Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

Two Heteroleptic Zinc(II) Complexes: [Zn(phen)(C9H15O6)2] and [Zn2(phen)2(H2O)2(C10H16O4)2] · 3H2O

Reactions of a freshly prepared Zn(OH)_2‐2x(CO₃)x · yH₂O precipitate, phenanthroline with azelaic and sebacic acid in CH₃OH/H₂O afforded [Zn(phen)(C₉H₁₅O₄)₂] ( 1 ) and [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] · 3H₂O ( 2 ), respectively. They were structurally characterized by X‐ray diffraction methods. Compound 1 consists of complex molecules [Zn(phen)(C₉H₁₅O₄)₂] in which the Zn atoms are tetrahedrally coordinated by two N atoms of one phen ligand and two O atoms of different monodentate hydrogen azelaato groups. Intermolecular C(alkyl)‐H···π interactions and the intermolecular C(aryl)‐H···O and O‐H···O hydrogen bonds are responsible for the supramolecular assembly of the [Zn(phen)(C₉H₁₅O₄)₂] complexes. Compound 2 is built up from crystal H₂O molecules and the centrosymmetric binuclear [Zn₂(phen)₂(H₂O)₂(C₁₀H₁₆O₄)₂] complex, in which two [Zn(phen)(H₂O)]²⁺ moieties are bridged by two sebacato ligands. Through the intermolecular C(alkyl)‐H···O hydrogen bonds and π‐π stacking interactions, the binuclear complex molecules are assembled into layers, between which the lattice H₂O molecules are sandwiched. Crystal data: ( 1 ) C2/c (no. 15), a = 13.887(2), b = 9.790(2), c = 22.887(3)Å, β = 107.05(1)°, U = 2974.8(8)ų, Z = 4; ( 2 ) P1¯ (no. 2), a = 8.414(1), b = 10.679(1), c = 14.076(2)Å, α = 106.52(1)°, β = 91.56(1)°, γ = 99.09(1)°, U = 1193.9(2)ų, Z = 1.     

Na2Co(H2PO4)4·4H2O

In the title compound, disodium cobalt tetrakis­(dihydrogen­phosphate) tetrahydrate, the Co^II ion lies on an inversion centre and is octahedrally surrounded by two water molecules and four H₂PO₄ groups to give a cobalt complex anion of the form [Co(H₂PO₄)₄(OH₂)]^2?. The three‐dimensional framework results from hydrogen bonding between the anions. The relationship with the structures of Co(H₂PO₄)₂·2H₂O and K₂CoP₄O₁₂·5H₂O is discussed.     

Co0.50VOPO4·2H2O

The crystal structure of cobalt vanadophosphate dihydrate {systematic name: poly[diaqua‐μ‐oxido‐μ‐phosphato‐hemicobalt(II)vanadium(II)]}, Co_0.50VOPO₄·2H₂O, shows a three‐dimensional framework assembled from VO₅ square pyramids, PO₄ tetrahedra and Co[O₂(H₂O)₄] octahedra. The Co^II ions have local 4/m symmetry, with the equatorial water molecules in the mirror plane, while the V and apical O atom of the vanadyl group are located on the fourfold rotation axis and the P atoms reside on sites. The PO₄ tetrahedra connect the VO₅ polyhedra to form a planar P–V–O layer. The [Co(H₂O)₄]²⁺ cations link adjacent P–V–O layers via vanadyl O atoms to generate an unprecedented three‐dimensional open framework. Powder diffraction measurements reveal that the framework collapses on removal of the water molecules.     

Syntheses and Structures of Two Selenite Chloride Hydrates: Co(HSeO3)Cl · 3 H2O and Cu(HSeO3)Cl · 2 H2O

The first selenite chloride hydrates, Co(HSeO₃)Cl · 3 H₂O and Cu(HSeO₃)Cl · 2 H₂O, have been prepared from solution and characterised by single‐crystal X‐ray diffraction. The cobalt phase adopts an unusual “one‐dimensional” structure built up from vertex‐sharing pyramidal [HSeO₃]^2–, and octahedral [CoO₂(H₂O)₄]^2– and [CoO₂(H₂O)₂Cl₂]^4– units. Inter‐chain bonding is by way of hydrogen bonds or van der Waals' interactions. The atomic arrangement of the copper phase involves [HSeO₃]^2– pyramids and Jahn‐Teller distorted [CuCl₂(H₂O)₄] and [CuO₄Cl₂]^8– octahedra, sharing vertices by way of Cu–O–Se and Cu–Cl–Cu bonds. Crystal data: Co(HSeO₃)Cl · 3 H₂O, M_r = 276.40, triclinic, space group P 1 (No. 2), a = 7.1657(5) Å, b = 7.3714(5) Å, c = 7.7064(5) Å, α = 64.934(1)°, β = 68.894(1)°, γ = 71.795(1)°, V = 337.78(7) ų, Z = 2, R(F) = 0.036, wR(F) = 0.049. Cu(HSeO₃)Cl · 2 H₂O, M_r = 263.00, orthorhombic, space group Pnma (No. 62), a = 9.1488(3) Å, b = 17.8351(7) Å, c = 7.2293(3) Å, V = 1179.6(2) ų, Z = 8, R(F) = 0.021, wR(F) = 0.024.     

3D Coordination Polymers with Chiral Structures, [Ln2(tda)2(H2O)3]·5H2O: Hydrothermal Synthesis,Structural Characterization,and Luminescent Properties

Reactions of H₃tda (H₃tda = 1H‐1, 2, 3‐triazole‐4, 5‐dicarboxylic acid) with Sm(NO₃)₃ · 6H₂O, Eu(NO₃)₃ · 6H₂O, and Tb(NO₃)₃ · 6H₂O, in the presence of NaOH under hydrothermal conditions, produced three new coordination polymers, [Ln₂(tda)₂(H₂O)₃] · 5H₂O [Ln = Sm ( 1 ), Eu ( 2 ), Tb ( 3 )]. These compounds were structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), PXRD and single‐crystal X‐ray diffraction. The single‐crystal X‐ray diffraction studies of compounds 1 – 3 reveal that all compounds are three‐dimensional porous structures with chiral frameworks. Furthermore, the luminescence studies of compound 2 and 3 in the solid state reveal that they are potential luminescent materials at room temperature.     

Competitive Coordination of the Uranyl ion by Perchlorate and Water – The Crystal Structures of UO2(ClO4)2·3H2O and UO2(ClO4)2·5H2O and a Redetermination of UO2(ClO4)2·7H2O (Z. Anorg. Allg. Chem. 2003, 629, 1012–1016)

In the article “Competitive Coordination of the Uranyl ion by Perchlorate and Water – The Crystal Structures of UO₂(ClO₄)₂·3H₂O and UO₂(ClO₄)₂·5H₂O and a Redetermination of UO₂(ClO₄)₂·7H₂O” (Z. Anorg. Allg. Chem. 2003 , 629, 1012–1016), some wrong parameters and bond lengths for UO₂(ClO₄)₂·7H₂O were given in table 1 and table 3 The correct parameters are: a = 1449.5(2) pm, b = 921.6(1) pm, c = 1067.5(2) pm, V = 1422.5(4)·10⁶ pm³, ρ = 2.712 g·cm^?3, μ = 119 cm^?1. The corrected bond lengths for this structure are U–O(1) 175.8(5) pm, U–O(2) 239.1(5) pm, U–O(3) 240.8(5), U–O(4) 242.0(7). A cif file with the correct data has been deposited with the ICSD.     

M(H2O)2(4,4′‐bipy)[C6H4(COO)2]·2H2O (M = Mn2+, Co2+) – Zwei isotype Koordinationspolymere mit Schichtstruktur

M(H₂O)₂(4,4′‐bipy)[C₆H₄(COO)₂]·2H₂O (M = Mn²⁺, Co²⁺) – Two Isotypic Coordination Polymers with Layered Structure Monoclinic single crystals of Mn(H₂O)₂(4,4′‐bipy)[C₆H₄(COO)₂]·2H₂O ( 1 ) and Co(H₂O)₂(4,4′‐bipy)[C₆H₄(COO)₂]· 2H₂O ( 2 ) have been prepared in aqueous solution at 80 °C. Space group P2/n (no. 13), Z = 2; 1 : a = 769.20(10), b = 1158.80(10), c = 1075.00(10) pm, β = 92.67(2)°, V = 0.9572(2) nm³; 2 : a = 761.18(9), b = 1135.69(9), c = 1080.89(9) pm, β = 92.276(7)°, V = 0.9337(2) nm³. M²⁺ (M = Mn, Co), which is situated on a twofold crystallographic axis, is coordinated in a moderately distorted octahedral fashion by two water molecules, two oxygen atoms of the phthalate anions and two nitrogen atoms of 4,4′‐biypyridine ( 1 : M–O 219.5(2), 220.1(2) pm, M–N 225.3(2), 227.2(2) pm; 2 : Co–O 212.7(2), 213.7(2) pm, Co–N 213.5(3), 214.9(3) pm). M²⁺ and [C₆H₄(COO)₂)]^2? build up chains, which are linked by 4,4′‐biyridine molecules to yield a two‐dimensional coordination polymer with layers parallel to (001).Thermogravimetric analysis in air of 1 indicated a loss of water of crystallization between 154 and 212 °C and in 2 between 169 and 222 °C.     

Crystal Structure of the Mixed‐Valent Basic Mercury Nitrate HgI2(NO3)2·HgII(OH)(NO3)·HgII(NO3)2·4HgIIO [= Hg8O4(OH)(NO3)5]

Light‐yellow single crystals of the mixed‐valent mercury‐rich basic nitrate Hg₈O₄(OH)(NO₃)₅ were obtained as a by‐product at 85 °C from a melt consisting of stoichiometric amounts of (Hg^I₂)(NO₃)₂·2H₂O and Hg^II(OH)(NO₃). The title compound, represented by the more detailed formula Hg^I₂(NO₃)₂·Hg^II(OH)(NO₃)·Hg^II(NO₃)₂·4Hg^IIO, exhibits a new structure type (monoclinic, C2/c, Z = 4, a = 6.7708(7), b = 11.6692(11), c = 24.492(2) Å, β = 96.851(2)°, 2920 structure factors, 178 parameters, R1[F² > 2σ(F²)] = 0.0316) and is made up of almost linear [O‐Hg^II‐O] and [O‐Hg^I‐Hg^I‐O] building blocks with typical Hg^II‐O distances around 2.06Å and a Hg^I‐O distance of 2.13Å. The Hg₂²⁺ dumbbell exhibits a characteristic Hg‐Hg distance of 2.5079(7) Å. The different types of mercury‐oxygen units form a complex three‐dimensional network exhibiting large cavities which are occupied by the nitrate groups. The NO₃^? anions show only weak interactions between the nitrate oxygen atoms and the mercury atoms which are at distances > 2.6Å from one another. One of the three crystallographically independent nitrate groups is disordered.     

Co(C2(COO)2)(H2O)4 · 2 H2O und Co(C2(COO)2)(H2O)2: zwei Koordinationspolymere mit dem Acetylendicarboxylat‐Dianion

Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O and Co(C₂(COO)₂)(H₂O)₂: Two Co‐ordination Polymers of the Acetylenedicarboxylate Dianion By reaction of CoCO₃ with an aqueous solution of acetylenedicarboxylic acid and subsequent crystallisation single‐crystals of Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O were obtained (P2₁/a, Z = 2). In the solid state structure cobalt is octahedrally surrounded by four water molecules and two oxygen atoms of the carboxylate anions. These octahedra are connected to chains by the dicarboxylates. Already at ambient conditions Co(C₂(COO)₂)(H₂O)₄ · 2 H₂O looses four water molecules to give Co(C₂(COO)₂)(H₂O)₂ (isotypic to Mn[C₂(COO)₂] · 2 H₂O, C2/c, Z = 4). The cobalt cation is now octahedrally co‐ordinated by two water molecules and four oxygen atoms of the dicarboxylate ligands, which connect the Co octahedra to a three dimensional network. Thermoanalytical investigations show another mass loss at about 200 °C, which leads to non‐crystalline products. Measurements of the magnetic susceptibilities result in the expected behaviour for Co²⁺ in an octahedral co‐ordination (high spin, ⁴T₁ ground state). The effective magnetic moment at room temperature is n_eff = 5.51 μ_B.     

Synthesis and Crystal Structure of [La(phen)2(H2O)2(NO3)2]NO3 · 2(phen)(H2O) with phen = 1,10‐phenanthroline

The title compound [La(phen)₂(H₂O)₂(NO₃)₂](NO₃) · 2(phen)(H₂O) with phen = 1,10‐phenanthroline was prepared by the stoichiometric reaction of La(NO₃)₃ · 6 H₂O and 1,10‐phenanthroline monohydrate in a CH₃OH–H₂O solution. The crystal structure (triclinic, P 1 (no. 2), a = 11.052(2), b = 13.420(2), c = 16.300(2) Å, α = 78.12(1)°, β = 88.77(1)°, γ = 83.03(1)°, Z = 2, R = 0.0488, wR² = 0.1028) consists of [La(phen)₂(H₂O)₂(NO₃)₂]²⁺ complex cations, NO₃^– anions, phen and H₂O molecules. The La atom is 10‐fold coordinated by four N atoms of two bidentate chelating phen ligands and six O atoms of two H₂O molecules and two bidentate chelating NO₃^2– ligands with d(La–O) = 2.522–2.640 Å and d(La–N) = 2.689–2.738 Å. The intermolecular π‐π stacking interactions play an essential role in the formation of two different 2 D layers parallel to (001), which are formed by complex cations and uncoordinating phen molecules, respectively. The uncoordinated NO₃^– anions and H₂O molecules are sandwiched between the cationic and phen layers.     

Preparation,Crystal Structure and Vibrational Spectra of Ca2P2O6·2H2O and [Ca(H2O)3(H2P2O6)]·0.5(C12H24O6)·H2O

The calcium salts Ca₂P₂O₆ · 2H₂O ( 1 ) and [Ca(H₂O)₃(H₂P₂O₆)] · 0.5(C₁₂H₂₄O₆) · H₂O ( 2 ) were prepared and structurally characterized by single‐crystal X‐ray diffraction. Compound 1 crystallizes in the orthorhombic space group Pbca and compound 2 in the monoclinic space group P2₁/n. The crystal structure of compound 1 consists of chains of edge‐sharing [CaO₇] polyhedra linked by hypodiphosphate(IV) anions to form a three‐dimensional network. The crystal structure of compound 2 consists of alternated layers of crown ether and water molecules and respective ionic units. Within the layers of ionic units the Ca²⁺ cations are octahedrally coordinated by three monodentate dihydrogenhypodiphosphate(IV) anions and three water molecules. The IR/Raman spectra of the title compounds were recorded and interpreted, especially with respect to the [P₂O₆]^4– and [H₂P₂O₆]^2– groups. The phase purity of 2 was verified by powder diffraction measurements.     

Three New Thioantimonates(V): Solvothermal Syntheses and Crystal Structures of [M(chxn)3]3(SbS4)2·4H2O (M = Ni,Co) and [Co(dien)2][Co(tren)SbS4]2·4H2O

The three new thioantimonates(V) [Ni(chxn)₃]₃(SbS₄)₂·4H₂O ( I ), [Co(chxn)₃]₃(SbS₄)₂·4H₂O ( II ) (chxn is trans‐1,2‐diaminocyclohexane) and [Co(dien)₂][Co(tren)SbS₄]₂·4H₂O ( III ) (dien is diethylenetriamine and tren is tris(2‐aminoethyl)amine) were synthesized under solvothermal conditions. Compounds I and II are isostructural crystallizing in space group C2/c. The structures are composed of isolated [M(chxn)₃]²⁺ complexes (M = Ni, Co), [SbS₄]^3? anions and crystal water molecules. Short S···N/S···O/O···O separations indicate hydrogen bonding interactions between the different constituents. Compound III crystallizes in space group and is composed of [Co(dien)₂]²⁺ and [Co(tren)SbS₄]^? anions and crystal water molecules. In the cationic complex the Co²⁺ ion is in an octahedral environment of two dien ligands whereas in [Co(tren)SbS₄]^? the Co²⁺ ion is in a trigonal bipyramidal coordination of four N atoms of tren and one S atom of the [SbS₄]^3? anion, i.e., two different coordination polyhedra around Co²⁺ coexist in this compound. Like in the former compounds an extended hydrogen bonding network connects the complexes and the water molecules into a three‐dimensional network.     

Hexachloroplatinates of the Lanthanides: Syntheses and Thermal Decomposition of [M(NO3)2(H2O)6]2[PtCl6]·2H2O (M = La,Pr) and [M(NO3)(H2O)7][PtCl6]·4H2O (M = Gd,Dy)

The reaction of the nitrates M(NO₃)₃·6H₂O (M = La, Pr) and (H₃O)₂PtCl₆ led to yellow single crystals of [M(NO₃)₂(H₂O)₆]₂[PtCl₆]·2H₂O (M = La, Pr) (monoclinic, P2₁/c, Z = 2, La/Pr: a = 697.4(3)/695.5(1), b = 1654.5(1)/1652.5(2), c = 1317.7(6)/1318.5(3) pm, β = 93.97°(7)/93.93°(2), R_all = 0.0169/0.0659) while the reaction of M(NO₃)₃·5H₂O (M = Gd, Dy) and (H₃O)₂PtCl₆ yielded yellow single crystals of [M(NO₃)(H₂O)₇][PtCl₆]·4H₂O (monoclinic, P2₁/n, Z = 4, Gd/Dy: a = 838.72(3)/838.40(2), b = 2131.98(6)/2139.50(7), c = 1142.63(3)/1143.10(3) pm, β = 95.670(4)/95.698(3), R_all = 0.0475/0.0337). The crystal structures consist of octahedral [PtCl₆]^2? anions and complex [M(NO₃)₂(H₂O)₆]₂⁺ and [M(NO₃)(H₂O)₇]²⁺ cations, respectively. The thermal decomposition of both types of compounds leads via various steps to elemental platinum and the oxide chlorides MOCl (M = La, Pr, Gd, Dy).     

Two saccharinate complexes: [Mn(phen)2(sac)(H2O)]+·sac– and [Co(bipy)2(sac)(H2O)]+·sac–

The title saccharinate complexes, aqua[1,2‐benzisothiazol‐3(2H)‐onato 1,1‐dioxide‐N]bis(1,10‐phenanthroline‐N,N′)man­ganese(II) 1,2‐benz­isothia­zol‐3(2H)‐onate 1,1‐dioxide,[Mn(C₇H₄NO₃S)(C₁₂H₈N₂)₂(H₂O)](C₇H₄NO₃S), and aqua[1,2‐benz­iso­thiazol‐3(2H)‐onato 1,1‐dioxide‐N]­bis­(2,2′‐bi­pyri­dine‐N,N′)­cobalt(II) 1,2‐benz­iso­thia­zol‐3(2H)‐onate 1,1‐di­oxide, [Co­(C₇H₄NO₃S)­(C₁₀H₈N₂)₂­(H₂O)]­(C₇H₄NO₃S), have been prepared and their crystal structures determined at 150 K. The structure of the manganese complex consists of repeated alternating [Mn(phen)₂(sac)(H₂O)]⁺ cations and non‐coordinated saccharinate anions. The water molecule, bound to manganese as part of a slightly distorted octahedral arrangement, is hydrogen bonded to an O atom of the SO₂ group in the saccharinate counter‐ion. In contrast, the cobalt complex has one pseudo‐octahedral [Co(bipy)₂(sac)(H₂O)]⁺ cation, with the cobalt‐bound water molecule hydrogen bonded to the N atom of the accompanying free saccharinate anion.     

Synthesis,Crystal Structure,and Thermal Properties of the Energetic Coordination Compound [Co(DAT)2(H2O)4](HTNR)2·2H2O (DAT = 1,5‐diaminotetrazole)

A new coordination complex, [Co(DAT)₂(H₂O)₄](HTNR)₂ · 2H₂O [DAT = 1,5‐diaminotetrazole, HTNR = 2,4,6‐trinitroresorcinol (styphnic acid)], was obtained in high yield and characterized by elemental analysis and Fourier‐transform infrared (FT‐IR) spectroscopy. The molecular structure of [Co(DAT)₂(H₂O)₄](HTNR)₂ · 2H₂O in the crystalline state is determined by X‐ray crystallography is as follows: monoclinic, C2/c, a = 19.216(3) Å, b = 5.4992(8) Å, c = 30.418(5) Å, β = 104.500(5), V = 3112.0(8) ų, Z = 4, ρ_calc. = 1.851 g · cm^–3, R₁ = 0.0271 and wR₂ = (all data) 0.0674. The central cobalt(II) cation is coordinated by two nitrogen atoms of two DAT and four oxygen atoms of four H₂O ligand molecules to form a six‐coordinate and slightly distorted octahedral structure. Extensive intermolecular hydrogen bonds link molecular units of [Co(DAT)₂(H₂O)₄(HTNR)₂ · 2H₂O together to form a 3D net structure with pore canals. The thermal decomposition mechanism for the title compound was predicted based on DSC, TG‐DTG, and FT‐IR analyses and non‐kinetic parameters of the first exothermic process were estimated by applying the Kissinger, Starink, and Ozawa–Doyle methods.     

Four Complexes with the Rigid Ligand 1,4‐Bis(1H‐imidazol‐4‐yl)benzene and Varied Carboxylate Ligands

Four metal‐organic coordination polymers [Co₂(L)₃(nipa)₂]·6H₂O ( 1 ), [Cd(L)(nipa)]·3H₂O ( 2 ), [Co(L) (Hoxba)₂] ( 3 ) and [Ni₂(L)₂(oxba)₂(H₂O)]·1.5L·3H₂O ( 4 ) were synthesized by reactions of the corresponding metal(II) salts with the rigid ligand 1,4‐bis(1H‐imidazol‐4‐yl)benzene (L) and different derivatives of 5‐nitroisophthalic acid (H₂nipa) and 4,4′‐oxybis(benzoic acid) (H₂oxba), respectively. The structures of the complexes were characterized by elemental analysis, FT‐IR spectroscopy and single‐crystal X‐ray diffraction. Complexes 1 and 3 have the same one‐dimensional (1D) chain while 2 is a 6‐connected twofold interpenetrating three‐dimensional (3D) network with α ‐Po 4¹²·6³ topology based on the binuclear Cd^II subunits. Compound 4 features a puckered two‐dimensional (2D) (4,4) network, and the large voids of the packing 2D nets have accommodated the uncoordinated L guest molecules. An abundant of N–H···O, O–H···O and C–H···O hydrogen bonding interactions exist in complexes 1–4 , which contributes to stabilize the crystal structure and extend the low‐dimensional entities into high‐dimensional frameworks. Lastly, the photoluminiscent properties of compounds 2 were also investigated.     

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H3O)2[(UO2)2(SO4)3­(H2O)]·7H2O and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O,and a Uranyl Selenate‐Selenite [C5H6N][(UO2)(SeO4)(HSeO3)]

Two uranyl sulfate hydrates, (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 7H₂O (NDUS) and (H₃O)₂[(UO₂)₂(SO₄)₃(H₂O)] · 4H₂O (NDUS1), and one uranyl selenate‐selenite [C₅H₆N][(UO₂)(SeO₄)(HSeO₃)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L ‐cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P2₁/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4) Å, β = 112.778(1)°, V = 2153.52(9) ų,Z = 4, the tetragonal space group P4₃2₁2, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) ų, Z = 8, and in the monoclinic space group P2₁/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) ų, Z = 4, respectively.The structural units of NDUS and NDUS1 are two‐dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two‐dimensional uranyl selenate‐selenite sheets with a U/Se ratio of 1/2. In‐situ reaction of the L ‐cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H₃O⁺ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C₅H₆N⁺ cations result from the cyclization of the carboxyl groups of L ‐cystine, balancing the charge of the sheets.     

Double complexes [Co(NH3)5(H2O)]2[Zr3F18]·6H2O and [Co(NH3)6]2[Zr3F18]·6H2O

The structures of orthorhombic bis[pentaammineaquacobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Ibam), [Co(NH₃)₅(H₂O)]₂[Zr₃F₁₈]·6H₂O, (I), and bis[hexaamminecobalt(III)] tetra‐μ₂‐fluorido‐tetradecafluoridotrizirconium(IV) hexahydrate (space group Pnna), [Co(NH₃)₆]₂[Zr₃F₁₈]·6H₂O, (II), consist of complex [Co(NH₃)_x(H₂O)_y]³⁺ cations with either m [in (I)] or and 2 [in (II)] symmetry, [Zr₃F₁₈]⁶⁻ anionic chains located on sites with 222 [in (I)] or 2 [in (II)] symmetry, and water molecules.     

Thermochemical Study on [La(Hsal)2•(tch)]•2H2O [Hsal＝salicylate ( ), tch＝thioprolinate (C4H6NO2S-)]

The product from reaction of lanthanum chloride heptahydrate with salicylic acid and thioproline, [La(Hsal)2•(tch)]•2H2O, was synthesized and characterized by IR, elemental analysis, molar conductance, thermogravimatric analysis and chemistry analysis. The standard molar enthalpies of solution of LaCl3•7H2O (s), [2C7H6O3 (s)], C4H7NO2S (s) and [La(Hsal)2•(tch)]•2H2O (s) in a mixed solvent of absolute ethyl alcohol, dimethyl sulfoxide (DMSO) and 3 mol•L－1 HCl were determined by calorimetry to be [LaCl3•7H2O (s), 298.15 K]＝(－102.36±0.66) kJ•mol－1, [2C7H6O3 (s), 298.15 K]＝(26.65±0.22) kJ•mol－1, [C4H7NO2S (s), 298.15 K]＝(－21.79±0.35) kJ•mol－1 and {[La(Hsal)2•(tch)]•2H2O (s), 298.15 K}＝(－41.10±0.32) kJ•mol－1. The enthalpy change of the reaction LaCl3•7H2O (s)＋2C7H6O3 (s)＋C4H7NO2S (s)＝[La(Hsal)2•(tch)]•2H2O (s)＋3HCl (g)＋5H2O (l) (Eq. 1) was determined to be ＝(41.02±0.85) kJ•mol－1. From date in the literature, through Hess’ law, the standard molar enthalpy of formation of [La(Hsal)2•(tch)]•2H2O (s) was estimated to be {[La(Hsal)2•(tch)]•2H2O (s), 298.15 K}＝(－3017.0±3.7) kJ•mol－1.