Ionothermal synthesis and crystal structures of novel aluminum phosphates with in situ generated templates

Article abstract of DOI:10.1039/c4dt03233k

Protic ionic liquids (PILs) are a subgroup of ionic liquids and easily formed by proton transfer from a Bronsted acid to a Bronsted base. Two new crystalline aluminophosphates, [C₅H₁₆N₂][Al(PO₄)(HPO₄)] (AlPO-PIL1) and [C₅H₁₆N₂][Al₂(OH)₂ (PO₄)₂] (AlPO-PIL2), are successfully prepared for the first time from a protic ionic liquid, 3-dimethylaminopropylamine acetate. Their structures were determined from single-crystal X-ray diffraction data. It was found that HF in the reaction mixture is crucial in determining the selectivity of the phase. In the absence of HF, AlPO-PIL1 with a one-dimensional chain structure was synthesized by templating the protonated 3-dimethylaminopropylamine cation of the PIL. Upon addition of HF to the initial reaction mixture, AlPO-PIL2 was obtained by templating the protonated N,N′-dimethyl-1,3-propanediamine, which was in situ generated from the protonated 3-dimethylaminopropylamine through migration of methyl groups during the crystallization. AlPO-PIL2 has a novel layered structure with a 3-connected 4·8·8 two-dimensional network which has never been found in the previously reported layered aluminophosphates.

Full text of DOI:10.1039/c4dt03233k

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Journal Name
RSCPublishing
ARTICLE
Ionothermal Synthesis and Crystal Structures of
Novel Aluminum Phosphates with in Situ Generated
Templates
Cite this: DOI: 10.1039/x0xx00000x
Shanshan Man, Zenglong Wang, Boya Zhao, Lei Liu* and Jinxiang Dong,
Received 00th January 2012,
Accepted 00th January 2012
Protic ionic liquids (PILs) are subgroup of ionic liquids and easily formed by proton transfer
from a Brønsted acid to a Brønsted base. Two new crystalline aluminophosphates,
DOI: 10.1039/x0xx00000x
[
C H N ][Al(PO )(HPO )] (AlPOꢀPIL1) and [C H N ][Al (OH) (PO ) ] (AlPOꢀPIL2), have
5 16 2 4 4 5 16 2 2 2 4 2
www.rsc.org/
been successfully prepared for the first time from
a
protic ionic liquid, 3ꢀ
dimethylaminopropylamine acetate. Their structures were determined from singleꢀcrystal Xꢀ
ray diffraction data. It was found that HF in the reaction mixture is crucial to determine the
selectivity of phase. In the absence of HF, AlPOꢀPIL1 with oneꢀdimensional chain structure
was synthesized by templating the protonated 3ꢀdimethylaminopropylamine cation of the PIL.
Upon addition of HF to the initial reaction mixture, AlPOꢀPIL2 was obtained by templating the
protonated N,N'ꢀdimethylꢀ1,3ꢀpropanediamine, which was in situ generated from the
protonated 3ꢀdimethylaminopropylamine through migration of methyl groups during the
crystallization. AlPOꢀPIL2 has a novel layered structure with 3ꢀconnected 4.8.8 2ꢀdimensional
network which has never been found in the previous reported layered aluminophosphates
.
primary, secondary and tertiary ammonium, and this will give
us the more possibilities of preparing novel metal phosphates
by choosing a suitable ionic liquid as solvent and template.
More recently, using a protic ionic liquid as solvent and
template, we have synthesized two zinc phosphates, both are
known framework structures. But these efforts encourage us
to further extend the possibility of application of PILs for the
synthesis of other metal phosphates. Herein, another protic
ionic liquid, 3ꢀdimethylaminopropylamine acetate, was used to
synthesize aluminophosphates for the first time. As a result,
Introduction
Since the discovery of microporous aluminophosphates by
Wilson and coꢀworkers
[
1]
in 1982, many openꢀframework
aluminophosphates with various architectures have been
synthesized. Most of these materials were achieved in the
presence of organic amines by using hydro/solvothermal
method, and it was found that the solvents and organic amines
are crucial to obtain the aluminophosphates with novel
[
19]
[
2ꢀ4]
structures.
Ionothermal synthesis, using ionic liquids or eutectic mixtures
as solvent and template, was firstly reported by Morris in
two
novel
crystalline
aluminum
phosphates,
[
C H N ][Al(PO )(HPO )] and [C H N ][Al (OH) (PO ) ],
5
16
2
4
4
5
16
2
2
2
4 2
[
5]
2
004. Nowadays, this emerging synthetic approach has been
have been successfully synthesized and their structures were
determined from the single crystal diffraction data. The powder
XRD, SEM, TGꢀDSC and CHN analysis were also used to
characterize the two materials.
shown a great potential to prepare crystalline solids with novel
[
6ꢀ
structures or improve the known phases for specific purposes.
1
4]
Also, these synthetic procedures can be performed at
ambient pressure, thus it could eliminate safety concerns
associated with high solvent pressures and provide more
conveniences to study the crystalline mechanism.
[
15ꢀ16]
Experimental
It is well known that the species and structure of ionic liquids
are very rich and dynamic, but so far much of the work on
ionothermal synthesis has concentrated predominantly on the
use of the imidazoleꢀbased ionic liquids and deep eutectic
Raw materials
Aluminum hydroxide (Al(OH) , 99.5wt%), orthophosphoric
3
acid (H PO , 85 wt% in water), 3ꢀdimethylaminopropylamine
3
4
[
5ꢀ7]
mixtures.
Many of these ionic liquids are structurally related
(
C H N , 99.5wt%), acetic acid (CH COOH, 99.5wt%)
5 14 2 3
to each other and often template the same frameworks. Protic
ionic liquids (PILs) are a subset of ionic liquids and are formed
through proton transfer from a Brønsted acid to a Brønsted
andabsolute alcohol(CH CH OH, 99.5wt%)were purchased
from Aladdin Reagent (China) Co., Ltd and used without
further purification.
3
2
[
17ꢀ18]
base.
Compared to imidazoleꢀbased ionic liquids, these
ionic liquids are generally lower cost and can be easily prepared
in high purity. Also, the cations of the PILs can be made up of
Synthesis
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Journal Name
The protic ionic liquid, 3ꢀdimethylaminopropylamine acetate [C H N ][Al (OH) (PO ) ] (AlPOꢀPIL2), have been obtained
5
16
2
2
2
4 2
(
designed as (HDMAPA)(Ac)), was prepared by neutralization in the absence and presence of HF in initial mixture,
of 3ꢀdimethylaminopropylamine (DMAPA) with acetic acid as respectively. Their structures were determined from singleꢀ
shown in Scheme S1. A flask was charged with DMAPA and crystal Xꢀray diffraction data. The experimental XRD patterns
placed in water bath, then an equimolar acetic acid was slowly for the two compounds are in good agreement with the
added with stirring in N atmosphere, (HDMAPA)(Ac) can be simulated patterns from single crystal Xꢀray structure data
2
obtained after reaction for 24 hours. The purity of PIL was (Figure S3), proving the phase purity of the asꢀsynthesized
1
13
confirmed using H and C nuclear magnetic resonance (NMR) products. The difference in reflection intensities between the
Figure S1 and S2), and its melting point is roughly 45°C which simulated and experimental patterns was due to the variation in
was measured by meltingꢀpoint apparatus. preferred orientation of the powder sample. The results of
(
Aluminium phosphates were prepared with the following elemental analysis (wt %) also confirmed the phase purity in
typical procedure: a Teflonꢀlined autoclave (15 mL) was each case (for AlPOꢀPIL1: Calcd. C, 18.63; N, 8.69; H, 5.28.
charged with Al(OH) , (HDMAPA)(Ac) and H PO , and heated Found: C, 18.29; N, 8.39; H, 5.12; for AlPOꢀPIL2: Calcd. C,
3
3
4
at 180°C for 3 days. The solid product was recovered by 15.70; N, 7.33; H,4.71. Found: C, 15.32; N, 7.12; H, 4.20). The
dissolving the reaction mixture in water and subsequent SEM images (Figure S4) show the different crystal
filtration, then washed thoroughly with absolute alcohol and morphologies of AlPOꢀPIL1 and AlPOꢀPIL2, also indicating
dried at room temperature. Detailed synthesis conditions and the purity of the asꢀsynthesized samples.
reaction results are presented in Table S1. It was found that For AlPOꢀPIL1, its asymmetric unit (Figure 1a) contains 18
P/Al ratios in initial mixture have no obvious influence on the nonꢀhydrogen atoms, of which 11 atoms belong to the
resulting phases, AlPOꢀPIL1 could be obtained with P/Al ratio aluminum phosphate chain and 7 atoms belong to the organic
in the range of 2 to 7, but upon the addition of a small amount specie,
diprotonated
DMAPA.
There
are
one
of HF, another phase was formed. The typical formulations in crystallographically distinct Al and two P atoms in the
molar ratio for AlPOꢀPIL1 and AlPOꢀPIL2, which are used for asymmetric unit. The Al atom is tetrahedrally coordinated by
single
crystal
structure
determination,
are four O atoms belonging to four different PO tetrahedra, with
4
1
Al(OH) :4H PO :10PIL and 1Al(OH) :1H PO :10PIL:0.5HF, AlꢀO bond lengths between 1.7284(18) and 1.7442(17) Å, and
3
3
4
3
3
4
respectively.
OꢀAlꢀO bond angles in the range of 105.92(9)°ꢀ112.51(9)°. PO4
tetrahedra share two O atoms with adjacent AlO tetrahedra and
4
the other two O atoms exist in the form of a terminal linkage,
and the PꢀO distances vary from 1.5106(18) to 1.5479(17) Å
and from 1.4755(18) to 1.5642(18) Å for the P1 and P2
phosphate groups, respectively. This dispersion is attributable
Characterization
Powder Xꢀray diffraction (XRD) patterns were collected on a
RigakuMiniflex Xꢀray diffractometer with CuꢀKα radiation
λ=1.5418 Å) in the 2θ range of 3ꢀ50
Ⅱ
(
°
and with a scan rate of to multipleꢀbond character and is often observed in the low
1
13
[21ꢀ22]
2
°/min. H and C NMR spectra for PIL in CDCl were dimensional aluminophosphates.
3
recorded using a DRX300 NMR spectrometer. CHN element
analysis was carried out on an ElementarVario EL analyzer.
Thermogravimetric analysis (TGA) was recorded on
SETARAM Labsys Evo instrument in air atmosphere with a
heating rate of 5°C/min. SEM images were obtained on a
Hitachi, TMꢀ3000 scanning electron microscope.
<
Figure 1>
AlPOꢀPIL1 has oneꢀdimensional chain structure with 4ꢀ
membered rings constructed from strictly alternating AlO and
PO /PO (OH) units, the inorganic chains [AlP O H] were
4
2ꢀ
4
3
2
8
separated by diprotonated DMAPA (Figure 2). The organic
cations between the chains not only balance the negative
charges of the macroanionic chains, but also interact with the
Structure Determination
The single crystals for AlPOꢀPIL1 and AlPOꢀPIL2 with a
suitable size were selected, then sets of single crystal Xꢀray
diffraction data were collected on a Bruker SMARTꢀ1000 CCD
area detector system using graphiteꢀmonochromated MoꢀKα
radiation(λ=0.71073 Å). The crystal structures were solved by
using direct methods and refined by fullꢀmatrix leastꢀsquares
terminal oxygen atoms of PO tetrahedral through NꢀH
…O
4
hydrogen bonds, with N
.783 Å.
…O distances in the range of 2.657 to
2
<Figure 2>
[
20]
with SHELXTL97 software package.
The aluminum and
phosphorus atoms were determined directly, and then the
carbon, nitrogen, and oxygen atoms were found in the
difference Fourier map. All nonꢀhydrogen atoms were refined
with anisotropic thermal parameters and the hydrogen atoms
were geometrically placed. A summary of the crystallographic
data and structure details is presented in Table 1.
In ionothermal synthesis, fluoride has often been used as a
mineralizer for crystallization of the desired aluminophosphate
materials, which seems to be important in determining the
[5]
phase selectivity of the reaction. In addition, there is evidence
that fluoride could result in the variation of the bulk ionic liquid
[23]
during the crystallization process.
In the present study, on
addition of HF to the reaction mixture, a novel layered
aluminophosphate, [C H N ][Al (OH) (PO ) ], was obtained.
<
Table 1>
5
16
2
2
2
4 2
It is interesting to note that the organic species in AlPOꢀPIL2
are the protonated N,N'ꢀdimethylꢀ1,3ꢀpropanediamine
DMPDA) instead of the original ionic liquid, the protonated 3ꢀ
Results and discussion
(
dimethylaminopropylamine (DMAPA). It is believed that the
DMPDA is in situ generated from the protonated DMAPA
1
. Crystal structures
From the PIL (HDMAPA)(Ac), two aluminophosphates, through intramolecular methyl migration during the
[
C H N ][Al(PO )(HPO )]
(AlPOꢀPIL1)
and crystallization. Intramolecular methyl migration is well known
5
16
2
4
4
2
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C4DT03233K
in the organometallic reactions and in the rearrangements of a gradual weight loss with about 4.5 wt%, corresponding to the
carbonium ions, intramolecular methyl migration in the dehydroxylation from the PꢀOH. For AlPOꢀPIL2, TGꢀDSC
pronated DMAPA and DMPDA were found to proceed by a curves (Figure S5b) show a major weight loss occurring around
[
24ꢀ25]
highꢀenergy inversion mechanism.
310°C accompanied by a marked endothermic effect. The total
The singleꢀcrystal structure analysis shows that AlPOꢀPIL2 weight loss of the compound between 240 and 600°C is about
involves a novel layer topology. Its asymmetric unit (Figure 1b) 28.6%, in accordance with the calculated value on the basis of
contains one crystallographically independent Al and P atoms. the empirical formula (23.8% for the decomposition of the
Each P atom is tetrahedrally coordinated by four oxygen atoms, template, 4.7% for dehydroxylation of AlꢀOH). Powder XRD
three of them bridge to adjacent Al atoms with PꢀO bond patterns of the two samples heated in air or N atmosphere at
2
lengths within 1.522(3) Åꢀ1.536(2) Å, the fourth oxygen atom different temperatures (Figure S6 and S7) show that, their
exists in the form of a terminal P=O linkage with P=O bond structures are retained on calcinations at 250°C, and become
length being 1.494(3) Å, which is very similar to those in other amorphous phase beyond 300°C.
[
21,26]
layered aluminophosphates containing terminal P=O bonds.
Each Al atom exists in the form of AlO (OH) tetrahedra, which
3
3. The effect of the crystallization time
shares three oxygen atoms with adjacent P atoms and leaves
one vertex for the terminal hydroxyl groups. The AlꢀOH bond
length is 1.657(2) Å, shorter than other AlꢀO bonds in this
structure with the average value being 1.726 Å. There are some
examples containing AlꢀOH groups in the previously reported
For ionothermal synthesis, generally the starting materials were
almost completely dissolved in the ionic liquid at crystallization
temperatures, and the synthesis mechanism is a crystallization
[
5]
from solution rather than a solidꢀtoꢀsolid transformation. To
describe the crystallization process, powder XRD patterns
(Figure S8) were recorded for the samples after different
crystallization times. For AlPOꢀPIL1, the nucleation and
crystallization rate of the crystal are very fast, the crystallinity
can reach a high level after reaction for 6h. By contrast, the
nucleation rate for AlPOꢀPIL2 seems to proceed in a slow
manner, the crystal nucleation was gradually generated and
began to grow after reaction for 12h. The reasons may attribute
to the formation of the new template agents for AlPOꢀPIL2, the
protonated DMPDA needs a period of time to be formed from
2
ꢀD
4
layered
aluminophosphates,
such
as
[
27]
[
(
C H N ][Al P O (OH) ] and
C N H )[AlPO (OH)] ·H O
12
2
2
2
8
2
[
28ꢀ29]
,
however,
the
Al
3
2
12
4
2
2
coordination in these compounds is more than four and the OH
ligands are found to connect the adjacent Al atoms in the form
of Alꢀ(OH)ꢀAl linkages.
<
Figure 3>
The structure (Figure 3a) is made up of macroanionic layers of the protonated DMAPA through intramolecular methyl
2−
empirical formula [Al (PO ) (OH) ]
with diprotonated migration at initial crystallization process.
2
4 2
2
DMPDA cations between the interlayer. The organic cations
located in the interlayer region not only balance the negative
charges of the macroanionic layers, but also hold the anionic
layers together through hydrogenꢀbonds in different ways. The
Conclusions
diprotonated DMPDA cations interact with the terminal O In conclusion, it was the first time that two novel
atoms of PO and AlO (OH) units through NꢀH
…
O hydrogen aluminophosphates, AlPOꢀPIL1 and AlPOꢀPIL2, were
4
3
successfully synthesized from the protic ionic liquid. The
former has a oneꢀdimensional chain structure, and the latter has
a novel layered structure with 3ꢀconnected 4.8.8 2ꢀdimensional
network which has never been found in the previous reported
layered aluminophosphates. AlPOꢀPIL2 was obtained by
templating the protonated N,N'ꢀdimethylꢀ1,3ꢀpropanediamines,
which was in situ generated from the protonated 3ꢀ
dimethylaminopropylamine through migration of methyl
groups upon the addition of HF to the initial reaction mixture.
Protic ionic liquids are a subset of ionic liquids and can be
easily prepared from prolific and available amine precursors. In
our study, we proved the feasibility for the ionothermal
synthesis of aluminophosphates from the protic ionic liquid,
and this will give us the more opportunities of preparing novel
crystalline materials by choosing a suitable ionic liquid as
solvent and template.
bonds, respectively, with N
to 3.078 Å.
…
O distances in the range of 2.721
Each P atom in the structure is connected with three Al atoms
through oxygen bridges and vice versa. PO and AlO (OH)
4
3
tetrahedra are linked in a strict alternation to form a single
chain with cornerꢀsharing Al P fourꢀmembered rings (Figure
2
2
3
c). The connectivity between the chains via Al–O–P linkages
2
ꢀ
leads to the anionic [Al P O (OH) ] layer with eightꢀ
2
2
8
2
membered rings, parallel to the bc plane (Figure 3b). In fact,
this structure can be regarded as a 3ꢀconnected 4.8.8 2ꢀ
dimensional network which could be found in 3ꢀdimensional
openꢀframework aluminophosphates and zeolites such as
[
30]
AlPO ꢀC, AlPO ꢀ15, GIS, MER and PHI structures.
This is
4
4
the first example for the layered aluminophosphate with 3ꢀ
connected 4.8.8 2ꢀdimensional network. As far as we know,
only 4.6.12ꢀ, 4.6.8ꢀ, 4.6ꢀ, 4.8ꢀ, 4.20ꢀ and 4.12 nets werereported
for
the
layered
aluminophosphates
with
various
[
2,4]
stoichiometries.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation (21276174, 21322608), Shanxi Province
2
. Thermal analysis
To investigate the thermal stability of the two materials, Science Foundation for Youths (2014021005), Program for
thermogravimetric analysis (TGꢀDSC) and powder XRD New Century Excellent Talents in University (NCETꢀ11ꢀ1038),
measurement were performed. For AlPOꢀPIL1, TGꢀDSC curves and A Foundation for the Author of National Excellent
(
FigureS5a) show an obvious weight loss of ca. 31 wt % in the Doctoral Dissertation of PR China (No. 201350).
region of 240ꢀ350°C, accompanied with a marked exothermic
peak, resulting from the remove of organic species between
chains with calculated value of 32 wt%. Above 350°C, there is
Notes and references
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Journal Name
Research Institute of Special Chemicals, Taiyuan University of
Technology, Taiyuan 030024, Shanxi, P. R. China. Fax: +86ꢀ351ꢀ
26.S. Oliver, A. Kuperman, A. Lough and G. A. Ozin, Chem.
Commun.,1996, 35, 1761.
6
†
111178; Tel: +86ꢀ351ꢀ6010550ꢀ5; Eꢀmail: liulei@tyut.edu.cn.
27.K. X. Wang, J. H. Yu, P. Miao, Y. Song, J.Y. Li, Z. Shi and R. R. Xu,
J. Mater. Chem., 2001, 11, 1898.
1
Electronic Supplementary Information (ESI) available: HꢀNMR and
1
3
CꢀNMR spectra of (HDMAPA)(Ac), powder XRD patterns, SEM
28.A. Tuel, V. Gramlich, C. Baerlocher, MicroporousMesoporous
Mater., 2000, 41, 217.
images and two CIF files for the two aluminophosphate materials. See
DOI:10.1039/b000000x/
29.H. M. Yuan, J. S. Chen, Z. Shi, W. Chen, Y. Wang, P. Zhang, J.H.
Yu andR. R. Xu, J. Chem. Soc. Dalton Trans., 2000, 1981.
1
. S.T.Wilson, B.M.Lok, C.A.Messian,T. R. Cannan and E. M.Flanigen,J. 30. C. Baerlocher, L. B. McCusker and D. H. Olson, Atlas of Zeolite
Am. Chem. Soc.,1982, 104, 1146.
Framework Types; Elsevier: Amsterdam, 2007.
2
3
4
. J. H. Yu and R. R. Xu, Acc. Chem. Res., 2003, 36, 481.
. J. H. Yu and R. R. Xu, Chem. Soc. Rev., 2006, 35,593.
. R. Murugavel, A. Choudhury, M. G. Walawalkar, R. Pothiraja and C.
N. R. Rao, Chem. Rev., 2008, 108, 3549.
5
. E. R. Cooper, C. D. Andrew, P. S. Wheatley, P. B. Webb, P. Wormald
and R. E. Morris, Nature., 2004, 430, 1012.
6
7
8
9
. E. R. Parnham and R. E. Morris, Acc. Chem. Res., 2007, 10, 1005.
. R. E. Morris, Chem. Commun., 2009, 2990.
. E. R. Parnham and R. E. Morris, J. Am. Chem. Soc., 2006, 128, 2204.
. H.Z. Xing, J.Y. Li, W.F. Yan, P. Chen, Z. Jin, J.H. Yu, S. Dai
andR.R.Xu, Chem. Mater., 2008, 20, 4179.
1
1
1
0.H. Z. Xing, W.T.Yang,T.Su,Y.Li,J.Xu, T.Nakano,J.H.Yu and R.R.Xu,
Angew. Chem. Int. Ed., 2010, 49, 2328.
1.T. Su, H.Z. Xing, J. Xu, J. H. Yu and R. R.Xu, Inorg. Chem.,2011, 50
,
1
073.
2.L. Liu, S. Ferdov, C. Coelho, K. Kong, L. Mafra, J. P. Li, J. X. Dong,
U. Kolitsch, R. S. Ferreira, E. Tillmanns, J. Rocha and Z. Lin,
Inorg.Chem., 2009, 48, 4598.
1
1
3.L. Liu, Z. F. Chen, H. B. Wei, Y. Li, Y.C. Fu, H. Xu, J. P. Li, M.Z.S.
Alexandra and J. X. Dong, Inorg. Chem., 2010, 49, 8270.
4.Y. Wei, Z.J. Tian, H. Gies, R.S. Xu, H.J. Ma, Pei, R.Y.; W. P. Zhang,
Y. P. Xu, L. Wang, K. D. Li, B.C. Wang, G. D.Wen and L.W.Lin,
Angew. Chem. Int. Ed., 2010, 49, 5367.
1
1
5.H. J. Ma, Z. J. Tian, R. S. Xu, B. C. Wang, Y. Wei, L. Wang, Y.P.
Xu, W. P. Zhang and L. W. Lin, J. Am. Chem. Soc., 2008, 130, 8120.
6.D.S.Wragg, P. J. Byrne, G. Giriat, B. L. Ouay, R. Gyepes, A.
Harrison, A. G. Whittaker and R. E. Morris,J. Phys. Chem.C, 2009,
113, 20553.
1
1
7.T. L. Greaves and C. J. Drummond, Chem. Rev., 2008,108,206.
8.B. Nuthakki, T. L. Greaves, I. Krodkiewska, A. Weerawardena, M. I.
Burgar, R. J. Mulder and C. J. Drummond, Aust. J. Chem., 2007, 60
1.
9.S.Y. Li, W. Wang, L. Liu and J.X. Dong, CrystEngComm.
013,15,6424.
,
2
1
2
2
2
,
2
0.G. M. Sheldrick, SHELXSꢀ97, Program for crystal structure solution;
University of Göttingen: Göttingen, 1997.
1.S. Oliver, A. Kuperman, A. Lough and G. A. Ozin, Inorg. Chem.
996, 35, 6373.
2.S. Oliver, A. Kuperman, A. Lough and G. A. Ozin,Chem. Mater.
996, , 2391.
,
1
,
1
8
2
2
2
3.E. R. Parnham and R. E. Morris, Chem. Mater., 2006, 18, 4882.
4.X. Zhang, S. J. Yao and Y. L. Guo,J. Mass Spectrom., 2008, 270, 31.
5.B. P. Callahan and R. Wolfenden, J. Am. Chem. Soc., 2003, 125, 310.
4
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DOI: 10.1039/C4DT03233K
Table 1 Crystal data and structure refinement for AlPOꢀPIL1 and AlPOꢀPIL2
Compounds
Chemical formula
Formula weight
Temperature (K)
Wavelength（Å）
Crystal system
Space group
a（Å）
AlPOꢀPIL1
AlPOꢀPIL2
[C H N ][Al(PO )(HPO )]
[C H N ][Al (OH) PO ) ]
5
16
2
4
4
5
16
2
2
2
4 2
322.13
298(2)
0.71073
382.11
298(2)
0.71073
Monoclinic
P2(1)/c
Monoclinic
C2/c
8.8966(8)
17.6602(16)
8.3738(9)
102.590(2)
1284.0(2)
4
15.5986(13)
9.6662(7)
10.0576(9)
100.048(2)
1493.2 (2)
4
b（Å）
c（Å）
β (°)
3
Volume (Å )
Z
ꢀ
3
ρcalc(mg. m )
1.666
1.700
−1
µ（mm ）
0.441
0.458
F(000)
672
792
Crystal size (mm)
θ range (°)
0.45×0.23×0.20
2.75 – 25.02
0.50×0. 38×0.37
2.65 – 25.02
Index ranges
ꢀ10≤ h ≤8, ꢀ21≤ k ≤16, ꢀ9≤ l ≤9 ꢀ18≤ h ≤18, ꢀ11≤ k ≤11, ꢀ11≤ l ≤7
Reflections collected
Independent reflections
Absorption correction
Refinement method
6321
3621
2258 [Rint = 0.0310]
'multiꢀscan'
1301 [Rint = 0.0464]
'multiꢀscan'
2
2
Fullꢀmatrix leastꢀsquares on F Fullꢀmatrix leastꢀsquareson F
2
Goodnessꢀofꢀfit onF
1.112
1.066
Final R indices [I>2δ(I )]
R indices (all data)
R = 0.0327, wR =0.0819
R = 0.0409, wR =0.1164
1
2
1
2
R = 0.0423, wR =0.0890
R = 0.0457, wR =0.1208
1 2
1
2
ꢀ
3
Largest diff. peakand hole [eꢁÅ ]0.257 and ꢀ0.338
CCDC number 974277
0.493 and ꢀ0.636
974278
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Figure captions
Figure 1.Thermal ellipsoid plot (50% probability) of a section of the structure of AlPOꢀPIL1 (a) and AlPOꢀPIL2 (b), showing the
atom labeling, the coordination about the independent Al and P atoms and the various organic templates
Figure 2.The structure of the AlPOꢀPIL1, [C5H16N2][Al(PO4)(HPO4)]. (a) projection along the a axis showing the chain and the
deprotonatedDMAPA between the chains; (b) a clear view of the chain structure built up from AlO4 and PO4 tetrahedra; (c)
projection along the c axis showing the polyhedral connectivity. (PO4/P: pink, AlO4/Al: turquoise, O: red, C: grey, N: blue,
H: white)
Figure 3.Projection of the structure of AlPOꢀPIL2, [C H N ][Al (OH) (PO ) ]: (a) view of the structure along b axis, showing the
5
16
2
2
2
4 2
inorganic layers intercalated by the diprotonated DMPDA cations. (b) an individual layer with 4.8.8 nets viewed along the
a axis, the O and H atoms are omitted for clarity.(c) the single chain with cornerꢀsharing Al2P2 fourꢀmembered rings. (PO4
/
P: pink, AlO4/Al: turquoise, O: red, C: grey, N: blue, H: white)
<
Figure 1>
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| J. Name., 2012, 00, 1-3
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<
Figure 2>
<
Figure 3>
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