(E)-Benzyl 2-{4-[eth­yl(2-hy­droxy­eth­yl)amino]­benzyl­idene}hydrazinecarbodi­thio­ate

Guo, H.; Du, W.; Zhou, H.

doi:10.1107/S2414314621009019

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 6| Part 9| September 2021| x210901

https://doi.org/10.1107/S2414314621009019

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(E)-Benzyl 2-{4-[ethyl(2-hydroxyethyl)amino]benzylidene}hydrazinecarbodithioate

Hui Guo,^a ^* Wenli Du ^a and Haoyu Zhou ^a

^aDepartment of Chemistry, Anhui University, Hefei, Anhui 230039, People's Republic of China
^*Correspondence e-mail: 1295913906@qq.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 8 June 2021; accepted 31 August 2021; online 3 September 2021)

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 crystal structure has triclinic (P $[\overline{1}]$ ) 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].

Figure 1
The molecular structure of the title compound showing 50% displacement ellipsoids.

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).

Table 1
Hydrogen-bond geometry (Å, °)

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) ; (ii) .

Figure 2
The intermolecular hydrogen bond diagram of compound. Symmetry codes: (i) −x + 1, −y, −z + 1; (ii) x + 1, y, z + 1

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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₉H₂₃N₃OS₂
M_r	373.52
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	120
a, b, c (Å)	9.1794 (18), 9.4642 (19), 11.665 (2)
α, β, γ (°)	101.78 (3), 107.81 (3), 93.57 (3)
V (Å³)	936.1 (4)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.30
Crystal size (mm)	0.12 × 0.11 × 0.1

Data collection
Diffractometer	Stoe X-AREA CCD
Absorption correction	Multi-scan (X-RED32; Stoe, 2018 )
T_min, T_max	0.342, 0.808
No. of measured, independent and observed [I > 2σ(I)] reflections	8565, 3419, 2508
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.097, 0.92
No. of reflections	3419
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.25
Computer programs: X-AREA (Stoe, 2018), SHELXT2018/2 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2106601

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314621009019/hb4387sup1.cif

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

checkCIF report

Computing details top

Data collection: X-AREA Pilatus3_SV (Stoe, 2018); cell refinement: 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).

(E)-Benzyl 2-{4-[ethyl(2-hydroxyethyl)amino]benzylidene}hydrazinecarbodithioate top

Crystal data top

C₁₉H₂₃N₃OS₂	Z = 2
M_r = 373.52	F(000) = 396
Triclinic, P1	D_x = 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

Data collection top

Stoe X-Area CCD diffractometer	2508 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.038
Absorption correction: multi-scan (X-Red32; Stoe, 2018)	θ_max = 25.6°, θ_min = 1.9°
T_min = 0.342, T_max = 0.808	h = −11→10
8565 measured reflections	k = −4→10
3419 independent reflections	l = −14→13

Refinement top

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(F_o²) + (0.0568P)²] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max = 0.001
3419 reflections	Δρ_max = 0.43 e Å⁻³
228 parameters	Δρ_min = −0.25 e Å⁻³
0 restraints

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	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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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