Bis(2-amino­pyrimidin-1-ium) sulfate

Hu, H.-L.; Yeh, C.-W.

doi:10.1107/S1600536812037725

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2925

https://doi.org/10.1107/S1600536812037725

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Bis(2-aminopyrimidin-1-ium) sulfate

Hui-Ling Hu ^a ‡ and Chun-Wei Yeh ^b ^*

^aDepartment of Chemical and Material Engineering, Taoyuan Innovation Institute of Technology, Jhongli 32091, Taiwan, and ^bDepartment of Chemistry, Chung-Yuan Christian University, Jhongli 32023, Taiwan
^*Correspondence e-mail: cwyeh@cycu.org.tw

(Received 21 August 2012; accepted 2 September 2012; online 12 September 2012)

In the title compound, 2C₄H₆N₃⁺·SO₄²⁻, the cations are each essentially planar with r.m.s. deviations of the fitted atoms of 0.008 and 0.002 Å. In the crystal, adjacent ions are linked by N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds, forming a three-dimensional network.

Related literature

For the crystal structures of 2-aminopyrimidinium salts with other anions, see: Cheng et al. (2010 ); Eshtiagh-Hosseini et al. (2010 ).

Experimental

Crystal data

2C₄H₆N₃⁺·SO₄²⁻
M_r = 288.30
Monoclinic, P 2₁ /n
a = 8.1215 (8) Å
b = 11.4853 (12) Å
c = 13.0407 (14) Å
β = 97.206 (2)°
V = 1206.8 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.45 × 0.29 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.880, T_max = 0.955
6656 measured reflections
2377 independent reflections
1976 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.093
S = 1.05
2377 reflections
196 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O1	0.86 (2)	1.99 (2)	2.853 (2)	175.5 (17)
N1—H1NB⋯O3ⁱ	0.91 (2)	1.97 (2)	2.882 (2)	176.9 (2)
N2—H2N⋯O2	0.86 (2)	1.79 (2)	2.640 (2)	174.7 (18)
N4—H4NA⋯O1	0.81 (2)	2.10 (2)	2.902 (2)	167.6 (19)
N4—H4NB⋯O3ⁱⁱ	0.78 (2)	2.19 (2)	2.962 (2)	171.0 (2)
N5—H5N⋯O4ⁱⁱ	0.80 (2)	1.84 (2)	2.631 (2)	172.6 (2)
C2—H2A⋯O4ⁱⁱⁱ	0.93	2.50	3.295 (2)	144
C3—H3A⋯N6^iv	0.93	2.58	3.382 (2)	145
C4—H4A⋯O1^v	0.93	2.57	3.231 (2)	128
C7—H7A⋯O2^vi	0.93	2.51	3.101 (2)	121
C8—H8A⋯O4^vii	0.93	2.59	3.237 (2)	127
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x, -y+1, -z+1; (iii) -x, -y+1, -z+2; (iv) -x+1, -y+1, -z+2; (v) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812037725/pv2583sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812037725/pv2583Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812037725/pv2583Isup3.cml

checkCIF report

Comment top

There are several supramolecular structures containing 2-aminopyrimidinium cations with other anions constructed by hydrogen bonds (Cheng, et al. 2010; Eshtiagh-Hosseini, et al., 2010). The asymmetric unit of the title compound, consists of two independent 2-aminopyrimidinium cations and a sulfate anion (Fig. 1). These two protonated pyrimidine rings are not co-planar but twisted with each other by an interplanar angle of 84.3 (1)°. The cations and anions are interlinked through N—H···O, C—H···O and C—H···N hydrogen bonds resulting in a three-dimensional net work (Fig. 2, Tab. 1).

Related literature top

For the crystal structures of 2-aminopyrimidinium salts with other anions, see: Cheng et al. (2010); Eshtiagh-Hosseini et al. (2010).

Experimental top

An aqueous solution (5.0 ml) of zinc sulfate (1.0 mmol) was layered carefully over a methanolic solution (5.0 ml) of 2-aminopyrimidine (1.0 mmol) in a tube. Colourless crystals were obtained after several weeks. These were washed with methanol and collected in 85.8% yield.

Structure description top

For the crystal structures of 2-aminopyrimidinium salts with other anions, see: Cheng et al. (2010); Eshtiagh-Hosseini et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. A view of the N—H···O, C—H···O and C—H···N hydrogen bonds (dotted lines) in the crystal structure of the title compound.

Bis(2-aminopyrimidin-1-ium) sulfate top

Crystal data top

2C₄H₆N₃⁺·SO₄²⁻	F(000) = 600
M_r = 288.30	D_x = 1.587 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3511 reflections
a = 8.1215 (8) Å	θ = 2.5–26.0°
b = 11.4853 (12) Å	µ = 0.29 mm⁻¹
c = 13.0407 (14) Å	T = 293 K
β = 97.206 (2)°	Plate, colourless
V = 1206.8 (2) Å³	0.45 × 0.29 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	2377 independent reflections
Radiation source: fine-focus sealed tube	1976 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
φ & ω scans	θ_max = 26.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −10→10
T_min = 0.880, T_max = 0.955	k = −14→8
6656 measured reflections	l = −16→14

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0546P)² + 0.1486P] where P = (F_o² + 2F_c²)/3
2377 reflections	(Δ/σ)_max = 0.001
196 parameters	Δρ_max = 0.19 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³

Crystal data top

2C₄H₆N₃⁺·SO₄²⁻	V = 1206.8 (2) Å³
M_r = 288.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.1215 (8) Å	µ = 0.29 mm⁻¹
b = 11.4853 (12) Å	T = 293 K
c = 13.0407 (14) Å	0.45 × 0.29 × 0.16 mm
β = 97.206 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	2377 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	1976 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.955	R_int = 0.032
6656 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.093	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.19 e Å⁻³
2377 reflections	Δρ_min = −0.40 e Å⁻³
196 parameters

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

	x	y	z	U_iso*/U_eq
S	0.01967 (5)	0.48062 (3)	0.75579 (3)	0.03308 (15)
C1	0.4028 (2)	0.33089 (14)	0.95900 (13)	0.0353 (4)
C2	0.3254 (2)	0.46070 (16)	1.08388 (13)	0.0422 (4)
H2A	0.2577	0.5207	1.1019	0.051*
C3	0.4431 (2)	0.41520 (16)	1.15527 (15)	0.0498 (5)
H3A	0.4602	0.4431	1.2227	0.060*
C4	0.5372 (2)	0.32455 (17)	1.12244 (15)	0.0507 (5)
H4A	0.6183	0.2919	1.1706	0.061*
C5	0.32224 (19)	0.58057 (14)	0.50457 (12)	0.0328 (4)
C6	0.4389 (2)	0.72057 (15)	0.40373 (14)	0.0435 (4)
H6A	0.4403	0.7583	0.3408	0.052*
C7	0.5485 (2)	0.75007 (17)	0.48542 (16)	0.0514 (5)
H7A	0.6271	0.8081	0.4808	0.062*
C8	0.5392 (2)	0.69007 (16)	0.57723 (15)	0.0483 (5)
H8A	0.6150	0.7092	0.6342	0.058*
N1	0.3820 (2)	0.29315 (15)	0.86293 (12)	0.0455 (4)
H1NA	0.312 (2)	0.3295 (18)	0.8188 (16)	0.050 (6)*
H1NB	0.435 (3)	0.227 (2)	0.8471 (16)	0.065 (6)*
N2	0.30658 (17)	0.41906 (12)	0.98686 (11)	0.0362 (3)
H2N	0.230 (2)	0.4489 (17)	0.9436 (15)	0.042 (5)*
N3	0.51952 (18)	0.28162 (13)	1.02800 (12)	0.0458 (4)
N4	0.2118 (2)	0.49912 (14)	0.51195 (14)	0.0425 (4)
H4NA	0.207 (2)	0.4694 (18)	0.5680 (17)	0.047 (6)*
H4NB	0.157 (2)	0.4774 (17)	0.4623 (17)	0.044 (6)*
N5	0.32700 (18)	0.63601 (13)	0.41351 (11)	0.0365 (3)
H5N	0.258 (3)	0.6232 (18)	0.3654 (17)	0.055 (6)*
N6	0.43008 (17)	0.60804 (13)	0.58842 (11)	0.0407 (4)
O1	0.16275 (15)	0.42397 (11)	0.71839 (9)	0.0458 (3)
O2	0.06654 (16)	0.51991 (11)	0.86283 (9)	0.0481 (3)
O3	−0.03729 (15)	0.57920 (10)	0.68927 (9)	0.0455 (3)
O4	−0.11722 (15)	0.39661 (11)	0.75484 (9)	0.0470 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0389 (2)	0.0320 (2)	0.0269 (2)	−0.00002 (16)	−0.00122 (16)	0.00050 (15)
C1	0.0331 (8)	0.0321 (8)	0.0402 (9)	−0.0035 (6)	0.0027 (7)	0.0042 (7)
C2	0.0478 (10)	0.0425 (10)	0.0379 (10)	−0.0031 (8)	0.0115 (8)	0.0015 (7)
C3	0.0645 (12)	0.0507 (12)	0.0324 (9)	−0.0060 (9)	−0.0003 (8)	0.0056 (8)
C4	0.0527 (11)	0.0497 (11)	0.0454 (11)	−0.0019 (9)	−0.0103 (9)	0.0149 (8)
C5	0.0334 (8)	0.0348 (9)	0.0300 (8)	0.0057 (7)	0.0039 (6)	−0.0010 (6)
C6	0.0446 (10)	0.0397 (10)	0.0475 (10)	0.0027 (8)	0.0106 (8)	0.0083 (8)
C7	0.0492 (11)	0.0425 (11)	0.0611 (12)	−0.0085 (9)	0.0010 (9)	0.0039 (9)
C8	0.0470 (10)	0.0452 (11)	0.0496 (11)	−0.0040 (9)	−0.0064 (8)	−0.0052 (9)
N1	0.0529 (10)	0.0413 (9)	0.0402 (9)	0.0099 (7)	−0.0023 (7)	−0.0033 (7)
N2	0.0327 (7)	0.0390 (8)	0.0359 (8)	0.0016 (6)	0.0011 (6)	0.0042 (6)
N3	0.0454 (8)	0.0429 (9)	0.0468 (9)	0.0057 (7)	−0.0030 (7)	0.0083 (7)
N4	0.0437 (9)	0.0510 (10)	0.0318 (8)	−0.0089 (7)	0.0005 (7)	0.0033 (7)
N5	0.0367 (8)	0.0414 (8)	0.0306 (8)	0.0012 (6)	0.0013 (6)	0.0015 (6)
N6	0.0427 (8)	0.0446 (9)	0.0334 (7)	−0.0002 (6)	−0.0012 (6)	−0.0012 (6)
O1	0.0516 (7)	0.0509 (8)	0.0354 (7)	0.0103 (6)	0.0074 (5)	0.0021 (5)
O2	0.0541 (8)	0.0532 (8)	0.0334 (7)	0.0134 (6)	−0.0093 (5)	−0.0125 (5)
O3	0.0528 (7)	0.0358 (7)	0.0451 (7)	−0.0001 (5)	−0.0055 (6)	0.0084 (5)
O4	0.0518 (8)	0.0488 (8)	0.0387 (7)	−0.0128 (6)	−0.0012 (5)	0.0086 (5)

Geometric parameters (Å, º) top

S—O3	1.4656 (12)	C5—N6	1.350 (2)
S—O1	1.4675 (13)	C5—N5	1.352 (2)
S—O4	1.4709 (12)	C6—C7	1.343 (3)
S—O2	1.4710 (12)	C6—N5	1.347 (2)
C1—N1	1.316 (2)	C6—H6A	0.9300
C1—N3	1.347 (2)	C7—C8	1.392 (3)
C1—N2	1.356 (2)	C7—H7A	0.9300
C2—N2	1.343 (2)	C8—N6	1.314 (2)
C2—C3	1.353 (3)	C8—H8A	0.9300
C2—H2A	0.9300	N1—H1NA	0.86 (2)
C3—C4	1.390 (3)	N1—H1NB	0.91 (2)
C3—H3A	0.9300	N2—H2N	0.86 (2)
C4—N3	1.318 (2)	N4—H4NA	0.81 (2)
C4—H4A	0.9300	N4—H4NB	0.78 (2)
C5—N4	1.308 (2)	N5—H5N	0.80 (2)

O3—S—O1	110.49 (8)	C7—C6—H6A	120.2
O3—S—O4	108.64 (7)	N5—C6—H6A	120.2
O1—S—O4	109.60 (8)	C6—C7—C8	117.11 (17)
O3—S—O2	110.46 (7)	C6—C7—H7A	121.4
O1—S—O2	109.27 (7)	C8—C7—H7A	121.4
O4—S—O2	108.34 (8)	N6—C8—C7	124.08 (17)
N1—C1—N3	119.53 (16)	N6—C8—H8A	118.0
N1—C1—N2	119.43 (16)	C7—C8—H8A	118.0
N3—C1—N2	121.03 (16)	C1—N1—H1NA	118.1 (14)
N2—C2—C3	119.86 (17)	C1—N1—H1NB	119.0 (14)
N2—C2—H2A	120.1	H1NA—N1—H1NB	122.7 (19)
C3—C2—H2A	120.1	C2—N2—C1	121.12 (15)
C2—C3—C4	116.45 (18)	C2—N2—H2N	117.7 (13)
C2—C3—H3A	121.8	C1—N2—H2N	121.2 (13)
C4—C3—H3A	121.8	C4—N3—C1	116.88 (16)
N3—C4—C3	124.65 (16)	C5—N4—H4NA	118.6 (14)
N3—C4—H4A	117.7	C5—N4—H4NB	119.6 (15)
C3—C4—H4A	117.7	H4NA—N4—H4NB	122 (2)
N4—C5—N6	119.26 (15)	C6—N5—C5	121.10 (16)
N4—C5—N5	119.79 (15)	C6—N5—H5N	118.3 (15)
N6—C5—N5	120.95 (15)	C5—N5—H5N	120.4 (15)
C7—C6—N5	119.64 (17)	C8—N6—C5	117.11 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O1	0.86 (2)	1.99 (2)	2.853 (2)	175.5 (17)
N1—H1NB···O3ⁱ	0.91 (2)	1.97 (2)	2.882 (2)	176.9 (2)
N2—H2N···O2	0.86 (2)	1.79 (2)	2.640 (2)	174.7 (18)
N4—H4NA···O1	0.81 (2)	2.10 (2)	2.902 (2)	167.6 (19)
N4—H4NB···O3ⁱⁱ	0.78 (2)	2.19 (2)	2.962 (2)	171.0 (2)
N5—H5N···O4ⁱⁱ	0.80 (2)	1.84 (2)	2.631 (2)	172.6 (2)
C2—H2A···O4ⁱⁱⁱ	0.93	2.50	3.295 (2)	144
C3—H3A···N6^iv	0.93	2.58	3.382 (2)	145
C4—H4A···O1^v	0.93	2.57	3.231 (2)	128
C7—H7A···O2^vi	0.93	2.51	3.101 (2)	121
C8—H8A···O4^vii	0.93	2.59	3.237 (2)	127

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

Experimental details

Crystal data
Chemical formula	2C₄H₆N₃⁺·SO₄²⁻
M_r	288.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.1215 (8), 11.4853 (12), 13.0407 (14)
β (°)	97.206 (2)
V (Å³)	1206.8 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.45 × 0.29 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.880, 0.955
No. of measured, independent and observed [I > 2σ(I)] reflections	6656, 2377, 1976
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.093, 1.05
No. of reflections	2377
No. of parameters	196
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.40

Computer programs: APEX2 (Bruker, 2010), SAINT (Bruker, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1NA···O1	0.86 (2)	1.99 (2)	2.853 (2)	175.5 (17)
N1—H1NB···O3ⁱ	0.91 (2)	1.97 (2)	2.882 (2)	176.9 (2)
N2—H2N···O2	0.86 (2)	1.79 (2)	2.640 (2)	174.7 (18)
N4—H4NA···O1	0.81 (2)	2.10 (2)	2.902 (2)	167.6 (19)
N4—H4NB···O3ⁱⁱ	0.78 (2)	2.19 (2)	2.962 (2)	171.0 (2)
N5—H5N···O4ⁱⁱ	0.80 (2)	1.84 (2)	2.631 (2)	172.6 (2)
C2—H2A···O4ⁱⁱⁱ	0.93	2.50	3.295 (2)	144.2
C3—H3A···N6^iv	0.93	2.58	3.382 (2)	144.8
C4—H4A···O1^v	0.93	2.57	3.231 (2)	128.2
C7—H7A···O2^vi	0.93	2.51	3.101 (2)	121.3
C8—H8A···O4^vii	0.93	2.59	3.237 (2)	126.9

Footnotes

‡Current address: Department of Hospitality Management, Taoyuan Innovation Institute of Technology, Jhongli 32091, Taiwan.

Acknowledgements

We are grateful to the National Science Council of the Republic of China and the Taoyuan Innovation Institute of Technology for support.

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2000). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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