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Acta Crystallogr Sect E Struct Rep Online. 2008 August 1; 64(Pt 8): o1653.
Published online 2008 July 31. doi:  10.1107/S1600536808023532
PMCID: PMC2962227

(R)-(+)-3-Hydr­oxy-2-methoxy­carbonyl-8-methyl-8-azoniabicyclo­[3.2.1]octane l-bitartrate

Abstract

(RS)-(±)-2-Methoxy­carbonyl-3-tropinone is an important inter­mediate for the preparation of cocaine and its derivatives. The molecule in the title compound, C10H16NO3 +·C4H5O6 , is present as the enol tautomer. The six-membered ring adopts a half boat conformation, and the five-membered ring a slightly distorted envelope conformation. There are intra- and inter­molecular hydrogen bonds involving the hydroxyl, carboxyl groups and quaternary ammonium groups.

Related literature

For related literature, see: Findlay (1957 [triangle]); Meltzer et al. (1994 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o1653-scheme1.jpg

Experimental

Crystal data

  • C10H16NO3 +·C4H5O6
  • M r = 347.32
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1653-efi3.jpg
  • a = 6.5030 (10) Å
  • b = 15.914 (3) Å
  • c = 7.6626 (12) Å
  • β = 96.497 (3)°
  • V = 787.9 (2) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.12 mm−1
  • T = 293 (2) K
  • 0.50 × 0.49 × 0.37 mm

Data collection

  • SMART 1K CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 2002 [triangle]) T min = 0.936, T max = 0.961
  • 4145 measured reflections
  • 1522 independent reflections
  • 1460 reflections with I > 2σ(I)
  • R int = 0.082

Refinement

  • R[F 2 > 2σ(F 2)] = 0.064
  • wR(F 2) = 0.154
  • S = 1.05
  • 1522 reflections
  • 226 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.38 e Å−3
  • Δρmin = −0.35 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023532/rk2093sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023532/rk2093Isup2.hkl

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

Acknowledgments

We thank the Shanghai Institute of Organic Chemistry for the X-ray data collection and analysis.

supplementary crystallographic information

Comment

The (RS)-(±)-2-carbomethoxy-3-tropinone, I is an important intermediate for preparation of cocaine and its derivatives (Meltzer et al., 1994). It could be resolved by recrystallizing its L- and D-bitartrates (Findlay, 1957). The molecular struture of I is the enol tautomer of the title compound. As shown on Fig. 1, the asymmetric unit of I contains a quaternary ammonium cation and a bitartrate. The 6-membered ring is nearly a chair conformation. The five-membered ring adopts nearly an envelope conformation with N1 atom deviation from C3/C4/C5/C6 plane 0.306 (2)Å. There are intra- and intermolecular hydrogen bonds involving the hydroxyl, carboxyl and quaternary ammonium ions. The system of these H-bond with formation a two-dimensional network presented on Fig. 2. All bond lengths and angles in I are normal.

Experimental

All reagents were of analytical grade and used without further purification. The title compound I was prepared by the general procedure (Findlay, 1957). The single crystals were obtained by evaporation of its methanol solution.

Refinement

H atoms were located in a difference Fourier map and refined isotropically with bond restraints N1–H1, other H atoms were positioned geometrically and treated as riding, with C–H and O–H bond lengths constrained to 0.96Å for methyl, 0.97Å for methylene, 0.98Å for methine and 0.82Å for hydroxyl, with Uiso(H) = 1.5Ueq(methyl C and hydroxyl O) and Uiso(H) = 1.2Ueq(methylene and methine C).

The 2813 Friedel pairs were merged.

Figures

Fig. 1.
The molecular structure of I with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are presented as a small spheres of arbitrary radius.
Fig. 2.
Parts of the two-dimensional network in I. H atoms not involved in hydrogen bonds have been omitted for clarity. Symmetry codes: (A) -x, y-1/2, -z+1; (B) x, y, z+1; (E) -x, y+1/2, -z+1.

Crystal data

C10H16NO3+·C4H5O6F000 = 368
Mr = 347.32Dx = 1.464 Mg m3
Monoclinic, P21Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 2848 reflections
a = 6.5030 (10) Åθ = 5.1–56.6º
b = 15.914 (3) ŵ = 0.12 mm1
c = 7.6626 (12) ÅT = 293 (2) K
β = 96.497 (3)ºPrism, colourless
V = 787.9 (2) Å30.50 × 0.49 × 0.37 mm
Z = 2

Data collection

SMART 1K CCD area-detector diffractometer1522 independent reflections
Radiation source: Fine-focus sealed tube1460 reflections with I > 2σ(I)
Monochromator: GraphiteRint = 0.082
T = 293(2) Kθmax = 25.5º
[var phi] and ω scansθmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 2002)h = −6→7
Tmin = 0.936, Tmax = 0.961k = −19→19
4145 measured reflectionsl = −9→8

Refinement

Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.064H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.154  w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1522 reflectionsΔρmax = 0.38 e Å3
226 parametersΔρmin = −0.35 e Å3
2 restraintsExtinction correction: None
Primary atom site location: Direct

Special details

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 F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > σ(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ 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)

xyzUiso*/Ueq
O10.4137 (5)0.42707 (19)1.0979 (4)0.0430 (7)
H1A0.33130.44111.01400.064*
O20.2485 (5)0.42415 (18)0.7727 (4)0.0424 (7)
O30.3452 (4)0.31950 (18)0.6043 (3)0.0394 (6)
O40.0156 (5)0.0122 (2)0.7351 (4)0.0490 (7)
O50.2813 (4)0.0965 (2)0.8123 (3)0.0443 (7)
H50.27350.07670.91010.066*
O6−0.0490 (4)0.0881 (2)0.4144 (4)0.0503 (7)
H6A−0.09710.04190.43460.076*
O70.2769 (6)−0.03238 (19)0.4196 (4)0.0533 (8)
H70.2713−0.04790.31710.080*
O80.3679 (5)0.16640 (19)0.2317 (4)0.0470 (7)
O90.2908 (5)0.0395 (2)0.1220 (3)0.0494 (8)
N10.6693 (4)0.20164 (19)1.0231 (4)0.0285 (6)
C10.5207 (5)0.3624 (2)1.0542 (5)0.0302 (7)
C20.6708 (6)0.3287 (2)1.1994 (5)0.0387 (9)
H2A0.59510.30541.29020.046*
H2B0.75620.37431.25090.046*
C30.8082 (5)0.2615 (3)1.1353 (5)0.0356 (8)
H30.88520.23191.23410.043*
C40.9545 (5)0.2942 (3)1.0073 (6)0.0483 (10)
H4A1.08710.26581.02630.058*
H4B0.97710.35411.02300.058*
C50.8474 (6)0.2756 (3)0.8221 (6)0.0437 (9)
H5A0.84670.32490.74750.052*
H5B0.91560.22990.76780.052*
C60.6273 (5)0.2510 (2)0.8544 (5)0.0304 (7)
H60.55960.21650.75870.036*
C70.4975 (5)0.3252 (2)0.8921 (5)0.0298 (7)
C80.3528 (5)0.3622 (2)0.7538 (5)0.0304 (7)
C90.2115 (7)0.3550 (3)0.4589 (6)0.0508 (11)
H9A0.08280.37170.49850.076*
H9B0.18560.31370.36770.076*
H9C0.27740.40310.41390.076*
C100.7663 (6)0.1188 (2)0.9999 (5)0.0390 (8)
H10A0.69430.09080.90030.058*
H10B0.75910.08541.10330.058*
H10C0.90860.12670.98120.058*
C110.1363 (5)0.0638 (2)0.7001 (4)0.0305 (7)
C120.1436 (5)0.0981 (2)0.5152 (4)0.0334 (8)
H120.17520.15820.52400.040*
C130.3152 (5)0.0546 (2)0.4291 (4)0.0327 (8)
H130.44750.06430.50100.039*
C140.3271 (5)0.0916 (3)0.2461 (4)0.0321 (7)
H10.543 (4)0.188 (2)1.068 (5)0.026 (9)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0541 (15)0.0441 (14)0.0301 (14)0.0102 (13)0.0021 (11)−0.0035 (13)
O20.0453 (13)0.0446 (14)0.0360 (15)0.0180 (12)−0.0015 (11)0.0030 (13)
O30.0432 (13)0.0527 (15)0.0200 (13)0.0097 (12)−0.0066 (9)0.0019 (12)
O40.0579 (15)0.0664 (18)0.0237 (13)−0.0218 (15)0.0089 (11)−0.0036 (14)
O50.0545 (14)0.0633 (16)0.0141 (12)−0.0159 (14)0.0000 (10)0.0055 (13)
O60.0430 (13)0.079 (2)0.0269 (14)0.0105 (15)−0.0062 (10)0.0089 (15)
O70.089 (2)0.0441 (15)0.0291 (16)0.0119 (16)0.0166 (15)0.0036 (13)
O80.0640 (17)0.0522 (17)0.0267 (15)−0.0055 (14)0.0139 (12)0.0041 (13)
O90.0798 (19)0.0564 (16)0.0124 (12)0.0012 (16)0.0067 (12)0.0005 (12)
N10.0293 (12)0.0377 (15)0.0176 (13)−0.0008 (11)−0.0007 (10)0.0038 (12)
C10.0320 (15)0.0308 (16)0.0272 (19)−0.0059 (14)0.0012 (12)0.0005 (14)
C20.0456 (18)0.044 (2)0.0238 (18)−0.0020 (17)−0.0083 (14)−0.0023 (17)
C30.0320 (15)0.0437 (18)0.0277 (18)−0.0068 (15)−0.0114 (13)0.0067 (16)
C40.0299 (17)0.057 (2)0.058 (3)−0.0043 (18)0.0027 (15)0.007 (2)
C50.0405 (18)0.048 (2)0.045 (2)0.0075 (16)0.0155 (15)0.0118 (19)
C60.0323 (15)0.0375 (18)0.0207 (17)−0.0010 (14)0.0000 (12)0.0056 (14)
C70.0285 (14)0.0363 (16)0.0235 (17)−0.0033 (13)−0.0010 (11)0.0032 (14)
C80.0294 (14)0.0359 (17)0.0255 (19)−0.0012 (14)0.0018 (13)0.0058 (14)
C90.055 (2)0.072 (3)0.0219 (19)0.016 (2)−0.0107 (16)0.007 (2)
C100.0442 (18)0.0422 (19)0.0292 (19)0.0088 (16)−0.0010 (14)0.0049 (16)
C110.0374 (15)0.0406 (17)0.0138 (16)−0.0002 (14)0.0043 (11)−0.0035 (15)
C120.0439 (17)0.0420 (18)0.0140 (16)0.0032 (16)0.0026 (13)0.0020 (15)
C130.0422 (17)0.0451 (19)0.0103 (16)0.0031 (15)0.0000 (12)0.0035 (14)
C140.0382 (16)0.046 (2)0.0118 (15)0.0002 (15)0.0041 (11)0.0018 (15)

Geometric parameters (Å, °)

O1—C11.307 (5)C3—C41.533 (6)
O1—H1A0.8200C3—H30.9800
O2—C81.215 (4)C4—C51.537 (7)
O3—C81.328 (5)C4—H4A0.9700
O3—C91.448 (4)C4—H4B0.9700
O4—C111.188 (5)C5—C61.531 (5)
O5—C111.309 (4)C5—H5A0.9700
O5—H50.8200C5—H5B0.9700
O6—C121.404 (4)C6—C71.498 (5)
O6—H6A0.8200C6—H60.9800
O7—C131.407 (5)C7—C81.459 (5)
O7—H70.8200C9—H9A0.9600
O8—C141.228 (5)C9—H9B0.9600
O9—C141.262 (5)C9—H9C0.9600
N1—C101.481 (5)C10—H10A0.9600
N1—C61.511 (4)C10—H10B0.9600
N1—C31.511 (4)C10—H10C0.9600
N1—H10.954 (19)C11—C121.524 (4)
C1—C71.369 (5)C12—C131.525 (5)
C1—C21.495 (5)C12—H120.9800
C2—C31.511 (6)C13—C141.531 (4)
C2—H2A0.9700C13—H130.9800
C2—H2B0.9700
C1—O1—H1A109.5N1—C6—C5100.9 (3)
C8—O3—C9115.2 (3)C7—C6—H6111.8
C11—O5—H5109.5N1—C6—H6111.8
C12—O6—H6A109.5C5—C6—H6111.8
C13—O7—H7109.5C1—C7—C8118.7 (3)
C10—N1—C6113.5 (3)C1—C7—C6120.6 (3)
C10—N1—C3113.2 (3)C8—C7—C6120.6 (3)
C6—N1—C3101.4 (3)O2—C8—O3123.4 (3)
C10—N1—H1103 (2)O2—C8—C7124.4 (3)
C6—N1—H1111 (2)O3—C8—C7112.2 (3)
C3—N1—H1115 (2)O3—C9—H9A109.5
O1—C1—C7124.5 (3)O3—C9—H9B109.5
O1—C1—C2114.5 (3)H9A—C9—H9B109.5
C7—C1—C2121.0 (3)O3—C9—H9C109.5
C1—C2—C3111.9 (3)H9A—C9—H9C109.5
C1—C2—H2A109.2H9B—C9—H9C109.5
C3—C2—H2A109.2N1—C10—H10A109.5
C1—C2—H2B109.2N1—C10—H10B109.5
C3—C2—H2B109.2H10A—C10—H10B109.5
H2A—C2—H2B107.9N1—C10—H10C109.5
C2—C3—N1107.1 (3)H10A—C10—H10C109.5
C2—C3—C4113.6 (3)H10B—C10—H10C109.5
N1—C3—C4103.0 (3)O4—C11—O5124.9 (3)
C2—C3—H3111.0O4—C11—C12123.2 (3)
N1—C3—H3111.0O5—C11—C12111.8 (3)
C4—C3—H3111.0O6—C12—C11110.6 (3)
C3—C4—C5106.0 (3)O6—C12—C13111.2 (3)
C3—C4—H4A110.5C11—C12—C13110.0 (3)
C5—C4—H4A110.5O6—C12—H12108.3
C3—C4—H4B110.5C11—C12—H12108.3
C5—C4—H4B110.5C13—C12—H12108.3
H4A—C4—H4B108.7O7—C13—C12109.5 (3)
C6—C5—C4103.5 (3)O7—C13—C14111.0 (3)
C6—C5—H5A111.1C12—C13—C14109.7 (3)
C4—C5—H5A111.1O7—C13—H13108.9
C6—C5—H5B111.1C12—C13—H13108.9
C4—C5—H5B111.1C14—C13—H13108.9
H5A—C5—H5B109.0O8—C14—O9126.3 (3)
C7—C6—N1107.2 (3)O8—C14—C13119.2 (3)
C7—C6—C5112.8 (3)O9—C14—C13114.4 (3)
O1—C1—C2—C3−172.8 (3)C5—C6—C7—C1−77.6 (4)
C7—C1—C2—C39.1 (5)N1—C6—C7—C8−151.1 (3)
C1—C2—C3—N1−47.1 (4)C5—C6—C7—C898.7 (4)
C1—C2—C3—C465.9 (4)C9—O3—C8—O23.7 (5)
C10—N1—C3—C2−160.7 (3)C9—O3—C8—C7−177.3 (3)
C6—N1—C3—C277.4 (3)C1—C7—C8—O2−0.7 (5)
C10—N1—C3—C479.3 (3)C6—C7—C8—O2−177.0 (3)
C6—N1—C3—C4−42.6 (3)C1—C7—C8—O3−179.7 (3)
C2—C3—C4—C5−96.8 (4)C6—C7—C8—O33.9 (4)
N1—C3—C4—C518.7 (4)O4—C11—C12—O623.5 (5)
C3—C4—C5—C611.9 (4)O5—C11—C12—O6−158.1 (3)
C10—N1—C6—C7170.3 (3)O4—C11—C12—C13−99.7 (4)
C3—N1—C6—C7−68.0 (3)O5—C11—C12—C1378.7 (4)
C10—N1—C6—C5−71.4 (4)O6—C12—C13—O7−62.8 (4)
C3—N1—C6—C550.2 (3)C11—C12—C13—O760.0 (4)
C4—C5—C6—C776.1 (4)O6—C12—C13—C1459.3 (4)
C4—C5—C6—N1−37.9 (4)C11—C12—C13—C14−177.9 (3)
O1—C1—C7—C83.8 (5)O7—C13—C14—O8−177.1 (3)
C2—C1—C7—C8−178.4 (3)C12—C13—C14—O861.7 (4)
O1—C1—C7—C6−179.8 (3)O7—C13—C14—O93.4 (4)
C2—C1—C7—C6−2.0 (5)C12—C13—C14—O9−117.8 (3)
N1—C6—C7—C132.6 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1A···O20.821.892.600 (4)145
O7—H7···O90.822.062.562 (4)120
N1—H1···O8i0.954 (19)1.82 (2)2.724 (4)158 (4)
O6—H6A···O2ii0.822.583.182 (4)132
O5—H5···O9i0.821.722.535 (4)172

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2093).

References

  • Bruker (2001). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Findlay, S. P. (1957). J. Org. Chem.22, 1385–1394.
  • Meltzer, P. C., Liang, A. Y. & Madras, B. K. (1994). J. Med. Chem.37, 2001-2010. [PubMed]
  • Sheldrick, G. M. (2002). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2008). publCIF. In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography