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COMMUNICATIONS
ISSN: 2056-9890
Volume 71| Part 11| November 2015| Pages 1278-1282
https://doi.org/10.1107/S2056989015017752

Crystal structure of 2α-(1,1-di­phenyl­eth­yl)-4-methyl-4α,5α-di­phenyl-1,3-dioxolane: the result of a non-acid pinacol rearrangement

Richard M. Kirchner,a* Peter W. R. Corfield,b Michelle Annabi,a John Regan,a Kevin Speina,a Anthony DiProperzio,a James A. Ciacciob and Joseph F. Capitania‡

aDepartment of Chemistry and Biochemistry, Manhattan College, 4513 Manhattan College Pkwy, Bronx NY 10471, USA, and bDepartment of Chemistry, Fordham University, 441 East Fordham Road, Bronx, NY 10458, USA
*Correspondence e-mail: richard.kirchner@manhattan.edu

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 2 September 2015; accepted 21 September 2015; online 3 October 2015)

The title compound, C30H28O2, was obtained during recrystallization of (±)-1,2-diphenyl-1,2-propane­diol in 1-butanol, from an unexpected non-acid-catalyzed pinacol rearrangement followed by acetal formation of the newly formed aldehyde with the diol. The tri-substituted dioxolane ring has a twist conformation on the C—O bond opposite the methyl-substituted C atom. There is an intra­molecular C—H⋯π inter­action present involving one of the di­phenyl­ethyl rings and an H atom of the phenyl ring in position 4 of the dioxolane ring. In the crystal, mol­ecules are linked by weak C—H⋯O hydrogen bonds, forming chains along [001]. The chains are linked by a second C—H⋯π inter­action, forming sheets parallel to the bc plane.

CCDC reference: 1426279

Similar articles

1. Chemical context

The pinacol rearrangement is a well-documented reaction (Collins, 1960[Collins, C. J. (1960). Q. Rev. Chem. Soc. 14, 357-377.]) that converts substituted 1,2-diols into aldehydes or ketones (pinacolone derivatives), usually with the aid of mineral or Lewis acid catalysis. In the present work, a pinacol rearrangement has occurred during recrystallization in the absence of a catalyst, thus transforming the intended object of our study (1), into the pinacol rearrangement aldehyde (3), which then reacts (by acetal formation) with another mol­ecule of (1) to form the unexpected product (2) presented in this paper, as shown in the scheme below.

[Scheme 1]

The pseudo-equatorial orientation of the di­phenyl­ethane group at C2 likely follows from thermodynamic control during the acetalization step. For the reaction conditions of our recrystallization, the acetalization step must proceed faster than pinacol rearrangement. A similar reaction has been described by Ciminale et al. (2005[Ciminale, F., Lopez, L., Nacci, A., D'Accolti, L. & Vitale, F. (2005). Eur. J. Org. Chem. pp. 1597-1603.]). There are very few other reports of the pinacol rearrangement occurring in the absence of catalysts: for example, the thermal rearrangement of pinacol to pinacolone in supercritical H2O (Ikushima et al., 2000[Ikushima, Y., Hatakeda, K., Sato, O., Yokoyama, T. & Arai, M. (2000). J. Am. Chem. Soc. 122, 1908-1918.]), the conversion of 1,1,2-tri­phenyl­ethane-1,2-diol to 1,2,2-tri­phenyl­ethan-1-one when heated above its melting point (Collins, 1960[Collins, C. J. (1960). Q. Rev. Chem. Soc. 14, 357-377.]), and a vinyl­ogous pinacol rearrangement thermally induced in the solid state (Sekiya et al., 2000[Sekiya, R., Kiyo-oka, K., Imakubo, T. & Kobayashi, K. (2000). J. Am. Chem. Soc. 122, 10282-10288.]).

2. Structural commentary

The mol­ecular structure of the title compound, (2), is illus­trated in Fig. 1[link]. The dioxolane five-membered ring has a twist configuration on bond O1—C2, with atoms O1 and C2 at distances of 0.314 (4) and −0.330 (3) Å above and below the plane through atoms O3/C4/C5. The dioxolane ring has bond angles and distances that are within ca 3σ (using the larger s.u. values from the reported structures) of the values found in published X-ray structures (see for example: Rao & Hong Chan, 2014[Rao, W. & Hong Chan, P. W. (2014). Chem. Eur. J. pp. 713-718.]; Jones et al., 1998[Jones, S. R., Selinsky, B. S., Rao, M. N., Zhang, X., Kinney, W. A. & Tham, F. S. (1998). J. Org. Chem. 63, 3786-3789.]). The planes of the two phenyl substituents on the dioxolane ring are inclined to one another by 44.67 (13)°. They and the di­phenyl­ethyl substituent are all cis to one another, in equatorial positions. The phenyl rings of the di­phenyl­ethyl substituent are inclined to one another by 68.16 (12)°. There is an intra­molecular C—H⋯π inter­action present involving one of the di­phenyl­ethyl rings (C91–C96) and an H atom of the phenyl ring in position 4 of the dioxolane ring (Table 1[link]).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 and Cg5 are the centroids of the C51–C56 and C91–C96 rings, respectively.
D—H⋯A D—H H⋯A D⋯A D—H⋯A
C53—H53⋯O3i 0.93 2.61 3.533 (3) 170
C85—H85⋯O1ii 0.93 2.50 3.411 (3) 167
C46—H46⋯Cg5 0.93 2.99 3.894 (3) 164
C86—H86⋯Cg3ii 0.93 2.91 3.799 (2) 160
Symmetry codes: (i) [x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]; (ii) [x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}].
[Figure 1]
Figure 1
The mol­ecular structure of the title compound, (2), with atom labeling. Displacement ellipsoids are drawn at the 50% probability level. One of the H atoms on the methyl group C10 was omitted for clarity.

3. Supra­molecular features

In the crystal, mol­ecules are linked by weak C—H⋯O hydrogen bonds, forming chains along [001]. The chains are linked by C—H⋯O bonds and by type I C—H⋯π inter­actions (Malone et al., 1997[Malone, J. F., Murray, C. M., Charlton, M. H., Docherty, R. & Lavery, A. J. (1997). Faraday Trans. 93, 3429-3436.]), forming sheets parallel to the bc plane (Table 1[link] and Fig. 2[link]).

[Figure 2]
Figure 2
A view in projection along the a axis of the crystal packing of the title compound, (2). The C—H⋯O hydrogen bonds are shown as double dashed lines.

4. Database survey

The Cambridge Structural Database (Version 5.36, last update February 2015; Groom & Allen 2014[Groom, C. R. & Allen, F. H. (2014). Angew. Chem. Int. Ed. 53, 662-671.]) was searched for structures containing the dioxolane ring. As there are several thousand dioxolane entries in the database, we selected only entries with the ring atoms plus one H atom each on C2 and C5, which includes the present structure. This search generated 594 hits, with 2227 sets of ring conformational angles that were reduced to 770 after removal of duplicates. There were 28 structures, 4% of the total, that contained near planar dioxolane rings, defined as rings where all torsional angles were less than 16°. Five-membered dioxolane rings have been described as `puckered envelopes', `half-chair' or `twisted'. Arbitrarily broad criteria were used for envelope or twist conformations. Structures were identified as envelope when one torsional angle was less than 10° and at least 10° less than the remaining angles, or twist when two torsional angles were below 20°, with less than 10° difference between them. In this way, all of the remaining structures could be classified as envelope (447 structures, or 58%) or twist (295 structures, or 38%). The envelope flap was most often one of the ring oxygen atoms (309 structures). In the twist structures, the twisted bond was usually either of the O1—C2 type (145 examples), as in the structure described in this paper, or of the O1–C5 type (123 examples). Of the twist structures, there were 39 like the present structure (2), close to an ideal symmetric twist configuration, where the two smallest torsional angles are within 3° of each other.

The wide variety of dioxolane ring conformations found in the structural literature reflects well the conclusion from our own calculations (see: Sections 5 and 6 below) as well as in Willy et al. (1970[Willy, W. E., Binsch, G. & Eliel, E. L. (1970). J. Am. Chem. Soc. 92, 5394-5402.]), that the dioxolane ring is highly flexible.

5. Density functional analysis

A B3LYP/6-311+G(d,p) density functional calculation (Spartan, 2006[Spartan (2006). Spartan '06. Wavefunction, Inc. Irvine CA.]) of the present mol­ecule in the gas phase shows minimum energy for a twist configuration with similar torsional angles to those in the structure presented here. A calculation where H atoms replace phenyl and di­phenyl­ethyl substituents on the dioxolane ring suggests that the large phenyl rings have little effect upon the ring conformation (Table 2[link]).

Table 2
Substituted 1,3-dioxolanes (Å, °)

Dioxolane is the title compound (2). The phenyl and diphenyl substituents are replaced by H atoms in column two, and CH3 groups in column three.
Parameter Ring with H atoms Ring with CH3 groups Dioxolane X-ray Dioxolane
Bond length        
O1—C2 1.41 1.43 1.39 1.406 (2)
C2—O3 1.41 1.43 1.39 1.408 (2)
O3—C4 1.43 1.45 1.42 1.444 (2)
C4—C5 1.55 1.57 1.59 1.577 (2)
C5—O1 1.43 1.45 1.40 1.427 (2)
         
Bond angle        
O1—C2—O3 106.3 105.7 104.4 104.5 (1)
C2—O3—O4 106.3 110.0 108.6 106.9 (1)
O3—C4—C5 104.3 101.3 101.5 102.2 (1)
C4—C5—O1 103.8 101.3 102.9 103.0 (1)
C5—O1—C2 104.5 110.0 105.8 103.4 (1)
         
Torsion angle        
O1—C2—O3—C4 −33.1 −11.8 −35.6 37.59 (2)
C2—O3—C4—C5 13.3 28.1 15.0 −14.28 (2)
O3—C4—C5—O1 10.3 −33.2 10.1 −13.50 (1)
C4—C5—O1—C2 −29.9 28.1 −31.6 35.50 (1)
C5—O1—C2—O3 39.9 −11.8 42.4 −46.21 (2)
         
Distance from plane        
C2⋯O3/C4/C5 −0.31 −0.64 +0.34 −0.330 (3)
O1⋯O3/C4/C5 +0.25 −0.78 −0.24 +0.314 (4)
C4⋯O1/C2/O3   +0.28    
C5⋯O1/C2/O3   −0.28    

6. Conformational analysis of 1,3-dioxolane rings

No organic five-membered ring is exactly planar because flat rings would have eclipsed C—C bonds that can have considerable torsional strain. Five-membered rings are usually identified as envelope or half-chair with more or less distortion. The planar part of the ring is described by a least-squares fit of three or four atoms in the ring, or by the torsional angle formed by four contingent atoms in the ring. When only one of the remaining atoms is a significant distance from the plane, this conformation is described as an `envelope'. The non-planar atom defines the flap of the envelope. The torsional angles of an ideal half-chair configuration have two small angles of a given sign, two medium angles of opposite sign, and a single large angle of the same sign as the first. The Database Survey reveals that any atom in the ring can be the flap atom. When two atoms (one up, the other down) are a significant but different distance from the plane through the other three atoms, the conformation can be described as `distorted envelope'. When two atoms have equal significant distances in opposite directions from the plane, the ring conformation can be described as `twist', as shown in Fig. 3[link]. A full range of conformations from ideal envelope to ideal twist is obtained with various substituents on the ring because the various ring conformations do not differ substanti­ally in conformational energy (Willy et al. 1970[Willy, W. E., Binsch, G. & Eliel, E. L. (1970). J. Am. Chem. Soc. 92, 5394-5402.]).

[Figure 3]
Figure 3
Ideal five-membered ring conformations.

To illustrate the conformational properties of the five-membered 1,3-dioxolane ring of the title compound, some B3LYP/6-311+G(d,p) density functional calculation results (Spartan, 2006[Spartan (2006). Spartan '06. Wavefunction, Inc. Irvine CA.]) are given in Table 2[link]. The atom numbering is shown in Fig. 4[link]. Column two of the table (Ring with H atoms) shows a pattern of dihedral angles similar to the near-perfect twist found in the present crystal structure, shown in column five, where O1—C2 is the twisted bond. Fig. 5[link] above offers two views of the density functional theory (DFT) optimized structure. The pattern shown in column three (Ring with CH3 groups), has a much larger (O3—C4—C5—O1) torsional angle. The calculated conformation is still that of a twist, but the twist bond in this CH3 model is C4—C5, not O1—C2. The best plane through O1—C2—O3 has C4 + 0.28 Å above the plane and C5 − 0.28 Å below the plane, giving the CH3 model an ideal twist conformation. The DFT-optimized CH3-substituted structure is depicted in Fig. 6[link]. Column four of Table 2[link] shows the DFT results for the title compound. The predicted conformation is similar to the conformation found in the crystal structure. The differences between columns four and five are presumably due to packing (inter­molecular) forces present in the X-ray structure. The Spartan DFT calculations do not include inter­molecular forces, but are calculations in the gas phase. Comparing distance and angle values in column two (dioxolane ring with only H atom substituents) to columns four and five (dioxolane rings with phenyl and di­phenyl­ethyl substituents) suggests these larger substituents have little effect upon the ring conformation. Fig. 7[link] views the title compound as a distorted envelope.

[Figure 4]
Figure 4
Atom numbering in the 1,3-dioxolane ring.
[Figure 5]
Figure 5
Perspective views of the dioxolane ring with hydrogen atoms as calculated with Spartan. Left: viewed as a distorted envelope. Right: viewed as twist.
[Figure 6]
Figure 6
Perspective views of dioxolane ring with methyl groups as calculated with Spartan. Left: viewed as distorted envelope. Right: viewed as twist.
[Figure 7]
Figure 7
Perspective view of the X-ray structure of the title compound, (2).

7. Synthesis and crystallization

A sample of (±)-1,2-diphenyl-1,2-propane­diol (Ciaccio et al., 2001[Ciaccio, J. A., Bravo, R. P., Drahus, A. L., Biggins, J. B., Concepcion, R. V. & Cabrera, D. (2001). J. Chem. Educ. 78, 531-533.]) was recrystallized in 1-butanol, as well as 2-butanol and 1-octa­nol. The solutions were mildly heated to obtain saturated solutions, cooled to room temperature and layered over water in an open test tube. In attempts to better characterize the rearrangements that occurred, we also recrystallized the starting material at the reflux temperature of 1-butanol. Thin layer chromatography revealed that the non-acid-catalyzed pinacol rearrangement was substanti­ally complete after 8 h, and that other unknown products were also present. The experimental density of a typical recrystallization product, determined by flotation, is 1.054 g ml−1. The melting point range was 435.9–443.2 K. Redoing the experimental density and melting point with hand-selected crystals with the same morphology as the X-ray data crystal gave values of 1.203 g ml−1 and 445.4–448.4 K, respectively.

The proton NMR spectrum was obtained with a Bruker AVANCE-400 NMR spectrometer using hand-picked crystals having the same morphology as the crystal used for the X-ray study. 1H NMR (400 MHz, CDCl3): δ 7.46 (d, 2H), 7.39 (d, 2H), 7.3–7.2 (m, 6H), 7.0-6.6 (m, 8H), 6.44 (d, 2H), 5.83 (s, 1H), 4.95 (s, 1H), 1.97 (s, 3H), 1.83 (s, 3H).

8. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3[link]. The H atoms were included in calculated positions and treated as riding atoms: C—H = 0.96-0.98 Å with Uiso(H) = 1.5Ueq(C) for methyl H atoms, Ueq(C) for methine H atoms, and 1.2Ueq(C) for other H atoms.

Table 3
Experimental details

Crystal data
Chemical formula C30H28O2
Mr 420.52
Crystal system, space group Monoclinic, P21/c
Temperature (K) 302
a, b, c (Å) 16.720 (3), 9.0056 (9), 16.6747 (12)
β (°) 112.040 (9)
V (Å3) 2327.3 (5)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.07
Crystal size (mm) 0.4 × 0.4 × 0.26
 
Data collection
Diffractometer Enraf–Nonius CAD-4
No. of measured, independent and observed [I > 2σ(I)] reflections 6377, 4547, 2612
Rint 0.025
(sin θ/λ)max (Å−1) 0.616
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.133, 1.03
No. of reflections 4547
No. of parameters 291
H-atom treatment H-atom parameters constrained
Δρmax, Δρmin (e Å−3) 0.16, −0.18
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994[Enraf-Nonius (1994). CAD-4 EXPRESS. Enraf-Nonius, Delft, The Netherlands.]), SUPERFLIP (Palatinus & Chapuis, 2007[Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790.]), SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]). Data reduction followed procedures in Corfield et al. (1973[Corfield, P. W. R., Dabrowiak, J. C. & Gore, E. S. (1973). Inorg. Chem. 12, 1734-1740.]) and data were averaged with a local version of SORTAV (Blessing, 1989[Blessing, R. H. (1989). J. Appl. Cryst. 22, 396-397.]),

Supporting information

CCDC reference: 1426279

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989015017752/su5202sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015017752/su5202Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015017752/su5202Isup3.cml

checkCIF report


Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: Data reduction followed procedures in Corfield et al. (1973); Data were averaged with a local version of SORTAV (Blessing, 1989); program(s) used to solve structure: Superflip (Palatinus & Chapuis, 2007); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

2-(1,1-Diphenylethyl)-4-methyl-4,5-diphenyl-1,3-dioxolane top
Crystal data top
C30H28O2F(000) = 896
Mr = 420.52Dx = 1.200 Mg m−3
Monoclinic, P21/cMelting point = 436–443 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 16.720 (3) ÅCell parameters from 25 reflections
b = 9.0056 (9) Åθ = 4.5–10.1°
c = 16.6747 (12) ŵ = 0.07 mm−1
β = 112.040 (9)°T = 302 K
V = 2327.3 (5) Å3Block, colourless
Z = 40.4 × 0.4 × 0.26 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.025
Radiation source: fine-focus sealed tubeθmax = 26.0°, θmin = 2.5°
Graphite monochromatorh = −20→19
θ/2θ scansk = 0→11
6377 measured reflectionsl = 0→20
4547 independent reflections3 standard reflections every 180 min
2612 reflections with I > 2σ(I) intensity decay: 3.1(8)
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)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.020P)2 + 0.5P]
where P = (Fo2 + 2Fc2)/3
4547 reflections(Δ/σ)max < 0.001
291 parametersΔρmax = 0.16 e Å−3
0 restraintsΔρmin = −0.18 e Å−3
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. In the monoclinic unit cell, the a and c axes are of very similar lengths, so that before data collection commenced, it was important to check that the Laue symmetry was indeed 2/m and not mmm. This was accomplished by temporarily transforming the cell to orthorhombic axes, and collecting all 8 forms of the (orthorhombic) 111 and 222 reflections. In each case, the 8 forms clearly split into two different sets of four, verifying the monoclinic symmetry.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.18420 (9)0.57319 (14)0.10104 (8)0.0484 (4)
O30.19021 (8)0.39714 (14)0.00987 (8)0.0419 (3)
C20.15272 (14)0.5361 (2)0.01270 (12)0.0416 (5)
H20.08990.5249−0.00830.042*
C40.19172 (13)0.3148 (2)0.08470 (12)0.0419 (5)
C410.27953 (14)0.2435 (2)0.12749 (12)0.0448 (5)
C420.29066 (18)0.1231 (3)0.18187 (15)0.0669 (7)
H420.24300.08220.18970.080*
C430.3712 (2)0.0626 (3)0.22479 (17)0.0879 (9)
H430.3775−0.01860.26120.105*
C440.4421 (2)0.1213 (4)0.21416 (18)0.0874 (9)
H440.49660.08100.24350.105*
C450.43208 (17)0.2395 (3)0.16012 (17)0.0770 (8)
H450.47990.27900.15200.092*
C460.35148 (15)0.3013 (3)0.11716 (14)0.0586 (6)
H460.34580.38260.08100.070*
C50.17302 (14)0.4396 (2)0.14164 (12)0.0441 (5)
H50.11230.43250.13480.044*
C510.22718 (15)0.4399 (2)0.23635 (12)0.0459 (5)
C520.19966 (18)0.3615 (3)0.29192 (14)0.0636 (7)
H520.14660.31340.27070.076*
C530.2504 (2)0.3536 (3)0.37949 (16)0.0801 (8)
H530.23210.29780.41640.096*
C540.3268 (2)0.4272 (3)0.41131 (16)0.0814 (9)
H540.36050.42280.47010.098*
C550.35420 (18)0.5080 (3)0.35694 (16)0.0758 (8)
H550.40630.55910.37900.091*
C560.30502 (16)0.5139 (3)0.26954 (14)0.0588 (6)
H560.32440.56800.23290.071*
C60.17518 (13)0.6541 (2)−0.04152 (11)0.0386 (5)
C70.13530 (15)0.8014 (2)−0.02620 (14)0.0543 (6)
H7A0.15140.8808−0.05550.081*
H7B0.15620.82220.03470.081*
H7C0.07360.7926−0.04830.081*
C810.13165 (12)0.6192 (2)−0.13860 (11)0.0373 (5)
C820.07434 (14)0.5033 (2)−0.17192 (13)0.0514 (6)
H820.06360.4371−0.13440.062*
C830.03285 (15)0.4846 (3)−0.26028 (14)0.0610 (6)
H83−0.00600.4069−0.28140.073*
C840.04836 (15)0.5791 (3)−0.31673 (14)0.0560 (6)
H840.01990.5667−0.37610.067*
C850.10630 (15)0.6922 (2)−0.28491 (13)0.0554 (6)
H850.11820.7559−0.32290.066*
C860.14699 (14)0.7122 (2)−0.19714 (12)0.0478 (5)
H860.18580.7903−0.17670.057*
C910.27312 (13)0.6670 (2)−0.01420 (12)0.0417 (5)
C920.31673 (14)0.5900 (2)−0.05657 (14)0.0518 (6)
H920.28620.5266−0.10170.062*
C930.40453 (15)0.6047 (3)−0.03367 (16)0.0679 (7)
H930.43220.5522−0.06380.082*
C940.45124 (17)0.6955 (3)0.03284 (19)0.0790 (8)
H940.51040.70640.04760.095*
C950.41022 (19)0.7700 (3)0.07731 (18)0.0783 (8)
H950.44190.83000.12370.094*
C960.32217 (16)0.7572 (3)0.05420 (14)0.0599 (6)
H960.29520.80990.08490.072*
C100.11855 (16)0.2027 (3)0.05553 (15)0.0652 (7)
H10A0.06600.25160.02050.098*
H10B0.11180.15960.10530.098*
H10C0.13160.12590.02230.098*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0752 (10)0.0384 (8)0.0376 (8)0.0104 (7)0.0280 (7)0.0030 (6)
O30.0587 (9)0.0362 (7)0.0341 (7)0.0042 (7)0.0212 (6)0.0009 (6)
C20.0501 (12)0.0423 (11)0.0353 (11)0.0070 (10)0.0192 (9)0.0005 (9)
C40.0543 (13)0.0391 (11)0.0353 (10)−0.0009 (10)0.0201 (9)0.0035 (9)
C410.0597 (14)0.0408 (11)0.0351 (10)0.0052 (11)0.0192 (10)−0.0053 (9)
C420.0881 (19)0.0587 (15)0.0575 (14)0.0193 (14)0.0313 (14)0.0118 (13)
C430.116 (3)0.081 (2)0.0603 (17)0.043 (2)0.0258 (18)0.0202 (15)
C440.080 (2)0.099 (2)0.0642 (17)0.041 (2)0.0058 (16)−0.0043 (17)
C450.0579 (17)0.093 (2)0.0720 (17)0.0099 (16)0.0146 (14)−0.0103 (17)
C460.0570 (16)0.0611 (15)0.0532 (13)0.0058 (13)0.0156 (12)−0.0017 (12)
C50.0502 (12)0.0476 (12)0.0418 (11)0.0040 (10)0.0256 (10)0.0055 (10)
C510.0666 (15)0.0406 (11)0.0386 (11)0.0077 (11)0.0289 (11)0.0003 (10)
C520.0938 (19)0.0587 (15)0.0499 (14)−0.0016 (14)0.0401 (13)0.0036 (12)
C530.133 (3)0.0688 (17)0.0516 (15)0.0109 (19)0.0500 (17)0.0131 (14)
C540.118 (3)0.0799 (19)0.0395 (14)0.0189 (19)0.0215 (16)0.0017 (14)
C550.0838 (19)0.0815 (19)0.0527 (16)0.0003 (16)0.0148 (14)−0.0081 (14)
C560.0742 (17)0.0582 (14)0.0469 (13)0.0010 (13)0.0261 (12)0.0010 (11)
C60.0482 (12)0.0341 (10)0.0358 (10)0.0042 (9)0.0185 (9)0.0009 (8)
C70.0690 (15)0.0445 (12)0.0512 (13)0.0141 (11)0.0246 (11)0.0017 (10)
C810.0391 (11)0.0370 (10)0.0376 (10)0.0061 (9)0.0166 (9)0.0044 (9)
C820.0552 (13)0.0549 (13)0.0423 (12)−0.0080 (12)0.0163 (10)0.0081 (11)
C830.0616 (15)0.0645 (15)0.0467 (13)−0.0164 (12)0.0086 (11)−0.0014 (12)
C840.0629 (15)0.0630 (15)0.0364 (11)0.0050 (13)0.0122 (11)0.0030 (11)
C850.0750 (16)0.0526 (14)0.0432 (12)0.0056 (13)0.0275 (12)0.0123 (11)
C860.0585 (14)0.0432 (12)0.0450 (12)−0.0043 (11)0.0231 (10)0.0027 (10)
C910.0507 (13)0.0354 (10)0.0372 (10)0.0011 (10)0.0143 (9)0.0040 (9)
C920.0471 (14)0.0550 (13)0.0491 (12)0.0028 (11)0.0131 (10)−0.0005 (11)
C930.0479 (15)0.0834 (18)0.0709 (16)0.0079 (14)0.0205 (13)0.0019 (15)
C940.0451 (15)0.084 (2)0.093 (2)−0.0030 (15)0.0084 (15)0.0103 (17)
C950.070 (2)0.0670 (17)0.0729 (17)−0.0140 (15)−0.0023 (15)−0.0068 (15)
C960.0648 (16)0.0535 (14)0.0530 (14)−0.0017 (12)0.0125 (12)−0.0055 (11)
C100.0717 (17)0.0556 (14)0.0643 (15)−0.0153 (13)0.0210 (13)0.0030 (12)
Geometric parameters (Å, º) top
O1—C21.406 (2)C56—H560.9300
O1—C51.427 (2)C6—C911.531 (3)
O3—C21.408 (2)C6—C811.538 (3)
O3—C41.444 (2)C6—C71.549 (3)
C2—C61.531 (3)C7—H7A0.9600
C2—H20.9800C7—H7B0.9600
C4—C411.513 (3)C7—H7C0.9600
C4—C101.519 (3)C81—C861.381 (3)
C4—C51.577 (3)C81—C821.385 (3)
C41—C421.381 (3)C82—C831.383 (3)
C41—C461.379 (3)C82—H820.9300
C42—C431.379 (4)C83—C841.364 (3)
C42—H420.9300C83—H830.9300
C43—C441.369 (4)C84—C851.368 (3)
C43—H430.9300C84—H840.9300
C44—C451.364 (4)C85—C861.375 (3)
C44—H440.9300C85—H850.9300
C45—C461.384 (3)C86—H860.9300
C45—H450.9300C91—C921.378 (3)
C46—H460.9300C91—C961.390 (3)
C5—C511.497 (3)C92—C931.378 (3)
C5—H50.9800C92—H920.9300
C51—C521.374 (3)C93—C941.363 (4)
C51—C561.380 (3)C93—H930.9300
C52—C531.388 (3)C94—C951.361 (4)
C52—H520.9300C94—H940.9300
C53—C541.358 (4)C95—C961.379 (3)
C53—H530.9300C95—H950.9300
C54—C551.368 (4)C96—H960.9300
C54—H540.9300C10—H10A0.9600
C55—C561.380 (3)C10—H10B0.9600
C55—H550.9300C10—H10C0.9600
C2—O1—C5103.44 (14)C51—C56—H56119.9
C2—O3—C4106.93 (13)C2—C6—C91110.44 (15)
O1—C2—O3104.48 (14)C2—C6—C81110.85 (15)
O1—C2—C6112.05 (16)C91—C6—C81111.09 (15)
O3—C2—C6112.72 (15)C2—C6—C7106.33 (15)
O1—C2—H2109.2C91—C6—C7111.39 (16)
O3—C2—H2109.2C81—C6—C7106.59 (15)
C6—C2—H2109.2C6—C7—H7A109.5
O3—C4—C41108.94 (15)C6—C7—H7B109.5
O3—C4—C10108.30 (16)H7A—C7—H7B109.5
C41—C4—C10113.07 (17)C6—C7—H7C109.5
O3—C4—C5102.18 (14)H7A—C7—H7C109.5
C41—C4—C5113.25 (16)H7B—C7—H7C109.5
C10—C4—C5110.42 (17)C86—C81—C82117.24 (18)
C42—C41—C46118.0 (2)C86—C81—C6118.70 (18)
C42—C41—C4120.7 (2)C82—C81—C6124.00 (17)
C46—C41—C4121.23 (19)C83—C82—C81120.9 (2)
C43—C42—C41121.1 (3)C83—C82—H82119.5
C43—C42—H42119.5C81—C82—H82119.5
C41—C42—H42119.5C84—C83—C82120.7 (2)
C44—C43—C42120.3 (3)C84—C83—H83119.7
C44—C43—H43119.8C82—C83—H83119.7
C42—C43—H43119.8C83—C84—C85119.1 (2)
C45—C44—C43119.3 (3)C83—C84—H84120.4
C45—C44—H44120.3C85—C84—H84120.4
C43—C44—H44120.3C84—C85—C86120.4 (2)
C44—C45—C46120.7 (3)C84—C85—H85119.8
C44—C45—H45119.6C86—C85—H85119.8
C46—C45—H45119.6C85—C86—C81121.6 (2)
C41—C46—C45120.6 (2)C85—C86—H86119.2
C41—C46—H46119.7C81—C86—H86119.2
C45—C46—H46119.7C92—C91—C96116.9 (2)
O1—C5—C51111.34 (17)C92—C91—C6121.47 (17)
O1—C5—C4102.98 (14)C96—C91—C6121.64 (19)
C51—C5—C4117.29 (17)C91—C92—C93121.6 (2)
O1—C5—H5108.3C91—C92—H92119.2
C51—C5—H5108.3C93—C92—H92119.2
C4—C5—H5108.3C94—C93—C92120.6 (2)
C52—C51—C56118.8 (2)C94—C93—H93119.7
C52—C51—C5119.2 (2)C92—C93—H93119.7
C56—C51—C5122.01 (18)C95—C94—C93119.1 (2)
C51—C52—C53120.6 (3)C95—C94—H94120.4
C51—C52—H52119.7C93—C94—H94120.4
C53—C52—H52119.7C94—C95—C96120.7 (2)
C54—C53—C52120.0 (2)C94—C95—H95119.7
C54—C53—H53120.0C96—C95—H95119.7
C52—C53—H53120.0C95—C96—C91121.1 (2)
C53—C54—C55120.0 (2)C95—C96—H96119.4
C53—C54—H54120.0C91—C96—H96119.4
C55—C54—H54120.0C4—C10—H10A109.5
C54—C55—C56120.4 (3)C4—C10—H10B109.5
C54—C55—H55119.8H10A—C10—H10B109.5
C56—C55—H55119.8C4—C10—H10C109.5
C55—C56—C51120.2 (2)H10A—C10—H10C109.5
C55—C56—H56119.9H10B—C10—H10C109.5
O1—C2—O3—C437.54 (19)C4—C5—O1—C235.48 (18)
C2—O3—C4—C5−14.20 (18)C5—O1—C2—O3−46.16 (18)
O3—C4—C5—O1−13.06 (18)
Hydrogen-bond geometry (Å, º) top
Cg3 and Cg5 are the centroids of the C51–C56 and C91–C96 rings, respectively.
D—H···AD—HH···AD···AD—H···A
C53—H53···O3i0.932.613.533 (3)170
C85—H85···O1ii0.932.503.411 (3)167
C46—H46···Cg50.932.993.894 (3)164
C86—H86···Cg3ii0.932.913.799 (2)160
Symmetry codes: (i) x, −y+1/2, z+1/2; (ii) x, −y+3/2, z−1/2.
Substituted 1,3-dioxolanes (Å, °) top
Dioxolane is the title compound (2). The phenyl and diphenyl substituents are replaced by H atoms in column two, and CH3 groups in column three.
ParameterRing with H atomsRing with CH3 groupsDioxolaneX-ray Dioxolane
Bond length
O1—C21.411.431.391.406 (2)
C2—O31.411.431.391.408 (2)
O3—C41.431.451.421.444 (2)
C4—C51.551.571.591.577 (2)
C5—O11.431.451.401.427 (2)
Bond angle
O1—C2—O3106.3105.7104.4104.5 (1)
C2—O3—O4106.3110.0108.6106.9 (1)
O3—C4—C5104.3101.3101.5102.2 (1)
C4—C5—O1103.8101.3102.9103.0 (1)
C5—O1—C2104.5110.0105.8103.4 (1)
Torsion angle
O1—C2—O3—C4-33.1-11.8-35.637.59 (2)
C2—O3—C4—C513.328.115.0-14.28 (2)
O3—C4—C5—O110.3-33.210.1-13.50 (1)
C4—C5—O1—C2-29.928.1-31.635.50 (1)
C5—O1—C2—O339.9-11.842.4-46.21 (2)
Distance from plane
C2···O3/C4/C5-0.31-0.64+0.34-0.330 (3)
O1···O3/C4/C5+0.25-0.78-0.24+0.314 (4)
C4···O1/C2/O3+0.28
C5···O1/C2/O3-0.28
 

Footnotes

‡Michael J. '58 and Aimee Rusinko Kakos Foundation Professor.

Acknowledgements

The authors thank Daniel Schiavone for recrystallization assistance, and also Corine Laplanche and Md Azim for experimental and computational assistance. Anthony DiProperzio gratefully thanks the Michael J. '58 and Aimee Rusinko Kakos Foundation for summer support. Thanks to the Dean of Science at Manhattan College and the Office of the Dean at Fordham University for research support.

References

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ISSN: 2056-9890
Volume 71| Part 11| November 2015| Pages 1278-1282
https://doi.org/10.1107/S2056989015017752
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