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Maleic acid and fumaric acid, the
Z and
E isomers of butenedioic acid, form 1:1 adducts with 2-amino-1,3-thiazole, namely 2-amino-1,3-thiazolium hydrogen maleate (2ATHM), C
3H
5N
2S
+·C
4H
3O
4−, and 2-amino-1,3-thiazolium hydrogen fumarate (2ATHF), C
3H
5N
2S
+·C
4H
3O
4−, respectively. In both compounds, protonation of the ring N atom of the 2-amino-1,3-thiazole and deprotonation of one of the carboxyl groups are observed. The asymmetric unit of 2ATHF contains three independent ion pairs. The hydrogen maleate ion of 2ATHM shows a short intramolecular O—H
O hydrogen bond with an O
O distance of 2.4663 (19) Å. An extensive hydrogen-bonded network is observed in both compounds, involving N—H
O and O—H
O hydrogen bonds. 2ATHM forms two-dimensional sheets parallel to the
ab plane, extending as independent parallel sheets along the
c axis, whereas 2ATHF forms two-dimensional zigzag layers parallel to the
bc plane, extending as independent parallel layers along the
a axis.
Supporting information
CCDC references: 737178; 751455
Equimolar quantities of 2-amino-1,3-thiazole (0.3 g, 3 mmol) and maleic acid
(0.35 g, 3 mmol) were dissolved in water and stirred. Concentrated
hydrochloric acid (2 ml) was added and the mixture was refluxed at 333 K for 6 h. Brown crystals of 2ATHM were harvested after a month from the slow
evaporation of the solvent. Similarly, equimolar quantities of
2-amino-1,3-thiazole (0.3 g, 3 mmol) and fumaric acid (0.35 g, 3 mmol) were
dissolved in acetonitrile and stirred. Dilute hydrochloric acid (2 ml) was
added and the stirred solution was refluxed at 333 K for 6 h. Brown crystals
of 2ATHF were harvested from the resulting solution after two weeks of
solvent evaporation.
The positions of H atoms bound to N and O atoms were identified from difference
electron-density maps and then constrained. For 2ATHM, these H atoms were
allowed to ride upon the parent atom, with N—H = 0.86 and O—H = 0.82 Å,
and Uiso(H) = 1.2Ueq(N,O). For 2ATHF, the O—H positions
were allowed to rotate around the C—O bond, with O—H = 0.82 Å and
Uiso(H) = 1.5Ueq(O), and N—H = 0.86 Å and
Uiso(H) = 1.2Ueq(N). [Please check added text for N-bound
H atoms] H atoms bound to C atoms were treated as riding, with C—H =
0.93 Å and Uiso(H) = 1.2Ueq(C). Three (for 2ATHM) and
seven (for 2ATHF) outlier reflections were excluded from the intensity data.
For both compounds, data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004) and SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
(2ATHM) 2-amino-1,3-thiazolium hydrogen maleate
top
Crystal data top
C3H5N2S+·C4H3O4− | F(000) = 448 |
Mr = 216.21 | Dx = 1.579 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 4591 reflections |
a = 6.3372 (4) Å | θ = 3.2–29.6° |
b = 22.4153 (14) Å | µ = 0.35 mm−1 |
c = 6.8618 (4) Å | T = 292 K |
β = 111.112 (2)° | Block, brown |
V = 909.29 (10) Å3 | 0.28 × 0.16 × 0.08 mm |
Z = 4 | |
Data collection top
Bruker Kappa APEXII CCD area-detector diffractometer | 2529 independent reflections |
Radiation source: fine-focus sealed tube | 2056 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
ω and ϕ scans | θmax = 29.6°, θmin = 3.3° |
Absorption correction: multi-scan (SADABS; Bruker 2004) | h = −8→8 |
Tmin = 0.909, Tmax = 0.973 | k = −31→31 |
11445 measured reflections | l = −6→9 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0616P)2 + 0.2435P] where P = (Fo2 + 2Fc2)/3 |
2529 reflections | (Δ/σ)max = 0.001 |
128 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C3H5N2S+·C4H3O4− | V = 909.29 (10) Å3 |
Mr = 216.21 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.3372 (4) Å | µ = 0.35 mm−1 |
b = 22.4153 (14) Å | T = 292 K |
c = 6.8618 (4) Å | 0.28 × 0.16 × 0.08 mm |
β = 111.112 (2)° | |
Data collection top
Bruker Kappa APEXII CCD area-detector diffractometer | 2529 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 2004) | 2056 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.973 | Rint = 0.028 |
11445 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.35 e Å−3 |
2529 reflections | Δρmin = −0.22 e Å−3 |
128 parameters | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell s.u.'s are taken
into account individually in the estimation of s.u.'s in distances, angles
and torsion angles; correlations between s.u.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | Uiso*/Ueq | |
S1 | 0.56775 (6) | 1.020194 (18) | 0.76736 (7) | 0.03488 (14) | |
O1 | −0.0110 (2) | 0.81152 (6) | 0.8246 (2) | 0.0494 (4) | |
O2 | 0.2255 (2) | 0.88013 (5) | 0.7936 (2) | 0.0468 (3) | |
C1 | 0.7308 (2) | 0.95801 (7) | 0.7824 (2) | 0.0301 (3) | |
O4 | −0.0229 (2) | 0.70180 (6) | 0.8455 (3) | 0.0552 (4) | |
H4 | −0.0256 | 0.7382 | 0.8327 | 0.066* | |
C3 | 0.7656 (3) | 1.06393 (7) | 0.7146 (3) | 0.0373 (4) | |
H3 | 0.7513 | 1.1048 | 0.6901 | 0.045* | |
N2 | 0.6760 (2) | 0.90400 (6) | 0.8202 (3) | 0.0421 (4) | |
H2A | 0.7658 | 0.8746 | 0.827 | 0.051* | |
H2B | 0.5503 | 0.8979 | 0.8383 | 0.051* | |
N1 | 0.9204 (2) | 0.97152 (6) | 0.7526 (2) | 0.0330 (3) | |
H1 | 1.0217 | 0.9455 | 0.7571 | 0.04* | |
O3 | 0.1971 (3) | 0.62793 (6) | 0.8319 (3) | 0.0670 (5) | |
C4 | 0.1679 (3) | 0.82723 (7) | 0.7994 (3) | 0.0351 (3) | |
C5 | 0.3251 (3) | 0.78120 (8) | 0.7723 (3) | 0.0430 (4) | |
H5 | 0.4474 | 0.7965 | 0.744 | 0.052* | |
C6 | 0.3200 (3) | 0.72225 (8) | 0.7817 (3) | 0.0430 (4) | |
H6 | 0.4399 | 0.7034 | 0.759 | 0.052* | |
C2 | 0.9405 (3) | 1.03152 (8) | 0.7135 (3) | 0.0366 (4) | |
H2 | 1.0641 | 1.0475 | 0.689 | 0.044* | |
C7 | 0.1578 (3) | 0.68076 (8) | 0.8220 (3) | 0.0404 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0289 (2) | 0.0270 (2) | 0.0532 (3) | 0.00284 (14) | 0.02014 (19) | 0.00037 (16) |
O1 | 0.0379 (7) | 0.0313 (6) | 0.0903 (10) | 0.0034 (5) | 0.0366 (7) | 0.0048 (6) |
O2 | 0.0364 (7) | 0.0260 (6) | 0.0845 (10) | 0.0015 (5) | 0.0297 (7) | 0.0025 (6) |
C1 | 0.0245 (7) | 0.0264 (7) | 0.0401 (8) | 0.0009 (5) | 0.0124 (6) | −0.0007 (6) |
O4 | 0.0513 (8) | 0.0293 (7) | 0.1008 (12) | −0.0020 (6) | 0.0463 (8) | 0.0028 (7) |
C3 | 0.0387 (9) | 0.0253 (7) | 0.0502 (9) | −0.0031 (6) | 0.0187 (8) | 0.0030 (7) |
N2 | 0.0327 (7) | 0.0255 (7) | 0.0752 (11) | 0.0010 (5) | 0.0279 (7) | 0.0054 (6) |
N1 | 0.0259 (6) | 0.0282 (7) | 0.0483 (8) | 0.0016 (5) | 0.0175 (6) | 0.0004 (5) |
O3 | 0.0711 (11) | 0.0250 (7) | 0.1186 (14) | −0.0021 (6) | 0.0506 (10) | −0.0046 (7) |
C4 | 0.0310 (8) | 0.0280 (8) | 0.0485 (9) | 0.0021 (6) | 0.0170 (7) | 0.0022 (6) |
C5 | 0.0362 (9) | 0.0302 (8) | 0.0730 (12) | −0.0014 (7) | 0.0321 (9) | −0.0030 (8) |
C6 | 0.0383 (9) | 0.0298 (8) | 0.0684 (12) | 0.0021 (7) | 0.0282 (9) | −0.0041 (8) |
C2 | 0.0319 (8) | 0.0325 (9) | 0.0490 (9) | −0.0052 (6) | 0.0188 (7) | 0.0012 (6) |
C7 | 0.0428 (9) | 0.0277 (8) | 0.0547 (10) | −0.0017 (7) | 0.0225 (8) | −0.0034 (7) |
Geometric parameters (Å, º) top
S1—C1 | 1.7159 (15) | N2—H2B | 0.86 |
S1—C3 | 1.7296 (17) | N1—C2 | 1.386 (2) |
O1—C4 | 1.257 (2) | N1—H1 | 0.86 |
O2—C4 | 1.2454 (19) | O3—C7 | 1.207 (2) |
C1—N2 | 1.311 (2) | C4—C5 | 1.492 (2) |
C1—N1 | 1.3243 (19) | C5—C6 | 1.324 (2) |
O4—C7 | 1.301 (2) | C5—H5 | 0.93 |
O4—H4 | 0.82 | C6—C7 | 1.484 (2) |
C3—C2 | 1.327 (2) | C6—H6 | 0.93 |
C3—H3 | 0.93 | C2—H2 | 0.93 |
N2—H2A | 0.86 | | |
| | | |
C1—S1—C3 | 90.39 (8) | O2—C4—C5 | 115.96 (15) |
N2—C1—N1 | 124.15 (14) | O1—C4—C5 | 119.95 (14) |
N2—C1—S1 | 124.42 (12) | C6—C5—C4 | 130.93 (16) |
N1—C1—S1 | 111.42 (12) | C6—C5—H5 | 114.5 |
C7—O4—H4 | 109.5 | C4—C5—H5 | 114.5 |
C2—C3—S1 | 111.13 (13) | C5—C6—C7 | 131.70 (16) |
C2—C3—H3 | 124.4 | C5—C6—H6 | 114.1 |
S1—C3—H3 | 124.4 | C7—C6—H6 | 114.1 |
C1—N2—H2A | 120 | C3—C2—N1 | 113.26 (14) |
C1—N2—H2B | 120 | C3—C2—H2 | 123.4 |
H2A—N2—H2B | 120 | N1—C2—H2 | 123.4 |
C1—N1—C2 | 113.79 (13) | O3—C7—O4 | 121.44 (17) |
C1—N1—H1 | 123.1 | O3—C7—C6 | 118.86 (17) |
C2—N1—H1 | 123.1 | O4—C7—C6 | 119.70 (15) |
O2—C4—O1 | 124.08 (15) | | |
| | | |
C3—S1—C1—N2 | −179.46 (16) | O1—C4—C5—C6 | −4.6 (3) |
C3—S1—C1—N1 | 1.07 (13) | C4—C5—C6—C7 | 0.1 (4) |
C1—S1—C3—C2 | −0.90 (14) | S1—C3—C2—N1 | 0.5 (2) |
N2—C1—N1—C2 | 179.53 (16) | C1—N1—C2—C3 | 0.3 (2) |
S1—C1—N1—C2 | −1.00 (18) | C5—C6—C7—O3 | −176.6 (2) |
O2—C4—C5—C6 | 175.9 (2) | C5—C6—C7—O4 | 3.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1 | 0.82 | 1.65 | 2.4663 (19) | 175 |
N2—H2A···O1i | 0.86 | 2.01 | 2.8618 (19) | 174 |
N2—H2B···O2 | 0.86 | 2.01 | 2.8453 (19) | 164 |
N1—H1···O2i | 0.86 | 1.91 | 2.7607 (18) | 171 |
C3—H3···O4ii | 0.93 | 2.57 | 3.410 (2) | 150 |
C2—H2···O3iii | 0.93 | 2.39 | 3.249 (2) | 153 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+3/2, y+1/2, −z+3/2. |
(2ATHF) 2-amino-1,3-thiazolium hydrogen fumarate
top
Crystal data top
C3H5N2S+·C4H3O4− | F(000) = 2688 |
Mr = 216.21 | Dx = 1.547 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5488 reflections |
a = 20.7129 (5) Å | θ = 2.9–25.5° |
b = 7.1803 (2) Å | µ = 0.34 mm−1 |
c = 37.4469 (9) Å | T = 292 K |
V = 5569.3 (2) Å3 | Block, brown |
Z = 24 | 0.3 × 0.2 × 0.2 mm |
Data collection top
Bruker Kappa APEXII CCD area-detector diffractometer | 5302 independent reflections |
Radiation source: fine-focus sealed tube | 4161 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.030 |
ω and ϕ scans | θmax = 25.8°, θmin = 1.1° |
Absorption correction: multi-scan (SADABS; Bruker 2004) | h = −25→25 |
Tmin = 0.905, Tmax = 0.935 | k = −8→8 |
44583 measured reflections | l = −33→45 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0716P)2 + 4.8111P] where P = (Fo2 + 2Fc2)/3 |
5302 reflections | (Δ/σ)max = 0.001 |
382 parameters | Δρmax = 0.77 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Crystal data top
C3H5N2S+·C4H3O4− | V = 5569.3 (2) Å3 |
Mr = 216.21 | Z = 24 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 20.7129 (5) Å | µ = 0.34 mm−1 |
b = 7.1803 (2) Å | T = 292 K |
c = 37.4469 (9) Å | 0.3 × 0.2 × 0.2 mm |
Data collection top
Bruker Kappa APEXII CCD area-detector diffractometer | 5302 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker 2004) | 4161 reflections with I > 2σ(I) |
Tmin = 0.905, Tmax = 0.935 | Rint = 0.030 |
44583 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.149 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.77 e Å−3 |
5302 reflections | Δρmin = −0.29 e Å−3 |
382 parameters | |
Special details top
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell s.u.'s are taken
into account individually in the estimation of s.u.'s in distances, angles
and torsion angles; correlations between s.u.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | Uiso*/Ueq | |
C1 | 0.25737 (12) | 0.5170 (4) | 0.89229 (7) | 0.0411 (6) | |
C2 | 0.19739 (12) | 0.4825 (4) | 0.91260 (7) | 0.0440 (6) | |
H2 | 0.1582 | 0.5163 | 0.9024 | 0.053* | |
C3 | 0.19714 (13) | 0.4072 (4) | 0.94391 (7) | 0.0452 (7) | |
H3 | 0.2369 | 0.376 | 0.9537 | 0.054* | |
C4 | 0.13873 (12) | 0.3661 (4) | 0.96573 (6) | 0.0372 (6) | |
C5 | 0.86090 (13) | 0.6438 (4) | 0.70563 (7) | 0.0436 (6) | |
C6 | 0.80118 (15) | 0.6140 (5) | 0.72760 (8) | 0.0598 (9) | |
H6 | 0.7618 | 0.6408 | 0.7168 | 0.072* | |
C7 | 0.79956 (14) | 0.5566 (5) | 0.75901 (8) | 0.0560 (8) | |
H7 | 0.8383 | 0.5315 | 0.7706 | 0.067* | |
C8 | 0.73750 (14) | 0.5263 (5) | 0.77895 (8) | 0.0517 (7) | |
C9 | 0.77805 (14) | 0.5346 (4) | 0.93029 (7) | 0.0475 (7) | |
C10 | 0.73045 (14) | 0.4872 (5) | 0.90186 (8) | 0.0578 (8) | |
H10 | 0.747 | 0.4582 | 0.8795 | 0.069* | |
C11 | 0.66998 (14) | 0.4826 (4) | 0.90524 (8) | 0.0510 (7) | |
H11 | 0.6525 | 0.5183 | 0.9271 | 0.061* | |
C12 | 0.62398 (13) | 0.4228 (4) | 0.87609 (7) | 0.0420 (6) | |
C13 | 0.39085 (15) | 0.1607 (5) | 0.81328 (9) | 0.0589 (8) | |
H13 | 0.3487 | 0.1163 | 0.8132 | 0.071* | |
C14 | 0.41948 (14) | 0.2358 (5) | 0.84128 (8) | 0.0535 (7) | |
H14 | 0.3992 | 0.2514 | 0.8632 | 0.064* | |
C15 | 0.50171 (12) | 0.2564 (4) | 0.80162 (6) | 0.0372 (6) | |
C16 | 0.59895 (15) | 0.8931 (5) | 0.84973 (8) | 0.0573 (8) | |
H16 | 0.6408 | 0.9389 | 0.8482 | 0.069* | |
C17 | 0.56693 (14) | 0.8182 (5) | 0.82280 (8) | 0.0533 (8) | |
H17 | 0.5842 | 0.8061 | 0.8 | 0.064* | |
C18 | 0.49081 (12) | 0.7891 (4) | 0.86561 (6) | 0.0381 (6) | |
C19 | 0.38371 (15) | 0.3360 (5) | 0.98867 (9) | 0.0633 (9) | |
H19 | 0.3402 | 0.3655 | 0.9911 | 0.076* | |
C20 | 0.41957 (14) | 0.2647 (5) | 1.01418 (8) | 0.0569 (8) | |
H20 | 0.4039 | 0.2384 | 1.0369 | 0.068* | |
C21 | 0.49482 (12) | 0.2793 (4) | 0.97054 (6) | 0.0366 (6) | |
N1 | 0.48214 (10) | 0.2887 (3) | 0.83475 (5) | 0.0408 (5) | |
H1A | 0.5065 | 0.3382 | 0.8507 | 0.049* | |
N2 | 0.55871 (11) | 0.2991 (4) | 0.78937 (6) | 0.0520 (6) | |
H2A | 0.5865 | 0.3519 | 0.8031 | 0.062* | |
H2B | 0.5685 | 0.2745 | 0.7676 | 0.062* | |
N3 | 0.50586 (10) | 0.7601 (3) | 0.83150 (5) | 0.0416 (5) | |
H3A | 0.4798 | 0.7099 | 0.8164 | 0.05* | |
N4 | 0.43638 (11) | 0.7409 (4) | 0.88036 (6) | 0.0564 (7) | |
H4A | 0.4071 | 0.6863 | 0.8679 | 0.068* | |
H4B | 0.4297 | 0.7638 | 0.9026 | 0.068* | |
N5 | 0.48241 (10) | 0.2326 (3) | 1.00419 (5) | 0.0406 (5) | |
H5A | 0.511 | 0.1868 | 1.0183 | 0.049* | |
N6 | 0.55055 (11) | 0.2572 (4) | 0.95520 (6) | 0.0595 (7) | |
H6A | 0.5822 | 0.2097 | 0.9669 | 0.071* | |
H6B | 0.5558 | 0.29 | 0.9333 | 0.071* | |
O1 | 0.24545 (9) | 0.5865 (4) | 0.86082 (5) | 0.0577 (6) | |
H1 | 0.2795 | 0.602 | 0.8501 | 0.087* | |
O2 | 0.31055 (9) | 0.4863 (3) | 0.90351 (5) | 0.0584 (6) | |
O3 | 0.08426 (9) | 0.3686 (3) | 0.95174 (4) | 0.0434 (5) | |
O4 | 0.14913 (9) | 0.3287 (3) | 0.99796 (5) | 0.0548 (6) | |
O5 | 0.85032 (9) | 0.6565 (4) | 0.67310 (5) | 0.0607 (6) | |
O6 | 0.91552 (9) | 0.6570 (3) | 0.71945 (5) | 0.0487 (5) | |
O7 | 0.68476 (11) | 0.5522 (4) | 0.76654 (6) | 0.0694 (7) | |
O8 | 0.74817 (10) | 0.4671 (4) | 0.81063 (6) | 0.0721 (7) | |
H8 | 0.7137 | 0.4496 | 0.8209 | 0.108* | |
O9 | 0.83375 (10) | 0.5238 (4) | 0.92449 (5) | 0.0663 (7) | |
O10 | 0.75331 (9) | 0.5916 (4) | 0.96080 (5) | 0.0588 (6) | |
H10A | 0.7824 | 0.6065 | 0.9754 | 0.088* | |
O11 | 0.64324 (9) | 0.3995 (3) | 0.84501 (5) | 0.0600 (6) | |
O12 | 0.56694 (9) | 0.4015 (3) | 0.88564 (4) | 0.0473 (5) | |
S1 | 0.44144 (4) | 0.15539 (11) | 0.776860 (19) | 0.0533 (2) | |
S2 | 0.55304 (4) | 0.89448 (11) | 0.887911 (18) | 0.0491 (2) | |
S3 | 0.42763 (4) | 0.36780 (11) | 0.95001 (2) | 0.0511 (2) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0324 (14) | 0.0494 (16) | 0.0415 (13) | −0.0039 (12) | 0.0040 (11) | 0.0025 (12) |
C2 | 0.0307 (13) | 0.0549 (17) | 0.0464 (15) | 0.0006 (12) | −0.0012 (11) | 0.0075 (13) |
C3 | 0.0316 (13) | 0.0630 (18) | 0.0409 (14) | −0.0020 (13) | −0.0001 (11) | 0.0027 (13) |
C4 | 0.0334 (13) | 0.0473 (15) | 0.0308 (12) | −0.0087 (11) | 0.0008 (10) | −0.0043 (11) |
C5 | 0.0387 (15) | 0.0515 (16) | 0.0405 (14) | −0.0142 (12) | 0.0070 (12) | −0.0072 (12) |
C6 | 0.0480 (17) | 0.086 (2) | 0.0456 (17) | −0.0077 (16) | 0.0024 (13) | −0.0026 (16) |
C7 | 0.0430 (16) | 0.071 (2) | 0.0542 (18) | −0.0037 (15) | −0.0048 (13) | 0.0108 (16) |
C8 | 0.0373 (16) | 0.0610 (19) | 0.0568 (18) | −0.0047 (14) | 0.0108 (13) | −0.0012 (15) |
C9 | 0.0449 (16) | 0.0566 (18) | 0.0412 (14) | −0.0014 (14) | −0.0096 (12) | −0.0046 (13) |
C10 | 0.0457 (17) | 0.080 (2) | 0.0473 (16) | 0.0016 (16) | 0.0010 (13) | −0.0036 (16) |
C11 | 0.0438 (16) | 0.0601 (19) | 0.0492 (16) | −0.0039 (14) | 0.0042 (13) | −0.0008 (14) |
C12 | 0.0414 (15) | 0.0487 (16) | 0.0359 (13) | −0.0077 (12) | −0.0075 (11) | 0.0073 (12) |
C13 | 0.0412 (16) | 0.066 (2) | 0.070 (2) | −0.0146 (15) | −0.0025 (15) | 0.0039 (17) |
C14 | 0.0452 (16) | 0.066 (2) | 0.0490 (16) | −0.0056 (15) | 0.0075 (13) | 0.0044 (15) |
C15 | 0.0398 (14) | 0.0410 (14) | 0.0309 (12) | −0.0002 (11) | −0.0054 (10) | 0.0034 (11) |
C16 | 0.0455 (17) | 0.070 (2) | 0.0562 (18) | −0.0179 (15) | −0.0034 (14) | 0.0053 (16) |
C17 | 0.0479 (17) | 0.071 (2) | 0.0411 (15) | −0.0113 (15) | 0.0039 (13) | 0.0003 (14) |
C18 | 0.0378 (14) | 0.0451 (15) | 0.0314 (12) | 0.0012 (11) | −0.0062 (10) | −0.0004 (11) |
C19 | 0.0411 (17) | 0.077 (2) | 0.072 (2) | 0.0157 (16) | 0.0009 (15) | −0.0061 (18) |
C20 | 0.0477 (17) | 0.075 (2) | 0.0484 (17) | 0.0086 (16) | 0.0114 (14) | −0.0033 (16) |
C21 | 0.0368 (13) | 0.0413 (14) | 0.0318 (12) | 0.0004 (11) | −0.0055 (10) | 0.0010 (11) |
N1 | 0.0403 (12) | 0.0524 (14) | 0.0295 (10) | −0.0060 (10) | −0.0021 (9) | 0.0002 (10) |
N2 | 0.0436 (13) | 0.0771 (18) | 0.0353 (12) | −0.0083 (12) | 0.0022 (10) | −0.0009 (12) |
N3 | 0.0411 (12) | 0.0538 (14) | 0.0299 (10) | −0.0062 (11) | −0.0049 (9) | −0.0043 (10) |
N4 | 0.0410 (13) | 0.093 (2) | 0.0350 (12) | −0.0102 (14) | −0.0016 (10) | −0.0088 (13) |
N5 | 0.0393 (12) | 0.0495 (13) | 0.0330 (10) | 0.0061 (10) | −0.0021 (9) | 0.0016 (10) |
N6 | 0.0386 (13) | 0.103 (2) | 0.0366 (12) | 0.0049 (14) | 0.0005 (10) | 0.0146 (14) |
O1 | 0.0332 (10) | 0.0933 (17) | 0.0467 (11) | −0.0075 (11) | 0.0024 (9) | 0.0213 (11) |
O2 | 0.0339 (11) | 0.0893 (17) | 0.0519 (12) | −0.0016 (11) | 0.0008 (9) | 0.0119 (11) |
O3 | 0.0344 (10) | 0.0631 (13) | 0.0325 (9) | −0.0060 (9) | 0.0017 (7) | 0.0001 (8) |
O4 | 0.0403 (11) | 0.0930 (16) | 0.0312 (9) | −0.0174 (11) | −0.0021 (8) | 0.0027 (10) |
O5 | 0.0407 (11) | 0.1045 (18) | 0.0369 (10) | −0.0230 (11) | −0.0018 (8) | −0.0033 (11) |
O6 | 0.0429 (11) | 0.0729 (14) | 0.0303 (9) | −0.0124 (10) | 0.0012 (8) | 0.0017 (9) |
O7 | 0.0598 (14) | 0.0997 (19) | 0.0486 (12) | −0.0030 (13) | 0.0054 (11) | 0.0174 (12) |
O8 | 0.0367 (11) | 0.116 (2) | 0.0636 (13) | −0.0100 (13) | 0.0070 (11) | 0.0262 (15) |
O9 | 0.0446 (12) | 0.1029 (19) | 0.0513 (12) | 0.0098 (12) | −0.0036 (10) | −0.0208 (12) |
O10 | 0.0276 (9) | 0.0932 (17) | 0.0557 (12) | −0.0071 (11) | −0.0017 (9) | −0.0097 (12) |
O11 | 0.0368 (11) | 0.0981 (18) | 0.0452 (11) | −0.0192 (11) | 0.0025 (9) | 0.0027 (11) |
O12 | 0.0369 (10) | 0.0716 (14) | 0.0335 (9) | −0.0090 (9) | −0.0027 (8) | 0.0009 (9) |
S1 | 0.0576 (5) | 0.0592 (5) | 0.0430 (4) | −0.0104 (4) | −0.0152 (3) | −0.0054 (3) |
S2 | 0.0518 (4) | 0.0564 (5) | 0.0392 (4) | −0.0095 (3) | −0.0138 (3) | −0.0049 (3) |
S3 | 0.0453 (4) | 0.0552 (5) | 0.0528 (4) | 0.0059 (3) | −0.0162 (3) | 0.0074 (3) |
Geometric parameters (Å, º) top
C1—O2 | 1.199 (3) | C15—N2 | 1.303 (3) |
C1—O1 | 1.304 (3) | C15—N1 | 1.326 (3) |
C1—C2 | 1.478 (3) | C15—S1 | 1.716 (3) |
C2—C3 | 1.291 (4) | C16—C17 | 1.321 (4) |
C2—H2 | 0.93 | C16—S2 | 1.717 (3) |
C3—C4 | 1.489 (3) | C16—H16 | 0.93 |
C3—H3 | 0.93 | C17—N3 | 1.371 (4) |
C4—O3 | 1.244 (3) | C17—H17 | 0.93 |
C4—O4 | 1.255 (3) | C18—N4 | 1.302 (3) |
C5—O5 | 1.241 (3) | C18—N3 | 1.331 (3) |
C5—O6 | 1.248 (3) | C18—S2 | 1.712 (3) |
C5—C6 | 1.501 (4) | C19—C20 | 1.314 (4) |
C6—C7 | 1.247 (4) | C19—S3 | 1.725 (3) |
C6—H6 | 0.93 | C19—H19 | 0.93 |
C7—C8 | 1.502 (4) | C20—N5 | 1.374 (4) |
C7—H7 | 0.93 | C20—H20 | 0.93 |
C8—O7 | 1.202 (4) | C21—N6 | 1.299 (3) |
C8—O8 | 1.279 (4) | C21—N5 | 1.329 (3) |
C9—O9 | 1.176 (3) | C21—S3 | 1.712 (2) |
C9—O10 | 1.317 (3) | N1—H1A | 0.86 |
C9—C10 | 1.491 (4) | N2—H2A | 0.86 |
C10—C11 | 1.259 (4) | N2—H2B | 0.86 |
C10—H10 | 0.93 | N3—H3A | 0.86 |
C11—C12 | 1.511 (4) | N4—H4A | 0.86 |
C11—H11 | 0.93 | N4—H4B | 0.86 |
C12—O11 | 1.242 (3) | N5—H5A | 0.86 |
C12—O12 | 1.244 (3) | N6—H6A | 0.86 |
C13—C14 | 1.320 (4) | N6—H6B | 0.86 |
C13—S1 | 1.720 (3) | O1—H1 | 0.82 |
C13—H13 | 0.93 | O8—H8 | 0.82 |
C14—N1 | 1.374 (3) | O10—H10A | 0.82 |
C14—H14 | 0.93 | | |
| | | |
O2—C1—O1 | 124.1 (2) | N1—C15—S1 | 110.91 (19) |
O2—C1—C2 | 124.1 (2) | C17—C16—S2 | 111.1 (2) |
O1—C1—C2 | 111.7 (2) | C17—C16—H16 | 124.4 |
C3—C2—C1 | 122.8 (2) | S2—C16—H16 | 124.4 |
C3—C2—H2 | 118.6 | C16—C17—N3 | 113.9 (3) |
C1—C2—H2 | 118.6 | C16—C17—H17 | 123 |
C2—C3—C4 | 125.8 (3) | N3—C17—H17 | 123 |
C2—C3—H3 | 117.1 | N4—C18—N3 | 124.6 (2) |
C4—C3—H3 | 117.1 | N4—C18—S2 | 124.2 (2) |
O3—C4—O4 | 124.3 (2) | N3—C18—S2 | 111.14 (19) |
O3—C4—C3 | 120.2 (2) | C20—C19—S3 | 111.3 (2) |
O4—C4—C3 | 115.5 (2) | C20—C19—H19 | 124.3 |
O5—C5—O6 | 124.2 (2) | S3—C19—H19 | 124.3 |
O5—C5—C6 | 113.8 (2) | C19—C20—N5 | 113.8 (3) |
O6—C5—C6 | 122.1 (2) | C19—C20—H20 | 123.1 |
C7—C6—C5 | 125.9 (3) | N5—C20—H20 | 123.1 |
C7—C6—H6 | 117 | N6—C21—N5 | 124.1 (2) |
C5—C6—H6 | 117 | N6—C21—S3 | 124.7 (2) |
C6—C7—C8 | 122.7 (3) | N5—C21—S3 | 111.23 (19) |
C6—C7—H7 | 118.7 | C15—N1—C14 | 114.0 (2) |
C8—C7—H7 | 118.7 | C15—N1—H1A | 123 |
O7—C8—O8 | 124.6 (3) | C14—N1—H1A | 123 |
O7—C8—C7 | 124.3 (3) | C15—N2—H2A | 120 |
O8—C8—C7 | 111.2 (3) | C15—N2—H2B | 120 |
O9—C9—O10 | 124.2 (3) | H2A—N2—H2B | 120 |
O9—C9—C10 | 120.1 (3) | C18—N3—C17 | 113.4 (2) |
O10—C9—C10 | 115.7 (3) | C18—N3—H3A | 123.3 |
C11—C10—C9 | 126.3 (3) | C17—N3—H3A | 123.3 |
C11—C10—H10 | 116.8 | C18—N4—H4A | 120 |
C9—C10—H10 | 116.8 | C18—N4—H4B | 120 |
C10—C11—C12 | 124.2 (3) | H4A—N4—H4B | 120 |
C10—C11—H11 | 117.9 | C21—N5—C20 | 113.5 (2) |
C12—C11—H11 | 117.9 | C21—N5—H5A | 123.2 |
O11—C12—O12 | 123.9 (2) | C20—N5—H5A | 123.2 |
O11—C12—C11 | 120.8 (2) | C21—N6—H6A | 120 |
O12—C12—C11 | 115.2 (2) | C21—N6—H6B | 120 |
C14—C13—S1 | 111.4 (2) | H6A—N6—H6B | 120 |
C14—C13—H13 | 124.3 | C1—O1—H1 | 109.5 |
S1—C13—H13 | 124.3 | C8—O8—H8 | 109.5 |
C13—C14—N1 | 113.3 (3) | C9—O10—H10A | 109.5 |
C13—C14—H14 | 123.3 | C15—S1—C13 | 90.31 (14) |
N1—C14—H14 | 123.3 | C18—S2—C16 | 90.47 (13) |
N2—C15—N1 | 124.4 (2) | C21—S3—C19 | 90.14 (14) |
N2—C15—S1 | 124.6 (2) | | |
| | | |
O2—C1—C2—C3 | −3.4 (5) | N2—C15—N1—C14 | 178.4 (3) |
O1—C1—C2—C3 | 177.2 (3) | S1—C15—N1—C14 | −0.4 (3) |
C1—C2—C3—C4 | −179.2 (3) | C13—C14—N1—C15 | 0.7 (4) |
C2—C3—C4—O3 | 14.6 (5) | N4—C18—N3—C17 | −178.0 (3) |
C2—C3—C4—O4 | −166.0 (3) | S2—C18—N3—C17 | 0.9 (3) |
O5—C5—C6—C7 | 163.1 (4) | C16—C17—N3—C18 | −0.5 (4) |
O6—C5—C6—C7 | −18.0 (5) | N6—C21—N5—C20 | −178.4 (3) |
C5—C6—C7—C8 | −178.6 (3) | S3—C21—N5—C20 | 0.5 (3) |
C6—C7—C8—O7 | 0.8 (6) | C19—C20—N5—C21 | −0.3 (4) |
C6—C7—C8—O8 | 180.0 (4) | N2—C15—S1—C13 | −178.8 (3) |
O9—C9—C10—C11 | 175.6 (4) | N1—C15—S1—C13 | 0.0 (2) |
O10—C9—C10—C11 | −6.0 (5) | C14—C13—S1—C15 | 0.5 (3) |
C9—C10—C11—C12 | −176.3 (3) | N4—C18—S2—C16 | 178.1 (3) |
C10—C11—C12—O11 | −10.4 (5) | N3—C18—S2—C16 | −0.8 (2) |
C10—C11—C12—O12 | 170.2 (3) | C17—C16—S2—C18 | 0.5 (3) |
S1—C13—C14—N1 | −0.8 (4) | N6—C21—S3—C19 | 178.4 (3) |
S2—C16—C17—N3 | −0.1 (4) | N5—C21—S3—C19 | −0.4 (2) |
S3—C19—C20—N5 | −0.1 (4) | C20—C19—S3—C21 | 0.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O6i | 0.86 | 2.02 | 2.860 (3) | 167 |
N3—H3A···O6ii | 0.86 | 1.93 | 2.773 (3) | 167 |
N4—H4A···O5ii | 0.86 | 1.95 | 2.748 (3) | 155 |
N4—H4B···O3iii | 0.86 | 2.01 | 2.858 (3) | 169 |
N5—H5A···O3iv | 0.86 | 1.93 | 2.775 (3) | 168 |
N6—H6A···O4iv | 0.86 | 1.93 | 2.762 (3) | 162 |
O1—H1···O5ii | 0.82 | 1.75 | 2.566 (3) | 175 |
O10—H10A···O4v | 0.82 | 1.8 | 2.607 (3) | 170 |
N1—H1A···O12 | 0.86 | 1.87 | 2.715 (3) | 169 |
N2—H2A···O11 | 0.86 | 1.99 | 2.815 (3) | 161 |
N6—H6B···O12 | 0.86 | 1.97 | 2.824 (3) | 172 |
O8—H8···O11 | 0.82 | 1.75 | 2.572 (3) | 175 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1/2, y, −z+3/2; (iii) −x+1/2, y+1/2, z; (iv) x+1/2, −y+1/2, −z+2; (v) −x+1, −y+1, −z+2. |
Experimental details
| (2ATHM) | (2ATHF) |
Crystal data |
Chemical formula | C3H5N2S+·C4H3O4− | C3H5N2S+·C4H3O4− |
Mr | 216.21 | 216.21 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca |
Temperature (K) | 292 | 292 |
a, b, c (Å) | 6.3372 (4), 22.4153 (14), 6.8618 (4) | 20.7129 (5), 7.1803 (2), 37.4469 (9) |
α, β, γ (°) | 90, 111.112 (2), 90 | 90, 90, 90 |
V (Å3) | 909.29 (10) | 5569.3 (2) |
Z | 4 | 24 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.35 | 0.34 |
Crystal size (mm) | 0.28 × 0.16 × 0.08 | 0.3 × 0.2 × 0.2 |
|
Data collection |
Diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer | Bruker Kappa APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker 2004) | Multi-scan (SADABS; Bruker 2004) |
Tmin, Tmax | 0.909, 0.973 | 0.905, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11445, 2529, 2056 | 44583, 5302, 4161 |
Rint | 0.028 | 0.030 |
(sin θ/λ)max (Å−1) | 0.696 | 0.611 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.117, 1.06 | 0.052, 0.149, 1.04 |
No. of reflections | 2529 | 5302 |
No. of parameters | 128 | 382 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.35, −0.22 | 0.77, −0.29 |
Hydrogen-bond geometry (Å, º) for (2ATHM) top
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1 | 0.82 | 1.65 | 2.4663 (19) | 175.1 |
N2—H2A···O1i | 0.86 | 2.01 | 2.8618 (19) | 173.9 |
N2—H2B···O2 | 0.86 | 2.01 | 2.8453 (19) | 163.9 |
N1—H1···O2i | 0.86 | 1.91 | 2.7607 (18) | 170.7 |
C3—H3···O4ii | 0.93 | 2.57 | 3.410 (2) | 149.8 |
C2—H2···O3iii | 0.93 | 2.39 | 3.249 (2) | 153.3 |
Symmetry codes: (i) x+1, y, z; (ii) −x+1/2, y+1/2, −z+3/2; (iii) −x+3/2, y+1/2, −z+3/2. |
Hydrogen-bond geometry (Å, º) for (2ATHF) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···O6i | 0.86 | 2.02 | 2.860 (3) | 166.7 |
N3—H3A···O6ii | 0.86 | 1.93 | 2.773 (3) | 166.5 |
N4—H4A···O5ii | 0.86 | 1.95 | 2.748 (3) | 154.9 |
N4—H4B···O3iii | 0.86 | 2.01 | 2.858 (3) | 169 |
N5—H5A···O3iv | 0.86 | 1.93 | 2.775 (3) | 168.2 |
N6—H6A···O4iv | 0.86 | 1.93 | 2.762 (3) | 162.3 |
O1—H1···O5ii | 0.82 | 1.75 | 2.566 (3) | 174.8 |
O10—H10A···O4v | 0.82 | 1.8 | 2.607 (3) | 169.7 |
N1—H1A···O12 | 0.86 | 1.87 | 2.715 (3) | 169.1 |
N2—H2A···O11 | 0.86 | 1.99 | 2.815 (3) | 160.5 |
N6—H6B···O12 | 0.86 | 1.97 | 2.824 (3) | 171.9 |
O8—H8···O11 | 0.82 | 1.75 | 2.572 (3) | 175.3 |
Symmetry codes: (i) −x+3/2, y−1/2, z; (ii) x−1/2, y, −z+3/2; (iii) −x+1/2, y+1/2, z; (iv) x+1/2, −y+1/2, −z+2; (v) −x+1, −y+1, −z+2. |
Comparision of selected geometric parameters (Å, °) of 2ATHM and 2ATHF with
neutral 2-amino-1,3-thiazole top | Neutral 2-amino-1,3-thiazole | 2ATHM | 2ATHF (Molecule A) | 2ATHF (Molecule B) | 2ATHF (Molecule C) |
C—N(ring)—C | 109.40 (5) | 113.79 (13) | 114.0 (2) | 113.4 (2) | 113.5 (2) |
C—S—C | 88.60 (3) | 90.39 (8) | 90.31 (14) | 90.47 (14) | 90.16 (14) |
N(ring)—C—S | 114.9 (5) | 111.41 (12) | 110.93 (18) | 111.15 (18) | 111.23 (19) |
N(ring)—C | 1.298 (6) | 1.324 (19) (N1—C1) | 1.326 (3) (N1—C15) | 1.331 (3) (N3—C18) | 1.329 (3) (N5—C21) |
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Many naturally occurring and synthetic thiazole derivatives exhibit biological activities, such as antibiotic, anti-inflammatory, antibacterial and anthelmintic properties (Metzger, 1984; Crews et al., 1988; Shinagawa et al., 1997; Shivarama Holla et al., 2003). Crystal structures and hydrogen-bonding patterns of derivatives of 2-amino-1,3-thiazole have already been reported (Lynch, 2002; Lynch & McClenaghan, 2004, 2005; Glidewell et al., 2004). Maleic acid, the Z isomer of butenedioic acid, is a simple building block in two- and three-dimensional supramolecular architectures (Bowes et al., 2003; Jin et al., 2003), and many crystal structures of 1:1 organic salts of maleic acid with organoamines have been reported to explain their aggregation patterns and hydrogen-bonding interactions (Alagar et al., 2001; Rajagopal et al., 2001; Lah & Leban, 2003). In all such structures, the maleic acid exists in either a monoionized state or its fully deprotonated form. Fumaric acid, the E isomer of butenedioic acid, is a key intermediate in the biosynthesis of organic acids (Natarajan et al., 2009). An extensive network of hydrogen bonding has been observed in the majority of the crystal structures of salts of fumaric acid (Alagar et al., 2003; Natarajan et al., 2009; Büyükgüngör et al., 2004).
The present study reports the structures of 2ATHM and 2ATHF, 1:1 organic salts of 2-amino-1,3-thiazole with the Z and E isomers of butenedioic acid, respectively. This work is a continuation of the study of the salts of the Z and E isomers of butenedioic acid with 8-hydroxyquinoline reported from our laboratory recently (Franklin & Balasubramanian, 2009). The crystal structure of the salt of 2-amino-1,3-thiazole with succinnic acid has also been reported by us recently (Fun et al., 2009). In the present study, the effect of the isomers on the conformational features and hydrogen-bonding networks in the 2-amino-1,3-thiazole adducts are analysed and compared with those of related structures.
The molecular structures of 2ATHM and 2ATHF are shown in Figs. 1 and 2, respectively. The asymmetric unit of 2ATHM consists of a semimaleate anion and a 2-amino-1,3-thiazolium cation, while that of 2ATHF consists of three independent semifumarate anions and 2-amino-1,3-thiazolium cations. The 2-amino-1,3-thiazolium cations in both compounds are protonated at their ring N atoms, which is confirmed by the widening of the internal C—N—C angle from the value in unprotonated 2-amino-1,3-thiazole (Caranoni & Reboul, 1982) (Table 1). A similar configuration was observed in 2,2'-diamino-4,4'-bi-1,3-thiazolium fumarate (Liu et al., 2003). There is an increase in the C—S—C bond angles and a decrease in the N—C—S bond angles of the cations of 2ATHM and 2ATHF from the value in neutral 2-amino-1,3-thiazole (Caranoni & Reboul, 1982) (Table 1). These observed values are comparable with those found in bis(2-amino-1,3-thiazolium) succinate succinic acid (Fun et al., 2009).
The 2-amino-1,3-thiazolium ring of 2ATHM is essentially planar, with the maximum deviation from planarity being 0.007 (1) Å for atom C1. Similarly, the three 2-amino-1,3-thiazolium rings of 2ATHF are essentially planar, with the maximum deviations from planarity being 0.004 (3) Å for atom C14, 0.006 (3) Å for atom C18 and 0.003 (3) Å for atom C21. The semimaleate and semifumarate anions are almost planar. The angle between the planes of the two halves of the semimaleate anion in 2ATHM (O1/O2/C4/C5 and O3/O4/C6/C7) is 5.81 (12)°, while the angles between the planes of two halves of the three semifumarate anions in 2ATHF are 11.76 (18), 16.3 (2) and 13.47 (19)° [Please refer angles to specific anions].
Extensive networks of N—H···O and O—H···O hydrogen bonds (Tables 2 and 3) are observed to stabilize the crystal packing of both 2ATHM and 2ATHF. Parts of the crystal packing of the molecules, depicting the hydrogen-bonding interactions and various hydrogen-bonded motifs formed in 2ATHM and 2ATHF, are shown in Figs. 3 and 4, respectively. In 2ATHM, an intramolecular hydrogen bond between atoms O1 and O4 of the semimaleate anion is asymmetric and generates an S(7) motif (Bernstein et al., 1995), as observed in 8-hydroxyquinolinium hydrogen maleate (Franklin & Balasubramanian, 2009). This intramolecular hydrogen bond with an S(7) motif is a common occurrence in several salts of maleate (Alagar et al., 2001, 2002; Rajagopal et al., 2001, 2002). The corresponding intramolecular hydrogen bond with an S(5) motif is found in the semifumarate anion of 8-hydroxyquinolinium hydrogen fumarate (Franklin & Balasubramanian, 2009) but is not observed here in the semifumarate anions of 2ATHF. The two structures here differ, with intermolecular hydrogen-bonding interactions observed between the semifumarate anions in 2ATHF but not between the semimaleate anions in 2ATHM. In both 2ATHM and 2ATHF, the Namine and Nring atoms of the 2-amino-1,3-thiazolium cations link with the deprotonated carboxylate groups of the anions through strong N—H···O hydrogen bonds, to form a common cyclic ring motif denoted by R22(8). Similar R22(8) motifs have been observed in the vast majority of adducts/organic salts comprising a 2-amino-heterocycle and a carboxylic acid molecule (Lynch, 2004; Büyükgüngör et al., 2004; Fun et al., 2009).
In 2ATHM, a pair of 2-amino-1,3-thiazolium cations is linked to a pair of maleate anions through Namine—H···O and Nring—H···O hydrogen bonds, in which the acceptor O atom forms a bifurcated interaction (entries 3 and 4 in Table 2), along with two C—H···O interactions (entries 5 and 6 in Table 2), resulting in a supramolecular ring motif of type R34(14). Two Namine—H···O hydrogen bonds (entries 2 and 3 in Table 2) and two C—H···O interactions (entries 5 and 6 in Table 2), along with an intramolecular O—H···O hydrogen bond, form a ring motif of type R44(16). The combination of these interactions with two other supramolecular R22(8) and R34(14) motifs forms two-dimensional sheets extending parallel to the ab plane (Fig. 5). The overall packing of the structure consists of supramolecular sheets built from anions and cations stacked discretely one above the other along the [001] direction.
In 2ATHF, a very simple one-dimensional substructure is generated by an intermolecular interaction between the anions alone. A second-level graph-set motif of D22(9) (Sudbeck et al., 1995) is formed by three independent fumarate anions linked through O—H···O hydrogen bonds (entries 8 and 12 in Table 3). These D22(9) motifs are linked through an O—H···O hydrogen bond (entry 7 in Table 3), forming a one-dimensional anionic chain extending along the [001] direction. A similar one-dimensional anionic chain is observed in most of the fumarate salts (Franklin & Balasubramanian, 2009; Bowes et al., 2003; Büyükgüngör et al., 2004). The cations are linked to these anionic chains through N—H···O hydrogen bonds to form a ring motif of type R54(24). These alternately fused R22(8) (mentioned earlier) and R54(24) supramolecular motifs combine with the D22(9) motif to generate a two-dimensional hydrogen-bonded zigzag layer extending parallel to the bc plane (Fig. 6). This matrix extends along the [100] direction as parallel independent layers, with no classical hydrogen bonds observed to bind the layers.