organic compounds
10-(4-Chlorophenyl)-14a-hydroxy-12-methyl-8,9,9a,10,12,13,14,14a-octahydro-5H-10a,14-methanoindeno[2′,1′:4,5]azepino[3,4-b]pyrrolizine-5,15(7H,11H)-dione
aDepartment of Physics, The Madura College, Madurai 625 011, India, bDepartment of Organic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625 021, India, and cDepartment of Food Science and Technology, University of Ruhuna, Mapalana, Kamburupitiya 81100, Sri Lanka
*Correspondence e-mail: plakshmannilantha@ymail.com
The 26H25ClN2O3, contains two independent molecules (A and B). The conformation of the two molecules differs essentially in the dihedral angle involving the two benzene rings. They are inclined to one another by 52.47 (10) in A and by 31.75 (11)° in B. In both molecules, the six-membered piperidin-3-one rings have chair conformations. In molecule A, all four five-membered rings have twist conformations. In molecule B, only three of the four five-membered rings have twist conformations. The fourth, of the inden-1-one moiety, has an with the spiro C atom, bonded to the N atom of the pyrrolidine ring, as the flap. A weak intramolecular O—H⋯N hydrogen bond occurs in each independent molecule while a C—H⋯O interaction is also observed in molecule A. In the crystal, pairs of O—H⋯O hydrogen bonds link the molecules, forming inversion dimers with graph-set motif R22(12). These dimers are further interconnected by C—H⋯O and C—H⋯π interactions, forming a three-dimensional network.
of the title compound, CCCDC reference: 977765
Related literature
For the importance of pyrrolizine derivatives, see: Anderson & Corey (1977); Makoni & Sugden (1980); Barsoum & Nawar (2003); Abbas et al. (2010). For the importance of piperidines, see: Rubiralta et al. (1991); Pinder (1992); Michael (2001). For puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2004); cell SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97.
Supporting information
CCDC reference: 977765
https://doi.org/10.1107/S1600536813034107/ds2236sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813034107/ds2236Isup2.hkl
A mixture of 1-methyl-3-[E-(4-chlorophenyl)methylidene]tetrahydro-2(1H)- pyridinone (1 mmol), ninhydrin (1 mmol) and proline (1 mmol) in methanol was refluxed for 3–4 h. After completion of the reaction as indicated by TLC the reaction mixture was poured into cold water. The solid precipitate obtained was filtered and dried. The product was purified by
using petroleum ether:ethylacetate mixture (90:10 V/V). Suitable crystals for the single-crystal-X-ray studies were obtained by recrystalizing the product from methanol. Yield: 57%, Melting point: 470–472 K.H atoms were placed at calculated positions and allowed to ride on their carrier atoms with C—H = 0.93–0.98 Å. Uiso = 1.2Ueq(C) for CH2 and CH groups and Uiso = 1.5Ueq(C) for CH3 group.
Pyrrolizine derivatives have antimicrobial (Barsoum & Nawar, 2003), anti- inflammatory (Abbas et al., 2010) and antileukemic (Anderson & Corey, 1977) activities. These derivatives are used as inhibitors of blood platelet aggregation (Makoni & Sugden, 1980), Functionalized piperidines are familiar substructures found in biologically active natural products and synthetic pharmaceuticals (Michael, 2001; Pinder, 1992; Rubiralta et al., 1991). Against this background and to ascertain the molecular structure and conformation, the X-ray
determination of the title compound has been carried out.The Φ2 = 13.0 (2) ° and q2 = 0.4096 (19) Å and Φ2 = 193.9 (3)° (Cremer & Pople, 1975), in molecule A and in molecule B respectively. The pyrrolidine rings (N2/C8—C11) adopt twisted conformation with the puckering parameters q2 = 0.453 (2) Å, Φ2 = 194.8 (3) ° and q2 = 0.461 (2) Å, Φ2 = 10.9 (3) ° (Cremer & Pople, 1975) respectively for molecule A and molecule B. The cyclopentane ring (C12A—C16A) in molecule A adopts a twisted conformation with the puckering parameters q2 = 0.0775 (19) Å and Φ2 = 18.0 (1) ° (Cremer & Pople, 1975). The cyclopentane ring (C12B—C16B) in molecule B adopts an envelop conformation with the puckering parameters q2 = 0.111 (2) Å and Φ2 = 186.4 (12) ° (Cremer & Pople, 1975). The C16—O2 distances in the indolone, in molecules A and B are 1.212 (2) ° and 1.208 (2) A °, respectively. The deviation of O2 from planarity seems to have considerably influenced, the torsion angles N2—C12–C16—O2 and C17—C15—C16—O2 (55.3 (2) ° and 7.2 (2)° in molecule A and -59.4 (2) ° and -1.1 (4)° in molecule B). The differences in these torsion angles may also be attributed due to O1—H1—N2 interaction in molecules A and B. The piperidine ring (N1/C2—C6) adopts a slightly twisted chair conformation in both molecules with the puckering parameters of Q = 0.668 (2) Å, Θ = 166.48 (2) ° and Φ = 22.0 (7) ° in molecule A, Q = 0.161 (2) Å, Θ = 13.97 (17)° and Φ = 203.5 (8) ° in molecule B (Cremer & Pople, 1975). Short contacts H26 ··· H8 (2.17 Å for molecule A and 2.20 Å for molecule B) result in substantial widening of the bond angles C7—C21—C26 (124.05I(17) ° for molecule A and 122.60 (18) ° for molecule B).
of the title compound (Fig 1) C37H28N2O3, comprises two independent molecules. In the pyrrazoline ring system, the pyrrolidine rings (N2/C8/C7/C5/C12) adopt twisted conformations with the puckering parameters q2 = 0.4373 (18) Å andThe structure features weak intra-molecular O—H···N, C—H···O interactions. The
features inter-molecular C—H···O and O—H···O interactions. The O1B—H1B···O3B interaction forms, inversely related dimers generating a graph set motif R22(12). These dimers are further interconnected by C1A—H3···O3B and C1A—H2···Cg1 inter-molecular interactions (where Cg1 is the ring centroid of (C21A—C26A) as shown in Fig 2.For the importance of pyrrolizine derivatives, see: Anderson & Corey (1977); Makoni & Sugden (1980); Barsoum & Nawar (2003); Abbas et al. (2010). For the importance of piperidines, see: Rubiralta et al. (1991); Pinder (1992); Michael (2001). For puckering parameters, see: Cremer & Pople (1975).
Data collection: APEX2 (Bruker, 2004); cell
SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).Fig. 1. The molecular structure of (I), showing 20% probability displacement ellipsoids and the atom-numbering scheme. H-atoms are omitted for clarity. | |
Fig. 2. Partial packing diagram. |
C26H25ClN2O3 | F(000) = 1888 |
Mr = 448.93 | Dx = 1.358 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2yn | Cell parameters from 2000 reflections |
a = 13.5839 (4) Å | θ = 2–31° |
b = 11.3764 (4) Å | µ = 0.21 mm−1 |
c = 28.5382 (9) Å | T = 293 K |
β = 95.120 (2)° | Block, colourless |
V = 4392.6 (2) Å3 | 0.21 × 0.19 × 0.18 mm |
Z = 8 |
Bruker Kappa APEXII diffractometer | 10365 independent reflections |
Radiation source: fine-focus sealed tube | 7088 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.041 |
Detector resolution: 0 pixels mm-1 | θmax = 27.8°, θmin = 1.4° |
ω and φ scans | h = −17→17 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −14→14 |
Tmin = 0.967, Tmax = 0.974 | l = −37→37 |
85408 measured reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0445P)2 + 2.0326P] where P = (Fo2 + 2Fc2)/3 |
10365 reflections | (Δ/σ)max < 0.001 |
591 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.38 e Å−3 |
C26H25ClN2O3 | V = 4392.6 (2) Å3 |
Mr = 448.93 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.5839 (4) Å | µ = 0.21 mm−1 |
b = 11.3764 (4) Å | T = 293 K |
c = 28.5382 (9) Å | 0.21 × 0.19 × 0.18 mm |
β = 95.120 (2)° |
Bruker Kappa APEXII diffractometer | 10365 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 7088 reflections with I > 2σ(I) |
Tmin = 0.967, Tmax = 0.974 | Rint = 0.041 |
85408 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.33 e Å−3 |
10365 reflections | Δρmin = −0.38 e Å−3 |
591 parameters |
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 F.2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
H2 | 0.2541 (19) | 0.164 (2) | 0.3395 (10) | 0.088 (9)* | |
H3 | 0.353 (2) | 0.193 (3) | 0.3711 (10) | 0.106 (10)* | |
C1A | 0.2818 (2) | 0.2028 (2) | 0.37004 (10) | 0.0629 (6) | |
C2A | 0.27703 (14) | 0.38693 (18) | 0.41290 (7) | 0.0479 (5) | |
H4 | 0.3484 | 0.3938 | 0.4175 | 0.057* | |
H5 | 0.2550 | 0.3433 | 0.4392 | 0.057* | |
C3A | 0.23041 (14) | 0.51019 (17) | 0.41138 (6) | 0.0452 (4) | |
H3A | 0.2476 | 0.5544 | 0.4404 | 0.054* | |
C4A | 0.26576 (14) | 0.56995 (17) | 0.36915 (7) | 0.0453 (4) | |
C5A | 0.21563 (12) | 0.50383 (15) | 0.32732 (6) | 0.0357 (4) | |
C6A | 0.27022 (13) | 0.38621 (16) | 0.32724 (6) | 0.0402 (4) | |
H6 | 0.2475 | 0.3409 | 0.2996 | 0.048* | |
H7 | 0.3408 | 0.3991 | 0.3270 | 0.048* | |
C7A | 0.20490 (13) | 0.57492 (16) | 0.28073 (6) | 0.0394 (4) | |
H7A | 0.2240 | 0.6563 | 0.2882 | 0.047* | |
C8A | 0.09354 (13) | 0.57262 (16) | 0.26891 (6) | 0.0408 (4) | |
H8A | 0.0747 | 0.4980 | 0.2534 | 0.049* | |
C9A | 0.03576 (16) | 0.67175 (19) | 0.24399 (7) | 0.0549 (5) | |
H8 | 0.0302 | 0.6607 | 0.2101 | 0.066* | |
H9 | 0.0663 | 0.7473 | 0.2515 | 0.066* | |
C10A | −0.06550 (16) | 0.6621 (2) | 0.26367 (8) | 0.0598 (6) | |
H10A | −0.0870 | 0.7385 | 0.2739 | 0.072* | |
H10B | −0.1145 | 0.6321 | 0.2399 | 0.072* | |
C11A | −0.05198 (14) | 0.5771 (2) | 0.30546 (8) | 0.0545 (5) | |
H11A | −0.0843 | 0.6062 | 0.3321 | 0.065* | |
H11B | −0.0774 | 0.4996 | 0.2970 | 0.065* | |
C12A | 0.10984 (12) | 0.48544 (15) | 0.34328 (6) | 0.0350 (4) | |
C13A | 0.11777 (13) | 0.50876 (16) | 0.39756 (6) | 0.0408 (4) | |
C14A | 0.06538 (13) | 0.40713 (17) | 0.41807 (6) | 0.0433 (4) | |
C15A | 0.03857 (13) | 0.32319 (17) | 0.38446 (7) | 0.0427 (4) | |
C16A | 0.06537 (13) | 0.36182 (16) | 0.33787 (6) | 0.0391 (4) | |
C17A | −0.00229 (14) | 0.2168 (2) | 0.39665 (8) | 0.0562 (5) | |
H17A | −0.0196 | 0.1600 | 0.3740 | 0.067* | |
C18A | −0.01649 (16) | 0.1976 (2) | 0.44325 (9) | 0.0693 (7) | |
H18A | −0.0435 | 0.1268 | 0.4522 | 0.083* | |
C19A | 0.00885 (17) | 0.2822 (3) | 0.47666 (9) | 0.0704 (7) | |
H19A | −0.0022 | 0.2681 | 0.5079 | 0.084* | |
C20A | 0.05034 (15) | 0.3872 (2) | 0.46474 (7) | 0.0572 (6) | |
H20A | 0.0679 | 0.4435 | 0.4876 | 0.069* | |
C21A | 0.26993 (14) | 0.53118 (16) | 0.24432 (6) | 0.0412 (4) | |
C22A | 0.36564 (15) | 0.57387 (19) | 0.24535 (7) | 0.0514 (5) | |
H22A | 0.3863 | 0.6312 | 0.2673 | 0.062* | |
C23A | 0.43091 (16) | 0.5337 (2) | 0.21480 (8) | 0.0575 (5) | |
H23A | 0.4950 | 0.5631 | 0.2162 | 0.069* | |
C24A | 0.39997 (16) | 0.44914 (18) | 0.18209 (7) | 0.0521 (5) | |
C25A | 0.30554 (17) | 0.40619 (18) | 0.17947 (7) | 0.0531 (5) | |
H25A | 0.2848 | 0.3503 | 0.1569 | 0.064* | |
C26A | 0.24137 (15) | 0.44680 (17) | 0.21074 (7) | 0.0475 (5) | |
H26A | 0.1775 | 0.4168 | 0.2092 | 0.057* | |
N1A | 0.24939 (11) | 0.32397 (13) | 0.36954 (5) | 0.0406 (3) | |
N2A | 0.05550 (11) | 0.57556 (13) | 0.31548 (5) | 0.0398 (3) | |
O1A | 0.07674 (12) | 0.61834 (13) | 0.40907 (5) | 0.0595 (4) | |
H1A | 0.0688 | 0.6592 | 0.3854 | 0.089* | |
O2A | 0.04810 (11) | 0.31079 (12) | 0.30075 (5) | 0.0524 (3) | |
O3A | 0.32204 (12) | 0.65099 (15) | 0.36775 (6) | 0.0709 (5) | |
Cl1 | 0.48368 (5) | 0.39797 (6) | 0.14410 (2) | 0.07186 (18) | |
H1 | 0.253 (2) | 0.162 (2) | 0.3931 (10) | 0.087 (9)* | |
C1B | 0.8571 (3) | 0.2820 (3) | 0.19339 (9) | 0.0890 (9) | |
H10 | 0.8604 | 0.1977 | 0.1933 | 0.134* | |
H11 | 0.7912 | 0.3063 | 0.1984 | 0.134* | |
H12 | 0.9025 | 0.3123 | 0.2182 | 0.134* | |
C2B | 0.97308 (15) | 0.27523 (19) | 0.13400 (7) | 0.0541 (5) | |
H13 | 0.9672 | 0.1903 | 0.1338 | 0.065* | |
H14 | 1.0282 | 0.2964 | 0.1564 | 0.065* | |
C3B | 0.99339 (14) | 0.31785 (17) | 0.08498 (7) | 0.0484 (5) | |
H3B | 1.0541 | 0.2838 | 0.0746 | 0.058* | |
C4B | 0.99805 (14) | 0.44975 (18) | 0.08757 (7) | 0.0492 (5) | |
C5B | 0.89285 (13) | 0.48782 (16) | 0.09453 (6) | 0.0408 (4) | |
C6B | 0.87928 (16) | 0.45404 (18) | 0.14540 (7) | 0.0502 (5) | |
H15 | 0.9314 | 0.4885 | 0.1665 | 0.060* | |
H16 | 0.8162 | 0.4825 | 0.1542 | 0.060* | |
C7B | 0.86807 (14) | 0.61561 (17) | 0.07776 (7) | 0.0447 (4) | |
H7B | 0.9238 | 0.6443 | 0.0614 | 0.054* | |
C8B | 0.78183 (14) | 0.59519 (18) | 0.04095 (7) | 0.0478 (5) | |
H8B | 0.7210 | 0.5887 | 0.0568 | 0.057* | |
C9B | 0.76111 (19) | 0.6683 (2) | −0.00292 (8) | 0.0667 (6) | |
H17 | 0.8218 | 0.6983 | −0.0139 | 0.080* | |
H18 | 0.7177 | 0.7336 | 0.0025 | 0.080* | |
C10B | 0.7105 (2) | 0.5801 (3) | −0.03822 (9) | 0.0782 (8) | |
H10C | 0.6413 | 0.5998 | −0.0452 | 0.094* | |
H10D | 0.7423 | 0.5803 | −0.0673 | 0.094* | |
C11B | 0.72132 (17) | 0.4603 (2) | −0.01442 (8) | 0.0650 (6) | |
H11C | 0.6618 | 0.4385 | −0.0001 | 0.078* | |
H11D | 0.7369 | 0.3996 | −0.0365 | 0.078* | |
C12B | 0.83195 (13) | 0.40302 (16) | 0.06015 (6) | 0.0397 (4) | |
C13B | 0.90496 (14) | 0.30332 (17) | 0.04781 (7) | 0.0438 (4) | |
C14B | 0.84778 (16) | 0.19125 (18) | 0.05099 (7) | 0.0508 (5) | |
C15B | 0.75861 (16) | 0.2098 (2) | 0.06915 (7) | 0.0563 (5) | |
C16B | 0.74522 (14) | 0.3361 (2) | 0.07891 (7) | 0.0520 (5) | |
C17B | 0.6951 (2) | 0.1162 (3) | 0.07601 (9) | 0.0800 (8) | |
H17B | 0.6345 | 0.1291 | 0.0880 | 0.096* | |
C18B | 0.7238 (3) | 0.0049 (3) | 0.06471 (11) | 0.0975 (12) | |
H18B | 0.6828 | −0.0588 | 0.0694 | 0.117* | |
C19B | 0.8123 (3) | −0.0127 (2) | 0.04657 (11) | 0.0929 (11) | |
H19B | 0.8302 | −0.0888 | 0.0389 | 0.111* | |
C20B | 0.8760 (2) | 0.0783 (2) | 0.03926 (8) | 0.0689 (7) | |
H20B | 0.9361 | 0.0646 | 0.0269 | 0.083* | |
C21B | 0.84957 (14) | 0.70415 (16) | 0.11559 (7) | 0.0438 (4) | |
C22B | 0.91994 (14) | 0.78879 (18) | 0.12870 (8) | 0.0512 (5) | |
H22B | 0.9783 | 0.7905 | 0.1139 | 0.061* | |
C23B | 0.90558 (16) | 0.87092 (18) | 0.16324 (8) | 0.0551 (5) | |
H23B | 0.9540 | 0.9266 | 0.1718 | 0.066* | |
C24B | 0.81938 (15) | 0.86902 (17) | 0.18455 (7) | 0.0497 (5) | |
C25B | 0.74774 (15) | 0.78766 (19) | 0.17235 (7) | 0.0521 (5) | |
H25B | 0.6892 | 0.7874 | 0.1870 | 0.063* | |
C26B | 0.76323 (15) | 0.70569 (18) | 0.13799 (7) | 0.0503 (5) | |
H26B | 0.7145 | 0.6502 | 0.1297 | 0.060* | |
N1B | 0.88309 (13) | 0.32669 (15) | 0.14848 (6) | 0.0501 (4) | |
N2B | 0.80391 (11) | 0.48068 (15) | 0.02110 (5) | 0.0452 (4) | |
O1B | 0.93885 (12) | 0.31807 (14) | 0.00264 (5) | 0.0630 (4) | |
H1B | 0.9168 | 0.3796 | −0.0090 | 0.095* | |
O2B | 0.67501 (11) | 0.38274 (17) | 0.09432 (6) | 0.0745 (5) | |
O3B | 1.06801 (11) | 0.51295 (14) | 0.08489 (7) | 0.0746 (5) | |
Cl2 | 0.80170 (5) | 0.97008 (5) | 0.22885 (2) | 0.07313 (18) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1A | 0.0832 (18) | 0.0509 (13) | 0.0561 (15) | 0.0182 (12) | 0.0141 (13) | 0.0135 (11) |
C2A | 0.0424 (10) | 0.0617 (13) | 0.0384 (10) | 0.0052 (9) | −0.0028 (8) | 0.0062 (9) |
C3A | 0.0483 (10) | 0.0522 (11) | 0.0334 (9) | −0.0043 (9) | −0.0057 (8) | −0.0070 (8) |
C4A | 0.0429 (10) | 0.0458 (11) | 0.0458 (11) | −0.0044 (8) | −0.0038 (8) | −0.0032 (9) |
C5A | 0.0365 (9) | 0.0366 (9) | 0.0337 (9) | −0.0017 (7) | 0.0016 (7) | 0.0008 (7) |
C6A | 0.0375 (9) | 0.0453 (10) | 0.0383 (10) | 0.0047 (8) | 0.0056 (7) | 0.0055 (8) |
C7A | 0.0474 (10) | 0.0330 (9) | 0.0375 (9) | −0.0033 (7) | 0.0025 (8) | 0.0024 (7) |
C8A | 0.0479 (10) | 0.0388 (9) | 0.0350 (9) | 0.0001 (8) | −0.0002 (8) | 0.0009 (7) |
C9A | 0.0659 (13) | 0.0500 (12) | 0.0469 (12) | 0.0064 (10) | −0.0058 (10) | 0.0101 (9) |
C10A | 0.0591 (13) | 0.0643 (14) | 0.0535 (13) | 0.0189 (11) | −0.0098 (10) | 0.0037 (11) |
C11A | 0.0427 (11) | 0.0656 (13) | 0.0545 (12) | 0.0108 (10) | −0.0006 (9) | 0.0048 (10) |
C12A | 0.0370 (9) | 0.0366 (9) | 0.0307 (8) | 0.0031 (7) | 0.0003 (7) | −0.0004 (7) |
C13A | 0.0458 (10) | 0.0422 (10) | 0.0340 (9) | 0.0070 (8) | 0.0015 (7) | −0.0031 (8) |
C14A | 0.0375 (9) | 0.0547 (11) | 0.0382 (10) | 0.0101 (8) | 0.0053 (8) | 0.0048 (8) |
C15A | 0.0340 (9) | 0.0488 (11) | 0.0457 (11) | 0.0022 (8) | 0.0050 (8) | 0.0059 (9) |
C16A | 0.0356 (9) | 0.0420 (10) | 0.0391 (10) | 0.0017 (7) | 0.0000 (7) | −0.0008 (8) |
C17A | 0.0430 (11) | 0.0598 (13) | 0.0659 (14) | −0.0051 (9) | 0.0045 (10) | 0.0123 (11) |
C18A | 0.0473 (12) | 0.0860 (18) | 0.0755 (17) | −0.0070 (12) | 0.0106 (11) | 0.0359 (15) |
C19A | 0.0529 (13) | 0.107 (2) | 0.0535 (14) | 0.0044 (13) | 0.0145 (11) | 0.0282 (14) |
C20A | 0.0499 (11) | 0.0825 (16) | 0.0401 (11) | 0.0112 (11) | 0.0093 (9) | 0.0062 (11) |
C21A | 0.0504 (11) | 0.0383 (9) | 0.0352 (9) | −0.0019 (8) | 0.0053 (8) | 0.0069 (8) |
C22A | 0.0543 (12) | 0.0544 (12) | 0.0458 (11) | −0.0083 (10) | 0.0059 (9) | −0.0021 (9) |
C23A | 0.0516 (12) | 0.0638 (14) | 0.0585 (13) | −0.0041 (10) | 0.0124 (10) | 0.0061 (11) |
C24A | 0.0629 (13) | 0.0488 (11) | 0.0470 (11) | 0.0094 (10) | 0.0177 (10) | 0.0113 (9) |
C25A | 0.0694 (14) | 0.0457 (11) | 0.0452 (11) | −0.0022 (10) | 0.0106 (10) | −0.0013 (9) |
C26A | 0.0534 (11) | 0.0449 (11) | 0.0448 (11) | −0.0056 (9) | 0.0077 (9) | 0.0001 (9) |
N1A | 0.0435 (8) | 0.0431 (8) | 0.0352 (8) | 0.0071 (7) | 0.0035 (6) | 0.0054 (7) |
N2A | 0.0413 (8) | 0.0422 (8) | 0.0353 (8) | 0.0064 (6) | −0.0007 (6) | 0.0024 (6) |
O1A | 0.0820 (10) | 0.0513 (8) | 0.0447 (8) | 0.0204 (8) | 0.0037 (8) | −0.0089 (7) |
O2A | 0.0661 (9) | 0.0468 (8) | 0.0429 (8) | −0.0086 (7) | −0.0028 (6) | −0.0062 (6) |
O3A | 0.0751 (11) | 0.0716 (11) | 0.0636 (10) | −0.0352 (9) | −0.0071 (8) | −0.0027 (8) |
Cl1 | 0.0799 (4) | 0.0717 (4) | 0.0688 (4) | 0.0167 (3) | 0.0327 (3) | 0.0072 (3) |
C1B | 0.136 (3) | 0.0754 (18) | 0.0601 (16) | 0.0138 (17) | 0.0306 (16) | 0.0153 (14) |
C2B | 0.0559 (12) | 0.0466 (11) | 0.0577 (13) | 0.0071 (9) | −0.0065 (10) | −0.0009 (10) |
C3B | 0.0371 (10) | 0.0468 (11) | 0.0621 (13) | 0.0059 (8) | 0.0082 (9) | 0.0007 (9) |
C4B | 0.0369 (10) | 0.0491 (11) | 0.0609 (13) | 0.0008 (9) | 0.0005 (9) | 0.0003 (10) |
C5B | 0.0365 (9) | 0.0420 (10) | 0.0436 (10) | 0.0026 (7) | 0.0018 (8) | −0.0028 (8) |
C6B | 0.0578 (12) | 0.0506 (11) | 0.0409 (10) | 0.0053 (9) | −0.0031 (9) | −0.0067 (9) |
C7B | 0.0409 (10) | 0.0455 (10) | 0.0480 (11) | 0.0061 (8) | 0.0052 (8) | 0.0006 (8) |
C8B | 0.0455 (10) | 0.0547 (12) | 0.0435 (11) | 0.0130 (9) | 0.0049 (8) | −0.0028 (9) |
C9B | 0.0735 (15) | 0.0728 (16) | 0.0533 (13) | 0.0269 (13) | 0.0033 (11) | 0.0065 (12) |
C10B | 0.0857 (18) | 0.098 (2) | 0.0486 (13) | 0.0361 (15) | −0.0093 (12) | −0.0017 (13) |
C11B | 0.0630 (14) | 0.0873 (17) | 0.0428 (12) | 0.0138 (12) | −0.0067 (10) | −0.0161 (12) |
C12B | 0.0353 (9) | 0.0482 (10) | 0.0363 (9) | 0.0007 (8) | 0.0063 (7) | −0.0041 (8) |
C13B | 0.0460 (10) | 0.0465 (11) | 0.0407 (10) | 0.0027 (8) | 0.0132 (8) | −0.0012 (8) |
C14B | 0.0658 (13) | 0.0490 (12) | 0.0365 (10) | −0.0062 (10) | −0.0011 (9) | −0.0019 (9) |
C15B | 0.0621 (13) | 0.0655 (14) | 0.0402 (11) | −0.0195 (11) | −0.0012 (9) | 0.0016 (10) |
C16B | 0.0410 (10) | 0.0768 (15) | 0.0389 (10) | −0.0083 (10) | 0.0068 (8) | −0.0053 (10) |
C17B | 0.0836 (18) | 0.097 (2) | 0.0556 (15) | −0.0411 (16) | −0.0118 (13) | 0.0175 (14) |
C18B | 0.131 (3) | 0.076 (2) | 0.077 (2) | −0.053 (2) | −0.038 (2) | 0.0258 (16) |
C19B | 0.146 (3) | 0.0473 (14) | 0.0761 (19) | −0.0202 (18) | −0.043 (2) | 0.0091 (13) |
C20B | 0.0987 (19) | 0.0507 (13) | 0.0542 (14) | 0.0024 (13) | −0.0109 (13) | −0.0009 (11) |
C21B | 0.0428 (10) | 0.0394 (10) | 0.0479 (11) | 0.0073 (8) | −0.0022 (8) | 0.0024 (8) |
C22B | 0.0422 (10) | 0.0484 (11) | 0.0624 (13) | 0.0042 (9) | 0.0023 (9) | 0.0035 (10) |
C23B | 0.0539 (12) | 0.0446 (11) | 0.0645 (14) | −0.0014 (9) | −0.0084 (10) | −0.0027 (10) |
C24B | 0.0556 (12) | 0.0412 (10) | 0.0501 (12) | 0.0096 (9) | −0.0066 (9) | −0.0023 (9) |
C25B | 0.0475 (11) | 0.0561 (12) | 0.0523 (12) | 0.0066 (9) | 0.0020 (9) | −0.0069 (10) |
C26B | 0.0451 (11) | 0.0499 (11) | 0.0553 (12) | 0.0006 (9) | 0.0006 (9) | −0.0071 (9) |
N1B | 0.0628 (10) | 0.0477 (9) | 0.0400 (9) | 0.0043 (8) | 0.0063 (8) | 0.0010 (7) |
N2B | 0.0442 (9) | 0.0554 (10) | 0.0364 (8) | 0.0084 (7) | 0.0048 (7) | −0.0028 (7) |
O1B | 0.0782 (10) | 0.0615 (10) | 0.0542 (9) | 0.0205 (8) | 0.0330 (8) | 0.0069 (7) |
O2B | 0.0466 (8) | 0.1099 (14) | 0.0703 (11) | −0.0027 (9) | 0.0236 (8) | −0.0088 (10) |
O3B | 0.0399 (8) | 0.0588 (10) | 0.1244 (16) | −0.0073 (7) | 0.0032 (9) | 0.0015 (10) |
Cl2 | 0.0842 (4) | 0.0606 (4) | 0.0737 (4) | 0.0030 (3) | 0.0022 (3) | −0.0226 (3) |
C1A—N1A | 1.447 (3) | C1B—N1B | 1.451 (3) |
C1A—H2 | 1.02 (3) | C1B—H10 | 0.9600 |
C1A—H3 | 0.96 (3) | C1B—H11 | 0.9600 |
C1A—H1 | 0.92 (3) | C1B—H12 | 0.9600 |
C2A—N1A | 1.450 (2) | C2B—N1B | 1.448 (3) |
C2A—C3A | 1.538 (3) | C2B—C3B | 1.529 (3) |
C2A—H4 | 0.9700 | C2B—H13 | 0.9700 |
C2A—H5 | 0.9700 | C2B—H14 | 0.9700 |
C3A—C4A | 1.500 (3) | C3B—C4B | 1.503 (3) |
C3A—C13A | 1.546 (3) | C3B—C13B | 1.539 (3) |
C3A—H3A | 0.9800 | C3B—H3B | 0.9800 |
C4A—O3A | 1.201 (2) | C4B—O3B | 1.200 (2) |
C4A—C5A | 1.520 (2) | C4B—C5B | 1.523 (3) |
C5A—C6A | 1.530 (2) | C5B—C6B | 1.529 (3) |
C5A—C7A | 1.552 (2) | C5B—C7B | 1.558 (3) |
C5A—C12A | 1.560 (2) | C5B—C12B | 1.560 (3) |
C6A—N1A | 1.449 (2) | C6B—N1B | 1.452 (3) |
C6A—H6 | 0.9700 | C6B—H15 | 0.9700 |
C6A—H7 | 0.9700 | C6B—H16 | 0.9700 |
C7A—C21A | 1.507 (3) | C7B—C21B | 1.514 (3) |
C7A—C8A | 1.520 (3) | C7B—C8B | 1.520 (3) |
C7A—H7A | 0.9800 | C7B—H7B | 0.9800 |
C8A—N2A | 1.469 (2) | C8B—N2B | 1.462 (2) |
C8A—C9A | 1.515 (3) | C8B—C9B | 1.508 (3) |
C8A—H8A | 0.9800 | C8B—H8B | 0.9800 |
C9A—C10A | 1.535 (3) | C9B—C10B | 1.539 (4) |
C9A—H8 | 0.9700 | C9B—H17 | 0.9700 |
C9A—H9 | 0.9700 | C9B—H18 | 0.9700 |
C10A—C11A | 1.534 (3) | C10B—C11B | 1.524 (4) |
C10A—H10A | 0.9700 | C10B—H10C | 0.9700 |
C10A—H10B | 0.9700 | C10B—H10D | 0.9700 |
C11A—N2A | 1.462 (2) | C11B—N2B | 1.462 (3) |
C11A—H11A | 0.9700 | C11B—H11C | 0.9700 |
C11A—H11B | 0.9700 | C11B—H11D | 0.9700 |
C12A—N2A | 1.456 (2) | C12B—N2B | 1.446 (2) |
C12A—C16A | 1.533 (2) | C12B—C16B | 1.538 (3) |
C12A—C13A | 1.566 (2) | C12B—C13B | 1.567 (3) |
C13A—O1A | 1.416 (2) | C13B—O1B | 1.417 (2) |
C13A—C14A | 1.503 (3) | C13B—C14B | 1.500 (3) |
C14A—C15A | 1.379 (3) | C14B—C15B | 1.376 (3) |
C14A—C20A | 1.384 (3) | C14B—C20B | 1.391 (3) |
C15A—C17A | 1.389 (3) | C15B—C17B | 1.395 (3) |
C15A—C16A | 1.476 (3) | C15B—C16B | 1.478 (3) |
C16A—O2A | 1.212 (2) | C16B—O2B | 1.208 (2) |
C17A—C18A | 1.378 (3) | C17B—C18B | 1.373 (5) |
C17A—H17A | 0.9300 | C17B—H17B | 0.9300 |
C18A—C19A | 1.376 (4) | C18B—C19B | 1.366 (5) |
C18A—H18A | 0.9300 | C18B—H18B | 0.9300 |
C19A—C20A | 1.377 (3) | C19B—C20B | 1.377 (4) |
C19A—H19A | 0.9300 | C19B—H19B | 0.9300 |
C20A—H20A | 0.9300 | C20B—H20B | 0.9300 |
C21A—C22A | 1.386 (3) | C21B—C22B | 1.385 (3) |
C21A—C26A | 1.387 (3) | C21B—C26B | 1.385 (3) |
C22A—C23A | 1.376 (3) | C22B—C23B | 1.385 (3) |
C22A—H22A | 0.9300 | C22B—H22B | 0.9300 |
C23A—C24A | 1.379 (3) | C23B—C24B | 1.367 (3) |
C23A—H23A | 0.9300 | C23B—H23B | 0.9300 |
C24A—C25A | 1.368 (3) | C24B—C25B | 1.365 (3) |
C24A—Cl1 | 1.740 (2) | C24B—Cl2 | 1.741 (2) |
C25A—C26A | 1.382 (3) | C25B—C26B | 1.383 (3) |
C25A—H25A | 0.9300 | C25B—H25B | 0.9300 |
C26A—H26A | 0.9300 | C26B—H26B | 0.9300 |
O1A—H1A | 0.8200 | O1B—H1B | 0.8200 |
N1A—C1A—H2 | 108.4 (15) | N1B—C1B—H10 | 109.5 |
N1A—C1A—H3 | 114.2 (19) | N1B—C1B—H11 | 109.5 |
H2—C1A—H3 | 106 (2) | H10—C1B—H11 | 109.5 |
N1A—C1A—H1 | 109.7 (17) | N1B—C1B—H12 | 109.5 |
H2—C1A—H1 | 104 (2) | H10—C1B—H12 | 109.5 |
H3—C1A—H1 | 114 (2) | H11—C1B—H12 | 109.5 |
N1A—C2A—C3A | 110.60 (15) | N1B—C2B—C3B | 111.03 (16) |
N1A—C2A—H4 | 109.5 | N1B—C2B—H13 | 109.4 |
C3A—C2A—H4 | 109.5 | C3B—C2B—H13 | 109.4 |
N1A—C2A—H5 | 109.5 | N1B—C2B—H14 | 109.4 |
C3A—C2A—H5 | 109.5 | C3B—C2B—H14 | 109.4 |
H4—C2A—H5 | 108.1 | H13—C2B—H14 | 108.0 |
C4A—C3A—C2A | 105.99 (16) | C4B—C3B—C2B | 106.37 (17) |
C4A—C3A—C13A | 100.39 (15) | C4B—C3B—C13B | 99.67 (15) |
C2A—C3A—C13A | 113.17 (16) | C2B—C3B—C13B | 113.77 (16) |
C4A—C3A—H3A | 112.2 | C4B—C3B—H3B | 112.1 |
C2A—C3A—H3A | 112.2 | C2B—C3B—H3B | 112.1 |
C13A—C3A—H3A | 112.2 | C13B—C3B—H3B | 112.1 |
O3A—C4A—C3A | 128.70 (18) | O3B—C4B—C3B | 128.70 (18) |
O3A—C4A—C5A | 126.59 (18) | O3B—C4B—C5B | 126.56 (19) |
C3A—C4A—C5A | 104.70 (15) | C3B—C4B—C5B | 104.74 (15) |
C4A—C5A—C6A | 104.52 (14) | C4B—C5B—C6B | 104.26 (15) |
C4A—C5A—C7A | 114.60 (15) | C4B—C5B—C7B | 113.88 (15) |
C6A—C5A—C7A | 117.58 (14) | C6B—C5B—C7B | 119.04 (15) |
C4A—C5A—C12A | 101.36 (14) | C4B—C5B—C12B | 101.13 (14) |
C6A—C5A—C12A | 110.02 (14) | C6B—C5B—C12B | 109.86 (15) |
C7A—C5A—C12A | 107.55 (13) | C7B—C5B—C12B | 107.22 (14) |
N1A—C6A—C5A | 107.18 (14) | N1B—C6B—C5B | 107.56 (15) |
N1A—C6A—H6 | 110.3 | N1B—C6B—H15 | 110.2 |
C5A—C6A—H6 | 110.3 | C5B—C6B—H15 | 110.2 |
N1A—C6A—H7 | 110.3 | N1B—C6B—H16 | 110.2 |
C5A—C6A—H7 | 110.3 | C5B—C6B—H16 | 110.2 |
H6—C6A—H7 | 108.5 | H15—C6B—H16 | 108.5 |
C21A—C7A—C8A | 118.30 (15) | C21B—C7B—C8B | 115.33 (15) |
C21A—C7A—C5A | 113.74 (15) | C21B—C7B—C5B | 116.54 (16) |
C8A—C7A—C5A | 101.33 (14) | C8B—C7B—C5B | 101.64 (15) |
C21A—C7A—H7A | 107.6 | C21B—C7B—H7B | 107.6 |
C8A—C7A—H7A | 107.6 | C8B—C7B—H7B | 107.6 |
C5A—C7A—H7A | 107.6 | C5B—C7B—H7B | 107.6 |
N2A—C8A—C9A | 101.46 (15) | N2B—C8B—C9B | 101.49 (16) |
N2A—C8A—C7A | 102.85 (14) | N2B—C8B—C7B | 103.40 (15) |
C9A—C8A—C7A | 123.70 (16) | C9B—C8B—C7B | 124.37 (19) |
N2A—C8A—H8A | 109.2 | N2B—C8B—H8B | 108.8 |
C9A—C8A—H8A | 109.2 | C9B—C8B—H8B | 108.8 |
C7A—C8A—H8A | 109.2 | C7B—C8B—H8B | 108.8 |
C8A—C9A—C10A | 102.64 (16) | C8B—C9B—C10B | 102.9 (2) |
C8A—C9A—H8 | 111.2 | C8B—C9B—H17 | 111.2 |
C10A—C9A—H8 | 111.2 | C10B—C9B—H17 | 111.2 |
C8A—C9A—H9 | 111.2 | C8B—C9B—H18 | 111.2 |
C10A—C9A—H9 | 111.2 | C10B—C9B—H18 | 111.2 |
H8—C9A—H9 | 109.2 | H17—C9B—H18 | 109.1 |
C11A—C10A—C9A | 106.28 (16) | C11B—C10B—C9B | 105.76 (18) |
C11A—C10A—H10A | 110.5 | C11B—C10B—H10C | 110.6 |
C9A—C10A—H10A | 110.5 | C9B—C10B—H10C | 110.6 |
C11A—C10A—H10B | 110.5 | C11B—C10B—H10D | 110.6 |
C9A—C10A—H10B | 110.5 | C9B—C10B—H10D | 110.6 |
H10A—C10A—H10B | 108.7 | H10C—C10B—H10D | 108.7 |
N2A—C11A—C10A | 102.00 (17) | N2B—C11B—C10B | 101.8 (2) |
N2A—C11A—H11A | 111.4 | N2B—C11B—H11C | 111.4 |
C10A—C11A—H11A | 111.4 | C10B—C11B—H11C | 111.4 |
N2A—C11A—H11B | 111.4 | N2B—C11B—H11D | 111.4 |
C10A—C11A—H11B | 111.4 | C10B—C11B—H11D | 111.4 |
H11A—C11A—H11B | 109.2 | H11C—C11B—H11D | 109.3 |
N2A—C12A—C16A | 114.52 (14) | N2B—C12B—C16B | 114.40 (15) |
N2A—C12A—C5A | 100.48 (13) | N2B—C12B—C5B | 101.26 (14) |
C16A—C12A—C5A | 117.31 (14) | C16B—C12B—C5B | 117.83 (15) |
N2A—C12A—C13A | 113.98 (14) | N2B—C12B—C13B | 113.41 (14) |
C16A—C12A—C13A | 104.28 (14) | C16B—C12B—C13B | 103.87 (16) |
C5A—C12A—C13A | 106.40 (13) | C5B—C12B—C13B | 106.16 (14) |
O1A—C13A—C14A | 112.15 (15) | O1B—C13B—C14B | 111.57 (16) |
O1A—C13A—C3A | 109.43 (16) | O1B—C13B—C3B | 108.50 (16) |
C14A—C13A—C3A | 113.63 (15) | C14B—C13B—C3B | 115.23 (16) |
O1A—C13A—C12A | 112.64 (14) | O1B—C13B—C12B | 112.47 (15) |
C14A—C13A—C12A | 105.17 (14) | C14B—C13B—C12B | 105.08 (15) |
C3A—C13A—C12A | 103.49 (14) | C3B—C13B—C12B | 103.77 (15) |
C15A—C14A—C20A | 120.2 (2) | C15B—C14B—C20B | 120.2 (2) |
C15A—C14A—C13A | 111.51 (16) | C15B—C14B—C13B | 111.76 (18) |
C20A—C14A—C13A | 128.05 (19) | C20B—C14B—C13B | 128.0 (2) |
C14A—C15A—C17A | 121.06 (19) | C14B—C15B—C17B | 120.9 (2) |
C14A—C15A—C16A | 110.43 (16) | C14B—C15B—C16B | 110.32 (18) |
C17A—C15A—C16A | 128.41 (19) | C17B—C15B—C16B | 128.8 (2) |
O2A—C16A—C15A | 126.89 (17) | O2B—C16B—C15B | 127.6 (2) |
O2A—C16A—C12A | 124.82 (17) | O2B—C16B—C12B | 124.3 (2) |
C15A—C16A—C12A | 108.00 (15) | C15B—C16B—C12B | 107.73 (17) |
C18A—C17A—C15A | 118.2 (2) | C18B—C17B—C15B | 118.6 (3) |
C18A—C17A—H17A | 120.9 | C18B—C17B—H17B | 120.7 |
C15A—C17A—H17A | 120.9 | C15B—C17B—H17B | 120.7 |
C19A—C18A—C17A | 120.7 (2) | C19B—C18B—C17B | 120.2 (3) |
C19A—C18A—H18A | 119.7 | C19B—C18B—H18B | 119.9 |
C17A—C18A—H18A | 119.7 | C17B—C18B—H18B | 119.9 |
C18A—C19A—C20A | 121.2 (2) | C18B—C19B—C20B | 122.3 (3) |
C18A—C19A—H19A | 119.4 | C18B—C19B—H19B | 118.9 |
C20A—C19A—H19A | 119.4 | C20B—C19B—H19B | 118.9 |
C19A—C20A—C14A | 118.6 (2) | C19B—C20B—C14B | 117.9 (3) |
C19A—C20A—H20A | 120.7 | C19B—C20B—H20B | 121.1 |
C14A—C20A—H20A | 120.7 | C14B—C20B—H20B | 121.1 |
C22A—C21A—C26A | 117.46 (18) | C22B—C21B—C26B | 117.33 (18) |
C22A—C21A—C7A | 118.44 (17) | C22B—C21B—C7B | 120.06 (18) |
C26A—C21A—C7A | 124.05 (17) | C26B—C21B—C7B | 122.60 (18) |
C23A—C22A—C21A | 121.8 (2) | C21B—C22B—C23B | 121.60 (19) |
C23A—C22A—H22A | 119.1 | C21B—C22B—H22B | 119.2 |
C21A—C22A—H22A | 119.1 | C23B—C22B—H22B | 119.2 |
C22A—C23A—C24A | 119.1 (2) | C24B—C23B—C22B | 119.13 (19) |
C22A—C23A—H23A | 120.5 | C24B—C23B—H23B | 120.4 |
C24A—C23A—H23A | 120.5 | C22B—C23B—H23B | 120.4 |
C25A—C24A—C23A | 120.89 (19) | C25B—C24B—C23B | 121.11 (19) |
C25A—C24A—Cl1 | 120.53 (17) | C25B—C24B—Cl2 | 119.43 (17) |
C23A—C24A—Cl1 | 118.58 (17) | C23B—C24B—Cl2 | 119.45 (16) |
C24A—C25A—C26A | 119.2 (2) | C24B—C25B—C26B | 119.2 (2) |
C24A—C25A—H25A | 120.4 | C24B—C25B—H25B | 120.4 |
C26A—C25A—H25A | 120.4 | C26B—C25B—H25B | 120.4 |
C25A—C26A—C21A | 121.61 (19) | C25B—C26B—C21B | 121.63 (19) |
C25A—C26A—H26A | 119.2 | C25B—C26B—H26B | 119.2 |
C21A—C26A—H26A | 119.2 | C21B—C26B—H26B | 119.2 |
C1A—N1A—C6A | 113.07 (16) | C2B—N1B—C1B | 112.85 (19) |
C1A—N1A—C2A | 114.00 (17) | C2B—N1B—C6B | 114.35 (17) |
C6A—N1A—C2A | 114.49 (15) | C1B—N1B—C6B | 113.15 (18) |
C12A—N2A—C11A | 124.31 (15) | C12B—N2B—C11B | 124.78 (17) |
C12A—N2A—C8A | 105.94 (13) | C12B—N2B—C8B | 107.15 (14) |
C11A—N2A—C8A | 104.43 (14) | C11B—N2B—C8B | 103.81 (15) |
C13A—O1A—H1A | 109.5 | C13B—O1B—H1B | 109.5 |
N1A—C2A—C3A—C4A | −57.63 (19) | N1B—C2B—C3B—C4B | 57.2 (2) |
N1A—C2A—C3A—C13A | 51.4 (2) | N1B—C2B—C3B—C13B | −51.5 (2) |
C2A—C3A—C4A—O3A | −110.9 (2) | C2B—C3B—C4B—O3B | 112.0 (3) |
C13A—C3A—C4A—O3A | 131.2 (2) | C13B—C3B—C4B—O3B | −129.5 (2) |
C2A—C3A—C4A—C5A | 68.25 (17) | C2B—C3B—C4B—C5B | −67.91 (19) |
C13A—C3A—C4A—C5A | −49.70 (18) | C13B—C3B—C4B—C5B | 50.53 (18) |
O3A—C4A—C5A—C6A | 105.8 (2) | O3B—C4B—C5B—C6B | −107.0 (2) |
C3A—C4A—C5A—C6A | −73.31 (17) | C3B—C4B—C5B—C6B | 72.93 (19) |
O3A—C4A—C5A—C7A | −24.3 (3) | O3B—C4B—C5B—C7B | 24.3 (3) |
C3A—C4A—C5A—C7A | 156.55 (15) | C3B—C4B—C5B—C7B | −155.75 (16) |
O3A—C4A—C5A—C12A | −139.8 (2) | O3B—C4B—C5B—C12B | 139.0 (2) |
C3A—C4A—C5A—C12A | 41.07 (17) | C3B—C4B—C5B—C12B | −41.10 (19) |
C4A—C5A—C6A—N1A | 65.78 (17) | C4B—C5B—C6B—N1B | −65.79 (19) |
C7A—C5A—C6A—N1A | −165.87 (14) | C7B—C5B—C6B—N1B | 165.98 (16) |
C12A—C5A—C6A—N1A | −42.34 (18) | C12B—C5B—C6B—N1B | 41.9 (2) |
C4A—C5A—C7A—C21A | 110.27 (18) | C4B—C5B—C7B—C21B | −112.93 (19) |
C6A—C5A—C7A—C21A | −13.1 (2) | C6B—C5B—C7B—C21B | 10.7 (2) |
C12A—C5A—C7A—C21A | −137.89 (15) | C12B—C5B—C7B—C21B | 136.07 (16) |
C4A—C5A—C7A—C8A | −121.68 (16) | C4B—C5B—C7B—C8B | 120.83 (17) |
C6A—C5A—C7A—C8A | 114.94 (16) | C6B—C5B—C7B—C8B | −115.54 (18) |
C12A—C5A—C7A—C8A | −9.84 (17) | C12B—C5B—C7B—C8B | 9.83 (18) |
C21A—C7A—C8A—N2A | 158.96 (15) | C21B—C7B—C8B—N2B | −159.34 (16) |
C5A—C7A—C8A—N2A | 33.91 (16) | C5B—C7B—C8B—N2B | −32.31 (18) |
C21A—C7A—C8A—C9A | −87.6 (2) | C21B—C7B—C8B—C9B | 86.4 (2) |
C5A—C7A—C8A—C9A | 147.30 (17) | C5B—C7B—C8B—C9B | −146.57 (19) |
N2A—C8A—C9A—C10A | −36.18 (19) | N2B—C8B—C9B—C10B | 34.9 (2) |
C7A—C8A—C9A—C10A | −150.26 (18) | C7B—C8B—C9B—C10B | 150.1 (2) |
C8A—C9A—C10A—C11A | 11.7 (2) | C8B—C9B—C10B—C11B | −8.9 (2) |
C9A—C10A—C11A—N2A | 17.2 (2) | C9B—C10B—C11B—N2B | −20.4 (2) |
C4A—C5A—C12A—N2A | 102.79 (14) | C4B—C5B—C12B—N2B | −103.29 (15) |
C6A—C5A—C12A—N2A | −147.00 (14) | C6B—C5B—C12B—N2B | 146.95 (14) |
C7A—C5A—C12A—N2A | −17.79 (16) | C7B—C5B—C12B—N2B | 16.24 (17) |
C4A—C5A—C12A—C16A | −132.43 (15) | C4B—C5B—C12B—C16B | 131.17 (18) |
C6A—C5A—C12A—C16A | −22.2 (2) | C6B—C5B—C12B—C16B | 21.4 (2) |
C7A—C5A—C12A—C16A | 106.99 (16) | C7B—C5B—C12B—C16B | −109.30 (19) |
C4A—C5A—C12A—C13A | −16.24 (17) | C4B—C5B—C12B—C13B | 15.37 (18) |
C6A—C5A—C12A—C13A | 93.97 (16) | C6B—C5B—C12B—C13B | −94.39 (17) |
C7A—C5A—C12A—C13A | −136.82 (14) | C7B—C5B—C12B—C13B | 134.90 (15) |
C4A—C3A—C13A—O1A | −83.08 (17) | C4B—C3B—C13B—O1B | 81.23 (18) |
C2A—C3A—C13A—O1A | 164.40 (15) | C2B—C3B—C13B—O1B | −165.97 (16) |
C4A—C3A—C13A—C14A | 150.71 (16) | C4B—C3B—C13B—C14B | −152.87 (17) |
C2A—C3A—C13A—C14A | 38.2 (2) | C2B—C3B—C13B—C14B | −40.1 (2) |
C4A—C3A—C13A—C12A | 37.21 (17) | C4B—C3B—C13B—C12B | −38.57 (18) |
C2A—C3A—C13A—C12A | −75.31 (18) | C2B—C3B—C13B—C12B | 74.23 (19) |
N2A—C12A—C13A—O1A | −4.5 (2) | N2B—C12B—C13B—O1B | 7.6 (2) |
C16A—C12A—C13A—O1A | −130.12 (16) | C16B—C12B—C13B—O1B | 132.37 (17) |
C5A—C12A—C13A—O1A | 105.25 (17) | C5B—C12B—C13B—O1B | −102.72 (18) |
N2A—C12A—C13A—C14A | 117.90 (16) | N2B—C12B—C13B—C14B | −113.99 (17) |
C16A—C12A—C13A—C14A | −7.68 (17) | C16B—C12B—C13B—C14B | 10.80 (18) |
C5A—C12A—C13A—C14A | −132.32 (14) | C5B—C12B—C13B—C14B | 135.71 (15) |
N2A—C12A—C13A—C3A | −122.62 (15) | N2B—C12B—C13B—C3B | 124.64 (16) |
C16A—C12A—C13A—C3A | 111.80 (15) | C16B—C12B—C13B—C3B | −110.56 (16) |
C5A—C12A—C13A—C3A | −12.83 (17) | C5B—C12B—C13B—C3B | 14.34 (18) |
O1A—C13A—C14A—C15A | 129.46 (17) | O1B—C13B—C14B—C15B | −130.14 (18) |
C3A—C13A—C14A—C15A | −105.78 (18) | C3B—C13B—C14B—C15B | 105.6 (2) |
C12A—C13A—C14A—C15A | 6.71 (19) | C12B—C13B—C14B—C15B | −8.0 (2) |
O1A—C13A—C14A—C20A | −56.2 (2) | O1B—C13B—C14B—C20B | 51.6 (3) |
C3A—C13A—C14A—C20A | 68.6 (2) | C3B—C13B—C14B—C20B | −72.7 (3) |
C12A—C13A—C14A—C20A | −178.91 (18) | C12B—C13B—C14B—C20B | 173.8 (2) |
C20A—C14A—C15A—C17A | −1.1 (3) | C20B—C14B—C15B—C17B | −0.1 (3) |
C13A—C14A—C15A—C17A | 173.81 (17) | C13B—C14B—C15B—C17B | −178.52 (19) |
C20A—C14A—C15A—C16A | −177.66 (17) | C20B—C14B—C15B—C16B | 179.84 (19) |
C13A—C14A—C15A—C16A | −2.8 (2) | C13B—C14B—C15B—C16B | 1.5 (2) |
C14A—C15A—C16A—O2A | −176.55 (18) | C14B—C15B—C16B—O2B | 178.9 (2) |
C17A—C15A—C16A—O2A | 7.2 (3) | C17B—C15B—C16B—O2B | −1.1 (4) |
C14A—C15A—C16A—C12A | −2.5 (2) | C14B—C15B—C16B—C12B | 5.9 (2) |
C17A—C15A—C16A—C12A | −178.77 (18) | C17B—C15B—C16B—C12B | −174.1 (2) |
N2A—C12A—C16A—O2A | 55.3 (2) | N2B—C12B—C16B—O2B | −59.4 (3) |
C5A—C12A—C16A—O2A | −62.1 (2) | C5B—C12B—C16B—O2B | 59.4 (3) |
C13A—C12A—C16A—O2A | −179.44 (17) | C13B—C12B—C16B—O2B | 176.43 (19) |
N2A—C12A—C16A—C15A | −118.90 (16) | N2B—C12B—C16B—C15B | 113.88 (18) |
C5A—C12A—C16A—C15A | 123.68 (16) | C5B—C12B—C16B—C15B | −127.31 (17) |
C13A—C12A—C16A—C15A | 6.34 (17) | C13B—C12B—C16B—C15B | −10.3 (2) |
C14A—C15A—C17A—C18A | 0.7 (3) | C14B—C15B—C17B—C18B | 0.6 (3) |
C16A—C15A—C17A—C18A | 176.67 (19) | C16B—C15B—C17B—C18B | −179.3 (2) |
C15A—C17A—C18A—C19A | 0.3 (3) | C15B—C17B—C18B—C19B | −0.8 (4) |
C17A—C18A—C19A—C20A | −1.0 (4) | C17B—C18B—C19B—C20B | 0.5 (4) |
C18A—C19A—C20A—C14A | 0.7 (3) | C18B—C19B—C20B—C14B | 0.0 (4) |
C15A—C14A—C20A—C19A | 0.4 (3) | C15B—C14B—C20B—C19B | −0.2 (3) |
C13A—C14A—C20A—C19A | −173.59 (19) | C13B—C14B—C20B—C19B | 177.9 (2) |
C8A—C7A—C21A—C22A | 154.36 (17) | C8B—C7B—C21B—C22B | −134.64 (19) |
C5A—C7A—C21A—C22A | −86.9 (2) | C5B—C7B—C21B—C22B | 106.3 (2) |
C8A—C7A—C21A—C26A | −28.4 (3) | C8B—C7B—C21B—C26B | 44.6 (3) |
C5A—C7A—C21A—C26A | 90.4 (2) | C5B—C7B—C21B—C26B | −74.4 (2) |
C26A—C21A—C22A—C23A | −0.8 (3) | C26B—C21B—C22B—C23B | 0.9 (3) |
C7A—C21A—C22A—C23A | 176.65 (19) | C7B—C21B—C22B—C23B | −179.83 (18) |
C21A—C22A—C23A—C24A | 0.4 (3) | C21B—C22B—C23B—C24B | −0.7 (3) |
C22A—C23A—C24A—C25A | 0.7 (3) | C22B—C23B—C24B—C25B | 0.1 (3) |
C22A—C23A—C24A—Cl1 | −179.32 (16) | C22B—C23B—C24B—Cl2 | 178.72 (16) |
C23A—C24A—C25A—C26A | −1.3 (3) | C23B—C24B—C25B—C26B | 0.3 (3) |
Cl1—C24A—C25A—C26A | 178.69 (15) | Cl2—C24B—C25B—C26B | −178.36 (16) |
C24A—C25A—C26A—C21A | 0.9 (3) | C24B—C25B—C26B—C21B | −0.1 (3) |
C22A—C21A—C26A—C25A | 0.2 (3) | C22B—C21B—C26B—C25B | −0.5 (3) |
C7A—C21A—C26A—C25A | −177.14 (18) | C7B—C21B—C26B—C25B | −179.77 (18) |
C5A—C6A—N1A—C1A | 169.67 (19) | C3B—C2B—N1B—C1B | 175.8 (2) |
C5A—C6A—N1A—C2A | −57.50 (19) | C3B—C2B—N1B—C6B | −53.0 (2) |
C3A—C2A—N1A—C1A | −173.92 (19) | C5B—C6B—N1B—C2B | 57.2 (2) |
C3A—C2A—N1A—C6A | 53.7 (2) | C5B—C6B—N1B—C1B | −171.7 (2) |
C16A—C12A—N2A—C11A | 34.4 (2) | C16B—C12B—N2B—C11B | −31.6 (2) |
C5A—C12A—N2A—C11A | 161.08 (17) | C5B—C12B—N2B—C11B | −159.41 (17) |
C13A—C12A—N2A—C11A | −85.6 (2) | C13B—C12B—N2B—C11B | 87.3 (2) |
C16A—C12A—N2A—C8A | −86.16 (17) | C16B—C12B—N2B—C8B | 89.63 (19) |
C5A—C12A—N2A—C8A | 40.51 (16) | C5B—C12B—N2B—C8B | −38.18 (17) |
C13A—C12A—N2A—C8A | 153.87 (15) | C13B—C12B—N2B—C8B | −151.47 (15) |
C10A—C11A—N2A—C12A | −162.38 (16) | C10B—C11B—N2B—C12B | 166.35 (17) |
C10A—C11A—N2A—C8A | −41.11 (19) | C10B—C11B—N2B—C8B | 43.6 (2) |
C9A—C8A—N2A—C12A | −177.77 (14) | C9B—C8B—N2B—C12B | 176.22 (16) |
C7A—C8A—N2A—C12A | −48.94 (17) | C7B—C8B—N2B—C12B | 46.38 (19) |
C9A—C8A—N2A—C11A | 49.47 (18) | C9B—C8B—N2B—C11B | −50.1 (2) |
C7A—C8A—N2A—C11A | 178.30 (15) | C7B—C8B—N2B—C11B | −179.94 (17) |
Cg1 is the centroid of the C21A–C26A ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N2A | 0.82 | 2.20 | 2.705 (2) | 120 |
O1B—H1B···N2B | 0.82 | 2.16 | 2.689 (2) | 123 |
C8A—H8A···O2A | 0.98 | 2.57 | 3.190 (2) | 122 |
O1B—H1B···O3Bi | 0.82 | 2.51 | 3.147 (2) | 135 |
C1A—H3···O3Bii | 0.96 (3) | 2.59 (3) | 3.164 (3) | 118 (2) |
C1A—H2···Cg1iii | 1.02 (3) | 2.70 (3) | 3.648 (3) | 155 (2) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2. |
Cg1 is the centroid of the C21A–C26A ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N2A | 0.82 | 2.20 | 2.705 (2) | 119.7 |
O1B—H1B···N2B | 0.82 | 2.16 | 2.689 (2) | 122.7 |
C8A—H8A···O2A | 0.98 | 2.57 | 3.190 (2) | 121.6 |
O1B—H1B···O3Bi | 0.82 | 2.51 | 3.147 (2) | 135.2 |
C1A—H3···O3Bii | 0.96 (3) | 2.59 (3) | 3.164 (3) | 118 (2) |
C1A—H2···Cg1iii | 1.02 (3) | 2.70 (3) | 3.648 (3) | 155 (2) |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1/2, y−1/2, −z+1/2. |
Acknowledgements
JS and RAN thank the management of the Madura College for their encouragement and support. RRK thanks the DST, New Delhi, for funds under the fast-track scheme (No. SR/FT/CS-073/2009).
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Pyrrolizine derivatives have antimicrobial (Barsoum & Nawar, 2003), anti- inflammatory (Abbas et al., 2010) and antileukemic (Anderson & Corey, 1977) activities. These derivatives are used as inhibitors of blood platelet aggregation (Makoni & Sugden, 1980), Functionalized piperidines are familiar substructures found in biologically active natural products and synthetic pharmaceuticals (Michael, 2001; Pinder, 1992; Rubiralta et al., 1991). Against this background and to ascertain the molecular structure and conformation, the X-ray crystal structure determination of the title compound has been carried out.
The asymmetric unit of the title compound (Fig 1) C37H28N2O3, comprises two independent molecules. In the pyrrazoline ring system, the pyrrolidine rings (N2/C8/C7/C5/C12) adopt twisted conformations with the puckering parameters q2 = 0.4373 (18) Å and Φ2 = 13.0 (2) ° and q2 = 0.4096 (19) Å and Φ2 = 193.9 (3)° (Cremer & Pople, 1975), in molecule A and in molecule B respectively. The pyrrolidine rings (N2/C8—C11) adopt twisted conformation with the puckering parameters q2 = 0.453 (2) Å, Φ2 = 194.8 (3) ° and q2 = 0.461 (2) Å, Φ2 = 10.9 (3) ° (Cremer & Pople, 1975) respectively for molecule A and molecule B. The cyclopentane ring (C12A—C16A) in molecule A adopts a twisted conformation with the puckering parameters q2 = 0.0775 (19) Å and Φ2 = 18.0 (1) ° (Cremer & Pople, 1975). The cyclopentane ring (C12B—C16B) in molecule B adopts an envelop conformation with the puckering parameters q2 = 0.111 (2) Å and Φ2 = 186.4 (12) ° (Cremer & Pople, 1975). The C16—O2 distances in the indolone, in molecules A and B are 1.212 (2) ° and 1.208 (2) A °, respectively. The deviation of O2 from planarity seems to have considerably influenced, the torsion angles N2—C12–C16—O2 and C17—C15—C16—O2 (55.3 (2) ° and 7.2 (2)° in molecule A and -59.4 (2) ° and -1.1 (4)° in molecule B). The differences in these torsion angles may also be attributed due to O1—H1—N2 interaction in molecules A and B. The piperidine ring (N1/C2—C6) adopts a slightly twisted chair conformation in both molecules with the puckering parameters of Q = 0.668 (2) Å, Θ = 166.48 (2) ° and Φ = 22.0 (7) ° in molecule A, Q = 0.161 (2) Å, Θ = 13.97 (17)° and Φ = 203.5 (8) ° in molecule B (Cremer & Pople, 1975). Short contacts H26 ··· H8 (2.17 Å for molecule A and 2.20 Å for molecule B) result in substantial widening of the bond angles C7—C21—C26 (124.05I(17) ° for molecule A and 122.60 (18) ° for molecule B).
The structure features weak intra-molecular O—H···N, C—H···O interactions. The crystal structure features inter-molecular C—H···O and O—H···O interactions. The O1B—H1B···O3B interaction forms, inversely related dimers generating a graph set motif R22(12). These dimers are further interconnected by C1A—H3···O3B and C1A—H2···Cg1 inter-molecular interactions (where Cg1 is the ring centroid of (C21A—C26A) as shown in Fig 2.