Bifurcated μ₂-I···(N,O) Halogen Bonding: The Case of (Nitrosoguanidinate)Ni^II Cocrystals with Iodine(I)-Based σ-Hole Donors

Abstract

Cocrystallization of the nitrosoguanidinate complexes [Ni{NHC(NR 2 )NN(O)} 2 ] (R 2 = Me 2 (1), Me/Ph (2), C 5 H 10 and 2•2C 2 I 4 ; all of these solids were studied by single-crystal X-ray diffraction. Each structure exhibits the asymmetric bifurcated halogen bond μ 2 -I•••(N,O) as a characteristic feature and a structure-directing contact. DFT calculations were used to evaluate the energetic features of the bifurcated halogen bonds that range from −6.7 to −8.3 kcal/mol; in general, the I•••O contact is stronger that the I•••N contact. Molecular electrostatic potential (MEP) surfaces along with the quantum theory of "atoms in molecules" (QTAIM) and the noncovalent interaction plot index (NCIPlot) computational tools were used to characterize the bifurcated halogen bonds in the cocrystals of 1−3. Various types of bifurcated halogen bonds involving nonmetal atoms as halogen-bond-accepting centers were systematized and categorized.

The Isocyanide Complexes cis-[MCl2(CNC6H4-4-X)2] (M = Pd, Pt; X = Cl, Br) as Tectons in Crystal Engineering Involving Halogen Bonds

“…Pursuing our interest in crystal engineering involving halogen bonding and their effect on properties and reactivity (for our recent works on HaBs see references [16,[50][51][52][53][54][55] and references therein), in the current study we undertook a joint synthetic and theoretical study concerning cis-bisisocyanide complexes cis-[PdCl 2 (CNC 6 H 4 -4-X) 2 ] (X = Cl 1, Br 2) and cis-[PtCl 2 (CNC 6 H 4 -4-Br) 2 ] (3), in which we explored the potential of these organometallics as useful 2σhD/2σhA systems for HaB-involving crystal engineering.…”

Weak Interactions in Cocrystals of Isoniazid with Glycolic and Mandelic Acids

“…For the former the BSSE correction [36] has been applied and for the latter we have used the kinetic energy density values at the bond critical points that emerge upon complexation, applying the methodology proposed by Espinosa et al [37]. This methodology has been recently used to evaluate non-covalent interactions in the solid state [38][39][40][41][42][43][44][45]. The NCI plot iso-surfaces [46,47] have been generated using the AIMAll program [35] using the PBE0-D3/def2-TZVP wavefunction.…”

H-Bonds, π-Stacking and (Water)O-H/π Interactions in (µ4-EDTA)Bis(Imidazole) Dicopper(II) Dihydrate

“…The def2-TZVP [14,15] basis set combined with the PBE0 functional [16,17] and the D3 dispersion correction [18,19] were used for the calculations. This level of theory (functional and basis set) has been used before to study noncovalent interactions in the solid state [20][21][22][23][24], including those analyzed in this work [25][26][27]. Moreover, X-ray coordinates instead of optimized geometries were used to investigate the energetic features of the noncovalent interactions in the solid state, because we were interested to analyze them as they stand in the solid state, instead of investigating the optimal complexation geometry.…”