Hydrogen-bonding patterns of two dihydroxylactone derivatives

Article abstract of DOI:10.1107/S0108270105000557

In the hydrogen-bonding networks of 8-hydroxy-5-hydroxymethyl-3,6- dioxatricyclo[6.3.1.0^1.5]dodecan-2-one and 5,7-bis(hydroxymethyl)-3, 6-dioxatricyclo[5.3.1.0^1.5]undecan-2-one, both C₁₁H ₁₆O₅, layers

Full text of DOI:10.1107/S0108270105000557

organic compounds
0.312 (2) A, and '2 = 23.3 (3) and 29.8 (4)ꢀ] indicate that
Ê
Acta Crystallographica Section C
Crystal Structure
1
the conformation in (I) is essentially T5 with a contribution
Communications
ISSN 0108-2701
Hydrogen-bonding patterns of two
dihydroxylactone derivatives
a
a
a
Â
Â
Â
M. L. Rodrõguez, M. Febles, C. Perez, N. Perez-
b
b
c
Â
Â
Hernandez, J. D. Martõn and C. Foces-Foces *
a
Â
Instituto de Bioorganica, Universidad de La Laguna±CSIC, Ctra. Vieja de la
Esperanza 2, 38206 La Laguna, Tenerife, Spain, bInstituto de Investigaciones
Â
Â
Quõmicas, CSIC, Americo Vespucio s/n, Isla de la Cartuja, 41092 Sevilla, Spain, and
c
Â
Instituto Rocasolano, CSIC, Departamento de Cristalografõa, Serrano 119, E-28006
Madrid, Spain
Correspondence e-mail: cfoces@iqfr.csic.es
Received 24 November 2004
Accepted 6 January 2005
Online 12 February 2005
from E5, while in (II), the conformation is E5 with a contri-
In the hydrogen-bonding networks of 8-hydroxy-5-hydroxy-
methyl-3,6-dioxatricyclo[6.3.1.01.5]dodecan-2-one and 5,7-bis-
(hydroxymethyl)-3,6-dioxatricyclo[5.3.1.01.5]undecan-2-one,
both C11H16O5, layers and double strands, respectively, lead
to the formation of chains connected by hydroxy-to-hydroxy
contacts, where the hydroxymethyl group, present in both
structures, acts as a donor. The secondary structures differ in
the hydrogen bonding of these chains via the second hydroxy
group, which is involved in hydroxy-to-carbonyl and hydroxy-
to-hydroxy bonds, respectively.
1
1
bution from T5. The cyclohexane ring adopts a C4 chair
conformation, slightly distorted towards a 1H6 half chair in (I)
and towards an E6 envelope in (II) for the sequences C1/C11±
Ê
C8/C12 and C1/C11/C7±C10 [Q = 0.602 (2) and 0.655 (2) A,
ꢁ = 15.4 (2) and 27.1 (2)ꢀ, and ' = 29.1 (5) and 59.1 (4)ꢀ].
The differences in the puckering amplitude could be ascribed
to the different size of the oxacycle bridge; the larger size of
the oxane ring in (I) compared with the oxolane ring in (II) is
associated with the lowest torsion angles in the bonds shared
1
with this ring (Tables 1 and 3). The oxane ring exhibits a C4
3
chair conformation distorted toward a H2 half chair for the
Comment
Ê
atom sequence C1/C12/C8/C7/O6/C5 [Q = 0.561 (2) A, ꢁ =
In the construction of hydrogen-bonded arrays by using
molecular descriptors with unbalanced hydrogen-bond donor/
acceptor ratios, the donor/acceptor imbalance might be
redressed by inclusion of molecules of water (Desiraju, 1990).
Bridged oxacycles in molecules possessing axially oriented
hydroxy/carboxylic acid groups were considered promising
candidates for studying the incorporation of water molecules
into their hydrogen-bond patterns (Carrasco et al., 2001). Our
continuous interest in the study of the hydrated/anhydrous
crystalline packing of such molecules has led us to consider the
synthesis of the hydroxy acid 5,7,7-tris(hydroxymethyl)-6-
oxabicyclo[3.2.1]octane-1-carboxylic acid, (III) (R = OH), a
dihydroxylated homologue of the diethyl derivative (IV) (R =
Me), which adopts a hydrated tubular-shaped structure in the
20.1 (1)ꢀ and ' = 81.4 (5)ꢀ], whereas the oxolane ring adopts a
1
conformation intermediate between T2 and E2 for the C1/
ꢀ
Ê
C11/C7/O6/C5 sequence [q2 = 0.474 (2) A and '2 = 26.9 (2) ].
Another difference between the two structures is that the
hydroxymethyl group attached to atom C5 is gauche- [in (I)]
and trans-oriented [in (II)] with respect to atom C1 (Tables 1
and 3, and Figs. 1 and 2). As far as conventional OÐHÁ Á ÁO
bonds are concerned, two hydrogen-bonding networks are
observed, viz. layers and staircase-ladders, which are closely
related to the relative disposition of the dialcohols in each
Â
solid state (Perez et al., 2000). In the present paper, we report
the crystal structures of the related lactones (I) and (II).
The molecular structures (Figs. 1 and 2) are quite rigid and
contain three structural moieties that will be discussed sepa-
rately. In both compounds and according to the notation of
Giacovazzo et al. (1992), the ꢀ-butyrolactone ring adopts
1
conformations intermediate between T5 half chair and E5
envelope. The ring puckering parameters (Cremer & Pople,
1975) for the atom sequence C1±C5 [q2 = 0.355 (2) and
Figure 1
The molecular structure of (I), shown with 30% probability displacement
ellipsoids.
o138 # 2005 International Union of Crystallography
DOI: 10.1107/S0108270105000557
Acta Cryst. (2005). C61, o138±o142

organic compounds
molecule, as previously observed in 1,3-diols (Nguyen et al.,
2001; Schmittel et al., 2004). In both crystal structures, mole-
cules connected by hydroxy-to-hydroxy bonds form chains,
although the structures differ in the chirality of the compo-
nents within each chain and the linkage between them, as
described below.
The molecules of (I) are linked into a sheet via a combi-
nation of hydroxy-to-hydroxy and hydroxy-to-carbonyl
hydrogen bonds (Table 2). The formation of these sheets can
be described in terms of chains with glide-related molecules
running in the (102) direction (Fig. 3). Hydroxy-to-carbonyl
contacts between chains, related by translation, are respon-
sible for the extension in the a direction, so producing the two-
dimensional network. CÐHÁ Á ÁO contacts exist (Table 2)
within the sheet and between centrosymmetric sheets (dashed
lines in Fig. 4), forming a three-dimensional framework.
In (II), each strand is formed by molecules related only by
translation along a, where the hydroxy group of the
hydroxymethyl group at atom C5 acts as a donor. The second
hydroxy group connects screw-related strands (Fig. 5), giving
rise to the staircase-ladder structure (Fig. 6a), as also observed
in some recently reported 1,3-dialcohol derivatives (Nguyen et
al., 2001). Another type of double-stranded ladder formed by
dialcohols is the step-ladder structure represented schemati-
cally in Fig. 6(b), which has also been observed in the hydroxy
acid analogues of (I) and (II) (Carrasco et al., 2001). In (II), as
pointed out by Nguyen et al. (2001), each hydroxy group
(gauche-oriented) acts as a donor and an acceptor of hydrogen
bonds, showing (i) the preference of this type of ladder
structure to be composed of only one enantiomer and (ii) the
Figure 2
The molecular structure of (II), shown with 30% probability displace-
ment ellipsoids.
Figure 4
A packing diagram of (I), illustrating the disposition of the sheets. Dotted
and dashed lines represent OÐHÁ Á ÁO and CÐHÁ Á ÁO hydrogen bonds,
respectively.
Figure 3
A
combination of hydroxy-to-hydroxy and hydroxy-to-carbonyl contacts.
two-dimensional hydrogen-bonded layer in (I), formed via
a
Figure 5
One-dimensional hydrogen-bonded staircase ladders in (II), formed by
1
1
[Symmetry codes: (i) x 1,
z + 12.]
y, z 12; (ii) 1 + x, y, z; (iii) x + 1,
y,
hydroxy-to-hydroxy bonds. [Symmetry codes: (vi) x 1, y, z; (vii) 12 + x,
2
2
y, 1 z; (viii) x + 1, y, z; (ix) 12 + x, 21 y, 1 z.]
1
2
ꢁ
Â
Acta Cryst. (2005). C61, o138±o142
Rodrõguez et al. C11H16O5 and C11H16O5 o139

organic compounds
twofold screw axis as the most probable symmetry for this type
of ladder.
The OÁ Á ÁO intramolecular (A = O14Á Á ÁO16), interstrand
(B = O16Á Á ÁO14ii) and intrastrand (C = O14Á Á ÁO16i) distances
Ê
(Figs. 5 and 6a) of 5.396 (2), 2.700 (2) and 2.682 (2) A char-
acterizing this ladder are in the upper and lower end of the
range reported by Nguyen et al. (2001). In (I), the intramol-
ecular (O15Á Á ÁO16), interstrand (O16Á Á ÁO13ii) and intra-
strand (O15Á Á ÁO16i) (Fig. 3) distances of 6.466 (3), 2.881 (2)
Ê
and 2.715 (2) A are all larger than the A, B and C distances in
(II). The structures of the two compounds highlight the
C
competition between the OÐHÁ Á ÁOH and OÐHÁ Á ÁO
hydrogen bonds. We also note that (II) is less dense than (I)
(the total packing coef®cients are 0.685 and 0.712) and has a
lower melting point (452±453 versus 464±465 K).
Only weak CÐHÁ Á ÁO interactions (Table 4) connect pairs
of double strands, related by glide planes, along c into a three-
dimensional network of corrugated centrosymmetric sheets
(dashed lines in Fig. 7). The larger displacement parameters
for atoms O3 and O12 in (II) can be associated with the lack of
OÐHÁ Á ÁO contacts for these atoms.
Dihydroxy like hydroxy/carboxylic acid functions are
hydrogen bonded in linear anhydrous strands with two
parallel strands crosslinked through additional hydrogen
bonds. It would also be expected that incorporation of water
molecules into dihydroxy hydogen-bonded networks might
disrupt the dimeric motif, creating single-strand arrays in a
favourable conformation for ring packing. Further extension
of the hydrogen bonding in the perpendicular direction can
lead to the formation of a hydrated tubular-shaped structure
in the solid state (Carrasco et al., 2001). Work toward this end
is in progress.
Figure 7
A packing diagram of (II), illustrating the disposition of the staircase
ladders. Dotted and dashed lines represent OÐHÁ Á ÁO and CÐHÁ Á ÁO
hydrogen bonds, respectively.
Experimental
A solution of lithium diisopropylamide was prepared by dissolving
diisopropylamine (8.3 g, 80 mmol) in anhydrous tetrahydrofuran
(THF, 100 ml), cooling the solution to 233 K in a dry ice±acetone bath
and adding n-butyllithium (80 mmol, 72.8 ml, 1.1 M in hexane) under
an atmosphere of argon. A solution of 3-methylenecyclohexane-
carboxylic acid (5.68 g, 40 mmol) in cold THF (233 K, 30 ml) was
injected via cannula and reacted for 40 min at 233 K. The reaction
mixture was heated to 323 K for an additional 2 h. The resulting
bright-yellow solution was cooled (233 K) and 2,2-dimethyl-1,3-
dioxan-5-one (5.20 g, 40 mmol) was added dropwise (via syringe
pump) over a period of 2 h. After completion of the addition, the
mixture was stirred for 2.5 h at 233 K. The quenched reaction mixture
was treated with aqueous HCl solution (5%, 200 ml) and the aqueous
phase was extracted with ether (150 ml). The organic phase was
washed with water, dried over MgSO4, concentrated and puri®ed on
silica gel to give (V) (yield 9.61 g, 35.6 mmol, 89%). To a solution of
(V) (8.10 g, 30 mmol) in acetone (130 ml), diisopropylamine
(4.6 ml, 30 mmol) was added dropwise. The resulting salt was
concentrated in vacuo and dissolved in anhydrous dichloromethane
(150 ml). Iodine (7.8 g, 30 mmol) in dichloromethane (150 ml) was
injected under argon and reacted for 48 h at room temperature. The
quenched reaction mixture was shaken with aqueous sodium thio-
sulfate (10%, 30 ml), dried and evaporated in vacuo. The residue was
puri®ed by chromatography on silica gel to afford an unstable solid
identi®ed as iodolactone (VI) (yield 10.8 g, 27.3 mmol, 91%). Iodo-
lactone (VI) (10 g, 25.3 mmol) was dissolved in THF (80 ml). To the
cold solution was added potassium hydroxide (2.13 g, 38 mmol)
dissolved in water (130 ml). After completion of the addition, the
mixture was stirred for 30 min at 298 K. The quenched reaction
mixture was treated with aqueous HCl solution (5%, 100 ml) and
water (100 ml). The organic phase was dried and concentrated to give
Figure 6
A schematic representation of the two categories of double-stranded
ladders, viz. (a) staircase and (b) step-ladder. A, B and C denote
intramolecular, interstrand and intrastrand distances, respectively.
The dialcohol molecules are represented as curved rods linking the two
±CH2OH groups and the oxacycle bridge.
ꢁ
Â
o140 Rodrõguez et al. C11H16O5 and C11H16O5
Acta Cryst. (2005). C61, o138±o142

organic compounds
the unstable epoxide (VII) (yield 6.95 g, 24.3 mmol, 96%). The white
solid so obtained was dried by passing argon through and transferred
under an anhydrous atmosphere. A solution of this solid in
dichloromethane (100 ml) was cooled (195 K) under argon and
treated with p-toluenesulfonic acid (3 mg) in dichloromethane
(60 ml). The reaction was stirred for 30 min at room temperature.
The quenched reaction was washed with water (60 ml), dried over
MgSO4 and concentrated in vacuo. The residue was puri®ed by
chromatography on silica gel (5±15% ethyl acetate in n-hexane) to
give dihydroxylactones (I) (2.72 g, 11.93 mmol) and (II) (2.80 g,
12.28 mmol). Single crystals of (I) and (II) suitable for X-ray analysis
were grown at room temperature from damp carbon tetrachloride/n-
hexane.
Table 3
Selected torsion angles (ꢀ) for (II).
C5ÐC1ÐC2ÐO3
C1ÐC2ÐO3ÐC4
C2ÐO3ÐC4ÐC5
O3ÐC4ÐC5ÐC1
C2ÐC1ÐC5ÐC4
C11ÐC1ÐC5ÐO6
C5ÐC1ÐC11ÐC7
O6ÐC7ÐC11ÐC1
C5ÐO6ÐC7ÐC11
C1ÐC5ÐO6ÐC7
22.1 (2)
3.6 (2)
C11ÐC7ÐC8ÐC9
C8ÐC7ÐC11ÐC1
C10ÐC1ÐC11ÐC7
C11ÐC1ÐC10ÐC9
C8ÐC9ÐC10ÐC1
C7ÐC8ÐC9ÐC10
C1ÐC5ÐC13ÐO14
O6ÐC7ÐC15ÐO16
O16ÐC15ÐC13ÐO14
57.2 (2)
73.9 (2)
75.5 (2)
57.6 (2)
36.6 (2)
36.5 (2)
174.4 (1)
64.9 (2)
62.2 (2)
16.5 (2)
28.6 (2)
30.0 (2)
33.7 (2)
46.1 (2)
43.3 (2)
22.9 (2)
7.4 (2)
Table 4
Hydrogen-bond geometry (A, ) for (II).
ꢀ
Ê
Compound (I)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Crystal data
O14ÐH14Á Á ÁO16vi
O16ÐH16Á Á ÁO14vii
C9ÐH9AÁ Á ÁO12viii
C13ÐH13BÁ Á ÁO12ix
0.82
0.82
0.97
0.97
1.87
1.88
2.55
2.57
2.682 (2)
2.700 (2)
3.470 (2)
3.512 (2)
173
173
159
163
3
C11H16O5
Mr = 228.24
Monoclinic, P21/c
Dx = 1.440 Mg m
Mo Kꢃ radiation
Cell parameters from 2404
re¯ections
Ê
a = 8.067 (3) A
b = 11.029 (3) A
ꢁ = 6.4±27.6ꢀ
ꢄ = 0.11 mm
T = 295 (2) K
1
Ê
Symmetry codes: (vi) x 1; y; z; (vii) x ‡ 12; y ‡ 21; z ‡ 1; (viii) x ‡ 1; y
(ix) x 12; y; z ‡ 32.
;
z ‡ 32;
2
1
Ê
c = 12.769 (4) A
ꢂ = 112.12 (2)ꢀ
V = 1052.4 (6) A
Z = 4
3
Ê
Prism, colourless
0.50 Â 0.20 Â 0.15 mm
Compound (II)
Data collection
Crystal data
Nonius KappaCCD diffractometer
' and ! scans
8698 measured re¯ections
2404 independent re¯ections
1989 re¯ections with I > 2ꢅ(I)
Rint = 0.043
ꢁmax = 27.6ꢀ
h = 8 ! 10
k = 14 ! 13
l = 16 ! 14
C11H16O5
Mr = 228.24
Orthorhombic, Pbca
Ê
a = 7.8896 (6) A
b = 12.7281 (10) A
c = 21.8425 (18) A
Ê
V = 2193.4 (3) A
Z = 8
Dx = 1.382 Mg m
Mo Kꢃ radiation
Cell parameters from 2511
re¯ections
ꢁ = 5.2±27.5ꢀ
ꢄ = 0.11 mm
T = 295 (2) K
1
Ê
Ê
Re®nement
3
Plate, colourless
0.50 Â 0.43 Â 0.15 mm
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.045
wR(F2) = 0.121
S = 1.08
2404 re¯ections
w = 1/[ꢅ2(F2o) + (0.0513P)2
+ 0.3909P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max < 0.001
3
Data collection
3
Ê
Áꢆmax = 0.29 e A
3
Ê
0.19 e A
Nonius KappaCCD diffractometer
' and ! scans
Rint = 0.065
ꢁmax = 27.5ꢀ
147 parameters
H-atom parameters constrained
Áꢆmin
=
10 431 measured re¯ections
2511 independent re¯ections
1623 re¯ections with I > 2ꢅ(I)
h = 10 ! 5
k = 16 ! 15
l = 23 ! 28
Table 1
Selected torsion angles (ꢀ) for (I).
Re®nement
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.053
wR(F2) = 0.132
S = 1.03
2511 re¯ections
w = 1/[ꢅ2(F2o) + (0.0653P)2
+ 0.1829P]
C5ÐC1ÐC2ÐO3
C1ÐC2ÐO3ÐC4
C2ÐO3ÐC4ÐC5
O3ÐC4ÐC5ÐC1
C2ÐC1ÐC5ÐC4
C12ÐC1ÐC5ÐO6
C5ÐC1ÐC12ÐC8
C7ÐC8ÐC12ÐC1
O6ÐC7ÐC8ÐC12
C5ÐO6ÐC7ÐC8
28.3 (2)
9.1 (2)
C1ÐC5ÐO6ÐC7
39.6 (2)
50.8 (2)
61.5 (2)
68.4 (2)
62.4 (2)
50.1 (2)
44.6 (2)
57.0 (2)
98.9 (3)
162.3 (2)
C12ÐC8ÐC9ÐC10
C9ÐC8ÐC12ÐC1
C11ÐC1ÐC12ÐC8
C12ÐC1ÐC11ÐC10
C9ÐC10ÐC11ÐC1
C8ÐC9ÐC10ÐC11
C1ÐC5ÐC14ÐO15
O16ÐC8ÐC14ÐO15
O16ÐC8ÐC5ÐC14
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.001
14.4 (2)
30.7 (1)
34.3 (1)
46.1 (2)
59.0 (2)
64.3 (2)
58.1 (2)
45.7 (2)
3
Ê
Áꢆmax = 0.24 e A
3
Ê
0.20 e A
147 parameters
H-atom parameters constrained
Áꢆmin
=
All H atoms were located in difference Fourier maps and subse-
quently allowed to re®ne as riding on their respective C and O atoms
Ê
Ê
[CÐH = 0.97 A, OÐH = 0.82 A and Uiso(H) = 1.2Ueq(C,O)]. The O
atoms, except O6 in (II), have elongated displacement ellipsoids;
however, split peaks for these atoms were not observed and conse-
quently a disorder model was not used in the re®nement.
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢀ
Ê
For both compounds, data collection: COLLECT (Nonius, 2000);
cell re®nement: SCALEPACK (Otwinowski & Minor, 1997); data
reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK;
structure solution: SIR97 (Altomare et al., 1999); structure re®ne-
ment: SHELXL97 (Sheldrick, 1997); molecular graphics: Xtal3.6
(Hall et al., 1999); publication software: SHELXL97, WinGX
(Farrugia, 1999) and PLATON (Spek, 2003).
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
O15ÐH15Á Á ÁO16i
O16ÐH16Á Á ÁO13ii
C14ÐH14AÁ Á ÁO13iv
C11ÐH11AÁ Á ÁO15v
Symmetry codes: (i)
x; y; z ‡ 1.
0.82
0.82
0.97
0.97
2.07
1.90
2.48
2.55
2.881 (2)
2.715 (2)
3.384 (2)
3.254 (2)
170
171
154
129
1
2
1
2
x
1; 12 y; z
;
(ii) 1 ‡ x; y; z; (iv) x; y ‡ 12; z
;
(v)
ꢁ
Â
Acta Cryst. (2005). C61, o138±o142
Rodrõguez et al. C11H16O5 and C11H16O5 o141

organic compounds
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837±838.
The authors thank the DGICYT of Spain for ®nancial
support (grant No. BQU2001-1137)
Giacovazzo, C., Monaco, H. L., Viterbo, D., Scodari, F., Gilli, G., Zanotti, G. &
Catti, M. (1992). Fundamentals of Crystallography, edited by C. Giacovazzo,
pp. 492±499. International Union of Crystallography/Oxford University
Press.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SQ1188). Services for accessing these data are
described at the back of the journal.
Hall, S. R., du Boulay, D. J. & Olthof-Hazekamp, R. (1999). Editors. Xtal3.6
User's Manual. The University of Western Australia: Lamb, Perth.
Nguyen, V. T., Ahn, P. D., Bishop, R., Scudder, M. L. & Craig, D. C. (2001).
Eur. J. Org. Chem. pp. 4489±4499.
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307±326. New York: Academic Press.
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Â
o142 Rodrõguez et al. C11H16O5 and C11H16O5
Acta Cryst. (2005). C61, o138±o142