2-Amino­pyrimidinium nitrate

Cheng, X.-L.; Gao, S.; Ng, S.W.

doi:10.1107/S1600536809052362

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 1| January 2010| Page o127

doi:10.1107/S1600536809052362

Open

access

2-Aminopyrimidinium nitrate

Xiao-Li Cheng,^a Shan Gao ^a and Seik Weng Ng ^b ^*

^aCollege of Chemistry and Materials Science, Heilongjiang University, Harbin 150080, People's Republic of China, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 4 December 2009; accepted 5 December 2009; online 12 December 2009)

In the title compound, C₄H₆N₃⁺·NO₃⁻, the cation is coplanar with the anion (r.m.s. deviation = 0.048 Å), and links to the anion via an N—H⋯O hydrogen bond, forming an ion pair. In the crystal, adjacent ion pairs are further linked by N—H⋯O hydrogen bonds into linear chains running along the b axis.

Related literature

For the crystal structures of the 2-aminopyrimidinium salts of other mineral acids, see: Czupiński et al. (2005 ); Lee et al. (2003 ); Ye et al. (2002 ).

Experimental

Crystal data

C₄H₆N₃⁺·NO₃⁻
M_r = 158.13
Monoclinic, C 2/c
a = 12.632 (2) Å
b = 6.2160 (8) Å
c = 17.727 (2) Å
β = 99.009 (3)°
V = 1374.8 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.968, T_max = 0.981
5139 measured reflections
1210 independent reflections
823 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.120
S = 0.99
1210 reflections
124 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (1)	1.87 (1)	2.742 (2)	177 (2)
N3—H11⋯O1	0.86 (1)	1.99 (1)	2.850 (3)	178 (2)
N3—H12⋯O2ⁱ	0.85 (1)	2.05 (1)	2.901 (2)	178 (2)
Symmetry code: (i) x, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalClear (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052362/xu2705sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809052362/xu2705Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of the 2-aminopyrimidinium salts of other mineral acids, see: Czupiński et al. (2005); Lee et al. (2003); Ye et al. (2002).

Experimental top

To an aqueous solution of 2-aminopyrimidine (0.19 g, 2 mmol) was added chromium nitrate nonahydrate (0.80 g, 2 mmol). The pale green solution was set aside for several days. Colorless crystals of the organic salt were isolated.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalClear (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of [C₄H₆N₄][NO₃] at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

2-Aminopyrimidinium nitrate top

Crystal data top

C₄H₆N₃⁺·NO₃⁻	F(000) = 656
M_r = 158.13	D_x = 1.528 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3773 reflections
a = 12.632 (2) Å	θ = 3.3–27.5°
b = 6.2160 (8) Å	µ = 0.13 mm⁻¹
c = 17.727 (2) Å	T = 293 K
β = 99.009 (3)°	Prism, colorless
V = 1374.8 (3) Å³	0.25 × 0.20 × 0.15 mm
Z = 8

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1210 independent reflections
Radiation source: fine-focus sealed tube	823 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ω scan	θ_max = 25.0°, θ_min = 3.3°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
T_min = 0.968, T_max = 0.981	k = −7→7
5139 measured reflections	l = −21→20

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0773P)²] where P = (F_o² + 2F_c²)/3
1210 reflections	(Δ/σ)_max = 0.001
124 parameters	Δρ_max = 0.19 e Å⁻³
6 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₄H₆N₃⁺·NO₃⁻	V = 1374.8 (3) Å³
M_r = 158.13	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 12.632 (2) Å	µ = 0.13 mm⁻¹
b = 6.2160 (8) Å	T = 293 K
c = 17.727 (2) Å	0.25 × 0.20 × 0.15 mm
β = 99.009 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1210 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	823 reflections with I > 2σ(I)
T_min = 0.968, T_max = 0.981	R_int = 0.028
5139 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	6 restraints
wR(F²) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.19 e Å⁻³
1210 reflections	Δρ_min = −0.15 e Å⁻³
124 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.61627 (16)	1.0844 (3)	0.47003 (8)	0.0892 (6)
O2	0.63012 (12)	1.3264 (2)	0.38605 (8)	0.0711 (5)
O3	0.61420 (14)	0.9926 (3)	0.35358 (9)	0.0797 (5)
N1	0.62478 (13)	0.3594 (3)	0.59174 (10)	0.0568 (5)
N2	0.62700 (13)	0.7155 (3)	0.63460 (9)	0.0575 (5)
N3	0.62544 (15)	0.6380 (3)	0.50731 (10)	0.0633 (5)
N4	0.62009 (13)	1.1341 (3)	0.40181 (9)	0.0560 (5)
C1	0.62639 (15)	0.5716 (3)	0.57800 (10)	0.0501 (5)
C2	0.62721 (17)	0.6376 (4)	0.70374 (12)	0.0616 (6)
C3	0.62702 (18)	0.4200 (4)	0.72104 (13)	0.0669 (6)
C4	0.62560 (17)	0.2810 (4)	0.66282 (13)	0.0638 (6)
H1	0.6222 (17)	0.268 (3)	0.5539 (10)	0.074 (7)*
H11	0.6213 (19)	0.7733 (19)	0.4964 (16)	0.083 (8)*
H12	0.6282 (16)	0.547 (3)	0.4718 (9)	0.068 (7)*
H2	0.6222 (18)	0.749 (3)	0.7401 (13)	0.079 (7)*
H3	0.628 (2)	0.378 (4)	0.7724 (10)	0.087 (7)*
H4	0.6234 (17)	0.130 (3)	0.6655 (12)	0.068 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1669 (17)	0.0547 (10)	0.0505 (9)	0.0094 (10)	0.0311 (9)	0.0031 (7)
O2	0.1061 (12)	0.0523 (10)	0.0576 (9)	−0.0043 (8)	0.0217 (8)	0.0025 (7)
O3	0.1178 (13)	0.0620 (11)	0.0620 (9)	−0.0010 (9)	0.0227 (8)	−0.0182 (8)
N1	0.0695 (11)	0.0435 (11)	0.0575 (10)	0.0026 (7)	0.0104 (8)	−0.0033 (8)
N2	0.0713 (11)	0.0478 (10)	0.0543 (9)	0.0030 (8)	0.0126 (8)	−0.0039 (8)
N3	0.0928 (13)	0.0486 (13)	0.0504 (10)	0.0032 (9)	0.0174 (9)	−0.0014 (8)
N4	0.0677 (10)	0.0512 (11)	0.0506 (10)	0.0046 (8)	0.0144 (8)	−0.0020 (8)
C1	0.0535 (11)	0.0447 (12)	0.0520 (10)	0.0022 (8)	0.0077 (8)	−0.0022 (8)
C2	0.0742 (14)	0.0584 (15)	0.0533 (12)	0.0030 (10)	0.0131 (10)	−0.0047 (10)
C3	0.0787 (15)	0.0674 (15)	0.0559 (12)	0.0022 (11)	0.0146 (11)	0.0062 (12)
C4	0.0736 (14)	0.0500 (14)	0.0676 (13)	0.0011 (10)	0.0104 (11)	0.0089 (11)

Geometric parameters (Å, º) top

O1—N4	1.257 (2)	N3—C1	1.318 (3)
O2—N4	1.239 (2)	N3—H11	0.86 (1)
O3—N4	1.221 (2)	N3—H12	0.85 (1)
N1—C1	1.342 (2)	C2—C3	1.387 (3)
N1—C4	1.350 (3)	C2—H2	0.953 (16)
N1—H1	0.87 (1)	C3—C4	1.344 (3)
N2—C2	1.318 (3)	C3—H3	0.944 (17)
N2—C1	1.344 (2)	C4—H4	0.942 (16)

C1—N1—C4	121.76 (19)	N3—C1—N2	119.96 (19)
C1—N1—H1	119.8 (16)	N1—C1—N2	121.17 (18)
C4—N1—H1	118.4 (17)	N2—C2—C3	124.4 (2)
C2—N2—C1	116.65 (18)	N2—C2—H2	111.8 (15)
C1—N3—H11	120.6 (19)	C3—C2—H2	123.6 (15)
C1—N3—H12	120.0 (16)	C4—C3—C2	117.2 (2)
H11—N3—H12	119 (3)	C4—C3—H3	123.9 (16)
O3—N4—O2	122.31 (17)	C2—C3—H3	118.9 (15)
O3—N4—O1	119.30 (18)	C3—C4—N1	118.8 (2)
O2—N4—O1	118.39 (16)	C3—C4—H4	126.9 (13)
N3—C1—N1	118.86 (18)	N1—C4—H4	114.3 (13)

C4—N1—C1—N3	−179.98 (18)	C1—N2—C2—C3	0.1 (3)
C4—N1—C1—N2	−1.2 (3)	N2—C2—C3—C4	−0.6 (3)
C2—N2—C1—N3	179.55 (19)	C2—C3—C4—N1	0.2 (3)
C2—N2—C1—N1	0.8 (3)	C1—N1—C4—C3	0.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (1)	1.87 (1)	2.742 (2)	177 (2)
N3—H11···O1	0.86 (1)	1.99 (1)	2.850 (3)	178 (2)
N3—H12···O2ⁱ	0.85 (1)	2.05 (1)	2.901 (2)	178 (2)

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₄H₆N₃⁺·NO₃⁻
M_r	158.13
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	12.632 (2), 6.2160 (8), 17.727 (2)
β (°)	99.009 (3)
V (Å³)	1374.8 (3)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.968, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	5139, 1210, 823
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.120, 0.99
No. of reflections	1210
No. of parameters	124
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.15

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalClear (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (1)	1.87 (1)	2.742 (2)	177 (2)
N3—H11···O1	0.86 (1)	1.99 (1)	2.850 (3)	178 (2)
N3—H12···O2ⁱ	0.85 (1)	2.05 (1)	2.901 (2)	178 (2)

Symmetry code: (i) x, y−1, z.

Acknowledgements

We thank the Key Project of the Natural Science Foundation of Heilongjiang Province (No. ZD200903), the Scientific Fund of Remarkable Teachers of Heilongjiang Province (No. 1054 G036), Heilongjiang University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Czupiński, O., Wojtaś, M., Ciunik, Z. & Jakubas, R. (2005). Solid State Sci. 8, 86–96. Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Lee, J.-H. P., Lewis, B. D., Mendes, J. M., Turnbull, M. M. & Awwadi, F. F. (2003). J. Coord. Chem. 56, 1425–1442. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalClear. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2009). publCIF. In preparation. Google Scholar
Ye, M.-D., Hu, M.-L. & Ye, C.-P. (2002). Z. Kristallogr. New Cryst. Struct. 217, 501–502. CAS Google Scholar