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

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.041
• wR factor = 0.099
• Data-to-parameter ratio = 16.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     --  C12     ..       6.17 su
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C3     -   C12    ...       1.43 Ang.
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         21
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT153_ALERT_1_C The su's on the Cell Axes   are Equal (x 100000)        400 Ang.
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         21

Alert level G
PLAT128_ALERT_4_G Non-standard setting of Space-group P21/c   ....      P21/n

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check


checkCIF publication errors

Alert level G
PUBL013_ALERT_1_G The _publ_section_comment (discussion of study) is
            missing. This is required for a full paper submission (but is
            optional for an electronic paper).

   0 ALERT level A = Data missing that is essential or data in wrong format
   1 ALERT level G = General alerts. Data that may be required is missing

---

Related literature

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

S1. 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.

S2. Refinement

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

Structure description

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

Computing details

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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 (Sheldrick, 2008).

Figures

Fig. 1.

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

Crystal data

C12H12N2O	F(000) = 424
Mr = 200.24	Dx = 1.327 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.484 (4) Å	Cell parameters from 2956 reflections
b = 11.033 (4) Å	θ = 3.1–27.5°
c = 10.419 (4) Å	µ = 0.09 mm^−1
β = 113.186 (5)°	T = 113 K
V = 1002.2 (7) Å^3	Prism, colourless
Z = 4	0.60 × 0.60 × 0.27 mm

Data collection

Rigaku AFC10/Saturn 724-Plus diffractometer	1872 reflections with I > 2σ(I)
Radiation source: rotating anode	Rint = 0.029
Graphite monochromator	θmax = 27.5°, θmin = 3.1°
Detector resolution: 28.5714 pixels mm^-1	h = −12→12
φ and ω scans	k = −14→11
7662 measured reflections	l = −12→12
2234 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.099	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0456P)^2 + 0.36P] where P = (Fo^2 + 2Fc^2)/3
2234 reflections	(Δ/σ)max = 0.001
136 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.16 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.53098 (12)	0.21116 (9)	−0.00129 (10)	0.0272 (3)
N1	0.81838 (14)	0.46062 (12)	1.07793 (13)	0.0275 (3)
N2	0.58259 (13)	0.37004 (10)	0.38573 (11)	0.0186 (3)
C1	0.74599 (15)	0.47583 (12)	0.59326 (14)	0.0178 (3)
H1	0.7933	0.5192	0.5421	0.021*
C2	0.79050 (15)	0.49646 (12)	0.73352 (14)	0.0186 (3)
H2	0.8679	0.5547	0.7788	0.022*
C3	0.72270 (15)	0.43219 (12)	0.81086 (14)	0.0177 (3)
C4	0.60810 (15)	0.34638 (12)	0.74350 (14)	0.0183 (3)
H4	0.5624	0.3022	0.7954	0.022*
C5	0.56183 (15)	0.32601 (12)	0.60278 (14)	0.0178 (3)
H5	0.4835	0.2683	0.5577	0.021*
C6	0.62984 (14)	0.39026 (12)	0.52463 (13)	0.0165 (3)
C7	0.49702 (15)	0.26581 (12)	0.30534 (14)	0.0178 (3)
H7A	0.3842	0.2751	0.2702	0.021*
H7B	0.5303	0.1871	0.3534	0.021*
C8	0.56407 (14)	0.29329 (12)	0.19522 (14)	0.0167 (3)
C9	0.65782 (15)	0.39702 (12)	0.28976 (13)	0.0177 (3)
H9A	0.7699	0.3827	0.3302	0.021*
H9B	0.6331	0.4782	0.2461	0.021*
C10	0.45979 (16)	0.31151 (12)	0.04116 (14)	0.0204 (3)
H10A	0.3499	0.2979	0.0208	0.024*
H10B	0.4749	0.3907	0.0037	0.024*
C11	0.63751 (16)	0.19237 (13)	0.14221 (14)	0.0226 (3)
H11A	0.7455	0.2092	0.1575	0.027*
H11B	0.6281	0.1114	0.1790	0.027*
C12	0.77569 (15)	0.44870 (12)	0.95891 (15)	0.0202 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0353 (6)	0.0266 (6)	0.0202 (5)	0.0027 (5)	0.0113 (5)	−0.0041 (4)
N1	0.0257 (7)	0.0323 (7)	0.0231 (7)	−0.0015 (5)	0.0082 (5)	−0.0038 (6)
N2	0.0203 (6)	0.0187 (6)	0.0180 (6)	−0.0073 (4)	0.0086 (5)	−0.0027 (5)
C1	0.0179 (6)	0.0147 (6)	0.0217 (7)	−0.0007 (5)	0.0086 (5)	0.0028 (5)
C2	0.0156 (6)	0.0151 (6)	0.0223 (7)	0.0007 (5)	0.0043 (5)	−0.0017 (5)
C3	0.0165 (6)	0.0176 (6)	0.0177 (7)	0.0041 (5)	0.0054 (5)	−0.0004 (5)
C4	0.0177 (6)	0.0181 (6)	0.0212 (7)	0.0025 (5)	0.0098 (5)	0.0022 (5)
C5	0.0157 (6)	0.0163 (6)	0.0212 (7)	−0.0017 (5)	0.0069 (5)	−0.0012 (5)
C6	0.0151 (6)	0.0147 (6)	0.0188 (7)	0.0023 (5)	0.0058 (5)	0.0008 (5)
C7	0.0184 (6)	0.0157 (6)	0.0195 (7)	−0.0029 (5)	0.0076 (5)	−0.0014 (5)
C8	0.0161 (6)	0.0149 (6)	0.0193 (7)	0.0004 (5)	0.0071 (5)	0.0002 (5)
C9	0.0171 (6)	0.0186 (6)	0.0172 (6)	−0.0020 (5)	0.0065 (5)	0.0004 (5)
C10	0.0210 (7)	0.0184 (6)	0.0195 (7)	−0.0010 (5)	0.0057 (5)	−0.0002 (6)
C11	0.0257 (7)	0.0215 (7)	0.0227 (7)	0.0046 (6)	0.0117 (6)	0.0016 (6)
C12	0.0175 (6)	0.0195 (6)	0.0235 (8)	0.0024 (5)	0.0079 (5)	−0.0010 (6)

Geometric parameters (Å, º)

O1—C11	1.4525 (17)	C5—C6	1.4125 (19)
O1—C10	1.4534 (17)	C5—H5	0.95
N1—C12	1.1504 (18)	C7—C8	1.5451 (18)
N2—C6	1.3544 (17)	C7—H7A	0.99
N2—C7	1.4653 (17)	C7—H7B	0.99
N2—C9	1.4695 (17)	C8—C11	1.5274 (18)
C1—C2	1.3711 (19)	C8—C10	1.5314 (18)
C1—C6	1.4127 (18)	C8—C9	1.5431 (18)
C1—H1	0.95	C9—H9A	0.99
C2—C3	1.4049 (19)	C9—H9B	0.99
C2—H2	0.95	C10—H10A	0.99
C3—C4	1.4034 (19)	C10—H10B	0.99
C3—C12	1.4335 (19)	C11—H11A	0.99
C4—C5	1.3734 (19)	C11—H11B	0.99
C4—H4	0.95
C11—O1—C10	90.79 (9)	H7A—C7—H7B	111.1
C6—N2—C7	128.02 (11)	C11—C8—C10	85.12 (10)
C6—N2—C9	130.44 (11)	C11—C8—C9	122.78 (11)
C7—N2—C9	94.47 (10)	C10—C8—C9	122.94 (11)
C2—C1—C6	120.13 (12)	C11—C8—C7	120.34 (11)
C2—C1—H1	119.9	C10—C8—C7	121.30 (11)
C6—C1—H1	119.9	C9—C8—C7	88.49 (10)
C1—C2—C3	120.61 (12)	N2—C9—C8	88.40 (10)
C1—C2—H2	119.7	N2—C9—H9A	113.9
C3—C2—H2	119.7	C8—C9—H9A	113.9
C4—C3—C2	119.53 (12)	N2—C9—H9B	113.9
C4—C3—C12	119.89 (12)	C8—C9—H9B	113.9
C2—C3—C12	120.49 (12)	H9A—C9—H9B	111.1
C5—C4—C3	120.22 (12)	O1—C10—C8	91.91 (10)
C5—C4—H4	119.9	O1—C10—H10A	113.3
C3—C4—H4	119.9	C8—C10—H10A	113.3
C4—C5—C6	120.45 (12)	O1—C10—H10B	113.3
C4—C5—H5	119.8	C8—C10—H10B	113.3
C6—C5—H5	119.8	H10A—C10—H10B	110.6
N2—C6—C5	119.95 (12)	O1—C11—C8	92.11 (10)
N2—C6—C1	121.00 (12)	O1—C11—H11A	113.3
C5—C6—C1	119.05 (12)	C8—C11—H11A	113.3
N2—C7—C8	88.47 (10)	O1—C11—H11B	113.3
N2—C7—H7A	113.9	C8—C11—H11B	113.3
C8—C7—H7A	113.9	H11A—C11—H11B	110.6
N2—C7—H7B	113.9	N1—C12—C3	179.26 (15)
C8—C7—H7B	113.9
C6—C1—C2—C3	0.67 (19)	N2—C7—C8—C11	130.78 (12)
C1—C2—C3—C4	−0.17 (18)	N2—C7—C8—C10	−125.31 (12)
C1—C2—C3—C12	176.30 (12)	N2—C7—C8—C9	3.04 (9)
C2—C3—C4—C5	−0.45 (19)	C6—N2—C9—C8	154.66 (13)
C12—C3—C4—C5	−176.95 (12)	C7—N2—C9—C8	3.21 (10)
C3—C4—C5—C6	0.57 (19)	C11—C8—C9—N2	−128.76 (12)
C7—N2—C6—C5	−18.4 (2)	C10—C8—C9—N2	123.99 (12)
C9—N2—C6—C5	−161.23 (13)	C7—C8—C9—N2	−3.04 (9)
C7—N2—C6—C1	162.08 (12)	C11—O1—C10—C8	−2.22 (10)
C9—N2—C6—C1	19.3 (2)	C11—C8—C10—O1	2.12 (10)
C4—C5—C6—N2	−179.56 (12)	C9—C8—C10—O1	128.42 (12)
C4—C5—C6—C1	−0.07 (19)	C7—C8—C10—O1	−120.66 (12)
C2—C1—C6—N2	178.93 (12)	C10—O1—C11—C8	2.22 (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—O1	121.54 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1^i	0.95	2.47	3.371 (2)	159

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