9,10 Bis(di­chloro­ethyl­amino­meth­yl)anthracene

organic papers

o2510

24H28Cl4N2 doi:10.1107/S1600536806019167 Acta Cryst.(2006). E62, o2510–o2511

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

9,10-Bis(dichloroethylaminomethyl)anthracene

Li-Na Yin, Qing-Xiang Liu,* Xiu-Mei Wu, Feng-Jin Cheng and Jian-Hua Guo

College of Chemistry and Life Science, Tianjin Normal University, Tianjin 300074, People’s Republic of China

Correspondence e-mail: qxliu@eyou.com

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C–C) = 0.003 A˚ Rfactor = 0.032 wRfactor = 0.089

Data-to-parameter ratio = 15.3

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

Received 26 April 2006 Accepted 23 May 2006

#2006 International Union of Crystallography All rights reserved

The title compound, C24H28Cl4N2, was obtained by the

reaction of 9,10-dichloromethylanthracene and dichloroethyl-amine. The molecule is centrosymmetric, with the substituents above and below the anthracene plane.

Comment

Fluorescent chemosensors constitute an important aspect of supramolecular chemistry (de Silver et al., 1997). Many of these fluorescent sensors with an anthracene ring system have been designed and investigated (Gunnlaugsson et al., 2002). Amine compounds with anthracene chromophores have attracted considerable attention in the past decade owing to their capability to monitor acidic changes of water in rivers (Luigi & Antonio, 1995). We report here the synthesis and crystal structure of the title compound, (2).

The molecule of (2) is centrosymmetric, with the substit-uents above and below the anthracene ring plane (Fig. 1). The

Figure 1

N—C bond lengths [1.459 (2), 1.452 (2) and 1.466 (2) A˚ ] are similar to those [1.509 (6) and 1.494 (6) A˚ ] of 9,10-dibenzyl-aminemethylanthracene (Changet al., 2000).

Experimental

To a toluene (100 ml) solution of 9,10-dichloromethyl-anthracene (5.00 g, 0.018 mol) were added dichloroethylamine (15.49 g, 0.109 mol) and K2CO3 (24.80 g, 0.180 mol) and the

solution was stirred for 6 h at 353 K. The toluene solution was washed with water (150 ml) and dried with anhydrous MgSO4,

then concentrated to 40 ml; hexane (5 ml) was added to give a yellow solid (yield: 7.20 g, 81.4%; m.p. 535–537 K). Crystals of (2) suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution at room temperature. Analysis calculated for C24H28Cl4N2: C 59.28, H 5.80, Cl 29.16,

N 5.76%; found C 59.11, H 5.34, Cl 28.96, N 5.42%.

Crystal data

C24H28Cl4N2

Mr= 486.28

Monoclinic,P21=c

a= 13.3505 (12) A˚

b= 10.6953 (10) A˚

c= 8.3412 (8) A˚

= 92.879 (1)

V= 1189.52 (19) A˚3

Z= 2

Dx= 1.358 Mg m 3

MoKradiation

= 0.51 mm 1

T= 293 (2) K Block, yellow 0.220.200.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.891,Tmax= 0.921

6278 measured reflections 2093 independent reflections 1669 reflections withI> 2(I)

Rint= 0.017

max= 25.0

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.032}

wR(F2) = 0.089

S= 1.07 2093 reflections 137 parameters

H-atom parameters constrained

w= 1/[2

(Fo2) + (0.0356P)2

+ 0.408P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.25 e A˚ 3

min= 0.25 e A˚ 3

Extinction correction:SHELXL97

Extinction coefficient: 0.0134 (15)

All H atoms were initially located in a difference Fourier map, but were then constrained to an ideal geometry, with C—H = 0.93–0.97 A˚ andUiso(H) = 1.2Ueq(C), and refined as riding on their parent atoms. Data collection:SMART(Bruker, 2000); cell refinement:SAINT (Bruker, 2000); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.

This project was supported by Tianjin Normal University Personnel Division (No. 5rl036).

References

Bruker (2000).SMARTandSAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chang, T., Heiss, A. M., Cantrill, S. J., Fyfe, M. C. T., Pease, A. R., Rowan, S. J., Stoddart, J. F. & Williams, D. J. (2000).Org. Lett.2, 2943–2946.

Gunnlaugsson, T., Bichell, B. & Nolan, C. (2002).Tetrahedron Lett.43, 4989– 4992.

Luigi, F. & Antonio, P. (1995).Chem. Soc. Rev.24, 197–202. Sheldrick, G. M. (1990).Acta Cryst.A46, 467–473.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997a).SHELXL97. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997b).SHELXTL. Version 5.10 for Windows NT. Bruker

AXS Inc., Madison, Wisconsin, USA.

supporting information

sup-1 Acta Cryst. (2006). E62, o2510–o2511

supporting information

Acta Cryst. (2006). E62, o2510–o2511 [https://doi.org/10.1107/S1600536806019167]

9,10-Bis(dichloroethylaminomethyl)anthracene

Li-Na Yin, Qing-Xiang Liu, Xiu-Mei Wu, Feng-Jin Cheng and Jian-Hua Guo

9,10-Bis(dichloroethylaminomethyl)anthracene

Crystal data

C24H28Cl4N2 Mr = 486.28

Monoclinic, P21/c

a = 13.3505 (12) Å

b = 10.6953 (10) Å

c = 8.3412 (8) Å

β = 92.879 (1)°

V = 1189.52 (19) Å3

Z = 2

F(000) = 508

Dx = 1.358 Mg m−3

Melting point: 162 K

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 2134 reflections

θ = 3.1–25.1°

µ = 0.51 mm−1

T = 293 K

Block, yellow

0.22 × 0.20 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.891, Tmax = 0.921

6278 measured reflections 2093 independent reflections 1669 reflections with I > 2σ(I)

Rint = 0.017

θmax = 25.0°, θmin = 3.1°

h = −15→15

k = −12→12

l = −7→9

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.032} wR(F2_{) = 0.089}

S = 1.07

2093 reflections 137 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) + (0.0356P)2 + 0.408P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.25 e Å−3

Δρmin = −0.25 e Å−3

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

Special details

Experimental. 1_{H NMR (300 MHZ, CDCl}

3, δ, p.p.m.): 3.483 (t, 8H, CH2), 3.992 (t, 8H, CH2), 4.70 (s, 4H, CH2), 7.50–

7.55 (m, 4H, AnH), 8.34–8.39 (m, 4H, AnH).

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

Cl1 0.31311 (4) 0.58536 (6) 0.11368 (6) 0.0739 (2)

Cl2 0.43369 (5) 0.28429 (6) 0.63139 (8) 0.0828 (2)

N1 0.28120 (10) 0.51499 (14) 0.58006 (17) 0.0439 (4)

C1 0.30892 (18) 0.5031 (2) 0.2998 (2) 0.0631 (6)

H1A 0.2608 0.4354 0.2882 0.076*

H1B 0.3742 0.4670 0.3268 0.076*

C2 0.28016 (14) 0.58725 (18) 0.4317 (2) 0.0480 (4)

H2A 0.3271 0.6562 0.4430 0.058*

H2B 0.2137 0.6212 0.4078 0.058*

C3 0.37449 (14) 0.5251 (2) 0.6764 (2) 0.0539 (5)

H3A 0.3685 0.5925 0.7531 0.065*

H3B 0.4280 0.5467 0.6069 0.065*

C4 0.40266 (15) 0.4070 (2) 0.7658 (3) 0.0649 (6)

H4A 0.3471 0.3806 0.8283 0.078*

H4B 0.4596 0.4234 0.8395 0.078*

C5 0.19394 (12) 0.53235 (19) 0.6777 (2) 0.0470 (4)

H5A 0.1969 0.6153 0.7247 0.056*

H5B 0.1974 0.4722 0.7648 0.056*

C6 0.09445 (12) 0.51724 (16) 0.5842 (2) 0.0413 (4)

C7 0.06525 (12) 0.39764 (16) 0.5287 (2) 0.0417 (4)

C8 0.12792 (14) 0.29072 (18) 0.5557 (2) 0.0513 (5)

H8 0.1903 0.3007 0.6089 0.062*

C9 0.09895 (16) 0.17556 (19) 0.5063 (2) 0.0587 (5)

H9 0.1411 0.1075 0.5266 0.070*

C10 0.00580 (17) 0.15792 (19) 0.4244 (3) 0.0593 (5)

H10 −0.0134 0.0783 0.3903 0.071*

C11 −0.05615 (15) 0.25555 (18) 0.3946 (2) 0.0527 (5)

H11 −0.1177 0.2416 0.3403 0.063*

C12 −0.03016 (12) 0.38025 (16) 0.4440 (2) 0.0415 (4)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

supporting information

sup-3 Acta Cryst. (2006). E62, o2510–o2511

Cl2 0.0764 (4) 0.0783 (4) 0.0935 (5) 0.0169 (3) 0.0014 (3) 0.0056 (3)

N1 0.0356 (8) 0.0567 (9) 0.0393 (8) −0.0015 (7) 0.0006 (6) 0.0055 (7)

C1 0.0807 (15) 0.0655 (13) 0.0428 (11) 0.0061 (11) 0.0008 (10) 0.0045 (9)

C2 0.0444 (10) 0.0538 (11) 0.0459 (10) 0.0017 (8) 0.0045 (8) 0.0063 (9)

C3 0.0380 (10) 0.0707 (13) 0.0526 (11) −0.0048 (9) −0.0024 (8) −0.0009 (10)

C4 0.0466 (11) 0.0925 (17) 0.0547 (12) 0.0057 (11) −0.0056 (9) 0.0074 (11)

C5 0.0412 (10) 0.0599 (11) 0.0399 (10) −0.0022 (8) 0.0012 (7) −0.0007 (9)

C6 0.0366 (9) 0.0512 (10) 0.0362 (9) −0.0028 (8) 0.0039 (7) 0.0007 (8)

C7 0.0382 (9) 0.0486 (10) 0.0387 (9) 0.0001 (8) 0.0065 (7) 0.0024 (8)

C8 0.0462 (10) 0.0543 (11) 0.0535 (11) 0.0043 (9) 0.0034 (8) 0.0044 (9)

C9 0.0625 (13) 0.0511 (12) 0.0631 (13) 0.0113 (10) 0.0090 (10) 0.0051 (10)

C10 0.0723 (14) 0.0438 (11) 0.0623 (13) −0.0035 (10) 0.0084 (11) −0.0035 (10)

C11 0.0512 (11) 0.0528 (11) 0.0541 (12) −0.0083 (9) 0.0026 (9) −0.0029 (9)

C12 0.0396 (9) 0.0469 (10) 0.0385 (9) −0.0036 (8) 0.0074 (7) −0.0006 (8)

Geometric parameters (Å, º)

Cl1—C1 1.787 (2) C5—H5A 0.970

Cl2—C4 1.788 (2) C5—H5B 0.970

N1—C3 1.452 (2) C6—C12i _{1.405 (2)}

N1—C2 1.459 (2) C6—C7 1.409 (2)

N1—C5 1.466 (2) C7—C8 1.428 (3)

C1—C2 1.487 (3) C7—C12 1.437 (2)

C1—H1A 0.970 C8—C9 1.349 (3)

C1—H1B 0.970 C8—H8 0.930

C2—H2A 0.970 C9—C10 1.401 (3)

C2—H2B 0.970 C9—H9 0.930

C3—C4 1.505 (3) C10—C11 1.347 (3)

C3—H3A 0.970 C10—H10 0.930

C3—H3B 0.970 C11—C12 1.433 (3)

C4—H4A 0.970 C11—H11 0.930

C4—H4B 0.970 C12—C6i _{1.405 (2)}

C5—C6 1.515 (2)

C3—N1—C2 113.68 (14) N1—C5—C6 113.66 (14)

C3—N1—C5 111.51 (14) N1—C5—H5A 108.8

C2—N1—C5 115.48 (14) C6—C5—H5A 108.8

C2—C1—Cl1 111.44 (15) N1—C5—H5B 108.8

C2—C1—H1A 109.3 C6—C5—H5B 108.8

Cl1—C1—H1A 109.3 H5A—C5—H5B 107.7

C2—C1—H1B 109.3 C12i_{—C6—C7 119.79 (15)}

Cl1—C1—H1B 109.3 C12i_{—C6—C5 121.04 (16)}

H1A—C1—H1B 108.0 C7—C6—C5 119.15 (15)

N1—C2—C1 108.39 (16) C6—C7—C8 121.65 (16)

N1—C2—H2A 110.0 C6—C7—C12 120.20 (15)

C1—C2—H2A 110.0 C8—C7—C12 118.15 (16)

N1—C2—H2B 110.0 C9—C8—C7 121.73 (18)

H2A—C2—H2B 108.4 C7—C8—H8 119.1

N1—C3—C4 113.46 (16) C8—C9—C10 120.38 (19)

N1—C3—H3A 108.9 C8—C9—H9 119.8

C4—C3—H3A 108.9 C10—C9—H9 119.8

N1—C3—H3B 108.9 C11—C10—C9 120.46 (19)

C4—C3—H3B 108.9 C11—C10—H10 119.8

H3A—C3—H3B 107.7 C9—C10—H10 119.8

C3—C4—Cl2 111.43 (15) C10—C11—C12 122.05 (18)

C3—C4—H4A 109.3 C10—C11—H11 119.0

Cl2—C4—H4A 109.3 C12—C11—H11 119.0

C3—C4—H4B 109.3 C6i_{—C12—C11 122.74 (16)}

Cl2—C4—H4B 109.3 C6i_{—C12—C7 120.02 (15)}

H4A—C4—H4B 108.0 C11—C12—C7 117.23 (16)

C3—N1—C2—C1 95.39 (19) C5—C6—C7—C12 178.09 (15)

C5—N1—C2—C1 −133.89 (17) C6—C7—C8—C9 178.25 (18)

Cl1—C1—C2—N1 −178.33 (13) C12—C7—C8—C9 −1.0 (3)

C2—N1—C3—C4 −146.04 (17) C7—C8—C9—C10 0.7 (3)

C5—N1—C3—C4 81.3 (2) C8—C9—C10—C11 −0.3 (3)

N1—C3—C4—Cl2 67.44 (19) C9—C10—C11—C12 0.2 (3)

C3—N1—C5—C6 −177.53 (15) C10—C11—C12—C6i _{−179.14 (18)}

C2—N1—C5—C6 50.7 (2) C10—C11—C12—C7 −0.5 (3)

N1—C5—C6—C12i _{−112.04 (18) C6—C7—C12—C6}i _{0.3 (3)}

N1—C5—C6—C7 69.6 (2) C8—C7—C12—C6i _{179.56 (15)}

C12i_{—C6—C7—C8 −179.54 (16) C6—C7—C12—C11 −178.41 (16)}

C5—C6—C7—C8 −1.2 (2) C8—C7—C12—C11 0.9 (2)

C12i_{—C6—C7—C12 −0.3 (3)}