ABSTRACT
The tetra-kis complex of neodymium(III), tetra-kis-{µ-N-[bis-(pyrrolidin-1-yl)phos-phor-yl]acet-am-id-ato}bis(pro-pan-2-ol)neodymiumsodium pro-pan-2-ol monosol-vate, [NaNd(C10H16Cl3N3O2)4(C3H8O)2]·C3H8O or NaNdPyr4(i-PrOH)2·i-PrOH, with the amide type CAPh ligand bis(N,N-tetra-methylene)(tri-chloro-acetyl)phos-phoric acid tri-amide (HPyr), has been synthesized, crystallized and characterized by X-ray diffraction. The complex does not have the tetra-kis-(CAPh)lanthanide anion, which is typical for ester-type CAPh-based coordin-ation compounds. Instead, the NdO8 polyhedron is formed by one oxygen atom of a 2-propanol mol-ecule and seven oxygen atoms of CAPh ligands in the title compound. Three CAPh ligands are coordinated in a bidentate chelating manner to the NdIII ion and simultaneously binding the sodium cation by µ2-bridging PO and CO groups while the fourth CAPh ligand is coordinated to the sodium cation in a bidentate chelating manner and, due to the µ2-bridging function of the PO group, also binds the neodymium ion.
ABSTRACT
The influence of the charge and steric hindrance on the spin state of a series of four monomeric Fe(II) complexes derived from the tridentate ligands 2-(1H-benzoimidazol-2-yl)-1,10-phenanthroline (Hphenbi) and 2-(1H-benzoimidazol-2-yl)-9-methyl-1,10-phenanthroline (Hmphenbi) and their deprotonated forms (phenbi(-), mphenbi(-)) are investigated. The crystal structure and magnetic properties show that [Fe(Hphenbi)2](BF4)2·1.5C6H5NO2·H2O (1) and its neutral form [Fe(phenbi)2](0)·2CHCl3·H2O (2) are low-spin complexes at 400 K due to the strong ligand field imparted by the terpyridine-like ligand. In contrast, the steric hindrance induced by the methyl group in [Fe(Hmphenbi)2](BF4)2 (3) stabilizes the high-spin state of the Fe(II) ion at all temperatures. Application of a hydrostatic pressure of 0.43 GPa shows that3 displays incomplete thermal-induced spin crossover behaviour. However, upon deprotonation of the ligand the resulting neutral complex [Fe(mphenbi)2]·2CHCl3 (4) shows a complete two-step spin crossover behaviour at ambient pressure.
ABSTRACT
In the title complex, [Cu(C8H11NO5PS)(C18H15P)2], the Cu(I) ion is coordinated by two tri-phenyl-phosphane mol-ecules and two O atoms of the chelating dimeth-yl(phenyl-sulfon-yl)amido-phosphate anion, generating a squashed CuO2P2 tetrahedron. In the six-membered chelate ring, the Cu, P and O atoms are almost coplanar (r.m.s. deviation = 0.024â Å), with the N and S atoms displaced in the same direction, by 0.708â (5) and 0.429â (2)â Å, respectively.
ABSTRACT
In the binuclear title complex, [Cu2(ClO4)1.5(NO3)1.5(C18H16N6Se)(H2O)5]NO3·H2O, both Cu(II) ions are hexa-coordinated by O and N atoms, thus forming axially elongated CuO4N2 octa-hedra. The equatorial plane of each octa-hedron is formed by one chelating pyrazole-pyridine fragment of the organic ligand and two water mol-ecules. The axial positions in one octa-hedron are occupied by a water mol-ecule and a monodentately coordinated perchlorate anion, while those in the other are occupied by a nitrate anion and a disordered perchlorate/nitrate anion with equal site occupancy. The pyrazole-pyridine units of the organic selenide are trans-oriented to each other with a C-Se-C angle of 96.01â (14)°. In the crystal, uncoordinated nitrate anions and the coordinating water mol-ecules are involved in O-Hâ¯O and N-Hâ¯O hydrogen bonds, forming a bridge between the pyrazole group and the coordinating water mol-ecules. Further O-Hâ¯O hydrogen bonds between the complex mol-ecules and a π-π stacking inter-action with a centroid-centroid distance of 3.834â (4)â Å are also observed.
ABSTRACT
In the title compound, 2C(10)H(15)N(4)Se(+)·Cl(-)·OH(-), a singly protonated mol-ecule of the organic selenide participates in hydrogen bonding with neighboring mol-ecules, forming zigzag chains along [001]. The molecule adapts a cis bridging mode with a C-Se-C angle of 102.13â (15)°. π-π stacking inter-actions are observed between the closest pyrazole rings of neighboring chains [centroid-centroid distance = 3.888â (1)â Å] and hydrogen bonding occurs through bridging chloride anions and hydroxide groups. Additionally, O-Hâ¯Cl hydrogen bonds are formed.
ABSTRACT
In the complex cation of the title compound, [Zn(C(24)H(27)N(7)O(3))](NO(3))(2), the tripodal tris-{[2-(5-hy-droxy-pyridin-2-yl)methyl-idene-imino]-eth-yl}amine ligand is coordin-ated to the Zn atom through the three pyridine and three imino N atoms. The coordination sphere of the Zn atom is based on an octahedron with a significant distortion towards trigonal prismatic, the twist angle being 45.58â (9)°. The crystal packing is formed by L and D anti-podes arranged in layers disposed parallel to the b axis. Strong O-Hâ¯O hydrogen bonding exists between the hy-droxy groups of the ligand and the nitrate anion.
ABSTRACT
In the cation of the title compound, C(7)H(12)ClN(2)Se(+)·Cl(-), the ethyl-ene groups and the Se-Cl fragment adopt a cis configuration with a C-Se-Cl angle of 96.09â (6)°. In the crystal, inter-molecular N-Hâ¯Cl hydrogen bonds link two cations and two chlorine anions into centrosymmetric clusters. π-π inter-actions between the pyrazole rings [centroid-centroid distance of 3.530â (2)â Å] link these clusters into columns along [001] with short inter-molecular Seâ¯Cl(-) contacts of 2.995â (1)â Å.
ABSTRACT
The title compound, {[Cu(C(10)H(14)N(4)Se)(2)(H(2)O)](BF(4))(2)·2C(18)H(15)PO·H(2)O}(n), has a polymeric structure where each Cu(II) ion adopts a square-pyramidal coordination constituted by four N atoms of pyrazole moieties in the equatorial plane and an axial O atom of a water mol-ecule. A pair of bis-(3,5-dimethyl-1H-pyrazol-4-yl) selenide ligands bridges the Cu(II) centres into a chain extending along the c axis. The water mol-ecules, anions and triphenyl-phosphine oxide mol-ecules are involved in inter-molecular hydrogen bonding, which links the chains into a three-dimensional network.
ABSTRACT
In the title compound, C(6)H(13)Cl(3)N(3)O(2)P or CCl(3)C(O)NHP(O)(N(CH(3))(2)), the phosphinoyl group is synclinal to the carbonyl group and acts as an acceptor for an inter-molecular N-Hâ¯O hydrogen bond from the amide group as the donor.
ABSTRACT
The title compound, [Zn(C(10)H(11)N(4)O(2))(2)]·2H(2)O, was prepared by the reaction between Zn(CH(3)COO)(2)·2H(2)O and 2-hydroxy-imino-N'-[1-(2-pyrid-yl)ethyl-idene]propano-hydrazide (Hpop). The central Zn(II) atom has a distorted tetra-gonal-bipyramidal coordination geometry formed by two amide O atoms and four N atoms of two azomethine and two pyridine groups. In the crystal, complex mol-ecules form layers parallel to the crystallographic b direction. The layers are connected by O-Hâ¯N and O-Hâ¯O hydrogen bonds involving the solvent water mol-ecules.
ABSTRACT
In the title compound, [UO(2)L(2)(NO(3))(2)] {L = N-{bis-[meth-yl(phen-yl)amino]phosphor-yl}-2,2,2-trichloro-acetamide, C(16)H(17)Cl(3)N(3)O(2)P}, the U(VI) ions are eight-coordinated by axial oxido ligands and six equatorial O atoms from the phosphoryl and nitrate groups in a distorted hexa-gonal-bipyramidal geometry. There are disordered fragments in the two coordinating L ligands: the trichloro-methyl group is rotationally disordered between two orientations [occupancy ratio 0.567â (15):0.433â (15)] in one ligand, and a meth-yl(phen-yl)amine fragment is disordered over two conformations [occupancy ratio 0.60â (4):0.40â (4)] in the other ligand. In the crystal structure, intra-molecular N-Hâ¯O hydrogen bonds between the amine and nitrate groups are observed.
ABSTRACT
The crystal structure of the title compound, [U(NO(3))(2)O(2)(C(10)H(17)Cl(3)N(3)O(2)P)(2)], is composed of centrosymmetric [UO(2)(L)(2)(NO(3))(2)] mol-ecules {L is N-[bis-(pyrrolidin-1-yl)phosphor-yl]-2,2,2-trichloro-acetamide, C(10)H(17)Cl(3)N(3)O(2)P}. The U(VI) ion, located on an inversion center, is eight-coordinated with axial oxido ligands and six equatorial oxygen atoms of the phosphoryl and nitrate groups in a slightly distorted hexa-gonal-bipyramidal geometry. One of the pyrrolidine fragments in the ligand is disordered over two conformation (occupancy ratio 0.58:0.42). Intra-molecular N-Hâ¯O hydrogen bonds between the amine and nitrate groups are found.
ABSTRACT
In the title compound, {[Cu(C(10)H(14)N(4)Se)(2)(H(2)O)]Cl(2)·H(2)O}(n), the Cu(II) ion, lying on a twofold rotation axis, has a square-pyramidal geometry constituted by four N atoms of pyrazolyl groups in the basal plane and an apical O atom of a water mol-ecule. A pair of bis-(3,5-dimethyl-1H-pyrazol-4-yl) selenide ligands bridge the Cu centers into a polymeric double-chain extending along [001]. The chloride anions are involved in inter-molecular N-Hâ¯Cl and O-Hâ¯Cl hydrogen bonds, which link the chains into a three-dimensional network.
ABSTRACT
The asymmetric unit of the title compound, [ErCl(3)(C(10)H(17)Cl(3)N(3)O(2)P)(3)], contains two independent mol-ecules. In each mol-ecule, the Er(III) ion is six-coordinated in a slightly distorted octa-hedral ErO(3)Cl(3) geometry with a fac-arrangement of the donor atoms. Intra-molecular N-Hâ¯Cl hydrogen bonds influence the mol-ecular conformations. Some of the pyrrolidine fragments in the N-[bis(pyrrolidin-1-yl)phosphoryl]-2,2,2-trichloroacetamide ligands are disordered over two conformations of equal occupancy. The unusually porous crystal packing exhibits voids of 162, 158 and 13â Å(3 )and short inter-molecular Clâ¯O contacts of 2.876â (3) and 3.022â (4)â Å.
ABSTRACT
In the asymmetric unit of the crystal structure of the title compound, C(16)H(17)Cl(3)N(3)O(2)P, there are two crystallograph-ically independent mol-ecules, which form dimers via N-Hâ¯O hydrogen bonding between the N-H group and the P=O group. In the mol-ecular structure, the phosphoryl group is anti to the carbonyl group. The two benzene rings are oriented at dihedral angles of 54.3â (2) and 49.7â (2)° in the two independent mol-ecules.
