Acta Cryst. (2007). E63, o2781 [ doi:10.1107/S1600536807020855 ]
The title compound, C12H16N3S, was prepared by the reaction of phenyl isothiocyanate with N-methylpiperazine. The crystal structure is stabilized by intermolecular N-H
S hydrogen-bonding interactions.
A mixture of the phenyl isothiocyanate (0.1 mol), and N-methypiperazine (0.1 mol) was stirred in refluxing ethanol (30 ml) for 5 h to afford the title compound (0.085 mol, yield 85%). Single crystals suitable of (I) for X-ray measurements were obtained by recrystallization from ethanol at room temperature.
The H atom bonded to the N atom was found from a difference Fourier map and refined freely. The other H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H = 0.93 - 0.97 Å, and Uiso(H) = 1.2–1.5Ueq(C).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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.
![[Figure 1]](./at2276fig1thm.gif)
| Fig. 1. The molecular structure of the title compound (I), showing 30% probability displacement ellipsoids and the atom-numbering scheme. |
| C12H17N3S | F(000) = 1008 |
| Mr = 235.35 | Dx = 1.189 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 2706 reflections |
| a = 12.615 (3) Å | θ = 2.5–22.9° |
| b = 9.564 (3) Å | µ = 0.23 mm−1 |
| c = 21.792 (6) Å | T = 294 K |
| V = 2629.4 (12) Å3 | Block, colourless |
| Z = 8 | 0.26 × 0.24 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 2683 independent reflections |
| Radiation source: fine-focus sealed tube | 1558 reflections with I > 2σ(I) |
| graphite | Rint = 0.063 |
| φ and ω scans | θmax = 26.4°, θmin = 1.9° |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −15→15 |
| Tmin = 0.944, Tmax = 0.956 | k = −11→11 |
| 14113 measured reflections | l = −12→27 |
| 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)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.113 | w = 1/[σ2(Fo2) + (0.0536P)2 + 0.208P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.00 | (Δ/σ)max = 0.002 |
| 2683 reflections | Δρmax = 0.19 e Å−3 |
| 150 parameters | Δρmin = −0.18 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: 0.0063 (8) |
| C12H17N3S | V = 2629.4 (12) Å3 |
| Mr = 235.35 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 12.615 (3) Å | µ = 0.23 mm−1 |
| b = 9.564 (3) Å | T = 294 K |
| c = 21.792 (6) Å | 0.26 × 0.24 × 0.20 mm |
| Bruker SMART CCD area-detector diffractometer | 2683 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1558 reflections with I > 2σ(I) |
| Tmin = 0.944, Tmax = 0.956 | Rint = 0.063 |
| 14113 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.113 | Δρmax = 0.19 e Å−3 |
| S = 1.00 | Δρmin = −0.18 e Å−3 |
| 2683 reflections | Absolute structure: ? |
| 150 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.36106 (5) | 0.99131 (5) | 0.40936 (3) | 0.0514 (2) | |
| N1 | 0.28317 (14) | 0.76356 (17) | 0.35338 (9) | 0.0524 (5) | |
| H1 | 0.2645 (18) | 0.680 (3) | 0.3598 (11) | 0.079* | |
| N3 | 0.61274 (14) | 0.5946 (2) | 0.44451 (8) | 0.0578 (5) | |
| C1 | 0.35271 (15) | 0.81840 (19) | 0.39467 (9) | 0.0398 (5) | |
| N2 | 0.41289 (14) | 0.72436 (17) | 0.42397 (8) | 0.0513 (5) | |
| C2 | 0.43330 (17) | 0.5809 (2) | 0.40281 (12) | 0.0640 (7) | |
| H2A | 0.3932 | 0.5626 | 0.3657 | 0.077* | |
| H2B | 0.4110 | 0.5147 | 0.4339 | 0.077* | |
| C3 | 0.55023 (19) | 0.5640 (3) | 0.39033 (11) | 0.0649 (7) | |
| H3A | 0.5642 | 0.4689 | 0.3772 | 0.078* | |
| H3B | 0.5710 | 0.6264 | 0.3574 | 0.078* | |
| C5 | 0.59229 (19) | 0.7363 (2) | 0.46428 (11) | 0.0610 (7) | |
| H5A | 0.6144 | 0.8008 | 0.4324 | 0.073* | |
| H5B | 0.6336 | 0.7561 | 0.5008 | 0.073* | |
| C6 | 0.47721 (17) | 0.7581 (2) | 0.47785 (10) | 0.0563 (6) | |
| H6A | 0.4562 | 0.6991 | 0.5120 | 0.068* | |
| H6B | 0.4653 | 0.8547 | 0.4895 | 0.068* | |
| C7 | 0.7257 (2) | 0.5730 (4) | 0.43281 (13) | 0.1001 (10) | |
| H7A | 0.7372 | 0.4786 | 0.4194 | 0.150* | |
| H7B | 0.7650 | 0.5895 | 0.4698 | 0.150* | |
| H7C | 0.7490 | 0.6367 | 0.4016 | 0.150* | |
| C8 | 0.22016 (16) | 0.8339 (2) | 0.30953 (10) | 0.0432 (5) | |
| C9 | 0.25884 (19) | 0.9421 (2) | 0.27394 (10) | 0.0520 (6) | |
| H9 | 0.3279 | 0.9738 | 0.2793 | 0.062* | |
| C10 | 0.1938 (2) | 1.0030 (3) | 0.23032 (11) | 0.0689 (7) | |
| H10 | 0.2191 | 1.0776 | 0.2072 | 0.083* | |
| C11 | 0.0929 (3) | 0.9551 (3) | 0.22057 (12) | 0.0768 (8) | |
| H11 | 0.0503 | 0.9964 | 0.1909 | 0.092* | |
| C12 | 0.0551 (2) | 0.8459 (3) | 0.25482 (12) | 0.0694 (7) | |
| H12 | −0.0128 | 0.8117 | 0.2479 | 0.083* | |
| C13 | 0.11814 (17) | 0.7868 (2) | 0.29968 (11) | 0.0549 (6) | |
| H13 | 0.0915 | 0.7143 | 0.3236 | 0.066* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0658 (4) | 0.0334 (3) | 0.0552 (4) | 0.0038 (2) | −0.0001 (3) | −0.0056 (3) |
| N1 | 0.0498 (11) | 0.0314 (9) | 0.0759 (14) | −0.0014 (8) | −0.0252 (10) | 0.0078 (10) |
| N3 | 0.0471 (12) | 0.0745 (14) | 0.0518 (12) | 0.0137 (9) | −0.0161 (9) | −0.0033 (10) |
| C1 | 0.0358 (11) | 0.0343 (10) | 0.0492 (13) | 0.0015 (9) | −0.0011 (10) | 0.0026 (9) |
| N2 | 0.0522 (11) | 0.0359 (9) | 0.0659 (13) | 0.0059 (8) | −0.0233 (10) | −0.0039 (9) |
| C2 | 0.0610 (16) | 0.0316 (12) | 0.099 (2) | 0.0065 (10) | −0.0346 (14) | −0.0050 (12) |
| C3 | 0.0723 (17) | 0.0549 (14) | 0.0675 (17) | 0.0161 (13) | −0.0263 (14) | −0.0118 (13) |
| C5 | 0.0598 (16) | 0.0717 (16) | 0.0514 (15) | −0.0095 (12) | −0.0195 (12) | −0.0046 (13) |
| C6 | 0.0581 (16) | 0.0569 (14) | 0.0539 (14) | 0.0070 (11) | −0.0159 (12) | −0.0036 (11) |
| C7 | 0.0569 (19) | 0.165 (3) | 0.078 (2) | 0.0280 (19) | −0.0138 (15) | −0.020 (2) |
| C8 | 0.0415 (13) | 0.0350 (11) | 0.0531 (13) | 0.0123 (9) | −0.0082 (10) | −0.0058 (10) |
| C9 | 0.0538 (14) | 0.0532 (13) | 0.0491 (14) | 0.0089 (11) | 0.0043 (12) | −0.0009 (12) |
| C10 | 0.089 (2) | 0.0688 (16) | 0.0495 (15) | 0.0142 (15) | 0.0017 (14) | 0.0138 (13) |
| C11 | 0.086 (2) | 0.0806 (19) | 0.0639 (18) | 0.0311 (17) | −0.0278 (16) | 0.0033 (15) |
| C12 | 0.0587 (16) | 0.0634 (16) | 0.0861 (19) | 0.0130 (13) | −0.0292 (15) | −0.0067 (16) |
| C13 | 0.0508 (15) | 0.0406 (12) | 0.0733 (17) | 0.0069 (10) | −0.0160 (12) | −0.0010 (11) |
| S1—C1 | 1.6878 (19) | C5—H5B | 0.9700 |
| N1—C1 | 1.362 (2) | C6—H6A | 0.9700 |
| N1—C8 | 1.414 (3) | C6—H6B | 0.9700 |
| N1—H1 | 0.84 (3) | C7—H7A | 0.9600 |
| N3—C5 | 1.446 (3) | C7—H7B | 0.9600 |
| N3—C3 | 1.450 (3) | C7—H7C | 0.9600 |
| N3—C7 | 1.462 (3) | C8—C13 | 1.380 (3) |
| C1—N2 | 1.339 (2) | C8—C9 | 1.382 (3) |
| N2—C6 | 1.463 (3) | C9—C10 | 1.384 (3) |
| N2—C2 | 1.470 (3) | C9—H9 | 0.9300 |
| C2—C3 | 1.509 (3) | C10—C11 | 1.369 (4) |
| C2—H2A | 0.9700 | C10—H10 | 0.9300 |
| C2—H2B | 0.9700 | C11—C12 | 1.369 (4) |
| C3—H3A | 0.9700 | C11—H11 | 0.9300 |
| C3—H3B | 0.9700 | C12—C13 | 1.381 (3) |
| C5—C6 | 1.496 (3) | C12—H12 | 0.9300 |
| C5—H5A | 0.9700 | C13—H13 | 0.9300 |
| C1—N1—C8 | 128.72 (17) | N2—C6—C5 | 110.41 (19) |
| C1—N1—H1 | 115.7 (17) | N2—C6—H6A | 109.6 |
| C8—N1—H1 | 113.9 (17) | C5—C6—H6A | 109.6 |
| C5—N3—C3 | 109.57 (18) | N2—C6—H6B | 109.6 |
| C5—N3—C7 | 111.0 (2) | C5—C6—H6B | 109.6 |
| C3—N3—C7 | 111.1 (2) | H6A—C6—H6B | 108.1 |
| N2—C1—N1 | 114.94 (17) | N3—C7—H7A | 109.5 |
| N2—C1—S1 | 122.16 (15) | N3—C7—H7B | 109.5 |
| N1—C1—S1 | 122.89 (14) | H7A—C7—H7B | 109.5 |
| C1—N2—C6 | 123.29 (17) | N3—C7—H7C | 109.5 |
| C1—N2—C2 | 125.20 (18) | H7A—C7—H7C | 109.5 |
| C6—N2—C2 | 111.13 (16) | H7B—C7—H7C | 109.5 |
| N2—C2—C3 | 109.16 (18) | C13—C8—C9 | 119.1 (2) |
| N2—C2—H2A | 109.8 | C13—C8—N1 | 118.29 (19) |
| C3—C2—H2A | 109.8 | C9—C8—N1 | 122.50 (19) |
| N2—C2—H2B | 109.8 | C8—C9—C10 | 119.4 (2) |
| C3—C2—H2B | 109.8 | C8—C9—H9 | 120.3 |
| H2A—C2—H2B | 108.3 | C10—C9—H9 | 120.3 |
| N3—C3—C2 | 111.3 (2) | C11—C10—C9 | 121.1 (3) |
| N3—C3—H3A | 109.4 | C11—C10—H10 | 119.4 |
| C2—C3—H3A | 109.4 | C9—C10—H10 | 119.4 |
| N3—C3—H3B | 109.4 | C12—C11—C10 | 119.6 (2) |
| C2—C3—H3B | 109.4 | C12—C11—H11 | 120.2 |
| H3A—C3—H3B | 108.0 | C10—C11—H11 | 120.2 |
| N3—C5—C6 | 111.28 (19) | C11—C12—C13 | 119.8 (2) |
| N3—C5—H5A | 109.4 | C11—C12—H12 | 120.1 |
| C6—C5—H5A | 109.4 | C13—C12—H12 | 120.1 |
| N3—C5—H5B | 109.4 | C8—C13—C12 | 120.9 (2) |
| C6—C5—H5B | 109.4 | C8—C13—H13 | 119.6 |
| H5A—C5—H5B | 108.0 | C12—C13—H13 | 119.6 |
| C8—N1—C1—N2 | −170.3 (2) | C1—N2—C6—C5 | −117.2 (2) |
| C8—N1—C1—S1 | 11.1 (3) | C2—N2—C6—C5 | 56.1 (2) |
| N1—C1—N2—C6 | −167.85 (19) | N3—C5—C6—N2 | −57.2 (2) |
| S1—C1—N2—C6 | 10.8 (3) | C1—N1—C8—C13 | −140.8 (2) |
| N1—C1—N2—C2 | 19.8 (3) | C1—N1—C8—C9 | 43.0 (3) |
| S1—C1—N2—C2 | −161.54 (17) | C13—C8—C9—C10 | 1.5 (3) |
| C1—N2—C2—C3 | 117.1 (2) | N1—C8—C9—C10 | 177.64 (19) |
| C6—N2—C2—C3 | −56.1 (3) | C8—C9—C10—C11 | −1.9 (3) |
| C5—N3—C3—C2 | −59.1 (3) | C9—C10—C11—C12 | 0.5 (4) |
| C7—N3—C3—C2 | 177.9 (2) | C10—C11—C12—C13 | 1.3 (4) |
| N2—C2—C3—N3 | 57.9 (3) | C9—C8—C13—C12 | 0.3 (3) |
| C3—N3—C5—C6 | 58.4 (3) | N1—C8—C13—C12 | −176.03 (19) |
| C7—N3—C5—C6 | −178.6 (2) | C11—C12—C13—C8 | −1.7 (4) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···S1i | 0.84 (3) | 2.64 (3) | 3.403 (2) | 152 (2) |
| Symmetry codes: (i) −x+1/2, y−1/2, z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···S1i | 0.84 (3) | 2.64 (3) | 3.403 (2) | 152 (2) |
| Symmetry codes: (i) −x+1/2, y−1/2, z. |
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Guzmán, J. F. B., Rodríguez, S. G. & Fernández-Bolaños, J. (1991). Carbohydr. Res. 210, 125–143.
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Thiourea derivatives have been used extensively as organical intermediate in the field of high polymer chemistry (Ballabeni et al., 1999). As part of our search for new compounds we synthesized the title compound (I), and describe its structure here.
Bond lengths and angles in (I) are normal. The C1—S1 distance of 1.688 (2) Å is longer than the distance of 1.700 Å reported by Ramnathan et al. (1996). The C1—N2 distance [1.339 (2) Å] is longer than the reported distance [1.339 Å] (Guzmán et al., 1991). The crystal structure of (I) is stabilized by intermolecular N—H···S hydrogen bonding interactions.