1,5-Bis(4-iso­propyl­benzyl­idene)thio­carbonohydrazide

Han, Y.-H.; Zhao, Q.; Wang, Y.

doi:10.1107/S1600536813027293

organic compounds

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ISSN: 2056-9890

Volume 69| Part 11| November 2013| Page o1663

doi:10.1107/S1600536813027293

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1,5-Bis(4-isopropylbenzylidene)thiocarbonohydrazide

Yan-Hua Han,^a Qiao Zhao ^b and Yong Wang ^b ^*

^aLiaocheng Technician College, Shandong 252059, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: yongwang@lcu.edu.cn

(Received 19 September 2013; accepted 4 October 2013; online 19 October 2013)

The title compound, C₂₁H₂₆N₄S, was synthesized by the condensation reaction of 4-isopropylbenzaldehyde with thiocarbohydrazide in ethanol. The planes of the two benzene rings in the molecule are inclined at 22.6 (1)°. In the crystal, pairs of intermolecular N—H⋯S hydrogen bonds link the molecules into inversion dimers.

CCDC reference: 964861

Related literature

For applications of thiocarbonohydrazide derivatives, see: Bacchi et al. (2005 ); Han et al. (2007 ). For the crystal structures of related compounds, see: Gao (2013 ); Yu et al. (2013 ).

Experimental

Crystal data

C₂₁H₂₆N₄S
M_r = 366.52
Monoclinic, P 2₁ /c
a = 18.082 (6) Å
b = 11.129 (4) Å
c = 10.617 (3) Å
β = 95.330 (6)°
V = 2127.2 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 296 K
0.21 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX diffractometer with a CCD area detector
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.967, T_max = 0.976
10028 measured reflections
3659 independent reflections
1635 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.078
wR(F²) = 0.236
S = 1.08
3659 reflections
239 parameters
410 restraints
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯S1ⁱ	0.86	2.58	3.381 (4)	155
Symmetry code: (i) -x, -y+2, -z.

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; 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.

Supporting information

CCDC reference: 964861

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813027293/cv5428sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027293/cv5428Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813027293/cv5428Isup3.cml

checkCIF report

Comment top

Schiff base ligands of thiocarbohydrazide have many applications in chemistry (Bacchi et al., 2005; Han et al., 2007). In a continuation of our structural study of thiocarbonohydrazides (Gao, 2013; Yu et al., 2013), we present here the title compound (I).

In (I) (Fig. 1), the bond lengths and angles are normal and correspond to those observed in 1,5-bis(2-methoxyphenyl)methylene-thiocarbonohydrazide methanol solvate (Yu et al., 2013) and 1,5-bis(1-(4-bromophenyl)ethylidene)thiocarbonohydrazide (Gao, 2013). The benzene rings C3—C8 and C13—C18 are inclined each to other at 22.6 (1)°.

In the crystal, pairs of intermolecular N—H···S hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers.

Related literature top

For applications of thiocarbonohydrazide derivatives, see: Bacchi et al. (2005); Han et al. (2007). For the crystal structures of related compounds, see: Gao et al. (2013); Yu et al. (2013); Yan et al. (2013).

Experimental top

A 50 ml flask was charged with a magnetic stir bar, p-isopropylbenzaldehyde (2 mmol), thiocarbohydrazide (1 mmol) in 20 ml ethanol. After 5 h stirring at 373 K, the resulting mixture was cooled down to room temperature, and recrystalized from ethanol, and afforded the title compound as a crystalline solid.

Computing details top

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).

Figures top

Fig. 1. The molecular structure of (I) showing the atomic numbering and 30% probability displacement ellipsoids. H atoms omitted for clarity.

1,5-Bis(4-isopropylbenzylidene)thiocarbonohydrazide top

Crystal data top

C₂₁H₂₆N₄S	F(000) = 784
M_r = 366.52	D_x = 1.144 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1030 reflections
a = 18.082 (6) Å	θ = 2.7–20.2°
b = 11.129 (4) Å	µ = 0.16 mm⁻¹
c = 10.617 (3) Å	T = 296 K
β = 95.330 (6)°	Block, yellow
V = 2127.2 (12) Å³	0.21 × 0.18 × 0.15 mm
Z = 4

Data collection top

Bruker SMART APEX with a CCD area detector diffractometer	3659 independent reflections
Radiation source: fine-focus sealed tube	1635 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
phi and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −17→21
T_min = 0.967, T_max = 0.976	k = −8→13
10028 measured 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)] = 0.078	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.236	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.1P)² + 0.1124P] where P = (F_o² + 2F_c²)/3
3659 reflections	(Δ/σ)_max < 0.001
239 parameters	Δρ_max = 0.38 e Å⁻³
410 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₂₁H₂₆N₄S	V = 2127.2 (12) Å³
M_r = 366.52	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 18.082 (6) Å	µ = 0.16 mm⁻¹
b = 11.129 (4) Å	T = 296 K
c = 10.617 (3) Å	0.21 × 0.18 × 0.15 mm
β = 95.330 (6)°

Data collection top

Bruker SMART APEX with a CCD area detector diffractometer	3659 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1635 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.976	R_int = 0.065
10028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.078	410 restraints
wR(F²) = 0.236	H-atom parameters constrained
S = 1.08	Δρ_max = 0.38 e Å⁻³
3659 reflections	Δρ_min = −0.47 e Å⁻³
239 parameters

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	U_iso*/U_eq
N1	0.1303 (2)	0.8272 (4)	0.2266 (4)	0.0648 (11)
H1	0.1163	0.8211	0.3016	0.078*
N2	0.1942 (2)	0.7702 (4)	0.1996 (4)	0.0649 (11)
N3	0.0291 (2)	0.9425 (4)	0.1818 (3)	0.0680 (11)
H3	0.0049	0.9959	0.1361	0.082*
N4	0.0053 (2)	0.9097 (3)	0.2969 (3)	0.0621 (10)
S1	0.11024 (8)	0.91415 (15)	−0.00810 (13)	0.0919 (6)
C1	0.0896 (3)	0.8915 (5)	0.1412 (4)	0.0630 (12)
C2	0.2323 (3)	0.7216 (4)	0.2937 (5)	0.0690 (12)
H2	0.2172	0.7302	0.3746	0.083*
C3	0.2989 (3)	0.6530 (5)	0.2757 (5)	0.0693 (12)
C4	0.3340 (3)	0.5859 (5)	0.3754 (6)	0.0888 (15)
H4	0.3173	0.5904	0.4555	0.107*
C5	0.3926 (3)	0.5138 (6)	0.3552 (7)	0.1026 (16)
H5	0.4145	0.4697	0.4231	0.123*
C6	0.4212 (3)	0.5025 (6)	0.2414 (7)	0.1014 (16)
C7	0.3874 (3)	0.5705 (6)	0.1433 (7)	0.1014 (15)
H7	0.4053	0.5660	0.0641	0.122*
C8	0.3284 (3)	0.6442 (5)	0.1592 (6)	0.0869 (14)
H8	0.3075	0.6893	0.0912	0.104*
C9	0.4818 (4)	0.4181 (7)	0.2203 (8)	0.1266 (19)
H9	0.4762	0.3718	0.2974	0.152*
C10	0.4599 (4)	0.3124 (7)	0.1311 (9)	0.156 (3)
H10A	0.4395	0.3429	0.0507	0.234*
H10B	0.4235	0.2636	0.1673	0.234*
H10C	0.5031	0.2648	0.1197	0.234*
C11	0.5593 (4)	0.4607 (8)	0.2642 (10)	0.176 (3)
H11A	0.5871	0.4714	0.1923	0.265*
H11B	0.5835	0.4020	0.3200	0.265*
H11C	0.5565	0.5357	0.3081	0.265*
C12	−0.0521 (3)	0.9657 (5)	0.3280 (4)	0.0636 (12)
H12	−0.0709	1.0296	0.2783	0.076*
C13	−0.0890 (2)	0.9318 (4)	0.4397 (4)	0.0607 (11)
C14	−0.0643 (3)	0.8389 (5)	0.5184 (5)	0.0752 (13)
H14	−0.0213	0.7975	0.5034	0.090*
C15	−0.1028 (3)	0.8071 (5)	0.6185 (5)	0.0846 (14)
H15	−0.0838	0.7461	0.6720	0.102*
C16	−0.1689 (3)	0.8621 (5)	0.6435 (5)	0.0716 (12)
C17	−0.1916 (3)	0.9581 (5)	0.5653 (5)	0.0731 (12)
H17	−0.2343	1.0001	0.5804	0.088*
C18	−0.1526 (3)	0.9926 (5)	0.4665 (4)	0.0699 (12)
H18	−0.1691	1.0577	0.4166	0.084*
C19	−0.2112 (3)	0.8149 (5)	0.7515 (6)	0.0901 (16)
H19	−0.1737	0.7960	0.8213	0.108*
C20	−0.2469 (4)	0.6994 (6)	0.7122 (7)	0.125 (2)
H20A	−0.2697	0.6653	0.7820	0.188*
H20B	−0.2100	0.6450	0.6860	0.188*
H20C	−0.2840	0.7131	0.6430	0.188*
C21	−0.2629 (4)	0.9014 (7)	0.8022 (6)	0.119 (2)
H21A	−0.3039	0.9159	0.7400	0.178*
H21B	−0.2373	0.9755	0.8224	0.178*
H21C	−0.2810	0.8689	0.8773	0.178*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.058 (2)	0.076 (3)	0.063 (2)	0.002 (2)	0.0203 (19)	−0.008 (2)
N2	0.056 (2)	0.071 (3)	0.070 (3)	−0.001 (2)	0.017 (2)	−0.010 (2)
N3	0.064 (2)	0.085 (3)	0.058 (2)	0.010 (2)	0.0209 (19)	−0.006 (2)
N4	0.058 (2)	0.074 (3)	0.056 (2)	−0.002 (2)	0.0155 (18)	−0.0111 (19)
S1	0.0794 (10)	0.1351 (15)	0.0648 (8)	0.0252 (9)	0.0251 (7)	0.0002 (8)
C1	0.058 (3)	0.073 (3)	0.060 (3)	0.002 (2)	0.016 (2)	−0.009 (2)
C2	0.060 (2)	0.068 (3)	0.081 (3)	−0.006 (2)	0.019 (2)	−0.007 (2)
C3	0.056 (2)	0.067 (3)	0.087 (3)	−0.005 (2)	0.016 (2)	−0.009 (2)
C4	0.073 (3)	0.092 (3)	0.103 (3)	0.002 (3)	0.013 (3)	−0.005 (3)
C5	0.083 (3)	0.098 (3)	0.125 (3)	0.010 (3)	0.001 (3)	−0.008 (3)
C6	0.071 (3)	0.100 (3)	0.133 (4)	0.013 (3)	0.012 (3)	−0.021 (3)
C7	0.074 (3)	0.109 (3)	0.124 (3)	0.007 (3)	0.024 (3)	−0.019 (3)
C8	0.063 (3)	0.094 (3)	0.106 (3)	0.004 (2)	0.022 (2)	−0.008 (3)
C9	0.094 (4)	0.124 (4)	0.161 (4)	0.018 (3)	0.010 (3)	−0.023 (4)
C10	0.127 (5)	0.125 (5)	0.218 (7)	0.023 (5)	0.018 (5)	−0.034 (5)
C11	0.118 (5)	0.178 (7)	0.231 (8)	0.042 (5)	0.001 (5)	−0.047 (6)
C12	0.061 (2)	0.072 (3)	0.060 (2)	0.009 (2)	0.015 (2)	0.000 (2)
C13	0.060 (2)	0.064 (3)	0.059 (2)	0.009 (2)	0.011 (2)	−0.001 (2)
C14	0.068 (3)	0.076 (3)	0.084 (3)	0.014 (2)	0.019 (2)	0.011 (2)
C15	0.083 (3)	0.081 (3)	0.092 (3)	0.010 (2)	0.014 (2)	0.022 (2)
C16	0.070 (3)	0.071 (3)	0.075 (3)	0.002 (2)	0.018 (2)	0.005 (2)
C17	0.067 (2)	0.080 (3)	0.075 (3)	0.014 (2)	0.019 (2)	0.004 (2)
C18	0.072 (3)	0.074 (3)	0.066 (2)	0.019 (2)	0.016 (2)	0.009 (2)
C19	0.086 (3)	0.086 (4)	0.101 (3)	−0.005 (3)	0.022 (3)	0.016 (3)
C20	0.126 (5)	0.117 (5)	0.136 (5)	−0.017 (4)	0.033 (4)	0.013 (4)
C21	0.119 (5)	0.128 (5)	0.117 (5)	−0.020 (4)	0.051 (4)	−0.003 (4)

Geometric parameters (Å, º) top

N1—C1	1.324 (6)	C10—H10C	0.9600
N1—N2	1.370 (5)	C11—H11A	0.9600
N1—H1	0.8600	C11—H11B	0.9600
N2—C2	1.279 (6)	C11—H11C	0.9600
N3—C1	1.339 (5)	C12—C13	1.463 (6)
N3—N4	1.381 (5)	C12—H12	0.9300
N3—H3	0.8600	C13—C14	1.376 (6)
N4—C12	1.280 (5)	C13—C18	1.387 (6)
S1—C1	1.681 (5)	C14—C15	1.369 (7)
C2—C3	1.453 (6)	C14—H14	0.9300
C2—H2	0.9300	C15—C16	1.390 (7)
C3—C8	1.394 (7)	C15—H15	0.9300
C3—C4	1.399 (7)	C16—C17	1.392 (7)
C4—C5	1.362 (8)	C16—C19	1.530 (7)
C4—H4	0.9300	C17—C18	1.371 (6)
C5—C6	1.363 (8)	C17—H17	0.9300
C5—H5	0.9300	C18—H18	0.9300
C6—C7	1.383 (9)	C19—C21	1.477 (8)
C6—C9	1.477 (9)	C19—C20	1.480 (8)
C7—C8	1.369 (7)	C19—H19	0.9800
C7—H7	0.9300	C20—H20A	0.9600
C8—H8	0.9300	C20—H20B	0.9600
C9—C11	1.511 (8)	C20—H20C	0.9600
C9—C10	1.538 (8)	C21—H21A	0.9600
C9—H9	0.9800	C21—H21B	0.9600
C10—H10A	0.9600	C21—H21C	0.9600
C10—H10B	0.9600

C1—N1—N2	122.2 (4)	C9—C11—H11B	109.5
C1—N1—H1	118.9	H11A—C11—H11B	109.5
N2—N1—H1	118.9	C9—C11—H11C	109.5
C2—N2—N1	115.9 (4)	H11A—C11—H11C	109.5
C1—N3—N4	120.3 (4)	H11B—C11—H11C	109.5
C1—N3—H3	119.9	N4—C12—C13	121.7 (4)
N4—N3—H3	119.9	N4—C12—H12	119.2
C12—N4—N3	115.3 (4)	C13—C12—H12	119.2
N1—C1—N3	115.3 (4)	C14—C13—C18	118.0 (4)
N1—C1—S1	124.7 (3)	C14—C13—C12	122.7 (4)
N3—C1—S1	120.0 (4)	C18—C13—C12	119.3 (4)
N2—C2—C3	120.8 (5)	C15—C14—C13	120.4 (5)
N2—C2—H2	119.6	C15—C14—H14	119.8
C3—C2—H2	119.6	C13—C14—H14	119.8
C8—C3—C4	116.7 (5)	C14—C15—C16	122.8 (5)
C8—C3—C2	122.9 (5)	C14—C15—H15	118.6
C4—C3—C2	120.3 (5)	C16—C15—H15	118.6
C5—C4—C3	120.0 (6)	C15—C16—C17	115.8 (4)
C5—C4—H4	120.0	C15—C16—C19	119.4 (5)
C3—C4—H4	120.0	C17—C16—C19	124.8 (5)
C4—C5—C6	123.9 (7)	C18—C17—C16	121.8 (5)
C4—C5—H5	118.0	C18—C17—H17	119.1
C6—C5—H5	118.0	C16—C17—H17	119.1
C5—C6—C7	116.1 (6)	C17—C18—C13	121.0 (5)
C5—C6—C9	122.7 (7)	C17—C18—H18	119.5
C7—C6—C9	121.1 (7)	C13—C18—H18	119.5
C8—C7—C6	122.0 (6)	C21—C19—C20	113.3 (5)
C8—C7—H7	119.0	C21—C19—C16	115.3 (5)
C6—C7—H7	119.0	C20—C19—C16	108.8 (5)
C7—C8—C3	121.2 (6)	C21—C19—H19	106.3
C7—C8—H8	119.4	C20—C19—H19	106.3
C3—C8—H8	119.4	C16—C19—H19	106.3
C6—C9—C11	115.7 (6)	C19—C20—H20A	109.5
C6—C9—C10	115.3 (6)	C19—C20—H20B	109.5
C11—C9—C10	127.4 (7)	H20A—C20—H20B	109.5
C6—C9—H9	94.1	C19—C20—H20C	109.5
C11—C9—H9	94.1	H20A—C20—H20C	109.5
C10—C9—H9	94.1	H20B—C20—H20C	109.5
C9—C10—H10A	109.5	C19—C21—H21A	109.5
C9—C10—H10B	109.5	C19—C21—H21B	109.5
H10A—C10—H10B	109.5	H21A—C21—H21B	109.5
C9—C10—H10C	109.5	C19—C21—H21C	109.5
H10A—C10—H10C	109.5	H21A—C21—H21C	109.5
H10B—C10—H10C	109.5	H21B—C21—H21C	109.5
C9—C11—H11A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1ⁱ	0.86	2.58	3.381 (4)	155

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···S1ⁱ	0.86	2.58	3.381 (4)	155.2

Symmetry code: (i) −x, −y+2, −z.

Acknowledgements

The authors gratefully acknowledge the financial support of the Students Technology Innovation Fund of Liaocheng University.

References

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