N,N′-(Propane-1,3-di­yl)bis­(p-toluene­sulfonamide)

Khan, I.U.; Sheikh, T.A.; Ejaz; Harrison, W.T.A.

doi:10.1107/S1600536811030820

organic compounds

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Volume 67| Part 9| September 2011| Page o2371

doi:10.1107/S1600536811030820

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N,N′-(Propane-1,3-diyl)bis(p-toluenesulfonamide)

Islam Ullah Khan,^a ^* Tahir Ali Sheikh,^a Ejaz ^a and William T. A. Harrison ^b

^aMaterials Chemistry Laboratory, Department of Chemistry, GC University, Lahore 54000, Pakistan, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: iuklodhi@yahoo.com

(Received 27 July 2011; accepted 1 August 2011; online 17 August 2011)

The complete molecule of the title compound, C₁₇H₂₂N₂O₄S₂, is generated by crystallographic twofold symmetry, with one C atom lying on the rotation axis. The dihedral angle between the benzene rings is 44.04 (7)° and the conformation of the central N—C—C—C group is gauche. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, generating corrugated (010) sheets, and weak C—H⋯O interactions consolidate the packing.

Related literature

For the related structure of N,N′-ethylenebis(p-toluenesulfonamide), see: Gajadhar-Plummer et al. (2001 ).

Experimental

Crystal data

C₁₇H₂₂N₂O₄S₂
M_r = 382.49
Orthorhombic, A b a 2
a = 12.3169 (9) Å
b = 18.0787 (15) Å
c = 8.3819 (5) Å
V = 1866.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.52 × 0.46 × 0.36 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.856, T_max = 0.897
4996 measured reflections
1625 independent reflections
1472 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.078
S = 1.07
1625 reflections
119 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ), 372 Friedel pairs
Flack parameter: 0.12 (11)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.82 (3)	2.24 (3)	2.974 (2)	149 (2)
C7—H7C⋯O1ⁱⁱ	0.96	2.45	3.264 (3)	142
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y, z-{\script{1\over 2}}]$ ; (ii) $[-x+1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (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: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 .

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811030820/om2455sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811030820/om2455Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811030820/om2455Isup3.cml

checkCIF report

Comment top

As part of our ongoing structural studies of sulfonamides, the synthesis and structure of the title compound, (I), are now described.

The complete molecule of (I) is generated by crystallographic twofold symmetry (Fig. 1) with atom C9 lying on the rotation axis. The diehdral angle between the benzene rings is 44.04 (7)°. The conformation of the atoms of the central chain is gauche [N1—C8—C9—C8ⁱ = 75.53 (14)°; (i) = 1–x, 1–y, z] whereas the torsion angle for S1—N1—C8—C9 of -163.87 (15)° indicates a near anti conformation for these atoms. The bond-angle sum for N1 of 341.7° seems to indicate an intermediate valence state between sp² and sp³ hybridization (expected bond angle sums = 328.5 and 360°, respectively).

In the crystal, the molecules are linked by N—H···O hydrogen bonds (Table 1), to generate corrugated (010) sheets (Fig. 2). A weak C—H···O interaction may help to consolidate the packing. There is no aromatic π-π stacking in the crystal of (I).

The structure of the related compound N,N'-ethylenebis(p-toluenesulfonamide), (II), has been reported (Gajadhar-Plummer et al., 2001), in which an ethlyene bridge links the p-toluenesulfonamide units compared to a propylene bridge in (I). The complete molcule of (II) is generated by crystallographic inversion symmetry, thus the central N—C—C—N bridge is constrained to have a perfect anti conformation. The S—N—C—C torsion angle of -98.0 (2)° in (II) is also quite different to the equivalent torsion angle in (I).

Related literature top

For the related structure of N,N'-ethylenebis(p-toluenesulfonamide), see: Gajadhar-Plummer et al. (2001).

Experimental top

A mixture of 1,3-diaminopropane (0.0067 mol, 0.561 ml) and p-toluenesulfonyl chloride (0.0135 mol, 2.55 g) was stirred in 20 ml distilled water while maintaining the pH of the solution at about 9.0 with sodium carbonate solution (3%). The progress of the reaction was monitored by TLC: on completion, the white precipitate formed was filtered, washed with distilled water and dried. Colourless blocks of (I) were recrystallized from methanol.

Computing details top

Data collection: APEX2 (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: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) showing 30% displacement ellipsoids. Symmetry code: (i) 1–x, 1–y, z.
	Fig. 2. View approximately down [001] of the packing in (I) showing the interdigitated (010) sheets of molecules. All C-bound H atoms are omitted for clarity.

N,N'-(Propane-1,3-diyl)bis(p-toluenesulfonamide) top

Crystal data top

C₁₇H₂₂N₂O₄S₂	F(000) = 808
M_r = 382.49	D_x = 1.361 Mg m⁻³
Orthorhombic, Aba2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: A 2 -2ac	Cell parameters from 2756 reflections
a = 12.3169 (9) Å	θ = 2.8–28.3°
b = 18.0787 (15) Å	µ = 0.31 mm⁻¹
c = 8.3819 (5) Å	T = 296 K
V = 1866.4 (2) Å³	Block, colourless
Z = 4	0.52 × 0.46 × 0.36 mm

Data collection top

Bruker APEXII CCD diffractometer	1625 independent reflections
Radiation source: fine-focus sealed tube	1472 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
ω scans	θ_max = 28.4°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −11→16
T_min = 0.856, T_max = 0.897	k = −24→23
4996 measured reflections	l = −11→6

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	w = 1/[σ²(F_o²) + (0.0475P)² + 0.2164P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
1625 reflections	Δρ_max = 0.21 e Å⁻³
119 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 372 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (11)

Crystal data top

C₁₇H₂₂N₂O₄S₂	V = 1866.4 (2) Å³
M_r = 382.49	Z = 4
Orthorhombic, Aba2	Mo Kα radiation
a = 12.3169 (9) Å	µ = 0.31 mm⁻¹
b = 18.0787 (15) Å	T = 296 K
c = 8.3819 (5) Å	0.52 × 0.46 × 0.36 mm

Data collection top

Bruker APEXII CCD diffractometer	1625 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	1472 reflections with I > 2σ(I)
T_min = 0.856, T_max = 0.897	R_int = 0.019
4996 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.078	Δρ_max = 0.21 e Å⁻³
S = 1.07	Δρ_min = −0.20 e Å⁻³
1625 reflections	Absolute structure: Flack (1983), 372 Friedel pairs
119 parameters	Absolute structure parameter: 0.12 (11)
1 restraint

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
C1	0.65494 (18)	0.85229 (12)	0.6032 (3)	0.0505 (5)
C2	0.7458 (2)	0.80891 (11)	0.5798 (3)	0.0568 (6)
H2	0.8048	0.8285	0.5251	0.068*
C3	0.75132 (18)	0.73752 (11)	0.6352 (3)	0.0510 (5)
H3	0.8135	0.7094	0.6189	0.061*
C4	0.66317 (14)	0.70786 (10)	0.7158 (3)	0.0384 (4)
C5	0.57086 (16)	0.75001 (10)	0.7395 (3)	0.0455 (5)
H5	0.5114	0.7303	0.7931	0.055*
C6	0.56785 (17)	0.82139 (11)	0.6830 (3)	0.0500 (5)
H6	0.5056	0.8496	0.6988	0.060*
C7	0.6512 (2)	0.93096 (14)	0.5432 (4)	0.0782 (9)
H7A	0.6955	0.9354	0.4495	0.117*
H7B	0.6780	0.9637	0.6244	0.117*
H7C	0.5776	0.9439	0.5175	0.117*
C8	0.52239 (18)	0.56829 (12)	0.5701 (3)	0.0480 (5)
H8A	0.5160	0.6123	0.5044	0.058*
H8B	0.4701	0.5718	0.6562	0.058*
C9	0.5000	0.5000	0.4707 (4)	0.0535 (8)
H9	0.4379	0.5094	0.4025	0.064*
S1	0.66864 (4)	0.61578 (2)	0.78225 (9)	0.04287 (14)
O1	0.59049 (15)	0.60730 (8)	0.9065 (2)	0.0615 (4)
O2	0.77949 (13)	0.59791 (8)	0.8137 (2)	0.0610 (5)
N1	0.63280 (15)	0.56284 (9)	0.6355 (2)	0.0414 (4)
H1	0.6771 (18)	0.5633 (14)	0.563 (3)	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0603 (13)	0.0396 (11)	0.0515 (13)	−0.0102 (9)	−0.0112 (10)	0.0031 (10)
C2	0.0545 (12)	0.0483 (11)	0.0675 (15)	−0.0129 (10)	0.0095 (13)	0.0028 (10)
C3	0.0442 (11)	0.0476 (10)	0.0613 (14)	−0.0010 (9)	0.0072 (11)	−0.0025 (10)
C4	0.0426 (11)	0.0346 (8)	0.0380 (9)	−0.0006 (7)	−0.0039 (9)	−0.0005 (7)
C5	0.0437 (10)	0.0421 (10)	0.0506 (13)	0.0009 (8)	0.0023 (9)	0.0025 (8)
C6	0.0481 (12)	0.0426 (10)	0.0594 (14)	0.0052 (9)	−0.0083 (10)	−0.0010 (9)
C7	0.094 (2)	0.0443 (13)	0.097 (2)	−0.0174 (12)	−0.0219 (18)	0.0166 (14)
C8	0.0488 (12)	0.0433 (10)	0.0519 (12)	−0.0037 (8)	−0.0063 (10)	0.0068 (9)
C9	0.0573 (19)	0.065 (2)	0.0387 (14)	−0.0183 (15)	0.000	0.000
S1	0.0551 (3)	0.0375 (2)	0.0360 (2)	0.00355 (18)	−0.0046 (3)	0.0038 (2)
O1	0.0904 (12)	0.0516 (9)	0.0425 (8)	−0.0022 (8)	0.0158 (9)	0.0068 (7)
O2	0.0633 (10)	0.0568 (9)	0.0627 (13)	0.0121 (7)	−0.0238 (9)	0.0014 (8)
N1	0.0462 (10)	0.0378 (8)	0.0403 (9)	0.0000 (7)	0.0016 (8)	−0.0001 (7)

Geometric parameters (Å, º) top

C1—C2	1.380 (3)	C7—H7B	0.9600
C1—C6	1.382 (3)	C7—H7C	0.9600
C1—C7	1.509 (3)	C8—N1	1.470 (3)
C2—C3	1.373 (3)	C8—C9	1.515 (3)
C2—H2	0.9300	C8—H8A	0.9700
C3—C4	1.387 (3)	C8—H8B	0.9700
C3—H3	0.9300	C9—C8ⁱ	1.515 (3)
C4—C5	1.383 (2)	C9—H9	0.9700
C4—S1	1.7567 (19)	S1—O1	1.4265 (17)
C5—C6	1.375 (3)	S1—O2	1.4276 (16)
C5—H5	0.9300	S1—N1	1.6199 (18)
C6—H6	0.9300	N1—H1	0.82 (3)
C7—H7A	0.9600

C2—C1—C6	117.9 (2)	C1—C7—H7C	109.5
C2—C1—C7	120.9 (2)	H7A—C7—H7C	109.5
C6—C1—C7	121.2 (2)	H7B—C7—H7C	109.5
C3—C2—C1	121.8 (2)	N1—C8—C9	108.60 (16)
C3—C2—H2	119.1	N1—C8—H8A	110.0
C1—C2—H2	119.1	C9—C8—H8A	110.0
C2—C3—C4	119.3 (2)	N1—C8—H8B	110.0
C2—C3—H3	120.4	C9—C8—H8B	110.0
C4—C3—H3	120.4	H8A—C8—H8B	108.4
C5—C4—C3	120.04 (19)	C8—C9—C8ⁱ	113.3 (3)
C5—C4—S1	120.55 (14)	C8—C9—H9	109.0
C3—C4—S1	119.40 (15)	C8ⁱ—C9—H9	108.8
C6—C5—C4	119.33 (19)	O1—S1—O2	119.10 (12)
C6—C5—H5	120.3	O1—S1—N1	107.88 (10)
C4—C5—H5	120.3	O2—S1—N1	105.50 (10)
C5—C6—C1	121.67 (19)	O1—S1—C4	107.90 (9)
C5—C6—H6	119.2	O2—S1—C4	108.04 (9)
C1—C6—H6	119.2	N1—S1—C4	107.97 (10)
C1—C7—H7A	109.5	C8—N1—S1	119.73 (14)
C1—C7—H7B	109.5	C8—N1—H1	109.8 (17)
H7A—C7—H7B	109.5	S1—N1—H1	112.2 (18)

C6—C1—C2—C3	−0.9 (4)	C5—C4—S1—O1	−22.6 (2)
C7—C1—C2—C3	179.2 (3)	C3—C4—S1—O1	159.14 (18)
C1—C2—C3—C4	0.5 (4)	C5—C4—S1—O2	−152.60 (18)
C2—C3—C4—C5	0.1 (3)	C3—C4—S1—O2	29.1 (2)
C2—C3—C4—S1	178.35 (19)	C5—C4—S1—N1	93.76 (19)
C3—C4—C5—C6	−0.3 (3)	C3—C4—S1—N1	−84.50 (19)
S1—C4—C5—C6	−178.50 (17)	C9—C8—N1—S1	−163.87 (15)
C4—C5—C6—C1	−0.2 (3)	O1—S1—N1—C8	53.02 (18)
C2—C1—C6—C5	0.7 (4)	O2—S1—N1—C8	−178.68 (15)
C7—C1—C6—C5	−179.4 (2)	C4—S1—N1—C8	−63.35 (17)
N1—C8—C9—C8ⁱ	75.53 (14)

Symmetry code: (i) −x+1, −y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱⁱ	0.82 (3)	2.24 (3)	2.974 (2)	149 (2)
C7—H7C···O1ⁱⁱⁱ	0.96	2.45	3.264 (3)	142

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

Experimental details

Crystal data
Chemical formula	C₁₇H₂₂N₂O₄S₂
M_r	382.49
Crystal system, space group	Orthorhombic, Aba2
Temperature (K)	296
a, b, c (Å)	12.3169 (9), 18.0787 (15), 8.3819 (5)
V (Å³)	1866.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.52 × 0.46 × 0.36

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.856, 0.897
No. of measured, independent and observed [I > 2σ(I)] reflections	4996, 1625, 1472
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.078, 1.07
No. of reflections	1625
No. of parameters	119
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)	0.21, −0.20
Absolute structure	Flack (1983), 372 Friedel pairs
Absolute structure parameter	0.12 (11)

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2ⁱ	0.82 (3)	2.24 (3)	2.974 (2)	149 (2)
C7—H7C···O1ⁱⁱ	0.96	2.45	3.264 (3)	142

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

Acknowledgements

IUK thanks the Higher Education Commission of Pakistan for financial support under the project to strengthen the Materials Chemistry Laboratory at GCUL.

References

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