organic compounds
(E)-Benzyl 2-{4-[ethyl(2-hydroxyethyl)amino]benzylidene}hydrazinecarbodithioate
aDepartment of Chemistry, Anhui University, Hefei, Anhui 230039, People's Republic of China
*Correspondence e-mail: 1295913906@qq.com
In the title compound, C19H23N3OS2, the dihedral angle between the aromatic rings is 86.80 (8)° and the tertiary amine grouping is almost planar (bond-angle sum at the N atom = 360.0°). In the crystal, pairwise N—H⋯O hydrogen bonds link the molecules into inversion dimers, and O—H⋯S hydrogen bonds link the dimers into [101] chains.
Keywords: Schiff base; crystal structure; intermolecular interactions.
CCDC reference: 2106601
Structure description
The title compound, C19H23N3OS2, is a D–π–A type Schiff base with an aniline derivative as the electron-donating (D) group and a hydrazinothioic acid benzyl ester as the electron-withdrawing (A) group. Schiff base ligands based on benzyl hydrazinothioate are an important class of compounds that have attracted widespread interest (Zhao et al., 2008).
The P) symmetry. The dihedral angle between the C3–C8 and C10–C15 benzene rings is 86.80 (8)° and the C1—N1—N2—C9 torsion angle is −170.6 (2)° (Fig. 1). This twisted conformation may effectively inhibit fluorescence quenching in the crystal by reducing π–π stacking between molecules. The S1/S2/N1/N2/C1 grouping is close to planar (r.m.s. deviation = 0.026 Å) and the geometry at N3 is almost planar (bond-angle sum = 360.0°) and C17 and C19 point from C13/C16/C18/N3 in opposite directions [deviations = −1.411 (2) and 1.334 (2) Å, respectively].
has triclinic (In the extended structure, pairwise N—H⋯O hydrogen bonds (Table 1) generate inversion dimers featuring R22(22) loops, and O—H⋯S hydrogen bonds link the dimers into [101] chains (Fig. 2).
Synthesis and crystallization
In a 100 ml round-bottomed flask, 3.40 g (0.17 mol) of benzylhydrazine carbon disulfide and 3.00 g (0.17 mol) of 4-(ethyl(2-hydroxyethyl) amino) benzaldehyde were dissolved in 50 ml of ethanol and stirred at room temperature for 15 minutes and then transferred to an oil bath for reflux at 353 K for 3 h. After the reaction was cooled to room temperature, a yellow solid 5.10 g (yield 84%) was precipitated out and recovered by filtration. Colourless blocks were recrystallized from ethanol solution.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 2106601
https://doi.org/10.1107/S2414314621009019/hb4387sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009019/hb4387Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314621009019/hb4387Isup3.cml
Data collection: X-AREA Pilatus3_SV (Stoe, 2018); cell
X-AREA Recipe (Stoe, 2018); data reduction: X-AREA Integrate (Stoe, 2018) X-AREA LANA (Stoe, 2018); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C19H23N3OS2 | Z = 2 |
Mr = 373.52 | F(000) = 396 |
Triclinic, P1 | Dx = 1.325 Mg m−3 |
a = 9.1794 (18) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.4642 (19) Å | Cell parameters from 8567 reflections |
c = 11.665 (2) Å | θ = 69.8–4.3° |
α = 101.78 (3)° | µ = 0.30 mm−1 |
β = 107.81 (3)° | T = 120 K |
γ = 93.57 (3)° | Block, colourless |
V = 936.1 (4) Å3 | 0.12 × 0.11 × 0.1 mm |
Stoe X-Area CCD diffractometer | 2508 reflections with I > 2σ(I) |
φ and ω scans | Rint = 0.038 |
Absorption correction: multi-scan (X-Red32; Stoe, 2018) | θmax = 25.6°, θmin = 1.9° |
Tmin = 0.342, Tmax = 0.808 | h = −11→10 |
8565 measured reflections | k = −4→10 |
3419 independent reflections | l = −14→13 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0568P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.92 | (Δ/σ)max = 0.001 |
3419 reflections | Δρmax = 0.43 e Å−3 |
228 parameters | Δρmin = −0.25 e Å−3 |
0 restraints |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 1.15987 (6) | 0.04410 (6) | 0.90983 (5) | 0.02333 (15) | |
S2 | 1.05575 (6) | 0.31931 (6) | 0.83421 (5) | 0.02330 (15) | |
O1 | 0.22245 (18) | 0.21535 (18) | 0.18795 (14) | 0.0262 (4) | |
H1 | 0.223336 | 0.181675 | 0.115767 | 0.039* | |
N1 | 0.8765 (2) | 0.0761 (2) | 0.79056 (16) | 0.0233 (4) | |
H1A | 0.850789 | −0.013576 | 0.794332 | 0.028* | |
N2 | 0.7650 (2) | 0.1512 (2) | 0.73042 (16) | 0.0228 (4) | |
N3 | 0.1089 (2) | 0.2823 (2) | 0.39125 (16) | 0.0224 (4) | |
C1 | 1.0235 (2) | 0.1382 (2) | 0.84322 (19) | 0.0223 (5) | |
C2 | 1.2647 (3) | 0.3598 (3) | 0.9062 (2) | 0.0290 (5) | |
H2A | 1.294123 | 0.355290 | 0.994245 | 0.035* | |
H2B | 1.315757 | 0.287256 | 0.863582 | 0.035* | |
C3 | 1.3150 (2) | 0.5093 (3) | 0.8965 (2) | 0.0238 (5) | |
C4 | 1.3139 (3) | 0.6313 (3) | 0.9856 (2) | 0.0273 (5) | |
H4 | 1.276995 | 0.620316 | 1.051407 | 0.033* | |
C5 | 1.3663 (3) | 0.7686 (3) | 0.9790 (2) | 0.0308 (6) | |
H5 | 1.365720 | 0.851217 | 1.040672 | 0.037* | |
C6 | 1.4193 (3) | 0.7867 (3) | 0.8836 (2) | 0.0320 (6) | |
H6 | 1.455293 | 0.881218 | 0.879535 | 0.038* | |
C7 | 1.4196 (3) | 0.6659 (3) | 0.7939 (2) | 0.0335 (6) | |
H7 | 1.455863 | 0.677709 | 0.728000 | 0.040* | |
C8 | 1.3675 (3) | 0.5285 (3) | 0.7997 (2) | 0.0298 (5) | |
H8 | 1.367371 | 0.446318 | 0.737304 | 0.036* | |
C9 | 0.6253 (2) | 0.0890 (2) | 0.6989 (2) | 0.0228 (5) | |
H9 | 0.606910 | 0.001568 | 0.723393 | 0.027* | |
C10 | 0.4956 (2) | 0.1479 (2) | 0.6275 (2) | 0.0220 (5) | |
C11 | 0.5133 (3) | 0.2530 (2) | 0.5624 (2) | 0.0231 (5) | |
H11 | 0.614400 | 0.293822 | 0.571093 | 0.028* | |
C12 | 0.3883 (2) | 0.2988 (2) | 0.4861 (2) | 0.0231 (5) | |
H12 | 0.405089 | 0.369235 | 0.442312 | 0.028* | |
C13 | 0.2348 (2) | 0.2430 (2) | 0.47130 (19) | 0.0208 (5) | |
C14 | 0.2178 (3) | 0.1427 (2) | 0.5421 (2) | 0.0240 (5) | |
H14 | 0.117263 | 0.107096 | 0.539112 | 0.029* | |
C15 | 0.3445 (3) | 0.0952 (3) | 0.6157 (2) | 0.0255 (5) | |
H15 | 0.328834 | 0.024729 | 0.659759 | 0.031* | |
C16 | 0.1209 (3) | 0.3845 (2) | 0.3153 (2) | 0.0243 (5) | |
H16A | 0.221483 | 0.447682 | 0.354456 | 0.029* | |
H16B | 0.038555 | 0.447687 | 0.313128 | 0.029* | |
C17 | 0.1074 (3) | 0.3110 (2) | 0.1842 (2) | 0.0243 (5) | |
H17A | 0.003408 | 0.255098 | 0.140883 | 0.029* | |
H17B | 0.122681 | 0.385034 | 0.138467 | 0.029* | |
C18 | −0.0480 (2) | 0.2184 (3) | 0.3739 (2) | 0.0244 (5) | |
H18A | −0.047229 | 0.114806 | 0.377521 | 0.029* | |
H18B | −0.116034 | 0.221695 | 0.290540 | 0.029* | |
C19 | −0.1142 (3) | 0.2960 (3) | 0.4705 (2) | 0.0324 (6) | |
H19A | −0.216151 | 0.244927 | 0.457563 | 0.049* | |
H19B | −0.123843 | 0.396399 | 0.462546 | 0.049* | |
H19C | −0.045187 | 0.296706 | 0.553457 | 0.049* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0216 (3) | 0.0248 (3) | 0.0193 (3) | 0.0069 (2) | 0.0006 (2) | 0.0039 (2) |
S2 | 0.0180 (3) | 0.0264 (3) | 0.0225 (3) | 0.0036 (2) | 0.0004 (2) | 0.0086 (2) |
O1 | 0.0268 (9) | 0.0339 (9) | 0.0189 (8) | 0.0075 (7) | 0.0093 (7) | 0.0048 (7) |
N1 | 0.0204 (10) | 0.0239 (10) | 0.0225 (10) | 0.0028 (7) | 0.0021 (8) | 0.0063 (8) |
N2 | 0.0201 (10) | 0.0292 (10) | 0.0175 (9) | 0.0060 (8) | 0.0026 (8) | 0.0064 (8) |
N3 | 0.0176 (9) | 0.0329 (11) | 0.0173 (9) | 0.0039 (7) | 0.0045 (7) | 0.0086 (8) |
C1 | 0.0237 (12) | 0.0291 (13) | 0.0131 (11) | 0.0043 (9) | 0.0048 (9) | 0.0041 (9) |
C2 | 0.0198 (12) | 0.0321 (13) | 0.0284 (13) | 0.0033 (9) | −0.0017 (10) | 0.0077 (10) |
C3 | 0.0151 (11) | 0.0304 (13) | 0.0225 (12) | 0.0031 (9) | 0.0002 (9) | 0.0075 (9) |
C4 | 0.0231 (12) | 0.0371 (14) | 0.0230 (12) | 0.0088 (10) | 0.0066 (10) | 0.0097 (10) |
C5 | 0.0267 (13) | 0.0301 (14) | 0.0300 (14) | 0.0075 (10) | 0.0017 (11) | 0.0049 (10) |
C6 | 0.0188 (12) | 0.0337 (14) | 0.0402 (15) | 0.0008 (10) | −0.0007 (11) | 0.0184 (12) |
C7 | 0.0213 (12) | 0.0544 (17) | 0.0271 (13) | 0.0045 (11) | 0.0068 (10) | 0.0164 (12) |
C8 | 0.0231 (12) | 0.0393 (14) | 0.0227 (12) | 0.0041 (10) | 0.0040 (10) | 0.0035 (10) |
C9 | 0.0226 (12) | 0.0241 (12) | 0.0200 (11) | 0.0021 (9) | 0.0055 (9) | 0.0041 (9) |
C10 | 0.0195 (11) | 0.0252 (12) | 0.0182 (11) | 0.0031 (9) | 0.0037 (9) | 0.0024 (9) |
C11 | 0.0178 (11) | 0.0318 (13) | 0.0195 (11) | 0.0010 (9) | 0.0079 (9) | 0.0031 (9) |
C12 | 0.0225 (12) | 0.0287 (13) | 0.0200 (12) | 0.0030 (9) | 0.0088 (9) | 0.0072 (9) |
C13 | 0.0205 (11) | 0.0255 (12) | 0.0137 (11) | 0.0026 (8) | 0.0041 (9) | 0.0011 (9) |
C14 | 0.0165 (11) | 0.0297 (13) | 0.0235 (12) | −0.0007 (9) | 0.0036 (9) | 0.0074 (9) |
C15 | 0.0224 (12) | 0.0294 (13) | 0.0228 (12) | −0.0009 (9) | 0.0036 (10) | 0.0090 (10) |
C16 | 0.0260 (12) | 0.0251 (12) | 0.0207 (12) | 0.0065 (9) | 0.0049 (10) | 0.0060 (9) |
C17 | 0.0240 (12) | 0.0287 (13) | 0.0203 (12) | 0.0056 (9) | 0.0055 (9) | 0.0081 (9) |
C18 | 0.0170 (11) | 0.0332 (13) | 0.0194 (11) | 0.0029 (9) | 0.0027 (9) | 0.0031 (9) |
C19 | 0.0261 (13) | 0.0457 (16) | 0.0237 (13) | 0.0038 (11) | 0.0104 (10) | 0.0013 (11) |
S1—C1 | 1.670 (2) | C8—H8 | 0.9500 |
S2—C1 | 1.751 (2) | C9—H9 | 0.9500 |
S2—C2 | 1.823 (2) | C9—C10 | 1.445 (3) |
O1—H1 | 0.8400 | C10—C11 | 1.398 (3) |
O1—C17 | 1.429 (3) | C10—C15 | 1.400 (3) |
N1—H1A | 0.8800 | C11—H11 | 0.9500 |
N1—N2 | 1.379 (3) | C11—C12 | 1.375 (3) |
N1—C1 | 1.338 (3) | C12—H12 | 0.9500 |
N2—C9 | 1.286 (3) | C12—C13 | 1.420 (3) |
N3—C13 | 1.371 (3) | C13—C14 | 1.411 (3) |
N3—C16 | 1.459 (3) | C14—H14 | 0.9500 |
N3—C18 | 1.464 (3) | C14—C15 | 1.380 (3) |
C2—H2A | 0.9900 | C15—H15 | 0.9500 |
C2—H2B | 0.9900 | C16—H16A | 0.9900 |
C2—C3 | 1.498 (3) | C16—H16B | 0.9900 |
C3—C4 | 1.390 (3) | C16—C17 | 1.509 (3) |
C3—C8 | 1.395 (3) | C17—H17A | 0.9900 |
C4—H4 | 0.9500 | C17—H17B | 0.9900 |
C4—C5 | 1.382 (3) | C18—H18A | 0.9900 |
C5—H5 | 0.9500 | C18—H18B | 0.9900 |
C5—C6 | 1.379 (3) | C18—C19 | 1.521 (3) |
C6—H6 | 0.9500 | C19—H19A | 0.9800 |
C6—C7 | 1.384 (4) | C19—H19B | 0.9800 |
C7—H7 | 0.9500 | C19—H19C | 0.9800 |
C7—C8 | 1.379 (4) | ||
C1—S2—C2 | 101.28 (11) | C15—C10—C9 | 120.5 (2) |
C17—O1—H1 | 109.5 | C10—C11—H11 | 119.1 |
N2—N1—H1A | 119.7 | C12—C11—C10 | 121.8 (2) |
C1—N1—H1A | 119.7 | C12—C11—H11 | 119.1 |
C1—N1—N2 | 120.63 (18) | C11—C12—H12 | 119.3 |
C9—N2—N1 | 114.97 (19) | C11—C12—C13 | 121.4 (2) |
C13—N3—C16 | 123.26 (18) | C13—C12—H12 | 119.3 |
C13—N3—C18 | 121.00 (18) | N3—C13—C12 | 122.15 (19) |
C16—N3—C18 | 115.70 (18) | N3—C13—C14 | 121.34 (19) |
S1—C1—S2 | 124.96 (13) | C14—C13—C12 | 116.5 (2) |
N1—C1—S1 | 120.51 (17) | C13—C14—H14 | 119.4 |
N1—C1—S2 | 114.53 (17) | C15—C14—C13 | 121.2 (2) |
S2—C2—H2A | 110.0 | C15—C14—H14 | 119.4 |
S2—C2—H2B | 110.0 | C10—C15—H15 | 119.0 |
H2A—C2—H2B | 108.4 | C14—C15—C10 | 121.9 (2) |
C3—C2—S2 | 108.51 (16) | C14—C15—H15 | 119.0 |
C3—C2—H2A | 110.0 | N3—C16—H16A | 108.9 |
C3—C2—H2B | 110.0 | N3—C16—H16B | 108.9 |
C4—C3—C2 | 120.6 (2) | N3—C16—C17 | 113.41 (19) |
C4—C3—C8 | 118.8 (2) | H16A—C16—H16B | 107.7 |
C8—C3—C2 | 120.6 (2) | C17—C16—H16A | 108.9 |
C3—C4—H4 | 119.8 | C17—C16—H16B | 108.9 |
C5—C4—C3 | 120.4 (2) | O1—C17—C16 | 108.64 (18) |
C5—C4—H4 | 119.8 | O1—C17—H17A | 110.0 |
C4—C5—H5 | 119.7 | O1—C17—H17B | 110.0 |
C6—C5—C4 | 120.6 (2) | C16—C17—H17A | 110.0 |
C6—C5—H5 | 119.7 | C16—C17—H17B | 110.0 |
C5—C6—H6 | 120.3 | H17A—C17—H17B | 108.3 |
C5—C6—C7 | 119.4 (2) | N3—C18—H18A | 109.0 |
C7—C6—H6 | 120.3 | N3—C18—H18B | 109.0 |
C6—C7—H7 | 119.8 | N3—C18—C19 | 113.08 (19) |
C8—C7—C6 | 120.4 (2) | H18A—C18—H18B | 107.8 |
C8—C7—H7 | 119.8 | C19—C18—H18A | 109.0 |
C3—C8—H8 | 119.8 | C19—C18—H18B | 109.0 |
C7—C8—C3 | 120.4 (2) | C18—C19—H19A | 109.5 |
C7—C8—H8 | 119.8 | C18—C19—H19B | 109.5 |
N2—C9—H9 | 119.0 | C18—C19—H19C | 109.5 |
N2—C9—C10 | 122.0 (2) | H19A—C19—H19B | 109.5 |
C10—C9—H9 | 119.0 | H19A—C19—H19C | 109.5 |
C11—C10—C9 | 122.4 (2) | H19B—C19—H19C | 109.5 |
C11—C10—C15 | 117.1 (2) | ||
S2—C2—C3—C4 | 86.2 (2) | C6—C7—C8—C3 | −0.5 (4) |
S2—C2—C3—C8 | −95.4 (2) | C8—C3—C4—C5 | −1.0 (3) |
N1—N2—C9—C10 | −175.48 (19) | C9—C10—C11—C12 | 174.2 (2) |
N2—N1—C1—S1 | −176.94 (15) | C9—C10—C15—C14 | −176.0 (2) |
N2—N1—C1—S2 | 2.7 (3) | C10—C11—C12—C13 | 1.0 (3) |
N2—C9—C10—C11 | 16.2 (3) | C11—C10—C15—C14 | 0.8 (3) |
N2—C9—C10—C15 | −167.2 (2) | C11—C12—C13—N3 | −176.9 (2) |
N3—C13—C14—C15 | 175.2 (2) | C11—C12—C13—C14 | 2.2 (3) |
N3—C16—C17—O1 | −56.2 (2) | C12—C13—C14—C15 | −3.9 (3) |
C1—S2—C2—C3 | 175.21 (17) | C13—N3—C16—C17 | 98.0 (2) |
C1—N1—N2—C9 | −170.6 (2) | C13—N3—C18—C19 | 84.7 (3) |
C2—S2—C1—S1 | 2.66 (17) | C13—C14—C15—C10 | 2.4 (4) |
C2—S2—C1—N1 | −176.95 (17) | C15—C10—C11—C12 | −2.6 (3) |
C2—C3—C4—C5 | 177.4 (2) | C16—N3—C13—C12 | −0.4 (3) |
C2—C3—C8—C7 | −177.4 (2) | C16—N3—C13—C14 | −179.4 (2) |
C3—C4—C5—C6 | 0.5 (3) | C16—N3—C18—C19 | −97.4 (2) |
C4—C3—C8—C7 | 1.1 (3) | C18—N3—C13—C12 | 177.3 (2) |
C4—C5—C6—C7 | 0.1 (4) | C18—N3—C13—C14 | −1.7 (3) |
C5—C6—C7—C8 | −0.1 (3) | C18—N3—C16—C17 | −79.8 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.88 | 2.06 | 2.933 (3) | 175 |
O1—H1···S1ii | 0.84 | 2.36 | 3.1749 (19) | 163 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z−1. |
Funding information
Funding for this research was provided by: National Natural Science Foundation of China (award No. 21871003; award No. 51672002).
References
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