7-Benzyl-2,7-diaza­spiro­[4.4]nonan-1-one

Guo, H.-M.

doi:10.1107/S1600536811034301

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2517

doi:10.1107/S1600536811034301

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7-Benzyl-2,7-diazaspiro[4.4]nonan-1-one

Huan-Mei Guo ^a ^*

^aMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: huanmeiguo@163.com

(Received 27 July 2011; accepted 21 August 2011; online 27 August 2011)

In the title compound, C₁₄H₁₈N₂O, both the spiro-linked five-membered rings adopt envelope conformations, with a C atom as the flap in one ring and an N atom in the other. The dihedral angle between the two four-atom planes is 80.46 (8)°. In the crystal, the molecules are linked by N—H⋯O hydrogen bonds to generate C(4) chains propagating in [010].

Related literature

For background to pyrrolidine derivatives, see: Kuroki et al. (1999 ); Hale et al. (2001 ); Shen et al. (2004 ).

Experimental

Crystal data

C₁₄H₁₈N₂O
M_r = 230.30
Orthorhombic, P b c a
a = 9.630 (2) Å
b = 8.4322 (18) Å
c = 29.848 (7) Å
V = 2423.8 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 173 K
0.21 × 0.18 × 0.17 mm

Data collection

MM007-HF CCD (Saturn 724+) diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007 ) T_min = 0.983, T_max = 0.986
9156 measured reflections
2761 independent reflections
2495 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.120
S = 1.16
2761 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.88	2.14	2.9839 (19)	160
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811034301/hb6338sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034301/hb6338Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811034301/hb6338Isup3.cml

checkCIF report

Comment top

While a great number of pyrrolidines and their derivatives with specific substitution pattern are of particular interest, new methods for their preparation are needed; e.g. Kuroki et al., (1999); Hale et al., (2001); Shen et al., (2004). As part of our research work in this area, the title compound, (I), was synthesized, and herein we report the structure of it.

In the molecule (Fig. 1), all bond lengths and angles are within normal ranges. Atoms C8, C9, C10, and C11 lie in a plane (p1),with a maximum deviation of 0.01102 (11)Å for C10; atoms C10, C13, C14, and N3 lie in a plane (p2) too, the maximum deviation is 0.0045 (10)Å for N3. The dihedral angle between the two plans is 80.46 (8)°. The dihedral angles made by the phenyl ring with p1anes p1 and p2 are 53.56 (9)° and 50.21 (6)°, respectively. The structure exhibits intermolecular N3—H···O1 hydrogen bonding interactions (Table 1), which link the molecules into chains.

Related literature top

For background to pyrrolidine derivatives, see: Kuroki et al. (1999); Hale et al. (2001); Shen et al., (2004).

Experimental top

The title molecule, C₁₄H₁₈N₂O₁, was synthesized from methyl 1-benzyl-3-(cyanomethyl) pyrrolidine-3-carboxylate and Raney Ni (w/w = 4: 1) in methanol under H₂ (50 Psi) atmosphere at room temperature. Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.

7-Benzyl-2,7-diazaspiro[4.4]nonan-1-one top

Crystal data top

C₁₄H₁₈N₂O	F(000) = 992
M_r = 230.30	D_x = 1.262 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 6994 reflections
a = 9.630 (2) Å	θ = 1.4–27.5°
b = 8.4322 (18) Å	µ = 0.08 mm⁻¹
c = 29.848 (7) Å	T = 173 K
V = 2423.8 (9) Å³	Block, colorless
Z = 8	0.21 × 0.18 × 0.17 mm

Data collection top

MM007-HF CCD (Saturn 724+) diffractometer	2761 independent reflections
Radiation source: rotating anode	2495 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.046
ω scans at fixed χ = 45°	θ_max = 27.5°, θ_min = 2.5°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	h = −7→12
T_min = 0.983, T_max = 0.986	k = −7→10
9156 measured reflections	l = −38→38

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H-atom parameters constrained
S = 1.16	w = 1/[σ²(F_o²) + (0.030P)² + 1.3429P] where P = (F_o² + 2F_c²)/3
2761 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₄H₁₈N₂O	V = 2423.8 (9) Å³
M_r = 230.30	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.630 (2) Å	µ = 0.08 mm⁻¹
b = 8.4322 (18) Å	T = 173 K
c = 29.848 (7) Å	0.21 × 0.18 × 0.17 mm

Data collection top

MM007-HF CCD (Saturn 724+) diffractometer	2761 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007)	2495 reflections with I > 2σ(I)
T_min = 0.983, T_max = 0.986	R_int = 0.046
9156 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	0 restraints
wR(F²) = 0.120	H-atom parameters constrained
S = 1.16	Δρ_max = 0.22 e Å⁻³
2761 reflections	Δρ_min = −0.19 e Å⁻³
154 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
O1	0.27133 (12)	0.12904 (14)	0.47500 (4)	0.0295 (3)
N1	0.48470 (14)	0.35120 (16)	0.37041 (4)	0.0226 (3)
N3	0.39956 (15)	−0.08606 (16)	0.45320 (5)	0.0265 (3)
H3	0.3485	−0.1589	0.4664	0.032*
C1	0.39718 (18)	0.6967 (2)	0.29710 (6)	0.0279 (4)
H1	0.3010	0.6777	0.2924	0.033*
C2	0.4556 (2)	0.8372 (2)	0.28234 (6)	0.0324 (4)
H2	0.3996	0.9135	0.2675	0.039*
C3	0.5953 (2)	0.8667 (2)	0.28919 (6)	0.0319 (4)
H3A	0.6352	0.9636	0.2793	0.038*
C4	0.67658 (19)	0.7545 (2)	0.31053 (6)	0.0305 (4)
H4	0.7726	0.7741	0.3153	0.037*
C5	0.61789 (17)	0.61353 (19)	0.32491 (6)	0.0255 (4)
H5	0.6746	0.5365	0.3392	0.031*
C6	0.47727 (17)	0.58284 (19)	0.31871 (5)	0.0228 (3)
C7	0.41177 (18)	0.4289 (2)	0.33361 (6)	0.0259 (4)
H7B	0.3149	0.4501	0.3430	0.031*
H7A	0.4085	0.3554	0.3078	0.031*
C8	0.48226 (19)	0.4420 (2)	0.41228 (5)	0.0266 (4)
H8A	0.3889	0.4870	0.4178	0.032*
H8B	0.5508	0.5294	0.4115	0.032*
C9	0.5201 (2)	0.3210 (2)	0.44804 (6)	0.0315 (4)
H9A	0.4680	0.3417	0.4760	0.038*
H9B	0.6207	0.3248	0.4547	0.038*
C10	0.47966 (17)	0.15873 (19)	0.42824 (5)	0.0237 (4)
C11	0.41627 (19)	0.2024 (2)	0.38238 (5)	0.0264 (4)
H11B	0.4358	0.1191	0.3599	0.032*
H11A	0.3145	0.2169	0.3848	0.032*
C12	0.59701 (18)	0.0370 (2)	0.42444 (6)	0.0310 (4)
H12A	0.6471	0.0487	0.3957	0.037*
H12B	0.6640	0.0489	0.4494	0.037*
C13	0.52313 (19)	−0.1232 (2)	0.42691 (6)	0.0317 (4)
H13A	0.4981	−0.1622	0.3967	0.038*
H13B	0.5814	−0.2036	0.4421	0.038*
C14	0.37117 (16)	0.06900 (19)	0.45541 (5)	0.0220 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0269 (6)	0.0299 (7)	0.0317 (6)	0.0042 (5)	0.0045 (5)	0.0012 (5)
N1	0.0255 (7)	0.0193 (7)	0.0231 (7)	−0.0027 (6)	−0.0004 (5)	0.0010 (5)
N3	0.0277 (7)	0.0197 (7)	0.0321 (8)	−0.0019 (6)	0.0035 (6)	0.0033 (6)
C1	0.0259 (8)	0.0299 (9)	0.0279 (8)	0.0013 (8)	−0.0008 (7)	0.0021 (7)
C2	0.0361 (10)	0.0283 (9)	0.0329 (9)	0.0047 (8)	−0.0023 (8)	0.0071 (7)
C3	0.0383 (10)	0.0255 (9)	0.0320 (9)	−0.0055 (8)	0.0031 (8)	0.0054 (7)
C4	0.0273 (9)	0.0283 (9)	0.0358 (9)	−0.0047 (7)	0.0024 (7)	−0.0001 (7)
C5	0.0246 (8)	0.0232 (8)	0.0289 (9)	0.0013 (7)	0.0008 (7)	0.0015 (7)
C6	0.0245 (8)	0.0214 (8)	0.0226 (8)	−0.0004 (7)	0.0007 (6)	−0.0006 (6)
C7	0.0244 (8)	0.0258 (9)	0.0276 (8)	−0.0035 (7)	−0.0021 (6)	0.0036 (7)
C8	0.0308 (9)	0.0227 (8)	0.0263 (8)	−0.0014 (7)	0.0028 (7)	−0.0020 (7)
C9	0.0399 (10)	0.0272 (9)	0.0273 (9)	−0.0090 (8)	−0.0052 (7)	0.0006 (7)
C10	0.0265 (8)	0.0209 (8)	0.0237 (8)	−0.0025 (7)	−0.0016 (6)	0.0012 (6)
C11	0.0307 (9)	0.0240 (8)	0.0245 (8)	−0.0058 (7)	−0.0035 (7)	0.0032 (7)
C12	0.0264 (9)	0.0344 (10)	0.0324 (9)	0.0023 (8)	0.0053 (7)	0.0032 (8)
C13	0.0352 (10)	0.0260 (9)	0.0341 (9)	0.0066 (8)	0.0034 (8)	−0.0010 (7)
C14	0.0218 (8)	0.0228 (8)	0.0214 (7)	−0.0004 (7)	−0.0019 (6)	0.0010 (6)

Geometric parameters (Å, º) top

O1—C14	1.2341 (19)	C7—H7B	0.9900
N1—C7	1.459 (2)	C7—H7A	0.9900
N1—C11	1.462 (2)	C8—C9	1.521 (2)
N1—C8	1.466 (2)	C8—H8A	0.9900
N3—C14	1.337 (2)	C8—H8B	0.9900
N3—C13	1.460 (2)	C9—C10	1.540 (2)
N3—H3	0.8800	C9—H9A	0.9900
C1—C2	1.383 (2)	C9—H9B	0.9900
C1—C6	1.390 (2)	C10—C14	1.524 (2)
C1—H1	0.9500	C10—C12	1.531 (2)
C2—C3	1.384 (3)	C10—C11	1.544 (2)
C2—H2	0.9500	C11—H11B	0.9900
C3—C4	1.384 (3)	C11—H11A	0.9900
C3—H3A	0.9500	C12—C13	1.529 (2)
C4—C5	1.384 (2)	C12—H12A	0.9900
C4—H4	0.9500	C12—H12B	0.9900
C5—C6	1.391 (2)	C13—H13A	0.9900
C5—H5	0.9500	C13—H13B	0.9900
C6—C7	1.510 (2)

C7—N1—C11	110.62 (13)	H8A—C8—H8B	108.9
C7—N1—C8	113.55 (13)	C8—C9—C10	105.45 (14)
C11—N1—C8	103.47 (13)	C8—C9—H9A	110.7
C14—N3—C13	113.77 (14)	C10—C9—H9A	110.7
C14—N3—H3	123.1	C8—C9—H9B	110.7
C13—N3—H3	123.1	C10—C9—H9B	110.7
C2—C1—C6	120.90 (16)	H9A—C9—H9B	108.8
C2—C1—H1	119.5	C14—C10—C12	102.28 (13)
C6—C1—H1	119.5	C14—C10—C9	114.22 (14)
C1—C2—C3	120.16 (17)	C12—C10—C9	115.95 (14)
C1—C2—H2	119.9	C14—C10—C11	108.61 (13)
C3—C2—H2	119.9	C12—C10—C11	112.71 (14)
C4—C3—C2	119.67 (17)	C9—C10—C11	103.19 (13)
C4—C3—H3A	120.2	N1—C11—C10	104.07 (13)
C2—C3—H3A	120.2	N1—C11—H11B	110.9
C3—C4—C5	119.94 (17)	C10—C11—H11B	110.9
C3—C4—H4	120.0	N1—C11—H11A	110.9
C5—C4—H4	120.0	C10—C11—H11A	110.9
C4—C5—C6	121.06 (16)	H11B—C11—H11A	109.0
C4—C5—H5	119.5	C13—C12—C10	104.21 (14)
C6—C5—H5	119.5	C13—C12—H12A	110.9
C1—C6—C5	118.26 (15)	C10—C12—H12A	110.9
C1—C6—C7	119.90 (15)	C13—C12—H12B	110.9
C5—C6—C7	121.82 (15)	C10—C12—H12B	110.9
N1—C7—C6	113.99 (13)	H12A—C12—H12B	108.9
N1—C7—H7B	108.8	N3—C13—C12	102.45 (13)
C6—C7—H7B	108.8	N3—C13—H13A	111.3
N1—C7—H7A	108.8	C12—C13—H13A	111.3
C6—C7—H7A	108.8	N3—C13—H13B	111.3
H7B—C7—H7A	107.7	C12—C13—H13B	111.3
N1—C8—C9	104.13 (14)	H13A—C13—H13B	109.2
N1—C8—H8A	110.9	O1—C14—N3	125.71 (15)
C9—C8—H8A	110.9	O1—C14—C10	125.64 (15)
N1—C8—H8B	110.9	N3—C14—C10	108.61 (14)
C9—C8—H8B	110.9

C6—C1—C2—C3	−0.4 (3)	C7—N1—C11—C10	−165.66 (13)
C1—C2—C3—C4	0.6 (3)	C8—N1—C11—C10	−43.71 (16)
C2—C3—C4—C5	0.0 (3)	C14—C10—C11—N1	149.00 (13)
C3—C4—C5—C6	−0.7 (3)	C12—C10—C11—N1	−98.41 (16)
C2—C1—C6—C5	−0.3 (2)	C9—C10—C11—N1	27.42 (17)
C2—C1—C6—C7	−178.67 (16)	C14—C10—C12—C13	28.06 (17)
C4—C5—C6—C1	0.9 (2)	C9—C10—C12—C13	153.01 (15)
C4—C5—C6—C7	179.16 (16)	C11—C10—C12—C13	−88.38 (16)
C11—N1—C7—C6	−179.16 (13)	C14—N3—C13—C12	17.26 (19)
C8—N1—C7—C6	65.02 (18)	C10—C12—C13—N3	−27.63 (17)
C1—C6—C7—N1	−156.04 (15)	C13—N3—C14—O1	178.80 (16)
C5—C6—C7—N1	25.7 (2)	C13—N3—C14—C10	0.86 (19)
C7—N1—C8—C9	162.37 (14)	C12—C10—C14—O1	163.51 (16)
C11—N1—C8—C9	42.41 (16)	C9—C10—C14—O1	37.4 (2)
N1—C8—C9—C10	−24.29 (18)	C11—C10—C14—O1	−77.1 (2)
C8—C9—C10—C14	−119.53 (15)	C12—C10—C14—N3	−18.55 (17)
C8—C9—C10—C12	121.90 (16)	C9—C10—C14—N3	−144.63 (14)
C8—C9—C10—C11	−1.82 (18)	C11—C10—C14—N3	100.81 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.88	2.14	2.9839 (19)	160

Symmetry code: (i) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₈N₂O
M_r	230.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	173
a, b, c (Å)	9.630 (2), 8.4322 (18), 29.848 (7)
V (Å³)	2423.8 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.21 × 0.18 × 0.17

Data collection
Diffractometer	MM007-HF CCD (Saturn 724+) diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2007)
T_min, T_max	0.983, 0.986
No. of measured, independent and observed [I > 2σ(I)] reflections	9156, 2761, 2495
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.120, 1.16
No. of reflections	2761
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.19

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.88	2.14	2.9839 (19)	160

Symmetry code: (i) −x+1/2, y−1/2, z.

Acknowledgements

The author thanks Shandong Provincial Natural Science Foundation, China (grant No. Y2008B29) and Yuandu Scholar of Weifang City for support.

References

Hale, J. J., Budhu, R. J., Mills, S. G., MacCoss, M., Malkowitz, L., Siciliano, S., Gould, S. L., DeMartino, J. A. & Springer, M. S. (2001). Bioorg. Med. Chem. Lett. 11, 1437–1440. CrossRef CAS Google Scholar
Kuroki, Y. & Iseki, K. (1999). Tetrahedron Lett. 40, 8231–8234. CAS Google Scholar
Rigaku (2007). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, D. M., et al. (2004). Bioorg. Med. Chem. Lett. 14, 953–957. Google Scholar