Synthesis and reactivity of 1-[(2-methoxy)benzene]-3-[benzothiazole] triazene with copper(II) or cobalt(II) chloride

Article abstract of DOI:10.1080/15533174.2011.615786

A new triazene, 1-[(2-methoxy)benzene]-3-[benzothiazole] triazene (HL), has been synthesized and charaterized. In the presence of Et₃N, the reaction of HL and CuCl₂·2H₂O or CoCl ₂·6H₂O gives the triazenide complexes [Cu ₄L′₄(μ-OMe)₄] 1 (L′1- [benzothiazole]triazene ion) and [Co₂L₄] 2, respectively. The X-ray crystal structures of both complexes have been obtained. Magnetic studies indicate significant antiferromagnetic coupling between the copper(II) centers or cobalt(II) centers for complexes 1 and 2, with coupling constants (J) of -587 cm^-1 for 1 and -147 cm^-1 for 2. Complex 2 shows one reversible one-electron redox wave at -0.835 V, and one irreversible oxidation at -0.193 V, which are in accord with the redox potentials of [Co ^III-Co^II]/[Co^II-Co^II] and [Co ^III-Co^III]/[Co^II-Co^II] couples, respectively.

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Synthesis and Reactivity of 1-[(2-methoxy)benzene]-
3-[benzothiazole]Triazene With Copper(II) or Cobalt(II)
Chloride
Qi-ying Lv a , Wei Li a & Shu-zhong Zhan a
a College of Chemistry & Chemical Engineering, South China University of Technology ,
Guangzhou , P. R. China
Accepted author version posted online: 27 Mar 2012.Published online: 04 Jun 2012.
To cite this article: Qi-ying Lv , Wei Li & Shu-zhong Zhan (2012) Synthesis and Reactivity of 1-[(2-methoxy)benzene]- 3-
[benzothiazole]Triazene With Copper(II) or Cobalt(II) Chloride, Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-
Metal Chemistry, 42:5, 764-769
To link to this article: http://dx.doi.org/10.1080/15533174.2011.615786
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 42:764–769, 2012
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.615786
Synthesis and Reactivity of 1-[(2-methoxy)benzene]-
3-[benzothiazole]Triazene With Copper(II) or Cobalt(II)
Chloride
Qi-ying Lv, Wei Li, and Shu-zhong Zhan
College of Chemistry & Chemical Engineering, South China University of Technology, Guangzhou,
P. R. China
as these compounds can serve as a monodentate (a),[1,2] a biden-
tate chelating (b),[3–5] or a bridging ligand (c) (Scheme 1).[1,2,6–8]
With this mind, we extended our interests to the synthesis and
their reactivity with transition metals of new triazenide ligands
(such as Scheme 1).
As part of this research, a new triazenide ligand, namely
1-[(2-methoxy)benzene]-3-[benzothiazole]triazene (HL), has
been synthesized from the reaction of o-anisidine, sodium ni-
trite, and 2-aminobenzothiazole. In the presence of Et3N, the re-
action of H2L and CuCl2·2H2O or CuCl2·2H2O or CoCl2·6H2O
affords the complex [Cu4Lꢁ4(µ-OMe)4] 1 or [Co2L4] 2, respec-
tively. In this paper, we present the synthesis and characteri-
zation of H2L, its complexes 1 and 2, as well as the possible
procedure of the formation of 1-[benzothiazole]triazene (Lꢁ)
from HL thereof.
A
new triazene, 1-[(2-methoxy)benzene]-3-[benzothiazole]
triazene (HL), has been synthesized and charaterized. In the
presence of Et3N, the reaction of HL and CuCl2·2H2O or
CoCl2·6H2O gives the triazenide complexes [Cu4Lꢀ4(µ-OMe)4] 1
(Lꢀ 1-[benzothiazole]triazene ion) and [Co2L4] 2, respectively. The
X-ray crystal structures of both complexes have been obtained.
Magnetic studies indicate significant antiferromagnetic coupling
between the copper(II) centers or cobalt(II) centers for complexes
1 and 2, with coupling constants (J) of –587 cm−1 for 1 and –147
cm−1 for 2. Complex 2 shows one reversible one-electron redox
wave at –0.835 V, and one irreversible oxidation at –0.193 V, which
are in accord with the redox potentials of [CoIII-CoII]/[CoII-CoII]
and [CoIII-CoIII]/[CoII-CoII] couples, respectively.
Keywords electrochemical property, C-N bond cleavage, crystal
structures, magnetic properties, reactivity of triazene
EXPERIMENTAL
INTRODUCTION
Physical Measurements
A fundamental aim of coordination chemistry is the assem-
bly of compounds that exhibit novel properties. An approach
toward this important goal is the preparation of unique ligands
that impart novel chemistry when incorporated into the metal
coordination sphere. By designing the appropriate ligands, we
can chelate metal centers in special frame and control the elec-
tron withdrawal from the metal ion core, thereby modifying
the intramolecular exchange interactions. The use of different
bridging and polydentate ligands has afforded an impressive ar-
ray of nuclear coordination complexes with new architectures.
Among them, the triazenide ligands have attracted our attention,
1H NMR spectrum was measured on a Bruker AM 500 spec-
trometer in CDCl3 (Switzerland). Magnetic susceptibility data
for crystal samples were collected in the temperature range of
2–300 K with a Quantum Design SQUID Magnetometer MPMS
XL-7 (USA). Effective magnetic moments were calculated by
ꢀ
the equation µeff = g[ ZS(S+1)]1/2, where χM is the molar
magnetic susceptibility. The electrolytic cell used was a con-
ventional three-compartment cell, in which a Pt working elec-
trode, a Pt auxiliary electrode, and a saturated calomel electrode
(SCE) was employed. The CV measurement was performed
at room temperature using 0.10 mol·L−1 tetrabutylammonium
hexafluorophosphate (TBAP) as the supporting electrolyte.
Synthesis of 1-[(2-methoxy)benzene]-3-[benzothiazole]
Triazene (HL)
Received 17 May 2011; accepted 16 August 2011.
This work was supported by the Research Foundation for Re-
turned Chinese Scholars Overseas of Chinese Education Ministry (No.
B7050170), the National Science Foundation of China (No. 20971045),
and the Student Research Program (SRP) of South China University of
Technology.
Address correspondence to Shu-zhong Zhan, College of Chem-
istry & Chemical Engineering, South China University of Technology,
Guangzhou 510640, P. R. China. E-mail: shzhzhan@scut.edu.cn
O-anisidine (1.23 g, 10 mmol) in water (5 mL) was mixed
with 1 mol·L−1 HCl 30 mL (30 mmol) at 0◦C. An aqueous
solution (15%) of sodium nitrite (15 mmol) was added dropwise
with stirring. Once the amine was dissolved, a 15% solution of
2-aminobenzothiazole in ethanol (1.50 g, 10 mmol) was added
at 0◦C and stirred for 8 h. The reaction mixture was neutralized
764

TRANSITION METAL COMPLEXES
765
TABLE 1
Crystallographic data for complexes 1 and 2
Parameter
1
2
Empirical formula C32H28Cu4N16O4S4 C56H44Co2N16O4S4
Formula weight
λ(Å)
Temperature (K)
Crystal system
Space group
1083.18
0.71073
295
triclinic
P-1
1251.17
0.71073
150
monoclinic
C2/c
SCH. 1. Generic triazenido binding modes and new triazenes.
with a 15% aqueous of CH3CO2Na to give a yellow precipitate.
The reaction mixture was filtered, and the solid was purified by
crystallization at –4◦C from 9:1 ethyl acetate/hexanes to obtain
yellow crystals. The crystals were collected and dried in vacuo
(1.89 g, 67%). Anal. Calcd. for C14H12N4OS: C, 59.16; H, 4.23;
N, 19.72. Found: C, 58.67; H, 4.19; N, 19.90. 1H NMR (CDCl3,
ppm): δ 13.04 (s, 1H, N-H), 8.09 (d, J = 2.7 Hz, 1H, Ar), 8.03
(d, J = 2.5 Hz, 1H, Ar), 7.96 (d, J = 2.8 Hz, 1H, Ar), 7.82 (d, J
= 2.5 Hz, 1H, Ar), 7.64 (t, J = 5.2 Hz, 1H, Ar), 7.47 (t, J = 5
Hz, 1H, Ar), 7.39 (t, J = 5 Hz, 1 Hz, Ar), 7.21 (t, J = 5 Hz, 1
Hz, Py), 3.99 (s, 3H, -OCH3).
Unit cell dimension (Å,◦)
8.976(6)
11.950(8)
12.065(8)
91.318(8)
100.804(8)
102.832(8)
1
a
b
c
α
β
γ
Z
31.977(3)
22.7264(19)
20.8859(17)
90.00
120.032(2)
90.00
8
Dc(Mgm−3
F(000)
)
1.455
1.265
544
5136
θ range for data
collection
Reflections
collected/unique
Data/restraints/
parameters
2.37–25.50◦
3.07–26.00◦
Synthesis of Complex [Cu4(␮-OMe)4Lꢀ4] 1
8066/4515
4515/0/271
1.045
28798/12507
12507/0/744
0.971
To a solution of HL (0.29 g, 1.0 mmol) and triethylamine
(0.10 g, 1.0 mmol) in ethanol (25 ml), CuCl2·2H2O (0.17 g,
1.0 mmol) was added and stirred for 30 min. Slow evaporation
afforded deep green crystals, which were collected and dried in
vacuo (0.15 g, 54.1%). Anal. Calcd. for C16H14Cu2N8O2S2: C,
35.45; H, 2.59; N, 20.68. Found: C, 35.89; H, 2.85; N, 20.12.
Goodness-of-fit on
F2
Final R indices
[I > 2σ(I)]
R1 = 0.0403
R1 = 0.0868
wR2 = 0.1166
R1 = 0.0565
wR2 = 0.1237
wR2 = 0.2280
R1 = 0.1479
wR2 = 0.2770
Synthesis of Complex [Co2L4] 2
R ´ındices (all data)
The procedure was performed in the same way as that for the
synthesis of complex 1 except that CuCl2·2H2O was replaced
by CoCl2·6H2O, complex 2 was obtained in 54.1% yield (0.15
g). Calcd for C56H44Co2N16O4S4: C, 53.71; H, 3.52; N, 17.90.
Found: C, 52.87; H, 3.46; N, 18.41.
RESULTS AND DISCUSSION
Synthesis
The reaction of o-anisidine, sodium nitrite, and 2-
aminobenzothiazole provided a triazene (HL). Complexes 1
and 2 were obtained by the reaction of HL and CuCl2·2H2O
or CoCl2·6H2O, respectively. Interestingly, the reaction of
HL and CuCl2·2H2O in the presence of Et3N provided
complex 1 [Cu4Lꢁ4(µ-OMe)4] with a new Lꢁ− ligand (1-
[benzothiazole]triazene ion) (Scheme 2). The procedure of the
formation of Lꢁ− can be illustrated by Scheme 3, the treat-
ment of HL with Et3N gives a triethylammonium triazenide salt
([Et3NH]L) A.[11] Furthermore, the rearrangement of A provides
an intermediate B. Finally, C-N bond cleavage of HL affords a
new Lꢁ− ligand, accompanied loss of phenyl methyl ether.
X-Ray Crystallography
Data were collected with a Bruker SMART CCD area de-
tector using graphite monochromated Mo-K radiation (0.71073
Å). All empirical absorption corrections were applied by using
the SADABS program.[9] The structures were solved using di-
rect methods and the corresponding non-hydrogen atoms were
refined anisotropically. All the hydrogen atoms of the ligands
were placed in calculated positions with fixed isotropic thermal
parameters and included in the structure factor calculations in
the final stage of full-matrix least-squares refinement. All cal-
culations were performed using the SHELXTL computer pro-
gram.[10] Table 1 lists details of the crystal parameters, data
collection, and refinement for complexes 1 and 2. The selected
bond distances and angles for complexes 1 and 2 are listed in
Tables 2 and 3.
Structures of Complexes 1 and 2
As shown in Figure 1, the metallic core comprises four cop-
per centers, all in distorted planar geometries, arranged in a

766
Q.-Y. LV ET AL.
TABLE 2
Selected bond distances (Å) and angles (◦) for complex 1
Cu(1)-N(5)
Cu(2)-N(6)
Cu(2)-O(1)#
Cu(2)-Cu(1)
O(1)-Cu(1)-O(2)
Cu(1)-(O(2)-Cu(2)#
Cu(1)-Cu(2)-Cu(2)#-Cu(1)#1
1.969 (3)
2.009 (3)
1.927 (3)
3.0163 (17)
77.09 (12)
102.33 (13)
0
Cu (1)-N(2)
Cu(2)-N(1)
Cu(2)-O(2)#
Cu (2)-Cu(1)#
Cu(1)-O(1)-Cu(2)#
2.025 (3)
1.979 (3)
1.907 (3)
2.9697 (15)
100.89 (12)
O(1)-Cu(1)-Cu(2)#-O(2)
5.91
Symmetry transformations used to generate equivalent atoms: –x, –y + 1, –z + 1.
square-planar array with the torsion angle Cu(1)-Cu(2)-Cu(2)#-
Cu(1)#1 of 0◦. The structure of 1 consists of two symmetry-
related di-µ2-methoxo-bridged copper(II) dimeric units (Cu(1)-
Cu(2)# and Cu(1)-Cu(2)#). The Cu-O bond lengths are within
the range of 1.906(3) to 1.927(3) Å, and Cu-O-Cu angles fall in
100.87(12) to 102.33(13)◦.
3.0163(17) Å is longer than that found in Cu2(Ac)3(triazenide)
(2.5316(6) Å).[15]
As shown in Figure 2, the structure of complex 2 shows the
L− ligand doesn’t bind in a bis(bidentate) manner bridging the
two cobalt centers, but coordinate to the cobalt center by two
terminal N atoms of each L− ligand. The average N-N-N angle
of 108.4(5)◦ and the average N-N bond length of 1.3219 Å agree
with those reported for the Co(dpt)3 complex.[17]
Similar to the “roof-shaped” Cu2(µ2-OMe)2 geometry
found in [Cu4Ldur(µ2-OMe)4]4+ (Ldur = 1,4,7-triazacyclonon)
complex,[12] the Cu2O2 bridging units in complex 1 also
adopt bent, or “roof-shaped” conformations. This distor-
tion is evident from the torsion angle O(1)-Cu(1)-Cu(2)#-
O(2) of 5.97◦. In the case of 1, the Cu···Cu separa-
tion (2.9697 Å) is similar to that found in [Cu4Ldur(µ2-
Two cobalt atoms are bridged by four L− ligands to form two
12-membered Co2N8C2 rings, which lie vertically. Each cobalt
sphere may be described as a distorted octahedral geometry
with axial and equatorial ligands, the axial atoms being N(1)
and N(9) for Co(1) and N(5) and N(13) for Co(2). The Co-Nax
distances are homogeneous with an average value of 2.133 Å,
but the Co-Neq distances are in the 2.148–2.226 Å range for
both cobalt spheres.
OMe)4]4+ (2.962(1) Å). “Roof-shaped” Cu2O2 cores have
[13]
been observed in [Cu2(C6H11NH2)4(µ2-OH)2](ClO4)2
and
[Cu2(CH3NH2)4(µ2-OH)2](SO4)·H2O,[14] and Cu···Cu dis-
tances of 2.934(8) and 2.782(5) Å, respectively.
The two Cu2O2 units are capped by four Lꢁ− ligands. The
bond distances of between Cu and N fall in the range 1.969(3)
to 2.025(3) Å, which are similar to those found in copper(II) tri-
azenide complexes 1.973 to 2.088 Å.[15,16] The Cu···Cu distance,
Magnetic Properties of Complexes 1 and 2
The magnetic behavior of 1 is shown in Figure 3 in the form
of χM versus T or χMT versus T. Copper(II), which has the
d9 configuration, is expected to exhibit paramagnetic behavior.
TABLE 3
Selected bond distances (Å) and angles (◦) for complex 2
Co(1)-N(9)
Co(1)-N(6)
Co(1)-N(8)
Co(2)-N(5)
Co(2)-N(2)
Co(2)-N(10)
N(2)-N(3)
2.124 (5)
2.148 (5)
2.187 (6)
2.120 (6)
2.148 (5)
2.184 (5)
1.325 (6)
1.371 (7)
1.330 (7)
1.340 (7)
166.85 (19)
59.60 (18)
58.66 (18)
108.9 (5)
108.7 (5)
Co(1)-N(1)
Co(1)-N(16)
Co(1)-N(14)
Co(2)-N(13)
Co(2)-N(12)
Co(2)-N(4)
N(3)-N(4)
N(7)-N(8)
N(11)-N(12)
N(15)-N(16)
N(14)-Co(1)-N(16)
N(5)-Co(2)-N(13)
N(2)-Co(2)-N(4)
N(8)-N(7)-N(6)
N(16)-N(15)-N(14)
2.136 (5)
2.179 (5)
2.208 (6)
2.146 (5)
2.172 (5)
2.226 (5)
1.304 (7)
1.289 (6)
1.295 (7)
1.321 (7)
58.7 (2)
N(6)-N(7)
N(10)-N(11)
N(14)-N(15)
N(1)-Co(1)-N(9)
N(6)-Co(1)-N(8)
N(10)-Co(2)-N(12)
N(4)-N(3)-N(2)
N(12)-N(11)-N(10)
166.96 (19)
58.48 (18)
108.2 (5)
107.8 (5)

TRANSITION METAL COMPLEXES
767
FIG. 1. X-ray structure of complex 1 (color figure available online).
SCH. 2. Schematic representation of the synthesis of HL, 1 and 2.
sis of the Heisenberg model H = –2JS1·S2. The molar magnetic
susceptibility for Cu(II)-Cu(II) units is expressed as Eq. 1.[18]
However, complex 1 is diamagnetic at 300 K, because of strong
coupled interactions between copper(II) ions.
Two different exchange pathways can occur in complex 1:
Cu-N-C-N-Cu and Cu-O-Cu. To explain the magnetic behavior
of complex 1, its structure can consequently be reduced to a cen-
ꢁ
ꢂ
ꢃꢄ−1
Nβ2g2
1
2J
kT
Nβ2g2
χM
=
1 + exp −
(1−ρ)+
ρ+Nα
3kT
3
4kT
[1]
Least-squares fitting of the experimental data led to J = –587
tral Cu4N4O4 core. The Cu-N-C-N-Cu pathway in complex 1, is cm−1, g = 2.1, Nα = 1.1 × 10−3 cm3mol−1, and ρ = 0.001.
assumed to have only a second-order effect on the magnetic ex- As a consequence, there are very strong antiferromagnetic ex-
change between the copper centers. The tetranuclear copper(II) change interactions between copper(II) ions. The major factor
complex 1 can be formally divided into two dinuclear Cu2O2 controlling the exchange interactions in hydroxy-, alkoxy-, and
subunits. The interdimer coupling via nitrogen atoms is assumed phenoxy-bridged copper(II) is the Cu-O-Cu bridge angle.[19,20]
to be weaker than the intradimer exchange interactions via the The average Cu-O-Cu bridge angle of 102◦ for 1 would re-
oxygen atoms (µ-OMe). Hence the data can be fitted on the ba- sult in an approximate J value of –350 cm−1 according to the
SCH. 3. The possible mechanism of the formation of Lꢁ.

768
Q.-Y. LV ET AL.
FIG. 4. Plot of the χMT versus T and χM versus T (inset) for complex 2 at
2000 Oe. Solid line corresponds to the best fit.
FIG. 2. X-ray structure of complex 2 (color figure available online).
two isolated CoII ions (S = 3/2) and decreases linearly with
decreasing temperature between 300–2 K, and reaches to 0.227
cm3Kmol−1 at 2.0 K.
empirical equation reported in the literature and it deviates ap-
preciably from the experimentally determined value of –585
cm−1 for complex 1. A possible reason for the strong exchange
coupling in complex 1 is that the methoxide ion, with shorter Cu-
O (average 1.923 Å) distance and a larger Cu(1)-O(5)-Cu(2)#
angle (102.89◦) than those with the phenoxide ion, provides a
better pathway for antiferromagnetic exchange coupling.[21–23]
The magnetic behavior of complex 2 is shown in Figure 4
in the form of χMT versus T or χMT versus T. With decreas-
ing temperature, the χMT value decreases rapidly in an unusual
linear fashion. This behavior can be ascribed to an antiferro-
magnetic interaction modified by the contribution of anisotropic
exchange. The value of χMT at 300 K, 5.16 cm3Kmol−1 (6.42
µB), is larger than the value of 3.75 cm3Kmol−1 (5.48 µB) of
The magnetism of 2 can be well reproduced by a modified
Bleaney-Bowers Eq. 2.[24]
ꢁ
ꢂ
ꢃꢄ−1
2Nβ2g2
kT
J
Nβ2g2
χM
=
3 + exp −
(1−ρ)+
ρ+2Nα
kT
2kT
[2]
Least-squares fitting of the experimental data led to J =
–147 cm−1, Nα = 7.1 × 10−3 cm3mol−1, and ρ = 0.007. As
a consequence, there are strong antiferromagnetic exchange in-
teractions between Co(II) ions.
Electrochemical Property of Complex 2
The electrochemical property of complex 2 was measured by
cyclic voltammetry in CH3CN. As shown in Figure 5, complex
FIG. 5. CV of complex 2 in CH3CN/0.1 mol·L−1 [Bu4N]PF6 at 100 mV s−1
FIG. 3. Plot of the χMT versus T and χM versus T (inset) for complex 1 at
3000 Oe. Solid line corresponds to the best fit.
scan rate.

TRANSITION METAL COMPLEXES
769
2 shows one reversible one-electron redox wave at –0.835 V,
and one irreversible oxidation at –0.193 V, which are in accord
with the redox potentials of [CoIII-CoII]/[CoII-CoII] and [CoIII-
CoIII]/[CoII-CoII] couples, respectively.
8. Lei, W.-J.; Tan, X.-W.; Han, L.-J.; Zhan, S.-Z.; Li, B.-T. Design, synthesis
and properties of a trinuclear copper(I) cluster with a triazenide ligand.
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Area Detector Data; University of Go¨ttingen: Go¨ttingen, Germany, 1996.
10. Sheldrick, G.M. SHELXS 97, Program for Crystal Structure Refinement;
University of Go¨ttingen: Go¨ttingen, Germany, 1997.
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tion of new triazenide salts. J. Org. Chem. 2006, 71, 4014–4017.
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Moubaraki, B.; Murray, K.S.; Spiccia, L. Syntheses, crystal structures,
magnetic properties, and EPR spectra of tetranuclear copper(II) complexes
featuring pairs of “roof-shaped” Cu2×2 dimers with hydroxide, methoxide,
and azide bridges. Inorg. Chem. 2001, 40, 1536–1543.
13. Charlot, M.F.; Jeannin, S.; Jeannin, Y.; Kahn, O.; Lucrece-Aubal,
J.; Martin-Frere, J.S. Crystal structure and magnetic properties of
tetrakis(cyclohexylamine)di-.mu.-hydroxo-dicopper(II) perchlorate. The
first example of a roof-shaped hydroxo-bridged copper(II) dimer. Inorg.
Chem. 1979, 18, 1675–1681.
1-[(2-methoxy)benzene]-3-[benzothiazole]triazene
(HL)
was synthesized by the reaction of o-anisidine and 2-
aminobenzothiazole, using half an equivalent of sodium nitrite.
This technique is facile and gives HL in high yield (67%). HL
can chelate and bridge copper or nickel centers to give two
complexes 1 and 2, which reveal significant antiferromagnetic
character. Currently we are exploring this area further, including
the design and synthesis of new triazenes, as well as their
reactivity with metals.
SUPPLEMENTARY MATERIALS
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roof-shaped hydroxo-bridged copper(II) dimmers. Inorg. Chem. 1980, 19,
1410–1411.
15. Rodriguez, J.G.; Parra-Hake, M.; Aguirre, G.; Ortega, F.; Walsh, P.J. Synthe-
sis and structure of a dinuclear copper complex of a bis(bidentate)triazenide
ligand. Polyhedron 1999, 18, 3051–3055.
16. Corbett, M.; Hoskins, B.F.; McLeod, N.J.; O’Day, B.P. Binuclear metal(II)
complexes of 1,3-diphenyltriazene: the crystal and molecular structures of
the nickel(II), palladium(II) and copper(II) derivatives. Aust. J. Chem. 1975,
28, 2377–2392.
CCDC 780722 & 780723 contain the supplementary
crystallographic data for complexes 1, and 2, respectively.
These data can be obtained free of charge via http://
www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cam-
bridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223–336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
17. Corbett, M.; Hoskins, B.F. An octahedral complex containing three four-
membered chelate rings. J. Am. Chem. Soc. 1967, 89, 1530–1532.
18. Mandal, S.K.; Thompson, L.K.; Newlands, M.J.; Gabe, E.J. Structural
and magnetic studies on macrocyclic dicopper(II) complexes. Influence of
electron-withdrawing axial ligands on spin exchange. Inorg. Chem. 1990,
29, 1324–1327.
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