Crystal structures of 2-Phenyl-2H-1,2,3-Triazol-4-carbaldehyde, an active α-glycosidase inhibition agent, and (1-phenyl-1H-1,2,3-triazol-4-yl)methyl benzoate and (2-(4-Fluorophenyl)-2H-1,2,3-triazole-4-yl)methanol, two moderately active compounds

Article abstract of DOI:10.1007/s10870-015-0629-4

The crystal structures of (1-phenyl-1H-1,2,3-triazol-4-yl)methyl benzoate, 1a, (2-(4-fluorophenyl)-2H-1,2,3-triazole-4-yl)methanol, 2a, and 2-phenyl-2H-1,2,3-triazol-4-carbaldehyde, 2b, are reported. Compounds 1a and 2a were recently reported to exhibit m

Full text of DOI:10.1007/s10870-015-0629-4

J Chem Crystallogr (2016) 46:67–76
DOI 10.1007/s10870-015-0629-4
ORIGINAL PAPER
Crystal Structures of 2-Phenyl-2H-1,2,3-Triazol-4-Carbaldehyde,
an Active a-Glycosidase Inhibition Agent, and (1-Phenyl-1H-1,2,3-
Triazol-4-yl)Methyl Benzoate and (2-(4-Fluorophenyl)-2H-1,2,3-
Triazole-4-yl)Methanol, Two Moderately Active Compounds
Daniel Gonzaga1 Fernando C. da Silva1 Vitor F. Ferreira1 James L. Wardell2,3
Solange M. S. V. Wardell4
•
•
•
•
Received: 13 August 2015 / Accepted: 23 November 2015 / Published online: 16 December 2015
Ó The Author(s) 2015. This article is published with open access at Springerlink.com
Abstract The crystal structures of (1-phenyl-1H-1,2,3-
triazol-4-yl)methyl benzoate, 1a, (2-(4-fluorophenyl)-2H-
1,2,3-triazole-4-yl)methanol, 2a, and 2-phenyl-2H-1,2,3-
triazol-4-carbaldehyde, 2b, are reported. Compounds 1a and
2a were recently reported to exhibit mild a-glycosidase
inhibition activity, while compound 2b exhibited a much
greater activity. Only small dihedral angles 6.52(4),
14.02(10) and 2.44(7)° are present between the triazolyl ring
and the attached aryl rings in 1a, 2a and 2b, respectively. The
relatively flat compounds 2a and 2b contrast with compound
1a, which is ‘‘V’’ shaped, with a dihedral angle between the
near planar phenyltriazolyl-CH2 and phenyl-CO2CH2 moi-
eties of 88.11(4)°. The intermolecular interactions in 1a are
C–HÁÁÁX (X = N or p(triazole) and p(triazole) ÁÁÁp(phenyl):
two different chains are formed, from (i) combinations of the
C–HÁÁÁN hydrogen bonds and (ii) combinations of the
C–HÁÁÁp and pÁÁÁp interactions.. The intermolecular interac-
tions in 2a are C–HÁÁÁO and C–FÁÁÁp(phenyl): the C–HÁÁÁO
interactions generate a sheet of molecules, containing a
network of rings.ÁClassical O–HÁÁÁO hydrogen bonds, and
weaker C–HÁÁÁp(triazolyl) and p(phenyl)ÁÁÁp(triazolyl)
interactions are present in 2b: all three interactions together
generate a chevron-type arrangement. Compound 1a crys-
tallizes in the monoclinic space group P21 with
˚
a = 4.5661(5), b = 10.5573(14), c = 13.9694(19) A,
b = 90.594(6)° and Z = 2. Compound 2a crystallizes in the
monoclinic space group P21 with a = 3.7175(7),
˚
b = 10.428(2), c = 10.689(3) A, b = 90.521(6)° and Z
= 2. Compound 2b crystallizes in the monoclinic space
group P21/c with a = 11.4130(5), b = 4.80280(10),
˚
c = 15.5916(11) A, b = 103.373(7)° and Z = 4.
Graphical Abstract The relatively flat compounds, (2-
(4-fluorophenyl)-2H-1,2,3-triazole-4-yl)methanol and 2-phe-
nyl-2H-1,2,3-triazol-4-carbaldehyde, contrast with compound
(1-phenyl-1H-1,2,3-triazol-4-yl)methyl benzoate, which is
‘‘V’’ shaped, with a dihedral angle between the near planar
phenyltriazolyl-CH2 and phenyl-CO2CH2 moieties of
88.11(4) o.
& James L. Wardell
j.wardell@abdn.ac.uk
1
´
Instituto de Quımica, Departamento de Quımica Organica,
Universidade Federal Fluminense, Campus do Valonguinho,
´
ˆ
´
24210-141 Niteroi, RJ, Brazil
2
FioCruz-Fundac¸a˜o Oswaldo Cruz, Instituto de Tecnologia em
´
Farmacos-Far-Manguinhos, Rua Sizenando Nabuco, 100,
Manguinhos, 21041-250 Rio De Janeiro, RJ, Brazil
3
4
Department of Chemistry, University of Aberdeen,
Old Aberdeen AB24 3UE, Scotland, UK
CHEMSOL, 1 Harcourt Road, Aberdeen AB15 5NY,
Scotland, UK
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Keywords 1H-1,2,3-triazole Á 2H-1,2,3-triazole Á a-
glycosidase inhibition Á Hydrogen bonds, pÁÁÁp interactions
Table 1 Compounds mentioned in this article
(1a: Ar = Ph, X = PhCO2CH2, Y = H)
(1b: Ar = 4-MeC6H4, X = H, Y = F2CH)
(1c: Ar = 4-O2NC6H4, X = Me, Y = MeCO)
(1d: Ar = Ph, X = H, Y = pyridin-3-ylCO2Me)
(1e: Ar = 4-MeC6H4, X = H, Y = OCH
(1f: Ar = 4-O2NC6H4, X = OCH, Y = Me3Si)
(1g: Ar = 3-ClC6H4, X = H, Y = HOCH2)
(1h: Ar = 3,5-Me2C6H3, X = H, Y = HOCH2)
(1i: Ar = 4-PhC6H4, X = H, Y = HOCH2)
(1j: Ar = 4-HO2CC6H4, X = H, Y = HOCH2)
(1k: Ar = 2-HO2CC6H3, X = H, Y = HOCH2)
(1l: Ar = 2-HOC6H4, X = H, Y = HOCH2)
(2b: Ar = 4-FC6H4, X = OCH, Y = H)
(2a: Ar = Ph, X = HOCH2, Y = H)
Ar
N
N
N
Introduction
X
Y
1,2,3-Triazole exists in two tautomeric forms, namely 1H-
1,2,3-triazole and 2H-1,2,3-triazole, see Fig. 1. Derivatives
of both forms have attracted much attention [1–3], in
particular for their biological activities, which include as
antiviral [4–6], antimalarial [7], antitubercular [8–10],
antifungal [11, 12] anti-HIV [13], b-lactamase inhibition
[14], anti-epileptic [15], anti-HSV [16], anti-inflammatory
[17], antimicrobial [18, 19] and a-glycosidase inhibition
agents [20–23]. Patents lodged in the period 2008–2011 for
1H-1,2,3-triazole and 2H-1,2,3-triazole derivatives have
been included in a general survey for all triazolyl com-
pounds [24].
Ar
N
N
X
N
A recent a-glycosidase inhibition study [23] involved a
number of different 1-phenyl-1H- and 2-phenyl-2H-1,2,3-
triazol derivatives. The crystal structures of three of the
compounds from that study [20] have been determined,
namely, (1-phenyl-1H-1,2,3-triazol-4-yl)methyl benzoate,
1a, (2-(4-fluorophenyl)-2H-1,2,3-triazole-4-yl)methanol,
2a and 2-phenyl-2H-1,2,3-triazole-4-carbaldehyde, 2b, see
Table 1. Compounds, 1a and 2a, exhibited little activity,
while compound 2b, exhibited a greater inhibition, as did
all the 2-aryl-2H-1,2,3-triazole-4-carbaldehyde derivatives.
It was suggested that the aldehydes act upon both yeast
maltase and PPA, with the aldehyde groups reacting with
amine groups in the enzyme polypeptide chain to form
Schiff bases.
Y
asymmetric unit in each case consists of a single molecule,
as illustrated in Fig. 2. Selected bond lengths and angles
are listed in Table 2. The bond lengths and angles associ-
ated with the 1,2,3-triazole rings are in the regions nor-
mally found for 1-aryl-1H-1,2,3,triazoles [see for example
25–28] and for 2-aryl-2H-1,2,3,triazoles [see for example
Refs. 28–33].
In each of 1a, 2a and 2b, the triazolyl ring is essentially
planar. The dihedral angles between the triazolyl and aryl
rings are listed in Table 3.
A large range of dihedral angles have been reported for
both 1-aryl-1H-1,2,3-triazole and 2-aryl-2H-1,2,3-triazole
compounds, for example the angles are 0.34(17) and
87.1(2)°, respectively, in 4-difluoromethyl-1-(4-methyl-
phenyl)-1H-1,2,3-triazole, 1b, [34] and in one independent
molecule of 1-[5-methyl-1-(4-nitrophenyl)-1H-1,2,3-tria-
zol-4-yl]ethanone, 1c [35], see Table 1. The carbon atoms
of the methylene units in 2b and 1a are essentially co-
planar with the attached triazolyl group. Compound 1a has
a ‘‘V’’ shape with the angle between the near planar
phenyltriazolyl-CH2 and phenyl-CO2CH2 moieties of
88.11(4)°.
We now wish to report our structural findings.
Results and Discussion
The compounds were prepared as previously reported, see
Scheme 1 [20].
Molecular Confirmations
Compounds 2a and 2b crystallize in the monoclinic space
group, P21 with Z = 2, while compound 2b crystallizes in
the monoclinic space group, P21/c with Z = 4. The
Crystal Structures
Compound 1a
Fig. 1 a 1H-1,2,3-triazole,
b 2H-1,2,3-triazole
H
N
H
N
N
H
N
H
N
N
The intermolecular interactions in 1a are all weak, being
C–HÁÁÁN hydrogen bonds, C–HÁÁÁp and p–p interactions. As
illustrated in Fig. 3a, chains of molecules are propagated in
the direction of the b axis, from combinations of C5–
H
H
(a)
(b)
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69
Scheme 1 Reagents; i = D-
glucose; ii = aq. CuSO4; D,
iii = NaIO4; iv = NaBH4,
MeOH; v = HC:C–CH2OH,
CuI; vi = PhCOCl
Fig. 2 Atom arrangements and the numbering schemes for 1a, 2a and 2b. Probability ellipsoids are drawn at the 50 % level. The intramolecular
hydrogen bond in 1a is drawn as a thin dashed line
H5ÁÁÁN3, C5–H5ÁÁÁN2 and C8–H8ÁÁÁN3 hydrogen bonds,
see Table 4 for the symmetry operations. Of these hydro-
gen bonds, the C5–H5ÁÁÁN3 is the most significant. With
C5–H5 acting as donor to two acceptors, N2 and N3, R12 (3)
rings are generated. The C5–H5ÁÁÁN3, C5–H5ÁÁÁN2, and
C8–H8ÁÁÁN3 hydrogen bonds individually generate C4, C4
and C6 chains of molecules.
The structure of a related compound, 1-phenyl-4-(pyr-
idine-3-yl-CO2CH2)-1H-1,2,3-triazole) (1d) [36] has been
reported. There are some structural similiarities between 1a
and 1d: (i) the molecule of 1d is also ‘‘V’’ shaped with the
angle between the planar phenyltriazolyl CH2 and phenyl-
CO2CH2 moieties of 83.84°, (ii) the dihedral angle between
the triazolyl and phenyl rings is 16.54 (11)°, and (iii) there
are similar C–HÁÁÁ p (triazole) and p(phenyl)ÁÁÁp(triazolyl)
Further, chain of molecules, this time propagated in
the direction of the a axis, are formed from combinations
of C6–H6AÁÁÁp(triazolyl) and p(phenyl)ÁÁÁp(triazolyl)
stacking interactions, see Fig. 3b; Table 4. This combi-
nation of interactions provides a chevron-type arrange-
ment. The perpendicular distance between the best planes
of combined triazolyl/ phenyl rings between layers is
˚
interactions [CgÁÁÁCg = 3.895(1) A]. However other
intermolecular interactions are different in 1d, being C–
HÁÁÁN(py), C–HÁÁÁO(carbonyl) and C–HÁÁÁp(triazolyl)
hydrogen bonds, which generate a different supramolecular
array to that of 1a.
˚
Compound 2a
3.359(3) A, and with the CgÁÁÁCg separations of
˚
3.738(3) A, these pÁÁÁp interactions are important. The
The intermolecular interactions in 2a are C8–H8ÁÁÁO2 and
C11–H11ÁÁÁO2 hydrogen bonds and C10–F1ÁÁÁ p(phenyl)
packing of the molecules looking down the b axis is
shown in Fig. 4.
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J Chem Crystallogr (2016) 46:67–76
˚
Table 2 Selected geometric parameters, A°
Table 3 Interplanar angles, °
1a
2a
2b
Compound
Angle between triazole and phenyl rings°
N1–N2
1.349(5)
1.323(5)
1.362(5)
1.375(5)
1.355(6)
106.8(3)
109.4(4)
108.0(4)
104.8(4)
110.9(4)
4.9(7)
1.354(2)
1.3356(12)
1.3410(12)
1.3358(13)
1.3999(15)
1.3309(15)
115.28(9)
103.69(8)
108.25(9)
109.43(10)
103.34(9)
1a
2a
2b
6.52(4)
N2–N3
1.325(2)
14.02(10)
2.44(7)
N3–C4
1.342(3)
C4–C5
1.409(3)
C5–N1
1.336(3)
N1–N2–N3
N2–N3–C4
N3–C4–C5
C4–C5–N1
C5–N1–N2
C5–N1–C7–C8
N2–N1–C7–C12
C5–N1–C7–C12
N2–N1–C7–C8
N1–N2–C7–C8
N1–N2–C7–C12
N3–N1–C7–C12
N3–N1–C7–C8
115.38(16)
104.10(16)
108.35(18)
108.91(18)
103.26(17)
interactions. Table 4 lists the symmetry operations
and geometric parameters. Combinations of the C8–
H8ÁÁÁO2 and C11–H11ÁÁÁO2 hydrogen bonds generate
sheets of molecules, composed of R43 (24) rings, see
Fig. 5a. The sheet undulates in the direction of the
b axis, as shown in Fig. 4b. Both the C–HÁÁÁO hydrogen
bonds building the sheets are on the weak side. Stacks of
molecules are generated from C10–F1ÁÁÁp(phenyl) inter-
actions, see Fig. 5c. The Cg(phenyl)–Cg(triazolyl) dis-
tances in adjacent layers within the stacks are 4.2623(17)
7.6(6)
174.7(4)
172.8(4)
164.27(19)
14.9(3)
0.70(15)
179.39(15)
3.04(14)
˚
A, which suggest any p(phenyl)– p(triazolyl) must be
very weak. Figure 6 illustrates the packing of molecules
168.6(2)
12.3(3)
176.87(9)
of 2a.
Fig. 3 Compound 1a. a A chain of molecules generated in the
direction of the b axis, from combinations of C5–H5ÁÁÁN3, C5–
H5ÁÁÁN2 and C8–H8ÁÁÁN3 hydrogen bonds, b a further chain of
molecules, propagated in the direction of the a axis, formed from C6–
H6AÁÁÁp(triazole)and weak p(phenyl)ÁÁÁp(triazole) interactions.
Table 4 lists the symmetry operations. Intermolecular interactions
are drawn as thin dashed lines
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71
˚
Table 4 Geometric parameters (A, °) for intra- and intermolecular interactions
Compound
D–HÁÁÁA
D–H
HÁÁÁA
DÁÁÁA
D–HÁÁÁA
(a) Hydrogen bonds
1a
1a
1a
1a
2a
2a
2b
C12–H12ÁÁÁN2
C5–H5ÁÁÁN2i
C5–H5ÁÁÁN3i
C8–H8ÁÁÁN3i
C8–H8ÁÁÁO2ii
C11–H11ÁÁÁO2iii
O1–H1ÁÁÁO1iv
0.95
0.95
0.95
0.95
0.95
0.95
0.84
2.48
2.61
2.31
2.62
2.59
2.61
1.89
2.799(6)
3.464(5)
3.239(5)
3.572(6)
3.251(3)
3.373(3)
2.7265(11)
100
150
165
174
126
138
174
Y–XÁÁÁCga
XÁÁÁCg
Xperp
c
Y–XÁÁÁCg
YÁÁÁCg
(b) Y–XÁÁÁp interactionsa
1a
2a
2b
C6–H6AÁÁÁCg1i
2.62
2.614
3.386
2.596
1.91
143
3.456(5)
3.490(3)
3.6500(11
C10–F1ÁÁÁCg2i
3.7752(18)
2.81
26.23
22.39
67.57(10)
143
C6–C6BÁÁÁCg1ii
Cg(I)ÁÁÁCg(J)
CgÁÁÁCg
a
b
c
CgIperp
CgJperp
(c) pÁÁÁp interactionsa
1a
1a
2a
2a
2b
2b
Cg1ÁÁÁCg2i
3.738(3)
6.54
22.39
28.00
33.50
39.64
24.57
25.43
28.00
22.39
39.64
33.50
25.43
24.57
3.301
3.457
3.282
3.554
3.411
3.435
3.456
3.301
3.554
3.282
3.435
3.411
Cg2ÁÁÁCg1ii
Cg1ÁÁÁCg2ii
Cg2ÁÁÁCg1i
Cg1ÁÁÁCg2iii
Cg2ÁÁÁCg1iv
3.738(3)
6.54
4.2623(17)
4.2624(17)
3.7771(7)
3.7771(7)
14.02
14.02
2.44
2.44
Symmetry operations for (a): i = 1 ? x, y, z; ii = -1 ? x, y, z; iii = x, 1 ? y, z; iv = x, -1 ? y, z
Symmetry codes for (b): i = -x,1/2 ? y, -z; ii = -x, ‘ ? y, 2-z; iii = 1 ? x, y, -1 ? z; iv = 1-x,-1/2 ? y, 3/2-z
Symmetry codes for (c): i = 1 ? x, y, z; ii = x, 1 ? y, z
a
Cg1 and Cg2 are the centroids of the rings, containing atoms, N2and C8, respectively; b is the angle between the vectors CgÁÁÁCg and CgIperp
where CgIperp is the perpendicular distance of CgI from the plane of ring J: c is the angle between the vectors CgÁÁÁCg and CgJperp
Compound 2b
The structure of 1e, which was only briefly discussed in
the original article [37], exhibits significant differences
with that of 2a. Features of the structure of 1e are (i) a near
planar molecule, as shown by the dihedral angle of 7.1°
between the triazolyl and the phenyl rings, (ii) C–H(phe-
nyl)ÁÁÁO(=C) and C5–H5ÁÁÁN3 hydrogen bonds forming
chains containing R22 (10) rings propagated in the direction
of the a axis, and relatively strong p(triazolyl)ÁÁÁp(triazolyl)
and (iii) p(phenyl)ÁÁÁp(phenyl) interactions.in which the
CgÁÁÁCg distances and perpendicular distances between
planes through the phenyltriazole fragments, in both cases
Present in 2b are classical O1–H1ÁÁÁO1 hydrogen bonds,
and C6–H6BÁÁÁp(triazolyl) and p(phenyl)ÁÁÁp(triazolyl)
interactions. All three interactions together generate a
chevron-type arrangement of molecules as illustrated in
Fig. 7. The most significant of these interactions are O1–
H1ÁÁÁO1 hydrogen bonds, which forms chains of molecules
in the direction of the b axis. The packing of the molecules
of 2b, looking down the b axis is illustrated in Fig. 8. As in
compound 2a, none of the triazolyl nitrogen atoms are
involved in any intermolecular interaction in 2b.
˚
are 3.865(4) and 3.436(4) A, respectively.
The position of the aldehyde group on C5 of the triazole
ring in 1f, results in a much larger dihedral angle between
the triazoleyland aryl planes of 62.34(5)°, compared to
those in 2a and 1e. Again the carbonyl oxygen is involved
in C–HÁÁÁO hydrogen bonds, this time with a CH unit in the
trimethylsilyl group: these C–HÁÁÁO hydrogen bonds pro-
duce chains of molecules.
Related Compounds
Comparisons of the structure of 2a can be made with those
reported for 1-(4-methylphenyl)-4-OCH-1H-1,2,3-triazole,
1e, [37] and 1-(4-nitrophenyl)-4-trimethylsilyl-1H-1,2,3-
triazol-5-carbaldehyde, 1f, [38].
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Fig. 4 Packing of molecules of
1a, looking down the b axis
Fig. 5 Compound 2a. a An
undulating sheet of molecules of
2a, formed from weak C11–
H11ÁÁÁO2 and C8–H8ÁÁÁO2
hydrogen bonds, and composed
of R43 (24) rings, b an alternate
view of the sheet shown in a,
clearly indicating its undulating
nature and its alignment along
the b axis, c a stack of
molecules, with p(phenyl)–
p(triazole) stacking interactions,
augmented by C10–
F1ÁÁÁp(phenyl) interactions.
Intermolecular interactions are
drawn as thin dashed lines.
Table 4 lists the symmetry
operations
Comparison of the structure of 2a can be made with the
hemihydrate of 1-(3-C6H4)-4-HOCH2-1H-1,2,3-triazole,
1g, [39], 1-(3,5-dimethylphenyl)-4-HOCH2-1H-1,2,3-
triazole, 1 h, [40] and 1-(4-biphenyl)-4-HOCH2-1H-1,2,3-
triazole. 1i [40] and 1-(4-HO2CC6H4-4-HOCH2-1H-1,2,3-
triazole. 1j [41], 1-(2-HO2CC6H4-4-HOCH2-1H-1,2,3-
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73
triazole. 1k [41] and 1-(2-HOC6H4-4-HOCH2-1H-1,2,3-
triazole. 1l [41].
In both 1-(4-biphenyl)-4-HOCH2-1H-1,2,3-triazole, 1i,
and 1-(3,5-dimethylphenyl)-4-HOCH2-1H-1,2,3-triazole,
1h, [40], there are O–HÁÁÁN3 hydrogen bonds involving the
hydroxyl group. However in 1i, these generate chains of
molecules, while in 1h centrosymmetric dimers, having R22
(10) rings, are formed. The dihedral angles between the
triazolyl and phenyl rings are 25.29(5) and 23.71(5)° in 1i
and 1h, respectively, and thus are much larger than that in
2b [2.44°] and must be a consequence of the crystal
packing rather than any steric effect arising from the sub-
stituents. Neither 1i nor 1h exhibits pÁÁÁp stacking
interactions.
Fig. 6 Packing of molecules of 2a, looking down the b axis
In the hemihydrate of 1-(3-ClC6H4)-4-HOCH2-1H-
1,2,3-triazole, [1g.0.5(H2O)] [39], the hydrate plays a
significant role in the supramolecular array. The most
important intermolecular interactions in [1g.0.5(H2O] are
Ow–HwÁÁÁN3 and Ow–HwÁÁÁOw hydrogen bonds, which
generate chains of molecules of water and 1g propa-
gated in the direction of the a-axis. Additional features
of the structure are O6H6 twelve-membered rings formed
from O–HÁÁÁO hydrogen bonds involving two hydrate
molecules and the hydroxyl groups of two molecules
each of the two independent molecules of 1g. Also
present in [(1g)2(H2O)] are weak p(phenyl)ÁÁÁp(phenyl)
interactions.
As illustrated by [1g.0.5(H2O)], the presence of addi-
tional donor centres radically changes the involvement of
the triazole bound hydroxyl group. This is also very clearly
illustrated by the group of compounds, 1j–1l [26], in which
the hydroxyl group on the triazole ring preferentially links
with the hydroxyl or carboxylic acid substituents on the
phenyl ring, leading to the formation of helices and other
supramolecular architectures.
Fig. 7 Chevron type arrangement of molecules of 2b, generated from
strong classical O1–H1ÁÁÁO 1 intermolecular hydrogen bonds and
weaker C6–H6BÁÁÁp(triazole) and p(triazole)ÁÁÁp(phenyl) interactions.
Table 4 lists the symmetry operations. Intermolecular interactions are
drawn as thin dashed lines
Conclusion
There appears to be no consistent intermolecular interac-
tion, nor dihedral angle between the aryl and triazole rings,
in either of the two series of aryl-1,2,3-triazoles . The
dependence of the supramolecular array on the sub-
stituent(s) is clearly apparent.
Experimental
The compounds, 1a, 2a and 2b, were prepared as reported
[23]. For the structure determinations, crystals of 1a were
obtained from MeOH, 2a from EtOH and 2b from Me2CO
solutions.
Fig. 8 Packing arrangement of molecules of 2b, looking down the
b axis
123

74
J Chem Crystallogr (2016) 46:67–76
Table 5 Crystal data and structure refinement
2b
1a
1b
Empirical formula
Formula weight
Temperature, K
C9H9N3O
175.19
C16H13N3O2
279.29
C9H6FN3 O
191.17
120(2)
100(2)
100(2)
˚
Wavelength, A
0.71075
0.71075
0.71075
Crystal system, space group
Unit cell dimensions
Monoclinic, P21/c
Monoclinic, P21
Monoclinic, P21
˚
a, A
11.4130(5)
4.5661(5)
3.7175(7)
˚
b, A
4.80280(10)
10.5573(14)
10.428(2)
˚
c, A
15.5916(11)
13.9694(19)
10.689(3)
a, °
b, °
c, °
90
90
90
103.373(7)
90.594(6)
90.521(6)
90
90
90
3
˚
Volume, A
831.47(7)
673.37(15)
414.35(16)
Z
4
2
2
Density (calculated) Mg/m3
Absorption coefficient, mm-1
F(000)
1.400
1.377
1.532
0.096
0.094
0.121
368
292
196
Crystal size, mm
Theta range for data collection, °
Index ranges
0.25 9 0.18 9 0.10
3.59–27.43
-14 \ = h \ = 14;
-5 \ = k \ = 6;
-20 \ = l \ = 19
8009
0.14 9 0.03 9 0.01
3.50–27.46
-5 \ = h \ = 5;
-13 \ = k \ = 13;
-18 \ = l \ = 18
4663
0.04 9 0.03 9 0.01
3.81–27.37
-4 \ = h \ = 3;
-13 \ = k \ = 13;
-13 \ = l \ = 13
5287
Reflections collected
Independent reflections
Reflections observed ([2r)
Data completeness
1881 [R(int) = 0.0164]
1642
2762 [R(int) = 0.0664]
1884
1863 [R(int) = 0.0512]
1513
0.99
1.00
1.00
Absorption correction
Refinement method
Semi-empirical from equivalents Semi-empirical from equivalents Semi-empirical from equivalents
Full-matrix least-squares on F2
Full-matrix least-squares on F2
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
Absolute structure parameter
Final R indices [I [ 2r(I)]
1881/0/120
2762/1/190
1863/1/130
0.99
1.04
0.90
–
0.00
0.00
R1 = 0.034
wR2 = 0.087
R1 = 0.039
wR2 = 0.091
0.24 and -0.24
1,417,606
R1 = 0.071
wR2 = 0.166
R1 = 0.109
wR2 = 0.196
0.34 and -0.34
1,417,783
R1 = 0.040
wR2 = 0.089
R1 = 0.054
wR2 = 0.097
0.18 and -0.19
1,417,607
R indices (all data)
-3
˚
Largest diff. peak and hole, e A
CCDC No
X-Ray Crystallography
COLLECT [42] programs. Correction for absorption was
achieved in each program SADABS 2007/2 [43]. The
program MERCURY [44] was used in the preparation of
the Figures. SHELXL97 [45] and PLATON [46] were used
in the calculation of molecular geometry. The structures
were solved by direct methods using SHELXS-97 [45] and
fully refined by means of the program SHELXL-97 [45].
Difference map provided position for the aldehydic
hydrogen atoms of 2b. All other hydrogen atoms were
Data for compounds 1a and 2b were obtained at 120(2) K
while data for compound 2a were collected at 100(2) K, all
with Mo-Ka radiation by means of a Bruker–Nonius Roper
CCD camera on kappa-goniostat instrument of the NCS
crystallographic service, based at the University of
Southampton. Data collection, data reduction and unit cell
refinement were achieved with DENZO [41] and
123

J Chem Crystallogr (2016) 46:67–76
75
FAFM, Camilo ALS, da Silva GP, Costa CCP (2011) J Med
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placed in calculated positions. Crystal data and structure
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Supplementary Material
Full details of the crystal structure determinations in cif
format are available in the online version, at doi: (to be
inserted), and have also been deposited with the Cambridge
Crystallographic Data Centre with deposition numbers,
1417606, 1417783 and 1417607, respectively for 1a, 2a
and 2b. Copies of these can be obtained free of charge on
written application to CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: ?44 1223 336033); on request by
e-mail to deposit@ccdc.cam.ac.uk or by access to http://
www.ccdc.cam.ac.uk.
Acknowledgments The use of the NCS crystallographic service at
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gratefully acknowledged. JLW thanks FAPERJ, Brazil for support.
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Open Access This article is distributed under the terms of the
Creative Commons Attribution 4.0 International License (http://crea
tivecommons.org/licenses/by/4.0/), which permits unrestricted use,
distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a
link to the Creative Commons license, and indicate if changes were
made.
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