Crystal structures of strontium and barium ethylenediaminetetraacetato cobaltates(III), Sr[CoEdta]2·9H2O and Ba[CoEdta]2·8H2O: Comparison of the structures of complexes in the series M’[CoEdta]2·nH2O (M’ = Mg, Ca, Sr, Ba; n = 7–10)

Cobalt(III) complexes, namely, Sr[CoEdta]₂·9H₂O (I) and Ba[CoEdta]₂·8H₂O (II) (where Edta ^4- is the ethylenediaminetetraacetate ion), are synthesized. The crystal structures of these compounds are determined using X-ray diffraction. Crystals of compound I are triclinic, a = 6.514(1) Å, b = 11.410(2) Å, c = 12.317(2) Å, α = 67.87(1)°, β = 88.73(2)°, γ = 84.22(2)°, V = 843.63(3) ų, Z = 1, space group P1, and R = 0.0295 for 4130 reflections with I > 2σ(I). Crystals of compound II are monoclinic, a = 6.543(2) Å, b = 12.895(3) Å, c = 19.489(4) Å, β = 95.24(3)°, V = 1637.5(5) ų, Z = 2, space group P2₁, and R = 0.050 for 3016 reflections with |F| > 3σ(|F|). The structures of compounds I and II are compared with those of the previously studied complexes Mg[CoEdta]₂·10H₂O (III) and Ca[CoEdta]₂·7H₂O (IV). The crystal structure of the cobalt(III) complex with the strontium cation (I) is topologically similar to the crystal structure of cobalt(III) complex with the calcium cation (IV). The former structure is built up of the two symmetrically independent homochiral anionic complexes [CoEdta]^? (A _I and B _I), the aqua cations [Sr(H₂O)₈]²⁺, and the molecules of crystalization water w _cr. The structure of compound II involves two independent anions [CoEdta]^? (A _II and B _II) with different chiralities (i.e., they are kryptoracemates). The A _II anions are linked via the barium cations into {Ba(H₂O)₇[CoEdta]} _1∞ ⁺ chain agglomerates due to the incorporation of two terminal oxygen atoms O_u of the anions neighboring in the chain into the coordination sphere of the barium atom. All four structures (I–IV) contain stacks composed of the [CoEdta]^? homochiral anions forming layers aligned parallel to the (001) plane. The aqua cations [Sr(H₂O)₈]²⁺, [Mg(H₂O)₆]²⁺, and [Ca(H₂O)₇]²⁺ or the partially hydrated barium cations [Ba(H₂O)₇(O_u)₂]²⁺ (in structure II), as well as water molecules w _cr, are located between the anion layers. The octahedral environment of the cobalt(III) atoms consists of donor atoms (2N and 4O) of the Edta ^4? ligand. The Co-N bonds in the A _I, B _I, A _II, and B _II anions [the mean bond lengths are 1.927(4), 1.921(4), 1.910(6), and 1.921(6) Å, respectively] are considerably longer than the Co-O bonds [the mean bond lengths are 1.908(5), 1.902(5), 1.904(6), and 1.908(6) Å, respectively]. The mean distances Sr-O_w and Ba-O_w in the strontium and barium polyhedra are 2.609(4) and 2.834(8) Å, respectively. The mean distance Ba-O_u is 2.814(7) Å.     

Formation of copper(II) coordination polymers by a flexible double betaine: [{Cu(L)X2(H2O)} n ]·2nH2O [X=Cl,Br] and [{Cu(L)(H2O)4} n ](ClO4)2n ·2nH2O [L=−O2CCH (Me3N+)CH2CH2CH(Me3N+)CO 2 − ]

Three polymeric copper(II) complexes of a flexible double betaine, namely, [{Cu(L)Cl₂(H₂O)} _n ]·2 _n H₂O (1), [{Cu(L)Br₂(H₂O)} _n ]·2nH₂O (2), and [{Cu(L)(H₂O)₄} _n ](ClO₄)_2n ·2nH₂O (3) [L=?O₂CCH(Me₃N⁺)CH₂CH₂CH(Me₃N⁺CO₂], have been prepared and characterized by singlecrystal X-ray analysis. Isomorphous complexes (1) and (2) crystallize in space groupC2/c (No. 15) witha=17.725(3),b=5.958(2),c=19.077(3) Å, β=110.70(1)^o,V=1881.4(4) ų, Z=4 anda=18.268(4),b=5.948(3),c=19.166(5) Å, β=109.08(2)^o,V=1964.7(9) ų, Z=4, respectively. Complex (3) belongs to space groupPī (No. 2) witha=6.203(1),b=9.293(2),c=12.035(2) Å, α=86.56(2), β=87.33(3), γ=71.23(2)^o,V=655.4(2) ų and Z=1. The crystal structure of (1) and (2) features an infinite zigzag chain composed of an alternate arrangement of metal atoms and double betaines ligands, with each Cu(II) atom in a distorted CuX₂O₃ [X-Cl, Br] square-pyramidal geometry, and hydrogen bonding between adjacent chains leads to a layer structure concentrated the (200) family of planes. Complex (3) exhibits a layer structure corresponding to the (001) family of planes, in which neighboring chains constructed from the metal atoms and the double betaine ligands are cross-linked by hydrogen bonding between the aqua ligands. The Cu(II) atom is coordinated in a CuO₆ octahedral geometry with Jahn-Teller distortion.     

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 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 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.     

Crystal structure of chloro[1-hydroxyethane-1,1-diphosphonato(3−)]ditin(II) monohydrate Sn2(HL)Cl · H2O

The synthesis and X-ray structure analysis of Sn₂(HL)Cl · H₂O, where HL ^3? is the anion of 1-hydroxyethane-1,1-diphosphonic acid, are reported. The coordination polyhedra of two independent tin(II) atoms are the Sn(1)O₂Cl and Sn(2)O₃ trigonal pyramids, in which one of the vertices is occupied by a lone electron pair (Sn-O, 2.144–2.218 Å and Sn-Cl, 2.573 Å). The pyramids are complemented by weaker Sn?O and Sn?Cl contacts to form severely distorted (3 + 3) octahedra. The SnO₂Cl and SnO₃ pyramids are linked by the HL ^3? bridging ligands into the [Sn₂(HL)Cl]₆ cyclic molecules, which, in turn, are joined by additional Sn?O, Sn?Cl, O(H₂O)?O(L), and O(H₂O)?Cl contacts with each other and with crystallization water molecules into a three-dimensional framework.     

Self-assemblies of Ni(II) with phenanthroline and maleate anions: [Ni(H2O)3(phen)L] ⋅ H2O (1) and [Ni(H2O)2(phen)L] ⋅ 2H2O (2) with H2L = maleic acid

The complex [Ni(H₂O)₃(phen)(C₄H₂O₄)] H₂O (1), which was obtained by reaction of phenanthroline, Ni(NO₃)₂ 6H₂O, and maleic acid in CH₃OH/H₂O at pH = 7.05, crystallized in the monoclinic space group P2₁ (no. 4) with cell dimensions: a = 9.350(1) Å, b = 7.631(1) Å, c = 12.821(1) Å, = 106.25(1), and D _calc = 1.607 g/cm³ for Z = 2. The Ni atoms are each octahe drally coordinated by one chelating phen ligand, three H₂O molecules and one monodentate maleato ligand to form [Ni(H₂O)₃(phen)(C₄H₂O₄)] complex molecules with d(Ni–O) = 2.038–2.090 Å, d(Ni–N) = 2.066, 2.089 Å. The formed complex molecules are, via the intermolecular hydrogen bonds, assembled into columnar 1D chains. Interdigitation of the chelating phen ligands of the neighboring chains leads to 2D layers and the crystal H₂O molecules are hydrogen bonded to the oxygen atoms of the maleate not coordinated to the Ni atom. However, reaction of NiCO₃, phen, and maleic acid in CH₃OH/H₂O at pH = 6.33 afforded [Ni(H₂O)₂(phen)(C₄H₂O₄)] 2H₂O (2), which crystallized in the triclinic space group (no. 2) with cell dimensions: a = 7.971(1) Å, b = 8.237(1) Å, c = 13.304(1) Å, = 81.005(6)°, = 87.877(8)°, = 78.322(8)°, and D _calc = 1.671 g/cm³ for Z = 2. The Ni atoms are each octahedrally coordinated by two N atoms of one phen ligand and four O atoms of two H₂O molecules and two bis–monodentate maleato ligands with d(Ni–O) = 2.041–2.120 Å and d(Ni–N) = 2.095 Å. The Ni atoms are bridged by the maleato ligands to generate 1D ¹ [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] chains along [100]. The supramolecular assemblies of the 1D chains via – stacking inter- actions result in thick 2D layers parallel to (001), between which the noncoordinating H₂O molecules are sandwiched. The paramagnetic [Ni(H₂O)₂(phen)(C₄H₂O₄)_2/2] 2H₂O (2) obeys the Curie–Weiss law _m(T-) = 1.139cm³ mol^–1 K with the Weiss constant = –0.95 K.     

Crystal structure of [Co(bipy)(maleato) (H2O)3]·H2O (bipy = 2,2′-bipyridine)

Preparation of the mononuclear cobalt(II) complex, [Co(bipy)(maleato) (H₂O)₃]·H₂O (1) where bipy = 2,2-bipyridine, were accomplished by reaction of an aqueous solution containing sodium maleate and an ethanolic solution of Co(NO₃)₂·6H₂O and bipy. The crystal structure of complex (1) was determined by X-ray crystallography. The complex crystallizes in the monoclinic space group P2₁/n with a = 9.477(3), b = 7.660(2), c =23.526 (3) Å, = 97.64(2)°, V = 1692.6(6) ų, and Z = 4. The structure consists of discrete mononuclear cobalt molecules. The cobalt atom is six-coordinate and presents a slightly distorted octahedral geometry, which consists of the two imine N atoms of bipy, a terminal carboxylate O atom from maleato ligand, and a water O atom in the basal plane with Co—N bond distances of 2.116(2) and 2.124(3) Å and Co—O distances of 2.075(2) and 2.088(2) Å, respectively. The relatively shorter Co—O distances are due to the trans effect of the bipy ligand. The octahedral coordination is completed the other two water molecules. The coordinate and the lattice water molecules were identified by TG study.     

Synthesis and crystal structures of 4,4′-bipyridinium and 2,2′-bipyridinium pentachloro complexes containing the polynuclear anions [Bi2Cl10]4− and [Bi4Cl20]8−

The compounds 4,4-bipyridinium(2+) pentachloro-bismuthate(III) (1), [4,4-(C₁₀H₈N₂)BiCl₅] and 2,2-bipyridinium(2+) pentachloro-bismuthate(III) (2), [2,2-(C₁₀H₈N₂)Bi₂Cl₁₀] have been obtained by reacting bismuthate oxide and 4,4-bipyridine or 2,2-bipyridine in HCl acid medium. They have been characterized by single crystal X-ray analysis. (1) crystallizes in the triclinic space group with a = 9.776(2), b = 11.009(3),c = 8.346(1) Å, = 101.58(2), = 98.63(2), and = 112.86(2)°. (2) crystallizes in the monoclinic space group P2₁/c with a = 14.239(2), b = 14.226(2), c = 16.275(3) Å, and = 110.15(2)°. The crystal structure of (1) consists of 4,4-bipyridinium(2+) cations interacting through hydrogen bonding with [Bi₂Cl₁₀]^2– dimers giving rise to endless double chains, while that of (2) is formed by 2,2-bipyridinium(2+) cations and [Bi₄Cl₂₀]^8– tetramers extensively interacting through hydrogen bonding. The different polynuclearity of the anions seems related to the different directions along which each cation can form hydrogen bond interactions.     

Crystal and molecular structure of di-μ-chlorobis[2-[[[(2-hydroxy-1-naphthyl)methyl]imino]-ethanolato]N,O,O′]di-copper(II) hemihydrate

The structure of the title compound [Cu₂Cl₂(C₁₃H₁₂NO₂)₂]·1/2 H₂O has been determined from single crystal X-ray diffraction data by direct methods. Full-matrix least-squares refinement of the structural parameters led to conventionalR factor of 0.037 for 4367 intensities above 3(I). The compound forms a dinuclear complex with distorted tetragonal-pyramidal geometry at each copper center. The unsymmetrical dimers are formed by weak axial coordination to one copper center by chloride ligands which are in the base plane of the adjacent copper atom. The apical Cu1-C12 and Cu2-C11 distances are 2.788(1) and 3.130(1) Å, respectively. The Cu1-Cu2 separation is 3.4995(3) Å in the dimers. A disorder of one five-membered chelate ring has been observed. Two alternative positionsa andb of the C26 atom were found and refined with constrained bond lengths. The geometry of the ligand and hydrogen bonds is discussed.     

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.     

Crystal structure of tisinalite Na2(Mn,Ca)1 − x (Ti,Zr,Nb,Fe3+)[Si6O8(O,OH)10]

Crystal structure of tisinalite from the Lovozero alkaline massif (the Kola Peninsula) was established by single-crystal X-ray diffraction analysis (SYNTEX $\bar P1$ diffractometer, λMoK_α radiation, 2θ/θ scanning mode). The structure solution (SHELX97 program package, R _hkl = 0.0565, 951 independent reflections, anisotropic refinement of thermal atomic displacements) confirmed that tisinalite belongs to the lovozerite structure type (sp. gr., $\bar P1$ , a = 10.036(5) Å, c = 12.876(9) Å, Z = 3). The difference between the structure of tisinalite and the structures of the minerals of the lovozerite group established earlier consists in the nature of the occupancy of both cation and anion positions.     

Crystal structure of [Mn(II)(phen)(ClCH2COO)2]n (phen = 1,10−phenanthroline)

A new polymeric manganese(II) complex, [Mn(II)(phen)(ClCH₂COO)₂]_n, was obtained from the reaction of Mn(ClCH₂COO)₂ with phen and its structure was determined by x-ray crystallography. The complex crystallizes in the monoclinic system, space group C2/c with a = 19.706(4), b = 11.381(3), c = 7.482(3) Å, = 94.01(3)°, V = 1674.0(8) ų, and Z = 4. The structure consists of an infinite chain. The manganese atom is located on a twofold axis and presents a distorted octahedral coordination sphere, which consists of the two N atoms of a phen ligand (Mn—N = 2.304(2) Å) and four carboxylato ligands. The Mn···Mn distance within the chain is 4.53 Å, and the carboxylato bridges present a syn-anti conformation.     

Crystal structures of double vanadates, Ca9 R(VO4)7 ⋅ III. R = Nd, Sm, Gd, or Ce

The crystal structures of Ca₉ R(VO₄)₇ (R = Nd (I), Sm (II), or Gd (III)) were studied by the Rietveld method. The compounds are isostructural to Ca₃(VO₄)₂ and are crystallized in the trigonal system (sp. gr. R3c, Z = 6). The unit-cell parameters are as follows: for I, a = 10.8720(5) Å, c = 38.121(1) Å; for II, a = 10.8652(5) Å, c = 38.098(1) Å; and for III, a = 10.8631(5) Å, c = 38.072(1) Å. In the structures of I and II, the M(1), M(2), and M(3) positions are statistically occupied by the rare-earth cations and calcium anions. In the structure of III, the Gd³⁺ cations occupy the _M(1) and _M(2) positions. The distributions of the R ³⁺ cations over the positions are characteristic of each structure. The composition of the cerium-ontaining compound Ca_9.81Ce_0.42(VO₄)₇ (a = 10.8552(5) Å, c = 38.037(1) Å) was refined and its crystal structure was solved from the X-ray powder data. In this compound, cerium atoms are in the oxidation states +3 and +4.     

Crystal structure of [WBr2(CO)(PPh2Cy)2(η2-MeC2Me)]·CH2Cl2 (Cy = cyclohexyl)

[WBr₂(Co)(PPh₂Cy)₂(²-MeC₂Me)]·CH₂Cl₂ (Cy = cyclohexyl) crystallizes in the monoclinic space group, P2₁/n, with a = 10.606(12), b = 23.11(3), c = 18.19(2) Å, = 106.070(10) D_calc = 1.610g cm^–3 for Z = 4. The tungsten coordination geometry can best be considered as a distorted octahedron, with the but-2-yne ligand occupying one coordination site, which has a trans-Br(2) group. The equatorial plane is made up of trans-PPh₂Cy groups, with the bromo and carbonyl ligands occupying the other two sites.     

[Co(dmg)2Cl2]3·[Co(dmg)2Cl(OH)]·[Co(dmg)(phen)]·(H2O)4的合成和晶体结构

本文合成了一个复杂的单核配合物 [Co(H2dmg)2Cl2]3·[Co(H2dmg)2Cl(OH)]·[Co(Hdmg)(phen)]·(H2O)4 (H2dmg＝dimethylglyoxime, phen＝1,10-Phenanthroline).通过X射线衍射技术获得其单晶结构.在单晶结构中,每五个单核钴(II)的配位结构形成一个重复单元,是一个较为复杂的单晶.其空间群为P-1,晶胞参数为a＝1.3738nm;b＝1.4396nm;c＝1.8656nm.本文中我们将讨论该化合物的分子结构及相关光谱性质.     

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.     

Synthesis,Structure, and Properties of the Tris(ethylendiamine)nickel(II) Dichloride Dihydrate [Ni(H2NCH2CH2NH2)3]Cl2 ⋅ 2H2O Crystals

Crystallography Reports - The conditions for synthesis of [Ni(H2NCH2CH2NH2)3]Cl2 ⋅ 2H2O ([Ni(en)3]Cl2 ⋅ 2H2O) crystals from aqueous solutions have been considered. The synthesized...