Hydrogen-Bonded Extended Arrays of the [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>]<sup>2+</sup> Core-Containing Clusters SelbyHugh D. RolandBryan K. CarducciMichael D. ZhengZhiping 2003 Site-differentiated solvated clusters of the general formula [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PEt<sub>3</sub>)<i><sub>n</sub></i>(MeCN)<sub>6</sub><sub>-</sub><i><sub>n</sub></i>](SbF<sub>6</sub>)<sub>2</sub> (<i>n</i> = 4, <i>cis</i> and <i>trans</i>; <i>n</i> = 5) undergo ligand substitution reaction with isonicotinamide to afford the corresponding amide derivatives, [Re<sub>6</sub>(μ<sub>3</sub>-Se)<sub>8</sub>(PEt<sub>3</sub>)<i><sub>n</sub></i>(isonicotinamide)<sub>6</sub><sub>-</sub><i><sub>n</sub></i>]<sup>2+</sup> [<b>1</b> (<i>n</i> = 5); <b>2</b> (<i>n</i> = 4, <i>trans</i>); <b>3</b> (<i>n</i> = 4, <i>cis</i>)]. Retention of stereochemistry in each case was confirmed by <sup>1</sup>H and <sup>31</sup>P NMR. The solid-state structures of all three compounds were established crystallographically, which revealed self-complementary hydrogen-bonding interactions between adjacent cluster units. While complex <b>1</b> exists as hydrogen-bonded dimers in the solid state, compounds <b>2</b> and <b>3</b> form one-dimensional chains of clusters bridged by paired hydrogen bonds. It is the rigid stereochemistry of the cluster, combined with the classic crystal engineering motif of complementary N−H···O amide hydrogen bonding, that affords the predictable solid-state structures and dimensionality.