4-({[(E)-Pyridin-3-yl­methyl­idene]amino}­meth­yl)cyclo­hexa­necarb­oxy­lic acid

Muhammad Nisar; Ihsan Ali; M Nawaz Tahir; Mughal Qayum; Inamullah Khan Marwat

doi:10.1107/S1600536811011779

. 2011 Apr 7;67(Pt 5):o1058. doi: 10.1107/S1600536811011779

4-({[(E)-Pyridin-3-ylmethylidene]amino}methyl)cyclohexanecarboxylic acid

Muhammad Nisar ^a, Ihsan Ali ^a, M Nawaz Tahir ^b,^*, Mughal Qayum ^c, Inamullah Khan Marwat ^c

PMCID: PMC3089300 PMID: 21754384

Abstract

The title compound, C₁₄H₁₈N₂O₂, contains two geometrically different molecules in the asymmetric unit: the basal plane of the cyclohexane chair and the N-[pyridin-3-ylmethylidene]methanamine moiety are oriented at dihedral angles of 71.77 (7)° and 83.42 (8)°. In the crystal, the molecules are linked by O—H⋯N hydrogen bonds, generating C(13) head-to-tail chains extending along the base vector [103]. R ₂ ²(26) ring motifs are formed due to the C—H⋯·O interactions that link neighbouring chains. There also exist π–π interactions [centroid–centroid separation = 3.6925 (12) Å] between the symmetry-related pyridine rings of one of the independent molecules.

Related literature

For related structures, see: Huh & Lee (2007 ▶): Shahzadi et al. (2007 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₈N₂O₂
M _r = 246.31
Monoclinic,
a = 12.7580 (6) Å
b = 11.2504 (6) Å
c = 18.8088 (7) Å
β = 94.720 (2)°
V = 2690.5 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.34 × 0.25 × 0.22 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.975, T _max = 0.983
24311 measured reflections
6635 independent reflections
3908 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.063
wR(F ²) = 0.207
S = 1.05
6635 reflections
327 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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, 1997 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811011779/hb5830sup1.cif

e-67-o1058-sup1.cif^{(34.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011779/hb5830Isup2.hkl

e-67-o1058-Isup2.hkl^{(318.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N4ⁱ	0.82	1.87	2.682 (2)	171
O3—H3⋯N2ⁱⁱ	0.82	1.89	2.685 (2)	164
C11—H11⋯O2ⁱⁱⁱ	0.93	2.56	3.478 (3)	168
C13—H13⋯O2^iv	0.93	2.57	3.316 (3)	137
C27—H27⋯O4^v	0.93	2.45	3.280 (3)	148

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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 the diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

Comment

The title compound (I, Fig. 1) has been prepared for the study of biological studies and for the synthesis of metallic complexes.

The crystal structure of (II) i.e., 4-(aminomethyl)cyclohexane-1-carboxylic acid (Shahzadi et al., 2007) and (III) i.e., N,N^'-bis(pyridin-3-ylmethylene)cyclohexane-trans-1,4-diamine (Huh & Lee, 2007) have been published which are related to the title compound.

The title compound consists of two molecules in the crystallographic asymmetric unit which differ from each other geometrically. In one molecules, the basal plane A (C3/C4/C6/C7) of cyclohexane and N-[pyridin-3-ylmethylidene]methanamine moiety B (C8—C14/N1/N2) are almost planar with r.m.s. deviation of 0.014 and 0.034 Å, respectively. The dihedral angle between A/B is 71.77 (7)°. The carboxylate group C (O1/C1/O2) is of course planar. The dihedral angle between A/C and B/C is 30.07 (15)° and 53.36 (15)°, respectively. In second molecules, the basal plane D (C17/C18/C20/C21) of cyclohexane and N-[pyridin-3-ylmethylidene]methanamine moiety E (C22—C28/N3/N4) are also almost planar with r.m.s. deviation of 0.006 and 0.047 Å, respectively. The dihedral angle between D/E is 83.42 (8)°. The carboxylate group F (O3/C15/O4) makes dihedral angle of 30.03 (26)° and 62.40 (14)° with D and E, respectively.

In the crystal, the molecules are stabilized in the form of infinite C(13) polymeric chains due to O—H···.N H-bonds (Table 1, Fig. 2) extending along the base vector [103]. Due to intermolecular H-bonding of C—H···.O type (Table 1, Fig. 2) ring motifs (Bernstein et al., 1995) R₂²(26) are formed. The molecules are further stabilized by the π···π interaction between the symmetry related pyridine ring (C24/C25/N4/C26/C27/C28) at a distance of 3.6925 (12) Å.

Experimental

A two-necked reaction flask equipped with a reflux condenser, serum cap and a magnet bar was charged with a methanolic solution (40 ml) of tranexamic acid (0.157 g, 1 mmol) and pyridine-3-carboxaldehyde (0.107 g, 1 mmol) at room temperature under nitrogen atmosphere. An excess amount of triethylamine (1 ml) was dropped into the reaction mixture through a serum cap and subsequently the reaction mixture was refluxed for about 20 h. The disappearance of the starting materials was ascertained by TLC (methanol:chloroform). After completion of the reaction, an equivalent quantity of glacial acetic acid was added to the mixture to ensure neutralization of triethylamine. Later on, the crude mixture was allowed to stand overnight which resulted gradually into crystallized material. The solid was collected by suction filtration, washed with diethyl ether and recrystalized from hot methanol to give colourless prisms of (I).