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The title compound, C20H25N3O, an important precursor for the preparation of benzovesamicol analogues for the diagnosis of Alzheimer's disease, has been synthesized and characterized by FT–IR, and 1H and 13C NMR spectroscopic analyses. The crystal structure was analysed using powder diffraction as no suitable single crystal was obtained. The piperazine ring has a chair conformation, while the cyclo­hexene ring assumes a half-chair conformation. The crystal packing is mediated by weak contacts, principally by complementary inter­molecular N—H...O hydrogen bonds that connect successive mol­ecules into a chain. Further stabilization is provided by weak C—H...N contacts and by a weak inter­molecular C—H...π inter­action.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111036869/fa3258sup1.cif
Contains datablocks global, I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270111036869/fa3258Isup2.rtv
Contains datablock I

CCDC reference: 794149

Comment top

Racemic (2RS,3RS)-5-amino-3-(4-phenylpiperazin-1-yl)-1,2,3,4-tetrahydronaphthalen-2-ol is a benzovesamicol analogue which is well known to be a stereoselective inhibitor of acetylcholine uptake in presynaptic cholinergic vesicles. Radiolabelled benzovesamicol analogues have been widely used as imaging probes in single photon emission computer tomography (SPECT) and positron emission tomography (PET) aimed at in vitro and in vivo studies of Alzheimer's disease (Alfonso et al., 1993; Efange et al., 1997; Auld et al., 2002; Mulholland & Jung, 1992; Mulholland et al., 1993; Nicolas et al., 2007; Rogers et al., 1989; Zea-Ponce et al., 2005).

The aims of the present study were the synthesis and the three-dimensional structure determination of the title compound, (2RS,3RS)-(I). The synthesis consisted of the addition of 1-phenylpiperazine to the 2,2,2-trifluoro-N-(1a,2,7,7a-tetrahydronaphtho[2,3-b]oxiren-3-yl)acetamide to obtain two regioisomers, which were separated by flash chromatography (silica gel; Et2O and Et3N, 10:1) (see Scheme). The compound (2RS,3RS)-(I) was characterized by IR and 13C, 1H NMR spectroscopy and yielded results consistent with the assigned structure.

(2RS,3RS)-(I) crystallizes as a very fine white powder. Since no single crystal of sufficient size and quality was obtained, a structure determination by powder X-ray diffraction was undertaken. In recent years the crystal structures of a number of compounds of pharmaceutical interest have been solved ab initio from powder X-ray diffraction data in the absence of single crystals of sufficient quality (Chan et al., 1999; Shankland et al., 2001; Chernyshev et al., 2003; Kiang et al., 2003; Rukiah et al., 2004; van der Lee et al., 2005; Rukiah & Assaad, 2010; Al-Ktaifani & Rukiah, 2010; Rukiah & Al-Ktaifani, 2011). We used in-house powder X-ray diffraction data to solve and refine the crystal structure of (2RS,3RS)-(I). For a 24-atom (non-H) problem such as this, careful measurement and interpretation are necessary in order to optimize the results.

(2RS,3RS)-(I) (Fig. 1) crystallizes with one molecule in the asymmetric unit in space group P21/c. Bond lengths and angles fall within their normal ranges (Allen et al., 1987). The molecule contains four six-membered rings (two phenyl, piperazine and cyclohexene rings). The piperazine ring adopts a chair conformation with puckering parameters (Cremer & Pople, 1975) Q = 0.603 (7) Å, θ = 12.5 (8)° and ϕ = 195 (2)°. Bond lengths and angles around C14 and C15 (Table 1) confirm the nature of the cyclohexene double bond. The cyclohexene ring assumes a conformation approximating a half-chair [puckering parameters Q = 0.471 (7) Å, θ = 54.1 (10)° and ϕ = 20.7 (12)°] with C13/C14/C15/C16 nearly coplanar [maximum deviation -0.148 (6) Å], and C11 and C12 situated 0.319 (7) and 0.283 (7) Å, respectively, on opposite sides of the mean plane. Cyclohexene is trans-fused to the adjacent phenyl ring (C14/C15/C20/C19/C18/C17) through C14 and C15.

As shown in Fig. 2, the most noteworthy non-covalent feature of the structure is an intramolecular contact between a hydroxy H atom and N of the piperazine ring (O1—H1O···N2) (Fig. 2, Table 2). In this interaction the angle at H is narrow (108°), outside the range normally considered for a hydrogen bond. H1O was observed in a difference map but refined with a bond-length constraint. It is possible that its position is not exact; but in any event the O1—H1O···N2 contact is not a proper hydrogen bond, as the narrow angle signifies that H1O does not present its most electropositive potential in the direction of N2.

The further contacts present (Table 2) have D···A distances at or beyond the sum of the van der Waals radii of the D and A atoms. N3—H1N3···O1i contacts [(i): x, -y-1/2, z-1/2] mediate the formation of chains running in opposite directions along [001] (Fig. 2). C18—H18···N3ii contacts [(ii): -x, y-1/2, -z+3/2], between adjacent chains and with amine N3 as acceptor, further stabilize the structure. Along the b axis the structure is supported by a weak C7—H7A···Cg4iii [(iii): x, y+1, z] C–H···π interaction, where Cg4 is the centre of gravity of the phenyl ring (C14/C15/C20/C19/C18/C17). This contact lies near the upper limit of H···Cg contact distances for such interactions to be considered significant. We can speculate that the fact that only fine powder is obtained for this compound may be related to the weak packing forces present.

Related literature top

For related literature, see: Al-Ktaifani & Rukiah (2010); Alfonso et al. (1993); Allen et al. (1987); Altomare et al. (2004); Auld et al. (2002); Bando et al. (2000, 2001); Boultif & Louër (2004); Chan et al. (1999); Chernyshev et al. (2003); Cremer & Pople (1975); Efange et al. (1997); Farrugia (1997); Favre-Nicolin & Černý (2002); Finger et al. (1994); Kiang et al. (2003); Larson & Von Dreele (2004); Le Bail, Duroy & Fourquet (1988); van der Lee et al. (2005); Mulholland & Jung (1992); Mulholland et al. (1993); Nicolas et al. (2007); Rodriguez-Carvajal (2001); Rogers et al. (1989); Roisnel & Rodriguez-Carvajal (2001); Rukiah & Al-Ktaifani (2011); Rukiah & Assaad (2010); Rukiah et al. (2004); Shankland et al. (2001); Thompson et al. (1987); Toby (2001); Von Dreele (1997); Zea-Ponce, Mavel, Assaad, Kruse, Parsons, Emond, Chalon, Kruse, Giboureau, Kassiou & Guilloteau (2005).

Experimental top

2,2,2-Trifluoro-N-(1a,2,7,7a-tetrahydronaphtho[2,3-b]oxiren-3 yl)acetamide was prepared by previously reported methods (Rukiah & Assaad, 2010). All other chemicals were obtained commercially and used without further purification. The title compound, (2RS,3RS)-(I), was prepared by a procedure similar to that reported in the literature (Bando et al., 2000, 2001).

For the synthesis of (2R,3R/2S,3S)-(I), 1-phenylpiperazine (3 g, 19 mmol) was added to a solution of 2,2,2-trifluoro-N-(1a,2,7,7a-tetrahydronaphtho[2,3-b]oxiren-3-yl)acetamide (1.9 g, 7.4 mmol) in ethanol (25 ml). The solution was allowed to reflux for 16 h and was then kept for 24 h at room temperature to produce a crystalline solid. The solid was filtered and dried under vacuum, then dissolved in methanol (25 ml) and treated with 1 N NaOH (15 ml). The mixture was stirred at room temperature for 16 h and then extracted with CH2Cl2 (3 x 25 ml). The organic layer was dried over anhydrous Na2SO4 and concentrated under reduced pressure. The resulting regioisomers were separated by silica gel chromatography with Et2O:Et3N (10:1), to give 665 mg (35%) of (2R,3R/2S,3S)-(I), Rf = 0.55 (m.p. 505 K) and 684 mg (36%) of (2R,3R/2S,3S)-(II), Rf = 0.26 (m.p. 445 K).

The powder sample of compound (2RS,3RS)-(I) was gently ground in a mortar, loaded between two Mylar foils and fixed in the sample holder with a mask of suitable internal diameter (7.0 mm). X-ray powder diffraction data were collected at room temperature with a Stoe Stadi P diffractometer using monochromatic Cu Kα1 radiation (λ = 1.54060 Å) selected with an incident beam curved-crystal germanium (111) monochromator, and using the Stoe transmission geometry (horizontal set-up) with a linear position-sensitive detector (PSD). The pattern was scanned over the angular range of 5–90° (2θ).

Spectroscopic data for (2RS,3RS)-(I): 1H-NMR (CDCl3):d 2.49–2.56 (m, 2H, 2H-10), 2.72–3.33 (m,12H, 2H-1, 2H-4,2H-10, 4H-9, H-3, OH), 3.60 (s, NH2), 3.91-3.97 (m, 1H, H-2), 6.57–6.63 (m, 2H, H-6, H-8), 6.91 (t, 2H, 3J = 7.2 Hz, 2HAr), 6.99–7.04 (m, 1H, H-7) 7.28–7.33 (m, 3H, 3HAr).13C-NMR (CDCl3): d 20.9 (2 C-10), 38.0 (C-1), 48.1 (C-4), 49.9 (C-3), 65.2 (C-2), 66.2 (2 C-9), 112.7 (CHAr), 116.3 (2CHAr), 119.3 (CAr),119.6 (CHAr), 120.0 (CHAr), 127.1(CHAr), 129.1 (2CHAr), 134.7 (CAr), 144.4 (C– NH2), 151.2 (CAr). IR (KBr, n cm-1): 3200–3350.4 (NH2), 3459.5 (OH), 3050 (CHCH, Ar), 2918.2–2850.9 (CH2, aliphatic), 2850.9 (CH2—NH2), 1636.6 (CC), 1137.6 (C—N, piperazine).

Refinement top

For pattern indexing, the extraction of the peak positions was carried out with the program WinPLOTR (Roisnel & Rodriguez-Carvajal, 2001). Pattern indexing was performed with the program DicVol4.0 (Boultif & Louër, 2004). The first 20 lines were completely indexed on the basis of a monoclinic cell. The absolute error on each observed line was fixed at 0.02° (2θ). The figures of merit [M(20) = 17.9, F(20) = 36.6] are sufficient to support the results obtained. The entire powder diffraction pattern from 5 to 90° (2θ) was subsequently refined with cell and resolution constraints (Le Bail et al., 1988) using a monoclinic space group without systematic absences, P2/m, using the `profile matching' option of the program FullProf (Rodriguez-Carvajal, 2001). The monoclinic space group P21/c was chosen with the help of the program Check Group interfaced by WinPLOTR. The number of molecules per unit cell was estimated to be Z = 4, giving Z' = 1 molecule per asymmetric unit for this space group. Structure solution was attempted ab initio by direct methods using the program EXPO2004 (Altomare et al., 2004), but with no success. Therefore, the direct space method was used (FOX, Favre-Nicolin & Černý, 2002) for finding the starting model. It is worth pointing out that FOX solves structures by altering the positions, orientations and conformations of the molecule(s) in the unit cell according to the constraints of space-group symmetry, until a good match is obtained between the calculated and observed intensities. The starting model was found using the `parallel tempering' algorithm of the Monte Carlo simulated annealing method. The 2θ angular range was restricted from 5.0 to 55.0° to speed up the Monte Carlo calculations. The profile parameter needed for the program was calculated from preliminary profile-matching refinements carried out with the program FOX itself. During the Monte Carlo simulated annealing calculations, each molecule was allowed to translate, to rotate around its centre of mass and to have its torsion angles vary. The molecule (2RS,3RS)-(I) has two independent torsion angles, so there are eight degrees of freedom to determine for the starting model. The hydrogen atoms were not included at this stage. After roughly one million cycles, the agreement factor Rwp was near 10% for a solution corresponding to a configuration which provided a credible starting model in terms of crystal packing. The shortest contact distance between neighbouring molecules was 3.15 Å between a hydroxy O and a neighbouring amine N, representing a possible hydrogen-bond distance.

The model found by this program was introduced in the program GSAS (Larson & Von Dreele, 2004) implemented in EXPGUI (Toby, 2001) for Rietveld refinements. The effect of the asymmetry of low-order peaks was corrected using a pseudo-Voigt description of the peak shape (Thompson et al., 1987) which allows for angle-dependent asymmetry with axial divergence (Finger et al., 1994). The two asymmetry parameters of this function S/L and D/L were both fixed at 0.0215 during the Rietveld refinement. Suitable restraints to their normal values were imposed on bond lengths for the coordinates of the 24 non-H atoms. Unit weights were used for these restraints. A global isotropic atomic displacement parameter was introduced for C, N and O. Intensities were corrected for absorption effects with a µ.d value of 0.164. Before the final refinement, aromatic H, H atoms of methylene and C—H methine groups were introduced at calculated positions (C—H 0.99 Å, CH2 0.98 Å). These H atoms were treated as riders. H atoms of hydroxy and amine were located in a difference Fourier synthesis and refined with constrained bond lengths (O—H 0.82 Å, NH2 0.87 Å) and angles. A spherical harmonic correction for preferred orientation (Von Dreele, 1997) was applied in the final refinement, with 16 coefficients. The use of the preferred orientation correction leads to better molecular geometry and better agreement factors. The final Rietveld plot of the X-ray diffraction pattern is given in Fig. 3.

Computing details top

Data collection: WinXPOW (Stoe & Cie,1999); cell refinement: GSAS (Larson & Von Dreele, 2004); data reduction: WinXPOW (Stoe & Cie, 1999); program(s) used to solve structure: FOX (Favre-Nicolin & Černý, 2002); program(s) used to refine structure: GSAS (Larson & Von Dreele, 2004); molecular graphics: ORTEP (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. The molecular structure of (2RS,3RS)-(I), showing the atom numbering. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing of (2RS,3RS)-(I) viewed normal to the b axis. Intra- and intermolecular O—H···N and N—H···O hydrogen bonds are shown as dashed lines. [Symmetry code: (i) x, -y-1/2, z-1/2.]
[Figure 3] Fig. 3. Final Rietveld plot for (2RS,3RS)-(I). Observed data points are indicated by dots and the best-fit profile (upper trace) and the difference pattern (lower trace) are shown with solid lines. The vertical bars indicate the positions of Bragg peaks.
(2RS,3RS)-5-amino-3-(4-phenylpiperazin-1-yl)-1,2,3,4- tetrahydronaphthalen-2-ol top
Crystal data top
C20H25N3OF(000) = 696
Mr = 323.44Dx = 1.237 Mg m3
Monoclinic, P21/cCu Kα1 radiation, λ = 1.5406 Å
Hall symbol: -P 2ybcµ = 0.61 mm1
a = 11.4132 (4) ÅT = 298 K
b = 8.8555 (3) ÅParticle morphology: Fine powder
c = 17.1797 (4) Åwhite
β = 90.5787 (17)°flat sheet, 7 × 7 mm
V = 1736.27 (9) Å3Specimen preparation: Prepared at 298 K and 101.3 kPa
Z = 4
Data collection top
Stoe transmission STADI P
diffractometer
Scan method: step
Radiation source: sealed X-ray tube, C-TechAbsorption correction: for a cylinder mounted on the ϕ axis
(GSAS; Larson & Von Dreele, 2004)
Ge 111 monochromatorTmin = 0.653, Tmax = 0.664
Specimen mounting: powder loaded between two Mylar foils2θmin = 4.972°, 2θmax = 89.952°, 2θstep = 0.02°
Data collection mode: transmission
Refinement top
Least-squares matrix: fullExcluded region(s): none
Rp = 0.020Profile function: CW Profile function number 4 with 21 terms Pseudovoigt profile coefficients as parameterized in (Thompson et al., 1987). Asymmetry correction of (Finger et al., 1994). Microstrain broadening by (Stephens, 1999). [Stephens, P. W. (1999). J. Appl. Cryst. 32, 281–289.] #1(GU) = 0.000 #2(GV) = 0.000 #3(GW) = 10.095 #4(GP) = 0.000 #5(LX) = 1.349 #6(ptec) = 0.00 #7(trns) = 0.00 #8(shft) = 0.0000 #9(sfec) = 0.00 #10(S/L) = 0.0225 #11(H/L) = 0.0225 #12(eta) = 0.5000 #13(S400 ) = 1.5E-02 #14(S040 ) = 6.8E-02 #15(S004 ) = 2.0E-03 #16(S220 ) = -3.0E-03 #17(S202 ) = 1.2E-02 #18(S022 ) = 3.8E-03 #19(S301 ) = 1.2E-02 #20(S103 ) = -3.7E-03 #21(S121 ) = 8.0E-03 Peak tails are ignored where the intensity is below 0.0010 times the peak Aniso. broadening axis 0.0 0.0 1.0
Rwp = 0.027190 parameters
Rexp = 0.02029 restraints
R(F2) = 0.07470H-atom parameters constrained
χ2 = 1.877(Δ/σ)max = 0.02
4250 data pointsBackground function: GSAS Background function number 1 with 20 terms. Shifted Chebyshev function of 1st kind 1: 2382.05 2: -2440.77 3: 1212.48 4: -223.136 5: -152.966 6: 162.127 7: -101.052 8: -8.07464 9: 43.2336 10: 38.2778 11: -89.5240 12: 63.8750 13: -2.24672 14: -37.7784 15: 28.2890 16: -2.11921 17: -14.9596 18: 26.8405 19: -28.3180 20: 19.4205
Crystal data top
C20H25N3OV = 1736.27 (9) Å3
Mr = 323.44Z = 4
Monoclinic, P21/cCu Kα1 radiation, λ = 1.5406 Å
a = 11.4132 (4) ŵ = 0.61 mm1
b = 8.8555 (3) ÅT = 298 K
c = 17.1797 (4) Åflat sheet, 7 × 7 mm
β = 90.5787 (17)°
Data collection top
Stoe transmission STADI P
diffractometer
Absorption correction: for a cylinder mounted on the ϕ axis
(GSAS; Larson & Von Dreele, 2004)
Specimen mounting: powder loaded between two Mylar foilsTmin = 0.653, Tmax = 0.664
Data collection mode: transmission2θmin = 4.972°, 2θmax = 89.952°, 2θstep = 0.02°
Scan method: step
Refinement top
Rp = 0.0204250 data points
Rwp = 0.027190 parameters
Rexp = 0.02029 restraints
R(F2) = 0.07470H-atom parameters constrained
χ2 = 1.877
Special details top

Experimental. The sample was ground lightly in a mortar, loaded between two Myler foils and fixed in the sample holder with a mask of 7.0 mm internal diameter.

Solvents were distilled before use. Thin-layer chromatographic (TLC) analysis was performed using Merck 60F254 silica gel plates. Flash chromatography was used for the purification of reaction products using silica gel (70–230 mesh). Visualization was accomplished under UV light or in an iodine chamber. NMR spectra were recorded on a Bruker Biospin 400 spectrometer (400 MHz for 1H, 100 MHz for 13C). Chemical shifts (δ) are expressed in p.p.m. relative to TMS as an internal standard. The IR spectrum was recorded on an FTIR-JASCO 300E. Melting-point determinations were performed with a digital melting-point instrument from Stuart, model SMP3.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.6298 (6)0.4956 (8)0.9143 (5)0.0650 (17)*
C20.7014 (6)0.6192 (8)0.8994 (5)0.0650 (17)*
C30.6639 (6)0.7308 (8)0.8488 (5)0.0650 (17)*
C40.5557 (6)0.7225 (8)0.8135 (5)0.0650 (17)*
C50.4847 (7)0.5963 (8)0.8255 (6)0.0650 (17)*
C60.5210 (10)0.4809 (12)0.8756 (6)0.0650 (17)*
C70.3239 (4)0.3664 (5)0.8827 (3)0.0650 (17)*
C80.2657 (4)0.2183 (6)0.8612 (3)0.0650 (17)*
C90.4949 (4)0.2155 (6)0.9272 (3)0.0650 (17)*
C100.4293 (4)0.0743 (5)0.8996 (3)0.0650 (17)*
C110.2098 (5)0.0244 (7)0.9004 (4)0.0650 (17)*
C120.2056 (5)0.1154 (7)0.9718 (4)0.0650 (17)*
C130.1083 (4)0.2327 (5)0.9647 (3)0.0650 (17)*
C140.0938 (9)0.3036 (10)0.8846 (5)0.0650 (17)*
C150.1571 (9)0.2495 (12)0.8209 (7)0.0650 (17)*
C160.2353 (4)0.1146 (6)0.8256 (3)0.0650 (17)*
C170.0277 (9)0.4382 (9)0.8833 (4)0.0650 (17)*
C180.0252 (9)0.5264 (9)0.8153 (4)0.0650 (17)*
C190.0849 (9)0.4745 (8)0.7497 (4)0.0650 (17)*
C200.1492 (9)0.3434 (11)0.7555 (6)0.0650 (17)*
N10.4499 (8)0.3449 (10)0.8835 (5)0.0650 (17)*
N20.3025 (7)0.0945 (10)0.9143 (5)0.0650 (17)*
N30.2054 (4)0.2932 (6)0.6882 (3)0.0650 (17)*
O10.1832 (9)0.0173 (7)1.0362 (4)0.0650 (17)*
H10.657680.414330.949660.075*
H20.778910.627660.925440.075*
H30.714010.820040.839790.075*
H40.530140.802870.776890.075*
H50.407410.589540.799120.075*
H7a0.302640.443640.844290.075*
H7b0.298120.398620.934270.075*
H8a0.287150.191480.807810.075*
H8b0.18040.230560.863770.075*
H9a0.481560.230640.98290.075*
H9b0.578910.203890.917780.075*
H10a0.44180.059820.843720.075*
H10b0.458310.014160.928130.075*
H110.133190.026650.893810.075*
H120.281780.166740.979850.075*
H13a0.034010.184480.978440.075*
H13b0.124560.313671.00230.075*
H16a0.22050.050110.780260.075*
H16b0.317560.146850.825950.075*
H170.014210.472020.930350.075*
H180.02070.621210.813270.075*
H190.084630.53370.700880.075*
H1N30.194750.358840.651080.075*
H2N30.280120.283430.697760.075*
H1o0.179270.07031.020790.075*
Geometric parameters (Å, º) top
C1—C21.391 (7)C11—C121.469 (8)
C1—C61.408 (9)C11—C161.543 (7)
C1—H10.993C11—N21.510 (9)
C2—C31.381 (7)C11—H110.989
C2—H20.990C12—C131.524 (7)
C3—C41.372 (7)C12—O11.432 (8)
C3—H30.989C12—H120.990
C4—C51.397 (7)C13—C141.520 (9)
C4—H40.992C13—H13a0.981
C5—C61.396 (9)C13—H13b0.982
C5—H50.990C14—C151.402 (10)
C6—N11.459 (10)C14—C171.411 (10)
C7—C81.514 (6)C15—C161.493 (10)
C7—N11.451 (9)C15—C201.399 (10)
C7—H7a0.980C16—H16a0.979
C7—H7b0.979C16—H16b0.981
C8—N21.484 (8)C17—C181.406 (7)
C8—H8a0.981C17—H170.990
C8—H8b0.981C18—C191.401 (7)
C9—C101.531 (6)C18—H180.990
C9—N11.460 (8)C19—C201.377 (9)
C9—H9a0.980C19—H190.988
C9—H9b0.979C20—N31.401 (10)
C10—N21.483 (8)N3—H1N30.871
C10—H10a0.980N3—H2N30.871
C10—H10b0.980O1—H1o0.821
C2—C1—C6120.2 (6)N2—C11—H11108.4
C2—C1—H1119.8C11—C12—C13109.7 (5)
C6—C1—H1119.8C11—C12—O1108.7 (5)
C1—C2—C3119.9 (4)C11—C12—H12109.4
C1—C2—H2120.0C13—C12—O1109.9 (6)
C3—C2—H2120.0C13—C12—H12109.6
C2—C3—C4120.8 (4)O1—C12—H12109.5
C2—C3—H3119.6C12—C13—C14115.3 (6)
C4—C3—H3119.6C12—C13—H13a108.3
C3—C4—C5119.9 (4)C12—C13—H13b108.2
C3—C4—H4120.0C14—C13—H13a108.2
C5—C4—H4120.0C14—C13—H13b108.2
C4—C5—C6120.5 (6)H13a—C13—H13b108.5
C4—C5—H5119.8C13—C14—C15120.9 (9)
C6—C5—H5119.7C13—C14—C17114.6 (6)
C1—C6—C5118.5 (7)C15—C14—C17123.8 (8)
C1—C6—N1121.4 (8)C14—C15—C16122.9 (9)
C5—C6—N1120.0 (7)C14—C15—C20113.2 (10)
C8—C7—N1108.7 (5)C16—C15—C20123.6 (9)
C8—C7—H7a109.6C11—C16—C15110.0 (6)
C8—C7—H7b109.8C11—C16—H16a109.1
N1—C7—H7a109.6C11—C16—H16b109.5
N1—C7—H7b109.7C15—C16—H16a109.0
H7a—C7—H7b109.4C15—C16—H16b109.8
C7—C8—N2111.6 (5)H16a—C16—H16b109.5
C7—C8—H8a109.0C14—C17—C18119.2 (5)
C7—C8—H8b109.1C14—C17—H17120.4
N2—C8—H8a108.9C18—C17—H17120.3
N2—C8—H8b109.2C17—C18—C19118.8 (4)
H8a—C8—H8b109.1C17—C18—H18120.4
C10—C9—N1108.3 (5)C19—C18—H18120.7
C10—C9—H9a109.5C18—C19—C20118.7 (5)
C10—C9—H9b109.8C18—C19—H19120.8
N1—C9—H9a109.8C20—C19—H19120.4
N1—C9—H9b109.7C15—C20—C19126.2 (8)
H9a—C9—H9b109.7C15—C20—N3116.6 (8)
C9—C10—N2108.9 (5)C19—C20—N3117.1 (6)
C9—C10—H10a109.6C6—N1—C7116.3 (7)
C9—C10—H10b109.7C6—N1—C9120.2 (8)
N2—C10—H10a109.5C7—N1—C9116.8 (6)
N2—C10—H10b109.6C8—N2—C10104.8 (5)
H10a—C10—H10b109.5C8—N2—C11103.0 (6)
C12—C11—C16114.8 (5)C10—N2—C11124.9 (6)
C12—C11—N2106.2 (6)C20—N3—H1N3109.3
C12—C11—H11108.0C20—N3—H2N3109.4
C16—C11—N2110.7 (6)H1N3—N3—H2N3109.5
C16—C11—H11108.4C12—O1—H1o109.5
C7—N1—C9—C1052.2 (8)N2—C11—C12—O156.3 (7)
C7—N1—C6—C1145.5 (9)N2—C11—C12—C13176.4 (5)
C6—N1—C9—C10157.6 (7)C16—C11—C12—O1179.1 (6)
C9—N1—C7—C849.6 (8)C16—C11—C12—C1360.8 (6)
C9—N1—C6—C5171.5 (8)N2—C11—C16—C15169.1 (7)
C6—N1—C7—C8159.0 (7)C12—C11—C16—C1548.8 (7)
C9—N1—C6—C14.9 (14)O1—C12—C13—C14157.6 (6)
C7—N1—C6—C538.1 (12)C11—C12—C13—C1438.3 (7)
C11—N2—C8—C7162.7 (5)C12—C13—C14—C157.3 (11)
C10—N2—C8—C765.4 (6)C12—C13—C14—C17163.5 (7)
C8—N2—C11—C12154.5 (5)C13—C14—C15—C164.3 (14)
C10—N2—C11—C1638.5 (9)C13—C14—C15—C20169.3 (8)
C8—N2—C10—C966.7 (6)C17—C14—C15—C16174.2 (9)
C11—N2—C10—C9175.4 (6)C17—C14—C15—C200.5 (15)
C8—N2—C11—C1680.2 (6)C13—C14—C17—C18169.4 (8)
C10—N2—C11—C1286.8 (8)C15—C14—C17—C181.0 (15)
C6—C1—C2—C32.5 (12)C14—C15—C16—C1115.0 (11)
C2—C1—C6—N1173.2 (8)C20—C15—C16—C11172.0 (9)
C2—C1—C6—C53.2 (14)C14—C15—C20—N3176.9 (8)
C1—C2—C3—C40.8 (12)C14—C15—C20—C191.8 (15)
C2—C3—C4—C53.3 (12)C16—C15—C20—N39.5 (14)
C3—C4—C5—C62.5 (13)C16—C15—C20—C19175.4 (9)
C4—C5—C6—C10.8 (14)C14—C17—C18—C192.5 (14)
C4—C5—C6—N1175.7 (9)C17—C18—C19—C203.6 (14)
N1—C7—C8—N255.7 (7)C18—C19—C20—N3178.5 (8)
N1—C9—C10—N260.1 (7)C18—C19—C20—C153.4 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N20.822.332.698 (12)108
N3—H1N3···O1i0.872.263.112 (8)166
C18—H18···N3ii0.992.603.537 (11)158
C7—H7a···Cg4iii0.982.883.605 (6)132
Symmetry codes: (i) x, y1/2, z1/2; (ii) x, y1/2, z+3/2; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formulaC20H25N3O
Mr323.44
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)11.4132 (4), 8.8555 (3), 17.1797 (4)
β (°) 90.5787 (17)
V3)1736.27 (9)
Z4
Radiation typeCu Kα1, λ = 1.5406 Å
µ (mm1)0.61
Specimen shape, size (mm)Flat sheet, 7 × 7
Data collection
DiffractometerStoe transmission STADI P
diffractometer
Specimen mountingPowder loaded between two Mylar foils
Data collection modeTransmission
Scan methodStep
Absorption correctionFor a cylinder mounted on the ϕ axis
(GSAS; Larson & Von Dreele, 2004)
Tmin, Tmax0.653, 0.664
2θ values (°)2θmin = 4.972 2θmax = 89.952 2θstep = 0.02
Refinement
R factors and goodness of fitRp = 0.020, Rwp = 0.027, Rexp = 0.020, R(F2) = 0.07470, χ2 = 1.877
No. of data points4250
No. of parameters190
No. of restraints29
H-atom treatmentH-atom parameters constrained

Computer programs: WinXPOW (Stoe & Cie,1999), GSAS (Larson & Von Dreele, 2004), WinXPOW (Stoe & Cie, 1999), FOX (Favre-Nicolin & Černý, 2002), ORTEP (Farrugia, 1997), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top
C13—C141.520 (9)C15—C161.493 (10)
C14—C151.402 (10)
C13—C14—C15120.9 (9)C14—C15—C16122.9 (9)
C15—C14—C17123.8 (8)C14—C15—C20113.2 (10)
C7—N1—C6—C538.1 (12)C13—C14—C15—C20169.3 (8)
C8—N2—C11—C12154.5 (5)C17—C14—C15—C16174.2 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1O···N20.822.332.698 (12)108
N3—H1N3···O1i0.872.263.112 (8)166
C18—H18···N3ii0.992.603.537 (11)158
C7—H7a···Cg4iii0.982.883.605 (6)132
Symmetry codes: (i) x, y1/2, z1/2; (ii) x, y1/2, z+3/2; (iii) x, y+1, z.
 

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