Iodo-nitroarenesulfonamides: interplay of hard and soft hydrogen bonds, I...O interactions and aromatic π...π stacking interactions

Abstract

Molecules of N‐(4′‐iodophenylsulfonyl)‐4‐nitroaniline, 4‐O2NC6H4NHSO2C6H4I‐4′ (1), are linked by three‐centre I⋯O2N interactions into chains and these chains are linked into a three‐dimensional framework by C—H⋯O hydrogen bonds. In the isomeric N‐(4′‐nitrophenylsulfonyl)‐4‐iodoaniline, 4‐IC6H4NHSO2C6H4NO2‐4′ (2), the chains generated by the I⋯O2N interactions are again linked into a three‐dimensional framework by C—H⋯O hydrogen bonds. Molecules of N,N‐bis(3′‐nitrophenylsulfonyl)‐4‐iodoaniline, 4‐IC6H4N(SO2C6H4NO2‐3′)2 (3), lie across twofold rotation axes in space group C2/c and they are linked into chains by paired I⋯O=S interactions: these chains are linked into sheets by a C—H⋯O hydrogen bond, and the sheets are linked into a three‐dimensional framework by aromatic π⋯π stacking interactions. In N‐(4′‐iodophenylsulfonyl)‐3‐nitroaniline, 3‐O2NC6H4NHSO2C6H4I‐4′ (4), there are rings formed by hard N—H⋯O=S hydrogen bonds and rings formed by two‐centre I⋯nitro interactions, which together generate a chain of fused rings: the combination of a C—H⋯O hydrogen bond and aromatic π⋯π stacking interactions links the chains into sheets. Molecules of N‐(4′‐iodophenylsulfonyl)‐4‐methyl‐2‐nitroaniline, 4‐CH3‐2‐O2NC6H3NHSO2C6H4I‐4′ (5), are linked by N—H⋯O=S and C—H⋯O(nitro) hydrogen bonds into a chain containing alternating and rings, but there are no I⋯O interactions of either type. There are two molecules in the asymmetric unit of N‐(4′‐iodophenylsulfonyl)‐2‐nitroaniline, 2‐O2NC6H4NHSO2C6H4I‐4′ (6), and the combination of an I⋯O=S interaction and a hard N—H⋯O(nitro) hydrogen bond links the two types of molecule to form a cyclic, centrosymmetric four‐component aggregate. C—H⋯O hydrogen bonds link these four‐molecule aggregates to form a molecular ladder. Comparisons are made with structures retrieved from the Cambridge Structural Database.

Structure-Directing Weak Interactions with 1,4-Diiodotetrafluorobenzene Convert One-Dimensional Arrays of [MII(acac)2] Species into Three-Dimensional Networks

“…Relevant bifurcated halogen bonding C–I···μ 2 -(O,O) was repeatedly reported. − Our CCDC search also allowed the verification of FIB-free structures where BXBs span 3–6-membered systems, viz. 3-membered cycles C–I···μ 2 -(O,O)-(ROOR), 4-membered systems C–I···μ 2 -(O,O)-(OXO) (where X = N, ,,,− C, S, , Cl, or such metal centers as Co, Cd, Cu), 5-membered moieties C–I···μ 2 -(O,O)-(OXXO) (X–X = C–C ,, ), and 6-membered species C–I···μ 2 -(O,O)-(OXXXO) (X–X–X = N–C–C, S–N–S). As far as metal-containing fragments C–I···μ 2 -(O,O)-(OMO) ,, (Figure ) are concerned, all these moieties are formed by bifunctional complexes featuring both XB donor (iodine) and XB acceptor (oxygen) centers in one molecule, whereas in our cases supramolecular organization is determined by an external XB donor (the iodines of FIB) and two oxygen centers of each of the acac complexes.…”

Graded IR Filters: Distinguishing Between Single and Multipoint NO2···I Halogen Bonded Supramolecular Synthons (P, Q, and R Synthons)

“…Step 2: Verifying the IR Characteristics with Other Molecules Having Known Synthons The IR characteristics mentioned in Step 1 are now mapped onto a second set of iodo and nitro group containing molecules (4, 5, and 6) [33,34,41] (Fig. 5), with known crystal structures but also having other functional groups.…”

“…Esters 6, 10, 11, 12, 13, and 14 (Chart 1) were prepared by following the reported procedure [33] and purified by crystallisation from ethanol for 6 and 10, from THF for 11, from methanol for 13, and from chloroform for 12 and 14. The sulfonamide 4 was synthesised according to a reported procedure [34] and purified through crystallisation from 1,2-dichloromethane. Imine 7 was synthesised according to a known procedure [24] and purified by crystallisation from ethanol.…”