Manganese(III) complexes with tetradentate (N2O2) Schiff bases and dicyanamide

Article abstract of DOI:10.1134/S107032841302005X

New Mn(III) complexes with Schiff bases and dicyanamide are synthesized: [Mn(Salpn)N(CN)₂] _n (two polymorphous modifications, Ia and Ib), {[Mn(5-BrSalen)N(CN)₂] · CH₃OH} _n (II), and [Mn(3-MeOSalen)N(CN)₂(H₂O)] (III), where SalpnH₂ = N,N′-bis(salicylidene)-1,3-diaminopropane, 5-BrSalenH₂ = N,N′-bis(5-bromosalicylidene)-1,2-diaminoethane, and 3-MeOSalenH₂ = N,N′-bis(3-methoxysalicylidene)-1,2- diaminoethane. Complexes Ia, Ib, and II have the polymer structure in which the dicyanamide anion binds the paramagnetic Mn(III) complexes with the Schiff bases into one-dimensional chains. Unlike them, in complex III the monomer units containing water and the dicyanamide anion as terminal ligands form dimers due to hydrogen bonds. The study of the magnetic properties of complexes Ia and II shows a weak antiferromagnetic interaction between the Mn³⁺ ions through the dicyanamide bridges in these complexes.

Full text of DOI:10.1134/S107032841302005X

ISSN 1070ꢀ3284, Russian Journal of Coordination Chemistry, 2013, Vol. 39, No. 2, pp. 201–208. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © V.A. Kopotkov, S.V. Simonov, A.V. Sadakov, E.B. Yagubskii, 2013, published in Koordinatsionnaya Khimiya, 2013, Vol. 39, No. 2, pp. 112–119.
Manganese(III) Complexes with Tetradentate (N2O2) Schiff Bases
and Dicyanamide
V. A. Kopotkova, *, S. V. Simonovb, A. V. Sadakovc, and E. B. Yagubskiia, *
a Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia
b Institute of Solid State Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia
c Lebedev Physical Institute, Russian Academy of Sciences, Leninskii pr. 53, Moscow, 119991 Russia
*eꢀmail: slavaoven@mail.ru; yagubski@icp.ac.ru
Received May 14, 2012
Abstract—New Mn(III) complexes with Schiff bases and dicyanamide are synthesized:
[Mn(Salpn)N(CN)2]n (two polymorphous modifications, Ia and Ib), {[Mn(5ꢀBrSalen)N(CN)2] · CH3OH}n
(
II), and [Mn(3ꢀMeOSalen)N(CN)2(H2O)] (III), where SalpnH2 = N,N'ꢀbis(salicylidene)ꢀ1,3ꢀdiaminoꢀ
propane, 5ꢀBrSalenH2 = N,N'ꢀbis(5ꢀbromosalicylidene)ꢀ1,2ꢀdiaminoethane, and 3ꢀMeOSalenH2 = N,N'ꢀ
bis(3ꢀmethoxysalicylidene)ꢀ1,2ꢀdiaminoethane. Complexes Ia Ib, and II have the polymer structure in
,
which the dicyanamide anion binds the paramagnetic Mn(III) complexes with the Schiff bases into oneꢀ
dimensional chains. Unlike them, in complex III the monomer units containing water and the dicyanamide
anion as terminal ligands form dimers due to hydrogen bonds. The study of the magnetic properties of comꢀ
plexes Ia and II shows a weak antiferromagnetic interaction between the Mn3+ ions through the dicyanamide
bridges in these complexes.
DOI: 10.1134/S107032841302005X
Manganese with the charge +3 forms highꢀspin features of the Schiff base, the nature of the terminal
= 2) complexes with tetradentate (N2O2) Schiff ligands, and the solvent, the complexes can exist in the
(S
bases of the N,N'ꢀbis(salicylidene)ꢀ1,2ꢀdiaminoethꢀ monomer paramagnetic or dimeric antiferromagnetic
ane (SalenH2, Scheme 1) type. Depending on steric and ferromagnetic forms (Scheme 2) [1–7].
R
R
R'
H
H
H
R''
H Salen
H Salpn
Br 5ꢀBrSalen
H 3ꢀMeOSalen
H
C
H
C
(CH2)2
R''
R''
N
N
(CH2)3
(CH2)3
(CH2)2
ᮎ
–
O
ᮎ
–
O
MeO
R'
R'
Scheme 1.
paramagnetic bridging groups [8–20]. For these purꢀ
poses, pseudohalide anions N3, CN, NCS, and NCO
are widely used as bridging ligands [8–14]. At the same
time, the polydentate dicyanamide anion [N(CN)2]–
(Dca) forming polymer structures of different dimenꢀ
sionalities [21–26] was poorly used as an apical ligand
in the Mn(III) complexes with Schiff bases. Only two
published works are known that describe three coordiꢀ
nation polymer Mn complexes with Schiff bases conꢀ
taining[N(CN)2]– as bridging ligands [27, 28]. In this
work we synthesized new Mn(III) complexes with
Schiff bases (Salpn, 5ꢀBrSalen, and 3ꢀMeOSalen;
Scheme 1) and dicyanamide: [Mn(Salpn)N(CN)2]n
(two polymorphous modification Ia and Ib), {[Mn(5ꢀ
2+
OH2
N
N
O
⊕
Mn
OH2
O
N
N
O
O
O
Mn
N
O
Mn
N
OH2
OH2
Scheme 2.
These complexes are building blocks for the prepaꢀ
ration of monoꢀ and heterometallic magnetic materiꢀ
als of different dimensionalities by the replacement in BrSalen)N(CN)2]
⋅
CH3OH}n
(
II), and [[Mn(3ꢀ
them of neutral terminal ligands by diamagnetic or MeOSalen)N(CN)2(H2O)]
(III). The syntheses and
201

202
KOPOTKOV et al.
crystal structures of these complexes and the magnetic
For C19H16N5O2Mn
properties of complexes Ia and II are described.
anal. calcd. (%): C, 56.86;
H, 3.99;
H, 3.88;
N, 17.45.
N, 17.40.
Found (%):
C, 57.04;
EXPERIMENTAL
IR,
ν
, cm–1: 2228, 2159
ν(C≡N); 1608 ν(C=N).
The following reagents were used for the syntheses of
the complexes: Mn(II) acetate tetrahydrate (
≥
99%
,
Synthesis of complex Ib was carried out according
Fluka), Mn(III) acetate dihydrate (97%, Aldrich), N,N'ꢀ to method (A) using Mn[N(CN)2]2 in a methanolic
bis(salicylidene)ꢀ1,3ꢀdiaminopropane (SalpnH2, 99%), solution as a precursor of the dicyanamide anion. The
2ꢀhydroxyꢀ5ꢀbromobenzaldehyde (98%), 2ꢀhydroxyꢀ3ꢀ yield was 65%.
IR, ν ν(C≡N); 1610 ν(C=N).
, cm–1: 2226, 2159
methoxybenzaldehyde (98%), ethylenediamide (99%,
SigmaꢀAldrich), and methanol (reagent grade). Comꢀ
plex [Mn(Salpn)(H2O)](ClO4) and simple and complex
Mn(II) and Ni(II) dicyanamides were synthesized
according to described procedures [1, 29, 30]. IR spectra
were recorded on a Varian 3100 FTꢀIR instrument in the
range from 600 to 4000 cm–1 using polycrystalline samꢀ
ples. Absorption bands in the IR spectra were assigned on
the basis of literature data [31]. Elemental analyses for C,
H, and N were carried out on a Vario MICRO Cube anaꢀ
lyzer. Magnetic measurements were carried out on an
MPMSꢀ5ꢀXL SQUID magnetometer (Quantum
Design) in a field of 100 Oe. The diamagnetic contribuꢀ
tions from the sample holder and internal diamagnetism
of the complexes calculated using Pascal’s tables were
taken into account in the calculation of the paramagnetic
Synthesis of complex II. Method (B). A dry mixture
of manganese(II) acetate tetrahydrate (0.123 g,
0.5 mmol) and 2ꢀhydroxyꢀ5ꢀbromobenzaldehyde
(0.201 g, 1 mmol) was dissolved in methanol (20 mL)
with stirring for 10–15 min, and then ethylenediamine
(0.03 g, 0.5 mmol) was poured dropwise. The reaction
mixture was heated to 50°С and stirred for 30–40 min,
then (Bu4N)Ni[N(CN)2]3 (0.244 g, 0.5 mmol) in
methanol (10 mL) was added, and the mixture was
stirred for 30–40 min more. Then water (20 mL) was
poured to the hot solution, and the resulting solution
was filtered. The mother liquor was left to evaporate
slowly at ambient temperature for a week. Dark brown
crystals that precipitated were washed with a miniꢀ
mum amount of water and dried in vacuo. The yield
was 48%.
component of magnetic susceptibility χ.
Synthesis of complex Ia. Method (A). A solution of
Schiff base SalpnH2 (0.352 g, 1.25 mmol) in methanol
(10 mL) was added to a solution of Mn(III) acetate
dihydrate (0.335 g, 1.25 mmol) in methanol (10 mL).
For C19H16N5O3 Br2Mn
anal. calcd. (%): C, 39.51;
Found (%): C, 39.49;
H, 2.77;
H, 2.48;
N, 12.13.
N, 12.02.
The mixture was heated to 50°С and stirred for 30–
40 min, then (Bu4N)Mn[N(CN)2]3 (0.309 g,
0.625 mmol) in methanol (10 mL) was added, and the
mixture was stirred for 30–40 min more. Then water
(20 mL) was poured to the hot solution, and the soluꢀ
tion was filtered. The mother liquor was left to evapoꢀ
rate slowly at ambient temperature for a week. Dark
brown crystals that precipitated were washed with a
minimum amount of water and dried in vacuo. The
yield was 72%.
IR,
ν
, cm–1: 2226, 2159
ν
(C
≡
N); 1610 ν(C=N).
Synthesis of complex III was similar to that of comꢀ
plex II (method C) using 2ꢀhydroxyꢀ3ꢀmethoxybenzꢀ
aldehyde instead of 2ꢀhydroxyꢀ5ꢀbromobenzaldeꢀ
hyde. The yield was 68%.
For C20H20N5O5Mn
anal. calcd. (%): C, 51.61;
Found (%): C, 51.72;
H, 4.30;
H, 4.51;
N, 15.05.
N, 14.97.
For C19H16N5O2Mn
anal. calcd. (%): C, 56.86;
Found (%): C, 56.58;
H, 3.99;
H, 3.89;
N, 17.45.
N, 17.31.
IR,
ν
, cm–1: 2251, 2144
ν
(C
≡
N); 1622 ν(C=N).
Complex III was synthesized by the same method
using Ni(Dca)2 in a methanolic solution as a precursor
of the dicyanamide anion. The yield was 65%.
IR,
ν
, cm–1: 2228, 2158
ν
(C≡
N); 1609 ν(C=N).
Method (B). A solution of tetraphenylphosphoꢀ
nium dicyanamide (Ph4P)[N(CN2)] (0.091 g,
0.213 mmol) in methanol (10 mL) was added to a
solution of complex [Mn(Salpn)(H2O)](ClO4) (0.1 g,
0.213 mmol) in methanol (20 mL). The mixture was
For C20H20N5O5Mn
anal. calcd. (%): C, 51.61;
Found (%): C, 51.76;
H, 4.30;
H, 4.52;
N, 15.05.
N, 14.99.
heated to 50°С and stirred for 30–40 min, then hot
water (20 mL) was added, and the solution was filꢀ
tered. The mother liquor was left to evaporate at ambiꢀ
IR,
Xꢀray diffraction analysis. Unit cell parameters
ν ν(C≡N); 1622 ν(C=N).
, cm–1: 2251, 2145
ent temperature for a week. Dark brown crystals that were determined for single crystals of all four comꢀ
precipitated were washed with a minimum amount of plexes, and threeꢀdimensional arrays of reflection
water and dried in vacuo. The yield was 63%.
intensities were collected on a fourꢀcircle diffractoꢀ
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MANGANESE(III) COMPLEXES WITH TETRADENTATE
203
Table 1. Main crystallographic data and refinement parameters for structures Ia
,
Ib,
II, and III
Value
Parameter
Ia
Ib
II
III
Crystal system
FW
Monoclinic
401.31
Monoclinic
401.31
Monoclinic
577.13
Monoclinic
465.35
Space group;
Z
P
21/
n
; 4
P21/
c
; 4
P
21/
c; 4
P21/c; 4
a
, Å
, Å
9.308(1)
7.2102(8)
15.177(1)
16.511(2)
95.70(1)
1797.9(3)
1.483
9.907(1)
16.480(2)
13.477(1)
102.448(9)
2148.6(4)
1.784
11.383(1)
22.017(2)
8.6293(8)
108.80(1)
2047.3(3)
1.51
b
14.858(2)
13.117(1)
99.32(1)
1790.1(3)
1.489
c
, Å
β
, deg
V
, Å3
ρcalcd, g/cm3
μ
θ
, cm–1
7.62
7.59
43.64
6.88
scan range, deg
2.09–28.28
1.83–31.1
1.98–32.85
1.89–29.55
Range of indices
h, k, l
–12 <
–19 <
–17 <
h < 12,
k < 19,
l < 17
–5 <
–20 <
–24 <
h < 10,
k < 20,
l < 19
–13 <
–24 <
–18 <
h < 14,
k < 24,
l < 20
–14 <
–27 <
–11 <
h < 15,
k < 30,
l < 11
N
N
measured
18340
4446
11971
4952
28791
7366
19423
5054
independent
Rint
,
Rσ
0.044, 0.04
245
0.041, 0.029
244
0.037, 0.034
273
0.039, 0.038
288
Number of parameters
S
1.072
1.053
1.05
1.068
R
factor (
I
> 2σ(
I
))
0.042
0.04
0.043
0.043
Δρmax/Δρmin
,
e
Å–3
0.729/–0.374
1.016/–0.946
0.276/–0.349
0.631/–0.346
meter with a CCD detector (Oxford Diffraction were refined in the anisotropic approximation, and
GeminiR, MoKα radiation, scan mode, graphite
ω
hydrogen atoms were specified geometrically with
the thermal parameters iso(H) = 1.2 eq(C) and
iso(H) = 1.5 eq(O). The main crystallographic data
and refinement parameters for the structures are listed
in Table 1. Selected bond lengths and bond angles are
monochromator) at ambient temperature. An absorpꢀ
tion correction was applied on intensities of diffracꢀ
tion reflections using the SCALE3 ABSPACK algoꢀ
rithm of the CrysAlisPro program [32]. The crystal
structures of complexes Ia and III were determined by
a direct method using the SIR2004 program [33], and
those of crystals Ib and II were determined by the ab
initio method using the Superflip program [34] and
refined by the leastꢀsquares method using the
U
U
U
U
given in Table 2. All crystallographic data Ia, Ib, II, III
were deposited with the Cambridge Crystallographic
Data Centre (nos. 875317, 875318, 875319, and
875320; deposit@ccdc.cam.ac.uk or http://www.ccdc.
SHELXL program [35]. All nonꢀhydrogen atoms cam.ac.uk/data_request/cif).
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204
KOPOTKOV et al.
Table 2. Selected bond lengths and bond angles in complexes Ia
,
Ib,
II, and III
*
Type of bond
Mn–Oeq, Å
Ia
Ib
II
III
1.887(1)
1.888(1)
1.876(1)
1.895(1)
1.873(2)
1.889(2)
1.883(1)
1.874(1)
Mn–Neq, Å
Mn–Nax, Å
(Mn–Oax)
2.036(2)
2.048(2)
2.027(2)
2.052(1)
1.984(2)
1.995(2)
1.981(2)
1.980(2)
2.266(2)
2.319(2)
2.260(2)
2.329(2)
2.295(2)
2.333(2)
2.262(2)
2.321(2)
(NMnN)ax, deg
(NMnO)
175.90(7)
174.60(6)
171.91(8)
173.99(7)
(Mn–Mn)chain, Å
(Mn–Mn)interchain, Å
(CNC)Dca, deg
8.637
7.405
7.871
7.210
8.407
7.003
4.890 (in dimer)
121.9(3)
122.3(2)
119.8(2)
121.4(3)
* (NMnN) is the angle between the axial bonds at Mn; (Mn–Mn)
is the closest distance between Mn in the chain; (Mn–
ax
interchain
chain
Mn)
bridge.
is the closest Mn–Mn distance between the chains; and (CNC)
is the angle at the central N atom in the dicyanamide
Dca
RESULTS AND DISCUSSION
bridging ligand (two polymorphous modifications Ia
and Ib and complex II), or as the terminal ligand
(complex III). The latter is the first Mn(III) complex
with the Schiff base containing the Dca– anion as the
terminal ligand. Probably, this is related to steric feaꢀ
tures of the Schiff base (3ꢀMeOSalen2–) bearing the
methoxy group in position 3.
The Mn3+ complexes with Schiff bases Salpn2–,
5ꢀBrSalen2–, 3ꢀMeOSalen2–) and dicyanamide were
synthesized using the following three approaches:
(A) the reaction between Mn3+ acetate, the correꢀ
sponding Schiff base, and a precursor of the dicyanꢀ
amide ligand, (B) the substitution of the terminal
ligand (H2O) in the starting Mn3+ complexes with
Schiff bases {[Mn(BS)H2O]ClO4} for the dicyanamide
ligand; and (C) the reaction between Mn2+ diacetate,
the corresponding salicylaldehyde and diamine, and a
precursor of the dicyanamide ligand. Precursors of the
dicyanamide ligands were NaN(CN)2, PPh4N(CN)2,
The molecular structures of complexes I–III are
shown in Fig. 1. The central Mn atom in all structures
has the octahedral coordination with the equatorial
plane formed by the O and N atoms of the Schiff base.
In complexes Ia, Ib, and II the axial positions are
occupied by the N atoms of the Dca ligand, whereas in
structure III the O atom of the water molecule occuꢀ
pies one of the axial positions. The shape of the octaꢀ
hedron is extended along the axial axis, which is charꢀ
acteristic of the Jahn–Teller ion of Mn(III) (Table 2).
The Mn–Oeq, Mn–Neq, and Mn–Nax bond lengths in
the synthesized complexes are close to similar disꢀ
tances in complex [Mn(Salen)N(CN)2]n [27, 28].
M[N(CN)2]2 (M = Mn, Ni) and nꢀBu4N{M[N(CN)2]3}
(M = Mn2+, Ni2+). It was assumed that the Mn(III)
complexes with Schiff bases containing paramagnetic
anions {M[N(CN)2]3}– as bridging ligands could posꢀ
sibly be synthesized in the case of complex Mn2+ and
Ni2+ dicyanamides. However, regardless of the nature
of the precursor of the dicyanamide ligand and
the synthesis method, we obtained complexes conꢀ
Structures Ia, Ib, and II are characterized by the
taining only the dicyanamide anion either as the chain structure through the bridging Dca groups in the
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MANGANESE(III) COMPLEXES WITH TETRADENTATE
205
Iа
Ib
II
III
Fig. 1. Molecular structures of complexes Ia
,
Ib,
II, and III with 30% thermal ellipsoids.
axial positions, whereas structure III is built of discrete bonds C–H⋅⋅⋅Br and O–H⋅⋅⋅
O with the salicylideneꢀ
dimers Mn(3ꢀMeOSalen)N(CN)2(H2O)]⋅⋅⋅[Mn(3ꢀ imine fragments of the complex.
[
MeOSalen) N(CN)2(H2O)].
The crystal structure of complex III is built of cenꢀ
trosymmetric dimers linked by hydrogen bonds
The projections of the crystal structures of polyꢀ
morphous phases Ia and Ib along the
shown in Fig. 2. The structures of these phases differ
by the internal structure of the polymer chain. First,
the angle between the Jahn–Teller axes in the chain is
44.5° for complex Ia and 69.9° for complex Ib. In
addition, the Mn(Salpn) fragments have different
conformations: the dihedral angles between the planes
O⎯H⋅⋅⋅O (Fig. 4a). The interplanar distance in the
dimer is 3.26 Å, and the type of overlapping is shown
in Fig. 4b. In crystal the dimers are formed into layers
х direction are
perpendicular to the
y direction (Fig. 4c). Inside the
layer, the Jahn–Teller axes at Mn(III) are parallel and
the angle between these axes from the adjacent layers
is 85.4
nearly planar, and the angle between the planes of
methoxysalicylideneimines is 10.3
°. The central fragment Mn(MeOSalen) is
of salicylideneimines (С7NO) are 52.5
°
in complex Ia
°.
and 73.6
°
in complex Ib. The chains in structures Ia
The magnetic properties of polycrystalline samples
and Ib pass along the directions [–1 0 1] and [0 1 0],
respectively. Both structures are characterized by
of complexes Ia and II were studied in a range of
2.0⎯300 K. The temperature dependences of χM T and
shortened contacts between the C–H⋅⋅⋅O, C–H⋅⋅⋅
C,
–1
χM are presented in Figs. 5 and 6. For both comꢀ
plexes, the product χM is almost temperatureꢀindeꢀ
and ⋅⋅⋅ chains ( interactions).
C
C
π–π
T
The projection of crystal structure II along the
direction is shown in Fig. 3. The Mn(BrSalen) fragꢀ
pendent down to ~50 K and decreases sharply with the
further temperature decrease down to 2 K. The values
x
of χM T
at 300 K (2.88 cm3 K/mol and 2.90 cm3 K/mol
ment in structure II is nearly planar: the angle between
the planes of bromosalicylideneimines is 7.8 . The
Jahn–Teller axes of the adjacent Mn(III) atoms in the
chain are arranged at an angle of 56.6 . The crystals
include the MeOH solvent molecule that is
localized between the chains and forms hydrogen susceptibility are well described by the Curie–Weiss
°
for complexes Ia and II, respectively) almost coincide
with a theoretical value of 3.00 cm3 K/mol for the
magnetically noninteracting Mn3+ ions with
S
= 2 and
°
g
= 2. The temperature dependences of the inverse
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206
KOPOTKOV et al.
0
z
y
Ia
z
y
0
Ib
Fig. 2. Projections of crystalline structures Ia and Ib along the
x
chain (hydrogen atoms are omitted for clarity).
z
0
y
Fig. 3. Projection of crystal structure II along the
x direction.
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MANGANESE(III) COMPLEXES WITH TETRADENTATE
207
(b)
(а)
(c)
z
y
0
Fig. 4. (a) General view of the dimer, (b) overlapping of molecules in the dimer, and (c) the projection of crystal structure III along
the
x
direction (hydrogen atoms are omitted for clarity).
3.0
2.5
2.0
1.5
1.0
(а)
3.0
2.8
2.6
2.4
2.2
2.0
1.8
1.6
(а)
125
(b)
100
75
50
25
0
120
100
80
60
40
20
0
(b)
0
50 100 150 200 250 300 350
, K
T
0
50 100 150 200 250 300
, K
T
–50
0
50 100 150 200 250 300 350
, K
T
–50
0
50 100 150 200 250 300 350
, K
T
–1
M
⎯ 1
Fig. 5. Temperature dependences of (a)
χ
T
and (b)
χ
Fig. 6. Temperature dependences of (a) χ T and (b) χ
M M
M
for complex Ia
.
for complex II
.
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208
KOPOTKOV et al.
13. Lu, Z., Yuan, M., Pan, F., et al., Inorg. Chem., 2006,
vol. 45, no. 9, p. 3538.
14. Sailaja, S., Reddy, K.R., Rajasekharan, M.V., et al.,
equation (
χ
=
C
/
T –
θ
) in the whole temperature
= 2.89 cm3 K/mol,
= –2 K
= –0.7 K for complexes Ia
range with parameters
С
θ
and
С
= 2.9 cm3 K/mol,
θ
Inorg. Chem., 2003, vol. 42, no. 1, p. 180.
and II, respectively (Figs. 5b and 6b). The low negative
values of Weiss constants indicate the existence of
weak antiferromagnetic exchange interactions
between the highꢀspin Mn3+ ions in the chains of comꢀ
plexes Ia and II through the bridging dicyanamide
15. Choi, H.ꢀL., Sokol, J.J., and Long, J.R., Inorg. Chem.
2004, vol. 43, no. 5, p. 1606.
,
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ACKNOWLEDGMENTS
The authors are grateful to L.A. Kushch and
R.P. Shibaeva for the discussion of the results.
This work was supported by the Russian Foundaꢀ
tion for Basic Research (grant no. 10ꢀ03ꢀ00128).
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2013