2-Amino-4-methyl­pyrimidinium dihydrogen phosphate

Abstract

A charge-assisted hydrogen-bonding network involving N—H⋯O and O—H⋯O hydrogen bonds stabilizes the crystal of the title salt, C₅H₈N₃ ⁺·H₂PO₄ ⁻. The dihydrogen phosphate anions form one-dimensional chains along [100], via O—H⋯O hydrogen bonds. The 2-amino-4-methyl­pyrimidinium cations are linked to these chains by means of two different kinds of N—H⋯O hydrogen bonds. Neighbouring chains are linked via C—H⋯N and C—H⋯O hydrogen bonds forming two-dimensional slab-like networks lying parallel to (01-1).

Related literature  

Intriguing anion clusters formed by the supra­molecular assembly of dihydrogen phosphates have been investigated recently (see: Hossain et al., 2012 ▶). Methyl­pyrimidine derivatives are known to be synthetic precursors to many bioactive pyrimidine derivatives (see: Xue et al., 1993 ▶). Metal complexes of pyrimidines (see: Zhu et al., 2008 ▶) and their proton transfer complexes with mineral acids are reported (see: Aakeroy et al., 2003 ▶). The infinite O—H⋯O hydrogen-bond chain present in this material is a structural feature suggestive of possible proton conducting behaviour (see: Haile et al., 2001 ▶).

Experimental  

Crystal data  

• C₅H₈N₃ ⁺·H₂PO₄ ⁻

• M _r = 207.13

• Triclinic,

• a = 6.1720 (2) Å

• b = 7.5616 (3) Å

• c = 9.9216 (4) Å

• α = 100.562 (3)°

• β = 99.821 (3)°

• γ = 102.279 (4)°

• V = 434.07 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 0.31 mm⁻¹

• T = 295 K

• 0.25 × 0.20 × 0.18 mm

Data collection  

• Oxford Xcalibur Eos (Nova) CCD detector diffractometer

• Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.928, T _max = 0.947

• 9718 measured reflections

• 1717 independent reflections

• 1546 reflections with I > 2σ(I)

• R _int = 0.027

Refinement  

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.088

• S = 1.08

• 1717 reflections

• 125 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.34 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED (Oxford Diffraction, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and WinGX (Farrugia, 2012 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

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⋯O4i	0.82	1.80	2.6100 (18)	168
N1—H1N⋯O2ii	0.86	2.14	3.000 (2)	177
O2—H2⋯O4iii	0.82	1.80	2.5843 (17)	161
N1—H2N⋯O3iv	0.86	2.01	2.845 (2)	163
N3—H3N⋯O3ii	0.90 (2)	1.73 (2)	2.6276 (19)	173 (2)
C4—H4⋯N2v	0.93	2.55	3.463 (2)	166
C5—H5B⋯O1vi	0.96	2.58	3.531 (3)	171

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

supplementary crystallographic information

Comment

The title compound, a multicomponent crystal, AMHP, crystallizes in triclinic P-1, with a protonated 2-amino-4-methylpyrimidine molecule and a dihydrogenphosphate moiety in the asymmetric unit (Fig. 1). The dihydrogenphosphate residue forms a chain via O—H···O hydrogen bonds. 2-Amino-4-methylpyrimidinium cations are linked to these chains by means of two different kinds of N—H···O hydrogen bonds. The crystal packing is stabilized by N—H···O and O—H···O hydrogen bonds and the resulting supramolecular assembly is shown in Figure 2. The infinite hydrogen bond chains present in this structure are of special interest due to the anticipated proton conductivity of the material (see: Haile et al.2001).

Experimental

The title compound was prepared by treating 2-amino 4-methyl pyramidine with phosphoric acid (H3PO4) in aqueous solution (Scheme 1) in 1:1 molar ratio. The crystals were harvested from the solution after 10 days and suitable crystal for single-crystal X-ray diffraction study were chosen using a polarizing microscope.

Refinement

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis PRO (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008), WinGX(Farrugia, 2012); molecular graphics: Mercury 2.3 (Macrae et al. 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

Fig. 1.

ORTEP view of the title compound with the atom numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Fig. 2.

A view of supramolecular chain showing the hydrogen bonding between dihydrogen phosphate residues and the interlinked 2-amino-4-methylpyrimidine molecules.

Crystal data

C5H8N3+·H2PO4−	Z = 2
Mr = 207.13	F(000) = 216
Triclinic, P1	Least Squares Treatment of 25 SET4 setting angles.
Hall symbol: -P 1	Dx = 1.585 Mg m−3
a = 6.1720 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.5616 (3) Å	Cell parameters from 326 reflections
c = 9.9216 (4) Å	θ = 2.8–26.0°
α = 100.562 (3)°	µ = 0.31 mm−1
β = 99.821 (3)°	T = 295 K
γ = 102.279 (4)°	Block, colourless
V = 434.07 (3) Å3	0.25 × 0.20 × 0.18 mm

Data collection

Oxford Xcalibur Eos (Nova) CCD detector diffractometer	1717 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1546 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
ω scans	θmax = 26.0°, θmin = 2.8°
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006)	h = −7→7
Tmin = 0.928, Tmax = 0.947	k = −9→9
9718 measured reflections	l = −12→12

Refinement

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.088	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0449P)2 + 0.1805P] where P = (Fo2 + 2Fc2)/3
1717 reflections	(Δ/σ)max < 0.001
125 parameters	Δρmax = 0.21 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.1136 (3)	0.3869 (2)	1.11795 (16)	0.0405 (5)
N2	−0.0464 (2)	0.1740 (2)	0.90738 (15)	0.0332 (4)
N3	0.3480 (2)	0.2530 (2)	0.99937 (15)	0.0326 (4)
C1	0.1379 (3)	0.2712 (2)	1.00803 (17)	0.0293 (5)
C2	−0.0146 (3)	0.0613 (2)	0.79698 (18)	0.0341 (5)
C3	0.2007 (3)	0.0371 (3)	0.7852 (2)	0.0407 (6)
C4	0.3796 (3)	0.1362 (3)	0.88869 (19)	0.0386 (6)
C5	−0.2202 (4)	−0.0381 (3)	0.6843 (2)	0.0507 (7)
P1	0.28422 (7)	0.48498 (6)	0.64883 (4)	0.0283 (1)
O1	0.0685 (2)	0.31898 (17)	0.59152 (14)	0.0418 (4)
O2	0.4901 (2)	0.39299 (18)	0.64980 (12)	0.0365 (4)
O3	0.2949 (2)	0.5709 (2)	0.79898 (13)	0.0439 (4)
O4	0.29115 (19)	0.61556 (16)	0.55043 (13)	0.0336 (4)
H1N	0.23060	0.44920	1.18240	0.0490*
H2N	−0.01930	0.40020	1.12510	0.0490*
H3	0.21960	−0.04470	0.70830	0.0490*
H3N	0.464 (4)	0.319 (3)	1.071 (2)	0.048 (6)*
H4	0.52500	0.12390	0.88380	0.0460*
H5A	−0.31890	−0.12620	0.71950	0.0760*
H5B	−0.17500	−0.10210	0.60520	0.0760*
H5C	−0.29890	0.05020	0.65580	0.0760*
H1	−0.03370	0.35420	0.54850	0.0630*
H2	0.53240	0.39280	0.57580	0.0550*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0258 (7)	0.0530 (9)	0.0348 (8)	0.0121 (7)	0.0011 (6)	−0.0069 (7)
N2	0.0252 (7)	0.0384 (8)	0.0319 (7)	0.0049 (6)	0.0049 (6)	0.0030 (6)
N3	0.0238 (7)	0.0423 (8)	0.0309 (7)	0.0087 (6)	0.0047 (6)	0.0069 (6)
C1	0.0241 (8)	0.0338 (8)	0.0303 (8)	0.0081 (6)	0.0052 (6)	0.0081 (7)
C2	0.0327 (9)	0.0334 (8)	0.0331 (9)	0.0033 (7)	0.0079 (7)	0.0048 (7)
C3	0.0410 (10)	0.0435 (10)	0.0373 (10)	0.0132 (8)	0.0140 (8)	0.0003 (8)
C4	0.0315 (9)	0.0494 (10)	0.0403 (10)	0.0173 (8)	0.0134 (8)	0.0103 (8)
C5	0.0393 (11)	0.0546 (12)	0.0424 (11)	−0.0023 (9)	0.0047 (8)	−0.0077 (9)
P1	0.0201 (2)	0.0388 (3)	0.0242 (2)	0.0076 (2)	0.0030 (2)	0.0046 (2)
O1	0.0294 (7)	0.0421 (7)	0.0492 (8)	0.0029 (5)	−0.0041 (6)	0.0177 (6)
O2	0.0300 (6)	0.0563 (8)	0.0293 (6)	0.0201 (6)	0.0081 (5)	0.0126 (6)
O3	0.0298 (7)	0.0705 (9)	0.0280 (7)	0.0165 (6)	0.0057 (5)	−0.0015 (6)
O4	0.0238 (6)	0.0396 (6)	0.0379 (7)	0.0078 (5)	0.0066 (5)	0.0106 (5)

Geometric parameters (Å, º)

P1—O3	1.4964 (13)	N1—H2N	0.8600
P1—O1	1.5623 (14)	N1—H1N	0.8600
P1—O2	1.5725 (14)	N3—H3N	0.90 (2)
P1—O4	1.5098 (13)	C2—C5	1.492 (3)
O1—H1	0.8200	C2—C3	1.401 (3)
O2—H2	0.8200	C3—C4	1.347 (3)
N1—C1	1.319 (2)	C3—H3	0.9300
N2—C2	1.329 (2)	C4—H4	0.9300
N2—C1	1.349 (2)	C5—H5C	0.9600
N3—C1	1.348 (2)	C5—H5A	0.9600
N3—C4	1.347 (2)	C5—H5B	0.9600
P1···H3Ni	2.89 (2)	C2···C1ix	3.481 (2)
P1···H2Nii	3.1000	C2···O1	3.099 (2)
P1···H1iii	2.8900	C3···O1	3.257 (2)
P1···H1Ni	3.0600	C4···O2	3.395 (2)
P1···H2iv	2.8800	C5···O1	3.277 (3)
O1···C3	3.257 (2)	C5···H4viii	2.9800
O1···C5	3.277 (3)	H1···P1iii	2.8900
O1···O4iii	2.6100 (18)	H1···O4iii	1.8000
O1···C2	3.099 (2)	H1···H1iii	2.5500
O2···N1i	3.000 (2)	H1N···H2i	2.5200
O2···C4	3.395 (2)	H1N···H3N	2.2400
O2···O4iv	2.5843 (17)	H1N···P1i	3.0600
O3···N1ii	2.845 (2)	H1N···O2i	2.1400
O3···N3i	2.6276 (19)	H2···O4iv	1.8000
O4···O1iii	2.6100 (18)	H2···H1Ni	2.5200
O4···O2iv	2.5843 (17)	H2···H2iv	2.4500
O1···H5Bv	2.5800	H2···P1iv	2.8800
O2···H1Ni	2.1400	H2N···P1ii	3.1000
O3···H3Ni	1.73 (2)	H2N···O3ii	2.0100
O3···H2Nii	2.0100	H3···O4x	2.9100
O4···H2iv	1.8000	H3···H5B	2.3900
O4···H1iii	1.8000	H3N···H1N	2.2400
O4···H3vi	2.9100	H3N···P1i	2.89 (2)
O4···H5Avii	2.8000	H3N···O3i	1.73 (2)
N1···O2i	3.000 (2)	H4···N2xi	2.5500
N1···O3ii	2.845 (2)	H4···C5xi	2.9800
N3···O3i	2.6276 (19)	H5A···O4xii	2.8000
N2···H4viii	2.5500	H5B···H3	2.3900
C1···C2ix	3.481 (2)	H5B···O1v	2.5800
O3—P1—O4	115.79 (8)	N2—C1—N3	121.54 (15)
O1—P1—O3	109.84 (8)	N2—C2—C3	122.14 (16)
O1—P1—O4	109.55 (7)	N2—C2—C5	116.73 (17)
O1—P1—O2	104.78 (7)	C3—C2—C5	121.13 (17)
O2—P1—O4	110.13 (7)	C2—C3—C4	117.84 (18)
O2—P1—O3	106.13 (7)	N3—C4—C3	120.03 (18)
P1—O1—H1	109.00	C2—C3—H3	121.00
P1—O2—H2	109.00	C4—C3—H3	121.00
C1—N2—C2	117.90 (15)	C3—C4—H4	120.00
C1—N3—C4	120.52 (15)	N3—C4—H4	120.00
H1N—N1—H2N	120.00	C2—C5—H5B	109.00
C1—N1—H1N	120.00	C2—C5—H5C	109.00
C1—N1—H2N	120.00	C2—C5—H5A	109.00
C1—N3—H3N	117.5 (15)	H5A—C5—H5C	109.00
C4—N3—H3N	121.9 (15)	H5B—C5—H5C	109.00
N1—C1—N3	118.80 (16)	H5A—C5—H5B	110.00
N1—C1—N2	119.66 (17)
C2—N2—C1—N1	178.81 (15)	C4—N3—C1—N2	0.1 (2)
C2—N2—C1—N3	−1.3 (2)	C1—N3—C4—C3	0.3 (3)
C1—N2—C2—C3	2.1 (2)	N2—C2—C3—C4	−1.7 (3)
C1—N2—C2—C5	−177.38 (16)	C5—C2—C3—C4	177.75 (19)
C4—N3—C1—N1	−179.98 (18)	C2—C3—C4—N3	0.4 (3)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x, −y+1, −z+2; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x, −y, −z+1; (vi) x, y+1, z; (vii) x+1, y+1, z; (viii) x−1, y, z; (ix) −x, −y, −z+2; (x) x, y−1, z; (xi) x+1, y, z; (xii) x−1, y−1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O4iii	0.82	1.80	2.6100 (18)	168
N1—H1N···O2i	0.86	2.14	3.000 (2)	177
O2—H2···O4iv	0.82	1.80	2.5843 (17)	161
N1—H2N···O3ii	0.86	2.01	2.845 (2)	163
N3—H3N···O3i	0.90 (2)	1.73 (2)	2.6276 (19)	173 (2)
C4—H4···N2xi	0.93	2.55	3.463 (2)	166
C5—H5B···O1v	0.96	2.58	3.531 (3)	171

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