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Kristallstruktur des Benzol‐Addukts des 1,2,3,4‐Tetramethylcyclobutadien‐nickel(II)‐chlorids, (C 8 H 12 , NiCl 2 ) 2 , C 6 H 6
Author(s) -
Dunitz J. D.,
Mez H. C.,
Mills O. S.,
Shearer H. M. M.
Publication year - 1962
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19620450231
Subject(s) - chemistry , cyclobutadiene , monoclinic crystal system , benzene , crystallography , nickel , dimer , molecule , ring (chemistry) , stereochemistry , steric effects , crystal structure , atom (system on chip) , organic chemistry , computer science , embedded system
Crystals of 1,2,3,4‐tetramethylcyclobutadiene‐nickel dichloride, C 8 H 12 NiCl 2 , are monoclinic, a = 16,01, b = 8,01, c = 16,45 Å; β = 111° 5′; Z = 8; Space group P 2 1/ n . Crystals of the benzene containing solvate, 2C 8 H 12 NiCl 2 , C 6 H 6 , lose benzene rapidly but are stable for several days when enclosed in glass tubes. The unit cell of the solvate is monoclinic, a = 8,311, b = 11,944, c = 12,715 Å; β = 103° 2′; space group P 2 1 / c ; it contains 4 molecules of complex plus 2 molecules of benzene. The approximate structure has been derived by standard methods and refined by least‐squares analysis to an R factor of 0,069. The molecule, as it exists in the solvate, is a dimer, C 8 H 12 Ni 2 Cl 4 C 8 H 12 . Each Ni atom has on one side the four atoms of the cyclobutadiene ring (Ni‐C, 2,00 to 2,05 Å), and on the other side 3 Cl neighbours, two shared with the second Ni to form a 4‐membered ring (Ni‐Cl, 2,35 Å) and one unshared (Ni‐Cl, 2,26 Å). The cyclobutadiene ring is planar and appears to be square or very nearly so (C‐C, 1,40 to 1,45 Å). The methyl groups are displaced outwards ( i.e. away from the Ni atom) by 0,12 to 0,19 Å, probably as a result of steric interference with the Cl atoms. The benzene rings lie between, and approximately parallel to, pairs of C 8 H 12 groups belonging to different molecules, and undergo a strong rotational disorder in their own planes.