N,N′-(Ethane-1,2-di­yl)bis­(methane­sulfon­amide)

Abstract

The mol­ecular structure of the title compound, C₄H₁₂N₂O₄S₂, has crystallographic inversion symmetry. The central N—C—C—N moiety was refined as disordered over two sets of sites with an approximate occupancy ratio of 3:1 [0.742 (15):0.258 (15). In the crystal, N—H⋯O hydrogen bonds link adjacent mol­ecules into a thick sheet structure parallel to the b-axis direction.

Related literature  

For analogous disulfonamide compounds, see: Al-Dajani et al. (2011a ▶,b ▶). For other analyses and properties of disulfonamide compounds, see: Alyar et al. (2011 ▶, 2012 ▶). For their biological and pharmaceutical activity, see: Sahu et al. (2007 ▶); Innocenti et al. (2008 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental  

Crystal data  

• C₄H₁₂N₂O₄S₂

• M _r = 216.28

• Monoclinic,

• a = 10.5668 (11) Å

• b = 5.6092 (6) Å

• c = 8.5141 (9) Å

• β = 109.790 (6)°

• V = 474.84 (9) ų

• Z = 2

• Mo Kα radiation

• μ = 0.54 mm⁻¹

• T = 296 K

• 0.30 × 0.28 × 0.10 mm

Data collection  

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.854, T _max = 0.948

• 10251 measured reflections

• 1115 independent reflections

• 1033 reflections with I > 2σ(I)

• R _int = 0.025

Refinement  

• R[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 0.099

• S = 1.10

• 1115 reflections

• 76 parameters

• 2 restraints

• H-atom parameters constrained

• Δρ_max = 0.31 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

CCDC reference: http://scripts.iucr.org/cgi-bin/cr.cgi?rm=csd&csdid=958589

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.86	2.46	3.009 (6)	122

Symmetry code: (i) .

supplementary crystallographic information

1. Comment

Sulfonamides have long been utilised as bacteriostatic agents in both human and veterinary medicine, and their derivatives have a wide range of pharmacological applications (Alyar et el., 2011, 2012). In recent years, concentrated effort has been made on the effectiveness of the disulfonamide compounds as antimicrobial agents, and reported here is the solid state structure of a related disulfonamide intended for further studies: N,N'-ethane-1,2-diyl-bis(methane-sulfonamide) (Figure 1). The asymmetric unit of the title consists of half of the molecule, as the central C-C bond sits on top of an inversion centre. This structure is directly analogous to several previously reported structures (e.g. Al-Dajani et al., 2011a,b; entries AYONOS and AYORUC in the Cambridge Structural Database (version 5.34, Allen (2002))), which all contains aryl sulfonamide moieties. Unlike these reported structures, the methyl group does not exert significant steric pressure on the neighbouring sulfur atom. While the bond angle surrounding the sulfonamide S atom ranges between 106.80 (11)° and 117.60 (13)°, the overall geometry does not significantly deviate from an ideal tetrahedral configuration (average bond angle = 109.4°). The molecule is also slightly twisted at the N atom (C1-S1-N1-C2 torsion angle = -56.19°). An extended network is formed through intramolecular hydrogen bonding. Any one molecule is hydrogen-bonded to four different neighbouring molecules (Figure 2, Table 1).

2. Experimental

THF solution of 1,2-diaminoethane was added dropwise to the tetrahydrofuran (THF) solution of methyl sufonyl chloride in equimolar fashion, with the temperature maintained between -5 and -10°C. The reaction mixture was allowed to warm and stirred for 24 h at room temperature. Upon completion of the reaction, the solvent was removed under vacuum, and the solid residue was purified by column chromatography. The product was identified with ¹H-NMR. To recrystallize, the product was disolved in minimum amount of hot dichloromethane (DCM), and colourless, plate-like crystals formed upon gradual cooling of the solution.

Please note that a polymorph (deposited with the Cambridge Crystallographic Data centre as CCDC 958590) of the title compound was obtained initially. Crystals of this polymorph were obtained at elevated temperature, in a complexation reaction using the title compound as a ligand. Unfortunately, the crystallization condition cannot be accurately identified, and independent crystallization using the condition stated gave the structure reported in this manuscript.

3. Refinement

Minor rotational disorder was modelled and the refined occupancy ratio is 0.742:0.258 (15). The SHELXL constraint RIGU was used for the disordered carbon of the minor component, and SADI to restrain the refinements of S—N' and N'-C' bond lengths. All protons were refined using suitable riding models. Terminal C—H bonds, ethyl C—H bonds and amido N—H bonds were assumed to be 0.960 Å, 0.970 Å and 0.860 Å, respectively. The U values of terminal methyl protons are set to be 1.5 times of that of the attached carbon, while all other protons are calculated to be 1.2 times of the U values of the attached atom.

Figures

Fig. 1.

Molecular structure of the title compound, with the ellipsoids drawn at 30% probability. Hydrogen atoms and disordered components are omitted in the figure. (Symmetry equilvalent atoms generated by -x, -y, -z)

Fig. 2.

Hydrogen bonding observed in the lattice, and only hydrogen bonding protons are shown. Disorder components are omitted. (Symmetry equivalent atoms generated by -x, -y, -z, -x, 1/2 + y, 0.5 - z and +x, -0.5 - y, 1/2 + z)

Fig. 3.

Packing diagram (viewed slightly off b-axis) showing hydrogen bonds (dashed lines). Disordered components are omitted.

Crystal data

C4H12N2O4S2	F(000) = 228
Mr = 216.28	Dx = 1.513 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.5668 (11) Å	Cell parameters from 5915 reflections
b = 5.6092 (6) Å	θ = 2.7–27.7°
c = 8.5141 (9) Å	µ = 0.54 mm−1
β = 109.790 (6)°	T = 296 K
V = 474.84 (9) Å3	Plate, colourless
Z = 2	0.30 × 0.28 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1033 reflections with I > 2σ(I)
phi and ω scans	Rint = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2001)	θmax = 27.7°, θmin = 2.1°
Tmin = 0.854, Tmax = 0.948	h = −13→13
10251 measured reflections	k = −7→7
1115 independent reflections	l = −11→11

Refinement

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032	w = 1/[σ2(Fo2) + (0.0579P)2 + 0.1493P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.099	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.31 e Å−3
1115 reflections	Δρmin = −0.32 e Å−3
76 parameters	Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.060 (8)

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.A disorder of the N—C—C—N chain in the molecule is observed. The occupancies were allowed to be refined freely. SADI restrains were used on the bond lengths of the S-N bond and the N—C bond. Furthermore, the hard constrain RIGU was placed on the displacement parameters of C2'. ISOR did not significantly improve the refinement.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	0.27263 (4)	0.10237 (7)	0.80849 (5)	0.0399 (2)
O1	0.22112 (17)	−0.0101 (3)	0.92544 (17)	0.0616 (4)
O2	0.34539 (14)	0.3196 (2)	0.85836 (18)	0.0564 (4)
C1	0.3769 (2)	−0.1041 (4)	0.7557 (3)	0.0599 (5)
H1A	0.4547	−0.1357	0.8519	0.090*
H1B	0.4046	−0.0397	0.6681	0.090*
H1C	0.3282	−0.2497	0.7184	0.090*
N1	0.1439 (6)	0.1585 (10)	0.6441 (5)	0.0419 (11)	0.742 (15)
H1	0.1218	0.3021	0.6106	0.050*	0.742 (15)
C2	0.0667 (4)	−0.0467 (5)	0.5549 (6)	0.0531 (12)	0.742 (15)
H2A	0.0546	−0.1622	0.6334	0.064*	0.742 (15)
H2B	0.1134	−0.1235	0.4882	0.064*	0.742 (15)
N1'	0.162 (2)	0.170 (3)	0.637 (2)	0.063 (5)	0.258 (15)
H1'	0.1771	0.2772	0.5731	0.076*	0.258 (15)
C2'	0.0165 (18)	0.026 (4)	0.5855 (12)	0.069 (5)	0.258 (15)
H2'A	0.0255	−0.1192	0.6502	0.082*	0.258 (15)
H2'B	−0.0520	0.1255	0.6046	0.082*	0.258 (15)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0482 (3)	0.0379 (3)	0.0328 (3)	−0.00469 (15)	0.01254 (19)	−0.00383 (13)
O1	0.0881 (10)	0.0592 (9)	0.0456 (8)	−0.0079 (8)	0.0331 (7)	0.0037 (6)
O2	0.0614 (8)	0.0464 (8)	0.0533 (8)	−0.0136 (6)	0.0088 (6)	−0.0113 (6)
C1	0.0590 (12)	0.0546 (12)	0.0642 (13)	0.0071 (9)	0.0185 (10)	−0.0093 (9)
N1	0.0397 (18)	0.0455 (19)	0.0334 (14)	−0.0088 (13)	0.0030 (11)	0.0088 (13)
C2	0.0401 (18)	0.0432 (13)	0.063 (2)	0.0043 (11)	0.0005 (15)	−0.0143 (12)
N1'	0.043 (6)	0.051 (7)	0.090 (11)	−0.003 (5)	0.015 (5)	−0.035 (7)
C2'	0.064 (7)	0.092 (11)	0.051 (5)	−0.034 (8)	0.021 (5)	−0.006 (5)

Geometric parameters (Å, º)

S1—O2	1.4267 (13)	N1—H1	0.8600
S1—O1	1.4327 (14)	C2—C2i	1.498 (6)
S1—N1'	1.574 (13)	C2—H2A	0.9700
S1—N1	1.619 (4)	C2—H2B	0.9700
S1—C1	1.758 (2)	N1'—C2'	1.66 (3)
C1—H1A	0.9600	N1'—H1'	0.8600
C1—H1B	0.9600	C2'—C2'i	1.41 (2)
C1—H1C	0.9600	C2'—H2'A	0.9700
N1—C2	1.465 (6)	C2'—H2'B	0.9700
O2—S1—O1	117.55 (9)	S1—N1—H1	121.5
O2—S1—N1'	103.0 (7)	N1—C2—C2i	106.8 (3)
O1—S1—N1'	114.5 (10)	N1—C2—H2A	110.4
O2—S1—N1	107.6 (2)	C2i—C2—H2A	110.4
O1—S1—N1	106.3 (2)	N1—C2—H2B	110.4
O2—S1—C1	108.52 (10)	C2i—C2—H2B	110.4
O1—S1—C1	107.80 (11)	H2A—C2—H2B	108.6
N1'—S1—C1	104.7 (7)	S1—N1'—C2'	117.2 (14)
N1—S1—C1	108.8 (2)	S1—N1'—H1'	121.4
S1—C1—H1A	109.5	C2'—N1'—H1'	121.4
S1—C1—H1B	109.5	C2'i—C2'—N1'	104.9 (14)
H1A—C1—H1B	109.5	C2'i—C2'—H2'A	110.8
S1—C1—H1C	109.5	N1'—C2'—H2'A	110.8
H1A—C1—H1C	109.5	C2'i—C2'—H2'B	110.8
H1B—C1—H1C	109.5	N1'—C2'—H2'B	110.8
C2—N1—S1	116.9 (3)	H2'A—C2'—H2'B	108.8
C2—N1—H1	121.5
O2—S1—N1—C2	170.3 (5)	O2—S1—N1'—C2'	−149.8 (15)
O1—S1—N1—C2	−63.0 (6)	O1—S1—N1'—C2'	−21.0 (18)
N1'—S1—N1—C2	113 (6)	N1—S1—N1'—C2'	−25 (5)
C1—S1—N1—C2	52.9 (6)	C1—S1—N1'—C2'	96.8 (17)
S1—N1—C2—C2i	162.7 (5)	S1—N1'—C2'—C2'i	−138 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ii	0.86	2.46	3.009 (6)	122

Symmetry code: (ii) x, −y+1/2, z−1/2.