The influence of sulfur substituents on the mol-ecular geometry and packing of thio derivatives of N-methyl-phenobarbital

Article abstract of DOI:10.1107/S0108270108043060

The room-temperature crystal structures of four new thio derivatives of N-methyl-phenobarbital [systematic name: 5-ethyl-1-methyl-5-phenyl-pyrimidine-2, 4,6(1H,3H,5H)-trione], Cl3H14N₂O₃, are compared with the structure of the parent

Full text of DOI:10.1107/S0108270108043060

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
hypnotic, amnesiac and anticonvulsant properties (Kushikata
et al., 2003; Huber et al., 2009). The structures of numerous
barbituric acid derivatives, such as phenobarbital, have been
studied with respect to their ability to form polymorphs
(Williams, 1973, 1974; Platteau et al., 2005; Day et al., 2007).
However, there are only a few examples of sulfur analogues of
barbiturates. Recently, the crystal structure of 5-benzyl-1,3,5-
trimethyltrithiobarbiturate was reported (Takechi et al., 2007).
ISSN 0108-2701
The influence of sulfur substituents on
the molecular geometry and packing
of thio derivatives of N-methyl-
phenobarbital
Alicja Janik,a* Andrzej Olech,a Anna Stasiewicz-Urbanb
and Katarzyna Stadnickaa
aFaculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland,
and bFaculty of Pharmacy, Medical College, Jagiellonian University, Medyczna 9,
30-688 Krakow, Poland
In this paper, we present the crystal structures of four thio
derivatives of N-methylphenobarbital, all crystallizing in the
centrosymmetric space group P21/n. The structural formulae
of the derivatives are given in the scheme. The asymmetric
units of N-methyl-2-thiophenobarbital, 2-TP, N-methyl-4-
Correspondence e-mail: janik@chemia.uj.edu.pl
Received 13 November 2008
Accepted 17 December 2008
Online 14 January 2009
The room-temperature crystal structures of four new thio
derivatives of N-methylphenobarbital [systematic name:
5-ethyl-1-methyl-5-phenylpyrimidine-2,4,6(1H,3H,5H)-trione],
C13H14N2O3, are compared with the structure of the parent
compound. The sulfur substituents in N-methyl-2-thio-
phenobarbital [5-ethyl-1-methyl-5-phenyl-2-thioxo-1,2-di-
hydropyrimidine-4,6(3H,5H)-dione], C13H14N2O2S, N-methyl-
4-thiophenobarbital [5-ethyl-1-methyl-5-phenyl-4-thioxo-
3,4-dihydropyrimidine-2,6(1H,5H)-dione], C13H14N2O2S, and
N-methyl-2,4,6-trithiophenobarbital [5-ethyl-1-methyl-5-
phenylpyrimidine-2,4,6(1H,3H,5H)-trithione], C13H14N2S3,
preserve the heterocyclic ring puckering observed for N-
methylphenobarbital (a half-chair conformation), whereas in
N-methyl-2,4-dithiophenobarbital [5-ethyl-1-methyl-5-phenyl-
2,4-dithioxo-1,2,3,4-tetrahydropyrimidine-6(5H)-one], C13H14-
N2OS2, significant flattening of the ring was detected. The
number and positions of the sulfur substituents influence the
packing and hydrogen-bonding patterns of the derivatives. In
the cases of the 2-thio, 4-thio and 2,4,6-trithio derivatives,
there is a preference for the formation of a ring motif of the
R22(8) type, which is also a characteristic of N-methyl-
phenobarbital, whereas a C(6) chain forms in the 2,4-dithio
derivative. The preferences for hydrogen-bond formation,
which follow the sequence of acceptor position 4 > 2 > 6,
confirm the differences in the nucleophilic properties of the C
atoms of the heterocyclic ring and are consistent with the
course of N-methylphenobarbital thionation reactions.
Comment
Barbiturates are a widespread group of compounds with
various pharmacological activities. In particular, pheno-
barbital, thiopental and pentobarbital have been the subjects
of extensive research due to their anaesthetic, sedative,
Figure 1
The asymmetric units of 2-TP, 4-TP, 2,4-DTP, 2,4,6-TTP and P, showing
the atom-numbering schemes. Displacement ellipsoids are drawn at the
50% probability level.
o70 # 2009 International Union of Crystallography
doi:10.1107/S0108270108043060
Acta Cryst. (2009). C65, o70–o75

organic compounds
Figure 3
The packing of the molecules in 2-TP with the N3—H3ꢃ ꢃ ꢃO4 R22(8)-type
hydrogen-bond system. H atoms, except for those involved in the
moderate hydrogen bonds, have been omitted for clarity.
Figure 2
Hydrogen-bond motifs observed in the crystal structures of 2-TP, 4-TP,
2,4-DTP, 2,4,6-TTP and P. [Symmetry codes: (i) 2 ꢂ x, 1 ꢂ y, ꢂz; (ii) 2 ꢂ x,
1 ꢂ y, 1 ꢂ z; (iii) 1 + x, y, z; (iv) 1 ꢂ x, 2 ꢂ y, 1 ꢂ z; (v) ꢂ x, ꢂy, 1 ꢂ z.]
thiophenobarbital, 4-TP, N-methyl-2,4-dithiophenobarbital,
2,4-DTP, N-methyl-2,4,6-trithiophenobarbital, 2,4,6-TTP, and
N-methylphenobarbital, P, are shown in Fig. 1. The structure
of the latter compound was redetermined at 293 (2) K, to
enable all five structures to be compared under the same
conditions. The previously published data for N-methyl-
phenobarbital were obtained at 163 K by Lewis et al. (2005)
and refined to R = 0.042. A determination at 295 K by Bideau
et al. (1969) was a low-quality determination with R = 0.107.
Selected geometric parameters at 293 (2) K for the crystal
structures of the thio derivatives are given in Table 1, together
with the values observed for N-methylphenobarbital at
293 (2) K and also at 163 (2) K (Lewis et al., 2005). The C—N
bond lengths are similar to those found in ꢀ-lactams (Csp2—
Figure 4
The packing of the molecules in 4-TP with the N3—H3ꢃ ꢃ ꢃO2 R22(8)-type
hydrogen-bond system. H atoms, except for those involved in the
moderate hydrogen bonds, have been omitted for clarity.
2
˚
Nsp = 1.385 A; Allen et al., 1995), indicating that the lone
pairs of the N1 and N3 atoms are conjugated with the carbonyl
or thiocarbonyl groups, which results in the C2—N1—C6 and
C2—N3—C4 angles being greater than 120ꢀ [the average
values are 123.4 (3) and 127.8 (7)ꢀ, respectively], whereas the
mean value of the C4—C5—C6 angle at the chiral centre is
112.8 (11)ꢀ. The heterocyclic ring in all the crystal structures
adopts a half-chair conformation; the torsion angles and ring-
puckering parameters are given in Table 1. The set of torsion
angles defining the heterocyclic ring conformation was found
to be similar for 2-TP, 2,4,6-TTP, 4-TP and P, whereas for
2,4-DTP all the torsion angles are close to zero, which indi-
cates that the ring is significantly flattened. The geometric
parameters of P at 293 (2) K are comparable with those found
at 163 (2) K.
The C S bond lengths in the thio derivatives are signifi-
˚
˚
cantly shortened [range 1.630–1.646 A, average 1.639 (6) A,
see Table 1] compared with the value characteristic for
˚
thioureas (1.681 A; Allen et al., 1995) and are similar
to those observed in 5-benzyl-1,3,5-trimethylpyrimidine-
2,4,6(1H,3H,5H)-trithione (Takechi et al., 2007). The average
˚
value of the C O bond lengths was found to be 1.212 (5) A,
which is also relatively short compared with the values
observed in ureas (Allen et al., 1995).
Both P and its thio derivatives possess only one hydrogen-
bond donor (the N3—H3 amide group), despite an excess of
acceptor groups, which limits the number of possible moderate
hydrogen bonds. The analysis of the hydrogen-bond para-
ꢁ
Acta Cryst. (2009). C65, o70–o75
Janik et al.
C13H14N2O2S, C13H14N2O2S, C13H14N2OS2, C13H14N2S3 and C13H14N2O3 o71

organic compounds
Figure 5
The packing of the molecules in 2,4-DTP with the N3—H3ꢃ ꢃ ꢃO6
hydrogen bonds forming a C(6)-type chain along the a direction. H atoms,
except for those involved in the moderate hydrogen bonds, have been
omitted for clarity.
Figure 7
Edge-to-face interactions stabilizing the crystal structure of (2-TP). Only
the H atom at N3 is shown.
Figure 8
Edge-to-face interactions stabilizing the crystal structure of (2,4,6-TTP).
Only the H atom at N3 is shown.
Figure 6
The packing of the molecules in 2,4,6-TTP with the N3—H3ꢃ ꢃ ꢃS4 R22(8)-
type hydrogen-bond system. H atoms, except for those involved in the
moderate hydrogen bonds, have been omitted for clarity.
system determines the specific packing pattern in the struc-
tures of the thio derivatives. The R22(8) ring composed of N3—
H3ꢃ ꢃ ꢃO4i [symmetry code: (i) 2 ꢂ x, 1 ꢂ y, ꢂz] hydrogen
bonds in 2-TP and that of N3—H3ꢃ ꢃ ꢃS4iv [symmetry code: (iv)
1 ꢂ x, 2 ꢂ y, 1 ꢂ z] in 2,4,6-TTP enforce the same molecular
packing arrangement shown in Figs. 3 and 6, respectively.
Although the R22(8) system is also observed in the structure of
4-TP, the packing of the molecules is different (Fig. 4) because
of the different acceptor type in the N3—H3ꢃ ꢃ ꢃO2ii [symmetry
code: (ii) 2 ꢂ x, 1 ꢂ y, 1 ꢂ z] hydrogen bond. In 2,4-DTP the
R22(8) ring is not preserved because the donor and acceptor
functional groups are not in adjacent positions on the
heterocyclic ring. Instead, the packing of the molecules (Fig. 5)
is dominated by a C(6) chain formed by the N3—H3ꢃ ꢃ ꢃO6iii
[symmetry code: (iii) x + 1, y, z] hydrogen bond (Fig. 2).
The preference of the moderate hydrogen-bond formation
seems to follow the acceptor atom position in the heterocyclic
ring according to the sequence 4 > 2 > 6, which corresponds
with the nucleophilic properties of the heterocyclic ring C
atoms. This finding is consistent with the order of the S atom
meters (Table 2) indicates the preferential acceptor properties
of the O atom in position 4. If position 4 is occupied by an S
atom, the role of the acceptor is taken over by the O atom in
position 2 (as in 4-TP). In the case of the 2,4-dithio derivative,
only the O atom in position 6 is available as the strong
acceptor (the electronegativity of the O atom is 3.44 whereas
that for the S atom is 2.58, which is comparable with that of a C
atom, 2.55). When all the O atoms are replaced by S atoms in
2,4,6-TTP, position 4 is preferred again for the N—Hꢃ ꢃ ꢃS
hydrogen bond.
As can be seen in Fig. 2, the structures of 2-TP, 4-TP and
2,4,6-TTP contain centrosymmetric hydrogen-bonded dimers,
like those observed in P, formed by the intermolecular N3—
H3ꢃ ꢃ ꢃO or N3—H3ꢃ ꢃ ꢃS interactions across a centre of inver-
sion. This hydrogen-bond motif can be recognized as the
typical R22(8) according to the graph-set approach (Etter et al.,
1990; Bernstein et al., 1995). The type of hydrogen-bond
ꢁ
o72 Janik et al. C13H14N2O2S, C13H14N2O2S, C13H14N2OS2, C13H14N2S3 and C13H14N2O3
Acta Cryst. (2009). C65, o70–o75

organic compounds
substitution in the thionation of N-methyphenobarbital, in
which the amount of the thio derivatives of P in the reaction
product was found to be: 4-TP 26% > 2,4-DTP 22% > 2-TP
16% (Stasiewicz-Urban et al., 2004).
4-TP
Crystal data
3
˚
V = 1269.13 (6) A
Z = 4
C13H14N2O2S
Mr = 262.32
Because the moderate hydrogen bonds form only discrete
dimers or one-dimensional chains, the three-dimensional
architecture of the molecular packing has to be provided by
weak intermolecular interactions, the geometric parameters of
which are summarized in Table 3. In the structures of 2-TP and
2,4,6-TTP, with the substituent in position 4 (O4 and S4,
respectively) serving as the acceptor for the N—H group, the
hydrophobic layers (depicted in Figs. 7 and 8) are formed as a
result of weak C—Hꢃ ꢃ ꢃꢁ edge-to-face interactions between
the benzene rings of adjacent molecules. Similar behaviour of
the molecules is observed in the structure of (P).
Monoclinic, P21=n
Mo Kꢂ radiation
ꢃ = 0.25 mmꢂ1
T = 293 (2) K
0.32 ꢄ 0.30 ꢄ 0.07 mm
˚
a = 11.5609 (3) A
˚
b = 9.5538 (3) A
˚
c = 11.7268 (3) A
ꢀ = 101.521 (2)ꢀ
Data collection
KappaCCD diffractometer
Absorption correction: multi-scan
(DENZO and SCALEPACK;
Otwinowski & Minor, 1997)
Tmin = 0.929, Tmax = 0.980
5542 measured reflections
3381 independent reflections
2494 reflections with I > 2ꢄ(I)
Rint = 0.021
Refinement
In all the structures studied, the methyl group in position 1
seems to be engaged as the donor in weak intramolecular C—
Hꢃ ꢃ ꢃO or C—Hꢃ ꢃ ꢃS hydrogen bonds. The differences in the
values of the torsion angle defining the spatial arrangement of
the substituents at position 5 (C4—C5—C7—C8 and C4—
C5—C9—C10, Table 1), observed even in the structures with
similar packing patterns, may be attributed to the resultant
effect of the different set of weak attractive, weak repulsive
and steric interactions. In the structure of 4-TP, atom O6 is
close to the centre of the neighbouring pyrimidine hetero-
R[F2 > 2ꢄ(F2)] = 0.050
wR(F2) = 0.145
S = 1.04
3381 reflections
168 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢅmax = 0.37 e A
ꢂ3
˚
Áꢅmin = ꢂ0.41 e A
2,4-DTP
Crystal data
3
˚
V = 1330.47 (13) A
Z = 4
C13H14N2OS2
Mr = 278.38
3
1
1
˚
cyclic ring [Cg2 at (ꢂx + , y + , ꢂz + ); 3.214 (2) A]. A
2
2
2
Monoclinic, P21=n
Mo Kꢂ radiation
ꢃ = 0.39 mmꢂ1
T = 293 (2) K
0.25 ꢄ 0.15 ꢄ 0.10 mm
similar observation can be made for the O2 atom in the
1
˚
a = 6.9600 (3) A
3
˚
structure of P [Cg2 at (ꢂx, y ꢂ , ꢂz + ); 2.921 (2) A].
˚
b = 14.9407 (7) A
2
2
˚
c = 13.1556 (10) A
ꢀ = 103.454 (2)ꢀ
Experimental
Data collection
The title compunds were obtained by the thionation of N-methyl-
phenobarbital with Lawesson’s reagent (Stasiewicz-Urban et al.,
2004). Crystals suitable for X-ray diffraction were grown by slow
evaporation at room temperature from a mixture of n-hexane and
ethyl acetate in the ratio 3:1 for 2-TP and 4-TP, from cyclohexane for
2,4-DTP, from n-hexane for 2,4,6-TTP and from ethanol for P.
KappaCCD diffractometer
Absorption correction: multi-scan
(DENZO and SCALEPACK;
Otwinowski & Minor, 1997)
Tmin = 0.916, Tmax = 0.955
5152 measured reflections
2856 independent reflections
2309 reflections with I > 2ꢄ(I)
Rint = 0.032
Refinement
R[F2 > 2ꢄ(F2)] = 0.046
wR(F2) = 0.114
S = 1.06
2856 reflections
168 parameters
H atoms treated by a mixture of
independent and constrained
refinement
2-TP
ꢂ3
˚
Áꢅmax = 0.21 e A
Crystal data
ꢂ3
˚
Áꢅmin = ꢂ0.29 e A
3
˚
C13H14N2O2S
Mr = 262.32
V = 1301.52 (6) A
Z = 4
Monoclinic, P21=n
Mo Kꢂ radiation
ꢃ = 0.24 mmꢂ1
T = 293 (2) K
0.35 ꢄ 0.30 ꢄ 0.12 mm
˚
a = 12.9315 (3) A
2,4,6-TTP
˚
b = 7.1804 (2) A
˚
c = 15.2362 (5) A
Crystal data
ꢀ = 113.077 (1)ꢀ
3
˚
V = 1406.56 (9) A
Z = 4
C13H14N2S3
Mr = 294.44
Data collection
Monoclinic, P21=n
Mo Kꢂ radiation
ꢃ = 0.51 mmꢂ1
T = 293 (2) K
0.19 ꢄ 0.15 ꢄ 0.05 mm
˚
a = 13.8686 (2) A
KappaCCD diffractometer
Absorption correction: multi-scan
(DENZO and SCALEPACK;
Otwinowski & Minor, 1997)
Tmin = 0.924, Tmax = 0.976
4964 measured reflections
2978 independent reflections
2293 reflections with I > 2ꢄ(I)
Rint = 0.021
˚
b = 7.2346 (4) A
˚
c = 14.9844 (5) A
ꢀ = 110.681 (1)ꢀ
Data collection
Refinement
KappaCCD diffractometer
Absorption correction: multi-scan
(DENZO and SCALEPACK;
Otwinowski & Minor, 1997)
Tmin = 0.905, Tmax = 0.975
5585 measured reflections
3201 independent reflections
2587 reflections with I > 2ꢄ(I)
Rint = 0.025
R[F2 > 2ꢄ(F2)] = 0.045
wR(F2) = 0.111
S = 1.02
164 parameters
H-atom parameteꢂrs3 constrained
˚
Áꢅmax = 0.24 e A
ꢂ3
˚
2978 reflections
Áꢅmin = ꢂ0.28 e A
ꢁ
Acta Cryst. (2009). C65, o70–o75
Janik et al.
C13H14N2O2S, C13H14N2O2S, C13H14N2OS2, C13H14N2S3 and C13H14N2O3 o73

organic compounds
Table 1
A comparison of selected geometric parameters and ring-puckering parameters (A, ) for the thio derivatives of N-methylphenobarbital.
ꢀ
˚
Ring-puckering parameters, defined according to Cremer & Pople (1975), were calculated using the PARST program (Nardelli, 1983).
2–TP
4–TP
2,4–DTP
2,4,6–TTP
P
P†
N1—C2
C2—N3
N3—C4
C4—C5
C5—C6
N1—C6
C2—O2/S2
C4—O4/S4
C6—O6/S6
1.371 (2)
1.371 (2)
1.364 (2)
1.512 (2)
1.526 (2)
1.402 (2)
1.6436 (17)
1.2147 (19)
1.2039 (19)
1.382 (2)
1.372 (2)
1.366 (2)
1.527 (2)
1.529 (2)
1.381 (2)
1.218 (2)
1.6297 (18)
1.211 (2)
1.371 (2)
1.377 (3)
1.361 (3)
1.525 (3)
1.523 (3)
1.389 (3)
1.646 (2)
1.635 (2)
1.210 (2)
1.377 (3)
1.376 (3)
1.352 (3)
1.520 (3)
1.543 (3)
1.383 (3)
1.640 (2)
1.643 (2)
1.632 (2)
1.384 (2)
1.377 (2)
1.363 (2)
1.525 (2)
1.525 (2)
1.380 (2)
1.2072 (19)
1.2176 (19)
1.221 (2)
1.391 (2)
1.379 (2)
1.365 (2)
1.528 (2)
1.528 (2)
1.386 (2)
1.2095 (19)
1.2184 (19)
1.2126 (19)
C2—N1—C6
N1—C2—N3
C2—N3—C4
N3—C4—C5
C4—C5—C6
N1—C6—C5
122.93 (14)
116.44 (14)
127.72 (14)
116.20 (13)
111.91 (13)
117.04 (14)
123.39 (14)
117.06 (14)
126.67 (15)
114.43 (15)
112.66 (14)
118.75 (14)
123.81 (17)
116.82 (17)
128.56 (18)
116.46 (17)
114.50 (16)
119.70 (16)
123.34 (18)
115.95 (19)
128.24 (19)
115.71 (18)
111.90 (16)
116.81 (18)
124.52 (13)
116.54 (13)
126.16 (13)
116.05 (13)
112.05 (13)
118.19 (13)
124.39 (13)
116.52 (13)
126.06 (13)
116.23 (13)
111.91 (13)
118.20 (13)
N1—C2—N3—C4
C2—N3—C4—C5
N3—C4—C5—C6
C4—C5—C6—N1
C5—C6—N1—C2
C6—N1—C2—N3
C4—C5—C7—C8
C4—C5—C9—C10
C4—C5—C9—C14
10.4 (3)
3.4 (2)
5.2 (3)
ꢂ25.1 (3)
30.1 (2)
ꢂ19.2 (2)
ꢂ0.1 (3)
8.6 (2)
ꢂ66.7 (2)
111.14 (19)
ꢂ69.7 (2)
2.4 (3)
ꢂ1.0 (3)
1.1 (3)
13.8 (4)
0.9 (3)
ꢂ5.4 (2)
22.5 (2)
5.9 (2)
ꢂ23.0 (2)
29.84 (18)
ꢂ23.27 (19)
8.1 (2)
ꢂ23.72 (19)
32.14 (18)
ꢂ20.9 (2)
ꢂ0.8 (2)
61.7 (2)
ꢂ23.0 (3)
ꢂ29.38 (19)
ꢂ2.7 (3)
32.1 (2)
22.8 (2)
ꢂ7.5 (2)
4.5 (3)
ꢂ19.9 (3)
ꢂ3.1 (3)
61.5 (2)
ꢂ4.1 (3)
ꢂ58.9 (2)
66.3 (2)
ꢂ113.3 (2)
ꢂ2.8 (2)
2.2 (2)
63.76 (19)
59.16 (18)
ꢂ121.73 (16)
ꢂ63.03 (19)
ꢂ59.21 (17)
ꢂ121.60 (15)
ꢂ3.4 (2)
ꢂ15.5 (3)
177.55 (15)
165.6 (2)
q2
q3
0.251 (1)
0.120 (2)
80.9 (4)
0.278 (2)
115.5 (3)
0.232 (2)
0.117 (2)
ꢂ154.1 (4)
0.260 (2)
63.3 (4)
0.019 (2)
0.023 (2)
ꢂ11 (5)
0.030 (2)
39 (4)
0.269 (2)
ꢂ0.107 (2)
80.8 (5)
0.289 (2)
111.8 (4)
0.198 (1)
ꢂ0.136 (2)
37.5 (5)
0.240 (2)
124.6 (3)
’
QT
2
ꢆ2
† The crystal structure of N-methylphenobarbital at 163 K was reported by Lewis et al. (2005) with R = 4.21%; Cambridge Structural Database (Allen, 2002) refcode: MEPBAB01.
Although all the derivatives studied have a chiral centre at the C5
atom, their crystal structures are centrosymmetric and so the crystals
contain racemates. All H atoms were initially located in difference
Fourier maps. The H atoms of the methyl (C1 and C8) and methylene
(C7) groups and those of the phenyl ring (C10–C14) were subse-
quently included in the refinement in geometrically idealized posi-
Refinement
R[F2 > 2ꢄ(F2)] = 0.048
wR(F2) = 0.116
S = 1.06
3201 reflections
166 parameters
1 restraint
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢅmax = 0.32 e A
ꢂ3
˚
Áꢅmin = ꢂ0.38 e A
˚
tions, with C—H = 0.96, 0.97 and 0.93 A, respectively, and refined
using the riding model with isotropic displacement parameters of
Uiso(H) = 1.2Ueq(parent atom). The H atom attached to the N3 atom
was constrained to an idealized position for 2-TP, with N—H =
P
Crystal data
˚
˚
0.86 A, restrained assuming a target N—H distance of 0.86 (1) A for
2,4,6-TTP and with Uiso(H) = 1.2Ueq(N) in both cases. For the
remaining structures, the positional and displacement parameters of
this H atom were refined freely. In the final stage of the refinement, a
few reflections, probably affected by absorption, were omitted
(4-TP: reflections 200 and 153; 2,4-DTP: 032, 0121, 793 and 210;
2,4,6-TTP: 200; P: 413, 620 and 114). Additionally, in the case of 2,4-
DTP, ꢆmax was also reduced from 27.41 to 27.00ꢀ (97 reflections
omitted) which improved the data completeness (0.976 to
0.986).
3
˚
V = 1212.84 (7) A
Z = 4
C13H14N2O3
Mr = 246.26
Monoclinic, P21=c
Mo Kꢂ radiation
ꢃ = 0.10 mmꢂ1
T = 293 (2) K
0.30 ꢄ 0.30 ꢄ 0.30 mm
˚
a = 13.7063 (5) A
˚
b = 7.2553 (2) A
˚
c = 12.6606 (4) A
ꢀ = 105.565 (2)ꢀ
Data collection
KappaCCD diffractometer
Absorption correction: multi-scan
(DENZO and SCALEPACK;
Otwinowski & Minor, 1997)
Tmin = 0.972, Tmax = 0.975
4931 measured reflections
2756 independent reflections
2230 reflections with I > 2ꢄ(I)
Rint = 0.019
For all compounds, data collection: COLLECT (Nonius, 1997); cell
refinement: DENZO-SMN (Otwinowski & Minor, 1997); data
reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997);
program(s) used to solve structure: SIR92 (Altomare et al., 1994);
program(s) used to refine structure: SHELXL97 (Sheldrick, 2008);
molecular graphics: PLATON (Spek, 2003), ORTEP-3 for Windows
(Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to
prepare material for publication: SHELXL97.
Refinement
R[F2 > 2ꢄ(F2)] = 0.051
wR(F2) = 0.143
S = 1.05
2756 reflections
167 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢅmax = 0.37 e A
ꢂ3
˚
Áꢅmin = ꢂ0.23 e A
ꢁ
o74 Janik et al. C13H14N2O2S, C13H14N2O2S, C13H14N2OS2, C13H14N2S3 and C13H14N2O3
Acta Cryst. (2009). C65, o70–o75

organic compounds
Table 2
Hydrogen-bond geometry (A, ).
Table 3
Weak interactions (A, ) and contacts (A).
ꢀ
ꢀ
˚
˚
˚
Cg1 is the centre of gravity of the C9–C14 benzene ring and Cg2 is the centre
of gravity of the heterocyclic ring.
D—Hꢃ ꢃ ꢃA
D—H
Hꢃ ꢃ ꢃA
2.12
Dꢃ ꢃ ꢃA
D—Hꢃ ꢃ ꢃA
157
2-TP
N3—H3ꢃ ꢃ ꢃO4i
D—Hꢃ ꢃ ꢃA
D—H Hꢃ ꢃ ꢃA Dꢃ ꢃ ꢃA
D—Hꢃ ꢃ ꢃA Notes
0.86
2.927 (2)
2.902 (2)
2.984 (2)
3.376 (2)
2.896 (2)
2-TP
4-TP
N3—H3ꢃ ꢃ ꢃO2ii
C1—H1aꢃ ꢃ ꢃO6
C8—H8aꢃ ꢃ ꢃCg1vi
C12—H12ꢃ ꢃ ꢃCg1vii
0.96
0.96
0.93
2.28
2.85
2.73
2.712 (3) 106
3.610 (2) 136
3.639 (2) 167
Intra
III†
Edge-to-
face, I†
0.83 (3)
0.83 (2)
0.87 (1)
0.90 (2)
2.08 (3)
2.15 (2)
2.53 (1)
1.99 (2)
170 (2)
176 (2)
164 (2)
178 (2)
2,4-DTP
N3—H3ꢃ ꢃ ꢃO6iii
4-TP
2,4,6-TTP
N3—H3ꢃ ꢃ ꢃS4iv
C1—H1aꢃ ꢃ ꢃO2
C1—H1cꢃ ꢃ ꢃCg1vii
O6ꢃ ꢃ ꢃC2viii
0.96
0.96
2.26
2.81
2.710 (2) 107
3.702 (2) 154
2.949 (2)
Intra
II†
P
O6ꢃ ꢃ ꢃCg2viii
3.214 (2)
N3—H3ꢃ ꢃ ꢃO4v
Symmetry codes: (i) ꢂx þ 2; ꢂy þ 1; ꢂz; (ii) ꢂx þ 2; ꢂy þ 1; ꢂz þ 1; (iii) x þ 1; y; z;
2,4-DTP
C1—H1aꢃ ꢃ ꢃO6
(iv) ꢂx þ 1; ꢂy þ 2; ꢂz þ 1; (v) ꢂx; ꢂy; ꢂz þ 1.
0.96
0.96
2.22
3.00
2.677 (3) 108
3.824
Intra
C1—H1bꢃ ꢃ ꢃS4ix
144
The authors thank the X-ray Laboratory, Faculty of
Chemistry, Jagiellonian University, for use of the Nonius
KappaCCD diffractometer.
2,4,6-TTP
C1—H1aꢃ ꢃ ꢃS6
C8—H8cꢃ ꢃ ꢃS4
C8—H8aꢃ ꢃ ꢃCg1x
C12—H12ꢃ ꢃ ꢃCg1vii
0.96
0.96
0.96
0.93
2.42
2.87
2.98
2.75
2.959 (3) 115
3.444 (3) 120
3.687 (3) 132
3.620 (3) 156
Intra
Intra
III†
Edge-to-
face, I†
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: LN3120). Services for accessing these data are
described at the back of the journal.
P
C1—H1aꢃ ꢃ ꢃO2
C1—H1cꢃ ꢃ ꢃCg1xi
C10—H10ꢃ ꢃ ꢃO4
C10—H10ꢃ ꢃ ꢃO6xii
C13—H13ꢃ ꢃ ꢃCg1xiii
0.96
0.96
0.93
0.93
0.93
2.28
3.00
2.59
2.59
2.90
2.724
3.931
108
165
Intra
II†
Intra
3.112 (2) 116
3.436 (2) 151
3.798 (2) 162
References
Edge-to-
face, I†
Allen, F. H. (2002). Acta Cryst. B58, 380–388.
O2ꢃ ꢃ ꢃC2xiv
3.087 (2)
2.921 (2)
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor,
R. (1995). International Tables for Crystallography, Vol. C, edited by A. J. C.
Wilson, ch. 9.5, pp. 685–706. Dordrecht: Kluwer Academic Publishers.
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C.,
Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
O2ꢃ ꢃ ꢃCg2xiv
† Category of weak Hꢃ ꢃ ꢃꢁ interaction according to the classification of Malone et al.
(1997). Symmetry codes: (vi) x; y þ 1; z; (vii) ꢂx þ 32 ; y ꢂ 21 ; ꢂz þ ; (viii)
1
2
ꢂx þ 23 ; y þ 21 ; ꢂz þ ; (ix) x ꢂ 12 ; ꢂy þ 23 ; z ꢂ ; (x) x; y þ 1; z; (xi) x; ꢂy ꢂ 12 ; z þ ;
1
2
1
2
3
2
1
2
(xii) x; ꢂy þ 12 ; z ꢂ ; (xiii) ꢂx þ 1; y ꢂ 21 ; ꢂz þ ; (xiv) ꢂx; y ꢂ 12 ; ꢂz þ .
1
2
3
2
Bideau, J.-P., Marly, L. & Housty, J. (1969). C. R. Acad. Sci. Ser. C (Chim.), 269,
549–551.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
Day, G. M., Motherwell, W. D. S. & Jones, W. (2007). Phys. Chem. Chem. Phys.
9, 1693–1704.
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142.
Nonius (1997). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307–326. New York: Academic Press.
Platteau, C., Lefebvre, J., Hemon, S., Baehtz, C., Danede, F. & Prevost, D.
(2005). Acta Cryst. B61, 80–88.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
˙
Stasiewicz-Urban, A., Kubaszek, M., Zylewski, M., Cegła, M. & Bojarski, J.
(2004). Pol. J. Chem. 78, 2105–2115.
Takechi, H., Kubo, K., Takahashi, H. & Matsumoto, T. (2007). Acta Cryst. E63,
o701–o703.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Huber, B., Bocchicchio, M., Hauser, I., Horstmann, V., Jokeit, G., May, T.,
Meinert, T., Robertson, E., Schorlemmer, H., Schulz, L., Wagner, W. &
Seidel, M. (2009). Seizure Eur. J. Epil. doi:10.1016/j.seizure.2008.07.006.
Kushikata, T., Hirota, K., Yoshida, H., Kudo, M., Lambert, D. G., Smart, D.,
Jerman, J. C. & Matsuki, A. (2003). Neuroscience, 121, 855–863.
Lewis, W., McKeown, R. H. & Robinson, W. T. (2005). Acta Cryst. E61, o799–
o800.
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.
Malone, J. F., Murray, C. M., Charlton, M. H., Docherty, R. & Lavery, A. J.
(1997). J. Chem. Soc. Faraday Trans. 93, 3429–3436.
Williams, P. P. (1973). Acta Cryst. B29, 1572–1579.
Williams, P. P. (1974). Acta Cryst. B30, 12–17.
ꢁ
Acta Cryst. (2009). C65, o70–o75
Janik et al.
C13H14N2O2S, C13H14N2O2S, C13H14N2OS2, C13H14N2S3 and C13H14N2O3 o75