2-Amino­pyrimidinium hydrogen sulfate

Adel Elboulali; Samah Toumi Akriche; Salem S Al-Deyab; Mohamed Rzaigui

doi:10.1107/S1600536811011123

. 2011 Mar 31;67(Pt 4):o1013. doi: 10.1107/S1600536811011123

2-Aminopyrimidinium hydrogen sulfate

Adel Elboulali ^a,^*, Samah Toumi Akriche ^a, Salem S Al-Deyab ^b, Mohamed Rzaigui ^a

PMCID: PMC3099826 PMID: 21754030

Abstract

In the crystal structure of the title compound, C₄H₆N₃ ⁺·HSO₄ ⁻, hydrogen sulfate anions self-assemble through O—H⋯O hydrogen bonds, forming chains along the b axis, while the cations form centrosymmetric pairs via N—H⋯N hydrogen bonds. The 2-aminopyrimidinium pairs are linked to the sulfate anions via N—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (10 Inline graphic ). In addition, weak intermolecular C—H⋯O contacts generate a three-dimensional network.

Related literature

For the biological properties of pyrimidines, see: Rabie et al. (2007 ▶); Rival et al. (1991 ▶). For applications of aminopyrimidines, see: Rospenk & Koll (2007 ▶). For aminopyrimidine salts, see: Hemamalini et al. (2005 ▶); Childs et al. (2007 ▶); Lee et al. (2003 ▶); Ye et al. (2002 ▶). For sulfate salts with organic cations, see: Xu et al. (2009a ▶,b ▶).

Experimental

Crystal data

C₄H₆N₃ ⁺·HSO₄ ⁻
M _r = 193.19
Monoclinic,
a = 8.388 (2) Å
b = 5.208 (3) Å
c = 18.468 (4) Å
β = 112.84 (2)°
V = 743.6 (5) Å³
Z = 4
Ag Kα radiation
λ = 0.56087 Å
μ = 0.22 mm⁻¹
T = 293 K
0.25 × 0.21 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
3738 measured reflections
3647 independent reflections
2520 reflections with I > 2σ(I)
R _int = 0.015
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.159
S = 1.07
3647 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.82 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995) ▶; program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011123/lh5222sup1.cif

e-67-o1013-sup1.cif^{(13.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011123/lh5222Isup2.hkl

e-67-o1013-Isup2.hkl^{(175.2KB, 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⋯O4ⁱ	0.82	1.79	2.6100 (19)	174
N1—H1B⋯O1ⁱⁱ	0.86	2.38	3.140 (2)	148
N1—H1B⋯O4	0.86	2.58	3.155 (2)	125
N1—H1A⋯N3ⁱⁱⁱ	0.86	2.16	3.017 (2)	172
N2—H2⋯O3	0.86	1.91	2.756 (2)	168
C2—H2A⋯O3^iv	0.93	2.40	3.294 (2)	160
C3—H3⋯O2^v	0.93	2.51	3.262 (3)	138
C4—H4⋯O4^vi	0.93	2.53	3.316 (2)	142

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

supplementary crystallographic information

Comment

Substantial attention has recently been focused on pyrimidine and its derivatives for their interesting properties as fungicides, vermicides, insecticides (Rabie et al., 2007), antifungal agents and antiviral agents (Rival et al., 1991). In particular, aminopyrimidines have been recognized as interesting nucleic bases, like cytosine, adenine and guanine which are responsible for molecular recognition and replication of DNA, through the formation and breakage of N—H···N hydrogen bonds (Rospenk & Koll, 2007). In continuation of our research on materials which could have interesting applications we report herein the synthesis and crystal structure of the title compound (I).

The asymmetric unit of the title compound (Fig. 1) consists of one hydrogen sulfate anion and one protonated 2-aminopyrimidine. The crystal packing of (I) is characterized by infinite chains built by HSO₄^- anions extending along the b-direction. These chains are interconnected by cationic moieties via intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) resulting in three-dimensional supra-molecular structure (Fig. 2).

As can be seen in table 1, the O1—H1···O4ⁱ hydrogen bond links two adjacent hydrogen sulfate anions generating corrugated chains stacked along c axis (Fig. 2). In the sulfate anion, the S—O bond [1.569 (2) Å] involving the O atom bearing the acid H atom is longer than the other three S—O bonds, which range from 1.429 (1) to 1.459 (1) Å because of the bond multiplicity and the electronic mesomerism as reported previously in the hydrogen sulfate ion (Xu et al., 2009a,b).

With regard to the organic framework, the neighbouring cations of 2-aminopyrimidine linked by the hydrogen bonds N1–H1A···N3 (2 - x, 1 - y, 1 - z) and N3···H1A–N1 (2 - x, 1 - y, 1 - z) form the cyclic dimer of [C₄N₂H₄NH₂]²⁺₂. The cationic arrangement in crystal structure of 2-amino-4,6-dimethylpyrimidinium hydrogen sulfate (Hemamalini et al., 2005) is closely related to that seen in the title compound. The dimers of the 2-aminopyrimidinium cations with planar rings (r.m.s. deviation = 0.008 Å) are connected to HSO₄^- chains by hydrogen bonds N1–H1B···O4, N1–H1B···O1 (x, y + 1, z) and N2–H2···O3 to form a two-dimensional network (Fig. 2) which is linked into a three-dimensional network through weak intermolecular hydrogen bonds. These observations are similar to that of other 2-aminopyrimidinium salts (Childs et al., 2007; Lee et al., 2003; Ye et al., 2002).

Experimental

To a solution of 2-aminopyrimidine (0.19 g, 2 mmol) dissolved in a mixture of water/ethanol (10/5 ml) was added dropwise 2 mmol (0.15 ml) of commercial H₂SO₄ (98%, Aldrich). The reaction mixture was stirred and left under slowly evaporation at room temperature until formation of large colorless single crystals of the title compound.