Poly[[bis(pyridine-kN)copper(II)]-μ35-hydroxyisophthalato- k3O:O':O ]

Article abstract of DOI:10.1107/S0108270104027660

The design and synthesis of supramolecular coordination in Poly[[bis(pyridine-κN)copper(II)]-μ₃-5-hydroxyisophthal ato-κ³O:O^′:O^″ polymer networks was investigated. In this complex the Cu atoms were found to be coordinated by two N atoms from the pyridine ligands and by three O atoms from hydroxyisophthalate ligands in a highly distorted triangular bipyramidal environment. The dihedral angle between the two py rings that coordinate to the same Cu atom is 75.41°. The results show that dihedral angle between two π-π interacting py rings is 22.83° and the distance between the centroids of the two py rings is 4.131 A.

Full text of DOI:10.1107/S0108270104027660

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
mimic for the third carboxy group, which remains protonated
in the reported layered and helical chain polymers (Foreman
et al., 1999; Cao et al., 2004), as well as in the title compound.
As part of our research interest in new poly(carboxylic acid)-
bridged polymeric complexes, the title complex, (I), was
obtained by the hydrothermal reaction of OH-H2BDC with
cupric acetate and pyridine (py).
ISSN 0108-2701
Poly[[bis(pyridine-jN)copper(II)]-l3-
5-hydroxyisophthalato-j3O:O0:O00]
Xin-Yi Cao,a,b Jian Zhang,a Yao Kang,a Jian-Kai Chenga
and Yuan-Gen Yaoa*
aThe State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002,
People's Republic of China, and bGraduate School, The Chinese Academy of
Sciences, Beijing 100039, People's Republic of China
Correspondence e-mail: yyg@ms.fjirsm.ac.cn
Received 14 September 2004
Accepted 28 October 2004
Online 23 November 2004
As shown in Fig. 1, the Cu atoms in (I) are ®ve-coordinate in
a highly distorted triangular bipyramidal environment invol-
ving two N atoms from the pyridine ligands and three O atoms
from hydroxyisophthalate ligands, with CuÐO distances in
In the title compound, [Cu(C8H4O5)(C5H5N)2]n or [Cu(OH-
BDC)(py)2]n (where OH-H2BDC is 5-hydroxyisophthalic acid
and py is pyridine), the Cu atoms are coordinated by two N
atoms from the pyridine ligands and by three O atoms from
hydroxyisophthalate ligands in a highly distorted triangular
bipyramidal environment, with CuÐO distances in the range
Ê
the range 1.941 (4)±2.225 (5) A and CuÐN distances of
Ê
2.014 (6) and 2.046 (6) A (Table 1). These bond distances are
similar to those found in {[Cu2(1,3-bdc)2(py)2]4}n (1,3-bdc is
1,3-benzenedicarboxylate; Bourne, Lu et al., 2001), [Cu3-
(TMA)2(H2O)3]n (TMA is benzene-1,3,5-tricarboxylate; Chui
et al., 1999), [Cu2(bdc)2(Q)2]n (Q is quinoline; Moulton et al.,
2003) and the closest relative catena-[(ꢁ3-benzene-1,3-dicar-
boxylato)bis(pyridine)copper], [Cu(1,3-bdc)(py)2]n (Bourne,
Mondal & Zaworotko, 2001). The dihedral angle between
the two py rings that coordinate to the same Cu atom is
75.41ꢀ. The asymmetric unit thus consists of one Cu atom,
two pyridine ligands and one hydroxyisophthalate ligand. The
Ê
1.941 (4)±2.225 (5) A and CuÐN distances of 2.014 (6) and
Ê
2.046 (6) A. The [Cu(OH-BDC)]n two-dimensional network is
built up from interlocking 22-, 15- and eight-membered rings
via sharing of Cu atoms and OÐHÁ Á ÁO hydrogen bonds.
Consolidation of the packing structure is achieved by edge- or
point-to-face CÐHÁ Á Áꢀ interactions and offset or slipped ꢀ±ꢀ
stacking interactions.
Comment
The design and syntheses of supramolecular coordination
polymer networks, especially those constructed via hydrogen
bonding and ꢀ±ꢀ stacking interactions, has been a ®eld of
rapid growth because of the special physical properties of
these compounds and their potential applications in functional
materials (Atwood et al., 1996; Barton et al., 1999). Coordi-
nation polymers containing symmetric multidentate
benzenecarboxylate molecules as bridging ligands have
attracted increasing attention because of their interesting
network structures and potential applications in many ®elds
(Li et al., 1999; Yaghi et al., 1995; Chui et al., 1999). Large
numbers of coordination polymers have been prepared from
metal ions and aromatic carboxylate ligands, such as
benzenehexacarboxylate (Wu et al., 1996), 1,3-benzenedi-
carboxylate (Reineke et al., 1999) and 1,3,5-benzenetri-
carboxylate (Yaghi et al., 1997; Daiguebonne et al., 1999;
Gutschke et al., 1996). 5-Hydroxyisophthalic acid, OH-
H2BDC, like benzene-1,3,5-tricarboxylic acid, has two
carboxylic acid groups arranged meta with respect to one
another, but with a phenol hydroxy group meta to both (Plate
et al., 2001). This phenol hydroxy group was intended as a
Figure 1
The structure of (I), showing the atom-numbering scheme. Displacement
ellipsoids are plotted at the 30% probability level. Atoms labeled with the
suf®xes A and B are at the symmetry positions ( x, 2 y, 1 z) and
(12 + x, 32 y, 12 + z), respectively.
m654 # 2004 International Union of Crystallography
DOI: 10.1107/S0108270104027660
Acta Cryst. (2004). C60, m654±m656

metal-organic compounds
Ê
5-hydroxyisophthalate group acts as a tridentate ligand in this
structure, with one carboxylate group bonding in a mono-
dentate fashion to one Cu atom and the two remaining O
atoms bonding in a monodentate fashion to two further Cu
atoms. As illustrated in Fig. 2, the interesting feature of
polymer (I) is that the OH-BDC ligands link copper centers in
different ways to produce three different subrings, CuÁ Á ÁCu
3.627 (8) and 3.653 (3) A, respectively (Janiak, 2000). The
dihedral angle between two ꢀ±ꢀ interacting py rings is 22.83ꢀ
and the distance between the centroids of the two py rings is
Ê
4.131 (1) A.
Experimental
For the preparation of the title compound, a mixture of Cu-
(CH3CO2)2ÁH2O (0.4 mmol), OH-H2BDC (0.3 mmol), pyridine
(0.6 mmol), NaOH (0.5 mmol) and water (15 ml) was sealed in a
25 ml stainless steel reactor with a Te¯on liner. The reaction system
was heated at 433 K for 60 h, and then cooled slowly to room
temperature. A large number of green crystals of the title complex
were obtained and collected by ®ltration, washed with water and
dried in air (56.2% yield based on H3OABDC).
Ê
distances of 16.935 (5), 9.814 (2) and 4.523 (3) A, respectively.
The two-dimensional network of [Cu(OH-BDC)]n moieties
also contains an OÐHÁ Á ÁO hydrogen bond [O5ÐH5A =
iii
iii
Ê
Ê
Ê
0.82 A, H5AÁ Á ÁO3 = 1.94 A, O5Á Á ÁO3 = 2.752 (8) A and
iii
1
Ê
O5ÐH5AÁ Á ÁO3 = 174 A; symmetry code: (iii)
x
12 ; y
;
2
z ‡ 32 ] and can be envisaged as being built up from inter-
locking R11ꢁ15†, R22ꢁ22† and eight-membered rings. The coor-
dinated pyridine rings point to the layer regions alternately
above and below the two-dimensional net as terminal ligands.
Finally, as illustrated in Fig. 3, the two-dimensional [Cu(OH-
BDC)(py)2]n layers are assembled into a three-dimensional
framework via edge- or point-to-face CÐHÁ Á Áꢀ interactions
and offset or slipped ꢀ±ꢀ stacking interactions, in which the
mean CÐHÁ Á Áꢀ and ꢀ±ꢀ hydrogen-bonding distances are
Crystal data
3
[Cu(C8H4O5)(C5H5N)2]
Mr = 401.85
Monoclinic, P21=n
Dx = 1.472 Mg m
Mo Kꢃ radiation
Cell parameters from 2698
re¯ections
Ê
a = 10.1055 (9) A
ꢄ = 2.7±25.1ꢀ
ꢁ = 1.24 mm
T = 293 (2) K
Ê
b = 11.6854 (11) A
1
Ê
c = 15.7236 (14) A
ꢂ = 102.415 (2)ꢀ
Ê
V = 1813.3 (3) A
Z = 4
3
Prism, green
0.40 Â 0.30 Â 0.20 mm
Data collection
Siemens SMART CCD area-
detector diffractometer
' and ! scans
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.802, Tmax = 1.000
5825 measured re¯ections
3159 independent re¯ections
2455 re¯ections with I > 2ꢅ(I)
Rint = 0.048
ꢄmax = 25.1ꢀ
h = 12 ! 7
k = 13 ! 12
l = 18 ! 16
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.071
wR(F2) = 0.192
S = 1.07
3159 re¯ections
w = 1/[ꢅ2(F2o) + (0.0665P)2
+ 13.3127P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max < 0.001
3
Ê
Áꢆmax = 0.72 e A
3
Ê
0.45 e A
235 parameters
H-atom parameters constrained
Áꢆmin
=
Figure 2
A view of (I), showing how the organization of the two different subrings
contributes to the construction of the [Cu(OH-BDC)]n two-dimensional
network.
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
CuÐO2
CuÐO4i
CuÐN2
1.941 (4)
1.955 (4)
2.014 (6)
CuÐN1
CuÐO1ii
2.046 (6)
2.225 (5)
O2ÐCuÐO4i
O2ÐCuÐN2
O4iÐCuÐN2
O2ÐCuÐN1
O4iÐCuÐN1
157.2 (2)
94.0 (2)
89.6 (2)
88.9 (2)
86.2 (2)
N2ÐCuÐN1
O2ÐCuÐO1ii
O4iÐCuÐO1ii
N2ÐCuÐO1ii
N1ÐCuÐO1ii
175.0 (2)
108.26 (19)
93.81 (18)
95.1 (2)
88.0 (2)
Symmetry codes: (i) 12 ‡ x; 23 y; z 21; (ii) x; 2 y; 1 z.
All H atoms were placed at calculated positions and re®ned with
isotropic displacement parameters, using a riding model [CÐH =
Ê
Ê
0.93 A, OÐH = 0.82 A, and Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O)].
Data collection: SMART (Siemens, 1996); cell re®nement: SMART
and SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL
(Siemens, 1994); 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.
Figure 3
A packing diagram of the title compound, showing the complex CÐ
HÁ Á Áꢀ and ꢀ±ꢀ interactions, with hydrogen bonds shown as dashed lines.
ꢂ
Acta Cryst. (2004). C60, m654±m656
Xin-Yi Cao et al. [Cu(C8H4O5)(C5H5N)2] m655

metal-organic compounds
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This work was supported by the National Natural Science
Foundation of China under project No. 20173063, the State
Key Basic Research and Development Plan of China (grant
No. 001CB108906), and the NSF of Fujian Province (grant No.
E0020001).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV1213). Services for accessing these data are
described at the back of the journal.
Plate, M. J., Foreman, M. R. St J., Howie, R. A., Skakle, J. M. S., McWilliam,
S. A., Coronado, E. & Gomez-Garcia, C. J. (2001). Polyhedron, 20, 2293±
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m656 Xin-Yi Cao et al. [Cu(C8H4O5)(C5H5N)2]
Acta Cryst. (2004). C60, m654±m656