Crystal structure of 4-{[(naphthalen-2-yl)sulfonyl­amino]­meth­yl}cyclo­hexa­necarb­oxy­lic acid

Muhammad Danish; Muhammad Nawaz Tahir; Asif Hussain; Muhammad Ashfaq; Muhammad Nadeem Sadiq

doi:10.1107/S2056989015002054

. 2015 Feb 4;71(Pt 3):o145. doi: 10.1107/S2056989015002054

Crystal structure of 4-{[(naphthalen-2-yl)sulfonylamino]methyl}cyclohexanecarboxylic acid

Muhammad Danish ^a, Muhammad Nawaz Tahir ^b,^*, Asif Hussain ^a, Muhammad Ashfaq ^a, Muhammad Nadeem Sadiq ^a

PMCID: PMC4350692 PMID: 25844218

Abstract

The title compound, C₁₈H₂₁NO₄S, is a new sulfonamide derivative of tranexamic acid. In the crystal, molecules form inversion dimers via O—H⋯O hydrogen bonds involving the carboxylic acid groups. Hydrogen bonding between the sulfonamide N—H group and the carboxylic acid O atom assembles the dimers into thick layers parallel to (100). The naphthalene groups of adjacent layers are arranged in a herring-bone motif. There are C—H⋯π interactions between the naphthalene rings of neighbouring layers.

Keywords: crystal structure, sulfonamides, tranexamic acid, hydrogen bonding, C—H⋯π interactions

Related literature

For related structures, see: Ashfaq et al. (2011a ▸,b ▸). graphic file with name e-71-0o145-scheme1.jpg

Experimental

Crystal data

C₁₈H₂₁NO₄S
M _r = 347.42
Monoclinic,
a = 16.5301 (13) Å
b = 6.0573 (4) Å
c = 17.0036 (12) Å
β = 100.810 (4)°
V = 1672.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.40 × 0.22 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.920, T _max = 0.956
13364 measured reflections
3636 independent reflections
2315 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.117
S = 1.02
3636 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.36 e Å⁻³

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 for Windows (Farrugia, 2012 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸) and PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015002054/gk2626sup1.cif

e-71-0o145-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002054/gk2626Isup2.hkl

e-71-0o145-Isup2.hkl^{(199.6KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015002054/gk2626Isup3.cml

Click here for additional data file.^{(1MB, tif)}

. DOI: 10.1107/S2056989015002054/gk2626fig1.tif

View of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H-atoms are shown by small circles of arbitrary radii.

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015002054/gk2626fig2.tif

View of the crystal packing in the title compound with hydrogen bonds shown as dashed lines.

CCDC reference: 1046512

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

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg2 are the centroids of the C9C12/C17/C18 and C12C17 rings, respectively.

DHA	DH	HA	D A	DHA
O1H1O2ⁱ	0.82	1.83	2.623(2)	163
N1H1AO2ⁱⁱ	0.86	2.46	3.043(2)	124
C11H11Cg1ⁱⁱⁱ	0.93	2.91	3.639(3)	137
C13H13Cg2ⁱⁱⁱ	0.93	2.82	3.527(3)	134

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

Acknowledgments

The authors acknowledge the provision of funds by the Higher Education Commission, Islamabad, Pakistan for project (P-2549).

supplementary crystallographic information

S1. Structural commentary

The title compound (Fig. 1), a derivative of tranexamic acid, was prepared as a part of our studies on sulfonamides. It is also planned to use this compound for complexing metal ions. The crystal structures of similar compounds have been reported earlier [4-((((4-methylphenyl)sulfonyl)amino)methyl)cyclohexanecarboxylic acid (Ashfaq et al., 2011a); 4-((4-methoxybenzenesulfonamido)methyl)cyclohexane-1- carboxylic acid (Ashfaq et al., 2011b).

The cyclohexyl ring of tranexamic acidic moiety is in a chair form. The atoms forming the basal plane A (C3/C4/C6/C7) are co-planar (r. m.s deviation of 0.0032 Å). The C2 and C5 atoms are at a distance of 0.653 (3) and 0.678 (3) Å from the plane A. The naphthalene ring B (C9—C18) is also planar with r. m.s deviation of 0.0051 Å. The dihedral angle between A/B is 45.76 (6)°. The carboxylic group is oriented at a dihedral angle of 38.5 (2)° with the plane A. The molecules form centrosymmetric dimers due to O—H···O type hydrogen bonds of the carboxylic groups and complete R₂²(8) ring motif. The dimers are interlinked through N—H···O bonds (Table 1, Fig. 2) completing R₂²(22) ring motif to form two dimensional polymeric network parallel to (100). There are C—H···π (Table 1) interactions between the naphthalene rings from neighboring (100) layers.

S2. Synthesis and crystallization

The title compound was prepared from 2-naphthalenesulfonyl chloride (1 mmol, 0.226 g) and tranexamic acid(1 mmol, 0.157 g) added to 20 ml of distilled water. The mixture was constantly stirred and its pH was maintained at 8–9 by using 1 M sodium bicarbonate solution. Completion of the reaction after 3 h was confirmed by observing clear solution. The final product was precipitated by adding 0.1 M HCl solution, separated and recrystallized from ethanol-water mixture in 1:1 volume ratio. Colorless needles suitable for X-ray data collection were obtained after one week (yield: 59%, m.p. 483 K).

S3. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 1. The H-atoms were positioned geometrically (C–H = 0.93—0.98 Å, N–H = 0.86 Å, O–H = 0.82 Å) and refined as riding with U_iso(H) = xU_eq (C, N, O), where x = 1.5 for hydroxy and x = 1.2 for all other H-atoms.