Magnetic structure and properties of Cu3(OH)4SO4 made of triple chains of spins s=1/2

Cu₃(OH)₄SO₄, obtained by hydrothermal synthesis from copper sulfate and soda in aqueous medium, is isostructural with the corresponding antlerite mineral, orthorhombic, space group Pnma (62), with a=8.289(1) b=6.079(1) and c=12.057(1) Å, V=607.5(2) ų, Z=4. Its crystalline structure has been refined from X-ray single crystal and powder neutron diffraction data at room temperature. It consists of copper (II) triple chains, running in the b-axis direction and connected to each other by sulfate groups. The magnetic structure, solved from powder neutron diffraction data at 1.4 K below the transition at 5 K evidenced by susceptibility and specific measurements, reveals that, inside a triple chain, the magnetic moments of the copper ions (μ_B=0.88(5) at 1.4 K) belonging to outer chains are oriented along the c-axis of the nuclear cell, with ferromagnetic order inside a chain and antiferromagnetic order between the two outer chains. No long-range magnetic order is obtained along the central chain with an idle spin behavior.     

Preparation, crystal structure, vibrational spectra and thermal behavior of selenites of ethylene diamine, 1,3-propylene diamine and 1,4-butylene diamine

Selenites of ethylene diamine, propylene diamine and butylene diamine were prepared by crystallization from aqueous solution. The crystal structure was solved for all the substances. Ethylene diammonium(2+) selenite crystallizes in the orthorhombic space group P2₁2₁2, a=11.3710(2) Å, b=11.4390(5) Å, c= 4.6290(4) Å, V= 602.11(6) ų, Z=4, R=0.0341 for 5729 observed reflections. 1,3-Propylene diammonium(2+) selenite dihydrate crystallizes in the monoclinic space group C2/c, a=16.241(14) Å, b=6.673(5) Å, c=17.731(14) Å, β=110.88(2)°, V=1795(3) ų, Z=8, R=0.0271 for 12,233 observed reflections. 1,4-Butylene diammonium(2+) selenite dihydrate crystallizes in the monoclinic space group P2₁/c, a=6.686(5) Å, b=16.597(14) Å, c=9.282(8) Å, β=96.653(14)°, V=1023.2(14) ų, Z=4, R=0.0465 for 2918 observed reflections. The FTIR an FT Raman spectra of all the compounds were recorded and interpreted. The thermoanalytical properties were studied by the TG, DTG, and DTA methods in the 293–633 K temperature range. DSC measurements were carried out in the range from 98 K to the temperature of decomposition of the compounds. No thermal effect indicating a phase transition was observed in this temperature region.     

Synthesis and Crystal Structure of a New Mixed Orthovanadate-Pyrovanadate Series: MBa2V3O11 or MBa2V2PO11 with M = Bi, In, or a Rare Earth

A new series of vanadates with the general formula M Ba₂V₃O₁₁, where M may be Bi, In, or a rare earth, has been synthesized and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction. The general formula may be rewritten as M Ba₂(VO₄)(V₂O₇) to emphasize that there is one orthovanadate group and one pyrovanadate group in each formula unit. Up to one-third of the vanadium may be replaced by phosphorous, leading to the general formula M Ba₂V₂PO₁₁. However, phosphorous shows no preference between the ortho and pyro groups. Both M Ba₂V₃O₁₁ and M Ba₂V₂PO₁₁ crystallize in the monoclinic system with the space group P2₁/_c and Z = 4. The cell parameters from single crystal X-ray data of BiBa₂V₃O₁₁ are a = 12.332(4) Å, b = 7.750(4) Å, c = 11.279(4) Å, β = 103.22(3)°, V = 1049(1) ų; and for BiBa₂PO₁₁ are a = 12.266(2) Å, b = 7.615(2) Å, c = 11.312(2) Å, β = 103.32(2)°, V = 1028.2(2) ų. The Bi atom coordinates to six oxygen atoms forming a distorted octahedron, and the edge sharing of BiO₆ octahedra results in a BiO₄ chain along the b axis. There are two types of Ba atoms with coordination numbers of 10 and 11. There are three types of tetrahedral (T) atoms in these structures. The nonequivalent T atoms of the pyro group give T-O-T angles of 167 and 171° in BiBa₂V₃O₁₁ and BiBa₂V₂PO₁₁, respectively. Isostructural M Ba₂V₃O₁₁ compounds were prepared in which M is In, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, or Lu.     

An XRPD ab-initio structural determination of La2RuO5

The crystal structure of a new oxide, La₂RuO₅, was determined ab initio using conventional laboratory X-ray powder diffraction. Combining X-ray and electron diffraction techniques, we found that the new phase crystallized in the monoclinic system with the space group P2₁/c (SG no.14) and the cell parameters a=9.1878(2) Å, b=5.8313(2) Å, c=7.9575(2) Å and β=100.773(2)° (V=418.8 ų, Z=4). The structural determination with the Patterson method and Fourier difference syntheses and the final Rietveld refinement were performed by means of the JANA2000 program. The structure is built up from the regular stacking of a two octahedra thick [LaRuO₄]_∞ zigzag perovskite slab and an original 3.4 Å thick [LaO]_∞ slab which constitutes the key feature of this new structure.     

Single-crystal characterization of Co7(OH)6(H2O)3(C4H4O4)47H2O; A new cobalt succinate identified through high-throughput synthesis

A new form of cobalt succinate has been discovered using high-throughput methods and its structure was solved by single crystal X-ray diffraction. Co₇(C₄H₄O₄)₄(OH)₆(H₂O)₃7H₂O crystallizes in the monoclinic space group P2₁/c with cell parameters: a=7.888(2) Å, b=19.082(6) Å, c=23.630(7) Å, β=91.700(5)°, V=3555(2) Å³, R₁=0.0469. This complex structure, containing 55 crystallographically distinct non-hydrogen atoms, is compared to the previously reported nickel phase, characterized using ab initio structure solution from synchrotron powder diffraction data.     

Crystal structure and Mössbauer spectroscopy of Y2SrFeCuO6.5, a double layer perovskite intergrowth phase

The crystal structure of Y₂SrFeCuO_6.5 was determined from single-crystal X-ray and neutron powder diffraction studies. M_r = 488.81, orthorhombic, Ibam, a = 5.4036(8)[5.4149(1)] Å, b = 10.702(1)[10.7244(1)] Å, c = 20.250(2)[20.2799(2)] Å; values in square brackets are neutron data. V = 1171.0(4), Z = 8, D_x = 5.544 g cm⁻³, λ = 0.71069 Å, μ = 345.1 cm⁻¹, R = 0.048 for 567 observed reflections. The Fe/Cu atoms occupy randomly the approximate center of oxygen pyramids. The pyramids share the apical oxygen and articulate laterally by corner sharing of oxygen to form a double pyramidal layer perpendicular to c. The pyramidal slabs are separated by double layers of Y that are in 7-fold coordination to oxygen, forming a defect fluorite unit. Mössbauer spectra indicate a unique iron environment and magnetic ordering at about 265 K. The paramagnetic phase coexists with the magnetic phase over an approximate temperature range 300-263 K, characteristic of magnetic ordering in 2-D magnetic structures. The isomer shift, 0.26, and quadrupole splitting, 0.56 mm sec⁻¹, are consistent with Fe³⁺ in 5-fold coordination and H_int values also indicate classic high spin Fe³⁺. The average Y---O bond length is 2.331(6) Å and Sr is in a dodecahedral environment in which, however, two oxygen atoms at the corners of the cube are missing. The average Sr---O bond length is 2.793(10) Å. The structure is derived from the Ruddlesden-Popper phase Sr_n+1Ti_nO_3n+1 with n = 2.     

Self-assembly of two novel bisupporting Keggin-polyoxometalate derivatives: Hydrothermal synthesis and structure characterization of (X = P, m = 1; X = Si, m = 2)

Two novel organic–inorganic hybrid polyoxometalates, (X = P, m = 1 1; X = Si, m = 2 2; 2,2′-bpy = 2,2′-bpyridine), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. They are isostructural, possessing orthorhombic, and the parameters of unit cells for compound 1 are space group Pbca, a = 17.317(4) Å, b = 17.092(3) Å, c = 20.587(4) Å, V = 6445(2) Å³, Z = 4; for compound 2 are space group Pcab, a = 17.181(3) Å, b = 18.198(4) Å, c = 20.672(4) Å, V = 6463(2) Å³, Z = 4. The two compounds show a layer framework constructed from Keggin-polyoxoanion clusters and [Cu (2, 2′-bpy)₂]²⁺ coordination polymer fragments via weak covalent interactions, resulting in a 3D network via supramolecular interactions. Their electrochemical properties are studied in detail.     

Hydrothermal Syntheses, Structures, and Properties of Two New Potassium Vanadium Phosphates: K3(VO) (V2O3) (PO4)2(HPO4) and K3 (VO) (HV2O3) (PO4)2(HPO4)

Two new potassium vanadium phosphates have been prepared and their structures have been determined from analysis of single crystal X-ray data. The two compounds, K₃(VO)(V₂O₃) (PO₄)₂(HPO₄) and K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), are isostructural, except for the incorporation of an extra hydrogen atom into the nearly identical frameworks. The structures consist of a three-dimensional network of [VO]_n chains connected through phosphate groups to a [V₂O₃] moiety. Magnetic susceptibility experiments indicate that in the case of the di-hydrogen compound, there are no significant magnetic interactions between the three independent vanadium (IV) centers. Crystal data: for K₃(VO)(V₂O₃)(PO₄)₂ (HPO₄), M_r = 620.02, orthorhombic space group Pnma (No. 62), a = 7.023(4) Å, b = 13.309(7) Å, c = 14.294(7) Å, V = 1336(2) ų, Z = 4, R = 5.02%, and R_w = 5.24% for 1238 observed reflections [I > 3σ(I)]; for K₃(VO)(HV₂O₃)(PO₄)₂(HPO₄), M_r = 621.04, orthorhombic space group Pnma (No. 62), a = 6.975(3) Å, b = 13.559(7) Å, c = 14.130(7) Å, V = 1336(1) ų, Z = 4, R = 6.02%, and R_w = 6.34% for 1465 observed reflections [I > 3σ(I)].     

Syntheses and characterization of Co(pydc)(H2O)2 and Ni(pydc)(H2O) (pydc = 3,5-pyridinedicarboxylate)

The hydrothermal reaction of 3,5-pyridinedicarboxylic acid (pydcH₂) and Co(NO₃)₂ or Ni(NO₃)₂ in the presence of 4,4′-bipyridine results in two novel compounds Co(pydc)(H₂O)₂ (1) and Ni(pydc)(H₂O) (2). Crystal data: 1, monoclinic, C2/c, a=9.900(2), b=11.984(2), c=7.3748(15) Å, β=105.37(3)°, V=843.7(3) Å³, Z=4; 2, monoclinic, P2₁/c, a=7.7496(6), b=15.0496(11), c=6.4224(5) Å, β=108.437(1)°, V=710.59(9) Å³, Z=4. The structure of 1 is composed of honeycomb layers built up from {CoO₄N} trigonal bipyramids and 3,5-pyridinedicarboxylate bridges. The structure of 2 adopts a three-dimensional framework structure in which the Ni atoms are coordinated by the pydc bridges both within the honeycomb layer and between the layers. The magnetic properties of 1 and 2 have been investigated.     

[{(NiOH)2Mo10O36(PO4)Ti2}n]: a novel chainlike trimetal heteropolyanion based on pseudo-keggin fragments

A new mixed Mo/Ni/Ti heteropoly compound [C₅H₅NH]₅ [(NiOH)₂Mo₁₀O₃₆(PO₄)Ti₂] has been hydrothermally synthesized and structurally determined by the single-crystal X-ray diffraction. Black prismatic crystals crystallize in the monoclinic system, space group P2(1)/n, a=11.2075(2), b=37.8328(5) c=13.0888(1) Å, β=101.4580(10)°, M=2276.13, V=5439.19(13) ų, Z=4. Data were collected on a Siemens SMART CCD diffractometer at 293(2) K in the range of 1.68<θ<25.09° using the ω-scan technique (λ=0.71073 Å R(F)=0.0872 for 9621 reflections). The title compound contains a trimetal heteropolyanion polymer and “trans-titanium”-bridging pseudo-Keggin fragments linked to a chain.     

The Crystal Structures of the Strontium Gallates Sr10Ga6O19 and Sr3Ga2O6

The crystal structures of Sr₁₀Ga₆O₁₉ and Sr₃Ga₂O₆ have been characterized using X-ray diffraction techniques. In the case of Sr₁₀Ga₆O₁₉, the structure was determined from a single crystal diffraction data set collected at room conditions and refined to a final R index of 0.061 for 3471 observed reflections (I>2 σ(I)). The compound is monoclinic with space group C12/c1 (a=34.973(4) Å, b=7.934(1) Å, c=15.943(2) Å, β=103.55(1)°, V=4300.7(6) ų, Z=8, D_calc=4.94 g/cm³, μ(MoKα)=32.04 mm⁻¹) and can be classified as an oligogallate. It is the first example of an inorganic compound where six [TO₄]-tetrahedra of only one chemical species occupying the tetrahedral centres are linked via bridging oxygen atoms to form [T₆O₁₉] groups. The hexamers are not linear, but highly puckered. Eleven symmetrically different Sr cations located in planes parallel (100) crosslink between the oligo-groups. They are coordinated by six to eight oxygen ligands. The structure of Sr₃Ga₂O₆ has been refined from powder diffraction data using the Rietveld method (space group Pa , a=16.1049(1), V=4177.1(1) ų, Z=24, D_calc=4.75 g/cm³). The compound is isostructural with tricalcium aluminate and contains highly puckered, six-membered [Ga₆O₁₈]¹⁸⁻ rings. The rings are linked by strontium cations having six to nine nearest oxygen neighbors.     

Synthesis and characterization of [Zn(2,2′-bipy)]2(H2PO3)4: A neutral zinc phosphite cluster containing ZnO3N2 and H2PO3 units

The hydrothermal synthesis, crystal structure and some properties of a zinc phosphite with a neutral cluster, [Zn(2,2′-bipy)]₂(H₂PO₃)₄, are reported. This compound crystallizes in the triclinic system of space group P-1 (No. 2), a=8.3067(5) Å, b=8.9545(4) Å, c=10.0893(6) Å, α=95.448(2)°, β=99.7530(10)°, γ=103.461(2)°, V=712.23(7) ų, Z=1. The cluster consists of 4-membered rings formed by alternating ZnO₃N₂ square pyramids and H₂PO₃ pseudo pyramids, with two “hanging” H₂PO₃ groups attached to each of the Zn centers. The clusters are linked together by extensive multipoint hydrogen bonding involving the phosphite units to form a sheet-like structure. This compound represents the first example of zinc phosphite with P---OH bonds. An intense photoluminescence was observed from this compound upon photoexcitation at 388 nm.     

New insight in the structure–luminescence relationships of Ca9Eu(PO4)7

The double phosphate Ca₉Eu(PO₄)₇, obtained by solid state reaction, was found to be isotypic with Ca₃(PO₄)₂, with space group R3c and unit cell parameters a=10.4546(1) Å, c=37.4050(3) Å, V=3540.67(9) Å³, Z=6. The structure parameters refined using the Rietveld method showed that europium shares positions M1, M2 and M3 with calcium, contradicting previously published Mössbauer results. Low temperature luminescence under selective excitation of Eu³⁺ in Ca₉Y_1−xEu_x(PO₄)₇ and in Ca₉Eu(PO₄)₇ samples was studied, confirming the Eu³⁺ distribution into these sites. At 10 K, ⁵D₀→⁷F₀ emission lines of Eu³⁺ were observed at 578.5, 579.5, 580.1 nm for the M3, M1 and M2 sites, respectively. High temperature X-ray powder diffraction evidenced a second-order phase transition around 573 °C.     

Synthesis and characterization of quaternary selenides Sn2Pb5Bi4Se13 and Sn8.65Pb0.35Bi4Se15

Quaternary selenides Sn₂Pb₅Bi₄Se₁₃ and Sn_8.65Pb_0.35Bi₄Se₁₅ were synthesized from the elements in sealed silica tubes; their crystal structures were determined by single-crystal and powder X-ray diffraction. Both compounds crystallize in monoclinic space group C2/m (No.12), with lattice parameters of Sn₂Pb₅Bi₄Se₁₃: a = 14.001(6) Å, b = 4.234(2) Å, c = 23.471(8) Å, V = 1376.2(1) Å³, R₁/wR₂ = 0.0584/0.1477, and GOF = 1.023; Sn_8.65Pb_0.35Bi₄Se₁₅: a = 13.872(3) Å, b = 4.2021(8) (4) Å, c = 26.855(5) Å, V = 1557.1(5) Å³, R₁/wR₂ = 0.0506/0.1227, and GOF = 1.425. These compounds exhibit tropochemical cell-twinning of NaCl-type structures with lillianite homologous series L(4, 5) and L(4, 7) for Sn₂Pb₅Bi₄Se₁₃ and Sn_8.65Pb_0.35Bi₄Se₁₅, respectively. Measurements of electrical conductivity indicate that these materials are semiconductors with narrow band gaps; Sn₂Pb₅Bi₄Se₁₃ is n-type, whereas Sn_8.65Pb_0.35Bi₄Se₁₅ is a p-type semiconductor with Seebeck coefficients −80(5) and 178(7) μV/K at 300 K, respectively.     

New Layered Materials in the K–In–Ge–As System: K8In8Ge5As17and K5In5Ge5As14

Exploratory synthesis in the K–In–Ge–As system has yielded the unusual layered compounds K₈In₈Ge₅As₁₇(1) and K₅In₅Ge₅As₁₄(2), both of which contain In–Ge–As layers with interleaved potassium ions, Ge–Ge bonds, InAs₄tetrahedra, As–As bonds, and rows of Ge₂As₆dimers. Compound 1 has As₃groups, while compound 2 has infinite As ribbons on both faces of each layer. Unlike compound 1, compound 2 has substitutional defects where indium partially occupies each of the three independent germanium sites in the ratio of 1:5 for In:Ge. This partial occupancy makes 2 an electron-precise compound. The Ge(In)–Ge(In) bond of 2 is longer than the Ge–Ge bond of 1, and this bond lengthening effect was confirmed by performing DFT-MO calculations on the model compounds H₃Ge–GeH₃and H₃Ge–InH⁻₃. Possible implications of electron imprecise formulas determined by X-ray crystal structure determinations are discussed. Compound 1: space groupP2₁/cwitha=18.394 (8) Å,b=19.087 (7) Å,c=25.360 (3) Å,β=105.71 (2)°,V=8571 (4) ų, andD_calcd=4.45g/cm³forZ=4. Refinement on 4455 reflections yieldedR(R_w)=6.8%(7.8%). Compound 2: space groupC2/mwitha=40.00 (1) Å,b=3.925 (2) Å,c=10.299 (3),β=99.97 (2)°,V=1592 (1) ų, andD_calcd= 4.55g/cm³forZ=8. Refinement on 1206 reflections yieldedR(R_w)=5.6% (5.7%).     

Diazabicyclo[2.2.2]octane-1,4-diium occluded in cubic anionic coordinated framework: the role of trifurcated hydrogen bonds of N–HO and C–HO

A unique coordinated molecular capsule compound is synthesized and characterized by X-ray diffraction. The compound crystallizes in cubic space group of Pa-3 with a=14.348(1), b=14.348(1), c=14.348(1) Å, V=2953.8(4) ų, Z=8. The diazabicyclo[2.2.2]octane-1,4-diium is occluded in the cubic anionic coordinated framework of K⁺ and (ClO₄)⁻ in a dimension of 7.174(1) Å, and assumes ordered feature. All of hydrogen atoms take parts in trifurcated hydrogen bonds of N–HO and C–HO type, respectively, the later being reported for the first time. The IR spectrum of the title compound shows significant shift of CH₂ vibrational bands, and are correlated with X-ray structural data.     

The Crystal Structures of Thallium(I) Fluoride

The effects of temperature and pressure on the crystal structures of thallium(I) fluoride have been investigated using powder neutron diffraction, with the aim of resolving the uncertainties present in the literature. Under ambient conditions, TlF adopts an orthorhombic structure in space group Pbcm with Z=4 and cell parameters a=6.09556(8) Å, b=5.48860(7) Å, and c=5.18300(7) Å. This structure can be derived from an idealized rocksalt-type arrangement, though with extensive distortions of the anion sublattice due to the presence of the 6s² inert pair of the Tl⁺ Above 355 K TlF becomes tetragonal with Z=2, a=3.78283(2) Å, c=6.12312(5) Å, and space group P4/nmm. The behavior of the compound is also studied under hydrostatic pressure but, contrary to previous reports, no structural transition was observed and TlF remains orthorhombic up to at least 3.5 GPa. The compressibility is greatest along the a and b axes. The relationship between the ambient- and high-temperature structures of TlF is described and the influence of the inert pair discussed in relation to the massicot structured polymorph of PbO.     

Synthesis, crystal structures, phase transition characterization and thermal decomposition of a new dabcodiium hexaaquairon(II) bis(sulfate): (C6H14N2)[Fe(H2O)6](SO4)2

The crystal structures of 1,4-diazabicyclo[2.2.2]octane (dabco)-templated iron sulfate, (C₆H₁₄N₂)[Fe(H₂O)₆](SO₄)₂, were determined at room temperature and at −173 °C from single-crystal X-ray diffraction. At 20 °C, it crystallises in the monoclinic symmetry, centrosymmetric space group P2₁/n, Z=2, a=7.964(5), b=9.100(5), c=12.065(5) Å, β=95.426(5)° and V=870.5(8) ų. The structure consists of [Fe(H₂O)₆]²⁺ and disordered (C₆H₁₄N₂)²⁺ cations and (SO₄)²⁻ anions connected together by an extensive three-dimensional H-bond network. The title compound undergoes a reversible phase transition of the first-order at −2.3 °C, characterized by DSC, dielectric measurement and optical observations, that suggests a relaxor–ferroelectric behavior. Below the transition temperature, the compound crystallizes in the monoclinic system, non-centrosymmetric space group Cc, with eight times the volume of the ambient phase: a=15.883(3), b=36.409(7), c=13.747(3) Å, β=120.2304(8)°, Z=16 and V=6868.7(2) ų. The organic moiety is then fully ordered within a supramolecular structure. Thermodiffractometry and thermogravimetric analyses indicate that its decomposition proceeds through three stages giving rise to the iron oxide.     

Synthesis, crystal structure, and preliminary study of luminescent properties of InTbGe2O7

A new indium terbium germanate InTbGe₂O₇, which is a member of the thortveitite family, was prepared as a polycrystalline powder material by high-temperature solid-state reaction. This new compound crystallizes in the monoclinic system, space group C2/c (No. 15), with unit cell parameters a=6.8818(2) Å, b=8.8774(3) Å, c=9.7892(4) Å, β=101.401(1)°, V=586.25(4) ų and Z=4. Its structure was characterized by Rietveld refinement of powder laboratory X-ray diffraction data. It consists of octahedral sheets that are held together by sheets of isolated Ge₂O₇ diorthogroups composed of two tetrahedra sharing a common vertex. It contains only one octahedral site occupied by In³⁺ and Tb⁺³ cations. The characteristic mirror plane in the thortveitite (Sc₂Si₂O₇) space group (C2/m, No. 12) is not present in this new compound. Besides, in InTbGe₂O₇, the Ge–O–Ge angle bridging two diorthogroups is 156.8(2)° as compared to the one in thortveitite, which is 180°. On the other hand, luminescent properties were observed when it is excited with 376.5 nm wavelength. The luminescence spectrum shows typical transitions from the ⁵D₄ multiplet belonging to the trivalent terbium ion.     

Flux synthesis of (3,4)-connected zinc phosphites with different framework topologies

Two three-dimensional open-framework zinc phosphites, H₂aem·Zn₃(HPO₃)₄·0.5H₂O (1) and H₂apm·Zn₃(HPO₃)₄ (2), have been synthesized by a phosphorous acid flux method, where aem=4-(2-aminoethyl)morpholine and apm=4-(3-aminopropyl)morpholine. Compound 1 crystallizes in the monoclinic system, P2₁/c, a=9.5852(7) Å, b=20.3941(8) Å, c=10.5339(8) Å, β=94.125(9)°, V=2053.8(2) Å³, Z=4, R₁=0.0319, wR₂=0.0628. Compound 2 crystallizes in the monoclinic system, P2₁/n, a=8.589(2) Å, b=14.020(3) Å, c=16.606(3) Å, β=97.190(8)°, V=1983.9(7) Å³, Z=4, R₁=0.0692, wR₂=0.1479. Both compounds are based on (3,4)-connected networks with 8- and 12-ring channels, which are constructed from Zn₃(HPO₃)₄ clusters as the same secondary building units. These inorganic clusters are spatially organized by different structure-directing agents into different three-dimensional frameworks.