3-Amino-2-methyl-4-oxo-3,4-dihydro­quinazolin-1-ium p-toluene­sulfonate monohydrate

Mohammad Arfan; M Nawaz Tahir; Rasool Khan; Mohammad S Iqbal

doi:10.1107/S1600536809013841

. 2009 Apr 18;65(Pt 5):o1051. doi: 10.1107/S1600536809013841

3-Amino-2-methyl-4-oxo-3,4-dihydroquinazolin-1-ium p-toluenesulfonate monohydrate

Mohammad Arfan ^a, M Nawaz Tahir ^b,^*, Rasool Khan ^a, Mohammad S Iqbal ^c

PMCID: PMC2977733 PMID: 21583869

Abstract

In the title hydrated molecular salt, C₉H₁₀N₃O⁺·C₇H₇O₃S⁻·H₂O, the cation is protonated at a quinazolinone N atom and an intramolecular N—H⋯O hydrogen bond occurs. In the crystal structure, intermolecular N—H⋯O and O—H⋯O hydrogen bonds and C—H⋯O, C—H⋯π and weak aromatic π–π stacking interactions [centroid–centroid separations = 3.8648 (12) and 3.9306 (13) Å] help to establish the packing; a short S=O⋯π contact is also seen.

Related literature

For a related structure, see: Atkinson & Meades (2000 ▶). For background on the properties of cyclic amidines and quinazolinones, see: Glaser & Traber (1984 ▶); Havera (1979 ▶); Hori et al. (1990 ▶); Liverton et al. (1998 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₉H₁₀N₃O⁺·C₇H₇O₃S⁻·H₂O
M _r = 365.40
Monoclinic,
a = 20.838 (1) Å
b = 6.2769 (3) Å
c = 14.7897 (7) Å
β = 116.676 (1)°
V = 1728.56 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.28 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.935, T _max = 0.958
9546 measured reflections
4390 independent reflections
3952 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.091
S = 1.00
4390 reflections
243 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ▶), 2109 Friedal pairs
Flack parameter: 0.04 (5)

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 (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/S1600536809013841/hb2950sup1.cif

e-65-o1051-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013841/hb2950Isup2.hkl

e-65-o1051-Isup2.hkl^{(210.8KB, 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
N1—H1⋯O4ⁱ	0.89 (3)	1.89 (3)	2.734 (3)	158 (3)
N3—H3A⋯O1	0.83 (3)	2.31 (4)	2.693 (3)	109 (3)
N3—H3B⋯O3ⁱⁱ	0.86 (3)	2.22 (3)	2.963 (3)	146 (3)
O5—H5A⋯O3ⁱ	0.73 (5)	2.16 (5)	2.871 (3)	166 (7)
O5—H5B⋯O2	0.82 (6)	2.07 (6)	2.862 (4)	162 (5)
C4—H4⋯O5ⁱⁱⁱ	0.93	2.58	3.423 (5)	152
C9—H9C⋯O4ⁱ	0.96	2.43	3.251 (3)	144
C2—H2⋯CgCⁱ	0.93	2.84	3.533 (2)	132
S1—O2⋯CgB	1.44 (1)	3.17 (1)	3.8430 (9)	107 (1)

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . CgB and CgC are the centroids of the C1/C6/C7/N2/C8/N1 and C10–C15 rings.

Acknowledgments

The authors acknowledge the Higher Education Commission, Islamabad, Pakistan, for funding the purchase of the diffractometer at GCU, Lahore.

supplementary crystallographic information

Comment

Cyclic amidines and quinazolinones, are known to possess diverse pharmacological activities as phosphodiesterase inhibitors (Glaser & Traber, 1984), anticonvulsants (Hori et al., 1990), antihypertensives (Glaser & Traber, 1984), vasodilators (Havera, 1979) and fibrinogen receptor antagonists (Liverton et al., 1998).

We now report synthesis and structure of the title compound (I), (Fig. 1), through a reaction of 2-aminobenzoic acid and hydrazine in presence of p-toluenesulfonic acid. A one pot, three component, p-toluenesulfonic acid catalyzed heterocyclization has yielded colourless prisms of (I) in the form of a p-toluenesulfonate salt with one water molecule of crystallization.

The crystal structure of (II) 3-(6-Azabicyclo(3.1.0)hex-2-en-6-yl)-2-((S)-1- hydroxy-2,2-dimethylpropyl)quinazolin-4(3H)-one (Atkinson & Meades, 2000) has been published. The title compound has also quinazoline with a chemically different attachements.

In the title compound the two fused rings A (C1—C6) and B(C1/C6/C7/N2/C8/N1) are essentially planar and the ring C (C10—C15) of the p-toluenesulfonate anion is of course planar. The title compound is stabillized due to intra- and intermolecular H-bonding as well as C–H···π and S1==O2···CgB interactions (Table 1). There also exist interactions between the centroids CgA–CgCⁱ [symmetry code: i = x, -y + 1, z + 1/2] and CgB–CgCⁱ at a distance of 3.8648 (12) and 3.9306 (13) Å, respectively. The water molecule connects the p-toluenesulfonate ions only. In the title compound there exist R₁¹(5) and R₂¹(6) ring motifs (Bernstein et al., 1995), (Fig 2).

Experimental

A mixture of anthranilic acid (0.14 g, 1 mmol), triethylorthoacetate (0.23 ml, 1.2 mmol), hydrazine hydrate (0.1 ml) and p-toluenesulfonic acid (1 g, 5 mmol) was stirred at room temperature for 1 h. After completion of the reaction as indicated by TLC, the reaction mixture was poured into water and allowed to settle, the product precipitated as colourless prisms of (I). The product was filtered, washed with water and dried. m.p. 585–594 K. yield: 72%.