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