2-Amino-5,7-bis­(4-fluoro­phen­yl)-1′,3′-dimethyl-7,8-dihydro­spiro­[pyrido[2,3-d]pyrimidine-6(5H),5′-pyrimidine]-2′,4,4′,6′(3H,1′H,3′H,5′H)-tetra­one ethanol solvate

Xiao-Tong Zhu; Ge Zhang; Ning Ma

doi:10.1107/S1600536809022946

. 2009 Jun 20;65(Pt 7):o1625. doi: 10.1107/S1600536809022946

2-Amino-5,7-bis(4-fluorophenyl)-1′,3′-dimethyl-7,8-dihydrospiro[pyrido[2,3-d]pyrimidine-6(5H),5′-pyrimidine]-2′,4,4′,6′(3H,1′H,3′H,5′H)-tetraone ethanol solvate

Xiao-Tong Zhu ^a,^*, Ge Zhang ^b, Ning Ma ^b

PMCID: PMC2969385 PMID: 21582892

Abstract

In the molecule of the title compound, C₂₄H₂₀F₂N₆O₄·C₂H₅OH, the pyrimidine ring is oriented at dihedral angles of 42.64 (3) and 62.94 (3)° with respect to the benzene rings, while the dihedral angle between the benzene rings is 74.45 (3)°. The pyridine ring adopts an envelope conformation. In the crystal structure, intermolecular N—H⋯O and O—H⋯N hydrogen bonds link the molecules into a two-dimensional network, forming R ₂ ²(8) ring motifs. π–π contacts between the pyrimidine and benzene rings [centroid–centroid distances = 3.516 (1) and 3.927 (1) Å] may further stabilize the structure.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For ring-motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₄H₂₀F₂N₆O₄·C₂H₆O
M _r = 540.53
Triclinic,
a = 9.2189 (15) Å
b = 12.5924 (17) Å
c = 14.100 (2) Å
α = 64.634 (2)°
β = 81.467 (3)°
γ = 69.027 (2)°
V = 1381.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 298 K
0.40 × 0.37 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.961, T _max = 0.988
7223 measured reflections
4773 independent reflections
1979 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.066
wR(F ²) = 0.120
S = 1.00
4773 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1999 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809022946/hk2707sup1.cif

e-65-o1625-sup1.cif^{(25.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022946/hk2707Isup2.hkl

e-65-o1625-Isup2.hkl^{(233.8KB, 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
N3—H3⋯O1ⁱ	0.86	1.88	2.737 (3)	177
N4—H4A⋯O5ⁱⁱ	0.86	2.07	2.890 (3)	160
O5—H5⋯N2ⁱⁱⁱ	0.82	2.19	2.779 (3)	129

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

Acknowledgments

The authors are grateful to the Foundation of Xuzhou Medical College (grant No. 08 K J06) for financial support.

supplementary crystallographic information

Comment

Domino reactions, in an environmentally benign and atom economic fashion, especially considering that certain complex compounds with high diastereoselectivities such as 6-spirosubstituted pyrido[2,3-d]pyrimidine, are of great significance and are very effective and attractive. Heterocyclic spirocompounds exhibiting structural rigidity due to conformational restriction are of interest in synthetic organic chemistry. Indeed, the presence of a spirocarbon atom induces a relatively large steric strain and allows thermal, base, acid or photo-promoted rearrangement of these products, yielding new and often unexpected heterocycles. Therefore, the syntheses of these spiral structures were of considerable interest in the pharmaceutical and agrocultural chemistry. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N2/N3//C1-C4), C (N5/N6/C6/C8-C10), D (C13-C18) and E (C19-C24) are, of course, planar. The dihedral angles between them are A/C = 86.54 (3), A/D = 61.88 (3), A/E = 55.57 (3), C/D = 42.64 (3), C/E = 62.94 (3) and D/E = 74.45 (3) °. Ring B (N1/C1/C4-C7) adopts envelope conformation with atom C6 displaced by -0.695 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular N-H···O and O-H···N hydrogen bonds (Table 1) link the molecules into a two-dimensional network forming R₂²(8) ring motifs (Bernstein et al., 1995), in which they may be effective in the stabilization of the structure. The π–π contacts between the pyrimidine and phenyl rings, Cg3—Cg4 and Cg3—Cg5, [where Cg3, Cg4 and Cg5 are centroids of the rings C (N5/N6/C6/C8-C10), D (C13-C18) and E (C19-C24), respectively] may further stabilize the structure, with centroid-centroid distances of 3.516 (1) and 3.927 (1) Å, respectively.

Experimental

The title compound was prepared in vial (10 ml), 2,6-diaminopyrimidine-4(3H)-one (126 mg, 1 mmol), 1,3-dimethylbarbituric acid (156 mg, 1 mmol), 4-fluorobenzaldehyde (248 mg, 2 mmol) and water (2.0 ml) were mixed, and then capped. The mixture was irradiated for 7 min at 373 K (initial power 150 W and maximum power 250 W).