Interesting fluorine anion water clusters [F-·(H2O)n] in metal complex crystals

Article abstract of DOI:10.1039/c8ce00532j

Three crystalline complexes containing fluorine anion water clusters, [Cd(Im)₆][F·H₂O]₂ (1), [Ni(Im)₆][F₂·(H₂O)₅] (2) and [Co(Im)₆][F·NO₃·(H₂O)

Full text of DOI:10.1039/c8ce00532j

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HIGHLIGHT
Tiddo J. Mooibroek, Antonio Frontera et al.
Towards design strategies for anion–π interactions in crystal engineering
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ꢀ
The Interesting Fluorine Anion Water Clusters [F ·(H O) ] in Metal
2
n
Complex Crystal
Fang Fang Jian*, Liu E, Junying Ma
School of Chemical Engineering and Pharmaceutics, Henan University of Science and Technology,
Luoyang, Henan, P. R. China
Eꢀmail: ffj2017@haust.edu.cn
ꢀ
5
Three crystalline complexes containing fluorine anion water
cluster, [Cd(Im) ][F·H O] (1), [Ni(Im) ][F ·(H O) ] (2) and
study of the X (H
2
O)
n
cluster is essential for understanding the
solvent and molecular recognition phenomena of the anionic
systems. In the halide series, the fluoride anion is different
6
2
2
6
2
2
5
6
[
Co(Im) ][F·NO ·(H O) ] (3), were reported. The interesting
6 3 2 4
from its congeners, displaying a high electronegativity and
hydration energy. This tiny anion has a high tendency to be
fluorine anion water clusters are described in this paper. The
single Xꢀray analysis shows that fluoride ions in water cluster
have the different coordination environments, with fourꢀ
coordinated in tetrahedron geometry for (1), fiveꢀcoordinated in
7
5
5
6
6
0
5
0
5
hydrated instead of being isolated, rendering it even more
challenging to bind with synthetic hosts in water. Cametti and
Rissanen recognized that a “hydrated fluoride” has more
relevance and importance than a “naked fluoride anion”
1
1
2
2
3
0
5
0
5
0
trigonal bipyramid geometry for (2), and threeꢀcoordinated in
−
plane trigonal geometry for (3). F (H O) is assembled by strong
2
n
8
within the anion recognition arena. Fluoride recognition is an
Hꢀbonding interactions [OH···F = 2.576(1) Å − 2.813(1) Å],
where a fluoride anion plays the important role to connect
area of immense research interest in the scientific community
9
due to its role in chemical, industrial, food and toxicity.
2+
imidazole ligand of host [M(Im) ] . The strength of an ionic
6
As we can know, the crystallographic structural studies of
the anionic water cluster stabilized in the lattices of crystal
hosts, rather than the spectroscopic investigations, should
provide much more detailed information characterizing these
intriguing and important clusters. So far, various models for
−
bond between host and guest is strongly influenced by F (H O)
2
n
water cluster adjacent to the ligand with NH···F distances of
.607 Å − 2.755 Å. The TGA, IR and XRD studies for above
2
three compounds at different testing temperature were suggested
ꢀ
that fluorine anion water cluster, F (H O) , was much stable.
ꢀ
2
n
the F (H O) anion water cluster have been theoretically
2
10
n
This result distinctly differentiates the reported compounds
containing neutral water cluster molecules. This phenomenon
ꢀ
predicted. However, precise crystal data for the F (H O)
2
n
anion cluster, to our knowledge, are very limited. With the
help of the Cambridge Crystallographic Data Centre, we
performed a Cambridge Structural Database (CSD) search for
was indicated the stronger anionic hydrogenꢀbonds interaction
ꢀ
between F and H O, which also confirmed the intracluster
2
ꢀ
ꢀ
ꢀ
proton transfer process F ·H O→HF·OH . This result suggests
a sample of hydrated structures containing discrete F anion
2
ꢀ
that the fluorine anions and water molecules are Hꢀbonded to
that have at least one F /water contact with an O···F distance
each other in an alternating fashion within the fluoride−water 70 less than the sum of their van der Waals radii (3.04 Å), and no
hybrid cluster, where a fluorine anion plays the important role of
connecting host metal complex and guest water cluster.
disorder, no errors and Rꢀfactor < 10%. We only found four
ꢀ
crystals structural information containing F (H O) anionic
2
n
1
1
12
water cluster; CSD refcodes BIPTAV,
OBIJAL,
1
3
14
Hydrated halide anions are a highly active area of research,
VAPKAY and XEFHOF. But, the structure and effects of
ꢀ
since they are the most common anions in nature due to their 75 F (H O) in those complexes did not be described in their
2
n
role in many chemicals, environmental, and biological
processes. Investigation of the structures of halideꢀwater
papers. In addition, there has been considerable interest to use
of graphꢀset analysis of hydrogenꢀbond patterns in the
crystal. The interactions between molecules are governed by
intermolecular forces whose energy and geometric properties
1
1
5
3
4
4
5
0
5
clusters in diverse environments is of fundamental importance
2
for our understanding of solvation phenomena, electrical
phenomena in the troposphere and ionosphere, and the 80 are much less well understood than those of classical chemical
3
15
16
mobility of ions in chemical and biological systems. The
bonds between atoms. M. C. Etter and J. Bernstein applied
graph theory to recognize the patterns of hydrogen bonding
for the understanding and design of molecular crystal.
According to their reports, the hydrogenꢀbond motifs of
ꢀ
anion water clusters of X (H O) have also been extensively
2
n
investigated both experimentally and theoretically due to their
suitable simplified model systems for aerosol study and
4
ꢀ
ꢀ
molecular recognition study to design the X receptors. The X
H O)n cluster shows a clear distinction from that of alkali
85 fluorine anion water clusters [F ·(H O) ] are not found or
2
n
(
introduced. The hydrogen bond patterns in our crystals are
completely novel, which will be useful to future scientific
research.
2
metal ions because the anion hydration tends to favor surface
5
states, while the cation hydration favors internal states. The
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 1

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DOI: 10.1039/C8CE00532J
In the study of anionic water cluster, we have started a
are crossꢀlinked by CꢀH···π stacking interactions, and are
phenomenon according to the TG analysis, the water 60 linked into twoꢀdimensional layers parallel to the
molecules in anionic water cluster all have obviously intense
thermal stability. In this paper, we report three crystal
structure data of imidazole metal complexes containing F
crystallographic bcꢀplane (Fig. 1a). The imidazole ligands
engage in headꢀtoꢀface CꢀH···π aromatic stacking interactions
[d(C···C) 3.731~3.848 Å for (1), 3.491 ~ 3.771 Å for (2) and
3.732~3.775 Å for (3)]. In the crystal, the adjacent 2D
ꢀ
5
0
5
0
5
0
5
0
5
0
5
(
[
H O)n anion water cluster; [Cd(Im) ][F·H O]
2
(1),
2
6
2
2
n+
Ni(Im) ][F ·(H O) ] (2) and [Co(Im) ] [F·NO ·(H O) ] (3). 65 supramolecule coordinated polymers units, [M(Im)6]n , form
6
2
2
5
6
3
2
4
Their TG analyst was studied. Processes of weight losing were
studied by XRD and IR spectra. The crystal structure data and
a large void space each other, in which the fluorine anion
ꢀ
water cluster, F (H O) , are sandwiched (Fig. 1b). The
2
n
2
+
1
1
2
2
3
3
4
4
5
5
TG analyst we can get two important structural information:
shortest distances between the adjacent 2D [M(Im)6] layers
ꢀ
(
1) the excess electron is trapped in F (H O) anion water
are about 4.483 Å for (1), 4.660 for (2) and 4.695 Å for (3).
2
n
2
+
cluster interior, and excess charge delocalization mediated by 70 The thickness of [M(Im)6] layers is about 8.071 Å for (1),
ꢀ
ꢀ
intracluster proton transfer [F ·(H O) → HF·OH (H O) →
nꢀ1
5.920 Å for (2) and 5.843 Å for (3), respectively. The
imidazoles play important roles in these three structures. One
is serving as a ligand covalently linked to the metal centers.
The second role is acting as linkers, the adjacent imidazole
2
n
2
ꢀ
HF(H O) ·OH ]. (2) the intracluster protonꢀtransfer process
2
nꢀ1
makes hydrogen bond strength become quite intense, for
example, exhibit extremely high thermal stability; no water
molecules were lost even if all imidazole entities were lost 75 rings are connected to each other by the significant CꢀH···π
ꢀ
under heating. Strong thermal stability [F(H O) ] anion water
stacking interactions. The third role is forming strong
2
n
ꢀ
cluster in metal salt will be useful to future.
hydrogen bonds with F (H O) to connect host and guest in
2
n
ꢀ
Three complexes containing F (H O) anion water cluster is
the crystal.
The interesting phenomenon is that compounds (1) and (2)
with fresh precipitation M(OH) in Teflon vessel according to 80 have the exact same coordination environment but the
2
n
synthesized easily. MF2 was prepared by reacting HF acid
2
mole ratio HF׃M(OH) =2׃1. Above solution was added
different structure of fluorine anion water cluster, although
only Cd is replaced by Ni. The secondary amine NH in four
imidazole ligands with the same planar are all forming strong
hydrogen bond with the F atom in the anion water cluster with
2
dropwise to an excess ethanolic solution of imidazole and
stirred at room temperature for 1 h. The clear solution was
filtered and yielded block crystals suitable for diffraction by
slow evaporation of mother liquor over three days. The 85 the distances of FꢁꢁꢁN 2.607(3) Å and 2.688(3) Å for (1),
composition of these complexes was determined by elemental
analysis and was justified by a single Xꢀray diffraction. Also,
the structures of these complexes were determined by UV and
2.6537(15) Å and 2.7553(15) Å for (2), respectively. The
secondary amine NH in axial position imidazole ligands is all
forming a hydrogen bond with water molecules. The distances
of OꢁꢁꢁN are 2.773(3) Å for (1), 2.7954(16) Å for (2),
ꢀ
FTꢀIR spectroscopy. The compound (3) has one NO3 anion in
the structure, we think it is fresh precipitation Co(OH)2 90 respectively (SI Table S1ꢀ2, S2ꢀ2). But, the supramolecule
absorbing a little NaNO or Co(NO ) .
configuration of compound (1) and (2) is different. F atoms
coordination environment in two compounds is also different.
For compound (1), the anion consists of an infinite chain with
3
3 2
These complexes have similar properties, such as a high
solubility in organic solvent, low solubility in water and better
thermal stability at room temperature. Also, the features of
—
a repeat unit of (···F H O···) to form fluorine anion water
2
n
ꢀ
nꢀ
this synthesis, such as mild conditions, high yield, simple 95 cluster polymers [F ·H O] along the (110) plane, and the
2
n
purification and short reaction period would make them
become a promising method in the future applications.
The structure unit of the compounds (1), (2) and (3) all
aggregate model is C2 according to the established
classification system of water cluster by L. Infantes and S.
1
8
ꢀ
Motherwell. Each F anion connect two water molecules
through FꢁꢁꢁO hydrogen bonds forming a Vꢀshaped structure.
2
+
consist of one discrete [M(Im)6] cations (M=Cd, Co or Ni)
ꢀ
and fluorine anionic water cluster F (H O) . The coordination 100 The FꢁꢁꢁO distances are 2.668(3) Å and 2.619(3) Å (SI Table
2
n
environments of metal atom are a little different. In compound
1), the Cd atom lies on an inversion centre. In compound (2),
S1ꢀ2), respectively, which indicate that these FꢀOw
interactions are stronger than the OwꢀOw interactions in ice
(
1
9
ꢀ
nꢀ
the Ni atom also lies on an inversion centre and all the oxygen
and fluorine atoms lie on mirror planes. In compound (3), the
Co atom is at a site with barꢀ3 symmetry, the F1 atom is at a 105 supramoleculea network with host [M(Im)6]n . Six F anion,
site with barꢀ6 symmetry, O1, O1w and O2w lie on mirror
planes, and N3 is at a site with barꢀ6 symmetry and it also lies
on mirror planes. Each metal atom is sixꢀcoordinated with six
I .
h
Though the infinite chain [F ·H O]
cluster is
2
n
independent, they are Hꢀbonded to imidazole ligands to form
2
n+
ꢀ
four water molecules, two Cd atoms and four imidazole rings
2
n+
form one macrocyclic structure, and the host [M(Im)6]n was
wrapped in the middle of the big ring (Figure 2). Each
N
atoms from imidazole ligands in slightly distorted
fluoride ion in the cluster is being coordinated by two
ꢀ
octahedron geometry. MꢀN bond lengths and NꢀMꢀN bond 110 imidazoles via strong N−H···F (2.607(3) Å and 2.688(3) Å)
ꢀ
angles are in good agreement with the similar structures we
and two water O−H···F (2.619(3) Å and 2.668(3) Å) Hꢀ
bonding interactions, and form a tetrahedral structure. The
tetrahedral vertex is occupied by two water molecules and two
1
7
2+
reported before. For one discrete [M(Im)6] cations, the
metal(II) atom lies on the centre of three C2 symmetry
operation and the opposite imidazole ligands being in the
ꢀ
NH of imidazole ligands. The shorter distance of N−H···F
ꢀ
same planar. The CꢀH···π aromatic stacking interactions play 115 and O−H···F shows high stability to fluoride−water cluster
an important role in the crystal packing. Adjacent cation units
entrapped in compound (1).
2
| Journal Name, [year], [vol], 00–00
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DOI: 10.1039/C8CE00532J
ꢀ
nꢀ
To the best of our knowledge, the infinite chain [F ·H O]
FꢁꢁꢁO and O···O hydrogen bonds; each O(4w) atom connects
2
n
cluster we reported here has been structurally characterized 60 O(2w), O(3w) and O(5w) through O···O hydrogen bonds; each
ꢀ
for the first time. Only the structure of the infinite chain [OH
O(5w) connects F(2), O(1w) and O(4w) through FꢁꢁꢁO and
O···O hydrogen bonds. The five oxygen atoms and two
fluorine atoms are all in the same planar with the maximum
deviation from the mean plane being 0.0001 Å. Twoꢀ
nꢀ
·
H O]n hydroxyl anion water cluster has been reported. In
2
Bernal’s review, he introduced two examples of hydroxyl
2
0
5
n+
anion water cluster [OH·H O]
with a repeat unit of
2
n
—
(
···OH H O···) in the crystal structure. The structure motif 65 dimensional fluorine anion water cluster polymers,
of [F ·H O] is much similar to that of [OH ·H O] , and
2
n
ꢀ
nꢀ
ꢀ
nꢀ
2nꢀ
[F ·(H O) ]
5 n
form independent fluorine anion water layers
2
n
2
n
2
2
hydrogen bond lengths and angles are also nearly equivalency.
Considering the Xꢀray structure is not refined at a level that
can isolate the position of the hydrogen atom, and it cannot
identify the position of the hydroxyl groups. We think the
study of a crystal structure for fluorine anion water cluster
instead of hydroxyl anion water cluster is better to understand
running parallel to (010). The distances between adjacent
fluorine anion water layers are approximately 10.570 Å
(Figure 3b).
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
70
There is obvious hydrogen bond connecting between host
2
+
[Ni(Im)6] cations and fluorine anionic water cluster as
shown in Figure 3b. F1 and F2 atoms form the strong
ꢀ
ꢀ
the electron binding motif of (H O) cluster. On the other
N−H···F hydrogen bonds interaction with the secondary
2
n
1
0c
side, McCoy etc studied the behaviour of a water molecule
in direct contact with small inorganic anions, X ·H O (X = F , 75 Å and 2.7553(15) Å, respectively. Each F atom is strongly
Cl , Br and OH ), by using the recent vibrational spectroscopy
and quantum chemistry calculation, and put forward the
excess charge was delocalized by intracluster proton transfer
amine NH in imidazole. The distances of FꢁꢁꢁN are 2.6537(15)
ꢀ
ꢀ
ꢀ
2
ꢀ
ꢀ
ꢀ
bonded with five Hꢀbondꢀdonors in a trigonal bipyramid
coordination geometry, and three water molecules lie on a
trigonal plane and two secondary amine lies on the vertex
(Figure 4a). For F1, the distances of F1···HꢀO2w, F1···Hꢀ
ꢀ
ꢀ
X ·H O→HX·OH . In fact, this conclusion was also confirmed
2
by our although the hydrogen bond lengths of their calculated 80 O3w and F1···HꢀN4 are 2.745(2) Å, 2.813(3)
Å and
ꢀ
structure for the X ·H O complexes are shorter than that of
2.7553(15) Å, respectively. For F2, the distances of F2···Hꢀ
O1w, F2···HꢀO3w, F1···HꢀO5w and F1···HꢀN2 are 2.577(2)
Å, 2.840(3) Å, 2.756(2) Å and 2.6537(15) Å, respectively.
Except for O1w, other water molecules all form a Yꢀshaped
2
ours. In compound (1), the fluorine anion water cluster exists
ꢀ
ꢀ
intracluster proton transfer F ·H O→HF·OH , the excess
2
ꢀ
nꢀ
charge was delocalized in the whole [F ·H O] 1D chain. The
2
n
TGA (thermogravimetric analysis) data of compound (1), 85 structure with the O···O distances of 2.652Åꢀ2.907Å, and
[
Cd(Im) ][F·H O] , showed that there are not any water
O···F of 2.744Å ꢀ2.842Å. O1w is bonded with two secondary
amine of O1w···N6 2.7954(16) Å, one O1w···O5w 2.652(2)
Å, and one O1w···F2 2.577(2) Å in a tetrahedral coordination
geometry (Figure 4b and SI Table S2ꢀ2).
6
2
2
molecules to be lost at the temperature of 170°C. The
compound, Cd(F·H O) , can stably exist at the temperature of
2
2
3
20°C.
In compound (2), the fluorine anion water cluster, [F2
(H O) ] , forms twoꢀdimension planar structure along the b
2
ꢀ
90
It is noteworthy that there is one longer and one shorter
distance for F···O(w), which suggests F anion with parts of
O(w) molecule have the stronger interactions. The distances of
2.577(2) Å for F(2)···O(1w) and 2.671(2) Å for F(1)···O(2w)
·
2
5 n
axis, the aggregate model is L6(6)6(6)8(6) (Figure 3a).
2
1
According to the reported by Mascal et al., a proper analysis
should be done when reporting any new water morphology in
a crystal lattice. We performed a Cambridge Structural
Database (CSD) search for this 2D planar water motif or
extended water motif with the help of the Cambridge
Crystallographic Data Centre and also consulted the result of
water cluster and extended water cluster in organic molecular
2
2
shows the shortest ones which were reported before.
ꢀ
ꢀ
95
In compound (3), the [F ·NO ·(H O) ] anion water cluster
3 2 4
forms supramolecule iceꢀlike hydrogen bonding arrangement
ꢀ
ꢀ
along the crystallographic c axis (Figure 5). The F , NO and
3
ꢀ
water molecules are in the same planar. Each F anion
connects to three water molecules through F···O hydrogen
1
8
crystal which have been reported by L. Infantes et. al. We 100 bonds forming a Yꢀshaped structure with the F···Ow distance
did not find the match structure of water in crystal hydrates of
organic compounds and coordination complexes for this
L6(6)6(6)8(6) aggregate modes. Therefore, there is no
structural information available for this planar cyclic
structureꢀshaped or its participation in the stabilization of a 105 molecules through an O···HꢀO2w hydrogen bond with the
supramolecule assembly to be reported so far.
of 2.671(2) Å, 2.745(2) Å and 2.813(3) Å, respectively.
Fluorine anion with water molecules forms 12ꢀmembers ring
ꢀ
as shown in Figure 5a. Each NO3 anion lies in the centre of
the 12ꢀmembered ring of F O , and connects three water
3
9
O···Ow distance of 2.741(3) Å, 2.853(3) Å and 2.908(3) Å,
respectively. (Figure 5b and SI Table S1ꢀ2).
Unlike compounds (1) and (2), fluorine anion did not
Without considering NꢀH···F or NꢀH···O hydrogen bond, in
ꢀ
above fluorine anion water clusters, each F anion connects to
2
+
ꢀ
three water molecules through FꢁꢁꢁO hydrogen bonds forming
a Yꢀshaped structure, and F(1) and F(2) have the triangle 110 anions play the connecting role between host [Co(Im) ] and
geometry. The five water molecules locate in a plane and do
not show a cyclic cluster. Five water molecules show different
connected manners. Each O(1w) atom connects to the F(2)
anion and the O(5w) through FꢁꢁꢁO and O···O hydrogen
connect host [Co(Im)6] cation with NH···F interaction. NO
3
2
+
6
ꢀ
ꢀ
guest [F ·NO ·(H O) ] water clusters with the distances of
3 2 4
O···HN 2.7954(16) Å. Each O atoms in NO connects the
adjacent host [Co(Im)6] as shown in Figure 6a. The layered
structure motif depicts two closely packed monolayers of [F
ꢀ
3
2
+
ꢀ
ꢀ
2+
bonds; each O(2w) atom connects to two F(1) and O(4w) and 115 ·NO ·(H O) ] anion clusters with the [Co(Im) ] cation at
3
2
4
6
each O(3w) atom connects to F(1), F(2) and O(4w) through
the center of the bilayer. Space filling model is as shown in
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DOI: 10.1039/C8CE00532J
2
+
Figure 6b depicts the [Co(Im) ] cation clefts interfacing the
coordinated water molecules in crystal we found so far the
6
ꢀ
ꢀ
27
supramolecule [F ·NO ·(H O) ] anion cluster bilayers. The 60 highest dehydration temperature was 225°C.
ballꢀandꢀstick perspective view shows how the [F ·NO3
(H O) ] anion cluster bilayers are juxtaposed with the
hydrogen bond leading 12ꢀmembered rings. Although no
direct intermolecular interactions are apparent between the
molecules of each monolayer, adjacent monolayers are held
together by hydrogen bonds formed between NO3 and
imidazole groups. Thus, within the bilayer, each molecule of
[Co(Im)6] cation layer interacts with three NO3 of the
adjacent [F ·NO ·(H O) ] layers. This intricate hydrogen
Repeated
3
2
4
ꢀ
ꢀ
ꢀ
experimental verification, fluorine anion water (F ·H O) are
2 n
·
the much higher thermal stability according to our analysis.
The TGA and DTG curves of complexes (1), (2) and (3) are
shown in Figure 8a, 8b, and 8c, respectively.
For compound (1), there is an obvious flat between 20°C to
173°C, indicating the compound (1) is very stable before
173°C. The weight loss begins at 173°C, and shows an
obvious inflexion at about 173.2°C. The first step corresponds
to the loss of three imidazole molecules per formula unit, and
2
4
5
0
5
0
5
0
5
0
5
0
5
65
ꢀ
2
+
ꢀ
1
1
2
2
3
3
4
4
5
5
ꢀ
ꢀ
3
2
4
bonded arrangement ensures that the bilayer is structurally 70 with the two heatꢀabsorption peaks (found 34.32% calc.
rigid. The interplanar spacing between the bestꢀfit planes
34.29%). There is an obvious inflexion at 305°C corresponds
to the loss of the last three imidazole molecules (found
34.02% calc. 34.29%) with the sharp heatꢀabsorption peak. At
this temperature, the residual compound is Cd(F·H O) (found
ꢀ
ꢀ
defined by the [F ·NO ·(H O) ] anion cluster layer is
3
2
4
approximately 10.539 Å.
ꢀ
ꢀ
ꢀ
In [F ·NO ·(H O) ] anion water clusters, three F and nine
3
2
4
2
2
ꢀ
water molecules form a 12ꢀmembered ring and NO3 lies in 75 31.66% calc. 31.30%). Over the temperature range of 340ꢀ
ꢀ
the center of the 12ꢀmembered ring. If we don’t consider NO3
440°C almost no weight loss was observed, suggesting the
ꢀ
anion, [F ·(H O) ] fluorine anion water cluster form the
residual compound Cd(F·H O)2 is much stability. Upon
2
4
2
aggregate mode of L12(6) which like shamrock (Fig. 7a). This
temperature increase, TGA shows the weightꢀloss of 27.24%
and the total weightꢀloss of 95.58% of above 720°C, which
2
3
L12(6) water layer structure has been reported by C. Janiak.
2
4
M. Mascal et al. also found 15 examples of this motif from 80 suggests the sublimation of Cd(F·H O) , in the respect that
2
2
CSD, and found L12(6) layers exist in 3 different topologies.
even if the final residue is metal Cd which the weight ratio
must be 18.89%. Among 720°C to 900°C, there is a flat curve,
the residual weight ratio of 5.42%, the better explaining is that
the part of Cd(F·H O) have sublimated.
For compound (2), the weight loss begins at about 160°C,
and shows three inflexions at 160°C, 190°C and 227°C. From
160 to 280°C, TGA shows three successive weight loss steps
with a total of 71.83%, which is corresponding to the lost of
six imidazole molecules and one water molecule (calc. 71.50
ꢀ
nꢀ
Although this [F ·(H O) ] fluorine anion water cluster could
2
4 n
be described to the topology of the (6,3) net, and there are
four other structures which present the same topology, this
shamrockꢀlike shaped pattern 12ꢀmembered ring was not
found in this crystal structure. On the other hand, if we only
2
2
85
ꢀ
consider the nitrate anion water cluster ignoring F anoin,
ꢀ
ꢀ
nꢀ
three NO3 with nine water molecules in [NO ·(H O) ]
4 n
3
2
water cluster form a 18ꢀmembered ring which like a maple
leaf (Fig. 7b), the aggregate model is L18(6). This L18(6) 90 %) with three obvious heatꢀabsorption peaks, and the residual
water layer structure was found in supramolecule (H O) compound maybe is NiF (H O) . From 280 to 380°C, there
2
18
2
2
4
2
5
water morphology reported by K. Raghuraman et al., the
topological equivalence is also the (6,3) net. However, this
maple leafꢀlike shaped pattern, to the best of our knowledge,
are not weight loss to be observed, indicating the residue
NiF (H O) is very stable. At 380.8°C, there is an intense
endothermic phenomenon, the weight loss of 9.54
2
2
4
%
was originally reported. It is worthy to note that the hydrogen 95 corresponding to 3 molecules water (calc. 9.00 %). Over the
atoms of water molecules of the compound (3) are different
with that for the compound (1) and (2). In compound (1) and
(2) all H atoms in water molecules are located in the same
plane with Ow and F atoms. But, in compound (3) the H
temperature range of 381ꢀ445°C, there is no weight loss to be
observed, suggest NiF (H O) is much stability. Upon the
temperature increase, as like to compound (1), the weightꢀlose
2
2
of 12.52% and the total weightꢀlose of 93.90% of above
atoms in H O are all departure from the plane of F, Ow, and 100 700°C also suggest the partial sublimation of NiF (H O).
2
2
2
ꢀ
ꢀ
nꢀ
NO . 12ꢀmembered ring [F ·(H O) ] fluorine anion water
cluster with an 18ꢀmembered ring [NO ·(H O) ]
4 n
anion water cluster are overlapped each other in a parallel
manner (SI Fig. S3ꢀ5).
According to the Xꢀray powder diffraction analysis for the
residue at 800°C for the compound (2), the residual compound
was NiO. But, the finding is only 7.78% and the real weight
ratio of NiO in the compound (2) is 12.55%.
3
2
4 n
ꢀ
nꢀ
nitrate
3
2
The three compounds (1), (2) and (3) all contain fluorine 105 For compound (3), the weight loss begins at about 130°C,
anion water cluster. To get more insight into the properties
relative to this fluorine anion and water molecules, their
dehydration behavior has been investigated using thermoꢀ
gravimetric analysis (TGA) and Xꢀray power diffraction. The
and shows an inflexion at about 131.3°C. From 130 to 185°C,
total weight loss of 64.67 % corresponds to the loss of six
imidazole molecules (calc. 65.70 %) with two obvious heatꢀ
absorption peaks, and the residual compound is
samples are carefully prepared as fellows: dry in a vacuum 110 CoFNO (H O) . From 185 to 265°C, there is no weight loss to
3
2
4
drying oven for 1 hour at 105ºC and 0.05MPa, then transfer to
weigh bottle with grinding mouth for the next experiment.
Figure 8a, 8b, and 8c we can see that these fluorine anion
water clusters keep the much higher thermal stability. To the
be observed, indicating the residue CoFNO (H O) is very
3 2 4
stable. During the temperature of 265~340 °C, there is a weak
endothermic phenomenon, the weight loss of 3.01
corresponding to one molecules water (calc. 2.90 %).
%
best our knowledge, the losses of all water molecules in 115 Afterward, from 340 to 430 °C there is also no weight loss to
2
6
neutral water cluster are all below 140°C. The losses of the
be
observed,
suggesting
the
residual
compound
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CoFNO (H O) is much stable. This phenomenon is easy to be
room temperature, 300°C and 400°C was shown in Figure 11.
3
2
3
evidenced by the crystal structure studies. In compound (3), 60 As shown in Figure 10 and 11, the characteristic peaks among
ꢀ
1
ꢀ1
ꢀ1
there are one O(1w) molecule and three O(2w) molecules.
O(1w) only forms neutral O(1w)···O(2w) hydrogen bond with
O(2w) molecules which do not exist the intermolecular proton
1500 cm to 2200 cm for imidazole ring and 2800 cm to
ꢀ
1
3100 cm for NꢀH vibration are disappeared (SI Fig. S4ꢀ4,
Standard imidazole IR spectrum), indicating that the
imidazole molecules are decomposed. The obvious unchanged
5
transfer process, while O(2w) form anionic hydrogen bonds
ꢀ
ꢀ1
ꢀ1
not only contacting with F anion [F···O(2w) distance of 65 peak at about 3500 cm for (1) and 3150 cm for (2) is
ꢀ
28
2
2
.726(1) Å] but also with NO3 anion [O···O(2w) distance of
attributed to hydrogenꢀbonded OH stretching vibration.
In summary, three supramolecule sandwich structures
containing fluorine anion water cluster polymer were obtained
.716(1) Å]. Thus, water molecules [this structure for O(2w)]
with anion F and NO forms the strongest hydrogen bond
because of the intracluster proton transfer process F ·H O →
ꢀ
ꢀ
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
3
ꢀ
and characterized by single Xꢀray. The bound water in the
2
ꢀ
ꢀ
ꢀ
2+
HF·OH and NO ·H O → HNO ·OH . The results of above 70 crystal host [M(Im)6] (M=Cd, Ni, Co) can form fluorine
3
2
3
data indicate the stronger anionic hydrogen bond interaction
than that of neutral hydrogen bond interaction. Upon the
temperature increase, the weightꢀloss of 20.93% suggest the
anion water cluster structure. The anion water cluster
aggregate mode, L6(6)6(6)8(6) for (2) has been first reported
experimentally. The shamrockꢀlike shaped pattern for fluorine
anion water cluster and the maple leaf like the pattern for
decomposing of
CoFNO (H O) . The final residual
3 2 3
compound maybe is CoO (Calc. 12.00%, Found 11.39%). 75 nitrate anion water cluster in the compound (3) was first
Hence, the key structural changes should be described as
following:
found. The precise structural information about these three
fluorine anion clusters is helpful for improving the model of
some unexplained properties of water and understanding
better the structure and behavior of water molecules in the
[Co(Im) ][F·NO ·(H O) → CoFNO (H O) → CoFNO (H O)
3
6
3
2
4
3
2
4
3
2
→
CoO.
In order to validate the results of thermogravimetric 80 chemical or physical process. The important thing is that we
ꢀ
ꢀ
ꢀ
analysis, and to examine whether the imidazole ligands lost
completely or water molecules are really existed in the residue
or not, we use the compound (2) as an example. The TG of
crystalline samples for (2) was done under the same apparatus
find F ·H O maybe form F ·H O↔HF·OH proton transfer
2 2
process, which can be existed stable at high temperature. The
fluorine anion water cluster could not be lost even if the
imidazole ligands were decomposed completely. These studies
and condition, the temperature ranges are selected from room 85 have shown that for hydrogen bond interaction, the relation
temperature to 300°C, from room temperature to 400°C and
from room temperature to 800°C. The three final residues
were collected, and together with the original compound (2)
were sent to do Xꢀray powder diffraction (XRPD) and infrared
spectrum (IR). There are only six sorts of elements (C, H, N,
O, F and Ni) and three units of molecules (NiF , Im and H O)
between the anion and water molecules differs from that
observed for pure water molecules or neutral water cluster.
The key here is the fact that we put forward an idea to
understand the bonding relationships in anion water cluster.
90
2
2
for compound [Ni(Im) ] [F ·(H O) ] (2). It will be very easy
6
2
2
5
for us to judge the possible structure or molecular formula
only depending on the XRPD or IR. As shown in Figure 9, the
positions of the most intensive line have disappeared to
compare b (residue at 300°C) and c (residue at 400°C)
comparing with a (original compound), which suggest the
main molecule, imidazole, should be lost or decomposed. To
compare with b and c, the key peaks remain unchanged, only
the peak at 2θ = 39.92 has disappeared for c, indicating that
the main framework structure for b and c is similar. In fact, by
the analysis of TG, b is NiF (H O) and c is NiF (H O),
2
2
4
2
2
respectively, only the water molecules quantities are different
for b and c. Thus, we think that the XRPD studies should be
in agreement with the TG data. The residual compound d at
1a
8
00°C can only be metallic Ni, NiF2 or NiO. Of PDF card
checking, the XRPD of d was in good agreement with the
compound nickel oxide (PDF number: 75ꢀ0269, 78ꢀ0643, 89ꢀ
3
080). Hence, key structural changes of compound (2) under
heating should be described as following:
Ni(Im) ][F ·(H O) ]→Ni[F ·(H O) ]→Ni[F ·(H O)]→NiO.
[
6
2
2
5
2
2
4
2
2
The IR spectrum can also afford the useful structural
information. We have done the IR structural characterization
of compounds (1) and (2) at a different temperature. The IR
spectra of compound (1) at 150°C, 300°C and 450°C was
shown in Figure 10, and the IR spectra of the compound (2) at
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DOI: 10.1039/C8CE00532J
1
b
20
4a
4b
2
+
Fig. 1. (1a) View of the discrete [M(Im)6] forming 2D
supramolecular coordinated polymer through the CꢀH···π
interactions. (1b) View of the fluorine anion water cluster
sandwiched between two nearly [M(Im)6]n polymers. Ball and
stick represent anion water cluster; YellowꢀF atom, RedꢀO atom.
Fig. 4. (4a) F1 and F2 all show the trigonal bipyramid
coordinated geometry for compound (2). (4b) O1w shows the
tetrahedron coordinated geometry and O2w, O3w, O4w, O5w all
show the plane trigonal coordinated geometry. Colours are below:
yellow, F1; green, F2; red, O1w; pink, O2w, blue, O3w; purple,
O4w; cyanine, O5w.
5
2
n+
25
2
n+
1
0
Fig. 2. View of host [M(Im)6]n being wrapped in
supramolecular macrocyclic structure along the ac plane.
5
a
5b
2
nꢀ
Fig. 5. (5a) Showing [F (H O) ]
4 n
fluorine anion water cluster
2
2
ꢀ
2+
30
polymer for compound (2), NO and [Co(Im) ] omitted for
3 6
ꢀ
ꢀ
nꢀ
4 n
clarity. (5b) Showing [F ·NO ·(H O) ] anion water cluster
polymer for compound (2), [Co(Im)6] omitted for clarity.
Colours are below: yellow, F; red, O1w; pink, O2w.
3
2
2+
35
6
a
2
ꢀ
Fig. 3. (a) [F2 ·(H O) ] anion water cluster polymer for
2
5 n
2
n+
1
5
compound (2). Host [M(Im)6]n was omitted for clarity. Colours
are as follows: yellow, F1; green F2, red, O1w; pink, O2w; blue,
O3w; purple, O4w; cyanine, O5w. (b) View of the distances
between the adjacent fluorine anion water layers.
6
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6
b
8
b
2
ꢀ
Fig. 6. (6a) View of O atoms of NO connecting two hosts
Co(Im)6] cation by O···HN interaction. (6b) View of the
distances between the adjacent [F ·NO ·(H O) ] water cluster
polymer layers, and the host [Co(Im) ] cations sandwiched
3
2+
[
ꢀ
ꢀ
5
3 2 4
2
+
6
ꢀ
ꢀ
between two planar [F ·NO ·(H O) ] layer.
3
2
4
7
a
20
8c
Fig. 8. TG and DTG analysis for compound 1 (8a), 2(8b) and 3
8c).
(
1
0
7
b
ꢀ
Fig. 7. (7a) [F ·(H O) ] fluorine anion water cluster show the
2
4 n
ꢀ
shamrockꢀlike shaped pattern. (7b) [NO ·(H O) ] anion water
3
2
4
cluster show the maple leaf shaped pattern.
aꢀcompound 2
bꢀ300°C
cꢀ400°C
dꢀ800°C
80
0
10
20
30
40
50
60
70
2
Theta
Fig.9. XPRD patterns for compound (2): (a) The original
crystalline samples of (2); (b) The residue of (2) at 300°C; (c)
The residue of (2) at 400°C; (d) The residue of (2) at 800°C.
25
1
5
8
a
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DOI: 10.1039/C8CE00532J
of (1), (2) and (3) are CCDCꢀ726796, CCDCꢀ726797, CCDCꢀ
26798.
7
Synthesis of 1 The novelty Cd(OH) was prepared by mixture
2
Cd(NO ) ·4H O (3.08 g, 10 mmol) with NaOH (0.80 g, 20
3
2
2
4
4
5
5
6
0
5
0
5
0
mmol) in water solution. After filtrated and washed with water,
solid Cd(OH) was added to the diluted hydrofluoric acid (0.4 g,
2
2
0 mmol) of water (20mL) in a plastic beaker (Hydrofluoric acid
is a colorless, smokeless liquid, highly corrosive.When using
hydrofluoric acid, you must wear a mask and latex gloves and
operate in a fume cupboard). The stirring did not stop until the
solid dissolved completely. The CdF solution was obtained by
2
modulating the pH value to 5~6. Ten drops of the prepared CdF2
solution was added in the solution of imidazole (2.04 g, 30 mmol)
in 40 mL solvent (EtOH: H O = 1: 4). The resulting solution was
2
refluxed for 2 hours and filtered. The colorless solution was
evaporated slowly, and after several days clear block single
crystal was obtained. They were submitted for elemental analysis.
Xꢀray crystallographic study has confirmed the existence of
Fig. 10. IR spectra of the sample (1). (a) At 150°C; (b) At
00°C; (c) At 450°C.
3
5
[
Cd(Im) ][F·H O] . Anal. Calc. for C H CdF N O 1: C,
6 2 2 18 28 2 12 2
36.31%; H, 4.71%; N, 28.33%, F, 6.39%; O, 5.38%; Cd, 18.89%.
Found: C, 36.29%; H, 4.67%; N, 28.36%.
c
Synthesis of 2. Same procedure as for 1. and. Use NiCl ·6H O
b
2
2
(
2.40 g, 10 mmol) to instead of Cd(NO ) ·4H O, purple crystal
3 2 2
[Ni(Im) ][F ·(H O) ]
2
was obtained. Anal. Calc. for
6
2
2
5
C H F N NiO : C, 36.29%; H, 5.71%; N, 28.22%, F, 6.38%; O,
18
34
2
12
5
1
3.44%; Ni, 9.86%. Found: C, 36.26%; H, 5.66%; N, 28.29%.
Synthesis of 3. The similar way of 1, except for the use of
Co(NO ) ·6H O (3.00 g, 10 mmol) instead of Cd(NO ) ·6H O.
65 Pink block crystal 3 was obtained. Xꢀray crystallographic study
3
2
2
3 2
2
a
has confirmed the existence of [Co(Im) ][F·NO ·(H O) ]. The
6
3
2
4
ꢀ
importing NO3 anions were because of Co(OH) absorbing some
2
Co(NO3)2 or NaNO3 not to be completely washed off from
Co(OH) colloid sedimentation. Anal. Calc. for C H CoFN O :
2
18 32
13
7
70
C, 34.81%; H, 5.16%; N, 29.33%, F, 3.06%; O, 18.05%; Co,
9.50%. Found: C, 34.79%; H, 5.54%; N, 29.38%.
3500
3000
2500
2000
1500
1000
500
Fig. 11. IR spectra of the sample (2). (a) The original crystalline
samples of (2); (b) The residue of (2) at 300°C; (c) The residue of
Electronic supplementary information (ESI) available: Crystal
data (Tables S1–S3) of compounds (1), (2) and (3), and spectra
data (XRD, UV, IR, Fluorescence) of all new products.
(2) at 400°C.
1
1
2
2
3
3
0
5
0
5
0
5
Experimental Section
75
Physical Measurements. Elemental analyses were measured
with a Perkinꢀ Elmer 1400C analyzer. Infrared spectra were
recorded on a Nicolet 170SX spectrometer using pressed KBr
1 (a) J. Wang, L. L. Zheng, C. J. Li, Y. Z. Zheng, M. L. Tong,
Cryst. Growth Des. 2006, 6, 357; (b) X. B. Wang, X. Yang, J. B.
Nicholas, L. S. Wang, Science 2001, 294, 1322; (c) W. H.
Robertson, E. G. Diken, E. A. Price, J. W. Shin, M. A. Johnson,
ꢀ
1
plates in the 4000ꢀ500 cm ranges. Thermogravimetry (TG) and
differential thermal gravimetric (DTG) analyses were recorded on 80 Science 2003, 299, 1367.
an SDT 2980 simultaneously for the crystalline samples under a
nitrogen atmosphere (150 mL/min) at a heating rate of 20°C/min.
The phase and purity of the asꢀprepared products were
determined by Xꢀray diffraction (XRD) and was performed on a
2 (a) H. Ohtaki, T. Radnai, Chem. Rev. 1993, 93, 1157; (b) A. W.
Castleman, K. H. Bowen, J. Phys. Chem, 1996 100, 12911.
3 R. Kumar, A. K. Pandey, M. K. Sharma, L. V. Panicker, S.
Sodaye, G. Suresh, S. V. Ramagiri, J. R. Bellare, A. Goswami, J.
D/maxꢀ2500 Xꢀray diffractometer equipped with graphite 85 Phys. Chem. B 2011, 115, 5856.
monochromatized Cu K radiation (λ=1.5406 Å).
Crystallographic Data Collection. The diffraction data were
collected on a SMART APEXII diffractometer with graphite
4 (a) U. Achatz, B. S. Fox, M. K. Beyer, V. E. Bondybey, J. Am.
α
Chem. Soc. 2001, 123, 6151. (b) B. S. Fox, M. K.Beyer, U.
Achatz, S. Joos, G. NiednerꢀSchatteburg, V. E. Bondybey, J.
Phys. Chem. A. 2000, 104, 1147; c) S. Irle, J. M. Bowman, J.
monchromatic MoꢀK (λ = 0.71073 Å, T = 293K) radiation.
α
Empirical absorption correction was carried out by using the 90 Chem. Phys. 2000, 113, 8401; c) M. MeotꢀNer, Chem. Rev. 2005,
SADABS program. Their structures were solved by direct
methods and refined by least squares on Fobs with SHELXTL
software package. All nonꢀH atoms were anisotropically refined.
The hydrogen atoms were located by difference synthesis and
105, 213.
2
5 (a) W. H. Thompson, J. T. Hynes, J. Am. Chem. Soc. 2000, 122,
6278; b) H. Y. Chen, W.ꢀS. Shen, Chem. Phys. Lett. 2001, 335,
475; c) J. Kim, H. M. Lee, S. B. Suh, D. Majumdar, K. S. Kim, J.
refined isotropically. The molecular graphics were plotted using 95 Chem. Phys. 2000, 113, 5259.
SHELXTL. Atomic scattering factors and anomalous dispersion
corrections were taken from International Tables for Xꢀray
6 a) H. M. Lee, D. Kim, K. S. Kim, J. Phys. Chem. 2002, 116,
5509; b) H. M. Lee, D. Kim, K. S. Kim, J. Phys. Chem. 2001,
114, 4461; c) G. M. Chaban, S. S. Xantheas, R. B. Gerber, J.
Phys. Chem. A, 2003, 107, 4952; d) O. M. Cabarcos, C. J.
Crystallography.
A summary of the key crystallographic
information for (1), (2) and (3) was given in Supporting
Information (SI) Table S1ꢀ1, S2ꢀ1 and S3ꢀ1. The CCDC numbers
8
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DOI: 10.1039/C8CE00532J
Weinheimer, J. M. Lisy, S. S. Xantheas, J. Chem. Phys. 1999,
1
7
6
10, 5.
W. H. Thompson, J. T. Hynes, J. Am. Chem. Soc. 2000, 122,
278.
5
8 C. G. Zhan, D. A. Dixon, J. Phys. Chem. A 2004, 108, 2020
M. Cametti, K. Rissanen, Chem. Commun. 2009, 2809.
9
2
(a) T. W. Hudnall, C. W. Chiu, F. P. Gabbai, Acc. Chem. Res.,
009, 42, 388; (b) I. Ravikumar, P. S. Lakshminarayanan, M.
Arunachalam, E. Suresh, P. Ghosh, Dalton Trans., 2009, 4160; (c)
M. Mascal, I. Yakovlev, E. B. Nikitin, J. C. Fettinger, Angew.
Chem., Int. Ed., 2007, 46, 8782; (d) S. O. Kang, D. VanderVelde,
D. Powell, K. BowmanꢀJames, J. Am. Chem. Soc., 2004, 126,
1
1
2
2
3
3
4
4
5
5
0
5
0
5
0
5
0
5
0
5
1
2272; (e) S. O. Kang, J. M. Llinares, D. Powell, D. VanderVelde,
K. BowmanꢀJames, J. Am. Chem. Soc., 2003, 125, 10152.
10 a) G. N. Merrill, S. P. Webb, J. Phys. Chem. A, 2003, 107,
7
852. b) L. S.Sremaniak, L. Perera, M. L. Berkowitz, J. Phys.
Chem. 1996, 100, 1350. c) J. R. Roscioli, E. G. Diken, M.
A.Johnson, S.Horvath,; A. B. McCoy, J. Phys. Chem. A, 2006,
1
10, 4943.
11 R. A. Jacobson, W. P. Jensen, Inorg. Chim. Acta, 1981, 52,
2
1
4
1
05.
2 A. L. Pickering, D. L. Long, L. Cronin, Inorg. Chem., 2004,
3, 4953.
3 J. Emsley, M. Arif, P. A. Bates, M. B. Hursthouse,
Chem.Commun., 1989, 738
1
2
1
4 J. Holzbock, W. Sawodny, U. Thewalt, Z. Anorg. Allg. Chem.,
000, 626, 2563.
5 M. C. Etter, J. C. MacDonald, J. Bernstein, Acta Crystallogr.,
Sect. B: Struct. Sci., 1990, B46, 256.
16 J. Bernstein, R. E. Davis, L. Shimoni, N.ꢀL. Chang, Angew.
Chem., Int. Ed. Engl., 1995, 34, 1555.
1
7 (a) F. F.Jian, Z. X. Wang, Z. P. Bai, X. Z. You, H. K.Fun, J.
Chem. Crystallogr. 1999, 29(3), 359. (b) Z. X. Wang, F. F. Jian,
Y. R.Zhang, F. S. Li, H. K.Fun, J. Chem. Crystallogr. 1999,
29(8), 885. (c) F. F. Jian, P. S. Zhao, H. L. Xiao, S. S. Zhang, J.
Chem. Crystallogr. 2002, 32(10), 395.
1
2
2
8 (a) L. Infantes, J. Chisholm, S. Motherwell, CrystEngComm.
003, 5, 480. (b) L. Infantes, S. Motherwell, CrystEngComm
002, 4, 454.
19 D.Eisenberg, W. Kauzmann, The Structure and Properties of
Water; Oxford University Press: New York, 1969.
2
2
2
0 I. Bernal, C. R. Chimie, 2007, 10, 1209.
1 M. Mascal, L. Infantes, J. Chisholm, Angew. Chem. Int. Ed.
006, 45, 32.
22 M. A. Hossain, M. A. Saeed, A. Pramanik, B. M. Wong, S. A.
Haque, D. R. Powell, J. Am. Chem. Soc., 2012, 134, 11892.
2
1
2
3 C. Janiak, T. G. Scharmann, J. Am. Chem. Soc. 2002, 124,
4010.
4 M. Mascal, L. Infantes, J. Chisholm, Angew. Chem. Int. Ed.
2006, 45, 32.
5 K. Raghuraman, K. K. Katti, L. J. Barbour, N. Pillarsetty, C.
L. Barnes, K. V. Katti, J. Am. Chem. Soc., 2003, 125, 6955.
6 (a) N. H. Hu, Z. G. Li, J. W. Xu, H. Q.Jia, J. J. Niu, Cryst.
2
2
Growth Des. 2007, 7, 15. (b) R. Sun, Y. Z. Li, J. F. Bai, Y. Pan,
Cryst. Growth Des. 2007, 7, 890. (c) I. Bernal, U. Mukhopadhyay,
Cryst. Growth Des. 2006, 6, 363. (d)G. Beobide, O. Castillo, A.
Luque, U. GarciaꢀCouceiro, J. P.GarciaꢀTeran, P. Roman, Inorg.
Chem. 2006, 45, 5367. (e)H. H. Song, B. Q. Ma, CrystEngComm.
2
007, 9, 625.
27 a) T. K. Prasad, M. V. Rajasekharan, Cryst. Growth Des. 2006,
, 488. b) X. L. Hong, Y. Z. Li, H. M. Hu, Y. Pan, J. F. Bai, X. Z.
You, Cryst. Growth Des. 2006, 6, 1221.
6
6
0
5
6
2
3
8 M. Miyazaki, A. Fujii, T. Ebata, N. Mikami, Science, 2004,
04, 1134.
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DOI: 10.1039/C8CE00532J
ꢀ
The Interesting Fluorine Anion Water Clusters [F ·(H O) ]
2
n
in Metal Complex Crystal
*
Fang Fang Jian*, Liu E, Junying Ma
Three crystalline complexes containing fluorine anion water cluster were reported.
The TGA, IR and XRD studies at different testing temperature were suggested that
ꢀ
fluorine anion water cluster, F (H
2
O)
n
, were much stable. This phenomenon was
ꢀ
indicated the strongest anionic hydrogenꢀbonds interaction between F and H O,
which confirmed the intracluster proton transfer process F ·H
2
O→HF·OH . This result
2
ꢀ
ꢀ
suggests that the fluoride anions and water molecules are Hꢀbonded to each other in
an alternating fashion within the fluoride−water hybrid cluster, where a fluoride anion
plays the important role of connecting host metal complex and guest water cluster.