Crystal structure of 8-hy-droxy-quinoline: a new monoclinic polymorph.

In an attempt to grow 8-hy-droxy-quinoline-acetamino-phen co-crystals from equimolar amounts of conformers in a chloro-form-ethanol solvent mixture at room temperature, the title compound, C9H7NO, was obtained. The mol-ecule is planar, with the hy-droxy H atom forming an intra-molecular O-H⋯N hydrogen bond. In the crystal, mol-ecules form centrosymmetric dimers via two O-H⋯N hydrogen bonds. Thus, the hy-droxy H atoms are involved in bifurcated O-H⋯N hydrogen bonds, leading to the formation of a central planar four-membered N2H2 ring. The dimers are bound by inter-molecular π-π stacking [the shortest C⋯C distance is 3.2997 (17) Å] and C-H⋯π inter-actions into a three-dimensional framework. The crystal grown represents a new monoclinic polymorph in the space group P21/n. The mol-ecular structure of the present monoclinic polymorph is very similar to that of the ortho-rhom-bic polymorph (space group Fdd2) studied previously [Roychowdhury et al. (1978 ▶). Acta Cryst. B34, 1047-1048; Banerjee & Saha (1986 ▶). Acta Cryst. C42, 1408-1411]. The structures of the two polymorphs are distinguished by the different geometries of the hydrogen-bonded dimers, which in the crystal of the ortho-rhom-bic polymorph possess twofold axis symmetry, with the central N2H2 ring adopting a butterfly conformation.

Related literature

For general background on cocrystallization of organic compounds, see: Bernstein (2002 ▶); Desiraju (2003 ▶); Dunitz (2003 ▶); Timofeeva et al. (2003 ▶); Aakeröy et al. (2009 ▶); Lemmerer et al. (2011 ▶). For cocrystallization of 8-hy­droxy­quinoline with different mol­ecules, see: Prout & Wheeler (1967 ▶); Castellano & Prout (1971 ▶); Liu & Meng (2006 ▶); Westcott et al. (2009 ▶). For crystal structure of the ortho­rhom­bic polymorph of 8-hy­droxy­quinoline, see: Roy­chowdhury et al. (1978 ▶); Banerjee & Saha (1986 ▶).

Experimental

Crystal data

C9H7NO

M = 145.16

Monoclinic,

a = 6.620 (3) Å

b = 9.243 (4) Å

c = 11.070 (4) Å

β = 90.718 (6)°

V = 677.3 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 100 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.972, T max = 0.981

7049 measured reflections

1795 independent reflections

1494 reflections with I > 2σ(I)

R int = 0.023

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.109

S = 1.08

1795 reflections

103 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814016110/rk2430sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016110/rk2430Isup2.hkl

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Supporting information file. DOI: 10.1107/S1600536814016110/rk2430Isup3.cml

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I . DOI: 10.1107/S1600536814016110/rk2430fig1.tif

Mol­ecular structure of I. Displacement ellipsoids are presented at the 50% probability level. H atoms are depicted as small spheres of arbitrary radius. The intra­molecular O—H⋯N hydrogen bond is drawn by dashed line.

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I . DOI: 10.1107/S1600536814016110/rk2430fig2.tif

The centrosymmetric H–bonded dimers in the monoclinic polymorph of I. The hydrogen bonds are drawn by dashed lines.

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I . DOI: 10.1107/S1600536814016110/rk2430fig3.tif

The H–bonded dimers in the ortho­rhom­bic polymorph of I, in which the mol­ecules are related by the twofold axis. The hydrogen bonds are drawn by dashed lines.

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I . DOI: 10.1107/S1600536814016110/rk2430fig4.tif

A portion of crystal packing of the H–bonded dimers in the monoclinic polymorph of I. The hydrogen bonds are drawn by dashed lines.

CCDC reference: 1013310

Additional supporting information: crystallographic information; 3D view; checkCIF report

C9H7NO	F(000) = 304
Mr = 145.16	Dx = 1.423 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2841 reflections
a = 6.620 (3) Å	θ = 4.2–34.9°
b = 9.243 (4) Å	µ = 0.09 mm−1
c = 11.070 (4) Å	T = 100 K
β = 90.718 (6)°	Prism, colourless
V = 677.3 (5) Å3	0.30 × 0.25 × 0.20 mm
Z = 4

Bruker APEXII CCD diffractometer	1795 independent reflections
Radiation source: fine–focus sealed tube	1494 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
φ and ω scans	θmax = 29.0°, θmin = 4.2°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.972, Tmax = 0.981	k = −12→12
7049 measured reflections	l = −15→15

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) = 0.109	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0558P)2 + 0.1943P] where P = (Fo2 + 2Fc2)/3
1795 reflections	(Δ/σ)max = 0.001
103 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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	0.34421 (12)	0.32417 (9)	1.07956 (7)	0.0200 (2)
H1	0.423 (2)	0.3920 (19)	1.0538 (14)	0.030*
N1	0.32084 (13)	0.48141 (10)	0.86794 (8)	0.0156 (2)
C2	0.30597 (17)	0.55312 (12)	0.76494 (10)	0.0176 (2)
H2	0.4192	0.6081	0.7398	0.021*
C3	0.13175 (17)	0.55296 (12)	0.68997 (10)	0.0180 (2)
H3	0.1291	0.6066	0.6168	0.022*
C4	−0.03295 (17)	0.47463 (11)	0.72420 (10)	0.0166 (2)
H4	−0.1519	0.4741	0.6753	0.020*
C4A	−0.02507 (15)	0.39431 (11)	0.83296 (9)	0.0139 (2)
C5	−0.18735 (16)	0.30848 (11)	0.87370 (10)	0.0161 (2)
H5	−0.3103	0.3046	0.8286	0.019*
C6	−0.16632 (16)	0.23086 (12)	0.97870 (10)	0.0168 (2)
H6	−0.2752	0.1726	1.0054	0.020*
C7	0.01393 (16)	0.23605 (12)	1.04765 (9)	0.0159 (2)
H7	0.0260	0.1805	1.1196	0.019*
C8	0.17237 (16)	0.32095 (11)	1.01141 (9)	0.0146 (2)
C8A	0.15734 (15)	0.40160 (11)	0.90195 (9)	0.0131 (2)

	U11	U22	U33	U12	U13	U23
O1	0.0147 (4)	0.0215 (4)	0.0238 (4)	−0.0034 (3)	−0.0053 (3)	0.0075 (3)
N1	0.0139 (4)	0.0140 (4)	0.0190 (5)	0.0000 (3)	0.0010 (3)	−0.0005 (3)
C2	0.0170 (5)	0.0162 (5)	0.0198 (5)	−0.0027 (4)	0.0025 (4)	0.0002 (4)
C3	0.0230 (6)	0.0165 (5)	0.0147 (5)	−0.0010 (4)	−0.0002 (4)	0.0016 (4)
C4	0.0180 (5)	0.0160 (5)	0.0158 (5)	0.0002 (4)	−0.0032 (4)	−0.0011 (4)
C4A	0.0139 (5)	0.0126 (5)	0.0152 (5)	0.0005 (4)	0.0002 (4)	−0.0021 (4)
C5	0.0134 (5)	0.0173 (5)	0.0175 (5)	−0.0016 (4)	−0.0011 (4)	−0.0019 (4)
C6	0.0147 (5)	0.0168 (5)	0.0190 (5)	−0.0031 (4)	0.0020 (4)	−0.0013 (4)
C7	0.0168 (5)	0.0156 (5)	0.0154 (5)	0.0004 (4)	0.0002 (4)	0.0013 (4)
C8	0.0133 (5)	0.0138 (5)	0.0166 (5)	0.0017 (4)	−0.0017 (4)	−0.0015 (4)
C8A	0.0122 (5)	0.0115 (4)	0.0157 (5)	0.0012 (3)	0.0008 (4)	−0.0021 (4)

O1—C8	1.3575 (13)	C4A—C5	1.4139 (15)
O1—H1	0.865 (17)	C4A—C8A	1.4224 (14)
N1—C2	1.3214 (14)	C5—C6	1.3716 (16)
N1—C8A	1.3667 (14)	C5—H5	0.9500
C2—C3	1.4125 (16)	C6—C7	1.4093 (15)
C2—H2	0.9500	C6—H6	0.9500
C3—C4	1.3664 (16)	C7—C8	1.3739 (15)
C3—H3	0.9500	C7—H7	0.9500
C4—C4A	1.4149 (15)	C8—C8A	1.4250 (15)
C4—H4	0.9500
C8—O1—H1	109.6 (10)	C6—C5—H5	120.2
C2—N1—C8A	117.24 (9)	C4A—C5—H5	120.2
N1—C2—C3	123.92 (10)	C5—C6—C7	121.16 (10)
N1—C2—H2	118.0	C5—C6—H6	119.4
C3—C2—H2	118.0	C7—C6—H6	119.4
C4—C3—C2	119.09 (10)	C8—C7—C6	120.38 (10)
C4—C3—H3	120.5	C8—C7—H7	119.8
C2—C3—H3	120.5	C6—C7—H7	119.8
C3—C4—C4A	119.54 (10)	O1—C8—C7	119.19 (10)
C3—C4—H4	120.2	O1—C8—C8A	120.68 (9)
C4A—C4—H4	120.2	C7—C8—C8A	120.11 (9)
C5—C4A—C4	123.08 (10)	N1—C8A—C4A	123.20 (9)
C5—C4A—C8A	119.91 (10)	N1—C8A—C8	118.01 (9)
C4—C4A—C8A	117.01 (9)	C4A—C8A—C8	118.79 (9)
C6—C5—C4A	119.63 (10)
C8A—N1—C2—C3	0.76 (16)	C2—N1—C8A—C4A	−0.76 (15)
N1—C2—C3—C4	−0.05 (17)	C2—N1—C8A—C8	178.60 (9)
C2—C3—C4—C4A	−0.66 (16)	C5—C4A—C8A—N1	179.57 (9)
C3—C4—C4A—C5	−178.83 (10)	C4—C4A—C8A—N1	0.07 (15)
C3—C4—C4A—C8A	0.64 (15)	C5—C4A—C8A—C8	0.21 (14)
C4—C4A—C5—C6	178.39 (10)	C4—C4A—C8A—C8	−179.28 (9)
C8A—C4A—C5—C6	−1.07 (15)	O1—C8—C8A—N1	0.19 (15)
C4A—C5—C6—C7	0.60 (16)	C7—C8—C8A—N1	−178.25 (9)
C5—C6—C7—C8	0.77 (16)	O1—C8—C8A—C4A	179.58 (9)
C6—C7—C8—O1	179.90 (9)	C7—C8—C8A—C4A	1.14 (15)
C6—C7—C8—C8A	−1.63 (16)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.865 (17)	2.310 (15)	2.7596 (15)	112.5 (12)
O1—H1···N1i	0.865 (17)	2.228 (17)	2.9072 (14)	135.3 (13)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N1	0.865 (17)	2.310 (15)	2.7596 (15)	112.5 (12)
O1—H1⋯N1i	0.865 (17)	2.228 (17)	2.9072 (14)	135.3 (13)

Symmetry code: (i) .