2-Amino-3-nitro­pyridinium hydrogen selenate

Samah Akriche; Mohamed Rzaigui

doi:10.1107/S1600536809022879

. 2009 Jun 20;65(Pt 7):o1648. doi: 10.1107/S1600536809022879

2-Amino-3-nitropyridinium hydrogen selenate

Samah Akriche ^a,^*, Mohamed Rzaigui ^a

PMCID: PMC2969471 PMID: 21582912

Abstract

The asymmetric unit of the title compound, C₅H₆N₃O₂ ⁺·HSeO₄ ⁻, contains two monoprotonated 2-amino-3-nitropyridinium cations and two hydrogen selenate anions which are connected through N—H⋯O and O—H⋯O hydrogen bonds, building chains parallel to the a direction. These chains are further connected to each other by weaker C—H⋯O hydrogen-bonding interactions, leading to the formation of a three-dimensional network.

Related literature

For related structures, see: Akriche et al. (2009 ▶); Fleck (2006 ▶); Le Fur, Masse & Nicoud (1998 ▶); Nicoud et al. (1997 ▶); Maalej et al. (2008 ▶).

Experimental

Crystal data

C₅H₆N₃O₂ ⁺·HSeO₄ ⁻
M _r = 284.10
Monoclinic,
a = 9.090 (3) Å
b = 20.130 (2) Å
c = 10.434 (4) Å
β = 104.84 (2)°
V = 1845.6 (10) Å³
Z = 8
Mo Kα radiation
μ = 4.09 mm⁻¹
T = 298 K
0.37 × 0.29 × 0.19 mm

Data collection

Enraf–Nonius Turbo-CAD-4 diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.145, T _max = 0.298 (expected range = 0.224–0.460)
7325 measured reflections
4433 independent reflections
2980 reflections with I > 2σ(I)
R _int = 0.040
2 standard reflections frequency: 120 min intensity decay: 4%

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.112
S = 1.01
4433 reflections
274 parameters
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022879/dn2458sup1.cif

e-65-o1648-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022879/dn2458Isup2.hkl

e-65-o1648-Isup2.hkl^{(212.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O6	0.82	1.75	2.565 (5)	170
O5—H5⋯O2ⁱ	0.82	1.80	2.601 (5)	167
N1—H1A⋯O4	0.86	1.84	2.679 (5)	166
N2—H2A⋯O3	0.86	2.02	2.870 (6)	172
N2—H2B⋯O9	0.86	2.09	2.675 (6)	124
N2—H2B⋯O8ⁱⁱ	0.86	2.28	2.933 (5)	133
N4—H4⋯O7	0.86	2.05	2.864 (5)	157
N5—H5A⋯O8	0.86	2.07	2.900 (5)	163
N5—H5B⋯O3ⁱⁱ	0.86	2.11	2.798 (5)	137
N5—H5B⋯O11	0.86	2.12	2.693 (5)	124
C3—H3⋯O5ⁱⁱⁱ	0.93	2.54	3.443 (5)	163
C4—H4A⋯O12^iv	0.93	2.47	3.290 (6)	148
C8—H8⋯O6ⁱⁱⁱ	0.93	2.57	3.463 (6)	162
C10—H10⋯O4^v	0.93	2.35	3.228 (6)	158

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

supplementary crystallographic information

Comment

The important advantage of hybrid organic inorganic salts is the opportunity offered by the chromophores that when anchored onto inorganic host matrices, lead to non-centrosymmetric frameworks suitable for NLO devices. The approach of this new engineering has been applied to 2-amino-3-nitropyridinium cation (2 A3NP⁺) encapsulated in various anionic subnetworks (Akriche et al., 2009, Nicoud et al.,1997, Le Fur et al., 1998). The attempt using (HSO₄^-) _n polymeric anions has been successful with the cristallization of the non-centrosymmetric 2-Amino-3-nitropyridinium sulfate (Le Fur et al., 1998). The encapsulation of this cation in (HSeO₄^-)_n polymeric anions leads to the title compound (I).

The asymmetric unit of (I) contains two monoprotonated 2-amino-3-nitropyridinium cations and two hydrogen selenate anions (Fig.1) which are connected through N—H···O, C—H···O and O—H···O hydrogen bonds. The hydrogen selenate anions are interconnected between themselves by H-bonds involving the proton of selenate groups leading to (HSeO₄^-) _n chains parallel to the a axis (Fig. 2).

In this atomic arrangement the HSeO₄^- tetraedra are slightly distorted with Se—O distances from 1.594 (6) to 1.713 (4) Å. The Se—O bonds in selenate tetrahedra depends greatly on the nature of the O atoms acting as an acceptor or a donor atoms: the longer bonds (1.713 (4) and 1.692 (5) Å) involve oxygen atoms acting as a H-donor whereas shorter bonds ranging from 1.594 (6) to 1.623 (4) relate to oxygen atoms acting as H-acceptor participating in hydrogen bonds of type N—H···O and C—H···O. As expected, the geometrical features of anion agree with those previously observed for this group in other analogues (Fleck, 2006, Maalej et al., 2008).

The 2-amino-3-nitropyridinium cations are onchored onto anionic chains through short hydrogen bonds originating from the NH₂ and NH⁺ groups. The unique inter-cation contact C4—H4A···O11(H4A···O11 = 2.45 Å) induces the aggregation of cations in pairs (2 A3NP⁺)₂ elongated in -(a+c) direction. Two hydrogen bonds, N2—H2B···O10 (2.10 Å) and N5—H5B···O12 (2.11 Å) (see Table 1) ensure the intra-cation links. This situation is well observed in nitroaniline derivatives in which nitro and amino groups are ortho to one another which precludes the rotation of the nitro group with respect to the pyridinium rings. The diedral angles between the planes of the NO₂ groups and the two pyridinium planes are 19.0 (3) and 15.9 (4) % indicating a distortion of the NO₂ groups under the influence of C—H···O hydrogn bonds of neighbouring cations. This situation is alawys observed in other 2-amino-3-nitropyridinium salts (Nicoud et al.,1997, Le Fur et al., 1998). The bond lengths and angles in (I) are normal and comparable with the corresponding values observed in the related structure (Akriche et al., 2009, Nicoud et al.,1997, Le Fur et al., 1998).

Experimental

The title compound (I) was cristallized by slow evaporation at room temperature of an aqueous solution (20 ml) of 2-amino-3-nitropyridine (4 mmol) and selenic acid (4 mmol) in a 1:1 stochiometric ratio.