New manganese complexes with 2-salicyloylhydrazono-1,3-dithiolane ligand and various coordination solvents

Article abstract of DOI:10.1016/j.ica.2005.06.037

The new Mn(HL)₂L₂′ complexes with 2-salicyloylhydrazono-1,3-dithiolane ligand (H₂L) have been obtained with good yields (≈85%) by reacting manganese (II) acetate tetrahydrate or manganese (II) acetylacetonate with 2-salicy

Full text of DOI:10.1016/j.ica.2005.06.037

Inorganica Chimica Acta 358 (2005) 3881–3888
www.elsevier.com/locate/ica
New manganese complexes with 2-salicyloylhydrazono-1,3-dithiolane
ligand and various coordination solvents
a
b,
a,
*
C. Beghidja , M. Wesolek *, R. Welter
a
Laboratoire DECMET, UMR CNRS 7513, Universite´ Louis Pasteur Strasbourg I, 4 rue Blaise Pascal, F-67070 Strasbourg Cedex, France
b
Laboratoire de Chimie des Me´taux de Transition et de Catalyse, UMR CNRS 7513, Universite´ Louis Pasteur Strasbourg I,
4 rue Blaise Pascal, F-67070 Strasbourg Cedex, France
Received 11 April 2005; accepted 10 June 2005
Available online 8 August 2005
Abstract
The new MnðHLÞ L02 complexes with 2-salicyloylhydrazono-1,3-dithiolane ligand (H2L) have been obtained with good yields
2
(ꢀ85%) by reacting manganese (II) acetate tetrahydrate or manganese (II) acetylacetonate with 2-salicyloylhydrazono-1,3-dithiolane
ligand in DMF, THF or Py (L0). These compounds have been fully characterized by spectroscopic methods and single crystal X-ray
diffraction. In the solid state, supramolecular networks are described and discussed in terms of weak H-bonds and short contacts.
The new monomeric complexes will be considered as candidates to obtain polynuclear complexes.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Manganese; Mn(II) complexes; Crystal structure; 2-salicyloylhydrazono-1,3-dithiolane; Magnetic measurement; Supramolecular netw-
ork; H-bond
1. Introduction
ium and silver surfaces by means of a series of ligands
containing heterocyclic sulfur and examined in detail
the electroreduction kinetics of these complexes ad-
sorbed via a bridging ligand at the different surfaces.
Such approach can be used in the aim of building new
magnetic system. In fact, in comparison with mineral
phases (such as intermetallic compounds, for instance),
magnetic interactions are usually very low in molecular
species [15]. The possibility to anchor molecular com-
pounds in specific surface [13,14] will be an interesting
way to generate, by thermal decomposition of the organ-
ic part of the molecule, new and potentially hard mag-
netic materials. In our research group, we focus our
attention more specifically on transition metal sublattice
magnetic interactions, taking into account our previous
works within magnetic properties of intermetallic system
framework [16]. Actually, we work more particularly on
the development of new manganese (+II and +III) base
molecular and/or supramolecular complexes, which can
be potentially deposited to gold surface.
The mediation of electron transfer reactions be-
tween transition metal centers to metal surfaces via
bridging organic ligands containing a sulfur atom
[1,2] has received a great deal of attention over the
last years. Particularly attractive candidates are
thiophenols [3], sulfides [4,5], disulfides [6], mercapto-
anilines [7], xanthates [8], thiocarbamates [9], and mer-
captoimidazoles [10,11], which form strong bonds to
gold surfaces and in many cases produce ordered
self-assembled monolayer and multilayer [12].
Tomi et al. [13,14] reported that transition metal
complexes could be anchored to gold, mercury, platin-
*
Corresponding authors. Tel.: +33 3 9024 1339; fax: +33 3 9024
1329 (M. Wesolek), Tel.: +33 3 9024 1593; fax: +33 3 9024 1232
(R. Welter).
E-mail addresses: wesolek@chimie.u-strasbg.fr (M. Wesolek),
welter@chimie.u-strasbg.fr (R. Welter).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.06.037

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C. Beghidja et al. / Inorganica Chimica Acta 358 (2005) 3881–3888
In this preliminary study, we report the synthesis of
2.2.2. Synthesis of complexes (2), (3) and (4)
three new manganese complexes prepared by using the
2-salicyloylhydrazono-1,3-dithiolane ligand [17], which
contains heterocyclic sulfur, allowing their potential
anchoring on gold surface (this aspect will be presented
in future works) and various coordination solvents fol-
lowed by the characterization of these complexes using
X-ray single crystal diffraction, infrared spectroscopy
and magnetic measurements.
2.2.2.1. Mn(HL)2(DMF)2 (2). The ligand H2L
(0.127 g, 0.5 mmol) was dissolved in DMF (3 ml). When
the ligand was dissolved completely, 0.63 g (0.25 mmol)
of manganese (II) acetate tetrahydrate was added. After
staying for one day, yellow rectangular crystals of 2 were
obtained (0.156 g, 88% yield). Anal. Calc. for C26H32-
MnN6O6S4: C, 44.12; H, 4.56; N, 11.88; S, 18.08.
Found: C, 44.4; H, 4.6; N, 11.9; S, 18.0%.
2.2.2.2. Mn(HL)2(THF)2 Æ THF (3). The ligand H2L
(0.127 g, 0.5 mmol) in THF (8 ml) was heated until dis-
solution. The manganese (II) acetylacetonate (0.67 g,
0.25 mmol) in THF (2 ml) was heated until dissolution
in another flask. The two solutions were mixed and
the combined solution was allowed to stand for one
day, yellow rectangular crystals of 3 were obtained
(0.168 g, 86.6% yield). Anal. Calc. for C28H34MnN6O7-
S4C4H8O: C, 49.41; H, 5.44; N, 7.2. Found: C, 48.5;
H, 5.4; N, 7.2%.
2. Experimental
2.1. General procedures
All reactions and manipulations, excepted for the
ligand H2L, were carried out under an inert atmo-
sphere of argon (AirLiquide, U-grade) using standard
Schlenk tube techniques. Solvents were dried under
nitrogen before use: tetrahydrofuran over sodium-ben-
zophenone, and dimethylformamide over sodium hy-
dride. Elemental C, H, N, and S analyses were
performed by the ꢀService de Microanalysesꢁ of Le
Bel Institute and Charles Sadron Institute (ULP,
Strasbourg, France). Infrared spectra were recorded
on a Perkin–Elmer 1600 series FTIR spectrometer.
The 1H NMR spectra were recorded at 300 MHz
and 13C{1H} NMR spectra at 75 MHz on a Bruker
AVANCE 300 instrument.
Compound 3 can be obtained by heating 2 in THF
until dissolution. The solution was allowed to stand
for two days, whereupon yellow rectangular crystals of
3 were obtained.
2.2.2.3. Mn(HL)2(py)2 [cis (4a) and trans (4b) iso-
mers]. Mn(HL)2(py)2 Æ MeOH (4a). We notice that this
cis-compound 4a has been obtained once in these condi-
tions. Ligand H2L (0.127 g, 0.5 mmol) was dissolved in
methanol/pyridine (11 ml, 10/1) mixed solvent. When
the ligand H2L was dissolved completely, the manganese
(II) acetylacetonate (0.67 g, 0.25 mmol) was added.
After staying for one day, yellow rectangular crystals
of 4a were obtained (0.155 g, 83% yield). Anal. Calc.
for C30H28MnN6O4S4: C, 50.06; H, 3.92; N, 11.68.
Found: C, 49.9; H, 4.1; N, 11.6%.
Magnetic data (complex 2) were obtained on
MANICS magnetometer (IPCMS Strasbourg) in the
temperature range 300–5 K.
2.2. Synthesis
2.2.1. Ligand 2-salicyloylhydrazono-1,3-dithiolane (H2L)
The ligand H2L was synthesized as previously
described [17]. To a well stirred solution of salicylhyd-
razide (2.525 g, 16.6 mmol) and NaOH (1.32 g,
33.2 mmol) in absolute ethanol (30 ml) at ambient tem-
perature, CS2 (1 ml, 16.6 mmol) and CH3I (2 ml,
33.2 mmol) are successively added dropwise. The time
between additions is 30 min. Stirring is continued for
8 h, the mixture is poured onto cooled water (25 ml),
and the resulting white precipitate was filtered and
rinsed with water. Recrystallization from DMF/water
affords compounds H2L (2.98 g, 70.5% yield). 1H
NMR (DMSO-d6): d 11.81, 10.99 (br s, br s, 2H, at
amide and phenolic OH), 7.95–7.93 (m, 1H, H at phe-
nyl), 7.44–7.38 (m, 1H, H at phenyl), 7.01–6.94 (m,
2H, Hs at phenyl), 3.77–3.73, 3.62–3.58 (m, m, 4H, Hs
at SCH2CH2S). 13C NMR (DMSO-d6): d = 36.09,
39.16 (2 CH2); 117.31, 120.15, 130.79, 133.87, 156.99
(Carom); 161.51 (CO); 163.50 (S–C–S). Anal. Calc. for
C10H10N2O2: C, 47.24; H, 3.96; N, 11.02. Found: C,
47.4; H, 4.1; N, 11.2%.
Mn(HL)2(py)2 (4b). Ligand H2L (0.127 g, 0.5 mmol)
was dissolved in methanol/pyridine (11 ml, 10/1) mixed
solvent. When the ligand H2L was dissolved com-
pletely, the manganese (II) acetate tetrahydrate
(0.63 g, 0.25 mmol) was added. After staying for one
day, yellow rectangular crystals of 4b were obtained
(0.151 g, 84% yield). Anal. Calc. for C30H28 MnN6-
O4S4: C, 50.06; H, 3.92; N, 11.68. Found: C, 50.2; H,
4.2; N, 11.7%.
2.3. Single crystals X-ray determination
Single crystals of H2L, 2, 3, 4a and 4b were mounted
on a Nonius Kappa-CCD area detector diffractometer
˚
(Mo Ka k = 0.71073 A). The complete conditions of
data collection (Denzo software)[18] and structure
refinements are given in Table 1. The cell parameters
were determined from reflections taken from one set of
10 frames (1.0ꢁ steps in phi angle), each at 20 s exposure.
The structures were solved using direct methods and

Table 1
´
´
´
´
Donnees cristallines et details de la determination structurale des composes (1), (2), (3), (4a) et (4b) (tous les cristaux sont jaunes)
Donne´es cristallines
(1)
(2)
(3)
(4a)
(4b)
Formula
C
10H10N2O2S2
C26H32MnN6O6S4
707.76
monoclinic
P21/n
9.276(1)
31.253(5)
11.384(2)
90
110.23(5)
90
3096.7(8)
4
1.518
0.747
1468
C28H34MnN4O6S4, C4H8
777.88
O
C30H28MnN6O4S4, CO
C30H28MnN6O4S4
719.76
orthorhombic
Pbca
Formula weight (g molꢁ1
Crystal system
Space group
)
254.32
orthorhombic
Pna21
12.636(2)
5.560(1)
15.845(2)
90
90
90
1113.2(3)
4
1.517
747.77
monoclinic
C2/c
32.027(5)
12.013(2)
17.409(3)
90
95.098(5)
90
6671(4)
8
monoclinic
C2/c
16.564(11)
25.302(8)
9.0920(10)
90
106.32(7)
90
3657(3)
4
˚
a (A)
11.133(1)
18.254(3)
16.068(3)
90.00
90.00
90.00
3265.4(9)
4
1.464
0.705
1484
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Density (calc) (g cmꢁ3
)
1.413
0.640
1628
1.489
0.696
3080
l (Mo Ka) (mmꢁ1
F(000)
)
0.463
528
Crystal size (mm)
0.13 · 0.10 · 0.08
0.09 · 0.10 · 0.13
0.11 · 0.10 · 0.09
0.10 · 0.12 · 0.08
0.13 · 0.10 · 0.15
Data collection
h Min–Max (ꢁ)
Dataset (h;k;l)
Total unique data, R(int)
Observed data (I > 2r(I))
2.57, 27.45
2.01, 30.03
1.51, 30.26
1.28, 30.00
2.23, 30.05
ꢁ16/14; ꢁ6/7; ꢁ20/15
7887, 2240, 0.051
1899
ꢁ8/13; ꢁ40/43; ꢁ15/16
17107, 8382, 0.048
6423
ꢁ23/22; 0/35; 0/12
5419, 5418, 0.069
2939
ꢁ44/44; ꢁ16/16; ꢁ18/24
39129, 9721, 0.063
6587
ꢁ9/15; ꢁ23/25; ꢁ20/22
25070, 4786, 0.049
3151
Refinement
N reflections, N parameters
R, wR2, Goodness-of-fit
P ¼ ðF 2o þ 2F 2c Þ=3
2240, 185
8382, 388
5418, 222
9721, 428
4786, 209
0.0456, 0.0737, 1.07
w ¼ 1=½r2ðF 2oÞþ
0.0717, 0.1563, 1.16
w ¼ 1=½r2ðF 2oÞþ
0.0885, 0.2120, 1.165
w ¼ 1=½r2ðF 2oÞþ
0.0584, 0.1177, 1.047
w ¼ 1=½r2ðF 2oÞþ
0.0471, 0.1171, 1.015
w ¼ 1=½r2ðF 2oÞþ
2
2
2
2
2
ð0.0176PÞ þ 0.2422Pꢂ
ð0.0524PÞ þ 3.7545Pꢂ
ð0.0500Þ þ 0.5000Pꢂ
ð0.0376PÞ þ 8.6294Pꢂ
ð0.0479PÞ þ 1.1321Pꢂ
Maximum and average
shift/error
0.001, 0.000
0.001, 0.000
0.002, 0.000
0.001, 0.000
0.00, 0.000
Flack x
0.10(9)
Minimum, maximum
residual density (e/A )
ꢁ0.291, 0.323
ꢁ0.583, 0.612
ꢁ0.529, 0.435
ꢁ0.45, 0.603
ꢁ0.318, 0.273
3
˚

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C. Beghidja et al. / Inorganica Chimica Acta 358 (2005) 3881–3888
refined against F2 using the SHELXL-97 software [19]. The
absorption was non-corrected.
1259 cmꢁ1 for 2, 1254 and 1258 cmꢁ1 for 4a and 4b,
respectively.
All non-hydrogen atoms (excepted for methanol in
4a) were refined anisotropically and hydrogen atoms
were introduced as fixed contribution (SHELXL-97) ac-
cepted for hydrogen (founded by Fourier differences)
in the case of ligand H2L and for the hydrogen of phenol
group for all complexes.
3.2. Description of the crystal structures
3.2.1. Ligand H2L (C10H10N2O2S2)
An ORTEP view of H2L in the crystal structure is
shown in Fig. 1. The molecule is planar except for the
two methylene groups. One intramolecular hydrogen-
bond between the nitrogen of the hydrazide group and
˚
3. Results and discussion
the oxygen of phenol group (d(N1–O2) = 2.62(1) A)
with an angle N1–H6–O2 = 138(1)ꢁ is observed.
There is an additional intermolecular hydrogen bond
between the oxygen of the carbonyl group O1 and the
oxygen of the phenol group O2 of the next adjacent mol-
ecule: O1–O2: 2.68(1) A with an angle O1–H5–O2:
169(1)ꢁ). These H-bonds connect adjacent molecules
perpendicularly along the a-axis as shown in Fig. 2.
3.1. Syntheses and IR characterization
The reaction in various organic solvents (L0) of
Mn(II) salt with 2-salicyloylhydrazono-1,3-dithiolane li-
gand H2L gives easily the disubstituted complexes
MnðHLÞ2L02. This reaction was made in various solvents
to see whether the change of reactional medium influ-
ences the mode of coordination of the ligand, according
to the reaction shown in Scheme 1.
˚
3.2.2. Complex Mn(HL)2 (DMF)2 (2)
An ORTEP view of the molecular structure of com-
plex 2 in the crystal is depicted in Fig. 3.
The manganese atom is surrounded by two cis-coor-
dinated solvent molecules of DMF (O5 and O6) and two
cis-coordinated HL ligands, coordinated by the hydra-
zide group (O1 and N2 atoms) of the first ligand and
the atoms O3 and N4 for the second ligand. The sur-
rounding appears to be octahedrally based, with an
The H2L ligand used in this synthesis was selected as
a tetradentate bridging ligand for connecting two man-
ganese centers using a hydrazide N–N group [20,21]
but the intramolecular hydrogen bonding (see below
and in Section 3.2.1.) (O–Hꢃ ꢃ ꢃN) prevented this bridging
by forming mononuclear complexes, which have been
characterized by elemental analysis (see Section 2), IR
spectroscopy and single crystal X-ray diffraction.
The IR spectrum of the ligand displays bands at 3199,
1637 and 1539 cmꢁ1, which may be assigned to m(N–H)
m(C@O) and m(N@C), respectively [22,23]. The presence
of m(OH) as a weak band in the 2853–3068 cmꢁ1 regions
suggests an intramolecular hydrogen bonding (O–
Hꢃ ꢃ ꢃO) [24].
In the complexes 2, 3, 4a and 4b, the band assigned to
m(N–H) and (C@O) disappears, but in the complex 2,
the band at 1665 cmꢁ1 is assigned to m(C@O) of the
DMF ligand. These complexes show bands assigned to
m(O–C@N) at 1585 cmꢁ1 for 2, 1593 and 1598 cmꢁ1
for 4a and 4b, respectively, and m(C–O) (enolic) at
˚
Fig. 1. ORTEP view of the ligand H2L. Selected distances ([A]): O1–
C1: 1.230(3); C1–N1: 1.342(3); C1–C2: 1.494(4); N1–N2: 1.385(3); N2–
C8: 1.281(4); C8–S1: 1.757(3); C8–S2: 1.755 (3).
O
N
S
N
H
2
2
S
OH
S
L' L'
S
Mn
N
O
N
H
N
O
N
O
O
N
H
O
H
N
S
S
Mn(OAc) .4H O
2
2
S
+
ou
Mn(Acac)
S
L'
OH
H L
2
(L') DMF, pyridine, THF
2
Scheme 1.

C. Beghidja et al. / Inorganica Chimica Acta 358 (2005) 3881–3888
3885
Fig. 2. Partial view ((a,c) projection) of H2L showing hydrogen bonds
between O1 and O2.
Fig. 5. ORTEP view of [Mn(HL)2(THF)2].THF (3). The hydrogen
atoms excepted for the phenol group and the solvent (one THF
˚
molecule) have been omitted for clarity. Selected bond distances ([A])
and angles (ꢁ): Mn–O1: 2.107(3), Mn–O5: 2.224(3), Mn–N2: 2.266(4),
O1–C1: 1.274(5), C1–N1: 1.327(5); O5–Mn–O50: 86.70(18), O5–Mn–
O1: 97.42(12), O5–Mn–N2: 89.78(13), O1–Mn–N2: 72.76(12). Sym-
metry operator for equivalent position (A ! A0): ꢁx ꢁ 1, y, ꢁz ꢁ 0.5.
154ꢁ), for the first ligand and O4–H2ꢃ ꢃ ꢃN3 (O4–N3:
˚
2.56 A with an angle O4–H6–N3: 149ꢁ) for the second
ligand, is observed.
The molecular structure of complex 2 is probably sta-
bilized by C–Hꢃ ꢃ ꢃO and C–Hꢃ ꢃ ꢃp intermolecular weak
hydrogen bonds [25–28] between C25–H25Aꢃ ꢃ ꢃO3
Fig. 3. ORTEP view of Mn(HL)2(DMF)2 (2). The hydrogen atoms
˚
excepted for the phenol group have been omitted for clarity. Selected
(C25–O3: 3.32 A with an angle C25–H25A–O3: 122ꢁ)
˚
bond distances ([A]) and angles (ꢁ): Mn–O1: 2.106(3), Mn–O3 2.109(2),
and C10–H10Aꢃ ꢃ ꢃp (C2 ! C7) (C10–(C2,C7)centro¨ıd:
Mn–N2: 2.289(3), Mn–N4: 2.358(3), Mn–O5: 2.147(2), Mn–O6:
2.196(2), O1–C1: 1.276(4), C1–N1: 1.320(4); O1–Mn–N2: 73.58(9),
O3–Mn–N4: 72.07(9), O1–Mn–N4: 93.96(9), O3–Mn–N2: 95.37(9),
O5–Mn–N2: 95.84(10), O6–Mn–N4: 83.50(10), O6–Mn–O3: 97.18(10),
O5–Mn–O3: 96.45(10), O6–Mn–O1: 92.99(9), O5–Mn–O1: 99.30(10),
O5–Mn–O6: 87.73(10).
˚
3.42 A with an angle C10–H10A–(C2,C7) centro¨ıd):
175.3ꢁ. From supramolecular point of view, this struc-
ture can be described as a zig-zag chain within which
the molecular complexes are connected to each other
via C–Hꢃ ꢃ ꢃO H-bond and C–Hꢃ ꢃ ꢃp H-bond alterna-
tively (see Fig. 4).
irregular equatorial (O1–O5–O3–N4) plane. An intra-
molecular hydrogen-bond between the nitrogen of the
hydrazide group and the oxygen of phenol group O2–
H1ꢃ ꢃ ꢃN1 (O2–N1: 2.56 A with an angle N1–H6–O2:
3.2.3. Complex [Mn(HL)2(THF)2] Æ THF (3)
An ORTEP view of the molecular structure of com-
plex (3) in the crystal is depicted in Fig. 5.
˚
Fig. 4. Supramolecular view of complex 2 (along b axis) showing weak hydrogen bonds (C25–H25Aꢃ ꢃ ꢃO3 and C10–(C2,C7)centro¨ıd) between
adjacent molecules.

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C. Beghidja et al. / Inorganica Chimica Acta 358 (2005) 3881–3888
Fig. 6. 3d view of 2 pseudo-dimeric chains connected via two solvent molecules by weak H-bonds (C–Hꢃ ꢃ ꢃS and C–Hꢃ ꢃ ꢃO).
In this case, the manganese atom is surmounted by
The substitution of DMF ligand in complex 2 by
THF ligand gives complex 3. This modification has an
effect on the crystal structure, which is probably stabi-
lized by C–Hꢃ ꢃ ꢃO and C–Hꢃ ꢃ ꢃS intermolecular weak
hydrogen bonds [27–29].
two cis-coordinated solvent molecules of THF (O5 and
O50) and two cis-coordinated HL ligands, coordinated
by the hydrazidate group (O1 and N2 atoms) of the first
ligand and the atoms O10 and N20 for the second ligand.
As in complex 2, the Mn surrounding appears to be
octahedrally based, with an irregular equatorial (O1–
O5–O10–N10) plane. The same intramolecular hydro-
gen-bond between the nitrogen of the hydrazide group
and the oxygen of phenol group (O2–H1ꢃ ꢃ ꢃN1:
˚
The C9–H9ꢃ ꢃ ꢃS1 (C9–S1: 3.63 A with an angle C9–
H9A–S1: 129ꢁ) H-bond connects a chain of complexes
along c-axis and a bifurcated H-bond C10–H10Aꢃ ꢃ ꢃS2
˚
(C10–S2: 3.65 A with an angle C10–H10A–S2: 128ꢁ)
˚
and C10–H10Aꢃ ꢃ ꢃO2 (C10–O2: 3.55 A with an angle
˚
2.564 A with an angle N1–H6–O2: 151.72ꢁ) is observed.
C10–H10A–O2: 149ꢁ) connects two adjacent chains
which are connected to each other via C29–H29Bꢃ ꢃ ꢃS2
˚
(C29–S2: 3.78 A, with an angle C29–H29B–S2: 141ꢁ)
H-bond as shown in Fig. 6.
3.2.4. Complex [Mn(L1)2(Py)2] Æ MeOH (4a)
An ORTEP view of the molecular structure of com-
plex 4a in the crystal is depicted in Fig. 7.
The manganese atom is surmounted by two cis-coor-
dinated solvent molecules of pyridine (N5 and N6) and
two cis-coordinated HL ligands, coordinated by the
Fig. 7. ORTEP view of [Mn(HL)2(Py)2] Æ MeOH (4a). The hydrogen
atoms excepted for the phenol group and the solvent have been
˚
omitted for clarity. Selected bond distances ([A]) and angles (ꢁ): Mn–
O1: 2.112(2), Mn–O3: 2.125(2), Mn–N2: 2.294(2), Mn–N4: 2.291(2),
Mn–N5: 2.272(2), Mn–N6: 2.250(2), O1–C1: 1.280(3), C1–N1:
1.323(3); O1–Mn–N5: 90.35(7), O1–Mn–N6: 94.50(7), O1–Mn–N2:
72.84(7), O1–Mn–N4: 102.15(7), O3–Mn–N6: 91.08(7), O3–Mn–N5:
96.19(7).
Fig. 8. 3d view of supramolecular connectivity in complex 4a via weak
H-bonds (C20–H20Bꢃ ꢃ ꢃO4).

C. Beghidja et al. / Inorganica Chimica Acta 358 (2005) 3881–3888
3887
Fig. 11. The temperature dependence of XT for complex 2.
with an angle C20–H20B–O4: 167ꢁ), and weak C–
Hꢃ ꢃ ꢃO (or S) H-bonds occurring between pseudo-trimer
chains (as draw in Fig. 8) and the MeOH solvent
molecules.
Fig. 9. ORTEP view of Mn(HL)2(Py)2 (4b). The hydrogen atoms
excepted for the phenol group have been omitted for clarity. Selected
˚
bond distances ([A]) and angles (ꢁ): Mn–O1: 2.093(1), Mn–N2:
2.252(2), Mn–N3: 2.308(2), O1–C1: 1.272(2), C1–N1: 1.329(2); O1–
Mn–N3: 88.80(6), N3–Mn–N2: 88.59(6), O1–Mn–N2: 74.45(5).
3.2.5. Complex [Mn(L1)2 (Py)2] (4b)
An ORTEP view of the molecular structure of com-
plex 4b in the crystal is depicted in Fig. 9.
The manganese atom is surmounted by two trans-
coordinated solvent molecules of pyridine (N3 and
N30) and two trans-coordinated HL ligands, coordi-
nated by the hydrazidate group (O1 and N2 atoms) of
the first ligand and the atoms O10 and N20 for the sec-
ond ligand. The intramolecular hydrogen-bond between
the nitrogen of the hydrazide group and the oxygen of
hydrazidate group (O1 and N2 atoms) of the first ligand
and the atoms O3 and N4 for the second ligand. The
surrounding appears to be octahedrally based, with an
irregular equatorial (O1–N6–O3–N4) plane. As in com-
plex 2, the intramolecular hydrogen-bond between the
nitrogen of the hydrazide group and the oxygen of phe-
˚
nol group (O2–H1ꢃ ꢃ ꢃN1: 2.554 A with an angle N1–H6–
˚
˚
phenol group (O2–H1ꢃ ꢃ ꢃN1: 2.593 A with an angle
O2: 149ꢁ, for the first ligand and O4–H2ꢃ ꢃ ꢃN3: 2.570 A
N1–H6–O2: 144ꢁ) is observed.
with an angle O4–H6–N3: 152ꢁ for the second ligand) is
observed.
As pointed out in Fig. 10(b), the crystal structure of
complex 4b is probably stabilized by C–Hꢃ ꢃ ꢃS [27–29]
intermolecular weak H-bonds between C12–H12ꢃ ꢃ ꢃS1
In this case, the crystal structure is probably stabi-
lized by both C–Hꢃ ꢃ ꢃO intermolecular weak hydrogen
˚
˚
(C12–S1: 3.58 A with an angle C12–H12–S1: 130ꢁ).
bonds [26] between C20–H20Bꢃ ꢃ ꢃO4 (C20–O4: 3.44 A
Fig. 10. 3d view of complex 4b showing pentamer connected via weak H–S bonds (a) and supramolecular arrangement in regular (bc) plane (b).

3888
C. Beghidja et al. / Inorganica Chimica Acta 358 (2005) 3881–3888
3.3. Magnetic measurements
Acknowledgements
´
To confirm the oxidation-state (+II) of the manga-
nese atom in these complexes, magnetic measurements
have been conducted on the first complex 2 obtained.
The thermal variation of the magnetic susceptibility is
reported in Fig. 11. Above 10 K, the magnetic suscepti-
bility obeys the Curie–Weiss law, fitted as:
The authors thank Dr. Andre DeCian for the help
during crystals selection and X-ray diffraction data col-
lection, and Alain Derory for the magnetic measure-
ments (IPCMS, Strasbourg).
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fðTÞ ¼ diaContrib þ CðT ꢁ hpÞ
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,
hp =
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4. Concluding remarks
In this work, we have demonstrated that the direct
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(H2L) with manganese (+II) acetate tetrahydrate and
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