TY - JOUR
T1 - Molecular complexes of diethyl N, N ′-1,3-phenyldioxalamate and resorcinols
T2 - Conformational switching through intramolecular three-centered hydrogen-bonding
AU - González-González, Juan Saulo
AU - Martínez-Martínez, Francisco J.
AU - García-Báez, Efrén V.
AU - Cruz, Alejandro
AU - Morín-Sánchez, Luis M.
AU - Rojas-Lima, Susana
AU - Padilla-Martínez, Itzia I.
PY - 2014/2/5
Y1 - 2014/2/5
N2 - The mechanochemically induced complexation between diethyl N,N′-1,3-phenyldioxalamate tweezers and resorcinol, orcinol, 4,6-di-tert-butyl-1,3-benzenediol, and 4-hexyl-1,3-benzenediol is described. IR-spectroscopy, X-ray powder diffraction, 13C CPMAS, and single X-ray diffraction allowed establishing the structures of the complexes as hydrogen-bonded heterodimers and heterotetramers. Complexation occurs through O-H···O=C hydrogen-bonding interactions with the participation of phenolic OH and amide carbonyl groups. The initial conformation and steric factors coming from the 1,3-benzenediols exert a strong influence on the final structure of the complex formed. Complexation twists both oxalyl arms by 180°, strengthens the intramolecular (amide) CO···H(Csp2)···OC(amide) three-centered hydrogen bond, and moves apart the oxalyl arms to allow the accommodation of the 1,3-benzenediol inside the cavity. The supramolecular architectures of the complexes in 1-D are directed by R1 2(6), R22(10), and R12(6) adjacent hydrogen-bonding ring motifs; meanwhile, the 2-D and 3-D arrays are driven by multipolar interactions. Theoretical DFT calculations at the B3LYP/6-31G(d,p) level of theory were performed to support the experimental findings. The complexes herein reported constitute the first examples of molecular complexes with phenyldioxalamate.
AB - The mechanochemically induced complexation between diethyl N,N′-1,3-phenyldioxalamate tweezers and resorcinol, orcinol, 4,6-di-tert-butyl-1,3-benzenediol, and 4-hexyl-1,3-benzenediol is described. IR-spectroscopy, X-ray powder diffraction, 13C CPMAS, and single X-ray diffraction allowed establishing the structures of the complexes as hydrogen-bonded heterodimers and heterotetramers. Complexation occurs through O-H···O=C hydrogen-bonding interactions with the participation of phenolic OH and amide carbonyl groups. The initial conformation and steric factors coming from the 1,3-benzenediols exert a strong influence on the final structure of the complex formed. Complexation twists both oxalyl arms by 180°, strengthens the intramolecular (amide) CO···H(Csp2)···OC(amide) three-centered hydrogen bond, and moves apart the oxalyl arms to allow the accommodation of the 1,3-benzenediol inside the cavity. The supramolecular architectures of the complexes in 1-D are directed by R1 2(6), R22(10), and R12(6) adjacent hydrogen-bonding ring motifs; meanwhile, the 2-D and 3-D arrays are driven by multipolar interactions. Theoretical DFT calculations at the B3LYP/6-31G(d,p) level of theory were performed to support the experimental findings. The complexes herein reported constitute the first examples of molecular complexes with phenyldioxalamate.
UR - http://www.scopus.com/inward/record.url?scp=84893709408&partnerID=8YFLogxK
U2 - 10.1021/cg401500k
DO - 10.1021/cg401500k
M3 - Artículo
SN - 1528-7483
VL - 14
SP - 628
EP - 642
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 2
ER -