The title compound, C
20H
12N
2, displays slightly lengthened C—C bonds at the central C atom of the triquinacene framework (mean 1.572 Å) and wide exocyclic angles at the benzo-annelation sites (
ca 127°). The packing is determined by two C—H
N contacts and one of the type C—H
π.
Supporting information
CCDC reference: 209972
Key indicators
- Single-crystal X-ray study
- T = 178 K
- Mean (C-C) = 0.005 Å
- R factor = 0.065
- wR factor = 0.216
- Data-to-parameter ratio = 12.8
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(9) - C(19) = 1.44 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared according to Witulski (1992) and recrystallized from chloroform/pentane.
H atoms were included using a riding model with fixed C—H bond lengths (Csp2—H = 0.95 Å and methine = 1.00 Å); Uiso(H) values were fixed at 1.2Ueq of the parent atom.
Data collection: P3 (Nicolet, 1987); cell refinement: P3; data reduction: XDISK (Nicolet, 1987); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 1994); software used to prepare material for publication: SHELXL97.
(3,4),(6,7)Dibenzo-9,10-dicyanotriquinacene
top
Crystal data top
C20H12N2 | F(000) = 584 |
Mr = 280.32 | Dx = 1.297 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 49 reflections |
a = 9.528 (4) Å | θ = 10–11.5° |
b = 12.401 (6) Å | µ = 0.08 mm−1 |
c = 12.265 (6) Å | T = 178 K |
β = 97.73 (4)° | Prism, colourless |
V = 1436.0 (12) Å3 | 0.50 × 0.35 × 0.25 mm |
Z = 4 | |
Data collection top
Nicolet R3 diffractometer | Rint = 0.053 |
Radiation source: fine-focus sealed tube | θmax = 25.1°, θmin = 3.0° |
Graphite monochromator | h = −4→11 |
ω scans | k = −13→14 |
4770 measured reflections | l = −14→14 |
2542 independent reflections | 3 standard reflections every 147 reflections |
1266 reflections with I > 2s(I) | intensity decay: none |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.217 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.4194P] where P = (Fo2 + 2Fc2)/3 |
2542 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C20H12N2 | V = 1436.0 (12) Å3 |
Mr = 280.32 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.528 (4) Å | µ = 0.08 mm−1 |
b = 12.401 (6) Å | T = 178 K |
c = 12.265 (6) Å | 0.50 × 0.35 × 0.25 mm |
β = 97.73 (4)° | |
Data collection top
Nicolet R3 diffractometer | Rint = 0.053 |
4770 measured reflections | 3 standard reflections every 147 reflections |
2542 independent reflections | intensity decay: none |
1266 reflections with I > 2s(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.217 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.22 e Å−3 |
2542 reflections | Δρmin = −0.28 e Å−3 |
199 parameters | |
Special details top
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 (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.3621 (4) | 0.7145 (4) | 0.2406 (3) | 0.0454 (10) | |
H1 | 0.2896 | 0.7641 | 0.2138 | 0.054* | |
C2 | 0.5117 (4) | 0.7477 (3) | 0.2839 (3) | 0.0384 (9) | |
H2 | 0.5139 | 0.7996 | 0.3465 | 0.046* | |
C3 | 0.5945 (4) | 0.7896 (3) | 0.1958 (3) | 0.0351 (9) | |
C4 | 0.7047 (4) | 0.7215 (3) | 0.1803 (3) | 0.0368 (9) | |
C5 | 0.7084 (4) | 0.6205 (3) | 0.2493 (3) | 0.0367 (9) | |
H5 | 0.8021 | 0.6112 | 0.2959 | 0.044* | |
C6 | 0.6646 (4) | 0.5205 (3) | 0.1848 (3) | 0.0388 (9) | |
C7 | 0.5360 (4) | 0.4797 (3) | 0.2061 (3) | 0.0411 (9) | |
C8 | 0.4732 (4) | 0.5471 (3) | 0.2893 (3) | 0.0402 (10) | |
H8 | 0.4566 | 0.5034 | 0.3549 | 0.048* | |
C9 | 0.3427 (4) | 0.6099 (4) | 0.2439 (3) | 0.0461 (10) | |
C10 | 0.5855 (4) | 0.6388 (3) | 0.3215 (3) | 0.0359 (9) | |
C11 | 0.5684 (4) | 0.8825 (3) | 0.1346 (3) | 0.0439 (10) | |
H11 | 0.4918 | 0.9284 | 0.1457 | 0.053* | |
C12 | 0.6547 (4) | 0.9074 (3) | 0.0575 (3) | 0.0494 (11) | |
H12 | 0.6364 | 0.9703 | 0.0137 | 0.059* | |
C13 | 0.7683 (5) | 0.8421 (4) | 0.0428 (3) | 0.0559 (12) | |
H13 | 0.8292 | 0.8618 | −0.0092 | 0.067* | |
C14 | 0.7940 (4) | 0.7483 (4) | 0.1032 (3) | 0.0488 (11) | |
H14 | 0.8713 | 0.7029 | 0.0924 | 0.059* | |
C15 | 0.7368 (4) | 0.4700 (3) | 0.1076 (3) | 0.0480 (11) | |
H15 | 0.8249 | 0.4977 | 0.0918 | 0.058* | |
C16 | 0.6785 (5) | 0.3793 (4) | 0.0544 (3) | 0.0586 (13) | |
H16 | 0.7277 | 0.3440 | 0.0022 | 0.070* | |
C17 | 0.5506 (6) | 0.3389 (4) | 0.0756 (4) | 0.0637 (13) | |
H17 | 0.5121 | 0.2767 | 0.0375 | 0.076* | |
C18 | 0.4775 (5) | 0.3883 (3) | 0.1523 (3) | 0.0574 (12) | |
H18 | 0.3895 | 0.3603 | 0.1678 | 0.069* | |
C19 | 0.2120 (5) | 0.5575 (4) | 0.2025 (4) | 0.0630 (13) | |
C20 | 0.6344 (4) | 0.6374 (3) | 0.4405 (3) | 0.0373 (9) | |
N1 | 0.1104 (4) | 0.5127 (4) | 0.1702 (4) | 0.0934 (16) | |
N2 | 0.6685 (4) | 0.6349 (3) | 0.5333 (3) | 0.0482 (9) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.042 (2) | 0.058 (3) | 0.038 (2) | 0.005 (2) | 0.0122 (17) | 0.0049 (19) |
C2 | 0.042 (2) | 0.039 (2) | 0.0338 (19) | 0.0021 (17) | 0.0040 (16) | −0.0001 (17) |
C3 | 0.044 (2) | 0.031 (2) | 0.0281 (18) | −0.0055 (17) | −0.0006 (15) | 0.0004 (16) |
C4 | 0.039 (2) | 0.040 (2) | 0.0306 (18) | −0.0088 (18) | 0.0014 (16) | 0.0013 (16) |
C5 | 0.038 (2) | 0.037 (2) | 0.0335 (19) | 0.0003 (17) | 0.0006 (16) | 0.0001 (16) |
C6 | 0.046 (2) | 0.036 (2) | 0.0326 (19) | 0.0077 (18) | −0.0015 (17) | 0.0011 (16) |
C7 | 0.051 (2) | 0.032 (2) | 0.039 (2) | −0.0027 (18) | −0.0011 (18) | 0.0036 (17) |
C8 | 0.041 (2) | 0.044 (2) | 0.0354 (19) | −0.0061 (18) | 0.0025 (17) | 0.0066 (17) |
C9 | 0.041 (2) | 0.060 (3) | 0.038 (2) | −0.008 (2) | 0.0065 (17) | 0.0067 (19) |
C10 | 0.041 (2) | 0.036 (2) | 0.0310 (18) | −0.0015 (17) | 0.0046 (16) | 0.0004 (16) |
C11 | 0.053 (2) | 0.042 (2) | 0.035 (2) | −0.0028 (19) | 0.0006 (18) | 0.0017 (18) |
C12 | 0.058 (3) | 0.045 (2) | 0.041 (2) | −0.013 (2) | −0.008 (2) | 0.0129 (19) |
C13 | 0.052 (3) | 0.069 (3) | 0.047 (2) | −0.020 (2) | 0.007 (2) | 0.013 (2) |
C14 | 0.040 (2) | 0.066 (3) | 0.040 (2) | 0.000 (2) | 0.0052 (18) | 0.005 (2) |
C15 | 0.051 (2) | 0.051 (3) | 0.039 (2) | 0.012 (2) | −0.0026 (19) | −0.0006 (19) |
C16 | 0.080 (3) | 0.053 (3) | 0.039 (2) | 0.027 (3) | −0.009 (2) | −0.005 (2) |
C17 | 0.090 (4) | 0.044 (3) | 0.051 (3) | 0.002 (3) | −0.013 (3) | −0.011 (2) |
C18 | 0.067 (3) | 0.049 (3) | 0.051 (3) | −0.011 (2) | −0.010 (2) | 0.002 (2) |
C19 | 0.048 (3) | 0.077 (3) | 0.062 (3) | −0.015 (3) | 0.001 (2) | 0.022 (3) |
C20 | 0.046 (2) | 0.031 (2) | 0.035 (2) | −0.0062 (17) | 0.0065 (17) | 0.0033 (16) |
N1 | 0.058 (3) | 0.118 (4) | 0.099 (3) | −0.031 (3) | −0.008 (3) | 0.030 (3) |
N2 | 0.057 (2) | 0.051 (2) | 0.0365 (18) | −0.0072 (17) | 0.0061 (15) | 0.0031 (16) |
Geometric parameters (Å, º) top
C1—C9 | 1.312 (6) | C8—H8 | 1.0000 |
C1—C2 | 1.510 (5) | C9—C19 | 1.436 (6) |
C1—H1 | 0.9500 | C10—C20 | 1.471 (5) |
C2—C3 | 1.513 (5) | C11—C12 | 1.369 (5) |
C2—C10 | 1.564 (5) | C11—H11 | 0.9500 |
C2—H2 | 1.0000 | C12—C13 | 1.383 (6) |
C3—C11 | 1.379 (5) | C12—H12 | 0.9500 |
C3—C4 | 1.381 (5) | C13—C14 | 1.383 (6) |
C4—C14 | 1.395 (5) | C13—H13 | 0.9500 |
C4—C5 | 1.509 (5) | C14—H14 | 0.9500 |
C5—C6 | 1.501 (5) | C15—C16 | 1.380 (6) |
C5—C10 | 1.577 (5) | C15—H15 | 0.9500 |
C5—H5 | 1.0000 | C16—C17 | 1.374 (7) |
C6—C7 | 1.383 (5) | C16—H16 | 0.9500 |
C6—C15 | 1.391 (5) | C17—C18 | 1.386 (6) |
C7—C18 | 1.390 (5) | C17—H17 | 0.9500 |
C7—C8 | 1.504 (5) | C18—H18 | 0.9500 |
C8—C9 | 1.508 (5) | C19—N1 | 1.140 (5) |
C8—C10 | 1.574 (5) | C20—N2 | 1.141 (4) |
| | | |
C9—C1—C2 | 112.9 (4) | C1—C9—C8 | 114.2 (3) |
C9—C1—H1 | 123.6 | C19—C9—C8 | 122.0 (4) |
C2—C1—H1 | 123.6 | C20—C10—C2 | 111.9 (3) |
C1—C2—C3 | 113.6 (3) | C20—C10—C8 | 110.8 (3) |
C1—C2—C10 | 103.5 (3) | C2—C10—C8 | 106.6 (3) |
C3—C2—C10 | 104.5 (3) | C20—C10—C5 | 113.3 (3) |
C1—C2—H2 | 111.6 | C2—C10—C5 | 107.3 (3) |
C3—C2—H2 | 111.6 | C8—C10—C5 | 106.6 (3) |
C10—C2—H2 | 111.6 | C12—C11—C3 | 118.9 (4) |
C11—C3—C4 | 121.4 (3) | C12—C11—H11 | 120.6 |
C11—C3—C2 | 127.0 (3) | C3—C11—H11 | 120.6 |
C4—C3—C2 | 111.6 (3) | C11—C12—C13 | 120.7 (4) |
C3—C4—C14 | 119.5 (3) | C11—C12—H12 | 119.6 |
C3—C4—C5 | 113.0 (3) | C13—C12—H12 | 119.6 |
C14—C4—C5 | 127.4 (4) | C14—C13—C12 | 120.6 (4) |
C6—C5—C4 | 114.0 (3) | C14—C13—H13 | 119.7 |
C6—C5—C10 | 103.9 (3) | C12—C13—H13 | 119.7 |
C4—C5—C10 | 103.5 (3) | C13—C14—C4 | 118.9 (4) |
C6—C5—H5 | 111.6 | C13—C14—H14 | 120.6 |
C4—C5—H5 | 111.6 | C4—C14—H14 | 120.6 |
C10—C5—H5 | 111.6 | C16—C15—C6 | 118.9 (4) |
C7—C6—C15 | 119.8 (4) | C16—C15—H15 | 120.5 |
C7—C6—C5 | 113.1 (3) | C6—C15—H15 | 120.5 |
C15—C6—C5 | 127.1 (4) | C17—C16—C15 | 121.2 (4) |
C6—C7—C18 | 121.1 (4) | C17—C16—H16 | 119.4 |
C6—C7—C8 | 111.7 (3) | C15—C16—H16 | 119.4 |
C18—C7—C8 | 127.2 (4) | C16—C17—C18 | 120.4 (4) |
C7—C8—C9 | 114.8 (3) | C16—C17—H17 | 119.8 |
C7—C8—C10 | 104.6 (3) | C18—C17—H17 | 119.8 |
C9—C8—C10 | 102.6 (3) | C17—C18—C7 | 118.5 (4) |
C7—C8—H8 | 111.4 | C17—C18—H18 | 120.8 |
C9—C8—H8 | 111.4 | C7—C18—H18 | 120.8 |
C10—C8—H8 | 111.4 | N1—C19—C9 | 177.8 (6) |
C1—C9—C19 | 123.8 (4) | N2—C20—C10 | 177.9 (4) |
| | | |
C9—C1—C2—C3 | 110.4 (4) | C1—C2—C10—C20 | −117.5 (3) |
C9—C1—C2—C10 | −2.3 (4) | C3—C2—C10—C20 | 123.3 (3) |
C1—C2—C3—C11 | 66.0 (5) | C1—C2—C10—C8 | 3.7 (3) |
C10—C2—C3—C11 | 178.1 (3) | C3—C2—C10—C8 | −115.5 (3) |
C1—C2—C3—C4 | −113.3 (4) | C1—C2—C10—C5 | 117.7 (3) |
C10—C2—C3—C4 | −1.1 (4) | C3—C2—C10—C5 | −1.5 (3) |
C11—C3—C4—C14 | 1.7 (5) | C7—C8—C10—C20 | −121.6 (3) |
C2—C3—C4—C14 | −179.0 (3) | C9—C8—C10—C20 | 118.1 (3) |
C11—C3—C4—C5 | −175.7 (3) | C7—C8—C10—C2 | 116.4 (3) |
C2—C3—C4—C5 | 3.6 (4) | C9—C8—C10—C2 | −3.8 (3) |
C3—C4—C5—C6 | 107.8 (4) | C7—C8—C10—C5 | 2.0 (3) |
C14—C4—C5—C6 | −69.4 (5) | C9—C8—C10—C5 | −118.2 (3) |
C3—C4—C5—C10 | −4.3 (4) | C6—C5—C10—C20 | 120.1 (3) |
C14—C4—C5—C10 | 178.5 (3) | C4—C5—C10—C20 | −120.6 (3) |
C4—C5—C6—C7 | −110.6 (4) | C6—C5—C10—C2 | −115.9 (3) |
C10—C5—C6—C7 | 1.3 (4) | C4—C5—C10—C2 | 3.4 (3) |
C4—C5—C6—C15 | 67.6 (5) | C6—C5—C10—C8 | −2.0 (3) |
C10—C5—C6—C15 | 179.5 (3) | C4—C5—C10—C8 | 117.3 (3) |
C15—C6—C7—C18 | 0.5 (6) | C4—C3—C11—C12 | −0.4 (5) |
C5—C6—C7—C18 | 178.9 (3) | C2—C3—C11—C12 | −179.6 (4) |
C15—C6—C7—C8 | −178.4 (3) | C3—C11—C12—C13 | −1.5 (6) |
C5—C6—C7—C8 | 0.0 (4) | C11—C12—C13—C14 | 2.2 (6) |
C6—C7—C8—C9 | 110.4 (4) | C12—C13—C14—C4 | −0.9 (6) |
C18—C7—C8—C9 | −68.4 (5) | C3—C4—C14—C13 | −1.0 (5) |
C6—C7—C8—C10 | −1.3 (4) | C5—C4—C14—C13 | 176.0 (4) |
C18—C7—C8—C10 | 179.9 (4) | C7—C6—C15—C16 | −0.6 (5) |
C2—C1—C9—C19 | −176.8 (3) | C5—C6—C15—C16 | −178.7 (3) |
C2—C1—C9—C8 | −0.3 (5) | C6—C15—C16—C17 | 0.6 (6) |
C7—C8—C9—C1 | −110.2 (4) | C15—C16—C17—C18 | −0.6 (6) |
C10—C8—C9—C1 | 2.7 (4) | C16—C17—C18—C7 | 0.6 (6) |
C7—C8—C9—C19 | 66.4 (5) | C6—C7—C18—C17 | −0.5 (6) |
C10—C8—C9—C19 | 179.3 (3) | C8—C7—C18—C17 | 178.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···N2i | 0.95 | 2.67 | 3.478 (5) | 144 |
C8—H8···N2ii | 1.00 | 2.59 | 3.528 (5) | 157 |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C20H12N2 |
Mr | 280.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 178 |
a, b, c (Å) | 9.528 (4), 12.401 (6), 12.265 (6) |
β (°) | 97.73 (4) |
V (Å3) | 1436.0 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.35 × 0.25 |
|
Data collection |
Diffractometer | Nicolet R3 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2s(I)] reflections | 4770, 2542, 1266 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.596 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.217, 1.04 |
No. of reflections | 2542 |
No. of parameters | 199 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.22, −0.28 |
Selected geometric parameters (Å, º) topC2—C10 | 1.564 (5) | C8—C10 | 1.574 (5) |
C5—C10 | 1.577 (5) | | |
| | | |
C11—C3—C2 | 127.0 (3) | C15—C6—C5 | 127.1 (4) |
C14—C4—C5 | 127.4 (4) | C18—C7—C8 | 127.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···N2i | 0.95 | 2.67 | 3.478 (5) | 144 |
C8—H8···N2ii | 1.00 | 2.59 | 3.528 (5) | 157 |
Symmetry codes: (i) x−1/2, −y+3/2, z−1/2; (ii) −x+1, −y+1, −z+1. |
Dibenzoisobullvalene dicarbonitrile [(1); Jones et al., 2003], readily available by photoisomerization of the corresponding dibenzoprebullvalene isomer (Hopf & Witulski, 1995), contains a vinylcyclopropane subunit that, in principle, can undergo thermal ring expansion to a five-membered ring. To test this possibility, we heated (1) in toluene in a sealed ampoule at 503 K. From the product mixture, the ring-expanded dinitrile (2), a derivative of dibenzotriquinacene, can indeed be isolated in good yield (86%). The structure of (2) was previously elucidated by its spectroscopic and analytical data (Witulski, 1992) and the X-ray structural analysis reported here.
The molecule of (2) is shown in Fig. 1. Bond lengths and angles may be regarded as normal; however, some deviations from standard values are observed, e.g. the slightly lengthened bonds to the central atom C10 of the triquinacene framework, and the widened exocyclic angles at the benzo-annelation sites (Table 1).
The molecules are linked to form corrugated layers parallel to (101) by two C—H···N contacts (Table 2). Additionally, the centroid (Cent) of ring C6/C7/C15–C18 is involved in a contact of the type C—H···π, viz. C17—H17···Cent(1 − x, 1 − y, −z), with H···Cent = 2.72 Å and an angle of 150°. This contact, not shown in Fig. 2, links the layers to complete the three-dimensional packing.