2,3-Diamino-pyridinium 4-meth-oxy-quinoline-2-carboxyl-ate.

In the 4-meth-oxy-quinoline-2-carboxyl-ate anion of the title salt, C5H8N3(+)·C11H8NO3(-), the dihedral angle between the quinoline ring system and the carboxyl-ate group is 16.54 (15)°. In the crystal, the cations and anions are linked via N-H⋯O and N-H⋯N hydrogen bonds, forming a centrosymmetric 2 + 2 aggregate with R2(2)(9) and R4(2)(8) ring motifs. These units are further connected via N-H⋯O hydrogen bonds into a layer parallel to the bc plane. The crystal structure is also stabilized by weak C-H⋯O hydrogen bonds and π-π inter-actions between pyridine rings [centroid-centroid distance = 3.5886 (8) Å] and between pyridine and benzene rings [centroid-centroid distance = 3.6328 (8) Å].

Related literature

For background to the chemistry of substituted pyridines, see: Pozharski et al. (1997 ▶); Katritzky et al. (1996 ▶). For background to and the biological activity of quinoline derivatives, see: Morimoto et al. (1991 ▶); Markees et al. (1970 ▶). For a related structure, see: Hemamalini & Fun (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C5H8N3 +·C11H8NO3 −

M = 312.33

Monoclinic,

a = 12.4338 (12) Å

b = 7.7462 (7) Å

c = 19.4626 (14) Å

β = 128.806 (4)°

V = 1460.8 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.24 × 0.21 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.976, T max = 0.989

17919 measured reflections

4820 independent reflections

3806 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.131

S = 1.02

4820 reflections

229 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.54 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812047642/is5215sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812047642/is5215Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812047642/is5215Isup3.cml

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

C5H8N3+·C11H8NO3−	F(000) = 656
Mr = 312.33	Dx = 1.420 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4575 reflections
a = 12.4338 (12) Å	θ = 2.7–31.3°
b = 7.7462 (7) Å	µ = 0.10 mm−1
c = 19.4626 (14) Å	T = 100 K
β = 128.806 (4)°	Block, brown
V = 1460.8 (2) Å3	0.24 × 0.21 × 0.11 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	4820 independent reflections
Radiation source: fine-focus sealed tube	3806 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 31.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −18→18
Tmin = 0.976, Tmax = 0.989	k = −11→11
17919 measured reflections	l = −28→28

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: inferred from neighbouring sites
wR(F2) = 0.131	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0667P)2 + 0.4735P] where P = (Fo2 + 2Fc2)/3
4820 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.54 e Å−3
0 restraints	Δρmin = −0.24 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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	1.05026 (9)	0.82361 (12)	0.41897 (6)	0.02018 (19)
O2	0.57301 (9)	0.98701 (12)	0.31851 (6)	0.02111 (19)
O3	0.59315 (10)	0.93999 (14)	0.43875 (7)	0.0273 (2)
N1	0.82921 (10)	0.75610 (13)	0.51232 (6)	0.0165 (2)
C1	0.96096 (11)	0.69323 (14)	0.55691 (7)	0.0157 (2)
C2	1.02304 (12)	0.60542 (16)	0.63772 (8)	0.0195 (2)
H2A	0.9720	0.5869	0.6583	0.023*
C3	1.15663 (13)	0.54699 (16)	0.68650 (8)	0.0214 (2)
H3A	1.1969	0.4874	0.7403	0.026*
C4	1.23432 (12)	0.57458 (16)	0.65750 (8)	0.0222 (2)
H4A	1.3269	0.5347	0.6921	0.027*
C5	1.17713 (12)	0.65876 (16)	0.57956 (8)	0.0193 (2)
H5A	1.2303	0.6772	0.5605	0.023*
C6	1.03897 (11)	0.71840 (15)	0.52728 (7)	0.0159 (2)
C7	0.97352 (11)	0.80680 (15)	0.44581 (8)	0.0156 (2)
C8	0.84151 (11)	0.87022 (15)	0.40172 (7)	0.0156 (2)
H8A	0.7961	0.9300	0.3474	0.019*
C9	0.77543 (11)	0.84423 (15)	0.43910 (7)	0.0151 (2)
C10	0.63500 (12)	0.92902 (15)	0.39471 (8)	0.0167 (2)
C11	0.98637 (14)	0.90182 (19)	0.33460 (9)	0.0239 (3)
H11A	1.0535	0.9092	0.3239	0.036*
H11B	0.9545	1.0180	0.3339	0.036*
H11C	0.9075	0.8316	0.2884	0.036*
N2	0.69022 (11)	0.60036 (14)	0.56941 (7)	0.0186 (2)
N3	0.61802 (11)	0.86007 (14)	0.58672 (7)	0.0187 (2)
N4	0.53416 (12)	0.68143 (16)	0.67353 (8)	0.0242 (2)
C12	0.63244 (11)	0.68819 (15)	0.59866 (7)	0.0156 (2)
C13	0.59474 (11)	0.59571 (16)	0.64456 (7)	0.0169 (2)
C14	0.62055 (13)	0.41992 (16)	0.65640 (8)	0.0205 (2)
H14A	0.5978	0.3557	0.6873	0.025*
C15	0.67973 (13)	0.33474 (17)	0.62363 (9)	0.0230 (3)
H15A	0.6954	0.2138	0.6316	0.028*
C16	0.71448 (13)	0.42631 (16)	0.58045 (8)	0.0222 (2)
H16A	0.7550	0.3702	0.5583	0.027*
H1	0.5578 (18)	0.916 (2)	0.5893 (11)	0.026 (4)*
H2	0.6256 (18)	0.899 (2)	0.5461 (11)	0.025 (4)*
H3	0.7185 (18)	0.663 (2)	0.5421 (12)	0.032 (5)*
H4	0.5352 (19)	0.630 (2)	0.7151 (12)	0.032 (5)*
H5	0.525 (2)	0.795 (3)	0.6708 (13)	0.041 (5)*

	U11	U22	U33	U12	U13	U23
O1	0.0191 (4)	0.0250 (4)	0.0228 (4)	0.0005 (3)	0.0162 (4)	0.0014 (3)
O2	0.0206 (4)	0.0255 (5)	0.0171 (4)	0.0057 (3)	0.0118 (3)	0.0008 (3)
O3	0.0298 (5)	0.0345 (5)	0.0303 (5)	0.0146 (4)	0.0251 (4)	0.0128 (4)
N1	0.0184 (4)	0.0158 (4)	0.0181 (4)	0.0026 (3)	0.0128 (4)	0.0007 (3)
C1	0.0179 (5)	0.0139 (5)	0.0172 (5)	0.0012 (4)	0.0119 (4)	−0.0007 (4)
C2	0.0222 (5)	0.0188 (5)	0.0184 (5)	0.0021 (4)	0.0132 (5)	0.0010 (4)
C3	0.0217 (5)	0.0193 (6)	0.0169 (5)	0.0013 (4)	0.0090 (4)	0.0009 (4)
C4	0.0161 (5)	0.0196 (6)	0.0229 (6)	0.0010 (4)	0.0083 (5)	−0.0010 (4)
C5	0.0158 (5)	0.0183 (5)	0.0226 (6)	−0.0006 (4)	0.0114 (4)	−0.0026 (4)
C6	0.0159 (5)	0.0139 (5)	0.0180 (5)	−0.0003 (4)	0.0107 (4)	−0.0024 (4)
C7	0.0167 (5)	0.0151 (5)	0.0189 (5)	−0.0021 (4)	0.0130 (4)	−0.0028 (4)
C8	0.0174 (5)	0.0151 (5)	0.0165 (5)	0.0003 (4)	0.0117 (4)	−0.0007 (4)
C9	0.0171 (5)	0.0142 (5)	0.0165 (5)	0.0013 (4)	0.0117 (4)	−0.0009 (4)
C10	0.0182 (5)	0.0155 (5)	0.0197 (5)	0.0020 (4)	0.0136 (4)	0.0005 (4)
C11	0.0258 (6)	0.0296 (7)	0.0236 (6)	0.0015 (5)	0.0191 (5)	0.0027 (5)
N2	0.0216 (5)	0.0197 (5)	0.0207 (5)	0.0027 (4)	0.0162 (4)	0.0017 (4)
N3	0.0231 (5)	0.0176 (5)	0.0226 (5)	0.0035 (4)	0.0178 (4)	0.0037 (4)
N4	0.0329 (6)	0.0248 (6)	0.0300 (6)	0.0098 (4)	0.0271 (5)	0.0095 (4)
C12	0.0149 (4)	0.0183 (5)	0.0146 (5)	0.0021 (4)	0.0097 (4)	0.0010 (4)
C13	0.0158 (5)	0.0205 (5)	0.0159 (5)	0.0015 (4)	0.0107 (4)	0.0023 (4)
C14	0.0218 (5)	0.0195 (5)	0.0231 (6)	0.0013 (4)	0.0154 (5)	0.0038 (4)
C15	0.0254 (6)	0.0174 (5)	0.0260 (6)	0.0029 (4)	0.0160 (5)	0.0017 (5)
C16	0.0263 (6)	0.0197 (6)	0.0237 (6)	0.0049 (4)	0.0172 (5)	0.0004 (5)

O1—C7	1.3509 (13)	C9—C10	1.5284 (15)
O1—C11	1.4351 (15)	C11—H11A	0.9800
O2—C10	1.2501 (14)	C11—H11B	0.9800
O3—C10	1.2537 (14)	C11—H11C	0.9800
N1—C9	1.3227 (15)	N2—C12	1.3475 (15)
N1—C1	1.3755 (14)	N2—C16	1.3688 (16)
C1—C2	1.4179 (16)	N2—H3	0.936 (18)
C1—C6	1.4185 (16)	N3—C12	1.3441 (15)
C2—C3	1.3743 (17)	N3—H1	0.893 (18)
C2—H2A	0.9500	N3—H2	0.905 (17)
C3—C4	1.4073 (19)	N4—C13	1.3634 (16)
C3—H3A	0.9500	N4—H4	0.893 (18)
C4—C5	1.3712 (18)	N4—H5	0.88 (2)
C4—H4A	0.9500	C12—C13	1.4337 (16)
C5—C6	1.4174 (15)	C13—C14	1.3848 (17)
C5—H5A	0.9500	C14—C15	1.4041 (18)
C6—C7	1.4242 (16)	C14—H14A	0.9500
C7—C8	1.3808 (15)	C15—C16	1.3606 (19)
C8—C9	1.4121 (16)	C15—H15A	0.9500
C8—H8A	0.9500	C16—H16A	0.9500
C7—O1—C11	117.67 (9)	O3—C10—C9	117.34 (10)
C9—N1—C1	117.42 (10)	O1—C11—H11A	109.5
N1—C1—C2	118.35 (10)	O1—C11—H11B	109.5
N1—C1—C6	122.84 (10)	H11A—C11—H11B	109.5
C2—C1—C6	118.76 (10)	O1—C11—H11C	109.5
C3—C2—C1	120.42 (11)	H11A—C11—H11C	109.5
C3—C2—H2A	119.8	H11B—C11—H11C	109.5
C1—C2—H2A	119.8	C12—N2—C16	123.66 (11)
C2—C3—C4	120.61 (11)	C12—N2—H3	117.9 (11)
C2—C3—H3A	119.7	C16—N2—H3	118.4 (11)
C4—C3—H3A	119.7	C12—N3—H1	119.7 (11)
C5—C4—C3	120.36 (11)	C12—N3—H2	113.9 (11)
C5—C4—H4A	119.8	H1—N3—H2	116.0 (16)
C3—C4—H4A	119.8	C13—N4—H4	117.5 (12)
C4—C5—C6	120.27 (11)	C13—N4—H5	122.8 (13)
C4—C5—H5A	119.9	H4—N4—H5	115.1 (17)
C6—C5—H5A	119.9	N3—C12—N2	118.40 (11)
C5—C6—C1	119.56 (11)	N3—C12—C13	122.85 (11)
C5—C6—C7	123.07 (11)	N2—C12—C13	118.68 (11)
C1—C6—C7	117.36 (10)	N4—C13—C14	122.73 (11)
O1—C7—C8	125.32 (11)	N4—C13—C12	119.69 (11)
O1—C7—C6	115.32 (10)	C14—C13—C12	117.57 (11)
C8—C7—C6	119.35 (10)	C13—C14—C15	121.28 (11)
C7—C8—C9	118.56 (10)	C13—C14—H14A	119.4
C7—C8—H8A	120.7	C15—C14—H14A	119.4
C9—C8—H8A	120.7	C16—C15—C14	119.68 (12)
N1—C9—C8	124.34 (10)	C16—C15—H15A	120.2
N1—C9—C10	117.26 (10)	C14—C15—H15A	120.2
C8—C9—C10	118.36 (10)	C15—C16—N2	119.11 (11)
O2—C10—O3	125.12 (11)	C15—C16—H16A	120.4
O2—C10—C9	117.50 (10)	N2—C16—H16A	120.4
C9—N1—C1—C2	177.07 (11)	C6—C7—C8—C9	−0.28 (16)
C9—N1—C1—C6	−0.38 (16)	C1—N1—C9—C8	3.32 (17)
N1—C1—C2—C3	−177.15 (11)	C1—N1—C9—C10	−174.09 (10)
C6—C1—C2—C3	0.41 (18)	C7—C8—C9—N1	−3.03 (18)
C1—C2—C3—C4	0.56 (19)	C7—C8—C9—C10	174.35 (10)
C2—C3—C4—C5	−0.68 (19)	N1—C9—C10—O2	−168.15 (11)
C3—C4—C5—C6	−0.19 (19)	C8—C9—C10—O2	14.27 (16)
C4—C5—C6—C1	1.15 (17)	N1—C9—C10—O3	14.14 (16)
C4—C5—C6—C7	179.93 (11)	C8—C9—C10—O3	−163.43 (11)
N1—C1—C6—C5	176.19 (11)	C16—N2—C12—N3	177.71 (11)
C2—C1—C6—C5	−1.25 (17)	C16—N2—C12—C13	0.46 (17)
N1—C1—C6—C7	−2.65 (16)	N3—C12—C13—N4	3.90 (17)
C2—C1—C6—C7	179.90 (11)	N2—C12—C13—N4	−178.98 (11)
C11—O1—C7—C8	−5.09 (17)	N3—C12—C13—C14	−176.96 (11)
C11—O1—C7—C6	176.10 (10)	N2—C12—C13—C14	0.16 (16)
C5—C6—C7—O1	2.97 (16)	N4—C13—C14—C15	178.25 (12)
C1—C6—C7—O1	−178.23 (10)	C12—C13—C14—C15	−0.86 (18)
C5—C6—C7—C8	−175.92 (11)	C13—C14—C15—C16	0.96 (19)
C1—C6—C7—C8	2.88 (16)	C14—C15—C16—N2	−0.34 (19)
O1—C7—C8—C9	−179.05 (11)	C12—N2—C16—C15	−0.37 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H2···O3	0.91 (2)	1.890 (19)	2.7670 (18)	162.8 (19)
N2—H3···N1	0.94 (2)	1.94 (3)	2.843 (2)	162.5 (19)
N3—H1···O3i	0.89 (2)	1.94 (2)	2.812 (2)	163.4 (16)
N4—H4···O2ii	0.893 (18)	1.978 (19)	2.8617 (15)	169.8 (17)
N4—H5···O2i	0.88 (2)	2.17 (3)	2.9419 (18)	146 (3)
C4—H4A···O2iii	0.95	2.45	3.3529 (15)	158

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H2⋯O3	0.91 (2)	1.890 (19)	2.7670 (18)	162.8 (19)
N2—H3⋯N1	0.94 (2)	1.94 (3)	2.843 (2)	162.5 (19)
N3—H1⋯O3i	0.89 (2)	1.94 (2)	2.812 (2)	163.4 (16)
N4—H4⋯O2ii	0.893 (18)	1.978 (19)	2.8617 (15)	169.8 (17)
N4—H5⋯O2i	0.88 (2)	2.17 (3)	2.9419 (18)	146 (3)
C4—H4A⋯O2iii	0.95	2.45	3.3529 (15)	158

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