Crystal structures of 1,4-diazabicyclo[2.2.2]octan-1-ium 4-nitrobenzoate dihydrate and 1,4-diazabicyclo[2.2.2]octane-1,4-diium bis(4-nitrobenzoate): the influence of solvent upon the stoichiometry of the formed salt

In the structures of 1:1 and 1:2 adducts of phosphanetricarbonitrile (C3N3P) with 1,4-diazabicyclo[2.2.2]octane (C6H12N2), the 1:1 adduct crystallizes in the orthorhombic space group, Pbcm, with four formula units in the unit cell (Z′ = 0.5). The P(CN)3 unit lies on a crystallographic mirror plane while the C6H12N2 unit lies on a crystallographic twofold axis passing through one of the C—C bonds. The P(CN)3 moiety has close to C 3v symmetry and is stabilized by forming adducts with two symmetry-related C6H12N2 units. The phosphorus atom is in a five-coordinate environment. As a result of the symmetry, the two trans angles are equal so τ5 = 0.00 and thus the geometrical description could be considered to be square pyramidal. However, the electronic geometry is distorted octahedral with the lone pair on the phosphorous occupying the sixth position. As would be expected from VSEPR considerations, the repulsion of the lone-pair electrons with the equatorial bonding electrons means that the trans angles for the latter are considerably reduced from 180° to 162.01 (4)°, so the best description of the overall geometry for phosphorus is distorted square pyramidal. The 1:2 adduct crystallizes in the monoclinic space group, P21/m with two formula units in the asymmetric unit (i.e. Z' = 1/2). The P(CN)3 moiety lies on a mirror plane and one of the two C6H12N2 (dabco) molecules also lies on a mirror plane. The symmetry of the P(CN)3 unit is close to C 3v. There are three P...N interactions and consequently the molecular geometry of the phosphorus atom is distorted octahedral. This must mean that the lone pair of electrons on the phosphorus atom is not sterically active. For the 1:1 adduct, there are weak associations between the phosphorus atom and one of the terminal nitrogen atoms from the C[triple-bond] N moiety, forming chains in the a-axis direction. In addition there are weak C—H...N interactions between a terminal nitrogen atoms from the C[triple-bond]N moiety and the C6H12N2 molecules, which form sheets perpendicular to the a axis.

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The structures of 1:1 and 1:2 adducts of phosphanetricarbonitrile with 1,4-diazabicyclo[2.2.2]octane

Purdy

Butcher

Klug

2021

Acta Cryst E

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Crystal structures of 1,4-diazabicyclo[2.2.2]octan-1-ium 4-nitrobenzoate dihydrate and 1,4-diazabicyclo[2.2.2]octane-1,4-diium bis(4-nitrobenzoate): the influence of solvent upon the stoichiometry of the formed salt

Abstract: Solvent-dependent outcomes are noted in co-crystallization experiments between DABCO and 4-nitrobenzoic acid with mono- and diprotonated forms of DABCO are isolated.

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The structures of 1:1 and 1:2 adducts of phosphanetricarbonitrile with 1,4-diazabicyclo[2.2.2]octane

The structures of 1:1 and 1:2 adducts of phosphanetricarbonitrile with 1,4-diazabicyclo[2.2.2]octane

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