Download citation
Download citation
link to html
The mol­ecule of the title compound, C18H18O2, is a substituted cyclo­propane ring. The electron density in this mol­ecule has been determined by refining single-crystal X-ray data using scattering factors derived from quantum mechanical calculations. Topological analysis of the electron densities in the three cyclo­propane C-C bonds was carried out. The results show the effects of this substitution on these C-C bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113017496/qs3027sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113017496/qs3027Isup2.hkl
Contains datablock I

mol

MDL mol file https://doi.org/10.1107/S0108270113017496/qs3027Isup3.mol
Supplementary material

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270113017496/qs3027Isup4.cml
Supplementary material

CCDC reference: 964813

Introduction top

The large departure of the bond angles in three-membered cyclo­propane rings from tetra­hedral angles and the resulting strain energy are of great theoretical inter­est. The research described in this paper is an attempt to extend the theoretical and qu­anti­tative information on the molecular structures and electron-density distributions of cyclo­propane molecules available through combining X-ray crystallography and quantum mechanical calculations of a substituted cyclo­propane. In their development of invarioms, Birger Dittrich and co-workers have defined a procedure by which Gaussian wavefunctions are used to project theoretical electron densities onto the multipole model (Dittrich et al., 2005). In this method, theoretical structure factors are generated by the program Tonto (Jayatilaka & Grimwood, 2003) from the Gaussian wavefunction and then least-squares refinements give the populations of the multipoles. We have determined the nature of the electron density in the cyclo­pro­propane ring in the title compound, (I), by this method and observed the effects of substitution on the covalent bonding between these C atoms.

Experimental top

Crystal data, data collection and structure refinement details are summarized in Table 1.

Synthesis and crystallization top

A mixture of trans-β-methyl­styrene (2.5 mmol) and AgOTf (0.05 mmol) was weighed into a 25 ml one-necked round-bottomed flask covered with aluminium foil to exclude light. The mixture was dissolved with di­chloro­methane (2 ml) and stirred at room temperature under an atmosphere of argon. Methyl phenyl­diazo­acetate (0.5 mmol) in di­chloro­methane (8 ml) was then added to the solution via syringe pump over a period of 3 h. After addition, the mixture was stirred for an additional 1 h and then concentrated in vacuo. Purification by silica-gel chromatography (using 20:1 v/v hexane–Et2O as the solvent system) gave the product in 64% yield (86 mg) as colorless crystals. 1H NMR (600 MHz, δ, p.p.m.): 7.11–7.7.13 (m, 2H), 6.76–7.05 (m, 6H), 7.02–7.06 (m, 2H), 3.65 (s, 3H), 3.08 (d, 1H, J = 7.8 Hz), 2.25 (dq, 1H, J = 7.2 and 6.0 Hz), 1.47 (d, 3H, J = 6.0 Hz); 13C NMR (100 MHz, δ, p.p.m.): 172.3, 137.0, 136.4, 131.3, 127.9, 127.8, 127.6, 126.9, 126.0, 52.3, 42.4, 37.7, 27.3, 12.9. The spectroscopic data are consistent with the previously reported results (Thompson & Davies, 2007).

Refinement top

The program InvariomTool (Hübschle et al., 2007) was used to prepare the master and input files for a multipole refinement with the XDLSM program of the XD2006 suite (Volkov et al., 2006). Nonspherical scattering factors were obtained from theoretical calculations of (I) by following a procedure developed by Dittrich et al. (2006). Density functional theory (DFT) calculations were carried out using the B3LYP method in the GAUSSIAN09 suite of programs (Frisch et al., 2009). A Dunning–Huzinaga full double-zeta basis set with 3df and 3dp polarization functions was used (Dunning & Hay, 1977). Calculations were carried out using 1164 basis functions. The wavefunction was calculated for the nuclear configuration geometry from the crystal structure. Electron densities were derived by evaluating the Gaussian orbitals using the programs AIMAII (Keith, 2012) and Tonto (Jayatilaka & Grimwood, 2003). An artificial crystal of (I) (space group P1), with a cubic cell edge of 30 Å and the molecule centered at the position (1/4, 1/4, 1/4), was constructed. Structure factors for this crystal were generated by Tonto up to a resolution of sinθ /λ = 1.15 Å-1. Thermal smearing was ignored and the contributions of the core electrons were included in structure-factor calculations. Least-squares refinements of the multipole populations parameters with these structure factors, and the fixed geometry from the crystal structure, yielded a multipole model suitable for reproducing the electron density in the molecule. This method provides a means of calculating the atomic electron densities without having to partition individual atoms into pseudo-atoms. These multipole parameters, together with orientation and symmetry of the local atomic coordinate system, were transferred to the input files for a refinement with the XDLSM program of the XD2006 suite. Full matrix least-squares refinements on F2 using complete multipole expansions were carried out with the program XDLSM using statistical weights. Only reflections with intensities I > 3σ(I) were included in the refinement. In the final cycles, all atom positions were refined freely. Positional and displacement (anisotropic for non-H atoms) parameters, but not multipoles, were refined. However, a hexadecapolar level of the multipole expansion was used for all atoms. The introduction of the multipole model improved R(F) from 0.043 to 0.030, while using the same weighting scheme {w = 1/[s2(Fo2)]} as with the spherical atom refinement, and improved the goodness-of-fit value from 2.819 to 1.597.

Results and discussion top

The molecular structure of (I) (Fig. 1) can be derived from that of cyclo­propane by replacing two H atoms on C2 by a methyl formate group and a phenyl ring, one H atom on C3 with a methyl group, and one H atom on C4 with a phenyl ring. The conformation of this compound is of inter­est. The phenyl rings across the C—C bond give rise to 1,3-steric repulsion, which favors a staggered arrangement in an unbridged C—C bond. The steric repulsion between these groups might influence the electron density in the bond and is likely to have an effect on the geometry of the molecule. The electronic inter­action between the substituents and the ring is also of inter­est. Methyl, phenyl and methyl formate groups might be expected to withdraw electron density and weaken the C—C bonds.

A large number of basis functions for atoms with a large number of electrons are needed to yield accurate results. This compound has 142 electrons, of which 71 are designated β electrons. Calculations were carried out using 1164 basis functions. The nuclear geometry from the crystal structure was used for the wavefunction calculations. Subsequent X-ray refinements with the new scattering factors yielded a geometry-optimized structure. Topological analysis of the resulting densities in the cyclo­propane C—C bonds, using AIMAII (Keith, 2012), was carried out and the values compared with those derived from X-ray refinements using scattering factors derived from the quantum mechanical calculations. This is useful for testing how well the calculated electron densities are projected onto multipole crystal structure refinements and whether the XD2006 (Volkov et al., 2006) densities represent the theoretical densities faithfully. The results are presented in Table 2. There is a correlation between the densities with some differences, but the match seems to be acceptable.

The C—C bonds are expected to be weakened by strain. The characteristic C—C bond length in cyclo­propane is 1.50 Å, shorter than the normal C—C bond length of 1.54 Å (Cambridge Structural Database, Version 5.34; Allen, 2002). The three C atoms in a symmetrically substituted cyclo­propane form the geometry of an equilateral triangle (see, for example, Hartman & Hirshfeld, 1966). In cyclo­propane (I), the ring does not have C3 symmetry but has two normal C—C bonds [1.5421 (4) and 1.5338 (4) Å] and one short bond [1.5019 (4) Å; Table 3]. The shortest C—C bond occurs between the hydrido-substituted C atoms distal to the formate group, while the longest bonds are to the C atom bonded to methyl formate. The basicity of the CO2 group is expected to reduce the electron density in the two C—C bonds attached to this C atom, lengthening these two bonds (and shortening the distal bond). This effect is reflected in the atomic charges and electron densities at the bond-critical points (Table 2). The shortest bond occurs where the phenyl and methyl substituents are trans, for which repulsion between these 1,4-bonded atoms will be less. The molecular graph is shown in Fig. 2. Bond-critical points were located between the nuclei. Another two bond-critical points were located that are not normally associated with chemical bonds. The distance between atoms H6 and C12 is only 2.709 (7) Å and a (3,-1) critical point exists between them. The second (3,-1) critical point is associated with a weak intra­molecular hydrogen bond (C11—H11A··· O2; Table 4). The existence of a (3,-1) critical point is insufficient evidence for chemical bonding between these two atoms (Haaland et al. (2004), but it does show that electron density is accumulating preferentially along this direction, thereby stabilizing this short contact.

A difference electron-density map in the plane of the cyclo­propane ring is shown in Fig. 3. It is evident from this plot that there is an accumulation of charge over the entire cyclo­propane triangle area and beyond the C—C bonds. Critical points (CP), due to C—C bonding, are displaced by 0.031–0.041 Å from the C—C inter­nuclear axes. The electron density at the critical points for the C—C bonds, calculated by XD2006, are in the range 1.48–1.61 e Å-3. The largest peak, and the shortest bond path, occur between atoms C3 and C4. The smallest bond-path angle (63.85°) corresponds to the inter­nuclear angle C4—C2—C3 and the longest C—C bonds. These distances indicate that the carboxyl­ate group withdraws some of the valence density from these bonds, thereby lengthening them and decreasing the angles between them. These bond-path angles are greater than the bond angles, but still substanti­ally smaller than the tetra­hedral angle normally associated with C—C bonds.

The electron density is at a minimum near the center of the plane of the three C atoms and this point is a (3,+1) critical point of the electron density. The electron density in this ring critical point is very large (0.190 e Å-3), even though this point is the local minimum of the electron density. The bond ellipticities give a measure of how much electron density accumulates normal to the direction of the bond. Single bonds in linear alkanes typically have ellipticities close to 0. The bond ellipticities in these three C—C bonds are very large, even considerably larger than those found in ethyl­ene and aromatic systems (Bader, 1983).

The bonding electron density has a flattened form in the plane of the ring, perpendicular to the bond paths. The small bond angles force the electron density to flatten out, away from the bond-path angles and towards the center of the ring [Original text not clear - please check].

Cyclo­propyl groups resemble π-systems (Bader, 1983), and the total charge distribution on this fragment of (I) makes it suitable for conjugation with the carboxyl group and the neighboring phenyl rings.

Conclusion top

These results show a cyclo­propane group with an asymmetric and highly flattened bonding charge density. Lengthening of the C2—C4 and C2—C3 bonds and shortening of the C3—C4 bond, due to the withdrawal of electron density by the carboxyl­ate group, is reflected by the electron densities at the bond-critical points. The spread out density is likely to have been enhanced by the proximity of the two phenyl rings and the carboxyl­ate group.

Related literature top

For related literature, see: Allen (2002); Bader (1983); Dittrich et al. (2005, 2006); Dunning & Hay (1977); Frisch (2009); Hübschle et al. (2007); Haaland et al. (2004); Hartman & Hirshfeld (1966); Jayatilaka & Grimwood (2003); Keith (2012); Thompson & Davies (2007); Volkov et al. (2006).

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: XD2006 (Volkov et al., 2006); molecular graphics: XD2006 (Volkov et al., 2006), OLEX2 (Dolomanov et al., 2009) and AIMAII (Keith, 2012); software used to prepare material for publication: XD2006 (Volkov et al., 2006).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A molecular graph of (I), with the positions of the bond (3,-1) and ring (3,+1) critical points shown as small spheres.
[Figure 3] Fig. 3. A deformation electron-density map of (I), in the plane of the C atoms belonging to the cyclopropane group. Contours are drawn at 0.02 e Å-3 intervals. Solid lines represent positive contours and dashed lines negative contours. The charge is concentrated in the plane of this ring, with the largest bonding concentrations lying outside the triangle shown. The charge drops off more quickly perpendicular to this plane, resulting in a flattened shape. The local charge concentrations are greatest between atoms C3—C4, distal to the carboxylate group.
[Figure 4] Fig. 4. A positive deformation density isosurface (0.009 e Å-3), viewed in the plane of the ring.
[Figure 5] Fig. 5. A contour plot of the negative Laplacian [-Δ2ρ(r)] of the charge density in the symmetry plane of the cyclopropane. Solid lines represent positive contours and dashed lines negative contours. [Ideally, atom labels should not have parens]
[Figure 6] Fig. 6. A relief plot of the negative Laplacian [-Δ2ρ(r)] of the charge density in the symmetry plane of the cyclopropane. The bonded concentrations between atoms C3 and C4 are the largest.
Methyl (1S,2S,3R)-2-methyl-1,3-diphenylcyclopropane-1-carboxylate top
Crystal data top
C18H18O2F(000) = 568
Mr = 266.32Dx = 1.231 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 16.9049 (7) ÅCell parameters from 9516 reflections
b = 7.4168 (3) Åθ = 2.5–44.4°
c = 11.7545 (5) ŵ = 0.08 mm1
β = 102.869 (2)°T = 173 K
V = 1436.76 (10) Å3Plate, colourless
Z = 40.74 × 0.54 × 0.26 mm
Data collection top
Bruker APEXII area-detector
diffractometer
9819 reflections with I > 3σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
Graphite monochromatorθmax = 44.9°
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2008)
h = 3332
Tmin = 0.829, Tmax = 1.000k = 014
52859 measured reflectionsl = 023
11659 independent reflections
Refinement top
Refinement on FPrimary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: difference Fourier map
wR(F2) = 0.027All H-atom parameters refined
S = 1.60 w1 = 1/[s2(Fo)]
9819 reflections(Δ/σ)max = 0.001
199 parametersΔρmax = 0.18 e Å3
0 restraintsΔρmin = 0.34 e Å3
Crystal data top
C18H18O2V = 1436.76 (10) Å3
Mr = 266.32Z = 4
Monoclinic, P21/cMo Kα radiation
a = 16.9049 (7) ŵ = 0.08 mm1
b = 7.4168 (3) ÅT = 173 K
c = 11.7545 (5) Å0.74 × 0.54 × 0.26 mm
β = 102.869 (2)°
Data collection top
Bruker APEXII area-detector
diffractometer
11659 independent reflections
Absorption correction: empirical (using intensity measurements)
(SADABS; Bruker, 2008)
9819 reflections with I > 3σ(I)
Tmin = 0.829, Tmax = 1.000Rint = 0.038
52859 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.027All H-atom parameters refined
S = 1.60Δρmax = 0.18 e Å3
9819 reflectionsΔρmin = 0.34 e Å3
199 parameters
Special details top

Experimental. Absorption correction: SADABS2008/1 (Bruker, 2008) was used for absorption correction. Rint was 0.0669 before and 0.0526 after correction. The ratio of minimum to maximum transmission is 0.8289. The λ/2 correction factor is 0.0015.

Refinement. An invariom refinement was performed initially (Dittrich, Acta Cryst. A62, 217). Improved multipole populations parameters were obtained from theoretical calculations of the title compound. This is similar to the Invariom approach, except that the multipole populations parameters were obtained from theoretical calculations of the title compound without geometry optimization.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.09722 (3)0.44089 (6)0.63043 (5)0.018
O20.11751 (3)0.68409 (7)0.74652 (5)0.021
C30.18684 (2)0.83592 (4)0.54491 (3)0.013
C120.227930 (15)0.49634 (3)0.53796 (2)0.010
C40.252358 (19)0.80448 (4)0.65247 (3)0.012
C130.289726 (15)0.38543 (3)0.59957 (2)0.013
C60.371088 (15)0.77696 (3)0.55323 (2)0.013
C20.196225 (18)0.64740 (4)0.59992 (3)0.011
C170.196782 (15)0.46292 (3)0.41957 (2)0.012
C140.319322 (16)0.24176 (3)0.54485 (3)0.015
C50.340212 (16)0.81407 (3)0.65204 (3)0.011
C100.394014 (16)0.87593 (3)0.75275 (2)0.014
C70.453071 (16)0.80206 (4)0.55524 (3)0.016
C150.286497 (17)0.20686 (3)0.42726 (3)0.015
C10.134438 (19)0.59621 (4)0.66799 (3)0.013
C160.225779 (17)0.31828 (3)0.36434 (3)0.014
C90.476275 (16)0.90094 (4)0.75516 (3)0.017
C110.11671 (2)0.96115 (5)0.54654 (4)0.019
C80.505856 (17)0.86423 (4)0.65620 (3)0.019
C180.03444 (3)0.38624 (7)0.68833 (5)0.025
H40.2400 (7)0.8482 (9)0.7281 (7)0.0124 (18)
H30.2070 (4)0.8390 (15)0.4698 (7)0.0107 (17)
H170.1551 (4)0.5418 (8)0.3754 (6)0.0197 (14)
H130.3125 (4)0.4125 (9)0.6818 (6)0.0221 (14)
H100.3727 (4)0.9060 (8)0.8215 (6)0.0207 (14)
H60.3338 (4)0.7359 (7)0.4811 (6)0.0176 (13)
H160.2035 (4)0.2960 (9)0.2817 (6)0.0227 (14)
H70.4737 (5)0.7777 (8)0.4851 (6)0.0251 (15)
H150.3062 (4)0.1028 (8)0.3884 (6)0.0198 (14)
H140.3634 (4)0.1675 (9)0.5896 (6)0.0235 (15)
H11A0.1015 (8)0.9544 (12)0.6185 (9)0.025 (2)
H11B0.0711 (7)0.9360 (12)0.4827 (10)0.031 (2)
H90.5129 (4)0.9458 (8)0.8258 (6)0.0245 (15)
H80.5633 (4)0.8827 (9)0.6571 (7)0.0300 (16)
H11C0.1340 (6)1.0826 (12)0.5366 (9)0.026 (2)
H18A0.0070 (8)0.4770 (17)0.6773 (10)0.040 (3)
H18B0.0140 (9)0.2774 (16)0.6524 (9)0.039 (3)
H18C0.0564 (7)0.3654 (17)0.7690 (9)0.031 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.01517 (14)0.01622 (14)0.0256 (2)0.00675 (13)0.01098 (14)0.00731 (14)
O20.02093 (17)0.02196 (17)0.0244 (2)0.00799 (15)0.01469 (17)0.01087 (17)
C30.01117 (11)0.01068 (11)0.01603 (14)0.00145 (9)0.00289 (10)0.00090 (10)
C120.00941 (9)0.00909 (9)0.01096 (11)0.00042 (7)0.00218 (7)0.00046 (8)
C40.01002 (11)0.01128 (10)0.01386 (13)0.00154 (9)0.00344 (9)0.00281 (10)
C130.01336 (9)0.01111 (9)0.01243 (11)0.00199 (7)0.00122 (7)0.00122 (7)
C60.01123 (9)0.01398 (9)0.01443 (11)0.00182 (7)0.00425 (8)0.00174 (8)
C20.00962 (10)0.01000 (10)0.01293 (13)0.00078 (9)0.00351 (9)0.00181 (9)
C170.01186 (9)0.01182 (9)0.01154 (10)0.00162 (7)0.00116 (7)0.00130 (7)
C140.01505 (10)0.01051 (9)0.01817 (13)0.00339 (8)0.00359 (8)0.00195 (8)
C50.00996 (9)0.01014 (9)0.01256 (11)0.00149 (7)0.00265 (8)0.00063 (8)
C100.01226 (9)0.01498 (10)0.01309 (11)0.00241 (8)0.00133 (8)0.00034 (8)
C70.01216 (10)0.01882 (11)0.01943 (13)0.00262 (8)0.00652 (9)0.00151 (9)
C150.01678 (10)0.01093 (9)0.01809 (12)0.00210 (8)0.00700 (9)0.00104 (8)
C10.01043 (11)0.01299 (11)0.01549 (14)0.00227 (9)0.00521 (10)0.00355 (11)
C160.01678 (10)0.01322 (9)0.01308 (11)0.00126 (8)0.00373 (8)0.00237 (8)
C90.01196 (10)0.02016 (11)0.01755 (13)0.00344 (8)0.00006 (8)0.00038 (9)
C110.01412 (13)0.01497 (13)0.0263 (2)0.00465 (11)0.00306 (13)0.00258 (13)
C80.01084 (10)0.02260 (12)0.02239 (14)0.00371 (9)0.00378 (9)0.00076 (10)
C180.01967 (16)0.02324 (17)0.0377 (3)0.00933 (15)0.01721 (18)0.00786 (18)
Geometric parameters (Å, º) top
C2—C31.5338 (4)C14—C151.3941 (5)
C3—C41.5019 (5)C14—H140.980 (7)
C4—C21.5421 (4)C5—C101.3999 (4)
C2—C11.4992 (4)C10—C91.3970 (4)
O1—C11.3395 (5)C10—H100.981 (6)
O2—C11.2150 (5)C7—C81.3948 (4)
C3—C111.5096 (5)C7—H70.980 (7)
C3—H31.015 (8)C15—C161.3948 (4)
C12—C131.3984 (4)C15—H150.991 (6)
C12—C21.4989 (4)C16—H160.974 (7)
C12—C171.3961 (4)C9—C81.3915 (5)
C4—C51.4880 (4)C9—H90.977 (7)
C4—H41.011 (8)C11—H11A0.939 (9)
C13—C141.3939 (4)C11—H11B0.966 (10)
C13—H130.978 (7)C11—H11C0.962 (9)
C6—C51.4026 (4)C8—H80.979 (7)
C6—C71.3933 (4)C18—H18A0.960 (11)
C6—H60.985 (6)C18—H18B0.940 (11)
C17—C161.3980 (4)C18—H18C0.951 (10)
C17—H170.973 (6)
C2—C4—C360.50 (2)C3—C2—C12119.41 (3)
C3—C2—C458.46 (2)C3—C2—C1115.91 (3)
C4—C3—C261.05 (2)C12—C2—C1115.92 (3)
C4—C3—C11121.26 (3)C12—C17—C16120.39 (2)
C4—C3—H3114.1 (5)C13—C14—C15119.67 (2)
C2—C3—C11124.29 (3)C4—C5—C6123.32 (3)
C2—C3—H3111.3 (6)C4—C5—C10118.28 (3)
C11—C3—H3114.4 (6)C6—C5—C10118.24 (2)
C13—C12—C2119.66 (3)C5—C10—C9121.13 (3)
C13—C12—C17118.96 (2)C6—C7—C8120.27 (3)
C2—C12—C17121.39 (2)C6—C7—H7120.0 (5)
C3—C4—C5122.63 (3)C14—C15—C16119.94 (2)
C3—C4—H4115.6 (6)C1—O1—C18115.32 (5)
C5—C4—H4112.9 (6)O1—C1—O2122.61 (4)
C12—C13—C14120.95 (3)O1—C1—C2111.95 (3)
C12—C13—H13118.4 (4)O2—C1—C2125.42 (4)
C14—C13—H13120.7 (4)C17—C16—C15120.07 (3)
C5—C6—C7120.79 (3)C10—C9—C8119.90 (3)
C5—C6—H6119.2 (4)C7—C8—C9119.67 (2)
C7—C6—H6120.0 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O21.01 (1)2.45 (1)2.8877 (6)105 (1)
C11—H11A···O20.94 (1)2.49 (1)3.1200 (7)125 (1)
C17—H17···O2i0.97 (1)2.53 (1)3.4020 (6)149 (1)
Symmetry code: (i) x, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC18H18O2
Mr266.32
Crystal system, space groupMonoclinic, P21/c
Temperature (K)173
a, b, c (Å)16.9049 (7), 7.4168 (3), 11.7545 (5)
β (°) 102.869 (2)
V3)1436.76 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.74 × 0.54 × 0.26
Data collection
DiffractometerBruker APEXII area-detector
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Bruker, 2008)
Tmin, Tmax0.829, 1.000
No. of measured, independent and
observed [I > 3σ(I)] reflections
52859, 11659, 9819
Rint0.038
(sin θ/λ)max1)0.993
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.027, 1.60
No. of reflections9819
No. of parameters199
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.18, 0.34

Computer programs: APEX2 (Bruker, 2011), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), XD2006 (Volkov et al., 2006), OLEX2 (Dolomanov et al., 2009) and AIMAII (Keith, 2012).

Analysis of the electron density at the critical points between C atoms C2—C3, C3—C4 and C4—C2. top
PropertyX-ray refinementGaussian wavefunction
C2—C3
Bond length (Å)1.5338 (4)1.5348
ρ(r) (e- Å-3)1.481.54
Bond path (Å)1.5381.537
Bond path angle (°) C4—C2—C367.6967.27
Ellipticity, ε0.6090.529
Δ2ρ(r) (e- Å-5)-4.589-2.875
λ1-10.157-10.679
λ2-6.31-6.99
λ311.887.39
C3—C4
Bond distance (Å)1.5019 (4)1.5016
ρ(r) (e- Å-3)1.621.67
Bond path (Å)1.5061.504
Bond path angle (°) C2—C3—C467.6967.27
Ellipticity, ε0.6090.529
Δ2ρ(r) (e- Å-5)-4.589-2.875
λ1-10.157-10.679
λ2-6.31-6.99
λ311.887.39
C4—C2
Bond distance (Å)1.5421 (4)1.54233
ρ(r) (e- Å-3)1.461.51
Bond path (Å)1.5451.544
Bond path angle (°) C3—C4—C263.8563.38
Ellipticity, ε0.670.57
Δ2ρ(r) (e- Å-5)-3.94-2.74
λ1-9.96-10.53
λ2-5.95-6.69
λ311.977.43
Selected geometric parameters (Å, º) top
C2—C31.5338 (4)C14—C151.3941 (5)
C3—C41.5019 (5)C14—H140.980 (7)
C4—C21.5421 (4)C5—C101.3999 (4)
C2—C11.4992 (4)C10—C91.3970 (4)
O1—C11.3395 (5)C10—H100.981 (6)
O2—C11.2150 (5)C7—C81.3948 (4)
C3—C111.5096 (5)C7—H70.980 (7)
C3—H31.015 (8)C15—C161.3948 (4)
C12—C131.3984 (4)C15—H150.991 (6)
C12—C21.4989 (4)C16—H160.974 (7)
C12—C171.3961 (4)C9—C81.3915 (5)
C4—C51.4880 (4)C9—H90.977 (7)
C4—H41.011 (8)C11—H11A0.939 (9)
C13—C141.3939 (4)C11—H11B0.966 (10)
C13—H130.978 (7)C11—H11C0.962 (9)
C6—C51.4026 (4)C8—H80.979 (7)
C6—C71.3933 (4)C18—H18A0.960 (11)
C6—H60.985 (6)C18—H18B0.940 (11)
C17—C161.3980 (4)C18—H18C0.951 (10)
C17—H170.973 (6)
C2—C4—C360.50 (2)C3—C2—C12119.41 (3)
C3—C2—C458.46 (2)C3—C2—C1115.91 (3)
C4—C3—C261.05 (2)C12—C2—C1115.92 (3)
C4—C3—C11121.26 (3)C12—C17—C16120.39 (2)
C4—C3—H3114.1 (5)C13—C14—C15119.67 (2)
C2—C3—C11124.29 (3)C4—C5—C6123.32 (3)
C2—C3—H3111.3 (6)C4—C5—C10118.28 (3)
C11—C3—H3114.4 (6)C6—C5—C10118.24 (2)
C13—C12—C2119.66 (3)C5—C10—C9121.13 (3)
C13—C12—C17118.96 (2)C6—C7—C8120.27 (3)
C2—C12—C17121.39 (2)C6—C7—H7120.0 (5)
C3—C4—C5122.63 (3)C14—C15—C16119.94 (2)
C3—C4—H4115.6 (6)C1—O1—C18115.32 (5)
C5—C4—H4112.9 (6)O1—C1—O2122.61 (4)
C12—C13—C14120.95 (3)O1—C1—C2111.95 (3)
C12—C13—H13118.4 (4)O2—C1—C2125.42 (4)
C14—C13—H13120.7 (4)C17—C16—C15120.07 (3)
C5—C6—C7120.79 (3)C10—C9—C8119.90 (3)
C5—C6—H6119.2 (4)C7—C8—C9119.67 (2)
C7—C6—H6120.0 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4···O21.011 (9)2.453 (11)2.8877 (6)105.2 (6)
C11—H11A···O20.939 (11)2.485 (9)3.1200 (7)125.0 (8)
C17—H17···O2i0.972 (7)2.530 (6)3.4020 (6)149.2 (5)
Symmetry code: (i) x, y+3/2, z1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds