The title compound, C
27H
22N
2O
3, comprises an indeno-quinoxaline system linked
via a spiro ring junction to a hexahydro-1
H-pyrrolizine unit. This in turn carries an indene-1,3-dione linked again by a spiro junction through the five-membered indenone ring. The pyrrolizidine moiety is folded and twisted about the N—C bond common to the two five-membered rings. In the crystal packing, an
R22(20) graph set involves a dimeric C—H
O hydrogen bond and ring motif. The packing is further stabilized by C—H
O and weak π–π interactions.
Supporting information
CCDC reference: 287728
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.047
- wR factor = 0.128
- Data-to-parameter ratio = 16.7
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95
Alert level C
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
3 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
0 ALERT type 2 Indicator that the structure model may be wrong or deficient
1 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Ninhydrin (1 mmol), o-phenylenediamine (1 mmol), 2-benzylidine–1,3-indanedione (1 mmol) and L-proline (1 mmol) were refluxed in methanol until the starting material disappeared. The crude product was purified by column chromatography (petroleum ether–ethyl acetate, 8:2) and the product, compound (I), was re-crystallized from methanol.
The crystals were weakly diffracting, particularly at high θ values. All H atoms were fixed geometrically and allowed to ride on their parent C atoms, with C—H distances fixed in the range 0.93–0.97 Å and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PARST (Nardelli, 1995).
1'-Phenyl-2',3',5',6',7',7a'-hexahydroindan-2-spiro-2'-1
H-pyrrolizidine-3'- spiro-11'-indeno[1,2-
b]quinoxaline-1,3-dione
top
Crystal data top
C35H25N3O2 | F(000) = 1088 |
Mr = 519.58 | Dx = 1.354 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2836 reflections |
a = 11.1149 (14) Å | θ = 2.3–25.2° |
b = 12.4670 (16) Å | µ = 0.09 mm−1 |
c = 18.646 (2) Å | T = 293 K |
β = 99.415 (2)° | Block, colourless |
V = 2548.9 (6) Å3 | 0.25 × 0.22 × 0.20 mm |
Z = 4 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4851 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.029 |
Graphite monochromator | θmax = 28.0°, θmin = 1.9° |
ω scans | h = −14→14 |
28930 measured reflections | k = −16→16 |
6030 independent reflections | l = −23→23 |
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) = 0.128 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0697P)2 + 0.4648P] where P = (Fo2 + 2Fc2)/3 |
6030 reflections | (Δ/σ)max = 0.001 |
361 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C35H25N3O2 | V = 2548.9 (6) Å3 |
Mr = 519.58 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.1149 (14) Å | µ = 0.09 mm−1 |
b = 12.4670 (16) Å | T = 293 K |
c = 18.646 (2) Å | 0.25 × 0.22 × 0.20 mm |
β = 99.415 (2)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 4851 reflections with I > 2σ(I) |
28930 measured reflections | Rint = 0.029 |
6030 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.34 e Å−3 |
6030 reflections | Δρmin = −0.18 e Å−3 |
361 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 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 | 0.65685 (11) | 1.16724 (10) | 0.22936 (6) | 0.0314 (3) | |
C2 | 0.76023 (11) | 1.08887 (10) | 0.26801 (6) | 0.0318 (3) | |
C3 | 0.69053 (11) | 1.02776 (11) | 0.31976 (7) | 0.0351 (3) | |
H3 | 0.6312 | 0.9820 | 0.2893 | 0.042* | |
C4 | 0.61781 (12) | 1.11704 (11) | 0.34902 (7) | 0.0376 (3) | |
H4 | 0.6665 | 1.1471 | 0.3930 | 0.045* | |
C5 | 0.48984 (14) | 1.09399 (14) | 0.36392 (9) | 0.0511 (4) | |
H5A | 0.4508 | 1.0380 | 0.3322 | 0.061* | |
H5B | 0.4908 | 1.0732 | 0.4141 | 0.061* | |
C6 | 0.42671 (14) | 1.20106 (15) | 0.34734 (9) | 0.0542 (4) | |
H6A | 0.4489 | 1.2513 | 0.3870 | 0.065* | |
H6B | 0.3388 | 1.1927 | 0.3382 | 0.065* | |
C7 | 0.47384 (13) | 1.23804 (13) | 0.27946 (8) | 0.0455 (3) | |
H7A | 0.4275 | 1.2060 | 0.2361 | 0.055* | |
H7B | 0.4701 | 1.3155 | 0.2749 | 0.055* | |
C8 | 0.69923 (11) | 1.26390 (10) | 0.18900 (7) | 0.0336 (3) | |
C9 | 0.77170 (12) | 1.34975 (11) | 0.21599 (8) | 0.0409 (3) | |
H9 | 0.8033 | 1.3539 | 0.2653 | 0.049* | |
C10 | 0.79648 (14) | 1.42914 (12) | 0.16883 (9) | 0.0482 (4) | |
H10 | 0.8460 | 1.4864 | 0.1868 | 0.058* | |
C11 | 0.74941 (15) | 1.42535 (13) | 0.09558 (9) | 0.0510 (4) | |
H11 | 0.7691 | 1.4787 | 0.0646 | 0.061* | |
C12 | 0.67336 (14) | 1.34261 (12) | 0.06834 (8) | 0.0461 (3) | |
H12 | 0.6396 | 1.3403 | 0.0193 | 0.055* | |
C13 | 0.64825 (12) | 1.26295 (11) | 0.11553 (7) | 0.0359 (3) | |
C14 | 0.56357 (11) | 1.17368 (10) | 0.10203 (7) | 0.0338 (3) | |
C15 | 0.41156 (12) | 1.06881 (11) | 0.04688 (7) | 0.0365 (3) | |
C16 | 0.32318 (14) | 1.04302 (12) | −0.01387 (8) | 0.0454 (3) | |
H16 | 0.3163 | 1.0845 | −0.0558 | 0.054* | |
C17 | 0.24800 (14) | 0.95764 (14) | −0.01120 (8) | 0.0497 (4) | |
H17 | 0.1899 | 0.9412 | −0.0515 | 0.060* | |
C18 | 0.25669 (13) | 0.89439 (13) | 0.05105 (8) | 0.0477 (3) | |
H18 | 0.2052 | 0.8357 | 0.0517 | 0.057* | |
C19 | 0.34050 (13) | 0.91813 (12) | 0.11119 (8) | 0.0422 (3) | |
H19 | 0.3453 | 0.8758 | 0.1527 | 0.051* | |
C20 | 0.41913 (11) | 1.00588 (10) | 0.11061 (7) | 0.0343 (3) | |
C21 | 0.56892 (11) | 1.11304 (10) | 0.16721 (6) | 0.0316 (3) | |
C22 | 0.81761 (12) | 1.01894 (11) | 0.21518 (7) | 0.0352 (3) | |
C23 | 0.93565 (12) | 1.06798 (12) | 0.20646 (7) | 0.0399 (3) | |
C24 | 1.01376 (14) | 1.04273 (15) | 0.15768 (9) | 0.0531 (4) | |
H24 | 0.9982 | 0.9848 | 0.1261 | 0.064* | |
C25 | 1.11488 (15) | 1.10661 (18) | 0.15781 (10) | 0.0644 (5) | |
H25 | 1.1673 | 1.0926 | 0.1248 | 0.077* | |
C26 | 1.14013 (15) | 1.19111 (16) | 0.20600 (11) | 0.0632 (5) | |
H26 | 1.2081 | 1.2338 | 0.2040 | 0.076* | |
C27 | 1.06659 (13) | 1.21324 (13) | 0.25693 (10) | 0.0520 (4) | |
H27 | 1.0857 | 1.2679 | 0.2908 | 0.062* | |
C28 | 0.96321 (12) | 1.15082 (11) | 0.25568 (7) | 0.0389 (3) | |
C29 | 0.86862 (11) | 1.15845 (11) | 0.30279 (7) | 0.0358 (3) | |
C30 | 0.76008 (13) | 0.95593 (11) | 0.37774 (7) | 0.0389 (3) | |
C31 | 0.88517 (15) | 0.94746 (15) | 0.39386 (10) | 0.0601 (5) | |
H31 | 0.9333 | 0.9873 | 0.3673 | 0.072* | |
C32 | 0.94052 (17) | 0.88068 (17) | 0.44891 (11) | 0.0725 (6) | |
H32 | 1.0251 | 0.8762 | 0.4586 | 0.087* | |
C33 | 0.87299 (18) | 0.82161 (14) | 0.48887 (10) | 0.0634 (5) | |
H33 | 0.9108 | 0.7780 | 0.5263 | 0.076* | |
C34 | 0.74820 (18) | 0.82731 (14) | 0.47311 (9) | 0.0591 (4) | |
H34 | 0.7008 | 0.7868 | 0.4997 | 0.071* | |
C35 | 0.69284 (15) | 0.89305 (13) | 0.41788 (9) | 0.0511 (4) | |
H35 | 0.6082 | 0.8952 | 0.4073 | 0.061* | |
N1 | 0.60093 (9) | 1.20003 (9) | 0.29150 (6) | 0.0350 (2) | |
N2 | 0.48671 (10) | 1.15466 (9) | 0.04253 (6) | 0.0388 (3) | |
N3 | 0.49948 (10) | 1.03088 (9) | 0.17295 (6) | 0.0350 (2) | |
O1 | 0.77482 (9) | 0.93715 (8) | 0.18751 (5) | 0.0476 (3) | |
O2 | 0.87610 (9) | 1.20940 (9) | 0.35810 (6) | 0.0496 (3) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0289 (6) | 0.0340 (6) | 0.0307 (6) | −0.0012 (5) | 0.0029 (5) | −0.0016 (5) |
C2 | 0.0301 (6) | 0.0357 (6) | 0.0285 (6) | 0.0000 (5) | 0.0014 (5) | 0.0002 (5) |
C3 | 0.0324 (6) | 0.0408 (7) | 0.0310 (6) | −0.0041 (5) | 0.0015 (5) | 0.0007 (5) |
C4 | 0.0346 (6) | 0.0469 (7) | 0.0308 (6) | −0.0039 (6) | 0.0045 (5) | −0.0009 (5) |
C5 | 0.0403 (8) | 0.0671 (10) | 0.0485 (8) | −0.0051 (7) | 0.0151 (6) | 0.0025 (7) |
C6 | 0.0386 (8) | 0.0736 (11) | 0.0525 (9) | 0.0043 (7) | 0.0141 (7) | −0.0067 (8) |
C7 | 0.0345 (7) | 0.0576 (9) | 0.0437 (7) | 0.0084 (6) | 0.0044 (6) | −0.0045 (7) |
C8 | 0.0305 (6) | 0.0343 (6) | 0.0365 (6) | 0.0026 (5) | 0.0068 (5) | 0.0009 (5) |
C9 | 0.0370 (7) | 0.0395 (7) | 0.0456 (7) | −0.0023 (6) | 0.0049 (6) | −0.0027 (6) |
C10 | 0.0422 (8) | 0.0390 (8) | 0.0635 (10) | −0.0066 (6) | 0.0089 (7) | 0.0001 (7) |
C11 | 0.0492 (8) | 0.0451 (8) | 0.0607 (9) | −0.0040 (7) | 0.0152 (7) | 0.0143 (7) |
C12 | 0.0489 (8) | 0.0484 (8) | 0.0416 (7) | −0.0005 (7) | 0.0091 (6) | 0.0091 (6) |
C13 | 0.0349 (6) | 0.0370 (7) | 0.0364 (6) | 0.0019 (5) | 0.0072 (5) | 0.0018 (5) |
C14 | 0.0339 (6) | 0.0362 (6) | 0.0313 (6) | 0.0033 (5) | 0.0055 (5) | 0.0006 (5) |
C15 | 0.0354 (6) | 0.0394 (7) | 0.0333 (6) | 0.0036 (5) | 0.0016 (5) | −0.0021 (5) |
C16 | 0.0485 (8) | 0.0502 (8) | 0.0336 (7) | 0.0012 (7) | −0.0043 (6) | −0.0009 (6) |
C17 | 0.0435 (8) | 0.0578 (9) | 0.0429 (8) | −0.0021 (7) | −0.0080 (6) | −0.0082 (7) |
C18 | 0.0403 (7) | 0.0468 (8) | 0.0533 (8) | −0.0073 (6) | −0.0001 (6) | −0.0063 (7) |
C19 | 0.0393 (7) | 0.0423 (7) | 0.0431 (7) | −0.0018 (6) | 0.0014 (6) | 0.0017 (6) |
C20 | 0.0319 (6) | 0.0362 (6) | 0.0335 (6) | 0.0023 (5) | 0.0013 (5) | −0.0020 (5) |
C21 | 0.0294 (6) | 0.0351 (6) | 0.0295 (6) | 0.0026 (5) | 0.0021 (5) | −0.0011 (5) |
C22 | 0.0350 (6) | 0.0392 (7) | 0.0292 (6) | 0.0054 (5) | −0.0013 (5) | 0.0010 (5) |
C23 | 0.0330 (6) | 0.0478 (8) | 0.0381 (7) | 0.0086 (6) | 0.0039 (5) | 0.0056 (6) |
C24 | 0.0443 (8) | 0.0695 (11) | 0.0466 (8) | 0.0167 (7) | 0.0107 (7) | 0.0022 (7) |
C25 | 0.0412 (8) | 0.0904 (14) | 0.0661 (11) | 0.0174 (9) | 0.0221 (8) | 0.0175 (10) |
C26 | 0.0340 (7) | 0.0739 (12) | 0.0836 (13) | 0.0018 (8) | 0.0151 (8) | 0.0233 (10) |
C27 | 0.0339 (7) | 0.0519 (9) | 0.0687 (10) | −0.0015 (6) | 0.0033 (7) | 0.0079 (8) |
C28 | 0.0298 (6) | 0.0422 (7) | 0.0433 (7) | 0.0030 (5) | 0.0021 (5) | 0.0058 (6) |
C29 | 0.0311 (6) | 0.0387 (7) | 0.0354 (6) | −0.0002 (5) | −0.0010 (5) | 0.0004 (5) |
C30 | 0.0429 (7) | 0.0394 (7) | 0.0324 (6) | −0.0034 (6) | 0.0001 (5) | 0.0008 (5) |
C31 | 0.0433 (8) | 0.0687 (11) | 0.0661 (10) | −0.0014 (8) | 0.0022 (7) | 0.0266 (9) |
C32 | 0.0509 (10) | 0.0766 (13) | 0.0830 (13) | −0.0008 (9) | −0.0095 (9) | 0.0317 (11) |
C33 | 0.0765 (12) | 0.0546 (10) | 0.0522 (9) | −0.0003 (9) | −0.0101 (8) | 0.0174 (8) |
C34 | 0.0743 (12) | 0.0517 (9) | 0.0505 (9) | −0.0094 (8) | 0.0080 (8) | 0.0142 (7) |
C35 | 0.0488 (8) | 0.0510 (9) | 0.0522 (9) | −0.0073 (7) | 0.0041 (7) | 0.0089 (7) |
N1 | 0.0311 (5) | 0.0423 (6) | 0.0313 (5) | 0.0019 (4) | 0.0045 (4) | −0.0021 (4) |
N2 | 0.0413 (6) | 0.0423 (6) | 0.0313 (5) | 0.0007 (5) | 0.0018 (5) | 0.0013 (5) |
N3 | 0.0332 (5) | 0.0377 (6) | 0.0324 (5) | −0.0010 (4) | 0.0007 (4) | 0.0012 (4) |
O1 | 0.0496 (6) | 0.0445 (6) | 0.0463 (6) | 0.0007 (5) | 0.0008 (4) | −0.0102 (4) |
O2 | 0.0439 (6) | 0.0581 (6) | 0.0444 (6) | −0.0058 (5) | 0.0001 (4) | −0.0146 (5) |
Geometric parameters (Å, º) top
C1—N1 | 1.460 (2) | C15—C20 | 1.4149 (18) |
C1—C8 | 1.5350 (17) | C16—C17 | 1.359 (2) |
C1—C21 | 1.5440 (17) | C16—H16 | 0.9300 |
C1—C2 | 1.5885 (17) | C17—C18 | 1.393 (2) |
C2—C22 | 1.5306 (17) | C17—H17 | 0.9300 |
C2—C3 | 1.5348 (17) | C18—C19 | 1.368 (2) |
C2—C29 | 1.5391 (17) | C18—H18 | 0.9300 |
C3—C30 | 1.5149 (18) | C19—C20 | 1.4013 (19) |
C3—C4 | 1.5278 (19) | C19—H19 | 0.9300 |
C3—H3 | 0.9800 | C20—N3 | 1.381 (2) |
C4—N1 | 1.480 (2) | C21—N3 | 1.298 (2) |
C4—C5 | 1.5205 (19) | C22—O1 | 1.205 (2) |
C4—H4 | 0.9800 | C22—C23 | 1.4803 (19) |
C5—C6 | 1.516 (2) | C23—C28 | 1.382 (2) |
C5—H5A | 0.9700 | C23—C24 | 1.392 (2) |
C5—H5B | 0.9700 | C24—C25 | 1.377 (3) |
C6—C7 | 1.518 (2) | C24—H24 | 0.9300 |
C6—H6A | 0.9700 | C25—C26 | 1.383 (3) |
C6—H6B | 0.9700 | C25—H25 | 0.9300 |
C7—N1 | 1.472 (2) | C26—C27 | 1.378 (2) |
C7—H7A | 0.9700 | C26—H26 | 0.9300 |
C7—H7B | 0.9700 | C27—C28 | 1.385 (2) |
C8—C9 | 1.3838 (19) | C27—H27 | 0.9300 |
C8—C13 | 1.3942 (18) | C28—C29 | 1.4792 (19) |
C9—C10 | 1.381 (2) | C29—O2 | 1.202 (2) |
C9—H9 | 0.9300 | C30—C31 | 1.378 (2) |
C10—C11 | 1.381 (2) | C30—C35 | 1.384 (2) |
C10—H10 | 0.9300 | C31—C32 | 1.385 (2) |
C11—C12 | 1.377 (2) | C31—H31 | 0.9300 |
C11—H11 | 0.9300 | C32—C33 | 1.358 (3) |
C12—C13 | 1.3851 (19) | C32—H32 | 0.9300 |
C12—H12 | 0.9300 | C33—C34 | 1.372 (3) |
C13—C14 | 1.4528 (19) | C33—H33 | 0.9300 |
C14—N2 | 1.306 (2) | C34—C35 | 1.380 (2) |
C14—C21 | 1.4242 (17) | C34—H34 | 0.9300 |
C15—N2 | 1.368 (2) | C35—H35 | 0.9300 |
C15—C16 | 1.4098 (18) | | |
| | | |
N1—C1—C8 | 111.95 (10) | C17—C16—C15 | 120.07 (14) |
N1—C1—C21 | 114.76 (10) | C17—C16—H16 | 120.0 |
C8—C1—C21 | 100.54 (10) | C15—C16—H16 | 120.0 |
N1—C1—C2 | 100.51 (9) | C16—C17—C18 | 120.95 (13) |
C8—C1—C2 | 116.62 (10) | C16—C17—H17 | 119.5 |
C21—C1—C2 | 113.17 (10) | C18—C17—H17 | 119.5 |
C22—C2—C3 | 115.35 (11) | C19—C18—C17 | 120.37 (14) |
C22—C2—C29 | 102.26 (10) | C19—C18—H18 | 119.8 |
C3—C2—C29 | 117.11 (10) | C17—C18—H18 | 119.8 |
C22—C2—C1 | 113.89 (9) | C18—C19—C20 | 120.30 (14) |
C3—C2—C1 | 100.87 (9) | C18—C19—H19 | 119.9 |
C29—C2—C1 | 107.62 (10) | C20—C19—H19 | 119.9 |
C30—C3—C4 | 114.44 (11) | N3—C20—C19 | 119.22 (12) |
C30—C3—C2 | 119.40 (11) | N3—C20—C15 | 121.55 (12) |
C4—C3—C2 | 102.35 (10) | C19—C20—C15 | 119.20 (12) |
C30—C3—H3 | 106.6 | N3—C21—C14 | 123.17 (11) |
C4—C3—H3 | 106.6 | N3—C21—C1 | 126.56 (11) |
C2—C3—H3 | 106.6 | C14—C21—C1 | 109.94 (11) |
N1—C4—C5 | 104.66 (11) | O1—C22—C23 | 126.68 (12) |
N1—C4—C3 | 105.20 (10) | O1—C22—C2 | 125.50 (12) |
C5—C4—C3 | 119.53 (12) | C23—C22—C2 | 107.79 (11) |
N1—C4—H4 | 109.0 | C28—C23—C24 | 120.57 (14) |
C5—C4—H4 | 109.0 | C28—C23—C22 | 109.86 (12) |
C3—C4—H4 | 109.0 | C24—C23—C22 | 129.57 (14) |
C6—C5—C4 | 102.23 (13) | C25—C24—C23 | 117.65 (17) |
C6—C5—H5A | 111.3 | C25—C24—H24 | 121.2 |
C4—C5—H5A | 111.3 | C23—C24—H24 | 121.2 |
C6—C5—H5B | 111.3 | C24—C25—C26 | 121.35 (15) |
C4—C5—H5B | 111.3 | C24—C25—H25 | 119.3 |
H5A—C5—H5B | 109.2 | C26—C25—H25 | 119.3 |
C5—C6—C7 | 103.06 (12) | C27—C26—C25 | 121.32 (16) |
C5—C6—H6A | 111.2 | C27—C26—H26 | 119.3 |
C7—C6—H6A | 111.2 | C25—C26—H26 | 119.3 |
C5—C6—H6B | 111.2 | C26—C27—C28 | 117.38 (16) |
C7—C6—H6B | 111.2 | C26—C27—H27 | 121.3 |
H6A—C6—H6B | 109.1 | C28—C27—H27 | 121.3 |
N1—C7—C6 | 103.21 (11) | C23—C28—C27 | 121.61 (14) |
N1—C7—H7A | 111.1 | C23—C28—C29 | 109.90 (12) |
C6—C7—H7A | 111.1 | C27—C28—C29 | 128.49 (14) |
N1—C7—H7B | 111.1 | O2—C29—C28 | 125.95 (12) |
C6—C7—H7B | 111.1 | O2—C29—C2 | 126.77 (12) |
H7A—C7—H7B | 109.1 | C28—C29—C2 | 107.28 (11) |
C9—C8—C13 | 118.86 (12) | C31—C30—C35 | 116.97 (14) |
C9—C8—C1 | 129.49 (12) | C31—C30—C3 | 125.45 (13) |
C13—C8—C1 | 111.53 (11) | C35—C30—C3 | 117.58 (13) |
C10—C9—C8 | 119.18 (13) | C30—C31—C32 | 121.19 (16) |
C10—C9—H9 | 120.4 | C30—C31—H31 | 119.4 |
C8—C9—H9 | 120.4 | C32—C31—H31 | 119.4 |
C9—C10—C11 | 121.49 (14) | C33—C32—C31 | 120.94 (17) |
C9—C10—H10 | 119.3 | C33—C32—H32 | 119.5 |
C11—C10—H10 | 119.3 | C31—C32—H32 | 119.5 |
C12—C11—C10 | 120.05 (14) | C32—C33—C34 | 118.99 (16) |
C12—C11—H11 | 120.0 | C32—C33—H33 | 120.5 |
C10—C11—H11 | 120.0 | C34—C33—H33 | 120.5 |
C11—C12—C13 | 118.56 (14) | C33—C34—C35 | 120.16 (16) |
C11—C12—H12 | 120.7 | C33—C34—H34 | 119.9 |
C13—C12—H12 | 120.7 | C35—C34—H34 | 119.9 |
C12—C13—C8 | 121.76 (13) | C34—C35—C30 | 121.71 (16) |
C12—C13—C14 | 129.15 (12) | C34—C35—H35 | 119.1 |
C8—C13—C14 | 108.93 (11) | C30—C35—H35 | 119.1 |
N2—C14—C21 | 123.96 (12) | C1—N1—C7 | 119.5 (1) |
N2—C14—C13 | 126.96 (12) | C1—N1—C4 | 111.1 (1) |
C21—C14—C13 | 108.86 (11) | C7—N1—C4 | 109.9 (1) |
N2—C15—C16 | 118.86 (12) | C14—N2—C15 | 114.35 (11) |
N2—C15—C20 | 122.05 (11) | C21—N3—C20 | 114.86 (11) |
C16—C15—C20 | 119.09 (13) | | |
| | | |
N1—C1—C2—C22 | 166.11 (10) | C2—C1—C21—C14 | −125.81 (11) |
C8—C1—C2—C22 | −72.68 (14) | C3—C2—C22—O1 | 34.82 (17) |
C21—C1—C2—C22 | 43.25 (14) | C29—C2—C22—O1 | 163.06 (13) |
N1—C1—C2—C3 | 41.93 (11) | C1—C2—C22—O1 | −81.15 (16) |
C8—C1—C2—C3 | 163.14 (10) | C3—C2—C22—C23 | −143.39 (11) |
C21—C1—C2—C3 | −80.93 (11) | C29—C2—C22—C23 | −15.15 (13) |
N1—C1—C2—C29 | −81.29 (11) | C1—C2—C22—C23 | 100.63 (12) |
C8—C1—C2—C29 | 39.92 (13) | O1—C22—C23—C28 | −169.94 (13) |
C21—C1—C2—C29 | 155.85 (10) | C2—C22—C23—C28 | 8.25 (14) |
C22—C2—C3—C30 | 67.19 (15) | O1—C22—C23—C24 | 11.0 (2) |
C29—C2—C3—C30 | −53.24 (16) | C2—C22—C23—C24 | −170.81 (14) |
C1—C2—C3—C30 | −169.64 (11) | C28—C23—C24—C25 | −3.4 (2) |
C22—C2—C3—C4 | −165.26 (10) | C22—C23—C24—C25 | 175.53 (14) |
C29—C2—C3—C4 | 74.31 (13) | C23—C24—C25—C26 | 1.8 (3) |
C1—C2—C3—C4 | −42.09 (11) | C24—C25—C26—C27 | 1.5 (3) |
C30—C3—C4—N1 | 157.45 (11) | C25—C26—C27—C28 | −3.0 (2) |
C2—C3—C4—N1 | 26.80 (12) | C24—C23—C28—C27 | 1.9 (2) |
C30—C3—C4—C5 | −85.46 (15) | C22—C23—C28—C27 | −177.24 (13) |
C2—C3—C4—C5 | 143.89 (12) | C24—C23—C28—C29 | −177.88 (13) |
N1—C4—C5—C6 | −30.28 (14) | C22—C23—C28—C29 | 2.96 (15) |
C3—C4—C5—C6 | −147.65 (13) | C26—C27—C28—C23 | 1.3 (2) |
C4—C5—C6—C7 | 41.04 (15) | C26—C27—C28—C29 | −178.89 (14) |
C5—C6—C7—N1 | −36.05 (15) | C23—C28—C29—O2 | 166.77 (14) |
N1—C1—C8—C9 | 51.58 (17) | C27—C28—C29—O2 | −13.0 (2) |
C21—C1—C8—C9 | 173.87 (13) | C23—C28—C29—C2 | −12.92 (14) |
C2—C1—C8—C9 | −63.38 (17) | C27—C28—C29—C2 | 167.29 (14) |
N1—C1—C8—C13 | −124.41 (11) | C22—C2—C29—O2 | −162.89 (14) |
C21—C1—C8—C13 | −2.12 (13) | C3—C2—C29—O2 | −35.78 (19) |
C2—C1—C8—C13 | 120.63 (12) | C1—C2—C29—O2 | 76.86 (16) |
C13—C8—C9—C10 | −3.24 (19) | C22—C2—C29—C28 | 16.79 (13) |
C1—C8—C9—C10 | −178.99 (13) | C3—C2—C29—C28 | 143.91 (11) |
C8—C9—C10—C11 | 0.8 (2) | C1—C2—C29—C28 | −103.46 (11) |
C9—C10—C11—C12 | 1.7 (2) | C4—C3—C30—C31 | −114.88 (17) |
C10—C11—C12—C13 | −1.6 (2) | C2—C3—C30—C31 | 6.8 (2) |
C11—C12—C13—C8 | −1.0 (2) | C4—C3—C30—C35 | 65.38 (17) |
C11—C12—C13—C14 | 173.86 (14) | C2—C3—C30—C35 | −172.90 (13) |
C9—C8—C13—C12 | 3.4 (2) | C35—C30—C31—C32 | −1.4 (3) |
C1—C8—C13—C12 | 179.88 (12) | C3—C30—C31—C32 | 178.86 (17) |
C9—C8—C13—C14 | −172.35 (11) | C30—C31—C32—C33 | −0.2 (3) |
C1—C8—C13—C14 | 4.12 (14) | C31—C32—C33—C34 | 1.2 (3) |
C12—C13—C14—N2 | −5.0 (2) | C32—C33—C34—C35 | −0.6 (3) |
C8—C13—C14—N2 | 170.32 (13) | C33—C34—C35—C30 | −1.0 (3) |
C12—C13—C14—C21 | −179.84 (14) | C31—C30—C35—C34 | 2.0 (2) |
C8—C13—C14—C21 | −4.49 (14) | C3—C30—C35—C34 | −178.25 (15) |
N2—C15—C16—C17 | 179.49 (13) | C8—C1—N1—C7 | 79.48 (14) |
C20—C15—C16—C17 | −1.1 (2) | C21—C1—N1—C7 | −34.29 (16) |
C15—C16—C17—C18 | 0.0 (2) | C2—C1—N1—C7 | −156.04 (12) |
C16—C17—C18—C19 | 0.8 (2) | C8—C1—N1—C4 | −151.01 (10) |
C17—C18—C19—C20 | −0.5 (2) | C21—C1—N1—C4 | 95.22 (12) |
C18—C19—C20—N3 | 177.34 (13) | C2—C1—N1—C4 | −26.53 (12) |
C18—C19—C20—C15 | −0.6 (2) | C6—C7—N1—C1 | 147.35 (12) |
N2—C15—C20—N3 | 2.89 (19) | C6—C7—N1—C4 | 17.32 (15) |
C16—C15—C20—N3 | −176.52 (12) | C5—C4—N1—C1 | −126.22 (12) |
N2—C15—C20—C19 | −179.17 (12) | C3—C4—N1—C1 | 0.58 (13) |
C16—C15—C20—C19 | 1.42 (19) | C5—C4—N1—C7 | 8.2 (1) |
N2—C14—C21—N3 | 1.9 (2) | C3—C4—N1—C7 | 134.98 (11) |
C13—C14—C21—N3 | 176.87 (11) | C21—C14—N2—C15 | −1.35 (18) |
N2—C14—C21—C1 | −171.89 (12) | C13—C14—N2—C15 | −175.42 (12) |
C13—C14—C21—C1 | 3.11 (14) | C16—C15—N2—C14 | 178.49 (12) |
N1—C1—C21—N3 | −53.88 (17) | C20—C15—N2—C14 | −0.92 (18) |
C8—C1—C21—N3 | −174.17 (12) | C14—C21—N3—C20 | 0.11 (18) |
C2—C1—C21—N3 | 60.69 (16) | C1—C21—N3—C20 | 172.80 (11) |
N1—C1—C21—C14 | 119.62 (12) | C19—C20—N3—C21 | 179.74 (12) |
C8—C1—C21—C14 | −0.68 (12) | C15—C20—N3—C21 | −2.32 (18) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N3 | 0.98 | 2.49 | 3.178 (2) | 127 |
C9—H9···O2 | 0.93 | 2.54 | 3.229 (2) | 131 |
C16—H16···O1i | 0.93 | 2.51 | 3.252 (2) | 137 |
C18—H18···O2ii | 0.93 | 2.57 | 3.344 (2) | 141 |
C19—H19···N1ii | 0.93 | 2.46 | 3.275 (2) | 147 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2. |
Experimental details
Crystal data |
Chemical formula | C35H25N3O2 |
Mr | 519.58 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.1149 (14), 12.4670 (16), 18.646 (2) |
β (°) | 99.415 (2) |
V (Å3) | 2548.9 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.25 × 0.22 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28930, 6030, 4851 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.661 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.128, 1.03 |
No. of reflections | 6030 |
No. of parameters | 361 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.18 |
Selected geometric parameters (Å, º) topC1—N1 | 1.460 (2) | C20—N3 | 1.381 (2) |
C4—N1 | 1.480 (2) | C21—N3 | 1.298 (2) |
C7—N1 | 1.472 (2) | C22—O1 | 1.205 (2) |
C14—N2 | 1.306 (2) | C29—O2 | 1.202 (2) |
| | | |
C1—N1—C7 | 119.5 (1) | C7—N1—C4 | 109.9 (1) |
C1—N1—C4 | 111.1 (1) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···N3 | 0.98 | 2.49 | 3.178 (2) | 127 |
C9—H9···O2 | 0.93 | 2.54 | 3.229 (2) | 131 |
C16—H16···O1i | 0.93 | 2.51 | 3.252 (2) | 137 |
C18—H18···O2ii | 0.93 | 2.57 | 3.344 (2) | 141 |
C19—H19···N1ii | 0.93 | 2.46 | 3.275 (2) | 147 |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y−1/2, −z+1/2. |
Pyrrolidine, the saturated tetrahydropyrrole, is a basic intermediate used in wide range of applications in organic synthesis. It has also gained much attention in the pharmacological industry for its medicinal value. Derivatives of pyrrolidine are found to have anticonvulsant (Obniska et al., 2002), antimicrobial and antifungal activity against various pathogens, except Bacillus subtilis (Amal Raj et al., 2003). Quinoxaline derivatives show antibacterial, antiviral and anticancer properties (Zarranz et al., 2003). The spiro ring system is a frequently encountered structural motif in many pharmacologically relevant alkaloids. Synthetic spiro-pyrrolidine derivatives have activity against the aldose reductase enzyme which controls influenza (Stylianakis et al., 2003). As spiro-pyrrolidine compounds are of great medicinal importance, we have undertaken the three-dimensional structure determination of the title compound, (I), by X-ray diffraction (Fig. 1).
The sum of the bond angles at N1 of the pyrrolidine ring [340.4 (1)°] indicates sp3 hybridization. The C14═N2 and C21═N3 bond distances are comparable with other reported values (Allen et al., 1987). The spiro junction at C2 in the indanedione group deviates from the mean plane (C22–C29) by 0.290 (1) Å. Atoms O1 and O2 deviate from the mean plane of the indanedione ring by −0.240 (1) and −0.351 (1) Å, respectively. Atom O2 displays a greater deviation than atom O1, as it is involved in both intra- and intermolecular interactions, whereas atom O1 only forms an intermolecular hydrogen bond (Table 2).
In the pyrrolizidine system (A/B), rings A and B adopt envelope and twisted conformations, respectively. The puckering parameters (Cremer & Pople, 1975) and smallest displacement asymmetry parameters (Nardelli, 1983) are, for ring A, N1/C1–C4, q2 = 0.445 (1) Å, ϕ = 72.5 (2)° and Δs(C2) = 0.003 (1), and for ring B, N1/C4–C7, q2 = 0.401 (2) Å, ϕ = −83.7 (2)°, ΔC2(N1) = 0.026 (1). The pyrrolizidine moiety is twisted and folded about the N1—C4 bond, as indicated by the torsion angles C7—N1—C4—C5 [8.2 (1)°] and C7—N1—C4—H4 [−108.2 (1)°]; a similar conformation was reported by Usha et al. (2005).
In the crystal packing, atom O2 is involved in both intra- and intermolecular hydrogen bonding and acts as a bifurcated acceptor; the angle C9···O2···C18i between the donors is 85.0 (4)° [symmetry code: (i) 1 − x, 1/2 + y, 1/2 − z]. The translated molecules are linked by C18—H18···O2 and C19—H19···N1 hydrogen bonds, forming a binary graph set R22(9) (Bernstein et al., 1995). Hence, a zigzag pattern is formed by chains parallel to the b axis. Weak intermolecular π–π interactions occur between the stacked pyrazine and benzene rings, with a centroid separation of 3.866 (1)%A. These, together with a dimeric C16–H16···O1 hydrogen bond, stabilize the structure further.