Ethyl 27-oxo-15-oxa-2,20-diaza­hexa­cyclo­[18.6.1.01,8.02,6.09,14.021,26]hepta­cosa-9,11,13,21,23,25-hexa­ene-7-carboxyl­ate

Narayanan, S.; Srinivasan, T.; Purushothaman, S.; Raghunathan, R.; Velmurugan, D.

doi:10.1107/S1600536812049082

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 1| January 2013| Pages o23-o24

https://doi.org/10.1107/S1600536812049082

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Ethyl 27-oxo-15-oxa-2,20-diazahexacyclo[18.6.1.0^1,8.0^2,6.0^9,14.0^21,26]heptacosa-9,11,13,21,23,25-hexaene-7-carboxylate

Sibi Narayanan,^a Thothadri Srinivasan,^a Santhanagopalan Purushothaman,^b Raghavachary Raghunathan ^b and Devadasan Velmurugan ^a ^*

^aCentre of Advanced Study in Crystallography and Biophysics, University of Madras, Guindy Campus, Chennai 600 025, India, and ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India
^*Correspondence e-mail: shirai2011@gmail.com

(Received 10 November 2012; accepted 29 November 2012; online 5 December 2012)

In the title compound, C₂₇H₃₀N₂O₄, the pyrrolidine ring adopts a twisted conformation. The indoline ring system is almost perpendicular to the mean plane of the pyrrolidine ring, making a dihedral angle of 81.7 (8)°. In the crystal, molecules are linked into centrosymmetric dimers with graph-set motif R₂²(16) via pairs of C—H⋯O hydrogen bonds. The terminal ethyl group of the ester group is disordered over two sets of sites, with a site-occupancy ratio of 0.587 (11):0.413 (11).

Related literature

For the biological activity of spiro-pyrrolidine derivatives, see: Obniska et al. (2003 ); Peddi et al. (2004 ); Christoph et al. (2011 ); Stylianakis et al. (2003 ); Waldmann (1995 ); Suzuki et al. (1994 ); Huryn et al. (1991 ). For a related structure, see: Ganesh et al. (2012 ). For puckering parameters, see: Cremer & Pople (1975 ) and for asymmetry parameters, see: Nardelli et al. (1983 ).

Experimental

Crystal data

C₂₇H₃₀N₂O₄
M_r = 446.53
Triclinic, $[P \overline 1]$
a = 8.9327 (5) Å
b = 10.0068 (5) Å
c = 14.6379 (11) Å
α = 103.988 (4)°
β = 95.023 (4)°
γ = 113.775 (3)°
V = 1136.41 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.30 × 0.30 × 0.25 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.974, T_max = 0.978
20472 measured reflections
5603 independent reflections
4378 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.125
S = 1.08
5603 reflections
319 parameters
40 restraints
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O1ⁱ	0.93	2.49	3.3957 (19)	164
C12—H12⋯O2ⁱⁱ	0.93	2.59	3.446 (2)	153
C13—H13⋯O4ⁱⁱ	0.93	2.47	3.3986 (17)	175
Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) x+1, y, z.

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812049082/bt6853sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049082/bt6853Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812049082/bt6853Isup3.cml

checkCIF report

Comment top

Spiro-pyrrolidine derivatives are unique tetracyclic 5-HT(2 A) receptor antagonists (Obniska et al., 2003; Peddi et al., 2004). These derivatives possess anticancer (Christoph et al., 2011) and anti-influenza virus (Stylianakis et al., 2003) activities. Highly functionalized pyrrolidines have gained much interest in the past few 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 these importance and in continuation of our work on the crystal structure analysis of spiro-pyrrolidine derivatives, the crystal structure of the title compound has been carried out and the results are presented here.

X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The bond lengths and angles are within normal ranges and comparable to those found in related structures (Ganesh et al., 2012). Terminal atoms C1 & C2 is substituted at propanate group, which is disordered over two positions [C1A/C1B & C2A/C2B] with a site-occupancy ratio of 0.604 (5):0.396 (5). The sum of the angles at N1 & N2 [339 (1)° & 348.7 (1)°] of the pyrrolidine and indole rings are in accordance with sp³ hybridization.

The indoline ring system is essentially planar, with maximum deviation of 0.038 (2) Å for atom C16. The pyrrolidine ring system makes dihedral angle of 81.7 (8)° with the indoline ring system, it clearly shows that both the rings are perpendicular to each other. The propanate group assumes an extended conformation which can be seen from the torsion angle [C4/C3/O2/C2= 179.3 (2)°].

The dihedral angle of the pyrrolidine ring and the benzene ring (C21—C26) is 36.5 (1)°. The atom O4 deviates by 0.102 (1) Å from the leastsquares plane of the indole ring. The pyrrolidine ring adopts twisted conformation [it is twisted about C1—C2], with the puckering parameters q₂ and φ (Cremer & Pople, 1975) and the smallest displacement asymmetric parameter, Δ_s, (Nardelli et al., 1983) as follows: q₂=0.4071 (2) Å, φ=82.0 (8)°, Δ_s(C4)=7.61 (2). The crystal packing is stabilized by C—H···O interactions.

Related literature top

For the biological activity of spiro-pyrrolidine derivatives, see: Obniska et al. (2003); Peddi et al. (2004); Christoph et al. (2011); Stylianakis et al. (2003); Waldmann (1995); Suzuki et al. (1994); Huryn et al. (1991). For a related structure, see: Ganesh et al. (2012). For puckering parameters, see: Cremer & Pople (1975) and for asymmetry parameters, see: Nardelli et al. (1983).

Experimental top

A solution of (E)-ethyl 3-(2-(4-(2,3-dioxoindolin-1-yl)butoxy)phenyl)acrylate (200 mg, 0.5 mmol) and L-proline (70 mg, 0.61 mmol) was refluxed in dry toluene under N₂ atmosphere for 8hrs under Dean-Stark apparatus. After the completion of reaction as indicated by TLC, toluene was evaporated under reduced pressure. The crude product was washed with water and extracted with dichloromethane (4x20mL). The combined organic layers were dried (MgSO₄) and filtered, concentrated in vacuum. The crude product was purified by column chromatography using hexane: EtOAc (8:2) as eluent.

Structure description top

For the biological activity of spiro-pyrrolidine derivatives, see: Obniska et al. (2003); Peddi et al. (2004); Christoph et al. (2011); Stylianakis et al. (2003); Waldmann (1995); Suzuki et al. (1994); Huryn et al. (1991). For a related structure, see: Ganesh et al. (2012). For puckering parameters, see: Cremer & Pople (1975) and for asymmetry parameters, see: Nardelli et al. (1983).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for figure clarity.
	Fig. 2. The crystal structure showing the formation of the centrosymmetric R₂²(16) dimer. H atoms are not involed in hydrogen bonds have been omitted.

Ethyl 27-oxo-15-oxa-2,20- diazahexacyclo[18.6.1.0^1,8.0^2,6.0^9,14.0^21,26]heptacosa- 9,11,13,21,23,25-hexaene-7-carboxylate top

Crystal data top

C₂₇H₃₀N₂O₄	Z = 2
M_r = 446.53	F(000) = 476
Triclinic, P1	D_x = 1.305 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9327 (5) Å	Cell parameters from 5603 reflections
b = 10.0068 (5) Å	θ = 1.5–28.3°
c = 14.6379 (11) Å	µ = 0.09 mm⁻¹
α = 103.988 (4)°	T = 293 K
β = 95.023 (4)°	Block, white crystalline
γ = 113.775 (3)°	0.30 × 0.30 × 0.25 mm
V = 1136.41 (13) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	5603 independent reflections
Radiation source: fine-focus sealed tube	4378 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and φ scans	θ_max = 28.3°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
T_min = 0.974, T_max = 0.978	k = −13→13
20472 measured reflections	l = −18→19

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0559P)² + 0.215P] where P = (F_o² + 2F_c²)/3
5603 reflections	(Δ/σ)_max = 0.002
319 parameters	Δρ_max = 0.23 e Å⁻³
40 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₇H₃₀N₂O₄	γ = 113.775 (3)°
M_r = 446.53	V = 1136.41 (13) Å³
Triclinic, P1	Z = 2
a = 8.9327 (5) Å	Mo Kα radiation
b = 10.0068 (5) Å	µ = 0.09 mm⁻¹
c = 14.6379 (11) Å	T = 293 K
α = 103.988 (4)°	0.30 × 0.30 × 0.25 mm
β = 95.023 (4)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	5603 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	4378 reflections with I > 2σ(I)
T_min = 0.974, T_max = 0.978	R_int = 0.025
20472 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	40 restraints
wR(F²) = 0.125	H-atom parameters constrained
S = 1.08	Δρ_max = 0.23 e Å⁻³
5603 reflections	Δρ_min = −0.22 e Å⁻³
319 parameters

Special details top

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 F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1A	−0.0430 (10)	1.0338 (8)	0.2839 (4)	0.0877 (18)	0.587 (11)
H1A1	0.0125	1.0358	0.2306	0.132*	0.587 (11)
H1A2	−0.0730	1.1174	0.2975	0.132*	0.587 (11)
H1A3	−0.1420	0.9386	0.2680	0.132*	0.587 (11)
C2A	0.0677 (12)	1.0483 (8)	0.3675 (6)	0.089 (3)	0.587 (11)
H2A1	0.0188	1.0599	0.4238	0.106*	0.587 (11)
H2A2	0.1740	1.1376	0.3795	0.106*	0.587 (11)
C1B	0.0656 (17)	1.0966 (9)	0.2980 (6)	0.088 (3)	0.413 (11)
H1B1	0.1845	1.1562	0.3183	0.131*	0.413 (11)
H1B2	0.0130	1.1639	0.3003	0.131*	0.413 (11)
H1B3	0.0393	1.0304	0.2334	0.131*	0.413 (11)
C2B	0.0054 (13)	1.0057 (11)	0.3611 (9)	0.072 (3)	0.413 (11)
H2B1	−0.1149	0.9451	0.3426	0.086*	0.413 (11)
H2B2	0.0346	1.0696	0.4274	0.086*	0.413 (11)
C3	0.21727 (18)	0.92280 (15)	0.41102 (10)	0.0423 (3)
C4	0.26073 (15)	0.78973 (13)	0.38728 (9)	0.0328 (3)
H4	0.3792	0.8281	0.4159	0.039*
C5	0.15967 (15)	0.66458 (14)	0.43037 (9)	0.0346 (3)
H5	0.0410	0.6419	0.4175	0.042*
C6	0.22279 (18)	0.69639 (17)	0.53715 (10)	0.0466 (3)
H6A	0.2708	0.8051	0.5713	0.056*
H6B	0.1334	0.6416	0.5664	0.056*
C7	0.3552 (2)	0.63749 (19)	0.53718 (11)	0.0550 (4)
H7A	0.4601	0.7115	0.5293	0.066*
H7B	0.3743	0.6130	0.5960	0.066*
C8	0.2771 (2)	0.49510 (18)	0.45101 (11)	0.0503 (4)
H8A	0.3628	0.4711	0.4251	0.060*
H8B	0.2022	0.4082	0.4687	0.060*
C9	0.24212 (14)	0.55059 (13)	0.28972 (9)	0.0314 (2)
C10	0.40719 (14)	0.54634 (14)	0.28034 (9)	0.0335 (3)
C11	0.56843 (16)	0.64768 (16)	0.32716 (11)	0.0433 (3)
H11	0.5907	0.7389	0.3736	0.052*
C12	0.69804 (17)	0.6109 (2)	0.30370 (12)	0.0531 (4)
H12	0.8079	0.6793	0.3342	0.064*
C13	0.66598 (19)	0.4754 (2)	0.23631 (12)	0.0552 (4)
H13	0.7541	0.4521	0.2231	0.066*
C14	0.50416 (19)	0.37281 (19)	0.18772 (11)	0.0491 (4)
H14	0.4821	0.2810	0.1419	0.059*
C15	0.37664 (16)	0.41162 (15)	0.20968 (9)	0.0373 (3)
C16	0.11869 (15)	0.40657 (14)	0.20770 (9)	0.0362 (3)
C17	0.1341 (2)	0.19559 (16)	0.08382 (11)	0.0528 (4)
H17A	0.0135	0.1469	0.0769	0.063*
H17B	0.1753	0.1226	0.0927	0.063*
C18	0.1747 (2)	0.23314 (18)	−0.00835 (11)	0.0552 (4)
H18A	0.1372	0.1376	−0.0597	0.066*
H18B	0.2953	0.2869	0.0004	0.066*
C19	0.0979 (2)	0.33016 (19)	−0.04075 (11)	0.0568 (4)
H19A	0.0621	0.2915	−0.1103	0.068*
H19B	−0.0013	0.3154	−0.0142	0.068*
C20	0.2087 (2)	0.49895 (18)	−0.01325 (10)	0.0531 (4)
H20A	0.3192	0.5157	−0.0248	0.064*
H20B	0.1635	0.5445	−0.0528	0.064*
C21	0.33250 (17)	0.72236 (15)	0.12529 (10)	0.0396 (3)
C22	0.4290 (2)	0.80905 (19)	0.07220 (11)	0.0536 (4)
H22	0.4166	0.7651	0.0066	0.064*
C23	0.5431 (2)	0.95975 (19)	0.11637 (12)	0.0592 (4)
H23	0.6082	1.0165	0.0806	0.071*
C24	0.5606 (2)	1.02605 (18)	0.21268 (12)	0.0565 (4)
H24	0.6379	1.1274	0.2427	0.068*
C25	0.46165 (18)	0.94020 (16)	0.26501 (11)	0.0473 (3)
H25	0.4736	0.9863	0.3302	0.057*
C26	0.34589 (15)	0.78868 (14)	0.22383 (9)	0.0350 (3)
C27	0.23201 (14)	0.69994 (13)	0.28114 (8)	0.0314 (2)
H27	0.1165	0.6710	0.2510	0.038*
N1	0.18398 (13)	0.53096 (12)	0.37981 (7)	0.0361 (2)
N2	0.20527 (14)	0.32851 (12)	0.16915 (8)	0.0398 (3)
O1	0.28603 (18)	1.03033 (14)	0.48165 (9)	0.0743 (4)
O2	0.09278 (16)	0.90670 (14)	0.34755 (9)	0.0684 (3)
O3	0.22133 (12)	0.57163 (11)	0.08703 (6)	0.0447 (2)
O4	−0.03046 (11)	0.36456 (11)	0.18380 (7)	0.0494 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1A	0.106 (4)	0.079 (3)	0.104 (3)	0.063 (3)	0.008 (3)	0.038 (3)
C2A	0.119 (6)	0.077 (4)	0.087 (4)	0.078 (4)	−0.009 (4)	0.002 (3)
C1B	0.131 (7)	0.069 (4)	0.074 (4)	0.046 (4)	0.027 (4)	0.032 (3)
C2B	0.092 (5)	0.072 (4)	0.087 (6)	0.058 (4)	0.041 (5)	0.038 (4)
C3	0.0498 (7)	0.0370 (7)	0.0411 (8)	0.0205 (6)	0.0135 (6)	0.0094 (6)
C4	0.0343 (6)	0.0329 (6)	0.0297 (6)	0.0152 (5)	0.0065 (5)	0.0064 (5)
C5	0.0346 (6)	0.0354 (6)	0.0328 (6)	0.0155 (5)	0.0097 (5)	0.0072 (5)
C6	0.0565 (8)	0.0451 (8)	0.0320 (7)	0.0163 (6)	0.0131 (6)	0.0103 (6)
C7	0.0570 (9)	0.0661 (10)	0.0420 (8)	0.0227 (8)	0.0038 (7)	0.0265 (7)
C8	0.0655 (9)	0.0601 (9)	0.0476 (9)	0.0391 (8)	0.0218 (7)	0.0304 (7)
C9	0.0315 (5)	0.0331 (6)	0.0300 (6)	0.0157 (5)	0.0067 (5)	0.0075 (5)
C10	0.0341 (6)	0.0377 (6)	0.0340 (6)	0.0193 (5)	0.0086 (5)	0.0128 (5)
C11	0.0360 (6)	0.0470 (8)	0.0474 (8)	0.0183 (6)	0.0062 (6)	0.0162 (6)
C12	0.0349 (7)	0.0702 (10)	0.0638 (10)	0.0254 (7)	0.0118 (7)	0.0319 (9)
C13	0.0528 (8)	0.0895 (12)	0.0568 (10)	0.0507 (9)	0.0274 (7)	0.0396 (9)
C14	0.0629 (9)	0.0646 (9)	0.0431 (8)	0.0460 (8)	0.0218 (7)	0.0208 (7)
C15	0.0433 (7)	0.0437 (7)	0.0347 (7)	0.0255 (6)	0.0126 (5)	0.0156 (5)
C16	0.0379 (6)	0.0353 (6)	0.0342 (7)	0.0161 (5)	0.0082 (5)	0.0081 (5)
C17	0.0673 (9)	0.0375 (7)	0.0460 (9)	0.0239 (7)	0.0076 (7)	−0.0002 (6)
C18	0.0703 (10)	0.0500 (9)	0.0403 (8)	0.0310 (8)	0.0085 (7)	−0.0018 (7)
C19	0.0667 (10)	0.0619 (10)	0.0342 (8)	0.0330 (8)	−0.0024 (7)	−0.0020 (7)
C20	0.0743 (10)	0.0599 (9)	0.0305 (7)	0.0375 (8)	0.0112 (7)	0.0090 (6)
C21	0.0473 (7)	0.0439 (7)	0.0353 (7)	0.0260 (6)	0.0094 (6)	0.0148 (6)
C22	0.0738 (10)	0.0600 (9)	0.0394 (8)	0.0345 (8)	0.0225 (7)	0.0230 (7)
C23	0.0705 (10)	0.0612 (10)	0.0576 (10)	0.0276 (8)	0.0278 (8)	0.0351 (8)
C24	0.0612 (9)	0.0471 (8)	0.0554 (10)	0.0138 (7)	0.0143 (8)	0.0226 (7)
C25	0.0530 (8)	0.0448 (8)	0.0388 (8)	0.0155 (6)	0.0103 (6)	0.0140 (6)
C26	0.0392 (6)	0.0386 (6)	0.0322 (6)	0.0201 (5)	0.0081 (5)	0.0134 (5)
C27	0.0331 (6)	0.0327 (6)	0.0287 (6)	0.0164 (5)	0.0046 (5)	0.0072 (5)
N1	0.0436 (6)	0.0373 (6)	0.0323 (6)	0.0210 (5)	0.0125 (4)	0.0115 (4)
N2	0.0451 (6)	0.0357 (6)	0.0365 (6)	0.0207 (5)	0.0071 (5)	0.0024 (4)
O1	0.0918 (9)	0.0525 (7)	0.0627 (8)	0.0368 (7)	0.0019 (7)	−0.0139 (6)
O2	0.0874 (8)	0.0622 (7)	0.0668 (8)	0.0558 (7)	−0.0023 (6)	0.0045 (6)
O3	0.0589 (6)	0.0458 (5)	0.0286 (5)	0.0243 (5)	0.0090 (4)	0.0078 (4)
O4	0.0336 (5)	0.0502 (6)	0.0515 (6)	0.0142 (4)	0.0025 (4)	0.0029 (5)

Geometric parameters (Å, º) top

C1A—C2A	1.443 (6)	C11—C12	1.3947 (19)
C1A—H1A1	0.9600	C11—H11	0.9300
C1A—H1A2	0.9600	C12—C13	1.373 (2)
C1A—H1A3	0.9600	C12—H12	0.9300
C2A—O2	1.487 (5)	C13—C14	1.385 (2)
C2A—H2A1	0.9700	C13—H13	0.9300
C2A—H2A2	0.9700	C14—C15	1.3827 (18)
C1B—C2B	1.438 (7)	C14—H14	0.9300
C1B—H1B1	0.9600	C15—N2	1.4011 (17)
C1B—H1B2	0.9600	C16—O4	1.2123 (15)
C1B—H1B3	0.9600	C16—N2	1.3701 (16)
C2B—O2	1.478 (6)	C17—N2	1.4524 (18)
C2B—H2B1	0.9700	C17—C18	1.521 (2)
C2B—H2B2	0.9700	C17—H17A	0.9700
C3—O1	1.1925 (18)	C17—H17B	0.9700
C3—O2	1.3145 (18)	C18—C19	1.530 (2)
C3—C4	1.5038 (17)	C18—H18A	0.9700
C4—C5	1.5333 (16)	C18—H18B	0.9700
C4—C27	1.5351 (17)	C19—C20	1.500 (2)
C4—H4	0.9800	C19—H19A	0.9700
C5—N1	1.4720 (16)	C19—H19B	0.9700
C5—C6	1.5241 (19)	C20—O3	1.4440 (16)
C5—H5	0.9800	C20—H20A	0.9700
C6—C7	1.520 (2)	C20—H20B	0.9700
C6—H6A	0.9700	C21—O3	1.3643 (16)
C6—H6B	0.9700	C21—C22	1.3930 (19)
C7—C8	1.511 (2)	C21—C26	1.4064 (18)
C7—H7A	0.9700	C22—C23	1.380 (2)
C7—H7B	0.9700	C22—H22	0.9300
C8—N1	1.4756 (17)	C23—C24	1.370 (2)
C8—H8A	0.9700	C23—H23	0.9300
C8—H8B	0.9700	C24—C25	1.3896 (19)
C9—N1	1.4867 (15)	C24—H24	0.9300
C9—C10	1.5093 (15)	C25—C26	1.3843 (19)
C9—C16	1.5442 (17)	C25—H25	0.9300
C9—C27	1.5669 (16)	C26—C27	1.5194 (16)
C10—C11	1.3734 (18)	C27—H27	0.9800
C10—C15	1.3934 (18)

C1A—C2A—O2	107.4 (5)	C14—C13—H13	119.5
C1A—C2A—H2A1	110.2	C15—C14—C13	117.71 (14)
O2—C2A—H2A1	110.2	C15—C14—H14	121.1
C1A—C2A—H2A2	110.2	C13—C14—H14	121.1
O2—C2A—H2A2	110.2	C14—C15—C10	121.80 (13)
H2A1—C2A—H2A2	108.5	C14—C15—N2	127.97 (13)
C2B—C1B—H1B1	109.5	C10—C15—N2	110.23 (10)
C2B—C1B—H1B2	109.5	O4—C16—N2	125.24 (12)
H1B1—C1B—H1B2	109.5	O4—C16—C9	126.60 (11)
C2B—C1B—H1B3	109.5	N2—C16—C9	108.07 (10)
H1B1—C1B—H1B3	109.5	N2—C17—C18	113.75 (12)
H1B2—C1B—H1B3	109.5	N2—C17—H17A	108.8
C1B—C2B—O2	103.0 (6)	C18—C17—H17A	108.8
C1B—C2B—H2B1	111.2	N2—C17—H17B	108.8
O2—C2B—H2B1	111.2	C18—C17—H17B	108.8
C1B—C2B—H2B2	111.2	H17A—C17—H17B	107.7
O2—C2B—H2B2	111.2	C17—C18—C19	115.73 (13)
H2B1—C2B—H2B2	109.1	C17—C18—H18A	108.3
O1—C3—O2	123.36 (13)	C19—C18—H18A	108.3
O1—C3—C4	123.34 (14)	C17—C18—H18B	108.3
O2—C3—C4	113.27 (12)	C19—C18—H18B	108.3
C3—C4—C5	111.85 (10)	H18A—C18—H18B	107.4
C3—C4—C27	118.71 (10)	C20—C19—C18	116.20 (14)
C5—C4—C27	102.81 (9)	C20—C19—H19A	108.2
C3—C4—H4	107.6	C18—C19—H19A	108.2
C5—C4—H4	107.6	C20—C19—H19B	108.2
C27—C4—H4	107.6	C18—C19—H19B	108.2
N1—C5—C6	105.91 (10)	H19A—C19—H19B	107.4
N1—C5—C4	103.94 (9)	O3—C20—C19	110.62 (13)
C6—C5—C4	115.22 (11)	O3—C20—H20A	109.5
N1—C5—H5	110.5	C19—C20—H20A	109.5
C6—C5—H5	110.5	O3—C20—H20B	109.5
C4—C5—H5	110.5	C19—C20—H20B	109.5
C7—C6—C5	103.05 (11)	H20A—C20—H20B	108.1
C7—C6—H6A	111.2	O3—C21—C22	123.50 (13)
C5—C6—H6A	111.2	O3—C21—C26	116.04 (11)
C7—C6—H6B	111.2	C22—C21—C26	120.46 (13)
C5—C6—H6B	111.2	C23—C22—C21	120.37 (14)
H6A—C6—H6B	109.1	C23—C22—H22	119.8
C8—C7—C6	102.04 (12)	C21—C22—H22	119.8
C8—C7—H7A	111.4	C24—C23—C22	120.23 (14)
C6—C7—H7A	111.4	C24—C23—H23	119.9
C8—C7—H7B	111.4	C22—C23—H23	119.9
C6—C7—H7B	111.4	C23—C24—C25	119.26 (15)
H7A—C7—H7B	109.2	C23—C24—H24	120.4
N1—C8—C7	105.66 (11)	C25—C24—H24	120.4
N1—C8—H8A	110.6	C26—C25—C24	122.54 (14)
C7—C8—H8A	110.6	C26—C25—H25	118.7
N1—C8—H8B	110.6	C24—C25—H25	118.7
C7—C8—H8B	110.6	C25—C26—C21	117.12 (12)
H8A—C8—H8B	108.7	C25—C26—C27	121.56 (11)
N1—C9—C10	116.46 (9)	C21—C26—C27	121.25 (11)
N1—C9—C16	106.22 (9)	C26—C27—C4	114.73 (10)
C10—C9—C16	101.89 (9)	C26—C27—C9	117.37 (9)
N1—C9—C27	104.52 (9)	C4—C27—C9	101.60 (9)
C10—C9—C27	115.18 (9)	C26—C27—H27	107.5
C16—C9—C27	112.44 (9)	C4—C27—H27	107.5
C11—C10—C15	119.80 (11)	C9—C27—H27	107.5
C11—C10—C9	131.67 (12)	C5—N1—C8	108.13 (10)
C15—C10—C9	108.54 (10)	C5—N1—C9	110.23 (9)
C10—C11—C12	118.65 (14)	C8—N1—C9	120.66 (10)
C10—C11—H11	120.7	C16—N2—C15	110.85 (10)
C12—C11—H11	120.7	C16—N2—C17	123.63 (11)
C13—C12—C11	121.05 (14)	C15—N2—C17	124.23 (11)
C13—C12—H12	119.5	C3—O2—C2B	124.6 (5)
C11—C12—H12	119.5	C3—O2—C2A	111.3 (3)
C12—C13—C14	120.93 (13)	C21—O3—C20	117.33 (11)
C12—C13—H13	119.5

O1—C3—C4—C5	89.09 (17)	C22—C21—C26—C27	175.06 (12)
O2—C3—C4—C5	−89.09 (14)	C25—C26—C27—C4	−2.05 (16)
O1—C3—C4—C27	−151.44 (14)	C21—C26—C27—C4	−178.96 (10)
O2—C3—C4—C27	30.38 (16)	C25—C26—C27—C9	−121.25 (13)
C3—C4—C5—N1	165.51 (10)	C21—C26—C27—C9	61.84 (15)
C27—C4—C5—N1	37.05 (11)	C3—C4—C27—C26	67.92 (14)
C3—C4—C5—C6	−79.07 (14)	C5—C4—C27—C26	−168.04 (9)
C27—C4—C5—C6	152.47 (10)	C3—C4—C27—C9	−164.39 (10)
N1—C5—C6—C7	28.37 (13)	C5—C4—C27—C9	−40.35 (11)
C4—C5—C6—C7	−85.91 (13)	N1—C9—C27—C26	155.06 (10)
C5—C6—C7—C8	−38.37 (13)	C10—C9—C27—C26	25.97 (15)
C6—C7—C8—N1	34.89 (14)	C16—C9—C27—C26	−90.16 (12)
N1—C9—C10—C11	−70.23 (17)	N1—C9—C27—C4	29.09 (11)
C16—C9—C10—C11	174.70 (13)	C10—C9—C27—C4	−99.99 (11)
C27—C9—C10—C11	52.69 (18)	C16—C9—C27—C4	143.88 (10)
N1—C9—C10—C15	110.05 (12)	C6—C5—N1—C8	−6.82 (13)
C16—C9—C10—C15	−5.02 (12)	C4—C5—N1—C8	115.00 (11)
C27—C9—C10—C15	−127.02 (11)	C6—C5—N1—C9	−140.65 (10)
C15—C10—C11—C12	−1.28 (19)	C4—C5—N1—C9	−18.83 (12)
C9—C10—C11—C12	179.03 (12)	C7—C8—N1—C5	−17.71 (14)
C10—C11—C12—C13	−1.0 (2)	C7—C8—N1—C9	110.39 (13)
C11—C12—C13—C14	1.7 (2)	C10—C9—N1—C5	121.72 (11)
C12—C13—C14—C15	−0.2 (2)	C16—C9—N1—C5	−125.67 (10)
C13—C14—C15—C10	−2.1 (2)	C27—C9—N1—C5	−6.59 (12)
C13—C14—C15—N2	178.71 (13)	C10—C9—N1—C8	−5.43 (16)
C11—C10—C15—C14	2.89 (19)	C16—C9—N1—C8	107.18 (12)
C9—C10—C15—C14	−177.35 (11)	C27—C9—N1—C8	−133.74 (11)
C11—C10—C15—N2	−177.82 (11)	O4—C16—N2—C15	177.33 (12)
C9—C10—C15—N2	1.94 (14)	C9—C16—N2—C15	−5.83 (14)
N1—C9—C16—O4	60.93 (16)	O4—C16—N2—C17	9.9 (2)
C10—C9—C16—O4	−176.69 (13)	C9—C16—N2—C17	−173.31 (12)
C27—C9—C16—O4	−52.82 (17)	C14—C15—N2—C16	−178.20 (13)
N1—C9—C16—N2	−115.86 (10)	C10—C15—N2—C16	2.56 (15)
C10—C9—C16—N2	6.52 (12)	C14—C15—N2—C17	−10.8 (2)
C27—C9—C16—N2	130.40 (10)	C10—C15—N2—C17	169.95 (12)
N2—C17—C18—C19	−66.50 (18)	C18—C17—N2—C16	96.75 (16)
C17—C18—C19—C20	97.32 (18)	C18—C17—N2—C15	−69.06 (18)
C18—C19—C20—O3	−76.86 (17)	O1—C3—O2—C2B	−9.2 (4)
O3—C21—C22—C23	−177.87 (14)	C4—C3—O2—C2B	169.0 (4)
C26—C21—C22—C23	2.2 (2)	O1—C3—O2—C2A	8.6 (5)
C21—C22—C23—C24	−0.9 (3)	C4—C3—O2—C2A	−173.2 (5)
C22—C23—C24—C25	−0.4 (3)	C1B—C2B—O2—C3	106.8 (10)
C23—C24—C25—C26	0.6 (2)	C1B—C2B—O2—C2A	52.4 (13)
C24—C25—C26—C21	0.6 (2)	C1A—C2A—O2—C3	167.2 (7)
C24—C25—C26—C27	−176.39 (13)	C1A—C2A—O2—C2B	−58.7 (15)
O3—C21—C26—C25	178.04 (12)	C22—C21—O3—C20	1.99 (19)
C22—C21—C26—C25	−1.99 (19)	C26—C21—O3—C20	−178.03 (11)
O3—C21—C26—C27	−4.92 (17)	C19—C20—O3—C21	173.01 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.93	2.49	3.3957 (19)	164
C12—H12···O2ⁱⁱ	0.93	2.59	3.446 (2)	153
C13—H13···O4ⁱⁱ	0.93	2.47	3.3986 (17)	175

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

Experimental details

Crystal data
Chemical formula	C₂₇H₃₀N₂O₄
M_r	446.53
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.9327 (5), 10.0068 (5), 14.6379 (11)
α, β, γ (°)	103.988 (4), 95.023 (4), 113.775 (3)
V (Å³)	1136.41 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.30 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.974, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	20472, 5603, 4378
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.125, 1.08
No. of reflections	5603
No. of parameters	319
No. of restraints	40
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.22

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O1ⁱ	0.93	2.49	3.3957 (19)	164.0
C12—H12···O2ⁱⁱ	0.93	2.59	3.446 (2)	152.9
C13—H13···O4ⁱⁱ	0.93	2.47	3.3986 (17)	174.6

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

Acknowledgements

The authors thank the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection. SN thanks the University Grant Commission (UGC), Government of India, New Delhi, for a Meritorious Fellowship under the SAP programme.

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Ethyl 27-oxo-15-oxa-2,20-di­aza­hexa­cyclo­[18.6.1.01,8.02,6.09,14.021,26]hepta­cosa-9,11,13,21,23,25-hexa­ene-7-carboxyl­ate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Ethyl 27-oxo-15-oxa-2,20-diazahexacyclo[18.6.1.0^1,8.0^2,6.0^9,14.0^21,26]heptacosa-9,11,13,21,23,25-hexaene-7-carboxylate