5-Amino-6-methyl-quinolin-1-ium hydrogen malonate-malonic acid (2/1).

The asymmetric unit of the title compound, 2C10H11N2(+)·2C3H3O4(-)·C3H4O4, consists of one 5-amino-6-methyl-quinolin-1-ium cation, one hydrogen malonate (2-carb-oxy-acetate) anion and one-half mol-ecule of malonic acid which lies on a twofold rotation axis. The quinoline ring system is essentially planar, with a maximum deviation of 0.062 (2) Å for all non-H atoms. In the anion, an intra-molecular O-H⋯O hydrogen bond generates an S(6) ring. In the crystal, the components are linked via N-H⋯O and O-H⋯O hydrogen bonds into layers parallel to the ac plane. The crystal structure also features weak C-H⋯O hydrogen bonds and a π-π stacking inter-action with a centroid-centroid distance of 3.8189 (10) Å.

Related literature

For background to and the biological activity of quinoline derivatives, see: Sasaki et al. (1998 ▶); Reux et al. (2009 ▶); Morimoto et al. (1991 ▶); Markees et al. (1970 ▶). For related structures, see: Thanigaimani et al. (2013a ▶,b ▶); Loh et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

2C10H11N2 +·2C3H3O4 −·C3H4O4

M = 628.59

Monoclinic,

a = 24.701 (2) Å

b = 4.8530 (4) Å

c = 25.063 (2) Å

β = 95.321 (3)°

V = 2991.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 297 K

0.35 × 0.24 × 0.09 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.962, T max = 0.990

25870 measured reflections

3835 independent reflections

2644 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.130

S = 1.03

3835 reflections

225 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.20 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/S1600536813002547/is5233sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813002547/is5233Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813002547/is5233Isup3.cml

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

2C10H11N2+·2C3H3O4−·C3H4O4	F(000) = 1320
Mr = 628.59	Dx = 1.396 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5351 reflections
a = 24.701 (2) Å	θ = 3.3–25.6°
b = 4.8530 (4) Å	µ = 0.11 mm−1
c = 25.063 (2) Å	T = 297 K
β = 95.321 (3)°	Block, orange
V = 2991.4 (4) Å3	0.35 × 0.24 × 0.09 mm
Z = 4

Bruker SMART APEXII DUO CCD area-detector diffractometer	3835 independent reflections
Radiation source: fine-focus sealed tube	2644 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
φ and ω scans	θmax = 28.6°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −31→32
Tmin = 0.962, Tmax = 0.990	k = −6→6
25870 measured reflections	l = −33→33

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) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ2(Fo2) + (0.0604P)2 + 1.0717P] where P = (Fo2 + 2Fc2)/3
3835 reflections	(Δ/σ)max < 0.001
225 parameters	Δρmax = 0.18 e Å−3
1 restraint	Δρmin = −0.20 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
O1	−0.13586 (5)	0.9772 (3)	0.04300 (6)	0.0754 (4)
O2	−0.07247 (5)	0.7142 (3)	0.01501 (6)	0.0746 (4)
O3	0.04562 (4)	1.0469 (3)	0.11941 (5)	0.0646 (3)
O4	0.02278 (5)	0.7599 (3)	0.05274 (5)	0.0690 (4)
O5	−0.04221 (5)	0.5560 (3)	0.16694 (5)	0.0732 (4)
O6	0.03881 (5)	0.3951 (3)	0.19696 (5)	0.0709 (4)
N1	0.14556 (5)	0.8482 (3)	0.09860 (5)	0.0512 (3)
N2	0.34061 (6)	0.9024 (4)	0.12530 (7)	0.0632 (4)
C1	0.14687 (6)	0.6550 (4)	0.06193 (7)	0.0565 (4)
H1A	0.1144	0.5844	0.0456	0.068*
C2	0.19582 (6)	0.5552 (4)	0.04724 (7)	0.0565 (4)
H2A	0.1966	0.4172	0.0216	0.068*
C3	0.24305 (6)	0.6638 (3)	0.07126 (6)	0.0513 (4)
H3A	0.2762	0.5997	0.0614	0.062*
C4	0.24260 (5)	0.8699 (3)	0.11047 (6)	0.0444 (3)
C5	0.29079 (6)	0.9876 (3)	0.13779 (6)	0.0475 (3)
C6	0.28603 (6)	1.1839 (4)	0.17747 (6)	0.0535 (4)
C7	0.23408 (7)	1.2695 (4)	0.18874 (7)	0.0577 (4)
H7A	0.2314	1.4035	0.2149	0.069*
C8	0.18716 (6)	1.1662 (4)	0.16329 (6)	0.0546 (4)
H8A	0.1534	1.2292	0.1716	0.066*
C9	0.19147 (6)	0.9639 (3)	0.12455 (6)	0.0456 (3)
C10	0.33584 (8)	1.3009 (5)	0.20828 (8)	0.0752 (6)
H10A	0.3588	1.3832	0.1838	0.113*
H10B	0.3553	1.1561	0.2278	0.113*
H10C	0.3253	1.4381	0.2329	0.113*
C11	−0.08862 (6)	0.9118 (3)	0.04500 (6)	0.0519 (4)
C12	−0.04600 (6)	1.0564 (4)	0.08107 (7)	0.0542 (4)
H12A	−0.0578	1.0564	0.1169	0.065*
H12B	−0.0449	1.2470	0.0696	0.065*
C13	0.01154 (6)	0.9451 (3)	0.08464 (7)	0.0518 (4)
C14	−0.00419 (6)	0.5507 (3)	0.20023 (6)	0.0508 (4)
C15	0.0000	0.7256 (5)	0.2500	0.0577 (6)
H15A	−0.0318	0.8431	0.2497	0.069*
H1N2	0.3459 (8)	0.782 (5)	0.0986 (8)	0.076 (6)*
H1N1	0.1100 (8)	0.914 (4)	0.1093 (8)	0.076 (6)*
H2N2	0.3720 (10)	0.970 (5)	0.1407 (9)	0.087 (7)*
H1O2	−0.0377 (4)	0.708 (5)	0.0215 (9)	0.101 (8)*
H106	0.0359 (11)	0.277 (6)	0.1633 (11)	0.118 (9)*

	U11	U22	U33	U12	U13	U23
O1	0.0428 (6)	0.0887 (9)	0.0941 (9)	0.0145 (6)	0.0024 (6)	−0.0245 (8)
O2	0.0540 (7)	0.0738 (8)	0.0968 (10)	0.0054 (6)	0.0106 (7)	−0.0355 (7)
O3	0.0419 (6)	0.0825 (8)	0.0691 (7)	0.0156 (6)	0.0030 (5)	−0.0146 (6)
O4	0.0498 (6)	0.0737 (8)	0.0849 (8)	0.0168 (6)	0.0147 (6)	−0.0213 (7)
O5	0.0489 (6)	0.0961 (10)	0.0726 (8)	0.0098 (6)	−0.0045 (6)	−0.0194 (7)
O6	0.0606 (7)	0.0848 (9)	0.0654 (8)	0.0233 (7)	−0.0046 (6)	−0.0097 (7)
N1	0.0367 (6)	0.0633 (8)	0.0538 (7)	0.0116 (6)	0.0049 (5)	0.0025 (6)
N2	0.0379 (7)	0.0767 (10)	0.0755 (10)	0.0060 (7)	0.0072 (7)	−0.0156 (8)
C1	0.0425 (8)	0.0668 (10)	0.0592 (9)	0.0066 (7)	−0.0009 (7)	0.0000 (8)
C2	0.0486 (8)	0.0628 (10)	0.0578 (9)	0.0086 (7)	0.0039 (7)	−0.0074 (8)
C3	0.0419 (8)	0.0590 (9)	0.0537 (9)	0.0118 (7)	0.0084 (6)	−0.0010 (7)
C4	0.0382 (7)	0.0500 (8)	0.0457 (7)	0.0089 (6)	0.0080 (6)	0.0074 (6)
C5	0.0400 (7)	0.0524 (8)	0.0507 (8)	0.0071 (6)	0.0076 (6)	0.0063 (7)
C6	0.0490 (8)	0.0601 (9)	0.0522 (9)	0.0032 (7)	0.0084 (6)	0.0002 (7)
C7	0.0597 (10)	0.0624 (10)	0.0525 (9)	0.0095 (8)	0.0131 (7)	−0.0059 (8)
C8	0.0469 (8)	0.0654 (10)	0.0530 (9)	0.0148 (7)	0.0127 (7)	0.0013 (7)
C9	0.0380 (7)	0.0535 (8)	0.0457 (8)	0.0103 (6)	0.0068 (6)	0.0090 (6)
C10	0.0613 (11)	0.0880 (14)	0.0763 (12)	−0.0041 (10)	0.0059 (9)	−0.0216 (11)
C11	0.0458 (8)	0.0521 (8)	0.0588 (9)	0.0081 (7)	0.0097 (7)	−0.0027 (7)
C12	0.0461 (8)	0.0580 (9)	0.0580 (9)	0.0166 (7)	0.0023 (7)	−0.0075 (7)
C13	0.0422 (8)	0.0588 (9)	0.0555 (9)	0.0132 (7)	0.0104 (7)	0.0015 (7)
C14	0.0442 (8)	0.0558 (9)	0.0529 (8)	0.0000 (7)	0.0066 (6)	0.0047 (7)
C15	0.0634 (14)	0.0508 (12)	0.0581 (13)	0.000	0.0020 (11)	0.000

O1—C11	1.2060 (18)	C4—C9	1.4178 (19)
O2—C11	1.3037 (19)	C4—C5	1.436 (2)
O2—H1O2	0.859 (10)	C5—C6	1.390 (2)
O3—C13	1.2556 (19)	C6—C7	1.402 (2)
O4—C13	1.2511 (19)	C6—C10	1.502 (2)
O5—C14	1.1973 (19)	C7—C8	1.365 (2)
O6—C14	1.3119 (19)	C7—H7A	0.9300
O6—H106	1.02 (3)	C8—C9	1.392 (2)
N1—C1	1.316 (2)	C8—H8A	0.9300
N1—C9	1.374 (2)	C10—H10A	0.9600
N1—H1N1	0.99 (2)	C10—H10B	0.9600
N2—C5	1.3619 (19)	C10—H10C	0.9600
N2—H1N2	0.91 (2)	C11—C12	1.497 (2)
N2—H2N2	0.90 (2)	C12—C13	1.515 (2)
C1—C2	1.384 (2)	C12—H12A	0.9700
C1—H1A	0.9300	C12—H12B	0.9700
C2—C3	1.368 (2)	C14—C15	1.504 (2)
C2—H2A	0.9300	C15—C14i	1.505 (2)
C3—C4	1.403 (2)	C15—H15A	0.9700
C3—H3A	0.9300
C11—O2—H1O2	105.8 (17)	C7—C8—H8A	121.0
C14—O6—H106	112.4 (15)	C9—C8—H8A	121.0
C1—N1—C9	123.32 (13)	N1—C9—C8	120.35 (13)
C1—N1—H1N1	119.8 (12)	N1—C9—C4	117.77 (14)
C9—N1—H1N1	116.9 (12)	C8—C9—C4	121.88 (14)
C5—N2—H1N2	124.0 (13)	C6—C10—H10A	109.5
C5—N2—H2N2	123.7 (15)	C6—C10—H10B	109.5
H1N2—N2—H2N2	112.1 (19)	H10A—C10—H10B	109.5
N1—C1—C2	120.93 (15)	C6—C10—H10C	109.5
N1—C1—H1A	119.5	H10A—C10—H10C	109.5
C2—C1—H1A	119.5	H10B—C10—H10C	109.5
C3—C2—C1	118.60 (16)	O1—C11—O2	121.09 (16)
C3—C2—H2A	120.7	O1—C11—C12	121.68 (14)
C1—C2—H2A	120.7	O2—C11—C12	117.22 (13)
C2—C3—C4	121.41 (14)	C11—C12—C13	118.13 (14)
C2—C3—H3A	119.3	C11—C12—H12A	107.8
C4—C3—H3A	119.3	C13—C12—H12A	107.8
C3—C4—C9	117.96 (13)	C11—C12—H12B	107.8
C3—C4—C5	123.90 (13)	C13—C12—H12B	107.8
C9—C4—C5	118.13 (14)	H12A—C12—H12B	107.1
N2—C5—C6	120.70 (15)	O4—C13—O3	123.50 (14)
N2—C5—C4	119.77 (15)	O4—C13—C12	118.75 (15)
C6—C5—C4	119.52 (13)	O3—C13—C12	117.74 (14)
C5—C6—C7	119.12 (15)	O5—C14—O6	123.80 (16)
C5—C6—C10	120.49 (15)	O5—C14—C15	123.69 (14)
C7—C6—C10	120.39 (16)	O6—C14—C15	112.50 (13)
C8—C7—C6	123.39 (16)	C14—C15—C14i	111.30 (19)
C8—C7—H7A	118.3	C14—C15—H15A	109.4
C6—C7—H7A	118.3	C14i—C15—H15A	109.4
C7—C8—C9	117.92 (14)
C9—N1—C1—C2	0.1 (3)	C6—C7—C8—C9	0.6 (3)
N1—C1—C2—C3	−0.7 (3)	C1—N1—C9—C8	−179.50 (15)
C1—C2—C3—C4	0.7 (3)	C1—N1—C9—C4	0.5 (2)
C2—C3—C4—C9	−0.2 (2)	C7—C8—C9—N1	178.46 (15)
C2—C3—C4—C5	178.70 (15)	C7—C8—C9—C4	−1.5 (2)
C3—C4—C5—N2	1.1 (2)	C3—C4—C9—N1	−0.4 (2)
C9—C4—C5—N2	−179.97 (14)	C5—C4—C9—N1	−179.35 (13)
C3—C4—C5—C6	−177.67 (14)	C3—C4—C9—C8	179.55 (14)
C9—C4—C5—C6	1.2 (2)	C5—C4—C9—C8	0.6 (2)
N2—C5—C6—C7	179.13 (16)	O1—C11—C12—C13	174.80 (16)
C4—C5—C6—C7	−2.1 (2)	O2—C11—C12—C13	−6.3 (2)
N2—C5—C6—C10	−1.5 (3)	C11—C12—C13—O4	8.8 (2)
C4—C5—C6—C10	177.31 (16)	C11—C12—C13—O3	−171.96 (15)
C5—C6—C7—C8	1.2 (3)	O5—C14—C15—C14i	119.16 (18)
C10—C6—C7—C8	−178.19 (18)	O6—C14—C15—C14i	−61.88 (12)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O3	1.00 (2)	1.76 (2)	2.7450 (17)	172.3 (18)
O2—H1O2···O4	0.86 (1)	1.64 (1)	2.4630 (18)	159 (2)
C1—H1A···O4	0.93	2.44	3.095 (2)	127
N2—H1N2···O1ii	0.91 (2)	2.11 (2)	3.012 (2)	173.4 (18)
N2—H2N2···O5iii	0.90 (2)	2.20 (2)	3.076 (2)	166 (2)
O6—H106···O3iv	1.02 (3)	1.60 (3)	2.5927 (19)	164 (2)
C1—H1A···O2v	0.93	2.28	3.106 (2)	148
C3—H3A···O1ii	0.93	2.34	3.2648 (19)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O3	1.00 (2)	1.76 (2)	2.7450 (17)	172.3 (18)
O2—H1O2⋯O4	0.86 (1)	1.64 (1)	2.4630 (18)	159 (2)
C1—H1A⋯O4	0.93	2.44	3.095 (2)	127
N2—H1N2⋯O1i	0.91 (2)	2.11 (2)	3.012 (2)	173.4 (18)
N2—H2N2⋯O5ii	0.90 (2)	2.20 (2)	3.076 (2)	166 (2)
O6—H106⋯O3iii	1.02 (3)	1.60 (3)	2.5927 (19)	164 (2)
C1—H1A⋯O2iv	0.93	2.28	3.106 (2)	148
C3—H3A⋯O1i	0.93	2.34	3.2648 (19)	174

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