2'-Hy-droxy-methyl-1'-(4-methyl-phen-yl)-2'-nitro-1',2',5',6',7',7a'-hexa-hydro-spiro-[indoline-3,3'-pyrrolizin]-2-one.

In the title compound, C(22)H(23)N(3)O(4), the tolyl ring is almost perpendicular [83.86 (7)°] to the best plane through the eight atoms of the pyrrolizidine ring system. The mol-ecular conformation is stabilized by an intra-molecular O-H⋯O hydrogen bond. The crystal packing features inversion dimers with R(2) (2)(8) motifs linked by pairs of N-H⋯O hydrogen bonds.

Related literature

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

Crystal data

C22H23N3O4

M = 393.43

Triclinic,

a = 8.9172 (4) Å

b = 9.9953 (4) Å

c = 11.5931 (6) Å

α = 81.257 (3)°

β = 76.638 (3)°

γ = 83.805 (2)°

V = 990.79 (8) Å3

Z = 2

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.20 × 0.18 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

18094 measured reflections

4912 independent reflections

3737 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.175

S = 1.25

4912 reflections

264 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.34 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811055449/bt5744sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055449/bt5744Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C22H23N3O4	Z = 2
Mr = 393.43	F(000) = 416
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
4912 reflections	(Δ/σ)max = 0.007
264 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

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)

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.

Table 1

Hydrogen-bond geometry (Å, °)

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) .