1,2-Bis(p-tolyl­sulfon­yl)hydrazine

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.065
• wR factor = 0.080
• Data-to-parameter ratio = 14.1

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   298.000
            Value of melting point given =     0.000
RINTA01_ALERT_3_C  The value of Rint is greater than 0.10
            Rint given   0.108
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         40 Perc.
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S1     --  O2      ..       6.93 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    S2     --  O4      ..       6.93 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C10
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C8
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT334_ALERT_2_C Small Average Benzene C-C Dist.  C8     -C13           1.36 Ang.
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT234_ALERT_4_C Large Hirshfeld Difference C8     --  C13     ..       0.13  Ang.
PLAT380_ALERT_4_C Check Incorrectly? Oriented X(sp2)-Methyl Moiety        C14

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
  13 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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

S2. Experimental

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

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

Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids (arbitrary spheres for the H atoms).

1,2-Bis(p-tolylsulfonyl)hydrazine

Crystal data

C14H16N2O4S2	F(000) = 712
Mr = 340.41	Dx = 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) Å^3	0.33 × 0.11 × 0.04 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	2808 independent reflections
Radiation source: fine-focus sealed tube	1132 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.108
ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −18→12
Tmin = 0.893, Tmax = 0.986	k = −12→12
7984 measured reflections	l = −11→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.065	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0003P)^2] where P = (Fo^2 + 2Fc^2)/3
2808 reflections	(Δ/σ)max < 0.001
199 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3^i	0.90	2.10	2.935 (5)	155
N2—H2A···O1^i	0.90	2.01	2.857 (5)	157

Symmetry code: (i) x, −y+3/2, z+1/2.