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Syntheses and characterizations of zinc phosphites with new templates generated by N-alkylation transformations
Inorganic Chemistry Communications 39 (2014) 94–98
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Syntheses and characterizations of zinc phosphites with new templates generated by N-alkylation transformations Guo-Ming Wang a,⁎, Ji-Qing Jiao a, Xiao Zhang a, Xiao-Meng Zhao a, Xue Yin a, Zong-Hua Wang a, Ying-Xia Wang b, Jian-Hua Lin b a Teachers College, College of Chemistry and Chemical Engineering, Institute of Hybrid Materials, Growing Base for State Key Laboratory of New Fiber and Modern Textile, Qingdao University, Shandong 266071, China b Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
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Article history: Received 23 October 2013 Accepted 13 November 2013 Available online 19 November 2013 Keywords: Zinc phosphite N-alkylation In situ Crystal structure 12-Ring channel
a b s t r a c t Two new organically templated zinc phosphites, [tmpip]0.5[Zn2(HPO3)2(H2PO 3)] (1) and [dmdabco] [Zn3(HPO3)4]·(H2O) (2), have been synthesized under solvothermal conditions, where tmpip = N,N,N′,N′tetramethyl-piperazinium and dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane. Note that the templating agents tmpip2+ and dmdabco2+ originated from in situ N-methylation transformations between CH3OH solvent and corresponding cyclic aliphatic amine precursors, i.e. piperazine, 1-methylpiperazine or 1,4-dimethylpiperazine in 1, and 1,4-diazabicyclo[2,2,2]octane in 2. Distinct from conventional Eschweiler–Clarke methylation with excess formic acid and formaldehyde, such direct methylation transformation from methanol molecules is unique. Compound 1 consists of ZnO4 tetrahedra, HPO3 and HPO2(OH) pseudopyramids, exhibiting a complex double layered structure with 12-ring windows. Compound 2 is constructed from strictly alternating ZnO4 tetrahedra and HPO3 pseudopyramids, and possesses a (3,4)-connected interrupted architecture with intersecting 8- and 12-ring channels. © 2013 Elsevier B.V. All rights reserved.
Crystalline microporous materials are of great importance for decades because of their rich structural chemistry and wide range of applications in catalysis, separation, ion-exchange and gas storage, etc [1]. The occurrence of microporous aluminophosphates in the 1980s spurred widespread enthusiasm in making non-aluminosilicate-based zeolitic materials [2], in which transition-metal phosphates constitute an important family. However, the structural diversity in this family arises mainly from the substitution of metal cations in architecture, and the replacement of various extra-framework cations as structuredirecting agents or templates. Recently, using pseudo-pyramidal phosphite groups to substitute tetrahedral phosphate anion parts of the inorganic network has resulted in a new class of metal phosphites with great success. Open-framework phosphite frameworks with transition metals of V, Cr, Mn, Fe, Co, Ni and Zn, as well as a few main-group elements have been successfully synthesized [3–13]. Compared to the four-connected {PO4} unit, the presence of three-connected {HPO3} groups might be expected to generate interrupted open structures with novel topologies, larger pore sizes and lower framework densities. Notable examples include TJPU-3 with 20R channels [14], Cr-NKU-24, ZnHPO-CJn (n = 1–4), [HR]2[Zn3(HPO3)4] (R = CHA, CHPA) and SCU-24 with extra-large 24R channels [15], bimetallic phosphite NTHU-5 with 26R channels [16], and NTHU-13 family with 28-, 40-, 48-, 56-, 64- and 72R channels [17]. ⁎ Corresponding author. Fax: +86 532 85956024. E-mail address: [email protected] (G.-M. Wang). 1387-7003/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.inoche.2013.11.013
The employment of organic species with different polarity, size and shape as templates in hydrothermal synthesis has been demonstrated to be an effective and promising method to tune the structures of metal phosphites. Thus, the judicious design or introduction of appropriate templates is crucial for the construction of microporous materials with specific structures and properties. Considered that most templates contained within porous framework are of still direct use, it would be highly desirable to generate new templates in situ from those most prolific and easily available amine precursors. In our effort to investigate insitu-template synthesis of microporous materials, two new organically templated metal phosphites, [tmpip]0.5[Zn2(HPO3)2(H2PO3)] (1) and [dmdabco][Zn3(HPO3)4]·(H2O) (2) were successfully realized [18], where tmpip = N,N,N′,N′-tetramethyl-piperazinium and dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane. Both of the compounds have been characterized by single-crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis. The phase purity of the crystalline solids has been confirmed by the powder XRD (Fig. S1). In the process of synthesizing both compounds, piperazine, 1methyl-piperazine, 1,4-dimethyl-piperazine and dabco were initially selected and introduced, but tmpip2+ and dmdabco2+ were found to act as the true templates, respectively. Obviously, the solvothermal in situ N-methylation reactions occurred in acidic solutions between the CH3 OH solvent and cyclic organic amines, i.e. piperazine, 1-methyl-piperazine and 1,4-dimethyl-piperazine in 1, and dabco in 2 (Scheme 1). Compared with the majority of organic amine templates directly entrained within porous materials in different forms of
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Scheme 1. In situ N-alkylation reactions between piperazine, 1-methylpiperazine, 1,4-dimethyl-piperazine and CH3OH, and dabco and CH3OH under solvothermal conditions, exhibiting the formation of tmpip2+ in 1 and dmdabco2+ in 2.
nonprotonated linkers or protonated countercations, the present templating species generated in situ are unique. More interestingly, such direct N-alkylation transformations are simpler and distinct from the typical Eschweiler–Clarke methylation [19], in which the primary (or secondary) amine is methylated by excess formic acid and formaldehyde. Single crystal X-ray analysis [20–22] of 1 reveals that the asymmetric unit contains 19 independent non-hydrogen atoms, 14 of which belong to the “host framework” (two Zn, three P and nine O atoms) and the remaining five to the guest species (one N and three C atoms) (Fig. 1a). Both the zinc atoms are tetrahedrally coordinated by oxygen atoms with Zn\O bond lengths in the range of 1.908(3) Å–1.940(3) Å (av. 1.924 Å) and O\Zn\O angles lying between 99.5(2)° and 117.4(2)°
(av. 109.3°). Of the three phosphorus atoms, P(1) and P(2) make three P\O\Zn linkages with the fourth vertex occupied by a terminal hydrogen atom, while P(3) only makes two P\O\Zn linkages with the remaining two vertexes occupied by terminal hydrogen and oxygen atoms, respectively. Bond valence sum values [23] indicate that the terminal P(3)\O(8) linkage with a P\O(8) distance of 1.544(4) Å is a terminal \OH group. Assuming the usual valence of Zn, P, O to be +2, + 3 and -2, respectively, the stoichiometry of [Zn2(HPO3)2(H2PO3)] creates a net charge of − 1, which can be balanced by half of a tmpip2 +. The P\O distances are in the range 1.471(3)–1.544(4) Å (av. 1.506 Å), and the O\P\O angles span from 107.4(2) to 114.6(2)° (av. 111.9°), in agreement with those of other open-framework zinc phosphites.
Fig. 1. (a) View of the coordination of the zinc and phosphorus atoms in 1, showing the atom-labeling scheme and 50% thermal ellipsoids. (b) Polyhedral view of the single layer of 1 with 12-ring windows. (c, d) View of the double layer in 1 made up of two single layer in staggered fashion, with terminal P\H and P\OH groups protruding alternately above and below the layers. (e) View of the packing of the double layers interconnected together by H-bonding.
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The structure of 1 consists of ZnO4 tetrahedra, HPO3 and HPO2(OH) units connected through their vertexes, giving rise to a layered architecture. Fig. 1b shows the single inorganic sheet viewed down the [100] direction. It only has large twelve-membered apertures defined by six ZnO4 tetrahedra, four HPO3 and two HPO2(OH) pseudopyramids. The free diameter size of the 12-membered ring is ca. 8.6 × 10.5 Å. Two such layers are fused together in staggered fashion to generate a complex double sheet, with those terminal H and \O(8)H groups exclusively protruding alternately above and below the layers (Fig. 1c, d). Obviously, the presence of terminal \OH groups is free and noncoordinated, thus making no contribution to the expansion of such layers into a high-dimensional architecture. Adjacent layers are further connected with each other through strong H-bonding interaction, O(8)\H(8A)⋯O(2) [d = 2.60], to form a supramolecular network (Fig. 1e). The guest tmpip2+ cations, compensating the negative charges of inorganic framework, are found perfectly arranged in the free region of the 12-ring apertures. Single crystal X-ray analysis of 2 reveals that the structure possesses an extended three-dimensional framework and crystallizes in the space group of P21/n [20–22]. The asymmetric unit contains 30 non-hydrogen atoms, of which three zinc atoms and four phosphorus atoms are crystallographically independent (Fig. 2a). All the zinc atoms are tetrahedrally coordinated by oxygen atoms, and each makes four linkages with adjacent phosphorus atoms via Zn\O\P linkages. The Zn\O bond lengths are in the range of 1.907(4) Å–1.954(4) Å (av. 1.927 Å), and the O\Zn\O angles are in the range of 98.8(2)–118.8(2)° (av. 109.3°). The four unique phosphorus atoms each share three oxygen atoms with adjacent zinc atoms, with the fourth vertex occupied by a terminal hydrogen atom. The P\O distances are in the range 1.490(4)–1.522(3) Å (av. 1.504 Å), and the O\P\O bond angles are in the range 108.7(2)–115.0(2)° (av. 112.0°). The inorganic framework of 2 is built up from strictly alternating ZnO4 tetrahedra and HPO3 pseudopyramids, linked through their vertexes forming a 3D architecture. Interestingly, the heptameric [Zn3(HPO3)4] cluster can be considered to be a secondary building unit (SBU) in the construction of the three-dimensional structure. As
shown in Fig. 2b, it is characterized by one cyclic 6-membered ring constituted by the strict alternation of three ZnO4 and three HPO3 groups, with the fourth HPO3 unit bridging two zinc centers of the above 6-MR. The presence of eight bridging oxygen sites, i.e. two O(2), two O(7), two O(8) and two O(10) atoms, protruding outside of the SBU, indicates that diverse connection ways may be adopted between adjacent SBUs. Along the [010] direction, each SBU is firstly connected to four neighboring units by sharing vertex O(7) and O(8) atoms, generating a two-dimensional layer with 12-ring apertures (Fig. 2c). Such 12-ring window, delimited by 6ZnO4 tetrahedra and 6HPO3 pseudo pyramids, has a pore size of ca. 8.3 × 10.2 Å. Adjacent inorganic layers are further stacked along the [010] direction in an –ABAB– sequence (Fig. 2d), and held together by the remaining O(2) and O(10) bridges to generate a complex three-dimensional framework. Therefore, each SBU is linked to six adjacent units to give the 3D architecture with pcu topology. The elliptical 12-ring channels in 2 are not straight along the [010] direction, and they propagate in a zigzag way and are simultaneously intersected by the multidirectional 8-ring channels with different apertures along the [100], [101] and [001] directions (Fig. 2e–g), respectively. The guest dmdabco2+ species reside in the free voids of 8-ring channels and compensate the negative charges of inorganic architecture. Thermogravimetric (TG) analyses of the title compounds were performed under a flow of N2 to investigate their thermal stabilities. As shown in Fig. 3, the TG curve of 1 shows that the structure remains stable up to 305 °C. On further heating, the initial weight loss between 305 and 535 °C should correspond to the decomposition of organic templates. However, the observed weight loss (14.21%) was lower than the expected value (18.52%). The lower reduction in this stage may be due to the partial retention of carbon in the solid residue (black in color). Similar phenomenon was also observed in other metal phosphite/phosphate systems [24]. The following two-step weight loss of 4.47% between 580–645 °C and 660–785 °C should be attributed to the removal of carbon from the black solid residue. The total observed weight loss for the three steps compared well with that calculated on the basis of the above interpretation (observed: 18.68%; expected: 18.52%). The TG curve of 2 shows the first weight loss occurred between
Fig. 2. (a) View of the coordination of the zinc and phosphorus atoms in 2, showing the atom-labeling scheme and 50% thermal ellipsoids. (b) View of the [Zn3(HPO3)4] secondary building unit. (c) Polyhedral view of single layer along the [010] direction with 12-ring windows. (d) A perspective view of the –ABAB– stacking of inorganic layers, showing the zigzag 12-ring channels. (e, f, g) Polyhedral view of the structure with regular 8-ring channels along the [100], [101] and [001] directions.
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Fig. 3. TG curve of 1 and 2.
88 and 135 °C, which is attributed to the departure of the free water molecule in the structure (observed: 2.38%; expected: 2.66%). The major weight loss between 210 and 690 °C is attributed to the decomposition of organic dmdabco molecules in the product (observed: 20.86%; expected: 21.03%). In summary, two new open-framework zinc phosphites, [tmpip]0.5 [Zn2(HPO3)2(H2PO3)] (1) and [dmdabco][Zn3(HPO3)4]·(H2O) (2), have been obtained as good quality single crystals under mild solvothermal conditions. For 1, the strict alternation of ZnO4 tetrahedra, HPO3 and HPO2(OH) pseudopyramids gives rise to a double layered structure with 12-ring windows. For 2, the connectivity of the ZnO4 tetrahedra and [HPO3] pseudopyramids results in a (3,4)-connected framework with intersecting 8- and 12-ring channels. It is of interest to note that both templating agents, tmpip2+ in 1 and dmdabco2+ in 2, were directly derived from the in situ N-methylation reactions between CH3OH solvent and corresponding cyclic aliphatic amine precursors. Given the large variety of new organic templates that may be generated in situ via different N-alkylation processes under methanol or other alcohol media, the scope for the synthesis of further novel metal phosphites/phosphates, even other related microporous materials, appears to be very large. And further work on this subject is in progress. Acknowledgments This work was supported by the NNSF (20901043), a Project of Shandong Province Higher Educational Science and Technology Program (J13LD18), the Beijing National Laboratory for Molecular Sciences (BNLMS), the Young Scientist Foundation of Shandong Province (BS2009CL041), the Development Project of Qingdao Science and Technology (13-1-4-187-jch) and the Taishan Scholar Program. Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.inoche.2013.11.013. References [1] (a) M.E. Davis, Ordered porous materials for emerging applications, Nature 417 (2002) 813–821; (b) J. Yu, R. Xu, Rich structure chemistry in the aluminophosphate family, Acc. Chem. Res. 36 (2003) 481–490; (c) E.R. Parnham, R.E. Morris, Ionothermal synthesis of zeolites, metal-organic frameworks, and inorganic–organic hybrids, Acc. Chem. Res. 40 (2007) 1005–1013. [2] A.K. Cheetham, G. Férey, T. Loiseau, Open-framework inorganic materials, Angew. Chem. Int. Ed. 38 (1999) 3268–3292.
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Wang, 26-Ring-channel structure constructed from bimetal phosphite helical chains, J. Am. Chem. Soc. 129 (2007) 5350–5351. [17] H.Y. Lin, C.Y. Chin, H.L. Huang, W.Y. Huang, M.J. Sie, L.H. Huang, Y.H. Lee, C.H. Lin, K.H. Lii, X.H. Bu, S.L. Wang, Crystalline inorganic frameworks with 56-ring, 64-ring, and 72-ring channels, Science 339 (2013) 811–813. [18] Synthesis of 1: A mixture of Zn(CH3COO)2·2H2O (0.22 g), H3PO3 (0.44 g), piperazine (0.30 g), methanol (3 mL) and H2O (2 mL) in the typical molar ratio of 1:5.4: 3.5:112:74 was sealed in a Teflon-lined autoclave and heated at 160 °C for 7 days. After cooling to room temperature, colorless crystals of 1 were recovered by filtration, washed with distilled water, and dried in air (82.6% yield based on zinc). Compound 1 can be prepared in a wide range of composition with Zn(CH3COO)2·2H2O or ZnO from 0.8 to 1.5, H3PO3 from 4.5 to 5.6, piperazine from 2.2 to 4.5, CH3OH from 45 to 100, and H2O from 50 to 170. Attempts to investigate the possible in-situ N-alkylation transformations by addition of other piperazine derivatives such as 1-methyl-piperazine and 1,4-dimethyl-piperazine under similar solvothermal conditions, also result in the formation of 1. Anal. calcd (wt.%) for C4H14NO9Zn2P3: C, 10.83; H, 3.18; N, 3.16. Found: C, 10.68; H, 3.06; N, 3.05. IR (KBr pellets, cm−1): 3412(m), 3046(w), 3010(w), 2418(s), 2386(m), 1629(m), 1473(s), 1381(w), 1136(s), 1105(s), 1060(s), 985(s), 924(m), 865(w), 588(s), 572(s), 528(m), 462(m). Synthesis of 2: It was prepared using the same procedure as described for 1 with Zn(CH3COO)2·2H2O (0.12 g), H3PO3 (0.42 g), 1,4diazabicyclo[2,2,2]octane (0.66 g), methanol (1 mL) and H2O (5 mL). Colorless crystals of 2 were collected in 62.5% yield on the basis of zinc. Anal. calcd (wt.%) for C8H24N2O13P4Zn3: C, 14.21; H, 3.58; N, 4.14. Found: C, 14.03; H, 3.42; N, 4.02. IR (KBr pellets, cm−1): 3437(s), 3032(s), 3010(w), 2368(s), 1660(m), 1475(s), 1375(w), 1164(s), 1108(s), 1022(s), 918(w), 879(m), 843(m), 608(s), 5161(m), 497(m), 430(w). [19] (a) H.T. Clarke, H.B. Gillespie, S.Z. Weisshaus, The action of formaldehyde on amines and amino acids, J. Am. Chem. Soc. 55 (1933) 4571–4578; (b) A.C. Cope, W.D. Burrows, Cyclization in the course of Clarke–Eschweiler methylation, J. Org. Chem. 30 (1965) 2163–2165. [20] Crystal data for 1: C4 H 14 NO9 Zn2 P 3 , M = 443.74, triclinic, P-1, a = 8.6827(7) Å, b = 9.6516(3) Å, c = 10.0450(5) Å, α = 115.930(4)°, β = 92.870(5)°, γ = 112.140(2)°, V = 677.50(7) Å 3 , T = 293(2) K, Z = 2, F(000) = 444, Dc = 2.175 g · cm − 3 , μ = 3.931 mm − 1 , 6728 reflections measured, 2796
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independent reflections (Rint = 0.0341), R1 = 0.0360 with I N 2σ(I), wR2 = 0.0896 and GOF = 1.068. For 2, C8H24N2O13P4Zn3, M = 676.28, monoclinic, P21/n, a = 10.0945(4) Å, b = 14.7356(3) Å, c = 14.4964(6) Å, β = 97.497(3)°, V = 1556.51(13) Å3, T = 293(2) K, Z = 4, F(000) = 1360, Dc = 2.101 g · cm−3, μ = 3.702 mm−1, 16,868 reflections measured, 4417 independent reflections (Rint = 0.0349), R1 = 0.0407 with I N 2σ(I), wR2 = 0.1096 and GOF = 1.057. The structures were solved by direct methods and refined with the full-matrix least-squares technique using the SHELXS-97 and SHELXL-97 programs. CCDC 964925 (1) and CCDC 964929 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/ conts/retrieving.html (or from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB21EZ, UK) fax: (+44) 1223-336-033; email: [email protected]. ac.uk. [21] G.M. Sheldrick, A Program for the Siemens Area Detector ABSorption correction, University of Göttingen, 1997.
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Syntheses and characterizations of zinc phosphites with new templates generated by N-alkylation transformations Guo-Ming Wang a,⁎, Ji-Qing Jiao a, Xiao Zhang a, Xiao-Meng Zhao a, Xue Yin a, Zong-Hua Wang a, Ying-Xia Wang b, Jian-Hua Lin b a Teachers College, College of Chemistry and Chemical Engineering, Institute of Hybrid Materials, Growing Base for State Key Laboratory of New Fiber and Modern Textile, Qingdao University, Shandong 266071, China b Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China
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Article history: Received 23 October 2013 Accepted 13 November 2013 Available online 19 November 2013 Keywords: Zinc phosphite N-alkylation In situ Crystal structure 12-Ring channel
a b s t r a c t Two new organically templated zinc phosphites, [tmpip]0.5[Zn2(HPO3)2(H2PO 3)] (1) and [dmdabco] [Zn3(HPO3)4]·(H2O) (2), have been synthesized under solvothermal conditions, where tmpip = N,N,N′,N′tetramethyl-piperazinium and dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane. Note that the templating agents tmpip2+ and dmdabco2+ originated from in situ N-methylation transformations between CH3OH solvent and corresponding cyclic aliphatic amine precursors, i.e. piperazine, 1-methylpiperazine or 1,4-dimethylpiperazine in 1, and 1,4-diazabicyclo[2,2,2]octane in 2. Distinct from conventional Eschweiler–Clarke methylation with excess formic acid and formaldehyde, such direct methylation transformation from methanol molecules is unique. Compound 1 consists of ZnO4 tetrahedra, HPO3 and HPO2(OH) pseudopyramids, exhibiting a complex double layered structure with 12-ring windows. Compound 2 is constructed from strictly alternating ZnO4 tetrahedra and HPO3 pseudopyramids, and possesses a (3,4)-connected interrupted architecture with intersecting 8- and 12-ring channels. © 2013 Elsevier B.V. All rights reserved.
Crystalline microporous materials are of great importance for decades because of their rich structural chemistry and wide range of applications in catalysis, separation, ion-exchange and gas storage, etc [1]. The occurrence of microporous aluminophosphates in the 1980s spurred widespread enthusiasm in making non-aluminosilicate-based zeolitic materials [2], in which transition-metal phosphates constitute an important family. However, the structural diversity in this family arises mainly from the substitution of metal cations in architecture, and the replacement of various extra-framework cations as structuredirecting agents or templates. Recently, using pseudo-pyramidal phosphite groups to substitute tetrahedral phosphate anion parts of the inorganic network has resulted in a new class of metal phosphites with great success. Open-framework phosphite frameworks with transition metals of V, Cr, Mn, Fe, Co, Ni and Zn, as well as a few main-group elements have been successfully synthesized [3–13]. Compared to the four-connected {PO4} unit, the presence of three-connected {HPO3} groups might be expected to generate interrupted open structures with novel topologies, larger pore sizes and lower framework densities. Notable examples include TJPU-3 with 20R channels [14], Cr-NKU-24, ZnHPO-CJn (n = 1–4), [HR]2[Zn3(HPO3)4] (R = CHA, CHPA) and SCU-24 with extra-large 24R channels [15], bimetallic phosphite NTHU-5 with 26R channels [16], and NTHU-13 family with 28-, 40-, 48-, 56-, 64- and 72R channels [17]. ⁎ Corresponding author. Fax: +86 532 85956024. E-mail address: [email protected] (G.-M. Wang). 1387-7003/$ – see front matter © 2013 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.inoche.2013.11.013
The employment of organic species with different polarity, size and shape as templates in hydrothermal synthesis has been demonstrated to be an effective and promising method to tune the structures of metal phosphites. Thus, the judicious design or introduction of appropriate templates is crucial for the construction of microporous materials with specific structures and properties. Considered that most templates contained within porous framework are of still direct use, it would be highly desirable to generate new templates in situ from those most prolific and easily available amine precursors. In our effort to investigate insitu-template synthesis of microporous materials, two new organically templated metal phosphites, [tmpip]0.5[Zn2(HPO3)2(H2PO3)] (1) and [dmdabco][Zn3(HPO3)4]·(H2O) (2) were successfully realized [18], where tmpip = N,N,N′,N′-tetramethyl-piperazinium and dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane. Both of the compounds have been characterized by single-crystal X-ray diffraction, elemental analysis, IR and thermogravimetric analysis. The phase purity of the crystalline solids has been confirmed by the powder XRD (Fig. S1). In the process of synthesizing both compounds, piperazine, 1methyl-piperazine, 1,4-dimethyl-piperazine and dabco were initially selected and introduced, but tmpip2+ and dmdabco2+ were found to act as the true templates, respectively. Obviously, the solvothermal in situ N-methylation reactions occurred in acidic solutions between the CH3 OH solvent and cyclic organic amines, i.e. piperazine, 1-methyl-piperazine and 1,4-dimethyl-piperazine in 1, and dabco in 2 (Scheme 1). Compared with the majority of organic amine templates directly entrained within porous materials in different forms of
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Scheme 1. In situ N-alkylation reactions between piperazine, 1-methylpiperazine, 1,4-dimethyl-piperazine and CH3OH, and dabco and CH3OH under solvothermal conditions, exhibiting the formation of tmpip2+ in 1 and dmdabco2+ in 2.
nonprotonated linkers or protonated countercations, the present templating species generated in situ are unique. More interestingly, such direct N-alkylation transformations are simpler and distinct from the typical Eschweiler–Clarke methylation [19], in which the primary (or secondary) amine is methylated by excess formic acid and formaldehyde. Single crystal X-ray analysis [20–22] of 1 reveals that the asymmetric unit contains 19 independent non-hydrogen atoms, 14 of which belong to the “host framework” (two Zn, three P and nine O atoms) and the remaining five to the guest species (one N and three C atoms) (Fig. 1a). Both the zinc atoms are tetrahedrally coordinated by oxygen atoms with Zn\O bond lengths in the range of 1.908(3) Å–1.940(3) Å (av. 1.924 Å) and O\Zn\O angles lying between 99.5(2)° and 117.4(2)°
(av. 109.3°). Of the three phosphorus atoms, P(1) and P(2) make three P\O\Zn linkages with the fourth vertex occupied by a terminal hydrogen atom, while P(3) only makes two P\O\Zn linkages with the remaining two vertexes occupied by terminal hydrogen and oxygen atoms, respectively. Bond valence sum values [23] indicate that the terminal P(3)\O(8) linkage with a P\O(8) distance of 1.544(4) Å is a terminal \OH group. Assuming the usual valence of Zn, P, O to be +2, + 3 and -2, respectively, the stoichiometry of [Zn2(HPO3)2(H2PO3)] creates a net charge of − 1, which can be balanced by half of a tmpip2 +. The P\O distances are in the range 1.471(3)–1.544(4) Å (av. 1.506 Å), and the O\P\O angles span from 107.4(2) to 114.6(2)° (av. 111.9°), in agreement with those of other open-framework zinc phosphites.
Fig. 1. (a) View of the coordination of the zinc and phosphorus atoms in 1, showing the atom-labeling scheme and 50% thermal ellipsoids. (b) Polyhedral view of the single layer of 1 with 12-ring windows. (c, d) View of the double layer in 1 made up of two single layer in staggered fashion, with terminal P\H and P\OH groups protruding alternately above and below the layers. (e) View of the packing of the double layers interconnected together by H-bonding.
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The structure of 1 consists of ZnO4 tetrahedra, HPO3 and HPO2(OH) units connected through their vertexes, giving rise to a layered architecture. Fig. 1b shows the single inorganic sheet viewed down the [100] direction. It only has large twelve-membered apertures defined by six ZnO4 tetrahedra, four HPO3 and two HPO2(OH) pseudopyramids. The free diameter size of the 12-membered ring is ca. 8.6 × 10.5 Å. Two such layers are fused together in staggered fashion to generate a complex double sheet, with those terminal H and \O(8)H groups exclusively protruding alternately above and below the layers (Fig. 1c, d). Obviously, the presence of terminal \OH groups is free and noncoordinated, thus making no contribution to the expansion of such layers into a high-dimensional architecture. Adjacent layers are further connected with each other through strong H-bonding interaction, O(8)\H(8A)⋯O(2) [d = 2.60], to form a supramolecular network (Fig. 1e). The guest tmpip2+ cations, compensating the negative charges of inorganic framework, are found perfectly arranged in the free region of the 12-ring apertures. Single crystal X-ray analysis of 2 reveals that the structure possesses an extended three-dimensional framework and crystallizes in the space group of P21/n [20–22]. The asymmetric unit contains 30 non-hydrogen atoms, of which three zinc atoms and four phosphorus atoms are crystallographically independent (Fig. 2a). All the zinc atoms are tetrahedrally coordinated by oxygen atoms, and each makes four linkages with adjacent phosphorus atoms via Zn\O\P linkages. The Zn\O bond lengths are in the range of 1.907(4) Å–1.954(4) Å (av. 1.927 Å), and the O\Zn\O angles are in the range of 98.8(2)–118.8(2)° (av. 109.3°). The four unique phosphorus atoms each share three oxygen atoms with adjacent zinc atoms, with the fourth vertex occupied by a terminal hydrogen atom. The P\O distances are in the range 1.490(4)–1.522(3) Å (av. 1.504 Å), and the O\P\O bond angles are in the range 108.7(2)–115.0(2)° (av. 112.0°). The inorganic framework of 2 is built up from strictly alternating ZnO4 tetrahedra and HPO3 pseudopyramids, linked through their vertexes forming a 3D architecture. Interestingly, the heptameric [Zn3(HPO3)4] cluster can be considered to be a secondary building unit (SBU) in the construction of the three-dimensional structure. As
shown in Fig. 2b, it is characterized by one cyclic 6-membered ring constituted by the strict alternation of three ZnO4 and three HPO3 groups, with the fourth HPO3 unit bridging two zinc centers of the above 6-MR. The presence of eight bridging oxygen sites, i.e. two O(2), two O(7), two O(8) and two O(10) atoms, protruding outside of the SBU, indicates that diverse connection ways may be adopted between adjacent SBUs. Along the [010] direction, each SBU is firstly connected to four neighboring units by sharing vertex O(7) and O(8) atoms, generating a two-dimensional layer with 12-ring apertures (Fig. 2c). Such 12-ring window, delimited by 6ZnO4 tetrahedra and 6HPO3 pseudo pyramids, has a pore size of ca. 8.3 × 10.2 Å. Adjacent inorganic layers are further stacked along the [010] direction in an –ABAB– sequence (Fig. 2d), and held together by the remaining O(2) and O(10) bridges to generate a complex three-dimensional framework. Therefore, each SBU is linked to six adjacent units to give the 3D architecture with pcu topology. The elliptical 12-ring channels in 2 are not straight along the [010] direction, and they propagate in a zigzag way and are simultaneously intersected by the multidirectional 8-ring channels with different apertures along the [100], [101] and [001] directions (Fig. 2e–g), respectively. The guest dmdabco2+ species reside in the free voids of 8-ring channels and compensate the negative charges of inorganic architecture. Thermogravimetric (TG) analyses of the title compounds were performed under a flow of N2 to investigate their thermal stabilities. As shown in Fig. 3, the TG curve of 1 shows that the structure remains stable up to 305 °C. On further heating, the initial weight loss between 305 and 535 °C should correspond to the decomposition of organic templates. However, the observed weight loss (14.21%) was lower than the expected value (18.52%). The lower reduction in this stage may be due to the partial retention of carbon in the solid residue (black in color). Similar phenomenon was also observed in other metal phosphite/phosphate systems [24]. The following two-step weight loss of 4.47% between 580–645 °C and 660–785 °C should be attributed to the removal of carbon from the black solid residue. The total observed weight loss for the three steps compared well with that calculated on the basis of the above interpretation (observed: 18.68%; expected: 18.52%). The TG curve of 2 shows the first weight loss occurred between
Fig. 2. (a) View of the coordination of the zinc and phosphorus atoms in 2, showing the atom-labeling scheme and 50% thermal ellipsoids. (b) View of the [Zn3(HPO3)4] secondary building unit. (c) Polyhedral view of single layer along the [010] direction with 12-ring windows. (d) A perspective view of the –ABAB– stacking of inorganic layers, showing the zigzag 12-ring channels. (e, f, g) Polyhedral view of the structure with regular 8-ring channels along the [100], [101] and [001] directions.
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Fig. 3. TG curve of 1 and 2.
88 and 135 °C, which is attributed to the departure of the free water molecule in the structure (observed: 2.38%; expected: 2.66%). The major weight loss between 210 and 690 °C is attributed to the decomposition of organic dmdabco molecules in the product (observed: 20.86%; expected: 21.03%). In summary, two new open-framework zinc phosphites, [tmpip]0.5 [Zn2(HPO3)2(H2PO3)] (1) and [dmdabco][Zn3(HPO3)4]·(H2O) (2), have been obtained as good quality single crystals under mild solvothermal conditions. For 1, the strict alternation of ZnO4 tetrahedra, HPO3 and HPO2(OH) pseudopyramids gives rise to a double layered structure with 12-ring windows. For 2, the connectivity of the ZnO4 tetrahedra and [HPO3] pseudopyramids results in a (3,4)-connected framework with intersecting 8- and 12-ring channels. It is of interest to note that both templating agents, tmpip2+ in 1 and dmdabco2+ in 2, were directly derived from the in situ N-methylation reactions between CH3OH solvent and corresponding cyclic aliphatic amine precursors. Given the large variety of new organic templates that may be generated in situ via different N-alkylation processes under methanol or other alcohol media, the scope for the synthesis of further novel metal phosphites/phosphates, even other related microporous materials, appears to be very large. And further work on this subject is in progress. Acknowledgments This work was supported by the NNSF (20901043), a Project of Shandong Province Higher Educational Science and Technology Program (J13LD18), the Beijing National Laboratory for Molecular Sciences (BNLMS), the Young Scientist Foundation of Shandong Province (BS2009CL041), the Development Project of Qingdao Science and Technology (13-1-4-187-jch) and the Taishan Scholar Program. Appendix A. Supplementary data Supplementary data to this article can be found online at http://dx. doi.org/10.1016/j.inoche.2013.11.013. References [1] (a) M.E. Davis, Ordered porous materials for emerging applications, Nature 417 (2002) 813–821; (b) J. Yu, R. Xu, Rich structure chemistry in the aluminophosphate family, Acc. Chem. Res. 36 (2003) 481–490; (c) E.R. Parnham, R.E. Morris, Ionothermal synthesis of zeolites, metal-organic frameworks, and inorganic–organic hybrids, Acc. Chem. Res. 40 (2007) 1005–1013. [2] A.K. Cheetham, G. Férey, T. Loiseau, Open-framework inorganic materials, Angew. Chem. Int. Ed. 38 (1999) 3268–3292.
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Xu, [Zn(HPO3)(C11 N2O2H12)] and [Zn3(H2O)(PO4)(HPO4)(C6H9N3O2)2(C6H8N3O2)]: homochiral zinc phosphite/phosphate networks with biofunctional amino acids, Dalton Trans. 39 (2010) 5439–5445. [11] G.M. Wang, X. Zhang, J.H. Li, Z.H. Wang, Y.X. Wang, J.H. Lin, A new hybrid zinc phosphite with a pillared layered structure: synthesis and characterization of [C6N2O2H16][Zn(HPO3)]2, Inorg. Chem. Commun. 36 (2013) 27–30. [12] Z. Yi, C. Chen, S. Li, G. Li, H. Meng, Y. Cui, Y. Yang, W. Pang, Hydrothermal synthesis and structural characterization of the first indium phosphite In2(HPO3)3(H2O), Inorg. Chem. Commun. 8 (2005) 166–169. [13] A. Lu, H. Song, N. Li, S. Xiang, N. Guan, H. Wang, Novel large aluminophosphite cage unit as the building blocks to form a framework structure containing multidimensional 12-ring channels, Chem. Mater. 29 (2007) 4142–4147. [14] Y. Yang, Y.N. Zhao, J.G. Yu, S.Z. Wu, R.J. Wang, Doping-induced structure variation of 1,3-cyclohexane-bis(methylamine)-templated zinc–phosphorus open structures, Inorg. Chem. 47 (2008) 769–771. [15] (a) Y. Yang, N. Li, H. Song, H. Wang, W. Chen, S. Xiang, Metal phosphite containing 24-ring channels with 10-ring windows, Chem. Mater. 19 (2007) 1889–1891; (b) J. Liang, J. Li, J. Yu, P. Chen, Q. Fang, F. Sun, R. Xu, [(C4H12N)2]-[Zn3(HPO3)4]: an open-framework zinc phosphite containing extra-large 24-ring channels, Angew. Chem. Int. Ed. 45 (2006) 2546–2548; (c) J. Li, L. Li, J. Liang, P. Chen, J. Yu, Y. Xu, R. Xu, Template-designed syntheses of open-framework zinc phosphites with extra-large 24-ring channels, Cryst. Growth Des. 8 (2008) 2318–2323; (d) X.C. Luo, D.B. Luo, H.M. Zeng, M.C. Gong, Y.Q. Chen, Z.E. Lin, A 3,4-connected beryllium phosphite framework containing 24-ring channels with a very low density, Inorg. Chem. 50 (2011) 8697–8699. [16] Y.L. Lai, K.H. Lii, S.L. Wang, 26-Ring-channel structure constructed from bimetal phosphite helical chains, J. Am. Chem. Soc. 129 (2007) 5350–5351. [17] H.Y. Lin, C.Y. Chin, H.L. Huang, W.Y. Huang, M.J. Sie, L.H. Huang, Y.H. Lee, C.H. Lin, K.H. Lii, X.H. Bu, S.L. Wang, Crystalline inorganic frameworks with 56-ring, 64-ring, and 72-ring channels, Science 339 (2013) 811–813. [18] Synthesis of 1: A mixture of Zn(CH3COO)2·2H2O (0.22 g), H3PO3 (0.44 g), piperazine (0.30 g), methanol (3 mL) and H2O (2 mL) in the typical molar ratio of 1:5.4: 3.5:112:74 was sealed in a Teflon-lined autoclave and heated at 160 °C for 7 days. After cooling to room temperature, colorless crystals of 1 were recovered by filtration, washed with distilled water, and dried in air (82.6% yield based on zinc). Compound 1 can be prepared in a wide range of composition with Zn(CH3COO)2·2H2O or ZnO from 0.8 to 1.5, H3PO3 from 4.5 to 5.6, piperazine from 2.2 to 4.5, CH3OH from 45 to 100, and H2O from 50 to 170. Attempts to investigate the possible in-situ N-alkylation transformations by addition of other piperazine derivatives such as 1-methyl-piperazine and 1,4-dimethyl-piperazine under similar solvothermal conditions, also result in the formation of 1. Anal. calcd (wt.%) for C4H14NO9Zn2P3: C, 10.83; H, 3.18; N, 3.16. Found: C, 10.68; H, 3.06; N, 3.05. IR (KBr pellets, cm−1): 3412(m), 3046(w), 3010(w), 2418(s), 2386(m), 1629(m), 1473(s), 1381(w), 1136(s), 1105(s), 1060(s), 985(s), 924(m), 865(w), 588(s), 572(s), 528(m), 462(m). Synthesis of 2: It was prepared using the same procedure as described for 1 with Zn(CH3COO)2·2H2O (0.12 g), H3PO3 (0.42 g), 1,4diazabicyclo[2,2,2]octane (0.66 g), methanol (1 mL) and H2O (5 mL). Colorless crystals of 2 were collected in 62.5% yield on the basis of zinc. Anal. calcd (wt.%) for C8H24N2O13P4Zn3: C, 14.21; H, 3.58; N, 4.14. Found: C, 14.03; H, 3.42; N, 4.02. IR (KBr pellets, cm−1): 3437(s), 3032(s), 3010(w), 2368(s), 1660(m), 1475(s), 1375(w), 1164(s), 1108(s), 1022(s), 918(w), 879(m), 843(m), 608(s), 5161(m), 497(m), 430(w). [19] (a) H.T. Clarke, H.B. Gillespie, S.Z. Weisshaus, The action of formaldehyde on amines and amino acids, J. Am. Chem. Soc. 55 (1933) 4571–4578; (b) A.C. Cope, W.D. Burrows, Cyclization in the course of Clarke–Eschweiler methylation, J. Org. Chem. 30 (1965) 2163–2165. [20] Crystal data for 1: C4 H 14 NO9 Zn2 P 3 , M = 443.74, triclinic, P-1, a = 8.6827(7) Å, b = 9.6516(3) Å, c = 10.0450(5) Å, α = 115.930(4)°, β = 92.870(5)°, γ = 112.140(2)°, V = 677.50(7) Å 3 , T = 293(2) K, Z = 2, F(000) = 444, Dc = 2.175 g · cm − 3 , μ = 3.931 mm − 1 , 6728 reflections measured, 2796
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independent reflections (Rint = 0.0341), R1 = 0.0360 with I N 2σ(I), wR2 = 0.0896 and GOF = 1.068. For 2, C8H24N2O13P4Zn3, M = 676.28, monoclinic, P21/n, a = 10.0945(4) Å, b = 14.7356(3) Å, c = 14.4964(6) Å, β = 97.497(3)°, V = 1556.51(13) Å3, T = 293(2) K, Z = 4, F(000) = 1360, Dc = 2.101 g · cm−3, μ = 3.702 mm−1, 16,868 reflections measured, 4417 independent reflections (Rint = 0.0349), R1 = 0.0407 with I N 2σ(I), wR2 = 0.1096 and GOF = 1.057. The structures were solved by direct methods and refined with the full-matrix least-squares technique using the SHELXS-97 and SHELXL-97 programs. CCDC 964925 (1) and CCDC 964929 (2) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/ conts/retrieving.html (or from the Cambridge Crystallographic Data Center, 12 Union Road, Cambridge CB21EZ, UK) fax: (+44) 1223-336-033; email: [email protected]. ac.uk. [21] G.M. Sheldrick, A Program for the Siemens Area Detector ABSorption correction, University of Göttingen, 1997.
[22] (a) G.M. Sheldrick, SHELXS97 Program for Solution of Crystal Structures, University of Göttingen, Göttingen, Germany, 1997.; (b) G.M. Sheldrick, SHELXL97 Program for Solution of Crystal Structures, University of Göttingen, Germany, 1997. [23] I.D. Brown, D. Aldermatt, Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database, Acta Crystallogr. Sect. B41 (1985) 244–247. [24] (a) Z.E. Lin, J. Zhang, Y.Q. Sun, G.Y. Yang, Ga(2,2′-bipy)(HPO4)(H2PO4): first layered inorganic–organic hybrid gallium phosphate with a neutral framework, Inorg. Chem. 43 (2004) 797–801; (b) L.L. Huang, T.Y. Song, Y. Fan, L. Yang, L.P. Yang, H. Zhang, L. Wang, J.N. Xu, Hydrothermal syntheses, characterizations of novel three-dimensional indium phosphite and indium phosphite-phosphate with intersecting 8-membered ring channels: [In3(H2PO3)3(HPO3)4]·(trans-C6N2H16) and [In6(HPO3)8(H2PO3)5 (H2P O4)]·(C3N2H12)2, Microporous Mesoporous Mater. 132 (2010) 409–413.