Four new alkylammonium bis(benzohydroximato)borates have been prepared and characterized by elemental analysis, IR and 1 H NMR spectra. The crystal and molecular structures of dicycohexylammonium bis(benzohydroximato)borate chloroform solvate (1.CHCl 3 ) and tetra-n-propylammonium bis(benzohydroximato)borate (3) have been determined by X-ray diffraction methods. In both examples the bis(hydroximato)borate anions show the expected spirochelate structure with slightly distorted tetrahedral BO 4 coordination. The C N as well as the C O bonds within the chelate rings have considerable double bond character. Bond lengths and angles of the BONCO heterocyle are in good agreement with those observed in N-methylacetohydroxamatoboron complexes (Can. J. Chem. 55 (1977) 1, Can. J. Chem. 56 (1978) 1676). In the crystal structure of 1.CHCl 3 the bis(benzoydroximato)borate anions are linked to the dicyclohexylammonium cations by strong N H...O and N H...N hydrogen bonds.