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

Zhu, X.-T.; Zhang, G.; Ma, N.

doi:10.1107/S1600536809022946

organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page o1625

doi:10.1107/S1600536809022946

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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 and Ning Ma ^b

^aDepartment of Chemistry, Xuzhou Medical College, Jiangsu 221004, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou 221116, People's Republic of China
^*Correspondence e-mail: laotu2001@263.net

(Received 6 June 2009; accepted 15 June 2009; online 20 June 2009)

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 R₂²(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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.066
wR(F²) = 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

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

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at 30% probability level.
	Fig. 2. A partial packing diagram for the title compound. Hydrogen bonds are shown as dashed lines.

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 top

Crystal data top

C₂₄H₂₀F₂N₆O₄·C₂H₆O	Z = 2
M_r = 540.53	F(000) = 564
Triclinic, P1	D_x = 1.300 Mg m⁻³
Hall symbol: -P 1	Melting point > 573 K
a = 9.2189 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.5924 (17) Å	Cell parameters from 1085 reflections
c = 14.100 (2) Å	θ = 2.5–26.2°
α = 64.634 (2)°	µ = 0.10 mm⁻¹
β = 81.467 (3)°	T = 298 K
γ = 69.027 (2)°	Block, colorless
V = 1381.0 (4) Å³	0.40 × 0.37 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4773 independent reflections
Radiation source: fine-focus sealed tube	1979 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
T_min = 0.961, T_max = 0.988	k = −14→14
7223 measured reflections	l = −15→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0296P)²] where P = (F_o² + 2F_c²)/3
4773 reflections	(Δ/σ)_max < 0.001
352 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₄H₂₀F₂N₆O₄·C₂H₆O	γ = 69.027 (2)°
M_r = 540.53	V = 1381.0 (4) Å³
Triclinic, P1	Z = 2
a = 9.2189 (15) Å	Mo Kα radiation
b = 12.5924 (17) Å	µ = 0.10 mm⁻¹
c = 14.100 (2) Å	T = 298 K
α = 64.634 (2)°	0.40 × 0.37 × 0.12 mm
β = 81.467 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4773 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1979 reflections with I > 2σ(I)
T_min = 0.961, T_max = 0.988	R_int = 0.036
7223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.00	Δρ_max = 0.16 e Å⁻³
4773 reflections	Δρ_min = −0.18 e Å⁻³
352 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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) top

	x	y	z	U_iso*/U_eq
F1	−0.6967 (3)	0.6507 (3)	0.4242 (2)	0.1682 (12)
F2	0.5065 (3)	−0.0663 (2)	0.3998 (2)	0.1646 (12)
O1	0.3825 (3)	0.4015 (2)	0.05479 (17)	0.0724 (7)
O2	−0.1950 (3)	0.3213 (2)	0.1939 (2)	0.0921 (9)
O3	−0.0319 (4)	0.1522 (3)	0.5289 (2)	0.1190 (11)
O4	0.0495 (3)	0.5117 (2)	0.31565 (17)	0.0687 (7)
O5	0.8805 (3)	0.9228 (2)	0.0997 (2)	0.0952 (8)
H5	0.9547	0.9075	0.0620	0.143*
N1	−0.1126 (3)	0.6500 (2)	0.1209 (2)	0.0631 (8)
H1	−0.1678	0.7246	0.1130	0.076*
N2	0.0779 (3)	0.7345 (2)	0.0419 (2)	0.0641 (8)
N3	0.3234 (3)	0.6058 (3)	0.01820 (19)	0.0644 (8)
H3	0.4169	0.6010	−0.0035	0.077*
N4	0.2777 (3)	0.8125 (3)	−0.0313 (2)	0.0967 (11)
H4A	0.2176	0.8855	−0.0376	0.116*
H4B	0.3725	0.8012	−0.0519	0.116*
N5	−0.1246 (3)	0.2430 (3)	0.3629 (3)	0.0754 (9)
N6	0.0080 (3)	0.3332 (3)	0.4216 (2)	0.0633 (8)
C1	0.0370 (4)	0.6286 (3)	0.0878 (2)	0.0542 (9)
C2	0.2236 (5)	0.7165 (4)	0.0104 (3)	0.0666 (10)
C3	0.2842 (4)	0.4988 (3)	0.0593 (2)	0.0572 (9)
C4	0.1348 (4)	0.5102 (3)	0.1027 (2)	0.0511 (8)
C5	0.0803 (3)	0.3989 (3)	0.1575 (2)	0.0534 (9)
H5A	0.0389	0.3884	0.1031	0.064*
C6	−0.0593 (3)	0.4266 (3)	0.2334 (2)	0.0508 (8)
C7	−0.1839 (4)	0.5532 (3)	0.1689 (3)	0.0587 (9)
H7	−0.2202	0.5436	0.1121	0.070*
C8	−0.1336 (4)	0.3270 (3)	0.2608 (3)	0.0645 (10)
C9	−0.0484 (5)	0.2372 (4)	0.4437 (3)	0.0788 (12)
C10	0.0015 (4)	0.4300 (3)	0.3251 (3)	0.0551 (9)
C11	−0.1894 (5)	0.1422 (4)	0.3883 (3)	0.1337 (18)
H11A	−0.2645	0.1673	0.3358	0.201*
H11B	−0.2387	0.1255	0.4557	0.201*
H11C	−0.1073	0.0683	0.3900	0.201*
C12	0.0864 (4)	0.3261 (4)	0.5089 (3)	0.0979 (13)
H12A	0.0106	0.3622	0.5507	0.147*
H12B	0.1590	0.3710	0.4813	0.147*
H12C	0.1408	0.2406	0.5517	0.147*
C13	0.2024 (4)	0.2751 (3)	0.2181 (3)	0.0566 (9)
C14	0.2005 (5)	0.1674 (4)	0.2162 (3)	0.0923 (13)
H14	0.1292	0.1720	0.1731	0.111*
C15	0.3015 (6)	0.0531 (4)	0.2763 (4)	0.1288 (19)
H15	0.2984	−0.0190	0.2744	0.155*
C16	0.4049 (6)	0.0471 (4)	0.3381 (4)	0.1049 (15)
C17	0.4125 (4)	0.1504 (4)	0.3425 (3)	0.0855 (12)
H17	0.4847	0.1443	0.3858	0.103*
C18	0.3109 (4)	0.2647 (3)	0.2815 (3)	0.0658 (10)
H18	0.3160	0.3362	0.2834	0.079*
C19	−0.3239 (4)	0.5881 (3)	0.2339 (3)	0.0614 (9)
C20	−0.4521 (4)	0.5589 (3)	0.2302 (3)	0.0846 (12)
H20	−0.4539	0.5245	0.1839	0.102*
C21	−0.5790 (5)	0.5796 (4)	0.2940 (4)	0.1103 (16)
H21	−0.6653	0.5586	0.2921	0.132*
C22	−0.5731 (6)	0.6310 (5)	0.3588 (4)	0.1072 (16)
C23	−0.4515 (5)	0.6654 (4)	0.3646 (3)	0.1005 (14)
H23	−0.4530	0.7024	0.4096	0.121*
C24	−0.3249 (4)	0.6426 (3)	0.3002 (3)	0.0776 (11)
H24	−0.2395	0.6646	0.3021	0.093*
C25	0.9345 (6)	0.8842 (4)	0.2021 (3)	0.1126 (15)
H25A	0.9644	0.7943	0.2376	0.135*
H25B	0.8507	0.9193	0.2416	0.135*
C26	1.0640 (7)	0.9217 (5)	0.2010 (4)	0.168 (2)
H26A	1.1452	0.8910	0.1588	0.251*
H26B	1.1015	0.8884	0.2713	0.251*
H26C	1.0323	1.0109	0.1720	0.251*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0895 (19)	0.212 (3)	0.191 (3)	−0.039 (2)	0.072 (2)	−0.101 (2)
F2	0.164 (3)	0.0856 (19)	0.182 (3)	0.0200 (18)	−0.073 (2)	−0.0244 (18)
N1	0.0516 (19)	0.0545 (17)	0.073 (2)	−0.0138 (16)	0.0088 (15)	−0.0226 (15)
N2	0.060 (2)	0.0560 (19)	0.0677 (19)	−0.0207 (17)	0.0147 (16)	−0.0208 (16)
N3	0.0527 (19)	0.0603 (19)	0.0658 (19)	−0.0183 (17)	0.0126 (15)	−0.0168 (16)
N4	0.083 (2)	0.067 (2)	0.123 (3)	−0.0329 (19)	0.026 (2)	−0.024 (2)
N5	0.076 (2)	0.069 (2)	0.085 (3)	−0.0421 (19)	0.011 (2)	−0.023 (2)
N6	0.071 (2)	0.067 (2)	0.0500 (19)	−0.0254 (17)	0.0058 (16)	−0.0221 (17)
O1	0.0607 (16)	0.0671 (16)	0.0791 (17)	−0.0149 (14)	0.0180 (13)	−0.0310 (13)
O2	0.087 (2)	0.0913 (19)	0.113 (2)	−0.0431 (16)	−0.0262 (17)	−0.0361 (17)
O3	0.171 (3)	0.085 (2)	0.075 (2)	−0.046 (2)	0.013 (2)	−0.0092 (17)
O4	0.0741 (17)	0.0823 (17)	0.0686 (16)	−0.0397 (15)	0.0053 (13)	−0.0379 (14)
O5	0.101 (2)	0.0892 (19)	0.0798 (19)	−0.0185 (16)	0.0004 (16)	−0.0310 (16)
C1	0.049 (2)	0.064 (2)	0.049 (2)	−0.018 (2)	0.0062 (17)	−0.0249 (18)
C2	0.069 (3)	0.054 (2)	0.063 (2)	−0.021 (2)	0.006 (2)	−0.013 (2)
C3	0.056 (3)	0.061 (2)	0.049 (2)	−0.014 (2)	0.0053 (18)	−0.0221 (19)
C4	0.048 (2)	0.049 (2)	0.053 (2)	−0.0141 (18)	0.0066 (17)	−0.0213 (17)
C5	0.052 (2)	0.059 (2)	0.054 (2)	−0.0166 (18)	0.0020 (17)	−0.0290 (18)
C6	0.044 (2)	0.057 (2)	0.056 (2)	−0.0205 (18)	−0.0025 (17)	−0.0224 (17)
C7	0.046 (2)	0.063 (2)	0.067 (2)	−0.0184 (19)	−0.0033 (19)	−0.0252 (19)
C8	0.046 (2)	0.067 (3)	0.082 (3)	−0.019 (2)	−0.004 (2)	−0.029 (2)
C9	0.088 (3)	0.068 (3)	0.063 (3)	−0.018 (3)	0.017 (3)	−0.021 (2)
C10	0.040 (2)	0.066 (2)	0.059 (2)	−0.0154 (19)	0.0091 (18)	−0.030 (2)
C11	0.154 (4)	0.114 (4)	0.155 (5)	−0.098 (4)	0.020 (4)	−0.037 (3)
C12	0.126 (4)	0.107 (3)	0.057 (3)	−0.029 (3)	−0.014 (3)	−0.034 (2)
C13	0.052 (2)	0.063 (2)	0.054 (2)	−0.016 (2)	0.0027 (18)	−0.0261 (18)
C14	0.103 (3)	0.058 (3)	0.117 (4)	−0.009 (3)	−0.029 (3)	−0.041 (3)
C15	0.140 (5)	0.065 (3)	0.173 (5)	−0.007 (3)	−0.055 (4)	−0.045 (3)
C16	0.106 (4)	0.059 (3)	0.112 (4)	0.005 (3)	−0.023 (3)	−0.019 (3)
C17	0.067 (3)	0.089 (3)	0.082 (3)	−0.009 (3)	−0.018 (2)	−0.026 (3)
C18	0.057 (2)	0.063 (2)	0.069 (2)	−0.013 (2)	0.000 (2)	−0.024 (2)
C19	0.037 (2)	0.071 (2)	0.071 (3)	−0.0140 (19)	0.0028 (19)	−0.028 (2)
C20	0.044 (2)	0.100 (3)	0.117 (3)	−0.024 (2)	0.006 (2)	−0.052 (3)
C21	0.055 (3)	0.125 (4)	0.156 (5)	−0.038 (3)	0.023 (3)	−0.063 (4)
C22	0.067 (4)	0.120 (4)	0.125 (4)	−0.027 (3)	0.042 (3)	−0.057 (3)
C23	0.073 (3)	0.120 (4)	0.117 (4)	−0.022 (3)	0.019 (3)	−0.069 (3)
C24	0.055 (3)	0.097 (3)	0.093 (3)	−0.022 (2)	0.016 (2)	−0.057 (3)
C25	0.147 (5)	0.107 (4)	0.082 (3)	−0.052 (3)	0.000 (3)	−0.028 (3)
C26	0.210 (7)	0.201 (6)	0.124 (4)	−0.119 (6)	−0.008 (4)	−0.051 (4)

Geometric parameters (Å, º) top

F1—C22	1.376 (5)	C7—C19	1.511 (4)
F2—C16	1.376 (4)	C7—H7	0.9800
N1—C1	1.357 (4)	C11—H11A	0.9600
N1—C7	1.453 (3)	C11—H11B	0.9600
N1—H1	0.8600	C11—H11C	0.9600
N2—C2	1.320 (4)	C12—H12A	0.9600
N2—C1	1.374 (4)	C12—H12B	0.9600
N3—C2	1.335 (4)	C12—H12C	0.9600
N3—C3	1.378 (4)	C13—C18	1.374 (4)
N3—H3	0.8600	C13—C14	1.375 (4)
N4—C2	1.338 (4)	C14—C15	1.373 (5)
N4—H4A	0.8600	C14—H14	0.9300
N4—H4B	0.8600	C15—C16	1.346 (5)
N5—C8	1.366 (4)	C15—H15	0.9300
N5—C9	1.388 (4)	C16—C17	1.355 (5)
N5—C11	1.478 (4)	C17—C18	1.379 (4)
N6—C10	1.375 (4)	C17—H17	0.9300
N6—C9	1.382 (4)	C18—H18	0.9300
N6—C12	1.474 (4)	C19—C20	1.372 (4)
O1—C3	1.258 (3)	C19—C24	1.374 (4)
O2—C8	1.209 (4)	C20—C21	1.384 (5)
O3—C9	1.203 (4)	C20—H20	0.9300
O4—C10	1.210 (3)	C21—C22	1.343 (6)
O5—C25	1.418 (4)	C21—H21	0.9300
O5—H5	0.8200	C22—C23	1.363 (5)
C1—C4	1.380 (4)	C23—C24	1.392 (5)
C3—C4	1.406 (4)	C23—H23	0.9300
C4—C5	1.508 (4)	C24—H24	0.9300
C5—C13	1.522 (4)	C25—C26	1.428 (5)
C5—C6	1.585 (4)	C25—H25A	0.9700
C5—H5A	0.9800	C25—H25B	0.9700
C6—C10	1.507 (4)	C26—H26A	0.9600
C6—C8	1.521 (4)	C26—H26B	0.9600
C6—C7	1.564 (4)	C26—H26C	0.9600

C1—N1—C7	123.3 (3)	H11A—C11—H11B	109.5
C1—N1—H1	118.3	N5—C11—H11C	109.5
C7—N1—H1	118.3	H11A—C11—H11C	109.5
C2—N2—C1	114.7 (3)	H11B—C11—H11C	109.5
C2—N3—C3	123.3 (3)	N6—C12—H12A	109.5
C2—N3—H3	118.4	N6—C12—H12B	109.5
C3—N3—H3	118.4	H12A—C12—H12B	109.5
C2—N4—H4A	120.0	N6—C12—H12C	109.5
C2—N4—H4B	120.0	H12A—C12—H12C	109.5
H4A—N4—H4B	120.0	H12B—C12—H12C	109.5
C8—N5—C9	125.8 (3)	C18—C13—C14	117.5 (3)
C8—N5—C11	117.4 (3)	C18—C13—C5	122.3 (3)
C9—N5—C11	116.5 (4)	C14—C13—C5	120.1 (3)
C10—N6—C9	125.3 (3)	C15—C14—C13	121.6 (4)
C10—N6—C12	118.7 (3)	C15—C14—H14	119.2
C9—N6—C12	116.0 (3)	C13—C14—H14	119.2
C25—O5—H5	109.5	C16—C15—C14	118.9 (4)
N1—C1—N2	113.2 (3)	C16—C15—H15	120.5
N1—C1—C4	121.5 (3)	C14—C15—H15	120.5
N2—C1—C4	125.3 (3)	C15—C16—C17	122.0 (4)
N2—C2—N3	123.5 (3)	C15—C16—F2	120.1 (5)
N2—C2—N4	119.7 (4)	C17—C16—F2	117.9 (5)
N3—C2—N4	116.8 (4)	C16—C17—C18	118.6 (4)
O1—C3—N3	118.3 (3)	C16—C17—H17	120.7
O1—C3—C4	126.1 (3)	C18—C17—H17	120.7
N3—C3—C4	115.6 (3)	C13—C18—C17	121.4 (4)
C1—C4—C3	117.1 (3)	C13—C18—H18	119.3
C1—C4—C5	121.4 (3)	C17—C18—H18	119.3
C3—C4—C5	121.4 (3)	C20—C19—C24	118.7 (3)
C4—C5—C13	116.7 (3)	C20—C19—C7	118.7 (4)
C4—C5—C6	109.9 (3)	C24—C19—C7	122.5 (3)
C13—C5—C6	109.1 (2)	C19—C20—C21	121.3 (4)
C4—C5—H5A	106.9	C19—C20—H20	119.3
C13—C5—H5A	106.9	C21—C20—H20	119.3
C6—C5—H5A	106.9	C22—C21—C20	117.6 (4)
C10—C6—C8	115.5 (3)	C22—C21—H21	121.2
C10—C6—C7	111.9 (3)	C20—C21—H21	121.2
C8—C6—C7	106.2 (3)	C21—C22—C23	124.2 (4)
C10—C6—C5	109.1 (2)	C21—C22—F1	118.7 (5)
C8—C6—C5	105.7 (3)	C23—C22—F1	117.0 (5)
C7—C6—C5	108.1 (2)	C22—C23—C24	117.0 (4)
N1—C7—C19	112.1 (3)	C22—C23—H23	121.5
N1—C7—C6	109.7 (2)	C24—C23—H23	121.5
C19—C7—C6	112.5 (3)	C19—C24—C23	121.1 (4)
N1—C7—H7	107.4	C19—C24—H24	119.5
C19—C7—H7	107.4	C23—C24—H24	119.5
C6—C7—H7	107.4	O5—C25—C26	112.3 (4)
O2—C8—N5	121.6 (3)	O5—C25—H25A	109.1
O2—C8—C6	120.8 (4)	C26—C25—H25A	109.1
N5—C8—C6	117.5 (3)	O5—C25—H25B	109.1
O3—C9—N6	121.7 (4)	C26—C25—H25B	109.1
O3—C9—N5	121.5 (4)	H25A—C25—H25B	107.9
N6—C9—N5	116.9 (4)	C25—C26—H26A	109.5
O4—C10—N6	119.6 (3)	C25—C26—H26B	109.5
O4—C10—C6	122.3 (3)	H26A—C26—H26B	109.5
N6—C10—C6	118.0 (3)	C25—C26—H26C	109.5
N5—C11—H11A	109.5	H26A—C26—H26C	109.5
N5—C11—H11B	109.5	H26B—C26—H26C	109.5

C7—N1—C1—N2	178.1 (3)	C10—N6—C9—O3	176.3 (3)
C7—N1—C1—C4	−3.3 (5)	C12—N6—C9—O3	−1.1 (5)
C2—N2—C1—N1	178.9 (3)	C10—N6—C9—N5	−3.5 (5)
C2—N2—C1—C4	0.4 (5)	C12—N6—C9—N5	179.1 (3)
C1—N2—C2—N3	2.5 (5)	C8—N5—C9—O3	−171.9 (4)
C1—N2—C2—N4	−177.2 (3)	C11—N5—C9—O3	2.4 (6)
C3—N3—C2—N2	0.5 (5)	C8—N5—C9—N6	7.8 (5)
C3—N3—C2—N4	−179.8 (3)	C11—N5—C9—N6	−177.9 (3)
C2—N3—C3—O1	173.9 (3)	C9—N6—C10—O4	177.2 (3)
C2—N3—C3—C4	−6.0 (5)	C12—N6—C10—O4	−5.5 (5)
N1—C1—C4—C3	175.8 (3)	C9—N6—C10—C6	−5.5 (5)
N2—C1—C4—C3	−5.8 (5)	C12—N6—C10—C6	171.9 (3)
N1—C1—C4—C5	−0.6 (5)	C8—C6—C10—O4	−172.6 (3)
N2—C1—C4—C5	177.8 (3)	C7—C6—C10—O4	−51.0 (4)
O1—C3—C4—C1	−171.8 (3)	C5—C6—C10—O4	68.6 (4)
N3—C3—C4—C1	8.1 (4)	C8—C6—C10—N6	10.1 (4)
O1—C3—C4—C5	4.6 (5)	C7—C6—C10—N6	131.7 (3)
N3—C3—C4—C5	−175.5 (3)	C5—C6—C10—N6	−108.7 (3)
C1—C4—C5—C13	−149.9 (3)	C4—C5—C13—C18	43.5 (4)
C3—C4—C5—C13	33.9 (4)	C6—C5—C13—C18	−81.7 (4)
C1—C4—C5—C6	−25.0 (4)	C4—C5—C13—C14	−140.8 (3)
C3—C4—C5—C6	158.7 (3)	C6—C5—C13—C14	94.0 (4)
C4—C5—C6—C10	−70.3 (3)	C18—C13—C14—C15	0.9 (6)
C13—C5—C6—C10	58.8 (3)	C5—C13—C14—C15	−174.9 (4)
C4—C5—C6—C8	164.9 (3)	C13—C14—C15—C16	−0.3 (7)
C13—C5—C6—C8	−66.0 (3)	C14—C15—C16—C17	−0.1 (8)
C4—C5—C6—C7	51.5 (3)	C14—C15—C16—F2	179.5 (4)
C13—C5—C6—C7	−179.4 (3)	C15—C16—C17—C18	−0.1 (7)
C1—N1—C7—C19	158.4 (3)	F2—C16—C17—C18	−179.7 (3)
C1—N1—C7—C6	32.6 (4)	C14—C13—C18—C17	−1.2 (5)
C10—C6—C7—N1	65.0 (3)	C5—C13—C18—C17	174.6 (3)
C8—C6—C7—N1	−168.2 (3)	C16—C17—C18—C13	0.8 (6)
C5—C6—C7—N1	−55.2 (3)	N1—C7—C19—C20	139.9 (3)
C10—C6—C7—C19	−60.5 (4)	C6—C7—C19—C20	−95.8 (4)
C8—C6—C7—C19	66.3 (4)	N1—C7—C19—C24	−43.2 (4)
C5—C6—C7—C19	179.3 (3)	C6—C7—C19—C24	81.1 (4)
C9—N5—C8—O2	175.8 (4)	C24—C19—C20—C21	−2.1 (6)
C11—N5—C8—O2	1.5 (5)	C7—C19—C20—C21	174.9 (4)
C9—N5—C8—C6	−2.5 (5)	C19—C20—C21—C22	0.9 (7)
C11—N5—C8—C6	−176.8 (3)	C20—C21—C22—C23	0.9 (8)
C10—C6—C8—O2	175.2 (3)	C20—C21—C22—F1	−179.0 (4)
C7—C6—C8—O2	50.6 (4)	C21—C22—C23—C24	−1.4 (7)
C5—C6—C8—O2	−64.1 (4)	F1—C22—C23—C24	178.5 (4)
C10—C6—C8—N5	−6.4 (4)	C20—C19—C24—C23	1.6 (5)
C7—C6—C8—N5	−131.0 (3)	C7—C19—C24—C23	−175.4 (3)
C5—C6—C8—N5	114.3 (3)	C22—C23—C24—C19	0.2 (6)

Hydrogen-bond geometry (Å, º) top

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

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

Experimental details

Crystal data
Chemical formula	C₂₄H₂₀F₂N₆O₄·C₂H₆O
M_r	540.53
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.2189 (15), 12.5924 (17), 14.100 (2)
α, β, γ (°)	64.634 (2), 81.467 (3), 69.027 (2)
V (Å³)	1381.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.40 × 0.37 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.961, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	7223, 4773, 1979
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.120, 1.00
No. of reflections	4773
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.18

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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

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

Acknowledgements

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (1998). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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