Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801001672/na6042sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801001672/na6042Isup2.hkl |
CCDC reference: 159760
Anhydrous ZnBr2 (50 mg) was added to a mixture of 1-(indolin-1-ylmethyl)benzotriazole (1.99 mmol) and dodecyl vinyl ether (4 mmol) in dry tetrahydrofuran (20 ml) and then stirred at room temperature for 3 h. The solvent was removed under vacuum and the residue was separated by column chromatography (gradient: hexane/ethyl acetate) affording, in addition to the expected compound 6-dodecyloxy-1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinoline (210 mg), the title compound as a by-product (160 mg, m.p. 422–423 K). Compound (I) crystallized directly from the chromatographic solvents (hexane/ethyl acetate 3:2), affording crystals suitable for X-ray diffraction.
Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976) and PLATON (Spek, 2000); software used to prepare material for publication: SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
Fig. 1. A view of the title molecule with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. A view of the crystal structure. |
C17H16N4 | Dx = 1.334 Mg m−3 |
Mr = 275.35 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 5825 reflections |
a = 10.7112 (3) Å | θ = 1.0–27.5° |
b = 10.8297 (3) Å | µ = 0.08 mm−1 |
c = 23.6321 (5) Å | T = 150 K |
V = 2741.56 (12) Å3 | Block, red |
Z = 8 | 0.30 × 0.20 × 0.20 mm |
F(000) = 1168 |
KappaCCD diffractometer | 3083 independent reflections |
Radiation source: fine-focus sealed X-ray tube | 2317 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
ϕ and ω scans with κ offsets | θmax = 27.4°, θmin = 1.7° |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | h = −13→13 |
Tmin = 0.976, Tmax = 0.984 | k = −13→14 |
10806 measured reflections | l = −27→29 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.27 | w = 1/[σ2(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3 |
3083 reflections | (Δ/σ)max < 0.001 |
190 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
C17H16N4 | V = 2741.56 (12) Å3 |
Mr = 275.35 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.7112 (3) Å | µ = 0.08 mm−1 |
b = 10.8297 (3) Å | T = 150 K |
c = 23.6321 (5) Å | 0.30 × 0.20 × 0.20 mm |
KappaCCD diffractometer | 3083 independent reflections |
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) | 2317 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.984 | Rint = 0.077 |
10806 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.112 | H-atom parameters constrained |
S = 1.27 | Δρmax = 0.17 e Å−3 |
3083 reflections | Δρmin = −0.22 e Å−3 |
190 parameters |
Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm (Fox & Holmes, 1966) which effectively corrects for absorption effects. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used. no transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental table are calculated from the 'size' command in the SHELXL97 input file. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.52393 (14) | 0.00297 (12) | 0.23920 (6) | 0.0396 (3) | |
C2 | 0.57262 (13) | −0.01163 (13) | 0.17862 (6) | 0.0402 (3) | |
N3 | 0.46252 (11) | 0.01106 (9) | 0.14332 (4) | 0.0322 (3) | |
C4 | 0.47813 (13) | 0.04207 (11) | 0.08388 (5) | 0.0330 (3) | |
C5 | 0.35003 (12) | 0.06262 (11) | 0.05862 (5) | 0.0326 (3) | |
C6 | 0.28081 (12) | 0.16998 (10) | 0.08674 (5) | 0.0305 (3) | |
C6A | 0.29648 (12) | 0.16893 (10) | 0.15056 (5) | 0.0291 (3) | |
C7 | 0.23095 (13) | 0.24471 (11) | 0.18800 (5) | 0.0349 (3) | |
C8 | 0.25715 (14) | 0.24317 (11) | 0.24530 (5) | 0.0396 (3) | |
C9A | 0.41727 (13) | 0.09237 (11) | 0.23103 (5) | 0.0340 (3) | |
C9 | 0.35090 (14) | 0.16726 (12) | 0.26727 (5) | 0.0388 (3) | |
C10B | 0.38753 (12) | 0.09318 (10) | 0.17352 (5) | 0.0298 (3) | |
N61 | 0.14927 (10) | 0.16840 (8) | 0.07061 (4) | 0.0314 (3) | |
N62 | 0.10258 (12) | 0.25838 (10) | 0.03668 (5) | 0.0398 (3) | |
N63 | −0.01431 (12) | 0.23478 (10) | 0.02593 (5) | 0.0433 (3) | |
C63A | −0.04553 (13) | 0.12619 (12) | 0.05275 (5) | 0.0349 (3) | |
C64 | −0.15776 (13) | 0.06061 (13) | 0.05325 (6) | 0.0412 (3) | |
C65 | −0.15915 (14) | −0.04872 (13) | 0.08263 (6) | 0.0432 (4) | |
C66 | −0.05330 (14) | −0.09096 (12) | 0.11197 (5) | 0.0390 (3) | |
C67 | 0.05720 (13) | −0.02748 (11) | 0.11262 (5) | 0.0334 (3) | |
C67A | 0.05891 (12) | 0.08272 (11) | 0.08148 (5) | 0.0299 (3) | |
H1A | 0.4944 | −0.0768 | 0.2547 | 0.047* | |
H1B | 0.5887 | 0.0376 | 0.2645 | 0.047* | |
H2A | 0.6392 | 0.0492 | 0.1705 | 0.048* | |
H2B | 0.6058 | −0.0958 | 0.1723 | 0.048* | |
H4A | 0.5212 | −0.0260 | 0.0639 | 0.040* | |
H4B | 0.5292 | 0.1178 | 0.0800 | 0.040* | |
H5A | 0.3000 | −0.0137 | 0.0629 | 0.039* | |
H5B | 0.3587 | 0.0797 | 0.0177 | 0.039* | |
H6 | 0.3180 | 0.2485 | 0.0722 | 0.037* | |
H7 | 0.1676 | 0.2979 | 0.1740 | 0.042* | |
H8 | 0.2107 | 0.2946 | 0.2701 | 0.047* | |
H9 | 0.3686 | 0.1673 | 0.3067 | 0.047* | |
H64 | −0.2298 | 0.0903 | 0.0342 | 0.049* | |
H65 | −0.2333 | −0.0969 | 0.0831 | 0.052* | |
H66 | −0.0587 | −0.1666 | 0.1322 | 0.047* | |
H67 | 0.1281 | −0.0562 | 0.1329 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0401 (9) | 0.0424 (8) | 0.0361 (7) | −0.0012 (6) | −0.0053 (6) | 0.0044 (6) |
C2 | 0.0373 (8) | 0.0404 (7) | 0.0428 (7) | 0.0045 (6) | −0.0045 (6) | 0.0041 (6) |
N3 | 0.0345 (7) | 0.0308 (6) | 0.0312 (5) | 0.0026 (5) | 0.0004 (4) | 0.0008 (4) |
C4 | 0.0340 (7) | 0.0313 (7) | 0.0337 (7) | −0.0013 (5) | 0.0037 (5) | −0.0015 (5) |
C5 | 0.0367 (8) | 0.0310 (7) | 0.0301 (6) | −0.0031 (6) | 0.0019 (5) | −0.0014 (5) |
C6 | 0.0330 (7) | 0.0250 (6) | 0.0336 (7) | −0.0038 (5) | −0.0017 (5) | 0.0018 (5) |
C6A | 0.0307 (7) | 0.0246 (6) | 0.0318 (6) | −0.0061 (5) | −0.0004 (5) | −0.0004 (5) |
C7 | 0.0342 (7) | 0.0306 (7) | 0.0399 (7) | −0.0014 (5) | −0.0005 (6) | −0.0034 (5) |
C8 | 0.0396 (8) | 0.0405 (8) | 0.0386 (7) | −0.0029 (7) | 0.0055 (6) | −0.0110 (6) |
C9A | 0.0364 (8) | 0.0335 (7) | 0.0323 (7) | −0.0071 (6) | −0.0020 (5) | 0.0017 (5) |
C9 | 0.0431 (9) | 0.0431 (8) | 0.0303 (7) | −0.0076 (6) | −0.0013 (6) | −0.0038 (6) |
C10B | 0.0317 (7) | 0.0250 (6) | 0.0327 (6) | −0.0063 (5) | 0.0010 (5) | −0.0012 (5) |
N61 | 0.0363 (7) | 0.0252 (5) | 0.0327 (6) | 0.0008 (5) | −0.0050 (4) | 0.0016 (4) |
N62 | 0.0487 (8) | 0.0300 (6) | 0.0408 (6) | 0.0047 (5) | −0.0106 (5) | 0.0056 (5) |
N63 | 0.0459 (8) | 0.0360 (6) | 0.0481 (7) | 0.0044 (5) | −0.0115 (6) | 0.0029 (5) |
C63A | 0.0385 (8) | 0.0325 (7) | 0.0338 (7) | 0.0058 (6) | −0.0051 (6) | −0.0049 (5) |
C64 | 0.0325 (8) | 0.0489 (8) | 0.0421 (8) | 0.0050 (7) | −0.0048 (6) | −0.0086 (6) |
C65 | 0.0354 (9) | 0.0479 (8) | 0.0464 (8) | −0.0066 (7) | 0.0034 (6) | −0.0089 (6) |
C66 | 0.0432 (9) | 0.0336 (7) | 0.0402 (7) | −0.0030 (6) | 0.0075 (6) | −0.0019 (6) |
C67 | 0.0371 (8) | 0.0307 (7) | 0.0325 (7) | 0.0023 (6) | 0.0011 (5) | 0.0001 (5) |
C67A | 0.0322 (7) | 0.0288 (6) | 0.0287 (6) | 0.0000 (5) | 0.0000 (5) | −0.0046 (5) |
C1—C9A | 1.510 (2) | C9A—C9 | 1.3773 (19) |
C1—C2 | 1.5317 (19) | C9A—C10B | 1.3959 (17) |
C2—N3 | 1.4654 (17) | N61—N62 | 1.3575 (14) |
N3—C10B | 1.3948 (16) | N61—C67A | 1.3652 (16) |
N3—C4 | 1.4539 (16) | N62—N63 | 1.3028 (16) |
C4—C5 | 1.5128 (18) | N63—C63A | 1.3771 (18) |
C5—C6 | 1.5308 (17) | C63A—C67A | 1.3908 (18) |
C6—N61 | 1.4598 (16) | C63A—C64 | 1.396 (2) |
C6—C6A | 1.5175 (17) | C64—C65 | 1.373 (2) |
C6A—C10B | 1.3851 (17) | C65—C66 | 1.406 (2) |
C6A—C7 | 1.3960 (17) | C66—C67 | 1.3688 (19) |
C7—C8 | 1.3832 (18) | C67—C67A | 1.4023 (17) |
C8—C9 | 1.3977 (19) | ||
C9A—C1—C2 | 101.79 (10) | C6A—C10B—N3 | 125.63 (11) |
N3—C2—C1 | 103.93 (11) | C6A—C10B—C9A | 123.08 (11) |
C10B—N3—C4 | 114.42 (10) | N3—C10B—C9A | 111.27 (11) |
C10B—N3—C2 | 106.20 (10) | N62—N61—C67A | 109.75 (11) |
C4—N3—C2 | 119.75 (11) | N62—N61—C6 | 120.10 (10) |
N3—C4—C5 | 108.11 (10) | C67A—N61—C6 | 130.02 (10) |
C4—C5—C6 | 112.32 (10) | N63—N62—N61 | 109.17 (10) |
N61—C6—C6A | 111.48 (10) | N62—N63—C63A | 108.13 (10) |
N61—C6—C5 | 110.19 (10) | N63—C63A—C67A | 108.57 (12) |
C6A—C6—C5 | 111.85 (10) | N63—C63A—C64 | 130.34 (12) |
C10B—C6A—C7 | 117.00 (11) | C67A—C63A—C64 | 121.08 (12) |
C10B—C6A—C6 | 118.14 (11) | C65—C64—C63A | 116.90 (13) |
C7—C6A—C6 | 124.73 (11) | C64—C65—C66 | 121.44 (13) |
C8—C7—C6A | 120.75 (12) | C67—C66—C65 | 122.66 (13) |
C7—C8—C9 | 121.10 (12) | C66—C67—C67A | 115.65 (12) |
C9—C9A—C10B | 118.94 (12) | N61—C67A—C63A | 104.38 (10) |
C9—C9A—C1 | 133.53 (12) | N61—C67A—C67 | 133.36 (12) |
C10B—C9A—C1 | 107.53 (11) | C63A—C67A—C67 | 122.26 (12) |
C9A—C9—C8 | 119.10 (12) | ||
C9A—C1—C2—N3 | −28.06 (13) | C9—C9A—C10B—C6A | 2.08 (19) |
C1—C2—N3—C10B | 29.98 (13) | C1—C9A—C10B—C6A | −177.46 (11) |
C1—C2—N3—C4 | 161.43 (10) | C9—C9A—C10B—N3 | −179.20 (11) |
C10B—N3—C4—C5 | −51.17 (13) | C1—C9A—C10B—N3 | 1.26 (14) |
C2—N3—C4—C5 | −178.93 (10) | C6A—C6—N61—N62 | 123.94 (11) |
N3—C4—C5—C6 | 61.63 (13) | C5—C6—N61—N62 | −111.24 (11) |
C4—C5—C6—N61 | −166.92 (10) | C6A—C6—N61—C67A | −60.65 (15) |
C4—C5—C6—C6A | −42.32 (14) | C5—C6—N61—C67A | 64.16 (15) |
N61—C6—C6A—C10B | 137.22 (11) | C67A—N61—N62—N63 | 0.79 (14) |
C5—C6—C6A—C10B | 13.34 (15) | C6—N61—N62—N63 | 177.05 (10) |
N61—C6—C6A—C7 | −46.99 (15) | N61—N62—N63—C63A | −0.67 (14) |
C5—C6—C6A—C7 | −170.87 (11) | N62—N63—C63A—C67A | 0.32 (14) |
C10B—C6A—C7—C8 | 0.11 (18) | N62—N63—C63A—C64 | −178.31 (13) |
C6—C6A—C7—C8 | −175.72 (12) | N63—C63A—C64—C65 | 177.62 (13) |
C6A—C7—C8—C9 | 0.9 (2) | C67A—C63A—C64—C65 | −0.86 (19) |
C2—C1—C9A—C9 | −162.53 (14) | C63A—C64—C65—C66 | 1.5 (2) |
C2—C1—C9A—C10B | 16.91 (14) | C64—C65—C66—C67 | −0.8 (2) |
C10B—C9A—C9—C8 | −0.98 (19) | C65—C66—C67—C67A | −0.63 (18) |
C1—C9A—C9—C8 | 178.41 (14) | N62—N61—C67A—C63A | −0.56 (13) |
C7—C8—C9—C9A | −0.5 (2) | C6—N61—C67A—C63A | −176.33 (11) |
C7—C6A—C10B—N3 | 179.84 (11) | N62—N61—C67A—C67 | 178.88 (12) |
C6—C6A—C10B—N3 | −4.04 (18) | C6—N61—C67A—C67 | 3.1 (2) |
C7—C6A—C10B—C9A | −1.62 (18) | N63—C63A—C67A—N61 | 0.15 (13) |
C6—C6A—C10B—C9A | 174.49 (11) | C64—C63A—C67A—N61 | 178.93 (11) |
C4—N3—C10B—C6A | 24.18 (18) | N63—C63A—C67A—C67 | −179.37 (11) |
C2—N3—C10B—C6A | 158.56 (12) | C64—C63A—C67A—C67 | −0.59 (19) |
C4—N3—C10B—C9A | −154.50 (11) | C66—C67—C67A—N61 | −178.05 (13) |
C2—N3—C10B—C9A | −20.12 (14) | C66—C67—C67A—C63A | 1.31 (18) |
Experimental details
Crystal data | |
Chemical formula | C17H16N4 |
Mr | 275.35 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 10.7112 (3), 10.8297 (3), 23.6321 (5) |
V (Å3) | 2741.56 (12) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.30 × 0.20 × 0.20 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | Multi-scan (DENZO-SMN; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.976, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10806, 3083, 2317 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.112, 1.27 |
No. of reflections | 3083 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.22 |
Computer programs: KappaCCD Server Software (Nonius, 1997), DENZO-SMN (Otwinowski & Minor, 1997), DENZO-SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976) and PLATON (Spek, 2000), SHELXL97 and WORDPERFECT macro PRPKAPPA (Ferguson, 1999).
C2—N3 | 1.4654 (17) | N61—N62 | 1.3575 (14) |
N3—C10B | 1.3948 (16) | N61—C67A | 1.3652 (16) |
N3—C4 | 1.4539 (16) | N62—N63 | 1.3028 (16) |
C6—N61 | 1.4598 (16) | N63—C63A | 1.3771 (18) |
C10B—N3—C4 | 114.42 (10) | N62—N61—C6 | 120.10 (10) |
C10B—N3—C2 | 106.20 (10) | C67A—N61—C6 | 130.02 (10) |
C4—N3—C2 | 119.75 (11) | N63—N62—N61 | 109.17 (10) |
N62—N61—C67A | 109.75 (11) | N62—N63—C63A | 108.13 (10) |
The title compound, (I), was obtained as a by-product in the preparation of tricyclic heterocycles by annelation using benzotriazole as a synthetic auxiliary (Katritzky et al., 1998). Derivatives of the tricyclic system 1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinoline, known as lilolidine (Katayama et al., 1985), i.e. pyroquilone (Bass et al., 1981; Muecke & Gross, 1986; Nakamura, 1986) and analogues (Bass et al., 1975a,b, 1976) have shown antifungal applications in rice crops.
Table 1 lists the geometric parameters, while Fig. 1 shows a view of the molecule. The only molecular interaction is π–π stacking between the benzotriazole groups in which the perpendicular distance between the triazole group at (x, y, z) and the benzene group at (-x, -y, -z) is 3.695 (1) Å, with a distance of 3.822 (2) Å between their centroids (Fig. 2). Examination of the structure with PLATON (Spek, 2000) showed that there were no solvent-accessible voids in the crystal lattice.