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. 2022 Aug 5;27(15):4995.
doi: 10.3390/molecules27154995.

A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)2 and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2':6',3″-terpyridin-4'-yl)benzene Ligands

Simona S Capomolla  1 , Giacomo Manfroni  1 , Alessandro Prescimone  1 , Edwin C Constable  1 , Catherine E Housecroft  1
Affiliations

A Tail Does Not Always Make a Difference: Assembly of cds Nets from Co(NCS)2 and 1,4-bis(n-Alkyloxy)-2,5-bis(3,2':6',3″-terpyridin-4'-yl)benzene Ligands

Simona S Capomolla et al. Molecules. .

Abstract

The consistent assembly of a (65.8) cds net is observed in reactions of cobalt(II) thiocyanate with 1,4-bis(n-alkyloxy)-2,5-bis(3,2':6',3″-terpyridin-4'-yl)benzene ligands in which the n-alkyloxy substituents are n-propyl (ligand 3), n-butyl (4), n-pentyl (5), n-hexyl (6), n-heptyl (7), and n-octyl (8). Crystals were grown by layering a methanol solution of Co(NCS)2 over a 1,2-dichlorobenzene solution of each ligand. The choice of crystallization solvents is critical in directing the assembly of the cds net. Single-crystal structures of [Co(NCS)2(3)]n.3.5nC6H4Cl2, [Co(NCS)2(4)]n.5.5nC6H4Cl2, [Co(NCS)2(5)]n.4nC6H4Cl2, [Co(NCS)2(6)]n.3.8nC6H4Cl2, [Co(NCS)2(7)]n.3.1nC6H4Cl2, and [Co(NCS)2(8)]n.1.6nC6H4Cl2.2nMeOH (C6H4Cl2 = 1,2-dichlorobenzene) are presented and compared. The n-alkyloxy chains exhibit close to extended conformations and are accommodated in cavities in the lattice without perturbation of the coordination framework.

Keywords: 3,2′:6′,3″-terpyridine; cobalt(II) thiocyanate; coordination network; solvent effects.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
The structures of the ditopic ligand 1, the first tetratopic ligand 2, containing two 3,2′:6′,3″-tpy metal-binding domains, and 4,2′:6′,4″-terpyridine.
Scheme 2
Scheme 2
Limiting planar conformations of the 3,2′:6′:3″-tpy metal-binding domain. Only the outer pyridine rings coordinate to metal ions.
Scheme 3
Scheme 3
The structures of ligands 3–12.
Figure 1
Figure 1
In [Co(NCS)2(3)]n.3.5nC6H4Cl2, both the Co atom and ligand 3 act as 4-connecting nodes. H atoms and solvent molecules are omitted for clarity.
Figure 2
Figure 2
(a) The cds network in [Co(NCS)2(3)]n.3.5nC6H4Cl2 viewed down the crystallographic b-axis. (b) The same network showing only the 4-connecting nodes.
Figure 3
Figure 3
Overlay of the ligand conformations showing the four coordinated trans-{Co(NCS)2(N)4} units in [Co(NCS)2(3)]n.3.5nC6H4Cl2 (red), [Co(NCS)2(4)]n.5.5nC6H4Cl2 (blue), [Co(NCS)2(5)]n.4nC6H4Cl2 (green), [Co(NCS)2(6)]n.3.8nC6H4Cl2 (yellow), [Co(NCS)2(7)]n.3.1nC6H4Cl2 (pale grey), and [Co(NCS)2(8)]n.1.6nC6H4Cl2.2nMeOH (black). In [Co(NCS)2(4)]n.5.5nC6H4Cl2, one of the two independent ligands is shown; both ligands have similar conformations (Table 2).
Figure 4
Figure 4
Packing diagrams of (a) [Co(NCS)2(3)]n.3.5nC6H4Cl2, (b) [Co(NCS)2(4)]n.5.5nC6H4Cl2, (c) [Co(NCS)2(5)]n.4nC6H4Cl2, (d) [Co(NCS)2(6)]n.3.8nC6H4Cl2, (e) [Co(NCS)2(7)]n.3.1nC6H4Cl2, and (f) [Co(NCS)2(8)]n.1.6nC6H4Cl2.2nMeOH. Solvent molecules have been removed. In (c–f), the packing diagram is viewed down the c-axis. In (b), there are two crystallographically independent ligands.
Figure 5
Figure 5
PXRD (CuKα1 radiation) patterns for [Co(NCS)2(6)]n.3.8nC6H4Cl2. Experimentally obtained pattern (red circles) is compared with the best fit from the Rietveld refinement analysis (black line). Bragg peak positions (green) and differences between the calculated and experimental plots (blue) are also shown.
See this image and copyright information in PMC

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