Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002532/dn6019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002532/dn6019Isup2.hkl |
CCDC reference: 182644
Key indicators
- Single-crystal X-ray study
- T = 300 K
- Mean (C-C) = 0.002 Å
- R factor = 0.049
- wR factor = 0.113
- Data-to-parameter ratio = 14.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N1A - HN1A ? PLAT_420 Alert C D-H Without Acceptor N2A - HN2A ? PLAT_420 Alert C D-H Without Acceptor N1B - HN1B ? PLAT_420 Alert C D-H Without Acceptor N2B - HN2B ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check
The title compound was prepared according to a new synthesis route of oligoanilines developed by Wang & MacDiarmid (2002). The phenyl-end tetramer of aniline in the reduced oxidation state is prepared from a reaction of dianiline(N-phenyl-1,4-phenylenediamine) with hydroquinone, using titanium(IV) n-butoxide as condensing reagent. A light-violet powder was obtained and recrystallized through sublimation under static secondary vacuum. Colorless crystals are grown at ca 483 K.
H atoms bonded to C atoms were placed at calculated positions. H atoms bonded to N atoms were located from difference Fourier syntheses and their positions refined. Riding isotropic displacement parameter was used for all H atoms.
Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: JANA2000 (Petricek & Dusek, 2000); molecular graphics: DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: JANA2000.
Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. |
C30H26N4 | Z = 2 |
Mr = 442.6 | F(000) = 468 |
Triclinic, P1 | Dx = 1.287 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 5.7328 (1) Å | Cell parameters from 23907 reflections |
b = 8.8866 (2) Å | θ = 4.1–26.4° |
c = 22.6889 (6) Å | µ = 0.08 mm−1 |
α = 82.7481 (8)° | T = 300 K |
β = 84.5281 (8)° | Plate, colourless |
γ = 88.4739 (11)° | 0.25 × 0.10 × 0.02 mm |
V = 1141.29 (4) Å3 |
KAPPACCD diffractometer | 3022 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.047 |
Graphite monochromator | θmax = 26.3°, θmin = 4.2° |
ϕ and ω scans | h = −7→7 |
23907 measured reflections | k = −11→10 |
4616 independent reflections | l = −28→28 |
Refinement on F2 | Weighting scheme based on measured s.u.'s w = 1/[σ2(I) + 0.001024I2] |
R[F2 > 2σ(F2)] = 0.049 | (Δ/σ)max = 0.0004 |
wR(F2) = 0.113 | Δρmax = 0.24 e Å−3 |
S = 1.54 | Δρmin = −0.21 e Å−3 |
4616 reflections | Extinction correction: B-C type 1 Gaussian isotropic |
320 parameters | Extinction coefficient: 1.21 (18) |
H atoms treated by a mixture of independent and constrained refinement |
C30H26N4 | γ = 88.4739 (11)° |
Mr = 442.6 | V = 1141.29 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.7328 (1) Å | Mo Kα radiation |
b = 8.8866 (2) Å | µ = 0.08 mm−1 |
c = 22.6889 (6) Å | T = 300 K |
α = 82.7481 (8)° | 0.25 × 0.10 × 0.02 mm |
β = 84.5281 (8)° |
KAPPACCD diffractometer | 3022 reflections with I > 2σ(I) |
23907 measured reflections | Rint = 0.047 |
4616 independent reflections |
R[F2 > 2σ(F2)] = 0.049 | 320 parameters |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.54 | Δρmax = 0.24 e Å−3 |
4616 reflections | Δρmin = −0.21 e Å−3 |
x | y | z | Uiso*/Ueq | ||
C1a | 0.8575 (2) | −0.05123 (13) | 0.45970 (5) | 0.0425 (4) | |
C2a | 1.0660 (2) | 0.02432 (14) | 0.43946 (5) | 0.0473 (4) | |
C3a | 1.2046 (2) | 0.07449 (13) | 0.47942 (6) | 0.0444 (4) | |
C4a | 0.6585 (2) | −0.03469 (14) | 0.36540 (6) | 0.0443 (4) | |
C5a | 0.5622 (2) | −0.11795 (13) | 0.32598 (6) | 0.0476 (4) | |
C6a | 0.4962 (2) | −0.05035 (14) | 0.27199 (6) | 0.0487 (5) | |
C7a | 0.5239 (2) | 0.10463 (14) | 0.25507 (6) | 0.0472 (5) | |
C8a | 0.6186 (2) | 0.18794 (14) | 0.29448 (6) | 0.0501 (5) | |
C9a | 0.6856 (2) | 0.12031 (14) | 0.34852 (6) | 0.0485 (5) | |
C10a | 0.3280 (2) | 0.11916 (15) | 0.16068 (6) | 0.0514 (5) | |
C11a | 0.1199 (2) | 0.04433 (15) | 0.18143 (6) | 0.0549 (5) | |
C12a | −0.0155 (2) | −0.01047 (17) | 0.14219 (7) | 0.0659 (6) | |
C13a | 0.0505 (3) | 0.0085 (2) | 0.08241 (8) | 0.0947 (8) | |
C14a | 0.2535 (3) | 0.0866 (2) | 0.06142 (8) | 0.1070 (9) | |
C15a | 0.3911 (2) | 0.1403 (2) | 0.10008 (7) | 0.0780 (7) | |
C1b | 0.6536 (2) | 0.43865 (13) | 0.54202 (6) | 0.0434 (4) | |
C2b | 0.4494 (2) | 0.51663 (15) | 0.55949 (6) | 0.0495 (4) | |
C3b | 0.3008 (2) | 0.57691 (14) | 0.51807 (6) | 0.0471 (4) | |
C4b | 0.8519 (2) | 0.41984 (14) | 0.63659 (6) | 0.0452 (4) | |
C5b | 0.9378 (2) | 0.31650 (13) | 0.68059 (6) | 0.0474 (5) | |
C6b | 0.9953 (2) | 0.35959 (14) | 0.73336 (6) | 0.0513 (5) | |
C7b | 0.9680 (2) | 0.50965 (15) | 0.74472 (6) | 0.0485 (5) | |
C8b | 0.8822 (2) | 0.61356 (13) | 0.70062 (6) | 0.0499 (5) | |
C9b | 0.8243 (2) | 0.57029 (14) | 0.64771 (6) | 0.0501 (5) | |
C10b | 1.1668 (2) | 0.49323 (16) | 0.83912 (6) | 0.0542 (5) | |
C11b | 1.3669 (2) | 0.41183 (16) | 0.82209 (6) | 0.0594 (5) | |
C12b | 1.5147 (2) | 0.35163 (18) | 0.86367 (8) | 0.0735 (7) | |
C13b | 1.4705 (3) | 0.3737 (2) | 0.92225 (9) | 0.0982 (9) | |
C14b | 1.2760 (4) | 0.4578 (3) | 0.93902 (8) | 0.1103 (10) | |
C15b | 1.1244 (2) | 0.5173 (2) | 0.89815 (8) | 0.0817 (7) | |
N1a | 0.7205 (2) | −0.11023 (12) | 0.42012 (5) | 0.0527 (4) | |
N2a | 0.4637 (2) | 0.17924 (13) | 0.19979 (5) | 0.0601 (5) | |
N1b | 0.8041 (2) | 0.36994 (13) | 0.58306 (5) | 0.0532 (4) | |
N2b | 1.0150 (2) | 0.55940 (14) | 0.79859 (5) | 0.0617 (5) | |
Hc2a | 1.1161 | 0.0424 | 0.3966 | 0.0473* | |
Hc3a | 1.3499 | 0.1267 | 0.4641 | 0.0444* | |
Hc5a | 0.5405 | −0.2275 | 0.3363 | 0.0476* | |
Hc6a | 0.4290 | −0.1131 | 0.2454 | 0.0487* | |
Hc8a | 0.6397 | 0.2966 | 0.2835 | 0.0501* | |
Hc9a | 0.7524 | 0.1823 | 0.3752 | 0.0485* | |
Hc11a | 0.0675 | 0.0301 | 0.2240 | 0.0549* | |
Hc12a | −0.1603 | −0.0647 | 0.1568 | 0.0659* | |
Hc13a | −0.0463 | −0.0339 | 0.0551 | 0.0947* | |
Hc14a | 0.3016 | 0.1036 | 0.0184 | 0.1070* | |
Hc15a | 0.5342 | 0.1948 | 0.0843 | 0.0780* | |
Hc2b | 0.4097 | 0.5285 | 0.6015 | 0.0495* | |
Hc3b | 0.1593 | 0.6317 | 0.5316 | 0.0471* | |
Hc5b | 0.9586 | 0.2099 | 0.6744 | 0.0474* | |
Hc6b | 1.0570 | 0.2823 | 0.7629 | 0.0513* | |
Hc8b | 0.8630 | 0.7204 | 0.7068 | 0.0499* | |
Hc9b | 0.7626 | 0.6470 | 0.6179 | 0.0501* | |
Hc11b | 1.4043 | 0.3960 | 0.7801 | 0.0594* | |
Hc12b | 1.6538 | 0.2915 | 0.8513 | 0.0735* | |
Hc13b | 1.5768 | 0.3289 | 0.9514 | 0.0982* | |
Hc14b | 1.2453 | 0.4770 | 0.9806 | 0.1103* | |
Hc15b | 0.9867 | 0.5766 | 0.9111 | 0.0817* | |
Hn1a | 0.636 (2) | −0.1750 (14) | 0.4353 (5) | 0.0527* | |
Hn2a | 0.554 (2) | 0.2391 (15) | 0.1847 (6) | 0.0601* | |
Hn1b | 0.892 (2) | 0.2982 (14) | 0.5719 (5) | 0.0532* | |
Hn2b | 0.921 (2) | 0.6220 (15) | 0.8108 (6) | 0.0617* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1a | 0.0390 (7) | 0.0403 (7) | 0.0496 (9) | 0.0010 (5) | −0.0068 (6) | −0.0092 (6) |
C2a | 0.0419 (7) | 0.0539 (8) | 0.0453 (8) | 0.0006 (6) | −0.0011 (6) | −0.0059 (6) |
C3a | 0.0365 (6) | 0.0477 (7) | 0.0484 (9) | −0.0034 (5) | −0.0018 (6) | −0.0043 (6) |
C4a | 0.0342 (6) | 0.0494 (7) | 0.0507 (9) | −0.0015 (5) | −0.0048 (6) | −0.0106 (6) |
C5a | 0.0430 (7) | 0.0441 (7) | 0.0577 (9) | −0.0036 (6) | −0.0086 (6) | −0.0099 (6) |
C6a | 0.0438 (7) | 0.0511 (8) | 0.0547 (9) | −0.0041 (6) | −0.0095 (6) | −0.0157 (6) |
C7a | 0.0393 (7) | 0.0525 (8) | 0.0506 (9) | −0.0020 (6) | −0.0057 (6) | −0.0081 (6) |
C8a | 0.0441 (7) | 0.0440 (7) | 0.0635 (10) | −0.0039 (6) | −0.0082 (7) | −0.0080 (6) |
C9a | 0.0412 (7) | 0.0488 (8) | 0.0592 (9) | −0.0027 (6) | −0.0101 (6) | −0.0168 (6) |
C10a | 0.0475 (8) | 0.0552 (8) | 0.0513 (9) | 0.0047 (6) | −0.0101 (7) | −0.0026 (6) |
C11a | 0.0530 (8) | 0.0613 (9) | 0.0500 (9) | 0.0026 (7) | −0.0066 (7) | −0.0042 (7) |
C12a | 0.0547 (9) | 0.0795 (11) | 0.0643 (12) | −0.0028 (7) | −0.0185 (8) | −0.0021 (8) |
C13a | 0.0793 (12) | 0.1451 (18) | 0.0644 (13) | −0.0195 (12) | −0.0267 (10) | −0.0124 (11) |
C14a | 0.0884 (13) | 0.187 (2) | 0.0450 (11) | −0.0179 (14) | −0.0122 (10) | −0.0041 (12) |
C15a | 0.0612 (9) | 0.1177 (14) | 0.0519 (11) | −0.0111 (9) | −0.0061 (8) | 0.0042 (9) |
C1b | 0.0393 (7) | 0.0422 (7) | 0.0490 (9) | −0.0020 (5) | −0.0049 (6) | −0.0053 (6) |
C2b | 0.0460 (7) | 0.0579 (8) | 0.0446 (8) | 0.0003 (6) | −0.0007 (6) | −0.0092 (6) |
C3b | 0.0396 (7) | 0.0496 (7) | 0.0522 (9) | 0.0025 (6) | −0.0004 (6) | −0.0104 (6) |
C4b | 0.0373 (7) | 0.0486 (8) | 0.0494 (9) | 0.0004 (5) | −0.0047 (6) | −0.0044 (6) |
C5b | 0.0443 (7) | 0.0425 (7) | 0.0559 (9) | 0.0027 (5) | −0.0089 (6) | −0.0050 (6) |
C6b | 0.0513 (8) | 0.0459 (8) | 0.0557 (9) | 0.0033 (6) | −0.0114 (6) | 0.0013 (6) |
C7b | 0.0427 (7) | 0.0519 (8) | 0.0513 (9) | −0.0015 (6) | −0.0032 (6) | −0.0085 (6) |
C8b | 0.0461 (7) | 0.0415 (7) | 0.0624 (10) | 0.0033 (6) | −0.0080 (7) | −0.0054 (6) |
C9b | 0.0473 (7) | 0.0445 (8) | 0.0576 (9) | 0.0023 (6) | −0.0105 (7) | 0.0005 (6) |
C10b | 0.0552 (9) | 0.0582 (9) | 0.0495 (10) | −0.0136 (7) | −0.0052 (7) | −0.0056 (7) |
C11b | 0.0568 (9) | 0.0666 (9) | 0.0558 (10) | −0.0044 (7) | −0.0067 (7) | −0.0095 (7) |
C12b | 0.0594 (9) | 0.0862 (12) | 0.0759 (13) | −0.0050 (8) | −0.0169 (9) | −0.0049 (9) |
C13b | 0.0765 (13) | 0.1479 (19) | 0.0702 (15) | −0.0062 (12) | −0.0270 (11) | 0.0029 (12) |
C14b | 0.0934 (15) | 0.190 (2) | 0.0514 (12) | −0.0022 (15) | −0.0118 (11) | −0.0245 (13) |
C15b | 0.0652 (10) | 0.1272 (15) | 0.0554 (11) | −0.0031 (10) | −0.0036 (9) | −0.0234 (10) |
N1a | 0.0547 (7) | 0.0521 (7) | 0.0528 (8) | −0.0143 (5) | −0.0093 (6) | −0.0060 (5) |
N2a | 0.0641 (8) | 0.0584 (8) | 0.0571 (9) | −0.0165 (6) | −0.0082 (6) | 0.0002 (6) |
N1b | 0.0541 (7) | 0.0531 (7) | 0.0534 (8) | 0.0151 (5) | −0.0104 (6) | −0.0102 (5) |
N2b | 0.0682 (8) | 0.0622 (8) | 0.0565 (9) | 0.0128 (6) | −0.0091 (7) | −0.0157 (6) |
C1a—C2a | 1.3968 (17) | C1b—N1b | 1.4018 (18) |
C1a—C3ai | 1.3841 (19) | C2b—C3b | 1.3774 (19) |
C1a—N1a | 1.4050 (19) | C2b—Hc2b | 0.9787 |
C2a—C3a | 1.382 (2) | C3b—Hc3b | 0.9794 |
C2a—Hc2a | 0.9800 | C4b—C5b | 1.3861 (18) |
C3a—Hc3a | 0.9771 | C4b—C9b | 1.3937 (18) |
C4a—C5a | 1.391 (2) | C4b—N1b | 1.3974 (19) |
C4a—C9a | 1.3910 (18) | C5b—C6b | 1.373 (2) |
C4a—N1a | 1.4068 (17) | C5b—Hc5b | 0.9772 |
C5a—C6a | 1.3767 (19) | C6b—C7b | 1.3918 (19) |
C5a—Hc5a | 0.9808 | C6b—Hc6b | 0.9808 |
C6a—C7a | 1.3914 (18) | C7b—C8b | 1.3902 (19) |
C6a—Hc6a | 0.9808 | C7b—N2b | 1.403 (2) |
C7a—C8a | 1.387 (2) | C8b—C9b | 1.378 (2) |
C7a—N2a | 1.4113 (18) | C8b—Hc8b | 0.9795 |
C8a—C9a | 1.380 (2) | C9b—Hc9b | 0.9807 |
C8a—Hc8a | 0.9744 | C10b—C11b | 1.389 (2) |
C9a—Hc9a | 0.9788 | C10b—C15b | 1.380 (2) |
C10a—C11a | 1.3940 (19) | C10b—N2b | 1.392 (2) |
C10a—C15a | 1.378 (2) | C11b—C12b | 1.377 (2) |
C10a—N2a | 1.397 (2) | C11b—Hc11b | 0.9811 |
C11a—C12a | 1.376 (2) | C12b—C13b | 1.367 (2) |
C11a—Hc11a | 0.9790 | C12b—Hc12b | 0.9856 |
C12a—C13a | 1.363 (2) | C13b—C14b | 1.376 (3) |
C12a—Hc12a | 0.9808 | C13b—Hc13b | 0.984 |
C13a—C14a | 1.384 (2) | C14b—C15b | 1.379 (2) |
C13a—Hc13a | 0.984 | C14b—Hc14b | 0.980 |
C14a—C15a | 1.370 (2) | C15b—Hc15b | 0.9798 |
C14a—Hc14a | 0.9810 | N1a—Hn1a | 0.786 (12) |
C15a—Hc15a | 0.9785 | N2a—Hn2a | 0.776 (13) |
C1b—C2b | 1.3952 (18) | N1b—Hn1b | 0.852 (13) |
C1b—C3bii | 1.387 (2) | N2b—Hn2b | 0.818 (14) |
C2a—C1a—C3ai | 118.06 (12) | C2b—C1b—C3bii | 117.63 (11) |
C2a—C1a—N1a | 121.43 (11) | C2b—C1b—N1b | 122.45 (12) |
C3ai—C1a—N1a | 120.40 (10) | C3bii—C1b—N1b | 119.83 (11) |
C3a—C2a—Hc2a | 119.06 | C3b—C2b—Hc2b | 119.24 |
C5a—C4a—C9a | 117.67 (12) | C5b—C4b—C9b | 117.64 (12) |
C5a—C4a—N1a | 118.80 (11) | C5b—C4b—N1b | 118.95 (11) |
C9a—C4a—N1a | 123.53 (12) | C9b—C4b—N1b | 123.37 (11) |
C6a—C5a—Hc5a | 118.51 | C6b—C5b—Hc5b | 118.40 |
C7a—C6a—Hc6a | 120.29 | C7b—C6b—Hc6b | 120.49 |
C8a—C7a—N2a | 119.09 (11) | C8b—C7b—N2b | 118.92 (12) |
C9a—C8a—Hc8a | 119.21 | C9b—C8b—Hc8b | 118.74 |
C11a—C10a—C15a | 118.50 (14) | C11b—C10b—C15b | 118.57 (14) |
C11a—C10a—N2a | 121.08 (12) | C11b—C10b—N2b | 122.76 (13) |
C15a—C10a—N2a | 120.32 (12) | C15b—C10b—N2b | 118.54 (13) |
C12a—C11a—Hc11a | 118.98 | C12b—C11b—Hc11b | 119.05 |
C13a—C12a—Hc12a | 118.94 | C13b—C12b—Hc12b | 119.34 |
C14a—C13a—Hc13a | 121.47 | C14b—C13b—Hc13b | 121.4 |
C15a—C14a—Hc14a | 118.9 | C15b—C14b—Hc14b | 119.2 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C30H26N4 |
Mr | 442.6 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 300 |
a, b, c (Å) | 5.7328 (1), 8.8866 (2), 22.6889 (6) |
α, β, γ (°) | 82.7481 (8), 84.5281 (8), 88.4739 (11) |
V (Å3) | 1141.29 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.25 × 0.10 × 0.02 |
Data collection | |
Diffractometer | KAPPACCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23907, 4616, 3022 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.113, 1.54 |
No. of reflections | 4616 |
No. of parameters | 320 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.21 |
Computer programs: COLLECT (Hooft, 1998), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXTL (Sheldrick, 1995), JANA2000 (Petricek & Dusek, 2000), DIAMOND (Brandenburg & Berndt, 1999), JANA2000.
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Recently, many oligoanilines have received particular attention due to their interesting physical properties. Indeed, their various ways of processing (crystal growth, ordered thin films, powders or solutions) make them good candidates for electronic devices. Several papers have already reported some of their potential applications, such as gas sensors (Feng & MacDiarmid, 1999) or FET transistor devices (Kuo & Weng, 2000). In the course of our work on those oligoanilines, we could obtain the phenyl-end-capped tetramer aniline, (I), and show that it resembles its phenyl-end-capped dimer counterpart (Boyer et al., 2000).
The crystal structure consists of two half molecules in the asymmetric unit (Fig. 1). Since, within each molecule, the (C—N—C) inter-ring links lie in the same plane, both molecules can easily be described in terms of torsion angles between rings. The departure of the rings from that plane are 44.0 [C1a through C3a], 13.1 [C4a through C9a] and 44.4° [C10a through C15a] in molecule A, and 32.1 [C1b through C3b], 22.7 [C4b through C9b] and 29.0° [C10b through C15b] in molecule B.