2-Amino-4-methyl-pyridinium trifluoro-acetate: a monoclinic polymorph.

The title salt, C(6)H(9)N(2) (+)·C(2)F(3)O(2) (-), is a monoclinic polymorph of a previously reported structure [Hemamalini & Fun (2010). Acta Cryst. E66, o781-o782]. In the crystal structure, the cations and anions are linked by two different types of N-H⋯O hydrogen bonds, forming cation-anion pairs. These pairs are hydrogen bonded to neighbouring pairs via another N-H⋯O hydrogen bonds involving an H atom of the NH(2) group and one of the O atoms of the COO(-) group into a chain extended along the b axis.

Related literature

For a related structure and the triclinic polymorph of the title salt, see: Hemamalini & Fun (2010a ▶,b ▶).

Experimental

Crystal data

C6H9N2 +·C2F3O2 −

M = 222.17

Monoclinic,

a = 8.5315 (7) Å

b = 11.4901 (9) Å

c = 9.7206 (8) Å

β = 90.820 (1)°

V = 952.79 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.15 mm−1

T = 100 K

0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer

10752 measured reflections

2197 independent reflections

1784 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.098

S = 1.06

2197 reflections

150 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.29 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT (Bruker 2005 ▶); 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008408/ng2740sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008408/ng2740Isup2.hkl

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

C6H9N2+·C2F3O2−	F(000) = 456
Mr = 222.17	Dx = 1.549 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5265 reflections
a = 8.5315 (7) Å	θ = 2.7–28.0°
b = 11.4901 (9) Å	µ = 0.15 mm−1
c = 9.7206 (8) Å	T = 100 K
β = 90.820 (1)°	Block, colorless
V = 952.79 (13) Å3	0.30 × 0.20 × 0.10 mm
Z = 4

Bruker SMART APEX diffractometer	1784 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.036
graphite	θmax = 28.2°, θmin = 2.4°
φ and ω scans	h = −5→11
10752 measured reflections	k = −14→14
2197 independent reflections	l = −12→12

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)] = 0.035	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098	w = 1/[σ2(Fo2) + (0.0474P)2 + 0.2454P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.001
2197 reflections	Δρmax = 0.29 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: 0.0084 (16)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
F1	0.16929 (11)	0.27679 (7)	1.06142 (10)	0.0350 (2)
F2	0.08357 (10)	0.40806 (8)	0.92121 (10)	0.0358 (2)
F3	0.25375 (10)	0.45302 (7)	1.07851 (9)	0.0316 (2)
O1	0.36035 (11)	0.23798 (8)	0.85540 (11)	0.0259 (2)
O2	0.41240 (11)	0.42938 (8)	0.83832 (10)	0.0257 (2)
N1	0.61429 (13)	0.37742 (9)	0.62595 (12)	0.0212 (2)
H1B	0.544 (2)	0.3930 (17)	0.699 (2)	0.048 (5)*
N2	0.56684 (13)	0.18015 (10)	0.63958 (12)	0.0223 (3)
H2C	0.504 (2)	0.1964 (16)	0.711 (2)	0.040 (5)*
H2B	0.588 (2)	0.1040 (16)	0.6158 (18)	0.034 (5)*
C1	0.68436 (16)	0.47274 (12)	0.56989 (15)	0.0251 (3)
H1A	0.6618	0.5480	0.6049	0.030*
C2	0.78596 (16)	0.46100 (12)	0.46475 (15)	0.0250 (3)
H2A	0.8341	0.5277	0.4261	0.030*
C3	0.81986 (15)	0.34848 (12)	0.41287 (14)	0.0214 (3)
C4	0.74763 (14)	0.25417 (11)	0.47012 (13)	0.0206 (3)
H4A	0.7689	0.1784	0.4359	0.025*
C5	0.64122 (14)	0.26797 (11)	0.58005 (14)	0.0196 (3)
C6	0.93335 (16)	0.33574 (13)	0.29694 (15)	0.0260 (3)
H6A	0.9287	0.2560	0.2612	0.039*
H6B	1.0398	0.3523	0.3307	0.039*
H6C	0.9055	0.3905	0.2233	0.039*
C7	0.34308 (14)	0.34184 (11)	0.88424 (14)	0.0200 (3)
C8	0.21258 (15)	0.36940 (11)	0.98849 (15)	0.0236 (3)

	U11	U22	U33	U12	U13	U23
F1	0.0412 (5)	0.0257 (5)	0.0385 (5)	−0.0036 (4)	0.0209 (4)	0.0027 (4)
F2	0.0220 (4)	0.0367 (5)	0.0488 (6)	0.0070 (3)	0.0017 (4)	−0.0026 (4)
F3	0.0328 (5)	0.0271 (5)	0.0350 (5)	−0.0012 (3)	0.0096 (4)	−0.0114 (4)
O1	0.0294 (5)	0.0168 (5)	0.0319 (6)	−0.0008 (4)	0.0099 (4)	−0.0027 (4)
O2	0.0292 (5)	0.0179 (5)	0.0303 (6)	−0.0033 (4)	0.0105 (4)	0.0005 (4)
N1	0.0223 (5)	0.0177 (5)	0.0237 (6)	0.0006 (4)	0.0044 (4)	−0.0015 (5)
N2	0.0250 (6)	0.0168 (6)	0.0253 (6)	−0.0007 (4)	0.0073 (5)	−0.0007 (5)
C1	0.0272 (7)	0.0168 (6)	0.0314 (8)	−0.0007 (5)	0.0026 (6)	−0.0014 (5)
C2	0.0250 (7)	0.0200 (7)	0.0302 (8)	−0.0033 (5)	0.0032 (5)	0.0040 (5)
C3	0.0181 (6)	0.0239 (7)	0.0223 (7)	−0.0005 (5)	0.0013 (5)	0.0008 (5)
C4	0.0206 (6)	0.0187 (6)	0.0224 (7)	0.0006 (5)	0.0019 (5)	−0.0010 (5)
C5	0.0185 (6)	0.0181 (6)	0.0221 (6)	0.0003 (4)	−0.0005 (5)	−0.0005 (5)
C6	0.0236 (7)	0.0298 (7)	0.0247 (7)	−0.0021 (5)	0.0052 (5)	0.0023 (6)
C7	0.0200 (6)	0.0185 (6)	0.0217 (7)	−0.0005 (5)	0.0022 (5)	−0.0010 (5)
C8	0.0227 (6)	0.0182 (6)	0.0299 (7)	−0.0008 (5)	0.0060 (5)	−0.0015 (5)

F1—C8	1.3337 (15)	C1—H1A	0.9500
F2—C8	1.3475 (16)	C2—C3	1.4190 (19)
F3—C8	1.3429 (16)	C2—H2A	0.9500
O1—C7	1.2352 (15)	C3—C4	1.3688 (18)
O2—C7	1.2523 (15)	C3—C6	1.5033 (18)
N1—C5	1.3552 (16)	C4—C5	1.4209 (17)
N1—C1	1.3650 (17)	C4—H4A	0.9500
N1—H1B	0.952 (19)	C6—H6A	0.9800
N2—C5	1.3290 (16)	C6—H6B	0.9800
N2—H2C	0.901 (18)	C6—H6C	0.9800
N2—H2B	0.923 (18)	C7—C8	1.5490 (18)
C1—C2	1.356 (2)
C5—N1—C1	122.40 (12)	N2—C5—N1	118.49 (12)
C5—N1—H1B	122.1 (12)	N2—C5—C4	123.85 (12)
C1—N1—H1B	115.5 (12)	N1—C5—C4	117.67 (12)
C5—N2—H2C	118.0 (12)	C3—C6—H6A	109.5
C5—N2—H2B	121.1 (11)	C3—C6—H6B	109.5
H2C—N2—H2B	120.5 (16)	H6A—C6—H6B	109.5
C2—C1—N1	120.62 (12)	C3—C6—H6C	109.5
C2—C1—H1A	119.7	H6A—C6—H6C	109.5
N1—C1—H1A	119.7	H6B—C6—H6C	109.5
C1—C2—C3	119.61 (12)	O1—C7—O2	129.54 (12)
C1—C2—H2A	120.2	O1—C7—C8	115.80 (11)
C3—C2—H2A	120.2	O2—C7—C8	114.62 (11)
C4—C3—C2	118.79 (12)	F1—C8—F3	107.24 (12)
C4—C3—C6	121.75 (12)	F1—C8—F2	106.89 (11)
C2—C3—C6	119.46 (12)	F3—C8—F2	106.54 (10)
C3—C4—C5	120.90 (12)	F1—C8—C7	113.06 (11)
C3—C4—H4A	119.5	F3—C8—C7	112.88 (11)
C5—C4—H4A	119.5	F2—C8—C7	109.85 (11)
C5—N1—C1—C2	−0.3 (2)	C3—C4—C5—N2	179.68 (13)
N1—C1—C2—C3	−0.1 (2)	C3—C4—C5—N1	−0.10 (19)
C1—C2—C3—C4	0.5 (2)	O1—C7—C8—F1	18.42 (18)
C1—C2—C3—C6	−179.60 (13)	O2—C7—C8—F1	−163.72 (12)
C2—C3—C4—C5	−0.37 (19)	O1—C7—C8—F3	140.38 (12)
C6—C3—C4—C5	179.73 (12)	O2—C7—C8—F3	−41.76 (17)
C1—N1—C5—N2	−179.33 (12)	O1—C7—C8—F2	−100.87 (14)
C1—N1—C5—C4	0.46 (19)	O2—C7—C8—F2	76.99 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O2	0.952 (19)	1.82 (2)	2.7724 (14)	177.4 (18)
N2—H2C···O1	0.901 (18)	1.938 (19)	2.8376 (15)	176.3 (17)
N2—H2B···O2i	0.923 (18)	2.055 (18)	2.8946 (15)	150.5 (15)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O2	0.952 (19)	1.82 (2)	2.7724 (14)	177.4 (18)
N2—H2C⋯O1	0.901 (18)	1.938 (19)	2.8376 (15)	176.3 (17)
N2—H2B⋯O2i	0.923 (18)	2.055 (18)	2.8946 (15)	150.5 (15)

Symmetry code: (i) .