Methyl 5′′-chloro-1′,1′′-dimethyl-2,2′′-dioxodi­spiro­[indoline-3,2′-pyrrolidine-3′,3′′-indoline]-4′-carboxyl­ate

Kannan, P.S.; Yuvaraj, P.S.; Manivannan, K.; Reddy, B.S.R.; SubbiahPandi, A.

doi:10.1107/S1600536813011501

Methyl 5′′-chloro-1′,1′′-dimethyl-2,2′′-dioxodispiro[indoline-3,2′-pyrrolidine-3′,3′′-indoline]-4′-carboxylate

P. S. Kannan, P. S. Yuvaraj, K. Manivannan, B. S. R. Reddy and A. SubbiahPandi

In the title compound, C₂₂H₂₀ClN₃O₄, the central pyrrolidine ring adopts an envelope conformation on the N atom. The indolinone systems are individually roughly planar, with maximum deviations from their mean planes of 0.130 Å for the spiro C atom of the indolinone unit and 0.172 Å for the carbonyl C atom of the 5-chloro-1-methylindolinone unit. They make dihedral angles of 77.7 (8) and 86.1 (8)° with the mean plane through the central pyrrolidine ring. In the crystal, molecules are linked by N—H

O hydrogen bonds supported by C—H

O contacts into chains along the ab diagonal. The structure also features C—H

O hydrogen bonds, forming R₂²(8) and R₂²(16) rings and generating a three-dimensional array.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536813011501/sj5312sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536813011501/sj5312Isup2.hkl Contains datablock I

CCDC reference: 954871

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.002 Å
R factor = 0.041
wR factor = 0.125
Data-to-parameter ratio = 18.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O3     --  C20     ..        6.1 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H5     ..  O3      ..       2.61 Ang.
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -2.350

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF          ?
PLAT128_ALERT_4_G Alternate Setting of Space-group P21/c   .......      P21/n
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT793_ALERT_4_G The Model has Chirality at C7      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C9      (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at C12     (Verify) ....          R
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         39

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   8 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   6 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Spiro-pyrrolidine derivatives are unique tetracyclic 5-HT(2A) receptor antagonists (Obniska et al., 2003; Peddi et al., 2004). These derivatives possess anticonvulsant (Kaminski & Obniska, 2008) 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 also been used as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis (Suzuki et al., 1994; Huryn et al., 1991).

X-Ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The geometries of the pyrrolidine and indole systems are comparable with those in related structures (Wei et al., 2011; Ganesh et al., 2012). The sum of the angles at N2 [336.9 (1)°] of the pyrrolidine rings is typical of sp³ hybridization. The indoline ring systems [N1/C1-C8 and N3/C12-C19] make dihedral angles of 77.7 (8) ° and 86.1(68° with respect to the mean plane of the central pyrrolidine ring system [N2/C7/C9/C10/C12]. This clearly shows that the indoline ring (N3/C12-C19) and the central pyrrolidine ring system are almost perpendicular to one another. The indole ring systems are essentially planar, with maximum deviations from the mean planes of 0.130 Å for the C12 and -0.172 Å for the C8 atoms, respectively.

The central pyrrolidine ring adopts an envelope conformation on the N2 atom, with puckering parameters q₂ = 0.419 (2) Å, ϕ = 1.555 (2)(Cremer & Pople, 1975 ). The pyrrolidine ring in the chloro-indole ring system adopts a twisted conformation on the C7 and C8 atoms, with puckering parameters of q₂ = 0.124 (2) Å, ϕ = 306.8 (7). The pyrrolidine ring in the indole ring system adopts an envelope conformation on the C12 atom, with puckering parameters q₂ = 0.113 (2) Å, ϕ = 251.6 (9).

In the crystal, six hydrogen bonds formed by each molecule. These include the formation of three inversion related contacts and atom O3 acting as a trifurcated acceptor. The molecules are stabilized by intermolecular C–H···O hydrogen bonds forming R²₂(8)rings from C9-H9···O3, contacts (Bernstein et al., 1995) while C5–H5···O3 contacts and C22-H22B···O3, H bonds generate R²₂(16) rings resulting in a three dimensional array Figure 2.

Related literature top

For the biological activity of spiro-pyrrolidine derivatives, see: Obniska et al. (2003); Peddi et al. (2004); Kaminski & Obniska (2008); Stylianakis et al. (2003); Waldmann (1995). For the use of optically active pyrrolidines as intermediates, chiral ligands or auxiliaries in controlled asymmetric synthesis, see: Suzuki et al. (1994); Huryn et al. (1991). For related structures, see: Ganesh et al. (2012); Wei et al. (2011). For puckering parameters, see: Cremer & Pople (1975) and for hydrogen-bond motifs see Bernstein et al. (1995).

Experimental top

A mixture of 1 equivalent of (E)-methyl 2-(5-chloro-1-methyl-2-oxoindolin-3-ylidene) acetate, 1 equivalent of isatin, 1H-indole-2,3-dione, and 1.5 equivalent of sarcosine, N-methylglycine were dissolved in acetonitrile. This reaction mixture was refluxed at 80°C for 8 hours. Progress of the reaction was monitored by thin layer chromatography. The product was dried and purified by column chromatography using ethyl acetate and hexane (1:9) as eluent to afford the title compound. (Yield = 90%). Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a solution in ethyl acetate at room temperature.

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 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The structure of showing the atom-numbering scheme. The displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular packing viewed along a. Dashed lines show the intermolecular N–H···O and C–H···O hydrogen bonds.

Methyl 5''-chloro-1',1''-dimethyl-2,2''-dioxodispiro[indoline-3,2'-pyrrolidine-3',3''-indoline]-4'-carboxylate top

Crystal data top

C₂₂H₂₀ClN₃O₄	F(000) = 888
M_r = 425.86	D_x = 1.394 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5021 reflections
a = 9.2543 (4) Å	θ = 2.0–28.3°
b = 18.1387 (7) Å	µ = 0.22 mm⁻¹
c = 12.5147 (5) Å	T = 293 K
β = 105.026 (2)°	Block, colourless
V = 2028.90 (14) Å³	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection top

Bruker APEXII CCD area detector diffractometer	5021 independent reflections
Radiation source: fine-focus sealed tube	3789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ω and ϕ scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −12→12
T_min = 0.936, T_max = 0.957	k = −24→24
18586 measured reflections	l = −16→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0572P)² + 0.6292P] where P = (F_o² + 2F_c²)/3
5021 reflections	(Δ/σ)_max < 0.001
278 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₂H₂₀ClN₃O₄	V = 2028.90 (14) Å³
M_r = 425.86	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.2543 (4) Å	µ = 0.22 mm⁻¹
b = 18.1387 (7) Å	T = 293 K
c = 12.5147 (5) Å	0.30 × 0.25 × 0.20 mm
β = 105.026 (2)°

Data collection top

Bruker APEXII CCD area detector diffractometer	5021 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3789 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.957	R_int = 0.030
18586 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.125	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.33 e Å⁻³
5021 reflections	Δρ_min = −0.21 e Å⁻³
278 parameters

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. 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 > 2sigma(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
C1	0.59371 (19)	0.05207 (9)	0.28439 (13)	0.0423 (4)
C2	0.45435 (17)	0.08424 (8)	0.24338 (12)	0.0358 (3)
H2	0.3891	0.0908	0.2880	0.043*
C3	0.41592 (15)	0.10629 (8)	0.13379 (12)	0.0301 (3)
C4	0.51723 (16)	0.09636 (8)	0.06936 (12)	0.0334 (3)
C5	0.65753 (18)	0.06619 (10)	0.11172 (15)	0.0446 (4)
H5	0.7247	0.0612	0.0683	0.053*
C6	0.69446 (19)	0.04367 (10)	0.22136 (16)	0.0486 (4)
H6	0.7877	0.0228	0.2525	0.058*
C7	0.27545 (15)	0.14084 (8)	0.06175 (11)	0.0294 (3)
C8	0.30532 (17)	0.13446 (8)	−0.05324 (12)	0.0340 (3)
C9	0.11746 (16)	0.10891 (9)	0.05792 (13)	0.0365 (3)
H9	0.0726	0.0954	−0.0194	0.044*
C10	0.02656 (18)	0.17386 (9)	0.08235 (17)	0.0473 (4)
H10A	−0.0777	0.1698	0.0417	0.057*
H10B	0.0331	0.1775	0.1608	0.057*
C11	0.0415 (2)	0.30826 (11)	0.0677 (2)	0.0601 (5)
H11A	0.0551	0.3134	0.1460	0.090*
H11B	−0.0631	0.3117	0.0308	0.090*
H11C	0.0949	0.3467	0.0417	0.090*
C12	0.25861 (16)	0.22640 (8)	0.08568 (12)	0.0319 (3)
C13	0.32532 (18)	0.24031 (8)	0.21214 (13)	0.0361 (3)
C14	0.47566 (18)	0.30011 (8)	0.12068 (13)	0.0362 (3)
C15	0.5915 (2)	0.34053 (11)	0.09938 (15)	0.0489 (4)
H15	0.6722	0.3557	0.1563	0.059*
C16	0.5830 (2)	0.35771 (11)	−0.00992 (16)	0.0536 (5)
H16	0.6609	0.3837	−0.0267	0.064*
C17	0.4617 (2)	0.33718 (11)	−0.09432 (15)	0.0507 (4)
H17	0.4572	0.3508	−0.1668	0.061*
C18	0.3457 (2)	0.29619 (9)	−0.07182 (14)	0.0426 (4)
H18	0.2630	0.2828	−0.1284	0.051*
C19	0.35598 (16)	0.27576 (8)	0.03628 (12)	0.0333 (3)
C20	0.12538 (16)	0.03924 (9)	0.12354 (14)	0.0397 (4)
C21	0.1033 (3)	−0.01945 (12)	0.2852 (2)	0.0683 (6)
H21A	0.0331	−0.0556	0.2467	0.102*
H21B	0.0828	−0.0082	0.3548	0.102*
H21C	0.2030	−0.0385	0.2980	0.102*
C22	0.5254 (2)	0.11715 (12)	−0.12913 (15)	0.0528 (5)
H22A	0.4533	0.1265	−0.1982	0.079*
H22B	0.5717	0.0701	−0.1322	0.079*
H22C	0.6004	0.1550	−0.1158	0.079*
N1	0.45105 (15)	0.11694 (7)	−0.04029 (10)	0.0367 (3)
N2	0.09833 (14)	0.23692 (7)	0.04428 (12)	0.0406 (3)
N3	0.45486 (16)	0.27829 (8)	0.22362 (12)	0.0406 (3)
O1	0.21387 (13)	0.14407 (7)	−0.14168 (9)	0.0467 (3)
O2	0.27254 (15)	0.22036 (7)	0.28633 (10)	0.0516 (3)
O3	0.16251 (15)	−0.01881 (7)	0.09239 (12)	0.0535 (3)
O4	0.08942 (15)	0.04712 (7)	0.21895 (11)	0.0513 (3)
Cl1	0.63981 (7)	0.01829 (3)	0.41915 (4)	0.07053 (19)
H3	0.513 (2)	0.2916 (11)	0.2850 (18)	0.049 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0456 (9)	0.0388 (8)	0.0358 (8)	0.0052 (7)	−0.0016 (7)	0.0025 (6)
C2	0.0376 (8)	0.0349 (7)	0.0336 (8)	0.0014 (6)	0.0071 (6)	0.0003 (6)
C3	0.0270 (6)	0.0294 (7)	0.0325 (7)	−0.0002 (5)	0.0053 (5)	−0.0014 (5)
C4	0.0305 (7)	0.0335 (7)	0.0356 (8)	−0.0014 (6)	0.0076 (6)	−0.0012 (6)
C5	0.0316 (8)	0.0501 (9)	0.0524 (10)	0.0058 (7)	0.0117 (7)	−0.0023 (8)
C6	0.0341 (8)	0.0506 (10)	0.0540 (10)	0.0111 (7)	−0.0014 (7)	−0.0009 (8)
C7	0.0263 (7)	0.0323 (7)	0.0286 (7)	−0.0005 (5)	0.0052 (5)	−0.0001 (5)
C8	0.0367 (8)	0.0330 (7)	0.0310 (7)	−0.0001 (6)	0.0067 (6)	−0.0023 (6)
C9	0.0269 (7)	0.0396 (8)	0.0411 (8)	−0.0036 (6)	0.0054 (6)	0.0015 (6)
C10	0.0304 (8)	0.0446 (9)	0.0689 (12)	0.0030 (7)	0.0162 (8)	0.0085 (8)
C11	0.0521 (11)	0.0455 (10)	0.0865 (15)	0.0154 (8)	0.0250 (10)	0.0088 (10)
C12	0.0308 (7)	0.0327 (7)	0.0323 (7)	0.0014 (6)	0.0082 (6)	0.0022 (6)
C13	0.0410 (8)	0.0346 (7)	0.0343 (8)	0.0038 (6)	0.0130 (6)	−0.0011 (6)
C14	0.0392 (8)	0.0342 (7)	0.0354 (8)	−0.0014 (6)	0.0099 (6)	−0.0026 (6)
C15	0.0441 (9)	0.0532 (10)	0.0481 (10)	−0.0141 (8)	0.0093 (8)	−0.0031 (8)
C16	0.0530 (11)	0.0557 (11)	0.0569 (11)	−0.0133 (8)	0.0231 (9)	0.0038 (9)
C17	0.0635 (11)	0.0524 (10)	0.0403 (9)	−0.0060 (9)	0.0206 (8)	0.0075 (8)
C18	0.0465 (9)	0.0432 (9)	0.0353 (8)	−0.0043 (7)	0.0057 (7)	0.0043 (7)
C19	0.0350 (7)	0.0313 (7)	0.0340 (7)	−0.0006 (6)	0.0100 (6)	−0.0004 (6)
C20	0.0264 (7)	0.0416 (8)	0.0490 (9)	−0.0062 (6)	0.0059 (6)	−0.0003 (7)
C21	0.0829 (16)	0.0602 (13)	0.0651 (14)	0.0020 (11)	0.0252 (12)	0.0181 (10)
C22	0.0556 (11)	0.0664 (12)	0.0441 (10)	0.0031 (9)	0.0265 (8)	0.0001 (8)
N1	0.0373 (7)	0.0425 (7)	0.0319 (6)	0.0029 (5)	0.0122 (5)	−0.0009 (5)
N2	0.0295 (6)	0.0379 (7)	0.0538 (8)	0.0059 (5)	0.0096 (6)	0.0070 (6)
N3	0.0455 (8)	0.0442 (8)	0.0300 (7)	−0.0070 (6)	0.0060 (6)	−0.0053 (6)
O1	0.0484 (7)	0.0567 (7)	0.0291 (6)	0.0048 (6)	−0.0004 (5)	−0.0010 (5)
O2	0.0606 (8)	0.0612 (8)	0.0394 (6)	−0.0015 (6)	0.0243 (6)	0.0023 (6)
O3	0.0497 (7)	0.0394 (7)	0.0746 (9)	0.0012 (5)	0.0218 (7)	−0.0042 (6)
O4	0.0610 (8)	0.0437 (7)	0.0529 (7)	0.0004 (6)	0.0213 (6)	0.0059 (6)
Cl1	0.0869 (4)	0.0727 (4)	0.0425 (3)	0.0259 (3)	−0.0003 (2)	0.0164 (2)

Geometric parameters (Å, º) top

C1—C6	1.377 (3)	C12—N2	1.4514 (18)
C1—C2	1.387 (2)	C12—C19	1.511 (2)
C1—Cl1	1.7403 (17)	C12—C13	1.563 (2)
C2—C3	1.384 (2)	C13—O2	1.2110 (19)
C2—H2	0.9300	C13—N3	1.358 (2)
C3—C4	1.398 (2)	C14—C15	1.381 (2)
C3—C7	1.5125 (19)	C14—C19	1.390 (2)
C4—C5	1.382 (2)	C14—N3	1.408 (2)
C4—N1	1.401 (2)	C15—C16	1.385 (3)
C5—C6	1.387 (3)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.378 (3)
C6—H6	0.9300	C16—H16	0.9300
C7—C8	1.539 (2)	C17—C18	1.393 (2)
C7—C9	1.5617 (19)	C17—H17	0.9300
C7—C12	1.596 (2)	C18—C19	1.382 (2)
C8—O1	1.2190 (18)	C18—H18	0.9300
C8—N1	1.354 (2)	C20—O3	1.203 (2)
C9—C20	1.499 (2)	C20—O4	1.328 (2)
C9—C10	1.524 (2)	C21—O4	1.452 (2)
C9—H9	0.9800	C21—H21A	0.9600
C10—N2	1.463 (2)	C21—H21B	0.9600
C10—H10A	0.9700	C21—H21C	0.9600
C10—H10B	0.9700	C22—N1	1.451 (2)
C11—N2	1.455 (2)	C22—H22A	0.9600
C11—H11A	0.9600	C22—H22B	0.9600
C11—H11B	0.9600	C22—H22C	0.9600
C11—H11C	0.9600	N3—H3	0.85 (2)

C6—C1—C2	122.50 (15)	C19—C12—C7	113.69 (12)
C6—C1—Cl1	118.94 (13)	C13—C12—C7	108.35 (11)
C2—C1—Cl1	118.52 (14)	O2—C13—N3	126.24 (15)
C3—C2—C1	117.63 (15)	O2—C13—C12	126.59 (15)
C3—C2—H2	121.2	N3—C13—C12	107.17 (13)
C1—C2—H2	121.2	C15—C14—C19	121.86 (15)
C2—C3—C4	119.74 (13)	C15—C14—N3	128.56 (15)
C2—C3—C7	132.13 (13)	C19—C14—N3	109.57 (13)
C4—C3—C7	108.12 (12)	C14—C15—C16	117.50 (16)
C5—C4—C3	122.27 (14)	C14—C15—H15	121.2
C5—C4—N1	127.60 (14)	C16—C15—H15	121.2
C3—C4—N1	110.03 (13)	C17—C16—C15	121.52 (17)
C4—C5—C6	117.53 (15)	C17—C16—H16	119.2
C4—C5—H5	121.2	C15—C16—H16	119.2
C6—C5—H5	121.2	C16—C17—C18	120.42 (16)
C1—C6—C5	120.29 (15)	C16—C17—H17	119.8
C1—C6—H6	119.9	C18—C17—H17	119.8
C5—C6—H6	119.9	C19—C18—C17	118.67 (16)
C3—C7—C8	101.03 (11)	C19—C18—H18	120.7
C3—C7—C9	121.19 (12)	C17—C18—H18	120.7
C8—C7—C9	109.70 (12)	C18—C19—C14	119.87 (14)
C3—C7—C12	113.69 (11)	C18—C19—C12	131.46 (14)
C8—C7—C12	107.37 (11)	C14—C19—C12	108.64 (13)
C9—C7—C12	103.31 (11)	O3—C20—O4	123.00 (16)
O1—C8—N1	125.30 (14)	O3—C20—C9	122.54 (16)
O1—C8—C7	126.00 (14)	O4—C20—C9	114.46 (14)
N1—C8—C7	108.70 (12)	O4—C21—H21A	109.5
C20—C9—C10	119.54 (14)	O4—C21—H21B	109.5
C20—C9—C7	112.55 (12)	H21A—C21—H21B	109.5
C10—C9—C7	105.56 (12)	O4—C21—H21C	109.5
C20—C9—H9	106.1	H21A—C21—H21C	109.5
C10—C9—H9	106.1	H21B—C21—H21C	109.5
C7—C9—H9	106.1	N1—C22—H22A	109.5
N2—C10—C9	102.60 (13)	N1—C22—H22B	109.5
N2—C10—H10A	111.2	H22A—C22—H22B	109.5
C9—C10—H10A	111.2	N1—C22—H22C	109.5
N2—C10—H10B	111.2	H22A—C22—H22C	109.5
C9—C10—H10B	111.2	H22B—C22—H22C	109.5
H10A—C10—H10B	109.2	C8—N1—C4	110.42 (12)
N2—C11—H11A	109.5	C8—N1—C22	124.27 (14)
N2—C11—H11B	109.5	C4—N1—C22	125.28 (14)
H11A—C11—H11B	109.5	C12—N2—C11	115.75 (14)
N2—C11—H11C	109.5	C12—N2—C10	106.81 (12)
H11A—C11—H11C	109.5	C11—N2—C10	114.29 (14)
H11B—C11—H11C	109.5	C13—N3—C14	111.86 (14)
N2—C12—C19	116.02 (12)	C13—N3—H3	125.2 (13)
N2—C12—C13	116.05 (12)	C14—N3—H3	122.7 (13)
C19—C12—C13	101.40 (12)	C20—O4—C21	114.76 (15)
N2—C12—C7	101.61 (11)

C6—C1—C2—C3	2.0 (2)	C19—C12—C13—N3	−11.00 (15)
Cl1—C1—C2—C3	−175.78 (11)	C7—C12—C13—N3	108.91 (13)
C1—C2—C3—C4	−0.6 (2)	C19—C14—C15—C16	1.4 (3)
C1—C2—C3—C7	178.34 (15)	N3—C14—C15—C16	−177.23 (17)
C2—C3—C4—C5	−1.2 (2)	C14—C15—C16—C17	1.8 (3)
C7—C3—C4—C5	179.57 (14)	C15—C16—C17—C18	−2.1 (3)
C2—C3—C4—N1	175.27 (13)	C16—C17—C18—C19	−0.9 (3)
C7—C3—C4—N1	−3.92 (16)	C17—C18—C19—C14	4.1 (2)
C3—C4—C5—C6	1.8 (2)	C17—C18—C19—C12	−173.57 (16)
N1—C4—C5—C6	−174.09 (15)	C15—C14—C19—C18	−4.4 (2)
C2—C1—C6—C5	−1.4 (3)	N3—C14—C19—C18	174.48 (14)
Cl1—C1—C6—C5	176.30 (14)	C15—C14—C19—C12	173.71 (16)
C4—C5—C6—C1	−0.5 (3)	N3—C14—C19—C12	−7.39 (17)
C2—C3—C7—C8	−169.10 (15)	N2—C12—C19—C18	−44.6 (2)
C4—C3—C7—C8	9.95 (15)	C13—C12—C19—C18	−171.21 (16)
C2—C3—C7—C9	−47.8 (2)	C7—C12—C19—C18	72.7 (2)
C4—C3—C7—C9	131.25 (14)	N2—C12—C19—C14	137.60 (14)
C2—C3—C7—C12	76.21 (19)	C13—C12—C19—C14	10.95 (15)
C4—C3—C7—C12	−104.73 (13)	C7—C12—C19—C14	−105.10 (14)
C3—C7—C8—O1	167.44 (15)	C10—C9—C20—O3	161.37 (16)
C9—C7—C8—O1	38.4 (2)	C7—C9—C20—O3	−73.93 (19)
C12—C7—C8—O1	−73.23 (18)	C10—C9—C20—O4	−19.2 (2)
C3—C7—C8—N1	−13.09 (15)	C7—C9—C20—O4	105.49 (15)
C9—C7—C8—N1	−142.15 (13)	O1—C8—N1—C4	−168.84 (15)
C12—C7—C8—N1	106.24 (13)	C7—C8—N1—C4	11.68 (16)
C3—C7—C9—C20	−5.1 (2)	O1—C8—N1—C22	9.1 (3)
C8—C7—C9—C20	111.93 (14)	C7—C8—N1—C22	−170.33 (15)
C12—C7—C9—C20	−133.82 (13)	C5—C4—N1—C8	171.24 (16)
C3—C7—C9—C10	126.97 (15)	C3—C4—N1—C8	−5.04 (17)
C8—C7—C9—C10	−116.01 (14)	C5—C4—N1—C22	−6.7 (3)
C12—C7—C9—C10	−1.77 (15)	C3—C4—N1—C22	177.01 (15)
C20—C9—C10—N2	154.82 (14)	C19—C12—N2—C11	−64.38 (19)
C7—C9—C10—N2	26.84 (17)	C13—C12—N2—C11	54.53 (19)
C3—C7—C12—N2	−157.26 (12)	C7—C12—N2—C11	171.79 (14)
C8—C7—C12—N2	91.88 (13)	C19—C12—N2—C10	167.10 (14)
C9—C7—C12—N2	−24.03 (14)	C13—C12—N2—C10	−73.99 (17)
C3—C7—C12—C19	77.35 (15)	C7—C12—N2—C10	43.27 (15)
C8—C7—C12—C19	−33.51 (15)	C9—C10—N2—C12	−45.11 (17)
C9—C7—C12—C19	−149.42 (12)	C9—C10—N2—C11	−174.47 (15)
C3—C7—C12—C13	−34.55 (16)	O2—C13—N3—C14	−173.29 (16)
C8—C7—C12—C13	−145.41 (12)	C12—C13—N3—C14	7.43 (17)
C9—C7—C12—C13	98.68 (13)	C15—C14—N3—C13	178.58 (17)
N2—C12—C13—O2	43.1 (2)	C19—C14—N3—C13	−0.23 (19)
C19—C12—C13—O2	169.72 (16)	O3—C20—O4—C21	2.0 (2)
C7—C12—C13—O2	−70.37 (19)	C9—C20—O4—C21	−177.38 (16)
N2—C12—C13—N3	−137.63 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.85 (2)	2.18 (2)	2.9112 (18)	143.3 (18)
C15—H15···O1ⁱ	0.93	2.46	3.156 (2)	132
C22—H22B···O3ⁱⁱ	0.96	2.56	3.324 (2)	137
C5—H5···O3ⁱⁱ	0.93	2.61	3.499 (2)	160
C9—H9···O3ⁱⁱⁱ	0.98	2.54	3.224 (2)	127
C9—H9···O1	0.98	2.42	2.932 (2)	112

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₀ClN₃O₄
M_r	425.86
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.2543 (4), 18.1387 (7), 12.5147 (5)
β (°)	105.026 (2)
V (Å³)	2028.90 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.936, 0.957
No. of measured, independent and observed [I > 2σ(I)] reflections	18586, 5021, 3789
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.125, 1.06
No. of reflections	5021
No. of parameters	278
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.21

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