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The crystal structure of the title compound, C10H10N2O2·H2O, also known as L-5-benzylhydantoin monohydrate, is described in terms of two-dimensional supra­molecular arrays built up from infinite chains assembled via N-H...O and O-H...O hydrogen bonds among the organic mol­ecules and solvent water mol­ecules, with graph-set R33(10)C(5)C22(6). The hydrogen-bond network is reinforced by stacking of the layers through C-H...[pi] inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107028090/sk3128sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107028090/sk3128Isup2.hkl
Contains datablock I

CCDC reference: 659125

Comment top

Imidazolidine-2,4-dione, or hydantoin, is a five-membered heterocycle ring containing a reactive cyclic urea nucleus. This heterocycle represents a significant molecular template in combinatorial chemistry libraries (Boeijen et al. 1998; Park et al., 2001), principally because of the four possible substitution points. Solid-phase syntheses including hydantoin as a starting building block have been reported recently (Ganesan, 2003; Vázquez et al., 2004; Alsina et al., 2005). Hydantoin derivatives have attracted great interest in drug innovation because of their wide range of therapeutic properties (Mutschler & Derendorf, 1995). In particular, the five-subtituted hydantoins have been found to be valuable precursors of a great variety of heterocyclic systems that are associated with a wide range of biological activities, including antiarrhythmic (Knabe et al., 1997), anticonvulsant (Singh et al., 2005) and antitumoral agents (Carmi et al., 2006). The best known hydantoin is 5,5-diphenylhydantoin, or phenytoin, which is the most widely use anti-epileptic drug since the experimental determination of its anticonvulsant properties (Putnam & Merrit, 1937). In addition, they are known for their uses as herbicides (Shiozaki, 2002) and fungicides (Marton et al., 1993). On the other hand, the biocatalytic conversion of 5-subtituted hydantoins and the related N-carbamoyl compounds to amino acids has recently received considerable attention for their potential applications in the industrial production of optically pure amino acids, through an enantioselective enzymatic reaction (Wilms et al., 2001; Chen et al., 2003; Burton & Dorrington, 2004).

Continuing with our studies on N-carbamoyl amino acids and hydantoin compounds (Seijas et al., 2006, 2007), in this work we report the crystal structure of the title compound (I), a new 5-subtituted hydantoin derivative.

The asymmetric unit of (I) consist of one (L)-5-benzyl hydantoin molecule and a crystallization water molecule. The dihedral angle between the hydantoin and benzene rings is 55.6 (3)°. The organic molecule adopts a gauche conformation (Fig. 1). The hydantoin ring is essentially planar, with maximum deviations of 0.024 (4) Å for C4 and -0.023 (4) Å for C5. The N1—C2—O2 bond angle [129.2 (3)°] is greater than the N3—C2—O2 angle [123.3 (3)°]. This difference is also observed in the hydantoin molecule (Yu et al., 2004) and 50 other hydantoin derivative compounds reported in the Cambridge Structural Database (Version 5.28; Allen, 2002) with both NH groups unsubstituted and sp3 hybridization at C5.

The structure of (I) is built up from the self-assembly of the hydantoin molecules with solvent water molecules via hydrogen-bonding interactions. The water molecule is involved as a donor and an acceptor of hydrogen bonds. Molecules of (I) form four conventional hydrogen bonds. The N3—H3···O1W(x + 1, y, z) and O1W—H1W···O4(x - 1, y - 1, z) form infinite chains, which run along the b axis. These chains may be described in graph-set notation as C22(6) (Bernstein et al., 1995) (Fig. 2). Adjacent chains are linked laterally by O1W—H2W···O2(x, y, z) and N1—H1···O4(x - 1, y - 1, z) [should this be the same as ii in table?] hydrogen bonds, to form infinite chains parallel to the a axis with graph set motifs C22(6) and C(5), respectively (Fig. 2). Together, these hydrogen-bond patterns produce a two-dimensional array parallel to the ab plane with graph set R33(10) and the formation of a 15 atom macrocycle (Fig. 2). This graph set is also observed in the hydantoin compounds ROKSOZ (Gauthier et al. 1997) and SINZEU (Galdecki & Karolak-Wojciechowska, 1986). Details of the hydrogen-bonding geometry are given in Table 2. Layers join pairwise by C—H···π interactions (Fig. 3). The C10/H10 group of the benzene ring is oriented towards the face of the aromatic ring of a neighboring molecule [C10—H10···Cg(x + 1, y - 1/2, 1 - z) = 3.13 (3) Å]; where Cg is the centroid of the C7–C12 ring. This interaction generates a herringbone-like array in the bc plane (Fig. 3).

Related literature top

For related literature, see: Allen (2002); Alsina et al. (2005); Bernstein et al. (1995); Boeijen et al. (1998); Burton & Dorrington (2004); Carmi et al. (2006); Chen et al. (2003); Galdecki & Karolak-Wojciechowska (1986); Ganesan (2003); Gauthier et al. (1997); Knabe et al. (1997); Marton et al. (1993); Mutschler & Derendorf (1995); Park et al. (2001); Putnam & Merrit (1937); Seijas et al. (2006, 2007); Shiozaki (2002); Singh et al. (2005); Vázquez et al. (2004); Wilms et al. (2001); Yu et al. (2004).

Experimental top

L-Phenylalanine (500 mg, 3.0 mmol) was dissolved in 20 ml of water and the solution was acidified with concentrated HCl (37% v/v) to pH 5.5. KOCN (1458 mg, 18.0 mmol) was then added to this solution. The mixture was warmed, with agitation, to 333 K over a period of 4 h. The resulting solution was cooled at room temperature and acidified with concentrated HCl (37% v/v) to pH 1, at which point a white solid precipitated. The solid was filtered off and washed with cool water (m.p. 467–469 K). Crystals of (I) suitable for X-ray diffraction analysis were obtained by slow evaporation of a 1:1 water–ethanol solution.

Refinement top

All H atoms attached to C atoms were positioned geometrically and assigned Uiso(H) values equal to 1.2 times Ueq(C). The H atoms of the water molecule were located in the final difference Fourier map and their Uiso(H) values were set to 1.5Ueq(O). The absolute structure was assigned from the known configuration of L-phenylalanine. Please check changes to text.

Computing details top

Data collection: MSC/AFC Difractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2001); software used to prepare material for publication: PLATON (Spek, 2003) and publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. Figure 1. A view of (I), with the atomic numbering scheme. Displacement ellipsoids are drawn at the 20% probability level and H atoms are shown as spheres of arbitrary radii.
[Figure 2] Fig. 2. Figure 2. A partial packing view of (I). Hydrogen bonds are shown as green lines. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) x + 1, y, z; (ii) x - 1, y, z; (iii) x - 1, y - 1, z.]
[Figure 3] Fig. 3. Figure 3. A packing view of (I) in the bc plane, showing the herringbone-like array. [Symmetry code: (v) -x + 1, y - 1/2, -z + 1.]
(S)-5-Benzylimidazolidine-2,4-dione monohydrate top
Crystal data top
C10H10N2O2·H2OF(000) = 220
Mr = 208.22Dx = 1.244 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ybCell parameters from 25 reflections
a = 6.229 (2) Åθ = 28.2–36.7°
b = 6.244 (3) ŵ = 0.09 mm1
c = 14.475 (3) ÅT = 293 K
β = 99.05 (3)°Laminar, colourless
V = 556.0 (3) Å30.40 × 0.36 × 0.20 mm
Z = 2
Data collection top
Rigaku AFC-7S
diffractometer
Rint = 0.006
Radiation source: normal-focus sealed tubeθmax = 25.0°, θmin = 2.9°
Graphite monochromatorh = 07
ω–2θ scansk = 07
1192 measured reflectionsl = 1717
1088 independent reflections3 standard reflections every 150 reflections
976 reflections with I > 2σ(I) intensity decay: none
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0901P)2 + 0.1492P]
where P = (Fo2 + 2Fc2)/3
1088 reflections(Δ/σ)max = 0.003
138 parametersΔρmax = 0.56 e Å3
1 restraintΔρmin = 0.27 e Å3
Crystal data top
C10H10N2O2·H2OV = 556.0 (3) Å3
Mr = 208.22Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.229 (2) ŵ = 0.09 mm1
b = 6.244 (3) ÅT = 293 K
c = 14.475 (3) Å0.40 × 0.36 × 0.20 mm
β = 99.05 (3)°
Data collection top
Rigaku AFC-7S
diffractometer
Rint = 0.006
1192 measured reflections3 standard reflections every 150 reflections
1088 independent reflections intensity decay: none
976 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0471 restraint
wR(F2) = 0.141H-atom parameters constrained
S = 1.06Δρmax = 0.56 e Å3
1088 reflectionsΔρmin = 0.27 e Å3
138 parameters
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
N10.3885 (4)1.1282 (5)0.1167 (2)0.0448 (8)
H10.25021.14670.11050.054*
C20.4809 (5)0.9464 (6)0.0966 (2)0.0404 (8)
O20.3953 (4)0.7774 (5)0.06779 (19)0.0538 (7)
N30.7053 (4)0.9776 (5)0.1134 (2)0.0414 (7)
H30.79930.88020.10670.050*
C40.7559 (5)1.1784 (6)0.1412 (2)0.0428 (8)
O40.9417 (4)1.2550 (5)0.15754 (19)0.0559 (7)
C50.5459 (5)1.2921 (6)0.1501 (3)0.0457 (8)
H50.52671.41620.10820.055*
C60.5379 (7)1.3635 (7)0.2513 (3)0.0607 (10)
H6A0.64871.47150.26910.073*
H6B0.39771.42840.25420.073*
C70.5730 (7)1.1823 (8)0.3196 (3)0.0606 (10)
C110.812 (1)0.9725 (17)0.4309 (4)0.113 (2)
H110.95000.94740.46420.136*
C80.4061 (9)1.0438 (10)0.3314 (3)0.0791 (15)
H80.26751.06780.29860.095*
C90.442 (1)0.8701 (13)0.3911 (4)0.101 (2)
H90.32950.77600.39730.121*
C100.646 (2)0.8380 (14)0.4412 (4)0.121 (3)
H100.66990.72340.48250.145*
C120.7775 (9)1.1473 (13)0.3708 (3)0.0853 (16)
H120.89111.24040.36490.102*
O1W0.0237 (5)0.6599 (6)0.0681 (3)0.0877 (12)
H1W0.02420.52490.10360.132*
H2W0.11280.69000.06880.132*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0285 (12)0.0458 (19)0.0591 (16)0.0041 (13)0.0034 (11)0.0047 (14)
C20.0308 (15)0.0403 (19)0.0510 (18)0.0002 (15)0.0089 (13)0.0034 (14)
O20.0406 (12)0.0442 (14)0.0771 (17)0.0078 (12)0.0106 (11)0.0098 (13)
N30.0274 (12)0.0367 (15)0.0610 (16)0.0024 (12)0.0094 (11)0.0023 (13)
C40.0337 (15)0.0431 (18)0.0517 (17)0.0005 (15)0.0071 (12)0.0052 (16)
O40.0391 (12)0.0527 (16)0.0747 (16)0.0087 (13)0.0047 (11)0.0008 (13)
C50.0402 (16)0.0371 (17)0.0596 (19)0.0021 (16)0.0074 (14)0.0010 (16)
C60.059 (2)0.053 (2)0.071 (2)0.0029 (19)0.0121 (18)0.019 (2)
C70.066 (2)0.068 (3)0.0496 (18)0.004 (2)0.0139 (17)0.014 (2)
C110.124 (5)0.144 (7)0.069 (3)0.033 (6)0.013 (3)0.024 (4)
C80.087 (3)0.091 (4)0.064 (3)0.001 (3)0.029 (2)0.006 (3)
C90.133 (6)0.099 (5)0.080 (3)0.004 (4)0.047 (4)0.007 (4)
C100.189 (8)0.106 (6)0.075 (4)0.025 (6)0.045 (4)0.029 (4)
C120.083 (3)0.111 (5)0.059 (2)0.003 (4)0.004 (2)0.003 (3)
O1W0.0459 (15)0.0506 (18)0.172 (3)0.0047 (15)0.0342 (18)0.009 (2)
Geometric parameters (Å, º) top
N1—C21.325 (5)C7—C81.383 (7)
N1—C51.447 (5)C7—C121.386 (7)
N1—H10.8600C11—C101.361 (12)
C2—O21.226 (5)C11—C121.391 (11)
C2—N31.394 (4)C11—H110.9300
N3—C41.339 (5)C8—C91.383 (9)
N3—H30.8600C8—H80.9300
C4—O41.240 (4)C9—C101.372 (10)
C4—C51.512 (5)C9—H90.9300
C5—C61.539 (5)C10—H100.9300
C5—H50.9800C12—H120.9300
C6—C71.496 (7)O1W—H1W0.99
C6—H6A0.9700O1W—H2W0.87
C6—H6B0.9700
C2—N1—C5112.6 (3)C5—C6—H6B109.0
C2—N1—H1123.7H6A—C6—H6B107.8
C5—N1—H1123.7C8—C7—C12118.7 (5)
O2—C2—N1129.2 (3)C8—C7—C6121.3 (4)
O2—C2—N3123.3 (3)C12—C7—C6119.9 (5)
N1—C2—N3107.5 (3)C10—C11—C12120.4 (6)
C4—N3—C2111.4 (3)C10—C11—H11119.8
C4—N3—H3124.3C12—C11—H11119.8
C2—N3—H3124.3C9—C8—C7121.1 (6)
O4—C4—N3125.9 (3)C9—C8—H8119.5
O4—C4—C5126.6 (4)C7—C8—H8119.5
N3—C4—C5107.4 (3)C10—C9—C8119.3 (7)
N1—C5—C4100.9 (3)C10—C9—H9120.3
N1—C5—C6113.7 (3)C8—C9—H9120.3
C4—C5—C6112.0 (3)C11—C10—C9120.6 (7)
N1—C5—H5110.0C11—C10—H10119.7
C4—C5—H5110.0C9—C10—H10119.7
C6—C5—H5110.0C7—C12—C11119.8 (7)
C7—C6—C5112.7 (3)C7—C12—H12120.1
C7—C6—H6A109.0C11—C12—H12120.1
C5—C6—H6A109.0H1W—O1W—H2W105
C7—C6—H6B109.0
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1Wi0.861.902.750 (4)169
O1W—H2W···O20.871.852.712 (4)175
N1—H1···O4ii0.862.243.040 (4)154
O1W—H1W···O4iii0.991.882.864 (5)172
C5—H5···O2iv0.982.443.336 (5)152
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z; (iii) x1, y1, z; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC10H10N2O2·H2O
Mr208.22
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)6.229 (2), 6.244 (3), 14.475 (3)
β (°) 99.05 (3)
V3)556.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.40 × 0.36 × 0.20
Data collection
DiffractometerRigaku AFC-7S
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
1192, 1088, 976
Rint0.006
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.141, 1.06
No. of reflections1088
No. of parameters138
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.56, 0.27

Computer programs: MSC/AFC Difractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2001), PLATON (Spek, 2003) and publCIF (Westrip, 2007).

Selected geometric parameters (Å, º) top
N1—C21.325 (5)N3—C41.339 (5)
N1—C51.447 (5)C4—O41.240 (4)
C2—O21.226 (5)C4—C51.512 (5)
C2—N31.394 (4)
C2—N1—C5112.6 (3)O4—C4—N3125.9 (3)
O2—C2—N1129.2 (3)O4—C4—C5126.6 (4)
O2—C2—N3123.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O1Wi0.861.902.750 (4)169
O1W—H2W···O20.871.852.712 (4)175
N1—H1···O4ii0.862.243.040 (4)154
O1W—H1W···O4iii0.991.882.864 (5)172
C5—H5···O2iv0.982.443.336 (5)152
Symmetry codes: (i) x+1, y, z; (ii) x1, y, z; (iii) x1, y1, z; (iv) x, y+1, z.
 

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