[C2N2H10]1.5[Nd(SO4)3(H2O)]·2H2O: The first organically templated neodymium sulfate with a layer structure

The first organically templated neodymium sulfate has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction analysis. [C₂N₂H₁₀]_1.5[Nd(SO₄)₃(H₂O)]·2H₂O crystallizes in the monoclinic space group P2₁/c with crystal data , , , β=104.399(5)°, , Z=4. Refinement gave R₁[I>2σ(I)]=0.0471, and wR₂[I>2σ(I)]=0.0899. The compound exhibits an infinite zigzag anionic layer structure, which consists of {Nd(SO₄)₃(H₂O)}³⁻ structural units connected together to form interesting eight-membered rings via corner-sharing and edge-sharing modes. The compound has the antiferromagnetic behavior and exhibits intense photoluminescence upon photo-excitation at 450 nm.     

Hydrothermal synthesis and crystal structure of a new inorganic/organic hybrid of scandium sulfate: (H2en)Sc2(SO4)4·(H2O)0.72

The first organically templated layered structure of scandium sulfate, (H₂en)Sc₂(SO₄)₄·(H₂O)_0.72, (en=ethylenediamine) was synthesized by a hydrothermal method and characterized by single crystal X-ray diffraction. In the title compound, scandium ions are bridged by sulfate groups with a ratio of 1:2 into a 4₃⁶ layer structure. These layers are parallel packed and separated from each other by ethylenediammonium dications and water molecules. The title compound crystallizes in the monoclinic space group P2/c, with cell parameters , , , β=91.210(3)°, and Z=2. Refinement gave R₁[I>2σ(I)]=0.0354 and wR₂[I>2σ(I)]=0.0878. Thermogravimetric analysis indicates that this material is thermally stable to above 400 °C.     

一种新型的一维杂化磷酸锌化合物(2,2′-bipy)2·Zn2(PO4H)(PO4H2)2的合成与结构表征

作为磷酸盐基空旷骨架(Open-framework)化合物的一个重要组成部分, 磷酸锌基空旷骨架化合物经过近10年的发展已经成为内涵丰富的一个族系[1～6]. 实验证明有机胺基团可以作为配体, 起到电荷平衡阳离子与磷酸锌构成骨架作用[1～6]. 我们认为, 有机胺和骨架上的部分锌原子键合方式与多金属氧酸盐中的配体-次级金属结构模型存在相似性. 因此, 将多金属氧酸盐的配体-次级金属模型向过渡金属磷酸盐领域进行"嫁接", 不仅存在着实验参考依据[3,4], 而且将会推动磷酸盐配位化学的发展. 与多面体构成的钼酸盐和钒酸盐相比较, 这种"嫁接"意味着以磷氧四面体为结构单元的过渡金属磷酸盐可能存在着新颖的拓扑结构. 我们选用2,2′-联吡啶作为螯合配体, 制备新颖的具有杂化磷酸锌骨架的化合物, 并通过刚性配体的空间效应在一定程度上限制磷酸锌聚合体的外延连接. 本文报道一种一维链状杂化磷酸盐(2,2′-bipy)2Zn2(PO4H)(PO4H2)2(以下简称FJ-10, FJ: Fujian Institute of Research on the Structure of Matter)的水热合成及单晶结构表征. 在磷酸锌体系中, FJ-10具有新颖的骨架拓扑结构和堆垛方式. 我们将对此类化合物的合成、结构与性质进行系列报道.     

Syntheses and structures of three new scandium selenites: Sc2(SeO3)3·H2O, Sc2 (SeO3)3·3H2O and CsSc3(SeO3)4 (HSeO3)2·2H2O

Three new hydrated scandium selenites have been hydrothermally synthesized as single crystals and structurally and physically characterized. Sc₂(SeO₃)₃·H₂O crystallizes as a new structure type containing novel ScO₇ pentagonal bipyramidal and ScO₆₊₁ capped octahedral coordination polyhedra. Sc₂(SeO₃)₃·3H₂O contains typical ScO₆ octahedra and is isostructural with its M₂(SeO₃)₃·3H₂O (M=Al, Cr, Fe, Ga) congeners. CsSc₃(SeO₃)₄(HSeO₃)₂·2H₂O contains near-regular ScO₆ octahedra and has essentially the same structure as its indium-containing analogue. All three phases contain the expected pyramidal [SeO₃]^2- selenite groups. Crystal data: Sc₂(SeO₃)₃·3H₂O, M_r=524.85, trigonal, R3c (No. 161), , , , Z=6, R(F)=0.018, wR(F²)=0.036; Sc₂(SeO₃)₃·H₂O, M_r=488.82, orthorhombic, P2₁2₁2₁ (No. 19), , , , , Z=4, R(F)=0.051, wR(F²)=0.086; CsSc₃(SeO₃)₄(HSeO₃)₂·2H₂O, M_r=1067.60, orthorhombic, Pnma (No. 62), , , , , Z=4, R(F)=0.035, wR(F²)=0.070.     

The synthesis and crystal structure of vanadium complexes: [VO2(phen)2]·6H2O and [2,2′-(bipy)2VO2](H2BO3)·3H2O

The organic-inorganic hybrid materials vanadium oxide [V^IVO₂(phen)₂]·6H₂O (1) and [(2,2′-bipy)₂V^VO₂](H₂BO₃)·3H₂O (2) have been conventional and hydrothermal synthesized and characterized by single crystal X-ray diffraction, elemental analyses, respectively. Although the method and the ligand had been used in the syntheses of the compounds (1) and (2) are different, they almost possess similar structure. They all exhibit the distorted octahedral [VO₂N₄] unit with organonitrogen donors of the phen and 2,2′-bipy ligands, respectively, which coordinated directly to the vanadium oxide framework. And they are both non-mixed-valence complexes. But the compound (1) is isolated, and the compound (2) consists of a cation of [(2,2′-bipy)₂V^VO₂]⁺ and an anion of (H₂BO₃)⁻. So the valence of vanadium of (1) and (2) are tetravalence and pentavalence, respectively. Meanwhile it is noteworthy that π-π stacking interaction between adjacent phen and 2,2′-bipy groups in compounds 1 and 2 also play a significant role in stabilization of the structure. Thus, the structure of [V^IVO₂(phen)₂]·6H₂O and [(2,2′-bipy)₂V^VO₂](H₂BO₃)·3H₂O are both further extended into interesting three-dimensional supramolecular. Crystal data: (1) Triclinic, a=8.481(4), b=12.097(5), and α=66.32(2), β=82.97(3), and γ=82.59(4)°, Z=2, R₁=0.0685, wR₂=0.1522. (2) Triclinic, a=6.643(13), b=11.794(2), and α=101.39(3), β=101.59(3), and γ=97.15(3)°, Z=2, R₁=0.0736, wR₂=0.1998.     

A novel 2D layer structure constructed from sandwich-type transition metal substituted tungstates and nickel coordination fragments: {[Ni(enMe)2]2[Ni(enMe)2(H2O)]2[As2W18Ni4(enMe)2O68]}·2H3O·2H2O

A novel polyoxometalate {[Ni(enMe)₂]₂[Ni(enMe)₂(H₂O)]₂[As₂W₁₈Ni₄(enMe)₂O₆₈]}·2H₃O·2H₂O (1) (enMe = 1,2-propylenediamine) has been synthesized and characterized, which is the first high-dimensional structure constructed from sandwich-type transition metal substituted tungstates and transition metal coordination groups.     

Hydrothermal synthesis and characterization of a new three-dimensional hybrid zinc phosphate [Zn2(HPO4)2(4,4′-bipy)]·3H2O with neutral porous framework

Employing 4,4′-bipyridine as a bridged ligand, a new three-dimensional (3-D) hybrid zinc phosphate [Zn₂(HPO₄)₂(4,4′-bipy)]·3H₂O has been prepared under hydrothermal conditions and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic space group C2/c, with cell parameters, , , , β=90.21(3)°, and Z=4. The connectivity of the ZnO₃N and HPO₄ tetrahedra results in a 2-D neutral layer that with interesting 4,8² net along the bc plane. Furthermore, the 4,4′-bipyridine molecule links the 4,8² net into a 3-D structure. The water molecules sit in the middle of the channels and interact with the framework via hydrogen bonds. The compound exhibits intense photoluminescence at room temperature.     

A mixed cation nickel diphosphate with a layered intergrowth structure: synthesis, structural and magnetic characterization of Na(NH4)[Ni3(P2O7)2(H2O)2]

A nickel diphosphate with mixed cations, Na(NH₄)[Ni₃(P₂O₇)₂(H₂O)₂] with a layered structure has been synthesized under hydrothermal conditions for the first time and characterized by single crystal X-ray diffraction, IR spectroscope and magnetization measurements. The structure consists of cis- and trans-edge sharing NiO₆ octahedral chains linked via P₂O₇ units to [Ni₃P₄O₁₆]²⁻ layers. The ammonium and sodium cations are alternately located in the interlayer spaces. The mixed cations play an important role in the structural formation of this layered compound, leading to a new layer-stacking variant. The magnetic susceptibility obeys a Curie–Weiss law with μ_eff of 3.32 μ_B, showing the Ni²⁺ character and weak antiferromagnetic interactions.     

Synthesis and structure of a novel three-dimensional metal selenite containing multidirectional intersecting double helical chains: [Fe2(H2O)4(SeO3)2]

A novel three-dimensional metal selenite [Fe₂(H₂O)₄(SeO₃)₂] (1) has been hydrothermally synthesized and characterized by the elemental analyses, IR spectrum, TG analysis and the single crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a=6.5283(13) Å, b=8.8754(18) Å, c=7.6798(15) Å, (=98.82(3)β, V=439.71(15) Å3, and Z=2. Compounds 1 exhibits interesting three-dimensional structure constructed from {FeO₆} octahedra and {SeO₃} pyramids linked via the corner- and/or edge-sharing mode. The most interesting structural feature of compound 1 is that the existence of multidirectional intersecting double helical chains in one compound.     

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.     

Synthesis, structure, and properties of the first trimetallic phosphate [Ni(H2O)4]Cd(VO)(PO4)2 with neutral 3-D pillared-layer framework

Hydrothermal reactions of VOSO₄·3H₂O, CdAc₂·2H₂O, NiCl₂·6H₂O, H₃PO₄, and H₂O yield the first example of trimetallic phosphate materials, [Ni(H₂O)₄]Cd(VO)(PO₄)₂1. The single-crystal X-ray diffraction shows that its structure consists of Cd/V/O binary metal oxide lamellas decorated by PO₄ tetrahedra, which are further pillared by NiO₂(H₂O)₄ octahedra to generate a neutral 3-D framework containing two intercrossing 8-MR channels where the coordinated water molecules protrude into. Thermal and magnetic behaviors of this material were also measured. Crystal data: CdNiVP₂O₁₃H₈, orthorhombic Ibca (No.73), a=7.1307(2) Å, b=18.6248(3) Å, c=14.8046(2) Å, V=1966.17(7) Å³, Z=8.     

[Zn(H2PO4)4] clusters and ∞[Zn2(HPO4)3(H2PO4)2] layers in two new zinc phosphates templated by [H2(4-amino-2.2.6.6-tetramethylpiperidine)] cations

Two zinc phosphates (ZnPO), [H₂(N₂C₉H₂₀)]·[Zn(H₂PO₄)₄] (I) and [H₂(N₂C₉H₂₀)]₂·[Zn₂(HPO₄)₃(H₂PO₄)₂]·H₂O (II), are synthesized under hydrothermal conditions using 4-amino-2.2.6.6-tetramethylpiperidine as organic template. I crystallizes in space group with , , , α=92.57(1)°, β=89.76(1)°, γ=102.16(2)°, and Z=2. Its structure, refined to R=0.029 and R_w=0.076 for 4279 independent reflections, consists of [Zn(H₂PO₄)₄]²⁻ clusters held together through strong hydrogen bonds to form pseudo-layers between which the doubly protonated amine molecules are inserted. II is monoclinic, C2, with , , , β=103.72(5)°, and Z=4 (R=0.079, R_w=0.268, 2477 independent reflections). The structure of II consists of _∞[Zn₂(HPO₄)₃(H₂PO₄)₂]⁴⁻ inorganic (2D) layers built up from vertex-sharing [ZnO₄] and [(H₂/H)PO₄] tetrahedra. Organic cations and water molecules ensure the connection between these layers via hydrogen bonds. It is shown that numerous (1D), (2D), e.g., [H₂(N₂C₉H₂₀)]₂·[Zn₂(HPO₄)₃(H₂PO₄)₂]·H₂O, and (3D) (ZnPO) result from the condensation of the [Zn(H₂PO₄)₄]²⁻ clusters.     

[NH3CH2CHCH3NH3]][B8O11(OH)4]·H2O: Synthesis and characterization of the first 1D borate templated by 1,2-diaminopropane

A new hydrated borate compound, [NH₃CH₂CHCH₃NH₃]][B₈O₁₁(OH)₄]·H₂O 1, has been synthesized in the presence of 1,2-diaminopropane acting as a structure-directing agent under mild conditions. Its structure was determined by single crystal X-ray diffraction and further characterized FTIR, elemental analysis, powder X-ray diffraction and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group P2₁/c (No. 14), a=10.0787(7) Å, b=8.8482(6) Å, c=19.3097(4) Å, β=91.352(6)°, V=1721.53(2) Å³, and Z=4. The structure consists of infinite open-branched borate chains constructed from [B₃O₆(OH)] units, onto which the [B₅O₇(OH)₃] groups are grafted. It represents the first example of one-dimensional borate templated by an organic amine. The adjacent borate chains are further linked together by extensive hydrogen bonds to form a 3D supramolecular network. The diprotonated organic amines and guest water molecules are filled in the free space of the hydrogen-bonded network and interact with the inorganic framework by extensive hydrogen bonds.     

Hydrothermal synthesis and characterization of layered vanadium phosphite: [HN(C2H4)3N][(VO)2(HPO3)2(OH)(H2O)]·H2O

A novel compound, [HN(C₂H₄)₃N][(VO)₂(HPO₃)₂(OH)(H₂O)]·H₂O, was hydrothermally synthesized and characterized by single crystal X-ray diffraction. This compound crystallizes in the monoclinic system with the space group C2/c and cell parameters a=11.0753(3) Å, b=17.8265(6) Å, c=16.5229(5) Å, and β=92.362(2)°. The structure of the compound consists of vanadium phosphite layers which are built up from the infinite one-dimensional chains of [(VO)(H₂O)(HPO₃)₂]²⁻ of octahedral VO₅(H₂O) and pseudo pyramidal [HPO₃], and bridging binuclear fragments of [VO(OH)]₂. Thermogravimetric analysis and magnetic susceptibility data for this compound are given.     

Synthesis and structural characterization of two polymorphs of Fe(2,2′-bpy)(HPO4)(H2PO4)

Two polymorphs of an organic-inorganic hybrid compound, Fe(2,2′-bpy)(HPO₄)(H₂PO₄) (1 and 2) (2,2′-bpy=2,2′-bipyridine), have been synthesized by hydrothermal methods and structurally characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and magnetic susceptibility. Crystal data are as follows: Polymorph 1, monoclinic, space group P2₁/n (No. 14), a=10.904(2) Å, b=6.423(1) Å, c=19.314(3) Å, β=101.161(3)°, and Z=4; Polymorph 2, monoclinic, space group P2₁/c (No. 14), a=11.014(1) Å, b=15.872(2) Å, c=8.444(1) Å, β=109.085(3)°, and Z=4. Polymorph 1 adopts a chain structure in which each iron atom is coordinated by two nitrogen atoms from 2,2′-bpy ligand and four phosphate oxygen atoms. These infinite chains are extended into a 3-D supramolecular array via π-π stacking interactions of the lateral 2,2′-bpy ligands. The structure of polymorph 2 consists of the same building units, namely FeO₄N₂ octahedron, HPO₄ and H₂PO₄ tetrahedra, and 2,2′-bpy ligand, which are linked through their vertices forming an undulated sheetlike structure with 4,12 network. Adjacent layers are extended into a 3-D array via π-π stacking interactions of the aromatic groups. Magnetic susceptibility measurement results confirm that the iron atoms in both compounds are present in the +3 oxidation state.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Self-assembly of polyoxometalate clusters into a 3-D heterometallic framework via covalent bonding: synthesis, structure and characterization of Na4[Nd8(dipic)12(H2O)9][Mo8O26]·8H2O

An unprecedented hybrid solid obtained by self-assembly of octamolybdate clusters into a three-dimensional alkali metal modified neodymium-organic heterometallic framework is described. Crystal data: monoclinic, space group P2₁/n, , , , β=98.90(3)°; ; Z=2, R (final)=0.0474. The data were collected on a Rigaku R-AXIS RAPID IP diffractometer at 293 K using graphite-monochromated MoKα radiation () and oscillation scans technique in the range of 1.98°<θ<27.48°.     

Syntheses and crystal structures of two new hydrated borates, Zn8[(BO3)3O2(OH)3] and Pb[B5O8(OH)]·1.5H2O

Two new hydrated borates, Zn₈[(BO₃)₃O₂(OH)₃] and Pb[B₅O₈(OH)]·1.5H₂O, have been prepared by hydrothermal reactions at 170 °C. Single-crystal X-ray structural analyses showed that Zn₈[(BO₃)₃O₂(OH)₃] crystallizes in a non-centrosymmetric space group R32 with a=8.006(2) Å, c=17.751(2) Å, Z=3 and Pb[B₅O₈(OH)]·1.5H₂O in a triclinic space group P1¯ with a=6.656(2) Å, b=6.714(2) Å, c=10.701(2) Å, α=99.07(2)°, β=93.67(2)°, γ=118.87(1)°, Z=2. Zn₈[(BO₃)₃O₂(OH)₃] represents a new structure type in which Zn-centered tetrahedra are connected via common vertices leading to helical ribbons _∞¹[Zn₈O₁₅(OH)₃]¹⁷⁻ that pack side by side and are further condensed through sharing oxygen atoms to form a three-dimensional _∞³[Zn₈O₁₁(OH)₃]⁹⁻ framework. The boron atoms are incorporated into the channels in the framework to complete the final structure. Pb[B₅O₈(OH)]·1.5H₂O is a layered compound containing double ring [B₅O₈(OH)]²⁻ building units that share exocyclic oxygen atoms to form a two-dimensional layer. Symmetry-center-related layers are stacked along the c-axis and held together by interlayer Pb²⁺ ions and water molecules via electrostatic and hydrogen bonding interactions. The IR spectra further confirmed the existence of both triangular BO₃ and OH groups in Zn₈[(BO₃)₃O₂(OH)₃], and BO₃, BO₄, OH groups as well as guest water molecules in Pb[B₅O₈(OH)]·1.5H₂O.     

Synthesis and characteristics of a novel 3-D organic amine oxalate: (enH2)1.5[Bi3(C2O4)6(CO2CONHCH2CH2NH3)]·6.5H2O

A novel 3-D compound of (enH₂)_1.5[Bi₃(C₂O₄)₆(CO₂CONHCH₂CH₂NH₃)]·6.5H₂O has been hydrothermally synthesized and characterized by IR, ultraviolet-visible diffuse reflection integral spectrum (UV-Vis DRIS), fluorescence spectra, TGA and single crystal X-ray diffraction. It crystallizes in the monoclinic system, space group C2/c with , , , β=112.419(3)°, , Z=8, R₁=0.0463 and wR₂=0.1393 for unique 7686 reflections I>2σ(I). In the title compound, the Bi atoms have eight-fold and nine-fold coordination with respect to the oxygen atoms, with the Bi atoms in distorted dodecahedron and monocapped square antiprism, respectively. The 3-D framework of the title compound contains channels and is composed of linkages between Bi atoms and oxalate units, forming honeycomb-like layers with two kinds of 6+6 membered aperture, and pillared by oxalate ligands and monamide groups. The channels have N-ethylamine oxalate monamide group ⁻CO₂CONHCH₂CH₂NH₃⁺, which is formed by the in situ reaction of en and oxalate acid. At room temperature, the complex exhibits intense blue luminescence with an emission peak at 445 nm.     

Hydrothermal synthesis and structure of the first tin(II) squarate Sn2O(C4O4)(H2O)—comparison with Sn2[Sn2O2F4]

A tin(II) squarate Sn₂O(C₄O₄)(H₂O) was synthesized by hydrothermal technique. It crystallizes in the monoclinic system, space group C2/m (no. 12) with lattice parameters a=12.7380(9) Å, b=7.9000(3) Å, c=8.3490(5) Å, β=121.975(3)°, V=712.69(7) Å³, Z=4. The crystal structure determined with an R=0.042 factor, consists of [(Sn₄O₁₀)(H₂O)₂] units connected from one another in the [101] and [010] directions via squarate groups to form layers separated by Sn(II) lone pairs. This compound presents the same remarkable structural arrangement as observed in the tin-oxo-fluoride Sn₂[Sn₂O₂F₄] inorganic compound with Sn(II) lone pairs E(1) and E(2) concentrated in large rectangular-shape tunnels running along [001] direction.