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Oct 2, 2017 - Department of Chemistry, National Institute of Technology Kurukshetra, Haryana-136119, India. •S Supporting Information. ABSTRACT: By ...
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Rare Examples of Amine-Templated Organophosphonate Open-Framework Compounds: Combined Role of Metal and Amine for Structure Building Avijit Kumar Paul, Rajendiran Kanagaraj, Neha Pant, and Kumari Naveen Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01110 • Publication Date (Web): 02 Oct 2017 Downloaded from http://pubs.acs.org on October 3, 2017

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Rare Examples of Amine-Templated Organophosphonate Open-Framework Compounds: Combined Role of Metal and Amine for Structure Building Avijit Kumar Paul*, Rajendiran Kanagaraj, Neha Pant and Kumari Naveen Department of Chemistry, National Institute of Technology Kurukshetra, Haryana-136119, India. Supporting Information Placeholder By introduction of 2-methyl-1,5diaminopentane (DAP) and 1,4-diaminobutane (DAB) as templated ions, three new amine-templated organophosphonate open-framework compounds [H2DAP][Zn6(Hhedp)2(hedp)2].4H2O, I, [H2DAB][Zn6(Hhedp)2(hedp)2].4H2O, II and [H2DAB][Zn3(hedp)2].2H2O, III have been synthesized, structurally analyzed, and characterized for the first time. Both the compound I and II have analogous 2-D sheet structure connecting through metal and diphosphonates (1hydroxyethane-1,1-diphosphonic acid), while the templated amines are different in the framework. Compound III consists of Zn ions and diphosphonate ligands with templated DAB, forming three-dimensional framework with interconnected 4-T, 8-T and 12-T ring channels. To the best of our knowledge, such structural modifications with coordination variation of metal ions applying same amine have never been reported in organophosphonates family. Presence of mixed metal as well as different aliphatic amines play a crucial role for the structure directing in open-framework compounds which is noteworthy.

structures by multiple coordination sites and possible functionalities. Even though few organophosphonate structures are reported,30-36 the investigations of amine-templated metal organaphosphonates are just beginning which may evolve a rich structural varieties.37-41 We have taken 1hydroxyethane-1,1-diphosphonic acid (hedpH4) as the diphosphonate ligand to build a new family of open-framework structures with templated aliphatic amines. Our efforts yielded two new two-dimensional layer structures and one three-dimensional structure, namely, [H2DAP][Zn6(Hhedp)2(hedp)2].4H2O, I, [H2DAB][Zn6(Hhedp)2(hedp)2].4H2O, II and [H2DAB][Zn3(hedp)2].2H2O, III. In this communication, we report the novel synthetic strategy and structural diversity of three organically templated open-framework compounds.

Investigation of new open-framework structure by the assemblage of hybrid inorganic-organic building blocks is a subject of intense research in material chemistry from last four decades, resulting in various applications such as proton conductor, catalysts, ion-exchangers, sensors, sorbents, charge storage materials and so on.1-9 Although the initial research of zeolite based open-frameworks focused on silicate and phosphate based networks, later on phosphite, sulfate, sulfite, selenate, selenite and borate based framework structures are also investigated in large number.10-26 Exploration and incorporation of newer anions as network builder is a major enduring challenge, the successful discovery of new frameworks with thiosulfate unit is an example in our earlier work.27-29 Selection of new building block with inorganic-organic moiety can combine the coordination versatility of the inorganic along with the functional diversity of the organic group. Hence, organophosphonate could be a possible replacement of traditional inorganic phosphate unit.

All the three compounds have been prepared hydrothermally and their structures were determined using single crystal X-ray diffraction studies (CCDC no: 1551491, 1551492 and 1495890).42 For the synthesis of I, we took a mixture of ZnSO4.H2O (0.179 g, 1 mmol), MoO3 (0.144 g, 1 mmol), 2methyl-1,5-diaminopentane (0.27 mL, 2 mmol), hedpH4 solution (0.28 mL, 2 mmol), and 10 mL distilled water. The resultant solution was mixed for 1 hr at room temperature, sealed in a 20mL teflon-lined stainless steel autoclave and o heated at 160 C for 72 hrs under autogenous pressure to obtain colorless plate type crystals. Compound II was also synthesized by following the similar reaction condition apart from the different amine i.e. 1,4-diaminobutane (DAB). Although both Zn and Mo metals were used in reaction mixture, the product contains only Zn in its structure. The minimum 0.75 mmol of MoO3 is required in each reaction mixtures to obtain the pure polycrystalline phase of I and II. To investigate the role of Mo in the product formation, we avoided MoO3 in a separate reaction mixture. Thus, compound III was obtained by the reaction mixture of ZnSO4.H2O, hedpH4 and DAB with the molar ratio of 1:2:2. We are not able to isolate any three-dimensional structure with DAP by using only Zn metal in reaction mixture. Similar reaction conditions are also followed with Zn(NO3)2.6H2O as starting material in place of ZnSO4.H2O. But the phase pure compounds were obtained only with ZnSO4.H2O (see ESI, Fig. s6)

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Continuous efforts have been made for synthesis of metal phosphonates, as one can expect a variety of interesting

Single crystal structural analysis showed that the compound I and II have the analogous structure with different

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The overall frameworks for I and II are the isostructural two-dimensional layers formed by the strictly alternative zinc and diphosphonate connectivity (Figure 1a). Out of two diphosphonate units, one diphosphonate unit (hedp4-) is coordinated with 5 zinc atoms (Zn1+2Zn2+2Zn3) whereas the other one (Hhedp3-) is coordinated with four zinc atoms (Zn1+2Zn2+Zn3). The hydroxyl group of hedp4- is coordinated with octahedral Zn atoms (Zn1) along with one free water molecule. In order to understand the structure connectivity, one can find that two Zn2 ions are connected with two CPO3 tetrahedra (from Hhedp3- unit) forming a dimeric units (see ESI Fig. S9a). Two such dimers are connected with two another diphosphonate unit (hedp4-) forming 12 membered ring constructed by Zn2-P1-Zn2-P4-C4-P3-Zn2-P1-Zn2-P4C4-P3 along ac plane (see ESI Fig. S9b). From this ring, free CPO3 tetrahedra of the Hhedp3- and hedp4- units are further connected with Zn1 and Zn3 atom in two different directions forming overall layer structure. The protonated aliphatic amines and lattice water molecules are present inside the layers (Figure 1b). Three-dimensional supramolecular structure is stabilized by amine and water molecules through the hydrogen bonding interactions. The asymmetric unit of III contains 33 non-hydrogen atoms of which three Zn atoms and four P atoms (two diphosphonate units) are crystallographically independent. All the three Zn atoms have distorted tetrahedral geometry connecting with four oxygen atoms of diphosphonate units (ZnO4, CN=4). The Zn–O distances are in the range of 1.899–1.984 Å with the average value of 1.943 Å. The O–Zn–O bond angles span from 100.3o to 126.2o with the average value of 109.3o in agreement with distorted tetrahedral coordination. Out of three zinc atoms, two are associated with three diphosphonate ligands and one zinc (Zn3) is associated with two diphosphonate ligand (see ESI, Fig. S11). Each diphosphonate ligands (hedp4-) are connected with four Zn atoms via corner-sharing connectivity (Figures 1d and 1e). The P–O dis-

tances are lying in the range of 1.507–1.529 Å with the average value of 1.519 Å. The O–P–O angles are in the range of 105.6 – 114.1o with the average value of 109.7o confirming the tetrahedral nature of phosphonate unit (Table T2-T3).

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Fig. 1: (a) Two-dimensional analogous layer structures of compounds I and II. (b) Polyhedral view of threedimensional packing arrangement of compound II. Note the DAB molecules inside the layers. All amine hydrogens are omitted for clarity. (c) Node connectivity between Zn and diphosphonate units in compounds II. Cyan color nodes represent zinc atom and violate color nodes represent diphosphonate units. The overall three-dimensional framework structure is observed due to the alternative connectivity of zinc ions and diphosphonate units (see ESI, Fig. S12). In this three-

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templated ions and crystallize in the triclinic P-1 space group (see ESI Table T1). Both the structures contain three zinc and four phosphorous (i.e two diphosphonate unit) atoms in the asymmetric unit. Out of three zinc ions, one zinc (Zn1) is distorted octaherdral and two zinc ions (Zn2 & Zn3) are tetrahedral in nature. Zn1 is connected with one terminal water, four oxygen and one hydroxyl ion from diphosphonate unit forming the octahedral environment {ZnO4(OH)(OH2), CN = 6}. The average Zn‒O bond distances are 2.034 Å (for I) and 2.022 Å (for II) ranging from 1.990 to 2.091 Å when the zinc ions are connected with oxygen of the diphosphonate unit. But the terminal water and hydroxyl ions are connected with Zn1 in a larger average Zn‒O distance of 2.298 Å (for I) and 2.348 Å (for II) ranging from 2.265 to 2.389 Å which may be the possible reason of distorted octahedral coordination. The average Zn‒O distance of the two tetrahedral Zn2+ ions (Zn2 and Zn3) are 1.938 Å (for I) and 1.935Å (for II) with the range from 1.907 to 1.975 Å which is lower than the octahedral Zn‒O distances. Two different diphosphonate units are present with ionic and coordination variation. The average P‒O bond distances are 1.522 Å (for I) and 1.524 Å (for II) with the span from 1.500 to 1.569 Å. The O–P–O bong angle are in the range of 107.4 –115.0o with the average value of 111.7o confirming the distorted tetrahedral nature of phosphonate unit (see ESI, Table T2-T3).

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dimensional structure, three different kinds of channels are observed namely; i) by two ZnO4 tetrahedra and two CPO3 tetrahedra, ii) four ZnO4 tetrahedra and four CPO3 tetrahedra, and iii) six ZnO4 tetrahedra and six CPO3 tetrahedra. All the channels are interconnected and extended along the entire three axes to form 3-D open-framework structure. Basically, there is a dimer formed by two zinc (Zn1) and two diphosphonate units (P1). These dimers are connected with 2 different Zn ions (Zn2) and 4 other CPO3 tetrahedra forming one-dimensional chain with 8-membered pore opening along a axis. The templated DAB unit is placed inside this channel (8-T) formed by four ZnO4 tetrahedra and four CPO3 tetrahedra with a pore size of 7.8 Å × 5.4 Å (shortest atom-atom contact distances, not including the van der Waals radii). The protonated DAB molecules occupy these channels and interacted with the framework through hydrogen bonds. Though the above channel is growing along the a aix, there is one bigger channel of size 12.3 Å × 6.3 Å (shortest atom-atom contact distances, not including the van der Waals radii) can be observed along ac plane in the three-dimensional structure (Figure 2a). This large channel of 12-rmembered ring (six ZnO4 tetrahedra and six CPO3 tetrahedra) is constructed by Zn2-P2-Zn1-P1-Zn3-P3-Zn2-P2-Zn1-P1-Zn3-P3 in ac plane (Figure 2a). Templated water and pendant –CH3 groups occupy this bigger channel and facilitate stabilization through hydrogen bonds with framework oxygens. The free protonated amine molecules are stabilized through extensive N─H···O hydrogen bonding interactions with the framework. (a)

phonate units in compounds III. Cyan color nodes represent zinc atom and violate color nodes represent diphosphonate units. All the compounds I‒III are showing the amine-templated open structures having the connectivity between the zinc and diphosphonate units. In present study, we have observed the structural differences mainly due to the presence of variable organic amine molecules and reaction mixture. Though the molybdenum (Mo) atoms are not participating in the structure building but the structural variation of II and III shows its presence in the reaction mixtures. Although few closely related amine-templated 2-D and 3-D structures are reported,37-41 but the role of aliphatic amines and supporting metal ions are not investigated so far. The EDAX analyses have also been carried out for confirming the absence of Mo in structures I and II (see ESI Fig. S13-S14). The observed results showed that the structure I contains the lesser % of Zn and higher % of C as one can calculate from the molecular weight. Hence, both the tetrahedral and octahedral sites are occupied by Zn ions in compounds I and II. The octahedral Zn ions of II are replaced by tetrahedral Zn ions in III and enhancing the overall dimensionality from 2-D to 3-D. Such involuted 2-D and 3-D framework structures can be simplified and well understood by the network connectivity. Hence, we have performed a detailed structural analysis using the TOPOS40 Program.43 Here, we have considered each zinc atom as one node (cyan color in Figure 1c and 2b) and each diphosphonate unit as one node (violet color in Figure 1c and 2b). The structures I and II contain total five nodes which are from three different Zn atoms and two different diphosphonate units. Zn1 is acting as connector whereas Zn2 and Zn3 are forming 4- and 3-connected nodes, respectively (Figure 1c). Two diphosponate units are forming 4- and 5connected nodes. Three Zn-nodes are associated with diphosphonate nodes and forming 3-, 4-, 5-, 6-, 7- and 8membered rings. The overall point symbol for 2-D net is 2 2 2 2 2 2 (3.4.5.6.7.8)(3.4.5)(3 .4 .5.6 .7 .8)(3 .4 .5.6). Similarly, from the structural analysis of III (Figure 2b) one can find three different zinc units are associated with various nets. Zn1 is associated with two 5-, one 6- and three 2 8-membered rings. The corresponding point symbol is 4.8 2 3 and 5 .6.8 . Unlike to Zn1, Zn2 is forming one 4-, one 5-, one 3 6- and three 8-membered rings with point symbol of 4.5.6.8 . Zn3 is acting as connecter as it is bidentate. Each diphosphonate (single node) unit is connected with four zinc atoms. First diphosphonate forms net with one 4-, one 6- and one 8membered ring with corresponding point symbol 4.6.8. Second diphosphonate unit forms two 5- and one 8-membered 2 ring with corresponding point symbol 5 .8. Hence the overall connectivity of zinc-nodes and diphosphonate-nodes form a three-dimensional network structure consisting of 4-, 5-, 6-, and 8-membered rings with point symbol 3 2 3 2 (4.5.6.8 )(4.6.8)(5 .6.8 )(5 .8). Hence, three-dimensional net is formed with bigger pore-channel than the twodimensional net.

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Fig. 2: (a) Three-dimensional polyhedral view of compound III along ac plane. Note that the amine molecules are not occupying the largest void made by 12-T ring channels. (b) Node connectivity between Zn and diphos-

In summary, two new isostructural two-dimensional and one three-dimensional zinc diphosphonate open-framework compounds have been synthesized under hydrothermal conditions by using aliphatic diamine as the templating agent. These are the first examples of secondary cation directed hierarchical structural modulation from 2-D to 3-D amine-

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templated open-framework structures in the family of metalorganophosphonates. The coordination variation from octahedral Zn centres (in II) to tetrahedral Zn centres (in III) plays a subtle role for the structural modification from 2-D sheet structure to 3-D framework. The combination of two metals and different aliphatic amines are playing the crucial role for the network building which is noteworthy. Present examples are not only enriching the field of amine-templated open-framework materials but also open possibilities for investigations of new phosphonates using different templates and metal combinations.

ASSOCIATED CONTENT Supporting Information Tables listing crystallographic data, selected bond lengths and angles for compounds I-III, PXRD patterns, IR spectrum, TGA plot, few structures, SEM image and EDAX analysis. This material is available free of charge via the Internet at http://pubs.acs.org.

Corresponding Author *Email: [email protected]

ACKNOWLEDGMENT The Science and Research Board (SERB), Government of India, is thanked for the award of Fast Track startup grant. The author also thanks the Department of Science and Technology (DST), Government of India, for INSPIRE Faculty Award and establishing SAIF for single crystal data collection at IIEST Shibpur.

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with a 3D Supramolecular Structure: Synthesis, Crystal Structure, Srface Photovoltage and Luminescence Properties. RSC Adv., 2014, 4, 46595–46601. (32) Sun, S.-H.; Sun, Z.-G.; Zhu, Y.-Y.; Dong, D.-P.; Jiao, C.-Q.; Zhu, J.; Li, J.; Chu, W.; Tian, H.; Zheng, M. J.; Shao, W.-Y.; Lu, Y.-F. Four Novel Oxomolybdenum-organodiphosphonate Hybrids in the Presence of Cu(II)-Organonitrogen Building Blocks: Synthesis, Crystal Structures, and Surface Photovoltage Properties. Cryst. Growth Des. 2013, 13, 226–238. (33) Wang, W.-N.; Sun, Z.-G.; Zhu, Y.-Y.; Dong, D.-P.; Li, J.; Tong, F.; Huang, C.-Y.; Chen, K.; Li, C.; Jiao, C.-Q.; Wang, C.-L. Hydrothermal Synthesis, Structures, and Luminescent Properties of Four New Zinc(II) Diphosphonate Hybrids with Mixed Ligands. CrystEngComm, 2011, 13, 6099-6106. (34) Dutta, A.; Mondal, J.; Patra, A. K.; Bhaumik, A. Synthesis and Temperature-Induced Morphological Control in a Hybrid Porous Iron-Phosphonate Nanomaterial and Its Excellent Catalytic Activity in the Synthesis of Benzimidazoles. Chem. Eur. J. 2012, 18, 1337213378. (35) Wu, J.; Hou, H.; Han, H; Fan, Y. Highly Selective Ferric Ion Sorption and Exchange by Crystalline Metal Phosphonates Constructed from Tetraphosphonic Acids. Inorg. Chem. 2007, 46, 79607970. (36) Zhou, T.-H.; Yi, F.-Y.; Li, P.-X.; Mao, J.-G. Synthesis, Crystal Structures, and Luminescent Properties of Two Series’of New Lanthanide(III) Amino-Carboxylate-Phosphonate. Inorg. Chem. 2010, 49, 905-915. (37) Li, J.-H.; Han, S.-D.; Pan, J.; Xue, Z.-Z.; Wang, G.-M.; Wang, Z.-H.; Bao, Z.-Z. Template synthesis and photochromism of a layered zinc diphosphonate. CrystEngComm. 2017, 19, 1160-1164. (38) Wang, G.-M.; Li, J.-H.; Pan, J.; Xue, Z.-Z.; Wei, L.; Han, S.-D.; Bao, Z.-Z.; Wang, Z.-H. Two hybrid transition metal triphosphonates decorated with tripodal imidazole ligand: synthesis, structure and properties. Dalton Trans. 2017, 46, 808-813. (39) Ni, A.-Y.; Pan, J.; Xue, Z.-Z.; han, S.-D.; Li, J.-H.; Wang, G.-M.; Wang, Z.-H. Synthesis and structural characterization of five zinc bisphosphonate compounds. Solid State Sciences. 2017, 70, 47-53. (40)Chen, H.; Sun, Z.; Dong, D.; Meng, L.; Zheng, X.; Zhu, Y.; Zhao, Y.; Zhang, J. Hydrothermal syntheses, crystal structures and thermal stability of two divalent metal phosphonates with a layered and a 3D structure. J. Coord. Chem. 2008, 61, 1316-1324. (41) Tong, F.; Zhu, Y.; Sun, Z.; Wang, W.; Zhao, Y.; Xu, L.; Gong, J. Mixed-solvothermal syntheses, structures and luminescence properties of two new zinc(II) phosphonates with layered and 3D framework structures. Inorg. Chim. Acta. 2011, 368, 200-206. (42) Crystal Data For I: Triclinic, P-1 (no. 2), a = 8.118(5), b = 11.489(5), c = 11.662(5) Å, α = 77.746(2)°, β = 77.556(5)°, γ = 85.149(5)°, V = 1037.1(9) Å3, Z= 2, ρcal = 2.178 g cm-3, μ(Mokα) = 3.827 mm-1, 28137 reflections, 4074 unique, 3726 observed I>2σ(I), R1 = 0.0545, wR2 = 0.1390 and GOF =1.097 for 275 parameters; For II: Triclinic, P1 (no. 2), a = 8.074(2), b = 11.185(3), c = 11.716(3) Å, α = 76.668 (14)°, β = 77.148(12)°, γ = 83.297(14)°, V = 1001.4(4) Å3, Z= 2, ρcal = 2.239 g cm-3, μ(Mokα) = 3.962 mm-1, 26811 reflections, 4715 unique, 4130 observed I>2σ(I), R1 = 0.0578, wR2 = 0.1443 and GOF =1.048 for 266 parameters; For III: monoclinic, C2/c (no. 15), a = 20.326(3), b = 9.214(2), c = 23.018(2) Å, β = 92.110(8)°, V = 4308.1(9) Å3, Z= 8, ρcal = 2.212 g cm-3, μ(Mokα) = 3.692 mm-1, 34444 reflections, 4990 unique, 4485 observed I>2σ(I), R1 = 0.0458, wR2 = 0.1358 and GOF =1.054 for 298 parameters. CCDC: 1551491(I), 1551492(II) and 1495890(III). (43) (a) Blatov, V. A. 2006. http://www.topos.ssu.samara.ru/; (b) Blatov, V. A.; Shevchenko, A. P.; Serezhkin, V. N. TOPOS3.2: A New Version of the Program Package for Multipurpose Crystal-Chemical Analysis. J. Appl. Crystallogr., 2000, 33, 1193.

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Crystal Growth & Design

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Crystal Growth & Design

Rare Examples of Amine-Templated Organophosphonate Open-Framework Compounds: Combined Role of Metal and Amine for Structure Building Avijit Kumar Paul*, Rajendiran Kanagaraj, Neha Pant and Kumari Naveen Department of Chemistry, National Institute of Technology Kurukshetra, Haryana-136119, Ind ia. Insert Table of Contents Graphic and Synopsis Here

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Two new isostructural two-dimensional and one three-dimensional amine templated zincorganophosphates have been obtained by varying the reaction compositions under hydrothermal conditions. The figure shows the various net structures obtained in the family of organphosphonates.

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