6-(4-Methyl­phen­yl)-1,3,5-triazine-2,4-di­amine–benzoic acid (1/1)

Kaliyaperumal Thanigaimani; Nuridayanti Che Khalib; Ibrahim Abdul Razak; Palanisamy Lavanya; Kasthuri Balasubramani

doi:10.1107/S1600536813013883

. 2013 May 25;69(Pt 6):o968–o969. doi: 10.1107/S1600536813013883

6-(4-Methylphenyl)-1,3,5-triazine-2,4-diamine–benzoic acid (1/1)

Kaliyaperumal Thanigaimani ^a, Nuridayanti Che Khalib ^a, Ibrahim Abdul Razak ^a,^*,^‡, Palanisamy Lavanya ^b, Kasthuri Balasubramani ^b

PMCID: PMC3685106 PMID: 23795125

Abstract

The benzoic acid molecule of the title adduct, C₁₀H₁₁N₅·C₇H₆O₂, is approximately planar, with a dihedral angle of 7.2 (3)° between the carboxylic acid group and the benzene ring. In the triazine molecule, the plane of the triazine ring makes a dihedral angle of 28.85 (9)° with that of the adjacent benzene ring. In the crystal, the two components are linked by N—H⋯O and O—H⋯N hydrogen bonds with an R ₂ ²(8) motif, thus generating a 1 + 1 unit of triazine and benzoic acid molecules. The acid–base units are further connected by N—H⋯N hydrogen bonds with R ₂ ²(8) motifs, forming a supramolecular ribbon along [101]. The crystal structure also features weak π–π [centroid–centroid distances = 3.7638 (12) and 3.6008 (12) Å] and C—H⋯π interactions.

Related literature

For the biological activity of triazine derivatives, see: Bork et al. (2003 ▶). For related structures, see: Thanigaimani et al. (2007 ▶, 2012a ▶,b ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-69-0o968-scheme1.jpg

Experimental

Crystal data

C₁₀H₁₁N₅·C₇H₆O₂
M _r = 323.36
Triclinic,
a = 7.4324 (5) Å
b = 10.9717 (3) Å
c = 11.2267 (3) Å
α = 117.202 (1)°
β = 101.645 (2)°
γ = 94.032 (2)°
V = 783.47 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100 K
0.53 × 0.43 × 0.21 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.952, T _max = 0.980
16402 measured reflections
4578 independent reflections
3744 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.157
S = 1.11
4578 reflections
238 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(25.5KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813013883/is5271sup1.cif

e-69-0o968-sup1.cif^{(25.5KB, cif)}

Click here for additional data file.^{(224.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813013883/is5271Isup2.hkl

e-69-0o968-Isup2.hkl^{(224.3KB, hkl)}

Click here for additional data file.^{(6.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813013883/is5271Isup3.cml

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

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

Cg2 is the centroid of the C2–C7 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H1N4⋯N2ⁱ	0.839 (19)	2.19 (2)	3.021 (2)	172 (2)
N4—H2N4⋯O2ⁱⁱ	0.86 (3)	2.11 (3)	2.965 (3)	172 (3)
N5—H1N5⋯N3ⁱⁱⁱ	0.85 (3)	2.14 (3)	2.984 (3)	169 (3)
O1—H1O1⋯N1^iv	0.83 (3)	1.80 (3)	2.613 (2)	167 (3)
C1—H1B⋯Cg2^v	0.98	2.75	3.661 (2)	156

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

Acknowledgments

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and USM Short Term Grant (No. 304/PFIZIK/6312078) to conduct this work. KT thanks The Academy of Sciences for the Developing World and USM for a TWAS–USM fellowship.

supplementary crystallographic information

Comment

Triazine derivatives show antitumor activity, as well as a broad range of biological activities, such as anti-angiogenesis and antimicrobial effects (Bork et al., 2003). Related crystal structures of 2,4-diamino-6-phenyl-1,3,5-triazine- sorbic acid (1/1) (Thanigaimani et al., 2007), 6-(4-methoxyphenyl)-1,3,5-triazine-2,4-diamine (Thanigaimani et al., 2012a) and adipic acid-2.4-diamino- 6-(4-methoxyphenyl)-1,3,5-triazine (1/2) (Thanigaimani et al., 2012b) have been reported. In the present study, hydrogen-bonding patterns in the 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine-benzoic acid (1/1) co-crystal are investigated.

The asymmetric unit (Fig. 1) contains one 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine molecule and one benzoic acid molecule. The dihedral angle between the triazine ring [N1/C10/N2/C8/N3/C9, maximum deviation = 0.006 (2) Å for atoms N2 & C10] and the plane formed by the benzoic acid molecule (O1/O2/C11–C17) is 11.16 (7)°. The triazine ring forms dihedral angle of 28.85 (9)° with the benzene ring (C2–C7). The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal (Fig. 2), the triazine molecules are base-paired [with a graph-set (Bernstein et al., 1995) of R₂²(8)] on either side via N4—H1N4···N2ⁱ and N5—H1N5···N3ⁱⁱⁱ hydrogen bonds (symmetry codes in Table 1), forming a supramolecular ribbon. Each triazine molecule interacts with the carboxyl group of benzoic acid molecule via N4—H2N4···O2ⁱⁱ and O1—H1O1···N1^iv hydrogen bonds (symmetry codes in Table 1), generating R₂²(8) ring motifs. The crystal structure is further stabilized by π–π interactions between the benzene (Cg2; C2–C7) rings [Cg2···Cg2= 3.7638 (12) Å; 1 - x, -y, 1 - z] and that between triazine (Cg1; N1/C9/N3/C8/N2/C10) and benzene rings (Cg3; C12–C17) [Cg1···Cg3= 3.6008 (12) Å; 2 - x,1 - y, 1 - z] and C—H···π interactions (Table 1) involving the C2–C7 (centroid Cg2) ring.

Experimental

Hot methanol solutions (20 ml) of 2,4-diamino-6-(4-methylphenyl)-1,3,5-triazine (50 mg, Aldrich) and benzoic acid (31 mg, Aldrich) were mixed and warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound (I) appeared after a few days.