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organic papers

Acta Cryst.(2005). E61, o2209–o2210 doi:10.1107/S1600536805019112 Zhuet al. C

20H16N2O2

o2209

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

2,5-Dibenzoyl-1,4-phenylenediamine

Hong-Jun Zhu, Dan-Dan Wang, Guang-Liang Song, Jin-Tang Wang and Ke-Le Wang*

Department of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People’s Republic of China

Correspondence e-mail: zhuhj@njut.edu.cn

Key indicators

Single-crystal X-ray study

T= 296 K

Mean(C–C) = 0.005 A˚

Rfactor = 0.054

wRfactor = 0.151

Data-to-parameter ratio = 12.9

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

The title compound, C20H16N2O2, was synthesized from the

reaction of 2,5-dibenzoylterephthalamide and sodium hypo-chlorite solution. The asymmetric unit contains one half-molecule, the molecule being centrosymmetric. Intra- and

intermolecular N—H O hydrogen bonds are highly effective

in forming a two-dimensional layer structure.

Comment

2,5-Dibenzoyl-1,4-phenylenediamine, (I), is a significant

material in the synthesis of extended lattice compounds with a centrosymmetric system. It is also an important compound in preparation of electron-transport materials (Tonzola et al., 2003). The synthesis of 2,5-dibenzoyl-1,4-phenylenediamine has been reported (Imaiet al., 1975).

The molecular structure of (I) is shown in Fig. 1 and selected bond lengths and angles are given in Table 1. The asymmetric unit contains one half molecule, the whole mole-cule being centrosymmetric.

The crystal packing is stabilized by intra- and

inter-molecular N—H O hydrogen bonds (Table 2), forming a

two-dimensional layer structure (Fig. 2).

Experimental

Sodium hypochlorite solution (10 ml, 5.25%) was added with stirring to a mixture of 2,5-dibenzoylterephthalamide (1 g, 2.7 mmol) and potassium hydroxide solution (30 ml, 10.45%) cooled in an ice-water bath for half an hour. The mixture was stirred for an additional hour at 343–353 K and the precipitate began to separate. The resulting precipitate was filtered off, washed with hot water and dried under reduced pressure. The crude product was obtained by slow evaporation of a solution in benzene (yield: 0.6 g, 71%; m.p. 492 K).

Crystal data

C20H16N2O2

Mr= 316.35 Orthorhombic,Pcab a= 7.4651 (15) A˚

b= 13.0034 (16) A˚

c= 15.9759 (18) A˚

V= 1550.8 (4) A˚3

Z= 4

Dx= 1.355 Mg m 3

MoKradiation Cell parameters from 25

reflections = 9–12 = 0.09 mm1

T= 296 (2) K Prism, brown 0.30.30.1 mm

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Data collection

Enraf–Nonius CAD-4 diffractometer !/2scans

Absorption correction: scan (XPREPinSHELXTL; Bruker, 2000)

Tmin= 0.974,Tmax= 0.991

1519 measured reflections 1519 independent reflections

614 reflections withI> 2(I) max= 26.0

h= 0!9

k= 0!16

l= 0!19

3 standard reflections every 200 reflections intensity decay: none

Refinement

Refinement onF2

R[F2> 2(F2)] = 0.054

wR(F2) = 0.151

S= 1.02 1519 reflections 118 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2(F

o2) + (0.0432P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.19 e A˚

3

min=0.18 e A˚

3

Extinction correction:SHELXL97

Extinction coefficient: 0.0047 (19)

Table 1

Selected geometric parameters (A˚ ,).

O—C4 1.231 (4)

C10—C4 1.478 (5)

N—C1 1.393 (4)

C3—C4 1.491 (4)

C2—C1—N 120.1 (3)

C1—C2—C3 122.4 (3)

C1i—C3—C4 120.7 (3) C10—C4—C3 120.9 (3)

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

Table 2

Hydrogen-bond geometry (A˚ ,).

D—H A D—H H A D A D—H A

N—H1 Oi

0.87 (4) 2.25 (4) 2.855 (5) 127 (3) N—H1 Oii

0.87 (4) 2.61 (4) 3.220 (5) 128 (3)

Symmetry codes: (i)x;y;z; (ii)1 2x;

1 2þy;z.

Atoms H1 and H3 were located in a difference synthesis and refined freely [N—H = 0.87 (4)–0.95 (5) A˚ ]. The remaining H atoms were positioned geometrically (C—H = 0.93 A˚ ) and refined as riding, withUiso(H) = 1.2Ueq(parent atom).

Data collection: CAD-4 Software (Enraf–Nonius,1989); cell refinement:CAD-4 Software; data reduction:XCAD4(Harms, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:SHELXTL (Sheldrick, 2001); software used to prepare material for publication:SHELXTL.

The authors thank the Center of Test and Analysis, Nanjing University, for support.

References

Bruker (2000).XSCANSandSHELXTL(Version 5.0). Bruker AXS Inc., Madison, Wisconsin, USA.

Enraf–Nonius (1989).CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.

Harms, K. (1995).XCAD4. University of Marburg, Germany.

Imai, Y., Johnson, E. F., Katto, T., Kurihara, M. & Stille, J. K. (1975).J. Polym. Sci.13, 2233–2249.

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

Tonzola, C. J., Alam, M. M., Kaminsky, W. & Jenekhe, S. A. (2003).J. Am. Chem. Soc.125, 13548–13558.

Figure 2

[image:2.610.315.564.71.181.2] [image:2.610.318.566.233.400.2]

The two-dimensional layer structure of (I). Dashed lines indicate hydrogen bonds.

Figure 1

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supporting information

sup-1 Acta Cryst. (2005). E61, o2209–o2210

supporting information

Acta Cryst. (2005). E61, o2209–o2210 [https://doi.org/10.1107/S1600536805019112]

2,5-Dibenzoyl-1,4-phenylenediamine

Hong-Jun Zhu, Dan-Dan Wang, Guang-Liang Song, Jin-Tang Wang and Ke-Le Wang

2,5-dibenzoyl-1,4-phenylenediamine

Crystal data

C20H16N2O2

Mr = 316.35

Orthorhombic, Pcab

Hall symbol: -P 2bc 2ac

a = 7.4651 (15) Å

b = 13.0034 (16) Å

c = 15.9759 (18) Å

V = 1550.8 (4) Å3

Z = 4

F(000) = 664

Dx = 1.355 Mg m−3 Melting point: 492 K

Mo radiation, λ = 0.71073 Å Cell parameters from 25 reflections

θ = 9–12°

µ = 0.09 mm−1

T = 296 K Prism, brown 0.3 × 0.3 × 0.1 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

ω/2θ scans

Absorption correction: ψ scan

(XPREP in SHELXTL; Bruker, 2000)

Tmin = 0.974, Tmax = 0.991 1519 measured reflections

1519 independent reflections 614 reflections with I > 2σ(I)

Rint = 0.000

θmax = 26.0°, θmin = 2.6°

h = 0→9

k = 0→16

l = 0→19

3 standard reflections every 200 reflections intensity decay: none

Refinement

Refinement on F2 Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.054

wR(F2) = 0.151

S = 1.02 1519 reflections 118 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) + (0.0432P)2] where P = (Fo2 + 2Fc2)/3 (Δ/σ)max = 0.001

Δρmax = 0.19 e Å−3 Δρmin = −0.18 e Å−3

(4)

Special details

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 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)

x y z Uiso*/Ueq

O −0.1312 (4) 0.2506 (2) 0.08228 (16) 0.0549 (8) N 0.3402 (5) −0.0911 (3) −0.0079 (2) 0.0490 (10) H1 0.349 (5) −0.154 (3) −0.025 (2) 0.044 (12)* H3 0.421 (7) −0.066 (3) 0.034 (3) 0.097 (18)* C1 0.1691 (5) −0.0489 (3) −0.0026 (2) 0.0341 (9) C2 0.1372 (5) 0.0349 (3) 0.0494 (2) 0.0345 (9) H2 0.2299 0.0592 0.0828 0.041* C3 −0.0277 (5) 0.0833 (2) 0.0531 (2) 0.0344 (9) C4 −0.0501 (5) 0.1747 (3) 0.1084 (2) 0.0378 (9) C5 0.0523 (5) 0.2689 (3) 0.2348 (2) 0.0474 (11) H5 0.0280 0.3302 0.2071 0.057* C6 0.1164 (6) 0.2708 (3) 0.3154 (3) 0.0599 (13) H6 0.1365 0.3337 0.3416 0.072* C7 0.1508 (6) 0.1818 (4) 0.3577 (2) 0.0626 (13) H7 0.1957 0.1841 0.4120 0.075* C8 0.1191 (6) 0.0889 (4) 0.3199 (2) 0.0587 (13) H8 0.1390 0.0281 0.3490 0.070* C9 0.0576 (6) 0.0860 (3) 0.2386 (2) 0.0469 (11) H9 0.0385 0.0227 0.2130 0.056* C10 0.0236 (5) 0.1754 (3) 0.1943 (2) 0.0360 (9)

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

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supporting information

sup-3 Acta Cryst. (2005). E61, o2209–o2210

Geometric parameters (Å, º)

O—C4 1.231 (4) C3—C1i 1.402 (5) C10—C9 1.384 (5) C3—C4 1.491 (4) C10—C5 1.394 (5) C5—C6 1.375 (5) C10—C4 1.478 (5) C5—H5 0.9300 N—C1 1.393 (4) C6—C7 1.364 (6) N—H1 0.87 (4) C6—H6 0.9300 N—H3 0.96 (5) C7—C8 1.371 (6) C1—C2 1.390 (4) C7—H7 0.9300 C1—C3i 1.402 (5) C8—C9 1.378 (5) C2—C3 1.384 (5) C8—H8 0.9300 C2—H2 0.9300 C9—H9 0.9300

C9—C10—C5 117.8 (3) C10—C4—C3 120.9 (3) C9—C10—C4 122.6 (3) C6—C5—C10 120.3 (4) C5—C10—C4 119.5 (3) C6—C5—H5 119.9 C1—N—H1 117 (3) C10—C5—H5 119.9 C1—N—H3 114 (3) C7—C6—C5 120.9 (4) H1—N—H3 119 (4) C7—C6—H6 119.5 C2—C1—C3i 117.7 (3) C5—C6—H6 119.5 C2—C1—N 120.1 (3) C8—C7—C6 119.7 (4) C3i—C1—N 122.0 (3) C8—C7—H7 120.1 C1—C2—C3 122.4 (3) C6—C7—H7 120.1 C1—C2—H2 118.8 C7—C8—C9 119.8 (4) C3—C2—H2 118.8 C7—C8—H8 120.1 C2—C3—C1i 119.9 (3) C9—C8—H8 120.1 C2—C3—C4 119.3 (3) C10—C9—C8 121.3 (4) C1i—C3—C4 120.7 (3) C10—C9—H9 119.3 O—C4—C10 119.6 (3) C8—C9—H9 119.3 O—C4—C3 119.5 (3)

C3i—C1—C2—C3 0.6 (5) C2—C3—C4—C10 −43.9 (5) N—C1—C2—C3 176.1 (3) C1i—C3—C4—C10 138.6 (4) C1—C2—C3—C1i −0.7 (6) C9—C10—C5—C6 1.5 (6) C1—C2—C3—C4 −178.1 (3) C4—C10—C5—C6 178.3 (3) C9—C10—C4—O 156.3 (4) C10—C5—C6—C7 −0.9 (6) C5—C10—C4—O −20.3 (5) C5—C6—C7—C8 −0.9 (7) C9—C10—C4—C3 −23.7 (5) C6—C7—C8—C9 1.9 (6) C5—C10—C4—C3 159.7 (3) C5—C10—C9—C8 −0.5 (6) C2—C3—C4—O 136.1 (4) C4—C10—C9—C8 −177.2 (4) C1i—C3—C4—O −41.3 (5) C7—C8—C9—C10 −1.2 (6)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

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N—H1···Oii 0.87 (4) 2.61 (4) 3.220 (5) 128 (3)

Figure

Figure 1A drawing of (I), with the atom-numbering scheme. Displacementellipsoids are drawn at the 50% probability level

References

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