2,4-Diamino-6-methyl-1,3,5-triazin-1-ium tetra-fluoro-borate.

In the crystal structure of the title salt, C(4)H(8)N(5) (+)·BF(4) (-), centrosymmetrically related cations undergo base pairing via a pair of N-H⋯N hydrogen bonds, forming an R(2) (2)(8) ring motif. The cations and anions inter-act via N-H⋯F hydrogen bonds, generating supra-molecular layers parallel to ([Formula: see text]20), which are in turn linked into a three-dimensional network, forming rings of R(6) (6)(24) graph-set motif. The crystal structure is further stabilized by π-π stacking inter-actions [centroid-centroid distance = 3.3361 (12) Å].

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter (1990 ▶). For related structures, see: Conant et al. (1964 ▶); Gokul Raj etal. (2006 ▶); Zimmermann et al. (1963 ▶); Hemamalini et al. (2005 ▶); Balasubramani et al. (2007 ▶); Li et al. (2011 ▶). For π–π stacking inter­actions, see: Hunter (1994 ▶).

Experimental

Crystal data

C4H8N5 +·BF4 −

M = 212.96

Triclinic,

a = 6.9982 (3) Å

b = 8.2887 (4) Å

c = 8.5353 (4) Å

α = 63.931 (2)°

β = 83.209 (3)°

γ = 85.057 (3)°

V = 441.29 (4) Å3

Z = 2

Mo Kα radiation

μ = 0.16 mm−1

T = 296 K

0.06 × 0.05 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.990, T max = 0.993

8850 measured reflections

2196 independent reflections

1842 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.203

S = 1.09

2196 reflections

128 parameters

H-atom parameters constrained

Δρmax = 0.52 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038797/rz2638sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038797/rz2638Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811038797/rz2638Isup3.cml

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

C4H8N5+·BF4−	Z = 2
Mr = 212.96	F(000) = 216
Triclinic, P1	Dx = 1.603 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9982 (3) Å	Cell parameters from 2196 reflections
b = 8.2887 (4) Å	θ = 2.7–28.4°
c = 8.5353 (4) Å	µ = 0.16 mm−1
α = 63.931 (2)°	T = 296 K
β = 83.209 (3)°	Prism, colourless
γ = 85.057 (3)°	0.06 × 0.05 × 0.04 mm
V = 441.29 (4) Å3

Bruker SMART APEXII CCD area-detector diffractometer	2196 independent reflections
Radiation source: fine-focus sealed tube	1842 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 28.4°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −9→9
Tmin = 0.990, Tmax = 0.993	k = −11→11
8850 measured reflections	l = −11→11

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.203	H-atom parameters constrained
S = 1.09	w = 1/[σ2(Fo2) + (0.1041P)2 + 0.234P] where P = (Fo2 + 2Fc2)/3
2196 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.52 e Å−3
0 restraints	Δρmin = −0.54 e Å−3

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.

	x	y	z	Uiso*/Ueq
N1	0.5137 (2)	0.7576 (2)	0.7766 (2)	0.0388 (5)
N2	0.6729 (3)	0.8579 (3)	0.9371 (3)	0.0502 (6)
N3	0.3894 (2)	0.7141 (2)	1.0587 (2)	0.0408 (5)
N4	0.1028 (3)	0.5754 (3)	1.1593 (2)	0.0524 (6)
N5	0.2262 (2)	0.6115 (2)	0.8873 (2)	0.0392 (5)
C2	0.5241 (3)	0.7772 (3)	0.9261 (3)	0.0376 (5)
C4	0.2430 (3)	0.6367 (3)	1.0340 (3)	0.0373 (5)
C6	0.3630 (3)	0.6734 (3)	0.7627 (3)	0.0380 (5)
C7	0.3631 (4)	0.6521 (4)	0.5987 (3)	0.0569 (8)
F1	0.7776 (3)	0.9140 (2)	0.4910 (2)	0.0732 (6)
F2	1.0031 (4)	0.9604 (5)	0.2703 (4)	0.1389 (14)
F3	0.9060 (4)	0.6845 (3)	0.4382 (3)	0.1076 (9)
F4	0.7146 (3)	0.8835 (4)	0.2567 (3)	0.1057 (10)
B1	0.8547 (3)	0.8604 (3)	0.3634 (3)	0.0433 (6)
H1	0.60230	0.79840	0.69160	0.0470*
H2A	0.75990	0.89850	0.85050	0.0600*
H2B	0.68300	0.86990	1.03080	0.0600*
H4A	0.10620	0.58540	1.25500	0.0630*
H4B	0.00750	0.52520	1.14560	0.0630*
H7A	0.28340	0.55470	0.61960	0.0850*
H7B	0.49230	0.62670	0.56130	0.0850*
H7C	0.31370	0.76110	0.50920	0.0850*

	U11	U22	U33	U12	U13	U23
N1	0.0350 (8)	0.0420 (8)	0.0385 (8)	−0.0107 (6)	0.0081 (6)	−0.0177 (7)
N2	0.0418 (9)	0.0603 (11)	0.0509 (10)	−0.0202 (8)	0.0034 (7)	−0.0250 (9)
N3	0.0361 (8)	0.0496 (9)	0.0389 (8)	−0.0098 (7)	0.0015 (6)	−0.0209 (7)
N4	0.0405 (9)	0.0788 (13)	0.0457 (10)	−0.0223 (9)	0.0106 (7)	−0.0340 (10)
N5	0.0337 (8)	0.0458 (9)	0.0423 (9)	−0.0083 (6)	0.0024 (6)	−0.0232 (7)
C2	0.0340 (9)	0.0364 (9)	0.0413 (10)	−0.0052 (7)	−0.0006 (7)	−0.0158 (7)
C4	0.0325 (9)	0.0412 (9)	0.0383 (9)	−0.0044 (7)	0.0013 (7)	−0.0180 (7)
C6	0.0362 (9)	0.0396 (9)	0.0398 (9)	−0.0040 (7)	0.0017 (7)	−0.0196 (8)
C7	0.0583 (14)	0.0756 (16)	0.0474 (12)	−0.0189 (12)	0.0079 (10)	−0.0366 (12)
F1	0.0826 (11)	0.0843 (11)	0.0659 (10)	−0.0301 (9)	0.0316 (8)	−0.0493 (9)
F2	0.125 (2)	0.192 (3)	0.123 (2)	−0.109 (2)	0.0860 (17)	−0.095 (2)
F3	0.166 (2)	0.0741 (12)	0.0727 (12)	0.0422 (14)	−0.0214 (13)	−0.0284 (10)
F4	0.0973 (16)	0.153 (2)	0.0885 (14)	0.0280 (15)	−0.0463 (12)	−0.0688 (15)
B1	0.0425 (11)	0.0504 (12)	0.0362 (10)	−0.0069 (9)	0.0042 (8)	−0.0191 (9)

F1—B1	1.386 (3)	N5—C4	1.376 (3)
F2—B1	1.331 (4)	N1—H1	0.8600
F3—B1	1.345 (4)	N2—H2A	0.8600
F4—B1	1.361 (3)	N2—H2B	0.8600
N1—C2	1.366 (3)	N4—H4B	0.8600
N1—C6	1.357 (3)	N4—H4A	0.8600
N2—C2	1.319 (3)	C6—C7	1.486 (4)
N3—C4	1.338 (3)	C7—H7B	0.9600
N3—C2	1.325 (3)	C7—H7C	0.9600
N4—C4	1.313 (3)	C7—H7A	0.9600
N5—C6	1.294 (3)
F1···N1	2.758 (2)	C2···F4i	3.014 (4)
F1···C6i	3.282 (3)	C2···N5iv	3.339 (3)
F2···N2ii	2.800 (4)	C2···C4iv	3.561 (4)
F3···N4iii	3.047 (3)	C2···C6iv	3.591 (4)
F3···N4iv	3.149 (3)	C4···N1iv	3.353 (3)
F3···F3v	3.000 (4)	C4···C2iv	3.561 (4)
F4···C2i	3.014 (4)	C6···F1i	3.282 (3)
F4···N2vi	2.877 (4)	C6···N3iv	3.317 (3)
F4···N1i	3.167 (4)	C6···C2iv	3.591 (4)
F1···H7Ci	2.7100	C6···H4Bx	3.0300
F1···H1	1.9000	B1···H1	2.9900
F2···H2Aii	2.0100	H1···H2A	2.2900
F3···H4Aiv	2.5900	H1···H7B	2.3700
F3···H7Avii	2.7200	H1···B1	2.9900
F3···H4Aiii	2.3400	H1···F1	1.9000
F4···H2Bvi	2.0200	H2A···F2ii	2.0100
N1···F4i	3.167 (4)	H2A···H1	2.2900
N1···C4iv	3.353 (3)	H2B···F4viii	2.0200
N1···F1	2.758 (2)	H4A···F3iv	2.5900
N2···F4viii	2.877 (4)	H4A···F3ix	2.3400
N2···F2ii	2.800 (4)	H4B···H7Ax	2.5900
N3···C6iv	3.317 (3)	H4B···N5x	2.1800
N4···F3ix	3.047 (3)	H4B···C6x	3.0300
N4···F3iv	3.149 (3)	H7A···F3vii	2.7200
N4···N5x	3.038 (3)	H7A···H4Bx	2.5900
N5···N4x	3.038 (3)	H7B···H1	2.3700
N5···C2iv	3.339 (3)	H7C···F1i	2.7100
N5···H4Bx	2.1800
C2—N1—C6	119.77 (17)	N3—C4—N4	118.8 (2)
C2—N3—C4	116.00 (18)	N1—C6—C7	117.1 (2)
C4—N5—C6	115.89 (18)	N5—C6—C7	121.1 (2)
C6—N1—H1	120.00	N1—C6—N5	121.9 (2)
C2—N1—H1	120.00	C6—C7—H7A	109.00
C2—N2—H2A	120.00	C6—C7—H7B	109.00
H2A—N2—H2B	120.00	C6—C7—H7C	109.00
C2—N2—H2B	120.00	H7A—C7—H7B	109.00
H4A—N4—H4B	120.00	H7A—C7—H7C	109.00
C4—N4—H4B	120.00	H7B—C7—H7C	109.00
C4—N4—H4A	120.00	F1—B1—F2	110.0 (3)
N1—C2—N2	118.6 (2)	F1—B1—F3	109.8 (2)
N2—C2—N3	120.5 (2)	F1—B1—F4	107.9 (2)
N1—C2—N3	120.9 (2)	F2—B1—F3	111.7 (3)
N3—C4—N5	125.55 (19)	F2—B1—F4	109.6 (2)
N4—C4—N5	115.7 (2)	F3—B1—F4	107.8 (3)
C6—N1—C2—N2	179.3 (2)	C2—N3—C4—N4	−178.4 (2)
C6—N1—C2—N3	0.4 (3)	C2—N3—C4—N5	2.8 (3)
C2—N1—C6—N5	0.6 (3)	C6—N5—C4—N3	−1.9 (3)
C2—N1—C6—C7	−178.4 (2)	C6—N5—C4—N4	179.3 (2)
C4—N3—C2—N1	−2.0 (3)	C4—N5—C6—N1	0.1 (3)
C4—N3—C2—N2	179.1 (2)	C4—N5—C6—C7	179.0 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···F1	0.86	1.90	2.758 (2)	173
N2—H2A···F2ii	0.86	2.01	2.800 (4)	152
N2—H2B···F4viii	0.86	2.02	2.877 (4)	177
N4—H4A···F3ix	0.86	2.34	3.047 (3)	139
N4—H4B···N5x	0.86	2.18	3.038 (3)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯F1	0.86	1.90	2.758 (2)	173
N2—H2A⋯F2i	0.86	2.01	2.800 (4)	152
N2—H2B⋯F4ii	0.86	2.02	2.877 (4)	177
N4—H4A⋯F3iii	0.86	2.34	3.047 (3)	139
N4—H4B⋯N5iv	0.86	2.18	3.038 (3)	178

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