Seven-coordinate Mn(II) and Co(II) complexes of the pentadentate ligand

2,6-diacetyl-4-carboxymethyl-pyridine bis(benzoylhydrazone): Synthesis,

crystal structure and magnetic properties
Frederik Schleife, Axel Rodenstein, Reinhard Kirmse, Berthold Kersting

Institut fr Anorganische Chemie, Universitt Leipzig, Johannisallee 29, 04103 Leipzig, Germany
a r t i c l e i n f o
Article history:
Available online 4 March 2011
Dedicated to Prof. Dr. Wolfgang Kaim on the
occasion of his 60th birthday
Keywords:
Benzoylhydrazones
Pentagonalbipyramidal complexes
Manganese
Cobalt
Crystal structure
Magnetic properties
a b s t r a c t
The metal complexation properties of a functionalized N
3
O
2
donor ligand H
2
L
2
, where H
2
L
2
stands for 2,6-
diacetyl-4-carboxymethyl-pyridine bis(benzoylhydrazone), are investigated by structural and spectro-
scopic (IR, ESI-MS and EPR) characterization of its Mn(II) and Co(II) complexes. The ligand H
2
L
2
is
observed to react essentially in the same fashion as its unmodied parent H
2
L
1
producing mixed-ligand
[M(H
2
L
2
)(Cl
2
)] complexes (M = Mn
II
(1), Co
II
(3)) upon treatment with MCl
2
. Complexes [M(HL
2
)(H
2
O)
(EtOH)]BPh
4
(M = Mn 2, M = Co 4), incorporating the supporting ligand in the partially deprotonated form
(HL
2
)

, are formed by salt elimination of the [M(H

2
L
2
)(Cl
2
)] compounds with NaBPh
4
. Compounds 2 and 4
are isostructural featuring distorted pentagonalbipyramidal coordinated Mn
II
and Co
II
ions, with the
H
2
O and EtOH ligands bound in axial positions. Intermolecular hydrogen bonding interactions of the type
MOH
2
OM involving the H
2
O ligands and the carbonyl functions of the supporting ligand assembles
the complexes into dimers. Temperature-dependent magnetic susceptibility measurements (2300 K)
show a substantially paramagnetic Curie behavior for the Mn
2+
compound (2) inuenced by zero-eld
splitting and signicant orbital angular momentum contribution for 4 (high-spin Co
II
). The exchange cou-
pling across the Mn
II
OH
2
OMn
II
bridges in 2 was found to be less than 0.1 cm
1
, suggesting that no
signicant intradimer exchange coupling occurs via this path.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The coordination chemistry of 2,6-diacetylpyridine bis(ben-
zoylhydrazone) H
2
L
1
[1] and its functionalized derivatives [2] has
been extensively investigated over the years owing to the fact that
such ligands support seven-coordinate complexes [310], are of
use in analytical chemistry and exhibit pharmacological activity
[1113]. The 2,6-diacetylpyridine bis(benzoylhydrazones) repre-
sent relatively rigid N
3
O
2
-donor ligands, generally binding in a
more or less distorted planar (pentagonal) fashion via the two car-
bonyl oxygen, the pyridine and the two hydrazone nitrogen atoms,
thereby providing the basis of a pentagonalbipyramidal coordina-
tion polyhedron. In some cases, however, the N
3
O
2
ligands wrap
around metal ions in a non-planar fashion [5,1417]. Given the
acidity of the benzoylhydrazone functions it is also not surprising
that the ligands can be present in protonated (H
2
L
1
) [1820],
deprotonated (L
1
)
2
and partially protonated forms (HL
1
)

[2123].
N
R
N N
NH HN
O O
H
2
L
1
(R = H)
H
2
L
2
(R = CO
2
CH
3
)
H
2
L
3
(R = CO
2
H)
As a consequence, several seven-coordinate complexes have
now been synthesized and structurally characterized. Most com-
plexes contain divalent 3d metal ions [2427], but some lantha-
nide [19,28,29], main group [12], 4d, and 5d elements [16,30]
form seven-coordinate complexes with H
2
L
1
equally well. The axial
coligands L
/
in these complexes are quite diverse and include H
2
O
[14,31], Cl

[19], NO
3

[6], CH
3
OH [27], Ph

[12] to name but a few.

As part of our studies into the construction of higher nuclearity
complexes [3235], we became interested in the use of 2,6-diace-
tylpyridine bis(benzoylhydrazone) complexes of the type
[ML
3
(L
/
)
2
] as coordinatively unsaturated metalloligands. Hence, it
was necessary to install an additional donor function into the
0020-1693/$ - see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2011.02.064

Corresponding author.
E-mail address: b.kersting@uni-leipzig.de (B. Kersting).
Inorganica Chimica Acta 374 (2011) 521527
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j our nal homepage: www. el sevi er . com/ l ocat e/ i ca
ligand framework of H
2
L
1
. We selected the derivative H
2
L
3
bearing
a carboxylate function in para-position of the pyridine ring. Our
rst efforts afforded two mononuclear Mn
II
and Co
II
complexes of
the proligand H
2
L
2
. Their preparation, spectroscopic properties
(IR, MS and EPR), X-ray crystal structures and magnetic properties
are reported herein.
2. Experimental
2.1. Materials and methods
Benzohydrazide was purchased from Alfa Aesar, cobalt(II) chlo-
ride hexahydrate and manganese(II) chloride tetrahydrate from
Merck. Methyl-2,6-diacetylisonicotinate was prepared according
to literature procedure [36]. All solvents used were of reagent
grade and obtained from Merck. Melting points were determined
with a Barnstead Electrothermal IA9100 instrument in open glass
capillaries and are uncorrected. IR spectra were recorded as KBr
pellets on a Bruker TENSOR 27 FT-IR-spectrometer. Elemental anal-
yses were carried out with a VARIO EL elemental analyzer. ESI-MS
experiments were performed with a 7 T APEX II from Bruker Dal-
tronics. NMR measurements were taken on a Bruker AVANCE
400 MHz spectrometer at room temperature. Variable temperature
magnetic susceptibility measurements were measured using a
Quantum Design MPMS XL-7 SQUID magnetometer in the temper-
ature range from 2 to 300 K at eld strengths of 1 T. Background
corrections for the sample holder assembly and diamagnetic com-
ponents of the complexes were applied. The data were processed
and analyzed with the program julX [37]. EPR spectra were re-
corded with an ESP 300E (BRUKER) EPR spectrometer at X-band
in the temperature range 5 _ T _ 20 K.
2.2. X-ray crystal structure determinations
Parameters of the crystal data collections and renements of
[Mn(HL
2
)(H
2
O)(EtOH)]BPh
4
EtOH (2) and [Co(HL
2
)(H
2
O)(EtOH)]
BPh
4
3EtOH (4) are summarized in Table 1. Diffraction-quality
crystals were grown as described below. The data were collected
on a STOE IPDS-1T diffractometer at 213 K using graphite-mono-
chromated Mo Ka radiation (0.71073 ). The intensity data were
processed with the program STOE X-AREA. The structures were
solved by direct methods [38] using the program SHELXS-97 and
rened by full-matrix least-squares on the basis of all data against
F
2
using the program SHELXL-97 [39]. Drawings were produced
with DIAMOND 3 [40]. The H atoms of the coordinated water
(H5A and H5B) and ethanol (H6A) molecules and the hydrazide
nitrogen atoms (H3A in 2 and H5C in 4) were located from nal dif-
ference Fourier maps, and were rened as riding atoms. All other H
atoms were placed at calculated positions and rened as riding
atoms with isotropic displacement parameters. In the case of the
cobalt complex 4 the EtOH ligand was indeed found disordered
over two positions. A split atom model has been used to account
for this disorder using the PART instruction implemented in the
SHELXTL software package. These site occupancies were found to
be 0.62 and 0.38 for the two orientations.
2.3. Synthesis
2.3.1. Synthesis of the ligand H
2
L
2
A solution of methyl-2,6-diacetylisonicotinate (0.885 g,
4.00 mmol) and benzohydrazide (1.089 g, 8.00 mmol) in 150 mL
methanol was reuxed for 20 h. The mixture was cooled to room
temperature and ltered. The resulting beige solid was washed
with cold methanol (50 mL), followed by diethyl ether
(2 40 mL) and dried in vacuum. Yield: 1.67 g, 91%. Mp: 269
270 C.
1
H NMR (DMSO-d
6
): d 2.57 (s, 6H), 3.97 (s, 3H), 7.55 (t,
J = 7.4 Hz, 4H), 7.63 (t, J = 7.4 Hz, 2H), 7.91 (m, 4H), 8.57 (m, 2H),
11.02 (m, 2H). Elemental Anal. Calc. for C
25
H
23
N
5
O
4
(457.48): C,
65.63; H, 5.07; N, 15.31. Found: C, 65.02; H, 5.08; N, 14.69%. Se-
lected IR bands (cm
1
): m 3186 (m, m
NH
), 3062 (w), 2953 (w),
1738 (s, m
C@O
, methyl ester), 1664 (vs, amide I), 1603 (sh), 1579
(s), 1558 (m), 1520 (m, amide II), 1438 (m), 1363 (s), 1257 (vs,
amide III), 1154 (s), 772 (s), 713 (s), 687 (s). ESI-MS (DMSO): m/z
456.0 [(HL
2
)

], 478.0 [(L
2
)
2
+ Na
+
].
2.3.2. [Mn(H
2
L
2
)(Cl)
2
]EtOH (1)
Solid MnCl
2
4H
2
O (100 mg, 0.50 mmol) was added to a suspen-
sion of H
2
L
2
(229 mg, 0.50 mmol) in 50 mL ethanol. After reuxing
for half an hour a clear solution resulted. The volume was reduced
till a yellow solid precipitated. This solid was isolated by ltration
and dried in a vacuum. Yield: 261 mg, 83%. Elemental Anal. Calc. for
C
27
H
29
Cl
2
MnN
5
O
5
(629.39): C, 51.52; H, 4.64; N, 11.13. Found: C,
50.26; H, 4.39; N, 10.94%. Selected IR bands (cm
1
): m 2954 (m),
1731 (s, m
C@O
, methyl ester), 1631 (vs, amide I), 1603 (sh), 1578
(s), 1523 (s, amide II), 1488 (m), 1437 (m), 1366 (m), 1286 (vs,
amide III) 1262 (sh), 1171 (s), 978 (w), 771 (w), 758 (w), 715
(m), 690 (m), 672 (m). ESI-MS
+
(MeOH): m/z 511.0 [Mn(HL
2
)]
+
,
533.0 [Mn(L
2
) + Na
+
], 547.1 [Mn(H
2
L
2
)Cl]
+
, 569.0
[Mn(HL
2
)Cl + Na
+
]; ESI-MS

(MeOH): m/z 545.1 [Mn(L

2
)Cl]

.
2.3.3. [Mn(HL
2
)(H
2
O)(EtOH)]BPh
4
(2)
A solution of sodium tetraphenylborate (96 mg, 0.28 mmol) in
ethanol (15 mL) was added dropwise to a solution of 1 (80 mg,
0.14 mmol) in ethanol (50 mL). The color turned from yellow to or-
ange while stirring at room temperature for 0.5 h. The solvent was
removed under reduced pressure to produce an orange solid. This
solid was recrystallized from ethanol yielding orange crystals suit-
able for X-ray crystallography. Selected IR bands (cm
1
): m 3056 (s),
3001 (m), 2984 (m), 1731 (s, m
C@O
, methyl ester), 1709 (s), 1630 (s,
Table 1
Crystal data and structure renement for [Mn(HL
2
)(H
2
O)(EtOH)]BPh
4
EtOH (2) and
[Co(HL
2
)(H
2
O)(EtOH)]BPh
4
3EtOH (4).
Compound C
53
H
56
BMnN
5
O
7
C
57
H
68
BCoN
5
O
9
Molecular mass 940.78 1036.90
Color orange red
T (K) 213(2) 213(2)
Crystal system monoclinic monoclinic
Space group P2
1
/n P2
1
/n
Z 4 4
a () 11.4079(8) 11.3405(6)
b () 35.044(3) 32.471(2)
c () 12.6351(8) 15.2285(8)
b () 100.510(5) 94.929(4)
V (
3
) 4966.5(6) 5586.9(6)
D
calc
(g cm
3
) 1.258 1.068
Absorption coefcient (mm
1
) 0.322 0.366
h () 2.0125.00 2.2025.00
Index ranges 13 6 h 6 13 13 6 h 6 12
41 6 k 6 41 38 6 k 6 38
14 6 l 6 15 18 6 l 6 15
F(0 0 0) 1980 1884
Radiation Mo Ka Mo Ka
k () 0.71073 0.71073
Measured reections 34 795 21 040
Independent reections 8282 9523
Observed reections [I > 2r(I)] 6118 7200
Number of parameters 625 587
Completeness of data (%) 94.6 96.7
R
int
0.0460 0.0259
Goodness-of-t 0.690 0.989
R, wR
2
[I > 2r(I)] 0.0310, 0.0728 0.0458, 0.1311
R, wR
2
(all data) 0.0498, 0.0867 0.0578, 0.1373
Residual e

density (e/
3
) 0.259/0.215 0.951/0.660
522 F. Schleife et al. / Inorganica Chimica Acta 374 (2011) 521527
amide I), 1580 (s), 1552 (s), 1510 (vs, amide II), 1483 (vs), 1427
(vs), 1354 (vs), 1303 (sh), 1262 (vs, amide III), 1172 (vs), 1068
(m), 1032 (m), 974 (m), 932 (w), 906 (w), 801 (w), 736 (vs, BPh
4

),
708 (vs, BPh
4

), 625 (s), 613 (s). ESI-MS (MeOH): m/z 511.0

[Mn(HL
2
)]
+
, 533.0 [Mn(L
2
) + Na
+
].
2.3.4. [Co(H
2
L
2
)(Cl)
2
]H
2
O (3)
A solution of CoCl
2
6H
2
O (72 mg, 0.3 mmol) in ethanol (15 mL)
was added to a suspension of H
2
L
2
(137 mg, 0.30 mmol) in ethanol
(25 mL). Upon reuxing for 1.5 h the green suspension turned into
a greenish-brown clear solution. By evaporating the solvent under
reduced pressure this compound precipitated as brown needles.
These needles were isolated by ltration and dried under vacuum.
Yield: 135 mg, 74%. Elemental Anal. Calc. for C
25
H
25
Cl
2
CoN
5
O
5
(605.34): C, 49.60; H, 4.16; N, 11.57. Found: C, 49.63; H, 4.15; N,
11.05%. Selected IR bands (cm
1
): m 2925 (w), 1728 (s, m
C@O
, methyl
ester), 1633 (vs, amide I), 1579 (s), 1523 (s, amide II), 1488 (m),
1437 (m), 1383 (m), 1289 (vs, amide III), 1262 (s), 1175 (s), 1137
(w), 1074 (w), 978 (w), 801 (w), 770 (w), 759 (w), 716 (m), 689
(m), 674 (m). ESI-MS (MeOH): m/z 515.10 [Co(HL
2
)]
+
, 551.08
[Co(H
2
L
2
)Cl]
+
, 1029.20 [Co
2
(HL
2
)(L
2
)]
+
.
2.3.5. [Co(HL
2
)(H
2
O)(EtOH)]BPh
4
(4)
Complex 3 (18.0 mg, 0.030 mmol) was dissolved in ethanol
(40 mL). Solid sodium tetraphenylborate (51.0 mg, 0.15 mmol)
was added. The solution was allowed to stir at room temperature
for 30 min, during which the color changed from orange to red.
After removing the solvent under reduced pressure the remaining
solid was recrystallized from ethanol yielding red crystals suitable
for X-ray crystallography. Selected IR bands (cm
- 1
): m 3056 (s),
3000 (m), 2985 (m), 1732 (s, m
C@O
, methyl ester), 1716 (sh), 1709
(s), 1633 (s, amide I), 1580 (s), 1553 (s), 1513 (vs, amide II), 1483
(vs), 1428 (vs), 1361 (vs), 1290 (s), 1266 (vs, amide III), 1175
(vs), 1149 (sh), 1070 (m), 1032 (m), 1001 (w), 976 (m), 909 (w),
801 (w), 769 (sh), 760 (sh), 736 (vs, BPh
4

), 708 (vs, BPh

4

), 625
(s), 613 (s). ESI-MS (MeOH): m/z 515.1 [Co(HL
2
)]
+
, 537.1
[Co(L
2
) + Na
+
].
3. Results and discussion
3.1. Synthesis and characterization
The synthesized compounds and their labels are shown in
Scheme 1. The bis(benzoylhydrazone) ligand H
2
L
2
was synthesized
by an imine condensation from methyl-2,6-diacetylisonicotinate
and benzohydrazide. Methyl-2,6-diacetylisonicotinate was pre-
pared from methyl isonicotinate, pyruvic acid, ammonium perox-
odisulfate and catalytic amounts of silver(I) nitrate in 0.4 M
sulfuric acid according to a literature procedure [36].
Adding MnCl
2
(H
2
O)
4
or CoCl
2
(H
2
O)
6
, respectively, to a suspen-
sion of the free ligand in ethanol provides the complexes
[Mn(H
2
L
2
)(Cl)
2
]EtOH (1) and [Co(H
2
L
2
)(Cl)
2
]H
2
O (3) with the sup-
porting ligand in the fully protonated form. These complexation
reactions appear to be not affected by the choice of supporting li-
gand, as one might expect. The carboxylated ligand H
2
L
2
reacts
essentially in the same fashion as H
2
L
1
producing mixed-ligand
[M(H
2
L
2
)(Cl
2
)] complexes with analogous structures in similar
good yields and reaction times [25]. The other two complexes of
this study, [M(HL
2
)(H
2
O)(EtOH)]BPh
4
(M = Mn 2, M = Co 4), with
the supporting ligand in the partially deprotonated form (HL
2
)

,
formed during salt elimination of the [M(H
2
L
2
)(Cl
2
)] compounds
with NaBPh
4
, the driving force for the deprotonation (and ligand
exchange) reaction being the low solubility of the products.
The new compounds gave satisfactory elemental analyses and
were further characterized by IR-spectroscopy, ESI mass spectrom-
etry, and in the case of 2 and 4 by X-ray crystallography. A compar-
ison of the infrared spectrum of the ligand with the spectra of the
transition metal complexes reveals characteristic shifts of the
absorptions of the coordinating moieties. The strong C@O absorp-
tion at 1664 cm
1
(amide I) in the ligand H
2
L
2
is shifted bathochro-
mically to 1631 cm
1
in the manganese complexes (1, 2) and to
1633 cm
1
in the cobalt complexes (3, 4). The CN absorption
(amide III), on the other hand, is shifted hypsochromically from
1257 to 1286 cm
1
and 1289 cm
1
in 1 and 3, respectively. Similar
IR shifts were recorded for Mn and Co complexes H
2
L
1
[25]. In
agreement with their formulation as complexes of fully protonated
(H
2
L
2
) and partially protonated ligands [(HL
2
)

], 14 show the
amide II vibration (NH-bending vibration) at -1520 cm
1
. The
IR spectra of the complexes 2 and 4 evidence the presence of the
tetraphenylborate counterion with typical very strong absorptions
at 736 and 708 cm
1
.
3.2. Description of the crystal structures
3.2.1. Description of the crystal structure of
[Mn(HL)(H
2
O)(EtOH)]BPh
4
EtOH (2)
The crystal structure of 2 comprises mononuclear [Mn(HL
2
)
(H
2
O)(EtOH)]
+
complex cations, tetraphenylborate anions and eth-
anol solvate molecules. Fig. 1 represents an ellipsoid plot of the
complex cation of 2. Selected bond lengths and angles are given
in Table 2. The manganese ion is seven-coordinated in a distorted
pentagonalbipyramidal fashion. The equatorial positions of the
coordination polyhedron are occupied by three N and two O donor
atoms from the supporting chelate ligand. The axial positions are
occupied by a water and an ethanol ligand. The Mn atom lies only
N
N N
O O
NH HN
O O
N
N N
O O
NH HN
O O
MCl
2
n H
2
O
M = Mn
II
,
Co
II
M
II
Cl Cl
N
N N
O O
N HN
O O
M
II
HOEt H
2
O
(BPh
4
)
-
NaBPh
4
EtOH EtOH
H
2
L
2
1 (M = Mn
II
)
3 (M = Co
II
)
2 (M = Mn
II
)
4 (M = Co
II
)
Scheme 1. Syntheses of compound 14 from H
2
L
2
.
F. Schleife et al. / Inorganica Chimica Acta 374 (2011) 521527 523
0.0336(2) above the best plane through the N
3
O
2
donor set (N1,
N2, N4, O3, O4) of the supporting ligand.
Charge considerations imply the presence of a mono-deproto-
nated supporting ligand deprotonated at N5 (assuming the pres-
ence of the singly deprotonated (HL
2
)

, one BPh
4

ion, and a
Mn
2+
ion). The presence of the mono-protonated supporting ligand
is reected in the different MnN2 (2.371(2) ) and MnN4
(2.263(2) ) and MnO3 (2.340(1) ) and MnO4 (2.254(1) )
bond distances. The bond lengths and angles are typical for se-
ven-coordinate Mn(II) complexes containing bis(hydrazone) li-
gands. The manganesepyridine nitrogen distance (MnN1
2.326(2) ), for example, is comparable to the Mnpy distance of
2.313(4) for the complex [Mn(H
2
L
1
)(OH
2
)Cl]Cl [where H
2
L
1
stands for non-deprotonated 2,6-diacetylpyridin bis(benzoylhyd-
razone)] reported by Lorenzini et al. [25]. The MnN
imine
bond
lengths in 2 are slightly longer than in the di-deprotonated manga-
nese complex of 2,6-bis(1-salicyloylhydrazonoethyl)pyridine
(H
2
daps) [2.280(6) and 2.292(5) ], reported by Bermejo et al.
[14]. Typical Mn
II
OH
2
distances in seven-coordinate structures
range from 2.136(2) to 2.258(4) [25,31]. In 2 the MnO
OH
2
dis-
tance is 2.206(1) (MnO5). The MnO
EtOH
distance in 2 is
2.215(2) (MnO6) and slightly shorter than in [Mn(H
2
daps)
(EtOH)(H
2
O)] complex (MnO
EtOH
= 2.227 ) [14].
The distortion from the ideal pentagonalbipyramidal geometry
is manifested by deviations of the bond angles from the ideal val-
ues. The largest deviations are 15 for O3MnO4 (89.14(5)) and
21 for the O5MnO6 bond angle (168.91(5)). The EtOH solvate
molecule is connected with the complex via a hydrogen bond
(O3H3a O7 2.43 ).
As can be seen in Fig. 2, the [Mn(HL
2
)(H
2
O)(EtOH)]
+
complex
cations are intermolecularly linked via four hydrogen bonds
involving the H
2
O ligands and the carbonyl oxygen atoms of the
hydrazone ligand of the adjacent complex. The hydrogen bonds
are of length 2.759(2) (O5 O3
/
) and 2.725(2) (O5 O4
/
),
resulting in a Mn Mn separation of 5.0306(5) . A similar situa-
tion has been observed in [Mn(H
2
daps)(EtOH)(H
2
O)] [14] and in
the Co
II
complex described below. The dimerization of the com-
plexes via hydrogen bonds also explains the presence of the two
different coligands in the axial positions, as it is energetically more
favorable to join the complexes via four OH
2
O than by two
EtOH O hydrogen bonding interactions.
3.2.2. Description of the crystal structure of
[Co(HL
2
)(H
2
O)(EtOH)]BPh
4
3EtOH (4)
The Co(II) 4 complex is isostructural with the Mn(II) complex 2.
Fig. 3 represents an ellipsoid plot of the [Co(HL
2
)(H
2
O)(EtOH)]
+
complex cation. Selected bond lengths and angles of 4 are given
in Table 3. The cobalt ion again is seven-coordinated through the
N
3
O
2
-donor set of the chelate ligand and two oxygen atoms of
the axial water and ethanol molecules. Like in 2, charge consider-
ations imply the presence of a mono-deprotonated supporting li-
gand deprotonated at N3 (assuming the presence of the singly
deprotonated (HL
2
)

, one BPh
4

ion, and a Co
2+
ion). The bond
lengths in 4 are all smaller than their corresponding ones in 2,
attributed to the smaller ionic radius of the cobalt(II) ion (Co
II
:
0.885 compared to Mn
II
: 0.97 ) [41]. This dependence of metri-
cal parameters upon metal ion radius appears in several other fea-
tures of the structures. For instance, there is a consistent decrease
in the deviations of the bond angles from the ideal values upon
going from 2 to 4. Thus, the coordination polyhedron in cobalt(II)
complex 4 is more regular than in the manganese compound 2.
Fig. 1. Ellipsoid plot of the molecular structure of the [Mn(HL
2
)(H
2
O)(EtOH)]
+
cation in crystals of 2. Displacement ellipsoids are drawn at the 50% probability
level.
Table 2
Selected bond lengths () and angles () in 2.
MnO3 2.340(1) C8N2 1.299(3)
MnN2 2.371(2) C17N4 1.294(2)
MnN1 2.326(2) C10N3 1.358(3)
MnN4 2.263(2) C19N5 1.329(3)
MnO4 2.254(1) C10O3 1.247(2)
MnO5 2.206(1) C19O4 1.292(2)
MnO6 2.215(2) N2N3 1.389(2)
N4N5 1.385(2)
O5MnO3 82.87(6) O6MnN1 98.38(6)
O5MnN2 85.47(6) O6MnN4 90.04(6)
O5MnN1 90.87(6) O6MnO4 88.33(6)
O5MnN4 99.09(6) O3MnN2 66.59(6)
O5MnO4 89.01(6) N2MnN1 66.67(6)
O5MnO6 168.87(6) N1MnN4 68.52(6)
O6MnO3 86.28(6) N4MnO4 69.53(6)
O6MnN2 92.50(6) O4MnO3 89.97(5)
Fig. 2. Intermolecular hydrogen bonding interactions between two molecules of
[Mn(HL
2
)(H
2
O)(EtOH)]
+
in the solid state. Displacement ellipsoids are drawn at the
50% probability level. The hydrogen bonds are shown as dashed lines. Symmetry
codes used to generate equivalent atoms: 1 x, 1 y, 1 z (
/
).
524 F. Schleife et al. / Inorganica Chimica Acta 374 (2011) 521527
The distances between the cobalt ion and the oxygen donor
atoms of the chelate ligand resemble those in other seven-coordi-
nated Co(II) bis(benzoylhydrazone) complexes (CoO3 2.163(2)
and CoO4 2.225(2) ) [6,20,24]. The same holds for the CoN
bond lengths ranging from 2.155(2) (CoN2) to 2.255(2)
(CoN4). As mentioned above the distortion fromthe ideal pentag-
onalbipyramidal geometry is less pronounced than in 2. The bond
angles differ only slightly from the ideal 72 angle [from 69.22(6)
(N4CoO4) to 77.67(6) (O3CoO4)], the ideal 90 angle [from
87.73(6) (O5CoN4) to 94.68(7) (O6CoO3)] and the ideal
180 angle [O5CoO6 177.26(7)].
The [Co(HL
2
)(H
2
O)(EtOH)]
+
complex cations are intermolecu-
larly linked via four hydrogen bonds involving the H
2
O ligands
and the carbonyl oxygen atoms of the hydrazone ligand of the
adjacent complex as in 2. The hydrogen bonds are of length
2.687(2) (O5 O3
/
) and 2.836(3) (O5 O4
/
). Two of the three
EtOH molecules are connected by OH O and OH N hydrogen
bonds with the EtOH coligand and the deprotonated nitrogen atom
of the supporting ligand (i.e. O6H6 O8 2.697 , O8H8 O9
2.790 , O9H9 N3 2.872 ). The third EtOH solvate molecule is
also involved in a hydrogen bonding interaction with the N5H5
group of the supporting ligand (N5H5 O7 2.829 ). The cobalt
ions are separated by 5.0943(5) .
3.3. Magnetic properties
3.3.1. SQUID measurements
Fig. 4 shows a plot of the temperature dependence of the effec-
tive magnetic moment l
eff
(per dimer) of the manganese complex
2. The data were measured over the range 2300 K in an applied
external magnetic eld of B = 1.0 T. At room temperature the value
of l
eff
per dimer of 2 is 8.25 l
B
(l
eff
= 5.84 l
B
per mononuclear
complex, which almost represents the spin-only value of
5.92 l
B
). With decreasing temperature the effective magnetic mo-
ment remains nearly constant down to 40 K. On lowering the tem-
perature further l
eff
decreases slightly to 7.57 l
B
at 2 K. This
decrease can be attributed to saturation effects, to the zero-eld
splitting of Mn(II) [42], or to a weak antiferromagnetic coupling
of the two high-spin Mn
II
ions in the dimeric, hydrogen-bonded
units of 2. Note that the OH O hydrogen bridges provide the
only plausible pathway for such a magnetic exchange interaction.
It should also be noted that a maximum in the v versus T curve
(not shown) cannot be detected.
In order to see whether an exchange interaction occurs in the
hydrogen-bonded units the susceptibility data were analyzed in
terms of the appropriate spin Hamiltonian in Eq. (1) [43], which
takes into account the isotropic HeisenbergDiracvan Vleck ex-
change, the single-ion zero-eld splitting and the single-ion Zee-
man interactions. The intramolecular exchange constant J is
dened for the isotropic HeisenbergDiracvan Vleck (HDvV) ex-
change Hamiltonian (H = 2JS
1
S
2
) (with S
1
= S
2
=
5
/
2
) for dinuclear
Mn(II) complexes [44]. The resulting Hamiltonian was diagonal-
ized numerically to obtain the magnetic susceptibility which was
used to t the v
M
T magnetic data for the manganese(II) com-
pounds [37]. Under these conditions the best t yields g = 1.97
and D = 0.61 cm
1
(or 0.61 cm
1
) [45]. The values are not
unusual for seven-coordinate Mn(II) compounds [31,46]. The
exchange coupling across the OH
2
O bridges was found to be
0.018 cm
1
, suggesting that no signicant intradimer exchange
coupling occurs in 2.
H = 2JS
1
S
2

X
2
i=1
D
i
S
_
2
zi
1=3(S
i
(S
i
1)) g
i
l
B
S
is
B
s

(s = x; y; z) (1)
Fig. 3. Ellipsoid plot of the molecular structure of the [Co(HL
2
)(H
2
O)(EtOH)]
+
cation
in crystals of 4. Only one orientation of the disordered EtOH ligand us shown
Displacement ellipsoids are drawn at the 50% probability level.
Table 3
Selected bond lengths () and angles () for 4.
CoO3 2.163(2) C8N2 1.295(3)
CoN2 2.155(2) C17N4 1.297(3)
CoN1 2.187(2) C10N3 1.334(3)
CoN4 2.255(2) C19N5 1.361(3)
CoO4 2.225(2) C10O3 1.280(3)
CoO5 2.146(2) C19O4 1.251(3)
CoO6 2.144(2) N2N3 1.390(3)
N4N5 1.379(3)
O5CoO3 88.05(6) O6CoN1 89.66(8)
O5CoN2 92.43(7) O6CoN4 89.82(7)
O5CoN1 88.33(7) O6CoO4 90.74(7)
O5CoN4 87.73(6) O3CoN2 71.70(6)
O5CoO4 89.56(7) N2CoN1 71.73(6)
O5CoO6 177.26(7) N1CoN4 69.84(6)
O6CoO3 94.68(7) N4CoO4 69.22(6)
O6CoN2 88.71(8) O4CoO3 77.67(6)
Fig. 4. l
eff
vs. T plot for dimeric units of 2. The solid line represents the best t to
the experimental data with J = 0.018 cm
1
, g = 1.97 and D = 0.61 cm
1
.
F. Schleife et al. / Inorganica Chimica Acta 374 (2011) 521527 525
There has been much interest in magnetic exchange interac-
tions via hydrogen bonds due to their important role in biological
processes [47]. The exchange interactions between metal ions
bridged by hydrogen bonds are typically very small (|J| - <1 cm
1
)
[48]. Our observation of negligible exchange interactions in 2 is in
good agreement with the reported trend.
Fig. 5 displays the temperature dependencies of l
eff
for the co-
balt(II) complex 4. The effective magnetic moment, l
eff
, has a value
of 4.37 l
B
at 295 K which is signicantly higher than the theoreti-
cal spin-only value of 3.88 l
B
for an S = 3/2 ion (g = 2.00). Decreas-
ing the temperature leads to a steadily decrease of l
eff
to a value of
3.20 l
B
at 2 K. This is indicative of a strong orbital-angular momen-
tum contribution to the magnetic moment which is typical for
high-spin cobalt(II) ions [49]. For lower temperatures it decreases
faster to 3.16 l
B
(2 K), due to the zero-eld splitting and the tem-
perature dependence of the effective magnetic moment.
The application of the spin-Hamiltonian approach is not appro-
priate for metal ions with a T ground state (in O
h
symmetry) due to
the rst-order orbital-angular momentum and in-state spinorbit
coupling [50]. However, the local symmetry (approximate C
S
) splits
the
4
T
1g
into orbitally non-degenerate states. This splitting affects a
quenching of the rst-order orbital-angular momentum. If this
splitting is large as compared to the spinorbit coupling, the
spinorbit coupling of excited states into the ground state can be
treated by a second-order perturbation. The resulting orbital-angu-
lar momentum contribution may then be treated phenomenologi-
cally by the zero-eld splitting in the spin-Hamiltonian approach
[51]. The actual energy splittings imposed by symmetry reduction
and by spinorbit coupling are difcult to evaluate. Thus, some
controversy exists in the literature for the applicability of the
spin-Hamiltonian approach for cobalt(II) complexes with lower
then cubic coordination environments [50,52]. However, a recent
review summarized a large number of applications of the spin-
Hamiltonian approach on cobalt(II) complexes [53]. Thus, the
least-square t to the experimental data for 4 was calculated as
above for the manganese complex 2, but neglecting the isotropic
HeisenbergDiracvan Vleck exchange. The g (isotropic average)
and D values are 2.25 and 27.65 cm
1
, respectively.
3.3.2. EPR spectroscopy
The high-spin pentagonalbipyramidal Co(II) complex 4 was
studied in CHCl
3
/EtOH (1:1) solutions (10
2
M) by X-band EPR.
Due to short spinlattice relaxation times low temperatures are re-
quired. Fig. 6 shows the experimentally obtained EPR spectrum to-
gether with its simulation which has been done using the program
package EasySpin [54].
The spectrum is axial symmetric and shows that the resonance
occurs in a Kramers doublet. Therefore, it can be analyzed by the
following spin Hamiltonian (2) with an effective spin of S
/
= .
The rst term stands for the electron Zeeman interaction. The sec-
ond term represents the nuclear hyperne interaction with the
59
Co nucleus (I = 7/2).
H
sp
=
X
(lg
/
i
B
i
S
/
i
A
/
i
S
/
i
I
/
i
); i = 1; 2; 3 (2)
The following principal values of g and the
59
Co hyperne
tensor A were obtained from the spectrum (T = 8 K):
g
/
1
= g
/
2
= 4.532, g
/
3
= 1.994, g
av
= 3.686, A
/
1
~ A
/
2
< 40 10
4
cm
1
,
A
/
3
= 117 10
4
cm
1
and A
av
~ 66 10
4
cm
1
(exper. errors:
g
/
i
0.003, A
/
3
2 10
4
cm
1
). A comparison of the principal
values of g and A found for 4 with those typically observed for
octahedral high-spin Co(II) complexes [55,56] shows some striking
differences:
(i) The anisotropy of the g tensor components of 4 is noticeably
smaller than that observed for octahedral Co(II) complexes
for which the g tensor components are observed in a range
from 1.5 to 8. Also, the average g value g
av
= 3.686 estimated
for complex 4 is smaller than those usually found for octahe-
dral Co(II) complexes. For the latter ones g
av
values in the
range of 44.3 are observed. Nevertheless, the g
av
value devi-
ates much from g = 2 indicating a large orbital contribution
to the g values.
(ii) In the powder EPR spectra of octahedral high-spin Co(II)
complexes the
59
Co hyperne splitting is usually resolved
only for the low-eld signal (largest g value). In contrast,
the pentagonalbipyramidal Co(II) complex 4 gives rise to
a well-resolved
59
Co hyperne structure octet for the high-
eld transition (lowest g value). This resembles to the spec-
tra of fourfold coordinated planar low-spin Co(II) complexes
with axially coordinated bases [57]. However, in these cases
the g anisotropy is much smaller than in our case.
4. Conclusions
In summary, a series of novel manganese(II) and cobalt(II)
complexes supported by the pentadentate ligand
Fig. 5. Temperature dependence of the effective magnetic moment, l
eff
, for 4 at
1.0 T. The solid line is a t to the experimental data using the spin-Hamiltonian (1)
with D = 27 cm
1
and g = 2.25.
Fig. 6. X-band EPR spectrum of 4 in CHCl
3
/EtOH (1:1) at T = 8 K.
526 F. Schleife et al. / Inorganica Chimica Acta 374 (2011) 521527
2,6-diacetyl-4-carboxymethyl-pyridine bis(benzoylhydrazone)
have been synthesized and characterized, namely [Mn(H
2
L
2
)(Cl
2
)]
(1), [Mn(HL
2
)(H
2
O)(EtOH)]BPh
4
(2), [Co(H
2
L
2
)(Cl
2
)] (3), and
[Co(HL
2
)(H
2
O)(EtOH)]BPh
4
(4). The crystal structures of 2 and 4
reveal distorted pentagonalbipyramidal coordinated Mn
II
and
Co
II
ions, with the H
2
O and EtOH ligands bound in axial posi-
tions. Intermolecular hydrogen bonding interactions of the type
MOH
2
OM involving the H
2
O ligands and the carbonyl
functions of the supporting ligand assembles the complexes into
dimers. Temperature-dependent magnetic susceptibility mea-
surements (2300 K) show a substantially paramagnetic Curie
behavior for the Mn
2+
compound (2) inuenced by zero-eld
splitting and signicant orbital angular momentum contribution
for 4 (high-spin Co
II
). The exchange coupling across the Mn
II

OH
2
OMn
II
bridges in 2 was found to be less than 0.1 cm
1
,
suggesting that no signicant intradimer exchange coupling
occurs via this path. Future work is focused on the hydrolysis
of the ester function in the periphery of the complexes.
Acknowledgements
We are thankful to Prof. Dr. H. Krautscheid for providing facili-
ties for X-ray crystallographic measurements. We thank Daniel
Lssig and Jrg Lincke for X-ray crystallographic measurements
and Jochen Lach for help with recieding magnetic susceptibility
data. This work was supported by the Deutsche Forschungsgeme-
inschaft (DFG FOR-1194, Towards Molecular Spintronics).
Appendix A. Supplementary material
CCDC 813616 and 813617 contain the supplementary crystallo-
graphic data for 2 and 4. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
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