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

In the title compound, C(6)H(9)N(2) (+)·C(7)H(4)NO(4) (-)·1.5H(2)O, extensive O-H⋯O, O-H⋯N, N-H⋯O and C-H⋯O hydrogen bonds, as well as ion pairing, π-π stacking inter-actions [centroid-centroid distances = 3.4690 (8) and 3.6932 (8) Å between aromatic rings] occur in the crystal. There are hydrogen-bonding inter-actions between water mol-ecules, which result in cyclic tetra-meric water clusters. One of the water O molecules has half occupancy. In the anion molecules, the -CO(2) and -CO(2)H groups make torsion angles of 1.73 (18) and -12.14 (18)° with respect to the ring.

Related literature

For background to hydrogen bonding involving water, see: Long et al. (2004 ▶); Atwood et al., 2001 ▶); Miyake & Aida (2003 ▶). For related structures, see: Aghabozorg et al. (2008 ▶); Tabatabaee et al. (2009 ▶).

Experimental

Crystal data

C6H9N2 +·C7H4NO4 −·1.5H2O

M = 302.29

Monoclinic,

a = 9.2373 (6) Å

b = 7.1972 (5) Å

c = 21.6495 (14) Å

β = 93.951 (1)°

V = 1435.90 (17) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 120 K

0.20 × 0.20 × 0.10 mm

Data collection

Bruker SMART 1000 CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.980, T max = 0.995

15297 measured reflections

3801 independent reflections

3077 reflections with I > 2.0σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.102

S = 0.99

3801 reflections

216 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.25 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; 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 (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I. DOI: 10.1107/S1600536810046866/pv2352sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046866/pv2352Isup2.hkl

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

C6H9N2+·C7H4NO4−·1.5H2O	F(000) = 636
Mr = 302.29	Dx = 1.398 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1125 reflections
a = 9.2373 (6) Å	θ = 2–25°
b = 7.1972 (5) Å	µ = 0.11 mm−1
c = 21.6495 (14) Å	T = 120 K
β = 93.951 (1)°	Rhombic, colorless
V = 1435.90 (17) Å3	0.20 × 0.20 × 0.10 mm
Z = 4

Bruker SMART 1000 CCD area detector diffractometer	3801 independent reflections
Radiation source: fine-focus sealed tube	3077 reflections with I > 2.0σ(I)
graphite	Rint = 0.026
φ and ω scans	θmax = 29.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −12→12
Tmin = 0.980, Tmax = 0.995	k = −9→9
15297 measured reflections	l = −29→29

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)] = 0.047	Hydrogen site location: mixed
wR(F2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ2(Fo2) + (0.0244P)2 + 1.3516P] where P = (Fo2 + 2Fc2)/3
3801 reflections	(Δ/σ)max = 0.001
216 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.25 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	Occ. (<1)
O1	0.26470 (12)	−0.06479 (14)	0.64545 (5)	0.0309 (2)
H1O	0.356 (3)	−0.019 (3)	0.6373 (11)	0.066 (7)*
O2	0.06351 (11)	0.00989 (15)	0.68870 (5)	0.0325 (2)
O3	0.64297 (10)	0.62489 (14)	0.66239 (5)	0.0288 (2)
O4	0.65846 (10)	0.32081 (14)	0.64256 (5)	0.0264 (2)
O1W	0.53707 (11)	0.96510 (15)	0.61389 (5)	0.0305 (2)
H1WA	0.5713	1.0680	0.6275	0.037*
H1WB	0.5756	0.8707	0.6320	0.037*
O2W	0.6530 (2)	1.0929 (3)	0.49926 (10)	0.0310 (5)	0.50
H2WB	0.5892	1.0666	0.4704	0.037*	0.50
H2WA	0.6142	1.0552	0.5315	0.037*	0.50
N1	0.38249 (11)	0.26733 (15)	0.67222 (5)	0.0192 (2)
N2	0.91543 (12)	0.37469 (16)	0.59293 (5)	0.0223 (2)
H2N	0.822 (2)	0.364 (3)	0.6099 (9)	0.043 (5)*
N3	0.93113 (13)	0.67564 (18)	0.62910 (6)	0.0270 (3)
H3NB	0.835 (2)	0.658 (3)	0.6447 (8)	0.037 (5)*
H3NA	0.986 (2)	0.776 (3)	0.6395 (9)	0.044 (5)*
C1	0.25047 (13)	0.23786 (18)	0.69207 (6)	0.0199 (2)
C2	0.17514 (14)	0.3666 (2)	0.72513 (6)	0.0232 (3)
H2A	0.0818	0.3388	0.7386	0.028*
C3	0.23996 (14)	0.5369 (2)	0.73793 (6)	0.0247 (3)
H3A	0.1922	0.6286	0.7607	0.030*
C4	0.37662 (14)	0.57143 (19)	0.71688 (6)	0.0223 (3)
H4A	0.4232	0.6876	0.7247	0.027*
C5	0.44366 (13)	0.43305 (18)	0.68430 (6)	0.0188 (2)
C6	0.18551 (15)	0.05222 (19)	0.67584 (7)	0.0246 (3)
C7	0.59368 (14)	0.46266 (18)	0.66116 (6)	0.0210 (3)
C8	0.99015 (14)	0.53539 (19)	0.59952 (6)	0.0213 (3)
C9	1.12726 (14)	0.5468 (2)	0.57398 (6)	0.0225 (3)
H9A	1.1815	0.6589	0.5776	0.027*
C10	1.18187 (14)	0.3971 (2)	0.54415 (6)	0.0236 (3)
C11	1.09980 (15)	0.2309 (2)	0.53908 (7)	0.0262 (3)
H11A	1.1361	0.1252	0.5189	0.031*
C12	0.96820 (15)	0.2250 (2)	0.56356 (7)	0.0260 (3)
H12A	0.9122	0.1143	0.5601	0.031*
C13	1.32713 (15)	0.4067 (2)	0.51713 (7)	0.0304 (3)
H13A	1.3607	0.5359	0.5172	0.046*
H13B	1.3184	0.3600	0.4745	0.046*
H13C	1.3971	0.3305	0.5420	0.046*

	U11	U22	U33	U12	U13	U23
O1	0.0254 (5)	0.0214 (5)	0.0463 (6)	−0.0024 (4)	0.0069 (4)	−0.0036 (4)
O2	0.0241 (5)	0.0321 (6)	0.0420 (6)	−0.0091 (4)	0.0083 (4)	0.0018 (5)
O3	0.0212 (5)	0.0213 (5)	0.0446 (6)	−0.0042 (4)	0.0074 (4)	−0.0023 (4)
O4	0.0197 (4)	0.0216 (5)	0.0390 (6)	0.0005 (4)	0.0097 (4)	−0.0001 (4)
O1W	0.0315 (5)	0.0227 (5)	0.0377 (6)	0.0012 (4)	0.0043 (4)	−0.0029 (4)
O2W	0.0253 (10)	0.0408 (12)	0.0271 (10)	0.0025 (9)	0.0032 (8)	−0.0036 (9)
N1	0.0168 (5)	0.0204 (5)	0.0208 (5)	0.0003 (4)	0.0027 (4)	0.0018 (4)
N2	0.0180 (5)	0.0242 (6)	0.0251 (5)	−0.0012 (4)	0.0040 (4)	0.0003 (4)
N3	0.0209 (6)	0.0264 (6)	0.0345 (7)	−0.0019 (5)	0.0076 (5)	−0.0054 (5)
C1	0.0181 (6)	0.0217 (6)	0.0201 (6)	−0.0010 (5)	0.0022 (4)	0.0027 (5)
C2	0.0188 (6)	0.0295 (7)	0.0219 (6)	0.0004 (5)	0.0046 (5)	0.0015 (5)
C3	0.0220 (6)	0.0287 (7)	0.0236 (6)	0.0040 (5)	0.0039 (5)	−0.0045 (5)
C4	0.0202 (6)	0.0216 (6)	0.0249 (6)	0.0000 (5)	0.0011 (5)	−0.0032 (5)
C5	0.0163 (5)	0.0207 (6)	0.0196 (6)	0.0008 (5)	0.0026 (4)	0.0010 (5)
C6	0.0235 (6)	0.0224 (6)	0.0280 (7)	−0.0027 (5)	0.0030 (5)	0.0041 (5)
C7	0.0177 (6)	0.0212 (6)	0.0242 (6)	−0.0007 (5)	0.0022 (5)	0.0015 (5)
C8	0.0182 (6)	0.0239 (6)	0.0219 (6)	0.0003 (5)	0.0019 (5)	0.0011 (5)
C9	0.0175 (6)	0.0263 (7)	0.0239 (6)	−0.0020 (5)	0.0025 (5)	0.0022 (5)
C10	0.0169 (6)	0.0325 (7)	0.0217 (6)	0.0024 (5)	0.0032 (5)	0.0034 (5)
C11	0.0248 (6)	0.0275 (7)	0.0266 (7)	0.0038 (5)	0.0038 (5)	−0.0028 (5)
C12	0.0248 (6)	0.0244 (7)	0.0288 (7)	−0.0012 (5)	0.0019 (5)	−0.0018 (5)
C13	0.0207 (6)	0.0409 (8)	0.0304 (7)	0.0028 (6)	0.0082 (5)	0.0023 (6)

O1—C6	1.3204 (17)	C2—C3	1.384 (2)
O1—H1O	0.93 (2)	C2—H2A	0.9500
O2—C6	1.2179 (17)	C3—C4	1.3937 (18)
O3—C7	1.2528 (16)	C3—H3A	0.9500
O4—C7	1.2632 (16)	C4—C5	1.3904 (18)
O1W—H1WA	0.8500	C4—H4A	0.9500
O1W—H1WB	0.8500	C5—C7	1.5206 (17)
O2W—H2WB	0.8500	C8—C9	1.4188 (17)
O2W—H2WA	0.8501	C9—C10	1.3701 (19)
N1—C1	1.3375 (16)	C9—H9A	0.9500
N1—C5	1.3379 (17)	C10—C11	1.416 (2)
N2—C8	1.3494 (17)	C10—C13	1.5019 (18)
N2—C12	1.3583 (18)	C11—C12	1.3598 (19)
N2—H2N	0.96 (2)	C11—H11A	0.9500
N3—C8	1.3320 (18)	C12—H12A	0.9500
N3—H3NB	0.978 (19)	C13—H13A	0.9800
N3—H3NA	0.90 (2)	C13—H13B	0.9800
C1—C2	1.3872 (18)	C13—H13C	0.9800
C1—C6	1.4966 (19)
C6—O1—H1O	114.2 (15)	O2—C6—C1	122.14 (13)
H1WA—O1W—H1WB	113.8	O1—C6—C1	117.35 (12)
H2WB—O2W—H2WA	102.8	O3—C7—O4	125.49 (12)
C1—N1—C5	117.44 (11)	O3—C7—C5	117.50 (12)
C8—N2—C12	122.13 (12)	O4—C7—C5	117.01 (11)
C8—N2—H2N	119.4 (12)	N3—C8—N2	118.49 (12)
C12—N2—H2N	118.5 (12)	N3—C8—C9	123.32 (13)
C8—N3—H3NB	118.6 (11)	N2—C8—C9	118.18 (12)
C8—N3—H3NA	119.0 (13)	C10—C9—C8	120.37 (13)
H3NB—N3—H3NA	121.7 (17)	C10—C9—H9A	119.8
N1—C1—C2	124.10 (12)	C8—C9—H9A	119.8
N1—C1—C6	115.21 (12)	C9—C10—C11	119.22 (12)
C2—C1—C6	120.69 (12)	C9—C10—C13	121.01 (13)
C3—C2—C1	118.01 (12)	C11—C10—C13	119.77 (13)
C3—C2—H2A	121.0	C12—C11—C10	118.97 (13)
C1—C2—H2A	121.0	C12—C11—H11A	120.5
C2—C3—C4	118.79 (12)	C10—C11—H11A	120.5
C2—C3—H3A	120.6	N2—C12—C11	121.12 (13)
C4—C3—H3A	120.6	N2—C12—H12A	119.4
C5—C4—C3	118.91 (13)	C11—C12—H12A	119.4
C5—C4—H4A	120.5	C10—C13—H13A	109.5
C3—C4—H4A	120.5	C10—C13—H13B	109.5
N1—C5—C4	122.74 (11)	H13A—C13—H13B	109.5
N1—C5—C7	116.28 (11)	C10—C13—H13C	109.5
C4—C5—C7	120.97 (12)	H13A—C13—H13C	109.5
O2—C6—O1	120.49 (13)	H13B—C13—H13C	109.5
C5—N1—C1—C2	−1.24 (19)	N1—C5—C7—O3	168.20 (12)
C5—N1—C1—C6	178.42 (11)	C4—C5—C7—O3	−12.68 (19)
N1—C1—C2—C3	0.6 (2)	N1—C5—C7—O4	−12.13 (17)
C6—C1—C2—C3	−179.05 (12)	C4—C5—C7—O4	166.98 (12)
C1—C2—C3—C4	0.4 (2)	C12—N2—C8—N3	−179.79 (13)
C2—C3—C4—C5	−0.6 (2)	C12—N2—C8—C9	0.82 (19)
C1—N1—C5—C4	0.94 (18)	N3—C8—C9—C10	179.92 (13)
C1—N1—C5—C7	−179.97 (11)	N2—C8—C9—C10	−0.72 (19)
C3—C4—C5—N1	0.0 (2)	C8—C9—C10—C11	0.0 (2)
C3—C4—C5—C7	−179.08 (12)	C8—C9—C10—C13	−179.71 (13)
N1—C1—C6—O2	−176.83 (13)	C9—C10—C11—C12	0.5 (2)
C2—C1—C6—O2	2.8 (2)	C13—C10—C11—C12	−179.69 (13)
N1—C1—C6—O1	1.73 (18)	C8—N2—C12—C11	−0.2 (2)
C2—C1—C6—O1	−178.60 (12)	C10—C11—C12—N2	−0.5 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O4i	0.85	2.01	2.846 (2)	169
O1W—H1WA···N1i	0.85	2.50	2.935 (2)	112
O1W—H1WB···O3	0.85	1.97	2.813 (2)	169
O2W—H2WB···O1Wii	0.85	2.11	2.944 (2)	167
O2W—H2WA···O1W	0.85	2.07	2.919 (2)	175
O1—H1O···O1Wiii	0.93 (3)	1.78 (3)	2.661 (2)	155 (2)
O1—H1O···N1	0.93 (3)	2.20 (2)	2.673 (2)	110 (2)
N2—H2N···O4	0.96 (2)	1.74 (2)	2.700 (2)	174 (2)
N3—H3NB···O3	0.98 (2)	1.86 (2)	2.829 (2)	172 (2)
N3—H3NA···O2iv	0.90 (2)	2.09 (2)	2.955 (2)	160 (2)
C2—H2A···O2v	0.95	2.47	3.158 (2)	129
C9—H9A···O1iv	0.95	2.56	3.399 (2)	147
C11—H11A···O2Wvi	0.95	2.55	3.405 (2)	149
Cg(1)N2/C8–C12—···.Cg(1)vi	.	.	3.4690 (8)	.
Cg(1)—···.Cg(2)N1/C1–C5vii	.	.	3.6932 (8)	.
C7—O3···Cg(2)viii	.	3.5023 (12)	.	124.86 (9)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O4i	0.85	2.01	2.846 (2)	169
O1W—H1WB⋯O3	0.85	1.97	2.813 (2)	169
O2W—H2WB⋯O1Wii	0.85	2.11	2.944 (2)	167
O2W—H2WA⋯O1W	0.85	2.07	2.919 (2)	175
O1—H1O⋯O1Wiii	0.93 (3)	1.78 (3)	2.661 (2)	155 (2)
N2—H2N⋯O4	0.96 (2)	1.74 (2)	2.700 (2)	174 (2)
N3—H3NB⋯O3	0.98 (2)	1.86 (2)	2.829 (2)	172 (2)
N3—H3NA⋯O2iv	0.90 (2)	2.09 (2)	2.955 (2)	160 (2)
C2—H2A⋯O2v	0.95	2.47	3.158 (2)	129
C9—H9A⋯O1iv	0.95	2.56	3.399 (2)	147
C11—H11A⋯O2Wvi	0.95	2.55	3.405 (2)	149

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