A phenyl-end-capped tetramer of aniline

Evain, M.; Quillard, S.; Corraze, B.; Wang, W.; MacDiarmid, A.G.

doi:10.1107/S1600536802002532

A phenyl-end-capped tetramer of aniline

M. Evain, S. Quillard, B. Corraze, W. Wang and A. G. MacDiarmid

The title compound, N,N'-bis[4-(phenylamino)phenyl]-1,4-phenylenediamine, C₆H₅(NHC₆H₄)₃NHC₆H₅ or C₃₀H₂₆N₄, has been obtained as large single crystals through sublimation under a static secondary vacuum, allowing for its structure determination. As in the phenyl-end-capped dimer, the (CNC) inter-ring links lie within a plane. The molecules have crystallographic twofold rotation symmetry, two half molecules making up the asymmetric unit.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002532/dn6019sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002532/dn6019Isup2.hkl Contains datablock I

CCDC reference: 182644

checkCIF report

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

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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

Comment top

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.

Experimental top

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.

Computing details top

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.

Figures top

Fig. 1. The molecular structure of (I) showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity.

(I) top

Crystal data top

C₃₀H₂₆N₄	Z = 2
M_r = 442.6	F(000) = 468
Triclinic, P1	D_x = 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

Data collection top

KAPPACCD diffractometer	3022 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 26.3°, θ_min = 4.2°
ϕ and ω scans	h = −7→7
23907 measured reflections	k = −11→10
4616 independent reflections	l = −28→28

Refinement top

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	Δρ_max = 0.24 e Å⁻³
S = 1.54	Δρ_min = −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

Crystal data top

C₃₀H₂₆N₄	γ = 88.4739 (11)°
M_r = 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)°

Data collection top

KAPPACCD diffractometer	3022 reflections with I > 2σ(I)
23907 measured reflections	R_int = 0.047
4616 independent reflections

Refinement top

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	Δρ_max = 0.24 e Å⁻³
4616 reflections	Δρ_min = −0.21 e Å⁻³

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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
M_r	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
R_int	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
Δρ_max, Δρ_min (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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