organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

aLaboratory of X-Ray Crystal Structure Analysis, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong S.A.R. , and bState Key Laboratory of Chirosciences and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong S.A.R.
*Correspondence e-mail: mankin.wong@polyu.edu.hk

(Received 13 November 2013; accepted 10 January 2014; online 15 January 2014)

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[Al-Dajani, M. T. M., Talaat, J., Mohamed, N., Hemamalini, M. & Fun, H.-K. (2011a). Acta Cryst. E67, o2214.],b[Al-Dajani, M. T. M., Wahab, H. A., Shamsuddin, S., Hemamalini, M. & Fun, H.-K. (2011b). Acta Cryst. E67, o2241.]). For other analyses and properties of disulfonamide compounds, see: Alyar et al. (2011[Alyar, S., Özbek, N., Kuzukiran, K. & Karacan, N. (2011). Med. Chem. Res. 20, 175-183.], 2012[Alyar, H., Ünal, A., Özbek, N., Alyar, S. & Karacan, N. (2012). Spectrochim. Acta Part A, 91, 39-47.]). For their biological and pharmaceutical activity, see: Sahu et al. (2007[Sahu, K. K., Ravichandran, V., Mourya, V. K. & Agrawal, R. K. (2007). Med. Chem. Res. 15, 418-430.]); Innocenti et al. (2008[Innocenti, A., Maresca, A., Scozzafava, A. & Supuran, C. T. (2008). Bioorg. Med. Chem. Lett. 18, 3938-3941.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C4H12N2O4S2

  • Mr = 216.28

  • Monoclinic, P 21 /c

  • a = 10.5668 (11) Å

  • b = 5.6092 (6) Å

  • c = 8.5141 (9) Å

  • β = 109.790 (6)°

  • V = 474.84 (9) Å3

  • 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[Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.854, Tmax = 0.948

  • 10251 measured reflections

  • 1115 independent reflections

  • 1033 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.099

  • S = 1.10

  • 1115 reflections

  • 76 parameters

  • 2 restraints

  • H-atom parameters constrained

  • Δρmax = 0.31 e Å−3

  • Δρmin = −0.32 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1⋯O1i 0.86 2.46 3.009 (6) 122
Symmetry code: (i) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

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).

Related literature top

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 top

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.

Refinement top

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.

Structure description top

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).

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).

Computing details top

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

Figures top
[Figure 1] 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)
[Figure 2] 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)
[Figure 3] Fig. 3. Packing diagram (viewed slightly off b-axis) showing hydrogen bonds (dashed lines). Disordered components are omitted.
N,N'-(Ethane-1,2-diyl)bis(methanesulfonamide) top
Crystal data top
C4H12N2O4S2F(000) = 228
Mr = 216.28Dx = 1.513 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 10.5668 (11) ÅCell parameters from 5915 reflections
b = 5.6092 (6) Åθ = 2.7–27.7°
c = 8.5141 (9) ŵ = 0.54 mm1
β = 109.790 (6)°T = 296 K
V = 474.84 (9) Å3Plate, colourless
Z = 20.30 × 0.28 × 0.10 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1033 reflections with I > 2σ(I)
phi and ω scansRint = 0.025
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
θmax = 27.7°, θmin = 2.1°
Tmin = 0.854, Tmax = 0.948h = 1313
10251 measured reflectionsk = 77
1115 independent reflectionsl = 1111
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-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 = 1.10Δρmax = 0.31 e Å3
1115 reflectionsΔρmin = 0.32 e Å3
76 parametersExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraintsExtinction coefficient: 0.060 (8)
Crystal data top
C4H12N2O4S2V = 474.84 (9) Å3
Mr = 216.28Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.5668 (11) ŵ = 0.54 mm1
b = 5.6092 (6) ÅT = 296 K
c = 8.5141 (9) Å0.30 × 0.28 × 0.10 mm
β = 109.790 (6)°
Data collection top
Bruker APEXII CCD area-detector
diffractometer
1115 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)
1033 reflections with I > 2σ(I)
Tmin = 0.854, Tmax = 0.948Rint = 0.025
10251 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0322 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.10Δρmax = 0.31 e Å3
1115 reflectionsΔρmin = 0.32 e Å3
76 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.

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.27263 (4)0.10237 (7)0.80849 (5)0.0399 (2)
O10.22112 (17)0.0101 (3)0.92544 (17)0.0616 (4)
O20.34539 (14)0.3196 (2)0.85836 (18)0.0564 (4)
C10.3769 (2)0.1041 (4)0.7557 (3)0.0599 (5)
H1A0.45470.13570.85190.090*
H1B0.40460.03970.66810.090*
H1C0.32820.24970.71840.090*
N10.1439 (6)0.1585 (10)0.6441 (5)0.0419 (11)0.742 (15)
H10.12180.30210.61060.050*0.742 (15)
C20.0667 (4)0.0467 (5)0.5549 (6)0.0531 (12)0.742 (15)
H2A0.05460.16220.63340.064*0.742 (15)
H2B0.11340.12350.48820.064*0.742 (15)
N1'0.162 (2)0.170 (3)0.637 (2)0.063 (5)0.258 (15)
H1'0.17710.27720.57310.076*0.258 (15)
C2'0.0165 (18)0.026 (4)0.5855 (12)0.069 (5)0.258 (15)
H2'A0.02550.11920.65020.082*0.258 (15)
H2'B0.05200.12550.60460.082*0.258 (15)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0482 (3)0.0379 (3)0.0328 (3)0.00469 (15)0.01254 (19)0.00383 (13)
O10.0881 (10)0.0592 (9)0.0456 (8)0.0079 (8)0.0331 (7)0.0037 (6)
O20.0614 (8)0.0464 (8)0.0533 (8)0.0136 (6)0.0088 (6)0.0113 (6)
C10.0590 (12)0.0546 (12)0.0642 (13)0.0071 (9)0.0185 (10)0.0093 (9)
N10.0397 (18)0.0455 (19)0.0334 (14)0.0088 (13)0.0030 (11)0.0088 (13)
C20.0401 (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) top
S1—O21.4267 (13)N1—H10.8600
S1—O11.4327 (14)C2—C2i1.498 (6)
S1—N1'1.574 (13)C2—H2A0.9700
S1—N11.619 (4)C2—H2B0.9700
S1—C11.758 (2)N1'—C2'1.66 (3)
C1—H1A0.9600N1'—H1'0.8600
C1—H1B0.9600C2'—C2'i1.41 (2)
C1—H1C0.9600C2'—H2'A0.9700
N1—C21.465 (6)C2'—H2'B0.9700
O2—S1—O1117.55 (9)S1—N1—H1121.5
O2—S1—N1'103.0 (7)N1—C2—C2i106.8 (3)
O1—S1—N1'114.5 (10)N1—C2—H2A110.4
O2—S1—N1107.6 (2)C2i—C2—H2A110.4
O1—S1—N1106.3 (2)N1—C2—H2B110.4
O2—S1—C1108.52 (10)C2i—C2—H2B110.4
O1—S1—C1107.80 (11)H2A—C2—H2B108.6
N1'—S1—C1104.7 (7)S1—N1'—C2'117.2 (14)
N1—S1—C1108.8 (2)S1—N1'—H1'121.4
S1—C1—H1A109.5C2'—N1'—H1'121.4
S1—C1—H1B109.5C2'i—C2'—N1'104.9 (14)
H1A—C1—H1B109.5C2'i—C2'—H2'A110.8
S1—C1—H1C109.5N1'—C2'—H2'A110.8
H1A—C1—H1C109.5C2'i—C2'—H2'B110.8
H1B—C1—H1C109.5N1'—C2'—H2'B110.8
C2—N1—S1116.9 (3)H2'A—C2'—H2'B108.8
C2—N1—H1121.5
O2—S1—N1—C2170.3 (5)O2—S1—N1'—C2'149.8 (15)
O1—S1—N1—C263.0 (6)O1—S1—N1'—C2'21.0 (18)
N1'—S1—N1—C2113 (6)N1—S1—N1'—C2'25 (5)
C1—S1—N1—C252.9 (6)C1—S1—N1'—C2'96.8 (17)
S1—N1—C2—C2i162.7 (5)S1—N1'—C2'—C2'i138 (2)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1ii0.862.463.009 (6)122
Symmetry code: (ii) x, y+1/2, z1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.862.463.009 (6)121.9
Symmetry code: (i) x, y+1/2, z1/2.
 

Acknowledgements

We are thankful for the financial support of the Hong Kong Research Grants Council (PolyU 5031/11p) and The Hong Kong Polytechnic University (PolyU Departmental General Research Funds, Competitive Research Grants for Newly Recruited Junior Academic Staff and SEG PolyU01).

References

First citationAl-Dajani, M. T. M., Talaat, J., Mohamed, N., Hemamalini, M. & Fun, H.-K. (2011a). Acta Cryst. E67, o2214.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationAl-Dajani, M. T. M., Wahab, H. A., Shamsuddin, S., Hemamalini, M. & Fun, H.-K. (2011b). Acta Cryst. E67, o2241.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
First citationAlyar, S., Özbek, N., Kuzukiran, K. & Karacan, N. (2011). Med. Chem. Res. 20, 175–183.  Web of Science CrossRef CAS Google Scholar
First citationAlyar, H., Ünal, A., Özbek, N., Alyar, S. & Karacan, N. (2012). Spectrochim. Acta Part A, 91, 39–47.  Web of Science CrossRef CAS Google Scholar
First citationBruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationInnocenti, A., Maresca, A., Scozzafava, A. & Supuran, C. T. (2008). Bioorg. Med. Chem. Lett. 18, 3938–3941.  Web of Science CrossRef PubMed CAS Google Scholar
First citationSahu, K. K., Ravichandran, V., Mourya, V. K. & Agrawal, R. K. (2007). Med. Chem. Res. 15, 418–430.  Web of Science CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds