2,4-Diamino-6-methyl-1,3,5-triazin-1-ium nitrate

Fan, Y.; You, W.; Qian, H.-F.; Liu, J.-L.; Huang, W.

doi:10.1107/S1600536809003900

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o494

doi:10.1107/S1600536809003900

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2,4-Diamino-6-methyl-1,3,5-triazin-1-ium nitrate

Ying Fan,^a Wei You,^a Hui-Fen Qian,^a ^* Jian-Lan Liu ^a and Wei Huang ^b ^*

^aCollege of Sciences, Nanjing University of Technology, Nanjing 210009, People's Republic of China, and ^bState Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, People's Republic of China
^*Correspondence e-mail: whuang@nju.edu.cn,

(Received 15 January 2009; accepted 2 February 2009; online 11 February 2009)

In the title salt, C₄H₈N₅⁺·NO₃⁻, a ring N atom of 2,6-diamino-4-methyltriazine is protonated. Each anion is connected to three neighbouring cations by multiple N—H⋯O hydrogen bonds which, together with N—H⋯N contacts, generate a layer structure.

Related literature

For 2,6-diamino-4-methyltriazine compounds, see: Kaczmarek et al. (2008 ); Perpétuo & Janczak (2007 ); Portalone & Colapietro (2007 ); Wijaya et al. (2004 ); Xiao (2008 ).

Experimental

Crystal data

C₄H₈N₅⁺·NO₃⁻
M_r = 188.16
Monoclinic, P 2₁ /n
a = 7.667 (1) Å
b = 10.338 (2) Å
c = 9.977 (1) Å
β = 93.384 (2)°
V = 789.4 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.14 mm⁻¹
T = 291 (2) K
0.13 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
4763 measured reflections
1867 independent reflections
1202 reflections with I > 2σ(I)
R_int = 0.070

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.178
S = 1.00
1867 reflections
138 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O3	0.88 (2)	2.62 (2)	3.414 (3)	150 (3)
N2—H2⋯O2	0.88 (2)	2.00 (3)	2.831 (3)	156 (3)
N4—H4D⋯O1ⁱ	0.87 (2)	2.17 (2)	3.031 (3)	175 (2)
N4—H4E⋯N3ⁱⁱ	0.87 (3)	2.24 (3)	3.105 (3)	177 (2)
N5—H5B⋯O3	0.90 (1)	2.20 (1)	3.083 (3)	167 (3)
N5—H5A⋯O3ⁱⁱⁱ	0.89 (1)	2.13 (1)	3.014 (3)	174 (3)
N5—H5A⋯O1ⁱⁱⁱ	0.89 (1)	2.49 (2)	3.046 (3)	121 (2)
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y, -z+2; (iii) $[-x-{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Bruker, 2000 ); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809003900/ng2537sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003900/ng2537Isup2.hkl

checkCIF report

Comment top

The crystal structures of 2,6-diamino-4-methayltriazine with methanol and ethanol solvates (Kaczmarek et al., 2008; Xiao, 2008) and its trifluoroacetate, dimesylamide and hydrogenchlorate (Perpétuo & Janczak 2007; Wijaya et al., 2004; Portalone et al., 2007) have been reported in literature. In this paper, we report the X-ray single-crystal structure of 2,4-diamino-6-methyl-1,3,5-triazin-1-ium nitrate (I).

The molecular structure of (I) is illustrated in Fig. 1. The bond distances and bond angles are similar to those reported structures. All the non-hydrogen atoms of cations and nitrate anions are coplanar with the mean deviation from least-squares plane is 0.0745 (3) Å. The proton is suggested to be delocalized within the aromatic ring although it is added to one of the nitrogen atoms. The molecules of (I) form a layer structure where intermolecular N—H···O, N—H···N hydrogen bonds are found between adjacent molecules (Table 1). Every nitrate is connected with three neighboring cations by multiple N—H···O hydrogen contacts (Fig. 2).

Related literature top

For 2,6-diamino-4-methyltriazine compounds, see: Kaczmarek et al. (2008); Perpétuo & Janczak (2007); Portalone & Colapietro (2007); Wijaya et al. (2004); Xiao (2008).

Experimental top

Experimental The title compound was obtained as a by-product from the reaction between CuNO₃.3H₂O (180 mg, 1.0 mmol) and 2,6-diamino-4-methayltriazine (935 mg, 5.0 mmol) in methanol (30 ml). Colourless crystals of (I) were obtained by slow evaporation of the mother liquid at room temperature in air after one week. Anal.Calcd. for C₄H₈N₆O₃: C: 25.55; H: 4.29; N: 44.67%. Found: C: 25.45; H: 4.34; N: 44.56%. Main FT—IR absorptions (KBr, cm^-1): 3384 (b, s), 2396 (m), 1763 (m), 1624 (s), 1384 (s), 825 (m), and 456 (m).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (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.
	Fig. 2. Perspective view of the hydrogen bonding interactions related to every nitrate anion where the hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x, y-1, z; (ii) -x-1/2, y-1/2, -z+3/2.]

2,4-Diamino-6-methyl-1,3,5-triazin-1-ium nitrate top

Crystal data top

C₄H₈N₅⁺·NO₃⁻	F(000) = 392
M_r = 188.16	D_x = 1.583 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1324 reflections
a = 7.667 (1) Å	θ = 2.8–26.0°
b = 10.338 (2) Å	µ = 0.14 mm⁻¹
c = 9.977 (1) Å	T = 291 K
β = 93.384 (2)°	Block, colourless
V = 789.4 (2) Å³	0.13 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1202 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.070
Graphite monochromator	θ_max = 28.0°, θ_min = 2.8°
ϕ and ω scans	h = −8→10
4763 measured reflections	k = −12→13
1867 independent reflections	l = −12→13

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.106P)²] where P = (F_o² + 2F_c²)/3
1867 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.30 e Å⁻³
5 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

C₄H₈N₅⁺·NO₃⁻	V = 789.4 (2) Å³
M_r = 188.16	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.667 (1) Å	µ = 0.14 mm⁻¹
b = 10.338 (2) Å	T = 291 K
c = 9.977 (1) Å	0.13 × 0.12 × 0.10 mm
β = 93.384 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1202 reflections with I > 2σ(I)
4763 measured reflections	R_int = 0.070
1867 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	5 restraints
wR(F²) = 0.178	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.30 e Å⁻³
1867 reflections	Δρ_min = −0.38 e Å⁻³
138 parameters

Special details top

Experimental. The structure was solved by direct methods (Bruker, 2000) and successive difference Fourier syntheses.

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
C1	0.0367 (3)	0.2000 (2)	0.8411 (2)	0.0350 (5)
C2	0.3207 (3)	0.2520 (2)	0.9243 (2)	0.0368 (5)
C3	0.2268 (3)	0.0451 (2)	0.9114 (2)	0.0340 (5)
C4	0.4496 (3)	0.3560 (2)	0.9556 (3)	0.0488 (6)
H4A	0.5589	0.3183	0.9872	0.073*
H4B	0.4074	0.4113	1.0239	0.073*
H4C	0.4661	0.4057	0.8761	0.073*
H2	0.129 (4)	0.372 (2)	0.858 (3)	0.067 (9)*
H4D	0.189 (3)	−0.137 (2)	0.909 (2)	0.034 (6)*
H4E	0.371 (4)	−0.096 (2)	0.965 (3)	0.044 (7)*
N1	0.0678 (2)	0.07622 (17)	0.85890 (19)	0.0366 (5)
N2	0.1626 (2)	0.29135 (19)	0.87137 (19)	0.0373 (5)
N3	0.3580 (2)	0.13121 (17)	0.94713 (19)	0.0358 (5)
N4	0.2668 (3)	−0.07814 (18)	0.9311 (2)	0.0415 (5)
N5	−0.1161 (3)	0.2428 (2)	0.7917 (2)	0.0484 (6)
H5A	−0.193 (3)	0.1810 (18)	0.771 (3)	0.082 (9)*
H5B	−0.131 (4)	0.3288 (11)	0.783 (3)	0.066 (9)*
N6	0.0038 (2)	0.61218 (18)	0.84158 (19)	0.0391 (5)
O1	−0.0186 (2)	0.73101 (16)	0.84536 (19)	0.0515 (5)
O2	0.1471 (2)	0.56484 (18)	0.8772 (2)	0.0582 (6)
O3	−0.1190 (3)	0.54094 (17)	0.7991 (2)	0.0596 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0308 (11)	0.0347 (12)	0.0391 (11)	0.0002 (8)	−0.0019 (8)	0.0011 (9)
C2	0.0326 (12)	0.0345 (12)	0.0426 (12)	−0.0011 (9)	−0.0030 (9)	−0.0022 (9)
C3	0.0316 (11)	0.0309 (11)	0.0394 (11)	−0.0013 (8)	0.0010 (9)	−0.0007 (8)
C4	0.0425 (14)	0.0299 (12)	0.0722 (16)	−0.0060 (9)	−0.0120 (12)	−0.0034 (11)
N1	0.0307 (10)	0.0306 (10)	0.0478 (11)	−0.0016 (7)	−0.0035 (8)	0.0007 (8)
N2	0.0337 (10)	0.0280 (10)	0.0493 (11)	0.0009 (7)	−0.0056 (8)	0.0022 (8)
N3	0.0315 (10)	0.0263 (9)	0.0488 (11)	−0.0008 (7)	−0.0054 (8)	−0.0018 (7)
N4	0.0322 (11)	0.0284 (11)	0.0629 (13)	−0.0031 (8)	−0.0070 (9)	0.0015 (8)
N5	0.0351 (11)	0.0422 (13)	0.0661 (13)	0.0015 (9)	−0.0122 (9)	0.0049 (10)
N6	0.0357 (11)	0.0339 (10)	0.0474 (11)	0.0038 (8)	−0.0007 (8)	0.0017 (8)
O1	0.0459 (10)	0.0359 (10)	0.0719 (12)	0.0047 (7)	−0.0045 (8)	−0.0026 (8)
O2	0.0414 (11)	0.0514 (12)	0.0796 (14)	0.0133 (8)	−0.0134 (9)	0.0030 (9)
O3	0.0468 (11)	0.0408 (10)	0.0896 (14)	−0.0073 (8)	−0.0107 (10)	−0.0001 (9)

Geometric parameters (Å, º) top

C1—N1	1.311 (3)	C4—H4B	0.9600
C1—N5	1.321 (3)	C4—H4C	0.9600
C1—N2	1.371 (3)	N2—H2	0.88 (2)
C2—N3	1.298 (3)	N4—H4D	0.87 (2)
C2—N2	1.356 (3)	N4—H4E	0.87 (3)
C2—C4	1.481 (3)	N5—H5A	0.888 (10)
C3—N4	1.322 (3)	N5—H5B	0.900 (10)
C3—N1	1.337 (3)	N6—O2	1.236 (2)
C3—N3	1.375 (3)	N6—O1	1.241 (2)
C4—H4A	0.9600	N6—O3	1.249 (3)

N1—C1—N5	121.8 (2)	C1—N1—C3	116.22 (18)
N1—C1—N2	121.5 (2)	C2—N2—C1	118.7 (2)
N5—C1—N2	116.6 (2)	C2—N2—H2	126 (2)
N3—C2—N2	122.7 (2)	C1—N2—H2	115 (2)
N3—C2—C4	121.6 (2)	C2—N3—C3	115.26 (18)
N2—C2—C4	115.7 (2)	C3—N4—H4D	119.0 (17)
N4—C3—N1	119.2 (2)	C3—N4—H4E	117.7 (17)
N4—C3—N3	115.2 (2)	H4D—N4—H4E	123 (2)
N1—C3—N3	125.6 (2)	C1—N5—H5A	114.3 (16)
C2—C4—H4A	109.5	C1—N5—H5B	118 (2)
C2—C4—H4B	109.5	H5A—N5—H5B	128 (3)
H4A—C4—H4B	109.5	O2—N6—O1	120.34 (19)
C2—C4—H4C	109.5	O2—N6—O3	120.2 (2)
H4A—C4—H4C	109.5	O1—N6—O3	119.42 (18)
H4B—C4—H4C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.88 (2)	2.62 (2)	3.414 (3)	150 (3)
N2—H2···O2	0.88 (2)	2.00 (3)	2.831 (3)	156 (3)
N4—H4D···O1ⁱ	0.87 (2)	2.17 (2)	3.031 (3)	175 (2)
N4—H4E···N3ⁱⁱ	0.87 (3)	2.24 (3)	3.105 (3)	177 (2)
N5—H5B···O3	0.90 (1)	2.20 (1)	3.083 (3)	167 (3)
N5—H5A···O3ⁱⁱⁱ	0.89 (1)	2.13 (1)	3.014 (3)	174 (3)
N5—H5A···O1ⁱⁱⁱ	0.89 (1)	2.49 (2)	3.046 (3)	121 (2)

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

Experimental details

Crystal data
Chemical formula	C₄H₈N₅⁺·NO₃⁻
M_r	188.16
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	7.667 (1), 10.338 (2), 9.977 (1)
β (°)	93.384 (2)
V (Å³)	789.4 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.14
Crystal size (mm)	0.13 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4763, 1867, 1202
R_int	0.070
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.178, 1.00
No. of reflections	1867
No. of parameters	138
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.38

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O3	0.88 (2)	2.62 (2)	3.414 (3)	150 (3)
N2—H2···O2	0.88 (2)	2.00 (3)	2.831 (3)	156 (3)
N4—H4D···O1ⁱ	0.87 (2)	2.17 (2)	3.031 (3)	175 (2)
N4—H4E···N3ⁱⁱ	0.87 (3)	2.24 (3)	3.105 (3)	177 (2)
N5—H5B···O3	0.90 (1)	2.20 (1)	3.083 (3)	167 (3)
N5—H5A···O3ⁱⁱⁱ	0.89 (1)	2.13 (1)	3.014 (3)	174 (3)
N5—H5A···O1ⁱⁱⁱ	0.89 (1)	2.49 (2)	3.046 (3)	121 (2)

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

Acknowledgements

WH acknowledges the National Natural Science Foundation of China (No. 20871065) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry, for financial aid.

References

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