1,2,3,4-Tetra­hydro-1,4-methano­naphthalene-2,3-diol

Xu, J.; Xu, H.; Quan, J.; Sha, F.; Yao, C.

doi:10.1107/S1600536808041068

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o79

doi:10.1107/S1600536808041068

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1,2,3,4-Tetrahydro-1,4-methanonaphthalene-2,3-diol

Jian Xu,^a Hao Xu,^a Ji-cai Quan,^a Fei Sha ^a and Cheng Yao ^a ^*

^aCollege of Science, Nanjing University of Technology, Xinmofan Road No. 5, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: yaocheng@njut.edu.cn

(Received 23 November 2008; accepted 5 December 2008; online 10 December 2008)

The title compound, C₁₁H₁₂O₂, is an intermediate in the synthesis of Varenicline, a nicotinic receptor partial agonist used to treat smoking addiction. In the crystal structure, there is an intramolecular O—H⋯O hydrogen bond that generates an S(5) ring motif. Intermolecular O—H⋯O hydrogen bonds form centrosymmetric dimers and also link these dimers into chains along the a axis.

Related literature

For background to the use of Varenicline to treat smoking addiction, see: Vetelino, (2004 ); Coe (2005 ). For details of graph-set analysis of hydrogen-bonding patterns, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₁H₁₂O₂
M_r = 176.21
Orthorhombic, P b c a
a = 10.240 (2) Å
b = 6.2370 (12) Å
c = 27.503 (6) Å
V = 1756.5 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 (2) K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.973, T_max = 0.991
1581 measured reflections
1581 independent reflections
1045 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.063
wR(F²) = 0.168
S = 1.03
1581 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2	0.85	2.16	2.578 (3)	110
O1—H1A⋯O2ⁱ	0.85	2.34	2.818 (3)	116
O2—H2A⋯O1ⁱⁱ	0.82	1.90	2.714 (3)	176
Symmetry codes: (i) -x+1, -y, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808041068/sj2556sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041068/sj2556Isup2.hkl

checkCIF report

Comment top

The title compound, I, is an important intermediate in the synthesis of Varenicline, a nicotinic receptor partial agonist used to treat smoking addiction (Vetelino, 2004). Varenicline came onto the market in 2006 and displays high affinity for neuronal nicotinic acetylcholine receptors (nAChRs), which mediate the dependence-producing effects of nicotine (Coe, 2005).

We report here the crystal structure of the title compound, (I), Fig. 1. The saturated six-membered C4,C5,C7···C10 ring of the anthracene group carries hydroxy substituents on C8 and C9 and is bridged by the C11 methylene group. In the crystal structure an intramolecular O1—H1A···O2 hydrogen bond generates an S5 ring motif (Bernstein et al., 1995). Intermolecular O1—H1A···O2 hydrogen bonds form centrosymmetric dimers and link these dimers into chains along the a axis, Table 2, Figure 2.

Related literature top

For background to the use of Varenicline to treat smoking addiction, see: Vetelino, (2004); Coe (2005). For details of graph-set analysis of hydrogen-bonding patterns, see: Bernstein et al. (1995).

Experimental top

1,4-Dihydro-1,4-methanonaphthalene (79.5 g, 560 mmol) in acetone (800 ml) and H₂O (100 ml) was stirred with N-methyl morpholine N-oxide (67.5 g, 576 mmol). OsO4 (15 ml of a 15 mol% t-BuOH solution, 1.48 mmol,0.26mol%) was added and the mixture was stirred vigorously. After 60 h, the solution was filtered, and the white solid product rinsed with acetone and air-dried (60.9 g). The mother liquor was partially concentrated to an oily solid which was triturated with acetone, filtered and rinsed with acetone to provide additional amounts of the title compound (27.4 g, total 88.3 g, 89%). An X-ray grade crystal of I was grown from acetone (10 ml) at room temperature.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and displacement ellipsoids at the 30% probability level.
	Fig. 2. Crystal packing of (I) viewed down the c axis with hydrogen bonds drawn as dashed lines.

1,2,3,4-Tetrahydro-1,4-methanonaphthalene-2,3-diol top

Crystal data top

C₁₁H₁₂O₂	F(000) = 752
M_r = 176.21	D_x = 1.333 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 10.240 (2) Å	θ = 10–13°
b = 6.2370 (12) Å	µ = 0.09 mm⁻¹
c = 27.503 (6) Å	T = 293 K
V = 1756.5 (6) Å³	White, colourless
Z = 8	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1045 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 25.2°, θ_min = 1.5°
ω/2θ scans	h = 0→12
Absorption correction: ψ scan (North et al., 1968)	k = 0→7
T_min = 0.973, T_max = 0.991	l = 0→32
1581 measured reflections	3 standard reflections every 200 reflections
1581 independent reflections	intensity decay: none

Refinement top

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.06P)² + 3P] where P = (F_o² + 2F_c²)/3
1581 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₁H₁₂O₂	V = 1756.5 (6) Å³
M_r = 176.21	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.240 (2) Å	µ = 0.09 mm⁻¹
b = 6.2370 (12) Å	T = 293 K
c = 27.503 (6) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1045 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.000
T_min = 0.973, T_max = 0.991	3 standard reflections every 200 reflections
1581 measured reflections	intensity decay: none
1581 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.063	0 restraints
wR(F²) = 0.168	H-atom parameters constrained
S = 1.03	Δρ_max = 0.24 e Å⁻³
1581 reflections	Δρ_min = −0.27 e Å⁻³
118 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
O1	0.65327 (18)	0.2295 (4)	0.51706 (7)	0.0289 (5)
H1A	0.6083	0.1798	0.4936	0.035*
C1	0.5544 (4)	0.5675 (6)	0.71478 (12)	0.0417 (9)
H1B	0.5950	0.6468	0.7391	0.050*
O2	0.40283 (18)	0.1947 (3)	0.51141 (7)	0.0287 (6)
H2A	0.3270	0.2214	0.5040	0.043*
C2	0.4181 (4)	0.5663 (6)	0.71136 (12)	0.0392 (9)
H2B	0.3686	0.6463	0.7332	0.047*
C3	0.3563 (3)	0.4465 (5)	0.67558 (11)	0.0333 (8)
H3A	0.2657	0.4456	0.6733	0.040*
C4	0.4303 (3)	0.3299 (5)	0.64387 (10)	0.0235 (7)
C5	0.5676 (3)	0.3324 (5)	0.64679 (10)	0.0258 (7)
C6	0.6296 (3)	0.4508 (6)	0.68204 (11)	0.0359 (8)
H6A	0.7203	0.4529	0.6840	0.043*
C7	0.3981 (3)	0.1886 (5)	0.60039 (10)	0.0260 (7)
H7A	0.3096	0.1286	0.6003	0.031*
C8	0.4366 (2)	0.3095 (5)	0.55428 (10)	0.0202 (6)
H8A	0.3991	0.4540	0.5540	0.024*
C9	0.5897 (2)	0.3180 (5)	0.55809 (10)	0.0214 (7)
H9A	0.6174	0.4673	0.5621	0.026*
C10	0.6168 (3)	0.1942 (5)	0.60542 (10)	0.0281 (8)
H10A	0.7059	0.1395	0.6091	0.034*
C11	0.5087 (3)	0.0226 (5)	0.60427 (11)	0.0313 (8)
H11A	0.5142	−0.0706	0.5761	0.038*
H11B	0.5046	−0.0617	0.6339	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0170 (9)	0.0410 (13)	0.0288 (11)	−0.0049 (10)	0.0050 (9)	−0.0077 (10)
C1	0.062 (2)	0.034 (2)	0.0297 (18)	−0.0094 (19)	−0.0103 (17)	−0.0012 (16)
O2	0.0185 (10)	0.0364 (13)	0.0311 (12)	0.0070 (10)	−0.0050 (9)	−0.0120 (10)
C2	0.056 (2)	0.034 (2)	0.0277 (18)	0.0070 (18)	0.0077 (16)	−0.0010 (15)
C3	0.0305 (17)	0.0378 (19)	0.0315 (17)	0.0057 (16)	0.0044 (14)	0.0014 (15)
C4	0.0233 (15)	0.0265 (17)	0.0206 (15)	0.0022 (13)	0.0038 (12)	0.0031 (13)
C5	0.0254 (15)	0.0266 (17)	0.0255 (16)	0.0016 (13)	−0.0039 (12)	0.0037 (13)
C6	0.0338 (18)	0.041 (2)	0.0324 (18)	−0.0073 (17)	−0.0066 (15)	0.0035 (16)
C7	0.0203 (14)	0.0264 (17)	0.0315 (17)	−0.0076 (13)	0.0012 (12)	−0.0020 (14)
C8	0.0156 (14)	0.0181 (15)	0.0270 (15)	0.0034 (12)	−0.0020 (12)	−0.0022 (13)
C9	0.0146 (13)	0.0233 (15)	0.0263 (15)	−0.0023 (12)	0.0022 (12)	−0.0024 (13)
C10	0.0200 (15)	0.0345 (19)	0.0297 (16)	0.0114 (14)	−0.0018 (12)	0.0050 (15)
C11	0.0453 (19)	0.0222 (16)	0.0265 (16)	0.0034 (15)	0.0021 (14)	0.0030 (14)

Geometric parameters (Å, º) top

O1—C9	1.415 (3)	C5—C10	1.513 (4)
O1—H1A	0.8501	C6—H6A	0.9300
C1—C6	1.390 (5)	C7—C8	1.527 (4)
C1—C2	1.399 (5)	C7—C11	1.538 (4)
C1—H1B	0.9300	C7—H7A	0.9800
O2—C8	1.422 (3)	C8—C9	1.572 (4)
O2—H2A	0.8200	C8—H8A	0.9800
C2—C3	1.388 (5)	C9—C10	1.539 (4)
C2—H2B	0.9300	C9—H9A	0.9800
C3—C4	1.365 (4)	C10—C11	1.540 (4)
C3—H3A	0.9300	C10—H10A	0.9800
C4—C5	1.408 (4)	C11—H11A	0.9700
C4—C7	1.522 (4)	C11—H11B	0.9700
C5—C6	1.374 (4)

C9—O1—H1A	119.8	C11—C7—H7A	115.1
C6—C1—C2	120.4 (3)	O2—C8—C7	112.1 (2)
C6—C1—H1B	119.8	O2—C8—C9	108.3 (2)
C2—C1—H1B	119.8	C7—C8—C9	102.6 (2)
C8—O2—H2A	109.5	O2—C8—H8A	111.1
C3—C2—C1	120.3 (3)	C7—C8—H8A	111.1
C3—C2—H2B	119.8	C9—C8—H8A	111.1
C1—C2—H2B	119.8	O1—C9—C10	113.4 (2)
C4—C3—C2	119.1 (3)	O1—C9—C8	113.1 (2)
C4—C3—H3A	120.4	C10—C9—C8	102.6 (2)
C2—C3—H3A	120.4	O1—C9—H9A	109.2
C3—C4—C5	120.8 (3)	C10—C9—H9A	109.2
C3—C4—C7	133.6 (3)	C8—C9—H9A	109.2
C5—C4—C7	105.5 (2)	C5—C10—C9	106.9 (2)
C6—C5—C4	120.5 (3)	C5—C10—C11	99.9 (2)
C6—C5—C10	133.1 (3)	C9—C10—C11	101.7 (2)
C4—C5—C10	106.4 (3)	C5—C10—H10A	115.5
C5—C6—C1	118.9 (3)	C9—C10—H10A	115.5
C5—C6—H6A	120.6	C11—C10—H10A	115.5
C1—C6—H6A	120.6	C7—C11—C10	93.6 (2)
C4—C7—C8	108.1 (2)	C7—C11—H11A	113.0
C4—C7—C11	100.1 (2)	C10—C11—H11A	113.0
C8—C7—C11	101.5 (2)	C7—C11—H11B	113.0
C4—C7—H7A	115.1	C10—C11—H11B	113.0
C8—C7—H7A	115.1	H11A—C11—H11B	110.4

C6—C1—C2—C3	0.8 (5)	C11—C7—C8—C9	−37.4 (3)
C1—C2—C3—C4	0.0 (5)	O2—C8—C9—O1	5.3 (3)
C2—C3—C4—C5	−0.7 (5)	C7—C8—C9—O1	124.1 (2)
C2—C3—C4—C7	−178.0 (3)	O2—C8—C9—C10	−117.2 (2)
C3—C4—C5—C6	0.7 (5)	C7—C8—C9—C10	1.5 (3)
C7—C4—C5—C6	178.6 (3)	C6—C5—C10—C9	−107.6 (4)
C3—C4—C5—C10	−177.9 (3)	C4—C5—C10—C9	70.6 (3)
C7—C4—C5—C10	0.1 (3)	C6—C5—C10—C11	146.8 (3)
C4—C5—C6—C1	0.2 (5)	C4—C5—C10—C11	−34.9 (3)
C10—C5—C6—C1	178.2 (3)	O1—C9—C10—C5	168.1 (2)
C2—C1—C6—C5	−0.9 (5)	C8—C9—C10—C5	−69.6 (3)
C3—C4—C7—C8	106.6 (4)	O1—C9—C10—C11	−87.6 (3)
C5—C4—C7—C8	−71.0 (3)	C8—C9—C10—C11	34.7 (3)
C3—C4—C7—C11	−147.6 (3)	C4—C7—C11—C10	−53.4 (2)
C5—C4—C7—C11	34.8 (3)	C8—C7—C11—C10	57.6 (2)
C4—C7—C8—O2	−176.5 (2)	C5—C10—C11—C7	53.4 (2)
C11—C7—C8—O2	78.7 (3)	C9—C10—C11—C7	−56.4 (2)
C4—C7—C8—C9	67.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.85	2.16	2.578 (3)	110
O1—H1A···O2ⁱ	0.85	2.34	2.818 (3)	116
O2—H2A···O1ⁱⁱ	0.82	1.90	2.714 (3)	176

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂O₂
M_r	176.21
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	10.240 (2), 6.2370 (12), 27.503 (6)
V (Å³)	1756.5 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.973, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	1581, 1581, 1045
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.063, 0.168, 1.03
No. of reflections	1581
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.27

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2	0.8500	2.1600	2.578 (3)	110.00
O1—H1A···O2ⁱ	0.8500	2.3400	2.818 (3)	116.00
O2—H2A···O1ⁱⁱ	0.8200	1.9000	2.714 (3)	176.00

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

Acknowledgements

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

References

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