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Acta Crystallogr Sect E Struct Rep Online. 2010 May 1; 66(Pt 5): o1179.
Published online 2010 April 28. doi:  10.1107/S1600536810012936
PMCID: PMC2979228

4-(2-Oxa-6-aza­spiro­[3.3]hept-6-yl)­benzo­nitrile

Abstract

In the title compound, C12H12N2O, the azetidine ring (r.m.s. deviation = 0.021 Å) and the oxetane ring (r.m.s. deviation = 0.014 Å) are nearly perpendicular to each other [dihedral angle = 89.7 (1)°]. The azetidine ring is twisted out of the plane of the benzene ring by 18.3 (1)°. In the crystal structure, mol­ecules are linked to form chains along the c axis by C—H(...)O hydrogen bonds.

Related literature

The title compound is a key inter­mediate to synthesize (pyrrolo[3,4-c]pyrazol-3-yl)benzamide derivatives. For the anti-tumor effect of these derivatives, see: Fancelli et al. (2005 [triangle]).

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Object name is e-66-o1179-scheme1.jpg

Experimental

Crystal data

  • C12H12N2O
  • M r = 200.24
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1179-efi1.jpg
  • a = 9.484 (4) Å
  • b = 11.033 (4) Å
  • c = 10.419 (4) Å
  • β = 113.186 (5)°
  • V = 1002.2 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 113 K
  • 0.60 × 0.60 × 0.27 mm

Data collection

  • Rigaku AFC10/Saturn 724-Plus diffractometer
  • 7662 measured reflections
  • 2234 independent reflections
  • 1872 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.041
  • wR(F 2) = 0.099
  • S = 1.00
  • 2234 reflections
  • 136 parameters
  • H-atom parameters constrained
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.16 e Å−3

Data collection: CrystalClear (Rigaku, 2008 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810012936/ci5062sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810012936/ci5062Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank Mr Kai-bei Yu of Beijing Institute of Technology for the X-ray data collection.

supplementary crystallographic information

Experimental

A DMSO solution of 2-oxa-6-azaspiro[3,3]heptane (0.99 g, 0.01 mol) with 4-fluorobenzonitrile (1.21 g, 0.01 mol) was heated to reflux for 5 h, then water (100 ml) was added into the solution. The mixture was extracted with CH2Cl2. Then the solvent was removed to give a red powder. Single crystals were obtained from a CH2Cl2 solution after 3 days.

Refinement

H atoms were placed in the calculated positions (C—H = 0.95–0.99 Å) and refined using a riding model with Uiso(H) = 1.2Ueq(C).

Figures

Crystal data

C12H12N2OF(000) = 424
Mr = 200.24Dx = 1.327 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.484 (4) ÅCell parameters from 2956 reflections
b = 11.033 (4) Åθ = 3.1–27.5°
c = 10.419 (4) ŵ = 0.09 mm1
β = 113.186 (5)°T = 113 K
V = 1002.2 (7) Å3Prism, colourless
Z = 40.60 × 0.60 × 0.27 mm

Data collection

Rigaku AFC10/Saturn 724-Plus diffractometer1872 reflections with I > 2σ(I)
Radiation source: rotating anodeRint = 0.029
graphiteθmax = 27.5°, θmin = 3.1°
Detector resolution: 28.5714 pixels mm-1h = −12→12
[var phi] and ω scansk = −14→11
7662 measured reflectionsl = −12→12
2234 independent reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.00w = 1/[σ2(Fo2) + (0.0456P)2 + 0.36P] where P = (Fo2 + 2Fc2)/3
2234 reflections(Δ/σ)max = 0.001
136 parametersΔρmax = 0.30 e Å3
0 restraintsΔρmin = −0.16 e Å3

Special details

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

xyzUiso*/Ueq
O10.53098 (12)0.21116 (9)−0.00129 (10)0.0272 (3)
N10.81838 (14)0.46062 (12)1.07793 (13)0.0275 (3)
N20.58259 (13)0.37004 (10)0.38573 (11)0.0186 (3)
C10.74599 (15)0.47583 (12)0.59326 (14)0.0178 (3)
H10.79330.51920.54210.021*
C20.79050 (15)0.49646 (12)0.73352 (14)0.0186 (3)
H20.86790.55470.77880.022*
C30.72270 (15)0.43219 (12)0.81086 (14)0.0177 (3)
C40.60810 (15)0.34638 (12)0.74350 (14)0.0183 (3)
H40.56240.30220.79540.022*
C50.56183 (15)0.32601 (12)0.60278 (14)0.0178 (3)
H50.48350.26830.55770.021*
C60.62984 (14)0.39026 (12)0.52463 (13)0.0165 (3)
C70.49702 (15)0.26581 (12)0.30534 (14)0.0178 (3)
H7A0.38420.27510.27020.021*
H7B0.53030.18710.35340.021*
C80.56407 (14)0.29329 (12)0.19522 (14)0.0167 (3)
C90.65782 (15)0.39702 (12)0.28976 (13)0.0177 (3)
H9A0.76990.38270.33020.021*
H9B0.63310.47820.24610.021*
C100.45979 (16)0.31151 (12)0.04116 (14)0.0204 (3)
H10A0.34990.29790.02080.024*
H10B0.47490.39070.00370.024*
C110.63751 (16)0.19237 (13)0.14221 (14)0.0226 (3)
H11A0.74550.20920.15750.027*
H11B0.62810.11140.17900.027*
C120.77569 (15)0.44870 (12)0.95891 (15)0.0202 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0353 (6)0.0266 (6)0.0202 (5)0.0027 (5)0.0113 (5)−0.0041 (4)
N10.0257 (7)0.0323 (7)0.0231 (7)−0.0015 (5)0.0082 (5)−0.0038 (6)
N20.0203 (6)0.0187 (6)0.0180 (6)−0.0073 (4)0.0086 (5)−0.0027 (5)
C10.0179 (6)0.0147 (6)0.0217 (7)−0.0007 (5)0.0086 (5)0.0028 (5)
C20.0156 (6)0.0151 (6)0.0223 (7)0.0007 (5)0.0043 (5)−0.0017 (5)
C30.0165 (6)0.0176 (6)0.0177 (7)0.0041 (5)0.0054 (5)−0.0004 (5)
C40.0177 (6)0.0181 (6)0.0212 (7)0.0025 (5)0.0098 (5)0.0022 (5)
C50.0157 (6)0.0163 (6)0.0212 (7)−0.0017 (5)0.0069 (5)−0.0012 (5)
C60.0151 (6)0.0147 (6)0.0188 (7)0.0023 (5)0.0058 (5)0.0008 (5)
C70.0184 (6)0.0157 (6)0.0195 (7)−0.0029 (5)0.0076 (5)−0.0014 (5)
C80.0161 (6)0.0149 (6)0.0193 (7)0.0004 (5)0.0071 (5)0.0002 (5)
C90.0171 (6)0.0186 (6)0.0172 (6)−0.0020 (5)0.0065 (5)0.0004 (5)
C100.0210 (7)0.0184 (6)0.0195 (7)−0.0010 (5)0.0057 (5)−0.0002 (6)
C110.0257 (7)0.0215 (7)0.0227 (7)0.0046 (6)0.0117 (6)0.0016 (6)
C120.0175 (6)0.0195 (6)0.0235 (8)0.0024 (5)0.0079 (5)−0.0010 (6)

Geometric parameters (Å, °)

O1—C111.4525 (17)C5—C61.4125 (19)
O1—C101.4534 (17)C5—H50.95
N1—C121.1504 (18)C7—C81.5451 (18)
N2—C61.3544 (17)C7—H7A0.99
N2—C71.4653 (17)C7—H7B0.99
N2—C91.4695 (17)C8—C111.5274 (18)
C1—C21.3711 (19)C8—C101.5314 (18)
C1—C61.4127 (18)C8—C91.5431 (18)
C1—H10.95C9—H9A0.99
C2—C31.4049 (19)C9—H9B0.99
C2—H20.95C10—H10A0.99
C3—C41.4034 (19)C10—H10B0.99
C3—C121.4335 (19)C11—H11A0.99
C4—C51.3734 (19)C11—H11B0.99
C4—H40.95
C11—O1—C1090.79 (9)H7A—C7—H7B111.1
C6—N2—C7128.02 (11)C11—C8—C1085.12 (10)
C6—N2—C9130.44 (11)C11—C8—C9122.78 (11)
C7—N2—C994.47 (10)C10—C8—C9122.94 (11)
C2—C1—C6120.13 (12)C11—C8—C7120.34 (11)
C2—C1—H1119.9C10—C8—C7121.30 (11)
C6—C1—H1119.9C9—C8—C788.49 (10)
C1—C2—C3120.61 (12)N2—C9—C888.40 (10)
C1—C2—H2119.7N2—C9—H9A113.9
C3—C2—H2119.7C8—C9—H9A113.9
C4—C3—C2119.53 (12)N2—C9—H9B113.9
C4—C3—C12119.89 (12)C8—C9—H9B113.9
C2—C3—C12120.49 (12)H9A—C9—H9B111.1
C5—C4—C3120.22 (12)O1—C10—C891.91 (10)
C5—C4—H4119.9O1—C10—H10A113.3
C3—C4—H4119.9C8—C10—H10A113.3
C4—C5—C6120.45 (12)O1—C10—H10B113.3
C4—C5—H5119.8C8—C10—H10B113.3
C6—C5—H5119.8H10A—C10—H10B110.6
N2—C6—C5119.95 (12)O1—C11—C892.11 (10)
N2—C6—C1121.00 (12)O1—C11—H11A113.3
C5—C6—C1119.05 (12)C8—C11—H11A113.3
N2—C7—C888.47 (10)O1—C11—H11B113.3
N2—C7—H7A113.9C8—C11—H11B113.3
C8—C7—H7A113.9H11A—C11—H11B110.6
N2—C7—H7B113.9N1—C12—C3179.26 (15)
C8—C7—H7B113.9
C6—C1—C2—C30.67 (19)N2—C7—C8—C11130.78 (12)
C1—C2—C3—C4−0.17 (18)N2—C7—C8—C10−125.31 (12)
C1—C2—C3—C12176.30 (12)N2—C7—C8—C93.04 (9)
C2—C3—C4—C5−0.45 (19)C6—N2—C9—C8154.66 (13)
C12—C3—C4—C5−176.95 (12)C7—N2—C9—C83.21 (10)
C3—C4—C5—C60.57 (19)C11—C8—C9—N2−128.76 (12)
C7—N2—C6—C5−18.4 (2)C10—C8—C9—N2123.99 (12)
C9—N2—C6—C5−161.23 (13)C7—C8—C9—N2−3.04 (9)
C7—N2—C6—C1162.08 (12)C11—O1—C10—C8−2.22 (10)
C9—N2—C6—C119.3 (2)C11—C8—C10—O12.12 (10)
C4—C5—C6—N2−179.56 (12)C9—C8—C10—O1128.42 (12)
C4—C5—C6—C1−0.07 (19)C7—C8—C10—O1−120.66 (12)
C2—C1—C6—N2178.93 (12)C10—O1—C11—C82.22 (10)
C2—C1—C6—C5−0.55 (19)C10—C8—C11—O1−2.12 (10)
C6—N2—C7—C8−155.71 (13)C9—C8—C11—O1−128.56 (12)
C9—N2—C7—C8−3.21 (10)C7—C8—C11—O1121.54 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C4—H4···O1i0.952.473.371 (2)159

Symmetry codes: (i) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5062).

References

  • Fancelli, D., Berta, D., Bindi, S., Cameron, A., Cappella, P., Carpinelli, P., Catana, C., Forte, B., Giordano, P., Giorgini, M. L., Mantegani, S., Marsiglio, A., Meroni, M., Moll, J., Pittal\’a, V., Roletto, F., Severino, D., Soncini, C., Storici, P., Tonani, R., Varasi, M., Vulpetti, A. & Vianello, P.et al. (2005). J. Med. Chem. 48, 3080–3084. [PubMed]
  • Rigaku (2008). CrystalClear Rigaku Corporation, The Woodlands, Texas, USA.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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