organic compounds
N1,N4-Diphenyl-3,6-bis(phenylimino)cyclohexa-1,4-diene-1,4-diamine
aDepartment of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan, and bComprehensive Analysis Center for Science, Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan
*Correspondence e-mail: fuji@chem.saitama-u.ac.jp
In the title compound, C30H24N4, the central benzoquinonediimine moiety is approximately planar, with a maximum deviation of 0.044 (14) Å. The four terminal phenyl rings are twisted by 44.95 (11), 54.90 (10), 44.98 (10) and 50.68 (11)° with respect to the mean plane the benzoquinonediimine unit. In the crystal, molecules are linked by weak C—H⋯π interactions into supramolecular chains running along the b-axis direction.
Related literature
For general background to the title compound, see: Kimish (1875); Rall et al. (1998); Frantz et al. (2004); Siri et al. (2005); Taquet et al. (2006); Schweinfurth et al. (2013); Jeon et al. (2013). For related structures, see: Hughes & Saunders (1956); Merchant et al. (1984); Siri & Braunstein (2000); Wenderski et al. (2004); Khramov et al. (2006); Boydston et al. (2006); Huang et al., (2008); Su et al. (2012).
Experimental
Crystal data
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Data collection: SMART (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536814002906/xu5766sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814002906/xu5766Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814002906/xu5766Isup3.cml
The VIV complex [VIV(O)(η2-ox)(H2O)3] was purchased as "VO(ox).nH2O" from Wako Chemicals, and used without further purification. A solution of aniline (27.9 g, 300 mmol) in EtOH (50 cm3) was added to a solution of VO(ox).nH2O (1.13 g, 3.00 mmol) in a mixture of EtOH (50 cm3) and H2O (100 cm3). The reaction mixture was set aside for 2 weeks at room temperature in air. The precipitated crystals were filterd off, washed with H2O and EtOH, successively, and dried. Yield 1.34 g. (5.1%). 1H NMR / CDCl3: δ 8.22 (s, 2H, NH), 7.41–6.88 (m, 20H, PhH), 6.21 (s, 2H, CH). MALDI TOF MS: 441 (M+1). UV-vis / CH2Cl2, λ/nm (ε/M-1cm-1): 290 (46000), 379 (30000).
The H atoms of NH moieies were located from a Fourier difference map and refined isotrpically. Other H atoms were placed at idealized positions with C—H = 0.95 Å, and refined in ridig mode with Ueq(H) = 1.2Uiso(C).
Data collection: SMART (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of I, with displacement ellipsoids drawn at the 50% probability level. |
C30H24N4 | Z = 2 |
Mr = 440.53 | F(000) = 464 |
Triclinic, P1 | Dx = 1.315 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8858 (12) Å | Cell parameters from 1264 reflections |
b = 10.0540 (13) Å | θ = 2.4–25.9° |
c = 13.2256 (18) Å | µ = 0.08 mm−1 |
α = 93.343 (3)° | T = 173 K |
β = 106.760 (3)° | Plate, red |
γ = 98.530 (3)° | 0.30 × 0.20 × 0.10 mm |
V = 1112.4 (3) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 5291 independent reflections |
Radiation source: fine-focus sealed tube | 3273 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.0°, θmin = 1.6° |
φ and ω scans | h = −10→11 |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | k = −12→13 |
Tmin = 0.977, Tmax = 0.992 | l = −17→8 |
8166 measured reflections |
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)] = 0.064 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0775P)2 + 0.0548P] where P = (Fo2 + 2Fc2)/3 |
5291 reflections | (Δ/σ)max < 0.001 |
315 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C30H24N4 | γ = 98.530 (3)° |
Mr = 440.53 | V = 1112.4 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8858 (12) Å | Mo Kα radiation |
b = 10.0540 (13) Å | µ = 0.08 mm−1 |
c = 13.2256 (18) Å | T = 173 K |
α = 93.343 (3)° | 0.30 × 0.20 × 0.10 mm |
β = 106.760 (3)° |
Bruker SMART APEX CCD area-detector diffractometer | 5291 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 3273 reflections with I > 2σ(I) |
Tmin = 0.977, Tmax = 0.992 | Rint = 0.031 |
8166 measured reflections |
R[F2 > 2σ(F2)] = 0.064 | 0 restraints |
wR(F2) = 0.172 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.32 e Å−3 |
5291 reflections | Δρmin = −0.24 e Å−3 |
315 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) 5.6034 (0.0038) x + 5.0416 (0.0058) y + 12.9434 (0.0071) z = 8.2491 (0.0021) * 0.0006 (0.0008) C10 * -0.0066 (0.0008) C11 * 0.0067 (0.0009) C12 * -0.0008 (0.0009) C13 * -0.0053 (0.0009) C14 * 0.0053 (0.0008) C15 Rms deviation of fitted atoms = 0.0049 - 7.4963 (0.0028) x + 1.7481 (0.0065) y + 10.6592 (0.0082) z = 4.5261 (0.0067) Angle to previous plane (with approximate e.s.d.) = 86.71 (0.03) * 0.0118 (0.0008) C4 * -0.0134 (0.0008) C5 * 0.0021 (0.0009) C6 * 0.0111 (0.0009) C7 * -0.0128 (0.0009) C8 * 0.0013 (0.0009) C9 Rms deviation of fitted atoms = 0.0101 - 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043) Angle to previous plane (with approximate e.s.d.) = 30.79 (0.06) * 0.0005 (0.0006) C1 * -0.0005 (0.0006) C2 * 0.0005 (0.0006) C3 * -0.0005 (0.0006) C1_$1 * 0.0005 (0.0006) C2_$1 * -0.0005 (0.0006) C3_$1 - 3.3572 (0.0015) C13_$2 - 3.6100 (0.0013) C14_$2 - 3.7830 (0.0014) C15_$2 Rms deviation of fitted atoms = 0.0005 - 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043) Angle to previous plane (with approximate e.s.d.) = 0.00 (0.10) * 0.0005 (0.0006) C1 * -0.0005 (0.0006) C2 * 0.0005 (0.0006) C3 * -0.0005 (0.0006) C1_$1 * 0.0005 (0.0006) C2_$1 * -0.0005 (0.0006) C3_$1 - 3.7228 (0.0017) C10_$2 - 3.4796 (0.0019) C11_$2 - 3.2849 (0.0018) C12_$2 Rms deviation of fitted atoms = 0.0005 - 5.6034 (0.0038) x + 5.0416 (0.0058) y + 12.9434 (0.0070) z = 2.9266 (0.0041) Angle to previous plane (with approximate e.s.d.) = 10.70 (0.08) * 0.0006 (0.0008) C10_$2 * -0.0066 (0.0008) C11_$2 * 0.0067 (0.0009) C12_$2 * -0.0008 (0.0009) C13_$2 * -0.0053 (0.0009) C14_$2 * 0.0053 (0.0008) C15_$2 Rms deviation of fitted atoms = 0.0049 - 4.5932 (0.0050) x + 6.9089 (0.0064) y + 12.6394 (0.0086) z = 6.3197 (0.0043) Angle to previous plane (with approximate e.s.d.) = 10.70 (0.08) * 0.0005 (0.0006) C1 * -0.0005 (0.0006) C2 * 0.0005 (0.0006) C3 * -0.0005 (0.0006) C1_$1 * 0.0005 (0.0006) C2_$1 * -0.0005 (0.0006) C3_$1 Rms deviation of fitted atoms = 0.0005 |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6215 (2) | 0.1790 (2) | 0.48956 (16) | 0.0279 (5) | |
C2 | 0.5987 (2) | 0.2013 (2) | 0.59667 (16) | 0.0272 (5) | |
C3 | 0.4786 (3) | 0.2780 (2) | 0.60555 (17) | 0.0291 (5) | |
H3 | 0.4665 | 0.2981 | 0.6736 | 0.035* | |
C4 | 0.3815 (3) | 0.3228 (2) | 0.51985 (17) | 0.0290 (5) | |
C5 | 0.3993 (2) | 0.2946 (2) | 0.41226 (16) | 0.0272 (5) | |
C6 | 0.5248 (3) | 0.2248 (2) | 0.40391 (17) | 0.0298 (5) | |
H6 | 0.5412 | 0.2100 | 0.3366 | 0.036* | |
C7 | 0.8056 (2) | 0.0811 (2) | 0.40583 (17) | 0.0305 (5) | |
C8 | 0.8318 (3) | 0.1764 (2) | 0.33796 (17) | 0.0340 (5) | |
H8 | 0.8037 | 0.2632 | 0.3456 | 0.041* | |
C9 | 0.8982 (3) | 0.1449 (2) | 0.26007 (18) | 0.0377 (6) | |
H9 | 0.9168 | 0.2109 | 0.2144 | 0.045* | |
C10 | 0.9386 (3) | 0.0192 (2) | 0.24679 (19) | 0.0392 (6) | |
H10 | 0.9830 | −0.0019 | 0.1918 | 0.047* | |
C11 | 0.9138 (3) | −0.0753 (2) | 0.31417 (19) | 0.0368 (6) | |
H11 | 0.9405 | −0.1624 | 0.3054 | 0.044* | |
C12 | 0.8501 (3) | −0.0439 (2) | 0.39462 (18) | 0.0336 (5) | |
H12 | 0.8368 | −0.1084 | 0.4424 | 0.040* | |
C13 | 0.6813 (3) | 0.1632 (2) | 0.77728 (16) | 0.0286 (5) | |
C14 | 0.5421 (3) | 0.1153 (2) | 0.80110 (18) | 0.0340 (5) | |
H14 | 0.4491 | 0.0748 | 0.7456 | 0.041* | |
C15 | 0.5379 (3) | 0.1259 (2) | 0.90426 (19) | 0.0400 (6) | |
H15 | 0.4413 | 0.0938 | 0.9191 | 0.048* | |
C16 | 0.6711 (3) | 0.1823 (2) | 0.98623 (19) | 0.0396 (6) | |
H16 | 0.6666 | 0.1908 | 1.0572 | 0.048* | |
C17 | 0.8115 (3) | 0.2265 (2) | 0.96395 (18) | 0.0381 (6) | |
H17 | 0.9048 | 0.2642 | 1.0202 | 0.046* | |
C18 | 0.8180 (3) | 0.2163 (2) | 0.86100 (17) | 0.0339 (5) | |
H18 | 0.9159 | 0.2457 | 0.8469 | 0.041* | |
C19 | 0.2077 (3) | 0.4243 (2) | 0.60850 (18) | 0.0324 (5) | |
C20 | 0.3155 (3) | 0.4832 (2) | 0.70564 (19) | 0.0386 (6) | |
H20 | 0.4267 | 0.5000 | 0.7138 | 0.046* | |
C21 | 0.2614 (3) | 0.5167 (2) | 0.78905 (19) | 0.0399 (6) | |
H21 | 0.3360 | 0.5538 | 0.8555 | 0.048* | |
C22 | 0.1014 (3) | 0.4976 (2) | 0.77844 (19) | 0.0411 (6) | |
H22 | 0.0655 | 0.5217 | 0.8369 | 0.049* | |
C23 | −0.0066 (3) | 0.4433 (2) | 0.68263 (19) | 0.0373 (6) | |
H23 | −0.1176 | 0.4322 | 0.6745 | 0.045* | |
C24 | 0.0450 (3) | 0.4049 (2) | 0.59809 (19) | 0.0352 (5) | |
H24 | −0.0305 | 0.3651 | 0.5327 | 0.042* | |
C25 | 0.2863 (2) | 0.3163 (2) | 0.22856 (17) | 0.0284 (5) | |
C26 | 0.2740 (3) | 0.1896 (2) | 0.17692 (18) | 0.0344 (5) | |
H26 | 0.2778 | 0.1129 | 0.2157 | 0.041* | |
C27 | 0.2564 (3) | 0.1740 (3) | 0.06994 (19) | 0.0426 (6) | |
H27 | 0.2469 | 0.0863 | 0.0354 | 0.051* | |
C28 | 0.2524 (3) | 0.2840 (3) | 0.01207 (19) | 0.0447 (6) | |
H28 | 0.2436 | 0.2729 | −0.0613 | 0.054* | |
C29 | 0.2612 (3) | 0.4105 (3) | 0.06249 (19) | 0.0401 (6) | |
H29 | 0.2575 | 0.4867 | 0.0232 | 0.048* | |
C30 | 0.2753 (3) | 0.4270 (2) | 0.16866 (17) | 0.0327 (5) | |
H30 | 0.2777 | 0.5139 | 0.2019 | 0.039* | |
H1 | 0.777 (3) | 0.075 (3) | 0.551 (2) | 0.049 (8)* | |
H2 | 0.197 (3) | 0.394 (3) | 0.453 (2) | 0.057 (8)* | |
N1 | 0.7414 (2) | 0.1088 (2) | 0.48930 (15) | 0.0334 (5) | |
N2 | 0.6936 (2) | 0.15137 (18) | 0.67317 (14) | 0.0296 (4) | |
N3 | 0.2589 (2) | 0.3886 (2) | 0.52080 (15) | 0.0361 (5) | |
N4 | 0.2966 (2) | 0.34011 (18) | 0.33658 (14) | 0.0300 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0257 (11) | 0.0305 (12) | 0.0276 (11) | 0.0063 (9) | 0.0076 (9) | 0.0019 (9) |
C2 | 0.0260 (11) | 0.0272 (11) | 0.0268 (11) | 0.0027 (9) | 0.0064 (9) | 0.0036 (9) |
C3 | 0.0331 (12) | 0.0324 (12) | 0.0248 (11) | 0.0103 (9) | 0.0111 (9) | 0.0036 (9) |
C4 | 0.0299 (11) | 0.0301 (12) | 0.0297 (12) | 0.0090 (9) | 0.0108 (9) | 0.0046 (9) |
C5 | 0.0267 (11) | 0.0277 (11) | 0.0262 (11) | 0.0043 (9) | 0.0064 (9) | 0.0053 (9) |
C6 | 0.0302 (12) | 0.0367 (13) | 0.0238 (11) | 0.0081 (9) | 0.0087 (9) | 0.0042 (9) |
C7 | 0.0223 (11) | 0.0398 (13) | 0.0277 (11) | 0.0074 (9) | 0.0037 (9) | 0.0035 (10) |
C8 | 0.0327 (12) | 0.0338 (13) | 0.0340 (13) | 0.0082 (10) | 0.0060 (10) | 0.0058 (10) |
C9 | 0.0393 (13) | 0.0411 (14) | 0.0336 (13) | 0.0088 (11) | 0.0108 (10) | 0.0070 (11) |
C10 | 0.0383 (14) | 0.0460 (15) | 0.0375 (13) | 0.0119 (11) | 0.0163 (11) | 0.0020 (11) |
C11 | 0.0336 (13) | 0.0325 (13) | 0.0443 (14) | 0.0100 (10) | 0.0104 (11) | 0.0005 (11) |
C12 | 0.0250 (11) | 0.0352 (13) | 0.0377 (13) | 0.0063 (9) | 0.0042 (9) | 0.0066 (10) |
C13 | 0.0326 (12) | 0.0269 (11) | 0.0273 (12) | 0.0129 (9) | 0.0059 (9) | 0.0068 (9) |
C14 | 0.0286 (12) | 0.0384 (13) | 0.0326 (13) | 0.0077 (10) | 0.0039 (9) | 0.0072 (10) |
C15 | 0.0387 (14) | 0.0473 (15) | 0.0390 (14) | 0.0117 (11) | 0.0159 (11) | 0.0127 (12) |
C16 | 0.0507 (16) | 0.0438 (14) | 0.0272 (12) | 0.0126 (12) | 0.0136 (11) | 0.0047 (11) |
C17 | 0.0424 (14) | 0.0383 (14) | 0.0282 (12) | 0.0047 (11) | 0.0036 (10) | 0.0010 (10) |
C18 | 0.0331 (12) | 0.0317 (12) | 0.0343 (13) | 0.0040 (10) | 0.0067 (10) | 0.0056 (10) |
C19 | 0.0375 (13) | 0.0299 (12) | 0.0332 (12) | 0.0106 (10) | 0.0126 (10) | 0.0082 (10) |
C20 | 0.0344 (13) | 0.0398 (14) | 0.0403 (14) | 0.0075 (11) | 0.0080 (11) | 0.0078 (11) |
C21 | 0.0470 (15) | 0.0392 (14) | 0.0313 (13) | 0.0135 (11) | 0.0058 (11) | −0.0002 (11) |
C22 | 0.0554 (17) | 0.0390 (14) | 0.0350 (14) | 0.0135 (12) | 0.0201 (12) | 0.0060 (11) |
C23 | 0.0391 (13) | 0.0354 (13) | 0.0445 (14) | 0.0117 (10) | 0.0196 (11) | 0.0108 (11) |
C24 | 0.0350 (13) | 0.0337 (13) | 0.0356 (13) | 0.0082 (10) | 0.0071 (10) | 0.0066 (10) |
C25 | 0.0220 (10) | 0.0360 (13) | 0.0271 (11) | 0.0080 (9) | 0.0058 (9) | 0.0040 (10) |
C26 | 0.0336 (12) | 0.0318 (12) | 0.0367 (13) | 0.0095 (10) | 0.0069 (10) | 0.0053 (10) |
C27 | 0.0419 (15) | 0.0423 (15) | 0.0397 (14) | 0.0115 (11) | 0.0061 (11) | −0.0066 (12) |
C28 | 0.0493 (16) | 0.0602 (18) | 0.0269 (13) | 0.0211 (13) | 0.0095 (11) | 0.0040 (12) |
C29 | 0.0467 (15) | 0.0441 (15) | 0.0314 (13) | 0.0148 (12) | 0.0097 (11) | 0.0120 (11) |
C30 | 0.0329 (12) | 0.0326 (12) | 0.0326 (12) | 0.0096 (10) | 0.0074 (10) | 0.0049 (10) |
N1 | 0.0346 (11) | 0.0441 (12) | 0.0255 (10) | 0.0177 (9) | 0.0088 (8) | 0.0089 (9) |
N2 | 0.0285 (10) | 0.0336 (10) | 0.0264 (10) | 0.0091 (8) | 0.0059 (8) | 0.0038 (8) |
N3 | 0.0407 (12) | 0.0476 (12) | 0.0264 (11) | 0.0233 (9) | 0.0111 (9) | 0.0085 (9) |
N4 | 0.0299 (10) | 0.0336 (10) | 0.0275 (10) | 0.0091 (8) | 0.0075 (8) | 0.0074 (8) |
C1—C6 | 1.360 (3) | C16—C17 | 1.380 (3) |
C1—N1 | 1.363 (3) | C16—H16 | 0.9500 |
C1—C2 | 1.497 (3) | C17—C18 | 1.378 (3) |
C2—N2 | 1.296 (3) | C17—H17 | 0.9500 |
C2—C3 | 1.433 (3) | C18—H18 | 0.9500 |
C3—C4 | 1.358 (3) | C19—C24 | 1.395 (3) |
C3—H3 | 0.9500 | C19—C20 | 1.397 (3) |
C4—N3 | 1.358 (3) | C19—N3 | 1.409 (3) |
C4—C5 | 1.492 (3) | C20—C21 | 1.368 (3) |
C5—N4 | 1.302 (3) | C20—H20 | 0.9500 |
C5—C6 | 1.429 (3) | C21—C22 | 1.370 (3) |
C6—H6 | 0.9500 | C21—H21 | 0.9500 |
C7—C12 | 1.385 (3) | C22—C23 | 1.374 (4) |
C7—C8 | 1.390 (3) | C22—H22 | 0.9500 |
C7—N1 | 1.412 (3) | C23—C24 | 1.381 (3) |
C8—C9 | 1.370 (3) | C23—H23 | 0.9500 |
C8—H8 | 0.9500 | C24—H24 | 0.9500 |
C9—C10 | 1.379 (3) | C25—C26 | 1.384 (3) |
C9—H9 | 0.9500 | C25—C30 | 1.402 (3) |
C10—C11 | 1.377 (3) | C25—N4 | 1.409 (3) |
C10—H10 | 0.9500 | C26—C27 | 1.375 (3) |
C11—C12 | 1.383 (3) | C26—H26 | 0.9500 |
C11—H11 | 0.9500 | C27—C28 | 1.380 (3) |
C12—H12 | 0.9500 | C27—H27 | 0.9500 |
C13—C14 | 1.388 (3) | C28—C29 | 1.382 (4) |
C13—C18 | 1.396 (3) | C28—H28 | 0.9500 |
C13—N2 | 1.412 (3) | C29—C30 | 1.371 (3) |
C14—C15 | 1.374 (3) | C29—H29 | 0.9500 |
C14—H14 | 0.9500 | C30—H30 | 0.9500 |
C15—C16 | 1.374 (3) | N1—H1 | 0.89 (3) |
C15—H15 | 0.9500 | N3—H2 | 0.91 (3) |
C6—C1—N1 | 126.3 (2) | C18—C17—H17 | 119.6 |
C6—C1—C2 | 120.17 (19) | C16—C17—H17 | 119.6 |
N1—C1—C2 | 113.47 (17) | C17—C18—C13 | 120.3 (2) |
N2—C2—C3 | 126.4 (2) | C17—C18—H18 | 119.8 |
N2—C2—C1 | 116.00 (19) | C13—C18—H18 | 119.8 |
C3—C2—C1 | 117.54 (18) | C24—C19—C20 | 118.5 (2) |
C4—C3—C2 | 122.1 (2) | C24—C19—N3 | 119.7 (2) |
C4—C3—H3 | 118.9 | C20—C19—N3 | 121.8 (2) |
C2—C3—H3 | 118.9 | C21—C20—C19 | 120.1 (2) |
N3—C4—C3 | 125.5 (2) | C21—C20—H20 | 119.9 |
N3—C4—C5 | 114.23 (18) | C19—C20—H20 | 119.9 |
C3—C4—C5 | 120.15 (19) | C20—C21—C22 | 121.1 (2) |
N4—C5—C6 | 128.0 (2) | C20—C21—H21 | 119.4 |
N4—C5—C4 | 114.12 (19) | C22—C21—H21 | 119.4 |
C6—C5—C4 | 117.92 (18) | C21—C22—C23 | 119.5 (2) |
C1—C6—C5 | 121.9 (2) | C21—C22—H22 | 120.2 |
C1—C6—H6 | 119.0 | C23—C22—H22 | 120.2 |
C5—C6—H6 | 119.0 | C22—C23—C24 | 120.5 (2) |
C12—C7—C8 | 119.1 (2) | C22—C23—H23 | 119.7 |
C12—C7—N1 | 118.3 (2) | C24—C23—H23 | 119.7 |
C8—C7—N1 | 122.5 (2) | C23—C24—C19 | 120.1 (2) |
C9—C8—C7 | 119.9 (2) | C23—C24—H24 | 119.9 |
C9—C8—H8 | 120.0 | C19—C24—H24 | 119.9 |
C7—C8—H8 | 120.0 | C26—C25—C30 | 118.5 (2) |
C8—C9—C10 | 121.1 (2) | C26—C25—N4 | 124.02 (19) |
C8—C9—H9 | 119.4 | C30—C25—N4 | 117.3 (2) |
C10—C9—H9 | 119.4 | C27—C26—C25 | 120.4 (2) |
C11—C10—C9 | 119.2 (2) | C27—C26—H26 | 119.8 |
C11—C10—H10 | 120.4 | C25—C26—H26 | 119.8 |
C9—C10—H10 | 120.4 | C26—C27—C28 | 120.9 (2) |
C10—C11—C12 | 120.2 (2) | C26—C27—H27 | 119.5 |
C10—C11—H11 | 119.9 | C28—C27—H27 | 119.5 |
C12—C11—H11 | 119.9 | C27—C28—C29 | 119.0 (2) |
C11—C12—C7 | 120.3 (2) | C27—C28—H28 | 120.5 |
C11—C12—H12 | 119.8 | C29—C28—H28 | 120.5 |
C7—C12—H12 | 119.8 | C30—C29—C28 | 120.6 (2) |
C14—C13—C18 | 118.3 (2) | C30—C29—H29 | 119.7 |
C14—C13—N2 | 122.83 (19) | C28—C29—H29 | 119.7 |
C18—C13—N2 | 118.66 (19) | C29—C30—C25 | 120.4 (2) |
C15—C14—C13 | 120.5 (2) | C29—C30—H30 | 119.8 |
C15—C14—H14 | 119.7 | C25—C30—H30 | 119.8 |
C13—C14—H14 | 119.7 | C1—N1—C7 | 128.76 (19) |
C16—C15—C14 | 121.0 (2) | C1—N1—H1 | 111.5 (17) |
C16—C15—H15 | 119.5 | C7—N1—H1 | 119.7 (17) |
C14—C15—H15 | 119.5 | C2—N2—C13 | 121.28 (19) |
C15—C16—C17 | 119.0 (2) | C4—N3—C19 | 127.73 (19) |
C15—C16—H16 | 120.5 | C4—N3—H2 | 110.8 (18) |
C17—C16—H16 | 120.5 | C19—N3—H2 | 120.5 (18) |
C18—C17—C16 | 120.7 (2) | C5—N4—C25 | 123.01 (19) |
C6—C1—C2—N2 | 178.4 (2) | C24—C19—C20—C21 | 2.0 (3) |
N1—C1—C2—N2 | −0.2 (3) | N3—C19—C20—C21 | 179.9 (2) |
C6—C1—C2—C3 | −3.3 (3) | C19—C20—C21—C22 | −2.2 (4) |
N1—C1—C2—C3 | 178.05 (19) | C20—C21—C22—C23 | 0.3 (4) |
N2—C2—C3—C4 | −178.1 (2) | C21—C22—C23—C24 | 1.7 (3) |
C1—C2—C3—C4 | 3.8 (3) | C22—C23—C24—C19 | −1.8 (3) |
C2—C3—C4—N3 | 175.7 (2) | C20—C19—C24—C23 | −0.1 (3) |
C2—C3—C4—C5 | −0.9 (3) | N3—C19—C24—C23 | −178.0 (2) |
N3—C4—C5—N4 | 1.4 (3) | C30—C25—C26—C27 | 2.0 (3) |
C3—C4—C5—N4 | 178.4 (2) | N4—C25—C26—C27 | 176.7 (2) |
N3—C4—C5—C6 | −179.6 (2) | C25—C26—C27—C28 | 0.7 (4) |
C3—C4—C5—C6 | −2.6 (3) | C26—C27—C28—C29 | −2.0 (4) |
N1—C1—C6—C5 | 178.3 (2) | C27—C28—C29—C30 | 0.6 (4) |
C2—C1—C6—C5 | −0.1 (3) | C28—C29—C30—C25 | 2.1 (4) |
N4—C5—C6—C1 | −178.1 (2) | C26—C25—C30—C29 | −3.4 (3) |
C4—C5—C6—C1 | 3.1 (3) | N4—C25—C30—C29 | −178.5 (2) |
C12—C7—C8—C9 | 1.2 (3) | C6—C1—N1—C7 | 8.2 (4) |
N1—C7—C8—C9 | 178.3 (2) | C2—C1—N1—C7 | −173.3 (2) |
C7—C8—C9—C10 | 0.6 (3) | C12—C7—N1—C1 | −142.5 (2) |
C8—C9—C10—C11 | −1.0 (4) | C8—C7—N1—C1 | 40.4 (3) |
C9—C10—C11—C12 | −0.4 (3) | C3—C2—N2—C13 | 3.3 (3) |
C10—C11—C12—C7 | 2.2 (3) | C1—C2—N2—C13 | −178.59 (18) |
C8—C7—C12—C11 | −2.6 (3) | C14—C13—N2—C2 | 57.2 (3) |
N1—C7—C12—C11 | −179.8 (2) | C18—C13—N2—C2 | −127.5 (2) |
C18—C13—C14—C15 | 2.9 (3) | C3—C4—N3—C19 | 0.3 (4) |
N2—C13—C14—C15 | 178.2 (2) | C5—C4—N3—C19 | 177.2 (2) |
C13—C14—C15—C16 | −0.8 (4) | C24—C19—N3—C4 | −136.7 (2) |
C14—C15—C16—C17 | −1.2 (4) | C20—C19—N3—C4 | 45.4 (3) |
C15—C16—C17—C18 | 1.0 (4) | C6—C5—N4—C25 | 5.4 (3) |
C16—C17—C18—C13 | 1.1 (3) | C4—C5—N4—C25 | −175.67 (18) |
C14—C13—C18—C17 | −3.0 (3) | C26—C25—N4—C5 | 51.4 (3) |
N2—C13—C18—C17 | −178.5 (2) | C30—C25—N4—C5 | −133.8 (2) |
Cg2 and Cg4 are the centroids of the C7–C12 and C19–C24 benzene rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Cg4i | 0.95 | 2.84 | 3.675 (2) | 148 |
C14—H14···Cg2ii | 0.95 | 2.81 | 3.673 (3) | 151 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Cg2 and Cg4 are the centroids of the C7–C12 and C19–C24 benzene rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···Cg4i | 0.95 | 2.8347 | 3.675 (2) | 148 |
C14—H14···Cg2ii | 0.95 | 2.8113 | 3.673 (3) | 151 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1. |
Acknowledgements
This work has been supported by the programs of the Grants-in-Aid for Scientific Research (to TF, No. 23510115) from the Japan Society for the Promotion of Science.
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
N1,N4-Diphenyl-3,6-bis(phenylimino)cyclohexa-1,4-diene-1,4-diamine (I) was synthesized as early as in 1875 (Kimish, 1875) and called azophenine. Then I and its derivatives were obtained from aniline or substituted anilines in various ways, e.g. the oxidation of N,N'-diphenyl-p-phenylenediamine with mercury(II) oxide to give p-benzoquinone diamine followed by heating with aniline (Hughes & Saunders, 1956), heating of anilines with dry copper(II) chloride on a steam bath (Merchant et al., 1984), and the Buchwald-Hartwig cross coupling reaction (Wenderski et al., 2004). The molecular structures of the derivatives except I have been investigated (Boydston et al., 2006; Khramov et al., 2006; Huang et al., 2008). This class of compounds forms various metal complexes (Rall et al., 1998; Siri & Braunstein, 2000; Frantz et al., 2004; Siri et al., 2005; Su et al., 2012), some of which exhibit novel properties (Taquet et al., 2006; Schweinfurth et al., 2013), e.g. one-electron reduced dinuclear Fe complex with I behaves as a single molecule magnet with the strongest exchange coupling (Jeon et al., 2013).
The crystals of I were obtained in the process of a preparation of VIV complex using aniline and [VIV(O)(η2-ox)(H2O)3] (ox2- = oxalate) in air. The reaction occurs neither under an argon atmosphere nor when less than four equivalents of aniline to [VIV(O)(η2-ox)(H2O)3] was used. These results suggest that the reaction proceeds through coordination of aniline to [VIV(O)(η2-ox)(H2O)3], which may act as a catalyst of oxidation pentamerization of aniline to form I.
The red crystals contain only I, and the structure is in triclinic P-1 space group. The atoms of diamino-benzoquinonediimine moiety of I are coplanar. The bond lengths of C(1)–N(1) and C(4)–N(3) correspond to C–N single bond, and that of C(2)–N(2) and C(5)–N(4) correspond to C–N double bond. The bond angles of C(1)—N(1)—C(7) and C(4)—N(3)—C(19) are 128.74 (18) and 127.80 (19)°, respectively, and that of C(2)═N(2)—C(13) and C(5)═N(4)—C(25) are 121.28 (18) and 123.00 (19)°, respectively, indicating that N(1 and 3) and N(2 and 4) are attributed to amine (sp3) and imine (sp2) nitrogen atoms, respectively. The bond length of C(2)–C(3) is similar with that of C(5)–C(6), corresponding to that of a single bond, and those of C(3)–C(4) and C(1)–C(6) are similar with each other, corresponding to that of a double bond. The bond lengths of C(1)–C(2) and C(4)–C(5) are slightly longer than the above mentioned single bonds. These results indicate that each of two N–C–C–C–N zigzag shaped moieties shows a bond alternation, but no conjugation between them.