Hydrogen bonding network assembled with 2-amino-3-hydroxypyridium and isonicotinate-N-oxide

Article abstract of DOI:10.1007/s10870-007-9200-2

The crystal structure of the compound (C₅H₇N ₂O)?(C₆H₄NO₃)?H ₂O (1) consisting of 2-amino-3-hydroxypyridium, isoniconate-N-oxide and lattice water was characterized by single-crystal X-ray diffraction analysis: monoclinic, P2₁/c, a = 9.6905(8), b = 6.0040(4), c = 21.039(2) A, β = 101.062(8)°, V = 1201.34(18) A³, Z = 4. In 1, the deprotonated isoniconate-N-oxide, the protonated 2-amino-3-hydroxypyridium and the lattice water are linked by a series of classical hydrogen bonds to form 2-D layer. Then, these 2-D sheets assemble to a 3-D network via weak hydrogen bonds.

Full text of DOI:10.1007/s10870-007-9200-2

J Chem Crystallogr (2007) 37:523–526
DOI 10.1007/s10870-007-9200-2
ORIGINAL PAPER
Hydrogen Bonding Network Assembled with
2-Amino-3-hydroxypyridium and Isonicotinate-N-oxide
Rui-Xiang Hu Æ Ling Huang Æ Hong Liang Æ
Kai-Bei Yu
Received: 8 October 2006 / Accepted: 2 April 2007 / Published online: 6 June 2007
ꢀ
Springer Science+Business Media, LLC 2007
Abstract The crystal structure of the compound
C H N O)Á(C H NO )ÁH O (1) consisting of 2-amino-3-
ysis [2–6], and display many interesting hydrogen bond
properties [7–9].
(
5
7
2
6
4
3
2
hydroxypyridium, isoniconate-N-oxide and lattice water
was characterized by single-crystal X-ray diffraction
On our continuing program of design and synthesis of
the Schiff base system of pyridine N-oxide, we serendipi-
tously obtained the hydrate 2-amino-3-hydroxypyridium
isoniconate-N-oxide (1). In this paper, we have reported
the synthesis and the crystal structure of compound 1, as
well as discussed the ion hydrogen bonds.
analysis: monoclinic, P2 /c, a = 9.6905(8), b = 6.0040(4),
1
3
˚
˚
c = 21.039(2) A, b = 101.062(8)ꢁ, V = 1201.34(18) A ,
Z = 4. In 1, the deprotonated isoniconate-N-oxide, the
protonated 2-amino-3-hydroxypyridium and the lattice
water are linked by a series of classical hydrogen bonds to
form 2-D layer. Then, these 2-D sheets assemble to a 3-D
network via weak hydrogen bonds.
Experiment
Keywords Pyridine N-oxide Á Hydrogen bond Á
Crystal structure Á Supramolecular
Physical Measurements
All chemical regents and solvents were used as received.
Element analysis (C, H) was carried out with a Pekin–
Elmer 2400 II analyzer. Infrared spectrum (400–
Introduction
–
1
4
,000 cm ) was recorded from KBr pellets on a Nicolet
1
Weak intermolecular interactions, such as H-bonding, van
der Waals interactions, and p–p stacking etc., play very
important roles in the formation of supramolecular struc-
tures and natural sciences. Among these weak intermo-
lecular interactions, the hydrogen bonds have attracted
many chemists’ attention for its wide range of existence,
various appearance, and crucial effect on the properties of
many materials [1]. As useful ligands, Pyridine N-oxide
derivatives have been widely applied in asymmetry catal-
360 FT-IR spectrometer. The H NMR spectrum was
obtained with a Burker Avance 500 MHz spectrometer in
DMSO solution.
Synthesis of the Hydrate 2-amino-3-hydroxypyridium
isoniconate-N-oxide (1)
Compound 1 was prepared from 4-picoline according to
the literature [6, 8, 10] and the reaction is shown in
Scheme 1. The yellow block crystals of 1 were filtered off,
washed with distilled water, and dried at ambient temper-
R.-X. Hu (&) Á L. Huang Á H. Liang
–
1
ature, yield: 80%. FTIR (in cm ): 3410(s), 3109(m),
2460(m), 2363(m), 2028(w), 1989(w), 1683(s), 1644(m),
College of Chemistry and Chemical Engineering, Guangxi
Normal University, Guilin, Guangxi 541004, P.R. China
e-mail: hurx@mailbox.gxnu.edu.cn
1
1
1
613(m), 1573(s), 1536(m), 1486(m), 1438(w), 1382(s),
297(s), 1234(s), 1217(s), 1180(m), 1142(m), 1108(w),
045(w), 1036(w), 998(w), 891(w), 875(w), 862(m),
K.-B. Yu
Chengdu Center of Analysis and Determination, Chinese
Academy of Science, Chengdu, Siquan 610041, P.R. China
786(m), 783(m), 751(w), 711(w), 686(w), 662(w), 640(s),
123

5
24
J Chem Crystallogr (2007) 37:523–526
Scheme 1
N
HC
O
SeO
2
H N
OH
3
0% H
2
O
2
2
1
pyridine, reflux, 24 h
CH
3
COOH, 75 , 12 h
95% ethanol, reflux, 24h
N
N
N
O
O
6
4
7
11(w), 581(m), 555(w), 524(w), 507(w), 474(w), 451(w),
1
Crystal Structure Determination
20(w). H NMR (DMSO in ppm): 8.19 ~ 8.17 (d, 2H),
3
.52 ~ 7.39 (d, 2H), 7.17 ~ 7.07 (m, 2H), 6.62 ~ 6.58(m,
A crystal of dimensions 0.58 · 0.46 · 0.32 mm was used
for data collection on a Siemens P4 diffractometer with Mo
H). Element analyses, calculated for C H N O : C,
1
1 13 3 5
˚
4
9.44; H, 4.90%. Found: C, 49.29; H, 4.65%.
Ka (k = 0.71073 A) using x scan method. The structure of
1
atoms were refined anisotropically by full-matrix least-
was solved by direct methods and all non-hydrogen
2
squares techniques based on F . The hydrogen atoms
residing on the pyridine rings 2-amino-3-hydroxypyridium
and isoniconate-N-oxide(H1, H2, H3, H6, H7, H9, H10)
were placed geometrically, while other hydrogen bonds
Table 1 Crystal data and structure refinement for title compound
CCDC no.
CCDC 286986
(H1O, H1N, H2A, H2B, H5A, H5B) were found in dif-
Compound
(C
5
H
7
N
2
O)Á(C
6 4
H NO
3
)ÁH
2
O
ference Fourier maps.
Color/shape
Orange/Prism
The experimental and computations were performed on
a PC computer using the programs of Bruker Smart and
Bruker SHELXTL package [11, 12]. Crystallographic data
are summarized in Table 1, and selected bond lengths are
listed in Table 2 while selected hydrogen bond lengths and
angles are presented in Table 3.
Chemical formula
Formula weight
Temperature (K)
11 13 3 5
C H N O
267.24
296(2)
˚
Wavelength (A)
0.71073
Monoclinic
P2 /c
Crystal system
Space group
1
˚
a (A)
9.6905(8)
6.0040(4)
21.039(2)
101.062(8)
Result and Discussion
˚
b (A)
˚
c (A)
The salt of hydrate 2-amino-3-hydroxypyridium isonico-
nate-N-oxide was synthesized as indicated in Scheme 1
b (ꢁ)
Volume (A )
3
˚
1201.34(18)
4
Z
–
Density (calculated) (g cm )
3
Table 2 Selected bond lengths( A˚ ) and angle (ꢁ) for 1
1.478
0.119
560
–
1
Absorption coefficient (mm )
F(000)
Bond lengths( A˚ )
O(1)–C(4)
1.3406(18)
1.3168(16)
1.2573(18)
1.2527(18)
1.3409(19)
1.361(2)
N(3)–C(10)
N(3)–C(6)
C(1)–C(2)
C(2)–C(3)
C(4)–C(5)
C(8)–C(11)
1.3456(19)
1.3502(19)
1.344(2)
1.404(2)
1.423(2)
1.505(2)
Crystal size (mm)
0.58 · 0.46 · 0.32
1.97 to 26.00
O(2)–N(3)
h range for data collection (ꢁ)
Limiting indices
O(3)–C(11)
0 < h < 11, 0 < k < 7, –
5 < l < 25
O(4)–C(11)
2
N(1)–C(5)
Reflections measured
2851
N(1)–C(1)
Independent/observed reflections
Absorption correction
2353 (Rint = 0.0113)
N(2)–C(5)
1.331(2)
None
2
Bond angles (ꢁ)
O(1)–C(4)–C(3)
O(1)–C(4)–C(5)
O(2)–N(3)–C(10)
O(2)–N(3)–C(6)
O(3)–C(11)–C(8)
O(4)–C(11)–C(8)
O(4)–C(11)–O(3)
Refinement method
Full-matrix least-squares on F
2353 / 0 / 197
126.64(15)
114.24(14)
119.37(12)
120.86(13)
117.61(14)
116.89(13)
125.50(15)
N(1)–C(5)–C(4)
N(2)–C(5)–C(4)
N(2)–C(5)–N(1)
C(3)–C(4)–C(5)
C(7)–C(8)–C(9)
C(7)–C(8)–C(11)
C(9)–C(8)–C(11)
118.29(14)
121.76(15)
119.95(15)
119.12(14)
116.90(14)
121.39(13)
121.71(14)
Data/restraints/parameters
2
Goodness of fit on F
0.998
Final R indices [I > 2r(I)]
R indices (all data)
R
1
1
= 0.0361, xR
2
2
= 0.0878
= 0.0941
R
= 0.0574, xR
Extinction coefficient
0.021(2)
Largest differentical peak and hole 0.171 and –0.140
(
–
3
˚
eA )
1
23

J Chem Crystallogr (2007) 37:523–526
525
˚
Table 3 Hydrogen bond lengths (A) and bond angles (ꢁ) for 1
equal to 6.97(8)ꢁ, which indicates that the two rings are al-
most coplanar.
Donor-HÁÁÁAcceptor
ARU
DÁÁÁA
D-HÁÁÁA
As shown in Fig. 2 and 3, hydrogen bonds are the
decisive factor governing the stacking pattern in the crystal
lattice of 1. According to the function of hydrogen bonds in
1, we classify them as four types: classical hydrogen bonds
for 1-D chain, classical hydrogen bonds for 1-D ribbon,
classical hydrogen bonds for 2-D layer, and unclassical
hydrogen bonds for 3-D network. At first, deprotonated
isoniconate-N-oxide and protonated 2-amino-3-hydroxyl-
pyridine connect with lattice water through ion hydrogen
Classical hydrogen bonds for 1-D chain
N(1)–H(1N)ÁÁÁO(4)
O(1)–H(10)ÁÁÁO(5)
N(2)–H(2A)ÁÁÁO(3)
O(5)–H(5A)ÁÁÁO(2)
1435
1435
2.6610(17)
2.5468(18)
2.871(2)
174.9(15)
174(2)
171.5(17)
178(2)
2.6646(18)
Classical hydrogen bonds for 1-D ribbon
N(2)–H(2B)ÁÁÁO(3) 3666
Classical hydrogen bonds for 2-D layer
O(5)–H(5B)ÁÁÁO(3) 3676
3.0916(19)
146.0(15)
167(2)
˚
2.7942(18)
bonds [14] of O(5)–H(5A)ÁÁÁO(2)[2.6646(18) A, 178(2)ꢁ]
˚
Nonclassical hydrogen bonds for 3-D network
and O(1)-H(1O)ÁÁÁO(5)[2.5468(18) A, 174(2)ꢁ] forming a
C(10)–H(10)ÁÁÁO(4) 2645 3.1884(18) 139.46(9)
Note Translation of ARU-code to equivalent position code:
3666] = 1 – x, 1 – y, 1 – z; [1435] = –1 + x, –2 + y, z;
2645] = 1 – x, –1/2 + y, 1/2 – z; [3676] = 1 – x, 2 – y, 1 – z
basic building unit. Neighboring units are further con-
+
–
nected by pairs of N –HÁÁÁO hydrogen bonds between
protonated 2-amino-3-hydroxylpyridine and carboxylate
group with fork-like pattern [15] [N(1)–H(1N)ÁÁÁO(4)
[
[
˚
˚
2
.6610(17) A, 174.9(15)ꢁ); N(2)–H(2A)ÁÁÁO(3) 2.871(2) A,
with 4-picoline and 2-amino-3-hydroxylpyridine as parent
reagents. Although our initial purpose of designing the
reaction was to synthesize the Schiff base of pyridine N-
oxide, but unexpected compound 1 was obtained because
the 4-pyridincarboxaldehyde-N-oxide was oxidized under
air condition.
171.5(17)ꢁ] to give rise to a infinite chain. It was worthy
noting that the fork-like hydrogen bonding pattern is
observed in cytosine carboxylate interactions [16–18].
Then, two antiparallel chains form a ribbon chain through
the linkage of hydrogen bond of N(2)–H(2B)ÁÁÁO(3)
˚
[3.0916(19) A, 146.0(15)ꢁ] (Fig. 2). Parallel ribbons are
An ORTEP diagram [13] is shown in Fig. 1. The asym-
metric unit of 1 consists of one 4-carboxylpyridine-N-oxide
anion, one 2-amino-3-hydroxylpyridine cation and one
water molecule. In the basic unit, the protonation of 2-amino-
linked with each other to form a 2-D layer via hydrogen
˚
bond of O(5)–H(5B)ÁÁÁO(3)[2.7942(18) A, 167(2)ꢁ]
(Fig. 3). Finally, these 2-D layers stack in ‘‘AB’’ pattern
along the c axis and interact through unclassical hydrogen
˚
3
-hydroxylpyridine is observed (N(1)–H(1N) = 0.9919,
bond of C(10)–H(10)ÁÁÁO(4) [3.1884(18) A, 139.46(9)ꢁ]
˚
N(1)–C(1) = 1.3614 and N(1)–C(5) = 1.3408 A), and the
dihedral angle between the pyridyl ring of 4-carboxylpyri-
dine-N-oxide and that of 2-amino-3-hydroxylpyridine is
constructing the resulting 3-D supramolecular network.
From above description, one can see that a series of clas-
sical hydrogen bonds construct the 2-D layer while the
Fig. 1 An ORTEP drawing of
title compound (50%
probability ellipsoids)
Fig. 2 One-dimensional ribbon
structures connected by
hydrogen bonds
123

5
26
J Chem Crystallogr (2007) 37:523–526
Fig. 3 View of the 2-D
hydrogen bonding layer
constructed by 1-D ribbons
unclassical hydrogen bond maintains the 3-D network of
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CCDC-286986 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
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1
(
CCDC), 12 Union Road, Cambridge CB21EZ, UK; fax:
C44(0)1223–336033; e-mail: deposit@ccdc.cam.ac.uk.
1
Acknowledgement The authors gratefully acknowledge the finan-
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