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The racemic title dipyrrolopyrrolizine compound crystallizes from dimethylformamide as a disolvate, C
55H
39Cl
2N
7O
6·2C
3H
7NO. None of the four fused heterocyclic rings is planar; one adopts an envelope conformation, two others adopt half-chair conformations and the fourth adopts a conformation intermediate between an envelope and a half-chair. The arrangement of the ring fusions is such as to preclude the possibility of internal mirror symmetry. The three independent molecular components are weakly linked by C-H
O hydrogen bonds, and the dipyrrolopyrrolizine molecules are linked by a combination of four C-H
O and one C-H
(arene) hydrogen bond to form a three-dimensional framework, from which the dimethylformamide solvent molecules are pendent. However, aromatic
-
stacking interactions are absent in the structure.
Supporting information
CCDC reference: 914650
A mixture of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde (0.2 mmol),
N-(4-chlorophenyl)maleimide (0.2 mmol) and methyl glycinate
hydrochloride (0.1 mmol) in toluene (10 ml) was heated under reflux overnight.
The reaction mixture was cooled to ambient temperature and the resulting
precipitate was collected by filtration and washed with hexane to obtain the
pure heterocyclic product (yield 80%; m.p. 541–3 K). MS (EI, 70 eV)
m/z (%): 963 (M+, 5), 756 (25), 525 (13), 273 (36), 233
(100), 207 (58), 77 (90). Crystals of the title solvate, (I), were grown by
slow evaporation, at ambient temperature and in air, of a solution in
ethanol–dimethylformamide (1:1 v/v).
All H atoms were located in difference maps and subsequently treated as riding
atoms in geometrically idealized positions, with C—H = 0.95 (aromatic,
formyl and pyrazole), 0.98 (methyl) or 1.00 Å (aliphatic CH), and with
Uiso(H) = kUeq(C), where k = 1.5 for the methyl
groups, which were permitted to rotate but not to tilt, and k = 1.2 for
all other H atoms.
Data collection: COLLECT (Nonius, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Methyl (3a
RS,3c
RS,6c
SR,7
RS,8
RS,8a
SR)-
2,5-bis(4-chlorophenyl)-7,9-bis(1,3-diphenyl-1
H-pyrazol-4-yl)-1,3,4,6-
tetraoxododecahydro-1
H-dipyrrolo[3,4-
a:3',4'-
f]pyrrolizine-3b-carboxylate dimethylformamide disolvate
top
Crystal data top
C55H39Cl2N7O6·2C3H7NO | Z = 2 |
Mr = 1111.02 | F(000) = 1160 |
Triclinic, P1 | Dx = 1.370 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 13.948 (3) Å | Cell parameters from 12351 reflections |
b = 14.279 (3) Å | θ = 2.5–27.5° |
c = 16.3474 (16) Å | µ = 0.19 mm−1 |
α = 70.147 (12)° | T = 120 K |
β = 86.297 (13)° | Prism, colourless |
γ = 62.265 (16)° | 0.45 × 0.19 × 0.18 mm |
V = 2693.4 (9) Å3 | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 12351 independent reflections |
Radiation source: Bruker Nonius FR591 rotating anode | 8531 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.5° |
ϕ and ω scans | h = −18→18 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −18→18 |
Tmin = 0.920, Tmax = 0.967 | l = −21→21 |
67989 measured reflections | |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0581P)2 + 1.125P] where P = (Fo2 + 2Fc2)/3 |
12351 reflections | (Δ/σ)max = 0.001 |
726 parameters | Δρmax = 0.26 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
Crystal data top
C55H39Cl2N7O6·2C3H7NO | γ = 62.265 (16)° |
Mr = 1111.02 | V = 2693.4 (9) Å3 |
Triclinic, P1 | Z = 2 |
a = 13.948 (3) Å | Mo Kα radiation |
b = 14.279 (3) Å | µ = 0.19 mm−1 |
c = 16.3474 (16) Å | T = 120 K |
α = 70.147 (12)° | 0.45 × 0.19 × 0.18 mm |
β = 86.297 (13)° | |
Data collection top
Bruker Nonius KappaCCD area-detector diffractometer | 12351 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 8531 reflections with I > 2σ(I) |
Tmin = 0.920, Tmax = 0.967 | Rint = 0.051 |
67989 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.125 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.26 e Å−3 |
12351 reflections | Δρmin = −0.32 e Å−3 |
726 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.59197 (14) | 0.43024 (15) | 0.75264 (12) | 0.0190 (4) | |
O1 | 0.54236 (10) | 0.39679 (11) | 0.72231 (8) | 0.0237 (3) | |
N2 | 0.60969 (12) | 0.40874 (12) | 0.84157 (10) | 0.0197 (3) | |
C3 | 0.65386 (14) | 0.47196 (15) | 0.85727 (12) | 0.0188 (4) | |
O3 | 0.67625 (10) | 0.46764 (11) | 0.92914 (8) | 0.0229 (3) | |
C3a | 0.66531 (14) | 0.54706 (15) | 0.76897 (11) | 0.0190 (4) | |
H3a | 0.6085 | 0.6276 | 0.7552 | 0.023* | |
C3b | 0.77993 (14) | 0.53746 (15) | 0.75821 (12) | 0.0190 (4) | |
C3c | 0.78734 (15) | 0.63688 (15) | 0.68061 (12) | 0.0207 (4) | |
H3c | 0.8148 | 0.6771 | 0.7042 | 0.025* | |
C4 | 0.68300 (15) | 0.72008 (15) | 0.62078 (12) | 0.0214 (4) | |
O4 | 0.60163 (11) | 0.79207 (11) | 0.63615 (9) | 0.0264 (3) | |
N5 | 0.69510 (12) | 0.70013 (12) | 0.54173 (10) | 0.0203 (3) | |
C6 | 0.80072 (15) | 0.61600 (15) | 0.53882 (12) | 0.0214 (4) | |
O6 | 0.82695 (11) | 0.58626 (11) | 0.47626 (8) | 0.0263 (3) | |
C6a | 0.86905 (15) | 0.57786 (15) | 0.62383 (12) | 0.0207 (4) | |
H6a | 0.9238 | 0.6062 | 0.6114 | 0.025* | |
C7 | 0.92677 (14) | 0.45137 (15) | 0.68358 (12) | 0.0196 (4) | |
H7 | 0.9800 | 0.4449 | 0.7260 | 0.024* | |
N7a | 0.84093 (12) | 0.43537 (12) | 0.73617 (9) | 0.0181 (3) | |
C8 | 0.76600 (14) | 0.41919 (15) | 0.68802 (11) | 0.0181 (4) | |
H8 | 0.7729 | 0.4465 | 0.6240 | 0.022* | |
C8a | 0.64809 (14) | 0.49793 (15) | 0.70454 (12) | 0.0186 (4) | |
H8a | 0.6035 | 0.5586 | 0.6490 | 0.022* | |
C21 | 0.57673 (15) | 0.33689 (15) | 0.90816 (12) | 0.0210 (4) | |
C22 | 0.61067 (15) | 0.22754 (16) | 0.91061 (13) | 0.0246 (4) | |
H22 | 0.6557 | 0.2005 | 0.8691 | 0.030* | |
C23 | 0.57798 (16) | 0.15831 (16) | 0.97460 (13) | 0.0276 (4) | |
H23 | 0.6006 | 0.0833 | 0.9774 | 0.033* | |
C24 | 0.51196 (16) | 0.20026 (16) | 1.03423 (12) | 0.0246 (4) | |
Cl24 | 0.46852 (4) | 0.11574 (4) | 1.11409 (3) | 0.03337 (13) | |
C25 | 0.47738 (16) | 0.30929 (17) | 1.03145 (12) | 0.0259 (4) | |
H25 | 0.4324 | 0.3364 | 1.0730 | 0.031* | |
C26 | 0.50936 (15) | 0.37827 (16) | 0.96713 (12) | 0.0233 (4) | |
H26 | 0.4851 | 0.4539 | 0.9635 | 0.028* | |
C31 | 0.83165 (15) | 0.52547 (15) | 0.84412 (12) | 0.0208 (4) | |
O31 | 0.90394 (11) | 0.44073 (11) | 0.89322 (8) | 0.0261 (3) | |
O32 | 0.78085 (11) | 0.62533 (11) | 0.85560 (8) | 0.0248 (3) | |
C32 | 0.82096 (19) | 0.6281 (2) | 0.93348 (15) | 0.0379 (5) | |
H32A | 0.8089 | 0.5765 | 0.9853 | 0.057* | |
H32B | 0.7821 | 0.7050 | 0.9346 | 0.057* | |
H32C | 0.8991 | 0.6045 | 0.9334 | 0.057* | |
C51 | 0.61161 (14) | 0.76378 (15) | 0.46882 (12) | 0.0211 (4) | |
C52 | 0.58316 (16) | 0.70722 (16) | 0.42880 (13) | 0.0247 (4) | |
H52 | 0.6181 | 0.6270 | 0.4502 | 0.030* | |
C53 | 0.50371 (16) | 0.76801 (16) | 0.35751 (13) | 0.0258 (4) | |
H53 | 0.4835 | 0.7301 | 0.3297 | 0.031* | |
C54 | 0.45438 (15) | 0.88471 (16) | 0.32758 (12) | 0.0246 (4) | |
Cl54 | 0.35482 (4) | 0.96110 (4) | 0.23794 (3) | 0.03206 (13) | |
C55 | 0.48141 (15) | 0.94247 (16) | 0.36696 (13) | 0.0241 (4) | |
H55 | 0.4463 | 1.0227 | 0.3454 | 0.029* | |
C56 | 0.56046 (15) | 0.88125 (16) | 0.43827 (12) | 0.0229 (4) | |
H56 | 0.5798 | 0.9194 | 0.4663 | 0.027* | |
N71 | 1.05304 (12) | 0.24859 (13) | 0.56853 (10) | 0.0222 (3) | |
N72 | 1.13209 (12) | 0.19709 (13) | 0.63693 (10) | 0.0233 (3) | |
C73 | 1.09425 (15) | 0.26395 (15) | 0.68484 (12) | 0.0219 (4) | |
C74 | 0.99132 (15) | 0.35961 (15) | 0.64693 (12) | 0.0214 (4) | |
C75 | 0.96899 (15) | 0.34560 (15) | 0.57256 (12) | 0.0221 (4) | |
H75 | 0.9059 | 0.3951 | 0.5313 | 0.027* | |
C711 | 1.06570 (16) | 0.20263 (15) | 0.50128 (12) | 0.0232 (4) | |
C712 | 0.97514 (17) | 0.22644 (17) | 0.45208 (13) | 0.0304 (5) | |
H712 | 0.9041 | 0.2697 | 0.4652 | 0.036* | |
C713 | 0.9886 (2) | 0.18683 (18) | 0.38333 (15) | 0.0392 (5) | |
H713 | 0.9264 | 0.2043 | 0.3486 | 0.047* | |
C714 | 1.0917 (2) | 0.12214 (18) | 0.36485 (14) | 0.0395 (6) | |
H714 | 1.1005 | 0.0953 | 0.3176 | 0.047* | |
C715 | 1.18193 (19) | 0.09673 (18) | 0.41548 (15) | 0.0364 (5) | |
H715 | 1.2528 | 0.0517 | 0.4032 | 0.044* | |
C716 | 1.17016 (17) | 0.13638 (17) | 0.48430 (14) | 0.0292 (4) | |
H716 | 1.2324 | 0.1185 | 0.5191 | 0.035* | |
C731 | 1.16154 (15) | 0.23431 (15) | 0.76469 (13) | 0.0232 (4) | |
C732 | 1.27475 (16) | 0.18880 (16) | 0.76550 (14) | 0.0289 (4) | |
H732 | 1.3081 | 0.1738 | 0.7157 | 0.035* | |
C733 | 1.33828 (17) | 0.16553 (18) | 0.83826 (14) | 0.0329 (5) | |
H733 | 1.4149 | 0.1358 | 0.8378 | 0.039* | |
C734 | 1.29103 (18) | 0.18521 (18) | 0.91212 (15) | 0.0355 (5) | |
H734 | 1.3351 | 0.1688 | 0.9622 | 0.043* | |
C735 | 1.17929 (17) | 0.22895 (18) | 0.91238 (14) | 0.0324 (5) | |
H735 | 1.1467 | 0.2423 | 0.9629 | 0.039* | |
C736 | 1.11443 (16) | 0.25348 (16) | 0.83931 (13) | 0.0267 (4) | |
H736 | 1.0378 | 0.2834 | 0.8401 | 0.032* | |
N81 | 0.88956 (12) | 0.11309 (12) | 0.79518 (10) | 0.0207 (3) | |
N82 | 0.84433 (12) | 0.11865 (13) | 0.72157 (10) | 0.0220 (3) | |
C83 | 0.79051 (14) | 0.22897 (15) | 0.67389 (12) | 0.0198 (4) | |
C84 | 0.80174 (14) | 0.29477 (15) | 0.71797 (11) | 0.0185 (4) | |
C85 | 0.86586 (15) | 0.21689 (15) | 0.79432 (12) | 0.0208 (4) | |
H85 | 0.8896 | 0.2327 | 0.8388 | 0.025* | |
C811 | 0.96205 (16) | 0.00528 (16) | 0.85661 (12) | 0.0241 (4) | |
C812 | 1.05119 (17) | −0.00673 (18) | 0.90020 (14) | 0.0336 (5) | |
H812 | 1.0619 | 0.0567 | 0.8921 | 0.040* | |
C813 | 1.1250 (2) | −0.1140 (2) | 0.95628 (15) | 0.0441 (6) | |
H813 | 1.1865 | −0.1237 | 0.9868 | 0.053* | |
C814 | 1.1094 (2) | −0.20603 (19) | 0.96779 (15) | 0.0433 (6) | |
H814 | 1.1609 | −0.2790 | 1.0052 | 0.052* | |
C815 | 1.01899 (18) | −0.19224 (17) | 0.92485 (14) | 0.0363 (5) | |
H815 | 1.0077 | −0.2556 | 0.9338 | 0.044* | |
C816 | 0.94458 (17) | −0.08626 (17) | 0.86877 (13) | 0.0298 (4) | |
H816 | 0.8825 | −0.0766 | 0.8391 | 0.036* | |
C831 | 0.73592 (15) | 0.26333 (15) | 0.58672 (12) | 0.0209 (4) | |
C832 | 0.76015 (17) | 0.18195 (17) | 0.54855 (14) | 0.0314 (5) | |
H832 | 0.8107 | 0.1053 | 0.5796 | 0.038* | |
C833 | 0.71173 (18) | 0.21127 (19) | 0.46643 (14) | 0.0364 (5) | |
H833 | 0.7281 | 0.1544 | 0.4422 | 0.044* | |
C834 | 0.63980 (17) | 0.32241 (18) | 0.41910 (13) | 0.0310 (5) | |
H834 | 0.6078 | 0.3424 | 0.3621 | 0.037* | |
C835 | 0.61488 (16) | 0.40441 (17) | 0.45571 (12) | 0.0258 (4) | |
H835 | 0.5657 | 0.4811 | 0.4237 | 0.031* | |
C836 | 0.66158 (15) | 0.37476 (16) | 0.53902 (12) | 0.0230 (4) | |
H836 | 0.6425 | 0.4314 | 0.5640 | 0.028* | |
C91 | 0.32649 (18) | 0.72970 (18) | 0.78748 (14) | 0.0337 (5) | |
H91 | 0.2740 | 0.7065 | 0.8117 | 0.040* | |
O91 | 0.42152 (12) | 0.65609 (13) | 0.80007 (10) | 0.0386 (4) | |
N91 | 0.28977 (14) | 0.83955 (15) | 0.74295 (11) | 0.0312 (4) | |
C92 | 0.36478 (19) | 0.8836 (2) | 0.70684 (16) | 0.0417 (6) | |
H92A | 0.3708 | 0.8880 | 0.6457 | 0.062* | |
H92B | 0.4367 | 0.8333 | 0.7408 | 0.062* | |
H92C | 0.3373 | 0.9592 | 0.7097 | 0.062* | |
C93 | 0.17302 (18) | 0.91999 (19) | 0.72402 (17) | 0.0433 (6) | |
H93A | 0.1315 | 0.8823 | 0.7562 | 0.065* | |
H93B | 0.1511 | 0.9476 | 0.6611 | 0.065* | |
H93C | 0.1585 | 0.9838 | 0.7421 | 0.065* | |
C94 | 1.09468 (18) | 0.55855 (19) | 0.80133 (15) | 0.0355 (5) | |
H94 | 1.0947 | 0.5704 | 0.8551 | 0.043* | |
O94 | 1.00634 (12) | 0.58666 (13) | 0.76586 (10) | 0.0391 (4) | |
N94 | 1.19134 (14) | 0.51277 (15) | 0.77202 (12) | 0.0350 (4) | |
C95 | 1.2004 (2) | 0.4879 (2) | 0.69203 (16) | 0.0439 (6) | |
H95A | 1.1275 | 0.5136 | 0.6653 | 0.066* | |
H95B | 1.2442 | 0.4063 | 0.7056 | 0.066* | |
H95C | 1.2357 | 0.5270 | 0.6512 | 0.066* | |
C96 | 1.29245 (19) | 0.4769 (2) | 0.82245 (18) | 0.0487 (6) | |
H96A | 1.2757 | 0.5007 | 0.8735 | 0.073* | |
H96B | 1.3341 | 0.5114 | 0.7858 | 0.073* | |
H96C | 1.3356 | 0.3944 | 0.8420 | 0.073* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0148 (8) | 0.0184 (9) | 0.0207 (9) | −0.0047 (7) | 0.0009 (7) | −0.0076 (7) |
O1 | 0.0241 (7) | 0.0278 (7) | 0.0243 (7) | −0.0151 (6) | 0.0029 (5) | −0.0108 (6) |
N2 | 0.0212 (8) | 0.0192 (8) | 0.0191 (8) | −0.0102 (6) | 0.0030 (6) | −0.0065 (6) |
C3 | 0.0149 (8) | 0.0183 (9) | 0.0225 (9) | −0.0059 (7) | 0.0039 (7) | −0.0094 (7) |
O3 | 0.0249 (7) | 0.0266 (7) | 0.0204 (7) | −0.0133 (6) | 0.0038 (5) | −0.0104 (6) |
C3a | 0.0172 (9) | 0.0179 (9) | 0.0220 (9) | −0.0077 (7) | 0.0034 (7) | −0.0083 (7) |
C3b | 0.0188 (9) | 0.0183 (9) | 0.0213 (9) | −0.0089 (7) | 0.0026 (7) | −0.0084 (7) |
C3c | 0.0220 (9) | 0.0196 (9) | 0.0236 (9) | −0.0110 (8) | 0.0045 (7) | −0.0097 (8) |
C4 | 0.0250 (10) | 0.0186 (9) | 0.0223 (9) | −0.0120 (8) | 0.0042 (8) | −0.0070 (8) |
O4 | 0.0265 (7) | 0.0211 (7) | 0.0269 (7) | −0.0068 (6) | 0.0056 (6) | −0.0101 (6) |
N5 | 0.0194 (8) | 0.0180 (8) | 0.0216 (8) | −0.0071 (6) | 0.0023 (6) | −0.0074 (6) |
C6 | 0.0223 (9) | 0.0184 (9) | 0.0235 (10) | −0.0107 (8) | 0.0057 (8) | −0.0064 (8) |
O6 | 0.0290 (7) | 0.0248 (7) | 0.0223 (7) | −0.0097 (6) | 0.0070 (6) | −0.0102 (6) |
C6a | 0.0201 (9) | 0.0196 (9) | 0.0230 (9) | −0.0097 (8) | 0.0048 (7) | −0.0082 (8) |
C7 | 0.0180 (9) | 0.0210 (9) | 0.0211 (9) | −0.0092 (7) | 0.0038 (7) | −0.0089 (7) |
N7a | 0.0177 (7) | 0.0183 (8) | 0.0204 (8) | −0.0087 (6) | 0.0034 (6) | −0.0089 (6) |
C8 | 0.0176 (9) | 0.0201 (9) | 0.0169 (9) | −0.0086 (7) | 0.0005 (7) | −0.0071 (7) |
C8a | 0.0183 (9) | 0.0179 (9) | 0.0188 (9) | −0.0078 (7) | 0.0013 (7) | −0.0066 (7) |
C21 | 0.0205 (9) | 0.0214 (9) | 0.0206 (9) | −0.0109 (8) | −0.0003 (7) | −0.0050 (8) |
C22 | 0.0238 (10) | 0.0228 (10) | 0.0272 (10) | −0.0101 (8) | 0.0069 (8) | −0.0106 (8) |
C23 | 0.0292 (11) | 0.0194 (10) | 0.0330 (11) | −0.0107 (8) | 0.0033 (9) | −0.0088 (8) |
C24 | 0.0258 (10) | 0.0264 (10) | 0.0214 (9) | −0.0156 (8) | 0.0013 (8) | −0.0032 (8) |
Cl24 | 0.0393 (3) | 0.0334 (3) | 0.0277 (3) | −0.0227 (2) | 0.0057 (2) | −0.0033 (2) |
C25 | 0.0275 (10) | 0.0322 (11) | 0.0224 (10) | −0.0167 (9) | 0.0067 (8) | −0.0114 (8) |
C26 | 0.0248 (10) | 0.0246 (10) | 0.0246 (10) | −0.0130 (8) | 0.0043 (8) | −0.0117 (8) |
C31 | 0.0202 (9) | 0.0221 (10) | 0.0240 (10) | −0.0121 (8) | 0.0063 (8) | −0.0101 (8) |
O31 | 0.0248 (7) | 0.0275 (7) | 0.0236 (7) | −0.0102 (6) | 0.0007 (6) | −0.0091 (6) |
O32 | 0.0282 (7) | 0.0272 (7) | 0.0257 (7) | −0.0137 (6) | 0.0038 (6) | −0.0160 (6) |
C32 | 0.0389 (13) | 0.0469 (14) | 0.0380 (12) | −0.0182 (11) | 0.0003 (10) | −0.0286 (11) |
C51 | 0.0189 (9) | 0.0214 (9) | 0.0216 (9) | −0.0090 (8) | 0.0052 (7) | −0.0073 (8) |
C52 | 0.0277 (10) | 0.0203 (9) | 0.0272 (10) | −0.0127 (8) | 0.0039 (8) | −0.0079 (8) |
C53 | 0.0282 (10) | 0.0279 (10) | 0.0276 (10) | −0.0171 (9) | 0.0045 (8) | −0.0115 (8) |
C54 | 0.0198 (9) | 0.0294 (11) | 0.0254 (10) | −0.0135 (8) | 0.0052 (8) | −0.0083 (8) |
Cl54 | 0.0264 (3) | 0.0361 (3) | 0.0308 (3) | −0.0162 (2) | −0.0027 (2) | −0.0052 (2) |
C55 | 0.0212 (9) | 0.0211 (9) | 0.0284 (10) | −0.0100 (8) | 0.0051 (8) | −0.0072 (8) |
C56 | 0.0228 (9) | 0.0229 (10) | 0.0271 (10) | −0.0127 (8) | 0.0059 (8) | −0.0113 (8) |
N71 | 0.0206 (8) | 0.0220 (8) | 0.0253 (8) | −0.0089 (7) | 0.0037 (6) | −0.0116 (7) |
N72 | 0.0205 (8) | 0.0225 (8) | 0.0267 (8) | −0.0092 (7) | 0.0024 (7) | −0.0098 (7) |
C73 | 0.0200 (9) | 0.0198 (9) | 0.0264 (10) | −0.0101 (8) | 0.0057 (8) | −0.0083 (8) |
C74 | 0.0198 (9) | 0.0214 (9) | 0.0242 (10) | −0.0108 (8) | 0.0047 (7) | −0.0081 (8) |
C75 | 0.0192 (9) | 0.0214 (9) | 0.0267 (10) | −0.0092 (8) | 0.0048 (8) | −0.0106 (8) |
C711 | 0.0297 (10) | 0.0204 (9) | 0.0234 (10) | −0.0140 (8) | 0.0070 (8) | −0.0095 (8) |
C712 | 0.0317 (11) | 0.0271 (11) | 0.0321 (11) | −0.0115 (9) | 0.0024 (9) | −0.0134 (9) |
C713 | 0.0493 (14) | 0.0316 (12) | 0.0348 (12) | −0.0139 (11) | −0.0030 (10) | −0.0157 (10) |
C714 | 0.0605 (16) | 0.0309 (12) | 0.0295 (11) | −0.0193 (11) | 0.0103 (11) | −0.0177 (10) |
C715 | 0.0433 (13) | 0.0296 (12) | 0.0421 (13) | −0.0185 (10) | 0.0213 (11) | −0.0204 (10) |
C716 | 0.0309 (11) | 0.0250 (10) | 0.0369 (11) | −0.0157 (9) | 0.0112 (9) | −0.0147 (9) |
C731 | 0.0213 (9) | 0.0180 (9) | 0.0285 (10) | −0.0076 (8) | −0.0004 (8) | −0.0080 (8) |
C732 | 0.0223 (10) | 0.0261 (11) | 0.0345 (11) | −0.0065 (8) | 0.0030 (8) | −0.0135 (9) |
C733 | 0.0206 (10) | 0.0320 (11) | 0.0407 (12) | −0.0067 (9) | −0.0016 (9) | −0.0141 (10) |
C734 | 0.0310 (11) | 0.0364 (12) | 0.0358 (12) | −0.0117 (10) | −0.0064 (9) | −0.0133 (10) |
C735 | 0.0341 (12) | 0.0372 (12) | 0.0289 (11) | −0.0173 (10) | 0.0043 (9) | −0.0146 (9) |
C736 | 0.0246 (10) | 0.0265 (10) | 0.0306 (11) | −0.0121 (8) | 0.0041 (8) | −0.0118 (9) |
N81 | 0.0212 (8) | 0.0169 (8) | 0.0201 (8) | −0.0066 (6) | −0.0013 (6) | −0.0049 (6) |
N82 | 0.0234 (8) | 0.0212 (8) | 0.0212 (8) | −0.0102 (7) | 0.0004 (6) | −0.0072 (7) |
C83 | 0.0192 (9) | 0.0198 (9) | 0.0200 (9) | −0.0092 (8) | 0.0018 (7) | −0.0067 (7) |
C84 | 0.0169 (9) | 0.0207 (9) | 0.0188 (9) | −0.0090 (7) | 0.0035 (7) | −0.0079 (7) |
C85 | 0.0214 (9) | 0.0202 (9) | 0.0220 (9) | −0.0103 (8) | 0.0025 (7) | −0.0083 (8) |
C811 | 0.0257 (10) | 0.0211 (10) | 0.0191 (9) | −0.0069 (8) | 0.0027 (8) | −0.0059 (8) |
C812 | 0.0356 (12) | 0.0282 (11) | 0.0306 (11) | −0.0101 (9) | −0.0065 (9) | −0.0084 (9) |
C813 | 0.0405 (13) | 0.0389 (13) | 0.0350 (13) | −0.0063 (11) | −0.0147 (10) | −0.0072 (10) |
C814 | 0.0465 (14) | 0.0266 (12) | 0.0307 (12) | −0.0021 (10) | −0.0035 (11) | −0.0008 (9) |
C815 | 0.0379 (12) | 0.0204 (10) | 0.0356 (12) | −0.0078 (9) | 0.0087 (10) | −0.0021 (9) |
C816 | 0.0290 (11) | 0.0240 (10) | 0.0317 (11) | −0.0104 (9) | 0.0062 (9) | −0.0082 (9) |
C831 | 0.0201 (9) | 0.0212 (9) | 0.0232 (9) | −0.0103 (8) | 0.0024 (7) | −0.0088 (8) |
C832 | 0.0356 (12) | 0.0248 (10) | 0.0310 (11) | −0.0093 (9) | −0.0040 (9) | −0.0125 (9) |
C833 | 0.0412 (13) | 0.0341 (12) | 0.0356 (12) | −0.0122 (10) | −0.0030 (10) | −0.0212 (10) |
C834 | 0.0288 (11) | 0.0409 (12) | 0.0245 (10) | −0.0150 (10) | −0.0003 (8) | −0.0144 (9) |
C835 | 0.0239 (10) | 0.0269 (10) | 0.0236 (10) | −0.0109 (8) | 0.0016 (8) | −0.0070 (8) |
C836 | 0.0229 (10) | 0.0253 (10) | 0.0232 (10) | −0.0117 (8) | 0.0026 (8) | −0.0108 (8) |
C91 | 0.0326 (12) | 0.0335 (12) | 0.0368 (12) | −0.0154 (10) | 0.0087 (9) | −0.0155 (10) |
O91 | 0.0297 (8) | 0.0346 (8) | 0.0430 (9) | −0.0082 (7) | 0.0016 (7) | −0.0138 (7) |
N91 | 0.0280 (9) | 0.0304 (10) | 0.0355 (10) | −0.0128 (8) | 0.0095 (8) | −0.0145 (8) |
C92 | 0.0385 (13) | 0.0436 (14) | 0.0476 (14) | −0.0251 (11) | 0.0063 (11) | −0.0135 (11) |
C93 | 0.0343 (13) | 0.0331 (13) | 0.0558 (15) | −0.0113 (10) | 0.0147 (11) | −0.0161 (11) |
C94 | 0.0333 (12) | 0.0400 (13) | 0.0372 (12) | −0.0214 (10) | 0.0050 (10) | −0.0126 (10) |
O94 | 0.0274 (8) | 0.0422 (9) | 0.0486 (10) | −0.0190 (7) | 0.0014 (7) | −0.0127 (8) |
N94 | 0.0254 (9) | 0.0346 (10) | 0.0424 (11) | −0.0154 (8) | 0.0027 (8) | −0.0087 (8) |
C95 | 0.0448 (14) | 0.0390 (13) | 0.0493 (15) | −0.0207 (11) | 0.0137 (11) | −0.0174 (11) |
C96 | 0.0302 (12) | 0.0464 (15) | 0.0652 (17) | −0.0196 (11) | −0.0051 (12) | −0.0105 (13) |
Geometric parameters (Å, º) top
C1—O1 | 1.210 (2) | C712—H712 | 0.9500 |
C1—N2 | 1.393 (2) | C713—C714 | 1.382 (3) |
C1—C8a | 1.508 (3) | C713—H713 | 0.9500 |
N2—C3 | 1.399 (2) | C714—C715 | 1.380 (3) |
N2—C21 | 1.437 (2) | C714—H714 | 0.9500 |
C3—O3 | 1.209 (2) | C715—C716 | 1.391 (3) |
C3—C3a | 1.529 (3) | C715—H715 | 0.9500 |
C3a—C8a | 1.533 (2) | C716—H716 | 0.9500 |
C3a—C3b | 1.543 (2) | C731—C736 | 1.397 (3) |
C3a—H3a | 1.0000 | C731—C732 | 1.399 (3) |
C3b—N7a | 1.463 (2) | C732—C733 | 1.380 (3) |
C3b—C31 | 1.541 (2) | C732—H732 | 0.9500 |
C3b—C3c | 1.591 (3) | C733—C734 | 1.388 (3) |
C3c—C4 | 1.507 (3) | C733—H733 | 0.9500 |
C3c—C6a | 1.540 (3) | C734—C735 | 1.383 (3) |
C3c—H3c | 1.0000 | C734—H734 | 0.9500 |
C4—O4 | 1.209 (2) | C735—C736 | 1.389 (3) |
C4—N5 | 1.399 (2) | C735—H735 | 0.9500 |
N5—C6 | 1.414 (2) | C736—H736 | 0.9500 |
N5—C51 | 1.436 (2) | N81—C85 | 1.355 (2) |
C6—O6 | 1.209 (2) | N81—N82 | 1.356 (2) |
C6—C6a | 1.520 (3) | N81—C811 | 1.426 (2) |
C6a—C7 | 1.554 (3) | N82—C83 | 1.339 (2) |
C6a—H6a | 1.0000 | C83—C84 | 1.428 (2) |
C7—N7a | 1.488 (2) | C83—C831 | 1.473 (2) |
C7—C74 | 1.501 (3) | C84—C85 | 1.367 (3) |
C7—H7 | 1.0000 | C85—H85 | 0.9500 |
N7a—C8 | 1.490 (2) | C811—C812 | 1.384 (3) |
C8—C84 | 1.504 (2) | C811—C816 | 1.386 (3) |
C8—C8a | 1.572 (2) | C812—C813 | 1.395 (3) |
C8—H8 | 1.0000 | C812—H812 | 0.9500 |
C8a—H8a | 1.0000 | C813—C814 | 1.379 (4) |
C21—C26 | 1.384 (3) | C813—H813 | 0.9500 |
C21—C22 | 1.391 (3) | C814—C815 | 1.383 (3) |
C22—C23 | 1.391 (3) | C814—H814 | 0.9500 |
C22—H22 | 0.9500 | C815—C816 | 1.388 (3) |
C23—C24 | 1.387 (3) | C815—H815 | 0.9500 |
C23—H23 | 0.9500 | C816—H816 | 0.9500 |
C24—C25 | 1.384 (3) | C831—C836 | 1.393 (3) |
C24—Cl24 | 1.742 (2) | C831—C832 | 1.398 (3) |
C25—C26 | 1.385 (3) | C832—C833 | 1.381 (3) |
C25—H25 | 0.9500 | C832—H832 | 0.9500 |
C26—H26 | 0.9500 | C833—C834 | 1.381 (3) |
C31—O31 | 1.198 (2) | C833—H833 | 0.9500 |
C31—O32 | 1.340 (2) | C834—C835 | 1.386 (3) |
O32—C32 | 1.443 (2) | C834—H834 | 0.9500 |
C32—H32A | 0.9800 | C835—C836 | 1.387 (3) |
C32—H32B | 0.9800 | C835—H835 | 0.9500 |
C32—H32C | 0.9800 | C836—H836 | 0.9500 |
C51—C52 | 1.389 (3) | C91—O91 | 1.223 (3) |
C51—C56 | 1.391 (3) | C91—N91 | 1.333 (3) |
C52—C53 | 1.387 (3) | C91—H91 | 0.9500 |
C52—H52 | 0.9500 | N91—C92 | 1.456 (3) |
C53—C54 | 1.383 (3) | N91—C93 | 1.466 (3) |
C53—H53 | 0.9500 | C92—H92A | 0.9800 |
C54—C55 | 1.385 (3) | C92—H92B | 0.9800 |
C54—Cl54 | 1.742 (2) | C92—H92C | 0.9800 |
C55—C56 | 1.384 (3) | C93—H93A | 0.9800 |
C55—H55 | 0.9500 | C93—H93B | 0.9800 |
C56—H56 | 0.9500 | C93—H93C | 0.9800 |
N71—C75 | 1.356 (2) | C94—O94 | 1.220 (2) |
N71—N72 | 1.361 (2) | C94—N94 | 1.336 (3) |
N71—C711 | 1.424 (2) | C94—H94 | 0.9500 |
N72—C73 | 1.338 (2) | N94—C95 | 1.451 (3) |
C73—C74 | 1.423 (3) | N94—C96 | 1.457 (3) |
C73—C731 | 1.475 (3) | C95—H95A | 0.9800 |
C74—C75 | 1.374 (3) | C95—H95B | 0.9800 |
C75—H75 | 0.9500 | C95—H95C | 0.9800 |
C711—C712 | 1.380 (3) | C96—H96A | 0.9800 |
C711—C716 | 1.392 (3) | C96—H96B | 0.9800 |
C712—C713 | 1.387 (3) | C96—H96C | 0.9800 |
| | | |
O1—C1—N2 | 124.61 (17) | C712—C711—C716 | 120.63 (18) |
O1—C1—C8a | 128.00 (16) | C712—C711—N71 | 120.08 (17) |
N2—C1—C8a | 107.36 (14) | C716—C711—N71 | 119.26 (17) |
C1—N2—C3 | 112.48 (15) | C711—C712—C713 | 119.5 (2) |
C1—N2—C21 | 122.84 (14) | C711—C712—H712 | 120.2 |
C3—N2—C21 | 124.47 (15) | C713—C712—H712 | 120.2 |
O3—C3—N2 | 124.53 (17) | C714—C713—C712 | 120.6 (2) |
O3—C3—C3a | 127.29 (16) | C714—C713—H713 | 119.7 |
N2—C3—C3a | 108.17 (14) | C712—C713—H713 | 119.7 |
C3—C3a—C8a | 103.06 (14) | C715—C714—C713 | 119.6 (2) |
C3—C3a—C3b | 115.13 (14) | C715—C714—H714 | 120.2 |
C8a—C3a—C3b | 105.30 (14) | C713—C714—H714 | 120.2 |
C3—C3a—H3a | 111.0 | C714—C715—C716 | 120.7 (2) |
C8a—C3a—H3a | 111.0 | C714—C715—H715 | 119.6 |
C3b—C3a—H3a | 111.0 | C716—C715—H715 | 119.6 |
N7a—C3b—C31 | 111.15 (14) | C715—C716—C711 | 118.9 (2) |
N7a—C3b—C3a | 103.87 (14) | C715—C716—H716 | 120.5 |
C31—C3b—C3a | 110.64 (14) | C711—C716—H716 | 120.5 |
N7a—C3b—C3c | 106.21 (14) | C736—C731—C732 | 118.87 (18) |
C31—C3b—C3c | 108.57 (14) | C736—C731—C73 | 121.38 (17) |
C3a—C3b—C3c | 116.24 (14) | C732—C731—C73 | 119.72 (18) |
C4—C3c—C6a | 105.76 (15) | C733—C732—C731 | 120.40 (19) |
C4—C3c—C3b | 114.70 (15) | C733—C732—H732 | 119.8 |
C6a—C3c—C3b | 104.83 (14) | C731—C732—H732 | 119.8 |
C4—C3c—H3c | 110.4 | C732—C733—C734 | 120.51 (19) |
C6a—C3c—H3c | 110.4 | C732—C733—H733 | 119.7 |
C3b—C3c—H3c | 110.4 | C734—C733—H733 | 119.7 |
O4—C4—N5 | 124.44 (17) | C735—C734—C733 | 119.55 (19) |
O4—C4—C3c | 127.60 (17) | C735—C734—H734 | 120.2 |
N5—C4—C3c | 107.97 (15) | C733—C734—H734 | 120.2 |
C4—N5—C6 | 112.95 (15) | C734—C735—C736 | 120.5 (2) |
C4—N5—C51 | 123.59 (15) | C734—C735—H735 | 119.8 |
C6—N5—C51 | 123.33 (15) | C736—C735—H735 | 119.8 |
O6—C6—N5 | 122.87 (17) | C735—C736—C731 | 120.20 (19) |
O6—C6—C6a | 129.29 (17) | C735—C736—H736 | 119.9 |
N5—C6—C6a | 107.81 (15) | C731—C736—H736 | 119.9 |
C6—C6a—C3c | 104.55 (14) | C85—N81—N82 | 111.85 (14) |
C6—C6a—C7 | 120.60 (15) | C85—N81—C811 | 128.59 (15) |
C3c—C6a—C7 | 103.85 (14) | N82—N81—C811 | 119.17 (14) |
C6—C6a—H6a | 109.1 | C83—N82—N81 | 105.05 (14) |
C3c—C6a—H6a | 109.1 | N82—C83—C84 | 110.88 (15) |
C7—C6a—H6a | 109.1 | N82—C83—C831 | 118.49 (16) |
N7a—C7—C74 | 113.75 (14) | C84—C83—C831 | 130.55 (16) |
N7a—C7—C6a | 104.41 (14) | C85—C84—C83 | 104.38 (16) |
C74—C7—C6a | 121.47 (15) | C85—C84—C8 | 124.54 (15) |
N7a—C7—H7 | 105.3 | C83—C84—C8 | 130.71 (16) |
C74—C7—H7 | 105.3 | N81—C85—C84 | 107.83 (16) |
C6a—C7—H7 | 105.3 | N81—C85—H85 | 126.1 |
C3b—N7a—C7 | 105.90 (13) | C84—C85—H85 | 126.1 |
C3b—N7a—C8 | 110.06 (13) | C812—C811—C816 | 121.31 (18) |
C7—N7a—C8 | 112.94 (13) | C812—C811—N81 | 119.15 (18) |
N7a—C8—C84 | 108.01 (13) | C816—C811—N81 | 119.48 (17) |
N7a—C8—C8a | 105.36 (13) | C811—C812—C813 | 118.6 (2) |
C84—C8—C8a | 117.30 (15) | C811—C812—H812 | 120.7 |
N7a—C8—H8 | 108.6 | C813—C812—H812 | 120.7 |
C84—C8—H8 | 108.6 | C814—C813—C812 | 120.6 (2) |
C8a—C8—H8 | 108.6 | C814—C813—H813 | 119.7 |
C1—C8a—C3a | 105.06 (14) | C812—C813—H813 | 119.7 |
C1—C8a—C8 | 111.22 (14) | C813—C814—C815 | 120.0 (2) |
C3a—C8a—C8 | 105.06 (14) | C813—C814—H814 | 120.0 |
C1—C8a—H8a | 111.7 | C815—C814—H814 | 120.0 |
C3a—C8a—H8a | 111.7 | C814—C815—C816 | 120.2 (2) |
C8—C8a—H8a | 111.7 | C814—C815—H815 | 119.9 |
C26—C21—C22 | 121.01 (18) | C816—C815—H815 | 119.9 |
C26—C21—N2 | 119.72 (16) | C811—C816—C815 | 119.2 (2) |
C22—C21—N2 | 119.25 (17) | C811—C816—H816 | 120.4 |
C23—C22—C21 | 119.26 (18) | C815—C816—H816 | 120.4 |
C23—C22—H22 | 120.4 | C836—C831—C832 | 117.74 (17) |
C21—C22—H22 | 120.4 | C836—C831—C83 | 122.90 (16) |
C24—C23—C22 | 119.10 (18) | C832—C831—C83 | 119.34 (17) |
C24—C23—H23 | 120.4 | C833—C832—C831 | 120.97 (19) |
C22—C23—H23 | 120.4 | C833—C832—H832 | 119.5 |
C25—C24—C23 | 121.72 (18) | C831—C832—H832 | 119.5 |
C25—C24—Cl24 | 118.34 (15) | C832—C833—C834 | 120.70 (19) |
C23—C24—Cl24 | 119.94 (15) | C832—C833—H833 | 119.6 |
C24—C25—C26 | 118.98 (18) | C834—C833—H833 | 119.6 |
C24—C25—H25 | 120.5 | C833—C834—C835 | 119.20 (18) |
C26—C25—H25 | 120.5 | C833—C834—H834 | 120.4 |
C21—C26—C25 | 119.91 (18) | C835—C834—H834 | 120.4 |
C21—C26—H26 | 120.0 | C834—C835—C836 | 120.18 (18) |
C25—C26—H26 | 120.0 | C834—C835—H835 | 119.9 |
O31—C31—O32 | 125.60 (17) | C836—C835—H835 | 119.9 |
O31—C31—C3b | 125.83 (16) | C835—C836—C831 | 121.17 (18) |
O32—C31—C3b | 108.56 (15) | C835—C836—H836 | 119.4 |
C31—O32—C32 | 115.24 (15) | C831—C836—H836 | 119.4 |
O32—C32—H32A | 109.5 | O91—C91—N91 | 126.0 (2) |
O32—C32—H32B | 109.5 | O91—C91—H91 | 117.0 |
H32A—C32—H32B | 109.5 | N91—C91—H91 | 117.0 |
O32—C32—H32C | 109.5 | C91—N91—C92 | 120.84 (19) |
H32A—C32—H32C | 109.5 | C91—N91—C93 | 122.02 (19) |
H32B—C32—H32C | 109.5 | C92—N91—C93 | 117.06 (18) |
C52—C51—C56 | 120.46 (17) | N91—C92—H92A | 109.5 |
C52—C51—N5 | 119.52 (16) | N91—C92—H92B | 109.5 |
C56—C51—N5 | 120.02 (16) | H92A—C92—H92B | 109.5 |
C53—C52—C51 | 119.93 (17) | N91—C92—H92C | 109.5 |
C53—C52—H52 | 120.0 | H92A—C92—H92C | 109.5 |
C51—C52—H52 | 120.0 | H92B—C92—H92C | 109.5 |
C54—C53—C52 | 118.82 (17) | N91—C93—H93A | 109.5 |
C54—C53—H53 | 120.6 | N91—C93—H93B | 109.5 |
C52—C53—H53 | 120.6 | H93A—C93—H93B | 109.5 |
C53—C54—C55 | 122.00 (18) | N91—C93—H93C | 109.5 |
C53—C54—Cl54 | 118.86 (15) | H93A—C93—H93C | 109.5 |
C55—C54—Cl54 | 119.14 (15) | H93B—C93—H93C | 109.5 |
C56—C55—C54 | 118.84 (18) | O94—C94—N94 | 126.4 (2) |
C56—C55—H55 | 120.6 | O94—C94—H94 | 116.8 |
C54—C55—H55 | 120.6 | N94—C94—H94 | 116.8 |
C55—C56—C51 | 119.94 (17) | C94—N94—C95 | 121.03 (19) |
C55—C56—H56 | 120.0 | C94—N94—C96 | 121.6 (2) |
C51—C56—H56 | 120.0 | C95—N94—C96 | 117.2 (2) |
C75—N71—N72 | 112.16 (14) | N94—C95—H95A | 109.5 |
C75—N71—C711 | 127.10 (16) | N94—C95—H95B | 109.5 |
N72—N71—C711 | 120.69 (15) | H95A—C95—H95B | 109.5 |
C73—N72—N71 | 104.20 (14) | N94—C95—H95C | 109.5 |
N72—C73—C74 | 112.02 (16) | H95A—C95—H95C | 109.5 |
N72—C73—C731 | 119.02 (16) | H95B—C95—H95C | 109.5 |
C74—C73—C731 | 128.92 (17) | N94—C96—H96A | 109.5 |
C75—C74—C73 | 103.80 (16) | N94—C96—H96B | 109.5 |
C75—C74—C7 | 130.51 (17) | H96A—C96—H96B | 109.5 |
C73—C74—C7 | 125.68 (16) | N94—C96—H96C | 109.5 |
N71—C75—C74 | 107.80 (16) | H96A—C96—H96C | 109.5 |
N71—C75—H75 | 126.1 | H96B—C96—H96C | 109.5 |
C74—C75—H75 | 126.1 | | |
| | | |
O1—C1—N2—C3 | −170.43 (17) | C3a—C3b—C31—O31 | 106.4 (2) |
C8a—C1—N2—C3 | 11.21 (19) | C3c—C3b—C31—O31 | −124.89 (19) |
O1—C1—N2—C21 | 4.4 (3) | C3a—C3b—C31—O32 | −72.43 (18) |
C8a—C1—N2—C21 | −173.92 (15) | C3c—C3b—C31—O32 | 56.23 (18) |
C1—N2—C3—O3 | −179.97 (17) | O31—C31—O32—C32 | 1.6 (3) |
C21—N2—C3—O3 | 5.3 (3) | C3b—C31—O32—C32 | −179.49 (16) |
C1—N2—C3—C3a | 1.36 (19) | C4—N5—C51—C52 | −130.36 (19) |
C21—N2—C3—C3a | −173.41 (15) | C4—N5—C51—C56 | 50.2 (2) |
O3—C3—C3a—C8a | 168.50 (17) | C6—N5—C51—C56 | −125.28 (19) |
N2—C3—C3a—C8a | −12.88 (18) | C56—C51—C52—C53 | 0.4 (3) |
O3—C3—C3a—C3b | 54.4 (2) | N5—C51—C52—C53 | −179.05 (17) |
N2—C3—C3a—C3b | −126.96 (15) | C51—C52—C53—C54 | 0.1 (3) |
C3—C3a—C3b—N7a | 80.68 (17) | C52—C53—C54—C55 | −0.4 (3) |
C8a—C3a—C3b—N7a | −32.09 (17) | C52—C53—C54—Cl54 | 179.87 (15) |
C3—C3a—C3b—C31 | −38.7 (2) | C53—C54—C55—C56 | 0.2 (3) |
C8a—C3a—C3b—C31 | −151.45 (14) | Cl54—C54—C55—C56 | 179.88 (14) |
C3—C3a—C3b—C3c | −163.07 (14) | C54—C55—C56—C51 | 0.4 (3) |
C8a—C3a—C3b—C3c | 84.16 (17) | C52—C51—C56—C55 | −0.7 (3) |
N7a—C3b—C3c—C4 | 107.66 (16) | N5—C51—C56—C55 | 178.80 (17) |
C31—C3b—C3c—C4 | −132.74 (16) | C75—N71—N72—C73 | 0.9 (2) |
C3a—C3b—C3c—C4 | −7.3 (2) | C711—N71—N72—C73 | 178.54 (16) |
N7a—C3b—C3c—C6a | −7.88 (17) | N71—N72—C73—C74 | −0.8 (2) |
C31—C3b—C3c—C6a | 111.73 (16) | N71—N72—C73—C731 | −178.76 (16) |
C3a—C3b—C3c—C6a | −122.82 (16) | N72—C73—C74—C75 | 0.4 (2) |
C6a—C3c—C4—O4 | −171.56 (18) | C731—C73—C74—C75 | 178.09 (19) |
C3b—C3c—C4—O4 | 73.4 (2) | N72—C73—C74—C7 | −179.63 (17) |
C6a—C3c—C4—N5 | 8.67 (19) | C731—C73—C74—C7 | −1.9 (3) |
C3b—C3c—C4—N5 | −106.33 (17) | N7a—C7—C74—C75 | 83.3 (2) |
O4—C4—N5—C6 | 176.14 (17) | C6a—C7—C74—C75 | −42.7 (3) |
C3c—C4—N5—C6 | −4.1 (2) | C6a—C7—C74—C73 | 137.29 (19) |
O4—C4—N5—C51 | 0.3 (3) | N72—N71—C75—C74 | −0.7 (2) |
C3c—C4—N5—C51 | −179.96 (15) | C711—N71—C75—C74 | −178.16 (17) |
C4—N5—C6—O6 | 179.48 (17) | C73—C74—C75—N71 | 0.2 (2) |
C51—N5—C6—O6 | −4.6 (3) | C7—C74—C75—N71 | −179.79 (18) |
C4—N5—C6—C6a | −2.4 (2) | C75—N71—C711—C712 | −27.1 (3) |
C51—N5—C6—C6a | 173.50 (15) | C75—N71—C711—C716 | 151.08 (19) |
O6—C6—C6a—C3c | −174.45 (19) | N72—N71—C711—C716 | −26.2 (3) |
N5—C6—C6a—C3c | 7.59 (19) | C716—C711—C712—C713 | −2.0 (3) |
O6—C6—C6a—C7 | −58.3 (3) | N71—C711—C712—C713 | 176.11 (18) |
N5—C6—C6a—C7 | 123.76 (17) | C711—C712—C713—C714 | 1.2 (3) |
C4—C3c—C6a—C6 | −9.73 (18) | C712—C713—C714—C715 | 0.1 (3) |
C3b—C3c—C6a—C6 | 111.86 (15) | C713—C714—C715—C716 | −0.6 (3) |
C4—C3c—C6a—C7 | −137.01 (14) | C714—C715—C716—C711 | −0.2 (3) |
C3b—C3c—C6a—C7 | −15.42 (17) | C712—C711—C716—C715 | 1.5 (3) |
C6—C6a—C7—N7a | −83.06 (19) | N71—C711—C716—C715 | −176.63 (18) |
C3c—C6a—C7—N7a | 33.46 (17) | N72—C73—C731—C736 | −143.85 (19) |
C6—C6a—C7—C74 | 47.1 (2) | C74—C73—C731—C736 | 38.6 (3) |
C3c—C6a—C7—C74 | 163.61 (16) | C74—C73—C731—C732 | −139.7 (2) |
C31—C3b—N7a—C7 | −88.53 (17) | C736—C731—C732—C733 | −1.3 (3) |
C3a—C3b—N7a—C7 | 152.47 (13) | C73—C731—C732—C733 | 176.99 (18) |
C3c—C3b—N7a—C7 | 29.37 (16) | C731—C732—C733—C734 | 1.0 (3) |
C31—C3b—N7a—C8 | 149.10 (14) | C732—C733—C734—C735 | −0.3 (3) |
C3a—C3b—N7a—C8 | 30.10 (18) | C733—C734—C735—C736 | −0.2 (3) |
C3c—C3b—N7a—C8 | −93.00 (16) | C734—C735—C736—C731 | −0.1 (3) |
C74—C7—N7a—C3b | −174.18 (14) | C732—C731—C736—C735 | 0.8 (3) |
C6a—C7—N7a—C3b | −39.60 (16) | C73—C731—C736—C735 | −177.43 (18) |
C74—C7—N7a—C8 | −53.66 (19) | C85—N81—N82—C83 | −0.4 (2) |
C6a—C7—N7a—C8 | 80.92 (16) | C811—N81—N82—C83 | −173.86 (16) |
C3b—N7a—C8—C84 | −142.18 (15) | N81—N82—C83—C84 | 0.0 (2) |
C7—N7a—C8—C84 | 99.71 (16) | N81—N82—C83—C831 | 177.14 (16) |
C3b—N7a—C8—C8a | −16.06 (18) | N82—C83—C84—C85 | 0.3 (2) |
C7—N7a—C8—C8a | −134.17 (14) | C831—C83—C84—C85 | −176.35 (19) |
O1—C1—C8a—C3a | 162.85 (17) | N82—C83—C84—C8 | 173.48 (17) |
N2—C1—C8a—C3a | −18.86 (18) | C831—C83—C84—C8 | −3.2 (3) |
O1—C1—C8a—C8 | −84.0 (2) | N7a—C8—C84—C85 | 19.7 (2) |
N2—C1—C8a—C8 | 94.28 (16) | C8a—C8—C84—C85 | −99.1 (2) |
C3—C3a—C8a—C1 | 18.78 (17) | C8a—C8—C84—C83 | 89.0 (2) |
C3b—C3a—C8a—C1 | 139.81 (14) | N82—N81—C85—C84 | 0.6 (2) |
C3—C3a—C8a—C8 | −98.64 (15) | C811—N81—C85—C84 | 173.32 (17) |
C3b—C3a—C8a—C8 | 22.39 (18) | C83—C84—C85—N81 | −0.5 (2) |
N7a—C8—C8a—C1 | −117.90 (15) | C8—C84—C85—N81 | −174.23 (16) |
C84—C8—C8a—C1 | 2.3 (2) | C85—N81—C811—C812 | −28.8 (3) |
N7a—C8—C8a—C3a | −4.75 (17) | C85—N81—C811—C816 | 153.89 (19) |
C84—C8—C8a—C3a | 115.42 (16) | N82—N81—C811—C816 | −33.8 (3) |
C1—N2—C21—C26 | −124.16 (19) | C816—C811—C812—C813 | 0.9 (3) |
C3—N2—C21—C26 | 50.1 (2) | N81—C811—C812—C813 | −176.3 (2) |
C1—N2—C21—C22 | 54.0 (2) | C811—C812—C813—C814 | 0.2 (4) |
N7a—C8—C84—C83 | −152.27 (18) | C812—C813—C814—C815 | −1.2 (4) |
N82—N81—C811—C812 | 143.45 (18) | C813—C814—C815—C816 | 1.2 (4) |
N82—C83—C831—C832 | −13.5 (3) | C812—C811—C816—C815 | −1.0 (3) |
N7a—C3b—C31—O31 | −8.4 (3) | N81—C811—C816—C815 | 176.28 (18) |
C6—N5—C51—C52 | 54.2 (2) | C814—C815—C816—C811 | −0.1 (3) |
N7a—C7—C74—C73 | −96.7 (2) | N82—C83—C831—C836 | 167.62 (18) |
N72—N71—C711—C712 | 155.67 (18) | C84—C83—C831—C836 | −15.9 (3) |
N72—C73—C731—C732 | 37.9 (3) | C84—C83—C831—C832 | 163.0 (2) |
N7a—C3b—C31—O32 | 172.70 (14) | C836—C831—C832—C833 | −0.1 (3) |
C3—N2—C21—C22 | −131.79 (18) | C83—C831—C832—C833 | −179.1 (2) |
C26—C21—C22—C23 | −1.3 (3) | C831—C832—C833—C834 | 1.4 (4) |
N2—C21—C22—C23 | −179.44 (16) | C832—C833—C834—C835 | −1.3 (3) |
C21—C22—C23—C24 | 0.2 (3) | C833—C834—C835—C836 | −0.2 (3) |
C22—C23—C24—C25 | 0.3 (3) | C834—C835—C836—C831 | 1.5 (3) |
C22—C23—C24—Cl24 | 179.17 (14) | C832—C831—C836—C835 | −1.3 (3) |
C23—C24—C25—C26 | 0.2 (3) | C83—C831—C836—C835 | 177.59 (18) |
Cl24—C24—C25—C26 | −178.62 (14) | O91—C91—N91—C92 | −2.7 (3) |
C22—C21—C26—C25 | 1.9 (3) | O91—C91—N91—C93 | 173.9 (2) |
N2—C21—C26—C25 | −179.99 (16) | O94—C94—N94—C95 | −2.0 (4) |
C24—C25—C26—C21 | −1.4 (3) | O94—C94—N94—C96 | −176.6 (2) |
Hydrogen-bond geometry (Å, º) topCg is the centroid of the C51-C56 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3a—H3a···O91 | 1.00 | 2.54 | 3.104 (3) | 115 |
C3c—H3c···O94 | 1.00 | 2.46 | 3.102 (3) | 121 |
C7—H7···O94 | 1.00 | 2.51 | 3.275 (3) | 134 |
C53—H53···O1i | 0.95 | 2.41 | 3.355 (3) | 170 |
C55—H55···O4ii | 0.95 | 2.53 | 3.392 (3) | 151 |
C814—H814···O3iii | 0.95 | 2.49 | 3.422 (3) | 164 |
C835—H835···O1i | 0.95 | 2.49 | 3.280 (3) | 141 |
C732—H732···Cgiv | 0.95 | 2.81 | 3.654 (3) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x+2, −y, −z+2; (iv) −x+2, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | C55H39Cl2N7O6·2C3H7NO |
Mr | 1111.02 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 13.948 (3), 14.279 (3), 16.3474 (16) |
α, β, γ (°) | 70.147 (12), 86.297 (13), 62.265 (16) |
V (Å3) | 2693.4 (9) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.19 |
Crystal size (mm) | 0.45 × 0.19 × 0.18 |
|
Data collection |
Diffractometer | Bruker Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.920, 0.967 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 67989, 12351, 8531 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.125, 1.05 |
No. of reflections | 12351 |
No. of parameters | 726 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.32 |
Selected torsion angles (º) topC1—N2—C21—C22 | 54.0 (2) | C6—N5—C51—C52 | 54.2 (2) |
N7a—C8—C84—C83 | −152.27 (18) | N7a—C7—C74—C73 | −96.7 (2) |
N82—N81—C811—C812 | 143.45 (18) | N72—N71—C711—C712 | 155.67 (18) |
N82—C83—C831—C832 | −13.5 (3) | N72—C73—C731—C732 | 37.9 (3) |
N7a—C3b—C31—O31 | −8.4 (3) | N7a—C3b—C31—O32 | 172.70 (14) |
Hydrogen-bond geometry (Å, º) topCg is the centroid of the C51-C56 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3a—H3a···O91 | 1.00 | 2.54 | 3.104 (3) | 115 |
C3c—H3c···O94 | 1.00 | 2.46 | 3.102 (3) | 121 |
C7—H7···O94 | 1.00 | 2.51 | 3.275 (3) | 134 |
C53—H53···O1i | 0.95 | 2.41 | 3.355 (3) | 170 |
C55—H55···O4ii | 0.95 | 2.53 | 3.392 (3) | 151 |
C814—H814···O3iii | 0.95 | 2.49 | 3.422 (3) | 164 |
C835—H835···O1i | 0.95 | 2.49 | 3.280 (3) | 141 |
C732—H732···Cgiv | 0.95 | 2.81 | 3.654 (3) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+2, −z+1; (iii) −x+2, −y, −z+2; (iv) −x+2, −y+1, −z+1. |
Ring-puckering parameters (Å, °) for the fused five-membered rings topRing | Q2 | ϕ2 |
N2/C1/C8a/C3a/C3 | 0.193 (2) | 257.2 (6) |
N5/C4/C3c/C6/C6 | 0.096 (2) | 95.9 (13) |
N7a/C3b/C3a/C8a/C8 | 0.311 (2) | 225.2 (4) |
N7a/C3b/C3c/C6a/C7 | 0.368 (2) | 155.0 (3) |
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Multicomponent reactions are of great synthetic importance because of their high levels of simplicity, diversity and selectivity. Equally, 1,3-dipolar cycloaddition reactions between azomethinic ylides and electrodeficient alkenes are an important method for the synthesis of pyrrolidinic-type heterocyclic compounds (Zhang & Chen, 2005; Cui et al., 2011; Quiroga et al., 2011). We report here the structure of the title compound, (I), as a dimethylformamide disolvate, prepared as an example of a catalyst-free tricomponent reaction between formyl-pyrazoles, N-arylmaleimides and methyl glycinate (see Scheme 1) for the synthesis of a pyrazole-substituted dipyrrolo[3,4-a:3',4'-f]pyrrolizine, where three important heterocyclic units of known biological potential, namely pyrrole, pyrazole and pyrrolizidine, have been incorporated into this product of a double-click reaction (Radwan & El-Kashef, 1998; Ribes et al., 2009). Few compounds containing the dipyrrolo[3,4-a:3',4'-f]pyrrolizine unit have been structurally characterized; these include compound (II) (see Scheme 2) [Cambridge Structural Database (CSD; Allen, 2002) refcode YARPUD; Gan, 2005] and several of its analogues containing additional ester groups on the molecular periphery (CSD refcodes YARQAK, YARQEO and YARQIS; Gan, 2005), and compound (III), which crystallizes as a 1:1 toluene solvate (CSD refcode GAWCUE; Cui et al., 2012).
The heterocyclic component methyl (3aRS,3cRS,6cSR,7RS,8RS,8aSR)-2,5-bis(4-chlorophenyl)-7,9-bis(1,3-diphenyl-1H-pyrazol-4-yl)-1,3,4,6-tetraoxododecahydro-1H-dipyrrolo[3,4-a:3',4'-f]pyrrolizine-3b-carboxylate, (A) (see Scheme 1), crystallizes from dimethylformamide solution as the disolvate, (I) (Fig. 1), and the three independent molecular components are weakly linked by C—H···O hydrogen bonds (Table 2). The constitution of the dipyrrolopyrrolizine component (A) is such that, with an appropriate arrangement of the ring-fusion geometry, it could in principle exhibit mirror symmetry across the plane through atoms N7a, C3b and C31 (see Scheme 1 and Fig. 1). In such circumstances, the members of each of the corresponding pairs of stereogenic centres in the two halves of the molecule would be of opposite configuration. In the event, the ring-fusion geometry is such that the two members of each pair have the same configuration. Thus, in the selected reference molecule, atoms C3a, C3c, C7 and C8 all have the R configuration, while atoms C6a and C8a both have the S configuration. This alone is sufficient to preclude any internal molecular symmetry. In addition, the torsion angles defining the orientations of the substituents at atoms N2 and N5, and at C7 and C8, together with those defining the orientation of the unsubstituted phenyl rings (Table 1), are significantly different between the two halves of the molecule. Finally, the orientation of the ester component is such that atoms O31 and O32 are displaced from the plane through atoms N7a, C3b and C31. Despite the presence of six stereogenic centres in the dipyrrolopyrrolizine molecule, this component is in fact racemic, as shown by the centrosymmetric space group.
None of the four fused rings is planar. The ring-puckering parameters (Cremer & Pople, 1975; Table 3) indicate that the ring containing atom C1 adopts a conformation very close to the envelope form, where the idealized value of ϕ2 is (36 × k)°, with the ring folded across the vector C1···C3a; the rings containing atoms C6 and C7 both adopt half-chair conformations, where the idealized value of ϕ2 is (18 + 36 x k)°; and the ring containing atom C8 adopts a conformation intermediate between the envelope and half-chair forms. These observations again preclude the possibility of any internal symmetry.
As noted above, the independent molecular components are weakly linked by C—H···O hydrogen bonds. However, atom O91 acts only as a single acceptor of hydrogen bonds, while atom O94 acts as a double acceptor (Table 2), forming an R21(6) (Bernstein et al., 1995) motif. Apart from these interactions, the dimethylformamide molecules do not participate in any other hydrogen bonds and hence they play no significant part in the supramolecular aggregation. On the basis of both the sparsity and the weakness of the C—H···O interactions involving the dimethylformamide molecules, it seems likely that they play an essentially passive role, simply occupying what would otherwise be empty spaces in the supramolecular structure defined by the dipyrrolopyrrolizine molecules, and interacting with this structure via little more than adventitious intermolecular contacts.
The heterocyclic molecules of (I) are linked into a three-dimensional framework structure of some complexity by a combination of C—H···O and C—H···π(arene) hydrogen bonds (Table 2), but the formation of the framework is readily analysed in terms of three one-dimensional substructures (Ferguson et al., 1998a,b; Gregson et al., 2000). In the analysis of the intermolecular interactions, C—H···O contacts in which the D—H···A angle is less than 140° have been discounted (Wood et al., 2009), aside from those noted earlier involving the dimethylformamide components, as have those involving C—H bonds in methyl groups. The C—H···O interaction involving atom C835 as the donor has a C—H···O angle of only 141° and so it is probably of fairly marginal significance (Wood et al., 2009). Its effect, if it were to be regarded as structurally significant, would simply be to reinforce the action of the near-linear hydrogen bond having atom C53 as the donor. Accordingly, this interaction need not be considered further in the description of the framework formation. It is interesting to note here that, despite the presence of six independent aryl groups, the crystal structure of (I) exhibits no aromatic π–π stacking interactions.
In the first substructure, a combination of two C—H···O hydrogen bonds, both involving atom O1 as the acceptor, and the C—H···π(arene) hydrogen bond link inversion-related molecules to generate a chain of rings running parallel to the [100] direction. Inversion-related pairs of C—H···O hydrogen bonds generate an R22(24) motif, and rings of this type, centred at (n+1/2, 1/2, 1/2), alternate with rings centred at (n, 1/2, 1/2), where n represents an integer in both cases, which are generated by inversion-related pairs of C—H···π(arene) hydrogen bonds (Fig. 2).
In the second substructure, a combination of two C—H···O hydrogen bonds, the donors of which both form part of the C51–C56 ring, link inversion-related molecules to form a chain of rings running parallel to the [010] direction, in which R22(14) rings centred at (1/2, n, 1/2) alternate with R22(24) rings centred at (1/2, n+1/2, 1/2), where n represents an integer in each case (Fig. 3).
In the final substructure, a combination of three C—H···O hydrogen bonds, two having atom O1 as the acceptor and the third having atom O3 as the acceptor, link inversion-related molecules to form a chain of rings running parallel to the [111] direction. In this chain, R22(24) centred at (n+1/2, 1/2-n, n+1/2) alternate with R22(26) rings centred at (n, 1-n, n), where n represents an integer in each case (Fig. 4). The combination of these three chains of rings, along [100], [010] and [111], respectively, all built from dipyrrolopyrrolizine molecules from which the dimethylformamide molecules are simply pendent, then generates a single three-dimensional framework structure.