4-Meth-oxy-quinolinium-2-carboxyl-ate dihydrate.

The title hydrated quinoline derivative, C(11)H(9)NO(3)·2H(2)O, crystallizes as a zwitterion in which the quinoline N atom is protonated. The quinoline ring is essentially planar, with a maximum deviation of 0.017 (2) Å. An intra-molecular N-H⋯O hydrogen bond between the protonated N atom and the O atom of the carboxyl-ate group in the zwitterion forms an S(5) ring motif. In the crystal, the zwitterions are connected into inversion dimers via pairs of N-H⋯O and C-H⋯O hydrogen bonds with R(2) (2)(4) and R(1) (2)(6) motifs. The water mol-ecules are connected via O-H⋯O hydrogen bonds, forming supra-molecular chains along the c axis. Furthermore, the chains and the dimers are connected via O-H⋯O hydrogen bonds, forming ladder-like supra-molecular ribbons along the c axis.

Related literature

For background to and the biological activity of quinoline derivatives, see: Morimoto et al. (1991 ▶); Michael (1997 ▶); Markees et al. (1970 ▶); Campbell et al. (1988 ▶); Zhou et al. (1989 ▶); Elman et al. (1985 ▶); Loh et al. (2010 ▶); Sasaki et al. (1998 ▶); Reux et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C11H9NO3·2H2O

M = 239.22

Monoclinic,

a = 5.7674 (11) Å

b = 21.196 (4) Å

c = 10.0993 (15) Å

β = 115.978 (8)°

V = 1109.9 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.23 × 0.13 × 0.09 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.974, T max = 0.990

8743 measured reflections

3176 independent reflections

2123 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.140

S = 1.01

3176 reflections

155 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.34 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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001541/is2654sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811001541/is2654Isup2.hkl

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

C11H9NO3·2H2O	F(000) = 504
Mr = 239.22	Dx = 1.432 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1896 reflections
a = 5.7674 (11) Å	θ = 3.0–29.6°
b = 21.196 (4) Å	µ = 0.11 mm−1
c = 10.0993 (15) Å	T = 100 K
β = 115.978 (8)°	Block, colourless
V = 1109.9 (3) Å3	0.23 × 0.13 × 0.09 mm
Z = 4

Bruker APEXII DUO CCD area-detector diffractometer	3176 independent reflections
Radiation source: fine-focus sealed tube	2123 reflections with I > 2σ(I)
graphite	Rint = 0.058
φ and ω scans	θmax = 30.0°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→8
Tmin = 0.974, Tmax = 0.990	k = −29→29
8743 measured reflections	l = −10→14

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0701P)2] where P = (Fo2 + 2Fc2)/3
3176 reflections	(Δ/σ)max = 0.001
155 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.34 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 s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	−0.5092 (2)	0.92971 (5)	0.52984 (13)	0.0215 (3)
O2	−0.2912 (2)	0.83869 (5)	0.60229 (13)	0.0215 (3)
O3	0.6369 (2)	0.91915 (5)	0.88880 (13)	0.0209 (3)
N1	−0.0747 (2)	0.99667 (6)	0.64651 (14)	0.0164 (3)
H1	−0.2351	1.0154	0.5860	0.020*
C1	−0.0569 (3)	0.93435 (7)	0.66638 (17)	0.0167 (3)
C2	0.1785 (3)	0.90548 (7)	0.74844 (17)	0.0179 (3)
H2A	0.1879	0.8620	0.7624	0.022*
C3	0.4006 (3)	0.94219 (7)	0.80976 (17)	0.0172 (3)
C4	0.3838 (3)	1.00878 (7)	0.78808 (17)	0.0165 (3)
C5	0.6021 (3)	1.04912 (7)	0.84392 (18)	0.0196 (3)
H5A	0.7657	1.0325	0.8995	0.024*
C6	0.5718 (3)	1.11260 (8)	0.81587 (18)	0.0215 (4)
H6A	0.7157	1.1388	0.8513	0.026*
C7	0.3247 (3)	1.13855 (7)	0.73390 (18)	0.0213 (3)
H7A	0.3077	1.1818	0.7171	0.026*
C8	0.1083 (3)	1.10119 (7)	0.67844 (17)	0.0192 (3)
H8A	−0.0542	1.1187	0.6248	0.023*
C9	0.1385 (3)	1.03559 (7)	0.70470 (17)	0.0163 (3)
C10	−0.3094 (3)	0.89756 (7)	0.59208 (17)	0.0165 (3)
C11	0.6630 (3)	0.85142 (7)	0.91289 (19)	0.0229 (4)
H11A	0.8409	0.8411	0.9726	0.034*
H11B	0.6036	0.8302	0.8198	0.034*
H11C	0.5617	0.8382	0.9622	0.034*
O1W	0.0737 (2)	0.75591 (5)	0.16811 (14)	0.0248 (3)
H2	0.1349	0.7589	0.2622	0.037*
H3	−0.0434	0.7242	0.1451	0.037*
O2W	0.2854 (2)	0.76156 (6)	0.47021 (14)	0.0283 (3)
H4	0.4092	0.7895	0.5074	0.042*
H5	0.2167	0.7580	0.5317	0.042*

	U11	U22	U33	U12	U13	U23
O1	0.0150 (5)	0.0235 (5)	0.0221 (7)	0.0015 (4)	0.0045 (4)	0.0012 (4)
O2	0.0189 (5)	0.0199 (5)	0.0235 (6)	−0.0012 (4)	0.0073 (5)	0.0017 (4)
O3	0.0162 (5)	0.0211 (5)	0.0204 (6)	0.0024 (4)	0.0034 (4)	0.0024 (4)
N1	0.0153 (6)	0.0185 (6)	0.0135 (7)	0.0000 (5)	0.0046 (5)	−0.0006 (5)
C1	0.0171 (7)	0.0205 (7)	0.0137 (8)	−0.0010 (6)	0.0077 (6)	−0.0016 (6)
C2	0.0172 (7)	0.0189 (7)	0.0168 (8)	0.0004 (6)	0.0066 (6)	−0.0002 (6)
C3	0.0152 (7)	0.0244 (7)	0.0118 (8)	0.0026 (6)	0.0056 (6)	0.0004 (6)
C4	0.0154 (7)	0.0216 (7)	0.0126 (7)	0.0001 (6)	0.0061 (5)	−0.0011 (6)
C5	0.0160 (7)	0.0253 (7)	0.0153 (8)	−0.0016 (6)	0.0050 (6)	−0.0024 (6)
C6	0.0201 (7)	0.0245 (7)	0.0196 (9)	−0.0049 (6)	0.0083 (6)	−0.0049 (6)
C7	0.0236 (8)	0.0191 (7)	0.0207 (9)	−0.0016 (6)	0.0094 (6)	−0.0019 (6)
C8	0.0199 (7)	0.0209 (7)	0.0168 (8)	0.0010 (6)	0.0080 (6)	0.0000 (6)
C9	0.0167 (7)	0.0199 (7)	0.0122 (7)	−0.0005 (6)	0.0064 (6)	−0.0011 (6)
C10	0.0159 (7)	0.0201 (7)	0.0134 (8)	−0.0008 (5)	0.0061 (6)	−0.0004 (6)
C11	0.0214 (8)	0.0216 (7)	0.0228 (9)	0.0042 (6)	0.0070 (6)	0.0047 (6)
O1W	0.0256 (6)	0.0228 (5)	0.0244 (7)	−0.0035 (5)	0.0093 (5)	0.0004 (5)
O2W	0.0256 (6)	0.0335 (6)	0.0255 (7)	−0.0098 (5)	0.0110 (5)	−0.0068 (5)

O1—C10	1.2461 (18)	C5—H5A	0.9300
O2—C10	1.2528 (18)	C6—C7	1.409 (2)
O3—C3	1.3337 (18)	C6—H6A	0.9300
O3—C11	1.4530 (18)	C7—C8	1.373 (2)
N1—C1	1.3332 (19)	C7—H7A	0.9300
N1—C9	1.3800 (19)	C8—C9	1.412 (2)
N1—H1	0.9437	C8—H8A	0.9300
C1—C2	1.385 (2)	C11—H11A	0.9600
C1—C10	1.528 (2)	C11—H11B	0.9600
C2—C3	1.391 (2)	C11—H11C	0.9600
C2—H2A	0.9300	O1W—H2	0.8586
C3—C4	1.425 (2)	O1W—H3	0.9083
C4—C9	1.411 (2)	O2W—H4	0.8759
C4—C5	1.419 (2)	O2W—H5	0.8743
C5—C6	1.370 (2)
C3—O3—C11	117.76 (12)	C7—C6—H6A	119.7
C1—N1—C9	122.17 (13)	C8—C7—C6	121.28 (14)
C1—N1—H1	120.2	C8—C7—H7A	119.4
C9—N1—H1	117.5	C6—C7—H7A	119.4
N1—C1—C2	121.24 (14)	C7—C8—C9	118.44 (14)
N1—C1—C10	115.95 (13)	C7—C8—H8A	120.8
C2—C1—C10	122.80 (13)	C9—C8—H8A	120.8
C1—C2—C3	119.30 (14)	N1—C9—C4	119.14 (13)
C1—C2—H2A	120.3	N1—C9—C8	119.69 (13)
C3—C2—H2A	120.3	C4—C9—C8	121.16 (14)
O3—C3—C2	124.18 (14)	O1—C10—O2	127.72 (14)
O3—C3—C4	115.95 (13)	O1—C10—C1	116.14 (13)
C2—C3—C4	119.86 (13)	O2—C10—C1	116.14 (13)
C9—C4—C5	118.55 (14)	O3—C11—H11A	109.5
C9—C4—C3	118.28 (13)	O3—C11—H11B	109.5
C5—C4—C3	123.16 (14)	H11A—C11—H11B	109.5
C6—C5—C4	119.94 (14)	O3—C11—H11C	109.5
C6—C5—H5A	120.0	H11A—C11—H11C	109.5
C4—C5—H5A	120.0	H11B—C11—H11C	109.5
C5—C6—C7	120.61 (15)	H2—O1W—H3	103.8
C5—C6—H6A	119.7	H4—O2W—H5	106.9
C9—N1—C1—C2	0.7 (2)	C5—C6—C7—C8	−0.8 (3)
C9—N1—C1—C10	−178.65 (13)	C6—C7—C8—C9	−0.3 (2)
N1—C1—C2—C3	−0.8 (2)	C1—N1—C9—C4	0.0 (2)
C10—C1—C2—C3	178.50 (15)	C1—N1—C9—C8	179.18 (15)
C11—O3—C3—C2	−0.4 (2)	C5—C4—C9—N1	178.33 (14)
C11—O3—C3—C4	−179.67 (14)	C3—C4—C9—N1	−0.5 (2)
C1—C2—C3—O3	−179.06 (15)	C5—C4—C9—C8	−0.9 (2)
C1—C2—C3—C4	0.2 (2)	C3—C4—C9—C8	−179.68 (15)
O3—C3—C4—C9	179.73 (14)	C7—C8—C9—N1	−178.06 (15)
C2—C3—C4—C9	0.4 (2)	C7—C8—C9—C4	1.1 (2)
O3—C3—C4—C5	1.0 (2)	N1—C1—C10—O1	−5.3 (2)
C2—C3—C4—C5	−178.38 (15)	C2—C1—C10—O1	175.42 (15)
C9—C4—C5—C6	−0.3 (2)	N1—C1—C10—O2	175.44 (14)
C3—C4—C5—C6	178.51 (16)	C2—C1—C10—O2	−3.9 (2)
C4—C5—C6—C7	1.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.94	2.31	2.6638 (18)	102
N1—H1···O1i	0.94	1.84	2.7608 (18)	164
O1W—H2···O2W	0.86	1.89	2.7478 (19)	176
O1W—H3···O2ii	0.91	1.86	2.7685 (16)	177
O2W—H4···O2iii	0.88	1.88	2.7498 (18)	171
O2W—H5···O1Wiv	0.87	1.91	2.7860 (19)	176
C6—H6A···O1Wv	0.93	2.59	3.418 (2)	149
C8—H8A···O1i	0.93	2.53	3.229 (2)	132
C11—H11A···O1Wvi	0.96	2.58	3.317 (2)	134
C11—H11B···O2iii	0.96	2.53	3.272 (2)	134

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1i	0.94	1.84	2.7608 (18)	164
O1W—H2⋯O2W	0.86	1.89	2.7478 (19)	176
O1W—H3⋯O2ii	0.91	1.86	2.7685 (16)	177
O2W—H4⋯O2iii	0.88	1.88	2.7498 (18)	171
O2W—H5⋯O1Wiv	0.87	1.91	2.7860 (19)	176
C6—H6A⋯O1Wv	0.93	2.59	3.418 (2)	149
C8—H8A⋯O1i	0.93	2.53	3.229 (2)	132
C11—H11A⋯O1Wvi	0.96	2.58	3.317 (2)	134
C11—H11B⋯O2iii	0.96	2.53	3.272 (2)	134

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