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

Three new compounds, a one-dimensional (1D) zinc phosphite, (C₄H₈N₂H₄)[Zn(HPO₃)₂] (I), two three-dimensional (3D) metal phosphites (C₄H₈N₂H₄)[Zn₃(HPO₃)₄] (II) and (C₄H₈N₂H₄)[Zn_(3−x)Co_x(HPO₃)₄(H₂O)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 Å³, Z=4. II, Monoclinic P2₁/c, a=9.9435(4) Å, b=10.1438(3) Å, c=17.8164(5) Å, β=95.665(2)°, V=1788.27 Å³, Z=4, and III, Monoclinic P2₁/c, a=7.2338(2) Å, b=15.0238(5) Å, c=9.2153(3) Å, β=107.741(2)°, V=953.88(5) Å³, Z=2.     

Synthesis, structure of [H3dien]·(MF6)·H2O (M=Cr, Fe) and Fe Mössbauer study of [H3dien]·(FeF6)·H2O

Single crystals of [H₃dien]·(FeF₆)·H₂O (I) and [H₃dien]·(CrF₆)·H₂O (II) are obtained by solvothermal synthesis under microwave heating. I is orthorhombic (Pna2₁) with a=11.530(2) Å, b=6.6446(8) Å, c=13.787(3) Å, V=1056.3(2) Å³ and Z=4. II is monoclinic (P2₁/c) with a=13.706(1) Å, b=6.7606(6) Å, c=11.3181(9) Å, β=99.38(1)°, V=1034.7(1) Å³ and Z=4. The structure determinations, performed from single crystal X-ray diffraction data, lead to the R₁/wR₂ reliability factors 0.028/0.066 for I and 0.035/0.102 for II. The structures of I and II are built up from isolated FeF₆ or CrF₆ octahedra, water molecules and triprotonated amines. In both structures, each octahedron is connected by hydrogen bonds to six organic cations and two water molecules. The iron-based compound is also characterized by ⁵⁷Fe Mössbauer spectrometry: the hyperfine structure confirms the presence of Fe³⁺ in octahedral coordination and reveals the existence of paramagnetic spin fluctuations.     

Hydrothermal synthesis and structures of two novel chain-like heteropolymolybdate formed by Keggin cluster units

Two novel heteropolymolybdate, [H₂bpy]₂ [Hbpy] [PCuMo₁₁O₃₉]·H₂O 1 and [H₂bpy]₂ [Hbpy] [PZnMo₁₁O₃₉]·2.75H₂O 2, have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the monoclinic space group P2(1)/n (No. 14) with a=13.440(3) Å, b=26.660(5) Å, c=15.240(3) Å, β=99.55(3)°, and Z=4 for the compound 1, and a=13.610(3) Å, b=26.781(5) Å, c=15.205(3) Å, β=100.40(3)°, and Z=4 for the compound 2. Compound 1 and 2 exhibit a zigzag chain structure in which Keggin anions are connected through a common oxygen atom. They are the first characterized compounds containing 1D chains of transition-metal substituted Keggin heteropolymolybdate. Other characterizations by elemental analysis, IR, EPR, TG, and XRPD are also described.     

Two new hydrogen bond-supported supramolecular compounds assembly from polyoxovanadate and organoamines

Two novel organic-inorganic hybrid compounds based on organoamines and polyoxovanadates formulated as (H₂dien)₄[H₁₀V₁₈O₄₂(PO₄)](PO₄)·2H₂O (1) (dien=diethylenetriamine) and (Him)₈[HV₁₈O₄₂(PO₄)] (2) (im=imidazole) have been prepared under hydrothermal conditions by using different starting materials, and characterized by elemental analyses, IR, ESR, XPS, TGA and single-crystal X-ray diffraction analyses. Crystal data for compound 1: C₁₆H₇₄N₁₂O₅₂V₁₈P₂, Monoclinic, space group C2/c, a=23.9593(4) Å, b=13.0098(2) Å, c=20.1703(4) Å, β=105.566(3)°, V=6056.6(19) Å³, Z=4; for compound 2, C₂₄H₄₁N₁₆O₄₆V₁₈P, Tetragonal, space group I4/mmm, a=13.5154(8) Å, b=13.5154(8) Å, c=19.1136 Å, β=90°, V=3491.4(3) Å³, Z=2. Compound 1 consists of protonated diens together with polyoxovanadates [H₁₀V₁₈O₄₂(PO₄)]⁵⁻. Compound 2 is composed of protonated ims and polyoxovanadates [HV₁₈O₄₂(PO₄)]⁸⁻. There are hydrogen-bonding interactions between polyoxovanadates and different organoamines in 1 and 2. Polyoxovanadates are linked through H₂dien into a three-dimensional network via hydrogen bonds in 1, while polyoxovanadates are linked by Him into a two-dimensional layer network via hydrogen bonds in 2. The crystal packing patterns of the two compounds reveal various supramolecular frameworks.     

Unusual one-dimensional branched-chain structures assembled by a novel imidazole-containing tripodal ligand with cadmium(II) salts and their fluorescent property

Three novel coordination polymers [Cd₃(L)₂(μ-Br)(μ-Cl)Br₃Cl] (1), [Cd₃(L)₂(μ-Cl)₂Cl₄] (2) and [Cd(L)Cl]₂[CdCl₄]·H₂O (3) were obtained by reactions of an imidazole-containing tripodal ligand N¹-(2-aminoethyl)-N¹-(2-imidazolethyl)-ethane-1,2-diamine (L) with Cd(II) salts. Their structures were determined by X-ray crystallography. Crystal data for 1, monoclinic system, P2₁/c, a=7.752(4) Å, b=31.70(2) Å, c=14.012(7) Å, β=109.439(7)°, V=3247(3) Å³, Z=4. 2, monoclinic system, P2₁/c, a=7.6564(15) Å, b=31.433(6) Å, c=13.925(3) Å, β=109.89(3)°, V=3151.1(11) Å³, Z=4. 3, orthorhombic system, Pbcn, a=22.950(2) Å, b=8.435(7) Å, c=17.360(2) Å, V=3360.3(51) Å³, Z=4. Complexes 1 and 2 have similar one-dimensional (1D) branched-chain structure while complex 3 features a 1D zigzag cationic chain with [CdCl₄]²⁻ serving as counter anion. The photoluminescent measurements reveal that all the complexes exhibit blue fluorescence at room temperature in the solid state.     

Crystal chemistry of thorium nitrates and chromates

The structures and infrared spectra of six novel thorium compounds are reported. Th(NO₃)₂(OH)₂(H₂O)₂ (1) crystallizes in space group C2/c, a=14.050(1), b=8.992(7), c=5.954(5) Å, β=101.014(2)°. K₂Th(NO₃)₆ (2), P-3, a=13.606(1), c=6.641(6) Å. (C₁₂H₂₈N)₂Th(NO₃)₆ (3), P2₁/c, a=14.643(4), b=15.772(5), c=22.316(5) Å, β=131.01(1)°. KTh(NO₃)₅(H₂O)₂ (4), P2₁/c, a=10.070(8), b=12.731(9), c=13.231(8) Å, β=128.647(4)°. Th(CrO₄)₂(H₂O)₂ (5), P2₁/n, a=12.731(1), b=9.469(8), c=12.972(1) Å, β=91.793(2)°. K₂Th₃(CrO₄)₇(H₂O)₁₀ (6), Ama2, a=19.302(8), b=15.580(6), c=11.318(6) Å. The coordination polyhedra about Th in these structures are diverse. Th is coordinated by 9 O atoms in 5 and 6, seven of which are from monodentate (CrO₄) tetrahedra and two are (H₂O). The Th in compound 1 is coordinated by ten O atoms, four of which are O atoms of two bidentate (NO₃) triangles and six of which are (OH) and (H₂O). In compounds 2, 3 and 4 the Th is coordinate by 12 O atoms. In 2 and 3 there are six bidentate (NO₃) triangles, and in 4 ten of the O atoms are part of five bidentate (NO₃) triangles and the others are (H₂O) groups. The structural units of these compounds consist of a chain of thorium and nitrate polyhedra (1), isolated thorium hexanitrate clusters (2, 3), an isolated thorium pentanitrate dihydrate cluster (4), and a sheet (6) and framework (5) of thorium and chromate polyhedra. These structures illustrate the complexity inherent in the crystal chemistry of Th.     

Ab-initio crystal structure of hydroxy adipate of nickel and hydroxy subarate of nickel and cobalt from synchrotron powder diffraction and magnetic properties

Organic-inorganic hybrid compounds Ni(II)₅(OH)₆(C₆H₈O₄)₂(1), Ni(II)₅(OH)₆(C₈H₁₂O₄)₂(2) and Co(II)₅(OH)₆(C₈H₁₂O₄)₂(3) have a similar layered structure as determined ab initio from synchrotron powder diffraction analysis. The metal sites are octahedrally coordinated by O atoms. The slabs are built from edge-sharing octahedra in such a way that channels with an average size of 4 Å are formed. Bis-bidentate and bridging dicarboxylate anions lead to a 3D framework. The compounds (1) and (2) order antiferromagnetically below T_N=26.5 and 19.3 K, respectively, while (3) is ferrimagnetic with T_C=16.2 K. Crystal data for compounds are as follows: (1)a=11.6504(1) Å, b=6.8021(3) Å, c=6.3603(1) Å, α=73.52(1)°, β=99.69(1)°, γ=96.16(1)°, R_B=0.070, 668 reflections; (2)a=13.9325(1) Å, b=6.7893(1) Å, c=6.3534(4) Å, α=73.63(1)°, β=95.14(1)°, γ=91.80(1)°, R_B=0.052, 804 reflections; (3)a=13.9806(1) Å, b=6.9588(1) Å, c=6.3967(1) Å, α=73.05(1)°, β=94.51(1)°, γ=92.19(1)°, R_B=0.048, 410 reflections. The space group is P−1 for the three compounds.     

An unprecedented extended architecture constructed from a 2-D interpenetrating cationic coordination framework templated by SiW12O40 anion

A novel inorganic-organic hybrid compound based on polyoxometalates (POMs) and organic ligand formulated as [Cu₂(bpp)₄(H₂O)₂](SiW₁₂O₄₀)∼6H₂O (1) [bpp=1,3-bis(4-pyridyl)propane], was hydrothermally synthesized and structurally characterized by elemental analysis, single-crystal X-ray diffraction analysis, IR, TG, and cyclic voltammetry. Crystal data for 1: Orthorhombic, Pbcn, a=23.0085(19) Å, b=14.6379(12) Å, c=23.6226(19) Å, V=7956.0(11) Å³, Z=4, Dc=3.315 g cm^-3, and R(final)=0.0826. X-ray diffraction study reveals that compound 1 was the first interpenetrating network of 2-D metal-organic cationic coordination framework [Cu₂(bpp)₄(H₂O)₂]_n⁴ⁿ⁺, in which Keggin-type anions SiW₁₂O₄₀^4- has been used as a non-coordinating anionic template. The electrochemical property of 1-bulk modified carbon paste electrode (1-CPE) has been studied, and the results indicate that 1-CPE has good electrocatalytic activities toward the reduction of nitrite in 1 M H₂SO₄ aqueous solution.     

A novel three-dimensional inorganic framework: hydrothermal synthesis and crystal structure of CuMo3O10·H2O

A novel three-dimensional inorganic bimetallic compound Cu[Mo₃O₁₀]·H₂O 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic system, space group Pnma, a=8.6085(17) Å, b=7.5822(15) Å, c=13.690(3) Å, V=893.6(3) Å³, Z=4, λ(MoKα) = 0.71073 Å (R(F)=0.0357 for 1101 reflections). The structure of compound 1 is based on [{Mo₃O₁₀}²⁻]_∞ isopolyoxomolybdate chains bonded together with CuO₄ tetrahedra into a three-dimensional inorganic open framework. Three types of Mo-Cu layers and one-dimensional tunnels are observed in the title compound.     

Os(CO)2(η-SC5H4N(O))(η-SC5H4N): structural evidence for the transformation of pyridine-2-thione N-oxide to pyridine-2-thiolate in osmium complexes

The reaction of Os₃(CO)₁₂ with an excess of 1-hydroxypyridine-2-thione and Me₃NO gives three mononuclear osmium complexes Os(CO)₂(η²-SC₅H₄N(O))₂ (1), Os(CO)₂(η²-SC₅H₄N(O))(η²-SC₅H₄N) (2), and Os(CO)₂(η²-SC₅H₄N)₂ (3). The results of single-crystal X-ray analyses reveal that complex 1 contains two O,S-chelate pyridine-2-thione N-oxide (PyOS) ligands, whereas complex 2 contains one O,S-chelate PyOS and one N,S-chelate pyridine-2-thiolate group. The unique structure of 2 provides evidence of the pathway for this transformation. When this reaction was monitored by ¹H NMR spectroscopy the triosmium complexes Os₃(CO)₁₀(μ-H)(μ-η¹-S-C₅H₄N(O)) (4) and Os₃(CO)₉(μ-H)(μ-η¹:η²-SC₅H₄N(O)) (5) were identified as intermediates in the formation of the mononuclear final products 1-3. The proposed pathway is further supported by the observation of several dinuclear osmium intermediates by electrospray ionization mass spectrometry. In addition, the reaction of Os₃(CO)₁₂ with 1-hydroxypyridine-2-thione in the absence of Me₃NO at 90 °C generated mononuclear complex 2 as the major product along with smaller amounts of complexes 1 and 3. These results suggest that the N-oxide facilitates the decarbonylation reaction. Crystal data for 1: monoclinic, space group C2/c, a = 26.9990(5) Å, b = 7.6230(7) Å, c = 14.2980(13) Å, β = 101.620(2)°, V = 2882.4(4) ų, Z = 8. Crystal data for 2: monoclinic, space group C2/c, a = 5.7884(3) Å, b = 13.9667(7) Å, c = 17.2575(9) Å, β = 96.686(1)°, V = 1385.69(12) ų, Z = 4.     

Structural variations of Sn pyridylphosphonates influenced by an uncommon Sn-N interaction

Four new Sn^II phosphonates have been synthesized by hydrothermal methods, and their structures determined by single-crystal X-ray diffraction. Tin(II) 3-pyridylphosphonate, SnO₃PC₅H₄N (I), crystallizes in P2₁/c with a=4.9595(8) Å, b=10.7673(18) Å, c=13.996(2) Å, and β=93.616(2)°. Tri-tin(II) (μ-3)-oxo-(bis)-4-pyridylphosphonate, Sn₃O(O₃PC₅H₄N)₂ (II), crystallizes in P-1 with a=7.2406(14) Å, b=9.9524(19) Å, c=12.604(3) Å, α=104.510(11)°, β=90.326(11)°, and γ=110.897(11)°. Tin(II) 6-methyl-2-pyridylphosphonate quadrahydrate, Sn(O₃PC₅H₃NCH₃)·0.25H₂O (III), crystallizes in Pna2₁, a=18.955(3) Å, b=9.7543(14) Å, and c=17.833(3) Å. Tin(II) 4-cyanophenylphosphonate, Sn(O₃PC₆H₄CN) (IV), crystallizes in P-1, a=5.0019(3) Å, b=8.4396(5) Å, c=10.3099(6) Å, α=90.352(3)°, β=94.894(3)°, and γ=92.236(4)°. I, II, and IV have ladder-type structures, and III is a layered compound. The structural variations show the effects of the Sn-N interaction on the final structures.     

Hydrothermal synthesis, crystal structure, thermal behavior and spectroscopic and magnetic properties of two new organically templated fluoro-vanadyl-hydrogenarsenates: (R)0.5[(VO)(HAsO4)F] (R: Ethylenediammonium and piperazinium)

Two new fluoro-vanadyl-hydrogenarsenate compounds templated by ethylenediamine and piperazine with formula, (C₂N₂H₁₀)_0.5[(VO)(HAsO₄)F] (1) and (C₄N₂H₁₂)_0.5[(VO)(HAsO₄)F] (2), respectively, have been synthesized by using mild hydrothermal conditions under autogenous pressure. The crystal structures have been solved from single-crystal X-ray diffraction data. The phases crystallize in the P2₁/c monoclinic space group with the unit-cell parameters a=7.8634(4) Å, b=7.7658(4) Å, c=10.4195(6) Å, β=101.524(5)° for compound (1) and a=6.301(1) Å, b=10.244(1) Å, c=10.248(1) Å and β=95.225(1)° for compound (2). These phases exhibit a layered inorganic framework. In both cases, the structure is built from secondary building units (SBU) which are formed by [V₂O₈F₂] edge-shared dimeric vanadyl octahedra, connected by the vertices to two hydrogenarsenate tetrahedra. The repetition of this SBU unit originates sheets along the [1 0 0] direction. The ethylenediammonium and piperazinium cations are located inside the interlayer space. The limit of thermal stability for compounds (1) and (2) is, approximately, 250 and 230 °C, respectively. Near this temperature, both phases loose their organic cations and the fluoride anions. The diffuse reflectance spectra confirm the presence of vanadyl ions, in which the vanadium(IV) cations have a d¹ electronic configuration in a slightly distorted octahedral environment. ESR spectra of both phases are isotropic with mean g-values of 1.93 and 1.96 for ethylendiamine and piperazine phases, respectively. Magnetic measurements for (1) and (2) indicate the existence of antiferromagnetic exchange couplings.     

Two unprecedented inorganic-organic boxlike and chainlike hybrids based on arsenic-vanadium clusters linked by nickel complexes

Two novel organic-inorganic hybrid arsenic-vanadates, [{Ni(en)₂}₄(4,4′-bipy)₄{Ni(H₂O)₂}]₂[As₈V₁₄O₄₂(NO₃)]₄·16H₂O 1 and [Ni(en)₂(H₂O)₂]₂[{Ni(en)₂(H₂O)}₂As₈V₁₄O₄₂(NO₃)][{Ni(en)₂}As₈V₁₄O₄₂(NO₃)]·6H₂O 2 are reported in this study. Crystal data for compound 1: Tetragonal, I4/m, a=27.507(4) Å, b=27.507(4) Å, c=22.101(4) Å; V=16722(5) Å³, Z=2, R(final)=0.0508. Crystal data for compound 2: Triclinic, P-1, a=11.530(2) Å, b=14.883(3) Å, c=21.330(4) Å, α=76.94(3)°, β=76.58(3)°, γ=69.54(3)°, V=3293.4(1) Å³, Z=1, R(final)=0.0559. The boxlike structure of compound 1 is designed from [{Ni(en)₂}₄(4,4′-bipy)₄{Ni(H₂O)₂}] sheets pillared by [α-As₈V₁₄O₄₂] clusters, which represents the first mixed-organic ligand-decorated tetrameric As-V-O cluster. Compound 2 is constructed from the rarely [β-As₈V₁₄O₄₂] clusters and Ni coordination complex fragments. The electrochemical property and magnetic property of compound 1 have been studied.     

Synthesis and characterization of two novel organocation containing group 13 metal ethylenediphosphonates

Two novel group 13 metal diphosphonates: (H₃NC₃H₆NH₃)₂[Al₂F₆(O₃PC₂H₄PO₃)]·H₂O (1) (monoclinic, C2/c, a=16.9697(7) Å, b=8.0273(4) Å, c=16.3797(8) Å, β=117.762(2)°, Z=4, R₁=4.66%, wR₂=11.82%), and (H₃NC₃H₆NH₃)[Ga₂F₄(O₃PC₂H₄PO₃)] (2) (triclinic, P-1, a=5.398(7) Å, b=8.122(6) Å, c=15.839(18) Å, α=78.89(4)°, β=89.60(7)°, γ=79.35(6)°, Z=2, R₁=2.90%, wR₂=3.17%) have been synthesized by solvothermal methods in the presence of the propyldiammonium cations and their structures determined using single and micro-crystal X-ray diffraction data, respectively. The structures of 1 and 2 are closely related and contain dimers of edge-sharing trivalent metal centered octahedra that are linked together by the ethylenediphosphonate groups to form chains and aperture-containing layers, respectively. The propyldiammonium cations surround the aluminum diphosphonate chains in 1 and separate the gallium diphosphonate layers in 2. Both compounds 1 and 2 are examples of metal phosphonate materials containing only one type of octahedral-tetrahedral secondary building unit (SBU-4).     

Hydrothermal syntheses and structures of the uranyl tellurates AgUO2(HTeO5) and Pb2UO2(TeO6)

Two uranyl tellurates, AgUO₂(HTeO₅) (1) and Pb₂UO₂(TeO₆) (2), were synthesized under hydrothermal conditions and were structurally, chemically, and spectroscopically characterized. 1 crystallizes in space group Pbca, a=7.085(2) Å, b=11.986(3) Å, c=13.913(4) Å, V=1181.5(5) Å³, Z=8; 2 is in P2(1)/c, a=5.742(1) Å, b=7.789(2) Å, c=7.928(2) Å, V=90.703(2) Å³, and Z=2. These are the first structures reported for uranyl compounds containing tellurate. The U⁶⁺ cations are present as (UO₂)²⁺ uranyl ions that are coordinated by O atoms to give pentagonal and square bipyramids in compounds 1 and 2, respectively. The structural unit in 1 is a sheet consisting of chains of edge-sharing uranyl pentagonal bipyramids that are one bipyramid wide, linked through the dimers of TeO₆ octahedra. In 2, uranyl square bipyramids share each of their equatorial vertices with different TeO₆ octahedra, giving a sheet with the autunite-type topology. Sheets in 1 and 2 are connected through the low-valence cations that are located in the interlayer region. The structures of 1 and 2 are compared to those of uranyl compounds containing octahedrally coordinated cations.     

A group of new selenite-chlorides of strontium and d-metals (Co,Ni): Synthesis, thermal behavior and crystal chemistry

The new selenite-chlorides with composition Sr₃(SeO₃)₂Cl₂ (I) and Sr₂M(SeO₃)₂Cl₂ (M=Co, Ni (II and III)) were obtained. They crystallize in monoclinic system I: space group C2/m, a=13.203(2) Å, b=5.5355(8) Å, c=6.6170(10) Å, β=95.89(1)°, Z=2; II Space group P2₁/n, a=5.3400(10) Å, b =6.4279(6) Å, c=12.322(1) Å, β=92.44(1)°, Z=2; III: space group P2₁/n, a=5.3254(11) Å, b=6.4363(13) Å, c=12.197(2), β=92.53(3)°, Z=2. All three compounds are constructed in the same manner. Sr polyhedra form infinite layers, which are interconnected into a 3D framework by means of Sr polyhedra in the case of I or Co and Ni polyhedra in the case of II and III. Se atoms are situated inside the channels of the 3D framework. The topological analysis of ELF for I confirmed that the lone electron pairs of SeO₃ groups are located inside these channels.     

Effect of synthetic conditions on the structures of silver(I)-hexamethylenetetramine coordination polymers: crystal structures of two three-dimensional frameworks featuring new topological motifs

Two novel coordination complexes, [Ag₃(μ₄-hmt)₂(μ-ssa)(H₂O)](NO₃)·3H₂O 1, and [Ag₈(μ₃-hmt)₂(μ₄-hmt)₂(μ-pma)₂(μ-H₂O)₃]·18H₂O 2 (hmt=hexamethylenetetramine, ssa=sulfosalicylate and pma=1,2,4,5-benzenetetracarboxylate), have been prepared and structurally characterized. Crystal data: 1 C₁₉H₃₃Ag₃N₉O₁₃S, orthorhombic, Pna2₁, a=20.483(7) Å, b=21.890(1) Å, c=6.493(2) Å, V=2911.3(13) Å³, Z=4; 2 C₄₄H₉₄Ag₈N₁₆O₃₇, monoclinic, C2/c, a=32.099(10) Å, b=12.916(3) Å, c=21.431(8) Å, β=126.74(1)°, V=7120(4) Å³, Z=4. Both complexes exhibit unprecedented and different topological motifs of Ag-hmt networks. Complex 1 is a novel three-dimensional cationic network with two types of channels, in which the larger one is the largest one in Ag-hmt networks; while 2 is a three-dimensional network with cylindrical channels, consisting of mixed μ₃- and μ₄-hmt ligands. The results demonstrate that under different synthetic conditions, such as the presence of multiple small counter anions or different pH values, different Ag-hmt linkages may be formed to generate new three-dimensional networks.     

New indium selenite-oxalate and indium oxalate with two- and three-dimensional structures

Two new indium(III) compounds with extended structures, [In₂(SeO₃)₂(C₂O₄)(H₂O)₂]·2H₂O (I) and [NH₃(CH₂)₂NH₃][In(C₂O₄)₂]₂·5H₂O (II), have been prepared under mild hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis and infrared spectroscopy. Compound I crystallizes in the triclinic system, space group P-1, with a=5.2596(11) Å, b=6.8649(14) Å, c=9.3289(19) Å, α=101.78(3)°, β=102.03(3)°, γ=104.52(3)°, while compound II crystallizes in the orthorhombic system, space group Fdd2, with a=15.856(3) Å, b=31.183(6) Å, c=8.6688(17) Å. In compound I, indium-selenite chains are bridged by oxalate units to form two-dimensional (2D) In₂(SeO₃)₂C₂O₄ layers, separated by non-coordinating water molecules. In compound II, the indium atoms are connected through the oxalate units to generate a 3D open framework containing cross-linked 12- and 8-membered channels.     

Syntheses, structures and magnetic properties of two new one-dimensional cobalt (II) phosphites with organic amines acting as ligands

Two new one-dimensional (1D) inorganic-organic hybrid cobalt (II) phosphites Co(HPO₃) (py) (1) and [Co(OH)(py)₃][Co(py)₂][HPO₂(OH)]₃ (2) have been prepared under solvothermal conditions in the presence of pyridine (py). Compound 1 crystallizes in the monoclinic system, space group p2(1)/c, a=5.3577(7) Å, b=7.7503(10) Å, c=17.816(2) Å, β=94.327(2)°, V=737.67(16) Å³, Z=4. Compound 2 is orthorhombic, Cmcm, a=16.3252(18) Å, b=15.7005(16) Å, c=13.0440(13) Å, β=90.00° V=3343.4(6) Å³ and Z=4. Compound 1 possesses a 1D ladder-like framework constructed from CoO₃N tetrahedral, HPO₃ pseudo-pyramids and pyridine ligands. While compound 2 is an unusual inorganic-organic hybrid 1D chain, which consists of corner-shared six-membered rings made of CoO₃N₃/CoO₄N₂ octahedra and HPO₃ pseudo-pyramids through sharing vertices.     

The first di-cadmium-substituted vanadoarsenate derived from α-{As8V14O42} shell

Two di-cadmium-substituted vanadoarsenates, [Cd(enMe)₃]₂{α-[(enMe)₂Cd₂As₈V₁₂O₄₀(0.5H₂O)]}·5.5H₂O (1, enMe=1,2-diaminopropane) and [Cd(enMe)₂]₂{β-[(enMe)₂Cd₂As₈V₁₂O₄₀(0.5H₂O)]} (2), were hydrothermally synthesized and characterized by elemental analyses, IR, TGA, UV-Vis, XRD, magnetic measurements and single crystal structural analyses. Crystal data for 1: monoclinic, P2(1)/c, a=15.040(9) Å, b=20.288(12) Å, c=27.873(17) Å, β=98.046(8)°, V=8421.3(19) Å³, Z=4; for 2: monoclinic, P2(1)/n, a=12.753(3) Å, b=19.334(5) Å, c=14.310(3) Å, β=99.984(3)°, V=3475.1(14) Å³, Z=2. X-ray diffraction analyses reveal that compounds 1 and 2 exhibit isolated and one-dimensional inorganic-organic hybrid structures, respectively. The former is the first di-cadmium-substituted vanadoarsenate derived from α-{As₈V₁₄O₄₂} shell, while the latter is another kind of di-cadmium-substituted vanadoarsenate derived from β-{As₈V₁₄O₄₂} shell. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interactions between V^IV cations in 1 and 2.