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Syntheses, Structures and Theoretical Investigations of 1λ 4 ,3λ 4 ,5λ 4 ‐Trithia‐2,4,6,8,9‐pentaazabicyclo[3.3.1]nona‐1(9),2,3,5,7‐pentaenes
Author(s) -
Knapp Carsten,
Lork Enno,
Borrmann Tobias,
Stohrer WolfDieter,
Mews Rüdiger
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200300111
Subject(s) - chemistry , stacking , crystallography , molecule , aryl , acceptor , bicyclic molecule , bond length , stereochemistry , computational chemistry , crystal structure , organic chemistry , alkyl , physics , condensed matter physics
The syntheses of the title compounds RCN 5 S 3 with electron‐withdrawing aryl substituents [R = 2‐FC 6 H 4 ( 1m ), 4‐FC 6 H 4 ( 1n ), 2,6‐F 2 C 6 H 3 ( 1o ), C 6 F 5 ( 1p ), 4‐NCC 6 H 4 ( 1q ) and Cl 3 C ( 1r )] are described. The X‐ray structures of 1n , 1o , 1q and 1r , together with those of Me 2 NCN 5 S 3 ( 1b ) and 4‐CH 3 C 6 H 4 CN 5 S 3 ( 1f ), are reported. The experimentally determined dependence of the bond lengths on the substituents R within the bicyclic system RCN 5 S 3 is well‐reflected in the results of the theoretical calculations (RHF, MP2, B3LYP). The bonding model developed shows that acceptor substituents do not influence bonding within the bicycle. In the solid state, two fundamentally different primary interactions of the RCN 5 S 3 molecules are observed; “stacking” and “dimerisation”, which can be rationalised by electrostatic interactions between the CN 5 S 3 units. However, secondary effects − the interactions between the R substituents − may be even more dominant. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)