(R,S)-2′-Amino-6′-methyl-2,5′,5′-trioxo-6′H-spiro­[indoline-3,4′-pyrano[3,2-c][2,1]benzo­thia­zine]-3′-carbo­nitrile di­methyl­formamide monosolvate

Svitlana V Shishkina; Igor V Ukrainets; Lidiya A Petrushova

doi:10.1107/S1600536814013634

. 2014 Jun 18;70(Pt 7):o786–o787. doi: 10.1107/S1600536814013634

(R,S)-2′-Amino-6′-methyl-2,5′,5′-trioxo-6′H-spiro[indoline-3,4′-pyrano[3,2-c][2,1]benzothiazine]-3′-carbonitrile dimethylformamide monosolvate

Svitlana V Shishkina ^a,^*, Igor V Ukrainets ^b, Lidiya A Petrushova ^b

PMCID: PMC4120564 PMID: 25161572

Abstract

The title solvate, C₂₀H₁₄N₄O₄S·C₃H₇NO, comprises a stereogenic centre but the centrosymmetric space group causes the presence of the racemate in the crystal. The spiro-joined fragments are almost orthogonal, with a dihedral angle of 86.8 (2)° between the mean planes of the pyrane ring and the dihydroindolone ring system. The atoms of the indolinone bicycle are coplanar, with an r.m.s. deviation of 0.005 Å. In the crystal, pairs of N—H⋯O hydrogen bonds link the molecules into centrosymmetric dimers which are linked to the dimethylformamide solvent molecules by further N—H⋯O hydrogen bonds. N—H⋯N hydrogen bonds link neighbouring dimers into [010] chains.

Related literature

A three-component condensation of 1-R-4-hydroxy-2-oxo-1,2-dihydroquinolines, isatin and malononitrile gave satisfactory yield of 4,3′-spiro[(6-R-2-amino-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3-carbonitrile)-2′-oxindoles], see: Ukrainets et al. (2009 ▶). For van der Waals radii, see: Zefirov (1997 ▶) and for puckering parameters, see: Zefirov et al. (1990 ▶). For mean bond lengths, see: Bürgi & Dunitz (1994 ▶). graphic file with name e-70-0o786-scheme1.jpg

Experimental

Crystal data

C₂₀H₁₄N₄O₄S·C₃H₇NO
M _r = 479.51
Orthorhombic,
a = 17.2493 (12) Å
b = 9.6046 (5) Å
c = 27.7664 (17) Å
V = 4600.1 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 293 K
0.30 × 0.02 × 0.02 mm

Data collection

Agilent Xcalibur"3 diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2011 ▶) T _min = 0.946, T _max = 0.996
30060 measured reflections
4049 independent reflections
2147 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.194
S = 0.99
4049 reflections
323 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis CCD (Agilent, 2011 ▶); cell refinement: CrysAlis RED (Agilent, 2011 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814013634/kp2471sup1.cif

e-70-0o786-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013634/kp2471Isup2.hkl

e-70-0o786-Isup2.hkl^{(198.5KB, hkl)}

CCDC reference: 1007876

Additional supporting information: 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—H1N⋯O5ⁱ	0.82 (5)	2.01 (5)	2.797 (7)	160 (5)
N3—H3NA⋯O1ⁱⁱ	0.86 (5)	2.22 (5)	3.051 (6)	162 (4)
N3—H3NB⋯N4ⁱⁱⁱ	0.83 (4)	2.37 (4)	3.159 (6)	160 (4)

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

supplementary crystallographic information

S1. Comment

A three-component condensation of 1-R-4-hydroxy-2-oxo-1,2-dihydro- quinolines, isatin, and malononitrile gave a satisfactory yields of 4,3'- spiro[(6-R-2-amino-5-oxo-5,6-dihydro-4H-pyrano[3,2-c]quinoline-3- carbonitrile)-2'-oxindoles] (Ukrainets et al., 2009). This is an interesting reaction takes place more easily with sulfo analogues of 1-R-4-hydroxy- 2-oxo-1,2-dihydroquinolines. For example, 1-methyl-4-oxo-3,4-dihydro-1H- 2λ⁶,1-benzothiazine-2,2-dione was already 15 minute after the start of the reaction forms the corresponding 2'-amino-6'-methyl-2-oxo-1,2-dihydro-6'H– spiro[indole-3,4'-pyrano[3,2-c][2,1]benzothiazine]3'-carbonitrile-5,5'- dioxide (I), which was isolated as a solvate of DMF. The spiro-joined tricyclic and bicyclic fragments of I are turned relatively to each other in such way that the dihedral angle between mean planes of the pyrane ring and dihydroindolone bicycle is 86.8°. At that the C1—C2 bond is elongated as compared with its mean value (Bürgi & Dunitz, 1994) 1.511 Å. The bicyclic fragment is slightly non-planar, the five-membered heterocycle adopts an envelope conformation with deviation of the C1 atom by 0.14 Å. In addition the dihedral angle between planar N1—C1(=O1)—C2 fragment and aromatic ring is 11.5 °. The pyrane ring adopts a boat conformation (the puckering parameters (Zefirov et al., 1990) are: S=0.24, Θ=73.0°, Ψ=9.1°). Deviations of the O2 and C2 atoms from the mean plane of the remaining atoms of this ring are 0.10 Å and 0.20 Å, respectivey. The benzothiazine ring adopts a twist-boat conformation (the puckering parameters are S=0.57, Θ=47.2°, Ψ=25.9°). Deviations of the S1 and C9 atoms from the mean plane of the remaining atoms of this ring are -0.76 Å and -0.23 Å, respectivey. The steric repulsion between methyl group and atoms of the C10···C15 ring (shortened intramolecular contacts are: H20b···C11 2.71 Å, H11···C20 2.50 Å as compared with van der Waals radii sum ((Zefirov, 1997) 2.87 Å and H11···H20b 2.26 Å (2.34 Å)) results in elongation of the N2—C10 bond up to 1.415 (6) Å as compared with its mean value 1.371 Å. In the crystal the molecules form the centrosymmetric dimers (Fig. 2) by N3—H3Na···O1' (1 - x, 1 - y, 1 - z) intermolecular hydrogen bonds (Table 1). Each monomer of such dimer is bonded with DMF solvate molecule by the N1—H···O5' (0.5 + x, y, 1.5 - z) hydrogen bond. N3—H3Nb···N4' (1 - x, -y, 1 - z) hydrogen bond is observed between neighboring dimers (Table 1).

S2. Experimental

A mixture of 1-methyl-4-oxo-3,4-dihydro-1H-2λ⁶,1-benzothiazine-2,2- dione (2.11 g, 0.01 mol), isatin (1.47 g, 0.01 mol), malononitrile (0.66 g, 0.01 mol), and triethylamine (1.4 ml, 0.01 mol) in methanol (20 ml) was refluxed for 15 min, and cooled. The precipitated were off, washed with methanol, and crystallized from DMF-H₂O (1:1). Prepared 3.21 g (67%) solvate crystals of the pyranobenzothiazine with DMF; mp 437-439 K (decomp.).