Catena-Poly[[aqua(2,2′-bipyridine-κ2N,N′) manganese(II)]-μ-tereph-thalato-κ3O,O′:O″]

Article abstract of DOI:10.1107/S0108270104007565

The title complex, [Mn(C₈H₄O₄)(C ₁₀H₈N₂)(H₂O)]_n, takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn^II center is surrounded by two tp ligands, one water molecule and one 2,2′-bipyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.97 (11)°. The complete solid-state structure can be described as a three-dimensional supramolecular framework stabilized by hydrogen-bonding interactions involving the coordinated water molecule and the carboxy O atoms of the tp ligands, and by π-π stacking interactions involving the bipy rings and the benzene ring of the tp ligand.

Full text of DOI:10.1107/S0108270104007565

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
(Hong & Do, 1997; Li et al., 2002; Yang Bian et al., 2003) and
four three-dimensional (Cano et al., 1994; Hong & Do, 1997;
Sun et al., 2001; Kaduk, 2002; Ma, Chen, Liu et al., 2003)
manganese(II)±terephthalate complexes, and various bonding
modes, including monodentate, bidentate and tetradentate for
the tp ligands, have been observed in these complexes. In the
present paper, we report the single-crystal structure of a new
polymeric MnII±terephthalate complex, (I), in which the tp
dianion acts as a tridentate bridging ligand, a rare coordina-
tion mode that has not been reported previously in manga-
nese±terephthalate complexes.
ISSN 0108-2701
catena-Poly[[aqua(2,20-bipyridine-
j2N,N0)manganese(II)]-l-tereph-
thalato-j3O,O0:O00]
Cheng-Bing Ma, Ming-Qiang Hu, Chun-Xia Zhang,
Feng Chen, Chang-Neng Chen and Qiu-Tian Liu*
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Fuzhou, Fujian 350002, People's Republic of China
Correspondence e-mail: lqt@ms.fjirsm.ac.cn
Received 10 March 2004
Accepted 30 March 2004
Online 31 May 2004
The title complex, [Mn(C8H4O4)(C10H8N2)(H2O)]n, takes the
form of a zigzag chain, with the terephthalate dianion (tp)
acting as a tridentate ligand. The MnII center is surrounded by
two tp ligands, one water molecule and one 2,20-bipyridine
(bipy) ligand and exhibits a severely distorted octahedral
coordination environment, with cis angles ranging from
57.31 (8) to 123.97 (11)ꢀ. The complete solid-state structure
can be described as a three-dimensional supramolecular
framework stabilized by hydrogen-bonding interactions invol-
ving the coordinated water molecule and the carboxy O atoms
of the tp ligands, and by ꢀ±ꢀ stacking interactions involving
the bipy rings and the benzene ring of the tp ligand.
Compound (I) consists of in®nite one-dimensional chains in
which successive MnII atoms are bridged by one tp ligand, as
shown in Fig. 1. Each MnII atom has a severely distorted six-
coordinate geometry (Table 1), with the three trans angles
[147.16 (10), 158.43 (11) and 143.66 (10)ꢀ] deviating signi®-
cantly from the ideal value of 180ꢀ. The Mn atom is coordi-
nated by three carboxy O atoms [MnÐO = 2.098 (2)±
Ê
Ê
2.281 (2) A] from two tp ligands, one water O atom [MnÐO5 =
2.160 (3) A] and two pyridyl N atoms [MnÐN = 2.235 (3) and
Ê
2.260 (3) A] from the chelating bipy ligand. The MnÐN and
MnÐOcarboxy bond lengths are similar to those found for
another ternary Mn±tp±bipy polymeric complex, [Mn2(tp)-
(bipy)2]n(ClO4)2n (Cano et al., 1994). The MnÐOwater distance
is comparable to those in other MnII±water complexes (Okabe
& Koizumi, 1997; Hao et al., 2000; Ma et al., 2002; Ma, Chen,
Chen & Liu, 2003; Schlueter & Geiser, 2003). The main
distortion from ideal octahedral geometry is caused by the
double chelation by the rigid bipy ligand and the chelating
carboxylate group of the tp ligand. The N1ÐMnÐN2 bipy
chelate angle [72.56 (11)ꢀ] is in agreement with those in other
bipy-containing MnII complexes (Baumeister & Hartung,
1997; Zhang et al., 2002; Shen, 2003). The O1ÐMnÐO2
carboxy chelate angle [57.31 (8)ꢀ] is very similar to that in
[Mn(tp)(4,40-bipy)]n [57.07 (11)ꢀ; Ma, Chen, Liu et al., 2003]
but signi®cantly larger than that in [Mn2(tp)(dca)2(terpy)2-
(MeOH)2]n [52.94 (10)ꢀ; Escuer et al., 2002].
Each tp dianion acts as a tridentate bridging ligand, joining
two Mn atoms in a head-to-tail fashion; one of the carboxylate
groups chelates one Mn atom, while the other binds the
second Mn atom in a monodentate fashion. The present work
is the ®rst time that this tridentate ꢁ2 bridging mode has been
observed for the tp ligand in Mn complexes, and to date this
mode has been encountered in just one ®ve-coordinate
copper(II) complex (Yang, Zeng et al., 2003). The two tp
Comment
Owing to the great variety of intriguing structural topologies
(Zaworotko, 1994) and potential applications in such ®elds as
catalysis (Fujita et al., 1994) and molecular magnetism (Miller
& Epstein, 1994), the crystal engineering of supramolecular
architectures organized by coordinate covalent bonds and/or
supramolecular contacts, such as hydrogen bonds and ꢀ±ꢀ
interactions, has been investigated actively. A commonly used
strategy for obtaining such systems is to select appropriate
bridging ligands with versatile bonding modes, in order to bind
more than one metal ion, and with the ability to form
hydrogen bonds. Aromatic chelating ligands, such as 2,20-bi-
pyridine (bipy) and 1,10-phenanthroline, are often introduced
as ancillary ligands, with the hope of providing potential
supramolecular recognition sites for ꢀ±ꢀ stacking inter-
actions.
Terephthalate (tp) is an appropriate bridging ligand for
mediating magnetic exchange interactions between para-
Ê
magnetic metal centers over a limited distance (about 11 A;
È
Burger et al., 1995). Its versatile binding ability has been
manifested by the formation of one mononuclear (Xiang et al.,
1998), one dinuclear (Cano et al., 1997), three one-dimensional
m288 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104007565
Acta Cryst. (2004). C60, m288±m290

metal-organic compounds
Figure 1
Aview of part of the polymeric chain of (I), showing the atom-labelling scheme and displacement ellipsoids at the 30% probability level. Atoms marked
1
2
1
2
with the suf®xes A and B are at the symmetry positions (1 x, 12 y, z 21 ) and (x
as double dashed lines.
,
y, 12 + z), respectively. Intrachain hydrogen bonds are depicted
ligands coordinated to a given Mn center are cis to one
another, resulting in a one-dimensional zigzag chain. The
MnÁ Á ÁMnÁ Á ÁMn angle formed by three successive Mn ions is
104.01 (2)ꢀ and successive bipy moieties are oriented at an
angle of 89.5 (8)ꢀ to one another. The intrachain MnÁ Á ÁMn
Ê
separation is 11.132 (2) A and the closest interchain contact is
Ê
5.642 (2) A. Neighboring chains are arranged in an anti-
parallel fashion (Fig. 2a).
The neighboring zigzag chains are crosslinked by O5Ð
H5BÁ Á ÁO1( x, y, z) hydrogen bonds, formed by the
coordinated water molecule and one of the chelating carboxy
O atoms of a symmetry-related chain (Table 2), thus resulting
in the formation of a two-dimensional hydrogen-bonded
pleated sheet, as shown in Fig. 2(b). The second water H atom
is donated to form an intrachain O5ÐH5CÁ Á ÁO4(x + 12, y + 21,
12 ) hydrogen bond with the uncoordinated carboxy O
atom. These two-dimensional hydrogen-bonded sheets are
further packed into a three-dimensional herring-bone-like
supramolecular network via two kinds of ꢀ±ꢀ stacking inter-
actions, namely one type between the bipy ligands and one
between the phenyl ring of the tp ligand and the bipy ligand,
with perpendicular ring separations of 3.459 (8) and
z
Ê
3.542 (9) A, respectively.
Experimental
A mixture of Mn(NO3)2Á6H2O (1 mmol, 0.28 g), dipotassium tereph-
thalate (1 mmol, 0.24 g) and 2,20-bipyridine (1 mmol, 0.16 g) in
methanol±water (1:2 v/v, 15 ml) was heated at 413 K for 4 d under
autogenous pressure in a 25 ml sealed Te¯on-lined stainless steel
vessel, and then cooled to room temperature over a period of 5 h,
yielding yellow crystals of (I). Analysis calculated for C18H14-
MnN2O5: C 54.98, H 3.59, N 7.12%; found: C 54.92, H 3.61, N 7.08%.
FT±IR (KBr, cm 1): 3205 (br, s), 1605 (s), 1577 (vs), 1531 (m), 1505
(m), 1475 (m), 1439 (s), 1379 (vs), 1313 (m), 1247 (w), 1151 (m), 1089
(w), 1050 (m), 1019 (m), 882 (w), 864 (w), 806 (m), 760 (s), 750 (s), 670
(m), 650 (m), 628 (m), 569 (w), 525 (m), 413 (m).
Figure 2
The crystal packing of (I), showing (a) the antiparallel relationship of
neighboring chains and the interchain hydrogen-bonding crosslinkage,
and (b) part of the two-dimensional hydrogen-bonded network. Bipy
ligands and H atoms have been omitted for clarity. Atoms labelled with
an ampersand (&) or dollar sign ($) are at the symmetry positions ( x,
y, z) and (x + 12, y + 21, z 12 ), respectively.
ꢁ
Acta Cryst. (2004). C60, m288±m290
Cheng-Bing Ma et al.
[Mn(C8H4O4)(C10H8N2)(H2O)] m289

metal-organic compounds
Crystal data
Data collection: SMART (Siemens, 1996); cell re®nement: SAINT
(Siemens, 1994); data reduction: SHELXTL (Siemens, 1994) and
SAINT; program(s) used to solve structure: SHELXTL; program(s)
used to re®ne structure: SHELXTL; molecular graphics: SHELXTL;
software used to prepare material for publication: SHELXTL.
3
[Mn(C8H4O4)(C10H8N2)(H2O)]
Mr = 393.25
Monoclinic, P21=n
Ê
a = 9.8637 (2) A
Dx = 1.543 Mg m
Mo Kꢃ radiation
Cell parameters from 2431
re¯ections
ꢄ = 2.3±25.0ꢀ
ꢁ = 0.81 mm
T = 293 (2) K
Ê
b = 16.3316 (5) A
1
Ê
c = 11.3110 (1) A
ꢂ = 111.726 (2)ꢀ
V = 1692.66 (6) A
Z = 4
This work was supported by the NNSFC (grant Nos.
30170229 and 29973047), the State Key Basic Research and
Development Plan of China (grant No. G1998010100), and the
Expert Project of Key Basic Research of the Ministry of
Science and Technology, People's Republic of China.
3
Ê
Block, pale yellow
0.54 Â 0.53 Â 0.30 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.626, Tmax = 0.784
5399 measured re¯ections
2973 independent re¯ections
2230 re¯ections with I > 2ꢅ(I)
Rint = 0.026
ꢄ
max = 25.0ꢀ
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA1056). Services for accessing these data are
described at the back of the journal.
h = 9 ! 11
k = 12 ! 19
l = 13 ! 9
Re®nement
References
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.046
wR(F2) = 0.150
S = 1.03
2973 re¯ections
243 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
Baumeister, U. & Hartung, H. (1997). Acta Cryst. C53, m1246±m1248.
È
Burger, K. S., Chaudhuri, P., Wieghardt, K. & Nuber, B. (1995). Chem. Eur. J.
1, 583±593.
w = 1/[ꢅ2(F2o) + (0.1P)2]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max < 0.001
Cano, J., Munno, G. D., Sanz, J. L., Ruiz, R., Faus, J., Lloret, F., Julve, M. &
Caneschi, A. (1997). J. Chem. Soc. Dalton Trans. pp. 1915±1923.
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3
Ê
Áꢆmax = 0.40 e A
3
Ê
0.30 e A
Áꢆmin
=
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
MnÐO3i
MnÐO5
MnÐN2
2.098 (2)
2.160 (3)
2.235 (3)
MnÐN1
MnÐO2
MnÐO1
2.260 (3)
2.271 (2)
2.281 (2)
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424.
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m518.
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m403.
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Okabe, N. & Koizumi, M. (1997). Acta Cryst. C53, 852±854.
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X-ray Instruments Inc., Madison, Wisconsin, USA.
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Madison, Wisconsin, USA.
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(1998). Inorg. Chim. Acta, 277, 21±25.
O3iÐMnÐO5
O3iÐMnÐN2
O5ÐMnÐN2
O3iÐMnÐN1
O5ÐMnÐN1
N2ÐMnÐN1
O3iÐMnÐO2
O5ÐMnÐO2
86.79 (10)
90.04 (10)
123.97 (11)
158.43 (11)
92.42 (11)
72.56 (11)
98.05 (10)
147.16 (10)
N2ÐMnÐO2
N1ÐMnÐO2
O3iÐMnÐO1
O5ÐMnÐO1
N2ÐMnÐO1
N1ÐMnÐO1
O2ÐMnÐO1
88.63 (10)
94.26 (10)
105.72 (9)
90.04 (10)
143.66 (10)
95.83 (10)
57.31 (8)
Symmetry code: (i) ‡ x; 12 y; z
.
1
2
1
2
Table 2
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O5ÐH5BÁ Á ÁO1ii
0.86 (2)
0.85 (2)
1.86 (2)
1.87 (3)
2.718 (4)
2.672 (4)
172 (5)
157 (5)
O5ÐH5CÁ Á ÁO4i
Symmetry codes: (i) ‡ x; 12 y; z 21; (ii) x; y; z.
1
2
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(2003). Transition Met. Chem. 28, 600±605.
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Inorg. Chem. Commun. 6, 1188±1191.
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Cryst. C58, m268±m269.
Water H atoms were located from difference maps and included
Ê
in the re®nement with a DFIX restraint of 0.85 (2) A. Aromatic
H atoms were placed in calculated positions and treated as riding
Ê
(CÐH = 0.93 A).
ꢁ
m290 Cheng-Bing Ma et al.
[Mn(C8H4O4)(C10H8N2)(H2O)]
Acta Cryst. (2004). C60, m288±m290