Catena-poly[[tetraaquamanganese(II)]-μ-4-(carboxylatomethylsulfanyl) phenoxyacetato]

Article abstract of DOI:10.1107/S010827010601184X

The title compound, [Mn(C₁₀H₈O₅S)(H ₂O)₄]_n, a one-dimensional manganese(II) complex comprising helical chains bridged by 4-(carboxylatomethylsulfanyl) phenoxyacetate ligands has been characterized by single-crystal X-ray diffraction analysis. Hydrogen-bonding interactions between adjacent chains extend the complex into a three-dimensional supramolecular architecture.

Full text of DOI:10.1107/S010827010601184X

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
different kinds of coordination polymers, including in®nite
one-dimensional chain compounds, two-dimensional layer
compounds and three-dimensional netlike compounds (Gao,
Huo et al., 2005; Gao, Su et al., 2005). We report here the title
novel one-dimensional manganese(II) complex, (I), com-
prising helical chains bridged by 4-(carboxylatomethylsul-
fanyl)phenoxyacetate (p-CMPT2 ).
ISSN 0108-2701
catena-Poly[[tetraaquamanganese(II)]-
l-4-(carboxylatomethylsulfanyl)-
phenoxyacetato]
Hong Su, Yun-Long Feng* and Yi-Hang Wen
The present X-ray diffraction analysis shows that complex
(I) possesses a one-dimensional single helical structure. The
fundamental unit of the crystal structure is illustrated in Fig. 1.
Each MnII ion is six-coordinated in a distorted octahedral
Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of
Physical Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004, People's
Republic of China
Correspondence e-mail: sky37@zjnu.cn
geometry. Its equatorial plane is de®ned by atoms O1, O1W,
O3W and O4i [symmetry code: (i) x + 1, y
Received 14 October 2005
Accepted 31 March 2006
Online 22 April 2006
1
2
,
an r.m.s. deviation of 0.075 (2) A; the deviation of the Mn
z + 1], with
II
Ê
Ê
atom from this plane is 0.0116 (2) A. The axial positions are
occupied by atoms O2W and O4W, with an angle of
170.53 (6)ꢀ. It is interesting to note that each p-CMPT2
ligand, serves as a bridging ligand to link two MnII atoms,
forming a single-strand helical coordination polymer. Both
carboxylate anions in one p-CMPT2 ligand are mono-coor-
dinated to the adjacent metal atom, with MnÐO distances of
The title compound, [Mn(C10H8O5S)(H2O)4]n, a one-dimen-
sional manganese(II) complex comprising helical chains
bridged by 4-(carboxylatomethylsulfanyl)phenoxyacetate
ligands has been characterized by single-crystal X-ray
diffraction analysis. Hydrogen-bonding interactions between
adjacent chains extend the complex into a three-dimensional
supramolecular architecture.
Ê
2.1599 (15) and 2.1528 (16) A (Fig. 2). In this way, each
p-CMPT2 acts as a bidentate group linking two metal atoms
and yields a half-turn unit of the helical structure. The distance
Ê
between neighbouring Mn atoms is 11.377 A. Extension of the
Comment
structure in one dimension along the b axis gives a one-
dimensional helical Mn±p-CMPT2 network (Fig. 2), resulting
from the unique coordination feature of the p-CMPT2
ligands. Each helical cycle contains three Mn atoms and two
bridging p-CMPT2 ligands.
The crystal engineering and synthesis of discrete metallo-
helicates and in®nite metal-containing helical coordination
polymers have received much attention from chemists,
because helicity is an essential feature of living systems and is
important in advanced materials, such as optical devices,
enantiomer separation, chiral synthesis, ligand exchange and
selective catalysis (Chen & Suslick, 1993; Woods et al., 1996;
Piguet et al., 1997; Qi et al., 2003). Most of the recent studies in
this area have been involved with the construction of
compounds from d10 transition metal ions and functional
ligands (Psillakes et al., 1997; Tong et al., 1998; Nomiya et al.,
2000). In this context, the ®ne-tuning of organic ligands and
the careful selection of metal ions are especially crucial to the
construction of desirable helical frameworks (Nishida et al.,
2001; Gao et al., 2003; Barnett & Champness, 2003). We are
interested in the solid-state coordination chemistry of 4-(car-
boxylatomethylsulfanyl)phenoxyacetic acid (p-CMPTH2),
which remains largely unexplored. Although this is a rather
simple molecule, it has the potential for coordinative inter-
action and hydrogen bonding. Firstly, it has two carboxyl
groups, one ether O atom and one thioether S atom, which
induce multiple coordination modes with transition metal ions.
Secondly, it can act not only as a hydrogen-bond donor but
also as hydrogen-bond acceptor, owing to the existence of
deprotonated and/or protonated carboxyl groups. Therefore,
it is regarded as an excellent candidate for the construction of
The structure of (I) also contains intermolecular hydrogen
bonds, which are formed between the free water molecules
Figure 1
A view of the title compound showing the atom-numbering scheme. Non-
water H atoms have been omitted for clarity. Displacement ellipsoids are
1
drawn at the 30% probability level. [Symmetry code: (i) 1 x, y
z.]
,
2
1
m208 # 2006 International Union of Crystallography
DOI: 10.1107/S010827010601184X
Acta Cryst. (2006). C62, m208±m210

metal-organic compounds
and uncoordinated carboxylate O atoms [OÁ Á ÁO = 2.676 (2)
chemistry of well de®ned helical coordination polymers is
necessary for the understanding of the detection and ampli-
®cation of chirality. There is increasing interest in dynamic
helical coordination polymers (Yamada et al., 2004; Matsuda et
al., 2004), the most important feature of which is high sensi-
tivity to a chiral environment, and therefore such systems
might provide the basis to construct a novel chirality-sensing
probe. This work has demonstrated that extended structural
motifs can be constructed through p-CMPT2 ligands bridging
neutral one-dimensional helical chains.
Ê
and 2.744 (2) A], resulting in a two-dimensional layer struc-
ture parallel to the bc plane. Adjacent two-dimensional layers
form a three-dimensional framework linked by further inter-
molecular hydrogen bonds formed between the water mol-
ecules, coordinated carboxylate O atoms and water molecules
Ê
of an adjacent layer [OÁ Á ÁO = 2.972 (3) and 2.878 (2) A]
(Fig. 3).
In summary, employing the ¯exibility and unique coordi-
nation feature of p-CMPT2 , we have successfully prepared a
one-dimensional chain coordination polymer consisting of
helical chains bridged by p-CMPT2 . Knowledge of the
Experimental
4-(Carboxymethylsulfanyl)phenoxyacetic acid was prepared follow-
ing the method described for the synthesis of benzene-1,2-dioxy-
acetic acid by Mirci (1990). MnCl2Á6H2O (0.099 g, 0.5 mmol) and
4-(carboxymethylsulfanyl)phenoxyacetic acid (0.224 g, 1 mmol) were
dissolved separately in water (25 ml) and the two solutions mixed
slowly with stirring for about 15 min at room temperature. The pH
was adjusted to 6 with 0.1 M sodium hydroxide. Colourless crystals of
(I) separated from the ®ltered solution after several days (yield ca
56%). Elemental analysis calculated for C10H16MnO9S: C 32.70, H
4.39%; found: C 33.02, H 4.41%.
Crystal data
[Mn(C10H8O5S)(H2O)4]
Mr = 367.24
Monoclinic, P21
Z = 2
Dx = 1.724 Mg m
Mo Kꢁ radiation
ꢂ = 1.12 mm
T = 295 (2) K
Prism, colourless
0.37 Â 0.25 Â 0.16 mm
3
1
Ê
a = 5.0977 (10) A
Ê
b = 11.444 (2) A
Ê
c = 12.183 (2) A
ꢀ = 95.58 (3)ꢀ
V = 707.4 (2) A
3
Ê
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Figure 2
Ball-and-stick (left) and space-®lling (right) plots of (I), showing the one-
dimensional helical Mn±p-CMPT2 network along the b axis. H atoms
have been omitted.
Mn1ÐO4i
Mn1ÐO1
Mn1ÐO3W
2.1528 (16)
2.1599 (15)
2.1881 (15)
Mn1ÐO4W
Mn1ÐO1W
Mn1ÐO2W
2.2164 (14)
2.2185 (15)
2.2435 (17)
O4iÐMn1ÐO1
91.66 (5)
96.94 (6)
170.43 (6)
87.97 (6)
91.00 (6)
85.13 (6)
176.68 (7)
O1ÐMn1ÐO1W
O3WÐMn1ÐO1W
O4WÐMn1ÐO1W
O4iÐMn1ÐO2W
O1ÐMn1ÐO2W
O3WÐMn1ÐO2W
O4WÐMn1ÐO2W
87.54 (6)
84.11 (6)
95.27 (6)
89.43 (6)
98.19 (6)
86.15 (6)
170.53 (6)
O4iÐMn1ÐO3W
O1ÐMn1ÐO3W
O4iÐMn1ÐO4W
O1ÐMn1ÐO4W
O3WÐMn1ÐO4W
O4iÐMn1ÐO1W
1
2
Symmetry code: (i) x ‡ 1; y
;
z ‡ 1.
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1WÐH10Á Á ÁO1ii
O1WÐH11Á Á ÁO2
O2WÐH12Á Á ÁO4iii
O2WÐH13Á Á ÁS1ii
O3WÐH14Á Á ÁO5i
O3WÐH15Á Á ÁO4Wii
O4WÐH16Á Á ÁO5iv
O4WÐH17Á Á ÁO2v
0.85 (3)
0.86 (2)
0.85 (2)
0.85 (2)
0.85 (2)
0.84 (2)
0.85 (2)
0.85 (2)
2.15 (3)
1.83 (3)
2.08 (3)
2.47 (3)
1.97 (3)
2.08 (3)
1.85 (2)
1.93 (3)
2.972 (3)
2.651 (2)
2.896 (2)
3.316 (2)
2.709 (2)
2.878 (2)
2.676 (2)
2.744 (2)
163 (2)
161 (3)
162 (3)
175 (3)
145 (2)
159 (2)
164 (2)
162 (2)
1
1
Figure 3
A packing diagram for (I). Hydrogen bonds are depicted as dashed lines.
Symmetry codes: (i) x ‡ 1; y
;
z ‡ 1; (ii) x ‡ 1; y; z; (iii) x ‡ 2; y
;
2
z ‡ 1; (iv)
2
1
2
x; y; z ‡ 1; (v) x ‡ 1; y
;
z ‡ 2.
ꢁ
Acta Cryst. (2006). C62, m208±m210
Su et al. [Mn(C10H8O5S)(H2O)4] m209

metal-organic compounds
Data collection
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: TY1014). Services for accessing these data are
described at the back of the journal.
Rigaku R-AXIS RAPID
diffractometer
! scans
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
Tmin = 0.709, Tmax = 0.840
6919 measured re¯ections
3164 independent re¯ections
2967 re¯ections with I > 2ꢃ(I)
Rint = 0.024
ꢄmax = 27.5ꢀ
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This project was supported by the Education Department of
Zhejiang Province (grant No. 20030711).
ꢁ
m210 Su et al. [Mn(C10H8O5S)(H2O)4]
Acta Cryst. (2006). C62, m208±m210