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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o953.
Published online 2009 April 2. doi:  10.1107/S1600536809011404
PMCID: PMC2977653

3-Amino-5-methyl-5-(4-pyrid­yl)hydantoin

Abstract

The title compound, 3-amino-5-methyl-5-(4-pyrid­yl)imid­azol­idine-2,4-dione, C9H10N4O2, was obtained by reaction of 5-methyl-5-(4-pyrid­yl)hydantoin with hydrazine. It crystallizes as a racemate in the tetra­gonal space group I41/a with one mol­ecule in the asymmetric unit. The dihedral angle between the pyridine ring and the five-membered hydantoin ring is 47.99 (3)° In the crystal structure, mol­ecules are joined in a three-dimensional hydrogen-bonded network by N—H(...)N and N—H(...)O links.

Related literature

For the biological activity of hydantoin derivatives and their metal complexes, see: Rajic et al. (2006 [triangle]); Bazil et al. (1998 [triangle]); Bakalova et al. (2005 [triangle], 2008 [triangle], 2009 [triangle]). For crystal structures of other 3-amino substituted hydantoins and their metal complexes, see: Shivachev et al. (2005 [triangle]); Bakalova et al. (2007 [triangle]). For the synthesis of 5-methyl-5-(4-pyridyl)-hydantoin, see: Chu & Teague (1958 [triangle]). For the preparation of 3-amino­hydantoins, see: Davidson (1964 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o953-scheme1.jpg

Experimental

Crystal data

  • C9H10N4O2
  • M r = 206.21
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-65-0o953-efi1.jpg
  • a = 12.8282 (5) Å
  • c = 22.9016 (17) Å
  • V = 3768.8 (3) Å3
  • Z = 16
  • Mo Kα radiation
  • μ = 0.11 mm−1
  • T = 100 K
  • 0.50 × 0.50 × 0.50 mm

Data collection

  • Bruker X8 APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.948, T max = 0.948
  • 51879 measured reflections
  • 2765 independent reflections
  • 2179 reflections with I > 2σ(I)
  • R int = 0.076

Refinement

  • R[F 2 > 2σ(F 2)] = 0.046
  • wR(F 2) = 0.127
  • S = 1.03
  • 2765 reflections
  • 144 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.56 e Å−3
  • Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011404/at2752sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011404/at2752Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors are indebted to Professor V. Arion of the Institute of Inorganic Chemistry of the University of Vienna for discussions about the X-ray data.

supplementary crystallographic information

Comment

Some hydantoin derivatives are biologically active molecules with anticonvulsive, antiarythmic, antimicrobial, antiviral or cytostatic activitiy (Rajic et al., 2006; Bazil et al., 1998). 5-Methyl-5-(4-pyridyl)hydantoin was synthesized by Chu (Chu et al. 1958). This compound was used as starting material for preparation of new 3-amino-5-methyl-5-(4-pyridyl)hydantoin (AMPH). These hydantoin derivatives were utilized as carrier ligands for synthesis of new platinum and palladium complexes with potential cytotoxic activity. (Bakalova et al., 2008, 2009). In the recent work we synthesized AMPH (I) by the method of Davidson (Davidson, 1964) with some modifications. The new compound was characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy and molar conductivity. Suitable crystals of AMPH for X-ray diffraction analysis have been isolated and its structure was determined. The result of X-ray diffraction study of 3-amino-5-methyl-5-(4-pyridyl)hydantoin is shown in Fig. 1. The racemic compound crystallizes in the tetragonal space group I41/a with one molecule in the asymmetric unit. The presence of the sp3-hybridized chiral carbon atom C1 is responsible for the dihedral angle between the pyridine ring and five-membered C3N2 ring of ca 48°. The sum of the angles around N4 is clearly smaller than 360° (327.0°), indicating its trigonal-pyramidal configuration. The lone-pair region at N4 is directed towards adjacent atom O1. The secondary amine nitrogen N2 acts as a proton donor in an intermolecular bifurcated hydrogen bonding interactions with the nitrogen atom N4 and oxygen atom O2 of the neighbouring molecule of AMPH (Fig. 2) The hydrazinic atom N4 is involved in two intermolecular H bonds with the atoms O1ii and O1iii of the two different neighbouring molecules (Table 1).

Experimental

3-Amino-5-methyl-5-(4-pyridyl)hydantoin was synthesized by dissolving 5-methyl-5(4-pyridyl)hydantoin (1.91 g, 10 mmol) in 98% N2H4.H2O (5 cm3) and refluxing the solution for 2 h. The reaction mixture was cooled to room temperature and water (15 cm3) was added. The solution was placed in refrigerator for 24 h. The white product was filtered off, recrystallized from ethanol and dried at 373 K for 5 h. The purity was checked by TLC. The substance is soluble in DMSO and weakly soluble in water and ethanol. Yield: 1.26 g, 61%, m.p. = 523.2–524.7 K. Crystals, suitable for X-ray data collection were grown by slow evaporation from ethanol solution at 277 K. Analysis calculated for C9H10N4O2: C 52.42, H 4.89, N 27.17%. Found: C 52.23, H 4.46, N 26.83%. λM = 0.979 S.cm2.mol-1; IR(pellets KBr)/cm-1: 3314.0, 3276.0, 1766.9, 1713.0, 1597.2 and 1411.1. 1H NMR (250 MHz; DMSO-d6): 8.95 (1H, s, N(1)—H), 8.59 (2H, d, J=7 Hz, H-2, H-6), 7.50 (2H, d, J=7 Hz, H-3, H-5), 4.80 (2H, s, NH2), 1.66 (3H, s, CH3). 13C NMR (62.5 MHz; DMSO-d6): 172.7 (C=O-4`), 155.5 (C=O-2`), 150.0 (C-2,C-6), 148.4 (C-4), 120.6 (C-3, C-5), 60.8 (C-5`), 24.7 (CH3).

Refinement

H atoms were placed at calculated positions [N—H = 0.88 Å, C—H = 0.95 and 0.98 Å] and refined as riding atoms in the subsequent least squares model refinements, except two hydrogen atoms at N4 which were localized from difference map. The isotropic thermal parameters of hydrogen atoms in the positions of which were calculated were estimated to be 1.2 or 1.5 times the values of the equivalent isotropic thermal parameters of the atoms to which H atoms were bonded.

Figures

Fig. 1.
View of the molecule of AMPH with atom labeling scheme; the thermal ellipsoids are drawn at 50% probability level.
Fig. 2.
Fragment of the crystal structure of AMPH showing the intermolecular hydrogen bonding interactions. [Symmetry codes: (i) –y +1.25, x – 0.25, z – 0.25; (ii) y – 0.25, –x + 1.25, –z + 0.25; (iii) –y ...

Crystal data

C9H10N4O2Dx = 1.454 Mg m3
Mr = 206.21Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 847 reflections
Hall symbol: -I 4adθ = 2.9–29.5°
a = 12.8282 (5) ŵ = 0.11 mm1
c = 22.9016 (17) ÅT = 100 K
V = 3768.8 (3) Å3Block, colourless
Z = 160.50 × 0.50 × 0.50 mm
F(000) = 1728

Data collection

Bruker X8 APEXII CCD diffractometer2765 independent reflections
Radiation source: fine-focus sealed tube2179 reflections with I > 2σ(I)
graphiteRint = 0.076
ω scansθmax = 30.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −18→18
Tmin = 0.948, Tmax = 0.948k = −18→18
51879 measured reflectionsl = −32→32

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.046Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H atoms treated by a mixture of independent and constrained refinement
S = 1.03w = 1/[σ2(Fo2) + (0.0631P)2 + 3.9566P] where P = (Fo2 + 2Fc2)/3
2765 reflections(Δ/σ)max < 0.001
144 parametersΔρmax = 0.56 e Å3
0 restraintsΔρmin = −0.44 e Å3

Special details

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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)

xyzUiso*/Ueq
O10.59104 (8)0.59567 (7)0.06315 (4)0.0171 (2)
O20.68145 (8)0.42948 (8)0.23252 (4)0.0203 (2)
N10.58287 (9)0.06249 (9)0.13055 (5)0.0176 (2)
N20.67304 (9)0.43740 (9)0.07949 (5)0.0150 (2)
H20.68200.41720.04310.018*
N30.62479 (8)0.53105 (8)0.15592 (5)0.0128 (2)
N40.57993 (10)0.61113 (9)0.18907 (5)0.0181 (2)
H4A0.5062 (15)0.6163 (15)0.1787 (8)0.027 (5)*
H4B0.6100 (16)0.6781 (17)0.1806 (9)0.036 (5)*
C10.70691 (10)0.37686 (10)0.12997 (5)0.0136 (3)
C20.65758 (10)0.26869 (10)0.13127 (5)0.0131 (2)
C30.63039 (11)0.21921 (10)0.07925 (6)0.0165 (3)
H30.63650.25470.04300.020*
C40.59419 (11)0.11717 (11)0.08121 (6)0.0178 (3)
H40.57640.08430.04540.021*
C50.60863 (11)0.11133 (11)0.18034 (6)0.0179 (3)
H50.60080.07420.21600.021*
C60.64606 (11)0.21278 (10)0.18292 (6)0.0165 (3)
H60.66350.24350.21940.020*
C70.82617 (11)0.36654 (11)0.13212 (7)0.0201 (3)
H7A0.85780.43600.13120.030*
H7B0.85020.32620.09840.030*
H7C0.84660.33080.16820.030*
C80.67014 (10)0.44623 (10)0.18059 (6)0.0139 (3)
C90.62667 (10)0.52740 (10)0.09462 (5)0.0132 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0197 (5)0.0162 (5)0.0154 (5)0.0016 (4)−0.0004 (3)0.0034 (3)
O20.0299 (6)0.0178 (5)0.0131 (5)0.0007 (4)−0.0040 (4)0.0002 (4)
N10.0152 (5)0.0153 (5)0.0223 (6)−0.0003 (4)0.0004 (4)0.0004 (4)
N20.0195 (5)0.0145 (5)0.0109 (5)0.0020 (4)0.0019 (4)0.0013 (4)
N30.0136 (5)0.0132 (5)0.0117 (5)0.0002 (4)0.0011 (4)−0.0005 (4)
N40.0194 (6)0.0169 (6)0.0180 (6)0.0016 (4)0.0023 (4)−0.0030 (4)
C10.0153 (6)0.0130 (6)0.0126 (6)0.0006 (4)0.0000 (4)0.0010 (4)
C20.0114 (5)0.0127 (6)0.0151 (6)0.0014 (4)0.0006 (4)0.0005 (4)
C30.0177 (6)0.0172 (6)0.0146 (6)0.0010 (5)−0.0012 (5)0.0008 (5)
C40.0178 (6)0.0172 (6)0.0183 (6)0.0000 (5)−0.0019 (5)−0.0027 (5)
C50.0193 (6)0.0162 (6)0.0182 (6)−0.0008 (5)0.0013 (5)0.0031 (5)
C60.0189 (6)0.0160 (6)0.0145 (6)−0.0008 (5)0.0005 (5)0.0006 (5)
C70.0140 (6)0.0175 (6)0.0286 (7)−0.0002 (5)0.0006 (5)0.0027 (5)
C80.0140 (6)0.0134 (6)0.0143 (6)−0.0025 (4)−0.0013 (4)−0.0001 (4)
C90.0120 (6)0.0151 (6)0.0126 (6)−0.0019 (5)0.0011 (4)0.0004 (4)

Geometric parameters (Å, °)

O1—C91.2229 (16)C1—C81.5355 (18)
O2—C81.2174 (16)C1—C71.5364 (19)
N1—C41.3378 (18)C2—C61.3913 (18)
N1—C51.3425 (18)C2—C31.3942 (18)
N2—C91.3442 (17)C3—C41.3897 (19)
N2—C11.4589 (16)C3—H30.9500
N2—H20.8800C4—H40.9500
N3—C81.3571 (17)C5—C61.3884 (19)
N3—N41.4010 (16)C5—H50.9500
N3—C91.4047 (17)C6—H60.9500
N4—H4A0.978 (19)C7—H7A0.9800
N4—H4B0.96 (2)C7—H7B0.9800
C1—C21.5254 (18)C7—H7C0.9800
C4—N1—C5116.49 (12)N1—C4—C3123.89 (13)
C9—N2—C1112.63 (11)N1—C4—H4118.1
C9—N2—H2123.7C3—C4—H4118.1
C1—N2—H2123.7N1—C5—C6123.97 (13)
C8—N3—N4122.57 (11)N1—C5—H5118.0
C8—N3—C9112.46 (10)C6—C5—H5118.0
N4—N3—C9124.96 (11)C5—C6—C2118.94 (12)
N3—N4—H4A108.4 (11)C5—C6—H6120.5
N3—N4—H4B112.4 (12)C2—C6—H6120.5
H4A—N4—H4B106.2 (17)C1—C7—H7A109.5
N2—C1—C2112.09 (10)C1—C7—H7B109.5
N2—C1—C8101.43 (10)H7A—C7—H7B109.5
C2—C1—C8112.65 (10)C1—C7—H7C109.5
N2—C1—C7111.58 (11)H7A—C7—H7C109.5
C2—C1—C7109.52 (11)H7B—C7—H7C109.5
C8—C1—C7109.37 (11)O2—C8—N3126.83 (12)
C6—C2—C3117.73 (12)O2—C8—C1126.77 (12)
C6—C2—C1121.97 (11)N3—C8—C1106.38 (11)
C3—C2—C1120.09 (11)O1—C9—N2128.95 (12)
C4—C3—C2119.00 (12)O1—C9—N3123.97 (12)
C4—C3—H3120.5N2—C9—N3107.08 (11)
C2—C3—H3120.5
C9—N2—C1—C2121.59 (12)N4—N3—C8—O2−2.7 (2)
C9—N2—C1—C81.19 (14)C9—N3—C8—O2178.47 (13)
C9—N2—C1—C7−115.16 (12)N4—N3—C8—C1178.74 (11)
N2—C1—C2—C6−155.89 (12)C9—N3—C8—C1−0.11 (14)
C8—C1—C2—C6−42.24 (17)N2—C1—C8—O2−179.19 (13)
C7—C1—C2—C679.71 (15)C2—C1—C8—O260.81 (17)
N2—C1—C2—C329.50 (16)C7—C1—C8—O2−61.23 (17)
C8—C1—C2—C3143.15 (12)N2—C1—C8—N3−0.61 (13)
C7—C1—C2—C3−94.90 (14)C2—C1—C8—N3−120.62 (11)
C6—C2—C3—C4−0.49 (19)C7—C1—C8—N3117.35 (12)
C1—C2—C3—C4174.35 (12)C1—N2—C9—O1179.01 (13)
C5—N1—C4—C30.0 (2)C1—N2—C9—N3−1.30 (14)
C2—C3—C4—N10.4 (2)C8—N3—C9—O1−179.43 (12)
C4—N1—C5—C6−0.4 (2)N4—N3—C9—O11.8 (2)
N1—C5—C6—C20.4 (2)C8—N3—C9—N20.86 (14)
C3—C2—C6—C50.1 (2)N4—N3—C9—N2−177.95 (11)
C1—C2—C6—C5−174.61 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O2i0.882.262.9184 (15)131
N2—H2···N4i0.882.693.526159
N4—H4A···O1ii0.977 (19)2.139 (19)3.0676 (16)158.07
N4—H4B···O1iii0.96 (2)2.17 (2)3.1003 (16)162.23

Symmetry codes: (i) −y+5/4, x−1/4, z−1/4; (ii) y−1/4, −x+5/4, −z+1/4; (iii) −y+5/4, x+1/4, −z+1/4.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: AT2752).

References

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