2-Amino-5-methyl-pyridinium trifluoro-acetate.

In the title salt, C6H9N2(+)·C2F3O2(-), the F atoms of the anion are disordered over two sets of sites, with refined occupancies in a ratio of 0.505 (17):0.495 (17). In the crystal, cations and anions are linked via N-H⋯O hydrogen bonds, forming R2(2)(8) ring motifs. The ionic units are linked into a two-dimensional network parallel to (100) by N-H⋯O and weak C-H⋯O hydrogen bonds. The crystal structure is further stabilized by weak C-H⋯F hydrogen bonds, resulting in a three-dimensional network.

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For details of hydrogen bonding, see: Jeffrey & Saenger (1991 ▶); Jeffrey (1997 ▶); Scheiner (1997 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). For a related structure, see: Rodrigues et al. (2001 ▶).

Experimental

Crystal data

C6H9N2 +·C2F3O2 −

M = 222.17

Orthorhombic,

a = 18.725 (4) Å

b = 4.6256 (10) Å

c = 11.319 (2) Å

V = 980.4 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 100 K

0.54 × 0.29 × 0.11 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.926, T max = 0.985

12012 measured reflections

3216 independent reflections

2627 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.114

S = 1.07

3216 reflections

177 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.23 e Å−3

Δρmin = −0.30 e Å−3

Absolute structure: Flack (1983 ▶), 1368 Friedel pairs

Flack parameter: −0.1 (7)

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812045291/lh5549sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045291/lh5549Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812045291/lh5549Isup3.cml

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

C6H9N2+·C2F3O2−	F(000) = 456
Mr = 222.17	Dx = 1.505 Mg m−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 4200 reflections
a = 18.725 (4) Å	θ = 2.8–32.5°
b = 4.6256 (10) Å	µ = 0.15 mm−1
c = 11.319 (2) Å	T = 100 K
V = 980.4 (3) Å3	Plate, colourless
Z = 4	0.54 × 0.29 × 0.11 mm

Bruker SMART APEXII DUO CCD area-detector diffractometer	3216 independent reflections
Radiation source: fine-focus sealed tube	2627 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
φ and ω scans	θmax = 32.7°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −28→28
Tmin = 0.926, Tmax = 0.985	k = −6→6
12012 measured reflections	l = −16→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)] = 0.046	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.114	w = 1/[σ2(Fo2) + (0.0538P)2 + 0.1405P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max < 0.001
3216 reflections	Δρmax = 0.23 e Å−3
177 parameters	Δρmin = −0.30 e Å−3
1 restraint	Absolute structure: Flack (1983), 1368 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.1 (7)

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	Occ. (<1)
F1	0.5951 (6)	−0.360 (3)	0.6163 (9)	0.0636 (17)	0.505 (17)
F2	0.5409 (3)	0.0250 (13)	0.6382 (9)	0.075 (2)	0.505 (17)
F3	0.5859 (5)	−0.076 (4)	0.4723 (7)	0.104 (4)	0.505 (17)
F1X	0.6094 (7)	−0.352 (2)	0.5755 (15)	0.097 (4)	0.495 (17)
F2X	0.5478 (4)	−0.032 (2)	0.6626 (5)	0.080 (2)	0.495 (17)
F3X	0.5752 (3)	0.0168 (15)	0.4869 (6)	0.0479 (14)	0.495 (17)
O1	0.67666 (7)	0.0887 (3)	0.73348 (10)	0.0384 (3)
O2	0.70767 (6)	0.1522 (3)	0.54434 (9)	0.0312 (3)
N1	0.80834 (7)	0.5530 (3)	0.60374 (10)	0.0248 (3)
N2	0.78211 (9)	0.5050 (4)	0.80182 (12)	0.0320 (3)
C1	0.81952 (8)	0.6336 (4)	0.71687 (12)	0.0257 (3)
C2	0.87136 (9)	0.8495 (4)	0.73742 (14)	0.0307 (3)
H2A	0.8806	0.9141	0.8156	0.037*
C3	0.90806 (9)	0.9649 (4)	0.64496 (15)	0.0316 (3)
H3A	0.9432	1.1084	0.6599	0.038*
C4	0.89527 (8)	0.8768 (4)	0.52703 (13)	0.0279 (3)
C5	0.84486 (8)	0.6703 (4)	0.51114 (12)	0.0257 (3)
H5A	0.8347	0.6054	0.4333	0.031*
C6	0.93586 (10)	1.0012 (4)	0.42471 (17)	0.0364 (4)
H6A	0.9186	0.9147	0.3510	0.055*
H6B	0.9868	0.9594	0.4342	0.055*
H6C	0.9286	1.2110	0.4221	0.055*
C7	0.59832 (9)	−0.0794 (4)	0.58757 (15)	0.0312 (3)
C8	0.66781 (9)	0.0707 (4)	0.62616 (13)	0.0268 (3)
H2N2	0.7456 (13)	0.369 (6)	0.785 (2)	0.040 (6)*
H1N2	0.7919 (14)	0.558 (6)	0.873 (3)	0.050 (7)*
H1N1	0.7723 (13)	0.405 (6)	0.585 (2)	0.043 (6)*

	U11	U22	U33	U12	U13	U23
F1	0.075 (3)	0.027 (2)	0.089 (4)	−0.0046 (19)	−0.017 (2)	0.007 (2)
F2	0.0328 (17)	0.044 (2)	0.148 (6)	0.0071 (15)	0.004 (3)	−0.043 (3)
F3	0.093 (4)	0.194 (10)	0.0252 (15)	−0.097 (5)	−0.010 (2)	0.014 (4)
F1X	0.092 (6)	0.021 (2)	0.177 (11)	0.005 (3)	−0.069 (7)	−0.017 (5)
F2X	0.041 (3)	0.154 (6)	0.044 (2)	−0.038 (3)	0.0180 (16)	−0.011 (3)
F3X	0.0410 (16)	0.060 (3)	0.042 (3)	−0.0108 (16)	−0.0251 (16)	0.0201 (19)
O1	0.0462 (7)	0.0534 (9)	0.0156 (5)	−0.0029 (6)	0.0001 (4)	0.0020 (5)
O2	0.0337 (5)	0.0450 (7)	0.0149 (4)	−0.0038 (5)	0.0021 (4)	−0.0058 (5)
N1	0.0316 (6)	0.0292 (7)	0.0136 (5)	0.0038 (5)	−0.0025 (4)	−0.0004 (5)
N2	0.0454 (8)	0.0368 (9)	0.0138 (5)	0.0023 (7)	0.0001 (5)	−0.0032 (5)
C1	0.0341 (7)	0.0277 (8)	0.0154 (6)	0.0089 (6)	−0.0027 (5)	−0.0032 (6)
C2	0.0412 (8)	0.0290 (9)	0.0220 (6)	0.0061 (7)	−0.0067 (6)	−0.0064 (6)
C3	0.0351 (8)	0.0299 (9)	0.0298 (7)	0.0036 (6)	−0.0051 (6)	−0.0059 (7)
C4	0.0305 (7)	0.0298 (9)	0.0235 (7)	0.0075 (6)	−0.0013 (5)	0.0003 (6)
C5	0.0321 (6)	0.0302 (8)	0.0147 (5)	0.0069 (6)	−0.0025 (5)	−0.0014 (5)
C6	0.0394 (8)	0.0377 (10)	0.0320 (7)	0.0008 (7)	0.0038 (7)	0.0033 (8)
C7	0.0380 (7)	0.0299 (9)	0.0255 (6)	−0.0003 (6)	−0.0007 (6)	0.0037 (6)
C8	0.0318 (7)	0.0305 (8)	0.0181 (6)	0.0052 (6)	−0.0001 (5)	−0.0008 (6)

F1—C7	1.341 (11)	N2—H1N2	0.86 (3)
F2—C7	1.311 (6)	C1—C2	1.412 (2)
F3—C7	1.325 (8)	C2—C3	1.361 (3)
F1X—C7	1.287 (11)	C2—H2A	0.9500
F2X—C7	1.290 (5)	C3—C4	1.416 (2)
F3X—C7	1.297 (6)	C3—H3A	0.9500
O1—C8	1.2289 (18)	C4—C5	1.355 (2)
O2—C8	1.2478 (19)	C4—C6	1.500 (2)
N1—C1	1.3500 (18)	C5—H5A	0.9500
N1—C5	1.3640 (19)	C6—H6A	0.9800
N1—H1N1	0.98 (3)	C6—H6B	0.9800
N2—C1	1.330 (2)	C6—H6C	0.9800
N2—H2N2	0.95 (3)	C7—C8	1.538 (2)
C1—N1—C5	122.78 (14)	C4—C6—H6A	109.5
C1—N1—H1N1	119.9 (15)	C4—C6—H6B	109.5
C5—N1—H1N1	117.3 (15)	H6A—C6—H6B	109.5
C1—N2—H2N2	121.8 (14)	C4—C6—H6C	109.5
C1—N2—H1N2	116.0 (19)	H6A—C6—H6C	109.5
H2N2—N2—H1N2	122 (2)	H6B—C6—H6C	109.5
N2—C1—N1	118.73 (15)	F1X—C7—F2X	110.9 (7)
N2—C1—C2	124.01 (14)	F1X—C7—F3X	107.3 (7)
N1—C1—C2	117.26 (14)	F2X—C7—F3X	106.0 (5)
C3—C2—C1	119.86 (14)	F2—C7—F1	102.4 (6)
C3—C2—H2A	120.1	F3—C7—F1	104.0 (8)
C1—C2—H2A	120.1	F1X—C7—C8	109.7 (5)
C2—C3—C4	121.77 (16)	F2X—C7—C8	110.8 (3)
C2—C3—H3A	119.1	F3X—C7—C8	112.1 (3)
C4—C3—H3A	119.1	F2—C7—C8	113.8 (3)
C5—C4—C3	116.49 (14)	F3—C7—C8	115.0 (4)
C5—C4—C6	121.40 (14)	F1—C7—C8	114.0 (5)
C3—C4—C6	122.10 (16)	O1—C8—O2	129.24 (16)
C4—C5—N1	121.84 (13)	O1—C8—C7	115.18 (15)
C4—C5—H5A	119.1	O2—C8—C7	115.57 (13)
N1—C5—H5A	119.1
C5—N1—C1—N2	−179.15 (15)	F2X—C7—C8—O1	32.3 (6)
C5—N1—C1—C2	0.2 (2)	F3X—C7—C8—O1	150.5 (4)
N2—C1—C2—C3	178.70 (16)	F2—C7—C8—O1	51.3 (5)
N1—C1—C2—C3	−0.6 (2)	F3—C7—C8—O1	174.4 (9)
C1—C2—C3—C4	0.7 (2)	F1—C7—C8—O1	−65.7 (5)
C2—C3—C4—C5	−0.4 (2)	F1X—C7—C8—O2	88.4 (9)
C2—C3—C4—C6	−179.53 (17)	F2X—C7—C8—O2	−148.9 (5)
C3—C4—C5—N1	−0.1 (2)	F3X—C7—C8—O2	−30.7 (4)
C6—C4—C5—N1	179.11 (15)	F2—C7—C8—O2	−129.9 (5)
C1—N1—C5—C4	0.1 (2)	F3—C7—C8—O2	−6.8 (9)
F1X—C7—C8—O1	−90.5 (9)	F1—C7—C8—O2	113.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O2	0.98 (3)	1.75 (3)	2.7281 (19)	177 (2)
N2—H2N2···O1	0.95 (3)	1.92 (3)	2.865 (2)	173 (2)
N2—H1N2···O2i	0.86 (3)	1.99 (3)	2.8347 (18)	167 (3)
C3—H3A···F2ii	0.95	2.51	3.429 (6)	164
C5—H5A···O1iii	0.95	2.27	3.1910 (19)	162

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.98 (3)	1.75 (3)	2.7281 (19)	177 (2)
N2—H2N2⋯O1	0.95 (3)	1.92 (3)	2.865 (2)	173 (2)
N2—H1N2⋯O2i	0.86 (3)	1.99 (3)	2.8347 (18)	167 (3)
C3—H3A⋯F2ii	0.95	2.51	3.429 (6)	164
C5—H5A⋯O1iii	0.95	2.27	3.1910 (19)	162

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