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The single-crystal X-ray diffraction study of the title compound, N-[3-methyl-1-(4-methyl-2,5-dioxoimidazolidin-4-yl)­buty]]­acet­amide monohydrate, C11H19N3O3·H2O, confirms that the imidazolidine­dione ring is in a planar conformation, as evidenced by NMR studies. There are chains of intermolecular hydrogen bonds involving the imido carbonyl-O atom and the acet­amido carbonyl-O atom as acceptors, and the water mol­ecule as donor. The crystal packing is also stabilized by N—H...O intermolecular interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004561/na6053sup1.cif
Contains datablocks org3, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004561/na6053Isup2.hkl
Contains datablock I

CCDC reference: 162838

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.057
  • wR factor = 0.166
  • Data-to-parameter ratio = 20.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry
Amber Alert Alert Level B:
PLAT_030 Alert B Refined Extinction parameter within range .... 1.50 Sigma
Yellow Alert Alert Level C:
SHFSU_01 Alert C The absolute value of parameter shift to su ratio > 0.05 Absolute value of the parameter shift to su ratio given 0.065 Additional refinement cycles may be required. WEIGH_01 Alert C Extra text has been found in the _refine_ls_weighting_scheme field. This should be in the _refine_ls_weighting_details field. Weighting scheme given as calc w = 1/[\s^2^(Fo^2^)+(0.1000P)^2^] wher Weighting scheme identified as calc
0 Alert Level A = Potentially serious problem
1 Alert Level B = Potential problem
2 Alert Level C = Please check

Comment top

Hydantoins, well known for their central nervous system activity (Tunnicliff, 1996; Morkunas & Miller, 1997), have been reported to possess a variety of pharmacological properties. 5,5-Disubstituted hydantoins often exhibit narcotic and hypnotic activity and have been used for the treatment of chorea and epilepsy. Amino hydantoins are used in the treatment of urinary tract infections, as muscle relaxants and as bactericides. The structure consists of a 2,4-imidazolidinedione ring (commonly known as hydantoin) with a methyl group substituted at the 5 position. A number of 2,4-imidazolidinedione derivatives have been shown to act as inhibitors of metalloproteins (Kelly et al., 1997) and exihibit anti-inflamatory and antifungal activities (Malhotra et al., 1990). Recently 5,5-disubstituted hydantoins have been reported to possess potent inhibitory activity towards HIV protease (Comber, 1992, 1997) and act as sodium channel blockers (Lang et al., 1997; Wayne et al., 1994). Also, hydantoins are attractive substrates for the synthesis of amino acids (Edward & Robert, 1994). In a continuation of our endeavour to design small antimicrobial peptidomimetics, the title compound, (I), was synthesized as an intermediate for an α,β-diamino acid. The structure was determined as a part of the characterization process. Of the two possible diastereomers, only one appears to have been selectively crystallized in our method. Preferential crystallization of hydantoin isomers has been reported in the literature (Ndzie et al., 1997).

Fig. 1 shows the ZORTEP plot (Zsolnai, 1997) of (I) along with the atom-numbering scheme. The whole molecule is not essentially planar, but the five-membered ring is essentially planar. The NMR spectrum of the title compound in DMSO-d6 shows two singlets at 10.67 and 7.62 p.p.m. corresponding to the imide and amide NH protons, respectively. This observation suggests a planar ring conformation, in agreement with a quasi-planar conformation proposed based on the existence of four-bond couplings between amide and imide protons in 1,3-positions of the imidazolidindione ring (Erzsebet et al., 1998). The dihedral angle between the least-squares plane through atoms C3/C8/C9/C10/C11 and the imidazolidine ring is 81.9 (1)°. The dihedral angle between the least-squares planes through atoms C3/C8/C9/C10/C11 and C3/N3/C2/O4/C1 is 77.3 (1)°. The dihedral angle between the least-squares planes through atoms C3/N3/C2/O4/C1 and the five-membered ring is 4.59 (1)°. In the imidazolidine ring, the values of the N1—C5 and C4—C5 distances, and the N1—C5—C4 angle (see Table 1) are in agreement with the literature data (Camerman & Camerman, 1971; Florencio et al., 1978; Verdier et al., 1977, 1979; Fujiwara et al., 1979; Koch et al., 1975), the observed values for the above are in the ranges 1.45–1.48, 1.51–1.55 Å and 99–101°, respectively. The torsion angle C5—C3—C8—C9 of -159.2 (2)° describes the conformation of the portion of the side chain as (-)antiperiplanar about C3—C8.

The packing is stabilized by O—H···O and N—H···O intermolecular hydrogen bonds·The solvent molecule plays a major role in the packing of the molecule. Packing shows that each molecule is bound to the neighbours through hydrogen bonds to form chains running parallel to one another in the crystal, as in the β form (Evans, 1979).

Experimental top

Potassium cyanide (1.3 g, 0.02 mol) and ammonium carbonate (6.283 g, 0.04 mol) were dissolved in aqueous ethanol (200 ml) and 3-acetamido-5 methyl-hexan-2-one (1.7 g, 0.01 mol) was added. The clear reaction mixture was heated at 333–343 K for 9 h and the solvent was removed by distillation. The solid obtained was extracted with ethyl acetate. Evaporation of the ethyl acetate gave a colourless solid which was recrystallized from 0.1 N hydrochloric acid. Crystallization: 750 mg of title compound was dissolved in 7.0 ml me thanol and 3.0 ml (3 N HCl) and the solution was refluxed on a water bath for 1 h and filtered using Whatmann filter paper. The hot solution was allowed to cool to room temprature while methanol was allowed to evaporate. When the volume of the solution was about 5.0 ml, 3–5 drops of conentrated HCl was added along the sides of the container. Needle-like crystals were seen after 16 h. The supernatant was transfered to another beaker and the crystals were dried on a bed of tissue paper.

Refinement top

All H atoms, except for the water H atoms were included at calculated positions and refined using a riding model. The water H atoms were found from difference Fourier syntheses and were refined isotropically.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai, 1997); software used to prepare material for publication: SHELX97 and PARST (Nardelli, 1983, 1995).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme.
5-(1-Acetamido-3-methyl)butyl-5methyl-2,4-imidazolidinedione top
Crystal data top
C11H19N3O3·H2OF(000) = 560
Mr = 259.31Dx = 1.191 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 6.2770 (1) Åθ = 1.5–28.3°
b = 19.7080 (4) ŵ = 0.09 mm1
c = 11.9399 (1) ÅT = 293 K
β = 101.64°Block, white
V = 1446.67 (4) Å30.40 × 0.30 × 0.26 mm
Z = 4
Data collection top
Siemens SMART CCD area-detector
diffractometer
2418 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.063
Graphite monochromatorθmax = 28.2°, θmin = 3.3°
ω scansh = 88
10168 measured reflectionsk = 2626
3536 independent reflectionsl = 159
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)] = 0.057H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.166Calculated w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.94(Δ/σ)max = 0.065
3536 reflectionsΔρmax = 0.34 e Å3
176 parametersΔρmin = 0.36 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.006 (4)
Crystal data top
C11H19N3O3·H2OV = 1446.67 (4) Å3
Mr = 259.31Z = 4
Monoclinic, P21/cMo Kα radiation
a = 6.2770 (1) ŵ = 0.09 mm1
b = 19.7080 (4) ÅT = 293 K
c = 11.9399 (1) Å0.40 × 0.30 × 0.26 mm
β = 101.64°
Data collection top
Siemens SMART CCD area-detector
diffractometer
2418 reflections with I > 2σ(I)
10168 measured reflectionsRint = 0.063
3536 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.166H atoms treated by a mixture of independent and constrained refinement
S = 0.94Δρmax = 0.34 e Å3
3536 reflectionsΔρmin = 0.36 e Å3
176 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
O10.31466 (19)0.44818 (6)0.39815 (12)0.0448 (3)
O20.8988 (2)0.41823 (7)0.43487 (12)0.0431 (3)
O30.7688 (2)0.60247 (7)0.28229 (13)0.0560 (4)
O40.2050 (2)0.78488 (6)0.14294 (15)0.0617 (5)
N10.2575 (2)0.55935 (6)0.33608 (12)0.0339 (3)
H10.12140.56310.33720.041*
N20.5788 (2)0.51240 (6)0.33750 (12)0.0334 (3)
H20.67710.48160.34200.040*
N30.0959 (2)0.68137 (7)0.18933 (13)0.0384 (4)
H30.01130.65830.20430.046*
C10.1523 (3)0.77553 (11)0.1853 (2)0.0645 (6)
H1A0.13610.79760.25820.097*
H1B0.25350.73870.18170.097*
H1C0.20580.80750.12560.097*
C20.0655 (3)0.74846 (8)0.17051 (16)0.0398 (4)
C30.2967 (2)0.64486 (8)0.18620 (14)0.0333 (4)
H3A0.40230.67750.16780.040*
C40.6048 (2)0.57753 (8)0.30615 (14)0.0336 (4)
C50.3908 (2)0.61488 (7)0.30639 (14)0.0312 (4)
C60.4305 (3)0.66987 (9)0.39918 (17)0.0491 (5)
H6A0.29410.68970.40630.074*
H6B0.52330.70440.37850.074*
H6C0.49900.65000.47080.074*
C70.3733 (2)0.50147 (7)0.36149 (14)0.0305 (3)
C80.2566 (3)0.59094 (9)0.09159 (16)0.0457 (5)
H8A0.37300.55780.10740.055*
H8B0.12180.56760.09430.055*
C90.2432 (4)0.61855 (10)0.02962 (17)0.0566 (5)
H90.15780.66050.03730.068*
C100.1258 (5)0.56736 (15)0.1183 (2)0.0895 (9)
H10A0.20430.52520.11020.134*
H10B0.11890.58500.19390.134*
H10C0.01890.55990.10610.134*
C110.4666 (6)0.63487 (17)0.0520 (3)0.1010 (10)
H11A0.53410.66890.00100.152*
H11B0.45300.65150.12870.152*
H11C0.55440.59460.04250.152*
H1O0.871 (4)0.3784 (13)0.414 (2)0.069 (7)*
H2O1.033 (5)0.4268 (13)0.420 (2)0.078 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0390 (6)0.0307 (6)0.0666 (9)0.0022 (5)0.0153 (6)0.0142 (5)
O20.0370 (6)0.0307 (7)0.0653 (9)0.0031 (5)0.0191 (6)0.0002 (6)
O30.0342 (6)0.0503 (8)0.0876 (11)0.0054 (6)0.0220 (7)0.0188 (7)
O40.0527 (8)0.0317 (7)0.1072 (13)0.0011 (6)0.0320 (8)0.0211 (7)
N10.0252 (6)0.0302 (7)0.0490 (9)0.0038 (5)0.0140 (6)0.0114 (6)
N20.0266 (6)0.0283 (7)0.0476 (8)0.0044 (5)0.0131 (6)0.0055 (5)
N30.0303 (7)0.0291 (7)0.0562 (9)0.0021 (5)0.0096 (6)0.0121 (6)
C10.0430 (10)0.0446 (11)0.1070 (19)0.0095 (9)0.0176 (11)0.0152 (11)
C20.0369 (8)0.0298 (8)0.0513 (11)0.0010 (7)0.0058 (7)0.0081 (7)
C30.0334 (7)0.0245 (7)0.0430 (10)0.0010 (6)0.0104 (7)0.0067 (6)
C40.0275 (7)0.0343 (8)0.0404 (9)0.0023 (6)0.0103 (6)0.0051 (6)
C50.0310 (7)0.0253 (7)0.0391 (9)0.0004 (6)0.0112 (6)0.0046 (6)
C60.0651 (12)0.0370 (9)0.0437 (11)0.0015 (8)0.0076 (9)0.0024 (7)
C70.0266 (7)0.0294 (8)0.0361 (8)0.0012 (6)0.0081 (6)0.0029 (6)
C80.0606 (11)0.0323 (9)0.0430 (11)0.0018 (8)0.0073 (9)0.0034 (7)
C90.0823 (15)0.0451 (11)0.0413 (11)0.0069 (10)0.0096 (10)0.0049 (8)
C100.126 (3)0.0854 (19)0.0504 (15)0.0083 (18)0.0027 (15)0.0112 (12)
C110.134 (3)0.101 (2)0.080 (2)0.026 (2)0.0509 (19)0.0090 (16)
Geometric parameters (Å, º) top
O1—C71.222 (2)C3—C81.534 (2)
O2—H1O0.83 (3)C3—H3A0.9800
O2—H2O0.91 (3)C4—C51.533 (2)
O3—C41.225 (2)C5—C61.534 (2)
O4—C21.227 (2)C6—H6A0.9600
N1—C71.354 (2)C6—H6B0.9600
N1—C51.464 (2)C6—H6C0.9600
N1—H10.8600C8—C91.532 (3)
N2—C41.356 (2)C8—H8A0.9700
N2—C71.393 (2)C8—H8B0.9700
N2—H20.8600C9—C111.514 (4)
N3—C21.348 (2)C9—C101.538 (3)
N3—C31.458 (2)C9—H90.9800
N3—H30.8600C10—H10A0.9600
C1—C21.511 (3)C10—H10B0.9600
C1—H1A0.9600C10—H10C0.9600
C1—H1B0.9600C11—H11A0.9600
C1—H1C0.9600C11—H11B0.9600
C3—C51.554 (2)C11—H11C0.9600
H1O—O2—H2O105 (2)C5—C6—H6A109.5
C7—N1—C5112.1 (1)C5—C6—H6B109.5
C7—N1—H1123.9H6A—C6—H6B109.5
C5—N1—H1123.9C5—C6—H6C109.5
C4—N2—C7111.8 (1)H6A—C6—H6C109.5
C4—N2—H2124.1H6B—C6—H6C109.5
C7—N2—H2124.1O1—C7—N1128.1 (1)
C2—N3—C3125.0 (1)O1—C7—N2124.4 (1)
C2—N3—H3117.5N1—C7—N2107.5 (1)
C3—N3—H3117.5C9—C8—C3114.77 (14)
C2—C1—H1A109.5C9—C8—H8A108.6
C2—C1—H1B109.5C3—C8—H8A108.6
H1A—C1—H1B109.5C9—C8—H8B108.6
C2—C1—H1C109.5C3—C8—H8B108.6
H1A—C1—H1C109.5H8A—C8—H8B107.6
H1B—C1—H1C109.5C8—C9—C11111.4 (2)
O4—C2—N3122.2 (2)C8—C9—C10110.15 (19)
O4—C2—C1122.4 (2)C11—C9—C10110.5 (2)
N3—C2—C1115.3 (2)C8—C9—H9108.2
N3—C3—C5109.5 (2)C11—C9—H9108.2
N3—C3—C8110.3 (2)C10—C9—H9108.2
C5—C3—C8113.07 (13)C9—C10—H10A109.5
N3—C3—H3A108.0C9—C10—H10B109.5
C5—C3—H3A108.0H10A—C10—H10B109.5
C8—C3—H3A108.0C9—C10—H10C109.5
O3—C4—N2126.7 (2)H10A—C10—H10C109.5
O3—C4—C5125.9 (2)H10B—C10—H10C109.5
N2—C4—C5107.4 (1)C9—C11—H11A109.5
N1—C5—C4100.7 (1)C9—C11—H11B109.5
N1—C5—C3112.2 (1)H11A—C11—H11B109.5
C4—C5—C3110.5 (1)C9—C11—H11C109.5
N1—C5—C6111.8 (1)H11A—C11—H11C109.5
C4—C5—C6109.0 (1)H11B—C11—H11C109.5
C3—C5—C6111.9 (1)
C3—N3—C2—O43.7 (3)N3—C3—C5—N169.7 (2)
C3—N3—C2—C1176.5 (2)C8—C3—C5—N153.66 (18)
C2—N3—C3—C5117.0 (2)N3—C3—C5—C4178.75 (12)
C2—N3—C3—C8118.03 (18)C8—C3—C5—C457.89 (18)
C7—N2—C4—O3178.4 (2)N3—C3—C5—C656.97 (17)
C7—N2—C4—C51.31 (18)C8—C3—C5—C6179.67 (15)
C7—N1—C5—C45.8 (2)C5—N1—C7—O1173.56 (16)
C7—N1—C5—C3123.4 (1)C5—N1—C7—N26.9 (2)
C7—N1—C5—C6109.85 (16)C4—N2—C7—O1175.4 (2)
O3—C4—C5—N1177.7 (2)C4—N2—C7—N15.03 (19)
N2—C4—C5—N12.6 (2)N3—C3—C8—C977.9 (2)
O3—C4—C5—C358.9 (2)C5—C3—C8—C9159.23 (16)
N2—C4—C5—C3121.37 (14)C3—C8—C9—C1177.0 (2)
O3—C4—C5—C664.6 (2)C3—C8—C9—C10160.0 (2)
N2—C4—C5—C6115.11 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.862.032.809 (2)151
N1—H1···O3i0.862.313.122 (2)157
N3—H3···O3i0.862.122.964 (2)166
O2—H1O···O4ii0.83 (3)1.99 (3)2.820 (2)177 (3)
O2—H2O···O1iii0.91 (3)1.89 (3)2.796 (2)176 (3)
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z+1/2; (iii) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC11H19N3O3·H2O
Mr259.31
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)6.2770 (1), 19.7080 (4), 11.9399 (1)
β (°) 101.64
V3)1446.67 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.40 × 0.30 × 0.26
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10168, 3536, 2418
Rint0.063
(sin θ/λ)max1)0.664
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.057, 0.166, 0.94
No. of reflections3536
No. of parameters176
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.36

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai, 1997), SHELX97 and PARST (Nardelli, 1983, 1995).

Selected geometric parameters (Å, º) top
O1—C71.222 (2)N2—C41.356 (2)
O3—C41.225 (2)N2—C71.393 (2)
O4—C21.227 (2)N3—C21.348 (2)
N1—C71.354 (2)N3—C31.458 (2)
N1—C51.464 (2)C4—C51.533 (2)
C7—N1—C5112.1 (1)O3—C4—N2126.7 (2)
C4—N2—C7111.8 (1)O3—C4—C5125.9 (2)
C2—N3—C3125.0 (1)N2—C4—C5107.4 (1)
O4—C2—N3122.2 (2)N1—C5—C4100.7 (1)
O4—C2—C1122.4 (2)N1—C5—C3112.2 (1)
N3—C2—C1115.3 (2)O1—C7—N1128.1 (1)
N3—C3—C5109.5 (2)O1—C7—N2124.4 (1)
N3—C3—C8110.3 (2)N1—C7—N2107.5 (1)
C3—N3—C2—O43.7 (3)N3—C3—C5—N169.7 (2)
C3—N3—C2—C1176.5 (2)C5—N1—C7—N26.9 (2)
C7—N2—C4—O3178.4 (2)C4—N2—C7—O1175.4 (2)
O3—C4—C5—N1177.7 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O20.862.032.809 (2)151
N1—H1···O3i0.862.313.122 (2)157
N3—H3···O3i0.862.122.964 (2)166
O2—H1O···O4ii0.83 (3)1.99 (3)2.820 (2)177 (3)
O2—H2O···O1iii0.91 (3)1.89 (3)2.796 (2)176 (3)
Symmetry codes: (i) x1, y, z; (ii) x+1, y1/2, z+1/2; (iii) x+1, y, z.
 

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