Adeninium 3-carboxy­anilinium bis­(perchlorate) trihydrate

Lamia Bendjeddou; Aouatef Cherouana; Nasreddine Hadjadj; Slimane Dahaoui; Claude Lecomte

doi:10.1107/S1600536809034199

. 2009 Sep 5;65(Pt 10):o2303–o2304. doi: 10.1107/S1600536809034199

Adeninium 3-carboxyanilinium bis(perchlorate) trihydrate

Lamia Bendjeddou ^a,^*, Aouatef Cherouana ^a, Nasreddine Hadjadj ^a, Slimane Dahaoui ^b, Claude Lecomte ^b

PMCID: PMC2970376 PMID: 21577777

Abstract

In the title salt, C₅H₆N₅ ⁺·C₇H₈NO₂ ⁺·2ClO₄ ⁻·3H₂O, the 3-carboxyanilinium and adeninium cations are monoprotonated at the amino group and at a pyrimidine N atom respectively. In the crystal, the components are involved in extensive three-dimensional hydrogen-bonding networks composed of O—H⋯O, N—H⋯O, O—H⋯N, N—H⋯N and C—H⋯O interactions. Bifurcated hydrogen bonds are observed between perchlorate O atoms and adeninium cations.

Related literature

For hydrogen bonds in hybrid compounds, see: Baker et al. (1992 ▶); Richards et al. (1972 ▶). Hydrogen-bonding patterns involving aminopyrimidine and carboxylates have been observed in drug-receptor interactions, protein-nucleic acid interactions and supramolecular architectures, see: Perutz & Ten Eyck (1972 ▶). For their applications in drug design and the crystal engineering of pharmaceuticals, see: Desiraju (1989 ▶). For the use of aminopyrimidine derivatives as antifolate drugs, see: Stanley et al. (2005 ▶); Hunt et al. (1980 ▶). For studies of cation–anion hydrogen-bonding in organic salts of carboxylic acids, see: Bendjeddou et al. (2003 ▶, 2009 ▶); Cherouana et al. (2003 ▶); Moussa Slimane et al. (2009 ▶). For the dependence of bond lengths and angles in adeninium cations on the degree of protonation, see: Hingerty et al. (1981 ▶); Langer & Huml (1978 ▶). For bond angles in unprotonated adenine, see: Voet & Rich (1970 ▶). For the hydrogen-bonding pattern in adeninium perchlorate adenine dihydrate, see: Zeleňák et al. (2004 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For a description of the Cambridge Structural Database, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₅H₆N₅ ⁺·C₇H₈NO₂ ⁺·2ClO₄ ⁻·3H₂O
M _r = 527.24
Triclinic,
a = 8.95610 (10) Å
b = 10.5563 (2) Å
c = 11.7362 (2) Å
α = 71.431 (7)°
β = 85.800 (5)°
γ = 78.192 (4)°
V = 1029.52 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 120 K
0.16 × 0.1 × 0.08 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
55756 measured reflections
6914 independent reflections
5822 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.098
S = 0.97
6914 reflections
316 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶), PARST97 (Nardelli, 1995 ▶), Mercury (Macrae et al., 2006 ▶) and POVRay (Persistence of Vision Team, 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809034199/at2870sup1.cif

e-65-o2303-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809034199/at2870Isup2.hkl

e-65-o2303-Isup2.hkl^{(331.5KB, 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
N1A—H1A⋯O2W	0.86	2.03	2.8135 (13)	151
N1A—H1A⋯O6	0.86	2.54	3.0145 (14)	115
O1M—H1M⋯N7Aⁱ	0.82	1.86	2.6676 (14)	167
N1—H1N⋯O1Wⁱⁱ	0.89	1.86	2.7381 (15)	171
N1—H2N⋯O2W	0.89	1.92	2.8111 (14)	174
N1—H3N⋯O7ⁱⁱⁱ	0.89	2.00	2.8539 (14)	162
N9A—H9A⋯N3A^iv	0.86	2.07	2.9013 (14)	163
O3W—H13W⋯O1^v	0.868 (15)	2.297 (14)	3.0378 (18)	143.5 (13)
O3W—H13W⋯O1Mⁱⁱⁱ	0.868 (15)	2.548 (16)	3.0127 (14)	114.5 (11)
O1W—H21W⋯O4ⁱⁱ	0.843 (15)	2.149 (13)	2.9329 (14)	154.6 (18)
O1W—H21W⋯O7^vi	0.843 (15)	2.49 (2)	3.0553 (14)	124.9 (14)
O2W—H22W⋯O3	0.841 (14)	2.466 (15)	2.9164 (16)	114.5 (13)
O2W—H22W⋯O3ⁱⁱ	0.841 (14)	2.161 (15)	2.9627 (16)	159.3 (16)
O3W—H23W⋯O6	0.869 (17)	2.062 (17)	2.9199 (14)	169.5 (16)
N6A—H61⋯O1W	0.86	2.46	2.9458 (15)	116
N6A—H61⋯O8^vi	0.86	2.33	3.0126 (15)	137
N6A—H62⋯O2M^vii	0.86	1.97	2.8187 (14)	167
C2A—H2A⋯O6	0.93	2.50	3.0047 (15)	115
C2A—H2A⋯O7ⁱⁱⁱ	0.93	2.48	3.2166 (15)	136
C5M—H5M⋯O1ⁱⁱ	0.93	2.52	3.3883 (17)	156
C8A—H8A⋯O5^viii	0.93	2.58	3.2881 (15)	133
C8A—H8A⋯O3W^ix	0.93	2.42	3.1994 (16)	142

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

Acknowledgments

Technical support (X-ray measurements at SCDRX) from Université Henry Poincaré, Nancy 1 is gratefully acknowledged.

supplementary crystallographic information

Comment

Hydrogen bonds of hybrid compounds are of interest because of their widespread biological occurrence (Baker et al., 1992), Richards et al., 1972). Hydrogen-bonding patterns involving aminopyrimidine and carboxylates have been observed in drug-receptor interactions, protein-nucleic acid interactions and supramolecular architectures (Perutz et al., 1972). Studies of such interactions are also of current interest because of their applications in drug design and the crystal engineering of pharmaceuticals (Desiraju et al., 1989). Pyrimidine and aminopyrimidine derivatives are biologically important as they occur in nature as components of nucleic acid. Some aminopyrimidine derivatives are used as antifolate drugs (Stanley et al., 2005; Hunt et al., 1980). The supramolecular networks become especially interesting when the cation and anion can participate in hydrogen-bonding. In this regard previous studies have been concerned with organic salts of carboxylic acids (Bendjeddou et al., 2003; 2009; Cherouana et al., 2003; Moussa Slimane et al., 2009)

Our investigations have focused on the use of perchloric, amino acids and/or nitrogen base acid as a structural building in the synthesis of hydrogen-bonded patterns inorganic-organic high-dimensional structure.

The asymmetric unit of (I) consists of two different monoprotonated adeninium and m-carboxyanilinium cations, two perchlorate anions and three water molecules (Fig. 1). A proton transfer from the perchloric acid to atom N1A of the imidazolyl moiety of adenine base and N1 of m-carboxyalinine acid resulted in the formation of salts. Adeninium cations can be either mono- or diprotonated and the bond lengths and angles are dependent on the degree of protonation (Hingerty et al., 1981; Langer & Huml, 1978). This form contains three basic N atoms, the most basic site is N1, which accepts the first proton, and the next protonation occurs at N7 and then at N3. In the title compound (I), only atom N1 is protonated. This is evident from the increase in the ring angle at the site of protonation, namely N1. The internal angles at N1 is increased from the reported values of 119.8 in unprotonated adenine (Voet & Rich, 1970). The bond lengths and angles of m-carboxyanilinium cation correspond to those expected for the atom types and the type of hybridization (Allen et al., 1987). All bond lengths and angles shows that the two perchlorate anions are tetrahedral.

The title compound is built on the basis of alternating cations and anions chains, the water molecules are sandwiched between them (Fig. 2). In (I), the cationic entities are connected into a two-dimensional hydrogen-bonded network via O—H..N, N—H···N and N—H···O hydrogen bonds, thus generating double layers, the junction between them is ensured by a N1A—H1A···O2w and N1—H2N···O2w hydrogen bonds via a water molecule (H2O(2)), forming a centrosymmetric rings a long [100] axe which can be described by the graph-set motif of R₆³(34) (Bernstein et al., 1995) (Fig. 3a).

The carbonyl O and the carboxyl H atoms participates in hydrogen bonding with a neighbouring adeninium cation through an N—H···O and O—H···N hydrogen bond. The combination of these two hydrogen bonds generates a noncentrosymmetric fused rings which can be described by the graph-set motif of R₂²(9). The adeninium cations are linked by two independents N—H···N hydrogen bonds (Table 3), atom N9A (x, y, z) acts as a hydrogen-bond donor to atom N3A at (-x, 1 - y,-z), so generating a Centrosymmetric ring R₂²(8). A similar pattern was also observed in the crystal structure of adeninium perchlorate adenine dihydrate (Zeleňák, et al., 2004) (Fig. 3 b).

The water molecules plays a pivotal role, they bridges the perchlorate anions as shown in Fig.4, so forming an alternating of R₂²(4) and an R₄⁴(12) rings running parallel to the [100] direction at a = 1/2 & 0 respectively.

The H atoms respectively from protonated atom N1 and atom C2A are involved in bifurcated hydrogen bonding with perchlorate atom O6 to form a five-membered hydrogen-bonded R₂¹(5) ring into a two-dimensional network (Fig.5).

Experimental

The compound was obtained as colourless crystals, after few days, by slow evaporation from an aqueous solution of adenine, m-carboxyphenyl ammonium and perchloric acid in stoechiometric ratio of 1:1:1.