The crystal structure of the title compound, C
10H
10N
2O
2·H
2O, 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
interactions.
Supporting information
CCDC reference: 659125
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.
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.
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).
(
S)-5-Benzylimidazolidine-2,4-dione monohydrate
top
Crystal data top
C10H10N2O2·H2O | F(000) = 220 |
Mr = 208.22 | Dx = 1.244 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2yb | Cell parameters from 25 reflections |
a = 6.229 (2) Å | θ = 28.2–36.7° |
b = 6.244 (3) Å | µ = 0.09 mm−1 |
c = 14.475 (3) Å | T = 293 K |
β = 99.05 (3)° | Laminar, colourless |
V = 556.0 (3) Å3 | 0.40 × 0.36 × 0.20 mm |
Z = 2 | |
Data collection top
Rigaku AFC-7S diffractometer | Rint = 0.006 |
Radiation source: normal-focus sealed tube | θmax = 25.0°, θmin = 2.9° |
Graphite monochromator | h = 0→7 |
ω–2θ scans | k = 0→7 |
1192 measured reflections | l = −17→17 |
1088 independent reflections | 3 standard reflections every 150 reflections |
976 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.141 | H-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 parameters | Δρmax = 0.56 e Å−3 |
1 restraint | Δρmin = −0.27 e Å−3 |
Crystal data top
C10H10N2O2·H2O | V = 556.0 (3) Å3 |
Mr = 208.22 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.229 (2) Å | µ = 0.09 mm−1 |
b = 6.244 (3) Å | T = 293 K |
c = 14.475 (3) Å | 0.40 × 0.36 × 0.20 mm |
β = 99.05 (3)° | |
Data collection top
Rigaku AFC-7S diffractometer | Rint = 0.006 |
1192 measured reflections | 3 standard reflections every 150 reflections |
1088 independent reflections | intensity decay: none |
976 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 1 restraint |
wR(F2) = 0.141 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.56 e Å−3 |
1088 reflections | Δρmin = −0.27 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
N1 | 0.3885 (4) | 1.1282 (5) | 0.1167 (2) | 0.0448 (8) | |
H1 | 0.2502 | 1.1467 | 0.1105 | 0.054* | |
C2 | 0.4809 (5) | 0.9464 (6) | 0.0966 (2) | 0.0404 (8) | |
O2 | 0.3953 (4) | 0.7774 (5) | 0.06779 (19) | 0.0538 (7) | |
N3 | 0.7053 (4) | 0.9776 (5) | 0.1134 (2) | 0.0414 (7) | |
H3 | 0.7993 | 0.8802 | 0.1067 | 0.050* | |
C4 | 0.7559 (5) | 1.1784 (6) | 0.1412 (2) | 0.0428 (8) | |
O4 | 0.9417 (4) | 1.2550 (5) | 0.15754 (19) | 0.0559 (7) | |
C5 | 0.5459 (5) | 1.2921 (6) | 0.1501 (3) | 0.0457 (8) | |
H5 | 0.5267 | 1.4162 | 0.1082 | 0.055* | |
C6 | 0.5379 (7) | 1.3635 (7) | 0.2513 (3) | 0.0607 (10) | |
H6A | 0.6487 | 1.4715 | 0.2691 | 0.073* | |
H6B | 0.3977 | 1.4284 | 0.2542 | 0.073* | |
C7 | 0.5730 (7) | 1.1823 (8) | 0.3196 (3) | 0.0606 (10) | |
C11 | 0.812 (1) | 0.9725 (17) | 0.4309 (4) | 0.113 (2) | |
H11 | 0.9500 | 0.9474 | 0.4642 | 0.136* | |
C8 | 0.4061 (9) | 1.0438 (10) | 0.3314 (3) | 0.0791 (15) | |
H8 | 0.2675 | 1.0678 | 0.2986 | 0.095* | |
C9 | 0.442 (1) | 0.8701 (13) | 0.3911 (4) | 0.101 (2) | |
H9 | 0.3295 | 0.7760 | 0.3973 | 0.121* | |
C10 | 0.646 (2) | 0.8380 (14) | 0.4412 (4) | 0.121 (3) | |
H10 | 0.6699 | 0.7234 | 0.4825 | 0.145* | |
C12 | 0.7775 (9) | 1.1473 (13) | 0.3708 (3) | 0.0853 (16) | |
H12 | 0.8911 | 1.2404 | 0.3649 | 0.102* | |
O1W | −0.0237 (5) | 0.6599 (6) | 0.0681 (3) | 0.0877 (12) | |
H1W | −0.0242 | 0.5249 | 0.1036 | 0.132* | |
H2W | 0.1128 | 0.6900 | 0.0688 | 0.132* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0285 (12) | 0.0458 (19) | 0.0591 (16) | 0.0041 (13) | 0.0034 (11) | −0.0047 (14) |
C2 | 0.0308 (15) | 0.0403 (19) | 0.0510 (18) | −0.0002 (15) | 0.0089 (13) | 0.0034 (14) |
O2 | 0.0406 (12) | 0.0442 (14) | 0.0771 (17) | −0.0078 (12) | 0.0106 (11) | −0.0098 (13) |
N3 | 0.0274 (12) | 0.0367 (15) | 0.0610 (16) | 0.0024 (12) | 0.0094 (11) | 0.0023 (13) |
C4 | 0.0337 (15) | 0.0431 (18) | 0.0517 (17) | −0.0005 (15) | 0.0071 (12) | 0.0052 (16) |
O4 | 0.0391 (12) | 0.0527 (16) | 0.0747 (16) | −0.0087 (13) | 0.0047 (11) | −0.0008 (13) |
C5 | 0.0402 (16) | 0.0371 (17) | 0.0596 (19) | 0.0021 (16) | 0.0074 (14) | 0.0010 (16) |
C6 | 0.059 (2) | 0.053 (2) | 0.071 (2) | 0.0029 (19) | 0.0121 (18) | −0.019 (2) |
C7 | 0.066 (2) | 0.068 (3) | 0.0496 (18) | 0.004 (2) | 0.0139 (17) | −0.014 (2) |
C11 | 0.124 (5) | 0.144 (7) | 0.069 (3) | 0.033 (6) | 0.013 (3) | 0.024 (4) |
C8 | 0.087 (3) | 0.091 (4) | 0.064 (3) | −0.001 (3) | 0.029 (2) | −0.006 (3) |
C9 | 0.133 (6) | 0.099 (5) | 0.080 (3) | −0.004 (4) | 0.047 (4) | 0.007 (4) |
C10 | 0.189 (8) | 0.106 (6) | 0.075 (4) | 0.025 (6) | 0.045 (4) | 0.029 (4) |
C12 | 0.083 (3) | 0.111 (5) | 0.059 (2) | 0.003 (4) | 0.004 (2) | −0.003 (3) |
O1W | 0.0459 (15) | 0.0506 (18) | 0.172 (3) | 0.0047 (15) | 0.0342 (18) | 0.009 (2) |
Geometric parameters (Å, º) top
N1—C2 | 1.325 (5) | C7—C8 | 1.383 (7) |
N1—C5 | 1.447 (5) | C7—C12 | 1.386 (7) |
N1—H1 | 0.8600 | C11—C10 | 1.361 (12) |
C2—O2 | 1.226 (5) | C11—C12 | 1.391 (11) |
C2—N3 | 1.394 (4) | C11—H11 | 0.9300 |
N3—C4 | 1.339 (5) | C8—C9 | 1.383 (9) |
N3—H3 | 0.8600 | C8—H8 | 0.9300 |
C4—O4 | 1.240 (4) | C9—C10 | 1.372 (10) |
C4—C5 | 1.512 (5) | C9—H9 | 0.9300 |
C5—C6 | 1.539 (5) | C10—H10 | 0.9300 |
C5—H5 | 0.9800 | C12—H12 | 0.9300 |
C6—C7 | 1.496 (7) | O1W—H1W | 0.99 |
C6—H6A | 0.9700 | O1W—H2W | 0.87 |
C6—H6B | 0.9700 | | |
| | | |
C2—N1—C5 | 112.6 (3) | C5—C6—H6B | 109.0 |
C2—N1—H1 | 123.7 | H6A—C6—H6B | 107.8 |
C5—N1—H1 | 123.7 | C8—C7—C12 | 118.7 (5) |
O2—C2—N1 | 129.2 (3) | C8—C7—C6 | 121.3 (4) |
O2—C2—N3 | 123.3 (3) | C12—C7—C6 | 119.9 (5) |
N1—C2—N3 | 107.5 (3) | C10—C11—C12 | 120.4 (6) |
C4—N3—C2 | 111.4 (3) | C10—C11—H11 | 119.8 |
C4—N3—H3 | 124.3 | C12—C11—H11 | 119.8 |
C2—N3—H3 | 124.3 | C9—C8—C7 | 121.1 (6) |
O4—C4—N3 | 125.9 (3) | C9—C8—H8 | 119.5 |
O4—C4—C5 | 126.6 (4) | C7—C8—H8 | 119.5 |
N3—C4—C5 | 107.4 (3) | C10—C9—C8 | 119.3 (7) |
N1—C5—C4 | 100.9 (3) | C10—C9—H9 | 120.3 |
N1—C5—C6 | 113.7 (3) | C8—C9—H9 | 120.3 |
C4—C5—C6 | 112.0 (3) | C11—C10—C9 | 120.6 (7) |
N1—C5—H5 | 110.0 | C11—C10—H10 | 119.7 |
C4—C5—H5 | 110.0 | C9—C10—H10 | 119.7 |
C6—C5—H5 | 110.0 | C7—C12—C11 | 119.8 (7) |
C7—C6—C5 | 112.7 (3) | C7—C12—H12 | 120.1 |
C7—C6—H6A | 109.0 | C11—C12—H12 | 120.1 |
C5—C6—H6A | 109.0 | H1W—O1W—H2W | 105 |
C7—C6—H6B | 109.0 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1Wi | 0.86 | 1.90 | 2.750 (4) | 169 |
O1W—H2W···O2 | 0.87 | 1.85 | 2.712 (4) | 175 |
N1—H1···O4ii | 0.86 | 2.24 | 3.040 (4) | 154 |
O1W—H1W···O4iii | 0.99 | 1.88 | 2.864 (5) | 172 |
C5—H5···O2iv | 0.98 | 2.44 | 3.336 (5) | 152 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x−1, y−1, z; (iv) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | C10H10N2O2·H2O |
Mr | 208.22 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.229 (2), 6.244 (3), 14.475 (3) |
β (°) | 99.05 (3) |
V (Å3) | 556.0 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.40 × 0.36 × 0.20 |
|
Data collection |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1192, 1088, 976 |
Rint | 0.006 |
(sin θ/λ)max (Å−1) | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.141, 1.06 |
No. of reflections | 1088 |
No. of parameters | 138 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.56, −0.27 |
Selected geometric parameters (Å, º) topN1—C2 | 1.325 (5) | N3—C4 | 1.339 (5) |
N1—C5 | 1.447 (5) | C4—O4 | 1.240 (4) |
C2—O2 | 1.226 (5) | C4—C5 | 1.512 (5) |
C2—N3 | 1.394 (4) | | |
| | | |
C2—N1—C5 | 112.6 (3) | O4—C4—N3 | 125.9 (3) |
O2—C2—N1 | 129.2 (3) | O4—C4—C5 | 126.6 (4) |
O2—C2—N3 | 123.3 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···O1Wi | 0.86 | 1.90 | 2.750 (4) | 169 |
O1W—H2W···O2 | 0.87 | 1.85 | 2.712 (4) | 175 |
N1—H1···O4ii | 0.86 | 2.24 | 3.040 (4) | 154 |
O1W—H1W···O4iii | 0.99 | 1.88 | 2.864 (5) | 172 |
C5—H5···O2iv | 0.98 | 2.44 | 3.336 (5) | 152 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x−1, y−1, z; (iv) x, y+1, z. |
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).