Quinoline

Acta Cryst.(2001). E57, o947±o949 DOI: 10.1107/S1600536801014891 Davies and Bond C₉H₇N

o947

organic papers

Acta Crystallographica Section E Structure Reports

Online

ISSN 1600-5368

Quinoline

John E. Davies and Andrew D. Bond*

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England

Correspondence e-mail: [email protected]

Key indicators Single-crystal X-ray study

T= 150 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.045

wRfactor = 0.124

Data-to-parameter ratio = 13.3

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2001 International Union of Crystallography Printed in Great Britain ± all rights reserved

The crystal structure of quinoline, C9H7N, has been

deter-mined at 150 (2) K. In space groupP21/c, the asymmetric unit

comprises two independent molecules. Molecules are linked

viaCÐH N interactions into two orthogonal sets of chains which are linkedviaan extensive network of edge-to-face CÐ H interactions.

Comment

Although the structure of naphthalene was one of the ®rst determined by X-ray crystallography (Bragg, 1922), this is the ®rst report of the structure of quinoline. This long delay may be attributed to the dif®culty of obtaining a suitable single crystal of quinoline. This work forms part of a study devoted to improving the techniques for determining the crystal structures of substances which are liquids at room tempera-ture [see, for example, Bondet al.(2001)].

Quinoline, (I), crystallizes in the space groupP21/cwith the

asymmetric unit comprising two independent molecules (denotedAandB, Fig. 1). Molecules of typeAare linkedvia

CÐH N interactions into chains running parallel to the c

direction [H6A N1Ai _{= 2.89 (2) AÊ, C6AÐH6A N1A}i ₌

141.1 (1)_{; symmetry code: (i) x,} 1

2ÿy, 12+z]. Molecules of

typeBare also linkedviaCÐH N interactions into chains running parallel to thebdirection [H3B N1Bii_{= 2.68 (2) AÊ,}

C3BÐH3B N1Bii _{= 171.1 (1); symmetry code: (ii) 2ÿx,} 1

2+y,32ÿz]. Thus, there exist in (I) two orthogonal sets of CÐ

H N hydrogen-bonded chains. Between these chains, an extensive network of edge-to-face CÐH interactions exists (Desiraju & Steiner, 1999). This network may be visualized most conveniently by considering that each edge of a molecule of (I) exposed in a typeBchain is `capped' by a molecule of typeA, and that these capped chains interlock to form two-dimensional layers parallel to (101) (Fig. 2). The layers may then be considered to stack in an ABCABC

arrangement perpendicular to (101) with the CÐH N interactions between typeAmolecules linking the layers (Fig. 3).

Experimental

The sample (98%) was obtained from the Aldrich Company and used without further puri®cation. The crystal was grown with dif®culty in a 0.3 mm glass capillary tube, obtained from the PANTAK company

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(PANTAK Company, Unit 30, The Robert Corl Industrial Estate, Britten Road, Reading, England), at 245 K (a temperature only slightly less than the melting point of the solid in the capillary tube). With the axis of the capillary parallel to the'axis and horizontal on the instrument, the crystal was eventually grown by moving a plug of solid material up and down the tube (the movement being controlled

with the standard Z (height) adjustment of the goniometer head). The goniometer head was a Nonius model 1516.916 X±Y±Z (Nonius BV, Delft, The Netherlands); this head is particularly well suited to the experiment described in this paper since it has an especially wide Z translation (8 mm). This method is effectively zone re®nement, similar to the industrial methods used to grow large single crystals of silicon for the electronics industry. The ®ne temperature control necessary for the successful growth of the crystal was provided by an Oxford Cryosystems Cryostream (Oxford Cryosystems, Lower Road, Long Hanborough, Oxford, England).

Crystal data C9H7N

Mr= 129.16

Monoclinic,P21/c

a= 9.9226 (5) AÊ

b= 10.8473 (7) AÊ

c= 13.3665 (7) AÊ

= 106.578 (3)

V= 1378.88 (13) AÊ3

Z= 8

Dx= 1.244 Mg mÿ3

MoKradiation Cell parameters from 6740

re¯ections

= 1.0±27.5 = 0.07 mmÿ1

T= 150 (2) K Cylinder, colourless 0.26 mm (radius) Data collection

Nonius KappaCCD diffractometer Thin-slice!and'scans 4851 measured re¯ections 3055 independent re¯ections 2337 re¯ections withI> 2(I)

Rint= 0.018 max= 27.4

h=ÿ12!12

k=ÿ12!14

l=ÿ17!17 Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.045}

wR(F2_{) = 0.124}

S= 1.04 3055 re¯ections 230 parameters

All H-atom parameters re®ned

w= 1/[2_(F

o2) + (0.0556P)2

+ 0.2728P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.002

max= 0.18 e AÊÿ3

min=ÿ0.18 e AÊÿ3

The positions of all H atoms were allowed to re®ne independently. Pairs of chemically equivalent H atoms in the two independent molecules were assigned common, isotropic displacement parameters (7 variables in total).

Data collection:COLLECT(Nonius, 1998); cell re®nement:HKL SCALEPACK(Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997);

Figure 3

Projection of (I) on to (010) showing layers stacked in anABCABC arrangement. CÐH N interactions between typeAmolecules link the layers and are shown as dotted lines (CAMERON; Watkinet al., 1996).

Figure 1

The asymmetric unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993). The two independent molecules adopt a geometry indicative of an edge-to-face CÐH interaction.

Figure 2

program(s) used to re®ne structure:SHELXL97 (Sheldrick, 1997); software used to prepare material for publication:SHELXL97.

We thank the EPSRC for ®nancial assistance towards the purchase of the Nonius CCD diffractometer.

References

Bond, A. D., Davies, J. E., Grif®ths, J. & Rawson, J. R. (2001).Acta Cryst.E57, o231±o233.

Bragg, W. H. (1922).Proc. Phys. Soc.(London),35, 167.

Desiraju, G. R. & Steiner, T. (1999).The Weak Hydrogen Bond In Structural Chemistry and Biology. New York: Oxford University Press.

Nonius (1998).COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). HKL DENZO and SCALEPACK. University of Texas, Southwestern Medical Center at Dallas, USA. Sheldrick, G. M. (1993).XP. University of GoÈttingen, Germany.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.

Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996).CAMERON. Chemical Crystallography Laboratory, University of Oxford, England.

Acta Cryst.(2001). E57, o947±o949 Davies and Bond C₉H₇N

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Acta Cryst. (2001). E57, o947–o949

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Acta Cryst. (2001). E57, o947–o949 [doi:10.1107/S1600536801014891]

Quinoline

John E. Davies and Andrew D. Bond

S1. Comment

Although the structure of naphthalene was one of the first determined by X-ray crystallography (Bragg, 1922), this is the

first report of the structure of quinoline. This long delay may be attributed to the difficulty of obtaining a suitable

single-crystal of quinoline. This work forms part of a study devoted to improving the techniques for determining the single-crystal

structures of substances which are liquids at room temperature [see, for example, Bond et al. (2001)].

Quinoline, (I), crystallizes in the space group P21/c with the asymmetric unit comprising two independent molecules

(denoted A and B, Fig. 1). Molecules of type A are linked via C—H···N interactions into chains running parallel to the c

direction [H6A···N1Ai _{= 2.89 (2) Å, C6A—H6A···N1A}i _{= 141.1 (1)°; symmetry code: (i) x, 0.5 - y, 0.5 + z]. Molecules of}

type B are also linked via C—H···N interactions into chains running parallel to the b direction [H3B···N1Bii _{= 2.68 (2) Å,}

C3B—H3B···N1Bii _{= 171.1 (1)°; symmetry code: (ii) 2 - x, 0.5 + y, 1.5 - z]. Thus, there exists in (I) two orthogonal sets}

of C—H···N hydrogen-bonded chains. Between these chains, an extensive network of edge-to-face C—H···π interactions

exists (Desiraju & Steiner, 1999). This network may be visualized most conveniently by considering that each edge of a

molecule of (I) exposed in a type B chain is `capped′ by a molecule of type A, and that these capped chains interlock to

form two-dimensional layers parallel to (101) (Fig. 2). The layers may then be considered to stack in an ABCABC

arrangement perpendicular to (101) with the C—H···N interactions between type A molecules linking the layers (Fig. 3).

S2. Experimental

The sample (98%) was obtained from the Aldrich Company and used without further purification. The crystal was grown

with difficulty in a 0.3 mm glass capillary tube, obtained from the PANTAK company (PANTAK Company, Unit 30, The

Robert Corl Industrial Estate, Britten Road, Reading, England), at 245 K (a temperature only slightly less than the

melting point of the solid in the capillary tube). With the axis of the capillary parallel to the phi axis and horizontal on the

instrument, the crystal was eventually grown by moving a plug of solid material up and down the tube (the movement

being controlled with the standard Z (height) adjustment of the goniometer head). The goniometer head was a Nonius

model 1516.916 X—Y—Z (Nonius BV, Delft, The Netherlands); this head is particularly well suited to the experiment

described in this paper since it has an especially wide Z translation (8 mm). This method is effectively zone refinement,

similar to the industrial methods used to grow large single crystals of silicon for the electronics industry. The fine

temperature control necessary for the successful growth of the crystal was provided by an Oxford Cryosystems

Cryostream (Oxford Cryosystems, Lower Road, Long Hanborough, Oxford, England).

S3. Refinement

The positions of all H atoms were allowed to refine independently. Pairs of chemically equivalent H atoms in the two

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Acta Cryst. (2001). E57, o947–o949

Figure 1

The asymmetric unit in (I) showing displacement ellipsoids at the 50% probability level (XP; Sheldrick, 1993). The two

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Acta Cryst. (2001). E57, o947–o949

Figure 2

Projection of (I) onto (101) showing type B molecules (coloured red) linked by C—H···N interactions into chains capped

at each exposed edge by type A molecules (coloured green). Adjacent chains interlock to form two-dimensional sheets.

Edge-to-face C—H···π interactions are shown as dotted lines only between the molecules at the edge of each chain

(interactions between chains are not drawn for the purposes of clarity) (CAMERON; Watkin et al., 1996).

Figure 3

Projection of (I) onto (010) showing layers stacked in an ABCABC arrangement. C—H···N interactions between type A

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Acta Cryst. (2001). E57, o947–o949

Quinoline

Crystal data

C9H7N Mr = 129.16

Monoclinic, P21/c a = 9.9226 (5) Å b = 10.8473 (7) Å c = 13.3665 (7) Å β = 106.578 (3)° V = 1378.88 (13) Å3 Z = 8

F(000) = 544

Dx = 1.244 Mg m−3

Melting point = 257–258 K Mo Kα radiation, λ = 0.7107 Å Cell parameters from 6740 reflections θ = 1.0–27.5°

µ = 0.07 mm−1 T = 150 K

Cylinder, colourless 0.26 mm (radius)

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Thin–slice ω and φ scans

4851 measured reflections 3055 independent reflections

2337 reflections with I > 2σ(I) Rint = 0.018

θmax = 27.4°, θmin = 3.6° h = −12→12

k = −12→14 l = −17→17

Refinement

Refinement on F2 Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.045} wR(F2_{) = 0.124} S = 1.04 3055 reflections 230 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: difference Fourier map All H-atom parameters refined

w = 1/[σ2_(Fo2_{) + (0.0556P)}2 _{+ 0.2728P]} where P = (Fo2 _{+ 2Fc}2_)/3

(Δ/σ)max = 0.002 Δρmax = 0.18 e Å−3 Δρmin = −0.18 e Å−3

Special details

Experimental. Grown in a 0.30 mm glass capillary tube at 245 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 F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

N1A 0.65225 (13) 0.07533 (12) 0.23904 (9) 0.0452 (3)

C2A 0.54448 (17) −0.00110 (16) 0.21851 (13) 0.0549 (4)

H2A 0.531 (2) −0.0560 (18) 0.1551 (15) 0.071 (4)*

C3A 0.45114 (17) −0.01252 (16) 0.27924 (15) 0.0582 (5)

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C4A 0.47055 (15) 0.05872 (15) 0.36503 (14) 0.0499 (4)

H4A 0.4112 (18) 0.0555 (15) 0.4118 (12) 0.052 (3)*

C5A 0.61552 (18) 0.21815 (14) 0.48250 (12) 0.0466 (4)

H5A 0.5547 (17) 0.2137 (15) 0.5255 (13) 0.053 (3)*

C6A 0.7300 (2) 0.29307 (14) 0.50649 (13) 0.0521 (4)

H6A 0.7558 (19) 0.3422 (17) 0.5694 (14) 0.063 (4)*

C7A 0.81915 (18) 0.29743 (13) 0.44123 (13) 0.0492 (4)

H7A 0.9067 (19) 0.3531 (17) 0.4611 (13) 0.063 (4)*

C8A 0.79123 (15) 0.22698 (13) 0.35304 (12) 0.0415 (3)

H8A 0.8508 (18) 0.2290 (15) 0.3062 (13) 0.057 (3)*

C9A 0.67380 (13) 0.14730 (12) 0.32681 (10) 0.0346 (3)

C10A 0.58453 (14) 0.14235 (12) 0.39252 (10) 0.0373 (3)

N1B 0.89070 (14) −0.18868 (13) 0.73237 (9) 0.0483 (3)

C2B 0.93813 (17) −0.07581 (17) 0.75730 (12) 0.0531 (4)

H2B 0.974 (2) −0.0584 (17) 0.8338 (15) 0.071 (4)*

C3B 0.93974 (15) 0.01761 (15) 0.68472 (12) 0.0473 (4)

H3B 0.9746 (19) 0.0981 (18) 0.7078 (13) 0.064 (4)*

C4B 0.89030 (14) −0.00839 (12) 0.58122 (11) 0.0372 (3)

H4B 0.8869 (17) 0.0548 (15) 0.5285 (12) 0.052 (3)*

C5B 0.78315 (14) −0.16227 (13) 0.44397 (10) 0.0380 (3)

H5B 0.7828 (17) −0.1016 (15) 0.3884 (12) 0.053 (3)*

C6B 0.72953 (16) −0.27704 (14) 0.41768 (12) 0.0471 (4)

H6B 0.6889 (18) −0.3002 (16) 0.3406 (14) 0.063 (4)*

C7B 0.72999 (17) −0.36330 (14) 0.49616 (14) 0.0511 (4)

H7B 0.6901 (18) −0.4468 (18) 0.4770 (13) 0.063 (4)*

C8B 0.78385 (15) −0.33428 (13) 0.59868 (13) 0.0456 (4)

H8B 0.7839 (18) −0.3935 (16) 0.6560 (13) 0.057 (3)*

C9B 0.83913 (13) −0.21504 (12) 0.62842 (10) 0.0343 (3)

C10B 0.83788 (12) −0.12738 (11) 0.54945 (9) 0.0305 (3)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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C6B 0.0476 (8) 0.0463 (8) 0.0462 (9) 0.0012 (7) 0.0117 (7) −0.0083 (7) C7B 0.0464 (8) 0.0328 (7) 0.0700 (11) −0.0008 (7) 0.0098 (7) −0.0016 (7) C8B 0.0399 (8) 0.0355 (7) 0.0614 (9) 0.0015 (6) 0.0144 (7) 0.0172 (7) C9B 0.0297 (6) 0.0369 (7) 0.0380 (7) 0.0069 (5) 0.0123 (5) 0.0093 (5) C10B 0.0277 (6) 0.0297 (6) 0.0365 (6) 0.0049 (5) 0.0132 (5) 0.0037 (5)

Geometric parameters (Å, º)

N1A—C2A 1.319 (2) N1B—C2B 1.320 (2)

N1A—C9A 1.3742 (17) N1B—C9B 1.3670 (18)

C2A—C3A 1.400 (3) C2B—C3B 1.406 (2)

C2A—H2A 1.01 (2) C2B—H2B 1.00 (2)

C3A—C4A 1.350 (3) C3B—C4B 1.359 (2)

C3A—H3A 0.98 (2) C3B—H3B 0.96 (2)

C4A—C10A 1.414 (2) C4B—C10B 1.4109 (18)

C4A—H4A 0.97 (2) C4B—H4B 0.98 (2)

C5A—C6A 1.358 (2) C5B—C6B 1.360 (2)

C5A—C10A 1.416 (2) C5B—C10B 1.4103 (18)

C5A—H5A 0.95 (2) C5B—H5B 0.99 (2)

C6A—C7A 1.410 (2) C6B—C7B 1.405 (2)

C6A—H6A 0.97 (2) C6B—H6B 1.02 (2)

C7A—C8A 1.365 (2) C7B—C8B 1.358 (2)

C7A—H7A 1.03 (2) C7B—H7B 0.99 (2)

C8A—C9A 1.412 (2) C8B—C9B 1.417 (2)

C8A—H8A 0.98 (2) C8B—H8B 1.00 (2)

C9A—C10A 1.4152 (18) C9B—C10B 1.4181 (17)

C2A—N1A—C9A 117.02 (13) C2B—N1B—C9B 116.98 (13)

N1A—C2A—C3A 124.48 (16) N1B—C2B—C3B 124.60 (14)

N1A—C2A—H2A 116.6 (11) N1B—C2B—H2B 115.5 (11)

C3A—C2A—H2A 118.9 (11) C3B—C2B—H2B 119.9 (11)

C4A—C3A—C2A 118.95 (16) C4B—C3B—C2B 118.74 (14)

C4A—C3A—H3A 121.7 (10) C4B—C3B—H3B 120.7 (10)

C2A—C3A—H3A 119.4 (10) C2B—C3B—H3B 120.6 (10)

C3A—C4A—C10A 119.83 (15) C3B—C4B—C10B 119.43 (13)

C3A—C4A—H4A 124.0 (10) C3B—C4B—H4B 121.1 (9)

C10A—C4A—H4A 116.2 (10) C10B—C4B—H4B 119.4 (9)

C6A—C5A—C10A 120.80 (14) C6B—C5B—C10B 120.97 (13)

C6A—C5A—H5A 121.5 (10) C6B—C5B—H5B 119.7 (9)

C10A—C5A—H5A 117.7 (10) C10B—C5B—H5B 119.3 (9)

C5A—C6A—C7A 120.28 (15) C5B—C6B—C7B 119.94 (14)

C5A—C6A—H6A 122.1 (11) C5B—C6B—H6B 119.8 (10)

C7A—C6A—H6A 117.6 (11) C7B—C6B—H6B 120.3 (10)

C8A—C7A—C6A 120.47 (15) C8B—C7B—C6B 121.04 (14)

C8A—C7A—H7A 120.0 (10) C8B—C7B—H7B 119.0 (10)

C6A—C7A—H7A 119.5 (10) C6B—C7B—H7B 119.9 (10)

C7A—C8A—C9A 120.44 (14) C7B—C8B—C9B 120.26 (13)

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C9A—C8A—H8A 117.6 (10) C9B—C8B—H8B 117.2 (10)

N1A—C9A—C8A 118.42 (12) N1B—C9B—C8B 118.61 (12)

N1A—C9A—C10A 122.40 (12) N1B—C9B—C10B 122.52 (12)

C8A—C9A—C10A 119.17 (13) C8B—C9B—C10B 118.87 (12)

C4A—C10A—C9A 117.32 (13) C5B—C10B—C4B 123.38 (12)

C4A—C10A—C5A 123.83 (13) C5B—C10B—C9B 118.90 (12)

C9A—C10A—C5A 118.83 (13) C4B—C10B—C9B 117.72 (12)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C3B—H3B···N1Bi _{0.96 (2) 2.68 (2) 3.626 (2) 171.1 (1)}

C6A—H6A···N1Aii _{0.97 (2) 2.89 (2) 3.696 (2) 141.1 (1)}