Effect of boron non-stoichiometry on B-site in perovskite type structure ScBxRh3 and CeBxRh3 on charges of atoms on A-site: study by X-ray photoelectron and nuclear magnetic resonance spectroscopies

The solid solutions of ScBRh₃-ScRh₃ and CeBRh₃-CeRh₃ are synthesized by the arc melting method, where RBRh₃ and RRh₃ (R=rare earth element) have perovskite and AuCu₃ type structures, respectively. The binding energy of Sc 2p_3/2 for ScB_xRh₃ increases with the boron concentration. The Knight shift of ⁴⁵Sc observed by nuclear magnetic resonance spectroscopy decreases with increase of boron concentration. The decrement of the Knight shift corresponds the Sc 4s electron density at the Fermi level. The intensity ratio of f²: f¹: f⁰ of Ce 3d XPS spectrum changes with boron concentration of CeB_xRh₃. It is concluded that in both cases of ScB_xRh₃ and CeB_xRh₃ the charge on the atoms on A-site changes with the concentration of the atoms on B-site, where the atoms are not directly bound.     

Magnetism and Raman spectroscopy of the dimeric lanthanide iodates Ln(IO3)3 (Ln=Gd, Er) and magnetism of Yb(IO3)3

Colorless single crystals of Gd(IO₃)₃ or pale pink single crystals of Er(IO₃)₃ have been formed from the reaction of Gd metal with H₅IO₆ or Er metal with H₅IO₆ under hydrothermal reaction conditions at 180 °C. The structures of both materials adopt the Bi(IO₃)₃ structure type. Crystallographic data are (MoKα, λ=0.71073 Å): Gd(IO₃)₃, monoclinic, space group P2₁/n, a=8.7615(3) Å, b=5.9081(2) Å, c=15.1232(6) Å, β=96.980(1)°, V=777.03(5) Z=4, R(F)=1.68% for 119 parameters with 1930 reflections with I>2σ(I); Er(IO₃)₃, monoclinic, space group P2₁/n, a=8.6885(7) Å, b=5.9538(5) Å, c=14.9664(12) Å, β=97.054(1)°, V=768.4(1) Z=4, R(F)=2.26% for 119 parameters with 1894 reflections with I>2σ(I). In addition to structural studies, Gd(IO₃)₃, Er(IO₃)₃, and the isostructural Yb(IO₃)₃ were also characterized by Raman spectroscopy and magnetic property measurements. The results of the Raman studies indicated that the vibrational profiles are adequately sensitive to distinguish between the structures of the iodates reported here and other lanthanide iodate systems. The magnetic measurements indicate that only in Gd(IO₃)₃ did the 3+ lanthanide ion exhibit its full 7.9 μ_B Hund's rule moment; Er³⁺ and Yb³⁺ exhibited ground state moments and gap energy scales of 8.3 μ_B/70 K and 3.8 μ_B/160 K, respectively. Er(IO₃)₃ exhibited extremely weak ferromagnetic correlations (+0.4 K), while the magnetic ions in Gd(IO₃)₃ and Yb(IO₃)₃ were fully non-interacting within the resolution of our measurements (∼0.2 K).     

A mass spectral study of some symmetric and unsymmetric sulfides,disulfanes, and trisulfanes

The low-resolution mass spectra of 13 trifluoromethyl and/or methyl sulfur-containing compounds (CF₃S_nCF₃, CF₃S_nCH₃, CH₃S_nCH₃, CF₃S_mCl, and CH₃S_mCl; n = 1, 2, 3; m = 1, 2) are reported and discussed. There is a considerable similarity between the fragmentation pattern of compounds with the same terminal groups. However, with a fluorinated and a non-fluorinated methyl group, the major fragmentation products produced are similar to those for the dimethyl compounds.     

Reactivity and Structural Properties of a Mechanochemically Treated Ag2O-V2O5 System in Relation to AgVO3 Polymorphs

Formation and chemical properties of amorphous AgVO₃, which was prepared by mechanochemical treatment of an Ag₂O-V₂O₅ mixture, and crystalline AgVO₃ were studied in relation to AgVO₃ polymorphs. A ball-milled sample of the mixture was assigned as a highly deformed β-AgVO₃ rather than the low density phase α-AgVO₃. Crystalline α-AgVO₃ and β-AgVO₃ were converted into deformed β-AgVO₃ by ball milling, which produced a clear change. δ-AgVO₃ is resistant to mechanical treatment and its structure was not markedly affected. The dissolved chemical species from the ball-milled sample precipitates to form α-AgVO₃ without a seeding crystal, but other polymorphs deposit if they are present; i.e., β-AgVO₃ and δ-AgVO₃ grow on the seeding crystal.     

Chemical behavior of ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligands in the presence of palladium(II) chloride

The synthesis, structural characterization, and coordination behavior of ditopic ortho-hydroquinone-based bis(pyrazol-1-yl)methane ligands (ortho-(OH)₂C₆H₃-4-CHpz₂, ortho-(OH)₂C₆H₃-4-CH(3-Phpz)₂, and ortho-(OH)₂C₆H₃-4-CH(3-tBupz)₂) with pyrazole, 3-phenylpyrazole, and 3-tert-butylpyrazole as donors are described. The reaction of a soluble PdCl₂-source with ortho-(OH)₂C₆H₃-4-CHpz₂ in acetonitrile yielded the related square-planar N,N-coordinated Pd(II) dichloride complex, whereas treatment of ortho-(OH)₂C₆H₃-4-CH(3-Phpz)₂ or ortho-(OH)₂C₆H₃-4-CH(3-tBupz)₂ with PdCl₂ in acetonitrile resulted in degradation of these ligands. The Pd(II) complexes trans-(3-PhpzH)₂PdCl₂ and trans-(3-tBupzH)₂PdCl₂ were isolated and fully characterized including X-ray diffraction analyses.     

Phase Equilibria in the Sc2S3-Ln2S3 (Ln = Dy,Er, or Tm) Systems

Phase diagrams for the Sc₂S₃-Ln₂S₃ (Ln = Dy, Er, or Tm) systems were designed in the range from 1000 K to melting temperatures. The Ln₃ScS₆ compounds that are formed in these systems crystallize in monoclinic space group P2₁/m, and melt congruently: for Dy₃ScS₆, a = 1.118 nm, b = 1.262 nm, c = 0.354 nm, β = 94.7°, 1800 K, H = 2600 MPa; for Er₃ScS₆, a = 1.113 nm, b = 1.258 nm, c = 0.353 nm, β = 94.5°, 1830 K, H = 2800 MPa; for Tm₃ScS₆, a = 1.112 nm, b = 1.229 nm, c = 0.352 nm, β = 94.3°, 1835 K, H = 2940 MPa. The LnScS₃ (Ln = Dy or Er) complex sulfides, with orthorhombic structures, space group Pnma, melt incongruently: for DyScS₃, a = 0.700 nm, b = 0.637 nm, c = 0.943 nm, 1810 K, H = 3800 MPa; and for ErScS₃, a = 0.697 nm, b = 0.633 nm, c = 0.942 nm, 1800 K, H = 3800 MPa. As the ionic radii rLn3+ and rSc3+ approach Ln Sc to each other in the row Dy-Er-Tm, the solubility in Sc₂S₃ increases, at 1670 K being equal to 13 mol % Dy₂S₃, 30 mol % Er₂S₃, and 40 mol % Tm₂S₃. LnScS₃ (Ln = Dy or Er) forms a two-sided homogeneity region, at 1670 K lying in ranges of 43–56 mol % Ln₂S₃. The eutectic temperatures and compositions are as follows: 1700 K and 66 mol % Dy₂S₃, 1730 K and 81 mol % Dy₂S₃, 1740 K and 65 mol % Er₂S₃, 1700 K and 83 mol % Er₂S₃, 1730 K and 70 mol % Tm₂S₃, and 1755 K and 84 mol % Tm₂S₃.     

Neutron powder diffraction and magnetic measurements on RbTil3, RbVI3, and CsVI3

CsVI₃ (a = 8.124(1) c = 6.774(1)Å,Z = 2, P6₃/mmc at 293 K) adopts the BaNiO₃ structure. Three-dimensional magnetic ordering takes place atT_c = 32(1)K. At 1.2 K the magnetic moment is 1.64(5) μ_B and it forms a 120° spin structure in the basal plane. RbVI₃ (a = 13.863(2) c = 6.807(1) Å,Z = 6, P6₃cmor P3¯c1 at 293 K) and RbTiI₃ (a = 14.024(3) Å,c = 6.796(2) Å,Z = 6, P6₃cm orP3¯c1 at 293 K) adopt a distorted BaNiO₃ structure, probably isostructural with KNiCl₃.T_c of RbVI₃ is 25(1) K. At 1.2 K, RbVI₃ has a spin structure similar to the one of CsVI₃ with a magnetic moment of 1.44(6) μ_B. RbTiI₃ shows no magnetic ordering at 4.2 K. It is shown that a deviation from the 120° structure is expected for compounds with a distorted BaNiO₃ structure such as RbVI₃. The cell dimensions of CsTiI₃ are reported.     

Thermodynamics of the URuC system

Thermodynamic measurements by the electromotive force method were made on the binary intermetallic phases URu₃ and U₃Ru₅ and on the ternary carbides URu₃C_0.7 and U₂RuC₂ of the URu and the URuC systems between 950 and 1200 K using galvanic cells with CaF₂ single crystal electrolytes: U, UF₃¦CaF₂¦UF₃, URu₃, Ru; U, UF₃¦CaF₂¦UF₃, U₃Ru₅, URu₃; Ru, URu₃, UF₃¦CaF₂¦UF₃, URu₃C_0.7, Ru, C; U, UF₃¦CaF₂¦UF₃, URu₃C_0.7, U₂RuC₂, C. The Gibbs energies of formation of URu₃, U₃Ru₅, URu₃C_0.7 and U₂RuC₂ were evaluated from the measured electromotive force which give ^fΔG^o〈URu₃〉 = −199 100 + 35.9 T J mol^−1fΔG^o〈U₃Ru₅〉 = −398 600 + 43.6 T J mol^−1fΔG^o〈URu₃C_0.7〉 = −192 600 + 2.5 T J mol^−1fΔG^o〈U₂RuC₂〉 = −380 200 + 52.5 T J mol⁻¹ The implications of these thermodynamic data for the behaviour of the fission product ruthenium in irradiated carbide fuels are discussed.     

Syntheses, structures, and vibrational spectroscopy of the two-dimensional iodates Ln(IO3)3 and Ln(IO3)3(H2O) (LnYb, Lu)

The reaction of Lu³⁺ or Yb³⁺ and H₅IO₆ in aqueous media at 180 °C leads to the formation of Yb(IO₃)₃(H₂O) or Lu(IO₃)₃(H₂O), respectively, while the reaction of Yb metal with H₅IO₆ under similar reaction conditions gives rise to the anhydrous iodate, Yb(IO₃)₃. Under supercritical conditions Lu³⁺ reacts with HIO₃ and KIO₄ to yield the isostructural Lu(IO₃)₃. The structures have been determined by single-crystal X-ray diffraction. Crystallographic data are (MoKα, λ=0.71073 Å): Yb(IO₃)₃, monoclinic, space group P2₁/n, a=8.6664(9) Å, b=5.9904(6) Å, c=14.8826(15) Å, β=96.931(2)°, V=766.99(13), Z=4, R(F)=4.23% for 114 parameters with 1880 reflections with I>2σ(I); Lu(IO₃)₃, monoclinic, space group P2₁/n, a=8.6410(9), b=5.9961(6), c=14.8782(16) Å, β=97.028(2)°, V=765.08(14), Z=4, R(F)=2.65% for 119 parameters with 1756 reflections with I>2σ(I); Yb(IO₃)₃(H₂O), monoclinic, space group C2/c, a=27.2476(15), b=5.6296(3), c=12.0157(7) Å, β=98.636(1)°, V=1822.2(2), Z=8, R(F)=1.51% for 128 parameters with 2250 reflections with I>2σ(I); Lu(IO₃)₃(H₂O), monoclinic, space group C2/c, a=27.258(4), b=5.6251(7), c=12.0006(16) Å, β=98.704(2)°, V=1818.8(4), Z=8, R(F)=1.98% for 128 parameters with 2242 reflections with I>2σ(I). The f elements in all of the compounds are found in seven-coordinate environments and bridged with monodentate, bidentate, or tridentate iodate anions. Both Lu(IO₃)₃(H₂O) and Yb(IO₃)₃(H₂O) display distinctively different vibrational profiles from their respective anhydrous analogs. Hence, the Raman profile can be used as a complementary diagnostic tool to discern the different structural motifs of the compounds.     

Synthèse et structures cristallines de Cs3MI4NO3 (M = Zn,Co, Cd): Un exemple de substitution sélective

The compounds Cs₃MX₅ (M is a bivalent metal, and X an halogen) consist of Cs⁺, I⁻, and distorted (MI₄)²⁻ ions. The separate X⁻ ion suggests a possible substitution by another monovalent anion. The new compounds Cs₃MI₄NO₃ (M = Zn, Co, Cd) have been synthesized and characterized by X-ray diffraction. They are orthorhombic Pnma, a = 10.114(4), b = 11.601(5), c = 14.290(9) Å for Cs₃ZnI₄ NO₃; a = 10.078(8), b = 11.621(4), c = 14.262(6) Å for Cs₃CoI₄NO₃; a = 10.177(4), b = 11.784(5), c = 14.336(7) Å for Cs₃CdI₄NO₃; Z = 4. The crystal structures are described. The NO₃ groups surrounded by six Cs⁺ cations occupy the same sites as the separate I⁻ ion in the Cs₃MI₅ compounds.     

Gas-phase solvation of protonated aliphatic amines: methyl,ethyl, n-propyl,and iso-propylamine

The thermodynamic quantities K_{n?1 n}, ΔG⁰_{n?1, n} and ΔS⁰_n?1, n for the gas phase equilibrium reactions RNH⁺₃(RNH₂)_n?1 + RNH₂ = RNH⁺₃(RNH₂)_n, where n ? 3 and R indicates an alkyl group (CH₃, C₂H₅, n-C₃H₇ and iso-C₃H₇), have been determined.     

Trivalent phosphorus derivatives of group via : IV. Infrared and pmr studies of the protonation of M(CO)6−n(PA3)n Complexes (M = Mo,W; A = CH3, OCH3; n = 2, 3, 4)

The action of trifluoroacetic acid on the series M(CO)_6?n(PA₃)_n (M = Mo, W; A = CH₃, OCH₃; n = 2, 3, 4) has shown that protonation occurs if n ? 3. For n = 3 the basicity of the ligand PA₃ plays a more important role in the stability of [HM(CO)₃(PA₃)₃]⁺complexes than for n = 4. Infrared and proton NMR give evidence of the stereochemical non-rigidity of the [HM(CO)_6?n(PA₃)_n]⁺ heptacoordinated cation.     

The role of boron trichloride in the synthesis of phenyltrichlorosilane from benzene and trichlorosilane

Benzene and trichlorosilane form phenyltrichlorosilane and hydrogen. Boron trichloride has long been used as the preferred catalyst for this process. The mechanism of catalysis is indicated as follows: BCl₃ + xHSiCl₃ → H_xBCl_3?x + xSiCl₄; H_xBCl_3?x + xC₆H₆ → (C₆H₅)_x + xH₂; (C₆H₅)_xBCl_3?x + xHSiCl₃ → H_xBCl_3?x + xC₆H₅SiCl₃.     

Gas-phase ion equilibria studies of protons and chloride ions in propanol and acetone

The gas-phase clustering reactions of proton in propanol and acetone, and chloride ions in acetone were investigated. The −ΔH_n−1,n values obtained for clustering reactions (n−1,n) were as follows: H⁺ (C₃H₇OH)_n−1 + C₃H₇OH ⇄ H⁺ (C₃H₇OH)_n, (2, 3) 18.9 kcal mol⁻¹, (3, 4) 14.2 kcal mol⁻¹, (4, 5) 11.7 kcal mol⁻¹; H⁺ (CH₃COCH₃)₂ + CH₃COCH₃ ⇄ H⁺ (CH₃COCH₃)₃, 14.2 kcal mol⁻¹; and Cl⁻ + CH₃COCH₃ ⇄ Cl⁻ (CH₃COCH₃), 12.4 kcal mol.⁻¹. For clustering reactions, Cl⁻ (CH₃COCH_3n−1 + CH₃COCH₃ ⇄ Cl⁻ (CH₃COCH₃)_n where n ≥ 2, the equilibria could not be established; probably due to the isomerization of ligand acetone molecules from the keto to enol form.     

Synthesis and crystal structure of three silver indium double phosphates

Three new silver indium double phosphates Ag₃In(PO₄)₂ (I), β-(II) and α-Ag₃In₂(PO₄)₃ (III) were synthesized by solid state method (I and II—700 °C, III—900 °C). Compounds I and II crystallize into a monoclinic system (I—sp. gr. C2/m, Z=2, a=8.7037(1)Å, b=5.4884(1)Å, c=7.3404(1)Å, β=93.897(1)°; II—sp. gr. C2/c, Z=4, a=12.6305(1)Å, b=12.8549(1)Å, c=6.5989(1)Å, β=113.842(1)°), and compound III crystallize into a hexagonal system (sp. gr. R-3c, Z=6, a=8.9943(1)Å, c=22.7134(1)Å). Their crystal structures were determined by the Rietveld analysis (I—R_p=6.47, R_wp=8.54; II—R_p=5.67, R_wp=6.40; III—R_p=7.30, R_wp=9.91). Structure of Ag₃In(PO₄)₂ is related to the sodium chromate structure type and is isotypic to α-Na₃In(PO₄)₂. The polymorphous modifications of β- and α-Ag₃In₂(PO₄)₃ are isostructural to sodium analogs (β- and α-Na₃In₂(PO₄)₃) and are related to alluaudite (II) and NASICON (III) structure types. Compounds I and II are not stable at temperature above 850 °C. Ag₃In(PO₄)₂ is decomposed providing silver orthophosphate Ag₃PO₄ and α-Ag₃In₂(PO₄)₂. β-Ag₃In₂(PO₄)₃ is transformed to α-Ag₃In₂(PO₄)_3.     

Metal carbonyl-trifluorophosphine systems : X. Mono-and triruthenium carbonyls

Triruthenium dodecacarbonyl reacts with high pressure PF₃ or with PF₃/CO mixtures to yield two series of compounds. At high PF₃ pressures, the mononuclear species Ru(PF₃)_x(CO)_5−x (x = 5, 4 and 3) are the main products with only traces of Ru(PF₃)₂(CO)₃ and Ru(PF₃)(CO)₄ being found. With high carbon monoxide pressure and less PF₃, the species Ru₃(PF₃)_y(CO)_12−y (y = 0–6) are the main products. It is seen that Ru₃(CO)₁₂ can have up to six CO groups replaced sequentially before the cluster is broken followed by the formation of the mononuclear species. The evidence shows that the Ru(PF₃)_x(CO)_5−x species are stereochemically non-rigid.     

Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster [V5O9(PhPO3)3(PhPO3H)2]2− and a comparison to the structure of the fully oxidized parent cluster [V5O7(OCH3)2(PhPO3)5]1−

The room temperature reaction of (Bu₄N)₃V₅O₁₄ with PhPO₃H₂ in methanol yields the pentanuclear V(V) cluster (Bu₄N)[V₅O₇(OCH₃)₂(PhPO₃)₅]·CH₃OH (1·CH₃OH). In contrast, the hydrothermal reaction of (Ph₄P) [VO₂Cl₂], PhPO₃H₂ and (NH₄)H₂PO₄ at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph₄P)₂[V₅O₉(PhPO₃)₃(PhPO₃H)₂] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P2₁/n,a=12.167(2) Å,b=23.348(5) Å,c=22.508(5) Å,β=98.49(2)°,V=6323.9(19) ų,Z=4,D _calc=1.558 g cm^?3; 3, triclinic, $P\bar 1$ ,a=13.478(3) Å,b=14.399(3) Å,c=23.638(5) Å,α=72.53(2)°,β=85.58(2)°,γ=69.88(4)°,V=4107.0(16) ų,Z=2, D_calc=1.479 g cm^?3.     

Trifluoromethylselenato(0) and trifluoromethyltellurato(0) complexes of platinum(II)

The series of cis/trans-trifluoromethylselenato complexes [Pt(SeCF₃)_2 − xCl_x(PPh₃)₂] (x = 0, 1) was identified by NMR spectroscopic methods. While in acetonitrile solution spectra are dominated by the resonances of the cis derivatives, those of pure cis-[Pt(SeCF₃)₂(PPh₃)₂] indicate cis-trans-isomerisation in CH₂Cl₂ solution. In contrast, exchange reactions of cis-[PtCl₂(PPh₃)₂] and [NMe₄]TeCF₃ only gave evidence for cis isomers. Molecular structures of cis- and trans-[Pt(SeCF₃)₂(PPh₃)₂] and cis-[Pt(TeCF₃)₂(PPh₃)₂] are discussed in comparison with related compounds.     

Haloalkyl complexes of the transition metals: IV. The formation of a cationic ylide complex of platinum(II) from a chloromethylplatinum(II) complex and the crystal structures of cis-[Pt(CH2PPh3)X(PPh3)2]I (X = Cl or I)

The reactions of Pt(PPH₃)₄ and Pt(C₂H₄)(PPh₃)₂ with CH₂ClI have been investigated. The product of the reaction of Pt(PPh₃)₄ with CH₂ClI is the cationic ylide complex cis-[Pt(CH₂PPh₃)Cl(PPh₃)2][I], whereas the reaction of Pt(C₂H₄)-(PPh₃)₂ gives the oxidative addition product Pt(CH₂Cl)I(PPh₃)₂. Reaction of cis- or trans-Pt(CH₂Cl)I(PPh₃)₂] with PPh₃ gives the complex cis-[Pt(CH₂PPh₃)-Cl(PPh₃)₂][I]. The structures of the complexes cis-[Pt(CH₂PPh₃X(PPh₃)₂][I] (where X = Cl or I) have been determined by X-ray crystallography. Both complexes crystalize in the monoclinic space group P2₁/n. For X = Cl a 1388.6(7), b 2026.7(10), c 1823.9(9) pm, β 96.51(2)° and R converged to 0.075 for 3542 observed reflections; structural parameters Pt-Cl 240(1), Pt-C(3) 212(2), Pt-P(2) (trans to Cl) 235(1) and Pt-P(1) (trans to CH₂PPh₃) 233(1) pm; Cl-Pt-C(3) 86.9(5), C(3)-Pt-P(2) 91.8(5), P(2)-Pt-P(1) 97.0(2) and P(1)-Pt-Cl 85.1(2)°. For X = I, a 1379.4(7), b 2044.4(10), c 1840.0(9) pm, β 96.09(2)° and R converged to 0.071 for 4333 observed reflections; structural parameters Pt-I 266(1), Pt-C(3) 212(2), Pt-P(2) (trans to I) 226(1) and Pt-P(1) (trans to CH₂PPh₃ 233(1) pm; I-Pt-C(3) 87.2(5), C(3)-Pt-P(2) 91.5(5), P(2)-Pt-P(1) 96.5(2) and P(1)-Pt-I 85.6(1)°. Some other complexes of the type cis-[Pt(CH₂PPh₃)X(PPh₃)₂]Y are also described.     

Hybrid open-frameworks (MIL-n): Syntheses and structures of 2-dimensional gallium methylphosphonates (MIL-23) and 3-dimensional copper vanadium methyldiphosphonate (MIL-24)

The hydrothermal synthesis and the structure determination from powder or single crystals X-ray diffraction of 3 new metallophosphonates are presented. Crystal data: Ga(OH)_0.28F_0.72PO₃(CH₃): P2₁/c (n∘ 14), a = 7.7912(7) Å, b = 7.2310(6) Å, c = 9.3114(8) Å, β = 106.873(2) °, V = 502.00(8) Å ³, Z = 4, R₁(F) = 0.0409, wR₂(F²) = 0.0933 for 1 266 reflections I > 2 σ (I) with 77 parameters. Ga₃(OH)₃F₃(MePO₃)₂ H₂N(CH₂)₃NH₃: P-3 (No. 147), a = b = 7.2514(2) Å, c = 7.9413(2) Å, V = 361.6(3) ų, Z = 6, R_F = 7.95, R_Bragg = 7.18, R_wp = 17.3, R_p = 12.0. (V^IVO(H₂O))(Cu^II(H₂O))O₃P-CH₂-PO₃: P2₁2₁2₁ (No. 19), a = 6.3884(3) Å, b = 10.7284(4) Å, c = 11.2762(5) Å, V = 772.84(6) ų, Z = 4, R₁(F) = 0.0395, wR₂(F²) = 0.0861 for 2 012 reflections I > 2 σ (I) and 128 parameters.