2-Amino-4-methyl-pyridinium 6-carb-oxy-pyridine-2-carboxyl-ate methanol monosolvate.

In the title solvated molecular salt, C(6)H(9)N(2) (+)·C(7)H(4)NO(4) (-)·CH(4)O, the pyridine N atom of 2-amino-4-methyl-pyridine is protonated and one carboxyl group of pyridine-2,6-dicarb-oxy-lic acid is deprotonated. The dihedral angles between the -CO(2) and -COH groups and the pyridine ring are 0.65 (13) and 7.4°. The crystal packing is stabilized by inter-molecular N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds.

Related literature

For background to proton-transfer compounds, see: Aghabozorg et al. (2008 ▶). For related structures, see: Aakeröy et al. (1998 ▶); Aghabozorg et al. (2006 ▶); Al-Allaf et al. (2003 ▶); Fu et al. (2005 ▶); Linden et al. (2003 ▶); Moghimi et al. (2004 ▶); Sheshmani et al. (2006 ▶); Thanigaimani et al. (2007 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4n class="Chemical">NO4 −·CH4O

M = 307.31

Triclinic,

a = 7.2191 (14) Å

b = 9.5095 (19) Å

c = 11.139 (2) Å

α = 94.44 (3)°

β = 99.76 (3)°

γ = 92.50 (3)°

V = 750.1 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.4 × 0.25 × 0.2 mm

Data collection

Stoe IPDS II diffractometer

8658 measured reflections

4005 independent reflections

2697 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.079

wR(F 2) = 0.216

S = 1.17

4005 reflections

222 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.26 e Å−3

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-AREA; 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810050245/bt5416sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810050245/bt5416Isup2.hkl

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

C6H9N2+·C7H4NO4−·CH4O	Z = 2
Mr = 307.31	F(000) = 324.0
Triclinic, P1	Dx = 1.361 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2191 (14) Å	Cell parameters from 4005 reflections
b = 9.5095 (19) Å	θ = 2.2–29.2°
c = 11.139 (2) Å	µ = 0.11 mm−1
α = 94.44 (3)°	T = 298 K
β = 99.76 (3)°	Block, colorless
γ = 92.50 (3)°	0.4 × 0.25 × 0.2 mm
V = 750.1 (3) Å3

Stoe IPDS II diffractometer	2697 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.058
graphite	θmax = 29.2°, θmin = 2.2°
Detector resolution: 0.15 mm pixels mm-1	h = −9→9
rotation method scans	k = −12→13
8658 measured reflections	l = −15→15
4005 independent reflections

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)] = 0.079	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.216	w = 1/[σ2(Fo2) + (0.0939P)2 + 0.144P] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max < 0.001
4005 reflections	Δρmax = 0.44 e Å−3
222 parameters	Δρmin = −0.26 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: 0.07 (2)

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
O1	0.0312 (3)	−0.1514 (2)	0.73074 (19)	0.0679 (6)
O2	0.2937 (3)	−0.1669 (2)	0.8602 (2)	0.0686 (6)
O3	−0.3748 (2)	0.20309 (19)	0.76854 (17)	0.0544 (5)
O4	−0.2965 (3)	0.3911 (2)	0.9022 (2)	0.0730 (7)
O5	0.7131 (3)	0.9637 (2)	0.6320 (2)	0.0685 (6)
N1	−0.0374 (3)	0.09454 (18)	0.84467 (16)	0.0381 (4)
N2	0.2829 (3)	0.3098 (2)	0.70000 (18)	0.0424 (5)
N3	0.3671 (4)	0.5125 (3)	0.8268 (3)	0.0689 (8)
C2	0.1276 (3)	0.0410 (2)	0.8845 (2)	0.0415 (5)
C3	0.2618 (4)	0.1087 (3)	0.9759 (3)	0.0567 (7)
H3	0.3748	0.0678	1.0017	0.068*
C4	0.2249 (4)	0.2381 (3)	1.0281 (3)	0.0587 (7)
H4	0.3135	0.2872	1.0890	0.070*
C5	0.0548 (4)	0.2936 (2)	0.9886 (2)	0.0501 (6)
H5	0.0264	0.3806	1.0229	0.060*
C6	−0.0741 (3)	0.2185 (2)	0.8971 (2)	0.0386 (5)
C1	0.1592 (4)	−0.1007 (3)	0.8243 (2)	0.0495 (6)
C7	−0.2648 (3)	0.2756 (2)	0.8524 (2)	0.0455 (5)
C8	0.2394 (3)	0.4369 (2)	0.7460 (2)	0.0447 (5)
C9	0.0583 (3)	0.4838 (3)	0.7033 (2)	0.0509 (6)
H9	0.0248	0.5712	0.7337	0.061*
C10	−0.0679 (3)	0.4020 (3)	0.6179 (2)	0.0478 (6)
C11	−0.0140 (4)	0.2706 (3)	0.5725 (2)	0.0545 (6)
H11	−0.0972	0.2136	0.5138	0.065*
C12	0.1599 (4)	0.2277 (3)	0.6147 (2)	0.0515 (6)
H12	0.1953	0.1408	0.5848	0.062*
C13	−0.2608 (4)	0.4518 (4)	0.5746 (3)	0.0691 (8)
H13A	−0.3498	0.4075	0.6168	0.104*
H13B	−0.2964	0.4272	0.4882	0.104*
H13C	−0.2592	0.5525	0.5910	0.104*
C14	0.5526 (5)	0.8734 (4)	0.6264 (4)	0.0877 (11)
H14A	0.5833	0.7775	0.6097	0.132*
H14B	0.4556	0.8979	0.5625	0.132*
H14C	0.5088	0.8831	0.7032	0.132*
H5A	0.700 (6)	1.030 (5)	0.676 (4)	0.097 (14)*
H2	0.392 (5)	0.282 (3)	0.727 (3)	0.058 (8)*
H1	−0.058 (6)	−0.094 (4)	0.713 (4)	0.095 (12)*
H3A	0.338 (5)	0.595 (4)	0.855 (3)	0.084 (11)*
H3B	0.465 (5)	0.479 (4)	0.861 (3)	0.068 (9)*

	U11	U22	U33	U12	U13	U23
O1	0.0737 (14)	0.0578 (11)	0.0673 (13)	0.0256 (10)	0.0023 (10)	−0.0158 (9)
O2	0.0602 (12)	0.0590 (11)	0.0874 (14)	0.0301 (9)	0.0100 (10)	0.0034 (10)
O3	0.0426 (9)	0.0509 (9)	0.0627 (11)	0.0152 (7)	−0.0078 (8)	−0.0096 (8)
O4	0.0609 (12)	0.0584 (11)	0.0882 (15)	0.0281 (9)	−0.0126 (10)	−0.0246 (10)
O5	0.0592 (12)	0.0678 (13)	0.0696 (13)	0.0078 (10)	−0.0027 (10)	−0.0227 (10)
N1	0.0377 (9)	0.0360 (9)	0.0402 (9)	0.0065 (7)	0.0046 (7)	0.0020 (7)
N2	0.0400 (10)	0.0427 (10)	0.0432 (10)	0.0103 (8)	0.0031 (8)	0.0000 (8)
N3	0.0466 (13)	0.0550 (13)	0.0925 (19)	0.0163 (11)	−0.0104 (12)	−0.0305 (13)
C2	0.0390 (11)	0.0390 (10)	0.0482 (12)	0.0102 (8)	0.0089 (9)	0.0069 (9)
C3	0.0380 (12)	0.0537 (14)	0.0738 (17)	0.0107 (10)	−0.0055 (11)	0.0060 (12)
C4	0.0488 (14)	0.0515 (14)	0.0654 (16)	−0.0006 (11)	−0.0137 (12)	−0.0053 (12)
C5	0.0527 (14)	0.0368 (11)	0.0546 (14)	0.0052 (10)	−0.0049 (11)	−0.0040 (10)
C6	0.0381 (11)	0.0355 (10)	0.0408 (11)	0.0061 (8)	0.0020 (8)	0.0031 (8)
C1	0.0512 (14)	0.0451 (12)	0.0546 (14)	0.0161 (10)	0.0137 (11)	0.0014 (10)
C7	0.0418 (12)	0.0420 (11)	0.0506 (13)	0.0132 (9)	0.0021 (9)	−0.0014 (9)
C8	0.0387 (11)	0.0413 (11)	0.0526 (13)	0.0072 (9)	0.0058 (9)	−0.0029 (9)
C9	0.0421 (12)	0.0462 (12)	0.0648 (15)	0.0127 (10)	0.0091 (11)	0.0011 (11)
C10	0.0370 (11)	0.0550 (13)	0.0519 (13)	0.0036 (10)	0.0043 (10)	0.0136 (10)
C11	0.0503 (14)	0.0585 (15)	0.0491 (14)	−0.0037 (11)	−0.0016 (11)	−0.0042 (11)
C12	0.0538 (14)	0.0449 (12)	0.0530 (14)	0.0051 (10)	0.0067 (11)	−0.0077 (10)
C13	0.0419 (14)	0.081 (2)	0.083 (2)	0.0088 (13)	−0.0001 (13)	0.0215 (16)
C14	0.078 (2)	0.076 (2)	0.106 (3)	−0.0007 (18)	0.012 (2)	0.003 (2)

O1—C1	1.315 (3)	C4—C5	1.375 (4)
O1—H1	0.87 (4)	C4—H4	0.9300
O2—C1	1.208 (3)	C5—C6	1.386 (3)
O3—C7	1.257 (3)	C5—H5	0.9300
O4—C7	1.240 (3)	C6—C7	1.520 (3)
O5—C14	1.401 (4)	C8—C9	1.417 (3)
O5—H5A	0.78 (5)	C9—C10	1.367 (4)
N1—C6	1.332 (3)	C9—H9	0.9300
N1—C2	1.335 (3)	C10—C11	1.407 (4)
N2—C8	1.347 (3)	C10—C13	1.504 (4)
N2—C12	1.356 (3)	C11—C12	1.356 (4)
N2—H2	0.85 (3)	C11—H11	0.9300
N3—C8	1.318 (3)	C12—H12	0.9300
N3—H3A	0.87 (4)	C13—H13A	0.9600
N3—H3B	0.83 (4)	C13—H13B	0.9600
C2—C3	1.378 (4)	C13—H13C	0.9600
C2—C1	1.503 (3)	C14—H14A	0.9600
C3—C4	1.376 (4)	C14—H14B	0.9600
C3—H3	0.9300	C14—H14C	0.9600
C1—O1—H1	112 (3)	O3—C7—C6	117.74 (19)
C14—O5—H5A	106 (3)	N3—C8—N2	118.9 (2)
C6—N1—C2	118.17 (19)	N3—C8—C9	123.1 (2)
C8—N2—C12	122.1 (2)	N2—C8—C9	118.0 (2)
C8—N2—H2	118 (2)	C10—C9—C8	120.7 (2)
C12—N2—H2	120 (2)	C10—C9—H9	119.6
C8—N3—H3A	118 (2)	C8—C9—H9	119.6
C8—N3—H3B	123 (2)	C9—C10—C11	118.7 (2)
H3A—N3—H3B	118 (3)	C9—C10—C13	120.3 (3)
N1—C2—C3	123.2 (2)	C11—C10—C13	121.0 (3)
N1—C2—C1	115.8 (2)	C12—C11—C10	119.6 (2)
C3—C2—C1	121.0 (2)	C12—C11—H11	120.2
C4—C3—C2	118.5 (2)	C10—C11—H11	120.2
C4—C3—H3	120.8	C11—C12—N2	120.9 (2)
C2—C3—H3	120.8	C11—C12—H12	119.5
C5—C4—C3	118.9 (2)	N2—C12—H12	119.5
C5—C4—H4	120.6	C10—C13—H13A	109.5
C3—C4—H4	120.6	C10—C13—H13B	109.5
C4—C5—C6	119.3 (2)	H13A—C13—H13B	109.5
C4—C5—H5	120.3	C10—C13—H13C	109.5
C6—C5—H5	120.3	H13A—C13—H13C	109.5
N1—C6—C5	122.0 (2)	H13B—C13—H13C	109.5
N1—C6—C7	117.22 (19)	O5—C14—H14A	109.5
C5—C6—C7	120.77 (19)	O5—C14—H14B	109.5
O2—C1—O1	121.0 (2)	H14A—C14—H14B	109.5
O2—C1—C2	122.2 (2)	O5—C14—H14C	109.5
O1—C1—C2	116.8 (2)	H14A—C14—H14C	109.5
O4—C7—O3	125.9 (2)	H14B—C14—H14C	109.5
O4—C7—C6	116.3 (2)
C6—N1—C2—C3	−0.8 (3)	N1—C6—C7—O4	−180.0 (2)
C6—N1—C2—C1	178.48 (19)	C5—C6—C7—O4	0.1 (4)
N1—C2—C3—C4	−0.5 (4)	N1—C6—C7—O3	−0.6 (3)
C1—C2—C3—C4	−179.8 (2)	C5—C6—C7—O3	179.4 (2)
C2—C3—C4—C5	1.1 (4)	C12—N2—C8—N3	−178.6 (3)
C3—C4—C5—C6	−0.4 (4)	C12—N2—C8—C9	0.4 (4)
C2—N1—C6—C5	1.5 (3)	N3—C8—C9—C10	178.9 (3)
C2—N1—C6—C7	−178.5 (2)	N2—C8—C9—C10	0.0 (4)
C4—C5—C6—N1	−0.9 (4)	C8—C9—C10—C11	−0.5 (4)
C4—C5—C6—C7	179.1 (2)	C8—C9—C10—C13	179.1 (2)
N1—C2—C1—O2	−172.4 (2)	C9—C10—C11—C12	0.5 (4)
C3—C2—C1—O2	6.9 (4)	C13—C10—C11—C12	−179.0 (3)
N1—C2—C1—O1	6.6 (3)	C10—C11—C12—N2	−0.1 (4)
C3—C2—C1—O1	−174.1 (2)	C8—N2—C12—C11	−0.3 (4)

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14C···O2i	0.96	2.59	3.488 (5)	157.
O5—H5A···O3ii	0.78 (5)	2.02 (5)	2.796 (3)	170 (4)
N3—H3B···O4iii	0.83 (4)	1.95 (4)	2.764 (3)	166 (3)
N3—H3A···O2i	0.87 (4)	2.30 (4)	3.122 (3)	158 (3)
N2—H2···O3iii	0.85 (3)	1.87 (3)	2.723 (3)	173 (3)
O1—H1···O5iv	0.87 (4)	1.87 (4)	2.689 (3)	156 (4)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14C⋯O2i	0.96	2.59	3.488 (5)	157
O5—H5A⋯O3ii	0.78 (5)	2.02 (5)	2.796 (3)	170 (4)
N3—H3B⋯O4iii	0.83 (4)	1.95 (4)	2.764 (3)	166 (3)
N3—H3A⋯O2i	0.87 (4)	2.30 (4)	3.122 (3)	158 (3)
N2—H2⋯O3iii	0.85 (3)	1.87 (3)	2.723 (3)	173 (3)
O1—H1⋯O5iv	0.87 (4)	1.87 (4)	2.689 (3)	156 (4)

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