1,5-Bis[1-(4-meth­oxy­phen­yl)ethyl­idene]thio­carbonohydrazide

Zhao, X.

doi:10.1107/S1600536811029023

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o2132

doi:10.1107/S1600536811029023

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1,5-Bis[1-(4-methoxyphenyl)ethylidene]thiocarbonohydrazide

Xinyu Zhao ^a ^*

^aSchool of Petrochemical Engineering, Shenyang University of Technology, Liaoyang 111003, People's Republic of China
^*Correspondence e-mail: xyzhaosut@163.com

(Received 24 May 2011; accepted 19 July 2011; online 23 July 2011)

In the title molecule, C₁₉H₂₂N₄O₂S, the two benzene rings form a dihedral angle of 9.16 (13)°. In the crystal, pairs of weak intermolecular C—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers, which are further linked through weak C—H⋯O interactions into sheets parallel to (012).

Related literature

For related Schiff base derivatives of thiocarbonohydrazide, see: Loncle et al. (2004 ); Camp et al. (2010 ). For a related structure, see: Affan et al. (2010 ).

Experimental

Crystal data

C₁₉H₂₂N₄O₂S
M_r = 370.47
Monoclinic, P 2₁ /n
a = 7.4225 (6) Å
b = 11.4705 (11) Å
c = 21.749 (2) Å
β = 91.781 (1)°
V = 1850.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 298 K
0.41 × 0.39 × 0.35 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.924, T_max = 0.935
9108 measured reflections
3256 independent reflections
1829 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.049
wR(F²) = 0.135
S = 1.05
3256 reflections
239 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O1ⁱ	0.93	2.59	3.478 (4)	161
C3—H3A⋯S1ⁱⁱ	0.96	2.90	3.503 (3)	122
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y, -z+2.

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

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811029023/cv5100sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811029023/cv5100Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811029023/cv5100Isup3.cml

checkCIF report

Comment top

Thiocarbonohydrazide and it's Schiff base derivatives have attracted considerable interest in the chemistry of metal complexes, owing to their wide range of biological activities and catalytical abilities (Loncle et al., 2004; Camp et al., 2010). Herein, we report the crystal structure of the title compound, (I), which is a new derivative of thiocarbonohydrazide.

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 C4-C9 form a dihedral angle of 12.20 (3) °. The benzene ring C4-C9 and the benzene ring C13-C18 form a dihedral angle of 9.16 (13) °.

In the crystal structure, weak intermolecular C—H···S hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers, which are further linked through the weak C—H···O interactions (Table 1) into sheets parallel to (012) plane.

Related literature top

For related Schiff base derivatives of thiocarbonohydrazide, see: Loncle et al. (2004); Camp et al. (2010). For a related structure, see: Affan et al. (2010).

Experimental top

4-Methoxylacetophenone (10.0 mmol), 30 ml of ethanol 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.

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. View of (I) showing the atomic numbering and 30% probability displacement ellipsoids.

1,5-Bis[1-(4-methoxyphenyl)ethylidene]thiocarbonohydrazide top

Crystal data top

C₁₉H₂₂N₄O₂S	F(000) = 784
M_r = 370.47	D_x = 1.330 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.4225 (6) Å	Cell parameters from 1954 reflections
b = 11.4705 (11) Å	θ = 2.6–21.8°
c = 21.749 (2) Å	µ = 0.20 mm⁻¹
β = 91.781 (1)°	T = 298 K
V = 1850.8 (3) Å³	Block, yellow
Z = 4	0.41 × 0.39 × 0.35 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3256 independent reflections
Radiation source: fine-focus sealed tube	1829 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.924, T_max = 0.935	k = −13→13
9108 measured reflections	l = −25→25

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0435P)² + 0.9707P] where P = (F_o² + 2F_c²)/3
3256 reflections	(Δ/σ)_max = 0.001
239 parameters	Δρ_max = 0.26 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₉H₂₂N₄O₂S	V = 1850.8 (3) Å³
M_r = 370.47	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.4225 (6) Å	µ = 0.20 mm⁻¹
b = 11.4705 (11) Å	T = 298 K
c = 21.749 (2) Å	0.41 × 0.39 × 0.35 mm
β = 91.781 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	3256 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1829 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.935	R_int = 0.050
9108 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.049	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.05	Δρ_max = 0.26 e Å⁻³
3256 reflections	Δρ_min = −0.21 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
S1	0.89899 (14)	0.14956 (8)	1.05758 (4)	0.0558 (3)
N1	0.9376 (4)	0.1693 (2)	0.93818 (11)	0.0464 (7)
H1	0.9799	0.0995	0.9382	0.056*
N2	0.9174 (4)	0.2304 (2)	0.88416 (12)	0.0441 (7)
N3	0.8371 (4)	0.3316 (2)	0.98297 (12)	0.0493 (7)
H3	0.8383	0.3611	0.9466	0.059*
N4	0.7809 (4)	0.3991 (2)	1.03058 (12)	0.0462 (7)
O1	0.8713 (4)	0.46947 (19)	0.62470 (10)	0.0617 (7)
O2	0.5350 (4)	0.78761 (19)	1.21510 (11)	0.0650 (7)
C1	0.8904 (4)	0.2201 (3)	0.99129 (14)	0.0416 (8)
C2	0.9728 (4)	0.1862 (3)	0.83430 (14)	0.0404 (8)
C3	1.0640 (6)	0.0700 (3)	0.83080 (16)	0.0620 (11)
H3A	1.1369	0.0577	0.8675	0.093*
H3B	1.1389	0.0682	0.7956	0.093*
H3C	0.9746	0.0097	0.8271	0.093*
C4	0.9453 (4)	0.2574 (3)	0.77845 (14)	0.0397 (8)
C5	0.8960 (5)	0.3744 (3)	0.78197 (15)	0.0489 (9)
H5	0.8768	0.4073	0.8203	0.059*
C6	0.8753 (5)	0.4419 (3)	0.73063 (15)	0.0515 (9)
H6	0.8451	0.5202	0.7345	0.062*
C7	0.8987 (5)	0.3951 (3)	0.67283 (15)	0.0456 (8)
C8	0.9468 (5)	0.2803 (3)	0.66780 (15)	0.0497 (9)
H8	0.9647	0.2478	0.6293	0.060*
C9	0.9687 (5)	0.2128 (3)	0.72022 (15)	0.0488 (9)
H9	1.0002	0.1347	0.7161	0.059*
C10	0.8880 (5)	0.4244 (3)	0.56465 (15)	0.0622 (10)
H10A	1.0064	0.3922	0.5605	0.093*
H10B	0.8695	0.4859	0.5352	0.093*
H10C	0.7995	0.3646	0.5574	0.093*
C11	0.7401 (4)	0.5055 (3)	1.01736 (14)	0.0424 (8)
C12	0.7505 (5)	0.5578 (3)	0.95444 (15)	0.0570 (10)
H12A	0.8587	0.5319	0.9356	0.085*
H12B	0.7517	0.6412	0.9577	0.085*
H12C	0.6476	0.5337	0.9297	0.085*
C13	0.6849 (4)	0.5776 (3)	1.06957 (14)	0.0393 (8)
C14	0.7042 (5)	0.5384 (3)	1.12935 (15)	0.0481 (9)
H14	0.7525	0.4646	1.1364	0.058*
C15	0.6550 (5)	0.6040 (3)	1.17903 (15)	0.0503 (9)
H15	0.6707	0.5749	1.2187	0.060*
C16	0.5819 (5)	0.7137 (3)	1.16945 (16)	0.0486 (9)
C17	0.5580 (5)	0.7541 (3)	1.11045 (16)	0.0566 (10)
H17	0.5070	0.8272	1.1036	0.068*
C18	0.6088 (5)	0.6877 (3)	1.06136 (16)	0.0539 (9)
H18	0.5919	0.7170	1.0217	0.065*
C19	0.5427 (5)	0.7484 (3)	1.27698 (16)	0.0628 (10)
H19A	0.4640	0.6827	1.2812	0.094*
H19B	0.5052	0.8102	1.3035	0.094*
H19C	0.6640	0.7260	1.2881	0.094*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0754 (7)	0.0489 (5)	0.0435 (5)	0.0089 (5)	0.0060 (4)	0.0056 (4)
N1	0.062 (2)	0.0384 (15)	0.0387 (16)	0.0058 (14)	0.0058 (14)	0.0021 (13)
N2	0.0564 (19)	0.0396 (15)	0.0365 (16)	0.0022 (14)	0.0035 (13)	0.0019 (13)
N3	0.069 (2)	0.0404 (16)	0.0390 (16)	0.0090 (15)	0.0065 (14)	0.0010 (12)
N4	0.0554 (19)	0.0411 (16)	0.0421 (16)	0.0063 (14)	0.0013 (13)	−0.0048 (13)
O1	0.090 (2)	0.0475 (14)	0.0473 (15)	−0.0034 (13)	0.0007 (13)	0.0103 (12)
O2	0.091 (2)	0.0421 (14)	0.0629 (17)	0.0096 (13)	0.0140 (14)	−0.0056 (12)
C1	0.043 (2)	0.0383 (18)	0.044 (2)	−0.0008 (16)	0.0024 (15)	−0.0028 (15)
C2	0.047 (2)	0.0327 (17)	0.0416 (19)	−0.0051 (15)	0.0052 (16)	−0.0004 (14)
C3	0.094 (3)	0.040 (2)	0.053 (2)	0.008 (2)	0.013 (2)	0.0044 (17)
C4	0.043 (2)	0.0341 (17)	0.0418 (19)	−0.0034 (15)	0.0047 (15)	−0.0017 (15)
C5	0.064 (2)	0.0397 (19)	0.043 (2)	−0.0035 (17)	0.0013 (17)	−0.0059 (16)
C6	0.071 (3)	0.0345 (18)	0.049 (2)	−0.0035 (17)	−0.0032 (18)	−0.0012 (17)
C7	0.051 (2)	0.0391 (19)	0.047 (2)	−0.0077 (16)	0.0031 (17)	0.0078 (16)
C8	0.064 (2)	0.047 (2)	0.039 (2)	0.0009 (18)	0.0059 (17)	−0.0002 (16)
C9	0.066 (3)	0.0331 (17)	0.048 (2)	0.0023 (17)	0.0079 (18)	−0.0005 (16)
C10	0.065 (3)	0.076 (3)	0.046 (2)	0.000 (2)	0.0095 (19)	0.0107 (19)
C11	0.041 (2)	0.0394 (19)	0.046 (2)	0.0008 (16)	−0.0027 (15)	0.0039 (15)
C12	0.070 (3)	0.047 (2)	0.053 (2)	0.0007 (19)	−0.0007 (19)	0.0031 (17)
C13	0.040 (2)	0.0346 (17)	0.043 (2)	−0.0029 (15)	−0.0017 (15)	0.0010 (15)
C14	0.055 (2)	0.0325 (17)	0.056 (2)	0.0041 (16)	0.0022 (18)	0.0044 (16)
C15	0.060 (2)	0.0436 (19)	0.048 (2)	0.0039 (18)	0.0044 (18)	0.0051 (16)
C16	0.049 (2)	0.0371 (19)	0.060 (2)	−0.0026 (17)	0.0070 (18)	−0.0017 (17)
C17	0.071 (3)	0.0379 (19)	0.060 (2)	0.0167 (19)	−0.001 (2)	0.0043 (18)
C18	0.068 (3)	0.044 (2)	0.050 (2)	0.0109 (19)	−0.0017 (18)	0.0056 (16)
C19	0.070 (3)	0.061 (2)	0.057 (2)	−0.006 (2)	0.011 (2)	−0.0051 (19)

Geometric parameters (Å, º) top

S1—C1	1.653 (3)	C8—C9	1.384 (4)
N1—C1	1.350 (4)	C8—H8	0.9300
N1—N2	1.372 (3)	C9—H9	0.9300
N1—H1	0.8600	C10—H10A	0.9600
N2—C2	1.277 (4)	C10—H10B	0.9600
N3—C1	1.349 (4)	C10—H10C	0.9600
N3—N4	1.368 (3)	C11—C13	1.473 (4)
N3—H3	0.8600	C11—C12	1.499 (4)
N4—C11	1.288 (4)	C12—H12A	0.9600
O1—C7	1.361 (4)	C12—H12B	0.9600
O1—C10	1.414 (4)	C12—H12C	0.9600
O2—C16	1.359 (4)	C13—C14	1.379 (4)
O2—C19	1.418 (4)	C13—C18	1.393 (4)
C2—C4	1.472 (4)	C14—C15	1.375 (4)
C2—C3	1.498 (4)	C14—H14	0.9300
C3—H3A	0.9600	C15—C16	1.383 (4)
C3—H3B	0.9600	C15—H15	0.9300
C3—H3C	0.9600	C16—C17	1.371 (4)
C4—C9	1.382 (4)	C17—C18	1.374 (4)
C4—C5	1.394 (4)	C17—H17	0.9300
C5—C6	1.364 (4)	C18—H18	0.9300
C5—H5	0.9300	C19—H19A	0.9600
C6—C7	1.383 (4)	C19—H19B	0.9600
C6—H6	0.9300	C19—H19C	0.9600
C7—C8	1.370 (4)

C1—N1—N2	119.2 (3)	O1—C10—H10A	109.5
C1—N1—H1	120.4	O1—C10—H10B	109.5
N2—N1—H1	120.4	H10A—C10—H10B	109.5
C2—N2—N1	119.7 (3)	O1—C10—H10C	109.5
C1—N3—N4	122.0 (3)	H10A—C10—H10C	109.5
C1—N3—H3	119.0	H10B—C10—H10C	109.5
N4—N3—H3	119.0	N4—C11—C13	115.4 (3)
C11—N4—N3	116.3 (3)	N4—C11—C12	124.4 (3)
C7—O1—C10	117.8 (3)	C13—C11—C12	120.1 (3)
C16—O2—C19	119.5 (3)	C11—C12—H12A	109.5
N3—C1—N1	112.2 (3)	C11—C12—H12B	109.5
N3—C1—S1	125.8 (2)	H12A—C12—H12B	109.5
N1—C1—S1	122.1 (2)	C11—C12—H12C	109.5
N2—C2—C4	116.1 (3)	H12A—C12—H12C	109.5
N2—C2—C3	123.7 (3)	H12B—C12—H12C	109.5
C4—C2—C3	120.2 (3)	C14—C13—C18	116.5 (3)
C2—C3—H3A	109.5	C14—C13—C11	121.3 (3)
C2—C3—H3B	109.5	C18—C13—C11	122.1 (3)
H3A—C3—H3B	109.5	C15—C14—C13	122.7 (3)
C2—C3—H3C	109.5	C15—C14—H14	118.7
H3A—C3—H3C	109.5	C13—C14—H14	118.7
H3B—C3—H3C	109.5	C14—C15—C16	119.5 (3)
C9—C4—C5	116.6 (3)	C14—C15—H15	120.3
C9—C4—C2	122.2 (3)	C16—C15—H15	120.3
C5—C4—C2	121.2 (3)	O2—C16—C17	116.4 (3)
C6—C5—C4	121.7 (3)	O2—C16—C15	124.4 (3)
C6—C5—H5	119.2	C17—C16—C15	119.2 (3)
C4—C5—H5	119.2	C16—C17—C18	120.6 (3)
C5—C6—C7	120.6 (3)	C16—C17—H17	119.7
C5—C6—H6	119.7	C18—C17—H17	119.7
C7—C6—H6	119.7	C17—C18—C13	121.5 (3)
O1—C7—C8	125.1 (3)	C17—C18—H18	119.2
O1—C7—C6	115.8 (3)	C13—C18—H18	119.2
C8—C7—C6	119.1 (3)	O2—C19—H19A	109.5
C7—C8—C9	119.8 (3)	O2—C19—H19B	109.5
C7—C8—H8	120.1	H19A—C19—H19B	109.5
C9—C8—H8	120.1	O2—C19—H19C	109.5
C4—C9—C8	122.2 (3)	H19A—C19—H19C	109.5
C4—C9—H9	118.9	H19B—C19—H19C	109.5
C8—C9—H9	118.9

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O1ⁱ	0.93	2.59	3.478 (4)	161
C3—H3A···S1ⁱⁱ	0.96	2.90	3.503 (3)	122

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₉H₂₂N₄O₂S
M_r	370.47
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.4225 (6), 11.4705 (11), 21.749 (2)
β (°)	91.781 (1)
V (Å³)	1850.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.20
Crystal size (mm)	0.41 × 0.39 × 0.35

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.924, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	9108, 3256, 1829
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.135, 1.05
No. of reflections	3256
No. of parameters	239
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O1ⁱ	0.93	2.59	3.478 (4)	160.5
C3—H3A···S1ⁱⁱ	0.96	2.90	3.503 (3)	121.9

Symmetry codes: (i) x−1/2, −y+3/2, z+1/2; (ii) −x+2, −y, −z+2.

Acknowledgements

The author acknowledges financial support by Shenyang University of Technology.

References

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