2,5-Dibenzoyl­benzene-1,4-diaminium dichloride

Deng, S.-P.; Liu, S.; Yang, F.; Xu, J.-L.; Zhu, H.-J.

doi:10.1107/S1600536807068730

organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o387

doi:10.1107/S1600536807068730

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2,5-Dibenzoylbenzene-1,4-diaminium dichloride

Shui-Ping Deng,^a Shan Liu,^a Fei Yang,^a Ji-Ling Xu ^a and Hong-Jun Zhu ^a ^*

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: zhuhj@njut.edu.cn

(Received 14 December 2007; accepted 29 December 2007; online 9 January 2008)

The asymmetric unit of the title compound, C₂₀H₁₈N₂O₂²⁺·2Cl⁻, is composed of one-half of the 2,5-dibenzoylbenzene-1,4-diaminium dication, located on a centre of inversion, and one Cl⁻ ion. The dihedral angle between the central benzene ring and the benzoyl phenyl ring is 53.3 (2)°. In the crystal structure, ions are linked to form a two-dimensional network parallel to the (10 $[\overline{1}]$ ) plane by N—H⋯Cl hydrogen bonds.

Related literature

For bond-length data, see: Allen et al. (1987 ). For general background, see: Antoniadis et al. (1994 ); Imai et al. (1975 ); Kolosov et al. (2002 ); Tonzola et al. (2003 ).

Experimental

Crystal data

C₂₀H₁₈N₂O₂²⁺·2Cl⁻
M_r = 389.26
Monoclinic, P 2₁ /n
a = 12.373 (3) Å
b = 5.195 (1) Å
c = 14.315 (3) Å
β = 104.46 (3)°
V = 891.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 298 (2) K
0.40 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.862, T_max = 0.963
1754 measured reflections
1754 independent reflections
1232 reflections with I > 2σ(I)
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.162
S = 1.08
1754 reflections
130 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯Cl1ⁱ	0.87 (4)	2.29 (4)	3.155 (3)	172 (4)
N1—H2N⋯Cl1	0.87 (4)	2.33 (4)	3.187 (3)	174 (4)
N1—H3N⋯Cl1ⁱⁱ	0.87 (3)	2.29 (3)	3.159 (4)	175 (2)
Symmetry codes: (i) x, y+1, z; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068730/ci2546sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068730/ci2546Isup2.hkl

checkCIF report

Comment top

2,5-Dibenzoyl-1,4-phenylenediamine (DBPDA) is one of the important monomers, being utilized to synthesize organic semiconductors and conjugated polymers containing anthrazoline unit (Tonzola et al., 2003), which are of wide current interest for applications in electronic and optoelectronic devices including light-emitting diodes (Kolosov et al., 2002), thin film transistors, and photovoltaic cells (Antoniadis et al., 1994). We report here the crystal structure of the title compound.

The asymmetric unit is composed of one-half of the 2,5-dibenzoyl-1,4-phenylenediaminium dication located on a centre of inversion, and one chloride ion (Fig.1). The bond lengths and angles are within normal ranges (Allen et al., 1987). The dihedral angle between the C1—C6 and C8—C10/C8A—C10A rings is 53.3 (2)°.

In the crystal structure, molecules are connected together by N—H···Cl hydrogen bonds (Table 1) to form a two-dimensional network parallel to the (1 0 1) plane (Fig. 2).

Related literature top

For bond-length data, see: Allen et al. (1987). For general background, see: Antoniadis et al. (1994); Imai et al. (1975); Kolosov et al. (2002); Tonzola et al. (2003).

Experimental top

2,5-Dibenzoyl-1,4-phenylenediamine was synthesized as reported elsewhere (Imai et al., 1975). Single crystals suitable for X-ray diffraction were obtained by dissolving the compound (2.0 g, 6.3 mmol) in hydrochloric acid (50 ml, 1.0 mol/l) and allowing the solution to evaporate at room temperature for about 25 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).

Figures top

	Fig. 1. The molecular structure of the title compound, showing 40% probability displacement ellipsoids. Atoms labelled with the suffix a are generated by the symmetry operations (1 - x, 1 - y, -z). Hydrogen bonds are shown as dashed lines.
	Fig. 2. Crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

2,5-Dibenzoylbenzene-1,4-diaminium dichloride top

Crystal data top

C₂₀H₁₈N₂O₂²⁺·2Cl⁻	F(000) = 404
M_r = 389.26	D_x = 1.451 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 12.373 (3) Å	θ = 9–13°
b = 5.195 (1) Å	µ = 0.38 mm⁻¹
c = 14.315 (3) Å	T = 298 K
β = 104.46 (3)°	Block, colourless
V = 891.0 (4) Å³	0.40 × 0.10 × 0.10 mm
Z = 2

Data collection top

Enraf–Nonius CAD-4 diffractometer	1232 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.000
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω/2θ scans	h = −15→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
T_min = 0.862, T_max = 0.963	l = 0→17
1754 measured reflections	3 standard reflections every 200 reflections
1754 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0704P)² + 0.5685P] where P = (F_o² + 2F_c²)/3
1754 reflections	(Δ/σ)_max = 0.001
130 parameters	Δρ_max = 0.31 e Å⁻³
3 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₂₀H₁₈N₂O₂²⁺·2Cl⁻	V = 891.0 (4) Å³
M_r = 389.26	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.373 (3) Å	µ = 0.38 mm⁻¹
b = 5.195 (1) Å	T = 298 K
c = 14.315 (3) Å	0.40 × 0.10 × 0.10 mm
β = 104.46 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	1754 independent reflections
Absorption correction: ψ scan (North et al., 1968)	1232 reflections with I > 2σ(I)
T_min = 0.862, T_max = 0.963	R_int = 0.000
1754 measured reflections	3 standard reflections every 200 reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	3 restraints
wR(F²) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.31 e Å⁻³
1754 reflections	Δρ_min = −0.28 e Å⁻³
130 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
O1	0.2971 (2)	0.0151 (5)	−0.11097 (19)	0.0386 (7)
N1	0.6436 (3)	0.5247 (6)	0.1879 (2)	0.0265 (7)
H1N	0.635 (4)	0.655 (7)	0.224 (3)	0.073 (17)*
H2N	0.633 (3)	0.394 (7)	0.222 (3)	0.045 (12)*
H3N	0.714 (2)	0.517 (8)	0.188 (3)	0.040 (12)*
C1	0.1700 (4)	0.2318 (8)	0.1666 (3)	0.0438 (10)
H1	0.1688	0.3459	0.2164	0.053*
C2	0.1003 (3)	0.0237 (9)	0.1510 (3)	0.0450 (10)
H2	0.0508	−0.0008	0.1896	0.054*
C3	0.1022 (3)	−0.1489 (8)	0.0793 (3)	0.0442 (10)
H3	0.0558	−0.2922	0.0706	0.053*
C4	0.1732 (3)	−0.1104 (7)	0.0200 (3)	0.0372 (9)
H4	0.1731	−0.2260	−0.0296	0.045*
C5	0.2448 (3)	0.1002 (7)	0.0339 (3)	0.0274 (8)
C6	0.2430 (3)	0.2733 (7)	0.1081 (3)	0.0352 (9)
H6	0.2902	0.4154	0.1184	0.042*
C7	0.3141 (3)	0.1395 (6)	−0.0361 (2)	0.0262 (8)
C8	0.4074 (3)	0.3311 (6)	−0.0166 (2)	0.0230 (7)
C9	0.4812 (3)	0.3497 (7)	0.0737 (2)	0.0250 (7)
H9	0.4697	0.2484	0.1239	0.030*
C10	0.5707 (3)	0.5142 (6)	0.0907 (2)	0.0230 (7)
Cl1	0.59773 (8)	0.02097 (17)	0.29914 (7)	0.0350 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0478 (16)	0.0345 (15)	0.0357 (14)	−0.0127 (13)	0.0148 (12)	−0.0065 (12)
N1	0.0268 (15)	0.0226 (16)	0.0272 (15)	−0.0029 (14)	0.0015 (12)	0.0026 (14)
C1	0.054 (3)	0.037 (2)	0.047 (2)	−0.004 (2)	0.025 (2)	−0.008 (2)
C2	0.039 (2)	0.051 (3)	0.050 (2)	0.002 (2)	0.0205 (19)	0.010 (2)
C3	0.041 (2)	0.035 (2)	0.060 (3)	−0.0108 (19)	0.019 (2)	0.004 (2)
C4	0.048 (2)	0.026 (2)	0.040 (2)	−0.0095 (18)	0.0165 (18)	−0.0018 (17)
C5	0.0274 (18)	0.0209 (17)	0.0343 (19)	−0.0024 (14)	0.0082 (15)	0.0009 (15)
C6	0.042 (2)	0.0258 (19)	0.039 (2)	−0.0010 (16)	0.0108 (17)	0.0012 (16)
C7	0.0291 (18)	0.0184 (16)	0.0309 (18)	0.0025 (14)	0.0070 (15)	0.0041 (14)
C8	0.0242 (16)	0.0171 (16)	0.0276 (17)	0.0007 (13)	0.0059 (13)	0.0017 (14)
C9	0.0307 (18)	0.0199 (17)	0.0254 (17)	−0.0008 (14)	0.0091 (14)	0.0050 (14)
C10	0.0284 (17)	0.0182 (16)	0.0214 (15)	0.0012 (14)	0.0046 (13)	−0.0003 (14)
Cl1	0.0418 (5)	0.0276 (5)	0.0393 (5)	0.0038 (4)	0.0168 (4)	0.0054 (4)

Geometric parameters (Å, º) top

O1—C7	1.223 (4)	C4—C5	1.390 (5)
N1—C10	1.458 (4)	C4—H4	0.93
N1—H1N	0.87 (3)	C5—C6	1.396 (5)
N1—H2N	0.87 (3)	C5—C7	1.487 (5)
N1—H3N	0.87 (2)	C6—H6	0.93
C1—C2	1.366 (6)	C7—C8	1.497 (5)
C1—C6	1.393 (5)	C8—C9	1.388 (5)
C1—H1	0.93	C8—C10ⁱ	1.409 (4)
C2—C3	1.367 (6)	C9—C10	1.372 (5)
C2—H2	0.93	C9—H9	0.93
C3—C4	1.381 (5)	C10—C8ⁱ	1.409 (4)
C3—H3	0.93

C10—N1—H1N	117 (3)	C4—C5—C6	119.0 (3)
C10—N1—H2N	111 (3)	C4—C5—C7	117.7 (3)
H1N—N1—H2N	102 (4)	C6—C5—C7	123.1 (3)
C10—N1—H3N	112 (3)	C1—C6—C5	119.6 (4)
H1N—N1—H3N	108 (4)	C1—C6—H6	120.2
H2N—N1—H3N	105 (4)	C5—C6—H6	120.2
C2—C1—C6	120.1 (4)	O1—C7—C5	121.1 (3)
C2—C1—H1	119.9	O1—C7—C8	118.1 (3)
C6—C1—H1	119.9	C5—C7—C8	120.9 (3)
C1—C2—C3	120.8 (4)	C9—C8—C10ⁱ	117.1 (3)
C1—C2—H2	119.6	C9—C8—C7	121.2 (3)
C3—C2—H2	119.6	C10ⁱ—C8—C7	121.6 (3)
C2—C3—C4	120.0 (4)	C10—C9—C8	121.5 (3)
C2—C3—H3	120.0	C10—C9—H9	119.2
C4—C3—H3	120.0	C8—C9—H9	119.2
C3—C4—C5	120.4 (4)	C9—C10—C8ⁱ	121.4 (3)
C3—C4—H4	119.8	C9—C10—N1	118.1 (3)
C5—C4—H4	119.8	C8ⁱ—C10—N1	120.5 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1ⁱⁱ	0.87 (4)	2.29 (4)	3.155 (3)	172 (4)
N1—H2N···Cl1	0.87 (4)	2.33 (4)	3.187 (3)	174 (4)
N1—H3N···Cl1ⁱⁱⁱ	0.87 (3)	2.29 (3)	3.159 (4)	175 (2)

Symmetry codes: (ii) x, y+1, z; (iii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₂O₂²⁺·2Cl⁻
M_r	389.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.373 (3), 5.195 (1), 14.315 (3)
β (°)	104.46 (3)
V (Å³)	891.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.38
Crystal size (mm)	0.40 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.862, 0.963
No. of measured, independent and observed [I > 2σ(I)] reflections	1754, 1754, 1232
R_int	0.000
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.162, 1.08
No. of reflections	1754
No. of parameters	130
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.28

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···Cl1ⁱ	0.87 (4)	2.29 (4)	3.155 (3)	172 (4)
N1—H2N···Cl1	0.87 (4)	2.33 (4)	3.187 (3)	174 (4)
N1—H3N···Cl1ⁱⁱ	0.87 (3)	2.29 (3)	3.159 (4)	175 (2)

Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

This work was supported by the innovation fund of Jiangsu Province, China. The authors thank the Center for Testing and Analysis, Nanjing University, for support.

References

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