(±)-6-benzyl-3,3-dimethylmorpholine- 2,5-dione and its 5-monothio and 2,5-dithio derivatives

Article abstract of DOI:10.1107/S0108270101003195

The morpholine ring of the title dione, C₁₃H₁₅NO₃, shows a boat conformation that is distorted towards a twist-boat, with the boat ends being the two Csp³ atoms of the ring. The benzyl substituent is in the favoured 'exo' position. In the monothione derivative, (±)-6-benzyl-3,3-dimethyl-5-thioxomorpholin-2-one, C₁₃H₁₅NO₂S, this ring has a much flatter conformation that is midway between a boat and an envelope, with the dimethyl end being almost planar. The orientation of the benzyl group is 'endo'. The dithione derivative, (±)-6-benzyl-3,3-dimethylmorpholine-2,5-dithione, C₁₃H₁₅NOS₂, has two symmetry-independent molecules, which show different puckering of the morpholine ring. One molecule has a flattened envelope conformation distorted towards a screw-boat, while the conformation in the other molecule is similar to that in the monothione derivative. Intermolecular hydrogen bonds link the molecules in the three compounds, respectively, into centrosymmetric dimers, infinite chains, and dimers made up of one of each of the symmetry-independent molecules.

Full text of DOI:10.1107/S0108270101003195

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
In connection with our investigations of 1,3-dipolar cyclo-
additions with thiocarbonyl compounds (cf. Heimgartner,
1986, 1991b; Linden et al., 1999; Mloston & Heimgartner,
2000), we also became interested in the thio analogues of
morpholinediones as C S dipolarophiles. The mono- and
dithio analogues are attractive models for the study of the
chemoselectivity (dipolarophilicity) of different ꢀ-systems in
1,3-dipolar cycloadditions. The racemic morpholine-2,5-dione
(IV) was prepared following the described protocol of
Obrecht & Heimgartner (1987). Subsequent successive thion-
ation with Lawesson reagent (LR) led almost quantitatively to
the monothione (V) and then to the morpholine-2,5-dithione
(VI), although the latter reaction was sluggish with a low yield.
As part of the full characterization of compounds (IV), (V),
and (VI), their low-temperature crystal structures have been
determined.
ISSN 0108-2701
(Æ)-6-Benzyl-3,3-dimethylmorpholine-
2,5-dione and its 5-monothio and
2,5-dithio derivatives
Anthony Linden,* Fatemeh Ghorbani-Salman Pour,
Roland A. Breitenmoser and Heinz Heimgartner
Institute of Organic Chemistry, University of Zurich, Winterthurerstrasse 190,
È
CH-8057 Zurich, Switzerland
È
Correspondence e-mail: alinden@oci.unizh.ch
Received 7 February 2001
Accepted 15 February 2001
The morpholine ring of the title dione, C13H15NO3, shows a
boat conformation that is distorted towards a twist-boat, with
the boat ends being the two Csp3 atoms of the ring. The benzyl
substituent is in the favoured `exo' position. In the mono-
thione
derivative,
(Æ)-6-benzyl-3,3-dimethyl-5-thioxo-
morpholin-2-one, C13H15NO2S, this ring has a much ¯atter
conformation that is midway between a boat and an envelope,
with the dimethyl end being almost planar. The orientation
of the benzyl group is `endo'. The dithione derivative,
(Æ)-6-benzyl-3,3-dimethylmorpholine-2,5-dithione, C13H15N-
OS2, has two symmetry-independent molecules, which show
different puckering of the morpholine ring. One molecule has
a ¯attened envelope conformation distorted towards a screw-
boat, while the conformation in the other molecule is similar
to that in the monothione derivative. Intermolecular hydrogen
bonds link the molecules in the three compounds, respectively,
into centrosymmetric dimers, in®nite chains, and dimers made
up of one of each of the symmetry-independent molecules.
In each compound, the bond lengths and angles are
generally within normal ranges. The amide C O and thio-
amide C S bonds in the dione, (IV), and the dithione, (VI),
respectively, are longer than the corresponding ester C
O
and thioester C S bonds (Tables 1 and 3). This re¯ects the
expected greater ꢀ-electron delocalization in (thio)amide
groups compared with (thio)ester groups and is consistent
with the trends for such groups derived from an examination
of the Cambridge Structural Database (CSD, October 2000
release; Allen & Kennard, 1993). The angles at the O and N
atoms of the morpholine rings (Tables 1, 3 and 5) are signi®-
Comment
Some years ago, we showed that diamides akin to compound
(III) (see Scheme), which are conveniently prepared by the
reaction of hydroxy acids with 3-amino-2H-azirines, can be
cyclized by treatment with HCl gas in a non-nucleophilic
solvent (Obrecht & Heimgartner, 1984, 1987; Heimgartner,
1991a; Heimgartner et al., 1999). This method, the so-called
`direct amide cyclization', has been used widely to prepare
cyclic depsipeptides by lactone formation (Obrecht & Heim-
gartner, 1984, 1990; Magirius, 1995; Koch & Heimgartner,
2000; Koch et al., 2000). In the case of larger rings, the cycli-
zation occurs via 1,3-oxazol-5(4H)-ones as intermediates and
ring enlargement by intramolecular nucleophilic attack of the
hydroxy group at the oxazolone C O group (Heimgartner et
al., 1999). On the other hand, a mechanism via an intermediate
oxonium ion is more likely for the formation of the six-
membered morpholine-2,5-diones.
Figure 1
The molecular structure of (IV) showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
ꢀ
634 # 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved
Acta Cryst. (2001). C57, 634±637

organic compounds
cantly larger than 120ꢁ, particularly in the presence of the ring
¯attening observed in the monothione, (V), and dithione,
(VI), derivatives, as described below.
tened envelope (nearest ideal values: ꢁ = 54.7, ' = 60ꢁ) and a
screw-boat (ꢁ = 67.5, ' = 90ꢁ) (Boeyens, 1978). In contrast to
compounds (IV) and (V), it is not an Csp3 atom that is out of
the plane, but the thioester C atom, C2. The r.m.s. deviation of
The morpholine ring of the dione, (IV), has puckering
Ê
Ê
parameters (Cremer & Pople, 1975) of Q = 0.463 (2) A, ꢁ =
O1, C3, N4, C5 and C6 from their mean plane is 0.022 A, while
Ê
C2 deviates from this plane by 0.250 (3) A. The phenyl ring is
92.4 (2)ꢁ and ' = 133.4 (2)ꢁ, which represent a conformation
midway between a boat (nearest ideal values: ꢁ = 90, ' = 120ꢁ)
and a twist-boat (ꢁ = 90, ' = 150ꢁ) (Boeyens, 1978), where the
boat ends are the two Csp3 atoms of the ring (Fig. 1) and the
twist results from a slight non-planarity of the four atoms
constituting the base of the boat. The r.m.s. deviation of O1,
positioned above the morpholine ring.
The morpholine ring in molecule B of (VI) has a ¯attened
boat conformation distorted towards an envelope, similar to,
but even ¯atter than, the conformation observed in compound
Ê
(V). The ring-puckering parameters are Q = 0.097 (2) A, ꢁ =
C2, N4 and C5 from their mean plane is 0.053 A, while C3 and
101.6 (12)ꢁ and ' = 120.5 (12)ꢁ. Using the inverted molecule,
which is also present in this racemic compound, ꢁ = 78.4 (12)ꢁ
and ' = 300.5 (12)ꢁ, which indicate a conformation similar to
that observed for compound (V). As in (V), the two Csp3
atoms of the ring form the ends of the boat, with the dimethyl
end being almost coplanar with the base of the boat. The r.m.s.
deviation of O21, C22, N24 and C25 from their mean plane is
Ê
Ê
C6 deviate from this plane by 0.363 (3) and 0.416 (3) A,
respectively. The benzyl substituent is in the favoured `exo'
position.
The morpholine ring of the monothione derivative, (V), has
a much ¯atter and less twisted boat conformation (Fig. 2). The
two Csp3 atoms of the ring again form the ends of the boat, but
the dimethyl end is almost coplanar with the base of the boat,
so that the ring is distorted towards an envelope conformation.
This is borne out by the ring-puckering parameters of Q =
Ê
only 0.0004 A, while C23 and C26 deviate from this plane by
Ê
0.056 (3) and 0.108 (3) A, respectively. The orientation of the
benzyl group is `endo', with the phenyl ring again being
positioned above the morpholine ring.
There are only two structure reports cited in the CSD of
compounds containing a morpholine-2,5-dione moiety, while
there are no reports of any structures involving 5-thioxo-
morpholin-2-one or morpholine-2,5-dithione moieties. Both
reported structures are simply substituted morpholine deri-
vatives. The morpholine ring in 3-benzyl-6-isopropyl-
ꢁ
ꢁ
Ê
0.139 (2) A, ꢁ = 75.2 (8) and ' = 298.3 (10) . The value of ' is
appropriate for either an envelope or boat conformation
(nearest ideal value is 300ꢁ) (Boeyens, 1978), while ꢁ lies
approximately midway between the ideal values for boat (90ꢁ)
and envelope (54.7ꢁ) conformations. The r.m.s. deviation of
Ê
O1, C2, N4 and C5 from their mean plane is only 0.002 A,
while C3 and C6 deviate from this plane by 0.069 (3) and
Ê
0.162 (3) A, respectively. The orientation of the benzyl group
is `endo', which brings the phenyl ring into a position above
the body of the morpholine ring.
morpholine-2,5-dione was reported as having a boat
conformation with the Csp3 atoms forming the boat ends
(Bolte & Egert, 1994). However, a closer examination of the
ꢁ
Ê
The asymmetric unit of the dithione derivative, (VI), has
two symmetry-independent molecules (Fig. 3) and PLATON
(Spek, 2001) con®rmed that there was no additional over-
looked symmetry, although the molecules are approximately
related by a non-crystallographic twofold axis. The two mol-
ecules have different puckering of the morpholine ring and the
orientation of the phenyl ring about the C9ÐC10 bond (C29Ð
C30 in molecule B) also differs by a twist of about 17ꢁ. The
morpholine ring of molecule A has puckeringꢁparameters of
puckering parameters [Q = 0.494 (2) A, ꢁ = 93.1 (2) and ' =
129.3 (2)ꢁ] shows that the ring has an un¯attened conforma-
tion that lies midway between a boat and a twist-boat, and
which is virtually identical to that in compound (IV).
Conversely,
in
3-benzyl-3-hydroxy-6-methylamino-6-(2-
methylpropyl)morpholine-2,5-dione (Iijima et al., 1992), the
ꢁ
Ê
Q = 0.185 (2) A, ꢁ = 62.8 (7) and ' = 75.2 (8) , which repre-
sent a conformation midway between that of a slightly ¯at-
Figure 3
The molecular structure of both symmetry-independent molecules of
(VI) showing the atom-labelling scheme and the hydrogen bonds (dashed
lines). Molecule A is on the left. Displacement ellipsoids are drawn at the
30% probability level. H atoms are represented by circles of arbitrary
size.
Figure 2
The molecular structure of (V) showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level.
ꢀ
Acta Cryst. (2001). C57, 634±637
Anthony Linden et al.
C13H15NO3, C13H15NO2S and C13H15NOS2 635

organic compounds
Compound (IV)
morpholine ring has an almost completely ¯attened boat
conformation, with the two Csp3 atoms being only 0.086 and
Ê
0.078 A from the plane de®ned by the other four ring atoms,
Crystal data
C13H15NO3
Mr = 233.27
Triclinic, P1
Z = 2
Dx = 1.281 Mg m
Mo Kꢂ radiation
Ê
which are all 0.002 A from their mean plane.
3
While a comparison of the structures of compounds (IV),
(V) and (VI) might induce one to conclude that an increasing
number of thione substituents in the morpholine ring leads to
a greater ¯attening of the ring, the two previously reported
structures of morpholine-2,5-dione derivatives contradict this
hypothesis and suggest that the cause of the ring ¯attening is
not necessarily related to the degree of thione substitution, but
to other effects which cannot readily be deduced from the
small number of determined structures of this class.
Ê
a = 5.699 (2) A
Cell parameters from 25
re¯ections
Ê
b = 10.347 (3) A
c = 11.327 (4) A
ꢁ = 19.0±20.0ꢁ
ꢅ = 0.09 mm
T = 173 (1) K
Ê
1
ꢂ = 67.51 (2)ꢁ
ꢃ = 80.38 (3)ꢁ
ꢄ = 80.35 (3)ꢁ
Plate, colourless
0.50 Â 0.38 Â 0.12 mm
3
Ê
V = 604.5 (4) A
Data collection
Rigaku AFC-5R diffractometer
!±2ꢁ scans
h = 7 ! 7
k = 13 ! 0
The amide NÐH group of compound (IV) forms an inter-
molecular hydrogen bond with the amide O atom of an
adjacent molecule (Table 2). This acceptor molecule then
donates back to the ®rst molecule, thereby linking pairs of
molecules into centrosymmetric dimers whose interactions
can be described by the graph-set motif of R22(8) (Bernstein et
al., 1995). In the monothione derivative, (V), a simple change
from the ester group of (IV) to a thioester group has drama-
tically altered the hydrogen-bonding pattern (Table 4). The
acceptor atom is now the morpholine ring O atom of a
neighbouring molecule and intermolecular interactions link
the molecules of (V) into in®nite one-dimensional chains
which run parallel to the [010] direction and have a graph-set
motif of C(5). In compound (VI), the hydrogen-bonding
pattern is similar to that in compound (IV). The acceptor atom
is the thioamide S atom of the other symmetry-independent
molecule in the asymmetric unit. This acceptor molecule then
donates back to the ®rst molecule, thus forming hydrogen-
bonded dimers comprised of one of each of the symmetry-
independent molecules (Table 6 and Fig. 3). These interactions
can again be described by the graph-set motif of R22(8).
2927 measured re¯ections
2773 independent re¯ections
1859 re¯ections with I > 2ꢆ(I)
Rint = 0.025
l = 14 ! 13
3 standard re¯ections
every 150 re¯ections
intensity decay: none
ꢁmax = 27.5ꢁ
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.047
wR(F2) = 0.130
S = 1.02
2773 re¯ections
160 parameters
H atoms: see below
w = 1/[ꢆ2(Fo2) + (0.0530P)2
+ 0.1854P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max = 0.001
3
Ê
Áꢇmax = 0.27 e A
3
Ê
0.23 e A
Áꢇmin
=
Table 1
Selected geometric parameters (A, ) for (IV).
ꢁ
Ê
O1ÐC2
O1ÐC6
O2ÐC2
1.340 (2)
1.457 (2)
1.199 (2)
O5ÐC5
N4ÐC5
N4ÐC3
1.236 (2)
1.323 (2)
1.460 (2)
C2ÐO1ÐC6
120.53 (13)
C5ÐN4ÐC3
124.06 (14)
Table 2
Hydrogen-bonding geometry (A, ) for (IV).
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
N4ÐH4Á Á ÁO5i
0.88 (2)
1.95 (2)
2.833 (2)
176 (2)
Experimental
Compound (III) was obtained in 92% yield by the reaction of dl-
phenyllactic acid, (I) (408 mg, 2.46 mmol), and 2,2,N-trimethyl-N-
phenyl-2H-azirin-3-amine, (II) (472 mg, 2.71 mmol), in acetonitrile
(20 ml) at room temperature following a known protocol (Obrecht &
Heimgartner, 1987). Treatment of a solution of (III) (2.19 g,
6.44 mmol) in toluene (300 ml) at 373 K with dry HCl gas for 15 min
yielded, after chromatography (silica gel, dichloromethane/diethyl
ether, 6:1) and crystallization from diethyl ether, compound (IV) in
27% yield as colourless plates (m.p. 437±438 K). Lawesson reagent
(Scheibye et al., 1978) (240 mg, 0.59 mmol) was added to a solution of
(IV) (276 mg, 1.19 mmol) in toluene (15 ml), and the mixture was
heated to 373 K for 30 min. After chromatography (silica gel, di-
chloromethane/hexane, 3:2) and crystallization from dichloro-
methane/diethyl ether, compound (V) was obtained in 96% yield as
colourless needles (m.p. 448±449 K). Heating a mixture of (V)
(95 mg, 0.38 mmol) and Lawesson reagent (3.84 mg, 0.95 mmol) in
toluene (10 ml) for 2 d under re¯ux led, after chromatographic
separation (silica gel, dichloromethane/hexane, 1:1), to compound
(VI) in 28% yield as yellow prisms (m.p. 396±397 K). Suitable single
crystals of (VI) were obtained by recrystallization from diethyl ether/
dichloromethane/hexane.
Symmetry code: (i) x; 1 y; 1 z.
Compound (V)
Crystal data
3
C13H15NO2S
Mr = 249.33
Monoclinic, P21/n
Dx = 1.335 Mg m
Mo Kꢂ radiation
Cell parameters from 24
re¯ections
Ê
a = 13.901 (4) A
ꢁ = 18.0±20.0ꢁ
ꢅ = 0.25 mm
T = 173 (1) K
Ê
b = 5.843 (6) A
1
Ê
c = 16.559 (5) A
ꢃ = 112.70 (2)ꢁ
V = 1240.7 (13) A
Z = 4
3
Ê
Needle, colourless
0.50 Â 0.20 Â 0.15 mm
Data collection
Rigaku AFC-5R diffractometer
!±2ꢁ scans
Absorption correction: scan
(North et al., 1968)
Tmin = 0.696, Tmax = 0.963
3261 measured re¯ections
2854 independent re¯ections
1926 re¯ections with I > 2ꢆ(I)
Rint = 0.034
ꢁmax = 27.5ꢁ
h = 0 ! 18
k = 0 ! 7
l = 21 ! 19
3 standard re¯ections
every 150 re¯ections
intensity decay: none
ꢀ
636 Anthony Linden et al.
C13H15NO3, C13H15NO2S and C13H15NOS2
Acta Cryst. (2001). C57, 634±637

organic compounds
Re®nement
Table 5
Selected geometric parameters (A, ) for (VI).
ꢁ
Ê
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.052
wR(F2) = 0.151
S = 1.04
2854 re¯ections
160 parameters
H atoms: see below
w = 1/[ꢆ2(Fo2) + (0.0820P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max = 0.001
S2ÐC2
S5ÐC5
O1ÐC2
O1ÐC6
N4ÐC5
N4ÐC3
1.624 (2)
1.670 (2)
1.331 (3)
1.455 (3)
1.319 (3)
1.473 (3)
S22ÐC22
S25ÐC25
O21ÐC22
O21ÐC26
N24ÐC25
N24ÐC23
1.628 (2)
1.685 (2)
1.331 (2)
1.458 (2)
1.308 (3)
1.476 (2)
3
Ê
Áꢇmax = 0.53 e A
3
Ê
0.36 e A
Áꢇmin
=
Table 3
Selected geometric parameters (A, ) for (V).
ꢁ
Ê
C2ÐO1ÐC6
C5ÐN4ÐC3
124.91 (18)
128.14 (19)
C22ÐO21ÐC26
C25ÐN24ÐC23
126.03 (16)
128.93 (18)
S5ÐC5
O1ÐC2
O1ÐC6
1.669 (2)
1.347 (3)
1.455 (3)
O2ÐC2
N4ÐC3
N4ÐC5
1.204 (3)
1.470 (3)
1.315 (3)
Table 6
Hydrogen-bonding geometry (A, ) for (VI).
ꢁ
Ê
C2ÐO1ÐC6
124.30 (19)
C5ÐN4ÐC3
128.6 (2)
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
Table 4
Hydrogen-bonding geometry (A, ) for (V).
N4ÐH4Á Á ÁS25
N24ÐH24Á Á ÁS5
0.89 (3)
0.91 (3)
2.58 (3)
2.42 (3)
3.469 (2)
3.293 (2)
173 (3)
163 (2)
ꢁ
Ê
DÐHÁ Á ÁA
N4ÐH4Á Á ÁO1i
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
The Swiss National Science Foundation and F. Hoffmann±
La Roche AG, Basel, are thanked for ®nancial support.
0.90 (3)
2.22 (3)
3.092 (4)
164 (2)
Symmetry code: (i) x; y 1; z.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1460). Services for accessing these data are
described at the back of the journal.
Compound (VI)
Crystal data
C13H15NOS2
Mr = 265.39
Triclinic, P1
Z = 4
Dx = 1.327 Mg m
Mo Kꢂ radiation
3
References
Ê
Allen, F. H. & Kennard, O. (1993). Chem. Des. Autom. News, 8, 1, 31±37.
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Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
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Int. Ed. Engl. 34, 1555±1573.
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(1999). J. Heterocycl. Chem. 36, 1539±1547.
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Ishizuka, M. & Takeuchi, T. (1992). J. Antibiot. 45, 1553±1556.
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Laboratory, Tennessee, USA.
Koch, K. N. & Heimgartner, H. (2000). Helv. Chim. Acta, 83, 1881±1900.
Koch, K. N., Linden, A. & Heimgartner, H. (2000). Helv. Chim. Acta, 83, 233±
257.
Linden, A., Awad, E. M. A. H. & Heimgartner, H. (1999). Acta Cryst. C55,
1877±1881.
Magirius, J. E. F. (1995). PhD thesis, University of Zurich, Switzerland.
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359.
Obrecht, D. & Heimgartner, H. (1984). Helv. Chim. Acta, 67, 526±533.
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Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of Gott-
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Spek, A. L. (2001). PLATON. University of Utrecht, The Netherlands.
a = 8.6915 (13) A
Ê
Cell parameters from 25
re¯ections
b = 11.896 (3) A
ꢁ = 19.0±20.0ꢁ
ꢅ = 0.38 mm
T = 173 (1) K
Ê
c = 13.661 (4) A
1
ꢂ = 75.62 (2)ꢁ
ꢃ = 76.211 (16)ꢁ
ꢄ = 84.971 (18)ꢁ
Prism, yellow
0.48 Â 0.40 Â 0.30 mm
3
Ê
V = 1328.2 (6) A
Data collection
Rigaku AFC-5R diffractometer
!±2ꢁ scans
Absorption correction: scan
(North et al., 1968)
Tmin = 0.781, Tmax = 0.891
6399 measured re¯ections
6101 independent re¯ections
4424 re¯ections with I > 2ꢆ(I)
Rint = 0.021
max = 27.5ꢁ
ꢁ
h = 11 ! 11
k = 15 ! 0
l = 17 ! 17
3 standard re¯ections
every 150 re¯ections
intensity decay: none
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.049
wR(F2) = 0.142
S = 1.05
6101 re¯ections
319 parameters
H atoms: see below
w = 1/[ꢆ2(Fo2) + (0.0823P)2
+ 0.0825P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢆ)max = 0.001
3
Ê
Áꢇmax = 0.54 e A
È
3
Ê
0.41 e A
Áꢇmin
=
For each compound, the methyl H atoms were constrained to an
ideal geometry with Uiso(H) = 1.5Ueq(C). The amino H atoms were
re®ned freely. All other H atoms were constrained to ride on their
parent atoms with Uiso(H) = 1.2Ueq(C). For (V), the scans showed a
more severe absorption pro®le than predicted theoretically and this is
attributed to the anisotropic shape of the crystal.
For all compounds, data collection and cell re®nement: MSC/AFC
Diffractometer Control Software (Molecular Structure Corporation,
1991); data reduction: TEXSAN (Molecular Structure Corporation,
1999); structure solution: SHELXS97 (Sheldrick, 1997); structure
re®nement: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEPII (Johnson, 1976).
ꢀ
Acta Cryst. (2001). C57, 634±637
Anthony Linden et al.
C13H15NO3, C13H15NO2S and C13H15NOS2 637