4,5-Diamino­benzene-1,2-dicarbonitrile

Zhang, X.; Wang, W.; Jiang, J.; Ni, Z.

doi:10.1107/S1600536809008733

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Page o837

doi:10.1107/S1600536809008733

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4,5-Diaminobenzene-1,2-dicarbonitrile

Xiuwen Zhang,^a Wei Wang,^a Jianzhuang Jiang ^a ^* and Zhonghai Ni ^a

^aSchool of Chemistry & Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: nizhh@sdu.edu.cn

(Received 3 March 2009; accepted 10 March 2009; online 25 March 2009)

The molecular skeleton of the title molecule, C₈H₆N₄, is essentially planar [maximum deviation from the mean plane of 0.037 (2) Å]. All N atoms are involved in the formation of intermolecular N—H⋯N hydrogen bonds. The crystal packing exhibits also dipole–dipole interactions between the cyano groups of neighbouring molecules [C⋯C 3.473 (2) Å].

Related literature

For details of the synthesis, see: Cheeseman (1962 ); Mitzel et al. (2003 ). For applications of diamido compounds, see: Rusanova et al. (2002 ); Youngblood (2006 ). For a related crystal structure, see: Zhang & Lu (2007 ).

Experimental

Crystal data

C₈H₆N₄
M_r = 158.17
Monoclinic, P 2₁ /c
a = 8.2966 (11) Å
b = 17.100 (2) Å
c = 5.5295 (7) Å
β = 102.256 (2)°
V = 766.60 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 273 K
0.20 × 0.18 × 0.14 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.980, T_max = 0.988
4031 measured reflections
1502 independent reflections
1201 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.146
S = 0.95
1502 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N3ⁱ	0.86	2.47	3.283 (2)	158
N2—H2B⋯N4ⁱⁱ	0.86	2.37	3.225 (2)	171
N1—H1A⋯N1ⁱⁱⁱ	0.86	2.52	3.3729 (16)	169
N1—H1B⋯N4ⁱⁱ	0.86	2.34	3.188 (2)	171
Symmetry codes: (i) -x+1, -y+1, -z; (ii) x-1, y, z-1; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2001 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XP in SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809008733/cv2527sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008733/cv2527Isup2.hkl

checkCIF report

Comment top

Diamido compounds have been paid much attention becuase of their wide application in the preparation of Schiff bases and other organic ligands. On the other hand, dicyano compounds have been widely used to synthesize many useful materials such as phthalocyanine dyes. Very recently, organic ligands with differernt functional groups have attracted intense interest in the design and synthesis of functional materials, among which the title compound (I) as an very interesting small organic bifunctional precursor have been synthesied and employed to design and synthesize phthalocyanine compounds (Rusanova et al., 2002; Mitzel et al., 2003; Youngblood et al., 2006). Herein, we report its crystal structure (Fig. 1).

The whole molecular structure of (I) is essentially planar with the largest deviation value of 0.037 (2) Å from the mean plane. The cyano groups bond lengths are 1.140 (2) and 1.142 (2) Å, respectively, which are similar to those in cyano-substituted organic ligands (Zhang et al., 2007).

In the crystal, the molecules are linked by four different N···H—N intermolecular hydrogen bonds (Table 2) between primary amido hydrogen atoms and amido and cyano nitrogen atoms. In additon, the crystal packing exhibits dipole-dipole interactions between the cyano groups of neighbouring molecules proved by short distance C6···C7(-x + 1, -y + 1, -z + 1) of 3.473 (2) Å (Table 1).

Related literature top

For details of the synthesis, see: Cheeseman (1962); Mitzel et al. (2003). For applications of diamido compounds, see: Rusanova et al. (2002); Youngblood et al. (2006). For a related crystal structure, see: Zhang & Lu (2007).

Experimental top

The title compound 4,5-diamido-1,2-dicyanobenzene was prepared by four steps reaction from the starting material 1,2-diamidobenzene according to the method reported in the literature (Cheeseman, 1962; Mitzel et al., 2003). A solid of 4,5-diamido-1,2-dicyanobenzene (0.5 mmol) was added to the acetone solution (8 ml). The solution was slowly evaporated to generate white block single crystals suitable for X-ray diffraction analysis. Elemental analysis [found (calculated)] for C₈H₆N₄: C 60.63 (60.75), H 3.77 (3.82), N 35.36% (35.42%).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: XP in SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. A view of (I) with the unique atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.

4,5-Diaminobenzene-1,2-dicarbonitrile top

Crystal data top

C₈H₆N₄	F(000) = 328
M_r = 158.17	D_x = 1.370 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1651 reflections
a = 8.2966 (11) Å	θ = 2.5–26.5°
b = 17.100 (2) Å	µ = 0.09 mm⁻¹
c = 5.5295 (7) Å	T = 273 K
β = 102.256 (2)°	Block, white
V = 766.60 (17) Å³	0.20 × 0.18 × 0.14 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1502 independent reflections
Radiation source: fine-focus sealed tube	1201 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
Detector resolution: 0 pixels mm^-1	θ_max = 26.0°, θ_min = 2.5°
ϕ and ω scans	h = −10→9
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→21
T_min = 0.980, T_max = 0.988	l = −5→6
4031 measured 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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H-atom parameters constrained
S = 0.95	w = 1/[σ²(F_o²) + (0.1P)² + 0.1224P] where P = (F_o² + 2F_c²)/3
1502 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₈H₆N₄	V = 766.60 (17) Å³
M_r = 158.17	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.2966 (11) Å	µ = 0.09 mm⁻¹
b = 17.100 (2) Å	T = 273 K
c = 5.5295 (7) Å	0.20 × 0.18 × 0.14 mm
β = 102.256 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1502 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1201 reflections with I > 2σ(I)
T_min = 0.980, T_max = 0.988	R_int = 0.018
4031 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.146	H-atom parameters constrained
S = 0.95	Δρ_max = 0.25 e Å⁻³
1502 reflections	Δρ_min = −0.21 e Å⁻³
109 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
N1	0.03342 (15)	0.30649 (8)	0.3604 (3)	0.0488 (4)
H1A	0.0217	0.2745	0.4754	0.059*
H1B	−0.0488	0.3167	0.2412	0.059*
N2	0.07879 (17)	0.40517 (9)	−0.0247 (3)	0.0548 (4)
H2A	0.0940	0.4338	−0.1457	0.066*
H2B	−0.0173	0.3862	−0.0256	0.066*
N3	0.78147 (18)	0.46391 (10)	0.3631 (3)	0.0667 (5)
N4	0.7218 (2)	0.32364 (11)	0.9135 (3)	0.0736 (5)
C1	0.36358 (19)	0.42015 (9)	0.1736 (3)	0.0449 (4)
H1C	0.3794	0.4522	0.0448	0.054*
C2	0.20725 (18)	0.38986 (9)	0.1690 (3)	0.0396 (4)
C3	0.18407 (17)	0.34143 (8)	0.3672 (3)	0.0378 (4)
C4	0.31750 (18)	0.32537 (8)	0.5584 (3)	0.0409 (4)
H4A	0.3022	0.2937	0.6886	0.049*
C5	0.47413 (18)	0.35546 (9)	0.5606 (3)	0.0411 (4)
C6	0.49666 (18)	0.40366 (9)	0.3661 (3)	0.0417 (4)
C7	0.6563 (2)	0.43676 (10)	0.3652 (3)	0.0492 (4)
C8	0.6111 (2)	0.33725 (10)	0.7576 (3)	0.0506 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0348 (7)	0.0570 (8)	0.0518 (8)	−0.0050 (6)	0.0027 (6)	0.0110 (6)
N2	0.0419 (8)	0.0688 (9)	0.0497 (8)	−0.0017 (6)	0.0008 (6)	0.0155 (7)
N3	0.0443 (9)	0.0755 (11)	0.0815 (12)	−0.0086 (7)	0.0157 (8)	0.0026 (8)
N4	0.0496 (9)	0.1007 (14)	0.0603 (10)	0.0000 (9)	−0.0112 (8)	0.0071 (9)
C1	0.0428 (9)	0.0485 (9)	0.0440 (9)	−0.0010 (7)	0.0103 (7)	0.0055 (7)
C2	0.0370 (8)	0.0410 (8)	0.0394 (8)	0.0035 (6)	0.0048 (6)	−0.0004 (6)
C3	0.0342 (7)	0.0375 (7)	0.0415 (8)	0.0009 (5)	0.0072 (6)	−0.0031 (6)
C4	0.0394 (9)	0.0446 (8)	0.0376 (8)	−0.0009 (6)	0.0054 (6)	0.0035 (6)
C5	0.0366 (8)	0.0448 (8)	0.0394 (8)	0.0008 (6)	0.0028 (6)	−0.0033 (6)
C6	0.0349 (8)	0.0463 (8)	0.0437 (8)	−0.0010 (6)	0.0080 (6)	−0.0030 (6)
C7	0.0425 (9)	0.0529 (9)	0.0527 (10)	−0.0008 (7)	0.0113 (7)	0.0011 (7)
C8	0.0399 (9)	0.0610 (10)	0.0480 (9)	−0.0040 (7)	0.0028 (7)	−0.0008 (7)

Geometric parameters (Å, º) top

N1—C3	1.3787 (19)	C1—C2	1.392 (2)
N1—H1A	0.8600	C1—H1C	0.9300
N1—H1B	0.8600	C2—C3	1.419 (2)
N2—C2	1.366 (2)	C3—C4	1.387 (2)
N2—H2A	0.8600	C4—C5	1.395 (2)
N2—H2B	0.8600	C4—H4A	0.9300
N3—C7	1.140 (2)	C5—C6	1.399 (2)
N4—C8	1.142 (2)	C5—C8	1.432 (2)
C1—C6	1.390 (2)	C6—C7	1.441 (2)

C6···C7ⁱ	3.473 (2)

C3—N1—H1A	120.0	N1—C3—C2	120.18 (13)
C3—N1—H1B	120.0	C4—C3—C2	119.18 (13)
H1A—N1—H1B	120.0	C3—C4—C5	121.64 (14)
C2—N2—H2A	120.0	C3—C4—H4A	119.2
C2—N2—H2B	120.0	C5—C4—H4A	119.2
H2A—N2—H2B	120.0	C4—C5—C6	119.15 (13)
C6—C1—C2	121.61 (14)	C4—C5—C8	120.90 (14)
C6—C1—H1C	119.2	C6—C5—C8	119.95 (13)
C2—C1—H1C	119.2	C1—C6—C5	119.61 (13)
N2—C2—C1	120.78 (14)	C1—C6—C7	119.94 (14)
N2—C2—C3	120.42 (14)	C5—C6—C7	120.45 (14)
C1—C2—C3	118.80 (14)	N3—C7—C6	179.01 (18)
N1—C3—C4	120.48 (14)	N4—C8—C5	178.92 (19)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱⁱ	0.86	2.47	3.283 (2)	158
N2—H2B···N4ⁱⁱⁱ	0.86	2.37	3.225 (2)	171
N1—H1A···N1^iv	0.86	2.52	3.3729 (16)	169
N1—H1B···N4ⁱⁱⁱ	0.86	2.34	3.188 (2)	171

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

Experimental details

Crystal data
Chemical formula	C₈H₆N₄
M_r	158.17
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	273
a, b, c (Å)	8.2966 (11), 17.100 (2), 5.5295 (7)
β (°)	102.256 (2)
V (Å³)	766.60 (17)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.14

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.980, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4031, 1502, 1201
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.146, 0.95
No. of reflections	1502
No. of parameters	109
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.21

Computer programs: APEX2 (Bruker, 2004), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N3ⁱ	0.86	2.47	3.283 (2)	158.1
N2—H2B···N4ⁱⁱ	0.86	2.37	3.225 (2)	171.0
N1—H1A···N1ⁱⁱⁱ	0.86	2.52	3.3729 (16)	169.3
N1—H1B···N4ⁱⁱ	0.86	2.34	3.188 (2)	171.2

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

Acknowledgements

This work was supported by the Postdoctoral Scientific Special Foundation of China (grant No. 200801414) and the Postdoctoral Scientific Foundation of Shandong Province (grant No. 200701010).

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