Polymeric manganese carboxylato compounds [{Mn[m-C6H4(COO)2](C5 H5N)2}n] and [{Mn(3-C5H4NCOO)2}n] with one- and three-dimensional extended structures

Article abstract of DOI:10.1246/bcsj.75.2609

Two catena manganese carboxylato complexes [{Mn[m-C₆H₄(COO)₂](C₅ H₅N)₂}_n] (1) and [{Mn(3-C₅H₄NCO-O)₂}_n] (2) were synthesized and structurally characterized. Isophthalate together with pyridine as a capping ligand leads to a 1-D alternating chain structure of complex 1, while 3-pyridinecarboxylate (also known as nicotinate) results in a 3-D network of complex 2, implying an effect of the ligand on the dimensionality of the extended structure. Stretching vibration differences, Δ(V_as-V_s) < 200 cm^-1, for the COO^- groups of both complexes were observed to be consistent with the bridging and chelating coordination modes. The variable-temperature conductance of 1 displays a semiconductor feature. Magnetic exchange interactions were analyzed using models composed of Mn₂(μ-COO)₂ and Mn₂(μ-acidate)₂ moieties, exhibiting an antiferromagnetic coupling behavior for each complex through Mn₂(μ-COO)₂ moieties. The magnetic interaction in the Mn₂(μ-acidate)₂ moieties is negligible.

Full text of DOI:10.1246/bcsj.75.2609

c. Jpn.
© 2002 The Chemical Society of Japan
Bull. Chem. Soc. Jpn., 75, 2609–2614 (2002) 2609
e Chemical
ciety of Ja-
n
e Chemical
ciety of Ja-
n
Polymeric Manganese Carboxylato Compounds
[{Mn[m-C6H4(COO)2](C5H5N)2}n] and [{Mn(3-C5H4NCOO)2}n] with
One- and Three-Dimensional Extended Structures
Polymeric Manganese Carboxylato Compounds
W. Wang et al.
02
09
14
Wenguo Wang,# Chengbing Ma, Xiaofeng Zhang, Changneng Chen, Qiutian Liu,* Feng Chen,
Daizheng Liao,† and Licun Li†
SJA8
09-2673
145
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy
of Sciences, Fuzhou, Fujian 350002, China
†Department of Chemistry, Nankai University, Tianjing 300071, China
(Received May 27, 2002)
02
02
Two catena manganese carboxylato complexes [{Mn[m-C6H4(COO)2](C5H5N)2}n] (1) and [{Mn(3-C5H4NCO-
O)2}n] (2) were synthesized and structurally characterized. Isophthalate together with pyridine as a capping ligand leads
to a 1-D alternating chain structure of complex 1, while 3-pyridinecarboxylate (also known as nicotinate) results in a 3-D
network of complex 2, implying an effect of the ligand on the dimensionality of the extended structure. Stretching vibra-
tion differences, ∆(νas−νs) < 200 cm−1, for the COO− groups of both complexes were observed to be consistent with the
bridging and chelating coordination modes. The variable-temperature conductance of 1 displays a semiconductor fea-
ture. Magnetic exchange interactions were analyzed using models composed of Mn2(µ-COO)2 and Mn2(µ-acidate)2 moi-
eties, exhibiting an antiferromagnetic coupling behavior for each complex through Mn2(µ-COO)2 moieties. The magnet-
ic interaction in the Mn2(µ-acidate)2 moieties is negligible.
Carboxylate as a versatile ligand has recently attracted more
attention in coordination chemistry. Polynuclear metal carbox-
ylates have been used to explore exchange coupling interac-
tions between adjacent metal ions.1 Metal complexes with ex-
tended structures have attracted great interest in studies of
magnetically coupling because of promising applications in
the field of molecular magnetism. Carboxylate connects para-
magnetic centers to build a spatially well-spanned framework
by various bridging modes, and mediates superexchange inter-
actions between the paramagnetic centers. The chemistry of
manganese has been especially well developed in recent years
because manganese is catalytically active in a variety of metal-
loenzymes.2 Poly(manganese carboxylate) complexes3 have
become an important research field for the simulation of rele-
vant manganese enzymes and the exploration of magnetism.
Phthalates have two p-, m-, or o-carboxylato groups which link
manganese sites in diversified modes, resulting in a series of
phthalato manganese polymers.4 It is interesting that m- and o-
phthalato manganese complexes have a one-dimensional (1-D)
extended structure, while terephthalato complexes have a
three-dimensional (3-D) structure.4b,c It is comprehensible that
the largest separation between both p-carboxylato groups low-
ers the crowding of the groups and, therefore, terephthalate
would be favorable to simultaneously connect with more Mn
ions to construct a network structure. The control of dimen-
sionality has become a major challenge for the rational design
of molecular architecture. To our knowledge, catena manga-
nese complexes possessing multidimensional extended struc-
tures are still rare.5 In this work we report on a preliminary at-
tempt to control the dimensionality of the extended structure
for the manganese complex. Isophthalic acid and pyridine
mixed ligands were used to build a one-dimensional manga-
nese complex [{Mn(m-phth)(py)2}n] (1, py = pyridine; phth =
phthalate), while 3-pyridinecarboxylic acid was used to pro-
duce a 3-D manganese complex [{Mn(3-C5H4NCOO)2}n] (2).
Results and Discussion
Complex 1 was synthesized in a MeOH/H2O solution at re-
flux temperature. The coordination sphere of Mn in 1 shown
in Fig. 1 is a distorted octahedron with two N atoms of pyri-
dine located at opposed positions with N–Mn–N angle of
168.44(8)°. Selected bond lengths and angles are listed in
Table 1. It is noted that when compared to the shorter Mn–
O3A and Mn–O4B bonds, carboxyl chelating Mn–O1and Mn–
O2 bonds are lengthened to 2.2480(17) and 2.2871(18) Å ow-
ing to an astriction of the chelating angle (58.08(6)°). Pyridine
caps the manganese site, forming the (py)2Mn moiety, which is
alternately linked by double µ-COO and double µ-isophthalate
bridges to make a 1-D alternating chain as shown in Fig. 1 with
Mn≥Mn separations of 4.582 Å and 7.024 Å, respectively.
This feature is different from that of the other isophthalate
4e
manganese complex, [{Mn2(m-phth)(phen)4}n](ClO4)2n
(phen = 1,10-phenanthroline), which contains (phen)2Mn
moieties linked by single µ-isophthalate bridges to form a zig-
zag 1-D chain. The existence of capping ligands (py and phen)
# Graduate School of the Chinese Academy of Sciences, Beijing,
China

2610 Bull. Chem. Soc. Jpn., 75, No. 12 (2002)
Polymeric Manganese Carboxylato Compounds
Table 1. Selected Bond Lengths [Å] and Angles [°] for
Complexes 1 and 2
in the Mn(Ⅱ) coordination spheres of these two complexes may
block the way towards a 3-D structure. N-containing ligands,
such as phen, N2O2 Schiff base and so on, were generally in-
volved in the Mn(Ⅱ) coordination sphere to construct indepen-
dent Mn/N moieties by chelation of the ligand to the manga-
nese atom, while the phthalate ligands link these Mn/N moi-
eties to result in 1-D chains. The amount of chelating donor
atoms may cause a variation of the chain structure as shown in
Scheme 1. Schiff base (N2O2 4 donor atoms) and phen (2 do-
nor atoms) engender single µ-phthalate4e,g or single µ-COO
bridges4d between the two Mn/N moieties, while pyridine con-
taining only one donor atom brings double bridges in complex
1. Nicotinate ligand possesses both carboxyl and an N donor
at the meta-position, which is difficult to chelate to the manga-
nese atom by N and O donors, and is able to coordinate simul-
taneously to three manganese ions in various directions and to
unlimitedly extend these coordination bonds. It is expected
that nicotinate would be favorable to construct 3-D network of
1a)
Mn–O4B
Mn–O2
Mn–N2
2.1115(18) Mn–O3A
2.2480(17) Mn–O1
2.1194(17)
2.2871(18)
2.307(2)
90.45(7)
84.90(7)
84.58(7)
90.20(7)
100.42(8)
88.38(7)
92.74(8)
2.295(2)
Mn–N1
O4B–Mn–O3A 105.48(7)
O4B–Mn–N2
O3A–Mn–N2
O2–Mn–N2
O1–Mn–N2
O4B–Mn–N1
O3A–Mn–N1
O1–Mn–N1
O4B–Mn–O2
O3A–Mn–O2
O4B–Mn–O1
O3A–Mn–O1
O2–Mn–O1
O2–Mn–N1
N2–Mn–N1
152.45(7)
101.05(7)
94.96(6)
158.99(7)
58.08(6)
87.50(7)
168.44(8)
2b)
Mn–O1C
Mn–O2E
Mn–N
O1C–Mn–O1B 87.75(14)
O1C–Mn–O2E 99.98(9)
O1B–Mn–O2E 90.23(9)
O1C–Mn–O2D 90.23(9)
O1B–Mn–O2D 99.98(9)
2.125(2)
2.197(2)
2.356(3)
Mn–O1B
Mn–O2D
Mn–NA
2.125(2)
2.197(2)
2.356(3)
84.86(9)
the manganese complexes, though only
a
complex
[{(H2O)2Mn(3-C5H4NCOO)2}n] with 2-D layer structure and
(H2O)2Mn capping moieties has been reported.6 We adopted
hydrothermal method instead of the conventional method to
enhance the chance of the ligands contacting to the Mn(Ⅱ) ion.
Complex 2 was hydrothermally synthesized by heating
MnCl2·4H2O and nicotinic acid in a mole ratio of 1:2.8. In the
structure of 2 shown in Fig. 2, the Mn(Ⅱ) ion locates on a 2-
fold axis and is coordinated by six nicotinate ligands, forming
a distorted octahedral sphere with the axial O–Mn–N(or O) an-
gles ranging from 165.86(13)° to 172.06(9)° and the other an-
gles of 84.86(9)°–100.76(14)°. Selected bond distances and
angles are also given in Table 1. Two types of moieties were
observed, one of which is Mn2(µ-COO)2 with the shortest
Mn≥Mn separation of 4.917 Å, the other is Mn2(µ-nicotinate-
N,O)2 with Mn≥Mn separation of 7.342 Å. The Mn2(µ-
COO)2 moiety forms 8 atomic plane with the largest deviation
of 0.168 Å; the Mn2(µ-nicotinate-N,O)2 moiety contains 12
atomic plane consisting of 2Mn, 2N, 2O and 6C atoms with the
O2D–Mn–N
O1C–Mn–NA 172.06(9)
O1B–Mn–NA 85.93(10)
O2E–Mn–NA 84.86(9)
O2D–Mn–NA 86.14(9)
O2E–Mn–O2D 165.86(13) N–Mn–NA
100.76(14)
172.06(9)
O1C–Mn–N
O2E–Mn–N
85.93(10)
86.14(9)
O1B–Mn–N
a) Symmetry transformations: A: −x+1, −y, −z+1; B: x,
y, z+1. b) Symmetry transformations: A, −x+1, y,
−z+1/2; B, x−1/2, y+1/2, z; C, −x+3/2, y+1/2, −z+1/
2; D, −x+3/2, −y+1/2, −z+1; E, x−1/2, −y+1/2, z−1/
2.
Fig. 1. ORTEP diagram of 1 showing the atom-numbering
scheme of a Mn(m-phth)(py)2 moiety and thermal ellip-
soids at 30% probability. Mn2(µ-CO2)2 and Mn2(µ-iso-
phthalate)2 moieties alternately link to form one-dimen-
sional chain of complex 1.
Scheme 1. (A) Single phthalate bridges between Mn moi-
eties of N2O2 Schiff base. (B) Single phthalate bridges be-
tween (phen)2Mn moieties. (C) Double phthalate bridges
between (py)2Mn moieties.

W. Wang et al.
Bull. Chem. Soc. Jpn., 75, No. 12 (2002) 2611
Fig. 2. Structure of complex 2 showing the coordination
sphere around Mn atom and the atom-numbering scheme.
Two Mn2(µ-COO)2 and two Mn2(µ-nicotinate-N,O)2 moi-
eties are around the Mn site with Mn≥Mn separations of
4.917 Å and 7.342 Å, respectively. The atoms are drawn at
a 30% probability level.
largest deviation of 0.171 Å from the least-squares plane.
Around each the manganese site, two Mn2(µ-COO)2 and two
Mn2(µ-nicotinate-N,O)2 moieties construct a distorted octahe-
dral coordination environment as shown in Fig. 2 with dihe-
drals of 79.2° between both the Mn2(µ-COO)2 moieties and
64.2° between both Mn2(µ-nicotinate-N,O)2. The dihedrals
between the Mn2(µ-COO)2 and Mn2(µ-nicotinate-N,O)2 moi-
eties are 11.3° and 71.0°. These moieties extend in space and
cross to each other to form 3-D network (Fig. 3). This struc-
ture makes complex 2 undissolvable in a variety of inorganic
and organic solvents.
Fig. 3. Packing diagram of unit cell of 2 shows 3-D network
structure.
The IR spectrum of complex 1 displays asymmetric stretch-
ing vibrations for the COO− groups at 1543–1610 cm−1 and
symmetric stretching vibrations at 1392–1477 cm−1 with the
differences between the two stretchings, ∆(νas−νs) = ca. 150
cm−1. It is noted that the carboxyl groups in 1 contain both
chelating and symmetrical bridging coordination modes,
which generally associate with a smaller ∆(νas−νs) value (<
200 cm−1).7 Compared with complex 2, which contains the
carboxyl groups coordinating to the Mn(Ⅱ) ions in the bridging
mode, it is reasonable to see that complex 2 has a larger ∆(νas−
νs) value than complex 1. In fact, the IR spectrum of complex
2 displays νas of 1566–1601 cm−1 and νs of 1389–1417 cm−1
with a difference value of ∆(νas−νs) = 180 cm−1. This obser-
Fig. 4. Plot of temperature-dependent conductance of com-
plex 1.
ments were performed from 300 to 4 K for 1 and 2. At room
temperature, the effective magnetic moment (µeff) values were
determined to be 6.01 BM (1) and 5.92 BM (2), which are
slightly larger or equal to the expected value for an indepen-
dent spin of S = 5/2 (5.92 BM). The χMT values smoothly de-
crease with the decrease of the temperature in the measured
range as shown in Fig. 5, indicating an antiferromagnetic spin-
exchange interaction in the two complex molecules. In view
of the structures of the two complexes, there are two possible
exchange pathways: through extended µ-dicarboxylato (or µ-
nicotinato-N,O) ligand bridges and through carboxyl µ-COO
bridges. According to the dissimilar chain structures of the
two compounds, two models were adopted to give a good fit
for their magnetic data.
vation is consistent with the general rule that ∆chelating < ∆bridg-
7,8
.
ing
Variable-temperature conductances (σ) of powdered sample
of complex 1 were determined in the range from 24 °C (8.16 ×
10−6 S cm−1) to 80 °C (1.38 × 10−5 S cm−1); and the tempera-
ture dependence of the electrical conductivity is shown in Fig.
4. The value of the conductance and its rising with the rising
of temperature display a semiconductor feature of the com-
pound.9 However, the conductivity of 2 is far from the conduc-
tance range (< 10−12 S cm−1) of a semiconductor, showing an
insulator feature.
Variable-temperature magnetic susceptibility measure-

2612 Bull. Chem. Soc. Jpn., 75, No. 12 (2002)
Polymeric Manganese Carboxylato Compounds
Scheme 2. Magnetic interaction model contains Mn2(µ-CO)2
and Mn2(µ-nicotinate-N,O)2 chains crossing to each other
for complex 2.
interaction in the Mn2(µ-CO2)2 chains with J representing the
interaction between neighboring magnetic species,
Ng2µ2
kT
χchain = (
B )[A + Bx2 ][1 + Cx + Dx3]-1,
(2)
where A = 2.9167, B = 208.04, C = 15.543, D = 2707.2, and
x = |J|/kT.
Subsequently, a molecular field approximation12 was used to
contain the Mn2(µ-nicotinate-N,O)2 chains which cross with
the aforementioned Mn2(µ-CO2)2 chains with interchain inter-
actions of ZJꢀ. The Z value is the number of nearest magnetic
species around a given magnetic site in the crystal lattice.
χchain
χM
=
(3)
[1 − χchain (2ZJꢀ / Ng2µB2 )]
On this basis, a least-squares fitting of the experimental data
led to J = −0.26 cm−1, ZJꢀ = −0.02 cm−1, g = 2.00 and R =
5.62 × 10−5, exhibiting that antiferromagnetic interactions are
present in the system. For the complexes reported in this work,
the J values are in the usual range of the caboxylate manga-
nese(Ⅱ) complexes,4,5,13 in which the µ-COO and µ-acidate
ligand bridges link the Mn(Ⅱ) sites. Weak antiferro- and ferro-
magnetic couplings were usually observed in these reported
systems, especially, the weak ferromagnetic contribution
sometimes occurs from a long pathway via the benzene ring of
the phthalate ligands4b or the µ-OCO bridges.4e In complex 1,
the weak ferromagnetic interaction occurs in Mn2(µ-phth)2
moieties, being a long pathway interaction. It is noted that the
coordination distortion of the Mn(Ⅱ) site from a regular octa-
hedron makes the two carboxyl groups of isophthalate to be
not coplanar (dihedral of 31° between both COO planes), and
may reduce the overlap integral between the magnetic orbit-
als.14 Thus, a weak ferromagnetic behavior through the long
pathway of isophthalate ligands may not be completely ruled
out, though the interaction is very weak. A better coplanarity
was observed in the Mn2(µ-COO)2 moieties of 1 and both of
the Mn2(µ-nicotinate-N,O)2 and Mn2(µ-COO)2 moieties of 2.
This would be favorable to increase the overlap integral for the
magnetic orbitals, and antiferromagnetic interactions would be
expected. However, the weak magnetic interactions for these
two complexes should be attributed to the long separation
(4.58–7.34 Å) between the manganese sites. Obviously, owing
to the shortening of the Mn≥Mn separation, stronger magnetic
interactions in the Mn2(µ-COO)2 moieties are observed than
those in the Mn2(µ-isophth)2 or in the Mn2(µ-nicotinate)2 moi-
Fig. 5. Temperature dependences of susceptibilities (χM) and
χMT for complexes 1 (A) and 2 (B). The solid lines repre-
sent the calculated values.
Complex 1 has an alternating chain structure (Fig. 1) com-
posed of Mn2(µ-COO)2 (J1) and Mn2(µ-phth)2 (J2) moieties.
Equation 1 for a homonuclear alternating chain was used while
referring to the literature.10
Ngꢀ2µB2 1 + u1 + u2 + u1u
(1)
χ
=
(
2 ),
3kT
1 − u1u2
Jꢀ
kT
kT
Jꢀ
kT
kT
u = Coth( 1 ) − ( ), u2 = Coth( 2 ) − ( ),
where
1
Jꢀ1
Jꢀ2
Jꢀi = JiS(S + 1) (i = 1, 2), and gꢀ = g[S(S + 1)]1/2.
A least-squares fitting of the experimental data led to J1 =
−0.942 cm−1, J2 = 0.096 cm−1 and g = 2.026. The agreement
factor, defined as R = Σ[(χMT)cal − (χMT)obsd]2/Σ[(χMT)obsd]2 is
1.49 × 10−4, exhibiting weak antiferro- and ferro-magnetic in-
teractions in the Mn2(µ-COO)2 and the Mn2(µ-phth)2 moieties,
respectively.
The structure of complex 2 consists of two types of chains
across each other, which contain Mn2(µ-CO2)2 and Mn2(µ-nic-
otinate)2 units, respectively, as shown in Fig. 3 and Scheme 2.
Equation 2 for a homonuclear chain11 was adopted to treat the

W. Wang et al.
Bull. Chem. Soc. Jpn., 75, No. 12 (2002) 2613
Table 2. Summary of Crystal Data for the Complexes 1
and 2
eties, implying that the magnetic coupling pathway can be bet-
ter afforded by µ-carboxyl bridges than µ-isophthalate (for 1)
or µ-nicotinate-N,O (for 2) bridges.
1
2
Formula
Mr
C18H14N2O4Mn1
377.25
C12H8Mn1N2O4
299.14
Experimental
All manipulations were performed under aerobic conditions
with materials used as received. IR spectra were recorded by a
Bio-Rad FTS-40 Model spectrophotometer. Variable-temperature
magnetic susceptibilities were measured on a Model CF-1 super-
conducting extraction sample magnetometer with a crystal sample
kept in a capsule at 5–300 K. Diamagnetic corrections were made
with Pascal’s constants. Electrical conductivities were determined
with pressed pellets on a ZL5-LCR conductometer. Elemental
analyses were performed using a Vario EL IIIElemental Analyzer.
[{Mn(m-phth)(py)2}n] (1). Isophthalic acid (0.332 g, 2.00
mmol) was dissolved in 30 cm3 of MeOH/H2O (v/v 1:4). To the
solution MnCl2•4H2O (0.397 g, 2.00 mmol) was added and stirred
for 3 h at the reflux temperature, resulting in white precipitates be-
ing deposited. Then pyridine was added drop-wise (ca. 5 cm3) un-
til the precipitates dissolved. After stirring for 4h, the solution
was allowed to stand for several days at room temperature, afford-
ing 0.25 g (yield 33.1%) of block crystals of 1. Anal. Calcd for
C36H28Mn2N4O8: C, 57.30; H, 3.74; N, 7.43; Mn, 14.56%. Found:
C 57.12; H 3.54; N 7.37; Mn, 14.7%. IR (KBr pellet) 1610, 1568,
1543 for νasym(CO2), 1477, 1444, 1392 cm−1 for νsym(CO2).
[{Mn(3-C5H4NCOO)2}n] (2). A mixture slurry composed of
MnCl2•4H2O (0.198 g, 1.00 mmol) and nicotinic acid (0.346 g,
2.81 mmol) in 10 cm3 of H2O was sealed into a teflon tube and
heated for 3 days at 160 °C under autogenous pressure. The re-
sulting solid phase consisting of light-red prisms of the complex
was filtered and dried at room temperature, affording 0.15 g (yield
50.1%) of 2. Anal. Calcd for C12H8MnN2O4: C, 48.16; H, 2.68; N,
9.36; Mn, 18.39%. Found: C 47.86; H 2.61; N 9.62; Mn, 17.91%.
IR (KBr pellet) 1601, 1566 for νasym(CO2), 1417, 1389 cm−1 for
Crystal system
Space group
Triclinic
P-1
Monoclinic
C2/c
14.7930(12)
9.6011(8)
8.7631(7)
a/Å
b/Å
c/Å
α/°
β/°
γ/°
9.0271(2)
9.6678(3)
10.2360(3)
75.732(1)
73.658(1)
87.958(1)
830.24(4)
2
114.229(2)
V/Å3
Z
1134.98(16)
4
1.751
1.174
293(2)
ρ
calc/g cm−3
1.509
0.820
293(2)
µ(Mo Kα)/cm−1
T/K
Unique reflections
2573 (I > 2σ(I)) 835 (I > 2σ(I))
0.0383, 0.1066
0.0432, 0.1093
a)
b)
R1 , wR2
R1, wR2 (all data)
0.0437, 0.1166
0.1166, 0.0543
a) R = ΣꢀFo| − |Fcꢀ/Σ|Fo|. b) Rw = [Σw(|Fo| − |Fc|)2/
2
2
ΣwFo ].1/2 1: w = 1/[S2(Fo ) + (0.0568P)2 + 0.0876P],
where P = (Fo + 2Fc2)/3. 2: w = 1/[S2(Fo ) +
2
2
(0.1000P)2 + 0.0000P], where P = (Fo2 + 2Fc2)/3.
References
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Crystallography. Intensity data for single crystals of the two
2
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29973047), the State Key Basic Research and Development
Plan of China (G1998010100), and Expert Project of Key Ba-
sic Research from Ministry of Sci&Tech.

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