Electrochemical synthesis and characterization of nickel(II) complexes with N-2-pyridyl-sulfonamide ligands

Article abstract of DOI:10.1002/zaac.200570024

Heteroleptic nickel(II) complexes [NiL₂L′] of a series of monoanionic and potentially bidentate N-2-pyridyl-sulfonamide ligands [HL] and 2,2′-bipyridine or 1,10-phenanthroline (L′) have been prepared by electrochemical oxidation of a nickel anode in an acetonitrile solution of the ligands. The complexes have been characterized by microanalysis, IR and electronic spectroscopy, magnetic measurements and LSI mass spectrometry. The crystal structure of [Ni(Ms6mepy)₂(bipy)] has been determined by x-ray diffraction and shows the metal in an octahedral NiN₆ environment. Octahedral structures are also proposed for the other complexes with the N-2-pyridyl-sulfonamide ligands acting as N,N′ or N,O bidentate systems, depending on the position of the methyl substituent on the pyridine ring.

Full text of DOI:10.1002/zaac.200570024

Electrochemical Synthesis and Characterization of Nickel(II) Complexes with
N-2-Pyridyl-sulfonamide Ligands
a
a
a,
b
b
´
´
´
´
´
Inmaculada Beloso , Paulo Perez-Lourido , Jesus Castro *, Jose A. Garcıa-Vazquez , and Jaime Romero
a
´
´
Vigo, Pontevedra/Spain, Departamento de Quımica Inorganica, Universidade de Vigo
b
´
´
Santiago de Compostela/Spain, Departamento de Quımica Inorganica, Universidad de Santiago de Compostela
Received November 30th, 2004; accepted March 10th, 2005.
Abstract. Heteroleptic nickel(II) complexes [NiL2LЈ] of a series of
monoanionic and potentially bidentate N-2-pyridyl-sulfonamide li-
gands [HL] and 2,2Ј-bipyridine or 1,10-phenanthroline (LЈ) have
been prepared by electrochemical oxidation of a nickel anode in
an acetonitrile solution of the ligands. The complexes have been
characterized by microanalysis, IR and electronic spectroscopy, ma-
gnetic measurements and LSI mass spectrometry. The crystal struc-
ture of [Ni(Ms6mepy)2(bipy)] has been determined by x-ray diffrac-
tion and shows the metal in an octahedral NiN6 environment. Oc-
tahedral structures are also proposed for the other complexes with
the N-2-pyridyl-sulfonamide ligands acting as N,NЈ or N,O biden-
tate systems, depending on the position of the methyl substituent
on the pyridine ring.
Keywords: Sulfonamide; Nickel; Electrochemical synthesis; Crystal
structures
1 Introduction
As a continuation of our work dealing with metal com-
plexes with different sulfonamide ligands, we report here
the synthesis of a series of heteroleptic neutral NiII com-
plexes with these ligands.
Amide ligands and their metal complexes have been widely
investigated due to their use as antibacterial drugs in the
field of medicine [1]. In particular, copper(II) [2] and zinc(II)
[3] complexes have been used in the treatment of numerous
diseases, AgI [4] complexes have been used for the treatment
of burns and the carbonic anhydrase inhibitory properties
were studied for NiII complexes [5].
On the other hand, the coordination chemistry of amides
suffers from an inherent drawback in that the replacement
of an amide proton by a metal ion is not easy [6]. However,
the electron-withdrawing effect of a sulfonyl group increases
the acidity of the NϪH group and metallic complexes are
easily obtained by deprotonation of the ligand [7].
In previous papers we described the synthesis and charac-
terization of copper(II) [8], zinc(II) [9] and cadmium(II) [10]
complexes with pyridine-functionalised ligands, which are
denoted as HTs3mepy, HMs3mepy, HTs6mepy and
HMs6mepy (see Scheme 1). These ligands are characterized
by the presence of an additional donor nitrogen atom be-
longing to a methyl-substituted pyridine ring (picoline
group) in the α-position with respect to the sufonamide ni-
trogen. Structural data for these complexes show that the
coordinative behaviour of the ligand (N,NЈ or N,O donor)
depends on the position of the methyl group on the pyridyl
ring. In addition to the picoline ring, the ligands contain a
p-toluene group or a mesitylene group bonded to the sul-
fonyl group and it is thought that this might introduce
steric hindrance.
2 Results and Discussion
Heteroleptic nickel complexes of a series of N-2-pyridyl-
sulfonamide ligands and 2,2Ј-bipyridine (bipy) or 1,10-
phenanthroline (phen) were easily prepared in good yield
by an electrochemical method similar to that described by
Tuck et al. [11]. In all cases, the product was isolated as a
crystalline species by concentration of the resulting solu-
tion. The analytical data are in good agreement with the
expected values. The complexes are stable at room tempera-
ture and soluble in common solvents.
The electrochemical efficiencies, defined as the amount of
metal dissolved per Faraday of charge, were close to
* Prof. Dr. J. Castro
Departam. de Quımica Inorganica
Universidade de Vigo
´
´
E-36200 Vigo, Galicia/Spain
E-mail: jesusc@uvigo.es
Scheme 1
Z. Anorg. Allg. Chem. 2005, 631, 2101Ϫ2106
DOI: 10.1002/zaac.200570024
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2101

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I. Beloso, P. Perez-Lourido, J. Castro, J. A. Garcıa-Vazquez, J. Romero
0.5 mol·FϪ1. This fact, along with the evolution of hydrogen
at the cathode, is compatible with the following mechanism:
Cathode: 2HL ϩ 2 eϪ Ǟ 2LϪ ϩ H2
Anode: Ni ϩ 2LϪ ϩ LЈ Ǟ [NiL2LЈ] ϩ 2 eϪ
The IR spectra of the complexes do not show the band
attributable to ν(NϪH), which in the free ligands appears at
3248Ϫ3222 cmϪ1, thus confirming that the hydrogen atom
of the amide group is lost during the electrolysis. A band
observed for the ligands in the range 1617Ϫ1593 cmϪ1
,
Scheme 2
which is attributed to ν(CϭN), appears in similar positions
for complexes containing Ts3mepyϪ and Ms3mepyϪ li-
gands, but in the complexes with Ts6mepyϪ and Ms6mepyϪ
ligands this band is shifted to lower frequencies as a result
of coordination through the sulfonamide nitrogen atom. A
different effect is experienced by the ligand band in the
range 1137Ϫ1125 cmϪ1, which is due to the νsym(SϭO).
This band appears in similar positions in the complexes de-
rived from Ts6mepyϪ and Ms6mepyϪ, but is shifted to
slightly lower frequencies in the spectra of complexes with
Ts3mepyϪ and Ms3mepyϪ ligands as a result of coordi-
nation through the sulfonyl group. The band attributed to
the νas(SO2) lies in the range of 1323-1332 cmϪ1 for the
Ts3mepyϪ and Ms3mepyϪ derivatives, close to the values
observed for the free ligand, and in the range of 1325-
1327 cmϪ1 for the Ts6mepyϪ and Ms6mepyϪ derivatives,
values which are quite different from those found for the
free ligand. (see experimental part). All these values are in
accordance with the observed in other complexes of these
ligands with cobalt(II) [12] copper(II) [8], zinc(II) [9] and
cadmium(II) [10] in which X-ray studies confirm that in the
3-Me derivatives the coordination take place, in all cases,
through nitrogen and oxygen atoms and in the 6-Me deriva-
tives this coordination is accomplished through both nitro-
gen atoms. The spectra also show bands in the aromatic re-
gion (1460Ϫ1415 cmϪ1), which are characteristic of the
In most cases, the LSI mass spectra show the molecular
ion with appropriate isotope distributions, as well as the
ions formed by the loss of one ligand from the initial com-
plex and a peak attributed to the free ligand.
These experimental data suggest that all complexes are
molecular with the metal in an octahedral environment co-
ordinated by two sulfonamide monoanionic ligands and a
bidentate neutral bipy or phen coligand (vide infra). The
IR data also suggest that the coordinative behaviour of the
sulfonamide ligands seems to depend on the location of the
methyl-substituent in the pyridine ring Ϫ a situation similar
to that found for the analogous CuII, ZnII and CdII com-
plexes mentioned before. Thus, if the substituent is located
in position 6, the sulfonamide ligands behave as (N,NЈ) bi-
dentate systems. However, when the substituent is in posi-
tion 3, the ligands behave as bidentate (N,O) donors. This
difference in behaviour can probably be attributed to a
steric effect. The substituent in position 3 pushes the sul-
fonyl group towards the metal and induces coordination
through the oxygen atom (see Scheme 2).
2.1 X-ray Structural Study
Molecular Structure of [Ni(Ms6mepy)2(bipy)]
ν(CϭC) vibrations, as well as a band at 2935Ϫ2915 cmϪ1
,
The molecular structure of the complex together with the
atomic numbering scheme adopted is shown in Figure 1. X-
which is attributable to ν(ϪCH3). In addition, typical ab-
sorption bands of coordinated 2,2Ј-bipyridine (765 and
735 cmϪ1
)
and 1,10-phenanthroline (1520, 850 and
720 cmϪ1) are also observed [8Ϫ10, 13].
The complexes were also studied by electronic spec-
troscopy in the solid state. All of the compounds show
bands at around 10400 and 17570 cmϪ1 with a shoulder at
12600 cmϪ1. These absorptions are within the accepted
range for hexacoordinated octahedral complexes of nickel(II)
and can be assigned to the transitions 3T2g ǟ 3A2g (ν1) and
3T1g
ǟ
3A2g (ν2), respectively [14]. The shoulder at
12600 cmϪ1 can be attributed to band splitting as a conse-
quence of the distortion of octahedral symmetry. The third
expected d-d transition is presumably hidden under the
strong
charge-transfer
band
observed
in
the
20000Ϫ30000 cmϪ1 region.
The magnetic susceptibility values at room temperature
are close to 2.9 BM in all cases, which is consistent with
octahedral d8 systems.
Figure 1 Molecular structure of [Ni(Ms6mepy)2bipy].
2102
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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Z. Anorg. Allg. Chem. 2005, 631, 2101Ϫ2106

Nickel(II) Complexes with N-2-Pyridyl-sulfonamide Ligands
˚
Table 1 Crystal data and structure refinement for
Table 3 Hydrogen bond parameters /A and ° for
[Ni(Ms6mepy)2bipy].
[Ni(Ms6mepy)2bipy].
Empirical formula
C40 H42 N6 O4 S2 Ni
DϪH...A
d(DϪH)
d(H...A)
d(D...A)
<(DHA)
Formula weight
Temperature
Wavelength
Crystal system
Space group
Unit cell dimensions
793.63
293(2) K
0.71073 A
monoclinic
C(113)ϪH(11A)...O(12)
C(113)ϪH(11C)...N(12)
C(14)ϪH(14)...O(12)
C(213)ϪH(21B)...N(22)
C(26)ϪH(26C)...O(11)
C(34)ϪH(34)...O(22a)
C(37)ϪH(37)...O(22a)
C(39)ϪH(39)...O(21b)
C(211)ϪH(211)...O(12c)
0.96
0.96
0.93
0.96
0.96
0.93
0.93
0.93
0.93
2.53
2.56
2.28
2.62
2.52
2.47
2.28
2.56
2.53
3.003(5)
3.189(5)
2.893(4)
3.323(4)
3.323(5)
3.394(4)
3.201(4)
3.332(4)
3.431(4)
110.3
123.3
123.2
130.4
141.0
169.9
171.2
140.7
163.1
˚
P21/c
˚
a ϭ 8.8186(7) A
˚
˚
b ϭ 31.599(2) A
c ϭ 14.277(1) A
β ϭ 106.010(2)°.
3824.1(5) A
3
˚
Volume
Z
4
Symmetry transformations used to generate equivalent atoms:
1.378 Mg/m3
a 1Ϫx, 2Ϫy, 1Ϫz; b xϩ1, y, z; c xϪ1, y, zϪ1
Density (calculated)
Absorption coefficient
F(000)
Crystal size
Theta range for data collection
Index ranges
0.666 mmϪ1
1664
0.27 ϫ 0.14 ϫ 0.10 mm3
1.29 to 28.10°.
Ϫ9ՅhՅ11
hedral arrangement (30°) and the dihedral angle formed by
the defined triangular faces is 10.9(1)° as a consequence of
the small bite of the sulfonamide ligands. The
NpyϪNiϪNsulfonamide angles are the main source of distor-
tion, with of values 63.09(10) and 63.13(9)°, respectively,
although these are not markedly different from those found
in similar complexes that have been reported previously
[16]. The NiϪN bond lengths from the bipyridine ligand
Ϫ40ՅkՅ41
Ϫ18ՅlՅ18
21935
8723 [R(int) ϭ 0.0626]
93.6 %
Reflections collected
Independent reflections
Completeness to theta
Absorption correction
Max. and min. Transmission
Data / restraints / parameters
Goodness-of-fit on F2
Final R indices [I>2sigma(I)]
R indices (all data)
Largest diff. peak and hole
SADABS
1.000 and 0.668061
8723 / 0 / 486
0.822
R1 ϭ 0.0476, wR2 ϭ 0.0842
R1 ϭ 0.1437, wR2 ϭ 0.0992
˚
are the shortest in the molecule at 2.047(3) and 2.062(3) A
Ϫ similar to those found in other six-coordinate bipyridine
complexes [17]. The NiϪN bond lengths from the sulfona-
mide ligands are in the range expected for this type of li-
gand [18]. It is worth comparing the coordinative behaviour
of the two sulfonamide ligands. One of these ligands is
bonded to the nickel atom with almost identical NiϪN
Ϫ3
˚
0.379 and Ϫ0.385 e.A
ray data are listed in Table 1 and selected bond distances
and angles are listed in Table 2.
The compound is formed by discrete molecules, although
some intermolecular interactions through non-classical hy-
drogen bonds are found between neighbouring molecules
(see Table 3). The nickel ion is coordinated by two anionic
(N,NЈ)-bidentate sulfonamide ligands and by one (N,NЈ)-
bidentate bipyridine molecule. In this arrangement the me-
tal atom is hexacoordinated in a NiN6 distorted octahedral
environment. The sulfonamide ligands form a chelate ring
with only four members, with a normalized bite b of average
1.046 [15]. This small value makes the octahedron distort
to a trigonal prism, but the values for the angles φ (see
Scheme 3) are 42.5(11), 43.7(1) and 44.7(1)°, respectively.
These angles are closer to the those expected for a octa-
˚
bond distances [2.117(2) and 2.119(2) A], whereas the other
is anisobidentate, with a NiϪNpy bond distance of
˚
˚
2.109(3) A and
a NiϪNsulfonamide bond distance of
2.140(2) A. This situation could be due to the fact that one
of the mesitylene groups forms a π,π-stacking interaction
with the bipyridine ligand, bringing the sulfonamide nitro-
gen atom nearer to the nickel atom to give a shorter
NiϪNsulfonamide bond distance. As found in previous stud-
ies, both ligands are coordinated to the metal in the amide
form, with average CpyϪNpy and CpyϪNsulfonamide bond
˚
distances of 1.356(4) and 1.378(4) A. The CpyϪNsulfonamide
bond length is significantly longer than that found in the
˚
free ligand, 1.347(2) A, whereas the CpyϪNpy bond length
˚
is slightly shorter than in the free ligand, 1.367(2) A [10].
˚
Table 2 Selected bond lengths/A and angles/° for
[Ni(Ms6mepy)2bipy].
The aforementioned π,π-stacking interaction is produced
between the mesitylene ring and the bipyridine molecule
[dihedral angle of 2.7(2)°] and it is of the offset or slipped-
NiϪN(32)
NiϪN(21)
NiϪN(11)
S(1)ϪO(11)
S(1)ϪN(12)
S(2)ϪO(22)
N(11)ϪC(15)
N(21)ϪC(25)
N(32)ϪNiϪN(31)
N(31)ϪNiϪN(21)
N(21)ϪNiϪN(12)
N(31)ϪNiϪN(11)
N(12)ϪNiϪN(11)
N(32)ϪNiϪN(22)
N(21)ϪNiϪN(22)
2.047(3)
2.109(3)
2.119(2)
1.418(3)
1.597(2)
1.440(2)
1.360(4)
1.353(4)
78.85(11)
100.01(11)
105.33(10)
164.10(10)
63.09(10)
98.68(9)
63.13(9)
NiϪN(31)
NiϪN(12)
NiϪN(22)
S(1)ϪO(12)
S(2)ϪO(21)
S(2)ϪN(22)
N(12)ϪC(15)
N(22)ϪC(25)
N(32)ϪNiϪN(21)
N(32)ϪNiϪN(12)
N(32)ϪNiϪN(11)
N(21)ϪNiϪN(11)
N(12)ϪNiϪN(22)
N(31)ϪNiϪN(22)
N(11)ϪNiϪN(22)
2.062(3)
2.117(2)
2.140(2)
1.438(3)
1.439(2)
1.599(2)
1.378(4)
1.379(4)
161.80(10)
92.62(10)
97.32(10)
88.39(10)
164.04(9)
91.81(10)
104.05(10)
Scheme 3
Z. Anorg. Allg. Chem. 2005, 631, 2101Ϫ2106
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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I. Beloso, P. Perez-Lourido, J. Castro, J. A. Garcıa-Vazquez, J. Romero
HTs3mepy: Anal. C, 58.7; H, 5.7; N, 10.2; S. 11.8 %. Calcd. for
C13N2H14O2S C, 59.5; H, 5.4; N, 10.7; S, 12.2 %.
1H NMR (CDCl3, ppm) δ ϭ 2.15 [s, 3H, CH3(py)]; 2.35 [s, 3H, CH3(tolyl)];
6.50 (t, 2H, tolyl); 7.21 (d, 1H, py); 7.40 (d, 1H, py); 7.49 (d, 1H, py); 7.85
(d, 2H, tolyl); 12.14 (b 1H, NH). IR (KBr, cmϪ1): 3248(m), 2920(w), 1593(s),
1543(s), 1399(m), 1371(m), 1342(s), 1255(m), 1127(s), 1080(m), 963(m),
767(w), 683(m), 570(w). EI MS: m/z: 262 (8 %, Mϩ); 108 (20 %, Mϩ
Ϫ
{O2S-tolyl}).
HMs3mepy: Anal. C, 61.3; H, 6.0; N, 9.3; S, 11.2 %. Calcd. for
C15N2H18O2S C, 62.1; H, 6.2, N, 9.6; S. 11.0 %.
1H NMR (CDCl3, ppm) δ ϭ 2.15 [s, 3H, CH3(py)]; 2.25 [s 3H, CH3(p-
mesityl)]; 2.71 [s, 6H, CH3(o-mesityl)]; 6.47 (t, 1H, py); 6.89 (s, 2H, tolyl);
7.36 (d, 1H, py); 7.42 (d, 1H, py); 12.33 (b, 1H, NH). IR (KBr, cmϪ1):
3222(m), 2940(w), 1633 (w), 1595(s), 1544(s), 1375(w), 1338(s), 1259(m),
1125(m), 1098(s), 1047(m), 780(m), 676(m). EI MS: m/z: 291 (100 %, Mϩ);
108 (10 %, Mϩ Ϫ {O2S-mesityl}).
HTs6mepy: Anal. C, 58.8; H, 5.6; N, 10.6; S, 12.3 %. Calcd. for
C13N2H14O2S C, 59.5; H, 5.4; N, 10.7; S, 12.2 %.
1H NMR (CDCl3, ppm) δ ϭ 2.36 [s, 3H, CH3(tolyl)]; 2.41 [s, 3H, CH3(py)];
6.60 (d, 1H, py); 7.06 (d, 1H, py); 7.22 (d, 2H, tolyl); 7.46 (t, 1H, py); 7.79
(d, 2H, tolyl); 9.95 (b 1H, NH). IR (KBr, cmϪ1): 3231(w), 3052(w), 2958(w),
1613(vs), 1534(m), 1369(s), 1252(m), 1135(s), 1089(m), 855(m), 787(m),
661(m), 572(m). EI MS: m/z: 262 (6 %, Mϩ); 108 (3 %, Mϩ Ϫ {O2S-tolyl}).
Figure 2 View of the π,π-stacking interaction between the bipyri-
dine molecule and mesitylene ring of [Ni(Ms6mepy)2bipy].
stacking type, since the distance between centroids of the
three rings are of 3.8887(2) and 4.4092(3) A, respectively.
HMs6mepy: Anal. C, 61.3; H, 6.4; N, 9.5; S, 10.9 %. Calcd. for
C15N2H18O2S C, 62.1; H, 6.2; N, 9.6; S, 11.0 %.
˚
However, the distance between the centre of the mesitylene
ring and the C(35)ϪC(36) bond is only 3.5556(2) A. The
1H NMR (CDCl3, ppm) δ ϭ 2.24 [s, 3H, CH3(p-mesityl)]; 2.37 [s, 3H,
CH3(py)]; 2.69 [s, 6H, CH3(o-mesityl)]; 6.55 (d, 1H, py); 6.74 (d, 1H, py);
6.88 (s, 2H, tolyl); 7.37 (t, 1H, py); 9.40 (b, 1H, NH). IR (KBr, cmϪ1):
3236(w), 2931(w), 1617(s), 1533(m), 1457(m), 1363(vs), 1290(m), 1137(s),
˚
distance from the plane of the bipyridine molecule to the
˚
1063 (w), 834(m), 656(m). EI MS: m/z: 291 (4 %, Mϩ); 108 (13 %, Mϩ
Ϫ
centroid of the mesitylene ring is about 3.51(1) A (see Fig-
{O2S-mesityl}).
ure 2)[8, 9, 19, 20]. In addition, some short contacts are
given in Table 4.
The dihedral angle between the rings in each sulfonamide
ligand are 66.49(8) and 88.14(13)°, while in the free ligand
both values were close to 90° [10], with the shorter value
another consequence of the π,π-stacking interaction.
Preparation of complexes
The complexes were obtained by following an electrochemical pro-
cedure. The cell consisted of a 100 mL tall-form beaker fitted with
a rubber bung through which the electrochemical leads entered.
An acetonitrile solution of the ligand (HL) and the coligand [2,2Ј-
bipyridine or 1,10-phenanthroline (LЈ)], containing a small amount
of tetraethylammonium perchlorate as a current carrier, was elec-
trolysed using a platinum wire as the cathode and a nickel plate
suspended from another platinum wire as the sacrificial anode. Di-
rect current was supplied by a purpose-built d. c. power supply.
Applied voltages of 5Ϫ10 volts allowed sufficient current flow for
smooth dissolution of the nickel metal. The current was maintained
at 10 mA during 1.5 h. In all cases, hydrogen was evolved from the
cathode. These cells can be summarised as:
3 Experimental Section
Acetonitrile, dichloromethane, 2-amino-3-picoline, 2-amino-6-pico-
line, p-toluenesulfonyl chloride, 2-mesitylenesulfonyl chloride, 2,2Ј-
bipyridine, 1,10-phenanthroline monohydrate, and all other re-
agents were commercial products and were used as supplied. Nickel
(Aldrich) was used as 2 ϫ 2 cm plates.
Preparation of ligands
Ni(ϩ) / CH3CN ϩ HL ϩ LЈ / Pt(Ϫ)
Ligands were prepared by reaction of the corresponding amine and
p-toluenesulfonyl or mesitylsulfonyl chloride in a 1:1 ratio in di-
chloromethane using an aqueous solution of sodium carbonate as
base [8Ϫ10].
After electrolysis the green solutions were filtered to remove any
particles of metal and then left to concentrate, yielding crystalline
products. The solids were washed with acetonitrile and diethyl ether
and dried at room temperature.
˚
Table 4 Some short contacts/A between rings for
[Ni(Ts3mepy)2bipy]. Electrolysis of a solution of the ligand (0.15 g,
0.57 mmol) and 2,2Ј-bipyridine (0.04 g, 0.28 mmol) in acetonitrile
(50 cm3) at 8 V and 10 mA for 1.5 h dissolved 16.7 mg of nickel,
Ef ϭ 0.51 mol·FϪ1. Anal. Calc. for NiC36H34N6O4S2: C, 58.7; H,
4.6; N, 11.4; S, 8.7. Found: C, 57.2; H, 4.5; N, 11.2; S, 8.2 %.
IR (KBr, cmϪ1): 2916(w), 1600(s), 1442(s), 1323(s), 1116(s), 768(m), 738(m).
LSIMS (m/z): 737 [Ni(Ts3mepy)2bipy]ϩ; 581 [Ni(Ts3mepy)2]ϩ; 475
[Ni(Ts3mepy)bipy]ϩ; 263 (Ts3mepy)ϩ. χ ϭ 2.9 BM.
[Ni(Ms6mepy)2bipy].
C17ϪN31
C112ϪC31
C111ϪC33
C111ϪC34
C17ϪC35
C111ϪC35
C17ϪC36
C19ϪC36
C18ϪN32
3.560(5)
3.729(6)
3.759(8)
3.541(7)
3.642(5)
3.746(6)
3.842(4)
3.695(5)
3.638(4)
C112ϪN31
C17ϪN32
C110ϪC34
C112ϪC34
C18ϪC35
C112ϪC35
C18ϪC36
C19ϪC37
3.593(5)
3.882(4)
3.717(8)
3.861(5)
3.806(5)
3.645(5)
3.543(5)
3.698(5)
[Ni(Ts3mepy)2phen]. A solution of the ligand (0.15 g, 0.57 mmol)
and 1,10-phenanthroline (0.05 g, 0.28 mmol) in acetonitrile
2104
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2101Ϫ2106

Nickel(II) Complexes with N-2-Pyridyl-sulfonamide Ligands
(50 cm3) was electrolyzed at 10 V and 10 mA during 1.5 h; 17.8 mg
Physical measurements
of nickel metal was dissolved from the anode, Ef ϭ 0.54 mol·FϪ1
.
The C, N, H and S contents of the compounds were determined
on a Carlo-Erba EA 1108 microanalyser. IR spectra were recorded
as KBr mulls on a Bruker Vector-22 spectrophotometer. Solid state
electronic spectra were recorded on a Shimadzu UV 3101 PC. Mag-
netic measurements at room temperature were made using a DMS
VSM 1160 instrument. Liquid Secondary Ion Mass Spectra
(LSIMS), using 3-nitro benzylalcohol as matrix, were recorded on
a Micromass VG Autospec M instrument.
Anal. Calc. For NiC38H34N6O4S2 : C, 59.9; H, 4.5; N, 11.0; S, 8.4.
Found: C, 55.8; H, 4.3; N, 11.4; S, 8.2 %.
IR (KBr, cmϪ1): 2922(w), 1598(m), 1518(w), 1418(s), 1332(m), 1117(s),
846(m), 727(w). LSIMS (m/z): 762 [Ni(Ts3mepy)2phen]ϩ; 500
[Ni(Ts3mepy)phen]ϩ; 263 (Ts3mepy)ϩ. χ ϭ 3.0 BM.
[Ni(Ms3mepy)2bipy]. Electrolysis of a solution of the ligand (0.15 g,
0.57 mmol) and 2,2Ј-bipyridine (0.04 g, 0.28 mmol) in acetonitrile
(50 cm3) at 8 V and 10 mA for 1.5 h dissolved 14.6 mg of nickel
from the anode, Ef
ϭ
0.45 mol·FϪ1
.
Anal. Calc. for
NiC40H42N6O4S2: C, 60.5; H, 5.3; N, 10.6; S, 8.1. Found: C, 61.2;
H, 5.5; N, 10.5; S, 8.2 %.
Crystal structure determination
IR (KBr, cmϪ1): 2926(w), 1596(s), 1447(s), 1338(s), 1119(s), 769(m), 740(w).
LSIMS (m/z): 794 [Ni(Ms3mepy)2bipy]ϩ; 503 [Ni(Ms3mepy)bipy]ϩ; 291
(Ms3mepy)ϩ. χ ϭ 3.1 BM.
The data collections were taken on a SIEMENS Smart CCD area-
detector diffractometer with graphite-monochromated Mo-Kα
radiation. Absorption corrections were carried out using SADABS
[21]. The structure of [Ni(M6mepy)2bipy] was solved by direct
methods and refined by full-matrix least-squares based on F2 [22].
All non-hydrogen atoms were refined with anisotropic displace-
ment parameters. Hydrogen atoms were also included in idealised
positions and refined with isotropic displacement parameters.
Atomic scattering factors and anomalous dispersion corrections for
all atoms were taken from International Tables for X-ray Crystal-
lography [23]. The atomic positions, full list of bond lengths and
angles and other crystallographic data are available on request from
J.C. Crystallographic data have been deposited with the CCDC, (12
Union Road, Cambridge CB2 1EZ, UK) and are available on re-
quest quoting the deposition number CCDC255739.
[Ni(Ms3mepy)2phen]. A solution of the ligand (0.15 g, 0.57 mmol)
and 1,10-phenanthroline (0.05 g, 0.28 mmol) in acetonitrile
(50 cm3) was electrolyzed at 8 V and 10 mA during 1.5 h; 15.6 mg
of nickel metal was dissolved from the anode, Ef ϭ 0.47 mol·FϪ1
.
Anal. Calc. for NiC42H42N6O4S2: C, 61.7; H, 5.2; N, 10.3; S, 7.8.
Found: C, 61.0; H, 5.5; N, 10.7; S, 8.2 %.
IR (KBr, cmϪ1): 2926(w), 1594(s), 1519(w), 1414(s), 1338(m), 1119(s),
850(m), 723(w). LSIMS (m/z): 528 [Ni(Ms3mepy)phen]ϩ; 291 [Ms3mepy]ϩ
χ ϭ 2.8 BM.
[Ni(Ts6mepy)2bipy]. Electrolysis of a solution of the ligand (0.15 g,
0.57 mmol) and 2,2Ј-bipyridine (0.04 g, 0.28 mmol) in acetonitrile
(50 cm3) at 8 V and 10 mA for 1.5 h dissolved 17.8 mg of nickel
from the anode, Ef
ϭ
0.54 mol·FϪ1
.
Anal. Calc. for
Acknowledgements. This work was supported by the XUNTA DE
GALICIA (Spain) under the grant PGIDT00PXI20305PR.
NiC36H34N6O4S2: C, 58.7; H, 4.6; N, 11.4; S, 8.7. Found: C, 55.7;
H, 4.5; N, 10.8; S, 8.3 %.
IR (KBr, cmϪ1): 2923(w), 1568(s), 1457(s), 1326(s), 1139(s), 768(m), 737(m).
LSIMS (m/z): 737 [Ni(Ts6mepy)2bipy]ϩ; 581 [Ni(Ts6mepy)2]ϩ; 475
[Ni(Ts6mepy)bipy]ϩ; 263 (Ts6mepy)ϩ. χ ϭ 2.9 BM.
References
[Ni(Ts6mepy)2phen]. A similar experiment to that described above
(8 V, 10 mA, 1.5 h.) with the same sulfonamide ligand (0.15 g,
0.57 mmol) and 1,10-phenanthroline (0.05 g, 0.28 mmol) in aceto-
nitrile (50 cm3) led to the dissolution of 15.2 mg of nickel, Ef ϭ
0.46 mol·FϪ1. Anal. Calc. for NiC38H34N6O4S2: C, 59.9; H, 4.5; N,
11.0; S, 8.4. Found: C, 59.0; H, 4.5; N, 11.2; S, 8.2 %.
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[Ni(Ts6mepy)phen]ϩ. χ ϭ 3.0 BM.
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H, 5.4; N, 10.5; S, 8.2 %.
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2.9 BM. Suitable crystals for X-ray studies were obtained by air concen-
tration of the resulting solution.
´
´
´
´
[8] I. Beloso, J. Borras, J. Castro, J. A. Garcıa-Vazquez, P. Perez-
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and 1,10-phenanthroline (0.05 g, 0.28 mmol) in acetonitrile
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´
´
´
of nickel metal was dissolved from the anode, Ef ϭ 0.45 mol·FϪ1
.
´
´
´
Anal. Calc. for NiC42H42N6O4S2: C, 61.7; H, 5.2; N, 10.3; S, 7.8.
Found: C, 60.4; H, 5.5; N, 9.8; S, 7.6 %.
IR (KBr, cmϪ1): 2935(w), 1591(m), 1517(w), 1427(s), 1327(m), 1128(s),
849(m), 727(w). LSIMS (m/z): 818 [Ni(Ms6mepy)2phen]ϩ; 528
[Ni(Ms6mepy)phen]ϩ; 291 [Ms6mepy]ϩ χ ϭ 3.1 BM.
´
´
´
Romero, A. Sousa, unpublished results.
Z. Anorg. Allg. Chem. 2005, 631, 2101Ϫ2106
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2105

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2106
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2101Ϫ2106