Journal of Molecular Structure 734 (2005) 8388

www.elsevier.com/locate/molstruc

Synthesis, structural characterisation and solvatochromism of a Ni(II)

and a Co(II) compound with 2-aminopyrimidine as a ligand
Yufei Songa, Chiara Masserab, Gerard A. van Albadaa,
Anna Maria Manotti Lanfredib, Jan Reedijka,*
a

Gorlaeus Laboratories, Leiden Institute of Chemistry, Leiden University, P.O. Box 9502, 2300 RA Leiden, The Netherlands.
b
Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universitadegli Studi di Parma,
Parco Area delle Scienze 17/A, 43100 Parma, Italy
Received 7 July 2004; accepted 20 September 2004
Available online 28 October 2004

Abstract
Two mononuclear complexes of formula [M(ampym)2(SCN)2(H2O)2]$2H2O (MZNi(II), Co(II); ampymZ2-aminopyrimidine) have been
synthesized and characterized by X-ray diffraction methods, IR and ligand-field spectra. The Ni(II) and Co(II) compounds, which crystallize
in the triclinic space group PK1, are isostructural, and their solid structures are stabilized by hydrogen bonding and pp interactions
between aminopyrimidine rings. The compounds exhibit solvatochromism as evidenced by a UV/Vis study in different solvents.
q 2004 Elsevier B.V. All rights reserved.
Keywords: Copper; Solvatochromism; 2-Aminopyrimidine; Thiocyanate

1. Introduction
Structure and magnetic studies of metal complexes with
2-aminopyrimidine (abbreviated as ampym) are of considerable interest due to the coordination diversity exhibited
by the ligand and metal ions [1,2]. With Cu(II), quite a large
number of different compounds have been reported and the
structures often depend on the nature of the anion and the
synthetic method [2,3]. With Ni(II) and Co(II) and ampym
as a ligand only a few complexes have been determined by
X-ray diffraction methods [4,5].
The investigation of the solvatochromic behavior [6] of
mixed-ligand metal complexes has been of importance,
because it provides a quantitative approach to recognize the
solvent behavior and the role of the solvent in physicochemical studies [7]; moreover, it is very helpful for
developing environmental sensor materials, which are
chromotropic and exhibit color change when exposed to
solvent or pollutant molecules [8].
* Corresponding author. Tel.: C31 71 5274450; fax: C31 71 5274671.
E-mail address: reedijk@chem.leidenuniv.nl (J. Reedijk).
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2004.09.007

In the present paper, the synthesis and characterization of

two mononuclear isostructural thiocyanato compounds with
the general formula [M(ampym)2(SCN)2(H2O)2]$2H2O
(MZNi(II), Co(II)) will be reported. In addition, the
solvatochromism of both compounds has been investigated
by UV/vis in different solvents.

2. Experimental section
2.1. General remarks and physical measurements
All starting reagents and solvents were purchased from
commercial sources and used as received. C, H, N analyses
were performed on a PerkinElmer 2400 series II analyzer.
Infrared spectra were recorded on a PerkinElmer Paragon
1000 spectrophotometer equipped with a Golden Gate ATR
device, using the diffuse reflectance technique. The UV/vis
spectrum of the compound was recorded in the 250800 nm
range with a Cary 50 Varian UV/vis/NIR spectrometer.
Electrospray ionization mass spectra (ESI-MS, Positive ion)
in MeOH solutions were recorded on a Thermo Finnigan

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Y. Song et al. / Journal of Molecular Structure 734 (2005) 8388

AQA apparatus. The ligand-field spectra of the solid

samples were recorded in the 2002000 nm range on a
PerkinElmer Lambda 900 UV/Vis/NIR spectrometer in the
diffuse reflectance mode with MgO as a reference. The
conductivity measurement was performed with a Philips
PW 9526 digital conductivity meter and PW 9551/60
measuring cell with a 1 mM solution of the complexes in
MeOH, H2O and MeCN.

The Co(II) compound (2) was synthesized in the similar

way, and blue crystals were collected after about 1 week.
Yield 60%. ESI-MS: m/zZ438.4. Elemental analysis
[found(calc.)] for C10H18CoN8O4S2: C 27.5 (27.4); H 4.2
(4.1); N 25.7 (25.6); S 14.5 (14.6). IR (cmK1): 3462.0 (w),
3332.0 (m), 2075.7 (s), 1627.9 (s), 1569.9 (s), 1486.0 (s),
1358.8 (m), 787.4 (m), 659.7 (m), 522.0 (m).
2.3. X-ray crystallographic study

2.2. General synthesis of the complexes

Ni(NO3)2$6H2O (10 mmol, 2.9 g) dissolved in water
(10 mL) was added to a solution of NH4SCN (20 mmol,
1.5 g) in water (30 mL), and the 2-aminopyrimidine
(20 mmol, 1.9 g) in 20 mL of methanol was added to the
well stirred aqueous solution. The resulting solution was
filtered and left to evaporate at room temperature. Blue
crystals were collected after 1 week. Yield 62%. For the
Ni(II) Compound (1): ESI-MS: m/zZ438.2; Elemental
analysis [found(calc.)] for C10H18NiN8O4S2: C 27.5 (27.4);
H 4.3 (4.1); N 25.7 (25.6); S 14.5 (14.6). IR (cmK1):
3460.3 (w), 3330.4 (m), 2084.7 (s), 1629.0 (s), 1569.7 (s),
1489.4 (s), 1360.0 (s), 1195.8 (s), 787.0 (s), 660.2 (s),
523.7 (s). (w, m and s represent the intensity of the
absorption peaks as weak, medium and strong,
respectively).

The molecular structure of both [M(ampym)2(SCN)2

(H2O)2]$2H2O (MZNi(II) and Co(II)) was determined by
single-crystal X-ray diffraction methods. Crystallographic
and experimental details for the two structures are summarized in Table 1. Intensity data and cell parameters were
recorded at room temperature (25 8C) on a Bruker AXS
Smart 1000 single-crystal diffractometer (Mo Ka radiation)
equipped with a CCD area detector. The data reduction was
performed using the SAINT and SADABS programs [9].
The structure was solved by Direct Methods using the
SIR97 program [10] and refined on F20 by full-matrix leastsquares procedures, using the SHELXL-97 program [11].
All non-hydrogen atoms were refined with anisotropic
atomic displacements. The hydrogen atoms were located
in the difference Fourier map with the exception of
the hydrogen atoms of the water molecules of

Table 1
Crystallographic data for [M(ampym)2(SCN)2(H2O)2]$2H2O (MZNi(II) and Co(II))
Compound
Empirical formula
Formula weight
Crystal system
Space group
)
a (A
)
b (A
)
c (A
a (8)
b (8)
g (8)
3)
V (A
Z
Dcalcd (g/cm3)
m(mmK1)
Crystal size (mm)
F(000)
T (K)
)
Radiation (A
Reflections collected
Indipendent reflections
Observed reflections [IO2s(I)]
Data/restraints/parameters
q range for data collection (8)
Index ranges
Goodness-of-fit on F2 a
Final R indices (obs. data)b
R indices (all data)b
K3)
Largest diff. peak and hole (e/A
a
b

[Ni(ampym)2(SCN)2(H2O)2]$2H2O
C10H18N8NiO4S2
437.15
Triclinic
PK1 (no. 2)
7.259(5)
7.895(5)
9.065(5)
67.578(5)
72.511(5)
76.860(5)
454.3(5)
1
1.598
1.331
0.13!0.16!0.20
226
293(2)
0.71069
5109
2050 [R(int)Z0.0340]
1467
2050/7/143
2.528.0
K9%h%9; K9 %k%10;K11%l%11
0.921
R1Z0.0384, wR2Z0.0840
R1Z0.0613, wR2Z0.0890
0.422 and K0.423

[Co(ampym)2(SCN)2(H2O)2]$2H2O
C10H18CoN8O4S2
437.37
Triclinic
PK1 (no. 2)
9.145(3)
7.943(3)
7.328(3)
103.311(5)
107.381(5)
67.378(5)
464.9(3)
1
1.562
1.180
0.16!0.18!0.24
225
293(2)
0.71069
3884
1926 [R(int)Z0.0169]
1839
1926/0/143
2.527.6
K11%h%11; K9%k%10; K9%l%9
1.08
R1Z0.0288, wR2Z0.0864
R1Z0.0301, wR2Z0.0876
0.500 and K0.345

P


Goodness-of-fit SZ
WFo K Fc 2 nK p1=2 , where n is the number of reflections and p the number of parameters.
P
P
P
1=2
P
R1 Z sFo jK Fc s
jFo j; wR2 Z
WFo K Fc 2
WFo .

Y. Song et al. / Journal of Molecular Structure 734 (2005) 8388

85

Molecular geometry calculations were carried out using

the PARST97 program [12]. Drawings were obtained by
ORTEP3 in the WinGX suite [13]. All calculations were
carried out on a DIGITAL Alpha Station 255 computer.

3. Results and discussion

3.1. Description of the structure
[M(ampym)2(SCN)2(H2O)2]$2H20 (MZNi(II) and Co(II))

Fig. 1. An ortep view (20% probability) of [Ni(ampym)2(SCN)2(H2O)2]$

2H2O with the used atomic numbering scheme.

crystallizations. The weighting scheme used in the last

cycle of refinement was wZ1=
s2 F02 C0:0456P2  and wZ
2 2
2
1=s F0 C0:0582P C0:1432P (where PZF02 C2Fc2 =3)
for (1) and (2), respectively.

The Ni(II) and Co(II) compounds are isostructural with

the metal ion lying on an inversion center; an ORTEP view
of the Ni(II) compound is depicted in Fig. 1. Selected bond
distances and angles for both complexes are reported in
Table 2.
A slightly distorted octahedral coordination is observed
around both metal ions: four short in-plane bonds involve
two trans oxygens from the water molecules [NiO1Z
,CoO1Z2.093(2) A
] and two trans nitrogen
2.072(2) A
atoms from the thiocyanate groups [NiN4Z
,CoN4Z2.107(2) A
]. The axial positions are
2.058(3) A
occupied by the N1 endocyclic nitrogen from two trans ,CoN1Z
oriented ampym ligands [NiN1Z2.147(2) A

2.217(2) A]. The S1C5N4 thiocyanate groups are nearly

linear with angles of 178.0(3)8 and 177.9(2)8 for the Ni(II)
and Co(II) compounds, respectively. The thiocyanate groups
are not linear coordinated to the metal ions (angles MNC
are 153 and 1548 for MZCo, and Ni, respectively), and the
origin from the deviation of 1808 appears to be related to
the hydrogen bonding in the lattice. The dihedral angles that
the least-square plane through NIN2C1C2C3C4 forms

Table 2
), angles (8) and hydrogen bonding parameters for [M(ampym)2(SCN)2(H2O)2]$2H2O (MZNi(II) and Co(II))
Selected bond lengths (A
[Ni(ampym)2(SCN)2(H2O)2]$2H2O
Bond lengths: Ni1O1 2.072(2); Ni1 N4 2.058(3); Ni1N1 2.147(2)
Bond angles: O1Ni1N1 89.38(8); N4Ni1O1 91.71(10); N4Ni1N1 92.04(10); S1C5N4 178.0(3); Ni1-N4C5 153.7(2)
Hydrogen bonds
)
)
DH/A
H/A(A
D/A (A
N3H1N/O1
2.23(4)
2.934(2)
N3H1N/N4
2.48(3)
3.073(4)
N3H2N/S1 (1Kx, Ky, 2Kz)
2.62(2)
3.499(3)
O1H2S/O1S
1.88(3)
2.768(3)
O1H1S/O1S (Kx, 1Ky, 1Kz)
1.90(3)
2.771(4)
C4H4/N4 (1Kx, 1Ky, 1Kz)
2.69(4)
3.077(5)
C4H4/O1 (1Kx, 1Ky, 1Kz)
2.66(3)
3.130(4)
[Co(ampym)2(SCN)2(H2O)2]$2H2O
Bond lengths: Co1O1 2.093(2); Co1N4 2.107(2); Co1N1 2.217(2)
Bond angles: O1Co1N4 88.71(7); O1Co1N1 91.06(6); N4Co1N1 92.29(6); N4C5S1 177.9(2); Co1N4C5 151.0(2)
Hydrogen bonds
)
)
DH/A
H/A(A
D/A (A
N3H2N/O1 (2Kx, 1Ky, Kz)
2.29(4)
2.983(3)
N3H2N/N4
2.49(3)
3.123(3)
N3H1N/S1 (1Kx, 2Ky, Kz)
2.67(3)
3.522(3)
O1H2S/O1S (2Kx, 1Ky, 1Kz)
1.97(3)
2.768(2)
O1H1S/O1S
2.06(4)
2.773(3)
C4H4/N4 (2Kx, 1Ky, Kz)
2.78(4)
3.135(3)
C4H4/O1
2.78(3)
3.220(3)

DH/A(8)
134(2)
124(2)
164(1)
169(3)
164(2)
105(2)
111(2)

DH/A(8)
134(4)
128(3)
170(3)
170(4)
167(3)
107(2)
107(2)

86

Y. Song et al. / Journal of Molecular Structure 734 (2005) 8388

with the equatorial plane, with the N1MO1 and with

N1MN4 moieties are 87.4(1), 43.8(1) and 47.9(1)8 in the
Ni(II) compound and 87.0(1), 44.4(1) and 46.9(1)8 in the
Co(II) complex.
To the best of our knowledge, the only related Ni(II) or
Co(II) complexes containing two ampym and two water
molecules in an octahedral arrangement around the metal
ion is the polymeric compound [Ni(SO 4)(C4 H5 N 3) 2
(H2O)2]$C6H5N3 [5]. In this complex, the sulfate ion acts
as a bridging moiety between the metal atoms which
present, in the equatorial plane, two mutually cis nitrogen
atoms from ampym and two mutually cis oxygen atoms
from the water molecules.
The configuration of the present complexes, with the
ampym ligands almost orthogonal to the equatorial plane
and nearly bisecting the O1MN4 bond angles, is
correlated to the bifurcated intramolecular hydrogen bonds
that a NH group from the ampym NH2 moieties forms with
the oxygen and nitrogen atoms of the adjacent water and
,N3/N4Z
thiocyanate ligands [N3/O1Z2.934(4) A
for the Ni(II) complex; N3/O1Z2.983(3) A
,
3.073(4) A
for the Co(II) compound; see also
N3/N4Z3.123(2) A
Table 2].
The structure is further stabilized by intermolecular
interactions between the other hydrogen atom of the NH2
groups and sulfur atoms from neighboring complexes
in NiII compound and N3/S1Z
[N3/S1Z3.499(3) A
II

3.522(2) A in Co complex] and by intermolecular hydrogen bonds that the coordinated water molecules form, as
hydrogen donors, with the solvate ones [O1/O1SZ
for the Ni(II) complex; O1/O1S
2.768(3) and 2.771(4) A
for the Co(II) compound; see
and O1/O1SZ2.768(2) A
also Table 3].
The inversion-related aromatic rings show a slipped
stacking to form chains running along the [001] (Ni) and
[100] (Co) directions with the shortest ringring distance of
in the Ni(II) and Co(II)
3.324(4) and 3.342(4) A
Table 3
UV/vis absorption of the two complexes in different solvents
Complexes/
solvents/color
MeCN
EtOH

DMF
Ether
MeOH
Aceton

l (nm) and 3 (l molK1 cmK1)

[Ni(ampym)2(SCN)2
(H2O)2]$2H2O

[Co(ampym)2(SCN)2
(H2O)2]$2H2O

383 (72.6); 625 (23.1);

light blue
400 (272); 664 (35);
737 (26); light green

563 (200.4); 630 (562);

blue
480 (33.2); 524 (46.8);
556 (44.2); 620 (57.1);
blue purple
485 (45.6); 587 (202);
625 (346); blue
563 (104.6); 610 (214.6);
635 (240.6); skyblue
519 (42.4); 480 (30.2);
pink
537 (214.0); 632 (449.2);
774 (9.6); deep blue

L402 (182); 679 (42);

737 (26); light green
Green (weak solubility)
397 (25.2); 666 (11.0);
737 (10.0); light blue
Green (weak solubility)

Fig. 2. Crystal packing of the [M(ampym)2(SCN)2(H2O)2]$2H2O complex

(MZNi(II) and Co(II)) showing the pp interactions between the aromatic
rings of neighboring molecules.

compounds, respectively (see Fig. 2). Also these interactions contribute to the stability of the complexes.
Although the two structures are very similar, slight
differences are visible. In the Ni(II) complex, the nearest
atom to the metal center is the equatorial nitrogen N4, while
in the Co(II) compound, it is the equatorial oxygen O1 from
the coordinated water molecule. This slight distortion from
octahedral could be induced by the hydrogen bond network,
which involves, besides the above cited hydrogen
bonds, also the intramolecular bifurcated interactions
CH/N(NCS) and CH/O(coordinated H2O) involving
, C4
the ampym C4H4 group [C4/N4Z3.077(5) A
for the Ni(II) complex; C4/N4Z
/O1Z3.130(4) A
, C4 /O1Z3.220(3) A
for the Co(II)
3.135(3) A
compound].
3.2. Infrared spectroscopy
The position of the bands of the thiocyanate group related
to the stretching frequency of the CN moiety can be used to
characterize the coordination mode of this ligand to the
metal ions. The CN stretching of a bridging thiocyanate is
usually found to be above 2100 cmK1 [14]. In the case of the
nickel(II) complex, the stretching frequency of the thiocyanate occurs at 2084 cmK1, which indicates normal end-on
NCS coordination. The bands corresponding to the stretching frequency of CS and NCS appear at 787 and 463 cmK1,
which is in good agreement with an end-on NCS
coordination. For the Co(II) complex, the typical stretching
frequency for the thiocyanate group can be observed at
2075 cmK1, while the band belonging to CS and the
deformation frequency NCS occur at 787 and 459 cmK1,
respectively.

Y. Song et al. / Journal of Molecular Structure 734 (2005) 8388

3.3. Ligand-field spectroscopy

The diffuse reflectance spectra of the solid Ni(II)
compound shows three strong bands at 9.8!103 cmK1
(s1; 3A2g3T2g), 15.8! 103 cmK1 (s2; 3A2g3T1g(F)) and
25.7! 103 cmK1 (s3; 3A2g3T1g(P)), which are the typical
absorption bands for an octahedral Ni(II) complex[15]. Two
strong bands at 30.3! 103 and 33.3!103 cmK1 are also
visible, which are attributable to the LMCT from the ligands
to the Ni(II) atom. The value calculated by semi-empirical
equation[15] for the Dq (the crystal-field parameter), B
(Racah parameter) and Dq/B are 980, 806 and 1.21 cmK1,
respectively.
The ligand-field spectrum of the solid Co(II) compound
shows a strong band at 30.7!103 cmK1 corresponding to
the ligand to metal charge transfer (LMCT) band, while
the bands at 19.9!103 cmK1 (s3; 4T1g(P)4T1g(F)) and
8.9!103 cmK1 (s1; 4T2g4T1g) are typical for octahedrally
coordinated Co(II) with this chromophore[16]. However, the
band for the transition from 4A2g4A1g (s2) is not observed in
the spectrum. The value calculated for the Dq, B and Dq/B [16]
are 890, 811 and 1.10 cmK1, respectively.
3.4. UV/vis spectra in solution
The two compounds exhibit solvatochromism (Table 3
and Fig. 3), and in the case of the Co(II) complex, the color
changes from light pink (in H2O), to pink (in MeOH), blue
purple (in EtOH) and sky blue (in diethyl ether) to deep blue
(in DMF, Aceton, MeCN). The dd bands of the Co(II)
compound can be found around 456, 506 nm in water and
478, 510 nm in MeOH, respectively. In ethanol, 3 dd bands
can be seen clearly in the UV/vis spectrum at 470 nm,
520 m and 604 nm. When the solvent used is MeCN, the
dd bands shift significantly to around 561 and 627 nm,
which indicates the change of the coordination geometry
around Co(II). The charge transfer band which is a shoulder

87

peak at around 320340 nm is overlapped by a very strong

band around 290 nm in different solvents. So we believe that
tetrahedral Co(II) or 5-coordinate Co(II) is present in the
aprotic solvents.
For the Ni(II) complex, the color changes are not so
strong, from light blue (MeOH, H2O), to light green (EtOH)
and to green (Ether, Aceton). The UV absorption bands can
be found in the region of 388395 nm for the LMCT and
two dd bands (one is in the range of 645654 and another
one is in the range of 708720 nm, see Table 3) in water,
methanol, EtOH and DMF. In Ether and MeCN, the charge
transfer band shifts to 379 and 374 nm, and only one dd
band in the visible range can be observed at 623 and
619 nm, respectively.
The solvatochromism is caused by the different coordination of the solvents to the metal centers and the resulting
change of the coordination environment around the metal
ions. For the Co(II) complex, the blue color in several
different solvents indicates that the geometry around
the metal must be distorted to tetrahedral or square
pyramidal. When the coordinated water molecules in
[Co(II)(ampym)2(SCN)2(H2O)2]$2H2O are replaced by
other solvents like aceton or acetonitrile, the coordination
around Co(II) may change from octahedral to a tetra- or
penta- coordination. For the Ni(II) complex, the color
change is not so evident, which may indicate that the
octahedral geometry around Ni(II) is maintained by
replacing the water molecules with different solvents.
The conductivities of these two complexes have been
studied in MeOH, water and MeCN. The obtained values are
quite small in MeOH and H2O, which is logical because the
complexes are crystallized from the mixture of MeOH and
water, and no dissociation occurs. In MeCN, the conductivities of these two compounds are still below 40 cm2 UK1
molK1, confirming that the thiocyanate groups are not
dissociated from the metal ions too. Therefore, though the
geometry around the metal ions may change in different
solvents, the thiocyanate groups are still kept in the
coordination surrounding around the metal ions.

4. Conclusions

Fig. 3. UV/Vis spectra of [Co(ampym)2(SCN)2(H2O)2]$2H2O in MeCN

(8.1!10K4 m), Acetone (9.2!10K4 M), Diethyl Ether (3.1!10K3 M),
DMF (7.0!10K4 M), EtOH (3.1!10K3 M) and MeOH (3.3!10K3 M).

In the present paper, two mononuclear isostructural

Ni(II) and Co(II) complexes have been obtained, which
show an octahedral geometry around the metal ions. Their
crystal structures are stabilized by hydrogen bonding and
pp interactions between 2-aminopyrimidine rings from
different molecules. Both the compounds show solvatochroism which is due to the substitution of the water molecules
arranged in an octahedral geometry around Ni(II) and Co(II)
by other solvents. The change of the geometry and
coordination environment around the metal centers leads
to the color change and the shift of the charge transfer and
dd bands in different solvents.

88

Y. Song et al. / Journal of Molecular Structure 734 (2005) 8388

5. Supplementary material
Crystallographic data (excluding structure factors) for
the structures reported have been deposited with the
Cambridge Crystallographic Data Center as supplementary
publication no. CCDC-242651 and 242652 for compounds
(1) and (2), respectively, and can be obtained free of charge
on application to the CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK. [Fax: (Internet.)C44-1223/336-033;
e-mail: deposit@ccdc.cam.ac.uk]

Acknowledgements
The work described here has been supported by the
Leiden University Study group WFMO (Werkgroep Fundamenteel Materialen-Onderzoek). Support from the NRSC
Catalysis (a Research School Combination of HRSMC and
NIOK) is kindly acknowledged.

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