[2‐{ E (CH 2 CH 2 ) 2 NCH 2 }C 6 H 4 ] n Bi X 3– n ( E = O, NMe; X = Cl, Br, I; n = 1–3) and [2‐(Me 2 NCH 2 )C 6 H 4 ]BiBr 2 – New Hypervalent Organobismuth(III) Compounds

The homoleptic [2‐{ E (CH 2 CH 2 ) 2 NCH 2 }C 6 H 4 ] 3 Bi [ E = O ( 1 ), MeN ( 2 )], the chlorides [2‐{ E (CH 2 CH 2 ) 2 NCH 2 }C 6 H 4 ] 2 BiCl [ E = O ( 3 ), MeN ( 4 )] and the dichlorides [2‐{ E (CH 2 CH 2 ) 2 NCH 2 }C 6 H 4 ]BiCl 2 [ E = O ( 5 ), MeN ( 6 )] were synthesized by reaction of the corresponding ortho ‐lithium derivative with BiCl 3 in corresponding molar ratios. The dihalides [2‐{ E (CH 2 CH 2 ) 2 NCH 2 }C 6 H 4 ]Bi X 2 [ X = Br, E = O ( 7 ), MeN ( 9 ); X = I, E = O ( 8 ), MeN ( 10 )] as well as [2‐(Me 2 NCH 2 )C 6 H 4 ]BiBr 2 ( 11 ) were obtained by halide exchange reactions between R BiCl 2 and excess aqueous solution of K X . The compounds were characterized by multinuclear ( 1 H, 13 C) NMR spectroscopy and mass spectrometry. The crystal and molecular structures of 1 – 5 and 11 were determined by single‐crystal X‐ray diffraction. In all compounds the (C 6 H 4 CH 2 )N nitrogen atoms are coordinated to bismuth. The crystals of 1 and 2 , as well as those of the chlorides 3 and 4 , contain discrete molecules. For R 3 Bi intramolecular N→Bi interactions of medium strength [Bi(1)–N(1) 3.170(7) Å for 1 and 3.211(5) Å for 2 ] result in an overall distorted octahedral ( C,N ) 3 Bi core. In the monochlorides one nitrogen atom is strongly coordinated to the bismuth atom [2.660(11) Å for 3 and 2.744(14) Å for 4 ] trans to the halogen atom, whereas the second one is involved in a weaker intramolecular N→Bi interaction [3.095(11) Å for 3 and 3.061(14) Å for 4 ] trans to a carbon atom. The overall ( C,N ) 2 BiCl core is distorted square‐pyramidal. The crystals of the monohalides 5 and 11 contain discrete dimer units. The pendant arm nitrogen atom is strongly coordinated [2.548(9) Å for 5 and 2.485(13) Å for 11 ] trans to the bridging halogen atom, thus resulting in an overall distorted square‐pyramidal ( C,N )Bi X 3 ( X = Cl, Br) core. The six‐membered morpholinyl and piperazinyl rings in 1 – 5 adopt the chair conformation, which prevents intramolecular coordination of the oxygen or N(Me) nitrogen atoms to bismuth. Supramolecular architectures based on intermolecular Bi ··· Br interactions, Cl ··· H, and Br ··· H contacts are formed in the crystals of 3 , 5 , and 11 .