3′-[Hy­droxy(4-oxo-4H-chromen-3-yl)meth­yl]-2-oxospiro­[indoline-3,2′-pyrrolidine]-3′-carbonitrile

Govindan, E.; SakthiMurugesan, K.; SubbiahPandi, A.; Yuvaraj, P.; Reddy, B.S.R.

doi:10.1107/S1600536811053098

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages o136-o137

doi:10.1107/S1600536811053098

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3′-[Hydroxy(4-oxo-4H-chromen-3-yl)methyl]-2-oxospiro[indoline-3,2′-pyrrolidine]-3′-carbonitrile

E. Govindan,^a K. SakthiMurugesan,^a A. SubbiahPandi,^a ^* P. Yuvaraj ^b and Boreddy S. R. Reddy ^b

^aDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^bIndustrial Chemistry Laboratory, Central Leather Research Institute, Adyar, Chennai 600 020, India
^*Correspondence e-mail: a_sp59@yahoo.in

(Received 12 October 2011; accepted 9 December 2011; online 17 December 2011)

In the title compound, C₂₃H₁₉N₃O₄, 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, molecules are connected by two unique N—H⋯O and O—H⋯O hydrogen-bonding interactions, which form centrosymmetric patterns described by graph-set motifs R₂²(18) and R₂²(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 interactions and by aromatic π–π stacking interactions between the pyran and benzene rings of neighbouring molecules [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_r = 401.41
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.106
S = 1.02
4841 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.21 e Å⁻³

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) -x, -y+1, -z+1; (ii) -x+1, -y+1, -z+1; (iii) x-1, y, z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811053098/nk2121sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811053098/nk2121Isup3.cml

checkCIF report

Comment top

Pyrrolidine derivatives are used as norepinephrine reuptake inhibitors and 5-HT(1 A) partial agonists for treating neuropsychiatric disorders including depression and anxiety (Pettersson et al., 2011). These derivatives are used as alpha-mannosidase inhibitors and with antitumor activities against hematological and solid malignancies (Bello et al., 2010). In view of these importance, we have undertaken the crystal structure determination of the title compound, a pyrrolidine derivative,and the results are presented here.

Single crystal X-ray analysis confirms the molecular structure and atom connectivity as illustrated in Fig. 1. The bond lengths and angles in (Fig. 1) agree with those observed in other pyrrolidine derivatives (Selvanayagam et al., 2011). The sum of the angles at N1 of the pyrrolidine ring [337.3 (2)°] is in accordance with sp³ hybridization. The pyran ring (O1/C1/C6–C9) adopts a half chair conformation with a local, non-crystallographic two fold rotation axis passing through the mid point of the [O1–C6] and [C9–C8] bonds; the puckering parameters Q, θ, ϕ (Cremer & Pople, 1975) and asymmetry parameter ΔC₂[O1–C6](Nardelli, 1983) are 0.1074 (15) Å, 78.8 (8)°, 192.7 (9)° and 4.6 (2) Å, respectively. The pyrrolidine (N3/C11/C13/C14/C16) and five membered in the indoline (N2/C16—C19) rings adopt an envelope conformation with the C16 (displacement 5.8 (1) Å) and C17 (displacement 0.7 (2) Å) atoms as the flap atoms and with puckering parameters, q₂ = 0.0888 (15) Å; ϕ₂ = 326.7 (2)°; and q₂ = 0.4459 (15) Å; ϕ₂ = 38.6 (9)° respectively. The pyrrolidine ring makes dihedral angles of 83.3 (1)° and 60.4 (1)° with mean plane fitted through all non-H atoms of the indoline (N2/C16–C23) ring system and the chromen (O1/C1–C9) ring system, respectively.

In the crystal, unique N2–H2A···O2 (at x,y,z and -x,1 - y,1 - z) and O3–H3A···O4 (at x,y,z and 1 - x,1 - y,1 - z) hydrogen bonding interactions form a cyclic centrosymmetric patterns, with the motif R²₂(18) and R²₂(14). These combine to form a zigzag chains which propagates in the a axis direction (Table 1 and Fig. 2). The crystal packing is further stabilized by π–π stacking interactions between the rings Cg1 and Cg2 (at x,y,z and -x, 2 - y, 1 - z) with the centroid-centroid distances equal to 3.755 (1) Å and slippage = 1.371 (2) Å (Fig. 2; Cg1 and Cg2 are the centroids of pyran (O1/C1/C6–C9) and benzene (C1–C6) ring, respectively).

Related literature top

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 top

2-(Hydroxyl(4-oxo-4H-chromen-3-yl)methyl)acrylonitrile was synthesized by the Baylis-Hillman reaction of chromene-3-aldehyde, acrylonitrile and 0.1 equivalent of DABCO as a catalyst, in the presence of 1-methyl-2-pyrrolidinone (NMP) as a solvent. Baylis-Hillman adduct underwent smooth reaction with non-stabilized azomethine ylide generated from isatin and sarcosine by refluxing in acetonitrile. After that, a mixture of 2-(Hydroxyl(4-oxo-4H-chromen-3-yl)methyl)acrylonitrile (100 mg, 0.404 mmol), sarcosine(1.2eq), and isatin (1.2eq.) in acetonitrile(2 ml) was refluxed for 6–12 h. Completion of reaction was indicated by TLC, the solvent was then removed in vacuo and the crude product subjected to column chromatography (100–200 mesh) using hexane-ethyl acetate as eluent. Single crystal suitable for X-ray diffraction were obtained by slow evaporation of a solution of the title compound in hexane at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (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. Part of the crystal packing of (I) showing N—H···O and O—H···O intermolecular hydrogen bonds showing R²₂(18) and R²₂(14) centrosymmetric dimers, respectively. [Symmetry codes: (i) -1 + x, y, z; (ii) -x, 1 - y, 1 - z; (iii) -1 + x, 1 - y, 1 - z; (iv) 1 + x, y, z; (v) 2 - x, 1 - y, 1 - z].
	Fig. 3. The π–π interactions shown as dotted lines in the title compound. Cg1 and Cg2 are the centroids of pyran (O1/C1/C6–C9) and benzene (C1–C6) ring, respectively. [Symmetry code: (i) -x, 2 - y, 1 - z]

3'-[Hydroxy(4-oxo-4H-chromen-3-yl)methyl]-2-oxospiro[indoline-3,2'- pyrrolidine]-3'-carbonitrile top

Crystal data top

C₂₃H₁₉N₃O₄	Z = 2
M_r = 401.41	F(000) = 420
Triclinic, P1	D_x = 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

Data collection top

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

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.106	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0425P)² + 0.2158P] where P = (F_o² + 2F_c²)/3
4841 reflections	(Δ/σ)_max < 0.001
273 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₃H₁₉N₃O₄	γ = 78.248 (5)°
M_r = 401.41	V = 969.32 (14) Å³
Triclinic, P1	Z = 2
a = 9.3483 (7) Å	Mo Kα radiation
b = 10.2256 (9) Å	µ = 0.10 mm⁻¹
c = 10.9080 (9) Å	T = 293 K
α = 71.832 (5)°	0.20 × 0.20 × 0.19 mm
β = 88.309 (5)°

Data collection top

Bruker APEXII CCD area detector diffractometer	4841 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3374 reflections with I > 2σ(I)
T_min = 0.981, T_max = 0.982	R_int = 0.028
17643 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.106	H-atom parameters constrained
S = 1.02	Δρ_max = 0.22 e Å⁻³
4841 reflections	Δρ_min = −0.21 e Å⁻³
273 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	0.01655 (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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₃H₁₉N₃O₄
M_r	401.41
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.3483 (7), 10.2256 (9), 10.9080 (9)
α, β, γ (°)	71.832 (5), 88.309 (5), 78.248 (5)
V (Å³)	969.32 (14)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.20 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.981, 0.982
No. of measured, independent and observed [I > 2σ(I)] reflections	17643, 4841, 3374
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.106, 1.02
No. of reflections	4841
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.21

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), 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
N2—H2A···O2ⁱ	0.86	2.01	2.8479 (14)	164.4
O3—H3A···O4ⁱⁱ	0.82	1.97	2.7631 (14)	163.7
C23—H23···O3ⁱⁱⁱ	0.93	2.58	3.2761 (18)	132.5

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

Acknowledgements

The authors thank Dr Babu Varghese, SAIF, IIT, Chennai, India, for the data collection.

References

Bello, C., Cea, M., Dal Bello, G., Garuti, A., Rocco, I., Cirmena, G., Moran, E., Nahimana, A., Duchosal, M. A., Fruscione, F., Pronzato, P., Grossi, F., Patrone, F., Ballestro, A., Dupuis, M., Sordat, B., Nencioni, A. & Vogel, P. (2010). Bioorg. Med. Chem. 18, 3320–3334. Web of Science CrossRef CAS PubMed Google Scholar
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Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Pettersson, M., Campbell, B. M., Dounary, A. B., Gray, D. L., Xie, L., O'Donnell, C. J., Stratman, N. C., Zoski, K., Drummond, E., Bora, G., Probert, A. & Whisman, T. (2011). Bioorg. Med. Chem. Lett. 21, 865–868. Web of Science CrossRef CAS PubMed Google Scholar
Selvanayagam, S., Sridhar, B., Ravikumar, K., Saravanan, P. & Raghunathan, R. (2011). Acta Cryst. E67, o629. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 68| Part 1| January 2012| Pages o136-o137

doi:10.1107/S1600536811053098

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

3′-[Hy­dr­oxy(4-oxo-4H-chromen-3-yl)meth­yl]-2-oxo­spiro­[indoline-3,2′-pyrrolidine]-3′-carbo­nitrile

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3′-[Hydroxy(4-oxo-4H-chromen-3-yl)methyl]-2-oxospiro[indoline-3,2′-pyrrolidine]-3′-carbonitrile