The nitrosoguanidinate complex [Ni{NH=C(NMe2)-NN(O)}(2).] (1) was cocrystallized with I-2 and sym-trifluorotriiodo-benzene (FIB) to give associates 1.2I(2) and 1.2FIB. Structures of these solid species were studied by XRD followed by topological analysis of the electron density distribution within the framework of Bader's approach (QTAIM) at the M06/DZP-DKH level of theory and Hirshfeld surface analysis. Our results along with inspection of XRD (CCDC) data, accompanied by the theoretical calculations, allowed the identification of three types of contacts. The Ni center dot center dot center dot I semicoordination of the electrophilic nickel(II) center with electron belt of 12 was observed in 1.2I(2), the metal -involving halogen bonding between the nucleophilic nickel(II)-d(z)(2) center and sigma-hole of iodine center was recognized and confirmed theoretically in the structure of [FeNi(CN)(4)(IPz)(H(2)0)](n) (IPz = 4-N-coordinated 2-I-pyrazine), whereas the arrangement of FIB in 1.2FIB provides a boundary case between the semicoordination and the halogen Ni center dot center dot center dot I bondings. In 1.2I(2) and 1.2FIB, noncovalent interactions were studied by variable temperature XRD detecting the expansion of noncovalent contacts with preservation of covalent bond lengths upon the temperature increase from 100 to 300 K. The nature and energies of all identified types of the Ni center dot center dot center dot I noncovalent interactions in the obtained (1.2I(2) and 1.2FIB) and in the previously reported ([FeNi(CN)(4)(IPz)(H2O)](n) [NiL2](I-3)(2)center dot 2I(2) (L = o-phenylene-bis(dimethylphosphine),[NiL]I-2 (L = 1,4,8,11-tetra-azacydotetradecane), Ni(en)(2)](n)[AgI2](2n) (en = ethylenediamine), and [NiL] (ClO4) (L = 4-iodo-2-(2-(2-(2-pyridyl)ethylsulfanypethylimino)methyl)-phenolate)) structures were studied theoretically. The estimated strengths of these noncovalent contacts vary from 1.6 to 4.1 kcal/mol and, as expected, become weaker on heating. This work is the first emphasizing electrophilic nucleophilic dualism of any metal center toward noncovalent interactions.