Cyclo­hexane-1-spiro-2′-imidazolidine-5′-spiro-1′′-cyclo­hexan-4′-one

T Kavitha; S Ponnuswamy; R Vijayalakshmi; M Thenmozhi; M N Ponnuswamy

doi:10.1107/S1600536810012468

. 2010 Apr 14;66(Pt 5):o1072. doi: 10.1107/S1600536810012468

Cyclohexane-1-spiro-2′-imidazolidine-5′-spiro-1′′-cyclohexan-4′-one

T Kavitha ^a, S Ponnuswamy ^b, R Vijayalakshmi ^c, M Thenmozhi ^a, M N Ponnuswamy ^a,^*

PMCID: PMC2979210 PMID: 21579127

Abstract

In the title compound, C₁₃H₂₂N₂O, the central imidazolidine ring is in an envelope conformation and the two cyclohexane rings adopt chair conformations. In the crystal structure, the molecules are linked into centrosymmetric R ₂ ²(8) dimers by pairs of N—H⋯O hydrogen bonds.

Related literature

For general background to imidazolidine derivatives, see: Tsao et al. (1991 ▶); Wang et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For ring conformational analysis, see: Cremer & Pople (1975 ▶); Nardelli (1995 ▶).

Experimental

Crystal data

C₁₃H₂₂N₂O
M _r = 222.33
Triclinic,
a = 5.8270 (8) Å
b = 10.1703 (5) Å
c = 10.6651 (4) Å
α = 86.103 (2)°
β = 81.331 (3)°
γ = 89.720 (3)°
V = 623.36 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.15 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.985, T _max = 0.989
11727 measured reflections
2311 independent reflections
2023 reflections with I > 2σ(I)
R _int = 0.020

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.104
S = 1.04
2311 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810012468/ci5049sup1.cif

e-66-o1072-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012468/ci5049Isup2.hkl

e-66-o1072-Isup2.hkl^{(111.2KB, 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	0.87 (2)	2.02 (2)	2.8821 (14)	172 (1)

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

TK thanks the CSIR, India, for financial support in the form of a Senior Research Fellowship. SP thanks the UGC, India, for financial support.

supplementary crystallographic information

Comment

Imidazolidines occupy a unique position among the five-membered heterocycles and are highly used in synthetic as well as mechanistic organic chemistry and biochemistry (Tsao et al., 1991). Imidazolidine derivatives are important intermediates and building blocks in the construction of various biologically active compounds (Wang et al., 1995).

In the title molecule (Fig. 1), the five-membered imidazolidine ring is transfused with two cyclohexane rings. The bond lengths are comparable to the reported values (Allen et al., 1987). The imidazolidine ring adopts an envelope conformation, with flap atom N1 deviating by 0.198 (2) Å from the C2/N3/C4/C5 plane. The asymmetry parameters for the imidazolidine ring shows that a mirror plane is passing through the atom N1 [ΔC_s = 2.7 (1)] (Nardelli, 1995); the puckering parameters [q2 = 0.128 (1) Å and φ(2) = 187.8 (5)°] (Cremer & Pople, 1975) also support the above fact. The sum of the bond angles around N1 (326.6°) shows sp³ hybridization and atom N3 (359.6°) is in accordance with sp² hybridization. The two cyclohexane rings adopt chair conformations.

In the crystal, molecules are linked into centrosymmetric R₂²(8) (Bernstein et al., 1995) dimers by pairs of N—H···O hydrogen bonds (Table 1).

Experimental

Potassium cyanide (20 mmol), ammonium chloride (20 mmol) and aqueous ammonium sulfide (30 ml) were dissolved in water (50 ml). Cyclohexanone (40 mmol) was slowly added into the above reaction mixture and stirred for 8 h at 333 K. The precipitated cyclohexan-1-spiro-2'-(imidazolidin-4'-thione)-5'-spiro-1''-cyclohexane was filtered. An ice-cold solution of the above imidazolidin-4-thione (5 mm0l) in glacial acetic acid (5 ml) was treated with hydrogen peroxide (30%, 5 ml) and kept at room temperature for 24 h. The reaction mixture was poured into crushed ice and extracted with ether (40 ml). Evaporation of ether yielded the title compound which was recrystallized by slow evaporation of a water–acetone (20:2) solution.