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Acta Cryst. (2013). E69, o44    [ doi:10.1107/S1600536812049495 ]

8-Hydroxy-5,7-dimethylquinolin-1-ium chloride dihydrate

K. Thanigaimani, N. C. Khalib, S. Arshad and I. A. Razak

Abstract top

In the title hydrated salt, C11H12NO+·Cl-·2H2O, the quinoline ring system is essentially planar, with a maximum deviation of 0.005 (1) Å for all non-H atoms. In the crystal, the three components are linked by O-H...O, N-H...O, O-H...Cl and weak C-H...O hydrogen bonds, forming a layer structure parallel to the ac plane. The crystal structure is further stabilized by [pi]-[pi] stacking interactions, with centroid-centroid distances of 3.5213 (6) and 3.7176 (6) Å.

Comment top

Recently, much attention has been devoted to the design and synthesis of supramolecular architectures assembled via various weak noncovalent interactions in the crystal structures of oxines (8-hydroxyquinoline), their derivatives and their complexes in a variety of crystalline environments (Balasubramanian & Muthiah, 1996a,b). Oxine is widely used as analytical reagent. Quinolines and their derivatives are very important compounds because of their wide occurrence in natural products (Morimoto et al., 1991) and biologically active compounds (Markees et al., 1970). In order to study potential hydrogen bonding interactions the crystal structure determination of the title compound (I) was carried out.

The asymmetric unit of the title compound, (I) contains a 8-hydroxy-5,7-dimethylquinolin-1-ium cation, a chloride anion and two water molecules as shown in Fig. 1. One proton is transferred from the hydrochloric acid to the atom N1 of 8-hydroxy-5,7-dimethylquinoline during the crystallization, resulting the formation of salt. The quinoline ring system (N1/C1–C9) is planar with a maximum deviation of 0.005 (1) Å at atom C7. The bond lengths (Allen et al., 1987) and angles are normal.

In the crystal packing (Fig. 2), the ion pairs and water molecules are linked via O2W—H2W2···Cl1, O1—H1O1···O1W, N1—H1N1···O1Wi, O1W—H2W1···Cl1i, O2W—H1W2···Cl1ii, O1W—H1W1···O2Wiii and weak C1—H1A···O2W hydrogen bonds (symmetry codes in Table 1), forming a layer. Furthermore, the crystal structure is stabilized by the following π–π interactions: (a) between pyridine (N1/C1–C4/C9, centroid Cg1) and benzene (C4–C9, centroid Cg2) rings Cg1···Cg2 (1 - x, -y, 1 - z) 3.5213 (6) Å and (b) between benzene rings (C4–C9, centroid Cg2) Cg2···Cg2 (-x, -y, 1 - z) 3.7176 (6) Å.

Related literature top

For background to and the biological activity of quinoline derivatives, see: Balasubramanian & Muthiah (1996a,b); Morimoto et al. (1991); Markees et al. (1970). 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 top

To a hot methanol solution (20 ml) of 8-hydroxy-5,7-dimethylquinoline (36 mg, Aldrich) was added a few drops of hydrochloric acid. The solution was warmed over a heating magnetic stirrer hotplate for a few minutes. The resulting solution was allowed to cool slowly at room temperature and crystals of the title compound (I) appeared after a few days.

Refinement top

O- and N-bound H atoms were located in a difference Fourier map and were refined freely [O—H = 0.76 (2)–0.873 (19) Å and N—H = 0.828 (19) Å]. The rest of the hydrogen atoms were positioned geometrically (C—H = 0.95–0.98 Å) and were refined using a riding model, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). A rotating-group model was used for the methyl group. Eight outliers were omitted (-3 1 0, 4 -6 2, -4 0 5, -4 -2 3, -4 -3 2, -4 1 5, -4 -3 3 and 3 4 1) in the final refinement.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with atom labels with 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The crystal packing of the title compound. The H atoms not involved in the intermolecular interactions (dashed lines) have been omitted for clarity.
8-Hydroxy-5,7-dimethylquinolin-1-ium chloride dihydrate top
Crystal data top
C11H12NO+·Cl−·2H2OZ = 2
Mr = 245.70F(000) = 260
Triclinic, P1Dx = 1.383 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.7990 (5) ÅCell parameters from 6250 reflections
b = 9.2215 (6) Åθ = 2.7–30.1°
c = 10.2123 (7) ŵ = 0.32 mm−1
α = 103.820 (1)°T = 100 K
β = 95.629 (1)°Block, yellow
γ = 105.517 (1)°0.38 × 0.20 × 0.14 mm
V = 590.04 (7) Å3
Data collection top
Bruker APEXII DUO CCD area-detector
diffractometer		3410 independent reflections
Radiation source: fine-focus sealed tube3153 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.018
φ and ω scansθmax = 30.1°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		h = −9→9
Tmin = 0.889, Tmax = 0.958k = −12→12
9368 measured reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H atoms treated by a mixture of independent and constrained refinement
S = 1.08 w = 1/[σ2(Fo2) + (0.058P)2 + 0.1137P]
where P = (Fo2 + 2Fc2)/3
3410 reflections(Δ/σ)max = 0.001
171 parametersΔρmax = 0.43 e Å−3
0 restraintsΔρmin = −0.26 e Å−3
Crystal data top
C11H12NO+·Cl−·2H2Oγ = 105.517 (1)°
Mr = 245.70V = 590.04 (7) Å3
Triclinic, P1Z = 2
a = 6.7990 (5) ÅMo Kα radiation
b = 9.2215 (6) ŵ = 0.32 mm−1
c = 10.2123 (7) ÅT = 100 K
α = 103.820 (1)°0.38 × 0.20 × 0.14 mm
β = 95.629 (1)°
Data collection top
Bruker APEXII DUO CCD area-detector
diffractometer		3410 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		3153 reflections with I > 2σ(I)
Tmin = 0.889, Tmax = 0.958Rint = 0.018
9368 measured reflectionsθmax = 30.1°
Refinement top
R[F2 > 2σ(F2)] = 0.028H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.092Δρmax = 0.43 e Å−3
S = 1.08Δρmin = −0.26 e Å−3
3410 reflectionsAbsolute structure: ?
171 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.22874 (4)0.70417 (3)0.91682 (2)0.01867 (8)
O1W0.49841 (12)0.45266 (8)0.25460 (7)0.01707 (15)
O10.34288 (12)0.31466 (8)0.43983 (7)0.01753 (15)
O2W0.22470 (13)0.42047 (10)1.03561 (8)0.02223 (16)
N10.35726 (12)0.22535 (9)0.66748 (8)0.01260 (15)
C10.36928 (14)0.19382 (11)0.78767 (9)0.01493 (17)
H1A0.41330.27700.86990.018*
C20.31746 (15)0.03900 (11)0.79353 (9)0.01541 (17)
H2A0.32590.01590.87930.018*
C30.25385 (14)−0.08005 (11)0.67341 (9)0.01452 (17)
H3A0.2176−0.18580.67690.017*
C40.24166 (13)−0.04734 (10)0.54510 (9)0.01229 (16)
C50.17880 (14)−0.16484 (10)0.41697 (9)0.01365 (17)
C60.17410 (14)−0.11634 (10)0.29989 (9)0.01398 (17)
H6A0.1328−0.19420.21430.017*
C70.22731 (13)0.04326 (10)0.29896 (9)0.01296 (17)
C80.29038 (13)0.15788 (10)0.42249 (9)0.01246 (16)
C90.29632 (13)0.11195 (10)0.54492 (9)0.01168 (16)
C100.11810 (16)−0.33626 (11)0.41114 (10)0.01908 (19)
H10A0.0812−0.39940.31530.029*
H10B−0.0012−0.36130.45730.029*
H10C0.2348−0.35950.45690.029*
C110.21195 (15)0.08368 (11)0.16520 (9)0.01676 (18)
H11A0.13070.15720.16800.025*
H11B0.1439−0.01180.09080.025*
H11C0.35130.13200.14940.025*
H1N10.389 (3)0.318 (2)0.6664 (18)0.037 (4)*
H2W10.584 (3)0.411 (2)0.2240 (19)0.040 (5)*
H2W20.228 (3)0.497 (2)1.001 (2)0.050 (5)*
H1O10.385 (3)0.347 (2)0.3707 (19)0.038 (4)*
H1W20.115 (3)0.390 (2)1.0495 (18)0.036 (4)*
H1W10.416 (3)0.446 (2)0.1895 (19)0.038 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.02078 (13)0.01844 (12)0.01979 (13)0.00704 (9)0.00619 (9)0.00844 (9)
O1W0.0219 (3)0.0155 (3)0.0134 (3)0.0053 (3)0.0038 (3)0.0035 (2)
O10.0275 (4)0.0127 (3)0.0126 (3)0.0050 (3)0.0048 (3)0.0046 (2)
O2W0.0205 (4)0.0251 (4)0.0262 (4)0.0094 (3)0.0057 (3)0.0130 (3)
N10.0138 (3)0.0131 (3)0.0105 (3)0.0039 (3)0.0020 (3)0.0027 (3)
C10.0157 (4)0.0183 (4)0.0103 (4)0.0050 (3)0.0021 (3)0.0032 (3)
C20.0165 (4)0.0192 (4)0.0119 (4)0.0058 (3)0.0029 (3)0.0061 (3)
C30.0146 (4)0.0160 (4)0.0143 (4)0.0048 (3)0.0033 (3)0.0061 (3)
C40.0112 (4)0.0142 (4)0.0120 (4)0.0044 (3)0.0021 (3)0.0040 (3)
C50.0134 (4)0.0131 (4)0.0140 (4)0.0040 (3)0.0025 (3)0.0029 (3)
C60.0140 (4)0.0147 (4)0.0118 (4)0.0040 (3)0.0019 (3)0.0015 (3)
C70.0123 (4)0.0158 (4)0.0110 (4)0.0046 (3)0.0022 (3)0.0038 (3)
C80.0133 (4)0.0134 (4)0.0114 (4)0.0044 (3)0.0028 (3)0.0041 (3)
C90.0108 (3)0.0142 (4)0.0100 (4)0.0041 (3)0.0022 (3)0.0028 (3)
C100.0241 (5)0.0128 (4)0.0187 (4)0.0039 (3)0.0031 (4)0.0033 (3)
C110.0208 (4)0.0188 (4)0.0100 (4)0.0052 (3)0.0015 (3)0.0040 (3)
Geometric parameters (Å, º) top
O1W—H2W10.828 (19)C4—C91.4160 (12)
O1W—H1W10.806 (19)C4—C51.4262 (12)
O1—C81.3558 (11)C5—C61.3735 (12)
O1—H1O10.873 (19)C5—C101.5079 (13)
O2W—H2W20.86 (2)C6—C71.4211 (12)
O2W—H1W20.76 (2)C6—H6A0.9500
N1—C11.3271 (11)C7—C81.3809 (12)
N1—C91.3686 (11)C7—C111.5006 (12)
N1—H1N10.828 (19)C8—C91.4129 (12)
C1—C21.3935 (13)C10—H10A0.9800
C1—H1A0.9500C10—H10B0.9800
C2—C31.3768 (13)C10—H10C0.9800
C2—H2A0.9500C11—H11A0.9800
C3—C41.4127 (12)C11—H11B0.9800
C3—H3A0.9500C11—H11C0.9800
H2W1—O1W—H1W1106.5 (17)C7—C6—H6A118.0
C8—O1—H1O1116.0 (11)C8—C7—C6118.69 (8)
H2W2—O2W—H1W2107.8 (19)C8—C7—C11121.56 (8)
C1—N1—C9123.25 (8)C6—C7—C11119.75 (8)
C1—N1—H1N1118.5 (12)O1—C8—C7126.20 (8)
C9—N1—H1N1118.2 (12)O1—C8—C9115.02 (8)
N1—C1—C2120.13 (8)C7—C8—C9118.75 (8)
N1—C1—H1A119.9N1—C9—C8118.85 (8)
C2—C1—H1A119.9N1—C9—C4118.90 (8)
C3—C2—C1119.17 (8)C8—C9—C4122.25 (8)
C3—C2—H2A120.4C5—C10—H10A109.5
C1—C2—H2A120.4C5—C10—H10B109.5
C2—C3—C4121.00 (8)H10A—C10—H10B109.5
C2—C3—H3A119.5C5—C10—H10C109.5
C4—C3—H3A119.5H10A—C10—H10C109.5
C3—C4—C9117.54 (8)H10B—C10—H10C109.5
C3—C4—C5123.88 (8)C7—C11—H11A109.5
C9—C4—C5118.58 (8)C7—C11—H11B109.5
C6—C5—C4117.73 (8)H11A—C11—H11B109.5
C6—C5—C10121.45 (8)C7—C11—H11C109.5
C4—C5—C10120.82 (8)H11A—C11—H11C109.5
C5—C6—C7123.99 (8)H11B—C11—H11C109.5
C5—C6—H6A118.0
C9—N1—C1—C2−0.37 (14)C11—C7—C8—O10.57 (14)
N1—C1—C2—C3−0.04 (14)C6—C7—C8—C9−1.01 (13)
C1—C2—C3—C40.35 (14)C11—C7—C8—C9178.35 (8)
C2—C3—C4—C9−0.27 (13)C1—N1—C9—C8−179.47 (8)
C2—C3—C4—C5179.45 (8)C1—N1—C9—C40.44 (13)
C3—C4—C5—C6−179.96 (8)O1—C8—C9—N1−1.49 (12)
C9—C4—C5—C6−0.25 (12)C7—C8—C9—N1−179.51 (8)
C3—C4—C5—C100.53 (13)O1—C8—C9—C4178.60 (8)
C9—C4—C5—C10−179.75 (8)C7—C8—C9—C40.59 (13)
C4—C5—C6—C7−0.21 (13)C3—C4—C9—N1−0.12 (12)
C10—C5—C6—C7179.30 (8)C5—C4—C9—N1−179.85 (8)
C5—C6—C7—C80.86 (14)C3—C4—C9—C8179.79 (8)
C5—C6—C7—C11−178.51 (9)C5—C4—C9—C80.06 (13)
C6—C7—C8—O1−178.78 (8)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O2W0.952.553.2871 (13)134
O2W—H2W2···Cl10.858 (19)2.274 (19)3.1306 (10)177.4 (18)
O1—H1O1···O1W0.874 (19)1.811 (19)2.6718 (10)167.9 (18)
N1—H1N1···O1Wi0.826 (18)1.977 (18)2.7516 (11)155.9 (17)
O1W—H2W1···Cl1i0.83 (2)2.27 (2)3.0758 (9)164.0 (18)
O2W—H1W2···Cl1ii0.76 (2)2.36 (2)3.1187 (10)177.7 (18)
O1W—H1W1···O2Wiii0.805 (19)1.86 (2)2.6690 (11)177.2 (19)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) x, y, z−1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1A···O2W0.952.553.2871 (13)134
O2W—H2W2···Cl10.858 (19)2.274 (19)3.1306 (10)177.4 (18)
O1—H1O1···O1W0.874 (19)1.811 (19)2.6718 (10)167.9 (18)
N1—H1N1···O1Wi0.826 (18)1.977 (18)2.7516 (11)155.9 (17)
O1W—H2W1···Cl1i0.83 (2)2.27 (2)3.0758 (9)164.0 (18)
O2W—H1W2···Cl1ii0.76 (2)2.36 (2)3.1187 (10)177.7 (18)
O1W—H1W1···O2Wiii0.805 (19)1.86 (2)2.6690 (11)177.2 (19)
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x, −y+1, −z+2; (iii) x, y, z−1.
Acknowledgements top

The authors thank the Malaysian Government and Universiti Sains Malaysia (USM) for the research facilities and USM Short Term Grant No. 304/PFIZIK/6312078 to conduct this work. KT thanks The Academy of Sciences for the Developing World and USM for a TWAS–USM fellowship.

references
References top

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