2,4-Diamino-6-methyl-1,3,5-triazin-1-ium hydrogen oxalate.

The title compound, C(4)H(8)N(5) (+)·C(2)HO(4) (-), was obtained from the reaction of oxalic acid and 2,4-diamino-6-methyl-1,3,5-triazine. The protonated triazine ring is essentially planar with a maximum deviation of 0.035 (1) Å, but the hydrogen oxalate anion is less planar, with a maximum deviation of 0.131 (1) Å for both carbonyl O atoms. In the crystal, the ions are linked by inter-molecular N-H⋯O, N-H⋯N, O-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional network. Weak π-π [centroid-centroid distance = 3.763 Å] and C-O⋯π inter-actions [O⋯centroid = 3.5300 (16) Å, C-O⋯centroid = 132.19 (10)°] are also present.

Related literature

For bond-length data see: Allen et al. (1987 ▶) and for a description of the Cambridge Structural Database, see: Allen (2002 ▶). For background to triazine derivatives, see: Sebenik et al. (1989 ▶). For related structures, see: Kaczmarek et al. (2008 ▶); Xiao (2008 ▶); Fan et al. (2009 ▶); Qian & Huang (2010 ▶).

Experimental

Crystal data

C4H8N5 +·C2HO4 −

M = 215.18

Triclinic,

a = 5.6208 (12) Å

b = 7.9828 (17) Å

c = 10.857 (2) Å

α = 76.846 (4)°

β = 75.882 (4)°

γ = 75.954 (4)°

V = 450.92 (17) Å3

Z = 2

Mo Kα radiation

μ = 0.13 mm−1

T = 298 K

0.50 × 0.22 × 0.19 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.935, T max = 0.974

5551 measured reflections

1959 independent reflections

1708 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.113

S = 1.03

1959 reflections

145 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.27 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812016637/zq2157sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812016637/zq2157Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812016637/zq2157Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C4H8N5+·C2HO4−	Z = 2
Mr = 215.18	F(000) = 224
Triclinic, P1	Dx = 1.585 Mg m−3
Hall symbol: -P 1	Melting point = 492.2–492.5 K
a = 5.6208 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9828 (17) Å	Cell parameters from 1963 reflections
c = 10.857 (2) Å	θ = 1.9–27.0°
α = 76.846 (4)°	µ = 0.13 mm−1
β = 75.882 (4)°	T = 298 K
γ = 75.954 (4)°	Block, colourless
V = 450.92 (17) Å3	0.50 × 0.22 × 0.19 mm

Bruker SMART APEX CCD area-detector diffractometer	1959 independent reflections
Radiation source: fine-focus sealed tube	1708 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 83.66 pixels mm-1	θmax = 27.0°, θmin = 1.9°
ω scan	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −10→10
Tmin = 0.935, Tmax = 0.974	l = −13→13
5551 measured reflections

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0664P)2 + 0.0976P] where P = (Fo2 + 2Fc2)/3
1959 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.25 e Å−3
1 restraint	Δρmin = −0.27 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	1.01323 (19)	0.22067 (16)	1.09284 (10)	0.0435 (3)
O2	1.20977 (17)	0.36561 (14)	0.91142 (9)	0.0383 (3)
O3	0.8189 (2)	0.38620 (18)	0.80042 (10)	0.0490 (3)
O4	0.60164 (18)	0.30135 (15)	0.99698 (10)	0.0401 (3)
H4	0.476 (3)	0.322 (3)	0.964 (2)	0.076 (7)*
N1	0.2651 (2)	0.08398 (15)	0.40173 (11)	0.0342 (3)
N2	0.3693 (2)	0.31924 (15)	0.46944 (11)	0.0326 (3)
N3	0.5937 (2)	0.21615 (15)	0.28003 (11)	0.0324 (3)
H3	0.733 (4)	0.221 (2)	0.2103 (19)	0.049 (5)*
N4	0.0411 (2)	0.18887 (17)	0.58245 (12)	0.0421 (3)
H4D	0.0102	0.2572	0.6377	0.051*
H4E	−0.0506	0.1130	0.5922	0.051*
N5	0.7025 (2)	0.43757 (17)	0.34456 (12)	0.0393 (3)
H5A	0.6827	0.5064	0.3983	0.047*
H5B	0.8206	0.4415	0.2771	0.047*
C1	0.4493 (3)	0.09606 (17)	0.30219 (13)	0.0307 (3)
C2	0.2280 (3)	0.20042 (18)	0.48339 (13)	0.0316 (3)
C3	0.5530 (3)	0.32675 (18)	0.36537 (12)	0.0302 (3)
C4	0.5070 (3)	−0.0268 (2)	0.21033 (15)	0.0400 (4)
H4A	0.5078	−0.1442	0.2574	0.060*
H4B	0.6685	−0.0204	0.1560	0.060*
H4C	0.3822	0.0048	0.1580	0.060*
C5	1.0268 (2)	0.30348 (18)	0.98158 (13)	0.0296 (3)
C6	0.8009 (2)	0.33563 (18)	0.91548 (13)	0.0301 (3)

	U11	U22	U33	U12	U13	U23
O1	0.0288 (5)	0.0646 (7)	0.0332 (6)	−0.0124 (5)	−0.0051 (4)	0.0009 (5)
O2	0.0237 (5)	0.0565 (7)	0.0344 (6)	−0.0147 (4)	−0.0014 (4)	−0.0052 (5)
O3	0.0351 (6)	0.0828 (9)	0.0297 (6)	−0.0157 (6)	−0.0046 (4)	−0.0093 (5)
O4	0.0234 (5)	0.0622 (7)	0.0351 (6)	−0.0161 (5)	−0.0038 (4)	−0.0035 (5)
N1	0.0374 (7)	0.0359 (6)	0.0315 (6)	−0.0161 (5)	0.0015 (5)	−0.0103 (5)
N2	0.0381 (6)	0.0360 (6)	0.0262 (6)	−0.0158 (5)	0.0009 (5)	−0.0091 (5)
N3	0.0344 (6)	0.0375 (6)	0.0265 (6)	−0.0140 (5)	0.0022 (5)	−0.0097 (5)
N4	0.0467 (7)	0.0500 (8)	0.0340 (7)	−0.0264 (6)	0.0091 (5)	−0.0165 (6)
N5	0.0447 (7)	0.0487 (7)	0.0297 (6)	−0.0263 (6)	0.0048 (5)	−0.0124 (5)
C1	0.0338 (7)	0.0308 (6)	0.0282 (7)	−0.0090 (5)	−0.0039 (5)	−0.0061 (5)
C2	0.0353 (7)	0.0343 (7)	0.0263 (7)	−0.0126 (6)	−0.0019 (5)	−0.0064 (5)
C3	0.0338 (7)	0.0337 (7)	0.0241 (6)	−0.0117 (5)	−0.0031 (5)	−0.0045 (5)
C4	0.0471 (9)	0.0389 (8)	0.0360 (8)	−0.0132 (6)	0.0003 (6)	−0.0147 (6)
C5	0.0222 (6)	0.0375 (7)	0.0291 (7)	−0.0064 (5)	−0.0002 (5)	−0.0110 (5)
C6	0.0247 (6)	0.0381 (7)	0.0289 (7)	−0.0084 (5)	−0.0013 (5)	−0.0103 (5)

O1—C5	1.2322 (17)	N4—C2	1.3112 (18)
O2—C5	1.2560 (16)	N4—H4D	0.8600
O3—C6	1.2093 (17)	N4—H4E	0.8600
O4—C6	1.2913 (16)	N5—C3	1.3104 (18)
O4—H4	0.831 (10)	N5—H5A	0.8600
N1—C1	1.3054 (18)	N5—H5B	0.8600
N1—C2	1.3727 (17)	C1—C4	1.4812 (19)
N2—C3	1.3329 (17)	C4—H4A	0.9600
N2—C2	1.3400 (17)	C4—H4B	0.9600
N3—C1	1.3465 (17)	C4—H4C	0.9600
N3—C3	1.3643 (18)	C5—C6	1.5476 (19)
N3—H3	0.950 (19)
C6—O4—H4	113.8 (16)	N2—C2—N1	124.86 (12)
C1—N1—C2	116.03 (12)	N5—C3—N2	120.67 (12)
C3—N2—C2	116.42 (11)	N5—C3—N3	118.55 (12)
C1—N3—C3	119.67 (12)	N2—C3—N3	120.76 (12)
C1—N3—H3	122.3 (11)	C1—C4—H4A	109.5
C3—N3—H3	117.8 (11)	C1—C4—H4B	109.5
C2—N4—H4D	120.0	H4A—C4—H4B	109.5
C2—N4—H4E	120.0	C1—C4—H4C	109.5
H4D—N4—H4E	120.0	H4A—C4—H4C	109.5
C3—N5—H5A	120.0	H4B—C4—H4C	109.5
C3—N5—H5B	120.0	O1—C5—O2	127.05 (13)
H5A—N5—H5B	120.0	O1—C5—C6	118.95 (12)
N1—C1—N3	122.20 (12)	O2—C5—C6	113.99 (12)
N1—C1—C4	119.85 (12)	O3—C6—O4	126.24 (13)
N3—C1—C4	117.95 (12)	O3—C6—C5	121.73 (12)
N4—C2—N2	119.38 (12)	O4—C6—C5	112.03 (11)
N4—C2—N1	115.75 (12)
C2—N1—C1—N3	−0.4 (2)	C2—N2—C3—N5	−179.22 (13)
C2—N1—C1—C4	178.65 (13)	C2—N2—C3—N3	−1.0 (2)
C3—N3—C1—N1	1.8 (2)	C1—N3—C3—N5	177.20 (13)
C3—N3—C1—C4	−177.27 (13)	C1—N3—C3—N2	−1.1 (2)
C3—N2—C2—N4	−178.67 (14)	O1—C5—C6—O3	−166.01 (14)
C3—N2—C2—N1	2.5 (2)	O2—C5—C6—O3	13.0 (2)
C1—N1—C2—N4	179.32 (13)	O1—C5—C6—O4	13.65 (18)
C1—N1—C2—N2	−1.8 (2)	O2—C5—C6—O4	−167.33 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1i	0.95 (2)	1.77 (2)	2.7134 (17)	174 (2)
N3—H3···O4i	0.95 (2)	2.50 (2)	2.9841 (17)	111.7 (16)
O4—H4···O2	0.83 (2)	1.66 (2)	2.4921 (16)	175 (2)
N4—H4D···O3ii	0.86	2.17	2.9902 (19)	160
N4—H4E···N1iii	0.86	2.18	3.0399 (19)	174
N5—H5A···N2iv	0.86	2.14	3.0027 (19)	179
N5—H5B···O2v	0.86	2.28	2.8558 (17)	124
N5—H5B···O3v	0.86	2.59	3.2337 (19)	133
C4—H4C···O1vi	0.96	2.49	3.339 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1i	0.95 (2)	1.77 (2)	2.7134 (17)	174 (2)
N3—H3⋯O4i	0.95 (2)	2.50 (2)	2.9841 (17)	111.7 (16)
O4—H4⋯O2	0.83 (2)	1.66 (2)	2.4921 (16)	175 (2)
N4—H4D⋯O3ii	0.86	2.17	2.9902 (19)	160
N4—H4E⋯N1iii	0.86	2.18	3.0399 (19)	174
N5—H5A⋯N2iv	0.86	2.14	3.0027 (19)	179
N5—H5B⋯O2v	0.86	2.28	2.8558 (17)	124
N5—H5B⋯O3v	0.86	2.59	3.2337 (19)	133
C4—H4C⋯O1vi	0.96	2.49	3.339 (2)	148

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