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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 69| Part 5| May 2013| Page o628
https://doi.org/10.1107/S1600536813007010

rac-(1S*,4aS*,8aS*)-4a-Hy­dr­oxy-2-methyl­perhydro­spiro­[iso­quinoline-4,1′-cyclo­hexa­n]-2′-one

Sorho Siaka,a* Anatoly T. Soldatenkov,b Anastasia V. Malkova,b Svetlana A. Soldatovab and Victor N. Khrustalevc

aInstitut National Polytechnique Félix Houphouët-Boigny, Enseignant-Chercheur à l'INP-HB de Yamoussoukro, BP 991 Yamoussoukro, Côte d'Ivoire, bOrganic Chemistry Department, Russian Peoples Friendship University, Miklukho-Maklaya St. 6, Moscow 117198, Russia, and cX-Ray Structural Centre, A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, B-334, Moscow 119991, Russian Federation
*Correspondence e-mail: ssiaka@inphb.edu.ci

(Received 7 March 2013; accepted 13 March 2013; online 5 April 2013)

In the title compound, C15H25NO2, all three six-membered rings adopt chair conformations. The cyclo­hexane and piperidine rings within the perhydro­isoquinoline are trans–trans fused. The N atom has a trigonal–pyramidal geometry (the sum of the bond angles is 328.0°). The methyl substituent occupies the sterically preferrable equatorial position. In the crystal, mol­ecules form infinite [100] chains via O—H⋯N hydrogen bonds.

Related literature

For general background to the synthesis, chemical properties and applications in medicine of the title compound, see: Plati & Wenner (1949[Plati, J. N. & Wenner, W. (1949). J. Org. Chem. 14, 543-549.]); Ellefson et al. (1978[Ellefson, C. R., Woo, C. M. & Cusic, J. W. (1978). J. Med. Chem. 21, 340-343.]); Soldatenkov et al. (2009[Soldatenkov, A. T., Soldatova, S. A., Malkova, A. V., Kolyadina, N. M. & Khrustalev, V. N. (2009). Chem. Heterocycl. Compd, 45, 1398-1400.]). For related compounds, see: Plati & Wenner (1950[Plati, J. N. & Wenner, W. (1950). J. Org. Chem. 15, 209-215.]); Soldatenkov et al. (2008[Soldatenkov, A. T., Volkov, S. V., Polyanskii, K. B. & Soldatova, S. A. (2008). Chem. Heterocycl. Compd, 44, 630-631.]); Soldatova et al. (2010[Soldatova, S. A., Soldatenkov, A. T., Kotsuba, V. E. & Khrustalev, V. N. (2010). Chem. Heterocycl. Compd, 46, 123-124.]); Siaka et al. (2012[Siaka, S., Soldatenkov, A. T., Malkova, A. V., Sorokina, E. A. & Khrustalev, V. N. (2012). Acta Cryst. E68, o3230.]).

[Scheme 1]

Experimental

Crystal data

  • C15H25NO2

  • Mr = 251.36

  • Monoclinic, P 21 /n

  • a = 5.8438 (2) Å

  • b = 18.5756 (7) Å

  • c = 12.2148 (5) Å

  • β = 95.116 (1)°

  • V = 1320.66 (9) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 100 K

  • 0.30 × 0.30 × 0.20 mm
Data collection

  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2003[Sheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.]) Tmin = 0.976, Tmax = 0.984

  • 17142 measured reflections

  • 3852 independent reflections

  • 3221 reflections with I > 2σ(I)

  • Rint = 0.028
Refinement

  • R[F2 > 2σ(F2)] = 0.037

  • wR(F2) = 0.102

  • S = 1.00

  • 3852 reflections

  • 167 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.48 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
O1—H1⋯N3i 0.830 (12) 2.195 (12) 2.8967 (10) 142.3 (12)
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536813007010/rk2397sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813007010/rk2397Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536813007010/rk2397Isup3.cml

checkCIF report


Comment top

It is well known that 3–aroyl–4–arylpiperidin–4–ols are intermediate products in the synthesis of important antihistaminic agents (Plati & Wenner, 1950; Ellefson et al., 1978). Such piperidols can be prepared in two steps via the condensation of the corresponding acetophenones with formaldehyde and alkylamines by heating of these mixtures in 36% HCl solution and the subsequent intramolecular cyclization of the yielded double Mannich bases under action of bases (Plati & Wenner, 1949).

However, we found that use of α–tetralone - the cyclic analogue of acetophenone (Soldatenkov et al., 2008) in the analogous syntheses results in very complex multicomponent mixtures instead of the expected γ–piperidol derivatives. These mixtures contain only trace quantities of the expected piperidols (identified by LC–MS method). It is interesing to note that heating of the analogous double Mannich base prepared from α–tetralone (Soldatenkov et al., 2009; Soldatova et al., 2010; Siaka et al., 2012) in HBr solution gives the expectable product of the cyclization, but in the dehydrated form. Its structure comprising the spiro–fused hexahydrobenzo[f]isoquinoline and tetrahydronaphthalenone systems was unambiguously established by X–ray diffraction study (Siaka et al., 2012). Thus, such a molecule appears to be much more stable than its 10b–hydroxy predecessor. Hence, we were not sure that structure of the main product would be chemically preferable in the analogous multicomponent condensation if we would use cyclohexanone as the ketone component (heating in HBr solution; Fig. 1). We have found that, in this case, 8a–hydroxy–3–methylperhydrospiro[isoquinoline–1,2'–cyclohexan]–1'–one is formed, which is very stable towards dehydration in acidic media. The first step of this cascade process is the formation of the double Mannich base, and the second one is aldol–type intramolecular cycloaddition of the two cyclohexenone moieties to each other. The structure of the spiro–derivative, C15H25NO2, (I) was unambiguously established by X–ray diffraction study.

The molecule of I comprises spiro–fused perhydroisoquinoline and cyclohexanone systems (Fig. 2). All the three saturated six–membered rings adopt chair conformations. The cyclohexane and piperidine rings within the perhydroisoquinoline are fused in trans–trans type. The nitrogen atom has a trigonal–pyramidal geometry (sum of the bond angles is 328.0 (2)°). The methyl substituent occupies the sterically preferrable equatorial position.

The molecule of I possesses three asymmetric centers at the C1, C4A and C8A carbon atoms and can have potentially eight diastereomers. The crystal of I is racemic and consists of enantiomeric pairs with the following relative configuration of the centers: rac–1S*,4aS*,8aS*.

In the crystal, molecules form infinite [1 0 0] chains via the intermolecular O1—H1···N3i hydrogen bonds (Fig. 3, Table 1). The chains are arranged at van–der–Waals distances. Symmetry code: (i) x+1, y, z.

Related literature top

For general background to the synthesis, chemical properties and applications in medicine of the title compound, see: Plati & Wenner (1949); Ellefson et al. (1978); Soldatenkov et al. (2009). For related compounds, see: Plati & Wenner (1950); Soldatenkov et al. (2008); Soldatova et al. (2010); Siaka et al. (2012).

Experimental top

A mixture of methylamine hydrochloride (14.0 g, 0.2 mol), cyclohexanone (41.4 ml, 0.4 mol) and formaldehyde (31 ml of 40% solution in water) in 48% HBr (80 ml) was boiled for 6 h. The reaction mixture was then cooled, poured into cold water (200 ml) and stirred at 293 K for 7 h. The pH of the mixture was then brought at 9, and the expected product was extracted by ether. The obtained extract was washed with water (50 ml), dried over disodium sulfate. After the solvent evaporation, the residue was purified by re–crystallization from ethanol to give 16.75 g of colorless crystals of I. Yield is 28%. M.p. = 437–439 K. IR (KBr), ν/cm-1: 3452, 3400, 1698. 1H NMR (CDCl3, 400 MHz, 300 K): δ = 1.19–1.65 (m, 7H, C—CH2), 1.68 (t, 2H, 3J = 11.7, C—CH2), 1.88 (t, 1H, 3J = 12.0, C—CH2), 1.94–2.06 (m, 4H, C—CH2), 2.18 (s, 3H, CH3), 2.22 (m, 1H, C—CH), 2.40 (d, 1H, 3J = 12.0, N—CH2), 2.43 (m, 1H, NCH2), 2.55–2.70 (m, 3H, NCH2 and C—CH2), 3.16 (d, 1H, 3J = 12.0, N—CH2), 5.00 (s, 1H, OH). Anal. Calcd for C15H25NO2: C, 71.67; H, 10.02; N, 5.57. Found: C, 71.83; H, 9.77; N, 5.41.

Refinement top

The hydrogen atom of the hydroxy group was localized in the difference Fourier map and refined isotropically with fixed isotropic displacement parameters Uiso(H) = 1.5Ueq(O). The other hydrogen atoms were placed in calculated positions with C—H = 0.98–1.00Å and refined in the riding model with fixed isotropic displacement parameters Uiso(H) = 1.5Ueq(C) for the methyl group and 1.2Ueq(C) for the other groups.

Structure description top

It is well known that 3–aroyl–4–arylpiperidin–4–ols are intermediate products in the synthesis of important antihistaminic agents (Plati & Wenner, 1950; Ellefson et al., 1978). Such piperidols can be prepared in two steps via the condensation of the corresponding acetophenones with formaldehyde and alkylamines by heating of these mixtures in 36% HCl solution and the subsequent intramolecular cyclization of the yielded double Mannich bases under action of bases (Plati & Wenner, 1949).

However, we found that use of α–tetralone - the cyclic analogue of acetophenone (Soldatenkov et al., 2008) in the analogous syntheses results in very complex multicomponent mixtures instead of the expected γ–piperidol derivatives. These mixtures contain only trace quantities of the expected piperidols (identified by LC–MS method). It is interesing to note that heating of the analogous double Mannich base prepared from α–tetralone (Soldatenkov et al., 2009; Soldatova et al., 2010; Siaka et al., 2012) in HBr solution gives the expectable product of the cyclization, but in the dehydrated form. Its structure comprising the spiro–fused hexahydrobenzo[f]isoquinoline and tetrahydronaphthalenone systems was unambiguously established by X–ray diffraction study (Siaka et al., 2012). Thus, such a molecule appears to be much more stable than its 10b–hydroxy predecessor. Hence, we were not sure that structure of the main product would be chemically preferable in the analogous multicomponent condensation if we would use cyclohexanone as the ketone component (heating in HBr solution; Fig. 1). We have found that, in this case, 8a–hydroxy–3–methylperhydrospiro[isoquinoline–1,2'–cyclohexan]–1'–one is formed, which is very stable towards dehydration in acidic media. The first step of this cascade process is the formation of the double Mannich base, and the second one is aldol–type intramolecular cycloaddition of the two cyclohexenone moieties to each other. The structure of the spiro–derivative, C15H25NO2, (I) was unambiguously established by X–ray diffraction study.

The molecule of I comprises spiro–fused perhydroisoquinoline and cyclohexanone systems (Fig. 2). All the three saturated six–membered rings adopt chair conformations. The cyclohexane and piperidine rings within the perhydroisoquinoline are fused in trans–trans type. The nitrogen atom has a trigonal–pyramidal geometry (sum of the bond angles is 328.0 (2)°). The methyl substituent occupies the sterically preferrable equatorial position.

The molecule of I possesses three asymmetric centers at the C1, C4A and C8A carbon atoms and can have potentially eight diastereomers. The crystal of I is racemic and consists of enantiomeric pairs with the following relative configuration of the centers: rac–1S*,4aS*,8aS*.

In the crystal, molecules form infinite [1 0 0] chains via the intermolecular O1—H1···N3i hydrogen bonds (Fig. 3, Table 1). The chains are arranged at van–der–Waals distances. Symmetry code: (i) x+1, y, z.

For general background to the synthesis, chemical properties and applications in medicine of the title compound, see: Plati & Wenner (1949); Ellefson et al. (1978); Soldatenkov et al. (2009). For related compounds, see: Plati & Wenner (1950); Soldatenkov et al. (2008); Soldatova et al. (2010); Siaka et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The cascade condensation of cyclohexanone with formaldehyde and methylamine.
[Figure 2] Fig. 2. Molecular structure of I with the atom numbering scheme. Displacement ellipsoids are shown at the 50% probability level. H atoms are presented as small spheres of arbitrary radius.
[Figure 3] Fig. 3. A portion of the crystal structure showing the packing of the H–bonded infinite chains of I. The intermolecular O—H···N hydrogen bonds are depicted by dashed lines.
rac-(1S*,4aS*,8aS*)-4a-Hydroxy-2-methylperhydrospiro[isoquinoline-4,1'-cyclohexan]-2'-one top
Crystal data top
C15H25NO2F(000) = 552
Mr = 251.36Dx = 1.264 Mg m−3
Monoclinic, P21/nMelting point = 437–439 K
Hall symbol: -P 2ynMo Kα radiation, λ = 0.71073 Å
a = 5.8438 (2) ÅCell parameters from 6340 reflections
b = 18.5756 (7) Åθ = 2.2–32.6°
c = 12.2148 (5) ŵ = 0.08 mm−1
β = 95.116 (1)°T = 100 K
V = 1320.66 (9) Å3Prism, colourless
Z = 40.30 × 0.30 × 0.20 mm
Data collection top
Bruker APEXII CCD
diffractometer		3852 independent reflections
Radiation source: fine–focus sealed tube3221 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
φ and ω scansθmax = 30.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −8→8
Tmin = 0.976, Tmax = 0.984k = −26→26
17142 measured reflectionsl = −17→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: calc
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.00 w = 1/[σ2(Fo2) + (0.055P)2 + 0.4P]
where P = (Fo2 + 2Fc2)/3
3852 reflections(Δ/σ)max < 0.001
167 parametersΔρmax = 0.48 e Å−3
0 restraintsΔρmin = −0.18 e Å−3
Crystal data top
C15H25NO2V = 1320.66 (9) Å3
Mr = 251.36Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.8438 (2) ŵ = 0.08 mm−1
b = 18.5756 (7) ÅT = 100 K
c = 12.2148 (5) Å0.30 × 0.30 × 0.20 mm
β = 95.116 (1)°
Data collection top
Bruker APEXII CCD
diffractometer		3852 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		3221 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.984Rint = 0.028
17142 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.00Δρmax = 0.48 e Å−3
3852 reflectionsΔρmin = −0.18 e Å−3
167 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
xyzUiso*/Ueq
O10.72882 (11)0.10966 (4)0.39294 (6)0.01342 (14)
H10.847 (2)0.1345 (7)0.3939 (11)0.020*
C10.47868 (14)0.21494 (5)0.37839 (7)0.00990 (16)
C20.38858 (15)0.19624 (5)0.49006 (7)0.01161 (17)
H2A0.51430.17410.53840.014*
H2B0.34210.24120.52570.014*
N30.19197 (13)0.14659 (4)0.47886 (6)0.01124 (15)
C40.26546 (15)0.07765 (5)0.43377 (7)0.01177 (17)
H4A0.13560.04320.42930.014*
H4B0.39190.05700.48340.014*
C4A0.34662 (15)0.08849 (5)0.31979 (7)0.01051 (16)
H4C0.21570.10890.27120.013*
C50.41334 (16)0.01620 (5)0.27117 (7)0.01355 (18)
H5A0.5389−0.00590.31970.016*
H5B0.2797−0.01680.26780.016*
C60.49189 (17)0.02548 (5)0.15586 (8)0.01609 (18)
H6A0.36190.04300.10530.019*
H6B0.5416−0.02160.12830.019*
C70.69080 (17)0.07913 (5)0.15765 (8)0.01640 (19)
H7A0.73260.08670.08170.020*
H7B0.82640.05880.20140.020*
C80.62793 (16)0.15179 (5)0.20703 (7)0.01312 (17)
H8A0.50390.17470.15860.016*
H8B0.76340.18400.21080.016*
C8A0.54791 (15)0.14266 (5)0.32298 (7)0.01031 (16)
C90.11013 (17)0.13529 (5)0.58766 (7)0.01506 (18)
H9A0.05650.18110.61580.023*
H9B0.23600.11660.63810.023*
H9C−0.01670.10060.58180.023*
O1'0.18262 (12)0.23557 (4)0.22802 (6)0.01587 (15)
C1'0.29057 (15)0.25807 (5)0.31084 (7)0.01110 (17)
C3'0.69183 (15)0.26497 (5)0.40043 (8)0.01269 (17)
H3A0.80800.23990.45070.015*
H3B0.76020.27320.33020.015*
C4'0.63912 (16)0.33810 (5)0.45054 (8)0.01341 (18)
H4D0.58140.33080.52350.016*
H4E0.78180.36700.46090.016*
C5'0.45977 (16)0.37870 (5)0.37603 (8)0.01372 (18)
H5C0.52370.39050.30580.016*
H5D0.42100.42440.41170.016*
C6'0.24123 (16)0.33311 (5)0.35295 (8)0.01422 (18)
H6C0.16350.32880.42140.017*
H6D0.13510.35810.29780.017*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0096 (3)0.0127 (3)0.0174 (3)0.0011 (2)−0.0015 (2)0.0010 (2)
C10.0095 (4)0.0095 (4)0.0106 (4)0.0001 (3)0.0002 (3)−0.0001 (3)
C20.0127 (4)0.0115 (4)0.0106 (4)−0.0004 (3)0.0008 (3)−0.0006 (3)
N30.0123 (3)0.0107 (3)0.0110 (3)−0.0001 (3)0.0026 (3)0.0001 (3)
C40.0127 (4)0.0104 (4)0.0124 (4)0.0005 (3)0.0019 (3)0.0009 (3)
C4A0.0109 (4)0.0095 (4)0.0111 (4)−0.0003 (3)0.0007 (3)−0.0004 (3)
C50.0169 (4)0.0101 (4)0.0138 (4)−0.0005 (3)0.0022 (3)−0.0010 (3)
C60.0218 (5)0.0125 (4)0.0144 (4)−0.0008 (3)0.0042 (3)−0.0031 (3)
C70.0189 (4)0.0149 (4)0.0164 (4)−0.0001 (3)0.0071 (3)−0.0024 (3)
C80.0148 (4)0.0120 (4)0.0129 (4)−0.0012 (3)0.0036 (3)−0.0005 (3)
C8A0.0101 (4)0.0099 (4)0.0108 (4)0.0006 (3)0.0003 (3)0.0004 (3)
C90.0172 (4)0.0168 (4)0.0117 (4)0.0010 (3)0.0040 (3)0.0019 (3)
O1'0.0163 (3)0.0156 (3)0.0149 (3)0.0008 (2)−0.0029 (2)−0.0001 (2)
C1'0.0104 (4)0.0107 (4)0.0124 (4)−0.0004 (3)0.0022 (3)0.0019 (3)
C3'0.0107 (4)0.0111 (4)0.0161 (4)−0.0007 (3)0.0001 (3)−0.0015 (3)
C4'0.0134 (4)0.0114 (4)0.0153 (4)−0.0015 (3)0.0005 (3)−0.0016 (3)
C5'0.0157 (4)0.0106 (4)0.0149 (4)0.0000 (3)0.0019 (3)−0.0004 (3)
C6'0.0128 (4)0.0120 (4)0.0176 (4)0.0023 (3)0.0000 (3)−0.0012 (3)
Geometric parameters (Å, º) top
O1—C8A1.4362 (10)C7—C81.5363 (13)
O1—H10.829 (14)C7—H7A0.9900
C1—C1'1.5393 (12)C7—H7B0.9900
C1—C21.5449 (12)C8—C8A1.5400 (12)
C1—C3'1.5581 (12)C8—H8A0.9900
C1—C8A1.5726 (12)C8—H8B0.9900
C2—N31.4701 (11)C9—H9A0.9800
C2—H2A0.9900C9—H9B0.9800
C2—H2B0.9900C9—H9C0.9800
N3—C91.4671 (11)O1'—C1'1.2175 (11)
N3—C41.4730 (11)C1'—C6'1.5223 (12)
C4—C4A1.5237 (12)C3'—C4'1.5326 (12)
C4—H4A0.9900C3'—H3A0.9900
C4—H4B0.9900C3'—H3B0.9900
C4A—C51.5328 (12)C4'—C5'1.5250 (13)
C4A—C8A1.5458 (12)C4'—H4D0.9900
C4A—H4C1.0000C4'—H4E0.9900
C5—C61.5296 (13)C5'—C6'1.5373 (13)
C5—H5A0.9900C5'—H5C0.9900
C5—H5B0.9900C5'—H5D0.9900
C6—C71.5297 (13)C6'—H6C0.9900
C6—H6A0.9900C6'—H6D0.9900
C6—H6B0.9900
C8A—O1—H1109.8 (9)C7—C8—C8A111.54 (7)
C1'—C1—C2107.88 (7)C7—C8—H8A109.3
C1'—C1—C3'107.69 (7)C8A—C8—H8A109.3
C2—C1—C3'108.16 (7)C7—C8—H8B109.3
C1'—C1—C8A114.36 (7)C8A—C8—H8B109.3
C2—C1—C8A108.00 (7)H8A—C8—H8B108.0
C3'—C1—C8A110.56 (7)O1—C8A—C8109.05 (7)
N3—C2—C1112.58 (7)O1—C8A—C4A104.79 (7)
N3—C2—H2A109.1C8—C8A—C4A109.95 (7)
C1—C2—H2A109.1O1—C8A—C1108.20 (7)
N3—C2—H2B109.1C8—C8A—C1114.37 (7)
C1—C2—H2B109.1C4A—C8A—C1110.01 (7)
H2A—C2—H2B107.8N3—C9—H9A109.5
C9—N3—C2108.70 (7)N3—C9—H9B109.5
C9—N3—C4110.10 (7)H9A—C9—H9B109.5
C2—N3—C4109.19 (7)N3—C9—H9C109.5
N3—C4—C4A110.58 (7)H9A—C9—H9C109.5
N3—C4—H4A109.5H9B—C9—H9C109.5
C4A—C4—H4A109.5O1'—C1'—C6'119.70 (8)
N3—C4—H4B109.5O1'—C1'—C1123.99 (8)
C4A—C4—H4B109.5C6'—C1'—C1116.31 (7)
H4A—C4—H4B108.1C4'—C3'—C1114.31 (7)
C4—C4A—C5110.42 (7)C4'—C3'—H3A108.7
C4—C4A—C8A111.17 (7)C1—C3'—H3A108.7
C5—C4A—C8A111.15 (7)C4'—C3'—H3B108.7
C4—C4A—H4C108.0C1—C3'—H3B108.7
C5—C4A—H4C108.0H3A—C3'—H3B107.6
C8A—C4A—H4C108.0C5'—C4'—C3'110.61 (7)
C6—C5—C4A111.44 (7)C5'—C4'—H4D109.5
C6—C5—H5A109.3C3'—C4'—H4D109.5
C4A—C5—H5A109.3C5'—C4'—H4E109.5
C6—C5—H5B109.3C3'—C4'—H4E109.5
C4A—C5—H5B109.3H4D—C4'—H4E108.1
H5A—C5—H5B108.0C4'—C5'—C6'110.64 (7)
C5—C6—C7110.51 (8)C4'—C5'—H5C109.5
C5—C6—H6A109.5C6'—C5'—H5C109.5
C7—C6—H6A109.5C4'—C5'—H5D109.5
C5—C6—H6B109.5C6'—C5'—H5D109.5
C7—C6—H6B109.5H5C—C5'—H5D108.1
H6A—C6—H6B108.1C1'—C6'—C5'112.77 (7)
C6—C7—C8111.71 (8)C1'—C6'—H6C109.0
C6—C7—H7A109.3C5'—C6'—H6C109.0
C8—C7—H7A109.3C1'—C6'—H6D109.0
C6—C7—H7B109.3C5'—C6'—H6D109.0
C8—C7—H7B109.3H6C—C6'—H6D107.8
H7A—C7—H7B107.9
C1'—C1—C2—N366.10 (9)C1'—C1—C8A—O1178.11 (7)
C3'—C1—C2—N3−177.68 (7)C2—C1—C8A—O1−61.79 (8)
C8A—C1—C2—N3−58.00 (9)C3'—C1—C8A—O156.37 (9)
C1—C2—N3—C9−176.76 (7)C1'—C1—C8A—C856.36 (10)
C1—C2—N3—C463.10 (9)C2—C1—C8A—C8176.46 (7)
C9—N3—C4—C4A178.93 (7)C3'—C1—C8A—C8−65.38 (9)
C2—N3—C4—C4A−61.80 (9)C1'—C1—C8A—C4A−67.95 (9)
N3—C4—C4A—C5−177.62 (7)C2—C1—C8A—C4A52.15 (9)
N3—C4—C4A—C8A58.53 (9)C3'—C1—C8A—C4A170.31 (7)
C4—C4A—C5—C6179.09 (7)C2—C1—C1'—O1'−111.77 (9)
C8A—C4A—C5—C6−57.05 (10)C3'—C1—C1'—O1'131.70 (9)
C4A—C5—C6—C756.19 (10)C8A—C1—C1'—O1'8.39 (12)
C5—C6—C7—C8−55.41 (11)C2—C1—C1'—C6'68.10 (9)
C6—C7—C8—C8A55.69 (10)C3'—C1—C1'—C6'−48.43 (10)
C7—C8—C8A—O159.18 (9)C8A—C1—C1'—C6'−171.74 (7)
C7—C8—C8A—C4A−55.19 (9)C1'—C1—C3'—C4'52.23 (10)
C7—C8—C8A—C1−179.54 (7)C2—C1—C3'—C4'−64.11 (9)
C4—C4A—C8A—O162.26 (9)C8A—C1—C3'—C4'177.83 (7)
C5—C4A—C8A—O1−61.17 (9)C1—C3'—C4'—C5'−58.21 (10)
C4—C4A—C8A—C8179.33 (7)C3'—C4'—C5'—C6'55.80 (10)
C5—C4A—C8A—C855.90 (9)O1'—C1'—C6'—C5'−129.56 (9)
C4—C4A—C8A—C1−53.84 (9)C1—C1'—C6'—C5'50.56 (10)
C5—C4A—C8A—C1−177.27 (7)C4'—C5'—C6'—C1'−52.24 (10)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N3i0.830 (12)2.195 (12)2.8967 (10)142.3 (12)
Symmetry code: (i) x+1, y, z.

Experimental details

Crystal data
Chemical formulaC15H25NO2
Mr251.36
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)5.8438 (2), 18.5756 (7), 12.2148 (5)
β (°) 95.116 (1)
V (Å3)1320.66 (9)
Z4
Radiation typeMo Kα
µ (mm−1)0.08
Crystal size (mm)0.30 × 0.30 × 0.20
Data collection
DiffractometerBruker APEXII CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.976, 0.984
No. of measured, independent and
observed [I > 2σ(I)] reflections		17142, 3852, 3221
Rint0.028
(sin θ/λ)max (Å−1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.102, 1.00
No. of reflections3852
No. of parameters167
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)0.48, −0.18

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N3i0.830 (12)2.195 (12)2.8967 (10)142.3 (12)
Symmetry code: (i) x+1, y, z.
 

References

First citationBruker (2001). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationBruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationEllefson, C. R., Woo, C. M. & Cusic, J. W. (1978). J. Med. Chem. 21, 340–343.  CrossRef CAS PubMed Web of Science Google Scholar
 First citationPlati, J. N. & Wenner, W. (1949). J. Org. Chem. 14, 543–549.  CrossRef CAS Web of Science Google Scholar
 First citationPlati, J. N. & Wenner, W. (1950). J. Org. Chem. 15, 209–215.  CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (2003). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
 First citationSiaka, S., Soldatenkov, A. T., Malkova, A. V., Sorokina, E. A. & Khrustalev, V. N. (2012). Acta Cryst. E68, o3230.  CSD CrossRef IUCr Journals Google Scholar
 First citationSoldatenkov, A. T., Soldatova, S. A., Malkova, A. V., Kolyadina, N. M. & Khrustalev, V. N. (2009). Chem. Heterocycl. Compd, 45, 1398–1400.  Google Scholar
 First citationSoldatenkov, A. T., Volkov, S. V., Polyanskii, K. B. & Soldatova, S. A. (2008). Chem. Heterocycl. Compd, 44, 630–631.  Web of Science CrossRef CAS Google Scholar
 First citationSoldatova, S. A., Soldatenkov, A. T., Kotsuba, V. E. & Khrustalev, V. N. (2010). Chem. Heterocycl. Compd, 46, 123–124.  CrossRef CAS Google Scholar

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ISSN: 2056-9890
Volume 69| Part 5| May 2013| Page o628
https://doi.org/10.1107/S1600536813007010
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