Hydantoin and hydrogen-bonding patterns in hydantoin derivatives

Yu, F.-L.; Schwalbe, C.H.; Watkin, D.J.

doi:10.1107/S0108270104017706

organic compounds

STRUCTURAL
CHEMISTRY

ISSN: 2053-2296

Volume 60| Part 10| October 2004| Pages o714-o717

doi:10.1107/S0108270104017706

Hydantoin and hydrogen-bonding patterns in hydantoin derivatives

Fang-Lei Yu,^a Carl H. Schwalbe ^a ^* and David J. Watkin ^b

^aAston Pharmacy School, Aston Triangle, Birmingham B4 7ET, England, and ^bChemical Crystallography Laboratory, 9 Parks Road, Oxford OX1 3PD, England
^*Correspondence e-mail: c.h.schwalbe@aston.ac.uk

(Received 21 June 2004; accepted 19 July 2004; online 4 September 2004)

The structure of hydantoin (imidazolidine-2,4-dione), C₃H₄N₂O₂, has been determined from a twinned crystal. The two carbonyl bond lengths are nearly equal, even though one of them adjoins electron-donating NH groups to either side while the other is adjacent to only one. Ab initio molecular-orbital calculations yield more negative Löwdin charge on the former than the latter. Hydantoin molecules form two chains linked by N—H⋯O hydrogen bonds, from which inversion centres create a `chain of rings'. Out of 50 hydantoin moieties in 49 independent molecules of hydantoin derivatives in the Cambridge Structural Database [Version 5.25; Allen (2002 ). Acta Cryst. B58, 380–388], five show this arrangement, six are a variant using the same O atom twice, five form a chain of edge-fused 12-membered hydrogen-bonded rings, and all but three of the remainder have one eight-membered ring and/or one chain connecting their hydantoin rings.

Comment

Hydantoin, (I), is of interest as the parent compound of the anti-epileptic drug diphenylhydantoin and as a supramolecular synthon in its own right. Possessing equal numbers of hydrogen-bond donor (two ring NH) groups and acceptor (two carbonyl O) atoms, it can form intricate networks, but with a different presentation of these groups compared with the six-membered rings so often studied. Probably due to the difficulties with twinning described below, no structure of hydantoin has appeared in the literature to date.

A view of (I) with the atom-numbering scheme is shown in Fig. 1. Electron donation from the ring N atoms to the carbonyl groups, as in resonance structures (Ia)–(Ic), would be expected to lengthen the C=O bonds and shorten the ring C—N bonds, C2=O2 being affected from both sides. The experimental bond distances (Table 1) show no significant differences between the two carbonyl bond lengths or between N1—C2 and N3—C4, but C2—N3 is longer than their average by 0.024 Å (6σ). Thus, resonance structure (Ib) appears to be of limited importance. Both carbonyl groups are bent towards atom N3; the angle O2—C2—N1 exceeds O2—C2—N3 by 3.8 (3)° and the angle O4—C4—C5 exceeds O4—C4—N3 by 2.6 (3)°.

A search group was defined, consisting of a hydantoin ring with both NH groups unsubstituted and sp³ hybridization at C5. With disorder, errors or ions excluded and R < 0.1 required, a search (Bruno et al., 2002 ) of the Cambridge Structural Database (CSD, Version 5.25; Allen, 2002) yielded 41 hits with 50 hydantoin rings in 49 independent molecules after removal of duplicate structure determinations. Mean values of the relevant bond distances, with standard error of the mean in parentheses, confirm the tendency in hydantoin: C2—O2 = 1.221 (1) Å, C4—O4 = 1.211 (1) Å, N1—C2 = 1.342 (2) Å, C2—N3 = 1.393 (2) Å and N3—C4 = 1.362 (1) Å. Bending of one carbonyl bond is common. The mean O2—C2—N1 angle is 127.9 (1)°, compared with 124.5 (1)° for O2—C2—N3, but the other C=O bond lies close to the exterior bisector, mean values being 126.8 (1)° for O4—C4—N3 and 126.3 (1)° for O4—C4—C5.

Ab initio molecular-orbital optimization of hydantoin with GAMESS (Schmidt et al., 1990 ) in the 6-31G* basis set corroborates the near equality of C=O distances and yields N1—C2, C2—N3 and N3—C4 distances of 1.356, 1.391 and 1.367 Å, respectively. Atomic charges were calculated by the method of Löwdin (1950 ), chosen because it is based on orthogonalized orbitals and appears to be consistent with electronegativity. Values of −0.350 on atom N1, −0.382 on O2, −0.275 on N3 and −0.348 on O4 suggest that more negative charge is received by O2 than O4, and more given up by N3 than by N1.

As seen in Fig. 2, each molecule of (I) participates in N—H⋯O hydrogen bonds (Table 2), forming a chain of centrosymmetric rings with graph set C₂²(9) [R₂²(8)] [R₂²(8)] (Etter, 1990 ; Bernstein et al., 1995 ). Of the 50 independent hydantoin rings found in the search of the CSD, this (pseudo-)centrosymmetric `chain of rings' arrangement occurred in five (Table 3; the atom-numbering scheme has always been made to agree with the IUPAC system used in the present study), while another six exhibited a variant form in which the more electron-dense atom O2 simultaneously accepts N1—H1⋯O2 and N3—H3⋯O2 hydrogen bonds, while atom O4 accepts none (Table 4).

Chains are also possible. Hydantoins can create an infinite chain in graph set C(5) with atom N1 as donor and atom O4 as acceptor, simultaneously with another C(4) motif having atom N3 as donor and atom O2 as acceptor, thereby creating edge-fused R₃³(12) rings. This network had five occurrences, always in a non-centrosymmetric space group (Table 5).

Many hydantoin derivatives carry polar substituents on the 5-position, which divert some or all of the hydrogen bonding away from the ring. Thus, 21 molecules participate in a single R₂²(8) motif, 11 involving atom N1 as donor and atom O2 as acceptor, seven with N3 and O2, two with N3 and O4, and one with heterogeneous involvement of N1 with O4 and N3 with O2 (Table 6). Single chains also occur frequently, two C(4) using atoms N1 and O2, five C(5) with N1 and O4, four C(4) with N3 and O2 but none with N3 and O4, and one with heterogeneous chains (Table 7). Finally, three rings only interact with side groups (Table 8). (The total exceeds 50 because two molecules forming one ring and one chain are double-counted.) Of the potential hydrogen-bond donors and acceptors, atom N1 is left unused only three times, O2 just once and N3 not at all, but the less highly charged and less accessible atom O4 is unused 24 times. Thus, hydantoin is a versatile supramolecular synthon providing a challenge to attempts at a priori prediction.

Figure 1
A view of the structure of (I

), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Figure 2
A view of two chains of (I

) extending through the unit cell, with atom N1 of four representative molecules bearing a label. The symmetry codes are: (ii) 1 − x, −y, 1 − z; (iii) $[{1 \over 2}]$ + x, $[{1 \over 2}]$ + y, z; (iv) $[{3 \over 2}]$ − x, $[{1 \over 2}]$ − y, 1 − z. Other molecules are generated from these by adding 1 to both x and z or subtracting 1 from both x and z. Hydrogen bonds are shown as dashed lines.

Experimental

Crystals of (I), in habits ranging from stubby needles to tabular blocks, were grown by slowly cooling to room temperature a saturated aqueous solution prepared at 353 K. An attempt to obtain a more tractable crystal form by diffusing acetic acid vapour into a sample of hydantoin in 12.5% sodium hydroxide solution yielded a conglomerate of sticky needles showing the same unit cell, space group and propensity to form twins.

Crystal data

C₃H₄N₂O₂
M_r = 100.08
Monoclinic, C2/c
a = 9.3538 (7) Å
b = 12.1757 (11) Å
c = 7.2286 (6) Å
β = 104.593 (4)°
V = 796.70 (11) Å³
Z = 8
D_x = 1.669 Mg m⁻³
Mo Kα radiation
Cell parameters from 730 reflections
θ = 5–27°
μ = 0.14 mm⁻¹
T = 190 K
Plate, colourless
0.18 × 0.10 × 0.02 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.99, T_max = 1.00
1593 measured reflections
886 independent reflections
886 reflections with I > −10σ(I)
R_int = 0.02
θ_max = 27.4°
h = −12 → 12
k = −14 → 15
l = −9 → 9

Refinement

Refinement on F²
R(F) = 0.061
wR(F²) = 0.131
S = 1.13
886 reflections
77 parameters
Only coordinates of H atoms refined
w = 1/[σ²(F*) + 1.89P] where P = $[{1 \over 3}]$ max(F_o²,0) + $[{2 \over 3}]$ F_c²
(Δ/σ)_max < 0.001
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C2—O2	1.222 (3)
C2—N1	1.371 (3)
C2—N3	1.393 (3)
N3—C4	1.367 (3)
C4—O4	1.225 (3)
C4—C5	1.460 (3)
C5—N1	1.457 (3)

O2—C2—N1	128.2 (2)
O2—C2—N3	124.4 (2)
N3—C2—N1	107.4 (2)
C4—N3—C2	111.67 (19)
O4—C4—C5	127.9 (2)
O4—C4—N3	125.3 (2)
C5—C4—N3	106.8 (2)
N1—C5—C4	104.7 (2)
C2—N1—C5	109.4 (2)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.95 (3)	2.01 (3)	2.913 (3)	158
N3—H3⋯O4ⁱⁱ	0.87 (4)	1.98 (4)	2.852 (3)	176
Symmetry codes: (i) 2-x,-y,2-z; (ii) 1-x,-y,1-z.

Table 3
Hydantoin derivatives in the CSD forming the same C₂²(9) [R₂²(8)] [R₂²(8)] network as hydantoin or a comparable network with a pseudo-centre of inversion

Refcode	Space group	D—H⋯A	Reference
BCOCHY	C2/m	N1—H⋯O2	Smith-Verdier et al. (1979a )
		N3—H⋯O4
GRNSHY, mol 1	P $[\overline 1]$	N1—H⋯O2′′	Florencio et al. (1980 )
		N3—H⋯O4′′
GRNSHY, mol 2	P $[\overline 1]$	N1—H′′⋯O2
		N3—H′′⋯O4
OCSHYD	C2/c	N1—H⋯O2	Miller & McPhail (1979 )
		N3—H⋯O4
VARBAR	P2₁/c	N1—H⋯O2	Rizzi et al. (1989 )
		N3—H⋯O4

Table 4
Hydantoin derivatives forming a C₁¹(4) C₁¹(4) [R₂²(8)] network based on N1—H⋯O2 and N3—H⋯O2 hydrogen bonds with O4 not used

Refcode	Space group	D—H⋯A	Reference
ADUQOF	P2₁2₁2₁	N1—H⋯O2	Beilles et al. (2001 )
		N3—H⋯O2
BEPNIT	P2₁2₁2₁	N1—H⋯O2	Cassady & Hawkinson (1982 )
		N3—H⋯O2
HPHCMS	P2₁	N1—H⋯O2	Koch et al. (1975 )
		N3—H⋯O4
OGUVIV	P2₁	N1—H⋯O2	Stalker et al. (2002 )
		N3—H⋯O4
XERTUJ, mol 1	P2₁	N1—H⋯O2′′	Koos et al. (2000 )
		N3—H⋯O2′′
XERTUJ, mol 2	P2₁	N1—H′′⋯O2
		N3—H′′⋯O2

Table 5
Hydantoin derivatives forming a chain of edge-fused R₃³(12) rings

Refcode	Space group	D—H⋯A	Reference
DAFFIZ01	P2₁2₁2₁	N1—H⋯O4	Sarges et al. (1985 )
		N3—H⋯O2
LABTIR	P2₁2₁2₁	N1—H⋯O4	Coquerel et al. (1993 )
		N3—H⋯O2
PHYDAN	Pn2₁a	N1—H⋯O4	Camerman & Camerman (1971 )
		N3—H⋯O2
PIPVAL	P2₁	N1—H⋯O4	Modric et al. (1993 )
		N3—H⋯O2
YECDOZ	P2₁2₁2₁	N1—H⋯O4	Park et al. (1994 )
		N3—H⋯O2

Table 6
Hydantoin derivatives forming a single R₂²(8) motif

Refcode	Space group	D—H⋯A	Reference
BICSIP	P2₁/n	N1—H⋯O2	Florencio et al. (1982 )
CECKUQ	P $[\overline 1]$	N1—H⋯O2	Galvez et al. (1983 )
DPHEAD20, mol 1	P $[\overline 1]$	N1—H⋯O2	Mastropaolo et al. (1983 )
EZOSHY	P2₁/c	N1—H⋯O2	Smith-Verdier et al. (1979b )
MANHDT10	P2₁/n	N1—H⋯O2	Vilches et al. (1981 )
MESYIS, mol 1	P1	N1—H⋯O2′′	Koos et al. (2001 )
MESYIS, mol 2	P1	N1—H′′⋯O2
MGSHYD10, mol 1	P2₁	N1—H⋯O2′′	Florencio et al. (1978a )
MGSHYD10, mol 2	P2₁	N1—H′′⋯O2
MZBSHY	P2₁/n	N1—H⋯O2	Florencio et al. (1979 )
TRSHYD10	P2₁/c	N1—H⋯O2	Smith-Verdier et al. (1977 )
ALATIN01	P2₁/c	N3—H⋯O2	Zhang et al. (1992 )
DPHEAD20, mol 2	P $[\overline 1]$	N3—H⋯O2	Mastropaolo et al. (1983)
DPHPZL	P $[\overline 1]$	N3—H⋯O2	Uno & Shimizu (1980 )
HEGRAH	P2₁/c	N3—H⋯O2	Florencio et al. (1978b )
VAPZUH	P2₁/c	N3—H⋯O2	Rizzi et al. (1989)
XERTOD, mol 1	P4₃	N3—H⋯O2′′	Koos et al. (2000)
XERTOD, mol 2	P4₃	N3—H′′⋯O2
AHINEK	P2₁/c	N3—H⋯O4	SethuSankar et al. (2002 )
NIVZOH	P2₁/c	N3—H⋯O4	Benedetti et al. (1997 )
COQQEE†	P2₁	N1—H⋯O4′′	Mullica et al. (1998 )
		N3—H′′⋯O2

†Although Z′ = 1, the molecule has an independent hydantoin ring at each end.

Table 7
Hydantoin derivatives forming a single chain motif

Refcode	Space group	D—H⋯A	Reference
NIVZOH	P2₁/c	N1—H⋯O2	Benedetti et al. (1997)
TOTPIB	P2₁	N1—H⋯O2	Bravo et al. (1996 )
BAGXOW	P2₁/c	N1—H⋯O4	Terzis et al. (1981 )
HOIMCU, mol 1	P2₁/n	N1—H⋯O4	Poje et al. (1980 )
ROKSOZ	Pna2₁	N1—H⋯O4	Gauthier et al. (1997 )
SINZEU	P2₁2₁2₁	N1—H⋯O4	Galdecki & Karolak-Wojciechowska (1986 )
VAPZUH	P2₁/c	N1—H⋯O4	Rizzi et al. (1989)
GODRAS	P2₁2₁2₁	N3—H⋯O2	Eknoian et al. (1999 )
GOPZIU, mol 1	P2₁	N3—H⋯O2′′	Agasimundin et al. (1998 )
GOPZIU, mol 2	P2₁	N3—H′′⋯O2
ROKSUF	P2₁/c	N3—H⋯O2	Gauthier et al. (1997)
COQQEE†	P2₁	N3—H⋯O2′′	Mullica et al. (1998)
		N1—H′′⋯O4

‡Although Z′ = 1, the molecule has an independent hydantoin ring at each end.

Table 8
Hydantoin derivatives without ring-to-ring hydrogen bonding

Refcode	Space group	D—H⋯A	Reference
HOIMCU, mol 2	P2₁/n	None	Poje et al. (1980)
JOPPAF	P2₁	None	Yamagishi et al. (1992 )
QIBNIY	P2₁/c	None	SethuSankar et al. (2001 )

H-atom positions were refined freely, and U_iso(H) values were set initially to 1.2U_eq(C,N) and not refined further. The data were refined as a two-component twin, (1 0 0, 0 1 0, 0 0 1) and (1 0 0.652, 0 $[\overline 1]$ 0, 0 0 $[\overline 1]$ ), with twin element scale factors of 0.869 (6) and 0.131 (6).

Data collection: COLLECT (Nonius, 1998 ); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ) and SHELXL97 (Sheldrick, 1997 ); program(s) used to refine structure: CRYSTALS (Watkin et al., 1999 ); molecular graphics: CAMERON (Watkin et al., 1996 ) and ORTEPII (Johnson, 1976 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S0108270104017706/gd1332sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S0108270104017706/gd1332Isup2.hkl

Comment top

Hydantoin, (I), is of interest as the parent compound of the antiepileptic drug diphenylhydantoin and as a supramolecular synthon in its own right. Possessing equal numbers of hydrogen-bond donor (two ring NH) groups and acceptor (two carbonyl O) atoms, it can form intricate networks, but with a different presentation of these groups compared with the six-membered rings so often studied. Probably due to the difficulties with twinning described below, no structure of hydantoin has appeared in the literature. \sch

The atom-numbering scheme is shown in Fig. 1. Electron donation from the ring N atoms to the carbonyl groups, as in resonance structures (Ia)-(Ic), would be expected to lengthen the C═O bonds and shorten the ring C—N bonds, C2═O2 being affected from both sides. The experimental bond distances show no significant differences between the two carbonyl bond lengths or between N1—C2 and N3—C4, but C2—N3 is longer than their average by 0.024 Å (6σ). Thus resonance structure (Ib) appears to be of limited importance. Both carbonyl groups are bent towards atom N3: the angle O2—C2—N1 exceeds O2—C2—N3 by 3.8 (3)° and O4—C4—C5 exceeds O4—C4—N3 by 2.6 (3)°.

A search group was defined, consisting of a hydantoin ring with both NH groups unsubstituted and sp³ hybridization at C5. With disorder, errors or ions excluded and R < 0.1 required, a search (Bruno et al., 2002) of the Cambridge Structural Database (CSD, Version?; Allen, 2002) yielded 41 hits with 50 hydantoin rings in 49 independent molecules after removal of duplicate structure determinations. Mean values of the relevant bond distances, with standard error of the mean in parentheses, confirm the tendency in hydantoin: C2—O2 1.221 (1), C4—O4 1.211 (1), N1—C2 1.342 (2), C2—N3 1.393 (2) and N3—C4 1.362 (1) Å. Bending of one carbonyl bond is common. The mean O2—C2—N1 angle is 127.9 (1)°, compared with 124.5 (1)° for O2—C2—N3, but the other C═O bond lies close to the exterior bisector, mean values being 126.8 (1)° for O4—C4—N3 and 126.3 (1)° for O4—C4—C5.

Ab initio molecular-orbital optimization of hydantoin with GAMESS (Schmidt et al., 1990) in the 6–31G* basis set corroborates the near equality of C═O distances and yields N1—C2, C2—N3 and N3—C4 distances of 1.356, 1.391 and 1.367 Å, respectively. Atomic charges were calculated by the method of Löwdin (1950), chosen because it is based on orthogonalized orbitals and appears to be consistent with electronegativity. Values of −0.350 on N1, −0.382 on O2, −0.275 on N3 and −0.348 on O4 suggest that more negative charge is received by O2 than O4, and more given up by N3 than by N1.

As seen in Fig. 2, each molecule of (I) participates in N—H···O hydrogen bonds, forming a chain of centrosymmetric rings with graph set C₂²(9) [R₂²(8)] [R₂²(8)] (Etter, 1990; Bernstein et al., 1995). Of the 50 independent hydantoin rings found in the search of the CSD, this (pseudo-)centrosymmetric `chain of rings' arrangement occurred in five (Table 3; the atom-numbering scheme has always been made to agree with the IUPAC system used in the present study), while another six exhibited a variant form in which the more electron-dense atom O2 simultaneously accepts N1—H1···O2 and N3—H3···O2 hydrogen bonds, while atom O4 accepts none (Table 4). Chains are also possible. Hydantoins can create an infinite chain in graph set C(5) with atom N1 as donor and atom O4 as acceptor, simultaneously with another C(4) motif having atom N3 as donor and atom O2 as acceptor, thereby creating edge-fused R₃³(12) rings. This network had five occurrences, always in a non-centrosymmetric space group (Table 5). Scheme 2 here.

Many hydantoin derivatives carry polar substituents on the 5-position, which divert some or all of the hydrogen bonding away from the ring. Thus 21 molecules participate in a single R₂²(8) motif, 11 involving atom N1 as donor and atom O2 as acceptor, seven with N3 and O2, two with N3 and O4 and one with heterogeneous involvement of N1 with O4 and N3 with O2 (Table 6). Single chains also occur frequently, two C(4) using atoms N1 and O2, five C(5) with N1 and O4, four C(4) with N3 and O2 but none with N3 and O4, and one with heterogeneous chains (Table 7). Finally, three rings only interact with side groups (Table 8). (The total exceeds 50 because two molecules forming one ring and one chain are double-counted.) Of the potential hydrogen-bond donors and acceptors, atom N1 is left unused only three times, O2 just once and N3 not at all, but the less highly charged and less accessible atom O4 is unused 24 times. Thus hydantoin is a versatile supramolecular synthon providing a challenge to attempts at a priori prediction.

Experimental top

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994) and SHELXL97 (Sheldrick, 1997); program(s) used to refine structure: CRYSTALS (Watkin et al., 1999); molecular graphics: CAMERON (Watkin et al., 1996) and ORTEPII (Johnson, 1976); software used to prepare material for publication: CRYSTALS.

Figures top

Fig. 1. A view of the structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are indicated by dashed lines.

Fig. 2. A view of two chains of (I) extending through the unit cell, with atom N1 of four representative molecules bearing a label. The symmetry codes are: (2) 1 − x, −y, 1 − z; (3) 1/2 + x, 1/2 + y, z; (4) 3/2 − x, 1/2 − y, 1 − z. Other molecules are generated from these by adding 1 to both x and z or subtracting 1 from both x and z. Hydrogen bonds are shown as dashed lines. The new figure does not match this caption. Do you wish to amend the figure or the caption?

imidazolidine-2,4-dione top

Crystal data top

C₃H₄N₂O₂	F(000) = 416.000
M_r = 100.08	D_x = 1.669 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 730 reflections
a = 9.3538 (7) Å	θ = 5–27°
b = 12.1757 (11) Å	µ = 0.14 mm⁻¹
c = 7.2286 (6) Å	T = 190 K
β = 104.593 (4)°	Plate, colourless
V = 796.70 (11) Å³	0.18 × 0.10 × 0.02 mm
Z = 8

Data collection top

Nonius KappaCCD area-detector diffractometer	886 reflections with I > −10σ(I)
Graphite monochromator	R_int = 0.02
ω scans	θ_max = 27.4°, θ_min = 5.5°
Absorption correction: multi-scan DENZO and SCALEPACK (Otwinowski & Minor, 1997)	h = −12→12
T_min = 0.99, T_max = 1.00	k = −14→15
1593 measured reflections	l = −9→9
886 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	Only H-atom coordinates refined
wR(F²) = 0.131	w = 1/[σ²(F) + 1.89P] where P = 0.333max(F_o²,0) + (1-0.333)F_c²
S = 1.13	(Δ/σ)_max = 0.000095
886 reflections	Δρ_max = 0.27 e Å⁻³
77 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints

Crystal data top

C₃H₄N₂O₂	V = 796.70 (11) Å³
M_r = 100.08	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 9.3538 (7) Å	µ = 0.14 mm⁻¹
b = 12.1757 (11) Å	T = 190 K
c = 7.2286 (6) Å	0.18 × 0.10 × 0.02 mm
β = 104.593 (4)°

Data collection top

Nonius KappaCCD area-detector diffractometer	886 independent reflections
Absorption correction: multi-scan DENZO and SCALEPACK (Otwinowski & Minor, 1997)	886 reflections with I > −10σ(I)
T_min = 0.99, T_max = 1.00	R_int = 0.02
1593 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	0 restraints
wR(F²) = 0.131	Only H-atom coordinates refined
S = 1.13	Δρ_max = 0.27 e Å⁻³
886 reflections	Δρ_min = −0.25 e Å⁻³
77 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.8510 (3)	0.10869 (19)	0.8685 (3)	0.0374
C2	0.7974 (3)	0.00484 (19)	0.8218 (3)	0.0271
N3	0.6630 (2)	0.01532 (16)	0.6856 (3)	0.0271
C4	0.6326 (3)	0.12247 (19)	0.6338 (3)	0.0280
C5	0.7522 (3)	0.1883 (2)	0.7508 (4)	0.0326
O4	0.5237 (2)	0.15458 (14)	0.5136 (3)	0.0376
O2	0.8518 (2)	−0.08264 (14)	0.8866 (3)	0.0366
H51	0.802 (3)	0.224 (3)	0.685 (5)	0.0388*
H52	0.723 (3)	0.236 (3)	0.815 (5)	0.0388*
H1	0.943 (3)	0.119 (2)	0.959 (4)	0.0309*
H3	0.610 (4)	−0.038 (3)	0.623 (5)	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0327 (12)	0.0373 (12)	0.0362 (13)	−0.004 (1)	−0.003 (1)	−0.0052 (9)
C2	0.0268 (12)	0.0249 (11)	0.0285 (11)	−0.0012 (9)	0.0050 (9)	0.0002 (9)
N3	0.027 (1)	0.0198 (9)	0.0303 (11)	−0.0027 (7)	−0.0006 (8)	−0.0005 (7)
C4	0.0328 (12)	0.0236 (11)	0.0255 (12)	−0.0033 (9)	0.0035 (9)	0.0005 (8)
C5	0.0474 (15)	0.0179 (11)	0.0314 (13)	−0.003 (1)	0.0077 (11)	0.0001 (9)
O4	0.0437 (11)	0.0257 (9)	0.035 (1)	0.0016 (7)	−0.0063 (8)	0.0020 (7)
O2	0.036 (1)	0.0262 (9)	0.0417 (11)	0.0036 (7)	−0.0009 (8)	0.0020 (7)

Geometric parameters (Å, º) top

C2—O2	1.222 (3)	C4—C5	1.460 (3)
C2—N1	1.371 (3)	C5—H52	0.83 (3)
C2—N3	1.393 (3)	C5—H51	0.86 (3)
N3—H3	0.87 (4)	C5—N1	1.457 (3)
N3—C4	1.367 (3)	N1—H1	0.95 (3)
C4—O4	1.225 (3)

O2—C2—N1	128.2 (2)	H52—C5—H51	105 (3)
O2—C2—N3	124.4 (2)	H52—C5—N1	113 (2)
N3—C2—N1	107.4 (2)	H51—C5—N1	108 (2)
H3—N3—C4	121 (2)	H52—C5—C4	114 (2)
H3—N3—C2	127 (2)	H51—C5—C4	114 (2)
C4—N3—C2	111.67 (19)	N1—C5—C4	104.7 (2)
O4—C4—C5	127.9 (2)	H1—N1—C2	120.5 (17)
O4—C4—N3	125.3 (2)	H1—N1—C5	130.0 (17)
C5—C4—N3	106.8 (2)	C2—N1—C5	109.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.95 (3)	2.01 (3)	2.913 (3)	158
N3—H3···O4ⁱⁱ	0.87 (4)	1.98 (4)	2.852 (3)	176

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₃H₄N₂O₂
M_r	100.08
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	190
a, b, c (Å)	9.3538 (7), 12.1757 (11), 7.2286 (6)
β (°)	104.593 (4)
V (Å³)	796.70 (11)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.18 × 0.10 × 0.02

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan DENZO and SCALEPACK (Otwinowski & Minor, 1997)
T_min, T_max	0.99, 1.00
No. of measured, independent and observed [I > −10σ(I)] reflections	1593, 886, 886
R_int	0.02
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.131, 1.13
No. of reflections	886
No. of parameters	77
H-atom treatment	Only H-atom coordinates refined
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.25

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994) and SHELXL97 (Sheldrick, 1997), CRYSTALS (Watkin et al., 1999), CAMERON (Watkin et al., 1996) and ORTEPII (Johnson, 1976), CRYSTALS.

Selected geometric parameters (Å, º) top

C2—O2	1.222 (3)	C4—C5	1.460 (3)
C2—N1	1.371 (3)	C5—H52	0.83 (3)
C2—N3	1.393 (3)	C5—H51	0.86 (3)
N3—H3	0.87 (4)	C5—N1	1.457 (3)
N3—C4	1.367 (3)	N1—H1	0.95 (3)
C4—O4	1.225 (3)

O2—C2—N1	128.2 (2)	O4—C4—N3	125.3 (2)
O2—C2—N3	124.4 (2)	C5—C4—N3	106.8 (2)
N3—C2—N1	107.4 (2)	N1—C5—C4	104.7 (2)
C4—N3—C2	111.67 (19)	C2—N1—C5	109.4 (2)
O4—C4—C5	127.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.95 (3)	2.01 (3)	2.913 (3)	158
N3—H3···O4ⁱⁱ	0.87 (4)	1.98 (4)	2.852 (3)	176

Symmetry codes: (i) −x+2, −y, −z+2; (ii) −x+1, −y, −z+1.

Hydantoin derivatives in the CSD forming the same C₂²(9)[R₂²(8)] [R₂²(8)] network as hydantoin, or a comparable network with a pseudo-centre of inversion top

Refcode	Space group	D-H···A	Reference
BCOCHY	C2/m	N1-H···O2	Smith-Verdier et al. (1979a)
		N3-H···O4
GRNSHY mol 1	P1	N1-H···O2"	Florencio et al. (1980)
		N3-H···O4"
GRNSHY mol 2	P1	N1-H"···O2
		N3-H"···O4
OCSHYD	C2/c	N1-H···O2	Miller and McPhail (1979)
		N3-H···O4
VARBAR	P2₁/c	N1-H···O2	Rizzi et al. (1989)
		N3-H···O4

Hydantoin derivatives forming a C₁¹(4) C₁¹(4) [R₂²(8)] network based on N1-H.·O2 and N3-H.·O2 hydrogen bonds with O4 not used top

Refcode	Space group	D-H···A	Reference
ADUQOF	P2₁2₁2₁	N1-H···O2	Beilles et al. (2001)
		N3-H···O2
BEPNIT	P2₁2₁2₁	N1-H···O2	Cassady and Hawkinson (1982)
		N3-H···O2
HPHCMS	P2₁	N1-H···O2	Koch et al. (1975)
		N3-H···O4
OGUVIV	P2₁	N1-H···O2	Stalker et al. (2002)
		N3-H···O4
XERTUJ mol 1	P2₁	N1-H···O2"	Koos et al. (2000)
		N3-H···O2"
XERTUJ mol 2	P2₁	N1-H"···O2
		N3-H"···O2

Hydantoin derivatives forming a chain of edge-fused R₃³(12) rings top

Refcode	Space group	D-H···A	Reference
DAFFIZ01	P2₁2₁2₁	N1-H···O4	Sarges et al. (1985)
		N3-H···O2
LABTIR	P2₁2₁2₁	N1-H···O4	Coquerel et al. (1993)
		N3-H···O2
PHYDAN	Pn2₁a	N1-H···O4	Camerman and Camerman (1971)
		N3-H···O2
PIPVAL	P2₁	N1-H···O4	Modric et al. (1993)
		N3-H···O2
YECDOZ	P2₁2₁2₁	N1-H···O4	Park et al. (1994)
		N3-H···O2

Hydantoin derivatives forming a single [R₂²(8)] motif top

Refcode	Space group	D-H···A	Reference
BICSIP	P2₁/n	N1-H···O2	Florencio et al. (1982)
CECKUQ	P1	N1-H···O2	Galvez et al. (1983)
DPHEAD20 mol 1	P1	N1-H···O2	Mastropaolo et al. (1983)
EZOSHY	P2₁/c	N1-H···O2	Smith-Verdier et al. (1979b)
MANHDT10	P2₁/n	N1-H···O2	Vilches et al. (1981)
MESYIS mol 1	P1	N1-H···O2"	Koos et al. (2001)
MESYIS mol 2	P1	N1-H"···O2
MGSHYD10 mol 1	P2₁	N1-H···O2"	Florencio et al. (1978a)
MGSHYD10 mol 2	P2₁	N1-H"···O2
MZBSHY	P2₁/n	N1-H···O2	Florencio et al. (1979)
TRSHYD10	P2₁/c	N1-H···O2	Smith-Verdier et al. (1977)
ALATIN01	P2₁/c	N3-H···O2	Zhang et al. (1992)
DPHEAD20 mol 2	P1	N3-H···O2	Mastropaolo et al. (1983)
DPHPZL	P1	N3-H···O2	Uno and Shimizu (1980)
HEGRAH	P2₁/c	N3-H···O2	Florencio et al. (1978b)
VAPZUH	P2₁/c	N3-H···O2	Rizzi et al. (1989)
XERTOD mol 1	P4₃	N3-H···O2"	Koos et al. (2000)
XERTOD mol 2	P4₃	N3-H"···O2
AHINEK	P2₁/c	N3-H···O4	SethuSankar et al. (2002)
NIVZOH	P2₁/c	N3-H···O4	Benedetti et al. (1997)
COQQEE^a	P2₁	N1-H···O4"	Mullica et al. (1998)
		N3-H"···O2

(a) Although Z'=1, the molecule has an independent hydantoin ring at each end.

Hydantoin derivatives forming a single chain motif top

Refcode	Space group	D-H···A	Reference
NIVZOH	P2₁/c	N1-H···O2	Benedetti et al. (1997)
TOTPIB	P2₁	N1-H···O2	Bravo et al. (1996)
BAGXOW	P2₁/c	N1-H···O4	Terzis et al. (1981)
HOIMCU mol 1	P2₁/n	N1-H···O4	Poje et al. (1980)
ROKSOZ	Pna2₁	N1-H···O4	Gauthier et al. (1997)
SINZEU	P2₁2₁2₁	N1-H···O4	Galdecki et al. (1986)
VAPZUH	P2₁/c	N1-H···O4	Rizzi et al. (1989)
GODRAS	P2₁2₁2₁	N3-H···O2	Eknoian et al. (1999)
GOPZIU mol 1	P2₁	N3-H···O2"	Agasimundin et al. (1998)
GOPZIU mol 2	P2₁	N3-H"···O2
ROKSUF	P2₁/c	N3-H···O2	Gauthier et al. (1997)
COQQEE^a	P2₁	N3-H···O2"	Mullica et al. (1998)
		N1-H"···O4

(a) Although Z'=1, the molecule has an independent hydantoin ring at each end.

Hydantoin derivatives without ring-to-ring hydrogen bonding top

Refcode	Space group	D-H···A	Reference
HOIMCU mol 2	P2₁/n	None	Poje et al. (1980)
JOPPAF	P2₁	None	Yamagishi et al. (1992)
QIBNIY	P2₁/c	None	SethuSankar et al. (2001)

Acknowledgements

The authors thank the Cambridge Crystallographic Data Centre for providing the CSD at Aston University.

References

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Volume 60| Part 10| October 2004| Pages o714-o717

doi:10.1107/S0108270104017706

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Hydantoin and hydrogen-bonding patterns in hydantoin derivatives

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds