organic compounds
2,3-Dihydro-1H-pyrrolo[1,2-a]indole-9-carbonitrile
aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Private Bag 3, PO WITS, 2050, Johannesburg, South Africa
*Correspondence e-mail: joseph.michael@wits.ac.za
The 12H10N2, which may serve as a model for mitosenes, contains two independent molecules. The conformation of the five-membered rings in both molecules is envelope, with the central CH2—CH2—CH2 C atom at the flap in each case. In the crystal, they interact by a combination of weak C—H⋯N and π–π interactions [centroid–centroid distances = 3.616 (1) and 3.499 (1) Å] and C—H⋯π contacts.
of the title compound, CRelated literature
For the synthesis of the title compound by intramolecular Heck reaction of [1-(2-bromophenyl)pyrrolidin-2-ylidene]-acetonitrile, see: Michael et al. (1993). For an alternative synthesis by of [2-(2-oxopyrrolidin-1-yl)phenyl]acetonitrile with sodium hydride, see: Verboom et al. (1986). For background to mitosenes, see: Franck (1978); Kasai & Kono (1992).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); 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 DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Supporting information
10.1107/S1600536812045345/bh2462sup1.cif
contains datablocks global, I. DOI:Supporting information file. DOI: 10.1107/S1600536812045345/bh2462Isup2.mol
Structure factors: contains datablock I. DOI: 10.1107/S1600536812045345/bh2462Isup3.hkl
Supporting information file. DOI: 10.1107/S1600536812045345/bh2462Isup4.cml
The title compound was prepared by reaction of [1-(2-bromophenyl)pyrrolidin-2-ylidene]acetonitrile (350 mg, 1.33 mmol) with palladium(II) acetate (299 mg, 1.33 mmol, 1 eq.), tri-o-tolylphosphine (407 mg, 1.33 mmol) and triethylamine (0.19 ml, 1.33 mmol), heated under reflux in acetonitrile (7 ml) for 96 h. The crude oil obtained after evaporation of the solvent (1.20 g) was purified by
on silica gel with hexane/ethyl acetate (5:1 v/v) as to yield a colourless solid (133 mg, 55%). Recrystallization from ethyl acetate produced colourless blocks, m.p. 400–401 K. An alternative synthesis is available from the literature, based on of [2-(2-oxopyrrolidin-1-yl)phenyl]acetonitrile with sodium hydride (Verboom et al., 1986).The C-bound H atoms were geometrically placed (C—H bond lengths of 0.95 for aromatic CH and 0.99 for methylene CH2) and refined as riding with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2005); cell
SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker 2004); 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 DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).Fig. 1. The asymmetric unit of (I) showing the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. | |
Fig. 2. View of the hydrogen bonds of (I). C—H···N are shown as dashed red lines and C—H···π as dashed blue lines. H atoms not involved in hydrogen bonding are omitted for clarity. |
C12H10N2 | Z = 4 |
Mr = 182.22 | F(000) = 384 |
Triclinic, P1 | Dx = 1.258 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.1383 (3) Å | Cell parameters from 3160 reflections |
b = 9.5340 (3) Å | θ = 2.4–28.2° |
c = 12.3138 (4) Å | µ = 0.08 mm−1 |
α = 90.794 (2)° | T = 173 K |
β = 90.528 (2)° | Block, colourless |
γ = 116.272 (2)° | 0.50 × 0.45 × 0.30 mm |
V = 961.78 (5) Å3 |
Bruker APEXII CCD area-detector diffractometer | 2809 reflections with I > 2σ(I) |
ω scans | Rint = 0.023 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | θmax = 25.5°, θmin = 1.7° |
Tmin = 0.963, Tmax = 0.978 | h = −10→11 |
7592 measured reflections | k = −11→11 |
3498 independent reflections | l = −14→14 |
Refinement on F2 | 0 constraints |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.038 | w = 1/[σ2(Fo2) + (0.0414P)2 + 0.2024P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.097 | (Δ/σ)max < 0.001 |
S = 1.04 | Δρmax = 0.19 e Å−3 |
3498 reflections | Δρmin = −0.15 e Å−3 |
254 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.027 (2) |
C12H10N2 | γ = 116.272 (2)° |
Mr = 182.22 | V = 961.78 (5) Å3 |
Triclinic, P1 | Z = 4 |
a = 9.1383 (3) Å | Mo Kα radiation |
b = 9.5340 (3) Å | µ = 0.08 mm−1 |
c = 12.3138 (4) Å | T = 173 K |
α = 90.794 (2)° | 0.50 × 0.45 × 0.30 mm |
β = 90.528 (2)° |
Bruker APEXII CCD area-detector diffractometer | 3498 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2809 reflections with I > 2σ(I) |
Tmin = 0.963, Tmax = 0.978 | Rint = 0.023 |
7592 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.19 e Å−3 |
3498 reflections | Δρmin = −0.15 e Å−3 |
254 parameters |
x | y | z | Uiso*/Ueq | ||
C1A | −0.10944 (18) | 0.17265 (18) | 0.14642 (13) | 0.0397 (4) | |
H1A1 | −0.1299 | 0.1843 | 0.2241 | 0.048* | |
H1A2 | −0.211 | 0.0937 | 0.1114 | 0.048* | |
C2A | −0.0463 (2) | 0.32983 (19) | 0.08862 (13) | 0.0447 (4) | |
H2A1 | −0.018 | 0.4164 | 0.1424 | 0.054* | |
H2A2 | −0.1311 | 0.3303 | 0.0382 | 0.054* | |
C3A | 0.10660 (19) | 0.35042 (18) | 0.02512 (13) | 0.0419 (4) | |
H3A1 | 0.0836 | 0.3383 | −0.0541 | 0.05* | |
H3A2 | 0.1987 | 0.4544 | 0.0405 | 0.05* | |
C4A | 0.14316 (17) | 0.22297 (16) | 0.06621 (11) | 0.0323 (3) | |
C5A | 0.25796 (16) | 0.16684 (15) | 0.05611 (11) | 0.0307 (3) | |
C6A | 0.20402 (16) | 0.02878 (15) | 0.12165 (11) | 0.0296 (3) | |
C7A | 0.26457 (17) | −0.07929 (17) | 0.14459 (12) | 0.0358 (3) | |
H7A | 0.3632 | −0.0697 | 0.1133 | 0.043* | |
C8A | 0.17821 (18) | −0.20006 (17) | 0.21350 (13) | 0.0407 (4) | |
H8A | 0.2178 | −0.2746 | 0.2291 | 0.049* | |
C9A | 0.03390 (18) | −0.21502 (18) | 0.26077 (12) | 0.0422 (4) | |
H9A | −0.0218 | −0.2986 | 0.3087 | 0.051* | |
C10A | −0.02975 (18) | −0.11093 (17) | 0.23936 (12) | 0.0375 (4) | |
H10A | −0.1283 | −0.1214 | 0.2712 | 0.045* | |
C11A | 0.05677 (16) | 0.00985 (16) | 0.16923 (11) | 0.0304 (3) | |
C12A | 0.40232 (18) | 0.23407 (17) | −0.00564 (12) | 0.0361 (3) | |
N1A | 0.02493 (14) | 0.13034 (13) | 0.13356 (9) | 0.0325 (3) | |
N2A | 0.52063 (17) | 0.28700 (16) | −0.05460 (11) | 0.0503 (4) | |
C1B | 0.49796 (18) | 0.56982 (17) | 0.73859 (12) | 0.0365 (3) | |
H1B1 | 0.6163 | 0.6215 | 0.7237 | 0.044* | |
H1B2 | 0.4801 | 0.5177 | 0.8096 | 0.044* | |
C2B | 0.4245 (2) | 0.68616 (19) | 0.73518 (13) | 0.0463 (4) | |
H2B1 | 0.5104 | 0.7941 | 0.7484 | 0.056* | |
H2B2 | 0.3405 | 0.6617 | 0.7915 | 0.056* | |
C3B | 0.34765 (17) | 0.67027 (16) | 0.62107 (12) | 0.0346 (3) | |
H3B1 | 0.2426 | 0.6768 | 0.6243 | 0.041* | |
H3B2 | 0.4221 | 0.7519 | 0.5724 | 0.041* | |
C4B | 0.32309 (15) | 0.51204 (15) | 0.58477 (11) | 0.0281 (3) | |
C5B | 0.24306 (16) | 0.40067 (15) | 0.50510 (11) | 0.0297 (3) | |
C6B | 0.27990 (16) | 0.27070 (15) | 0.52490 (11) | 0.0292 (3) | |
C7B | 0.23096 (18) | 0.12242 (16) | 0.47682 (12) | 0.0375 (4) | |
H7B | 0.1594 | 0.0902 | 0.4153 | 0.045* | |
C8B | 0.28912 (19) | 0.02423 (17) | 0.52084 (13) | 0.0422 (4) | |
H8B | 0.2565 | −0.0768 | 0.4891 | 0.051* | |
C9B | 0.39485 (19) | 0.06978 (17) | 0.61108 (13) | 0.0406 (4) | |
H9B | 0.4336 | −0.0004 | 0.6387 | 0.049* | |
C10B | 0.44413 (17) | 0.21428 (16) | 0.66078 (12) | 0.0344 (3) | |
H10B | 0.5156 | 0.2452 | 0.7224 | 0.041* | |
C11B | 0.38481 (16) | 0.31282 (15) | 0.61696 (11) | 0.0285 (3) | |
C12B | 0.14474 (18) | 0.41506 (17) | 0.42058 (12) | 0.0359 (3) | |
N1B | 0.40605 (13) | 0.45930 (12) | 0.65134 (9) | 0.0282 (3) | |
N2B | 0.06647 (18) | 0.42763 (17) | 0.35107 (12) | 0.0546 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0365 (8) | 0.0434 (9) | 0.0459 (9) | 0.0241 (7) | −0.0033 (7) | −0.0072 (7) |
C2A | 0.0552 (10) | 0.0451 (9) | 0.0449 (9) | 0.0325 (8) | −0.0066 (8) | −0.0048 (7) |
C3A | 0.0459 (9) | 0.0358 (8) | 0.0463 (9) | 0.0202 (7) | −0.0062 (7) | 0.0025 (7) |
C4A | 0.0342 (8) | 0.0300 (7) | 0.0291 (7) | 0.0111 (6) | −0.0051 (6) | −0.0002 (6) |
C5A | 0.0299 (7) | 0.0304 (7) | 0.0295 (7) | 0.0113 (6) | −0.0013 (6) | 0.0010 (6) |
C6A | 0.0268 (7) | 0.0304 (7) | 0.0285 (7) | 0.0100 (6) | −0.0044 (6) | −0.0013 (6) |
C7A | 0.0294 (7) | 0.0363 (8) | 0.0416 (8) | 0.0147 (6) | −0.0052 (6) | 0.0001 (6) |
C8A | 0.0386 (8) | 0.0353 (8) | 0.0490 (9) | 0.0172 (7) | −0.0094 (7) | 0.0060 (7) |
C9A | 0.0397 (9) | 0.0385 (8) | 0.0403 (9) | 0.0098 (7) | −0.0012 (7) | 0.0101 (7) |
C10A | 0.0316 (8) | 0.0392 (8) | 0.0369 (8) | 0.0111 (7) | 0.0024 (6) | 0.0042 (6) |
C11A | 0.0302 (7) | 0.0316 (7) | 0.0285 (7) | 0.0131 (6) | −0.0028 (6) | −0.0015 (6) |
C12A | 0.0379 (8) | 0.0341 (8) | 0.0345 (8) | 0.0142 (7) | 0.0007 (7) | 0.0028 (6) |
N1A | 0.0317 (6) | 0.0331 (6) | 0.0344 (6) | 0.0160 (5) | 0.0001 (5) | −0.0001 (5) |
N2A | 0.0452 (8) | 0.0503 (8) | 0.0512 (8) | 0.0169 (7) | 0.0130 (7) | 0.0078 (7) |
C1B | 0.0389 (8) | 0.0356 (8) | 0.0350 (8) | 0.0169 (7) | −0.0070 (6) | −0.0070 (6) |
C2B | 0.0563 (10) | 0.0428 (9) | 0.0467 (9) | 0.0287 (8) | −0.0098 (8) | −0.0113 (7) |
C3B | 0.0345 (8) | 0.0295 (7) | 0.0429 (8) | 0.0171 (6) | 0.0002 (6) | −0.0007 (6) |
C4B | 0.0263 (7) | 0.0274 (7) | 0.0319 (7) | 0.0131 (6) | 0.0043 (6) | 0.0047 (6) |
C5B | 0.0272 (7) | 0.0297 (7) | 0.0304 (7) | 0.0111 (6) | −0.0003 (6) | 0.0034 (6) |
C6B | 0.0271 (7) | 0.0274 (7) | 0.0313 (7) | 0.0105 (6) | 0.0036 (6) | 0.0029 (6) |
C7B | 0.0376 (8) | 0.0310 (8) | 0.0381 (8) | 0.0102 (6) | −0.0006 (7) | −0.0028 (6) |
C8B | 0.0489 (9) | 0.0264 (7) | 0.0503 (9) | 0.0158 (7) | 0.0057 (8) | −0.0028 (7) |
C9B | 0.0460 (9) | 0.0325 (8) | 0.0507 (9) | 0.0237 (7) | 0.0073 (7) | 0.0077 (7) |
C10B | 0.0342 (8) | 0.0351 (8) | 0.0379 (8) | 0.0188 (6) | 0.0019 (6) | 0.0047 (6) |
C11B | 0.0272 (7) | 0.0263 (7) | 0.0318 (7) | 0.0115 (6) | 0.0043 (6) | 0.0035 (5) |
C12B | 0.0352 (8) | 0.0347 (8) | 0.0375 (8) | 0.0153 (7) | −0.0025 (7) | 0.0012 (6) |
N1B | 0.0285 (6) | 0.0279 (6) | 0.0297 (6) | 0.0139 (5) | −0.0022 (5) | −0.0002 (5) |
N2B | 0.0565 (9) | 0.0606 (9) | 0.0494 (9) | 0.0287 (8) | −0.0155 (7) | 0.0012 (7) |
C1A—N1A | 1.4616 (17) | C1B—N1B | 1.4624 (17) |
C1A—C2A | 1.535 (2) | C1B—C2B | 1.530 (2) |
C1A—H1A1 | 0.99 | C1B—H1B1 | 0.99 |
C1A—H1A2 | 0.99 | C1B—H1B2 | 0.99 |
C2A—C3A | 1.544 (2) | C2B—C3B | 1.540 (2) |
C2A—H2A1 | 0.99 | C2B—H2B1 | 0.99 |
C2A—H2A2 | 0.99 | C2B—H2B2 | 0.99 |
C3A—C4A | 1.4891 (19) | C3B—C4B | 1.4852 (18) |
C3A—H3A1 | 0.99 | C3B—H3B1 | 0.99 |
C3A—H3A2 | 0.99 | C3B—H3B2 | 0.99 |
C4A—N1A | 1.3517 (18) | C4B—N1B | 1.3552 (16) |
C4A—C5A | 1.3784 (19) | C4B—C5B | 1.3767 (19) |
C5A—C12A | 1.419 (2) | C5B—C12B | 1.4161 (19) |
C5A—C6A | 1.4455 (19) | C5B—C6B | 1.4437 (19) |
C6A—C7A | 1.3990 (19) | C6B—C7B | 1.4005 (19) |
C6A—C11A | 1.4104 (19) | C6B—C11B | 1.4114 (19) |
C7A—C8A | 1.380 (2) | C7B—C8B | 1.379 (2) |
C7A—H7A | 0.95 | C7B—H7B | 0.95 |
C8A—C9A | 1.396 (2) | C8B—C9B | 1.397 (2) |
C8A—H8A | 0.95 | C8B—H8B | 0.95 |
C9A—C10A | 1.381 (2) | C9B—C10B | 1.378 (2) |
C9A—H9A | 0.95 | C9B—H9B | 0.95 |
C10A—C11A | 1.3896 (19) | C10B—C11B | 1.3882 (18) |
C10A—H10A | 0.95 | C10B—H10B | 0.95 |
C11A—N1A | 1.3800 (17) | C11B—N1B | 1.3818 (17) |
C12A—N2A | 1.1508 (19) | C12B—N2B | 1.1515 (18) |
N1A—C1A—C2A | 102.51 (12) | N1B—C1B—C2B | 101.64 (11) |
N1A—C1A—H1A1 | 111.3 | N1B—C1B—H1B1 | 111.4 |
C2A—C1A—H1A1 | 111.3 | C2B—C1B—H1B1 | 111.4 |
N1A—C1A—H1A2 | 111.3 | N1B—C1B—H1B2 | 111.4 |
C2A—C1A—H1A2 | 111.3 | C2B—C1B—H1B2 | 111.4 |
H1A1—C1A—H1A2 | 109.2 | H1B1—C1B—H1B2 | 109.3 |
C1A—C2A—C3A | 107.49 (12) | C1B—C2B—C3B | 106.64 (12) |
C1A—C2A—H2A1 | 110.2 | C1B—C2B—H2B1 | 110.4 |
C3A—C2A—H2A1 | 110.2 | C3B—C2B—H2B1 | 110.4 |
C1A—C2A—H2A2 | 110.2 | C1B—C2B—H2B2 | 110.4 |
C3A—C2A—H2A2 | 110.2 | C3B—C2B—H2B2 | 110.4 |
H2A1—C2A—H2A2 | 108.5 | H2B1—C2B—H2B2 | 108.6 |
C4A—C3A—C2A | 103.49 (12) | C4B—C3B—C2B | 102.46 (11) |
C4A—C3A—H3A1 | 111.1 | C4B—C3B—H3B1 | 111.3 |
C2A—C3A—H3A1 | 111.1 | C2B—C3B—H3B1 | 111.3 |
C4A—C3A—H3A2 | 111.1 | C4B—C3B—H3B2 | 111.3 |
C2A—C3A—H3A2 | 111.1 | C2B—C3B—H3B2 | 111.3 |
H3A1—C3A—H3A2 | 109 | H3B1—C3B—H3B2 | 109.2 |
N1A—C4A—C5A | 109.25 (12) | N1B—C4B—C5B | 109.20 (11) |
N1A—C4A—C3A | 110.47 (12) | N1B—C4B—C3B | 110.27 (11) |
C5A—C4A—C3A | 140.26 (13) | C5B—C4B—C3B | 140.53 (12) |
C4A—C5A—C12A | 126.19 (12) | C4B—C5B—C12B | 125.28 (13) |
C4A—C5A—C6A | 106.83 (12) | C4B—C5B—C6B | 106.93 (11) |
C12A—C5A—C6A | 126.98 (13) | C12B—C5B—C6B | 127.78 (13) |
C7A—C6A—C11A | 118.89 (12) | C7B—C6B—C11B | 118.82 (12) |
C7A—C6A—C5A | 134.72 (13) | C7B—C6B—C5B | 134.60 (13) |
C11A—C6A—C5A | 106.40 (12) | C11B—C6B—C5B | 106.53 (11) |
C8A—C7A—C6A | 118.66 (14) | C8B—C7B—C6B | 118.46 (14) |
C8A—C7A—H7A | 120.7 | C8B—C7B—H7B | 120.8 |
C6A—C7A—H7A | 120.7 | C6B—C7B—H7B | 120.8 |
C7A—C8A—C9A | 121.37 (14) | C7B—C8B—C9B | 121.55 (13) |
C7A—C8A—H8A | 119.3 | C7B—C8B—H8B | 119.2 |
C9A—C8A—H8A | 119.3 | C9B—C8B—H8B | 119.2 |
C10A—C9A—C8A | 121.45 (14) | C10B—C9B—C8B | 121.40 (13) |
C10A—C9A—H9A | 119.3 | C10B—C9B—H9B | 119.3 |
C8A—C9A—H9A | 119.3 | C8B—C9B—H9B | 119.3 |
C9A—C10A—C11A | 117.06 (14) | C9B—C10B—C11B | 117.09 (14) |
C9A—C10A—H10A | 121.5 | C9B—C10B—H10B | 121.5 |
C11A—C10A—H10A | 121.5 | C11B—C10B—H10B | 121.5 |
N1A—C11A—C10A | 130.29 (13) | N1B—C11B—C10B | 130.31 (13) |
N1A—C11A—C6A | 107.14 (11) | N1B—C11B—C6B | 106.98 (11) |
C10A—C11A—C6A | 122.57 (13) | C10B—C11B—C6B | 122.67 (13) |
N2A—C12A—C5A | 178.68 (16) | N2B—C12B—C5B | 179.15 (17) |
C4A—N1A—C11A | 110.38 (11) | C4B—N1B—C11B | 110.34 (11) |
C4A—N1A—C1A | 114.62 (11) | C4B—N1B—C1B | 113.89 (11) |
C11A—N1A—C1A | 134.86 (12) | C11B—N1B—C1B | 135.75 (11) |
N1A—C1A—C2A—C3A | 11.78 (15) | N1B—C1B—C2B—C3B | −21.63 (16) |
C1A—C2A—C3A—C4A | −10.85 (16) | C1B—C2B—C3B—C4B | 21.44 (16) |
C2A—C3A—C4A—N1A | 5.68 (16) | C2B—C3B—C4B—N1B | −13.05 (15) |
C2A—C3A—C4A—C5A | −175.95 (17) | C2B—C3B—C4B—C5B | 166.94 (17) |
N1A—C4A—C5A—C12A | −178.53 (13) | N1B—C4B—C5B—C12B | −179.62 (13) |
C3A—C4A—C5A—C12A | 3.1 (3) | C3B—C4B—C5B—C12B | 0.4 (3) |
N1A—C4A—C5A—C6A | 0.56 (15) | N1B—C4B—C5B—C6B | 0.12 (15) |
C3A—C4A—C5A—C6A | −177.82 (17) | C3B—C4B—C5B—C6B | −179.87 (16) |
C4A—C5A—C6A—C7A | 179.59 (15) | C4B—C5B—C6B—C7B | 176.58 (15) |
C12A—C5A—C6A—C7A | −1.3 (3) | C12B—C5B—C6B—C7B | −3.7 (3) |
C4A—C5A—C6A—C11A | −0.40 (14) | C4B—C5B—C6B—C11B | −0.84 (15) |
C12A—C5A—C6A—C11A | 178.68 (13) | C12B—C5B—C6B—C11B | 178.89 (13) |
C11A—C6A—C7A—C8A | −0.4 (2) | C11B—C6B—C7B—C8B | −0.8 (2) |
C5A—C6A—C7A—C8A | 179.65 (14) | C5B—C6B—C7B—C8B | −177.95 (15) |
C6A—C7A—C8A—C9A | −0.5 (2) | C6B—C7B—C8B—C9B | −0.2 (2) |
C7A—C8A—C9A—C10A | 0.9 (2) | C7B—C8B—C9B—C10B | 0.7 (2) |
C8A—C9A—C10A—C11A | −0.4 (2) | C8B—C9B—C10B—C11B | −0.3 (2) |
C9A—C10A—C11A—N1A | −179.53 (14) | C9B—C10B—C11B—N1B | 176.69 (13) |
C9A—C10A—C11A—C6A | −0.5 (2) | C9B—C10B—C11B—C6B | −0.7 (2) |
C7A—C6A—C11A—N1A | −179.89 (12) | C7B—C6B—C11B—N1B | −176.67 (12) |
C5A—C6A—C11A—N1A | 0.10 (14) | C5B—C6B—C11B—N1B | 1.24 (14) |
C7A—C6A—C11A—C10A | 0.9 (2) | C7B—C6B—C11B—C10B | 1.2 (2) |
C5A—C6A—C11A—C10A | −179.10 (13) | C5B—C6B—C11B—C10B | 179.14 (12) |
C5A—C4A—N1A—C11A | −0.52 (15) | C5B—C4B—N1B—C11B | 0.68 (15) |
C3A—C4A—N1A—C11A | 178.38 (11) | C3B—C4B—N1B—C11B | −179.33 (11) |
C5A—C4A—N1A—C1A | −176.82 (11) | C5B—C4B—N1B—C1B | 179.18 (11) |
C3A—C4A—N1A—C1A | 2.08 (16) | C3B—C4B—N1B—C1B | −0.83 (16) |
C10A—C11A—N1A—C4A | 179.36 (14) | C10B—C11B—N1B—C4B | −178.89 (14) |
C6A—C11A—N1A—C4A | 0.25 (15) | C6B—C11B—N1B—C4B | −1.21 (15) |
C10A—C11A—N1A—C1A | −5.4 (3) | C10B—C11B—N1B—C1B | 3.1 (3) |
C6A—C11A—N1A—C1A | 175.50 (14) | C6B—C11B—N1B—C1B | −179.25 (14) |
C2A—C1A—N1A—C4A | −8.84 (16) | C2B—C1B—N1B—C4B | 14.35 (16) |
C2A—C1A—N1A—C11A | 176.06 (14) | C2B—C1B—N1B—C11B | −167.66 (15) |
Cg1 and Cg2 are the centroids of the C6A–C11A and C6B–C11B rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1A—H1A1···N2B | 0.99 | 2.68 | 3.338 (2) | 124 |
C2A—H2A1···N2B | 0.99 | 2.66 | 3.373 (2) | 129 |
C3A—H3A2···N2Ai | 0.99 | 2.66 | 3.634 (2) | 168 |
C3B—H3B1···N2Bii | 0.99 | 2.57 | 3.495 (2) | 156 |
C3A—H3A1···Cg1iii | 0.99 | 2.79 | 3.545 (2) | 135 |
C3B—H3B2···Cg2iv | 0.99 | 2.67 | 3.523 (2) | 146 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z; (iv) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C12H10N2 |
Mr | 182.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 9.1383 (3), 9.5340 (3), 12.3138 (4) |
α, β, γ (°) | 90.794 (2), 90.528 (2), 116.272 (2) |
V (Å3) | 961.78 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.45 × 0.30 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.963, 0.978 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7592, 3498, 2809 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.097, 1.04 |
No. of reflections | 3498 |
No. of parameters | 254 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.19, −0.15 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Cg1 and Cg2 are the centroids of the C6A–C11A and C6B–C11B rings, respectively. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1A—H1A1···N2B | 0.99 | 2.68 | 3.338 (2) | 124 |
C2A—H2A1···N2B | 0.99 | 2.66 | 3.373 (2) | 129 |
C3A—H3A2···N2Ai | 0.99 | 2.66 | 3.634 (2) | 168 |
C3B—H3B1···N2Bii | 0.99 | 2.57 | 3.495 (2) | 156 |
C3A—H3A1···Cg1iii | 0.99 | 2.79 | 3.545 (2) | 135 |
C3B—H3B2···Cg2iv | 0.99 | 2.67 | 3.523 (2) | 146 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z+1; (iii) −x, −y, −z; (iv) −x+1, −y+1, −z+1. |
Acknowledgements
This work was supported by the University of the Witwatersrand and the Molecular Sciences Institute, which are thanked for providing the infrastructure required to do this work. Ms C. Wilson is thanked for carrying out the preliminary synthesis.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The mitosenes, naturally occurring biologically active degradation products of the important mitomycin antibiotics (Franck, 1978; Kasai & Kono, 1992) are characterized by the presence of a pyrrolo[1,2-a]indole core. The title compound, 2,3-dihydro-1H-pyrrolo[1,2-a]indole-9-carbonitrile, was prepared as part of a model study on the use of intramolecular Heck reactions for creating this core from various [1-(2-bromoaryl)pyrrolidin-2-ylidene]acetates and analogues (Michael et al., 1993).
The asymmetric unit of (I) consists of two molecules, labelled A and B, on general positions. Fig. 1 shows the atomic numbering scheme. The hydrogen bonding of (I) consists of weak C—H···N hydrogen bonds and various π–π interactions. Each molecule in the asymmetric unit makes centrosymmetric dimers using the C3A—H3A2···N2A and C3B—H3B1···N2B hydrogen bonds, shown explicitly for the B molecule in Fig. 2. Between the A and B molecules, two ethylene groups from the A molecule hydrogen bond to the cyanide N atom of the B molecule, through C1A—H1A1···N2B and C2A—H2A1···N2B hydrogen bonds. In addition, both A/A and B/B molecules sit parallel to each other and undergo π–π interactions, with distances of 3.616 (1) Å for A···A and 3.499 (1) Å for B···B (Fig. 2). Also C—H···π contacts are formed between those same A/A and B/B molecules, C3A—H3A1···Cg1iii [Cg1: C6A to C11A; symmetry operator: (iii) -x, -y, -z] and C3B—H3B2···Cg2iv [Cg2: C6B to C11B; symmetry operator: (iv) 1-x, 1-y, 1-z].