5,7 Di­bromo N tosyl­quinolin 8 amine

organic papers

Acta Cryst.(2005). E61, o3435–o3436 doi:10.1107/S160053680502773X Silvaet al. _C

16H12Br2N2O2S

o3435

Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

5,7-Dibromo-

N

-tosylquinolin-8-amine

Luiz Everson da Silva,a,b Antonio Carlos Joussef,aSabine Foroband Boris Schmidtb*

a_{Departamento de Quı´mica–UFSC, 88040-900}

Floriano´polis, SC, Brazil, andb

Clemens-Scho¨pf-Institut fu¨r Organische Chemie und Biochemie, Technische Universita¨t Darmstadt,

Petersenstrasse 22, D-64287 Darmstadt, Germany

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study

T= 299 K

Mean(C–C) = 0.007 A˚

Rfactor = 0.041

wRfactor = 0.109

Data-to-parameter ratio = 14.3

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

#2005 International Union of Crystallography

Printed in Great Britain – all rights reserved

In the crystal structure of the title compound, C16H12Br2N2O2S, molecules are linked by two hydrogen

bonds to form a three-dimensional network. The H atom of the NH group has two intermolecular contacts; one to a sulfonyl O atom (H O = 2.22 A˚ ) and the other to the Br at the quinoline C-7 position (H Br = 3.11 A˚ ).

Comment

The investigation of the crystal structure of the title compound, (I), is part of our search for Zinquin Ester analogues (Kimberet al., 2000). This class of compounds has been shown to be effective in the detection of zinc (II) in a range of mammalian cells (Pearceet al., 2001).

The molecular structure of the title compound (I) is illus-trated in Fig. 1. The quinoline ring system is planar and inclined to the benzene ring of the tosyl moiety [torsion angle C1—N1—S1—C10 being 76.5 (3)_].

The crystal packing of (I) is stabilized through a hydrogen-bonding network, as shown in Fig. 2. Details of the hydrogen bonding are given in Table 1.

Experimental

Compound (I) was prepared according to the literature procedure (Xueet al., 2000). Suitable crystals were obtained by recrystallization from methanol-dichloromethane (1:1).

Crystal data

C16H12Br2N2O2S Mr= 456.16

Orthorhombic,P2₁2₁2₁ a= 4.939 (1) A˚ b= 16.595 (3) A˚ c= 20.254 (4) A˚ V= 1660.1 (6) A˚3 Z= 4

Dx= 1.825 Mg m 3

CuKradiation Cell parameters from 25

reflections

= 5.3–18.8

= 7.46 mm1 T= 299 (2) K

Long needle, light brown 0.650.080.05 mm

Data collection

Nonius CAD-4 diffractometer

!/2scans

Absorption correction: scan (Northet al., 1968) Tmin= 0.486,Tmax= 0.708 3465 measured reflections 2997 independent reflections 2758 reflections withI> 2(I)

Rint= 0.019

max= 68.0

h= 0!5 k= 0!19 l=24!24 3 standard reflections

frequency: 120 min intensity decay: 1.0%

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.041} wR(F2_{) = 0.109} S= 1.08 2997 reflections 209 parameters

H-atom parameters constrained w= 1/[2

(Fo2) + (0.076P)2 + 0.4357P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.69 e A˚

3

min=0.92 e A˚

3

Extinction correction:SHELXL97 Extinction coefficient: 0.0012 (2) Absolute structure: Flack (1983) Flack parameter:0.01 (3)

Table 1

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N1—H1N O1i 0.86 2.22 2.884 (4) 134 N1—H1N Br1i

0.86 3.11 3.873 (3) 149

Symmetry code: (i)x1;y;z.

The H atoms were included in idealized positions and refined as riding atoms withUiso(H) = 1.2Ueq(parent atom), and N—H = 0.86 A˚

and C—H = 0.93 A˚ (0.96 A˚ for methyl groups).

Data collection:Nonius Diffractometer Control Software(Nonius, 1996); cell refinement:Nonius Diffractometer Control Software; data reduction: REDU4 (Stoe & Cie, 1987); program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

PLATON (Spek, 2003); software used to prepare material for publication:SHELXL97.

The authors thank Professor Dr Hartmut Fuess, FG Strukturforschung, FB Material- und Geowissenschaften, Technische Universita¨t Darmstadt, Petersenstrasse 23, 64287 Darmstadt, for diffractometer time.

References

Flack, H. D. (1983).Acta Cryst.A39, 876–881.

Kimber, M. C., Mahadevan, I. B., Lincoln, S. F., Ward, A. D. & Tiekink, E. R. T. (2000).J. Org. Chem.65, 8204–8209.

Nonius (1996). Nonius Diffractometer Control Software. PC Version 2.0. Nonius GmbH, Solingen, Germany.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351– 359.

Pearce, D. A., Jotterand, N., Carrico, I. S. & Imperiali, B. (2001).J. Am. Chem. Soc.123, 5160–5161.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Spek, A. L. (2003).J. Appl. Cryst.36, 7–13.

Stoe & Cie. (1987).REDU4. Version 6.2c. Stoe & Cie GmbH, Darmstadt, Germany.

[image:2.610.310.563.70.281.2] [image:2.610.44.298.73.232.2]

Xue, G., Bradshaw, Jerald S., Dalley, N. K., Savage, P. B., Izatt, R. M., Prodi, L., Montalti, M. & Zaccheroni, N. (2000).Tetrahedron,58, 4809–4815. Figure 1

Molecular structure of (I), showing the atom labeling and displacement ellipsoids drawn at the 50% probability level.

Figure 2

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Acta Cryst. (2005). E61, o3435–o3436

supporting information

Acta Cryst. (2005). E61, o3435–o3436 [doi:10.1107/S160053680502773X]

5,7-Dibromo-

N

-tosylquinolin-8-amine

Luiz Everson da Silva, Antonio Carlos Joussef, Sabine Foro and Boris Schmidt

S1. Comment

The investigation of the crystal structure of the title compound, (I), is part of our search for Zinquin Ester analogues (Kimber et al., 2000). This class of the compounds has been shown to be effective in the detection of zinc (II) in a range of mammalian cells (Pearce et al., 2001).

The molecular structure of the title compound (I) is illustrated in Fig. 1. The quinoline ring system is planar and inclined to the phenyl ring of the tosyl moiety [torsion angle C1—N1—S1—C10 being 76.5 (3)°].

The crystal packing of (I) is stabilized through a hydrogen-bonding network, as shown in Fig. 2. Details of the hydrogen bonding are given in Table 1. The H atom of the NH group has an intermolecular contact to atom O1, with an H···O distance of 2.22 Å, and is also connected to the bromine atom, indicating very weak N—H···Br hydrogen bonding, with an H···Br distance of 3.11 Å.

S2. Experimental

Compound (I) was prepared according to the literature procedure (Xue et al., 2000). Suitable crystals were obtained by recrystallization from methanol-dichloromethane (1:1).

S3. Refinement

The H atoms were included in idealized positions and refined as riding atoms with Uiso(H) = 1.2Ueq(parent atom), and N

[image:4.610.130.479.76.301.2]

Figure 1

Molecular structure of (I), showing the atom labeling and displacement ellipsoids drawn at the 50% probability level.

Figure 2

[image:4.610.125.482.343.642.2]

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Acta Cryst. (2005). E61, o3435–o3436

5,7-Dibromo-N-tosylquinolin-8-amine

Crystal data

C16H12Br2N2O2S Mr = 456.16

Orthorhombic, P212121

Hall symbol: P 2ac 2ab

a = 4.939 (1) Å

b = 16.595 (3) Å

c = 20.254 (4) Å

V = 1660.1 (6) Å3 Z = 4

F(000) = 896

Dx = 1.825 Mg m−3

Cu Kα radiation, λ = 1.54180 Å Cell parameters from 25 reflections

θ = 5.3–18.8°

µ = 7.46 mm−1 T = 299 K

Long needle, light brown 0.65 × 0.08 × 0.05 mm

Data collection

Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: psi-scan (North et al., 1968)

Tmin = 0.486, Tmax = 0.708

3465 measured reflections

2997 independent reflections 2758 reflections with I > 2σ(I)

Rint = 0.019

θmax = 68.0°, θmin = 3.4° h = 0→5

k = 0→19

l = −24→24

3 standard reflections every 120 min intensity decay: 1.0%

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.041} wR(F2_{) = 0.109} S = 1.08 2997 reflections 209 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-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.076P)2 + 0.4357P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.69 e Å−3

Δρmin = −0.92 e Å−3

Extinction correction: SHELXL97, Fc*_{=kFc[1+0.001xFc}2_λ3_/sin(2θ)]-1/4

Extinction coefficient: 0.0012 (2) Absolute structure: Flack (1983) Absolute structure parameter: −0.01 (3)

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su'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

S1 0.45127 (18) 0.15331 (5) 0.33555 (5) 0.0360 (3) O1 0.7323 (5) 0.14564 (17) 0.31743 (15) 0.0460 (8) O2 0.3241 (7) 0.09229 (18) 0.37390 (16) 0.0534 (10) N1 0.2761 (6) 0.15936 (18) 0.26682 (15) 0.0364 (9) N2 0.0963 (8) 0.3138 (2) 0.24236 (19) 0.0459 (11) C1 0.3804 (8) 0.2041 (2) 0.21271 (19) 0.0368 (10) C2 0.5625 (10) 0.1704 (3) 0.1682 (2) 0.0470 (12) C3 0.6661 (11) 0.2144 (3) 0.1149 (2) 0.0543 (16) C4 0.5827 (10) 0.2916 (3) 0.1050 (2) 0.0510 (16) C5 0.3953 (9) 0.3298 (2) 0.1475 (2) 0.0443 (12) C6 0.3020 (13) 0.4095 (3) 0.1402 (2) 0.0600 (14) C7 0.1102 (12) 0.4385 (3) 0.1829 (3) 0.0650 (16) C8 0.0162 (12) 0.3887 (3) 0.2315 (3) 0.0603 (17) C9 0.2905 (8) 0.2838 (2) 0.20064 (19) 0.0397 (11) C10 0.4153 (8) 0.2452 (2) 0.37766 (18) 0.0369 (10) C11 0.5991 (9) 0.3069 (3) 0.3663 (2) 0.0470 (12) C12 0.5790 (11) 0.3769 (3) 0.4025 (2) 0.0537 (16) C13 0.3806 (11) 0.3870 (3) 0.4501 (2) 0.0553 (16) C14 0.1963 (11) 0.3243 (3) 0.4598 (2) 0.0581 (15) C15 0.2108 (9) 0.2538 (3) 0.4241 (2) 0.0483 (12) C16 0.3710 (16) 0.4613 (4) 0.4915 (3) 0.080 (2) H1N 0.12190 0.13560 0.26360 0.0440* H3 0.79130 0.19110 0.08650 0.0650* H6 0.37000 0.44210 0.10680 0.0720* H7 0.04530 0.49090 0.17890 0.0780* H8 −0.11600 0.40930 0.25950 0.0720* H11 0.73420 0.30100 0.33470 0.0560* H12 0.70150 0.41840 0.39470 0.0650* H14 0.06040 0.33020 0.49120 0.0700* H15 0.08570 0.21280 0.43090 0.0580* H16A 0.34950 0.50760 0.46360 0.0960* H16B 0.53630 0.46610 0.51610 0.0960* H16C 0.22090 0.45800 0.52150 0.0960*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2005). E61, o3435–o3436

C5 0.047 (2) 0.042 (2) 0.044 (2) −0.0095 (16) −0.0116 (17) 0.0056 (16) C6 0.074 (3) 0.051 (2) 0.055 (2) −0.012 (2) −0.011 (3) 0.017 (2) C7 0.075 (3) 0.043 (2) 0.077 (3) 0.004 (2) −0.019 (3) 0.009 (2) C8 0.063 (3) 0.049 (3) 0.069 (3) 0.007 (2) −0.003 (3) 0.000 (2) C9 0.0370 (19) 0.0425 (19) 0.0397 (18) −0.0062 (17) −0.0089 (16) 0.0006 (15) C10 0.0319 (18) 0.0452 (19) 0.0336 (17) 0.0004 (15) −0.0018 (14) 0.0053 (15) C11 0.041 (2) 0.048 (2) 0.052 (2) −0.0017 (18) 0.0074 (18) 0.0003 (18) C12 0.052 (3) 0.050 (2) 0.059 (3) −0.002 (2) −0.006 (2) −0.004 (2) C13 0.068 (3) 0.056 (3) 0.042 (2) 0.019 (2) −0.013 (2) −0.0046 (19) C14 0.056 (3) 0.081 (3) 0.0374 (19) 0.010 (3) 0.007 (2) −0.002 (2) C15 0.037 (2) 0.062 (2) 0.046 (2) 0.0037 (19) 0.0098 (18) 0.0038 (19) C16 0.107 (5) 0.071 (3) 0.061 (3) 0.024 (3) −0.015 (3) −0.019 (3)

Geometric parameters (Å, º)

Br1—C2 1.887 (5) C10—C15 1.388 (6) Br2—C4 1.893 (4) C10—C11 1.388 (6) S1—O1 1.441 (3) C11—C12 1.377 (7) S1—O2 1.422 (3) C12—C13 1.385 (7) S1—N1 1.642 (3) C13—C16 1.492 (8) S1—C10 1.756 (4) C13—C14 1.396 (7) N1—C1 1.421 (5) C14—C15 1.377 (7) N2—C8 1.323 (6) C3—H3 0.9300 N2—C9 1.372 (5) C6—H6 0.9300 N1—H1N 0.8600 C7—H7 0.9300 C1—C2 1.391 (6) C8—H8 0.9300 C1—C9 1.416 (5) C11—H11 0.9300 C2—C3 1.400 (6) C12—H12 0.9300 C3—C4 1.361 (7) C14—H14 0.9300 C4—C5 1.414 (6) C15—H15 0.9300 C5—C6 1.408 (6) C16—H16A 0.9600 C5—C9 1.417 (5) C16—H16B 0.9600 C6—C7 1.370 (8) C16—H16C 0.9600 C7—C8 1.367 (8)

Br1···S1 3.7413 (14) C15···C14vii _{3.600 (7)}

Br1···O1 3.210 (3) C8···H11v _2.9000

Br1···N1 3.137 (3) C10···H14vii _3.0200

Br1···C7i _{3.686 (6) C11···H8}ii _3.0900

Br1···C12i _{3.662 (5) C12···H14}ii _3.0800

Br1···H1Nii _{3.1100 C13···H15}vii _3.0900

Br1···H16Ai _{2.9600 C14···H15}vii _3.0000

Br2···H6 2.8100 C15···H11v _3.0700

S1···Br1 3.7413 (14) C15···H14vii _2.8000

O1···Br1 3.210 (3) C16···H6viii _3.0700

O1···N1ii _{2.884 (4) H1N···Br1}v _3.1100

O1···C2 3.164 (5) H1N···O1v _2.2200

O1···H11 2.6000 H6···C16ix _3.0700

O1···H7i _{2.7900 H6···H16C}ix _2.4400

O2···H15 2.5900 H7···O1vi _2.7900

O2···H16Biii _{2.8100 H7···O2}x _2.7000

O2···H7iv _{2.7000 H8···C11}v _3.0900

N1···Br1 3.137 (3) H8···H11v _2.4700

N1···O1v _{2.884 (4) H11···O1 2.6000}

N1···N2 2.757 (5) H11···N2ii _2.6000

N2···N1 2.757 (5) H11···C8ii _2.9000

N2···C10 3.360 (5) H11···C15ii _3.0700

N2···H11v _{2.6000 H11···H8}ii _2.4700

C2···O1 3.164 (5) H14···C12v _3.0800

C7···Br1vi _{3.686 (6) H14···H16C 2.3500}

C10···N2 3.360 (5) H14···C10iii _3.0200

C11···C14ii _{3.517 (7) H14···C15}iii _2.8000

C11···C15ii _{3.358 (6) H15···O2 2.5900}

C12···Br1vi _{3.662 (5) H15···C13}iii _3.0900

C12···C14ii _{3.377 (7) H15···C14}iii _3.0000

C14···C15iii _{3.600 (7) H16A···Br1}vi _2.9600

C14···C11v _{3.517 (7) H16B···O2}vii _2.8100

C14···C12v _{3.377 (7) H16C···H14 2.3500}

C15···C11v _{3.358 (6) H16C···H6}viii _2.4400

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Acta Cryst. (2005). E61, o3435–o3436

N2—C8—C7 125.9 (5) C13—C16—H16B 109.00 N2—C9—C5 121.8 (3) C13—C16—H16C 109.00 C1—C9—C5 121.3 (3) H16A—C16—H16B 109.00 N2—C9—C1 116.9 (3) H16A—C16—H16C 109.00 C11—C10—C15 120.9 (4) H16B—C16—H16C 109.00 S1—C10—C11 119.6 (3)

O1—S1—N1—C1 −38.8 (3) C2—C3—C4—Br2 −178.3 (4) O2—S1—N1—C1 −168.2 (3) C2—C3—C4—C5 0.7 (7) C10—S1—N1—C1 76.5 (3) Br2—C4—C5—C9 177.5 (3) N1—S1—C10—C11 −90.6 (3) C3—C4—C5—C9 −1.5 (7) O1—S1—C10—C15 −152.4 (3) Br2—C4—C5—C6 −1.3 (7) O2—S1—C10—C15 −21.6 (4) C3—C4—C5—C6 179.7 (5) N1—S1—C10—C15 92.4 (3) C6—C5—C9—N2 2.7 (6) O1—S1—C10—C11 24.7 (4) C6—C5—C9—C1 −177.9 (4) O2—S1—C10—C11 155.5 (3) C4—C5—C6—C7 176.9 (5) S1—N1—C1—C2 84.2 (4) C9—C5—C6—C7 −1.9 (7) S1—N1—C1—C9 −99.0 (4) C4—C5—C9—C1 3.2 (6) C8—N2—C9—C1 179.0 (4) C4—C5—C9—N2 −176.2 (4) C8—N2—C9—C5 −1.6 (6) C5—C6—C7—C8 0.2 (8) C9—N2—C8—C7 −0.3 (8) C6—C7—C8—N2 1.0 (9) N1—C1—C9—N2 −1.5 (5) S1—C10—C15—C14 175.8 (3) N1—C1—C9—C5 179.0 (4) C15—C10—C11—C12 0.9 (6) C9—C1—C2—C3 3.2 (6) S1—C10—C11—C12 −176.1 (3) C2—C1—C9—C5 −4.0 (6) C11—C10—C15—C14 −1.2 (6) N1—C1—C2—Br1 2.5 (6) C10—C11—C12—C13 0.3 (7) C2—C1—C9—N2 175.4 (4) C11—C12—C13—C14 −1.1 (7) N1—C1—C2—C3 −179.9 (4) C11—C12—C13—C16 176.5 (5) C9—C1—C2—Br1 −174.4 (3) C16—C13—C14—C15 −176.9 (5) Br1—C2—C3—C4 176.1 (4) C12—C13—C14—C15 0.8 (7) C1—C2—C3—C4 −1.6 (7) C13—C14—C15—C10 0.4 (7)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x+1, y, z; (iii) x−1/2, −y+1/2, −z+1; (iv) −x, y−1/2, −z+1/2; (v) x−1, y, z; (vi) −x+1, y+1/2, −z+1/2; (vii)

x+1/2, −y+1/2, −z+1; (viii) −x+1/2, −y+1, z+1/2; (ix) −x+1/2, −y+1, z−1/2; (x) −x, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

N1—H1N···O1v _{0.86 2.22 2.884 (4) 134}

N1—H1N···Br1v _{0.86 3.11 3.873 (3) 149}

C6—H6···Br2 0.93 2.81 3.209 (5) 107 C11—H11···N2ii _{0.93 2.60 3.514 (6) 169}

C15—H15···O2 0.93 2.59 2.921 (6) 101