Acta Cryst. (2009). E65, o744 [ doi:10.1107/S1600536809007004 ]
In the title compound, 2C3H5N2S+·C4H4O42-·C4H6O4, the thiazolium ring is almost planar, with the maximum deviation from planarity being 0.0056 (8) Å for the C atom carrying the amine substituent. The N atom of the 2-aminothiazole molecule is protonated. Both the anion and the acid lie across inversion centres. The crystal packing is consolidated by intermolecular O-H
O, N-HO and C-HO hydrogen bonds. Molecules are stacked down the b axis.
2- Aminothiazole (0.100 g, 1 mmol) and succinic acid (0.118 g, 1 mmol) were dissolved in ethanol (25 ml) in a 1:1 molar ratio. The clear brown solution obtained was refluxed for 6 h at a temperature of 323 K. Brown coloured crystals were harvested after two weeks on slow evaporation of the solvent.
All the hydrogen atoms were located from the Fourier map and were allowed to refine freely with isotropic displacement parameters.
Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./sj2582fig1thm.gif)
| Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom numbering scheme. [symmetry operators used to generate equivalent atoms are (i) -x + 1, -y + 2, -z and (ii) -x + 2, -y + 2, -z for the anion and acid respectively]. |
![[Figure 2]](./sj2582fig2thm.gif)
| Fig. 2. The crystal packing of the title compound, viewed along the b axis. Dashed lines indicate the hydrogen bonding. |
| 2C3H5N2S+·C4H4O42−·C4H6O4 | F(000) = 456 |
| Mr = 436.46 | Dx = 1.581 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 9994 reflections |
| a = 10.1680 (2) Å | θ = 2.3–40.1° |
| b = 5.1012 (1) Å | µ = 0.34 mm−1 |
| c = 18.3850 (4) Å | T = 100 K |
| β = 105.961 (1)° | Block, yellow |
| V = 916.85 (3) Å3 | 0.58 × 0.42 × 0.32 mm |
| Z = 2 |
| Bruker SMART APEXII CCD area-detector diffractometer | 3691 independent reflections |
| Radiation source: fine-focus sealed tube | 3442 reflections with I > 2σ(I) |
| graphite | Rint = 0.022 |
| φ and ω scans | θmax = 34.0°, θmin = 2.1° |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | h = −16→16 |
| Tmin = 0.826, Tmax = 0.897 | k = −7→7 |
| 16689 measured reflections | l = −28→24 |
| 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)] = 0.027 | Hydrogen site location: difference Fourier map |
| wR(F2) = 0.077 | All H-atom parameters refined |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0423P)2 + 0.2556P] where P = (Fo2 + 2Fc2)/3 |
| 3691 reflections | (Δ/σ)max = 0.001 |
| 167 parameters | Δρmax = 0.45 e Å−3 |
| 0 restraints | Δρmin = −0.35 e Å−3 |
| 2C3H5N2S+·C4H4O42−·C4H6O4 | V = 916.85 (3) Å3 |
| Mr = 436.46 | Z = 2 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 10.1680 (2) Å | µ = 0.34 mm−1 |
| b = 5.1012 (1) Å | T = 100 K |
| c = 18.3850 (4) Å | 0.58 × 0.42 × 0.32 mm |
| β = 105.961 (1)° |
| Bruker SMART APEXII CCD area-detector diffractometer | 3691 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2005) | 3442 reflections with I > 2σ(I) |
| Tmin = 0.826, Tmax = 0.897 | Rint = 0.022 |
| 16689 measured reflections | θmax = 34.0° |
| R[F2 > 2σ(F2)] = 0.027 | All H-atom parameters refined |
| wR(F2) = 0.077 | Δρmax = 0.45 e Å−3 |
| S = 1.04 | Δρmin = −0.35 e Å−3 |
| 3691 reflections | Absolute structure: ? |
| 167 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. |
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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.398521 (18) | 0.38496 (4) | 0.154349 (10) | 0.01603 (6) | |
| O1 | 0.64045 (5) | 0.89655 (11) | 0.12963 (3) | 0.01367 (10) | |
| O2 | 0.77343 (5) | 1.19344 (12) | 0.09559 (3) | 0.01562 (10) | |
| O3 | 0.80012 (6) | 0.57645 (12) | 0.00894 (3) | 0.01703 (11) | |
| O4 | 0.99583 (6) | 0.66022 (12) | 0.09808 (3) | 0.01646 (11) | |
| N1 | 0.52407 (6) | 0.60443 (12) | 0.27794 (3) | 0.01361 (11) | |
| N2 | 0.63526 (6) | 0.22575 (14) | 0.25269 (4) | 0.01565 (12) | |
| C1 | 0.32820 (7) | 0.66562 (16) | 0.18253 (4) | 0.01749 (13) | |
| C2 | 0.40776 (7) | 0.75502 (15) | 0.24905 (4) | 0.01599 (13) | |
| C3 | 0.53433 (7) | 0.39842 (14) | 0.23509 (4) | 0.01261 (12) | |
| C4 | 0.66461 (6) | 1.05440 (14) | 0.08264 (4) | 0.01101 (11) | |
| C5 | 0.56100 (7) | 1.09079 (14) | 0.00653 (4) | 0.01307 (12) | |
| C6 | 0.91584 (7) | 0.70771 (13) | 0.03682 (4) | 0.01173 (11) | |
| C7 | 0.93722 (7) | 0.91684 (14) | −0.01673 (4) | 0.01291 (12) | |
| H1 | 0.2400 (13) | 0.731 (3) | 0.1506 (7) | 0.027 (3)* | |
| H2 | 0.3948 (13) | 0.900 (2) | 0.2779 (7) | 0.023 (3)* | |
| H7A | 0.8557 (13) | 1.025 (3) | −0.0314 (7) | 0.023 (3)* | |
| H7B | 0.9449 (13) | 0.826 (3) | −0.0630 (7) | 0.025 (3)* | |
| H1N2 | 0.7022 (15) | 0.248 (3) | 0.2933 (8) | 0.035 (4)* | |
| H2N2 | 0.6384 (13) | 0.100 (3) | 0.2197 (7) | 0.025 (3)* | |
| H1C5 | 0.6093 (14) | 1.070 (3) | −0.0333 (8) | 0.030 (3)* | |
| H2C5 | 0.5330 (13) | 1.280 (3) | 0.0047 (8) | 0.030 (3)* | |
| H1N1 | 0.5877 (14) | 0.640 (3) | 0.3188 (8) | 0.031 (3)* | |
| H1O3 | 0.7940 (17) | 0.447 (4) | 0.0401 (9) | 0.052 (5)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.01505 (8) | 0.01672 (9) | 0.01227 (8) | −0.00239 (5) | −0.00303 (6) | 0.00025 (5) |
| O1 | 0.0141 (2) | 0.0152 (2) | 0.0103 (2) | −0.00308 (17) | 0.00095 (16) | 0.00264 (16) |
| O2 | 0.0127 (2) | 0.0175 (2) | 0.0136 (2) | −0.00582 (18) | −0.00159 (17) | 0.00353 (18) |
| O3 | 0.0150 (2) | 0.0181 (3) | 0.0151 (2) | −0.00693 (18) | −0.00061 (18) | 0.00485 (19) |
| O4 | 0.0145 (2) | 0.0178 (2) | 0.0146 (2) | −0.00236 (18) | −0.00011 (18) | 0.00380 (19) |
| N1 | 0.0128 (2) | 0.0147 (3) | 0.0116 (2) | 0.00017 (19) | 0.00047 (19) | −0.00062 (19) |
| N2 | 0.0141 (2) | 0.0176 (3) | 0.0128 (2) | 0.0022 (2) | −0.0003 (2) | −0.0030 (2) |
| C1 | 0.0137 (3) | 0.0171 (3) | 0.0189 (3) | −0.0001 (2) | −0.0001 (2) | 0.0044 (3) |
| C2 | 0.0141 (3) | 0.0152 (3) | 0.0179 (3) | 0.0014 (2) | 0.0031 (2) | 0.0022 (2) |
| C3 | 0.0119 (3) | 0.0143 (3) | 0.0102 (2) | −0.0016 (2) | 0.0008 (2) | 0.0004 (2) |
| C4 | 0.0106 (2) | 0.0116 (3) | 0.0097 (2) | −0.0009 (2) | 0.00098 (19) | 0.0002 (2) |
| C5 | 0.0115 (2) | 0.0153 (3) | 0.0101 (2) | −0.0035 (2) | −0.0009 (2) | 0.0027 (2) |
| C6 | 0.0113 (2) | 0.0111 (3) | 0.0127 (3) | −0.0006 (2) | 0.0032 (2) | 0.0002 (2) |
| C7 | 0.0129 (3) | 0.0129 (3) | 0.0122 (3) | −0.0022 (2) | 0.0023 (2) | 0.0018 (2) |
| S1—C3 | 1.7285 (7) | N2—H2N2 | 0.888 (13) |
| S1—C1 | 1.7416 (9) | C1—C2 | 1.3468 (11) |
| O1—C4 | 1.2538 (8) | C1—H1 | 0.986 (13) |
| O2—C4 | 1.2802 (8) | C2—H2 | 0.941 (13) |
| O3—C6 | 1.3281 (8) | C4—C5 | 1.5139 (9) |
| O3—H1O3 | 0.887 (18) | C5—C5i | 1.5135 (14) |
| O4—C6 | 1.2185 (8) | C5—H1C5 | 0.993 (14) |
| N1—C3 | 1.3346 (9) | C5—H2C5 | 1.003 (14) |
| N1—C2 | 1.3877 (9) | C6—C7 | 1.5075 (10) |
| N1—H1N1 | 0.864 (14) | C7—C7ii | 1.5153 (14) |
| N2—C3 | 1.3233 (9) | C7—H7A | 0.970 (13) |
| N2—H1N2 | 0.868 (15) | C7—H7B | 0.989 (13) |
| C3—S1—C1 | 90.47 (3) | O1—C4—C5 | 119.82 (6) |
| C6—O3—H1O3 | 109.7 (10) | O2—C4—C5 | 116.75 (6) |
| C3—N1—C2 | 113.99 (6) | C5i—C5—C4 | 113.78 (7) |
| C3—N1—H1N1 | 121.0 (9) | C5i—C5—H1C5 | 111.6 (8) |
| C2—N1—H1N1 | 125.0 (9) | C4—C5—H1C5 | 108.0 (8) |
| C3—N2—H1N2 | 119.6 (10) | C5i—C5—H2C5 | 111.7 (8) |
| C3—N2—H2N2 | 118.9 (8) | C4—C5—H2C5 | 105.5 (8) |
| H1N2—N2—H2N2 | 121.0 (13) | H1C5—C5—H2C5 | 105.7 (11) |
| C2—C1—S1 | 110.81 (6) | O4—C6—O3 | 123.50 (6) |
| C2—C1—H1 | 130.3 (8) | O4—C6—C7 | 124.39 (6) |
| S1—C1—H1 | 118.9 (8) | O3—C6—C7 | 112.10 (6) |
| C1—C2—N1 | 113.33 (7) | C6—C7—C7ii | 112.82 (7) |
| C1—C2—H2 | 129.5 (8) | C6—C7—H7A | 108.6 (7) |
| N1—C2—H2 | 117.2 (8) | C7ii—C7—H7A | 110.8 (8) |
| N2—C3—N1 | 124.12 (6) | C6—C7—H7B | 106.9 (8) |
| N2—C3—S1 | 124.49 (5) | C7ii—C7—H7B | 110.7 (7) |
| N1—C3—S1 | 111.38 (5) | H7A—C7—H7B | 106.8 (10) |
| O1—C4—O2 | 123.42 (6) | ||
| C3—S1—C1—C2 | 0.33 (6) | C1—S1—C3—N1 | −0.78 (6) |
| S1—C1—C2—N1 | 0.18 (9) | O1—C4—C5—C5i | −4.29 (11) |
| C3—N1—C2—C1 | −0.80 (9) | O2—C4—C5—C5i | 176.67 (8) |
| C2—N1—C3—N2 | −178.46 (7) | O4—C6—C7—C7ii | −5.84 (12) |
| C2—N1—C3—S1 | 1.04 (8) | O3—C6—C7—C7ii | 175.31 (7) |
| C1—S1—C3—N2 | 178.72 (7) |
| Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+2, −y+2, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H1N2···O1iii | 0.868 (15) | 1.974 (15) | 2.8156 (9) | 163.0 (14) |
| N2—H2N2···O1iv | 0.889 (14) | 1.959 (13) | 2.8297 (9) | 165.7 (13) |
| N1—H1N1···O2iii | 0.865 (14) | 1.823 (14) | 2.6868 (8) | 176.2 (15) |
| O3—H1O3···O2iv | 0.888 (19) | 1.696 (19) | 2.5820 (8) | 176.5 (19) |
| C1—H1···O4v | 0.985 (13) | 2.431 (14) | 3.3086 (10) | 148.2 (12) |
| Symmetry codes: (iii) −x+3/2, y−1/2, −z+1/2; (iv) x, y−1, z; (v) x−1, y, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H1N2···O1i | 0.868 (15) | 1.974 (15) | 2.8156 (9) | 163.0 (14) |
| N2—H2N2···O1ii | 0.889 (14) | 1.959 (13) | 2.8297 (9) | 165.7 (13) |
| N1—H1N1···O2i | 0.865 (14) | 1.823 (14) | 2.6868 (8) | 176.2 (15) |
| O3—H1O3···O2ii | 0.888 (19) | 1.696 (19) | 2.5820 (8) | 176.5 (19) |
| C1—H1···O4iii | 0.985 (13) | 2.431 (14) | 3.3086 (10) | 148.2 (12) |
| Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) x−1, y, z. |
HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No.1001/PFIZIK/811012.
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2-Aminothiazole derivatives have shown heribicidal, anti-inflammatory, anti-microbial and antiparasitic activities (Saarnivaara & Matilla, 1974). 2-Aminothiazole is listed as a thyroid inhibitor (Windholz, 2001). The orthorhombic form of 2-amino-1,3-thiazole has been reported (Caranoni & Reboul, 1982). Succinic acid is a dicarboxylic acid and is a precursor for many chemicals of industrial importance (Zeikus et al., 1999; Song & Lee, 2006). Succinic acid derivatives are mostly used in chemicals, food and pharmaceuticals (Sauer et al., 2008). The crystal structure of succinic acid has been reported (Gopalan et al., 2000; Leviel et al. 1981). Due to all these important properties, the title compound (I) has been synthesized and is reported here.
The asymmetric unit of (I) (Fig. 1) contains one molecule of protonated 2-aminothiazole, a half molecule of succinate and a half molecule of succinic acid. The anion and the acid lie across different inversion centres [symmetry codes (i) -x + 1, -y + 2, -z and (ii) -x + 2, -y + 2, -z respectively]. The thiazolium ring is planar with the maximum deviation from planarity being 0.0056 (8)Å for atom C3. The ring nitrogen of the 2-aminothiazole molecule is protonated thereby leading to a widening of the corresponding internal angle (C2–N1–C3) of the thiazolium ring to 113.99 (6)° [which is 109.4 (5)° in the unprotonated form of 2-aminothiazole] and an increase in the bond lengths of N1–C3 to 1.334 (9)Å and N1–C2 to 1.387 (9)Å [which are 1.298 (6)Å and 1.375 (6)Å respectively in its uncomplexed form] (Caranoni & Reboul, 1982). An increase in the C1–S1–C3 bond angle to 90.47 (3)° [which is 88.6 (3)° in the unprotonated form] and a decrease in the S1–C3–N1 bond angle to 111.38 (5)° [which is 114.9 (5)° in the uncomplexed form of 2-aminothiazole] (Caranoni & Reboul, 1982) are also observed.
The bond lengths and bond angles of the succinate and succinic acid are found to have normal values (Gopalan et al., 2000; Leviel & Auvert, 1981). The crystal packing is consolidated by O—H···O, N—H···O and C—H···O intermolecular hydrogen bonds (Table 1) together with intermolecular [O—Oi = 2.5820 (8) Å; O—Nii-iii = 2.6868 (8) to 2.8297 (9) Å, short contacts [symmetry code: (i) x,-1 + y,z; (ii) 3/2 - x,1/2 + y,1/2 - z; (iii) x,1 + y,z]. Molecules are stacked down the b axis(Fig.2).