1-Benzyl-3′-[(1H-indol-3-yl)carbon­yl]-1′-methyl-2-oxo-4′-(pyridin-3-yl)spiro­[indoline-3,2′-pyrrolidine]-3′-carbo­nitrile

Seethalakshmi, P.; Palanivel, C.

doi:10.1107/S2414314616016862

organic compounds

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ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161686

https://doi.org/10.1107/S2414314616016862

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1-Benzyl-3′-[(1H-indol-3-yl)carbonyl]-1′-methyl-2-oxo-4′-(pyridin-3-yl)spiro[indoline-3,2′-pyrrolidine]-3′-carbonitrile

P. Seethalakshmi ^a and C. Palanivel ^b,^a ^*

^aDepartment of Chemistry, Jawahar Science College, Cuddalore, Neyveli 607 803, India, and ^bPG & Research Department of Chemistry, Government Arts College, Chidambaram, Tamilnadu, India
^*Correspondence e-mail: palanivelchem@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 12 September 2016; accepted 20 October 2016; online 1 November 2016)

In the title compound, C₃₄H₂₇N₅O₂, the central pyrrolidine ring adopts an envelope conformation, with the N atom as the flap. The mean planes of the two indoline ring systems are inclined to the mean plane of the central pyrrolidine ring by 86.26 (9) and 69.30 (9)°, respectively. The dihedral angle between the benzene and pyridine rings is 75.09 (11)°. In the crystal, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds, forming sheets parallel to the ab plane.

Keywords: crystal structure; spiro-pyrrolidine derivatives; N—H⋯N hydrogen bonds; C—H⋯N hydrogen bonds.

CCDC reference: 1510867

Structure description

Spiro-pyrrolidine derivatives are unique tetracyclic 5-HT(2A) receptor antagonists (Obniska et al., 2003 ; Peddi et al., 2004 ). These derivatives possess anticancer (Zapf et al., 2011 ) and anti-influenza virus (Stylianakis et al., 2003 ) activities. Highly functionalized pyrrolidines have attracted much interest in recent years as they constitute the main structural element of many natural and synthetic pharmacologically active compounds (Waldmann, 1995 ). Optically active pyrrolidines have been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis (Suzuki et al., 1994 ; Huryn et al., 1991 ). In view of their importance and in continuation of our work on the crystal structure analysis of spiro-pyrrolidine derivatives, we report herein on the synthesis and crystal structure of a new spiro-pyrrolidine derivative.

The molecular structure of the title compound is illustrated in Fig. 1. The five-membered ring (N2/C6–C9) in the pyrrolidine moiety adopts an envelope conformation, with atom N2 as the flap atom [puckering parameters: q₂ = 0.410 (2) Å and φ₂ = 181.7 (3)°], and the pyridine ring (N1/C1–C5) exhibits a slightly twisted conformation [puckering parameters: q₂ = 0.093 (2) Å and Φ₂ = 49.9 (2)°]. The sum of angles at atom N2 [328.4 (15)°] is in accordance with sp²-hybiridization, and the sum of angles at atom N3 [313.6 (14)°] is in accordance with sp³-hybridization. The dihedral angle between the benzene (C20–C25) and pyridine (N1/C1–C5) rings is 75.09 (11)°.

Figure 1
The molecular structure of the title compound, showing the atom labelling and 20% probability displacement ellipsoids.

In the crystal, molecules are linked by N—H⋯N and C—H⋯N hydrogen bonds, forming sheets parallel to the ab plane (Table 1 and Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5⋯N1ⁱ	0.86	1.96	2.812 (2)	170
C19—H19A⋯N4ⁱⁱ	0.97	2.46	3.370 (3)	157
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x-{\script{1\over 2}}, y, -z+{\script{1\over 2}}]$ .

Figure 2
The crystal packing of the title compound, viewed along the c axis. Hydrogen bonds are shown as dashed lines (see Table 1

) and, for clarity, only H atoms H5 and H19A have been included.

Synthesis and crystallization

N-Benzylisatin, (1) (0.3 mmol), was mixed with sarcosine, (2) (0.3 mmol), and (E)-2-[(1H-indol-3-yl)carbonyl]-3-(pyridin-3-yl)acrylonitrile in ethanol (10 ml) in a round-bottomed flask. The reaction mixture was heated at 358 K for 3 h. After cooling to ambient temperature, the reaction mixture was filtered to afford the pure title product as a white solid (yield 92%). The filtrate was left to evaporate slowly and after 48 h yellow crystals of the title compound were obtained.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₃₄H₂₇N₅O₂
M_r	537.60
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	14.7421 (6), 17.5573 (6), 21.4675 (9)
V (Å³)	5556.5 (4)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.08
Crystal size (mm)	0.25 × 0.16 × 0.12

Data collection
Diffractometer	Bruker APEXII CCD
No. of measured, independent and observed [I > 2σ(I)] reflections	22838, 4884, 3251
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.095, 0.97
No. of reflections	4884
No. of parameters	372
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.17
Computer programs: APEX2 and SAINT (Bruker, 2014 ), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 1510867

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616016862/su4077sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016862/su4077Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616016862/su4077Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

1-Benzyl-3'-[(1H-indol-3-yl)carbonyl]-1'-methyl-2-oxo-4'-(pyridin-3-yl)spiro[indoline-3,2'-pyrrolidine]-3'-carbonitrile top

Crystal data top

C₃₄H₂₇N₅O₂	D_x = 1.285 Mg m⁻³
M_r = 537.60	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 5384 reflections
a = 14.7421 (6) Å	θ = 2.3–24.1°
b = 17.5573 (6) Å	µ = 0.08 mm⁻¹
c = 21.4675 (9) Å	T = 296 K
V = 5556.5 (4) Å³	Rectangular, yellow
Z = 8	0.25 × 0.16 × 0.12 mm
F(000) = 2256

Data collection top

Bruker APEXII CCD diffractometer	R_int = 0.031
φ and ω scans	θ_max = 25.0°, θ_min = 1.9°
22838 measured reflections	h = −14→17
4884 independent reflections	k = −20→20
3251 reflections with I > 2σ(I)	l = −18→25

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0237P)² + 2.8668P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.095	(Δ/σ)_max < 0.001
S = 0.97	Δρ_max = 0.13 e Å⁻³
4884 reflections	Δρ_min = −0.17 e Å⁻³
372 parameters	Extinction correction: SHELXL2014 (Sheldrick 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.00063 (9)

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.

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

	x	y	z	U_iso*/U_eq
C1	0.63234 (14)	−0.06447 (11)	0.42023 (9)	0.0517 (5)
H1	0.6404	−0.0377	0.4572	0.062*
C2	0.70167 (15)	−0.10825 (13)	0.39656 (11)	0.0627 (6)
H2	0.7568	−0.1116	0.4174	0.075*
C3	0.68837 (16)	−0.14676 (12)	0.34183 (11)	0.0644 (6)
H3	0.7358	−0.1758	0.3259	0.077*
C4	0.54388 (15)	−0.10303 (11)	0.33427 (10)	0.0524 (5)
H4	0.4889	−0.1024	0.3131	0.063*
C5	0.55064 (13)	−0.06054 (10)	0.38871 (9)	0.0438 (5)
C6	0.47250 (13)	−0.01328 (10)	0.41220 (9)	0.0445 (5)
H6	0.4907	0.0063	0.4531	0.053*
C7	0.38438 (14)	−0.05742 (11)	0.42225 (10)	0.0537 (5)
H7A	0.3763	−0.0960	0.3904	0.064*
H7B	0.3837	−0.0817	0.4628	0.064*
C8	0.33670 (12)	0.04828 (10)	0.36441 (9)	0.0419 (5)
C9	0.44388 (13)	0.05810 (10)	0.37192 (8)	0.0405 (4)
C10	0.31830 (13)	0.01138 (11)	0.29978 (10)	0.0458 (5)
C11	0.24722 (13)	0.12705 (11)	0.29981 (9)	0.0470 (5)
C12	0.19527 (15)	0.18821 (12)	0.28185 (11)	0.0637 (6)
H12	0.1732	0.1926	0.2414	0.076*
C13	0.17724 (17)	0.24293 (13)	0.32648 (13)	0.0788 (8)
H13	0.1433	0.2855	0.3155	0.095*
C14	0.20803 (18)	0.23604 (13)	0.38641 (12)	0.0757 (7)
H14	0.1939	0.2734	0.4155	0.091*
C15	0.26003 (15)	0.17389 (11)	0.40409 (10)	0.0593 (6)
H15	0.2804	0.1689	0.4449	0.071*
C16	0.28089 (13)	0.11976 (10)	0.35996 (9)	0.0455 (5)
C17	0.22168 (15)	−0.02969 (13)	0.41757 (12)	0.0748 (7)
H17A	0.1792	0.0112	0.4119	0.112*
H17B	0.2097	−0.0547	0.4565	0.112*
H17C	0.2155	−0.0656	0.3841	0.112*
C18	0.48887 (13)	0.05771 (10)	0.31095 (10)	0.0426 (5)
C19	0.24710 (15)	0.04824 (13)	0.19947 (10)	0.0622 (6)
H19A	0.1814	0.0489	0.1969	0.075*
H19B	0.2673	−0.0025	0.1883	0.075*
C20	0.28439 (15)	0.10381 (12)	0.15286 (9)	0.0522 (5)
C21	0.22805 (17)	0.13774 (15)	0.10973 (11)	0.0762 (7)
H21	0.1660	0.1283	0.1113	0.091*
C22	0.2618 (2)	0.18511 (17)	0.06460 (13)	0.0908 (9)
H22	0.2226	0.2070	0.0357	0.109*
C23	0.3517 (2)	0.20027 (16)	0.06171 (13)	0.0888 (9)
H23	0.3743	0.2321	0.0308	0.107*
C24	0.40917 (18)	0.16848 (16)	0.10455 (12)	0.0805 (8)
H24	0.4708	0.1797	0.1033	0.097*
C25	0.37569 (15)	0.11979 (13)	0.14957 (10)	0.0620 (6)
H25	0.4153	0.0975	0.1780	0.074*
C26	0.47020 (13)	0.13396 (10)	0.40690 (9)	0.0453 (5)
C27	0.47548 (13)	0.20507 (10)	0.37413 (9)	0.0455 (5)
C28	0.44590 (14)	0.22198 (11)	0.31459 (10)	0.0528 (5)
H28	0.4239	0.1863	0.2863	0.063*
C29	0.48880 (14)	0.33263 (11)	0.35534 (10)	0.0531 (5)
C30	0.50841 (16)	0.40925 (12)	0.36446 (13)	0.0700 (7)
H30	0.4986	0.4452	0.3334	0.084*
C31	0.54281 (18)	0.42924 (13)	0.42120 (14)	0.0776 (8)
H31	0.5563	0.4801	0.4291	0.093*
C32	0.55800 (16)	0.37571 (13)	0.46725 (12)	0.0710 (7)
H32	0.5813	0.3914	0.5054	0.085*
C33	0.53938 (14)	0.29933 (12)	0.45804 (10)	0.0565 (6)
H33	0.5506	0.2637	0.4892	0.068*
C34	0.50338 (13)	0.27721 (10)	0.40092 (9)	0.0465 (5)
N1	0.61087 (13)	−0.14454 (9)	0.31048 (8)	0.0588 (5)
N2	0.31418 (11)	0.00086 (9)	0.41796 (8)	0.0509 (4)
N3	0.27357 (10)	0.06328 (9)	0.26387 (7)	0.0477 (4)
N4	0.52502 (12)	0.05610 (10)	0.26381 (8)	0.0572 (5)
N5	0.45319 (12)	0.29669 (9)	0.30315 (8)	0.0587 (5)
H5	0.4382	0.3189	0.2690	0.070*
O1	0.34090 (10)	−0.05210 (7)	0.28292 (7)	0.0599 (4)
O2	0.48569 (11)	0.12999 (7)	0.46262 (7)	0.0646 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0643 (14)	0.0493 (12)	0.0416 (12)	−0.0037 (11)	−0.0093 (11)	0.0065 (10)
C2	0.0557 (14)	0.0682 (14)	0.0643 (16)	0.0042 (12)	−0.0136 (12)	0.0109 (13)
C3	0.0679 (16)	0.0581 (13)	0.0671 (16)	0.0158 (12)	−0.0047 (13)	0.0013 (13)
C4	0.0580 (13)	0.0468 (11)	0.0525 (14)	0.0043 (10)	−0.0129 (11)	−0.0027 (11)
C5	0.0566 (13)	0.0371 (10)	0.0377 (11)	−0.0020 (9)	−0.0059 (10)	0.0053 (9)
C6	0.0592 (13)	0.0388 (10)	0.0354 (11)	−0.0025 (9)	−0.0034 (10)	0.0058 (9)
C7	0.0684 (14)	0.0415 (11)	0.0512 (13)	−0.0009 (10)	0.0045 (11)	0.0087 (10)
C8	0.0483 (11)	0.0384 (10)	0.0388 (11)	−0.0013 (8)	0.0022 (9)	−0.0019 (9)
C9	0.0496 (11)	0.0392 (10)	0.0326 (11)	−0.0036 (9)	−0.0018 (9)	0.0026 (9)
C10	0.0423 (11)	0.0433 (11)	0.0516 (13)	−0.0045 (9)	−0.0008 (10)	−0.0034 (10)
C11	0.0439 (11)	0.0456 (11)	0.0515 (13)	0.0002 (9)	0.0001 (10)	−0.0020 (10)
C12	0.0667 (15)	0.0608 (13)	0.0638 (15)	0.0106 (12)	−0.0107 (12)	−0.0001 (12)
C13	0.0919 (19)	0.0590 (14)	0.086 (2)	0.0292 (14)	−0.0058 (16)	−0.0034 (15)
C14	0.100 (2)	0.0584 (14)	0.0689 (18)	0.0263 (14)	0.0033 (15)	−0.0124 (13)
C15	0.0755 (15)	0.0527 (12)	0.0495 (13)	0.0070 (11)	0.0058 (12)	−0.0051 (11)
C16	0.0474 (12)	0.0430 (10)	0.0460 (12)	−0.0008 (9)	0.0037 (10)	−0.0013 (10)
C17	0.0643 (16)	0.0686 (15)	0.0914 (19)	−0.0096 (12)	0.0192 (14)	0.0141 (14)
C18	0.0445 (11)	0.0431 (11)	0.0401 (12)	−0.0027 (9)	−0.0077 (10)	0.0038 (10)
C19	0.0595 (14)	0.0734 (15)	0.0535 (14)	−0.0075 (12)	−0.0152 (12)	−0.0114 (12)
C20	0.0577 (14)	0.0597 (12)	0.0393 (12)	0.0074 (11)	−0.0110 (11)	−0.0101 (11)
C21	0.0650 (16)	0.105 (2)	0.0589 (16)	0.0134 (15)	−0.0171 (14)	−0.0009 (16)
C22	0.099 (2)	0.113 (2)	0.0605 (18)	0.0353 (19)	−0.0144 (17)	0.0123 (17)
C23	0.112 (3)	0.095 (2)	0.0593 (18)	0.0244 (19)	0.0108 (17)	0.0166 (15)
C24	0.0728 (17)	0.103 (2)	0.0654 (17)	0.0064 (15)	0.0134 (15)	0.0091 (16)
C25	0.0571 (15)	0.0769 (15)	0.0520 (14)	0.0146 (12)	−0.0048 (12)	0.0003 (13)
C26	0.0529 (12)	0.0434 (11)	0.0397 (12)	−0.0050 (9)	−0.0050 (10)	0.0033 (10)
C27	0.0533 (13)	0.0407 (10)	0.0426 (12)	−0.0071 (9)	−0.0053 (10)	0.0067 (10)
C28	0.0608 (13)	0.0461 (11)	0.0516 (14)	−0.0110 (10)	−0.0063 (11)	0.0084 (10)
C29	0.0521 (13)	0.0463 (11)	0.0611 (14)	−0.0071 (10)	0.0001 (11)	0.0064 (11)
C30	0.0755 (17)	0.0464 (13)	0.0882 (19)	−0.0106 (11)	0.0065 (15)	0.0124 (13)
C31	0.0872 (19)	0.0482 (13)	0.097 (2)	−0.0185 (13)	0.0103 (17)	−0.0056 (15)
C32	0.0763 (17)	0.0647 (15)	0.0719 (17)	−0.0191 (13)	0.0038 (14)	−0.0151 (14)
C33	0.0570 (13)	0.0539 (12)	0.0585 (14)	−0.0078 (10)	−0.0008 (11)	−0.0026 (11)
C34	0.0448 (11)	0.0435 (11)	0.0512 (13)	−0.0059 (9)	−0.0001 (10)	0.0024 (10)
N1	0.0668 (12)	0.0492 (10)	0.0603 (12)	0.0118 (9)	−0.0086 (10)	−0.0058 (9)
N2	0.0547 (11)	0.0461 (9)	0.0518 (11)	−0.0049 (8)	0.0098 (9)	0.0080 (8)
N3	0.0474 (10)	0.0515 (9)	0.0440 (10)	−0.0014 (8)	−0.0062 (8)	−0.0062 (8)
N4	0.0557 (11)	0.0711 (12)	0.0447 (11)	0.0006 (9)	0.0005 (9)	0.0045 (10)
N5	0.0698 (12)	0.0487 (10)	0.0575 (12)	−0.0070 (9)	−0.0063 (10)	0.0211 (9)
O1	0.0665 (10)	0.0466 (8)	0.0666 (10)	0.0015 (7)	−0.0079 (8)	−0.0144 (7)
O2	0.1075 (13)	0.0464 (8)	0.0399 (9)	−0.0101 (8)	−0.0152 (9)	0.0022 (7)

Geometric parameters (Å, º) top

C1—C2	1.376 (3)	C17—H17A	0.9600
C1—C5	1.383 (3)	C17—H17B	0.9600
C1—H1	0.9300	C17—H17C	0.9600
C2—C3	1.370 (3)	C18—N4	1.144 (2)
C2—H2	0.9300	C19—N3	1.460 (2)
C3—N1	1.327 (3)	C19—C20	1.502 (3)
C3—H3	0.9300	C19—H19A	0.9700
C4—N1	1.329 (2)	C19—H19B	0.9700
C4—C5	1.390 (3)	C20—C25	1.377 (3)
C4—H4	0.9300	C20—C21	1.379 (3)
C5—C6	1.507 (3)	C21—C22	1.370 (4)
C6—C7	1.528 (3)	C21—H21	0.9300
C6—C9	1.580 (2)	C22—C23	1.353 (4)
C6—H6	0.9800	C22—H22	0.9300
C7—N2	1.458 (2)	C23—C24	1.369 (3)
C7—H7A	0.9700	C23—H23	0.9300
C7—H7B	0.9700	C24—C25	1.381 (3)
C8—N2	1.458 (2)	C24—H24	0.9300
C8—C16	1.504 (2)	C25—H25	0.9300
C8—C10	1.555 (3)	C26—O2	1.220 (2)
C8—C9	1.598 (3)	C26—C27	1.435 (2)
C9—C18	1.467 (3)	C27—C28	1.383 (3)
C9—C26	1.578 (2)	C27—C34	1.451 (2)
C10—O1	1.218 (2)	C28—N5	1.339 (2)
C10—N3	1.364 (2)	C28—H28	0.9300
C11—C12	1.374 (3)	C29—C30	1.390 (3)
C11—C16	1.389 (3)	C29—N5	1.389 (3)
C11—N3	1.414 (2)	C29—C34	1.397 (3)
C12—C13	1.383 (3)	C30—C31	1.365 (3)
C12—H12	0.9300	C30—H30	0.9300
C13—C14	1.370 (3)	C31—C32	1.382 (3)
C13—H13	0.9300	C31—H31	0.9300
C14—C15	1.387 (3)	C32—C33	1.383 (3)
C14—H14	0.9300	C32—H32	0.9300
C15—C16	1.377 (3)	C33—C34	1.391 (3)
C15—H15	0.9300	C33—H33	0.9300
C17—N2	1.465 (3)	N5—H5	0.8600

C2—C1—C5	119.6 (2)	H17A—C17—H17C	109.5
C2—C1—H1	120.2	H17B—C17—H17C	109.5
C5—C1—H1	120.2	N4—C18—C9	178.5 (2)
C3—C2—C1	119.1 (2)	N3—C19—C20	114.55 (17)
C3—C2—H2	120.5	N3—C19—H19A	108.6
C1—C2—H2	120.5	C20—C19—H19A	108.6
N1—C3—C2	123.0 (2)	N3—C19—H19B	108.6
N1—C3—H3	118.5	C20—C19—H19B	108.6
C2—C3—H3	118.5	H19A—C19—H19B	107.6
N1—C4—C5	124.34 (19)	C25—C20—C21	117.8 (2)
N1—C4—H4	117.8	C25—C20—C19	121.6 (2)
C5—C4—H4	117.8	C21—C20—C19	120.5 (2)
C1—C5—C4	116.54 (19)	C22—C21—C20	121.2 (3)
C1—C5—C6	121.97 (18)	C22—C21—H21	119.4
C4—C5—C6	121.49 (18)	C20—C21—H21	119.4
C5—C6—C7	114.71 (15)	C23—C22—C21	120.5 (3)
C5—C6—C9	117.24 (15)	C23—C22—H22	119.8
C7—C6—C9	104.63 (15)	C21—C22—H22	119.8
C5—C6—H6	106.5	C22—C23—C24	119.7 (3)
C7—C6—H6	106.5	C22—C23—H23	120.2
C9—C6—H6	106.5	C24—C23—H23	120.2
N2—C7—C6	103.80 (15)	C23—C24—C25	120.1 (3)
N2—C7—H7A	111.0	C23—C24—H24	120.0
C6—C7—H7A	111.0	C25—C24—H24	120.0
N2—C7—H7B	111.0	C20—C25—C24	120.8 (2)
C6—C7—H7B	111.0	C20—C25—H25	119.6
H7A—C7—H7B	109.0	C24—C25—H25	119.6
N2—C8—C16	113.72 (15)	O2—C26—C27	121.35 (17)
N2—C8—C10	115.22 (15)	O2—C26—C9	117.69 (16)
C16—C8—C10	101.27 (15)	C27—C26—C9	120.97 (17)
N2—C8—C9	101.96 (14)	C28—C27—C26	128.52 (18)
C16—C8—C9	117.23 (15)	C28—C27—C34	105.57 (16)
C10—C8—C9	107.90 (15)	C26—C27—C34	125.49 (18)
C18—C9—C26	108.50 (15)	N5—C28—C27	110.76 (18)
C18—C9—C6	111.34 (15)	N5—C28—H28	124.6
C26—C9—C6	110.09 (14)	C27—C28—H28	124.6
C18—C9—C8	110.89 (15)	C30—C29—N5	129.2 (2)
C26—C9—C8	112.48 (15)	C30—C29—C34	122.9 (2)
C6—C9—C8	103.51 (14)	N5—C29—C34	107.86 (17)
O1—C10—N3	125.13 (19)	C31—C30—C29	116.8 (2)
O1—C10—C8	126.77 (18)	C31—C30—H30	121.6
N3—C10—C8	108.09 (16)	C29—C30—H30	121.6
C12—C11—C16	122.13 (19)	C30—C31—C32	121.6 (2)
C12—C11—N3	128.23 (19)	C30—C31—H31	119.2
C16—C11—N3	109.63 (16)	C32—C31—H31	119.2
C11—C12—C13	117.1 (2)	C33—C32—C31	121.7 (2)
C11—C12—H12	121.4	C33—C32—H32	119.2
C13—C12—H12	121.4	C31—C32—H32	119.2
C14—C13—C12	121.7 (2)	C32—C33—C34	118.2 (2)
C14—C13—H13	119.1	C32—C33—H33	120.9
C12—C13—H13	119.1	C34—C33—H33	120.9
C13—C14—C15	120.7 (2)	C33—C34—C29	118.79 (18)
C13—C14—H14	119.7	C33—C34—C27	134.53 (18)
C15—C14—H14	119.7	C29—C34—C27	106.67 (18)
C16—C15—C14	118.6 (2)	C3—N1—C4	117.45 (19)
C16—C15—H15	120.7	C8—N2—C7	106.80 (15)
C14—C15—H15	120.7	C8—N2—C17	114.61 (17)
C15—C16—C11	119.75 (18)	C7—N2—C17	113.82 (16)
C15—C16—C8	130.88 (19)	C10—N3—C11	110.69 (16)
C11—C16—C8	109.36 (16)	C10—N3—C19	122.93 (17)
N2—C17—H17A	109.5	C11—N3—C19	125.88 (17)
N2—C17—H17B	109.5	C28—N5—C29	109.12 (17)
H17A—C17—H17B	109.5	C28—N5—H5	125.4
N2—C17—H17C	109.5	C29—N5—H5	125.4

C5—C1—C2—C3	0.4 (3)	C21—C22—C23—C24	−0.5 (4)
C1—C2—C3—N1	−0.7 (3)	C22—C23—C24—C25	1.5 (4)
C2—C1—C5—C4	0.8 (3)	C21—C20—C25—C24	0.2 (3)
C2—C1—C5—C6	−179.71 (17)	C19—C20—C25—C24	177.1 (2)
N1—C4—C5—C1	−1.9 (3)	C23—C24—C25—C20	−1.4 (4)
N1—C4—C5—C6	178.56 (18)	C18—C9—C26—O2	−139.91 (19)
C1—C5—C6—C7	−123.4 (2)	C6—C9—C26—O2	−17.8 (2)
C4—C5—C6—C7	56.0 (2)	C8—C9—C26—O2	97.0 (2)
C1—C5—C6—C9	113.2 (2)	C18—C9—C26—C27	40.2 (2)
C4—C5—C6—C9	−67.3 (2)	C6—C9—C26—C27	162.28 (17)
C5—C6—C7—N2	−156.36 (16)	C8—C9—C26—C27	−82.8 (2)
C9—C6—C7—N2	−26.51 (19)	O2—C26—C27—C28	−168.1 (2)
C5—C6—C9—C18	10.9 (2)	C9—C26—C27—C28	11.8 (3)
C7—C6—C9—C18	−117.49 (17)	O2—C26—C27—C34	3.4 (3)
C5—C6—C9—C26	−109.52 (18)	C9—C26—C27—C34	−176.69 (18)
C7—C6—C9—C26	122.14 (17)	C26—C27—C28—N5	172.8 (2)
C5—C6—C9—C8	130.04 (16)	C34—C27—C28—N5	−0.1 (2)
C7—C6—C9—C8	1.70 (18)	N5—C29—C30—C31	179.6 (2)
N2—C8—C9—C18	142.99 (15)	C34—C29—C30—C31	−0.4 (3)
C16—C8—C9—C18	−92.16 (19)	C29—C30—C31—C32	0.4 (4)
C10—C8—C9—C18	21.2 (2)	C30—C31—C32—C33	0.2 (4)
N2—C8—C9—C26	−95.31 (16)	C31—C32—C33—C34	−0.8 (4)
C16—C8—C9—C26	29.5 (2)	C32—C33—C34—C29	0.8 (3)
C10—C8—C9—C26	142.95 (15)	C32—C33—C34—C27	−179.9 (2)
N2—C8—C9—C6	23.50 (17)	C30—C29—C34—C33	−0.2 (3)
C16—C8—C9—C6	148.35 (16)	N5—C29—C34—C33	179.80 (18)
C10—C8—C9—C6	−98.24 (16)	C30—C29—C34—C27	−179.7 (2)
N2—C8—C10—O1	−48.4 (3)	N5—C29—C34—C27	0.3 (2)
C16—C8—C10—O1	−171.61 (19)	C28—C27—C34—C33	−179.5 (2)
C9—C8—C10—O1	64.7 (2)	C26—C27—C34—C33	7.4 (4)
N2—C8—C10—N3	132.87 (16)	C28—C27—C34—C29	−0.2 (2)
C16—C8—C10—N3	9.69 (19)	C26—C27—C34—C29	−173.29 (19)
C9—C8—C10—N3	−113.99 (16)	C2—C3—N1—C4	−0.4 (3)
C16—C11—C12—C13	−0.2 (3)	C5—C4—N1—C3	1.7 (3)
N3—C11—C12—C13	178.6 (2)	C16—C8—N2—C7	−169.48 (16)
C11—C12—C13—C14	−1.3 (4)	C10—C8—N2—C7	74.2 (2)
C12—C13—C14—C15	1.1 (4)	C9—C8—N2—C7	−42.32 (18)
C13—C14—C15—C16	0.7 (4)	C16—C8—N2—C17	63.5 (2)
C14—C15—C16—C11	−2.2 (3)	C10—C8—N2—C17	−52.8 (2)
C14—C15—C16—C8	178.4 (2)	C9—C8—N2—C17	−169.36 (16)
C12—C11—C16—C15	1.9 (3)	C6—C7—N2—C8	44.46 (19)
N3—C11—C16—C15	−177.05 (17)	C6—C7—N2—C17	171.97 (17)
C12—C11—C16—C8	−178.56 (18)	O1—C10—N3—C11	172.32 (19)
N3—C11—C16—C8	2.4 (2)	C8—C10—N3—C11	−9.0 (2)
N2—C8—C16—C15	48.1 (3)	O1—C10—N3—C19	−0.1 (3)
C10—C8—C16—C15	172.3 (2)	C8—C10—N3—C19	178.67 (16)
C9—C8—C16—C15	−70.7 (3)	C12—C11—N3—C10	−174.6 (2)
N2—C8—C16—C11	−131.37 (17)	C16—C11—N3—C10	4.3 (2)
C10—C8—C16—C11	−7.2 (2)	C12—C11—N3—C19	−2.5 (3)
C9—C8—C16—C11	109.90 (19)	C16—C11—N3—C19	176.42 (18)
N3—C19—C20—C25	52.9 (3)	C20—C19—N3—C10	−122.3 (2)
N3—C19—C20—C21	−130.3 (2)	C20—C19—N3—C11	66.5 (3)
C25—C20—C21—C22	0.7 (3)	C27—C28—N5—C29	0.3 (3)
C19—C20—C21—C22	−176.1 (2)	C30—C29—N5—C28	179.6 (2)
C20—C21—C22—C23	−0.6 (4)	C34—C29—N5—C28	−0.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N5—H5···N1ⁱ	0.86	1.96	2.812 (2)	170
C19—H19A···N4ⁱⁱ	0.97	2.46	3.370 (3)	157

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

Acknowledgements

PS and CP thank the Department of Chemistry, IIT, Chennai, India, for the X-ray diffraction data collection.

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