2-Amino-3-nitro­pyridinium hydrogen oxalate

Akriche, S.; Rzaigui, M.

doi:10.1107/S1600536809008666

organic compounds

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Volume 65| Part 4| April 2009| Page o793

doi:10.1107/S1600536809008666

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2-Amino-3-nitropyridinium hydrogen oxalate

Samah Akriche ^a ^* and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia
^*Correspondence e-mail: samah.akriche@fsb.rnu.tn

(Received 4 February 2009; accepted 9 March 2009; online 19 March 2009)

In the non-centrosymetric title compound, C₅H₆N₃O₂⁺·C₂HO₄⁻, the hydrogen oxalate anions form corrugated chains parallel to the c axis, linked by O—H⋯O hydrogen bonds. The 2-amino-3-nitropyridinium cations are anchored between theses chains by N—H⋯O and C—H⋯O hydrogen bonds and van der Waals and electrostatic interactions, creating a three-dimensional network.

Related literature

For related structures, see: Akriche & Rzaigui (2000 , 2009 ); Le Fur et al. (1998 ); Nicoud et al. (1997 ); For a discussion of hydrogen bonding, see: Desiraju (1989 , 1995 ).

Experimental

Crystal data

C₅H₆N₃O₂⁺·C₂HO₄⁻
M_r = 229.16
Orthorhombic, P n a 2₁
a = 15.268 (4) Å
b = 6.921 (3) Å
c = 8.807 (2) Å
V = 930.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.15 mm⁻¹
T = 293 K
0.33 × 0.25 × 0.21 mm

Data collection

Enraf–Nonius Turbo CAD-4 diffractometer
Absorption correction: none
2228 measured reflections
1190 independent reflections
1003 reflections with I > 2σ(I)
R_int = 0.020
2 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.088
S = 1.06
1190 reflections
147 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2ⁱ	0.82	1.82	2.632 (2)	171
N1—H1⋯O2	0.86	1.85	2.706 (3)	175
N2—H2A⋯O1	0.86	1.99	2.837 (3)	170
N2—H2B⋯O5	0.86	2.09	2.673 (3)	124
N2—H2B⋯O4ⁱⁱ	0.86	2.51	3.188 (3)	136
C3—H3A⋯O5ⁱⁱⁱ	0.93	2.44	3.178 (3)	136
C4—H4⋯O1^iv	0.93	2.33	3.258 (3)	174
C5—H5⋯O6^v	0.93	2.57	3.262 (3)	132
Symmetry codes: (i) $[-x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (iii) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (iv) x, y, z-1; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ .

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008666/kj2116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008666/kj2116Isup2.hkl

checkCIF report

Comment top

The search for new molecular materials for the non-linear optics lies at the basis of our ongoing study of 2-amino-3-nitropyridinium salts. Our strategy is aimed at the production of very cohesive non-centrosymmetric packing of chromophores. We have previously reported two centrosymetric structures of 2-amino-3-nitropyridinium (Akriche & Rzaigui, 2000; Akriche & Rzaigui, 2009). We report here a new non-centrosymmetric structure, 2-amino-3-nitropyridinium hydrogenoxalate.

The asymmetric unit of the title compound consists of one (HC₂O₄)^- anion and one (2-NH₂-3-NO₂C₅H₃NH)⁺ cation (Fig. 1). In the hydrogenoxalate (HC₂O₄)^-, the H atom is located at O3 as is also indicated by elongation of the corresponding C—O distance [O3—C7 is 1.314 (3) Å]. The bond length of C6—C7 is relatively long [1.545 (3) Å] as expected for an oxalate anion. In the 2-amino-3-nitropyridinium cation, nitro and amino groups are ortho to one another, which explains the presence of the intra-cation contact N2—H2B···O5 (Le Fur et al., 1998; Nicoud et al.,1997).

The structure projection in Fig. 2 shows that the oxalate ions are organized in corrugated chains extending along the c axis. The cations are located between these chains and manifest multiple H-bonds. In fact, in this structure there are three categories of H-bond (Table 1), O—H···O, N—H···O and C—H···O. Within each oxalate chain, the (HC₂O₄)^- groups are interconnected by strong O—H···O hydrogen bonds. These chains are themselves interconnected by N—H···O interactions originating from the NH⁺ and NH₂ groups of the cations. It is worth noticing the presence of long C—H···O contacts (Desiraju, 1989; Desiraju, 1995) occurring between cations and between cations and anions. The density of this H-bond scheme constitutes probably the main factor responsible for the formation of a non-centrosymetric material.

Related literature top

For related structures, see: Akriche & Rzaigui (2000, 2009); Le Fur et al. (1998); Nicoud et al. (1997); For a discussion of hydrogen bonding, see: Desiraju (1989, 1995)

Experimental top

An aqueous solution containing 0.004 mol of H₂C₂O₄ in 10 ml of water, was added to 0.004 mol of 2-amino-3-nitropyridine in 20 ml of pure acetic acid. The obtained yellow solution was stirred at 333 K for 10 min and then left to stand at room temperature. Yellow single crystals of the title compound were obtained after some days.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are represented as dashed lines.
	Fig. 2. A perspective view of the packing of the title compound. Hydrogen bonds are represented as dashed lines.

2-Amino-3-nitropyridinium hydrogen oxalate top

Crystal data top

C₅H₆N₃O₂⁺·C₂HO₄⁻	D_x = 1.636 Mg m⁻³
M_r = 229.16	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna2₁	Cell parameters from 25 reflections
a = 15.268 (4) Å	θ = 9–11°
b = 6.921 (3) Å	µ = 0.15 mm⁻¹
c = 8.807 (2) Å	T = 293 K
V = 930.6 (5) Å³	Rectangular prism, yellow
Z = 4	0.33 × 0.25 × 0.21 mm
F(000) = 472

Data collection top

Enraf–Nonius Turbo CAD-4 diffractometer	R_int = 0.020
Radiation source: Enraf–Nonius FR590	θ_max = 28.0°, θ_min = 2.7°
Graphite monochromator	h = −20→0
Nonprofiled ω scans	k = −7→9
2228 measured reflections	l = −11→0
1190 independent reflections	2 standard reflections every 120 min
1003 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.088	w = 1/[σ²(F_o²) + (0.0559P)² + 0.0295P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.001
1190 reflections	Δρ_max = 0.33 e Å⁻³
147 parameters	Δρ_min = −0.20 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.053 (6)

Crystal data top

C₅H₆N₃O₂⁺·C₂HO₄⁻	V = 930.6 (5) Å³
M_r = 229.16	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 15.268 (4) Å	µ = 0.15 mm⁻¹
b = 6.921 (3) Å	T = 293 K
c = 8.807 (2) Å	0.33 × 0.25 × 0.21 mm

Data collection top

Enraf–Nonius Turbo CAD-4 diffractometer	R_int = 0.020
2228 measured reflections	2 standard reflections every 120 min
1190 independent reflections	intensity decay: 1%
1003 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.034	1 restraint
wR(F²) = 0.088	H-atom parameters constrained
S = 1.06	Δρ_max = 0.33 e Å⁻³
1190 reflections	Δρ_min = −0.20 e Å⁻³
147 parameters

Special details top

Geometry. H atoms were treated as riding, with C—H = 0.93 A °, N—H = 0.86 A ° and O—H = 0.82 A °, and with U_iso(H) = 1.2Ueq(C,N) and 1.5Ueq(O). 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

	x	y	z	U_iso*/U_eq
O1	0.18864 (12)	0.6389 (3)	0.4311 (2)	0.0512 (5)
O2	0.10055 (11)	0.5552 (3)	0.2423 (2)	0.0408 (4)
O3	0.05130 (11)	0.5172 (3)	0.6129 (2)	0.0391 (4)
H3	0.0051	0.5043	0.6593	0.059*
O4	−0.03139 (11)	0.6833 (3)	0.4481 (2)	0.0494 (5)
O5	0.49613 (12)	0.5813 (3)	0.1226 (3)	0.0532 (5)
O6	0.52023 (11)	0.6750 (3)	−0.1071 (3)	0.0545 (5)
N1	0.23161 (12)	0.5903 (3)	0.0374 (3)	0.0375 (5)
H1	0.1920	0.5818	0.1065	0.045*
N2	0.33259 (15)	0.6060 (3)	0.2291 (3)	0.0462 (6)
H2A	0.2900	0.6012	0.2930	0.055*
H2B	0.3857	0.6133	0.2612	0.055*
N3	0.47122 (12)	0.6244 (3)	−0.0050 (3)	0.0367 (5)
C1	0.31649 (14)	0.6020 (3)	0.0827 (3)	0.0321 (5)
C2	0.37793 (14)	0.6148 (3)	−0.0380 (3)	0.0318 (5)
C3	0.35201 (16)	0.6188 (4)	−0.1871 (3)	0.0363 (5)
H3A	0.3936	0.6300	−0.2638	0.044*
C4	0.26384 (17)	0.6061 (4)	−0.2236 (3)	0.0437 (6)
H4	0.2452	0.6078	−0.3241	0.052*
C5	0.20572 (16)	0.5911 (4)	−0.1078 (3)	0.0421 (6)
H5	0.1463	0.5811	−0.1298	0.050*
C6	0.11677 (14)	0.5994 (3)	0.3773 (3)	0.0303 (5)
C7	0.03636 (14)	0.6065 (3)	0.4838 (3)	0.0302 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0315 (8)	0.0930 (14)	0.0292 (9)	−0.0146 (10)	−0.0004 (7)	−0.0040 (10)
O2	0.0286 (7)	0.0684 (11)	0.0254 (8)	−0.0040 (8)	0.0007 (7)	−0.0037 (9)
O3	0.0300 (8)	0.0618 (12)	0.0256 (7)	0.0005 (8)	0.0063 (7)	0.0065 (8)
O4	0.0346 (9)	0.0660 (12)	0.0475 (11)	0.0110 (8)	0.0040 (8)	0.0115 (10)
O5	0.0342 (9)	0.0727 (13)	0.0528 (12)	0.0094 (9)	−0.0082 (9)	0.0076 (11)
O6	0.0330 (9)	0.0779 (13)	0.0526 (12)	−0.0118 (9)	0.0125 (8)	−0.0050 (11)
N1	0.0243 (9)	0.0522 (14)	0.0361 (12)	−0.0015 (8)	0.0039 (8)	−0.0004 (9)
N2	0.0317 (10)	0.0773 (18)	0.0296 (11)	−0.0022 (10)	0.0002 (8)	0.0046 (11)
N3	0.0259 (9)	0.0401 (10)	0.0440 (12)	0.0007 (8)	0.0035 (9)	−0.0039 (9)
C1	0.0271 (10)	0.0372 (12)	0.0319 (12)	−0.0008 (9)	0.0024 (9)	0.0020 (9)
C2	0.0252 (10)	0.0356 (11)	0.0347 (12)	0.0013 (8)	0.0024 (9)	−0.0014 (10)
C3	0.0352 (12)	0.0427 (14)	0.0311 (12)	0.0002 (10)	0.0057 (10)	−0.0004 (10)
C4	0.0407 (13)	0.0592 (17)	0.0311 (13)	0.0026 (11)	−0.0038 (10)	−0.0018 (11)
C5	0.0271 (10)	0.0585 (16)	0.0406 (15)	0.0020 (10)	−0.0049 (10)	−0.0044 (12)
C6	0.0279 (10)	0.0391 (11)	0.0240 (10)	−0.0029 (9)	0.0015 (9)	0.0033 (9)
C7	0.0263 (10)	0.0382 (11)	0.0261 (11)	−0.0040 (8)	−0.0003 (8)	−0.0026 (9)

Geometric parameters (Å, º) top

O1—C6	1.226 (3)	N2—H2A	0.8600
O2—C6	1.252 (3)	N2—H2B	0.8600
O3—C7	1.314 (3)	N3—C2	1.455 (3)
O3—H3	0.8200	C1—C2	1.420 (3)
O4—C7	1.205 (3)	C2—C3	1.372 (3)
O5—N3	1.223 (3)	C3—C4	1.387 (3)
O6—N3	1.221 (3)	C3—H3A	0.9300
N1—C5	1.338 (4)	C4—C5	1.356 (4)
N1—C1	1.358 (3)	C4—H4	0.9300
N1—H1	0.8600	C5—H5	0.9300
N2—C1	1.313 (3)	C6—C7	1.545 (3)

C7—O3—H3	109.5	C2—C3—C4	120.0 (2)
C5—N1—C1	124.2 (2)	C2—C3—H3A	120.0
C5—N1—H1	117.9	C4—C3—H3A	120.0
C1—N1—H1	117.9	C5—C4—C3	117.8 (2)
C1—N2—H2A	120.0	C5—C4—H4	121.1
C1—N2—H2B	120.0	C3—C4—H4	121.1
H2A—N2—H2B	120.0	N1—C5—C4	121.7 (2)
O6—N3—O5	123.8 (2)	N1—C5—H5	119.1
O6—N3—C2	117.8 (2)	C4—C5—H5	119.1
O5—N3—C2	118.5 (2)	O1—C6—O2	126.8 (2)
N2—C1—N1	117.9 (2)	O1—C6—C7	118.0 (2)
N2—C1—C2	127.6 (2)	O2—C6—C7	115.25 (19)
N1—C1—C2	114.5 (2)	O4—C7—O3	125.6 (2)
C3—C2—C1	121.8 (2)	O4—C7—C6	122.5 (2)
C3—C2—N3	118.2 (2)	O3—C7—C6	111.85 (19)
C1—C2—N3	120.0 (2)

C5—N1—C1—N2	177.8 (3)	C1—C2—C3—C4	−1.3 (4)
C5—N1—C1—C2	−0.2 (4)	N3—C2—C3—C4	178.7 (2)
N2—C1—C2—C3	−176.6 (3)	C2—C3—C4—C5	0.4 (4)
N1—C1—C2—C3	1.2 (3)	C1—N1—C5—C4	−0.7 (5)
N2—C1—C2—N3	3.3 (4)	C3—C4—C5—N1	0.6 (4)
N1—C1—C2—N3	−178.8 (2)	O1—C6—C7—O4	134.2 (3)
O6—N3—C2—C3	14.8 (3)	O2—C6—C7—O4	−45.0 (3)
O5—N3—C2—C3	−165.1 (2)	O1—C6—C7—O3	−46.9 (3)
O6—N3—C2—C1	−165.2 (2)	O2—C6—C7—O3	133.9 (2)
O5—N3—C2—C1	15.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	1.82	2.632 (2)	171
N1—H1···O2	0.86	1.85	2.706 (3)	175
N2—H2A···O1	0.86	1.99	2.837 (3)	170
N2—H2B···O5	0.86	2.09	2.673 (3)	124
N2—H2B···O4ⁱⁱ	0.86	2.51	3.188 (3)	136
C3—H3A···O5ⁱⁱⁱ	0.93	2.44	3.178 (3)	136
C4—H4···O1^iv	0.93	2.33	3.258 (3)	174
C5—H5···O6^v	0.93	2.57	3.262 (3)	132

Symmetry codes: (i) −x, −y+1, z+1/2; (ii) x+1/2, −y+3/2, z; (iii) −x+1, −y+1, z−1/2; (iv) x, y, z−1; (v) x−1/2, −y+3/2, z.

Experimental details

Crystal data
Chemical formula	C₅H₆N₃O₂⁺·C₂HO₄⁻
M_r	229.16
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	15.268 (4), 6.921 (3), 8.807 (2)
V (Å³)	930.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.15
Crystal size (mm)	0.33 × 0.25 × 0.21

Data collection
Diffractometer	Enraf–Nonius Turbo CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2228, 1190, 1003
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.088, 1.06
No. of reflections	1190
No. of parameters	147
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.20

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2ⁱ	0.82	1.82	2.632 (2)	171.2
N1—H1···O2	0.86	1.85	2.706 (3)	175.1
N2—H2A···O1	0.86	1.99	2.837 (3)	169.9
N2—H2B···O5	0.86	2.09	2.673 (3)	124.2
N2—H2B···O4ⁱⁱ	0.86	2.51	3.188 (3)	136.4
C3—H3A···O5ⁱⁱⁱ	0.93	2.44	3.178 (3)	135.9
C4—H4···O1^iv	0.93	2.33	3.258 (3)	173.9
C5—H5···O6^v	0.93	2.57	3.262 (3)	131.8

Symmetry codes: (i) −x, −y+1, z+1/2; (ii) x+1/2, −y+3/2, z; (iii) −x+1, −y+1, z−1/2; (iv) x, y, z−1; (v) x−1/2, −y+3/2, z.

References

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doi:10.1107/S1600536809008666

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