Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807023690/at2296sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807023690/at2296Isup2.hkl |
CCDC reference: 651501
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- R factor = 0.032
- wR factor = 0.085
- Data-to-parameter ratio = 12.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H2A .. S1 .. 2.94 Ang. PLAT731_ALERT_1_C Bond Calc 0.90(2), Rep 0.899(9) ...... 2.22 su-Ra N2 -H2A 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.91(2), Rep 0.909(9) ...... 2.22 su-Ra N2 -H2B 1.555 1.555 PLAT731_ALERT_1_C Bond Calc 0.902(19), Rep 0.902(9) ...... 2.11 su-Ra N4 -H4A 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.90(2), Rep 0.899(9) ...... 2.22 su-Ra N2 -H2A 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.90(2), Rep 0.899(9) ...... 2.22 su-Ra N2 -H2A 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.91(2), Rep 0.909(9) ...... 2.22 su-Ra N2 -H2B 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.902(19), Rep 0.902(9) ...... 2.11 su-Ra N4 -H4A 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 6
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 7 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
3-Amino-2-thioxo-thiazolidin-4-one (1 g) was added to an anhydrous ethanol (50 ml), with stirring at 350 K. The resulting colourless solution was filtered and the filtrate was allowed to stand in air at room temperature for 10 d, yielding colourless crystals of (I).
H atoms of the amino group were found from difference Fourier map and refined freely. H atoms of the methylene group were placed in calculated positions with C—H = 0.97 Å and refined using a riding model, with Uiso(H) = 1.2Ueq(C).
In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry, we report the synthesis and structure of the title compound, (I).
The asymmetric unit of (I) comprises two independent molecules (Fig. 1), lying on the mirror planes, one at z = 0 and the other at z = 1/2. The two molecules differ in the orientation of the Amino group by a 180° rotation around its bond with the thiazoline ring. In both molecules the geometric parameters are normal. Each independent molecule is linked to a symmetry-equivalent molecule by intermolecular N—H···O and N—H···N hydrogen bonds,and linked to himself by N—H···S hydrogen bonds (Table 1), forming a three-dimensional network which leads to a stable crystal structure (Fig. 2).
For related literature, see: Belloni et al. (2005); Parashar et al. (1988); Santos et al. (2001); Tynan et al. (2005).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
C3H4N2OS2 | F(000) = 608 |
Mr = 148.20 | Dx = 1.668 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2513 reflections |
a = 9.8257 (17) Å | θ = 3.1–26.2° |
b = 9.3118 (16) Å | µ = 0.80 mm−1 |
c = 13.416 (2) Å | T = 294 K |
β = 105.924 (3)° | Block, colourless |
V = 1180.4 (3) Å3 | 0.30 × 0.26 × 0.20 mm |
Z = 8 |
Bruker SMART CCD area-detector diffractometer | 2052 independent reflections |
Radiation source: fine-focus sealed tube | 1686 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
φ and ω scans | θmax = 25.0°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→9 |
Tmin = 0.797, Tmax = 0.857 | k = −9→11 |
5324 measured reflections | l = −15→15 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0389P)2 + 0.5975P] where P = (Fo2 + 2Fc2)/3 |
2052 reflections | (Δ/σ)max = 0.001 |
161 parameters | Δρmax = 0.34 e Å−3 |
6 restraints | Δρmin = −0.34 e Å−3 |
C3H4N2OS2 | V = 1180.4 (3) Å3 |
Mr = 148.20 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.8257 (17) Å | µ = 0.80 mm−1 |
b = 9.3118 (16) Å | T = 294 K |
c = 13.416 (2) Å | 0.30 × 0.26 × 0.20 mm |
β = 105.924 (3)° |
Bruker SMART CCD area-detector diffractometer | 2052 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1686 reflections with I > 2σ(I) |
Tmin = 0.797, Tmax = 0.857 | Rint = 0.028 |
5324 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 6 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.34 e Å−3 |
2052 reflections | Δρmin = −0.34 e Å−3 |
161 parameters |
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 | 0.42862 (7) | 0.22451 (7) | 0.88952 (5) | 0.0471 (2) | |
S2 | 0.45652 (7) | 0.17983 (7) | 1.11280 (5) | 0.0469 (2) | |
S3 | 0.74095 (8) | 0.46329 (7) | 0.97871 (6) | 0.0562 (2) | |
S4 | 0.94214 (8) | 0.65599 (8) | 1.12373 (5) | 0.0547 (2) | |
O1 | 0.13941 (19) | −0.0621 (2) | 0.80930 (12) | 0.0521 (5) | |
O2 | 0.8082 (2) | 0.6549 (2) | 0.74386 (13) | 0.0655 (6) | |
N1 | 0.28161 (19) | 0.03994 (19) | 0.95556 (13) | 0.0320 (4) | |
N2 | 0.2236 (2) | −0.0421 (2) | 1.02200 (14) | 0.0384 (5) | |
N3 | 0.87489 (19) | 0.66393 (19) | 0.91821 (13) | 0.0332 (4) | |
N4 | 0.9526 (2) | 0.7909 (2) | 0.92041 (18) | 0.0447 (5) | |
C1 | 0.3843 (2) | 0.1415 (2) | 0.99099 (17) | 0.0326 (5) | |
C2 | 0.2310 (2) | 0.0216 (3) | 0.84990 (17) | 0.0368 (5) | |
C3 | 0.3057 (3) | 0.1194 (3) | 0.79385 (17) | 0.0436 (6) | |
H3A | 0.2381 | 0.1814 | 0.7470 | 0.052* | |
H3B | 0.3554 | 0.0638 | 0.7537 | 0.052* | |
C4 | 0.8593 (2) | 0.6040 (2) | 1.00653 (17) | 0.0356 (5) | |
C5 | 0.7091 (3) | 0.4857 (3) | 0.8416 (2) | 0.0552 (7) | |
H5A | 0.7339 | 0.3987 | 0.8108 | 0.066* | |
H5B | 0.6099 | 0.5064 | 0.8098 | 0.066* | |
C6 | 0.7985 (3) | 0.6077 (3) | 0.82491 (18) | 0.0427 (6) | |
H2A | 0.295 (2) | −0.080 (3) | 1.0717 (15) | 0.067 (9)* | |
H2B | 0.174 (2) | 0.021 (2) | 1.0505 (17) | 0.060 (8)* | |
H4A | 0.974 (3) | 0.788 (3) | 0.8592 (10) | 0.076 (10)* | |
H4B | 1.0315 (17) | 0.790 (3) | 0.9741 (12) | 0.065 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0468 (4) | 0.0497 (4) | 0.0476 (4) | −0.0103 (3) | 0.0177 (3) | 0.0000 (3) |
S2 | 0.0439 (4) | 0.0494 (4) | 0.0388 (3) | 0.0025 (3) | −0.0031 (3) | −0.0089 (3) |
S3 | 0.0545 (5) | 0.0407 (4) | 0.0734 (5) | −0.0070 (3) | 0.0178 (4) | 0.0075 (3) |
S4 | 0.0518 (4) | 0.0744 (5) | 0.0339 (3) | 0.0148 (4) | 0.0048 (3) | −0.0048 (3) |
O1 | 0.0526 (11) | 0.0622 (12) | 0.0380 (9) | −0.0170 (9) | 0.0066 (8) | −0.0129 (8) |
O2 | 0.1022 (17) | 0.0598 (12) | 0.0319 (9) | 0.0172 (11) | 0.0136 (10) | 0.0003 (9) |
N1 | 0.0328 (10) | 0.0334 (10) | 0.0291 (9) | 0.0017 (8) | 0.0074 (8) | −0.0010 (8) |
N2 | 0.0419 (12) | 0.0391 (11) | 0.0347 (10) | −0.0022 (9) | 0.0114 (9) | 0.0031 (9) |
N3 | 0.0347 (11) | 0.0297 (10) | 0.0338 (10) | 0.0020 (8) | 0.0073 (8) | −0.0014 (8) |
N4 | 0.0437 (13) | 0.0348 (11) | 0.0580 (14) | −0.0057 (10) | 0.0178 (11) | 0.0014 (10) |
C1 | 0.0285 (12) | 0.0301 (11) | 0.0379 (12) | 0.0056 (10) | 0.0069 (9) | −0.0031 (9) |
C2 | 0.0357 (13) | 0.0411 (13) | 0.0326 (12) | 0.0047 (11) | 0.0078 (10) | −0.0041 (10) |
C3 | 0.0495 (15) | 0.0491 (15) | 0.0343 (12) | 0.0028 (12) | 0.0149 (11) | 0.0000 (11) |
C4 | 0.0328 (13) | 0.0355 (12) | 0.0390 (12) | 0.0091 (10) | 0.0108 (10) | 0.0028 (10) |
C5 | 0.0480 (16) | 0.0411 (14) | 0.0646 (18) | 0.0005 (13) | −0.0048 (13) | −0.0139 (13) |
C6 | 0.0501 (15) | 0.0366 (13) | 0.0363 (13) | 0.0111 (11) | 0.0036 (11) | −0.0054 (11) |
S1—C1 | 1.722 (2) | N2—H2B | 0.909 (9) |
S1—C3 | 1.793 (2) | N3—C4 | 1.356 (3) |
S2—C1 | 1.633 (2) | N3—C6 | 1.374 (3) |
S3—C4 | 1.724 (2) | N3—N4 | 1.403 (3) |
S3—C5 | 1.792 (3) | N4—H4A | 0.902 (9) |
S4—C4 | 1.633 (2) | N4—H4B | 0.902 (10) |
O1—C2 | 1.202 (3) | C2—C3 | 1.495 (3) |
O2—C6 | 1.201 (3) | C3—H3A | 0.9700 |
N1—C1 | 1.370 (3) | C3—H3B | 0.9700 |
N1—C2 | 1.378 (3) | C5—C6 | 1.490 (4) |
N1—N2 | 1.408 (3) | C5—H5A | 0.9700 |
N2—H2A | 0.899 (9) | C5—H5B | 0.9700 |
C1—S1—C3 | 93.10 (11) | N1—C2—C3 | 110.7 (2) |
C4—S3—C5 | 92.92 (11) | C2—C3—S1 | 107.43 (15) |
C1—N1—C2 | 117.77 (19) | C2—C3—H3A | 110.2 |
C1—N1—N2 | 122.88 (17) | S1—C3—H3A | 110.2 |
C2—N1—N2 | 119.31 (19) | C2—C3—H3B | 110.2 |
N1—N2—H2A | 108.4 (19) | S1—C3—H3B | 110.2 |
N1—N2—H2B | 105.7 (17) | H3A—C3—H3B | 108.5 |
H2A—N2—H2B | 109.9 (14) | N3—C4—S4 | 125.01 (18) |
C4—N3—C6 | 118.4 (2) | N3—C4—S3 | 110.78 (16) |
C4—N3—N4 | 121.30 (19) | S4—C4—S3 | 124.21 (14) |
C6—N3—N4 | 119.9 (2) | C6—C5—S3 | 107.41 (17) |
N3—N4—H4A | 102.4 (19) | C6—C5—H5A | 110.2 |
N3—N4—H4B | 110.5 (19) | S3—C5—H5A | 110.2 |
H4A—N4—H4B | 111.3 (14) | C6—C5—H5B | 110.2 |
N1—C1—S2 | 125.08 (17) | S3—C5—H5B | 110.2 |
N1—C1—S1 | 110.96 (15) | H5A—C5—H5B | 108.5 |
S2—C1—S1 | 123.96 (14) | O2—C6—N3 | 121.8 (2) |
O1—C2—N1 | 124.1 (2) | O2—C6—C5 | 127.7 (2) |
O1—C2—C3 | 125.2 (2) | N3—C6—C5 | 110.5 (2) |
C2—N1—C1—S2 | 179.48 (16) | C6—N3—C4—S4 | 179.53 (17) |
N2—N1—C1—S2 | 1.5 (3) | N4—N3—C4—S4 | −8.4 (3) |
C2—N1—C1—S1 | −0.6 (2) | C6—N3—C4—S3 | 0.2 (3) |
N2—N1—C1—S1 | −178.61 (15) | N4—N3—C4—S3 | 172.31 (16) |
C3—S1—C1—N1 | −0.33 (17) | C5—S3—C4—N3 | −0.39 (18) |
C3—S1—C1—S2 | 179.58 (15) | C5—S3—C4—S4 | −179.72 (16) |
C1—N1—C2—O1 | −178.7 (2) | C4—S3—C5—C6 | 0.45 (19) |
N2—N1—C2—O1 | −0.6 (3) | C4—N3—C6—O2 | −179.4 (2) |
C1—N1—C2—C3 | 1.4 (3) | N4—N3—C6—O2 | 8.4 (3) |
N2—N1—C2—C3 | 179.52 (18) | C4—N3—C6—C5 | 0.2 (3) |
O1—C2—C3—S1 | 178.6 (2) | N4—N3—C6—C5 | −172.1 (2) |
N1—C2—C3—S1 | −1.5 (2) | S3—C5—C6—O2 | 179.1 (2) |
C1—S1—C3—C2 | 1.05 (18) | S3—C5—C6—N3 | −0.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.90 (1) | 2.38 (2) | 3.049 (3) | 131 (2) |
N2—H2A···S1ii | 0.90 (1) | 2.95 (2) | 3.708 (2) | 144 (2) |
N2—H2B···N4iii | 0.91 (1) | 2.25 (1) | 3.130 (3) | 164 (2) |
N4—H4A···O1iv | 0.90 (1) | 2.38 (2) | 2.994 (3) | 126 (2) |
N4—H4B···N2iv | 0.90 (1) | 2.40 (2) | 3.061 (3) | 130 (2) |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z+2; (iii) −x+1, −y+1, −z+2; (iv) x+1, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C3H4N2OS2 |
Mr | 148.20 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 9.8257 (17), 9.3118 (16), 13.416 (2) |
β (°) | 105.924 (3) |
V (Å3) | 1180.4 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.30 × 0.26 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.797, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5324, 2052, 1686 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.085, 1.03 |
No. of reflections | 2052 |
No. of parameters | 161 |
No. of restraints | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.34, −0.34 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O2i | 0.899 (9) | 2.38 (2) | 3.049 (3) | 131 (2) |
N2—H2A···S1ii | 0.899 (9) | 2.945 (15) | 3.708 (2) | 143.8 (19) |
N2—H2B···N4iii | 0.909 (9) | 2.246 (11) | 3.130 (3) | 164 (2) |
N4—H4A···O1iv | 0.902 (9) | 2.38 (2) | 2.994 (3) | 126 (2) |
N4—H4B···N2iv | 0.902 (10) | 2.40 (2) | 3.061 (3) | 130 (2) |
Symmetry codes: (i) x−1/2, −y+1/2, z+1/2; (ii) −x+1, −y, −z+2; (iii) −x+1, −y+1, −z+2; (iv) x+1, y+1, z. |
In order to establish control over the preparation of crystalline solid materials so that their architecture and properties are predictable (Belloni et al., 2005; Tynan et al., 2005; Parashar et al., 1988), the synthesis of new and designed crystal structures has become a major strand of modern chemistry, we report the synthesis and structure of the title compound, (I).
The asymmetric unit of (I) comprises two independent molecules (Fig. 1), lying on the mirror planes, one at z = 0 and the other at z = 1/2. The two molecules differ in the orientation of the Amino group by a 180° rotation around its bond with the thiazoline ring. In both molecules the geometric parameters are normal. Each independent molecule is linked to a symmetry-equivalent molecule by intermolecular N—H···O and N—H···N hydrogen bonds,and linked to himself by N—H···S hydrogen bonds (Table 1), forming a three-dimensional network which leads to a stable crystal structure (Fig. 2).