Charge-assisted hydrogen-bonded supra-molecular networks in acetoguanaminium hydrogen phthalate, acetoguanaminium hydrogen maleate and acetoguanaminium 3-hydroxy-picolinate monohydrate

Article abstract of DOI:10.1107/S0108270110014150

In 2,4-diamino-6-methyl-1,3,5-triazin-1-ium (acetoguan-amin-ium) hydrogen phthalate, C₄H₈N₅⁺·C ₈H₅₄ ^-, (I), aceto-guan-aminium hydrogen maleate, C₄H₈N₅ ⁺· C₄H₃O₄ ^-, (II), and acetoguanaminium 3-hydroxy-picolinate monohydrate, C₄H₈N₅ ⁺·C₆H₄NO₃ ^-·H₂O, (III), the acetoguanaminium cations inter-act with the carboxyl-ate groups of the corresponding anions via a pair of nearly parallel N - H...O hydrogen bonds, forming R₂ ²(8) ring motifs. In (II) and (III), N - H...N base-pairing is observed, while there is none in (I). In (II), a series of fused R ₃²(8), R₂²(8) and R₃ ²(8) hydrogen-bonded rings plus fused R₂²(8), R₆²(12) and R₂²(8) ring motifs occur alternately, aggregating into a supra-molecular ladder-like arrangement. In (III), R₂²(8) motifs occur on either side of a further ring formed by pairs of N - H...O hydrogen bonds, forming an array of three fused hydrogen-bonded rings. In (I) and (II), the anions form a typical intra-molecular O - H...O hydrogen bond with graph set S(7), whereas in (III) an intra-molecular hydrogen bond with graph set S(6) is formed.

Full text of DOI:10.1107/S0108270110014150

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
inorganic complexes of triazine form well defined noncovalent
supramolecular architectures via multiple hydrogen bonds,
because of the presence of arrays of hydrogen-bonding sites
(MacDonald & Whitesides, 1994). 2,4-Diamino-6-methyl-
ISSN 0108-2701
1,3,5-triazine (acetoguanamine) is used as an intermediate for
pharmaceuticals, and as a modifier and flexibilizer of formal-
dehyde resins (Sebenik et al., 1989; Tashiro & Oiwa, 1981).
Hydrogen-bonded carboxylic acid adducts with 2-amino
Charge-assisted hydrogen-bonded
supramolecular networks in aceto-
guanaminium hydrogen phthalate,
acetoguanaminium hydrogen maleate
and acetoguanaminium 3-hydroxy-
picolinate monohydrate
heterocyclic ring systems frequently form a graph-set motif
2
(Etter, 1990; Bernstein et al., 1995) of R (8) (Lynch & Jones,
2004).
2
a
a
Kaliyaperumal Thanigaimani, Periasamy Devi,
a
b
Packianathan Thomas Muthiah, * Daniel E. Lynch and
c
Ray J. Butcher
a
School of Chemistry, Bharathidasan University, Tiruchirappalli 620 024,
b
Tamilnadu, India, Faculty of Health and Life Sciences, Coventry University, Priory
Street, Coventry CV1 5FB, England, and Exilica Limited, The Technocentre, Puma
c
Way, Coventry CV1 2TT, England, and Department of Chemistry, Howard
University, Washington, DC 20059, USA
Correspondence e-mail: tommtrichy@yahoo.co.in
Received 9 February 2010
Accepted 16 April 2010
Online 5 June 2010
In 2,4-diamino-6-methyl-1,3,5-triazin-1-ium (acetoguanamin-
+
ꢁ
ium) hydrogen phthalate, C H N ꢀC H O , (I), acetoguan-
4
8
5
8
5
4
+
ꢁ
4
aminium hydrogen maleate, C H N ꢀC H O , (II), and
4
8
5
4
3
acetoguanaminium 3-hydroxypicolinate monohydrate,
The crystal structures of 2,4-diamino-6-methyl-1,3,5-triazine
Aoki et al., 1994), 2,4-diamino-6-methyl-1,3,5-triazin-1-ium
+
5
ꢁ
C H N ꢀC H NO ꢀH O, (III), the acetoguanaminium
4
8
6
4
3
2
(
cations interact with the carboxylate groups of the corre-
sponding anions via a pair of nearly parallel N—Hꢀ ꢀ ꢀO
trifluoroacetate (Perp e´ tuo & Janczak, 2007), 4-(dimethyl-
amino)benzaldehyde and 6-phenyl-1,3,5-triazine-2,4-diamine
2
2
hydrogen bonds, forming R (8) ring motifs. In (II) and (III),
N—Hꢀ ꢀ ꢀN base-pairing is observed, while there is none in (I).
(Habibi et al., 2007), acetoguanaminium chloride–acetoguan-
amine (Portalone & Colapietro, 2007), acetoguanaminium
N,N-dimethylformamide solvate (Portalone, 2008), 2,4-di-
amino-6-methyl-1,3,5-triazine methanol solvate (Kaczmarek
2
3
2
2
2
3
In (II), a series of fused R (8), R (8) and R (8) hydrogen-
2
2
6
2
2
bonded rings plus fused R (8), R (12) and R (8) ring motifs
2
occur alternately, aggregating into a supramolecular ladder-
2
like arrangement. In (III), R (8) motifs occur on either side of
2
a further ring formed by pairs of N—Hꢀ ꢀ ꢀO hydrogen bonds,
forming an array of three fused hydrogen-bonded rings. In (I)
and (II), the anions form a typical intramolecular O—Hꢀ ꢀ ꢀO
hydrogen bond with graph set S(7), whereas in (III) an
intramolecular hydrogen bond with graph set S(6) is formed.
Comment
Aminopyrimidinium and aminotriazinium ions and their
derivatives easily form acid–base complexes with carboxylate
+
ꢁ
anions, which are linked by strong N —Hꢀ ꢀ ꢀO (ꢂ) charge-
assisted hydrogen bonds (Gilli et al., 2000; Ferretti et al., 2004).
Triazine derivatives show antitumour activity, as well as a
broad range of biological activities, such as anti-angiogenesis
and antimicrobial effects (Bork et al., 2003). The organic and
Figure 1
The asymmetric unit of (I), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii. Dashed lines indicate
hydrogen bonds.
o324 # 2010 International Union of Crystallography
doi:10.1107/S0108270110014150
Acta Cryst. (2010). C66, o324–o328

organic compounds
Figure 2
The asymmetric unit of (II), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii. Dashed lines indicate
hydrogen bonds.
Figure 4
Hydrogen-bonding patterns in (I). Dashed lines indicate hydrogen bonds.
H atoms not involved in hydrogen bonding have been omitted.
1
1
2
[
Symmetry codes: (i) ꢁx + 1, ꢁy + 1, ꢁz; (ii) ꢁx + 1, y + , ꢁz + ; (iii)
2
3
2
1
2
x, ꢁy + , z + .]
Figure 3
The asymmetric unit of (III), showing the atom-numbering scheme.
Displacement ellipsoids are drawn at the 50% probability level and H
atoms are shown as small spheres of arbitrary radii. Dashed lines indicate
hydrogen bonds.
et al., 2008) and 2,4-diamino-6-methyl-1,3,5-triazine ethanol
solvate (Xiao, 2008) have been reported. Salts and cocrystals
involving 2,4-diamino-6-methyl-1,3,5-triazine and various
aliphatic dicarboxylic acids have been reported (Delori et al.,
Figure 5
The DADA array of hydrogen bonds in (II), leading to a supramolecular
ladder. Dashed lines indicate hydrogen bonds. H atoms not involved in
hydrogen bonding have been omitted. [Symmetry codes: (i) ꢁx, ꢁy + 1,
2
008). In this context, we present the synthesis and crystal
structures of three organic salts, namely acetoguanaminium
hydrogen phthalate, (I), acetoguanaminium hydrogen
maleate, (II), and acetoguanaminium 3-hydroxypicolinate
monohydrate, (III).
Views of compounds (I)–(III) are shown in Figs. 1–3. In (I)
and (II), the asymmetric unit contains one acetoguanaminium
cation and a hydrogen phthalate/hydrogen maleate anion. In
ꢁ
z; (ii) ꢁx + 1, ꢁy, ꢁz + 1; (iii) x + 1, y ꢁ 1, z + 1; (iv) ꢁx, ꢁy + 2, ꢁz + 1.]
ii
H4Aꢀ ꢀ ꢀN3 in (II) [symmetry code: (ii) ꢁx + 1, ꢁy, ꢁz + 1]
iv
and N4—H4Bꢀ ꢀ ꢀN5 in (III) [symmetry code: (iv) ꢁx, ꢁy + 1,
ꢁz].
2
2
(III), the asymmetric unit contains one acetoguanaminium
cation, a 3-hydroxypicolinate anion and a water molecule. As
In (I) and (II), inversion-related R (8) ring motifs (triaz-
4
inium–carboxylate) lie on either side of an R (12) motif
6
expected for all three structures, the acetoguanaminium
(
carboxylate groups of the anions (hydrogen phthalate,
hydrogen maleate and 3-hydroxypicolinate, respectively)
interact with the protonated triazinium moiety of the aceto-
formed by N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀO (intramolecular)
+
AceguH ) moieties are protonated at N1. In (I)–(III), the
hydrogen bonds (Tables 1 and 2). The graph-set notation of
2
4
2
the ring system is R (8), R (12) and R (8) (Fig. 4). Similar
6
2 2
types of interactions were also observed in trimethoprim
hydrogen phthalate (Muthiah et al., 2006). One of the H atoms
of the 2-amino group forms a bifurcated hydrogen bond with
guanaminium cations through a pair of linear N—Hꢀ ꢀ ꢀO
2
2
hydrogen bonds to form an eight-membered R (8) ring motif
the carboxyl O atoms of the hydrogen phthalate and hydrogen
2
(Figs. 1–3). This is one of the 24 most frequently observed
bimolecular cyclic hydrogen-bonded motifs in organic crystal
structures (Allen et al., 1998). In (II) and (III), the triazine
+
moieties of the AceguH cations are centrosymmetrically
maleate anions, represented by graph-set R (4). In the
1
hydrogen phthalate anion of (I), there is a very strong intra-
ꢁ
molecular [O—Hꢀ ꢀ ꢀO] hydrogen bond, graph-set notation
˚
S(7) [O2ꢀ ꢀ ꢀO3 = 2.393 (13) A], which is a result of the nega-
paired through N—Hꢀ ꢀ ꢀN hydrogen bonds, viz. N4—
tive charge-assisted effect described by Gilli et al. (1994).
+
4ꢁ
ꢃ
Acta Cryst. (2010). C66, o324–o328
Thanigaimani et al.
C H N
4 8 5
ꢀC H O
8 5
and two analogues o325

organic compounds
2
2
ment (Fig. 5). Adjacent ladders are crosslinked by R (8) ring
motifs of the inversely paired hydrogen maleate anions via
iv
C9—H9ꢀ ꢀ ꢀO1 hydrogen bonds [symmetry code: (iv) ꢁx,
ꢁ
y + 2, ꢁz + 1]. The crosslinked motifs generate a large 26-
4
6
membered [R (26)] ring motif (Fig. 5). The hydrogen maleate
anion posseses nearly planar geometry and displays a strong
intramolecular O3—H3ꢀ ꢀ ꢀO2 hydrogen bond [Table 2; graph-
set notation S(7)] (Lah & Leban, 2003).
2
ii
In (III), the R (8) motifs are linked by N2—H2Aꢀ ꢀ ꢀO1
2
hydrogen bonds (symmetry code as in Table 3), forming a ring
1
1
spanning the centre of symmetry at (1, , ) to produce a
DDAA array of four hydrogen bonds. This set of fused rings
2
2
2
2
2
4
can be represented by the graph-set notations R (8), R (8) and
2
R (8) (Fig. 6). This type of motif has been reported in the
2
crystal structures of trimethoprim hydrogen glutarate (Robert
et al., 2001), trimethoprim formate (Umadevi et al., 2002) and
pyrimethamine 3,5-dinitrobenzoate (Subashini et al., 2007).
The 2-amino group at N2 forms a bifurcated hydrogen bond
Figure 6
The DDAA hydrogen-bonding pattern in (III). Dashed lines indicate
hydrogen bonds. H atoms not involved in hydrogen bonding have been
3
1
ii
ii
omitted. [Symmetry codes: (i) x, ꢁy + , z ꢁ ; (ii) ꢁx + 2, ꢁy + 1, ꢁz + 1;
2
2
(Table 3) with carboxyl atom O1 and atom N6 of a 3-hy-
2
(iii) ꢁx + 1, ꢁy + 1, ꢁz; (iv) ꢁx, ꢁy + 1, ꢁz.]
droxypicolinate anion [graph-set R (5)]. These types of
1
interactions are extended along the a axis to form a supra-
molecular ribbon. The ribbons are linked by the bridging
water molecule into a two-dimensional net in the (102) plane.
These two-dimensional nets are further linked into the three-
dimensional structure by the interactions shown in Fig. 7. An
intramolecular hydrogen bond between the hydroxy and
carboxylate groups of the 3-hydroxypicolinate anion forms a
six-membered hydrogen-bonded ring [S(6); Fig. 3].
In (I) and (III), ꢀ–ꢀ stacking interactions between the
aromatic rings are observed. In (I), there are two distinct
stacking interactions. Using the phthalate ring of the base
asymmetric unit as reference, this ring has an interaction with
the cation located at (1 ꢁ x, 1 ꢁ y, 1 ꢁ z), with a dihedral angle
ꢄ
˚
of 1.76 (6) , a centroid-to-centroid distance of 3.6545 (8) A, a
˚
perpendicular distance of 3.314 (6) A and a slip angle of
ꢄ
2
4.94 . The second interaction, which has the same dihedral
angle, is with the cation located at (2 ꢁ x, 1 ꢁ y, 1 ꢁ z), with a
˚
perpendicular separation of 3.367 (5) A, a centroid-to-
Figure 7
ꢄ
The supramolecular chain of 3-hydroxypicolinate anions and water
molecules in (III). Dashed lines indicate hydrogen bonds. H atoms not
involved in hydrogen bonding have been omitted. [Symmetry code: (i) x,
˚
centroid distance of 3.5929 (8) A and a slip angle of 20.45 . A
stack is thus formed parallel to the a axis. In (III), a ꢀ–ꢀ
interaction is observed between two 2,4-diamino-6-methyl-
3
2
1
2
ꢁ
y + , z ꢁ .]
1,3,5-triazinium cations, with a centroid-to-centroid distance
of 3.5906 (12) A, an interplanar distance of 3.2875 (6) A, a
˚
˚
˚
ꢄ
In (II), the 2- and 4-amino groups of the paired triazinium
ring offset of 1.444 A and a slip angle of 23.71 . These are in
agreement with typical aromatic stacking values (Hunter,
1994).
cations further interact with one of the carboxyl O atoms (O4)
of the adjacent anions, leading to a complementary DADA
array (D is a hydrogen-bond donor and A is a hydrogen-bond
acceptor) of four hydrogen bonds. This type of interaction has
already been reported in trimethoprim hydrogen maleate
In conclusion, in all three title crystal structures, the
acetoguanaminium cation interacts with the carboxylate O
atoms via N—Hꢀ ꢀ ꢀO hydrogen bonds to form the frequently
2
2
(
(
Prabakaran et al., 2001), trimethoprim trifluoroacetate
Francis et al., 2002), pyrimethaminium formate (Stanley et al.,
observed hydrogen-bonded eight-membered R (8) ring motif.
In (II) and (III), N—Hꢀ ꢀ ꢀN base pairing is observed, while
2
2
2002), trimethoprim tetrafluroborate (Hemamalini et al., 2005)
there is none in (I). In (II), the DADA [fused R (8), R (8) and
3 2
2
2
2
2
and trimethoprim hydrogen phthalate (Muthiah et al., 2006).
The DADA hydrogen-bonding motif can be represented in
R (8) rings] array and R (8), R (12) and R (8) ring motifs
6
3 2 2
occur alternately, aggregating into a supramolecular ladder-
2
2
2
2
2
3
the form of fused R (8), R (8) and R (8) rings. The DADA
2
like arrangement. In (III), the R (8) motifs lie on either side of
2
3
4
6
2
2
arrays and R (8), R (12) and R (8) ring motifs occur alter-
2
a ring formed by N—Hꢀ ꢀ ꢀO hydrogen bonds, forming fused
rings through a DDAA array of four hydrogen bonds.
nately, aggregating into a supramolecular ladder-like arrange-
+
5
4ꢁ
and two analogues
ꢃ
o326 Thanigaimani et al.
4 8
C H N
ꢀC H O
8 5
Acta Cryst. (2010). C66, o324–o328

organic compounds
Experimental
Table 3
Hydrogen-bond geometry (A, ) for (III).
˚
ꢄ
Compounds (I)–(III) were prepared by mixing hot methanolic solu-
tions (20 ml) of 2,4-diamino-6-methyl-1,3,5-triazine (acetoguanam-
ine) (31 mg, Aldrich) with hot aqueous solutions (20 ml) of the
corresponding acids [phthalic acid (41 mg, Loba Chemie), maleic acid
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
i
O1W—H1Wꢀ ꢀ ꢀO3
O1W—H2Wꢀ ꢀ ꢀO2
N1—H1ꢀ ꢀ ꢀO2
0.796 (18)
0.82 (2)
0.86
0.86
0.86
0.86
0.82
0.86
0.86
2.112 (18)
2.07 (2)
2.04
2.44
2.11
1.94
1.80
2.06
2.14
2.875 (2)
2.880 (3)
2.890 (2)
2.912 (2)
2.965 (2)
2.787 (2)
2.526 (2)
2.898 (2)
2.994 (2)
161 (3)
166 (3)
169
115
172
169
147
164
175
(29 mg, Loba Chemie) or 3-hydroxypicolinic acid (35 mg, Loba
ii
Chemie), respectively] in a 1:1 molar ratio, and warming the mixtures
for 30 min over a water bath. Each solution was cooled slowly and
kept at room temperature. After a few days, colourless crystals of the
title compounds were obtained.
N2—H2Aꢀ ꢀ ꢀO1
ii
N2—H2Aꢀ ꢀ ꢀN6
N2—H2Bꢀ ꢀ ꢀO1
O3—H3ꢀ ꢀ ꢀO2
iii
N4—H4Aꢀ ꢀ ꢀO1W
iv
N4—H4Bꢀ ꢀ ꢀN5
3
1
Symmetry codes: (i) x; ꢁy þ ; z ꢁ ; (ii) ꢁx þ 2; ꢁy þ 1; ꢁz þ 1; (iii) ꢁx þ 1; ꢁy þ 1,
2
2
Compound (I)
ꢁz; (iv) ꢁx; ꢁy þ 1; ꢁz.
Crystal data
+
4ꢁ
˚
V = 1286.53 (5) A
3
C
4
H
8
N
5
ꢀC
8
H
5
O
Compound (II)
M
r
= 291.27
Z = 4
Mo Kꢂ radiation
Monoclinic, P2 =c
1
ꢁ1
Crystal data
+
˚
a = 7.0743 (2) A
ꢃ = 0.12 mm
T = 120 K
˚
b = 23.4468 (5) A
ꢁ
4
ꢄ
ꢆ = 91.032 (3)
V = 536.58 (4) A
Z = 2
C H N ꢀC H O
4
8
5
4
3
˚
ꢄ
˚
3
c = 8.1134 (1) A
= 107.063 (1)
0.54 ꢅ 0.30 ꢅ 0.25 mm
M = 241.22
r
Triclinic, P1
a = 7.1921 (3) A
b = 8.2359 (3) A
˚
c = 9.4775 (4) A
ꢁ
˚
˚
Mo Kꢂ radiation
ꢁ1
ꢃ = 0.12 mm
T = 293 K
Data collection
ꢄ
Bruker–Nonius KappaCCD area-
detector diffractometer
2918 independent reflections
2586 reflections with I > 2ꢄ(I)
ꢂ = 98.287 (2)
ꢁ = 104.656 (2)
0.22 ꢅ 0.18 ꢅ 0.16 mm
ꢄ
14262 measured reflections
Rint = 0.032
Data collection
Refinement
2
Bruker Kappa APEXII CCD area-
detector diffractometer
Absorption correction: multi-scan
(Blessing, 1995)
13516 measured reflections
3779 independent reflections
2607 reflections with I > 2ꢄ(I)
2
R[F > 2ꢄ(F )] = 0.044
wR(F ) = 0.127
S = 1.12
H atoms treated by a mixture of
independent and constrained
refinement
2
Rint = 0.032
˚
ꢁ3
Tmin = 0.974, Tmax = 0.981
2
1
918 reflections
96 parameters
Áꢅmax = 0.39 e A
Áꢅmin = ꢁ0.54 e A˚
ꢁ3
Refinement
2
2
R[F > 2ꢄ(F )] = 0.050
wR(F ) = 0.168
156 parameters
H-atom parameters constrained
2
˚
ꢁ3
Áꢅmax = 0.37 e A
Table 1
Hydrogen-bond geometry (A, ) for (I).
S = 1.04
3779 reflections
ꢁ3
˚
ꢄ
Áꢅmin = ꢁ0.26 e A˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1—H1ꢀ ꢀ ꢀO1
N2—H2Aꢀ ꢀ ꢀO3
N2—H2Aꢀ ꢀ ꢀO4
N2—H2Bꢀ ꢀ ꢀO2
O3—H3ꢀ ꢀ ꢀO2
N4—H4Aꢀ ꢀ ꢀO4
0.86
0.86
0.86
0.86
1.12 (2)
0.86
0.86
1.80
2.59
2.08
2.06
1.28 (2)
2.10
2.14
2.6587 (14)
3.0541 (14)
2.9223 (14)
2.9074 (15)
2.3916 (13)
2.8748 (15)
2.9555 (15)
173
115
167
168
175 (2)
149
158
Compound (III)
i
i
Crystal data
+
ꢁꢀH
O
˚
V = 1299.9 (5) A
3
C
4
H
8
N
5
ꢀC
6
H NO
4
3
2
ii
M
r
= 282.27
Z = 4
Mo Kꢂ radiation
iii
N4—H4Bꢀ ꢀ ꢀN3
Monoclinic, P2 =c
1
˚
a = 7.0397 (16) A
ꢁ1
ꢃ = 0.11 mm
T = 296 K
1
2
1
2
3
2
Symmetry codes: (i) ꢁx þ 1; ꢁy þ 1; ꢁz; (ii) ꢁx þ 1; y þ ; ꢁz þ ; (iii) x; ꢁy þ ,
˚
b = 24.680 (5) A
1
z þ .
2
˚
c = 7.5047 (19) A
0.56 ꢅ 0.42 ꢅ 0.28 mm
ꢄ
ꢁ
= 94.462 (7)
Data collection
Table 2
Hydrogen-bond geometry (A, ) for (II).
˚
ꢄ
Bruker APEXII CCD area-detector
diffractometer
Absorption correction: multi-scan
10842 measured reflections
3233 independent reflections
2090 reflections with I > 2ꢄ(I)
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
(SADABS; Sheldrick, 1996)
Rint = 0.050
N1—H1ꢀ ꢀ ꢀO1
N2—H2Aꢀ ꢀ ꢀO3
N2—H2Aꢀ ꢀ ꢀO4
N2—H2Bꢀ ꢀ ꢀO2
O3—H3ꢀ ꢀ ꢀO2
0.86
0.86
0.86
0.86
0.82
0.86
0.86
0.93
1.88
2.59
2.09
1.93
1.62
2.21
2.19
2.58
2.7423 (15)
3.0650 (15)
2.9406 (16)
2.7852 (16)
2.4375 (15)
3.0660 (17)
2.8346 (17)
3.4143 (17)
179
116
169
177
176
173
132
150
Tmin = 0.939, Tmax = 0.969
i
i
Refinement
2
2
R[F > 2ꢄ(F )] = 0.051
wR(F ) = 0.154
S = 1.03
H atoms treated by a mixture of
independent and constrained
refinement
ii
N4—H4Aꢀ ꢀ ꢀN3
N4—H4Bꢀ ꢀ ꢀO4
2
iii
iv
C9—H9ꢀ ꢀ ꢀO1
˚
ꢁ3
Áꢅmax = 0.24 e A
3
233 reflections
91 parameters
Áꢅmin = ꢁ0.19 e A˚
ꢁ3
1
3 restraints
Symmetry codes: (i) ꢁx; ꢁy þ 1; ꢁz; (ii) ꢁx þ 1; ꢁy; ꢁz þ 1; (iii) x þ 1; y ꢁ 1; z þ 1;
(iv) ꢁx; ꢁy þ 2; ꢁz þ 1.
+
4ꢁ
ꢃ
Acta Cryst. (2010). C66, o324–o328
Thanigaimani et al.
C H N
4 8 5
ꢀC H O
8 5
and two analogues o327

organic compounds
In (I), atom H3 (on O3) was located in a difference Fourier map
and refined freely. The H atoms of the water molecule in (III) were
located in a difference Fourier map and their positional parameters
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Delori, A., Suresh, E. & Pedireddi, V. R. (2008). Chem. Eur. J. 14, 6967–
6977.
˚
were initially refined with O—H distance restraints of 0.82 A and
Etter, M. C. (1990). Acc. Chem. Res. 23, 120–126.
Ferretti, V., Bertolasi, V. & Pretto, L. (2004). New. J. Chem. 28, 646–
651.
˚
Hꢀ ꢀ ꢀH restraints of 1.297 A. The other H atoms in (I)–(III) were
positioned geometrically and refined using a riding model, with
˚
N—H = 0.86 A and C—H = 0.93–0.96 A in (I)–(III), and O—H =
˚
Francis, S., Muthiah, P. T., Bocelli, G. & Righi, L. (2002). Acta Cryst. E58,
o717–o719.
Gamez, P. & Reedijk, J. (2006). Eur. J. Inorg. Chem. pp. 29–42.
Gilli, P., Bertolasi, V., Ferretti, V. & Gilli, G. (1994). J. Am. Chem. Soc. 116,
909–915.
˚
.82 A in (II) and (III), and with Uiso(H) = 1.5Ueq(C,O) for OH
0
groups and all methyl groups, or 1.2Ueq(C,N) for other H atoms.
Data collection: COLLECT (Hooft, 1998) for (I); APEX2
Gilli, P., Bertolasi, V., Ferretti, V. & Gilli, G. (2000). J. Am. Chem. Soc. 122,
(
Bruker, 2004) for (II) and (III). Cell refinement: DENZO (Otwin-
owski & Minor, 1997) and COLLECT for (I); APEX2 and SAINT
Bruker, 2004) for (II); SAINT for (III). Data reduction: DENZO
1
0405–10417.
Habibi, M. H., Zendehdel, M., Barati, K., Harrington, R. W. & Clegg, W.
2007). Acta Cryst. C63, o474–o476.
(
(
and COLLECT for (I); SAINT and XPREP (Bruker, 2004) for (II);
SAINT for (III). For all three compounds, program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97 (Sheldrick, 2008); molecular graphics:
ORTEPII (Johnson, 1976) and PLATON (Spek, 2009); software used
to prepare material for publication: PLATON.
Hemamalini, M., Muthiah, P. T. & Lynch, D. E. (2005). Acta Cryst. E61, o4107–
o4109.
Hooft, R. (1998). COLLECT. Nonius BV, Delft, The Netherlands.
Hunter, C. A. (1994). Chem. Soc. Rev. 23, 101–109.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National
Laboratory, Tennessee. USA.
Kaczmarek, M., Radecka-Paryzek, W. & Kubicki, M. (2008). Acta Cryst. E64,
o269.
Lah, N. & Leban, I. (2003). Acta Cryst. C59, o537–o538.
Lynch, D. E. & Jones, G. D. (2004). Acta Cryst. B60, 748–754.
MacDonald, J. C. & Whitesides, G. M. (1994). Chem. Rev. 94, 2383–2420.
Muthiah, P. T., Francis, S., Rychlewska, U. & Warzajtis, B. (2006). Beilstein J.
Org. Chem. 2, article 8.
KT thanks the UGC (New Delhi) for a UGC–Rajiv Gandhi
Senior Research Fellowship [reference No. F.16-12/2000 (SA-
II)]. DL thanks the EPSRC National Crystallography Service
(
Southampton, England) for the X-ray data collection for
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.
Perp e´ tuo, G. J. & Janczak, J. (2007). Acta Cryst. C63, o271–o273.
Portalone, G. (2008). Acta Cryst. E64, o1685.
compound (I). The authors thank the SAIF at IIT, Madras (a
facility funded by the DST, New Delhi), for the X-ray data
collection for compound (II).
Portalone, G. & Colapietro, M. (2007). Acta Cryst. C63, o655–o658.
Prabakaran, P., Robert, J. J., Thomas Muthiah, P., Bocelli, G. & Righi, L.
(2001). Acta Cryst. C57, 459–461.
Robert, J. J., Raj, S. B. & Muthiah, P. T. (2001). Acta Cryst. E57, o1206–
o1208.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: FA3215). Services for accessing these data are
described at the back of the journal.
Sebenik, A., Osredkar, U. & Zigon, M. (1989). Polym. Bull. 22, 155–161.
Sheldrick, G. M. (1996). SADABS. University of Gottingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
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+
5
4ꢁ
and two analogues
ꢃ
o328 Thanigaimani et al.
4 8
C H N
ꢀC H O
8 5
Acta Cryst. (2010). C66, o324–o328