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Acta Cryst. (2011). E67, o525-o526    [ doi:10.1107/S1600536811003126 ]

2-Amino-3-carboxypyrazin-1-ium nitrate monohydrate

F. Berrah, A. Ouakkaf, S. Bouacida and T. Roisnel

Abstract top

In crystal structure of the title compound, C5H6N3O2+·NO3-·H2O, intermolecular N-H...O, O-H...N and O-H...O hydrogen bonds link the cations, anions and water molecules into ribbons extending in [\overline{1}10]. Weak intermolecular C-H...O hydrogen bonds further link these ribbons into sheets parallel to (\overline{1}\overline{1}3).

Comment top

As a part of our search for new hybrid compounds based on protonated amines (Berrah et al. 2005a,b; Bouacida et al. 2005; 2009), we present the crystal structure of the title compound, (I).

The asymmetric unit of (I) contains one cation, one anion and one water molecule linked trough hydrogen bonds (Fig. 1). Bond distances and angles are similar to those encountered in analogous compounds (Berrah el al. 2005a,b; Dobson & Gerkin, 1996).

The crystal packing in the title structure can be described by considering sheets parallel to (-1-13) plane (Fig. 2). A sheet is an alternation of ribbons joined by a weak hyrogen bonds C4—H4···O4 and extended in direction [-110] (Fig. 2, Table 1). 3-Amino-pyrazinium 2-carboxylic acid cations, of the same ribbon, form centrosymetric dimers via N2—H2B···O2 hyrogen bonds. Each dimer is surrounded by two NO3- anions and four H2O molecules, and all its atoms (except C5) are involved in N—H···O, O—H···N and O—H···O H-bonds. While nitrate anions are only acceptor of H-bonds, water molecules are at the same time donor and acceptor (Table 1). The resulting 2D hydrogen-bonded network exhibit rings with R44(8), R24(10), R22(8), R33(10), R22(4) and R21(5) graph set motifs (Etter et al., 1990; Bernstein et al., 1995) (Fig. 2).

Related literature top

For similar compounds, see: Berrah et al. (2005a,b); Bouacida et al. (2005, 2009); Dobson & Gerkin (1996). For hydrogen-bond graph-set motifs, see: Etter et al. (1990); Bernstein et al. (1995).

Experimental top

The title compound was synthesized by reacting 3-amino-pyrazine 2- carboxylic acid with some excess of nitric acid in aqueous solution. Slow evaporation leads to well crystallized yellow needles.

Refinement top

H atoms of water molecule were located in difference Fourier map and included in the subsequent refinement with Uiso(H) = 1.5Ueq(O). The remaining H atoms were localized on Fourier maps but introduced in calculated positions and treated as riding on their parent atoms, with C—H = 0.95 Å, O—H = 0.84 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2 Ueq(C or N) and Uiso(H = 1.5 Ueq(O).

Computing details top

Data collection: APEX2 (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick,2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg & Berndt, 2001); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. Ortep-3 (Farrugia, 1997) view of (I) showing the atomic labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
[Figure 2] Fig. 2. DIAMOND (Brandenburg & Berndt, 2001) view of a portion of hydrogen-bonded sheet in (I) showing the graph set motif notations. Hydrogen bonds are shown as dashed lines.
2-Amino-3-carboxypyrazin-1-ium nitrate monohydrate top
Crystal data top
C5H6N3O2+·NO3−·H2OZ = 2
Mr = 220.15F(000) = 228
Triclinic, P1Dx = 1.66 Mg m−3
a = 5.1277 (4) ÅMo Kα radiation, λ = 0.71073 Å
b = 7.6368 (6) ÅCell parameters from 2815 reflections
c = 12.1571 (10) Åθ = 2.8–27.5°
α = 97.872 (3)°µ = 0.15 mm−1
β = 100.588 (3)°T = 150 K
γ = 106.194 (3)°Prism, yellow
V = 440.37 (6) Å30.58 × 0.49 × 0.42 mm
Data collection top
Bruker APEXII
diffractometer		1693 reflections with I > 2σ(I)
graphiteRint = 0.028
CCD rotation images, thin slices scansθmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		h = −6→6
Tmin = 0.773, Tmax = 0.938k = −9→9
5333 measured reflectionsl = −15→15
1967 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.097H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0451P)2 + 0.1681P]
where P = (Fo2 + 2Fc2)/3
1967 reflections(Δ/σ)max < 0.001
143 parametersΔρmax = 0.36 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C5H6N3O2+·NO3−·H2Oγ = 106.194 (3)°
Mr = 220.15V = 440.37 (6) Å3
Triclinic, P1Z = 2
a = 5.1277 (4) ÅMo Kα radiation
b = 7.6368 (6) ŵ = 0.15 mm−1
c = 12.1571 (10) ÅT = 150 K
α = 97.872 (3)°0.58 × 0.49 × 0.42 mm
β = 100.588 (3)°
Data collection top
Bruker APEXII
diffractometer		1967 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2002)		1693 reflections with I > 2σ(I)
Tmin = 0.773, Tmax = 0.938Rint = 0.028
5333 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.036H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.097Δρmax = 0.36 e Å−3
S = 1.03Δρmin = −0.25 e Å−3
1967 reflectionsAbsolute structure: ?
143 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.3536 (3)0.81463 (18)0.56444 (11)0.0213 (3)
C20.5373 (3)0.93343 (17)0.67594 (11)0.0196 (3)
C30.5053 (3)1.11068 (18)0.71720 (11)0.0206 (3)
C40.8826 (3)1.14836 (19)0.87398 (11)0.0243 (3)
H4A1.00581.22180.94340.029*
C50.9034 (3)0.97938 (19)0.83049 (11)0.0239 (3)
H51.04200.93540.87020.029*
N10.4633 (3)1.60420 (16)0.88650 (10)0.0226 (3)
N20.3198 (3)1.18108 (16)0.66687 (11)0.0270 (3)
H2A0.31371.29050.69800.032*
H2B0.20191.11880.60210.032*
N30.6850 (2)1.20958 (15)0.81712 (10)0.0228 (3)
H30.67191.31810.84600.027*
N40.7294 (2)0.87393 (15)0.73168 (9)0.0219 (3)
O10.3992 (2)0.65591 (14)0.54062 (9)0.0303 (3)
H10.30040.59770.47590.045*
O20.1873 (2)0.86840 (14)0.50431 (9)0.0288 (3)
O30.4414 (2)1.75010 (14)0.93506 (9)0.0326 (3)
O40.6850 (2)1.56230 (14)0.91237 (9)0.0279 (3)
O50.2640 (2)1.49165 (15)0.80957 (9)0.0337 (3)
O1W0.8473 (3)0.53972 (18)0.65527 (11)0.0490 (4)
H1W0.979 (6)0.543 (4)0.704 (3)0.074*
H2W0.793 (6)0.637 (4)0.671 (2)0.074*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0231 (6)0.0211 (6)0.0170 (6)0.0071 (5)0.0009 (5)0.0001 (5)
C20.0215 (6)0.0196 (6)0.0156 (6)0.0051 (5)0.0021 (5)0.0017 (5)
C30.0209 (6)0.0205 (6)0.0174 (6)0.0035 (5)0.0043 (5)−0.0001 (5)
C40.0246 (7)0.0254 (7)0.0157 (6)0.0011 (5)0.0002 (5)0.0009 (5)
C50.0236 (7)0.0255 (7)0.0178 (6)0.0050 (5)−0.0014 (5)0.0029 (5)
N10.0265 (6)0.0208 (5)0.0185 (6)0.0066 (5)0.0036 (5)0.0014 (4)
N20.0284 (6)0.0234 (6)0.0255 (6)0.0119 (5)−0.0023 (5)−0.0038 (5)
N30.0253 (6)0.0195 (5)0.0189 (6)0.0049 (5)0.0017 (5)−0.0029 (4)
N40.0242 (6)0.0212 (5)0.0173 (6)0.0055 (5)0.0011 (4)0.0023 (4)
O10.0380 (6)0.0252 (5)0.0214 (5)0.0159 (4)−0.0088 (4)−0.0075 (4)
O20.0300 (5)0.0276 (5)0.0243 (5)0.0135 (4)−0.0071 (4)−0.0016 (4)
O30.0406 (6)0.0231 (5)0.0337 (6)0.0116 (5)0.0108 (5)−0.0023 (4)
O40.0256 (5)0.0275 (5)0.0250 (5)0.0093 (4)−0.0031 (4)−0.0030 (4)
O1W0.0619 (9)0.0472 (7)0.0308 (6)0.0396 (7)−0.0220 (6)−0.0188 (5)
O50.0284 (6)0.0316 (6)0.0316 (6)0.0109 (4)−0.0085 (4)−0.0070 (4)
Geometric parameters (Å, °) top
C1—O21.2162 (17)C5—H50.9500
C1—O11.3017 (16)N1—O31.2314 (14)
C1—C21.5050 (18)N1—O41.2621 (15)
C2—N41.3132 (17)N1—O51.2635 (15)
C2—C31.4420 (17)N2—H2A0.8800
C3—N21.3150 (18)N2—H2B0.8800
C3—N31.3580 (17)N3—H30.8800
C4—N31.3488 (18)O1—H10.8400
C4—C51.3663 (19)O1W—H1W0.81 (3)
C4—H4A0.9500O1W—H2W0.88 (3)
C5—N41.3520 (17)
O2—C1—O1125.51 (12)C4—C5—H5119.6
O2—C1—C2121.65 (11)O3—N1—O4121.00 (12)
O1—C1—C2112.82 (12)O3—N1—O5120.97 (12)
N4—C2—C3121.68 (12)O4—N1—O5118.02 (11)
N4—C2—C1118.46 (11)C3—N2—H2A120.0
C3—C2—C1119.83 (12)C3—N2—H2B120.0
N2—C3—N3118.84 (12)H2A—N2—H2B120.0
N2—C3—C2125.70 (12)C4—N3—C3122.72 (11)
N3—C3—C2115.46 (12)C4—N3—H3118.6
N3—C4—C5119.16 (12)C3—N3—H3118.6
N3—C4—H4A120.4C2—N4—C5120.09 (11)
C5—C4—H4A120.4C1—O1—H1109.5
N4—C5—C4120.89 (13)H1W—O1W—H2W110 (3)
N4—C5—H5119.6
O2—C1—C2—N4−174.02 (13)N3—C4—C5—N40.1 (2)
O1—C1—C2—N44.43 (18)C5—C4—N3—C3−0.5 (2)
O2—C1—C2—C34.1 (2)N2—C3—N3—C4−179.55 (13)
O1—C1—C2—C3−177.47 (12)C2—C3—N3—C40.68 (19)
N4—C2—C3—N2179.80 (13)C3—C2—N4—C50.1 (2)
C1—C2—C3—N21.8 (2)C1—C2—N4—C5178.13 (12)
N4—C2—C3—N3−0.45 (19)C4—C5—N4—C20.1 (2)
C1—C2—C3—N3−178.48 (11)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1Wi0.841.692.5233 (17)168
O1W—H1W···O5ii0.80 (3)1.93 (3)2.7152 (18)167 (3)
O1W—H2W···O10.88 (3)2.39 (3)2.8825 (19)116 (2)
O1W—H2W···N40.88 (3)1.99 (3)2.8566 (18)170 (2)
N2—H2A···O50.882.012.8549 (17)161
N2—H2B···O20.882.082.7163 (17)128
N2—H2B···O2iii0.882.202.9125 (18)137
N3—H3···O40.881.912.7825 (16)174
C4—H4A···O4iv0.952.243.1818 (17)169
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y−1, z; (iii) −x, −y+2, −z+1; (iv) −x+2, −y+3, −z+2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1—H1···O1Wi0.841.692.5233 (17)168
O1W—H1W···O5ii0.80 (3)1.93 (3)2.7152 (18)167 (3)
O1W—H2W···O10.88 (3)2.39 (3)2.8825 (19)116 (2)
O1W—H2W···N40.88 (3)1.99 (3)2.8566 (18)170 (2)
N2—H2A···O50.882.012.8549 (17)161
N2—H2B···O20.882.082.7163 (17)128
N2—H2B···O2iii0.882.202.9125 (18)137
N3—H3···O40.881.912.7825 (16)174
C4—H4A···O4iv0.952.243.1818 (17)169
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x+1, y−1, z; (iii) −x, −y+2, −z+1; (iv) −x+2, −y+3, −z+2.
Acknowledgements top

We are grateful to the LCATM Laboratory, Université Larbi Ben M'Hidi, Oum El Bouaghi, Algeria, for financial support.

references
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