(E)-N′-(2-Thienyl­methyl­idene)-p-toluene­sulfono­hydrazide

Asiri, A.M.; Zayed, M.E.M.; Ng, S.W.

doi:10.1107/S1600536810032708

organic compounds

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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2360

https://doi.org/10.1107/S1600536810032708

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(E)-N′-(2-Thienylmethylidene)-p-toluenesulfonohydrazide

Abdullah M. Asiri,^a Mohie E. M. Zayed ^a and Seik Weng Ng ^b ^*

^aChemistry Department, Faculty of Science, King Abdul Aziz University, PO Box 80203, Jeddah 21589, Saudi Arabia, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 12 August 2010; accepted 14 August 2010; online 21 August 2010)

The S—N(H)—N=C linkage in the title molecule, C₁₂H₁₂N₂O₂S₂, is non-planar [torsion angle = 15.5 (1)°] as the amino N atom is pyramidally coordinated. The amino group acts as a hydrogen-bond donor to an O atom of an adjacent molecule, generating chains running parallel to the c axis.

Related literature

For the structure of the (E)-N′-benzylidene-p-toluenesulfonohydrazide homolog, see: Mehrabi et al. (2008 ).

Experimental

Crystal data

C₁₂H₁₂N₂O₂S₂
M_r = 280.36
Monoclinic, P 2₁ /c
a = 14.3758 (10) Å
b = 9.8613 (7) Å
c = 9.6172 (7) Å
β = 104.981 (1)°
V = 1317.03 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 100 K
0.40 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.857, T_max = 0.925
8238 measured reflections
3022 independent reflections
2728 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.085
S = 1.04
3022 reflections
168 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86 (1)	2.06 (1)	2.874 (2)	159 (2)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810032708/pk2261sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810032708/pk2261Isup2.hkl

checkCIF report

Comment top

p-Toluenesulfonyl hydrazide, CH₃-4-C₆H₄SO₂NHNH₂, condenses with carbonyl compounds to form Schiff bases, and among the plethora nearly a hundred have had their crystal structures determined. The compounds have the azomethine double-bond in an E-configuration. In the Schiff base product between p-toluenesulfonyl hydrazide and thiophene-2-carboxaldehyde, the S–N(H)–N═C linkage is non-planar [torsion angle 15.5 (1) °] because the amino nitrogen atom (which bears a hydrogen atom) is pyramidally coordinated (Fig. 1). The amino group acts as a hydrogen-bond donor to an oxygen atom of an adjacent molecule to generate a chain running along the c-axis of the monoclinic cell (Fig. 2). The oxygen atom involved in hydrogen bonding [S–O 1.4355 (10) Å] is marginally farther from the sulfur atom than the oxygen that is not involved in hydrogen bonding [S–O 1.4288 (10) Å].

Related literature top

For the structure of the (E)-N'-benzylidene-p-toluenesulfonohydrazide homolog, see: Mehrabi et al. (2008).

Experimental top

p-Toluenesulfonyl hydrazide (4.66 g, 2.5 mmol) and thiophene-2-carboxaldehyde (2.80 g, 2.5 mmol) were heated in methanol (50 ml) for two hours. The cool solution yielded a precipitate that was recrystallized from ethanol and collected in 90% yield.

Structure description top

For the structure of the (E)-N'-benzylidene-p-toluenesulfonohydrazide homolog, see: Mehrabi et al. (2008).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of C₁₂H₁₂N₂O₂S₂ at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. A view of the chain structure resulting from N—H···O hydrogen-bonding.

(E)-N'-(2-Thienylmethylidene)-p-toluenesulfonohydrazide top

Crystal data top

C₁₂H₁₂N₂O₂S₂	F(000) = 584
M_r = 280.36	D_x = 1.414 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4750 reflections
a = 14.3758 (10) Å	θ = 2.5–28.3°
b = 9.8613 (7) Å	µ = 0.40 mm⁻¹
c = 9.6172 (7) Å	T = 100 K
β = 104.981 (1)°	Prism, yellow
V = 1317.03 (16) Å³	0.40 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	3022 independent reflections
Radiation source: fine-focus sealed tube	2728 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ω scans	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −18→18
T_min = 0.857, T_max = 0.925	k = −12→12
8238 measured reflections	l = −8→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0458P)² + 0.7746P] where P = (F_o² + 2F_c²)/3
3022 reflections	(Δ/σ)_max = 0.001
168 parameters	Δρ_max = 0.42 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₂H₁₂N₂O₂S₂	V = 1317.03 (16) Å³
M_r = 280.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.3758 (10) Å	µ = 0.40 mm⁻¹
b = 9.8613 (7) Å	T = 100 K
c = 9.6172 (7) Å	0.40 × 0.20 × 0.20 mm
β = 104.981 (1)°

Data collection top

Bruker SMART APEX diffractometer	3022 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2728 reflections with I > 2σ(I)
T_min = 0.857, T_max = 0.925	R_int = 0.020
8238 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.42 e Å⁻³
3022 reflections	Δρ_min = −0.36 e Å⁻³
168 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	0.16267 (2)	0.25347 (3)	0.52894 (3)	0.01262 (10)
S2	0.51633 (3)	0.43030 (4)	0.75091 (4)	0.02186 (11)
O1	0.18378 (8)	0.21042 (11)	0.67638 (11)	0.0176 (2)
O2	0.08674 (7)	0.18970 (10)	0.42362 (11)	0.0174 (2)
N1	0.26105 (9)	0.22234 (13)	0.47478 (13)	0.0148 (2)
H1	0.2522 (14)	0.235 (2)	0.3840 (11)	0.024 (5)*
N2	0.34437 (9)	0.28097 (12)	0.56466 (13)	0.0156 (2)
C1	0.14605 (10)	0.42992 (14)	0.52115 (15)	0.0136 (3)
C2	0.08653 (10)	0.48722 (15)	0.39742 (15)	0.0159 (3)
H2	0.0530	0.4313	0.3203	0.019*
C3	0.07698 (10)	0.62763 (15)	0.38847 (15)	0.0170 (3)
H3	0.0360	0.6673	0.3048	0.020*
C4	0.12658 (10)	0.71101 (15)	0.50031 (16)	0.0172 (3)
C5	0.18520 (11)	0.65074 (15)	0.62312 (16)	0.0206 (3)
H5	0.2189	0.7065	0.7003	0.025*
C6	0.19530 (11)	0.51082 (15)	0.63480 (15)	0.0191 (3)
H6	0.2353	0.4710	0.7192	0.023*
C7	0.11737 (12)	0.86307 (15)	0.48857 (17)	0.0216 (3)
H7A	0.1290	0.9025	0.5851	0.032*
H7B	0.0524	0.8870	0.4322	0.032*
H7C	0.1647	0.8987	0.4408	0.032*
C8	0.41651 (11)	0.28677 (14)	0.51016 (16)	0.0169 (3)
H8	0.4109	0.2523	0.4161	0.020*
C9	0.50662 (10)	0.34545 (15)	0.59069 (16)	0.0173 (3)
C10	0.59275 (11)	0.34852 (15)	0.55085 (17)	0.0208 (3)
H10	0.6019	0.3079	0.4658	0.025*
C11	0.66556 (11)	0.41995 (16)	0.65279 (19)	0.0235 (3)
H11	0.7291	0.4324	0.6431	0.028*
C12	0.63483 (11)	0.46843 (16)	0.76529 (18)	0.0238 (3)
H12	0.6745	0.5179	0.8432	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.01349 (18)	0.01241 (17)	0.01124 (17)	−0.00057 (12)	0.00189 (13)	0.00002 (11)
S2	0.0198 (2)	0.0240 (2)	0.0209 (2)	−0.00308 (14)	0.00374 (15)	−0.00061 (14)
O1	0.0225 (5)	0.0173 (5)	0.0128 (5)	−0.0004 (4)	0.0045 (4)	0.0019 (4)
O2	0.0160 (5)	0.0164 (5)	0.0175 (5)	−0.0029 (4)	0.0002 (4)	−0.0010 (4)
N1	0.0137 (6)	0.0176 (6)	0.0120 (6)	0.0007 (4)	0.0014 (4)	−0.0019 (4)
N2	0.0142 (6)	0.0142 (5)	0.0163 (6)	−0.0001 (4)	0.0000 (5)	0.0006 (4)
C1	0.0136 (6)	0.0128 (6)	0.0149 (6)	0.0002 (5)	0.0048 (5)	0.0003 (5)
C2	0.0133 (6)	0.0180 (7)	0.0152 (6)	−0.0005 (5)	0.0018 (5)	−0.0011 (5)
C3	0.0136 (6)	0.0192 (7)	0.0168 (7)	0.0024 (5)	0.0017 (5)	0.0031 (5)
C4	0.0161 (7)	0.0159 (7)	0.0210 (7)	0.0011 (5)	0.0073 (6)	0.0017 (5)
C5	0.0249 (7)	0.0170 (7)	0.0177 (7)	−0.0016 (6)	0.0013 (6)	−0.0032 (6)
C6	0.0226 (7)	0.0179 (7)	0.0138 (7)	0.0015 (6)	−0.0005 (5)	0.0002 (5)
C7	0.0246 (8)	0.0143 (7)	0.0256 (8)	0.0008 (6)	0.0062 (6)	0.0017 (6)
C8	0.0184 (7)	0.0140 (6)	0.0176 (7)	0.0017 (5)	0.0032 (5)	0.0006 (5)
C9	0.0169 (7)	0.0145 (6)	0.0199 (7)	0.0012 (5)	0.0038 (5)	0.0026 (5)
C10	0.0203 (7)	0.0163 (7)	0.0248 (8)	−0.0010 (6)	0.0040 (6)	0.0040 (6)
C11	0.0164 (7)	0.0190 (7)	0.0340 (9)	−0.0011 (6)	0.0048 (6)	0.0077 (6)
C12	0.0189 (7)	0.0192 (7)	0.0293 (8)	−0.0042 (6)	−0.0006 (6)	0.0035 (6)

Geometric parameters (Å, º) top

S1—O2	1.4288 (10)	C4—C7	1.507 (2)
S1—O1	1.4355 (10)	C5—C6	1.389 (2)
S1—N1	1.6572 (13)	C5—H5	0.9500
S1—C1	1.7553 (14)	C6—H6	0.9500
S2—C12	1.7148 (16)	C7—H7A	0.9800
S2—C9	1.7270 (15)	C7—H7B	0.9800
N1—N2	1.4074 (16)	C7—H7C	0.9800
N1—H1	0.859 (9)	C8—C9	1.447 (2)
N2—C8	1.279 (2)	C8—H8	0.9500
C1—C6	1.3901 (19)	C9—C10	1.388 (2)
C1—C2	1.3932 (19)	C10—C11	1.422 (2)
C2—C3	1.392 (2)	C10—H10	0.9500
C2—H2	0.9500	C11—C12	1.357 (2)
C3—C4	1.395 (2)	C11—H11	0.9500
C3—H3	0.9500	C12—H12	0.9500
C4—C5	1.394 (2)

O2—S1—O1	119.85 (6)	C4—C5—H5	119.3
O2—S1—N1	104.68 (6)	C1—C6—C5	119.03 (13)
O1—S1—N1	106.02 (6)	C1—C6—H6	120.5
O2—S1—C1	109.60 (6)	C5—C6—H6	120.5
O1—S1—C1	109.08 (7)	C4—C7—H7A	109.5
N1—S1—C1	106.74 (6)	C4—C7—H7B	109.5
C12—S2—C9	91.59 (8)	H7A—C7—H7B	109.5
N2—N1—S1	113.01 (9)	C4—C7—H7C	109.5
N2—N1—H1	116.3 (13)	H7A—C7—H7C	109.5
S1—N1—H1	112.1 (13)	H7B—C7—H7C	109.5
C8—N2—N1	114.73 (12)	N2—C8—C9	120.48 (14)
C6—C1—C2	120.95 (13)	N2—C8—H8	119.8
C6—C1—S1	119.95 (11)	C9—C8—H8	119.8
C2—C1—S1	119.03 (11)	C10—C9—C8	126.88 (14)
C1—C2—C3	119.03 (13)	C10—C9—S2	111.33 (11)
C1—C2—H2	120.5	C8—C9—S2	121.73 (11)
C3—C2—H2	120.5	C9—C10—C11	111.76 (14)
C4—C3—C2	121.08 (13)	C9—C10—H10	124.1
C4—C3—H3	119.5	C11—C10—H10	124.1
C2—C3—H3	119.5	C12—C11—C10	113.01 (14)
C3—C4—C5	118.60 (13)	C12—C11—H11	123.5
C3—C4—C7	120.76 (13)	C10—C11—H11	123.5
C5—C4—C7	120.65 (14)	C11—C12—S2	112.32 (12)
C6—C5—C4	121.31 (14)	C11—C12—H12	123.8
C6—C5—H5	119.3	S2—C12—H12	123.8

O2—S1—N1—N2	178.54 (9)	C3—C4—C5—C6	0.5 (2)
O1—S1—N1—N2	−53.83 (11)	C7—C4—C5—C6	−179.24 (15)
C1—S1—N1—N2	62.38 (11)	C2—C1—C6—C5	−0.6 (2)
S1—N1—N2—C8	−164.50 (11)	S1—C1—C6—C5	176.50 (12)
O2—S1—C1—C6	163.60 (12)	C4—C5—C6—C1	0.2 (2)
O1—S1—C1—C6	30.58 (14)	N1—N2—C8—C9	179.61 (12)
N1—S1—C1—C6	−83.57 (13)	N2—C8—C9—C10	174.24 (14)
O2—S1—C1—C2	−19.24 (14)	N2—C8—C9—S2	−9.0 (2)
O1—S1—C1—C2	−152.26 (11)	C12—S2—C9—C10	−0.45 (12)
N1—S1—C1—C2	93.59 (12)	C12—S2—C9—C8	−177.63 (13)
C6—C1—C2—C3	0.2 (2)	C8—C9—C10—C11	177.28 (14)
S1—C1—C2—C3	−176.95 (11)	S2—C9—C10—C11	0.27 (16)
C1—C2—C3—C4	0.6 (2)	C9—C10—C11—C12	0.12 (19)
C2—C3—C4—C5	−1.0 (2)	C10—C11—C12—S2	−0.46 (18)
C2—C3—C4—C7	178.80 (14)	C9—S2—C12—C11	0.52 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86 (1)	2.06 (1)	2.874 (2)	159 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₂N₂O₂S₂
M_r	280.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	14.3758 (10), 9.8613 (7), 9.6172 (7)
β (°)	104.981 (1)
V (Å³)	1317.03 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.40 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.857, 0.925
No. of measured, independent and observed [I > 2σ(I)] reflections	8238, 3022, 2728
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.085, 1.04
No. of reflections	3022
No. of parameters	168
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.36

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86 (1)	2.06 (1)	2.874 (2)	159 (2)

Symmetry code: (i) x, −y+1/2, z−1/2.

Acknowledgements

We thank King Abdul Aziz University and the University of Malaya for supporting this study.

References

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