J Chem Crystallogr (2012) 42:345351

DOI 10.1007/s10870-011-0251-z

ORIGINAL PAPER

X-Ray Crystal Structure of BetulinDMSO Solvate

Stanisaw Boryczka Ewa Michalik
Maria Jastrzebska Joachim Kusz
Maciej Zubko Ewa Bebenek

Received: 7 July 2011 / Accepted: 3 December 2011 / Published online: 21 December 2011
Springer Science+Business Media, LLC 2011

Abstract Betulin is a lupane triterpenoid [lup-20(29)-ene3b,28-diol, C30H50O2] showing high biological activity.
This activity is supposed to be strongly affected by the
molecular structure of its polymorphic forms. Different
solvate polymorphic forms of betulin have aroused
increasing interest as the possible anticancer agents of natural origin. X-ray diffraction was used to investigate crystal
structure of (1:1) betulinDMSO solvate. Title compound
crystallizes in the orthorhombic P212121 space group. Unit
, b =
cell parameters are as follows: a = 7.0006(2) A
, c = 33.6991(8) A
, Z = 4. Crystal packing
12.1623(3) A
and selected geometric parameters are described. It has been
found that the hydrogen bonding and the dipoledipole
interaction between DMSO molecules play the major role in
the formation of the crystal structure.
Keywords X-ray crystal structure
Betulin
DMSO

Hydrogen bonds
Polymorphism

S. Boryczka (&)
E. Michalik
E. Bebenek

Department of Organic Chemistry, Silesian Medical University,
4 Jagiellonska Str., 41-200 Sosnowiec, Poland
e-mail: boryczka@sum.edu.pl
M. Jastrzebska
Department of Solid State Physics, Institute of Physics,
University of Silesia, 4 Uniwersytecka Str., 40-007 Katowice,
Poland
J. Kusz
M. Zubko
Department of Physics of Crystals, Institute of Physics,
University of Silesia, 4 Uniwersytecka Str., 40-007 Katowice,
Poland

Introduction
Betulin [lup-20(29)-ene-3b,28-diol, C30H50O2] (1), also
known as betulinic alcohol, is a pentacyclic triterpene of
the lupane type which was one of the first natural products
identified and isolated from plants as a pure chemical
substance in 1788 by Lowitz [1]. Betulin can be obtained
from the birch bark either by sublimation or by the
extraction with organic solvents. The still growing interest
in betulin (1) and its derivatives results from their wide
spectrum of biological activities such as: anticancer, antiviral, antibacterial or hepatoprotective properties [13].
The structure of 1 is based on a 30-carbon skeleton comprising of four 6-membered rings and one 5-membered
ring. Betulin (1) has three available sites for simple
chemical modification, namely: secondary hydroxyl group
at position C-3, primary hydroxyl group at position C-28
and isopropenyl side chain at position C-20. The high
content of betulin (up to 30%) in white birch bark and the
ease of its isolation in almost any amount, make it
important starting material for synthesis of new compounds
with various interesting biological activities. In the last few
years a large number of betulin derivatives have been
reported to possess anticancer, anti-inflammatory, anti-HIV
and anti-leishmanial activity [1, 4]. Figure 1 shows the
numbering scheme for betulin (1).
It is well known that the large numbers of natural
molecules are capable of exhibiting polymorphism or
pseudopolymorphism [5]. More importantly, different
polymorphic forms of pharmaceutical compounds display
varying physicochemical properties, such as: solubility,
stability, density as well as bioavailability, particularly
when the drug substance is poorly soluble. Various solvent
used in the crystallization process and different melting
points reported may indicate the existence of several

123

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J Chem Crystallogr (2012) 42:345351

29

et al. [9]. They found three sites, where the hydrogen bonds
were formed.
In this work, we describe the crystal structure of the new
betulinDMSO (1:1) solvate in order to gain better
understanding of this important molecule.

CH2
20

30

H3C
18
12
26

11

25

DH

10

24

CH3
7

27

H
CH3
23

Fig. 1 Atomic numbering scheme of betulin (1)

crystal polymorphic forms of betulin. It is therefore

important to investigate molecular structure of different
polymorphs of betulin and describe how their properties
may differ.
Dimethyl sulfoxide (DMSO) is a commercially important product, commonly used in chemical laboratories and
in cosmetology and pharmaceutical industry, particularly
as an excellent aprotic solvent. DMSO has been intensively
studied for its pharmacological activity, as it has many
effects; e.g. it has been found to relieve symptoms of
arthritis, secondary amyloidosis associated with rheumatoid arthritis, bursitis and myositis [6]. The semipolar sulphur-oxygen linkages in DMSO have a full or partial
positive charge on the sulphur and the negative charge on
the oxygen atom. Therefore SO bonds can interact or
associate with various reagents both through the sulphur
and oxygen atoms or form the hydrogen bonds with water,
alcohols, phenols, proteins, carbohydrates, nucleic acid and
other H-donor compounds of living systems [7]. The
molecular and crystal structure of DMSO was described in
detail by Thomas et al. [8].
Biological activity of a drug substance is usually tested in
the solvent environment. The most frequently solvents used
are water and DMSOwater mixtures. Solvent molecules can
strongly affect the energies of different conformations, the
hydrogen bonding pattern as well as the hydrophilic/hydrophobic group exposures to protein molecules.
Biological activity of the betulin is supposed to be
strongly affected by the ability of its polymorphs to form
hydrogen bonds. In our work it has been found, that in the
crystal structure of betulinDMSO solvate the hydrogen
bonding plays a major role.
The hydrogen bonding in the crystal structure of betulin
ethanol solvate was reported previously by Drebushchak

123

General Techniques

BH
6

HO
H3C

16

Experimental

CH2OH

15

22
28

13
14

E
17

C CH3

CH3

21

19

Melting points were determined in open capillary tubes on

a Boetius melting point apparatus and were uncorrected.
NMR spectra were recorded on a Bruker MSL 600 spectrometer in CDCl3 solvents with tetramethylsilane as
internal standard; chemical shifts are reported in ppm (d)
and J values in Hz. Multiplicity is designated as singlet (s),
doublet (d), multiplet (m). IR spectra (KBr, pellet) were
recorded on a IRAffinity-1 Shimadzu spectrophotometer.
TLC was performed on silica gel 60 254F plates (Merck)
using a mixture of dichloromethane and ethanol (20:1, v/v)
as an eluent. Spots were detected by spraying a solution of
5% sulfuric acid, followed by gentle heating. Column
chromatography was performed on silica gel 60, \63 lm
(Merck) using a mixture of dichloromethane and ethanol
(40:1 v/v) as an eluent. Solvents were dried and purified
according to usual procedures.
Isolation of Betulin (1)
Betulin (1) was isolated from the bark of birch (Betula
verrucosa), collected in Poland, by extraction with
dichloromethane. The crude betulin was purified by column chromatography using a mixture of dichloromethane
and ethanol (40:1, v/v) as an eluent. Recrystallization from
DMSOwater solution (9:1, v/v) afforded (1) as a white
crystals, Rf 0.35 (silica gel, dichloromethane-ethanol, 20:1,
v/v), mp 245-247 C. 1H NMR (600 MHz, CDCl3) d: 0.76
(s, 3H, CH3), 0.82 (s, 3H, CH3), 0.97 (s, 3H, CH3), 0.98 (s,
3H, CH3), 1.02 (s, 3H, CH3), 1.68 (s, 3H, CH3), 1.021.94
(m, 25H, CH, CH2), 2.39 (m, 1H, H-19), 2.67 (s, 6H,
2xCH3), 3.19 (m, 1H, H-3), 3.34 (d, J = 10.8 Hz, 1H,
H-28), 3.81 (d, J = 10.8 Hz, 1H, H-28), 4.58 (s, 1H,
H-29), 4.69 (s, 1H, H-29). 13C NMR (150 Hz, CDCl3) d:
14.76 (C27), 15.37 (C26), 15.93 (C24), 16.07 (C25), 18.24
(C6), 19.03 (C30), 20.77 (C11), 25.13 (C12), 26.99 (C15),
27.30 (C2), 27.94 (C23), 29.11 (C16), 29.68 (C21), 33.93
(C7), 34.16 (C22), 37.09 (C10), 37.24 (C13), 38.64 (C1),
38.81 (C4), 40.64 [(CH3)2SO], 40.85 (C8), 42.66 (C14),
47.73 (C17, C19), 48.69 (C18), 50.33 (C9), 55.22 (C5),
60.47 (C28), 78.96 (C3), 109.66 (C29), 150.45 (C20). IR
(KBr, cm-1) m: 3328, 2943, 1626, 1449, 1375, 1244, 1043,
1006, 882.

J Chem Crystallogr (2012) 42:345351

347

X-Ray Diffraction Experiment

X-Ray Crystal Structure

The single crystal X-ray experiment was performed at

100.0(1) K. For this measurement, a colourless single
crystal (0.15 9 0.22 9 0.60 mm3) of good quality was
preselected under a polarizing microscope. The crystal was
mounted on a quartz capillary and cooled down by a cold,
dry nitrogen gas stream (Oxford Cryosystems equipment).
The data were collected using Oxford Diffraction kappa
diffractometer with Sapphire3 CCD detector. Accurate cell
parameters were determined and refined with using program CrysAllis CCD (Oxford Diffraction, 2008) [10]. For
the integration of the collected data the program CrysAllis
RED was used (Oxford Diffraction, 2008).

BetulinDMSO solvate (1:1) crystallizes in the orthorhombic, P212121 space group. Table 1 shows crystal parameters,
data collections and refinement details. The asymmetric unit
contains one betulin molecule and one DMSO molecule.
They are shown in Fig. 2 with displacement ellipsoids of
50% probability. The unit cell contains four molecules of
betulin and DMSO (Z = 4). The selected bond lengths, bond
angles and torsion angles are presented in Table 2. Bond
lengths and valency angles have typical values for this type
of compound [12].
Six-members ring have chair conformation, while the
cyclopentane ring adopts twisted conformation as shown
by the Cremer and Pople parameters [13] [ring A:
, h = 4.17 and u = 110.54; B: Q =
Q = 0.5480 A

,
0.5813 A, h = 10.47 and u = 358.76; C: Q = 0.6079 A

h = 9.95 and u = 319.02; D: Q = 0.5685 A, h =

, u2 = 3.92].
168.36 and u = 102.42; E: q2 = 0.4397 A
The calculations were made by PLATON program [14].
All ring junctions in the betulinDMSO solvate are
trans-fused. A similar ring conformation was also observed
in 3,28-O,O-diacetylbetulin [15], 3,28-O,O-diacetyl-29bromobetulin [16], and betulinethanol solvate [9].

Refinement
The structure was solved using direct method with SHELXS97 software and then the solution was refined using
SHELXL97 program [11]. The aromatic hydrogen atoms
were treated as riding on their parent carbon atoms with
and assigned isotropic atomic displaced(CH) = 0.95 A
ment parameters equal to 1.2 times the value of the equivalent
atomic displacement parameters of the parent carbon atom
(Uiso(H) = 1.2Ueq(C)). The methylene H atoms were con
strained to an ideal geometry with d(CH) = 0.99 A
or

d(CH) = 0.95 A (for terminal methylene group) and Uiso

(H) = 1.2Ueq(C). Methyl H atoms were constrained as riding

atoms, fixed to the parent atoms with distance of 0.98 A

and
Uiso(H) = 1.5Ueq(C). The methyl group at C31 and C32 were
constrained as riding atoms and torsion angle were refined.
Hydrogen atoms involved in hydrogen bonding were refined
freely with isotropic atomic displacement parameters.

Results and Discussion

Chemistry
Betulin (1) was isolated from the bark of birch by extraction with dichloromethane. The crude betulin was purified
by column chromatography using a mixture of dichloromethane and ethanol. Crystals of betulin (1) for X-ray
structural analysis were grown from a DMSOwater (9:1,
v/v) solution. Full structural elucidation of the new betulin
DMSO solvate was made using 1H, 13C NMR and IR
spectroscopy, and assignments were performed based on
our analysis and related literature. The significant feature
of the 1H and 13C NMR spectra of betulinDMSO solvate
lies in the presence of characteristic signals for the protons
and carbons atoms of methyl groups at 2.67 and
40.64 ppm, respectively, attributed to the DMSO.

Table 1 Crystal parameters, data collection and refinement details

for studied compound
Chemical formula

C30H50O2
C2H6OS

Formula mass

520.83

Crystal system
Space group
)
a (A

Orthorhombic
P212121

)
b (A

c (A)

12.1623(3)

7.0006(2)
33.6991(8)

a ()

90.00

b ()

90.00

c ()

90.00

3)
Unit cell volume (A

2869.26(13)

No. of formula units per unit cell, Z

Temperature (K)

100(1)

Crystal size (mm3)

0.60 9 0.22 9 0.15

Radiation type

MoKa
-1

Absorption coefficient (l/mm )

0.144

No. of reflections measured

17,912

No. of independent reflections

5,093

Rint
Final R1 values (I [ 2r(I))

0.0286
0.0786

Final wR(F2) values (I [ 2r(I))

0.2195

Final R1 values (all data)

0.0858

Final wR(F2) values (all data)

0.2243

Goodness of fit on F2

1.061

Flack parameter

0.1(4)

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J Chem Crystallogr (2012) 42:345351

Fig. 2 Molecular structure with

atomic numbering scheme of
betulinDMSO solvate with
displacement ellipsoids of 50%
probability

, ) for the crystal strucTable 2 Selected geometric parameters (A

ture of betulinDMSO solvate
O1C3

1.426(4)

C29C20C30

O2C28

1.425(5)

C29C20C19

120.1(4)
118.4(4)

C17C28

1.538(6)

C30C20C19

121.4(4)

C17C22

1.538(5)

O2C28C17

111.6(3)

C17C18

1.549(5)

O1C3C4C23

67.1(4)

C18C19

1.546(5)

O1C3C4C5

C19C20

1.519(6)

C18C19C20C29

146.5(4)

C19C21

1.569(6)

C21C19C20C29

-96.8(5)

C20C29

1.386(7)

C18C19C20C30

-36.8(6)

C20C30
S1O3

1.424(7)
1.552(12)

C21C19C20C30
C16C17C28O2

79.9(5)
66.3(4)

O1C3C2

107.3(3)

C22C17C28O2

-62.6(4)

O1C3C4

113.0(3)

C18C17C28O2

-173.3(3)

C20C19C18

116.0(3)

O3S1O3iS1i

-144.3(11)

C20C19C21

110.0(3)

Symmetry codes: (i) x - 1/2, -y ? 3/2, -z ? 1

Fig. 3 Different orientations of

the isopropenyl groups (marked
as a circle) towards the C18
C19C21C22 plane: a betulin
DMSO solvate (this work) and
b betulinethanol solvate
(according to Drebushchak et al.
[9])

123

-176.9(3)

The cyclopentane ring is characterized by envelope

conformation with the C17 atom being displaced from C18
so that the C17C18
C19C21C22 plane about 0.668 A
C19C21 and C19C21C22C17 torsion angles are equal
to 28.76 and -24.26 correspondingly (for betulinethanol
, 29.23 and -23.06, respectively [9]).
solvate 0.654 A
It is important to emphasize that the C29C20C19
C21 torsion angle describing the orientation of the isopropenyl group is equal to -96.84, while for betulin
ethanol solvate and the 3,28-O,O-diacetylbetulin it was
88.64 [9] and -107.18 [15], respectively. Figure 3 shows
different orientations of isopropenyl group in two conformational polymorphic structures of betulin. The OH group
is attached to the atom C3 of the ring A in an equatorial
orientation, while the hydroxymethyl group is attached to
the atom C17 of the ring D in an axial orientation.
The hydroxyl group of betulin is involved in intermolecular O1H1


O2 hydrogen bonding, which links the
molecules into chains running along the a axis. The crystal

J Chem Crystallogr (2012) 42:345351

349

packing is further stabilized by weak intermolecular

CH


O hydrogen bonds. In the chain, betulin molecules
are zigzag arranged and linked head-to-tail by the
O1H1


O2 hydrogen bonds. Similar arrangement was
found in the betulinethanol solvate crystal [9]. However,
in the ethanol solvate the O1H1


O2 hydrogen bond was
found stronger in comparison to our result for DMSO solvate. According to Drebushchak et al. [9], the H


A distance
and 172 whereas for
and DHA angle were equal to 2.01 A
and 146, respecbetulinDMSO solvate they are 2.16 A
tively. In Table 3, the main parameters of the all hydrogen
bonds found in the betulinDMSO solvate are collected.
Beside the hydrogen bonds between betulin molecules,
there exist also H-bonds between betulin and solvent
, ) for the betulinDMSO
Table 3 Hydrogen-bond parameters (A
solvate
DH


A

DH

H


A

D


A

DH


A

O1H1


O2i

0.72(6)

2.16(6)

2.793(4)

146(6)

O2H2


O3ii

0.72(7)

1.85(7)

2.570(7)

175(8)

C22H22A


O2

0.99

2.53

2.944(6)

105

C31H31B


O2iii

0.98

2.46

3.168(11)

129

C31H31C


O3iv

0.98

2.51

3.070(17)

116

0.98

2.21

2.926(11)

129

C32H32B


O1v

0.98

2.51

3.209(12)

128

C31H31C


O1

Symmetry codes: (i) -x ? 2, y ? 1/2, -z ? 1/2; (ii) x, y - 1, z;

(iii) x, y ? 1, z; (iv) x - 1/2, -y ? 3/2, -z ? 1; (v) -x ? 1, y ? 1/2,
-z ? 1/2

molecules. The oxygen atom of DMSO and the hydroxymethyl group of betulin are involved in the O2H2


O3
bond, which is relatively strong with short H


A distance
) and almost linear directionality (Table 3). This is
(1.85 A
the strongest H-bond in the betulinDMSO solvate complex and play an important role in determining the solidstate.
It should be noted, that in the betulinDMSO solvate the
O1H1


O3 hydrogen bond has not been detected. It can
be due to the fact that the hydroxymethyl group of betulin
acts as stronger proton donor than the secondary OH group
at C3. The strength of the H-bond depends on the relative
acidities and basicities of the donor and acceptor sites and
in the case of intramolecular bonds, on the spatial
arrangement present [17]. However, the H-bond of
O3H3


O1 involving the proton from the OH group at C3,
was observed by Drebushchak et al. [9] in the betulin
ethanol solvate. The hydroxyl group at C28 in betulin
molecule participates in two hydrogen bonds acting as both
donor and acceptor of protons (Fig. 4). It results in
enhancing the hydrogen bond energy over that of the sum
of individual bond energies. It can also contribute to the
fact that the O1H1


O2 bond has been found weaker than
reported earlier by Drebushchak et al. [9] for the betulin
ethanol solvate (Table 3).
BetulinDMSO solvate was prepared using DMSO
water (9:1) mixture. DMSO molecules were found to predominate the formation of H-bonds in the solvate.
According to literature data, DMSO oxygen can act as a

Fig. 4 View of the O1H1


O2

and O2H2


O3 hydrogen
bonds in betulinDMSO solvate

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successful competitor in hydrogen bonding against water

[18].
Beside the H-bonding between betulin and DMSO
molecules, solvent molecules interact also between themselves via a electrostatic interaction. In the DMSO molecule, the partial positive and negative charges on sulphur
and oxygen atoms, respectively, give rise to the large
dipole moment (4.1 D, gas phase [19]). The length of the
[20], while in our
S=O bond for free molecule was 1.495 A
measurements the length is found to be longer
) due to the H-bond formation with the betulin
(1.552(12) A
molecule (see Fig. 5; Table 2). Wiewior et al. [19] calculated the electrostatic potential (ESP) for the gas phase
DMSO molecule using the B3LYP/6-311??G(d,p)
geometry optimization. They determined the hemispherical
symmetric ESP about the oxygen atom. The DMSO oxygen charge was about -0.56e-, that is enough to form two
or more hydrogen bonds or other weak electrostatic interactions. They found also that depending on the basis of the
ESP calculation, the sulphur charge was varying from
?0.343 to ?0.725e-.
Considering the large dipole moment of the DMSO
molecules and the short distance between them
; Table 2, Fig. 5), the interaction of DMSO
(3.2244(12) A
DMSO occurs most probably via dipoledipole interaction.
Such dipoledipole interaction was observed earlier by
Tukhvatullin et al. [21] in pure liquid DMSO.
Our measurements have shown, that H-bonding and
dipoledipole interaction play the crucial role in the formation of the crystal structure of DMSObetulin solvate. As
it is seen in Fig. 6, H-bonds link betulin molecules into
zigzag arranged ribbons laying in the bc plane. DMSO
molecules form columns in a direction by dipoledipole
interactions. Neighbouring betulin ribbons are connected
via H-bonds to DMSO columns giving the final three
dimensional network (Fig. 6). Longitudinal structures of
DMSODMSO associations were also observed in crystal
structures of two solvents of 9,10-anthraquinonecarboxylic
Fig. 5 View of the DMSO
dipoledipole interaction in
betulinDMSO solvate

123

J Chem Crystallogr (2012) 42:345351

Fig. 6 Hydrogen bonds in betulinDMSO solvate crystal structure:

a view down the a axis and b view down the b axis

acids and DMSO [22], however the dipoledipole interaction was not stated.

Conclusions
BetulinDMSO (1:1) solvate crystallizes in the orthorhombic P212121 space group. It was found that the

J Chem Crystallogr (2012) 42:345351

hydrogen bonding is the major bond responsible for the

crystal structure of the solvate. H-bonds occur between
betulinbetulin as well as betulinDMSO molecules. The
DMSO oxygen and the hydroxymethyl group of betulin are
involved in the strongest H-bond in the solvate. The column-like structures of the DMSO molecules coupled by the
dipoledipole interactions were found in the crystal lattice.
They were H-bonded to betulin molecules giving the final
3-D crystal structure.
DMSO is one of the most frequently used solvents in the
medicinal chemistry and its interaction with the biologically active substances like betulin is of great importance.

Supplementary Material
X-ray crystallographic data reported in this paper is
deposited at the Cambridge Crystallographic Data Centre
as supplementary publication number CCDC 810332.
Acknowledgments This work was supported by the Medical University of Silesia, Poland, Grant No KNW-1-073/P/1/0. The work of
M.Z. was partially supported by PhD scholarship within the framework of the University as a Partner of the Economy Based on Science (UPGOW) project, subsidized by the European Social Fund
(EFS) of the European Union.

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