Melaminium hydrogen malonate.

The melaminium (2,4,6-triamino-1,3,5-triazin-1-ium) cation in the title compound, C(3)H(7)N(6) (+)·C(3)H(3)O(4) (-), is essentially planar, with a r.m.s. deviation of the non-H atoms of 0.0085 Å. Extensive hydrogen bonding of the types N-H⋯N and N-H⋯O between cations and cations and between cations and hydrogen malonate (2-carb-oxy-ethano-ate) anions leads to the formation of supra-molecular layers parallel to (1-2-1). An intra-molecular O-H⋯O hydrogen bond in the single deprotonated malonate anion also occurs.

Related literature

For the use of melaminium salts in polymer science, see: Weinstabl et al. (2001 ▶). For structural studies of melaminium salts of purely organic carb­oxy­lic acids, see: Choi et al. (2004 ▶); Janczak & Perpétuo (2001 ▶, 2002 ▶, 2003 ▶, 2004 ▶); Karle et al. (2003 ▶); Marchewka et al. (2003 ▶); Perpétuo & Janczak (2002 ▶, 2005 ▶); Perpétuo et al. (2005 ▶); Prior et al. (2009 ▶); Su et al. (2009 ▶); Udaya Lakshmi et al. (2006 ▶); Froschauer & Weil (2012 ▶); Zhang et al. (2004 ▶, 2005 ▶).

Experimental

Crystal data

C3H7N6 +·C3H3O4 −

M = 230.20

Triclinic,

a = 5.1996 (15) Å

b = 7.499 (2) Å

c = 13.119 (4) Å

α = 100.206 (5)°

β = 98.014 (5)°

γ = 106.534 (5)°

V = 472.7 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.14 mm−1

T = 293 K

0.23 × 0.18 × 0.12 mm

Data collection

Siemens SMART CCD diffractometer

4807 measured reflections

2354 independent reflections

1190 reflections with I > 2σ(I)

R int = 0.078

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.105

S = 0.89

2354 reflections

150 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.23 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: Mercury (Macrae et al., 2006 ▶) and ATOMS (Dowty, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812033016/cv5323sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812033016/cv5323Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812033016/cv5323Isup3.cml

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

C3H7N6+·C3H3O4−	Z = 2
Mr = 230.20	F(000) = 240
Triclinic, P1	Dx = 1.617 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1996 (15) Å	Cell parameters from 950 reflections
b = 7.499 (2) Å	θ = 2.9–25.6°
c = 13.119 (4) Å	µ = 0.14 mm−1
α = 100.206 (5)°	T = 293 K
β = 98.014 (5)°	Irregular, colourless
γ = 106.534 (5)°	0.23 × 0.18 × 0.12 mm
V = 472.7 (2) Å3

Siemens SMART CCD diffractometer	1190 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.078
Graphite monochromator	θmax = 28.5°, θmin = 2.9°
ω scans	h = −6→6
4807 measured reflections	k = −10→10
2354 independent reflections	l = −17→17

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.038P)2] where P = (Fo2 + 2Fc2)/3
S = 0.89	(Δ/σ)max < 0.001
2354 reflections	Δρmax = 0.23 e Å−3
150 parameters	Δρmin = −0.23 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.058 (10)

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
H10	1.131 (4)	0.844 (3)	0.9236 (18)	0.068 (7)*
O1	1.0512 (3)	0.8287 (2)	0.84785 (11)	0.0556 (5)
N1	0.2299 (3)	0.7179 (2)	0.29981 (11)	0.0321 (4)
H1	0.1159	0.6950	0.2412	0.038*
N2	0.3254 (3)	0.6667 (2)	0.47008 (11)	0.0313 (4)
O2	0.6330 (3)	0.6777 (2)	0.75923 (10)	0.0490 (4)
N3	0.6677 (3)	0.8814 (2)	0.40391 (11)	0.0322 (4)
N4	−0.0943 (3)	0.5082 (2)	0.36078 (11)	0.0385 (4)
H3	−0.1474	0.4505	0.4089	0.046*
H2	−0.2036	0.4858	0.3011	0.046*
C1	0.1545 (3)	0.6307 (2)	0.37848 (13)	0.0294 (4)
C3	0.4874 (3)	0.8417 (2)	0.31493 (14)	0.0311 (4)
C5	0.7245 (4)	0.6701 (3)	0.94033 (14)	0.0429 (5)
H8	0.6323	0.5333	0.9229	0.051*
H9	0.5920	0.7311	0.9605	0.051*
C2	0.5776 (3)	0.7909 (2)	0.47902 (13)	0.0288 (4)
N6	0.5500 (3)	0.9219 (2)	0.23620 (11)	0.0452 (5)
H6	0.7104	1.0015	0.2423	0.054*
H7	0.4304	0.8946	0.1787	0.054*
N5	0.7554 (3)	0.8292 (2)	0.56860 (11)	0.0387 (4)
H4	0.7090	0.7756	0.6190	0.046*
H5	0.9175	0.9078	0.5766	0.046*
C6	0.7986 (3)	0.7256 (3)	0.84124 (14)	0.0337 (5)
O4	0.8950 (3)	0.6463 (2)	1.11234 (10)	0.0585 (5)
C4	0.9489 (4)	0.7151 (3)	1.03630 (15)	0.0394 (5)
O3	1.1859 (2)	0.8250 (2)	1.03379 (10)	0.0528 (4)

	U11	U22	U33	U12	U13	U23
O1	0.0362 (8)	0.0771 (11)	0.0396 (9)	−0.0090 (7)	0.0065 (7)	0.0240 (8)
N1	0.0280 (8)	0.0396 (9)	0.0232 (8)	0.0021 (7)	0.0000 (6)	0.0118 (7)
N2	0.0264 (8)	0.0365 (9)	0.0258 (8)	0.0008 (7)	0.0023 (6)	0.0110 (7)
O2	0.0391 (8)	0.0689 (10)	0.0324 (8)	0.0037 (7)	0.0010 (6)	0.0218 (7)
N3	0.0280 (8)	0.0395 (9)	0.0275 (8)	0.0042 (6)	0.0043 (6)	0.0153 (7)
N4	0.0290 (8)	0.0480 (10)	0.0293 (9)	−0.0025 (7)	−0.0005 (7)	0.0152 (7)
C1	0.0274 (9)	0.0309 (10)	0.0273 (10)	0.0048 (8)	0.0050 (8)	0.0075 (8)
C3	0.0284 (10)	0.0324 (10)	0.0307 (11)	0.0055 (8)	0.0061 (8)	0.0098 (8)
C5	0.0295 (10)	0.0590 (13)	0.0356 (11)	0.0024 (9)	0.0034 (8)	0.0208 (10)
C2	0.0253 (9)	0.0306 (10)	0.0281 (10)	0.0065 (8)	0.0017 (8)	0.0077 (8)
N6	0.0338 (9)	0.0611 (11)	0.0309 (9)	−0.0052 (8)	0.0003 (7)	0.0232 (8)
N5	0.0307 (8)	0.0493 (10)	0.0286 (9)	−0.0019 (7)	−0.0002 (7)	0.0183 (7)
C6	0.0288 (10)	0.0397 (11)	0.0312 (11)	0.0064 (8)	0.0044 (9)	0.0132 (9)
O4	0.0481 (9)	0.0789 (11)	0.0345 (8)	−0.0047 (8)	−0.0037 (7)	0.0274 (8)
C4	0.0344 (11)	0.0459 (12)	0.0330 (11)	0.0065 (9)	0.0033 (8)	0.0100 (9)
O3	0.0327 (8)	0.0700 (10)	0.0404 (9)	−0.0041 (7)	−0.0012 (6)	0.0140 (7)

O1—C6	1.303 (2)	C3—N6	1.318 (2)
O1—H10	0.99 (2)	C5—C6	1.501 (2)
N1—C3	1.359 (2)	C5—C4	1.509 (3)
N1—C1	1.361 (2)	C5—H8	0.9700
N1—H1	0.8600	C5—H9	0.9700
N2—C1	1.326 (2)	C2—N5	1.321 (2)
N2—C2	1.351 (2)	N6—H6	0.8600
O2—C6	1.207 (2)	N6—H7	0.8600
N3—C3	1.320 (2)	N5—H4	0.8600
N3—C2	1.355 (2)	N5—H5	0.8600
N4—C1	1.318 (2)	O4—C4	1.232 (2)
N4—H3	0.8600	C4—O3	1.281 (2)
N4—H2	0.8600	O3—H10	1.47 (2)
C6—O1—H10	101.7 (12)	C4—C5—H9	107.6
C3—N1—C1	119.22 (15)	H8—C5—H9	107.0
C3—N1—H1	120.4	N5—C2—N2	117.92 (16)
C1—N1—H1	120.4	N5—C2—N3	116.12 (15)
C1—N2—C2	115.93 (15)	N2—C2—N3	125.96 (15)
C3—N3—C2	115.32 (15)	C3—N6—H6	120.0
C1—N4—H3	120.0	C3—N6—H7	120.0
C1—N4—H2	120.0	H6—N6—H7	120.0
H3—N4—H2	120.0	C2—N5—H4	120.0
N4—C1—N2	120.72 (15)	C2—N5—H5	120.0
N4—C1—N1	117.93 (15)	H4—N5—H5	120.0
N2—C1—N1	121.35 (15)	O2—C6—O1	121.35 (17)
N6—C3—N3	121.03 (15)	O2—C6—C5	121.91 (16)
N6—C3—N1	116.77 (15)	O1—C6—C5	116.74 (16)
N3—C3—N1	122.21 (15)	O4—C4—O3	123.80 (18)
C6—C5—C4	118.87 (15)	O4—C4—C5	118.79 (17)
C6—C5—H8	107.6	O3—C4—C5	117.40 (17)
C4—C5—H8	107.6	C4—O3—H10	98.9 (8)
C6—C5—H9	107.6

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4i	0.86	1.82	2.6785 (19)	176
N4—H2···O2ii	0.86	2.17	2.8350 (19)	134
N4—H3···N2ii	0.86	2.14	2.994 (2)	171
N5—H4···O2	0.86	2.14	2.998 (2)	172
N5—H5···N3iii	0.86	2.23	3.091 (2)	178
N6—H6···O1iii	0.86	2.15	2.8592 (19)	140
N6—H7···O3i	0.86	2.02	2.880 (2)	173
O1—H10···O3	1.00 (2)	1.47 (2)	2.450 (2)	165 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4i	0.86	1.82	2.6785 (19)	176
N4—H2⋯O2ii	0.86	2.17	2.8350 (19)	134
N4—H3⋯N2ii	0.86	2.14	2.994 (2)	171
N5—H4⋯O2	0.86	2.14	2.998 (2)	172
N5—H5⋯N3iii	0.86	2.23	3.091 (2)	178
N6—H6⋯O1iii	0.86	2.15	2.8592 (19)	140
N6—H7⋯O3i	0.86	2.02	2.880 (2)	173
O1—H10⋯O3	1.00 (2)	1.47 (2)	2.450 (2)	165 (2)

Symmetry codes: (i) ; (ii) ; (iii) .