Poly[μ2-4-amino-benzoato-aqua-μ2-nitrato-zinc]

Article abstract of DOI:10.1107/S0108270107036256

In the title compound, [Zn(C7H6NO2)(NO3)(H2O)] n , the Zn atom is coordinated by two nitrate ions, one aqua mol-ecule and two 4-amino-benzoate ions in a distorted octa-hedral geometry. The structure of the compound exhibits a two-dimensional layer, which is formed by the inter-connection of [Zn(C7H6NO2)(H2O)] n chains via 2-nitrate bridges or by the inter-connection of [Zn(NO3)(H2O)] n chains via 2-4-amino-benzoate bridges. International Union of Crystallography 2007.

Full text of DOI:10.1107/S0108270107036256

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
a carboxylate O atom (Sundberg et al., 1998; Chandrasekhar et
al., 1988; Amiraslanov et al., 1979), chelating and/or bridging
ligands through its amide and/or carboxylate groups (Zheng et
al., 2001; Rzaezynska & Belskii, 1994; Hauptmann et al., 2000).
Finally, 4-abaH may be protonated to form organic cation
templating agents (Wang et al., 2002). Recently, a compound
containing mixed 4-aminobenzoate and another nitrogen-
donor ligand has been synthesized in our group (Zhang & Lu,
2005). As part of our continuing investigation of this type of
compound, we report here the synthesis and characterization
of the title complex, (I).
ISSN 0108-2701
Poly[l2-4-aminobenzoato-aqua-l2-
nitrato-zinc]
Quan-Zheng Zhang
As shown in Fig. 1, the Zn atom of (I) is coordinated by two
chelating carboxylate O atoms from one 4-aminobenzoate
ion, two bridging nitrate O atoms, an N atom from another
4-aminobenzoate ion and one coordinated water molecule in a
distorted octahedral geometry. The two nitrate O atoms [O4
Department of Chemistry and Materials Engineering, Hefei University, Hefei, Anhui
230022, People's Republic of China
Correspondence e-mail: zqz@hfuu.edu.cn
Received 17 June 2007
Accepted 24 July 2007
Online 9 August 2007
and O5ii; symmetry code: (ii) + x,
y, + z] are at the
1
1
1
2
2
2
Ê
apical positions [ZnÐO = 2.124 (2) and 2.333 (2) A, and
OÐZnÐO = 165.97 (8)ꢀ], while the two carboxylate O atoms
[O1i and O2i; symmetry code: (i) 21 + x, 21 y, 21 + z], the amine
N atom (N1) and the water O atom (O3) de®ne the equatorial
In the title compound, [Zn(C7H6NO2)(NO3)(H2O)]n, the Zn
atom is coordinated by two nitrate ions, one aqua molecule
and two 4-aminobenzoate ions in a distorted octahedral
geometry. The structure of the compound exhibits a two-
dimensional layer, which is formed by the interconnection of
[Zn(C7H6NO2)(H2O)]n chains via ꢀ2-nitrate bridges or by the
interconnection of [Zn(NO3)(H2O)]n chains via ꢀ2-4-amino-
benzoate bridges.
Ê
plane (mean deviation = 0.224 A). The Zn atom is raised
Ê
above the equatorial plane by 0.284 A towards the apical atom
O4.
The 4-aminobenzoate ligand adopts a chelating/bridging
coordination mode (Wang et al., 2002), linking two neigh-
bouring Zn coordination centres to form a one-dimensional
chain, [Zn(ꢀH2O)(C7H6NO2)]n, with a ZnÐNÐC bond angle
Comment
Ê
of 115.9 (2) and a ZnÁ Á ÁZn separation of 9.40 (2) A. Similarly,
Metal±organic framework materials have made rapid progress
in recent years because this class of materials may have
interesting physicochemical properties and potential applica-
tions such as adsorption, ion exchange and shape-selective
catalysis, and as nonlinear optical and magnetic materials. A
number of rigid or ¯exible bridging ligands have been
employed to construct metal±organic materials, including
one-, two- or three-dimensional frameworks. Generally, the
construction of frameworks can be achieved using either
covalent bonds or weaker intermolecular forces, e.g. hydrogen
bonds, aryl±aryl interactions, etc.
the nitrate ion acts as a ꢀ2-bridge (Huang et al., 2004; Ling et
al., 2004), linking two neighbouring metal centres to form
another one-dimensional chain, [Zn(NO3)(H2O)]n, with ZnÐ
OÐN bond angles of 112.5 (2) and 124.9 (2)ꢀ, and a ZnÁ Á ÁZn
Ê
separation of 5.74 (3) A. Thus, compound (I) exhibits a two-
dimensional layer-like structure (Fig. 2), which is formed by
the interconnection of neighbouring [Zn(H2O)(C7H6NO2)]n
chains via ꢀ2-nitrate bridges or by the interconnection of
neighbouring [Zn(NO3)(H2O)]n chains via ꢀ2-4-amino-
benzoate bridges. The two-dimensional layer consists of
Ê
rectangular grids with dimensions of 9.40 (2) Â 5.74 (3) A,
based on the ZnÁ Á ÁZn distances.
As a bifunctional organic ligand, 4-aminobenzoic acid
(4-abaH) has been reported in coordination chemistry
because of the richness of its coordination modes. Firstly,
4-abaH can act as a carboxylic acid synthon and also as a good
monodentate ligand through the amine group (Le Fur &
Masse, 1996; Chen & Chen, 2002). Secondly, deprotonated
4-aminobenzoic acid can act as a monodentate ligand through
Figure 1
A locally expanded unit of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level and H
atoms are shown as small spheres of arbitrary radii. [Symmetry codes: (i)
1
2
1
2
+ x, 12 y, 21 + z; (ii) 12 + x,
y, 12 + z.]
Acta Cryst. (2007). C63, m405±m406
DOI: 10.1107/S0108270107036256
# 2007 International Union of Crystallography m405

metal-organic compounds
Table 1
Selected geometric parameters (A, ).
It is noteworthy that there is hydrogen bonding in the title
compound. One weak interaction occurs between the layers.
The water ligand forms hydrogen bonds with the carboxylate
O atoms of the 4-aminobenzoate, with OÐHÁ Á ÁO distances of
ꢀ
Ê
Zn1ÐO2i
Zn1ÐO3
Zn1ÐN1
1.998 (2)
2.009 (2)
2.045 (3)
Zn1ÐO4
Zn1ÐO5ii
Zn1ÐO1i
2.124 (2)
2.333 (2)
2.470 (2)
Ê
2.720 (3) and 2.721 (3) A (Table 2). Such hydrogen-bonding
interactions consolidate the structural architecture and further
extend the two-dimensional layers into a three-dimensional
framework.
O2iÐZn1ÐO3
O2iÐZn1ÐN1
O3ÐZn1ÐN1
O2iÐZn1ÐO4
O3ÐZn1ÐO4
N1ÐZn1ÐO4
105.20 (9)
143.27 (9)
109.52 (10)
99.50 (9)
87.83 (10)
93.47 (10)
O3ÐZn1ÐO5ii
N1ÐZn1ÐO5ii
O4ÐZn1ÐO5ii
O3ÐZn1ÐO1i
N1ÐZn1ÐO1i
O4ÐZn1ÐO1i
78.81 (10)
87.07 (10)
165.97 (8)
148.46 (9)
86.17 (8)
119.26 (8)
1
2
Symmetry codes: (i) x
;
y ‡ 12; z ‡ 21; (ii) x ‡ 21; y ‡ 12; z ‡ 12.
Table 2
Hydrogen-bond geometry (A, ).
ꢀ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O3ÐH3BÁ Á ÁO2iii
0.83 (4)
0.85 (5)
1.89 (4)
1.88 (5)
2.720 (3)
2.721 (3)
177 (4)
171 (5)
O3ÐH3CÁ Á ÁO1iv
Symmetry codes: (iii) x ‡ 32; y ‡ 21; z ‡ 21; (iv) x ‡ 2; y ‡ 1; z ‡ 1.
Data collection: SMART (Siemens, 1996); cell re®nement:
SMART; data reduction: SAINT (Siemens, 1994); program(s) used to
solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXTL (Siemens, 1994); software used to prepare material for
publication: SHELXL97.
Figure 2
The two-dimensional structure of (I). All H atoms have been omitted for
clarity.
Experimental
An ethanol solution (8 ml) of 2,20-bipyridine (1.2 mmol) and 4-amino-
benzoic acid (1.6 mmol) was added slowly to an aqueous solution
(10 ml) of Zn(NO3)2Á6H2O (1 mmol) with continuous stirring for
30 min. The reaction mixture was then allowed to stand at room
temperature undisturbed for two weeks, resulting in colourless
crystals of (I) (yield 71%). Analysis calculated for C7H8N2O6Zn:
C 29.86, H 2.86, N 9.95%; found: C 29.81, H 2.71, N 9.89%.
This work was supported by the Start-up Fund of Hefei
University (grant No. 600811) and the Fund of Anhui
Provincial Education Department (grant No. KJ2007A014).
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV3098). Services for accessing these data are
described at the back of the journal.
Crystal data
3
Ê
References
[Zn(C7H6NO2)(NO3)(H2O)]
Mr = 281.52
V = 984.1 (2) A
Z = 4
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Ê
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Ê
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Ê
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Ê
Áꢄmax = 0.59 e A
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Ê
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=
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The H atoms of the coordinated water molecule were located in a
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Ê
atoms were constrained to an ideal geometry, with NÐH = 0.90 A
Ê
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ꢁ
m406 Quan-Zheng Zhang
[Zn(C7H6NO2)(NO3)(H2O)]
Acta Cryst. (2007). C63, m405±m406