New three-dimensional (3,4)-net zincophosphites templated by linear diammonium cations: H3N(CH2)5NH3·Zn3(HPO3)4 and β-H3N(CH2)6NH3·Zn3(HPO3)4

The mild-condition syntheses, single-crystal structures and properties of H₃N(CH₂)₅NH₃·Zn₃(HPO₃)₄ and β-H₃N(CH₂)₆NH₃·Zn₃(HPO₃)₄ are reported. Both are constructed from (3,4)-nets of ZnO₄ tetrahedra and HPO₃ pyramids, sharing vertices to result in three-dimensional anionic open-frameworks. In both materials, the organic species interacts with the framework by way of N–H⋯O bonds. Crystal data: H₃N(CH₂)₅NH₃·Zn₃(HPO₃)₄, M_r = 620.22, orthorhombic, Pccn (No. 56), a = 9.5364 (9) Å, b = 21.8015 (19) Å, c = 9.1118 (7) Å, V = 1894.4 (3) Å³, Z = 4, R(F) = 0.044, wR(F²) = 0.111. β-H₃N(CH₂)₆NH₃·Zn₃(HPO₃)₄, M_r = 634.25, monoclinic, P2₁/n (No. 14), a = 8.7627 (1) Å, b = 13.8117 (2) Å, c = 16.6187 (3) Å, β = 92.680 (1)°, V = 2009.12 (5) Å³, Z = 4, R(F) = 0.072, wR(F²) = 0.187.     

Synthesis and structural characterization of a photoresponsive organodirhodium complex with active S–S bonds: [(CpPhRh)2(μ-CH2)2(μ-O2SSO2)] (CpPh = η5-C5Me4Ph)

A photoresponsive rhodium dinuclear complex having phenyltetramethylcyclopentadienyl (Cp^Ph = η⁵-C₅Me₄Ph) and photosensitive dithionite (μ-O₂SSO₂) ligands, [(Cp^PhRh)₂(μ-CH₂)₂(μ-O₂SSO₂)] (1), has been synthesized. The crystal of complex 1 (monoclinic, C2/m (No. 12), a = 24.805(2) Å, b = 29.111(2) Å, c = 10.8475(11) Å, β = 105.9830(7)°, V = 7530.0(12) Å³, Z = 8) consists of two independent molecules, 1-cis and 1-trans, with different arrangement of the Cp^Ph ligands. The flexibility, volume, and shape of the reaction cavities around the dithionite unit of 1-cis and 1-trans in the crystal are discussed. The crystal structures of the precursors of 1, trans-[(Cp^PhRh)₂(μ-Cl)₂Cl₂] and trans-[(Cp^PhRh)₂(μ-CH₂)₂Me₂], are also reported.     

Two novel Keggin tungstocobaltates grafted by cobaltII complex group(s): K[Co(phen)2(H2O)]2[HCoW12O40]·2H2O and [Co(2,2′-bipy)3]1.5{[Co(2,2′-bipy)2(H2O)][HCoW12O40]}·0.5H2O

Two novel inorganic–organic hybrid compounds composed of Keggin tungstocobaltate framework and cobalt(II)–N coordination complexes, K[Co(phen)₂(H₂O)]₂[HCoW₁₂O₄₀]·2H₂O (1) (phen = 1,10-phenanthroline) and [Co(2,2′-bipy)₃]_1.5{[Co(2,2′-bipy)₂(H₂O)][HCoW₁₂O₄₀]·0.5H₂O (2) (bipy = bipyridine), have been synthesized under hydrothermal conditions by directly using Keggin POMs as starting materials, which were characterized by elemental analyses, IR, TG analyses and X-ray single crystal diffraction. Crystal data for compound 1: C₄₈H₄₁Co₃KN₈O₄₄W_12, triclinic, space group P-1, a = 10.918(5) Å, b = 13.401(5) Å, c = 13.693(5) Å, α = 69.291(5)°, β = 71.568(5)°, γ = 78.421(5)°, V = 1768.9(12) Å³, Z = 1; for compound 2: C₁₃₀H₁₀₄Co₇N₂₆O₈₃W_24, orthorhombic, space group, C2/c, a = 46.839(9) Å, b = 14.347(3) Å, c = 26.147(5) Å, α = β = γ = 90°, V = 17,570(6) Å³, Z = 4. Compound 1 exhibits a pseudo-1D chainlike structure, in which potassium ions act as linkages of Keggin unit doubly grafted by [Co(phen)₂(H₂O)] complex. Compound 2 represents a [Co(2,2′-bipy)₂(H₂O)]²⁺ mono-grafted Keggin tungstocobaltate derivative with 1.5[Co(2,2′-bipy)₃]²⁺ countercations. The cyclic voltammetric behavior of 1-CPE is similar to the parent 3-CPE, but the cyclic voltammetric behavior of Co^II shows a little difference. Variable-temperature magnetic susceptibility measurement of compound 1 demonstrates the presence of antiferromagnetic interactions.     

Synthesis,crystal structure and thermal behaviour of [La(hfa)3(Phen)2] (hfa = hexafluoroacetylacetonate,Phen = o-phenanthroline)

The mixed ligand complex [La(hfa)₃(Phen)₂] (I) was obtained by the interaction of La(hfa)₃ and Phen; its composition does not depend on the stoichiometry of the reagents. According to the X-ray single crystal analysis data, complex I crystallizes in the monoclinic space group P2₁/n, with a = 13.583(3) Å, b = 16.959(3) Å, c = 18.860(4) Å, β = 94.71(3)° and Z = 4. The structure of I consists of isolated mononuclear molecules, the coordination number of La being 10. Thermal behaviour and composition of the vapor phase have been studied for I by thermal analysis and mass-spectrometry using a Knudsen cell. The mixed ligand complex I was found to sublime congruently in the temperature range 370–460 K: [La(hfa)₃(Phen)₂]_(s) = [La(hfa)₃(Phen)]_(g) + Phen_(g), Δ_rH⁰(T) = 316.2 ± 1.8 kJ/mol.     

Crystal structures of Th(OH)PO4, U(OH)PO4 and Th2O(PO4)2. Condensation mechanism of MIV(OH)PO4 (M = Th,U) into M2O(PO4)2

Three new crystal structures, isotypic with β-Zr₂O(PO₄)₂, have been resolved by the Rietveld method. All crystallize with an orthorhombic cell (S.G.: Cmca) with a = 7.1393(2) Å, b = 9.2641(2) Å, c = 12.5262(4) Å, V = 828.46(4) Å³ and Z = 8 for Th(OH)PO₄; a = 7.0100(2) Å, b = 9.1200(2) Å, c = 12.3665(3) Å, V = 790.60(4) Å³ and Z = 8 for U(OH)PO₄; a = 7.1691(3) Å, b = 9.2388(4) Å, c = 12.8204(7) Å, V = 849.15(7) Å³ and Z = 4 for Th₂O(PO₄)₂. By heating, the M(OH)PO₄ (M = Th, U) compounds condense topotactically into M₂O(PO₄)₂, with a change of the environment of the tetravalent cation that lowers from 8 to 7 oxygen atoms. The lower stability of Th₂O(PO₄)₂ compared to that of U₂O(PO₄)₂ seems to result from this unusual environment for tetravalent thorium.     

Syntheses and crystal structures of new vanadium(IV) oxyphosphates M(VO)2(PO4)2 with M = Co,Ni

We have extended our research interest on titanium oxyphosphates (M^II(TiO)₂(PO₄)₂, with M^II = Mg, Fe, Co, Ni, Cu, Zn) to vanadium oxyphosphates M^II(V^IVO)₂(PO₄)₂ (M^II = Co, Ni). For each compound two phases, named α and β according to synthesis conditions, have been stabilized at room temperature, then characterized. The four crystal structures M(VO)₂(PO₄)₂ (α and β for M = Co, Ni) have been determined in monoclinic P2₁/c space group using X-ray single crystals diffraction data. Structure of the α phase is derived from the Li(TiO)(PO₄) (orthorhombic Pnma) and LiNi_0.50(TiO)₂(PO₄)₂ (monoclinic P2₁/c) types, with cell parameters: a = 6.310(1) Å, b = 7.273(1) Å, c = 7.432(1) Å, β = 90.43(1)° for M = Co, and a = 6.297(2) Å, b = 7.230(2) Å, c = 7.421(2) Å, β = 90.36(2)° for M = Ni. Structure of the β phase is derived from the Ni(TiO)₂(PO₄)₂-type (monoclinic P2₁/c) with cell parameters: a = 7.2742(2) Å, b = 7.2802(2) Å, c = 7.4550(2) Å, β = 120.171(2)° for M = Co, and a = 7.2691(2) Å, b = 7.2366(2) Å, c = 7.4453(2) Å, β = 120.231(2)° for M = Ni. All these structures consist of a three dimensional (3D) framework built up of infinite chains of tilted corner-sharing [VO₆] octahedra, cross-linked by corner-sharing [PO₄] tetrahedra. The M²⁺ ion (M = Co, Ni) is located in a triangular based antiprism which shares faces with two [VO₆] octahedra. Structural filiation is discussed based on a common structural unit, a sheet where divalent cations M²⁺ (M = Co, Ni) are inserted. A thermal study of the α ? β transition is also presented.     

Synthesis,crystal structure,and magnetic properties of K4Mn3(HPO4)4(H2PO4)2

A new layered compound, K₄Mn₃(HPO₄)₄(H₂PO₄)₂ (1), has been synthesized under hydrothermal conditions. It crystallizes in the monoclinic space group P2₁/n with a = 8.874(2) Å, b = 6.554(1) Å, c = 18.075(4) Å, and β = 93.39(3)°. The structure consists of zigzag [Mn₃O₁₄]_n chains of edge-sharing MnO₆ octahedrons and MnO₇ pentagonal bi-pyramids, which form layers of formula [Mn₃(HPO₄)₄(H₂PO₄)₂]^4? in the ab plane via H₂PO₄ and HPO₄ units with vertex-sharing. Potassium ions lie between these layers. Magnetic measurements indicate Curie–Weiss behavior above 6 K for 1. A Heisenberg model, with alternating exchange interactions J₁J₁J₂… within the chain and exchange interactions J₃J₃… between the chains, is proposed to describe the magnetic behavior.     

Structure cristalline d'un nouvel hydroxyphosphate naturel de strontium,fer et aluminium (lulzacite), Sr2Fe(Fe0,63Mg0,37)2Al4(PO4)4(OH)10

Crystal structure of a new natural strontium, iron and aluminium hydroxyphosphate (lulzacite): Sr₂Fe(Fe_0.63Mg_0.37)₂Al₄(PO₄)₄(OH)₁₀. The crystal structure of a new natural strontium, iron and aluminium hydroxyphosphate (lulzacite) has been solved through an X-ray study of a single crystal:– symmetry: triclinic (P1̄);– unit cell parameters: a=5.457(1) Å, b=9.131(2) Å, c=9.769(2) Å, α=108.47(3)°, β=91.72(3)° and γ=97.44(3);– structural formula: (Sr_0.96Ba_0.04)₂Fe(Fe_0.63Mg_0.37)₂Al₄[(P_0.98V_0.02)O₄]₄(OH)₁₀ (Z=1).The structure presents along the b axis the alternation, on one hand of infinite chains of edge sharing octahedra (one Fe²⁺O₆ and an AlO₆ pair), and, on the other hand, of trimers with a central AlO₆ octahedron framed by two mixed (Fe²⁺,Mg)O₆ octahedra. Trimers and chains are linked by the corners of one AlO₆ octahedron and two PO₄ tetrahedra. Strontium ions are located in the channels of the structure. This structure is isotypic with that of jamesite, a lead arsenate. Similar octahedral building blocks are present in other mineral species: trimers in ludlamite (iron phosphate), chains in various hydroxysalts. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASlulzacite / hydroxyphosphate / phosphate / strontium / iron / aluminium     

Ab initio crystal structure of nickel(II) hydroxy-terephthalate by synchrotron powder diffraction and magnetic study

The structure of the new hybrid compound [Ni₃(OH)₂(tp)₂(H₂O)₄]·2H₂O (tp = C₈H₄O₄²⁻) has been determined ab initio from synchrotron powder diffraction data and refined with the Rietveld method: space group P-1, a = 10.2077(6) Å, b = 8.0135(5) Å, c = 6.3337(4) Å, α = 97.70 (1)°, β = 97.21(1)°, γ = 108.77(1)°, D_x = 2.124 g/cm³, Rp = 0.045, R_B = 0.095 (757 independent reflections). H atoms were placed geometrically and their position optimized by DFT calculation. The repeating structural unit is the chain [Ni(1)O₆]₂Ni(2)O₆, consisting of two edges sharing octahedrons related by the symmetry center and linked via μ3-OH to a vertex of Ni(2) octahedron. The Ni(1) coordination is ensured by two oxygen atoms from two water molecules, two OH and two oxygen atoms from carboxylate groups. The linkage of the chains by the tp anions forms infinite layers parallel to the (010) planes. Interchain hydrogen bonds between the water molecules coordinating the metal ensure the cohesion of the 2D structure. The structural and magnetic properties are compared with that of the 3D fumarate-based compound [Ni₃(OH)₂(fum)₂(H₂O)₄]·2H₂O (fum = C₄H₂O₄²⁻).     

Synthesis and characterization of a novel three-dimensional open-framework: Metal diphosphonate,Zn[HO3PCH2(C6H4)CH2PO3H]

A novel zinc diphosphonate, Zn[HO₃PCH₂(C₆H₄)CH₂PO₃H] (1) was synthesized from tetraethyl para-xylylenediphosphonate, Et₂O₃PCH₂C₆H₄CH₂PO₃Et₂, and Zn (AcO)₂·2H₂O under solvothermal conditions. The structure of compound 1 was determined by single-crystal X-ray diffraction, which reveals that the structure crystallizes in the monoclinic space group C2/c (No. 15), with a = 22.4844(19) Å, b = 6.4361(5) Å, c = 8.1194(7) Å, β = 102.595(2)°, V = 1146.70(16) Å³, T = 298(2) K, Z = 8. The novel three-dimensional (3D) construction is simply built up from linear inorganic chains of corner-sharing four-rings of tetrahedral [ZnO₄] and [PO₃C] which connected adjacent chains by the organophosphorus ligand para-xylylenediphosphonate. The framework has 10 Å × 4 Å (containing the van der Waals radii of atoms) channels running along the b-axis.     

Ce(H2O)(PO4)3/2(H3O)1/2(H2O)1/2, a second entry in the structural chemistry of cerium(IV) phosphates

A cerium(IV) phosphate has been prepared using precipitation methods and its structure has been solved by single crystal X-ray diffraction (R₁ = 0.0292 for 3092 reflections with I>2σ(I) and wR₂ = 0.0540). Ce(H₂O)(PO₄)_3/2(H₃O)_1/2(H₂O)_1/2 crystallises in the monoclinic space group C2/c (a = 15.7058(17) Å, b = 9.6261(9) Å, c = 10.1632(4) Å, ß = 121.623(7)°, and V = 1308.4 (2) Å³). Its structure is based on a negatively charged 3D framework, made of cerium atoms connected by PO₄ tetrahedra. There are two types of PO₄ units; one shares only corners with the cerium coordination polyhedra while the other one shares edges and corners. This structure also includes hydronium cations, to balance the framework charge, and water molecules. One special feature of this 3D framework is the formation of interconnected tunnels which extend along the c axis and contain the hydronium cations and the water molecules. This open framework and the presence of cationic species in the tunnels are in perfect agreement with the previously reported ion exchange properties.     

Structure and magnetic properties of a novel copper diphosphonate with pillared layered structure:: Cu2(H2O)2{O3PCH2N(C2H4)2NCH2PO3}

Compound Cu₂(H₂O)₂{O₃PCH₂N(C₂H₄)₂NCH₂PO₃} (1) has a pillared layered structure in which the organic groups of N,N′-piperazinebis(methylenephosphonate) are sandwiched between the inorganic layers. Compared with other copper phosphonates with layered or pillared layered structures, the inorganic layer in 1 is unique in that each {CPO₃} tetrahedron is corner-shared with three {CuO₄N} square pyramids through three oxygen donors. Ferromagnetic interactions are mediated between the metal centers. Crystal data: Pbca, a=10.0830(16) Å, b=9.4517(15) Å, c=13.218(2) Å, V=1259.7(3) Å³, Z=4.     

The dimeric unit [La(H2O)4(m-PO3C6H4COOH)(m-PO2(OH)C6H4COOH)(m-PO(OH)2C6H4COOH)]2 as building block of layered hybrid material

A new hybrid organic–inorganic material with the structural formula unit [La(H₂O)₄(m-PO₃C₆H₄COOH)(m-PO₂(OH)C₆H₄COOH)(m-PO(OH)₂C₆H₄COOH)]₂ (or [La(H₂O)₄C₂₁H₁₈O₁₅P₃]₂) has been synthesized under hydrothermal condition from La(NO₃)₃·6H₂O and 3-phosphonobenzoic acid (m-PO(OH)₂–C₆H₄–COOH) which is a rigid organic precursor possessing two types of functional groups: phosphonic acid and carboxylic acid. The two units of the produced hybrid are linked together by hydrogen bonds leading to a layered framework composing of by a repetition of inorganic and organic slices. The organic layers consist of dimeric units made of two meta-phosphono-benzoic acid linked together by hydrogen bonds involving their COOH groups. Two kinds of dimeric units are observed: PO₃C₆H₄COOH?HOOCC₆H₄PO(OH)₂, present 2 times in the structure, and PO₂(OH)C6H4COOH?HOOCC₆H₄PO₂(OH). The material crystallises in a monoclinic cell (C2/c (15) space group) with the following parameters: a = 42.515(4) Å, b = 7.4378(6) Å, c = 20.307(2) Å, β = 118.031(6)°, V = 5668.2(9) Å³, Z = 4, density = 1.908 g/cm³.     

Two coordination polymers of manganese(II) isophthalate and their preparation,structures, and magnetic properties

Two manganese coordination polymers, [Mn₂(ip)₂(dmf)]·dmf (1) and [Mn₄(ip)₄(dmf)₆]·2dmf (2) (ip=isophthalate; dmf=N,N-dimethylformamide), have been synthesized and characterized. X-ray crystal structural data reveal that compound 1 crystallizes in triclinic space group P?1, a=9.716(3) Å, b=12.193(3) Å, c=12.576(3) Å, α=62.19(2)°, β=66.423(17)°, γ=72.72(2)°, Z=2, while compound 2 crystallizes in monoclinic space group Cc, a=19.80(3) Å, b=20.20(2) Å, c=18.01(3) Å, β=108.40(4)°, Z=4. Variable-temperature magnetic susceptibilities of compounds 1 and 2 exhibit overall weak antiferromagnetic coupling between the adjacent Mn(II) ions.     

[H4tren]3/2·(Al6F24)·3H2O,the most condensed fluoride in the Al(OH)3-tren-HFaq.-ethanol system

The most condensed crystalline fluoride that appears in the Al(OH)₃-tren-HF_aq.-ethanol system at 190 °C is found to be [H₄tren]_3/2·(Al₆F₂₄)·3H₂O. The structure is monoclinic, P2₁/c, with a = 21.939(1) Å, b = 6.7180(2) Å, c = 23.329(1) Å, β = 111.324(2)°. _∞(Al₆F₂₄) chains result from the connection of (Al₇F₃₀)⁹⁻ polyanions by opposite AlF₆ octahedra. Hydrogen bonds are established between the _∞(Al₆F₂₄) chains and ordered or disordered [H₄tren]⁴⁺ cations and water molecules.     

The crystal structure of potassium ammonium hexamolybdotellurate with telluric acid K5NH4[TeMo6O24].Te(OH)6.6H2O

An inorganic compound formulated as K₅NH₄[TeMo₆O₂₄].Te(OH)₆.6H₂O (1) has been isolated by conventional solution method and structurally characterized by single-crystal X-ray diffraction methods, scanning electron microscopy (SEM), IR, UV–vis spectra, and cyclic voltammetry measurements. This compound crystallizes in the monoclinic system, space group C2/c with unit a = 18.6841(1) Å, b = 10.0513(1) Å, c = 21.1065(1) Å, β = 116.495(1)°, V = 3547.49(4) ų, Z = 4, R = 0.033 and wR (F²) = 0.087 for 3432 unique observed reflexions [I > 2σ(I)]. The crystal structure of (1) is built up from an Anderson clusters connected through hydrogen-bonding interactions into a three-dimensional supramolecular network.     

(Solid + solute) phase equilibria in aqueous solution. XIII. Thermodynamic properties of hydrozincite and predominance diagrams for (Zn2 + + H2O + CO2)

The thermodynamic properties ofZn₅(OH)₆(CO₃)₂ , hydrozincite, have been determined by performing solubility and d.s.c. measurements. The solubility constant in aqueous NaClO₄media has been measured at temperatures ranging from 288.15 K to 338.15 K at constant ionic strength (I =  1.00 mol · kg ^− 1). Additionally, the dependence of the solubility constant on the ionic strength has been investigated up to I =  3.00 mol · kg ^− 1NaClO₄at T =  298.15 K. The standard molar heat capacity C_{p, m}^ofunction fromT =  318.15 K to T =  418.15 K, as well as the heat of decomposition of hydrozincite, have been obtained from d.s.c. measurements. All experimental results have been simultaneously evaluated by means of the optimization routine of ChemSage yielding an internally consistent set of thermodynamic data (T =  298.15 K): solubility constant log ^* K_{ps 0}⁰ =  (9.0  ±  0.1), standard molar Gibbs energy of formationΔ_fG_m^o {Zn₅(OH)₆(CO₃)₂ }  =  ( − 3164.6  ±  3.0)kJ · mol ^− 1, standard molar enthalpy of formation Δ_fH_m^o{Zn₅(OH)₆(CO₃)₂ }  =  ( − 3584  ±  15)kJ · mol ^− 1, standard molar entropy S_m^o{Zn₅(OH)₆(CO₃)₂ }  =  (436  ±  50)J · mol ^− 1· K ^− 1and C_p,m^o / (J · mol ^− 1· K ^− 1)  =  (119  ±  11)  +  (0.834  ±  0.033)T / K. A three-dimensional predominance diagram is introduced which allows a comprehensive thermodynamic interpretation of phase relations in(Zn^2 +  +  H₂O  +  CO₂) . The axes of this phase diagram correspond to the potential quantities: temperature, partial pressure of carbon dioxide and pH of the aqueous solution. Moreover, it is shown how the stoichiometric composition{n(CO₃) / n(Zn)} of the solid compoundsZnCO₃ and Zn₅(OH)₆(CO₃)₂can be checked by thermodynamically analysing the measured solubility data.     

Syntheses,structures and single-molecule magnetic behaviors of two dicubane Mn4 complexes

The reaction of MnX₂ · 4H₂O (X = Cl or Br) with 2,6-bis(hydroxymethyl)-4-methylphenol (H₃L) and NaOH in methanol solution yielded two tetranuclear manganese complexes, [Mn₄(HL)₄(MeOH)₄Cl₂] (1) and [Mn₄(HL)₄(MeOH)₄Br₂] (2). Both compounds crystallize in the monoclinic space group C₂/c with cell parameters: a = 26.0945(19) Å, b = 11.4999(8) Å, c = 21.2188(16) Å, β = 121.050(1)° and z = 4 for 1 · 2Et₂O; a = 25.8145(3) Å, b = 11.6734(2) Å, c = 21.3956(3) Å, β = 120.1277(6)° and z = 4 for 2 · 2Et₂O. Both complexes consist of a mixed-valence dicubane structure, which comprises two Mn^II and two Mn^III ions. Magnetic susceptibilities and magnetization of complexes 1 and 2 in the solid state indicate that two clusters have an S = 9 ground state. Frequency-dependent out-of-phase signals of alternating current magnetic susceptibilities were observed in the low temperature range (<3 K) for both complexes indicating a slow magnetic relaxation.     

Synthesis,structure and NMR characterization of a new monomeric aluminophosphate [dl-Co(en)3]2[Al(HPO4)2(H1.5PO4)2(H2PO4)2](H3PO4)4 containing four different types of monophosphates

A new zero-dimensional (0D) aluminophosphate monomer [dl-Co(en)₃]₂[Al(HPO₄)₂(H_1.5PO₄)₂(H₂PO₄)₂](H₃PO₄)₄ (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en)₃Cl₃ as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO₄)₂(H_1.5PO₄)₂(H₂PO₄)₂]^6? monomer. Notably, there exists intramolecular symmetrical O?H?O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by ³¹P NMR and ¹H NMR spectra. The crystal data are as follows: AlPO-CJ38, [dl-Co(en)₃]₂[Al(HPO₄)₂(H_1.5PO₄)₂(H₂PO₄)₂](H₃PO₄)₄, M = 1476.33, monoclinic, C2/c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å³_, Z = 4, R₁ = 0.0509 (I > 2σ(I)) and wR₂ = 0.1074 (all data). CCDC number 689491.