Acta Cryst. (2011). E67, o2133 [ doi:10.1107/S1600536811029035 ]
In the title compound, C17H18N4O2S·CH3OH, the two benzene rings in the thiocarbonohydrazide molecule form a dihedral angle of 22.42 (18)°. Pairs of N-H
S hydrogen bonds link thiocarbonohydrazide molecules into centrosymmetric dimers. Methanol solvent molecules serve as donors (O-HS and O-HN) and acceptors (N-HO and C-HO) of weak intermolecular hydrogen bonds, which link further these dimers into double ribbons along the b axis.
4-Methoxybenzaldehyde (10.0 mmol), 30 ml e thanol and thiocarbohydrazide (5.0 mmol) were mixed in 50 ml flash After stirring 3 h at 373 K, the resulting mixture was cooled to room temperature, and recrystalized from ethanol, and afforded the title compound as a crystalline solid.
All H atoms were placed in geometrically idealized positions (N—H 0.86; O—H 0.82 and C—H 0.93–0.96 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2–1.5Ueq of the parent atom.
Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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).
![[Figure 1]](./cv5128fig1thm.gif)
| Fig. 1. View of (I) showing the atomic numbering and 30% probability displacement ellipsoids. Dashed lines denote hydrogen bonds. |
| C17H18N4O2S·CH4O | Z = 2 |
| Mr = 374.46 | F(000) = 396 |
| Triclinic, P1 | Dx = 1.306 Mg m−3 |
| a = 8.8021 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
| b = 9.9949 (10) Å | Cell parameters from 1379 reflections |
| c = 11.5902 (13) Å | θ = 2.7–25.2° |
| α = 83.132 (1)° | µ = 0.20 mm−1 |
| β = 84.179 (2)° | T = 298 K |
| γ = 70.505 (1)° | Block, red |
| V = 952.24 (16) Å3 | 0.42 × 0.39 × 0.32 mm |
| Bruker SMART APEX CCD area-detector diffractometer | 3302 independent reflections |
| Radiation source: fine-focus sealed tube | 1934 reflections with I > 2σ(I) |
| graphite | Rint = 0.023 |
| phi and ω scans | θmax = 25.0°, θmin = 2.7° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −7→10 |
| Tmin = 0.923, Tmax = 0.940 | k = −11→11 |
| 4936 measured reflections | l = −13→12 |
| 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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.137 | H-atom parameters constrained |
| S = 1.01 | w = 1/[σ2(Fo2) + (0.0585P)2 + 0.1975P] where P = (Fo2 + 2Fc2)/3 |
| 3302 reflections | (Δ/σ)max < 0.001 |
| 239 parameters | Δρmax = 0.21 e Å−3 |
| 0 restraints | Δρmin = −0.18 e Å−3 |
| C17H18N4O2S·CH4O | γ = 70.505 (1)° |
| Mr = 374.46 | V = 952.24 (16) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 8.8021 (6) Å | Mo Kα radiation |
| b = 9.9949 (10) Å | µ = 0.20 mm−1 |
| c = 11.5902 (13) Å | T = 298 K |
| α = 83.132 (1)° | 0.42 × 0.39 × 0.32 mm |
| β = 84.179 (2)° |
| Bruker SMART APEX CCD area-detector diffractometer | 3302 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1934 reflections with I > 2σ(I) |
| Tmin = 0.923, Tmax = 0.940 | Rint = 0.023 |
| 4936 measured reflections | θmax = 25.0° |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.137 | Δρmax = 0.21 e Å−3 |
| S = 1.01 | Δρmin = −0.18 e Å−3 |
| 3302 reflections | Absolute structure: ? |
| 239 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 | 0.63183 (11) | 0.63686 (9) | −0.08592 (7) | 0.0604 (3) | |
| N1 | 0.6991 (3) | 0.8790 (2) | −0.00620 (19) | 0.0435 (6) | |
| N2 | 0.6220 (3) | 0.8089 (2) | 0.07669 (19) | 0.0445 (6) | |
| H2 | 0.5951 | 0.8368 | 0.1454 | 0.053* | |
| N3 | 0.5206 (3) | 0.6273 (2) | 0.1308 (2) | 0.0487 (7) | |
| H3 | 0.5021 | 0.5523 | 0.1154 | 0.058* | |
| N4 | 0.4772 (3) | 0.6718 (2) | 0.2409 (2) | 0.0458 (6) | |
| O1 | 1.0808 (3) | 1.2665 (2) | −0.28491 (19) | 0.0653 (7) | |
| O2 | 0.1682 (3) | 0.6793 (2) | 0.76724 (19) | 0.0688 (7) | |
| C1 | 0.5902 (3) | 0.6955 (3) | 0.0468 (2) | 0.0424 (7) | |
| C2 | 0.7256 (3) | 0.9876 (3) | 0.0215 (2) | 0.0412 (7) | |
| H2A | 0.6890 | 1.0203 | 0.0944 | 0.049* | |
| C3 | 0.8135 (3) | 1.0612 (3) | −0.0612 (2) | 0.0388 (7) | |
| C4 | 0.8918 (4) | 1.0014 (3) | −0.1615 (2) | 0.0471 (8) | |
| H4A | 0.8839 | 0.9150 | −0.1773 | 0.057* | |
| C5 | 0.9813 (4) | 1.0662 (3) | −0.2389 (3) | 0.0522 (8) | |
| H5 | 1.0332 | 1.0239 | −0.3057 | 0.063* | |
| C6 | 0.9927 (4) | 1.1946 (3) | −0.2158 (3) | 0.0463 (8) | |
| C7 | 0.9135 (3) | 1.2564 (3) | −0.1173 (3) | 0.0473 (8) | |
| H7 | 0.9189 | 1.3442 | −0.1029 | 0.057* | |
| C8 | 0.8264 (3) | 1.1902 (3) | −0.0399 (2) | 0.0439 (7) | |
| H8 | 0.7757 | 1.2323 | 0.0272 | 0.053* | |
| C9 | 1.1754 (5) | 1.1998 (4) | −0.3814 (3) | 0.0838 (12) | |
| H9A | 1.1057 | 1.1927 | −0.4373 | 0.126* | |
| H9B | 1.2437 | 1.1062 | −0.3555 | 0.126* | |
| H9C | 1.2410 | 1.2554 | −0.4168 | 0.126* | |
| C10 | 0.3907 (4) | 0.6071 (3) | 0.3027 (3) | 0.0501 (8) | |
| H10 | 0.3638 | 0.5391 | 0.2686 | 0.060* | |
| C11 | 0.3309 (4) | 0.6312 (3) | 0.4222 (2) | 0.0458 (8) | |
| C12 | 0.3712 (4) | 0.7200 (3) | 0.4869 (3) | 0.0589 (9) | |
| H12 | 0.4377 | 0.7710 | 0.4525 | 0.071* | |
| C13 | 0.3152 (4) | 0.7345 (3) | 0.6009 (3) | 0.0639 (10) | |
| H13 | 0.3445 | 0.7943 | 0.6433 | 0.077* | |
| C14 | 0.2149 (4) | 0.6601 (3) | 0.6531 (3) | 0.0498 (8) | |
| C15 | 0.1720 (4) | 0.5731 (3) | 0.5907 (3) | 0.0540 (8) | |
| H15 | 0.1037 | 0.5236 | 0.6248 | 0.065* | |
| C16 | 0.2307 (4) | 0.5589 (3) | 0.4766 (3) | 0.0573 (9) | |
| H16 | 0.2017 | 0.4984 | 0.4347 | 0.069* | |
| C17 | 0.0688 (5) | 0.6007 (4) | 0.8248 (3) | 0.0738 (11) | |
| H17A | 0.1258 | 0.5005 | 0.8237 | 0.111* | |
| H17B | −0.0289 | 0.6249 | 0.7854 | 0.111* | |
| H17C | 0.0429 | 0.6239 | 0.9040 | 0.111* | |
| O3 | 0.5382 (3) | 0.9498 (3) | −0.2485 (2) | 0.0849 (8) | |
| H3A | 0.5673 | 0.8888 | −0.1940 | 0.127* | |
| C18 | 0.6365 (5) | 0.9076 (5) | −0.3470 (3) | 0.0884 (13) | |
| H18A | 0.5743 | 0.9401 | −0.4144 | 0.133* | |
| H18B | 0.6812 | 0.8055 | −0.3413 | 0.133* | |
| H18C | 0.7224 | 0.9477 | −0.3540 | 0.133* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0755 (7) | 0.0533 (5) | 0.0593 (5) | −0.0349 (5) | 0.0242 (5) | −0.0148 (4) |
| N1 | 0.0458 (15) | 0.0437 (14) | 0.0427 (14) | −0.0205 (12) | 0.0033 (12) | 0.0020 (11) |
| N2 | 0.0531 (16) | 0.0473 (14) | 0.0359 (13) | −0.0236 (13) | 0.0047 (12) | −0.0001 (11) |
| N3 | 0.0550 (16) | 0.0413 (14) | 0.0514 (15) | −0.0228 (13) | 0.0114 (13) | −0.0019 (12) |
| N4 | 0.0468 (16) | 0.0451 (14) | 0.0437 (15) | −0.0162 (13) | 0.0036 (12) | 0.0016 (12) |
| O1 | 0.0743 (16) | 0.0593 (14) | 0.0680 (15) | −0.0371 (13) | 0.0204 (13) | −0.0045 (12) |
| O2 | 0.0862 (18) | 0.0785 (16) | 0.0553 (14) | −0.0468 (14) | 0.0218 (13) | −0.0227 (12) |
| C1 | 0.0329 (17) | 0.0382 (16) | 0.0516 (18) | −0.0106 (14) | 0.0059 (14) | 0.0037 (14) |
| C2 | 0.0401 (18) | 0.0455 (17) | 0.0389 (16) | −0.0152 (14) | −0.0007 (14) | −0.0048 (13) |
| C3 | 0.0348 (16) | 0.0412 (16) | 0.0418 (16) | −0.0138 (13) | −0.0008 (13) | −0.0056 (13) |
| C4 | 0.0506 (19) | 0.0429 (17) | 0.0529 (19) | −0.0220 (15) | 0.0043 (16) | −0.0104 (15) |
| C5 | 0.059 (2) | 0.0518 (19) | 0.0490 (18) | −0.0235 (17) | 0.0127 (16) | −0.0134 (15) |
| C6 | 0.0450 (19) | 0.0436 (18) | 0.0522 (19) | −0.0202 (15) | −0.0008 (15) | 0.0028 (15) |
| C7 | 0.0495 (19) | 0.0382 (17) | 0.0580 (19) | −0.0193 (15) | 0.0007 (16) | −0.0082 (15) |
| C8 | 0.0434 (18) | 0.0430 (17) | 0.0474 (18) | −0.0158 (15) | 0.0011 (15) | −0.0109 (14) |
| C9 | 0.087 (3) | 0.075 (3) | 0.084 (3) | −0.033 (2) | 0.040 (2) | −0.004 (2) |
| C10 | 0.056 (2) | 0.0481 (18) | 0.0496 (19) | −0.0248 (16) | −0.0010 (16) | 0.0049 (15) |
| C11 | 0.0470 (19) | 0.0447 (17) | 0.0461 (18) | −0.0194 (15) | 0.0039 (15) | 0.0011 (14) |
| C12 | 0.067 (2) | 0.054 (2) | 0.065 (2) | −0.0360 (18) | 0.0159 (19) | −0.0095 (17) |
| C13 | 0.077 (3) | 0.060 (2) | 0.068 (2) | −0.041 (2) | 0.014 (2) | −0.0211 (17) |
| C14 | 0.053 (2) | 0.0495 (18) | 0.0498 (19) | −0.0210 (16) | 0.0049 (16) | −0.0088 (15) |
| C15 | 0.060 (2) | 0.063 (2) | 0.0486 (19) | −0.0372 (18) | 0.0078 (16) | −0.0024 (16) |
| C16 | 0.074 (2) | 0.063 (2) | 0.049 (2) | −0.0430 (19) | 0.0036 (18) | −0.0061 (16) |
| C17 | 0.089 (3) | 0.092 (3) | 0.052 (2) | −0.049 (2) | 0.019 (2) | −0.0131 (19) |
| O3 | 0.095 (2) | 0.0784 (18) | 0.0610 (16) | −0.0093 (15) | 0.0104 (15) | 0.0029 (13) |
| C18 | 0.091 (3) | 0.115 (3) | 0.062 (2) | −0.040 (3) | 0.002 (2) | −0.003 (2) |
| S1—C1 | 1.673 (3) | C8—H8 | 0.9300 |
| N1—C2 | 1.267 (3) | C9—H9A | 0.9600 |
| N1—N2 | 1.377 (3) | C9—H9B | 0.9600 |
| N2—C1 | 1.346 (3) | C9—H9C | 0.9600 |
| N2—H2 | 0.8600 | C10—C11 | 1.449 (4) |
| N3—C1 | 1.337 (3) | C10—H10 | 0.9300 |
| N3—N4 | 1.377 (3) | C11—C12 | 1.378 (4) |
| N3—H3 | 0.8600 | C11—C16 | 1.379 (4) |
| N4—C10 | 1.272 (3) | C12—C13 | 1.369 (4) |
| O1—C6 | 1.367 (3) | C12—H12 | 0.9300 |
| O1—C9 | 1.417 (4) | C13—C14 | 1.385 (4) |
| O2—C14 | 1.362 (3) | C13—H13 | 0.9300 |
| O2—C17 | 1.429 (4) | C14—C15 | 1.359 (4) |
| C2—C3 | 1.455 (4) | C15—C16 | 1.376 (4) |
| C2—H2A | 0.9300 | C15—H15 | 0.9300 |
| C3—C4 | 1.383 (4) | C16—H16 | 0.9300 |
| C3—C8 | 1.384 (4) | C17—H17A | 0.9600 |
| C4—C5 | 1.379 (4) | C17—H17B | 0.9600 |
| C4—H4A | 0.9300 | C17—H17C | 0.9600 |
| C5—C6 | 1.379 (4) | O3—C18 | 1.380 (4) |
| C5—H5 | 0.9300 | O3—H3A | 0.8200 |
| C6—C7 | 1.375 (4) | C18—H18A | 0.9600 |
| C7—C8 | 1.374 (4) | C18—H18B | 0.9600 |
| C7—H7 | 0.9300 | C18—H18C | 0.9600 |
| C2—N1—N2 | 117.7 (2) | O1—C9—H9C | 109.5 |
| C1—N2—N1 | 117.9 (2) | H9A—C9—H9C | 109.5 |
| C1—N2—H2 | 121.0 | H9B—C9—H9C | 109.5 |
| N1—N2—H2 | 121.0 | N4—C10—C11 | 125.0 (3) |
| C1—N3—N4 | 122.9 (2) | N4—C10—H10 | 117.5 |
| C1—N3—H3 | 118.5 | C11—C10—H10 | 117.5 |
| N4—N3—H3 | 118.5 | C12—C11—C16 | 117.2 (3) |
| C10—N4—N3 | 113.5 (3) | C12—C11—C10 | 124.0 (3) |
| C6—O1—C9 | 117.8 (2) | C16—C11—C10 | 118.7 (3) |
| C14—O2—C17 | 117.2 (2) | C13—C12—C11 | 121.2 (3) |
| N3—C1—N2 | 116.1 (3) | C13—C12—H12 | 119.4 |
| N3—C1—S1 | 119.4 (2) | C11—C12—H12 | 119.4 |
| N2—C1—S1 | 124.5 (2) | C12—C13—C14 | 120.1 (3) |
| N1—C2—C3 | 119.8 (3) | C12—C13—H13 | 120.0 |
| N1—C2—H2A | 120.1 | C14—C13—H13 | 120.0 |
| C3—C2—H2A | 120.1 | C15—C14—O2 | 124.4 (3) |
| C4—C3—C8 | 118.0 (3) | C15—C14—C13 | 119.8 (3) |
| C4—C3—C2 | 120.8 (3) | O2—C14—C13 | 115.7 (3) |
| C8—C3—C2 | 121.2 (3) | C14—C15—C16 | 119.2 (3) |
| C5—C4—C3 | 121.9 (3) | C14—C15—H15 | 120.4 |
| C5—C4—H4A | 119.0 | C16—C15—H15 | 120.4 |
| C3—C4—H4A | 119.0 | C15—C16—C11 | 122.4 (3) |
| C6—C5—C4 | 119.1 (3) | C15—C16—H16 | 118.8 |
| C6—C5—H5 | 120.4 | C11—C16—H16 | 118.8 |
| C4—C5—H5 | 120.4 | O2—C17—H17A | 109.5 |
| O1—C6—C7 | 116.3 (3) | O2—C17—H17B | 109.5 |
| O1—C6—C5 | 124.1 (3) | H17A—C17—H17B | 109.5 |
| C7—C6—C5 | 119.6 (3) | O2—C17—H17C | 109.5 |
| C8—C7—C6 | 120.9 (3) | H17A—C17—H17C | 109.5 |
| C8—C7—H7 | 119.6 | H17B—C17—H17C | 109.5 |
| C6—C7—H7 | 119.6 | C18—O3—H3A | 109.5 |
| C7—C8—C3 | 120.5 (3) | O3—C18—H18A | 109.5 |
| C7—C8—H8 | 119.8 | O3—C18—H18B | 109.5 |
| C3—C8—H8 | 119.8 | H18A—C18—H18B | 109.5 |
| O1—C9—H9A | 109.5 | O3—C18—H18C | 109.5 |
| O1—C9—H9B | 109.5 | H18A—C18—H18C | 109.5 |
| H9A—C9—H9B | 109.5 | H18B—C18—H18C | 109.5 |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···N1 | 0.82 | 2.55 | 3.171 (3) | 134. |
| O3—H3A···S1 | 0.82 | 2.58 | 3.346 (3) | 156. |
| N2—H2···O3i | 0.86 | 2.45 | 3.174 (3) | 142. |
| N3—H3···S1ii | 0.86 | 2.61 | 3.446 (3) | 165. |
| C2—H2A···O3i | 0.93 | 2.51 | 3.300 (4) | 143. |
| Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O3—H3A···N1 | 0.82 | 2.55 | 3.171 (3) | 134. |
| O3—H3A···S1 | 0.82 | 2.58 | 3.346 (3) | 156. |
| N2—H2···O3i | 0.86 | 2.45 | 3.174 (3) | 142. |
| N3—H3···S1ii | 0.86 | 2.61 | 3.446 (3) | 165. |
| C2—H2A···O3i | 0.93 | 2.51 | 3.300 (4) | 143. |
| Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+1, −z. |
The authors acknowledge financial support by Shenyang University of Technology.
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In recent years, there has been considerable interest in the chemistry of thiocarbohydrazide Schiff base derivatives (Loncle et al., 2004; Camp et al., 2010), because these derivatives offer opportunities for tuning the metal centred electronic factor, enhancing the solubility and stability of either homogeneous or heterogeneous catalysts (Opstal et al., 2003). Herein we present the title compound, (I).
In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in 1,5-bis[(E)-1-(2-hydroxyphenyl)ethylidene] thiocarbonohydrazide monohydrate (Affan et al., 2010). Four N atoms and the C=S are almost coplanar, the N1/N2/C2 plane and the benzene ring C3–C8 form a dihedral angle of 12.32 (3)°. The benzene rings C3–C8 and C11–C16 form a dihedral angle of 22.42 (18) °.
In the crystal structure, intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers. Solvent molecules serve as donors [O—H···S and O—H···N] and acceptors [N—H···O and C—H···O] of the weak intermolecular hydrogen bonds (Table 1), which link further these dimers into doubled ribbons along axis b.