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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 quinoline-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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012479/tk6113sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012479/tk6113Isup2.hkl
Contains datablock I

CCDC reference: 217462

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.044
  • wR factor = 0.098
  • Data-to-parameter ratio = 11.2

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

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.

Experimental top

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.

Refinement top

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 riding-model approximation.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular configuration and atom-naming scheme for (I), with atoms drawn as 30% probability ellipsoids.
[Figure 2] Fig. 2. Packing in the unit cell, viewed down a, showing hydrogen-bonding interactions as broken lines,
8-quinolinylurea top
Crystal data top
C10H9N3OF(000) = 392
Mr = 187.20Dx = 1.402 Mg m3
Monoclinic, P21/nMelting point = 476–477 K
Hall symbol: -P 2y nMo Kα radiation, λ = 0.71073 Å
a = 7.1436 (8) ÅCell parameters from 978 reflections
b = 8.1394 (9) Åθ = 2.7–22.1°
c = 15.2836 (17) ŵ = 0.10 mm1
β = 93.333 (2)°T = 293 K
V = 887.16 (17) Å3Block, colourless
Z = 40.32 × 0.16 × 0.10 mm
Data collection top
Bruker CCD area-detector
diffractometer
1133 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.050
Graphite monochromatorθmax = 25.0°, θmin = 2.7°
ϕ and ω scansh = 86
4542 measured reflectionsk = 99
1566 independent reflectionsl = 1518
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.044H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.098 w = 1/[σ2(Fo2) + (0.0391P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.97(Δ/σ)max < 0.001
1566 reflectionsΔρmax = 0.13 e Å3
140 parametersΔρmin = 0.12 e Å3
0 restraintsExtinction correction: SHELXTL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0062 (18)
Crystal data top
C10H9N3OV = 887.16 (17) Å3
Mr = 187.20Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.1436 (8) ŵ = 0.10 mm1
b = 8.1394 (9) ÅT = 293 K
c = 15.2836 (17) Å0.32 × 0.16 × 0.10 mm
β = 93.333 (2)°
Data collection top
Bruker CCD area-detector
diffractometer
1133 reflections with I > 2σ(I)
4542 measured reflectionsRint = 0.050
1566 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0440 restraints
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 0.97Δρmax = 0.13 e Å3
1566 reflectionsΔρmin = 0.12 e Å3
140 parameters
Special details top

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 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
O210.3942 (2)0.85917 (16)0.19967 (8)0.0791 (6)
N10.2027 (2)0.35554 (16)0.03980 (9)0.0479 (5)
N110.3135 (2)0.6068 (2)0.14424 (10)0.0530 (6)
N310.3128 (3)0.6553 (3)0.29036 (12)0.0873 (9)
C20.1491 (3)0.2315 (2)0.01131 (12)0.0554 (7)
C30.1322 (3)0.2386 (2)0.10303 (12)0.0620 (8)
C40.1725 (3)0.3823 (2)0.14244 (12)0.0603 (8)
C50.2810 (3)0.6708 (2)0.12906 (12)0.0633 (8)
C60.3394 (3)0.7968 (2)0.07680 (13)0.0657 (8)
C70.3541 (3)0.7802 (2)0.01482 (13)0.0582 (7)
C80.3079 (2)0.6349 (2)0.05384 (11)0.0465 (6)
C90.2336 (2)0.5182 (2)0.09216 (11)0.0497 (7)
C100.2471 (2)0.4995 (2)0.00024 (11)0.0430 (6)
C210.3420 (3)0.7169 (2)0.21112 (13)0.0601 (8)
H20.1205000.1326000.0154000.0660*
H30.0943000.1471000.1359000.0740*
H40.1596000.3909000.2032000.0720*
H50.2720000.6846000.1896000.0760*
H60.3704000.8964000.1020000.0790*
H70.3956000.8684000.0494000.0700*
H110.276 (3)0.510 (2)0.1571 (11)0.065 (6)*
H31A0.256 (3)0.557 (3)0.2977 (14)0.108 (9)*
H31B0.323 (3)0.725 (2)0.3359 (14)0.092 (7)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O210.1126 (13)0.0523 (9)0.0718 (10)0.0103 (8)0.0004 (8)0.0133 (7)
N10.0531 (10)0.0437 (8)0.0469 (9)0.0044 (7)0.0030 (7)0.0024 (7)
N110.0683 (12)0.0444 (10)0.0461 (10)0.0008 (8)0.0005 (7)0.0059 (8)
N310.144 (2)0.0723 (14)0.0451 (12)0.0189 (14)0.0019 (11)0.0138 (11)
C20.0618 (13)0.0473 (11)0.0572 (12)0.0006 (9)0.0039 (9)0.0041 (9)
C30.0723 (15)0.0595 (13)0.0537 (12)0.0031 (10)0.0003 (10)0.0154 (10)
C40.0709 (15)0.0692 (14)0.0409 (11)0.0097 (11)0.0029 (9)0.0059 (10)
C50.0754 (15)0.0669 (13)0.0484 (11)0.0059 (11)0.0115 (10)0.0110 (10)
C60.0758 (15)0.0568 (12)0.0656 (14)0.0006 (11)0.0148 (11)0.0131 (11)
C70.0595 (13)0.0489 (11)0.0666 (13)0.0031 (9)0.0063 (10)0.0028 (9)
C80.0431 (11)0.0491 (11)0.0473 (11)0.0059 (8)0.0031 (8)0.0026 (8)
C90.0512 (12)0.0549 (11)0.0434 (11)0.0106 (9)0.0074 (8)0.0002 (9)
C100.0409 (11)0.0448 (10)0.0438 (10)0.0091 (8)0.0061 (7)0.0005 (8)
C210.0699 (15)0.0548 (12)0.0546 (13)0.0027 (10)0.0052 (10)0.0106 (10)
Geometric parameters (Å, º) top
O21—C211.232 (2)C5—C91.413 (2)
N1—C21.320 (2)C5—C61.351 (3)
N1—C101.368 (2)C6—C71.405 (3)
N11—C81.399 (2)C7—C81.373 (2)
N11—C211.366 (2)C8—C101.430 (2)
N31—C211.338 (3)C9—C101.411 (2)
N11—H110.859 (17)C2—H20.9306
N31—H31A0.91 (2)C3—H30.9298
N31—H31B0.90 (2)C4—H40.9305
C2—C31.401 (3)C5—H50.9306
C3—C41.354 (2)C6—H60.9298
C4—C91.402 (2)C7—H70.9297
C2—N1—C10117.22 (14)N1—C10—C8118.18 (15)
C8—N11—C21128.79 (16)N1—C10—C9122.26 (15)
C8—N11—H11112.6 (11)C8—C10—C9119.56 (15)
C21—N11—H11117.8 (11)O21—C21—N31123.03 (19)
C21—N31—H31A122.5 (14)N11—C21—N31114.03 (17)
H31A—N31—H31B118.6 (19)O21—C21—N11122.93 (18)
C21—N31—H31B117.1 (12)N1—C2—H2117.75
N1—C2—C3124.46 (16)C3—C2—H2117.79
C2—C3—C4118.19 (16)C2—C3—H3120.86
C3—C4—C9120.34 (17)C4—C3—H3120.95
C6—C5—C9120.27 (17)C3—C4—H4119.84
C5—C6—C7121.27 (16)C9—C4—H4119.82
C6—C7—C8120.65 (16)C6—C5—H5119.82
C7—C8—C10119.03 (16)C9—C5—H5119.90
N11—C8—C10115.80 (15)C5—C6—H6119.33
N11—C8—C7125.17 (16)C7—C6—H6119.41
C4—C9—C10117.50 (15)C6—C7—H7119.69
C4—C9—C5123.29 (16)C8—C7—H7119.66
C5—C9—C10119.21 (15)
C10—N1—C2—C31.0 (3)C9—C5—C6—C70.2 (3)
C2—N1—C10—C8179.20 (16)C5—C6—C7—C80.5 (3)
C2—N1—C10—C91.2 (2)C6—C7—C8—N11178.49 (17)
C21—N11—C8—C78.6 (3)C6—C7—C8—C100.9 (3)
C21—N11—C8—C10170.82 (17)C7—C8—C10—N1179.64 (15)
C8—N11—C21—O2110.6 (3)C7—C8—C10—C90.8 (2)
C8—N11—C21—N31170.96 (17)N11—C8—C10—N10.9 (2)
N1—C2—C3—C40.3 (3)N11—C8—C10—C9178.71 (13)
C2—C3—C4—C91.5 (3)C4—C9—C10—N10.1 (2)
C3—C4—C9—C5178.91 (19)C5—C9—C10—C80.1 (3)
C3—C4—C9—C101.3 (3)C4—C9—C10—C8179.70 (15)
C6—C5—C9—C4179.84 (19)C5—C9—C10—N1179.72 (15)
C6—C5—C9—C100.3 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N10.859 (17)2.227 (17)2.685 (2)113.3 (14)
N31—H31A···O21i0.91 (2)1.94 (2)2.836 (3)171 (2)
N31—H31B···N1ii0.90 (2)2.19 (2)3.072 (2)166.1 (18)
C7—H7···O210.932.302.895 (2)122
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC10H9N3O
Mr187.20
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)7.1436 (8), 8.1394 (9), 15.2836 (17)
β (°) 93.333 (2)
V3)887.16 (17)
Z4
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.32 × 0.16 × 0.10
Data collection
DiffractometerBruker CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4542, 1566, 1133
Rint0.050
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.044, 0.098, 0.97
No. of reflections1566
No. of parameters140
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.13, 0.12

Computer programs: SMART (Bruker, 2000), SMART, SAINT (Bruker, 1999), SHELXTL97 (Bruker, 1997), SHELXTL97, PLATON for Windows (Spek, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···N10.859 (17)2.227 (17)2.685 (2)113.3 (14)
N31—H31A···O21i0.91 (2)1.94 (2)2.836 (3)171 (2)
N31—H31B···N1ii0.90 (2)2.19 (2)3.072 (2)166.1 (18)
C7—H7···O210.932.302.895 (2)122
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1/2, y+1/2, z+1/2.
 

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