Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

Ammonium and potassium citratogermanates(IV): Synthesis, chemical compositions, and structures. The crystal structures of (NH4)[Ge(OH)(H2Cit)2] · H2O and K4[Ge(HCit)2(H2Cit)] · 3H2O

Methods for the synthesis of ammonium citratogermanate (NH₄)[Ge(OH)(H₂Cit)₂] · H₂O (I) and potassium citratogermanate (K₄[Ge(HCit)₂(H₂Cit)] · 3H₂O (II), where H₄Cit is citric acid) in aqueous MeCN were developed. The individuality, chemical composition, and thermal stability of complexes I and II were proved by elemental analysis, thermogravimetry, and IR spectroscopy. According to X-ray diffraction data, the coordination numbers of the Ge atoms are 5 and 6 and their coordination polyhedra are a square pyramid and an octahedron in complexes I and II, respectively. In both complexes, the Ge atom coordinates the deprotonated OH group and the α-carboxyl group of the ligands H _n Cit^4?n to form five-membered chelate rings. Hydrogen bonds in I as well as potassium cations in II serve to unite these complexes into frameworks.     

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.     

Synthesis and properties of tetraalkylammonium chlorides peroxosolvates (CH3)4NCI·H2O2 and (C2H5)4NCl·H2O2

Tetraalkylammonium chlorides peroxosolvates (CH₃)₄NCl·H₂O₂ and (C₂H₅)₄NCl·H₂O₂ were synthesized. The composition of the solvates was proved by chemical analysis; their X-ray patterns, IR spectra, and thermograms were obtained. The solubility of the solvates in water and their stability in aqueous solutions were investigated.     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

Synthesis,Structure and Characterization of Three Metal Molybdate Hydrates: Fe(H2O)2(MoO4)2·H3O,NaCo2(MoO4)2(H3O2)and Mn2(MoO4)3·2H3O

Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...     

The thermal dehydration and decomposition of Ba[Cu(C2O4)2(H2O)]·5H2O

The thermal behaviour of Ba[Cu(C₂O₄)₂(H₂O)]·5H₂O in N₂ and in O₂ has been examined using thermogravimetry (TG) and differential scanning calorimetry (DSC). The dehydration starts at relatively low temperatures (about 80°C), but continues until the onset of the decomposition (about 280°C). The decomposition takes place in two major stages (onsets 280 and 390°C). The mass of the intermediate after the first stage corresponded to the formation of barium oxalate and copper metal and, after the second stage, to the formation of barium carbonate and copper metal. The enthalpy for the dehydration was found to be 311±30 kJ mol^–1 (or 52±5 kJ (mol of H₂O)^–1). The overall enthalpy change for the decomposition of Ba[Cu(C₂O₄)₂] in N₂ was estimated from the combined area of the peaks of the DSC curve as –347 kJ mol^–1. The kinetics of the thermal dehydration and decomposition were studied using isothermal TG. The dehydration was strongly deceleratory and the -time curves could be described by the three dimensional diffusion (D3) model. The values of the activation energy and the pre-exponential factor for the dehydration were 125±4 kJ mol^–1 and (1.38±0.08)×10¹⁵ min^–1, respectively. The decomposition was complex, consisting of at least two concurrent processes. The decomposition was analysed in terms of two overlapping deceleratory processes. One process was fast and could be described by the contracting-geometry model withn=5. The other process was slow and could also be described by the contracting-geometry model, but withn=2.The values ofE _a andA were 206±23 kJ mol^–1 and (2.2±0.5)×10¹⁹ min^–1, respectively, for the fast process, and 259±37 kJ mol^–1 and (6.3±1.8)×10²³ min^–1, respectively, for the slow process.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthday     

Synthesis, Crystal Structure and Luminescence Property of [Co(hmz)2(H2O)4]·2H2O

A new mononuclear Co(Ⅱ) complex, [Co(hmz)2(H2O)4]·2H2O, has been synthesized by the reaction of Co(CH3COO)2·4H2O with 1-(4-hydroxyphenyl)-5-mercaptotetrazole (Hhmz). It crystallizes in the monoclinic system, space group P21/n with a = 13.502(5), b = 6.718(3), c = 13.972(6) (A), β = 117.532(4)°, V = 1123.9(8) (A)3, Z = 2, M r = 553.45, F(000) = 570, Dc = 1.635 g/cm3, μ = 1.008 mm-1, the final R = 0.0272 and wR = 0.0684 for 2194 observed reflections (Ⅰ＞ 2σ(Ⅰ)). The Co(Ⅱ) is six-coordinated by two nitrogen atoms from two hmz-1 ligands and four water molecules, forming an octahedral geometry. The intermolecular hydrogen bonding and offset-panel π-π stacking interactions between the adjacent molecules extend the compound into a three- dimensional supramolecular framework. The title compound emits strong blue fluorescent light (λem(max) = 427 nm) at room temperature and is red-shifted compared with free ligand Hhmz (λem(max) = 342 nm).     

An analysis of the vibrational frequencies and amplitudes of the H5O+2 ion in H4SiW12O40·6H2O (TSA·6H2O) and H3PW12O40·6H2O (TPA·6H2O)

The infrared, Raman and inelastic neutron scattering (INS) spectra of TSA·6H₂O and TPA·6H₂O are in agreement with those expected for the presence of H₅O⁺₂ ions. Force fields for different assignment schemes are compared with the observed vibrational frequencies and the INS spectral profile. All but two schemes are eliminated. Whilst low-resolution INS spectroscopy cannot distinguish between these two schemes, the orientations of the vibrational ellipsoids for one scheme are in better agreement with those reported from low-temperature crystallographic studies of the H₅O⁺₂ ion.     

Copper(II) malonate coordination frameworks with amino-1,2,4-triazole: Crystal structures and magnetic properties of [Cu2(mal)2(datz)2(H2O)]·5H2O and [Cu2(mal)2(atz)2(H2O)]·3H2O

Two new malonato-bridged copper(II) complexes of the composition [Cu₂(mal)₂(datz)₂(H₂O)]·5H₂O (1) and [Cu₂(mal)₂(atz)₂(H₂O)]·3H₂O (2) (mal = malonate, atz = 4-amino-1,2,4-triazole, datz = 3,5-diamino-1,2,4-triazole) are prepared and characterized by X-ray crystal structure determination and magnetic studies. The environment of each copper atom in 1 and 2 has distorted square pyramidal and octahedral geometries. The intrachain copper-copper separation is 6.305 Å and 3.640 Å across the carboxylates and trizolates bridges respectively for complexes 1 and 2. The magnetic properties of 1 and 2 are investigated in the temperature range 2–300 K. The overall antiferromagnetic behavior is observed in both cases.     

Synthesis and Structure of a Novel Compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O

A novel compound [Cu2(EDTA)(Py)2(H2O)2]·2H2O was synthesized by the reaction of CuSO4(5H2O with H4EDTA in pyridine/water (V/V = 1/4) solvent, and characterized by elemental analysis, IR spectrum and X-ray single-crystal diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 1.26974(6), b = 0.67949(3), c = 1.48548(3) nm, β = 91.454(2)o, V = 1.28122(9) nm3, Z = 2, Dc = 1.673 g/cm3, Mr = 645.56, F(000) = 664, μ(MoKα) = 1.729 mm-1, the final R = 0.0353 and wR = 0.0832 for 1920 observed reflections (I > 2((I)). The compound is a centrosymmetric binuclear molecule with bridged EDTA group. Each Cu(II) atom is linked to two oxygen atoms and one nitrogen atom of EDTA, one oxygen atom of water and one nitrogen atom of pyridine to form a distorted square pyramidal environment. There exist face-to-face π-π stacking interactions between pyridine rings from neighboring molecule with the interplanar distance of 0.3670 nm and hydrogen bonding between EDTA and water molecules.     

Synthesis and Crystal Structure of {Cu2(pdc)2(4,4′-bipy)(H2O)·(3H2O}2

The title compound {Cu2(pdc)2(4,4′-bipy)(H2O)(3H2O}2 1 (H2pdc = pyridine-2,6- dicarboxylic acid, also known as dipicolinic acid; 4,4′-bipy = 4,4′-bipyridine) has been synthesized by the hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group Pī with a = 7.2278(3), b = 10.6259(4), c = 17.7614(6)A, α= 79.5990(10), β = 83.6300(10), γ = 71.8280(10)o, V = 1272.60(8)A3, C48H44Cu4N8O24, Mr = 1371.07, Z = 1, Dc = 1.789 g/cm3, μ = 1.747 mm-1, F(000) = 696, R = 0.0397 and wR = 0.1137 for 3938 observed reflections (I > 2σ(I)). There are two kinds of Cu coordination environments, and each central copper(II) atom is five-coordinated in a distorted square-based pyramidal coordination geo- metry. Four copper(II) atoms are linked by four pdc and two 4,4′-bipy ligands to form an annular rectangle structure. Extensive hydrogen-bonding interactions involving carboxylate O atoms as well as coordinated and free water molecules lead to the formation of a three-dimensional network struc- ture.     

Tetrameric complexes of germanium(IV) and cobalt(II), Nickel(II), or Zinc(II) with 1,3-Diamino-2-propanol-tetraacertic acid: crystal and molecular structures of [(OH)2Ge2(μ-Hpdta)2Zn2(H2O)4] · 12H2O

Heteronuclear germanium(IV) and Zn(II) (Co(II), Ni(II)) complexes with 1,3-diamino-2-propanol-tetraacetic acid (H₅Hpdta) were synthesized. The compounds were characterized by elemental analysis, thermogravimetry, and IR spectroscopy. X-ray diffraction analysis of the crystals of [(OH)₂Ge₂(??-Hpdta)₂Zn₂(H₂O)₄] · 12H₂O (I) was performed. The crystals are tetragonal, a = 15.2022(9)?, c = 20.932(3) ?, V = 4837.5(7) ?³, Z = 4, space group P4₃, R1 = 0.0449 over 11399 reflections with I > 2??(I). The structural units of the crystal are tetrametric complex molecules [(OH)₂Ge₂(??-Hpdta)₂Zn₂(H₂O)₄] and water molecules of crystallization. The tetramer is composed of two similar neutral dimeric molecules [(OH)Ge(??-Hpdta)Zn(H₂O)₂]. The germanium and zinc atoms in the dimer are linked by the bridging oxygen atom of the deprotonated isopropanol group of the Hpdta^5? ligand (average Ge-O, 1.844(2)?; Zn-O, 2.192(3)?). The coordination sphere of the Ge and Zn atoms contains also one nitrogen atom (average Ge-N, 2.074(4)?; Zn-N, 2.156(3)?), four oxygen atoms belonging to four acetate branches of the octadentate Hpdta^5? ligands including two carboxyl O atoms for each Ge atom (average Ge-O, 1.912(3)?) and two carbonyl O atoms for each Zn (average Zn-O, 2.065(3)?). The coordination polyhedron of each Ge atom is completed to a distorted octahedron by the oxygen atom of the terminal hydroxy group (average Ge-O, 1.772(2)?) and the carboxyl oxygen atom of the bridging acetate branch (average Ge-O, 1.926(3)?) coordinated through carbonyl oxygen to Zn atom (average Zn-O, 2.148(3)?) of the second dimeric molecule. The distorted octahedron around each Zn atom is completed by oxygens of two water molecules at substantially different distances (average Zn-O, 1.984(3) and 2.100(3)?). The structural units are combined by O-H??O hydrogen bonds to form a framework.     

Syntheses and structures of seven-coordinate K3[Cd(Dtpa)], K2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O, and Na2[Cd(H2O)4][Cd(Edta)(H2O)]2 · 2H2O complexes

The title complexes, K₃[Cd(Dtpa)] (H₅Dtpa = diethylenetriamine-N,N,N,N′,N′-pentaacetic acid, (I)), K₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (H₄Edta = ethylenediamine-N,N,N′,N′-tetraacetic acid, (II)), and Na₂[Cd(H₂O)₄][Cd(Edta)(H₂O)]₂ · 2H₂O (III), were prepared, and their compositions and structures were determined by elemental analyses, IR spectra, and single-crystal X-ray diffraction techniques, respectively. In complex I, the Cd is seven-coordinated by one Dtpa ligand yielding a pseudo-monocapped trigonal prism conformation, and the complex crystallizes in the triclinic crystal system with the Pi space group. The crystal data are as follows: a = 8.7300(17), b = 9.1200(18), c = 15.110(3) Å, α = 95.52(3)°, β = 96.59(3)°, γ = 99.63(3)°, V = 1170.0(4) ų, Z = 2, ρ = 1.754 g/cm³, μ = 1.519 mm^?1, F(000) = 616, R = 0.0644 and wR = 0.1712 for 3842 observed reflections with I ≥ 2σ(I). For complex II, in the [Cd(Edta)(H₂O)]^2? complex anion the Cd²⁺ ion is seven-coordinated by one Edta ligand and one water molecule, yielding a pseudo-pentagonal bipyramid conformation. In the [Cd(H₂O)₄]²⁺ cation, the bridged Cd is six-coordinated, yielding an almost standard octahedral conformation. The complex crystallizes in the monoclinic system with P2₁/n space group. The crystal data are as follows: a = 9.098(3), b = 16.442(6), c = 12.023(4) Å, β = 91.053(6)°, V = 1798.3(12) ų, Z = 2, ρ = 2.098 g/cm³, μ = 2.086 mm^?1, F(000) =1124, R = 0.0406 and wR = 0.1152 for 3680 observed reflections with I ≥ 2σ(I). In complex III, the conformations of Cd²⁺ ions are similar to those of the potassium salt complex, and the complex also crystallizes in the monoclinic crystal system with the P2₁/n space group. The crystal data are as follows: a = 9.134(7), b = 16.500(13), c = 12.075(10) Å, β = 91.054(12)°, V = 1820(2) ų, Z = 2, ρ = 2.015 g/cm³, μ = 1.856 mm^?1, F(000) = 1092, R = 0.0363 and wR = 0.0879 for 3707 observed reflections with I ≥ 2σ(I).     

Solid state synthesis,spectroscopic and X-ray studies of metal complexes of 2-picolinic acid and vapochromic behavior of [Co(Pic)2(H2O)2]·2H2O

Three compounds, [Cu(Pic)₂(H₂O)] (1a), [M(Pic)₂(H₂O)₂]·2H₂O] (M=Co (2a), Zn (3a), Pic = 2-picolinic acid) were obtained by solvent-free synthesis through grinding of metal acetate salt with 2-picolinic acid. Favorable comparison of solvent-free with solution based method of 1b, 2b and 3b was observed. Good resemblance of identity of compounds obtained through the two methods was confirmed by elemental analysis, spectroscopic techniques (UV-Vis and FTIR), TGA and PXRD. The single crystal diffraction data for [Co(Pic)₂(H₂O)₂]·2H₂O obtained from the Cambridge structure database (CSD), its PXRD simulated patterns closely matched that of complex 2a by solvent-free synthesis. Vapochromic behavior of this complex was studied using colour change, FT-IR, TGA, PXRD and solid state UV-visible spectroscopies. This complex generated specific colour which is also evident in the shifting of the vibrational frequencies (νO-H and ν C=O bands). The resulting inclusion compounds have different colours depending on the solvent used. In addition, exposure of the resultant inclusion compounds to ambient environment or heating for a few minutes regenerate the original material without degradation even after exposure/heating cycles as evident from TGA/DTG thermograms.     

Synthesis and Crystal Structure of [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O

A novel complex [Zn(FcCOO)2(2,2′-bipy)(H2O)]2·H2O (Fc = (η5-C5H5)Fe(η5-C5H4), 2,2′-bipy = 2,2′-bipyridine) has been synthesized and characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 6.8187(4), b = 21.7155(13), c = 19.7411(12) (A), α = 90, β = 97.7420(10), γ = 90°, C64H58Fe4Zn2N4O11, Mr = 1413.28, V = 2896.4(3) (A)3, Dc = 1.620 g/cm3, Z = 2, F(000) = 1444, μ(MoKα) = 1.857 mm-1, R = 0.0523 and wR = 0.0982 for 3219 observed reflections (I ＞ 2σ(I)). Structural analysis shows that the zinc atom is coordinated with three oxygen atoms from two ferrocenemonocarboxylates and one water molecule together with two nitrogen atoms from 2,2′-bipyridine, giving a distorted square-pyramidal coordination geometry. The complex molecules are linked to form an infinite one-dimensional chain by both intermolecular hydrogen bonds and π-π stacking interactions of the bipyridine rings.     

Syntheses and Crystal Structures of Two Cyano-bridged Bimetallic Complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O and [La(DMSO)4(H2O)3Co(CN)6]·H2O (DMSO = Dimethylsulfoxide)

Two new bimetallic cyano-bridged complexes [Ce(DMSO)4(H2O)3Fe(CN)6]·H2O 1 and [La(DMSO)4(H2O)3Co(CN)6]·H2O 2 have been prepared by the ball milling reaction method and structurally characterized by X-ray single-crystal structure analyses. Crystallographic data for 1:C14H32CeFeN6O8S4, Mr = 736.67, monoclinic, space group P21/n, a = 14.952(1), b =13.7276(9), c = 15.392(1) (A), β = 108.288(1)°, V = 2999.6(4) (A)3, Z = 4, Dc= 1.631 g/cm3,μ =2.304 mm-1, F(000) = 1480, R = 0.0593 and wR = 0.1611; and those for 2: C14H32CoLaN6O8S4,Mr=738.54, monoclinic, space group P21/n, a = 14.945(3), b = 13.731(3), c = 15.300(3) (A), β=107.806(1)°, V= 2989.3(11) (A)3, Z = 4, Dc = 1.641 g/cm3,μ = 2.288 mm-1, F(000) = 1480, R =0.0383 and wR = 0.1132. In both complexes the lanthanide ion is eight-coordinated in a square antiprism arrangement, and the Fe(Ⅲ) or Co(Ⅲ) ion in a nearly regular octahedral environment.The [LnM(CN)6(DMSO)4(H2O)3]·H2O (Ln = Ce and M = Fe for 1; Ln = La and M = Co for 2)species are held together via hydrogen bonds by coordinated water molecules, lattice water molecules and nitrogen atoms of cyanide groups to form a three-dimensional framework.