ABSTRACT
The isomers 3,3'-(1,2-ethynediyl)bis(2-pyridone), (I), and 6,6'-(1,2-ethynediyl)bis(2-pyridone), (II), were designed to form a hydrogen-bonded pair through alignment of their complementary cyclic lactam moieties. Instead, an equimolar mixture of (I) and (II) dissolved in methanol produced crystals of 3,3'-(1,2-ethynediyl)bis(2-pyridone)-6,6'-(1,2-ethynediyl)bis(2-pyridone)-methanol (1/2/2), 0.5C(12)H(8)N(2)O(2) x C(12)H(8)N(2)O(2) x CH(4)O, in which one molecule of (I), situated at a center of symmetry, is hydrogen bonded to two molecules of (II) and to two molecules of methanol.
Subject(s)
Pyridones/chemistry , Crystallography, X-Ray , Hydrogen Bonding , Models, Molecular , Molecular Conformation , StereoisomerismABSTRACT
The complex between (R)-4,5,7,8,10,11,13,14,16,17-decahydro-2,19- diphenyldinaphtho[2,1-q:1',2'-s][1,4,7,- 10,13,16]hexaoxa[2,5,8,11,14,17,19]cycloicosaheptene {Chemical Abstracts name: (R)-4,5,7,8,10,11,13,14,16,17-decahydro-2,19- diphenyldinaphtho[2,1-q:1',2'-s][1,4,7,-10,13,16]hexaoxacycloic osin} and D-2-phenylglycinium methyl ester perchlorate, C9H12NO2+.ClO4-.C42H40O6.-H2O, crystallizes in the orthorhombic space group P2(1)2(1)2(1) with two C9H12NO2+.C42H40O6 complexes, two ClO4- ions and two molecules of water in the asymmetric unit. Crystal data: M(r) = 924.44, a = 23.048 (7), b = 34.383 (6), c = 11.992 (6) A, V = 9503 (6) A3, Z = 8, Dx = 1.292 Mg m-3, F(000) = 3904, mu(Cu K alpha) = 1.261 mm-1, T = 175 K, R = 0.0896 for all 7784 reflections, 1208 parameters refined in three blocks with 29 restraints. Nearly twenty years elapsed between the first data collection and the solution of the structure with the direct-methods program CRUNCH. The structural details are of interest because enantiomers of this host show a high degree of discrimination between enantiomers of alpha-amino acids and their esters. The crystal structure demonstrates the influence of C-H...O and C-H...pi interactions on the unexpected orientation of the guest in the host cavity. The same orientation is found in both of the unique complexes, and the geometric details are in agreement with solution studies.
Subject(s)
Computer Simulation , Crown Ethers , Ethers, Cyclic/chemistry , Glycine/analogs & derivatives , Models, Molecular , Software , Crystallization , Crystallography, X-Ray/methods , Glycine/chemistry , Molecular Structure , Stereoisomerism , ThermodynamicsABSTRACT
In the title complex, tert-butylammonium perchlorate-2,5,8,11,14,17-hexaoxatricyclo[16.8.0.0(20,25]hexac osa- 1(26),18,20(25),21,23-pentaene-ethyl acetate-dichloromethane (4/4/1/1), C4H12N+.C20H26O6.ClO4-.0.25C4-H8O2.0.25CH2Cl2 , the tert-butylammonium cation binds to the macrocyclic host (Chemical Abstracts name: 2,3,5,6,8,9,11,12,14,15-decahydro-1,4,7,10,13,16-hexaoxanaphtho [2,3- b]cyclooctadecin) in the expected tripod arrangement, while the perchlorate anion links naphthyl groups in the crystal through C-H...O-Cl-O...H-C interactions. Thermal motion analysis indicates that the tert-butylammonium group and the perchlorate anion each librate with respect to the host, with amplitudes of 6.2 (4) and 11.4 (2) degrees, respectively.
