organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

(2SR,4aSR,8aSR)-6-Oxoperhydro­naphthalene-2-carboxylic acid

aCarl A. Olson Memorial Laboratories, Department of Chemistry, Rutgers University, Newark, NJ 07102, USA
*Correspondence e-mail: rogerlal@andromeda.rutgers.edu

(Received 12 November 2008; accepted 15 December 2008; online 20 December 2008)

In the title racemic compound, C11H16O3, the mol­ecule adopts a conformation that places its carboxyl group in an equatorial position. Mol­ecules aggregate by hydrogen-bond pairing of carboxyl groups, yielding centrosymmetric dimers that are arranged into layers in the (020) planes.

Related literature

For related structures, see: Efthimiopoulos et al. (2008[Efthimiopoulos, G., Lalancette, R. A. & Thompson, H. W. (2008). Acta Cryst. E64, o2292.]); Lalancette et al. (2007[Lalancette, R. A., Thompson, H. W., Kikolski, E. M. & Davison, M. (2007). Acta Cryst. E63, o1949-o1951.]). For other related literature, see: Borthwick (1980[Borthwick, P. W. (1980). Acta Cryst. B36, 628-632.]); Steiner (1997[Steiner, T. (1997). Chem. Commun. pp. 727-734.]).

[Scheme 1]

Experimental

Crystal data
  • C11H16O3

  • Mr = 196.24

  • Monoclinic, P 21 /n

  • a = 5.3568 (1) Å

  • b = 22.3758 (2) Å

  • c = 8.3376 (1) Å

  • β = 99.593 (1)°

  • V = 985.39 (2) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 0.78 mm−1

  • T = 100 (2) K

  • 0.24 × 0.20 × 0.08 mm

Data collection
  • Bruker SMART APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a[Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.]) Tmin = 0.836, Tmax = 0.941

  • 8305 measured reflections

  • 1675 independent reflections

  • 1578 reflections with I > 2σ(I)

  • Rint = 0.019

Refinement
  • R[F2 > 2σ(F2)] = 0.034

  • wR(F2) = 0.089

  • S = 1.05

  • 1675 reflections

  • 130 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.24 e Å−3

  • Δρmin = −0.18 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3⋯O2i 0.85 (2) 1.81 (2) 2.6555 (13) 177.4 (18)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2006[Bruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b[Sheldrick, G. M. (2008b). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

Our study of H-bonding modes in crystalline ketocarboxylic acids includes a variety of examples based on the naphthalene skeleton. Many of these are accessible from cyclohexanones via annulation reactions yielding enones, from which subsequent alkene reduction may then provide additional isoskeletal keto acids. The title racemate is the reduction product of an unsaturated keto acid whose structure we have previously reported (Efthimiopoulos et al., 2008), and we have also reported the structure of the isoskeletal trans isomer (Lalancette et al., 2007).

Fig. 1 shows the molecular structure and conformation. The unfavorable alternative conformer would place the carboxyl group at C2 not only on an axial bond, but inside the molecule's C-shaped curvature, while the observed conformer orients the carboxyl equatorially, with far less strain due to hindrance. This leaves as the only conformational option the rotational orientation of the carboxyl, which is turned so that the O2—C9—C2—C1 torsion angle is 31.57 (17) Å, presumably minimizing steric interactions with nearby H atoms at C1, C2 and C3. Although disorder-averaging of C—O bond lengths and C—C—O angles is common in carboxyl dimers, this is not observed in the current structure, where these values conform to ones typical for highly ordered cases (Borthwick, 1980).

Fig. 2 illustrates the packing of the chosen cell with centrosymmetrically hydrogen-bonded pairs of molecules; carboxyl dimers are centered at 1/2,1/2,1/2 and, in a second orientation, at 0,0,0. No intermolecular close contacts were found within the 2.6 Å range we standardly survey for C—H···O packing interactions (Steiner, 1997).

Related literature top

For related structures, see: Efthimiopoulos et al. (2008); Lalancette et al. (2007). For other related literature, see: Borthwick (1980); Steiner (1997).

Experimental top

The title compound was synthesized from the isoskeletal unsaturated keto acid we have previously reported (Efthimiopoulos et al., 2008), by room-temperature catalytic hydrogenation over 5% Pd/C in absolute EtOH at atmospheric pressure. This yielded the expected cis stereochemistry, and recrystallization from methyl pivalate gave material suitable for X-ray diffraction analysis (mp 399 K). The solid-state (KBr) infrared spectrum features a single broad peak at 1705 cm-1 for both C=O functions, typical of unstrained carboxyl-paired keto acids. In CHCl3 solution this combined absorption is seen at 1706 cm-1.

Refinement top

All H atoms were visible in Fourier difference maps. The position of the acid H was allowed to refine with its displacement parameter fixed at Uiso(H) = 1.5Ueq(O). The methylene and methine H atoms were placed in geometrically idealized positions and constrained to ride on their parent C atoms with C—H distances of 0.99 and 1.00 Å, respectively, and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008b); program(s) used to refine structure: SHELXTL (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top
[Figure 1] Fig. 1. Molecular structure showing displacement ellipsoids at the 40% probability level for non-H atoms.
[Figure 2] Fig. 2. Partial packing diagram illustrating the pairing of molecules into centrosymmetric dimers centered at 1/2,1/2,1/2 and 0,0,0. All carbon-bound H atoms are omitted and displacement ellipsoids are drawn at the 40% probability level for non-H atoms.
(2SR,4aSR,8aSR)-6-Oxoperhydronaphthalene-2-carboxylic acid top
Crystal data top
C11H16O3F(000) = 424
Mr = 196.24Dx = 1.323 Mg m3
Monoclinic, P21/nMelting point: 399 K
Hall symbol: -P 2ynCu Kα radiation, λ = 1.54178 Å
a = 5.3568 (1) ÅCell parameters from 6674 reflections
b = 22.3758 (2) Åθ = 4.0–66.9°
c = 8.3376 (1) ŵ = 0.78 mm1
β = 99.593 (1)°T = 100 K
V = 985.39 (2) Å3Plate, colourless
Z = 40.24 × 0.20 × 0.08 mm
Data collection top
Bruker SMART APEXII CCD
diffractometer
1675 independent reflections
Radiation source: fine-focus sealed tube1578 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ϕ and ω scansθmax = 67.1°, θmin = 4.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 56
Tmin = 0.836, Tmax = 0.941k = 2625
8305 measured reflectionsl = 99
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0431P)2 + 0.4735P]
where P = (Fo2 + 2Fc2)/3
1675 reflections(Δ/σ)max < 0.001
130 parametersΔρmax = 0.24 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C11H16O3V = 985.39 (2) Å3
Mr = 196.24Z = 4
Monoclinic, P21/nCu Kα radiation
a = 5.3568 (1) ŵ = 0.78 mm1
b = 22.3758 (2) ÅT = 100 K
c = 8.3376 (1) Å0.24 × 0.20 × 0.08 mm
β = 99.593 (1)°
Data collection top
Bruker SMART APEXII CCD
diffractometer
1675 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
1578 reflections with I > 2σ(I)
Tmin = 0.836, Tmax = 0.941Rint = 0.019
8305 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0340 restraints
wR(F2) = 0.089H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.24 e Å3
1675 reflectionsΔρmin = 0.18 e Å3
130 parameters
Special details top

Experimental. Crystal mounted on a Cryoloop using Paratone-N

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
xyzUiso*/Ueq
C11.0882 (2)0.57235 (6)0.84872 (15)0.0191 (3)
H1A1.14960.53050.85410.023*
H1B0.94630.57490.91080.023*
O11.1205 (2)0.70766 (5)1.31469 (12)0.0309 (3)
O20.62595 (18)0.52821 (4)0.67302 (11)0.0234 (3)
C20.9937 (2)0.58935 (6)0.67109 (15)0.0188 (3)
H21.13660.58440.60880.023*
O30.76368 (19)0.54230 (4)0.43725 (11)0.0234 (3)
H30.636 (4)0.5206 (8)0.403 (2)0.035*
C30.9059 (3)0.65526 (6)0.65699 (15)0.0204 (3)
H3A0.85450.66600.54100.024*
H3B0.75760.66060.71230.024*
C41.1206 (3)0.69626 (6)0.73474 (16)0.0214 (3)
H4A1.05820.73800.73070.026*
H4B1.26000.69430.67050.026*
C4A1.2244 (3)0.67983 (6)0.91180 (15)0.0199 (3)
H4A11.38010.70430.94680.024*
C51.0342 (3)0.69538 (6)1.02598 (16)0.0224 (3)
H5A1.00790.73921.02530.027*
H5B0.86940.67630.98420.027*
C61.1230 (3)0.67503 (6)1.19831 (16)0.0216 (3)
C71.2161 (3)0.61130 (6)1.21789 (16)0.0233 (3)
H7A1.07000.58371.19480.028*
H7B1.29910.60471.33180.028*
C81.4047 (3)0.59715 (6)1.10296 (16)0.0219 (3)
H8A1.56400.61931.13970.026*
H8B1.44430.55391.10910.026*
C8A1.3030 (2)0.61380 (6)0.92609 (15)0.0189 (3)
H8A11.44540.60860.86350.023*
C90.7790 (2)0.54990 (6)0.59572 (15)0.0182 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0197 (7)0.0186 (6)0.0189 (7)0.0004 (5)0.0027 (5)0.0005 (5)
O10.0357 (6)0.0353 (6)0.0219 (5)0.0016 (4)0.0059 (4)0.0084 (4)
O20.0235 (5)0.0279 (5)0.0191 (5)0.0076 (4)0.0046 (4)0.0034 (4)
C20.0176 (7)0.0214 (7)0.0174 (6)0.0011 (5)0.0036 (5)0.0015 (5)
O30.0223 (6)0.0310 (5)0.0162 (5)0.0079 (4)0.0015 (4)0.0029 (4)
C30.0218 (7)0.0214 (7)0.0174 (6)0.0004 (5)0.0020 (5)0.0021 (5)
C40.0243 (7)0.0196 (6)0.0202 (7)0.0021 (5)0.0035 (5)0.0015 (5)
C4A0.0197 (7)0.0209 (7)0.0188 (7)0.0042 (5)0.0028 (5)0.0003 (5)
C50.0237 (7)0.0215 (7)0.0215 (7)0.0015 (5)0.0030 (5)0.0022 (5)
C60.0162 (7)0.0288 (7)0.0206 (7)0.0034 (5)0.0053 (5)0.0034 (6)
C70.0241 (8)0.0281 (7)0.0174 (7)0.0009 (5)0.0028 (5)0.0015 (5)
C80.0195 (7)0.0249 (7)0.0206 (7)0.0004 (5)0.0011 (5)0.0000 (5)
C8A0.0160 (7)0.0226 (7)0.0185 (7)0.0001 (5)0.0036 (5)0.0004 (5)
C90.0193 (7)0.0168 (6)0.0181 (6)0.0034 (5)0.0023 (5)0.0001 (5)
Geometric parameters (Å, º) top
C1—C21.5311 (17)C4—H4B0.990
C1—C8A1.5336 (18)C4A—C8A1.5355 (18)
C1—H1A0.990C4A—C51.5454 (18)
C1—H1B0.990C4A—H4A11.000
O1—C61.2162 (16)C5—C61.5066 (18)
O2—C91.2245 (16)C5—H5A0.990
C2—C91.5020 (18)C5—H5B0.990
C2—C31.5464 (18)C6—C71.5107 (19)
C2—H21.000C7—C81.5365 (18)
O3—C91.3210 (15)C7—H7A0.990
O3—H30.85 (2)C7—H7B0.990
C3—C41.5286 (18)C8—C8A1.5305 (17)
C3—H3A0.990C8—H8A0.990
C3—H3B0.990C8—H8B0.990
C4—C4A1.5329 (18)C8A—H8A11.000
C4—H4A0.990
C2—C1—C8A111.14 (10)C6—C5—C4A112.57 (11)
C2—C1—H1A109.4C6—C5—H5A109.1
C8A—C1—H1A109.4C4A—C5—H5A109.1
C2—C1—H1B109.4C6—C5—H5B109.1
C8A—C1—H1B109.4C4A—C5—H5B109.1
H1A—C1—H1B108.0H5A—C5—H5B107.8
C9—C2—C1111.44 (10)O1—C6—C5122.40 (13)
C9—C2—C3109.07 (10)O1—C6—C7121.85 (12)
C1—C2—C3110.96 (10)C5—C6—C7115.74 (11)
C9—C2—H2108.4C6—C7—C8111.51 (11)
C1—C2—H2108.4C6—C7—H7A109.3
C3—C2—H2108.4C8—C7—H7A109.3
C9—O3—H3109.1 (12)C6—C7—H7B109.3
C4—C3—C2110.02 (11)C8—C7—H7B109.3
C4—C3—H3A109.7H7A—C7—H7B108.0
C2—C3—H3A109.7C8A—C8—C7112.66 (11)
C4—C3—H3B109.7C8A—C8—H8A109.1
C2—C3—H3B109.7C7—C8—H8A109.1
H3A—C3—H3B108.2C8A—C8—H8B109.1
C3—C4—C4A113.01 (11)C7—C8—H8B109.1
C3—C4—H4A109.0H8A—C8—H8B107.8
C4A—C4—H4A109.0C8—C8A—C1112.32 (11)
C3—C4—H4B109.0C8—C8A—C4A110.97 (10)
C4A—C4—H4B109.0C1—C8A—C4A111.87 (10)
H4A—C4—H4B107.8C8—C8A—H8A1107.1
C4—C4A—C8A110.87 (10)C1—C8A—H8A1107.1
C4—C4A—C5111.65 (11)C4A—C8A—H8A1107.1
C8A—C4A—C5111.66 (10)O2—C9—O3122.68 (12)
C4—C4A—H4A1107.5O2—C9—C2123.08 (11)
C8A—C4A—H4A1107.5O3—C9—C2114.19 (11)
C5—C4A—H4A1107.5
C8A—C1—C2—C9178.60 (10)C6—C7—C8—C8A51.60 (15)
C8A—C1—C2—C356.84 (14)C7—C8—C8A—C170.54 (14)
C9—C2—C3—C4179.35 (10)C7—C8—C8A—C4A55.51 (15)
C1—C2—C3—C456.23 (14)C2—C1—C8A—C8178.96 (11)
C2—C3—C4—C4A55.28 (14)C2—C1—C8A—C4A55.48 (14)
C3—C4—C4A—C8A53.90 (15)C4—C4A—C8A—C8179.55 (11)
C3—C4—C4A—C571.29 (14)C5—C4A—C8A—C854.37 (14)
C4—C4A—C5—C6175.30 (11)C4—C4A—C8A—C153.25 (14)
C8A—C4A—C5—C650.55 (15)C5—C4A—C8A—C171.94 (13)
C4A—C5—C6—O1131.55 (13)C1—C2—C9—O231.57 (17)
C4A—C5—C6—C748.38 (16)C3—C2—C9—O291.28 (14)
O1—C6—C7—C8131.49 (13)C1—C2—C9—O3150.80 (11)
C5—C6—C7—C848.44 (16)C3—C2—C9—O386.36 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.85 (2)1.81 (2)2.6555 (13)177.4 (18)
Symmetry code: (i) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formulaC11H16O3
Mr196.24
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)5.3568 (1), 22.3758 (2), 8.3376 (1)
β (°) 99.593 (1)
V3)985.39 (2)
Z4
Radiation typeCu Kα
µ (mm1)0.78
Crystal size (mm)0.24 × 0.20 × 0.08
Data collection
DiffractometerBruker SMART APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008a)
Tmin, Tmax0.836, 0.941
No. of measured, independent and
observed [I > 2σ(I)] reflections
8305, 1675, 1578
Rint0.019
(sin θ/λ)max1)0.598
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.089, 1.05
No. of reflections1675
No. of parameters130
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.18

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2005), SHELXTL (Sheldrick, 2008b).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.85 (2)1.81 (2)2.6555 (13)177.4 (18)
Symmetry code: (i) x+1, y+1, z+1.
 

Acknowledgements

HWT is grateful to Professor Gree Loober Spoog for helpful discussions. The authors acknowledge support in the form of NSF-CRIF grant No. 0443538.

References

First citationBorthwick, P. W. (1980). Acta Cryst. B36, 628–632.  CrossRef CAS IUCr Journals Web of Science Google Scholar
First citationBruker (2005). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBruker (2006). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationEfthimiopoulos, G., Lalancette, R. A. & Thompson, H. W. (2008). Acta Cryst. E64, o2292.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationLalancette, R. A., Thompson, H. W., Kikolski, E. M. & Davison, M. (2007). Acta Cryst. E63, o1949–o1951.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.  Google Scholar
First citationSheldrick, G. M. (2008b). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSteiner, T. (1997). Chem. Commun. pp. 727–734.  CrossRef Web of Science Google Scholar

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