NDLI: Endo and Exo Coordination to Cofacial Binuclear Copper(II) Complexes

Content Provider	SpringerLink
Author	Maverick, Andrew W. Billodeaux, Damon R. Ivie, Michael L. Fronczek, Frank R. Maverick, Emily F.
Copyright Year	2001
Abstract	A structural study of internal (endo) and external (exo) coordination to cofacial binuclear complexes is reported.Cu$_{2}$(NBA)$_{2}$(NBAH$_{2}$=3,3'-[2,7-naphthalenediylbis(methylene)]-bis(2,4-pentanedione)) is large enough to accommodate 2-methylpyrazine as an intramolecularly coordinated guest molecule Cu$_{2}$(NBA)$_{2}$(μ(2Mepyz))ċ4CH$_{2}$Cl$_{2}$Cu$_{2}$C$_{53}$H$_{58}$N$_{2}$O$_{8}$Cl$_{8}$, orthorhombic, space group Pnma (No. 62); a = 22.4674(11); b = 22.230(2); c = 11.4520(6) Å V = 5719.6(6) Å$^{3}$ (at 100 K); Z = 4; R = 0.058; R $_{w}$ = 0.167 for 344 parameters and 5339 reflections with I > 2σ(I). The Cu$_{2}$(NBA)$_{2}$(μ-(2-Mepyz)) molecules possess crystallographic m symmetry, with the CuċCu vector (CuċCu' 7.4801(8) Å) perpendicular to the mirror plane; this requires disorder in the 2-Mepyz guests. The two ``Cu(acac)$_{2}$'' moieties (acacH = 2,4-pentanedione) are not quite parallel (dihedral angle between (acac)$_{2}$ planes = 3.93(7)$^{circ}$), forming a slightly wider opening on the side of the methyl group in the 2-Mepyz guest. On the other hand, the cavity in Cu$_{2}$(XBA)$_{2}$ (XBAH$_{2}$ = 3,3'-[1,3-phenylenebis(methylene)]-bis(2,4-pentanedione)) is smaller, so that CH$_{3}$CN must bind externally.Cu$_{2}$(XBA)$_{2}$(CH$_{3}$CN)$_{2ċ}$1.5CH$_{3}$CNċH$_{2}$O,Cu$_{2}$C$_{43}$H$_{52.5}$N$_{3.5}$O$_{9}$, monoclinic, space group P2$_{1}$/c (No. 14); a = 11.7361(16); b = 14.197(3); c = 13.299(3) Å; β = 92.22(2)$^{^}$; V = 2214.3(7) Å$^{3}$ (at 100 K); Z = 2; R = 0.044; R $_{w}$ = 0.124 for 275 parameters and 4983 reflections with I > 2σ (I). This structure contains centrosymmetric Cu$_{2}$(XBA)$_{2}$ units (CuċCu' 4.8302(12) Å) with externally coordinated CH$_{3}$CN ligands. The crystal packing in Cu$_{2}$(NBA)$_{2}$(μ(2Mepyz))ċ4CH$_{2}$Cl$_{2}$,which contains close π contacts between layers of Cu$_{2}$(NBA)$_{2}$(μ-(2-Mepyz)) moieties, is also similar to that in three other crystalline host–guest adducts M$_{2}$(NBA)$_{2}$(μ-G). Cu$_{2}$(XBA)$_{2}$(CH$_{3}$CN)$_{2}$ċ1.5CH$_{3}$-CNċH$_{2}$O does not contain similar layers of molecules, presumably because the adduct molecules do not have the same type of exposed flat surfaces.
Starting Page	19
Ending Page	26
Page Count	8
File Format	PDF
ISSN	09230750
Journal	Journal of Inclusion Phenomena and Macrocyclic Chemistry
Volume Number	39
Issue Number	1-2
e-ISSN	15731111
Language	English
Publisher	Kluwer Academic Publishers
Publisher Date	2001-01-01
Publisher Place	Dordrecht
Access Restriction	Subscribed
Subject Keyword	Food Science Organic Chemistry Crystallography
Content Type	Text
Resource Type	Article

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