1'-Acetyl-3-phenyl-6-oxa-4-thia-2-aza-spiro-[bicyclo-[3.2.0]hept-2-ene-7,3'-indolin]-2'-one.

In the title indoline compound, C(19)H(14)N(2)O(3)S, the pyrrolidine ring adopts an envelope conformation with the four-connected (spiro) C atom as the flap [displacement = 0.148 (3) Å]. The mean plane formed through the indoline unit is inclined at dihedral angles of 89.92 (16) and 59.54 (12)° with the thia-zole and phenyl rings, respectively; the dihedral angle between the latter rings is 9.55 (14)°. In the crystal, pairs of inter-molecular C-H⋯O hydrogen bonds link neighbouring mol-ecules into inversion dimers, producing R(2) (2)(6) hydrogen-bond ring motifs. Weak inter-molecular C-H⋯π as well as π-π inter-actions [centroid-centroid distance = 3.4041 (15) Å] further consolidate the crystal structure.

Related literature

For general background to and applications of compounds related to the title indoline compound, see: Aanandhi et al. (2008 ▶); Crews et al. (1988 ▶); Cutignano et al. (2001 ▶); DeRoy & Charette (2003 ▶); Gao et al. (2010 ▶); Kaleta et al. (2006 ▶); Lawrence et al. (2008 ▶); Muthukumar et al. (2008 ▶); Shi et al. (2010 ▶); Tsuruni et al. (1995 ▶); Wang et al. (2005 ▶); Williams et al. (2001 ▶); Xue et al. (2000 ▶); Yoshimura et al. (1995 ▶); Zhang et al. (2004 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For graph-set theory of hydrogen-bond ring motifs, see: Bernstein et al. (1995 ▶). For closely related structures, see: Fun et al. (2010 ▶); Usman et al. (2001 ▶, 2002 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C19H14N2O3S

M = 350.38

Triclinic,

a = 7.5054 (3) Å

b = 9.4936 (3) Å

c = 11.6359 (4) Å

α = 103.502 (3)°

β = 91.163 (3)°

γ = 100.200 (3)°

V = 791.79 (5) Å3

Z = 2

Mo Kα radiation

μ = 0.23 mm−1

T = 100 K

0.24 × 0.10 × 0.05 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.948, T max = 0.989

10748 measured reflections

3627 independent reflections

2548 reflections with I > 2σ(I)

R int = 0.062

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.128

S = 1.05

3627 reflections

227 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.42 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810031016/hb5595sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810031016/hb5595Isup2.hkl

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

C19H14N2O3S	Z = 2
Mr = 350.38	F(000) = 364
Triclinic, P1	Dx = 1.470 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.5054 (3) Å	Cell parameters from 2361 reflections
b = 9.4936 (3) Å	θ = 2.5–29.9°
c = 11.6359 (4) Å	µ = 0.23 mm−1
α = 103.502 (3)°	T = 100 K
β = 91.163 (3)°	Block, colourless
γ = 100.200 (3)°	0.24 × 0.10 × 0.05 mm
V = 791.79 (5) Å3

Bruker SMART APEXII CCD diffractometer	3627 independent reflections
Radiation source: fine-focus sealed tube	2548 reflections with I > 2σ(I)
graphite	Rint = 0.062
φ and ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −9→9
Tmin = 0.948, Tmax = 0.989	k = −12→10
10748 measured reflections	l = −15→15

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0437P)2 + 0.6382P] where P = (Fo2 + 2Fc2)/3
3627 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.35 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1)K.

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	0.31424 (10)	0.63788 (7)	0.48799 (6)	0.01816 (18)
O1	0.5459 (3)	0.90182 (19)	0.58975 (16)	0.0190 (4)
O2	0.6257 (3)	0.7176 (2)	0.74453 (17)	0.0244 (5)
O3	0.8183 (3)	0.9955 (2)	1.07309 (17)	0.0229 (5)
N1	0.6758 (3)	0.9398 (2)	0.89013 (19)	0.0156 (5)
N2	0.2265 (3)	0.7250 (2)	0.70929 (19)	0.0158 (5)
C1	0.5502 (4)	1.0821 (3)	0.7864 (2)	0.0161 (6)
C2	0.5067 (4)	1.2098 (3)	0.7631 (2)	0.0186 (6)
H2A	0.4462	1.2074	0.6919	0.022*
C3	0.5566 (4)	1.3413 (3)	0.8498 (3)	0.0204 (6)
H3A	0.5333	1.4291	0.8358	0.025*
C4	0.6407 (4)	1.3411 (3)	0.9567 (3)	0.0212 (6)
H4A	0.6693	1.4293	1.0143	0.025*
C5	0.6845 (4)	1.2135 (3)	0.9816 (2)	0.0180 (6)
H5A	0.7404	1.2149	1.0540	0.022*
C6	0.6399 (4)	1.0849 (3)	0.8924 (2)	0.0159 (6)
C7	0.6062 (4)	0.8429 (3)	0.7805 (2)	0.0173 (6)
C8	0.5034 (4)	0.9279 (3)	0.7127 (2)	0.0161 (6)
C9	0.2983 (4)	0.8603 (3)	0.6760 (2)	0.0156 (6)
H9A	0.2192	0.9334	0.6934	0.019*
C10	0.3596 (4)	0.8344 (3)	0.5480 (2)	0.0168 (6)
H10A	0.3038	0.8885	0.4995	0.020*
C11	0.2314 (4)	0.6112 (3)	0.6260 (2)	0.0156 (6)
C12	0.1634 (4)	0.4594 (3)	0.6374 (2)	0.0157 (6)
C13	0.0699 (4)	0.4403 (3)	0.7366 (2)	0.0180 (6)
H13A	0.0553	0.5223	0.7949	0.022*
C14	−0.0011 (4)	0.3003 (3)	0.7486 (2)	0.0198 (6)
H14A	−0.0637	0.2881	0.8148	0.024*
C15	0.0213 (4)	0.1773 (3)	0.6613 (3)	0.0213 (6)
H15A	−0.0262	0.0829	0.6691	0.026*
C16	0.1142 (4)	0.1963 (3)	0.5632 (3)	0.0217 (6)
H16A	0.1287	0.1142	0.5050	0.026*
C17	0.1866 (4)	0.3371 (3)	0.5504 (2)	0.0181 (6)
H17A	0.2497	0.3491	0.4844	0.022*
C18	0.7757 (4)	0.9051 (3)	0.9798 (2)	0.0170 (6)
C19	0.8273 (4)	0.7560 (3)	0.9534 (3)	0.0240 (7)
H19D	0.8923	0.7446	1.0216	0.036*
H19A	0.9029	0.7467	0.8875	0.036*
H19B	0.7197	0.6812	0.9343	0.036*

	U11	U22	U33	U12	U13	U23
S1	0.0253 (4)	0.0130 (3)	0.0158 (3)	0.0014 (3)	0.0011 (3)	0.0044 (3)
O1	0.0228 (11)	0.0163 (9)	0.0174 (10)	0.0026 (8)	0.0010 (8)	0.0037 (8)
O2	0.0338 (13)	0.0134 (10)	0.0266 (11)	0.0091 (9)	−0.0044 (9)	0.0030 (8)
O3	0.0289 (12)	0.0223 (10)	0.0180 (10)	0.0053 (9)	0.0006 (9)	0.0060 (9)
N1	0.0201 (13)	0.0111 (10)	0.0167 (11)	0.0030 (9)	0.0020 (9)	0.0054 (9)
N2	0.0177 (12)	0.0115 (11)	0.0184 (12)	0.0027 (9)	0.0012 (9)	0.0042 (9)
C1	0.0174 (15)	0.0109 (12)	0.0202 (14)	0.0008 (11)	0.0042 (11)	0.0052 (11)
C2	0.0188 (15)	0.0152 (13)	0.0237 (14)	0.0041 (11)	−0.0008 (12)	0.0081 (11)
C3	0.0198 (15)	0.0101 (13)	0.0332 (16)	0.0044 (11)	0.0041 (12)	0.0074 (12)
C4	0.0237 (17)	0.0133 (13)	0.0241 (15)	0.0022 (12)	0.0052 (12)	0.0002 (11)
C5	0.0167 (15)	0.0166 (13)	0.0196 (14)	0.0016 (11)	0.0023 (11)	0.0034 (11)
C6	0.0167 (15)	0.0125 (12)	0.0204 (14)	0.0027 (11)	0.0025 (11)	0.0075 (11)
C7	0.0210 (16)	0.0120 (13)	0.0192 (14)	0.0026 (11)	0.0010 (11)	0.0050 (11)
C8	0.0226 (16)	0.0111 (12)	0.0151 (13)	0.0020 (11)	0.0023 (11)	0.0049 (11)
C9	0.0196 (15)	0.0118 (12)	0.0162 (13)	0.0018 (11)	0.0015 (11)	0.0055 (11)
C10	0.0193 (15)	0.0116 (12)	0.0202 (14)	0.0018 (11)	−0.0006 (11)	0.0062 (11)
C11	0.0160 (14)	0.0149 (13)	0.0180 (13)	0.0045 (11)	0.0003 (11)	0.0066 (11)
C12	0.0145 (14)	0.0134 (12)	0.0191 (14)	0.0012 (11)	−0.0019 (11)	0.0049 (11)
C13	0.0235 (16)	0.0155 (13)	0.0149 (13)	0.0045 (12)	0.0013 (11)	0.0027 (11)
C14	0.0211 (16)	0.0212 (14)	0.0193 (14)	0.0032 (12)	0.0025 (12)	0.0100 (12)
C15	0.0213 (16)	0.0119 (13)	0.0314 (16)	0.0016 (11)	0.0001 (13)	0.0079 (12)
C16	0.0244 (17)	0.0136 (13)	0.0256 (15)	0.0046 (12)	0.0013 (13)	0.0011 (12)
C17	0.0175 (15)	0.0171 (14)	0.0197 (14)	0.0044 (11)	0.0029 (11)	0.0033 (11)
C18	0.0166 (15)	0.0184 (13)	0.0178 (14)	0.0017 (11)	0.0025 (11)	0.0086 (11)
C19	0.0275 (17)	0.0188 (14)	0.0282 (16)	0.0086 (12)	−0.0068 (13)	0.0083 (12)

S1—C11	1.790 (3)	C7—C8	1.538 (4)
S1—C10	1.801 (3)	C8—C9	1.568 (4)
O1—C8	1.446 (3)	C9—C10	1.544 (4)
O1—C10	1.452 (3)	C9—H9A	0.9800
O2—C7	1.201 (3)	C10—H10A	0.9800
O3—C18	1.212 (3)	C11—C12	1.479 (4)
N1—C18	1.406 (3)	C12—C17	1.390 (4)
N1—C7	1.415 (3)	C12—C13	1.393 (4)
N1—C6	1.444 (3)	C13—C14	1.382 (4)
N2—C11	1.278 (3)	C13—H13A	0.9300
N2—C9	1.444 (3)	C14—C15	1.396 (4)
C1—C6	1.385 (4)	C14—H14A	0.9300
C1—C2	1.393 (3)	C15—C16	1.380 (4)
C1—C8	1.490 (4)	C15—H15A	0.9300
C2—C3	1.396 (4)	C16—C17	1.394 (4)
C2—H2A	0.9300	C16—H16A	0.9300
C3—C4	1.383 (4)	C17—H17A	0.9300
C3—H3A	0.9300	C18—C19	1.498 (4)
C4—C5	1.400 (4)	C19—H19D	0.9600
C4—H4A	0.9300	C19—H19A	0.9600
C5—C6	1.389 (4)	C19—H19B	0.9600
C5—H5A	0.9300
C11—S1—C10	90.03 (12)	C8—C9—H9A	113.1
C8—O1—C10	92.80 (19)	O1—C10—C9	91.54 (19)
C18—N1—C7	126.1 (2)	O1—C10—S1	116.58 (17)
C18—N1—C6	124.7 (2)	C9—C10—S1	106.43 (17)
C7—N1—C6	109.1 (2)	O1—C10—H10A	113.4
C11—N2—C9	112.1 (2)	C9—C10—H10A	113.4
C6—C1—C2	121.3 (2)	S1—C10—H10A	113.4
C6—C1—C8	110.1 (2)	N2—C11—C12	122.6 (2)
C2—C1—C8	128.5 (2)	N2—C11—S1	118.4 (2)
C1—C2—C3	117.9 (3)	C12—C11—S1	118.90 (19)
C1—C2—H2A	121.0	C17—C12—C13	120.0 (2)
C3—C2—H2A	121.0	C17—C12—C11	121.5 (2)
C4—C3—C2	120.0 (2)	C13—C12—C11	118.5 (2)
C4—C3—H3A	120.0	C14—C13—C12	120.3 (2)
C2—C3—H3A	120.0	C14—C13—H13A	119.8
C3—C4—C5	122.7 (3)	C12—C13—H13A	119.8
C3—C4—H4A	118.7	C13—C14—C15	119.9 (3)
C5—C4—H4A	118.7	C13—C14—H14A	120.0
C6—C5—C4	116.4 (3)	C15—C14—H14A	120.0
C6—C5—H5A	121.8	C16—C15—C14	119.7 (2)
C4—C5—H5A	121.8	C16—C15—H15A	120.2
C1—C6—C5	121.6 (2)	C14—C15—H15A	120.2
C1—C6—N1	109.4 (2)	C15—C16—C17	120.8 (3)
C5—C6—N1	128.9 (2)	C15—C16—H16A	119.6
O2—C7—N1	126.9 (2)	C17—C16—H16A	119.6
O2—C7—C8	125.5 (2)	C12—C17—C16	119.3 (3)
N1—C7—C8	107.6 (2)	C12—C17—H17A	120.3
O1—C8—C1	117.7 (2)	C16—C17—H17A	120.3
O1—C8—C7	111.3 (2)	O3—C18—N1	119.7 (2)
C1—C8—C7	102.8 (2)	O3—C18—C19	123.0 (2)
O1—C8—C9	90.84 (19)	N1—C18—C19	117.2 (2)
C1—C8—C9	118.2 (2)	C18—C19—H19D	109.5
C7—C8—C9	116.3 (2)	C18—C19—H19A	109.5
N2—C9—C10	113.0 (2)	H19D—C19—H19A	109.5
N2—C9—C8	116.6 (2)	C18—C19—H19B	109.5
C10—C9—C8	84.8 (2)	H19D—C19—H19B	109.5
N2—C9—H9A	113.1	H19A—C19—H19B	109.5
C10—C9—H9A	113.1
C6—C1—C2—C3	0.1 (4)	C11—N2—C9—C8	−94.8 (3)
C8—C1—C2—C3	176.1 (3)	O1—C8—C9—N2	114.4 (2)
C1—C2—C3—C4	−2.3 (4)	C1—C8—C9—N2	−123.2 (2)
C2—C3—C4—C5	2.1 (4)	C7—C8—C9—N2	0.0 (3)
C3—C4—C5—C6	0.4 (4)	O1—C8—C9—C10	1.18 (17)
C2—C1—C6—C5	2.4 (4)	C1—C8—C9—C10	123.6 (2)
C8—C1—C6—C5	−174.2 (3)	C7—C8—C9—C10	−113.2 (2)
C2—C1—C6—N1	−177.0 (3)	C8—O1—C10—C9	1.27 (18)
C8—C1—C6—N1	6.4 (3)	C8—O1—C10—S1	−107.98 (19)
C4—C5—C6—C1	−2.6 (4)	N2—C9—C10—O1	−117.9 (2)
C4—C5—C6—N1	176.7 (3)	C8—C9—C10—O1	−1.18 (17)
C18—N1—C6—C1	175.4 (3)	N2—C9—C10—S1	0.4 (3)
C7—N1—C6—C1	−0.3 (3)	C8—C9—C10—S1	117.15 (17)
C18—N1—C6—C5	−3.9 (4)	C11—S1—C10—O1	99.1 (2)
C7—N1—C6—C5	−179.7 (3)	C11—S1—C10—C9	−1.19 (19)
C18—N1—C7—O2	−2.6 (5)	C9—N2—C11—C12	−179.1 (2)
C6—N1—C7—O2	173.1 (3)	C9—N2—C11—S1	−2.2 (3)
C18—N1—C7—C8	178.8 (2)	C10—S1—C11—N2	2.1 (2)
C6—N1—C7—C8	−5.6 (3)	C10—S1—C11—C12	179.2 (2)
C10—O1—C8—C1	−124.1 (2)	N2—C11—C12—C17	−173.5 (3)
C10—O1—C8—C7	117.6 (2)	S1—C11—C12—C17	9.6 (3)
C10—O1—C8—C9	−1.26 (18)	N2—C11—C12—C13	8.2 (4)
C6—C1—C8—O1	−132.0 (2)	S1—C11—C12—C13	−168.7 (2)
C2—C1—C8—O1	51.7 (4)	C17—C12—C13—C14	−0.5 (4)
C6—C1—C8—C7	−9.3 (3)	C11—C12—C13—C14	177.8 (3)
C2—C1—C8—C7	174.4 (3)	C12—C13—C14—C15	0.2 (4)
C6—C1—C8—C9	120.4 (3)	C13—C14—C15—C16	−0.1 (4)
C2—C1—C8—C9	−55.9 (4)	C14—C15—C16—C17	0.2 (4)
O2—C7—C8—O1	−42.9 (4)	C13—C12—C17—C16	0.6 (4)
N1—C7—C8—O1	135.8 (2)	C11—C12—C17—C16	−177.7 (3)
O2—C7—C8—C1	−169.8 (3)	C15—C16—C17—C12	−0.4 (4)
N1—C7—C8—C1	8.9 (3)	C7—N1—C18—O3	−175.5 (3)
O2—C7—C8—C9	59.3 (4)	C6—N1—C18—O3	9.5 (4)
N1—C7—C8—C9	−122.0 (2)	C7—N1—C18—C19	5.5 (4)
C11—N2—C9—C10	1.1 (3)	C6—N1—C18—C19	−169.5 (2)

Cg1 is the centroid of C1–C6 phenyl ring.

D—H···A	D—H	H···A	D···A	D—H···A
C10—H10A···O1i	0.98	2.56	3.261 (3)	129
C14—H14A···Cg1ii	0.93	2.67	3.423 (3)	139

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1–C6 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C10—H10A⋯O1i	0.98	2.56	3.261 (3)	129
C14—H14A⋯Cg1ii	0.93	2.67	3.423 (3)	139

Symmetry codes: (i) ; (ii) .