A one-dimensional ladder-like coordination polymer derived from chains formed via hydrogen bonds: Catena-poly[[aquadipyridinenickel(II)]-μ-2,2′-dithiodibenzoato-K 3O,O′:O″]

Article abstract of DOI:10.1107/S0108270104017469

The synthesis and crystal structure of [Ni(C₁₄H ₈O₄S₂)(C₅H ₅N) ₂(H₂O)]_n, (I), was analyzed. It was observed that compound (I) was synthesized by hydrothermal reaction of an Ni ^II salt with the ligand and pyridine in a 1:1:4 molar ratio at 383 K for 2d. The compound (I) had each Ni^II cation coordinated by two N atoms from two pyridine ligands, three carboxylate oxygen atoms from two different dithiodibenzoate ligands and one oxygen atom from coordinated water molecule in distorted octahedral gemotry. The results show that compound possesses a ladder-like structure due to hydrogen bond interactions between two shoulder to shoulder chains.

Full text of DOI:10.1107/S0108270104017469

metal-organic compounds
with the different coordination modes of 2,20-dtdb, should
allow the fabrication of different coordination polymer
topologies. Finally, the ligand has a strong capability of
forming hydrogen bonds, which play an important role in the
assembly of supramolecular compounds. Thus, we prepared
the title compound, (I), by the hydrothermal reaction of an
NiII salt with the ligand and pyridine in a 1:1:4 molar ratio at
383 K for 2 d.
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
A one-dimensional ladder-like
coordination polymer derived from
chains formed via hydrogen bonds:
catena-poly[[aquadipyridinenickel(II)]-
l-2,20-dithiodibenzoato-j3O,O0:O00]
Wen-Na Zhao,* Jian-Wei Zou and Qing-Shen Yu
Nibo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315104,
People's Republic of China
The present crystallographic analysis reveals that (I) is a
one-dimensional ladder-like coordination polymer. As shown
in Fig. 1, each NiII cation is coordinated by two N atoms from
two pyridine ligands, three carboxylate O atoms from two
different dithiodibenzoate ligands and one O atom from a
coordinated water molecule. One N atom (N2) and three O
atoms (O1, O2 and O3A) form the equatorial plane, while the
axial positions are occupied by one N atom (N1) and one O
atom (O5), with an N1ÐNi1ÐO5 bond angle of 177.25 (5)ꢀ.
Thus, the coordination environment around the NiII centre
can be best described as having a distorted octahedral
geometry. The NiII cation is approximately coplanar with the
coordination atoms in the equatorial plane, with a slight
Correspondence e-mail: wnzhao@163.com
Received 14 May 2004
Accepted 16 July 2004
Online 11 August 2004
The title one-dimensional chain nickel(II)±disul®de complex,
[Ni(C14H8O4S2)(C5H5N)2(H2O)]n, has each NiII cation coor-
dinated by two N atoms from two pyridine ligands, three
carboxylate O atoms from two different dithiodibenzoate
ligands and one O atom from a coordinated water molecule, in
a distorted octahedral coordination geometry. Each dithio-
dibenzoate ion links two NiII cations through its carboxylate O
atoms, making the structure polymeric. Hydrogen-bond
interactions between two shoulder-to-shoulder chains lead to
the formation of a ladder-like structure.
Ê
deviation of 0.001 A. The NiÐN and NiÐO distances are in
the ranges 2.0594 (14)±2.1279 (14) and 2.0216 (13)±
Ê
2.1588 (11) A, respectively (Table 1), which are typical values
for NiÐN and NiÐO coordination distances (Kongshaug &
Comment
Fgellvag, 2003).
The two carboxylate groups of each 2,20-dtdb ligand adopt
different coordination modes, namely monodentate and
chelating±bidentate. As a result, the O1ÐC1ÐO2 angle
[120.07 (13)ꢀ] is about 5ꢀ smaller than that of O3ÐC14ÐO4
[125.22 (14)ꢀ]. The dihedral angle between the two phenyl
The rational design of coordination polymers has attracted
much attention, due to the potential applications of these
materials, which range from gas storage and ion exchange to
heterogeneous catalysis (Moulton & Zaworotko, 2001; Janiak,
2003). The construction of metal±organic frameworks can be
achieved via two kinds of interaction, i.e. coordinate covalent
bonds and weaker intermolecular forces. Weaker non-covalent
interactions, such as hydrogen bonds or ꢀ±ꢀ interactions, are
important for the packing of one-dimensional chains, two-
dimensional nets and three-dimensional open frameworks.
Furthermore, the selection or design of suitable ligands
containing certain features, such as ¯exibility and versatile
binding modes, is crucial for the construction of speci®c
supramolecular architectures. This concept has been demon-
strated by the great variety of structural topologies of discrete
supramolecular complexes or in®nite supramolecular arrays
(Leininger et al., 2000; Janiak, 2003).
Against this background, we chose 2,20-dithiodibenzoic acid
(2,20-H2dtdb) as an organic ligand for study, based on the
following considerations. Firstly, the twisted binding site
passing through the centre of the SÐS bond makes the ligand
¯exible. Secondly, the carboxylate binding groups, coupled
Figure 1
A perspective view of (I), with the atom-numbering scheme. Displace-
ment ellipsoids are drawn at the 30% probability level and H atoms are
shown as small spheres of arbitrary radii. [Symmetry code: (i) x, y, z 1.]
Acta Cryst. (2004). C60, m443±m444
DOI: 10.1107/S0108270104017469
# 2004 International Union of Crystallography m443

metal-organic compounds
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.028
wR(F2) = 0.082
S = 1.07
5535 re¯ections
315 parameters
H atoms: see below
w = 1/[ꢅ2(Fo2) + (0.0509P)2]
2
where P = (Fo + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢆmax = 0.43 e A
3
Ê
0.43 e A
Áꢆmin
=
Figure 2
Table 1
Selected geometric parameters (A, ).
A view of the one-dimensional ladder-like structure in (I), which
propagates along the c axis. Hydrogen-bond interactions are indicated by
dashed lines.
ꢀ
Ê
Ni1ÐO3i
Ni1ÐN2
Ni1ÐO5
Ni1ÐO2
Ni1ÐN1
2.0216 (13)
2.0594 (14)
2.0877 (13)
2.1079 (12)
2.1279 (14)
Ni1ÐO1
S1ÐC7
S1ÐS2
S2ÐC8
2.1588 (11)
1.7976 (18)
2.0502 (7)
1.7970 (17)
rings is 96.7 (5)ꢀ, which is close to the angle in the analogous
Co±2,20-dtdb complex (Ganesh et al., 1990).
Each dithiodibenzoate anion links two NiII cations through
its carboxylate O atoms, making the structure polymeric. The
NiÁ Á ÁNi distance bridged by 2,2 -dtdb is 12.581 (8) A.
Furthermore, hydrogen-bond interactions between two
shoulder-to-shoulder chains lead to the formation of a ladder-
like structure (Fig. 2). The hydrogen-bond distances of O5Ð
O3iÐNi1ÐN2
O3iÐNi1ÐO5
N2ÐNi1ÐO5
O3iÐNi1ÐO2
N2ÐNi1ÐO2
O5ÐNi1ÐO2
O3iÐNi1ÐN1
N2ÐNi1ÐN1
O5ÐNi1ÐN1
97.68 (6)
91.87 (6)
91.92 (6)
97.87 (5)
164.42 (5)
88.65 (5)
90.23 (6)
89.56 (6)
177.25 (5)
O2ÐNi1ÐN1
O3iÐNi1ÐO1
N2ÐNi1ÐO1
O5ÐNi1ÐO1
O2ÐNi1ÐO1
N1ÐNi1ÐO1
C7ÐS1ÐS2
89.31 (5)
159.57 (5)
102.73 (5)
86.58 (5)
61.75 (4)
90.84 (5)
106.17 (6)
104.46 (6)
0
Ê
C8ÐS2ÐS1
H5AÁ Á ÁO4(x, y, z 1) and O5ÐH5CÁ Á ÁO1(1 x, 1 y,
Symmetry code: (i) x; y; z 1.
Ê
z) are 2.6642 (19) and 2.837 (2) A, respectively (Table 2).
1
A bimetallic six-membered hydrogen-bonded ring is thus
Table 2
Hydrogen-bonding geometry (A, ).
Ê
formed, with an NiÁ Á ÁNi distance of 5.374 (8) A.
ꢀ
Ê
The bimetallic unit can be viewed as the basic building
block of the structure, and these are joined together through
sharing of the NiII apices with 2,20-dtdb ligands to give the ®nal
one-dimensional polymer, which consists of rectangular grids
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O5ÐH5AÁ Á ÁO4i
0.74 (2)
0.78 (3)
1.96 (2)
2.06 (3)
2.6642 (19)
2.837 (2)
159 (2)
173 (3)
O5ÐH5CÁ Á ÁO1ii
Ê
with dimensions of 12.6 Â 5.4 A, based on the metal-to-metal
Symmetry codes: (i) x; y; z 1; (ii) 1 x; 1 y; 1 z.
distances. Therefore, the presence of hydrogen bonds in (I)
plays an important role in the formation of the ®nal ladder-
like coordination polymer, which is notably different from
other ladder-like structures based on coordinate covalent
bonds (Liu et al., 2004).
H atoms on C atoms were generated geometrically and allowed to
=
Ê
ride on their respective parent atoms, with CÐH = 0.95 A and Uiso
1.2Ueq(C). Water H atoms were located in difference maps and
re®ned freely.
Data collection: SMART (Siemens, 1994); cell re®nement: SMART
and SAINT (Siemens, 1994); data reduction: SHELXTL (Sheldrick,
1997a); program(s) used to solve structure: SHELXS97 (Sheldrick,
1997b); program(s) used to re®ne structure: SHELXL97 (Sheldrick,
1997b); molecular graphics: SHELXTL.
Experimental
For the preparation of (I), a mixture of Ni(NO3)2Á6H2O (0.2 mmol)
with 2,20-H2dtdb (0.2 mmol) and pyridine (0.4 mmol) in a 1:1:4 molar
ratio dissolved in water (10 ml) was sealed in a stainless-steel reactor
with a Te¯on liner and heated at 383 K for 2 d. A number of green
prism-shaped crystals of (I) were obtained after cooling the solution
to room temperature. The yield of (I) was ca 65%, based on 2,20-dtdb.
This work was supported by the Natural Science Founda-
tion of China.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ1161). Services for accessing these data are
described at the back of the journal.
Crystal data
3
[Ni(C14H8O4S2)(C5H5N)2(H2O)]
Mr = 539.25
Monoclinic, P21=c
a = 13.925 (3) A
b = 15.099 (3) A
Ê
c = 12.581 (3) A
ꢁ = 114.00 (3)ꢀ
V = 2416.5 (11) A
Z = 4
Dx = 1.482 Mg m
Mo Kꢂ radiation
Cell parameters from 5535
re¯ections
References
Ê
Ê
ꢃ = 1.6±27.5ꢀ
ꢄ = 1.01 mm
T = 293 (2) K
Ganesh, V., Radha, A., Seshasayee, M., Subrahmaniyan, T. & Aravamudan, G.
(1990). Acta Cryst. C46, 2302±2305.
1
Janiak, C. (2003). J. Chem. Soc. Dalton Trans. pp. 2781±2804.
Kongshaug, K. O. & Fgellvag, H. (2003). Solid State Sci. 5, 303±310.
Leininger, S., Olenvuk, B. & Stang, P. J. (2000). Chem. Rev. 100, 853±908.
Liu, Z., Zhang, D., Liu, C. & Zhu, D. (2004). Chem. Lett. 33, 180±181.
Moulton, B. & Zaworotko, M. Z. (2001). Chem. Rev. 101, 1629±1658.
3
Ê
Prism, green
0.26 Â 0.20 Â 0.18 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
5535 independent re¯ections
4673 re¯ections with I > 2ꢅ(I)
ꢃmax = 27.5ꢀ
È
Sheldrick G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (1997a). SHELXTL. Version 5.10. Bruker AXS Inc.,
Madison, Wisconsin, USA.
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.784, Tmax = 0.833
5535 measured re¯ections
h = 18 ! 16
Sheldrick, G. M. (1997b). SHELXS97 and SHELXL97. University of
GoÈttingen, Germany.
Siemens (1994). SMART and SAINT. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
k = 19 ! 0
l = 0 ! 16
ꢁ
m444 Zhao, Zou and Yu [Ni(C14H8O4S2)(C5H5N)2(H2O)]
Acta Cryst. (2004). C60, m443±m444