Four N 7-alkoxy-benzyl-substituted 4,5,6,7-tetra-hydro-1H- pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclo-hexane-2′,6′-diones: Hydrogen-bonded supra-molecular structures in zero, one, two or three dimensions

Article abstract of DOI:10.1107/S0108270108038778

3-tert-Butyl-7-(4-methoxy-benz-yl)-4′,4′-dimethyl-1-phenyl-4,5, 6,7-tetra-hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclohex-ane- 2′,6′-dione, C₃₁H₃₇N₃O₃, (I), 3-tert-butyl-7-(2,3-dimethoxy-benz-yl)-4′,4′-dimethyl-1- phenyl-4,5,6,7-tetra-hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclo- hexane-2′,6′-dione, C₃₂H₃₉N₃O ₄, (II), 3-tert-butyl-4′,4′-dimethyl-7-(3,4-methyl-ene- dioxy-benz-yl)-1-phenyl-4,5,6,7-tetra-hydro-1H-pyrazolo[3,4-b] pyridine-5-spiro-1′-cyclo-hexane-2′,6′-dione, C ₃₁H₃₅N₃O₄, (III), and 3-tert-butyl-4′,4′-dimethyl-1-phenyl-7-(3,4,5-trimethoxy-benz-yl)-4, 5,6,7-tetra-hydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-1′-cyclo-hexane- 2′,6′-dione ethanol 0.67-solvate, C₃₃H₄₁N ₃O₅·0.67C₂H₆O, (IV), all contain reduced pyridine rings having half-chair conformations. The mol-ecules of (I) and (II) are linked into centrosymmetric dimers and simple chains, respectively, by C - H...O hydrogen bonds, augmented only in (I) by a C - H...π hydrogen bond. The mol-ecules of (III) are linked by a combination of C - H...O and C - H...π hydrogen bonds into a chain of edge-fused centrosymmetric rings, further linked by weak hydrogen bonds into supra-molecular arrays in two or three dimensions. The heterocyclic mol-ecules in (IV) are linked by two independent C - H...O hydrogen bonds into sheets, from which the partial-occupancy ethanol mol-ecules are pendent. The significance of this study lies in its finding of a very wide range of supra-molecular aggregation modes dependent on rather modest changes in the peripheral substituents remote from the main hydrogen-bond acceptor sites.

Full text of DOI:10.1107/S0108270108038778

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Comment
In continuation of our structural study of N7-benzyl-substi-
tuted pyrazolo[3,4-b]pyridine-5-spiro-10-cyclohexane-20,60-di-
ones (Cruz et al., 2008) – itself part of a programme exploring
the use of multicomponent condensation reactions, especially
those induced by microwave irradiation under solvent-free
conditions, for the synthesis of novel heterocycles – we now
report the molecular and supramolecular structures of four
N7-alkoxybenzyl derivatives, (I)–(IV) (Figs. 1–4). Compounds
(I)–(IV) were synthesized using the reaction between a sub-
stituted N-benzylaminopyrazole, 5,5-dimethylcyclohexane-
1,3-dione (dimedone) and excess paraformaldehyde, under
solvent-free conditions, in a straightforward modification of
the synthetic method employed by Cruz et al. (2008).
ISSN 0108-2701
Four N7-alkoxybenzyl-substituted
4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]-
pyridine-5-spiro-10-cyclohexane-20,60-
diones: hydrogen-bonded supra-
molecular structures in zero, one,
two or three dimensions
Jorge Trilleras,a Jairo Quiroga,a Justo Cobo,b John N. Lowc
and Christopher Glidewelld*
a
´
´
´
Grupo de Investigacion de Compuestos Heterocıclicos, Departamento de Quımica,
b
´
Universidad de Valle, AA 25360, Cali, Colombia, Departamento de Quımica
Inorganica y Organica, Universidad de Jaen, 23071 Jaen, Spain, cDepartment of
Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE,
Scotland, and dSchool of Chemistry, University of St Andrews, Fife KY16 9ST,
Scotland
´
´
´
´
Correspondence e-mail: cg@st-andrews.ac.uk
Received 18 November 2008
Accepted 19 November 2008
Online 27 November 2008
3-tert-Butyl-7-(4-methoxybenzyl)-40,40-dimethyl-1-phenyl-4,5,-
6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-10-cyclo-
hexane-20,60-dione, C31H37N3O3, (I), 3-tert-butyl-7-(2,3-dimeth-
oxybenzyl)-40,40-dimethyl-1-phenyl-4,5,6,7-tetrahydro-1H-pyra-
zolo[3,4-b]pyridine-5-spiro-10-cyclohexane-20,60-dione, C32H39-
N3O4, (II), 3-tert-butyl-40,40-dimethyl-7-(3,4-methylenedioxy-
benzyl)-1-phenyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyri-
dine-5-spiro-10-cyclohexane-20,60-dione, C31H35N3O4, (III),
and 3-tert-butyl-40,40-dimethyl-1-phenyl-7-(3,4,5-trimethoxy-
benzyl)-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-5-spiro-
10-cyclohexane-20,60-dione ethanol 0.67-solvate, C33H41N3O5ꢀ-
0.67C2H6O, (IV), all contain reduced pyridine rings having
half-chair conformations. The molecules of (I) and (II) are
linked into centrosymmetric dimers and simple chains,
respectively, by C—Hꢀ ꢀ ꢀO hydrogen bonds, augmented only
in (I) by a C—Hꢀ ꢀ ꢀꢀ hydrogen bond. The molecules of (III)
are linked by a combination of C—Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀꢀ
hydrogen bonds into a chain of edge-fused centrosymmetric
rings, further linked by weak hydrogen bonds into supra-
molecular arrays in two or three dimensions. The heterocyclic
molecules in (IV) are linked by two independent C—Hꢀ ꢀ ꢀO
hydrogen bonds into sheets, from which the partial-occupancy
ethanol molecules are pendent. The significance of this study
lies in its finding of a very wide range of supramolecular
aggregation modes dependent on rather modest changes in
the peripheral substituents remote from the main hydrogen-
bond acceptor sites.
Compounds (I)–(III) crystallized in solvent-free form, but
compound (IV) was found to be a partial ethanol solvate, with
0.67 molecules of ethanol per molecule of the pyrazolopyr-
idine in the crystal selected for data collection. We have not
investigated systematically the stoichiometry of this solvate,
but it is possible that different individual crystals might yield
somewhat different values for the occupancy of the ethanol
sites. Equally it is possible that for any such crystal, exposure
to the X-ray beam might cause progressive loss of the ethanol
component over time or that the occupancy of the ethanol
sites throughout a crystal so exposed to X-rays may become
spacially inhomogeneous, or that both effects may be present.
Such spacial and/or temporal variation in the ethanol occu-
pancy, with the associated degradation of the crystal quality,
might well be expected to compromise the quality of the
refinement indicators. Examination using PLATON (Spek,
2003) of the refined structure of (IV), but with the ethanol
component omitted, found eight voids, each of volume ca
3
˚
96 A and together accounting for some 12.2% of the unit-cell
volume. It is possible that the ethanol of solvation is present in
this strucuture merely as a placeholder component, occupying
what would otherwise be empty space.
In each compound, the reduced pyridine ring adopts a half-
chair conformation, as shown (Table 1) by the ring-puckering
parameters (Cremer & Pople, 1975), defined here for the
Acta Cryst. (2008). C64, o665–o670
doi:10.1107/S0108270108038778
# 2008 International Union of Crystallography o665

organic compounds
atom-sequence N7—C6—C5—C4—C3A—C7A. For an idea-
lized half-chair ring with equal bond lengths throughout, the
ring-puckering angles are ꢁ = 50.8ꢁ and ’ = (60k + 30)ꢁ, where
k represents an integer.
(IV). Associated with each of these effectively in-plane
methoxy groups is a marked difference between the two
exocyclic C—C—O angles, typically almost 10ꢁ. By contrast,
the C74/O74/C741 plane in (IV) is almost orthogonal to the
˚
The rest of the molecular conformation is determined by
the orientation of the three pendent substituents relative to
the heterocyclic molecular core, and by the orientation of the
alkoxy substituents relative to the adjacent aryl ring (Table 1).
As indicated by the relevant torsion angles (Table 1), while the
orientation of the phenyl and benzyl units relative to the
molecular core is fairly similar in each compound, there is
considerable variation in the degree to which the tert-butyl
group has been rotated about the C3—C31 bond. Since the
rotational barrier about this bond approximates to a sixfold
barrier, as found when a fragment of local C3 symmetry, such
as a tert-butyl group, is bonded to a fragment with effective
local C2 symmetry, such as a planar ring, it can be expected
that the barrier is exceptionally low, no more than a few tens
of Joules per mole (Tannenbaum et al., 1956; Naylor & Wilson,
1957), so accounting for the variation in the relative orienta-
tion of the tert-butyl group.
adjacent ring, with atom C741 displaced by 1.058 (5) A from
The orientations of the methoxy substituents in (I), (II) and
(IV) show some interesting variations. As shown by the rele-
vant torsion angles (Table 1), the single methoxy group in (I),
that at C73 in (II), and those at C73 and C75 in (IV) are all
almost coplanar with the adjacent aryl rings. The deviations
˚
from the mean planes of these rings are 0.235 (3) A for atom
˚
C741 in (I), 0.006 (3) A for atom C731 in (II), and 0.147 (5)
˚
and 0.164 (5) A for atoms C731 and C751, respectively, in
Figure 2
The molecular structure of (II). Displacement ellipsoids are drawn at the
30% probability level.
Figure 1
The molecular structure of (I). Displacement ellipsoids are drawn at the
30% probability level.
Figure 3
The molecular structure of (III). Displacement ellipsoids are drawn at the
30% probability level.
ꢂ
o666 Trilleras et al. C31H37N3O3, C32H39N3O4, C31H35N3O4 and C33H41N3O5ꢀ0.67C2H6O
Acta Cryst. (2008). C64, o665–o670

organic compounds
the ring plane, while atom C721 in (II) is displaced from the
˚
adjacent ring plane by 0.944 (3) A. At the same time, in (IV),
In compound (I), pairs of molecules are linked by the co-
operative action of C—Hꢀ ꢀ ꢀO and C—Hꢀ ꢀ ꢀꢀ hydrogen bonds
into centrosymmetric dimers, within which the paired C—
Hꢀ ꢀ ꢀO hydrogen bonds define an R22(22) (Bernstein et al.,
1995) motif (Fig. 5), but there are no direction-specific inter-
actions between these dimers; hence the supramolecular
aggregation in compound (I) can be regarded as finite, or zero-
dimensional.
the exocyclic C—C—O angles at atom C74 are identical within
experimental uncertainty, and those at atom C72 in (II) differ
by less than 3ꢁ. Although the in-plane conformation appears
to be the most favoured and of lowest energy, maximizing the
orbital overlap between the ꢀ orbitals of the ring and formally
nonbonding 2p orbital on the O atom, this orientation is
nonetheless rather easily disrupted by nonbonded (steric)
interactions between adjacent substituents. In (III), the five-
membered ring formed by the methylenedioxy unit adopts an
envelope conformation, folded across the line O71ꢀ ꢀ ꢀO72.
Although compounds (I)–(IV) all contain potential
hydrogen-bond acceptors – in the methoxy groups in (I), (II)
and (IV), and in the methylenedioxy unit in (III) – in no case
do these O atoms play any significant role in the supra-
molecular aggregation. There is a rather long C—Hꢀ ꢀ ꢀO
contact involving such an O atom in (III) (Table 2), although
this is possibly only of marginal structural significance, at best,
while the methoxy O atoms in the other three compounds do
not form even weak contacts of this type. The principal
intermolecular interactions in this series are of C—Hꢀ ꢀ ꢀꢀ type
and of C—Hꢀ ꢀ ꢀO type utilizing carbonyl O atoms as the
hydrogen-bond acceptors. There are no ꢀ–ꢀ stacking inter-
actions in any of (I)–(IV). The partial-occupancy ethanol
component in (IV) is connected to the heterocyclic compo-
nent by a three-point linkage (Table 2), but it plays no role in
the supramolecular aggregation, acting simply as a pendent
group.
A single C—Hꢀ ꢀ ꢀO hydrogen bond links molecules of (II),
3
which are related by the 21 screw axis along (12, y, ), into a
4
simple C(11) chain running parallel to the [010] direction
(Fig. 6). Two chains of this type related to one another by
inversion pass through each unit cell, but there are no direc-
tion-specific interactions between adjacent chains.
In (III), a combination of a C—Hꢀ ꢀ ꢀO hydrogen bond, with
C15 as the donor, and a C—Hꢀ ꢀ ꢀꢀ hydrogen bond links the
molecules into a chain of centrosymmetric edge-fused rings
running parallel to the [100] direction (Fig. 7). Within this
chain, R22(22) rings exactly analogous to those observed in (I)
Figure 5
Part of the crystal structure of (I), showing the formation of a
centrosymmetric dimer. For the sake of clarity, H atoms not involved in
the motifs shown have been omitted. Atoms marked with an asterisk (*)
are at the symmetry position (ꢃx, 1 ꢃ y, 1 ꢃ z).
Figure 4
Figure 6
The molecular structure of (IV). The ethanol component has occupancy
0.670 (7) (see Experimental). Displacement ellipsoids are drawn at the
30% probability level.
A stereoview of part of the crystal structure of (II), showing the
formation of a C(11) chain along [010]. For the sake of clarity, H atoms
not involved in the motif shown have been omitted.
ꢂ
Acta Cryst. (2008). C64, o665–o670
Trilleras et al.
C31H37N3O3, C32H39N3O4, C31H35N3O4 and C33H41N3O5ꢀ0.67C2H6O o667

organic compounds
Figure 8
A stereoview of part of the crystal structure of (IV), showing the
formation of a sheet parallel to (001). For the sake of clarity, the partial-
occupancy ethanol component and H atoms bonded to C atoms not
involved in the motifs shown have been omitted.
Figure 7
A stereoview of part of the crystal structure of (III), showing the
formation of a chain along [100] containing two types of centrosymmetric
ring. For the sake of clarity, H atoms bonded to C atoms not involved in
the motifs shown have been omitted.
that, as the degree of methoxy substitution increases, so too
does the dimensionality of the hydrogen-bonded structure,
from zero-dimensional in the monomethoxy compound (I) to
one-dimensional in the dimethoxy compound (II) to two-
dimensional in the trimethoxy compound (IV). It is interesting
to note that the variations in the molecular constitution occur
solely in the substituted benzyl ring, which is, of course,
remote from the main hydrogen-bond acceptor sites, the
carbonyl O atoms and the main hydrogen-bond donor sites,
most of which are provided by the unsubstituted phenyl ring.
1
2
1
2
are centred at (n, , ), where n represents an integer, and
these alternate with rings formed by pairs of C—Hꢀ ꢀ ꢀꢀ
1
2
1 1
2 2
hydrogen bonds, centred at (n + , , ), where n represents
zero or an integer. Within the structure of (III), there are two
further C—Hꢀ ꢀ ꢀO contacts, both rather long, and it is of
interest to examine their possible structural effects. The
interaction involving C13 as the donor links the chains of rings,
which are related by translation along [010], while that
involving C72 as the donor links the R22(22) rings into a chain
along [001]. Thus, if these two interactions are regarded as
structurally significant, the supramolecular structure is based
on the one-dimensional chains of rings along [100] (Fig. 7),
which become successively linked into two-dimensional and
three-dimensional arrays.
The heterocyclic components in (IV) are linked into a sheet
by two C—Hꢀ ꢀ ꢀO hydrogen bonds, both utilizing the same
carbonyl acceptor atom, and the formation of the sheet is
readily analysed in terms of the individual actions of the two
hydrogen bonds. The aryl atom C13 at (x, y, z) acts as a
Experimental
Microwave-induced syntheses were carried out using a focused
microwave reactor (CEM Discover TM). A mixture of the appro-
priately substituted N-benzylaminopyrazole (2 mmol), 5,5-dimethyl-
cyclohexane-1,3-dione (2 mmol) and an excess of paraformaldehyde
(80–100 mg) was exposed to microwave radiation at 473 K with a
maximum power of 300 W for 25 min. The reaction mixtures were
dissolved in hot ethanol. After cooling these solutions, the solid
products were collected by filtration and washed with ethanol and
then with hexane (2 ꢄ 5 ml) to afford the pure products. Colourless
crystals suitable for single-crystal X-ray diffraction were grown by
slow evaporation of solutions in ethanol. For (I), yield 75%, m.p. 445–
447 K; HRMS found 499.2835, C31H37N3O3 requires 499.2835. For
(II), yield 85%, m.p. 503–505 K; HRMS found 529.2941, C32H39N3O4
requires 529.2941. For (III), yield 70%, m.p. 475–477 K; HRMS found
513.2635, C31H35N3O4 requires 513.2628. For (IV), yield 71%, m.p.
456–458 K; HRMS found 559.3032, C33H41N3O5 requires 559.3046.
1
hydrogen-bond donor to carbonyl atom O51 at (ꢃx, ꢃ + y,
2
1
ꢃ z), so linking molecules related by the 21 screw axis along
2
(0, y, 14 ), and so forming a C(11) chain running parallel to the
[010] direction. In the second substructure, methylene atom
C77 at (x, y, z) acts as a hydrogen-bond donor to atom O51 at
(12 ꢃ x, ꢃ + y, z), thus linking molecules related by the b-glide
1
2
plane at x = 14 into a C(7) chain, again running parallel to the
[010] direction. The combination of these two chain motifs
generates a sheet of R34(28) rings lying parallel to (001) (Fig. 8)
and occupying the domain 0 < z < 12. A second sheet, related to
the first by inversion, occupies the domain 12 < z < 1, but there
are no direction-specific interactions between adjacent sheets.
As noted above, the partial-occupancy ethanol molecules are
pendent from this sheet, but they play no role in its formation.
Although the methoxy substituents in (I), (II) and (IV) play
no direct role in the supramolecular aggregation, it is striking
Compound (I)
Crystal data
C31H37N3O3
Mr = 499.64
Triclinic, P1
a = 9.5971 (8) A
b = 11.2549 (16) A
˚
c = 12.1452 (14) A
ꢂ = 86.979 (11)ꢁ
ꢃ = 85.487 (10)ꢁ
ꢄ = 87.216 (7)ꢁ
3
˚
V = 1304.7 (3) A
Z = 2
˚
Mo Kꢂ radiation
ꢅ = 0.08 mmꢃ1
T = 120 (2) K
0.51 ꢄ 0.36 ꢄ 0.18 mm
˚
ꢂ
o668 Trilleras et al. C31H37N3O3, C32H39N3O4, C31H35N3O4 and C33H41N3O5ꢀ0.67C2H6O
Acta Cryst. (2008). C64, o665–o670

organic compounds
Table 1
Selected geometric parameters (A, ) for (I)–(IV).
Table 2
Hydrogen bonds and short intermolecular contacts (A, ) for (I)–(IV).
ꢁ
ꢁ
˚
˚
(a) Ring-puckering parameters for the atom sequence N7—C6—C5—C4—
C3A—C7A
Compound D—Hꢀ ꢀ ꢀA
D—H Hꢀ ꢀ ꢀA Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
(I)
C15—H15ꢀ ꢀ ꢀO55i
0.95
0.95
2.54
2.88
3.229 (3) 130
3.589 (3) 132
3.256 (3) 140
C16—H16ꢀ ꢀ ꢀCg1i,a
C74—H74ꢀ ꢀ ꢀO55ii
Parameter
(I)
(II)
(III)
(IV)
Q
ꢁ
’
0.441 (3)
50.5 (4)
80.8 (4)
0.450 (2)
50.3 (3)
86.0 (4)
0.426 (3)
51.6 (4)
72.2 (4)
0.460 (4)
53.6 (5)
81.6 (6)
(II)
0.95
2.47
(III)
C13—H13ꢀ ꢀ ꢀO51iii
C15—H15ꢀ ꢀ ꢀO55iv
C72—H72ꢀ ꢀ ꢀO71v
C6—H6Aꢀ ꢀ ꢀCg2vi,b
0.95
0.95
0.95
0.99
2.58
2.46
2.60
2.69
3.182 (3) 121
3.173 (3) 132
3.503 (3) 160
3.670 (3) 169
(b) Torsion angles
(I)
(II)
(III)
(IV)
(IV)
O81—H81ꢀ ꢀ ꢀCg2b
C6—H6Aꢀ ꢀ ꢀO81
C52—H52Aꢀ ꢀ ꢀO81
C13—H13ꢀ ꢀ ꢀO51vii
0.84
0.99
0.99
0.95
2.69
2.58
2.48
2.43
2.45
3.423 (4) 147
3.406 (6) 141
3.470 (6) 174
3.194 (5) 137
3.193 (4) 131
N2—C3—C31—C32
N2—C3—C31—C33
N2—C3—C31—C34
N2—N1—C11—C12
C6—N7—C77—C71
N7—C77—C71—C72
C71—C72—O72—C721
C72—C73—O73—C731
C73—C74—O74—C741
C76—C75—O75—C751
C72—C73—O71—C78
C75—C74—O72—C78
ꢃ165.1 (2)
ꢃ127.3 (2)
ꢃ7.0 (3)
112.8 (2)
ꢃ130.9 (2)
72.0 (2)
ꢃ156.3 (2)
125.3 (2)
177.0 (2)
–
ꢃ127.3 (3)
ꢃ6.5 (4)
113.3 (3)
ꢃ149.1 (3)
66.8 (3)
ꢃ156.8 (2)
–
ꢃ103.6 (4)
16.2 (5)
136.9 (4)
ꢃ138.5 (3)
59.8 (4)
ꢃ131.5 (3)
–
5.6 (5)
ꢃ88.9 (5)
4.0 (6)
–
ꢃ43.4 (3)
C77—H77Bꢀ ꢀ ꢀO51viii 0.99
74.5 (3)
ꢃ133.8 (2)
Notes: (a) Cg1 represents the centroid of the N1/N2/C3/C3A/C7A ring; (b) Cg2
represents the centroid of the C71–C76 ring. Symmetry codes: (i) ꢃx; ꢃy þ 1; ꢃz þ 1;
69.7 (3)
ꢃ143.6 (2)
3
2
(ii) ꢃx þ 1; y þ 12 ; ꢃz þ ; (iii) x; y ꢃ 1; z; (iv) ꢃx þ 2; ꢃy þ 1; ꢃz þ 1; (v) ꢃx þ 2,
–
–
1
2
1
2
ꢃy þ 1; ꢃz þ 2; (vi) ꢃx þ 1; ꢃy þ 1; ꢃz þ 1; (vii) ꢃx; y ꢃ 12 ; ꢃz þ ; (viii) ꢃx þ ,
–
–
–
y ꢃ 12 ; z.
ꢃ5.3 (4)
–
–
–
–
–
–
170.3 (3)
ꢃ170.5 (3)
–
Data collection
Bruker–Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.965, Tmax = 0.990
45254 measured reflections
6394 independent reflections
4404 reflections with I > 2ꢆ(I)
Rint = 0.065
(c) Bond angles
(I)
(II)
(III)
(IV)
C71—C72—O72
C73—C72—O72
C72—C73—O73
C74—C73—O73
C73—C74—O74
C75—C74—O74
C74—C75—O75
C76—C75—O75
–
–
–
118.5 (2)
120.9 (2)
115.9 (2)
124.3 (2)
–
–
–
–
–
–
–
–
–
–
–
–
–
–
123.9 (3)
115.5 (3)
120.0 (3)
120.4 (3)
115.2 (3)
124.6 (3)
–
124.7 (2)
115.6 (2)
–
–
Refinement
R[F2 > 2ꢆ(F2)] = 0.061
wR(F2) = 0.138
S = 1.18
359 parameters
H-atom parameteꢃrs3 constrained
˚
Áꢇmax = 0.28 e A
Áꢇmin = ꢃ0.31 e A
ꢃ3
˚
6394 reflections
Data collection
Bruker–Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.971, Tmax = 0.985
36057 measured reflections
5986 independent reflections
3281 reflections with I > 2ꢆ(I)
Rint = 0.081
Compound (III)
Crystal data
C31H35N3O4
Mr = 513.62
Triclinic, P1
a = 9.2691 (14) A
b = 11.0898 (11) A
ꢄ = 91.070 (11)ꢁ
˚
V = 1308.6 (3) A
Z = 2
3
˚
Mo Kꢂ radiation
ꢅ = 0.09 mmꢃ1
T = 120 (2) K
0.54 ꢄ 0.29 ꢄ 0.10 mm
˚
Refinement
˚
c = 12.802 (2) A
ꢂ = 92.844 (10)ꢁ
ꢃ = 95.185 (12)ꢁ
R[F2 > 2ꢆ(F2)] = 0.060
wR(F2) = 0.199
S = 1.04
5986 reflections
340 parameters
H-atom parameteꢃrs3 constrained
˚
Áꢇmax = 0.31 e A
Áꢇmin = ꢃ0.39 e A
ꢃ3
˚
Data collection
Bruker–Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.964, Tmax = 0.991
36798 measured reflections
6010 independent reflections
2954 reflections with I > 2ꢆ(I)
Rint = 0.129
Compound (II)
Crystal data
3
˚
V = 2791.7 (5) A
Z = 4
C32H39N3O4
Mr = 529.66
Refinement
Monoclinic, P21=c
Mo Kꢂ radiation
ꢅ = 0.08 mmꢃ1
T = 120 (2) K
0.32 ꢄ 0.25 ꢄ 0.12 mm
R[F2 > 2ꢆ(F2)] = 0.063
wR(F2) = 0.171
S = 1.06
348 parameters
H-atom parameteꢃrs3 constrained
˚
a = 12.4683 (15) A
˚
b = 10.2892 (12) A
˚
c = 21.7635 (16) A
˚
Áꢇmax = 0.31 e A
Áꢇmin = ꢃ0.34 e A
ꢃ3
ꢃ = 90.843 (10)ꢁ
6010 reflections
˚
ꢂ
Acta Cryst. (2008). C64, o665–o670
Trilleras et al.
C31H37N3O3, C32H39N3O4, C31H35N3O4 and C33H41N3O5ꢀ0.67C2H6O o669

organic compounds
ethanol sites. Subsequent examination of the original frames showed
some diffuse diffraction streaks, again consistent with degradation of
the crystal quality, even at 120 K. Attempts to crystallize compound
(IV) from an alternative solvent (dimethylformamide) gave no
crystalline material.
Compound (IV)
Crystal data
3
˚
V = 6328.0 (15) A
Z = 8
Mo Kꢂ radiation
ꢅ = 0.08 mmꢃ1
T = 120 (2) K
C33H41N3O5ꢀ0.67C2H6O
Mr = 590.55
Orthorhombic, Pbca
For all compounds, data collection: COLLECT (Hooft, 1999); cell
refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction:
EVALCCD (Duisenberg et al., 2003); program(s) used to solve
structure: SIR2004 (Burla et al., 2005); program(s) used to refine
structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick,
2008); molecular graphics: PLATON (Spek, 2003); software used to
prepare material for publication: SHELXL97 and PRPKAPPA
(Ferguson, 1999).
˚
a = 13.5770 (17) A
˚
b = 17.476 (3) A
˚
c = 26.670 (3) A
0.32 ꢄ 0.32 ꢄ 0.28 mm
Data collection
Bruker–Nonius KappaCCD
diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.974, Tmax = 0.977
53340 measured reflections
7255 independent reflections
4959 reflections with I > 2ꢆ(I)
Rint = 0.058
Refinement
´
The authors thank ‘Servicios Tecnicos de Investigacion of
Universidad de Jaen’ and the staff for data collection. JC
´
R[F2 > 2ꢆ(F2)] = 0.087
wR(F2) = 0.206
S = 1.17
407 parameters
H-atom parameteꢃrs3 constrained
´
´
´
thanks the Consejerıa de Innovacion, Ciencia y Empresa
˚
Áꢇmax = 0.59 e A
ꢃ3
´
´
˚
(Junta de Andalucıa, Spain) and the Universidad de Jaen for
financial support. JT and JQ thank COLCIENCIAS and
UNIVALLE (Universidad del Valle, Colombia) for financial
support.
7255 reflections
Áꢇmin = ꢃ0.36 e A
For (II) and (IV), the space groups P21/c and Pbca, respectively,
were uniquely assigned from the systematic absences. Crystals of (I)
and (III) are triclinic; for each, the space group P1 was selected and
then confirmed by the structure analysis. All H atoms were located in
difference maps and then treated as riding atoms in geometrically
idealized positions, with C—H distances of 0.95 (aromatic), 0.98
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3276). Services for accessing these data are
described at the back of the journal.
˚
˚
(CH3) or 0.99 A (CH2) and an O—H distance of 0.84 A, and with
Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl and hydroxy H
atoms, and k = 1.2 for all other H atoms. In the crystal of (IV) selected
for data collection, the site occupancy for the ethanol component
refined to a value of 0.670 (7). Crystals of (III) diffracted rather
weakly, even at 120 K, with only 49% of the data labelled ‘observed’;
the merging index was also fairly high, at 0.129. The crystals of (IV)
consistently exhibited internal fissures, and all attempts to cut small
fragments from larger crystals resulted in destruction and the
formation of powdery residues. This behaviour is certainly consistent
with progressive loss of the ethanol component. The data set
collected for compound (IV) appeared to be entirely satisfactory, as
judged by the data completeness (99.7% at ꢁ = 27.51ꢁ), the merging
index, and the precision of the unit-cell dimensions. However, the
refinement converged at a rather high R value, with a fairly large
linear term in the weighting scheme. Scrutiny of the resulting
interatomic distances and the Uij values in compound (IV), and
comparison with the corresponding parameters in compounds (I)–
(III) showed no anomalies. In the crystal selected for data collection,
the occupancy of the ethanol site refined to 0.670 (7) but, as noted in
the Comment section, it is possible that different individual crystals
might yield somewhat different values for the occupancy of the
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ꢂ
o670 Trilleras et al. C31H37N3O3, C32H39N3O4, C31H35N3O4 and C33H41N3O5ꢀ0.67C2H6O
Acta Cryst. (2008). C64, o665–o670