Proton-transfer compounds of isonipecotamide with the aromatic dicarb-oxy-lic acids 4-nitro-phthalic, 4,5-dichloro-phthalic, 5-nitro-iso-phthalic and terephthalic acid

Article abstract of DOI:10.1107/S0108270111020518

The structures of the 1:1 proton-transfer compounds of isonipecotamide (piperidine-4-carboxamide) with 4-nitro-phthalic acid [4-carbamoylpiperidinium 2-carb-oxy-4-nitro-benzoate, C₆H₁₃N₂O ₈ ⁺·C8H4O6 ^-, (I)], 4,5-dichloro- phthalic acid [4-carbamoylpiperidinium 2-carb-oxy-4,5-dichloro-benzo-ate, C ₆H₁₃N₂O₈ ⁺·C ₈H₃Cl₂O₄ ^-, (II)] and 5-nitro-isophthalic acid [4-carbamoylpiperidinium 3-carb-oxy-5-nitro-benzoate, C₆H₁₃N₂O₈ ⁺·C ₈H₄O₆ ^-, (III)], as well as the 2:1 compound with terephthalic acid [bis-(4-carbamoylpiperidinium) benzene-1,2-dicarboxyl-ate dihydrate, 2C₆H₁₃N ₂O₈ ⁺·C₈H₄O ₄ ^2-·2H₂O, (IV)], have been determined at 200 K. All salts form hydrogen-bonded structures, viz. one-dimensional in (II) and three-dimensional in (I), (III) and (IV). In (I) and (III), the centrosymmetric R 2 ²(8) cyclic amide-amide association is found, while in (IV) several different types of water-bridged cyclic associations are present [graph sets R₄ ²(8), R₄ ³(10), R₄ ⁴(12), R₃ ³(18) and R₆⁴(22)]. The one-dimensional structure of (I) features the common planar hydrogen 4,5-dichloro-phthalate anion, together with enlarged cyclic R₃ ³(13) and R₄ ³(17) associations. In the structures of (I) and (III), the presence of head-to-tail hydrogen phthalate chain substructures is found. In (IV), head-to-tail primary cation-anion associations are extended longitudinally into chains through the water-bridged cation associations, and laterally by piperidinium-carboxylate N-H...O and water-carboxylate O-H...O hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen-bonded structures. An additional example of cation-anion association with this cation is also shown in the asymmetric three-centre piperidinium-carboxylate N-H...O,O′ inter-action in the first-reported structure of a 2:1 isonipecotamide-carboxyl-ate salt.

Full text of DOI:10.1107/S0108270111020518

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
Comment
Our project investigating the hydrogen-bonding modes in salts
of the Lewis base piperidine-4-carboxamide (isonipecotamide;
INIPA) with carboxylic acids has provided a considerable
number of structures, the majority being anhydrous 1:1 salts
with aromatic acids (Smith & Wermuth, 2010d,f, 2011a).
Solvated examples are the nicotinate (a partial hydrate; Smith
& Wermuth, 2011c), the acetate (a monohydrate; Smith &
Wermuth, 2010e) and the 6-carboxypyridine-2-carboxylate (a
methanol monosolvate; Smith & Wermuth, 2011c), while with
o-phthalic acid a 1:1 hydrogen phthalate–phthalic acid salt
adduct is formed (Smith & Wermuth, 2011b). Anhydrous
picrates are also known (Smith & Wermuth, 2010c), together
with a 2:1 salt with bipyridine-4,40-disulfonate (Smith et al.,
2010). In the light of the unusual formation of a 1:1:1 cation–
anion–phthalic acid adduct from a 1:1 stoichiometric reaction
(Smith & Wermuth, 2011b), our further aim was to investigate
the nature of the products formed from similar reactions of
INIPA with a series of aromatic dicarboxylic acids in various
ISSN 0108-2701
Proton-transfer compounds of
isonipecotamide with the aromatic
dicarboxylic acids 4-nitrophthalic,
4,5-dichlorophthalic, 5-nitroiso-
phthalic and terephthalic acid
Graham Smitha* and Urs D. Wermuthb
aSchool of Physical and Chemical Sciences, Queensland University of Technology,
GPO Box 2434, Brisbane, Queensland 4001, Australia, and bSchool of Biomolecular
and Physical Sciences, Griffith University, Nathan, Queensland 4111, Australia
Correspondence e-mail: g.smith@qut.edu.au
Received 21 April 2011
Accepted 28 May 2011
Online 23 June 2011
The structures of the 1:1 proton-transfer compounds of
isonipecotamide (piperidine-4-carboxamide) with 4-nitro-
phthalic acid [4-carbamoylpiperidinium 2-carboxy-4-nitro-
+
benzoate, C6H13N2O8 ꢀC8H4O6ꢁ, (I)], 4,5-dichlorophthalic
acid [4-carbamoylpiperidinium 2-carboxy-4,5-dichlorobenzo-
+
ate, C6H13N2O8 ꢀC8H3Cl2O4ꢁ, (II)] and 5-nitroisophthalic acid
[4-carbamoylpiperidinium 3-carboxy-5-nitrobenzoate, C6H13-
+
N2O8 ꢀC8H4O6ꢁ, (III)], as well as the 2:1 compound with
terephthalic acid [bis(4-carbamoylpiperidinium) benzene-1,2-
+
dicarboxylate dihydrate, 2C6H13N2O8 ꢀC8H4O42ꢁꢀ2H2O,
(IV)], have been determined at 200 K. All salts form
hydrogen-bonded structures, viz. one-dimensional in (II)
and three-dimensional in (I), (III) and (IV). In (I) and (III),
the centrosymmetric R22(8) cyclic amide–amide association is
found, while in (IV) several different types of water-bridged
cyclic associations are present [graph sets R42(8), R43(10),
R44(12), R33(18) and R64(22)]. The one-dimensional structure of
(I) features the common ‘planar’ hydrogen 4,5-dichloro-
phthalate anion, together with enlarged cyclic R33(13) and
R43(17) associations. In the structures of (I) and (III), the
presence of head-to-tail hydrogen phthalate chain substruc-
tures is found. In (IV), head-to-tail primary cation–anion
associations are extended longitudinally into chains through
the water-bridged cation associations, and laterally by
piperidinium–carboxylate N—Hꢀ ꢀ ꢀO and water–carboxylate
O—Hꢀ ꢀ ꢀO hydrogen bonds. The structures reported here
further demonstrate the utility of the isonipecotamide cation
as a synthon for the generation of stable hydrogen-bonded
structures. An additional example of cation–anion association
with this cation is also shown in the asymmetric three-centre
piperidinium–carboxylate N—Hꢀ ꢀ ꢀO,O0 interaction in the
first-reported structure of a 2:1 isonipecotamide–carboxylate
salt.
alcoholic and aqueous alcoholic solutions. Examples included
4-nitrophthalic acid (NPHA), 4,5-dichlorophthalic acid
(DCPA), 5-nitroisophthalic acid (NIPA) and terephthalic acid
(TPA), which provided good crystalline products. The 1:1
anhydrous salts of 4-carbamoylpiperidinium 2-carboxy-4-
nitrobenzoate, (I), 4-carbamoylpiperidinium 2-carboxy-4,5-
dichlorobenzoate, (II), and 4-carbamoylpiperidinium 3-car-
boxy-5-nitrobenzoate, (III), were obtained, and the 2:1 hy-
drated salt of the terephthalate, bis(4-carbamoylpiperidinium)
benzene-1,2-dicarboxylate dihydrate, (IV), was also identified.
The structures of (I)–(IV) are described here.
Acta Cryst. (2011). C67, o259–o264
doi:10.1107/S0108270111020518
# 2011 International Union of Crystallography o259

organic compounds
Figure 3
The molecular conformation and atom-numbering scheme for the INIPA
cation and NIPA monoanion in (III). Displacement ellipsoids are drawn
at the 40% probability level. The inter-species hydrogen bond is shown as
a dashed line.
Figure 1
The molecular conformation and atom-numbering scheme for the INIPA
cation and NPHA monoanion in (I). Displacement ellipsoids are drawn at
the 40% probability level and the inter-species hydrogen bond is shown as
a dashed line.
Figure 2
The molecular configuration and atom-numbering scheme for the INIPA
cation and DCPA monoanion in (II). Displacement ellipsoids are drawn
at the 40% probability level and the inter-species hydrogen bond is shown
as a dashed line.
Figure 4
The molecular conformation and atom-numbering scheme for the INIPA
cation, the TPA dianion and the solvent water molecule in the asymmetric
unit of (IV). The dianion has inversion symmetry [symmetry code: (i) ꢁx,
ꢁy + 1, ꢁz]. Displacement ellipsoids are drawn at the 40% probability
level and inter-species hydrogen bonds are shown as dashed lines.
With the 1:1 salts, (I)–(III) (Figs. 1–4), proton transfer has
occurred to the hetero N atom of the piperidine ring, while
with the terephthalate salt, (IV), a two-proton transfer is
involved, with the formation of a dianion. The resulting
piperidinium group of the anion in each salt, together with the
hydrogen donor and acceptor p-related substituent amide
group, are subsequently involved in hydrogen-bonding inter-
actions. These result in supramolecular structures, which are
three-dimensional in (I), (III) and (IV), and one-dimensional
in (II) (Figs. 5–8). A feature of the hydrogen bonding in (I)
and (III) is the presence of the centrosymmetric cyclic
homomolecular N—Hꢀ ꢀ ꢀO hydrogen-bonded amide–amide
motif (Allen et al., 1998), with graph set R22(8) (Etter et al.,
1990; Bernstein et al., 1995). This motif has now been found in
11 of the 24 known structures of INIPA proton-transfer salts,
including the present examples.
In the structure of the 1:1 INIPA salt with 4-nitrophthalic
acid, (I), the 1-carboxy rather than the 2-carboxy group is
deprotonated (Fig. 1), giving a primary piperidinium–
carboxylate N—Hꢀ ꢀ ꢀO ion-pair interaction. The hydrogen
phthalate anions form head-to-tail hydrogen-bonded chain
substructures featuring short carboxy–carboxylate O—Hꢀ ꢀ ꢀO
hydrogen bonds [graph set C(7); Fig. 5]. These substructures
Figure 5
The two-dimensional hydrogen-bonded network structure of (I),
extending across the bOc plane of the unit cell, showing hydrogen-
bonding associations as dashed lines. Graph sets for cyclic hydrogen-
bonding associations are also indicated. Non-interactive H atoms have
been omitted. (For symmetry codes, see Table 1.)
o260 Smith and Wermuth C6H13N2O+ꢀC8H4NO6 and three analogues
Acta Cryst. (2011). C67, o259–o264
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organic compounds
Figure 7
Figure 6
The one-dimensional hydrogen-bonded ribbon structure of (II),
A perspective view of the three-dimensional hydrogen-bonded frame-
work structure of (III), showing the NIPA chain substructures and
amide–amide dimer associations. Hydrogen bonds are shown as dashed
lines. Graph sets for cyclic hydrogen-bonding associations are also
indicated. Non-interactive H atoms have been omitted. [Symmetry code:
extending along the
b cell direction, showing hydrogen-bonding
associations as dashed lines. Graph sets for cyclic hydrogen-bonding
associations are also indicated. Non-interactive H atoms have been
omitted. (For symmetry codes, see Table 2.)
1
1
(v) ꢁx + 1, y ꢁ , ꢁz + ; for other codes, see Table 3.]
2
2
are common among hydrogen phthalate salt structures
(Glidewell et al., 2005; Smith & Wermuth, 2010b). The
peripherally bound INIPA anions give structure extension
across (011) through classic centrosymmetric R22(8) amide–
amide N—Hꢀ ꢀ ꢀO hydrogen-bonded dimer associations. In
addition, amide–nitro N—Hꢀ ꢀ ꢀO and piperidinium–carbox-
ylate N—Hꢀ ꢀ ꢀO associations (Table 1) result in a three-
dimensional structure. In the nitrophthalate anion, the
carboxylate group is rotated significantly out of the benzene
plane [torsion angle C2—C1—C11—O12 = ꢁ76.7 (2)ꢃ], while
the carboxylic acid and nitro groups are essentially coplanar
with the benzene plane [torsion angles C1—C2—C21—O22 =
169.25 (16)ꢃ and C3—C4—N4—O42 = ꢁ174.03 (18)ꢃ].
˚
short hydrogen bond [2.393 (3) A] in the ‘planar’ DCPA anion
in (II) results in a C2—C1—C11—O11 torsion angle of
174.1 (3)ꢃ, while another feature of this conformation is
elongation of the C1—C11 and C2—C21 bonds [1.522 (4) and
˚
1.533 (4) A, respectively] and distortion of the external bond
angles at C1 and C2 [128.1 (2) and 128.8 (2)ꢃ, respectively;
Smith & Wermuth, 2010a].
In the structure of the hydrogen 5-nitroisphthalate salt, (III)
(Fig. 3), the primary cation–anion interaction has a second
longer
N—Hꢀ ꢀ ꢀOcarboxylate
contact
[N1Aꢀ ꢀ ꢀO12
=
ꢃ
˚
3.0366 (19) A and N1A—H12Aꢀ ꢀ ꢀO12 = 118.1 (17) ], similar
to that in (II). The cation–anion associations are also similar in
some respects to those of (I). The hydrogen isophthalate
anions give zigzag head-to-tail hydrogen-bonded chain
substructures through carboxy–carboxylate O—Hꢀ ꢀ ꢀO
hydrogen bonds (Table 3) but these are classified as graph set
C(8), rather than C(7) as in (I). In addition, the centrosym-
metric R22(8) hydrogen-bonded INPA amide–amide dimers
give peripheral structure extension through piperidinium–
carboxylate N—Hꢀ ꢀ ꢀO hydrogen bonds which involve two
anions, enclosing cyclic R33(10) rings (Fig. 7). The three-
dimensional framework structure is generated through amide–
carboxylate N—Hꢀ ꢀ ꢀO hydrogen-bonding associations. The
nitro O atoms are unassociated, except for weak inter-
In the structure of the 1:1 INIPA salt with 4,5-dichloro-
phthalic acid, (II) (Fig. 2), one of the two primary piper-
idinium cation–anion associations also involves a secondary
˚
longer three-centre interaction [N1Aꢀ ꢀ ꢀO12 = 3.042 (4) A and
N1A—H11Aꢀ ꢀ ꢀO12 = 117 (3)ꢃ], which is probably an artefact
of the overall cyclic hydrogen-bonding motif. This association
[graph set R34(17)] involves piperidinium–carboxylate N—
Hꢀ ꢀ ꢀO, amide–carboxylate N—Hꢀ ꢀ ꢀO and amide–amide N—
Hꢀ ꢀ ꢀO hydrogen bonds from two INIPA cations and one
DCPA anion, and is closed by the intramolecular carboxy–
carboxylate O—Hꢀ ꢀ ꢀO hydrogen bond (Fig. 6). A second
cyclic association [graph set R33(13)] involves one piperidinium
and two amide–carboxyl hydrogen bonds (Table 2), and the
two motifs link the DCPA anions peripherally into head-to-
head N—Hꢀ ꢀ ꢀO amide-linked cation chain substructures. This
results in one-dimensional ribbon structures which extend
along the b cell direction. In the crystal structures of DCPA
salts with Lewis bases, this low dimensionality in the
hydrogen-bonded structures is commonly associated with the
‘planar’ DCPA monoanion, which features the cyclic intra-
molecular carboxy–carboxylate O—Hꢀ ꢀ ꢀO hydrogen-bonding
association [graph set S(7); Smith & Wermuth, 2010a]. The
molecular cation C—Hꢀ ꢀ ꢀO associations [C2Aꢀ ꢀ ꢀO52ii
=
ii
ꢃ
˚
3.308 (2) A and C2A—H22Aꢀ ꢀ ꢀO52 = 151 ] (see Table 3 for
symmetry code). The anion in (III) is essentially planar, but
with the carboxylate group rotated slightly out of the plane of
the benzene ring [torsion angle C2—C1—C11—O11 =
ꢁ161.47 (16)ꢃ, cf. C2—C3—C31—O32 = 172.04 (15)ꢃ (the
carboxylic acid group) and C4—C5—N51—O52
175.06 (17)ꢃ (the nitro group)].
With the terephthalate salt, (IV), one of the piperidinium–
=
carboxylate N—Hꢀ ꢀ ꢀO hydrogen bonds seen in Fig. 4
C6H13N2O+ꢀC8H4NO6 and three analogues o261
ꢁ
ꢂ
Smith and Wermuth
Acta Cryst. (2011). C67, o259–o264

organic compounds
Table 1
Hydrogen-bond geometry (A, ) for (I).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1A—H11Aꢀ ꢀ ꢀO11i
N1A—H12Aꢀ ꢀ ꢀO21
N41A—H42Aꢀ ꢀ ꢀO41Aii
N41A—H43Aꢀ ꢀ ꢀO42iii
O22—H22ꢀ ꢀ ꢀO12iv
0.98 (3)
0.93 (3)
0.92 (3)
0.83 (3)
0.99
1.77 (3)
1.92 (3)
1.99 (3)
2.40 (3)
1.47
2.729 (2)
2.803 (2)
2.907 (3)
3.200 (3)
2.4562 (19)
163 (2)
158 (2)
176 (2)
161 (3)
179
3
2
3
1
Symmetry codes: (i) x ꢁ 1; y; z; (ii) ꢁx þ 1; ꢁy þ 2; ꢁz þ 1; (iii) x ꢁ ; ꢁy þ ; z ꢁ ; (iv)
2
2
1
2
1
2
3
2
ꢁx þ ; y þ ; ꢁz þ .
Compound (I)
Crystal data
C6H13N2O+ꢀC8H4NO6
ꢁ
3
˚
V = 1519.6 (2) A
Z = 4
Mr = 339.31
Monoclinic, P21=n
Figure 8
Mo Kꢁ radiation
ꢂ = 0.12 mmꢁ1
T = 200 K
0.40 ꢄ 0.40 ꢄ 0.12 mm
The three-dimensional hydrogen-bonded framework structure of (IV), in
a perspective view of the unit cell, showing hydrogen-bonding associa-
tions as dashed lines. Graph sets for cyclic hydrogen-bonding associations
are also indicated. Non-interactive H atoms have been omitted. [For
symmetry code (i), see Fig. 1; for other codes, see Table 4.]
˚
a = 5.8637 (5) A
˚
b = 11.2707 (8) A
˚
c = 23.0268 (19) A
ꢀ = 93.082 (8)ꢃ
Data collection
Oxford Gemini-S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2009)
10364 measured reflections
2989 independent reflections
2375 reflections with I > 2ꢃ(I)
Rint = 0.023
is accompanied by an asymmetric three-centre piperidinium–
carboxylate N—Hꢀ ꢀ ꢀO,O0 interaction [graph set R21(4)] with
the centrosymmetric terephthalate dianion (Fig. 8). This
second association links two INIPA cations to the terephtha-
late dianion, which is extended longitudinally in the approx-
imate b cell direction through centrosymmetric cyclic water-
bridged amide–amide associations [graph set R44(12)]. The
water molecules also act as acceptors in bridging these chains
laterally through amide N—Hꢀ ꢀ ꢀO hydrogen bonds (Table 4),
forming centrosymmetric cyclic R24(8) associations. The lateral
piperidinium–carboxylate N—Hꢀ ꢀ ꢀO hydrogen bonds shown
in Fig. 4, together with the water–carboxylate O—Hꢀ ꢀ ꢀO
associations [graph sets R34(10), R33(18) and R46(22)], complete
a three-dimensional framework structure. The centrosym-
metric terephthalate dianion deviates slightly from planarity
[torsion angle C2—C1—C11—O11 = 169.25 (12)ꢃ].
The structures reported here further demonstrate the utility
of the isonipecotamide cation as a synthon for the generation
of stable hydrogen-bonded structures. An additional example
of INIPA cation–anion association is also shown in the
asymmetric three-centre piperidinium–carboxylate N—Hꢀ ꢀ ꢀ
O,O0 interaction in the first-reported structure of a 2:1 iso-
nipecotamide carboxylate salt.
Tmin = 0.915, Tmax = 0.980
Refinement
R[F2 > 2ꢃ(F2)] = 0.046
wR(F2) = 0.114
S = 1.05
2989 reflections
233 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢁ3
˚
Áꢄmax = 0.35 e A
ꢁ3
˚
Áꢄmin = ꢁ0.26 e A
Compound (II)
Crystal data
C6H13N2O+ꢀC8H3Cl2O4
ꢁ
3
˚
V = 1570.15 (15) A
Z = 4
Mr = 363.19
Monoclinic, P21=n
Mo Kꢁ radiation
ꢂ = 0.44 mmꢁ1
T = 200 K
0.30 ꢄ 0.25 ꢄ 0.20 mm
˚
a = 6.6897 (4) A
˚
b = 9.7392 (5) A
˚
c = 24.1222 (13) A
ꢀ = 92.479 (4)ꢃ
Data collection
Oxford Gemini S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2009)
19231 measured reflections
3084 independent reflections
2777 reflections with I > 2ꢃ(I)
Rint = 0.028
Tmin = 0.908, Tmax = 0.980
Experimental
The title compounds were synthesized by heating together under
reflux for 10 min piperidine-4-carboxamide (isonipecotamide,
1 mmol) with either 4-nitrophthalic acid (1 mmol) for (I), 4,5-di-
chlorophthalic acid (1 mmol) for (II), 5-nitroisophthalic acid
(1 mmol) for (III) or terephthalic acid (1 mmol) for (IV), in either
methanol (50 ml) for (III), methanol–water (80%, 50 ml) for (I) and
(IV), or ethanol–water (50%, 50 ml) for (II). After concentration to
ca 30 ml, partial room-temperature evaporation of the hot-filtered
solutions gave colourless plates of (I) and (III), blocks of (II) or
prisms of (IV).
Table 2
Hydrogen-bond geometry (A, ) for (II).
ꢃ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1A—H11Aꢀ ꢀ ꢀO11
N1A—H12Aꢀ ꢀ ꢀO22i
N41A—H41Aꢀ ꢀ ꢀO21ii
N41A—H42Aꢀ ꢀ ꢀO41Aiii
O12—H12ꢀ ꢀ ꢀO21
0.92 (4)
0.87 (4)
0.82 (4)
0.93 (4)
1.00
1.90 (4)
1.96 (4)
2.48 (4)
2.19 (4)
1.40
2.810 (3)
2.753 (3)
3.158 (3)
3.086 (4)
2.393 (3)
170 (3)
152 (3)
142 (4)
163 (3)
180
3
2
1
2
1
2
3
2
1
2
1
2
Symmetry codes: (i) x; y ꢁ 1; z; (ii) ꢁx þ ; y ꢁ ; ꢁz þ ; (iii) ꢁx þ ; y þ ; ꢁz þ .
o262 Smith and Wermuth C6H13N2O+ꢀC8H4NO6 and three analogues
Acta Cryst. (2011). C67, o259–o264
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organic compounds
Table 3
Hydrogen-bond geometry (A, ) for (III).
Table 4
Hydrogen-bond geometry (A, ) for (IV).
ꢃ
ꢃ
˚
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1A—H11Aꢀ ꢀ ꢀO31i
N1A—H12Aꢀ ꢀ ꢀO11
N1A—H12Aꢀ ꢀ ꢀO12
N41A—H41Aꢀ ꢀ ꢀO11ii
N41A—H42Aꢀ ꢀ ꢀO41Aiii
O32—H32ꢀ ꢀ ꢀO12iv
0.93 (2)
0.98 (2)
0.98 (2)
0.822 (19)
0.940 (19)
0.93 (2)
2.06 (2)
1.87 (2)
2.45 (2)
2.298 (19)
1.996 (19)
1.63 (2)
2.9236 (18)
2.8229 (16)
3.0366 (19)
3.0669 (19)
2.9321 (18)
2.5336 (17)
153.6 (17)
164 (2)
118.1 (17)
155.9 (17)
174.1 (16)
164 (3)
N1A—H11Aꢀ ꢀ ꢀO11
N1A—H12Aꢀ ꢀ ꢀO11i
N1A—H12Aꢀ ꢀ ꢀO12i
N41A—H41Aꢀ ꢀ ꢀO1Wii
N41A—H42Aꢀ ꢀ ꢀO1W
O1W—H11Wꢀ ꢀ ꢀO41Aiii
O1W—H12Wꢀ ꢀ ꢀO12iv
0.966 (17)
0.979 (17)
0.979 (17)
0.927 (17)
0.95 (2)
1.856 (18)
1.847 (17)
2.367 (19)
2.045 (17)
2.111 (19)
1.892 (18)
1.833 (19)
2.7937 (16)
2.8030 (15)
3.1200 (16)
2.9181 (16)
2.9870 (17)
2.7410 (15)
2.7632 (15)
162.9 (14)
164.7 (17)
133.3 (14)
156.5 (17)
153.2 (14)
168.7 (17)
175.6 (19)
0.861 (18)
0.932 (19)
1
3
2
1
1
Symmetry codes: (i) ꢁx þ 2; y þ ; ꢁz þ ; (ii) ꢁx þ 1; y þ ; ꢁz þ ; (iii) ꢁx þ 1,
2
2
2
1
3
2
ꢁy þ 2; ꢁz þ 1; (iv) ꢁx þ 2; y ꢁ ; ꢁz þ .
Symmetry codes: (i) ꢁx þ 1; ꢁy þ 2; ꢁz; (ii) ꢁx þ 1; ꢁy; ꢁz þ 1; (iii) x þ 1; y; z; (iv)
2
ꢁx þ 1; ꢁy þ 1; ꢁz.
Refinement
R[F2 > 2ꢃ(F2)] = 0.046
wR(F2) = 0.113
S = 1.30
3084 reflections
224 parameters
H atoms treated by a mixture of
independent and constrained
refinement
Refinement
R[F2 > 2ꢃ(F2)] = 0.034
wR(F2) = 0.093
S = 1.05
2177 reflections
169 parameters
H atoms treated by a mixture of
independent and constrained
refinement
ꢁ3
˚
Áꢄmax = 0.37 e A
ꢁ3
˚
Áꢄmin = ꢁ0.29 e A
ꢁ3
˚
Áꢄmax = 0.23 e A
ꢁ3
˚
Áꢄmin = ꢁ0.16 e A
Compound (III)
H atoms involved in hydrogen-bonding interactions were located
by difference methods and, with the exception of the carboxylic acid
H atoms in (I) and (II), which were set to ride on their parent atoms
with Uiso(H) = 1.2Ueq(O) in the final cycles of refinement, their
positional and isotropic displacement parameters were refined. Other
H atoms were included in the refinements at calculated positions
Crystal data
C6H13N2O+ꢀC8H4NO6
ꢁ
3
˚
V = 1502.27 (11) A
Z = 4
Mo Kꢁ radiation
ꢂ = 0.12 mmꢁ1
T = 200 K
Mr = 339.31
Monoclinic, P21=c
˚
a = 9.4117 (4) A
˚
b = 14.3552 (5) A
˚
c = 11.4490 (5) A
0.45 ꢄ 0.40 ꢄ 0.18 mm
˚
˚
ꢀ = 103.787 (4)ꢃ
(aliphatic C—H = 0.97 or 0.98 A, and aromatic C—H = 0.93 A) using
a riding-model approximation, with Uiso(H) = 1.2Ueq(C).
Data collection
For all four compounds, data collection: CrysAlis PRO (Oxford
Diffraction, 2009); cell refinement: CrysAlis PRO; data reduction:
CrysAlis PRO. Program(s) used to solve structure: SIR92 (Altomare
et al., 1994) for (I), (II) and (III); SHELXS97 (Sheldrick, 2008) for
(IV). For all compounds, program(s) used to refine structure:
SHELXL97 (Sheldrick, 2008) within WinGX (Farrugia, 1999);
molecular graphics: PLATON (Spek, 2009); software used to prepare
material for publication: PLATON.
Oxford Gemini-S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2009)
9866 measured reflections
2940 independent reflections
2284 reflections with I > 2sI)
Rint = 0.025
Tmin = 0.980, Tmax = 0.990
Refinement
R[F2 > 2ꢃ(F2)] = 0.037
wR(F2) = 0.106
S = 1.01
2940 reflections
237 parameters
H atoms treated by a mixture of
independent and constrained
refinement
The authors acknowledge financial support from the
Australian Research Council, the Faculty of Science and
Technology, Queensland University of Technology, and the
School of Biomolecular and Physical Sciences, Griffith
University.
ꢁ3
˚
Áꢄmax = 0.35 e A
ꢁ3
˚
Áꢄmin = ꢁ0.24 e A
Compound (IV)
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SU3064). Services for accessing these data are
described at the back of the journal.
Crystal data
+
2C6H13N2O8 ꢀC8H4O42ꢁꢀ2H2O
ꢅ = 80.885 (7)ꢃ
V = 556.89 (9) A
Z = 1
Mo Kꢁ radiation
ꢂ = 0.11 mmꢁ1
T = 200 K
3
˚
Mr = 458.51
Triclinic, P1
a = 6.5099 (5) A
˚
˚
References
b = 7.7777 (6) A
c = 11.6865 (12) A
Allen, F. H., Raithby, P. R., Shields, P. & Taylor, R. (1998). Chem. Commun. pp.
1043–1044.
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.
˚
ꢁ = 76.429 (8)ꢃ
ꢀ = 76.968 (7)ꢃ
0.50 ꢄ 0.15 ꢄ 0.08 mm
Data collection
Oxford Gemini-S CCD area-
detector diffractometer
Absorption correction: multi-scan
(CrysAlis PRO; Oxford
Diffraction, 2009)
6562 measured reflections
2177 independent reflections
1746 reflections with I > 2ꢃ(I)
Rint = 0.024
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Glidewell, C., Low, J. N., Skakle, J. M. S. & Wardell, J. L. (2005). Acta Cryst.
C61, o276–o280.
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton,
Oxfordshire, England.
Tmin = 0.965, Tmax = 0.990
C6H13N2O+ꢀC8H4NO6 and three analogues o263
ꢁ
ꢂ
Smith and Wermuth
Acta Cryst. (2011). C67, o259–o264

organic compounds
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Smith, G. & Wermuth, U. D. (2010f). Acta Cryst. E66, o3260.
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Smith, G. & Wermuth, U. D. (2011b). Acta Cryst. E67, o566.
Smith, G. & Wermuth, U. D. (2011c). Unpublished results.
Smith, G., Wermuth, U. D. & Young, D. J. (2010). Acta Cryst. E66, o3160–o3161.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
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Smith, G. & Wermuth, U. D. (2010c). Acta Cryst. C66, o609–o613.
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o264 Smith and Wermuth C6H13N2O+ꢀC8H4NO6 and three analogues
Acta Cryst. (2011). C67, o259–o264
ꢁ
ꢂ