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The interaction of Np(V) with all isomers of pyridinemonocarboxylic acid has been investigated, stability constants have been calculated using NIR spectroscopy. Single crystals of [NpO 2 (Pic)(H 2 O) 2 ] ( 1 ), Cs[NpO 2 (Pic) 2 (HPic)]·3H 2 O ( 2 ), [NpO 2 (Nic)(H 2 O)] ( 3 ), and [NpO 2 (iso-Nic)(H 2 O)] ( 4 ) have been synthesized. Compound  1  contains infinite chains; compound  2  consists of isolated Cs + , [NpO 2 (Pic) 2 (HPic)] -  groups and water molecules. In both  3  and  4  neptunoyl-ion NpO 2  acts as monodentate ligand with one of the O atoms of NpO 2  group entering in coordination polyhedron of the adjacent Np atom. Compounds  3  and  4  have layered and three-dimensional topologies, respectively. Crystallographic data: [NpO 2 (Pic)(H 2 O) 2 ], space group  P ¯1, triclinic,  a  = 6.380(2),  b  = 7.733(2),  c  = 10.700(4) Å, α = 96.49(3), β = 106.78(3), γ = 103.83(3)°, and  Z  = 2 ( 1 ); Cs[NpO 2 (Pic) 2 (HPic)]·3H 2 O, space group  P ¯1, triclinic,  a  = 8.707(2),  b  = 9.777(2),  c  = 14.640(3) Å, α = 76.633(15), β = 78.75(2), γ = 86.55(2)°, and  Z  = 2 ( 2 ); [NpO 2 (Nic)(H 2 O)], space group  P 2 1 / n , monoclinic,  a  = 11.901(4),  b  = 5.5628(15),  c  = 12.124(3) Å, β = 101.05(2)°, and  Z  = 4 ( 3 ); [NpO 2 (iso-Nic)(H 2 O)], space group  P 2 1 2 1 2 1 , orthorhombic,  a  = 5.742(3),  b  = 8.550(5),  c  = 18.512(10) Å, and  Z  = 4 ( 4 ). Electron and IR spectra of solid compounds have been measured.

Interaction of neptunium(V) with picolinic, nicotinic and isonicotinic acids