5′-Benzyl­idene-1′′-methyl-4′′-phenyl­tri­spiro­[1,3-dioxolane-2,1′-cyclo­hexane-3′,3′′-pyrrolidine-2′′,3′′′-indole]-4′,2′′′-dione

Chandralekha, K.; Gavaskar, D.; Sureshbabu, A.R.; Lakshmi, S.

doi:10.1107/S2414314617006393

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 5| May 2017| x170639

https://doi.org/10.1107/S2414314617006393

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5′-Benzylidene-1′′-methyl-4′′-phenyltrispiro[1,3-dioxolane-2,1′-cyclohexane-3′,3′′-pyrrolidine-2′′,3′′′-indole]-4′,2′′′-dione

Kuppan Chandralekha,^a Deivasigamani Gavaskar,^b Adukamparai Rajukrishnan Sureshbabu ^c and Srinivasakannan Lakshmi ^a ^*

^aDepartment of Physics, S. D. N. B. Vaishnav College for Women, Chromepet, Chennai 600 004, India, ^bSchool of Basic Sciences, Vels University, Pallavaram, Chennai, India, and ^cDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: lakssdnbvc@gmail.com

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 14 April 2017; accepted 28 April 2017; online 9 May 2017)

In the title compound, C₃₂H₃₀N₂O₄, two spiro links connect the methyl-substituted pyrrolidine ring to the oxindole and cyclohexanone rings. The cyclohexanone ring is further connected to the dioxalane ring by a third spiro junction. Both the pyrrolidine and dioxalane rings adopt a twist conformation. The indole ring is nearly planar, with a maximum deviation of 0.0296 (7) Å, and the cyclohexanone ring adopts a distorted boat conformation. In the crystal, C—H⋯O and N—H⋯N hydrogen-bonding interactions connect molecules into chains running parallel to the b axis, which are further linked into layers parallel to the ab plane by C—H⋯O hydrogen bonds.

Keywords: crystal structure; trispiropyrrolidine; spirooxindole; dioxalane.

CCDC reference: 1546766

Structure description

Spiro compounds are present in many natural products (James et al., 1991 ) and possess anticancer (Chin et al., 2008 ), antibacterial (Sar et al., 2006 ), antioxidant (Sarma et al., 2010 ) and anticonvulsant activities (Obniska & Kamiński, 2006 ). Some spiro compounds act as pain-relief agents (Frank et al., 2008 ) and pesticides (Wei et al., 2009 ). Spiro pyrrolidine derivatives exhibit antimicrobial and neurotoxic properties (Obniska et al., 2006 ). Oxindole derivatives are found to have antimicrobial (Karki et al., 2011 ) and antioxidant (Rindhe et al., 2011 ) properties. Spirooxindole derivatives act as inhibitors of human NK-1 receptor. Alkaloids containing a spiroindolepyrrolidine nucleus are found to be useful in cancer chemotherapy (Fischer et al., 2000 ). Spiropyrrolidine compounds containing oxindole and cyclohexanone ring systems are found to have antimicrobial and antifungal activities (Raj et al., 2003 ). Dioxalane moieties play a significant role in stabilizing mutant HIV-1 RT and nucleoside triphosphate and act as nucleoside reverse transcriptase inhibitors (NRTIs) (Liang et al., 2006 ).

In the title compound (Fig. 1) the methyl-substituted pyrrolidine ring (N1/C10/C16/C17/C8) and the dioxalane ring (O3/O2/C12/C14/C15) both adopt a twist conformation with puckering parameters q₂ = 0.480 (8) Å, φ₂ = 313.34 (6)° and q₂ = 0.221 (9) Å, φ₂ = 350.46 (3)°, respectively. The six-membered cyclohexanone ring (C8–C13) adopts a distorted boat conformation [Q_T = 0.666 (2) Å, θ = 99.42 (16)°, φ = 71.38 (7)°]. The pyrrolidine ring mean plane forms dihedral angles of 58.10 (1) and 87.45 (9)°, respectively, with the mean planes of the benzene ring and the mean plane of the cyclohexanone rings The cyclohexanone ring makes a dihedral angle of 84.14 (1)° with the mean plane of the dioxalane ring. The indole ring (C21–C26/N2/C19/C20) is nearly planar with a maximum deviation of 0.0296 (7) Å for atom C23. An intramolecular C—H⋯O hydrogen bond occurs. The geometrical parameters of the title compound are in good agreement with those previously reported for trispiropyrrolidine compounds (Chandralekha et al., 2015 , 2016 ).

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 30% probability level.

In the crystal, molecules are linked by weak C—H⋯O and N—H⋯O interactions (Table 1), forming chains extending along the b-axis direction (Fig. 2). The chains are further linked into layers parallel to the ab plane by C—H⋯O hydrogen bonds.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H34⋯N1ⁱ	0.90 (2)	2.36 (2)	3.251 (2)	174.3 (18)
C4—H4⋯O1ⁱⁱ	0.93	2.49	3.340 (2)	152
C11—H11B⋯O4	0.97	2.27	3.045 (2)	137
C22—H22⋯O4ⁱ	0.93	2.43	3.302 (2)	157
C32—H32⋯O4ⁱⁱⁱ	0.93	2.59	3.504 (3)	167
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
Partial crystal packing of the title compound showing the C—H⋯O and N—H⋯N hydrogen bonds (dashed lines), forming chains parallel to the b axis. H atoms not involved in hydrogen bonding are omitted for clarity.

Synthesis and crystallization

An equimolar mixture of 7,9-bis[(E)-benzylidine)]-1,4-dioxospiro[4,5]decane-8-one (1 mmol), isatin (1 mmol) and sarcosine (1 mmol) in methanol (25–30 ml) was refluxed for 3 h. After the completion of the reaction as indicated by TLC, the crude product was purified by column chromatography using a mixture of petroleum ether and ethylacetate (8:2 v/v). Crystals of the title compound were obtained by the slow evaporation of a methanol solution at room temperature.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₃₂H₃₀N₂O₄
M_r	506.58
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	13.9601 (2), 11.1172 (2), 16.7313 (3)
β (°)	96.019 (1)
V (Å³)	2582.34 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.15 × 0.11

Data collection
Diffractometer	Bruker SMART APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008 )
T_min, T_max	0.744, 0.859
No. of measured, independent and observed [I > 2σ(I)] reflections	24317, 6395, 3887
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.130, 1.04
No. of reflections	6395
No. of parameters	349
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2008), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1546766

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006393/rz4014sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617006393/rz4014Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617006393/rz4014Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

5'-Benzylidene-1''-methyl-4''-phenyltrispiro[1,3-dioxolane-2,1'-cyclohexane- 3',3''-pyrrolidine-2'',3'''-indole]-4',2'''-dione top

Crystal data top

C₃₂H₃₀N₂O₄	F(000) = 1072
M_r = 506.58	D_x = 1.303 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 13.9601 (2) Å	Cell parameters from 6394 reflections
b = 11.1172 (2) Å	θ = 1.8–28.4°
c = 16.7313 (3) Å	µ = 0.09 mm⁻¹
β = 96.019 (1)°	T = 296 K
V = 2582.34 (8) Å³	Block, colorless
Z = 4	0.23 × 0.15 × 0.11 mm

Data collection top

Bruker SMART APEXII area-detector diffractometer	3887 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
ω and φ scans	θ_max = 28.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −18→14
T_min = 0.744, T_max = 0.859	k = −14→14
24317 measured reflections	l = −22→22
6395 independent reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.045	w = 1/[σ²(F_o²) + (0.0534P)² + 0.3939P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.130	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.18 e Å⁻³
6395 reflections	Δρ_min = −0.19 e Å⁻³
349 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0017 (6)

Special details top

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.

Refinement. The N-bound indole H atom was located in a difference Fourier map and refined freely. All other H atoms were placed geometrically and refined using a riding atom approximation, with C–H = 0.93–0.97 \%A, and with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C) for methyl H atoms. A rotating model was used for the methyl group.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
H34	0.2804 (14)	−0.0171 (18)	0.2545 (12)	0.075 (6)*
O1	0.55773 (8)	0.20767 (10)	0.13693 (6)	0.0542 (3)
O2	0.60579 (9)	0.38736 (11)	0.31054 (7)	0.0640 (3)
O3	0.50902 (10)	0.40585 (12)	0.41115 (7)	0.0714 (4)
O4	0.27663 (10)	0.19821 (11)	0.30938 (8)	0.0711 (4)
N1	0.26684 (9)	0.33561 (12)	0.15637 (9)	0.0563 (4)
N2	0.30089 (10)	0.04319 (13)	0.22479 (9)	0.0539 (3)
C1	0.56550 (15)	−0.05286 (18)	0.39691 (13)	0.0785 (6)
H1	0.5130	−0.0036	0.4033	0.094*
C2	0.5949 (2)	−0.1353 (2)	0.45585 (15)	0.1011 (8)
H2	0.5617	−0.1414	0.5010	0.121*
C3	0.67203 (17)	−0.2077 (2)	0.44884 (15)	0.0856 (6)
H3	0.6933	−0.2607	0.4899	0.103*
C4	0.71750 (14)	−0.20157 (17)	0.38123 (15)	0.0763 (6)
H4	0.7690	−0.2526	0.3751	0.092*
C5	0.68774 (13)	−0.12001 (16)	0.32126 (12)	0.0647 (5)
H5	0.7191	−0.1176	0.2749	0.078*
C6	0.61193 (11)	−0.04194 (14)	0.32915 (10)	0.0529 (4)
C7	0.58309 (11)	0.04513 (14)	0.26516 (10)	0.0510 (4)
H7	0.5944	0.0223	0.2135	0.061*
C8	0.54258 (11)	0.15314 (13)	0.27172 (9)	0.0462 (4)
C9	0.51663 (10)	0.22333 (13)	0.19660 (9)	0.0431 (3)
C10	0.43116 (11)	0.31046 (13)	0.19660 (9)	0.0439 (3)
C11	0.43230 (12)	0.37857 (14)	0.27751 (9)	0.0499 (4)
H11A	0.4331	0.4644	0.2671	0.060*
H11B	0.3735	0.3603	0.3012	0.060*
C12	0.51770 (12)	0.34690 (15)	0.33712 (9)	0.0537 (4)
C13	0.52437 (13)	0.21313 (14)	0.34906 (10)	0.0560 (4)
H13A	0.5763	0.1945	0.3903	0.067*
H13B	0.4648	0.1832	0.3666	0.067*
C14	0.62840 (17)	0.4986 (2)	0.34848 (13)	0.0810 (6)
H14A	0.6055	0.5650	0.3140	0.097*
H14B	0.6974	0.5068	0.3619	0.097*
C15	0.5784 (2)	0.4959 (3)	0.42173 (17)	0.1216 (11)
H15A	0.6237	0.4787	0.4683	0.146*
H15B	0.5483	0.5730	0.4298	0.146*
C16	0.42296 (11)	0.39768 (13)	0.12265 (9)	0.0477 (4)
H16	0.4426	0.3513	0.0773	0.057*
C17	0.31406 (12)	0.41924 (16)	0.10477 (11)	0.0585 (4)
H17A	0.2982	0.5018	0.1169	0.070*
H17B	0.2933	0.4036	0.0486	0.070*
C18	0.17083 (14)	0.2983 (2)	0.12196 (15)	0.0858 (6)
H18A	0.1756	0.2573	0.0720	0.129*
H18B	0.1305	0.3678	0.1126	0.129*
H18C	0.1434	0.2451	0.1587	0.129*
C19	0.33456 (11)	0.23636 (14)	0.17605 (9)	0.0478 (4)
C20	0.30084 (11)	0.16007 (15)	0.24632 (10)	0.0527 (4)
C21	0.32460 (11)	0.02762 (14)	0.14589 (9)	0.0478 (4)
C22	0.33136 (13)	−0.07893 (15)	0.10525 (11)	0.0602 (4)
H22	0.3184	−0.1521	0.1288	0.072*
C23	0.35801 (13)	−0.07359 (16)	0.02831 (11)	0.0633 (5)
H23	0.3651	−0.1444	0.0000	0.076*
C24	0.37418 (13)	0.03456 (17)	−0.00690 (10)	0.0619 (5)
H24	0.3911	0.0363	−0.0592	0.074*
C25	0.36575 (13)	0.14113 (16)	0.03418 (10)	0.0578 (4)
H25	0.3757	0.2142	0.0093	0.069*
C26	0.34236 (11)	0.13880 (14)	0.11277 (9)	0.0472 (4)
C27	0.48698 (12)	0.50767 (14)	0.13050 (9)	0.0513 (4)
C28	0.57991 (13)	0.49828 (17)	0.10901 (11)	0.0620 (5)
H28	0.5999	0.4264	0.0877	0.074*
C29	0.64358 (15)	0.5941 (2)	0.11874 (12)	0.0752 (6)
H29	0.7059	0.5856	0.1047	0.090*
C30	0.61510 (18)	0.70108 (19)	0.14885 (13)	0.0801 (6)
H30	0.6579	0.7652	0.1557	0.096*
C31	0.52327 (18)	0.71291 (18)	0.16884 (13)	0.0813 (6)
H31	0.5035	0.7858	0.1888	0.098*
C32	0.45946 (15)	0.61805 (16)	0.15977 (12)	0.0674 (5)
H32	0.3971	0.6280	0.1734	0.081*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0603 (7)	0.0571 (7)	0.0482 (6)	0.0074 (5)	0.0201 (5)	−0.0006 (5)
O2	0.0668 (8)	0.0686 (8)	0.0587 (7)	−0.0144 (6)	0.0169 (6)	−0.0134 (6)
O3	0.0961 (10)	0.0747 (8)	0.0465 (7)	−0.0110 (7)	0.0218 (6)	−0.0175 (6)
O4	0.0849 (9)	0.0665 (8)	0.0694 (8)	−0.0102 (6)	0.0441 (7)	−0.0104 (6)
N1	0.0473 (8)	0.0520 (8)	0.0710 (9)	0.0041 (6)	0.0122 (7)	0.0024 (7)
N2	0.0617 (8)	0.0473 (8)	0.0562 (8)	−0.0055 (6)	0.0232 (7)	0.0015 (6)
C1	0.0779 (13)	0.0704 (12)	0.0926 (15)	0.0236 (10)	0.0340 (11)	0.0289 (11)
C2	0.125 (2)	0.0888 (16)	0.0965 (17)	0.0344 (15)	0.0462 (15)	0.0448 (13)
C3	0.0870 (15)	0.0738 (14)	0.0952 (16)	0.0150 (11)	0.0054 (13)	0.0334 (12)
C4	0.0584 (11)	0.0577 (11)	0.1112 (17)	0.0115 (9)	0.0019 (11)	0.0116 (11)
C5	0.0608 (11)	0.0547 (10)	0.0798 (13)	0.0059 (8)	0.0131 (9)	0.0003 (9)
C6	0.0486 (9)	0.0457 (9)	0.0642 (10)	0.0006 (7)	0.0048 (8)	0.0056 (7)
C7	0.0488 (9)	0.0500 (9)	0.0546 (9)	0.0010 (7)	0.0076 (7)	0.0013 (7)
C8	0.0473 (8)	0.0463 (9)	0.0459 (8)	−0.0016 (7)	0.0097 (7)	0.0028 (7)
C9	0.0476 (8)	0.0397 (8)	0.0435 (8)	−0.0018 (6)	0.0113 (7)	−0.0023 (6)
C10	0.0500 (8)	0.0405 (8)	0.0432 (8)	0.0011 (6)	0.0139 (7)	0.0009 (6)
C11	0.0624 (10)	0.0414 (8)	0.0488 (9)	0.0006 (7)	0.0191 (7)	−0.0027 (7)
C12	0.0666 (10)	0.0566 (10)	0.0404 (8)	−0.0044 (8)	0.0173 (7)	−0.0059 (7)
C13	0.0693 (11)	0.0558 (10)	0.0441 (9)	0.0043 (8)	0.0119 (8)	0.0047 (7)
C14	0.0905 (15)	0.0779 (13)	0.0751 (13)	−0.0227 (11)	0.0114 (11)	−0.0172 (11)
C15	0.156 (3)	0.120 (2)	0.0979 (19)	−0.0632 (19)	0.0531 (18)	−0.0549 (16)
C16	0.0562 (9)	0.0433 (8)	0.0450 (8)	0.0043 (7)	0.0120 (7)	0.0023 (6)
C17	0.0593 (10)	0.0574 (10)	0.0589 (10)	0.0069 (8)	0.0072 (8)	0.0074 (8)
C18	0.0533 (11)	0.0822 (14)	0.1205 (19)	0.0042 (10)	0.0019 (11)	0.0063 (13)
C19	0.0497 (9)	0.0455 (8)	0.0504 (9)	0.0013 (7)	0.0155 (7)	−0.0006 (7)
C20	0.0496 (9)	0.0541 (10)	0.0577 (10)	−0.0018 (7)	0.0213 (8)	−0.0009 (8)
C21	0.0452 (8)	0.0493 (9)	0.0503 (9)	−0.0027 (7)	0.0117 (7)	−0.0012 (7)
C22	0.0674 (11)	0.0469 (9)	0.0683 (11)	−0.0082 (8)	0.0175 (9)	−0.0052 (8)
C23	0.0685 (11)	0.0583 (11)	0.0646 (11)	−0.0092 (9)	0.0143 (9)	−0.0183 (9)
C24	0.0699 (11)	0.0695 (12)	0.0473 (9)	−0.0115 (9)	0.0113 (8)	−0.0110 (8)
C25	0.0724 (11)	0.0552 (10)	0.0464 (9)	−0.0079 (8)	0.0082 (8)	−0.0003 (8)
C26	0.0468 (8)	0.0480 (9)	0.0476 (9)	−0.0030 (7)	0.0086 (7)	−0.0020 (7)
C27	0.0604 (10)	0.0468 (9)	0.0477 (9)	0.0020 (7)	0.0112 (7)	0.0121 (7)
C28	0.0660 (11)	0.0575 (10)	0.0648 (11)	0.0005 (9)	0.0172 (9)	0.0160 (8)
C29	0.0698 (12)	0.0789 (14)	0.0778 (13)	−0.0103 (10)	0.0122 (10)	0.0303 (11)
C30	0.0956 (17)	0.0639 (13)	0.0779 (14)	−0.0256 (12)	−0.0035 (12)	0.0208 (11)
C31	0.1030 (17)	0.0495 (11)	0.0910 (15)	−0.0065 (11)	0.0088 (13)	0.0022 (10)
C32	0.0745 (12)	0.0492 (10)	0.0798 (13)	0.0032 (9)	0.0150 (10)	0.0040 (9)

Geometric parameters (Å, º) top

O1—C9	1.2149 (16)	C13—H13B	0.9700
O2—C14	1.411 (2)	C14—C15	1.473 (3)
O2—C12	1.424 (2)	C14—H14A	0.9700
O3—C15	1.391 (3)	C14—H14B	0.9700
O3—C12	1.4176 (18)	C15—H15A	0.9700
O4—C20	1.2174 (19)	C15—H15B	0.9700
N1—C18	1.462 (2)	C16—C27	1.512 (2)
N1—C19	1.468 (2)	C16—C17	1.537 (2)
N1—C17	1.471 (2)	C16—H16	0.9800
N2—C20	1.348 (2)	C17—H17A	0.9700
N2—C21	1.405 (2)	C17—H17B	0.9700
N2—H34	0.90 (2)	C18—H18A	0.9600
C1—C6	1.369 (2)	C18—H18B	0.9600
C1—C2	1.377 (3)	C18—H18C	0.9600
C1—H1	0.9300	C19—C26	1.528 (2)
C2—C3	1.359 (3)	C19—C20	1.562 (2)
C2—H2	0.9300	C21—C22	1.374 (2)
C3—C4	1.356 (3)	C21—C26	1.388 (2)
C3—H3	0.9300	C22—C23	1.378 (2)
C4—C5	1.384 (3)	C22—H22	0.9300
C4—H4	0.9300	C23—C24	1.368 (2)
C5—C6	1.386 (2)	C23—H23	0.9300
C5—H5	0.9300	C24—C25	1.381 (2)
C6—C7	1.468 (2)	C24—H24	0.9300
C7—C8	1.337 (2)	C25—C26	1.388 (2)
C7—H7	0.9300	C25—H25	0.9300
C8—C9	1.491 (2)	C27—C28	1.386 (2)
C8—C13	1.501 (2)	C27—C32	1.390 (2)
C9—C10	1.537 (2)	C28—C29	1.386 (3)
C10—C11	1.550 (2)	C28—H28	0.9300
C10—C16	1.567 (2)	C29—C30	1.367 (3)
C10—C19	1.587 (2)	C29—H29	0.9300
C11—C12	1.514 (2)	C30—C31	1.365 (3)
C11—H11A	0.9700	C30—H30	0.9300
C11—H11B	0.9700	C31—C32	1.379 (3)
C12—C13	1.502 (2)	C31—H31	0.9300
C13—H13A	0.9700	C32—H32	0.9300

C14—O2—C12	107.23 (13)	C14—C15—H15A	110.3
C15—O3—C12	108.77 (14)	O3—C15—H15B	110.3
C18—N1—C19	114.64 (14)	C14—C15—H15B	110.3
C18—N1—C17	113.39 (15)	H15A—C15—H15B	108.6
C19—N1—C17	106.80 (12)	C27—C16—C17	117.02 (13)
C20—N2—C21	112.12 (14)	C27—C16—C10	116.00 (13)
C20—N2—H34	124.1 (12)	C17—C16—C10	103.83 (12)
C21—N2—H34	123.3 (12)	C27—C16—H16	106.4
C6—C1—C2	121.37 (19)	C17—C16—H16	106.4
C6—C1—H1	119.3	C10—C16—H16	106.4
C2—C1—H1	119.3	N1—C17—C16	106.39 (13)
C3—C2—C1	120.8 (2)	N1—C17—H17A	110.5
C3—C2—H2	119.6	C16—C17—H17A	110.5
C1—C2—H2	119.6	N1—C17—H17B	110.5
C4—C3—C2	119.13 (19)	C16—C17—H17B	110.5
C4—C3—H3	120.4	H17A—C17—H17B	108.6
C2—C3—H3	120.4	N1—C18—H18A	109.5
C3—C4—C5	120.44 (18)	N1—C18—H18B	109.5
C3—C4—H4	119.8	H18A—C18—H18B	109.5
C5—C4—H4	119.8	N1—C18—H18C	109.5
C4—C5—C6	121.04 (18)	H18A—C18—H18C	109.5
C4—C5—H5	119.5	H18B—C18—H18C	109.5
C6—C5—H5	119.5	N1—C19—C26	117.99 (13)
C1—C6—C5	117.13 (16)	N1—C19—C20	109.83 (12)
C1—C6—C7	123.03 (15)	C26—C19—C20	100.67 (12)
C5—C6—C7	119.82 (16)	N1—C19—C10	99.85 (11)
C8—C7—C6	128.21 (16)	C26—C19—C10	113.46 (12)
C8—C7—H7	115.9	C20—C19—C10	115.80 (13)
C6—C7—H7	115.9	O4—C20—N2	125.11 (15)
C7—C8—C9	117.92 (14)	O4—C20—C19	126.60 (15)
C7—C8—C13	125.54 (14)	N2—C20—C19	108.28 (13)
C9—C8—C13	116.48 (13)	C22—C21—C26	123.09 (15)
O1—C9—C8	121.57 (13)	C22—C21—N2	127.33 (15)
O1—C9—C10	121.59 (13)	C26—C21—N2	109.57 (13)
C8—C9—C10	116.73 (12)	C21—C22—C23	117.67 (16)
C9—C10—C11	111.79 (12)	C21—C22—H22	121.2
C9—C10—C16	112.48 (12)	C23—C22—H22	121.2
C11—C10—C16	112.37 (12)	C24—C23—C22	120.86 (16)
C9—C10—C19	108.36 (11)	C24—C23—H23	119.6
C11—C10—C19	111.94 (12)	C22—C23—H23	119.6
C16—C10—C19	99.22 (12)	C23—C24—C25	120.88 (16)
C12—C11—C10	113.41 (12)	C23—C24—H24	119.6
C12—C11—H11A	108.9	C25—C24—H24	119.6
C10—C11—H11A	108.9	C24—C25—C26	119.76 (16)
C12—C11—H11B	108.9	C24—C25—H25	120.1
C10—C11—H11B	108.9	C26—C25—H25	120.1
H11A—C11—H11B	107.7	C21—C26—C25	117.68 (14)
O3—C12—O2	106.42 (13)	C21—C26—C19	109.09 (13)
O3—C12—C13	110.57 (13)	C25—C26—C19	133.19 (14)
O2—C12—C13	108.10 (14)	C28—C27—C32	117.30 (16)
O3—C12—C11	109.55 (13)	C28—C27—C16	118.51 (15)
O2—C12—C11	111.54 (13)	C32—C27—C16	124.17 (15)
C13—C12—C11	110.58 (14)	C27—C28—C29	121.18 (18)
C8—C13—C12	109.82 (13)	C27—C28—H28	119.4
C8—C13—H13A	109.7	C29—C28—H28	119.4
C12—C13—H13A	109.7	C30—C29—C28	120.28 (19)
C8—C13—H13B	109.7	C30—C29—H29	119.9
C12—C13—H13B	109.7	C28—C29—H29	119.9
H13A—C13—H13B	108.2	C31—C30—C29	119.42 (19)
O2—C14—C15	104.66 (17)	C31—C30—H30	120.3
O2—C14—H14A	110.8	C29—C30—H30	120.3
C15—C14—H14A	110.8	C30—C31—C32	120.8 (2)
O2—C14—H14B	110.8	C30—C31—H31	119.6
C15—C14—H14B	110.8	C32—C31—H31	119.6
H14A—C14—H14B	108.9	C31—C32—C27	120.97 (19)
O3—C15—C14	107.05 (17)	C31—C32—H32	119.5
O3—C15—H15A	110.3	C27—C32—H32	119.5

C6—C1—C2—C3	0.7 (4)	C17—N1—C19—C26	−78.91 (16)
C1—C2—C3—C4	−2.8 (4)	C18—N1—C19—C20	−66.90 (19)
C2—C3—C4—C5	2.0 (4)	C17—N1—C19—C20	166.60 (13)
C3—C4—C5—C6	0.8 (3)	C18—N1—C19—C10	170.95 (15)
C2—C1—C6—C5	2.1 (3)	C17—N1—C19—C10	44.45 (15)
C2—C1—C6—C7	−179.7 (2)	C9—C10—C19—N1	−164.64 (11)
C4—C5—C6—C1	−2.8 (3)	C11—C10—C19—N1	71.64 (14)
C4—C5—C6—C7	178.88 (16)	C16—C10—C19—N1	−47.12 (13)
C1—C6—C7—C8	30.7 (3)	C9—C10—C19—C26	−38.16 (16)
C5—C6—C7—C8	−151.10 (17)	C11—C10—C19—C26	−161.88 (12)
C6—C7—C8—C9	−177.82 (15)	C16—C10—C19—C26	79.36 (14)
C6—C7—C8—C13	4.9 (3)	C9—C10—C19—C20	77.57 (15)
C7—C8—C9—O1	−25.1 (2)	C11—C10—C19—C20	−46.16 (17)
C13—C8—C9—O1	152.40 (15)	C16—C10—C19—C20	−164.92 (12)
C7—C8—C9—C10	151.08 (14)	C21—N2—C20—O4	174.93 (16)
C13—C8—C9—C10	−31.41 (19)	C21—N2—C20—C19	−3.78 (18)
O1—C9—C10—C11	−142.89 (14)	N1—C19—C20—O4	−48.5 (2)
C8—C9—C10—C11	40.92 (17)	C26—C19—C20—O4	−173.63 (17)
O1—C9—C10—C16	−15.4 (2)	C10—C19—C20—O4	63.6 (2)
C8—C9—C10—C16	168.44 (12)	N1—C19—C20—N2	130.20 (14)
O1—C9—C10—C19	93.29 (16)	C26—C19—C20—N2	5.05 (16)
C8—C9—C10—C19	−82.90 (15)	C10—C19—C20—N2	−117.70 (15)
C9—C10—C11—C12	1.45 (17)	C20—N2—C21—C22	179.89 (16)
C16—C10—C11—C12	−126.14 (14)	C20—N2—C21—C26	0.63 (19)
C19—C10—C11—C12	123.22 (14)	C26—C21—C22—C23	0.6 (3)
C15—O3—C12—O2	11.2 (2)	N2—C21—C22—C23	−178.53 (16)
C15—O3—C12—C13	128.3 (2)	C21—C22—C23—C24	−2.0 (3)
C15—O3—C12—C11	−109.5 (2)	C22—C23—C24—C25	1.1 (3)
C14—O2—C12—O3	−22.49 (19)	C23—C24—C25—C26	1.2 (3)
C14—O2—C12—C13	−141.28 (16)	C22—C21—C26—C25	1.6 (2)
C14—O2—C12—C11	96.94 (16)	N2—C21—C26—C25	−179.14 (14)
C10—C11—C12—O3	−175.50 (12)	C22—C21—C26—C19	−176.40 (15)
C10—C11—C12—O2	66.95 (17)	N2—C21—C26—C19	2.89 (17)
C10—C11—C12—C13	−53.39 (17)	C24—C25—C26—C21	−2.5 (2)
C7—C8—C13—C12	156.55 (16)	C24—C25—C26—C19	174.90 (16)
C9—C8—C13—C12	−20.8 (2)	N1—C19—C26—C21	−124.11 (14)
O3—C12—C13—C8	−174.84 (13)	C20—C19—C26—C21	−4.70 (16)
O2—C12—C13—C8	−58.72 (17)	C10—C19—C26—C21	119.67 (14)
C11—C12—C13—C8	63.64 (17)	N1—C19—C26—C25	58.4 (2)
C12—O2—C14—C15	24.4 (2)	C20—C19—C26—C25	177.77 (17)
C12—O3—C15—C14	3.9 (3)	C10—C19—C26—C25	−57.9 (2)
O2—C14—C15—O3	−17.5 (3)	C17—C16—C27—C28	−150.01 (15)
C9—C10—C16—C27	−82.41 (16)	C10—C16—C27—C28	86.82 (18)
C11—C10—C16—C27	44.81 (17)	C17—C16—C27—C32	31.5 (2)
C19—C10—C16—C27	163.24 (12)	C10—C16—C27—C32	−91.68 (19)
C9—C10—C16—C17	147.76 (13)	C32—C27—C28—C29	2.0 (3)
C11—C10—C16—C17	−85.03 (15)	C16—C27—C28—C29	−176.65 (16)
C19—C10—C16—C17	33.40 (14)	C27—C28—C29—C30	−1.0 (3)
C18—N1—C17—C16	−150.61 (15)	C28—C29—C30—C31	−0.4 (3)
C19—N1—C17—C16	−23.37 (17)	C29—C30—C31—C32	0.7 (3)
C27—C16—C17—N1	−137.40 (14)	C30—C31—C32—C27	0.4 (3)
C10—C16—C17—N1	−8.18 (17)	C28—C27—C32—C31	−1.7 (3)
C18—N1—C19—C26	47.6 (2)	C16—C27—C32—C31	176.86 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H34···N1ⁱ	0.90 (2)	2.36 (2)	3.251 (2)	174.3 (18)
C4—H4···O1ⁱⁱ	0.93	2.49	3.340 (2)	152
C11—H11B···O4	0.97	2.27	3.045 (2)	137
C22—H22···O4ⁱ	0.93	2.43	3.302 (2)	157
C32—H32···O4ⁱⁱⁱ	0.93	2.59	3.504 (3)	167

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1/2, y+1/2, −z+1/2.

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection.

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