8-Hy­droxy-5-(hy­droxy­meth­yl)quinolin-1-ium chloride

Abstract

The title compound, C₁₀H₁₀NO₂ ⁺·Cl⁻, contains a quinoline ring system which is essentially planar, with the largest deviation from the mean plane being 0.017 (1) Å. In the crystal, the ion pairs and their inversion-symmetry-related partners are linked by N—H⋯Cl and O—H⋯Cl hydrogen bonds to form tetramers which are further connected through O—H⋯O hydrogen bonds, building infinite one-dimensional chains parallel to the [010] direction.

Related literature  

For anti­oxidant properties, see: Kayyali et al. (1998 ▶). For the synthesis of some substituted 8-quinolinol derivatives, see: Mishra et al. (2004 ▶). For the application of the corresponding aluminium complexes, see: Tang et al. (1989 ▶); Chen & Shi (1998 ▶); Shougen et al. (2000 ▶). For application as a promising display, see: Cao et al. (1996 ▶); Wu et al. (2003 ▶). For the synthesis, see: Zheng et al. (2005 ▶).

Experimental  

Crystal data  

• C₁₀H₁₀NO₂ ⁺·Cl⁻

• M _r = 211.64

• Monoclinic,

• a = 6.9081 (5) Å

• b = 8.0577 (5) Å

• c = 17.1890 (11) Å

• β = 101.183 (3)°

• V = 938.63 (11) ų

• Z = 4

• Mo Kα radiation

• μ = 0.38 mm⁻¹

• T = 296 K

• 0.54 × 0.43 × 0.12 mm

Data collection  

• Bruker X8 APEX diffractometer

• 22727 measured reflections

• 4615 independent reflections

• 3679 reflections with I > 2σ(I)

• R _int = 0.024

Refinement  

• R[F ² > 2σ(F ²)] = 0.039

• wR(F ²) = 0.124

• S = 1.07

• 4615 reflections

• 127 parameters

• H-atom parameters constrained

• Δρ_max = 0.50 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812024233/fj2562Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1	0.86	2.24	3.0261 (8)	152
O1—H1O⋯O2i	0.82	1.78	2.5841 (10)	166
O2—H2O⋯Cl1ii	0.82	2.21	3.0281 (8)	172

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

8-Quinolinol is a strong iron chelator with antioxidant property (Kayyali et al. 1998). 5-Chloromethyl-8-hydroxyquinoline hydrochloride (I) is used as an intermediate in the synthesis of 5-hydroxymethyl-8-quinolinol and some substituted 8-quinolinol derivatives (Mishra et al. (2004). The corresponding aluminium complexes has been used as an excellent Organic Light-Emitting Diodes (OLEDs) (Tang et al. (1989), Chen & Shi (1998), Shougen et al. (2000)) witch are currently under intensive investigation for application as a promising display technology due to their high luminous efficiency and capability of emitting full colour flat displays (Cao et al. (1996), Wu et al. (2003)). The present work describes the crystal structure of C₁₀H₁₀NO₂.Cl (scheme 1) obtained from the X-ray diffraction data on single-crystal.

The 5-(hydroxymethyl)-8-quinolinol hydrochloride molecule structure is built up from two fused six-membered rings linked to CH₂OH and to OH groups as shown in Fg.1. The fused-ring system is essentially planar, with the maximum deviation of 0.017 (1) Å from C7 atom. The dihedral angle between them does not exceed 1.15 (5)°. The hydroxide O2—H linked to –C10H₂– form an angle of 56.68 (6) ° with the mean plane of the quinolin ring. In the crystal, each molecule and its symmetry through the inversion center are linked by N—H···Cl and O—H···Cl hydrogen bonds in the way to form dimers as shown in Fig.2. These dimers are further connected through O—H···O hydrogen bonds building infinite one-dimensional chains parallel to [0 1 0] direction (Table 1).

Experimental

5-Chloromethyl-8-hydroxyquinoline hydrochloride (I) was synthesized according to the method described by Zheng et al. (2005). A mixture of 10.0 g (0.068 mol) of 8-hydroxyquinoline, 11 ml of concentrated hydrochloric acid, and 11 ml (0.397 mol) of 37% formaldehyde was treated with hydrogen chloride gas and stirred for 6 h. The solution was allowed to stand at room temperature for 2 h without stirring. The yellow solid obtained was collected on a filter, washed with acetone or alcohol, and dried under vacuum to give 5-chloromethyl-8-hydroxyquinoline hydrochloride (I) (13.0 g, 98%). The compound obtained was dissolved in distilled water in a box Petrys and let in air at room temperature. After 10 days, transparent single crystals as platelets were isolated. X-ray diffraction analysis shows that the obtained product is the 5-(hydroxymethyl)-8-quinolinol hydrochloride.

Refinement

H atoms were located in a difference map and treated as riding with N—H = 0.86 Å, C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene) and O—H = 0.82 Å with U_iso(H) = 1.2 U_eq (aromatic, methylene) and U_iso(H)= 1.5 U_eq (OH).

Figures

Fig. 1.

Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.

Fig. 2.

Molecule and its symmetry through the inversion center linked by hydrogen bonds and building dimers.

Crystal data

C10H10NO2+·Cl−	F(000) = 440
Mr = 211.64	Dx = 1.498 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p_2ybc	Cell parameters from 4615 reflections
a = 6.9081 (5) Å	θ = 2.8–36.5°
b = 8.0577 (5) Å	µ = 0.38 mm−1
c = 17.1890 (11) Å	T = 296 K
β = 101.183 (3)°	Needle, colourless
V = 938.63 (11) Å3	0.54 × 0.43 × 0.12 mm
Z = 4

Data collection

Bruker X8 APEX diffractometer	3679 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.024
Graphite monochromator	θmax = 36.5°, θmin = 2.8°
φ and ω scans	h = −11→11
22727 measured reflections	k = −12→13
4615 independent reflections	l = −28→28

Refinement

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)] = 0.039	Hydrogen site location: difference Fourier map
wR(F2) = 0.124	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0694P)2 + 0.1142P] where P = (Fo2 + 2Fc2)/3
4615 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.16928 (4)	0.17354 (3)	0.310398 (15)	0.03843 (8)
O1	0.30276 (12)	0.22164 (9)	0.51946 (4)	0.03652 (16)
H1O	0.3342	0.1525	0.5547	0.055*
O2	0.44071 (12)	0.98428 (9)	0.61542 (5)	0.03859 (17)
H2O	0.5509	0.9455	0.6316	0.058*
N1	0.19725 (11)	0.47152 (9)	0.41916 (4)	0.02749 (14)
H1N	0.1996	0.3699	0.4041	0.033*
C1	0.14320 (16)	0.58746 (13)	0.36492 (5)	0.03366 (18)
H1	0.1075	0.5578	0.3118	0.040*
C2	0.13937 (16)	0.75383 (12)	0.38682 (6)	0.0362 (2)
H2	0.1026	0.8355	0.3486	0.043*
C3	0.19059 (14)	0.79558 (11)	0.46549 (6)	0.03077 (17)
H3	0.1887	0.9064	0.4804	0.037*
C4	0.24629 (12)	0.67260 (10)	0.52439 (5)	0.02444 (14)
C5	0.24952 (12)	0.50630 (10)	0.49814 (5)	0.02361 (14)
C6	0.30430 (13)	0.37354 (10)	0.55186 (5)	0.02688 (15)
C7	0.35081 (16)	0.40924 (12)	0.63135 (5)	0.03253 (18)
H7	0.3846	0.3239	0.6679	0.039*
C8	0.34767 (16)	0.57403 (12)	0.65797 (5)	0.03347 (18)
H8	0.3807	0.5948	0.7121	0.040*
C9	0.29775 (14)	0.70577 (11)	0.60713 (5)	0.02761 (15)
C10	0.29652 (17)	0.87978 (12)	0.63908 (6)	0.03501 (19)
H10A	0.1669	0.9279	0.6209	0.042*
H10B	0.3200	0.8753	0.6965	0.042*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cl1	0.04035 (14)	0.03721 (14)	0.03423 (12)	0.00236 (9)	−0.00147 (9)	−0.00972 (8)
O1	0.0523 (4)	0.0204 (3)	0.0344 (3)	0.0019 (3)	0.0024 (3)	0.0011 (2)
O2	0.0372 (4)	0.0224 (3)	0.0521 (4)	−0.0014 (2)	−0.0014 (3)	0.0061 (3)
N1	0.0306 (3)	0.0242 (3)	0.0260 (3)	−0.0013 (2)	0.0016 (2)	−0.0007 (2)
C1	0.0395 (5)	0.0317 (4)	0.0265 (4)	−0.0006 (3)	−0.0018 (3)	0.0027 (3)
C2	0.0431 (5)	0.0286 (4)	0.0326 (4)	0.0007 (4)	−0.0034 (4)	0.0066 (3)
C3	0.0334 (4)	0.0218 (3)	0.0342 (4)	0.0001 (3)	−0.0006 (3)	0.0035 (3)
C4	0.0243 (3)	0.0209 (3)	0.0274 (3)	−0.0018 (2)	0.0033 (3)	0.0011 (2)
C5	0.0242 (3)	0.0209 (3)	0.0251 (3)	−0.0015 (2)	0.0034 (2)	0.0013 (2)
C6	0.0304 (4)	0.0207 (3)	0.0289 (3)	−0.0018 (3)	0.0043 (3)	0.0028 (3)
C7	0.0432 (5)	0.0253 (4)	0.0277 (4)	−0.0024 (3)	0.0037 (3)	0.0053 (3)
C8	0.0450 (5)	0.0295 (4)	0.0254 (3)	−0.0046 (4)	0.0057 (3)	0.0009 (3)
C9	0.0317 (4)	0.0232 (3)	0.0280 (3)	−0.0040 (3)	0.0060 (3)	−0.0014 (3)
C10	0.0425 (5)	0.0263 (4)	0.0369 (4)	−0.0026 (3)	0.0094 (4)	−0.0061 (3)

Geometric parameters (Å, º)

O1—C6	1.3439 (11)	C3—H3	0.9300
O1—H1O	0.8200	C4—C5	1.4155 (11)
O2—C10	1.4225 (13)	C4—C9	1.4229 (12)
O2—H2O	0.8200	C5—C6	1.4158 (11)
N1—C1	1.3215 (12)	C6—C7	1.3721 (13)
N1—C5	1.3644 (11)	C7—C8	1.4059 (14)
N1—H1N	0.8600	C7—H7	0.9300
C1—C2	1.3941 (14)	C8—C9	1.3757 (13)
C1—H1	0.9300	C8—H8	0.9300
C2—C3	1.3718 (14)	C9—C10	1.5065 (12)
C2—H2	0.9300	C10—H10A	0.9700
C3—C4	1.4155 (12)	C10—H10B	0.9700
C6—O1—H1O	109.5	C4—C5—C6	121.75 (7)
C10—O2—H2O	109.5	O1—C6—C7	125.81 (8)
C1—N1—C5	122.74 (8)	O1—C6—C5	115.99 (8)
C1—N1—H1N	118.6	C7—C6—C5	118.19 (8)
C5—N1—H1N	118.6	C6—C7—C8	120.44 (8)
N1—C1—C2	120.45 (9)	C6—C7—H7	119.8
N1—C1—H1	119.8	C8—C7—H7	119.8
C2—C1—H1	119.8	C9—C8—C7	122.67 (8)
C3—C2—C1	119.16 (8)	C9—C8—H8	118.7
C3—C2—H2	120.4	C7—C8—H8	118.7
C1—C2—H2	120.4	C8—C9—C4	118.25 (8)
C2—C3—C4	121.05 (8)	C8—C9—C10	120.34 (8)
C2—C3—H3	119.5	C4—C9—C10	121.41 (8)
C4—C3—H3	119.5	O2—C10—C9	113.14 (8)
C3—C4—C5	116.98 (8)	O2—C10—H10A	109.0
C3—C4—C9	124.33 (8)	C9—C10—H10A	109.0
C5—C4—C9	118.69 (7)	O2—C10—H10B	109.0
N1—C5—C4	119.60 (7)	C9—C10—H10B	109.0
N1—C5—C6	118.65 (7)	H10A—C10—H10B	107.8

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1	0.86	2.24	3.0261 (8)	152
O1—H1O···O2i	0.82	1.78	2.5841 (10)	166
O2—H2O···Cl1ii	0.82	2.21	3.0281 (8)	172

Symmetry codes: (i) x, y−1, z; (ii) −x+1, −y+1, −z+1.