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Acta Cryst.(2005). E61, o3269–o3270 doi:10.1107/S1600536805028023 Caudleet al. C

4H8N2O

o3269

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

Anhydrous 1-methylimidazolidin-2-one

M. Tyler Caudle,* Erica Tassone and Thomas L. Groy

Department of Chemistry and Biochemistry, Arizona State University, Box 871604, Tempe, AZ 85287-1604, USA

Correspondence e-mail: tcaudle@asu.edu

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.004 A˚

Rfactor = 0.070

wRfactor = 0.161

Data-to-parameter ratio = 13.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2005 International Union of Crystallography Printed in Great Britain – all rights reserved

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.

Comment

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 character-istics of this unit be well understood. In the course of our work on biomimetic carbon dioxide fixation, we crystallized anhy-drous 1-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 A˚ . 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 withN-silyl-substituted imidazolidin-2-ones (Szalay

et al., 2005), as well as withN10-methoxycarbonylbiotin methyl

[image:1.610.259.411.596.730.2]

Received 11 August 2005 Accepted 6 September 2005 Online 17 September 2005

Figure 1

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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 consid-erablesp3character (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 A˚ ). Neighboring hydrogen-bonded chains are packed to form a two-dimensional sheet (Fig. 2). The individual hydrogen-bonding interactions are inclined at 19.8

to the heterocycle plane, and may be indicative of some pyramidalization of the —NH group.

Experimental

The title compound was purchased from Aldrich. The microcrystal-line 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.

Crystal data

C4H8N2O Mr= 100.12 Monoclinic,P21=c a= 7.5746 (11) A˚ b= 9.3984 (13) A˚ c= 7.9482 (11) A˚

= 117.139 (2) V= 503.53 (12) A˚3 Z= 4

Dx= 1.321 Mg m 3

MoKradiation Cell parameters from 1593

reflections

= 3.0–31.6

= 0.10 mm1 T= 298 (2) K Block, colorless 0.380.300.10 mm

Data collection

Bruker SMART APEX diffractometer

!scans

Absorption correction: scan (Blessing, 1995)

Tmin= 0.94,Tmax= 0.99

3853 measured reflections

888 independent reflections 712 reflections withI> 2(I) Rint= 0.092

max= 25.0 h=9!9 k=11!11 l=9!9

Refinement

Refinement onF2 R[F2> 2(F2)] = 0.070 wR(F2) = 0.161 S= 1.16 888 reflections 65 parameters

H-atom parameters constrained

w= 1/[2(F

o2) + (0.0535P)2

+ 0.1874P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.14 e A˚

3

min=0.18 e A˚

3

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

the rest.

Data collection:SMART(Bruker, 1997); cell refinement: SAINT-Plus(Bruker, 1997); data reduction:SAINT-Plus; 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.

References

Attwood, P. V. & Wallace, J. C. (2002).Acc. Chem. Res.35, 113–120. Blessing, R. H. (1995).Acta Cryst.A51, 33–38.

Bruker (1997).SMART(Version 5.625), SAINT-Plus (Version 6.28a) and SHELXTL(Version 5.1). Bruker AXS Inc., Madison, Wisconsin, USA. Carey, P., Soennichsen, F. & Yee, V. (2004).IUBMB Life,56, 575–583. DeTitta, G. T., Edmonds, J. W., Stallings, W. & Donohue, J. (1976).J. Am.

Chem. Soc.98, 1920–1926.

Kapon, M. & Reisner, G. M. (1989).Acta Cryst.C45, 780–782.

Meier, R. J. & Coussens, B. (1992).J. Mol. Struct. (Theochem),253, 25–33. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Stallings, W. C., Monti, C. T., Lane, M. D. & DeTitta, G. T. (1980).Proc. Natl Acad. Sci. USA,77, 1260–1264.

[image:2.610.315.564.70.315.2]

Szalay, R., Pongor, G., Harmat, V., Boecskei, Z. & Knausz, D. (2005). J. Organomet. Chem.690, 1498–1506.

Figure 2

Solid-state packing diagram of (I), viewed down the crystallographica

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supporting information

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Acta Cryst. (2005). E61, o3269–o3270

supporting information

Acta Cryst. (2005). E61, o3269–o3270 [doi:10.1107/S1600536805028023]

Anhydrous 1-methylimidazolidin-2-one

M. Tyler Caudle, Erica Tassone and Thomas L. Groy

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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

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[image:4.610.122.483.68.390.2]

Figure 1

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supporting information

[image:5.610.127.482.71.416.2]

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Acta Cryst. (2005). E61, o3269–o3270

Figure 2

Solid-state packing diagram of (I), viewed down the crystallographic a axis.

N-methylimidazolidin-2-one

Crystal data

C4H8N2O Mr = 100.12

Monoclinic, P21/c Hall symbol: -P 2ybc

a = 7.5746 (11) Å

b = 9.3984 (13) Å

c = 7.9482 (11) Å

β = 117.139 (2)°

V = 503.53 (12) Å3 Z = 4

F(000) = 216

Dx = 1.321 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 1593 reflections

θ = 3.0–31.6°

µ = 0.10 mm−1 T = 298 K Block, colorless 0.38 × 0.30 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω scans

Absorption correction: ψ scan (Blessing, 1995)

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θmax = 25.0°, θmin = 3.0° h = −9→9

l = −9→9

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.070 wR(F2) = 0.161 S = 1.16 888 reflections 65 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2(F

o2) + (0.0535P)2 + 0.1874P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001 Δρmax = 0.14 e Å−3 Δρmin = −0.18 e Å−3

Special details

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)

x y z Uiso*/Ueq

O1 0.7224 (3) 1.23376 (17) −0.0327 (3) 0.0607 (7) C1 0.7478 (4) 1.1137 (3) 0.0358 (4) 0.0422 (7) N2 0.7386 (4) 0.9918 (2) −0.0542 (3) 0.0570 (8) C2 0.6997 (5) 0.9812 (3) −0.2483 (4) 0.0610 (9) H2A 0.6795 1.0746 −0.3028 0.092* H2B 0.5829 0.9247 −0.3170 0.092* H2C 0.8107 0.9371 −0.2550 0.092* C3 0.7750 (4) 0.8699 (3) 0.0645 (4) 0.0565 (8) H3A 0.8956 0.8215 0.0827 0.068* H3B 0.6650 0.8035 0.0114 0.068* C4 0.7961 (4) 0.9324 (3) 0.2486 (4) 0.0556 (8) H4A 0.6873 0.9032 0.2734 0.067* H4B 0.9206 0.9043 0.3541 0.067* N5 0.7908 (4) 1.0826 (2) 0.2151 (3) 0.0601 (8) H5A 0.8129 1.1459 0.3007 0.072*

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

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supporting information

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Acta Cryst. (2005). E61, o3269–o3270

N2 0.090 (2) 0.0353 (12) 0.0456 (14) 0.0022 (11) 0.0304 (14) −0.0031 (9) C2 0.079 (2) 0.0567 (19) 0.0485 (18) −0.0074 (15) 0.0303 (17) −0.0119 (13) C3 0.067 (2) 0.0361 (15) 0.067 (2) 0.0078 (13) 0.0305 (17) 0.0036 (12) C4 0.065 (2) 0.0481 (16) 0.0527 (17) 0.0075 (14) 0.0256 (15) 0.0124 (13) N5 0.101 (2) 0.0390 (13) 0.0485 (14) 0.0025 (12) 0.0414 (14) −0.0005 (10)

Geometric parameters (Å, º)

O1—C1 1.229 (3) C3—C4 1.516 (4)

C1—N2 1.336 (3) C3—H3A 0.9700

C1—N5 1.341 (3) C3—H3B 0.9700

N2—C3 1.429 (3) C4—N5 1.434 (4)

N2—C2 1.436 (3) C4—H4A 0.9700

C2—H2A 0.9600 C4—H4B 0.9700

C2—H2B 0.9600 N5—H5A 0.8600

C2—H2C 0.9600

O1—C1—N2 126.2 (2) C4—C3—H3A 111.1 O1—C1—N5 125.7 (2) N2—C3—H3B 111.1 N2—C1—N5 108.1 (2) C4—C3—H3B 111.1 C1—N2—C3 112.7 (2) H3A—C3—H3B 109.1 C1—N2—C2 124.8 (2) N5—C4—C3 102.7 (2) C3—N2—C2 122.5 (2) N5—C4—H4A 111.2 N2—C2—H2A 109.5 C3—C4—H4A 111.2 N2—C2—H2B 109.5 N5—C4—H4B 111.2 H2A—C2—H2B 109.5 C3—C4—H4B 111.2 N2—C2—H2C 109.5 H4A—C4—H4B 109.1 H2A—C2—H2C 109.5 C1—N5—C4 112.6 (2) H2B—C2—H2C 109.5 C1—N5—H5A 123.7 N2—C3—C4 103.3 (2) C4—N5—H5A 123.7 N2—C3—H3A 111.1

Figure

Figure 1Displacement ellipsoid drawing of (I) (35% probability ellipsoids).
Figure 2
Figure 1
Figure 2

References

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