Two regioisomers of condensed thio-heterocyclic triazine synthesized from 6-phenyl-3-thioxo-2,3,4,5-tetra-hydro-1,2,4-triazin-5-one

Article abstract of DOI:10.1107/S0108270109043728

In the crystal structure of 6-phenyl-3-thioxo-2,3,4,5-tetra-hydro-1,2,4- triazin-5-one, C₉H₇N₃OS, (I), the 1,2,4-triazine moieties are connected by face-to-face contacts through two kinds of double hydrogen bonds (N - H...

Full text of DOI:10.1107/S0108270109043728

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Database (CSD, Version 5.30 of November 2008; Allen, 2002).
Thus, we hope that this paper concerning the results of
structural studies of (I) and the reaction products 6-phenyl-
2,3-dihydro-7H-1,3-thiazolo[3,2-b][1,2,4]triazin-7-one, (II),
and 3-phenyl-6,7-dihydro-4H-1,3-thiazolo[2,3-c][1,2,4]triazin-
ISSN 0108-2701
4
-one, (III), will provide a good basis for understanding the
Two regioisomers of condensed thio-
heterocyclic triazine synthesized from
intermolecular interactions and for designing further reac-
tions.
6
1
-phenyl-3-thioxo-2,3,4,5-tetrahydro-
,2,4-triazin-5-one
a,b
a
a
Akiko Hori, * Yasuhide Ishida, Takahiro Kikuchi,
a
a
Kumiko Miyamoto and Hiroshi Sakaguchi
a
School of Science, Kitasato University, Kitasato 1-15-1, Sagamihara, Kanagawa
b
2
28-8555, Japan, and PRESTO, JST, Honcho 4-1-8, Kawaguchi, Saitama, Japan
Correspondence e-mail: hori@kitasato-u.ac.jp
Received 14 October 2009
Accepted 22 October 2009
Online 7 November 2009
In the crystal structure of 6-phenyl-3-thioxo-2,3,4,5-tetra-
hydro-1,2,4-triazin-5-one, C H N OS, (I), the 1,2,4-triazine
9
7
3
Generally, two isomeric substances of thiazolotriazinone,
viz. 7H-thiazolo[3,2-b][1,2,4]triazin-7-one and 4H-thiazolo-
moieties are connected by face-to-face contacts through two
kinds of double hydrogen bonds (N—Hꢀ ꢀ ꢀO and N—Hꢀ ꢀ ꢀS),
which form planar ribbons along the a axis. The ribbons are
crosslinked through C—Hꢀ ꢀ ꢀꢀ interactions between the
phenyl rings. The molecular structures of two regioisomeric
compounds, namely 6-phenyl-2,3-dihydro-7H-1,3-thiazolo[3,2-b]-
[
(
2,3-c][1,2,4]triazin-4-one derivatives [analogues of (II) and
III), respectively], are obtained by the reaction of the
respective dihalogenoalkanes and thioxotriazinones [analo-
gues of (I)], which can be substituted by various alkyl, cyclo-
alkyl, aryl, heteroaryl and benzyl groups. However, the
isomers have been mainly identified from the synthetic
procedures and by spectroscopic studies. Only one crystal-
lographic study has been carried out, on benzyl-substituted
[1,2,4]triazin-7-one, C H N OS, (II), and 3-phenyl-6,7-di-
hydro-4H-1,3-thiazolo[2,3-c][1,2,4]triazin-4-one, C H N OS,
11 9 3
11
9
3
(
(
III), which were prepared by the condensation reaction of
I) with 1,2-dibromoethane, have been characterized by X-ray
7
H-thiazolo[3,2-b][1,2,4]triazin-7-one (Miyamoto et al., 1991).
crystallography and spectroscopic studies. The crystal struc-
tures of (II) and (III) both show two crystallographically
independent molecules. While the two compounds are
isomers, the unit-cell parameters and crystal packing are quite
different and (II) has a chiral crystal structure.
Thus, we considered that a full characterization of the two
isomers was essential for understanding the difference in the
molecular structures and the spectroscopic results. Therefore,
the crystal structures of the starting compound, (I), and both
of the phenyl-substituted isomers, (II) and (III), are now
discussed, along with the results of the condensation reaction.
In the crystal structure of (I), the phenyl and heterocyclic
rings are not coplanar and the dihedral angle between the
planes of the two rings defined by atoms N1/N2/C3/N4/C5/C6
Comment
6
-Phenyl-3-thioxo-2,3,4,5-tetrahydro-1,2,4-triazin-5-one, (I),
ꢁ
was prepared as an intermediate in the synthesis of thio-
heterocyclic derivatives (Arndt et al., 1984; Nyitrai et al., 1967),
which are used in the creation of biologically active reagents
and C11–C16 is 31.38 (4) (Fig. 1). The bond lengths in the
heterocyclic ring are given in Table 1. The N1—N2, N2—C3,
(Odds & Abbott, 1984; Boschelli et al., 1993). Because the
base part of thioxotriazinone, i.e. 5-hydroxy-3-mercapto-1,2,4-
triazine, in (I) is widely considered to be an active constituent
of biomolecules (Fotouhi et al., 2008), information about its
structure and intermolecular interactions is crucial for
chemists and pharmacologists. While many synthetic studies
have been reported, few crystal structure analyses of deriva-
tives of thioxotriazinone are known. Only four reports of the
methyl derivatives (Ferrari et al., 1995; Voutsas et al., 1978)
and its coordination complexes (Ghassemzadeh et al., 2004,
Figure 1
The molecular structure of (I) at 100 K, showing the atom-labelling
scheme. Displacement ellipsoids are drawn at the 50% probability level.
2005) were found during a search of the Cambridge Structural
Acta Cryst. (2009). C65, o593–o597
doi:10.1107/S0108270109043728
# 2009 International Union of Crystallography o593

organic compounds
Figure 2
Aview of part of the crystal structure of (I), showing the one-dimensional
hydrogen-bonded ribbons generated by pairs of N—Hꢀ ꢀ ꢀO and N—
Hꢀ ꢀ ꢀS hydrogen bonds. Symmetry codes are as in Table 2.
Figure 3
One of the two symmetry-independent molecules in each of (a) (II) and
(b) (III) at 100 K, showing the atom-labelling schemes. Displacement
ellipsoids are drawn at the 50% probability level.
C3—N4 and N4—C5 distances correspond with those
predicted for the conjugated bond lengths between the single
and double bonds, and the bond distances C6—C5 and
C6—N1 are those for localized single and double bonds,
respectively. The heterocyclic ring is planar and the r.m.s.
greater yield of (II) compared with that of (III) is consistent
with the previous report (Arndt et al., 1984), indicating that
the acidity of the H atom at N2—H2 is higher than that at
N4—H4 in starting compound (I) because of the expanding ꢀ-
conjugation of N2. Accordingly, the N2—C3 bond length in (I)
deviation of the six ring atoms from the mean ring plane is
˚
0.006 A. In the crystal packing (Fig. 2), there are pairs of N—
Hꢀ ꢀ ꢀO hydrogen bonds that link amino atom N4 in the
reference molecule at (x, y, z), via atom H4, across a centre of
inversion to carbonyl atom O1 of the molecule at (ꢂx, ꢂy + 1,
ꢂz + 2) and vice versa, while pairs of N—Hꢀ ꢀ ꢀS hydrogen
bonds link amino atom N2, via atom H2, across a centre of
inversion on the other side of the reference molecule to
thiocarbonyl atom S1 of the molecule at (ꢂx + 1, ꢂy + 1,
ꢂz + 2) and back again (Table 2). Accordingly, these inter-
actions link the molecules of (I) into one-dimensional ribbons
which propagate parallel to the [100] direction. The ribbons
are crosslinked by two different intermolecular C—Hꢀ ꢀ ꢀ
˚
[1.3487 (18) A] is slightly but significantly shorter than that of
˚
C3—N4 [1.3670 (17) A].
The crystal structures of (II) and (III) each have two crys-
tallographically independent molecules in the asymmetric
unit. Here, only one of the symmetry-independent molecules
of each structure, viz. (IIa) and (IIIa), is shown in Fig. 3.
Selected bond lengths in the heterocyclic rings are summar-
ized in Table 1. The molecular structure of (IIa) in Fig. 3(a)
shows that the lateral ethylene chain links atoms N2 and S1 in
a pseudo-eclipsed conformation; the torsion angle S1—C1—
ꢁ
ꢀ
(arene) interactions between the phenyl groups of adjacent
C2—N2 is ꢂ28.20 (17) and S2—C21—C22—N22 in (IIb) is
iii
iii
ꢁ
˚
molecules: C12ꢀ ꢀ ꢀCg1 = 3.4527 (15) A, H12ꢀ ꢀ ꢀCg1
=
=
=
26.76 (16) . C3—N4 and C6—N1 in the heterocyclic ring are
double bonds and C5—C6 is a single bond. The phenyl and
six-membered heterocyclic rings are not coplanar and the
iii
ꢁ
iv
˚
2
3
1
.76 A, C12—H12ꢀ ꢀ ꢀCg1
=
130 , C15ꢀ ꢀ ꢀCg1
iv
iv
˚
˚
.5085 (16) A, H15ꢀ ꢀ ꢀCg1 = 2.77 A, C15—H15ꢀ ꢀ ꢀCg1
ꢁ
ꢁ
35 , where Cg1 is the centroid of the phenyl ring [symmetry
3
dihedral angle between them is 26.17 (8) in (IIa) and
ꢁ
1
1
1
codes: (iii) ꢂx + , y ꢂ , z; (iv) ꢂx, y + , ꢂz + ].
44.25 (5) in (IIb). The molecular structure of (IIIa) in Fig. 3(b)
shows that the lateral ethylene chain links atoms N4 and S1 in
an eclipsed conformation; the torsion angle S1—C1—C2—N4
2
2
2
2
The same hydrogen-bonded ribbons are also found in the
methyl-substituted derivative (Ferrari et al., 1995). The
overlay (Macrae et al., 2006) of the atoms of the thio-
heterocyclic rings of (I) and the methyl derivative shows the
same structural characteristics (the r.m.s. deviation of the
ꢁ
ꢁ
is 11.09 (19) and S2—C21—C22—N24 in (IIIb) is ꢂ9.3 (2) .
N2—C3 and C6—N1 in the heterocyclic ring are double bonds
and C5—C6 is a single bond. The phenyl and six-membered
heterocyclic rings are almost coplanar, the dihedral angle
˚
atoms is 0.03 A), which indicates that the conformations of the
thioheterocyclic rings are almost independent of the substi-
tution of the phenyl and methyl groups.
ꢁ
ꢁ
between these rings being 7.38 (10) in (IIIa) and 7.81 (11) in
(IIIb). The molecules of (III) are overall much more planar
than those of (II), being influenced by the crystal packing as
discussed below. The five-membered rings, including the S
atom and Csp atoms, in (III) are flatter than those in (II); the
r.m.s. deviation of the ring atoms from their mean planes is
The reaction of (I) and 1,2-dibromoethane gave the thio-
heterocyclic compounds (II) and (III) in respective yields of
52 and 19%. Both compounds were isolated by column
chromatography and crystallized from 2-propanol. The
3
ꢃ
o594 Hori et al.
C H
9
7
N
3
OS, C11
H
9
N
3
OS and C11
H
9 3
N OS
Acta Cryst. (2009). C65, o593–o597

organic compounds
Figure 4
Conformational differences between the molecules in the different
structures estimated by superposition of the six-membered heterocyclic
˚
ring atoms plus atoms O1 and S1; (a) the average r.m.s. value is 0.07 A
˚
between (I) (black) and (IIa) (grey); (b) the average r.m.s. is 0.07 A
between (I) (black) and (IIIa) (grey).
˚
˚
.1272 A in (IIa), 0.1256 A in (IIb), 0.0532 A in (IIIa) and
˚
0
˚
.0450 A in (IIIb). The changes in the conformations of the
0
Figure 5
a) The crystal packing of (II), viewed along the c axis, and (b) that of
(III) viewed along the a axis.
heterocyclic six-membered ring in (I) upon the condensation
reaction to give (II) and (III) have been analysed by super-
imposing the molecules and finding the best fit to the six-
membered heterocyclic ring atoms plus atoms O1 and S1.
Because the average r.m.s. deviations of these atoms in the
overlay between (I)/(IIa) [or (IIIa)] is smaller than that of (I)/
(IIb) [or (IIIb)], the conformational difference after the
reaction was estimated by using (IIa) and (IIIa) in Fig. 4.
While the average r.m.s. deviations for (I)/(II) and (I)/(III)
˚
show great similarity, 0.07 A, the differences in the positions of
atoms N4, C3 and S1 in (II) and atoms N2, C3 and S1 in (III)
are larger than those for the other atoms.
Characterization of derivatives (II) and (III) was also
performed using IR and NMR spectroscopies, and mass
(
tion cannot expand to the N2 atoms, the fragment of m/z = 103
was observed for (II). These differences were also observed
for the methyl- and ethyl-substituted derivatives. Additionally,
the heteronuclear multiple bond correlation (HMBC) of the
two-dimensional NMR spectrum of (III) showed a correlation
peak between C5 and H2, while no correlation was observed
between C5 and the ethylene H atoms for (II).
The crystal packings of (II) and (III) are quite different, as
shown in Figs. 5(a) and 5(b), respectively. In the crystal of (II),
the planes of the condensed heterocyclic rings in (IIa) and
(IIb) involve a significant offset of the centroids of the rings to
give columnar arrangements of alternating (IIa) and (IIb)
molecules along the a axis. The five-membered rings and the
phenyl rings have face-to-face contact, but this does not
appear to involve ꢀ–ꢀ stacking. The columns are linked
spectrometry (MS). In the IR spectra, the distinctive C
O
ꢂ1
ꢂ1
band is observed at 1665 cm for (II) and 1669 cm for (III).
The differences in the C O, N4—C5 and C5—C6 bond
lengths for compounds (II) and (III) indicate that the double
bond of (II) is more localized than that of (III). Because the ꢀ-
conjugation is less expanded in (II) than in (III), the lower
energy of the C O stretching for (II) is consistent. Here, IR
shifts between the phenyl-substituted derivatives were smaller
than for the methyl- and ethyl-substituted derivatives (see
Experimental), probably because the ꢀ-systems compensate
for the localization of the C O double bonds. In the detailed
analysis of the mass spectra fragments, the peak at m/z = 128
was observed without the ‘phenyl/C6—N1 unit (m/z = 103)’
for (II) and the peak at m/z = 203 was observed without the
i
ii
through C1—H1Bꢀ ꢀ ꢀO1 , C13—H13ꢀ ꢀ ꢀO1 and C21—
iii
H21Bꢀ ꢀ ꢀN24 hydrogen-bond interactions (symmetry codes
are as in Table 3). In the crystal packing of (III), however, the
molecules associate pairwise between (IIIa)/(IIIa) or (IIIb)/
(IIIb). These pairs of molecules clearly show intermolecular
ꢀ–ꢀ stacking between the electron-rich phenyl ring and the
electron-poor six-membered ring of centrosymmetrically
related molecules. The shortest intermolecular atom-to-atom
ii
ii
distances are 3.320 (2) (C3ꢀ ꢀ ꢀC15 ), 3.332 (2) (C5ꢀ ꢀ ꢀC11 ),
iii
iii
˚
‘
ethylene unit (m/z = 28)’ for (III). These facts are compatible
with the crystal structures. Because the C6—N1 bond length of
II) is shorter than that of (III) and the localized ꢀ-conjuga-
3.342 (2) (C25ꢀ ꢀ ꢀC31 ) and 3.362 (2) A (C26ꢀ ꢀ ꢀC26 ), while
the centroid–centroid distances between the rings containing
ii
atoms C3 and C15 and between the rings containing atoms
(
ꢃ
Acta Cryst. (2009). C65, o593–o597
Hori et al.
9
C H
7 3 9 3 9 3
N OS, C11H N OS and C11H N OS o595

organic compounds
iii
˚
C25 and C31 are 3.7000 (11) and 3.6689 (12) A, respectively,
with corresponding angles between the ring planes of 5.78 (8)
Refinement
2
2
R[F > 2ꢃ(F )] = 0.030
wR(F ) = 0.082
127 parameters
H-atom parameters constrained
ꢁ
2
and 7.33 (9) [symmetry codes: (ii) ꢂx + 1, ꢂy + 1, ꢂz + 1; (iii)
˚
ꢂ3
Áꢄmax = 0.35 e A
S = 1.07
2023 reflections
ꢂx, ꢂy + 1, ꢂz]. The pairs are further linked through weak
ꢂ3
Áꢄmin = ꢂ0.23 e A˚
i
i
C2—H2Bꢀ ꢀ ꢀN1 and C22—H22Aꢀ ꢀ ꢀN21 hydrogen bonds
1
2
1
2
[
symmetry code: (i) x, ꢂy + , z + ] (Table 4).
Table 1
Selected bond distances (A) for (I), (II) and (III).
In conclusion, this study clearly characterizes two isomers of
˚
the phenyl-substituted thioheterocyclic triazine by means of
crystal structure analyses and spectroscopic studies, and
highlights the ꢀ-conjugation within the triazine ring of (II) and
(I)
(IIa)
(IIb)
(IIIa)
(IIIb)
N1—N2
N2—C3
C3—N4
N4—C5
C6—C5
C6—N1
C3—S1
C5—O1
1.3603 (16)
1.3487 (18)
1.3670 (17)
1.3789 (17)
1.4823 (19)
1.3059 (17)
1.6673 (14)
1.2236 (17)
1.352 (2)
1.347 (2)
1.303 (3)
1.390 (2)
1.493 (3)
1.303 (2)
1.7436 (17)
1.219 (2)
1.3556 (19)
1.353 (2)
1.302 (2)
1.385 (2)
1.494 (2)
1.300 (2)
1.7467 (17)
1.224 (2)
1.374 (2)
1.298 (2)
1.354 (2)
1.385 (2)
1.477 (2)
1.311 (2)
1.7462 (18)
1.221 (2)
1.375 (2)
1.297 (2)
1.354 (2)
1.382 (2)
1.474 (2)
1.311 (2)
1.7452 (18)
1.224 (2)
(III).
Experimental
Compound (I) was prepared by procedures similar to those reported
previously by Arndt et al. (1984). Typically, an aqueous solution
(
400 ml) of methyl benzoylformate (150 mmol) and thiosemi-
carbazide (150 mmol) was stirred at 343 K for 1.5 h. After cooling,
0% aqueous NaOH (ca 40 ml) was added slowly to the solution to
Table 2
Hydrogen-bond geometry (A, ) for (I).
3
˚
ꢁ
adjust the pH to 11 and the mixture was then stirred at 353 K for 4 h.
By the addition of 6 M HCl to pH = 1, a white powder of (I) was
obtained (62% yield). The products of (I) (50 mmol) and dibromo-
ethylene (50 mmol) were added to an EtOH solution (30 ml) of Na
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
i
N4—H4ꢀ ꢀ ꢀO1
0.88
0.88
1.96
2.46
2.8307 (15)
3.3166 (13)
169
163
ii
N2—H2ꢀ ꢀ ꢀS1
2 3
(50 mmol), then the mixture was refluxed for 1 h. Na CO (25 mmol)
Symmetry codes: (i) ꢂx; ꢂy þ 1; ꢂz þ 2; (ii) ꢂx þ 1; ꢂy þ 1; ꢂz þ 2.
was added to the solution and the mixture refluxed for 10 h. After
removing the solid by filtration, the solvent was evaporated to give a
white powder of compounds (II) and (III). The products were puri-
fied by column chromatography (silica gel, AcOEt) to give pure
products of (II) in 52% yield and (III) in 19% yield. Single crystals of
Compound (II)
Crystal data
(I), (II) and (III) suitable for X-ray crystallography were obtained by
cooling hot solutions of 2-propanol.
˚
V = 1033.72 (8) A
3
C
11
9 3
H N OS
M
r
= 231.27
Z = 4
Mo Kꢁ radiation
IR, MS and NMR spectra were measured using Shimadzu FT–IR-
400S (KBr disc), Shimadzu GCMS QP2010Plus and Varian NMR
Monoclinic, P21
a = 8.1257 (4) A˚
b = 11.3239 (5) A
c = 11.3860 (5) A
ꢅ = 99.3630 (10)
ꢂ1
8
ꢂ = 0.29 mm
T = 100 K
˚
˚
ꢁ
(Mercury-300 and UNITY-400) spectrometers, respectively. IR data
on C O stretching bands and MS fragments are as follows. For (II),
0.45 ꢄ 0.40 ꢄ 0.20 mm
ꢂ1
IR: 1665 cm ; MS: 231, 128, 60 m/z; 6-methyl-2,3-dihydro-7H-thia-
ꢂ1
zolo[3,2-b][1,2,4]triazin-7-one (methyl derivative), IR: 1637 cm
MS: 169, 128, 60 m/z; 6-ethyl-2,3-dihydro-7H-thiazolo[3,2-b][1,2,4]tri-
;
Data collection
ꢂ1
Bruker APEXII CCD
diffractometer
Absorption correction: empirical
(using intensity measurements)
5756 measured reflections
2992 independent reflections
2939 reflections with I > 2ꢃ(I)
azin-7-one (ethyl derivative), IR: 1649 cm ; MS: 183, 128, 60 m/z.
ꢂ1
For (III), IR: 1669 cm ; MS: 231, 203, 103 m/z; 3-methyl-6,7-dihy-
dro-4H-thiazolo[2,3-c][1,2,4]triazin-4-one (methyl derivative), IR:
Rint = 0.014
ꢂ1
(SADABS; Sheldrick, 1996)
1
684 cm ; MS: 169, 141, 56 m/z; 3-ethyl-6,7-dihydro-4H-thiazolo-
ꢂ1
Tmin = 0.880, Tmax = 0.944
[
2,3-c][1,2,4]triazin-4-one (ethyl derivative), IR: 1672 cm ; MS: 183,
154, 56 m/z.
Refinement
2
2
˚
ꢂ3
Áꢄmax = 0.29 e A
R[F > 2ꢃ(F )] = 0.024
wR(F ) = 0.061
S = 1.04
2
2
1
2
˚
ꢂ3
Áꢄmin = ꢂ0.20 e A
Compound (I)
Absolute structure: Flack &
Bernardinelli (2000), 577
Friedel pairs
992 reflections
90 parameters
restraint
Crystal data
˚
V = 1778.1 (3) A
3
C
9
7 3
H N OS
Flack parameter: 0.02 (7)
M
r
= 205.24
Orthorhombic, Pbca
Z = 8
Mo Kꢁ radiation
ꢂ = 0.33 mm
T = 100 K
H-atom parameters constrained
˚
a = 11.1891 (11) A
b = 7.4401 (7) A
˚
c = 21.359 (2) A
ꢂ1
˚
Table 3
Hydrogen-bond geometry (A, ) for (II).
0.30 ꢄ 0.20 ꢄ 0.06 mm
˚
ꢁ
Data collection
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
Bruker APEXII CCD
diffractometer
Absorption correction: empirical
9167 measured reflections
2023 independent reflections
1746 reflections with I > 2ꢃ(I)
i
C1—H1Bꢀ ꢀ ꢀO1
0.99
0.95
0.99
2.50
2.56
2.45
3.183 (2)
3.150 (2)
3.351 (2)
126
120
151
ii
C13—H13ꢀ ꢀ ꢀO1
iii
C21—H21Bꢀ ꢀ ꢀN24
(using intensity measurements)
R
int = 0.021
1
2
1
2
1
2
(
T
SADABS; Sheldrick, 1996)
min = 0.908, Tmax = 0.981
Symmetry codes: (i) ꢂx þ 1; y þ ; ꢂz þ 1; (ii) ꢂx þ 1; y þ ; ꢂz; (iii) ꢂx þ 2; y ꢂ ,
ꢂz.
ꢃ
o596 Hori et al.
C H
9
7
N
3
OS, C11
H
9
N
3
OS and C11
H
9 3
N OS
Acta Cryst. (2009). C65, o593–o597

organic compounds
Table 4
Hydrogen-bond geometry (A, ) for (III).
For all compounds, data collection: APEX2 (Bruker, 2006); cell
refinement: SAINT (Bruker, 2006); data reduction: SAINT;
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: SHELXTL (Sheldrick, 2008); software used to
prepare material for publication: SHELXTL.
˚
ꢁ
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
i
C2—H2Bꢀ ꢀ ꢀN1
0.99
0.99
2.40
2.40
3.338 (2)
3.325 (2)
158
155
i
C22—H22Aꢀ ꢀ ꢀN21
Symmetry code: (i) x; ꢂy þ ; z þ .
1
2
1
2
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: LN3135). Services for accessing these data are
described at the back of the journal.
Compound (III)
Crystal data
References
˚
3
C
M
11
H
9
N
3
OS
= 231.27
V = 2020.6 (4) A
Z = 8
r
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
Arndt, F., Franke, W., Klose, W., Lorenz, J. & Schwarz, K. (1984). Liebigs Ann.
Chem. pp. 1302–1307.
Boschelli, D. H., Conner, D. T., Bornemeier, D. A., Dyer, R. D., Kennedy, J. A.,
Kuipers, P. J., Okonkwo, G. C., Schrier, D. J. & Wright, C. D. (1993). J. Med.
Chem. 36, 1802–1810.
Monoclinic, P2 =c
Mo Kꢁ radiation
1
˚
a = 21.627 (3) A
ꢂ1
ꢂ = 0.30 mm
T = 100 K
˚
b = 8.1222 (10) A
˚
c = 11.8888 (15) A
0.30 ꢄ 0.30 ꢄ 0.10 mm
ꢁ
ꢅ = 104.638 (2)
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Data collection
Ferrari, M. B., Fava, G. G., Pelosi, G., Rodriguez-Arguelles, M. C. & Tarasconi,
P. (1995). J. Chem. Soc. Dalton Trans. pp. 3035–3040.
Flack, H. D. & Bernardinelli, G. (2000). J. Appl. Cryst. 33, 1143–1148.
Fotouhi, L., Hekmatshoar, R., Heravi, M. M., Sadjadi, S. & Rasmi, V. (2008).
Tetrahedron Lett. 49, 6628–6630.
Bruker APEXII CCD
diffractometer
Absorption correction: empirical
10860 measured reflections
4517 independent reflections
3632 reflections with I > 2ꢃ(I)
(using intensity measurements)
Rint = 0.023
Ghassemzadeh, M., Heravi, M. M. & Neumuller, B. (2005). Z. Anorg. Allg.
Chem. 631, 2401–2407.
(
T
SADABS; Sheldrick, 1996)
min = 0.916, Tmax = 0.971
Ghassemzadeh, M., Pooramini, M. M., Tabatabaee, M., Heravi, M. M. &
Neumuller, B. (2004). Z. Anorg. Allg. Chem. 630, 403–406.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor,
R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
Miyamoto, K., Sakaguchi, H., Yoshii, S., Takayanagi, H., Ogura, H. & Iitaka, Y.
Refinement
2
2
R[F > 2ꢃ(F )] = 0.040
wR(F ) = 0.101
289 parameters
H-atom parameters constrained
2
˚
ꢂ3
Áꢄmax = 0.56 e A
(
1991). Anal. Sci. 7, 831–832.
Nyitrai, J., Bekassy, S. & Lempert, K. (1967). Acta Chim. Acad. Sci. Hung. 53,
11–314.
S = 1.03
4517 reflections
Áꢄmin = ꢂ0.50 e A˚
ꢂ3
3
Odds, F. C. & Abbott, A. B. (1984). J. Antimicrob. Chemother. 14, 105–114.
Sheldrick, G. M. (1996). SADABS. University of G o¨ ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Voutsas, G. P., Venetopoulos, C. C., Kalman, A., Parkanyi, L., Hornyak, G. &
Lempert, K. (1978). Tetrahedron Lett. pp. 4431–4434.
All H atoms were placed in geometrically idealized positions and
˚
refined as riding, with aromatic C—H = 0.95 A, aliphatic C—H =
˚ ˚
.99 A and N—H = 0.88 A, and with Uiso(H) = 1.2Ueq(parent atom).
0
ꢃ
Acta Cryst. (2009). C65, o593–o597
Hori et al.
9
C H
7 3 9 3 9 3
N OS, C11H N OS and C11H N OS o597