2-Amino-1-methyl-1H-imidazol-4(5H)-one dimethyl sulfoxide monosolvate

Tutughamiarso, M.; Bolte, M.

doi:10.1107/S1600536810038997

organic compounds

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ISSN: 2056-9890

Volume 66| Part 11| November 2010| Page o2714

https://doi.org/10.1107/S1600536810038997

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2-Amino-1-methyl-1H-imidazol-4(5H)-one dimethyl sulfoxide monosolvate

Maya Tutughamiarso ^a and Michael Bolte ^b ^*

^aInstitut für Organische Chemie und Chemische Biologie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, and ^bInstitut für Anorganische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 21 September 2010; accepted 29 September 2010; online 2 October 2010)

In the title compound, C₄H₇N₃O·C₂H₆OS, creatinine [2-amino-1-methyl-1H-imidazol-4(5H)one] exists in the amine form. The ring is planar (r.m.s. deviation for all non-H atoms = 0.017 Å). In the crystal, two creatinine molecules form centrosymmetric hydrogen-bonded dimers linked by pairs of N—H⋯N hydrogen bonds. In addition, creatinine is linked to a dimethyl sulfoxide molecule by an N—H⋯O interaction. The packing shows layers parallel to (120).

Related literature

For information about creatinine, see: Narayanan & Appleton (1980 ). For related structures, see: Bell et al. (1995 ). For co-crystallization experiments, see: Ton & Bolte (2009 ). For hydrogen-bond patterns, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₄H₇N₃O·C₂H₆OS
M_r = 191.25
Triclinic, $[P \overline 1]$
a = 5.8997 (10) Å
b = 7.3018 (13) Å
c = 11.276 (2) Å
α = 75.861 (18)°
β = 83.763 (16)°
γ = 79.694 (13)°
V = 462.36 (14) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 173 K
0.50 × 0.40 × 0.40 mm

Data collection

Siemens SMART 1K CCD diffractometer
8161 measured reflections
2997 independent reflections
2597 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.082
S = 0.98
2997 reflections
120 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N51—H51A⋯O1D	0.823 (18)	2.028 (18)	2.8403 (13)	169.3 (17)
N51—H51B⋯N1ⁱ	0.887 (16)	2.040 (16)	2.9225 (14)	172.9 (14)
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 ) and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810038997/bx2310sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810038997/bx2310Isup2.hkl

checkCIF report

Comment top

Creatinine is an important end product of nitrogen metabolism and appears in the urine of healthy individuals (Narayanan & Appleton, 1980). Due to the tautomerism, creatinine can exist in two forms, the amine and the imine form. Spectroscopic studies show that the amine form is preferred in the solid state (Bell et al., 1995). To better understand the binding of creatinine to its receptor, we cocrystallized creatinine together with model compounds containing complementary functional groups. During the cocrystallization screening, a creatinine dimethylsulfoxide solvate was obtained. In this structure, the planar creatinine exist also in the amine form (r.m.s. deviation = 0.017 Å for all non-H atoms). The C═N bond is longer than the C—NH₂bond [bond lenghts = 1.359 (1) Å and 1.327 (1) Å]. This reversed relation between bond length and nitrogen valence shows that the π- electron density is delocalized over the amine-imine group. Creatinine is linked to the solvate molecule by a N—H···O interaction (Fig. 1). This hydrogen-bonded entity is further connected by two N—H···N hydrogen bonds with a R²₂(8) pattern forming a centrosymmetric dimer (Bernstein et al., 1995; Fig. 2). The packing shows layers parallel to the (1 2 0) plane.

Related literature top

For information about creatinine, see: Narayanan & Appleton (1980). For related structures, see: Bell et al. (1995). For co-crystallization experiments, see: Ton & Bolte (2009). For hydrogen-bond patterns, see: Bernstein et al. (1995).

Experimental top

Single crystals of title compound were obtained by cocrystallization of the commercially available 5-fluorocytosine (2.0 mg) and creatinine (2.1 mg) from dimethylsufoxide (100 µL) at 323 K.

Structure description top

For information about creatinine, see: Narayanan & Appleton (1980). For related structures, see: Bell et al. (1995). For co-crystallization experiments, see: Ton & Bolte (2009). For hydrogen-bond patterns, see: Bernstein et al. (1995).

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008) and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A perspective view of the title compound, 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. The dashed line indicates the N—H···O interaction.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

2-Amino-1-methyl-1H-imidazol-4(5H)-one dimethyl sulfoxide monosolvate top

Crystal data top

C₄H₇N₃O·C₂H₆OS	Z = 2
M_r = 191.25	F(000) = 204
Triclinic, P1	D_x = 1.374 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8997 (10) Å	Cell parameters from 131 reflections
b = 7.3018 (13) Å	θ = 1.9–32.6°
c = 11.276 (2) Å	µ = 0.32 mm⁻¹
α = 75.861 (18)°	T = 173 K
β = 83.763 (16)°	Block, colorless
γ = 79.694 (13)°	0.50 × 0.40 × 0.40 mm
V = 462.36 (14) Å³

Data collection top

Siemens SMART 1K CCD diffractometer	2597 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 32.6°, θ_min = 1.9°
ω scans	h = −8→8
8161 measured reflections	k = −10→10
2997 independent reflections	l = −16→16

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0417P)² + 0.166P] where P = (F_o² + 2F_c²)/3
2997 reflections	(Δ/σ)_max = 0.001
120 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₄H₇N₃O·C₂H₆OS	γ = 79.694 (13)°
M_r = 191.25	V = 462.36 (14) Å³
Triclinic, P1	Z = 2
a = 5.8997 (10) Å	Mo Kα radiation
b = 7.3018 (13) Å	µ = 0.32 mm⁻¹
c = 11.276 (2) Å	T = 173 K
α = 75.861 (18)°	0.50 × 0.40 × 0.40 mm
β = 83.763 (16)°

Data collection top

Siemens SMART 1K CCD diffractometer	2597 reflections with I > 2σ(I)
8161 measured reflections	R_int = 0.022
2997 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.29 e Å⁻³
2997 reflections	Δρ_min = −0.32 e Å⁻³
120 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	U_iso*/U_eq
N1	0.82954 (15)	0.63634 (13)	0.38132 (8)	0.01974 (17)
C2	0.72822 (18)	0.72352 (15)	0.27441 (9)	0.01971 (19)
C3	0.48598 (18)	0.82480 (16)	0.30299 (9)	0.0218 (2)
H3A	0.4687	0.9638	0.2660	0.026*
H3B	0.3661	0.7699	0.2743	0.026*
N4	0.47636 (15)	0.78571 (13)	0.43582 (8)	0.02055 (18)
C5	0.67429 (17)	0.67487 (14)	0.47372 (9)	0.01701 (18)
O21	0.81565 (15)	0.72319 (13)	0.17026 (7)	0.02772 (18)
C41	0.27148 (18)	0.84273 (17)	0.50969 (11)	0.0239 (2)
H41A	0.1484	0.7740	0.5006	0.036*
H41B	0.2206	0.9807	0.4824	0.036*
H41C	0.3068	0.8120	0.5959	0.036*
N51	0.72130 (16)	0.60912 (14)	0.59037 (8)	0.02144 (18)
H51A	0.630 (3)	0.632 (2)	0.6476 (16)	0.038 (4)*
H51B	0.856 (3)	0.534 (2)	0.6059 (14)	0.029 (4)*
O1D	0.45535 (15)	0.70620 (14)	0.79813 (8)	0.0308 (2)
S2D	0.29265 (4)	0.65071 (4)	0.90915 (2)	0.02067 (8)
C3D	0.3041 (2)	0.81135 (17)	1.00396 (10)	0.0247 (2)
H3D1	0.4563	0.7846	1.0372	0.037*
H3D2	0.1847	0.7944	1.0715	0.037*
H3D3	0.2775	0.9433	0.9552	0.037*
C4D	0.0081 (2)	0.7428 (2)	0.86076 (12)	0.0327 (3)
H4D1	−0.0012	0.8787	0.8203	0.049*
H4D2	−0.1033	0.7278	0.9322	0.049*
H4D3	−0.0275	0.6725	0.8032	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0168 (4)	0.0224 (4)	0.0181 (4)	0.0009 (3)	−0.0003 (3)	−0.0043 (3)
C2	0.0190 (5)	0.0190 (5)	0.0200 (4)	−0.0022 (4)	−0.0009 (3)	−0.0031 (4)
C3	0.0190 (5)	0.0246 (5)	0.0195 (4)	0.0001 (4)	−0.0031 (4)	−0.0025 (4)
N4	0.0145 (4)	0.0256 (4)	0.0195 (4)	0.0024 (3)	−0.0013 (3)	−0.0052 (3)
C5	0.0148 (4)	0.0162 (4)	0.0202 (4)	−0.0018 (3)	−0.0013 (3)	−0.0049 (3)
O21	0.0282 (4)	0.0329 (4)	0.0189 (4)	−0.0009 (3)	0.0024 (3)	−0.0044 (3)
C41	0.0148 (4)	0.0272 (5)	0.0284 (5)	0.0016 (4)	0.0016 (4)	−0.0088 (4)
N51	0.0173 (4)	0.0274 (5)	0.0173 (4)	0.0033 (3)	−0.0008 (3)	−0.0059 (3)
O1D	0.0254 (4)	0.0441 (5)	0.0239 (4)	−0.0052 (4)	0.0076 (3)	−0.0141 (4)
S2D	0.01945 (13)	0.02222 (13)	0.02000 (12)	−0.00115 (9)	−0.00068 (9)	−0.00608 (9)
C3D	0.0250 (5)	0.0292 (5)	0.0210 (5)	−0.0033 (4)	0.0003 (4)	−0.0096 (4)
C4D	0.0202 (5)	0.0450 (7)	0.0337 (6)	−0.0024 (5)	−0.0056 (4)	−0.0110 (5)

Geometric parameters (Å, º) top

N1—C5	1.3591 (13)	C41—H41C	0.9800
N1—C2	1.3644 (13)	N51—H51A	0.823 (18)
C2—O21	1.2306 (13)	N51—H51B	0.887 (16)
C2—C3	1.5269 (15)	O1D—S2D	1.5109 (9)
C3—N4	1.4514 (14)	S2D—C3D	1.7833 (12)
C3—H3A	0.9900	S2D—C4D	1.7844 (13)
C3—H3B	0.9900	C3D—H3D1	0.9800
N4—C5	1.3426 (13)	C3D—H3D2	0.9800
N4—C41	1.4487 (13)	C3D—H3D3	0.9800
C5—N51	1.3269 (13)	C4D—H4D1	0.9800
C41—H41A	0.9800	C4D—H4D2	0.9800
C41—H41B	0.9800	C4D—H4D3	0.9800

C5—N1—C2	106.69 (8)	H41A—C41—H41C	109.5
O21—C2—N1	126.20 (10)	H41B—C41—H41C	109.5
O21—C2—C3	124.36 (10)	C5—N51—H51A	123.0 (12)
N1—C2—C3	109.44 (9)	C5—N51—H51B	117.3 (10)
N4—C3—C2	101.23 (8)	H51A—N51—H51B	119.7 (16)
N4—C3—H3A	111.5	O1D—S2D—C3D	106.00 (6)
C2—C3—H3A	111.5	O1D—S2D—C4D	106.16 (6)
N4—C3—H3B	111.5	C3D—S2D—C4D	97.79 (6)
C2—C3—H3B	111.5	S2D—C3D—H3D1	109.5
H3A—C3—H3B	109.3	S2D—C3D—H3D2	109.5
C5—N4—C41	128.18 (9)	H3D1—C3D—H3D2	109.5
C5—N4—C3	108.39 (8)	S2D—C3D—H3D3	109.5
C41—N4—C3	123.06 (9)	H3D1—C3D—H3D3	109.5
N51—C5—N4	124.29 (10)	H3D2—C3D—H3D3	109.5
N51—C5—N1	121.51 (9)	S2D—C4D—H4D1	109.5
N4—C5—N1	114.19 (9)	S2D—C4D—H4D2	109.5
N4—C41—H41A	109.5	H4D1—C4D—H4D2	109.5
N4—C41—H41B	109.5	S2D—C4D—H4D3	109.5
H41A—C41—H41B	109.5	H4D1—C4D—H4D3	109.5
N4—C41—H41C	109.5	H4D2—C4D—H4D3	109.5

C5—N1—C2—O21	179.20 (11)	C41—N4—C5—N51	−5.49 (18)
C5—N1—C2—C3	−0.46 (12)	C3—N4—C5—N51	−178.65 (10)
O21—C2—C3—N4	−177.89 (11)	C41—N4—C5—N1	175.64 (10)
N1—C2—C3—N4	1.78 (11)	C3—N4—C5—N1	2.48 (13)
C2—C3—N4—C5	−2.45 (11)	C2—N1—C5—N51	179.85 (10)
C2—C3—N4—C41	−176.03 (10)	C2—N1—C5—N4	−1.25 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N51—H51A···O1D	0.823 (18)	2.028 (18)	2.8403 (13)	169.3 (17)
N51—H51B···N1ⁱ	0.887 (16)	2.040 (16)	2.9225 (14)	172.9 (14)

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₄H₇N₃O·C₂H₆OS
M_r	191.25
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	5.8997 (10), 7.3018 (13), 11.276 (2)
α, β, γ (°)	75.861 (18), 83.763 (16), 79.694 (13)
V (Å³)	462.36 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.50 × 0.40 × 0.40

Data collection
Diffractometer	Siemens SMART 1K CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	8161, 2997, 2597
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.757

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 0.98
No. of reflections	2997
No. of parameters	120
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.32

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008) and XP (Sheldrick, 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N51—H51A···O1D	0.823 (18)	2.028 (18)	2.8403 (13)	169.3 (17)
N51—H51B···N1ⁱ	0.887 (16)	2.040 (16)	2.9225 (14)	172.9 (14)

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

We thank Professor Dr E. Egert (Goethe-Universität Frankfurt, Germany) for helpful discussions.

References

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