N - H...O, O - n...-bonded supra molecular sheet formation in the bis (2-amino anilinium) fumarate, 3-methyl anilinium hydrogen fumarate and 4-chloro anilinium hydrogen fumarate salts

Article abstract of DOI:10.1107/S0108270113017629

In bis (2-amino anilinum) fumarate, 2C6H9N2 ⁺·C4H2O4 ^2-, (I), the asymmetric unit consists of two amino anilinium cations and one fumarate dianion, whereas in 3-methyl anilinium hydrogen fumarate, C7H10N⁺·C4H3O4 ^-, (II), and 4-chloro anilinium hydrogen fumarate, C6H7ClN⁺·C4H3O4 ^-, (III), the asymmetric unit contains two symmetry-independent hydrogen fumate anions and anilinium cations with a slight difference in their geometric parameters; the two salts are isostructural. In (II) and (III), the carb oxy lic acid H atoms of the anions are disordered across both ends of the anion, with equal site occupancies of 0.50. Both the 4-chloro anilinium cations of (III) are disordered over two orientations with major occupancies fixed at 0.60 in each case. The hydrogen fumarate anions of (II) and (III) form one-dimensional anionic chains linked through O - H...O hydrogen bonds. Salts (II) and (III) form two-dimensional supra molecular sheets built from R 4 ⁴(16), R 4 ⁴(18), R 5 ⁵(25) and C 2 ²(14) motifs extending parallel to the (010) plane, whereas in (I), an (010) sheet is formed built from two R 4 ³(13) motifs, two R 2 ²(9) motifs and an R 4 ⁴(18) motif.

Full text of DOI:10.1107/S0108270113017629

organic compounds
Acta Crystallographica Section C
Crystal Structure
such as nonlinear optical, magnetic, catalytic and storage
´
properties (Gomes et al., 2006; Fabry et al., 2000; Ivasenko &
Communications
Perepichka, 2011). Dicarboxylic acids possessing very good
donors and acceptors are of special interest in forming strong
intermolecular hydrogen bonds between cations, anions or
molecular constituents when they form salts or cocrystals with
amines, amides and other metal complexes (Jagan & Siva-
kumar, 2011; Lyakhov et al., 2012; Jin et al., 2011; Farrell et al.,
2002). Maleic and fumaric acids are the Z and E isomers,
respectively, of butenedioic acid, and they form interesting
one-, two- and three-dimensional supramolecular archi-
tectures as adducts with various amines (Franklin & Balasu-
bramanian, 2009; Bowes et al., 2003; Jin et al., 2003; Batchelor
et al., 2000). Cis- and trans-dicarboxylic acids such as maleic
and fumaric acids have the interesting property of forming
ISSN 0108-2701
N—Hꢀ ꢀ ꢀO, O—Hꢀ ꢀ ꢀO hydrogen-
bonded supramolecular sheet forma-
tion in the bis(2-aminoanilinium)
fumarate, 3-methylanilinium hydrogen
fumarate and 4-chloroanilinium
hydrogen fumarate salts
D. Sathya,a R. Jagan,a R. Padmavathy,b R. Mohan Kumarc
and K. Sivakumara*
aDepartment of Physics, Anna University, Chennai 600 025, India, bDepartment of
Physics, Quaid-E-Millath Government College for Women, Chennai 600 002, India,
and cDepartment of Physics, Presidency College, Chennai 600 005, India
Correspondence e-mail: ksivakumar@annauniv.edu
Received 28 April 2013
Accepted 26 June 2013
+
In bis(2-aminoanilinum) fumarate, 2C6H9N2 ꢀC4H2O42ꢁ, (I),
the asymmetric unit consists of two aminoanilinium cations
and one fumarate dianion, whereas in 3-methylanilinium
hydrogen fumarate, C7H10N+ꢀC4H3O4ꢁ, (II), and 4-chloro-
anilinium hydrogen fumarate, C6H7ClN+ꢀC4H3O4ꢁ, (III), the
asymmetric unit contains two symmetry-independent
hydrogen fumate anions and anilinium cations with a slight
difference in their geometric parameters; the two salts are
isostructural. In (II) and (III), the carboxylic acid H atoms of
the anions are disordered across both ends of the anion, with
equal site occupancies of 0.50. Both the 4-chloroanilinium
cations of (III) are disordered over two orientations with
major occupancies fixed at 0.60 in each case. The hydrogen
fumarate anions of (II) and (III) form one-dimensional
anionic chains linked through O—Hꢀ ꢀ ꢀO hydrogen bonds.
Salts (II) and (III) form two-dimensional supramolecular
sheets built from R44(16), R44(18), R55(25) and C22(14) motifs
extending parallel to the (010) plane, whereas in (I), an (010)
sheet is formed built from two R34(13) motifs, two R22(9) motifs
and an R44(18) motif.
isomers on changes in their physical environment, such as
heat, light etc., thereby enhancing their hydrogen-bonding
capability (Kalita & Baruah, 2010). Consequently, numerous
recent articles have focused on the construction of fumarate
salts with different bases, showing innovative supramolecular
assemblies (Haynes & Pietersen, 2008; Hemamalini & Fun,
2010). We report herein the crystal structures of the title salts,
bis(2-aminoanilinum) fumarate, (I), 3-methylanilinium
hydrogen fumarate, (II), and 4-chloroanilinium hydrogen
fumarate, (III), in order to study their hydrogen-bonding
patterns and the consequent network present in the solid state.
Even though we have chosen maleic acid for (I) in the
preparation of the salt, unexpectedly the isomerization of
maleic to fumaric acid has taken place in the formation of the
title salt. A similar kind of geometric isomerization has been
observed in the previously reported structures of 4,40-bi-
pyridylamine and 4,40-trimethylenedipyridine fumaric acids
(Chatterjee et al., 1998; Bowes et al., 2003).
Keywords: crystal structure; hydrogen bonding; fumarate salts.
1. Introduction
Hydrogen bonding is considered to be one of the best
noncovalent interactions in supramolecular networks because
of its strength and highly directional nature (Desiraju, 2002;
Aakeroy et al., 2005). Various hydrogen-bonded motifs and
frameworks revealed in the field of crystal engineering have
become tools to explain various physicochemical properties,
904 # 2013 International Union of Crystallography
doi:10.1107/S0108270113017629
Acta Cryst. (2013). C69, 904–909

organic compounds
Table 1
Experimental details.
(I)
(II)
(III)
Crystal data
Chemical formula
Mr
+
2ꢂ
ꢂ
ꢂ
2C6H9N2 ꢁC4H2O4
C7H10N+ꢁC4H3O4
C6H7ClN+ꢁC4H3O4
332.36
Orthorhombic, Iba2
296
10.0424 (2), 42.9871 (11), 7.4930 (2)
90, 90, 90
3234.68 (14)
8
223.22
Monoclinic, P21/n
296
9.4576 (3), 20.8915 (6), 10.8787 (3)
243.64
Monoclinic, P21/n
Crystal system, space group
Temperature (K)
293
9.2335 (4), 23.8248 (11), 10.4424 (5)
˚
a, b, c (A)
ꢀ, ꢁ, ꢂ (ꢃ)
90, 92.611 (2), 90
2147.22 (11)
8
Mo Kꢀ
0.11
90, 94.338 (2), 90
2290.60 (18)
8
Mo Kꢀ
0.33
3
˚
V (A )
Z
Radiation type
Mo Kꢀ
0.10
ꢃ (mmꢂ1
Crystal size (mm)
)
0.35 ꢄ 0.30 ꢄ 0.20
0.35 ꢄ 0.30 ꢄ 0.25
0.35 ꢄ 0.30 ꢄ 0.25
Data collection
Diffractometer
Bruker Kappa APEXII CCD
area-detector diffractometer
Multi-scan
Bruker Kappa APEXII CCD
area-detector diffractometer
Multi-scan
Bruker Kappa APEXII CCD
area-detector diffractometer
Multi-scan
Absorption correction
(SADABS; Bruker, 2004)
0.916, 0.980
9034, 3406, 2751
(SADABS; Bruker, 2004)
0.904, 0.974
37301, 6714, 5066
(SADABS; Bruker, 2004)
0.903, 0.912
25081, 5334, 3844
Tmin, Tmax
No. of measured,
independent and
observed [I > 2ꢄ(I)]
reflections
Rint
0.035
0.639
0.036
0.720
0.032
0.655
ꢂ1
˚
(sin ꢅ/ꢆ)max (A
)
Refinement
R[F2 > 2ꢄ(F2)], wR(F2), S
No. of reflections
0.049, 0.140, 1.05
3406
0.044, 0.130, 1.04
6714
0.043, 0.122, 1.03
5334
No. of parameters
No. of restraints
H-atom treatment
247
11
322
10
428
186
H atoms treated by a mixture of
independent and constrained
refinement
0.47, ꢂ0.23
H atoms treated by a mixture of
independent and constrained
refinement
0.38, ꢂ0.21
H atoms treated by a mixture of
independent and constrained
refinement
ꢂ3
˚
Áꢇmax, Áꢇmin (e A
)
0.40, ꢂ0.35
Computer programs: APEX2, SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), Mercury (Macrae et al.,
2008) and PLATON (Spek, 2009).
and O4B, revealed the presence of H atoms. The carboxyl
C—O bond lengths and the improvement in the refinement
confirmed the occupancy of the H atoms. Both the 4-chloro-
anilinium cations of (III) are disordered over two orientations.
The site occupancies of the two orientations of each cation
were initially refined and then fixed with the major occupancy
being 0.60 in each case. For the disordered cations of (III), the
disordered C—C bond lengths of the benzene rings were
2. Experimental
2.1. Synthesis and crystallization
A solution containing equimolar quantities of maleic acid
and 2-aminoaniline in methanol was warmed for 10 min and
set aside to crystallize. Brown crystals suitable for diffraction
analysis were obtained by slow evaporation after a few days.
Unexpectedly, the isomerization of maleic to fumaric acid had
taken place during the salt formation. The resulting salt, (I),
contained a 1:2 molar ratio of the fumarate dianion and the
2-aminoanilinium cation. Similarly, salts (II) and (III) were
prepared from equimolar ratios of fumaric acid with
3-methylaniline and 4-chloroaniline, respectively, dissolved in
ethanol. Both ethanol solutions were mixed together and
stirred for 20 min and the resulting mixture was kept for
crystallization. Good diffraction-quality colourless crystals
were obtained by slow evaporation after a few days.
˚
restrained to a distance of 1.39 (1) A and the C—Cl bond
˚
lengths were restrained to 1.72 (1) A. The atomic displace-
ment parameters of the disordered components were made
similar to those of neighbouring atoms using standard simi-
2
larity restraints, with an s.u. of 0.02 A for ring atoms or
˚
2
0.04 A for terminal atoms, followed by rigid-bond restraints,
˚
˚
with an s.u. of 0.01 A. Finally, the disordered cations were also
restrained to be planar. Salt (I) shows a meaningless Flack
parameter (Flack, 1983) value of 0.1 (18). This is due to the
molecular structure of (I) having light atoms (<Si) with no
significant anomalous scattering effects. In this case, the Flack
parameter is indeterminate with Mo radiation and hence the
absolute structure cannot be determined. The positions of all
the H atoms were initially identified from the difference
electron-density map. The positions of the C-bound H atoms
were then idealized and allowed to ride on their parent atom,
2.2. Refinement
Crystal data, data collection and structure refinement
details are summarized in Table 1. In salts (II) and (III), the
carboxylic acid H atoms of the anions were disordered across
both ends of the anion showing equal site occupancies of 0.50.
The appearance of strong difference electron-density peaks,
and their distances from the nearest atoms O1A, O1B, O4A
˚
with C—H = 0.96 A and Uiso(H) = 1.5Ueq(C) for CH3, and
+
2ꢂ
ꢀ
Acta Cryst. (2013). C69, 904–909
Sathya et al.
2C6H9N2 ꢁC4H2O4 and two analogues 905

organic compounds
Table 2
Hydrogen-bond geometry (A, ) for (I).
ꢃ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N4—H4Cꢁ ꢁ ꢁO4i
N2—H2Aꢁ ꢁ ꢁO2ii
N3—H3Aꢁ ꢁ ꢁO3iii
N1—H1Aꢁ ꢁ ꢁO1iv
N2—H2Bꢁ ꢁ ꢁO3v
N4—H4Aꢁ ꢁ ꢁO1vi
N3—H3Bꢁ ꢁ ꢁO3
N1—H1Bꢁ ꢁ ꢁO1
N4—H4Bꢁ ꢁ ꢁO4
N2—H2Cꢁ ꢁ ꢁO2
0.90 (1)
0.90 (1)
0.90 (1)
0.90 (1)
0.92 (1)
0.91 (1)
0.90 (1)
0.90 (1)
0.90 (1)
0.90 (1)
1.85 (1)
1.85 (1)
2.29 (2)
2.23 (2)
1.91 (1)
1.93 (1)
2.06 (1)
2.05 (1)
1.87 (1)
1.90 (2)
2.728 (3)
2.729 (3)
3.106 (3)
3.101 (3)
2.811 (3)
2.820 (3)
2.956 (4)
2.926 (4)
2.756 (3)
2.758 (4)
165 (3)
166 (3)
150 (2)
161 (3)
170 (2)
167 (2)
175 (3)
166 (3)
166 (3)
159 (3)
Figure 1
Displacement ellipsoid plot of salt (I), drawn at the 40% probability level
and showing the atom-labelling scheme. The dashed lines between the
ions represent hydrogen bonds.
1
2
1
2
1
2
Symmetry codes: (i) ꢂx; y; z þ ; (ii) ꢂx þ 1; y; z ꢂ ; (iii) ꢂx þ 1; y; z þ ; (iv)
1
2
ꢂx; y; z ꢂ ; (v) x; y; z ꢂ 1; (vi) x; y; z þ 1.
˚
C—H = 0.93 A and Uiso(H) = 1.2Ueq(C) for aromatic H atoms.
O-bound H atoms were positioned from the difference elec-
tron-density map and refined with O—H distance restraints of
˚
0.85 (1) A for salts (II) and (III), with Uiso(H) = 1.2Ueq(O).
The H atoms associated with both the NH2 and NH3+ groups
˚
were refined with N—H distance restraints of 0.90 (1) A for
(I), (II) and (III), with Uiso(H) = 1.2Ueq(N).
3. Results and discussion
The asymmetric unit of (I) (Fig. 1) contains two 2-amino-
anilinium cations and one fumarate dianion, whereas salts (II)
and (III) (Figs. 2 and 3) consist of two sets of symmetry-
independent cations and anions having a slight difference in
their geometric parameters. The C—O bond lengths of (I)
˚
˚
[C1—O1 = 1.242 (3) A, C1—O2 = 1.259 (3) A, C4—O3 =
˚
˚
1.256 (3) A and C4—O4 = 1.265 (3) A] suggest the two
carboxylate groups are deprotonated in the crystal structure.
In salts (II) and (III), the carboxylic acid H atoms of the
hydrogen fumarate anions are disordered over equally occu-
pied alternate positions at opposite ends of the anion. Also in
Figure 2
Displacement ellipsoid plot of salt (II), drawn at the 40% probability
level and showing the atom-labelling scheme. The dashed lines between
the ions represent hydrogen bonds.
Figure 3
Displacement ellipsoid plot of salt (III), drawn at the 40% probability
level and showing the atom-labelling scheme. The dashed lines between
the ions represent hydrogen bonds. The bonds in the minor components
of the disordered cations are represented as single dashed lines.
Figure 4
Part of the crystal structure of (I), showing the formation of the
supramolecular ladder linked through N—Hꢁ ꢁ ꢁO hydrogen bonds.
1
1
[Symmetry codes: (iii) ꢂx + 1, y, z + ; (iv) ꢂx, y, z ꢂ .]
2
2
+
2ꢂ
ꢀ
906 Sathya et al.
2C6H9N2 ꢁC4H2O4 and two analogues
Acta Cryst. (2013). C69, 904–909

organic compounds
Figure 5
Part of the crystal strucure of (II), showing the formation of the one-dimensional anionic chain linked through O4A—H4Aꢁ ꢁ ꢁO1Biv and O4B—
H4Bꢁ ꢁ ꢁO1A hydrogen bonds. [Symmetry code: (iv) x ꢂ 1, y, z + 1.]
(III), both of the 4-chloroanilinium cations are disordered
over two orientations with major occupancies of 0.60 in each
case. In salt (I), the fumarate anion is almost planar compared
with the hydrogen fumarate anions of (II) and (III), as shown
by the dihedral angles between the carboxylic acid–
carboxylate groups of 1.57 (6)ꢃ for (I), 40.03 (7) and 25.93 (2)ꢃ
for (II), and 25.80 (3) and 42.43 (1)ꢃ for (III). Interestingly, the
adjacent hydrogen fumarate anions of (II) and (III) form very
strong hydrogen bonds, with donor–acceptor distances in the
forming a molecular ladder in which the cations form the
uprights and the anions form the rungs, built through R24(18)
and two R22(9) motifs, as illustrated in Fig. 4. The molecular
ladder runs along the line at (x, 14, 0). Protonated atoms N2 and
N4 of the cations at (x, y, z) form hydrogen bonds with
1
acceptors O2 at (ꢂx + 1, y, z ꢂ ) and O3 at (x, y, z ꢂ 1), and
2
with O1 at (x, y, z + 1) and O4 at (ꢂx, y, z + 12), respectively,
connecting adjacent molecular ladders and hence generating
an infinite two-dimensional sheet parallel to the (010) plane.
The (010) molecular sheet is constructed through two R34(13)
motifs, two R22(9) motifs and an R44(18) motif.
˚
range 2.45–2.47 A (Tables 3 and 4).
In (I), all the O atoms in the fumarate dianion form bifur-
cated hydrogen bonds with the anilinium cations. In the
asymmetric unit, both carboxylate O atoms of the anion
interact with adjacent 2-aminoanilinium cations through four
N—Hꢁ ꢁ ꢁO hydrogen bonds (N1—H1Bꢁ ꢁ ꢁO1, N2—H2Cꢁ ꢁ ꢁO2,
N3—H3Bꢁ ꢁ ꢁO3 and N4—H4Bꢁ ꢁ ꢁO4; Table 2) forming two
R22(9) motifs (Bernstein et al., 1995). These asymmetric unit
pairs are further linked through four N—Hꢁ ꢁ ꢁO hydrogen
bonds (N1—H1Aꢁ ꢁ ꢁO1iv, N3—H3Aꢁ ꢁ ꢁO3iii, N2iii—H2Aꢁ ꢁ ꢁO2
and N4iv—H4Cꢁ ꢁ ꢁO4; see Table 2 for symmetry codes),
Adjacent A and B hydrogen fumarate anions of (II) are
interlinked through two O—Hꢁ ꢁ ꢁO hydrogen bonds (O4A—
H4Aꢁ ꢁ ꢁO1Biv and and O4B—H4Bꢁ ꢁ ꢁO1A; see Table 3 for
details), forming a C22(14) chain motif which extends further
along the [101] direction, generating an infinite cationic chain
(Fig. 5). The disorder found in the positions of the carboxylic
acid H atoms in the cations merely reflects a reversal in the
direction of propagation of the hydrogen bonds in the chains
represented by Fig. 5, as a consequence of a switch of which
Figure 6
Part of the crystal structure of (II), showing the formation of the O—Hꢁ ꢁ ꢁO and N—Hꢁ ꢁ ꢁO hydrogen-bonded supramolecular R44(16) and R66(32) motifs
constructing a two-dimensional brick-wall structure propagating parallel to the (010) plane. The symmetry codes are as in Table 3.
+
2ꢂ
ꢀ
Acta Cryst. (2013). C69, 904–909
Sathya et al.
2C6H9N2 ꢁC4H2O4 and two analogues 907

organic compounds
Table 3
Hydrogen-bond geometry (A, ) for (II).
ꢃ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N1B—H1BBꢁ ꢁ ꢁO2Ai
N1A—H1ABꢁ ꢁ ꢁO2Bii
N1B—H1BCꢁ ꢁ ꢁO1Bii
N1A—H1ACꢁ ꢁ ꢁO4Biii
O4A—H4Aꢁ ꢁ ꢁO1Biv
O1B—H1Bꢁ ꢁ ꢁO4Av
N1A—H1AAꢁ ꢁ ꢁO3A
N1B—H1BAꢁ ꢁ ꢁO3B
O4B—H4Bꢁ ꢁ ꢁO1A
O1A—H1Aꢁ ꢁ ꢁO4B
0.90 (1)
0.93 (1)
0.91 (1)
0.91 (1)
0.85 (1)
0.86 (1)
0.90 (1)
0.91 (1)
0.85 (1)
0.85 (1)
2.01 (1)
1.86 (1)
1.93 (1)
1.92 (1)
1.62 (1)
1.62 (1)
1.97 (1)
1.87 (1)
1.62 (1)
1.62 (1)
2.8924 (14)
2.7777 (15)
2.8111 (14)
2.7993 (15)
2.4703 (11)
2.4703 (11)
2.8539 (15)
2.7757 (13)
2.4678 (11)
2.4678 (11)
168 (1)
168 (1)
165 (2)
162 (1)
175 (3)
176 (3)
168 (1)
173 (1)
175 (3)
176 (3)
Symmetry codes: (i) ꢂx þ 1; ꢂy þ 1; ꢂz þ 1; (ii) ꢂx þ 1; ꢂy þ 1; ꢂz; (iii) x ꢂ 1; y; z;
(iv) x ꢂ 1; y; z þ 1; (v) x þ 1; y; z ꢂ 1.
Table 4
Hydrogen-bond geometry (A, ) for (III).
ꢃ
˚
D—Hꢁ ꢁ ꢁA
D—H
Hꢁ ꢁ ꢁA
Dꢁ ꢁ ꢁA
D—Hꢁ ꢁ ꢁA
N1A—H1A2ꢁ ꢁ ꢁO3Bi
N1A—H1A3ꢁ ꢁ ꢁO4Aii
N1B—H1B2ꢁ ꢁ ꢁO3Aii
N1B—H1B3ꢁ ꢁ ꢁO2Aiii
O2B—H2Dꢁ ꢁ ꢁO4Aiv
N1A—H1A1ꢁ ꢁ ꢁO1A
N1B—H1B1ꢁ ꢁ ꢁO1B
O2A—H2Cꢁ ꢁ ꢁO4B
0.91 (1)
0.90 (1)
0.91 (1)
0.91 (1)
0.85 (1)
0.91 (1)
0.91 (1)
0.85 (1)
1.89 (1)
2.00 (1)
1.84 (1)
2.03 (2)
1.62 (1)
1.83 (1)
1.89 (1)
1.61 (1)
2.7958 (19)
2.8759 (19)
2.7354 (19)
2.860 (2)
2.4592 (15)
2.7302 (18)
2.787 (2)
175 (3)
162 (2)
170 (3)
153 (2)
172 (6)
172 (3)
173 (3)
175 (6)
2.4590 (15)
Symmetry codes: (i) ꢂx þ 1; ꢂy þ 1; ꢂz þ 1; (ii) ꢂx þ 1; ꢂy þ 1; ꢂz þ 2; (iii)
x þ 1; y; z; (iv) x þ 1; y; z ꢂ 1.
The cations of salts (I), (II) and (III) are closely similar, as
all three have cations which are substituted anilines with a
protonated NH3+ group. The substitution differs in each, being
2-amino in (I), 3-methyl in (II) and 4-chloro in (III). Inter-
estingly, salts (II) and (III) show similar hydrogen-bonded
supramolecular architectures, as described above. It is
observed that, for (I), the anion is doubly dissociated,
although the difference in the supramolecular networks can be
explained by the presence of the amino group in the ortho
position which forms additional hydrogen-bond donors with
neighbouring acceptor O atoms. The methyl and chloro
substitutents in (II) and (III) are nonfunctional groups and do
not form hydrogen bonds with adjacent anions.
Figure 7
The inversion-related (010) brick-wall structures fused together to form a
two-dimensional supramolecular sheet of anions and cations extending
parallel to the (010) plane, with the cations pendant from both faces,
observed in (a) salt (II) and (b) salt (III). The two different colours
represent the two inversion-related sheets.
side of the Oꢁ ꢁ ꢁO contact each H atom is occupying. A similar
type of motif is also observed in (III), as these two salts are
isostructural. The molecular planes of the hydrogen fumarate
anions are approximately perpendicular to one another, with
angles between the planes of 87.70 (4)ꢃ for (II) and 87.64 (5)ꢃ
for (III). Parallel anionic chains are crosslinked in (II) or (III)
by anilinium cations through four N—Hꢁ ꢁ ꢁO hydrogen bonds
[for example, in (III), N1A—H1ACꢁ ꢁ ꢁO4Biii, N1A—
H1AAꢁ ꢁ ꢁO3A, N1B—H1BBꢁ ꢁ ꢁO2Ai and N1B—H1BCꢁ ꢁ ꢁ
O1Bii; see Table 3 for details], forming R44(16) and R66(32)
motifs to construct a two-dimensional brick-wall structure
propagating parallel to the (010) plane (Fig. 6). Inversion-
related two-dimensional (010) brick-wall structures are fused
together through two N—Hꢁ ꢁ ꢁO hydrogen bonds (N1B—
H1BAꢁ ꢁ ꢁO3B and N1A—H1ABꢁ ꢁ ꢁO2Bii; Table 3) to form a
molecular sheet built from a combination of R44(16), R44(18),
R55(25) and C22(14) motifs and extending parallel to the ac
plane. The A and B cations are pendant from both faces of the
molecular network (Fig. 7a). Salt (III) (Table 4) also shows a
similar two-dimensional supramolecular sheet along the (010)
plane, with cations pendant from both faces of the (010) sheet
(Fig. 7b).
A search for fumarate salts in the Cambridge Structural
Database (CSD, Version 5.31; Allen, 2002) shows some
specific features. The supramolecular frameworks observed in
bis(2-phenylethylammonium) fumarate fumaric acid (CSD
refcode COCPEQ; Haynes & Pietersen, 2008), bis(anilinium)
fumarate fumaric acid (COCPOA; Haynes & Pietersen, 2008)
and benzylammonium hydrogen fumarate (XINSAO; Ballabh
et al., 2002), the cations of which are closely similar to the
+
NH3 substitution, form one-dimensional anionic supra-
molecular chains similar to those observed in (II) and (III).
+
The presence of the NH3 group in (II) and (III) results in
strong N—Hꢁ ꢁ ꢁO hydrogen bonds interconnecting the anionic
chains through R44(16) and R55(25) motifs, constructing a two-
dimensional sheet along with the C22(14) chain. In all these
structures, cations pendant from both faces of the two-
dimensional supramolecular network are observed, as in (II)
and (III). Also, bis(2-cyanoethylammonium) fumarate (CSD
+
2ꢂ
ꢀ
908 Sathya et al.
2C6H9N2 ꢁC4H2O4 and two analogues
Acta Cryst. (2013). C69, 904–909

organic compounds
refcode JIZJUX; Fawcett et al., 1991) and bis(isopropyl-
ammonium) fumarate (NARDIT; Hosomi et al., 1998), though
References
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Supplementary data for this paper are available from the IUCr electronic
archives (Reference: UK3068). Services for accessing these data are
described at the back of the journal.
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Sathya et al.
2C6H9N2 ꢁC4H2O4 and two analogues 909