organic compounds
rac-12-Selena-13,14-diazatricyclo[9.3.0.02,4]tetradeca-11,13-diene
aJohannes Gutenberg University Mainz, Department of Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
*Correspondence e-mail: detert@uni-mainz.de
The centrosymmetric 11H16N2Se, is built up from alternating strands of (R,R)- and (S,S)-enantiomers. These strands, which propagate along the c-axis direction, are composed of homochiral molecules related to each other by twofold screw axes. The shape of the molecule is an almost planar unit around the selenadiazole ring with a hexamethylene chain as an arched handle.
of the title compound, CKeywords: crystal structure; heterocycles; medium-sized ring; selenium.
CCDC reference: 2021398
Structure description
1,2,3-Selenadiazoles are synthesized from SeO2-oxidation of (Yalpani et al., 1971; Al-Smadi & Ratrout, 2004) and are important intermediates for the synthesis of medium-sized (Meier, 1972), heterocyclic (Detert, 2011), and strained cycloalkynes (Bissinger et al. 1988).
The arbitrarily chosen asymmetric molecule of the title compound (Fig. 1) has S configurations for atoms C5 and C6 but crystal symmetry generates a The selenadiazole ring with the directly bound carbon atoms and one bond of the cyclopropane ring is almost planar, with a maximum deviation from this plane of 0.037 (2) Å at C12 and the dihedral angle between the selenadiazole ring and the cyclopropane ring is 69.0 (2)°. Though the carbocyclic part is of medium ring size, the hexamethylene tether appears to be free of Pitzer and Prelog strain.
No directional interactions beyond normal van der Waals contacts could be identified in the crystal. The packing consists of strands of homochiral molecules, related to each other by twofold screw axes, propagating along the c-axis direction. The (R,R)- and (S,S)-enantiomers alternate along the a-axis direction, being related by crystallographic c-glides (Fig. 2).
Synthesis and crystallization
The title compound was prepared in ten steps from cyclooctene according to Moore & Ward (1963), Moore & Bertelson (1962), Gardner & Narayana (1961), Detert & Meier (1997) and Whitham & Zaidlewicz (1972). Recrystallization from petroleum ether gave slightly pinkish crystals with m.p. 369 K.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 1Structural data
CCDC reference: 2021398
https://doi.org/10.1107/S2414314620010810/hb4354sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620010810/hb4354Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314620010810/hb4354Isup3.cml
Data collection: X-AREA WinXpose (Stoe & Cie, 2019); cell
X-AREA Recipe (Stoe & Cie, 2019); data reduction: X-AREA Integrate (Stoe & Cie, 2019); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2020).C11H16N2Se | F(000) = 520 |
Mr = 255.22 | Dx = 1.588 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 12.0239 (6) Å | Cell parameters from 11220 reflections |
b = 7.1317 (3) Å | θ = 2.9–28.5° |
c = 12.6836 (7) Å | µ = 3.48 mm−1 |
β = 101.104 (4)° | T = 120 K |
V = 1067.27 (9) Å3 | Plate, colourless |
Z = 4 | 0.55 × 0.47 × 0.10 mm |
Stoe IPDS 2T diffractometer | 2570 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2364 reflections with I > 2σ(I) |
Detector resolution: 6.67 pixels mm-1 | Rint = 0.021 |
rotation method, ω scans | θmax = 28.0°, θmin = 3.3° |
Absorption correction: integration | h = −15→15 |
Tmin = 0.228, Tmax = 0.704 | k = −9→9 |
5541 measured reflections | l = −15→16 |
Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.035 | H-atom parameters constrained |
wR(F2) = 0.097 | w = 1/[σ2(Fo2) + (0.0573P)2 + 1.4452P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
2570 reflections | Δρmax = 1.13 e Å−3 |
127 parameters | Δρmin = −0.90 e Å−3 |
0 restraints |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Hydrogen atoms attached to carbon atoms were placed at calculated positions and were refined in the riding-model approximation with C—H = 0.95 Å and Uiso(H) = 1.2 Ueq(C). |
x | y | z | Uiso*/Ueq | ||
Se1 | 0.01806 (2) | 0.53889 (3) | 0.19801 (2) | 0.01717 (11) | |
N2 | 0.08518 (19) | 0.7735 (3) | 0.24245 (18) | 0.0195 (4) | |
N3 | 0.16960 (17) | 0.7494 (3) | 0.31890 (17) | 0.0167 (4) | |
C4 | 0.1961 (2) | 0.5686 (3) | 0.35355 (19) | 0.0131 (4) | |
C5 | 0.2954 (2) | 0.5360 (3) | 0.4406 (2) | 0.0144 (4) | |
H5 | 0.337544 | 0.417298 | 0.433140 | 0.017* | |
C6 | 0.2942 (2) | 0.5921 (3) | 0.55614 (18) | 0.0149 (4) | |
H6 | 0.225279 | 0.662016 | 0.567102 | 0.018* | |
C7 | 0.3456 (2) | 0.4626 (3) | 0.6468 (2) | 0.0177 (5) | |
H7A | 0.375621 | 0.539411 | 0.711012 | 0.021* | |
H7B | 0.410401 | 0.396039 | 0.626172 | 0.021* | |
C8 | 0.2633 (2) | 0.3164 (4) | 0.67731 (19) | 0.0178 (5) | |
H8A | 0.203057 | 0.382731 | 0.705866 | 0.021* | |
H8B | 0.305015 | 0.236704 | 0.735703 | 0.021* | |
C9 | 0.2071 (2) | 0.1890 (3) | 0.58429 (19) | 0.0173 (5) | |
H9A | 0.260533 | 0.170100 | 0.534790 | 0.021* | |
H9B | 0.192121 | 0.064881 | 0.613659 | 0.021* | |
C10 | 0.09558 (19) | 0.2684 (3) | 0.52058 (18) | 0.0154 (4) | |
H10A | 0.035621 | 0.252598 | 0.563508 | 0.018* | |
H10B | 0.105037 | 0.404482 | 0.509630 | 0.018* | |
C11 | 0.0569 (2) | 0.1748 (3) | 0.41110 (19) | 0.0170 (5) | |
H11A | −0.022326 | 0.212211 | 0.382070 | 0.020* | |
H11B | 0.058059 | 0.037076 | 0.421121 | 0.020* | |
C12 | 0.1307 (2) | 0.2250 (3) | 0.32802 (19) | 0.0147 (4) | |
H12A | 0.210110 | 0.187617 | 0.356552 | 0.018* | |
H12B | 0.103796 | 0.153162 | 0.261179 | 0.018* | |
C13 | 0.1270 (2) | 0.4310 (3) | 0.30231 (19) | 0.0143 (4) | |
C14 | 0.3690 (2) | 0.6950 (4) | 0.4927 (2) | 0.0195 (5) | |
H14A | 0.451685 | 0.673076 | 0.511923 | 0.023* | |
H14B | 0.346890 | 0.824166 | 0.468684 | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Se1 | 0.01788 (15) | 0.01843 (16) | 0.01400 (15) | 0.00192 (8) | 0.00010 (10) | 0.00198 (8) |
N2 | 0.0245 (10) | 0.0147 (9) | 0.0200 (11) | 0.0019 (8) | 0.0059 (8) | 0.0027 (8) |
N3 | 0.0199 (10) | 0.0135 (9) | 0.0180 (10) | 0.0013 (8) | 0.0068 (8) | 0.0017 (7) |
C4 | 0.0150 (10) | 0.0136 (9) | 0.0112 (10) | 0.0013 (8) | 0.0038 (8) | 0.0011 (8) |
C5 | 0.0148 (10) | 0.0156 (11) | 0.0130 (11) | −0.0013 (8) | 0.0034 (9) | −0.0015 (8) |
C6 | 0.0164 (10) | 0.0163 (10) | 0.0117 (10) | −0.0020 (9) | 0.0021 (8) | −0.0022 (8) |
C7 | 0.0177 (11) | 0.0213 (12) | 0.0135 (11) | −0.0028 (9) | 0.0017 (9) | −0.0002 (8) |
C8 | 0.0199 (11) | 0.0200 (11) | 0.0130 (11) | −0.0020 (9) | 0.0021 (9) | 0.0013 (9) |
C9 | 0.0218 (11) | 0.0166 (10) | 0.0128 (11) | −0.0008 (9) | 0.0013 (9) | 0.0013 (8) |
C10 | 0.0170 (10) | 0.0162 (10) | 0.0136 (11) | −0.0025 (8) | 0.0044 (9) | 0.0010 (8) |
C11 | 0.0184 (11) | 0.0157 (10) | 0.0166 (11) | −0.0058 (9) | 0.0027 (9) | −0.0015 (9) |
C12 | 0.0176 (10) | 0.0127 (10) | 0.0134 (10) | −0.0011 (8) | 0.0022 (8) | −0.0013 (8) |
C13 | 0.0154 (10) | 0.0166 (10) | 0.0109 (10) | 0.0020 (9) | 0.0027 (8) | 0.0024 (8) |
C14 | 0.0211 (11) | 0.0197 (11) | 0.0179 (12) | −0.0054 (10) | 0.0040 (9) | −0.0016 (9) |
Se1—C13 | 1.841 (2) | C8—H8A | 0.9900 |
Se1—N2 | 1.896 (2) | C8—H8B | 0.9900 |
N2—N3 | 1.273 (3) | C9—C10 | 1.535 (3) |
N3—C4 | 1.379 (3) | C9—H9A | 0.9900 |
C4—C13 | 1.367 (3) | C9—H9B | 0.9900 |
C4—C5 | 1.480 (3) | C10—C11 | 1.530 (3) |
C5—C14 | 1.510 (3) | C10—H10A | 0.9900 |
C5—C6 | 1.522 (3) | C10—H10B | 0.9900 |
C5—H5 | 1.0000 | C11—C12 | 1.544 (3) |
C6—C14 | 1.507 (3) | C11—H11A | 0.9900 |
C6—C7 | 1.511 (3) | C11—H11B | 0.9900 |
C6—H6 | 1.0000 | C12—C13 | 1.504 (3) |
C7—C8 | 1.538 (3) | C12—H12A | 0.9900 |
C7—H7A | 0.9900 | C12—H12B | 0.9900 |
C7—H7B | 0.9900 | C14—H14A | 0.9900 |
C8—C9 | 1.538 (3) | C14—H14B | 0.9900 |
C13—Se1—N2 | 87.26 (10) | C8—C9—H9A | 108.9 |
N3—N2—Se1 | 109.79 (16) | C10—C9—H9B | 108.9 |
N2—N3—C4 | 118.1 (2) | C8—C9—H9B | 108.9 |
C13—C4—N3 | 115.9 (2) | H9A—C9—H9B | 107.7 |
C13—C4—C5 | 124.8 (2) | C11—C10—C9 | 113.5 (2) |
N3—C4—C5 | 119.3 (2) | C11—C10—H10A | 108.9 |
C4—C5—C14 | 121.9 (2) | C9—C10—H10A | 108.9 |
C4—C5—C6 | 121.4 (2) | C11—C10—H10B | 108.9 |
C14—C5—C6 | 59.64 (15) | C9—C10—H10B | 108.9 |
C4—C5—H5 | 114.4 | H10A—C10—H10B | 107.7 |
C14—C5—H5 | 114.4 | C10—C11—C12 | 113.84 (19) |
C6—C5—H5 | 114.4 | C10—C11—H11A | 108.8 |
C14—C6—C7 | 120.4 (2) | C12—C11—H11A | 108.8 |
C14—C6—C5 | 59.79 (15) | C10—C11—H11B | 108.8 |
C7—C6—C5 | 119.6 (2) | C12—C11—H11B | 108.8 |
C14—C6—H6 | 115.3 | H11A—C11—H11B | 107.7 |
C7—C6—H6 | 115.3 | C13—C12—C11 | 112.17 (19) |
C5—C6—H6 | 115.3 | C13—C12—H12A | 109.2 |
C6—C7—C8 | 114.7 (2) | C11—C12—H12A | 109.2 |
C6—C7—H7A | 108.6 | C13—C12—H12B | 109.2 |
C8—C7—H7A | 108.6 | C11—C12—H12B | 109.2 |
C6—C7—H7B | 108.6 | H12A—C12—H12B | 107.9 |
C8—C7—H7B | 108.6 | C4—C13—C12 | 127.5 (2) |
H7A—C7—H7B | 107.6 | C4—C13—Se1 | 108.95 (17) |
C7—C8—C9 | 114.6 (2) | C12—C13—Se1 | 123.47 (18) |
C7—C8—H8A | 108.6 | C6—C14—C5 | 60.58 (15) |
C9—C8—H8A | 108.6 | C6—C14—H14A | 117.7 |
C7—C8—H8B | 108.6 | C5—C14—H14A | 117.7 |
C9—C8—H8B | 108.6 | C6—C14—H14B | 117.7 |
H8A—C8—H8B | 107.6 | C5—C14—H14B | 117.7 |
C10—C9—C8 | 113.3 (2) | H14A—C14—H14B | 114.8 |
C10—C9—H9A | 108.9 | ||
C13—Se1—N2—N3 | 0.23 (17) | C7—C8—C9—C10 | −89.4 (3) |
Se1—N2—N3—C4 | 0.2 (3) | C8—C9—C10—C11 | 163.53 (19) |
N2—N3—C4—C13 | −0.8 (3) | C9—C10—C11—C12 | −70.9 (3) |
N2—N3—C4—C5 | 178.6 (2) | C10—C11—C12—C13 | −62.5 (3) |
C13—C4—C5—C14 | 179.2 (2) | N3—C4—C13—C12 | −175.5 (2) |
N3—C4—C5—C14 | −0.1 (3) | C5—C4—C13—C12 | 5.1 (4) |
C13—C4—C5—C6 | −109.3 (3) | N3—C4—C13—Se1 | 0.9 (3) |
N3—C4—C5—C6 | 71.3 (3) | C5—C4—C13—Se1 | −178.47 (18) |
C4—C5—C6—C14 | −111.1 (2) | C11—C12—C13—C4 | 89.1 (3) |
C4—C5—C6—C7 | 138.9 (2) | C11—C12—C13—Se1 | −86.8 (2) |
C14—C5—C6—C7 | −110.0 (2) | N2—Se1—C13—C4 | −0.62 (17) |
C14—C6—C7—C8 | −159.1 (2) | N2—Se1—C13—C12 | 175.9 (2) |
C5—C6—C7—C8 | −88.8 (3) | C7—C6—C14—C5 | 108.7 (2) |
C6—C7—C8—C9 | 56.9 (3) | C4—C5—C14—C6 | 110.3 (2) |
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