1
62
KOVALENKO et al.
–1
For the mixture of crystals, IR (
925, 2855, 2084, 2017, 1824, 1736, 1728, 1469, 1426, are given in Table 1. A semiempirical absorption corꢀ
375, 1318, 1228, 1187, 1153, 969, 829, 806, 756, 673, rection was applied with the SADABS program [14]
ν
, cm ): 3442, graphic parameters and the data collection statistics
2
1
5
99, 560, 452.
from the intensities of equivalent reflections. The
structures were solved by the direct methods and
Synthesis of inclusion compound II. A degassed
refined anisotropically (for the nonꢀhydrogen atoms)
solution of CoCl2
water (40 ml) and {Cyclen@CB[8]}
0.060 g, 0.032 mmol) was refluxed in an inert atmoꢀ
sphere for 2 h and then concentrated to half the initial
volume by heating in air. The large crimson crystals
that formed after a day were filtered off, washed with a
small amount of cold water, and dried in air. When
heated, the crystals are moderately soluble in water.
⋅
6H O (0.142 g, 0.597 mmol) in
2
2
by the fullꢀmatrix leastꢀsquares method on
F
with the
⋅
4HCl 13H O
⋅
2
SHELXꢀ97 program package [15]. The hydrogen
atoms of cucurbit[8]uril and the organic ligands were
located geometrically and refined using a rigidꢀbody
model. The water H atoms were not refined. The
atomic coordinates have been deposited with the
Cambridge Crystallographic Data Collection
(
(
nos. 779413–779415 for structures I–III, respecꢀ
The yield was 0.050 g (76% from {Cyclen@CB[8]}
HCl 13H O).
⋅
tively; deposit@ccdc.cam.ac.uk or http://www.ccdc.
cam.ac.uk).
4
⋅
2
For C H N O Cl Co (with the loss of five water molecules)
56
100 36 32
3
RESULTS AND DISCUSSION
anal. calcd. (%): C, 34.41;
Found (%): C, 34.5;
H, 5.16;
H, 5.0;
N, 25.79.
N, 25.6.
Macrocyclic molecules of cucurbit[
n]urils
(
C H N O , CB[ = 5–10) having an open
n]; n
6n
6n
4n
2n
–
1
hydrophobic cavity are cavitands; i.e., they can
host guest molecules of an appropriate size to produce
inclusion compounds [13, 16]. Inclusion compounds
IR (ν, cm ): 3428, 2963, 2934, 2875, 1724, 1471,
1
7
424, 1384, 1316, 1230, 1189, 1154, 968, 830, 807,
57, 674, 451, 370.
I–III were obtained by reactions of iron(0) pentacarꢀ
–1
–1
UVꢀVIS (
191).
ESI MS (m/z (I, %)): 779.7 (80) {[Co(Cyclen)] + in the CB[8] cavity. In this case, a direct synthesis from
λ
, nm ( , l mol cm )): 365 (153), 521
ε
bonyl and cobalt(II) and nickel(II) chlorides with the
(
polyamine ligands cyclam and cyclen preꢀembedded
2+
2+
2+
CB[8]} , 527.5 (100) {[Co(Cyclen)] + CB[8] + metal complexes with cyclam (or cyclen) as guests and
+
3+
Na }
.
CB[8] as a host is impossible: the complexes are conꢀ
formationally more rigid than the free ligands, which
precludes them from entering the portal of the cavꢀ
itand [10, 11].
Synthesis of inclusion compound III. A mixture of
Cyclen@CB[8]} · 4HCl · 13H O (0.060 g,
.032 mmol) and a solution of NiCl · 6H O (0.144 g,
{
2
0
0
2
2 2
.606 mmol) in water (14 ml) was refluxed in air for
h. Slow cooling produced pale blue crystals, which mixture of {Cyclam@CB[8]}
Inclusion compound
I
was obtained by heating a
4HCl 18H O, Fe(CO)5,
⋅
⋅
2
were filtered off, washed with a small amount of cold and water in a sealed tube at 130°C. After the tube was
water, and dried in air. When heated, the crystals are cooled, the solution was left for a month to produce a
moderately soluble in water. The yield was 0.050 g difficultꢀtoꢀseparate mixture of orange and pale green
(
84% from {Cyclen@CB[8]}
⋅
4HCl
⋅
13H O).
crystals.
2
Based on IR spectra, one can assume that orange
crystals are binuclear iron carbonyl formed under the
reaction conditions. The IR spectrum of the reaction
mixture shows intense bands due to the vibrations of
For C H N O Cl Ni
92 36 28
56
2
anal. calcd. (%):
Found (%):
C, 36.09;
H, 5.04;
H, 5.1;
N, 27.07.
N, 27.0.
C, 36.4;
the terminal and bridging CO groups in Fe (CO)9
2
–
1
(
2084, 2017, and 1824 cm [17]). Characteristic
bands of CB[8] appear in the 1800–400 cm range;
the bands at 2925 and 2855 cm can be assigned to the
–1
IR (
ν
, cm ): 3433, 3001, 2926, 1725, 1470, 1425,
–1
1
7
374, 1317, 1288, 1229, 1187, 1154, 968, 829, 806,
56, 673, 628, 446.
–1
N–H stretching vibrations in cyclam.
2+
ESI MS (m/z (I, %)): 779.2 (100) {[Ni(Cyclen)] +
According to Xꢀray diffraction data, pale green
crystals selected from the mixture obtained are incluꢀ
+
3+
2+
CB[8] + Na } , 527.2 (25) {[Ni(Cyclen)]
+
2+
CB[8]}
.
sion compound
Xꢀray diffraction analysis. Reflection intensities the cavity of each cavitand molecule. A slightly disꢀ
from compounds III were collected according to a torted octahedral environment of the iron atom is
standard procedure at 150 K (Mo radiation, made up of four N atoms of cyclam, the carbonyl C
.71073 Å, graphite monochromator). Crystalloꢀ atom, and the O atom of the formate anion formed
I, in which the iron(II) complex is in
I–
K
λ
=
α
0
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 37
No. 3
2011