(2S,3S)-3-(4-Chloro-phen-yl)-8-methyl-tropane-2-carboxylic acid.

In the title compound, C(15)H(18)ClNO(2), the inter-nal torsion angles of the tropane ring are comparable to those of tropane rings in the crystal structures reported for cocaine and its derivatives. There is an intra-molecular hydrogen bond between the N atom in the tropane ring and the O atom of the carboxyl group. The crystal structure is further stabilized by many weak C-H⋯O inter-actions between the mol-ecules in the ab plane, forming a two-dimensional supra-molecular network.

Related literature

For general background, see: Clarke et al. (1973 ▶); Carroll et al. (1991 ▶, 2005 ▶). For related structures, see: Meltzer et al. (1997 ▶, 2001 ▶); Zhu et al. (1999 ▶). For related literature, see: Meegalla et al. (1997 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C15H18ClNO2

M = 279.75

Monoclinic,

a = 8.219 (6) Å

b = 6.501 (4) Å

c = 12.731 (8) Å

β = 100.692 (10)°

V = 668.4 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.28 mm−1

T = 293 (2) K

0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T min = 0.956, T max = 0.976

3374 measured reflections

2760 independent reflections

2264 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.125

S = 0.99

2760 reflections

177 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 1135 Friedel pairs

Flack parameter: −0.15 (9)

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808025002/fj2136sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808025002/fj2136Isup2.hkl

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

C15H18ClNO2	F000 = 296
Mr = 279.75	Dx = 1.390 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 742 reflections
a = 8.219 (6) Å	θ = 3.3–26.8º
b = 6.501 (4) Å	µ = 0.28 mm−1
c = 12.731 (8) Å	T = 293 (2) K
β = 100.692 (10)º	Block, white
V = 668.4 (8) Å3	0.20 × 0.10 × 0.10 mm
Z = 2

Bruker SMART APEX CCD diffractometer	2760 independent reflections
Radiation source: fine-focus sealed tube	2264 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.042
T = 293(2) K	θmax = 27.2º
φ and ω scans	θmin = 1.6º
Absorption correction: multi-scan(SADABS; Bruker, 2001)	h = −8→10
Tmin = 0.956, Tmax = 0.976	k = −8→8
3374 measured reflections	l = −16→13

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.052	w = 1/[σ2(Fo2) + (0.0695P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.125	(Δ/σ)max < 0.001
S = 0.99	Δρmax = 0.25 e Å−3
2760 reflections	Δρmin = −0.21 e Å−3
177 parameters	Extinction correction: none
2 restraints	Absolute structure: Flack (1983), 1135 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.15 (9)
Secondary atom site location: difference Fourier map

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) 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. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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.

	x	y	z	Uiso*/Ueq
Cl1	0.58072 (10)	0.59422 (16)	0.46455 (6)	0.0650 (3)
O1	0.9356 (2)	1.0348 (4)	0.03436 (15)	0.0508 (6)
O2	0.7924 (2)	1.2275 (4)	0.12844 (18)	0.0614 (6)
C1	0.9057 (3)	0.6847 (5)	0.2742 (2)	0.0414 (7)
H2	0.9376	0.6170	0.2169	0.050*
C2	0.7841 (3)	0.6008 (5)	0.3216 (2)	0.0439 (7)
H3	0.7354	0.4763	0.2972	0.053*
C3	0.7350 (3)	0.7004 (5)	0.4043 (2)	0.0433 (7)
C4	0.8053 (4)	0.8847 (5)	0.4423 (2)	0.0464 (7)
H4	0.7703	0.9523	0.4985	0.056*
C5	0.9290 (3)	0.9666 (5)	0.3950 (2)	0.0432 (7)
H5	0.9779	1.0902	0.4206	0.052*
C6	0.9824 (3)	0.8694 (4)	0.3104 (2)	0.0335 (6)
C7	1.1233 (3)	0.9616 (4)	0.2641 (2)	0.0350 (6)
H7	1.2084	0.9996	0.3256	0.042*
C8	1.0761 (3)	1.1622 (4)	0.2018 (2)	0.0333 (6)
H8	1.0536	1.2665	0.2528	0.040*
C9	1.2231 (3)	1.2388 (5)	0.1525 (2)	0.0361 (6)
H9	1.1976	1.3707	0.1159	0.043*
N10	1.2558 (3)	1.0745 (4)	0.07558 (17)	0.0362 (5)
H10X	1.157 (2)	1.032 (5)	0.045 (2)	0.039 (8)*
C11	1.3402 (4)	0.9115 (5)	0.1503 (2)	0.0463 (8)
H11	1.3969	0.8117	0.1121	0.056*
C12	1.2061 (4)	0.8080 (4)	0.1992 (2)	0.0413 (7)
H12A	1.2545	0.6967	0.2454	0.050*
H12B	1.1233	0.7497	0.1428	0.050*
C13	1.3871 (3)	1.2488 (5)	0.2315 (3)	0.0478 (8)
H13A	1.3688	1.2814	0.3027	0.057*
H13B	1.4592	1.3524	0.2099	0.057*
C14	1.4630 (3)	1.0344 (6)	0.2289 (2)	0.0532 (8)
H14A	1.5688	1.0420	0.2057	0.064*
H14B	1.4797	0.9717	0.2992	0.064*
C15	0.9197 (3)	1.1414 (4)	0.1143 (2)	0.0377 (6)
C16	1.3556 (4)	1.1475 (5)	−0.0028 (2)	0.0484 (8)
H16A	1.3583	1.0429	−0.0557	0.073*
H16B	1.4664	1.1766	0.0334	0.073*
H16C	1.3068	1.2702	−0.0369	0.073*

	U11	U22	U33	U12	U13	U23
Cl1	0.0584 (5)	0.0864 (7)	0.0526 (4)	−0.0214 (5)	0.0165 (4)	0.0042 (5)
O1	0.0448 (12)	0.0607 (15)	0.0420 (11)	−0.0054 (10)	−0.0048 (9)	−0.0107 (10)
O2	0.0358 (11)	0.0697 (15)	0.0758 (16)	0.0112 (11)	0.0029 (11)	−0.0032 (13)
C1	0.0427 (15)	0.0443 (18)	0.0368 (14)	−0.0029 (13)	0.0060 (12)	−0.0063 (12)
C2	0.0450 (15)	0.0397 (16)	0.0451 (15)	−0.0061 (14)	0.0033 (12)	−0.0024 (14)
C3	0.0341 (14)	0.059 (2)	0.0348 (14)	−0.0067 (13)	0.0003 (12)	0.0086 (14)
C4	0.0455 (17)	0.060 (2)	0.0342 (15)	−0.0006 (15)	0.0076 (12)	−0.0077 (14)
C5	0.0429 (16)	0.0426 (17)	0.0424 (15)	−0.0034 (13)	0.0036 (12)	−0.0102 (14)
C6	0.0327 (14)	0.0343 (15)	0.0311 (13)	0.0039 (11)	−0.0008 (11)	0.0017 (11)
C7	0.0349 (14)	0.0312 (14)	0.0366 (13)	0.0003 (11)	0.0008 (11)	−0.0014 (11)
C8	0.0336 (13)	0.0300 (14)	0.0352 (13)	−0.0006 (10)	0.0035 (11)	−0.0050 (11)
C9	0.0365 (14)	0.0340 (15)	0.0352 (14)	−0.0047 (12)	0.0001 (11)	−0.0025 (12)
N10	0.0327 (11)	0.0390 (13)	0.0359 (11)	−0.0026 (10)	0.0041 (9)	−0.0007 (10)
C11	0.0444 (17)	0.0428 (18)	0.0535 (18)	0.0140 (13)	0.0141 (14)	0.0073 (14)
C12	0.0468 (17)	0.0317 (15)	0.0478 (17)	0.0072 (12)	0.0152 (14)	0.0047 (12)
C13	0.0370 (16)	0.059 (2)	0.0447 (17)	−0.0138 (15)	0.0005 (13)	−0.0033 (15)
C14	0.0316 (14)	0.074 (2)	0.0516 (18)	0.0067 (15)	0.0024 (13)	0.0168 (16)
C15	0.0334 (14)	0.0333 (14)	0.0441 (15)	−0.0019 (11)	0.0012 (12)	0.0058 (12)
C16	0.0463 (16)	0.055 (2)	0.0462 (15)	−0.0037 (14)	0.0140 (13)	0.0037 (14)

Cl1—C3	1.742 (3)	C9—N10	1.506 (4)
O1—C15	1.258 (3)	C9—C13	1.526 (4)
O2—C15	1.229 (3)	C9—H9	0.9800
C1—C2	1.373 (4)	N10—C16	1.482 (3)
C1—C6	1.394 (4)	N10—C11	1.505 (4)
C1—H2	0.9300	N10—H10X	0.881 (17)
C2—C3	1.360 (4)	C11—C14	1.511 (5)
C2—H3	0.9300	C11—C12	1.520 (4)
C3—C4	1.378 (5)	C11—H11	0.9800
C4—C5	1.380 (4)	C12—H12A	0.9700
C4—H4	0.9300	C12—H12B	0.9700
C5—C6	1.388 (4)	C13—C14	1.530 (5)
C5—H5	0.9300	C13—H13A	0.9700
C6—C7	1.517 (4)	C13—H13B	0.9700
C7—C12	1.533 (4)	C14—H14A	0.9700
C7—C8	1.538 (4)	C14—H14B	0.9700
C7—H7	0.9800	C16—H16A	0.9599
C8—C15	1.542 (4)	C16—H16B	0.9599
C8—C9	1.544 (4)	C16—H16C	0.9599
C8—H8	0.9800
C2—C1—C6	121.2 (3)	C11—N10—C9	101.8 (2)
C2—C1—H2	119.4	C16—N10—H10X	112.8 (17)
C6—C1—H2	119.4	C11—N10—H10X	110 (2)
C3—C2—C1	119.7 (3)	C9—N10—H10X	104.4 (19)
C3—C2—H3	120.1	N10—C11—C14	102.7 (3)
C1—C2—H3	120.1	N10—C11—C12	106.7 (2)
C2—C3—C4	121.4 (3)	C14—C11—C12	114.1 (3)
C2—C3—Cl1	119.8 (2)	N10—C11—H11	111.0
C4—C3—Cl1	118.8 (2)	C14—C11—H11	111.0
C3—C4—C5	118.5 (3)	C12—C11—H11	111.0
C3—C4—H4	120.8	C11—C12—C7	111.1 (2)
C5—C4—H4	120.8	C11—C12—H12A	109.4
C4—C5—C6	121.8 (3)	C7—C12—H12A	109.4
C4—C5—H5	119.1	C11—C12—H12B	109.4
C6—C5—H5	119.1	C7—C12—H12B	109.4
C5—C6—C1	117.4 (3)	H12A—C12—H12B	108.0
C5—C6—C7	119.7 (2)	C9—C13—C14	105.1 (3)
C1—C6—C7	122.8 (2)	C9—C13—H13A	110.7
C6—C7—C12	113.6 (2)	C14—C13—H13A	110.7
C6—C7—C8	113.4 (2)	C9—C13—H13B	110.7
C12—C7—C8	111.7 (2)	C14—C13—H13B	110.7
C6—C7—H7	105.8	H13A—C13—H13B	108.8
C12—C7—H7	105.8	C11—C14—C13	105.7 (2)
C8—C7—H7	105.8	C11—C14—H14A	110.6
C7—C8—C15	113.2 (2)	C13—C14—H14A	110.6
C7—C8—C9	109.9 (2)	C11—C14—H14B	110.6
C15—C8—C9	110.2 (2)	C13—C14—H14B	110.6
C7—C8—H8	107.8	H14A—C14—H14B	108.7
C15—C8—H8	107.8	O2—C15—O1	126.1 (3)
C9—C8—H8	107.8	O2—C15—C8	118.2 (3)
N10—C9—C13	102.5 (2)	O1—C15—C8	115.7 (2)
N10—C9—C8	106.5 (2)	N10—C16—H16A	109.5
C13—C9—C8	114.1 (2)	N10—C16—H16B	109.5
N10—C9—H9	111.1	H16A—C16—H16B	109.5
C13—C9—H9	111.1	N10—C16—H16C	109.5
C8—C9—H9	111.1	H16A—C16—H16C	109.5
C16—N10—C11	113.8 (2)	H16B—C16—H16C	109.5
C16—N10—C9	113.5 (2)
C6—C1—C2—C3	1.0 (4)	C13—C9—N10—C16	−77.9 (3)
C1—C2—C3—C4	−0.2 (4)	C8—C9—N10—C16	162.0 (2)
C1—C2—C3—Cl1	−180.0 (2)	C13—C9—N10—C11	44.8 (3)
C2—C3—C4—C5	−0.6 (4)	C8—C9—N10—C11	−75.3 (2)
Cl1—C3—C4—C5	179.2 (2)	C16—N10—C11—C14	77.3 (3)
C3—C4—C5—C6	0.6 (5)	C9—N10—C11—C14	−45.3 (2)
C4—C5—C6—C1	0.2 (4)	C16—N10—C11—C12	−162.4 (2)
C4—C5—C6—C7	−177.7 (3)	C9—N10—C11—C12	75.1 (3)
C2—C1—C6—C5	−1.0 (4)	N10—C11—C12—C7	−62.0 (3)
C2—C1—C6—C7	176.8 (3)	C14—C11—C12—C7	50.7 (3)
C5—C6—C7—C12	160.8 (2)	C6—C7—C12—C11	177.2 (2)
C1—C6—C7—C12	−16.9 (4)	C8—C7—C12—C11	47.4 (3)
C5—C6—C7—C8	−70.3 (3)	N10—C9—C13—C14	−27.1 (3)
C1—C6—C7—C8	112.0 (3)	C8—C9—C13—C14	87.5 (3)
C6—C7—C8—C15	−53.2 (3)	N10—C11—C14—C13	28.0 (3)
C12—C7—C8—C15	76.6 (3)	C12—C11—C14—C13	−87.0 (3)
C6—C7—C8—C9	−177.0 (2)	C9—C13—C14—C11	−0.5 (3)
C12—C7—C8—C9	−47.1 (3)	C7—C8—C15—O2	109.1 (3)
C7—C8—C9—N10	62.1 (2)	C9—C8—C15—O2	−127.3 (3)
C15—C8—C9—N10	−63.3 (3)	C7—C8—C15—O1	−70.6 (3)
C7—C8—C9—C13	−50.1 (3)	C9—C8—C15—O1	53.0 (3)
C15—C8—C9—C13	−175.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N10—H10X···O1	0.881 (17)	1.80 (2)	2.599 (3)	150 (3)
C9—H9···O1i	0.98	2.28	3.148 (4)	146
C16—H16A···O2ii	0.96	2.48	3.282 (4)	141
C14—H14A···O2iii	0.97	2.54	3.439 (4)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N10—H10X⋯O1	0.881 (17)	1.80 (2)	2.599 (3)	150 (3)
C9—H9⋯O1i	0.98	2.28	3.148 (4)	146
C16—H16A⋯O2ii	0.96	2.48	3.282 (4)	141
C14—H14A⋯O2iii	0.97	2.54	3.439 (4)	154

Symmetry codes: (i) ; (ii) ; (iii) .