The crystal structure of the title iodo­bismuthate complex, 4,4′-bipyridinium(2+) di-μ-iodo-bis­[(4,4′-bipyridyl)­tri­iodo­bis­muth(III)], formulated as [4,4′-H2bipy]2+[Bi2I8(4,4′-bipy)2]2− or (C10H10N2)[Bi2I8(C10H8N2)2], has been determined. The compound is isostructural with its antimony analogue, each containing layers of hydrogen-bonded ribbon polymers in which anionic dinuclear complexes are linked through hydrogen bonding with 4,4′-H2bipy cations.

The chloro-aryl bismuth thiolate Bi(SC6Cl5)3 has been prepared from the reaction between BiPh3 and the thiol HSC6Cl5 by analogy with the previously described synthesis of the fluoro-aryl species Bi(SC6F5)3. The compound Bi(SC6Cl5)3 is only sparingly soluble but can be isolated as a dmf adduct [Bi(SC6Cl5)3(dmf)2] (dmf = N,N-dimethylformamide) which adopts a five-coordinate square-based pyramidal geometry in which the two dmf ligands lie in the basal plane with a mutually cis configuration. Treatment of either Bi(SC6F5)3 or Bi(SC6Cl5)3 with pyridine or 2,2′-bipyridyl ligands affords the coordination complexes fac-[Bi(SC6F5)3(py)3] (two crystalline polymorphs), fac-[Bi(SC6Cl5)3(py)3], fac-[Bi(SC6F5)3(4-pic)3] (4-pic = 4-picoline), [Bi(SC6Cl5)3(4-pic)2], [Bi(SC6F5)3(bipy)] (bipy = 2,2′-bipyridyl), [Bi(SC6Cl5)3(bipy)], [Bi2(SC6Cl5)6(2-pic)3] (2-pic = 2-picoline) and [Bi(SC6F5)3(4-pic)]. Five- and four-coordinate complexes adopt square-based pyramidal and equatorially vacant, trigonal bipyramidal (disphenoidal) geometries respectively, the former having the two ligands cis to each other in the basal plane. The compound [Bi2(SC6Cl5)6(2-pic)3] contains both five- and four-coordinate mononuclear units. A salt with the formula [4-picH][(4-pic)2H][Bi3(SC6F5)11] was also isolated in which the anion contains a central bismuth bonded to five thiolate ligands with a square-based pyramidal geometry. Two cis-basal thiolates act as bridging groups to two outer bismuth centres each of which is four-coordinate with the expected disphenoidal geometry in which the bridging thiolate is in an axial position. The structure of the dinuclear arylbismuth thiolate compound [Bi2Ph2(SC6F5)4(4-pic)2] is also described. Intramolecular conformations and intermolecular associations in all structures are dominated by π–π-interactions.

The crystal structure of the title iodo­antimonate complex, 4,4′-bipyridinium(2+) di-μ-iodo-bis­[(4,4′-bipyridyl)­tri­iodo­anti­mony(III)], formulated as [4,4′-H 2 bipy] 2+ [Sb 2 I 8 (4,4′-bipy) 2 ] 2− or (C 10 H 10 N 2 )[Sb 2 I 8 (C 10 H 8 N 2 ) 2 ], contains layers of hydrogen-bonded ribbon polymers in which anionic dimetal complexes are linked through hydrogen bonding with 4,4′-H 2 bipy cations. The complex is isostructural with its bismuth analogue.

The crystal structure of tetra(4-hydroxy­pyridinium) di-μ-iodo-bis­[tetra­iodo­bismuthate(III)] 4-pyridone tetrasolvate, (C 5 H 6 NO) 4 [Bi 2 I 10 ]·4C 5 H 5 NO, has been determined. The structure contains discrete centrosymmetric [Bi 2 I 10 ] 4− anions enclosed in a hydrogen-bonded array of 4-hydroxy­pyridinium cations and 4-pyridone mol­ecules.

The crystal structure of the title compound, (C 4 H 12 N)[BiCl 2 (C 6 H 5 ) 2 ], contains a [BiCl 2 Ph 2 ] − anion with an equatorially vacant trigonal-bipyramidal geometry.

The crystal structure of the title compound, (C4H12N)[BiCl2(C6H5)(2)], contains a [BiCl2Ph2](-) anion with an equatorially vacant trigonal-bipyramidal geometry.

The crystal structure of tetra(4-hydroxypyridinium) di-mu-iodo-bis[tetraiodobismuthate(III)] 4-pyridone tetrasolvate, (C5H6NO)(4)[Bi2I10].4C(5)H(5)NO, has been determined. The structure contains discrete centrosymmetric [Bi2I10](4-) anions enclosed in a hydrogen-bonded array of 4-hydroxypyridinium cations and 4-pyridone molecules.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

New layer and three-dimensional 4,4′-bipyridinium salts of Cl−, [MCl6]2− (M = Os, Pt) and [FeCl5]2− contain NH⋯(Cl)2⋯HN interactions which form hydrogen bonded ribbons which in turn give one-, two-, or three-dimensional periodic networks; two related families of homologous motifs are present in these salts together with those of square planar, polymeric and tetrahedral [MCl4]2− (M = Pt, Pd, Mn, Cd, Pb, Co, Zn, Hg), planar [Cu2Cl6]2− and square pyramidal [SbCl5]2− dianions.

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Reaction between BiX2Ph (X = Cl or I) and 4,4'-bipy afforded crystals of complexes trans-[BiX2Ph(4,4'-bipy)]n as solvates in which an anticipated combination of dative (Bi?bipy) and secondary bonding (Bi⋯X) leads to a controlled polymeric structure.

The reaction between 1,2-B2Cl2(MMe2)(2) and disodium catecholate Na-2[1,2-O2C6H4] affords the cyclic diborane(4) compound 1,2-B-2(NMe2)(2)(cat) (cat = 1,2-O2C6H4), whereas a similar reaction using dilithium thiocatecholate Li-2[1,2- S2C6H4] affords the 1,1-isomer 1,1-B-2(NMe2)(2)(thiocat) (thiocat = 1,2-S2C6H4). Both compounds can be used to prepare unsymmetric diborane(4) species.

MX . . . HN+ hydrogen bond synthons have been exploited in preparation of crystalline salts [4,4'-H(2)bipy][MX4] [X=Cl, M=Pd, Pt, Co, Zn, Hg, Mn, Cd and Pb; X=Br, M=Pd, Co, Zn and Mn]. In these salts three structural forms for the halometallate species are observed: mononuclear square planar (M=Pd, Pt) or tetrahedral (M=Co, Zn, Hg) and polymeric cis edge-sharing octahedral (M=Mn, Cd, Pb). These correspond to three structural motifs which form the basis of the crystal structures formed in their [4,4'-H(2)bipy](2+) salts: ribbon polymer (M=Pt, Pd); herring-bone packing of cyclic dimers (M=Co, Zn, Hg); layer cross-linked polymers [{MX4}(n)](2n-) (M=Mn, Cd, Pb). The factors controlling the structures adopted, the hierarchy of intermolecular interactions present in these crystals and the principles that may be inferred and exploited further are considered.

The platinum catalysed diboration of alkynes using the diborane(4) compound 1,2-B2Cl2(NMe2)(2) affords high yields of cyclic 1-azonia-2-borata-5-borole compounds, which arise from redistribution of B-Cl and B-NMe2 bonds.

In the crystal structures of the three title complexes, (benzene-1,2-diolato-O,O')bis(triphenylphosphine)platinum(II), [Pt(C 6 H 4 O 2 )(C 18 H 15 P) 2 ], (1), (benzene-1,2-dithiolato-S,S') bis (triphenylphosphine)platinum(II), [Pt(C 6 H 4 S 2 )(C 18 H 15 P) 2 ] (2), and the n-hexane hemisolvate of (benzene-1,2-diolato-O,O')-bis(tricyclohexylphosphine)platinum(II), [Pt(C 6 H 4 O 2 )(C 18 H 33 P) 2 ].0.5C 6 H 14 , (3), the Pt atoms are tetracoordinate with distorted square-planar geometry. Compounds (1) and (2) are isostructural.

The synthesis and X-ray crystal structure of the [4]ferrocenophane compound [1,2-B2(NMe2)2{1,1′-(SC5H4)2Fe}] which contains a B–B bond are described. The ferrocene-1,1′-dithiolate group bridges the B–B bond of the diborane(4) unit [B–B 1.709(9) Å] in a 1,2- fashion. Each boron centre is trigonal planar, the angle between these planes being 82.0° such that the conformation about the B–B bond is staggered rather than eclipsed. All other angles fall within expected ranges indicating that there is little strain present in this compound.

The cis-MCl2... HN+ chelated hydrogen bond synthon has been exploited in preparation of crystalline [4,4'- H(2)bipy][MCl4] (M = Mn 2 and Cd 3), which shows a one-dimensional substructure of the form [{MCl4}(n)](2n-) consisting of a kinked chain of doubly edge sharing MCl6 octahedra. These chains are cross-linked by hydrogen bonding to the [4,4'-H(2)bipy](2+) ions.

The crystal chemistry and torsional profiles of three polymorphic diarylamines have been compared and contrasted. Although they have similar potential energy surfaces (PESs) for the main rotatable bond, the torsional distribution of the observed polymorphs differs greatly. In particular there are reported crystal structures for some but not all of the molecules at various positions on the PES, some of which are either maxima or non-stationary points on the gas phase surface. We have explained the distribution of the observed torsion values and postulated new packing motifs based on those found in the other molecules. According to lattice energy calculations, some of these 'new polymorphs' are predicted to be more stable than those reported in the literature.

The reaction between the platinum(II) bis(boryl) complex cis-[Pt(PPh3)(2)(Bcat)(2)] (cat = 1,2-O2C6H4) and the tertiary phosphines PMe3, PEt3, PMe2Ph, PMePh2 and dcpe [1,2-bis(dicyclohexylphosphino)ethane] and the phosphite P(OEt)(3) afforded the new complexes cis-[Pt(PR3)(2)(Bcat)(2)] (PR3 = PMe3, PEt3, PMe2Ph or PMePh2), cis-[Pt(dcpe)-(Bcat)(2)] and cis-[Pt{P(OEt)(3)}(2)(Bcat)(2)]. With PCy3 the mixed phosphine species cis-[Pt(PCy3)(PPh3) (Bcat)(2)] is the major product and was characterised by X-ray crystallography. With P(OMe)(3) reductive elimination of B-2(cat)(2) and the formation of platinum(0) products occurs exclusively whereas with dmpe [1,2-bis(dimethylphosphino)ethane] the only identifiable product is the platinum(II) species [Pt(dmpe)(2)]Cl-2. With dppm [bis(diphenylphosphino)methane] a reaction occurs to give a product assigned the structure cis-[Pt(dppm)(Bcat)(2)] or [Pt-2(dppm)(2)(Bcat)(4)] but two binuclear products were isolated as minor products, namely [Pt-2(PPh3)(mu-dppm)(2)(Bcat)(mu-Bcat)] and [Pt-2(kappa(1)-dppm)-(mu-dppm)(2)(Bcat)(mu-Bcat)]. Both compounds were characterised by X-ray crystallography and shown to contain unusual semi-bridging Beat groups. The reaction between [Pt(PPh3)(2)(eta-C2H4)] and the diborane(4) compound 1,2-B2Cl2(NMe2)(2) is also described which results in B-B bond oxidative addition yielding cis-[Pt(PPh3)(2){BCl(NMe2)}(2)] and a complex to which this bis(boryl) subsequently rearranges, namely trans-[PtCl(PPh3)(2){BCl(NMe2)}]. Both of these complexes were characterised by X-ray crystallography and have geometries typical of cis-bis(boryl) and trans-boryl chloride complexes respectively.