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The title compound, C4H8N2O, crystallizes from the vapor phase in sheets supported by a one-dimensional hydrogen-bonded network. The mol­ecular unit shows planar ureido -NCH3 groups, but the slight out-of-plane hydrogen-bond geometry may be indicative of some pyramidalization of the ureido -NH groups.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028023/ac6191sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028023/ac6191Isup2.hkl
Contains datablock I

CCDC reference: 287426

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.070
  • wR factor = 0.161
  • Data-to-parameter ratio = 13.7

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The imidazolidin-2-one functional group is of primary importance in the transfer of carbon dioxide by biotin-dependent enzymes (Carey et al., 2004; Attwood & Wallace, 2002). It is therefore important that the structural characteristics of this unit be well understood. In the course of our work on biomimetic carbon dioxide fixation, we crystallized anhydrous N-methylimidazolidin-2-one, (I), and report here its crystal structure.

The molecular unit in (I) shows the five-membered heterocycle. The ring is only slightly enveloped, with an average internal torsion angle of 4.6° and a mean deviation from planarity of 0.0273 Å. The metrical parameters in the heterocycle are essentially identical to those in unsubstituted imidazolidin-2-one (Kapon & Reisner, 1989), and to those in biotin itself (DeTitta et al., 1976). Methylated atom N2 is planar, indicative of largely sp2-hybrid character. This is consistent with N-silyl-substituted imidazolidin-2-ones (Szalay et al., 2005), as well as with N1'-methoxycarbonylbiotin methyl ester (Stallings et al., 1980), which also exhibit essentially planar ureido N atoms. However, the planar N atoms are at variance with some theoretical work which seems to indicate that the N atoms in urea and related molecules have considerable sp3 character·(Meier & Coussens, 1992). Some insight may be gained from the solid state packing in (I), which is supported by a one-dimensional network of hydrogen bonds (O···N = 2.87 Å). Neighboring hydrogen-bonded chains are packed to form a two-dimensional sheet (Fig. 2). The individual hydrogen-bonding interactions are 19.8° out of the heterocycle plane, and may be indicative of some pyramidalization of the —NH group.

Experimental top

The title compopund was purchased from Aldrich. The microcrystalline powder was placed in a flame-sealed ampoule and the apparatus stored in a 363 K oven for one week. This procedure gave colorless blocks suitable for X-ray diffraction.

Refinement top

H atoms were added in idealized positions as riding atoms with C—H distances of 0.96 Å for methyl and 0.96 Å for the rest; The N—H distance is 0.86 Å. The isotropic displacement parameters were set at 1.5Ueq of the parent atom for the methyl H atoms and 1.2Ueq for the rest.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Displacement ellipsoid drawing of (I) (35% probability ellipsoids).
[Figure 2] Fig. 2. Solid-state packing diagram of (I), viewed down the crystallographic a axis.
N-methylimidazolidin-2-one top
Crystal data top
C4H8N2OF(000) = 216
Mr = 100.12Dx = 1.321 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1593 reflections
a = 7.5746 (11) Åθ = 3.0–31.6°
b = 9.3984 (13) ŵ = 0.10 mm1
c = 7.9482 (11) ÅT = 298 K
β = 117.139 (2)°Block, colorless
V = 503.53 (12) Å30.38 × 0.30 × 0.10 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer
888 independent reflections
Radiation source: fine-focus sealed tube712 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.092
ω scansθmax = 25.0°, θmin = 3.0°
Absorption correction: ψ scan
(Blessing, 1995)
h = 99
Tmin = 0.94, Tmax = 0.99k = 1111
3853 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.161H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0535P)2 + 0.1874P]
where P = (Fo2 + 2Fc2)/3
888 reflections(Δ/σ)max < 0.001
65 parametersΔρmax = 0.14 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C4H8N2OV = 503.53 (12) Å3
Mr = 100.12Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5746 (11) ŵ = 0.10 mm1
b = 9.3984 (13) ÅT = 298 K
c = 7.9482 (11) Å0.38 × 0.30 × 0.10 mm
β = 117.139 (2)°
Data collection top
Bruker SMART APEX
diffractometer
888 independent reflections
Absorption correction: ψ scan
(Blessing, 1995)
712 reflections with I > 2σ(I)
Tmin = 0.94, Tmax = 0.99Rint = 0.092
3853 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0700 restraints
wR(F2) = 0.161H-atom parameters constrained
S = 1.16Δρmax = 0.14 e Å3
888 reflectionsΔρmin = 0.18 e Å3
65 parameters
Special details top

Experimental. Add this here

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.7224 (3)1.23376 (17)0.0327 (3)0.0607 (7)
C10.7478 (4)1.1137 (3)0.0358 (4)0.0422 (7)
N20.7386 (4)0.9918 (2)0.0542 (3)0.0570 (8)
C20.6997 (5)0.9812 (3)0.2483 (4)0.0610 (9)
H2A0.67951.07460.30280.092*
H2B0.58290.92470.31700.092*
H2C0.81070.93710.25500.092*
C30.7750 (4)0.8699 (3)0.0645 (4)0.0565 (8)
H3A0.89560.82150.08270.068*
H3B0.66500.80350.01140.068*
C40.7961 (4)0.9324 (3)0.2486 (4)0.0556 (8)
H4A0.68730.90320.27340.067*
H4B0.92060.90430.35410.067*
N50.7908 (4)1.0826 (2)0.2151 (3)0.0601 (8)
H5A0.81291.14590.30070.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1007 (18)0.0342 (11)0.0614 (13)0.0035 (10)0.0492 (13)0.0068 (9)
C10.0468 (16)0.0392 (14)0.0435 (15)0.0003 (11)0.0232 (13)0.0008 (11)
N20.090 (2)0.0353 (12)0.0456 (14)0.0022 (11)0.0304 (14)0.0031 (9)
C20.079 (2)0.0567 (19)0.0485 (18)0.0074 (15)0.0303 (17)0.0119 (13)
C30.067 (2)0.0361 (15)0.067 (2)0.0078 (13)0.0305 (17)0.0036 (12)
C40.065 (2)0.0481 (16)0.0527 (17)0.0075 (14)0.0256 (15)0.0124 (13)
N50.101 (2)0.0390 (13)0.0485 (14)0.0025 (12)0.0414 (14)0.0005 (10)
Geometric parameters (Å, º) top
O1—C11.229 (3)C3—C41.516 (4)
C1—N21.336 (3)C3—H3A0.9700
C1—N51.341 (3)C3—H3B0.9700
N2—C31.429 (3)C4—N51.434 (4)
N2—C21.436 (3)C4—H4A0.9700
C2—H2A0.9600C4—H4B0.9700
C2—H2B0.9600N5—H5A0.8600
C2—H2C0.9600
O1—C1—N2126.2 (2)C4—C3—H3A111.1
O1—C1—N5125.7 (2)N2—C3—H3B111.1
N2—C1—N5108.1 (2)C4—C3—H3B111.1
C1—N2—C3112.7 (2)H3A—C3—H3B109.1
C1—N2—C2124.8 (2)N5—C4—C3102.7 (2)
C3—N2—C2122.5 (2)N5—C4—H4A111.2
N2—C2—H2A109.5C3—C4—H4A111.2
N2—C2—H2B109.5N5—C4—H4B111.2
H2A—C2—H2B109.5C3—C4—H4B111.2
N2—C2—H2C109.5H4A—C4—H4B109.1
H2A—C2—H2C109.5C1—N5—C4112.6 (2)
H2B—C2—H2C109.5C1—N5—H5A123.7
N2—C3—C4103.3 (2)C4—N5—H5A123.7
N2—C3—H3A111.1
C1—N2—C3—C43.9 (4)C4—N5—C1—N25.0 (4)
N2—C3—C4—N56.2 (3)N5—C1—N2—C30.4 (4)
C3—C4—N5—C17.1 (4)

Experimental details

Crystal data
Chemical formulaC4H8N2O
Mr100.12
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)7.5746 (11), 9.3984 (13), 7.9482 (11)
β (°) 117.139 (2)
V3)503.53 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.38 × 0.30 × 0.10
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionψ scan
(Blessing, 1995)
Tmin, Tmax0.94, 0.99
No. of measured, independent and
observed [I > 2σ(I)] reflections
3853, 888, 712
Rint0.092
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.161, 1.16
No. of reflections888
No. of parameters65
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.14, 0.18

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker 1997), SHELXTL.

 

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