Zinc Phosphite Research Articles

A novel layered bimetallic phosphite intercalating with organic amines: Synthesis and characterization of Co(H 2O) 4Zn 4(HPO 3) 6·C 2N 2H 10

A new layered cobalt–zinc phosphite, Co(H 2O) 4Zn 4(HPO 3) 6·C 2N 2H 10 has been synthesized in the presence of ethylenediamine as the structure-directing agent. The compound crystallizes in the monoclinic system, space group Cc (No. 9), a=18.2090(8), b=9.9264(7), c=15.4080(7) Å, β=114.098(4)°, V=2542.3(2) Å 3, Z=4, R=0.0323, w R=0.0846. The structure consists of ZnO 4 tetrahedra, CoO 6 octahedra and HPO 3 pseudopyramids through their vertices forming bimetallic phosphite layers parallel to the ab plane. Organic cations, which reside between the inorganic layers, are mobile and can be exchanged by NH 4 + cations without the collapse of the framework.

A tetranuclear zinc cluster, (bipy) 4Zn 4(HPO 3) 4, that stabilizes a hydrogen bonded chain of water molecules: Transformation of a zinc phosphite 4-ring to a cluster

An infinite chain of hydrogen bonded loops of 8 and 10 water molecules are stabilized by the neutral zinc phosphite cluster [Zn 4(HPO 3) 4(2,2′-bipy) 4] · 11H 2O. The cluster is prepared either by direct synthesis or by transformation of a (2,2′-bipy) 2Zn 2(HPO 3) 2 4-ring.

Synthesis and Characterization of a New Layered Zinc Phosphite (NH4)[{Zn(H2O)4}0.5Zn2(HPO3)3

AbstractA new layered zinc phosphite with the formula (NH4)[{Zn(H2O)4}0.5Zn2(HPO3)3] has been synthesized under hydrothermal conditions. Its structure was determined by single‐crystal X‐ray diffraction. The compound crystallizes in the triclinic system, space group $P{\bar 1}$ (No. 2), a = 7.2507(4), b = 9.7982(6), c = 10.2642(6) Å, α = 63.425(2), β = 87.165(2), γ = 72.999(3)°, V = 620.84(6) Å3, Z = 2. The connectivity of ZnO4 tetrahedra, HPO3 pseudo pyramids and ZnO2(H2O)4 octahedra results in macroanionic layers with 4.8 net.

Synthesis and Characterization of a Two-Dimensional Zinc Phosphite, Zn3(tren)(HPO3)3·xH2O (x ≈ 0.5; tren = tris(2-aminoethyl)amine)

A new zinc phosphite with the formula Zn3(tren)(HPO3)3·xH2O (x≈0.5) has been synthesized under hydrothermal conditions and characterized by FTIR, elemental analysis, powder X-ray diffraction, single-crystal X-ray diffraction, thermogravimetric analysis and its fluorescent spectrum. The compound crystallizes in the triclinic system, space group (No.2), a = 10.1188(9) Å, b = 10.4194(9) Å, c = 10.5176(9) Å, α = 60.763(2)°, β = 70.6150(10)°, γ = 80.725(2)°, V = 912.77(14) Å3, Z = 2. The structure consists of double crankshaft chains, which are linked by Zn-O-P bonds to form 8- and 12-membered channels along the [100] direction. The claw-like Zn-centered complexes of Zn(N4C6H18) as the supported templates, hang into the 12-MR channels through Zn-O-P linkages with framework.

Synthesis and characterization of two new open-framework zinc phosphites [ M(C 6N 4H 18)][Zn 3(HPO 3) 4] ( M=Ni, Co) with multi-directional intersecting 12-membered ring channels

Two new open-framework zinc phosphites, [ M(C 6N 4H 18)][Zn 3(HPO 3) 4] ( M=Ni, Co), have been prepared under hydrothermal conditions. Single-crystal X-ray diffraction analysis shows that [Ni(C 6N 4H 18)][Zn 3(HPO 3) 4] ( 1) and [Co(C 6N 4H 18)][Zn 3(HPO 3) 4] ( 2) are isostructural and both crystallize in the monoclinic space group C2/ c with a = 15.325 ( 3 ) Å , b = 9.792 ( 2 ) Å , c = 14.514 ( 3 ) Å , β = 109.83 ( 3 ) °, V = 2048.8 ( 7 ) Å 3 , Z = 4 , R 1 = 0.0408 ( I > 2 σ ( I ) ), and w R 2 = 0.1104 (all data) for 1, and a = 15.277 ( 2 ) Å , b = 9.8831 ( 13 ) Å , c = 14.534 ( 2 ) Å , β = 109.328 ( 2 ) ° , V = 2070.7 ( 5 ) Å 3 , Z = 4 , R 1 = 0.0380 ( I > 2 σ ( I ) ), and w R 2 = 0.1093 (all data) for 2. The structures of 1 and 2 are built up from strictly alternating ZnO 4 tetrahedra and HPO 3 pseudo-pyramids linked through oxygen vertices to form the three-dimensional (3-D) open-frameworks with multi-directional intersecting 12-membered ring (12-MR) channels. The M(TETA) ( M=Ni, Co) complexes self-assembled under hydrothermal system connect with the inorganic host via M–O–P linkages and interact with inorganic framework through weak H-bonds. The two compounds show intense photoluminescence upon photoexcitation at 235 nm.

Syntheses and characterization of two new zinc phosphites with 1D chains decorated by Zn-centered complexes

Two inorganic–organic hybrid solids, Zn 2(phen)(HPO 3) 2 ( 1) and Zn(phen)(HPO 3) ( 2), have been synthesized under solvothermal conditions in the presence of 1,10-phenanthroline (phen) ligands. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectra. Compound 1 crystallizes in the triclnic system, space group P-1, a = 8.1813 ( 3 ) Å , b = 8.5535 ( 3 ) Å , c = 12.3031 ( 5 ) Å , α = 75.609 ( 1 ) ° , β = 79.145 ( 2 ) ° , γ = 67.157 ( 2 ) ° , V = 764.46 ( 5 ) Å 3 , Z = 2 . Compound 2 is monoclinic, C 2 / c , a = 16.1044 ( 7 ) Å , b = 18.9447 ( 6 ) Å , c = 8.1713 ( 6 ) Å , β = 94.175 ( 4 ) ° , V = 2486.4 ( 2 ) Å 3 , Z = 8 . Both structures consist of 1D chains constructed from strictly alternating ZnO 4 and HPO 3 polyhedra through sharing vertices. The chains are further decorated by Zn-centered complex architectures, [Zn(phen)] 2+ for 1 and [Zn(phen) 2] 2+ for 2. The 2D and 3D supramolecular arrays for 1 and 2 are stably stacked via strong π– π interactions of the phen groups, respectively.

Five New Zinc Phosphite Structures: Tertiary Building Blocks in the Construction of Hybrid Materials

The syntheses and structures of five new zinc phosphites [Zn(HPO(3))(C(4)H(6)N(2))] (1), [Zn(2)(HPO(3))(2)(C(10)H(10)N(2))(2)](2) (2), [Zn(HPO(3))(C(14)H(14)N(4))(0.5)] (3), [Zn(2)(HPO(3))(2)(C(14)H(14)N(4))].0.4H(2)O (4), and [Zn(2)(HPO(3))(2)(C(14)H(14)N(4))] (5) are reported. In compounds 1-3, the zinc atoms are ligated by 1-methylimidazole, 1-benzylimidazole, and 1,4-bis(imidazol-1-ylmethyl)benzene, respectively, while compounds 4 and 5 are synthesized in the presence of the same bifunctional ligand, 1,3-bis(imidazol-1-ylmethyl)benzene. The inorganic framework of compound 1 is composed of vertex-shared ZnO(3)N and HPO(3) tetrahedra that form 4-rings, which, in turn, are linked to generate a one-dimensional ladder structure. In 2, the inorganic framework is composed of 4-rings and 8-rings to form the well-known 4.8(2) 2D network. This is connected via C-H...pi interactions between 1-benzylimidazole ligand to generate a pseudo-pillared-layer structure. In 3, the inorganic framework again has the 4.8(2) topology pillared by the bis(imidazole) ligand, 1,3-bis(imidazol-1-ylmethyl)benzene. In 4, a new layer pattern is observed. Specifically, three edge-sharing 4-rings form triple-fused 4-rings. These tertiary building units are further connected to form 12-rings. The alternating triple 4-rings and 12-rings form a previously unknown 2D inorganic sheet. The sheets are joined together by the bis(imidazole) ligand, 1,3-bis(imidazol-1-ylmethyl)benzene, to generate a 3D pillared-layer structure. In 4, benzene rings and imidazole rings stack in a zigzag pattern in the interlayer space. A significant role for the triple 4-ring tertiary building unit in the formation of hybrid inorganic/organic metal phosphite structures is proposed for 4 and 5. In 5, the triple 4-rings fuse to give a 1D stair-step structure. Calculations show that the triple 4-ring pattern observed in the linear ladder structure of 1 is more stable than that in the stair step pattern of 5.

Syntheses and Characterization of Two New Open-Framework Zinc Phosphites with 12-Ring Channels, [H3N(CH2)4NH3]·[Zn3(HPO3)4]·H2O and [C3N2H5]2·[Zn3(HPO3)4

Two new organically templated zinc phosphites, [H3N(CH2)4NH3]·[Zn3(HPO3)4]·H2O (1) and [C3N2H5]2·[Zn3(HPO3)4] (2) have been synthesized under mild hydrothermal conditions. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, inductively coupled plasma (ICP) analysis, powder X-ray diffraction, and thermogravimetric analysis. In addition to the same anionic framework compositions of [Zn3(HPO3)4]2-, both phases consist of strictly alternating ZnO4 tetrahedra and HPO3 pseudo-pyramids linked through their vertexes to generate the three-dimensional frameworks with intersecting 8- and 12-membered ring channels, where the template molecules reside. Compound 1 crystallizes in the triclinic system, space group P1 with the following cell parameters: a = 7.7703(4) A; b = 9.1499(4) A; c = 14.4685(3) A; α = 89.965(2)°; β = 87.050(2)°; γ = 65.332(2)°; V = 933.31(7) A3; Z = 2. Compound 2 crystallizes in the triclinic system, space group P1 with the...

Organically Templated Zinc Selenites: MIL‐86 or [H2N(CH2)2NH2] 2×Zn4(SeO3)4 and MIL‐87 or [H3N(CH2)3NH3] 4×Zn4(SeO3)8.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Synthesis and characterization of a new inorganic–organic hybrid open-framework zinc phosphite: (C 6N 3H 12) 2 · Zn 5(HPO 3) 6

A new inorganic–organic hybrid open-framework zinc phosphite, (C 6N 3H 12) 2 · Zn 5(HPO 3) 6, has been hydrothermally synthesized in the presence of 1-(3-aminopropyl)imidazole amine as a structure-directing agent. Its structure was determined by single-crystal X-ray diffraction and further characterized by powder X-ray diffraction (PXRD), IR spectroscopy, ICP, elemental, and TG analyses. This compound crystallizes in the orthorhombic system, space group C222 1 (no. 20), a = 9.9512(4), b = 14.7129(6), c = 22.50660(10) Å, V = 3295.21(19) Å 3, Z = 4. The connectivity of the strictly alternating Zn-centered tetrahedra and HPO 3 pseudopyramids results in a 3D framework with intersecting 8- and 12-membered ring channels, where organic amines reside. It is worth noting that the title compound is the first metal phosphite to be prepared with a metal: phosphorus ratio of 5:6.

Building three-dimensional metal phosphites from the corner-shared four-membered rings chain

Three new compounds, a one-dimensional (1D) zinc phosphite, (C 4H 8N 2H 4)[Zn(HPO 3) 2] ( I), two three-dimensional (3D) metal phosphites (C 4H 8N 2H 4)[Zn 3(HPO 3) 4] ( II) and (C 4H 8N 2H 4)[Zn (3− x) Co x (HPO 3) 4(H 2O) 2] ( x≈0.83) ( III) have been synthesized under hydrothermal conditions templated by piperazine and characterized by single-crystal X-ray diffraction, XRD, IR, UV-vis spectra and SQUID magnetometer. Compound I displays 1D chain-like structure, containing corner-shared (cs) four-membered rings. Interestingly, the structures of II and III show 1D chains similar to those observed in I. It is noteworthy that III represents the first cobalt-substituted zinc-phosphite. Crystal data: I, monoclinic, C2/ c, a=17.748(2) Å, b=7.428(9) Å, c=8.8071(11) Å, β=105.345(3)°, V=1091.9 Å 3, Z=4. II, Monoclinic P2 1/ c, a=9.9435(4) Å, b=10.1438(3) Å, c=17.8164(5) Å, β=95.665(2)°, V=1788.27 Å 3, Z=4, and III, Monoclinic P2 1/ c, a=7.2338(2) Å, b=15.0238(5) Å, c=9.2153(3) Å, β=107.741(2)°, V=953.88(5) Å 3, Z=2.

Synthesis and Characterization of Organically Templated Zinc Phosphites with Two‐ and Three‐Dimensional Structures, (C2N2H10)Zn2 (HPO3)3 and (C4N2H12)Zn3 (HPO3)4.

AbstractFor Abstract see ChemInform Abstract in Full Text.

A Novel Open‐Framework Zinc Phosphite, Zn3(HPO3)4×Ni(en)2 (H2O)2, Templated by a Transition‐Metal Complex.

AbstractFor Abstract see ChemInform Abstract in Full Text.

Two zincophosphite frameworks templated by 1,4-diaminobenzene: syntheses and structures of C 6N 2H 10·Zn(HPO 3) 2 and (C 6N 2H 8) 0.5·ZnHPO 3

The solution-mediated syntheses and single crystal structures of C 6N 2H 10·Zn(HPO 3) 2 ( I) and (C 6N 2H 8) 0.5·ZnHPO 3 ( II) are reported. Slight variation of the synthesis conditions led to two quite different phases. I contains infinite chains of ZnO 4 and HPO 3 groups with the protonated organic moiety acting as a template and interacting with the chains by NH⋯O hydrogen bonds and possible CH⋯O interactions. In II, the neutral 1,4-diamino benzene molecule bonds to Zn (as a ligand) and an unusual composite, “pillared”, structure results, with the organic species bridging 6 3 polyhedral sheets, although NH⋯O bonds are also present. Similarities and differences to other zinc phosphites and phosphates are briefly discussed for I and II. Crystal data: C 6N 2H 10·Zn(HPO 3) 2, M r=335.48, monoclinic, C2/ c (No. 15), a=17.2471 (14) Å, b=9.0720 (8) Å, c=7.6529 (6) Å, β=103.752 (2)°, V=1163.09 (7) Å 3, Z=4, R( F)=0.038, wR( F 2)=0.084. (C 6N 2H 8) 0.5·ZnHPO 3, M r=199.42, orthorhombic, Pbca (No. 61), a=8.0314 (16) Å, b=8.1299 (16) Å, c=18.830 (4) Å, V=1229.5 (4) Å 3, Z=8, R( F)=0.026, wR( F 2)=0.055.

Synthesis and characterization of organically templated zinc phosphites with two- and three-dimensional structures, (C 2N 2H 10)Zn 2(HPO 3) 3 and (C 4N 2H 12)Zn 3(HPO 3) 4

Two organically templated zinc phosphites, (C 2N 2H 10)Zn 2(HPO 3) 3 ( 1) and (C 4N 2H 12)Zn 3(HPO 3) 4 ( 2), were hydrothermally synthesized and structurally characterized. Compound 1 crystallized in the triclinic system, space group P-1 (No. 2), a=8.6357(14) Å, b=8.8197(14) Å, c=9.9665(16) A ̊ , α=64.645(2), β=65.922(2), γ=81.049(2)°, V=626.12(17) A ̊ 3 , Z=2. The connectivity of the strictly alternating ZnO 4 and HPO 3 polyhedra results in infinite macroanionic layers with 4.8-net. The organic cations locate in the interlayer region and hold the macroanionic sheets together by strong H-bonds. Compound 2 crystallized in the monoclinic system, space group P2 1/ c (No. 14), a=9.9352(14) A ̊ , b=10.1487(14) A ̊ , c=17.8257(13) A ̊ , β=95.701(7), V=1788.5(4) A ̊ 3 , Z=4. The structure of 2 consists of ZnO 4 tetrahedra and HPO 3 pseudo-pyramids with shared vertices, forming a 3D framework with 8-ring channels. Both compounds were characterized by FTIR, elemental analysis, ICP analysis and thermogravimetric analysis.

A Novel Open‐Framework Zinc Phosphite, Zn3(HPO3)4·Ni(en)2(H2O)2, Templated by a Transition‐Metal Complex

AbstractA new three‐dimensional zinc phosphite, Zn3(HPO3)4· Ni(en)2(H2O)2, which is the first example of an open‐framework metal phosphite templated by a transition‐metal complex, was hydrothermally synthesized. The connectivity of the strictly alternating ZnO4 and HPO3 units results in a three‐dimensional framework with intersecting 8‐ring and 12‐ring channels, in which the transition‐metal complexes reside. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Organically templated zinc selenites: MIL-86 or [H 2N(CH 2) 2NH 2] 2·Zn 4(SeO 3) 4 and MIL-87 or [H 3N(CH 2) 3NH 3] 4·Zn 4(SeO 3) 8

Two new organically templated zinc selenites MIL-86 or [H 2N(CH 2) 2NH 2] 2·Zn 4(SeO 3) 4 and MIL-87 or [H 3N(CH 2) 3NH 3] 4·Zn 4(SeO 3) 8 have been prepared by the reaction of ZnO with SeO 2 under hydrothermal conditions in the presence of organic amines. Crystal data: MIL-86, monoclinic, space group P2 1/ n, a=6.7712(4) Å, b=9.4520(5) Å, c=8.0295(4) Å, β=113.601(1)°, V=470.91(4) Å 3; MIL-87, orthorhombic, space group Pbcm, a=8.8311(3) Å, b=7.8391(2) Å, c=16.2992(4) Å, V=1128.36(6) Å 3. MIL-86 combines the structural features of templated networks and coordination polymers. Its structure is built up from ZnO 3N tetrahedra and SeO 3 pseudo-pyramids as the polyhedral building units. The ZnN bond corresponds to a direct link between zinc and the ethylenediamine template. In the other hand, MIL-87 is built up from chains of vertex-linked ZnO 4 and SeO 3 building units crosslinked by 1,3-diammonium propane cations. These structures are understood by comparison with the already known organically templated zinc phosphites.

Synthesis and characterization of a new hybrid zinc phosphite (4,4 ′-bipy)[Zn(HPO 3)] 2 with a pillared layer structure

A new inorganic–organic hybrid solid, (4,4 ′-bipy)[Zn(HPO 3)] 2 (4,4 ′-bipy=4,4 ′-bipyridine), has been hydrothermally synthesized in the presence of 4,4 ′-bipy ligand. Its structure was determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, ICP analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectrum. It crystallized in the monoclinic space group, P2 1/ c, with a=9.741(2), b=7.4423(16), c=10.271(2) Å, β=100.038(4)°, V=733.3(3) Å 3, Z=2. The structure consists of neutral sheets of zinc phosphite which is pillared through 4,4 ′-bipy ligands to generate a 3D framework. The compound shows relatively high thermal stability and exhibits intense photoluminescence upon photo-excitation at 362 nm.

Synthesis and characterization of a novel open-framework nickel–zinc phosphite with intersecting three-dimensional 16-ring channels

A new inorganic–organic hybrid solid, Ni(DETA)(H2O)Zn2(HPO3)3 (FJ-14), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, thermogravimetric analysis and magnetic susceptibility measurements. The compound is novel in the sense that it represents the first example of open- framework bimetallic phosphite. The structure of the compound consists of strictly alternating ZnO4 and HPO3 polyhedra through their vertices, forming zinc phosphite layers parallel to the bc plane. These layers are further pillared by Ni2(DETA)2(H2O)2O2 dinuclear units to generate a 3D framework with intersecting three-dimensional 16-ring channels.

Hydrothermal synthesis and structural characterization of novel organically templated zincophosphites: [C 6H 4(CH 2NH 3) 2]·[Zn 3(HPO 3) 4] and [CH 3CH 2CH 2NH 3] 2·[Zn 3(HPO 3) 4

Two novel organically templated zincophosphites, [C 6H 4(CH 2NH 3) 2]·[Zn 3(HPO 3) 4] and [CH 3CH 2CH 2NH 3] 2·[Zn 3(HPO 3) 4] have been synthesized under hydrothermal conditions with different template 1,3-Bis(aminomethyl)benzene and propylamine, and characterized by single-crystal X-ray diffraction. [C 6H 4(CH 2NH 3) 2]·[Zn 3(HPO 3) 4] crystallizes in the monoclinic space group P2 1/ c, with cell parameters, a=9.5467(10) Å, b=26.405(2) Å, c=7.9946(8) Å, and β=99.472(2)°. [CH 3CH 2CH 2NH 3] 2·[Zn 3(HPO 3) 4] crystallizes in the orthorhombic space group Pccn, with cell parameters, a=9.8162(15) Å, b=23.284(4) Å, and c=8.9306(12) Å. Two compounds consist of vertex linking of ZnO 4 tetrahedral and [HPO 3 2−] pseudopyramidal units. They have similar inorganic frameworks with the same compositions. They are both built up from two-dimensional layers with four- and eight-membered rings and one-dimensional chains composed of four-memberd rings, but their layered structures are different due to the influence of corresponding organic template. To our knowledge, [C 6H 4(CH 2NH 3) 2]·[Zn 3(HPO 3) 4] is the first mention of a zinc phosphite material with an aromatic template. Two compounds were also characterized by IR spectroscopy, thermogravimetric and differential thermal analyses, and proton-decoupled 31P MAS solid-state NMR spectroscopy.