J Chem Crystallogr (2009) 39:24–27
25
Dehydroepiandrosterone was subjected to Oppenauer
oxidation with aluminium isopropoxide in toluene and
cyclohexanone to yield the desired compound 4-andro-
stene-3,17-dione (4). The material was dissolved in acetone
and a few drops of methanol were added to the solution to
achieve quality crystallization. The chemical structure
has been assigned on the basis of IR, UV, NMR and mass
spectral data [8].
Table 1 Crystal data and other experimental details
Empirical formula
Formula weight
19 26 2
C H O
286.40
˚
0.71073 A
Wavelength
Crystal system, space group
Unit cell dimensions
1 1 1
Orthorhombic, P2 2 2
˚
a = 7.330(2) A, a = 90°
˚
b = 13.095(11) A, b = 90°
c = 16.856(17) A, c = 90°
˚
The three-dimensional data were collected by using Mo
˚
3
1,618(5) A , 4
˚
Volume, Z
Ka radiation (k = 0.71073 A) [9]. x/2h scan mode in the
3
Calculated density
Absorption coefficient
F(000)
1.176 Mg/m
h-range of 2.42–24.98°. The cell parameters were refined
from accurately determined 25 reflections in the h-range
of 12.4–14.8°. A total number of 1,653 reflections were
collected and the same number were found to be unique
0.074 mm
624
Crystal size
0.5 9 0.45 9 0.3 mm
Theta range for data collection
Limiting indices
2.42–24.98°
0 B h B 8, 0 B k B 15,
(
0 B h B 8, 0 B k B 15, 0 B l B 20) whereas 1,307 were
treated as observed reflections [F [ 4r(F )]. The reflec-
o
o
0
B l B 20
tion data were corrected for Lorentz and polarization
Reflections collected/unique
1,655/1,655 [R(int) = 0.0000]
-
effects. The absorption (0.074 mm ) and extinction
1
Maximum and minimum
transmission
0.978 and 0.964
[
0.012(2)] corrections were not applied.
The structure has been solved by direct methods using
2
Refinement method
Full-matrix least-squares on F
1,655/0/191
SHELXS97 program [10]. All non-hydrogen atoms of the
molecule were located from the E-map. Using SHELXL97
program [11] carried out full-matrix least-squares refine-
ment of the structure. Final refinement with anisotropic
thermal parameters of non-hydrogen atoms and fixing the
hydrogen atoms stereochemically resulted R = 0.0331,
wR = 0.0876. The hydrogen atoms were fixed at chemi-
cally acceptable positions and were allowed to ride on their
parent atoms. Atomic scattering factors can be obtained
from International Tables for Crystallography (1992,
Vol. C Tables 4.2.6.8 and 6.1.1.4). The crystallographic
data are listed in Table 1.
Data/restraints/parameters
2
Goodness-of-fit on F
1.036
Final R indices [F
o
[ 4r(F
o
)]
R = 0.0331, wR = 0.0876
R = 0.0500, wR = 0.0966
0.012(2)
R indices (all data)
Extinction coefficient
-3
˚
0.114 and -0.106 e A
Largest diff. peak and hole
range 108.8(1)–124.7(3)° [average value being 112.8(2)°]
for the five-membered ring bond angles fall in the range
101.6(2)–108.4(2)° [average value being 104.5(2)°]. The
3
2
2
C2(sp )–C3(sp )–C4(sp ) bond angle is exactly equal
[
116.4(2)°] to the average value of this bond angle of 60
androstane derivatives.
Results and Discussion
Ring A adopts sofa conformation [asymmetry parameter
DC (C1–C4) = 7.96] [20]. Ring B and C depicts chair
s
Bond distances and bond angles for non-hydrogen atoms
are listed in Table 2. An ORTEP view of the molecules
indicating atomic-numbering scheme (thermal ellipsoids
drawn at 50% probability) is shown in Fig. 1 [12]. The
geometrical calculations were performed using PARST
program [13].
conformation [asymmetry parameter DC2 (C5–C10) =
5.60, DC (C5–C8) = 1.06 and DC (C9–C11) = 3.40, DC
(C9–C13) = 3.26] [23]. The five-membered ring D occurs
s
2
s
in envelope conformation [DC (C14–C16) = 3.05] [23]
s
with a phase angle of pseudorotation D = -4.35° and
maximum angle of torsion / = 40.8° [21].
m
The bond distances and bond angles were found to be in
good agreement with some analogous structures [7, 14–17].
The hydrogen bonding network is shown in Fig. 2. In
orthorhombic space group P2 2 2 , the molecules of 4-
1
1 1
3
The mean bond lengths, [C(sp )–C (sp )] = 1.523(4),
3
androstene-3,17-dione are linked by paired C–HꢀꢀꢀO
3
2
2
2
C(sp )–C(sp )] = 1.486(4), [C(sp )–C (sp )] = 1.330(3),
2
2
[
[
hydrogen bonds into R ð6Þ graph set, where R refers to
3
C(sp )–O] = 1.216(3) A, are quite close to the standard
˚
Ring [22]. The C(16)–H(16B)ꢀꢀꢀO(1) intermolecular
hydrogen interaction results into a ring like configuration
which makes the dimers. The molecules are linked by
another C(2)–H(2A)ꢀꢀꢀO(2) which connects the dimers and
it shows that the crystal could be pictorially described as
supramolecular structure which is being formed by chains
of dimers diagonally along the bc-plane as shown in Fig. 3.
2
values [18, 19]. The values of bond distances C3(sp )–
3
C2(sp ) = 1.503(4) A [1.499 A] and C3(sp )–C4(sp ) =
2
2
˚
˚
˚ ˚
.447(5) A [1.459 A] are found quite close, when com-
1
pared with the average values of 60 analogous androstane
derivatives. The endocyclic bond angles in the steroid
nucleus comprising three six-membered rings fall in the
123
Rajnikant, Verma
