3'-[Hy-droxy(4-oxo-4H-chromen-3-yl)meth-yl]-2-oxospiro-[indoline-3,2'-pyrrolidine]-3'-carbonitrile.

In the title compound, C(23)H(19)N(3)O(4), the pyran ring adopts a half-chair conformation, while the pyrrolidine (with a C atom as the flap atom) and the five-membered ring in the indoline (with a C atom as the flap atom) ring system adopt slight envelope conformations. The pyrrolidine ring makes dihedral angles of 83.3 (1) and 60.4 (1)° with the mean plane through all non-H atoms of the indoline and chromene ring systems, respectively. In the crystal, mol-ecules are connected by two unique N-H⋯O and O-H⋯O hydrogen-bonding inter-actions, which form centrosymmetric patterns described by graph-set motifs R(2) (2)(18) and R(2) (2)(14). These two motifs combine to form a hydrogen-bonded chain which propagates in the a-axis direction. The crystal structure is also stablized by C-H⋯O inter-actions and by aromatic π-π stacking inter-actions between the pyran and benzene rings of neighbouring mol-ecules [centroid-centroid distance = 3.755 (1) Å and slippage = 1.371 (2) Å].

Related literature

For general background to the biological use of pyrrolidine derivatives, see: Pettersson et al. (2011 ▶); Bello et al. (2010 ▶). For ring puckering parameters, see: Cremer & Pople (1975 ▶) and for asymmetry parameters, see: Nardelli (1983 ▶). For the structure of another pyrrolidine derivatie, see: Selvanayagam et al. (2011 ▶).

Experimental

Crystal data

C23H19N3O4

M = 401.41

Triclinic,

a = 9.3483 (7) Å

b = 10.2256 (9) Å

c = 10.9080 (9) Å

α = 71.832 (5)°

β = 88.309 (5)°

γ = 78.248 (5)°

V = 969.32 (14) Å3

Z = 2

Mo Kα radiation

μ = 0.10 mm−1

T = 293 K

0.20 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) ▶ T min = 0.981, T max = 0.982

17643 measured reflections

4841 independent reflections

3374 reflections with I > 2σ(I)

R int = 0.028

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.106

S = 1.02

4841 reflections

273 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.21 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811053098/nk2121sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053098/nk2121Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053098/nk2121Isup3.cml

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

C23H19N3O4	Z = 2
Mr = 401.41	F(000) = 420
Triclinic, P1	Dx = 1.375 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3483 (7) Å	Cell parameters from 4841 reflections
b = 10.2256 (9) Å	θ = 2.0–28.4°
c = 10.9080 (9) Å	µ = 0.10 mm−1
α = 71.832 (5)°	T = 293 K
β = 88.309 (5)°	Block, white
γ = 78.248 (5)°	0.20 × 0.20 × 0.19 mm
V = 969.32 (14) Å3

Bruker APEXII CCD area detector diffractometer	4841 independent reflections
Radiation source: fine-focus sealed tube	3374 reflections with I > 2σ(I)
graphite	Rint = 0.028
ω and φ scans	θmax = 28.4°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.981, Tmax = 0.982	k = −13→13
17643 measured reflections	l = −14→14

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.106	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0425P)2 + 0.2158P] where P = (Fo2 + 2Fc2)/3
4841 reflections	(Δ/σ)max < 0.001
273 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.21 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	0.01655 (15)	0.90996 (14)	0.37494 (13)	0.0379 (3)
C2	−0.12747 (17)	0.90527 (17)	0.41086 (16)	0.0507 (4)
H2	−0.1515	0.8200	0.4571	0.061*
C3	−0.2338 (2)	1.0263 (2)	0.37808 (19)	0.0652 (5)
H3	−0.3298	1.0227	0.4010	0.078*
C4	−0.1974 (2)	1.1539 (2)	0.3107 (2)	0.0701 (5)
H4	−0.2698	1.2354	0.2897	0.084*
C5	−0.0581 (2)	1.16225 (17)	0.27475 (17)	0.0610 (5)
H5	−0.0347	1.2483	0.2300	0.073*
C6	0.04833 (18)	1.03947 (15)	0.30641 (14)	0.0449 (3)
C7	0.28974 (17)	0.93517 (15)	0.28421 (14)	0.0448 (3)
H7	0.3811	0.9453	0.2511	0.054*
C8	0.27088 (15)	0.80437 (14)	0.34502 (12)	0.0345 (3)
C9	0.13386 (15)	0.78375 (14)	0.40633 (12)	0.0345 (3)
C10	0.39326 (14)	0.67953 (14)	0.35242 (12)	0.0351 (3)
H10	0.3858	0.6033	0.4319	0.042*
C11	0.39211 (14)	0.62424 (13)	0.23496 (12)	0.0324 (3)
C12	0.40376 (15)	0.74112 (15)	0.11646 (13)	0.0377 (3)
C13	0.52387 (15)	0.50169 (15)	0.24145 (14)	0.0411 (3)
H13A	0.6075	0.5376	0.2003	0.049*
H13B	0.5515	0.4463	0.3304	0.049*
C14	0.47078 (16)	0.41335 (15)	0.16957 (15)	0.0442 (3)
H14A	0.5333	0.4056	0.0986	0.053*
H14B	0.4697	0.3197	0.2272	0.053*
C15	0.23476 (19)	0.40250 (18)	0.08659 (16)	0.0541 (4)
H15A	0.2815	0.3681	0.0199	0.081*
H15B	0.1394	0.4580	0.0558	0.081*
H15C	0.2256	0.3245	0.1610	0.081*
C16	0.26018 (14)	0.56017 (13)	0.21551 (11)	0.0318 (3)
C17	0.22340 (15)	0.45055 (14)	0.34238 (12)	0.0361 (3)
C18	0.00806 (15)	0.59547 (14)	0.25514 (13)	0.0363 (3)
C19	0.11179 (14)	0.65327 (14)	0.17285 (12)	0.0335 (3)
C20	0.06507 (16)	0.77525 (15)	0.07153 (13)	0.0423 (3)
H20	0.1312	0.8141	0.0131	0.051*
C21	−0.08275 (18)	0.83888 (17)	0.05857 (16)	0.0515 (4)
H21	−0.1149	0.9213	−0.0088	0.062*
C22	−0.18214 (17)	0.78190 (18)	0.14373 (17)	0.0528 (4)
H22	−0.2799	0.8274	0.1341	0.063*
C23	−0.13801 (16)	0.65743 (17)	0.24364 (15)	0.0470 (4)
H23	−0.2047	0.6174	0.3006	0.056*
N1	0.41798 (16)	0.83035 (15)	0.02676 (13)	0.0575 (4)
N3	0.32235 (12)	0.48890 (12)	0.12161 (10)	0.0369 (3)
N2	0.07765 (13)	0.47154 (12)	0.34909 (11)	0.0403 (3)
H2A	0.0321	0.4158	0.4043	0.048*
O1	0.18680 (13)	1.05308 (10)	0.26729 (11)	0.0532 (3)
O2	0.11877 (11)	0.66834 (10)	0.47960 (9)	0.0429 (2)
O3	0.53230 (11)	0.71535 (13)	0.35228 (10)	0.0496 (3)
H3A	0.5622	0.6968	0.4269	0.074*
O4	0.31198 (11)	0.35561 (11)	0.41684 (10)	0.0493 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0380 (8)	0.0409 (7)	0.0372 (7)	−0.0030 (6)	0.0020 (6)	−0.0189 (6)
C2	0.0414 (9)	0.0560 (9)	0.0579 (9)	−0.0047 (7)	0.0053 (7)	−0.0260 (8)
C3	0.0431 (10)	0.0754 (12)	0.0775 (12)	0.0055 (9)	−0.0012 (9)	−0.0356 (10)
C4	0.0646 (13)	0.0602 (11)	0.0767 (12)	0.0199 (9)	−0.0136 (10)	−0.0281 (10)
C5	0.0707 (13)	0.0436 (9)	0.0613 (10)	0.0050 (8)	−0.0045 (9)	−0.0160 (8)
C6	0.0520 (9)	0.0413 (8)	0.0410 (7)	−0.0027 (7)	0.0008 (7)	−0.0165 (6)
C7	0.0455 (9)	0.0446 (8)	0.0467 (8)	−0.0126 (7)	0.0116 (7)	−0.0164 (6)
C8	0.0342 (7)	0.0403 (7)	0.0323 (6)	−0.0093 (6)	0.0042 (5)	−0.0154 (5)
C9	0.0376 (8)	0.0378 (7)	0.0325 (6)	−0.0091 (6)	0.0048 (5)	−0.0166 (5)
C10	0.0297 (7)	0.0438 (7)	0.0327 (6)	−0.0089 (6)	0.0032 (5)	−0.0126 (5)
C11	0.0269 (7)	0.0380 (7)	0.0326 (6)	−0.0074 (5)	0.0047 (5)	−0.0115 (5)
C12	0.0348 (8)	0.0444 (7)	0.0386 (7)	−0.0127 (6)	0.0084 (6)	−0.0172 (6)
C13	0.0285 (7)	0.0478 (8)	0.0459 (8)	−0.0025 (6)	0.0049 (6)	−0.0169 (6)
C14	0.0399 (8)	0.0427 (8)	0.0497 (8)	−0.0022 (6)	0.0080 (6)	−0.0186 (6)
C15	0.0573 (11)	0.0598 (10)	0.0600 (10)	−0.0207 (8)	0.0081 (8)	−0.0346 (8)
C16	0.0301 (7)	0.0357 (6)	0.0299 (6)	−0.0070 (5)	0.0047 (5)	−0.0107 (5)
C17	0.0373 (8)	0.0382 (7)	0.0343 (6)	−0.0106 (6)	0.0047 (6)	−0.0121 (5)
C18	0.0316 (7)	0.0435 (7)	0.0381 (7)	−0.0100 (6)	0.0032 (5)	−0.0177 (6)
C19	0.0291 (7)	0.0401 (7)	0.0341 (6)	−0.0080 (5)	0.0017 (5)	−0.0152 (5)
C20	0.0400 (8)	0.0462 (8)	0.0389 (7)	−0.0083 (6)	−0.0015 (6)	−0.0108 (6)
C21	0.0446 (9)	0.0515 (9)	0.0534 (9)	0.0006 (7)	−0.0133 (7)	−0.0145 (7)
C22	0.0314 (8)	0.0645 (10)	0.0673 (10)	−0.0005 (7)	−0.0066 (7)	−0.0325 (9)
C23	0.0298 (8)	0.0627 (10)	0.0569 (9)	−0.0133 (7)	0.0075 (6)	−0.0289 (8)
N1	0.0658 (10)	0.0599 (8)	0.0469 (7)	−0.0260 (7)	0.0109 (7)	−0.0093 (6)
N3	0.0354 (6)	0.0406 (6)	0.0387 (6)	−0.0081 (5)	0.0067 (5)	−0.0183 (5)
N2	0.0363 (7)	0.0448 (6)	0.0405 (6)	−0.0161 (5)	0.0109 (5)	−0.0104 (5)
O1	0.0591 (7)	0.0378 (5)	0.0605 (7)	−0.0115 (5)	0.0125 (5)	−0.0122 (5)
O2	0.0431 (6)	0.0395 (5)	0.0455 (5)	−0.0111 (4)	0.0140 (4)	−0.0120 (4)
O3	0.0338 (6)	0.0765 (7)	0.0456 (6)	−0.0193 (5)	0.0021 (4)	−0.0244 (5)
O4	0.0472 (6)	0.0489 (6)	0.0416 (5)	−0.0078 (5)	−0.0029 (5)	−0.0006 (5)

C1—C6	1.389 (2)	C13—H13B	0.9700
C1—C2	1.397 (2)	C14—N3	1.4663 (18)
C1—C9	1.4682 (19)	C14—H14A	0.9700
C2—C3	1.376 (2)	C14—H14B	0.9700
C2—H2	0.9300	C15—N3	1.4562 (18)
C3—C4	1.388 (3)	C15—H15A	0.9600
C3—H3	0.9300	C15—H15B	0.9600
C4—C5	1.361 (3)	C15—H15C	0.9600
C4—H4	0.9300	C16—N3	1.4750 (16)
C5—C6	1.388 (2)	C16—C19	1.5070 (18)
C5—H5	0.9300	C16—C17	1.5658 (17)
C6—O1	1.3714 (19)	C17—O4	1.2281 (16)
C7—C8	1.3401 (19)	C17—N2	1.3389 (18)
C7—O1	1.3464 (18)	C18—C23	1.375 (2)
C7—H7	0.9300	C18—C19	1.3952 (18)
C8—C9	1.4506 (18)	C18—N2	1.4047 (17)
C8—C10	1.5137 (19)	C19—C20	1.3838 (19)
C9—O2	1.2346 (15)	C20—C21	1.393 (2)
C10—O3	1.4202 (16)	C20—H20	0.9300
C10—C11	1.5545 (17)	C21—C22	1.378 (2)
C10—H10	0.9800	C21—H21	0.9300
C11—C12	1.4806 (18)	C22—C23	1.388 (2)
C11—C13	1.5536 (18)	C22—H22	0.9300
C11—C16	1.5577 (18)	C23—H23	0.9300
C12—N1	1.1370 (18)	N2—H2A	0.8600
C13—C14	1.525 (2)	O3—H3A	0.8200
C13—H13A	0.9700
C6—C1—C2	118.17 (14)	N3—C14—H14A	110.8
C6—C1—C9	119.37 (13)	C13—C14—H14A	110.8
C2—C1—C9	122.46 (13)	N3—C14—H14B	110.8
C3—C2—C1	120.25 (16)	C13—C14—H14B	110.8
C3—C2—H2	119.9	H14A—C14—H14B	108.8
C1—C2—H2	119.9	N3—C15—H15A	109.5
C2—C3—C4	119.87 (18)	N3—C15—H15B	109.5
C2—C3—H3	120.1	H15A—C15—H15B	109.5
C4—C3—H3	120.1	N3—C15—H15C	109.5
C5—C4—C3	121.35 (17)	H15A—C15—H15C	109.5
C5—C4—H4	119.3	H15B—C15—H15C	109.5
C3—C4—H4	119.3	N3—C16—C19	113.02 (10)
C4—C5—C6	118.53 (17)	N3—C16—C11	99.38 (10)
C4—C5—H5	120.7	C19—C16—C11	120.44 (11)
C6—C5—H5	120.7	N3—C16—C17	110.39 (10)
O1—C6—C5	116.38 (14)	C19—C16—C17	101.30 (10)
O1—C6—C1	121.81 (13)	C11—C16—C17	112.55 (10)
C5—C6—C1	121.81 (16)	O4—C17—N2	126.16 (12)
C8—C7—O1	125.13 (14)	O4—C17—C16	125.96 (12)
C8—C7—H7	117.4	N2—C17—C16	107.66 (11)
O1—C7—H7	117.4	C23—C18—C19	122.99 (13)
C7—C8—C9	119.49 (13)	C23—C18—N2	127.48 (13)
C7—C8—C10	120.12 (12)	C19—C18—N2	109.50 (12)
C9—C8—C10	120.38 (11)	C20—C19—C18	118.68 (13)
O2—C9—C8	121.90 (12)	C20—C19—C16	132.64 (12)
O2—C9—C1	123.19 (12)	C18—C19—C16	108.66 (11)
C8—C9—C1	114.91 (12)	C19—C20—C21	118.85 (14)
O3—C10—C8	111.26 (11)	C19—C20—H20	120.6
O3—C10—C11	104.83 (10)	C21—C20—H20	120.6
C8—C10—C11	113.27 (10)	C22—C21—C20	121.21 (15)
O3—C10—H10	109.1	C22—C21—H21	119.4
C8—C10—H10	109.1	C20—C21—H21	119.4
C11—C10—H10	109.1	C21—C22—C23	120.75 (15)
C12—C11—C13	107.68 (11)	C21—C22—H22	119.6
C12—C11—C10	107.99 (10)	C23—C22—H22	119.6
C13—C11—C10	112.06 (10)	C18—C23—C22	117.45 (14)
C12—C11—C16	108.36 (10)	C18—C23—H23	121.3
C13—C11—C16	102.03 (10)	C22—C23—H23	121.3
C10—C11—C16	118.22 (10)	C15—N3—C14	113.60 (12)
N1—C12—C11	177.45 (15)	C15—N3—C16	116.64 (11)
C14—C13—C11	105.22 (11)	C14—N3—C16	106.96 (10)
C14—C13—H13A	110.7	C17—N2—C18	111.97 (11)
C11—C13—H13A	110.7	C17—N2—H2A	124.0
C14—C13—H13B	110.7	C18—N2—H2A	124.0
C11—C13—H13B	110.7	C7—O1—C6	118.17 (11)
H13A—C13—H13B	108.8	C10—O3—H3A	109.5
N3—C14—C13	104.94 (11)
C6—C1—C2—C3	0.3 (2)	C10—C11—C16—C19	71.10 (15)
C9—C1—C2—C3	−179.39 (14)	C12—C11—C16—C17	−171.44 (11)
C1—C2—C3—C4	−0.9 (3)	C13—C11—C16—C17	75.12 (12)
C2—C3—C4—C5	0.7 (3)	C10—C11—C16—C17	−48.25 (15)
C3—C4—C5—C6	0.3 (3)	N3—C16—C17—O4	63.93 (17)
C4—C5—C6—O1	179.54 (15)	C19—C16—C17—O4	−176.09 (13)
C4—C5—C6—C1	−1.0 (2)	C11—C16—C17—O4	−46.11 (18)
C2—C1—C6—O1	−179.85 (13)	N3—C16—C17—N2	−110.91 (12)
C9—C1—C6—O1	−0.2 (2)	C19—C16—C17—N2	9.07 (13)
C2—C1—C6—C5	0.7 (2)	C11—C16—C17—N2	139.05 (11)
C9—C1—C6—C5	−179.63 (13)	C23—C18—C19—C20	−2.9 (2)
O1—C7—C8—C9	−4.4 (2)	N2—C18—C19—C20	178.87 (11)
O1—C7—C8—C10	177.16 (13)	C23—C18—C19—C16	178.50 (12)
C7—C8—C9—O2	−168.83 (13)	N2—C18—C19—C16	0.27 (14)
C10—C8—C9—O2	9.61 (19)	N3—C16—C19—C20	−65.67 (18)
C7—C8—C9—C1	10.87 (18)	C11—C16—C19—C20	51.41 (19)
C10—C8—C9—C1	−170.68 (11)	C17—C16—C19—C20	176.24 (14)
C6—C1—C9—O2	171.04 (13)	N3—C16—C19—C18	112.66 (12)
C2—C1—C9—O2	−9.3 (2)	C11—C16—C19—C18	−130.27 (12)
C6—C1—C9—C8	−8.66 (18)	C17—C16—C19—C18	−5.43 (13)
C2—C1—C9—C8	171.01 (13)	C18—C19—C20—C21	2.6 (2)
C7—C8—C10—O3	29.78 (17)	C16—C19—C20—C21	−179.22 (14)
C9—C8—C10—O3	−148.65 (11)	C19—C20—C21—C22	−0.6 (2)
C7—C8—C10—C11	−88.01 (15)	C20—C21—C22—C23	−1.3 (2)
C9—C8—C10—C11	93.56 (14)	C19—C18—C23—C22	1.0 (2)
O3—C10—C11—C12	−63.12 (13)	N2—C18—C23—C22	178.92 (13)
C8—C10—C11—C12	58.35 (14)	C21—C22—C23—C18	1.1 (2)
O3—C10—C11—C13	55.30 (13)	C13—C14—N3—C15	−161.39 (12)
C8—C10—C11—C13	176.78 (11)	C13—C14—N3—C16	−31.23 (14)
O3—C10—C11—C16	173.51 (11)	C19—C16—N3—C15	−56.75 (15)
C8—C10—C11—C16	−65.02 (15)	C11—C16—N3—C15	174.33 (11)
C13—C11—C12—N1	−49 (3)	C17—C16—N3—C15	55.90 (15)
C10—C11—C12—N1	72 (3)	C19—C16—N3—C14	174.84 (11)
C16—C11—C12—N1	−159 (3)	C11—C16—N3—C14	45.93 (12)
C12—C11—C13—C14	−89.80 (13)	C17—C16—N3—C14	−72.51 (13)
C10—C11—C13—C14	151.59 (11)	O4—C17—N2—C18	175.49 (13)
C16—C11—C13—C14	24.15 (13)	C16—C17—N2—C18	−9.68 (15)
C11—C13—C14—N3	2.87 (14)	C23—C18—N2—C17	−171.89 (13)
C12—C11—C16—N3	71.75 (12)	C19—C18—N2—C17	6.24 (16)
C13—C11—C16—N3	−41.69 (11)	C8—C7—O1—C6	−5.0 (2)
C10—C11—C16—N3	−165.06 (10)	C5—C6—O1—C7	−173.25 (14)
C12—C11—C16—C19	−52.08 (15)	C1—C6—O1—C7	7.3 (2)
C13—C11—C16—C19	−165.52 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O2i	0.86	2.01	2.8479 (14)	164.
O3—H3A···O4ii	0.82	1.97	2.7631 (14)	164.
C23—H23···O3iii	0.93	2.58	3.2761 (18)	133.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O2i	0.86	2.01	2.8479 (14)	164
O3—H3A⋯O4ii	0.82	1.97	2.7631 (14)	164
C23—H23⋯O3iii	0.93	2.58	3.2761 (18)	133

Symmetry codes: (i) ; (ii) ; (iii) .