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Acta Cryst. (2011). E67, o2666-o2667    [ doi:10.1107/S1600536811036737 ]

2,2'-[1,5-Bis(4-aminophenyl)-1,5-dihydrobenzo[1,2-d;4,5-d']diimidazole-2,6-diyl]diphenol

A. Blagus and B. Kaitner

Abstract top

The title molecule, C32H24N6O2, has a crystallographic inversion centre in the middle of the benzodiimidazole core. It exists as the enol-imine tautomeric form and exhibits a strong intramolecular O-H...N hydrogen bond. The dihedral angles between the planes of the 2-hydroxyphenyl and 4-aminophenyl substituents and the plane of the benzodiimidazole unit [12.69 (8) and 84.71 (8)°, respectively] differ significantly due to steric reasons. In the crystal, molecules are linked by C-H...[pi] interactions, forming a two-dimensional network.

Comment top

Benzodiimidazole and its derivatives are capable of adopting various coordination modes as well as forming multiple hydrogen bonds, which may provide a tool in crystal-engineering design for assembling building blocks into multi-dimensional structures (Aakeröy et al., 2001; Holman et al., 2001; Lin et al., 2004; Boydston et al., 2006; Boydston et al., 2007; Jiang et al., 2008). These compounds as potential complexing agents have been extensively investigated in recent years and were found to have a broad scope for spin crossover and biological activity. Benzodiimidazole and its derivatives are potential antitumor agents as inhibitors (Schulz & Skibo, 2000; Ansari & Lal, 2009; Demirayak, et al., 2011) and some of their metal complexes have the property of metal-to-ligand charge-transfer excited states (Ohno et al.,1992; Wang et al., 2011).

In this paper we report the synthesis and solid state structure of a novel heterocyclic system, the compound (I) containing benzodiimidazole core as a central moiety. The imidazole rings of later are substituted with 2–OH– and 4–aminobenzyl. Molecule is centrosymmetric with imposed inversion centre and placed in 2(a) special position of the space group P21/c. Molecular stereochemistry is defined by orientation of 2–OH– and 4–aminobenzyl substituent planes to the plane of benzodiimidazole (Fig. 1). Although 2-OH-benzyl is involved in forming of strong intramolecular O1–H···N2 hydrogen bond [O1-H···N2, 2.582 (2) Å] with benzodiimidazole moiety its plane deviates significantly from coplanarity with benzodiimidazole (interplanar angle 12.69°). Due to the spatial reasons the interplanar angle between the planes of 4–aminobenzyl and benzodiimidazole is 84.71°. A weak intermolecular hydrogen interactions C14–H14···πi [3.514 Å (i): x, –y–1/2, z –1/2; π refers to the C1–C6 aromatic system centroid] linked molecules into a two-dimensional network. Surprisingly, primary N3 amino groups are not involved in significant intermolecular interactions. Nevertheless, weak attraction probably exists between primary amino group with C12-to-C17 aromatic ring at the distance slightly less than 3.5 Å (Fig. 2). Crystal packing is shown in Fig. 3.

Related literature top

Benzodiimidazole and its derivatives are capable of adopting various coordination modes as well as forming multiple hydrogen bonds, see: Aakeröy et al. (2001); Holman et al. (2001). For the structures of benzodiimidazole derivatives with aromatic substituents, see: Boydston et al. (2006, 2007); Lin et al. (2004). For their pharmacological applications, see: Ansari & Lal (2009); Demirayak et al. (2011); Schulz & Skibo (2000). For applications of benzodiimidazole derivatives as ligands in coordination chemistry, see: Jiang et al. (2008). Some of their metal complexes have the property of metal-to-ligand charge-transfer excited states, see: Wang et al. (2011); Ohno et al. (1992).

Experimental top

The title compound has been prepared as a part of an investigation of the synthesis and characterisation of Schiff base ligands and their metal complexes. The compound (I) was derived from 1,5-dihydrobenzo[1,2 - d;4,5-d']diimidazole in an attempt of template synthesis of copper(II) complexes with Schiff base ligand prepared from p-phenylenediamine and salycylaldehyde. It is known that metal Shiff base complexes have very low solubility and that it is hard to prepare appropriate single crystals for the X-ray structure analysis. For these reasons we examined the possibility of getting crystal suitable for X-ray analysis by slow synthesis reaction through liquid diffusion method. The expected compound was prepared in U-tube in such a way that one arm contained ethanolic metal-aldehydate solution (1 mmol of copper(II) chloride dihydrate and 2 mmol of salycilaldehyde) and the other one ethanolic diamine solution (2 mmol of p-phenylenediamine). Chloroform was in between two solutions. The resulting precipitate was orange plated crystals.

Refinement top

The position of hydrogen atoms bounded to N3 and O1 were located in the difference Fourier map and refined. Hydrogen atoms bounded to carbon were treated as riding atoms with C–H = 0.93 Å. Isotropic thermal parameters were set up as Uiso(H) = 1.2 Ueq.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999), PARST97 (Nardelli, 1995) and Mercury (Macrae et al., 2008).

Figures top
[Figure 1] Fig. 1. An ORTEPIII presentation of the molecule in a general orientation showing crystallographic numbering scheme. Anisotropic thermal ellipsoids are pictured with 30% of probability level.
[Figure 2] Fig. 2. Two symmetry related molecules of (I), one in x, y, z and the another one in –x + 1, –y – 1, –z (i) position, showing spatial relationship between primary amino group N3 with C12-to-C17 aromatic ring.
[Figure 3] Fig. 3. The projection down b-shows the orientation of symmetry related molecules in (000) and (001) planes, towards those in (001/2) plane.
2,2'-[1,5-Bis(4-aminophenyl)-1,5- dihydrobenzo[1,2-d;4,5-d']diimidazole-2,6-diyl]diphenol top
Crystal data top
C32H24N6O2F(000) = 548
Mr = 524.57Dx = 1.403 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybcCell parameters from 2702 reflections
a = 6.5181 (3) Åθ = 4–27°
b = 13.3206 (7) ŵ = 0.09 mm−1
c = 14.3081 (7) ÅT = 298 K
β = 91.680 (4)°Prism, brown
V = 1241.77 (11) Å30.3 × 0.1 × 0.1 mm
Z = 2
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer		1605 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.052
graphiteθmax = 27.0°, θmin = 3.7°
ω scansh = −8→8
15503 measured reflectionsk = −16→17
2702 independent reflectionsl = −18→18
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.02 w = 1/[σ2(Fo2) + (0.0516P)2 + 0.1714P]
where P = (Fo2 + 2Fc2)/3
2702 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.17 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C32H24N6O2V = 1241.77 (11) Å3
Mr = 524.57Z = 2
Monoclinic, P21/cMo Kα radiation
a = 6.5181 (3) ŵ = 0.09 mm−1
b = 13.3206 (7) ÅT = 298 K
c = 14.3081 (7) Å0.3 × 0.1 × 0.1 mm
β = 91.680 (4)°
Data collection top
Oxford Diffraction Xcalibur CCD
diffractometer		1605 reflections with I > 2σ(I)
15503 measured reflectionsRint = 0.052
2702 independent reflectionsθmax = 27.0°
Refinement top
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123Δρmax = 0.17 e Å−3
S = 1.02Δρmin = −0.16 e Å−3
2702 reflectionsAbsolute structure: ?
190 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
O1−0.6794 (3)0.55326 (12)0.29326 (12)0.0681 (5)
H1−0.549 (4)0.5627 (18)0.3187 (17)0.082*
N1−0.2776 (2)0.35831 (11)0.44335 (11)0.0445 (4)
N2−0.3419 (2)0.51109 (12)0.38381 (11)0.0482 (4)
N3−0.3167 (4)−0.02530 (16)0.60297 (17)0.0715 (6)
H3A−0.295 (4)−0.077 (2)0.5640 (19)0.086*
H3B−0.424 (4)−0.0300 (19)0.6421 (19)0.086*
C1−0.7197 (3)0.45382 (16)0.29194 (14)0.0492 (5)
C2−0.5877 (3)0.38185 (15)0.33432 (13)0.0446 (5)
C3−0.6341 (3)0.28103 (16)0.31968 (15)0.0534 (6)
H3−0.54610.23250.34480.064*
C4−0.8066 (3)0.25088 (17)0.26907 (15)0.0593 (6)
H4−0.83270.18300.25930.071*
C5−0.9399 (3)0.32224 (19)0.23309 (16)0.0618 (6)
H5−1.05910.30240.20090.074*
C6−0.8976 (3)0.42242 (18)0.24457 (15)0.0582 (6)
H6−0.98910.47000.22030.070*
C7−0.4052 (3)0.41599 (15)0.38676 (13)0.0449 (5)
C9−0.1660 (3)0.51705 (14)0.44101 (13)0.0444 (5)
C10−0.1229 (3)0.42139 (14)0.47848 (14)0.0438 (5)
C110.0420 (3)0.40088 (14)0.53848 (14)0.0463 (5)
H110.06760.33730.56300.056*
C12−0.3013 (3)0.25779 (13)0.47880 (13)0.0410 (5)
C13−0.4253 (3)0.24106 (15)0.55365 (14)0.0481 (5)
H13−0.50270.29320.57770.058*
C14−0.4337 (3)0.14674 (16)0.59246 (15)0.0552 (6)
H14−0.51820.13580.64270.066*
C15−0.3202 (3)0.06807 (15)0.55872 (15)0.0502 (5)
C16−0.2049 (3)0.08554 (16)0.48043 (17)0.0604 (6)
H16−0.13490.03260.45350.072*
C17−0.1923 (3)0.17967 (16)0.44203 (16)0.0560 (6)
H17−0.10990.19060.39100.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0738 (11)0.0511 (10)0.0777 (12)0.0089 (8)−0.0240 (9)−0.0015 (8)
N10.0454 (9)0.0404 (10)0.0473 (10)−0.0055 (7)−0.0058 (8)0.0064 (7)
N20.0500 (10)0.0449 (11)0.0492 (10)−0.0047 (8)−0.0061 (8)0.0068 (8)
N30.0841 (15)0.0528 (13)0.0764 (16)−0.0128 (11)−0.0182 (12)0.0168 (11)
C10.0499 (12)0.0538 (14)0.0438 (12)0.0053 (10)0.0007 (10)−0.0017 (10)
C20.0428 (11)0.0497 (13)0.0414 (11)−0.0026 (9)0.0003 (9)0.0031 (9)
C30.0566 (13)0.0503 (13)0.0527 (13)−0.0070 (10)−0.0088 (10)0.0101 (10)
C40.0654 (14)0.0585 (15)0.0534 (14)−0.0162 (12)−0.0074 (11)0.0032 (11)
C50.0514 (13)0.0803 (18)0.0532 (14)−0.0080 (12)−0.0085 (11)−0.0006 (12)
C60.0496 (12)0.0732 (17)0.0513 (14)0.0106 (11)−0.0057 (10)−0.0036 (11)
C70.0471 (11)0.0445 (13)0.0431 (12)−0.0009 (9)−0.0004 (9)0.0047 (9)
C90.0456 (11)0.0450 (12)0.0424 (12)−0.0014 (9)−0.0015 (9)0.0056 (9)
C100.0441 (11)0.0420 (12)0.0451 (12)−0.0061 (9)0.0002 (9)0.0038 (9)
C110.0508 (11)0.0381 (12)0.0495 (12)−0.0032 (9)−0.0038 (9)0.0102 (9)
C120.0434 (10)0.0351 (11)0.0441 (12)−0.0027 (8)−0.0042 (9)0.0062 (9)
C130.0573 (12)0.0428 (12)0.0444 (12)−0.0050 (9)0.0048 (10)−0.0067 (9)
C140.0681 (14)0.0530 (14)0.0447 (13)−0.0141 (11)0.0073 (11)0.0008 (10)
C150.0524 (12)0.0429 (13)0.0544 (14)−0.0091 (10)−0.0129 (10)0.0077 (10)
C160.0605 (13)0.0451 (13)0.0756 (17)0.0090 (11)0.0030 (12)0.0007 (11)
C170.0539 (12)0.0515 (14)0.0634 (15)0.0031 (10)0.0168 (11)0.0080 (11)
Geometric parameters (Å, °) top
O1—C11.350 (2)C5—C61.372 (3)
O1—H10.92 (3)C5—H50.9300
N1—C71.378 (2)C6—H60.9300
N1—C101.395 (2)C9—C11i1.386 (3)
N1—C121.442 (2)C9—C101.407 (3)
N2—C71.334 (2)C10—C111.383 (3)
N2—C91.391 (2)C11—C9i1.386 (3)
N3—C151.395 (3)C11—H110.9300
N3—H3A0.90 (3)C12—C171.373 (3)
N3—H3B0.91 (2)C12—C131.379 (3)
C1—C61.390 (3)C13—C141.375 (3)
C1—C21.413 (3)C13—H130.9300
C2—C31.391 (3)C14—C151.378 (3)
C2—C71.460 (3)C14—H140.9300
C3—C41.379 (3)C15—C161.387 (3)
C3—H30.9300C16—C171.372 (3)
C4—C51.377 (3)C16—H160.9300
C4—H40.9300C17—H170.9300
C1—O1—H1108.4 (15)N1—C7—C2126.65 (17)
C7—N1—C10107.06 (15)C11i—C9—N2129.41 (18)
C7—N1—C12130.96 (15)C11i—C9—C10121.67 (17)
C10—N1—C12121.10 (15)N2—C9—C10108.92 (17)
C7—N2—C9106.63 (16)C11—C10—N1130.18 (17)
C15—N3—H3A113.7 (17)C11—C10—C9123.91 (17)
C15—N3—H3B109.8 (16)N1—C10—C9105.91 (16)
H3A—N3—H3B118 (2)C10—C11—C9i114.41 (17)
O1—C1—C6117.47 (19)C10—C11—H11122.8
O1—C1—C2122.94 (19)C9i—C11—H11122.8
C6—C1—C2119.6 (2)C17—C12—C13119.79 (18)
C3—C2—C1117.61 (18)C17—C12—N1120.46 (17)
C3—C2—C7123.25 (18)C13—C12—N1119.65 (17)
C1—C2—C7119.06 (18)C14—C13—C12119.50 (19)
C4—C3—C2122.0 (2)C14—C13—H13120.3
C4—C3—H3119.0C12—C13—H13120.3
C2—C3—H3119.0C13—C14—C15121.7 (2)
C5—C4—C3119.4 (2)C13—C14—H14119.2
C5—C4—H4120.3C15—C14—H14119.2
C3—C4—H4120.3C14—C15—C16117.68 (19)
C6—C5—C4120.3 (2)C14—C15—N3121.4 (2)
C6—C5—H5119.9C16—C15—N3120.9 (2)
C4—C5—H5119.9C17—C16—C15121.1 (2)
C5—C6—C1120.9 (2)C17—C16—H16119.4
C5—C6—H6119.6C15—C16—H16119.4
C1—C6—H6119.6C16—C17—C12120.1 (2)
N2—C7—N1111.48 (16)C16—C17—H17120.0
N2—C7—C2121.87 (17)C12—C17—H17120.0
Symmetry codes: (i) −x, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.921.762.582 (2)147
C14—H14···Cgii0.932.603.514 (2)167
Symmetry codes: (ii) x, −y+1/2, z+1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.921.762.582 (2)147
C14—H14···Cgi0.932.603.514 (2)167
Symmetry codes: (i) x, −y+1/2, z+1/2.
Acknowledgements top

Financial support by the Ministry of Science, Education and Sport of the Republic of Croatia is gratefully acknowledged (grant No. 119–1193079–3069).

references
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