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Acta Cryst. (2007). E63, o3952    [ doi:10.1107/S1600536807041992 ]

Dinaphtho[2,3-a,2',3'-h]phenazine

C. Kitamura, C. Sakamoto, N. Kawatsuki and A. Yoneda

Abstract top

The title compound, C28H16N2, also known as anthrazine, possesses a crystallographic center of inversion; thus half of the formula unit is crystallographically independent. The heptacyclic ring system is essentially planar. In the crystal structure, the molecular packing is characterized by a combination of a columnar stacking and a herringbone arrangement. Along the a axis, the molecules in one column form face-to-face slipped [pi]-stacks. The interplanar face-to-face distance between neighboring molecules is 3.495 (3) Å.

Comment top

The title compound, dinaphtho[2,3 − a,2',3'-h]phenazine, (I), is an old member of the acene family. The preparation of (I) was first reported by Scholl & Berblinger (1903) in the early 20 t h century. Several decades later, a highly simple synthetic method using the mild oxygen-oxidation of 2-aminoanthracene was developed by Oda's group (Kawabata et al., 1964). Since then, the procurement of the material is easy. From the viewpoint of organic semiconducting materials, (I) may be of potential use because of the large π-system. The photoconductivity of (I) was investigated by Inokuchi (1953), who showed the relation between the spectral response of photoconductivity and the optical energy gap. In the physical properites, intermolecular interactions are critical factors. However, the molecular arrangement of (I) in the solid state has not been unveiled yet. Here we report the crystal structure of (I).

The molecular structure of (I) is shown in Fig. 1. The structure is confirmed to be heptacyclic. The bond lengths and angles are all within the expected ranges. The molecule possesses a crystallographic center of inversion, and then half of the formula unit is crystallographically independent. In addition, the molecule is essentially planar. The maximum deviation from the mean plane of the aromatic ring is 0.048 (2) Å for C10. As shown in Fig. 2, the crystal structure is characterized by the column-by- column stacking mode, which contains two symmetry-independent stacks along the a axis. The interplanar tilt angle between the aromatic rings in two adjacent columns is 71.13°. The columns are seen to pack in a herringbone arrangement, when the crystal is viewed along the c axis. Along the a axis, the molecules form face-to-face slipped π-stacks. The interplanar face-to-face distance between the neighboring molecules is 3.495 (3) Å. There are neither C—H···N nor C—H···π hydrogen bonds in the crystal structure.

Related literature top

An improved synthesis of the title compound is described by Kawabata et al. (1964). The photoconductivity is reported by Inokuchi (1953). For related literature, see: Scholl & Berblinger (1903); Wolak et al. (2004).

Experimental top

The title compound was prepared according to the modified method described by Kawabata et al. (1964). To a solution of KOtBu (183 mg, 1.64 mmol) in DMSO (4 ml) and tBuOH (1 ml), 2-aminoanthracene (155 mg, 0.80 mmol) was added under air, and then the reaction mixture was stirred at room temperature overnight. The mixture was pourd into cold water, and acidified with conc. HCl. The resulting brown precipitate was filtered off, washed with water, and dried under vacuum to produce a crude product (135 mg, 88%). Vacuum sublimation in gradient-temperature tube-furnace as described by Wolak et al. (2004) gave brown needle-shaped crystals suitable for X-ray analysis.

Refinement top

All the H atoms were located from the difference Fourier map and refined isotropically. The C—H distances are in the range 0.96 (2)–0.99 (3) Å.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2001); cell refinement: CrystalClear (Rigaku/MSC, 2001); data reduction: WinGX (Farrugia, 1999); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids for non-H atoms. The unlabeled stoms are related to the labeled ones by the symmetry code (−x, 1 − y, 1 − z).
[Figure 2] Fig. 2. The packing diagram of (I), viewed down the a axis. Hydrogen atoms are omitted for clarity.
Dinaphtho[2,3 − a,2',3'-h]phenazine top
Crystal data top
C28H16N2F000 = 396
Mr = 380.43Dx = 1.411 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1843 reflections
a = 4.515 (3) Åθ = 3.2–27.5º
b = 10.325 (6) ŵ = 0.08 mm−1
c = 19.28 (1) ÅT = 223 K
β = 95.127 (7)ºNeedle, brown
V = 895.2 (9) Å30.6 × 0.03 × 0.03 mm
Z = 2
Data collection top
Rigaku/MSC Mercury CCD area-detector
diffractometer		2015 independent reflections
Radiation source: rotating-anode X-ray tube1606 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
Detector resolution: 14.6199 pixels mm-1θmax = 27.5º
T = 223 Kθmin = 4.3º
ω scansh = −5→3
Absorption correction: numerical
(NUMABS; Higashi, 1999)		k = −13→11
Tmin = 0.994, Tmax = 0.998l = −23→24
6727 measured reflections
Refinement top
Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.072  w = 1/[σ2(FO2) + (0.0645P)2 + 0.2734P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.162(Δ/σ)max < 0.001
S = 1.23Δρmax = 0.26 e Å−3
2015 reflectionsΔρmin = −0.14 e Å−3
168 parametersExtinction correction: none
Crystal data top
C28H16N2V = 895.2 (9) Å3
Mr = 380.43Z = 2
Monoclinic, P21/nMo Kα
a = 4.515 (3) ŵ = 0.08 mm−1
b = 10.325 (6) ÅT = 223 K
c = 19.28 (1) Å0.6 × 0.03 × 0.03 mm
β = 95.127 (7)º
Data collection top
Rigaku/MSC Mercury CCD area-detector
diffractometer		2015 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)		1606 reflections with I > 2σ(I)
Tmin = 0.994, Tmax = 0.998Rint = 0.034
6727 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.072168 parameters
wR(F2) = 0.162All H-atom parameters refined
S = 1.23Δρmax = 0.26 e Å−3
2015 reflectionsΔρmin = −0.14 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.2051 (4)0.41851 (18)0.53097 (9)0.0220 (4)
C20.0906 (4)0.40351 (19)0.46010 (9)0.0227 (4)
C30.1953 (4)0.2991 (2)0.41947 (10)0.0276 (5)
C40.3987 (4)0.2143 (2)0.44742 (11)0.0283 (5)
C50.5201 (4)0.22354 (19)0.51910 (10)0.0247 (4)
C60.7253 (4)0.1343 (2)0.54795 (11)0.0275 (5)
C70.8404 (4)0.14200 (18)0.61788 (11)0.0255 (4)
C81.0472 (4)0.0495 (2)0.64880 (12)0.0333 (5)
C91.1514 (4)0.0595 (2)0.71718 (12)0.0364 (5)
C101.0542 (4)0.1604 (2)0.75901 (12)0.0361 (5)
C110.8577 (4)0.2512 (2)0.73117 (11)0.0312 (5)
C120.7453 (4)0.24478 (18)0.65992 (10)0.0252 (4)
C130.5393 (4)0.33602 (19)0.63034 (10)0.0250 (4)
C140.4242 (4)0.32624 (18)0.56151 (10)0.0228 (4)
N1−0.1132 (3)0.48528 (16)0.42973 (8)0.0239 (4)
H10.120 (4)0.292 (2)0.3702 (12)0.032 (6)*
H20.473 (5)0.139 (2)0.4197 (12)0.039 (6)*
H30.788 (4)0.065 (2)0.5195 (12)0.030 (6)*
H41.119 (5)−0.019 (2)0.6190 (13)0.038 (6)*
H51.294 (5)−0.003 (3)0.7385 (14)0.048 (7)*
H61.126 (5)0.163 (2)0.8083 (13)0.043 (7)*
H70.783 (5)0.319 (2)0.7588 (13)0.037 (6)*
H80.471 (5)0.406 (2)0.6576 (12)0.033 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0215 (8)0.0214 (10)0.0232 (10)−0.0019 (6)0.0019 (6)0.0014 (7)
C20.0230 (8)0.0227 (10)0.0219 (10)−0.0013 (7)0.0001 (6)0.0014 (8)
C30.0319 (9)0.0297 (11)0.0207 (10)0.0021 (8)−0.0001 (7)−0.0038 (8)
C40.0320 (9)0.0280 (11)0.0252 (11)0.0029 (8)0.0043 (7)−0.0051 (8)
C50.0240 (8)0.0238 (10)0.0263 (11)−0.0009 (7)0.0029 (7)0.0007 (8)
C60.0300 (9)0.0235 (10)0.0297 (11)0.0047 (7)0.0066 (7)−0.0021 (9)
C70.0236 (8)0.0236 (10)0.0296 (10)0.0007 (7)0.0039 (7)0.0046 (8)
C80.0308 (10)0.0316 (12)0.0374 (12)0.0076 (8)0.0033 (8)0.0061 (10)
C90.0315 (10)0.0390 (13)0.0380 (12)0.0065 (9)−0.0007 (8)0.0122 (10)
C100.0349 (10)0.0425 (13)0.0297 (12)0.0022 (9)−0.0045 (8)0.0075 (10)
C110.0310 (9)0.0337 (12)0.0285 (11)0.0010 (8)−0.0003 (8)0.0024 (9)
C120.0234 (8)0.0241 (10)0.0281 (11)−0.0022 (7)0.0016 (7)0.0031 (8)
C130.0275 (9)0.0224 (10)0.0252 (10)0.0016 (7)0.0024 (7)0.0000 (8)
C140.0230 (8)0.0204 (10)0.0251 (10)−0.0026 (7)0.0018 (7)0.0006 (8)
N10.0261 (7)0.0218 (8)0.0234 (8)0.0008 (6)0.0002 (6)−0.0002 (7)
Geometric parameters (Å, °) top
C1—N1i1.337 (2)C7—C81.428 (3)
C1—C21.425 (3)C8—C91.364 (3)
C1—C141.459 (2)C8—H40.99 (3)
C2—N11.344 (2)C9—C101.411 (3)
C2—C31.437 (3)C9—H50.98 (3)
C3—C41.346 (3)C10—C111.367 (3)
C3—H10.98 (2)C10—H60.98 (2)
C4—C51.444 (3)C11—C121.423 (3)
C4—H21.01 (2)C11—H70.96 (2)
C5—C61.387 (3)C12—C131.408 (3)
C5—C141.430 (3)C13—C141.385 (3)
C6—C71.403 (3)C13—H80.96 (2)
C6—H30.96 (2)N1—C1i1.337 (2)
C7—C121.425 (3)
N1i—C1—C2121.30 (16)C9—C8—H4121.0 (14)
N1i—C1—C14119.32 (16)C7—C8—H4118.4 (14)
C2—C1—C14119.37 (17)C8—C9—C10120.7 (2)
N1—C2—C1121.66 (17)C8—C9—H5120.8 (16)
N1—C2—C3118.64 (17)C10—C9—H5118.5 (16)
C1—C2—C3119.70 (16)C11—C10—C9120.4 (2)
C4—C3—C2121.03 (18)C11—C10—H6120.5 (15)
C4—C3—H1120.3 (13)C9—C10—H6119.1 (15)
C2—C3—H1118.7 (13)C10—C11—C12120.7 (2)
C3—C4—C5121.83 (18)C10—C11—H7122.0 (14)
C3—C4—H2122.0 (13)C12—C11—H7117.2 (14)
C5—C4—H2116.1 (13)C13—C12—C11121.71 (18)
C6—C5—C14119.26 (18)C13—C12—C7119.31 (18)
C6—C5—C4121.51 (18)C11—C12—C7118.97 (18)
C14—C5—C4119.22 (17)C14—C13—C12121.13 (18)
C5—C6—C7121.61 (18)C14—C13—H8117.9 (13)
C5—C6—H3119.1 (13)C12—C13—H8120.9 (13)
C7—C6—H3119.2 (13)C13—C14—C5119.70 (17)
C6—C7—C12118.97 (17)C13—C14—C1121.46 (17)
C6—C7—C8122.36 (19)C5—C14—C1118.84 (17)
C12—C7—C8118.66 (19)C1i—N1—C2117.04 (16)
C9—C8—C7120.6 (2)
N1i—C1—C2—N10.2 (3)C10—C11—C12—C70.1 (3)
C14—C1—C2—N1179.48 (16)C6—C7—C12—C13−0.1 (3)
N1i—C1—C2—C3179.84 (17)C8—C7—C12—C13−179.40 (18)
C14—C1—C2—C3−0.9 (3)C6—C7—C12—C11178.81 (17)
N1—C2—C3—C4−179.81 (18)C8—C7—C12—C11−0.4 (3)
C1—C2—C3—C40.5 (3)C11—C12—C13—C14−177.86 (17)
C2—C3—C4—C50.2 (3)C7—C12—C13—C141.1 (3)
C3—C4—C5—C6178.72 (19)C12—C13—C14—C5−1.3 (3)
C3—C4—C5—C14−0.6 (3)C12—C13—C14—C1178.43 (17)
C14—C5—C6—C70.2 (3)C6—C5—C14—C130.7 (3)
C4—C5—C6—C7−179.07 (18)C4—C5—C14—C13−179.99 (17)
C5—C6—C7—C12−0.5 (3)C6—C5—C14—C1−179.10 (17)
C5—C6—C7—C8178.73 (19)C4—C5—C14—C10.2 (3)
C6—C7—C8—C9−179.26 (19)N1i—C1—C14—C130.0 (3)
C12—C7—C8—C90.0 (3)C2—C1—C14—C13−179.28 (16)
C7—C8—C9—C100.9 (3)N1i—C1—C14—C5179.79 (16)
C8—C9—C10—C11−1.2 (3)C2—C1—C14—C50.5 (2)
C9—C10—C11—C120.7 (3)C1—C2—N1—C1i−0.2 (3)
C10—C11—C12—C13179.02 (19)C3—C2—N1—C1i−179.83 (16)
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

We thank the Research Center for Molecular-Scale Nanoscience, the Institute for Molecular Science, for the collection of the X-ray data. This work was partially supported by a Grant-in-Aid (No. 18750123) for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

references
References top

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