Crystal and molecular structure of four copper(II) ethylenediaminedisuccinates, [Cu2(RR,SS-Edds)] · 6H2O, Ba2[Cu(RR,SS-Edds)](ClO4)2 · 8H2O, Ba[Cu(SS-HEdds)]ClO4 · 2H2O, and Ba3[Cu2(RR,SS-Edds)2](ClO4)2 · 6H2O

Four Cu(II) complexes with the RR,SS-Edds ^4? and SS-HEdds ^3? anions are synthesized, and their crystal structures are studied. In the compounds [Cu2(RR,SS-Edds)] · 6H₂O (I) and Ba2[Cu(RR,SS-Edds)](ClO₄)₂ · 8H₂O (II), the ligand forms hexacoordinate chelate [Cu(Edds)]^2? complexes with the N atoms and O atoms of the propionate groups in the equatorial positions and the O atoms of the acetate groups in the axial vertices. In the compounds Ba[Cu(SS-HEdds)]ClO₄ · 2H₂O (III) and Ba3[Cu2(RR,SS-Edds)₂](ClO₄)₂ · 6H₂O (IV), one of the propionate arms, the protonated arm in III and the deprotonated arm in IV, does not enter into the coordination sphere of the Cu atom. An acetate arm moves to its position in the equatorial plane, and the free axial vertex is occupied by an O atom of the perchlorate ion. In I–IV, the lengths of the equatorial Cu-N and Cu-O bonds fall in the ranges 1.970–2.014 and 1.921–1.970 Å, respectively. The axial Cu-O bonds with the acetate groups and ClO ₄ ^? anions are elongated to 2.293–2.500 and 2.727–2.992 Å, respectively. In structure I, the second Cu atom acts as a counterion forming bonds with the O atoms of two water molecules and three O atoms of the Edds ligands. In II–IV, the Ba²⁺ cations are hydrated and bound to the O atoms of the anionic complexes and (except for one of the cations in IV) ClO ₄ ^? anions. The coordination number of the Ba cations is nine. The structural units in I–IV are connected into layers. In I, an extended system of hydrogen bonds links the layers into a framework. In II and III, the layers are linked only by weak hydrogen bonds, one bond per structural unit. In IV, ClO ₄ ^? anions are bound to the Ba and Cu atoms of neighboring layers, thus serving as bridges between the layers.     

Crystal structure of aqua[S-prolinato-N-monoacetato)copper(II) dihydrate [Cu(Proma)H2O] ⋅ 2H2O

The crystal structure of [Cu(C₇H₉NO₄)H₂O] ? 2H₂O is determined by X-ray diffraction (λMo, R = 0.0316 for 857 reflections). The crystals are tetragonal, a = 8.219(1) Å, c = 17.449(3) Å, Z = 4, ρ_calcd = 1.627 g cm^?3, and space group P4₃. The coordination polyhedron of the Cu atom is a tetragonal pyramid with the O atom of the acetate arm of the prolinatomonoacetate ion (Proma) in the apical position [Cu-O 2.312(6) Å]. The O atom of the water molecule and the N and O atoms of the prolinate group of the Proma ligand lie in the basal plane. The Cu-N bond length is 2.044(6) Å, and the Cu-O bond lengths are 1.932(7) and 1.927(6) Å. The O atom of the acetate arm of the neighboring Proma ion completes the basal plane [Cu-O 1.951(6) Å], thus linking the copper complexes into infinite chains.     

Crystal structure of [Co(Ox)(NH3)4][Bi(Edta)] ⋅ 3H2O

The crystal structure of [Co(Ox)(NH₃)₄][Bi(Edta)] ? 3H₂O is determined. The crystals are monoclinic, a = 9.291 Å, b = 22.275 Å, c = 11.402 Å, β = 105.79°, V = 2270.7 ų, Z = 4, and space group P2₁/c. The [Bi(Edta)]^? anionic complexes are linked into polymeric chains through two Bi-O bonds with the neighboring complexes.     

Crystal and molecular structure of [Cu2(3,5-dihydroxybenzoate)4 (acetonitrile)2] ⋅ 8H2O

The crystal and molecular structure of the title compound, [Cu₂(3,5-dihydroxybenzoate)₄ (acetonitrile)₂] 8H₂O 1, is reported. Crystal data for 1: tetragonal, space group I 4/m, a = 11.720(2) Å, c = 15.304(3) Å, V = 2102.4(6), and D _c = 1.53 g/cm³, for Z = 2. The metal and organic components crystallize to form a Cu paddle-wheel complex, of idealized D_4h symmetry, that assembles in the solid-state, along with eight equivalents of water, to form a 3D hydrogen-bonded network held together by O–H O hydrogens bonds. The metal complexes pack to form a 2D layered structure.     

Crystal structure of neptunium(V) sulfate hexahydrate, (NpO2)2SO4 · 6H2O

Single crystals of (NpO₂)₂SO₄ · 6H₂O are obtained, and their structure is determined. The structure is built of NpO ₂ ⁺ dioxo cations, SO ₄ ^2? anions, and molecules of coordination and crystallization water. The NpO ₂ ⁺ ions are linked into cationic ribbons stretched along the [001] direction. In the ribbons, neptunoyl ions of one type act as monodentate ligands, whereas neptunoyl ions of the other type coordinate the neighboring neptunoyl groups by two oxygen atoms. The Np(1) and Np(2) atoms have oxygen environments in the shape of a pentagonal bipyramid whose equatorial plane consists of oxygen atoms of the neighboring dioxo cations, sulfate ions, and water molecules. The sulfate ion acts as a bidentate ligand bridging the two neighboring atoms Np(1) and Np(2). Six water molecules are revealed in the structure; one of them is a crystallization water molecule. Hydrogen bonds link cationic ribbons into a three-dimensional network.     

Stereochemical activity of a lone electron pair in antimony(III) and bismuth(III) chelates: Crystal structures of Ca[Sb(Edta)]2 ⋅ 8H2O and Ba{[Bi(Edta)] 2H2O ⋅ H2O

The crystal structures of Ca[Sb(Edta)]₂ ? 8H₂O (I) and Ba{ [Bi(Edta)]₂H₂O} ? H₂O (II) are determined by X-ray diffraction. Crystals I are monoclinic, a = 7.132 Å, b = 21.906 Å, c = 10.896 Å, β = 91.13°, Z = 2, and space group P2₁/n. Crystals II are triclinic, a = 8.995 Å, b = 12.750 Å, c = 13.577 Å, α = 77.42°, β = 73.90°, γ = 86.53°, Z = 2, and space group $P\bar 1$ . In structure I, the coordination number of the antimony atom is 6 + LEP (lone electron pair), and the polyhedron is a ψ-pentagonal bipyramid with the lone electron pair at an equatorial position. In structure II, two crystallographically independent complexes Bi(Edta)^? and the coordination water molecule form tetranuclear associates. The environments of two independent bismuth atoms (the coordination number is eight) are similar, and their polyhedra can be described as distorted dodecahedra. The effect of the lone electron pair on the structures of polyhedra of antimony and bismuth is discussed.     

Crystal structure of triaquamaleatostrontium(II) monohydrate, [Sr(C4H2O4)(OH2)3]·H2O

[Sr(C₄H₂O₄)(OH₂)₃]·H₂O is monoclinic, P2₁/n, witha=11.476(2),b=7.027(1),c=12.344(2) Å, =115.74(3)°,V=896.67 ų,Z=4. The Sr atom is surrounded by nine oxygen atoms which come from four different maleate anions and three water molecules. The Sr–O distances range from 2.546(2) to 2.808(2) Å. The C–O distances are equal within the standard deviation 1.263(3) to 1.258(3) Å). In the maleate anion, the planes that contain the carboxylate groups form an angle of 74.44(9)°. Both carboxylate groups deviate significantly from planarity. The different coordination modes of the carboxylate group and the extensive hydrogen bonding present are responsible for the polymeric nature of the structure.     

Crystal and molecular structure of complex compound [Fe3O(CH3COO)6(H2O)3]2[ZnCl4] ⋅ 2H2O

The X-ray crystal structure of trinuclear iron acetate [Fe₃O(CH₃COO)₆(H₂O)₃]₂ [ZnCl₄] ? 2H₂O was determined. The crystal has a ionic structure. It is monoclinic, a = 25.363(7), b = 14.533(4), c = 15.692(4) Å, β = 103.11(2)°, space group _C2/c, and R = 0.0685. The structure of the cationic complex [Fe₃O(CH₃COO)₆(H₂O)₃]⁺ is typical of trinuclear iron(III) compounds containing a μ₃-O bridge: the iron atoms are situated at the vertices of an almost equilateral triangle with the O atom at the center. Each Fe atom is coordinated by four O atoms of bridging carboxy groups, the μ₃-bridging O atom, and the water molecule in the trans position to the latter O atom. Mössbauer spectroscopy evidence indicates the high-spin state (_S = 5/2) of the iron(III) ions.     

Crystal structure of strontium aqua(ethylenediaminetetraacetato)cobaltate(II) tetrahydrate Sr[CoEdta(H2O)] · 4H2O

The complex Sr[Co^II Edta] · 5H₂O (I) (where Edta ^4? is the ethylenediaminetetraacetate ion) has been synthesized. The crystal structure of this compound is determined by X-ray diffraction. Crystals are monoclinic, a = 7.906(2) Å, b = 12.768(2) Å, c = 18.254(3) Å, β = 95.30(3)°, V = 1834.8 ų, space group P2₁/n, Z = 4, and R = 0.036. The structure is built up of the binuclear complex fragments {Sr(H₂O)₃[CoEdta(H₂O)]}, which consist of the anionic [CoEdta(H₂O)]^2? and cationic [Sr(H₂O)₃]²⁺ units linked by the Sr-O bonds into a three-dimensional framework. The coordination polyhedra of the Co and Sr atoms are mono-and bicapped trigonal prisms. The coordination sphere of the Co atom (the coordination number is equal to 6 + 1) involves six donor atoms (2N and 4O) of the Edta ^4? ligand and the O_w atom of water molecule. One of the Co-O distances (2.718 Å) is considerably longer than the other Co-O_lig distances (2.092–2.190 Å) and the Co-O_w(1) distance (2.079 Å). The Sr coordination polyhedron (the coordination number is eight) contains three water molecules, three carbonyl O atoms of the three different anionic complexes, and two O atoms of one acetate group of the fourth anionic complex. The Sr-O distances fall in the range 2.535–2.674 Å. The structural formula of the compound is {Sr(H₂O)₃[CoEdta(H₂O)]}_3∞ · H₂O.     

Structure of a Cu(II)-containing peptide,diaquo-gly-l-tyr Cu(II) dihydrate, [Cu(C11N2O4H13)(H2O)2·2H2O

The structure of the Cu(II) complex of gly-l-tyr [Cu(C₁₁N₂O₄H₁₃) (H₂O)₂]·2H₂O has been solved by X-ray diffraction methods. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=11.970(2) Å,b=12.485(2) Å andc=10.418(3) Å, respectively, (MoK)=0.710 Å,D _c =1.59 Mgm^–3,D _m =1.59 Mgm^–3, finalR=0.04. The structure was solved by heavy atom (Cu) phased Fourier and refined by full-matrix least squares methods. The coordination geometry of the ligand around the Cu(II) ion has been established as a distorted tetragonal pyramid. The peptide molecule behaves as a tridentate ligand via its amino (N2), amido (N1) nitrogens and carboxyl (O2) oxygens. The peptide nitrogen is found to be deprotonated.     

Crystal structure of aminoguanidinium hexahydro-closo-hexaborate dihydrate, (CN4H7)2B6H6 · 2H2O

The (HAgu)₂B₆H₆ · 2H₂O compound was synthesized and its crystal structure was determined [R = 0.0385 for 2018 reflections with I > 2σ(I)]. The structure consists of HAgu ⁺ cations, centrosymmetric B₆H ₆ ^2? anions, and water molecules. The anions have an almost regular octahedral structure. The bond lengths and angles lie within the following narrow ranges: B-B, 1.715–1.726(2) Å; B-H, 1.08–1.14(2) Å; B-B-B, 59.72°–60.29(9)° and 89.63°–90.20(11)°; and B-B-H, 133.2°–137.0(9)°. The HAgu ⁺ cations and water molecules are involved in the O-H?O, N-H?O, and N-N?N hydrogen bonds and participate in numerous (N, O)-H?H-B specific interactions with the B₆H ₆ ^2? anions, which results in splitting and high-frequency shift of the band of B-H stretching vibrations in the IR spectrum.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Crystal structures of acid ethylenediaminetetraacetates [Cd(H2 Edta)(H2O)] · 2H2O and [Mn(H2O)4][Mn(HEdta)(H2O)]2 · 4H2O

The crystal structures of [Cd(H₂ Edta)(H₂O)] · 2H₂O (I) and [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ · 4H₂O (II) are studied by X-ray diffraction [R ₁ = 0.0209 (0.0272), wR ₂ = 0.0571 (0.0730) for 2551 (4025) reflections with I > 2σ(I) in I (II), respectively]. Structure I contains mononuclear [Cd(H₂ Edta)(H₂O)] complexes with the C ₂ symmetry, and structure II contains centrosymmetric trinuclear [Mn(H₂O)₄][Mn(HEdta)(H₂O)]₂ complexes. In I and II, the protonated ligands are hexadentate (2N + 4O), and the water molecule increases the coordination number of the metal atom to seven. The acid protons participate in short intermolecular hydrogen bonds, which are symmetric in II and asymmetric in I.     

Crystal and molecular structure of 2,9-di-(methylnitronato)-3,5,10,12-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) di-triethylammonium diperchlorate,C16H28N6O4Ni·2(C2H5)3NH·2ClO4

The crystal and molecular structure of 2,9-di-(methylnitronato)-3,5,10,12-tetramethyl-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) di-triethylammonium diperchlorate (2c) has been determined of the basis of X-ray diffraction data. The crystals are monoclinic, space groupP2₁/c,Z=2; cell constants=11.478(3),b=15.177(3),c=11.431(3) Å,=99.34(2)°. The structure was refined (full matrix, least squares) with 3408 unique reflections givingR=0.0616. An octahedral configuration of the Ni(II) coordination sphere was found to consist of the macrocycle N₄ atoms occupying the equatorial plane of the octahedron with the O-atoms of the nitronato groups in the apical positions. The triethylammonium cations are hydrogen-bonded to the remaining O-atoms of the nitronato groups.     

X-ray structural investigation of paramagnetic molecular compound of 2,5,9,12-tetramethyl-1,8-cis-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) diperchlorate,trans-diaquo-2,5,9,12-eramehyl-1,8-trans-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) diperchlorate,and water 2[cis-C14H28N4Ni](ClO4)2·[trans-C14H28N4Ni· 2H2O](ClO4)2·2H2O

The structure of molecular compoundI (2IA·IB·2H₂O), whereIA is a square-planar 2(e),5,9(a),12-tetramethyl-1,8-cis-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) diperchlorate andIB is an octahedraltrans-diaquo-2(e),5,9(e),12-tetramethyl-1,8-trans-1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) diperchlorate has been investigated by X-ray diffractometric methods. Compound I crystallizes in an orthorhombic system, space groupPbca, Z=12,a=26.321(3),b=19.919(2),c=13.306(1) Å. The structure was solved by the heavy-atom method followed by a series of Fourier syntheses and refined by full-matrix least-squares to giveR=0.060 (for 3757 independent reflections). Conformations were ascribed to chelate rings and to the macrocyclic rings ofIA andIB, and the results were compared with those of some known 1,4,8,11-tetraazacyclotetradeca-4,11-dienenickel(II) complexes. The relative configurations were found 1RS,2SR,8RS,9RS (a racemate) forIA and 1R,2S,8S,9R (ameso-form) forIB. They differ each from the other by configuration on one nitrogen centre (N-epimeric compounds).     

New boron-oxygen layer in the structure of barium hydrodecaborate Ba5[B20O33(OH)4] ⋅ H2O

The crystal structure of the new synthetic compound Ba₅[B₂₀O₃₃(OH)₄] ? H₂O was established by the methods of X-ray diffraction (a Stoe IPDS diffractometer, λMoK _α?, 1860 independent reflections, anisotropic refinement, R = 1.95%, localization of hydrogen atoms): a = 9.495(2) Å, b = 6.713(1) Å, c = 11.709(2) Å, β = 95.09(1)°, sp. gr. P2, Z = 1. The structure is based on double pseudohexagonal layers consisting of BO₄-tetrahedra and BO₃ triangles linked into three-membered rings in two mutually perpendicular directions. The double layers adjacent along the [100] direction are linked together through the Ba-polyhedra and hydrogen bonds with the participation of the OH-groups occupying the “end” vertices of two B-triangles. The interlayer space is also filled with a sheet of Ba-polyhedra. The structure of the compound is compared to the structures of topologically similar Ba and Ca borates and hydroborates.     

Crystal structure of a new double salt hydrate SrCd2Cl6⋅8H2O

SrCd₂Cl₆8H₂O crystallizes in the space group and has the unit cell dimensions a = 9.688(2) Å, b = 11.212(2) Å, c = 7.732(3) Å, = 99.85(21)°, = 89.95(22)°, = 75.81(13)°, and Z = 2. After refinement through full-matrix least-squares methods, the reliability factor R in the final cycle is 4.65%. A very persistent occurrence of twinning by pseudosymmetry was observed. The twin element is a twofold axis [001]. The title compound exhibits five endothermic peaks, which have been detected by differential scanning calorimetry and interpreted from thermogravimetry.     

Crystal structure of calcium trans-N-(nitrilotriacetato)(pyridine-2-carboxylato)cobaltate(III) hexahydrate, Ca[Co(Nta)(Pic)]2] · 6H2O

Crystals of Ca[Co^III (Nta)(Pic)]₂ · 6H₂O (I) (where Nta ^3? and Pic ^? are the nitrilotriacetate and picolinate ions, respectively) are prepared and characterized by the X-ray diffraction technique. Crystals I are monoclinic, a = 18.599(4) Å, b = 12.556(3) Å, c = 14.042(3) Å, β = 102.90(3)°, V = 3196(1) ų, Z = 4, space group P2₁/c, R1 = 0.0278, wR2 = 0.0716, and Goof = 1.054 for 4982 reflections with I > 2σ(I). Structure I is built of the { Ca(H₂O)₄[Co(Nta)(Pic)]₂{ _1∞ polymer ribbons and molecules of crystallization water. One of the two symmetrically independent anionic complexes (B) is included in the chain and alternates with cationic units, whereas the other anionic complex (A) forms a branch of this chain. The cationic and anionic units are interlinked via the interactions of the Ca²⁺ cations with the carbonyl atoms of the main (Nta ^3?) and additional (Pic ^?1) ligands. The octahedral environment of the Co(III) atoms consists of donor atoms of the Nta ^3? (N + 3O) and Pic ^? (N + O) ligands. The coordination polyhedron of the Ca atom (pentagonal bipyramid) includes two carbonyl O atoms of two Nta ^3? ligands, one O_Pic atom, and four O_w atoms of water molecules.     

Crystal structure of cobalt(III) compound with ethylenediamine-N,N′-Di-3-propionic acid, [Co(H2 Eddp)(HEddp)]Br2 ⋅ 4H2O

The crystal structure of [Co(H₂ Eddp)(HEddp)]Br₂ ? 4H₂O is determined [R1 = 0.0551 and wR2 = 0.1298 for 2580 reflections with I > 2σ(I)]. The structure consists of the [Co(H₂ Eddp)(tHEddp)]²⁺ cationic complexes, Br^? anions, and molecules of crystallization water. Two tridentate ligands, which differ in the degree of protonation, coordinate the Co atom by two N atoms and one O atom, each forming a meridional isomer. In the complex, the configurations of the N(2) and N(4) atoms, which are included in two chelate rings each, differ from those of the N(1) and N(3) atoms, which are included only in the five-membered rings and bear uncoordinated propionate groups. The Co-N(1) and Co-N(3) bonds are longer than the Co-N(2) and Co-N(4) bonds (mean 1.987 and 1.957 Å, respectively). The Co-O(5) bond with the neutral ligand is longer than the Co-O(1) bond with the negatively charged carboxyl group (1.927 and 1.901 Å, respectively). The C(13)-O(5) carbonyl bond in the coordinated COOH group is elongated to 1.266 Å. The system of hydrogen bonds interlinks the cationic complexes, Br^? anions, and water molecules into a three-dimensional framework.     

Phenylmercury(II) dithiophosphates. Crystal structure of (O,O′-diethyldithiophosphate) phenylmercury(II)

The phenylmercury(II) derivatives PhHgS₂P(OR)₂ (R=C₂H₅, C₆H₁₁ and C₆H₅) have been synthesized. (O,O-diethyldithiophosphate) phenylmercury(II), C₁₀H₁₅HgO₂PS₂, crystallizes in the monoclinic space groupP2₁/c (n° 14) witha=7.330(5),b=18.085(2),c=11.552(4)Å,=105.96(5)°,V=1472.3(6)ų,Z=4,D=2.088 g.cm^–3. The mercury atom is coordinated to the phenyl carbon atom and to a ligand sulphur atom in an almost linear arrangement (C-Hg-S angle, 176.0(2)°. The ligand is almost monodentate, its second sulphur atom only being involved in a weak secondary intermolecular bond.IR and Raman studies of the other two compounds suggest the same coordination scheme. Positive ion FAB and¹³C,³¹P and¹⁹⁹Hg NMR spectra are also discussed.