2-Amino-6-methyl-pyridinium 2,2,2-tri-chloro-acetate.

In the asymmetric unit of the title mol-ecular salt, C6H9N2 (+)·C2Cl3O2 (-), there are two independent 2-amino-6-methyl-pyridinium cations and two independent tri-chloro-acetate anions. The pyridine N atom of the 2-amino-6-methyl-pyridine mol-ecule is protonated and the geometries of these cations reveal amine-imine tautomerism. Both protonated 2-amino-6-methyl-pyridinium cations are essentially planar [maximum deviations = 0.026 (2) and 0.012 (2) Å]. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl-ate O atoms of the anion via a pair of N-H⋯O hydrogen bonds, forming an R 2 (2)(8) ring motif. These motifs are connected via N-H⋯O and C-H⋯O hydrogen bonds to form slabs parallel to (101).

Related literature

For applications of pyridinium derivatives, see: Akkurt et al. (2005 ▶). For pyridine derivatives as templating agents, see: Desiraju (2001 ▶); Jeffrey (1997 ▶). For details of 2-amino­pyridine and its derivatives, see: Katritzky et al. (1996 ▶); Tomaru et al. (1991 ▶). For bond lengths and angles in similar structures, see: Jin, Shun et al. (2005 ▶); Feng et al. (2007 ▶); Nahringbauer & Kvick (1977 ▶). For other 2-amino­pyridinium structures, see: Jin et al. (2000 ▶, 2001 ▶); Jin, Tu et al. (2005 ▶). For studies on the tautomeric forms of 2-amino­pyridine systems, see: Ishikawa et al. (2002 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C6H9N2 +·C2Cl3O2 −

M = 271.52

Monoclinic,

a = 11.6376 (5) Å

b = 14.6648 (6) Å

c = 13.9100 (6) Å

β = 96.024 (1)°

V = 2360.81 (17) Å3

Z = 8

Mo Kα radiation

μ = 0.76 mm−1

T = 293 K

0.35 × 0.30 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.777, T max = 0.805

39609 measured reflections

5784 independent reflections

3922 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.129

S = 1.04

5784 reflections

297 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.66 e Å−3

Δρmin = −0.64 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814004553/su2705sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814004553/su2705Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814004553/su2705Isup3.cml

CCDC reference: 988938

Additional supporting information: crystallographic information; 3D view; checkCIF report

C6H9N2+·C2Cl3O2−	F(000) = 1104
Mr = 271.52	Dx = 1.528 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5784 reflections
a = 11.6376 (5) Å	θ = 2.0–28.1°
b = 14.6648 (6) Å	µ = 0.76 mm−1
c = 13.9100 (6) Å	T = 293 K
β = 96.024 (1)°	Block, colourless
V = 2360.81 (17) Å3	0.35 × 0.30 × 0.30 mm
Z = 8

Bruker Kappa APEXII CCD diffractometer	5784 independent reflections
Radiation source: fine-focus sealed tube	3922 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ω and φ scans	θmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −15→12
Tmin = 0.777, Tmax = 0.805	k = −19→19
39609 measured reflections	l = −16→18

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0512P)2 + 1.4785P] where P = (Fo2 + 2Fc2)/3
5784 reflections	(Δ/σ)max < 0.001
297 parameters	Δρmax = 0.66 e Å−3
6 restraints	Δρmin = −0.64 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
C1	0.3813 (2)	0.07767 (18)	0.03971 (18)	0.0507 (6)
C2	0.3271 (3)	0.0212 (2)	0.1018 (2)	0.0713 (8)
H2	0.3343	0.0326	0.1679	0.086*
C3	0.2640 (3)	−0.0500 (3)	0.0649 (3)	0.0852 (10)
H3	0.2284	−0.0880	0.1063	0.102*
C4	0.2509 (3)	−0.0681 (2)	−0.0346 (3)	0.0751 (9)
H4	0.2071	−0.1176	−0.0588	0.090*
C5	0.3029 (2)	−0.01251 (17)	−0.0952 (2)	0.0549 (6)
C6	0.2932 (3)	−0.0214 (2)	−0.2021 (2)	0.0737 (9)
H6A	0.2729	0.0366	−0.2311	0.111*
H6B	0.2345	−0.0653	−0.2226	0.111*
H6C	0.3658	−0.0412	−0.2216	0.111*
C7	0.49848 (19)	0.20079 (16)	0.35230 (16)	0.0429 (5)
C8	0.5578 (2)	0.29325 (16)	0.33022 (17)	0.0464 (5)
C9	0.3521 (2)	−0.03512 (16)	0.41212 (17)	0.0476 (5)
C10	0.2838 (3)	−0.1102 (2)	0.4323 (2)	0.0663 (8)
H10	0.2952	−0.1667	0.4044	0.080*
C11	0.2013 (3)	−0.0996 (2)	0.4928 (2)	0.0753 (9)
H11	0.1557	−0.1492	0.5060	0.090*
C12	0.1831 (3)	−0.0162 (2)	0.5356 (2)	0.0710 (9)
H12	0.1254	−0.0100	0.5766	0.085*
C13	0.2502 (2)	0.0565 (2)	0.51737 (16)	0.0544 (6)
C14	0.2420 (3)	0.1494 (2)	0.5583 (2)	0.0767 (9)
H14A	0.3029	0.1580	0.6096	0.115*
H14B	0.1686	0.1565	0.5832	0.115*
H14C	0.2490	0.1939	0.5086	0.115*
C15	0.0091 (2)	0.26412 (17)	0.33994 (19)	0.0491 (6)
C16	0.0641 (2)	0.19779 (16)	0.26897 (18)	0.0460 (5)
N1	0.36821 (17)	0.05787 (13)	−0.05609 (15)	0.0459 (4)
N3	0.33292 (17)	0.04379 (13)	0.45650 (13)	0.0437 (4)
N2	0.4457 (2)	0.14867 (19)	0.06970 (17)	0.0668 (6)
N4	0.4353 (2)	−0.03672 (15)	0.35294 (18)	0.0605 (6)
O1	0.48960 (16)	0.14569 (12)	0.28478 (12)	0.0549 (4)
O2	0.46713 (18)	0.19317 (14)	0.43335 (12)	0.0660 (5)
O3	−0.01711 (18)	0.34018 (12)	0.30739 (14)	0.0637 (5)
O4	0.0005 (2)	0.23281 (15)	0.42110 (15)	0.0791 (6)
Cl1	0.55673 (9)	0.37373 (6)	0.42317 (6)	0.0896 (3)
Cl2	0.70242 (6)	0.27091 (5)	0.31008 (6)	0.0710 (2)
Cl3	0.48451 (7)	0.34145 (5)	0.22382 (6)	0.0752 (2)
Cl4	0.21459 (6)	0.22009 (6)	0.28120 (6)	0.0697 (2)
Cl5	0.01042 (7)	0.21709 (6)	0.14738 (5)	0.0719 (2)
Cl6	0.04405 (9)	0.08231 (5)	0.29620 (7)	0.0861 (3)
H4B	0.463 (2)	0.0160 (11)	0.3358 (19)	0.059 (8)*
H2B	0.474 (2)	0.1848 (16)	0.0269 (17)	0.064 (9)*
H4A	0.447 (3)	−0.0864 (14)	0.320 (2)	0.082 (10)*
H2A	0.455 (3)	0.157 (2)	0.1332 (8)	0.082 (10)*
H1A	0.403 (2)	0.0949 (15)	−0.0955 (16)	0.057 (8)*
H3A	0.379 (2)	0.0908 (13)	0.446 (2)	0.061 (8)*

	U11	U22	U33	U12	U13	U23
C1	0.0481 (14)	0.0549 (14)	0.0483 (13)	0.0081 (11)	0.0017 (10)	0.0075 (11)
C2	0.0690 (19)	0.084 (2)	0.0605 (17)	−0.0020 (16)	0.0039 (14)	0.0247 (16)
C3	0.078 (2)	0.083 (2)	0.095 (3)	−0.0068 (19)	0.0106 (19)	0.039 (2)
C4	0.0634 (19)	0.0526 (16)	0.108 (3)	−0.0103 (14)	0.0013 (17)	0.0084 (17)
C5	0.0451 (14)	0.0417 (12)	0.0764 (18)	0.0072 (10)	−0.0007 (12)	−0.0040 (12)
C6	0.076 (2)	0.0650 (18)	0.079 (2)	0.0008 (15)	0.0022 (16)	−0.0237 (16)
C7	0.0384 (11)	0.0478 (12)	0.0423 (12)	−0.0102 (10)	0.0031 (9)	0.0052 (10)
C8	0.0464 (13)	0.0488 (13)	0.0453 (12)	−0.0116 (10)	0.0105 (10)	0.0016 (10)
C9	0.0539 (14)	0.0453 (13)	0.0428 (12)	−0.0052 (11)	0.0019 (10)	0.0071 (10)
C10	0.079 (2)	0.0514 (15)	0.0682 (18)	−0.0218 (14)	0.0046 (15)	0.0071 (13)
C11	0.077 (2)	0.084 (2)	0.0644 (18)	−0.0401 (18)	0.0034 (15)	0.0191 (16)
C12	0.0600 (17)	0.104 (2)	0.0517 (15)	−0.0272 (17)	0.0167 (13)	0.0075 (16)
C13	0.0502 (14)	0.0788 (18)	0.0352 (12)	−0.0098 (13)	0.0087 (10)	0.0016 (12)
C14	0.082 (2)	0.092 (2)	0.0611 (17)	−0.0084 (18)	0.0311 (16)	−0.0186 (17)
C15	0.0401 (12)	0.0493 (14)	0.0595 (15)	−0.0035 (10)	0.0123 (10)	−0.0009 (11)
C16	0.0422 (12)	0.0440 (12)	0.0525 (13)	−0.0031 (10)	0.0074 (10)	0.0012 (10)
N1	0.0439 (11)	0.0427 (10)	0.0513 (11)	0.0070 (9)	0.0057 (9)	0.0027 (9)
N3	0.0475 (11)	0.0494 (11)	0.0349 (9)	−0.0116 (9)	0.0073 (8)	0.0031 (8)
N2	0.0811 (17)	0.0736 (16)	0.0452 (13)	−0.0144 (13)	0.0042 (12)	−0.0005 (12)
N4	0.0733 (16)	0.0448 (12)	0.0675 (14)	−0.0029 (11)	0.0263 (12)	−0.0012 (11)
O1	0.0684 (11)	0.0488 (9)	0.0492 (10)	−0.0155 (8)	0.0144 (8)	−0.0021 (8)
O2	0.0833 (14)	0.0737 (12)	0.0437 (10)	−0.0383 (11)	0.0188 (9)	−0.0022 (9)
O3	0.0745 (13)	0.0496 (10)	0.0696 (12)	0.0085 (9)	0.0205 (10)	0.0019 (9)
O4	0.1060 (18)	0.0731 (13)	0.0642 (13)	0.0115 (12)	0.0377 (12)	0.0076 (10)
Cl1	0.1227 (8)	0.0727 (5)	0.0798 (5)	−0.0399 (5)	0.0406 (5)	−0.0284 (4)
Cl2	0.0438 (4)	0.0737 (5)	0.0975 (6)	−0.0119 (3)	0.0168 (3)	0.0099 (4)
Cl3	0.0823 (5)	0.0593 (4)	0.0805 (5)	−0.0066 (4)	−0.0083 (4)	0.0246 (4)
Cl4	0.0392 (3)	0.0947 (6)	0.0764 (5)	0.0005 (3)	0.0112 (3)	−0.0015 (4)
Cl5	0.0810 (5)	0.0774 (5)	0.0538 (4)	0.0001 (4)	−0.0092 (3)	−0.0080 (3)
Cl6	0.1113 (7)	0.0446 (4)	0.1068 (7)	−0.0056 (4)	0.0323 (5)	0.0062 (4)

C1—N2	1.324 (4)	C10—C11	1.350 (5)
C1—N1	1.357 (3)	C10—H10	0.9300
C1—C2	1.394 (4)	C11—C12	1.385 (5)
C2—C3	1.346 (5)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.362 (4)
C3—C4	1.401 (5)	C12—H12	0.9300
C3—H3	0.9300	C13—N3	1.360 (3)
C4—C5	1.360 (4)	C13—C14	1.483 (4)
C4—H4	0.9300	C14—H14A	0.9600
C5—N1	1.361 (3)	C14—H14B	0.9600
C5—C6	1.485 (4)	C14—H14C	0.9600
C6—H6A	0.9600	C15—O3	1.230 (3)
C6—H6B	0.9600	C15—O4	1.232 (3)
C6—H6C	0.9600	C15—C16	1.569 (3)
C7—O2	1.226 (3)	C16—Cl6	1.756 (2)
C7—O1	1.235 (3)	C16—Cl5	1.763 (3)
C7—C8	1.567 (3)	C16—Cl4	1.772 (2)
C8—Cl1	1.752 (2)	N1—H1A	0.898 (10)
C8—Cl2	1.765 (3)	N3—H3A	0.896 (10)
C8—Cl3	1.776 (3)	N2—H2B	0.885 (10)
C9—N4	1.335 (3)	N2—H2A	0.886 (10)
C9—N3	1.341 (3)	N4—H4B	0.881 (10)
C9—C10	1.404 (3)	N4—H4A	0.879 (10)
N2—C1—N1	118.6 (2)	C10—C11—C12	121.4 (3)
N2—C1—C2	123.3 (3)	C10—C11—H11	119.3
N1—C1—C2	118.0 (3)	C12—C11—H11	119.3
C3—C2—C1	119.2 (3)	C13—C12—C11	119.7 (3)
C3—C2—H2	120.4	C13—C12—H12	120.2
C1—C2—H2	120.4	C11—C12—H12	120.2
C2—C3—C4	121.5 (3)	N3—C13—C12	117.7 (3)
C2—C3—H3	119.3	N3—C13—C14	116.3 (2)
C4—C3—H3	119.3	C12—C13—C14	126.0 (3)
C5—C4—C3	119.3 (3)	C13—C14—H14A	109.5
C5—C4—H4	120.3	C13—C14—H14B	109.5
C3—C4—H4	120.3	H14A—C14—H14B	109.5
C4—C5—N1	118.2 (3)	C13—C14—H14C	109.5
C4—C5—C6	125.2 (3)	H14A—C14—H14C	109.5
N1—C5—C6	116.6 (2)	H14B—C14—H14C	109.5
C5—C6—H6A	109.5	O3—C15—O4	129.4 (2)
C5—C6—H6B	109.5	O3—C15—C16	115.6 (2)
H6A—C6—H6B	109.5	O4—C15—C16	115.0 (2)
C5—C6—H6C	109.5	C15—C16—Cl6	112.94 (17)
H6A—C6—H6C	109.5	C15—C16—Cl5	112.14 (17)
H6B—C6—H6C	109.5	Cl6—C16—Cl5	108.66 (13)
O2—C7—O1	129.1 (2)	C15—C16—Cl4	106.82 (16)
O2—C7—C8	116.1 (2)	Cl6—C16—Cl4	108.04 (13)
O1—C7—C8	114.87 (19)	Cl5—C16—Cl4	108.03 (13)
C7—C8—Cl1	113.64 (16)	C1—N1—C5	123.7 (2)
C7—C8—Cl2	108.53 (17)	C1—N1—H1A	117.3 (18)
Cl1—C8—Cl2	108.85 (13)	C5—N1—H1A	118.9 (18)
C7—C8—Cl3	108.95 (16)	C9—N3—C13	124.6 (2)
Cl1—C8—Cl3	107.87 (14)	C9—N3—H3A	117.3 (18)
Cl2—C8—Cl3	108.92 (12)	C13—N3—H3A	118.1 (18)
N4—C9—N3	117.7 (2)	C1—N2—H2B	120 (2)
N4—C9—C10	124.9 (3)	C1—N2—H2A	115 (2)
N3—C9—C10	117.4 (2)	H2B—N2—H2A	125 (3)
C11—C10—C9	119.2 (3)	C9—N4—H4B	117.6 (19)
C11—C10—H10	120.4	C9—N4—H4A	120 (2)
C9—C10—H10	120.4	H4B—N4—H4A	120 (3)
N2—C1—C2—C3	−179.4 (3)	C11—C12—C13—N3	0.3 (4)
N1—C1—C2—C3	−0.2 (4)	C11—C12—C13—C14	−179.4 (3)
C1—C2—C3—C4	−0.6 (5)	O3—C15—C16—Cl6	−154.9 (2)
C2—C3—C4—C5	0.0 (5)	O4—C15—C16—Cl6	26.5 (3)
C3—C4—C5—N1	1.4 (4)	O3—C15—C16—Cl5	−31.7 (3)
C3—C4—C5—C6	−177.7 (3)	O4—C15—C16—Cl5	149.7 (2)
O2—C7—C8—Cl1	−5.5 (3)	O3—C15—C16—Cl4	86.5 (2)
O1—C7—C8—Cl1	174.28 (18)	O4—C15—C16—Cl4	−92.2 (2)
O2—C7—C8—Cl2	115.8 (2)	N2—C1—N1—C5	−179.0 (2)
O1—C7—C8—Cl2	−64.5 (2)	C2—C1—N1—C5	1.7 (4)
O2—C7—C8—Cl3	−125.8 (2)	C4—C5—N1—C1	−2.3 (4)
O1—C7—C8—Cl3	54.0 (3)	C6—C5—N1—C1	176.9 (2)
N4—C9—C10—C11	−179.3 (3)	N4—C9—N3—C13	178.8 (2)
N3—C9—C10—C11	1.5 (4)	C10—C9—N3—C13	−1.9 (4)
C9—C10—C11—C12	−0.3 (5)	C12—C13—N3—C9	1.0 (4)
C10—C11—C12—C13	−0.6 (5)	C14—C13—N3—C9	−179.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3i	0.90 (1)	1.96 (1)	2.856 (3)	172 (3)
N2—H2B···O4i	0.89 (1)	1.95 (1)	2.825 (3)	167 (3)
N2—H2A···O1	0.89 (1)	2.11 (1)	2.982 (3)	167 (3)
N3—H3A···O2	0.90 (1)	1.84 (1)	2.729 (2)	175 (3)
N4—H4B···O1	0.88 (1)	2.06 (1)	2.929 (3)	167 (3)
N4—H4A···O3ii	0.88 (1)	2.29 (2)	3.096 (3)	152 (3)
C6—H6C···O1iii	0.96	2.50	3.413 (4)	158
C11—H11···O4iv	0.93	2.50	3.371 (4)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.90 (1)	1.96 (1)	2.856 (3)	172 (3)
N2—H2B⋯O4i	0.89 (1)	1.95 (1)	2.825 (3)	167 (3)
N2—H2A⋯O1	0.89 (1)	2.11 (1)	2.982 (3)	167 (3)
N3—H3A⋯O2	0.90 (1)	1.84 (1)	2.729 (2)	175 (3)
N4—H4B⋯O1	0.88 (1)	2.06 (1)	2.929 (3)	167 (3)
N4—H4A⋯O3ii	0.88 (1)	2.29 (2)	3.096 (3)	152 (3)
C6—H6C⋯O1iii	0.96	2.50	3.413 (4)	158
C11—H11⋯O4iv	0.93	2.50	3.371 (4)	157

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