Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009835/os1113sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009835/os1113Isup2.hkl |
CCDC reference: 152627
Compound (I) was obtained by reacting 1-(2-hydroxyethyl)imidazolidin-2-one with a large excess of methyl 2-methylprop-2-enoate, as reported previously by Riondel & Herbst (1995). Slow recrystallization from a solution of (I) in methyl methacrylate at room temperature afforded colourless tabular crystals suitable for X-ray analysis.
All H atoms were located from difference Fourier maps and were refined isotropically.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXTL-Plus.
C9H14N2O3 | F(000) = 424 |
Mr = 198.22 | Dx = 1.319 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.6304 (8) Å | Cell parameters from 39 reflections |
b = 11.3329 (10) Å | θ = 5–25° |
c = 7.0306 (6) Å | µ = 0.10 mm−1 |
β = 97.197 (6)° | T = 293 K |
V = 998.42 (14) Å3 | Tabular, colourless |
Z = 4 | 0.4 × 0.3 × 0.2 mm |
Siemens R3m/V 4 diffractometer | 1287 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
ω/2θ scans | h = −14→14 |
Absorption correction: ψ-scan (North et al., 1968) | k = 0→13 |
Tmin = 0.933, Tmax = 0.980 | l = 0→8 |
1866 measured reflections | 3 standard reflections every 97 reflections |
1739 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.032 | All H-atom parameters refined |
wR(F2) = 0.090 | w = 1/[σ2(Fo2) + (0.0521P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
1737 reflections | Δρmax = 0.16 e Å−3 |
184 parameters | Δρmin = −0.12 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc2=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.024 (8) |
C9H14N2O3 | V = 998.42 (14) Å3 |
Mr = 198.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.6304 (8) Å | µ = 0.10 mm−1 |
b = 11.3329 (10) Å | T = 293 K |
c = 7.0306 (6) Å | 0.4 × 0.3 × 0.2 mm |
β = 97.197 (6)° |
Siemens R3m/V 4 diffractometer | 1287 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.933, Tmax = 0.980 | 3 standard reflections every 97 reflections |
1866 measured reflections | intensity decay: none |
1739 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.090 | All H-atom parameters refined |
S = 0.95 | Δρmax = 0.16 e Å−3 |
1737 reflections | Δρmin = −0.12 e Å−3 |
184 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.37741 (10) | 0.01561 (10) | 0.31547 (18) | 0.0479 (4) | |
C2 | 0.40906 (11) | −0.09828 (12) | 0.3120 (2) | 0.0425 (4) | |
O2 | 0.45777 (9) | −0.14318 (9) | 0.18905 (16) | 0.0588 (3) | |
N3 | 0.37725 (12) | −0.15247 (13) | 0.4640 (2) | 0.0635 (4) | |
H3 | 0.4044 (14) | −0.2177 (18) | 0.505 (3) | 0.069 (6)* | |
C4 | 0.33111 (16) | −0.07326 (15) | 0.5895 (3) | 0.0585 (5) | |
H4 | 0.2625 (16) | −0.0998 (16) | 0.620 (2) | 0.070 (5)* | |
H4' | 0.3752 (16) | −0.0636 (19) | 0.714 (3) | 0.095 (7)* | |
C5 | 0.32236 (15) | 0.04172 (14) | 0.4776 (2) | 0.0537 (4) | |
H5 | 0.2518 (17) | 0.0634 (17) | 0.440 (3) | 0.077 (6)* | |
H5' | 0.3614 (14) | 0.1111 (17) | 0.559 (2) | 0.072 (5)* | |
C6 | 0.38685 (13) | 0.09691 (14) | 0.1601 (2) | 0.0514 (4) | |
H6 | 0.4253 (13) | 0.1710 (16) | 0.216 (3) | 0.070 (5)* | |
H6' | 0.4270 (12) | 0.0529 (14) | 0.070 (2) | 0.053 (4)* | |
C7 | 0.28199 (14) | 0.13312 (14) | 0.0510 (3) | 0.0560 (4) | |
H7 | 0.2940 (14) | 0.1761 (17) | −0.068 (3) | 0.075 (5)* | |
H7' | 0.2357 (14) | 0.1804 (16) | 0.123 (2) | 0.063 (5)* | |
O8 | 0.22224 (8) | 0.02686 (9) | −0.00198 (16) | 0.0550 (3) | |
O9 | 0.11230 (10) | 0.12760 (11) | −0.21436 (19) | 0.0756 (4) | |
C9 | 0.13597 (12) | 0.03736 (13) | −0.1317 (2) | 0.0485 (4) | |
C10 | 0.07659 (12) | −0.07629 (14) | −0.1588 (2) | 0.0500 (4) | |
C11 | −0.01372 (16) | −0.07624 (19) | −0.2786 (3) | 0.0686 (5) | |
H11 | −0.0539 (16) | −0.1449 (19) | −0.303 (3) | 0.086 (6)* | |
H11' | −0.0353 (16) | −0.001 (2) | −0.343 (3) | 0.090 (7)* | |
C12 | 0.11847 (19) | −0.18016 (17) | −0.0493 (3) | 0.0681 (5) | |
H12 | 0.0709 (14) | −0.2483 (19) | −0.076 (3) | 0.078 (6)* | |
H12' | 0.1158 (19) | −0.164 (2) | 0.100 (4) | 0.131 (9)* | |
H12'' | 0.1830 (17) | −0.197 (2) | −0.070 (3) | 0.088 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0581 (7) | 0.0345 (6) | 0.0532 (8) | 0.0054 (5) | 0.0146 (6) | 0.0019 (5) |
C2 | 0.0412 (7) | 0.0326 (7) | 0.0539 (9) | −0.0034 (6) | 0.0060 (7) | −0.0030 (6) |
O2 | 0.0674 (7) | 0.0437 (6) | 0.0695 (7) | 0.0026 (5) | 0.0242 (6) | −0.0103 (5) |
N3 | 0.0768 (10) | 0.0436 (8) | 0.0755 (10) | 0.0131 (7) | 0.0305 (8) | 0.0138 (7) |
C4 | 0.0608 (10) | 0.0580 (10) | 0.0595 (11) | 0.0008 (8) | 0.0184 (9) | 0.0019 (8) |
C5 | 0.0525 (9) | 0.0515 (9) | 0.0586 (10) | 0.0079 (8) | 0.0125 (8) | −0.0030 (8) |
C6 | 0.0570 (9) | 0.0401 (8) | 0.0579 (10) | −0.0031 (7) | 0.0102 (8) | 0.0039 (7) |
C7 | 0.0678 (10) | 0.0335 (8) | 0.0647 (10) | −0.0047 (7) | 0.0008 (9) | 0.0051 (7) |
O8 | 0.0616 (7) | 0.0346 (6) | 0.0659 (7) | −0.0044 (5) | −0.0035 (6) | 0.0042 (5) |
O9 | 0.0836 (9) | 0.0538 (8) | 0.0835 (9) | 0.0025 (6) | −0.0122 (7) | 0.0197 (7) |
C9 | 0.0541 (9) | 0.0453 (9) | 0.0472 (9) | 0.0036 (7) | 0.0108 (7) | 0.0007 (7) |
C10 | 0.0520 (9) | 0.0495 (9) | 0.0512 (9) | −0.0012 (7) | 0.0171 (8) | −0.0059 (7) |
C11 | 0.0620 (12) | 0.0690 (13) | 0.0750 (13) | −0.0032 (10) | 0.0094 (10) | −0.0086 (10) |
C12 | 0.0752 (13) | 0.0455 (10) | 0.0841 (15) | −0.0091 (9) | 0.0122 (11) | 0.0050 (9) |
N1—C2 | 1.3523 (18) | C6—H6' | 0.994 (16) |
N1—C5 | 1.438 (2) | C7—O8 | 1.4450 (19) |
N1—C6 | 1.4451 (19) | C7—H7 | 0.998 (19) |
C2—O2 | 1.2318 (16) | C7—H7' | 0.981 (18) |
C2—N3 | 1.3374 (19) | O8—C9 | 1.3357 (18) |
O2—N3i | 2.9151 (18) | O9—C9 | 1.1956 (18) |
N3—C4 | 1.433 (2) | C9—C10 | 1.491 (2) |
N3—H3 | 0.85 (2) | C10—C11 | 1.330 (3) |
C4—C5 | 1.519 (2) | C10—C12 | 1.468 (3) |
C4—H4 | 0.968 (19) | C11—H11 | 0.93 (2) |
C4—H4' | 0.98 (2) | C11—H11' | 0.99 (2) |
C5—H5 | 0.93 (2) | C12—H12 | 0.98 (2) |
C5—H5' | 1.058 (19) | C12—H12' | 1.07 (3) |
C6—C7 | 1.502 (2) | C12—H12'' | 0.87 (2) |
C6—H6 | 1.024 (18) | ||
C2—N1—C5 | 112.60 (12) | N1—C6—H6' | 105.0 (9) |
C2—N1—C6 | 122.83 (13) | C7—C6—H6' | 107.4 (9) |
C5—N1—C6 | 124.16 (12) | H6—C6—H6' | 113.7 (13) |
O2—C2—N3 | 126.69 (14) | O8—C7—C6 | 107.61 (12) |
O2—C2—N1 | 125.58 (14) | O8—C7—H7 | 108.6 (11) |
N3—C2—N1 | 107.73 (13) | C6—C7—H7 | 110.2 (10) |
C2—O2—N3i | 122.55 (9) | O8—C7—H7' | 105.2 (10) |
C2—N3—C4 | 113.00 (14) | C6—C7—H7' | 115.4 (10) |
C4—N3—O2 | 138.32 (12) | H7—C7—H7' | 109.4 (15) |
C2—N3—H3 | 121.4 (12) | C9—O8—C7 | 117.19 (12) |
C4—N3—H3 | 120.9 (12) | O9—C9—O8 | 122.76 (15) |
N3—C4—C5 | 103.11 (13) | O9—C9—C10 | 125.86 (15) |
N3—C4—H4 | 112.9 (11) | O8—C9—C10 | 111.38 (13) |
C5—C4—H4 | 111.9 (11) | C11—C10—C12 | 123.79 (17) |
N3—C4—H4' | 112.9 (12) | C11—C10—C9 | 117.28 (16) |
C5—C4—H4' | 111.2 (13) | C12—C10—C9 | 118.91 (15) |
H4—C4—H4' | 105.0 (15) | C10—C11—H11 | 121.3 (13) |
N1—C5—C4 | 102.89 (12) | C10—C11—H11' | 117.2 (12) |
N1—C5—H5 | 111.6 (12) | H11—C11—H11' | 121.5 (18) |
C4—C5—H5 | 112.4 (12) | C10—C12—H12 | 111.1 (11) |
N1—C5—H5' | 110.1 (9) | C10—C12—H12' | 109.0 (14) |
C4—C5—H5' | 110.9 (10) | H12—C12—H12' | 103.0 (17) |
H5—C5—H5' | 108.9 (15) | C10—C12—H12'' | 111.7 (15) |
N1—C6—C7 | 114.15 (14) | H12—C12—H12" | 111.5 (18) |
N1—C6—H6 | 108.1 (10) | H12'—C12—H12" | 110 (2) |
C7—C6—H6 | 108.6 (10) | ||
N1—C6—C7—O8 | −50.8 (2) |
Symmetry code: (i) x, −y−1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H14N2O3 |
Mr | 198.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 12.6304 (8), 11.3329 (10), 7.0306 (6) |
β (°) | 97.197 (6) |
V (Å3) | 998.42 (14) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.4 × 0.3 × 0.2 |
Data collection | |
Diffractometer | Siemens R3m/V 4 diffractometer |
Absorption correction | ψ-scan (North et al., 1968) |
Tmin, Tmax | 0.933, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1866, 1739, 1287 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.090, 0.95 |
No. of reflections | 1737 |
No. of parameters | 184 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.16, −0.12 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1991), SHELXTL-Plus.
N1—C2 | 1.3523 (18) | C4—C5 | 1.519 (2) |
N1—C5 | 1.438 (2) | C6—C7 | 1.502 (2) |
N1—C6 | 1.4451 (19) | C7—O8 | 1.4450 (19) |
C2—O2 | 1.2318 (16) | O8—C9 | 1.3357 (18) |
C2—N3 | 1.3374 (19) | O9—C9 | 1.1956 (18) |
O2—N3i | 2.9151 (18) | C9—C10 | 1.491 (2) |
N3—C4 | 1.433 (2) | C10—C11 | 1.330 (3) |
N3—H3 | 0.85 (2) | C10—C12 | 1.468 (3) |
C2—N1—C5 | 112.60 (12) | N1—C6—C7 | 114.15 (14) |
C2—N1—C6 | 122.83 (13) | O8—C7—C6 | 107.61 (12) |
C5—N1—C6 | 124.16 (12) | C9—O8—C7 | 117.19 (12) |
O2—C2—N3 | 126.69 (14) | O9—C9—O8 | 122.76 (15) |
O2—C2—N1 | 125.58 (14) | O9—C9—C10 | 125.86 (15) |
N3—C2—N1 | 107.73 (13) | O8—C9—C10 | 111.38 (13) |
C2—N3—C4 | 113.00 (14) | C11—C10—C12 | 123.79 (17) |
N3—C4—C5 | 103.11 (13) | C11—C10—C9 | 117.28 (16) |
N1—C5—C4 | 102.89 (12) | C12—C10—C9 | 118.91 (15) |
N1—C6—C7—O8 | −50.8 (2) |
Symmetry code: (i) x, −y−1/2, z−1/2. |
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2-(2-Oxoimidazolidinyl)ethyl 2-methylprop-2-enoate, or more simply ethylimidazolidone methacrylate, (I), is used commercially as an additive to paints, paper, textiles and leather because it favours adhesiveness on wet surfaces. It is synthesized by a transesterification reaction between 1-(2-hydroxyethyl)imidazolidin-2-one and methyl 2-methylprop-2-enoate. The synthesis requires a catalyst in order to achieve a complete conversion into the ester (I) at temperature below 373 K and several catalysts have recently been patented (Riondel & Herbst, 1995, 1994; Herbst & Riondel, 1994). Compound (I) readily forms large crystals (up to 2 cm wide) from solution in methyl methacrylate and we wished to understand the origin of this behaviour, hence the present study. It should also be noted here that numerous reports have been devoted to the crystallographic structures of compounds containing imidazolidin-2-one as a part of a bicyclo[3.3.0] unit, for instance in biotin. However, only three X-ray crystal structures are known so far in which an uncomplexed imidazolidin-2-one group is substituted on at least one of the N atoms and does not feature substituents directly grafted onto its ethylene moiety (Peeters et al., 1984; Ueda et al., 1986; Jensen, 1988). \sch
The refined molecular structure of (I) is shown in Fig. 1 together with the atom-numbering scheme. Bond lengths and angles in the imidazolidin-2-one ring compare favourably with the values observed in niridazole (Peeters et al., 1984) and in the irindalone ion (Jensen, 1988). The imidazolidin-2-one ring is almost planar, with a mean deviation of 0.034 (2) Å from the least-squares plane through the atoms N1, C2, O2, N3, C4 and C5. A similar planar arrangement was found in the case of niridazole (Peeters et al., 1984), but the ring of irindalone has a significantly more twisted conformation (mean deviation 0.097 Å; Jensen, 1988).
The crystal of (I) is composed of layers packed along the b axis. In each layer, the imidazolidin-2-one rings are parallel to each other. The stacking of the layers is supported by hydrogen bonding between O2 and N3i, as shown in Fig. 2 [symmetry code: (i) x, −1/2 − y, z − 1/2]. The N3i···O2 distance between two hydrogen-bonded molecules is 2.915 (2) Å. These intermolecular hydrogen bond interactions do not influence the conformation of the molecule. Indeed, an MM2 computation (Allinger, 1977) starting from the crystallographic conformation of (I) brings only negligible changes in the molecular conformation. The relative orientation of the ester and imidazolidin-2-one groups remains essentially unaltered and the ethyl groups keep their fully staggered conformation as found in the solid state. The only significant difference between the crystallographic and MM2 structures of (I) is a reduction of the C2—N1—C6—C7 torsion angle from −110.9 to 90.2° (query signs). The two protons on C6 are then more staggered with respect to the imidazolidone.
The large size of the crystals of (I) is tentatively ascribed to the energetically favourable arrangement of the molecule and to the hydrogen-bond network, although the latter is not oriented along the principal growing direction.