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Three open-framework gallium phosphates [C6H16N2][Ga(HPO4)(PO4)] (1), {H[C6H16N2]2[Ga7(OH)2(PO4)8]} (2), and {H[C4H12N2]2[Ga7(OH)2(PO4)8]·2H2O} (3) were solvothermally synthesized in the presence of 2,6-dimethylpyrazine, N-ethylpiperazine, and piperazine as templates, respectively. Compound 1 possesses an infinite one-dimensional chain structure connected by hydrogen-bond interactions to generate a 3D supramolecular framework. Compounds 2 and 3 show similar inorganic framework structures, which may be viewed as the assembly of a secondary building unit (SBU), Ga6P8 containing two GaO4, two GaO5, two GaO6 as well as eight PO4 groups. The SBUs are linked with each other by vertexsharing oxygen atoms to form 2D sheets, which are further connected by GaO4 tetrahedra to result in the final 3D open-framework with leftand right-handed helical chains. In these materials, the well-ordered organic species reside in the voids of structures and interact with the framework by way of hydrogen bonds. [ABSTRACT FROM AUTHOR]

Two isomorphic organically templated zinc/cobalt oxalates, (dmdabco)[Zn2(C2O4)3]·4H2O (1), and (dmdabco)[Co2(C2O4)3]·4H2O (2) (C2O42− = oxalate; dmdabco = N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane), have been prepared under solvothermal conditions and characterized by X-ray structural analyses. The dmdabco2+templating agent was derived from simplein situN-alkylation between methanol and 1,4-diazabicyclo[2,2,2]octane (dabco). Distinct from conventionalEschweiler-Clarkemethylation containing excess formic acid and formaldehyde, such one-step methylation from methanol molecules is convenient. Both1and2exhibit a uninodal 3-connected 3-D interrupted open-framework, in which oxalate ligands havein-planeandout-of-planeconnection modes. [ABSTRACT FROM AUTHOR]

Two new inorganic–organic hybrids, (H ampy )Zn 2 (PO 4 ) (HPO 3 ) ( 1 ) and ( ampy )Zn 2 (HPO 3 ) 2 ( 2 ), where ampy = 3-(aminomethyl)pyridine, have been solvothermally prepared and structurally characterized. Compound 1 exhibits an unusual two-dimensional layer structure, which possesses a central 4.8 2 zincophosphate sheet wrapped by infinite zincophosphite chains. Left- and right-handed helical chains participate in the formation of the zincophosphate layer. Compound 2 features a three-dimensional pillared-layer structure, in which two-dimensional Zn II (HPO 3 ) inorganic sheets were cross-linked by ampy ligands. The simultaneous occurrence of zinc-amine helical chains in 2 is unique and, to the best of our knowledge, firstly encountered in phosphite/phosphate hybrid materials. Different coordination modes and roles of the same ampy ligand were observed in the formation of the hybrid structures. [ABSTRACT FROM AUTHOR]

A novel open-framework beryllium phosphite, [H4tren][Be6(HPO3)8]·(H2O)3 (1, tren = tris(2-aminoethyl)amine), was synthesized under solvothermal conditions. Its structure features a 3D interrupted network with a low density (1.594 g cm−3), and 1 represents the first example of a beryllium phosphite material with extra-large 18-ring channels. [ABSTRACT FROM AUTHOR]

Two novel Fe II -oxalate framework with the formulas of [NH 4 ][Fe II Li 3 (C 2 O 4 ) 3 ] ( 1 ) and [NH 4 ] 2 [Fe II (C 2 O 4 ) 2 ]·H 2 O ( 2 ) have been prepared by an oxalic acid flux approach and structurally characterized by IR, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Heterometallic compound 1 displays a three-dimensional (3D) framework with a pto topology, while homometallic compound 2 features a pillar-layer architecture with a hms topology. Thermal analysis indicates that the two compounds can be stable up to 300 °C and 200 °C, respectively. Magnetic investigations suggest that the Fe II ions in 1 and 2 exhibit weak magnetic exchange interactions. [ABSTRACT FROM AUTHOR]

Two organically templated beryllium phosphite and phosphate, [H2tmpda][Be3(HPO3)4] ( 1) and [H2ampy][Be3(HPO4)4] ( 2) [tmpda = N,N,N′,N′-tetramethyl-1,3-propanediamine, ampy = 3-(aminomethyl)pyridine], were synthesized and structurally characterized. Compound 1 exhibits a (3,4)-connected layered structure with eight-ring windows, and it has a 44 grid topology by regarding the heptameric [Be3(HPO3)4] group as a 4-connected node in the layer. Compound 2 possesses a different (3,4)-connected three-dimensional framework with multidirectional 8-ring channels and zigzag 12-ring channels. This 3D architecture shows a pcu topology when the heptameric [Be3(HPO4)4] groups are regarded as 6-connected secondary building units. Crystal data: 1, monoclinic, P21/ m, a = 8.0217(6) Å, b = 13.7969(5) Å, c = 8.6581(2) Å, β = 92.315(3)°, V = 957.45(8) Å3, Z = 2, R1 = 0.0761, wR2 = 0.1640; 2, monoclinic, P21/ n, a = 7.5292(5) Å, b = 14.0999(8) Å, c = 16.5910(3) Å, β = 95.740(3)°, V = 1752.49(16) Å3, Z = 4, R1 = 0.0434, wR2 = 0.1017. [ABSTRACT FROM AUTHOR]

Three new organically templated zinc phosphates, namely, [dmdabco][Zn2(HPO4)3]·(H2O) (1), [tmpip]0.5[Zn2(HPO4)2(H2PO4)] (2) and [tmpip][Zn3(HPO4)4] (3) (dmdabco=N,N′-dimethyl-1,4-diazabicyclo[2,2,2]octane, tmpip=N,N,N′,N′-tetramethyl-piperazinium), were successfully synthesized under solvothermal reactions and structurally characterized by single-crystal X-ray diffraction. The dmdabco2+ and tmpip2+ templating agents were derived respectively from simple in situ N-alkylation transformations between the methanol solvent and organic cyclic aliphatic diamines, 1,4-diazabicyclo[2,2,2]octane (dabco) in 1 and 1-methylpiperazine in 2 and 3. Such direct methylation feature is unique, and quite different from conventional Eschweiler-Clarke methylation in which an excess of formic acid and formaldehyde was required. Compound 1 exhibits a 4-connected 2D (4, 4) net with pentameric [Zn2(HPO4)3] clusters as secondary building units (SBUs); 2 possesses a complex double layered structure with 12-ring windows. Compound 3 has a (3, 4)-connected 3D pcu architecture with heptameric [Zn3(HPO4)4] clusters as SBUs, forming intersecting 8- and 12-ring channels. [ABSTRACT FROM AUTHOR]

Abstract: Employing the common pyridine (=py) solvent as the source of structure-directing agents (SDAs), a novel three-dimensional open-framework beryllium phosphite (Hpy)4[Be6(HPO3)8]·H2O (1), has been solvothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. It crystallizes in the orthorhombic system, space group Pbca (No. 61), a = 20.0034(4) Å, b = 20.2188(4) Å, c = 20.9731(3) Å, V = 8482.5(3) Å3, and Z = 8. The alternating connection of BeO4 tetrahedra and HPO3 pseudopyramids give rise to a (3, 4)-connected network with multidirectional intersecting 12-ring channels. The compound possesses a low density and a new {4.8.10}{42.6.8.10.12}{42.6}3{42.8.102.12}{43.62.8} topology. [Copyright &y& Elsevier]

Abstract: Two new organically templated zinc phosphites, [H2 dmpip][Zn3(HPO3)4] (1) and [HMedmpip][Zn3(HPO3)4] (2), where dmpip =2,6-dimethyl-piperazine and Medmpip = N-methyl-2,6-dimethyl-piperazinium, have been synthesized and structurally characterized. Note that the new Medmpip 2+ template in 2 is generated from in situ N-methylation reaction between CH3OH and the dmpip amine precursor, which is used to serve as template in 1. Such direct N-methylation transformation is unique, and quite different from conventional Eschweiler–Clarke methylation in which an excess of formic acid and formaldehyde was required. Both compounds are constructed from strictly alternating ZnO4 and HPO3 units, and possess different (3,4)-connected interrupted frameworks with intersecting 8-, 10- and 12-ring channels (for 1), and 8-, 12-ring channels (for 2), respectively. The occurrence of helical channels in the open structure of 1, and fascinating hydrogen-bonded helices between the host inorganic chains and guest organic templates are also noteworthy. [Copyright &y& Elsevier]

Abstract: A novel 3d-4f heterometallic coordination polymer, {[Tm5(μ3-OH)2(BDC)6(IN)2Cu(H2O)2]·(H2O)3}n (1) [BDC = benzene-1,2-dicarboxylate, IN = isonicotinate], has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. The compound crystallizes in monoclinic system, space group P21 /c (No. 14), a = 13.7302(5) Å, b = 23.5428(3) Å, c = 21.5789(2) Å, β = 91.491(3)°, V = 6973.0(3) Å3, and Z = 4. The structure exhibits unusual two-dimensional Tm-carboxylate layer, which is constructed from the expansion of novel pentanuclear {Tm5} clusters. More interestingly, the heterometallic Cu(I) ions were successfully planted into such Ln-carboxylate layer by the bifunctional IN bridging ligands, resulting in the formation of an unprecedented 2D heterometallic lanthanide-transition-metal framework. [Copyright &y& Elsevier]

Two new gallium phosphate/phosphite-oxalates hybrid solids, {[H 2 dmpip][Ga 2 (HPO 4 ) 2 (PO 4 )(C 2 O 4 ) 0.5 ]·H 2 O} ( 1 ) and [H 2 apm][Ga 2 (H 2 PO 3 ) 2 (HPO 3 ) 2 (C 2 O 4 )] ( 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 1 possesses a two-dimensional layer structure, in which the C 2 O 4 units via an in-plane linkage connect two Ga center within the sheet. While in 2 , the C 2 O 4 units serve as bis-bidentates ligands bridging two GaO 6 octahedra from two distinct 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 interlayer region and interact with the layers by way of hydrogen-bonds. [ABSTRACT FROM AUTHOR]

Three new organically templated beryllium phosphate and phosphites, [C 2 H 8 N][Be 2 (PO 4 ) (HPO 4 ) (H 2 O)]·(H 2 O) 0.5 ( 1 ), [C 3 H 12 N 2 ][Be 3 (HPO 3 ) 4 ] ( 2 ) and [C 6 H 18 N 2 ][Be 3 (HPO 3 ) 4 ] ( 3 ), have been synthesized and structurally characterized by single-crystal X-ray diffraction analyses. The structure of 1 consists of BeO 4 and PO 4 tetrahedra, displaying a double-layered structure with [Be 4 (PO 4 ) 2 (HPO 4 ) 2 (H 2 O) 2 ] D4R-analogue as SBUs. Compound 2 presents a three-dimensional (3D) interrupted open-framework, constructed from two-dimensional layers pillared by phosphite nodes. Left- and right-handed helical channels occurred along the [010] direction in 2 . For 3 , adjacent sheets arrange in an –ABAB– staggered stacking mode to give a (3,4)-connected 3D structure with zigzag 12-ring channels. In 1 – 3 , different protonated amine templates reside in the voids of structures and interact with the inorganic frameworks through hydrogen-bonds. [ABSTRACT FROM AUTHOR]

Employing diethylenetriamine (=dien) as a structure-directing agent, a new open-framework beryllium phosphite H2dien·Be3(HPO3)4 (1), has been synthesized hydrothermally and structurally characterized by single crystal X-ray diffraction. The structure of 1 features a (3, 4)-connected framework with 8- and 12-ring channels, which is constructed from strictly alternating BeO4 tetrahedra and HPO3 2− pseudopyramids. The 3-D framework possesses a pcu topology when the heptameric [Be3(HPO3)4] clusters are regarded as 6-connected secondary building units. Crystal data: 1, monoclinic, C2/c (no. 15), a = 8.7350(3) Å, b = 15.1704(6) Å, c = 13.0851(4) Å, β = 101.223(5)°, V = 1700.79(10) Å3, Z = 4, R 1 = 0.0625, wR 2 = 0.1692. [ABSTRACT FROM AUTHOR]

Abstract: By using flexible 1,2-bis(2-aminoethoxy)ethane (BAEOE) as a pillaring ligand, a new inorganic–organic hybrid open-framework zinc phosphite, [C6N2O2H16][Zn(HPO3)]2 (1), has been hydrothermally synthesized and structurally characterized by IR, elemental analysis, thermogravimetric analysis, powder and single-crystal X-ray diffractions. The structure of 1 consists of neutral layers of zinc phosphite which are further pillared through linear BAEOE ligands, generating a 3D framework with unusual (3, 4)-connected dmc topology. The participation of left-handed and right-handed helical chains in the construction of puckered sheet structure with 4.82-net is also noteworthy. [Copyright &y& Elsevier]

Abstract: Two new three-dimensional open-framework zinc phosphites, [HCHA]2[Zn3(HPO3)4] (1) and [HCHPA]2[Zn3(HPO3)4] (2), have been synthesized under hydrothermal conditions, where CHA = cyclohexylamine and CHPA = cycloheptylamine. Both compounds are isostructural and exhibit a similar three-dimensional 3, 4-connected framework constructed by strictly alternating ZnO4 tetrahedra and pseudopyramids. The occurrence of extra-large tubular channels constructed by the concatenation of 24- and 30-ring windows along the [001] direction in the two structures is very unusual in known extra-large micropore materials. Crystal data: 1, rhombohedral, R-3, a = 32.9618(5) Å, c = 13.2818(3) Å, V = 12497.1(4) Å3, Z = 18, R 1 = 0.0445, wR 2 = 0.1068; 2, rhombohedral, R-3, a = 33.2184(4) Å, c = 13.1697(6) Å, V = 12585.3(6) Å3, Z = 18, R 1 = 0.0401, wR 2 = 0.0974. [Copyright &y& Elsevier]

The hydrothermal reaction of zinc ions with 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) in the presence of additives such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,3-propanediamine, imidazole and isonipecotic acid, afforded five metal phosphonates, namely, [H 2 DABCO]{Zn 3 [CH 3 C(OH)(PO 3 ) 2 ] 2 } ( 1 ), [C 3 H 14 N 2 ]{Zn 3 [CH 3 C(OH)(PO 3 ) 2 ] 2 } ( 2 ), [C 3 H 5 N 2 ] 2 {Zn 3 [CH 3 C(OH)(PO 3 ) 2 ] 2 } ( 3 ), {Zn 2 [CH 3 C(OH)(PO 3 ) 2 ][C 3 H 4 N 2 ] 2 } ( 4 ) and {Zn 2 [CH 3 C(OH)(PO 3 ) 2 ][C 6 H 11 NO 2 ] 2 [H 2 O] 2 }·H 2 O ( 5 ). Compounds 1 and 2 are isostructural and adopt a pillar-layered 3D structure. Compound 3 is a 3D framework in which [ZnO 4 ] tetrahedra are connected by HEDP molecules with tetradentate mode. The [ZnO 3 N] tetrahedra in 4 shares corners with the [CPO 3 ] tetrahedra into a 3D framework with twelve-membered ring. It is also found that 4 displays interesting left-handed helical chains along [100] direction. In 5 , HEDP molecules exhibit tetradentate coordination fashion to combine Zn atoms into a complicated 2D hybrid layer, resulting in the coordinated isonipecotic acid rings being sandwiched between the layers. All the compounds have been characterized by infrared spectra (IR), elemental analyses, powder X-ray diffraction (PXRD) and thermogravimetric (TG) analyses. [ABSTRACT FROM AUTHOR]

A series of aluminophosphates (AlPOs) with open architectures, namely [ dmdabco ][Al 2 (HPO 4 ) 4 ] ( 1 , dmdabco = N , N -dimethyl-1,4-diazabicyclo[2,2,2]octane), [ tmpip ] 0.5 [Al(HPO 4 ) 2 ] ( 2 , tmpip = N,N,N,N-tetramethylpiperazinium) and [ tmpip ][Al 6 (PO 4 ) 6 (HPO 4 )] ( 3 ) have been solvothermally synthesized and structurally characterized. The in situ generated templates ( dmdabco 2+ and tmpip 2+ ) originated from the methylation reactions between methanol solvent and their corresponding aliphatic organic-amine parents: 1,4-diazabicyclo[2,2,2]octane ( dabco ) for 1 , 1-methylpiperazine for 2 and 3 . Such a characteristic in situ methylation is distinct from conventional Eschweiler–Clarke methylation with excessive formic acid and formaldehyde. Compounds 1 and 2 possess the same infinite inorganic chains, which are further linked by hydrogen bonds to form 3D supramolecular framework. Compound 3 is built from Al 6 P 6 and Al 6 P 8 building units, giving rise to an open architecture with three-dimensional channel system. [ABSTRACT FROM AUTHOR]