Racemic 1,2,3,4,7,8,9,10-octa-fluoro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazo-cine: an octa-fluorinated analogue of Tröger's base.

The title compound, C(15)H(6)F(8)N(2), possesses a non-crystal-lographic twofold axis. The dihedral angle between the two benzene rings is 98.4 (2)°. The crystal structure involves intermolecular C-H⋯F hydrogen bonds.

Related literature

For recent reviews on the chemistry of Tröger’s base (Tröger, 1887 ▶; Spielman, 1935 ▶), see: Valík et al. (2005 ▶) and Dolensky et al. (2007 ▶). For related literature on the chirality of Tröger’s base, see: Prelog & Wieland (1944 ▶); for mol­ecular clefts, see: Wilcox et al. (1987 ▶) and Artacho et al. (2006 ▶) and references cited therein; for (poly)halo-substituted Tröger’s base analogues, see: Jensen & Wärnmark (2001 ▶), Sergeyev & Diederich (2004 ▶), Hansson et al. (2003 ▶), Li et al. (2005 ▶) and Faroughi et al. (2006 ▶). For related literature, see: Zabrodsky et al. (1993 ▶).

Experimental

Crystal data

C15H6F8N2

M = 366.22

Monoclinic,

a = 8.075 (3) Å

b = 10.469 (2) Å

c = 17.628 (6) Å

β = 117.15 (2)°

V = 1326.0 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.19 mm−1

T = 290 (1) K

0.3 × 0.2 × 0.2 mm

Data collection

Enraf–Nonius MACH3 diffractometer

Absorption correction: none

5028 measured reflections

2412 independent reflections

1353 reflections with I > 2σ(I)

R int = 0.078

3 standard reflections every 73 reflections intensity decay: 4%

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.128

S = 1.03

2412 reflections

251 parameters

All H-atom parameters refined

Δρmax = 0.20 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002602/pk2080sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808002602/pk2080Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C15H6F8N2	Dx = 1.834 Mg m−3
Mr = 366.22	Melting point: 192(1) K
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.075 (3) Å	θ = 5–12º
b = 10.469 (2) Å	µ = 0.19 mm−1
c = 17.628 (6) Å	T = 290 (1) K
β = 117.15 (2)º	Cell measurement pressure: 101(1) kPa
V = 1326.0 (8) Å3	Rhomb, colourless
Z = 4	0.3 × 0.2 × 0.2 mm
F000 = 728

Enraf–Nonius MACH3 diffractometer	Rint = 0.078
Radiation source: sealed tube	θmax = 25.3º
Monochromator: pyrolytic graphite	θmin = 2.3º
T = 290(1) K	h = 0→9
P = 101(1) kPa	k = −12→12
profiled ω/2θ scans	l = −21→18
Absorption correction: none	3 standard reflections
5028 measured reflections	every 73 reflections
2412 independent reflections	intensity decay: 4%
1353 reflections with I > 2σ(I)

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All H-atom parameters refined
R[F2 > 2σ(F2)] = 0.044	w = 1/[σ2(Fo2) + (0.06P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.128	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.20 e Å−3
2412 reflections	Δρmin = −0.25 e Å−3
251 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (2)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
H131	−0.193 (4)	0.216 (3)	0.8025 (17)	0.051 (8)*
H121	0.305 (4)	0.121 (3)	0.810 (2)	0.069 (9)*
H122	0.136 (5)	0.176 (3)	0.726 (2)	0.077 (10)*
H62	−0.105 (5)	0.310 (3)	0.9326 (17)	0.057 (9)*
H132	−0.111 (4)	0.269 (3)	0.741 (2)	0.060 (9)*
H61	0.092 (4)	0.374 (3)	0.9788 (19)	0.053 (9)*
F7	0.1474 (3)	0.21118 (18)	1.10195 (11)	0.0715 (6)
F10	0.2539 (3)	−0.08189 (16)	0.87533 (11)	0.0699 (6)
F1	0.5029 (3)	0.29145 (19)	0.78363 (12)	0.0679 (6)
F9	0.3839 (3)	−0.15905 (16)	1.03755 (11)	0.0729 (6)
N11	0.0509 (3)	0.1395 (2)	0.81513 (13)	0.0506 (6)
F8	0.3308 (3)	−0.01382 (19)	1.15148 (10)	0.0730 (6)
C12A	0.2581 (4)	0.3151 (3)	0.81963 (16)	0.0467 (7)
F4	0.1600 (3)	0.58222 (17)	0.92368 (14)	0.0845 (7)
F3	0.4753 (3)	0.66558 (18)	0.92211 (15)	0.0919 (7)
C10A	0.1288 (4)	0.1067 (3)	0.90262 (15)	0.0417 (6)
C9	0.2933 (4)	−0.0464 (3)	1.01318 (17)	0.0489 (7)
F2	0.6451 (3)	0.5220 (2)	0.85025 (14)	0.0852 (6)
C7	0.1727 (4)	0.1397 (3)	1.04471 (16)	0.0471 (7)
N5	−0.0035 (3)	0.3514 (2)	0.85287 (15)	0.0570 (7)
C4A	0.1674 (4)	0.3903 (3)	0.85490 (17)	0.0488 (7)
C1	0.4148 (4)	0.3626 (3)	0.81791 (18)	0.0510 (8)
C8	0.2668 (4)	0.0260 (3)	1.07054 (16)	0.0491 (7)
C10	0.2252 (4)	−0.0074 (3)	0.93048 (16)	0.0450 (7)
C6A	0.1055 (4)	0.1831 (3)	0.96176 (17)	0.0460 (7)
C13	−0.0834 (5)	0.2423 (4)	0.7960 (2)	0.0611 (9)
C2	0.4898 (4)	0.4799 (3)	0.8519 (2)	0.0583 (8)
C4	0.2450 (5)	0.5081 (3)	0.88958 (18)	0.0584 (8)
C3	0.4040 (5)	0.5512 (3)	0.8886 (2)	0.0616 (9)
C6	0.0168 (5)	0.3137 (3)	0.9374 (2)	0.0577 (9)
C12	0.1908 (5)	0.1805 (3)	0.78815 (19)	0.0530 (8)

	U11	U22	U33	U12	U13	U23
F7	0.1095 (15)	0.0648 (11)	0.0538 (10)	0.0031 (11)	0.0490 (11)	−0.0071 (9)
F10	0.1081 (15)	0.0474 (10)	0.0537 (10)	0.0049 (10)	0.0364 (10)	−0.0103 (8)
F1	0.0709 (12)	0.0683 (12)	0.0764 (12)	0.0122 (10)	0.0440 (10)	0.0101 (10)
F9	0.0981 (15)	0.0433 (10)	0.0660 (12)	0.0137 (10)	0.0276 (10)	0.0114 (9)
N11	0.0534 (14)	0.0571 (16)	0.0335 (12)	0.0002 (13)	0.0130 (10)	0.0035 (11)
F8	0.1033 (15)	0.0666 (12)	0.0379 (9)	0.0000 (11)	0.0224 (9)	0.0098 (9)
C12A	0.0484 (17)	0.0506 (16)	0.0352 (14)	0.0092 (14)	0.0139 (12)	0.0113 (13)
F4	0.1074 (17)	0.0539 (11)	0.1061 (16)	0.0224 (11)	0.0607 (14)	−0.0004 (11)
F3	0.1082 (17)	0.0477 (11)	0.1105 (17)	−0.0089 (12)	0.0419 (14)	−0.0055 (12)
C10A	0.0435 (15)	0.0430 (14)	0.0348 (14)	−0.0044 (13)	0.0144 (12)	0.0002 (12)
C9	0.0557 (17)	0.0351 (15)	0.0481 (16)	0.0008 (14)	0.0170 (14)	0.0039 (13)
F2	0.0694 (13)	0.0731 (13)	0.1142 (16)	−0.0077 (11)	0.0429 (12)	0.0129 (12)
C7	0.0589 (18)	0.0477 (17)	0.0397 (15)	−0.0058 (15)	0.0268 (13)	−0.0068 (13)
N5	0.0536 (15)	0.0572 (15)	0.0577 (15)	0.0156 (14)	0.0233 (12)	0.0161 (13)
C4A	0.0512 (17)	0.0468 (17)	0.0455 (16)	0.0137 (15)	0.0195 (14)	0.0172 (14)
C1	0.0523 (17)	0.0547 (19)	0.0478 (16)	0.0145 (16)	0.0244 (14)	0.0120 (14)
C8	0.0609 (18)	0.0467 (16)	0.0316 (14)	−0.0078 (15)	0.0140 (13)	0.0058 (13)
C10	0.0570 (17)	0.0389 (15)	0.0376 (14)	−0.0047 (14)	0.0201 (13)	−0.0074 (13)
C6A	0.0489 (17)	0.0457 (16)	0.0443 (15)	0.0000 (13)	0.0220 (13)	0.0014 (13)
C13	0.0468 (19)	0.078 (2)	0.0480 (19)	0.0021 (17)	0.0123 (15)	0.0164 (18)
C2	0.0519 (19)	0.0541 (18)	0.067 (2)	0.0070 (16)	0.0250 (16)	0.0183 (16)
C4	0.072 (2)	0.0476 (18)	0.0587 (19)	0.0222 (17)	0.0330 (17)	0.0108 (16)
C3	0.067 (2)	0.0402 (17)	0.067 (2)	0.0048 (16)	0.0217 (17)	0.0091 (15)
C6	0.058 (2)	0.058 (2)	0.064 (2)	0.0141 (17)	0.0335 (18)	0.0116 (17)
C12	0.063 (2)	0.0587 (19)	0.0358 (15)	0.0005 (16)	0.0215 (15)	0.0011 (14)

F7—C7	1.345 (3)	F2—C2	1.342 (3)
F10—C10	1.347 (3)	C7—C8	1.373 (4)
F1—C1	1.348 (3)	C7—C6A	1.384 (4)
F9—C9	1.350 (3)	N5—C4A	1.423 (4)
N11—C10A	1.417 (3)	N5—C13	1.461 (4)
N11—C13	1.454 (4)	N5—C6	1.476 (4)
N11—C12	1.476 (4)	C4A—C4	1.393 (5)
F8—C8	1.343 (3)	C1—C2	1.380 (5)
C12A—C1	1.372 (4)	C6A—C6	1.513 (4)
C12A—C4A	1.400 (4)	C13—H131	0.98 (3)
C12A—C12	1.520 (4)	C13—H132	0.93 (3)
F4—C4	1.346 (3)	C2—C3	1.365 (5)
F3—C3	1.343 (4)	C4—C3	1.368 (5)
C10A—C10	1.387 (4)	C6—H62	0.95 (3)
C10A—C6A	1.393 (4)	C6—H61	0.95 (3)
C9—C8	1.357 (4)	C12—H121	1.03 (3)
C9—C10	1.365 (4)	C12—H122	0.98 (3)
C10A—N11—C13	110.2 (2)	C7—C6A—C10A	118.7 (3)
C10A—N11—C12	113.3 (2)	C7—C6A—C6	120.2 (3)
C13—N11—C12	108.1 (3)	C10A—C6A—C6	121.0 (3)
C1—C12A—C4A	118.7 (3)	N11—C13—N5	111.7 (2)
C1—C12A—C12	120.5 (3)	N11—C13—H131	112.5 (18)
C4A—C12A—C12	120.7 (3)	N5—C13—H131	106.2 (17)
C10—C10A—C6A	118.3 (2)	N11—C13—H132	105.1 (19)
C10—C10A—N11	119.5 (2)	N5—C13—H132	107 (2)
C6A—C10A—N11	122.1 (3)	H131—C13—H132	114 (3)
F9—C9—C8	119.9 (3)	F2—C2—C3	120.8 (3)
F9—C9—C10	119.8 (3)	F2—C2—C1	120.8 (3)
C8—C9—C10	120.3 (3)	C3—C2—C1	118.4 (3)
F7—C7—C8	119.0 (2)	F4—C4—C3	119.3 (3)
F7—C7—C6A	119.3 (3)	F4—C4—C4A	119.2 (3)
C8—C7—C6A	121.7 (3)	C3—C4—C4A	121.6 (3)
C4A—N5—C13	111.1 (3)	F3—C3—C2	119.2 (3)
C4A—N5—C6	113.0 (2)	F3—C3—C4	120.3 (3)
C13—N5—C6	107.1 (3)	C2—C3—C4	120.5 (3)
C4—C4A—C12A	118.1 (3)	N5—C6—C6A	110.4 (3)
C4—C4A—N5	120.1 (3)	N5—C6—H62	106.7 (17)
C12A—C4A—N5	121.8 (3)	C6A—C6—H62	109 (2)
F1—C1—C12A	119.3 (3)	N5—C6—H61	109.5 (17)
F1—C1—C2	118.0 (3)	C6A—C6—H61	109.4 (18)
C12A—C1—C2	122.7 (3)	H62—C6—H61	112 (2)
F8—C8—C9	120.2 (3)	N11—C12—C12A	110.5 (3)
F8—C8—C7	120.5 (3)	N11—C12—H121	113.2 (18)
C9—C8—C7	119.3 (2)	C12A—C12—H121	107.9 (19)
F10—C10—C9	118.6 (3)	N11—C12—H122	109 (2)
F10—C10—C10A	119.8 (2)	C12A—C12—H122	111 (2)
C9—C10—C10A	121.6 (3)	H121—C12—H122	105 (3)
C13—N11—C10A—C10	164.7 (3)	F7—C7—C6A—C6	4.4 (4)
C12—N11—C10A—C10	−74.1 (3)	C8—C7—C6A—C6	−174.9 (3)
C13—N11—C10A—C6A	−12.6 (4)	C10—C10A—C6A—C7	−2.5 (4)
C12—N11—C10A—C6A	108.7 (3)	N11—C10A—C6A—C7	174.8 (2)
C1—C12A—C4A—C4	−2.4 (4)	C10—C10A—C6A—C6	174.6 (3)
C12—C12A—C4A—C4	174.4 (3)	N11—C10A—C6A—C6	−8.1 (4)
C1—C12A—C4A—N5	175.1 (2)	C10A—N11—C13—N5	53.2 (3)
C12—C12A—C4A—N5	−8.2 (4)	C12—N11—C13—N5	−71.2 (3)
C13—N5—C4A—C4	165.8 (3)	C4A—N5—C13—N11	51.4 (3)
C6—N5—C4A—C4	−73.8 (3)	C6—N5—C13—N11	−72.5 (3)
C13—N5—C4A—C12A	−11.6 (3)	F1—C1—C2—F2	0.4 (4)
C6—N5—C4A—C12A	108.8 (3)	C12A—C1—C2—F2	178.8 (3)
C4A—C12A—C1—F1	−179.6 (2)	F1—C1—C2—C3	−178.4 (3)
C12—C12A—C1—F1	3.7 (4)	C12A—C1—C2—C3	0.0 (4)
C4A—C12A—C1—C2	2.0 (4)	C12A—C4A—C4—F4	179.9 (2)
C12—C12A—C1—C2	−174.7 (3)	N5—C4A—C4—F4	2.4 (4)
F9—C9—C8—F8	0.1 (4)	C12A—C4A—C4—C3	0.9 (4)
C10—C9—C8—F8	178.7 (3)	N5—C4A—C4—C3	−176.6 (3)
F9—C9—C8—C7	−179.3 (3)	F2—C2—C3—F3	1.1 (5)
C10—C9—C8—C7	−0.8 (4)	C1—C2—C3—F3	179.9 (3)
F7—C7—C8—F8	0.7 (4)	F2—C2—C3—C4	179.6 (3)
C6A—C7—C8—F8	179.9 (3)	C1—C2—C3—C4	−1.6 (5)
F7—C7—C8—C9	−179.8 (3)	F4—C4—C3—F3	0.7 (4)
C6A—C7—C8—C9	−0.6 (4)	C4A—C4—C3—F3	179.7 (3)
F9—C9—C10—F10	−1.3 (4)	F4—C4—C3—C2	−177.8 (3)
C8—C9—C10—F10	−179.9 (3)	C4A—C4—C3—C2	1.2 (5)
F9—C9—C10—C10A	179.0 (3)	C4A—N5—C6—C6A	−75.7 (4)
C8—C9—C10—C10A	0.5 (4)	C13—N5—C6—C6A	47.0 (3)
C6A—C10A—C10—F10	−178.4 (2)	C7—C6A—C6—N5	166.7 (3)
N11—C10A—C10—F10	4.2 (4)	C10A—C6A—C6—N5	−10.4 (4)
C6A—C10A—C10—C9	1.2 (4)	C10A—N11—C12—C12A	−75.3 (3)
N11—C10A—C10—C9	−176.2 (3)	C13—N11—C12—C12A	47.2 (3)
F7—C7—C6A—C10A	−178.5 (3)	C1—C12A—C12—N11	166.2 (2)
C8—C7—C6A—C10A	2.3 (4)	C4A—C12A—C12—N11	−10.5 (4)

C—H···F	C—H	H···F	C···F	C—H···F
C13—H132···F10i	0.93 (3)	2.41 (3)	3.257 (4)	151 (3)
C13—H131···F1ii	0.98 (4)	2.46 (3)	3.287 (5)	143 (2)
C12—H122···F7iii	0.98 (3)	2.52 (3)	3.336 (4)	141 (3)

Table 1

C—H ⋯ F contacts (Å, °)

C—H⋯F	C—H	H⋯F	C⋯F	C—H⋯F
C13—H132⋯F10i	0.93 (3)	2.41 (3)	3.257 (4)	151 (3)
C13—H131⋯F1ii	0.98 (4)	2.46 (3)	3.287 (5)	143 (2)
C12—H122⋯F7iii	0.98 (3)	2.52 (3)	3.336 (4)	141 (3)

Symmetry codes: (i) , (ii) , (iii) .