5,12-Bis(4-tert-butylphen­yl)-6,11-diphenyl­naphthacene

The title compound, C₅₀H₄₄, is a derivative of rubrene in which tert-butyl side groups are added to two of the pendant aromatic rings. The complete mol­ecule is generated by a mirror plane, and the unsubstituted and substituted pendant aromatic rings are almost perpendicular to the main backbone of the mol­ecule, which is essentially planar.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.074
• wR factor = 0.207
• Data-to-parameter ratio = 12.2

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT220_ALERT_2_A Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       5.27 Ratio

Author Response: excesssive vibration/disorder in the tert-butyl group

Alert level B
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.65 Ratio
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C40

Alert level C
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size .......       0.80 mm
PLAT213_ALERT_2_C Atom C42     has ADP max/min Ratio .............       3.50 prola
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          5

   1 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The electronic properties of rubrene and rubrene derivatives are of great interest owing to fundamental questions on electron transport and associated applications (Sundar et al., 2004; Goldmann et al., 2004). The electric transport properties will be published elsewhere (Stassen et al., 2007).

The crystal structure of the title compound is orthorombic, with space group Pnma. The unit cell contains four molecules (Fig. 1). In (I), the in-plane arrangement of the molecules is very similar to that of rubrene (Jurchescu et al., 2006). Noteworthy is the somewhat shorter distance of 3.55 Å between the naphthacene backbones compared to 3.74 Å in rubrene. However, the addition of the tert-butyl groups increases the inter-layer spacing by 31%. Interestingly, it leaves the backbone almost perfectly planar (Fig. 2). Both the pendant aromatic rings are almost perpendicular to the main backbone of the molecule: atoms C20—C25 and C30—C35 make dihedral angles of 85.04 (13)° and 84.55 (11)°, respectively, with the backbone carbon atoms.

Related literature

For related literature, see: Dodge et al. (1990); Goldmann et al. (2004); Jurchescu et al. (2006); Kloc et al. (1997); Laudize et al. (1998); Stassen et al. (2007); Sundar et al. (2004).

S2. Experimental

The title compound was synthesized according to the mehthod of Dodge et al. (1990). Single crystals of (I) were grown by physical vapour transport (Kloc et al., 1997, Laudize et al., 1998) at 533 K using high purity argon as the transport gas.

S3. Refinement

The H atoms in the aromatic units were located in difference maps and were refined freely along with individual isotropic displacement parameters. The H atoms of the methyl groups were positioned geometrically and were refined as riding on the parent C atoms, U_iso(H) values were set at 1.2U_eq of the parent atom.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), showing displacement ellipsoids at the 50% probability level (arbitrary spheres for the H atoms). The unlabelled atoms are generated by the symmetry operation (x, 3/2 - y, z).
	Fig. 2. The crystal packing of the title compound, viewed (a) down the b axis and (b) viewed down the c axis.

5,12-Bis(4-tert-butyl-phenyl)-6,11-diphenylnaphthacene

Crystal data

C50H44	F(000) = 1376
Mr = 644.90	Dx = 1.184 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 3136 reflections
a = 14.158 (2) Å	θ = 3.0–25.0°
b = 35.390 (5) Å	µ = 0.07 mm^−1
c = 7.2215 (11) Å	T = 292 K
V = 3618.4 (9) Å^3	Plate, translucent orange
Z = 4	0.80 × 0.32 × 0.06 mm

Data collection

Siemens SMART CCD area-detector diffractometer	3446 independent reflections
Radiation source: fine-focus sealed tube	2208 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.060
φ and ω scans	θmax = 25.6°, θmin = 1.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996; Blessing, 1995)	h = −17→17
Tmin = 0.988, Tmax = 0.996	k = −42→42
28135 measured reflections	l = −8→8

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difmap and geom
R[F^2 > 2σ(F^2)] = 0.074	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.207	w = 1/[σ^2(Fo^2) + (0.0891P)^2 + 1.9474P] where P = (Fo^2 + 2Fc^2)/3
S = 1.15	(Δ/σ)max < 0.001
3446 reflections	Δρmax = 0.44 e Å^−3
282 parameters	Δρmin = −0.40 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0146 (15)

Special details

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.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.93705 (17)	0.70977 (7)	0.3527 (4)	0.0340 (6)
C2	0.89917 (17)	0.72967 (7)	0.2033 (3)	0.0350 (6)
C3	0.85410 (19)	0.71093 (9)	0.0504 (4)	0.0424 (7)
C5	0.98466 (18)	0.72940 (7)	0.4982 (3)	0.0317 (6)
C6	1.03201 (17)	0.70973 (7)	0.6438 (4)	0.0326 (6)
C8	1.11360 (19)	0.71085 (9)	0.9468 (4)	0.0396 (7)
C7	1.06983 (17)	0.72991 (7)	0.7940 (3)	0.0320 (6)
C4	0.8150 (2)	0.73005 (9)	−0.0912 (4)	0.0479 (8)
C9	1.1524 (2)	0.73011 (8)	1.0896 (4)	0.0440 (7)
H8	1.1141 (19)	0.6838 (8)	0.942 (4)	0.043 (8)*
H3	0.8547 (19)	0.6831 (8)	0.045 (4)	0.045 (8)*
H31	0.948 (2)	0.6491 (8)	0.807 (4)	0.051 (8)*
H34	1.219 (3)	0.6126 (10)	0.480 (5)	0.074 (11)*
H25	0.798 (2)	0.6770 (9)	0.527 (5)	0.068 (10)*
H32	1.000 (2)	0.5855 (9)	0.807 (5)	0.067 (10)*
H24	0.745 (3)	0.6144 (11)	0.534 (6)	0.092 (13)*
H35	1.171 (2)	0.6769 (8)	0.470 (4)	0.055 (9)*
H21	1.019 (3)	0.6479 (9)	0.194 (5)	0.070 (10)*
H23	0.828 (3)	0.5687 (11)	0.359 (5)	0.081 (11)*
H4	0.787 (2)	0.7156 (8)	−0.197 (4)	0.047 (8)*
H22	0.964 (3)	0.5854 (10)	0.196 (5)	0.082 (12)*
H9	1.179 (2)	0.7171 (8)	1.191 (4)	0.057 (9)*
C20	0.91358 (19)	0.66864 (7)	0.3598 (4)	0.0387 (7)
C30	1.05447 (18)	0.66849 (7)	0.6373 (4)	0.0361 (6)
C31	1.0058 (2)	0.64137 (8)	0.7376 (4)	0.0446 (7)
C21	0.9614 (2)	0.64110 (8)	0.2608 (4)	0.0503 (8)
C35	1.1346 (2)	0.65679 (8)	0.5419 (4)	0.0455 (7)
C25	0.8324 (2)	0.65765 (9)	0.4549 (5)	0.0508 (8)
C24	0.8020 (3)	0.62075 (10)	0.4534 (6)	0.0681 (10)
C34	1.1634 (2)	0.61949 (9)	0.5450 (5)	0.0569 (9)
C32	1.0352 (3)	0.60433 (9)	0.7392 (5)	0.0539 (8)
C33	1.1156 (2)	0.59238 (8)	0.6449 (5)	0.0553 (9)
C22	0.9308 (3)	0.60409 (10)	0.2607 (6)	0.0661 (10)
C23	0.8510 (3)	0.59405 (11)	0.3566 (6)	0.0745 (11)
C40	1.1464 (3)	0.55077 (10)	0.6420 (6)	0.0786 (12)
C42	1.1059 (6)	0.52857 (12)	0.8005 (9)	0.167 (3)
H42A	1.0383	0.5278	0.7896	0.200*
H42B	1.1229	0.5404	0.9153	0.200*
H42C	1.1305	0.5033	0.7979	0.200*
C41	1.2544 (4)	0.54734 (13)	0.6482 (8)	0.121 (2)
H41A	1.2777	0.5588	0.7596	0.146*
H41B	1.2811	0.5599	0.5427	0.146*
H41C	1.2719	0.5211	0.6463	0.146*
C43	1.1162 (4)	0.53380 (12)	0.4580 (8)	0.129 (2)
H43A	1.1357	0.5078	0.4524	0.155*
H43B	1.1450	0.5476	0.3585	0.155*
H43C	1.0487	0.5352	0.4467	0.155*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0293 (14)	0.0368 (14)	0.0360 (15)	0.0011 (10)	0.0026 (11)	−0.0043 (12)
C2	0.0258 (14)	0.0460 (14)	0.0331 (15)	−0.0011 (11)	0.0012 (11)	−0.0022 (11)
C3	0.0375 (16)	0.0488 (18)	0.0410 (17)	0.0013 (13)	−0.0007 (13)	−0.0089 (14)
C5	0.0271 (12)	0.0350 (13)	0.0331 (13)	0.0012 (11)	0.0014 (10)	0.0001 (12)
C6	0.0292 (13)	0.0346 (14)	0.0339 (14)	−0.0016 (10)	0.0021 (11)	0.0007 (11)
C8	0.0377 (16)	0.0435 (17)	0.0377 (16)	0.0012 (12)	−0.0028 (12)	0.0048 (13)
C7	0.0269 (13)	0.0370 (13)	0.0321 (14)	−0.0001 (10)	0.0018 (11)	0.0020 (11)
C4	0.0404 (17)	0.0676 (19)	0.0359 (16)	−0.0018 (14)	−0.0066 (13)	−0.0082 (14)
C9	0.0391 (16)	0.0563 (17)	0.0365 (16)	0.0014 (13)	−0.0064 (13)	0.0074 (13)
C20	0.0406 (15)	0.0393 (15)	0.0361 (15)	−0.0003 (12)	−0.0070 (12)	−0.0027 (12)
C30	0.0362 (15)	0.0365 (14)	0.0355 (15)	0.0005 (11)	−0.0061 (12)	0.0030 (12)
C31	0.0508 (19)	0.0387 (16)	0.0443 (17)	0.0015 (13)	0.0038 (14)	0.0042 (13)
C21	0.061 (2)	0.0449 (18)	0.0454 (18)	0.0049 (15)	0.0008 (16)	−0.0076 (15)
C35	0.0405 (17)	0.0431 (17)	0.0529 (18)	0.0015 (13)	0.0033 (14)	0.0020 (14)
C25	0.0416 (17)	0.0468 (18)	0.064 (2)	−0.0018 (14)	0.0005 (15)	0.0016 (16)
C24	0.062 (2)	0.054 (2)	0.088 (3)	−0.0155 (18)	−0.002 (2)	0.008 (2)
C34	0.0497 (19)	0.0500 (19)	0.071 (2)	0.0126 (15)	0.0013 (17)	−0.0047 (17)
C32	0.073 (2)	0.0387 (17)	0.0505 (19)	−0.0047 (16)	0.0000 (17)	0.0070 (15)
C33	0.071 (2)	0.0374 (16)	0.058 (2)	0.0110 (15)	−0.0107 (17)	−0.0009 (15)
C22	0.095 (3)	0.0441 (19)	0.060 (2)	0.010 (2)	−0.012 (2)	−0.0107 (18)
C23	0.092 (3)	0.045 (2)	0.087 (3)	−0.020 (2)	−0.018 (2)	0.002 (2)
C40	0.110 (3)	0.0417 (19)	0.084 (3)	0.023 (2)	−0.014 (2)	−0.0067 (19)
C42	0.281 (9)	0.049 (3)	0.171 (6)	0.058 (4)	0.069 (6)	0.049 (3)
C41	0.135 (5)	0.080 (3)	0.150 (5)	0.061 (3)	−0.029 (4)	−0.014 (3)
C43	0.169 (5)	0.060 (3)	0.158 (5)	0.033 (3)	−0.051 (4)	−0.044 (3)

Geometric parameters (Å, º)

C1—C2	1.396 (4)	C35—C34	1.382 (4)
C1—C5	1.429 (4)	C35—H35	1.02 (3)
C1—C20	1.494 (4)	C25—C24	1.375 (4)
C2—C3	1.437 (4)	C25—H25	0.99 (3)
C2—C2^i	1.439 (5)	C24—C23	1.365 (6)
C3—C4	1.345 (4)	C24—H24	1.02 (4)
C3—H3	0.99 (3)	C34—C33	1.378 (5)
C5—C6	1.428 (4)	C34—H34	0.95 (4)
C5—C5^i	1.458 (5)	C32—C33	1.392 (5)
C6—C7	1.405 (4)	C32—H32	0.97 (3)
C6—C30	1.495 (3)	C33—C40	1.536 (4)
C8—C9	1.353 (4)	C22—C23	1.371 (6)
C8—C7	1.434 (4)	C22—H22	0.94 (4)
C8—H8	0.96 (3)	C23—H23	0.96 (4)
C7—C7^i	1.422 (5)	C40—C42	1.502 (6)
C4—C4^i	1.412 (6)	C40—C43	1.520 (6)
C4—H4	1.00 (3)	C40—C41	1.534 (6)
C9—C9^i	1.408 (6)	C42—H42A	0.9600
C9—H9	0.95 (3)	C42—H42B	0.9600
C20—C21	1.385 (4)	C42—H42C	0.9600
C20—C25	1.395 (4)	C41—H41A	0.9600
C30—C31	1.386 (4)	C41—H41B	0.9600
C30—C35	1.390 (4)	C41—H41C	0.9600
C31—C32	1.376 (4)	C43—H43A	0.9600
C31—H31	1.00 (3)	C43—H43B	0.9600
C21—C22	1.380 (5)	C43—H43C	0.9600
C21—H21	0.98 (4)
C2—C1—C5	120.3 (2)	C20—C25—H25	117.9 (19)
C2—C1—C20	115.6 (2)	C23—C24—C25	120.2 (4)
C5—C1—C20	123.6 (2)	C23—C24—H24	123 (2)
C1—C2—C3	122.1 (2)	C25—C24—H24	117 (2)
C1—C2—C2^i	120.30 (15)	C33—C34—C35	121.9 (3)
C3—C2—C2^i	117.48 (16)	C33—C34—H34	119 (2)
C4—C3—C2	122.3 (3)	C35—C34—H34	119 (2)
C4—C3—H3	118.4 (17)	C31—C32—C33	122.2 (3)
C2—C3—H3	119.3 (17)	C31—C32—H32	120 (2)
C6—C5—C1	121.7 (2)	C33—C32—H32	117.5 (19)
C6—C5—C5^i	119.17 (14)	C34—C33—C32	116.5 (3)
C1—C5—C5^i	119.09 (14)	C34—C33—C40	121.4 (3)
C7—C6—C5	120.0 (2)	C32—C33—C40	122.0 (3)
C7—C6—C30	116.1 (2)	C23—C22—C21	120.3 (4)
C5—C6—C30	123.6 (2)	C23—C22—H22	119 (2)
C9—C8—C7	121.7 (3)	C21—C22—H22	121 (2)
C9—C8—H8	121.8 (17)	C24—C23—C22	119.9 (3)
C7—C8—H8	116.6 (17)	C24—C23—H23	118 (2)
C6—C7—C7^i	120.55 (14)	C22—C23—H23	122 (2)
C6—C7—C8	121.3 (2)	C42—C40—C43	110.6 (4)
C7^i—C7—C8	118.05 (16)	C42—C40—C41	108.5 (5)
C3—C4—C4^i	120.20 (18)	C43—C40—C41	106.0 (4)
C3—C4—H4	119.0 (16)	C42—C40—C33	112.5 (4)
C4^i—C4—H4	120.8 (16)	C43—C40—C33	108.1 (3)
C8—C9—C9^i	120.26 (18)	C41—C40—C33	111.0 (4)
C8—C9—H9	120.8 (19)	C40—C42—H42A	109.5
C9^i—C9—H9	119.0 (18)	C40—C42—H42B	109.5
C21—C20—C25	117.4 (3)	H42A—C42—H42B	109.5
C21—C20—C1	124.0 (3)	C40—C42—H42C	109.5
C25—C20—C1	118.2 (2)	H42A—C42—H42C	109.5
C31—C30—C35	117.3 (3)	H42B—C42—H42C	109.5
C31—C30—C6	123.7 (2)	C40—C41—H41A	109.5
C35—C30—C6	118.7 (2)	C40—C41—H41B	109.5
C32—C31—C30	120.9 (3)	H41A—C41—H41B	109.5
C32—C31—H31	120.2 (16)	C40—C41—H41C	109.5
C30—C31—H31	118.9 (16)	H41A—C41—H41C	109.5
C22—C21—C20	121.0 (3)	H41B—C41—H41C	109.5
C22—C21—H21	120 (2)	C40—C43—H43A	109.5
C20—C21—H21	119 (2)	C40—C43—H43B	109.5
C34—C35—C30	121.2 (3)	H43A—C43—H43B	109.5
C34—C35—H35	121.8 (17)	C40—C43—H43C	109.5
C30—C35—H35	117.1 (16)	H43A—C43—H43C	109.5
C24—C25—C20	121.2 (3)	H43B—C43—H43C	109.5
C24—C25—H25	121 (2)

Symmetry code: (i) x, −y+3/2, z.