Structural systematics of 4,4′-disubstituted benzenesulfonamidobenzenes. 1. Overview and dimer-based isostructures

Abstract

One hundred 4,4'-disubstituted benzenesulfonamidobenzenes, X-C(6)H(5)-SO(2)-NH-C(6)H(5)-Y, where X, Y = NO(2), CN, CF(3), I, Br, Cl, F, H, Me, OMe, have been synthesized and their crystal structures determined. The resulting set of 133 structures, which includes polymorphic forms, is used to make a comparative study of the molecular packing and the nature of the intermolecular interactions, including the formation of hydrogen-bonding motifs and the influence of the two substituents X and Y on these features. Nine distinct supramolecular connectivity motifs of hydrogen bonding are encountered. There are 74% of all the structures investigated which exhibit one of two motifs based on N-H...O=S interactions, a dimer or a chain. There are three other, infrequent motifs, also employing N-H...O=S links, which exhibit more complexity. Four different chain motifs result from either N-H...O=N, N-H...C[triple-bond]N or N-H...OMe interactions, arising from the presence of a nitro (position Y), nitrile (X or Y) or methoxy (Y) substituent. The program XPac [Gelbrich & Hursthouse (2005). CrystEngComm, 7, 324-336] was used to systematically analyse the packing relationships between crystal structures. Similar discrete (zero-dimensional) and extended (one-dimensional and two-dimensional) structure components, as well as cases of isostructurality were identified. A hierarchy for the classification of the 56 distinct structure types of this set is presented. The most common type, a series of 22 isostructures containing the simple centrosymmetric N-H...O=S-bonded dimer, is discussed in detail.

(E)-6-Chloro-2-(furan-2-ylmethylidene)-2,3,4,9-tetrahydro-1H-carbazol-1-one

“…The two benzene rings in (I) are tilted relative to each other by 38.3 (1)°, compared to the values of 49.4 (1)° in (II), 68.4 (1)° in (III) and 64.8 (1)° in (IV). The other bond parameters in (I) are similar to those observed in (II), (III), (IV) and other aryl sulfonamides (Perlovich et al, 2006;Gelbrich et al, 2007). The packing of molecules via N-H···O hydrogen bonds (Table 1) into infinite chains is shown in Fig.…”

At the Interface of Isomorphous Behavior in a 3 × 3 Isomer Grid of Monochlorobenzamides: Analyses of the Interaction Landscapes via Contact Enrichment Studies

“…45 In the literature there is considerable on-going interest on groups of isomorphous structures that exhibit structural diversity. [69][70][71][72] The Clpp structure contains an intramolecular C26-H26…O1 contact (C26…O1 = 2.891(2) Å, C-H…O = 117). The classic N-H…N intermolecular interaction [N1…N24 i = 3.114(2) Å, 139.2(17); symmetry code i = 1-x, y+½, ½-z, ESI, Table S2a] with C(6) motif is the principal hydrogen bond and the remaining intermolecular interactions comprise C-H…O [3.3482(2) Å, 130] and Cl14…C() halogen bonding contacts [3.3269(18) Å, C14-Cl14…C21 xix = 150.10(7); symmetry code xix = x,½-y,½+z], [31][32][33][34][35][36][37][38][39] linking the non-planar molecules into a 3D structure (Figure 1), together with C-H… and aromatic stacking.…”

“…Subtle differences at the molecular level do not impact on the overall molecular aggregation (isomorphous series) and differences between the crystal structures are noted at the secondary level. [40][41][42][65][66][67][68][69][70][71][72] Why is there such a considerable overlap between Clxx, Brxx but not with Fxx or Mxx?…”

N-(2,6-Dimethylphenyl)-4-methylbenzenesulfonamide

“…The molecule is bent at the S atom ( Fig. 1) with the C1-SO 2 -NH-C7 torsion angle of 88.0 (2)°, compared to the values of -51.6 (3)° in N-(phenyl)4-methylbenzenesulfonamide (II) (Gowda et al, 2009), -78.7 (2)° in N-(2,6-dimethylphenyl)-benzenesulfonamide (III) (Gowda et al, 2008) (Perlovich et al, 2006;Gelbrich et al, 2007).…”

“…For our study of the effect of substituents on the structures of N-(aryl)-arylsulfonamides, see: Gowda et al (2008Gowda et al ( , 2009Gowda et al ( , 2010. For related structures, see: Gelbrich et al (2007); Perlovich et al (2006). Table 1 Hydrogen-bond geometry (Å , ).…”