Crystal structure of ethyl 1',1''-dimethyl-2'',3-dioxo-3H-di-spiro-[benzo[b]thio-phene-2,3'-pyrrolidine-2',3''-indoline]-4'-carboxyl-ate.

In the title compound, C23H22N2O4S, the pyrrolidine ring has an envelope conformation with the spiro C atom, shared with the indoline ring system, as the flap. The mean planes of the benzo-thio-phene and indoline ring systems are inclined to the mean plane of the pyrrolidine ring by 88.81 (8) and 79.48 (8)°, respectively, and to each other by 68.12 (5)°. In the crystal, mol-ecules are linked via C-H⋯O hydrogen bonds, forming chains propagating along [001].

Related literature

For various biological activities of indole derivatives, see: Harris & Uhle (1960 ▸); Ho et al. (1986 ▸); Stevenson et al. (2000 ▸). For the crystal structures of two very similar compounds, see: Savithri et al. (2014 ▸).

Experimental

Crystal data

C23H22N2O4S

M = 422.49

Monoclinic,

a = 23.7049 (11) Å

b = 8.2632 (3) Å

c = 22.1003 (8) Å

β = 102.337 (2)°

V = 4229.0 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.19 mm−1

T = 293 K

0.35 × 0.30 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.896, T max = 0.910

22087 measured reflections

4621 independent reflections

3869 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.105

S = 1.03

4618 reflections

275 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015002042/su5065sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015002042/su5065Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S2056989015002042/su5065fig1.tif

The mol­ecular structure of the title compound with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015002042/su5065fig2.tif

The crystal packing of the title compound viewed along the b axis. Dashed lines shows the inter­molecular C—H⋯O hydrogen bonds. H atoms not involved in hydrogen bonding have been omitted for clarity.

CCDC reference: 1046459

Additional supporting information: crystallographic information; 3D view; checkCIF report

C23H22N2O4S	F(000) = 1776
Mr = 422.49	Dx = 1.327 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4634 reflections
a = 23.7049 (11) Å	θ = 2.3–27.0°
b = 8.2632 (3) Å	µ = 0.19 mm−1
c = 22.1003 (8) Å	T = 293 K
β = 102.337 (2)°	Block, colourless
V = 4229.0 (3) Å3	0.35 × 0.30 × 0.30 mm
Z = 8

Bruker Kappa APEXII CCD diffractometer	4621 independent reflections
Radiation source: fine-focus sealed tube	3869 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
ω and φ scans	θmax = 27.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −30→30
Tmin = 0.896, Tmax = 0.910	k = −10→8
22087 measured reflections	l = −22→28

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H-atom parameters constrained
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0502P)2 + 2.8328P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
4618 reflections	Δρmax = 0.40 e Å−3
275 parameters	Δρmin = −0.20 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0025 (2)

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.

	x	y	z	Uiso*/Ueq
S1	0.141873 (15)	0.31779 (4)	0.413751 (16)	0.03357 (12)
C11	0.13418 (6)	0.09712 (17)	0.41066 (6)	0.0316 (3)
N1	0.16154 (6)	−0.18548 (15)	0.30761 (6)	0.0390 (3)
C1	0.18787 (6)	0.08191 (18)	0.32013 (6)	0.0319 (3)
O2	0.05531 (5)	−0.07835 (14)	0.36475 (6)	0.0499 (3)
O1	0.17197 (6)	−0.27090 (14)	0.40812 (6)	0.0515 (3)
C8	0.18360 (6)	0.02047 (17)	0.38341 (6)	0.0318 (3)
C12	0.07265 (6)	0.05908 (19)	0.37426 (7)	0.0350 (3)
C14	0.07062 (6)	0.34826 (19)	0.37340 (7)	0.0352 (3)
C7	0.17122 (6)	−0.16405 (18)	0.37017 (7)	0.0364 (3)
N2	0.23289 (5)	0.05295 (16)	0.43401 (6)	0.0384 (3)
C13	0.03980 (6)	0.2070 (2)	0.35486 (7)	0.0380 (3)
C6	0.17075 (6)	−0.04172 (19)	0.27721 (7)	0.0356 (3)
C2	0.20526 (7)	0.2287 (2)	0.30060 (8)	0.0395 (4)
H2	0.2187	0.3105	0.3290	0.047*
O4	0.06476 (6)	0.13849 (16)	0.49836 (6)	0.0556 (3)
C10	0.14909 (7)	0.0263 (2)	0.47706 (7)	0.0405 (4)
H10	0.1360	−0.0865	0.4747	0.049*
C9	0.21520 (8)	0.0253 (2)	0.49324 (8)	0.0495 (4)
H9A	0.2298	0.1104	0.5226	0.059*
H9B	0.2296	−0.0780	0.5110	0.059*
C15	0.04484 (7)	0.4995 (2)	0.36049 (8)	0.0471 (4)
H15	0.0654	0.5942	0.3726	0.056*
C20	0.28698 (7)	−0.0239 (2)	0.42869 (9)	0.0541 (5)
H20A	0.2826	−0.1394	0.4290	0.081*
H20B	0.3170	0.0083	0.4630	0.081*
H20C	0.2969	0.0088	0.3906	0.081*
C18	−0.01766 (8)	0.2148 (2)	0.32301 (9)	0.0539 (5)
H18	−0.0384	0.1206	0.3105	0.065*
C21	0.12051 (9)	0.1125 (2)	0.52268 (7)	0.0498 (4)
C5	0.16713 (7)	−0.0205 (2)	0.21453 (7)	0.0474 (4)
H5	0.1547	−0.1032	0.1863	0.057*
C3	0.20234 (8)	0.2522 (2)	0.23745 (8)	0.0489 (4)
H3	0.2136	0.3508	0.2236	0.059*
O3	0.14426 (8)	0.1504 (2)	0.57445 (6)	0.0794 (5)
C4	0.18291 (8)	0.1304 (3)	0.19547 (8)	0.0530 (5)
H4	0.1803	0.1495	0.1535	0.064*
C19	0.15024 (10)	−0.3419 (2)	0.27783 (10)	0.0598 (5)
H19A	0.1551	−0.4252	0.3088	0.090*
H19B	0.1767	−0.3596	0.2511	0.090*
H19C	0.1114	−0.3445	0.2538	0.090*
C16	−0.01201 (9)	0.5045 (3)	0.32919 (11)	0.0646 (5)
H16	−0.0300	0.6043	0.3204	0.078*
C17	−0.04313 (8)	0.3642 (3)	0.31035 (11)	0.0686 (6)
H17	−0.0814	0.3713	0.2891	0.082*
C22	0.03086 (12)	0.2257 (3)	0.53552 (11)	0.0763 (7)
H22A	0.0519	0.3201	0.5544	0.092*
H22B	0.0230	0.1565	0.5682	0.092*
C23	−0.02388 (11)	0.2757 (3)	0.49378 (13)	0.0819 (7)
H23A	−0.0156	0.3458	0.4621	0.123*
H23B	−0.0475	0.3320	0.5172	0.123*
H23C	−0.0440	0.1815	0.4749	0.123*

	U11	U22	U33	U12	U13	U23
S1	0.0366 (2)	0.0301 (2)	0.03283 (19)	−0.00394 (14)	0.00468 (14)	−0.00350 (15)
C11	0.0373 (7)	0.0291 (7)	0.0280 (6)	−0.0048 (6)	0.0063 (5)	−0.0004 (6)
N1	0.0449 (7)	0.0305 (7)	0.0405 (7)	−0.0051 (5)	0.0066 (5)	−0.0084 (6)
C1	0.0295 (7)	0.0325 (8)	0.0336 (7)	0.0001 (5)	0.0066 (5)	−0.0022 (6)
O2	0.0461 (6)	0.0378 (7)	0.0646 (8)	−0.0129 (5)	0.0090 (6)	−0.0061 (6)
O1	0.0686 (8)	0.0314 (6)	0.0514 (7)	−0.0028 (5)	0.0059 (6)	0.0072 (6)
C8	0.0346 (7)	0.0279 (7)	0.0309 (7)	−0.0026 (6)	0.0028 (5)	−0.0017 (6)
C12	0.0363 (7)	0.0380 (8)	0.0319 (7)	−0.0083 (6)	0.0103 (6)	−0.0018 (6)
C14	0.0354 (7)	0.0394 (8)	0.0314 (7)	−0.0017 (6)	0.0087 (6)	0.0023 (6)
C7	0.0374 (8)	0.0297 (8)	0.0402 (8)	−0.0012 (6)	0.0042 (6)	−0.0028 (7)
N2	0.0368 (7)	0.0393 (7)	0.0344 (6)	−0.0001 (5)	−0.0027 (5)	−0.0052 (6)
C13	0.0351 (7)	0.0424 (9)	0.0363 (8)	−0.0039 (6)	0.0074 (6)	0.0016 (7)
C6	0.0324 (7)	0.0380 (8)	0.0357 (7)	−0.0004 (6)	0.0056 (6)	−0.0049 (6)
C2	0.0405 (8)	0.0361 (8)	0.0447 (9)	−0.0032 (6)	0.0153 (7)	−0.0022 (7)
O4	0.0676 (8)	0.0583 (8)	0.0484 (7)	−0.0018 (6)	0.0292 (6)	−0.0051 (6)
C10	0.0561 (9)	0.0360 (8)	0.0286 (7)	−0.0033 (7)	0.0071 (6)	0.0036 (6)
C9	0.0574 (10)	0.0516 (10)	0.0339 (8)	0.0029 (8)	−0.0028 (7)	0.0021 (8)
C15	0.0486 (9)	0.0402 (9)	0.0527 (10)	0.0024 (7)	0.0116 (8)	0.0048 (8)
C20	0.0412 (9)	0.0573 (11)	0.0574 (11)	0.0070 (8)	−0.0038 (8)	−0.0107 (9)
C18	0.0388 (9)	0.0560 (11)	0.0624 (11)	−0.0086 (8)	0.0010 (8)	0.0020 (9)
C21	0.0757 (12)	0.0444 (10)	0.0326 (8)	−0.0061 (9)	0.0187 (8)	0.0056 (7)
C5	0.0516 (9)	0.0556 (11)	0.0341 (8)	0.0001 (8)	0.0075 (7)	−0.0095 (8)
C3	0.0518 (10)	0.0489 (10)	0.0511 (10)	0.0011 (8)	0.0223 (8)	0.0104 (8)
O3	0.1083 (13)	0.0999 (13)	0.0299 (6)	0.0017 (10)	0.0146 (7)	−0.0060 (7)
C4	0.0585 (11)	0.0672 (12)	0.0359 (8)	0.0068 (9)	0.0160 (7)	0.0067 (9)
C19	0.0756 (13)	0.0414 (10)	0.0633 (12)	−0.0176 (9)	0.0168 (10)	−0.0216 (9)
C16	0.0524 (11)	0.0571 (12)	0.0803 (14)	0.0142 (9)	0.0051 (10)	0.0150 (11)
C17	0.0396 (9)	0.0744 (14)	0.0835 (15)	0.0060 (10)	−0.0054 (9)	0.0138 (12)
C22	0.1001 (18)	0.0769 (16)	0.0680 (14)	0.0025 (13)	0.0542 (14)	−0.0079 (12)
C23	0.0883 (17)	0.0679 (15)	0.106 (2)	0.0066 (13)	0.0587 (16)	−0.0015 (14)

S1—C14	1.7516 (15)	C10—H10	0.9800
S1—C11	1.8324 (15)	C9—H9A	0.9700
C11—C12	1.540 (2)	C9—H9B	0.9700
C11—C10	1.5487 (19)	C15—C16	1.378 (3)
C11—C8	1.561 (2)	C15—H15	0.9300
N1—C7	1.364 (2)	C20—H20A	0.9600
N1—C6	1.405 (2)	C20—H20B	0.9600
N1—C19	1.449 (2)	C20—H20C	0.9600
C1—C2	1.380 (2)	C18—C17	1.377 (3)
C1—C6	1.394 (2)	C18—H18	0.9300
C1—C8	1.511 (2)	C21—O3	1.204 (2)
O2—C12	1.2107 (18)	C5—C4	1.393 (3)
O1—C7	1.2153 (19)	C5—H5	0.9300
C8—N2	1.4592 (18)	C3—C4	1.379 (3)
C8—C7	1.568 (2)	C3—H3	0.9300
C12—C13	1.464 (2)	C4—H4	0.9300
C14—C13	1.391 (2)	C19—H19A	0.9600
C14—C15	1.394 (2)	C19—H19B	0.9600
N2—C20	1.458 (2)	C19—H19C	0.9600
N2—C9	1.475 (2)	C16—C17	1.389 (3)
C13—C18	1.395 (2)	C16—H16	0.9300
C6—C5	1.381 (2)	C17—H17	0.9300
C2—C3	1.396 (2)	C22—C23	1.481 (4)
C2—H2	0.9300	C22—H22A	0.9700
O4—C21	1.333 (2)	C22—H22B	0.9700
O4—C22	1.457 (2)	C23—H23A	0.9600
C10—C21	1.508 (2)	C23—H23B	0.9600
C10—C9	1.531 (2)	C23—H23C	0.9600
C14—S1—C11	92.67 (7)	C10—C9—H9B	110.7
C12—C11—C10	114.63 (12)	H9A—C9—H9B	108.8
C12—C11—C8	114.87 (11)	C16—C15—C14	117.94 (17)
C10—C11—C8	100.04 (11)	C16—C15—H15	121.0
C12—C11—S1	107.34 (10)	C14—C15—H15	121.0
C10—C11—S1	109.86 (10)	N2—C20—H20A	109.5
C8—C11—S1	109.95 (9)	N2—C20—H20B	109.5
C7—N1—C6	111.44 (12)	H20A—C20—H20B	109.5
C7—N1—C19	123.43 (14)	N2—C20—H20C	109.5
C6—N1—C19	124.72 (14)	H20A—C20—H20C	109.5
C2—C1—C6	119.63 (14)	H20B—C20—H20C	109.5
C2—C1—C8	131.94 (13)	C17—C18—C13	118.84 (17)
C6—C1—C8	108.43 (12)	C17—C18—H18	120.6
N2—C8—C1	116.51 (12)	C13—C18—H18	120.6
N2—C8—C11	100.00 (11)	O3—C21—O4	124.29 (18)
C1—C8—C11	115.14 (11)	O3—C21—C10	124.94 (19)
N2—C8—C7	114.14 (12)	O4—C21—C10	110.76 (14)
C1—C8—C7	101.59 (11)	C6—C5—C4	117.01 (16)
C11—C8—C7	109.90 (11)	C6—C5—H5	121.5
O2—C12—C13	126.37 (14)	C4—C5—H5	121.5
O2—C12—C11	122.04 (14)	C4—C3—C2	120.62 (17)
C13—C12—C11	111.58 (12)	C4—C3—H3	119.7
C13—C14—C15	120.82 (14)	C2—C3—H3	119.7
C13—C14—S1	114.70 (12)	C3—C4—C5	121.49 (16)
C15—C14—S1	124.48 (13)	C3—C4—H4	119.3
O1—C7—N1	125.43 (14)	C5—C4—H4	119.3
O1—C7—C8	127.09 (14)	N1—C19—H19A	109.5
N1—C7—C8	107.43 (12)	N1—C19—H19B	109.5
C20—N2—C8	115.60 (12)	H19A—C19—H19B	109.5
C20—N2—C9	115.19 (13)	N1—C19—H19C	109.5
C8—N2—C9	108.58 (12)	H19A—C19—H19C	109.5
C14—C13—C18	120.33 (15)	H19B—C19—H19C	109.5
C14—C13—C12	113.66 (13)	C15—C16—C17	121.70 (18)
C18—C13—C12	125.96 (15)	C15—C16—H16	119.2
C5—C6—C1	122.43 (15)	C17—C16—H16	119.2
C5—C6—N1	127.21 (15)	C18—C17—C16	120.38 (17)
C1—C6—N1	110.28 (13)	C18—C17—H17	119.8
C1—C2—C3	118.71 (15)	C16—C17—H17	119.8
C1—C2—H2	120.6	O4—C22—C23	107.59 (18)
C3—C2—H2	120.6	O4—C22—H22A	110.2
C21—O4—C22	118.09 (16)	C23—C22—H22A	110.2
C21—C10—C9	115.47 (14)	O4—C22—H22B	110.2
C21—C10—C11	114.26 (13)	C23—C22—H22B	110.2
C9—C10—C11	103.79 (12)	H22A—C22—H22B	108.5
C21—C10—H10	107.6	C22—C23—H23A	109.5
C9—C10—H10	107.6	C22—C23—H23B	109.5
C11—C10—H10	107.6	H23A—C23—H23B	109.5
N2—C9—C10	105.23 (12)	C22—C23—H23C	109.5
N2—C9—H9A	110.7	H23A—C23—H23C	109.5
C10—C9—H9A	110.7	H23B—C23—H23C	109.5
N2—C9—H9B	110.7
C14—S1—C11—C12	1.58 (10)	S1—C14—C13—C12	1.56 (17)
C14—S1—C11—C10	−123.66 (11)	O2—C12—C13—C14	178.78 (15)
C14—S1—C11—C8	127.17 (10)	C11—C12—C13—C14	−0.26 (18)
C2—C1—C8—N2	−45.8 (2)	O2—C12—C13—C18	1.3 (3)
C6—C1—C8—N2	133.48 (13)	C11—C12—C13—C18	−177.73 (15)
C2—C1—C8—C11	70.9 (2)	C2—C1—C6—C5	−3.9 (2)
C6—C1—C8—C11	−109.88 (13)	C8—C1—C6—C5	176.69 (14)
C2—C1—C8—C7	−170.46 (15)	C2—C1—C6—N1	172.93 (13)
C6—C1—C8—C7	8.80 (14)	C8—C1—C6—N1	−6.44 (16)
C12—C11—C8—N2	−169.56 (12)	C7—N1—C6—C5	177.34 (15)
C10—C11—C8—N2	−46.29 (13)	C19—N1—C6—C5	4.5 (3)
S1—C11—C8—N2	69.26 (11)	C7—N1—C6—C1	0.65 (17)
C12—C11—C8—C1	64.75 (16)	C19—N1—C6—C1	−172.18 (15)
C10—C11—C8—C1	−171.98 (12)	C6—C1—C2—C3	3.3 (2)
S1—C11—C8—C1	−56.43 (14)	C8—C1—C2—C3	−177.51 (15)
C12—C11—C8—C7	−49.19 (16)	C12—C11—C10—C21	−73.44 (17)
C10—C11—C8—C7	74.08 (13)	C8—C11—C10—C21	163.12 (13)
S1—C11—C8—C7	−170.37 (9)	S1—C11—C10—C21	47.50 (16)
C10—C11—C12—O2	−57.80 (19)	C12—C11—C10—C9	159.94 (13)
C8—C11—C12—O2	57.28 (19)	C8—C11—C10—C9	36.51 (14)
S1—C11—C12—O2	179.88 (12)	S1—C11—C10—C9	−79.11 (13)
C10—C11—C12—C13	121.29 (14)	C20—N2—C9—C10	−148.67 (14)
C8—C11—C12—C13	−123.63 (13)	C8—N2—C9—C10	−17.23 (17)
S1—C11—C12—C13	−1.03 (14)	C21—C10—C9—N2	−139.30 (14)
C11—S1—C14—C13	−1.87 (12)	C11—C10—C9—N2	−13.45 (17)
C11—S1—C14—C15	177.39 (14)	C13—C14—C15—C16	0.3 (2)
C6—N1—C7—O1	−172.45 (15)	S1—C14—C15—C16	−178.89 (14)
C19—N1—C7—O1	0.5 (3)	C14—C13—C18—C17	0.0 (3)
C6—N1—C7—C8	5.18 (17)	C12—C13—C18—C17	177.33 (18)
C19—N1—C7—C8	178.12 (15)	C22—O4—C21—O3	3.3 (3)
N2—C8—C7—O1	42.9 (2)	C22—O4—C21—C10	−177.97 (16)
C1—C8—C7—O1	169.17 (15)	C9—C10—C21—O3	−15.2 (3)
C11—C8—C7—O1	−68.47 (19)	C11—C10—C21—O3	−135.47 (19)
N2—C8—C7—N1	−134.66 (13)	C9—C10—C21—O4	166.10 (14)
C1—C8—C7—N1	−8.42 (15)	C11—C10—C21—O4	45.81 (19)
C11—C8—C7—N1	113.95 (13)	C1—C6—C5—C4	1.6 (2)
C1—C8—N2—C20	−63.90 (18)	N1—C6—C5—C4	−174.69 (15)
C11—C8—N2—C20	171.35 (14)	C1—C2—C3—C4	−0.5 (2)
C7—C8—N2—C20	54.10 (18)	C2—C3—C4—C5	−1.8 (3)
C1—C8—N2—C9	164.88 (13)	C6—C5—C4—C3	1.2 (3)
C11—C8—N2—C9	40.13 (14)	C14—C15—C16—C17	−0.5 (3)
C7—C8—N2—C9	−77.11 (16)	C13—C18—C17—C16	−0.2 (3)
C15—C14—C13—C18	−0.1 (2)	C15—C16—C17—C18	0.4 (4)
S1—C14—C13—C18	179.19 (13)	C21—O4—C22—C23	165.63 (18)
C15—C14—C13—C12	−177.72 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3i	0.93	2.46	3.212 (2)	138

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
C5H5O3i	0.93	2.46	3.212(2)	138

Symmetry code: (i) .