2-[1′-(Benz­yloxy)spiro­[indane-1,2′-pyrrolidine]-5′-yl]aceto­nitrile

Moreno-Fuquen, R.; Soto, D.M.; Jaramillo-Gómez, L.M.; Ellena, J.; Tenorio, J.C.

doi:10.1107/S1600536813017674

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Pages o1192-o1193

doi:10.1107/S1600536813017674

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2-[1′-(Benzyloxy)spiro[indane-1,2′-pyrrolidine]-5′-yl]acetonitrile

Rodolfo Moreno-Fuquen,^a ^* Diana M. Soto,^a Luz M. Jaramillo-Gómez,^a Javier Ellena ^b and Juan C. Tenorio ^b

^aDepartamento de Química, Facultad de Ciencias, Universidad del Valle, Apartado 25360, Santiago de Cali, Colombia, and ^bInstituto de Física de São Carlos, IFSC, Universidade de São Paulo, USP, São Carlos, SP, Brazil
^*Correspondence e-mail: rodimo26@yahoo.es

(Received 20 June 2013; accepted 26 June 2013; online 3 July 2013)

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 q₂ = 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 q₂ = 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, molecules are linked via C—H⋯N, enclosing R²₂(20) rings, forming chains propagating along [100]. The acetonitrile 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_r = 318.41
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.059
wR(F²) = 0.191
S = 1.05
3617 reflections
249 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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
Symmetry codes: (i) -x+2, -y+2, -z+1.

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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813017674/hg5325sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536813017674/hg5325Isup3.cml

checkCIF report

Comment top

The title compound, 1'-(benzyloxy)-5'-cyanomethyl-2,3-dihydrospiro [inden-1,2'-pyrrolidine], (trans-IIIa), belongs to the family of spirocyclic compounds. It is worthwhile to stand out the natural occurring and synthetic cyclic alkaloids which contain a nitrogen atom adjacent to the spiro carbon. Of special interest are the structures exhibiting the 1-azaspiro[4.4]nonane (I) system (El Bialy et al., 2004) which represents the central core of the cephalotaxine, a natural occurring product isolated from evergreen plum yews of the genus Cephalotaxus (Paudler et al., 1963; Planas et al., 2004), whose ester derivatives as homoharringtonine exhibited a pronounced antileukemic activity (Benderra et al., 1998; Kantarjian et al., 2001; Lévy et al., 2006). Pyrrolidine is a heterocyclic amine used as building block or base in pharmaceutical and fine chemical manufacturing (Boyd et al., 1999; Chen et al., 2012). Therefore, considerable attention has been focused toward the synthesis of molecules with the embedded 1-azaspiro [4.4]nonane (I) system in their structures, using mainly ionic strategy and only scarce examples via radical cyclisation to form out them (El Bialy et al., 2004; Dake, 2006).

Continuing with our current interest in applying tandem reactions under radical conditions, with the participation of aryl and neutral alkyl oxyaminyl radicals (Jaramillo-Gómez et al. 2006), we are reporting here, the synthesis of the azaspirocyclic 1'-(benzyloxy)-5'-cyanomethyl-2,3-dihydrospiro [inden-1,2'-pyrrolidine] (III), as a mixture of the diastereomers cis and trans, being able to crystallize in the pure form, the isomer trans IIIa. The interesting azaspiro [4.4] nonano (I) framework embedded in (III) was obtained in one single synthetic step, from the oxime ether 6-(benzyloxy-imino)-8-(2-iodophenyl)oct-2-enenitrile (II), through a sequential process of two closures 5-exo under standard radical conditions, (scheme 2). The molecular structure of (trans IIIa) is shown in Fig. 1.

The title compound crystallizes in the monoclinic space group P2₁/c. The two phenyl rings are oriented to each other with a dihedral angle of 89.51 (7)°. Analysis of torsion angles, and least-square plane calculation, indicate that pyrrolidine ring shows a puckering amplitude q₂= 0.418 (3) and pseudo-rotation phase angle ϕ₂= -166.8 (5) adopting a twist conformation T with the N atom above the mean plane of the ring. In the same way the other five member ring shows a puckering amplitude q₂= 0.247 (2) and pseudo-rotation phase angle ϕ₂= -173.7 (5) adopting an envelope conformation E with the atom C9 below the mean plane of the ring (Cremer & Pople, 1975). The N-O bond length is close to the mean value [1.463 (12) Å] reported in the literature (Allen et al., 1987) and the torsion angle formed by the atoms [N1-O1-C15-C16] which links the pyrrolidine and phenyl rings is 179.41 (13)°. The crystal packing reveals that the molecules are linked through a network of weak C—H···N and C—H···O intermolecular interactions (see Table 1, Nardelli, 1995). The C21 atom in the molecule at (x,y,z) donates a proton to N2a y N2b atoms in the molecule at (-x+2,-y+2,-z+1), forming as a result of these interactions R²₂(20) rings (Etter, 1990). These rings are in turn linked by a weak C-H···O interaction. Indeed, the C23 atom in the molecule at (x,y,z) donates a proton to O1 atom of the molecule at (-x+1,-y+2,-z+1) forming layers parallel to (001) as shown in Fig. 2.

Related literature top

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 top

The reagents and solvents for the synthesis were obtained from the Aldrich Chemical Co., and were used without additional purification. A solution of 6-(benzyloxyimino)-8-(2-iodophenyl)oct-2-enenitrile (II) (129 mg, 0.29 mmol), 2,2'-azobisisobutyronitrile (AIBN, 14 mg, 0.09 mmol) and tributyltin hydride (n-Bu₃SnH, 0.09 ml, 0.35 mmol) in cyclohexane (Cy, 13 mL) was degassed for 1 h by bubbling dry argon, and subsequently stirred at 353 K for 7 h. After cooling to room temperature the solvent was removed under reduced pressure and the crude product treated with a mixture of 20% KF aqueous solution (2 mL) and ethyl acetate (2 mL), stirring overnight. The organic layer was separated, dried with anhydrous Na₂SO₄ and filtered over silica gel. The purification was carried out by flash column chromatography with 60-95% benzene/hexane (gradient 5%) to afford a mixture of two diastereomers IIIa and IIIb (59 mg, 65%) as yellow oil. By addition of hexane to this oil, white crystals suitable for X-ray diffraction, fell down [20 mg, 21%, m.p. 372 (1) K] of the diastereomeric spirocycle trans-IIIa suitable for X-ray analysis. Elemental Analysis: Calculated: C 79.20, H 6.98, N 8.80; Found: C 79.25, H 6.73, N 8.85.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); 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).

Figures top

	Fig. 1. Molecular conformation and atom numbering scheme for the title compound with displacement ellipsoids drawn at the 50% probability level. H atoms were omitted for more clarity.
	Fig. 2. Part of the crystal structure of (IIIa), forming layers in the ab plane. Symmetry code: (i) -x+2,-y+2,-z+1; (ii) -x+1,-y+2,-z+1.
	Fig. 3. Reaction scheme.

2-[1'-(Benzyloxy)spiro[indane-1,2'-pyrrolidine]-5'-yl]acetonitrile top

Crystal data top

C₂₁H₂₂N₂O	Z = 2
M_r = 318.41	F(000) = 340
Triclinic, P1	D_x = 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

Data collection top

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

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) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0894P)² + 0.0489P] where P = (F_o² + 2F_c²)/3
3617 reflections	(Δ/σ)_max < 0.001
249 parameters	Δρ_max = 0.11 e Å⁻³
3 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₂₁H₂₂N₂O	γ = 110.403 (4)°
M_r = 318.41	V = 893.17 (7) Å³
Triclinic, P1	Z = 2
a = 9.1688 (4) Å	Mo Kα radiation
b = 10.0800 (4) Å	µ = 0.07 mm⁻¹
c = 11.4141 (6) Å	T = 295 K
α = 98.826 (2)°	0.29 × 0.25 × 0.15 mm
β = 108.777 (2)°

Data collection top

Nonius KappaCCD diffractometer	2307 reflections with I > 2σ(I)
6429 measured reflections	R_int = 0.063
3617 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	3 restraints
wR(F²) = 0.191	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.11 e Å⁻³
3617 reflections	Δρ_min = −0.13 e Å⁻³
249 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₂N₂O
M_r	318.41
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	9.1688 (4), 10.0800 (4), 11.4141 (6)
α, β, γ (°)	98.826 (2), 108.777 (2), 110.403 (4)
V (Å³)	893.17 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.29 × 0.25 × 0.15

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6429, 3617, 2307
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.191, 1.05
No. of reflections	3617
No. of parameters	249
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.11, −0.13

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C21—H21···N2Bⁱ	0.93	2.61	3.511 (15)	164.4
C21—H21···N2Aⁱ	0.93	2.48	3.390 (18)	168.0
C13B—H134···O1ⁱⁱ	0.97	2.87	3.389 (9)	114.5

Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y+2, −z+1.

Acknowledgements

RMF and LMJG are grateful to the Universidad del Valle, Colombia, for partial financial support.

References

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