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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1051.
Published online 2009 April 18. doi:  10.1107/S1600536809013841
PMCID: PMC2977733

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

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 [triangle]). For background on the properties of cyclic amidines and quinazolinones, see: Glaser & Traber (1984 [triangle]); Havera (1979 [triangle]); Hori et al. (1990 [triangle]); Liverton et al. (1998 [triangle]). For graph-set notation, see: Bernstein et al. (1995 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1051-scheme1.jpg

Experimental

Crystal data

  • C9H10N3O+·C7H7O3S·H2O
  • M r = 365.40
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1051-efi3.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.22 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2109 Friedal pairs
  • Flack parameter: 0.04 (5)

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013841/hb2950sup1.cif

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

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

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%.

Refinement

The coordinates of H-atoms connected with water molecule and NH2 group were refined. C-bound H-atoms were positioned geometrically (C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.2Ueq(C, N, O) or 1.5Ueq(methyl C).

Figures

Fig. 1.
The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. H-atoms are shown by small spheres of arbitrary radius and hydrogen bonds by dotted lines.
Fig. 2.
A fragment of the packing of (I) showing R11(5) and R21(6) ring motifs.

Crystal data

C9H10N3O+·C7H7O3S·H2OF(000) = 768
Mr = 365.40Dx = 1.404 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 4390 reflections
a = 20.838 (1) Åθ = 2.9–28.9°
b = 6.2769 (3) ŵ = 0.22 mm1
c = 14.7897 (7) ÅT = 296 K
β = 116.676 (1)°Prism, colourless
V = 1728.56 (14) Å30.28 × 0.24 × 0.20 mm
Z = 4

Data collection

Bruker Kappa APEXII CCD diffractometer4390 independent reflections
Radiation source: fine-focus sealed tube3952 reflections with I > 2σ(I)
graphiteRint = 0.022
Detector resolution: 7.30 pixels mm-1θmax = 28.9°, θmin = 2.9°
ω scansh = −28→28
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −8→6
Tmin = 0.935, Tmax = 0.958l = −19→20
9546 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.091w = 1/[σ2(Fo2) + (0.0508P)2 + 0.3201P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
4390 reflectionsΔρmax = 0.19 e Å3
243 parametersΔρmin = −0.22 e Å3
2 restraintsAbsolute structure: Flack (1983), 2109 Friedal pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (5)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.12729 (10)0.3093 (3)0.49282 (14)0.0676 (6)
N10.15599 (8)0.8870 (3)0.40550 (11)0.0404 (4)
N20.19969 (9)0.5856 (3)0.49997 (11)0.0442 (5)
N30.26093 (12)0.4718 (4)0.56765 (18)0.0611 (7)
C10.08550 (9)0.8146 (3)0.36387 (13)0.0421 (5)
C20.02990 (11)0.9399 (4)0.29579 (15)0.0534 (6)
C3−0.03899 (12)0.8605 (5)0.25562 (17)0.0676 (8)
C4−0.05286 (12)0.6617 (5)0.28300 (18)0.0723 (9)
C50.00197 (13)0.5380 (4)0.34994 (17)0.0607 (8)
C60.07242 (10)0.6139 (3)0.39165 (14)0.0458 (6)
C70.13149 (12)0.4861 (3)0.46325 (15)0.0483 (7)
C80.21066 (10)0.7761 (3)0.46961 (13)0.0407 (5)
C90.28411 (11)0.8657 (4)0.50903 (18)0.0573 (6)
S10.19585 (2)0.35554 (7)0.26006 (3)0.0413 (1)
O20.19879 (10)0.5841 (2)0.27106 (14)0.0654 (5)
O30.24598 (7)0.2742 (3)0.22604 (11)0.0595 (5)
O40.20275 (8)0.2499 (3)0.35157 (10)0.0551 (4)
C100.10901 (9)0.2884 (3)0.16552 (13)0.0390 (5)
C110.09715 (10)0.0902 (3)0.12006 (14)0.0443 (5)
C120.02813 (11)0.0315 (3)0.05242 (15)0.0504 (6)
C13−0.02945 (11)0.1669 (4)0.02991 (15)0.0528 (6)
C14−0.01601 (12)0.3654 (4)0.07515 (18)0.0593 (7)
C150.05282 (11)0.4272 (3)0.14287 (15)0.0497 (6)
C16−0.10500 (13)0.1024 (6)−0.0422 (2)0.0780 (9)
O50.30414 (16)0.8511 (4)0.2540 (3)0.1157 (13)
H10.1621 (12)1.020 (4)0.3909 (17)0.0485*
H20.038971.074320.277720.0641*
H3−0.076740.941970.209380.0809*
H3A0.2495 (16)0.346 (5)0.551 (2)0.0734*
H3B0.2630 (16)0.493 (5)0.626 (2)0.0734*
H4−0.099830.611620.255730.0867*
H5−0.007660.403790.367590.0728*
H9A0.314360.767700.495990.0688*
H9B0.303170.888500.580610.0688*
H9C0.282370.998730.476010.0688*
H110.13528−0.002980.134860.0532*
H120.02028−0.101450.021500.0605*
H14−0.053970.459450.059830.0712*
H150.060920.561330.172690.0596*
H16A−0.132440.08167−0.005320.0934*
H16B−0.10387−0.02800−0.075430.0934*
H16C−0.126810.21226−0.091840.0934*
H5A0.284 (3)0.949 (8)0.248 (4)0.1388*
H5B0.271 (3)0.770 (8)0.245 (4)0.1388*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0927 (12)0.0463 (8)0.0836 (11)−0.0072 (9)0.0571 (10)0.0044 (8)
N10.0439 (7)0.0344 (7)0.0429 (7)−0.0061 (6)0.0195 (6)−0.0032 (6)
N20.0556 (9)0.0390 (8)0.0417 (8)0.0027 (7)0.0252 (7)−0.0019 (6)
N30.0707 (12)0.0523 (12)0.0608 (12)0.0167 (10)0.0299 (10)0.0081 (9)
C10.0436 (8)0.0496 (10)0.0373 (8)−0.0099 (7)0.0218 (7)−0.0078 (7)
C20.0488 (10)0.0620 (13)0.0474 (10)−0.0027 (9)0.0197 (8)0.0049 (9)
C30.0440 (10)0.103 (2)0.0505 (11)−0.0070 (11)0.0166 (9)0.0046 (12)
C40.0484 (11)0.114 (2)0.0559 (12)−0.0311 (13)0.0247 (10)−0.0118 (13)
C50.0637 (12)0.0704 (15)0.0578 (12)−0.0289 (11)0.0361 (10)−0.0144 (10)
C60.0545 (10)0.0497 (11)0.0427 (9)−0.0131 (8)0.0304 (8)−0.0092 (8)
C70.0670 (13)0.0425 (11)0.0494 (11)−0.0065 (9)0.0387 (10)−0.0048 (8)
C80.0475 (9)0.0374 (9)0.0388 (8)−0.0016 (7)0.0207 (7)−0.0063 (7)
C90.0430 (9)0.0518 (12)0.0664 (12)−0.0025 (9)0.0150 (9)−0.0011 (10)
S10.0448 (2)0.0404 (2)0.0389 (2)−0.0109 (2)0.0191 (2)−0.0002 (2)
O20.0721 (9)0.0420 (7)0.0751 (10)−0.0179 (8)0.0267 (8)−0.0047 (8)
O30.0470 (7)0.0789 (11)0.0566 (8)−0.0051 (7)0.0269 (7)−0.0023 (7)
O40.0604 (8)0.0616 (9)0.0386 (6)−0.0227 (7)0.0180 (6)0.0002 (6)
C100.0436 (8)0.0402 (9)0.0353 (8)−0.0043 (7)0.0197 (7)0.0000 (7)
C110.0449 (9)0.0429 (10)0.0463 (9)−0.0019 (7)0.0215 (7)−0.0053 (7)
C120.0517 (10)0.0508 (11)0.0472 (10)−0.0104 (9)0.0209 (8)−0.0081 (8)
C130.0438 (9)0.0718 (14)0.0432 (10)−0.0085 (9)0.0198 (8)0.0012 (9)
C140.0447 (10)0.0708 (15)0.0591 (13)0.0161 (10)0.0204 (9)0.0053 (10)
C150.0572 (11)0.0434 (10)0.0492 (10)0.0058 (9)0.0246 (9)−0.0023 (8)
C160.0473 (12)0.114 (2)0.0647 (16)−0.0166 (13)0.0180 (11)−0.0023 (15)
O50.1089 (19)0.0754 (15)0.205 (3)−0.0269 (14)0.108 (2)−0.0230 (18)

Geometric parameters (Å, °)

S1—O31.4412 (17)C8—C91.482 (3)
S1—O41.4551 (16)C2—H20.9300
S1—O21.4420 (13)C3—H30.9300
S1—C101.7707 (19)C4—H40.9300
O1—C71.210 (3)C5—H50.9300
O5—H5B0.82 (6)C9—H9C0.9600
O5—H5A0.73 (5)C9—H9B0.9600
N1—C11.390 (3)C9—H9A0.9600
N1—C81.308 (3)C10—C111.383 (3)
N2—N31.412 (3)C10—C151.375 (3)
N2—C71.418 (3)C11—C121.383 (3)
N2—C81.333 (3)C12—C131.384 (3)
N1—H10.89 (3)C13—C141.382 (3)
N3—H3A0.83 (3)C13—C161.507 (4)
N3—H3B0.86 (3)C14—C151.386 (3)
C1—C61.390 (3)C11—H110.9300
C1—C21.388 (3)C12—H120.9300
C2—C31.377 (4)C14—H140.9300
C3—C41.382 (4)C15—H150.9300
C4—C51.369 (4)C16—H16C0.9600
C5—C61.396 (4)C16—H16A0.9600
C6—C71.453 (3)C16—H16B0.9600
O2—S1—C10107.61 (11)C2—C3—H3119.00
O2—S1—O3113.02 (12)C5—C4—H4120.00
O2—S1—O4111.53 (11)C3—C4—H4120.00
O4—S1—C10105.38 (9)C4—C5—H5120.00
O3—S1—O4112.26 (10)C6—C5—H5120.00
O3—S1—C10106.50 (9)C8—C9—H9A109.00
H5A—O5—H5B96 (7)C8—C9—H9B109.00
C1—N1—C8123.39 (18)C8—C9—H9C109.00
N3—N2—C7118.69 (19)H9A—C9—H9B109.00
N3—N2—C8117.1 (2)H9A—C9—H9C109.00
C7—N2—C8124.06 (17)H9B—C9—H9C110.00
C1—N1—H1116.1 (17)S1—C10—C11119.63 (15)
C8—N1—H1120.3 (17)S1—C10—C15119.88 (15)
N2—N3—H3A103 (2)C11—C10—C15120.33 (18)
H3A—N3—H3B109 (3)C10—C11—C12119.49 (19)
N2—N3—H3B105 (2)C11—C12—C13121.21 (19)
C2—C1—C6121.2 (2)C12—C13—C14118.2 (2)
N1—C1—C2120.53 (19)C14—C13—C16120.3 (2)
N1—C1—C6118.30 (17)C12—C13—C16121.5 (2)
C1—C2—C3118.5 (2)C13—C14—C15121.4 (2)
C2—C3—C4121.0 (2)C10—C15—C14119.38 (19)
C3—C4—C5120.5 (3)C12—C11—H11120.00
C4—C5—C6119.8 (2)C10—C11—H11120.00
C5—C6—C7120.83 (19)C11—C12—H12119.00
C1—C6—C7120.12 (19)C13—C12—H12119.00
C1—C6—C5119.05 (19)C15—C14—H14119.00
N2—C7—C6114.30 (17)C13—C14—H14119.00
O1—C7—N2119.2 (2)C10—C15—H15120.00
O1—C7—C6126.5 (2)C14—C15—H15120.00
N2—C8—C9120.72 (19)C13—C16—H16B109.00
N1—C8—N2119.8 (2)C13—C16—H16C109.00
N1—C8—C9119.51 (19)C13—C16—H16A109.00
C1—C2—H2121.00H16A—C16—H16C109.00
C3—C2—H2121.00H16B—C16—H16C109.00
C4—C3—H3120.00H16A—C16—H16B109.00
O4—S1—C10—C11−78.48 (18)N1—C1—C6—C70.6 (3)
O4—S1—C10—C1596.94 (18)C2—C1—C6—C50.1 (3)
O2—S1—C10—C11162.40 (17)C1—C2—C3—C40.7 (4)
O2—S1—C10—C15−22.2 (2)C2—C3—C4—C5−0.8 (4)
O3—S1—C10—C1140.94 (19)C3—C4—C5—C60.6 (4)
O3—S1—C10—C15−143.64 (17)C4—C5—C6—C7179.7 (2)
C1—N1—C8—C9179.25 (18)C4—C5—C6—C1−0.2 (3)
C8—N1—C1—C6−0.1 (3)C5—C6—C7—N2−179.2 (2)
C1—N1—C8—N2−1.8 (3)C1—C6—C7—O1−179.4 (2)
C8—N1—C1—C2−179.68 (19)C1—C6—C7—N20.7 (3)
N3—N2—C7—O12.0 (3)C5—C6—C7—O10.7 (4)
C7—N2—C8—C9−177.77 (19)S1—C10—C11—C12174.65 (16)
N3—N2—C7—C6−178.09 (19)C15—C10—C11—C12−0.8 (3)
C8—N2—C7—O1177.4 (2)S1—C10—C15—C14−174.44 (17)
C8—N2—C7—C6−2.7 (3)C11—C10—C15—C140.9 (3)
N3—N2—C8—N1178.78 (19)C10—C11—C12—C13−0.5 (3)
N3—N2—C8—C9−2.3 (3)C11—C12—C13—C141.5 (3)
C7—N2—C8—N13.3 (3)C11—C12—C13—C16−178.8 (2)
C2—C1—C6—C7−179.83 (19)C12—C13—C14—C15−1.3 (4)
N1—C1—C6—C5−179.51 (19)C16—C13—C14—C15179.0 (2)
N1—C1—C2—C3179.3 (2)C13—C14—C15—C100.1 (3)
C6—C1—C2—C3−0.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O4i0.89 (3)1.89 (3)2.734 (3)158 (3)
N3—H3A···O10.83 (3)2.31 (4)2.693 (3)109 (3)
N3—H3B···O3ii0.86 (3)2.22 (3)2.963 (3)146 (3)
O5—H5A···O3i0.73 (5)2.16 (5)2.871 (3)166 (7)
O5—H5B···O20.82 (6)2.07 (6)2.862 (4)162 (5)
C4—H4···O5iii0.932.583.423 (5)152
C9—H9C···O4i0.962.433.251 (3)144
C2—H2···CgCi0.932.843.533 (2)132
S1—O2···CgB1.4420 (13)3.169 (2)3.8430 (9)106.86 (10)

Symmetry codes: (i) x, y+1, z; (ii) x, −y+1, z+1/2; (iii) x−1/2, y−1/2, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB2950).

References

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