Trigonal Prismatic Environment Research Articles

(Nitrato-κO){N,N,N′,N′-tetrakis[(1H-benzimidazol-2-yl-κN3)methyl]cyclohexane-1,2-diamine}lead(II) hemiaqua{N,N,N′,N′-tetrakis[(1H-benzimidazol-2-yl-κN3)methyl]cyclohexane-1,2-diamine}lead(II) trinitrate dihydrate

In the title compound, [Pb(NO3)(C38H38N10)][Pb(C38H38N10)(H2O)0.5](NO3)3·2H2O, both PbII ions are coordinated in a distorted trigonal–prismatic environment by a hexa­dentate N,N,N′,N′-tetra­kis­[(1H-benzimidazol-2-yl)meth­yl]cyclo­hex­ane-1,2-diamine ligand. A nitrate and a half-occupancy water ligand form long coordination bonds to the PbII ions capping the trigonal–prismatic environment. In the crystal, the components are linked by N—H⋯O and O—H⋯O hydrogen bonds, forming a three-dimensional network. C—H⋯O inter­actions also occur.

Poly[[aqua(μ5-3,4,5,6-tetracarboxycyclohexane-1,2-dicarboxylato)strontium] monohydrate

In the title compound, {[Sr(C12H10O12)(H2O)]·H2O}n, the SrII ion is coordinated by six O atoms of five symmetry-related 3,4,5,6-tetra­carb­oxy­cyclo­hexane-1,2-dicarboxyl­ate ligands and one water mol­ecule in a slightly distorted monocapped trigonal–prismatic environment. The ligands bridge the SrII ions, forming a two-dimensional structure. In the crystal, O—H⋯O hydrogen bonds further connect the structure into a three-dimensional network. The H atoms of two of the carboxyl groups were refined as half-occupancy.

Poly[[tetraaqua-μ4-fumarato-di-μ3-fumarato-dineodymium(III)] trihydrate

The title coordination polymer, {[Nd2(C4H2O4)3(H2O)4]·3H2O}, was synthesized by the reaction of neodymium(III) nitrate hexa­hydrate with fumaric acid in a water–methanol (7:3) solution. The asymmetric unit comprises two Nd3+ cations, three fumarate dianions (L 2−), four aqua ligands and three uncoordinated water mol­ecules. The carboxyl­ate groups of the fumarate dianions exhibit different coordination modes. In one fumarate dianion, two carboxyl­ate groups chelate two Nd3+ cations, while one of the O atoms is coordinated to another Nd3+ cation. Another fumarate dianion bridges three Nd3+ cations: one of the carboxyl­ate groups chelates one Nd3+ cation, while the other carboxyl­ate group bridges two Nd3+ cations in a monodentate mode. The third fumarate dianion bridges four Nd3+ cations, where one of the carboxyl­ate groups chelates one Nd3+ cation and coordinates in a monodentate mode to a second Nd3+, while the second carboxyl­ate groups bridges two Nd3+ cations in a monodentate mode and one O atom is coordinated to one Nd3+ cation. The Nd3+ cations are in a distorted tricapped–trigonal prismatic environment and coordinated by seven O atoms from the fumarate ligands and two O atoms from water mol­ecules. The Nd3+ cations are linked by two carboxyl­ate O atoms and two carboxyl­ate groups, generating infinite Nd–O chains to form a three-dimensional framework. There are O—H⋯O and C—H⋯O hydrogen-bonding interactions between the coordin­ated and uncoordinated water mol­ecules and carboxyl­ate O atoms.

Poly[tetraaqua(μ8-butane-1,2,3,4-tetracarboxylato)distrontium

In the title compound, [Sr2(C8H6O8)(H2O)4)]n, the SrII ion is coordinated by six O atoms of four symmetry-related ligands and two water mol­ecules in a distorted bicapped trigonal–prismatic environment. The butane-1,2,3,4-tetra­carboxyl­ate ligands lie on inversion centers and bridge SrII ions, forming a three-dimensional network. Within the three-dimensional structure, there are O—H⋯O hydrogen bonds involving the water mol­ecules and carboxyl­ate O atoms.

Poly[diaquabis(μ4-fumarato-κ4O1:O1′:O4:O4′)(μ4-fumarato-κ6O1:O1,O1′:O4:O4,O4′)(μ2-fumaric acid-κ2O1:O4)dipraseodymium(III)

The title complex, [Pr2(C4H2O4)3(C4H4O4)(H2O)2]n, was synthesized by reaction of praseodymium(III) nitrate hexa­hydrate with fumaric acid in a water–ethanol (4:1) solution. The asymmetric unit comprises a Pr3+ cation, one and a half fumarate dianions (L 2−), one half-mol­ecule of fumaric acid (H2L) and one coordinated water mol­ecule. The carboxyl­ate groups of the fumarate dianion and fumaric acid exhibit different coordination modes. In one fumarate dianion, two carboxyl­ate groups are chelating with two Pr3+ cations, and the other two O atoms each coordinate a Pr3+ cation. Each O atom of the second fumarate dianion binds to a different Pr3+ cation. The fumaric acid employs one O atom at each end to bridge two Pr3+ cations. The Pr3+ cation is coordinated in a distorted tricapped trigonal–prismatic environment by eight O atoms of fumarate dianion or fumaric acid ligands and one water O atom. The PrO9 coordination polyhedra are edge-shared through one carboxyl­ate O atom and two carboxyl­ate groups, generating infinite praseodymium–oxygen chains, which are further connected by the ligands into a three-dimensional framework. The crystal structure is stabilized by O—H⋯O hydrogen-bond inter­actions between the coordin­ated water mol­ecule and the carboxyl­ate O atoms.

Tetrakis(μ-4-tert-butylbenzoato)-κ3O:O,O′;κ3O,O′:O′;κ4O:O′-bis[aquabis(4-tert-butylbenzoato-κ2O,O′)(4-tert-butylbenzoic acid-κO)praseodymium(III)

The reaction of praseodymium nitrate and 4-tert-butyl­benzoic acid (tBBAH) in aqueous solution yielded the dinuclear title complex, [Pr2(C11H13O2)6(C11H14O2)2(H2O)2], which has non-crystallographic Ci symmetry. The two PrIII ions are linked by two bridging and two bridging–chelating tBBA ligands, with a Pr⋯Pr separation of 4.0817 (9) Å. Each PrIII ion is nine-coordinated by one chelating tBBA ion, one monodentate tBBAH ligand and one water mol­ecule in a distorted tricapped trigonal–prismatic environment. The complex mol­ecules are linked into infinite chains along the c axis by inter­molecular O—H⋯O hydrogen bonds.

Poly[[diaqua-μ6-succinato-di-μ5-succinato-didysprosium(III)] monohydrate

The title compound, {[Dy2(C4H4O4)3(H2O)2]·H2O}n, is isostructural with other lanthanide succinates of the same formula. The DyIII atom is nine-coordinated in a tricapped trigonal–prismatic environment by eight O atoms, derived from six carboxyl­ate groups and a water mol­ecule. One of the independent succinate anions is located about a crystallographic inversion center and the uncoordinated water mol­ecule lies on a twofold axis. The crystal structure comprises edge-shared DyO9 polyhedra linked by succinate bridges, forming a three-dimensional network architecture. Intra- and inter­molecular O—H⋯O hydrogen bonds are present in the crystal structure.

Tetrakis(μ-4-tert-butylbenzoato)-κ4O:O′;κ3O,O′:O′;κ3O:O,O′-bis[aqua(4-tert-butylbenzoato-κ2O,O′)(4-tert-butylbenzoic acid-κO)neodymium(III)

The reaction of neodymium nitrate and 4-tert-butyl­benzoic acid (tBBAH) in aqueous solution yielded the dinuclear title complex, [Nd2(C11H13O2)6(C11H14O2)2(H2O)2], which has non-crystallographic Ci symmetry. The two NdIII ions are linked by two bridging and two bridging–chelating tBBA ligands with an Nd⋯Nd separation of 4.0624 (5) Å. Moreover, each NdIII ion is coordinated by one chelating tBBA ion, one monodentate tBBAH ligand and one water mol­ecule. The nine-coordinated NdIII ion is in a distorted tricapped trigonal–prismatic environment. The mol­ecules are linked into infinite chains along the c axis by inter­molecular O—H⋯O hydrogen bonds. Three of the tert-butyl groups are disordered over two sets of sites with equal occupancies.

Propane-1,2-diaminium tris(pyridine-2,6-dicarboxylato-κ3O2,N,O6)zirconate(IV) trihydrate

In the title compound, (C3H12N2)[Zr(C7H3NO4)3]·3H2O, the ZrIV cation is chelated by three pyridine-2,6-dicarboxyl­ate anions in a distorted tricapped trigonal–prismatic environment. The crystal structure is stabilized by inter­molecular N—H⋯O and O—H⋯O hydrogen bonds.

Experimental and theoretical properties of S–Mo–Co–S clusters

In this work we propose that certain structures found in real commercial catalysts may be related to low dimensional structures. These structures are S–Mo–S and S–Mo–Co–S nanowires which were characterized by High Resolution Scanning Transmission Electron Microscopy (HR-STEM), Electron Diffraction (ED) and Electron Dispersive X-ray analysis (STEM-EDAX). Furthermore, a structural model was constructed with the one dimensional structures in order as to investigate their electronic properties. Energy band analysis on the samples yield indication about the semi metallic behavior, while a careful analysis to the partial Density of States (PDOS) in the vicinity of the Fermi level, provided indication for the existence of strong hybridization between S p- with Mo d- and Co d- and p-orbitals for the samples enunciated formerly. In addition, a very important issue to be mentioned is that in the construction of the 1T-S–Mo–Co–S nanowires, the Co and Mo atoms are not in their pure trigonal prismatic environment as compared to the bulk 2H-MoS 2. This issue could be deleterious for future catalytic applications.

Molecular models for WH6 under pressure

At atmospheric pressure, some tungsten hydrides exist as discrete molecular complexes in low temperature matrices, but are very reactive and cannot be isolated in bulk at room temperature. Under pressure, one observes WH in experiment at room temperature, and calculations indicate several other stoichiometries are stable, all extended and not molecular. This work aims at constructing a bridge between discrete molecules and the pressurized extended structures, with the emblematic example of WH6. The equilibrium structure, known as a distorted trigonal prismatic molecule, is likely to be a good acceptor. In numerical experiments, discrete WH6 molecular complexes are allowed to interact with each other in their ground states at T = 0 K and P = 1 atm. They spontaneously rearrange to form 1D-chains, with the W centers adopting a tricapped trigonal prismatic environment. The electronic structure of these chains is examined and related to that of the monomer and extended solids.

Tetra-kis[μ-2-(3,4-dimeth-oxy-phen-yl)acetato]-κO:O';κO,O':O;κO:O,O'-bis-{[2-(3,4-dimeth-oxy-phen-yl)acetato-κO,O'](1,10-phenanthroline-κN,N')samarium(III)}.

In the centrosymmetric dinuclear title complex, [Sm2(C10H11O4)6(C12H8N2)2], the SmIII ion is nine-coordinated by seven O atoms of five 2-(3,4-dimeth­oxy­phen­yl)acetate (DMPA) ligands and two N atoms of one bis-chelating 1,10-phenanthroline (phen) ligand, forming a distorted tricapped trigonal-prismatic environment. The DMPA ligands coordinate in bis-chelate, bridging and bridging tridentate modes. An intra­molecular C—H⋯O hydrogen bond occurs. Inter­molecular C—H⋯O inter­actions are also present in the crystal.

Triimidazolium tris(pyridine-2,6-dicarboxylato)dysprosate(III) trihydrate

The structure of the title compound, (C3N2H5)3[Dy(C7H3NO4)3]·3H2O, contains a mononuclear DyIII complex with the rare earth metal cation in a distorted tricapped trigonal–prismatic environment. The DyIII ion is in each case O,N,O′-chelated by three tridentate pyridine-2,6-dicarboxyl­ate anions. Three protonated imidazole mol­ecules act as counter-cations and three lattice water mol­ecules are also present. Numerous N—H⋯O and O—H⋯O hydrogen bonding inter­actions, some of which are bifurcated, help to stabilize the packing of the structure.

Poly[diaquabis(μ3-2,2-dimethylpropanedioato)calcium(II)copper(II)

The title complex, [CaCu(C(5)H(6)O(4))(2)(H(2)O)(2)](n), is the first heterobimetallic complex based on a substituted malonate dianion. The Cu(II) cation and two independent 2,2-dimethylmalonate (or 2,2-dimethylpropanedioate) dianions build up a robust dianionic [Cu(C(5)H(6)O(4))(2)](2-) complex, which acts as a building block to coordinate to four Ca(2+) cations. Each Cu(II) centre is in a four-coordinate square plane of dimethylmalonate O atoms, while each Ca(II) atom is in an eight-coordinate distorted bicapped trigonal-prismatic environment of six O atoms from four different dimethylmalonate groups and two water molecules. This arrangement creates a two-dimensional layer connectivity of the structure. The dianionic [Cu(C(5)H(6)O(4))(2)](2-) units are involved in different intermolecular hydrogen-bonding interactions with water molecules via the formation of hydrogen-bonded rings of graph sets R(1)(2)(8) and R(6) within this layer. The crystal was nonmerohedrally twinned by rotation about [011] with a major twin volume fraction of 0.513 (3).

The new ternary phases of La3(Zn0.874Mg0.126)11and Ce3(Zn0.863Mg0.137)11

The new ternary intermetallic title compounds, namely trilanthanum undeca(zinc/magnesium), La(3)(Zn(0.874)Mg(0.126))(11), (I), and tricerium undeca(zinc/magnesium), Ce(3)(Zn(0.863)Mg(0.137))(11), (II), are isostructural and crystallize in the orthorhombic La(3)Al(11) structure type. These three phases belong to the same structural family, the representative members of which may be derived from the tetragonal BaAl(4) structure type by a combination of internal deformation and multiple substitution. Compared to the structure of La(3)Al(11), in (I), a significant decrease of 11.9% in the unit-cell b axis and an increase in the other two directions, of 3.6% along a and 5.2% along c, are observed. Such an atypical deformation is caused by the closer packing of atoms in the unit cell due to atom shifts that reflect strengthening of metallic-type bonding. This structural change is also manifested in a significant difference in the coordination around the smaller atoms at the 8l Wyckoff position (site symmetry m). The Al atom in La(3)Al(11) is in a tricapped trigonal prismatic environment (coordination number 9), while the Zn atoms in (I) and (II) are situated in a tetragonal antiprism with two added atoms (coordination number 10).

Poly[diaquatris(μ4-isophthalato)dilanthanum(III)

In the title coordination polymer, [La2(C8H4O4)3(H2O)2]n, there are two independent LaIII atoms which are coordinated differently in slightly distorted penta­gonal-bipyramidal and slightly disorted bicapped trigonal-prismatic environments. The LaIII ions are bridged by μ4-isophthalate ligands, forming two-dimensional layers. In the crystal structure, these layers are connected by inter­molecular O—H⋯O hydrogen bonds into a three-dimensional network.

Tetrakis(μ2-3,4-dimethoxyphenylacetato)-κ3O,O′:O′;κ3O:O:O′;κ2O:O′;κ2O:O′-bis[(3,4-dimethoxyphenylacetato-κ2O,O′)(1,10-phenanthroline-κ2N,N)thulium(III)

In the title centrosymmetric dinuclear complex, [Tm2(C10H11O4)6(C12H8N2)2], the unique TmIII ion is coordin­ated by five 3,4-dimethoxy­phenyl­acetate (DMPA) ligands and and a bis-chelating 1,10-phenanthroline (phen) ligand via seven O atoms and two N atoms, forming a distorted tricapped trigonal-prismatic environment. The DMPA ligands coordin­ate in the bis-chelate, bridging and bridging tridentate modes.

Pr4S3[AsS3]2: Praseodym(III)‐Sulfid‐Thioarsenat(III) mit Ketten und Schichten aus kondensierten [SPr4]‐Tetraedern

AbstractSingle crystals of Pr4S3[AsS3]2 can be obtained through the reaction between the elements praseodymium, arsenic and sulfur using CsCl as fluxing agent in torch‐sealed evacuated silica ampoules. The starting materials were heated for ten days at 700 °C and then cooled down slowly to room temperature. The transparent, pale greenish yellow platelets crystallize orthorhombically (a = 2910.6(2), b = 699.74(5), c = 704.51(5) pm) in space group Pbcn (no. 60) with Z = 4. The new compound Pr4As2S9 (≡ Pr4S3[AsS3]2) contains two crystallographically independent Pr3+ cations. (Pr1)3+ shows a bicapped trigonal prismatic environment of eight sulfur atoms (CN = 8), whereas (Pr2)3+ is surrounded by only seven sulfur atoms in the shape of a monocapped trigonal prism (CN = 7). The isolated pyramidal thioarsenate(III) anions [AsS3]3– are formed as ψ1‐tetrahedra by the three sulfur atoms (d(As3+–S2–) = 223–228 pm, ∢(S–As–S) = 94–104°) and a non‐binding electron pair (lone pair) at each As3+ cation. Two of the five crystallographically different sulfur atoms (S1 and S2) are not connected to As3+ at all, but coordinated by four Pr3+ cations each to build up slightly distorted [SPr4]10+ tetrahedra (d(S2––Pr3+) = 281–289 pm, ∢(Pr–S–Pr) = 98–146°). Thus the crystal structure of Pr4S3[AsS3]2 exhibits endless {}^1_∞{[(S1)Pr4/2]4+} chains and {}^2_∞{[(S2)Pr4/4]+} layers, which consist of trans‐edge condensed [(S1)Pr4]10+ tetrahedra for the chains and [(S2)Pr4]10+ tetrahedra sharing four common edges for layers. The lone pairs at the As3+ cations close around the{}^1_∞{[(S1)Pr4/2]4+} chains running along [001]. The {}^2_∞{[(S2)Pr4/4]+} layers spread out parallel to the (100) plane and complete the crystal structure of Pr4S3[AsS3]2 according to {}^1_∞{[(S1)(Pr1)4/2]4+}{}^2_∞{([(S2)(Pr2)4/4]+)2} {}^0_∞{([As(S3)(S4)(S5)]3–)2}.

Pr2CBr: Ein Ferromagnet mit Pr2C-Schichten/ Pr2CBr: A Ferromagnet with Pr2C Layers

Single-phase Pr2CBr was prepared by heating a mixture of PrBr3, Pr and C (1 : 5:3) to 1140 °C for 18 d. The crystal structure was investigated by X-ray single crystal diffraction (space group P63/mmc, a = 3.8071(3), c = 14.7787(12) Å). In the structure the Pr atoms form C-centered octahedra condensed into Pr2C sheets via common edges; these sheets are separated by the Br atoms which are in a trigonal prismatic environment of Pr atoms. Pr2CBr is a black shiny compound with metallic conductivity. It is a ferromagnet with Tc = 13.8(5) K.

C 4− carbide ligand in the trigonal prismatic environment of rheniums in [Re 12CS 17(CN) 6] n− complexes

The electronic state of carbon in trigonal prismatic environment in [Re 12CS 17(CN) 6] n − complexes with variable redox state n = 6 ↔ 8 was studied by molecular orbital method and electron localization function. The state is characterized by sp 2-hybridisation and oxidation state −4. A weak long-distance interaction between μ 6-С and μ 2-S in the group [(μ 6-С)(μ 2-S) 3] was discovered for n = 6, the interaction disappears for n = 8.