Racemic (1,4-dioxan-2-yl)diphenylmethanol

Article abstract of DOI:10.1107/S0108270111008419

The title compound, C₁₇H₁₈O₃, prepared by microwave irradiation of benzophenone and dioxane, crystallizes in a racemic mixture that forms onedimensional chains via strong hydrogen bonding of the hydroxy group to the adjacent symmetry-generated 1,4-dioxan-2-yl group; the O - H...O distance is 1.99 (3) A and the O - H...O angle is 160 (2)°.

Full text of DOI:10.1107/S0108270111008419

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
Racemic (1,4-dioxan-2-yl)diphenyl-
methanol
Tomi Hsiao, Robert M. Buchanan and Mark S. Mashuta*
Department of Chemistry, University of Louisville, Louisville, KY 40292, USA
Correspondence e-mail: msmashuta.xray@louisville.edu
Received 11 February 2011
Accepted 5 March 2011
Online 11 March 2011
Figure 1
A view of the S enantiomer of (I), showing 50% probability displacement
ellipsoids.
The title compound, C17H18O3, prepared by microwave
irradiation of benzophenone and dioxane, crystallizes in a
racemic mixture that forms one-dimensional chains via strong
hydrogen bonding of the hydroxy group to the adjacent
symmetry-generated 1,4-dioxan-2-yl group; the O—Hꢀ ꢀ ꢀO
crystallizes with one molecule in the asymmetric unit in the
noncentrosymmetric space group Cc, which was confirmed
using the program PLATON (routines ADDSYM and
NEWSYM; Spek, 2009). Two enantiomeric forms are present
and the structure of the S form is shown in Fig. 1. The Hooft
analysis parameters P2(true) = 1.000, P3(true) = 1.000,
P3(false) = 0.000 and Hooft y = 0.14 (7) obtained from
PLATON were used to assign the absolute configuration
(Hooft et al., 2008).
The C—C and C—O bond distances and associated bond
angles around atoms C1 [average = 109.04 (17)ꢁ] and C2
[average = 109.48 (14)ꢁ] are consistent with sp3 hybridization
(Table 1). The C—C and C—O distances, and respective
angles, for the phenyl and dioxanyl groups are normal. The
phenyl rings adopt a twisted arrangement, minimizing ring-to-
ring and Hꢀ ꢀ ꢀH atom interactions, while the dioxanyl group
adopts a distorted-chair conformation.
ꢁ
˚
distance is 1.99 (3) A and the O—Hꢀ ꢀ ꢀO angle is 160 (2) .
Comment
The formation of C—C bonds is an important synthetic step in
organic synthesis, and there are several well known methods
that efficiently promote this bond-formation process. One
frequently used method involves the coupling of carbon
radicals generated during photolysis (Ohkura et al., 2004;
Derk et al., 2008), radiolysis (Burr & Strong, 1959), oxidation
reactions (Beccalli et al., 2007; Yu et al., 2009) and organo-
metallic catalysed reactions (Hartwig, 2008). The known title
compound, (I), was synthesized using microwave irradiation to
promote C—C bond coupling between dioxane and benzo-
phenone, and was isolated as a racemic mixture upon crys-
tallization. (I) has been prepared previously by UV irradiation
1
of benzophenone in dioxane, and characterized by H and
13C NMR and mass spectrometry (Bakar Bin Baba et al., 1985;
Droste et al., 1969). However, to date, no crystal structure of
(I) has been reported.
Figure 2
A packing diagram for (I), showing the intermolecular hydrogen-bonding
The C—C bond coupling between the 2-position C atom of
dioxane and the carbonyl C atom of benzophenone results in
the formation of a stereocenter at atom C2. Compound (I)
interactions between atoms H30A and O2i of adjacent S and R
1
2
enantiomers. [Symmetry code: (i) x, ꢂy + 1, z ꢂ .]
Acta Cryst. (2011). C67, o129–o130
doi:10.1107/S0108270111008419
# 2011 International Union of Crystallography o129

organic compounds
Compound (I) displays intermolecular O—Hꢀ ꢀ ꢀO0
hydrogen bonding between dioxanyl and hydroxy groups
(Desiraju, 1995). A view of the interlinked one-dimensional
hydrogen-bonded chain of molecules of (I), projected along
the crystallographic c axis, is shown in Fig. 2, illustrating the
strong hydrogen-bonding interaction, with dimensions as
listed in Table 2.
Table 1
Selected geometric parameters (A, ).
ꢁ
˚
C1—O3
C1—C12
C1—C6
1.418 (2)
1.530 (3)
1.539 (3)
C1—C2
C2—O1
C2—C3
1.546 (3)
1.417 (2)
1.500 (3)
O3—C1—C12
O3—C1—C6
C12—C1—C6
O3—C1—C2
C12—C1—C2
C6—C1—C2
106.56 (16)
111.66 (17)
107.32 (16)
108.80 (17)
111.38 (18)
111.05 (16)
O1—C2—C3
O1—C2—C1
C3—C2—C1
O1—C2—H2
C3—C2—H2
C1—C2—H2
110.31 (17)
107.07 (17)
114.93 (18)
106.8 (12)
107.4 (12)
110.1 (11)
Experimental
The synthesis of (I) and 1,1,2,2-tetraphenylethane-1,2-diol from
dioxane and benzophenone has been described in the literature
(Droste et al., 1969). Irradition of a dioxane solution containing
benzophenone for 20 h with a mercury arc lamp (340 nm) and a
nickel sulfate aqueous filter produces (I) and 1,1,2,2-tetraphenyl-
ethane-1,2-diol as the major products. We have prepared (I) by an
alternative method using microwave irradiation by the following
procedure. Benzophenone (0.55 mmol) was placed in a 125 ml
Erlenmeyer flask containing Zn dust (1.02 mmol), ammonium
formate (3.96 mmol) and dioxane (5 ml). The reactants were irra-
diated in a domestic microwave oven (70% power, 1.05 kW) with a
heat sink for three periods of 5 min, yielding an amber-colored
solution. Excess dioxane was added, the Zn dust was removed by
filtration and the filtrate was concentrated by rotoevaporation.
Removal of the solvent yielded an amber-colored oil and white
crystals. The white solid was the major product. It was easily removed
by filtration with a cold methanol wash and was determined to be
1,1,2,2-tetraphenylethane-1,2-diol (m.p. 443–444 K). The amber-
colored oil was determined to be a mixture of (I) and several
unknown by-products. It was purified by chromatography using a
5:2:1 solution of ethyl acetate–toluene–methanol on silica gel. Com-
pound (I) was crystallized by slow diffusion of toluene, yielding
colorless crystals [m.p. 387 K; literature value 388 K (Bakar Bin Baba
Table 2
Hydrogen-bond geometry (A, ).
ꢁ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
1.99 (3)
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O3—H30Aꢀ ꢀ ꢀO2i
Symmetry code: (i) x; ꢂy þ 1; z ꢂ .
0.86 (3)
2.813 (2)
160 (2)
1
2
tion: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to
solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to
refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
SHELXTL (Sheldrick, 2008); software used to prepare material for
publication: ORTEP-3 (Farrugia, 1997), PLATON (Spek, 2009) and
publCIF (Westrip, 2010).
MSM thanks the Department of Energy (grant No.
DEFG02-08CH11538), and the Kentucky Research Challenge
Trust Fund for upgrade of our X-ray facilities. RMB thanks
the Kentucky Science and Engineering Foundation (grant No.
KSEF-275-RDE-003) for financial support of this research.
1
et al., 1985)]. The H NMR (CDCl3) spectrum corresponds to that
reported in the literature. MALDI–TOF MS: [M + H]+ 271 m/z.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OV3002). Services for accessing these data are
described at the back of the journal.
Crystal data
3
˚
C17H18O3
V = 1398.59 (14) A
Z = 4
Cu Kꢁ radiation
ꢂ = 0.70 mmꢂ1
T = 100 K
Mr = 270.31
Monoclinic, Cc
a = 12.9108 (8) A
References
˚
˚
b = 10.5408 (5) A
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Beccalli, E. M., Broggini, G., Martinelli, M. & Sottocornola, S. (2007). Chem.
Rev. 107, 5318–5365.
˚
c = 10.3022 (7) A
0.37 ꢃ 0.11 ꢃ 0.04 mm
ꢀ = 94.016 (6)ꢁ
Data collection
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Oxford GEMINI CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2010)
4014 measured reflections
2064 independent reflections
1805 reflections with I > 2ꢃ(I)
Rint = 0.015
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Refinement
R[F2 > 2ꢃ(F2)] = 0.030
wR(F2) = 0.070
S = 1.04
2064 reflections
251 parameters
All H-atom parameters refined
Áꢄmax = 0.18 e A
ꢂ3
˚
ꢂ3
˚
Áꢄmin = ꢂ0.14 e A
Absolute structure: Hooft et al.
(2008), with 723 Friedel pairs
Flack parameter: ꢂ0.2 (2)
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell
refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduc-
ꢄ
o130 Hsiao et al. C17H18O3
Acta Cryst. (2011). C67, o129–o130