organic papers
Acta Cryst.(2005). E61, o667–o668 doi:10.1107/S1600536805004484 Dyakonenkoet al. C
18H17N3O2
o667
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
2,2-Dimethyl-6-(4-nitrophenyl)-4-phenyl-1,3-diaza-bicyclo[3.1.0]hex-3-ene
Viktoria V. Dyakonenko,* Oleg V. Shishkin, Alexandr V. Zbruev and Sergey M. Desenko
Institute for Scintillation Materials, STC ‘Institute for Single Crystals’, National Academy of Sciences of Ukraine, 60 Lenina Ave., Kharkov 61001, Ukraine
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 294 K
Mean(C–C) = 0.004 A˚
Rfactor = 0.067
wRfactor = 0.198
Data-to-parameter ratio = 10.1
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
In the crystal structure of the title compound, C18H17N3O2, the
imidazoline ring has a very flattened envelope conformation, with a twisted endocyclic C N double bond.
Comment
Bicyclic aziridines represent a very interesting class of organic compounds, possessing unique photochromic properties. It has been demonstrated that these compounds form deeply colored, fairly stable materials under UV radiation (Orlovet al., 1988). This property allows us to consider bicyclic azir-idines as possible candidates in the search for radiochromic materials. Among these compounds, 2,2-dimethyl-6-(4-nitro-phenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene, (I), is one of the most interesting, and we have carried out an X-ray diffraction study of it.
The imidazoline ring has a very flattened envelope confor-mation. The deviation of atom N2 from the mean plane of the remaining ring atoms is 0.09 (1) A˚ . This conformation of the five-membered ring results in a slight twisting of the C N double bond, the C3—N2—C2—C1 torsion angle being 5.8 (2). There is a similar twisting of the C N double bond in compounds (II) (3.2; Orlov et al., 1991) and (III) (2.7;
Kaluski et al., 1994). The C1—C2 bond is shortened, to 1.488 (3) A˚ , compared with the average value of 1.512 A˚ (Bu¨rgi & Dunitz, 1994).
The aziridine and imidazoline rings arecis-fused, the H1— C1—N1—Lp (where Lp is the N lone pair) torsion angle being 2. The angle between the two ring planes is 113 (2). The same conformation is observed for compounds (II) and (III). The phenyl substituent is rotated with respect to the N2 C2 double bond, the N2—C2—C5—C10 torsion angle being 14.2 (3). In turn, the p-nitrophenyl substituent is
rotated with respect to the aziridine plane, the N1—C4— C13—C18 torsion angle being 19.5 (3); this compares with a
value of 29.1 in compound (II). In (III), however, the
corresponding angle is 113.9. The nitro group is coplanar with
the attached aromatic ring, the O2—N3–C16—C15 torsion angle being 1.8 (3).
Experimental
The title compound was prepared according to the procedure of Heineet al. (1968).
Crystal data
C18H17N3O2 Mr= 307.35 Triclinic,P1 a= 9.535 (3) A˚ b= 9.539 (3) A˚ c= 10.093 (3) A˚ = 103.89 (2)
= 92.05 (3)
= 113.50 (2)
V= 808.3 (5) A˚3
Z= 2
Dx= 1.263 Mg m3 MoKradiation Cell parameters from 24
reflections = 10–14
= 0.08 mm1 T= 294 (2) K Block, blue 0.40.20.2 mm
Data collection
Siemens P3/PC diffractometer –2scans
Absorption correction: none 2960 measured reflections 2786 independent reflections 2425 reflections withI> 2(I) Rint= 0.038
max= 25.1 h= 0!11 k=11!10 l=12!11 2 standard reflections
every 98 reflections intensity decay: 5%
Refinement
Refinement onF2 R[F2> 2(F2)] = 0.067 wR(F2) = 0.198 S= 1.08 2786 reflections 276 parameters
All H-atom parameters refined
w= 1/[2(F
o2) + (0.1417P)2 + 0.1312P]
whereP= (Fo2+ 2Fc2)/3 (/)max< 0.001
max= 0.42 e A˚
3
min=0.25 e A˚
3 Extinction correction: none
Table 1
Selected interatomic distances (A˚ ).
N1—C1 1.470 (2) N1—C4 1.476 (3) N1—C3 1.487 (3) N2—C2 1.283 (3) N2—C3 1.479 (3) C1—C2 1.488 (3)
C1—C4 1.506 (3) C2—C5 1.475 (3) C3—C11 1.516 (3) C3—C12 1.527 (3) C4—C13 1.479 (3)
The H atom parameters were freely refined and the C—H distances lie in the range 0.86 (3)–1.02 (3) A˚ .
Data collection: P3 (Siemens,1989); cell refinement: P3; data reduction:XDISK(Siemens, 1991); program(s) used to solve struc-ture:SHELXS97(Sheldrick, 1990); program(s) used to refine struc-ture: SHELXL97 (Sheldrick, 1997); molecular graphics: XP
(Siemens, 1991); software used to prepare material for publication:
SHELXL97.
References
Bu¨rgi, H.-B. & Dunitz, J. D. (1994).Structure Correlation, Vol. 2, pp. 767–784. Weinheim: VCH.
Heine, H., Smith, A. B. & Bower, D. (1968).J. Org. Chem.33, 1097–1099. Kaluski, Z., Figas, E., Vorobyova, N. & Orlov, V. (1994).J. Struct. Chem.35,
146–149.
Orlov, V., Kaluski, Z., Figas, E., Vorobyova, N., Bakumenko, A. & Yaremenko, F. (1991).Chem. Heterocycl. Compd.pp. 1060–1066.
Orlov, V., Yaremenko, F., Vorobyova, N. & Demenkova, N. (1988).Chem. Heterocycl. Compd.pp. 328–333.
Sheldrick, G. M. (1990).Acta Cryst.A46, 467–473.
Sheldrick, G. M. (1997).SHELXL97. University of Go¨ttingen, Germany. Siemens (1989).P3. Siemens Analytical X-ray Instruments Inc., Karlsruhe,
Germany.
[image:2.610.45.298.70.235.2]Siemens (1991).XDISKandXP. Siemens Analytical X-ray Instruments Inc., Karlsruhe, Germany.
Figure 1
supporting information
sup-1 Acta Cryst. (2005). E61, o667–o668
supporting information
Acta Cryst. (2005). E61, o667–o668 [https://doi.org/10.1107/S1600536805004484]
2,2-Dimethyl-6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene
Viktoria V. Dyakonenko, Oleg V. Shishkin, Alexandr V. Zbruev and Sergey M. Desenko
2,2-Dimethyl-6-(4-nitrophenyl)-4-phenyl-1,3-diazabicyclo[3.1.0]hex-3-ene
Crystal data
C18H17N3O2 Mr = 307.35 Triclinic, P1 Hall symbol: -P 1
a = 9.535 (3) Å
b = 9.539 (3) Å
c = 10.093 (3) Å
α = 103.89 (2)°
β = 92.05 (3)°
γ = 113.50 (2)°
V = 808.3 (5) Å3
Z = 2
F(000) = 324
Dx = 1.263 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 24 reflections
θ = 10–14°
µ = 0.08 mm−1 T = 294 K Block, blue 0.4 × 0.2 × 0.2 mm
Data collection
Siemens P3/PC diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
θ–2θ scans
2960 measured reflections 2786 independent reflections 2425 reflections with I > 2σ(I)
Rint = 0.038
θmax = 25.1°, θmin = 2.1° h = 0→11
k = −11→10
l = −12→11
2 standard reflections every 98 reflections intensity decay: 5%
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.067 wR(F2) = 0.198 S = 1.08 2786 reflections 276 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: difference Fourier map All H-atom parameters refined
w = 1/[σ2(F
o2) + (0.1417P)2 + 0.1312P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.42 e Å−3
Δρmin = −0.25 e Å−3
Special details
Refinement. Refinement of F2 against ALL reflections. The weightedR-factorwRand goodness of fitSare 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 calculatingR-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)
x y z Uiso*/Ueq
N1 0.26673 (18) 0.40846 (19) 0.24562 (17) 0.0471 (4)
N2 0.41115 (19) 0.67009 (19) 0.39695 (17) 0.0487 (5)
N3 0.3035 (2) −0.2645 (2) −0.0357 (2) 0.0635 (5)
O1 0.2305 (3) −0.3187 (3) −0.1523 (2) 0.0982 (7)
O2 0.3723 (3) −0.3295 (2) 0.0127 (2) 0.0881 (7)
C1 0.4233 (2) 0.4805 (2) 0.2106 (2) 0.0446 (5)
H1 0.440 (3) 0.460 (3) 0.116 (3) 0.055 (6)*
C2 0.4980 (2) 0.6418 (2) 0.31003 (19) 0.0430 (5)
C3 0.2566 (2) 0.5351 (2) 0.3587 (2) 0.0503 (5)
C4 0.3804 (2) 0.3488 (2) 0.2800 (2) 0.0448 (5)
H4 0.426 (3) 0.377 (3) 0.376 (2) 0.050 (6)*
C5 0.6566 (2) 0.7576 (2) 0.31004 (19) 0.0455 (5)
C6 0.7559 (3) 0.7109 (3) 0.2332 (3) 0.0574 (6)
H6 0.720 (3) 0.606 (3) 0.179 (3) 0.061 (7)*
C7 0.9047 (3) 0.8217 (4) 0.2336 (3) 0.0714 (7)
H7 0.971 (4) 0.793 (4) 0.182 (3) 0.076 (8)*
C8 0.9525 (3) 0.9777 (4) 0.3081 (3) 0.0776 (8)
H8 1.049 (5) 1.048 (5) 0.306 (4) 0.107 (11)*
C9 0.8548 (3) 1.0239 (3) 0.3834 (3) 0.0760 (8)
H9 0.889 (5) 1.138 (5) 0.440 (4) 0.113 (12)*
C10 0.7069 (3) 0.9155 (3) 0.3852 (2) 0.0585 (6)
H10 0.636 (3) 0.947 (3) 0.443 (3) 0.065 (7)*
C11 0.2028 (3) 0.4776 (3) 0.4833 (3) 0.0659 (7)
H11C 0.274 (4) 0.437 (4) 0.524 (3) 0.095 (10)*
H11B 0.193 (3) 0.560 (4) 0.551 (3) 0.077 (8)*
H11A 0.101 (4) 0.398 (4) 0.450 (3) 0.079 (8)*
C12 0.1470 (3) 0.5923 (3) 0.2983 (3) 0.0649 (6)
H12A 0.179 (3) 0.620 (3) 0.213 (3) 0.069 (7)*
H12B 0.042 (4) 0.509 (4) 0.277 (3) 0.093 (9)*
H12C 0.141 (4) 0.679 (4) 0.370 (4) 0.095 (10)*
C13 0.3525 (2) 0.1862 (2) 0.1995 (2) 0.0452 (5)
C14 0.4261 (2) 0.1056 (2) 0.2493 (2) 0.0519 (5)
H14 0.492 (3) 0.159 (3) 0.337 (3) 0.064 (7)*
C15 0.4087 (3) −0.0423 (3) 0.1738 (2) 0.0555 (5)
H15 0.464 (3) −0.096 (4) 0.207 (3) 0.076 (8)*
C16 0.3164 (2) −0.1101 (2) 0.0470 (2) 0.0501 (5)
C17 0.2394 (3) −0.0356 (3) −0.0045 (3) 0.0600 (6)
H17 0.182 (4) −0.073 (4) −0.084 (3) 0.080 (9)*
C18 0.2572 (3) 0.1129 (3) 0.0732 (2) 0.0568 (6)
supporting information
sup-3 Acta Cryst. (2005). E61, o667–o668
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
N1 0.0420 (8) 0.0441 (9) 0.0548 (10) 0.0165 (7) 0.0098 (7) 0.0150 (7)
N2 0.0459 (9) 0.0429 (9) 0.0530 (9) 0.0147 (7) 0.0128 (7) 0.0122 (7)
N3 0.0669 (12) 0.0500 (11) 0.0667 (12) 0.0202 (9) 0.0161 (10) 0.0107 (9)
O1 0.1034 (16) 0.0711 (13) 0.0922 (15) 0.0335 (11) −0.0160 (12) −0.0165 (11)
O2 0.1295 (18) 0.0698 (12) 0.0857 (13) 0.0632 (13) 0.0226 (12) 0.0194 (10)
C1 0.0461 (10) 0.0447 (10) 0.0451 (10) 0.0183 (8) 0.0118 (8) 0.0164 (8)
C2 0.0435 (10) 0.0415 (10) 0.0463 (10) 0.0176 (8) 0.0093 (8) 0.0166 (8)
C3 0.0416 (10) 0.0465 (11) 0.0593 (12) 0.0158 (8) 0.0137 (8) 0.0126 (9)
C4 0.0465 (10) 0.0414 (10) 0.0466 (11) 0.0168 (8) 0.0090 (8) 0.0151 (8)
C5 0.0419 (10) 0.0485 (10) 0.0484 (10) 0.0167 (8) 0.0074 (8) 0.0217 (8)
C6 0.0541 (12) 0.0602 (13) 0.0697 (14) 0.0285 (10) 0.0193 (10) 0.0293 (11)
C7 0.0504 (12) 0.098 (2) 0.0802 (16) 0.0350 (13) 0.0228 (12) 0.0410 (15)
C8 0.0457 (13) 0.087 (2) 0.0787 (17) 0.0029 (12) 0.0071 (12) 0.0305 (15)
C9 0.0601 (14) 0.0614 (15) 0.0787 (17) −0.0001 (11) 0.0073 (12) 0.0161 (13)
C10 0.0516 (12) 0.0518 (12) 0.0605 (13) 0.0114 (9) 0.0090 (10) 0.0133 (10)
C11 0.0617 (14) 0.0630 (14) 0.0676 (15) 0.0184 (12) 0.0278 (12) 0.0195 (12)
C12 0.0516 (13) 0.0649 (14) 0.0817 (17) 0.0287 (11) 0.0148 (11) 0.0185 (13)
C13 0.0446 (10) 0.0419 (10) 0.0486 (10) 0.0144 (8) 0.0118 (8) 0.0176 (8)
C14 0.0550 (11) 0.0467 (11) 0.0520 (11) 0.0188 (9) 0.0024 (9) 0.0155 (9)
C15 0.0615 (12) 0.0500 (11) 0.0601 (12) 0.0267 (10) 0.0073 (10) 0.0188 (9)
C16 0.0519 (11) 0.0423 (10) 0.0557 (11) 0.0173 (8) 0.0165 (9) 0.0159 (9)
C17 0.0645 (13) 0.0549 (13) 0.0523 (12) 0.0206 (11) −0.0010 (10) 0.0092 (10)
C18 0.0647 (13) 0.0504 (12) 0.0556 (12) 0.0267 (10) −0.0008 (10) 0.0120 (9)
Geometric parameters (Å, º)
N1—C1 1.470 (2) C8—C9 1.364 (5)
N1—C4 1.476 (3) C8—H8 0.90 (4)
N1—C3 1.487 (3) C9—C10 1.381 (3)
N2—C2 1.283 (3) C9—H9 1.01 (4)
N2—C3 1.479 (3) C10—H10 0.99 (3)
N3—O2 1.225 (3) C11—H11C 1.02 (3)
N3—O1 1.225 (3) C11—H11B 0.95 (3)
N3—C16 1.462 (3) C11—H11A 0.95 (3)
C1—C2 1.488 (3) C12—H12A 0.99 (3)
C1—C4 1.506 (3) C12—H12B 0.97 (4)
C1—H1 0.95 (3) C12—H12C 0.98 (4)
C2—C5 1.475 (3) C13—C18 1.386 (3)
C3—C11 1.516 (3) C13—C14 1.388 (3)
C3—C12 1.527 (3) C14—C15 1.373 (3)
C4—C13 1.479 (3) C14—H14 0.96 (3)
C4—H4 0.98 (2) C15—C16 1.378 (3)
C5—C6 1.385 (3) C15—H15 0.96 (3)
C5—C10 1.387 (3) C16—C17 1.371 (3)
C6—H6 0.94 (3) C17—H17 0.86 (3)
C7—C8 1.372 (4) C18—H18 0.95 (3)
C7—H7 0.91 (3)
C1—N1—C4 61.48 (12) C9—C8—H8 121 (2)
C1—N1—C3 104.80 (15) C7—C8—H8 119 (2)
C4—N1—C3 115.01 (16) C8—C9—C10 120.7 (3)
C2—N2—C3 108.40 (16) C8—C9—H9 121 (2)
O2—N3—O1 123.3 (2) C10—C9—H9 119 (2)
O2—N3—C16 118.3 (2) C9—C10—C5 119.9 (2)
O1—N3—C16 118.3 (2) C9—C10—H10 121.4 (15)
N1—C1—C2 105.26 (15) C5—C10—H10 118.6 (15)
N1—C1—C4 59.46 (12) C3—C11—H11C 113.0 (19)
C2—C1—C4 112.94 (16) C3—C11—H11B 109.6 (18)
N1—C1—H1 120.0 (14) H11C—C11—H11B 111 (3)
C2—C1—H1 122.5 (15) C3—C11—H11A 103.9 (19)
C4—C1—H1 119.7 (14) H11C—C11—H11A 113 (3)
N2—C2—C5 123.08 (18) H11B—C11—H11A 106 (3)
N2—C2—C1 113.30 (16) C3—C12—H12A 110.2 (15)
C5—C2—C1 123.62 (16) C3—C12—H12B 110 (2)
N2—C3—N1 107.74 (15) H12A—C12—H12B 109 (3)
N2—C3—C11 110.61 (19) C3—C12—H12C 109 (2)
N1—C3—C11 112.42 (18) H12A—C12—H12C 114 (3)
N2—C3—C12 107.32 (18) H12B—C12—H12C 104 (3)
N1—C3—C12 106.80 (18) C18—C13—C14 118.81 (19)
C11—C3—C12 111.7 (2) C18—C13—C4 121.63 (19)
N1—C4—C13 116.57 (17) C14—C13—C4 119.54 (18)
N1—C4—C1 59.06 (12) C15—C14—C13 120.9 (2)
C13—C4—C1 119.98 (17) C15—C14—H14 121.8 (15)
N1—C4—H4 119.2 (13) C13—C14—H14 117.2 (15)
C13—C4—H4 114.0 (13) C14—C15—C16 118.8 (2)
C1—C4—H4 117.3 (13) C14—C15—H15 120.8 (17)
C6—C5—C10 119.3 (2) C16—C15—H15 120.3 (17)
C6—C5—C2 120.58 (19) C17—C16—C15 121.9 (2)
C10—C5—C2 120.12 (18) C17—C16—N3 119.4 (2)
C5—C6—C7 119.9 (2) C15—C16—N3 118.7 (2)
C5—C6—H6 119.2 (16) C16—C17—C18 118.6 (2)
C7—C6—H6 120.9 (16) C16—C17—H17 125 (2)
C8—C7—C6 120.2 (2) C18—C17—H17 116 (2)
C8—C7—H7 119 (2) C17—C18—C13 120.9 (2)
C6—C7—H7 121 (2) C17—C18—H18 120.7 (16)
C9—C8—C7 120.0 (2) C13—C18—H18 118.4 (16)
C4—N1—C1—C2 −107.94 (17) C1—C2—C5—C10 166.39 (19)
C3—N1—C1—C2 2.80 (18) C10—C5—C6—C7 0.9 (3)
C3—N1—C1—C4 110.75 (16) C2—C5—C6—C7 179.60 (19)
C3—N2—C2—C5 174.79 (17) C5—C6—C7—C8 −1.1 (4)
supporting information
sup-5 Acta Cryst. (2005). E61, o667–o668
N1—C1—C2—N2 1.9 (2) C7—C8—C9—C10 −0.4 (4)
C4—C1—C2—N2 −61.0 (2) C8—C9—C10—C5 0.2 (4)
N1—C1—C2—C5 −178.68 (16) C6—C5—C10—C9 −0.4 (3)
C4—C1—C2—C5 118.47 (19) C2—C5—C10—C9 −179.1 (2)
C2—N2—C3—N1 7.4 (2) N1—C4—C13—C18 19.5 (3)
C2—N2—C3—C11 130.65 (19) C1—C4—C13—C18 −48.4 (3)
C2—N2—C3—C12 −107.26 (19) N1—C4—C13—C14 −162.02 (17)
C1—N1—C3—N2 −6.0 (2) C1—C4—C13—C14 130.0 (2)
C4—N1—C3—N2 59.0 (2) C18—C13—C14—C15 1.8 (3)
C1—N1—C3—C11 −128.14 (19) C4—C13—C14—C15 −176.72 (19)
C4—N1—C3—C11 −63.1 (2) C13—C14—C15—C16 −0.1 (3)
C1—N1—C3—C12 109.02 (18) C14—C15—C16—C17 −1.3 (3)
C4—N1—C3—C12 174.07 (17) C14—C15—C16—N3 177.43 (18)
C1—N1—C4—C13 −110.59 (19) O2—N3—C16—C17 −179.5 (2)
C3—N1—C4—C13 155.56 (16) O1—N3—C16—C17 4.0 (3)
C3—N1—C4—C1 −93.85 (17) O2—N3—C16—C15 1.8 (3)
C2—C1—C4—N1 94.72 (17) O1—N3—C16—C15 −174.8 (2)
N1—C1—C4—C13 104.8 (2) C15—C16—C17—C18 0.9 (4)
C2—C1—C4—C13 −160.44 (17) N3—C16—C17—C18 −177.8 (2)
N2—C2—C5—C6 167.06 (18) C16—C17—C18—C13 0.9 (4)
C1—C2—C5—C6 −12.3 (3) C14—C13—C18—C17 −2.2 (3)
