2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium 4-methyl­benzene­sulfonate

Thayanithi, V.; Kumar, P.P.; Chakkaravarthi, G.

doi:10.1107/S2414314616011251

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 7| July 2016| x161125

https://doi.org/10.1107/S2414314616011251

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2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium 4-methylbenzenesulfonate

V. Thayanithi,^a P. Praveen Kumar ^a ^* and G. Chakkaravarthi ^b ^*

^aDepartment of Physics, Presidency College, Chennai 600 005, India, and ^bDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India
^*Correspondence e-mail: ppkpresidency@gmail.com, chakkaravarthi_2005@yahoo.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 24 June 2016; accepted 11 July 2016; online 15 July 2016)

The title molecular salt, C₄H₈N₃O⁺·C₇H₇O₃S⁻, is composed of a 2-amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium cation and a 4-methylbenzenesulfonate anion. The cation is protonated at its N atom and the anion is deprotonated at its hydroxy O atom. The imidazole ring is planar (r.m.s. deviation = 0.033 Å) and makes a dihedral angle of 7.87 (10)° with the benzene ring of the anion. In the crystal, the anions and cations are connected by two N—H⋯O hydrogen bonds, generating an R₂²(8) ring motif. These units are linked by further N—H⋯O hydrogen bonds and C—H⋯O and C—H⋯π contacts to form chains propagating along the a-axis direction.

Keywords: crystal structure; molecular salt; hydrogen bonding.

CCDC reference: 1491856

Structure description

Creatinine is found in the muscle tissue of vertebrates, mainly in the form of phosphocreatine, and supplies energy for muscle contraction. It has been proven that determination of creatinine is more valuable for the detection of renal dysfunction than that of urea (Sharma et al., 2004 ). Abnormal levels of creatinine in biological fluids is an indicator of various disease states (Narayanan & Appleton, 1980 ). Benzenesulfonic acid is a particularly strong organic acid which is capable of protonating N-containing heterocycles and other Lewis bases (Wang & Wei, 2007 ). We report herein on the synthesis and crystal structure of the title molecular salt. The geometric parameters are comparable with those of similar structures (Moghimi et al., 2004 ; Hemamalini et al., 2005 )

The title molecular salt, Fig. 1, contains a 2-amino-1-methyl-5H-imidazolium-4-one cation (protonated at the N atom, N1, in the imidazole unit) and a 4-methylbenzenesulfonate anion (deprotonated at the hydroxyl O atom, O1). The imidazole ring is almost planar (r.m.s. deviation = 0.033 Å) and makes a dihedral angle of 7.87 (10)° with the benzene ring (C1–C6) of the anion.

Figure 1
The molecular structure of the title molecular salt, showing the atom labelling and 30% probability displacement ellipsoids.

In the crystal, the anions and cations are connected by two N—H⋯O hydrogen bonds, generating an $[R_{2}^{2}]$ (8) ring motif (Table 1 and Fig. 2). These units are linked by further N—H⋯O hydrogen bonds and C—H⋯O and C—H⋯π contacts to form chains propagating along the a-axis direction (Table 1 and Figs. 2 and 3).

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2ⁱ	0.89 (1)	2.09 (1)	2.967 (2)	171 (2)
N1—H1⋯O3ⁱⁱ	0.87 (1)	1.94 (1)	2.811 (2)	173 (2)
N3—H3B⋯O1ⁱⁱ	0.88 (1)	1.96 (1)	2.813 (2)	163 (2)
C10—H10B⋯O2	0.97	2.59	3.463 (3)	150
C11—H11C⋯Cg1	0.96	2.78	3.537 (2)	136
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Figure 2
A partial view of the crystal packing of the title salt, showing the formation of the $[R_{2}^{2}]$ (8) ring motifs. Hydrogen bonds (see Table 1

) are shown as dashed lines and C-bound H atoms have been omitted for clarity.

Figure 3
The crystal packing of the title compound, viewed along the a axis. The hydrogen bonds (see Table 1

) are shown as dashed lines and C-bound H atoms have been omitted for clarity.

Synthesis and crystallization

Creatinine (2-amino-1-methyl-5H-imidazol-4-one) (1.13 g, 0.01 mol) and 4-methylbenzenesulfonic acid monohydrate (1.90 g, 0.01 mol) were dissolved in deionized water. The solution was stirred well for 3 h, filtered and kept in a dust-free environment for evaporation. Crystals were obtained over a period of five days by slow evaporation of the solvent, and subjected to single-crystal X-ray diffraction analysis.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₄H₈N₃O⁺·C₇H₇O₃S⁻
M_r	285.32
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	7.0564 (4), 7.8593 (5), 24.1907 (18)
V (Å³)	1341.58 (15)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.26
Crystal size (mm)	0.28 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.932, 0.951
No. of measured, independent and observed [I > 2σ(I)] reflections	19256, 4179, 3607
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.743

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.110, 1.05
No. of reflections	4179
No. of parameters	185
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.35
Absolute structure	Flack (1983 ), 1712 Friedal pairs
Absolute structure parameter	0.04 (8)
Computer programs: APEX2 and SAINT (Bruker, 2004), SHELXS97 and SHELXL97 (Sheldrick, 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1491856

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616011251/su4059sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616011251/su4059Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616011251/su4059Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium 4-methylbenzenesulfonate top

Crystal data top

C₄H₈N₃O⁺·C₇H₇O₃S⁻	F(000) = 600
M_r = 285.32	D_x = 1.413 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8207 reflections
a = 7.0564 (4) Å	θ = 2.2–27.9°
b = 7.8593 (5) Å	µ = 0.26 mm⁻¹
c = 24.1907 (18) Å	T = 295 K
V = 1341.58 (15) Å³	Block, colourless
Z = 4	0.28 × 0.24 × 0.20 mm

Data collection top

Bruker Kappa APEXII CCD diffractometer	4179 independent reflections
Radiation source: fine-focus sealed tube	3607 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω and φ scan	θ_max = 31.9°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −10→10
T_min = 0.932, T_max = 0.951	k = −10→11
19256 measured reflections	l = −33→35

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.110	w = 1/[σ²(F_o²) + (0.0598P)² + 0.2554P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
4179 reflections	Δρ_max = 0.23 e Å⁻³
185 parameters	Δρ_min = −0.35 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 1712 Friedal pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (8)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.5492 (2)	0.7635 (2)	0.66004 (6)	0.0310 (3)
C2	0.3811 (3)	0.8465 (2)	0.64735 (8)	0.0393 (4)
H2	0.3669	0.9012	0.6135	0.047*
C3	0.2352 (3)	0.8472 (3)	0.68525 (9)	0.0466 (5)
H3	0.1229	0.9033	0.6767	0.056*
C4	0.2524 (3)	0.7658 (3)	0.73601 (8)	0.0448 (4)
C5	0.4206 (3)	0.6824 (3)	0.74788 (8)	0.0447 (4)
H5	0.4342	0.6262	0.7815	0.054*
C6	0.5697 (3)	0.6816 (3)	0.71009 (7)	0.0386 (4)
H6	0.6824	0.6261	0.7186	0.046*
C7	0.0916 (4)	0.7681 (4)	0.77703 (11)	0.0697 (8)
H7A	0.0593	0.8838	0.7857	0.105*
H7B	0.1297	0.7102	0.8102	0.105*
H7C	−0.0165	0.7118	0.7614	0.105*
C8	0.5860 (3)	0.3940 (2)	0.50931 (8)	0.0369 (4)
C9	0.3041 (2)	0.4880 (2)	0.53959 (7)	0.0306 (3)
C10	0.5602 (3)	0.3361 (2)	0.56814 (8)	0.0394 (4)
H10A	0.5554	0.2129	0.5705	0.047*
H10B	0.6614	0.3778	0.5916	0.047*
C11	0.2787 (4)	0.3750 (3)	0.63391 (8)	0.0493 (5)
H11A	0.3625	0.3192	0.6593	0.074*
H11B	0.1728	0.3022	0.6261	0.074*
H11C	0.2341	0.4793	0.6500	0.074*
N1	0.4224 (2)	0.47883 (19)	0.49552 (6)	0.0322 (3)
N2	0.3792 (2)	0.41182 (19)	0.58312 (6)	0.0340 (3)
N3	0.1389 (2)	0.5624 (2)	0.53732 (7)	0.0436 (4)
O1	0.6482 (2)	0.73257 (19)	0.55797 (5)	0.0480 (3)
O2	0.8645 (2)	0.6292 (2)	0.62769 (6)	0.0511 (4)
O3	0.8221 (2)	0.93207 (17)	0.61315 (6)	0.0462 (3)
O4	0.7202 (2)	0.3721 (2)	0.47927 (7)	0.0546 (4)
S1	0.73557 (6)	0.76400 (5)	0.611355 (17)	0.03468 (11)
H1	0.395 (3)	0.515 (3)	0.4624 (5)	0.038 (5)*
H3A	0.061 (3)	0.572 (3)	0.5658 (7)	0.045 (6)*
H3B	0.116 (4)	0.625 (3)	0.5079 (7)	0.053 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0325 (7)	0.0309 (8)	0.0295 (7)	−0.0004 (7)	0.0009 (6)	−0.0016 (6)
C2	0.0398 (9)	0.0396 (9)	0.0384 (9)	0.0066 (8)	−0.0043 (8)	−0.0004 (7)
C3	0.0336 (9)	0.0477 (10)	0.0586 (12)	0.0060 (9)	−0.0010 (9)	−0.0108 (8)
C4	0.0412 (9)	0.0459 (9)	0.0472 (10)	−0.0100 (10)	0.0114 (8)	−0.0155 (8)
C5	0.0532 (11)	0.0513 (11)	0.0297 (8)	−0.0059 (9)	0.0067 (8)	−0.0004 (8)
C6	0.0389 (9)	0.0438 (9)	0.0332 (8)	0.0034 (8)	0.0009 (7)	0.0036 (7)
C7	0.0570 (13)	0.0796 (17)	0.0726 (16)	−0.0192 (15)	0.0322 (12)	−0.0239 (15)
C8	0.0359 (9)	0.0302 (8)	0.0445 (9)	0.0041 (7)	0.0001 (7)	−0.0047 (7)
C9	0.0309 (8)	0.0293 (7)	0.0316 (7)	−0.0009 (6)	0.0008 (6)	−0.0014 (6)
C10	0.0363 (9)	0.0351 (8)	0.0467 (10)	0.0047 (7)	−0.0060 (8)	0.0020 (7)
C11	0.0627 (13)	0.0521 (11)	0.0332 (9)	−0.0030 (11)	0.0058 (9)	0.0066 (8)
N1	0.0319 (7)	0.0340 (7)	0.0308 (7)	0.0033 (6)	0.0019 (6)	−0.0013 (5)
N2	0.0363 (7)	0.0334 (7)	0.0324 (7)	0.0006 (6)	0.0000 (6)	0.0017 (6)
N3	0.0337 (8)	0.0569 (11)	0.0403 (8)	0.0115 (8)	0.0074 (7)	0.0066 (8)
O1	0.0643 (9)	0.0496 (8)	0.0302 (6)	−0.0154 (7)	0.0044 (6)	−0.0034 (6)
O2	0.0428 (8)	0.0538 (8)	0.0566 (9)	0.0138 (7)	0.0147 (7)	0.0062 (7)
O3	0.0536 (8)	0.0428 (7)	0.0423 (7)	−0.0149 (6)	0.0040 (6)	−0.0015 (6)
O4	0.0444 (8)	0.0545 (8)	0.0649 (10)	0.0167 (7)	0.0172 (7)	−0.0022 (7)
S1	0.0365 (2)	0.0351 (2)	0.03242 (18)	−0.00248 (17)	0.00560 (16)	0.00011 (15)

Geometric parameters (Å, º) top

C1—C6	1.379 (2)	C8—C10	1.505 (3)
C1—C2	1.388 (3)	C9—N3	1.305 (2)
C1—S1	1.7655 (16)	C9—N2	1.322 (2)
C2—C3	1.378 (3)	C9—N1	1.356 (2)
C2—H2	0.9300	C10—N2	1.455 (2)
C3—C4	1.390 (3)	C10—H10A	0.9700
C3—H3	0.9300	C10—H10B	0.9700
C4—C5	1.386 (3)	C11—N2	1.448 (2)
C4—C7	1.508 (3)	C11—H11A	0.9600
C5—C6	1.394 (3)	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600
C6—H6	0.9300	N1—H1	0.872 (9)
C7—H7A	0.9600	N3—H3A	0.885 (9)
C7—H7B	0.9600	N3—H3B	0.882 (10)
C7—H7C	0.9600	O1—S1	1.4523 (14)
C8—O4	1.206 (2)	O2—S1	1.4510 (15)
C8—N1	1.374 (2)	O3—S1	1.4559 (13)

C6—C1—C2	120.22 (16)	N2—C9—N1	110.85 (15)
C6—C1—S1	120.55 (13)	N2—C10—C8	102.59 (14)
C2—C1—S1	119.22 (13)	N2—C10—H10A	111.2
C3—C2—C1	119.54 (18)	C8—C10—H10A	111.2
C3—C2—H2	120.2	N2—C10—H10B	111.2
C1—C2—H2	120.2	C8—C10—H10B	111.2
C2—C3—C4	121.36 (19)	H10A—C10—H10B	109.2
C2—C3—H3	119.3	N2—C11—H11A	109.5
C4—C3—H3	119.3	N2—C11—H11B	109.5
C5—C4—C3	118.41 (17)	H11A—C11—H11B	109.5
C5—C4—C7	120.9 (2)	N2—C11—H11C	109.5
C3—C4—C7	120.7 (2)	H11A—C11—H11C	109.5
C4—C5—C6	120.83 (18)	H11B—C11—H11C	109.5
C4—C5—H5	119.6	C9—N1—C8	110.61 (15)
C6—C5—H5	119.6	C9—N1—H1	124.5 (15)
C1—C6—C5	119.63 (18)	C8—N1—H1	124.7 (15)
C1—C6—H6	120.2	C9—N2—C11	124.78 (17)
C5—C6—H6	120.2	C9—N2—C10	109.78 (14)
C4—C7—H7A	109.5	C11—N2—C10	124.02 (16)
C4—C7—H7B	109.5	C9—N3—H3A	124.1 (15)
H7A—C7—H7B	109.5	C9—N3—H3B	116.8 (18)
C4—C7—H7C	109.5	H3A—N3—H3B	118 (2)
H7A—C7—H7C	109.5	O2—S1—O1	112.60 (10)
H7B—C7—H7C	109.5	O2—S1—O3	113.02 (10)
O4—C8—N1	125.64 (19)	O1—S1—O3	111.04 (9)
O4—C8—C10	128.43 (18)	O2—S1—C1	106.48 (8)
N1—C8—C10	105.93 (16)	O1—S1—C1	106.04 (9)
N3—C9—N2	126.45 (16)	O3—S1—C1	107.14 (8)
N3—C9—N1	122.70 (16)

C6—C1—C2—C3	0.3 (3)	O4—C8—N1—C9	−176.92 (19)
S1—C1—C2—C3	−179.74 (15)	C10—C8—N1—C9	3.4 (2)
C1—C2—C3—C4	−0.3 (3)	N3—C9—N2—C11	9.9 (3)
C2—C3—C4—C5	−0.3 (3)	N1—C9—N2—C11	−169.69 (16)
C2—C3—C4—C7	179.9 (2)	N3—C9—N2—C10	176.69 (18)
C3—C4—C5—C6	0.7 (3)	N1—C9—N2—C10	−2.86 (19)
C7—C4—C5—C6	−179.5 (2)	C8—C10—N2—C9	4.62 (19)
C2—C1—C6—C5	0.1 (3)	C8—C10—N2—C11	171.58 (17)
S1—C1—C6—C5	−179.85 (15)	C6—C1—S1—O2	16.90 (18)
C4—C5—C6—C1	−0.6 (3)	C2—C1—S1—O2	−163.02 (15)
O4—C8—C10—N2	175.6 (2)	C6—C1—S1—O1	137.03 (16)
N1—C8—C10—N2	−4.70 (19)	C2—C1—S1—O1	−42.88 (17)
N3—C9—N1—C8	179.99 (17)	C6—C1—S1—O3	−104.31 (16)
N2—C9—N1—C8	−0.4 (2)	C2—C1—S1—O3	75.78 (16)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱ	0.89 (1)	2.09 (1)	2.967 (2)	171 (2)
N1—H1···O3ⁱⁱ	0.87 (1)	1.94 (1)	2.811 (2)	173 (2)
N3—H3B···O1ⁱⁱ	0.88 (1)	1.96 (1)	2.813 (2)	163 (2)
C10—H10B···O2	0.97	2.59	3.463 (3)	150
C11—H11C···Cg1	0.96	2.78	3.537 (2)	136

Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+1.

Acknowledgements

The authors acknowledge the SAIF, IIT, Madras, for the data collection.

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