The dispersion type Bi···π arene interaction is one of the important structural features in the assembly process of arylbismuth compounds. Several triarylbismuth compounds and polymorphs are discussed and compared based on the analysis of single crystal X-ray diffraction data and computational studies. First, the crystal structures of polymorphs of Ph3Bi (1) are described emphasizing on the description of London dispersion type bismuth···π arene interactions and other van der Waals interactions in the solid state and the effect of it on polymorphism. For comparison we have chosen the substituted arylbismuth compounds (C6H4-CH═CH2-4)3Bi (2), (C6H4-OMe-4)3Bi (3), (C6H3-t-Bu2-3,5)3Bi (4) and (C6H3-t-Bu2-3,5)2BiCl (5). The structural analyses revealed that only two of them show London dispersion type bismuth···π arene interactions. One of them is the styryl derivative 2, for which two polymorphs were isolated. Polymorph 2a crystallizes in the orthorhombic space group P212121, while polymorph 2b exhibits the monoclinic space group P21/c. The general structure of 2a is similar to the monoclinic C2/c modification of Ph3Bi (1a), which leads to the formation of zig-zag Bi–arenecentroid ribbons formed as a result of bismuth···π arene interactions and π···π intermolecular contacts. In the crystal structures of the polymorph 2b as well as for 4 bismuth···π arene interactions are not observed, but both compounds revealed C–HPh···π intermolecular contacts, as likewise observed in all of the three described polymorphs of Ph3Bi. For compound 3 intermolecular contacts as a result of coordination of the methoxy group to neighboring bismuth atoms are observed overruling Bi···π arene contacts. Compound 5 shows a combination of donor acceptor Bi···Cl and Bi···π arene interactions, resulting in an intermolecular pincer-type coordination at the bismuth atom. A detailed analysis of three polymorphs of Ph3Bi (1), which were chosen as model systems, at the DFT-D level of theory supported by DLPNO-CCSD(T) calculations reveals how van der Waals interactions between different structural features balance in order to stabilize molecular arrangements present in the crystal structure. Furthermore, the computational results allow to group this class of compounds into the range of heavy main group element compounds which have been characterized as dispersion energy donors in previous work.

The reaction of 2-(RN=CH)C(6)H(4)MgBr [R = 2',4',6'-Me(3)C(6)H(2) (R(1)), 2',6'-(i)Pr(2)C(6)H(3) (R(2))] [prepared from 2-(R(1)N=CH)C(6)H(4)Br (1) or 2-(R(2)N=CH)C(6)H(4)Br (2) and Mg] with SbCl(3) in a 2 : 1 and 1 : 1 molar ratio followed by treatment with an aqueous KBr solution gave [2-(R(1)N=CH)C(6)H(4)](2)SbBr (3) and [2-(R(2)N=CH)C(6)H(4)](2)SbBr (4) as well as [2-(R(1)N=CH)C(6)H(4)]SbBr(2) (6) and [2-(R(2)N=CH)C(6)H(4)]SbBr(2) (7). Treatment of 4 with Na(2)S·9H(2)O provided the dinuclear [{2-(R(2)N=CH)C(6)H(4)}(2)Sb](2)S (5). Heterocyclic species, i.e. the oxide cyclo-[{2-(R(2)N=CH)C(6)H(4)}SbO](3) (8) and the sulfides cyclo-[{2-(R(1)N=CH)C(6)H(4)}SbS](2) (9) and cyclo-[{2-(R(2)N=CH)C(6)H(4)}SbS](2) (10), were obtained by reacting dibromides 6 and 7 with KOH and Na(2)S·9H(2)O, respectively, in a water-toluene solvent mixture. The sulfide 10 reacted with [W(CO)(5)(thf)] to yield the heterometallic complex cyclo-[{2-(R(2)N=CH)C(6)H(4)}SbS](2)[W(CO)(5)] (11). The compounds were characterised by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. The molecular structures of 4, 5, 6·CHCl(3), 7, 9·CH(2)Cl(2), 10 and 11·0.25CH(3)OH were established by single-crystal X-ray diffraction. Theoretical calculations using DFT methods were carried out on bromide 7 and the geometrical isomers of its dimer association as well as the geometrical isomers of sulfide 10 and its monomer.

Two polymorphs of tris(thienyl)bismuthine Bi(2-CHS) (1) were isolated upon crystallization from n-hexane at different temperatures. The high temperature form 1-HT crystallized at 269 K in the trigonal space group R3[combining macron], whereas the low temperature form 1-LT crystallized at 245 K in the triclinic space group P1[combining macron]. An enantiotropic phase transition was observed at 250 K showing a transition energy of 1.4 kJ mol. Both polymorphs reveal the formation of centrosymmetric dimers that are based on London dispersion type bismuthπ heteroarene interactions. These primary building units show additional dispersion type interactions between neighbouring dimers and as a result 2D networks are formed. DFT calculations on the model systems BiXπ thiophene (X = Cl, Me) verify the hypothesis of a soft and shallow binding potential of the London dispersion type bismuthπ heteroarene interaction, providing an explanation for the reversibility of the phase transition.

The alkoxide Bi[OCMe(2-CHS)] (1) is formed by the reaction of three equiv. of the alcohol HOCMe(2-CHS) with Bi(OBu) and subsequent hydrolysis provides the bismuth oxido cluster [BiO{OCMe(2-CHS)}] (2). In contrast, the reaction of Bi(OBu) and Bi[N(SiMe)] with the silanols HOSiMe(2-CHX) (X = O, S, Se, and NMe), HOSiMe(2-CHS-5-SiMe) and HOSiMe(3-CHS) leads to the formation of tris(heteroaryl)bismuthines Bi(2-CHX-5-R) [where X = O, R = H (3); X = S, R = H (4); X = S, R = SiMe (5); X = NMe, R = H (6); X = Se, R = H (7)] and Bi(3-CHS) (8). For the silanols, bismuth-carbon bond formation is observed rather than silanol-alcoholate or silanol-amide exchange. The structures of compounds 1, 2, and 4-7a in the solid state were established by single crystal X-ray diffraction and all compounds except 5 show London dispersion type bismuthπ heteroarene interactions. For the bismuthine Bi(2-CHSe) (7), two polymorphs were isolated depending on the conditions of crystallization. At 8 °C, polymorph I (7a) crystallizes from an n-hexane solution in the triclinic space group P1[combining macron], whereas polymorph II (7b) crystallizes at 20 °C from a CHCl/n-pentane solution in the monoclinic space group P2/c. The heteroaryl bismuthines 3 and 4 exhibit 2D network structures as a result of bismuthπ heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.

Studies on a series of spirocyclic tin salicyl alcoholates regarding their molecular structures and their reactivity in twin polymerization are presented.

Compounds containing the [2‐(Me2NCH2)C6H4]2Sb moiety were prepared by using R2SbX [X = Cl (1), Br (2)] as starting materials. The reaction of 1 with Me3SiCH2MgCl gave the mixed alkyl–aryl stibine R2SbCH2SiMe3 (3). Reduction of 2 with Mg in thf followed by in situ air oxidation or treatment with S8 resulted in the isolation of (R2Sb)2E [E = O (4), S (5)]. Compound 5 is also formed from R2SbCl and Na2S. The reaction of 4 with [W(CO)5(thf)] gives the unexpected complex [(R2SbOH)W(CO)5] (6). The new compounds were investigated by IR, 1H, and 13C NMR spectroscopy, as well as by mass spectrometry. The structures of 3–6 were determined by single‐crystal X‐ray diffraction. For compounds 3–5, both nitrogen atoms from the pendant arms are involved in intramolecular N→Sb coordination, which results in distorted square‐pyramidal (C,N)2SbC or (C,N)2SbE (E = O, S) cores. By contrast, in 6 only one nitrogen atom is strongly coordinated to the antimony center, whereas the second nitrogen atom is involved in N···H–O bonding. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

The reaction of germanium(II)‐bis(2‐methoxyphenyl)methoxide with methanesulfonic acid provides the germanium(II) sulfonate Ge(CH3SO3)2 (1), which was characterized by X‐ray diffraction, elemental analysis, NMR spectroscopy, and IR spectroscopy. The decomposition process of 1 was investigated by thermal gravimetric analysis (TGA) and temperature‐dependent X‐ray powder diffraction (PXRD) and both are consistent with the formation of GeO2 as major final product. Single crystal X‐ray diffraction at 110 K revealed the chiral tetragonal space group P41212 and formation of a three‐dimensional (3D) coordination network solid. The 3D network is composed of interconnected twenty four‐membered rings comprising bridging methanesulfonate groups, which link the germanium atoms.

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