2,4-Diamino-6-methyl-1,3,5-triazin-1-ium hydrogen oxalate

Leila Narimani; Bohari M Yamin

doi:10.1107/S1600536812016637

. 2012 Apr 21;68(Pt 5):o1475. doi: 10.1107/S1600536812016637

2,4-Diamino-6-methyl-1,3,5-triazin-1-ium hydrogen oxalate

Leila Narimani ^a, Bohari M Yamin ^a,^*

PMCID: PMC3344586 PMID: 22590348

Abstract

The title compound, C₄H₈N₅ ⁺·C₂HO₄ ⁻, was obtained from the reaction of oxalic acid and 2,4-diamino-6-methyl-1,3,5-triazine. The protonated triazine ring is essentially planar with a maximum deviation of 0.035 (1) Å, but the hydrogen oxalate anion is less planar, with a maximum deviation of 0.131 (1) Å for both carbonyl O atoms. In the crystal, the ions are linked by intermolecular N—H⋯O, N—H⋯N, O—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network. Weak π–π [centroid–centroid distance = 3.763 Å] and C—O⋯π interactions [O⋯centroid = 3.5300 (16) Å, C—O⋯centroid = 132.19 (10)°] are also present.

Related literature

For bond-length data see: Allen et al. (1987 ▶) and for a description of the Cambridge Structural Database, see: Allen (2002 ▶). For background to triazine derivatives, see: Sebenik et al. (1989 ▶). For related structures, see: Kaczmarek et al. (2008 ▶); Xiao (2008 ▶); Fan et al. (2009 ▶); Qian & Huang (2010 ▶).

Experimental

Crystal data

C₄H₈N₅ ⁺·C₂HO₄ ⁻
M _r = 215.18
Triclinic,
a = 5.6208 (12) Å
b = 7.9828 (17) Å
c = 10.857 (2) Å
α = 76.846 (4)°
β = 75.882 (4)°
γ = 75.954 (4)°
V = 450.92 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 K
0.50 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.935, T _max = 0.974
5551 measured reflections
1959 independent reflections
1708 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.113
S = 1.03
1959 reflections
145 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812016637/zq2157sup1.cif

e-68-o1475-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016637/zq2157Isup2.hkl

e-68-o1475-Isup2.hkl^{(96.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812016637/zq2157Isup3.cml

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
N3—H3⋯O1ⁱ	0.95 (2)	1.77 (2)	2.7134 (17)	174 (2)
N3—H3⋯O4ⁱ	0.95 (2)	2.50 (2)	2.9841 (17)	111.7 (16)
O4—H4⋯O2	0.83 (2)	1.66 (2)	2.4921 (16)	175 (2)
N4—H4D⋯O3ⁱⁱ	0.86	2.17	2.9902 (19)	160
N4—H4E⋯N1ⁱⁱⁱ	0.86	2.18	3.0399 (19)	174
N5—H5A⋯N2^iv	0.86	2.14	3.0027 (19)	179
N5—H5B⋯O2^v	0.86	2.28	2.8558 (17)	124
N5—H5B⋯O3^v	0.86	2.59	3.2337 (19)	133
C4—H4C⋯O1^vi	0.96	2.49	3.339 (2)	148

Open in a new tab

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

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Kebangsaan Malaysia for the research grants UKM-GUP-NBT-68–27–110.

supplementary crystallographic information

Comment

It is known that many triazine derivatives possess biological properties beside its usefullness as intermediates in the pharmaceutical industry (Sebenik et al., 1989). 2,4-diamino-6-1,3,5-triazine has been reported to co-crystallize with methanol (Kaczmarek et al., 2008) and ethanol (Xiao, 2008). On the other hand, the triazine nitrogen atom at position 1 can be easily protonated as in compound (C₄H₈N₅)Cl (Qian & Huang, 2010) and (C₄H₈N₅)NO₃ (Fan et al., 2009) which were obtained from the normal acid-base reaction. The title compound is a similar salt but having a hydrogen oxalate as counter anion (Fig.1). The non hydrogen triazine ring, C1/N1/C2/N2/C3/N3, is planar with a maximum deviation of 0.035 (1) Å from the least square plane for N3 atom. The hydrogen oxalate anion O1/C1/O2/C2/O3/O4, is less planar with a maximum deviation of 0.131 (1) Å for O1 and O4 atoms. The bond lengths and angles are in normal ranges (Allen et al., 1987; Allen, 2002). In the crystal structure the molecules are linked by N—H···O, N—H···N, O—H···O and C—H···O intermolecular hydrogen bonds (symmetry codes as in Table 2) to form a three-dimensional network (Fig. 2). In addition, there are weak π–π interactions between the triazine ring centroids Cg1 (symmetry code: 1-x, -y, 1-z) with a distance of 3.763 Å and a C6—O3···π involving the triazine (C1/N1/C2/N2/C3/N3) centroid (symmetry code: 1-x, 1-y, 1-z) with a O3···Cg1 distance of 3.5300 (16) Å and a C6—O3—Cg1 bond angle of 132.19 (10)°.

Experimental

10 ml aqueous solution of ammonium thiocyanate (0.152 g, 2 mmol) was added into a beaker containing oxalate acid (0.126 g, 1 mmol) and 2,4-diamino- 6-methyl-1,3,5-triazine (2 mmol) in 40 ml distilled water. After one week of evaporation at room temperature colourless crystals were obtained. Yield 92%; Melting point: 457.1–458.3 K.