Tetraaqua(2,2′-bipyridine)nickel(II) terephthalate

Article abstract of DOI:10.1107/S0108270103002087

The reaction of nickel(II) nitrate with terephthalic acid and 2.2′-bipyridine in dimethylformamide solution gives the title complex, [Ni(C₁₀H₈N₂)(H₂O)₄] (C₈H₄O₄). The Ni^II ion is octahedrally coordinated to one 2,2′-bipyridine and four water molecules and does not coordinate to the terephthalate anion. Hydrogen bonds between the terephthalate anions and the [Ni(2,2′-bipy) (H₂O)₄]²⁺ cations produce a two-dimensional hydrogen-bonding architecture with double sheets.

Full text of DOI:10.1107/S0108270103002087

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
described as distorted octahedral, and it associates with four
water O atoms and the two N atoms of a 2,20-bipyridine ligand
(Fig. 1). It should be pointed out that ta2 is a free anion and
does not coordinate to the Ni atom, although IR data indicates
that the ta2 anion has a bridging coordination mode (Rogan
et al., 2000).
ISSN 0108-2701
Tetraaqua(2,20-bipyridine)nickel(II)
terephthalate
The cations and anions of (I) form a two-dimensional
hydrogen-bonding network (Fig. 2). Each cation, simpli®ed as
[Ni(H2O)4]2+, is linked to six terephthalate anions through
hydrogen bonds (Fig. 3a), in which four of the six terephtha-
late anions are from one sheet of the two-dimensional network
and the remaining two are from another sheet. Each tereph-
thalate anion is in turn linked to six [Ni(H2O)4]2+ cations
through hydrogen bonds (Fig. 3b), four of which are from one
sheet of the two-dimensional network and the remaining two
are from another sheet. Each terephthalate carboxylate group
is linked to three [Ni(H2O)4]2+ cations. There are two
hydrogen bonds between terephthalate atom O2 and two
[Ni(H2O)4]2+ cations from the same sheet. The second
carboxylate O atom, O1, forms hydrogen bonds with two
[Ni(H2O)4]2+ cations from different sheets. Therefore, each
terephthalate anion forms eight hydrogen bonds with
[Ni(H2O)4]2+ cations, producing a two-dimensional hydrogen-
bonding network with double sheets.
Hong-Ping Xiao,a Zhan Shi,b Long-Guan Zhu,a* Ru-Ren
Xua,b and Wen-Qin Panga,b
aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, People's
Republic of China, and bCollege of Chemistry, Jilin University, State Key Laboratory
of Inorganic Synthesis and Preparative Chemistry, Changchun 130023, People's
Republic of China
Correspondence e-mail: chezlg@zju.edu.cn
Received 2 January 2003
Accepted 23 January 2003
Online 18 February 2003
The reaction of nickel(II) nitrate with terephthalic acid and
2,20-bipyridine in dimethylformamide solution gives the title
complex, [Ni(C10H8N2)(H2O)4](C8H4O4). The NiII ion is
octahedrally coordinated to one 2,20-bipyridine and four
water molecules and does not coordinate to the terephthalate
anion. Hydrogen bonds between the terephthalate anions and
the [Ni(2,20-bipy)(H2O)4]2+ cations produce a two-dimen-
sional hydrogen-bonding architecture with double sheets.
Comment
In recent years, signi®cant research effort has been focused on
coordination polymers, due to their potential applications in
catalysis, ion exchange and gas adsorption (Eddaoudi et al.,
2002; Moulton & Zaworotko, 2001); popular bridging ligands
in this ®eld are terephthalic acid (H2ta) and 4,40-bipyridine,
and their derivatives (Eddaoudi et al., 2001). Numerous
Figure 1
View of the title compound, showing the atom-labelling scheme and
displacement ellipsoids at the 50% probability level.
complexes with the ta2 ligand have been extensively studied,
while new complexes are constantly being synthesized.
Although the ta2 ligand has many coordination modes,
reports of complexes in which the terephthalate anion is used
as a synthon to generate supramolecular networks are still
relatively rare (Allen et al., 1999; Burrows et al., 1996, 1997).
We report here an example of ta2 as a hydrogen-bonding
linker in the presence of N-donor ligands. The title compound,
(I), consists of an [Ni(2,20-bipy)(H2O)4]2+ cation and a
terephthalate anion. The geometry around the NiII ion is best
Figure 2
View of the two-dimensional hydrogen-bonding network in (I).
m82 # 2003 International Union of Crystallography
DOI: 10.1107/S0108270103002087
Acta Cryst. (2003). C59, m82±m83

metal-organic compounds
Crystal data
3
[Ni(C10H8N2)(H2O)4](C8H4O4)
Mr = 451.07
Monoclinic, P21/c
Dx = 1.555 Mg m
Mo Kꢁ radiation
Cell parameters from all data
ꢂ = 2.07±29.97ꢀ
Ê
a = 7.5503 (2) A
b = 23.5347 (9) A
1
Ê
ꢃ = 1.06 mm
T = 293 (2) K
Ê
c = 11.1050 (4) A
ꢀ = 102.427 (2)ꢀ
V = 1927.06 (11) A
Z = 4
Block, green
0.40 Â 0.20 Â 0.20 mm
3
Ê
Data collection
Bruker SMART CCD area-detector
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.611, Tmax = 0.810
15 571 measured re¯ections
5600 independent re¯ections
3567 re¯ections with I > 2ꢄ(I)
Rint = 0.045
ꢂmax = 30.0ꢀ
h = 10 ! 10
k = 33 ! 13
l = 15 ! 15
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.048
wR(F2) = 0.126
S = 0.95
5600 re¯ections
294 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢄ2(Fo2) + (0.068P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 1.62 e A
3
Ê
0.72 e A
Áꢅmin
=
H atoms bonded to C atoms were treated as riding atoms, with a
Ê
CÐH distance of 0.93 A. The H atoms of the water molecules were
re®ned isotropically; see Table 1 for OÐH distances.
Data collection: SMART (Bruker, 1997); cell re®nement: SMART;
data reduction: SAINT (Bruker, 1997); program(s) used to solve
structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
SHELXP97 (Sheldrick, 1997); software used to prepare material for
publication: SHELXTL (Bruker, 1997).
Figure 3
The hydrogen bonds formed (a) by the cations [symmetry codes: (A)
3
3
1 + x, y, 1 + z; (B) x,
y, 12 + z; (C) 1 + x, y, z; (D) 1 + x,
y,
2
2
12 + z; (E) x, y, 1 + z] and (b) by the anions [symmetry codes: (A) x,
y, 12 + z; (B) 1 + x, y, z; (C) 1 + x, y, 1 + z; (D) x, y, 1 + z; (E) 1 + x,
y, 12 + z]. The 2,2-bipyridine ligand has been omitted for clarity.
The authors thank the National Natural Science Foundation
of China (No. 50073019) and the State Key Laboratory of
Inorganic Synthesis and Preparative Chemistry.
3
2
3
2
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GD1242). Services for accessing these data are
described at the back of the journal.
Experimental
A solution (10 ml) of dimethylformamide containing Ni(NO3)2Á6H2O
(0.5 mmol) and H2ta (0.5 mmol, 0.083 g) was added slowly to a
solution (10 ml) of dimethylformamide containing 2,20-bipyridine
(0.5 mmol). The starting mixture was stirred for a few minutes and
left to stand at room temperature for about one month. Green block-
shaped crystals of (I) were obtained.
References
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Table 1
Hydrogen-bonding geometry (A, ).
ꢀ
Ê
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DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O1WÐH1WAÁ Á ÁO1i
O1WÐH1WBÁ Á ÁO4ii
O2WÐH2WAÁ Á ÁO3ii
O2WÐH2WBÁ Á ÁO2iii
O3WÐH3WAÁ Á ÁO1
O3WÐH3WBÁ Á ÁO4iv
O4WÐH4WAÁ Á ÁO3v
O4WÐH4WBÁ Á ÁO2
0.842 (18)
0.863 (18)
0.870 (18)
0.800 (18)
0.893 (18)
0.837 (18)
0.853 (18)
0.853 (18)
1.92 (2)
1.78 (2)
1.87 (2)
2.00 (2)
1.753 (18)
1.91 (2)
1.98 (2)
1.899 (19)
2.719 (3)
2.634 (3)
2.726 (3)
2.748 (3)
2.644 (3)
2.722 (3)
2.795 (3)
2.745 (3)
157 (3)
167 (4)
168 (4)
156 (4)
175 (3)
163 (4)
158 (4)
171 (3)
È
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (1997). SHELXL97, SHELXS97 and SHELXP97. University
È
of Gottingen, Germany.
Symmetry codes: (i) x; 32 y; z
1 ‡ x; 32 y; z 12; (v) x; y; z 1.
;
(ii) 1 ‡ x; y; z 1; (iii) 1 ‡ x; y; z; (iv)
1
2
ꢁ
Acta Cryst. (2003). C59, m82±m83
Hong-Ping Xiao et al.
[Ni(C10H8N2)(H2O)4](C8H4O4) m83