Structure of N-aromatic amides. II. XC6H4NHCOY

Abstract

Introduction. In the previous work on N-aromatic amides, the crystal structures of the amides have been classified by the scheme of the N-H...O=C hydrogen bonds into three types: 21, glide and translation (Haisa, Kashino, Ueno, Shinozaki & Matsuzaki, 1980). However, factors other than the hydrogen bonds might also dominate the structures. In the present work, the structures of salicylanilide (1), o-nitroacetanilide (2) and p-acetamidobenzoic acid (3) have been determined in order to examine the effects of polar groups on the structure of acetanilides as part of a study on the systematization of the crystal structures of aromatic compounds (Halsa, 1978). (2) and Discussion. The final atomic parameters of (1)-(3) are listed in Table 2.* The thermal ellipsoids of the molecules are shown in Fig. 1, with atomic numbering. Bond lengths and interbond angles are listed in Table 3.The molecule of (1) (5) 1198 (2) 4.16 (6) C(I)715 (1) 2321.8 (6) 1309 (2) 3.64 (7) C (2) 1731 (I) 2084.9 (7) 541 (2) 3.72 (7) C (3) 1886 (2) 1531-2 (7) 553 (2) 4.45 (8) C (4) 1039 (2) 1205.8 (7) 1360 (3) 5-14 (9) C (5) 31 (2) 1428.7 (7) 2140 (2) 4.94 (9) C(6) -127 (1) 1980.7 (7) 2098 (2) 4-20 (8) C (7) 462 (1) 2912.7 (7) 1395 (2) 3.77 (8) C (8) 1458 (l) 3813.3 (7) 1215 (2) 4.05 (8) C (9) 520 (2) 4141.8 (8) 1757 (3) 5.40 (9) C (10) 675 (2) 4694. l (8) 1719 (3) 6-8 (1) C(i l)1740 (2) 4923.3 (8) 1197 (3) 7.4 (1) C (12) 2679 (2) 4597-3 (9) 682 (3) 6.8 (1) C (13) 2542 (2) 4042.2 (8) 693 (3) 5.36 (9) (2) o-Nitroacetanilide O(1) 5167.9 (7) 0(2) 2581.3 (6) 0(3) 1379-5 (7) N(I) 4027-0 (7) N (2) 2167.6 (7) C(I)3515.3 (8) 2134 (3) 7056 (1) 6.14 (6) -3590 (2) 6666 (1) 4.62 (5) -1623 (3) 6002 (1) 6.28 (7) -741 (2) 6612 (1) 4.12 (5) -1810 (2) 6064 (1) 3.95 (5) 625 (3) 5662 (1) 3-76 (6) C (2) 2621.0 (8) 147 (3) 5383 (1) 3.59 (6) C (3) 2107 (1) 1544 (3) 4445 (I) 4.27 (7) C (4) 2477 (1) 3421 (3) 3756 (I) 4.81 (7) C (5) 3357 (1) 3924 (3) 4014 (2) 5.07 (7) C (6) 3869 (1) 2569 (3) 4936 (2) 4.68 (7) C (7) 4787.7 (8) 122 (3) 7282 (1) 4.35 (7) C (8) 5102 (1) -1683 (4) 8348 (2) 5.60 (8) (3) p-Acetamidobenzoie acid358 (2) 3284 (1) 1287 (3) 3.62 (6) C (1) 5694 ( , N(1)-- In the molecule of (3), the benzene ring (I), amide group (II) and carboxyl group (III) are planar within 0.008 (2), 0.006 (2) and 0.002 (2)/k, respectively. The dihedral angles between these planes are 40.40 (7) ° for C13HllNO2, C8H8N203 AND C9H9NO 3 nitro group [N(1)...O(2) 2.657(2), N(1)--H(5) 0.84(2), H(5)...O(2) 2.01(2)A1.397 (3) C(9)--C(10) 1.380 (3) C(1)-C (6) 1.396 (3) C(10)-C(I 1) 1.365 (4) C(1)-C (7) 1.492 (3) (2) o-Nitroacetanilide .86 (2), H(5)...O(3) 2.10 (2) A, N(1)-H(5)...O(3) 179 (2), H(5)...O(3)-C(8) 174.6 (6)°]. The other hydrogen bond is formed between the earboxyl groups related by T as found in many carboxylic acids, (Kashino & Haisa, 1980) [O(2)...O(1) 2.625 (1), O(2)--H(9) 1.14, n(9)...O(1) 1.49(3)/k, 0(2)--n(9)...O(1) 172 (3), H(9)...O(1)-C (7) 119 (1) (1) to (3) the C-N-C angles tend to increase with decrease in the dihedral angle between the planes of the benzene ring ...

6-Oxo-6-(phenylamino)hexanoic acid [two polymorphic forms, (I) and (II)] and 4-oxo-4-(N-methylphenylamino)butanoic acid (III)

“…The bond angles and distances found for (I), (II) and (III) are consistent with those observed in pacetanisidide (Haisa, Kashino, Ueno, Shinozaki & Matsuzaki, 1980) and p-acetamidobenzoic acid (Kashino, Matsushita, Iwamoto, Yamaguchi & Haisa, 1986). The two C--O bond distances of the carboxyl group in (II) are only just significantly different (5tr), suggesting a partially disordered model.…”

Crystal Structure of the 5-Chloro Salicylamides: Three Different Types of the H-bonding Influenced Linear Chain Formation in the Solid State

“…All bond lengths and angles (see Table 1) in 2a are in the usual ranges reported in the literature [40]. The structure comparison of 2a with the series of reported salicylanilides [29][30][31][32][33][34][35][36][37][38][39] shows only some small changes mainly in the degree of planarity of compounds and the intramolecular architecture driven by the differences in the types of H-bonding. The second compound 2b containing a methylene linker between the amide nitrogen and the benzene ring is no longer planar but has a bent shape ( Figure 4) due to the impossibility of delocalization of a nitrogen lone electron pair into the benzene ring resulting from lack of electronic coupling, and broken by the methylene spacer with saturated bonds.…”

“…However the situation is completely different in the solid phase. Regardless of substitution on both aromatic rings, all known salicylanilides [29][30][31][32][33][34][35][36][37][38][39] exclusively exist in the "open-ring" β-form. If two stable polymorphs exist [32], then they differ only in their packing patterns and not in their hydrogen bonds patterns.…”

3-(Acetylamino)benzoic acid

“…The crystal structures of 2-acetylaminobenzoic acid, (I) (Kovalevsky, 1999;Mascarenhas et al, 1980;Rajnikant & Deshmukh, 2004), and 4-acetylaminobenzoic acid, (III) (Kashino et al, 1986;Feeder & Jones, 1992), have been described in the literature. The crystal structure of the title compound (II) has not been solved to date.…”

“…For the crystal structures of the ortho-and para-isomers of the title compound, see : Feeder & Jones (1992); Kashino et al (1986); Kovalevsky (1999); Mascarenhas et al (1980); Rajnikant & Deshmukh (2004).…”