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ISSN: 2052-5206

The low-temperature and high-pressure crystal structures of cyclo­butanol (C4H7OH)

aSchool of Physics and Astronomy, The University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JZ, Scotland, bCentre for Science at Extreme Conditions, The University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JZ, Scotland, and cSchool of Chemistry, The University of Edinburgh, King's Buildings, West Mains Road, Edinburgh EH9 3JJ, Scotland
*Correspondence e-mail: d.r.allan@ed.ac.uk

(Received 19 January 2005; accepted 16 June 2005)

The low-temperature and high-pressure crystal structures of cyclobutanol (C4H7OH) have been determined using single-crystal X-ray diffraction techniques. At temperatures below 220 K, cyclobutanol crystallizes in the Aba2 space group (Z′ =  2) and its crystal structure is composed of pseudo-threefold hydrogen-bonded molecular catemers [assigned as [C_2^2(4)] in graph-set notation], which lie parallel to the crystallographic a axis. At a pressure of 1.3 GPa, the crystal symmetry changes to Pna21 (Z′  =  1) and the molecular catemers [expressed as C(2) in graph-set notation] adopt a pseudo-twofold arrangement. This structural behaviour is in agreement with our previous observations for phenol and its halogenated derivatives 2-chlorophenol and 4-fluorophenol, where pressure was found to favour a molecular packing more closely associated with small alkyl groups rather than that of relatively bulky alkyl groups. In addition, an examination of the molecular coordination environment in the low-temperature and high-pressure structures of cyclobutanol reveals that the change in structure on application of pressure appears to be driven by the molecules assuming a packing arrangement which more closely resembles that adopted in hard-sphere structures.

1. Introduction

In the mono-alcohols (ROH) there is competition between the packing requirements of the relatively bulky R group and the demand for the small hydroxyl groups to be sufficiently close for hydrogen bonding to occur. Brock & Duncan (1994[Brock, C. P. & Duncan, L. L. (1994). Chem. Mater. 6, 1307-1312.]) have described the general features of the packing motifs adopted by mono-alcohols. They found that if the molecules containing the hydroxyl groups are relatively `thin' (by Brock and Duncan's terminology) then they can form catemers where the molecules are symmetry-related by either a glide plane or a 21-screw axis so that the molecules form an approximately coplanar alternating sequence about the central chain of hydrogen bonds. For bulkier R groups, steric hindrance often prohibits the molecules adopting this simple arrangement and, instead, these systems often form chains about three-, four- or sixfold screw axes, or adopt crystal structures with more than one molecule in the asymmetric unit. If the R group is particularly bulky, then the molecules may no longer form hydrogen-bonded chains or catemers, but cyclic dimer, trimer, tetramer or hexamer rings can be created.

In our recent high-pressure structural studies of phenol (Allan et al., 2002[Allan, D. R., Clark, S. J., Dawson, A., McGregor, P. A. & Parsons, S. (2002). Acta Cryst. B58, 1018-1024.]) and its halogenated derivatives 2-chloro­phenol and 4-fluorophenol (Oswald et al., 2005[Oswald, I. D. H., Allan, D. R., Motherwell, W. D. S. & Parsons, S. (2005). Acta Cryst. B61, 69-79.]), we have observed a clear change in the nature of the R-group packing behaviour. All three systems form crystal structures at ambient pressure, characterized by the formation of hydrogen-bonding schemes associated with bulky R groups. Both phenol and 2-chlorophenol form crystal structures where the molecules are hydrogen bonded into pseudo-threefold chains. The ambient-pressure structure of 4-fluorophenol has a markedly different packing arrangement with the molecules hydrogen bonding to form hexamer rings about threefold rotoinversion sites. After the application of pressure, however, all three systems form crystal structures with the molecules disposed along chains that are generated by 21 screw axes. In effect, pressure has transformed the packing behaviour of the phenyl and halophenyl groups from having characteristics more closely associated with bulky groups to those more typical of small groups.

Here we report the crystal structure of the high-pressure phase of cyclobutanol (C4H7OH) along with the crystal structure of its low-temperature phase, which, to the best of our knowledge, has not been reported previously. The low-temperature crystal structure (space group Aba2, Z′  =  2) is composed of pseudo-threefold hydrogen-bonded molecular catemers which lie parallel to the crystallographic a-axis. At high-pressure, the crystal symmetry changes to Pna21 (Z′  =  1) and the molecular catemers, which are generated by the a-glide symmetry, adopt a pseudo-twofold arrangement. This structural behaviour parallels what we have observed previously for phenol and 2-chlorophenol and is in agreement with the favouring of a small-group packing behaviour under pressure.

2. Experimental

Cyclobutanol (C4H8O) is a clear, colourless liquid with a melting point of 221 K and a boiling point of 395 K. It is a secondary alcohol which consists of four sp3 hybridized C atoms arranged in a puckered four-membered ring. The puckering of the ring increases the angle strain in the molecule, but relieves the eclipsing interactions of adjacent C—H bonds.

2.1. Differential scanning calorimetry (DSC)

Before proceeding with structure characterization using single-crystal X-ray diffraction methods, a survey of the low-temperature phase behaviour of cyclobutanol was undertaken using a Perkin-Elmer Pyris differential scanning calorimeter DSC-1. The sample of cyclobutanol (99.5 %, obtained from Sigma-Aldrich) was contained in a sealed aluminium pan. Fig. 1[link] shows that super-cooling occurs in the sample and the liquid does not crystallize until it is warmed where the exothermic crystallization peak occurs at 180 K (event C in Fig. 1[link]). The small endothermic event which occurs in this first scan at approximately 138 K (event B in Fig. 1[link]) is a glass transition in which some degree of ordering occurs in the glassy phase. This does not occur in the polycrystalline material. Melting occurs at 221 K (event A in Fig. 1[link]). The DSC experiment showed that no phase change occurs in the material down to temperatures as low as 105 K after initial crystallization. Therefore, a single crystal could be grown at a temperature just below the 221 K melting point and then safely cooled for subsequent X-ray data collection.

[Figure 1]
Figure 1
The relationship between heat flow versus temperature for cyclobutanol. The sample was loaded into the differential scanning calorimeter as a liquid at room temperature, 273 K. The sample temperature was cycled from 273 to 105 K and finally back to room temperature at a rate of 10 K min−1. A = melting, B = glass transition, C = crystallization of glass.

2.2. Low-temperature crystal growth of phase I

Liquid cyclobutanol was loaded into a capillary of 0.33 mm diameter. This was attached to a goniometer head and mounted on a BRUKER SMART-APEX (Siemens, 1993[Siemens (1993). SMART. Siemens Industrial Autom., Inc., Madison, Wisconsin, USA.]) diffractometer, equipped with an Oxford Cryosystems low-temperature device and an OHCD laser-assisted crystallization device (Boese & Nussbaumer, 1994[Boese, R. & Nussbaumer, M. (1994). Correlations, Transformations and Interactions in Organic Chemistry, IUCr Crystallographic Symposia, Vol. 7, edited by D. W. Jones & A. Katrusiak. Oxford University Press.]). The sample was cooled to just below the melting point. A solid–liquid equilibrium was established at approximately 1.5 W laser power and a crystal was grown by applying the same laser power along approximately 0.5 mm of the capillary over a duration of 30 min. The laser power was subsequently reduced to 0 W over a further period of 20 min at the end of the cycle.

A hemisphere of data was collected in the range 2θ < 52° and the resulting diffraction pattern was indexed using GEMINI (Sparks, 1999[Sparks, R. A. (1999). Bruker AXS, Madison Wisconsin, USA.]) and integrated with SAINT (Siemens, 1995[Siemens (1995). SAINT. Siemens Industrial Autom., Inc: Madison, Wisconsin, USA.]). An absorption correction was applied using SADABS (Sheldrick, 2001[Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany, and Bruker AXS, Madison, Wisconsin, USA.]). The structure was initially solved by direct methods in the space group C2 and the symmetry was later increased to Aba2 after analysis with the program MISSYM, as incorporated into PLATON (Spek, 2001[Spek, A. L. (2001). PLATON. Utrecht University, The Netherlands.]). The structure was refined by full-matrix least-squares against |F2| (SHELXTL; Sheldrick, 2001[Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany, and Bruker AXS, Madison, Wisconsin, USA.]). Initially, the H atoms were located using difference Fourier maps and, in subsequent cycles of refinement, their positions were idealized and constrained geometrically. All non-H atoms were modeled with anisotropic displacement parameters and, as the data were of sufficient quality, the H atoms could be refined isotropically. The sample was then cooled to 100 K and a second set of intensity data were collected, following the same strategy as that employed for the 220 K data set. Refinement details and statistics are shown in Table 1[link].1

Table 1
Refinement statistics for the low-temperature, Aba2, and high-pressure, Pna21, phases of cyclobutanol

Temperature (K); pressure (GPa) 220; 0 100; 0 293; 1.3
Crystal data      
Chemical formula C4H8O C4H8O C4H8O
Mr 72.10 72.10 72.10
Cell setting, space group Orthorhombic, Aba2 Orthorhombic, Aba2 Orthorhombic, Pna21
a, b, c (Å) 9.379 (2), 13.658 (2), 13.661 (2) 9.331 (2), 13.642 (2), 13.619 (2) 4.9208 (4), 8.230 (1), 9.598 (2)
V3) 1749.9 (5) 1733.7 (5) 388.71 (9)
Z 16 16 4
Dx (Mg m−3) 1.095 1.105 1.232
Radiation type Mo Kα Mo Kα Mo Kα
No. reflections for cell parameters 2278 3363 479
θ range (°) 3–26 3.8–28.4 3–20
μ (mm−1) 0.08 0.08 0.09
Temperature (K) 220 (2) 100 (2) 293 (2)
Crystal form, colour Cylinder, colourless Cylinder, colourless Prism, colourless
Crystal size (mm) 0.50 × 0.33 × 0.33 0.50 × 0.33 × 0.33 0.02 × 0.02 × 0.01
       
Data collection      
Diffractometer CCD area detector CCD area detector CCD area detector
Data collection method φ and ω scans φ and ω scans φ and ω scans
Absorption correction Multi-scan (based on symmetry-related measurements) Multi-scan (based on symmetry-related measurements) Multi-scan (based on symmetry-related measurements)
Tmax 0.693 0.766 0.425
Tmin 1.000 1.000 0.928
No. of measured, independent and observed reflections 4279, 918, 824 5003, 1093, 922 747, 225, 197
Criterion for observed reflections I > 2σ(I) I > 2σ(I) I > 2σ(I)
Rint 0.046 0.051 0.073
θmax (°) 26.4 28.6 20.0
Range of h, k, l −11 → h → 11 −12 → h → 12 −4 → h → 4
  −17 → k → 14 −17 → k → 14 −7 → k → 7
  −14 → l → 17 −17 → l → 15 −6 → l → 6
       
Refinement      
Refinement on F2 F2 F2
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.104, 1.07 0.047, 0.106, 1.00 0.071, 0.162, 1.14
No. of reflections 918 1093 225
No. of parameters 108 108 23
H-atom treatment Riding Riding Riding
Weighting scheme w = 1/[σ2(Fo2) + (0.0702P)2], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0649P)2], where P = (Fo2 + 2Fc2)/3 w = 1/[σ2(Fo2) + (0.0788P)2 + 0.4005P], where P = (Fo2 + 2Fc2)/3
(Δ/σ)max 0.051 <0.0001 <0.0001
Δρmax, Δρmin(e Å3) 0.17, −0.17 0.25, −0.22 0.20, −0.19
Extinction method SHELXTL SHELXTL None
Extinction coefficient 0.013 (2) 0.0080 (4)
Absolute structure Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]) Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.])
Flack parameter −10 (10) −10 (10) 1 (10)
Computer programs used: SMART (Siemens, 1993[Siemens (1993). SMART. Siemens Industrial Autom., Inc., Madison, Wisconsin, USA.]), SAINT (Siemens, 1995[Siemens (1995). SAINT. Siemens Industrial Autom., Inc: Madison, Wisconsin, USA.]), SHELXTL, SHELXS97, SHELXL97 (Sheldrick, 2001[Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany, and Bruker AXS, Madison, Wisconsin, USA.]).

2.3. High-pressure crystal growth of phase II

Liquid cyclobutanol was loaded and pressurized in a Merrill–Bassett diamond–anvil cell (Merrill & Bassett, 1974[Merrill, L. & Bassett, W. A. (1974). Rev. Sci. Instrum. 45, 290-294.]) equipped with 600 µm culet diamonds and a tungsten gasket. After the nucleation of several crystallites the temperature was cycled close to the melting curve, in order to reduce the number of crystallites. Finally, a single crystal was obtained at approximately 1.3 GPa that entirely filled the 175 µm gasket hole.

Data were collected with the cell mounted in a single orientation and the subsequent diffraction pattern was indexed with the program GEMINI (Sparks, 1999[Sparks, R. A. (1999). Bruker AXS, Madison Wisconsin, USA.]). Data integration (to 2θ = 45°) was performed using SAINT (Siemens, 1995[Siemens (1995). SAINT. Siemens Industrial Autom., Inc: Madison, Wisconsin, USA.]) with dynamic masking to account for the shading from the steel body of the diamond-anvil cell. The program SHADE (Parsons, 2004[Parsons, S. (2004). SHADE. The University of Edinburgh, Scotland.]) was used to take account of absorption effects due to the pressure cell and further systematic errors were treated using SADABS (Sheldrick, 2001[Sheldrick, G. M. (2001). SADABS. University of Göttingen, Germany, and Bruker AXS, Madison, Wisconsin, USA.]) before merging in SORTAV (Blessing, 1997[Blessing, R. H. (1997). J. Appl. Cryst. 30, 421-426.]). More detailed data collection and processing procedures used in our laboratory have been described in Dawson et al. (2004[Dawson, A., Allan, D. R., Parsons, S. & Ruf, M. (2004). J. Appl. Cryst. 37, 410-416.]). Structure solution and refinement procedures were similar to those outlined for the low-temperature data sets, with the exception that the H-atom positions could not be observed in the Fourier difference maps and they had to be located and constrained in the refinement using geometrical considerations. The final refinement statistics are listed in Table 1[link].

3. Results

3.1. The low-temperature phase I crystal structure

The crystal structure of phase I of cyclobutanol has two molecules in the asymmetric unit and it is characterized by the presence of binary hydrogen-bonded chains of cyclobutanol molecules aligned parallel to the crystallographic a axis. The two molecules in the asymmetric unit are hydrogen bonded together to form a single section of the chain and the b-glide symmetry links these sections in pairs to construct the complete catemer. These catemers are not strictly helical in nature, as helices are not supported by the b glide. The chains are assigned the graph-set notation [C_2^2(4)] – having two unique hydrogen-bond donors and two unique hydrogen-bond acceptors involving a total of four atoms. Fig. 2[link] shows an individual hydrogen-bonded chain, while the complete structure is shown in projection along the a axis in Fig. 3[link]. From this a-axis projection, the pseudo-threefold nature of the chains is apparent and it can also be observed that the alkyl groups of molecules in neighbouring chains lie on top of one another to form an intertwining arrangement. The chains themselves are stacked in layers perpendicular to the crystallographic b axis and, in the crystal structure as a whole, each molecule occupies a volume of 109.4 (1) Å3 at 220 K and 108.4 (1) Å3 at 100 K (a difference of 0.9%).

[Figure 2]
Figure 2
A view of the hydrogen-bonded molecular chains in the low-temperature, Aba2, crystal structure of cyclobutanol. The chains are aligned parallel to the crystallographic a axis.
[Figure 3]
Figure 3
Packing plot of cyclobutanol phase I viewed parallel to the crystallographic a axis showing the intertwining of the chains via neighbouring alkyl groups is readily apparent (the b axis is directed towards the right of the page, the c axis is directed down the page).

3.2. The high-pressure phase II crystal structure

The crystal structure of phase II of cyclobutanol has one molecule in the asymmetric unit that acts dually as a hydrogen-bond donor and a hydrogen-bond acceptor. Consequently, there is one unique hydrogen bond in the structure and this links neighbouring molecules to form hydrogen-bonded chains expressed as C(2) in graph-set notation – the repeating unit contains one hydrogen-bond donor and one hydrogen-bond acceptor. At a pressure of 1.3 GPa, each molecule occupies 97.2 (1) Å3 and comparing this to the volume of the low-temperature phase gives a 10.3% reduction in volume with respect to the 100 K structure and an 11.2% reduction in volume compared with the 220 K structure.

Fig. 4[link] shows the hydrogen-bonded chains of cyclobutanol molecules. The chains involve a repeating unit of two molecules related by the a glide symmetry. The wave-like chains are aligned in layers stacked along the c axis, as shown in Fig. 5[link] and, unlike the chains in the low-temperature phase, the packing does not result in an intertwining of the alkyl groups.

[Figure 4]
Figure 4
The wave-like hydrogen-bonded chains of the high-pressure, Pna21, phase of cyclobutanol. The chains are aligned parallel to the crystallographic a axis.
[Figure 5]
Figure 5
Packing plot of the high-pressure phase of cyclobutanol viewed down the crystallographic a axis (the b axis is directed towards the left of the page, the c axis is directed up the page).

4. Discussion and comparison of the low-temperature and high-pressure phases

Perhaps the most significant difference between the low-temperature and the high-pressure polymorphs is the reduction in molecular volume. At ambient pressure and 220 K, each molecule occupies 108.4 (1) Å3 compared with 96.8 (1) Å3 at room temperature and 1.3 GPa, a decrease of approximately 10%. It would naturally be assumed that this reduction in molecular volume with pressure would be accommodated by the intermolecular contacts and that the hydrogen bonds should exhibit a strong pressure effect. This does not appear to be the case and the donor–acceptor distances for the low-temperature phase are somewhat shorter than those in the high-pressure phase, see Table 2[link]. Although this observation is perhaps counter-intuitive, a similar affect also been observed on comparison of the crystal structures of the low-temperature and high-pressure phases of phenol (Allan et al., 2002[Allan, D. R., Clark, S. J., Dawson, A., McGregor, P. A. & Parsons, S. (2002). Acta Cryst. B58, 1018-1024.]) and of the halophenols (Oswald et al., 2005[Oswald, I. D. H., Allan, D. R., Motherwell, W. D. S. & Parsons, S. (2005). Acta Cryst. B61, 69-79.]). It was suggested that the reason for the increase in the hydrogen-bond distance with pressure for the phenols was due, principally, to steric effects. The observation that there is a similar effect in cyclobutanol provides further evidence that this lengthening of the hydrogen bond is linked to steric considerations.

Table 2
The donor–acceptor O⋯O distances in the low-temperature, Aba2, and high-pressure, Pna21, crystal structures of cyclobutanol

Phase I O2⋯O1 (Å) O⋯O2i (Å)
220 K 2.709 (3) 2.742 (2)
110 K 2.703 (3) 2.736 (2)
     
Phase II O1⋯O1i (Å)  
1.3 GPa 2.809 (4)  
Symmetry code: (i) [1 x-{1\over 2}, -y-{1\over 2}, z].

It is interesting to note that the apparent increase in hydrogen-bond length between the high-pressure and low-temperature phases of cyclobutanol, phenol and the halophenols is paralleled by strikingly similar changes to the arrangement of the molecules themselves within the hydrogen-bonded chains. The a-glide which generates the hydrogen-bonded molecular chains in both the low-temperature, Aba2, and high-pressure, Pna21, crystal structures, is basically a twofold symmetry operation. Brock & Duncan (1994[Brock, C. P. & Duncan, L. L. (1994). Chem. Mater. 6, 1307-1312.]) have demonstrated that small molecules pack along 21 screw axes or glides, and hence the high-pressure behaviour of cyclobutanol is typical of them. An analogous structural transformation is also observed in phenol, where the same topological change from pseudo-threefold to pseudo-twofold occurs between the low-temperature and high-pressure phases, respectively (where both polymorphs have the same P21 space group). This trend is also observed in three halophenol systems studied by Oswald et al. (2005[Oswald, I. D. H., Allan, D. R., Motherwell, W. D. S. & Parsons, S. (2005). Acta Cryst. B61, 69-79.]). Although they form crystal structures at ambient pressure which are typical of molecules containing bulky R groups, at high pressure they adopt crystal structures with the molecules disposed along chains that are generated by 21 screw axes.

Finally, given that the reduction in molecular volume at pressure cannot be attributed to the shortening of intermolecular hydrogen bonding, and indeed the converse appears to be the case, it would be valuable, therefore, to compare other structural features, such as the molecular packing, as this is indicative of overall intermolecular contacts. The topological characteristics of packing in molecular crystal structures have been studied by Blatov and co-workers (Blatov et al., 2000[Blatov, V. A., Shevchenko, A. P. & Serezhkin, V. N. (2000). J. Appl. Cryst. 33, 1193.]). The coordination environment of a molecule in a crystal structure can be visualized using a Voronoi–Dirichlet polyhedron or VDP (Peresypkina & Blatov, 2000a[Peresypkina, E. V. & Blatov, V. A. (2000a). Acta Cryst. B56, 501-511.],b[Peresypkina, E. V. & Blatov, V. A. (2000b). Acta Cryst. B56, 1035-1045.]). The greater efficiency of packing in cyclobutanol-II (the high pressure phase) can be gauged by comparison of the lattice VDPs of the two phases. In both phases the molecular coordination number (MCN) is 14. Fourteen is the most commonly observed value in molecular structures and ideally the VDP is a cuboctahedron, as observed in the body-centred cubic structure of tungsten (Fig. 6[link]a); this VDP is characterized by a covering coefficient (Peresypkina & Blatov, 2000a[Peresypkina, E. V. & Blatov, V. A. (2000a). Acta Cryst. B56, 501-511.]) of 1.46. The VDPs of the two independent molecules in cyclobutanol-I are shown in Figs. 6[link](b) and (c), and they clearly correspond to distorted versions of the cuboctahedron shown in Fig. 6[link](a). The covering coefficients are 1.98 and 2.00. The VDP of cyclobutanol-II (Fig. 6[link]d) is still a distorted version of Fig. 6[link](a), but the distortion is less than for phase I, with a covering coefficient of 1.69. The change in the crystal structure of cyclobutanol on application of pressure can thus be considered to be driven by the adoption of a packing arrangement which more closely resembles that adopted in hard-sphere structures.

[Figure 6]
Figure 6
Lattice Voronoi–Dirichlet polyhedra. (a) The perfect body-centred cubic structure of tungsten at room-temperature. (b) and (c) The components of the asymmetric unit of cyclobutanol-I at 100 K. (d) Cyclobutanol-II at 1.3 GPa.

5. Conclusions

The structural changes exhibited between the low-temperature phase of cyclobutanol and its corresponding high-pressure phase are strongly paralleled by the changes we have observed previously between the low-temperature and high-pressure phases of phenol and its halogenated derivatives 2-chlorophenol and 4-fluorophenol (Oswald et al., 2005[Oswald, I. D. H., Allan, D. R., Motherwell, W. D. S. & Parsons, S. (2005). Acta Cryst. B61, 69-79.]). The general structural change accompanying the helical to coplanar structural rearrangement of the molecules in these systems results in a marked improvement in packing efficiency and would appear to be driven by the steric hindrance of the phenyl groups. For cyclobutanol, an analogous affect appears to be influencing the high-pressure structural behaviour as the change of structure appears to be in response to the molecules adopting an arrangement analogous to the packing of hard spheres.

Supporting information


Computing details top

Data collection: BRUKER-SMART for cb220k, cbutan; Bruker SMART for cb100k. Cell refinement: BRUKER-SMART for cb220k, cbutan; Bruker SMART for cb100k. Data reduction: BRUKER-SAINT for cb220k, cbutan; Bruker SAINT for cb100k. Program(s) used to solve structure: BRUKER-SHELXTL for cb220k; Bruker SHELXTL for cb100k; SHELXS97 (Sheldrick, 1990) for cbutan. For all compounds, program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: BRUKER-SHELXTL for cb220k, cbutan; Bruker SHELXTL for cb100k. Software used to prepare material for publication: BRUKER-SHELXTL for cb220k, cbutan; Bruker SHELXTL for cb100k.

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
[Figure 5]
[Figure 6]
(cb220k) top
Crystal data top
C4H8ODx = 1.095 Mg m3
Mr = 72.10Melting point: 220 K
Orthorhombic, Aba2Mo Kα radiation, λ = 0.71073 Å
a = 9.3789 (16) ÅCell parameters from 2278 reflections
b = 13.658 (2) Åθ = 3–26°
c = 13.661 (2) ŵ = 0.08 mm1
V = 1749.9 (5) Å3T = 220 K
Z = 16Cylinder, colourless
F(000) = 6400.50 × 0.33 × 0.33 mm
Data collection top
CCD-area detector
diffractometer
918 independent reflections
Radiation source: fine-focus sealed tube824 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
phi and ω scansθmax = 26.4°, θmin = 3.0°
Absorption correction: multi-scan
SADABS
h = 1111
Tmin = 0.693, Tmax = 1.000k = 1714
4279 measured reflectionsl = 1417
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullRiding
R[F2 > 2σ(F2)] = 0.042 w = 1/[σ2(Fo2) + (0.0702P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.104(Δ/σ)max = 0.051
S = 1.07Δρmax = 0.17 e Å3
918 reflectionsΔρmin = 0.17 e Å3
108 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.013 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 10 (10)
Crystal data top
C4H8OV = 1749.9 (5) Å3
Mr = 72.10Z = 16
Orthorhombic, Aba2Mo Kα radiation
a = 9.3789 (16) ŵ = 0.08 mm1
b = 13.658 (2) ÅT = 220 K
c = 13.661 (2) Å0.50 × 0.33 × 0.33 mm
Data collection top
CCD-area detector
diffractometer
918 independent reflections
Absorption correction: multi-scan
SADABS
824 reflections with I > 2σ(I)
Tmin = 0.693, Tmax = 1.000Rint = 0.046
4279 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042Riding
wR(F2) = 0.104Δρmax = 0.17 e Å3
S = 1.07Δρmin = 0.17 e Å3
918 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
108 parametersAbsolute structure parameter: 10 (10)
1 restraint
Special details top

Experimental. Low melting point material contained in a thin walled glass capilliary

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. 061_ALERT_3_B Tmax/Tmin Range Test RR' too Large ·········.. 0.70 062_ALERT_4_C Rescale T(min) & T(max) by ··················. 0.98

SADABS corrects for all systematic errors that lead to disparities in the intensities of equivalent data. It is possible that the larger than expected range of transmission is accounted for by crystal decay or absorption by the mounting fibre.

028_ALERT_3_C _diffrn_measured_fraction_theta_max Low ···.. 0.99 125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ? No action taken.

089_ALERT_3_C Poor Data / Parameter Ratio ·················· 8.50 223_ALERT_4_C Large Solvent/Anion H Ueq(max)/Ueq(min). 3.26 Ratio

This is discussed.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C110.0552 (2)0.22614 (18)0.79482 (17)0.0450 (5)
H110.14800.20310.76920.027 (5)*
O10.06454 (17)0.23641 (13)0.89748 (12)0.0510 (5)
H10.00490.26820.91770.058 (8)*
C120.0639 (3)0.16372 (19)0.75122 (18)0.0510 (6)
H1220.15090.16190.79090.049 (6)*
H1210.03390.09770.73220.067 (8)*
C130.0696 (3)0.23728 (19)0.66552 (17)0.0527 (6)
H1310.01210.21810.60880.084 (10)*
H1320.16650.25560.64580.070 (10)*
C140.0032 (3)0.31213 (17)0.73273 (19)0.0516 (6)
H1410.07990.34920.70110.088 (11)*
H1420.06320.35580.76680.071 (9)*
C210.3225 (2)0.08035 (17)0.98968 (17)0.0447 (5)
H210.42090.06131.00790.052 (7)*
O20.32034 (15)0.18196 (10)0.97174 (12)0.0429 (4)
H20.23870.19880.95530.044 (7)*
C220.2203 (4)0.03520 (19)1.0629 (2)0.0633 (8)
H2210.12850.06911.06780.079 (10)*
H2220.26190.02401.12780.102 (13)*
C230.2176 (3)0.05606 (19)0.9972 (2)0.0662 (8)
H2310.28610.10681.01640.092 (12)*
H2320.12220.08380.98760.087 (11)*
C240.2680 (3)0.00845 (19)0.9134 (2)0.0619 (7)
H2410.19070.03420.87260.052 (7)*
H2420.34320.02110.87330.100 (13)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.0425 (11)0.0584 (13)0.0339 (10)0.0071 (9)0.0023 (9)0.0018 (10)
O10.0439 (9)0.0737 (11)0.0352 (8)0.0145 (7)0.0070 (6)0.0006 (7)
C120.0602 (14)0.0475 (11)0.0452 (12)0.0016 (11)0.0058 (10)0.0004 (10)
C130.0596 (16)0.0679 (15)0.0307 (11)0.0069 (11)0.0005 (10)0.0017 (10)
C140.0575 (14)0.0542 (13)0.0430 (11)0.0030 (11)0.0011 (10)0.0093 (10)
C210.0392 (11)0.0412 (11)0.0537 (14)0.0060 (9)0.0051 (9)0.0023 (9)
O20.0395 (8)0.0408 (8)0.0484 (8)0.0003 (6)0.0048 (7)0.0002 (7)
C220.088 (2)0.0492 (13)0.0525 (15)0.0048 (13)0.0046 (13)0.0053 (11)
C230.0778 (19)0.0397 (12)0.081 (2)0.0025 (12)0.0061 (16)0.0025 (13)
C240.0779 (18)0.0505 (13)0.0572 (15)0.0032 (13)0.0093 (13)0.0137 (11)
Geometric parameters (Å, º) top
C11—O11.412 (3)C21—O21.409 (3)
C11—C121.526 (4)C21—C221.517 (4)
C11—C141.529 (3)C21—C241.520 (3)
C11—H110.9900C21—H210.9900
O1—H10.8300O2—H20.8300
C12—C131.544 (3)C22—C231.536 (4)
C12—H1220.9800C22—H2210.9800
C12—H1210.9800C22—H2220.9800
C13—C141.534 (4)C23—C241.520 (4)
C13—H1310.9800C23—H2310.9800
C13—H1320.9800C23—H2320.9800
C14—H1410.9800C24—H2410.9800
C14—H1420.9800C24—H2420.9800
O1—C11—C12119.3 (2)O2—C21—C22120.4 (2)
O1—C11—C14119.6 (2)O2—C21—C24120.8 (2)
C12—C11—C1488.81 (18)C22—C21—C2488.68 (19)
O1—C11—H11109.2O2—C21—H21108.4
C12—C11—H11109.2C22—C21—H21108.4
C14—C11—H11109.2C24—C21—H21108.4
C11—O1—H1109.5C21—O2—H2109.5
C11—C12—C1387.59 (18)C21—C22—C2387.4 (2)
C11—C12—H122114.1C21—C22—H221114.1
C13—C12—H122114.1C23—C22—H221114.1
C11—C12—H121114.1C21—C22—H222114.1
C13—C12—H121114.1C23—C22—H222114.1
H122—C12—H121111.2H221—C22—H222111.3
C14—C13—C1287.96 (18)C24—C23—C2287.98 (19)
C14—C13—H131114.0C24—C23—H231114.0
C12—C13—H131114.0C22—C23—H231114.0
C14—C13—H132114.0C24—C23—H232114.0
C12—C13—H132114.0C22—C23—H232114.0
H131—C13—H132111.2H231—C23—H232111.2
C11—C14—C1387.83 (18)C23—C24—C2187.9 (2)
C11—C14—H141114.0C23—C24—H241114.0
C13—C14—H141114.0C21—C24—H241114.0
C11—C14—H142114.0C23—C24—H242114.0
C13—C14—H142114.0C21—C24—H242114.0
H141—C14—H142111.2H241—C24—H242111.2
(cb100k) top
Crystal data top
C4H8ODx = 1.105 Mg m3
Dm = 0 Mg m3
Dm measured by not measured
Mr = 72.10Melting point: 220 K
Orthorhombic, Aba2Mo Kα radiation, λ = 0.71073 Å
a = 9.3312 (15) ÅCell parameters from 3363 reflections
b = 13.642 (2) Åθ = 3.8–28.4°
c = 13.619 (2) ŵ = 0.08 mm1
V = 1733.7 (5) Å3T = 100 K
Z = 16Cylinder, colourless
F(000) = 6400.50 × 0.33 × 0.33 mm
Data collection top
CCD area detector
diffractometer
1093 independent reflections
Radiation source: fine-focus sealed tube922 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
phi and ω scansθmax = 28.6°, θmin = 3.0°
Absorption correction: multi-scan
Ref: SADABS
h = 1212
Tmin = 0.766, Tmax = 1.000k = 1714
5003 measured reflectionsl = 1715
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullRiding
R[F2 > 2σ(F2)] = 0.047 w = 1/[σ2(Fo2) + (0.0649P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.106(Δ/σ)max < 0.001
S = 1.00Δρmax = 0.25 e Å3
1093 reflectionsΔρmin = 0.22 e Å3
108 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0080 (14)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 10 (10)
Crystal data top
C4H8OV = 1733.7 (5) Å3
Mr = 72.10Z = 16
Orthorhombic, Aba2Mo Kα radiation
a = 9.3312 (15) ŵ = 0.08 mm1
b = 13.642 (2) ÅT = 100 K
c = 13.619 (2) Å0.50 × 0.33 × 0.33 mm
Data collection top
CCD area detector
diffractometer
1093 independent reflections
Absorption correction: multi-scan
Ref: SADABS
922 reflections with I > 2σ(I)
Tmin = 0.766, Tmax = 1.000Rint = 0.051
5003 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047Riding
wR(F2) = 0.106Δρmax = 0.25 e Å3
S = 1.00Δρmin = 0.22 e Å3
1093 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
108 parametersAbsolute structure parameter: 10 (10)
1 restraint
Special details top

Experimental. Low melting point sample - liquid loaded into a thin walled glass capilliary

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. 061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ·········.. 0.78 062_ALERT_4_C Rescale T(min) & T(max) by ··················. 0.98

SADABS corrects for all systematic errors that lead to disparities in the intensities of equivalent data. It is possible that the larger than expected range of transmission is accounted for by crystal decay or absorption by the mounting fibre.

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···..

No action taken.

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
C110.0545 (3)0.22494 (19)0.79351 (17)0.0293 (5)
H110.14770.20060.76660.020 (6)*
O10.06638 (17)0.23508 (13)0.89729 (12)0.0331 (4)
H10.00370.26730.91860.044 (8)*
C120.0687 (3)0.16276 (19)0.75094 (17)0.0316 (5)
H1220.15620.16200.79200.043 (8)*
H1210.04010.09560.73160.036 (7)*
C130.0742 (3)0.23692 (18)0.66429 (17)0.0332 (6)
H1310.01740.21670.60630.050 (9)*
H1320.17240.25660.64520.043 (9)*
C140.0032 (3)0.31201 (18)0.73171 (18)0.0320 (5)
H1410.08130.34850.69890.052 (9)*
H1420.06240.35700.76690.040 (8)*
C210.3245 (2)0.08065 (18)0.99115 (17)0.0286 (5)
H210.42340.06141.01180.039 (8)*
O20.32292 (16)0.18252 (11)0.97302 (12)0.0281 (4)
H20.24000.19980.95630.042 (8)*
C220.2170 (3)0.03517 (18)1.06350 (18)0.0380 (6)
H2210.12370.06951.06640.045 (8)*
H2220.25630.02391.13010.067 (10)*
C230.2171 (3)0.05692 (19)0.9973 (2)0.0408 (7)
H2310.28540.10831.01830.043 (8)*
H2320.12060.08480.98550.052 (8)*
C240.2725 (3)0.00793 (18)0.9131 (2)0.0387 (6)
H2410.35060.02220.87430.057 (9)*
H2420.19620.03400.87000.038 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C110.0253 (11)0.0445 (14)0.0181 (10)0.0048 (10)0.0018 (9)0.0004 (10)
O10.0266 (9)0.0553 (11)0.0174 (8)0.0096 (7)0.0037 (7)0.0002 (7)
C120.0336 (13)0.0369 (12)0.0244 (11)0.0003 (10)0.0026 (10)0.0003 (10)
C130.0349 (14)0.0478 (14)0.0168 (10)0.0032 (11)0.0003 (10)0.0010 (10)
C140.0339 (13)0.0386 (13)0.0234 (11)0.0025 (11)0.0002 (9)0.0037 (10)
C210.0249 (11)0.0318 (12)0.0293 (12)0.0043 (9)0.0022 (9)0.0022 (9)
O20.0231 (9)0.0342 (9)0.0270 (8)0.0007 (7)0.0027 (7)0.0004 (7)
C220.0485 (17)0.0376 (13)0.0278 (13)0.0030 (12)0.0021 (10)0.0028 (10)
C230.0442 (16)0.0338 (13)0.0445 (15)0.0013 (11)0.0043 (13)0.0018 (12)
C240.0436 (15)0.0408 (13)0.0316 (13)0.0011 (12)0.0071 (11)0.0084 (11)
Geometric parameters (Å, º) top
C11—O11.424 (3)C21—O21.411 (3)
C11—C141.533 (3)C21—C241.532 (3)
C11—C121.542 (3)C21—C221.537 (3)
C11—H111.0000C21—H211.0000
O1—H10.8400O2—H20.8400
C12—C131.555 (3)C22—C231.547 (3)
C12—H1220.9900C22—H2210.9900
C12—H1210.9900C22—H2220.9900
C13—C141.553 (4)C23—C241.537 (4)
C13—H1310.9900C23—H2310.9900
C13—H1320.9900C23—H2320.9900
C14—H1410.9900C24—H2410.9900
C14—H1420.9900C24—H2420.9900
O1—C11—C14119.6 (2)O2—C21—C24120.9 (2)
O1—C11—C12119.0 (2)O2—C21—C22120.2 (2)
C14—C11—C1289.25 (19)C24—C21—C2288.66 (18)
O1—C11—H11109.1O2—C21—H21108.5
C14—C11—H11109.1C24—C21—H21108.5
C12—C11—H11109.1C22—C21—H21108.5
C11—O1—H1109.5C21—O2—H2109.5
C11—C12—C1387.24 (17)C21—C22—C2387.3 (2)
C11—C12—H122114.1C21—C22—H221114.1
C13—C12—H122114.1C23—C22—H221114.1
C11—C12—H121114.1C21—C22—H222114.1
C13—C12—H121114.1C23—C22—H222114.1
H122—C12—H121111.3H221—C22—H222111.3
C14—C13—C1288.01 (18)C24—C23—C2288.13 (18)
C14—C13—H131114.0C24—C23—H231114.0
C12—C13—H131114.0C22—C23—H231114.0
C14—C13—H132114.0C24—C23—H232114.0
C12—C13—H132114.0C22—C23—H232114.0
H131—C13—H132111.2H231—C23—H232111.2
C11—C14—C1387.63 (17)C21—C24—C2387.8 (2)
C11—C14—H141114.0C21—C24—H241114.0
C13—C14—H141114.0C23—C24—H241114.0
C11—C14—H142114.0C21—C24—H242114.0
C13—C14—H142114.0C23—C24—H242114.0
H141—C14—H142111.2H241—C24—H242111.2
(cbutan) top
Crystal data top
C4H8ODx = 1.232 Mg m3
Mr = 72.10Melting point: 220 K
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
a = 4.9208 (4) ÅCell parameters from 479 reflections
b = 8.2302 (10) Åθ = 3–20°
c = 9.5980 (16) ŵ = 0.09 mm1
V = 388.71 (9) Å3T = 293 K
Z = 4Prism, colourless
F(000) = 1600.02 × 0.02 × 0.01 mm
Data collection top
CCD-area detector
diffractometer
225 independent reflections
Radiation source: fine-focus sealed tube197 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.073
Phi and ω scansθmax = 20.0°, θmin = 3.3°
Absorption correction: multi-scan
?
h = 44
Tmin = 0.425, Tmax = 0.928k = 77
747 measured reflectionsl = 66
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.071Riding
wR(F2) = 0.162 w = 1/[σ2(Fo2) + (0.0788P)2 + 0.4005P]
where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
225 reflectionsΔρmax = 0.20 e Å3
23 parametersΔρmin = 0.19 e Å3
6 restraintsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 1 (10)
Crystal data top
C4H8OV = 388.71 (9) Å3
Mr = 72.10Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 4.9208 (4) ŵ = 0.09 mm1
b = 8.2302 (10) ÅT = 293 K
c = 9.5980 (16) Å0.02 × 0.02 × 0.01 mm
Data collection top
CCD-area detector
diffractometer
225 independent reflections
Absorption correction: multi-scan
?
197 reflections with I > 2σ(I)
Tmin = 0.425, Tmax = 0.928Rint = 0.073
747 measured reflectionsθmax = 20.0°
Refinement top
R[F2 > 2σ(F2)] = 0.071Riding
wR(F2) = 0.162Δρmax = 0.20 e Å3
S = 1.15Δρmin = 0.19 e Å3
225 reflectionsAbsolute structure: Flack H D (1983), Acta Cryst. A39, 876-881
23 parametersAbsolute structure parameter: 1 (10)
6 restraints
Special details top

Experimental. High Pressure data collection − 1.2 GPa. Opening angle of the diamond-anvil cell theta=40 degrees Absorption effects from Be ring and diamond SHADE absorption correct also applied omitting intense data where theta > 40 degrees

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. 023_ALERT_3_A Resolution (too) Low [sin(th)/Lambda < 0.6]··· 19.99 Deg. 028_ALERT_3_A _diffrn_measured_fraction_theta_max Low ···.. 0.66 029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ···.. 0.66 061_ALERT_3_A Tmax/Tmin Range Test RR' too Large ·········.. 0.46 201_ALERT_2_B Isotropic non-H Atoms in Main Residue(s) = 5 210_ALERT_3_B No Anisotropic ADP's Found in CIF ············ ? 340_ALERT_3_B Low Bond Precision on C—C bonds (x 1000) Ang.. 14 024_ALERT_4_C Merging of Friedel Data Preferred for ZSi.. ! 062_ALERT_4_C Rescale T(min) & T(max) by ··················. 1.08 089_ALERT_3_C Poor Data / Parameter Ratio ·················· 9.78 241_ALERT_2_C Check High U(eq) as Compared to Neighbors.. C(3)

All of the above are due to restrictions of the high pressure cell, and difficulties in data processing all of which are discussed.

125_ALERT_4_C No _symmetry_space_group_name_Hall Given ···.. ? No action taken.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3773 (15)0.0358 (8)0.2542 (11)0.031 (2)*
H1A0.54110.03160.26030.037*
O10.4261 (10)0.1676 (6)0.1630 (12)0.040 (2)*
H10.30660.23610.17290.016 (17)*
C20.1304 (14)0.0731 (8)0.2301 (13)0.035 (3)*
H2A0.17470.17770.18930.042*
H2B0.01540.02050.17920.042*
C30.0851 (17)0.0791 (10)0.3853 (14)0.056 (3)*
H3A0.10150.05910.41290.067*
H3B0.15570.17640.42930.067*
C40.272 (2)0.0706 (9)0.4002 (15)0.045 (3)*
H4A0.40900.05970.47250.054*
H4B0.17560.17280.40850.054*
Geometric parameters (Å, º) top
C1—O11.415 (11)C2—H2B0.9700
C1—C41.520 (16)C3—C41.545 (12)
C1—C21.527 (10)C3—H3A0.9700
C1—H1A0.9800C3—H3B0.9700
O1—H10.8200C4—H4A0.9700
C2—C31.507 (17)C4—H4B0.9700
C2—H2A0.9700
O1—C1—C4118.9 (7)C2—C3—C488.7 (7)
O1—C1—C2119.4 (8)C2—C3—H3A113.9
C4—C1—C288.9 (6)C4—C3—H3A113.9
O1—C1—H1A109.3C2—C3—H3B113.9
C4—C1—H1A109.3C4—C3—H3B113.9
C2—C1—H1A109.3H3A—C3—H3B111.1
C1—O1—H1109.5C1—C4—C388.1 (7)
C3—C2—C189.2 (8)C1—C4—H4A114.0
C3—C2—H2A113.8C3—C4—H4A114.0
C1—C2—H2A113.8C1—C4—H4B114.0
C3—C2—H2B113.8C3—C4—H4B114.0
C1—C2—H2B113.8H4A—C4—H4B111.2
H2A—C2—H2B111.0

Experimental details

(cb220k)(cb100k)(cbutan)
Crystal data
Chemical formulaC4H8OC4H8OC4H8O
Mr72.1072.1072.10
Crystal system, space groupOrthorhombic, Aba2Orthorhombic, Aba2Orthorhombic, Pna21
Temperature (K)220100293
a, b, c (Å)9.3789 (16), 13.658 (2), 13.661 (2)9.3312 (15), 13.642 (2), 13.619 (2)4.9208 (4), 8.2302 (10), 9.5980 (16)
V3)1749.9 (5)1733.7 (5)388.71 (9)
Z16164
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.080.080.09
Crystal size (mm)0.50 × 0.33 × 0.330.50 × 0.33 × 0.330.02 × 0.02 × 0.01
Data collection
DiffractometerCCD-area detector
diffractometer
CCD area detector
diffractometer
CCD-area detector
diffractometer
Absorption correctionMulti-scan
SADABS
Multi-scan
Ref: SADABS
Multi-scan
Tmin, Tmax0.693, 1.0000.766, 1.0000.425, 0.928
No. of measured, independent and
observed [I > 2σ(I)] reflections
4279, 918, 824 5003, 1093, 922 747, 225, 197
Rint0.0460.0510.073
θmax (°)26.428.620.0
(sin θ/λ)max1)0.6250.6730.481
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.104, 1.07 0.047, 0.106, 1.00 0.071, 0.162, 1.15
No. of reflections9181093225
No. of parameters10810823
No. of restraints116
H-atom treatmentRidingRidingRiding
Δρmax, Δρmin (e Å3)0.17, 0.170.25, 0.220.20, 0.19
Absolute structureFlack H D (1983), Acta Cryst. A39, 876-881Flack H D (1983), Acta Cryst. A39, 876-881Flack H D (1983), Acta Cryst. A39, 876-881
Absolute structure parameter10 (10)10 (10)1 (10)

Computer programs: BRUKER-SMART, Bruker SMART, BRUKER-SAINT, Bruker SAINT, BRUKER-SHELXTL, Bruker SHELXTL, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997).

 

Footnotes

1Supplementary data for this paper are available from the IUCr electronic archives (Reference: WS5024 ). Services for accessing these data are described at the back of the journal.

Acknowledgements

We would like to offer our thanks to S. A. Moggach for his help in the preparation of this paper. We also thank the EPSRC for funding this work and for supporting DRA through his EPSRC Advanced Fellowship.

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