Molecular structure of PhOCH2CH(OH)CH2OPH

Article abstract of DOI:10.1023/A:1009594732642

The molecular structure of PhOCH₂CH(OH)CH₂OPh has been determined. The C - O -C - C - C - O - C backbone adopts an anti-anti-anti-anti conformation. Inter-molecular O - H ... O hydrogen-bonding results in dimeric units which stack into zig-zag tapes. Crystal data: orthorhombic, Pbca, a = 10.383(1), b = 8.0532(0), c = 31.295(3) A, V = 2616.8(3) A³, and Z = 8.

Full text of DOI:10.1023/A:1009594732642

Journal of Chemical Crystallography, Vol. 29, No. 2, 1999
Note
Molecular structure of PhOCH2CH(OH)CH2OPh
Yoshihiro Koide,(1) Simon G. Bott,(2)* and Andrew R. Barron(1)*
Received November 23, 1998
The molecular structure of PhOCH2CH(OH)CH2OPh has been determined. The CUOU
CUCUCUOUC backbone adopts an anti-anti-anti-anti conformation. Inter-molecular
OUH иии O hydrogen-bonding results in dimeric units which stack into zig-zag tapes. Crystal
3
˚
˚
data: orthorhombic, Pbca, a ϭ 10.383(1), b ϭ 8.0532(0), c ϭ 31.295(3) A, V ϭ 2616.8(3) A ,
and Z ϭ 8.
KEY WORDS: Alcohol; phenyl; ether.
Introduction
noxypropane (II), with phenol or amines (as models
for the functional groups on the carboxylate-alumox-
As part of a study of the formation of inorganic–
anes). All of the model compounds were character-
ized by IR and NMR spectroscopy and mass spec-
trometry.1 In the case of the reaction with phenol the
structure of the product, PhOCH2CH(OH)CH2OPh,
has also been confirmed by X-ray crystallography.
organic hybrid materials, we have investigated the
reaction of chemically functionalized alumina nano-
particles (carboxylate-alumoxanes) with epoxide res-
ins.1 Para-hydroxybenzoic acid or lysine derivatized
alumoxanes are readily prepared from the reaction
of boehmite [Al(O)(OH)]n with the appropriate
acid.2 The surface hydroxides and amines of these
carboxylate-alumoxanes are reacted directly with ep-
oxide resins, such as the diglycidylether of bisphenol-
A (I), to form a new class of hybrid material. In order
to facilitate the structural elucidation of these hybrid
materials we prepared a series of model compounds
by the reaction of a mono-epoxide, 1,2-epoxy-3-phe-
Experimental
A crystal of PhOCH2CH(OH)CH2OPh was
sealed in a glass capillary under argon and mounted
on the goniometer of an Enraf-Nonius CAD-4 auto-
mated diffractometer. Data collection and unit cell
and space group determination were all carried out
in a manner previously described in detail.3 Pertinent
details are given in Table 1. The structure was solved
by direct methods (SIR),4 and the model was refined
using full-matrix least squares techniques. The hy-
droxide hydrogen was located and freely refined. All
(1) Department of Chemistry, Rice University, Houston, Texas
77005.
(2) Department of Chemistry, University of Houston, Houston,
Texas 77204.
* To whom correspondence should be addressed (http://python.
rice.edu/ȁarb/Barron.html).
247
1074-1542/99/0200-0247$16.00/0 1999 Plenum Publishing Corporation

248
Koide, Bott, and Barron
Table 1. Summary of X-Ray Diffraction Data for
nar and adopts a staggered anti-anti-anti-anti confor-
mation, see Fig. 1. The only other planar backbone
has been observed for the bis-sodium 2-carboxychro-
mon-5-yloxy derivative which adopts an anti-anti-
synn-anti conformation.8 Both of these structures
contrast with the conformations observed for the cy-
clic and other non-cyclic compounds, which generally
adopt an anti-gauche-gauche-anti conformation.
The primary level of hierachial architecture11
within the crystal packing of PhOCH2CH(OH)-
CH2OPh consists of inter-molecular hydrogen-
bonded dimers (see Fig. 2). The O(3)иииO(3Ј) distance
PhOCH2CH(OH)CH2OPh
Compound
PhOCH2CH(OH)CH2OPh
CCDC deposit no.
Empirical formula
Mw
CCDC-1003/5496
C15H16O3
244.29
Crystal size, mm
Crystal system
space group
0.17 ϫ 0.31 ϫ 0.72
Orthorhombic
Pbca
˚
a, A
10.383(1)
8.0532(9)
31.295(3)
2616.8(3)
˚
b, A
˚
C, A
3
˚
V, A
Z
8
˚
of 2.89 A is consistent with an OUHиииO interac-
Dcalc, g/cm3
1.240
0.78
tion.12 The formation of simple dimers for PhOCH2-
CH(OH)CH2OPh is in contrast to the sheet or chain
types of inter-molecular hydrogen bonding ordinarily
observed for 1,3-diglycerides in the solid state.7,9,10
The hydrogen bonded dimers resulting packing
leads to a crinkled (zig-zag) tape secondary level of
hierachial architecture.11 It is worth noting that de-
spite the near planar backbone in PhOCH2CH(OH)-
CH2OPh, there appears to be no direct ȏ-stacking of
the aromatic rings, since the phenyl rings are posi-
tioned above the ether linkages of an adjacent mole-
cule. However, the closest O(ether) иии C(Ph) intermolecu-
Ȑ, cmϪ1
temp, K
298
2␪ range, deg
No. collected
No. ind
3.0–50.0
2686
2686
No. obsvd
weighting scheme
R
1081 (FFoF Ͼ 6.0␴FFoF)
wϪ1 ϭ 0.04(FFoF)2 ϩ ␴(FFoF)2
0.0410
0.0546
0.13
Rw
Ϫ3
˚
Largest diff peak, eA
˚
the hydrogen atoms bonded to carbon were placed
in calculated positions [Uiso ϭ 1.3U(C); d(C-H) ϭ 0.95
lar distance [O(1)иииC(54Ј) ϭ 3.64 A] is outside of
13
˚
the sum of their van der Waals radii (3.25 A).
˚
A] for refinement. Neutral-atom scattering factors
were taken from the usual source.5 Refinement of
positional and anisotropic thermal parameters led to
convergence (see Table 1). Atomic parameters (with
esd’s) are given in Table 2 and selected bond lengths
and angles are dispalyed in Table 3.
Table 2. Fractional Atomic Coordinates and Equivalent
2
2
˚
Isotropic Displacement Coefficients (A ϫ 10 ) for
PhOCH2CH(OH)CH2OPh
x
y
z
U(eq)a
O(1)
O(3)
O(5)
C(2)
C(3)
C(4)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
0.4289(2)
0.3787(2)
0.4477(2)
0.3677(3)
0.4207(3)
0.3780(3)
0.4043(3)
0.4846(3)
0.4671(4)
0.3694(4)
0.2910(3)
0.3074(3)
0.4211(3)
0.3338(3)
0.3155(3)
0.3825(3)
0.4699(3)
0.4894(3)
0.3649(3)
0.4795(3)
0.2402(3)
0.2664(4)
0.3162(4)
0.2000(4)
0.3296(4)
0.4050(4)
0.3771(4)
0.2767(4)
0.2026(4)
0.2272(4)
0.1544(4)
0.0267(4)
Ϫ0.0490(5)
Ϫ0.0013(5)
0.1263(4)
0.2035(4)
Ϫ0.11573(6)
Ϫ0.03014(6)
0.03064(6)
Ϫ0.08401(9)
Ϫ0.04147(9)
Ϫ0.00713(9)
Ϫ0.15762(9)
Ϫ0.1871(1)
Ϫ0.2299(1)
Ϫ0.2438(1)
Ϫ0.21464(9)
Ϫ0.17171(9)
0.06742(8)
0.07048(9)
0.1096(1)
5.73(5)
5.85(5)
5.56(5)
4.84(7)
4.54(7)
5.10(7)
4.45(7)
5.58(8)
6.35(9)
6.38(9)
5.80(8)
4.84(7)
4.48(6)
5.37(7)
6.22(8)
5.71(8)
5.34(8)
4.65(7)
Results and discussion
The molecular structure of PhOCH2CH(OH)-
CH2OPh is shown in Fig. 1; selected bond lengths
and angles are given in Table 3. There is a paucity
of structural data on 1,3-diglycerides, and the major-
ity of those reported are cyclic.6 However, a few
examples of simple non-cyclic 1,3-diglycerides
ROCH2CH(OH)CH2ORЈ have been structurally
characterized, including: RuRЈuC(O)C10H20Br,7
sodium
2-carboxychromon-5-yloxy,8
C(O)CH2
SC9H19,9 and RuEt, RЈuC6H4U4UN(H)C(O)
C2H4SMe2ϩ.10 All the bond lengths and angles in
PhOCH2CH(OH)CH2OPh are within the ranges ob-
served for other 1,3-diglycerides.7–10
0.1448(1)
0.14149(9)
0.10317(9)
a Equivalent isotropic U defined as one third of the trace of the
orthogonalized Uij tensor.
The diglyceride CUOUCUCUCUOUC
backbone in PhOCH2CH(OH)CH2OPh is near pla-

PhOCH2CH(OH)CH2OPh
249
˚
Table 3. Selected Bond Lengths (A) and Angles (Њ) for
PhOCH2CH(OH)CH2OPh
O(1)UC(2)
1.421(4)
1.430(4)
1.370(3)
1.492(4)
O(1)UC(11)
O(5)UC(4)
C(2)UC(3)
1.366(3)
1.423(4)
1.495(4)
O(3)UC(3)
O(5)UC(51)
C(3)UC(4)
C(2)UO(1)UC(11)
O(1)UC(2)UC(3)
O(3)UC(3)UC(4)
O(5)UC(4)UC(3)
118.1(2)
107.9(2)
107.9(2)
107.8(2)
C(4)UO(5)UC(51)
O(3)UC(3)UC(2)
C(2)UC(3)UC(4)
118.8(2)
110.8(2)
111.3(2)
Acknowledgments
Financial support for this work is provided by
the Office of Naval Research (ONR) and the Defense
Advanced Research Projects Agency (DARPA).
Fig. 1. The molecular structure of PhOCH2CH(OH)CH2OPh.
Thermal ellipsoids are shown at the 20% level.
Fig. 3. Unit cell diagram of PhOCH2CH(OH)-
CH2OPh viewed along the z-axis showing the stack-
ing of the zig-zag tapes. Hydrogen atoms, except
those bonded to oxygen, are omitted for clarity.
Fig. 2. View of a hydrogen bonded dimer of
PhOCH2CH(OH)CH2OPh.

250
Koide, Bott, and Barron
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