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phosphite-oxalates
Accepted Manuscript Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates Zhen-Zhen Xue, Jie Pan, Jin-Hua Li, Zong-Hua Wang, Guo-Ming Wang PII:
S0022-2860(17)30259-4
DOI:
10.1016/j.molstruc.2017.02.102
Reference:
MOLSTR 23496
To appear in:
Journal of Molecular Structure
Received Date: 10 January 2017 Revised Date:
20 February 2017
Accepted Date: 28 February 2017
Please cite this article as: Z.-Z. Xue, J. Pan, J.-H. Li, Z.-H. Wang, G.-M. Wang, Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.02.102. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates
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Zhen-Zhen Xue, Jie Pan, Jin-Hua Li, Zong-Hua Wang and Guo-Ming Wang*
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Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates Zhen-Zhen Xue, Jie Pan, Jin-Hua Li, Zong-Hua Wang and Guo-Ming Wang* (College of Chemistry and Chemical Engineering, Collaborative Innovation Center for
Abstract Two
new
gallium
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E-mail address: [email protected] (G. -M. Wang)
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Marine Biomass Fiber Materials and Textiles, Qingdao University, Shandong 266071, China)
phosphate/phosphite-oxalates
(1)
solids, and
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{[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O}
hybrid
[H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2), where dmpip = 2,6-dimethyl-piperazine and apm = N-(3-aminopropyl)morpholine, have been synthesized and structurally characterized. Both of compounds 1 and 2 are formed by the connectivity of the Ga-based polyhedral, phosphite/phosphate groups as well as oxalate units. Compound
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1 possesses a two-dimensional layer structure, in which the C2O4 units via an in-plane linkage connect two Ga center within the sheet. While in 2, the C2O4 units serve as bis-bidentates
ligands
bridging
two
GaO6
octahedra
from
two
distinct
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gallium-phosphite chains to give rise to inorganic-organic hybrid layer with 8-membered rings. In these materials, the structure-directing amines reside in the
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interlayer region and interact with the layers by way of hydrogen-bonds.
Keywords: Gallium; Phosphate/phosphate; oxalates; Crystal structure; Hybrid material
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1. Introduction Microporous materials continue to be the subject of intense research in the fields of materials science and crystal engineering, owing not only to their diverse structural chemistry but also to their potential applications for magnetism, fluorescence,
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electronics, gas absorption, ion exchange, heterogeneous catalysis, and so on [1-6]. Since the pioneering work reporting the crystalline aluminophosphate molecular sieves in 1982, a huge number of metal phosphates and phosphites with a variety of rich compositional and structural features have been reported in the literature [7-10].
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Among them the gallium-phosphates/phosphites are an important family, and huge number of such solids with zero-(monomer), one-(chain, ladder), two-(layer), and
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three-dimensional (3D) architectures have been synthesized and successfully characterized [11-15]. Compared to aluminum, the larger size of gallium may give rise to variable coordination geometry (GaO4 tetrahedra, GaO5 trigonal bipyramids, and GaO6 octahedra) for the metal centre. The geometrical feature induced the formation of inorganic networks exhibiting a rich structural diversity, including the
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production of large pore system. Typical examples include gallium phosphate [Ga2(DETA)(PO4)2]·2H2O (NTHU-1, DETA = diethylenetriamine) and gallium phosphite
(H5TEPA)1.2[(GaOH)9(HPO3)12]·xH2O
(NTHU-15,
TEPA
=
[16-17].
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tetraethylenepentamine) possessing extra-large 24- and 18-ring channels, respectively
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Recent developments in the area of hybrid open-frameworks have placed special emphasis on the introduction of rigid organic linkers. For instance, the oxalates, as part of the inorganic framework has opened up tremendous possibilities for research in this area giving rise to new inorganic-organic hybrid materials. The use of oxalate anions along with phosphates or phosphites has been successfully accomplished, and phosphate/phosphite-oxalate structures are beginning to emerge as an important family
[18-20].
Similar
to
other
known
microporous
materials,
the
phosphate/phosphite-oxalate structures appear to show structural diversity and porous nature since the different coordination modes of MOx polyhedra, PO4 units, HPO3
ACCEPTED MANUSCRIPT pseudo-tetrahedra and oxalate groups [21-24]. During the last couple of years, a variety of crystalline metal (Al, Zn, Fe, Mn, In, Co, Sn, etc.) phosphate-oxalates and phosphite-oxalates have been prepared since the first organically templated vanadyl arsenato- and phosphato-oxalates were obtained [25-29]. For example, the 3D
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structures of [H3N(CH2)3NH3][Mn2(HPO4)2(C2O4)(H2O)2] is constructed from manganese phosphate layers bridged by oxalate groups [30]; the 3D open-framework indium phosphite-oxalates [C6H14N2][In2(HPO3)3(C2O4)] is constructed from InO6 octahedra, HPO3 and C2O4 units, containing 12-members ring channels [31]. However,
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the reports on organically template gallium-based phosphate/ phosphite-oxalates are relatively rare, which may be due to the difficulties in preparing high quality
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single-crystals for the X-ray structural analysis [32-33]. It is worth noting that rational design and fabrication of gallium-based phosphate/ phosphite-oxalates are influenced by many factors such as synthetic methods, reaction conditions, metal/ligands ratio, organic templates, solvents, pH, temperature, etc. Moreover, in the earlier literature studies on open-frameworks, several compounds exhibiting different structures are
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also synthesized with the same template under different reaction conditions [34-35]. With the aim of searching novel organically template gallium-based phosphate/phosphite-oxalates, we conducted our study on the hydrothermal synthesis phosphate/phosphite-oxalates-amine
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in
phosphate/phosphite-oxalates
systems.
compounds
gallium, (1)
two
new namely, and
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{[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O}
of
Presently,
[H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2) have been successfully prepared by employing 2,6-dimethyl-pyrazine and N-(3-aminopropyl)morpholine as organic templates, respectively. In this paper, we report the syntheses, structures and characterization studies of the above compounds.
2. Experimental section 2.1 Materials and general methods All chemicals purchased commercially were used as received without further purification. Infrared spectra were recorded in the range of 400-4000 cm−1 on an ABB
ACCEPTED MANUSCRIPT Bomen MB 102 series FT-IR spectrophotometer using KBr pellets. Elemental analyses of carbon, hydrogen and nitrogen atoms were performed using an Elemental Vario EL III instrument. Powder X-ray diffraction (PXRD) measurements for 1 and 2 were recorded on a Philips X’Pert-MPD diffractometer with Cu-Kα1 radiation (λ =
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1.54076 Å). Thermogravimetric analyses were carried out in the temperature range of 30-800 °C with a heating rate of 10 °C min−1 using a Mettler Toledo TGA/SDTA 851e analyzer.
2.2 Synthesis of {[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O} (1) A mixture of
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Ga2O3, H3PO4, 2,6-dimethyl-piperazine, oxalic acid, H2O and methanol with a molar composition of 0.74: 4.6: 3.5: 1: 222: 25 was sealed in a Teflon-lined autoclave and
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heated at 160°C for 8 days. Anal. calcd for C7H20Ga2N2O15P3 (fw 604.61): C, 13.91%; H, 3.33%; N, 4.63%. Found: C, 13.86%; H, 3.51%; N, 4.71%. IR (KBr, cm 1): −
3458(m), 2959(w), 1631(m), 1562(s), 1430(m), 1333(m), 1131(w), 965(w), 784(w), 715(w) (Fig. S1).
Synthesis of [H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2) Compound 2 was prepared
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using the same procedure as described for 1. The mixture of Ga2O3, H3PO3, N-(3-aminopropyl)morpholine, oxalic acid and H2O with a molar composition of 0.6: 6: 2.5: 4: 11 was heated at 160°C for 5 days. Anal. calcd for C9H24Ga2N2O17P4 (fw 695.63): C, 15.54%; H, 3.48%; N, 4.03%. Found: C, 15.48%; H, 3.41%; N, 4.11%. IR −
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(KBr, cm 1): 3432(m), 3162(w), 2412(m), 1695(s), 1616(w), 1481(w), 1382(w),
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1123(s), 1011(w), 899(w).
2.3 X-Ray crystallography The data for compounds 1 and 2 were collected using a Rigaku XtaLAB mini CCD diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. The structures were resolved by direct methods and refined by full-matrix least-squares fitting on F2 by SHELX-97 [36]. All non-hydrogen atoms were refined with anisotropic thermal parameters. The positions of hydrogen atoms on the organic amine were generated geometrically and refined using a riding model. C5 and C6 atoms of H2apm cation in compound 2 were disordered and were refined using it split over two sites with a total occupancy of 1. Crystallographic data and structure
ACCEPTED MANUSCRIPT refinement parameters for 1 and 2 are summarized in Table 1. Selected bond lengths and angles are collated in Table S1. CCDC 1501026 and 1501027 contain the supplementary crystallographic data for this paper.
3. Results and discussion
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3.1 Crystal structure of {[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O} (1). X-ray diffraction analysis reveals that compound 1 crystallizes in the monoclinic system with P21/c space group. The asymmetric unit of compound 1 consists of 29 nonhydrogen atoms, including two gallium atoms, three phosphorus atoms, fifteen
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oxygen atoms, seven carbon atoms and two nitrogen atoms. There are two different types of gallium in the structure. As shown in Fig. 1, the Ga(1) atom is
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six-coordinated by oxygen atoms from one oxalate ligand, one PO4 group as well as two individual HPO4 units, displaying a slightly distorted GaO6 octahedral geometry (Ga-O = 1.912(4)-2.066(4) Å). The remaining Ga(2) center is four-coordinated by oxygen atoms from two PO43- anions and two HPO42- anions, displaying typical GaO4 tetrahedral coordination with distance of Ga-O ranging from 1.811(4) to 1.832(3) Å.
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All phosphorus atoms adopt tetrahedral coordination geometry: P(1) forms four P-O-Ga linkages; P(2) forms only one P-O-Ga linkage and possess one terminal OH group and two terminal O atoms; P(3) produces three P-O-Ga bonds keeping one
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terminal OH group. The P-O distances are in the range of 1.505(4)-1.570(4) Å, and the O-P-O bond angles are in the scope of 103.9-115.7°.
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The alternative linkage of GaOx (x = 4, 6) and PO4 tetrahedral groups forms typical four-membered ring (4MR), which is further connected with each other to form 1D chains along the a axis (Fig. 2a). These chains are further held together via corner sharing of the phosphate tetrahedra, to generate gallium-phosphate puckered layer structure with 8-membered rings (Fig. 2b). It is obvious that the uncoordinated P-O and P-OH linkages of HP(2)O4 units point into the interlayer space, preventing the linkage between the neighbouring layers into a higher dimensional architecture. In addition, oxalate units via an in-plane linkage coordinate to Ga(1) and Ga(2) atoms, filling in the {P(1)O4-Ga(2)O4-HP(3)O4-Ga(1)O6}2 8-memberd windows to produce
ACCEPTED MANUSCRIPT the final hybrid layer (Fig. 2c). For the common 3D metal phosphate-oxalates, oxalates connect layers by participating in the coordination of metal atoms belong to the adjacent sheets [37]. While for 1, each oxygen atom belongs to the oxalate ligand has been coordinated to the Ga atom within the same sheet, it cannot expand to 3D
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structure. According to the literature, there are at least four topological analogues of compound 1 [32, 38-40]. Though using different organic templates, the phosphate anion in 1 shows the same coordination behavior with above mentioned four compounds, which may be due to the same coordination number of gallium atoms.
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The diprotonated H2dmpip2+ cations locate in the interlayer region and balance the overall negative electrostatic charge of the [Ga2(HPO4)2(PO4)(C2O4)0.5] layers.
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Moreover, these organic templates interact with the layers through multiple H-bonds with N-H···O distance in the range of 2.702(6)-3.222(6) Å. The adjacent phosphate-oxalate layers are stacked along the [100] direction in an -ABAB- fashion, and further connected with each other through strong H-bonding interactions to give 3D supramolecular framework (Fig. 2d). The details of hydrogen bonds are given in
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Table S2. A void space analysis using the program PLATON indicates that these extra-framework organic cations and lattice water molecules occupy 48.1% of the unit cell volume [41].
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Crystal structure of [H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2). Compound 2 crystallizes in the orthorhombic system with Pbcm space group. There are one crystallographically distinct gallium atom, two halves of H2PO3 units, one HPO3
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group, one half oxalate ligand and one half H2apm cation in the asymmetric unit. As depicted in Fig.3a, the Ga(1) atom adopts six-coordinated geometry to construct an octahedron from six surrounding oxygen atoms. Each shares four bridging oxygen atoms (O(1), O(3), O(5) and O(7)) with the adjacent phosphorus atoms with an average Ga-O bond length of 1.969 Å and Ga-O-P bond angles in the range of 133.1-143.2°. The remaining two coordination sites are occupied by the oxalate anion (O(8) and O(9)) which acts as a bis-bidentate ligand between two GaO6 octahedra. The slight distortion for GaO6 octahedra is due to the attached oxalate anions, as indicated by the Ga-O bond lengths ranging from 1.909(5)-2.059(5) Å as well as the
ACCEPTED MANUSCRIPT small O-Ga-O bond angles (80.8-178.4°), similar to distortions observed in other metal phosphite-oxalates [23, 31]. The coordination environment around all phosphorus atoms is pseudo-tetrahedra. Each of them makes two P-O-Ga linkages and possesses one terminal P-O bond and one P-H bond. The longest P(1)-O(2) and
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P(2)-O(4) bonds correspond to the terminal P-OH linkages with the distances of 1.525(6) Å and 1.539(8) Å, respectively. The existence of P-H bonds is also confirmed by the characteristic band of phosphite anions (νH-P = 2412 cm-1) in the IR spectrum. The P-O distances are in the range 1.496(5)-1.539(8) Å, and the O-P-O
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bond angles are in the range 107.6-114.6°.
The strictly alternating GaO6 octahedra and P-centered pseudo-tetrahedra form
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typical four- and eight-membered apertures, which are linked through their corners forming the neutral one-dimensional ladder-like chains (Fig. 3b). As shown in Fig. 3c, the metal-phosphite inorganic chains are, in turn, connected via an oxalate bridge which links the Ga centers from two different chains to give rise to a two-dimensional hybrid layer architecture with the formula [Ga2(H2PO3)2(HPO3)2(C2O4)]. Charge
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neutrality is achieved by the incorporation of the amine molecule in its diprotonated form; there is one half [H2apm]2+ ion per framework formula unit. The protonated apm molecules are involved hydrogen bonding through non-coordinated N(2) atoms
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with the bridging oxygen atoms (O(1), O(3) and O(5)) in the negative layer. Moreover, the overall 3D supermolecule is formed by week van der Waals interactions between the layers and attached [H2apm]2+ cations (Fig. 3d). A void space analysis performed
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by the program PLATON indicates that these extra-framework species occupy 41.0% of the unit cell volume.
In the materials of phosphate/phosphite-oxalates reported, the oxalates ligand
normally plays two roles, that is, one as an integral part with the metalphosphate/phosphite to form hybrid layers and the other as the pillars to link the inorganic ladders to form hybrid layers [42]. In the present structures, compound 2 represents the pillar-based hybrid layers, while compound 1 represents the former. Compared with compound 1, the difference is that oxalate anions act as bis-bidentate ligands to the adjacent GaO6 units which belongs two distinct inorganic chains in 2.
ACCEPTED MANUSCRIPT 3.2 XRD Patterns and Thermal Analyses To confirm the phase purity of these compounds, the PXRD patterns were recorded for 1 and 2, and they were comparable to the corresponding simulated patterns calculated from the single-crystal diffraction data (Fig. 4), indicating a pure
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phase of each bulky sample. Thermal gravimetric analyses were carried out to examine the thermal stabilities of compounds 1 and 2. For compound 1, two-step weight-loss processes are present from room temperature to 800 °C. As shown in Fig.5, the weight loss before 155 °C is
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caused by release of one lattice water molecule (found: 3.11%; calcd: 2.98%). The weight variation in the temperature range of 155-460 °C is attributed to the release of
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organic molecule in the product (found: 19.26%; calcd: 19.22%). The remaining residue for the sample is amorphous, and its phase is unidentified. For compound 2, the structure remains stable up to 240 °C, and then undergoes a weight loss of 20.11% in the temperature range of 240-312 °C which corresponding to the release of organic molecule (calcd: 20.73%). Upon further heating, the whole structure then starts to
4. Conclusion In
summary,
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collapse.
two
new
organic
template-directed
gallium
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phosphate/phosphite-oxalates hybrid materials have been hydrothermally synthesized using 2,6-dimethyl-piperazine and N-(3-aminopropyl)morpholine as the SDAs.
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Compound 1 is comprised of gallium phosphate-oxalate hybrid layers with 4,8-MRs that are stacked in ABAB fashion. Compound 2 is formed by the edge-shared GaO6 and HPO3 polyhedra forming a gallium-phosphite chain, that are connected with the oxalate units generating two-dimensional layer architecture. In 1 and 2, the oxalate units have a dual functionality of connecting within the plane of the layer as well as linking the inorganic ladders as pillars. The hydrogen bonding interactions between host-guest molecules stabilize the placement of the organic ammonium cations in the interlayer region. Our investigation suggests that it is possible to make new members of the gallium phosphate/phosphite-oxalates system by suitable choice of other novel
ACCEPTED MANUSCRIPT templates. These materials will be potentially useful in adsorption and separation if the open framework does not collapse when the templates are removed or exchanged. Work on this theme is currently in progress. Acknowledgments
and
21601100),
the
Natural
Science
Foundation
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This work was supported by the Natural Science Foundation of China (21571111 of
(ZR2016BP02), and Taishan Scholar Program (ts201511027). References
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ACCEPTED MANUSCRIPT Table 1 Crystal data and structure refinements for compounds 1 and 2. Compounds
1
2
C7H20Ga2N2O15P3
C9H24Ga2N2O17P4
Formula weight
604.61
695.63
Temperature (K)
293 (2)
293 (2)
Crystal system
monoclinic
orthorhombic
Space group
P21/c
Pbcm
a [Å]
8.9044(18)
8.5689(17)
b [Å]
28.036(6)
20.245(4)
c [Å]
8.1727(16)
12.604(3)
α [o]
90.00
β [o]
100.74(3)
V [Å ] Z 3
Dc [g/cm ]
90.00
90.00
90.00
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90.00 3
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γ [o]
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Empirical formula
2004.5(7)
2186.5(8)
4
4
1.997
2.113
µ [mm ]
3.003
2.845
F(000)
1204
1400
θ range ( ° )
3.1-27.6
3.0-27.6
16880
17985
4559
2018
1.093
1.065
264
170
0.0710
0.0890
0.2048
0.3420
Collected reflections Unique reflections 2
Parameters a
R1( I >2σ( I))
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GOF on F
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wR2( I >2σ(I ))b a
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-1
R1 = Σ||Fo| - |Fc||/Σ|Fo|. b wR2 = [Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2.
ACCEPTED MANUSCRIPT Figure captions: Fig. 1 View of the coordination of the gallium and phosphorus atoms in 1, showing the atom-labeling scheme and 50% thermal ellipsoids. Fig. 2 (a) view of the inorganic Ga-O-P chain in 1 along the [010] direction; (b) View
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of the gallium-phosphate inorganic layer with 8-ring windows parallel to the ac plane; (c) oxalate units fill in the 8-MR; (d) view of the structure along the [100] direction showing the hybrid layers intercalated with organic cations.
Fig. 3 (a) The coordination environment of the gallium and phosphorus atoms in 2; (b)
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the ladder-like gallium phosphite substructure; (c) view of the layered structure with gallium phosphite ladders bridged by oxalate ligands; (d) interlayer A–A–A packing
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model. Fig. 4 PXRD patterns of compounds 1 and 2.
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Fig. 5 TGA carves of compounds 1 and 2.
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Figure 5
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Highlights (1) Two new gallium phosphate/phosphite-oxalates have been synthesized. (2) Different organic templates are used in the syntheses of 1-2.
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(3) Distinct types of two-dimensional layer structure are formed.
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(4) The oxalate ligands play two roles in the construction of 1-2.
S0022-2860(17)30259-4
DOI:
10.1016/j.molstruc.2017.02.102
Reference:
MOLSTR 23496
To appear in:
Journal of Molecular Structure
Received Date: 10 January 2017 Revised Date:
20 February 2017
Accepted Date: 28 February 2017
Please cite this article as: Z.-Z. Xue, J. Pan, J.-H. Li, Z.-H. Wang, G.-M. Wang, Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates, Journal of Molecular Structure (2017), doi: 10.1016/j.molstruc.2017.02.102. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates
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Zhen-Zhen Xue, Jie Pan, Jin-Hua Li, Zong-Hua Wang and Guo-Ming Wang*
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Synthesis, structure and characterization of two new organic template-directed gallium phosphate/phosphite-oxalates Zhen-Zhen Xue, Jie Pan, Jin-Hua Li, Zong-Hua Wang and Guo-Ming Wang* (College of Chemistry and Chemical Engineering, Collaborative Innovation Center for
Abstract Two
new
gallium
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E-mail address: [email protected] (G. -M. Wang)
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Marine Biomass Fiber Materials and Textiles, Qingdao University, Shandong 266071, China)
phosphate/phosphite-oxalates
(1)
solids, and
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{[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O}
hybrid
[H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2), where dmpip = 2,6-dimethyl-piperazine and apm = N-(3-aminopropyl)morpholine, have been synthesized and structurally characterized. Both of compounds 1 and 2 are formed by the connectivity of the Ga-based polyhedral, phosphite/phosphate groups as well as oxalate units. Compound
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1 possesses a two-dimensional layer structure, in which the C2O4 units via an in-plane linkage connect two Ga center within the sheet. While in 2, the C2O4 units serve as bis-bidentates
ligands
bridging
two
GaO6
octahedra
from
two
distinct
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gallium-phosphite chains to give rise to inorganic-organic hybrid layer with 8-membered rings. In these materials, the structure-directing amines reside in the
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interlayer region and interact with the layers by way of hydrogen-bonds.
Keywords: Gallium; Phosphate/phosphate; oxalates; Crystal structure; Hybrid material
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1. Introduction Microporous materials continue to be the subject of intense research in the fields of materials science and crystal engineering, owing not only to their diverse structural chemistry but also to their potential applications for magnetism, fluorescence,
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electronics, gas absorption, ion exchange, heterogeneous catalysis, and so on [1-6]. Since the pioneering work reporting the crystalline aluminophosphate molecular sieves in 1982, a huge number of metal phosphates and phosphites with a variety of rich compositional and structural features have been reported in the literature [7-10].
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Among them the gallium-phosphates/phosphites are an important family, and huge number of such solids with zero-(monomer), one-(chain, ladder), two-(layer), and
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three-dimensional (3D) architectures have been synthesized and successfully characterized [11-15]. Compared to aluminum, the larger size of gallium may give rise to variable coordination geometry (GaO4 tetrahedra, GaO5 trigonal bipyramids, and GaO6 octahedra) for the metal centre. The geometrical feature induced the formation of inorganic networks exhibiting a rich structural diversity, including the
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production of large pore system. Typical examples include gallium phosphate [Ga2(DETA)(PO4)2]·2H2O (NTHU-1, DETA = diethylenetriamine) and gallium phosphite
(H5TEPA)1.2[(GaOH)9(HPO3)12]·xH2O
(NTHU-15,
TEPA
=
[16-17].
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tetraethylenepentamine) possessing extra-large 24- and 18-ring channels, respectively
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Recent developments in the area of hybrid open-frameworks have placed special emphasis on the introduction of rigid organic linkers. For instance, the oxalates, as part of the inorganic framework has opened up tremendous possibilities for research in this area giving rise to new inorganic-organic hybrid materials. The use of oxalate anions along with phosphates or phosphites has been successfully accomplished, and phosphate/phosphite-oxalate structures are beginning to emerge as an important family
[18-20].
Similar
to
other
known
microporous
materials,
the
phosphate/phosphite-oxalate structures appear to show structural diversity and porous nature since the different coordination modes of MOx polyhedra, PO4 units, HPO3
ACCEPTED MANUSCRIPT pseudo-tetrahedra and oxalate groups [21-24]. During the last couple of years, a variety of crystalline metal (Al, Zn, Fe, Mn, In, Co, Sn, etc.) phosphate-oxalates and phosphite-oxalates have been prepared since the first organically templated vanadyl arsenato- and phosphato-oxalates were obtained [25-29]. For example, the 3D
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structures of [H3N(CH2)3NH3][Mn2(HPO4)2(C2O4)(H2O)2] is constructed from manganese phosphate layers bridged by oxalate groups [30]; the 3D open-framework indium phosphite-oxalates [C6H14N2][In2(HPO3)3(C2O4)] is constructed from InO6 octahedra, HPO3 and C2O4 units, containing 12-members ring channels [31]. However,
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the reports on organically template gallium-based phosphate/ phosphite-oxalates are relatively rare, which may be due to the difficulties in preparing high quality
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single-crystals for the X-ray structural analysis [32-33]. It is worth noting that rational design and fabrication of gallium-based phosphate/ phosphite-oxalates are influenced by many factors such as synthetic methods, reaction conditions, metal/ligands ratio, organic templates, solvents, pH, temperature, etc. Moreover, in the earlier literature studies on open-frameworks, several compounds exhibiting different structures are
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also synthesized with the same template under different reaction conditions [34-35]. With the aim of searching novel organically template gallium-based phosphate/phosphite-oxalates, we conducted our study on the hydrothermal synthesis phosphate/phosphite-oxalates-amine
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in
phosphate/phosphite-oxalates
systems.
compounds
gallium, (1)
two
new namely, and
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{[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O}
of
Presently,
[H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2) have been successfully prepared by employing 2,6-dimethyl-pyrazine and N-(3-aminopropyl)morpholine as organic templates, respectively. In this paper, we report the syntheses, structures and characterization studies of the above compounds.
2. Experimental section 2.1 Materials and general methods All chemicals purchased commercially were used as received without further purification. Infrared spectra were recorded in the range of 400-4000 cm−1 on an ABB
ACCEPTED MANUSCRIPT Bomen MB 102 series FT-IR spectrophotometer using KBr pellets. Elemental analyses of carbon, hydrogen and nitrogen atoms were performed using an Elemental Vario EL III instrument. Powder X-ray diffraction (PXRD) measurements for 1 and 2 were recorded on a Philips X’Pert-MPD diffractometer with Cu-Kα1 radiation (λ =
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1.54076 Å). Thermogravimetric analyses were carried out in the temperature range of 30-800 °C with a heating rate of 10 °C min−1 using a Mettler Toledo TGA/SDTA 851e analyzer.
2.2 Synthesis of {[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O} (1) A mixture of
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Ga2O3, H3PO4, 2,6-dimethyl-piperazine, oxalic acid, H2O and methanol with a molar composition of 0.74: 4.6: 3.5: 1: 222: 25 was sealed in a Teflon-lined autoclave and
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heated at 160°C for 8 days. Anal. calcd for C7H20Ga2N2O15P3 (fw 604.61): C, 13.91%; H, 3.33%; N, 4.63%. Found: C, 13.86%; H, 3.51%; N, 4.71%. IR (KBr, cm 1): −
3458(m), 2959(w), 1631(m), 1562(s), 1430(m), 1333(m), 1131(w), 965(w), 784(w), 715(w) (Fig. S1).
Synthesis of [H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2) Compound 2 was prepared
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using the same procedure as described for 1. The mixture of Ga2O3, H3PO3, N-(3-aminopropyl)morpholine, oxalic acid and H2O with a molar composition of 0.6: 6: 2.5: 4: 11 was heated at 160°C for 5 days. Anal. calcd for C9H24Ga2N2O17P4 (fw 695.63): C, 15.54%; H, 3.48%; N, 4.03%. Found: C, 15.48%; H, 3.41%; N, 4.11%. IR −
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(KBr, cm 1): 3432(m), 3162(w), 2412(m), 1695(s), 1616(w), 1481(w), 1382(w),
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1123(s), 1011(w), 899(w).
2.3 X-Ray crystallography The data for compounds 1 and 2 were collected using a Rigaku XtaLAB mini CCD diffractometer equipped with graphite-monochromated Mo Kα radiation (λ = 0.71073 Å) at room temperature. The structures were resolved by direct methods and refined by full-matrix least-squares fitting on F2 by SHELX-97 [36]. All non-hydrogen atoms were refined with anisotropic thermal parameters. The positions of hydrogen atoms on the organic amine were generated geometrically and refined using a riding model. C5 and C6 atoms of H2apm cation in compound 2 were disordered and were refined using it split over two sites with a total occupancy of 1. Crystallographic data and structure
ACCEPTED MANUSCRIPT refinement parameters for 1 and 2 are summarized in Table 1. Selected bond lengths and angles are collated in Table S1. CCDC 1501026 and 1501027 contain the supplementary crystallographic data for this paper.
3. Results and discussion
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3.1 Crystal structure of {[H2dmpip][Ga2(HPO4)2(PO4)(C2O4)0.5]·H2O} (1). X-ray diffraction analysis reveals that compound 1 crystallizes in the monoclinic system with P21/c space group. The asymmetric unit of compound 1 consists of 29 nonhydrogen atoms, including two gallium atoms, three phosphorus atoms, fifteen
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oxygen atoms, seven carbon atoms and two nitrogen atoms. There are two different types of gallium in the structure. As shown in Fig. 1, the Ga(1) atom is
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six-coordinated by oxygen atoms from one oxalate ligand, one PO4 group as well as two individual HPO4 units, displaying a slightly distorted GaO6 octahedral geometry (Ga-O = 1.912(4)-2.066(4) Å). The remaining Ga(2) center is four-coordinated by oxygen atoms from two PO43- anions and two HPO42- anions, displaying typical GaO4 tetrahedral coordination with distance of Ga-O ranging from 1.811(4) to 1.832(3) Å.
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All phosphorus atoms adopt tetrahedral coordination geometry: P(1) forms four P-O-Ga linkages; P(2) forms only one P-O-Ga linkage and possess one terminal OH group and two terminal O atoms; P(3) produces three P-O-Ga bonds keeping one
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terminal OH group. The P-O distances are in the range of 1.505(4)-1.570(4) Å, and the O-P-O bond angles are in the scope of 103.9-115.7°.
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The alternative linkage of GaOx (x = 4, 6) and PO4 tetrahedral groups forms typical four-membered ring (4MR), which is further connected with each other to form 1D chains along the a axis (Fig. 2a). These chains are further held together via corner sharing of the phosphate tetrahedra, to generate gallium-phosphate puckered layer structure with 8-membered rings (Fig. 2b). It is obvious that the uncoordinated P-O and P-OH linkages of HP(2)O4 units point into the interlayer space, preventing the linkage between the neighbouring layers into a higher dimensional architecture. In addition, oxalate units via an in-plane linkage coordinate to Ga(1) and Ga(2) atoms, filling in the {P(1)O4-Ga(2)O4-HP(3)O4-Ga(1)O6}2 8-memberd windows to produce
ACCEPTED MANUSCRIPT the final hybrid layer (Fig. 2c). For the common 3D metal phosphate-oxalates, oxalates connect layers by participating in the coordination of metal atoms belong to the adjacent sheets [37]. While for 1, each oxygen atom belongs to the oxalate ligand has been coordinated to the Ga atom within the same sheet, it cannot expand to 3D
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structure. According to the literature, there are at least four topological analogues of compound 1 [32, 38-40]. Though using different organic templates, the phosphate anion in 1 shows the same coordination behavior with above mentioned four compounds, which may be due to the same coordination number of gallium atoms.
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The diprotonated H2dmpip2+ cations locate in the interlayer region and balance the overall negative electrostatic charge of the [Ga2(HPO4)2(PO4)(C2O4)0.5] layers.
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Moreover, these organic templates interact with the layers through multiple H-bonds with N-H···O distance in the range of 2.702(6)-3.222(6) Å. The adjacent phosphate-oxalate layers are stacked along the [100] direction in an -ABAB- fashion, and further connected with each other through strong H-bonding interactions to give 3D supramolecular framework (Fig. 2d). The details of hydrogen bonds are given in
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Table S2. A void space analysis using the program PLATON indicates that these extra-framework organic cations and lattice water molecules occupy 48.1% of the unit cell volume [41].
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Crystal structure of [H2apm][Ga2(H2PO3)2(HPO3)2(C2O4)] (2). Compound 2 crystallizes in the orthorhombic system with Pbcm space group. There are one crystallographically distinct gallium atom, two halves of H2PO3 units, one HPO3
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group, one half oxalate ligand and one half H2apm cation in the asymmetric unit. As depicted in Fig.3a, the Ga(1) atom adopts six-coordinated geometry to construct an octahedron from six surrounding oxygen atoms. Each shares four bridging oxygen atoms (O(1), O(3), O(5) and O(7)) with the adjacent phosphorus atoms with an average Ga-O bond length of 1.969 Å and Ga-O-P bond angles in the range of 133.1-143.2°. The remaining two coordination sites are occupied by the oxalate anion (O(8) and O(9)) which acts as a bis-bidentate ligand between two GaO6 octahedra. The slight distortion for GaO6 octahedra is due to the attached oxalate anions, as indicated by the Ga-O bond lengths ranging from 1.909(5)-2.059(5) Å as well as the
ACCEPTED MANUSCRIPT small O-Ga-O bond angles (80.8-178.4°), similar to distortions observed in other metal phosphite-oxalates [23, 31]. The coordination environment around all phosphorus atoms is pseudo-tetrahedra. Each of them makes two P-O-Ga linkages and possesses one terminal P-O bond and one P-H bond. The longest P(1)-O(2) and
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P(2)-O(4) bonds correspond to the terminal P-OH linkages with the distances of 1.525(6) Å and 1.539(8) Å, respectively. The existence of P-H bonds is also confirmed by the characteristic band of phosphite anions (νH-P = 2412 cm-1) in the IR spectrum. The P-O distances are in the range 1.496(5)-1.539(8) Å, and the O-P-O
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bond angles are in the range 107.6-114.6°.
The strictly alternating GaO6 octahedra and P-centered pseudo-tetrahedra form
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typical four- and eight-membered apertures, which are linked through their corners forming the neutral one-dimensional ladder-like chains (Fig. 3b). As shown in Fig. 3c, the metal-phosphite inorganic chains are, in turn, connected via an oxalate bridge which links the Ga centers from two different chains to give rise to a two-dimensional hybrid layer architecture with the formula [Ga2(H2PO3)2(HPO3)2(C2O4)]. Charge
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neutrality is achieved by the incorporation of the amine molecule in its diprotonated form; there is one half [H2apm]2+ ion per framework formula unit. The protonated apm molecules are involved hydrogen bonding through non-coordinated N(2) atoms
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with the bridging oxygen atoms (O(1), O(3) and O(5)) in the negative layer. Moreover, the overall 3D supermolecule is formed by week van der Waals interactions between the layers and attached [H2apm]2+ cations (Fig. 3d). A void space analysis performed
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by the program PLATON indicates that these extra-framework species occupy 41.0% of the unit cell volume.
In the materials of phosphate/phosphite-oxalates reported, the oxalates ligand
normally plays two roles, that is, one as an integral part with the metalphosphate/phosphite to form hybrid layers and the other as the pillars to link the inorganic ladders to form hybrid layers [42]. In the present structures, compound 2 represents the pillar-based hybrid layers, while compound 1 represents the former. Compared with compound 1, the difference is that oxalate anions act as bis-bidentate ligands to the adjacent GaO6 units which belongs two distinct inorganic chains in 2.
ACCEPTED MANUSCRIPT 3.2 XRD Patterns and Thermal Analyses To confirm the phase purity of these compounds, the PXRD patterns were recorded for 1 and 2, and they were comparable to the corresponding simulated patterns calculated from the single-crystal diffraction data (Fig. 4), indicating a pure
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phase of each bulky sample. Thermal gravimetric analyses were carried out to examine the thermal stabilities of compounds 1 and 2. For compound 1, two-step weight-loss processes are present from room temperature to 800 °C. As shown in Fig.5, the weight loss before 155 °C is
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caused by release of one lattice water molecule (found: 3.11%; calcd: 2.98%). The weight variation in the temperature range of 155-460 °C is attributed to the release of
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organic molecule in the product (found: 19.26%; calcd: 19.22%). The remaining residue for the sample is amorphous, and its phase is unidentified. For compound 2, the structure remains stable up to 240 °C, and then undergoes a weight loss of 20.11% in the temperature range of 240-312 °C which corresponding to the release of organic molecule (calcd: 20.73%). Upon further heating, the whole structure then starts to
4. Conclusion In
summary,
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collapse.
two
new
organic
template-directed
gallium
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phosphate/phosphite-oxalates hybrid materials have been hydrothermally synthesized using 2,6-dimethyl-piperazine and N-(3-aminopropyl)morpholine as the SDAs.
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Compound 1 is comprised of gallium phosphate-oxalate hybrid layers with 4,8-MRs that are stacked in ABAB fashion. Compound 2 is formed by the edge-shared GaO6 and HPO3 polyhedra forming a gallium-phosphite chain, that are connected with the oxalate units generating two-dimensional layer architecture. In 1 and 2, the oxalate units have a dual functionality of connecting within the plane of the layer as well as linking the inorganic ladders as pillars. The hydrogen bonding interactions between host-guest molecules stabilize the placement of the organic ammonium cations in the interlayer region. Our investigation suggests that it is possible to make new members of the gallium phosphate/phosphite-oxalates system by suitable choice of other novel
ACCEPTED MANUSCRIPT templates. These materials will be potentially useful in adsorption and separation if the open framework does not collapse when the templates are removed or exchanged. Work on this theme is currently in progress. Acknowledgments
and
21601100),
the
Natural
Science
Foundation
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This work was supported by the Natural Science Foundation of China (21571111 of
(ZR2016BP02), and Taishan Scholar Program (ts201511027). References
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ACCEPTED MANUSCRIPT Table 1 Crystal data and structure refinements for compounds 1 and 2. Compounds
1
2
C7H20Ga2N2O15P3
C9H24Ga2N2O17P4
Formula weight
604.61
695.63
Temperature (K)
293 (2)
293 (2)
Crystal system
monoclinic
orthorhombic
Space group
P21/c
Pbcm
a [Å]
8.9044(18)
8.5689(17)
b [Å]
28.036(6)
20.245(4)
c [Å]
8.1727(16)
12.604(3)
α [o]
90.00
β [o]
100.74(3)
V [Å ] Z 3
Dc [g/cm ]
90.00
90.00
90.00
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90.00 3
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γ [o]
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Empirical formula
2004.5(7)
2186.5(8)
4
4
1.997
2.113
µ [mm ]
3.003
2.845
F(000)
1204
1400
θ range ( ° )
3.1-27.6
3.0-27.6
16880
17985
4559
2018
1.093
1.065
264
170
0.0710
0.0890
0.2048
0.3420
Collected reflections Unique reflections 2
Parameters a
R1( I >2σ( I))
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GOF on F
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wR2( I >2σ(I ))b a
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-1
R1 = Σ||Fo| - |Fc||/Σ|Fo|. b wR2 = [Σw(Fo2 - Fc2)2/Σw(Fo2)2]1/2.
ACCEPTED MANUSCRIPT Figure captions: Fig. 1 View of the coordination of the gallium and phosphorus atoms in 1, showing the atom-labeling scheme and 50% thermal ellipsoids. Fig. 2 (a) view of the inorganic Ga-O-P chain in 1 along the [010] direction; (b) View
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of the gallium-phosphate inorganic layer with 8-ring windows parallel to the ac plane; (c) oxalate units fill in the 8-MR; (d) view of the structure along the [100] direction showing the hybrid layers intercalated with organic cations.
Fig. 3 (a) The coordination environment of the gallium and phosphorus atoms in 2; (b)
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the ladder-like gallium phosphite substructure; (c) view of the layered structure with gallium phosphite ladders bridged by oxalate ligands; (d) interlayer A–A–A packing
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model. Fig. 4 PXRD patterns of compounds 1 and 2.
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Fig. 5 TGA carves of compounds 1 and 2.
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Figure 1
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Figure 2
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Figure 3
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Figure 4
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Figure 5
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Highlights (1) Two new gallium phosphate/phosphite-oxalates have been synthesized. (2) Different organic templates are used in the syntheses of 1-2.
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(3) Distinct types of two-dimensional layer structure are formed.
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(4) The oxalate ligands play two roles in the construction of 1-2.