Volume 234, Issue 3

Single crystals of new Mn 2 [Bi 2 O](SeO 3 ) 4 ( I ), MnBi(SeO 3 ) 2 Cl ( II ), Mn II Mn III (SeO 3 ) 2 Cl ( III ), Mn 5 (SeO 3 ) 2 Cl 6 ( IV ), and Mn 4 (Mn 5 ,Bi)(SeO 3 ) 8 Cl 5 ( V ) have been synthesized by chemical vapour transport and hydrothermal methods. They have been structurally characterized by single crystal X-ray diffraction analysis. The compounds II–V are the first Mn selenite chlorides, while the I , II and V compounds are the first Bi-containing Mn oxoselenites. Structural relationships of the new phases with other compounds are discussed. An overview of the mixed-ligand MnO m Cl n polyhedra in inorganic compounds is given.

The reaction of bis (isocyanide)palladium complex cis -[PdCl 2 (CNXyl) 2 ] (Xyl=2,6-Me 2 C 6 H 3 ) with excess of 4,5-dichlorobenzene-1,2-amine in a C 2 H 4 Cl 2 /MeOH mixture affords monocationic bis (diaminocarbene) complex cis -[PdCl C {(NHXyl)=NHC 6 H 2 Cl 2 N H 2 }{ C (NHXyl)=NHC 6 H 2 Cl 2 NH 2 }]Cl ( 3 ) in moderate yield (42%). Complex 3 exists in the solid phase in the H-bonded dimeric associate of two single charged organometallic cations and two chloride anions according to X-ray diffraction data. The Hirshfeld surface analysis for the X-ray structure of 3 reveals that the crystal packing is determined primarily by intermolecular contacts H–Cl, H–H, and H–C. The intermolecular hydrogen bonds N–H···Cl and C–H···Cl in the H-bonded dimeric associate of 3 were studied by DFT calculations and topological analysis of the electron density distribution within the framework of QTAIM method, and estimated energies of these supramolecular contacts vary from 1.6 to 9.1 kcal/mol. Such non-covalent bonding means that complex 3 is an anionic receptor for the chloride anions.

The crystal and molecular structures of the one-dimensional coordination polymer [Zn(S 2 COEt) 2 ( 4 LH 2 )] n ( 1 ) and binuclear [Zn(S 2 COCy) 2 ] 2 ( 4 LH 2 ) ( 2 ) are described, where 4 LH 2 is N,N′-bis(pyridin-4-ylmethyl)ethanediamide. In 1 , the Zn(S 2 COEt) 2 entities are linked by bidentate bridging 4 LH 2 ligands through the pyridyl-N atoms to generate a twisted supramolecular chain. As a result of monodentate xanthate ligands, the N 2 S 4 donor set defines a distorted tetrahedral coordination geometry and, crucially, allows the participation of the non-coordinating sulfur atoms in supramolecular association. Thus, in the crystal amide-N–H···O(amide) and amide-N–H···S(thione) hydrogen bonds link chains into a three-dimensional architecture. The substitution of the ethyl group in the xanthate ligand with a cyclohexyl group results in very different structural outcomes. In 2 , a binuclear molecule is observed with the coordination geometry for zinc being defined by chelating xanthate ligands and a pyridyl-N atom with the NS 4 donor set defining a highly distorted geometry. In the molecular packing, amide-N–H···S(thione) hydrogen bonds stabilise a supramolecular chain along the a-axis and these are connected into a three-dimensional arrangement by methylene-C–H···O and methylene-C–H···π(pyridyl) interactions. The relative importance of the specified intermolecular interactions and weaker, contributing contacts has been revealed by an analysis of the calculated Hirshfeld surfaces of 1 and 2 .

A novel thulium p -hydroxybenzenesulfonate complex [Tm(C 6 H 5 O 4 S) 2 (H 2 O) 6 ](C 6 H 5 O 4 S)·3H 2 O ( 1 ) was solvothermally synthesized and characterized by elemental analyses, photoluminescence, solid-state UV/vis diffuse reflectance, magnetic measurements and single-crystal X-ray diffraction. Complex 1 features an ionic structure with the thulium ion possessing a square antiprismatic geometry. Complex 1 crystallized in the monoclinic system with space group P 2 1 . Photoluminescent measurements with solid-state sample demonstrate that the anti-Stokes emission bands in the red/NIR spectral region 710 and 812 nm are observed from the Tm 3+ 4f intrashell transitions from the 3 F 2,3 excited states to the 3 H 6 and 1 G 4 excited state to the 3 H 5 state, respectively. Solid-state UV/vis diffuse reflectance spectra of complex 1 show the existence of a wide optical band gap of 3.56 eV. Variable-temperature magnetic susceptibility and field dependence magnetization measurements are also studied and the magnetic susceptibility obeys the Curie-Weiss law ( χ m = c /( T − θ )) with the value C being of 8.6 K and a negative Weiss constant θ being of −0.2 K.

X-ray crystallography reveals the common feature of the title compounds is a 1,4-naphthoquinone ring system with a substituted phenoxy residue adjacent to an oxo-group to give 1 (H), 2 (3-Br), 3 (3-CF 3 ), 4 (4-CN) and 5 (4-NO 2 ). To a first approximation the fused ring system along with the two oxo substituents is planar with the major difference between the molecules relating to the relative orientations of the pendant phenoxy residues: dihedral angles range from 56.56(4)° ( 3 ) to 87.52(10)° ( 2 ). The presence of intermolecular C–H···O interactions is the common feature of the supramolecular association in the crystals of 1–5 . In each of 1 and 5 , these extend in three-dimensions but, only to supramolecular dimers in 4 , chains in 2 and layers in 3 . Each crystal also features C=O···π interactions, pointing to the importance of these points of contact in this series di-oxocompounds. In 2 , these, along with C–Br···π interactions lead to a three-dimensional architecture. For 3 , the C=O···π and π···π interactions occur within the layers which stack without directional interactions between them. In 4 , C–H···O and C=O···π interactions combine to give a supramolecular layer, which also stack without directional interactions in the inter-layer region. Further analysis of the molecular packing was conducted by a Hirshfeld surface analysis (HSA). This points to the significant role of H···H, C···H/H···C and O···H/H···O contacts in the packing of 1 . Notably different roles for these contacts are found in the other crystals correlating with the participation of the respective substituents in the molecular packing. The HSA suggests the association between layers in 3 (weak F···F and H···F interactions) and 4 (weak H···N interactions) is contributed by the phenoxy-substituents.

A new simple approach to quantitative measures of coordination polyhedra distortions from ideal symmetry is provided with PolyDis. Within the mathematical basis, it minimizes the normalized displacements of given polyhedra to the ideal shape. Applications are discussed, where PolyDis was used to analyze the temperature dependent distortion of LaAlO 3 , rare earth metal radius dependent distortion of R MnO 3 and the increasing structural distortion of ( A 3 N)As with varying alkaline earth metal, all being perovskites. Additionally, the more complex structures of SrCu R Se 3 and CsCu 3 R 2 Se 5 comprising trigonal prisms, octahedra and tetrahedra are treated with PolyDis.