Crystal structure of 5,5′-bis­(di­methyl­amino)-N,N′-(3-methyl-3-aza­pentane-1,5-di­yl)di(naphthalene-1-sulfonamide)

Toyketa V Horne; Syed A Haque; Adrianne Barton; Md Alamgir Hossain

doi:10.1107/S2056989015021714

. 2015 Nov 21;71(Pt 12):o959–o960. doi: 10.1107/S2056989015021714

Crystal structure of 5,5′-bis(dimethylamino)-N,N′-(3-methyl-3-azapentane-1,5-diyl)di(naphthalene-1-sulfonamide)

Toyketa V Horne ^a, Syed A Haque ^a, Adrianne Barton ^a, Md Alamgir Hossain ^a,^*

PMCID: PMC4719922 PMID: 26870550

Abstract

In the title compound, C₂₉H₃₇N₅O₄S₂, two arms substituted with dansyl derivatives are connected to a central tertiary amine, where the dihedral angle between the planes of two dansyl units is 56.39 (4)°. Each arm contains a sulfonamide functional group and both N—H groups in the compound are pointed to the same side. The central part of the molecule is disordered over three sets of sites with a refined occupancy ratio of 0.547 (4):0.328 (4):0.125 (3). No intramolecular π–π or hydrogen-bonding interactions are observed. In the crystal, molecules are linked via pairs of N—H⋯O interactions involving the same acceptor atom, forming inversion dimers. In addition, C—H⋯O interactions exist between molecules, providing further stabilization of dimers.

Keywords: crystal structure, sulfonamide, dansyl derivative, hydrogen bonding

Related literature

For general background to anion binding, see: Hossain (2008 ▸). For sulfonamide-based compounds as anion receptors, see: Kavallieratos et al. (2005 ▸). For related compounds, see: Basaran et al. (2015 ▸). For the antibacterial activity of sulfonamide-based compounds as drugs, see: Brackett et al. (2004 ▸). graphic file with name e-71-0o959-scheme1.jpg

Experimental

Crystal data

C₂₉H₃₇N₅O₄S₂
M _r = 583.75
Triclinic,
a = 10.5216 (5) Å
b = 11.3826 (5) Å
c = 13.9579 (6) Å
α = 107.8976 (7)°
β = 90.3662 (8)°
γ = 113.7328 (7)°
V = 1439.89 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.40 × 0.32 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▸) T _min = 0.914, T _max = 0.964
13576 measured reflections
7004 independent reflections
5916 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.122
S = 1.00
7004 reflections
466 parameters
655 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.06 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: APEX2 (Bruker, 1998 ▸); cell refinement: SAINT (Bruker, 1998 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▸); software used to prepare material for publication: SHELXL2014.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015021714/ds2245sup1.cif

e-71-0o959-sup1.cif^{(486KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015021714/ds2245Isup2.hkl

e-71-0o959-Isup2.hkl^{(556.4KB, hkl)}

Click here for additional data file.^{(11.2KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015021714/ds2245Isup3.cml

Click here for additional data file.^{(386.7KB, tif)}

. DOI: 10.1107/S2056989015021714/ds2245fig1.tif

The molecular structure of the title compound (1) showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level (The minor components of the primed and double primed atoms are not shown for clarity).

Click here for additional data file.^{(2.3MB, tif)}

a . DOI: 10.1107/S2056989015021714/ds2245fig2.tif

A unit cell of the title compound as viewed along the a axis showing hydrogen bonding interactions as dashed lines.

CCDC reference: 1437206

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
N4A—H4A⋯O7B ⁱ	0.88 (2)	2.38 (2)	3.223 (2)	162 (2)
C20A—H20B⋯N4A ⁱⁱ	0.98	2.60	3.494 (2)	152
C2B"—H2B6⋯O6B ⁱ	0.99	2.54	3.359 (13)	140
N4B—H4B⋯O7B ⁱ	0.84 (2)	2.41 (2)	3.2108 (19)	159 (2)
C9B—H9B⋯O7A ⁱ	0.95	2.44	3.147 (2)	131
C21—H21B⋯O6B ⁱ	0.98	2.65	3.203 (4)	116

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The National Science Foundation is acknowledged for a CAREER award (CHE-1056927) to MAH. The NMR core facility at Jackson State University is supported by the National Institutes of Health (G12RR013459). AB was supported by the National Institutes of Health (NIH)–Minority Access to Research Careers/Undergraduate Student Training in Academic Research (NIH-MARC/U*STAR) Program (grant No. 5 T34GM007672–34). The authors thank Dr Douglas R. Powell at the University of Oklahoma for the X-ray analysis of this compound.

supplementary crystallographic information

S1. Chemical context

Sulfonamide-based compounds are potential receptors for anions interacting via hydrogen bonding interactions under neutral conditions (Kavallieratos, et al. 2005). This class of compounds are also known to possess antibacterial activities and widely used as antibiotics (Brackett et al. 2004). Previous studies suggest that tweezer-type compounds are effective in binding a variety of anions in solution (Basaran, et al. 2015). As a part of our ongoing research on anion chemistry (Hossain, 2008), we have been interested in synthesizing sulfonamide-based neutral receptors. Herein, we report the crystal structure of the title compound, which is being studied in order to explore its ability to bind anions.

S2. Structural commentary

The molecule adopts a bowl-like shape with the dihedral angle of 56.39 ° between the planes of two dansyl units. The hydrogen atoms of NH groups are positioned at the same side in the compound and are pointed inside the cavity formed by the NH—C—C—N—C—C—N chain of the central part (Fig. 1). TheC-N and C—C bond lengths in the aliphatic groups are in the range of 1-451 (3) to 1.491 (5) Å and 1.484(10 to 1.539 (4) Å, respectively; which are consistent with the literature value (Basaran, et al. 2015). The central part of the molecule containing N1, C2A, C3A, C2B, C3B, and C21 is disordered and chemically-equivalent distances are set to be approximately the same. Displacement parameters of disordered atoms are set to be approximately the same along each chemical bond. The sum of the three occupancies is set to 1.0. Details of the specific restraints are available in the *.cif. No intramolecular π–π or hydrogen bonding interactions are observed. However, two molecules are linked via NH···O interactions [2.28 (2)–2.41 (2) Å] from two NH groups of one molecule with one oxygen group of other molecule (Fig. 2).

S3. Synthesis and crystallization

2,2'-Diamino-N-methyldiethylamine (0.20 g, 1.71 mmol) and dansyl chloride (0.92 g, 3.43 mmol) were dissolved separately in 100 mL of CH₃CN. The solution of dansyl chloride was added dropwise to the solution of 2,2'-diamino-N-methyldiethylamine containing K₂CO₃ (1.0 g) in a round bottom flask under constant stirring at room temperature. The mixture was allowed to stir over night at room temperature and the clear solution was separated by filtration. The solvent was evaporated under reduced pressure, and the product was purified by column chromatography on neutral alumina using 2% methanol in dichloromethane. The greenish yellow powder thus obtained was redissolved in methanol and crystals suitable for X-ray analysis were grown from the slow evaporation of the solvent.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms on C were placed in idealized positions with C—H distances 0.95 - 0.99 Å and thereafter treated as riding. The coordinates of those on N were refined. U_iso for H was assigned as 1.2 times U_eq of the attached atom (1.5 for methyl). A torsional parameter was refined for each methyl group. The largest residual density peak was 1.50 Å from O2.