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Acta Cryst. (2009). E65, o104    [ doi:10.1107/S1600536808041883 ]

rac-1-Acetyl-5-benzyl-2-thioxoimidazolidin-4-one

M. C. Uzcátegui, G. E. Delgado, A. J. Mora, T. González and A. Briceño

Abstract top

In the title compound, C12H12N2O2S, the molecules have a wing-like conformation, with a distance of 3.797 (2) Å between the centroids of the five- and six-membered rings. In the crystal structure, molecules are linked by N-H...O hydrogen bonds, forming infinite one-dimensional zigzag chains, running along [001], with a C(4) graph-set motif.

Comment top

In continuation of our study of N-carbamoyl, hydantoin and thiohydantoin derivatives of α-amino acids (Seijas et al., 2006, 2007; Delgado et al., 2007; Sulbaran et al., 2007), we report here the structure of the title compound (I) - the N-acetylthiohydantoin derivative of the α-amino acid L-phenylalanine.

Compound (I) (Fig. 1) crystallizes in a centrosymmetric space group, which implies that L-phenylalanine suffered an amino acid racemization produced by the use of acetic acid in the synthesis (Yamada et al. 1983; Yoshioka, 2007). All bond distances and angles are normal (Allen, 2002). The thiohydantoin ring is essentially planar with a maximum deviations of 0.023 (1) Å in C4 and -0.025 (2) Å in C5. The molecular structure and crystal packing of (I) are stabilized by intermolecular N3—H3···O4 (x, 1/2 - y, 1/2 + z) hydrogen bonds (Table 1), forming infinite one-dimentional zigzag chains that run along [001] direction, which can be described in graph-set notation as C(4) (Etter, 1990) (Figure 2).

Related literature top

For related compounds, see: Seijas et al. (2006, 2007); Delgado et al. (2007); Sulbaran et al. (2007). For amino acids racemization, see: Yamada et al. (1983); Yoshioka (2007). For reference structural data, see: Allen et al. (2002); For hydrogen-bond motifs in graph-set notation, see Etter (1990).

Experimental top

L-phenylalanine (3.4 mmol) and NH4SCN (3.4 mmol) was dissolved in a 9 ml acetic anhydride - 1 ml acetic acid mixture and transferred in a round-bottom flask. The mixture was warmed, with agitation, to 363 K over a period of 30 min. The resulting solution was cooled in a ice/water mixture and stored in a freezer overnight. The resulting white solid was filtered off and washed with cool water (m.p. 441–443 K). Crystal of (I) suitable for X-ray diffraction analysis were obtained by slow evaporation of a 1:1 ethanol-methanol solution.

Refinement top

All H atoms were placed at calculated positions and treated using the riding model, with C—H distances of 0.93–0.98 A, and N—H distances of 0.86 A. The Uiso(H) parameters were fixed at 1.2Ueq(C, N) and 1.5Ueq(methyl).

Computing details top

Data collection: CrystalClear (Rigaku, 2002); cell refinement: CrystalClear (Rigaku, 2002); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: PLATON (Spek, 2003) and publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement elipsoids are drawn at the 25% probability level and H atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. A portion of the crystal packing viewed along the a-axis. Hydrogen bonds are marked with dashed lines. H atoms not involved in hydrogen bonding have been omitted for clarity.
rac-1-Acetyl-5-benzyl-2-thioxoimidazolidin-4-one top
Crystal data top
C12H12N2O2SF(000) = 520
Mr = 248.30Dx = 1.351 Mg m−3
Monoclinic, P21/cMelting point = 441–443 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71070 Å
a = 11.696 (5) ÅCell parameters from 4020 reflections
b = 13.479 (6) Åθ = 2.4–27.8°
c = 7.767 (4) ŵ = 0.26 mm−1
β = 94.41 (1)°T = 298 K
V = 1220.8 (9) Å3Block, colourless
Z = 40.4 × 0.3 × 0.2 mm
Data collection top
Rigaku AFC-7S Mercury
diffractometer		2349 independent reflections
Radiation source: Normal-focus sealed tube2065 reflections with I > 2σ(I)
graphiteRint = 0.026
Detector resolution: 14.6306 pixels mm-1θmax = 28.0°, θmin = 2.3°
ω scansh = −13→13
Absorption correction: multi-scan
(Jacobson, 1998)		k = −15→15
Tmin = 0.900, Tmax = 0.950l = −9→6
12945 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.124 w = 1/[σ2(Fo2) + (0.0616P)2 + 0.4929P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2349 reflectionsΔρmax = 0.24 e Å−3
156 parametersΔρmin = −0.27 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.013 (2)
Crystal data top
C12H12N2O2SV = 1220.8 (9) Å3
Mr = 248.30Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.696 (5) ŵ = 0.26 mm−1
b = 13.479 (6) ÅT = 298 K
c = 7.767 (4) Å0.4 × 0.3 × 0.2 mm
β = 94.41 (1)°
Data collection top
Rigaku AFC-7S Mercury
diffractometer		2349 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)		2065 reflections with I > 2σ(I)
Tmin = 0.900, Tmax = 0.950Rint = 0.026
12945 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.124Δρmax = 0.24 e Å−3
S = 1.05Δρmin = −0.27 e Å−3
2349 reflectionsAbsolute structure: ?
156 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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
S20.84958 (5)0.53330 (4)0.61947 (7)0.0501 (2)
O20.88296 (18)0.61004 (12)0.0516 (2)0.0689 (5)
O40.87718 (14)0.24785 (10)0.23095 (18)0.0512 (4)
N10.85248 (14)0.50588 (12)0.26762 (19)0.0366 (4)
N30.86134 (14)0.37142 (11)0.42952 (19)0.0383 (4)
H30.86220.33430.51960.046*
C20.85359 (16)0.47307 (13)0.4365 (2)0.0356 (4)
C40.86755 (17)0.33477 (14)0.2669 (2)0.0378 (4)
C50.85594 (17)0.42208 (14)0.1459 (2)0.0385 (4)
H50.92370.42720.07960.046*
C60.86200 (19)0.60326 (15)0.2013 (3)0.0476 (5)
C70.8434 (2)0.69011 (16)0.3128 (3)0.0626 (7)
H7A0.84210.74950.24450.094*
H7B0.90460.69410.40240.094*
H7C0.77160.68290.36370.094*
C80.74690 (19)0.41292 (17)0.0231 (3)0.0487 (5)
H8A0.73750.4732−0.04460.058*
H8B0.75650.3585−0.05610.058*
C90.63988 (19)0.39550 (17)0.1147 (3)0.0496 (5)
C100.5823 (2)0.4733 (2)0.1867 (3)0.0634 (7)
H100.61010.53760.17860.076*
C110.4837 (3)0.4563 (3)0.2707 (4)0.0837 (10)
H110.44630.50920.31900.100*
C120.4967 (3)0.2862 (3)0.2141 (7)0.1180 (15)
H120.46810.22230.22370.142*
C130.4415 (3)0.3629 (4)0.2826 (5)0.1022 (12)
H130.37490.35180.33780.123*
C140.5954 (3)0.3015 (2)0.1296 (5)0.0825 (9)
H140.63190.24780.08260.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S20.0680 (4)0.0440 (4)0.0399 (3)−0.0022 (2)0.0150 (2)−0.0088 (2)
O20.1084 (15)0.0490 (10)0.0522 (10)0.0001 (9)0.0243 (9)0.0161 (7)
O40.0777 (11)0.0330 (8)0.0435 (8)0.0035 (7)0.0093 (7)−0.0038 (6)
N10.0462 (10)0.0304 (8)0.0341 (8)0.0014 (7)0.0091 (6)0.0021 (6)
N30.0531 (10)0.0312 (8)0.0312 (8)−0.0013 (7)0.0075 (6)0.0022 (6)
C20.0369 (10)0.0348 (10)0.0358 (10)−0.0015 (7)0.0081 (7)0.0009 (7)
C40.0439 (11)0.0342 (10)0.0356 (10)0.0009 (8)0.0067 (7)−0.0014 (7)
C50.0491 (12)0.0344 (10)0.0335 (10)0.0021 (8)0.0118 (8)0.0006 (7)
C60.0571 (14)0.0352 (11)0.0516 (13)0.0004 (9)0.0110 (10)0.0083 (9)
C70.0881 (19)0.0330 (12)0.0679 (16)0.0020 (11)0.0140 (13)0.0055 (10)
C80.0588 (14)0.0552 (13)0.0319 (10)0.0042 (10)0.0029 (9)−0.0021 (9)
C90.0471 (13)0.0623 (14)0.0385 (11)0.0045 (10)−0.0029 (8)−0.0030 (9)
C100.0547 (15)0.0767 (19)0.0582 (15)0.0128 (12)−0.0001 (11)−0.0111 (12)
C110.0587 (18)0.126 (3)0.0657 (18)0.0246 (18)0.0017 (13)−0.0179 (18)
C120.070 (2)0.102 (3)0.186 (4)−0.022 (2)0.034 (3)0.016 (3)
C130.060 (2)0.144 (4)0.106 (3)0.000 (2)0.0263 (18)0.009 (2)
C140.0598 (17)0.0713 (19)0.118 (3)−0.0079 (14)0.0165 (16)−0.0138 (17)
Geometric parameters (Å, °) top
S2—C21.6402 (19)C7—H7C0.9600
O2—C61.210 (3)C8—C91.505 (3)
O4—C41.212 (2)C8—H8A0.9700
N1—C21.384 (2)C8—H8B0.9700
N1—C61.418 (2)C9—C141.378 (4)
N1—C51.476 (2)C9—C101.387 (3)
N3—C41.363 (2)C10—C111.387 (4)
N3—C21.374 (2)C10—H100.9300
N3—H30.8600C11—C131.358 (5)
C4—C51.506 (3)C11—H110.9300
C5—C81.537 (3)C12—C131.349 (5)
C5—H50.9800C12—C141.386 (5)
C6—C71.482 (3)C12—H120.9300
C7—H7A0.9600C13—H130.9300
C7—H7B0.9600C14—H140.9300
C2—N1—C6130.19 (17)H7B—C7—H7C109.5
C2—N1—C5111.36 (15)C9—C8—C5113.59 (16)
C6—N1—C5117.97 (16)C9—C8—H8A108.8
C4—N3—C2113.97 (15)C5—C8—H8A108.8
C4—N3—H3123.0C9—C8—H8B108.8
C2—N3—H3123.0C5—C8—H8B108.8
N3—C2—N1106.08 (15)H8A—C8—H8B107.7
N3—C2—S2122.29 (14)C14—C9—C10117.5 (2)
N1—C2—S2131.63 (15)C14—C9—C8121.1 (2)
O4—C4—N3125.20 (18)C10—C9—C8121.3 (2)
O4—C4—C5128.11 (17)C9—C10—C11120.9 (3)
N3—C4—C5106.65 (16)C9—C10—H10119.6
N1—C5—C4101.76 (14)C11—C10—H10119.6
N1—C5—C8113.36 (16)C13—C11—C10120.3 (3)
C4—C5—C8110.80 (17)C13—C11—H11119.9
N1—C5—H5110.2C10—C11—H11119.9
C4—C5—H5110.2C13—C12—C14120.9 (4)
C8—C5—H5110.2C13—C12—H12119.5
O2—C6—N1116.53 (19)C14—C12—H12119.5
O2—C6—C7123.47 (19)C12—C13—C11119.8 (3)
N1—C6—C7119.98 (18)C12—C13—H13120.1
C6—C7—H7A109.5C11—C13—H13120.1
C6—C7—H7B109.5C12—C14—C9120.7 (3)
H7A—C7—H7B109.5C12—C14—H14119.7
C6—C7—H7C109.5C9—C14—H14119.7
H7A—C7—H7C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O4i0.861.982.834 (2)175
Symmetry codes: (i) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O4i0.861.982.834 (2)175
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

This work was supported by Consejo de Desarrollo Científico, Humanístico y Tecnológico de la Universidad de Los Andes, CDCHT-ULA (grants C-1616–08-A and C-1617–08-F) and Fondo Nacional de Ciencia, Tecnología e Innovación, FONACIT (grant LAB-97000821).

references
References top

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