Crystal and molecular structure and ion selective and complexing properties of 1,5-bis[2-(dioxyphosphoryl-4-methoxy)phenoxy]-3-oxapentane dihydrate [(OH)2(O)P(C6H3OCH3)(OCH2CH2)2 O(C6H4OCH3)P(O)(OH)2] · 2H2O

Ion selective and complexing properties of 1,5-bis[2-(dioxyphosphoryl-4-methoxy)phenoxy]-3-oxapentane dihydrate H₄M² · 2H₂O (I) were described. X-ray diffraction analysis for compound I was performed. The crystals are orthorhombic, a = 7.9818(16) ?, b = 30.553(6) ?, c = 9.0559(17) ?, V = 2208.5(8) ?³, Z = 4, space group Pnma, R = 0.0500 over 1372 reflections with I > 2??(I). In I, the H₄M² molecules are combined by hydrogen bonds (HB) with two crystallographically independent H₂O(7) and H₂O(8) molecules to give neutral H₄M² · 2H₂O aggregates. The HB between the phosphoryl and hydroxyl oxygen atoms of the aggregates and the donor O(7)-H??O(8) HB give rise to a layered structure. Conclusions about the Cu(H₂M²) compound structure were drawn based on the X-ray diffraction, DTA, and vibrational spectroscopy data.     

The effect of pressure on the raman spectrum of ice at low temperature

Extensive experimental studies of the Raman spectra of H₂O and D₂O ice in the lattice translational and OH (OD) stretching regions are reported for the first time at 88 K and from 0→6 kbar. An unambiguous transformation from ice I_h to ice IX has been observed, although previous studies suggest that a transition to ice II would have occurred. The ice I_h data are analysed in terms of various coefficients.     

Correlation effects on energy curves for proton transfer. The cation [H5O2]+

Potential curves for proton transfer in [H₅O₂]⁺ and for the dissociation of one OH bond in [H₃O]⁺ were calculated by both ab initio and semi-empirical LCAO MO SCF CI methods. The energy barrier of the symmetric double minimum potential in [H₅O₂]⁺ is very sensitive to electron correlation. At an OO distance of 2.74 Å it decreases from the HF value of 9.5 kcal/mole to about 7.0 kcal/mole. The results of the semi-empirical calculations agree well with the ab initio data as long as only relative effects are regarded. The partitioning of correlation energy into contributions of individual electron pairs is very similar for proton transfer in [H₅O₂]⁺ and for the dissociation of one OH bond in [H₃O]⁺. In this example the proton transfer appears as a superposition of two “contracted ionic dissociation” processes. An interpretation of the behaviour of correlation during these processes is presented.     

Diaquabromo(18-crown-6)rubidium and triaqua(18-crown-6)barium dibromide monohydrate: Synthesis and crystal structures

Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H₂O)₂] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H₂O)₃]²⁺ 2Br^? · H₂O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). The complex molecule [RbBr(18-crown-6)(H₂O)₂] in compound I and the randomly disordered cation [Ba(18-crown-6)(H₂O)₃]²⁺ in compound II are of the host-guest type: their Rb⁺ or Ba²⁺ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb⁺ is a distorted hexagonal pyramid with a triple apex at the Br^? ligand and two O atoms of the water molecules. In structure II, the Ba²⁺ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules.     

Simultaneous proton transfer along a linear water polymer

SCF CNDO calculations were performed for species H₃O⁺·(H₂O)_n·OH^? where n was varied from one to three. The position of the intervening protons was changed simultaneously while the oxygens and remaining hydrogens were kept fixed. It was found that only one minimum occurs when n is one or two while an asymmetric double minimum potential is found when n is equal to three. A barrier of 10.4 kcal/mole was found.     

Ion-selective properties of 1,8-bis [2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H4L3), synthesis and vibrational spectra of copper and zinc complexes with H4L3, and crystal and molecular structure of [Cu(H4L3)(H2O)3][(H2L3)(H2O)]

The ion-selective properties of 1,8-bis[2-(dihydroxyphosphinyl)phenoxy]-3,6-dioxaoctane (H₄L³) have been studied and its potentiometric selectivity coefficients have been determined. New complexes [Cu(H₄L³)(H₂O)₃][(H₂L³)(H₂O)] (I) and Zn(H₄L³)(H₂L³) · 3H₂O, and Cu(H₂L³) · 2(H₂O) have been synthesized and characterized. The crystal and molecular structure of I has been determined by X-ray crystallography and vibrational spectroscopy. The crystals are monoclinic, a = 10.279(5) Å, b = 26.532(13) Å, c = 8.399(4) Å, β = 99.270(8)°, V = 2260.8(7) ų, Z = 2, space group Cm, R = 0.0347 for 4325 reflections with I > 2σ(I). Ionic compound I is composed of the [Cu(H₄L³)(H₂O)₃]²⁺ complex cations and [(H₂L³)(H₂O)]^2? anions. In the cation, the Cu²⁺ cation located in the m plane is bound to a tetragonal pyramidal (TP) array. The equatorial plane of the TP is formed by two phosphoryl oxygen atoms of the podand (Cu(1)-O, 1.921(2) Å) and two O atoms of two water molecules (av. Cu(1)-O, 1.981(3) Å). The third water molecule is at the axial vertex of the TP at a considerably larger distance (Cu(1)-O, 2.139(3) Å). The anion is of the host-guest type. The host is the deprotonated podand (H₂L³)^2?, and the guest is the water molecule. The latter is bound to the terminal hydroxyl groups of two phosphoryl groups of the podand by two acceptor hydrogen bonds and to two central ether oxygen atoms of the (H₂L³)^2? anion by one donor bifurcated hydrogen bond. The cations and anions in the structure are linked by hydrogen bonds to form chains parallel to the c axis.     

Photoionization of aqueous indole: Conduction band edge and energy gap in liquid water

Previous work on the determination of the photoionization threshold (I_sol) of tryptophan has now been extended to indole as a solute, both in tetramethylsilane (TMSi) and H₂O solvents. In TMSi, electron scavenging by N₂O or photoconductivity measurements lead to the same I_sol value: 4.95 ± 0.1 eV. In water, I_sol is found equal to 4.35 ± 0.1 eV. From these experiments, information on the ionization mechanism, on the oxidized solute and on the solvent can be gained: (i) the scavenger electron affinity does not intervene in the energy balance providing I_sol; (ii) an “effective” ionic radius of indole (1.40 Å) is estimated which suggests that the positive charge remains highly localized on the N-atom of the indole ring; (iii) a value of ?1.2 ± 0.1 eV can be deduced for V_o, the conduction band edge of water; (iiii) from the above findings, the energy gap E_G of pure water, considered as a semi-conductor, would be close to 7 eV. Such a result is discussed in terms of literature data pertaining to electron ejection in pure liquid water and X-ray photoelectron spectroscopy of amorphous ice.     

Synthesis and crystal structure of diaquadibenzoatobis(nicotinamide)nickel(II)

A coordination compound of nickel(II) benzoate with nicotinamide [Ni(C₆H₅COO)₂(L)₂(H₂O)₂] (I) (L is nicotinic acid amide) is synthesized and studied by IR spectroscopy. Its crystal structure is solved by X-ray crystallography. The crystals of compound I are monoclinic: a = 7.152 Å, b = 18.266 Å, c = 10.341 Å, β = 109.24°, V = 1275.4 ų, Z = 2, space group P2₁/c. Structural units of a crystal of I are centrosymmetric octahedral complex molecules. The coordination environment of the Ni atom contains two O atoms (Ni-O(1) 2.066(2) Å) and two N atoms (Ni-N(1) 2.091(2) Å) of the monodentate-coordinated benzoate anions and nicotinamide molecules, respectively, as well as two O atoms of the H₂O molecules (Ni-O(1w) 2.110(2) Å).     

Thermogravimetric investigation of the dehydration thermodynamics of amorphous silica after its hydrothermal and thermovaporous treatment

After hydrothermal and thermovaporous treatment of chemically pure amorphous aqueous silicic acid in solutions of NaOH and NH₄OH and in water vapour it is possible, using complex thermal analysis, to detect the weight loss and heat effects corresponding to evaporation of various forms of combined water, and to estimate the heats of evaporation of these forms. From the obtained data, the following water forms have been identified: (1) at 200–300° capillary-condensed water formations of the cluster type evaporate;ΔH _deh is about 8 kcal/mole H₂O; (2) at 250–400°, molecules of water linked by hydrogen bonds with hydroxyl groups on the surface and in the volume of the particles;ΔH _deh. is about 5 kcal/mole H₂O; (3) at 350 600°, molecules of water coordinated to silicon atoms in the volume of the particles;ΔH _deh is approximately 1 kcal/mole H₂O. The total evaporation heat changes from 10 kcal/mole H₂O when water of form 1 predominates, to 5 kcal/mole H₂O when forms 2 and 3 predominate.     

The structure of the H3O+ (hydronium) ion

Near Hartree-Fock level ab initio molecular orbital calculations on H₃O⁺ and a minimum energy structure with θ(HOH) = 112.5° and r(OH) = 0.963 Å and an inversion barrier of 1.9 kcal/mole. By comparing these results to calculations on NH₃ and H₂O, where precise experimental geometries are known, we estimate the “true” geometry of isolated H₃O⁺ to have a structure with θ(HOH) = 110-112°, r(OH) = 0.97–0.98 Å and an inversion barrier of 2–3 kcal/mole. Our prediction for the proton affinity of water is ≈ 170 kcal/mole, which is somewhat smaller than the currently accepted value.     

Ab initio valence-bond calculations of H2O

The first and second bond dissociation energies for H₂O have been calculated in anab initio manner using a multistructure valence-bond scheme. The basis set consisted of a minimal number of non-orthogonal atomic orbitals expressed in terms of gaussian-lobe functions. The valence-bond structures considered properly described the change in the molecular system as the hydrogen atoms were individually removed to infinity. The calculated equilibrium geometry for the H₂O molecule has an O-H bond length of 1.83 Bohrs and an HOH bond angle of 106.5°. With 49 valence-bond structures the energy of H₂O at this geometry was ?76.0202 Hartrees. The calculated equilibrium bond length for the OH radical was 1.86 Bohrs and the energy, using the same basis set, was ?75.3875 Hartrees. After correction for zero point energies the calculated bond dissociation energies are: H₂O → OH + H, D₁=75.38 kcal/mole and OH → O+H, D₂=54.79 kcal/mole.     

Hydrothermal syntheses and structures of two novel vanadium selenites, {[VO(OH)(H2O)](SeO3)}4·2H2O and (H3NCH2CH2NH3)[(VO)(SeO3)2]

Two novel vanadium selenites {[VO(OH)(H₂O)](SeO₃)}₄·2H₂O 1 and (H₃NCH₂CH₂NH₃)[(VO)(SeO₃)₂] 2 were synthesized by hydrothermal method and their crystal structures were determined by single-crystal X-ray diffraction. It is characterized by inductively coupled plasma (ICP), thermogravimetric (TG) and elemental analyses. Compound 1 crystallizes in the monoclinic system, space group C2/c, a=21.2250(11) Å, b=12.6309(6) Å, c=17.0249(10) Å, β=96.830(3)°, V=4531.8(4) Å³ and Z=8, R₁ [I>2σ(I)]=0.0344, wR₂ [I>2σ(I)]=0.119; Compound 2 crystallizes in the monoclinic system, space group P2₁/c, a=9.6389(4) Å, b=6.9922(3) Å, c=15.0324(5) Å, β=102.297(2)°, V=989.90(7) Å³ and Z=4, R₁ [I>2σ(I)]=0.0452, wR₂ [I>2σ(I)]=0.117. {[VO(OH)(H₂O)](SeO₃)}₄·2H₂O has a 1D structure constructed from the {[VO(OH)(H₂O)](SeO₃)}_∞ chains. (H₃NCH₂CH₂NH₃)[(VO)(SeO₃)₂] has a layered structure composed of alternating VO₅ and SeO₃ units with protonated ethylenediamine as interlayer guest.     

The electrochemical Peltier effect observed with electrode reactions of Fe(II)/Fe(III) redox couples at a gold electrode

The electrochemical Peltier effect was studied at a gold electrode in solutions containing some Fe(II)/Fe(III) redox couples by measuring the local temperature change in the electrode/solution interphase under controlled-potential and controlled-current polarization. Relative values of the electrochemical Peltier coefficient for the cathodic process at equilibrium potential, which is denoted by (Π_c)_I=0, were determined by analyzing the observed temperature change as a function of current. The values of (Π_c)_I=0 were found to be positive for the Fe(H₂O)₆²⁺/Fe(H₂O)₆³⁺ systems in HClO₄ (1 M), HNO₃ (1 M), H₂SO₄ (0.5 M), and HCl (1 M), their magnitudes being very similar in the first three acid solutions, but smaller in the HCl solution. On the other hand, a negative value of (Π_c)_I=0 was obtained in the case of a Fe(CN)₆^4?/Fe(CN)₆^3? couple in a H₂SO₄ (0.5 M) solution. Such a difference in the Peltier coefficient is considered to be due to the difference in the ionic species of iron involved in the electrode reaction.     

A new binuclear germanium(IV) and copper(II) complex with 1,3-diamino-2-propanoltetraacetic acid: Crystal and molecular structure of [(H2O)(OH)Ge(μ-Hpdta)Cu(H2O)] · 3H2O

A heteronuclear germanium(IV) and copper(II) complex with 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) has been synthesized for the first time. The compound has been characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The structure of the complex [(H₂O)(OH)Ge(μ-Hpdta)Cu(H₂O)] · 3H₂O (I) has been determined by single-crystal X-ray diffraction. The crystals of I are monoclinic, a = 1 5.327(4) Å, b = 11.626(3) Å, c =21.058(3) Å, β = 96.35(2)°, V = 3729.2(2) ų, Z = 8, space group C2/c, R1 = 0.0551 on 3090 reflections with I > 2σ(I). The structural units of the crystal of I are binuclear complex molecules [(H₂O)(OH)Ge(μ-Hpdta)Cu(H₂O)] and crystal water molecules. The germanium and copper atoms are linked by the bridging oxygen atom of the deprotonated isopropanol group of the Hpdta^5? ligand (Ge-O, 1.843(3) Å; Cu-O, 2.221(3) Å). The coordination spheres of the Ge and Cu atoms contain each one nitrogen atom (Ge-N, 2.090(4) Å; Cu-N, 2.000(4) Å) and two carboxyl oxygen atoms from four acetate arms of the heptadentate Hpdta^5? ligand (av. Ge-O, 1.909(3) Å; Cu-O, 1.948(3) Å). The coordination polyhedron of the Ge atom is completed to a distorted octahedron by the oxygen atoms of the terminal hydroxy group (Ge-O, 1.786(3) Å) and a water molecule (Ge-O, 1.904(3)Å). The coordination polyhedron of the copper atom is completed to a prolate tetragonal pyramid (4 + 1) by the oxygen atom of a water molecule in the equatorial position (Cu-O, 1.955(4) Å) and the bridging O(11) atom (Hpdta^5?) in the apical position. Binuclear molecules are linked pairwise in a head-to-head manner via double Cu-O(2) bridges to form the centrosymmetric tetranuclear supramolecule {[(H₂O)(OH)Ge(μ-Hpdta)Cu(H₂O)]}₂. The coordination of the Cu atom is completed by the weak Cu-O(2A) contact (3.303 Å) to an asymmetrically elongated tetragonal bipyramid (4 + 1 +1). In the crystal, the complex molecules and crystal water molecules are combined by a system of hydrogen bonds into a three-dimensional framework.     

3-(diallylamino)propanenitrile ((C3H5)2NC2H4CN, L) π-complexes with copper(I) ionic salts. Syntheses and crystal structures of compounds [Cu(H+L)ClO4]ClO4 · H2O, [Cu(H+L)BF4]BF4 · H2O, and [Cu(H+L)(H2O)]SiF6 · H2O

Qualitative single crystals of ??-complexes Cu(H⁺L)(ClO₄)]ClO₄ · H₂O (I), Cu(H⁺L)(BF₄)]BF₄ · H₂O (II), and [Cu(H⁺L)(H₂O)]SiF₆ · H₂O (III) are synthesized from solutions of 3-(diallylamino)propanenitrile (L) in propanol, ethanol, and methanol-water acidified with the corresponding acid to pH 3.5?C5 and from the copper(II) salts (Cu(ClO₄)₂ · 6H₂O, Cu(BF₄)₂ · 6H₂O, and CuSiF₆ · 4H₂O) using the alternating-current electrochemical method on copper wire electrodes. The crystal structures of the complexes are determined. All compounds crystallize in the monoclinic crystal system: complexes I and II are isostructural, space group P2₁/n, Z = 4. For compound III, space group P2₁/c, Z = 8. Unit cell parameters: for I a =7.8153(3), b = 16.7824(7), c = 12.4426(5) ?, ?? = 93.410(2)°, V = 1629.1(1) ?³; for II, a = 7.6755(4), b = 16.7119(7), c = 12.3784(6) ?, ?? = 94.354(2)°, V = 1583.2(1); and for III a = 9.826(2), b = 24.009(3), c = 12.061(2) ?, ?? = 91.820(6)°, V = 2843.9(7) ?³. The trigonal pyramidal coordination of the copper atom in complexes I-III is formed by two C=C bonds of the allyl groups of H⁺L, the nitrile N atom of the adjacent cation of the ligand, and the O or F atom of the ClO ₄ ^? or BF ₄ ^? anions. In structure III, the apical position of the pyramid is occupied by the O atom of the water molecule, since the SiF ₆ ^2? anion is considerably remote from the copper(I) atom. However, this anion is bound to the organic cation by hydrogen bonds F??H (2.05?C2.51 ?).     

The energy of the N→O bond in 3-nitroisoxazoline N-oxide

The enthalpy of combustion of 3-nitroisoxazoline has been determined as ΔH _c ^298.15 =?414±0.3 kcal/mole and that of 3-nitroisoxazoline N-oxide as ΔH _c ^298.15 =?406.6±0.5 kcal/mole. From the values for the heats of combustion and evaporation, the standard enthalpies of formation have been calculated and the energy of the N→O bond has been evaluated at 64±3 kcal/mole.     

Thulium(III) trifluoroacetates Tm(CF3COO)3 · 3H2O and Tm2(CF3COO)6 · 2CF3COOH · 3H2O: Synthesis and crystal structure

Thulium trifluoroacetate compounds have been synthesized, Tm(CF₃COO)₃ · 3H₂O (I) and Tm₂(CF₃COO)₆ · 2CF₃COOH · 3H₂O (II). The structure of I has been refined by the Rietveld method on the basis of the structural data for Cd(CF₃COO)₃ · 3H₂O. The structure of II has been solved in a single-crystal X-ray diffraction study. Compound I has been studied by thermal analysis. Crystals of I and II are monoclinic: for I a = 9.062(2) Å, b = 18.678(3) Å, c = 9.687(2) Å, β = 113.93(1)°, Z = 2, space group P2₁/c, R ₁ = 0.062; for II a = 8.560(4) Å, b = 19.866(5) Å, c = 20.813(7) Å, β = 101.69(4)°, Z = 8, space group C2/c, R ₁ = 0.0392. In the molecular structure of I, thulium atoms are bonded in pairs through four bridging trifluoroacetate anions to form dimers. The coordination polyhedron of the thulium atom also includes the three O atoms of the water molecules and the O atom of the monodentate trifluoroacetate group; the coordination number of the thulium atom is eight. In the chain structure of II, there are two crystallographically independent thulium atoms with coordination numbers 8 and 9. The coordination polyhedra of the Tm(1) and Tm(2) atoms are a distorted monocapped tetragonal antiprism and a distorted tetragonal antiprism, respectively. The Tm-O bond lengths are in the range 2.28(1)–2.85(2) Å. The thulium atoms are bound into chains through carboxylate groups. These chains are linked into layers through hydrogen bonds.     

Syntheses and structures of nine-coordinate K3[DyIII(nta)2(H2O)]·5H2O and eight-coordinate (NH4)3[DyIII(nta)2] complexes

K₃[Dy^III(nta)₂(H₂O)]·5H₂O and (NH₄)₃[Dy^III(nta)₂] have been synthesized in aqueous solution and characterized by IR, elemental analysis and single-crystal X-ray diffraction techniques. In K₃[Dy^III(nta)₂(H₂O)]·5H₂O the Dy^III ion is nine coordinated yielding a tricapped trigonal prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 15.373(5) Å, b = 12.896(4) Å, c = 26.202(9) Å; β = 96.122(5)°, V = 5165(3) ų, Z = 8, D _c = 1.965 g·cm^?3, μ = 3.458 mm^?1, F(000) = 3016, R ₁ = 0.0452 and wR ₂ = 0.1025 for 4550 observed reflections with I ≥ 2σ(I). In (NH₄)₃[Dy^III(nta)₂] the Dy^III ion is eight coordinated yielding a usual dicapped trigonal anti-prismatic conformation, and its crystal belongs to monoclinic system and C2/c space group. The crystal data are as follows: a = 13.736(3) Å, b = 7.9389(16) Å, c = 18.781(4) Å; β = 104.099(3)°, V = 1986.3(7) ų, Z = 2, D _c = 1.983 g·cm^?3, μ = 3.834 mm^?1, F(000) = 1172, R ₁ = 0.0208 and wR ₂ = 0.0500 for 2022 observed reflections with I ≥ 2σ(I). The results indicate that the difference in counter ion also influences coordination numbers and structures of rare earth metal complexes with aminopolycarboxylic acid ligands.     

Synthesis, crystal structure, and luminescent property of [Zn2(Ox)3]H2L · 4H2O (L = 2,2′-(1,4-butanediyl-bis(1H-benzimidazole))

A new complex [Zn₂(Ox)₃]H₂L · 4H₂O (L = 2,2??-(1,4-butanediyl)-bis(1H-benzimidazole)) (I) has been hydrothermally synthesized and characterized by the elemental analysis, IR spectroscopy, and single crystal X-ray diffraction. It crystallizes in monoclinic space group P2₁/c with a = 10.108(2), b = 15.600(4), c = 9.768(2) ?, ?? = 105.289(3)·, V = 1485.7(6) ?³, Z = 4. Complex I is a 2D honeycomb-like polymer with pro-toned L and water molecules intercalating in the cavities. The luminescent spectra shows the emission peak of complex I is at 455 nm which is attributed to ligand-to-metal charge transfer.     

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.