organic compounds
2-Amino-1-methyl-4-oxo-4,5-dihydro-1H-imidazol-3-ium 4-methylbenzenesulfonate
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
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 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.
In the crystal, the anions and cations are connected by two N—H⋯O hydrogen bonds, generating an (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).
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 .
details are summarized in Table 2
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Structural data
CCDC reference: 1491856
https://doi.org/10.1107/S2414314616011251/su4059sup1.cif
contains datablocks I, global. DOI: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
Data collection: APEX2 (Bruker, 2004); cell
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).C4H8N3O+·C7H7O3S− | F(000) = 600 |
Mr = 285.32 | Dx = 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 |
Bruker Kappa APEXII CCD diffractometer | 4179 independent reflections |
Radiation source: fine-focus sealed tube | 3607 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω and φ scan | θmax = 31.9°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.932, Tmax = 0.951 | k = −10→11 |
19256 measured reflections | l = −33→35 |
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(Fo2) + (0.0598P)2 + 0.2554P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
4179 reflections | Δρmax = 0.23 e Å−3 |
185 parameters | Δρmin = −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) |
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. |
x | y | z | Uiso*/Ueq | ||
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)* |
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) |
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) |
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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