The X-ray crystal structure determinations of four new oligomeric cyclophane
esters are reported. They are: (3a) monomeric 1,4-xylylene
(1,4-phenylene)diacetate,
P21/n
(No. 14), a 5·959(5), b
15·795(5), c 8·094(5) Å, β
108·060(5)°, V 724·3(8)
Å3 , Z 2,
R1(2σ) 0·0522,
wR2 0·125; (3b) monomeric
1,4-xylylene (1,4-phenylene)dipropionate,
P21/c
(No. 14), a 5·878(1), b
14·642(2), c 18·909(2) Å, β
96·00(10)°, V 1618·5(4)
Å3 , Z 4,
R1(2σ) 0·053,
wR2 0·165; (3c) dimeric
1,4-xylylene (1,4-phenylene)diacetate,
P-1 (No. 2),
a 14·633(2), b
17·529(2), c 5·736(1) Å, α
98·30(10), β 90·60(10), γ 95·40(10)°,
V 1449·0(4) Å3,
Z 2,
R1(2σ) 0·057,
wR2 0·158; (3d) dimeric
1,4-xylylene (1,4-phenylene)dipropionate,
P21/a
(No. 14), a 8·145(1), b
11·379(2), c 17·401(2) Å, β
101·40(10)°, V 1580·9(4)
Å3, Z 4,
R1(2σ) 0·034,
wR2 0·095. Monomeric
cyclophanes (3a,b) exhibit a well defined cleft, while dimeric (3c,d) adopt a
flat conformation devoid of cavities. Binding properties were determined by
1H n.m.r. titrations in CDCl3 at
T = 296 K. Complexation experiments with
quaternary ammonium salts revealed that host (3c) possesses appreciable
binding ability toward N-methylpyridinium
(–ΔG° = 5·9 kJ
mol-1), tetramethylammonium
(–ΔG° = 8·8 kJ
mol-1) and acetylcholine
(–ΔG° = 7·5 kJ
mol-1) cations, despite its lack of a preorganized
cavity.