1,2-Bis(p-tolyl­sulfon­yl)hydrazine

Zhang, W.-F.; Li, R.-B.; Tai, X.-S.; Tang, S.-H.; Tang, J.-B.

doi:10.1107/S1600536808034314

organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page o2182

doi:10.1107/S1600536808034314

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1,2-Bis(p-tolylsulfonyl)hydrazine

Wei-Fen Zhang,^a ^* Ruo-Bao Li,^a Xi-Shi Tai,^b Shu-Hong Tang ^c and Jin-Bao Tang ^a

^aDepartment of Basic Medicine, Weifang Medical University, Weifang 261053, People's Republic of China, ^bDepartment of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^cCollege of Information and Control Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: taixishi@lzu.edu.cn

(Received 20 October 2008; accepted 21 October 2008; online 25 October 2008)

In the title compound, C₁₄H₁₆N₂O₄S₂, the dihedral angle between the aromatic ring planes is 76.8 (3)° and the S—N—N—S torsion angle is 122.5 (3)°. In the crystal structure, molecules form a chain structure by way of N—H⋯O hydrogen bonds.

Related literature

For background on aroylhydrazines, see: Bu et al. (2001 ); Ranford et al. (1998 ), Agarwal & Sharma (1993 ).

Experimental

Crystal data

C₁₄H₁₆N₂O₄S₂
M_r = 340.41
Monoclinic, P 2₁ /c
a = 15.7318 (16) Å
b = 10.7016 (12) Å
c = 9.4943 (9) Å
β = 90.102 (2)°
V = 1598.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 298 (2) K
0.33 × 0.11 × 0.04 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.893, T_max = 0.986
7984 measured reflections
2808 independent reflections
1132 reflections with I > 2σ(I)
R_int = 0.108

Refinement

R[F² > 2σ(F²)] = 0.065
wR(F²) = 0.080
S = 0.97
2808 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.90	2.10	2.935 (5)	155
N2—H2A⋯O1ⁱ	0.90	2.01	2.857 (5)	157
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); 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 global, I. DOI: 10.1107/S1600536808034314/hb2824sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034314/hb2824Isup2.hkl

checkCIF report

Comment top

Aroylhydrazines have drawn much attention in recent years due to their wide biological and pharmacological activities, such as antitumor (Ranford et al., 1998), antidiabetic (Bu et al., 2001) antitubercular (Agarwal & Sharma, 1993) activities. As part of our studies in this area, we now report the synthesis and crystal structure of the title compound, (I).

In (I), the dihedral angle between the two phenyl rings of (C1—C6 and C8—C13) is 76.8 (3)°. The S=O bond distances are characteristic of double bonds. The N1—N2 single bond of 1.407 (4) is in agreement with that of other acylhydrazone compounds in which the acylhydrazone takes a ketonic form.

In the crystal, N—H···O hydrogen bonds (Table 1) help to establish the packing.

Related literature top

For background on aroylhydrazines, see: Bu et al. (2001); Ranford et al. (1998), Agarwal & Sharma (1993).

Experimental top

5 mmol of 4-toluene sulfonyl chloride (5 mmol) was added to a solution of hydrazine (2.5 mmol) in 10 ml of ethanol at room temperature. The mixture was continuously stirred for 2 h at temperature, the solid product was collected by filtration and dried in vacuo (yield 58%). Clear blocks of (I) were obtained by evaporation from a methanol/water solution after 10 days.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 30% displacement ellipsoids (arbitrary spheres for the H atoms).

1,2-Bis(p-tolylsulfonyl)hydrazine top

Crystal data top

C₁₄H₁₆N₂O₄S₂	F(000) = 712
M_r = 340.41	D_x = 1.415 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 586 reflections
a = 15.7318 (16) Å	θ = 2.3–25.0°
b = 10.7016 (12) Å	µ = 0.35 mm⁻¹
c = 9.4943 (9) Å	T = 298 K
β = 90.102 (2)°	Flake, colourless
V = 1598.4 (3) Å³	0.33 × 0.11 × 0.04 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2808 independent reflections
Radiation source: fine-focus sealed tube	1132 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.108
ω scans	θ_max = 25.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −18→12
T_min = 0.893, T_max = 0.986	k = −12→12
7984 measured reflections	l = −11→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)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.080	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0003P)²] where P = (F_o² + 2F_c²)/3
2808 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₄H₁₆N₂O₄S₂	V = 1598.4 (3) Å³
M_r = 340.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.7318 (16) Å	µ = 0.35 mm⁻¹
b = 10.7016 (12) Å	T = 298 K
c = 9.4943 (9) Å	0.33 × 0.11 × 0.04 mm
β = 90.102 (2)°

Data collection top

Bruker SMART CCD diffractometer	2808 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1132 reflections with I > 2σ(I)
T_min = 0.893, T_max = 0.986	R_int = 0.108
7984 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.065	0 restraints
wR(F²) = 0.080	H-atom parameters constrained
S = 0.97	Δρ_max = 0.23 e Å⁻³
2808 reflections	Δρ_min = −0.27 e Å⁻³
199 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	0.82111 (9)	0.60680 (14)	−0.00482 (14)	0.0542 (4)
S2	0.70156 (9)	0.91574 (15)	−0.01299 (15)	0.0588 (4)
N1	0.7517 (2)	0.7008 (4)	0.0725 (4)	0.0513 (12)
H1	0.7484	0.6794	0.1640	0.062*
N2	0.7743 (2)	0.8278 (4)	0.0630 (4)	0.0535 (12)
H2A	0.7823	0.8571	0.1508	0.064*
O1	0.82411 (18)	0.6447 (3)	−0.1491 (3)	0.0628 (10)
O2	0.7938 (2)	0.4847 (3)	0.0334 (4)	0.0682 (11)
O3	0.6846 (2)	0.8623 (3)	−0.1482 (3)	0.0701 (11)
O4	0.7356 (2)	1.0395 (3)	−0.0015 (4)	0.0771 (13)
C1	0.9213 (3)	0.6382 (5)	0.0667 (5)	0.0446 (14)
C2	0.9673 (4)	0.7381 (5)	0.0188 (6)	0.0602 (17)
H2	0.9458	0.7892	−0.0520	0.072*
C3	1.0465 (4)	0.7620 (5)	0.0775 (6)	0.0634 (17)
H3	1.0772	0.8310	0.0467	0.076*
C4	1.0807 (3)	0.6865 (5)	0.1799 (6)	0.0534 (16)
C5	1.0339 (4)	0.5857 (5)	0.2236 (5)	0.0579 (15)
H5	1.0567	0.5327	0.2915	0.069*
C6	0.9547 (3)	0.5604 (5)	0.1703 (6)	0.0538 (15)
H6	0.9238	0.4923	0.2030	0.065*
C7	1.1679 (3)	0.7141 (5)	0.2376 (6)	0.080 (2)
H7A	1.1862	0.6461	0.2962	0.121*
H7B	1.1661	0.7895	0.2924	0.121*
H7C	1.2071	0.7245	0.1611	0.121*
C8	0.6086 (3)	0.9042 (5)	0.0880 (5)	0.0472 (14)
C9	0.6008 (4)	0.9722 (5)	0.2078 (6)	0.087 (2)
H9	0.6448	1.0240	0.2374	0.104*
C10	0.5265 (4)	0.9636 (6)	0.2860 (6)	0.095 (2)
H10	0.5214	1.0115	0.3673	0.115*
C11	0.4622 (4)	0.8893 (6)	0.2488 (6)	0.0659 (18)
C12	0.4712 (4)	0.8228 (5)	0.1302 (7)	0.087 (2)
H12	0.4274	0.7698	0.1025	0.104*
C13	0.5441 (4)	0.8306 (5)	0.0467 (6)	0.083 (2)
H13	0.5480	0.7851	−0.0365	0.100*
C14	0.3808 (3)	0.8797 (5)	0.3358 (6)	0.091 (2)
H14A	0.3852	0.9327	0.4170	0.136*
H14B	0.3727	0.7947	0.3654	0.136*
H14C	0.3332	0.9055	0.2794	0.136*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0498 (10)	0.0731 (11)	0.0398 (9)	0.0048 (9)	0.0043 (7)	−0.0049 (8)
S2	0.0622 (11)	0.0726 (11)	0.0417 (10)	0.0093 (10)	0.0038 (8)	0.0035 (9)
N1	0.052 (3)	0.068 (3)	0.034 (3)	0.010 (3)	0.004 (2)	0.002 (2)
N2	0.054 (3)	0.068 (3)	0.038 (3)	0.010 (3)	−0.001 (2)	−0.003 (3)
O1	0.058 (2)	0.099 (3)	0.031 (2)	0.011 (2)	0.0041 (17)	−0.007 (2)
O2	0.066 (3)	0.056 (2)	0.083 (3)	−0.009 (2)	0.003 (2)	−0.001 (2)
O3	0.073 (3)	0.104 (3)	0.033 (2)	0.021 (2)	0.0053 (19)	−0.004 (2)
O4	0.087 (3)	0.062 (2)	0.082 (3)	−0.014 (2)	0.012 (2)	0.010 (2)
C1	0.038 (3)	0.051 (4)	0.045 (4)	0.006 (3)	0.006 (3)	−0.005 (3)
C2	0.048 (4)	0.071 (4)	0.061 (4)	0.005 (4)	0.004 (3)	0.022 (3)
C3	0.048 (4)	0.076 (5)	0.066 (5)	−0.007 (4)	0.011 (3)	0.008 (4)
C4	0.051 (4)	0.058 (4)	0.051 (4)	0.007 (4)	−0.003 (3)	−0.013 (3)
C5	0.067 (4)	0.058 (4)	0.049 (4)	0.014 (4)	−0.012 (3)	0.002 (3)
C6	0.058 (4)	0.056 (4)	0.047 (4)	0.004 (3)	0.009 (3)	−0.001 (3)
C7	0.052 (4)	0.096 (5)	0.093 (6)	0.005 (4)	−0.012 (4)	−0.017 (4)
C8	0.049 (4)	0.055 (4)	0.038 (3)	0.006 (3)	−0.002 (3)	−0.003 (3)
C9	0.081 (5)	0.112 (5)	0.067 (5)	−0.030 (4)	0.015 (4)	−0.043 (4)
C10	0.094 (6)	0.124 (6)	0.069 (5)	−0.008 (5)	0.034 (4)	−0.042 (4)
C11	0.057 (4)	0.082 (5)	0.058 (4)	0.020 (4)	0.005 (4)	0.010 (4)
C12	0.057 (5)	0.112 (5)	0.092 (6)	−0.024 (4)	0.007 (4)	−0.029 (5)
C13	0.071 (5)	0.103 (5)	0.075 (5)	−0.003 (4)	0.001 (4)	−0.031 (4)
C14	0.068 (4)	0.132 (5)	0.072 (5)	0.026 (4)	0.017 (3)	0.020 (4)

Geometric parameters (Å, º) top

S1—O2	1.423 (3)	C5—H5	0.9300
S1—O1	1.429 (3)	C6—H6	0.9300
S1—N1	1.657 (3)	C7—H7A	0.9600
S1—C1	1.748 (5)	C7—H7B	0.9600
S2—O3	1.430 (3)	C7—H7C	0.9600
S2—O4	1.433 (3)	C8—C13	1.343 (6)
S2—N2	1.648 (4)	C8—C9	1.356 (6)
S2—C8	1.754 (4)	C9—C10	1.389 (6)
N1—N2	1.407 (4)	C9—H9	0.9300
N1—H1	0.9001	C10—C11	1.333 (7)
N2—H2A	0.8998	C10—H10	0.9300
C1—C2	1.369 (6)	C11—C12	1.340 (7)
C1—C6	1.391 (6)	C11—C14	1.529 (6)
C2—C3	1.387 (7)	C12—C13	1.398 (6)
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.373 (7)	C13—H13	0.9300
C3—H3	0.9300	C14—H14A	0.9600
C4—C5	1.370 (6)	C14—H14B	0.9600
C4—C7	1.507 (6)	C14—H14C	0.9600
C5—C6	1.371 (6)

O2—S1—O1	121.0 (2)	C5—C6—C1	119.0 (5)
O2—S1—N1	104.1 (2)	C5—C6—H6	120.5
O1—S1—N1	106.0 (2)	C1—C6—H6	120.5
O2—S1—C1	110.5 (3)	C4—C7—H7A	109.5
O1—S1—C1	106.6 (2)	C4—C7—H7B	109.5
N1—S1—C1	107.8 (2)	H7A—C7—H7B	109.5
O3—S2—O4	120.5 (2)	C4—C7—H7C	109.5
O3—S2—N2	107.0 (2)	H7A—C7—H7C	109.5
O4—S2—N2	103.6 (2)	H7B—C7—H7C	109.5
O3—S2—C8	107.9 (2)	C13—C8—C9	119.3 (5)
O4—S2—C8	109.6 (2)	C13—C8—S2	120.8 (4)
N2—S2—C8	107.4 (2)	C9—C8—S2	119.8 (5)
N2—N1—S1	113.0 (3)	C8—C9—C10	119.4 (6)
N2—N1—H1	108.8	C8—C9—H9	120.3
S1—N1—H1	108.2	C10—C9—H9	120.3
N1—N2—S2	113.8 (3)	C11—C10—C9	122.5 (6)
N1—N2—H2A	108.2	C11—C10—H10	118.8
S2—N2—H2A	107.5	C9—C10—H10	118.8
C2—C1—C6	120.2 (5)	C10—C11—C12	117.3 (6)
C2—C1—S1	119.9 (5)	C10—C11—C14	122.2 (6)
C6—C1—S1	119.9 (4)	C12—C11—C14	120.5 (7)
C1—C2—C3	119.1 (5)	C11—C12—C13	122.2 (6)
C1—C2—H2	120.5	C11—C12—H12	118.9
C3—C2—H2	120.5	C13—C12—H12	118.9
C4—C3—C2	121.7 (5)	C8—C13—C12	119.3 (6)
C4—C3—H3	119.1	C8—C13—H13	120.3
C2—C3—H3	119.1	C12—C13—H13	120.3
C5—C4—C3	117.9 (6)	C11—C14—H14A	109.5
C5—C4—C7	122.2 (6)	C11—C14—H14B	109.5
C3—C4—C7	119.8 (6)	H14A—C14—H14B	109.5
C4—C5—C6	122.1 (5)	C11—C14—H14C	109.5
C4—C5—H5	119.0	H14A—C14—H14C	109.5
C6—C5—H5	119.0	H14B—C14—H14C	109.5

O2—S1—N1—N2	172.0 (3)	C4—C5—C6—C1	1.3 (8)
O1—S1—N1—N2	−59.3 (4)	C2—C1—C6—C5	0.2 (7)
C1—S1—N1—N2	54.6 (4)	S1—C1—C6—C5	179.1 (4)
S1—N1—N2—S2	122.5 (3)	O3—S2—C8—C13	13.6 (5)
O3—S2—N2—N1	−55.6 (3)	O4—S2—C8—C13	146.6 (4)
O4—S2—N2—N1	176.0 (3)	N2—S2—C8—C13	−101.5 (5)
C8—S2—N2—N1	60.1 (4)	O3—S2—C8—C9	−165.1 (4)
O2—S1—C1—C2	165.9 (4)	O4—S2—C8—C9	−32.1 (5)
O1—S1—C1—C2	32.5 (4)	N2—S2—C8—C9	79.8 (5)
N1—S1—C1—C2	−80.9 (4)	C13—C8—C9—C10	0.4 (9)
O2—S1—C1—C6	−13.1 (4)	S2—C8—C9—C10	179.1 (5)
O1—S1—C1—C6	−146.4 (4)	C8—C9—C10—C11	1.0 (10)
N1—S1—C1—C6	100.2 (4)	C9—C10—C11—C12	−0.9 (10)
C6—C1—C2—C3	−1.5 (8)	C9—C10—C11—C14	179.6 (6)
S1—C1—C2—C3	179.6 (4)	C10—C11—C12—C13	−0.5 (10)
C1—C2—C3—C4	1.5 (9)	C14—C11—C12—C13	179.0 (5)
C2—C3—C4—C5	−0.2 (8)	C9—C8—C13—C12	−1.7 (8)
C2—C3—C4—C7	178.3 (5)	S2—C8—C13—C12	179.5 (4)
C3—C4—C5—C6	−1.2 (8)	C11—C12—C13—C8	1.9 (9)
C7—C4—C5—C6	−179.7 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.90	2.10	2.935 (5)	155
N2—H2A···O1ⁱ	0.90	2.01	2.857 (5)	157

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₆N₂O₄S₂
M_r	340.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	15.7318 (16), 10.7016 (12), 9.4943 (9)
β (°)	90.102 (2)
V (Å³)	1598.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.33 × 0.11 × 0.04

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.893, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	7984, 2808, 1132
R_int	0.108
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.065, 0.080, 0.97
No. of reflections	2808
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.27

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), 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
N1—H1···O3ⁱ	0.90	2.10	2.935 (5)	155
N2—H2A···O1ⁱ	0.90	2.01	2.857 (5)	157

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

The authors thank the National Natural Science Foundation of China (20671073), Shandong Province Scientific and Technological Brainstorm Project (2008 GG10002022), the National Natural Science Foundation of Shandong (Y2007B60) and the Science and Technology Foundation of Weifang for research grants.

References

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