Polyhedron 26 (2007) 4470–4478

www.elsevier.com/locate/poly

Synthesis, structure and spectroscopic characterization of Ni(II), Co(II),

Cu(II) and Zn(II) complexes with saccharinate and pyrazole
a,*
Grettel Valle-Bourrouet , Leslie W. Pineda a, Larry R. Falvello b, Rosa Lusar c,
Thomas Weyhermueller d
a
Escuela de Quı́mica Universidad de Costa Rica, Ciudad Universitaria ‘‘Rodrigo Facio’’, 2060 San José, Costa Rica
b
Department of Inorganic Chemistry and ICMA, University of Zaragoza-CSIC, Plaza San Francisco s/n, E-50009 Zaragoza, Spain
c
Departament de Ciencies Experimentals, Campus Riu Sec, Universitat Jaume I, POB 224, E-12071 Castelló, Spain
d
Max Planck Institut for Bioinorganic Chemistry, 45470 Muelheim, Stiftstr. 34-36, Germany

Received 1 February 2007; accepted 1 June 2007

Available online 10 June 2007

Abstract

Four mononuclear mixed-ligand complexes of Co(II), Ni(II), Cu(II) and Zn(II), with saccharin (sac) and pyrazole (Hpz) were syn-
thesized and characterized on the basis of elemental analysis, FT-IR spectroscopy, magnetic susceptibility, thermal analysis data and
X-ray diffraction. The [Co(sac)2(Hpz)2(H2O)2] (1) and [Ni(sac)2(Hpz)2(H2O)2] (2) had similar molecular structures but distinct mono-
clinic crystal structure types (space group P21/n for 1 and P21/c for 2); the members of each pair of ligands were mutually trans. The
saccharinate ligands were N-coordinated. The copper complex showed the same coordination environment as the Co and Ni complexes
but crystallizes in the triclinic space group P 1 and presented pseudo-Jahn–Teller distortion along the O(w)–Cu–O(w) bonds. The
[Zn(sac)2(pz)2] complex was tetrahedrally coordinated and crystallized in the monoclinic space group C2/c. Thermal decomposition
of the complexes in a nitrogen atmosphere resulted in removal of the water molecules and pyrazole ligands at relatively low temperature
and formation of stable metal saccharinates as intermediates, which also decomposed at higher temperatures, about 300 C.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Saccharinate complexes; Hydrogen bonds; Pyrazole metal complexes; Cooper; Cobalt; Nickel

1. Introduction considerable changes in the atomic positions around the

metal ions without collapsing. The overall structure is rela-
The hydrogen bond is the most important of all tively open and hence flexible in its response to the electron-
directional intermolecular interactions. It is operative in ically induced stereochemical demands of the metal ions,
determining molecular conformation and molecular aggre- such as Jahn–Teller distortions in chromium and copper
gation, and it is the fundamental feature of a vast number compounds, without inducing changes in the general com-
of chemical systems, ranging from inorganic to biological plex geometry.
[1]. The saccharinate, (sac), complexes [M(C7H4NO3S)2- Substitution of two or more coordinated water mole-
(H2O)4] Æ 2H2O, with M = first row transition metal ions, cules by non-hydrogen bonding ligands disrupts this net-
have an extensive hydrogen bonding network, as shown in work. The resulting molecular geometry is due primarily
Scheme 1, and form an isostructural series [2–4]. Due to to intrinsic metal ion stereochemistry and electronic
the structural importance of this non-covalent interaction, demands. As examples, the reaction of vanadium(II) [3]
the structure is relatively flexible in the sense of tolerating and (II) [5] saccharinates with pyridine, yields the com-
plexes [M(sac)(py)4] Æ 2py, in which the saccharinate ion
*
Corresponding author. Tel.: +506 2074232; fax: +506 2535020. is O-bonded to the metal center, and the reaction with
E-mail address: gvalle@equi.ucr.ac.cr (G. Valle-Bourrouet). chromium(II) saccharinate [6] produces [Cr(sac)2(py)3],

0277-5387/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2007.06.001
 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478 4471

O acceptor and/or hydrogen donor sites [13,14]. We were suc-

O N cessful in preparing and characterizing complexes with the
SO formula [M(sac)2(Hpz)2(H2O)2], M = Co(II), Ni(II) and
SO
N O Cu (II); with zinc(II) the product was [Zn(sac)2(Hpz)2].
O H We describe here the crystal structures, spectroscopic and
O thermogravimetric properties of the products obtained.
H O
H H
O S 2. Experimental
NO
O H H
H O O
2.1. Methods and materials
M H
H H
O O
O N
Solvents, methanol, ethanol, pyrazole (Hpz), nickel(II)
S H nitrate, cobalt(II) nitrate, copper(II) nitrate, zinc(II) nitrate
O
O H
and sodium saccharinate were used as purchased. The tran-
sition metal saccharinates, [M(sac)2(H2O)4] Æ 2H2O, where
Scheme 1. Hydrogen bond network for [M(sac)2(H2O)4] Æ 2H2O M = Ni(II), Co(II), Cu(II) and Zn(II), were prepared as
complexes.
described in the literature [15] and isolated as crystalline
materials.
which is in chemical equilibrium with the dimeric com-
pound [Cr2(sac)4(py)2]. 2.2. Synthesis of the complexes
Another relevant feature is that the saccharinate ion is a
multifunctional ligand. This molecule has three coordina- 2.2.1. [Co(sac)2(Hpz)2(H2O)2]
tion centers: the carbonyl and the sulphonyl oxygen atoms A sample of pyrazole, 0.27 g, (4.0 mmol) was added to a
and the nitrogen atom, see Scheme 2. It can bind to a metal solution of 0.53 g (1.0 mmol) of cobalt(II) saccharinate in
ion as a monodentate ligand, as is observed in the isostruc- 25.0 mL of water. The reaction mixture was refluxed for
tural set of compounds of general formula [M(C7H4NO3S)2- 40 min. The solution was cooled to room temperature
(H2O)4] Æ 2H2O, or as a bidentate ligand as in [Cr2(sac)4], and after two days red crystals were obtained. They were
[Cu2(sac)4(Himid)4], (Himid = imidazole) and [Cd2(sac)4- filtered off and washed with cold water. Yield: 0.48 g
(Himid)4] [7–9]. (81%). Crystals suitable for X-ray measurements were
This feature has attracted interest on the use of saccha- obtained by slow evaporation of the mother liquid over a
rinate compounds as starting materials to prepare mixed- few days. Anal. Calc. for C20H20N6O8S2Co: C, 40.3; H,
ligand complexes, using monodentate or bidentate ligands 3.4; N, 14.1; Co, 9.9. Found: C, 40.9; H, 3.4; N, 13.8;
such as pyridine [3,5,6], imidazole [10] phosphine [11], or Co, 9.9%. IR (KBr pellet, cm1): 3513(s), 3310 (s),
2,2-bipyridine [12]. 1635(vs), 1586(m), 1344(m), 1264(m), 1150(m), 1054(m),
The aim of this work was to study the effect of the pyr- 953(m), 895(m), 754(m), 721(m), 681(m). leff (298 K):
azole, (Hpz), molecule as co-ligand in mixed-ligand saccha- 4.87 B.M. kmax (H2O) (e M1 cm1): 470sh, 490sh, 524(22).
rinate complexes. Pyrazole molecule has the dual capability
of to act as a monodentate or as a bridging ligand when 2.2.2. [Ni(sac)2(Hpz)2(H2O)2]
deprotonated or using the N–H group to participated in Pyrazole, 0.27 g (4.0 mmol) was added to a solution of
hydrogen bond formation with available hydrogen bond 0.53 g (1.0 mmol) of nickel saccharinate in 25.0 mL of

O O
O O
O O

S S
S
M
N- N-
N- M

III O M
I O II O

O O O M
O O O
M
S S S
-
-
N N NH

O O M O
IV V VI

Scheme 2. Coordination modes of saccharinate ion I.

4472 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478

water. The reaction mixture was refluxed for 1 h. The hot 3089(m), 3068(m), 1611(vs), 1579(vs), 1347(m), 1298(vs),
solution was filtered, and the resulting solution was left 1263(s), 1171(s), 1158(m), 1070(m), 1059(m), 950(s),
standing overnight. A light blue microcrystalline solid was 859(m), 783(m), 754(s), 680(m), 594(m), 539(m). leff: 1.90
obtained. It was filtered and washed with cold water. Yield B.M. UV–Vis (k, nm (e, M1 cm1)): 670(81).
was 0.42 g (71%). Crystals suitable for X-ray measurements
were obtained by slow evaporation of a water solution of the 2.2.4. [Zn(sac)2(Hpz)2]
compound. Anal. Calc. for C20H20N6O8S2Ni: C, 40.3; H, Pyrazole, 0.27 g (4.0 mmol) was added to a solution of
3.3; N, 14.1; Ni, 9.8. Found: C, 40.6; H, 3.6; N, 13.7; Ni, 0.53 g (1.0 mmol) of zinc saccharinate in 50.0 mL of water.
9.6%. IR (KBr pellet, cm1): 3519(m), 3312 (s), 3005(s), The reaction mixture was refluxed for 45 min. The resulting
1636(vs), 1586(vs), 1344(m), 1266(vs), 1151(vs), 1055(m), solution was cooled and allowed to evaporate slowly over a
953(s), 859(m), 754(m), 682(m). leff (299 K): 3.2 B.M. kmax few days at room temperature and a crop of crystals was
(H2O) (e M1 cm1): 380(15), 630(7) 1031(5) nm. obtained. The colorless crystals were collected by suction
filtration and dried in air. The crystals obtained in this
2.2.3. [Cu(sac)2(Hpz)2(H2O)2] way were suitable for X-ray analysis. Yield was 0.35 g
A sample of pyrazole, 0.27 g (4.0 mmol) was added to a (62%). Anal. Calc. for C20H16N6O6S2Zn: C, 42.4; H, 4.7;
solution of 0.53 g (1.0 mmol) of copper saccharinate in N, 16.6; Zn, 11.6. Found: C, 42.6; H, 4.6; N, 16.9; Zn,
75 mL of water. The reaction mixture was refluxed for 11.6%. IR (KBr pellet, cm1): 3108(s), 1656(vs), 1591(vs),
20 min while stirring. The resulting solution was cooled 1528(m), 1456(m), 1359(m), 1308(s), 1256(s), 1171(s),
and allowed to evaporate slowly few days at room tempera- 1071(m), 947(s), 784(m), 751(s), 677(m), 594(m).
ture. The resulting deep blue crystals were collected by suc-
tion filtration and dried in air. The crystals obtained in this 2.3. Physical measurements
way were suitable for X-ray analysis. Yield was 0.31 g
(50%). Anal. Calc. for C20H20N6O8S2Cu: C, 39.9; H, 3.0; FT-IR spectra were recorded for KBr pellets with a
N, 14.0; Cu, 10.6. Found: C, 39.9; H, 2.9; N, 13.9; Cu, Perkin–Elmer Spectrum 1000. Thermal analyses were
10.6%. IR (KBr pellet, cm1): 3543(m), 3334 (m), 3141(s), performed on a Texas Instruments Thermal Advantage

Table 1
Summary of crystallographic data collection and structure refinements of 1–4
1 2 3 4
Empirical formula C20H20N6O8S2Co C20H20N6O8S2Ni C20H20N6O8S2Cu C20H16N6O6S2Zn
FW 595.47 545.25 600.08 565.88
Crystal system monoclinic monoclinic triclinic monoclinic
Space group P21/n P21/c P 1 C2/c
a (Å) 12.3254(18) 10.3299(15) 7.2946(4) 18.2138(12)
b (Å) 8.3149(12) 8.3317(12) 8.6074(8) 10.2481(8)
c (Å) 12.6947(18) 14.377(2) 10.5153(6) 13.0634(10)
a () 90 90 76.87 90
b () 109.231(3) 93.238(3) 69.91(1) 109.24(1)
c () 90 90 67.90 90
V (Å3) 1228.4(3) 1235.4(3) 570.85(6) 2302.2(3)
Z 2 2 1 4
Radiation used, k (Å) Mo Ka (0.71073) Mo Ka (0.71073) Mo Ka (0.71073) Mo Ka (0.71073)
T (K) 295(2) 298(2) 100(2) 100(2)
Dcalc (g cm3) 1.610 1.600 1.746 2.302
l(Mo Ka) (mm1) 0.927 1.012 1.202 1.299
F(0 0 0) 610 612 307 1152
Crystal color red light blue blue color less
Crystal shape block block block parallelepiped
Crystal size (mm) 0.36 · 0.26 · 0.23 0.48 · 0.45 · 0.20 0.4 · 0.32 · 0.23 0.46 · 0.34 · 0.20
Diffractometer type CCD CCD Siemens Smart CCD Novius Kappa CCD
Data collection method psi + omega-scan psi + omega-scan psi + omega-scan psi + omega-scan
Tmax/Tmin 0.963/0.674 rel. 1.96/rel. 1.29 0.7918/0.5981 0.7812/0.5864
Total reflections/hmax () 10054/30.52 9993/30.51 6186/33.22 15104/33.22
Unique (Rint) 3743 (0.0322) 3741 (0.0446) 3731 (0.0283) 4235 (0.0641)
Refinement data F2 F2 F2 F2
H-atom treatment mixed refined mixed calculated
Data/parameters 3743, 197 3741, 211 3730, 178 4235, 159
Data with [I > 2r(I)] 2882 2555 3372 4050
Goodness-of-fit 1.017 0.999 1.057 1.067
R1, wR2 [I > 2r(I)] 0.0533, 0.1362 0.0424, 0.1049 0.0294, 0.0773 0.0291, 0.0797
R1, wR2 (all data) 0.0694, 0.1490 0.0610, 0.1084 0.0336, 0.0802 0.0307, 0.0810
qmax/qmin (e Å3) 3.343/0.557 1.678/1.182 0.630/0.498 0.571/0.821
 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478 4473

Universal Analysis 2000, under a dynamic nitrogen atmo- a second ligand in the coordination sphere of saccharinate
sphere with the sample kept in aluminum crucibles (alumi- complexes could produce N- or O-coordination of the sac-
num oxide a standard; constant heating rate 10 K min1). charinate ion, as observed in [Cu2(sac)4(Himid)4], [V(sac)2-
Magnetic susceptibility was measured using a Johnson (py)4] and [Ni(sac)2(py)4] and recently in [Cu(sac)2(Hpz)4]
Matthey MSB-1 balance at 25 C. Electronic spectra of [19]. The reaction with pyrazole in water solution yields
freshly prepared DMF solutions of the complexes were compounds of the formula M(sac)2(Hpz)2(H2O)2 for M =
recorded on a Shimadzu spectrophotometer UV-1601 PC, Co(II), Ni(II), Cu(II), and Zn(sac)2(Hpz)2, all with saccha-
using 10 mm quartz cells. rinate ions N-coordinated. Their compositions were
checked by analysis of their C, H and N content. The values
2.4. X-ray crystallography are in good agreement with the above formulas.

Single-crystal X-ray diffraction data for compounds 1 3.2. Description of the crystal structures
and 2 were gathered at room temperature, while data for
compound 3 were collected at 100 K using a Siemens Figs. 1–4 give the thermal ellipsoid drawings of the
SMART CCD-based diffractometer. The reflections were structures of the Ni, Co, Cu and Zn compounds, indicating
integrated using the commercial program SAINT, and cor- the atom numbering schemes. Bond lengths and angles are
rected for systematic errors with the public-domain pro- given in Table 2. The complexes 1, 2 and 3 have the gen-
gram SADABS [16–18]. Compound 4 was measured on a eral molecular formula [M(sac)2(HPz)2(H2O)2] and 4 is
Nonius Kappa-CCD diffractometer equipped with a nitro- Zn(sac)2(Hpz)2. The metal atoms in 1, 2 and 3 are located
gen cold stream operating at 100 K and a Mo-target rotat- on crystallographic inversion centers and have distorted
ing-anode X-ray source. Final cell constants were obtained pseudo-octahedral geometry. The coordination environ-
from least squares fits of all integrated reflections. Struc- ment of each metal center is made up of two pyrazole mol-
tures were solved by direct methods [17] and refined to F2 ecules, two water molecules and two saccharinate ligands,
by full-matrix least-squares [18]. The refinements con- all in the trans configurations. It can be affirmed that the
verged with the residuals given in Table 1, which summa- saccharinate and the two non-substituted water molecules
rizes the most important crystal data and refinement of the original saccharinate complexes are retained. In
parameters. the original series of saccharinate complexes, two different
orientations were found for the coordinated water mole-
3. Results and discussion cules – the so called flat and pyramidal cases [2]. In the ide-
alized flat case, the M–O bond lies in the plane of the water
3.1. Synthesis molecule; all four atoms are coplanar. In the pyramidal
case the M–O and two H–O bonds point roughly at three
The aim of this work was to study the effects of a pyrazole of the four vertices of a tetrahedron. In the structures con-
co-ligand on the coordination mode of saccharinate in sidered in this work, only the pyramidal case is present; the
mixed-ligand complexes. Previous observations showed that other water molecules were substituted by a nitrogen atom

Fig. 1. Drawing of the compound 1 showing 50% probability displacement ellipsoids.

4474 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478

Fig. 2. Drawing of the compound 2 showing 50% probability displacement ellipsoids.

Fig. 3. Drawing of the compound 3 showing 50% probability displacement ellipsoids.

of the pyrazole ring. It is likely that the water molecules are comes close enough to the ideal case that the vibronic prob-
pyramidal here in conjunction with the formation of strong lem envisioned in the work by Jahn and Teller plays a role
intramolecular hydrogen bonds with the carbonyl oxygen in the structures of this work. The distortion causes the
of the saccharinate ligand. The N–H group forms hydrogen arrangement around the metal ion to change with respect
bonds with the saccharinate sulfonyl oxygen atoms in the to the cobalt(II) and nickel(II) complexes, as shown in
cobalt and nickel complexes. In the copper complex, the Fig. 5. In the Ni(II) and Co(II)-complexes, the saccharinate
hydrogen bonding is formed with the coordinate water and water molecules are on the same plane but, in the cop-
molecule oxygen atom, see Table 3. As expected for a metal per compound they are not. The bond distances M–Nsac
ion with a d9 electronic configuration, the copper complex and M–Ow are longer than in the former saccharinate com-
shows an elongated axis along the O–Cu–O bonds plexes [4], the M–NHpz distances are shorter than the M–
2.4266(11) Å. In spite of the mixed ligand set (4N and Nsac for the Co(II), Ni(II) and Cu(II)-complexes. The zinc
2O) there is not a rigorously, octahedral coordination complex shows a pseudo-tetrahedral coordination around
sphere, and hence, no rigorous electronic degeneracy is the metal ion. There is no difference between the Zn–N
possible. It would appear, however, that the structure bonds, and the N–Zn–N angles are around 112.
 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478 4475

Table 3
Hydrogen bonds distances for 1, 2 and 3
D–H  A D(D  A)
[Co(sac)2(Hpz)2(H2O)2]
N(2)  O(3)#1 2.987(3)
N(2)  O(2)#2 3.133(3)
O(4)  O(1)#1 2.626(3)
O(4)  O(3)#3 2.941(2)
O(4)  O(2) 3.008(3)
[Ni(sac)2(Hpz)2(H2O)2]
N(2)  O(3)#1 2.967(3)
O(4)  O(1)#1 2.610(3)
O(4)  O(3)#2 2.951(3)
[Cu(sac)2(Hpz)2(H2O)2]
N(22)  O(30) 2.652
O(10)  O(30) 2.799
O(10)  O(30A) 2.908

Fig. 4. Drawing of the compound 4 showing 50% probability displace-

ment ellipsoids.
ger than normal residual peaks in their final difference-
Fourier maps. An explanation for these peaks, in terms
The final difference-Fourier maps for 1 and 2 show, of polymorphic intergrowths, can be understood through
respectively, two peaks and one peak greater than 1.0 e/ an examination of the packing patterns of the two struc-
Å3. The peaks can be explained in both cases by the pres- tures. The two crystal structures, which are based on
ence of intergrowths, as detailed below. almost isostructural molecules, are nevertheless quite
Evidence for polymorphic intergrowths in the structures distinct, but related crystal structure types. Beginning
of compounds 1 and 2. Both structures, 1 and 2, have lar- with the unit cell of 2, the nickel complex, the following
Table 2
Selected bond distances (Å) and angles () for [Co(sac)2(Hpz)2(H2O)2] (1), [Ni(sac)2(Hpz)2(H2O)2] (2), [Cu(sac)2(Hpz)2(H2O)2] (3) and [Zn(sac)2(Hpz)2] (4)
Co(sac)2(Hpz)2(H2O)2 (1) Ni(sac)2(Hpz)2(H2O)2 (2) [Cu(sac)2(Hpz)2(H2O)2] (3) [Zn(sac)2(Hpz)2] (4)
Bond lengths
M–N(1) 2.1143(18) 2.0839(19)
M–N(3) 2.2154(18) 2.1874(18)
M–O(4) 2.1286(18) 2.0828(19)
Cu–N(21)#1 1.9805(11)
Cu–N(2)#1 2.0902(11)
Cu–O(30)#1 2.4266(11)
Zn–N(2) 1.9974(9)
Zn–N(21) 1.9991(10)
Bond angles
N(1)–M–O(4) 93.65(7) 93.58(8)
N(1)–M–O(4)#1 86.35(7) 86.42(8)
N(1)–M–N(3) 87.92(7) 88.40(7)
N(1)–M–N(3)#1 92.08(7) 91.60(7)
O(4)–M–N(3) 88.13(7) 87.72(7)
O(4)–M–N(3)#1 91.87(7) 92.28(7)
N(21)–Cu–N(21)#1 180.0
N(21)–Cu–N(2)j 92.50(5)
N(21)#–Cu–N(2) 87.50(5)
N(2)–Cu–N(2)#1 180.0
N(21)–Cu–O(30) 94.40(4)
N(21)#1–Cu–O(30) 85.60(4)
N(2)–Cu–O(30) 90.54(4)
N(2)#1–Cu–O(30) 89.46(4)
O(30)–Cu–O(30)#1 180.0
N(2)–Zn–N(2)#1 116.17(6)
N(2)–Zn–N(21)#1 111.16(4)
N(2)–Zn–N(21) 103.11(4)
N(21)#1–Zn–N(21) 112.45(5)
Symmetry transformations for 1, #1 (1  x, 1  y, z); for 2, #1 (x, y, z).
Symmetry transformations for 3: #1 (x, y, z).
Symmetry transformations for 4: #1 (1  x + 1, y + 1, z + 1) #2 (x, y + 1, z + 1).
4476 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478

b 0 = 110.36. These values can be compared to the cell

parameters of 1, (Table 1.) The transformation is not, in
fact, valid, as it involves non-integral lattice translations
that are not present in the structure of 2. Thus, while the
two cells have a geometrical relationship, the structures
are not the same; detailed examination of the packing pat-
terns indeed establishes that the structure types are differ-
ent, see Fig. 6.
In the final difference-Fourier map for the nickel com-
plex, 2, there is a peak of 1.68 e/Å3, located at (0, 0.5, 0).
Taking due account of symmetry and cell transformations,
these coordinates represent the difference between the prin-
cipal M–M Patterson vector in 1 and that in 2. (It is one of
several possibilities, all related by symmetry.) This differ-
ence peak could arise if a small component of a polymorph,
with the same structure type as 1 was present in the sample
of 2 from which the X-ray data were gathered. In a similar
fashion, the final difference map for the cobalt complex, 1,
shows two residual peaks with densities greater than 1.0 e/
Å3 – one of 3.34 e/Å3 at (0.5, 0, 0) and a second, 1.85 e/Å3
at (0.2164, 0.8707, 0.1139). Again, taking appropriate
account of cell transformations and symmetry, the rela-
tionship of the first peak to the cobalt atom, and of the sec-
ond peak to the sulfur atom, represent the differences
between the relative locations of these atoms in the two
structures. Taken together with what is observed in the dif-
ference map for the nickel complex, this provides strong
Fig. 5. Ligand orientation around the metal ion and hydrogen bonds evidence that both of these structures are affected, albeit
interactions in compounds 2 and 3.
to different degrees, by minor intergrowths of a second
polymorph with the structure of the nickel complex repre-
senting the polymorphic type for the cobalt compound and
transformation, if valid, would give a unit cell almost iden- vice versa.
tical to that of the cobalt complex: a 0 = a + 0.5c; b 0 = b; A more detailed analysis of this structural feature will be
c 0 =  a + 0.5c. a 0 = 12.247, b 0 = 8.332, c 0 = 12.914 Å, published elsewhere.

Fig. 6. Packing diagram of the compounds 1, a and 2, b, shown as the a-b face.
 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478 4477

Table 4 Table 5
Assignment of the most characteristic IR bands of 1, 2, 3 and 4 Thermoanalytical data for the metal complexes 1, 2, 3 and 4
Modes 1 2 3 4 Compound/ Temperature DTGbmax, Removed Mass loss (%)
Stagea range, C C groupa
m(O–H) with intramolecular 3513/ 3519/ 3546/ Calculated Found
hydrogen bonds 3310 3312 f 3337 f
[Co(sac)2(pz)2(H2O)2]
m(N–H) 3066 3063 3141/3089/3068 3187/3108 1 40–148 129() H2O 3.53 3.02
m(C@O) 1635 1636 1611 1656
2 148–197 176() H2O 3.8 3.05
mas(SO2) 1264 1266 1285 1298
3 178–374 335(+) 2Hpz 25.3 22.8
ms(SO2) 1151 1151 1158 1171
4 375–512 408(+) Hsac 31.02 30.6
[Ni(sac)2(pz)2(H2O)2]
1 46–198 167() Hpz 10.95 11.42
3.3. Spectroscopic and magnetic properties
2 198–260 207() 2H2O 6.42 6.02
3 260–373 337() Hpz 14.37 11.42
The most significant frequencies in the IR spectra of the 4 374–512 425(+) Hsac 35.95 30.06
metal complexes are given in Table 4. The IR spectra of the
[Cu(sac)2(pz)2(H2O)2]
Ni(II), Co(II) and, Cu(II)-complexes resemble each other 1 79–145 110() 2H2O 6.48 6.00
indicating a similar structural pattern. The strong and 2 145–239 219() Hpz 11.46 11.33
sharp bands in the range 3546–3310 cm1 are attributed 3 239–304 281() Hpz 18.29 11.33
to the m(OH) vibrations of water molecules with intramo- 4 383–790 344() Hsac 23.88 30.34
5 404–512 468(+) 20.11
lecular hydrogen bond interactions [20]. As shown in Figs.
1 and 2, the water molecules form hydrogen bonds with the [Zn(sac)2(pz)2]
carbonyl oxygen atom and intermolecular interactions with 1 28–225 192() 2.1
2 225–375 355() 2Hpz 21.98 24.07
the sulfonyl groups for 1 and 2, and with the carbonyl 3 275–512 441 Hsac 33.51 32.2
group in 3, the O  O distance being ca. 2.9 Å. The Zn(II) a
pz: pyrazole, sac: saccharinate ion.
compound shows no O–H bands. The N–H stretching b
(+) and () donate endothermic and exothermic processes,
vibrations for the pyrazole moiety appear in the range respectively.
3066–3187 cm1 as sharp bands. The copper compound
displays three bands, with a splitting pattern that can be
attributed to the hydrogen bonding interactions. The lytical data (decomposition stages, temperature ranges,
m(CO) bands of the sac ligands appear at 1635 in 1 and 2, peak maxima and mass losses) for the metal complexes
1656 in 3 and 1611 cm1 in 4. The low frequency in the lat- are summarized in Table 5. The degradation of compounds
ter compound could be attributed to the intra- and inter- 1, 2 and 3 occurs in four or five successive TG steps. In the
molecular hydrogen bonds; this is in agreement with the first two steps the mass loss corresponds to the release of
higher frequency of the carbonyl stretching vibration in two water molecules for 1 and 3. For the case of compound
the zinc(II) complex where there are no hydrogen bonds. 2, two steps correspond to two water molecules and one
The masym(SO2) sac absorptions appear as strong bands pyrazole. It is accompanied by two endothermic DTA sig-
between 1264 and 1285 cm1, while msym(SO2) bands occur nals. The next step involves the loss of two pyrazole mole-
as strong bands at ca. 1150 cm1. The SO2 vibration fre- cules, with an endothermic DTA signal. In the last step,
quencies in these complexes are similar to those for the an exothermic process takes place, which corresponds to
sodium saccharinate monohydrate; the sulfonyl groups the elimination of a saccharinate molecule.
are less susceptible to changes in the vibration frequency The degradation of the zinc complex, 4 takes place with
as a result of hydrogen bonding interactions. a smoothly continuous loss of mass, with one medium
The spectroscopic data are consistent with octahedral endothermic DTA signal, and two small DTA signals –
coordination geometry and indicate that the structure one endothermic and one exothermic at 355 and 441 C,
showed in solid state is preserved in solution. The kmax val- respectively. This behavior is different from the other three
ues are blue-shifted, respect to tetra-hydrated sacharinate compounds that show clear and defined step wise degrada-
complexes, as expected for pyrazole as stronger ligand than tion. Probably, the absence of hydrogen bond in the zinc
water [21]. The effective magnetic moments at room tem- compound could be the determinant factor for the
perature are in the range for high-spin complexes with observed continuous degradation.
octahedral coordination geometry, as observed in the crys-
tal structures [22]. 4. Conclusion

3.4. Thermal analysis The results of this work show how hydrogen bonds
between the ligands in the complex favored the arrange-
The thermal behavior of the compounds was investigated ment around the central ion, for the Ni, Co and Cu com-
by means of thermogravimetric (TG) and differentia-ther- pounds. This can be better observed, if it is compared
mal analysis (DTA) measurements in a flowing nitrogen with reported saccharinate–imidazole complexes, which
atmosphere (temperature range 25–512 C). Thermo-ana- show the following formula: [M(Himid)4(H2O)2] Æ 2sac for
4478 G. Valle-Bourrouet et al. / Polyhedron 26 (2007) 4470–4478

M = Co, Ni, [23,24], [Cu2(sac)4(Himid)4], [8], Here, the [3] F.A. Cotton, L.R. Falvello, R. Llusar, E. Libby, C.A. Murillo, W.
position of the second nitrogen atom in the imidazole ring, Schwotzer, Inorg. Chem. (1986) 4967.
[4] S.Z. Haider, K.M. Malik, K.J. Ahmed, H. Hess, R. Riffel, M.B.
does not favor hydrogen bonding with the water molecules Hursthouse, Inorg. Chim. Acta 72 (1983) 21.
in the complex. The Zn compound in both cases, has the [5] O.V. Quinzani, S. Tarulli, C. Marcos, S. Garcı́a Granda, E.J. Baran,
formula [Zn (sac)2(am)2], am = Hpz or Himid, [25]. In this Z. Anorg. Allg. Chem. 625 (1999) 1948.
case, probably as a d10 complex, the tetrahedral compound [6] N.M. Alfaro, F.A. Cotton, L.M. Daniels, C.A. Murillo, Inorg. Chem.
is kinetically favored. (1992) 2718.
[7] F.A. Cotton, L.R. Falvello, C.A. Murillo, G. Valle-Bourrouet, Inorg.
Chim. Acta 190 (1991) 89.
Acknowledgements [8] S. Liu, J. Huang, J. Li, W. Li, Acta Crystallogr., Sect. C C47 (1991)
41.
This work was supported by Vice-Rectory for Research, [9] P. Naumov, G. Jovanovski, Acta Chim. Slov. 46 (1999) 389.
[10] P. Naumov, G. Jovanovski, A. Todorovka, J. Mol. Struct. 563–564
University of Costa Rica, grant 115-98-375. L.W. Pineda (2001) 341.
acknowledges a DAAD fellowship. We thank the Spanish [11] L. Falvello, J. Gómez, I. Pascual, M. Tomas, E. Urriolabeitia, A.J.
Ministery of Science and Technology for financial support Schultz, Inorg. Chem. 40 (2001) 4455.
under Grant BQU2002-00554. We are indebted to the ‘‘Ser- [12] C.A. Johns, G.M.G. Hossain, K.M.A. Malik, S.Z. Haider, U.K.R.
vei Central d’Instrumentació Cientı́fica (SCIC) of the Uni- Romman, Polyhedron 20 (2001) 721.
[13] M.F. Iskander, T.E. Khalil, W. Haase, R. Werner, I. Svoboda, H.
versity Jaume I for the use of the X-ray diffraction facilities. Fuess, Polyhedron 20 (2001) 2787.
[14] C.S. Hong, J.H. Yoon, Y.S. You, Inorg. Chim. Acta 358 (2005)
Appendix A. Supplementary material 3341.
[15] S.Z. Haider, K.M. Malik, K.J. Ahmed, Inorg. Synth. 23 (1985) 47.
[16] (a) Data collection: SMART, Siemens Analytical X-ray instruments,
CCDC 259785, 259786, 259787 and 259788 contain the Inc., Madison, WI, 1996;
supplementary crystallographic data for this paper. These (b) Integration: SAINT, Siemens Analytical X-ray Instruments, Inc.,
data can be obtained free of charge via http://www.ccdc. Madison, WI, 1996;
cam.ac.uk/conts/retrieving.html, or from the Cambridge (c) Corrections G.M. Sheldrick, SADABS, Göttingen University, 1996.
Crystallographic Data Centre, 12 Union Road, Cambridge [17] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
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CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@ [19] P. Naumov, G. Jovanosvski, M.G.B. Drew, S.W. Ng, Inorg. Chim.
ccdc.cam.ac.uk. Supplementary data associated with this Acta 314 (2001) 154.
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[21] A.B.P. Lever, Inorganic Electronic Spectroscopy, second ed., Else-
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