The first nitrite complex of actinide metal, {C(NH2)(3)}(2)[NpO2-(NO2)(Pic)(2)] was synthesized, and its crystal structure was determined using X-ray diffractometry and confirmed by NIR and IR spectroscopies. Main crystallographic data: space group Pi, triclinic, a = 8.9329(1) angstrom, b = 11.6669(2) angstrom, c = 11.6698(2) angstrom, a = 68.080(1)degrees, beta = 88.213(1)degrees, gamma = 73.254(1)degrees, V = 1076.45(3) angstrom(3), and Z = 2.