Imidazolidinone with endocyclic ammonium N atom Russ.Chem.Bull., Int.Ed., Vol. 58, No. 1, January, 2009
239
The molecular packing in the crystal structure of comꢀ
pound 1 can be described as a system of corrugated
layers consisting of parallel hydrogenꢀbonded chains,
which are in the perpendicular arrangement in the
adjacent layers.
O(2)
C(6)
C(2)
N(1)
C(7)
N(3)
C(8)
O(21)
S(20)
O(23)
C(5)
O(10)
Experimental
С(4)
C(14)
C(10)
C(9)
C(11)
F(22)
O(22)
C(20)
The 1H NMR spectrum was recorded on a Bruker MSLꢀ400
instrument operating at 250 MHz with respect to the signals for
the residual protons of the deuterated solvent (DMSOꢀd6) at 20 °C.
The IR spectrum of a crystalline sample was measured in an KBr
pellet on an URꢀ20 spectrophotometer in the 400—3600 cm–1
region.
C(15)
C(13)
C(12)
F(23)
F(21)
O(12)
5ꢀ(2,4ꢀDihydroxyꢀ3ꢀmethylphenyl)ꢀ1,1,3ꢀtrimethylꢀ2ꢀoxoꢀ
imidazolidinium triflate (1). A solution of 1ꢀ(2,2ꢀdimethoxyethyl)ꢀ
1,3,3ꢀtrimethylurea (1.53 g, 8.06 mmol), 2ꢀmethylresorcinol
(1.0 g, 8.06 mmol), and trifluoromethanesulfonic acid (2.41 g,
16.13 mmol) in dioxane (10 mL) was kept at 110 °C for 8 h.
Then the solvent was removed, ethanol (3 mL) was added to the
residue, and the reaction mixture was kept for 4 h. The precipiꢀ
tate that formed was filtered off, washed with diethyl ether, and
dried in vacuo. The yield was 1.61 g (44.5%), m.p. 154 °C.
Found (%): C, 41.98; H, 4.68; N, 7.10. C14H19F3N2O6S.
Calculated (%): C, 42.00; H, 4.78; N, 7.00. 1H NMR, δ: 2.05
(s, 3 H, C(15)H3); 2.72 (s, 3 H, C(6)H3); 3.04 (s, 3 H, C(7)H3);
Fig. 1. Molecular structure of compound 1 with displacement
ellipsoids drawn at the 50% probability level.
from this plane by 0.513(4) Å. The resorcinol substituent
at the C(5) atom is in the equatorial position and is
unsymmetrically twisted around the C(5)—C(9) bond.
The plane of the resorcinol substituent does not coincide
with the bisecting plane of the C(4)—C(5)—N(1) angle
and is almost orthogonal to the N(1)—C(5) bond (N(1)—
C(5)—C(9)—C(10), –96.4(4)°; C(4)—C(5)—C(9)—C(14),
–29.5(5)°; H(5)—C(5)—C(9)—C(14), 24°). The N(3)
atom has a trigonalꢀplanar coordination. The C(2)—N(3)
bond (1.303(6) Å) is strongly shortened, which is indicaꢀ
tive of the conjugation between the lone pair and the
C=O bond. A slight elongation of the C=O bond to
1.197(5) Å is also consistent with this fact. The geometric
parameters of the resorcinol substituent and the anion
have standard values.
1
3.11 (s, 3 H, C(8)H3); 3.77 (dd, 1 H, C(4)H, JH,H = 8.05 Hz,
2JH,H = 10.73 Hz); 4.16 (t, 1 H, C(5)H, 1JH,H = 10.73 Hz); 5.66
1
2
(dd, 1 H, C(4)H, JH,H = 8.05 Hz, JH,H = 10.73 Hz); 6.50 (d,
1 H, C(13)H, 1JH,H = 8.71 Hz); 7.22 (d, 1 H, C(14)H, JH,H
=
1
8.71 Hz). IR, ν/cm–1: 1610 (arom.), 1819 (C=O), 3334 (OH).
Xꢀray diffraction study of compound 1. Crystals are orthoꢀ
rhombic, C13H19N2O3•CF3SO3, M = 400.38, a = 28.584(4) Å,
3
b = 23.566(5) Å, c = 10.518(3) Å, V = 7085(3) Å , Z = 16,
dcalc = 1.501 g cm–3, space group Fdd2. The intensities of 3150
independent reflections (2012 reflections were with I ≥ 2σ)
were measured on an EnrafꢀNonius CADꢀ4 diffractometer
(ω/2θꢀscanning technique, θ ≤ 26.29°, λ(MoꢀKα), graphite
monochromator, Rint = 0.0515) at 20 °C. The intensities of three
check reflections showed no decrease in the course of Xꢀray data
collection. The absorption correction was not applied because
the absorption coefficient was small (μ(Mo) = 2.47 cm–1). The
stability of the crystals was monitored at 2 h intervals by measurꢀ
ing three check reflections. The orientation was monitored at
200 reflection intervals by centering two check reflections. The
structure was solved by direct methods using the SIR program14
and refined first isotropically and then anisotropically with the
use of the SHELXꢀ97 program package.15 The hydrogen atoms
at the O(10) and O(12) atoms were located in difference elecꢀ
tron density maps and refined isotropically. The coordinates of
the other hydrogen atoms were calculated based on the stereoꢀ
chemical criteria and refined using a riding model. All calculaꢀ
tions were carried out with the use of the MolEN16 and WinGX17
programs. The final R factors were Rob = 0.0508 and Rwob = 0.1124
(GOOF = 0.978) based on 2012 independent reflections with
In the crystal structure of compound 1, the cations
and anions form infinite zigzag chains along the diagonal
a0c through hydrogen bonds between the hydrogen atoms
of the hydroxy groups of the cations and the oxygen
atoms of the anions (Fig. 2). The hydrogen bond paramꢀ
eters are as follows: for O(10)—H(10)…O(22´) (–3/2 – x,
1 – y, –1/2 + z), O(10)—H(10), 0.85(3) Å; H(10)…O(22´),
1.98(4) Å; O(10)…O(22´), 2.803(5) Å; O(10)—H(10)…O(22´),
162(5)°; for O(12)—H(12)...O(23″) (–7/4 – x, 1/4 + y,
1/4 + z), O(12)—H(12), 0.84(4) Å; H(12)…O(23″), 1.97(4) Å;
O(12)…O(23″), 2.800(5) Å; O(12)—H(12)…O(23″), 172(5)°.
H(10)
O(10)
O(23´)
O(22″)
H(12)
2
F2 ≥ 2σ . The intermolecular interactions were analyzed and the
O(23″)
O(22´)
O(12)
figures were drawn with the use of the PLATON program.18
Complete tables of atomic coordinates, thermal parameters,
bond lengths, and bond angles were deposited with the Cambridge
Structural Database.
Fig. 2. Hydrogen bonds in the crystal structure of compound 1.
Gazizov
