The crystal structure of 2-[5-(di­methyl­amino)­naphthalene-1-sulfonamido]­phenyl 5-(di­methyl­amino)­naphthalene-1-sulfonate

Kittipong Chainok; Tanwawan Duangthongyou; Thawatchai Tuntulani; Apinya Chuenka; Boontana Wannalerse

doi:10.1107/S2056989015016199

. 2015 Sep 12;71(Pt 10):o721–o722. doi: 10.1107/S2056989015016199

The crystal structure of 2-[5-(dimethylamino)naphthalene-1-sulfonamido]phenyl 5-(dimethylamino)naphthalene-1-sulfonate

Kittipong Chainok ^a, Tanwawan Duangthongyou ^b, Thawatchai Tuntulani ^c, Apinya Chuenka ^d, Boontana Wannalerse ^d,^*

PMCID: PMC4647440 PMID: 26594442

Abstract

The complete molecule of the title compound, C₃₀H₂₉N₃O₅S₂, is generated by a crystallographic twofold axis: the O atom and NH group attached to the central benzene ring are statistically disordered. The dihedral angle between the naphthalene ring system and the central benzene ring is 52.99 (6)°, while the pendant naphthalene ring systems subtend a dihedral angle of 68.17 (4)°. An intramolecular C—H⋯O hydrogen bond closes an S(6) ring. In the crystal, the molecules are linked by weak C—H⋯O hydrogen bonds.

Keywords: crystal structure, dansyl derivatives, disorder, hydrogen bonding, π-stacking

Related literature

For the use of dansyl tags to monitor biological activity in enzyme systems, see: Brown et al. (1970 ▸); Liu et al. (2010 ▸). Dansyl-conjugated liposome has been used to modulate the fluorescence resonance energy transfer (FRET) mechanism, see: Li et al. (2006 ▸). Dansyl fluorogenic sensors have been used for the recognition and detection of targets such as cationic and anionic species, see: Cao et al. (2014 ▸); Jisha et al. (2009 ▸); Bhalla et al. (2007 ▸). For crystal structures of dansyl derivatives, see: Bhatt et al. (2011 ▸); Zhang et al. (2009 ▸) and of metal–calix[4]arene complexes bearing two dansyl carboxamide units, see: Buie et al. (2008 ▸). graphic file with name e-71-0o721-scheme1.jpg

Experimental

Crystal data

C₃₀H₂₉N₃O₅S₂
M _r = 575.68
Monoclinic,
a = 12.7594 (13) Å
b = 13.3481 (14) Å
c = 16.4331 (17) Å
β = 98.349 (4)°
V = 2769.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 K
0.26 × 0.22 × 0.22 mm

Data collection

Bruker D8 QUEST CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T _min = 0.698, T _max = 0.746
17644 measured reflections
3444 independent reflections
2246 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.113
S = 1.03
3444 reflections
186 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXT (Sheldrick, 2015a ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015016199/gw2153sup1.cif

e-71-0o721-sup1.cif^{(536.4KB, cif)}

Structure factors: contains datablock(s) bw6. DOI: 10.1107/S2056989015016199/gw2153Isup2.hkl

e-71-0o721-Isup2.hkl^{(189.2KB, hkl)}

Click here for additional data file.^{(5.1KB, cdx)}

Supporting information file. DOI: 10.1107/S2056989015016199/gw2153Isup3.cdx

Click here for additional data file.^{(10.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015016199/gw2153Isup4.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015016199/gw2153fig1.tif

The molecular structure of the title compound with 30% probability ellipsoids and atom numbering. Hydrogen atoms are omitted for clarity.

Click here for additional data file.^{(2MB, tif)}

. DOI: 10.1107/S2056989015016199/gw2153fig2.tif

The crystal packing of the title compound, viewed along the [110] direction.

CCDC reference: 1421273

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
C7H7O3	0.93	2.37	3.030(2)	128
C13H13O3ⁱ	0.93	2.73	3.386(2)	129

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Thailand Research Fund (MRG 5580182), the Center of Excellence for Innovation in Chemistry (PERCH-CIC), Commission on Education, Ministry of Education, Kasetsart University Research and Development Institute and the Department of Chemistry, Faculty of Science, Kasetsart University for financial support.

supplementary crystallographic information

S1. Introduction

Dansyl derivatives can be widely used as fluorescence probes in biological and environmental systems. Dansyl tags have been increasingly used to monitor biological activities in the enzyme system for providing the accurate information (Brown et al., 1970; Liu et al., 2010). An example is dansyl-conjugated liposome for modulating fluorescence resonance energy transfer (FRET) mechanism (Li et al. 2006). Furthermore, dansyl fluorogenic sensors were prepared for recognition and detection of many targets such as cationic and anionic species (Cao et al., 2014; Jisha et al., 2009; Bhalla et al., 2007). Crystal structures of dansyl derivatives (Bhatt et al., 2011; Zhang et al., 2009) and metal complexes of calix[4]arene bearing two dansyl carboxamide units have been reported (Buie et al., 2008).

S2. Synthesis and crystallization

The title compound was synthesized by condensation of 2-aminophenol (0.55 g, 5.04 mmol) and dansyl chloride (2.72 g, 10.08 mmol) using potassium carbonate (17.27 g, 12.50 mmol) as a base in acetonitrile (30 ml). The solution was heated and stirred under N₂ atmosphere for 24 h. The solvent was then removed by a rotary evaporator. Water (10 ml) was added to the residue and the organic phase was extracted with dichloromethane (3 x 20 ml). The organic layer was dried with Na₂SO₄. The product was purified by column chromatography using dichloromethane as an eluent. The solvent was evaporated to afford a yellow crystalline solid in 55% yield. Single crystals suitable for X-ray measurements were obtained by recrystallization using the mixture solution of dichloromethane and hexane (1:1, v/v) at room temperature.

S3. Refinement

Atom O1 and the N1H1 group attached to the central benzene ring are statistically disordered and were refined with the occupancies of the N, H and O atoms fixed at 0.5. All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 Å for aryl and 0.96 Å for methyl H atoms, U_iso (H) = 1.2U_eq (C) for aryl and 1.5U_eq (C) for methyl H atoms. The N-bound H-atom was refined with N—H = 0.86 Å, and with U_iso(H) = 1.2U_eq(N).