(1RS,2SR,5SR)-9-Benzyl-2-[(1RS)-1-hy-droxy-benz-yl]-9-aza-bicyclo-[3.3.1]nonan-3-one from synchrotron data.

In the crystal structure of the racemic title compound, C(22)H(25)NO(2), solved and refined against sychrotron diffraction data, the hy-droxy group and the carbonyl O atom participate in the formation of O-H⋯O hydrogen bonds between pairs of enanti-omers related by a crystallographic centre of symmetry.

Related literature

For recent background literature on the synthesis, structure and applications of related granatane-derived aldols, see: Lazny et al. (2011a ▶) and references cited therein. For the stereoselective syntheses, applications and structures of related tropinone aldols, see: Sienkiewicz et al. (2009 ▶); Lazny et al. (2011b ▶); Brzezinski et al. (2012 ▶) and for related nortropin­one aldols, see: Lazny et al. (2001 ▶, 2010 ▶); Lazny & Nodzewska (2003 ▶).

Experimental

Crystal data

C22H25NO2

M = 335.43

Monoclinic,

a = 14.380 (3) Å

b = 9.3100 (19) Å

c = 13.270 (3) Å

β = 106.21 (3)°

V = 1705.9 (6) Å3

Z = 4

Synchrotron radiation

λ = 0.61992 Å

μ = 0.08 mm−1

T = 100 K

0.3 × 0.1 × 0.1 mm

Data collection

Mar Research MAR315 CCD diffractometer

Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 2003 ▶) T min = 0.975, T max = 0.992

64629 measured reflections

8582 independent reflections

7757 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.119

S = 1.03

8582 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.58 e Å−3

Δρmin = −0.30 e Å−3

Data collection: NECAT APS beamline software; cell refinement: HKL-2000 (Otwinowski & Minor, 1997 ▶); data reduction: HKL-2000; 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812014754/kp2402sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014754/kp2402Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812014754/kp2402Isup3.cml

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

C22H25NO2	F(000) = 720
Mr = 335.43	Dx = 1.306 Mg m−3
Monoclinic, P21/c	Synchrotron radiation, λ = 0.61992 Å
Hall symbol: -P 2ybc	Cell parameters from 8582 reflections
a = 14.380 (3) Å	θ = 2.4–31.7°
b = 9.3100 (19) Å	µ = 0.08 mm−1
c = 13.270 (3) Å	T = 100 K
β = 106.21 (3)°	Needle, colourless
V = 1705.9 (6) Å3	0.3 × 0.1 × 0.1 mm
Z = 4

Mar Research MAR315 CCD diffractometer	8582 independent reflections
Radiation source: NECAT 24ID-C synchrotron beamline APS, USA	7757 reflections with I > 2σ(I)
Si111 double crystal monochromator	Rint = 0.046
ω scans	θmax = 31.7°, θmin = 2.4°
Absorption correction: multi-scan (SCALEPACK; Otwinowski et al., 2003)	h = −24→23
Tmin = 0.975, Tmax = 0.992	k = −15→0
64629 measured reflections	l = 0→22

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.076P)2 + 0.3P] where P = (Fo2 + 2Fc2)/3
8582 reflections	(Δ/σ)max = 0.001
227 parameters	Δρmax = 0.58 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Experimental. The crystal was mounted with vaseline on a pin-attached capillary. Upon mounting, the crystal was quenched to 100 K in a nitrogen-gas stream supplied by an Oxford Cryo-Jet. Diffraction data were measured at the station 24-ID—C of the APS synchrotron by rotation method.

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.

	x	y	z	Uiso*/Ueq
C1	0.30958 (3)	0.78442 (5)	0.11193 (4)	0.00793 (8)
H1	0.2751	0.7328	0.1570	0.010*
C2	0.36548 (3)	0.67096 (5)	0.06626 (4)	0.00840 (8)
H2	0.4214	0.6355	0.1241	0.010*
C3	0.40394 (4)	0.73073 (6)	−0.02043 (4)	0.01010 (8)
O3	0.48222 (3)	0.69336 (5)	−0.03110 (4)	0.01510 (8)
C4	0.33793 (4)	0.83261 (6)	−0.09524 (4)	0.01142 (9)
H4A	0.2903	0.7762	−0.1489	0.014*
H4B	0.3768	0.8897	−0.1317	0.014*
C5	0.28317 (4)	0.93572 (6)	−0.04151 (4)	0.01032 (8)
H5	0.2313	0.9837	−0.0976	0.012*
C6	0.34966 (4)	1.05349 (6)	0.02088 (4)	0.01288 (9)
H6A	0.3832	1.1020	−0.0254	0.015*
H6B	0.3099	1.1261	0.0443	0.015*
C7	0.42514 (4)	0.99255 (6)	0.11677 (4)	0.01233 (9)
H7A	0.4588	1.0726	0.1614	0.015*
H7B	0.4740	0.9370	0.0933	0.015*
C8	0.37747 (4)	0.89508 (6)	0.18111 (4)	0.01071 (8)
H8A	0.3402	0.9548	0.2178	0.013*
H8B	0.4284	0.8442	0.2350	0.013*
N9	0.23546 (3)	0.85037 (5)	0.02376 (3)	0.00863 (7)
C10	0.29832 (3)	0.54154 (6)	0.02123 (4)	0.00928 (8)
H10	0.2345	0.5823	−0.0194	0.011*
O10	0.33364 (3)	0.45861 (5)	−0.05034 (3)	0.01360 (8)
H10A	0.3898	0.4294	−0.0203	0.020*
C11	0.27972 (3)	0.45235 (5)	0.10896 (4)	0.00883 (8)
C12	0.18961 (4)	0.45726 (6)	0.12906 (4)	0.01206 (9)
H12	0.1403	0.5180	0.0881	0.014*
C13	0.17105 (4)	0.37413 (7)	0.20856 (5)	0.01465 (10)
H13	0.1093	0.3782	0.2213	0.018*
C14	0.24272 (4)	0.28511 (6)	0.26930 (4)	0.01428 (10)
H14	0.2298	0.2270	0.3227	0.017*
C15	0.33362 (4)	0.28183 (6)	0.25111 (4)	0.01342 (9)
H15	0.3833	0.2228	0.2933	0.016*
C16	0.35203 (4)	0.36467 (6)	0.17144 (4)	0.01158 (9)
H16	0.4141	0.3616	0.1595	0.014*
C17	0.16235 (4)	0.93738 (6)	0.05545 (4)	0.01253 (9)
H17A	0.1176	0.9806	−0.0079	0.015*
H17B	0.1954	1.0166	0.1014	0.015*
C18	0.10470 (4)	0.85031 (6)	0.11268 (4)	0.01131 (9)
C19	0.13134 (4)	0.84836 (6)	0.22226 (4)	0.01282 (9)
H19	0.1831	0.9076	0.2603	0.015*
C20	0.08325 (4)	0.76093 (7)	0.27672 (5)	0.01567 (10)
H20	0.1035	0.7585	0.3512	0.019*
C21	0.00550 (4)	0.67733 (7)	0.22170 (5)	0.01794 (11)
H21	−0.0269	0.6164	0.2584	0.022*
C22	−0.02467 (4)	0.68332 (8)	0.11257 (5)	0.01934 (11)
H22	−0.0794	0.6292	0.0749	0.023*
C23	0.02508 (4)	0.76839 (7)	0.05837 (5)	0.01621 (10)
H23	0.0047	0.7707	−0.0162	0.019*

	U11	U22	U33	U12	U13	U23
C1	0.00930 (16)	0.00893 (19)	0.00596 (16)	0.00061 (13)	0.00280 (13)	−0.00010 (13)
C2	0.00893 (16)	0.00910 (19)	0.00783 (16)	−0.00015 (13)	0.00343 (13)	−0.00046 (13)
C3	0.01167 (18)	0.0101 (2)	0.01030 (18)	−0.00211 (14)	0.00599 (14)	−0.00254 (14)
O3	0.01403 (16)	0.01532 (19)	0.01972 (19)	0.00038 (13)	0.01092 (14)	−0.00186 (15)
C4	0.01423 (19)	0.0137 (2)	0.00782 (17)	−0.00160 (15)	0.00560 (15)	0.00005 (15)
C5	0.01295 (18)	0.0109 (2)	0.00784 (17)	−0.00003 (15)	0.00418 (14)	0.00183 (14)
C6	0.0171 (2)	0.0097 (2)	0.0129 (2)	−0.00171 (16)	0.00595 (16)	0.00079 (15)
C7	0.01364 (19)	0.0116 (2)	0.01232 (19)	−0.00284 (15)	0.00451 (15)	−0.00222 (16)
C8	0.01263 (18)	0.0115 (2)	0.00778 (17)	−0.00095 (15)	0.00251 (14)	−0.00161 (14)
N9	0.00942 (15)	0.01032 (18)	0.00683 (15)	0.00179 (12)	0.00338 (12)	0.00153 (12)
C10	0.01063 (17)	0.0100 (2)	0.00774 (17)	−0.00114 (14)	0.00340 (13)	−0.00120 (14)
O10	0.01844 (17)	0.01365 (18)	0.01040 (15)	−0.00106 (13)	0.00681 (13)	−0.00429 (13)
C11	0.00996 (17)	0.00859 (19)	0.00832 (17)	−0.00088 (13)	0.00316 (13)	−0.00087 (13)
C12	0.01043 (18)	0.0135 (2)	0.0130 (2)	−0.00065 (15)	0.00445 (15)	0.00118 (16)
C13	0.0149 (2)	0.0158 (2)	0.0156 (2)	−0.00242 (17)	0.00802 (17)	0.00100 (18)
C14	0.0206 (2)	0.0125 (2)	0.01139 (19)	−0.00221 (17)	0.00719 (17)	0.00027 (16)
C15	0.0181 (2)	0.0119 (2)	0.01043 (19)	0.00227 (16)	0.00425 (16)	0.00130 (16)
C16	0.01218 (18)	0.0124 (2)	0.01057 (18)	0.00178 (15)	0.00386 (14)	0.00047 (15)
C17	0.01361 (19)	0.0129 (2)	0.0126 (2)	0.00440 (16)	0.00617 (15)	0.00246 (16)
C18	0.01020 (17)	0.0139 (2)	0.01086 (18)	0.00307 (15)	0.00472 (14)	0.00007 (15)
C19	0.01191 (18)	0.0166 (2)	0.01089 (19)	0.00131 (16)	0.00477 (15)	−0.00027 (16)
C20	0.0147 (2)	0.0212 (3)	0.0132 (2)	0.00182 (18)	0.00730 (17)	0.00159 (18)
C21	0.0158 (2)	0.0205 (3)	0.0214 (3)	−0.00107 (19)	0.01156 (19)	−0.0008 (2)
C22	0.0138 (2)	0.0253 (3)	0.0208 (3)	−0.00457 (19)	0.00800 (19)	−0.0067 (2)
C23	0.01207 (19)	0.0241 (3)	0.0130 (2)	−0.00040 (18)	0.00449 (16)	−0.00376 (19)

C1—N9	1.4784 (8)	O10—H10A	0.8400
C1—C8	1.5353 (8)	C11—C12	1.3947 (8)
C1—C2	1.5496 (7)	C11—C16	1.3977 (8)
C1—H1	1.0000	C12—C13	1.3931 (8)
C2—C3	1.5147 (7)	C12—H12	0.9500
C2—C10	1.5554 (8)	C13—C14	1.3910 (9)
C2—H2	1.0000	C13—H13	0.9500
C3—O3	1.2236 (7)	C14—C15	1.3942 (9)
C3—C4	1.5033 (8)	C14—H14	0.9500
C4—C5	1.5374 (8)	C15—C16	1.3924 (8)
C4—H4A	0.9900	C15—H15	0.9500
C4—H4B	0.9900	C16—H16	0.9500
C5—N9	1.4778 (7)	C17—C18	1.5075 (8)
C5—C6	1.5362 (8)	C17—H17A	0.9900
C5—H5	1.0000	C17—H17B	0.9900
C6—C7	1.5324 (9)	C18—C23	1.3969 (9)
C6—H6A	0.9900	C18—C19	1.3966 (8)
C6—H6B	0.9900	C19—C20	1.3936 (8)
C7—C8	1.5326 (8)	C19—H19	0.9500
C7—H7A	0.9900	C20—C21	1.3903 (10)
C7—H7B	0.9900	C20—H20	0.9500
C8—H8A	0.9900	C21—C22	1.3920 (10)
C8—H8B	0.9900	C21—H21	0.9500
N9—C17	1.4782 (7)	C22—C23	1.3941 (9)
C10—O10	1.4232 (7)	C22—H22	0.9500
C10—C11	1.5133 (7)	C23—H23	0.9500
C10—H10	1.0000
N9—C1—C8	113.09 (5)	O10—C10—C2	112.19 (4)
N9—C1—C2	108.16 (4)	C11—C10—C2	110.71 (4)
C8—C1—C2	112.25 (4)	O10—C10—H10	106.9
N9—C1—H1	107.7	C11—C10—H10	106.9
C8—C1—H1	107.7	C2—C10—H10	106.9
C2—C1—H1	107.7	C10—O10—H10A	109.5
C3—C2—C1	112.69 (4)	C12—C11—C16	118.86 (5)
C3—C2—C10	108.18 (4)	C12—C11—C10	120.15 (5)
C1—C2—C10	110.12 (4)	C16—C11—C10	120.99 (4)
C3—C2—H2	108.6	C13—C12—C11	120.75 (5)
C1—C2—H2	108.6	C13—C12—H12	119.6
C10—C2—H2	108.6	C11—C12—H12	119.6
O3—C3—C4	122.33 (5)	C14—C13—C12	120.14 (5)
O3—C3—C2	121.74 (5)	C14—C13—H13	119.9
C4—C3—C2	115.87 (4)	C12—C13—H13	119.9
C3—C4—C5	113.48 (4)	C13—C14—C15	119.45 (5)
C3—C4—H4A	108.9	C13—C14—H14	120.3
C5—C4—H4A	108.9	C15—C14—H14	120.3
C3—C4—H4B	108.9	C16—C15—C14	120.36 (5)
C5—C4—H4B	108.9	C16—C15—H15	119.8
H4A—C4—H4B	107.7	C14—C15—H15	119.8
N9—C5—C6	112.88 (4)	C15—C16—C11	120.42 (5)
N9—C5—C4	108.53 (5)	C15—C16—H16	119.8
C6—C5—C4	111.92 (4)	C11—C16—H16	119.8
N9—C5—H5	107.8	N9—C17—C18	112.54 (5)
C6—C5—H5	107.8	N9—C17—H17A	109.1
C4—C5—H5	107.8	C18—C17—H17A	109.1
C7—C6—C5	111.92 (5)	N9—C17—H17B	109.1
C7—C6—H6A	109.2	C18—C17—H17B	109.1
C5—C6—H6A	109.2	H17A—C17—H17B	107.8
C7—C6—H6B	109.2	C23—C18—C19	118.50 (5)
C5—C6—H6B	109.2	C23—C18—C17	121.36 (5)
H6A—C6—H6B	107.9	C19—C18—C17	120.13 (5)
C6—C7—C8	111.01 (4)	C20—C19—C18	121.06 (6)
C6—C7—H7A	109.4	C20—C19—H19	119.5
C8—C7—H7A	109.4	C18—C19—H19	119.5
C6—C7—H7B	109.4	C21—C20—C19	119.83 (6)
C8—C7—H7B	109.4	C21—C20—H20	120.1
H7A—C7—H7B	108.0	C19—C20—H20	120.1
C7—C8—C1	111.89 (4)	C22—C21—C20	119.68 (6)
C7—C8—H8A	109.2	C22—C21—H21	120.2
C1—C8—H8A	109.2	C20—C21—H21	120.2
C7—C8—H8B	109.2	C21—C22—C23	120.25 (6)
C1—C8—H8B	109.2	C21—C22—H22	119.9
H8A—C8—H8B	107.9	C23—C22—H22	119.9
C5—N9—C1	109.70 (4)	C22—C23—C18	120.58 (6)
C5—N9—C17	110.82 (4)	C22—C23—H23	119.7
C1—N9—C17	114.54 (4)	C18—C23—H23	119.7
O10—C10—C11	112.85 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10A···O3i	0.84	2.11	2.9298 (9)	165

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10A⋯O3i	0.84	2.11	2.9298 (9)	165

Symmetry code: (i) .