supplementary materials
1-(3,4-Dimethylbenzylidene)-4-ethylthiosemicarbazide
The title compound, C12H17N3S, was prepared by the reaction of 4-ethylthiosemicarbazide and 3,4-dimethylbenzaldehyde. The dihedral angle between the thiourea unit and the benzene ring is 7.09 (8)°. In the crystal, inversion dimers linked by pairs of N-H
S hydrogen bonds occur.
A mixture of the 4-ethylthiosemicarbazide (0.1 mol) and 3,4-dimethylbenzaldehyde
(0.1 mol) was stirred in refluxing ethanol (30 mL) for 2 h to afford the title
compound (0.085 mol, yield 85%). Single crystals suitable for X-ray
measurements were obtained by recrystallization of a solution of the title
compound in ethanol at room temperature.
H atoms were fixed geometrically and allowed to ride on their attached atoms,
with C—H distances = 0.93-0.97 Å; N-H = 0.86Å, and with Uiso =
1.2Ueq(C,N) or 1.2Ueq(Cmethyl).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
1-(3,4-Dimethylbenzylidene)-4-ethylthiosemicarbazide
top
Crystal data top
| C12H17N3S | F(000) = 504 |
| Mr = 235.35 | Dx = 1.189 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2429 reflections |
| a = 8.6659 (17) Å | θ = 3.3–27.5° |
| b = 15.207 (3) Å | µ = 0.23 mm−1 |
| c = 9.993 (2) Å | T = 293 K |
| β = 93.47 (3)° | Block, colorless |
| V = 1314.5 (5) Å3 | 0.22 × 0.20 × 0.18 mm |
| Z = 4 | |
Data collection top
Bruker SMART CCD
diffractometer | 2429 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.056 |
| graphite | θmax = 27.5°, θmin = 3.3° |
| φ and ω scans | h = −11→11 |
| 12215 measured reflections | k = −19→19 |
| 3006 independent reflections | l = −12→11 |
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)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.206 | H-atom parameters constrained |
| S = 1.05 | w = 1/[σ2(Fo2) + (0.1293P)2 + 0.2681P]
where P = (Fo2 + 2Fc2)/3 |
| 3006 reflections | (Δ/σ)max < 0.001 |
| 145 parameters | Δρmax = 0.39 e Å−3 |
| 0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
| C12H17N3S | V = 1314.5 (5) Å3 |
| Mr = 235.35 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 8.6659 (17) Å | µ = 0.23 mm−1 |
| b = 15.207 (3) Å | T = 293 K |
| c = 9.993 (2) Å | 0.22 × 0.20 × 0.18 mm |
| β = 93.47 (3)° | |
Data collection top
Bruker SMART CCD
diffractometer | 2429 reflections with I > 2σ(I) |
| 12215 measured reflections | Rint = 0.056 |
| 3006 independent reflections | θmax = 27.5° |
Refinement top
| R[F2 > 2σ(F2)] = 0.065 | H-atom parameters constrained |
| wR(F2) = 0.206 | Δρmax = 0.39 e Å−3 |
| S = 1.05 | Δρmin = −0.34 e Å−3 |
| 3006 reflections | Absolute structure: ? |
| 145 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top| | x | y | z | Uiso*/Ueq | |
| S1 | 0.84996 (8) | 0.11266 (4) | 0.92188 (6) | 0.0702 (3) | |
| N1 | 1.02915 (18) | 0.11306 (10) | 1.28935 (16) | 0.0480 (4) | |
| N2 | 0.9879 (2) | 0.08927 (11) | 1.15935 (16) | 0.0532 (4) | |
| H2A | 1.0235 | 0.0415 | 1.1269 | 0.064* | |
| C9 | 1.1228 (2) | 0.06157 (13) | 1.35388 (19) | 0.0513 (4) | |
| H9A | 1.1574 | 0.0115 | 1.3114 | 0.062* | |
| N3 | 0.8377 (2) | 0.21192 (12) | 1.14109 (18) | 0.0581 (4) | |
| H3A | 0.8630 | 0.2193 | 1.2249 | 0.070* | |
| C4 | 1.1328 (3) | 0.15253 (16) | 1.5627 (2) | 0.0597 (5) | |
| H4A | 1.0691 | 0.1947 | 1.5206 | 0.072* | |
| C8 | 1.2782 (2) | 0.01920 (13) | 1.5576 (2) | 0.0544 (5) | |
| H8A | 1.3120 | −0.0293 | 1.5108 | 0.065* | |
| C3 | 1.1773 (2) | 0.07867 (13) | 1.49181 (19) | 0.0487 (4) | |
| C10 | 0.8916 (2) | 0.14075 (13) | 1.08270 (19) | 0.0485 (4) | |
| C7 | 1.3299 (2) | 0.03031 (14) | 1.6911 (2) | 0.0571 (5) | |
| C6 | 1.2793 (3) | 0.10241 (17) | 1.7607 (2) | 0.0644 (6) | |
| C5 | 1.1829 (3) | 0.16286 (18) | 1.6946 (2) | 0.0708 (6) | |
| H5A | 1.1511 | 0.2120 | 1.7409 | 0.085* | |
| C2 | 1.4415 (3) | −0.0353 (2) | 1.7562 (3) | 0.0837 (8) | |
| H2B | 1.4651 | −0.0188 | 1.8480 | 0.126* | |
| H2C | 1.5348 | −0.0360 | 1.7092 | 0.126* | |
| H2D | 1.3956 | −0.0927 | 1.7530 | 0.126* | |
| C12 | 0.5844 (3) | 0.2822 (2) | 1.1272 (4) | 0.0950 (9) | |
| H12A | 0.5239 | 0.3265 | 1.0800 | 0.143* | |
| H12B | 0.5935 | 0.2963 | 1.2210 | 0.143* | |
| H12C | 0.5348 | 0.2261 | 1.1149 | 0.143* | |
| C11 | 0.7391 (3) | 0.27866 (18) | 1.0749 (3) | 0.0787 (7) | |
| H11A | 0.7289 | 0.2663 | 0.9796 | 0.094* | |
| H11B | 0.7881 | 0.3357 | 1.0868 | 0.094* | |
| C1 | 1.3292 (4) | 0.1167 (3) | 1.9069 (3) | 0.0973 (11) | |
| H1B | 1.2832 | 0.1698 | 1.9380 | 0.146* | |
| H1C | 1.4397 | 0.1216 | 1.9166 | 0.146* | |
| H1D | 1.2962 | 0.0679 | 1.9589 | 0.146* | |
Atomic displacement parameters (Å2) top| | U11 | U22 | U33 | U12 | U13 | U23 |
| S1 | 0.0834 (5) | 0.0734 (4) | 0.0509 (4) | 0.0196 (3) | −0.0188 (3) | −0.0005 (2) |
| N1 | 0.0472 (8) | 0.0524 (8) | 0.0437 (8) | 0.0018 (6) | −0.0027 (6) | 0.0016 (6) |
| N2 | 0.0575 (9) | 0.0541 (8) | 0.0464 (8) | 0.0123 (7) | −0.0088 (7) | −0.0005 (7) |
| C9 | 0.0536 (10) | 0.0496 (9) | 0.0496 (10) | 0.0050 (7) | −0.0049 (8) | 0.0006 (8) |
| N3 | 0.0575 (9) | 0.0611 (10) | 0.0554 (9) | 0.0163 (8) | 0.0018 (7) | 0.0074 (7) |
| C4 | 0.0582 (11) | 0.0668 (13) | 0.0535 (11) | 0.0141 (9) | −0.0015 (8) | −0.0024 (9) |
| C8 | 0.0552 (10) | 0.0493 (9) | 0.0572 (11) | −0.0028 (8) | −0.0075 (8) | 0.0059 (8) |
| C3 | 0.0461 (9) | 0.0515 (9) | 0.0481 (9) | −0.0020 (7) | −0.0019 (7) | 0.0045 (8) |
| C10 | 0.0414 (9) | 0.0526 (9) | 0.0510 (10) | 0.0036 (7) | −0.0019 (7) | 0.0086 (8) |
| C7 | 0.0505 (10) | 0.0641 (11) | 0.0554 (11) | −0.0114 (8) | −0.0088 (8) | 0.0156 (9) |
| C6 | 0.0523 (11) | 0.0943 (16) | 0.0459 (11) | −0.0092 (10) | −0.0025 (8) | 0.0010 (10) |
| C5 | 0.0677 (14) | 0.0861 (16) | 0.0580 (12) | 0.0112 (11) | 0.0003 (10) | −0.0162 (11) |
| C2 | 0.0802 (16) | 0.0911 (18) | 0.0768 (16) | 0.0046 (13) | −0.0208 (13) | 0.0262 (14) |
| C12 | 0.0636 (15) | 0.0908 (19) | 0.128 (3) | 0.0270 (14) | −0.0117 (15) | −0.0062 (18) |
| C11 | 0.0817 (16) | 0.0739 (15) | 0.0810 (16) | 0.0347 (13) | 0.0081 (12) | 0.0185 (12) |
| C1 | 0.089 (2) | 0.150 (3) | 0.0508 (14) | −0.0023 (18) | −0.0132 (13) | −0.0072 (15) |
Geometric parameters (Å, °) top
| S1—C10 | 1.681 (2) | C7—C2 | 1.509 (3) |
| N1—C9 | 1.275 (2) | C6—C5 | 1.383 (3) |
| N1—N2 | 1.375 (2) | C6—C1 | 1.514 (3) |
| N2—C10 | 1.349 (2) | C5—H5A | 0.9300 |
| N2—H2A | 0.8600 | C2—H2B | 0.9600 |
| C9—C3 | 1.453 (3) | C2—H2C | 0.9600 |
| C9—H9A | 0.9300 | C2—H2D | 0.9600 |
| N3—C10 | 1.328 (3) | C12—C11 | 1.468 (4) |
| N3—C11 | 1.459 (3) | C12—H12A | 0.9600 |
| N3—H3A | 0.8600 | C12—H12B | 0.9600 |
| C4—C5 | 1.371 (3) | C12—H12C | 0.9600 |
| C4—C3 | 1.395 (3) | C11—H11A | 0.9700 |
| C4—H4A | 0.9300 | C11—H11B | 0.9700 |
| C8—C7 | 1.392 (3) | C1—H1B | 0.9600 |
| C8—C3 | 1.395 (3) | C1—H1C | 0.9600 |
| C8—H8A | 0.9300 | C1—H1D | 0.9600 |
| C7—C6 | 1.384 (3) | | |
| | | |
| C9—N1—N2 | 115.95 (16) | C4—C5—C6 | 122.0 (2) |
| C10—N2—N1 | 120.03 (16) | C4—C5—H5A | 119.0 |
| C10—N2—H2A | 120.0 | C6—C5—H5A | 119.0 |
| N1—N2—H2A | 120.0 | C7—C2—H2B | 109.5 |
| N1—C9—C3 | 122.03 (18) | C7—C2—H2C | 109.5 |
| N1—C9—H9A | 119.0 | H2B—C2—H2C | 109.5 |
| C3—C9—H9A | 119.0 | C7—C2—H2D | 109.5 |
| C10—N3—C11 | 125.4 (2) | H2B—C2—H2D | 109.5 |
| C10—N3—H3A | 117.3 | H2C—C2—H2D | 109.5 |
| C11—N3—H3A | 117.3 | C11—C12—H12A | 109.5 |
| C5—C4—C3 | 119.9 (2) | C11—C12—H12B | 109.5 |
| C5—C4—H4A | 120.0 | H12A—C12—H12B | 109.5 |
| C3—C4—H4A | 120.0 | C11—C12—H12C | 109.5 |
| C7—C8—C3 | 121.9 (2) | H12A—C12—H12C | 109.5 |
| C7—C8—H8A | 119.0 | H12B—C12—H12C | 109.5 |
| C3—C8—H8A | 119.0 | N3—C11—C12 | 112.7 (2) |
| C8—C3—C4 | 117.90 (18) | N3—C11—H11A | 109.0 |
| C8—C3—C9 | 119.30 (18) | C12—C11—H11A | 109.0 |
| C4—C3—C9 | 122.80 (18) | N3—C11—H11B | 109.0 |
| N3—C10—N2 | 116.46 (17) | C12—C11—H11B | 109.0 |
| N3—C10—S1 | 124.51 (14) | H11A—C11—H11B | 107.8 |
| N2—C10—S1 | 119.02 (15) | C6—C1—H1B | 109.5 |
| C6—C7—C8 | 119.00 (19) | C6—C1—H1C | 109.5 |
| C6—C7—C2 | 121.4 (2) | H1B—C1—H1C | 109.5 |
| C8—C7—C2 | 119.6 (2) | C6—C1—H1D | 109.5 |
| C5—C6—C7 | 119.1 (2) | H1B—C1—H1D | 109.5 |
| C5—C6—C1 | 119.6 (2) | H1C—C1—H1D | 109.5 |
| C7—C6—C1 | 121.2 (2) | | |
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···S1i | 0.86 | 2.65 | 3.4929 (18) | 168 |
| Symmetry codes: (i) −x+2, −y, −z+2. |
Table 1
Hydrogen-bond geometry (Å, °) top
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2A···S1i | 0.86 | 2.65 | 3.4929 (18) | 168 |
| Symmetry codes: (i) −x+2, −y, −z+2. |
Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Casas, J. S., Garcia-Tasende, M. S. & Sordo, J. (2000). Coord. Chem. Rev. 209, 197–261.
Habermehl, N. C., Angus, P. M. & Kilah, N. L. (2006). Inorg. Chem. 45, 1445–1462.
Li, Y.-F. & Jian, F.-F. (2010). Acta Cryst. E66, o1399.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
![[Figure 1]](./lh5136fig1thm.gif)
Schiff-bases have attracted attention because they can be utilized as effective ligands in coordination chemistry (Casas et al., 2000). They are important intermediates which have been reported to form chiral coordination compounds with many interesting properties (Habermehl et al., 2006). As part of our research on new Schiff-base compounds we synthesized the title compound (I), and have determined its crystal structure. The molecular structure is shown in Fig. 1. The dihedral angle between the benzene ring and the thiourea unit is 7.09 (8)°. The bond lengths and angles agree with those observed in 4-Ethyl-1-(4-methylbenzylidene)thiosemicarbazide (Li & Jian, 2010). In the crystal structure, centrosymmetric dimers are formed by pairs of intermolecular N—H···S hydrogen bonds.