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In the crystal structure of the title compound, C9H14N2O3, the molecules are linked by N-H...O=C bonds into chains parallel to [001]. Large crystals are readily obtained, presumably because of the hydrogen bonds and an energetically stable conformation of the mol­ecule.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100009835/os1113sup1.cif
Contains datablocks methacry, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100009835/os1113Isup2.hkl
Contains datablock I

CCDC reference: 152627

Comment top

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.

Experimental top

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.

Refinement top

All H atoms were located from difference Fourier maps and were refined isotropically.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labelling scheme and with 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The crystal packing in (I). Dashed lines represent hydrogen bonds.
2-(2-oxoimidazolidinyl)ethyl 2-methylprop-2-enoate top
Crystal data top
C9H14N2O3F(000) = 424
Mr = 198.22Dx = 1.319 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 12.6304 (8) ÅCell parameters from 39 reflections
b = 11.3329 (10) Åθ = 5–25°
c = 7.0306 (6) ŵ = 0.10 mm1
β = 97.197 (6)°T = 293 K
V = 998.42 (14) Å3Tabular, colourless
Z = 40.4 × 0.3 × 0.2 mm
Data collection top
Siemens R3m/V 4
diffractometer
1287 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
Graphite monochromatorθmax = 25.0°, θmin = 2.4°
ω/2θ scansh = 1414
Absorption correction: ψ-scan
(North et al., 1968)
k = 013
Tmin = 0.933, Tmax = 0.980l = 08
1866 measured reflections3 standard reflections every 97 reflections
1739 independent reflections intensity decay: none
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032All 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 reflectionsΔρmax = 0.16 e Å3
184 parametersΔρmin = 0.12 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc2=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.024 (8)
Crystal data top
C9H14N2O3V = 998.42 (14) Å3
Mr = 198.22Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.6304 (8) ŵ = 0.10 mm1
b = 11.3329 (10) ÅT = 293 K
c = 7.0306 (6) Å0.4 × 0.3 × 0.2 mm
β = 97.197 (6)°
Data collection top
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 = 0.9803 standard reflections every 97 reflections
1866 measured reflections intensity decay: none
1739 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.090All H-atom parameters refined
S = 0.95Δρmax = 0.16 e Å3
1737 reflectionsΔρmin = 0.12 e Å3
184 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
N10.37741 (10)0.01561 (10)0.31547 (18)0.0479 (4)
C20.40906 (11)0.09828 (12)0.3120 (2)0.0425 (4)
O20.45777 (9)0.14318 (9)0.18905 (16)0.0588 (3)
N30.37725 (12)0.15247 (13)0.4640 (2)0.0635 (4)
H30.4044 (14)0.2177 (18)0.505 (3)0.069 (6)*
C40.33111 (16)0.07326 (15)0.5895 (3)0.0585 (5)
H40.2625 (16)0.0998 (16)0.620 (2)0.070 (5)*
H4'0.3752 (16)0.0636 (19)0.714 (3)0.095 (7)*
C50.32236 (15)0.04172 (14)0.4776 (2)0.0537 (4)
H50.2518 (17)0.0634 (17)0.440 (3)0.077 (6)*
H5'0.3614 (14)0.1111 (17)0.559 (2)0.072 (5)*
C60.38685 (13)0.09691 (14)0.1601 (2)0.0514 (4)
H60.4253 (13)0.1710 (16)0.216 (3)0.070 (5)*
H6'0.4270 (12)0.0529 (14)0.070 (2)0.053 (4)*
C70.28199 (14)0.13312 (14)0.0510 (3)0.0560 (4)
H70.2940 (14)0.1761 (17)0.068 (3)0.075 (5)*
H7'0.2357 (14)0.1804 (16)0.123 (2)0.063 (5)*
O80.22224 (8)0.02686 (9)0.00198 (16)0.0550 (3)
O90.11230 (10)0.12760 (11)0.21436 (19)0.0756 (4)
C90.13597 (12)0.03736 (13)0.1317 (2)0.0485 (4)
C100.07659 (12)0.07629 (14)0.1588 (2)0.0500 (4)
C110.01372 (16)0.07624 (19)0.2786 (3)0.0686 (5)
H110.0539 (16)0.1449 (19)0.303 (3)0.086 (6)*
H11'0.0353 (16)0.001 (2)0.343 (3)0.090 (7)*
C120.11847 (19)0.18016 (17)0.0493 (3)0.0681 (5)
H120.0709 (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)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0581 (7)0.0345 (6)0.0532 (8)0.0054 (5)0.0146 (6)0.0019 (5)
C20.0412 (7)0.0326 (7)0.0539 (9)0.0034 (6)0.0060 (7)0.0030 (6)
O20.0674 (7)0.0437 (6)0.0695 (7)0.0026 (5)0.0242 (6)0.0103 (5)
N30.0768 (10)0.0436 (8)0.0755 (10)0.0131 (7)0.0305 (8)0.0138 (7)
C40.0608 (10)0.0580 (10)0.0595 (11)0.0008 (8)0.0184 (9)0.0019 (8)
C50.0525 (9)0.0515 (9)0.0586 (10)0.0079 (8)0.0125 (8)0.0030 (8)
C60.0570 (9)0.0401 (8)0.0579 (10)0.0031 (7)0.0102 (8)0.0039 (7)
C70.0678 (10)0.0335 (8)0.0647 (10)0.0047 (7)0.0008 (9)0.0051 (7)
O80.0616 (7)0.0346 (6)0.0659 (7)0.0044 (5)0.0035 (6)0.0042 (5)
O90.0836 (9)0.0538 (8)0.0835 (9)0.0025 (6)0.0122 (7)0.0197 (7)
C90.0541 (9)0.0453 (9)0.0472 (9)0.0036 (7)0.0108 (7)0.0007 (7)
C100.0520 (9)0.0495 (9)0.0512 (9)0.0012 (7)0.0171 (8)0.0059 (7)
C110.0620 (12)0.0690 (13)0.0750 (13)0.0032 (10)0.0094 (10)0.0086 (10)
C120.0752 (13)0.0455 (10)0.0841 (15)0.0091 (9)0.0122 (11)0.0050 (9)
Geometric parameters (Å, º) top
N1—C21.3523 (18)C6—H6'0.994 (16)
N1—C51.438 (2)C7—O81.4450 (19)
N1—C61.4451 (19)C7—H70.998 (19)
C2—O21.2318 (16)C7—H7'0.981 (18)
C2—N31.3374 (19)O8—C91.3357 (18)
O2—N3i2.9151 (18)O9—C91.1956 (18)
N3—C41.433 (2)C9—C101.491 (2)
N3—H30.85 (2)C10—C111.330 (3)
C4—C51.519 (2)C10—C121.468 (3)
C4—H40.968 (19)C11—H110.93 (2)
C4—H4'0.98 (2)C11—H11'0.99 (2)
C5—H50.93 (2)C12—H120.98 (2)
C5—H5'1.058 (19)C12—H12'1.07 (3)
C6—C71.502 (2)C12—H12''0.87 (2)
C6—H61.024 (18)
C2—N1—C5112.60 (12)N1—C6—H6'105.0 (9)
C2—N1—C6122.83 (13)C7—C6—H6'107.4 (9)
C5—N1—C6124.16 (12)H6—C6—H6'113.7 (13)
O2—C2—N3126.69 (14)O8—C7—C6107.61 (12)
O2—C2—N1125.58 (14)O8—C7—H7108.6 (11)
N3—C2—N1107.73 (13)C6—C7—H7110.2 (10)
C2—O2—N3i122.55 (9)O8—C7—H7'105.2 (10)
C2—N3—C4113.00 (14)C6—C7—H7'115.4 (10)
C4—N3—O2138.32 (12)H7—C7—H7'109.4 (15)
C2—N3—H3121.4 (12)C9—O8—C7117.19 (12)
C4—N3—H3120.9 (12)O9—C9—O8122.76 (15)
N3—C4—C5103.11 (13)O9—C9—C10125.86 (15)
N3—C4—H4112.9 (11)O8—C9—C10111.38 (13)
C5—C4—H4111.9 (11)C11—C10—C12123.79 (17)
N3—C4—H4'112.9 (12)C11—C10—C9117.28 (16)
C5—C4—H4'111.2 (13)C12—C10—C9118.91 (15)
H4—C4—H4'105.0 (15)C10—C11—H11121.3 (13)
N1—C5—C4102.89 (12)C10—C11—H11'117.2 (12)
N1—C5—H5111.6 (12)H11—C11—H11'121.5 (18)
C4—C5—H5112.4 (12)C10—C12—H12111.1 (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—C7114.15 (14)H12—C12—H12"111.5 (18)
N1—C6—H6108.1 (10)H12'—C12—H12"110 (2)
C7—C6—H6108.6 (10)
N1—C6—C7—O850.8 (2)
Symmetry code: (i) x, y1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC9H14N2O3
Mr198.22
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)12.6304 (8), 11.3329 (10), 7.0306 (6)
β (°) 97.197 (6)
V3)998.42 (14)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.4 × 0.3 × 0.2
Data collection
DiffractometerSiemens R3m/V 4
diffractometer
Absorption correctionψ-scan
(North et al., 1968)
Tmin, Tmax0.933, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
1866, 1739, 1287
Rint0.020
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.090, 0.95
No. of reflections1737
No. of parameters184
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.16, 0.12

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1991), SHELXTL-Plus.

Selected geometric parameters (Å, º) top
N1—C21.3523 (18)C4—C51.519 (2)
N1—C51.438 (2)C6—C71.502 (2)
N1—C61.4451 (19)C7—O81.4450 (19)
C2—O21.2318 (16)O8—C91.3357 (18)
C2—N31.3374 (19)O9—C91.1956 (18)
O2—N3i2.9151 (18)C9—C101.491 (2)
N3—C41.433 (2)C10—C111.330 (3)
N3—H30.85 (2)C10—C121.468 (3)
C2—N1—C5112.60 (12)N1—C6—C7114.15 (14)
C2—N1—C6122.83 (13)O8—C7—C6107.61 (12)
C5—N1—C6124.16 (12)C9—O8—C7117.19 (12)
O2—C2—N3126.69 (14)O9—C9—O8122.76 (15)
O2—C2—N1125.58 (14)O9—C9—C10125.86 (15)
N3—C2—N1107.73 (13)O8—C9—C10111.38 (13)
C2—N3—C4113.00 (14)C11—C10—C12123.79 (17)
N3—C4—C5103.11 (13)C11—C10—C9117.28 (16)
N1—C5—C4102.89 (12)C12—C10—C9118.91 (15)
N1—C6—C7—O850.8 (2)
Symmetry code: (i) x, y1/2, z1/2.
 

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