3-Acetyl-1,6,7,12b-tetrahydroindolo[2,3-
a]quinolizin-2(12
H)-one, C
17H
16N
2O
2, consists of two symmetry-independent molecules and each forms a layered structure stabilized by N—H
O and C—H
O hydrogen bonds. In 3-acetyl-6,7-dihydroindolo[2,3-
a]quinolizin-4(12
H)-one monohydrate, C
17H
14N
2O
2·H
2O, the structure is stabilized by O—H
O, N—H
O and C—H
O hydrogen bonds, with the ordered water molecule playing a crucial role in the self-assembly. Contribution from the weak interactions to the strong hydrogen-bonded network is a common feature in both structures.
Supporting information
CCDC references: 158268; 158269
The synthesis of (1) and (2) have been reported previously (Giri et al.,
1984, 1995). Orange needle-shaped crystals of compounds (1) and (2) were
obtained from 1:1 mixtures of methanol and chloroform.
In both structures, C—H distances were constrained to distances in the range
0.93–0.98 Å, depending on c-atom type, with Uiso = 1.2Ueq
for the C atom (1.5 for methyl). N—H distances were constrained to be 0.86 Å, with Uiso = 1.2Ueq. Water H atoms in (2) were refined
isotropically.
For both compounds, data collection: CAD-4 Software (Enraf-Nonius, 1989); cell refinement: CAD-4 Software; data reduction: Xtal (Hall et al., 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLUTON-(C) (Spek, 1979-1997); software used to prepare material for publication: SHELXL97.
(1) 3-Acetyl-1,2,6,7,12,12
b-hexahydroindolo[2,3-
a]quinolizin-2-one.
top
Crystal data top
C17H16N2O2 | Z = 4 |
Mr = 280.32 | F(000) = 592 |
Triclinic, P1 | Dx = 1.340 Mg m−3 |
a = 8.169 (16) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 12.841 (3) Å | Cell parameters from 25 reflections |
c = 14.772 (3) Å | θ = 9.1–18.2° |
α = 72.60 (3)° | µ = 0.09 mm−1 |
β = 75.54 (3)° | T = 293 K |
γ = 72.64 (3)° | Needles, orange |
V = 1389 (3) Å3 | 0.52 × 0.48 × 0.32 mm |
Data collection top
CAD4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 1.7° |
Graphite monochromator | h = 0→9 |
ω scan | k = −14→15 |
4883 measured reflections | l = −16→17 |
4883 independent reflections | 3 standard reflections every 100 reflections |
3225 reflections with I > 2σ(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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0564P)2 + 0.2875P] where P = (Fo2 + 2Fc2)/3 |
4883 reflections | (Δ/σ)max = 0.004 |
379 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.22 e Å−3 |
Crystal data top
C17H16N2O2 | γ = 72.64 (3)° |
Mr = 280.32 | V = 1389 (3) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.169 (16) Å | Mo Kα radiation |
b = 12.841 (3) Å | µ = 0.09 mm−1 |
c = 14.772 (3) Å | T = 293 K |
α = 72.60 (3)° | 0.52 × 0.48 × 0.32 mm |
β = 75.54 (3)° | |
Data collection top
CAD4 diffractometer | Rint = 0.000 |
4883 measured reflections | 3 standard reflections every 100 reflections |
4883 independent reflections | intensity decay: none |
3225 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.20 e Å−3 |
4883 reflections | Δρmin = −0.22 e Å−3 |
379 parameters | |
Special details top
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 | 0.5851 (3) | 0.3160 (2) | 0.01938 (16) | 0.0513 (6) | |
H1B | 0.5278 | 0.3900 | −0.0047 | 0.062* | |
C2 | 0.6863 (3) | 0.2508 (2) | −0.04178 (18) | 0.0613 (7) | |
H2A | 0.6990 | 0.2817 | −0.1079 | 0.074* | |
C3 | 0.7706 (3) | 0.1395 (2) | −0.00736 (18) | 0.0635 (7) | |
H3A | 0.8384 | 0.0972 | −0.0508 | 0.076* | |
C4 | 0.7554 (3) | 0.0906 (2) | 0.09016 (18) | 0.0570 (6) | |
H4A | 0.8114 | 0.0159 | 0.1132 | 0.068* | |
C5 | 0.6538 (3) | 0..15648 (19) | 0.15270 (16) | 0.0434 (5) | |
C6 | 0.5688 (3) | 0.26972 (18) | 0.11867 (15) | 0.0414 (5) | |
C7 | 0.4787 (3) | 0.31179 (17) | 0.20191 (15) | 0.0402 (5) | |
C8 | 0.5109 (3) | 0.22554 (17) | 0.28016 (15) | 0.0397 (5) | |
C9 | 0.3757 (3) | 0.42663 (18) | 0.21131 (16) | 0.0482 (6) | |
H9A | 0.2583 | 0.4389 | 0.2005 | 0.058* | |
H9B | 0.4292 | 0.4829 | 0.1635 | 0.058* | |
C10 | 0.3698 (3) | 0.43724 (18) | 0.31155 (15) | 0.0488 (6) | |
H10A | 0.4823 | 0.4440 | 0.3162 | 0.059* | |
H10B | 0.2838 | 0.5050 | 0.3227 | 0.059* | |
C11 | 0.4420 (3) | 0.22816 (17) | 0.38277 (15) | 0.0393 (5) | |
H11A | 0.5398 | 0.2172 | 0.4146 | 0.047* | |
C12 | 0.3426 (3) | 0.13922 (17) | 0.43730 (15) | 0.0424 (5) | |
H12A | 0.2528 | 0.1449 | 0.4025 | 0.051* | |
H12B | 0.4217 | 0.0654 | 0.4403 | 0.051* | |
C13 | 0.2591 (3) | 0.15046 (18) | 0.53838 (15) | 0.0416 (5) | |
C14 | 0.1835 (3) | 0.26439 (17) | 0.54585 (15) | 0.0413 (5) | |
C15 | 0.2143 (3) | 0.35051 (18) | 0.46543 (15) | 0.0434 (5) | |
H15A | 0.1497 | 0.4229 | 0.4684 | 0.052* | |
C16 | 0.0682 (3) | 0.2987 (2) | 0.63011 (16) | 0.0491 (6) | |
C17 | 0.0233 (4) | 0.2126 (2) | 0.72053 (18) | 0.0764 (9) | |
H17A | −0.0529 | 0.2499 | 0.7684 | 0.115* | |
H17B | 0.1280 | 0.1676 | 0.7443 | 0.115* | |
H17C | −0.0338 | 0.1651 | 0.7068 | 0.115* | |
N1 | 0.6158 (2) | 0.13122 (15) | 0.25181 (12) | 0.0447 (5) | |
H1A | 0.6518 | 0.0671 | 0.2896 | 0.054* | |
N2 | 0.3255 (2) | 0.33976 (14) | 0.38562 (12) | 0.0421 (4) | |
O1 | 0.2539 (2) | 0.06512 (13) | 0.60409 (11) | 0.0601 (5) | |
O2 | 0.0058 (2) | 0.39867 (15) | 0.62885 (12) | 0.0705 (5) | |
C18 | −0.1661 (3) | 0.1609 (2) | 1.47365 (16) | 0.0492 (6) | |
H18A | −0.1410 | 0.0827 | 1.4910 | 0.059* | |
C19 | −0.2608 (3) | 0.2217 (2) | 1.53990 (17) | 0.0571 (7) | |
H19A | −0.3010 | 0.1843 | 1.6022 | 0.069* | |
C20 | −0.2974 (3) | 0.3387 (2) | 1.51464 (17) | 0.0588 (7) | |
H20A | −0.3625 | 0.3781 | 1.5606 | 0.071* | |
C21 | −0.2396 (3) | 0.3976 (2) | 1.42341 (16) | 0.0527 (6) | |
H21A | −0.2631 | 0.4757 | 1.4074 | 0.063* | |
C22 | −0.1452 (3) | 0.33613 (18) | 1.35647 (15) | 0.0420 (5) | |
C23 | −0.1076 (3) | 0.21772 (18) | 1.38001 (15) | 0.0405 (5) | |
C24 | −0.0084 (3) | 0.18310 (17) | 1.29447 (15) | 0.0404 (5) | |
C25 | 0.0087 (3) | 0.27825 (17) | 1.22554 (15) | 0.0395 (5) | |
C26 | 0.1064 (3) | 0.28455 (17) | 1.12534 (15) | 0.0411 (5) | |
H26A | 0.1945 | 0.3266 | 1.1148 | 0.049* | |
C27 | 0.2400 (3) | 0.07979 (19) | 1.19933 (16) | 0.0517 (6) | |
H27A | 0.3257 | 0.0952 | 1.2255 | 0.062* | |
H27B | 0.2906 | 0.0090 | 1.1807 | 0.062* | |
C28 | 0.0785 (3) | 0.07027 (18) | 1.27585 (16) | 0.0492 (6) | |
H28A | −0.0003 | 0.0435 | 1.2538 | 0.059* | |
H28B | 0.1106 | 0.0172 | 1.3346 | 0.059* | |
C29 | −0.0034 (3) | 0.34039 (18) | 1.04736 (15) | 0.0442 (5) | |
H29A | −0.0928 | 0.3005 | 1.0574 | 0.053* | |
H29B | −0.0609 | 0.4170 | 1.0518 | 0.053* | |
C30 | 0.1046 (3) | 0.34160 (18) | 0.94821 (16) | 0.0445 (5) | |
C31 | 0.2436 (3) | 0.24310 (18) | 0.94250 (16) | 0.0454 (5) | |
C32 | 0.2672 (3) | 0.15935 (19) | 1.02625 (17) | 0.0479 (6) | |
H32A | 0.3391 | 0.0897 | 1.0195 | 0.057* | |
C33 | 0.3611 (3) | 0.2209 (2) | 0.85389 (18) | 0.0580 (7) | |
C34 | 0.3713 (4) | 0.3148 (3) | 0.76508 (19) | 0.0856 (10) | |
H34A | 0.4539 | 0.2866 | 0.7139 | 0.128* | |
H34B | 0.4077 | 0.3726 | 0.7780 | 0.128* | |
H34C | 0.2588 | 0.3453 | 0.7464 | 0.128* | |
N3 | −0.0733 (2) | 0.37142 (15) | 1.26140 (13) | 0.0461 (5) | |
H3B | −0.0787 | 0.4401 | 1.2298 | 0.055* | |
N4 | 0.1968 (2) | 0.16994 (14) | 1.11444 (13) | 0.0435 (4) | |
O3 | 0.0624 (2) | 0.42082 (13) | 0.87975 (12) | 0.0640 (5) | |
O4 | 0.4549 (3) | 0.12762 (17) | 0.85210 (15) | 0.0902 (7) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0451 (13) | 0.0623 (15) | 0.0373 (13) | −0.0122 (11) | −0.0038 (10) | −0.0022 (12) |
C2 | 0.0579 (16) | 0.0805 (19) | 0.0379 (14) | −0.0175 (14) | −0.0015 (12) | −0.0083 (13) |
C3 | 0.0631 (17) | 0.0759 (19) | 0.0488 (16) | −0.0144 (14) | 0.0050 (13) | −0.0261 (14) |
C4 | 0.0517 (14) | 0.0514 (15) | 0.0568 (16) | −0.0045 (12) | 0.0018 (12) | −0.0144 (13) |
C5 | 0.0347 (11) | 0.0490 (13) | 0.0409 (13) | −0.0127 (10) | −0.0013 (10) | −0.0048 (10) |
C6 | 0.0330 (11) | 0.0485 (13) | 0.0374 (12) | −0.0118 (10) | −0.0027 (9) | −0.0037 (10) |
C7 | 0.0350 (11) | 0.0418 (12) | 0.0365 (12) | −0.0086 (9) | −0.0057 (9) | −0.0001 (10) |
C8 | 0.0314 (11) | 0.0431 (12) | 0.0371 (12) | −0.0061 (9) | −0.0045 (9) | −0.0031 (10) |
C9 | 0.0472 (13) | 0.0454 (13) | 0.0413 (13) | −0.0089 (11) | −0.0060 (10) | 0.0014 (10) |
C10 | 0.0568 (14) | 0.0393 (13) | 0.0443 (14) | −0.0182 (11) | −0.0021 (11) | −0.0005 (10) |
C11 | 0.0323 (11) | 0.0406 (12) | 0.0368 (12) | −0.0041 (9) | −0.0072 (9) | −0.0012 (9) |
C12 | 0.0409 (12) | 0.0371 (12) | 0.0388 (13) | −0.0038 (9) | −0.0033 (10) | −0.0027 (10) |
C13 | 0.0374 (11) | 0.0398 (12) | 0.0371 (12) | −0.0053 (9) | −0.0055 (9) | 0.0013 (10) |
C14 | 0.0416 (12) | 0.0407 (12) | 0.0341 (12) | −0.0070 (10) | −0.0056 (9) | −0.0022 (10) |
C15 | 0.0488 (13) | 0.0373 (12) | 0.0382 (13) | −0.0051 (10) | −0.0061 (10) | −0.0072 (10) |
C16 | 0.0526 (14) | 0.0451 (14) | 0.0405 (14) | −0.0054 (11) | −0.0039 (11) | −0.0072 (11) |
C17 | 0.100 (2) | 0.0620 (17) | 0.0451 (16) | −0.0181 (16) | 0.0178 (15) | −0.0074 (13) |
N1 | 0.0395 (10) | 0.0424 (11) | 0.0377 (11) | −0.0025 (8) | −0.0025 (8) | 0.0003 (8) |
N2 | 0.0472 (11) | 0.0369 (10) | 0.0343 (10) | −0.0101 (8) | −0.0017 (8) | −0.0019 (8) |
O1 | 0.0638 (11) | 0.0443 (9) | 0.0439 (10) | −0.0012 (8) | 0.0034 (8) | 0.0076 (8) |
O2 | 0.0893 (14) | 0.0501 (11) | 0.0502 (11) | 0.0007 (9) | 0.0055 (9) | −0.0125 (8) |
C18 | 0.0461 (13) | 0.0526 (14) | 0.0396 (13) | −0.0097 (11) | −0.0101 (11) | 0.0022 (11) |
C19 | 0.0541 (15) | 0.0719 (18) | 0.0346 (13) | −0.0125 (13) | −0.0039 (11) | −0.0033 (12) |
C20 | 0.0580 (15) | 0.0733 (18) | 0.0396 (14) | −0.0086 (13) | −0.0024 (12) | −0.0183 (13) |
C21 | 0.0552 (14) | 0.0521 (14) | 0.0455 (15) | −0.0075 (12) | −0.0051 (11) | −0.0126 (12) |
C22 | 0.0371 (11) | 0.0480 (13) | 0.0351 (12) | −0.0084 (10) | −0.0046 (9) | −0.0048 (10) |
C23 | 0.0317 (11) | 0.0474 (13) | 0.0373 (12) | −0.0082 (9) | −0.0087 (9) | −0.0021 (10) |
C24 | 0.0344 (11) | 0.0425 (12) | 0.0395 (12) | −0.0082 (9) | −0.0061 (9) | −0.0043 (10) |
C25 | 0.0376 (11) | 0.0391 (12) | 0.0363 (12) | −0.0063 (9) | −0.0040 (9) | −0.0064 (10) |
C26 | 0.0399 (12) | 0.0371 (12) | 0.0407 (13) | −0.0093 (9) | −0.0020 (10) | −0.0054 (10) |
C27 | 0.0473 (13) | 0.0440 (13) | 0.0494 (15) | 0.0024 (11) | −0.0082 (11) | −0.0042 (11) |
C28 | 0.0510 (14) | 0.0430 (13) | 0.0441 (14) | −0.0071 (11) | −0.0082 (11) | −0.0014 (11) |
C29 | 0.0455 (12) | 0.0392 (12) | 0.0409 (13) | −0.0060 (10) | −0.0047 (10) | −0.0064 (10) |
C30 | 0.0547 (14) | 0.0391 (13) | 0.0393 (13) | −0.0147 (11) | −0.0056 (11) | −0.0078 (10) |
C31 | 0.0478 (13) | 0.0444 (13) | 0.0412 (13) | −0.0124 (10) | −0.0010 (10) | −0.0110 (11) |
C32 | 0.0436 (13) | 0.0428 (13) | 0.0520 (15) | −0.0067 (10) | 0.0000 (11) | −0.0144 (11) |
C33 | 0.0597 (16) | 0.0624 (17) | 0.0495 (16) | −0.0135 (13) | 0.0022 (12) | −0.0207 (13) |
C34 | 0.095 (2) | 0.089 (2) | 0.0484 (17) | −0.0197 (18) | 0.0178 (16) | −0.0097 (16) |
N3 | 0.0519 (11) | 0.0386 (10) | 0.0387 (11) | −0.0082 (9) | −0.0016 (9) | −0.0042 (8) |
N4 | 0.0401 (10) | 0.0388 (10) | 0.0410 (11) | −0.0018 (8) | −0.0027 (8) | −0.0058 (8) |
O3 | 0.0868 (13) | 0.0474 (10) | 0.0424 (10) | −0.0069 (9) | −0.0079 (9) | −0.0006 (8) |
O4 | 0.0989 (16) | 0.0715 (14) | 0.0720 (14) | 0.0088 (12) | 0.0155 (11) | −0.0310 (11) |
Geometric parameters (Å, º) top
C1—C2 | 1.366 (3) | C18—C19 | 1.372 (3) |
C1—C6 | 1.397 (3) | C18—C23 | 1.396 (3) |
C1—H1B | 0.9300 | C18—H18A | 0.9300 |
C2—C3 | 1.389 (4) | C19—C20 | 1.392 (3) |
C2—H2A | 0.9300 | C19—H19A | 0.9300 |
C3—C4 | 1.379 (3) | C20—C21 | 1.377 (3) |
C3—H3A | 0.9300 | C20—H20A | 0.9300 |
C4—C5 | 1.387 (3) | C21—C22 | 1.385 (3) |
C4—H4A | 0.9300 | C21—H21A | 0.9300 |
C5—N1 | 1.376 (3) | C22—N3 | 1.374 (3) |
C5—C6 | 1.408 (3) | C22—C23 | 1.409 (3) |
C6—C7 | 1.433 (3) | C23—C24 | 1.436 (3) |
C7—C8 | 1.358 (3) | C24—C25 | 1.355 (3) |
C7—C9 | 1.492 (3) | C24—C28 | 1.485 (3) |
C8—N1 | 1.372 (3) | C25—N3 | 1.373 (3) |
C8—C11 | 1.486 (3) | C25—C26 | 1.487 (3) |
C9—C10 | 1.515 (3) | C26—N4 | 1.473 (3) |
C9—H9A | 0.9700 | C26—C29 | 1.511 (3) |
C9—H9B | 0.9700 | C26—H26A | 0.9800 |
C10—N2 | 1.466 (3) | C27—N4 | 1.465 (3) |
C10—H10A | 0.9700 | C27—C28 | 1.518 (3) |
C10—H10B | 0.9700 | C27—H27A | 0.9700 |
C11—N2 | 1.471 (3) | C27—H27B | 0.9700 |
C11—C12 | 1.513 (3) | C28—H28A | 0.9700 |
C11—H11A | 0.9800 | C28—H28B | 0.9700 |
C12—C13 | 1.509 (3) | C29—C30 | 1.508 (3) |
C12—H12A | 0.9700 | C29—H29A | 0.9700 |
C12—H12B | 0.9700 | C29—H29B | 0.9700 |
C13—O1 | 1.231 (2) | C30—O3 | 1.235 (3) |
C13—C14 | 1.434 (3) | C30—C31 | 1.434 (3) |
C14—C15 | 1.389 (3) | C31—C32 | 1.387 (3) |
C14—C16 | 1.458 (3) | C31—C33 | 1.466 (3) |
C15—N2 | 1.312 (3) | C32—N4 | 1.316 (3) |
C15—H15A | 0.9300 | C32—H32A | 0.9300 |
C16—O2 | 1.228 (3) | C33—O4 | 1.217 (3) |
C16—C17 | 1.502 (3) | C33—C34 | 1.497 (4) |
C17—H17A | 0.9600 | C34—H34A | 0.9600 |
C17—H17B | 0.9600 | C34—H34B | 0.9600 |
C17—H17C | 0.9600 | C34—H34C | 0.9600 |
N1—H1A | 0.8600 | N3—H3B | 0.8600 |
| | | |
C2—C1—C6 | 119.0 (2) | C19—C18—C23 | 119.3 (2) |
C2—C1—H1B | 120.5 | C19—C18—H18A | 120.4 |
C6—C1—H1B | 120.5 | C23—C18—H18A | 120.4 |
C1—C2—C3 | 121.5 (2) | C18—C19—C20 | 120.6 (2) |
C1—C2—H2A | 119.3 | C18—C19—H19A | 119.7 |
C3—C2—H2A | 119.3 | C20—C19—H19A | 119.7 |
C4—C3—C2 | 121.1 (2) | C21—C20—C19 | 121.8 (2) |
C4—C3—H3A | 119.4 | C21—C20—H20A | 119.1 |
C2—C3—H3A | 119.4 | C19—C20—H20A | 119.1 |
C3—C4—C5 | 117.7 (2) | C20—C21—C22 | 117.5 (2) |
C3—C4—H4A | 121.1 | C20—C21—H21A | 121.3 |
C5—C4—H4A | 121.1 | C22—C21—H21A | 121.3 |
N1—C5—C4 | 130.6 (2) | N3—C22—C21 | 130.3 (2) |
N1—C5—C6 | 107.70 (19) | N3—C22—C23 | 107.83 (19) |
C4—C5—C6 | 121.7 (2) | C21—C22—C23 | 121.8 (2) |
C1—C6—C5 | 119.0 (2) | C18—C23—C22 | 119.0 (2) |
C1—C6—C7 | 134.3 (2) | C18—C23—C24 | 134.4 (2) |
C5—C6—C7 | 106.69 (18) | C22—C23—C24 | 106.62 (18) |
C8—C7—C6 | 106.81 (19) | C25—C24—C23 | 106.64 (19) |
C8—C7—C9 | 121.9 (2) | C25—C24—C28 | 121.2 (2) |
C6—C7—C9 | 131.19 (19) | C23—C24—C28 | 132.00 (19) |
C7—C8—N1 | 110.24 (19) | C24—C25—N3 | 110.55 (19) |
C7—C8—C11 | 126.6 (2) | C24—C25—C26 | 126.3 (2) |
N1—C8—C11 | 123.18 (18) | N3—C25—C26 | 123.16 (18) |
C7—C9—C10 | 109.05 (18) | N4—C26—C25 | 109.14 (17) |
C7—C9—H9A | 109.9 | N4—C26—C29 | 107.90 (18) |
C10—C9—H9A | 109.9 | C25—C26—C29 | 115.10 (18) |
C7—C9—H9B | 109.9 | N4—C26—H26A | 108.2 |
C10—C9—H9B | 109.9 | C25—C26—H26A | 108.2 |
H9A—C9—H9B | 108.3 | C29—C26—H26A | 108.2 |
N2—C10—C9 | 111.50 (18) | N4—C27—C28 | 110.67 (18) |
N2—C10—H10A | 109.3 | N4—C27—H27A | 109.5 |
C9—C10—H10A | 109.3 | C28—C27—H27A | 109.5 |
N2—C10—H10B | 109.3 | N4—C27—H27B | 109.5 |
C9—C10—H10B | 109.3 | C28—C27—H27B | 109.5 |
H10A—C10—H10B | 108.0 | H27A—C27—H27B | 108.1 |
N2—C11—C8 | 108.16 (17) | C24—C28—C27 | 108.47 (18) |
N2—C11—C12 | 108.92 (16) | C24—C28—H28A | 110.0 |
C8—C11—C12 | 113.40 (18) | C27—C28—H28A | 110.0 |
N2—C11—H11A | 108.8 | C24—C28—H28B | 110.0 |
C8—C11—H11A | 108.8 | C27—C28—H28B | 110.0 |
C12—C11—H11A | 108.8 | H28A—C28—H28B | 108.4 |
C13—C12—C11 | 112.51 (18) | C30—C29—C26 | 111.82 (18) |
C13—C12—H12A | 109.1 | C30—C29—H29A | 109.3 |
C11—C12—H12A | 109.1 | C26—C29—H29A | 109.3 |
C13—C12—H12B | 109.1 | C30—C29—H29B | 109.3 |
C11—C12—H12B | 109.1 | C26—C29—H29B | 109.3 |
H12A—C12—H12B | 107.8 | H29A—C29—H29B | 107.9 |
O1—C13—C14 | 126.4 (2) | O3—C30—C31 | 126.0 (2) |
O1—C13—C12 | 119.4 (2) | O3—C30—C29 | 119.3 (2) |
C14—C13—C12 | 114.04 (18) | C31—C30—C29 | 114.53 (19) |
C15—C14—C13 | 118.3 (2) | C32—C31—C30 | 118.3 (2) |
C15—C14—C16 | 116.2 (2) | C32—C31—C33 | 116.3 (2) |
C13—C14—C16 | 125.42 (19) | C30—C31—C33 | 125.3 (2) |
N2—C15—C14 | 126.4 (2) | N4—C32—C31 | 125.6 (2) |
N2—C15—H15A | 116.8 | N4—C32—H32A | 117.2 |
C14—C15—H15A | 116.8 | C31—C32—H32A | 117.2 |
O2—C16—C14 | 120.8 (2) | O4—C33—C31 | 120.9 (2) |
O2—C16—C17 | 118.5 (2) | O4—C33—C34 | 119.3 (2) |
C14—C16—C17 | 120.8 (2) | C31—C33—C34 | 119.8 (2) |
C16—C17—H17A | 109.5 | C33—C34—H34A | 109.5 |
C16—C17—H17B | 109.5 | C33—C34—H34B | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34B | 109.5 |
C16—C17—H17C | 109.5 | C33—C34—H34C | 109.5 |
H17A—C17—H17C | 109.5 | H34A—C34—H34C | 109.5 |
H17B—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
C8—N1—C5 | 108.56 (17) | C25—N3—C22 | 108.36 (18) |
C8—N1—H1A | 125.7 | C25—N3—H3B | 125.8 |
C5—N1—H1A | 125.7 | C22—N3—H3B | 125.8 |
C15—N2—C10 | 122.00 (19) | C32—N4—C27 | 121.97 (19) |
C15—N2—C11 | 117.85 (17) | C32—N4—C26 | 116.62 (18) |
C10—N2—C11 | 118.04 (17) | C27—N4—C26 | 119.82 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.04 | 2.888 (2) | 167 |
N3—H3B···O3ii | 0.86 | 2.03 | 2.863 (3) | 162 |
C10—H10B···O2iii | 0.97 | 2.36 | 3.245 (3) | 151 |
C12—H12B···O1i | 0.97 | 2.72 | 3.594 (3) | 150 |
C15—H15A···O2iii | 0.93 | 2.48 | 3.265 (3) | 142 |
C27—H27B···O4iv | 0.97 | 2.34 | 3.191 (3) | 146 |
C29—H29B···O3ii | 0.97 | 2.57 | 3.410 (3) | 145 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+2; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z+2. |
(2) 3-Acetyl-4-oxo-6,7-dihydro-12
H-indolo[2,3-
a]quinolizine
monohydrate
top
Crystal data top
C17H14N2O2·H2O | F(000) = 312 |
Mr = 296.32 | Dx = 1.383 Mg m−3 |
Triclinic, P1 | Melting point: 543K K |
a = 7.307 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.405 (2) Å | Cell parameters from 25 reflections |
c = 10.989 (2) Å | θ = 9.1–18.2° |
α = 94.82 (3)° | µ = 0.10 mm−1 |
β = 108.84 (3)° | T = 293 K |
γ = 90.96 (3)° | Needles, orange |
V = 712 (2) Å3 | 0.48 × 0.36 × 0.28 mm |
Z = 2 | |
Data collection top
CAD-4 diffractometer | Rint = 0.000 |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.0° |
Graphite monochromator | h = 0→8 |
ω scan | k = −11→11 |
2490 measured reflections | l = −13→12 |
2490 independent reflections | 3 standard reflections every 100 reflections |
1072 reflections with I > 2σ(I) | intensity decay: none |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.062 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.117 | w = 1/[σ2(Fo2) + (0.0604P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2490 reflections | Δρmax = 0.25 e Å−3 |
208 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.038 (4) |
Crystal data top
C17H14N2O2·H2O | γ = 90.96 (3)° |
Mr = 296.32 | V = 712 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.307 (15) Å | Mo Kα radiation |
b = 9.405 (2) Å | µ = 0.10 mm−1 |
c = 10.989 (2) Å | T = 293 K |
α = 94.82 (3)° | 0.48 × 0.36 × 0.28 mm |
β = 108.84 (3)° | |
Data collection top
CAD-4 diffractometer | Rint = 0.000 |
2490 measured reflections | 3 standard reflections every 100 reflections |
2490 independent reflections | intensity decay: none |
1072 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.062 | 0 restraints |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.25 e Å−3 |
2490 reflections | Δρmin = −0.20 e Å−3 |
208 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 on F2 for ALL reflections except for 0 with very negative
F2 or flagged by the user for potential systematic errors. Weighted
R-factors wR and all goodnesses of fit S are based on
F2, conventional R-factors R are based on F,
with F set to zero for negative F2. The observed criterion of
F2 > σ(F2) is used only for calculating R-factor-obs
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 | 0.1660 (5) | 1.0457 (4) | −0.3310 (3) | 0.0575 (11) | |
H1A | 0.1212 | 0.9649 | −0.3889 | 0.069* | |
C2 | 0.1997 (5) | 1.1742 (4) | −0.3748 (4) | 0.0631 (12) | |
H2A | 0.1791 | 1.1795 | −0.4623 | 0.076* | |
C3 | 0.2648 (5) | 1.2962 (4) | −0.2875 (4) | 0.0610 (12) | |
H3A | 0.2856 | 1.3819 | −0.3186 | 0.073* | |
C4 | 0.2986 (5) | 1.2928 (4) | −0.1576 (4) | 0.0537 (11) | |
H4A | 0.3400 | 1.3747 | −0.1008 | 0.064* | |
C5 | 0.2688 (5) | 1.1621 (4) | −0.1132 (3) | 0.0442 (9) | |
C6 | 0.2001 (5) | 1.0384 (4) | −0.1984 (3) | 0.0444 (9) | |
C7 | 0.1850 (5) | 0.9281 (3) | −0.1214 (3) | 0.0422 (9) | |
C8 | 0.2472 (4) | 0.9857 (3) | 0.0036 (3) | 0.0378 (8) | |
C9 | 0.2567 (5) | 0.9114 (3) | 0.1142 (3) | 0.0399 (9) | |
C10 | 0.1912 (6) | 0.6915 (4) | −0.0396 (3) | 0.0571 (11) | |
H10A | 0.1084 | 0.6063 | −0.0515 | 0.069* | |
H10B | 0.3170 | 0.6609 | −0.0404 | 0.069* | |
C11 | 0.1078 (5) | 0.7777 (4) | −0.1523 (3) | 0.0536 (11) | |
H11A | 0.1391 | 0.7355 | −0.2263 | 0.064* | |
H11B | −0.0321 | 0.7755 | −0.1748 | 0.064* | |
C12 | 0.3024 (5) | 0.9745 (4) | 0.2362 (3) | 0.0473 (10) | |
H12A | 0.3302 | 1.0725 | 0.2528 | 0.057* | |
C13 | 0.3075 (5) | 0.8927 (4) | 0.3361 (3) | 0.0517 (10) | |
H13A | 0.3372 | 0.9371 | 0.4195 | 0.062* | |
C14 | 0.2699 (5) | 0.7476 (4) | 0.3154 (3) | 0.0491 (10) | |
C15 | 0.2282 (5) | 0.6782 (4) | 0.1880 (3) | 0.0486 (10) | |
C16 | 0.2832 (6) | 0.6692 (4) | 0.4284 (4) | 0.0636 (12) | |
C17 | 0.1977 (6) | 0.5208 (4) | 0.4120 (4) | 0.0793 (14) | |
H17A | 0.2199 | 0.4868 | 0.4953 | 0.119* | |
H17B | 0.2572 | 0.4595 | 0.3628 | 0.119* | |
H17C | 0.0610 | 0.5205 | 0.3674 | 0.119* | |
N1 | 0.2954 (4) | 1.1288 (3) | 0.0089 (3) | 0.0467 (8) | |
H1B | 0.3354 | 1.1870 | 0.0777 | 0.056* | |
N2 | 0.2145 (4) | 0.7664 (3) | 0.0896 (2) | 0.0423 (8) | |
O1 | 0.2090 (4) | 0.5469 (3) | 0.1593 (2) | 0.0641 (8) | |
O2 | 0.3593 (5) | 0.7280 (3) | 0.5366 (3) | 0.1071 (13) | |
O3 | 0.5232 (5) | 0.6586 (3) | 0.7891 (3) | 0.0751 (10) | |
H3B | 0.463 (7) | 0.674 (5) | 0.703 (4) | 0.119 (18)* | |
H3C | 0.611 (8) | 0.602 (6) | 0.797 (5) | 0.16 (3)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.056 (2) | 0.069 (3) | 0.047 (2) | 0.001 (2) | 0.0151 (19) | 0.013 (2) |
C2 | 0.055 (2) | 0.087 (3) | 0.047 (2) | −0.001 (2) | 0.0107 (19) | 0.026 (2) |
C3 | 0.053 (2) | 0.070 (3) | 0.061 (3) | −0.003 (2) | 0.015 (2) | 0.026 (2) |
C4 | 0.044 (2) | 0.050 (2) | 0.063 (3) | 0.0028 (18) | 0.0096 (19) | 0.0163 (19) |
C5 | 0.043 (2) | 0.046 (2) | 0.043 (2) | 0.0032 (17) | 0.0119 (16) | 0.0109 (17) |
C6 | 0.0335 (19) | 0.053 (2) | 0.047 (2) | −0.0028 (17) | 0.0138 (16) | 0.0075 (18) |
C7 | 0.040 (2) | 0.041 (2) | 0.047 (2) | −0.0005 (16) | 0.0139 (16) | 0.0102 (17) |
C8 | 0.0387 (19) | 0.0347 (19) | 0.0401 (19) | 0.0000 (16) | 0.0120 (15) | 0.0084 (16) |
C9 | 0.0402 (19) | 0.039 (2) | 0.040 (2) | 0.0071 (16) | 0.0100 (16) | 0.0098 (16) |
C10 | 0.071 (3) | 0.048 (2) | 0.048 (2) | −0.002 (2) | 0.015 (2) | −0.0018 (19) |
C11 | 0.057 (2) | 0.055 (2) | 0.043 (2) | −0.0047 (19) | 0.0068 (18) | 0.0061 (18) |
C12 | 0.055 (2) | 0.042 (2) | 0.044 (2) | 0.0034 (18) | 0.0133 (18) | 0.0059 (17) |
C13 | 0.055 (2) | 0.060 (3) | 0.039 (2) | 0.008 (2) | 0.0150 (18) | 0.0042 (19) |
C14 | 0.048 (2) | 0.056 (2) | 0.044 (2) | 0.0065 (19) | 0.0134 (17) | 0.0118 (18) |
C15 | 0.041 (2) | 0.051 (2) | 0.051 (2) | 0.0008 (18) | 0.0089 (17) | 0.0107 (19) |
C16 | 0.077 (3) | 0.060 (3) | 0.059 (3) | 0.024 (2) | 0.027 (2) | 0.014 (2) |
C17 | 0.093 (3) | 0.082 (3) | 0.076 (3) | 0.015 (3) | 0.037 (3) | 0.039 (2) |
N1 | 0.0560 (18) | 0.0425 (18) | 0.0407 (17) | −0.0002 (14) | 0.0146 (14) | 0.0033 (14) |
N2 | 0.0461 (17) | 0.0410 (17) | 0.0389 (16) | 0.0047 (14) | 0.0117 (13) | 0.0073 (14) |
O1 | 0.087 (2) | 0.0434 (16) | 0.0570 (17) | 0.0002 (14) | 0.0131 (14) | 0.0165 (13) |
O2 | 0.175 (4) | 0.090 (2) | 0.0470 (18) | 0.016 (2) | 0.019 (2) | 0.0210 (17) |
O3 | 0.103 (2) | 0.0631 (19) | 0.0500 (18) | 0.0149 (18) | 0.0123 (17) | 0.0005 (15) |
Geometric parameters (Å, º) top
C1—C2 | 1.385 (5) | C10—H10A | 0.9700 |
C1—C6 | 1.404 (5) | C10—H10B | 0.9700 |
C1—H1A | 0.9300 | C11—H11A | 0.9700 |
C2—C3 | 1.402 (5) | C11—H11B | 0.9700 |
C2—H2A | 0.9300 | C12—C13 | 1.384 (4) |
C3—C4 | 1.371 (5) | C12—H12A | 0.9300 |
C3—H3A | 0.9300 | C13—C14 | 1.373 (5) |
C4—C5 | 1.399 (5) | C13—H13A | 0.9300 |
C4—H4A | 0.9300 | C14—C15 | 1.429 (5) |
C5—N1 | 1.357 (4) | C14—C16 | 1.474 (5) |
C5—C6 | 1.406 (4) | C15—O1 | 1.242 (4) |
C6—C7 | 1.417 (4) | C15—N2 | 1.397 (4) |
C7—C8 | 1.360 (4) | C16—O2 | 1.217 (4) |
C7—C11 | 1.485 (4) | C16—C17 | 1.493 (5) |
C8—N1 | 1.377 (4) | C17—H17A | 0.9600 |
C8—C9 | 1.436 (4) | C17—H17B | 0.9600 |
C9—C12 | 1.354 (4) | C17—H17C | 0.9600 |
C9—N2 | 1.377 (4) | N1—H1B | 0.8600 |
C10—N2 | 1.488 (4) | O3—H3B | 0.93 (5) |
C10—C11 | 1.503 (4) | O3—H3C | 0.82 (6) |
| | | |
C2—C1—C6 | 119.4 (4) | C7—C11—H11A | 109.4 |
C2—C1—H1A | 120.3 | C10—C11—H11A | 109.4 |
C6—C1—H1A | 120.3 | C7—C11—H11B | 109.4 |
C1—C2—C3 | 120.1 (4) | C10—C11—H11B | 109.4 |
C1—C2—H2A | 119.9 | H11A—C11—H11B | 108.0 |
C3—C2—H2A | 119.9 | C9—C12—C13 | 119.7 (3) |
C4—C3—C2 | 121.8 (4) | C9—C12—H12A | 120.1 |
C4—C3—H3A | 119.1 | C13—C12—H12A | 120.1 |
C2—C3—H3A | 119.1 | C14—C13—C12 | 121.7 (3) |
C3—C4—C5 | 117.9 (4) | C14—C13—H13A | 119.2 |
C3—C4—H4A | 121.0 | C12—C13—H13A | 119.2 |
C5—C4—H4A | 121.0 | C13—C14—C15 | 119.4 (3) |
N1—C5—C4 | 129.8 (3) | C13—C14—C16 | 117.7 (3) |
N1—C5—C6 | 108.5 (3) | C15—C14—C16 | 122.8 (3) |
C4—C5—C6 | 121.7 (3) | O1—C15—N2 | 118.2 (3) |
C1—C6—C5 | 119.0 (3) | O1—C15—C14 | 125.2 (4) |
C1—C6—C7 | 134.6 (3) | N2—C15—C14 | 116.5 (3) |
C5—C6—C7 | 106.4 (3) | O2—C16—C14 | 119.5 (4) |
C8—C7—C6 | 107.1 (3) | O2—C16—C17 | 119.5 (4) |
C8—C7—C11 | 119.5 (3) | C14—C16—C17 | 120.9 (3) |
C6—C7—C11 | 133.3 (3) | C16—C17—H17A | 109.5 |
C7—C8—N1 | 109.7 (3) | C16—C17—H17B | 109.5 |
C7—C8—C9 | 125.9 (3) | H17A—C17—H17B | 109.5 |
N1—C8—C9 | 124.4 (3) | C16—C17—H17C | 109.5 |
C12—C9—N2 | 120.1 (3) | H17A—C17—H17C | 109.5 |
C12—C9—C8 | 124.4 (3) | H17B—C17—H17C | 109.5 |
N2—C9—C8 | 115.5 (3) | C5—N1—C8 | 108.2 (3) |
N2—C10—C11 | 115.4 (3) | C5—N1—H1B | 125.9 |
N2—C10—H10A | 108.4 | C8—N1—H1B | 125.9 |
C11—C10—H10A | 108.4 | C9—N2—C15 | 122.3 (3) |
N2—C10—H10B | 108.4 | C9—N2—C10 | 121.0 (3) |
C11—C10—H10B | 108.4 | C15—N2—C10 | 115.6 (3) |
H10A—C10—H10B | 107.5 | H3B—O3—H3C | 111 (5) |
C7—C11—C10 | 111.2 (3) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O3i | 0.86 | 1.98 | 2.819 (4) | 164 (4) |
O3—H3C···O1ii | 0.83 (6) | 1.92 (6) | 2.735 (4) | 168 (6) |
O3—H3B···O2 | 0.93 (5) | 1.86 (5) | 2.783 (4) | 173 (4) |
C10—H10B···O3iii | 0.97 | 2.76 | 3.522 (6) | 136 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1. |
Experimental details
| (1) | (2) |
Crystal data |
Chemical formula | C17H16N2O2 | C17H14N2O2·H2O |
Mr | 280.32 | 296.32 |
Crystal system, space group | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 293 | 293 |
a, b, c (Å) | 8.169 (16), 12.841 (3), 14.772 (3) | 7.307 (15), 9.405 (2), 10.989 (2) |
α, β, γ (°) | 72.60 (3), 75.54 (3), 72.64 (3) | 94.82 (3), 108.84 (3), 90.96 (3) |
V (Å3) | 1389 (3) | 712 (2) |
Z | 4 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.10 |
Crystal size (mm) | 0.52 × 0.48 × 0.32 | 0.48 × 0.36 × 0.28 |
|
Data collection |
Diffractometer | CAD4 diffractometer | CAD-4 diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4883, 4883, 3225 | 2490, 2490, 1072 |
Rint | 0.000 | 0.000 |
(sin θ/λ)max (Å−1) | 0.594 | 0.594 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.131, 1.07 | 0.062, 0.117, 1.03 |
No. of reflections | 4883 | 2490 |
No. of parameters | 379 | 208 |
H-atom treatment | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.22 | 0.25, −0.20 |
Hydrogen-bond geometry (Å, º) for (1) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.86 | 2.04 | 2.888 (2) | 167 |
N3—H3B···O3ii | 0.86 | 2.03 | 2.863 (3) | 162 |
C10—H10B···O2iii | 0.97 | 2.36 | 3.245 (3) | 151 |
C12—H12B···O1i | 0.97 | 2.72 | 3.594 (3) | 150 |
C15—H15A···O2iii | 0.93 | 2.48 | 3.265 (3) | 142 |
C27—H27B···O4iv | 0.97 | 2.34 | 3.191 (3) | 146 |
C29—H29B···O3ii | 0.97 | 2.57 | 3.410 (3) | 145 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+2; (iii) −x, −y+1, −z+1; (iv) −x+1, −y, −z+2. |
Hydrogen-bond geometry (Å, º) for (2) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1B···O3i | 0.86 | 1.98 | 2.819 (4) | 164 (4) |
O3—H3C···O1ii | 0.83 (6) | 1.92 (6) | 2.735 (4) | 168 (6) |
O3—H3B···O2 | 0.93 (5) | 1.86 (5) | 2.783 (4) | 173 (4) |
C10—H10B···O3iii | 0.97 | 2.76 | 3.522 (6) | 136 (3) |
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1. |
Indole alkaloids and their derivatives continue to attract the attention of organic and medicinal chemists because of their physiological importance as well as structural diversity. Compound (1) was synthesized with a view to obtaining different indole alkaloids from a common intermediate. Compound (2) was synthesized to obtain the alkaloid flavopereirine, which inhibits cancer producing cells (Giri et al., 1984, 1995). There are ca 90 hits in the Cambridge Structural Database (version 5.19, April 2000, 215 403 entries; Allen, 1998) that contain the tetracyclic skeleton of (1) and (2). However, none of these structures are closely related to the title compounds. Given the novelty of (1) and (2) and the fact that their conformation and packing motifs in the solid state will provide useful inputs for structural and medicinal studies currently ongoing in our laboratories, their crystallographic analysis was performed. \sch
There are two symmetry-independent molecules (A and B) with similar conformations in the crystal structure of (1). Compound (2) crystallizes as a hydrate. The indole moiety is planar while the quinolizine portion adopts chair, half-chair, boat conformations in both compounds. The bond distances and angles in both molecules are in the expected ranges (Orpen et al., 1989). The molecular geometry and numbering of (1) and (2) are displayed in Figs. 1 and 2 (ORTEPII; Johnson, 1976).
The crystal packing in (1) consists of separate hydrogen-bonded layers of A and B molecules, which in turn are close-packed through van der Waals interactions. The A and B molecules are in different conformations with maximum deviation in the C11—C15 ring portion and orientation of the acetyl group. The mean r.m.s. deviation in the overlay of skeletal atoms in the two molecules is 0.2616 Å. The A layer in (1) is shown in Fig. 3. Inversion-related molecules are connected by N—H···O and C—H···O hydrogen bonds through the multi-point recognition synthon I. C—H···O hydrogen bonds on the other side of the molecule extend through synthon II to form a molecular tape. The molecule being donor rich, both the carbonyl O atoms are bifurcated acceptors to N—H and C—H donors (N1—H1A···O1 2.04, C12—H12B···O1 2.72, C10—H10B···O2 2.36, C15—H15···O2 2.48 Å). It may be noted that the C—H···O bond that is donating together with the N—H group to O1 (synthon I) is significantly longer than the two C—H···O bonds of synthon II that is solely formed with the weak interactions. Layer B (not shown) is constituted with synthons III and IV mediated through one strong and two weak hydrogen bonds (N3—H3B···O3 2.03, C29—H29B···O3 2.57, C27—H27B···O4 2.34 Å). The presence of multiple molecules in the asymmetric unit of a crystal is often difficult to rationalize (Steiner, 2000). In the present case, it may be ascribed to different conformations and to distinct intermolecular synthons for each symmetry-independent molecule.
In hydrate (2), translation-related molecules are connected by four different types of hydrogen bonds to the water molecule (Fig. 4) [O3—H3C···O1 1.92 (6), O3—H3B···O2 1.86 (5), N1—H1A···O3 1.98, C10—H10B···O3 2.76 Å]. In this structure, the ordered water molecule donates hydrogen bonds to different carbonyl groups of the heterocycle and accepts from N—H and C—H donors (Desiraju & Steiner, 1999). The water O atom is tetracoordinated, though the geometry is far from ideal (107.3, 100.3, 78.4, 120.5, 123.2, 123.3°). Both these crystal structures illustrate the fortification of N—H···O and O—H···O networks by the weak C—H···O hydrogen bonds.