2-[1'-(Benz-yloxy)spiro-[indane-1,2'-pyrrolidine]-5'-yl]aceto-nitrile.

In the title compound, C21H22N2O, the planes of the two six-membered rings make a dihedral angle of 89.51 (7)°. The pyrrolidine ring has a puckering amplitude q 2 = 0.418 (3) and a pseudo-rotation phase angle ϕ2 = -166.8 (5), adopting a twist conformation (T). The other five-membered ring has a puckering amplitude q 2 = 0.247 (2) and a pseudo-rotation phase angle ϕ2 = -173.7 (5), adopting an envelope conformation with the CH2 atom adjacent to the C atom common with the pyrrolidine ring as the flap. In the crystal, mol-ecules are linked via C-H⋯N, enclosing R (2) 2(20) rings, forming chains propagating along [100]. The aceto-nitrile group is disordered over two positions and was refined with a fixed occupancy ratio of 0.56:0.44.

Related literature

For radical cyclization of 1-aza­spiro compounds, see: El Bialy et al. (2004 ▶); Dake (2006 ▶). For cephalotaxine synthesis, see: Paudler et al. (1963 ▶); Planas et al. (2004 ▶). For esters with anti­leukemic activity, see: Benderra et al. (1998 ▶); Kantarjian et al. (2001 ▶); Lévy et al. (2006 ▶). For pyrrolidine properties, see: Chen et al. (2012 ▶); Boyd et al. (1999 ▶). For tandem reactions under radical conditions, see: Jaramillo-Gómez et al. (2006 ▶). For bond-length data, see: Allen et al. (1987 ▶). For hydrogen bonding, see: Nardelli (1995 ▶) and for hydrogen-bond motifs, see: Etter (1990 ▶). For ring torsion angles, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C21H22N2O

M = 318.41

Triclinic,

a = 9.1688 (4) Å

b = 10.0800 (4) Å

c = 11.4141 (6) Å

α = 98.826 (2)°

β = 108.777 (2)°

γ = 110.403 (4)°

V = 893.17 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.07 mm−1

T = 295 K

0.29 × 0.25 × 0.15 mm

Data collection

Nonius KappaCCD diffractometer

6429 measured reflections

3617 independent reflections

2307 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.191

S = 1.05

3617 reflections

249 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.11 e Å−3

Δρmin = −0.13 e Å−3

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813017674/hg5325sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813017674/hg5325Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813017674/hg5325Isup3.cml

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

C21H22N2O	Z = 2
Mr = 318.41	F(000) = 340
Triclinic, P1	Dx = 1.184 Mg m−3
Hall symbol: -P 1	Melting point: 372(1) K
a = 9.1688 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.0800 (4) Å	Cell parameters from 5157 reflections
c = 11.4141 (6) Å	θ = 2.9–25.7°
α = 98.826 (2)°	µ = 0.07 mm−1
β = 108.777 (2)°	T = 295 K
γ = 110.403 (4)°	Block, white
V = 893.17 (7) Å3	0.29 × 0.25 × 0.15 mm

Nonius KappaCCD diffractometer	2307 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.063
Graphite monochromator	θmax = 26.4°, θmin = 3.0°
CCD rotation images, thick slices scans	h = −11→10
6429 measured reflections	k = −12→12
3617 independent reflections	l = −14→14

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) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0894P)2 + 0.0489P] where P = (Fo2 + 2Fc2)/3
3617 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.11 e Å−3
3 restraints	Δρmin = −0.13 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
O1	0.48268 (14)	0.93003 (12)	0.30050 (11)	0.0770 (4)
N1	0.46487 (19)	0.78319 (16)	0.30577 (14)	0.0779 (4)
C1	0.2926 (2)	0.66924 (19)	0.20916 (18)	0.0789 (5)
C2	0.1560 (2)	0.72661 (18)	0.18692 (19)	0.0784 (5)
C3	0.0707 (3)	0.7469 (2)	0.2642 (2)	0.1021 (7)
H3	0.0910	0.7198	0.3401	0.123*
C4	−0.0441 (3)	0.8075 (3)	0.2276 (3)	0.1190 (8)
H4	−0.1011	0.8212	0.2794	0.143*
C5	−0.0749 (3)	0.8472 (3)	0.1174 (3)	0.1224 (9)
H5	−0.1503	0.8905	0.0955	0.147*
C6	0.0039 (3)	0.8241 (3)	0.0373 (2)	0.1114 (8)
H6	−0.0198	0.8491	−0.0396	0.134*
C7	0.1202 (2)	0.7625 (2)	0.07324 (19)	0.0878 (5)
C8	0.2196 (3)	0.7262 (3)	0.0030 (2)	0.1071 (7)
H8A	0.3110	0.8155	0.0083	0.128*
H8B	0.1470	0.6717	−0.0876	0.128*
C9	0.2901 (3)	0.6305 (2)	0.07358 (19)	0.0958 (6)
H9A	0.2181	0.5260	0.0281	0.115*
H9B	0.4041	0.6519	0.0789	0.115*
C10	0.2684 (4)	0.5431 (3)	0.2722 (3)	0.1171 (8)
H10A	0.1538	0.5014	0.2686	0.141*
H10B	0.2867	0.4648	0.2269	0.141*
C11	0.3975 (4)	0.6097 (3)	0.4117 (3)	0.1284 (10)
H11A	0.3433	0.5835	0.4703	0.154*
H11B	0.4862	0.5751	0.4251	0.154*
C12	0.4700 (4)	0.7747 (3)	0.4335 (2)	0.1040 (7)
C15	0.6189 (2)	0.9965 (2)	0.2623 (2)	0.0990 (7)
H15A	0.5962	0.9367	0.1778	0.119*
H15B	0.7253	1.0050	0.3246	0.119*
C16	0.6290 (2)	1.1473 (2)	0.2575 (2)	0.0853 (5)
C17	0.4913 (2)	1.1636 (2)	0.1765 (2)	0.1015 (7)
H17	0.3909	1.0799	0.1244	0.122*
C18	0.5008 (3)	1.3020 (2)	0.1720 (2)	0.1035 (7)
H18	0.4072	1.3108	0.1167	0.124*
C19	0.6473 (3)	1.4269 (2)	0.2482 (2)	0.0987 (6)
H19	0.6535	1.5203	0.2450	0.118*
C20	0.7837 (3)	1.4125 (2)	0.3289 (2)	0.0985 (7)
H20	0.8833	1.4968	0.3811	0.118*
C21	0.7759 (2)	1.2749 (2)	0.3340 (2)	0.0913 (6)
H21	0.8704	1.2674	0.3896	0.110*
N2A	0.8984 (16)	0.801 (2)	0.4992 (18)	0.115 (3)	0.44
C13A	0.6184 (11)	0.8347 (10)	0.5469 (9)	0.097 (2)	0.44
H131	0.5934	0.8012	0.6163	0.116*	0.44
H132	0.6644	0.9421	0.5727	0.116*	0.44
C14A	0.7383 (11)	0.7889 (10)	0.5243 (10)	0.088 (2)	0.44
N2B	0.8463 (15)	0.7591 (16)	0.5103 (16)	0.131 (3)	0.56
C13B	0.6718 (10)	0.8878 (9)	0.5325 (7)	0.1077 (18)	0.56
H133	0.6979	0.9843	0.5184	0.129*	0.56
H134	0.6827	0.9002	0.6214	0.129*	0.56
C14B	0.7995 (10)	0.8369 (8)	0.5167 (8)	0.0904 (18)	0.56
H12	0.400 (3)	0.821 (2)	0.454 (2)	0.109 (6)*

	U11	U22	U33	U12	U13	U23
O1	0.0734 (7)	0.0694 (7)	0.0904 (8)	0.0416 (6)	0.0252 (6)	0.0203 (6)
N1	0.0945 (10)	0.0754 (9)	0.0749 (9)	0.0552 (8)	0.0267 (8)	0.0232 (7)
C1	0.0921 (12)	0.0670 (10)	0.0862 (12)	0.0423 (9)	0.0369 (10)	0.0232 (8)
C2	0.0791 (10)	0.0624 (9)	0.0939 (13)	0.0315 (8)	0.0337 (9)	0.0232 (8)
C3	0.1121 (15)	0.0891 (13)	0.1370 (18)	0.0530 (12)	0.0723 (14)	0.0453 (13)
C4	0.1025 (16)	0.1018 (17)	0.175 (3)	0.0558 (14)	0.0705 (17)	0.0389 (17)
C5	0.0930 (15)	0.1002 (16)	0.161 (3)	0.0525 (13)	0.0300 (16)	0.0244 (17)
C6	0.1009 (15)	0.0993 (16)	0.1069 (16)	0.0462 (13)	0.0078 (13)	0.0261 (13)
C7	0.0812 (11)	0.0782 (11)	0.0837 (12)	0.0311 (9)	0.0157 (9)	0.0162 (9)
C8	0.1162 (15)	0.1236 (18)	0.0698 (12)	0.0529 (13)	0.0265 (10)	0.0182 (11)
C9	0.1021 (13)	0.0907 (13)	0.0840 (13)	0.0428 (11)	0.0335 (11)	0.0031 (10)
C10	0.157 (2)	0.0902 (15)	0.156 (2)	0.0813 (15)	0.084 (2)	0.0627 (15)
C11	0.203 (3)	0.153 (2)	0.135 (2)	0.135 (2)	0.107 (2)	0.0954 (19)
C12	0.1553 (19)	0.1313 (18)	0.0756 (12)	0.1116 (16)	0.0472 (12)	0.0407 (11)
C15	0.0703 (11)	0.0884 (14)	0.1379 (18)	0.0410 (10)	0.0376 (11)	0.0254 (12)
C16	0.0615 (9)	0.0775 (11)	0.1134 (15)	0.0298 (8)	0.0346 (9)	0.0204 (10)
C17	0.0653 (10)	0.0742 (12)	0.1411 (18)	0.0269 (9)	0.0232 (11)	0.0170 (11)
C18	0.0837 (12)	0.0872 (14)	0.1346 (18)	0.0407 (11)	0.0354 (12)	0.0290 (12)
C19	0.1060 (15)	0.0746 (12)	0.1174 (16)	0.0322 (11)	0.0545 (14)	0.0286 (11)
C20	0.0870 (13)	0.0801 (13)	0.1029 (15)	0.0109 (10)	0.0380 (12)	0.0208 (11)
C21	0.0659 (10)	0.0980 (14)	0.0982 (14)	0.0245 (10)	0.0316 (10)	0.0269 (11)
N2A	0.096 (7)	0.119 (8)	0.122 (5)	0.060 (6)	0.022 (5)	0.029 (5)
C13A	0.146 (5)	0.111 (6)	0.080 (3)	0.097 (4)	0.048 (2)	0.041 (3)
C14A	0.086 (5)	0.081 (5)	0.090 (4)	0.042 (4)	0.020 (4)	0.024 (4)
N2B	0.109 (7)	0.124 (8)	0.146 (6)	0.070 (6)	0.026 (5)	0.011 (5)
C13B	0.171 (3)	0.120 (5)	0.060 (2)	0.103 (3)	0.032 (3)	0.031 (3)
C14B	0.090 (5)	0.080 (4)	0.089 (3)	0.046 (3)	0.013 (3)	0.017 (3)

O1—C15	1.434 (2)	C11—H11A	0.9700
O1—N1	1.4444 (17)	C11—H11B	0.9700
N1—C12	1.460 (3)	C12—C13A	1.395 (9)
N1—C1	1.502 (2)	C12—C13B	1.670 (8)
C1—C2	1.520 (2)	C12—H12	0.97 (2)
C1—C9	1.528 (3)	C15—C16	1.501 (3)
C1—C10	1.540 (3)	C15—H15A	0.9700
C2—C7	1.369 (3)	C15—H15B	0.9700
C2—C3	1.390 (3)	C16—C17	1.384 (3)
C3—C4	1.378 (3)	C16—C21	1.387 (3)
C3—H3	0.9300	C17—C18	1.377 (3)
C4—C5	1.351 (4)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.371 (3)
C5—C6	1.375 (4)	C18—H18	0.9300
C5—H5	0.9300	C19—C20	1.364 (3)
C6—C7	1.396 (3)	C19—H19	0.9300
C6—H6	0.9300	C20—C21	1.374 (3)
C7—C8	1.491 (3)	C20—H20	0.9300
C8—C9	1.529 (3)	C21—H21	0.9300
C8—H8A	0.9700	N2A—C14A	1.553 (17)
C8—H8B	0.9700	C13A—C14A	1.410 (16)
C9—H9A	0.9700	C13A—H131	0.9700
C9—H9B	0.9700	C13A—H132	0.9700
C10—C11	1.514 (4)	N2B—C14B	1.021 (17)
C10—H10A	0.9700	C13B—C14B	1.481 (13)
C10—H10B	0.9700	C13B—H133	0.9700
C11—C12	1.505 (4)	C13B—H134	0.9700
C15—O1—N1	109.50 (12)	C10—C11—H11B	110.7
O1—N1—C12	107.46 (13)	H11A—C11—H11B	108.8
O1—N1—C1	110.06 (12)	C13A—C12—N1	124.5 (4)
C12—N1—C1	106.19 (16)	C13A—C12—C11	105.6 (4)
N1—C1—C2	112.94 (14)	N1—C12—C11	101.52 (17)
N1—C1—C9	111.30 (15)	N1—C12—C13B	103.0 (3)
C2—C1—C9	101.77 (16)	C11—C12—C13B	122.4 (3)
N1—C1—C10	100.66 (17)	C13A—C12—H12	103.9 (13)
C2—C1—C10	115.07 (17)	N1—C12—H12	107.9 (12)
C9—C1—C10	115.58 (17)	C11—C12—H12	113.9 (13)
C7—C2—C3	119.32 (19)	C13B—C12—H12	106.6 (13)
C7—C2—C1	111.24 (17)	O1—C15—C16	106.64 (14)
C3—C2—C1	129.44 (18)	O1—C15—H15A	110.4
C4—C3—C2	119.6 (2)	C16—C15—H15A	110.4
C4—C3—H3	120.2	O1—C15—H15B	110.4
C2—C3—H3	120.2	C16—C15—H15B	110.4
C5—C4—C3	120.8 (3)	H15A—C15—H15B	108.6
C5—C4—H4	119.6	C17—C16—C21	117.70 (19)
C3—C4—H4	119.6	C17—C16—C15	121.00 (17)
C4—C5—C6	120.7 (2)	C21—C16—C15	121.30 (18)
C4—C5—H5	119.6	C18—C17—C16	120.93 (19)
C6—C5—H5	119.6	C18—C17—H17	119.5
C5—C6—C7	118.9 (2)	C16—C17—H17	119.5
C5—C6—H6	120.5	C19—C18—C17	120.5 (2)
C7—C6—H6	120.5	C19—C18—H18	119.7
C2—C7—C6	120.5 (2)	C17—C18—H18	119.7
C2—C7—C8	110.62 (18)	C20—C19—C18	119.1 (2)
C6—C7—C8	128.8 (2)	C20—C19—H19	120.4
C7—C8—C9	103.76 (17)	C18—C19—H19	120.4
C7—C8—H8A	111.0	C19—C20—C21	120.88 (19)
C9—C8—H8A	111.0	C19—C20—H20	119.6
C7—C8—H8B	111.0	C21—C20—H20	119.6
C9—C8—H8B	111.0	C20—C21—C16	120.8 (2)
H8A—C8—H8B	109.0	C20—C21—H21	119.6
C1—C9—C8	106.36 (16)	C16—C21—H21	119.6
C1—C9—H9A	110.5	C12—C13A—C14A	109.0 (8)
C8—C9—H9A	110.5	C12—C13A—H131	109.9
C1—C9—H9B	110.5	C14A—C13A—H131	109.9
C8—C9—H9B	110.5	C12—C13A—H132	109.9
H9A—C9—H9B	108.6	C14A—C13A—H132	109.9
C11—C10—C1	106.99 (19)	H131—C13A—H132	108.3
C11—C10—H10A	110.3	C13A—C14A—N2A	158.1 (9)
C1—C10—H10A	110.3	C14B—C13B—C12	115.0 (6)
C11—C10—H10B	110.3	C14B—C13B—H133	108.5
C1—C10—H10B	110.3	C12—C13B—H133	108.5
H10A—C10—H10B	108.6	C14B—C13B—H134	108.5
C12—C11—C10	105.04 (17)	C12—C13B—H134	108.5
C12—C11—H11A	110.7	H133—C13B—H134	107.5
C10—C11—H11A	110.7	N2B—C14B—C13B	152.4 (10)
C12—C11—H11B	110.7
C15—O1—N1—C12	127.02 (18)	C2—C1—C10—C11	−105.6 (2)
C15—O1—N1—C1	−117.76 (16)	C9—C1—C10—C11	136.2 (2)
O1—N1—C1—C2	−31.15 (19)	C1—C10—C11—C12	10.2 (3)
C12—N1—C1—C2	84.87 (17)	O1—N1—C12—C13A	−78.5 (5)
O1—N1—C1—C9	82.60 (17)	C1—N1—C12—C13A	163.7 (5)
C12—N1—C1—C9	−161.38 (16)	O1—N1—C12—C11	163.27 (17)
O1—N1—C1—C10	−154.38 (14)	C1—N1—C12—C11	45.5 (2)
C12—N1—C1—C10	−38.36 (19)	O1—N1—C12—C13B	−69.3 (3)
N1—C1—C2—C7	102.02 (18)	C1—N1—C12—C13B	173.0 (3)
C9—C1—C2—C7	−17.40 (19)	C10—C11—C12—C13A	−164.3 (5)
C10—C1—C2—C7	−143.16 (19)	C10—C11—C12—N1	−33.3 (2)
N1—C1—C2—C3	−77.2 (2)	C10—C11—C12—C13B	−146.9 (4)
C9—C1—C2—C3	163.37 (19)	N1—O1—C15—C16	179.41 (14)
C10—C1—C2—C3	37.6 (3)	O1—C15—C16—C17	−59.3 (3)
C7—C2—C3—C4	−2.2 (3)	O1—C15—C16—C21	120.56 (19)
C1—C2—C3—C4	176.98 (19)	C21—C16—C17—C18	0.3 (3)
C2—C3—C4—C5	0.1 (4)	C15—C16—C17—C18	−179.8 (2)
C3—C4—C5—C6	1.9 (4)	C16—C17—C18—C19	−0.3 (4)
C4—C5—C6—C7	−1.7 (4)	C17—C18—C19—C20	0.0 (4)
C3—C2—C7—C6	2.4 (3)	C18—C19—C20—C21	0.2 (3)
C1—C2—C7—C6	−176.96 (17)	C19—C20—C21—C16	−0.1 (3)
C3—C2—C7—C8	−177.52 (18)	C17—C16—C21—C20	−0.2 (3)
C1—C2—C7—C8	3.2 (2)	C15—C16—C21—C20	−179.98 (18)
C5—C6—C7—C2	−0.4 (3)	N1—C12—C13A—C14A	−49.7 (7)
C5—C6—C7—C8	179.4 (2)	C11—C12—C13A—C14A	66.6 (6)
C2—C7—C8—C9	12.6 (2)	C13B—C12—C13A—C14A	−73.4 (17)
C6—C7—C8—C9	−167.3 (2)	C12—C13A—C14A—N2A	105 (3)
N1—C1—C9—C8	−96.19 (19)	C13A—C12—C13B—C14B	93.7 (19)
C2—C1—C9—C8	24.4 (2)	N1—C12—C13B—C14B	−66.5 (5)
C10—C1—C9—C8	149.8 (2)	C11—C12—C13B—C14B	46.4 (6)
C7—C8—C9—C1	−23.2 (2)	C12—C13B—C14B—N2B	−51 (3)
N1—C1—C10—C11	16.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···N2Bi	0.93	2.61	3.511 (15)	164
C21—H21···N2Ai	0.93	2.48	3.390 (18)	168
C13B—H134···O1ii	0.97	2.87	3.389 (9)	115

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯N2B i	0.93	2.61	3.511 (15)	164
C21—H21⋯N2A i	0.93	2.48	3.390 (18)	168

Symmetry codes: (i) .