The title compound, C
12H
11N
3O
2S, was synthesized by a condensation reaction of 2-acetylindan-1,3-dione and thiosemicarbazide in ethanol in the presence of glacial acetic acid. The molecule adopts a thioketone form. The dihedral angle between the mean planes of 1
H-inden-1,3(2
H)-dione and hydrazinecarbothioamide units is 86.32 (7)°. Weak intramolecular N—H

O and C—H

O hydrogen bonds are observed. In the crystal, molecules are linked
via pairs of weak intermolecular N—H

O hydrogen bonds, forming inversion dimers. The dimers are further linked into a three-dimensional network through N—H

S and N—H

O hydrogen bonds, and π–π interactions [centroid–centroid distances = 3.5619 (10)–3.9712 (9) Å].
Supporting information
CCDC reference: 1857321
Key indicators
- Single-crystal X-ray study
- T = 99 K
- Mean
(C-C) = 0.003 Å
- R factor = 0.063
- wR factor = 0.173
- Data-to-parameter ratio = 18.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for S1 --C1 . 6.9 s.u.
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.2 Note
PLAT906_ALERT_3_C Large K Value in the Analysis of Variance ...... 3.167 Check
Alert level G
PLAT063_ALERT_4_G Crystal Size Likely too Large for Beam Size .... 0.76 mm
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical ? Check
PLAT072_ALERT_2_G SHELXL First Parameter in WGHT Unusually Large 0.12 Report
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels .......... 4 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min). 1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density. 5 Info
0 ALERT level A = Most likely a serious problem - resolve or explain
0 ALERT level B = A potentially serious problem, consider carefully
3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
6 ALERT level G = General information/check it is not something unexpected
1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
2 ALERT type 4 Improvement, methodology, query or suggestion
0 ALERT type 5 Informative message, check
Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).
2-[1-(1,3-Dioxo-1,3-dihydro-2
H-inden-2-ylidene)ethyl]hydrazinecarbothioamide
top
Crystal data top
C12H11N3O2S | Dx = 1.440 Mg m−3 |
Mr = 261.30 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 6090 reflections |
a = 15.0751 (6) Å | θ = 2.4–29.6° |
b = 7.6891 (4) Å | µ = 0.27 mm−1 |
c = 20.7891 (9) Å | T = 99 K |
V = 2409.75 (19) Å3 | Rod, brown |
Z = 8 | 0.76 × 0.25 × 0.25 mm |
F(000) = 1088 | |
Data collection top
Bruker D8 Venture diffractometer | 2712 reflections with I > 2σ(I) |
profile data from θ/2θ scans | Rint = 0.073 |
Absorption correction: multi-scan (SADABS; Bruker, 2014) | θmax = 29.6°, θmin = 2.4° |
Tmin = 0.824, Tmax = 0.937 | h = −20→18 |
18247 measured reflections | k = −8→10 |
3382 independent reflections | l = −28→28 |
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)] = 0.063 | Hydrogen site location: mixed |
wR(F2) = 0.173 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.117P)2 + 0.3104P] where P = (Fo2 + 2Fc2)/3 |
3382 reflections | (Δ/σ)max = 0.001 |
181 parameters | Δρmax = 0.79 e Å−3 |
0 restraints | Δρmin = −1.00 e Å−3 |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.43388 (3) | 0.69858 (6) | 0.75750 (2) | 0.01816 (17) | |
O1 | 0.86124 (9) | 0.5148 (2) | 0.58244 (8) | 0.0294 (4) | |
O2 | 0.58261 (8) | 0.40510 (17) | 0.48472 (6) | 0.0202 (3) | |
N1 | 0.50396 (12) | 0.8510 (2) | 0.65405 (8) | 0.0213 (4) | |
HN1 | 0.4960 (17) | 0.948 (4) | 0.6726 (15) | 0.043 (8)* | |
HN2 | 0.5428 (16) | 0.853 (3) | 0.6251 (14) | 0.025 (6)* | |
N2 | 0.52093 (10) | 0.5557 (2) | 0.66273 (7) | 0.0162 (3) | |
HN3 | 0.5202 (14) | 0.465 (3) | 0.6853 (13) | 0.024 (6)* | |
N3 | 0.57075 (10) | 0.5469 (2) | 0.60634 (7) | 0.0150 (3) | |
HN4 | 0.5434 (15) | 0.516 (3) | 0.5700 (14) | 0.027 (6)* | |
C1 | 0.49117 (11) | 0.7065 (2) | 0.68685 (8) | 0.0152 (4) | |
C2 | 0.66012 (11) | 0.5365 (2) | 0.60836 (8) | 0.0141 (3) | |
C3 | 0.70518 (11) | 0.4833 (2) | 0.55397 (8) | 0.0151 (3) | |
C4 | 0.80153 (11) | 0.4714 (2) | 0.54558 (10) | 0.0191 (4) | |
C5 | 0.81627 (12) | 0.3939 (2) | 0.48089 (10) | 0.0209 (4) | |
C6 | 0.89580 (14) | 0.3553 (3) | 0.45015 (12) | 0.0308 (5) | |
H6 | 0.951321 | 0.377395 | 0.470159 | 0.037* | |
C7 | 0.89078 (15) | 0.2830 (3) | 0.38902 (12) | 0.0366 (6) | |
H7 | 0.944060 | 0.256797 | 0.366630 | 0.044* | |
C8 | 0.81003 (16) | 0.2482 (3) | 0.35982 (11) | 0.0349 (5) | |
H8 | 0.809265 | 0.197883 | 0.318095 | 0.042* | |
C9 | 0.72982 (15) | 0.2855 (3) | 0.39040 (10) | 0.0268 (5) | |
H9 | 0.674394 | 0.261752 | 0.370510 | 0.032* | |
C10 | 0.73498 (12) | 0.3592 (2) | 0.45145 (8) | 0.0177 (4) | |
C11 | 0.66251 (11) | 0.4159 (2) | 0.49572 (8) | 0.0149 (3) | |
C12 | 0.70463 (12) | 0.5863 (3) | 0.67010 (9) | 0.0215 (4) | |
H12A | 0.684628 | 0.702208 | 0.683240 | 0.026* | |
H12B | 0.769069 | 0.587450 | 0.663875 | 0.026* | |
H12C | 0.689323 | 0.501675 | 0.703566 | 0.026* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0289 (3) | 0.0173 (3) | 0.0083 (2) | −0.00088 (16) | 0.00634 (15) | −0.00102 (15) |
O1 | 0.0189 (7) | 0.0388 (9) | 0.0304 (9) | 0.0005 (6) | −0.0073 (6) | 0.0053 (6) |
O2 | 0.0190 (6) | 0.0289 (7) | 0.0128 (6) | 0.0048 (5) | −0.0024 (5) | −0.0033 (5) |
N1 | 0.0347 (9) | 0.0172 (8) | 0.0120 (8) | 0.0020 (7) | 0.0095 (6) | 0.0015 (6) |
N2 | 0.0263 (8) | 0.0151 (7) | 0.0073 (7) | 0.0003 (6) | 0.0054 (6) | 0.0000 (6) |
N3 | 0.0190 (7) | 0.0219 (8) | 0.0042 (7) | 0.0015 (5) | 0.0020 (5) | −0.0013 (5) |
C1 | 0.0193 (8) | 0.0168 (8) | 0.0094 (8) | −0.0013 (6) | −0.0018 (6) | −0.0021 (6) |
C2 | 0.0188 (8) | 0.0141 (8) | 0.0095 (8) | −0.0012 (6) | −0.0021 (6) | 0.0032 (6) |
C3 | 0.0164 (8) | 0.0179 (8) | 0.0110 (8) | 0.0020 (6) | −0.0013 (6) | 0.0028 (6) |
C4 | 0.0167 (8) | 0.0207 (9) | 0.0200 (9) | 0.0026 (6) | 0.0004 (6) | 0.0086 (7) |
C5 | 0.0232 (9) | 0.0171 (9) | 0.0223 (10) | 0.0058 (7) | 0.0088 (7) | 0.0080 (7) |
C6 | 0.0256 (10) | 0.0230 (10) | 0.0436 (13) | 0.0052 (8) | 0.0169 (9) | 0.0101 (9) |
C7 | 0.0424 (13) | 0.0228 (11) | 0.0444 (14) | 0.0086 (9) | 0.0313 (11) | 0.0070 (9) |
C8 | 0.0565 (14) | 0.0243 (11) | 0.0239 (11) | 0.0098 (10) | 0.0237 (10) | 0.0024 (9) |
C9 | 0.0420 (12) | 0.0239 (10) | 0.0146 (9) | 0.0070 (8) | 0.0083 (8) | 0.0011 (7) |
C10 | 0.0240 (9) | 0.0173 (8) | 0.0118 (8) | 0.0053 (7) | 0.0066 (6) | 0.0043 (7) |
C11 | 0.0200 (8) | 0.0164 (8) | 0.0082 (8) | 0.0048 (6) | 0.0020 (6) | 0.0029 (6) |
C12 | 0.0263 (9) | 0.0268 (10) | 0.0113 (8) | −0.0015 (7) | −0.0062 (7) | −0.0009 (7) |
Geometric parameters (Å, º) top
S1—C1 | 1.7050 (18) | C4—C5 | 1.488 (3) |
O1—C4 | 1.228 (2) | C5—C6 | 1.391 (3) |
O2—C11 | 1.229 (2) | C5—C10 | 1.395 (3) |
N1—C1 | 1.318 (2) | C6—C7 | 1.389 (4) |
N1—HN1 | 0.85 (3) | C6—H6 | 0.9500 |
N1—HN2 | 0.84 (3) | C7—C8 | 1.386 (4) |
N2—C1 | 1.340 (2) | C7—H7 | 0.9500 |
N2—N3 | 1.394 (2) | C8—C9 | 1.396 (3) |
N2—HN3 | 0.84 (2) | C8—H8 | 0.9500 |
N3—C2 | 1.350 (2) | C9—C10 | 1.392 (3) |
N3—HN4 | 0.89 (3) | C9—H9 | 0.9500 |
C2—C3 | 1.381 (2) | C10—C11 | 1.493 (2) |
C2—C12 | 1.498 (2) | C12—H12A | 0.9800 |
C3—C11 | 1.466 (2) | C12—H12B | 0.9800 |
C3—C4 | 1.466 (2) | C12—H12C | 0.9800 |
| | | |
C1—N1—HN1 | 119 (2) | C7—C6—C5 | 117.3 (2) |
C1—N1—HN2 | 119.0 (17) | C7—C6—H6 | 121.3 |
HN1—N1—HN2 | 114 (2) | C5—C6—H6 | 121.3 |
C1—N2—N3 | 122.48 (15) | C8—C7—C6 | 121.71 (18) |
C1—N2—HN3 | 120.3 (17) | C8—C7—H7 | 119.1 |
N3—N2—HN3 | 115.8 (16) | C6—C7—H7 | 119.1 |
C2—N3—N2 | 120.94 (15) | C7—C8—C9 | 121.4 (2) |
C2—N3—HN4 | 118.1 (15) | C7—C8—H8 | 119.3 |
N2—N3—HN4 | 118.4 (15) | C9—C8—H8 | 119.3 |
N1—C1—N2 | 119.14 (16) | C10—C9—C8 | 116.8 (2) |
N1—C1—S1 | 123.34 (14) | C10—C9—H9 | 121.6 |
N2—C1—S1 | 117.46 (13) | C8—C9—H9 | 121.6 |
N3—C2—C3 | 118.86 (15) | C9—C10—C5 | 121.78 (17) |
N3—C2—C12 | 117.30 (15) | C9—C10—C11 | 129.77 (18) |
C3—C2—C12 | 123.84 (16) | C5—C10—C11 | 108.44 (16) |
C2—C3—C11 | 124.43 (15) | O2—C11—C3 | 127.43 (15) |
C2—C3—C4 | 127.10 (16) | O2—C11—C10 | 125.64 (16) |
C11—C3—C4 | 108.34 (15) | C3—C11—C10 | 106.93 (14) |
O1—C4—C3 | 129.43 (19) | C2—C12—H12A | 109.5 |
O1—C4—C5 | 124.29 (17) | C2—C12—H12B | 109.5 |
C3—C4—C5 | 106.28 (16) | H12A—C12—H12B | 109.5 |
C6—C5—C10 | 121.0 (2) | C2—C12—H12C | 109.5 |
C6—C5—C4 | 129.0 (2) | H12A—C12—H12C | 109.5 |
C10—C5—C4 | 109.99 (15) | H12B—C12—H12C | 109.5 |
| | | |
C1—N2—N3—C2 | 97.7 (2) | C4—C5—C6—C7 | −179.82 (18) |
N3—N2—C1—N1 | 4.8 (3) | C5—C6—C7—C8 | −0.9 (3) |
N3—N2—C1—S1 | −178.07 (12) | C6—C7—C8—C9 | 0.5 (3) |
N2—N3—C2—C3 | 163.37 (16) | C7—C8—C9—C10 | 0.0 (3) |
N2—N3—C2—C12 | −17.4 (2) | C8—C9—C10—C5 | −0.2 (3) |
N3—C2—C3—C11 | −7.9 (3) | C8—C9—C10—C11 | 179.00 (18) |
C12—C2—C3—C11 | 172.90 (16) | C6—C5—C10—C9 | −0.2 (3) |
N3—C2—C3—C4 | 176.93 (16) | C4—C5—C10—C9 | −179.77 (17) |
C12—C2—C3—C4 | −2.3 (3) | C6—C5—C10—C11 | −179.53 (16) |
C2—C3—C4—O1 | −4.8 (3) | C4—C5—C10—C11 | 0.9 (2) |
C11—C3—C4—O1 | 179.40 (19) | C2—C3—C11—O2 | 4.2 (3) |
C2—C3—C4—C5 | 175.41 (17) | C4—C3—C11—O2 | −179.82 (17) |
C11—C3—C4—C5 | −0.42 (19) | C2—C3—C11—C10 | −175.02 (16) |
O1—C4—C5—C6 | 0.3 (3) | C4—C3—C11—C10 | 0.94 (19) |
C3—C4—C5—C6 | −179.83 (19) | C9—C10—C11—O2 | 0.3 (3) |
O1—C4—C5—C10 | 179.86 (18) | C5—C10—C11—O2 | 179.61 (16) |
C3—C4—C5—C10 | −0.3 (2) | C9—C10—C11—C3 | 179.59 (18) |
C10—C5—C6—C7 | 0.7 (3) | C5—C10—C11—C3 | −1.14 (19) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12B···O1 | 0.98 | 2.26 | 3.033 (3) | 135 |
N2—HN3···S1i | 0.84 (2) | 2.47 (2) | 3.2796 (16) | 163 (2) |
N1—HN1···S1ii | 0.85 (3) | 2.63 (3) | 3.3764 (19) | 147 (2) |
N1—HN2···O1iii | 0.84 (3) | 2.11 (3) | 2.816 (2) | 142 (2) |
N3—HN4···O2 | 0.89 (3) | 2.05 (3) | 2.7592 (19) | 135 (2) |
N3—HN4···O2iv | 0.89 (3) | 2.30 (2) | 3.0107 (19) | 137 (2) |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+1, y+1/2, −z+3/2; (iii) −x+3/2, y+1/2, z; (iv) −x+1, −y+1, −z+1. |