2-Amino-4-methyl-pyridinium 4-amino-benzoate.

In the structure of the title salt, C(6)H(9)N(2) (+)·C(7)H(6)NO(2) (-), the 4-amino-benzoate anions are linked to adjacent anions and 2-amino-4-methyl-pyridinium cations via N-H⋯O hydrogen bonds, forming a three-dimensional supra-molecular structure. The crystal structure also shows a weak C-H⋯O hydrogen bond between adjacent anions. Within the 4-amino-benzoate anion, the carboxyl-ate group is twisted by 14.0 (4)° with respect to the benz-ene ring.

Related literature

For general background, see: Choudhury et al. (2007 ▶); Halvorson et al. (1987 ▶); Geiser et al. (1986 ▶); Geiser & Willett (1984 ▶). For related structures, see: Kaabi & Khedhiri (2004 ▶); Chtioui et al. (2006 ▶). For a description of the Cambridge Structural Database, see Allen (2002 ▶).

Experimental

Crystal data

C6H9N2 +·C7H6NO2 −

M = 245.28

Orthorhombic,

a = 5.5734 (14) Å

b = 8.8154 (16) Å

c = 25.374 (5) Å

V = 1246.6 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 295 (2) K

0.46 × 0.38 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer

Absorption correction: none

14099 measured reflections

1451 independent reflections

1126 reflections with I > 2σ(I)

R int = 0.059

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.095

S = 1.04

1451 reflections

165 parameters

H-atom parameters constrained

Δρmax = 0.13 e Å−3

Δρmin = −0.12 e Å−3

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); 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/S1600536808014839/ng2457sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808014839/ng2457Isup2.hkl

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

C6H9N2+·C7H6NO2–	F000 = 520
Mr = 245.28	Dx = 1.307 Mg m−3
Orthorhombic, P212121	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2654 reflections
a = 5.5734 (14) Å	θ = 2.0–25.2º
b = 8.8154 (16) Å	µ = 0.09 mm−1
c = 25.374 (5) Å	T = 295 (2) K
V = 1246.6 (5) Å3	Chunk, light brown
Z = 4	0.46 × 0.38 × 0.30 mm

Rigaku R-AXIS RAPID IP diffractometer	1451 independent reflections
Radiation source: fine-focus sealed tube	1126 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.059
Detector resolution: 10.00 pixels mm-1	θmax = 26.0º
T = 295(2) K	θmin = 1.6º
ω scans	h = −6→6
Absorption correction: none	k = −10→10
14099 measured reflections	l = −30→29

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037	w = 1/[σ2(Fo2) + (0.0449P)2 + 0.1505P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.095	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.13 e Å−3
1451 reflections	Δρmin = −0.12 e Å−3
165 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.015 (3)
Secondary atom site location: difference Fourier map

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
N1	−0.5107 (5)	0.2323 (3)	0.74214 (9)	0.0710 (7)
H1A	−0.4459	0.1947	0.7712	0.106*
H1B	−0.6362	0.1981	0.7267	0.106*
N2	0.5736 (4)	0.8834 (2)	0.61196 (7)	0.0520 (6)
H2N	0.4548	0.8231	0.6256	0.078*
N3	0.4308 (5)	0.8308 (3)	0.52906 (8)	0.0660 (7)
H3A	0.4443	0.8528	0.4934	0.099*
H3B	0.3098	0.7766	0.5454	0.099*
O1	0.0737 (4)	0.6432 (2)	0.57815 (6)	0.0692 (6)
O2	0.2584 (3)	0.6999 (2)	0.65310 (6)	0.0562 (5)
C1	−0.0644 (4)	0.5269 (3)	0.65687 (9)	0.0451 (6)
C2	−0.0117 (4)	0.4843 (3)	0.70832 (9)	0.0497 (6)
H2	0.1249	0.5233	0.7244	0.060*
C3	−0.1565 (5)	0.3857 (3)	0.73617 (9)	0.0523 (7)
H3	−0.1139	0.3568	0.7702	0.063*
C4	−0.3654 (5)	0.3295 (3)	0.71361 (9)	0.0488 (6)
C5	−0.4210 (5)	0.3741 (3)	0.66250 (10)	0.0581 (7)
H5	−0.5612	0.3388	0.6468	0.070*
C6	−0.2727 (5)	0.4694 (3)	0.63474 (10)	0.0550 (7)
H6	−0.3129	0.4960	0.6004	0.066*
C7	0.0980 (5)	0.6303 (3)	0.62688 (9)	0.0479 (6)
C8	0.5886 (5)	0.9037 (3)	0.55940 (9)	0.0482 (6)
C9	0.7670 (5)	1.0014 (3)	0.53990 (10)	0.0520 (6)
H9	0.7815	1.0156	0.5037	0.062*
C10	0.9189 (5)	1.0757 (3)	0.57306 (10)	0.0551 (7)
C11	0.8960 (6)	1.0501 (3)	0.62760 (11)	0.0668 (8)
H11	0.9977	1.0989	0.6512	0.080*
C12	0.7262 (6)	0.9547 (3)	0.64526 (10)	0.0636 (8)
H12	0.7131	0.9372	0.6813	0.076*
C13	1.1031 (6)	1.1849 (3)	0.55251 (12)	0.0742 (8)
H13A	1.1123	1.1766	0.5148	0.111*
H13B	1.2567	1.1615	0.5676	0.111*
H13C	1.0582	1.2865	0.5619	0.111*

	U11	U22	U33	U12	U13	U23
N1	0.0621 (14)	0.0843 (17)	0.0664 (14)	−0.0162 (14)	−0.0039 (12)	0.0169 (13)
N2	0.0637 (14)	0.0562 (12)	0.0360 (11)	0.0004 (12)	0.0035 (11)	0.0007 (9)
N3	0.0751 (15)	0.0825 (16)	0.0403 (11)	−0.0200 (16)	0.0037 (12)	−0.0003 (11)
O1	0.0800 (14)	0.0940 (14)	0.0336 (9)	−0.0151 (13)	−0.0001 (10)	0.0088 (9)
O2	0.0660 (11)	0.0651 (10)	0.0374 (9)	−0.0093 (11)	0.0020 (10)	0.0024 (8)
C1	0.0495 (14)	0.0509 (13)	0.0350 (12)	0.0068 (13)	0.0035 (12)	0.0009 (10)
C2	0.0508 (14)	0.0590 (14)	0.0391 (13)	−0.0028 (13)	−0.0028 (11)	0.0011 (12)
C3	0.0537 (16)	0.0673 (16)	0.0360 (12)	−0.0002 (14)	−0.0013 (11)	0.0086 (13)
C4	0.0489 (15)	0.0536 (14)	0.0440 (14)	0.0021 (13)	0.0023 (12)	0.0017 (12)
C5	0.0525 (15)	0.0734 (18)	0.0484 (15)	−0.0043 (16)	−0.0046 (14)	−0.0018 (13)
C6	0.0599 (17)	0.0668 (17)	0.0383 (14)	0.0070 (16)	−0.0040 (13)	0.0035 (12)
C7	0.0559 (16)	0.0525 (14)	0.0354 (13)	0.0065 (14)	0.0036 (12)	0.0021 (11)
C8	0.0554 (15)	0.0498 (13)	0.0395 (13)	0.0042 (14)	0.0032 (12)	0.0006 (11)
C9	0.0635 (16)	0.0517 (13)	0.0409 (13)	0.0048 (15)	0.0058 (13)	0.0019 (11)
C10	0.0574 (16)	0.0479 (14)	0.0598 (16)	0.0027 (14)	0.0011 (15)	0.0004 (12)
C11	0.076 (2)	0.0692 (18)	0.0554 (17)	−0.0099 (18)	−0.0100 (16)	−0.0047 (14)
C12	0.082 (2)	0.0698 (18)	0.0387 (14)	0.0010 (19)	−0.0040 (15)	−0.0012 (13)
C13	0.0708 (19)	0.0678 (18)	0.084 (2)	−0.0106 (19)	0.0038 (18)	−0.0001 (16)

N1—C4	1.384 (3)	C3—H3	0.9300
N1—H1A	0.8846	C4—C5	1.390 (3)
N1—H1B	0.8568	C5—C6	1.373 (4)
N2—C8	1.348 (3)	C5—H5	0.9300
N2—C12	1.354 (3)	C6—H6	0.9300
N2—H2N	0.9167	C8—C9	1.405 (4)
N3—C8	1.334 (3)	C9—C10	1.361 (4)
N3—H3A	0.9287	C9—H9	0.9300
N3—H3B	0.9252	C10—C11	1.408 (4)
O1—C7	1.249 (3)	C10—C13	1.501 (4)
O2—C7	1.272 (3)	C11—C12	1.343 (4)
C1—C6	1.385 (4)	C11—H11	0.9300
C1—C2	1.390 (3)	C12—H12	0.9300
C1—C7	1.494 (3)	C13—H13A	0.9600
C2—C3	1.381 (3)	C13—H13B	0.9600
C2—H2	0.9300	C13—H13C	0.9600
C3—C4	1.389 (3)
C4—N1—H1A	115.4	C1—C6—H6	119.3
C4—N1—H1B	117.1	O1—C7—O2	123.4 (2)
H1A—N1—H1B	125.7	O1—C7—C1	119.6 (2)
C8—N2—C12	121.1 (2)	O2—C7—C1	117.0 (2)
C8—N2—H2N	119.7	N3—C8—N2	117.8 (2)
C12—N2—H2N	119.2	N3—C8—C9	124.0 (2)
C8—N3—H3A	114.1	N2—C8—C9	118.3 (2)
C8—N3—H3B	118.1	C10—C9—C8	121.1 (2)
H3A—N3—H3B	127.2	C10—C9—H9	119.4
C6—C1—C2	117.3 (2)	C8—C9—H9	119.4
C6—C1—C7	121.7 (2)	C9—C10—C11	118.3 (3)
C2—C1—C7	121.0 (2)	C9—C10—C13	121.3 (2)
C3—C2—C1	121.8 (2)	C11—C10—C13	120.4 (3)
C3—C2—H2	119.1	C12—C11—C10	119.5 (3)
C1—C2—H2	119.1	C12—C11—H11	120.3
C2—C3—C4	120.2 (2)	C10—C11—H11	120.3
C2—C3—H3	119.9	C11—C12—N2	121.7 (2)
C4—C3—H3	119.9	C11—C12—H12	119.1
N1—C4—C3	119.7 (2)	N2—C12—H12	119.1
N1—C4—C5	122.2 (2)	C10—C13—H13A	109.5
C3—C4—C5	118.1 (2)	C10—C13—H13B	109.5
C6—C5—C4	121.1 (3)	H13A—C13—H13B	109.5
C6—C5—H5	119.4	C10—C13—H13C	109.5
C4—C5—H5	119.4	H13A—C13—H13C	109.5
C5—C6—C1	121.4 (2)	H13B—C13—H13C	109.5
C5—C6—H6	119.3

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2i	0.89	2.19	3.021 (3)	157
N2—H2N···O2	0.92	1.69	2.606 (3)	174
N3—H3A···O1ii	0.93	1.95	2.844 (3)	160
N3—H3B···O1	0.92	1.95	2.872 (3)	174
C3—H3···O2i	0.93	2.52	3.301 (3)	142

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2i	0.89	2.19	3.021 (3)	157
N2—H2N⋯O2	0.92	1.69	2.606 (3)	174
N3—H3A⋯O1ii	0.93	1.95	2.844 (3)	160
N3—H3B⋯O1	0.92	1.95	2.872 (3)	174
C3—H3⋯O2i	0.93	2.52	3.301 (3)	142

Symmetry codes: (i) ; (ii) .