Piperazine-functionalized C₆₀ and diiodine or iodine monochloride as components in forming supramolecular assemblies

Abstract

The reaction of the piperazine mono-adduct, N(CHCH)NC, with diiodine produced well ordered, black crystals of (IN(CHCH)NI)C·2.884(CH)·0.116I, which contains two nearly linear N-I-I units. Reaction of N(CHCH)NC with iodine monochloride produced two materials: the dihalogen adduct, (ClIN(CHCH)NICl)C·2.3(CS)·0.7(CHCl), when crystallization occurred rapidly from carbon disulfide/dichloromethane solution or the salt, [(N(CHCH)NH)C][ICl]·CS, when crystallization happened more slowly from toluene/dichloromethane solution where hydrolysis of the iodine monochloride by adventitious water presumably occurred.

The relationship between the crystal habit and the energy framework pattern: a case study involving halogen bonding on the edge of a covalent bond

“…37 Analogous short I⋯N distances were observed in the 2 : 1 complexes of ICl with fullerene-fused DABCO and in the 1 : 1 complex of IBr with cationic ( N -methylsubstituted) DABCO. 38,39 We showed earlier that adjusting the strength of HaB donor in the complexes of bromosubstituted electrophiles with DABCO or variation of HaB acceptor in the complexes of I 2 with aromatic N-oxides allows one to gradually modulate the strength (and ultimately, the nature) of interactions in such associations from supramolecular to covalent bonding. 40,41 Wide variations of N⋯I distances were also observed in complexes of I 2 , IBr, and ICl molecules with pyridine derivatives.…”

Mono- and Bis-Carbonyl Hypoiodites of the Tertiary Amines Quinuclidine and DABCO

“…Only four prior solid-state examples of DABCO acting as a ditopic halogen bond acceptor exist in the literature, two of which involve halogen bonding to the bromine atoms of two molecules of Br 2 or N -bromosuccinimide. , The only iodine examples are both of a piperazine-functionalized fullerene coordinating to two molecules of ICl or I 2 with I–N bond lengths of 2.429(3)/2.459(3) Å or 2.606(4) Å, respectively, though the latter is perhaps best described as N···I–I coordination . The use of HMTA as a ditopic halogen bond acceptor has also been explored with HMTA·(ICl) 2 , with I–N bond lengths of 2.328(3)/2.360(3) Å.…”

“…54,55 The only iodine examples are both of a piperazine-functionalized fullerene coordinating to two molecules of ICl or I 2 with I−N bond lengths of 2.429(3)/2.459(3) Å or 2.606(4) Å, respectively, though the latter is perhaps best described as N•••I−I coordination. 56 The use of HMTA as a ditopic halogen bond acceptor has also been explored with HMTA•(ICl) 2 , 57 with I− N bond lengths of 2.328(3)/2.360(3) Å.…”

Halogen Bonding and/or Covalent Bond: Analogy of 3c–4e N···I···X (X = Cl, Br, I, and N) Interactions in Neutral, Cationic, and Anionic Complexes

“…, 1,4-diazabicyclo[2.2.2]-octane (DABCO) are characterized by the very short I···N bonds of about 2.25–2.30 Å, which are close to that in the cationic or anionic associations comprising N–I + –N fragments [ e.g. , bis­(1,4-diazabicyclo[2.2.2]­octane)­iodine­(I), or 1,1′-iodanylbis­(pyrrolidine-2,5-dione)]. − Computational analysis also demonstrated that many characteristics of the bonding in complexes of DABCO with IX are close to those in the trihalide anions . Similar short N–I distances were also observed in the complexes of some nucleophiles with N -iodosaccharin and N -iodosuccinimide. − As such, several previous publications suggested that the interaction in the strong HaB complexes ( e.g.…”