Crystal structure of 4-{[(2,4-di­hydroxy­benzyl­idene)amino]­meth­yl}cyclo­hexane­carb­oxy­lic acid

Muhammad Danish; Saba Akbar; Muhammad Nawaz Tahir; Rabia Ayub Butt; Muhammad Ashfaq

doi:10.1107/S2056989015022343

. 2015 Nov 28;71(Pt 12):o995–o996. doi: 10.1107/S2056989015022343

Crystal structure of 4-{[(2,4-dihydroxybenzylidene)amino]methyl}cyclohexanecarboxylic acid

Muhammad Danish ^a, Saba Akbar ^a, Muhammad Nawaz Tahir ^b,^*, Rabia Ayub Butt ^a, Muhammad Ashfaq ^a

PMCID: PMC4719941 PMID: 26870569

Abstract

In the title compound, C₁₅H₁₉NO₄, the cyclohexyl ring adopts a chair conformation with both exocyclic C—C bonds in equatorial orientations. The dihedral angle between the basal plane of cyclohexyl ring and the 2,4-dihydroxybenzaldehyde moiety is 84.13 (13)°. An intramolecular O—H⋯N hydrogen bonds closes an S(6) ring. In the crystal, O_c—H⋯O_p (c = carboxylic acid, p = phenol) hydrogen bonds link the molecules into [100] C(13) chains whereas an O_p—H⋯O_c hydrogen bond generates [101] C(15) chains. Together, these bonds generate (010) sheets incorporating R ₂ ²(20) loops. Weak C—H⋯O and C—H⋯π interactions also occur.

Keywords: crystal structure, Schiff base, benzaldehyde, hydrogen bonding

Related literature

For the crystal structures of related Schiff bases, see: Shuja et al. (2006 ▸, 2007 ▸); Nisar et al. (2011 ▸).

Experimental

Crystal data

C₁₅H₁₉NO₄
M _r = 277.31
Monoclinic,
a = 6.2399 (17) Å
b = 10.222 (2) Å
c = 22.251 (6) Å
β = 90.232 (8)°
V = 1419.2 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.33 × 0.27 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▸) T _min = 0.970, T _max = 0.988
10670 measured reflections
2580 independent reflections
1222 reflections with I > 2σ(I)
R _int = 0.095

Refinement

R[F ² > 2σ(F ²)] = 0.077
wR(F ²) = 0.214
S = 1.01
2580 reflections
186 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.26 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: SHELXL2014/6 (Sheldrick, 2015 ▸); 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/S2056989015022343/hb7548sup1.cif

e-71-0o995-sup1.cif^{(367.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015022343/hb7548Isup2.hkl

e-71-0o995-Isup2.hkl^{(206.6KB, hkl)}

Click here for additional data file.^{(5.7KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015022343/hb7548Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S2056989015022343/hb7548fig1.tif

View of the title compound with displacement ellipsoids drawn at the 50% probability level. The dotted line represents the intramolecular hydrogen bonding.

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

. DOI: 10.1107/S2056989015022343/hb7548fig2.tif

A partial packing diagram, showig that molecules form Inline graphic (20) and (15) ring motifs. H atoms not involved in hydrogen-bonding interactions are omitted for clarity.

CCDC reference: 1438286

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

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

Cg2 is the centroid of the C10–C15 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.88 (5)	1.58 (5)	2.447 (4)	168 (5)
O3—H3⋯N1	0.82	1.92	2.667 (4)	150
O4—H4⋯O2ⁱⁱ	0.82	1.85	2.669 (4)	174
C9—H9⋯O1ⁱⁱⁱ	0.93	2.42	3.338 (5)	170
C14—H14⋯O3^iv	0.93	2.60	3.499 (5)	164
C5—H5⋯Cg2^v	0.98	2.97	3.772 (5)	140

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by the Ex-Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

S1. Comment

The title compound (I, Fig. 1) is the Schiff base ligand synthesized from tranexamic acid and 2,4-dihydroxybenzaldehyde. The reported crystal structures of the Schiff bases of tranexamic acid are 2-[(4-carboxycyclohexyl)methylammoniomethyl]-6-hydroxyphenolate (Shuja et al., 2006), 4-((E)-(5-bromo-2-hydroxybenzylidene)aminomethyl)cyclohexane-1-carboxylic acid (Shuja et al., 2007) and 4-({[(E)-pyridin-3-ylmethylidene]amino}-methyl)cyclohexanecarboxylic acid (Nisar et al., 2011). The title compound is synthesized for various studies and complexation with different metals.

In (I), the basal plane A (C3/C4/C6/C7) of cyclohexyl ring and the part of 2,4-dihydroxybenzaldehyde B (C9—C14) are planar with r. m. s. deviation of 0.0101 Å and 0.0387 Å, respectively. The dihedral angle between A/B is 84.13 (13)°. The apical C-atoms C2 and C5 are almost at an equal distance of −0.680 (6) Å and 0.648 (6) Å, respectively from the plane A. The carboxylic part C (O1/C1/O2) is oriented at dihedral angles of 31.6 (3)° from planes A.

There exist S(6) ring motif due to O—H···N interactions (Table 1, Fig. 1). Each molecule is linked to four molecules due to O—H···O interactions (Table 1, Fig. 2) with C(13) and C(15) chains. C(13) chains exist from the 2-hydroxy and carboxyl hydroxy groups, where as C(15) chains are created when 4-hydroxy and carbonyl O-atom interlink. The C9—H9···O1ⁱⁱⁱ [iii = −x, −y + 1, −z] interactions generate R₂²(20) ring motif (Table 1, Fig. 2). Similarly, the O4—H4···O2ⁱⁱ [ii = x + 1, −y + 3/2, z + 1/2], C9—H9···O1ⁱⁱⁱ and C14—H14···O3^iv [iv = −x + 1, y − 1/2, −z + 1/2] interactions complete R₃³(15) ring motifs. In this way, the alternate R₃³(15) and R₂²(20) ring motifs stabilize the molecules in the form of two-dimensional network with base vectors [1 0 0], [0 0 1] in the plane (0 1 0). A C—H···π interaction (Table 1) is also involved in the packing.

S2. Experimental

Tranexamic acid (0.786 g, 5 mmol) and 2,4-dihydroxybenzaldehyde (0.661 g, 5 mmol) were disolved in 10 ml distilled water and 10 ml e thanol separately. These mixture were mixed and refluxed for 4 h to yield orange precipitate. The precipitates obtained were filtered and dried from which light orange plates of (I) were obtained after recrystallization in ethanol after one week.

Yield: 83%

Melting point:512 K.