N,N′-Diethyl-4-nitro-benzene-1,3-diamine, 2,6-bis-(ethyl-amino)-3- nitro-benzonitrile and bis-(4-ethyl-amino-3-nitro-phenyl) sulfone

Article abstract of DOI:10.1107/S0108270110023188

N,N′-Diethyl-4-nitro-benzene-1,3-diamine, C₁₀H ₁₅N₃O₃, (I), crystallizes with two independent mol-ecules in the asymmetric unit, both of which are nearly planar. The mol-ecules differ in the conformation of the

Full text of DOI:10.1107/S0108270110023188

organic compounds
Acta Crystallographica Section C
Crystal Structure
atom, the molecules of (III) adopt an overall V shape. There
are no intermolecular amine–nitro hydrogen bonds. Rather,
˚
Communications
each amine H atom has a long (Hꢀ ꢀ ꢀO ca 2.8 A) interaction
ISSN 0108-2701
with one of the sulfone O atoms. Molecules of (III) are thus
linked by amine–sulfone N—Hꢀ ꢀ ꢀO hydrogen bonds into
zigzag double chains running along [001]. Taken together,
these structures demonstrate that small changes in the
functionalization of ethylamine–nitroarenes cause significant
differences in the intermolecular interactions and packing.
N,N0-Diethyl-4-nitrobenzene-1,3-
diamine, 2,6-bis(ethylamino)-3-nitro-
benzonitrile and bis(4-ethylamino-3-
nitrophenyl) sulfone
Comment
Thomas J. Payne,a Chad R. Thurman,a Hao Yu,a Qian Sun,a
Dillip K. Mohanty,a* Philip J. Squattrito,a* Mark-Robin
Giolando,b Christopher R. Brueb and Kristin Kirschbaumb
As part of a continuing investigation of polyamine polymers
(Teng et al., 2006; Wang et al., 2009), we have prepared and
structurally characterized several series of aromatic nitro
compounds with aliphatic amine groups as model compounds
for the polymers (Walczak et al., 2008; Teng et al., 2009).
Detailed knowledge of the intra- and intermolecular inter-
actions in the model compounds may be useful in interpreting
the physical properties (solvent resistance, etc.) of polymers
containing the same functional groups. In this report, we
present the structures of N,N0-diethyl-4-nitrobenzene-1,3-di-
amine, (I), 2,6-bis(ethylamino)-3-nitrobenzonitrile, (II), and
bis(4-ethylamino-3-nitrophenyl) sulfone, (III).
aDepartment of Chemistry, Central Michigan University, Mount Pleasant, MI 48859,
USA, and bDepartment of Chemistry, University of Toledo, Toledo, OH 43606, USA
Correspondence e-mail: mohan1dk@cmich.edu, p.squattrito@cmich.edu
Received 11 June 2010
Accepted 15 June 2010
Online 23 June 2010
N,N0-Diethyl-4-nitrobenzene-1,3-diamine, C10H15N3O2, (I),
crystallizes with two independent molecules in the asymmetric
unit, both of which are nearly planar. The molecules differ in
the conformation of the ethylamine group trans to the nitro
group. Both molecules contain intramolecular N—Hꢀ ꢀ ꢀO
hydrogen bonds between the adjacent amine and nitro groups
and are linked into one-dimensional chains by intermolecular
N—Hꢀ ꢀ ꢀO hydrogen bonds. The chains are organized in layers
˚
parallel to (101) with separations of ca 3.4 A between adjacent
sheets. The packing is quite different from what was observed
in isomeric 1,3-bis(ethylamino)-2-nitrobenzene. 2,6-Bis(ethyl-
amino)-3-nitrobenzonitrile, C11H14N4O2, (II), differs from (I)
only in the presence of the nitrile functionality between the
two ethylamine groups. Compound (II) crystallizes with one
unique molecule in the asymmetric unit. In contrast with (I),
one of the ethylamine groups, which is disordered over two
sites with occupancies of 0.75 and 0.25, is positioned so that
the methyl group is directed out of the plane of the ring by
approximately 85ꢁ. This ethylamine group forms an intra-
molecular N—Hꢀ ꢀ ꢀO hydrogen bond with the adjacent nitro
group. The packing in (II) is very different from that in (I).
Molecules of (II) are linked by both intermolecular amine–
nitro N—Hꢀ ꢀ ꢀO and amine–nitrile N—Hꢀ ꢀ ꢀN hydrogen bonds
into a two-dimensional network in the (102) plane. Alter-
nating molecules are approximately orthogonal to one
another, indicating that ꢀ–ꢀ interactions are not a significant
factor in the packing. Bis(4-ethylamino-3-nitrophenyl) sul-
fone, C16H18N4O6S, (III), contains the same ortho nitro/
ethylamine pairing as in (I), with the position para to the nitro
group occupied by the sulfone instead of a second ethylamine
group. Each 4-ethylamino-3-nitrobenzene moiety is nearly
planar and contains the typical intramolecular N—Hꢀ ꢀ ꢀO
hydrogen bond. Due to the tetrahedral geometry about the S
Compounds (I) and (II) differ only in the presence of a
nitrile group between the ethylamine groups on the latter,
while (III) has two nitro- and ethylamine-substituted arene
moieties similar to those in (I) joined via a sulfone group. In
addition, (I) is an isomer of 1,3-bis(ethylamino)-2-nitroben-
zene, the structure of which we reported recently (Walczak et
al., 2008). Despite the chemical similarities between these
compounds, their structures reveal substantial differences in
intermolecular interactions and crystal packing.
Compound (I) crystallizes in the monoclinic space group
P21/c with two independent molecules in the asymmetric unit
(Fig. 1). Both molecules are essentially flat and coplanar [the
dihedral angle between the arene planes is 4.56 (7)ꢁ], but they
differ in terms of the conformation of the ethylamine group
para to the nitro group. In one molecule, both ethylamine
groups are positioned such that the methylene C atoms eclipse
atom C2 of the arene ring (i.e. the C2—C1—N1—C7 and C2—
C3—N2—C9 torsion angles are both close to 0ꢁ). In the other
Acta Cryst. (2010). C66, o369–o373
doi:10.1107/S0108270110023188
# 2010 International Union of Crystallography o369

organic compounds
Figure 1
Figure 3
The molecular structure of (I), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii. The asymmetric unit
consists of two molecules. Hydrogen bonds are shown as dashed lines.
The molecular structure of (II), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii. The asymmetric unit
consists of one molecule. The hydrogen bond is shown as a dashed line.
N—Hꢀ ꢀ ꢀO hydrogen bonds (Panunto et al., 1987). The chains
in (I) are positioned in the (101) planes of the crystal structure,
˚
with the resulting layers separated by ca 3.4 A. The closest
rings in adjacent layers are slipped past one another, negating
the possibility of significant ꢀ–ꢀ interactions between mol-
ecules in neighbouring sheets.
Previously, we reported the structure of 1,3-bis(ethyl-
amino)-2-nitrobenzene, an isomer of (I) (Walczak et al., 2008).
When the nitro group is located between the amine groups,
both form intramolecular N—Hꢀ ꢀ ꢀO hydrogen bonds and the
molecules pack without forming any intermolecular hydrogen
bonds. The packing is instead dominated by hydrophobic
attractions between the alkyl groups. The difference in inter-
molecular interactions is reflected in the higher melting point
of (I) (381 K) compared with its isomer (336 K).
Compound (II) has the nitro and ethylamine groups
arranged as in (I), with an added nitrile functionality between
the two ethylamine groups. Compound (II) also crystallizes in
P21/c, but with one independent molecule in the asymmetric
unit (Fig. 3). The conformation of the ethylamine group ortho
to the nitro group is quite different from that in (I). Atoms C8
and C9 are disordered over two positions, A and B, with
occupancies of 0.75 and 0.25, respectively; only the major
component is shown in Figs. 3 and 4. The C8A—C9A ethyl
group is positioned so that methyl atom C9A is directed out of
the plane of the ring at an angle of approximately 85ꢁ [C2—
N2—C8A—C9A torsion angle ꢂ85.4 (2)ꢁ], whereas the rest of
the molecule is nearly planar.
As in (I) and all of the amine/nitro-substituted molecules
we have examined so far (Walczak et al., 2008; Teng et al.,
2009), there is an intramolecular hydrogen bond between the
adjacent amine and nitro groups of (II) (Table 2). Molecules of
(II) are associated via two types of intermolecular hydrogen
bonds. First, there is a fairly long amine–nitro N2—H2Nꢀ ꢀ ꢀO2i
interaction [symmetry code: (i) ꢂx, y + 12, ꢂz + 21] that connects
the molecules into chains along [010] (Fig. 4). Amine atom
H2N thus participates in a three-centre hydrogen bond with
acceptor atoms O2 (intramolecular) and O2i (intermolecular).
In addition, pairs of molecules are joined by a centrosym-
metric pair of hydrogen bonds between the amine group trans
to the nitro group and the nitrile N atom, viz. N4—H4Nꢀ ꢀ ꢀN1ii
Figure 2
Molecules of (I) linked into chains by N—Hꢀ ꢀ ꢀO amine–nitro hydrogen
bonds (dashed lines). Portions of two chains are shown and the view is on
to the (101) plane. [Symmetry code: (#) x + 1, y, z ꢂ 1.]
molecule, the ethylamine group ortho to the nitro group is
oriented similarly, while that para to the nitro group is rotated
in the opposite direction, such that the C12—C13—N5—C19
torsion angle is 168.42 (16)ꢁ. As a result, the latter molecule is
slightly less planar than the former.
Both molecules of (I) feature an intramolecular hydrogen
bond between the amine H atom and the O atom of the
adjacent nitro group (Table 1). This type of interaction is
typical for arenes with an amine group ortho to a nitro group
(Panunto et al., 1987). The two independent molecules are
linked by an intermolecular N—Hꢀ ꢀ ꢀO hydrogen bond
between the amine group on one molecule and the nitro group
on the other. Nitro atom O4 thus serves as an acceptor for
both intra- and intermolecular hydrogen bonds. Molecules of
(I) are linked into one-dimensional chains (Fig. 2) by two
amine–nitro hydrogen bonds, viz. the N2—H2Nꢀ ꢀ ꢀO4 inter-
action shown in Fig. 1 and an N5—H5Nꢀ ꢀ ꢀO1i interaction
[symmetry code: (i) x ꢂ 1, y, z + 1] (Table 1). Chains are
commonly formed by similarly functionalized arenes via
ꢃ
o370 Payne et al. C10H15N3O2, C11H14N4O2 and C16H18N4O6S
Acta Cryst. (2010). C66, o369–o373

organic compounds
Figure 5
The molecular structure of (III), showing the atom-labelling scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are
shown as dashed lines.
Figure 4
Molecules of (II) linked by N—Hꢀ ꢀ ꢀO amine–nitro hydrogen bonds
(dashed lines) into chains running along [010]. Pairs of molecules are also
linked across centres of inversion by N—Hꢀ ꢀ ꢀN amine–nitrile hydrogen
bonds. Two unit cells are shown and the view is along the b axis.
1
1
[Symmetry codes: (#) ꢂx, y + , ꢂz + ; ($) ꢂx + 1, ꢂy + 1, ꢂz + 1.]
2
2
[symmetry code: (ii) 1 ꢂ x, 1 ꢂ y, 1 ꢂ z] (Table 2). The overall
result is a two-dimensional network parallel to the (102) plane.
Unlike in (I), the molecules of (II) are not all parallel. Rather,
alternating molecules are approximately orthogonal to one
another [the dihedral angle between the molecules at (x, y, z)
Figure 6
Molecules of (III) linked by N—Hꢀ ꢀ ꢀO hydrogen bonds (dashed lines)
between the amine H atom and sulfone O atom into double chains
running along the [001] direction. A single such chain is shown.
[Symmetry codes: (#) x, ꢂy + 12, z + 21; ($) x, y, z + 1.]
1
1
and (ꢂx, y + , ꢂz + ) is 87.53 (6)ꢁ], suggesting that ꢀ–ꢀ
2
2
˚
Hꢀ ꢀ ꢀO distances > 2.6 A and N—Hꢀ ꢀ ꢀO angles roughly
interactions are not a significant factor in the packing.
Compound (III) contains the same ortho nitro/ethylamine
pairing as in (I), with the position para to the nitro group
occupied by the sulfone instead of a second ethylamine group.
It also crystallizes in P21/c with one independent molecule in
the asymmetric unit (Fig. 5). Each 4-ethylamino-3-nitro-
benzene moiety is nearly planar and contains the expected
intramolecular N—Hꢀ ꢀ ꢀO hydrogen bond. The bond distances
and angles around the S atom are within the ranges reported
in a recent study of a number of diaryl sulfones, including
some with amine and nitro groups on the rings (Rudolph et al.,
2009). Due to the tetrahedral geometry around the S atom, the
molecules adopt an overall V shape [the dihedral angle
between the arene rings is 70.93 (4)ꢁ].
between 90 and 120ꢁ. Molecules of (III) are thus linked
through the N—Hꢀ ꢀ ꢀOsulfone hydrogen bonds into zigzag
double chains running along [001] (Fig. 6). The arene rings of
neighbouring molecules in the double chain face each other at
˚
a separation of ca 3.4 A.
Despite the presence of the ortho amine and nitro func-
tionalities in all three molecules, the intermolecular hydrogen-
bonding patterns and molecular packing are quite different. In
particular, one might expect (II) to adopt a similar network of
amine–nitro hydrogen bonds to (I), where the Hꢀ ꢀ ꢀO
˚
distances are around 2.10 A. Instead, only one weaker three-
˚
centre N—Hꢀ ꢀ ꢀO interaction [Hꢀ ꢀ ꢀO = 2.47 (2) A] and a
weaker N—Hꢀ ꢀ ꢀN amine–nitrile interaction [Hꢀ ꢀ ꢀN
=
˚
2.361 (19) A] serve to link the molecules of (II). Inspection of
Fig. 2 suggests that the network in (I) would be impossible for
(II) because the nitrile N atom would have an unacceptably
close contact with a nitro O atom. In the case of (III), the
absence of intermolecular N—Hꢀ ꢀ ꢀO amine–nitro hydrogen
bonds is consistent with previous studies of sulfone molecules
containing N—H or O—H bonds, in which it was found that
intermolecular N—Hꢀ ꢀ ꢀO or O—Hꢀ ꢀ ꢀO hydrogen bonds
involving the sulfone O atoms are favoured over other inter-
actions (Glidewell et al., 2001; Glidewell & Ferguson, 1996). In
particular, in the crystal structure of 4-aminophenyl 4-nitro-
There are no intermolecular amine–nitro hydrogen bonds
in the structure of (III). Rather, each amine H atom has a long
interaction with sulfone atom O2, viz. N1—H1Nꢀ ꢀ ꢀO2i
ii
1
2
1
1
2
1
[symmetry code: (i) x, ꢂy + , z + ] and N3—H3Nꢀ ꢀ ꢀO2
[symmetry code: (ii) x, ꢂy + , z ꢂ ] (Table 3). Thus, each
2
2
amine H atom participates in a three-centre hydrogen bond
with two acceptors (an intramolecular nitro O atom and an
intermolecular sulfone O atom), while atom O2 serves as an
acceptor for both H atoms. A study of N—Hꢀ ꢀ ꢀO hydrogen
bonds in sulfonates (Pirard et al., 1995) finds a small cluster of
three-centre interactions similar to those found in (III) with
ꢃ
Acta Cryst. (2010). C66, o369–o373
Payne et al.
C10H15N3O2, C11H14N4O2 and C16H18N4O6S o371

organic compounds
38.49, 15.73, 14.68; IR (NaCl, ꢂ, cmꢂ1): 3330, 3264, 2977, 2201, 1576,
1522, 1496, 1372, 1228, 1163; MS (m/z) (% base peak): 234 (67.7), 217
(25), 201 (55.8), 200 (39.6), 199 (28.7), 185 (100), 159 (30.4).
phenyl sulfone (Bertolasi et al., 1993), which contains all of the
donor and acceptor groups found in (III), the molecules are
linked by amine–sulfone hydrogen bonds only, with no amine–
nitro interactions.
Compound (III) was prepared by a similar procedure from
anhydrous potassium carbonate (0.935 g, 0.0075 mol) and a solution
of ethylamine (0.489 g, 0.0109 mol; 70% in water) in N-methyl-2-
pyrrolidone (NMP, 10 ml), to which was added bis(4-fluoro-3-nitro-
benzene) sulfone (1.320 g, 0.00383 mol) in NMP (5 ml). Additional
NMP (5 ml) was used to wash the transfer container and this was
added to the reaction mixture, followed by toluene (20 ml). The
bright-yellow and slightly opaque reaction mixture was heated to
333 K, held at that temperature for 30 min and gradually raised to
393 K over a period of 3 h. The bright-yellow product was isolated
and purified as for (I). Crystals of (III) suitable for X-ray diffraction
were obtained by recrystallization from hexane (yield 69.8%; m.p.
574–576 K). Spectroscopic analysis for (III): 1H NMR (300 MHz,
CDCl3): ꢁ 8.7 (s, 2H), 8.3 (m, 2H), 7.9 (m, 2H), 6.9 (m, 2H), 3.4 (m,
4H), 1.4 (t, 6H); 13C NMR (300 MHz, CDCl3): ꢁ 147.66, 133.94, 130.15,
128.04, 128.00, 115.00, 38.31, 14,34; IR (neat, ꢂ > 1400 cmꢂ1): 3372,
2928, 2860, 1618, 1570, 1522, 1472; MS (m/z) (% base peak): 394 (85),
285 (20), 213 (100), 197 (20), 132 (15).
Experimental
For the preparation of (I), anhydrous potassium carbonate (5.095 g,
0.036 mol) and a solution of ethylamine (5.714 g, 0.0886 mol; 70% in
water) in dimethylacetamide (DMAC, 8 ml) were combined in a
100 ml three-necked round-bottomed flask fitted with a nitrogen
inlet, thermometer, magnetic stirring bar, and a Dean–Stark trap
fitted with a condenser. To the stirred solution was added 2,4-
difluoronitrobenzene (2.349 g, 0.0148 mol) in DMAC (5 ml). Addi-
tional DMAC (8 ml) was used to wash the transfer container and this
was added to the reaction mixture, followed by toluene (20 ml). The
temperature of the reaction mixture was raised to 333 K, held at that
temperature for 3 h, then raised to 393 K and the reaction allowed to
continue for another 3 h. The colour of the reaction mixture turned
bright orange when the temperature reached 393 K. Water, the by-
product of the reaction, was removed via azeotropic distillation with
toluene. On completion of the reaction, the mixture was allowed to
cool to room temperature and diluted with dichloromethane (30 ml).
The resulting heterogeneous mixture was filtered through Celite at
reduced pressure, and the solvents from the dark–orange filtrate were
removed under high vacuum to yield a bright-orange solid residue.
The crude product was dissolved in dichloromethane (15 ml), trans-
ferred to a separation funnel and washed repeatedly with deionized
water. The organic layer was collected, dried over magnesium sulfate,
filtered, and the filtrate evaporated using a rotary evaporator to yield
a bright-orange solid. Crystals of (I) suitable for X-ray diffraction
were obtained by recrystallization from an ethanol–dichloromethane
solution (3:1 v/v) (yield 73.4%; m.p. 381–382 K). Spectroscopic
analysis for (I): 1H NMR (300 MHz, CDCl3): ꢁ 8.4 (t, 1H), 8.0 (m, 1H),
5.9 (m, 1H), 5.6 (m, 1H), 4.4 (t, 1H), 3.3 (m, 4H), 1.3 (t, 6H); 13C NMR
(300 MHz, CDCl3): ꢁ 200.59, 154.52, 148.70, 129.47, 104.90, 90.10,
38.10, 37.76, 14.61, 14.42; IR (NaCl, ꢂ > 1400 cmꢂ1): 3340, 3307, 2973,
1623, 1551, 1460, 1397, 1322, 1268, 1197, 1169, 1149; MS (m/z) (%
base peak): 209 (100), 194 (24.5), 176 (62.8), 160 (44.9), 149 (23.9), 134
(20.2).
Compound (I)
Crystal data
3
˚
C10H15N3O2
Mr = 209.25
V = 2172.2 (2) A
Z = 8
Monoclinic, P21=c
Mo Kꢄ radiation
ꢅ = 0.09 mmꢂ1
T = 140 K
0.22 ꢄ 0.18 ꢄ 0.04 mm
˚
a = 7.8148 (5) A
˚
b = 20.9889 (14) A
˚
c = 13.2464 (9) A
ꢃ = 91.210 (2)ꢁ
Data collection
Bruker SMART 6000 CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.559, Tmax = 1.000
23033 measured reflections
4717 independent reflections
3307 reflections with I > 2ꢆ(I)
Rint = 0.059
Refinement
R[F2 > 2ꢆ(F2)] = 0.048
wR(F2) = 0.139
S = 0.97
391 parameters
All H-atom parameters refined
Compound (II) was prepared using a similar reaction setup to (I).
The flask was charged with anhydrous potassium carbonate (2.246 g,
0.016 mol). Ethylamine (0.573 g, 0.013 mol) was weighed in a one-
dram glass vial and dissolved in DMAC (5 ml). The solution was
added dropwise to the reaction mixture and the vial was subsequently
rinsed with DMAC (5 ml) to ensure complete transfer of the ethyl-
amine. 2,6-Difluoro-3-nitrobenzonitrile (1.197, 0.00650 mol) in
DMAC (5 ml) was added, leading to the formation of a cloudy yellow
reaction mixture. Additional DMAC (5 ml) was used to wash the
transfer container and this was added to the reaction mixture,
followed by toluene (20 ml). At approximately 363 K, the colour of
the reaction mixture was a cloudy orange. The temperature was
raised to 393 K and the reaction allowed to continue at this
temperature for 7 h. The crude product was isolated as for (I) and
purified by silica-gel chromatography (20% dichloromethane in
hexane, v/v), to give a bright-yellow solid. Crystals of (II) suitable for
X-ray diffraction were obtained by recrystallization from methanol
(yield 71%; m.p. 420–422 K). Spectroscopic analysis for (II): 1H NMR
(300 MHz, CDCl3): ꢁ 9.10 (t, 1H), 8.31 (m, 1H), 6.00 (m, 1H), 5.45 (t,
1H), 3.84 (m, 2H), 3.36 (m, 2H), 1.35 (m, 6H); 13C NMR (300 MHz,
CDCl3): ꢁ 157.40, 149.44, 134.17, 124.30, 118.28, 99.67, 77.26, 40.23,
ꢂ3
˚
Áꢇmax = 0.35 e A
Áꢇmin = ꢂ0.26 e A
ꢂ3
˚
4717 reflections
Compound (II)
Crystal data
3
˚
V = 1133.9 (17) A
Z = 4
C11H14N4O2
Mr = 234.26
Monoclinic, P21=c
Mo Kꢄ radiation
ꢅ = 0.10 mmꢂ1
T = 150 K
0.55 ꢄ 0.40 ꢄ 0.18 mm
˚
a = 10.988 (8) A
˚
b = 4.865 (4) A
˚
c = 21.220 (18) A
ꢃ = 91.62 (4)ꢁ
Data collection
Bruker SMART 6000 CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.819, Tmax = 1.000
11551 measured reflections
2745 independent reflections
2346 reflections with I > 2ꢆ(I)
Rint = 0.020
ꢃ
o372 Payne et al. C10H15N3O2, C11H14N4O2 and C16H18N4O6S
Acta Cryst. (2010). C66, o369–o373

organic compounds
Refinement
Table 1
Hydrogen-bond geometry (A, ) for (I).
ꢁ
˚
R[F2 > 2ꢆ(F2)] = 0.045
wR(F2) = 0.131
S = 1.04
2745 reflections
228 parameters
H atoms treated by a mixture of
independent and constrained
refinement
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
ꢂ3
˚
Áꢇmax = 0.40 e A
N1—H1Nꢀ ꢀ ꢀO2
N2—H2Nꢀ ꢀ ꢀO4
N4—H4Nꢀ ꢀ ꢀO4
N5—H5Nꢀ ꢀ ꢀO1i
0.86 (2)
1.950 (19)
2.12 (2)
1.961 (17)
2.079 (18)
2.6091 (18)
2.9835 (18)
2.6330 (16)
2.9507 (18)
132.3 (17)
167.8 (16)
134.8 (13)
170.0 (15)
ꢂ3
˚
Áꢇmin = ꢂ0.39 e A
0.878 (19)
0.854 (17)
0.881 (18)
Compound (III)
Symmetry code: (i) x ꢂ 1; y; z þ 1.
Crystal data
3
˚
V = 1799.8 (11) A
Z = 4
Mo Kꢄ radiation
ꢅ = 0.22 mmꢂ1
T = 210 K
C16H18N4O6S
Mr = 394.40
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢁ
˚
Monoclinic, P21=c
˚
a = 15.514 (5) A
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
˚
b = 8.573 (4) A
˚
c = 15.012 (5) A
ꢃ = 115.647 (12)ꢁ
0.20 ꢄ 0.15 ꢄ 0.09 mm
N2—H2Nꢀ ꢀ ꢀO2
N2—H2Nꢀ ꢀ ꢀO2i
N4—H4Nꢀ ꢀ ꢀN1ii
Symmetry codes: (i) ꢂx; y þ ; ꢂz þ ; (ii) ꢂx þ 1; ꢂy þ 1; ꢂz þ 1.
0.89 (2)
0.89 (2)
0.873 (18)
1.88 (2)
2.47 (2)
2.361 (19)
2.610 (2)
3.123 (2)
3.198 (3)
138.8 (19)
130.7 (17)
160.7 (15)
Data collection
1
2
1
2
Bruker SMART 6000 CCD area-
detector diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
Tmin = 0.793, Tmax = 1.000
14699 measured reflections
3539 independent reflections
3011 reflections with I > 2ꢆ(I)
Rint = 0.030
Table 3
Hydrogen-bond geometry (A, ) for (III).
ꢁ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
Refinement
N1—H1Nꢀ ꢀ ꢀO3
N3—H3Nꢀ ꢀ ꢀO6
N1—H1Nꢀ ꢀ ꢀO2i
N3—H3Nꢀ ꢀ ꢀO2ii
0.846 (19)
0.86 (2)
0.846 (19)
0.86 (2)
1.972 (19)
2.00 (2)
2.862 (19)
2.80 (2)
2.646 (2)
2.644 (2)
3.332 (2)
3.201 (2)
135.9 (17)
131.2 (19)
117.0 (15)
110.4 (17)
R[F2 > 2ꢆ(F2)] = 0.034
wR(F2) = 0.095
S = 1.02
316 parameters
All H-atom parameters refined
ꢂ3
˚
Áꢇmax = 0.33 e A
ꢂ3
˚
3539 reflections
Áꢇmin = ꢂ0.27 e A
1
1
1
2
1
2
Symmetry codes: (i) x; ꢂy þ ; z þ ; (ii) x; ꢂy þ ; z ꢂ .
2
2
The disordered ethyl C atoms in (II) were located in a difference
Fourier synthesis. The occupancies of the two sets of atoms,
constrained to sum to 1, were initially refined with the Uiso values of
all four atoms fixed to the same value. At a later stage of the
refinement, the occupancies were fixed to the approximate refined
values (i.e. 0.75 and 0.25) and the atomic displacement parameters
were refined. All H atoms were located in difference Fourier synth-
˚
eses and refined isotropically [C—H = 0.88 (2)–1.05 (4) A], except for
those of the minor-occupancy ethyl fragment of (II), which were
˚
treated as riding, with C—H = 0.99 A and Uiso(H) = 1.2Ueq(C)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK3377). Services for accessing these data are
described at the back of the journal.
References
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DKM acknowledges financial support for this project from
the Research Excellence Fund of Michigan and a President’s
Bridge to Commercialization Grant, and sabbatical support
from Central Michigan University. The authors thank the
College of Arts and Sciences of the University of Toledo and
the Ohio Board of Regents for generous financial support of
the X-ray diffraction facility.
ꢃ
Acta Cryst. (2010). C66, o369–o373
Payne et al.
C10H15N3O2, C11H14N4O2 and C16H18N4O6S o373