Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041992/im2032sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041992/im2032Isup2.hkl |
CCDC reference: 663684
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.
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.
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.
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).
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).
C28H16N2 | F(000) = 396 |
Mr = 380.43 | Dx = 1.411 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1843 reflections |
a = 4.515 (3) Å | θ = 3.2–27.5° |
b = 10.325 (6) Å | µ = 0.08 mm−1 |
c = 19.28 (1) Å | T = 223 K |
β = 95.127 (7)° | Needle, brown |
V = 895.2 (9) Å3 | 0.6 × 0.03 × 0.03 mm |
Z = 2 |
Rigaku/MSC Mercury CCD area-detector diffractometer | 2015 independent reflections |
Radiation source: rotating-anode X-ray tube | 1606 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
Detector resolution: 14.6199 pixels mm-1 | θmax = 27.5°, θmin = 4.3° |
ω scans | h = −5→3 |
Absorption correction: numerical (NUMABS; Higashi, 1999) | k = −13→11 |
Tmin = 0.994, Tmax = 0.998 | l = −23→24 |
6727 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.072 | All H-atom parameters refined |
wR(F2) = 0.162 | w = 1/[σ2(FO2) + (0.0645P)2 + 0.2734P] where P = (Fo2 + 2Fc2)/3 |
S = 1.23 | (Δ/σ)max < 0.001 |
2015 reflections | Δρmax = 0.26 e Å−3 |
168 parameters | Δρmin = −0.14 e Å−3 |
C28H16N2 | V = 895.2 (9) Å3 |
Mr = 380.43 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 4.515 (3) Å | µ = 0.08 mm−1 |
b = 10.325 (6) Å | T = 223 K |
c = 19.28 (1) Å | 0.6 × 0.03 × 0.03 mm |
β = 95.127 (7)° |
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 = 0.998 | Rint = 0.034 |
6727 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | 0 restraints |
wR(F2) = 0.162 | All H-atom parameters refined |
S = 1.23 | Δρmax = 0.26 e Å−3 |
2015 reflections | Δρmin = −0.14 e Å−3 |
168 parameters |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2051 (4) | 0.41851 (18) | 0.53097 (9) | 0.0220 (4) | |
C2 | 0.0906 (4) | 0.40351 (19) | 0.46010 (9) | 0.0227 (4) | |
C3 | 0.1953 (4) | 0.2991 (2) | 0.41947 (10) | 0.0276 (5) | |
C4 | 0.3987 (4) | 0.2143 (2) | 0.44742 (11) | 0.0283 (5) | |
C5 | 0.5201 (4) | 0.22354 (19) | 0.51910 (10) | 0.0247 (4) | |
C6 | 0.7253 (4) | 0.1343 (2) | 0.54795 (11) | 0.0275 (5) | |
C7 | 0.8404 (4) | 0.14200 (18) | 0.61788 (11) | 0.0255 (4) | |
C8 | 1.0472 (4) | 0.0495 (2) | 0.64880 (12) | 0.0333 (5) | |
C9 | 1.1514 (4) | 0.0595 (2) | 0.71718 (12) | 0.0364 (5) | |
C10 | 1.0542 (4) | 0.1604 (2) | 0.75901 (12) | 0.0361 (5) | |
C11 | 0.8577 (4) | 0.2512 (2) | 0.73117 (11) | 0.0312 (5) | |
C12 | 0.7453 (4) | 0.24478 (18) | 0.65992 (10) | 0.0252 (4) | |
C13 | 0.5393 (4) | 0.33602 (19) | 0.63034 (10) | 0.0250 (4) | |
C14 | 0.4242 (4) | 0.32624 (18) | 0.56151 (10) | 0.0228 (4) | |
N1 | −0.1132 (3) | 0.48528 (16) | 0.42973 (8) | 0.0239 (4) | |
H1 | 0.120 (4) | 0.292 (2) | 0.3702 (12) | 0.032 (6)* | |
H2 | 0.473 (5) | 0.139 (2) | 0.4197 (12) | 0.039 (6)* | |
H3 | 0.788 (4) | 0.065 (2) | 0.5195 (12) | 0.030 (6)* | |
H4 | 1.119 (5) | −0.019 (2) | 0.6190 (13) | 0.038 (6)* | |
H5 | 1.294 (5) | −0.003 (3) | 0.7385 (14) | 0.048 (7)* | |
H6 | 1.126 (5) | 0.163 (2) | 0.8083 (13) | 0.043 (7)* | |
H7 | 0.783 (5) | 0.319 (2) | 0.7588 (13) | 0.037 (6)* | |
H8 | 0.471 (5) | 0.406 (2) | 0.6576 (12) | 0.033 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0215 (8) | 0.0214 (10) | 0.0232 (10) | −0.0019 (6) | 0.0019 (6) | 0.0014 (7) |
C2 | 0.0230 (8) | 0.0227 (10) | 0.0219 (10) | −0.0013 (7) | 0.0001 (6) | 0.0014 (8) |
C3 | 0.0319 (9) | 0.0297 (11) | 0.0207 (10) | 0.0021 (8) | −0.0001 (7) | −0.0038 (8) |
C4 | 0.0320 (9) | 0.0280 (11) | 0.0252 (11) | 0.0029 (8) | 0.0043 (7) | −0.0051 (8) |
C5 | 0.0240 (8) | 0.0238 (10) | 0.0263 (11) | −0.0009 (7) | 0.0029 (7) | 0.0007 (8) |
C6 | 0.0300 (9) | 0.0235 (10) | 0.0297 (11) | 0.0047 (7) | 0.0066 (7) | −0.0021 (9) |
C7 | 0.0236 (8) | 0.0236 (10) | 0.0296 (10) | 0.0007 (7) | 0.0039 (7) | 0.0046 (8) |
C8 | 0.0308 (10) | 0.0316 (12) | 0.0374 (12) | 0.0076 (8) | 0.0033 (8) | 0.0061 (10) |
C9 | 0.0315 (10) | 0.0390 (13) | 0.0380 (12) | 0.0065 (9) | −0.0007 (8) | 0.0122 (10) |
C10 | 0.0349 (10) | 0.0425 (13) | 0.0297 (12) | 0.0022 (9) | −0.0045 (8) | 0.0075 (10) |
C11 | 0.0310 (9) | 0.0337 (12) | 0.0285 (11) | 0.0010 (8) | −0.0003 (8) | 0.0024 (9) |
C12 | 0.0234 (8) | 0.0241 (10) | 0.0281 (11) | −0.0022 (7) | 0.0016 (7) | 0.0031 (8) |
C13 | 0.0275 (9) | 0.0224 (10) | 0.0252 (10) | 0.0016 (7) | 0.0024 (7) | 0.0000 (8) |
C14 | 0.0230 (8) | 0.0204 (10) | 0.0251 (10) | −0.0026 (7) | 0.0018 (7) | 0.0006 (8) |
N1 | 0.0261 (7) | 0.0218 (8) | 0.0234 (8) | 0.0008 (6) | 0.0002 (6) | −0.0002 (7) |
C1—N1i | 1.337 (2) | C7—C8 | 1.428 (3) |
C1—C2 | 1.425 (3) | C8—C9 | 1.364 (3) |
C1—C14 | 1.459 (2) | C8—H4 | 0.99 (3) |
C2—N1 | 1.344 (2) | C9—C10 | 1.411 (3) |
C2—C3 | 1.437 (3) | C9—H5 | 0.98 (3) |
C3—C4 | 1.346 (3) | C10—C11 | 1.367 (3) |
C3—H1 | 0.98 (2) | C10—H6 | 0.98 (2) |
C4—C5 | 1.444 (3) | C11—C12 | 1.423 (3) |
C4—H2 | 1.01 (2) | C11—H7 | 0.96 (2) |
C5—C6 | 1.387 (3) | C12—C13 | 1.408 (3) |
C5—C14 | 1.430 (3) | C13—C14 | 1.385 (3) |
C6—C7 | 1.403 (3) | C13—H8 | 0.96 (2) |
C6—H3 | 0.96 (2) | N1—C1i | 1.337 (2) |
C7—C12 | 1.425 (3) | ||
N1i—C1—C2 | 121.30 (16) | C9—C8—H4 | 121.0 (14) |
N1i—C1—C14 | 119.32 (16) | C7—C8—H4 | 118.4 (14) |
C2—C1—C14 | 119.37 (17) | C8—C9—C10 | 120.7 (2) |
N1—C2—C1 | 121.66 (17) | C8—C9—H5 | 120.8 (16) |
N1—C2—C3 | 118.64 (17) | C10—C9—H5 | 118.5 (16) |
C1—C2—C3 | 119.70 (16) | C11—C10—C9 | 120.4 (2) |
C4—C3—C2 | 121.03 (18) | C11—C10—H6 | 120.5 (15) |
C4—C3—H1 | 120.3 (13) | C9—C10—H6 | 119.1 (15) |
C2—C3—H1 | 118.7 (13) | C10—C11—C12 | 120.7 (2) |
C3—C4—C5 | 121.83 (18) | C10—C11—H7 | 122.0 (14) |
C3—C4—H2 | 122.0 (13) | C12—C11—H7 | 117.2 (14) |
C5—C4—H2 | 116.1 (13) | C13—C12—C11 | 121.71 (18) |
C6—C5—C14 | 119.26 (18) | C13—C12—C7 | 119.31 (18) |
C6—C5—C4 | 121.51 (18) | C11—C12—C7 | 118.97 (18) |
C14—C5—C4 | 119.22 (17) | C14—C13—C12 | 121.13 (18) |
C5—C6—C7 | 121.61 (18) | C14—C13—H8 | 117.9 (13) |
C5—C6—H3 | 119.1 (13) | C12—C13—H8 | 120.9 (13) |
C7—C6—H3 | 119.2 (13) | C13—C14—C5 | 119.70 (17) |
C6—C7—C12 | 118.97 (17) | C13—C14—C1 | 121.46 (17) |
C6—C7—C8 | 122.36 (19) | C5—C14—C1 | 118.84 (17) |
C12—C7—C8 | 118.66 (19) | C1i—N1—C2 | 117.04 (16) |
C9—C8—C7 | 120.6 (2) | ||
N1i—C1—C2—N1 | 0.2 (3) | C10—C11—C12—C7 | 0.1 (3) |
C14—C1—C2—N1 | 179.48 (16) | C6—C7—C12—C13 | −0.1 (3) |
N1i—C1—C2—C3 | 179.84 (17) | C8—C7—C12—C13 | −179.40 (18) |
C14—C1—C2—C3 | −0.9 (3) | C6—C7—C12—C11 | 178.81 (17) |
N1—C2—C3—C4 | −179.81 (18) | C8—C7—C12—C11 | −0.4 (3) |
C1—C2—C3—C4 | 0.5 (3) | C11—C12—C13—C14 | −177.86 (17) |
C2—C3—C4—C5 | 0.2 (3) | C7—C12—C13—C14 | 1.1 (3) |
C3—C4—C5—C6 | 178.72 (19) | C12—C13—C14—C5 | −1.3 (3) |
C3—C4—C5—C14 | −0.6 (3) | C12—C13—C14—C1 | 178.43 (17) |
C14—C5—C6—C7 | 0.2 (3) | C6—C5—C14—C13 | 0.7 (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—C8 | 178.73 (19) | C4—C5—C14—C1 | 0.2 (3) |
C6—C7—C8—C9 | −179.26 (19) | N1i—C1—C14—C13 | 0.0 (3) |
C12—C7—C8—C9 | 0.0 (3) | C2—C1—C14—C13 | −179.28 (16) |
C7—C8—C9—C10 | 0.9 (3) | N1i—C1—C14—C5 | 179.79 (16) |
C8—C9—C10—C11 | −1.2 (3) | C2—C1—C14—C5 | 0.5 (2) |
C9—C10—C11—C12 | 0.7 (3) | C1—C2—N1—C1i | −0.2 (3) |
C10—C11—C12—C13 | 179.02 (19) | C3—C2—N1—C1i | −179.83 (16) |
Symmetry code: (i) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C28H16N2 |
Mr | 380.43 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 223 |
a, b, c (Å) | 4.515 (3), 10.325 (6), 19.28 (1) |
β (°) | 95.127 (7) |
V (Å3) | 895.2 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.6 × 0.03 × 0.03 |
Data collection | |
Diffractometer | Rigaku/MSC Mercury CCD area-detector |
Absorption correction | Numerical (NUMABS; Higashi, 1999) |
Tmin, Tmax | 0.994, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6727, 2015, 1606 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.162, 1.23 |
No. of reflections | 2015 |
No. of parameters | 168 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.26, −0.14 |
Computer programs: CrystalClear (Rigaku/MSC, 2001), WinGX (Farrugia, 1999), SIR2004 (Burla et al., 2005), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997).
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.