(2R)-8-Benzyl-2-[(S)-hy­droxy(phen­yl)meth­yl]-8-aza­bicyclo­[3.2.1]octan-3-one

Brzezinski, K.; Lazny, R.; Sienkiewicz, M.; Wojtulewski, S.; Dauter, Z.

doi:10.1107/S1600536811053190

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages o149-o150

doi:10.1107/S1600536811053190

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(2R)-8-Benzyl-2-[(S)-hydroxy(phenyl)methyl]-8-azabicyclo[3.2.1]octan-3-one

Krzysztof Brzezinski,^a ^* Ryszard Lazny,^b Michal Sienkiewicz,^b Sławomir Wojtulewski ^b and Zbigniew Dauter ^a

^aSynchrotron Radiation Research Section, MCL, National Cancer Institute, Argonne National Laboratory, Biosciences Division, Bldg. 202, Argonne, IL 60439, USA, and ^bInstitute of Chemistry, University of Bialystok, Hurtowa 1, 15-399 Bialystok, Poland
^*Correspondence e-mail: kbrzezinski@anl.gov

(Received 4 November 2011; accepted 9 December 2011; online 17 December 2011)

The crystal of the title compound, C₂₁H₂₃NO₂, was chosen from a conglomerate formed by a racemic mixture. An intramolecular hydrogen bond is formed between hydroxy group and heterocyclic N atom of the azabicyclo[3.2.1]octan-3-one system. The crystal structure is stabilized by C—H⋯O interactions between aliphatic C—H groups and the carbonyl O atom. For the title chiral crystal, the highly redundant and accurate diffraction data set collected with low energy copper radiation gave a Flack parameter of 0.12 (18) for anomalous scattering effects originating from O atoms.

Related literature

For recent background literature on the chemistry of related tropane-derived aldols and their applications, including stereoselective syntheses of bioactive alkaloids, see: Lazny et al. (2011 ); Sienkiewicz et al. (2009 ) and references cited therein. For stereoselective syntheses of related nortropinone aldols, see: Lazny et al. (2001 ); Lazny & Nodzewska (2003 ). For a representative review of the biological activity of tropane derivatives, see: Singh (2000 ).

Experimental

Crystal data

C₂₁H₂₃NO₂
M_r = 321.40
Orthorhombic, P 2₁ 2₁ 2₁
a = 5.9354 (1) Å
b = 13.3091 (2) Å
c = 22.1511 (3) Å
V = 1749.82 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.61 mm⁻¹
T = 100 K
0.65 × 0.25 × 0.19 mm

Data collection

Oxford Diffraction SuperNova Dual diffractometer
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011 ) T_min = 0.75, T_max = 0.89
32829 measured reflections
3323 independent reflections
3276 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.070
S = 1.18
3323 reflections
218 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.16 e Å⁻³
Absolute structure: Flack (1983 ), 1257 Friedel pairs
Flack parameter: 0.12 (18)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9⋯N8	0.84	1.99	2.7280 (13)	146
C6—H6B⋯O3ⁱ	0.99	2.61	3.3414 (15)	131
C7—H7A⋯O3ⁱ	0.99	2.52	3.2954 (15)	135
C16—H16A⋯O3ⁱ	0.99	2.60	3.5846 (16)	173
Symmetry code: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXD (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and pyMOL (DeLano, 2002 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811053190/gk2429sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811053190/gk2429Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811053190/gk2429Isup3.cml

checkCIF report

Comment top

Tropane (8-methyl-8-azabicyclo[3.2.1]octane) and nortropane (8-azabicyclo[3.2.1]octane) are known scaffolds of numerous natural alkaloids, many of which demonstrate a range of biological activities. Many synthetic derivatives and unnatural analogues of tropane alkaloids have been synthesized and studied as potential agrochemically or pharmaceutically useful agents (Singh, 2000). Diastereomerically and enantimerically pure aldols of tropinone were used as key intermediates in stereoselective synthesis of unnatural enantiomer of cocaine (ent-cocaine), knightinol, alkaloid KD–B and ferrugine (Sienkiewicz et al., 2009). Stereoselective syntheses of nortropinone aldols (Lazny & Nodzewska, 2003; Lazny et al., 2001) is more complicated and remains a challenge. Therefore synthetically equivalent N-benzylnortropinone aldols may open a route to synthetic availability of nor-analogues of potential pharmaceutical importance. Knowledge of the structure and reactivity of the N-benzyl analogues of tropanes is also used for modeling reactivity of nortropanes anchored through nitrogen on commonly used solid-phase supports with benzyl derived linkers. The solid-phase immobilization and subsequent transformations are typically used in combinatorial approaches to preparation of libraries of potentially bioactive substances.

The studied N-benzyl compound was prepared by a procedure analogous to method known for N-methyl aldols. The synthetic procedure gave a racemic mixture, however homochiral crystals were formed spontaneously. An enantiomorphic crystal was picked at random.

The crystal structure of the title compound contains one molecule in the asymmetric unit (Fig. 1). The Flack parameter is equal to 0.12 (18) for the crystals containing (2R)-8-benzyl-2-[(S)-hydroxy(phenyl)methyl]-8-azabicyclo[3.2.1] octan-3-one enantiomer. The intramolecular hydrogen bond is formed between hydroxyl group and heterocyclic nitrogen atom from the azabicyclo[3.2.1]octan-3-one system. The carbonyl oxygen atom is located near equatorial hydrogen atoms of C6 and C7, as well as, the H16A atom. Intra- and intermolecular interactions are shown in Fig. 2 and summarized in Table 1.

Related literature top

For recent background literature on the chemistry of related tropane-derived aldols and their applications, including stereoselective syntheses of bioactive alkaloids, see: Lazny et al. (2011); Sienkiewicz et al. (2009) and references cited therein. For stereoselective syntheses of related nortropinone aldols, see: Lazny et al. (2001); Lazny & Nodzewska (2003). For a representative review of the biological activity of tropane derivatives, see: Singh (2000).

Experimental top

A solution of n-butyllithium in hexane (2.4 M, 0.50 ml, 1.2 mmol) was added dropwise to a cooled (273 K) solution of diisopropylamine (0.168 ml, 1.2 mmol) in tetrahydrofuran (10 ml). The mixture was stirred for 30 min, then cooled to 195 K and a solution of N-benzylnortropinone (0.215 g, 1 mmol) in tetrahydrofuran (7 ml) was added dropwise. After stirring for 2 h, benzaldehyde (0.117 ml, 1.15 mmol) was added dropwise and the mixture was stirred for another 10 min. The reaction was quenched with saturated aq. NH₄Cl (4 ml), allowed to warm to room temperature, and extracted with dichloromethane (3 × 10 ml). The combined extracts were dried over MgSO₄ and concentrated to give the crude product. Crystallization from mixed solvent system hexane/dichloromethane gave the the major product (0.243 g, 75%) as white crystals [m.p. 372–377 K; R_f = 0.77 (10% methanol/dichloromethane); HR (MS-ESI): MNa+, found 344,1640, C₂₁H₂₃NNaO₂ requires 344,1626; ¹H NMR (CDCl₃): 7.43–7.21 (m, 10H), 5.11 (d, J = 3 Hz, 1H), 3.73–3.65 (m, 3H), 3.58–3.57 (m, 1H), 2.82 (ddd, J₁ = 1.5 Hz, J₂ = 4.5 Hz, J₃ = 6 Hz, 1H), 2.45–2.44 (m, 1H), 2.36–2.32 (m, 3H), 1.70–1.66 (m, 2H)].

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and pyMOL (DeLano, 2002); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Crystal packing viewed along the a axis. Dashed lines represent hydrogen bonds. For clarity, only hydrogen atoms involved in the intra- and intermolecular interactions are shown.

(2R)-8-Benzyl-2-[(S)-hydroxy(phenyl)methyl]-8- azabicyclo[3.2.1]octan-3-one top

Crystal data top

C₂₁H₂₃NO₂	F(000) = 688
M_r = 321.40	D_x = 1.220 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54180 Å
Hall symbol: P 2ac 2ab	Cell parameters from 23874 reflections
a = 5.9354 (1) Å	θ = 3.3–73.6°
b = 13.3091 (2) Å	µ = 0.61 mm⁻¹
c = 22.1511 (3) Å	T = 100 K
V = 1749.82 (5) Å³	Needle, colourless
Z = 4	0.65 × 0.25 × 0.19 mm

Data collection top

Oxford Diffraction SuperNova Dual diffractometer	3323 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3276 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.026
Detector resolution: 10.4052 pixels mm^-1	θ_max = 73.6°, θ_min = 3.9°
ω scans	h = −7→6
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011)	k = 0→16
T_min = 0.75, T_max = 0.89	l = 0→27
32829 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	w = 1/[σ²(F_o²) + (0.0283P)² + 0.4297P] where P = (F_o² + 2F_c²)/3
S = 1.18	(Δ/σ)_max < 0.001
3323 reflections	Δρ_max = 0.16 e Å⁻³
218 parameters	Δρ_min = −0.16 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 1257 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.12 (18)

Crystal data top

C₂₁H₂₃NO₂	V = 1749.82 (5) Å³
M_r = 321.40	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 5.9354 (1) Å	µ = 0.61 mm⁻¹
b = 13.3091 (2) Å	T = 100 K
c = 22.1511 (3) Å	0.65 × 0.25 × 0.19 mm

Data collection top

Oxford Diffraction SuperNova Dual diffractometer	3323 independent reflections
Absorption correction: analytical (CrysAlis PRO; Agilent, 2011)	3276 reflections with I > 2σ(I)
T_min = 0.75, T_max = 0.89	R_int = 0.026
32829 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.070	Δρ_max = 0.16 e Å⁻³
S = 1.18	Δρ_min = −0.16 e Å⁻³
3323 reflections	Absolute structure: Flack (1983), 1257 Friedel pairs
218 parameters	Absolute structure parameter: 0.12 (18)
0 restraints

Special details top

Geometry. All e.s.d.'s 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.

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 > 2σ(F²) is used only for calculating R-factors 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.8760 (2)	0.63105 (8)	0.16890 (5)	0.0158 (2)
H1	0.9172	0.6656	0.1304	0.019*
C2	0.8530 (2)	0.51680 (8)	0.15913 (5)	0.0153 (2)
H2	1.0031	0.4903	0.1462	0.018*
C3	0.7921 (2)	0.46720 (9)	0.21973 (5)	0.0169 (3)
O3	0.88275 (17)	0.38983 (7)	0.23623 (4)	0.0256 (2)
C4	0.6185 (2)	0.52123 (8)	0.25898 (5)	0.0177 (3)
H4A	0.6293	0.4967	0.3011	0.021*
H4B	0.4649	0.5066	0.2439	0.021*
C5	0.6612 (2)	0.63510 (8)	0.25734 (5)	0.0164 (2)
H5	0.5476	0.6719	0.2823	0.020*
C6	0.9079 (2)	0.65823 (10)	0.27939 (6)	0.0202 (3)
H6A	0.9603	0.6067	0.3084	0.024*
H6B	0.9166	0.7252	0.2987	0.024*
C7	1.0516 (2)	0.65523 (9)	0.21957 (6)	0.0204 (3)
H7A	1.1253	0.7208	0.2121	0.025*
H7B	1.1686	0.6024	0.2218	0.025*
N8	0.65350 (19)	0.66906 (7)	0.19242 (4)	0.0150 (2)
O9	0.45290 (16)	0.52672 (6)	0.12196 (4)	0.0204 (2)
H9	0.4614	0.5808	0.1414	0.031*
C9	0.6768 (2)	0.49154 (9)	0.10786 (5)	0.0165 (3)
H9C	0.7269	0.5263	0.0701	0.020*
C10	0.6686 (2)	0.38004 (9)	0.09495 (5)	0.0166 (3)
C11	0.8557 (3)	0.33441 (10)	0.06662 (5)	0.0210 (3)
H11	0.9814	0.3742	0.0551	0.025*
C12	0.8568 (3)	0.23166 (10)	0.05557 (6)	0.0238 (3)
H12	0.9833	0.2009	0.0369	0.029*
C13	0.6694 (3)	0.17393 (9)	0.07224 (6)	0.0241 (3)
H13	0.6699	0.1035	0.0652	0.029*
C14	0.4813 (3)	0.21910 (10)	0.09918 (6)	0.0226 (3)
H14	0.3537	0.1794	0.1093	0.027*
C15	0.4803 (2)	0.32179 (9)	0.11116 (5)	0.0196 (3)
H15	0.3539	0.3522	0.1301	0.023*
C16	0.6383 (2)	0.78046 (8)	0.19028 (5)	0.0171 (3)
H16A	0.7639	0.8098	0.2138	0.020*
H16B	0.4952	0.8022	0.2091	0.020*
C17	0.6486 (2)	0.81981 (8)	0.12530 (6)	0.0176 (3)
C18	0.4719 (3)	0.80051 (9)	0.08410 (6)	0.0212 (3)
H18	0.3449	0.7626	0.0969	0.025*
C19	0.4813 (3)	0.83679 (10)	0.02427 (6)	0.0252 (3)
H19	0.3614	0.8234	−0.0030	0.030*
C20	0.6690 (3)	0.89285 (10)	0.00518 (6)	0.0262 (3)
H20	0.6763	0.9177	−0.0350	0.031*
C21	0.8457 (3)	0.91194 (9)	0.04567 (6)	0.0265 (3)
H21	0.9729	0.9494	0.0326	0.032*
C22	0.8362 (3)	0.87590 (9)	0.10572 (6)	0.0227 (3)
H22	0.9564	0.8895	0.1328	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0150 (6)	0.0132 (5)	0.0194 (6)	0.0009 (5)	0.0025 (5)	−0.0001 (4)
C2	0.0143 (6)	0.0129 (5)	0.0186 (5)	0.0017 (5)	−0.0010 (5)	−0.0008 (4)
C3	0.0174 (7)	0.0140 (5)	0.0192 (6)	−0.0017 (5)	−0.0041 (5)	−0.0006 (5)
O3	0.0324 (6)	0.0175 (4)	0.0269 (5)	0.0076 (4)	−0.0038 (4)	0.0032 (4)
C4	0.0197 (7)	0.0154 (5)	0.0178 (5)	0.0003 (5)	0.0000 (5)	0.0026 (4)
C5	0.0180 (7)	0.0157 (5)	0.0156 (5)	0.0014 (5)	0.0006 (5)	−0.0002 (4)
C6	0.0210 (8)	0.0187 (6)	0.0207 (6)	0.0000 (5)	−0.0046 (5)	−0.0004 (5)
C7	0.0147 (7)	0.0183 (6)	0.0283 (7)	0.0003 (5)	−0.0008 (5)	−0.0043 (5)
N8	0.0169 (6)	0.0120 (4)	0.0160 (5)	0.0020 (4)	0.0010 (4)	0.0004 (4)
O9	0.0178 (5)	0.0165 (4)	0.0269 (5)	0.0037 (3)	−0.0038 (4)	−0.0048 (4)
C9	0.0179 (7)	0.0157 (5)	0.0159 (5)	0.0005 (5)	0.0003 (5)	0.0004 (4)
C10	0.0207 (7)	0.0166 (5)	0.0126 (5)	0.0006 (5)	−0.0028 (5)	−0.0009 (4)
C11	0.0220 (7)	0.0223 (6)	0.0187 (6)	−0.0001 (5)	0.0002 (5)	−0.0029 (5)
C12	0.0260 (8)	0.0246 (6)	0.0209 (6)	0.0072 (6)	−0.0024 (6)	−0.0065 (5)
C13	0.0371 (9)	0.0155 (6)	0.0196 (6)	0.0019 (6)	−0.0052 (6)	−0.0030 (5)
C14	0.0309 (8)	0.0194 (6)	0.0175 (6)	−0.0055 (6)	−0.0018 (6)	0.0006 (5)
C15	0.0228 (7)	0.0197 (6)	0.0162 (5)	−0.0005 (5)	0.0008 (5)	−0.0012 (5)
C16	0.0188 (7)	0.0118 (5)	0.0206 (6)	0.0014 (5)	−0.0005 (5)	−0.0013 (4)
C17	0.0194 (7)	0.0110 (5)	0.0224 (6)	0.0034 (5)	0.0025 (6)	0.0002 (4)
C18	0.0228 (8)	0.0171 (6)	0.0238 (6)	0.0003 (5)	0.0003 (5)	0.0034 (5)
C19	0.0302 (8)	0.0218 (6)	0.0235 (6)	0.0036 (6)	−0.0033 (6)	0.0021 (5)
C20	0.0369 (9)	0.0192 (6)	0.0226 (6)	0.0066 (6)	0.0074 (6)	0.0049 (5)
C21	0.0261 (8)	0.0187 (6)	0.0347 (7)	0.0010 (6)	0.0113 (6)	0.0046 (5)
C22	0.0226 (8)	0.0153 (5)	0.0303 (7)	0.0009 (5)	0.0020 (6)	0.0007 (5)

Geometric parameters (Å, º) top

C1—N8	1.5071 (16)	C10—C15	1.4068 (19)
C1—C2	1.5419 (15)	C10—C11	1.4127 (19)
C1—C7	1.5648 (18)	C11—C12	1.3893 (18)
C1—H1	1.0000	C11—H11	0.9500
C2—C3	1.5390 (16)	C12—C13	1.401 (2)
C2—C9	1.5801 (16)	C12—H12	0.9500
C2—H2	1.0000	C13—C14	1.401 (2)
C3—O3	1.2180 (15)	C13—H13	0.9500
C3—C4	1.5279 (18)	C14—C15	1.3923 (17)
C4—C5	1.5368 (15)	C14—H14	0.9500
C4—H4A	0.9900	C15—H15	0.9500
C4—H4B	0.9900	C16—C17	1.5329 (16)
C5—N8	1.5082 (14)	C16—H16A	0.9900
C5—C6	1.5742 (18)	C16—H16B	0.9900
C5—H5	1.0000	C17—C22	1.4091 (19)
C6—C7	1.5762 (18)	C17—C18	1.4140 (19)
C6—H6A	0.9900	C18—C19	1.4116 (18)
C6—H6B	0.9900	C18—H18	0.9500
C7—H7A	0.9900	C19—C20	1.406 (2)
C7—H7B	0.9900	C19—H19	0.9500
N8—C16	1.4861 (14)	C20—C21	1.403 (2)
O9—C9	1.4430 (16)	C20—H20	0.9500
O9—H9	0.8400	C21—C22	1.4151 (19)
C9—C10	1.5121 (16)	C21—H21	0.9500
C9—H9C	1.0000	C22—H22	0.9500

N8—C1—C2	107.58 (10)	O9—C9—H9C	107.8
N8—C1—C7	105.46 (9)	C10—C9—H9C	107.8
C2—C1—C7	111.25 (10)	C2—C9—H9C	107.8
N8—C1—H1	110.8	C15—C10—C11	120.07 (11)
C2—C1—H1	110.8	C15—C10—C9	121.20 (12)
C7—C1—H1	110.8	C11—C10—C9	118.73 (12)
C3—C2—C1	108.74 (9)	C12—C11—C10	120.33 (13)
C3—C2—C9	112.33 (10)	C12—C11—H11	119.8
C1—C2—C9	111.67 (9)	C10—C11—H11	119.8
C3—C2—H2	108.0	C11—C12—C13	119.32 (13)
C1—C2—H2	108.0	C11—C12—H12	120.3
C9—C2—H2	108.0	C13—C12—H12	120.3
O3—C3—C4	121.66 (11)	C12—C13—C14	120.62 (11)
O3—C3—C2	121.38 (12)	C12—C13—H13	119.7
C4—C3—C2	116.94 (10)	C14—C13—H13	119.7
C3—C4—C5	109.85 (10)	C15—C14—C13	120.37 (13)
C3—C4—H4A	109.7	C15—C14—H14	119.8
C5—C4—H4A	109.7	C13—C14—H14	119.8
C3—C4—H4B	109.7	C14—C15—C10	119.27 (13)
C5—C4—H4B	109.7	C14—C15—H15	120.4
H4A—C4—H4B	108.2	C10—C15—H15	120.4
N8—C5—C4	108.25 (9)	N8—C16—C17	111.62 (9)
N8—C5—C6	105.38 (10)	N8—C16—H16A	109.3
C4—C5—C6	109.80 (10)	C17—C16—H16A	109.3
N8—C5—H5	111.1	N8—C16—H16B	109.3
C4—C5—H5	111.1	C17—C16—H16B	109.3
C6—C5—H5	111.1	H16A—C16—H16B	108.0
C5—C6—C7	103.74 (10)	C22—C17—C18	118.94 (12)
C5—C6—H6A	111.0	C22—C17—C16	120.10 (12)
C7—C6—H6A	111.0	C18—C17—C16	120.96 (12)
C5—C6—H6B	111.0	C19—C18—C17	120.96 (13)
C7—C6—H6B	111.0	C19—C18—H18	119.5
H6A—C6—H6B	109.0	C17—C18—H18	119.5
C1—C7—C6	104.36 (10)	C20—C19—C18	119.68 (13)
C1—C7—H7A	110.9	C20—C19—H19	120.2
C6—C7—H7A	110.9	C18—C19—H19	120.2
C1—C7—H7B	110.9	C21—C20—C19	119.74 (12)
C6—C7—H7B	110.9	C21—C20—H20	120.1
H7A—C7—H7B	108.9	C19—C20—H20	120.1
C16—N8—C1	112.14 (10)	C20—C21—C22	120.66 (13)
C16—N8—C5	109.34 (9)	C20—C21—H21	119.7
C1—N8—C5	101.69 (9)	C22—C21—H21	119.7
C9—O9—H9	109.5	C17—C22—C21	120.02 (13)
O9—C9—C10	109.26 (11)	C17—C22—H22	120.0
O9—C9—C2	112.65 (9)	C21—C22—H22	120.0
C10—C9—C2	111.47 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···N8	0.84	1.99	2.7280 (13)	146
C6—H6B···O3ⁱ	0.99	2.61	3.3414 (15)	131
C7—H7A···O3ⁱ	0.99	2.52	3.2954 (15)	135
C16—H16A···O3ⁱ	0.99	2.60	3.5846 (16)	173

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₂₃NO₂
M_r	321.40
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.9354 (1), 13.3091 (2), 22.1511 (3)
V (Å³)	1749.82 (5)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.61
Crystal size (mm)	0.65 × 0.25 × 0.19

Data collection
Diffractometer	Oxford Diffraction SuperNova Dual diffractometer
Absorption correction	Analytical (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.75, 0.89
No. of measured, independent and observed [I > 2σ(I)] reflections	32829, 3323, 3276
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.622

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.070, 1.18
No. of reflections	3323
No. of parameters	218
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.16
Absolute structure	Flack (1983), 1257 Friedel pairs
Absolute structure parameter	0.12 (18)

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXD (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and pyMOL (DeLano, 2002).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9···N8	0.84	1.99	2.7280 (13)	146
C6—H6B···O3ⁱ	0.99	2.61	3.3414 (15)	131
C7—H7A···O3ⁱ	0.99	2.52	3.2954 (15)	135
C16—H16A···O3ⁱ	0.99	2.60	3.5846 (16)	173

Symmetry code: (i) −x+2, y+1/2, −z+1/2.

Acknowledgements

This work was supported in part by the University of Bialystok (BST-125), the Polish Ministry of Science and Higher Education (grant No. N N204 546939), the Intramural Research Program of the NIH, National Cancer Institute, Center for Cancer Research, and with Federal funds from the National Cancer Institute, National Institutes of Health, under contract HHSN2612008000001E.

References

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
DeLano, W. L. (2002). The pyMOL Molecular Graphics System. DeLano Scientific, San Carlos, CA, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Lazny, R. & Nodzewska, A. (2003). Tetrahedron Lett. 44, 2441–2444. Web of Science CrossRef CAS Google Scholar
Lazny, R., Nodzewska, A. & Tomczuk, I. (2011). Tetrahedron Lett. 52, 5680–5683. Web of Science CrossRef CAS Google Scholar
Lazny, R., Sienkiewicz, M. & Bräse, S. (2001). Tetrahedron, 57, 5825–5832. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sienkiewicz, M., Wilkaniec, U. & Lazny, R. (2009). Tetrahedron Lett. 50, 7196–7198. Web of Science CrossRef CAS Google Scholar
Singh, S. (2000). Chem. Rev. 100, 925–1024. Web of Science CrossRef PubMed CAS Google Scholar

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Volume 68| Part 1| January 2012| Pages o149-o150

doi:10.1107/S1600536811053190

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

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(2R)-8-Benzyl-2-[(S)-hydroxy(phenyl)methyl]-8-azabicyclo[3.2.1]octan-3-one