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Issue 42, 2013
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Completing a family: LiCN3H4, the lightest alkali metal guanidinate

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A family of alkali-metal guanidinates (M = Na–Cs) has been reported recently, representing all-nitrogen analogues of alkali bicarbonates and containing the elusive guanidinate monoanion CN3H4. Here, we describe the synthesis and characterisation of LiCN3H4 as the last representative of alkali guanidinates. Single crystals of LiCN3H4 were obtained using a solvothermal route in liquid ammonia, and the crystal structure was determined at 100 K using single-crystal X-ray diffraction (monoclinic, P21/c, Z = 4, a = 7.251(2) Å, b = 4.532(2) Å, c = 9.051(2) Å, β = 103.315(3)°). The structure of LiCN3H4 is reminiscent of the previously reported NaCN3H4 type in that both guanidinates contain tetrahedrally nitrogen-coordinated alkali-metal cations. The linking of these tetrahedra differs, however: they share corners in NaCN3H4 to form one-dimensionally infinite chains running through the crystal, whereas isolated, edge-sharing tetrahedra (Li2N6 motif) are found in the LiCN3H4 structure described here. Periodic density-functional theory (DFT) computations at the dispersion-corrected PBE + D2 level not only correctly reproduce the structural preferences, but also indicate that a NaCN3H4 polymorph should be viable adopting the lithium guanidinate type but much less easily so vice versa.

Graphical abstract: Completing a family: LiCN3H4, the lightest alkali metal guanidinate

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Publication details

The article was received on 06 Jul 2013, accepted on 12 Aug 2013 and first published on 13 Aug 2013

Article type: Paper
DOI: 10.1039/C3DT51820E
Dalton Trans., 2013,42, 15080-15087

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    Completing a family: LiCN3H4, the lightest alkali metal guanidinate

    P. K. Sawinski, V. L. Deringer and R. Dronskowski, Dalton Trans., 2013, 42, 15080
    DOI: 10.1039/C3DT51820E

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