3ClO-donor atom sets, respectively. The
electron paramagnetic resonance (EPR) spectra of both complexes are discussed. Variable temperature magnetic
susceptibility data confirmed the absence of magnetic interactions in 1 while a weak antiferromagnetic interaction
between copper(II) centres occurs in 2.
Manuscript received: 8 March 2012.
Manuscript accepted: 24 April 2012.
Published online: 24 May 2012.
Introduction
versatile ligand systems for a range of transition and post-
transition metal ions.
The syntheses, crystal structures, and magnetic properties of
low-dimensional transition metal complexes continue to receive
a great deal of attention, in part motivated by the desire to
uncover new functional materials.[1] In view of this, such studies
have typically focussed on elucidating structure/function rela-
tionships. We now report the results of a further investigation of
this type involving the synthesis of two copper(II) complexes of
the new polyamine ligands L1 and L2 (see Scheme 1). In this
context it is noted that ligands incorporating both aliphatic and
heterocyclic nitrogen donor groups (including such ‘classic’
ligand systems as 2,20-dipyridylamine, 2-picolylamine, and
their derivatives)[2] have been very well documented to provide
Results and Discussion
Ligand and Complex Synthesis
The syntheses of L1 and L2 employed conventional organic
procedures and are summarised in Scheme 1 (parts (a) and (b)).
Reaction of copper(II) chloride with L1 in methanol followed by
chromatography on SP Sephadex C-25 and addition of per-
chlorate led to the isolation of blue crystals whose microanalysis
and X-ray structure determination (see below) confirmed that
they were a 1 : 1 complex of type [Cu(L1)](ClO4)2 (1). A similar
*Dedicated to Allan H. White – a fine crystallographer and solid-state chemist.
Journal compilation Ó CSIRO 2012
www.publish.csiro.au/journals/ajc

Pyridyl–Aliphatic Amine Ligands
927
(a)
(i)
H2N
(i)
N
Ts
NH HN
N
N
HN
N
N
CHO
(ii)
(ii)
NaBH4
H2SO4
NH2 NH2
N
N
L1
(b)
(i)
N
N
CHO
H
N
H
N
H2N
NH2
(ii)
NaBH4
N
(i)
CN
N
N
(ii)
Raney-Ni/NaBH4
N
N
H2N
NH2
L2
Scheme 1. Outline of the synthetic procedure used to prepare (a) L1 and (b) L2.
N4
N2
N2
N5
Cu2
N3
N1
N5
Cu1
Cl1
Cu
O1
N1
N4
N6
Cl3
Cl2
N3
Fig. 2. View of complex 2. The displacement ellipsoids are represented at
the 30 % probability level. The hydrogen atoms of carbons and counterions
are omitted.
Addison et al.[3] where b is the largest and a is the second largest
basal angle, respectively, the experimental t value of 1 is 0.36. It
reflects that 1 has a distorted square pyramidal geometry. The
Fig. 1. View of complex 1. The displacement ellipsoids are represented at
the 30 % probability level. The counterions are omitted.
˚
Cu atom is displaced by 0.2138(11) A from the basal plane, on
the same side as atom N1. The packing displays an alternation of
sheets of complex molecules separated by sheets of counterions
parallel to the ab plane. The protons bound to N3 and N5 are
involved in hydrogen bonds with the perchlorate counterions.
The X-ray structure of 2 (Fig. 2) shows that this dinuclear
complex displays an unusual unsymmetrical structure in which
the two copper centres are non-equivalent. While both metal
cations are characterised by 5-coordination, they are associated
with different donor atom sets, N3Cl2 and N3ClO for Cu1 and
Cu2, respectively. Both cations are in distorted square pyrami-
dal environments, with the basal planes defined by the three
procedure using copper(II) chloride and L2 yielded blue crystals
that, following microanalysis and X-ray structure determina-
tion, were shown to be a complex of type [Cl2Cu(L2)CuCl
(H2O)]ClO4 (2).
X-Ray Structures
The X-ray structure of 1 (Fig. 1) confirms that the five nitrogen
atoms of L1 coordinate to the central copper to give a distorted
square pyramidal environment, with the atoms N2, N3, N4, and
N5 defining the basal plane (root mean square (rms) deviation
˚
˚
0.20 A) and atom N1 in the axial position. According to the
definition of the distortion parameter t [t ¼ (b 2 a)/60] by
nitrogen atoms and Cl1 for Cu1 (rms deviation 0.21 A) or Cl3 for
˚
Cu2 (rms deviation 0.13 A). The experimental t values by

928
Y. H. Lee et al.
2.0
1.5
1.0
0.5
0
(a)
Sim.
(b)
0
100
200
300
Temperature [K]
Fig. 4. The xmT versus temperature curve for 2.
presence of longer CuII–Neq bond lengths than is usual for
related systems.
2500
3000
3500
Field strength [G]
The EPR spectrum of 2 exhibits a broad band from 2690 to
3420 G, in accord with the presence of a dipolar interaction
between the two copper(II) centres (Fig. 3b). The width of this
feature is close to the overall EPR spectroscopic width for 1,
perhaps suggesting that both 1 and 2 have similar electronic
structures.
Fig. 3. Electron paramagnetic resonance spectra (solid lines) obtained for
the frozen solution state of (a) 1 and (b) 2 in frozen 0.5 mM DMF at 110 K,
along with the numerical simulation (dotted line) for the spectrum of 1.
Addison et al.[3] for Cu1 and Cu2 are 0.35 and 0.24, respectively,
and indicate that both geometries are best described as disor-
dered square pyramidal. The metal atoms are at 0.3267(9) and
Magnetic Studies
The temperature-dependent magnetic susceptibilities of both
1 and 2 were measured in the temperature range from 2 to 300 K
in the form of the xmT versus T curve, where xm is the molar
magnetic susceptibility and T the temperature. The mononuclear
complex 1 exhibits a xmT value of 0.5 cm3 K molꢁ1, which is
close to the spin-only value for the copper(II) ion over the whole
temperature range; no long-range (internuclear) interactions
were detected in this case.
˚
0.2445(8) A, respectively, from the planes, and they are on the
same side as the axial donor atoms (Cl2 and O1, respectively).
The two basal planes make a dihedral angle of 48.66(3)8. The
molecule assumes an S shape which brings the three aromatic
rings in a suitable position for the formation of intramolecular
p-stacking interactions, with centroidꢀꢀꢀcentroid distances of
˚
3.6955(13) and 3.7572(13) A, and dihedral angles of 30.70(11)
and 31.44(11)8. Moreover, two N–HꢀꢀꢀCl hydrogen bonds join
the two halves of the molecule, while the water ligand is
hydrogen bonded to the Cl2 atom pertaining to a neighbouring
molecule, and to the perchlorate anion. The complex molecules
are stacked so as to form columns parallel to the a axis, between
which the counterions are located.
The xmT value of the binuclear complex 2 at 300 K
is 1.02 cm3 K molꢁ1, which is consistent with the spin-only
value for two copper(II) ions. However, on cooling, the value
decreases gradually, and the xmT versus T profile indicates
antiferromagnetic coupling (Fig. 4). The xm versus T data
were fitted to the Bleaney–Bowers equation[6] (H ¼ ꢁ2JS1ꢀS2)
where 2J is the singlet–triplet splitting, and the solid line in
Fig. 4 represents the best-fit situation with g ¼ 2.18 and 2J ¼
ˆ
ˆ
EPR Studies
The EPR spectrum of 1 in a frozen DMF solution at 110 K and its
numerical simulation is given in Fig. 3a. The spectrum displays
the axial characteristics of the g-tensor and the copper nuclear
hyperfine couplings; typical for a copper(II) ion with a dx2–y2
ground state.[4] The spectrum is well simulated with the axial
g-tensor (S ¼ 1/2, g! ¼ 2.215, g| ¼ 2.050) and the axial copper
nuclear hyperfine tensor (I ¼ 3/2, A! ¼ 170 G). These values fall
in the range of those for the EPR of type 2 copper centres or
model complexes with square planar or square pyramidal
coordination geometries, in good agreement with the crystal
structure of 1.[5a–d] The observed g-values also preclude the
possibility that complex 1 has the electronic structure of a tri-
gonal bipyramid where g| is generally larger than g!.[5e]
The 14Neq (I ¼ 1) nuclear super-hyperfine couplings between
copper(II) and the equatorial nitrogen atoms, which are often
observed in copper(II) complexes with square-plane-based
geometries, are not resolved in 1. This may be due to the
ꢁ1.23 cmꢁ1. The CuꢀꢀꢀCu distance is 4.9529(5) A. This result
˚
indicates that a weak antiferromagnetic interaction is operative
in the intramolecular CuꢀꢀꢀCu core of this complex.
Conclusion
The synthesis of the copper(II) complexes of two new mixed
pyridyl–aliphatic amine ligands is reported along with their
X-ray structures and variable temperature magnetic behaviour.
Unusual non-symmetric coordination behaviour was observed
for the dinuclear species, [Cl2Cu(L2)CuCl(H2O)]ClO4 (2),
which also shows weak antiferromagnetic coupling between its
copper(II) centres.
Experimental
All reagents were purchased from Aldrich and used as received.
Chromatography was conducted using a glass column under

Pyridyl–Aliphatic Amine Ligands
929
gravity flow employing SP-Sephadex C25 (Naþ form) ion
exchange resin. Electronic absorption spectra were measured
with a SCINCO S-2100 diode array spectrophotometer and
elemental analysis on a Chemtronics TEA-3000 analyser.
Crystals used for X-ray diffraction were stored under the cor-
responding reaction solution before mounting on the diffrac-
tometer. Samples for microanalysis were dried at 608C in air. An
X-Band (9 GHz) EPR spectrum was recorded on a Jeol (Japan)
JES-TE300 ESR spectrometer using a 100 kHz field modulation
and a Jeol ES-DVT3 variable temperature controller. The
spectroscopic simulation was performed using the program
Simfonia (v. 1.25, Bruker Instruments Inc.). Magnetic suscep-
tibilities of ground samples were measured on a super-
mixture was heated at 808C for 12 h under nitrogen. The pale
yellow solution was cooled to room temperature and NaBH4
(12.0 g) was slowly added. The mixture was stirred overnight
and then 1.0 mol Lꢁ1 HCl (5 mL) followed by 1.0 mol Lꢁ1
NaOH (5 mL) were added and the solution was evaporated to
dryness under reduced pressure and the residue dissolved in
water (100 mL). The solution was extracted with dichlor-
omethane (50 mL ꢂ 5), the combined extracts were washed with
water (50 mL ꢂ 3) and then dried over Na2SO4. This solution
was evaporated under reduced pressure to give the product as a
brown oil which was used for complex formation without further
purification (yield: 11.7 g).
The above product (7.7 g) was dissolved in acrylonitrile
(38.0 g) and glacial acetic acid (2.9 g) was added. The mixture
was heated at reflux for 72 h under a nitrogen atmosphere. The
resulting deep brown solution was evaporated to dryness under
reduced pressure. Dichloromethane (100 mL) was added and the
solution was washed with 0.88 mol Lꢁ1 NH3 (100 mL) and then
water (3 ꢂ 100 mL) and the organic phase was dried over
Na2SO4. The solution then was evaporated to dryness under
reduced pressure to give a yellow oil which was dissolved in
methanol (50 mL). Raney-Ni (4.0 g) in water (20 mL) was added
followed by slow addition of NaBH4 (18.9 g) in 4 % NaOH
(200 mL) with vigorous stirring at 608C. The mixture was stirred
overnight and then filtered through Celite and evaporated to
dryness under reduced pressure. The residue was dissolved in
8 mol Lꢁ1 NaOH (50 mL) and extracted with dichloromethane
(5 ꢂ 50 mL). The combined extracts were dried over anhydrous
Na2SO4 and evaporated under reduced pressure to give L2 as a
brown oil that was used for complex formation without further
purification (yield: 6.8 g).
The above product (5.4 g) was dissolved in methanol
(100 mL) and CuCl2ꢀ2H2O (4.3 g) in methanol (100 mL) was
added with stirring. The blue mixture was evaporated to dryness
under reduced pressure and the residue was dissolved in water
(1 L) and the solution was filtered. The filtrate was applied to a
SP-Sephadex C-25 (Naþ form) in a column which was initially
washed with water (300 mL) and then eluted with 0.3 mol Lꢁ1
NaCl. The (major) blue band was separated and the eluent
evaporated to dryness under reduced pressure. The complex
product was then extracted several times into ethanol to remove
NaCl. The extracts were evaporated to dryness under reduced
pressure (yield: 5.2 g). The residue was dissolved in a minimum
volume of water and slow evaporation of the solution at ambient
temperature after addition of LiClO4 provided blue crystals
suitable for a structure determination. (Anal. Calc. for
C26H38Cl4Cu2N6O5: C 39.86, H 4.89, N 10.73. Found: C 39.2,
H 4.87, N 10.5 %.) lmax (water)/nm (e/Mꢁ1 cmꢁ1) 625 (2105).
conducting
quantum
interference
device
(SQUID)
magnetometer (Quantum Design MPMS-5S) under an external
field of 5000 Oe. The EPR spectra were measured using the
following conditions: microwave frequency, 9.133 GHz;
microwave power, 1.0 mW; modulation amplitude, 10 G; time
constant, 0.3 s; scan speed, 1250 G minꢁ1. Simulation para-
meters for EPR of 1: g ¼ [2.050 2.050 2.215]; ACu ¼ [0 0 170] G;
linewidth ¼ [45 45 45] G along the g-tensor frame.
[CuL1](ClO4)2 (1) (where L1 5 N1-(2-aminoethyl)-2,2-
dimethyl-N1,N3-bis(pyridin-2-ylmethyl)- propane-
1,3-diamine))
2,2-Dimethylpropane-1,3-diamine (5.1 g) and 2-pyridine-
carboxaldehyde (10.7 g) were reacted in methanol (100 mL) and
treated with NaBH4 (8.0 g) in an analogous manner to that
described for the initial step in the above procedure to give the
crude product (yield: 11.1 g). The product (8.0 g) was dissolved
in acetonitrile (150 mL), tosylaziridine (11.2 g) was added, and
then the mixture was heated at the reflux for 6 h. The dark red
solution was evaporated under reduced pressure to give a dark
red oil. Concentrated H2SO4 (100 mL) was slowly added and the
mixture was heated with continuous stirring at 1308C for 72 h.
The solution was cooled in an ice bath and ethanol/diethyl ether
(1 : 1, 1500 mL) was slowly added to give a hygroscopic dark
brown precipitate that was separated by filtration and then
immediately dissolved in 5 mol Lꢁ1 NaOH (150 mL) and
extracted with chloroform (3 ꢂ 100 mL). The combined extracts
were evaporated under reduced pressure to give a red oil. This
was dissolved in methanol (150 mL) and CuCl2ꢀ2H2O (4.8 g)
was added with stirring and stirring was continued for 30 min.
The mixture was evaporated to dryness under reduced pressure.
The blue residue was dissolved in water (500 mL) and chro-
matographed on an SP Sephadex column with 0.3 mol Lꢁ1 NaCl
as per the method above. The blue major band was collected, the
solution was evaporated to dryness under reduced pressure, and
the residue was extracted with ethanol to separate NaCl. The
ethanol solution was then evaporated under reduced pressure to
give a blue powder (yield: 4.3 g). This was dissolved in a min-
imum volume of warm water containing an excess of LiClO4ꢀ
Slow evaporation of the solution at ambient temperature yielded
blue crystals suitable for a structure determination. (Anal. Calc.
for C19H29Cl2CuN5O8: C 38.68, H 4.96, N 11.87. Found: C 38.8,
H 5.01, N 11.6 %.) lmax (water)/nm (e/Mꢁ1 cmꢁ1) 633 (1265).
Crystallography
The data were collected at 150(2) K on a Nonius Kappa-CCD
area detector diffractometer[7] using graphite-monochromated
˚
MoKa radiation (l 0.71073 A). The crystals were introduced into
glass capillaries with a protecting ‘Paratone-N’ oil (Hampton
Research) coating. The unit cell parameters were determined
from 10 frames, and then refined on all data. The data (combi-
nations of j- and v-scans with a minimum redundancy of 4 for
90 % of the reflections) were processed with HKL2000.[8]
Absorption effects were corrected empirically with the program
SCALEPACK.[8] The structures were solved by direct methods
with SHELXS-97, expanded by subsequent Fourier-difference
synthesis and refined by full-matrix least-squares on F2 with
0
[Cl2Cu(L2)CuCl(H2O)]ClO4 (2) (where L2 5 N1,N1 -(1,3-
phenylenebis(methylene))bis(N1-(pyridin-2-ylmethyl)
propane-1,3-diamine))
m-Xylylenediamine (5.1 g) was dissolved in dry ethanol
(100 mL), 2-pyridine-carboxaldehyde (8.1 g) was added, and the

930
Y. H. Lee et al.
Table 1. Crystal data and structure refinement details
SHELXL-97.[9] All non-hydrogen atoms were refined with ani-
sotropic displacement parameters. The hydrogen atoms bound
to oxygen and nitrogen atoms were found on Fourier-difference
maps, and the carbon-bound hydrogen atoms were introduced at
calculated positions. All hydrogen atoms were treated as riding
atoms with an isotropic displacement parameter equal to 1.2
times that of the parent atom (1.5 for CH3).
1
2
Empirical formula
M [g molꢁ1
C19H29Cl2CuN5O8
589.91
C26H38Cl4Cu2N6O5
783.50
]
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
P21/c
˚
a [A]
˚
b [A]
˚
c [A]
Crystal data and structure refinement parameters are given in
Table 1 and selected bond lengths and angles in Table 2. The
molecular plots were drawn with SHELXTL.[9] Full crystallo-
graphic data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif under CCDC numbers 870461 and 870462.
18.1096(9)
8.9447(5)
15.8658(4)
110.935(3)
2400.4(2)
4
11.4897(2)
16.0924(2)
17.5316(3)
98.8066(6)
3203.32(9)
4
b [deg.]
3
˚
V [A ]
Z
Dcalc [g cmꢁ3
]
1.632
1.625
F(000)
m(MoKa) [mmꢁ1
Measured reflections
1220
1608
Acknowledgement
]
1.188
1.708
This research was supported by Basic Science Research Program through the
National Research Foundation of Korea (NRF) funded by the Ministry of
Education, Science and Technology (2011-0011187) (YK) and the Austra-
lian Research Council (LFL).
90603
107701
Independent reflections
4533
8278
Observed reflections
3973
6960
[I . 2s(I)]
Rint
0.023
318
0.030
388
References
Parameters refined
R1
wR2
S
0.036
0.098
1.045
ꢁ0.57
0.79
0.033
0.087
1.040
ꢁ0.68
0.64
[1] (a) Y.-Q. Zheng, D.-Y. Cheng, B.-B. Liu, W.-X. Huang, Dalton Trans.
2010, 40, 277. doi:10.1039/B916719F
(b) A. Woo, Y. H. Lee, S. Hayami, L. F. Lindoy, P. Thue´ry, Y. Kim,
J. Incl. Phenom. Macrocycl. Chem. 2011, 71, 409. doi:10.1007/S10847-
011-0030-7
ꢁ3
˚
Drmin [e Aꢁ3
]
˚
Drmax [e A
]
(c) C. Nunez, R. Bastida, L. Lezama, A. Macias, P. Perez-Lourido,
L. Valencia, Inorg. Chem. 2011, 50, 5596. doi:10.1021/IC200287F
(d) A. Escuer, G. Vlahopoulou, S. P. Perlepes, M. Font-Bardia,
T. Calvet, Dalton Trans. 2011, 40, 225. doi:10.1039/C0DT00720J
(e) M. Kim, C. Mora, Y. H. Lee, J. K. Clegg, L. F. Lindoy, K. S. Min,
P. Thue´ry, Y. Kim, Inorg. Chem. Commun. 2010, 13, 1148. doi:10.1016/
J.INOCHE.2010.06.033
˚
Table 2. Selected bond lengths [A] and angles [deg.] for 1 and 2
(f) V. Mathrubootham, A. W. Addison, K. T. Holman, E. Sinn,
L. K. Thompson, Dalton Trans. 2009, 8111. doi:10.1039/B910188H
(g) S. Turba, O. Walter, S. Schindler, L. P. Nielsen, A. Hazell,
C. J. McKenzie, F. Lloret, J. Cano, M. Julve, Inorg. Chem. 2008, 47,
9612. doi:10.1021/IC800244G
1
2
Cu–N(1)
Cu–N(2)
Cu–N(3)
Cu–N(4)
Cu–N(5)
2.158(2)
2.086(2)
2.035(2)
2.016(2)
2.030(2)
Cu(1)–N(1)
Cu(1)–N(2)
Cu(1)–N(3)
Cu(2)–N(4)
Cu(2)–N(5)
Cu(2)–N(6)
Cu(1)–Cl(1)
Cu(1)–Cl(2)
Cu(2)–Cl(3)
Cu(2)–O(1)
2.1209(18)
2.0085(16)
1.9909(19)
2.0757(17)
2.0086(17)
1.9891(17)
2.3291(7)
2.4992(6)
2.3000(6)
2.2101(17)
[2] (a) C. R. K. Glasson, L. F. Lindoy, G. V. Meehan, Coord. Chem. Rev.
2008, 252, 940. doi:10.1016/J.CCR.2007.10.013
(b) B. Antonioli, D. J. Bray, J. K. Clegg, K. Gloe, K. Gloe, O. Kataeva,
L. F. Lindoy, J. C. McMurtrie, P. J. Steel, C. J. Sumby, M. Wenzel,
Dalton Trans. 2006, 4783 and reference therein. doi:10.1039/
B609738C
N(4)–Cu–N(5)
N(4)–Cu–N(3)
N(5)–Cu–N(3)
N(4)–Cu–N(2)
N(5)–Cu–N(2)
N(3)–Cu–N(2)
N(4)–Cu–N(1)
N(5)–Cu–N(1)
N(3)–Cu–N(1)
N(2)–Cu–N(1)
95.64(9)
81.23(9)
156.57(10)
178.10(8)
85.72(8)
96.99(8)
98.84(8)
100.22(8)
103.21(9)
82.20(8)
[3] A. W. Addison, T. N. Rao, J. Reedijk, J. van Rijn, G. C. Verschoor,
J. Chem. Soc., Dalton Trans. 1984, 1349. doi:10.1039/DT9840001349
[4] E. Garribba, G. Micera, J. Chem. Educ. 2006, 83, 1229. doi:10.1021/
ED083P1229
[5] (a) V. Noethig-Laslo, N. Paulid, Monatsh. Chem. 1997, 128, 1101.
doi:10.1007/BF00807560
N(3)–Cu(1)–N(2)
N(3)–Cu(1)–N(1)
N(2)–Cu(1)–N(1)
N(3)–Cu(1)–Cl(1)
N(2)–Cu(1)–Cl(1)
N(1)–Cu(1)–Cl(1)
N(3)–Cu(1)–Cl(2)
N(2)–Cu(1)–Cl(2)
N(1)–Cu(1)–Cl(2)
Cl(1)–Cu(1)–Cl(2)
N(6)–Cu(2)–N(5)
N(6)–Cu(2)–N(4)
N(5)–Cu(2)–N(4)
N(6)–Cu(2)–O(1)
N(5)–Cu(2)–O(1)
N(4)–Cu(2)–O(1)
N(6)–Cu(2)–Cl(3)
N(5)–Cu(2)–Cl(3)
N(4)–Cu(2)–Cl(3)
O(1)–Cu(2)–Cl(3)
172.01(8)
92.26(8)
81.54(7)
88.80(7)
94.27(5)
151.65(5)
93.17(7)
93.33(5)
105.37(5)
102.86(2)
172.75(7)
92.28(7)
83.09(7)
98.20(7)
87.98(7)
97.97(7)
88.04(5)
94.41(5)
159.93(5)
101.85(5)
(b) S. S. Lemos, M. L. P. Collins, S. S. Eaton, G. R. Eaton,
W. E. Antholine, Biophys. J. 2000, 79, 1085. doi:10.1016/S0006-3495
(00)76362-4
(c) P. J. van Dam, E. J. Reijerse, M. J. van der Meer, R. Guajardo,
P. K. Mascharak, E. de Boer, Appl. Magn. Reson. 1996, 10, 71.
doi:10.1007/BF03163100
(d) E. I. Solomon, U. M. Sundaram, T. E. Machonkin, Chem. Rev. 1996,
96, 2563. doi:10.1021/CR950046O
(e) E. Garribba, G. Micera, J. Chem. Educ. 2006, 83, 1229. doi:10.1021/
ED083P1229
[6] B. Bleaney, K. D. Bowers, Proc. Roy. Soc. Lond. A 1952, 214, 451.
[7] R. W. W. Hooft, COLLECT 1998 (Nonius BV: Delft, The Netherlands).
[8] Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307.
doi:10.1016/S0076-6879(97)76066-X
[9] G. M. Sheldrick, Acta Crystallogr. A 2008, 64, 112. doi:10.1107/
S0108767307043930