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

Journal logoSTRUCTURAL
CHEMISTRY
ISSN: 2053-2296

The mol­ecular conformation of pentan-3-one studied in cholic acid pentan-3-one solvate

aInstitute of Inorganic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany
*Correspondence e-mail: ullrich.englert@ac.rwth-aachen.de

(Received 14 March 2011; accepted 4 May 2011; online 12 May 2011)

The crystal structure of cholic acid–pentan-3-one (1/1), C5H10O·C24H40O5, has been determined in order to deduce the mol­ecular conformation of the small volatile ketone. Data were collected at 100 K to a resolution of (sin θ)/λ = 0.91 Å−1. The structure contains a hydrogen-bonded cholic acid host network, forming only van der Waals inter­actions with the guest pentan-3-one mol­ecules. The ketone mol­ecules are disordered on general positions, with two clearly identifiable conformations. The majority conformer exhibits approximate C2 symmetry and is similar to that recently observed by microwave spectroscopy in the gas phase.

Comment

Many solvates of cholic acid have been studied, often with the focus on crystal engineering: Version 5.31 of the Cambridge Structural Database (CSD; Allen, 2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]) contains 247 error-free organic structures in which the steroid acts as a guest for small organic host mol­ecules. We have recently identified cocrystallization with cholic acid as an effective strategy to obtain high-resolution data sets on low-melting compounds, provided the intensity data collections are performed at reasonably low temperatures. Crystals obtained with the odorants allyl ­acetate and isopropyl ­acetate have been of sufficient quality even for charge-density studies (Mouhib et al., 2011[Mouhib, H., Jelisavac, D., Stahl, W., Wang, R., Kalf, I. & Englert, U. (2011). ChemPhysChem, 12, 761-764.]). We intended to obtain information about possible conformations of the small volatile mol­ecule pentan-3-one, also known as diethyl ­ketone, in the solid state. In view of its relatively low melting point of ca 233 K and our previous successful experiments, we decided to grow cocrystals with cholic acid and to study the crystal structure of the title cocrystal, (I)[link], at low temperature.

The structure of (I)[link] at room temperature has been reported previously (Caira et al., 1994a[Caira, M. R., Nassimbeni, L. R. & Scott, J. L. (1994a). J. Chem. Crystallogr. 24, 783-791.]). The compound crystallizes in the space group P21 with lattice parameters similar to those of related compounds (Caira et al., 1994b[Caira, M. R., Nassimbeni, L. R. & Scott, J. L. (1994b). J. Chem. Soc. Perkin Trans. 2, pp. 623-628.]). A displacement ellipsoid plot of the contents of the asymmetric unit is shown in Fig. 1[link]. Our redetermination fully confirms the conclusions of the earlier authors with respect to the host structure, but the previously published data cannot provide details about the conformation of the guest mol­ecule. In contrast, our intensity data collected at low temperature and up to high resolution

[Scheme 1]
allow us to compare the conformation of the ketone in the solid to that in the gas phase. Although single crystals of (I)[link] were well diffracting up to a resolution (sin θ)/λ = 0.91 Å−1, the resulting intensity data are not suitable for a charge-density study. After completion of the conventional refinement reported here, a difference Fourier synthesis shows local electron-density maxima centred on covalent bonds of the steroid host, in agreement with the expecta­tion and in favour of a potential charge-density study. In the neighbourhood of the guest mol­ecule, however, a less clear-cut and chemically not meaningful distribution is observed for the residual maxima, which precludes a more demanding inter­pretation of the electron density.

Classical O—H⋯O hydrogen bonds link the cholic acid mol­ecules into layers parallel to the (10[\overline{1}]) planes (Fig. 2[link] and Table 2[link]). Pairs of the host mol­ecules reside in a comparatively large cavity with a volume of 366 Å3 (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]). One of the ethyl substituents in the pentan-3-one mol­ecule is disordered over two conformations with a 0.545 (12):0.455 (12) ratio between the site occupancies. The majority conformation shown in Fig. 3[link](a) deviates only slightly from C2 symmetry, in good agreement with the experimental results for the gas-phase conformation obtained from Fourier transform microwave spectroscopy, and also with the expecta­tion from theory (Nguyen & Stahl, 2011[Nguyen, H. V. L. & Stahl, W. (2011). ChemPhysChem, doi:10.1002/cphc.201001021.]). The minority conformer (Fig. 3[link]b) is less symmetrical and belongs to point group C1. The only previous low-temperature crystal structure containing pentan-3-one (Goldup et al., 2008[Goldup, S. M., Leigh, D. A., Lusby, P. J., McBurney, R. T. & Slawin, A. M. Z. (2008). Angew. Chem. Int. Ed. 47, 3381-3384.]) shows an unexpected C—C—C bond angle of 141° in one of the ethyl substituents and therefore does not allow one to deduce the conformation of this mol­ecule reliably.

[Figure 1]
Figure 1
The mol­ecular structure of (I)[link], with displacement ellipsoids drawn at the 50% probability level. Atoms belonging to the minor conformer of pentan-3-one and all H atoms have been omitted for clarity.
[Figure 2]
Figure 2
Packing diagram of (I)[link], viewed along [010], showing the hydrogen-bonded layers of cholic acid host mol­ecules in black and the pentan-3-one guest mol­ecules in grey.
[Figure 3]
Figure 3
The mol­ecular conformations of pentan-3-one in (I)[link], showing (a) the major conformer, similar to the gas-phase structure, and (b) the minor conformer.

Experimental

Single crystals of (I)[link] were obtained by dissolving cholic acid (30 mg, 0.07 mmol) in pentan-3-one (10 ml) at 313 K. Slow evaporation over a period of ca 7 d at room temperature afforded colourless plates. The crystal fragment chosen for the diffraction experiment was cut to an appropriate size while covered with mother liquor and transferred directly to the stream of cold N2 (100 K) on the diffractometer.

Crystal data
  • C5H10O·C24H40O5

  • Mr = 494.69

  • Monoclinic, P 21

  • a = 12.5606 (7) Å

  • b = 8.0425 (5) Å

  • c = 13.9139 (8) Å

  • β = 102.002 (3)°

  • V = 1374.84 (14) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 100 K

  • 0.16 × 0.13 × 0.11 mm

Data collection
  • Bruker SMART APEX CCD diffractometer

  • 33615 measured reflections

  • 13745 independent reflections

  • 9042 reflections with I > 2σ(I)

  • Rint = 0.070

Refinement
  • R[F2 > 2σ(F2)] = 0.081

  • wR(F2) = 0.200

  • S = 1.06

  • 13745 reflections

  • 357 parameters

  • 26 restraints

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

  • Δρmax = 0.69 e Å−3

  • Δρmin = −0.44 e Å−3

Table 1
Selected geometric parameters (Å, °)

O1—C1 1.321 (2)
O2—C1 1.213 (2)
O3—C7 1.446 (2)
O4—C11 1.435 (2)
O5—C15 1.438 (2)
C1—C2 1.512 (3)
C2—C3 1.519 (3)
C3—C4 1.540 (3)
O6—C25 1.216 (4)
C25—C26 1.493 (5)
C25—C28A 1.507 (5)
C25—C28B 1.566 (7)
C26—C27 1.519 (5)
C28A—C29A 1.512 (10)
C28B—C29B 1.531 (12)
O6—C25—C26 123.0 (3)
O6—C25—C28A 124.6 (3)
C26—C25—C28A 111.2 (3)
O6—C25—C28B 111.1 (5)
C26—C25—C28B 122.8 (5)
C25—C26—C27 115.1 (2)
C25—C28A—C29A 113.1 (7)
C29B—C28B—C25 107.4 (8)
O6—C25—C26—C27 16.7 (5)
O6—C25—C28A—C29A 17.7 (9)
O6—C25—C28B—C29B −66.6 (12)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O1—H1⋯O4i 0.87 (3) 1.84 (3) 2.672 (2) 160 (4)
O3—H3⋯O2i 0.83 (2) 2.08 (2) 2.879 (2) 160 (2)
O4—H4⋯O5ii 0.86 (2) 1.81 (2) 2.6499 (19) 165 (2)
O5—H5⋯O3ii 0.82 (2) 2.10 (3) 2.869 (2) 157 (2)
Symmetry codes: (i) [-x+1, y+{\script{1\over 2}}, -z+2]; (ii) [-x, y-{\script{1\over 2}}, -z+1].

A total of 22 similarity restraints (C—C distances, C—C—C angles and displacement parameters for split positions) were used to model the disordered ethyl group of the solvent mol­ecule. Coordinates and isotropic displacement parameters were refined for H atoms attached to O atoms, with O—H distances restrained to 0.85 (2) Å. H atoms attached to C atoms were treated as riding, with C—H = 0.98 Å for CH3, C—H = 0.99 Å for CH2 and C—H = 1.00 Å for CH groups, and with Uiso(H) = 1.2 or 1.5Ueq(C). Methyl groups were allowed to rotate about their local threefold axes. In the absence of significant anomalous scattering effects, the Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) parameter is indeterminate. The absolute structure is assigned on the basis of the known configuration of the chiral cholic acid mol­ecule. Friedel pairs were not merged.

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1999[Bruker (1999). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

Many solvates of cholic acid have been studied, often with the focus on crystal engineering: Version 5.31 of the Cambridge Structural Database (CSD; Allen, 2002) contains 247 error-free organic structures in which the steroid acts as a guest for small organic host molecules. We have recently identified co-crystallization with cholic acid as an effective strategy to obtain high-resolution data sets on low-melting compounds, provided the intensity data collections are performed at reasonably low temperatures. Crystals obtained with the odorants allylacetate and isopropylacetate have been of sufficient quality even for charge-density studies (Mouhib et al., 2011). We intended to obtain information about possible conformations of the small volatile molecule pentan-3-one, also known as diethylketone, in the solid state. In view of its relatively low melting point of ca 233 K and our previous successful experiments, we decided to grow co-crystals with cholic acid and to study the crystal structure of the title compound, (I), at low temperature.

The structure of (I) at room temperature has been reported previously (Caira et al., 1994a). The compound crystallizes in space group P21 with lattice parameters similar to those of related compounds (Caira et al., 1994b). A displacement ellipsoid plot of the content of the asymmetric unit is shown in Fig. 1. Our redetermination fully confirms the conclusions of the earlier authors with respect to the host structure, but the previously published data cannot provide details about the conformation of the guest molecule. In contrast, our intensity data collected at low temperature and up to high resolution allow us to compare the conformation of the ketone in the solid to that in the gas phase. Although single crystals of (I) were well diffracting up to a resolution (sinθ)/λ = 0.91 Å-1, the resulting intensity data are not suitable for a charge-density study. After completion of the conventional refinement reported here, a difference Fourier synthesis shows local electron-density maxima centred on covalent bonds of the steroid host, in agreement with the expectation and in favour of a potential charge-density study. In the neighbourhood of the guest molecule, however, a less clear-cut and chemically not meaningful distribution is observed for the residual maxima, which precludes a more demanding interpretation of the electron density.

Classical O—H···O hydrogen bonds link the cholic acid molecules into layers parallel to the (1 0 1) planes (Fig. 2, Table 2). Pairs of the host molecules reside in a comparatively large cavity with a volume of 366 Å3 (Spek, 2009). One of the ethyl substituents in the pentan-3-one molecule is disordered over two conformations with a 0.545 (12): 0.455 (12) ratio between the site occupancies. The majority conformation shown in Fig. 3(a) deviates only slightly from C2 symmetry, in good agreement with the experimental results for the gas-phase conformation obtained from Fourier transform microwave spectroscopy, and also with the expectation from theory (Nguyen & Stahl, 2011). The minority conformer (Fig. 3b) is less symmetrical and belongs to point group C1. The only previous low-temperature crystal structure containing pentan-3-one (Goldup et al., 2008) shows an unexpected C—C—C bond angle of 141° in one of the ethyl substituents and therefore does not allow one to deduce the conformation of this molecule reliably.

Related literature top

For related literature, see: Allen (2002); Caira et al. (1994a, 1994b); Goldup et al. (2008); Mouhib et al. (2011); Nguyen & Stahl (2011); Spek (2009).

Experimental top

Single crystals of (I) were obtained by dissolving cholic acid (30 mg, 0.07 mmol) in pentan-3-one (10 ml) at 313 K. Slow evaporation over ca 7 d at room temperature afforded colourless plates. The crystal fragment chosen for the diffraction experiment was cut to an appropriate size while covered with mother liquor and transferred directly to the stream of cold N2 (100 K) on the diffractometer.

Refinement top

A total of 22 similarity restraints (C—C distances, C—C—C angles, displacement parameters for split positions) were used to model the disordered solvent molecule. Coordinates and isotropic displacement parameters were refined for H atoms attached to O, with O—H distances restrained to 0.85 (2) Å. H atoms attached to C were treated as riding with C—H = 0.98 Å for CH3, C—H = 0.99 Å for CH2 and C—H = 1.00 Å for CH groups, and with Uiso(H) = 1.2 or 1.5Ueq(C). Methyl groups were allowed to rotate about their local threefold axes. In the absence of significant anomalous scattering effects, the Flack parameter is indeterminate. The absolute structure is assigned on the basis of the known configuration of the chiral cholic acid molecule. Friedel pairs were not merged.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level. Atoms belonging to the minor conformer of pentan-3-one and all H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Packing diagram of (I), viewed along [010], showing the hydrogen-bonded layers of cholic acid host molecules in black and the pentan-3-one guest molecules in grey.
[Figure 3] Fig. 3. The molecular conformations of pentan-3-one in (I): (a) the major conformer, similar to the gas-phase structure, and (b) the minor conformer.
cholic acid–pentan-3-one (1/1) top
Crystal data top
C5H10O·C24H40O5F(000) = 544
Mr = 494.69Dx = 1.195 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 4097 reflections
a = 12.5606 (7) Åθ = 2.5–29.1°
b = 8.0425 (5) ŵ = 0.08 mm1
c = 13.9139 (8) ÅT = 100 K
β = 102.002 (3)°Fragment, colourless
V = 1374.84 (14) Å30.16 × 0.13 × 0.11 mm
Z = 2
Data collection top
Bruker SMART APEX CCD
diffractometer
9042 reflections with I > 2σ(I)
Radiation source: Incoatec microsourceRint = 0.070
Multilayer optics monochromatorθmax = 40.4°, θmin = 1.7°
ω scansh = 2214
33615 measured reflectionsk = 1414
13745 independent reflectionsl = 1424
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)] = 0.081Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.200H atoms treated by a mixture of independent and constrained refinement
S = 1.06 w = 1/[σ2(Fo2) + (0.085P)2 + 0.250P]
where P = (Fo2 + 2Fc2)/3
13745 reflections(Δ/σ)max = 0.002
357 parametersΔρmax = 0.69 e Å3
26 restraintsΔρmin = 0.44 e Å3
Crystal data top
C5H10O·C24H40O5V = 1374.84 (14) Å3
Mr = 494.69Z = 2
Monoclinic, P21Mo Kα radiation
a = 12.5606 (7) ŵ = 0.08 mm1
b = 8.0425 (5) ÅT = 100 K
c = 13.9139 (8) Å0.16 × 0.13 × 0.11 mm
β = 102.002 (3)°
Data collection top
Bruker SMART APEX CCD
diffractometer
9042 reflections with I > 2σ(I)
33615 measured reflectionsRint = 0.070
13745 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.08126 restraints
wR(F2) = 0.200H atoms treated by a mixture of independent and constrained refinement
S = 1.06Δρmax = 0.69 e Å3
13745 reflectionsΔρmin = 0.44 e Å3
357 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
xyzUiso*/UeqOcc. (<1)
O10.69836 (14)0.71124 (18)1.27098 (11)0.0233 (3)
H10.762 (2)0.670 (5)1.270 (3)0.058 (11)*
O20.66149 (14)0.46199 (19)1.20162 (12)0.0265 (3)
O30.19334 (13)0.68117 (17)0.77718 (10)0.0187 (3)
H30.2435 (18)0.749 (3)0.7951 (19)0.020 (6)*
O40.08920 (12)0.14850 (16)0.70817 (10)0.0183 (3)
H40.086 (2)0.052 (2)0.682 (2)0.028 (7)*
O50.09985 (14)0.37263 (17)0.39354 (10)0.0210 (3)
H50.131 (2)0.300 (3)0.3570 (19)0.028 (7)*
C10.63263 (18)0.6008 (2)1.21892 (14)0.0198 (4)
C20.51952 (19)0.6700 (3)1.18229 (16)0.0269 (4)
H2A0.52500.78891.16550.032*
H2B0.47820.66271.23550.032*
C30.45794 (18)0.5775 (3)1.09263 (15)0.0205 (4)
H3A0.45950.45721.10790.025*
H3B0.49660.59351.03820.025*
C40.33861 (16)0.6315 (2)1.05719 (13)0.0168 (3)
H4A0.30000.61631.11260.020*
C50.28543 (17)0.5161 (2)0.97245 (13)0.0161 (3)
H5A0.32620.53020.91840.019*
C60.16201 (16)0.5336 (2)0.92592 (13)0.0145 (3)
C70.12530 (16)0.6728 (2)0.84903 (13)0.0153 (3)
H70.12940.78190.88410.018*
C80.00800 (16)0.6458 (2)0.79326 (13)0.0162 (3)
H8A0.00990.73240.74180.019*
H8B0.04120.66180.83960.019*
C90.01560 (16)0.4732 (2)0.74399 (13)0.0140 (3)
H90.02750.46590.69130.017*
C100.02636 (17)0.3340 (2)0.81938 (13)0.0158 (3)
H100.01880.33690.87070.019*
C110.01322 (17)0.1614 (2)0.77187 (13)0.0166 (3)
H110.03270.07620.82500.020*
C120.10390 (18)0.1316 (2)0.71865 (14)0.0193 (4)
H12A0.14980.11990.76810.023*
H12B0.10740.02520.68230.023*
C130.15184 (16)0.2700 (2)0.64605 (13)0.0160 (3)
H130.23200.24940.62690.019*
C140.10709 (17)0.2569 (2)0.55196 (13)0.0168 (3)
H14A0.02690.26800.56920.020*
H14B0.12420.14520.52300.020*
C150.15237 (17)0.3868 (2)0.47568 (13)0.0171 (3)
H150.23260.37040.45300.021*
C160.12999 (17)0.5590 (2)0.52070 (14)0.0179 (3)
H16A0.16200.64440.47200.022*
H16B0.05050.57810.53880.022*
C170.17912 (17)0.5745 (2)0.61221 (14)0.0183 (3)
H17A0.25910.56320.59210.022*
H17B0.16360.68750.63990.022*
C180.13689 (16)0.4454 (2)0.69420 (13)0.0157 (3)
C190.21174 (18)0.4604 (3)0.76871 (15)0.0227 (4)
H19A0.18420.38900.82550.034*
H19B0.28560.42570.73750.034*
H19C0.21300.57620.79050.034*
C200.14312 (16)0.3667 (2)0.87001 (13)0.0149 (3)
H200.18660.37070.81750.018*
C210.19700 (18)0.2374 (2)0.94500 (14)0.0193 (4)
H21A0.21980.13850.91190.023*
H21B0.14700.20170.98750.023*
C220.29609 (18)0.3295 (2)1.00487 (15)0.0205 (4)
H22A0.36430.28140.99180.025*
H22B0.29730.31971.07600.025*
C230.09651 (17)0.5475 (2)1.00720 (14)0.0182 (4)
H23A0.12230.46381.05790.027*
H23B0.01920.52870.97910.027*
H23C0.10620.65871.03650.027*
C240.33062 (19)0.8150 (2)1.02697 (15)0.0221 (4)
H24A0.36630.83170.97140.033*
H24B0.36660.88371.08250.033*
H24C0.25390.84711.00770.033*
O60.46564 (18)0.0848 (3)0.38832 (16)0.0496 (6)
C250.5509 (2)0.0080 (5)0.4042 (2)0.0446 (7)
C260.5881 (2)0.0944 (3)0.3280 (3)0.0416 (7)
H26A0.64700.03370.30550.050*
H26B0.61960.19920.35890.050*
C270.5002 (2)0.1373 (4)0.2388 (2)0.0431 (7)
H27A0.46470.03500.21020.065*
H27B0.53310.19440.19000.065*
H27C0.44610.21010.25880.065*
C28A0.6190 (5)0.0254 (8)0.5050 (3)0.0383 (15)0.544 (12)
H28A0.60830.14240.52300.046*0.544 (12)
H28B0.69680.01100.50290.046*0.544 (12)
C29A0.5915 (13)0.0875 (14)0.5832 (8)0.047 (2)0.544 (12)
H29A0.51610.06820.58900.070*0.544 (12)
H29B0.64050.06390.64630.070*0.544 (12)
H29C0.60010.20370.56500.070*0.544 (12)
C28B0.6306 (7)0.0765 (15)0.4975 (6)0.062 (2)0.456 (12)
H28C0.64040.19790.49150.075*0.456 (12)
H28D0.70260.02220.50510.075*0.456 (12)
C29B0.5804 (18)0.038 (2)0.5864 (10)0.062 (3)0.456 (12)
H29D0.54870.07350.57960.093*0.456 (12)
H29E0.63700.04400.64660.093*0.456 (12)
H29F0.52350.12000.58990.093*0.456 (12)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0219 (9)0.0233 (6)0.0229 (7)0.0010 (6)0.0007 (6)0.0021 (5)
O20.0246 (9)0.0228 (6)0.0288 (8)0.0018 (6)0.0024 (6)0.0033 (6)
O30.0204 (8)0.0212 (6)0.0143 (6)0.0028 (5)0.0033 (5)0.0012 (5)
O40.0217 (8)0.0167 (5)0.0160 (6)0.0024 (5)0.0029 (5)0.0039 (5)
O50.0325 (9)0.0191 (6)0.0113 (5)0.0044 (6)0.0046 (5)0.0006 (5)
C10.0210 (10)0.0230 (8)0.0138 (7)0.0014 (7)0.0006 (7)0.0011 (6)
C20.0228 (12)0.0302 (10)0.0247 (10)0.0051 (8)0.0019 (8)0.0086 (8)
C30.0182 (10)0.0230 (8)0.0183 (8)0.0025 (7)0.0008 (7)0.0030 (6)
C40.0161 (9)0.0209 (7)0.0125 (7)0.0010 (6)0.0011 (6)0.0009 (6)
C50.0164 (10)0.0184 (7)0.0127 (7)0.0020 (6)0.0012 (6)0.0022 (6)
C60.0166 (9)0.0144 (6)0.0118 (7)0.0031 (6)0.0019 (6)0.0014 (5)
C70.0194 (10)0.0138 (6)0.0123 (7)0.0019 (6)0.0022 (6)0.0009 (5)
C80.0188 (10)0.0159 (6)0.0132 (7)0.0026 (6)0.0016 (6)0.0001 (6)
C90.0152 (9)0.0153 (6)0.0117 (7)0.0017 (6)0.0030 (6)0.0015 (5)
C100.0206 (10)0.0158 (6)0.0117 (7)0.0029 (6)0.0048 (6)0.0016 (5)
C110.0229 (10)0.0146 (6)0.0119 (7)0.0022 (6)0.0027 (6)0.0019 (5)
C120.0253 (11)0.0175 (7)0.0155 (8)0.0039 (7)0.0048 (7)0.0022 (6)
C130.0144 (9)0.0183 (7)0.0149 (7)0.0040 (6)0.0026 (6)0.0013 (6)
C140.0205 (10)0.0158 (6)0.0136 (7)0.0007 (6)0.0025 (7)0.0005 (6)
C150.0198 (10)0.0177 (7)0.0124 (7)0.0017 (6)0.0001 (6)0.0012 (6)
C160.0200 (10)0.0163 (7)0.0160 (8)0.0001 (6)0.0004 (7)0.0017 (6)
C170.0158 (10)0.0197 (7)0.0181 (8)0.0023 (7)0.0007 (7)0.0004 (6)
C180.0146 (9)0.0182 (7)0.0141 (7)0.0001 (6)0.0024 (6)0.0015 (6)
C190.0187 (11)0.0293 (9)0.0210 (9)0.0009 (8)0.0064 (8)0.0006 (7)
C200.0201 (10)0.0131 (6)0.0113 (7)0.0029 (6)0.0025 (6)0.0003 (5)
C210.0242 (11)0.0148 (7)0.0161 (8)0.0032 (7)0.0019 (7)0.0010 (6)
C220.0212 (11)0.0161 (7)0.0209 (9)0.0034 (7)0.0030 (7)0.0004 (6)
C230.0215 (10)0.0206 (7)0.0128 (7)0.0030 (7)0.0039 (7)0.0030 (6)
C240.0264 (11)0.0206 (8)0.0176 (8)0.0010 (7)0.0007 (8)0.0007 (6)
O60.0309 (12)0.0763 (16)0.0382 (11)0.0096 (11)0.0003 (9)0.0100 (10)
C250.0201 (14)0.076 (2)0.0350 (13)0.0049 (13)0.0010 (10)0.0122 (13)
C260.0292 (15)0.0341 (12)0.0613 (18)0.0059 (10)0.0088 (13)0.0112 (12)
C270.0371 (17)0.0327 (12)0.0599 (18)0.0066 (11)0.0110 (14)0.0003 (12)
C28A0.035 (3)0.041 (3)0.032 (2)0.010 (2)0.0076 (19)0.002 (2)
C29A0.044 (4)0.052 (5)0.038 (3)0.010 (4)0.003 (3)0.016 (3)
C28B0.040 (4)0.070 (6)0.067 (4)0.012 (4)0.014 (3)0.008 (4)
C29B0.064 (7)0.076 (9)0.040 (4)0.000 (7)0.004 (4)0.023 (5)
Geometric parameters (Å, º) top
O1—C11.321 (2)C15—C161.522 (2)
O1—H10.863 (18)C15—H151.00
O2—C11.213 (2)C16—C171.531 (3)
O3—C71.446 (2)C16—H16A0.99
O3—H30.829 (17)C16—H16B0.99
O4—C111.435 (2)C17—C181.552 (3)
O4—H40.853 (17)C17—H17A0.99
O5—C151.438 (2)C17—H17B0.99
O5—H50.819 (17)C18—C191.542 (3)
C1—C21.512 (3)C19—H19A0.98
C2—C31.519 (3)C19—H19B0.98
C2—H2A0.99C19—H19C0.98
C2—H2B0.99C20—C211.528 (2)
C3—C41.540 (3)C20—H201.00
C3—H3A0.99C21—C221.536 (3)
C3—H3B0.99C21—H21A0.99
C4—C241.533 (3)C21—H21B0.99
C4—C51.539 (3)C22—H22A0.99
C4—H4A1.00C22—H22B0.99
C5—C61.557 (3)C23—H23A0.98
C5—C221.565 (3)C23—H23B0.98
C5—H5A1.00C23—H23C0.98
C6—C231.535 (3)C24—H24A0.98
C6—C201.545 (2)C24—H24B0.98
C6—C71.551 (2)C24—H24C0.98
C7—C81.531 (3)O6—C251.216 (4)
C7—H71.00C25—C261.493 (5)
C8—C91.549 (2)C25—C28A1.507 (5)
C8—H8A0.99C25—C28B1.566 (7)
C8—H8B0.99C26—C271.519 (5)
C9—C101.549 (2)C26—H26A0.99
C9—C181.553 (3)C26—H26B0.99
C9—H91.00C27—H27A0.98
C10—C201.512 (3)C27—H27B0.98
C10—C111.532 (2)C27—H27C0.98
C10—H101.00C28A—C29A1.512 (10)
C11—C121.522 (3)C28A—H28A0.99
C11—H111.00C28A—H28B0.99
C12—C131.539 (3)C29A—H29A0.98
C12—H12A0.99C29A—H29B0.98
C12—H12B0.99C29A—H29C0.98
C13—C141.532 (3)C28B—C29B1.531 (12)
C13—C181.556 (3)C28B—H28C0.99
C13—H131.00C28B—H28D0.99
C14—C151.513 (3)C29B—H29D0.98
C14—H14A0.99C29B—H29E0.98
C14—H14B0.99C29B—H29F0.98
C1—O1—H1102 (3)C16—C15—H15109.7
C7—O3—H3110.1 (18)C15—C16—C17110.16 (15)
C11—O4—H4110 (2)C15—C16—H16A109.6
C15—O5—H5108 (2)C17—C16—H16A109.6
O2—C1—O1123.3 (2)C15—C16—H16B109.6
O2—C1—C2124.76 (19)C17—C16—H16B109.6
O1—C1—C2111.94 (17)H16A—C16—H16B108.1
C1—C2—C3112.27 (17)C16—C17—C18114.91 (15)
C1—C2—H2A109.2C16—C17—H17A108.5
C3—C2—H2A109.2C18—C17—H17A108.5
C1—C2—H2B109.2C16—C17—H17B108.5
C3—C2—H2B109.2C18—C17—H17B108.5
H2A—C2—H2B107.9H17A—C17—H17B107.5
C2—C3—C4114.88 (16)C19—C18—C17106.18 (15)
C2—C3—H3A108.5C19—C18—C9111.55 (15)
C4—C3—H3A108.5C17—C18—C9112.66 (15)
C2—C3—H3B108.5C19—C18—C13108.94 (15)
C4—C3—H3B108.5C17—C18—C13107.34 (15)
H3A—C3—H3B107.5C9—C18—C13109.99 (15)
C24—C4—C5112.17 (15)C18—C19—H19A109.5
C24—C4—C3111.29 (17)C18—C19—H19B109.5
C5—C4—C3108.30 (15)H19A—C19—H19B109.5
C24—C4—H4A108.3C18—C19—H19C109.5
C5—C4—H4A108.3H19A—C19—H19C109.5
C3—C4—H4A108.3H19B—C19—H19C109.5
C4—C5—C6120.00 (15)C10—C20—C21116.68 (15)
C4—C5—C22111.09 (15)C10—C20—C6114.70 (15)
C6—C5—C22102.97 (15)C21—C20—C6104.34 (14)
C4—C5—H5A107.4C10—C20—H20106.8
C6—C5—H5A107.4C21—C20—H20106.8
C22—C5—H5A107.4C6—C20—H20106.8
C23—C6—C20112.62 (15)C20—C21—C22103.65 (15)
C23—C6—C7109.12 (14)C20—C21—H21A111.0
C20—C6—C7106.72 (14)C22—C21—H21A111.0
C23—C6—C5109.88 (15)C20—C21—H21B111.0
C20—C6—C599.58 (14)C22—C21—H21B111.0
C7—C6—C5118.64 (15)H21A—C21—H21B109.0
O3—C7—C8107.52 (14)C21—C22—C5107.16 (15)
O3—C7—C6112.12 (14)C21—C22—H22A110.3
C8—C7—C6111.33 (15)C5—C22—H22A110.3
O3—C7—H7108.6C21—C22—H22B110.3
C8—C7—H7108.6C5—C22—H22B110.3
C6—C7—H7108.6H22A—C22—H22B108.5
C7—C8—C9115.26 (15)C6—C23—H23A109.5
C7—C8—H8A108.5C6—C23—H23B109.5
C9—C8—H8A108.5H23A—C23—H23B109.5
C7—C8—H8B108.5C6—C23—H23C109.5
C9—C8—H8B108.5H23A—C23—H23C109.5
H8A—C8—H8B107.5H23B—C23—H23C109.5
C8—C9—C10109.93 (14)C4—C24—H24A109.5
C8—C9—C18113.95 (15)C4—C24—H24B109.5
C10—C9—C18111.23 (14)H24A—C24—H24B109.5
C8—C9—H9107.1C4—C24—H24C109.5
C10—C9—H9107.1H24A—C24—H24C109.5
C18—C9—H9107.1H24B—C24—H24C109.5
C20—C10—C11111.43 (15)O6—C25—C26123.0 (3)
C20—C10—C9110.51 (14)O6—C25—C28A124.6 (3)
C11—C10—C9111.81 (14)C26—C25—C28A111.2 (3)
C20—C10—H10107.6O6—C25—C28B111.1 (5)
C11—C10—H10107.6C26—C25—C28B122.8 (5)
C9—C10—H10107.6C25—C26—C27115.1 (2)
O4—C11—C12112.81 (15)C25—C26—H26A108.5
O4—C11—C10107.84 (15)C27—C26—H26A108.5
C12—C11—C10111.06 (16)C25—C26—H26B108.5
O4—C11—H11108.3C27—C26—H26B108.5
C12—C11—H11108.3H26A—C26—H26B107.5
C10—C11—H11108.3C26—C27—H27A109.5
C11—C12—C13114.33 (15)C26—C27—H27B109.5
C11—C12—H12A108.7H27A—C27—H27B109.5
C13—C12—H12A108.7C26—C27—H27C109.5
C11—C12—H12B108.7H27A—C27—H27C109.5
C13—C12—H12B108.7H27B—C27—H27C109.5
H12A—C12—H12B107.6C25—C28A—C29A113.1 (7)
C14—C13—C12110.39 (15)C25—C28A—H28A109.0
C14—C13—C18113.39 (14)C29A—C28A—H28A109.0
C12—C13—C18112.17 (15)C25—C28A—H28B109.0
C14—C13—H13106.8C29A—C28A—H28B109.0
C12—C13—H13106.8H28A—C28A—H28B107.8
C18—C13—H13106.8C29B—C28B—C25107.4 (8)
C15—C14—C13113.64 (16)C29B—C28B—H28C110.2
C15—C14—H14A108.8C25—C28B—H28C110.2
C13—C14—H14A108.8C29B—C28B—H28D110.2
C15—C14—H14B108.8C25—C28B—H28D110.2
C13—C14—H14B108.8H28C—C28B—H28D108.5
H14A—C14—H14B107.7C28B—C29B—H29D109.5
O5—C15—C14109.59 (16)C28B—C29B—H29E109.5
O5—C15—C16108.85 (15)H29D—C29B—H29E109.5
C14—C15—C16109.21 (15)C28B—C29B—H29F109.5
O5—C15—H15109.7H29D—C29B—H29F109.5
C14—C15—H15109.7H29E—C29B—H29F109.5
O2—C1—C2—C321.4 (3)C14—C15—C16—C1757.0 (2)
O1—C1—C2—C3157.19 (18)C15—C16—C17—C1858.4 (2)
C1—C2—C3—C4174.76 (18)C16—C17—C18—C19169.14 (16)
C2—C3—C4—C2461.3 (2)C16—C17—C18—C968.5 (2)
C2—C3—C4—C5174.98 (17)C16—C17—C18—C1352.7 (2)
C24—C4—C5—C660.7 (2)C8—C9—C18—C1959.65 (19)
C3—C4—C5—C6176.08 (16)C10—C9—C18—C1965.29 (18)
C24—C4—C5—C22179.25 (17)C8—C9—C18—C1759.65 (19)
C3—C4—C5—C2256.0 (2)C10—C9—C18—C17175.40 (14)
C4—C5—C6—C2346.1 (2)C8—C9—C18—C13179.35 (14)
C22—C5—C6—C2377.91 (17)C10—C9—C18—C1355.70 (17)
C4—C5—C6—C20164.52 (15)C14—C13—C18—C19163.94 (17)
C22—C5—C6—C2040.51 (16)C12—C13—C18—C1970.2 (2)
C4—C5—C6—C780.4 (2)C14—C13—C18—C1749.4 (2)
C22—C5—C6—C7155.63 (15)C12—C13—C18—C17175.25 (16)
C23—C6—C7—O3172.37 (15)C14—C13—C18—C973.51 (19)
C20—C6—C7—O365.68 (19)C12—C13—C18—C952.37 (19)
C5—C6—C7—O345.5 (2)C11—C10—C20—C2153.6 (2)
C23—C6—C7—C867.13 (18)C9—C10—C20—C21178.56 (14)
C20—C6—C7—C854.82 (18)C11—C10—C20—C6176.03 (14)
C5—C6—C7—C8166.04 (14)C9—C10—C20—C659.00 (18)
O3—C7—C8—C969.17 (18)C23—C6—C20—C1059.83 (19)
C6—C7—C8—C954.01 (19)C7—C6—C20—C1059.89 (19)
C7—C8—C9—C1050.4 (2)C5—C6—C20—C10176.19 (14)
C7—C8—C9—C18176.02 (14)C23—C6—C20—C2169.1 (2)
C8—C9—C10—C2050.60 (18)C7—C6—C20—C21171.23 (15)
C18—C9—C10—C20177.76 (14)C5—C6—C20—C2147.30 (17)
C8—C9—C10—C11175.35 (16)C10—C20—C21—C22162.53 (15)
C18—C9—C10—C1157.48 (19)C6—C20—C21—C2234.85 (19)
C20—C10—C11—O454.32 (18)C20—C21—C22—C58.5 (2)
C9—C10—C11—O469.92 (19)C4—C5—C22—C21150.16 (16)
C20—C10—C11—C12178.40 (14)C6—C5—C22—C2120.46 (19)
C9—C10—C11—C1254.16 (19)O6—C25—C26—C2716.7 (5)
O4—C11—C12—C1369.58 (19)C28A—C25—C26—C27151.5 (4)
C10—C11—C12—C1351.6 (2)C28B—C25—C26—C27175.2 (5)
C11—C12—C13—C1476.0 (2)O6—C25—C28A—C29A17.7 (9)
C11—C12—C13—C1851.5 (2)C26—C25—C28A—C29A174.4 (6)
C12—C13—C14—C15178.72 (16)C28B—C25—C28A—C29A55.7 (9)
C18—C13—C14—C1554.5 (2)O6—C25—C28B—C29B66.6 (12)
C13—C14—C15—O5175.71 (15)C26—C25—C28B—C29B132.7 (10)
C13—C14—C15—C1656.6 (2)C28A—C25—C28B—C29B55.7 (12)
O5—C15—C16—C17176.63 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.87 (3)1.84 (3)2.672 (2)160 (4)
O3—H3···O2i0.83 (2)2.08 (2)2.879 (2)160 (2)
O4—H4···O5ii0.86 (2)1.81 (2)2.6499 (19)165 (2)
O5—H5···O3ii0.82 (2)2.10 (3)2.869 (2)157 (2)
Symmetry codes: (i) x+1, y+1/2, z+2; (ii) x, y1/2, z+1.

Experimental details

Crystal data
Chemical formulaC5H10O·C24H40O5
Mr494.69
Crystal system, space groupMonoclinic, P21
Temperature (K)100
a, b, c (Å)12.5606 (7), 8.0425 (5), 13.9139 (8)
β (°) 102.002 (3)
V3)1374.84 (14)
Z2
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.16 × 0.13 × 0.11
Data collection
DiffractometerBruker SMART APEX CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
33615, 13745, 9042
Rint0.070
(sin θ/λ)max1)0.911
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.081, 0.200, 1.06
No. of reflections13745
No. of parameters357
No. of restraints26
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.69, 0.44

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top
O1—C11.321 (2)O6—C251.216 (4)
O2—C11.213 (2)C25—C261.493 (5)
O3—C71.446 (2)C25—C28A1.507 (5)
O4—C111.435 (2)C25—C28B1.566 (7)
O5—C151.438 (2)C26—C271.519 (5)
C1—C21.512 (3)C28A—C29A1.512 (10)
C2—C31.519 (3)C28B—C29B1.531 (12)
C3—C41.540 (3)
O6—C25—C26123.0 (3)C26—C25—C28B122.8 (5)
O6—C25—C28A124.6 (3)C25—C26—C27115.1 (2)
C26—C25—C28A111.2 (3)C25—C28A—C29A113.1 (7)
O6—C25—C28B111.1 (5)C29B—C28B—C25107.4 (8)
O6—C25—C26—C2716.7 (5)O6—C25—C28B—C29B66.6 (12)
O6—C25—C28A—C29A17.7 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O4i0.87 (3)1.84 (3)2.672 (2)160 (4)
O3—H3···O2i0.83 (2)2.08 (2)2.879 (2)160 (2)
O4—H4···O5ii0.855 (18)1.81 (2)2.6499 (19)165 (2)
O5—H5···O3ii0.82 (2)2.10 (3)2.869 (2)157 (2)
Symmetry codes: (i) x+1, y+1/2, z+2; (ii) x, y1/2, z+1.
 

Acknowledgements

Halima Mouhib and Wolfgang Stahl are acknowledged for the fruitful co-operation in our project dedicated to the conformation of volatile compounds in the gas and solid phases.

References

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First citationBruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationCaira, M. R., Nassimbeni, L. R. & Scott, J. L. (1994a). J. Chem. Crystallogr. 24, 783–791.  CrossRef CAS
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First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals

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