2′-Hy­droxy­methyl-1′-(4-methyl­phen­yl)-2′-nitro-1′,2′,5′,6′,7′,7a′-hexa­hydro­spiro­[indoline-3,3′-pyrrolizin]-2-one

Sathya, S.; Bhaskaran, S.; Usha, G.; Sivakumar, N.; Bakthadoss, M.

doi:10.1107/S1600536811055449

2′-Hydroxymethyl-1′-(4-methylphenyl)-2′-nitro-1′,2′,5′,6′,7′,7a′-hexahydrospiro[indoline-3,3′-pyrrolizin]-2-one

S. Sathya, S. Bhaskaran, G. Usha, N. Sivakumar and M. Bakthadoss

In the title compound, C₂₂H₂₃N₃O₄, the tolyl ring is almost perpendicular [83.86 (7)°] to the best plane through the eight atoms of the pyrrolizidine ring system. The molecular conformation is stabilized by an intramolecular O—H

O hydrogen bond. The crystal packing features inversion dimers with R₂²(8) motifs linked by pairs of N—H

O hydrogen bonds.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536811055449/bt5744sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536811055449/bt5744Isup2.hkl Contains datablock I

CCDC reference: 868042

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.002 Å
R factor = 0.048
wR factor = 0.175
Data-to-parameter ratio = 18.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C12
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         37

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT007_ALERT_5_G Note: Number of Unrefined D-H Atoms ............          2
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 C8      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C9      (Verify) ....          S
PLAT793_ALERT_4_G The Model has Chirality at C14     (Verify) ....          R
PLAT793_ALERT_4_G The Model has Chirality at C15     (Verify) ....          R

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   2 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
   0 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

Comment top

The indole unit is observed in plants (Nigović et al., 2000). Some of the indole derivatives exhibit anti-tumour (Schollmeyer et al., 1995) and anti-bacterial (Okabe & Adachi,1998) activities. Sumatriptan, an indole derivative has been introduced into medicine as a drug for the treatment of migraine (Oxford, 1995). Pyrido [1, 2 - a]indole derivatives have been observed as potent inhibitors of HIV-typeI (Taylor et al., 1999). Spiro-indoles have been reported to exhibit fungicidal activity(Ali et al., 1989). In view of the wide spectrum of biological activity of indole and pyrrolizidine derivatives, the X-ray analysis of the title compound has been undertaken and the crystallographic details are reported in this communication. Bond lengths and bond angles of the pyrrolizidine group and the indole unit are in the same range as observed in reported structures (Usha et al., 2005) The C7 = O4 double bond is slightly elongated [1.225 (2) Å] and this may be due to the active involvement of O4 both in intra and intermolecular hydrogen bonding. The pyrrolizidine ring is perpendicular to the methyl benzyl ring [89.8 (1)°]. The pyrrolizidine and methyl benzyl ring make angles of 81.7 (1) and 68.9 (1)°, respectively, with the oxindole system. The sum of the angles around N2 and N3 [360 and 341.7°], indicates sp² and sp³ hybridization, respectively. The N3/C11—C14 ring adopts a half chair conformation with the smallest asymmetry parameter (Nardelli, 1983) of D2 (N3) = 0.018 (1)°. The asymmetry parameter DS (C9)= 0.024 (1)° indicates the half chair conformation of the N3/C8/C9/C15/C14 ring. The overall conformation of the pyrrolizidine ring is folded about the bridging bond N3—C14. In the title compound, each molecule is linked to two of its adjacent centro-symmetrically related molecules through N—H···O and C—H···O hydrogen bonds, forming dimers described by R²₂(8) and R²₂(18) rings. The atom O3 acts as a donor for an intrammolecular hydrogen bond.

Related literature top

For indole derivatives, see: Ali et al. (1989); Nigović et al. (2000); Okabe & Adachi (1998); Oxford (1995); Schollmeyer et al. (1995); Taylor et al. (1999). For a related structure, see: Usha et al. (2005). For ring conformations, see Nardelli (1983).

Experimental top

A mixture of (E)-2- nitro-3-p-tolylprop-2-en-1-ol(2 mmol, 0.39 g),isatin(2 mmol, 0.29 g)and l-proline (2 mmol, 0.23 g) in acetonitrile(8 ml) was refluxed for 2 h. After the completion of the reaction as indicated by TLC, the reaction mixture was concentrated and the resulting crude mass was diluted with water (20 ml) and extracted with ethyl acetate (3x10ml) and dried over anhydrous NaSO4 The organic layer was concentrated and purified by column chromatography on silica gel (Acme 100–200 mesh), usingethyl acetate: hexanes (3:7) to provide as a colorless solid in 59% (0.46 g)yield.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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, 1997); 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, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The packing of the molecules in the crystal structure. The dashed lines indicate the hydrogen bonds.

2'-Hydroxymethyl-1'-(4-methylphenyl)-2'-nitro-1',2',5',6',7',7a'- hexahydrospiro[indoline-3,3'-pyrrolizin]-2-one top

Crystal data top

C₂₂H₂₃N₃O₄	Z = 2
M_r = 393.43	F(000) = 416
Triclinic, P1	D_x = 1.319 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9172 (4) Å	Cell parameters from 4951 reflections
b = 9.9953 (4) Å	θ = 1.8–28.3°
c = 11.5931 (6) Å	µ = 0.09 mm⁻¹
α = 81.257 (3)°	T = 293 K
β = 76.638 (3)°	Block, colorless
γ = 83.805 (2)°	0.20 × 0.18 × 0.18 mm
V = 990.79 (8) Å³

Data collection top

Bruker Kappa APEXII CCD diffractometer	3737 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.028
Graphite monochromator	θ_max = 28.4°, θ_min = 1.8°
ω and ϕ scan	h = −11→11
18094 measured reflections	k = −13→13
4912 independent reflections	l = −15→11

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.25	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
4912 reflections	(Δ/σ)_max = 0.007
264 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₂₂H₂₃N₃O₄	γ = 83.805 (2)°
M_r = 393.43	V = 990.79 (8) Å³
Triclinic, P1	Z = 2
a = 8.9172 (4) Å	Mo Kα radiation
b = 9.9953 (4) Å	µ = 0.09 mm⁻¹
c = 11.5931 (6) Å	T = 293 K
α = 81.257 (3)°	0.20 × 0.18 × 0.18 mm
β = 76.638 (3)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	3737 reflections with I > 2σ(I)
18094 measured reflections	R_int = 0.028
4912 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.25	Δρ_max = 0.50 e Å⁻³
4912 reflections	Δρ_min = −0.34 e Å⁻³
264 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
C1	0.21898 (19)	0.62617 (16)	0.42758 (14)	0.0478 (4)
H1	0.1948	0.7087	0.4579	0.057*
C2	0.1894 (2)	0.50533 (18)	0.50230 (16)	0.0597 (5)
H2	0.1468	0.5068	0.5833	0.072*
C3	0.2229 (2)	0.38237 (18)	0.45695 (18)	0.0665 (5)
H3	0.2010	0.3023	0.5080	0.080*
C4	0.2878 (2)	0.37652 (16)	0.33808 (17)	0.0606 (5)
H4	0.3103	0.2940	0.3076	0.073*
C5	0.31830 (18)	0.49813 (14)	0.26526 (14)	0.0431 (3)
C6	0.28473 (16)	0.62292 (13)	0.30774 (13)	0.0371 (3)
C7	0.40581 (16)	0.64665 (13)	0.10119 (13)	0.0378 (3)
C8	0.33024 (15)	0.73416 (12)	0.20230 (12)	0.0329 (3)
C9	0.19143 (14)	0.83335 (12)	0.17272 (12)	0.0323 (3)
C10	0.20643 (18)	0.88938 (15)	0.03935 (13)	0.0426 (3)
H10A	0.2125	0.8142	−0.0059	0.051*
H10B	0.1143	0.9472	0.0299	0.051*
C11	0.56071 (19)	0.78765 (17)	0.27409 (19)	0.0574 (5)
H11A	0.6583	0.7713	0.2186	0.069*
H11B	0.5377	0.7054	0.3290	0.069*
C12	0.5667 (2)	0.9037 (2)	0.3407 (2)	0.0771 (7)
H12A	0.6405	0.9662	0.2935	0.093*
H12B	0.5966	0.8709	0.4159	0.093*
C13	0.40563 (19)	0.97253 (16)	0.36233 (15)	0.0511 (4)
H13A	0.4066	1.0672	0.3718	0.061*
H13B	0.3392	0.9272	0.4325	0.061*
C14	0.35435 (15)	0.95803 (13)	0.24826 (13)	0.0360 (3)
H14	0.3882	1.0341	0.1870	0.043*
C15	0.18254 (15)	0.94197 (12)	0.25671 (12)	0.0328 (3)
H15	0.1407	0.8995	0.3382	0.039*
C16	0.08246 (15)	1.07192 (13)	0.23587 (12)	0.0365 (3)
C17	−0.06238 (17)	1.08928 (15)	0.31073 (15)	0.0471 (4)
H17	−0.0947	1.0221	0.3739	0.056*
C18	−0.15936 (19)	1.20451 (16)	0.29307 (16)	0.0521 (4)
H18	−0.2560	1.2128	0.3442	0.063*
C19	−0.11602 (18)	1.30755 (15)	0.20124 (15)	0.0473 (4)
C20	0.0293 (2)	1.29239 (15)	0.12843 (15)	0.0497 (4)
H20	0.0624	1.3614	0.0672	0.060*
C21	0.12749 (18)	1.17662 (14)	0.14433 (14)	0.0443 (3)
H21	0.2243	1.1690	0.0933	0.053*
C22	−0.2232 (2)	1.42970 (17)	0.17871 (19)	0.0633 (5)
H22A	−0.3157	1.4262	0.2406	0.095*
H22B	−0.2490	1.4310	0.1026	0.095*
H22C	−0.1735	1.5104	0.1785	0.095*
N1	0.38738 (15)	0.51498 (12)	0.14359 (12)	0.0456 (3)
H1A	0.4148	0.4495	0.1010	0.055*
N2	0.04800 (14)	0.75474 (12)	0.20397 (12)	0.0422 (3)
N3	0.43621 (12)	0.83081 (11)	0.20981 (11)	0.0381 (3)
O1	−0.06118 (13)	0.78766 (13)	0.28004 (13)	0.0675 (4)
O2	0.05119 (15)	0.65971 (13)	0.14818 (13)	0.0665 (4)
O3	0.33650 (13)	0.96383 (11)	−0.00794 (10)	0.0511 (3)
H3A	0.4152	0.9135	−0.0065	0.077*
O4	0.47420 (14)	0.69055 (10)	0.00021 (10)	0.0502 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0539 (9)	0.0497 (8)	0.0399 (9)	0.0035 (7)	−0.0110 (7)	−0.0100 (6)
C2	0.0661 (11)	0.0658 (11)	0.0403 (9)	0.0023 (9)	−0.0074 (8)	0.0034 (8)
C3	0.0788 (13)	0.0494 (9)	0.0619 (12)	0.0034 (8)	−0.0128 (10)	0.0120 (8)
C4	0.0760 (13)	0.0385 (8)	0.0622 (12)	0.0062 (8)	−0.0124 (10)	−0.0019 (7)
C5	0.0454 (8)	0.0383 (7)	0.0451 (9)	0.0042 (6)	−0.0102 (7)	−0.0086 (6)
C6	0.0384 (7)	0.0374 (6)	0.0366 (7)	0.0021 (5)	−0.0115 (6)	−0.0066 (5)
C7	0.0365 (7)	0.0376 (7)	0.0417 (8)	−0.0003 (5)	−0.0070 (6)	−0.0164 (6)
C8	0.0322 (7)	0.0335 (6)	0.0348 (7)	−0.0006 (5)	−0.0067 (5)	−0.0127 (5)
C9	0.0279 (6)	0.0335 (6)	0.0367 (7)	−0.0031 (5)	−0.0075 (5)	−0.0077 (5)
C10	0.0473 (8)	0.0464 (8)	0.0363 (8)	−0.0036 (6)	−0.0115 (6)	−0.0086 (6)
C11	0.0405 (8)	0.0548 (9)	0.0891 (13)	0.0092 (7)	−0.0314 (9)	−0.0296 (9)
C12	0.0755 (13)	0.0767 (12)	0.1030 (17)	0.0189 (10)	−0.0583 (13)	−0.0437 (12)
C13	0.0588 (10)	0.0488 (8)	0.0568 (10)	0.0035 (7)	−0.0270 (8)	−0.0244 (7)
C14	0.0352 (7)	0.0335 (6)	0.0431 (8)	0.0002 (5)	−0.0114 (6)	−0.0143 (5)
C15	0.0317 (7)	0.0334 (6)	0.0328 (7)	0.0009 (5)	−0.0051 (5)	−0.0083 (5)
C16	0.0352 (7)	0.0366 (6)	0.0387 (8)	0.0021 (5)	−0.0083 (6)	−0.0114 (5)
C17	0.0423 (8)	0.0444 (8)	0.0492 (9)	0.0032 (6)	−0.0003 (7)	−0.0094 (6)
C18	0.0387 (8)	0.0524 (9)	0.0638 (11)	0.0091 (7)	−0.0055 (7)	−0.0207 (8)
C19	0.0476 (9)	0.0398 (7)	0.0627 (10)	0.0066 (6)	−0.0251 (8)	−0.0186 (7)
C20	0.0558 (10)	0.0395 (7)	0.0556 (10)	−0.0003 (7)	−0.0198 (8)	−0.0029 (7)
C21	0.0405 (8)	0.0410 (7)	0.0489 (9)	0.0015 (6)	−0.0066 (7)	−0.0062 (6)
C22	0.0604 (11)	0.0472 (9)	0.0901 (14)	0.0132 (8)	−0.0346 (10)	−0.0176 (9)
N1	0.0561 (8)	0.0340 (6)	0.0454 (7)	0.0031 (5)	−0.0045 (6)	−0.0154 (5)
N2	0.0355 (6)	0.0417 (6)	0.0514 (8)	−0.0069 (5)	−0.0139 (6)	−0.0031 (5)
N3	0.0280 (6)	0.0383 (6)	0.0525 (7)	0.0012 (4)	−0.0111 (5)	−0.0192 (5)
O1	0.0370 (6)	0.0687 (8)	0.0894 (10)	−0.0126 (6)	0.0076 (6)	−0.0141 (7)
O2	0.0668 (8)	0.0596 (7)	0.0847 (10)	−0.0225 (6)	−0.0224 (7)	−0.0237 (7)
O3	0.0543 (7)	0.0523 (6)	0.0417 (6)	−0.0083 (5)	−0.0003 (5)	−0.0035 (5)
O4	0.0595 (7)	0.0436 (6)	0.0429 (6)	−0.0035 (5)	0.0053 (5)	−0.0169 (5)

Geometric parameters (Å, º) top

C1—C6	1.381 (2)	C12—H12A	0.9700
C1—C2	1.387 (2)	C12—H12B	0.9700
C1—H1	0.9300	C13—C14	1.527 (2)
C2—C3	1.386 (3)	C13—H13A	0.9700
C2—H2	0.9300	C13—H13B	0.9700
C3—C4	1.373 (3)	C14—N3	1.4732 (16)
C3—H3	0.9300	C14—C15	1.5367 (18)
C4—C5	1.385 (2)	C14—H14	0.9800
C4—H4	0.9300	C15—C16	1.5153 (17)
C5—C6	1.3878 (19)	C15—H15	0.9800
C5—N1	1.3950 (19)	C16—C17	1.390 (2)
C6—C8	1.5331 (19)	C16—C21	1.392 (2)
C7—O4	1.2274 (18)	C17—C18	1.383 (2)
C7—N1	1.3465 (18)	C17—H17	0.9300
C7—C8	1.5532 (18)	C18—C19	1.381 (2)
C8—N3	1.4472 (16)	C18—H18	0.9300
C8—C9	1.5686 (18)	C19—C20	1.381 (2)
C9—N2	1.5167 (16)	C19—C22	1.496 (2)
C9—C10	1.543 (2)	C20—C21	1.389 (2)
C9—C15	1.5493 (17)	C20—H20	0.9300
C10—O3	1.4028 (18)	C21—H21	0.9300
C10—H10A	0.9700	C22—H22A	0.9600
C10—H10B	0.9700	C22—H22B	0.9600
C11—N3	1.4680 (19)	C22—H22C	0.9600
C11—C12	1.499 (2)	N1—H1A	0.8600
C11—H11A	0.9700	N2—O1	1.2067 (18)
C11—H11B	0.9700	N2—O2	1.2223 (17)
C12—C13	1.507 (2)	O3—H3A	0.8200

C6—C1—C2	119.44 (15)	C12—C13—H13A	111.4
C6—C1—H1	120.3	C14—C13—H13A	111.4
C2—C1—H1	120.3	C12—C13—H13B	111.4
C1—C2—C3	120.40 (17)	C14—C13—H13B	111.4
C1—C2—H2	119.8	H13A—C13—H13B	109.2
C3—C2—H2	119.8	N3—C14—C13	104.96 (11)
C4—C3—C2	121.25 (16)	N3—C14—C15	105.21 (10)
C4—C3—H3	119.4	C13—C14—C15	118.35 (12)
C2—C3—H3	119.4	N3—C14—H14	109.3
C3—C4—C5	117.47 (16)	C13—C14—H14	109.3
C3—C4—H4	121.3	C15—C14—H14	109.3
C5—C4—H4	121.3	C16—C15—C14	116.15 (11)
C4—C5—C6	122.65 (15)	C16—C15—C9	117.55 (11)
C4—C5—N1	126.82 (14)	C14—C15—C9	101.87 (10)
C6—C5—N1	110.52 (12)	C16—C15—H15	106.8
C1—C6—C5	118.79 (14)	C14—C15—H15	106.8
C1—C6—C8	133.01 (12)	C9—C15—H15	106.8
C5—C6—C8	108.19 (12)	C17—C16—C21	117.36 (13)
O4—C7—N1	125.80 (13)	C17—C16—C15	119.24 (13)
O4—C7—C8	125.37 (12)	C21—C16—C15	123.40 (12)
N1—C7—C8	108.81 (12)	C18—C17—C16	121.25 (15)
N3—C8—C6	119.23 (11)	C18—C17—H17	119.4
N3—C8—C7	109.64 (10)	C16—C17—H17	119.4
C6—C8—C7	100.66 (10)	C17—C18—C19	121.52 (15)
N3—C8—C9	100.32 (9)	C17—C18—H18	119.2
C6—C8—C9	114.29 (11)	C19—C18—H18	119.2
C7—C8—C9	113.20 (10)	C18—C19—C20	117.47 (13)
N2—C9—C10	104.26 (11)	C18—C19—C22	121.66 (15)
N2—C9—C15	112.33 (11)	C20—C19—C22	120.85 (16)
C10—C9—C15	115.03 (11)	C19—C20—C21	121.66 (15)
N2—C9—C8	108.15 (10)	C19—C20—H20	119.2
C10—C9—C8	115.16 (11)	C21—C20—H20	119.2
C15—C9—C8	101.99 (10)	C20—C21—C16	120.71 (14)
O3—C10—C9	113.06 (12)	C20—C21—H21	119.6
O3—C10—H10A	109.0	C16—C21—H21	119.6
C9—C10—H10A	109.0	C19—C22—H22A	109.5
O3—C10—H10B	109.0	C19—C22—H22B	109.5
C9—C10—H10B	109.0	H22A—C22—H22B	109.5
H10A—C10—H10B	107.8	C19—C22—H22C	109.5
N3—C11—C12	104.69 (13)	H22A—C22—H22C	109.5
N3—C11—H11A	110.8	H22B—C22—H22C	109.5
C12—C11—H11A	110.8	C7—N1—C5	111.50 (12)
N3—C11—H11B	110.8	C7—N1—H1A	124.3
C12—C11—H11B	110.8	C5—N1—H1A	124.2
H11A—C11—H11B	108.9	O1—N2—O2	123.69 (13)
C11—C12—C13	105.71 (14)	O1—N2—C9	119.96 (12)
C11—C12—H12A	110.6	O2—N2—C9	116.35 (12)
C13—C12—H12A	110.6	C8—N3—C11	119.86 (12)
C11—C12—H12B	110.6	C8—N3—C14	111.92 (10)
C13—C12—H12B	110.6	C11—N3—C14	109.93 (11)
H12A—C12—H12B	108.7	C10—O3—H3A	109.5
C12—C13—C14	102.09 (13)

C6—C1—C2—C3	−1.1 (3)	N2—C9—C15—C16	−76.79 (15)
C1—C2—C3—C4	0.9 (3)	C10—C9—C15—C16	42.26 (16)
C2—C3—C4—C5	−0.1 (3)	C8—C9—C15—C16	167.64 (11)
C3—C4—C5—C6	−0.6 (3)	N2—C9—C15—C14	155.06 (11)
C3—C4—C5—N1	178.06 (17)	C10—C9—C15—C14	−85.88 (13)
C2—C1—C6—C5	0.5 (2)	C8—C9—C15—C14	39.49 (13)
C2—C1—C6—C8	179.21 (15)	C14—C15—C16—C17	−136.58 (14)
C4—C5—C6—C1	0.4 (2)	C9—C15—C16—C17	102.44 (15)
N1—C5—C6—C1	−178.47 (13)	C14—C15—C16—C21	43.66 (18)
C4—C5—C6—C8	−178.65 (15)	C9—C15—C16—C21	−77.31 (17)
N1—C5—C6—C8	2.51 (17)	C21—C16—C17—C18	1.6 (2)
C1—C6—C8—N3	56.6 (2)	C15—C16—C17—C18	−178.20 (13)
C5—C6—C8—N3	−124.58 (13)	C16—C17—C18—C19	−0.6 (2)
C1—C6—C8—C7	176.41 (15)	C17—C18—C19—C20	−1.0 (2)
C5—C6—C8—C7	−4.77 (14)	C17—C18—C19—C22	177.39 (15)
C1—C6—C8—C9	−61.95 (19)	C18—C19—C20—C21	1.7 (2)
C5—C6—C8—C9	116.88 (12)	C22—C19—C20—C21	−176.77 (14)
O4—C7—C8—N3	−46.30 (18)	C19—C20—C21—C16	−0.7 (2)
N1—C7—C8—N3	132.12 (12)	C17—C16—C21—C20	−0.9 (2)
O4—C7—C8—C6	−172.79 (14)	C15—C16—C21—C20	178.82 (13)
N1—C7—C8—C6	5.63 (14)	O4—C7—N1—C5	173.80 (14)
O4—C7—C8—C9	64.80 (18)	C8—C7—N1—C5	−4.61 (17)
N1—C7—C8—C9	−116.79 (13)	C4—C5—N1—C7	−177.40 (16)
N3—C8—C9—N2	−160.20 (10)	C6—C5—N1—C7	1.38 (19)
C6—C8—C9—N2	−31.39 (14)	C10—C9—N2—O1	−119.17 (15)
C7—C8—C9—N2	83.07 (13)	C15—C9—N2—O1	6.03 (18)
N3—C8—C9—C10	83.67 (12)	C8—C9—N2—O1	117.81 (14)
C6—C8—C9—C10	−147.53 (11)	C10—C9—N2—O2	60.59 (15)
C7—C8—C9—C10	−33.06 (15)	C15—C9—N2—O2	−174.22 (12)
N3—C8—C9—C15	−41.62 (12)	C8—C9—N2—O2	−62.43 (16)
C6—C8—C9—C15	87.19 (12)	C6—C8—N3—C11	34.10 (18)
C7—C8—C9—C15	−158.34 (10)	C7—C8—N3—C11	−81.02 (16)
N2—C9—C10—O3	−178.62 (11)	C9—C8—N3—C11	159.63 (13)
C15—C9—C10—O3	57.92 (16)	C6—C8—N3—C14	−96.79 (14)
C8—C9—C10—O3	−60.29 (15)	C7—C8—N3—C14	148.08 (11)
N3—C11—C12—C13	27.5 (2)	C9—C8—N3—C14	28.74 (14)
C11—C12—C13—C14	−35.8 (2)	C12—C11—N3—C8	−139.59 (16)
C12—C13—C14—N3	30.41 (17)	C12—C11—N3—C14	−7.8 (2)
C12—C13—C14—C15	147.33 (15)	C13—C14—N3—C8	121.37 (13)
N3—C14—C15—C16	−151.72 (11)	C15—C14—N3—C8	−4.22 (15)
C13—C14—C15—C16	91.49 (15)	C13—C14—N3—C11	−14.42 (16)
N3—C14—C15—C9	−22.68 (13)	C15—C14—N3—C11	−140.01 (13)
C13—C14—C15—C9	−139.47 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O4ⁱ	0.86	2.00	2.8401 (15)	167
O3—H3A···O4	0.82	2.23	2.8686 (15)	135

Symmetry code: (i) −x+1, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₃N₃O₄
M_r	393.43
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.9172 (4), 9.9953 (4), 11.5931 (6)
α, β, γ (°)	81.257 (3), 76.638 (3), 83.805 (2)
V (Å³)	990.79 (8)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII CCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	18094, 4912, 3737
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.175, 1.25
No. of reflections	4912
No. of parameters	264
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.34

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).