3-Amino-5-methyl-5-(4-pyrid-yl)hydantoin.

The title compound, 3-amino-5-methyl-5-(4-pyrid-yl)imid-azol-idine-2,4-dione, C(9)H(10)N(4)O(2), was obtained by reaction of 5-methyl-5-(4-pyrid-yl)hydantoin with hydrazine. It crystallizes as a racemate in the tetra-gonal space group I4(1)/a with one mol-ecule 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, mol-ecules 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 ▶); Bazil et al. (1998 ▶); Bakalova et al. (2005 ▶, 2008 ▶, 2009 ▶). For crystal structures of other 3-amino substituted hydantoins and their metal complexes, see: Shivachev et al. (2005 ▶); Bakalova et al. (2007 ▶). For the synthesis of 5-methyl-5-(4-pyridyl)-hydantoin, see: Chu & Teague (1958 ▶). For the preparation of 3-amino­hydantoins, see: Davidson (1964 ▶).

Experimental

Crystal data

C9H10N4O2

M = 206.21

Tetragonal,

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

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

C9H10N4O2	Dx = 1.454 Mg m−3
Mr = 206.21	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 847 reflections
Hall symbol: -I 4ad	θ = 2.9–29.5°
a = 12.8282 (5) Å	µ = 0.11 mm−1
c = 22.9016 (17) Å	T = 100 K
V = 3768.8 (3) Å3	Block, colourless
Z = 16	0.50 × 0.50 × 0.50 mm
F(000) = 1728

Bruker X8 APEXII CCD diffractometer	2765 independent reflections
Radiation source: fine-focus sealed tube	2179 reflections with I > 2σ(I)
graphite	Rint = 0.076
ω scans	θmax = 30.1°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −18→18
Tmin = 0.948, Tmax = 0.948	k = −18→18
51879 measured reflections	l = −32→32

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0631P)2 + 3.9566P] where P = (Fo2 + 2Fc2)/3
2765 reflections	(Δ/σ)max < 0.001
144 parameters	Δρmax = 0.56 e Å−3
0 restraints	Δρmin = −0.44 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.59104 (8)	0.59567 (7)	0.06315 (4)	0.0171 (2)
O2	0.68145 (8)	0.42948 (8)	0.23252 (4)	0.0203 (2)
N1	0.58287 (9)	0.06249 (9)	0.13055 (5)	0.0176 (2)
N2	0.67304 (9)	0.43740 (9)	0.07949 (5)	0.0150 (2)
H2	0.6820	0.4172	0.0431	0.018*
N3	0.62479 (8)	0.53105 (8)	0.15592 (5)	0.0128 (2)
N4	0.57993 (10)	0.61113 (9)	0.18907 (5)	0.0181 (2)
H4A	0.5062 (15)	0.6163 (15)	0.1787 (8)	0.027 (5)*
H4B	0.6100 (16)	0.6781 (17)	0.1806 (9)	0.036 (5)*
C1	0.70691 (10)	0.37686 (10)	0.12997 (5)	0.0136 (3)
C2	0.65758 (10)	0.26869 (10)	0.13127 (5)	0.0131 (2)
C3	0.63039 (11)	0.21921 (10)	0.07925 (6)	0.0165 (3)
H3	0.6365	0.2547	0.0430	0.020*
C4	0.59419 (11)	0.11717 (11)	0.08121 (6)	0.0178 (3)
H4	0.5764	0.0843	0.0454	0.021*
C5	0.60863 (11)	0.11133 (11)	0.18034 (6)	0.0179 (3)
H5	0.6008	0.0742	0.2160	0.021*
C6	0.64606 (11)	0.21278 (10)	0.18292 (6)	0.0165 (3)
H6	0.6635	0.2435	0.2194	0.020*
C7	0.82617 (11)	0.36654 (11)	0.13212 (7)	0.0201 (3)
H7A	0.8578	0.4360	0.1312	0.030*
H7B	0.8502	0.3262	0.0984	0.030*
H7C	0.8466	0.3308	0.1682	0.030*
C8	0.67014 (10)	0.44623 (10)	0.18059 (6)	0.0139 (3)
C9	0.62667 (10)	0.52740 (10)	0.09462 (5)	0.0132 (3)

	U11	U22	U33	U12	U13	U23
O1	0.0197 (5)	0.0162 (5)	0.0154 (5)	0.0016 (4)	−0.0004 (3)	0.0034 (3)
O2	0.0299 (6)	0.0178 (5)	0.0131 (5)	0.0007 (4)	−0.0040 (4)	0.0002 (4)
N1	0.0152 (5)	0.0153 (5)	0.0223 (6)	−0.0003 (4)	0.0004 (4)	0.0004 (4)
N2	0.0195 (5)	0.0145 (5)	0.0109 (5)	0.0020 (4)	0.0019 (4)	0.0013 (4)
N3	0.0136 (5)	0.0132 (5)	0.0117 (5)	0.0002 (4)	0.0011 (4)	−0.0005 (4)
N4	0.0194 (6)	0.0169 (6)	0.0180 (6)	0.0016 (4)	0.0023 (4)	−0.0030 (4)
C1	0.0153 (6)	0.0130 (6)	0.0126 (6)	0.0006 (4)	0.0000 (4)	0.0010 (4)
C2	0.0114 (5)	0.0127 (6)	0.0151 (6)	0.0014 (4)	0.0006 (4)	0.0005 (4)
C3	0.0177 (6)	0.0172 (6)	0.0146 (6)	0.0010 (5)	−0.0012 (5)	0.0008 (5)
C4	0.0178 (6)	0.0172 (6)	0.0183 (6)	0.0000 (5)	−0.0019 (5)	−0.0027 (5)
C5	0.0193 (6)	0.0162 (6)	0.0182 (6)	−0.0008 (5)	0.0013 (5)	0.0031 (5)
C6	0.0189 (6)	0.0160 (6)	0.0145 (6)	−0.0008 (5)	0.0005 (5)	0.0006 (5)
C7	0.0140 (6)	0.0175 (6)	0.0286 (7)	−0.0002 (5)	0.0006 (5)	0.0027 (5)
C8	0.0140 (6)	0.0134 (6)	0.0143 (6)	−0.0025 (4)	−0.0013 (4)	−0.0001 (4)
C9	0.0120 (6)	0.0151 (6)	0.0126 (6)	−0.0019 (5)	0.0011 (4)	0.0004 (4)

O1—C9	1.2229 (16)	C1—C8	1.5355 (18)
O2—C8	1.2174 (16)	C1—C7	1.5364 (19)
N1—C4	1.3378 (18)	C2—C6	1.3913 (18)
N1—C5	1.3425 (18)	C2—C3	1.3942 (18)
N2—C9	1.3442 (17)	C3—C4	1.3897 (19)
N2—C1	1.4589 (16)	C3—H3	0.9500
N2—H2	0.8800	C4—H4	0.9500
N3—C8	1.3571 (17)	C5—C6	1.3884 (19)
N3—N4	1.4010 (16)	C5—H5	0.9500
N3—C9	1.4047 (17)	C6—H6	0.9500
N4—H4A	0.978 (19)	C7—H7A	0.9800
N4—H4B	0.96 (2)	C7—H7B	0.9800
C1—C2	1.5254 (18)	C7—H7C	0.9800
C4—N1—C5	116.49 (12)	N1—C4—C3	123.89 (13)
C9—N2—C1	112.63 (11)	N1—C4—H4	118.1
C9—N2—H2	123.7	C3—C4—H4	118.1
C1—N2—H2	123.7	N1—C5—C6	123.97 (13)
C8—N3—N4	122.57 (11)	N1—C5—H5	118.0
C8—N3—C9	112.46 (10)	C6—C5—H5	118.0
N4—N3—C9	124.96 (11)	C5—C6—C2	118.94 (12)
N3—N4—H4A	108.4 (11)	C5—C6—H6	120.5
N3—N4—H4B	112.4 (12)	C2—C6—H6	120.5
H4A—N4—H4B	106.2 (17)	C1—C7—H7A	109.5
N2—C1—C2	112.09 (10)	C1—C7—H7B	109.5
N2—C1—C8	101.43 (10)	H7A—C7—H7B	109.5
C2—C1—C8	112.65 (10)	C1—C7—H7C	109.5
N2—C1—C7	111.58 (11)	H7A—C7—H7C	109.5
C2—C1—C7	109.52 (11)	H7B—C7—H7C	109.5
C8—C1—C7	109.37 (11)	O2—C8—N3	126.83 (12)
C6—C2—C3	117.73 (12)	O2—C8—C1	126.77 (12)
C6—C2—C1	121.97 (11)	N3—C8—C1	106.38 (11)
C3—C2—C1	120.09 (11)	O1—C9—N2	128.95 (12)
C4—C3—C2	119.00 (12)	O1—C9—N3	123.97 (12)
C4—C3—H3	120.5	N2—C9—N3	107.08 (11)
C2—C3—H3	120.5
C9—N2—C1—C2	121.59 (12)	N4—N3—C8—O2	−2.7 (2)
C9—N2—C1—C8	1.19 (14)	C9—N3—C8—O2	178.47 (13)
C9—N2—C1—C7	−115.16 (12)	N4—N3—C8—C1	178.74 (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—C6	79.71 (15)	C2—C1—C8—O2	60.81 (17)
N2—C1—C2—C3	29.50 (16)	C7—C1—C8—O2	−61.23 (17)
C8—C1—C2—C3	143.15 (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—N3	117.35 (12)
C1—C2—C3—C4	174.35 (12)	C1—N2—C9—O1	179.01 (13)
C5—N1—C4—C3	0.0 (2)	C1—N2—C9—N3	−1.30 (14)
C2—C3—C4—N1	0.4 (2)	C8—N3—C9—O1	−179.43 (12)
C4—N1—C5—C6	−0.4 (2)	N4—N3—C9—O1	1.8 (2)
N1—C5—C6—C2	0.4 (2)	C8—N3—C9—N2	0.86 (14)
C3—C2—C6—C5	0.1 (2)	N4—N3—C9—N2	−177.95 (11)
C1—C2—C6—C5	−174.61 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2i	0.88	2.26	2.9184 (15)	131
N2—H2···N4i	0.88	2.69	3.526	159
N4—H4A···O1ii	0.977 (19)	2.139 (19)	3.0676 (16)	158.07
N4—H4B···O1iii	0.96 (2)	2.17 (2)	3.1003 (16)	162.23

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N4i	0.88	2.69	3.526	159
N2—H2⋯O2i	0.88	2.26	2.9184 (15)	131
N4—H4A⋯O1ii	0.977 (19)	2.139 (19)	3.0676 (16)	158.07
N4—H4B⋯O1iii	0.96 (2)	2.17 (2)	3.1003 (16)	162.23

Symmetry codes: (i) ; (ii) ; (iii) .