Crystal structure of (5′S,8′S)-3-(2,5-di­methyl­phen­yl)-8-meth­oxy-3-nitro-1-aza­spiro­[4.5]decane-2,4-dione

Gao-Bo Hu; Da-Wei Jiang; Jiang-Yan Li; Yan Rao; Li-Yuan Jiang

doi:10.1107/S2056989015004715

. 2015 Mar 14;71(Pt 4):o238–o239. doi: 10.1107/S2056989015004715

Crystal structure of (5′S,8′S)-3-(2,5-dimethylphenyl)-8-methoxy-3-nitro-1-azaspiro[4.5]decane-2,4-dione

Gao-Bo Hu ^a, Da-Wei Jiang ^a, Jiang-Yan Li ^a, Yan Rao ^a, Li-Yuan Jiang ^a,^*

PMCID: PMC4438798 PMID: 26029433

Abstract

The title compound, C₁₈H₂₂N₂O₅, was synthesized by nitrification of its enol precursor. The pyrrolidine ring plane adopts a twisted conformation about the C—C bond linking the spiro centre and the C=O group remote from the N atom. It makes dihedral angles of 71.69 (9) and 88.92 (9)°, respectively, with the benzene ring plane and the plane defined by the four C atoms that form the seat of the of the cyclohexane chair. At the spiro centre, the NH group is axial and the C=O group is equatorial with respect to the cyclohexane ring. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R ₂ ²(8) loops. The dimers are linked by C—H⋯O interactions, generating a three-dimensional network.

Keywords: crystal structure; 1-azaspiro[4.5]decane-2,4-dione; hydrogen bonding; pesticide; spirotetramat

Related literature

For the pesticide spirotetramat, the central unit of the title compound, see: Fischer & Weiss (2008 ▸); Maus (2008 ▸); Bruck et al. (2009 ▸); Campbell et al. (1985 ▸); Schobert & Schlenk (2008 ▸). For structures of spirotetramat derivatives, see: Fischer et al. (2010 ▸). graphic file with name e-71-0o238-scheme1.jpg

Experimental

Crystal data

C₁₈H₂₂N₂O₅
M _r = 346.38
Monoclinic,
a = 9.5707 (9) Å
b = 8.4181 (7) Å
c = 22.8720 (19) Å
β = 100.703 (8)°
V = 1810.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 170 K
0.36 × 0.32 × 0.23 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) T _min = 0.954, T _max = 1.000
6891 measured reflections
3308 independent reflections
2600 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.139
S = 1.04
3308 reflections
229 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015004715/hb7342sup1.cif

e-71-0o238-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015004715/hb7342Isup2.hkl

e-71-0o238-Isup2.hkl^{(162.3KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015004715/hb7342Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015004715/hb7342fig1.tif

The molecular structure of title molecule, showing 50% displacement ellipsoids.

Click here for additional data file.^{(877.4KB, tif)}

. DOI: 10.1107/S2056989015004715/hb7342fig2.tif

Reaction scheme.

CCDC reference: 1052631

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N2H2O3ⁱ	0.88	2.02	2.8853(19)	167
C4H4O5ⁱⁱ	0.95	2.57	3.287(3)	132
C7H7BO1ⁱⁱⁱ	0.98	2.49	3.454(3)	168
C14H14BO2^iv	0.99	2.54	3.265(3)	130

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

supplementary crystallographic information

S1. Comment

Spirotetramat is a new systemic insecticide which chemically belongs to the class of spirocyclic tetramic acid derivatives and be developed by Bayer CropScience AG (Fischer et al., 2008; Maus, 2008). A unique mode of action coupled with a high degree of activity on targeted pests and low toxicity to nontarget organisms make spirocyclic tetronic acid compounds as a new tool for integrated pest management (Bruck et al., 2009; Campbell et al.,1985; Schobert et al., 2008) In order to study the influence of new substituents on the activity of the Spirotetramat derivative, the title compound, has been synthesized and its structure has been determined (Fig. 1). The molecule contains one benzene ring, one six membered ring, and one five membered ring. The cyclohexane ring adopts a chair conformation;the C13, C14, C16 and C17 atoms are on one plane with C15 and C11 deviating by 0.658 (5)and -0.676 (9) Å, respectively. There are three planes in the molecule: atoms of C10, C11, C12 and N2 generate the pyrrolidine plane (I), C1—C6 yield the benzene plane (II) and C13—C14 and C16—C17 form the cyclohexane plane(III). The angle between planes I and II is 71.69 (9) °, and that between planes I and III is 88.92 (9) °. The space arrangement might result from the space factor between groups.

S2. Experimental

A solution of fuming nitric acid (0.92 g, 16mmoL) in anhydrous chloroform (10 ml) was added dropwise to a solution of compound 2 (1.78 g, 5.9mmoL) in anhydrous chloroform (20 ml) at 0 degree and stirred for 2 h. The reaction mixture was then washed with ice water (15 ml), and saturated sodium chloride solution and dried over anhydrous Na₂SO₄. The solvent was evaporated, and the residual solid was crystallized from ethanol to afford 1.84 g compound 3 as a pale yellow solid: yield 90%. The 1H NMR, 13 C-NMR and ESI-MS data testified the title compound's structure. ESI-MS: 347 (M+H)+ (100%); 1H NMR (500 MHz, CDCl3): 7.48 (s, 1H, –NH–),7.55 (s, 1H, Ph—H), 7.14 (d, 1H, Ph—H), 7.07 (d, 1H, Ph—H), 3.54 (s, 3H, –OCH3), 3.34–3.33 (m, 1H, –CH—O—C–), 2.36 (s, 3H, Ph—Me), 2.27 (s, 3H, Ph—Me), 2.12–2.07 (m, 4H, Cyclohexane-H4), 1.99–1.56 (m, 4H, Cyclohexane-H4); 13 C-NMR (100 MHz, CDCl3): 199.9, 165.1, 136.7, 136.0, 133.2, 131.5, 129.7, 127.4, 95.8, 76.8, 75.6, 66.1, 55.7, 32.5, 31.5, 26.4, 26.3, 21.0, 20.3.