Role of the kinetic template effect in the preparation of an original copper complex

Article abstract of DOI:10.1016/j.poly.2018.06.056

Reaction of diethylenetriamine with phenol derivatives possessing a phenyl ester function yields a ligand corresponding to the monocondensation of diethylenetriamine with the phenol derivative. In a following step, its coordination to copper ions gives a neutral complex that is able to react with orthovanillin in order to yield an original complex made of a non symmetric ligand possessing three nitrogen, amide, imine and secondary amine, and four oxygen, amide, phenol (2) and methoxy donor atoms, thanks to the kinetic template effect. In our example, the copper center brings the three reactive functions (first primary amine and aldehyde, then amide) in close vicinity so that the formation of an imine function and the protonation of the amide function can occur. The structural determination of the resulting complex confirms an unexpected copper coordination.

Full text of DOI:10.1016/j.poly.2018.06.056

Polyhedron 153 (2018) 158–162
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Role of the kinetic template effect in the preparation of an original
copper complex
⇑
Jean-Pierre Costes , Carine Duhayon, Laure Vendier
LCC-CNRS, Université de Toulouse, CNRS, Toulouse, France
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of diethylenetriamine with phenol derivatives possessing a phenyl ester function yields a ligand
corresponding to the monocondensation of diethylenetriamine with the phenol derivative. In a following
step, its coordination to copper ions gives a neutral complex that is able to react with orthovanillin in
order to yield an original complex made of a non symmetric ligand possessing three nitrogen, amide,
imine and secondary amine, and four oxygen, amide, phenol (2) and methoxy donor atoms, thanks to
the kinetic template effect. In our example, the copper center brings the three reactive functions (first pri-
mary amine and aldehyde, then amide) in close vicinity so that the formation of an imine function and
the protonation of the amide function can occur. The structural determination of the resulting complex
confirms an unexpected copper coordination.
Received 21 June 2018
Accepted 30 June 2018
Available online 11 July 2018
Keywords:
Coordination chemistry
Template effect
Structural Determination
Copper
Ó 2018 Elsevier Ltd. All rights reserved.
1. Introduction
complex is able to further react with the aldehyde function of a
phenol derivative in order to check if the kinetic template effect
Some years ago a new class of non symmetric ligands involving
amide, imine and phenol functions were used in the syntheses of
complexes associating 3d and 4f ions [1,2]. They have several
advantages. First of all they are trianionic for they have three func-
tions that can be deprotonated. Then they possess two coordina-
tion sites showing different affinities for metal ions, so that 3d-4f
complexes can be isolated. Presence of supplementary donor
atoms that do not belong to these coordination sites allows associ-
ation of these 3d-4f entities. Such ligands are prepared in a two
step process: the first step results in the reaction of phenol deriva-
tives possessing ester functions (phenyl salicylate or phenyl-3-
methoxysalicylate) with one primary amine of a diamine synthon,
which yields ligands very often called as ‘‘half-unit” ligands for
they still have a primary amine function that can be reacted in a
second step with aldehyde derivatives possessing again phenol
functions. These ‘‘half-unit” ligands present one phenol and one
amide functions that can be deprotonated and at least three donor
atoms, so that they are likely to coordinate 3d ions in their oxida-
tion state II to give neutral complexes. The present work is directed
toward the syntheses of ‘‘half-unit” ligands derived from
diethylenetriamine along with the structural determination of
one of these neutral copper complexes. In a following step we try
to verify if the coordinated primary amine of the neutral copper
is still working. A positive response would open a way yielding
original copper complexes.
2. Experimental
2.1. Materials
Phenyl salicylate, ortho-vanillin (Hovan), 3-methoxysalicylic
acid, 1,3-dicyclohexylcarbodiimide, diethylenetriamine, piperi-
dine, picric acid, phenol, Cu(OAc)2Á2H2O, NaClO4 (Aldrich) were
used as purchased. High-grade solvents (diethyl oxide, 2-propanol,
acetone, THF, methanol) and distilled water were used for the syn-
theses of ligands and complexes.
Caution! Because of their explosive character, perchlorate salts
and picric acid should be handled with care and in low amounts.
2.2. Ligand
L1H2. A mixture of phenyl salicylate (2.14 g, 1 Â 10À2 mol) and
diethylenetriamine (1.03 g, 1 Â 10À2 mol) was refluxed for 30
min and then cooled to room temperature with stirring. The result-
ing pasty product was dissolved in methanol. Addition of picric
acid induced a quick precipitation that was separated by filtration.
The new precipitate that appeared in the filtrate was filtered off,
washed with diethyl oxide and dried. This precipitate corresponds
to the picrate salt of the desired ligand. Yield: 1.3 g (29%). Anal.
⇑
Corresponding author.
E-mail address: jean-pierre.costes@lcc-toulouse.fr (J.-P. Costes).
https://doi.org/10.1016/j.poly.2018.06.056
0277-5387/Ó 2018 Elsevier Ltd. All rights reserved.

J.-P. Costes et al. / Polyhedron 153 (2018) 158–162
159
Calc. for C17H20N6O9 (452.38): C, 45.14; H, 4.46; N, 18.58. Found: C,
44.81; H, 4.33; N, 18.23. 1H NMR (250 MHz, 20 °C, dmso d6): d 3.22
(m, 4H, CH2N), 3.39 (m, 2H, CH2N), 3.61 (m, 2H, CH2N), 6.90 (t, J = 7
Hz, 1H, C(5)H), 6.91 (d, J = 7 Hz, 1H, C(3)H), 7.41 (t, J = 7 Hz, 1H, C
(4)H), 7.81 (d, J = 7 Hz, 1H, C(6)H), 8.10 (l, 3H, NH), 8.59 (s, 2H,
CH pic), 8.92 (t, J = 6 Hz, 1H, OCNH), 12.20 (l, 2H, OH). 13C{1H}
NMR (62.896 MHz, 20 °C, dmso d6): d 35.67 (s, CH2NH), 36.16 (s,
CH2NH), 44.65 (s, CH2NH2), 47.36 (s, CH2NHCO), 115.89 (s, ArC(1)
H), 117.75(s, ArC(3)), 119.17 (s, ArC(5)H), 124.90 (s, picCpNO2),
125.72 (s, picCH), 128.74 (s, ArC(6)H), 134.35 (s, ArC(4)), 142.22
(s, picCoNO2), 159.94 (s, ArC(2)OH), 161.32 (s, picCO), 169.80 (s,
OCNH).
Physical measurements: C, H, and N elemental analyses were
carried out at the Laboratoire de Chimie de Coordination, Microan-
alytical department, in Toulouse, France. IR spectra were recorded
with a Perkin-Elmer Spectrum 100FTIR using the ATR mode. Mag-
netic data of complex 3 were obtained with a Quantum Design
MPMS SQUID susceptometer, in the 2–300 K temperature range
and a 0.1 T applied magnetic field. Diamagnetic corrections were
applied by using Pascal’s constants [3].
2.4. Crystallographic data collection and structure determination for
complexes 2 and 3
Crystals of complexes 2 and 3 were kept in the mother liquor
until they were dipped into oil. The chosen crystals were mounted
on a Mitegen micromount and quickly cooled down to 100 K (2) or
140 K (3). Selected crystals of 2 (blue, 0.06 Â 0.10 Â 0.25 mm3) and
3 (dark green, 0.20 Â 0.20 Â 0.20 mm3) were mounted on an
Oxford Diffraction Gemini (2) or a Bruker Kappa APEX II (3) using
molybdenum (k = 0.71073 Å) radiation and equipped with an
Oxford Cryosystems cooler device (2) or an Oxford Cryosystems
Cryostream Cooler Device (3). The unit cell determination and data
integration were carried out using CrysAlis RED package (2) or SAINT
2.3. Complexes
[CuL1ÁH2O] (1). A mixture of phenyl salicylate (2.14 g, 1 Â 10À2
mol) and diethylenetriamine (1.03 g, 1 Â 10À2 mol) was refluxed
for 30 min and then cooled to room temperature with stirring.
The resulting pasty product was dissolved in acetone (50 mL). Cop-
per acetate (2.0 g, 1 Â 10À2 mol) and piperidine (2 mL, 2 Â 10À2
mol) were added and the solution was refluxed and stirred for
1 h. The resulting violet precipitate was filtered off from the cooled
solution and dried. Yield: 0.9 g (31%). Anal. Calc. for C11H15CuN3O2
(284.80): C, 46.39; H, 5.31; N, 14.75. Found: C, 46.03; H, 5.18; N,
14.48. IR (ATR): 3248s, 3103m, 2930m, 2876m, 1592m, 1558s,
1520s, 1461m, 1440m, 1385s, 1324m, 1316m, 1258m, 1237w,
1155m, 1145w, 1099m, 1091m, 1038m, 961w, 890w, 842w,
760m, 704w, 651w.
APEX II (3) [4–6]. The structures have been solved using SIR92 [7],
SUPERFLIP [8] or SHELXS-97 [9] and refined by least-squares procedures
using the software packages CRYSTALS [10] or WinGX version 1.63
[11]. Atomic Scattering Factors were taken from the International
tables for X-ray Crystallography [12]. All hydrogen atoms were
refined by using a riding model. All non-hydrogen atoms were
anisotropically refined. Drawings of molecules have been per-
formed with the program Mercury [13]. For 3, it was not possible
to resolve accurately residuals (enclosed solvent molecules). Treat-
ment with the SQUEEZE facility from PLATON [14] resulted in a smooth
refinement. Cif data for 2 and 3 have been deposited at CCDC with
references CCDC 1842689–1842690.
[CuL2ÁH2O] (2). A mixture of 3-methoxysalicylic acid (1.68 g,
1 Â 10À2 mol), phenol (2.82 g, 3 Â 10À2 mol) and 1,3-dicyclohexyl-
carbodiimide (2.06 g, 1 Â 10À2 mol) in THF (100 mL) was stirred
for 24 h at room temperature. The solution was filtered off and
THF eliminated with use of a rotavapor. The resulting oil was
poured into 2-propanol (40 mL) and diethylenetriamine (1.03 g,
1 Â 10À2 mol) in 2-propanol (10 mL) was added dropwise, refluxed
for thirty minutes and then cooled down to room temperature
under stirring. Addition of diethyl oxide (60 mL) induced formation
of a white precipitate which was filtered off, and washed with
Crystal data for 2. C12H23CuN3O6, M = 368.88, monoclinic, C2/c,
Z = 8, a = 20.9842(6), b = 7.36425(18), c = 20.1435(5) Å,
a = c = 90°,
b = 108.237(3)°, V = 2956.47(14) Å3, 39819 collected reflections,
4633 unique reflections (Rint = 0.023), R-factor = 0.022, weighted
R-factor = 0.024 for 4208 contributing reflections [I > 3
199 parameters. CCDC 1842690.
r (I)] and
diethyl oxide.
A mixture of this crude precipitate (0.25 g,
1 Â 10À3 mol) with copper acetate (0.20 g, 1 Â 10À3 mol) and
piperidine (0.2 mL, 2 Â 10À3 mol) in acetone (30 mL) was refluxed
and stirred for 30 min. The resulting violet precipitate was filtered
off from the cooled solution. Crystals suitable for X-ray diffraction
were obtained by slow diffusion of acetone to a methanol/water
solution of the isolated complex. Note that the colour change from
violet (CuL2) to blue (CuL2ÁH2O) observed during the crystallization
process is due to water coordination. Yield: 0.10 g (30%). Anal. Calc.
for C12H23CuN3O6 (368.88): C, 39.07; H, 6.28; N, 11.39. Found: C,
38.91; H, 6.18; N, 11.28. IR (ATR): 3221m, 3119m, 2911m,
2872m, 1591w, 1566s, 1532s, 1448m, 1433s, 1391s, 1336m,
1259w, 1225s, 1202s, 1149w, 1106w, 1080m, 1064m, 1001w,
964w, 853w, 804w, 739m, 614w.
Crystal data for 3.
monoclinic, P21/n, Z = 4,
c = 21.8194(4) Å, a = c
= 90°, b = 94.1770(10)°, V = 4220.13(15) Å3,
C38H42ClCu2N6NaO12
,
M = 960.32,
a = 13.7780(3),
b = 14.0751(3),
61973 collected reflections, 16540 unique reflections
(Rint = 0.0497), R-factor = 0.047, weighted R-factor = 0.051 for
11401 contributing reflections [I > 3r (I)] and 541 parameters.
CCDC 1842689.
3. Results
The ligands prepared in the present work are reported on the
following Scheme 1. The L1H2 and L2H2 ligands result from reaction
of diethylenetriamine (dien) with the phenyl ester of salicylic acid
or 3-methoxy-salicylic acid. Only L1H2 has been isolated as a
picrate salt and characterized by 1H and 13C NMR while L2H2 has
been directly reacted with copper ions. A structural determination
confirms monocondensation of diethylenetriamine and presence of
a primary amine function coordinated to the copper ion that
should be able to react with an aldehyde function to give original
non symmetric ligands. This is exemplified by the reaction of
CuL2ÁH2O with ortho-vanillin (Hovan) that yields the [(CuL3H)2Na]
ClO4 complex. Its structural determination demonstrates the non
symmetry of the ligand coordinated to the copper ion along with
the role of the kinetic template effect in the original coordination
of such a ligand.
[(CuL3H)2NaClO4] (3).
A
methanol solution (10 mL) of
[CuL2ÁH2O] (0.28 g, 1 Â 10À3 mol), ortho-vanillin (0.15 g, 1 Â 10À3
mol), sodium perchlorate (0.12 g, 1 Â 10À3 mol) and piperidine
(0.30 mL, 3 Â 10À3 mol) was stirred and refluxed for 20 min. The
resulting green solution was cooled down, filtered and left aside.
Crystals suitable for X-ray appeared three days later. They were
isolated by filtration and dried. Yield: 0.30 g, 62.5%. Calc. for
C38H42ClCu2N6NaO12 (960.32): C, 47.53; H, 4.41; N, 8.75. Found:
C, 47.23; H, 4.32; N, 8.52. IR (ATR): 3262w, 3183w, 1628s,
1606m, 1593w, 1551w, 1537w, 1463m, 1449s, 1439s, 1399w,
1313m, 1289w, 1243m, 1219s, 1195w, 1154w, 1081s, 1066s,
1023m, 995w, 970m, 884w, 856w, 818w, 778w, 760m, 736m,
696m, 622m cmÀ1
.

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J.-P. Costes et al. / Polyhedron 153 (2018) 158–162
Scheme 1. Ligands used in this work.
Fig. 1. Molecular plot for complex 2 R along with selected bond lengths and angles.
Hydrogen atoms are omitted for clarity, except for the water molecule and the
secondary amine function. Cu1 N1 1.9317(6), Cu1 N2 2.0056(6), Cu1 N3 2.0515(6),
Cu1 O2 1.9254(5), Cu1 O4 2.3734(6), C8 N1 1.3124(9), C8 O3 1.2880(9) Å; N1 Cu1
N2 83.76(3), N2 Cu1 N3 84.12(3), N1 Cu1 O2 95.24(3), N3 Cu1 O2 96.18(3)°.
3.1. Structural characterizations
The molecular plot of the neutral CuL2ÁH2O complex is shown in
Fig. 1 with relevant bond lengths and angles collated in the Fig-
ure caption. It crystallizes in the monoclinic C2/c space group with
one molecule in the unit cell. Once coordinated, the nitrogen atom
of the secondary amine function is chiral. Crystallization in a cen-
trosymmetric space group confirms presence of the two chiralities
R and S. In its equatorial plane, the Cu ion is coordinated to three
nitrogen and one oxygen atoms of the main ligand, surrounded
by two five- membered and one six-membered cycles. An axial
water molecule completes the square pyramidal copper environ-
ment, with an axial CuAO4 bond length (2.3734(6) Å) larger than
the equatorial one (1.9254(5) Å). The CuAN bond lengths increase
on going from imine (1.9317(6) Å) to secondary amine (2.0056(6)
Å) and to primary amine (2.0515(6) Å) nitrogen atoms. The oxygen
atom of the amide function characterized by NAC and CAO bond
lengths respectively equal to 1.3124(9) and 1.2880(9) Å, is not
involved in coordination.
Fig. 2. Molecular plot of the cationic part of complex 3 along with selected bond
lengths and angles. Hydrogen atoms are omitted for clarity. Cu1 N1 2.8371(14), Cu1
N2 2.0083(14), Cu1 N3 1.9430(14), Cu1 O3 1.8996(12), Cu1 O5 1.9418(12), Cu2 N4
2.6861(15), Cu2 N5 2.0210(13), Cu2 N6 1.9364(14), Cu2 O1 1.9630(11), Cu2 O7
1.9037(11), Na1 O1 2.7596(15), Na1 O3 2.2221(14), Na1 O4 2.4134(16), Na1 O5
2.5840(15), Na1 O7 2.2371(14), Na1 O8 2.3447(15), C7 N1 1.353(2), C7 O2 1.2381
(18), C26 N4 1.357(2), C26 O6 1.239(2) Å; N2 Cu1 N3 82.42(6), N3 Cu1 O3 92.43(6),
N2 Cu1 O5 96.24(6), O3 Cu1 O5 91.11(5), N5 Cu2 N6 84.47(6), N5 Cu2 O1 92.43(5),
N6 Cu2 O7 91.99(6), O1 Cu2 O7 92.37(5), O3 Na1 O5 69.12(5), O1 Na1 O7 66.95(4),
Na1 O3 Cu1 105.62(6), Na1 O5 Cu1 92.12(5), Cu2 O1 Na1 89.46(5), Na1 O7 Cu2
108.76(5)°.
cules are assembled by a sodium ion bridged to the two deproto-
nated phenoxo oxygen atoms, thus giving a central CuA(O2)A
NaA(O2)ACu core. The two CuA(O2)ANa bridging networks are
not planar, with hinge angles between the (OACuAO) and
(OANaAO) planes equal to 14.2(7) and 15.5(6)°. Furthermore the
two O2ANa planes (O3ANaAO5 and O1ANaAO7) make an angle
of 70.2(3)°. The Cu1. . .Na and Cu2. . .Na distances are respectively
equal to 3.298(7) and 3.372(7) Å while the Cu1. . .Cu2 distance is
5.472(7) Å, so that these three ions are at the edges of a nearly
The molecular plot of the cationic [(CuL3H)2Na](ClO4) complex
is shown in Fig. 2 with relevant bond lengths and angles collated
in the Figure caption. It crystallizes in the monoclinic P21/n space
group with one molecule in the unit cell. Two neutral CuL3H mole-

J.-P. Costes et al. / Polyhedron 153 (2018) 158–162
161
isosceles triangle. The Na coordination sphere is completed to six
by the methoxy oxygen atoms of each ligand. The two amide func-
tions are protonated. Each copper ion is linked to one L3H ligand by
the phenoxo oxygen and imine nitrogen atoms of the ovan part of
the ligand and to the secondary amine nitrogen atom, the fourth in
plane coordination coming from the phenoxo oxygen atom located
in the vicinity of the amide function and belonging to the second
L3H ligand. They can be considered in a square planar environment,
the Cu. . .NH(amide) nitrogen atom in axial position being located
at 2.683(3) (Cu2. . .N4) and 2.837(5) Å (Cu1. . .N1). These metal
coordinations lead to a surprising arrangement of the ligands,
where the two phenyl cycles of each L3H ligand are roughly in a
parallel position.
imine formation. In the present work, the starting copper complex
possessing a primary amine function coordinated to the copper ion
is a neutral complex. Nevertheless reaction occurs. The resulting
complex, which was expected to be an anionic entity in view of
previous results [2], is a neutral complex isolated as a cationic
[(CuL3H)2Na]+ species, with two neutral CuL3H complexes linked
by their methoxy and two phenoxo oxygen atoms to a six-coordi-
nate sodium ion. The N3O coordination site of the starting copper
complex becomes a N2O2 coordination site in the final complex,
by replacement of the amidato nitrogen atom by the nitrogen atom
of the primary amine function, which becomes an imine nitrogen
atom. Here the kinetic template effect induces replacement of
the axially coordinated water ligand present in the starting copper
complex by the deprotonated phenoxo oxygen atom in a first step.
In a following step, the phenoxo function that enters in the copper
coordination sphere in an axial position ends up in an equatorial
position. Simultaneously the basic amidato nitrogen atom is able
to pick the hydrogen proton coming from the deprotonation of
the entering phenol function. This protonation induces its rejection
out of the Cu coordination sphere, thus allowing isolation of an
original copper complex CuL3H that could not be prepared by reac-
tion of the isolated L3H3 ligand with a copper salt. This result con-
firms that the kinetic template effect, which works in the case of
cationic copper complexes [15] is also effective with neutral cop-
per complexes. In our example, the copper centre brings the three
reactive functions (first primary amine and aldehyde, then amide)
in close vicinity so that the formation of an imine function and pro-
tonation of the amide function can occur.
3.2. Magnetic study
The magnetic behavior for complex 3 in the form of the thermal
variation of the
bility corrected for the diamagnetism of the ligands) [3] is reported
as a Supplementary Information (Fig. S1). The MT product, which
is equal to 0.81 cm3 molÀ1 K at 300 K, decreases smoothly to 0.78
vMT product (vM is the molar magnetic suscepti-
v
cm3 molÀ1 K at 2 K.
vMT is in the range of the expected value for
two isolated Cu ions (0.75 cm3 molÀ1 K). These data confirm
absence of Cu–Cu interaction through the sodium ion.
4. Discussion
Reaction of diethylenetriamine (dien) with the phenyl ester of
salicylic acid or 3-methoxy salicylic acid is able to yield a neutral
complex involving a ligand resulting from a monocondensation
of dien with the phenyl ester. The L1H2 ligand, which is an oily pro-
duct, can also be isolated as a picrate salt precipitating in alcohol
solution. Its 1H and 13C NMR spectra allow a straightforward char-
acterization, easily evidenced by the non symmetry of the 13C sig-
nals coming from the dien part of the ligand. The resulting copper
complex is a neutral compound, the phenol and amide functions
being deprotonated while a water molecule is linked to copper in
axial position. Although coordinated to the copper ion, the primary
amine function can react with orthovanillin in presence of piperi-
dine in order to yield a new copper complex made of a ligand pos-
5. Conclusion
The present paper is devoted to the syntheses of neutral copper
complexes resulting from reaction of diethylenetriamine with phe-
nol derivatives possessing ester functions. The ligand formation
results from a pure organic reaction between the ester and one pri-
mary amine function, followed by complexation to the copper ion.
The primary amine function linked to the copper ion can, in a fol-
lowing step, react with a new aldehyde derivative to yield neutral
complexes involving amide-imine ligands, thanks to the kinetic
template effect of the copper ion. Such a reaction, that was previ-
ously observed in the case of cationic copper complexes, is possible
even in the case of neutral starting complexes. The three reactive
functions, that are initially coordinated to the copper centre, allow
formation of a coordinated imine function and protonation of the
amide function that becomes free, out of the copper coordination
sphere. This result clearly evidences the interest of the kinetic tem-
plate effect of metal ions in the synthesis of new complexes.
sessing two phenol and one amide functions. Such
a non
symmetric and trianionic ligand is original and belongs to a family
of rather uncommon ligands [1,2]. The structural determination of
the resulting complex demonstrates that it has been isolated under
a cationic form [(CuL3H)2Na]+, with a sodium ion linked to the phe-
noxo and methoxy oxygen atoms of two CuL3H entities. The two
phenol functions of each CuL3H entity are deprotonated in the final
complex while the amide function, that was deprotonated in the
starting complex, is now protonated.
Appendix A. Supplementary data
We have previously shown that cationic copper complexes pos-
sessing a primary amine function coordinated to the copper ion
can react with salicylaldehyde or pyrrole-carboxaldehyde for
example to yield non symmetric Schiff base complexes [15]. The
first reaction step corresponds to the deprotonation of the phenol
or pyrrole function that enters into the coordination sphere of
the cationic copper complex and facilitates the primary amine
nucleophilic attack of the aldehyde function brought by the phenol
or pyrrole derivative. Such a reaction occurs thanks to the kinetic
template effect of the copper ion [16,17] that positions the two
reacting functions in a close vicinity. Note that if the two reacting
functions (primary amine and aldehyde) are coordinated to the
metal ion, no reaction occurs [15]. If it is clear that one over the
two reacting functions must not be coordinated to the copper
ion, here the aldehyde function, we cannot specify that a coordina-
tion release of the primary amine function is necessary to induce
CCDC 1842689–1842690 contains the supplementary crystallo-
graphic data for 2 and 3. 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, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk. Supplementary data associated with this
article can be found, in the online version, at https://doi.org/10.
1016/j.poly.2018.06.056.
References
[1] (a) T. Ueno, T. Fujinami, N. Matsumoto, M. Furusawa, R. Irie, N. Re, T.
Kanetomo, T. Ishida, Y. Sunatsuki, Inorg. Chem. 56 (2017) 1679;
(b) Y. Shimogori, T. Hamamatsu, T. Fujinami, H. Hagiwara, N. Matsumoto, N.
Re, J. Mrozinski, Y. Ishikawa, A. Igashira-Kamiyama, T. Konno, Polyhedron 30
(2011) 1127;

162
J.-P. Costes et al. / Polyhedron 153 (2018) 158–162
c(c) S. Osa, T. Kido, N. Matsumoto, N. Re, A. Pochaba, J. Am. Chem. Soc. 126
(2004) 420;
[7] SIR92 – A program for crystal structure solution A. Altomare, G. Cascarano, C.
Giacovazzo, A. Guagliardi J. Appl. Crystallogr. 26 (1993) 343.
(d) T. Kido, Y. Ikuta, Y. Sunatsuki, Y. Ogawa, N. Matsumoto, Inorg. Chem. 42
[8] L. Superflip, G. Palatinus, J. Chapuis, Appl. Cryst. 40 (2007) 786.
(2003) 398;
[9] SHELX97 [Includes SHELXS97, SHELXL97, CIFTAB] – Programs for Crystal
(e) T. Kido, S. Nagasato, Y. Sunatsuki, N. Matsumoto, Chem. Commun. (2000)
2113.
[2] (a) J.P. Costes, C. Duhayon, S. Mallet-Ladeira, S. Shova, L. Vendier, Chem. Eur. J.
22 (2016) 2171;
Structure Analysis (Release 97-2). G. M. Sheldrick, Institüt für Anorganische
Chemie der Universität, Tammanstrasse 4, D-3400 Göttingen, Germany, 1998.
[10] CRYSTALS P.W. Betteridge, J.R. Carruthers, R.I. Cooper, C.K. Prout, D.J. Watkin :
J. Appl. Cryst. 36 (2003) 1487.
(b) V. Gomez, L. Vendier, M. Corbella, J.P. Costes, Inorg. Chem. 51 (2012) 6396;
(c) V. Gomez, L. Vendier, M. Corbella, J.P. Costes, Eur. J. Inorg. Chem. (2011)
2653;
[11] WINGX – 1.63 Integrated System of Windows Programs for the Solution,
Refinement and Analysis of Single Crystal X-ray Diffraction Data. L. Farrugia J.
Appl. Crystallogr. 32 (1999) 837.
(d) J.P. Costes, S. Shova, W. Wernsdorfer, Dalton Trans. (2008) 1843;
(e) J.P. Costes, M. Auchel, F. Dahan, V. Peyrou, S. Shova, W. Wernsdorfer, Inorg.
Chem. 45 (2006) 1924;
[12] International tables for X-ray crystallography, Vol IV, Kynoch press,
Birmingham, England, 1974.
[13] C.F. Macrae, P.R. Edgington, P. McCabe, E. Pidcock, G.P. Shields, R. Taylor, M.
Towler, J. van de Streek, J. Appl. Cryst. 39 (2006) 453–457.
[14] A. Spek, Acta Crystallogr., Sect. C 71 (2015) 9.
[15] J.P. Costes, F.Z. Chiboub Fellah, F. Dahan, C. Duhayon, Polyhedron 52 (2013)
1065.
[16] (a) M.C. Thompson, D.H. Busch, J. Am. Chem. Soc. 86 (1964) 213;
(b) M.C. Thompson, D.H. Busch, J. Am. Chem. Soc. 86 (1964) 3651;
(c) E.L. Blinn, D.H. Busch, Inorg. Chem. 7 (1968) 820.
(f) J.P. Costes, S. Shova, J.M. Clemente, N. Suet, Dalton Trans. (2005) 2830;
(g) J.P. Costes, F. Dahan, B. Donnadieu, M.J. Rodriguez Douton, M.I. Fernandez
Garcia, A. Bousseksou, J.P. Tuchagues, Inorg. Chem. 43 (2004) 2736;
(h) J.P. Costes, F. Dahan, C.R. Acad. Sci., Ser. IIc 4 (2001) 97.
[3] G.A. Bain, J.F. Berry, J. Chem. Educ. 85 (2008) 532.
[4] Agilent Technologies, Xcalibur CCD System, CrysAlisPro Software system,
Version 1.171.35.19, Agilent Technologies UK Ltd., Oxford, UK, 2011.
[5] CrysAlis CCD, CrysAlis RED and associated programs: Oxford Diffraction.
Program name(s). Oxford Diffraction Ltd, Abingdon, England, 2006.
[6] SAINT Bruker. Bruker AXS Inc., Madison, Wisconsin, USA, 2007.
[17] J.E. Beves, B.A. Blight, C.J. Campbell, D.A. Leigh, R.T. McBurney, Angew. Chem.,
Int. Ed. 50 (2011) 9260.