(R)-(+)-3-Hydr-oxy-2-methoxy-carbonyl-8-methyl-8-azoniabicyclo-[3.2.1]octane l-bitartrate.

(RS)-(±)-2-Methoxy-carbonyl-3-tropinone is an important inter-mediate for the preparation of cocaine and its derivatives. The molecule in the title compound, C(10)H(16)NO(3) (+)·C(4)H(5)O(6) (-), 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 inter-molecular hydrogen bonds involving the hydroxyl, carboxyl groups and quaternary ammonium groups.

Related literature

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

Experimental

Crystal data

C10H16NO3 +·C4H5O6 −

M = 347.32

Monoclinic,

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 (; Sheldrick, 2002 ▶) 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 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2008 ▶).

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

C10H16NO3+·C4H5O6–	F000 = 368
Mr = 347.32	Dx = 1.464 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2848 reflections
a = 6.5030 (10) Å	θ = 5.1–56.6º
b = 15.914 (3) Å	µ = 0.12 mm−1
c = 7.6626 (12) Å	T = 293 (2) K
β = 96.497 (3)º	Prism, colourless
V = 787.9 (2) Å3	0.50 × 0.49 × 0.37 mm
Z = 2

SMART 1K CCD area-detector diffractometer	1522 independent reflections
Radiation source: Fine-focus sealed tube	1460 reflections with I > 2σ(I)
Monochromator: Graphite	Rint = 0.082
T = 293(2) K	θmax = 25.5º
φ and ω scans	θmin = 2.6º
Absorption correction: multi-scan(SADABS; Sheldrick, 2002)	h = −6→7
Tmin = 0.936, Tmax = 0.961	k = −19→19
4145 measured reflections	l = −9→8

Refinement on F2	Secondary atom site location: Difmap
Least-squares matrix: Full	Hydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.064	H 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 reflections	Δρmax = 0.38 e Å−3
226 parameters	Δρmin = −0.35 e Å−3
2 restraints	Extinction correction: None
Primary atom site location: Direct

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.

	x	y	z	Uiso*/Ueq
O1	0.4137 (5)	0.42707 (19)	1.0979 (4)	0.0430 (7)
H1A	0.3313	0.4411	1.0140	0.064*
O2	0.2485 (5)	0.42415 (18)	0.7727 (4)	0.0424 (7)
O3	0.3452 (4)	0.31950 (18)	0.6043 (3)	0.0394 (6)
O4	0.0156 (5)	0.0122 (2)	0.7351 (4)	0.0490 (7)
O5	0.2813 (4)	0.0965 (2)	0.8123 (3)	0.0443 (7)
H5	0.2735	0.0767	0.9101	0.066*
O6	−0.0490 (4)	0.0881 (2)	0.4144 (4)	0.0503 (7)
H6A	−0.0971	0.0419	0.4346	0.076*
O7	0.2769 (6)	−0.03238 (19)	0.4196 (4)	0.0533 (8)
H7	0.2713	−0.0479	0.3171	0.080*
O8	0.3679 (5)	0.16640 (19)	0.2317 (4)	0.0470 (7)
O9	0.2908 (5)	0.0395 (2)	0.1220 (3)	0.0494 (8)
N1	0.6693 (4)	0.20164 (19)	1.0231 (4)	0.0285 (6)
C1	0.5207 (5)	0.3624 (2)	1.0542 (5)	0.0302 (7)
C2	0.6708 (6)	0.3287 (2)	1.1994 (5)	0.0387 (9)
H2A	0.5951	0.3054	1.2902	0.046*
H2B	0.7562	0.3743	1.2509	0.046*
C3	0.8082 (5)	0.2615 (3)	1.1353 (5)	0.0356 (8)
H3	0.8852	0.2319	1.2341	0.043*
C4	0.9545 (5)	0.2942 (3)	1.0073 (6)	0.0483 (10)
H4A	1.0871	0.2658	1.0263	0.058*
H4B	0.9771	0.3541	1.0230	0.058*
C5	0.8474 (6)	0.2756 (3)	0.8221 (6)	0.0437 (9)
H5A	0.8467	0.3249	0.7475	0.052*
H5B	0.9156	0.2299	0.7678	0.052*
C6	0.6273 (5)	0.2510 (2)	0.8544 (5)	0.0304 (7)
H6	0.5596	0.2165	0.7587	0.036*
C7	0.4975 (5)	0.3252 (2)	0.8921 (5)	0.0298 (7)
C8	0.3528 (5)	0.3622 (2)	0.7538 (5)	0.0304 (7)
C9	0.2115 (7)	0.3550 (3)	0.4589 (6)	0.0508 (11)
H9A	0.0828	0.3717	0.4985	0.076*
H9B	0.1856	0.3137	0.3677	0.076*
H9C	0.2774	0.4031	0.4139	0.076*
C10	0.7663 (6)	0.1188 (2)	0.9999 (5)	0.0390 (8)
H10A	0.6943	0.0908	0.9003	0.058*
H10B	0.7591	0.0854	1.1033	0.058*
H10C	0.9086	0.1267	0.9812	0.058*
C11	0.1363 (5)	0.0638 (2)	0.7001 (4)	0.0305 (7)
C12	0.1436 (5)	0.0981 (2)	0.5152 (4)	0.0334 (8)
H12	0.1752	0.1582	0.5240	0.040*
C13	0.3152 (5)	0.0546 (2)	0.4291 (4)	0.0327 (8)
H13	0.4475	0.0643	0.5010	0.039*
C14	0.3271 (5)	0.0916 (3)	0.2461 (4)	0.0321 (7)
H1	0.543 (4)	0.188 (2)	1.068 (5)	0.026 (9)*

	U11	U22	U33	U12	U13	U23
O1	0.0541 (15)	0.0441 (14)	0.0301 (14)	0.0102 (13)	0.0021 (11)	−0.0035 (13)
O2	0.0453 (13)	0.0446 (14)	0.0360 (15)	0.0180 (12)	−0.0015 (11)	0.0030 (13)
O3	0.0432 (13)	0.0527 (15)	0.0200 (13)	0.0097 (12)	−0.0066 (9)	0.0019 (12)
O4	0.0579 (15)	0.0664 (18)	0.0237 (13)	−0.0218 (15)	0.0089 (11)	−0.0036 (14)
O5	0.0545 (14)	0.0633 (16)	0.0141 (12)	−0.0159 (14)	0.0000 (10)	0.0055 (13)
O6	0.0430 (13)	0.079 (2)	0.0269 (14)	0.0105 (15)	−0.0062 (10)	0.0089 (15)
O7	0.089 (2)	0.0441 (15)	0.0291 (16)	0.0119 (16)	0.0166 (15)	0.0036 (13)
O8	0.0640 (17)	0.0522 (17)	0.0267 (15)	−0.0055 (14)	0.0139 (12)	0.0041 (13)
O9	0.0798 (19)	0.0564 (16)	0.0124 (12)	0.0012 (16)	0.0067 (12)	0.0005 (12)
N1	0.0293 (12)	0.0377 (15)	0.0176 (13)	−0.0008 (11)	−0.0007 (10)	0.0038 (12)
C1	0.0320 (15)	0.0308 (16)	0.0272 (19)	−0.0059 (14)	0.0012 (12)	0.0005 (14)
C2	0.0456 (18)	0.044 (2)	0.0238 (18)	−0.0020 (17)	−0.0083 (14)	−0.0023 (17)
C3	0.0320 (15)	0.0437 (18)	0.0277 (18)	−0.0068 (15)	−0.0114 (13)	0.0067 (16)
C4	0.0299 (17)	0.057 (2)	0.058 (3)	−0.0043 (18)	0.0027 (15)	0.007 (2)
C5	0.0405 (18)	0.048 (2)	0.045 (2)	0.0075 (16)	0.0155 (15)	0.0118 (19)
C6	0.0323 (15)	0.0375 (18)	0.0207 (17)	−0.0010 (14)	0.0000 (12)	0.0056 (14)
C7	0.0285 (14)	0.0363 (16)	0.0235 (17)	−0.0033 (13)	−0.0010 (11)	0.0032 (14)
C8	0.0294 (14)	0.0359 (17)	0.0255 (19)	−0.0012 (14)	0.0018 (13)	0.0058 (14)
C9	0.055 (2)	0.072 (3)	0.0219 (19)	0.016 (2)	−0.0107 (16)	0.007 (2)
C10	0.0442 (18)	0.0422 (19)	0.0292 (19)	0.0088 (16)	−0.0010 (14)	0.0049 (16)
C11	0.0374 (15)	0.0406 (17)	0.0138 (16)	−0.0002 (14)	0.0043 (11)	−0.0035 (15)
C12	0.0439 (17)	0.0420 (18)	0.0140 (16)	0.0032 (16)	0.0026 (13)	0.0020 (15)
C13	0.0422 (17)	0.0451 (19)	0.0103 (16)	0.0031 (15)	0.0000 (12)	0.0035 (14)
C14	0.0382 (16)	0.046 (2)	0.0118 (15)	0.0002 (15)	0.0041 (11)	0.0018 (15)

O1—C1	1.307 (5)	C3—C4	1.533 (6)
O1—H1A	0.8200	C3—H3	0.9800
O2—C8	1.215 (4)	C4—C5	1.537 (7)
O3—C8	1.328 (5)	C4—H4A	0.9700
O3—C9	1.448 (4)	C4—H4B	0.9700
O4—C11	1.188 (5)	C5—C6	1.531 (5)
O5—C11	1.309 (4)	C5—H5A	0.9700
O5—H5	0.8200	C5—H5B	0.9700
O6—C12	1.404 (4)	C6—C7	1.498 (5)
O6—H6A	0.8200	C6—H6	0.9800
O7—C13	1.407 (5)	C7—C8	1.459 (5)
O7—H7	0.8200	C9—H9A	0.9600
O8—C14	1.228 (5)	C9—H9B	0.9600
O9—C14	1.262 (5)	C9—H9C	0.9600
N1—C10	1.481 (5)	C10—H10A	0.9600
N1—C6	1.511 (4)	C10—H10B	0.9600
N1—C3	1.511 (4)	C10—H10C	0.9600
N1—H1	0.954 (19)	C11—C12	1.524 (4)
C1—C7	1.369 (5)	C12—C13	1.525 (5)
C1—C2	1.495 (5)	C12—H12	0.9800
C2—C3	1.511 (6)	C13—C14	1.531 (4)
C2—H2A	0.9700	C13—H13	0.9800
C2—H2B	0.9700
C1—O1—H1A	109.5	N1—C6—C5	100.9 (3)
C8—O3—C9	115.2 (3)	C7—C6—H6	111.8
C11—O5—H5	109.5	N1—C6—H6	111.8
C12—O6—H6A	109.5	C5—C6—H6	111.8
C13—O7—H7	109.5	C1—C7—C8	118.7 (3)
C10—N1—C6	113.5 (3)	C1—C7—C6	120.6 (3)
C10—N1—C3	113.2 (3)	C8—C7—C6	120.6 (3)
C6—N1—C3	101.4 (3)	O2—C8—O3	123.4 (3)
C10—N1—H1	103 (2)	O2—C8—C7	124.4 (3)
C6—N1—H1	111 (2)	O3—C8—C7	112.2 (3)
C3—N1—H1	115 (2)	O3—C9—H9A	109.5
O1—C1—C7	124.5 (3)	O3—C9—H9B	109.5
O1—C1—C2	114.5 (3)	H9A—C9—H9B	109.5
C7—C1—C2	121.0 (3)	O3—C9—H9C	109.5
C1—C2—C3	111.9 (3)	H9A—C9—H9C	109.5
C1—C2—H2A	109.2	H9B—C9—H9C	109.5
C3—C2—H2A	109.2	N1—C10—H10A	109.5
C1—C2—H2B	109.2	N1—C10—H10B	109.5
C3—C2—H2B	109.2	H10A—C10—H10B	109.5
H2A—C2—H2B	107.9	N1—C10—H10C	109.5
C2—C3—N1	107.1 (3)	H10A—C10—H10C	109.5
C2—C3—C4	113.6 (3)	H10B—C10—H10C	109.5
N1—C3—C4	103.0 (3)	O4—C11—O5	124.9 (3)
C2—C3—H3	111.0	O4—C11—C12	123.2 (3)
N1—C3—H3	111.0	O5—C11—C12	111.8 (3)
C4—C3—H3	111.0	O6—C12—C11	110.6 (3)
C3—C4—C5	106.0 (3)	O6—C12—C13	111.2 (3)
C3—C4—H4A	110.5	C11—C12—C13	110.0 (3)
C5—C4—H4A	110.5	O6—C12—H12	108.3
C3—C4—H4B	110.5	C11—C12—H12	108.3
C5—C4—H4B	110.5	C13—C12—H12	108.3
H4A—C4—H4B	108.7	O7—C13—C12	109.5 (3)
C6—C5—C4	103.5 (3)	O7—C13—C14	111.0 (3)
C6—C5—H5A	111.1	C12—C13—C14	109.7 (3)
C4—C5—H5A	111.1	O7—C13—H13	108.9
C6—C5—H5B	111.1	C12—C13—H13	108.9
C4—C5—H5B	111.1	C14—C13—H13	108.9
H5A—C5—H5B	109.0	O8—C14—O9	126.3 (3)
C7—C6—N1	107.2 (3)	O8—C14—C13	119.2 (3)
C7—C6—C5	112.8 (3)	O9—C14—C13	114.4 (3)
O1—C1—C2—C3	−172.8 (3)	C5—C6—C7—C1	−77.6 (4)
C7—C1—C2—C3	9.1 (5)	N1—C6—C7—C8	−151.1 (3)
C1—C2—C3—N1	−47.1 (4)	C5—C6—C7—C8	98.7 (4)
C1—C2—C3—C4	65.9 (4)	C9—O3—C8—O2	3.7 (5)
C10—N1—C3—C2	−160.7 (3)	C9—O3—C8—C7	−177.3 (3)
C6—N1—C3—C2	77.4 (3)	C1—C7—C8—O2	−0.7 (5)
C10—N1—C3—C4	79.3 (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—O3	3.9 (4)
N1—C3—C4—C5	18.7 (4)	O4—C11—C12—O6	23.5 (5)
C3—C4—C5—C6	11.9 (4)	O5—C11—C12—O6	−158.1 (3)
C10—N1—C6—C7	170.3 (3)	O4—C11—C12—C13	−99.7 (4)
C3—N1—C6—C7	−68.0 (3)	O5—C11—C12—C13	78.7 (4)
C10—N1—C6—C5	−71.4 (4)	O6—C12—C13—O7	−62.8 (4)
C3—N1—C6—C5	50.2 (3)	C11—C12—C13—O7	60.0 (4)
C4—C5—C6—C7	76.1 (4)	O6—C12—C13—C14	59.3 (4)
C4—C5—C6—N1	−37.9 (4)	C11—C12—C13—C14	−177.9 (3)
O1—C1—C7—C8	3.8 (5)	O7—C13—C14—O8	−177.1 (3)
C2—C1—C7—C8	−178.4 (3)	C12—C13—C14—O8	61.7 (4)
O1—C1—C7—C6	−179.8 (3)	O7—C13—C14—O9	3.4 (4)
C2—C1—C7—C6	−2.0 (5)	C12—C13—C14—O9	−117.8 (3)
N1—C6—C7—C1	32.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.82	1.89	2.600 (4)	145
O7—H7···O9	0.82	2.06	2.562 (4)	120
N1—H1···O8i	0.954 (19)	1.82 (2)	2.724 (4)	158 (4)
O6—H6A···O2ii	0.82	2.58	3.182 (4)	132
O5—H5···O9i	0.82	1.72	2.535 (4)	172

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.82	1.89	2.600 (4)	145
O7—H7⋯O9	0.82	2.06	2.562 (4)	120
N1—H1⋯O8i	0.954 (19)	1.82 (2)	2.724 (4)	158 (4)
O6—H6A⋯O2ii	0.82	2.58	3.182 (4)	132
O5—H5⋯O9i	0.82	1.72	2.535 (4)	172

Symmetry codes: (i) ; (ii) .