8 Quinolinyl­urea

organic papers

o972

Structure Reports Online

ISSN 1600-5368

8-Quinolinylurea

Graham Smith,a_{* Urs D.} Wermutha_{and Jonathan M.} Whiteb

a_{School of Physical and Chemical Sciences,}

Queensland University of Technology, GPO Box 2434, Brisbane 4001, Australia, and

b_{School of Chemistry, University of Melbourne,}

Parkville 3010, Australia

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 293 K

Mean(C±C) = 0.002 AÊ

Rfactor = 0.044

wRfactor = 0.098

Data-to-parameter ratio = 11.2

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

#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved

The crystal structure of 8-quinolinylurea, C10H9N3O, shows

the urea moiety to be close to coplanar with the quinoline ring, due to intramolecular hydrogen bonding between the quino-line-N atom and the H atom on the nearest urea N, and between the urea O atom and a quinoline-ring H atom. The molecules associate, through hydrogen bonds involving all potential donor and acceptor sites, to form a two-dimensional sheet structure.

Comment

We have previously reported the synthesis and crystal struc-tures of unsymmetrically substituted ureas together with their adducts with a number of carboxylic acids. These ureas included phenylurea (Kashino & Haisa, 1977; Bottet al., 2000) and 1,1-diethylurea (Smith & Kennard, 2000; Smith et al., 2000). These unsymmetrically substituted ureas are of interest because of their potential herbicidal properties,e.g.monuron [3-(4-chlorophenyl)-1,1-dimethylurea; Baughman, Hembreet al., 1980] and diuron [3-(3,4-dichlorophenyl) 1,1-dimethyl-urea; Baughman, Samset al., 1980] are commercial herbicides. The structure of the 1:1 proton-transfer compound of the unsymmetrical Lewis base-substituted urea (8-quinolinyl)urea with 3,5-dinitrosalicylic acid has previously been reported (Smithet al., 2001) and we report here the crystal structure of the parent urea compound, (8-quinolinyl)urea, (I), which has also been investigated for its phytotoxic properties (Paganiet al., 1983; Smithet al., 1997).

This determination shows only minor deviations from planarity in the overall molecule (Fig. 1), with the torsion angles C7ÐC8ÐN11ÐC21 and C8ÐN11ÐC21ÐN31 being 8.6 (3) and 171.0 (1) AÊ, respectively. This is largely due to the presence of intramolecular hydrogen bonds, on one side between the hetero-N atom of the quinoline residue and the H atom on the nearest urea-N atom [N11 N1 = 2.685 (2) AÊ], and on the other side between the urea O atom and a quinoline ring H atom [O21 C7 = 2.895 (2) AÊ]. The (8-quinolinium)urea cations in the 1:1 proton-transfer compound with 3,5-dinitrosalicylic acid are considerably different conformationally, with the urea side chain inverted and non-coplanar with the quinoline ring and with no intramolecular

hydrogen bonds. The molecules of (I) also form a cyclic hydrogen-bonding association through the urea functional groups and the hetero-N atom of the quinoline ring (Fig. 2 and Table 1). These dimers are then extended into a convoluted two-dimensional sheet structurevia n-glide-related molecules, with a separation ofca3.8 AÊ [Cg1 Cg1 = 3.838 (3) AÊ (Cg1 is the centroid of the N11-containing ring) and = 0.02 (2)_] between the sheets.

Experimental

The title compound, (I), was synthesized using the Vogel (1989) procedure. 8±Aminoquinoline (10 g, 0,069 mmol) was dissolved in 10 ml of hot glacial acetic acid and a solution of NaCNO (4.51 g, 0.069 mmol) in 50 ml of warm water was added with stirring, and the warmed solution stirred for a further 30 min. The mixture was cooled on an ice bath for 30 min and the precipitate of (I) removed by vacuum ®ltration and vacuum dried, giving 10 g of off-white product (77% yield). Recrystallization from absolute ethanol gave colourless crystals (m.p. 476±477 K) suitable for X-ray diffraction.

Crystal data

C10H9N3O

Mr= 187.20

Monoclinic,P21=n

a= 7.1436 (8) AÊ

b= 8.1394 (9) AÊ

c= 15.2836 (17) AÊ

= 93.333 (2) V= 887.16 (17) AÊ3

Z= 4

Dx= 1.402 Mg mÿ3

MoKradiation Cell parameters from 978

re¯ections

= 2.7±22.1

= 0.10 mmÿ1

T= 293 (2) K Block, colourless 0.100.160.32 mm

Data collection

Bruker CCD area-detector diffractometer

'and!scans

Absorption correction: none 4542 measured re¯ections 1566 independent re¯ections

1133 re¯ections withI> 2(I)

Rint= 0.050

max= 25.0

h=ÿ8!6

k=ÿ9!9

l=ÿ15!18

Re®nement

Re®nement onF2

R[F2_{> 2(F}2_{)] = 0.044}

wR(F2_{) = 0.098}

S= 0.97 1566 re¯ections 140 parameters

H atoms treated by a mixture of independent and constrained re®nement

w= 1/[2_(F

o2) + (0.0391P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.13 e AÊÿ3

min=ÿ0.12 e AÊÿ3

Extinction correction:SHELXTL97 Extinction coef®cient: 0.0062 (18)

Table 1

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

N11ÐH11 N1 0.859 (17) 2.227 (17) 2.685 (2) 113.3 (14) N31ÐH31A O21i _{0.91 (2) 1.94 (2) 2.836 (3) 171 (2)}

N31ÐH31B N1ii _{0.90 (2) 2.19 (2) 3.072 (2) 166.1 (18)}

C7ÐH7 O21 0.93 2.30 2.895 (2) 122

Symmetry codes: (i)1

2ÿx;ÿ12‡y;12ÿz; (ii)12ÿx;12‡y;12ÿz.

H atoms attached to N11 and N31 (H11, H31Aand H31B) were located in difference syntheses and their positional and isotropic displacement parameters were re®ned. Other H atoms were included in the re®nement in the riding-model approximation.

Data collection:SMART(Bruker, 2000); cell re®nement:SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXTL97 (Bruker, 1997); program(s) used to re®ne structure:SHELXTL97; molecular graphics:PLATON for Windows (Spek, 1999); software used to prepare material for publication: SHELXTL97.

The authors acknowledge ®nancial support from The School of Physical and Chemical Sciences of the Queensland University of Technology and The University of Melbourne.

References

Baughman, R. G., Hembre, R. I., Helland, B. J. & Jacobson, R. A. (1980).

Cryst. Struct. Commun.9, 749±752.

Baughman, R. G., Sams, D. D., Helland, B. J. & Jacobson, R. A. (1980).Cryst. Struct. Commun.9, 885±889.

Bott, R. C., Smith, G., Wermuth, U. D. & Dwyer, N. C. (2000).Aust. J. Chem.

53, 767±777.

Bruker (1997).SHELXTL97. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (1999).SAINT. Version 6.02. Bruker AXS Inc., Madison, Wisconsin,

USA.

Bruker (2000).SMART. Version 5.55. Bruker AXS Inc., Madison, Wisconsin, USA.

Kashino, S. & Haisa, M. (1977).Acta Cryst.B33, 855±860.

Acta Cryst.(2003). E59, o972±o974 Graham Smithet al. C₁₀H₉N₃O

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organic papers

Figure 1

The molecular con®guration and atom-labelling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.

Figure 2

organic papers

o974

Pagani, G., Carmellino, M. L., Caccialanza, G. & Borgna, P. (1983).Dip. Chim. Farm.38, 128±134.

Smith, C. J., Hansch, C. & Morton, M. J. (1997).Mutat. Res.379, 167±175. Smith, G., Bott, R. C., & Wermuth, U. D. (2001).Acta Cryst.E57, o895±o897. Smith, G., Coyne, M. G. & White, J. M. (2000).Aust. J. Chem.53, 203±208.

Smith, G. & Kennard, C. H. L. (2000).Aust. J. Chem.53, 999±1001. Spek, A. L. (1999). PLATON for Windows. September 1999 Version.

University of Utrecht, The Netherlands.

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Acta Cryst. (2003). E59, o972–o974 [doi:10.1107/S1600536803012479]

8-Quinolinylurea

Graham Smith, Urs D. Wermuth and Jonathan M. White

S1. Comment

We have previously reported the synthesis and crystal structures of unsymmetrically substituted ureas together with their

adducts with a number of carboxylic acids. These ureas included phenylurea (Kashino & Haisa, 1977; Bott et al., 2000)

and 1,1-diethylurea (Smith & Kennard, 2000; Smith et al., 2000). These unsymmetrically substituted ureas are of interest

because of their potential herbicidal properties, e.g. monuron [3-(4-chlorophenyl)-1,1-dimethylurea; Baughman, Hembre

et al., 1980] and diuron [3-(3,4-dichlorophenyl) 1,1-dimethylurea; Baughman, Sams et al., 1980] are commercial

herbicides. The structure of the 1:1 proton-transfer compound of the unsymmetrical Lewis base-substituted urea

(8-quinolinyl)urea with 3,5-dinitrosalicylic acid has previously been reported (Smith et al., 2001) and we report here the

crystal structure of the parent urea compound, (8-quinolinyl)urea, (I), which has also been investigated for its phytotoxic

properties (Pagani et al., 1983; Smith et al., 1997). This determination shows only minor deviations from planarity in the

overall molecule (Fig. 1) with the torsion angles C7–C8–N11–C21 and C8–N11–C21–N31 being 8.6 (3) and 171.0 (1) Å,

respectively. This is largely due to the presence of intramolecular hydrogen bonds, on one side between the proton on the

first urea-N atom and the hetero-N atom of the quinoline residue [N11···N1 = 2.685 (2) Å], and on the other side between

the urea O atom and a quinoline ring H atom [O21···C7 = 2.895 (2) Å]. The (8-quinolinium)urea cations in the 1:1

proton-transfer compound with 3,5-dinitrosalicylic acid are considerably different conformationally, with the urea side

chain inverted and non-coplanar with the quinoline ring and with no intramolecular hydrogen bonds. The molecules of (I)

also give a cyclic hydrogen-bonding association through the urea functional groups and the hetero-N atom of the

quinoline ring (Fig. 2 and Table 1). These dimers then are then extended into a convoluted two-dimensional sheet

structure via similar peripheral n-glide-related molecules with a separation of ca 3.8 Å [Cg1···Cg1 = 3.838 (3) Å and α =

2.89 (2)°] between the sheets.

S2. Experimental

The title compound, (I), was synthesized using the Vogel (1989) procedure. 8-Aminoquinoline (10 g, 0,069 mmol) was

dissolved in 10 ml of hot glacial acetic acid and a solution of NaCNO (4.51 g, 0.069 mmol) in 50 ml of warm water was

added with stirring, and the warmed solution stirred for a further 30 min. The mixture was cooled on an ice bath for 30

min and the precipitate of (I) removed by vacuum filtration and vacuum dried, giving 10 g of off-white product (77%

yield). Recrystallization from absolute ethanol gave colourless data crystals (m.p. 476–477 K) suitable for X-ray

diffraction.

S3. Refinement

H atoms involved in hydrogen-bonding inetractions (H11, H31A and H31B) were located by difference syntheses and

their positional and isotropic displacement parameters were refined. Other H atoms were included in the refinement in the

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Figure 1

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Figure 2

Packing in the unit cell, viewed down a, showing hydrogen-bonding interactions as broken lines,

8-quinolinylurea

Crystal data

C10H9N3O

Mr = 187.20 Monoclinic, P21/n

Hall symbol: -P 2y n

a = 7.1436 (8) Å

b = 8.1394 (9) Å

c = 15.2836 (17) Å

β = 93.333 (2)°

V = 887.16 (17) Å3

Z = 4

F(000) = 392

Dx = 1.402 Mg m−3

Melting point = 476–477 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 978 reflections

θ = 2.7–22.1°

µ = 0.10 mm−1

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Data collection

Bruker CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

4542 measured reflections 1566 independent reflections

1133 reflections with I > 2σ(I)

Rint = 0.050

θmax = 25.0°, θmin = 2.7°

h = −8→6

k = −9→9

l = −15→18

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.044}

wR(F2_{) = 0.098}

S = 0.97 1566 reflections 140 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0391P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.13 e Å−3

Δρmin = −0.12 e Å−3

Extinction correction: SHELXTL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.0062 (18)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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

O21 0.3942 (2) 0.85917 (16) 0.19967 (8) 0.0791 (6)

N1 0.2027 (2) 0.35554 (16) 0.03980 (9) 0.0479 (5)

N11 0.3135 (2) 0.6068 (2) 0.14424 (10) 0.0530 (6)

N31 0.3128 (3) 0.6553 (3) 0.29036 (12) 0.0873 (9)

C2 0.1491 (3) 0.2315 (2) −0.01131 (12) 0.0554 (7)

C3 0.1322 (3) 0.2386 (2) −0.10303 (12) 0.0620 (8)

C4 0.1725 (3) 0.3823 (2) −0.14244 (12) 0.0603 (8)

C5 0.2810 (3) 0.6708 (2) −0.12906 (12) 0.0633 (8)

C6 0.3394 (3) 0.7968 (2) −0.07680 (13) 0.0657 (8)

C7 0.3541 (3) 0.7802 (2) 0.01482 (13) 0.0582 (7)

C8 0.3079 (2) 0.6349 (2) 0.05384 (11) 0.0465 (6)

C9 0.2336 (2) 0.5182 (2) −0.09216 (11) 0.0497 (7)

C10 0.2471 (2) 0.4995 (2) −0.00024 (11) 0.0430 (6)

C21 0.3420 (3) 0.7169 (2) 0.21112 (13) 0.0601 (8)

H2 0.120500 0.132600 0.015400 0.0660*

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H4 0.159600 0.390900 −0.203200 0.0720*

H5 0.272000 0.684600 −0.189600 0.0760*

H6 0.370400 0.896400 −0.102000 0.0790*

H7 0.395600 0.868400 0.049400 0.0700*

H11 0.276 (3) 0.510 (2) 0.1571 (11) 0.065 (6)*

H31A 0.256 (3) 0.557 (3) 0.2977 (14) 0.108 (9)*

H31B 0.323 (3) 0.725 (2) 0.3359 (14) 0.092 (7)*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

O21 0.1126 (13) 0.0523 (9) 0.0718 (10) −0.0103 (8) 0.0004 (8) −0.0133 (7)

N1 0.0531 (10) 0.0437 (8) 0.0469 (9) 0.0044 (7) 0.0030 (7) −0.0024 (7)

N11 0.0683 (12) 0.0444 (10) 0.0461 (10) −0.0008 (8) 0.0005 (7) −0.0059 (8)

N31 0.144 (2) 0.0723 (14) 0.0451 (12) −0.0189 (14) 0.0019 (11) −0.0138 (11)

C2 0.0618 (13) 0.0473 (11) 0.0572 (12) 0.0006 (9) 0.0039 (9) −0.0041 (9)

C3 0.0723 (15) 0.0595 (13) 0.0537 (12) 0.0031 (10) 0.0003 (10) −0.0154 (10)

C4 0.0709 (15) 0.0692 (14) 0.0409 (11) 0.0097 (11) 0.0029 (9) −0.0059 (10)

C5 0.0754 (15) 0.0669 (13) 0.0484 (11) 0.0059 (11) 0.0115 (10) 0.0110 (10)

C6 0.0758 (15) 0.0568 (12) 0.0656 (14) −0.0006 (11) 0.0148 (11) 0.0131 (11)

C7 0.0595 (13) 0.0489 (11) 0.0666 (13) −0.0031 (9) 0.0063 (10) −0.0028 (9)

C8 0.0431 (11) 0.0491 (11) 0.0473 (11) 0.0059 (8) 0.0031 (8) −0.0026 (8)

C9 0.0512 (12) 0.0549 (11) 0.0434 (11) 0.0106 (9) 0.0074 (8) 0.0002 (9)

C10 0.0409 (11) 0.0448 (10) 0.0438 (10) 0.0091 (8) 0.0061 (7) 0.0005 (8)

C21 0.0699 (15) 0.0548 (12) 0.0546 (13) 0.0027 (10) −0.0052 (10) −0.0106 (10)

Geometric parameters (Å, º)

O21—C21 1.232 (2) C5—C9 1.413 (2)

N1—C2 1.320 (2) C5—C6 1.351 (3)

N1—C10 1.368 (2) C6—C7 1.405 (3)

N11—C8 1.399 (2) C7—C8 1.373 (2)

N11—C21 1.366 (2) C8—C10 1.430 (2)

N31—C21 1.338 (3) C9—C10 1.411 (2)

N11—H11 0.859 (17) C2—H2 0.9306

N31—H31A 0.91 (2) C3—H3 0.9298

N31—H31B 0.90 (2) C4—H4 0.9305

C2—C3 1.401 (3) C5—H5 0.9306

C3—C4 1.354 (2) C6—H6 0.9298

C4—C9 1.402 (2) C7—H7 0.9297

C2—N1—C10 117.22 (14) N1—C10—C8 118.18 (15)

C8—N11—C21 128.79 (16) N1—C10—C9 122.26 (15)

C8—N11—H11 112.6 (11) C8—C10—C9 119.56 (15)

C21—N11—H11 117.8 (11) O21—C21—N31 123.03 (19)

C21—N31—H31A 122.5 (14) N11—C21—N31 114.03 (17)

H31A—N31—H31B 118.6 (19) O21—C21—N11 122.93 (18)

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N1—C2—C3 124.46 (16) C3—C2—H2 117.79

C2—C3—C4 118.19 (16) C2—C3—H3 120.86

C3—C4—C9 120.34 (17) C4—C3—H3 120.95

C6—C5—C9 120.27 (17) C3—C4—H4 119.84

C5—C6—C7 121.27 (16) C9—C4—H4 119.82

C6—C7—C8 120.65 (16) C6—C5—H5 119.82

C7—C8—C10 119.03 (16) C9—C5—H5 119.90

N11—C8—C10 115.80 (15) C5—C6—H6 119.33

N11—C8—C7 125.17 (16) C7—C6—H6 119.41

C4—C9—C10 117.50 (15) C6—C7—H7 119.69

C4—C9—C5 123.29 (16) C8—C7—H7 119.66

C5—C9—C10 119.21 (15)

C10—N1—C2—C3 −1.0 (3) C9—C5—C6—C7 −0.2 (3)

C2—N1—C10—C8 −179.20 (16) C5—C6—C7—C8 −0.5 (3)

C2—N1—C10—C9 1.2 (2) C6—C7—C8—N11 −178.49 (17)

C21—N11—C8—C7 8.6 (3) C6—C7—C8—C10 0.9 (3)

C21—N11—C8—C10 −170.82 (17) C7—C8—C10—N1 179.64 (15)

C8—N11—C21—O21 −10.6 (3) C7—C8—C10—C9 −0.8 (2)

C8—N11—C21—N31 170.96 (17) N11—C8—C10—N1 −0.9 (2)

N1—C2—C3—C4 −0.3 (3) N11—C8—C10—C9 178.71 (13)

C2—C3—C4—C9 1.5 (3) C4—C9—C10—N1 −0.1 (2)

C3—C4—C9—C5 178.91 (19) C5—C9—C10—C8 0.1 (3)

C3—C4—C9—C10 −1.3 (3) C4—C9—C10—C8 −179.70 (15)

C6—C5—C9—C4 −179.84 (19) C5—C9—C10—N1 179.72 (15)

C6—C5—C9—C10 0.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N11—H11···N1 0.859 (17) 2.227 (17) 2.685 (2) 113.3 (14)

N31—H31A···O21i _{0.91 (2) 1.94 (2) 2.836 (3) 171 (2)}

N31—H31B···N1ii _{0.90 (2) 2.19 (2) 3.072 (2) 166.1 (18)}

C7—H7···O21 0.93 2.30 2.895 (2) 122