research communications
S,2′S,3S)-1′-benzoyl-2′-(4-methoxyphenyl)-1-methyl-2′,5′,6′,10b′-tetrahydro-1′H-spiro[indoline-3,3′-pyrrolo[2,1-a]isoquinolin]-2-one
of (1′aDepartment of Physics, St.Peter's University, Avadi, Chennai-600054, Tamilnadu, India, bApplied Organic Chemistry Group, Chemical Science and Technology Division, CSIR-North East Institute of Science and Technology, Jorhat-785006, India, cAcademy of Scientific and Innovative Research (AcSIR), CSIR-NEIST Campus, India, dCSIR-North East Institute of Science and Technology (NEIST), Branch Laboratory, Lamphepat-795004, Imphal, Manipur, India, and eDepartment of Physics, Kings Engineering College, Irungattukottai, Sriperumbudur, Chennai–602117, Tamilnadu, India
*Correspondence e-mail: drkannan1208kings@gmail.com
In the title spiro compound, C34H30N2O3, the central pyrrolidine ring is fused with the tetrahydroisoquinoline ring, both having distorted envelope conformations, with the flap atoms being C and N, respectively. The methoxyphenyl group is attached to the pyrrolidine ring, and is disordered over two positions, with refined occupancies of 0.638 (6):0.362 (6) Å. The central pyrrolidine ring is inclined relative to the tetrahydroisoquinoline group, such that the dihedral between the non-flap atoms of each ring system is 11.29 (7)°. The spiro-linkage creates a dihedral angle of 83.26 (5)° between the indolinone ring and the non-flap atoms of the pyrrolidine ring. In the crystal, molecules are linked via C—H⋯O hydrogen bonds. For the major disorder component, these form C(11) chains that propagate parallel to the a axis.
Keywords: crystal structure; spiro; indoline; tetrahydroisoquinoline; pyrrolidine.
CCDC reference: 1983982
1. Chemical context
Spiro frameworks are often utilized in drug design as a result of their three-dimensionality and structural diversity, which provide a framework for the attachment of pharmaceutically relevant active sites (Kobayashi et al., 1991). The spiro-pyrrolidine structural motif is present in numerous naturally occurring and pharmacologically important The spiro-pyrrolidine-indolin-2-one framework in particular is found in a number of of biological significance (Hilton et al., 2000). Some of these compounds have been used as antimicrobial and antitumour agents (Sundar et al., 2011), or have analgesic (Crooks & Sommerville, 1982) and anti-influenza properties (Stylianakis et al., 2003). Taking into account the significance of in this context, the single-crystal X-ray structure of the title compound, 1, was determined.
2. Structural commentary
An ellipsoid plot of 1 is shown in Fig. 1. The bond lengths (Allen et al., 1998) and bond angles are all normal. The tetrahydroisoquinoline (N2/C11–C19) and pyrrolidine (N2/C1/C9–C11) rings each have envelope conformations, with the maximum deviation of the flap atoms being −0.363 (1) Å (for N2) and 0.253 (2) Å (for C11), respectively. These non-planar ring systems are fused at N2/C11, such that the dihedral angle between their non-flap atoms is 11.29 (7)°. The N-methyl indolinone ring system (N1/C1–C8/O1/C34) is essentially planar, with the maximum deviation being 0.030 (2) Å for the oxygen atom (O1). This group is attached to the pyrrolidine ring via the spiro-linkage, forming a dihedral angle with the non-flap atoms (N2/C1/C9/C10) of the pyrrolidine of 83.26 (5)°. The sum of the bond angles around N1 and N2 (360.0 and 338.33°, respectively) is in accordance with sp2 and sp3 states (Beddoes et al., 1986).
The methoxyphenyl group is disordered over two orientations, with refined occupancies of 0.638 (6):0.362 (6). The disordered methoxyphenyl ring major (C27–C33/O3) and minor (C27D–C33D/O3D) components are largely planar, with the maximum deviations from their respective mean planes being observed for the methyl carbons, C33 [0.303 (7) Å] and C33D [0.130 (12) Å].
3. Supramolecular features
In the crystal packing of 1, there are no classical hydrogen bonds or π–π interactions between the various rings of adjacent molecules. There are, however, different weak C—H⋯O close contacts for the two disorder components (Table 1). For the major component, there is a close contact between translation-related molecules, C33—H33B⋯O2i, of 3.490 (5) Å [symmetry code: (i) x + 1, y, z], while for the minor component there is a close contact between glide-related molecules, C4—H4⋯O3ii, of 3.559 (6) Å [symmetry code: (ii) x − 1, −y + , z − ]. For the major component, these generate C(11) chains (Bernstein et al., 1995) that propagate parallel to the a axis (Fig. 2).
4. Database survey
A search in the Cambridge Structural Database (CSD, version 5.39, update August 2018; Groom et al., 2016) using pyrrolidine as the search fragment produced over 11600 hits. For the core spiro-pyrrolidine/N-methyl pyrrolidone fragment, the yield was a more modest 88 hits. These 88 structures show many different substitution patterns. The four structures with the most features in common with 1 are probably RAQCIY (Du et al., 2017), IFETAR (Guo et al., 2018), DOHMEV (Boudriga et al., 2019), and KIFRID (Zhang et al., 2018), though none of these are especially similar to 1.
5. Synthesis and crystallization
In a 50 mL round-bottom flask, 1-methylisatin (0.5 mmol) was dissolved in toluene (5 mL) followed by the addition of 1,2,3,4-tetrahydroisoquinoline (0.5 mmol) and the mixture was stirred at room temperature for half an hour. After that, (E)-3-(4-methoxyphenyl)-1-phenylprop-2-en-1-one (0.5 mmol) was added to the reaction mixture and stirring was continued at 383 K for 10 h. The reaction was monitored for the formation of the product by TLC at regular intervals. Soon after the formation of the product, the reaction mixture was concentrated under reduced pressure and extracted with ethyl acetate/water (v/v = 75:25). The organic layer was dried over anhydrous sodium sulfate and concentrated under vacuum to yield the crude product, which was purified by using ethyl acetate/n-hexane (3:17) as 0.2g of the compound were dissolved in ethanol and the solution was kept undisturbed in the open air for one week. After five days, crystals started to appear and were separated carefully.
1H NMR (500 MHz, CDCl3) δ 7.60 (d, J = 8.7 Hz, 2H), 7.28–7.22 (m, 3H), 7.14–7.03 (m, 5H), 7.02–6.98 (m, 1H), 6.96–6.90 (m, 3H), 6.92–6.85 (m, 1H), 6.75 (d, J = 7.8 Hz, 1H), 6.32 (d, J = 7.7 Hz, 1H), 5.15 (d, J = 10.1 Hz, 1H), 4.52 (d, J = 9.7 Hz, 1H), 4.24 (t, J = 9.9 Hz, 1H), 3.81 (s, 3H), 3.07 (s, 3H), 2.92 (d, J = 7.7 Hz, 2H), 2.65 (d, J = 12.3 Hz, 1H), 2.52–2.47 (m, 1H).
13C NMR (126 MHz, CDCl3) δ 197.0, 178.63, 158.55, 143.58, 138.24, 137.45, 134.71, 133.83, 132.39, 130.02, 129.07, 128.78, 127.77, 127.46, 127.12, 126.26, 126.15, 125.46, 125.04, 123.04, 114.43, 107.16, 70.87, 64.13, 63.59, 55.26, 49.83, 42.39, 30.32, 25.89.
6. Refinement
Crystal data, data collection and structure . Hydrogen atoms were positioned geometrically (C—H = 0.93–0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl H and 1.2Ueq (C) for other H atoms. The occupancies of the disorder group of the methoxy phenyl moiety were initially allowed to ride then it was fixed and refined. The benzene rings were refined as rigid hexagons with C—C distances of 1.39 Å. The other bond lengths of the major and the minor components were made similar using similarity restraints with an s.u. of 0.01 Å. The positions of the methoxyphenyl moiety (C30/O3/C33) atoms are disordered over two positions with site occupancy factors of 0.638 (6) and 0.362 (6), respectively.
details are summarized in Table 2Supporting information
CCDC reference: 1983982
https://doi.org/10.1107/S2056989020010300/tx2027sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989020010300/tx2027Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989020010300/tx2027Isup3.cml
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2020); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2020).C34H30N2O3 | F(000) = 1088 |
Mr = 514.60 | Dx = 1.274 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5632 (1) Å | Cell parameters from 4055 reflections |
b = 17.8067 (3) Å | θ = 2.3–26.3° |
c = 16.1958 (3) Å | µ = 0.08 mm−1 |
β = 103.463 (1)° | T = 294 K |
V = 2682.18 (7) Å3 | Block, colourless |
Z = 4 | 0.26 × 0.24 × 0.13 mm |
Bruker D8 QUEST diffractometer | 4055 reflections with I > 2σ(I) |
Radiation source: PHOTON-100 | Rint = 0.055 |
ω and φ scans | θmax = 26.3°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→11 |
Tmin = 0.565, Tmax = 0.746 | k = −22→22 |
24289 measured reflections | l = −20→19 |
5392 independent reflections |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.053 | w = 1/[σ2(Fo2) + (0.0587P)2 + 0.8201P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.144 | (Δ/σ)max = 0.001 |
S = 1.06 | Δρmax = 0.26 e Å−3 |
5392 reflections | Δρmin = −0.22 e Å−3 |
411 parameters | Extinction correction: SHELXL2018/3 (Sheldrick 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
155 restraints | Extinction coefficient: 0.0198 (18) |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
C1 | 0.45235 (17) | 0.17258 (8) | 0.65452 (10) | 0.0364 (4) | |
C2 | 0.5169 (2) | 0.13834 (10) | 0.58323 (12) | 0.0478 (4) | |
C3 | 0.2724 (2) | 0.12535 (11) | 0.54118 (12) | 0.0564 (5) | |
C4 | 0.1366 (3) | 0.10549 (16) | 0.49517 (17) | 0.0892 (8) | |
H4 | 0.123305 | 0.082582 | 0.442303 | 0.107* | |
C5 | 0.0218 (3) | 0.12087 (19) | 0.5305 (2) | 0.0981 (9) | |
H5 | −0.070659 | 0.108839 | 0.500441 | 0.118* | |
C6 | 0.0409 (2) | 0.15319 (15) | 0.60827 (19) | 0.0800 (7) | |
H6 | −0.038455 | 0.162177 | 0.630907 | 0.096* | |
C7 | 0.1778 (2) | 0.17310 (11) | 0.65468 (14) | 0.0553 (5) | |
H7 | 0.190555 | 0.195187 | 0.707949 | 0.066* | |
C8 | 0.29367 (18) | 0.15934 (9) | 0.61985 (11) | 0.0423 (4) | |
C9 | 0.50774 (16) | 0.25579 (8) | 0.67048 (10) | 0.0348 (3) | |
H9 | 0.571274 | 0.266515 | 0.632400 | 0.042* | |
C10 | 0.59873 (16) | 0.25791 (8) | 0.76320 (10) | 0.0346 (3) | |
H10 | 0.534885 | 0.273687 | 0.799327 | 0.042* | |
C11 | 0.63486 (17) | 0.17511 (8) | 0.78236 (10) | 0.0372 (4) | |
H11 | 0.713397 | 0.160425 | 0.756183 | 0.045* | |
C12 | 0.67101 (18) | 0.15111 (9) | 0.87455 (11) | 0.0414 (4) | |
C13 | 0.74885 (19) | 0.19684 (11) | 0.93799 (11) | 0.0511 (4) | |
H13 | 0.778245 | 0.244022 | 0.924110 | 0.061* | |
C14 | 0.7837 (2) | 0.17333 (13) | 1.02196 (13) | 0.0617 (5) | |
H14 | 0.834330 | 0.204991 | 1.064128 | 0.074* | |
C15 | 0.7430 (2) | 0.10303 (13) | 1.04259 (13) | 0.0659 (6) | |
H15 | 0.767707 | 0.086545 | 1.098588 | 0.079* | |
C16 | 0.6659 (2) | 0.05745 (12) | 0.98034 (13) | 0.0637 (6) | |
H16 | 0.638727 | 0.010029 | 0.994909 | 0.076* | |
C17 | 0.6272 (2) | 0.08009 (10) | 0.89584 (12) | 0.0507 (4) | |
C18 | 0.5325 (3) | 0.03000 (11) | 0.83073 (13) | 0.0681 (6) | |
H18A | 0.438282 | 0.027019 | 0.843204 | 0.082* | |
H18B | 0.573028 | −0.020202 | 0.835908 | 0.082* | |
C19 | 0.5152 (2) | 0.05639 (9) | 0.74011 (12) | 0.0531 (5) | |
H19A | 0.597674 | 0.041031 | 0.718941 | 0.064* | |
H19B | 0.429728 | 0.034133 | 0.704261 | 0.064* | |
C20 | 0.38421 (17) | 0.31188 (9) | 0.65193 (11) | 0.0405 (4) | |
C21 | 0.31331 (18) | 0.32852 (10) | 0.56177 (11) | 0.0442 (4) | |
C22 | 0.3755 (2) | 0.31242 (12) | 0.49476 (12) | 0.0568 (5) | |
H22 | 0.466022 | 0.290241 | 0.505273 | 0.068* | |
C23 | 0.3042 (2) | 0.32906 (17) | 0.41218 (14) | 0.0801 (7) | |
H23 | 0.346605 | 0.317979 | 0.367452 | 0.096* | |
C24 | 0.1710 (3) | 0.36189 (19) | 0.39643 (16) | 0.0921 (9) | |
H24 | 0.123408 | 0.373183 | 0.340935 | 0.111* | |
C25 | 0.1074 (2) | 0.37819 (18) | 0.46183 (17) | 0.0871 (8) | |
H25 | 0.016691 | 0.400127 | 0.450662 | 0.105* | |
C26 | 0.1781 (2) | 0.36202 (13) | 0.54426 (15) | 0.0650 (6) | |
H26 | 0.134985 | 0.373605 | 0.588563 | 0.078* | |
C27 | 0.7190 (15) | 0.3150 (7) | 0.7744 (19) | 0.0357 (9) | 0.638 (6) |
C28 | 0.7031 (10) | 0.3858 (5) | 0.8046 (9) | 0.0496 (12) | 0.638 (6) |
H28 | 0.619848 | 0.397017 | 0.822432 | 0.060* | 0.638 (6) |
C29 | 0.8066 (7) | 0.4410 (4) | 0.8093 (6) | 0.0575 (14) | 0.638 (6) |
H29 | 0.793034 | 0.488124 | 0.830907 | 0.069* | 0.638 (6) |
C30 | 0.9290 (6) | 0.4261 (3) | 0.7822 (4) | 0.0445 (13) | 0.638 (6) |
C31 | 0.9504 (6) | 0.3562 (3) | 0.7532 (5) | 0.0490 (13) | 0.638 (6) |
H31 | 1.035161 | 0.345029 | 0.736969 | 0.059* | 0.638 (6) |
C32 | 0.8453 (7) | 0.3019 (3) | 0.7481 (7) | 0.0489 (13) | 0.638 (6) |
H32 | 0.859666 | 0.254900 | 0.726375 | 0.059* | 0.638 (6) |
O3 | 1.0252 (4) | 0.4834 (2) | 0.7876 (2) | 0.0793 (11) | 0.638 (6) |
C33 | 1.1100 (5) | 0.4875 (3) | 0.7290 (3) | 0.0908 (16) | 0.638 (6) |
H33A | 1.052694 | 0.475989 | 0.673456 | 0.136* | 0.638 (6) |
H33B | 1.187392 | 0.452012 | 0.743852 | 0.136* | 0.638 (6) |
H33C | 1.148553 | 0.537251 | 0.729088 | 0.136* | 0.638 (6) |
C27D | 0.731 (3) | 0.3074 (12) | 0.770 (3) | 0.0357 (9) | 0.362 (6) |
C28D | 0.7249 (19) | 0.3815 (10) | 0.7913 (17) | 0.0496 (12) | 0.362 (6) |
H28D | 0.641424 | 0.400216 | 0.803831 | 0.060* | 0.362 (6) |
C29D | 0.8417 (12) | 0.4297 (6) | 0.7949 (9) | 0.049 (2) | 0.362 (6) |
H29D | 0.835755 | 0.479685 | 0.810273 | 0.059* | 0.362 (6) |
C30D | 0.9633 (9) | 0.4034 (5) | 0.7761 (8) | 0.041 (2) | 0.362 (6) |
C31D | 0.9735 (11) | 0.3295 (5) | 0.7567 (10) | 0.050 (2) | 0.362 (6) |
H31D | 1.057299 | 0.311310 | 0.744188 | 0.061* | 0.362 (6) |
C32D | 0.8595 (15) | 0.2815 (6) | 0.7556 (13) | 0.0489 (13) | 0.362 (6) |
H32D | 0.869624 | 0.230713 | 0.745157 | 0.059* | 0.362 (6) |
O3D | 1.0812 (5) | 0.4476 (3) | 0.7781 (4) | 0.0670 (17) | 0.362 (6) |
C33D | 1.0613 (13) | 0.5235 (6) | 0.7809 (10) | 0.132 (4) | 0.362 (6) |
H33D | 1.151938 | 0.548557 | 0.786794 | 0.198* | 0.362 (6) |
H33E | 1.021434 | 0.535591 | 0.828434 | 0.198* | 0.362 (6) |
H33F | 0.996448 | 0.539583 | 0.729374 | 0.198* | 0.362 (6) |
C34 | 0.4232 (4) | 0.08287 (19) | 0.43976 (16) | 0.1045 (10) | |
H34A | 0.377044 | 0.115249 | 0.394113 | 0.157* | |
H34B | 0.380274 | 0.033877 | 0.431461 | 0.157* | |
H34C | 0.523694 | 0.079156 | 0.440781 | 0.157* | |
N1 | 0.4056 (2) | 0.11377 (10) | 0.52023 (10) | 0.0611 (5) | |
N2 | 0.50281 (15) | 0.13804 (7) | 0.73799 (8) | 0.0379 (3) | |
O1 | 0.64375 (16) | 0.13463 (9) | 0.58338 (10) | 0.0689 (4) | |
O2 | 0.34147 (16) | 0.34041 (8) | 0.70952 (9) | 0.0624 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0427 (8) | 0.0343 (8) | 0.0314 (8) | 0.0025 (6) | 0.0071 (7) | −0.0015 (6) |
C2 | 0.0607 (11) | 0.0420 (9) | 0.0424 (10) | 0.0081 (8) | 0.0155 (9) | −0.0025 (8) |
C3 | 0.0646 (12) | 0.0542 (11) | 0.0428 (11) | −0.0016 (9) | −0.0030 (9) | −0.0054 (9) |
C4 | 0.0880 (19) | 0.100 (2) | 0.0612 (15) | −0.0108 (15) | −0.0211 (13) | −0.0222 (14) |
C5 | 0.0588 (15) | 0.115 (2) | 0.104 (2) | −0.0155 (14) | −0.0164 (15) | −0.0115 (18) |
C6 | 0.0485 (12) | 0.0855 (17) | 0.102 (2) | −0.0072 (11) | 0.0103 (12) | 0.0003 (15) |
C7 | 0.0472 (10) | 0.0543 (11) | 0.0634 (13) | −0.0030 (8) | 0.0108 (9) | 0.0003 (9) |
C8 | 0.0474 (9) | 0.0361 (8) | 0.0397 (9) | −0.0032 (7) | 0.0027 (7) | 0.0009 (7) |
C9 | 0.0364 (8) | 0.0346 (8) | 0.0334 (8) | 0.0012 (6) | 0.0079 (6) | 0.0016 (6) |
C10 | 0.0392 (8) | 0.0330 (8) | 0.0314 (8) | 0.0012 (6) | 0.0076 (6) | 0.0003 (6) |
C11 | 0.0404 (8) | 0.0337 (8) | 0.0362 (9) | 0.0031 (6) | 0.0062 (7) | −0.0011 (7) |
C12 | 0.0428 (9) | 0.0410 (9) | 0.0381 (9) | 0.0065 (7) | 0.0049 (7) | 0.0045 (7) |
C13 | 0.0500 (10) | 0.0578 (11) | 0.0413 (10) | −0.0048 (8) | 0.0019 (8) | 0.0049 (8) |
C14 | 0.0592 (12) | 0.0800 (15) | 0.0398 (11) | −0.0069 (10) | −0.0010 (9) | 0.0024 (10) |
C15 | 0.0699 (13) | 0.0818 (15) | 0.0403 (11) | 0.0028 (11) | 0.0013 (9) | 0.0189 (10) |
C16 | 0.0803 (14) | 0.0555 (12) | 0.0516 (12) | 0.0036 (10) | 0.0081 (10) | 0.0180 (10) |
C17 | 0.0626 (11) | 0.0406 (9) | 0.0453 (10) | 0.0065 (8) | 0.0052 (8) | 0.0074 (8) |
C18 | 0.1057 (17) | 0.0350 (9) | 0.0558 (13) | −0.0070 (10) | 0.0028 (12) | 0.0072 (9) |
C19 | 0.0723 (12) | 0.0310 (9) | 0.0506 (11) | 0.0010 (8) | 0.0031 (9) | −0.0033 (8) |
C20 | 0.0429 (9) | 0.0334 (8) | 0.0449 (10) | 0.0006 (7) | 0.0098 (7) | 0.0026 (7) |
C21 | 0.0399 (9) | 0.0421 (9) | 0.0484 (10) | −0.0010 (7) | 0.0055 (7) | 0.0099 (8) |
C22 | 0.0462 (10) | 0.0761 (13) | 0.0460 (11) | 0.0065 (9) | 0.0064 (8) | 0.0113 (10) |
C23 | 0.0601 (13) | 0.133 (2) | 0.0449 (12) | 0.0098 (13) | 0.0070 (10) | 0.0145 (13) |
C24 | 0.0613 (14) | 0.155 (3) | 0.0520 (14) | 0.0119 (15) | −0.0034 (11) | 0.0281 (15) |
C25 | 0.0482 (12) | 0.130 (2) | 0.0766 (17) | 0.0222 (13) | 0.0007 (11) | 0.0321 (16) |
C26 | 0.0499 (11) | 0.0825 (15) | 0.0617 (13) | 0.0149 (10) | 0.0107 (10) | 0.0182 (11) |
C27 | 0.041 (2) | 0.037 (2) | 0.027 (3) | 0.000 (2) | 0.0048 (18) | 0.000 (2) |
C28 | 0.041 (3) | 0.0396 (13) | 0.071 (5) | 0.0006 (17) | 0.0188 (16) | −0.0077 (15) |
C29 | 0.043 (3) | 0.042 (2) | 0.090 (4) | −0.0038 (19) | 0.019 (2) | −0.023 (2) |
C30 | 0.038 (3) | 0.045 (3) | 0.049 (2) | −0.007 (2) | 0.006 (2) | −0.009 (2) |
C31 | 0.046 (2) | 0.050 (3) | 0.054 (2) | −0.002 (2) | 0.019 (2) | −0.007 (3) |
C32 | 0.0555 (18) | 0.039 (3) | 0.057 (2) | −0.002 (2) | 0.0224 (17) | −0.007 (3) |
O3 | 0.068 (2) | 0.062 (2) | 0.111 (2) | −0.0330 (17) | 0.0269 (16) | −0.0194 (18) |
C33 | 0.073 (3) | 0.074 (3) | 0.136 (4) | −0.025 (2) | 0.046 (3) | 0.007 (3) |
C27D | 0.041 (2) | 0.037 (2) | 0.027 (3) | 0.000 (2) | 0.0048 (18) | 0.000 (2) |
C28D | 0.041 (3) | 0.0396 (13) | 0.071 (5) | 0.0006 (17) | 0.0188 (16) | −0.0077 (15) |
C29D | 0.047 (5) | 0.029 (3) | 0.076 (5) | 0.002 (3) | 0.023 (4) | −0.007 (3) |
C30D | 0.031 (3) | 0.045 (5) | 0.045 (4) | 0.002 (3) | 0.006 (3) | −0.001 (4) |
C31D | 0.041 (3) | 0.048 (5) | 0.067 (4) | 0.005 (3) | 0.020 (3) | −0.006 (5) |
C32D | 0.0555 (18) | 0.039 (3) | 0.057 (2) | −0.002 (2) | 0.0224 (17) | −0.007 (3) |
O3D | 0.040 (2) | 0.052 (3) | 0.106 (4) | −0.0002 (19) | 0.010 (2) | 0.007 (3) |
C33D | 0.104 (6) | 0.075 (5) | 0.215 (9) | −0.006 (5) | 0.034 (6) | 0.009 (6) |
C34 | 0.148 (3) | 0.121 (2) | 0.0454 (14) | 0.018 (2) | 0.0227 (15) | −0.0299 (15) |
N1 | 0.0810 (12) | 0.0650 (11) | 0.0350 (9) | 0.0052 (9) | 0.0087 (8) | −0.0150 (7) |
N2 | 0.0476 (7) | 0.0300 (7) | 0.0331 (7) | −0.0004 (5) | 0.0032 (6) | −0.0005 (5) |
O1 | 0.0658 (9) | 0.0790 (10) | 0.0696 (10) | 0.0142 (7) | 0.0309 (8) | −0.0106 (8) |
O2 | 0.0726 (9) | 0.0613 (9) | 0.0524 (8) | 0.0279 (7) | 0.0125 (7) | −0.0047 (7) |
C1—N2 | 1.461 (2) | C21—C22 | 1.384 (3) |
C1—C8 | 1.509 (2) | C21—C26 | 1.392 (3) |
C1—C2 | 1.555 (2) | C22—C23 | 1.385 (3) |
C1—C9 | 1.575 (2) | C22—H22 | 0.9300 |
C2—O1 | 1.214 (2) | C23—C24 | 1.371 (3) |
C2—N1 | 1.364 (3) | C23—H23 | 0.9300 |
C3—C8 | 1.382 (3) | C24—C25 | 1.369 (4) |
C3—C4 | 1.384 (3) | C24—H24 | 0.9300 |
C3—N1 | 1.408 (3) | C25—C26 | 1.379 (3) |
C4—C5 | 1.378 (4) | C25—H25 | 0.9300 |
C4—H4 | 0.9300 | C26—H26 | 0.9300 |
C5—C6 | 1.358 (4) | C27—C28 | 1.373 (7) |
C5—H5 | 0.9300 | C27—C32 | 1.390 (8) |
C6—C7 | 1.396 (3) | C28—C29 | 1.385 (7) |
C6—H6 | 0.9300 | C28—H28 | 0.9300 |
C7—C8 | 1.377 (3) | C29—C30 | 1.369 (5) |
C7—H7 | 0.9300 | C29—H29 | 0.9300 |
C9—C20 | 1.523 (2) | C30—C31 | 1.362 (6) |
C9—C10 | 1.551 (2) | C30—O3 | 1.363 (5) |
C9—H9 | 0.9800 | C31—C32 | 1.383 (6) |
C10—C27 | 1.514 (10) | C31—H31 | 0.9300 |
C10—C27D | 1.522 (17) | C32—H32 | 0.9300 |
C10—C11 | 1.529 (2) | O3—C33 | 1.386 (6) |
C10—H10 | 0.9800 | C33—H33A | 0.9600 |
C11—N2 | 1.457 (2) | C33—H33B | 0.9600 |
C11—C12 | 1.514 (2) | C33—H33C | 0.9600 |
C11—H11 | 0.9800 | C27D—C28D | 1.369 (12) |
C12—C13 | 1.385 (3) | C27D—C32D | 1.383 (12) |
C12—C17 | 1.400 (2) | C28D—C29D | 1.399 (12) |
C13—C14 | 1.387 (3) | C28D—H28D | 0.9300 |
C13—H13 | 0.9300 | C29D—C30D | 1.353 (9) |
C14—C15 | 1.375 (3) | C29D—H29D | 0.9300 |
C14—H14 | 0.9300 | C30D—C31D | 1.361 (9) |
C15—C16 | 1.368 (3) | C30D—O3D | 1.370 (9) |
C15—H15 | 0.9300 | C31D—C32D | 1.382 (12) |
C16—C17 | 1.392 (3) | C31D—H31D | 0.9300 |
C16—H16 | 0.9300 | C32D—H32D | 0.9300 |
C17—C18 | 1.511 (3) | O3D—C33D | 1.367 (11) |
C18—C19 | 1.513 (3) | C33D—H33D | 0.9600 |
C18—H18A | 0.9700 | C33D—H33E | 0.9600 |
C18—H18B | 0.9700 | C33D—H33F | 0.9600 |
C19—N2 | 1.459 (2) | C34—N1 | 1.460 (3) |
C19—H19A | 0.9700 | C34—H34A | 0.9600 |
C19—H19B | 0.9700 | C34—H34B | 0.9600 |
C20—O2 | 1.214 (2) | C34—H34C | 0.9600 |
C20—C21 | 1.490 (2) | ||
N2—C1—C8 | 111.44 (13) | C22—C21—C26 | 118.54 (17) |
N2—C1—C2 | 114.79 (13) | C22—C21—C20 | 123.15 (15) |
C8—C1—C2 | 101.60 (13) | C26—C21—C20 | 118.31 (17) |
N2—C1—C9 | 102.60 (12) | C21—C22—C23 | 120.53 (19) |
C8—C1—C9 | 118.61 (13) | C21—C22—H22 | 119.7 |
C2—C1—C9 | 108.32 (13) | C23—C22—H22 | 119.7 |
O1—C2—N1 | 126.10 (17) | C24—C23—C22 | 119.9 (2) |
O1—C2—C1 | 126.08 (17) | C24—C23—H23 | 120.0 |
N1—C2—C1 | 107.82 (15) | C22—C23—H23 | 120.0 |
C8—C3—C4 | 121.8 (2) | C25—C24—C23 | 120.5 (2) |
C8—C3—N1 | 109.83 (16) | C25—C24—H24 | 119.8 |
C4—C3—N1 | 128.4 (2) | C23—C24—H24 | 119.8 |
C5—C4—C3 | 117.6 (2) | C24—C25—C26 | 119.9 (2) |
C5—C4—H4 | 121.2 | C24—C25—H25 | 120.0 |
C3—C4—H4 | 121.2 | C26—C25—H25 | 120.0 |
C6—C5—C4 | 121.4 (2) | C25—C26—C21 | 120.6 (2) |
C6—C5—H5 | 119.3 | C25—C26—H26 | 119.7 |
C4—C5—H5 | 119.3 | C21—C26—H26 | 119.7 |
C5—C6—C7 | 120.9 (2) | C28—C27—C32 | 116.1 (7) |
C5—C6—H6 | 119.5 | C28—C27—C10 | 121.0 (6) |
C7—C6—H6 | 119.5 | C32—C27—C10 | 122.7 (7) |
C8—C7—C6 | 118.5 (2) | C27—C28—C29 | 122.3 (5) |
C8—C7—H7 | 120.7 | C27—C28—H28 | 118.8 |
C6—C7—H7 | 120.7 | C29—C28—H28 | 118.8 |
C7—C8—C3 | 119.72 (17) | C30—C29—C28 | 119.9 (5) |
C7—C8—C1 | 130.92 (16) | C30—C29—H29 | 120.1 |
C3—C8—C1 | 109.32 (16) | C28—C29—H29 | 120.1 |
C20—C9—C10 | 114.19 (13) | C31—C30—O3 | 123.6 (5) |
C20—C9—C1 | 111.66 (12) | C31—C30—C29 | 119.7 (4) |
C10—C9—C1 | 105.86 (12) | O3—C30—C29 | 116.7 (5) |
C20—C9—H9 | 108.3 | C30—C31—C32 | 119.6 (5) |
C10—C9—H9 | 108.3 | C30—C31—H31 | 120.2 |
C1—C9—H9 | 108.3 | C32—C31—H31 | 120.2 |
C27—C10—C11 | 119.6 (7) | C31—C32—C27 | 122.4 (6) |
C27D—C10—C11 | 113.6 (12) | C31—C32—H32 | 118.8 |
C27—C10—C9 | 111.8 (12) | C27—C32—H32 | 118.8 |
C27D—C10—C9 | 110 (2) | C30—O3—C33 | 119.3 (4) |
C11—C10—C9 | 102.84 (12) | O3—C33—H33A | 109.5 |
C27—C10—H10 | 107.3 | O3—C33—H33B | 109.5 |
C11—C10—H10 | 107.3 | H33A—C33—H33B | 109.5 |
C9—C10—H10 | 107.3 | O3—C33—H33C | 109.5 |
N2—C11—C12 | 109.33 (13) | H33A—C33—H33C | 109.5 |
N2—C11—C10 | 101.99 (12) | H33B—C33—H33C | 109.5 |
C12—C11—C10 | 117.46 (13) | C28D—C27D—C32D | 117.0 (13) |
N2—C11—H11 | 109.2 | C28D—C27D—C10 | 119.6 (12) |
C12—C11—H11 | 109.2 | C32D—C27D—C10 | 123.5 (12) |
C10—C11—H11 | 109.2 | C27D—C28D—C29D | 121.5 (11) |
C13—C12—C17 | 119.24 (16) | C27D—C28D—H28D | 119.3 |
C13—C12—C11 | 121.72 (15) | C29D—C28D—H28D | 119.3 |
C17—C12—C11 | 119.02 (15) | C30D—C29D—C28D | 119.9 (9) |
C12—C13—C14 | 120.99 (18) | C30D—C29D—H29D | 120.0 |
C12—C13—H13 | 119.5 | C28D—C29D—H29D | 120.0 |
C14—C13—H13 | 119.5 | C29D—C30D—C31D | 119.8 (8) |
C15—C14—C13 | 119.7 (2) | C29D—C30D—O3D | 122.8 (9) |
C15—C14—H14 | 120.1 | C31D—C30D—O3D | 117.3 (8) |
C13—C14—H14 | 120.1 | C30D—C31D—C32D | 120.1 (9) |
C16—C15—C14 | 119.70 (19) | C30D—C31D—H31D | 119.9 |
C16—C15—H15 | 120.2 | C32D—C31D—H31D | 119.9 |
C14—C15—H15 | 120.2 | C31D—C32D—C27D | 121.5 (11) |
C15—C16—C17 | 121.8 (2) | C31D—C32D—H32D | 119.3 |
C15—C16—H16 | 119.1 | C27D—C32D—H32D | 119.3 |
C17—C16—H16 | 119.1 | C33D—O3D—C30D | 116.6 (8) |
C16—C17—C12 | 118.50 (18) | O3D—C33D—H33D | 109.5 |
C16—C17—C18 | 119.64 (18) | O3D—C33D—H33E | 109.5 |
C12—C17—C18 | 121.76 (16) | H33D—C33D—H33E | 109.5 |
C17—C18—C19 | 113.98 (17) | O3D—C33D—H33F | 109.5 |
C17—C18—H18A | 108.8 | H33D—C33D—H33F | 109.5 |
C19—C18—H18A | 108.8 | H33E—C33D—H33F | 109.5 |
C17—C18—H18B | 108.8 | N1—C34—H34A | 109.5 |
C19—C18—H18B | 108.8 | N1—C34—H34B | 109.5 |
H18A—C18—H18B | 107.7 | H34A—C34—H34B | 109.5 |
N2—C19—C18 | 108.81 (15) | N1—C34—H34C | 109.5 |
N2—C19—H19A | 109.9 | H34A—C34—H34C | 109.5 |
C18—C19—H19A | 109.9 | H34B—C34—H34C | 109.5 |
N2—C19—H19B | 109.9 | C2—N1—C3 | 111.40 (15) |
C18—C19—H19B | 109.9 | C2—N1—C34 | 123.9 (2) |
H19A—C19—H19B | 108.3 | C3—N1—C34 | 124.7 (2) |
O2—C20—C21 | 120.82 (15) | C11—N2—C19 | 112.57 (13) |
O2—C20—C9 | 120.50 (15) | C11—N2—C1 | 109.09 (12) |
C21—C20—C9 | 118.63 (14) | C19—N2—C1 | 116.67 (13) |
N2—C1—C2—O1 | −58.2 (2) | C9—C20—C21—C22 | −18.0 (2) |
C8—C1—C2—O1 | −178.62 (18) | O2—C20—C21—C26 | −15.4 (3) |
C9—C1—C2—O1 | 55.7 (2) | C9—C20—C21—C26 | 162.11 (17) |
N2—C1—C2—N1 | 122.25 (16) | C26—C21—C22—C23 | −0.3 (3) |
C8—C1—C2—N1 | 1.87 (18) | C20—C21—C22—C23 | 179.9 (2) |
C9—C1—C2—N1 | −123.79 (15) | C21—C22—C23—C24 | 0.1 (4) |
C8—C3—C4—C5 | 0.1 (4) | C22—C23—C24—C25 | −0.2 (5) |
N1—C3—C4—C5 | 178.0 (2) | C23—C24—C25—C26 | 0.5 (5) |
C3—C4—C5—C6 | −1.1 (5) | C24—C25—C26—C21 | −0.6 (4) |
C4—C5—C6—C7 | 1.0 (5) | C22—C21—C26—C25 | 0.5 (3) |
C5—C6—C7—C8 | 0.1 (4) | C20—C21—C26—C25 | −179.6 (2) |
C6—C7—C8—C3 | −1.0 (3) | C11—C10—C27—C28 | −143.2 (18) |
C6—C7—C8—C1 | −178.42 (19) | C9—C10—C27—C28 | 97 (2) |
C4—C3—C8—C7 | 1.0 (3) | C11—C10—C27—C32 | 43 (3) |
N1—C3—C8—C7 | −177.27 (17) | C9—C10—C27—C32 | −77 (2) |
C4—C3—C8—C1 | 178.9 (2) | C32—C27—C28—C29 | 0 (3) |
N1—C3—C8—C1 | 0.6 (2) | C10—C27—C28—C29 | −174.9 (16) |
N2—C1—C8—C7 | 53.4 (2) | C27—C28—C29—C30 | 1 (2) |
C2—C1—C8—C7 | 176.10 (18) | C28—C29—C30—C31 | −2.2 (13) |
C9—C1—C8—C7 | −65.4 (2) | C28—C29—C30—O3 | 179.1 (9) |
N2—C1—C8—C3 | −124.20 (15) | O3—C30—C31—C32 | −178.6 (7) |
C2—C1—C8—C3 | −1.48 (18) | C29—C30—C31—C32 | 2.8 (11) |
C9—C1—C8—C3 | 117.03 (16) | C30—C31—C32—C27 | −2.3 (19) |
N2—C1—C9—C20 | −119.90 (14) | C28—C27—C32—C31 | 1 (3) |
C8—C1—C9—C20 | 3.37 (19) | C10—C27—C32—C31 | 175.4 (15) |
C2—C1—C9—C20 | 118.32 (15) | C31—C30—O3—C33 | 32.0 (9) |
N2—C1—C9—C10 | 4.93 (15) | C29—C30—O3—C33 | −149.3 (7) |
C8—C1—C9—C10 | 128.20 (14) | C11—C10—C27D—C28D | −151 (3) |
C2—C1—C9—C10 | −116.85 (14) | C9—C10—C27D—C28D | 94 (4) |
C20—C9—C10—C27 | −87.6 (4) | C11—C10—C27D—C32D | 28 (5) |
C1—C9—C10—C27 | 149.2 (4) | C9—C10—C27D—C32D | −87 (4) |
C20—C9—C10—C27D | −95.6 (7) | C32D—C27D—C28D—C29D | 3 (6) |
C1—C9—C10—C27D | 141.2 (7) | C10—C27D—C28D—C29D | −178 (3) |
C20—C9—C10—C11 | 142.92 (13) | C27D—C28D—C29D—C30D | 1 (4) |
C1—C9—C10—C11 | 19.68 (15) | C28D—C29D—C30D—C31D | −2 (2) |
C27—C10—C11—N2 | −161.6 (11) | C28D—C29D—C30D—O3D | 179.7 (16) |
C27D—C10—C11—N2 | −156 (2) | C29D—C30D—C31D—C32D | 0 (2) |
C9—C10—C11—N2 | −37.08 (14) | O3D—C30D—C31D—C32D | 178.5 (14) |
C27—C10—C11—C12 | 78.9 (11) | C30D—C31D—C32D—C27D | 3 (4) |
C27D—C10—C11—C12 | 84 (2) | C28D—C27D—C32D—C31D | −5 (6) |
C9—C10—C11—C12 | −156.53 (13) | C10—C27D—C32D—C31D | 176 (3) |
N2—C11—C12—C13 | −152.60 (16) | C29D—C30D—O3D—C33D | −14.6 (17) |
C10—C11—C12—C13 | −37.1 (2) | C31D—C30D—O3D—C33D | 167.5 (12) |
N2—C11—C12—C17 | 28.8 (2) | O1—C2—N1—C3 | 178.84 (19) |
C10—C11—C12—C17 | 144.31 (16) | C1—C2—N1—C3 | −1.6 (2) |
C17—C12—C13—C14 | −0.1 (3) | O1—C2—N1—C34 | −3.9 (3) |
C11—C12—C13—C14 | −178.63 (17) | C1—C2—N1—C34 | 175.6 (2) |
C12—C13—C14—C15 | 1.3 (3) | C8—C3—N1—C2 | 0.7 (2) |
C13—C14—C15—C16 | −1.3 (3) | C4—C3—N1—C2 | −177.4 (2) |
C14—C15—C16—C17 | 0.1 (4) | C8—C3—N1—C34 | −176.5 (2) |
C15—C16—C17—C12 | 1.1 (3) | C4—C3—N1—C34 | 5.4 (4) |
C15—C16—C17—C18 | −175.4 (2) | C12—C11—N2—C19 | −60.40 (17) |
C13—C12—C17—C16 | −1.1 (3) | C10—C11—N2—C19 | 174.56 (13) |
C11—C12—C17—C16 | 177.49 (17) | C12—C11—N2—C1 | 168.44 (12) |
C13—C12—C17—C18 | 175.28 (19) | C10—C11—N2—C1 | 43.40 (15) |
C11—C12—C17—C18 | −6.1 (3) | C18—C19—N2—C11 | 66.5 (2) |
C16—C17—C18—C19 | −172.27 (19) | C18—C19—N2—C1 | −166.23 (16) |
C12—C17—C18—C19 | 11.4 (3) | C8—C1—N2—C11 | −158.00 (13) |
C17—C18—C19—N2 | −39.1 (3) | C2—C1—N2—C11 | 87.21 (16) |
C10—C9—C20—O2 | −17.6 (2) | C9—C1—N2—C11 | −30.05 (15) |
C1—C9—C20—O2 | 102.41 (18) | C8—C1—N2—C19 | 73.08 (18) |
C10—C9—C20—C21 | 164.84 (13) | C2—C1—N2—C19 | −41.7 (2) |
C1—C9—C20—C21 | −75.12 (17) | C9—C1—N2—C19 | −158.97 (14) |
O2—C20—C21—C22 | 164.45 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C33—H33B···O2i | 0.96 | 2.61 | 3.490 (5) | 153 |
C4—H4···O3Dii | 0.93 | 2.65 | 3.559 (6) | 166 |
Symmetry codes: (i) x+1, y, z; (ii) x−1, −y+1/2, z−1/2. |
Acknowledgements
YP and JBD are grateful to the Director, CSIR-NEIST, Jorhat, Assam, India, for his keen interest in this work.
Funding information
JBD and YP thank the Science and Engineering Research Board (SERB), New Delhi (Ref. No. EEQ/2017/000161) for financial support.
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