N,N′-Bis(2,2,3,3,4,4,4-hepta­fluoro­butyl)naphthalene-1,4:5,8-tetra­carboximide

The title mol­ecule, C₂₂H₈F₁₄N₂O₄, lies across a crystallographic inversion center with the naphthalene diimide core essentially planar (mean deviation from plane is 0.0583 Å). The CF₂ groups in the perfluorobutyl chains are in an energetically favorable all trans conformation. In the crystal structure, mol­ecules are packed in slightly displaced layers so that the side chains overlap the aromatic naphthalene diimide rings, thus minimizing any possible π–π overlap.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.067
• wR factor = 0.223
• Data-to-parameter ratio = 11.0

checkCIF/PLATON results

No syntax errors found



Alert level C
            Value of measurement temperature given =   293.000
            Value of melting point given =     0.000
PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low ....       0.90
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low ....         43 Perc.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96

Author Response: ... The crystals were weakly diffracting, but we were unable to get better quality crystals. Diffraction data were collected on various crystals, best data set results are reported here.

PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C10
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8
PLAT234_ALERT_4_C Large Hirshfeld Difference F4     --  C10     ..       0.10  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference F7     --  C11     ..       0.13  Ang.
PLAT234_ALERT_4_C Large Hirshfeld Difference N1     --  C7      ..       0.13  Ang.

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

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

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S1. Comment

Amongst n-type semiconductors used in organic thin film transistors, perylene diimides (PDIs) and naphthalene diimides (NDIs) have attracted considerable attention. The π -orbital wavefunctions in these systems form nodes at the two nitrogen positions in the imide rings. Indeed, it has been shown that semiconducting properties and device performance of these materials is very sensitive to the nature of substituents on the diimide nitrogen atoms. The title compound N,N'-Bis(1H,1H-perfluorobutyl) naphthalene- 1,4,5,8-tetracarboxylic acid diimide(I) has been shown to exhibit good n-type semiconducting behavior and OTFTs made incorporating I can be operated in air. The latter property has been ascribed to the denser packing of fluorinated alkyl chains in thin film.

Naphthalene diimide (NDI) and perylene diimide (PDI) based systems have been studied extensively (Chesterfield, et al., 2004a; Chesterfield et al., 2004b; Facceti et al., 2008; Jones, et al., 2004; Katz, et al., 2000a; Katz, et al., 2000b). We report here the structure of the title diimide molecule (I) (Fig. 1 and Fig 2). In the crystal structure, molecules are packed in slightly displaced layers so that the side chains overlap the aromatic naphthalene diimide rings, thus resulting in minimizing any possible π-π overlap (Fig .3).

Related literature

For general background on the semic-conducting properties and use of this class of materials in organic thin-film transistor applications, see: Chesterfield et al. (2004a,b); Facceti et al. (2008); Jones et al. (2004); Katz et al. (2000a,b); Kazmaier & Hoffmann (1994); Klebe et al. (1989); Shukla et al. (2008); Wurthner (2004).

S2. Experimental

The method described in Katz et al., 2000a, was followed for preparation of the title compound (I). Crystals of title (I) appeared during powder X-ray diffraction data collection of the dry lot sample. The crystals were weakly diffracting, but we were unable to get better quality crystals. Diffraction data were collected on various crystals, and the results of structure determination using best data set results are reported here.

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.93 Å, U_iso=1.2U_eq (C) for aromatic 0.97 Å, U_iso = 1.2U_eq (C) for CH₂ atoms.

Computing details

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Materials Studio (Accelrys, 2002); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures

	Fig. 1. Molecular structure of the title compound, with the atom numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are omitted for clarity.
	Fig. 2. A diagram illustrating planar naphthalene diimide core and trans configuration of perfluorobutyl chains on diiimide N atoms.
	Fig. 3. Unit cell packing showing layered structure.

N,N'-Bis(2,2,3,3,4,4,4-heptafluorobutyl)naphthalene-1,4:5,8- tetracarboximide

Crystal data

C22H8F14N2O4	Z = 1
Mr = 630.30	F(000) = 312
Triclinic, P1	Dx = 1.904 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.1910 (5) Å	Cell parameters from 4558 reflections
b = 10.1459 (12) Å	θ = 1.0–26.7°
c = 11.5988 (15) Å	µ = 0.21 mm^−1
α = 66.693 (4)°	T = 293 K
β = 79.064 (4)°	Needle, pink
γ = 89.115 (7)°	0.15 × 0.10 × 0.05 mm
V = 549.64 (11) Å^3

Data collection

Nonius KappaCCD diffractometer	909 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.057
Graphite monochromator	θmax = 26.6°, θmin = 4.1°
Detector resolution: 9 pixels mm^-1	h = −6→6
ϕ and ω scans	k = −12→11
3049 measured reflections	l = −14→12
2094 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.223	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.1P)^2 + 0.3623P] where P = (Fo^2 + 2Fc^2)/3
2094 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.23 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

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
F1	0.1050 (6)	0.4145 (3)	0.7561 (3)	0.0814 (11)
F2	0.1713 (6)	0.5174 (3)	0.8788 (3)	0.0828 (12)
F3	0.5849 (6)	0.3623 (4)	0.9393 (3)	0.0873 (12)
F4	0.5572 (7)	0.2684 (3)	0.8049 (3)	0.0883 (12)
F5	0.3622 (7)	0.0974 (4)	1.0537 (3)	0.0931 (12)
F6	0.0806 (7)	0.2472 (4)	1.0654 (4)	0.1050 (15)
F7	0.0800 (9)	0.1477 (4)	0.9346 (4)	0.1234 (17)
O1	0.2493 (8)	0.6081 (4)	0.4924 (4)	0.0742 (12)
O2	0.5194 (8)	0.8024 (4)	0.7439 (4)	0.0725 (12)
N1	0.3566 (7)	0.6967 (4)	0.6298 (4)	0.0484 (11)
C1	0.2325 (10)	0.7037 (5)	0.5308 (5)	0.0528 (14)
C2	0.0799 (9)	0.8305 (5)	0.4790 (5)	0.0467 (12)
C3	−0.0607 (10)	0.8401 (5)	0.3865 (5)	0.0562 (14)
H3	−0.0557	0.7679	0.3559	0.067*
C4	−0.2109 (10)	0.9584 (5)	0.3386 (5)	0.0541 (14)
H4	−0.3058	0.9637	0.2767	0.065*
C5	0.0752 (9)	0.9387 (5)	0.5243 (4)	0.0440 (12)
C6	0.2199 (9)	0.9345 (5)	0.6184 (5)	0.0482 (13)
C7	0.3779 (10)	0.8079 (5)	0.6691 (5)	0.0523 (14)
C8	0.4892 (9)	0.5658 (5)	0.6912 (5)	0.0537 (14)
H8A	0.6355	0.5891	0.7224	0.064*
H8B	0.5580	0.5257	0.6292	0.064*
C9	0.2958 (10)	0.4562 (6)	0.8023 (5)	0.0544 (14)
C10	0.4188 (10)	0.3238 (5)	0.8827 (5)	0.0550 (14)
C11	0.2281 (13)	0.2022 (6)	0.9871 (6)	0.0676 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F1	0.061 (2)	0.082 (2)	0.086 (2)	−0.0057 (16)	−0.0279 (18)	−0.0114 (19)
F2	0.091 (2)	0.063 (2)	0.074 (2)	0.0213 (17)	0.0167 (18)	−0.0222 (18)
F3	0.074 (2)	0.098 (3)	0.083 (3)	−0.0005 (18)	−0.0340 (18)	−0.021 (2)
F4	0.108 (3)	0.077 (2)	0.070 (2)	0.0396 (19)	−0.0012 (19)	−0.0278 (19)
F5	0.107 (3)	0.071 (2)	0.078 (2)	0.025 (2)	−0.018 (2)	−0.0064 (19)
F6	0.101 (3)	0.087 (3)	0.082 (3)	0.023 (2)	0.026 (2)	−0.007 (2)
F7	0.147 (4)	0.081 (3)	0.125 (4)	−0.039 (3)	−0.057 (3)	−0.008 (3)
O1	0.095 (3)	0.070 (3)	0.073 (3)	0.031 (2)	−0.024 (2)	−0.042 (2)
O2	0.079 (3)	0.067 (3)	0.080 (3)	0.0131 (19)	−0.038 (2)	−0.029 (2)
N1	0.054 (2)	0.040 (2)	0.051 (3)	0.0061 (18)	−0.010 (2)	−0.018 (2)
C1	0.059 (3)	0.046 (3)	0.052 (3)	0.009 (3)	−0.006 (3)	−0.021 (3)
C2	0.049 (3)	0.048 (3)	0.044 (3)	0.003 (2)	−0.002 (2)	−0.023 (3)
C3	0.068 (3)	0.051 (3)	0.057 (3)	0.006 (3)	−0.015 (3)	−0.028 (3)
C4	0.064 (3)	0.058 (3)	0.047 (3)	0.005 (3)	−0.016 (2)	−0.026 (3)
C5	0.045 (3)	0.044 (3)	0.038 (3)	0.001 (2)	−0.002 (2)	−0.014 (2)
C6	0.046 (3)	0.051 (3)	0.041 (3)	0.003 (2)	−0.003 (2)	−0.014 (3)
C7	0.051 (3)	0.052 (3)	0.044 (3)	0.000 (2)	−0.004 (3)	−0.012 (3)
C8	0.050 (3)	0.055 (3)	0.051 (3)	0.009 (2)	−0.010 (2)	−0.017 (3)
C9	0.053 (3)	0.056 (3)	0.057 (4)	0.010 (3)	−0.010 (3)	−0.026 (3)
C10	0.060 (3)	0.058 (3)	0.054 (3)	0.014 (3)	−0.011 (3)	−0.031 (3)
C11	0.085 (4)	0.056 (4)	0.058 (4)	0.003 (3)	−0.024 (4)	−0.015 (3)

Geometric parameters (Å, º)

F1—C9	1.357 (6)	C2—C5	1.389 (6)
F2—C9	1.341 (6)	C3—C4	1.402 (7)
F3—C10	1.325 (6)	C3—H3	0.9300
F4—C10	1.338 (6)	C4—C6^i	1.360 (7)
F5—C11	1.321 (6)	C4—H4	0.9300
F6—C11	1.294 (7)	C5—C6	1.425 (6)
F7—C11	1.314 (6)	C5—C5^i	1.435 (9)
O1—C1	1.213 (6)	C6—C4^i	1.360 (7)
O2—C7	1.223 (6)	C6—C7	1.491 (7)
N1—C7	1.387 (6)	C8—C9	1.522 (7)
N1—C1	1.398 (6)	C8—H8A	0.9700
N1—C8	1.467 (6)	C8—H8B	0.9700
C1—C2	1.477 (7)	C9—C10	1.513 (7)
C2—C3	1.380 (7)	C10—C11	1.539 (8)
C7—N1—C1	124.8 (4)	N1—C8—C9	109.7 (4)
C7—N1—C8	117.3 (5)	N1—C8—H8A	109.7
C1—N1—C8	117.8 (4)	C9—C8—H8A	109.7
O1—C1—N1	120.4 (5)	N1—C8—H8B	109.7
O1—C1—C2	123.0 (5)	C9—C8—H8B	109.7
N1—C1—C2	116.6 (5)	H8A—C8—H8B	108.2
C3—C2—C5	120.2 (5)	F2—C9—F1	105.5 (4)
C3—C2—C1	119.6 (5)	F2—C9—C10	108.6 (4)
C5—C2—C1	120.2 (5)	F1—C9—C10	108.7 (4)
C2—C3—C4	120.1 (5)	F2—C9—C8	110.1 (4)
C2—C3—H3	119.9	F1—C9—C8	109.2 (4)
C4—C3—H3	119.9	C10—C9—C8	114.3 (4)
C6^i—C4—C3	120.9 (5)	F3—C10—F4	107.7 (4)
C6^i—C4—H4	119.6	F3—C10—C9	109.0 (4)
C3—C4—H4	119.6	F4—C10—C9	108.5 (4)
C2—C5—C6	122.3 (5)	F3—C10—C11	107.7 (5)
C2—C5—C5^i	120.6 (6)	F4—C10—C11	107.2 (5)
C6—C5—C5^i	117.2 (6)	C9—C10—C11	116.4 (5)
C4^i—C6—C5	121.0 (5)	F6—C11—F7	109.6 (6)
C4^i—C6—C7	121.4 (5)	F6—C11—F5	108.2 (5)
C5—C6—C7	117.7 (5)	F7—C11—F5	107.3 (5)
O2—C7—N1	121.5 (5)	F6—C11—C10	111.6 (5)
O2—C7—C6	120.7 (5)	F7—C11—C10	110.2 (5)
N1—C7—C6	117.8 (5)	F5—C11—C10	109.8 (5)
C7—N1—C1—O1	171.2 (4)	C4^i—C6—C7—N1	173.8 (4)
C8—N1—C1—O1	−4.5 (7)	C5—C6—C7—N1	−5.4 (6)
C7—N1—C1—C2	−9.8 (7)	C7—N1—C8—C9	95.1 (5)
C8—N1—C1—C2	174.5 (4)	C1—N1—C8—C9	−88.9 (5)
O1—C1—C2—C3	2.8 (8)	N1—C8—C9—F2	−50.4 (6)
N1—C1—C2—C3	−176.1 (4)	N1—C8—C9—F1	65.0 (6)
O1—C1—C2—C5	−178.0 (5)	N1—C8—C9—C10	−173.0 (5)
N1—C1—C2—C5	3.1 (7)	F2—C9—C10—F3	−59.0 (5)
C5—C2—C3—C4	−0.6 (7)	F1—C9—C10—F3	−173.3 (4)
C1—C2—C3—C4	178.6 (4)	C8—C9—C10—F3	64.4 (6)
C2—C3—C4—C6^i	0.4 (8)	F2—C9—C10—F4	−176.0 (4)
C3—C2—C5—C6	−179.1 (4)	F1—C9—C10—F4	69.7 (5)
C1—C2—C5—C6	1.7 (7)	C8—C9—C10—F4	−52.6 (6)
C3—C2—C5—C5^i	0.0 (8)	F2—C9—C10—C11	63.0 (6)
C1—C2—C5—C5^i	−179.2 (5)	F1—C9—C10—C11	−51.3 (7)
C2—C5—C6—C4^i	−179.8 (4)	C8—C9—C10—C11	−173.5 (5)
C5^i—C5—C6—C4^i	1.1 (8)	F3—C10—C11—F6	65.9 (6)
C2—C5—C6—C7	−0.6 (7)	F4—C10—C11—F6	−178.4 (5)
C5^i—C5—C6—C7	−179.7 (5)	C9—C10—C11—F6	−56.8 (7)
C1—N1—C7—O2	−169.7 (5)	F3—C10—C11—F7	−172.1 (5)
C8—N1—C7—O2	6.0 (7)	F4—C10—C11—F7	−56.4 (6)
C1—N1—C7—C6	11.0 (7)	C9—C10—C11—F7	65.2 (7)
C8—N1—C7—C6	−173.3 (4)	F3—C10—C11—F5	−54.1 (7)
C4^i—C6—C7—O2	−5.5 (7)	F4—C10—C11—F5	61.6 (6)
C5—C6—C7—O2	175.3 (4)	C9—C10—C11—F5	−176.8 (5)

Symmetry code: (i) −x, −y+2, −z+1.