Formation of a one-dimensional water chain containing two linking patterns of planar water tetra-mers

Article abstract of DOI:10.1107/S0108270107047294

The self-assembly of the title dinuclear complex, namely (-p-phenyl-enediamine-N,N,N′,N′-tetra-acetato)bis-[aqua-(1, 10-phenanthroline)nickel(II)] dodecahydrate, [Ni2(C14H12N2O8)(C12H8N2)2(H2O)2] ·12H2O, through intricate noncovalent inter-actions results in a two-dimensional sheet-like structure. The dimer lies about an inversion centre at the centre of the p-phenylenediamine ring. Uncoordinated water mol-ecules form one-dimensional chains in which cyclic water tetra-mers act as two types of building blocks. The water mol-ecules play a significant role in the stabilization of the three-dimensional supra-molecular framework. Intra-molecular aryl-metal chelate ring π-π inter-actions are also observed. International Union of Crystallography 2007.

Full text of DOI:10.1107/S0108270107047294

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ecule is one of the key factors in the formation of organic or
metal±organic supramolecular frameworks in which water
molecules are encapsulated as guests. The work presented
here reports the structural architectural system of hydrogen
bonding and ꢁ±ꢁ stacking interactions which assembles
the title complex, [Ni (dbta)(phen) (H O) ]Á12H O (dbta is
ISSN 0108-2701
2
2
2
2
2
0
0
Formation of a one-dimensional water p-phenylenediamine-N,N,N ,N -tetraacetate and phen is
chain containing two linking patterns
of planar water tetramers
1,10-phenanthroline), (I), in which interesting polymeric water
chains are found.
a
a
a
Xiang-Dong Zhang, * Chun-Hua Ge, Fang Yu, Qi-Tao
a
b
Liu and Miao-Li Zhu
a
College of Chemistry, Liaoning University, Shenyang 110036, People's Republic of
b
China, and Institute of Molecular Science, Key Laboratory of Chemical Biology and
Molecular Engineering of the Education Ministry, Shanxi University, Taiyuan
030006, People's Republic of China
II
Correspondence e-mail: xdzhang@lnu.edu.cn
Compound (I) consists of two Ni cations, two phen ligands,
one dbta ligand, two coordinated water molecules and 12
uncoordinated solvent water molecules. Each metal ion is six-
coordinated in a slightly distorted octahedral geometry, with
equatorial coordination by two carboxylate O atoms from
dbta and two N atoms from phen. The axial sites are occupied
by an aqua O atom and an N atom from dbta (Table 1).
The complex displays a zigzag-like shape (Fig. 1). In this
arrangement, the benzene ring of dbta is ®xed between two
phen rings, similar to the mixed-ligand Ni or Co complexes
(Hao, Li, Chen & Zhang, 2006; Hao, Li, Chen, Zhang et al.,
2006). The dimer lies about an inversion centre at the centre
of the p-phenylenediamine ring. The centroid-to-centroid
distance between the Ni±(N-heterocyclic) chelate ring and the
Received 15 August 2007
Accepted 26 September 2007
Online 13 October 2007
The self-assembly of the title dinuclear complex, namely (ꢀ-p-
phenylenediamine-N,N,N ,N -tetraacetato)bis[aqua(1,10-phen-
anthroline)nickel(II)] dodecahydrate, [Ni (C H N O )-
0
0
2
14 12
2
8
(
C H N ) (H O) ]Á12H O, through intricate noncovalent
1
2
8
2 2
2
2
2
interactions results in a two-dimensional sheet-like structure.
The dimer lies about an inversion centre at the centre of the p-
phenylenediamine ring. Uncoordinated water molecules form
one-dimensional chains in which cyclic water tetramers act as
two types of building blocks. The water molecules play a
signi®cant role in the stabilization of the three-dimensional
supramolecular framework. Intramolecular `aryl±metal
chelate ring' ꢁ±ꢁ interactions are also observed.
Ê
benzene ring is 3.45 A and the dihedral angle between the
ꢀ
planes of these rings is 19.3 . These parameters suggest that
Comment
Water is one of the most challenging targets in biology and
chemistry. In these ®elds, intense study is currently devoted to
a variety of water clusters and low-dimensional polymeric
water/ice assemblies (Chacko & Saenger, 1981; Ludwig &
Appelhagen, 2005; Moorthy et al., 2002; Wei et al., 2006; Zabel
et al., 1986). The number of different water clusters, including
dimers (Chand & Bharadwaj, 1998; Manikumari et al., 2002),
tetramers (Beobide et al., 2006; Lakshminarayanan et al., 2005;
Supriya & Das, 2003), pentamers (Infantes & Motherwell,
2
2
002; Ma et al., 2004a), hexamers (Zhang, Fang & Wu et al.,
005), octamers (Atwood et al., 2001; Blanton et al., 1999),
decamers (Barbour et al., 2000, 1998), dodecamers (Neogi et
al., 2004), tetradecamers (Ghosh et al., 2005), hexadecamers
(
Ghosh & Bharadwaj, 2004) and octadecamers (Raghuraman
et al., 2003), and in®nite one- (Neogi & Bharadwaj, 2005) and
two-dimensional (Janiak & Scharman, 2002; Ma et al., 2004b;
Zhang, Lin, Huang & Chen, 2005) polymers, has increased
dramatically in the past decade. Crystal engineering provides a
powerful tool to reveal the nature of the interactions between
water molecules. Investigation suggests that the water mol-
Figure 1
A perspective view of the zigzag-like structure of (I), showing the atom-
numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level. H atoms and uncoordinated water molecules have been
omitted for clarity. Unlabelled atoms are related to labelled atoms by the
symmetry operator (� x ‡ 1; � y ‡ 1; � z).
Acta Cryst. (2007). C63, m519±m521
DOI: 10.1107/S0108270107047294
# 2007 International Union of Crystallography m519

metal-organic compounds
there are intramolecular `metal-chelate ring±aromatic ring'
ꢁ
±ꢁ interactions. These structural features can be viewed as
evidence of metalloaromaticity (Casti nÄ eiras et al., 2002; Masui,
001). Weak intra- and intermolecular ꢁ±ꢁ stacking inter-
2
Ê
actions between benzene rings (3.53±3.69 A) (Fig. 2), accom-
panied by double hydrogen bonds between the coordinated
water molecule and a carboxylate O atom of an adjacent
Ê
complex [O1Á Á ÁO4(� x, � y, � z) = 2.776 (2) A and O1Ð
ꢀ
H1AÁ Á ÁO4 = 177 ], connect the complexes to form a two-
dimensional sheet.
Uncoordinated solvent water molecules are trapped in the
host framework as in®nite parallel chains. A closer view of the
water chain is depicted in Fig. 3, and important bond distances
and angles related to the water chain are given in Table 1. The
primary parts of the chain are two tetrameric cyclic rings
formed by atoms O6 and O8 and their symmetry-related
Figure 4
A space-®lling view, along the b axis, of the one-dimensional water chains
in the structure of (I).
iii
iii
their symmetry-related atoms O9 and O10 (ring B) (see
Fig. 3 for symmetry codes). It is interesting that the cyclic
water tetramer can provide a model for understanding liquid
water and ice in theoretical and experimental studies (Ludwig,
i
i
atoms O6 and O8 (ring A), and by atoms O9 and O10 and
2
001; Herbert & Head-Gordon, 2006). The H and O atoms
involved in these rings are almost coplanar. The con®gurations
of the cyclic water tetramers, rings A and B, are uudd (u is up
and d is down; Long et al., 2004; Ugalde et al., 2000). For ring
A, the H atoms on atoms O6 and O8 not included in the ring
Ê
are 0.43 and 0.76 A above the ring, respectively, while the H
i
atoms of atoms O6 and O8 are 0.43 and 0.76 A, respectively,
i
Ê
iii
below the ring. For ring B, the H atoms on atoms O9 and O10
Ê
are 0.46 and 0.40 A, respectively, above the ring, while the H
Figure 2
iii
atoms on atoms O9 and O10 are 0.46 and 0.40 A, respectively
Ê
The intra- and intermolecular ꢁ±ꢁ interactions in (I), indicated as dashed
lines.
below the ring. In the ring, each water molecule acts as both
hydrogen-bond donor and acceptor. Water molecules
containing atoms O8, O10 and O11 are tetrahedrally
connected by means of four hydrogen-bonding interactions
and atoms O6, O7 and O9 are involved in three hydrogen
bonds. As a building block, the planar water tetramer ring A
exhibits a side-linking pattern and ring B exhibits a diagonal-
iv
linking pattern. Atoms O7 and O11 bridge rings A and B to
Ê
form a chain via hydrogen bonds [O6Á Á ÁO7 = 2.834 (3) A and
ꢀ
Ê
O6ÐH6AÁ Á ÁO7 = 174 ; O7Á Á ÁO10 = 2.781 (3) A and O7Ð
ꢀ
i
iv
Ê
i
H7BÁ Á ÁO10 = 171 ; O8 Á Á ÁO11 = 2.896 (3) A and O8 Ð
i
iv
ꢀ
iii
iv
iii
Ê
H8A Á Á ÁO11 = 170 ; O10 Á Á ÁO11 = 2.789 (3) A and O10 Ð
iii
iv
ꢀ
H10 BÁ Á ÁO11 = 175 ; for symmetry codes, see the caption to
Fig. 3].
The water chains are gathered between the two-dimen-
sional sheets by means of hydrogen bonds involving the
coordinated water and the dbta ligand O atoms (Fig. 4 and
Table 1).
The broad IR band of (I) centred around 3466 and
�
1
3
400 cm can be attributed to the OÐH stretching frequency
of the coordinated water molecules and water tetramer
Zuhayra et al., 2006).
(
Experimental
Figure 3
The water chain in the structure of (I), showing the hydrogen-bonding
environment of water molecules in the chain. Displacement ellipsoids are
drawn at the 50% probability and H atoms are shown as small spheres of
arbitrary radii. Hydrogen bonds are indicated by dashed lines [Symmetry
codes: (i) � x + 1, � y, � z + 1; (ii) � x + 1, � y + 1, � z + 1; (iii) � x, � y,
All reagents were commercial grade materials and were used as
4
received. H dbta was obtained by the direct reaction of p-phenyl-
enediamine with sodium chloroacetate in alkaline aqueous solution.
Elemental analyses were determined on an Elementar Vario EL
elemental analyser. IR spectra were measured as KBr pellets on a
�
z + 1; (iv) x, y � 1, z.]
ꢁ
m520 Zhang et al. [Ni
2 12 2
(C14H N O
8 8 2
)(C12H N )
2 2
(H O)
2
2
]Á12H O
Acta Cryst. (2007). C63, m519±m521

metal-organic compounds
�
1
Perkin±Elmer spectrophotometer in the 4000±400 cm region. 1,10-
Phenanthroline (1.5 mmol) and nickel nitrate (1 mmol) were
dissolved in water (20 ml) and the solution was re¯uxed for 1.5 h.
This project was supported by the Natural Science Foun-
dation of the Education Bureau of Liaoning Province. MLZ
acknowledges the National Natural Science Foundation of
China (grant No. 20471033), the Provincial Natural Science
Foundation of Shanxi Province of China (grant No. 20051013)
and the Overseas Returned Scholar Foundation of Shanxi
Province of China in 2006 for ®nancial support.
After ®ltration, the solution was added to H
10 ml), and the mixture was re¯uxed for 4 h, ®ltered and left to stand
at room temperature. Blue single crystals of (I) were obtained after
2 h (yield 48% based on Ni). Analysis calculated for C38
Ni 22: C 42.80, H 5.29, N 7.88%; found: C 43.11, H 5.44, N 7.86%.
Selected IR frequencies (KBr, ꢂ, cm ): 3466 (vs), 3400 (vs), 1623 (s),
4
dbta (0.5 mmol) in water
(
1
56
H -
N
6
2
O
�
1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV3107). Services for accessing these data are
described at the back of the journal.
1
519 (m), 1431 (m), 1385 (m), 1328 (m), 1272 (m), 1208 (m), 1151 (m),
06 (m), 871 (m), 858 (m).
9
Crystal data
References
ꢀ
ꢀ
Ê
[
Ni
(
2
(C14
H
12
N
2
O
8
)(C12
H
8
N
2
)
2
-
ꢄ = 108.4260 (10)
ꢅ = 107.5360 (10)
H
= 1066.31
2
O)
2
]Á12H
2
O
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3
M
r
V = 1175.71 (14) A
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Triclinic, P1
a = 10.2082 (7) A
b = 10.3481 (7) A
c = 12.4101 (8) A
ꢃ = 91.3360 (10)
Ê
Ê
Mo Kꢃ radiation
� 1
ꢀ = 0.89 mm
T = 183 (2) K
Ê
ꢀ
0.28 Â 0.25 Â 0.19 mm
Data collection
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T
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min = 0.777, Tmax = 0.849
Rint = 0.016
Re®nement
2
R[F > 2ꢆ(F )] = 0.033
wR(F ) = 0.083
2
307 parameters
H-atom parameters constrained
2
Ê
� 3
Áꢇmax = 0.32 e A
44, 3856±3862.
S = 1.06
4
Áꢇmin = � 0.21 e AÊ
� 3
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Hydrogen-bond geometry (A, ).
Ê
ꢀ
1
4282±14287.
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
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i
O1ÐH1AÁ Á ÁO4
0.85
0.85
0.85
0.85
0.85
0.85
0.84
0.85
0.84
0.85
0.79
0.76
0.85
0.85
1.93
1.93
1.99
2.06
1.94
2.05
1.92
2.05
2.04
2.05
2.00
2.02
1.93
1.83
2.776 (2)
2.773 (2)
2.834 (3)
2.887 (3)
2.781 (3)
2.887 (2)
2.761 (3)
2.896 (3)
2.874 (2)
2.882 (3)
2.789 (3)
2.758 (3)
2.772 (2)
2.665 (2)
177
173
174
165
171
170
177
170
170
167
175
164
169
164
ii
O1ÐH1BÁ Á ÁO8
7
540±7546.
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798±3800.
O6ÐH6AÁ Á ÁO7
ii
O6ÐH6BÁ Á ÁO8
O7ÐH7BÁ Á ÁO10
O7ÐH7AÁ Á ÁO3
O8ÐH8BÁ Á ÁO6
O8ÐH8AÁ Á ÁO11
O9ÐH9AÁ Á ÁO2
O9ÐH9BÁ Á ÁO10
3
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iii
iv
O10ÐH10BÁ Á ÁO11
v
O10ÐH10AÁ Á ÁO9
O11ÐH11BÁ Á ÁO3
1, 3417±3420.
vi
O11ÐH11AÁ Á ÁO5
Symmetry codes: (i) � x; � y; � z; (ii) � x ‡ 1; � y; � z ‡ 1; (iii) � x ‡ 1; � y ‡ 1; � z ‡ 1;
(
iv) � x; � y ‡ 1; � z ‡ 1; (v) � x; � y; � z ‡ 1; (vi) � x; � y ‡ 1; � z.
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H atoms attached to C atoms were placed in geometrically idea-
2
Ê
3
Ê
lized positions, with Csp ÐH = 0.93 A and Csp ÐH = 0.97 A, and
re®ned with Uiso(H) = 1.2Ueq(C). H atoms attached to O atoms were
located in a difference Fourier map and re®ned as riding in their as-
found positions, with Uiso(H) = 1.5Ueq(O). The OÐH distances are in
7
21.
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Ê
the range 0.762±0.853 A.
1
Data collection: SMART (Bruker, 2001); cell re®nement: SAINT
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(
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publication: SHELXL97.
3146±3150.
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ꢁ
Acta Cryst. (2007). C63, m519±m521
Zhang et al.
[Ni (C14H
2 12
N O )(C12H
2 8 8
N )
2
2
(H
2
O)
2
]Á12H
2
O
m521