Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805042388/sj6174sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805042388/sj6174Isup2.hkl |
CCDC reference: 296662
Dilute hydrochloric acid (Volume?) was added to a solution of 2-mercapto-1,3,4-thiadiazole (1 g) in water (20 ml). Subsequent crystallization over 2 weeks gave colourless needle-like crystals of (I) suitable for X-ray diffraction analysis.
H atoms were treated as riding, with C—H = 0.93 Å and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(C,N).
Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2004); software used to prepare material for publication: SHELXTL.
C2H2N2S2 | F(000) = 480 |
Mr = 118.18 | Dx = 1.688 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4625 reflections |
a = 8.623 (2) Å | θ = 3.1–28.3° |
b = 8.249 (2) Å | µ = 0.97 mm−1 |
c = 13.075 (3) Å | T = 296 K |
V = 930.0 (4) Å3 | Needle, colourless |
Z = 8 | 0.32 × 0.13 × 0.13 mm |
Bruker APEX-2 CCD area-detector diffractometer | 1066 independent reflections |
Radiation source: fine-focus sealed tube | 1000 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 27.5°, θmin = 3.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.747, Tmax = 0.884 | k = −10→10 |
7289 measured reflections | l = −16→16 |
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)] = 0.021 | H-atom parameters constrained |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0291P)2 + 0.2499P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
1066 reflections | Δρmax = 0.26 e Å−3 |
56 parameters | Δρmin = −0.19 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.069 (3) |
C2H2N2S2 | V = 930.0 (4) Å3 |
Mr = 118.18 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.623 (2) Å | µ = 0.97 mm−1 |
b = 8.249 (2) Å | T = 296 K |
c = 13.075 (3) Å | 0.32 × 0.13 × 0.13 mm |
Bruker APEX-2 CCD area-detector diffractometer | 1066 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1000 reflections with I > 2σ(I) |
Tmin = 0.747, Tmax = 0.884 | Rint = 0.020 |
7289 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.056 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.26 e Å−3 |
1066 reflections | Δρmin = −0.19 e Å−3 |
56 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 | 0.09586 (4) | 0.15440 (4) | 0.60840 (2) | 0.03849 (13) | |
S2 | 0.21697 (4) | −0.03176 (4) | 0.79383 (2) | 0.04018 (14) | |
N1 | 0.37514 (12) | 0.09299 (14) | 0.63640 (8) | 0.0365 (2) | |
H1 | 0.4600 | 0.0562 | 0.6620 | 0.044* | |
N2 | 0.37633 (13) | 0.17856 (15) | 0.54651 (8) | 0.0431 (3) | |
C1 | 0.23979 (14) | 0.06778 (14) | 0.68338 (9) | 0.0307 (2) | |
C2 | 0.23609 (15) | 0.21803 (17) | 0.52344 (10) | 0.0408 (3) | |
H2 | 0.2121 | 0.2769 | 0.4649 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.03080 (19) | 0.0484 (2) | 0.0362 (2) | 0.00549 (12) | −0.00182 (11) | 0.00581 (13) |
S2 | 0.0376 (2) | 0.0481 (2) | 0.0349 (2) | 0.00590 (13) | 0.00539 (11) | 0.01104 (13) |
N1 | 0.0294 (5) | 0.0484 (6) | 0.0317 (5) | 0.0021 (4) | 0.0011 (4) | 0.0060 (4) |
N2 | 0.0400 (6) | 0.0561 (7) | 0.0332 (6) | −0.0003 (5) | 0.0047 (4) | 0.0093 (5) |
C1 | 0.0303 (5) | 0.0329 (5) | 0.0289 (5) | 0.0023 (4) | −0.0001 (4) | −0.0018 (4) |
C2 | 0.0449 (7) | 0.0486 (7) | 0.0290 (6) | 0.0035 (6) | 0.0005 (5) | 0.0057 (5) |
S1—C2 | 1.7238 (14) | N1—N2 | 1.3709 (15) |
S1—C1 | 1.7356 (12) | N1—H1 | 0.8600 |
S2—C1 | 1.6727 (13) | N2—C2 | 1.2882 (17) |
N1—C1 | 1.3353 (16) | C2—H2 | 0.9300 |
C2—S1—C1 | 89.30 (6) | N1—C1—S1 | 107.52 (9) |
C1—N1—N2 | 118.76 (10) | S2—C1—S1 | 127.28 (7) |
C1—N1—H1 | 120.6 | N2—C2—S1 | 115.51 (10) |
N2—N1—H1 | 120.6 | N2—C2—H2 | 122.2 |
C2—N2—N1 | 108.89 (10) | S1—C2—H2 | 122.2 |
N1—C1—S2 | 125.20 (9) | ||
C1—N1—N2—C2 | −0.94 (17) | C2—S1—C1—S2 | 179.59 (9) |
N2—N1—C1—S2 | −179.26 (9) | N1—N2—C2—S1 | −0.02 (16) |
N2—N1—C1—S1 | 1.39 (14) | C1—S1—C2—N2 | 0.66 (12) |
C2—S1—C1—N1 | −1.08 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S2i | 0.86 | 2.40 | 3.2527 (13) | 170 |
Symmetry code: (i) x+1/2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | C2H2N2S2 |
Mr | 118.18 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 8.623 (2), 8.249 (2), 13.075 (3) |
V (Å3) | 930.0 (4) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.97 |
Crystal size (mm) | 0.32 × 0.13 × 0.13 |
Data collection | |
Diffractometer | Bruker APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.747, 0.884 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7289, 1066, 1000 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.056, 1.06 |
No. of reflections | 1066 |
No. of parameters | 56 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.19 |
Computer programs: APEX2 (Bruker, 2004), APEX2, SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2004), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S2i | 0.86 | 2.40 | 3.2527 (13) | 170 |
Symmetry code: (i) x+1/2, y, −z+3/2. |
Thiadiazoles have attracted increasing attention because of their potential applications in pharmaceutial, agricultural, industrial, coordination and polymer chemistry (Coyanis et al., 2002; Wang & Cao, 2005).
Molecules of the title compound, (I), exist in the crystal structure in a zwitterionic form, with the thiadiazole atom N1 protonated and the thiol substituent deprotonated (Fig. 1). The thiodiazole ring is planar, with a maximum deviation from the ring plane of 0.0082 (7) Å for atom N1. The thiolate atom S2 lies 0.018 (6) Å from that plane.
N1—H1···S2 hydrogen bonds link adjacent molecules in a zigzag network parallel to the ac plane (Figs. 2 and 3).