Synthesis and Characterization of the New Copper Indium Phosphate Cu8In8P4O30

The system CuO/In₂O₃/P₂O₅ has been investigated using solid state reaction between CuO, In₂O₃ and (NH₄)₂HPO₄ in silica glass crucibles at 900 °C. The powder samples were characterized by X‐ray diffraction, thermal analysis and FT‐IR spectroscopy. Orange single crystals of the new quaternary phase were achieved by the process of crystallization with mineralizers in sealed silica glass ampoules. They were then analyzed with EDX and single‐crystal X‐ray analysis in which the composition Cu₈In₈P₄O₃₀ with the triclinic space group P$\bar{1}$ (No 2) with a = 7,2429(14) Å, b = 8,8002(18) Å, c = 10,069(2) Å, α = 103,62(3)°, β = 106,31(3)°, γ = 101,55(3)° and Z = 1 was found. The three‐dimensional framework consists of [InO₆] octahedra and distorted [CuO₆] octahedra, overcaped [InO₇] prisms and [PO₄] tetrahedra, also trigonal [(CuIn)O₅] bipyramids and distorted [(CuIn)O₆] octahedra, where copper and indium are partly exchanged against each other. Cu₈In₈P₄O₃₀ exhibits an incongruent melting point at 1023 °C.     

Synthesis,Crystal Structure and Characterization of the Copper Iron Phosphate Cu8Fe2O5(PO4)4

The system CuO‐Fe₂O₃‐P₂O₅ has been investigated by means of the solid state reaction between CuO, Fe₂O₃ and (NH₄)₂HPO₄ in quartz crucibles at 900 °C. The powder samples were characterized by X‐ray diffraction, IR spectroscopy and TG/DTA. Single crystals of a new quaternary phase Cu₈Fe₂P₄O₂₁ were achieved by cooling from the melt of the compound in a sealed, evacuated quartz ampoule. Cu₈Fe₂O₅(PO₄)₄ crystallizes in the monoclinic space group C2/m (No 12) with a = 15.9733(8) Å, b = 5.9438(3) Å, c = 9.5530(5) Å, β = 113.76(1)°, Z = 2. The three‐dimensional framework consists of [FeO₆] octahedra, three different [CuO₅] polyhedra and [PO₄] tetrahedra. Cu₈Fe₂P₄O₂₁ exhibits an incongruently melting point at 945 °C.     

A New Compound in the Cu‐In System – the Synthesis and Structure of Cu10In7

A new binary phase, Cu₁₀In₇, was found during the investigation of the η‐phase field in the Cu‐In system. Single crystals of Cu₁₀In₇ were grown from a melt under an inert atmosphere. The compound crystallizes in the monoclinic space group C2/m with cell parameters a = 13.8453(2) Å, b = 11.8462(1) Å, c = 6.7388(1) Å and β = 91.063(1). The structure is based on a unit of face‐sharing octahedra consisting of five Cu₄In₂ octahedra terminated by Cu₅In octahedra at both ends. The crystal structure is closely related to the Cu₁₁In₉ structure type.     

Silver Vanadyl(IV) ortho‐Pyrophosphate: Synthesis,Crystal Structure,and Characterization of the (V≡O)2+ Group

Ag₆(V^IVO)₂(PO₄)₂(P₂O₇) was obtained by reaction of Ag₃PO₄ and (VO)₂P₂O₇ (sealed ampoule, 550 °C, 3 d). The crystal structure of the new mixed ortho‐pyrophosphate was determined from X‐ray single‐crystal data [Pnma, Z = 4, a = 12.759(3) Å, b = 17.340(4) Å, c = 6.418(1) Å, R₁ = 0.071, wR₂ = 0.184 for 3174 unique reflections with F_o > 4σ(F_o), 141 variables]. Ag⁺ ions are located in between layers [(V^IVO)₂(PO₄)₂(P₂O₇)]^6–. Equilibrium relations of the new phosphate to neighboring phases were determined. The electronic structure of the (V^IV≡O)²⁺ group was investigated by polarized electronic absorption spectroscopy (ν̃_1a = 9450 cm^–1, ν̃_1b = 9950 cm^–1, ν̃₂ = 14750 cm^–1), EPR spectroscopy [X‐ and Q‐band, powder and single crystal, orthorhombic crystal g‐tensor with g₁ = 1.9445(3), g₂ = 1.9521(3), g₃ = 1.9695(3)], and magnetic measurements (powder, μ_exp/μ_B = 1.71, Θ_p = –1.7 K).     

Preparation and Crystal Structure of Potassium Iron Hydrogen Phosphate,KFe3(HPO4)2(H2PO4)6 · 4 H2O

Single crystals of potassium iron hydrogen phosphate, KFe₃(HPO₄)₂(H₂PO₄)₆ · 4 H₂O, were prepared hydrothermally by heating a mixture of Fe₂O₃, H₃PO₄ and K₂CO₃ with a small amount of water. It crystallizes monoclinic, space group C2/c (N° 15 Int. Tab.) with Z = 4 and a = 1701(2), b = 960.4(5), c = 1750(1) pm, β = 90.88(7)°. The crystal structure was solved by using 1716 unique reflections F₀ > 4σ(F₀) with a final wR2 value of 0.126 (SHELXL-93). The main feature of the crystal structure are layers formed by PO₄-tetrahedra around the FeO₆-octahedra parallel to (001). K⁺ and H₂O molecules connect these layers. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), Charge Distribution (CHARDI) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound. The existence of hydrogen bonds is confirmed by these calculations.     

Preparation and Crystal Structure of Sodium Iron Hydrogen Phosphate,NaFe(HPO4)(H2PO4)2 · H2O

Single crystals of sodium iron hydrogen phosphate, NaFe(HPO₄)(H₂PO₄)₂ · H₂O, were prepared hydrothermally by heating a mixture of Fe₂O₃, H₃PO₄ and Na₂CO₃ with a small amount of water. It crystallizes orthorhombic (Pbcn (N° 60), Z = 8, a = 872.91(7), b = 1249.54(8), c = 1894.4(1) pm). The crystal structure was solved by using 1121 unique reflections I > 2σ(I) and refined for a final conventional residual R = 0.039 (188 variables, 25 atoms including hydrogen in the asymmetric unit). The main feature of the crystal structure is a ReO₃-like network formed by hydrogenphosphate-, dihydrogenphosphate-groups and Fe O₆ octahedra with channels along the [201], [010] and [201] directions. Na⁺ and H₂O molecules are occupying these channels. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR) and the Madelung Part of Lattice Energy (MAPLE) are calculated for the title compound.     

Synthesis and Crystal Structure of a Novel A‐Zeolite‐like Copper Complex: [Cu12(SO4)12(3H2O)]·H2O

The reaction of CuBr₂, N(CH₂CH₂COOH)₃, and Nd(NO₃)₃·6H₂O in water adjusted pH = 5‐6 with H₂SO₄ at constant 55 °C afforded a novel three‐dimensional coordination complex [Cu₁₂(SO₄)₁₂(3H₂O)]·H₂O, ( 1 ), which was characterized by IR, elemental analysis, and X‐ray diffraction. The crystal structure data of 1 as follows: Cubic, , a = b = c = 24.018(2) Å, V = 13855 (3) ų, Z = 968, D_c = 1.905 g/cm³, F(000) = 7712, R₁ = 0.0352, wR₂ = 0.0866 (I > 2σ(I)), R₁ = 0.0449, wR₂ = 0.0927 (for all data) and S = 1.075. The analysis of crystal structure indicates that the structure of 1 is similar to that of silicate zeolite (Na₁₂[Al₁₂Si₁₂O₄₈]·27H₂O).     

Synthesis,Crystal Structure,and Characterization of a New Adduct 3-Ammoniumphenyl Sulfone Dihydrogenphosphate Phosphoric Acid [C12H14N2SO2](H2PO4)2H3PO4

Abstract

A new adduct 3-ammoniumphenyl sulfone dihydrogenphosphate phosphoric acid, [C₁₂H₁₄N₂O₂S](H₂PO₄)₂H₃PO₄, has been synthesized by slow evaporation at room temperature using 3-aminophenyl sulfone as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 293 K, can be described as inorganic layers built by H₂PO₄ ^? groups and H₃PO₄ molecules, parallel to the (a, c) planes at y = 0.5, between which molecules of the organic group [C₁₂H₁₄N₂O₂S]²⁺ are inserted. In this atomic arrangement, hydrogen bonds and van der Waals interactions between the different species play an important role in the tri-dimensional network cohesion. Solid-state ¹³C and ³¹P MAS NMR spectroscopies are in agreement with the X-ray structure.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Tables S1 and S2. Figures S1 and S2.]

GRAPHICAL ABSTRACT      

High‐Pressure Synthesis and Single‐Crystal Structure Elucidation of the Indium Oxide‐Borate In4O2B2O7

The indium oxide‐borate In₄O₂B₂O₇ was synthesized under high‐pressure/high‐temperature conditions at 12.5 GPa/1420 K using a Walker‐type multianvil apparatus. Single‐crystal X‐ray structure elucidation showed edge‐sharing OIn₄ tetrahedra and B₂O₇ units building up the oxide‐borate. It crystallizes with Z = 8 in the monoclinic space group P2₁/n (no. 14) with a = 1016.54(3), b = 964.55(3), c = 1382.66(4) pm, and β = 109.7(1)°. The compound was also characterized by powder X‐ray diffraction and vibrational spectroscopy.     

Synthesis and Characterization of New Copper(I) Complexes Containing Thione Derivatives of 1, 2, 4‐Triazine. Crystal Structure of [Cu(PPh3)2(ATTO)]NO3 (ATTO = 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one)

The reaction of 4‐amino‐1, 2, 4‐triazin‐3(2H)‐thione‐5‐one (ATTO, 1 ) with [Cu(PPh₃)₂]NO₃ in ethanol led to the complex [Cu(PPh₃)₂(ATTO)]NO₃ ( 2 ). 2 was characterized by elemental analyses, IR, ¹H NMR and Raman spectroscopy. A single‐crystal X‐ray diffraction of compound 2 revealed that ATTO acts as a bidentate ligand via its nitrogen and sulfur atoms. Crystal data for 2 at 20 °C: space group P2₁/n with a = 975.7(1), b = 1533.5(2), c = 2504.2(3) pm, β = 92.25(1)°, Z = 4, R₁ = 0.0632.     

Synthesis and Characterization of the New Copper Tetraphosphonate Cu2[(HO3PCH2)4C6H2]·2H2O

Following the strategy of using polyfunctional phosphonic acids for the synthesis of three‐dimensional metal phosphonates, the ethyl ester of a tetraphosphonic acid, i. e. 1,2,4,5‐(Et₂O₃PCH₂)₄C₆H₂, was used in the hydrothermal synthesis of the new copper tetraphosphonate, Cu₂[(HO₃PCH₂)₄C₆H₂]·2H₂O ( 1 ). The in situ hydrolysis of the ethyl ester leads to the acid (1,2,4,5‐(H₂O₃PCH₂)₄C₆H₂) which reacts with the Cu²⁺ ions to form the green coarse‐crystalline product. The title compound is the first fully characterized copper tetraphosphonate. Its structure was solved from single crystal data ( 1 : triclinic, , a = 4.9262(10), b = 8.1890(16), c = 11.800(2) Å, α = 71.17(3), β = 89.15(3), γ = 88.56(3)°, V = 450.39(16) ų, Z = 2, R1 = 0.0284, wR₂ = 0.0682). The structure is built up from edge‐sharing CuO₅ polyhedra each containing a single H₂O molecule. Thus, dimeric [Cu₂O₈] units are formed. In the second coordination sphere of each of the Cu²⁺ ions four HO₃PCH₂R units are observed. The [Cu₂O₈] polyhedra are connected to eight other [Cu₂O₈] polyhedra by these organic linkers and a three‐dimensional framework structure is formed. Thermogravimetric, magnetic, and temperature dependent powder XRD measurements and the Raman‐spectrum are also presented.     

Solvothermal Synthesis, Crystal Structure Determination, and Properties of the Thioantimonate [Ph4P]2[Sb6S10]

Summary.  The reaction of elemental antimony with elemental sulfur and [Ph₄P]Br in an aqueous solution of neopentanediamine under solvothermal conditions yields yellow needles of the new thioantimonate(III) [Ph₄P]₂[Sb₆S₁₀]. The structure consists of [Ph₄P]⁺ cations and infinite one-dimensional anionic (Sb₆S₁₀ ²⁻)_n chains running along the crystallographic a axis. The chains are composed of 10-membered Sb₅S₅ rings with alternating Sb and S atoms and separated by the tetraphenylphosphonium cations. Upon heating the compound decomposes in two distinct steps, starting at about 100°C. The final product was identified by X-ray powder diffractometry as Sb₂S₃. Received December 17, 1999. Accepted (revised) February 7, 2000     

A New Dinuclear Copper (II) Complex of a Bis‐macrocyclic Ligand: Synthesis,Characterization, Crystal Structure and Magnetic Properties

A new dinuclear Cu(II) complex, [Cu₂L(N₃)₂](ClO₄)₁.₅ (OH)_4.5 · 2H₂O 0.5C₂H₅OH (1), of a bis‐macrocyclic ligand, 2,6‐bis(l,4,7,10‐tetraazacyclododecan‐10‐ylmethyl)‐methoxybenzene (L), has been synthesized, characterized and structurally determined by X‐ray diffraction analysis. Complex 1 crystallizes in orthorhombic crystal system, Pca2(l) space group with a = 1.5371(3), b = 1.6641(3), c = 3.0950(6) nm, V = 7.917(3) nm³, F_w = 904.62, Z=8, D_c= 1.529 g/cm³ and final R = 0.0568, wR = 0.1406 for 10410 observed reflections with I≥2σ (I). Both Cu(II) centers in the structure are coordinated by four nitrogen atoms of 1,4,7, 10‐tetraazacyclododecane (cyclen) and a nitrogen donor of the axial azide anion. Each Cu(II) center is in a square‐pyramidal coordination environment, and the intra‐and nearest inter‐molecular Cu? Cu nonbonding distances are 0.9855 and 0.7298 nm, respectively. Variable temperature magnetic susceptibility measurements in the range of 4.2–300 K indicate mat there exists weak intra‐ and inter‐molecular antiferromagnetic coupling between the Cu(II) centers with 27= ?4.2 cm^?1 and Θ = ?0.47 K.     

Synthesis,Structure, and Spectroscopic Properties of Copper(II) and Nickel(II) Complexes Containing the 1, 4, 7‐Triisopropyl‐1, 4, 7‐triazacyclononane Ligand

Three new complexes [CuL(N₃)₂] ( 1 ), [CuL(SCN)₂] ( 2 ), and [NiL(SCN)₂] ( 3 ) (L = 1, 4, 7‐triisopropyl‐1, 4, 7‐triazacyclononane, [—NR—C₂H₄—NR—C₂H₄—NR—C₂H₄—], R = i‐Pr) have been synthesized and structurally characterized. The three complexes all crystallize in the monoclinic space group P2₁/n, with the unit cell parameters a = 9.100(5), b = 19.492(11), c = 11.646(6)Å, β = 94.526(9)° for 1 , a = 10.148(3), b = 13.611(5), c = 15.777(6)Å, β = 95.412(6)° for 2 and a = 9.270(7), b = 16.629(14), c = 14.886(12)Å, β = 101.217(15)° for 3 . The central copper(II) and nickel(II) ions are coordinated to five nitrogen atoms, three of which from the L and two from N₃^— or SCN^—, forming a slightly distorted square pyramidal geometry. Moreover, elemental analysis, IR, UV‐vis and ESR spectra of complexes 1 ‐ 3 were also determined.     

Further Examples of the P‐O‐P Connection in Borophosphates: Synthesis and Characterization of Li2Cs2B2P4O15, LiK2BP2O8, and Li3M2BP4O14 (M=K,Rb)

A new series of anhydrous mixed alkali‐metal borophosphates—Li₂Cs₂B₂P₄O₁₅ ( 1 ), LiK₂BP₂O₈ ( 2 ), Li₃K₂BP₄O₁₄ ( 3 ), and Li₃Rb₂BP₄O₁₄ ( 4 )—have been successfully synthesized by using the conventional solid‐state reaction method. Compound 1 contains a novel fundamental building unit (FBU), [B₄P₈O₃₀], with B/P=1:2. Compound 2 contains an FBU of [B₂P₄O₁₆] with B/P=1:2. Compounds 3 and 4 are isotypic, and they have a [B(P₂O₇)₂] unit as their FBU. In all four compounds, their FBUs are connected through corner sharing to generate layered anionic partial structures, and then further linked with metallic polyhedra to form three‐dimensional (3D) frameworks. Most interestingly, three of the four compounds contain direct P‐O‐P connections in their structures, which is extremely rare among borophosphates. Thermal analyses, IR spectroscopy, and UV/Vis/near‐IR diffuse reflectance spectroscopy have also been performed on the four title compounds.     

Synthesis and Characterization of the first Copper(II) Complex of 6‐Azathymine. The Crystal Structure of [[CuCl2(H2O)2(AT)}2] · 2H2O; (AT = 6‐Azathymine)

The reaction of 3, 4‐dihydro‐6‐methyl‐3‐thioxo‐1, 2, 4‐triazin‐5(2H)‐one (6‐aza‐2‐thiothymine, AAT, 1 ) with copper(I) chloride in presence of hydrochloric acid in methanol gives the complex [{CuCl₂(H₂O)₂(AT)}₂] · 2H₂O, 2 , AT = 6‐azathymine) in excellent yield. 2 was characterized by IR spectroscopy and elemental analyses as well as mass spectrometry. Also single‐crystal X‐ray diffraction studies on compound 2 revealed that AT acts as a monodentate ligand in the centrosymmetric binuclear complex via its oxygen atom. Crystal data for 2 at —80 °C: space group P2₁/c with a = 550.1(1), b = 2712.5(1), c = 729.7(1) pm, β = 95.99(1)°, Z = 2, R₁ = 0.0213.     

Synthesis, Structure and Characterization of Two-dimensional Network Copper Complex [Cu_3(nta)_2(azpy)_2(H_2O)_2]·6H_2O

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不对称大环双核铜(Ⅱ)配合物[Cu2(C23H26Cl2N4O2)](ClO4)2的合成、晶体结构及磁性

大环双核铜(Ⅱ)配合物由N,N′-二甲基-N,N′-二(3-甲酰基-5-氯水杨醛)乙二胺和1,3-丙二胺,与铜(Ⅱ)反应形成的,经过X-射线单晶衍射结果表明：a=0.871 05(16) nm,b=0.957 78(18) nm,c=1.810 4(3) nm,β=100.761(18)°,V=1.483 8(5) nm³,Z=2,D_c=1.762 Mg·m^-3,μ=1.85 mm^-1,F(000)=796,and final R₁=0.061,wR₂=0.126。晶体结构表明：两个铜离子位于双核大环中间,与大环的胺、亚胺以及酚羟基的氧进行配位。磁性结果表明配合物为反铁磁性。     

Synthesis and Characterization of the Manganese Hydroxide Halides Mn(OH)X (X = Br,I) and Crystal Structure of trans‐MnBr2·4H2O

The pale‐pink, hygroscopic compounds Mn(OH)X (X = Br, I) were obtained by high‐pressure synthesis in a Walker‐type multianvil apparatus. They crystallize in the space group P2₁/c with a = 640.48(3), b = 698.80(3), c = 615.54(2) pm, β = 110.30(1)° at 183(1) K (X = Br), and a = 686.18(3), b = 713.08(3), c = 637.18(3) pm, β = 109.51(1)° at 150(1) K (X = I). The crystal structures are isotypic to Cu(OH)Cl and consist of edge‐sharing distorted Mn(OH)₃X₃ octahedra arranged in sheets parallel to the bc‐plane. Spin‐polarized scalar‐relativistic DFT+U calculations predict an intrinsic magnetic insulating state (ca. 3.5 eV bandgap) that is proximate to frustration. Calculated effective magnetic moments equal to 4.34 μ_B/f.u. for Mn(OH)Br and 4.33 μ_B/f.u. for Mn(OH)I. FT‐IR spectroscopy confirmed interlayer hydrogen bonding. As a side result of the experiments, the compound trans‐MnBr₂ · 4H₂O was obtained. It crystallizes in the space group Cmcm with a = 438.64(2), b = 1167.84(6), and c = 730.95(4) pm.     

A Novel Dinuclear Copper(II) Complex Molecule: Synthesis and Crystal Structure of Cu2(phen)2(H2O)2(C5H6O4)2 with phen = 1,10‐phenanthroline

Blue crystals of Cu₂(phen)₂(H₂O)₂(C₅H₆O₄)₂ were obtained from a CH₃OH–H₂O solution containing CuCl₂, 1,10‐phenanthroline (phen), glutaric acid and Na₂CO₃. The crystal structure (monoclinic, P2₁/c (no. 14), a = 10.271(1), b = 10.595(1), c = 15.585(1) Å, β = 107.105(3)°, Z = 2, R = 0.0328, wR² = 0.1027 for 3376 observed reflections (F ≥ 2σ(F ) out of 3728 unique reflections) is built up of dinuclear Cu₂(phen)₂(H₂O)₂(C₅H₆O₄)₂ complex molecules centered at inversion centers. The Cu atoms are square‐pyramidally coordinated by two nitrogen atoms of one bidentate chelating phen ligand and three oxygen atoms from two bridging glutarate anions and one axial water molecule (d(Cu–N) = 2.018(2), 2.024(2) Å; basal d(Cu–O) = 1.949(2), 1.956(2) Å; axial d(Cu–O) = 2.382(2) Å). Through the π‐π stacking interactions extending in a direction, the complex molecules are interlinked into 2 D layers parallel to the ac plane. The resultant 2 D layers are held together by hydrogen bonds between water molecules and uncoordinated carboxyl oxygen atoms.