2-(5-Fluoro-2,3-dioxoindolin-1-yl)ethyl 4-methyl-piperazine-1-carbodithio-ate.

In the title compound, C(16)H(18)FN(3)O(2)S(2), the methyl-piperazine ring adopts a chair conformation, while the (2,3-dioxoindolin-1-yl)ethyl unit is linked to one of the N atoms of the piperazine ring via the carbodithio-ate group. In the crystal, each mol-ecule is linked to its neighbors within the ([Formula: see text]03) plane through weak C-H(methyl-ene)⋯O, C-H(ar-yl)⋯O and C-H(methyl-ene)⋯S inter-actions. Perpendicular to this plane mol-ecules are connected through inter-molecular short N⋯π(pyrrole ring) contacts [N⋯C centroid = 3.232 (2) Å], another set of C-H(methyl-ene)⋯O inter-actions and through short contacts between carbodithio-ate S atoms and the pyrrole rings [C⋯centroid = 3.695 (3), S⋯centroid = 3.403 (2) Å].

Related literature

For background to indoline-2,3-dione and its derivatives, see: Bhattacharya & Chakrabarti (1998 ▶); Sridhar & Ramesh (2001 ▶); Medvedev et al. (1996 ▶) and to dithio­carbamates, see: Ozkirimli et al. (2005 ▶); Cao et al. (2005 ▶); Gaspari et al. (2006 ▶). For analogues of 5-fluoro­indoline-2,3-dione, see: Wang et al. (2010 ▶). For N⋯π contacts, see: Black et al. (2007 ▶). For van der Waals radii, see Bondi (1964 ▶). For the thickness of phenyl rings, see: Malone et al. (1997 ▶). For C=O⋯π (pyrid­yl) contacts, see: Wan et al. (2008 ▶)

Experimental

Crystal data

C16H18FN3O2S2

M = 367.45

Monoclinic,

a = 10.0258 (4) Å

b = 15.9925 (6) Å

c = 11.0016 (5) Å

β = 106.656 (3)°

V = 1689.96 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.34 mm−1

T = 296 K

0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker 2007 ▶) T min = 0.658, T max = 0.746

18809 measured reflections

3861 independent reflections

3058 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.100

S = 1.04

3861 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.22 e Å−3

Δρmin = −0.20 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: APEX2 and 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052494/zl2432sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052494/zl2432Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811052494/zl2432Isup3.cml

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

C16H18FN3O2S2	F(000) = 768
Mr = 367.45	Dx = 1.444 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 222 reflections
a = 10.0258 (4) Å	θ = 2.3–27.6°
b = 15.9925 (6) Å	µ = 0.34 mm−1
c = 11.0016 (5) Å	T = 296 K
β = 106.656 (3)°	Block, colorless
V = 1689.96 (12) Å3	0.30 × 0.30 × 0.20 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	3861 independent reflections
Radiation source: fine-focus sealed tube	3058 reflections with I > 2σ(I)
graphite	Rint = 0.031
CCD area detector scans	θmax = 27.6°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker 2007)	h = −13→13
Tmin = 0.658, Tmax = 0.746	k = −20→20
18809 measured reflections	l = −11→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0506P)2 + 0.3797P] P = (Fo2 + 2Fc2)/3
3861 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.22 e Å−3
0 restraints	Δρmin = −0.20 e Å−3

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	0.91389 (4)	0.66656 (2)	0.57656 (4)	0.04717 (13)
S2	0.69048 (4)	0.53592 (2)	0.54985 (5)	0.04795 (14)
N1	1.04768 (13)	0.40980 (8)	0.72003 (13)	0.0436 (3)
N2	0.64449 (12)	0.69676 (7)	0.54089 (14)	0.0423 (3)
N3	0.42553 (14)	0.81754 (8)	0.50085 (14)	0.0466 (3)
O1	1.22167 (14)	0.21917 (7)	0.75006 (15)	0.0677 (4)
O2	0.93355 (12)	0.28341 (8)	0.68042 (13)	0.0580 (3)
F1	1.60973 (12)	0.46870 (8)	0.86069 (15)	0.0840 (4)
C1	1.24078 (19)	0.51646 (9)	0.77343 (17)	0.0477 (4)
H1A	1.1821	0.5626	0.7618	0.057*
C2	1.3845 (2)	0.52580 (10)	0.80939 (19)	0.0554 (4)
H2A	1.4233	0.5790	0.8224	0.066*
C3	1.46982 (18)	0.45705 (11)	0.82584 (19)	0.0555 (5)
C4	1.41990 (17)	0.37630 (10)	0.80778 (18)	0.0502 (4)
H4A	1.4793	0.3305	0.8192	0.060*
C5	1.27711 (16)	0.36716 (9)	0.77186 (16)	0.0419 (4)
C6	1.19005 (16)	0.29208 (9)	0.74546 (17)	0.0465 (4)
C7	1.03847 (16)	0.32457 (10)	0.70982 (17)	0.0449 (4)
C8	1.18809 (15)	0.43610 (9)	0.75556 (15)	0.0397 (3)
C9	0.92604 (17)	0.46265 (11)	0.70586 (17)	0.0488 (4)
H9A	0.9553	0.5161	0.7465	0.059*
H9B	0.8643	0.4365	0.7483	0.059*
C10	0.84770 (16)	0.47709 (10)	0.56780 (17)	0.0446 (4)
H10A	0.8247	0.4235	0.5257	0.054*
H10B	0.9073	0.5069	0.5269	0.054*
C11	0.74743 (15)	0.64129 (9)	0.55535 (15)	0.0368 (3)
C12	0.50387 (16)	0.67350 (10)	0.5460 (2)	0.0531 (5)
H12A	0.5005	0.6763	0.6331	0.064*
H12B	0.4842	0.6164	0.5168	0.064*
C13	0.39430 (17)	0.73083 (11)	0.4648 (2)	0.0545 (4)
H13A	0.3903	0.7235	0.3763	0.065*
H13B	0.3040	0.7163	0.4745	0.065*
C14	0.55667 (18)	0.83880 (10)	0.47625 (18)	0.0507 (4)
H14A	0.5765	0.8976	0.4946	0.061*
H14B	0.5482	0.8297	0.3872	0.061*
C15	0.67565 (16)	0.78703 (9)	0.55582 (18)	0.0470 (4)
H15A	0.7590	0.7989	0.5309	0.056*
H15B	0.6935	0.8024	0.6443	0.056*
C16	0.3137 (2)	0.87270 (12)	0.4299 (2)	0.0615 (5)
H16A	0.2276	0.8563	0.4449	0.092*
H16B	0.3051	0.8686	0.3410	0.092*
H16C	0.3350	0.9294	0.4575	0.092*

	U11	U22	U33	U12	U13	U23
S1	0.03141 (19)	0.0426 (2)	0.0657 (3)	−0.00238 (15)	0.01100 (18)	−0.00061 (18)
S2	0.03104 (19)	0.03047 (19)	0.0770 (3)	0.00221 (13)	0.00697 (18)	0.00188 (17)
N1	0.0375 (6)	0.0350 (6)	0.0536 (9)	0.0071 (5)	0.0055 (6)	0.0042 (6)
N2	0.0310 (6)	0.0303 (6)	0.0618 (9)	0.0001 (5)	0.0072 (6)	−0.0043 (6)
N3	0.0431 (7)	0.0370 (7)	0.0530 (9)	0.0105 (5)	0.0030 (6)	−0.0005 (6)
O1	0.0549 (7)	0.0274 (6)	0.1107 (12)	0.0032 (5)	0.0075 (7)	−0.0003 (6)
O2	0.0407 (6)	0.0551 (7)	0.0713 (9)	−0.0104 (5)	0.0047 (6)	0.0008 (6)
F1	0.0452 (6)	0.0693 (8)	0.1238 (12)	−0.0187 (5)	0.0025 (7)	0.0018 (7)
C1	0.0571 (9)	0.0290 (7)	0.0549 (10)	0.0053 (7)	0.0127 (8)	0.0033 (7)
C2	0.0618 (11)	0.0337 (8)	0.0655 (12)	−0.0110 (7)	0.0102 (9)	−0.0015 (7)
C3	0.0416 (9)	0.0483 (9)	0.0680 (12)	−0.0110 (7)	0.0019 (8)	0.0006 (8)
C4	0.0386 (8)	0.0371 (8)	0.0670 (12)	0.0029 (6)	0.0026 (8)	0.0035 (7)
C5	0.0388 (8)	0.0278 (7)	0.0531 (10)	0.0014 (6)	0.0039 (7)	0.0020 (6)
C6	0.0402 (8)	0.0306 (7)	0.0621 (11)	0.0000 (6)	0.0041 (7)	0.0013 (7)
C7	0.0378 (8)	0.0399 (8)	0.0516 (10)	−0.0002 (6)	0.0042 (7)	0.0028 (7)
C8	0.0403 (7)	0.0315 (7)	0.0434 (9)	0.0046 (6)	0.0058 (7)	0.0038 (6)
C9	0.0428 (8)	0.0481 (9)	0.0556 (11)	0.0139 (7)	0.0144 (8)	0.0060 (7)
C10	0.0357 (7)	0.0366 (7)	0.0582 (10)	0.0080 (6)	0.0083 (7)	−0.0004 (7)
C11	0.0326 (7)	0.0332 (7)	0.0411 (8)	0.0000 (5)	0.0047 (6)	−0.0016 (6)
C12	0.0321 (7)	0.0320 (7)	0.0921 (14)	0.0004 (6)	0.0130 (8)	−0.0041 (8)
C13	0.0341 (8)	0.0466 (9)	0.0742 (12)	0.0037 (7)	0.0014 (8)	−0.0134 (8)
C14	0.0519 (9)	0.0373 (8)	0.0588 (11)	0.0038 (7)	0.0092 (8)	0.0006 (7)
C15	0.0410 (8)	0.0300 (7)	0.0660 (11)	−0.0022 (6)	0.0090 (8)	−0.0053 (7)
C16	0.0582 (11)	0.0553 (11)	0.0632 (12)	0.0224 (9)	0.0050 (9)	0.0085 (9)

S1—C11	1.6673 (15)	C4—H4A	0.9300
S2—C11	1.7747 (15)	C5—C8	1.397 (2)
S2—C10	1.7973 (15)	C5—C6	1.464 (2)
N1—C7	1.369 (2)	C6—C7	1.547 (2)
N1—C8	1.413 (2)	C9—C10	1.514 (2)
N1—C9	1.4550 (19)	C9—H9A	0.9700
N2—C11	1.3353 (19)	C9—H9B	0.9700
N2—C12	1.4746 (19)	C10—H10A	0.9700
N2—C15	1.4763 (19)	C10—H10B	0.9700
N3—C13	1.452 (2)	C12—C13	1.511 (2)
N3—C14	1.457 (2)	C12—H12A	0.9700
N3—C16	1.464 (2)	C12—H12B	0.9700
O1—C6	1.2056 (18)	C13—H13A	0.9700
O2—C7	1.2039 (19)	C13—H13B	0.9700
F1—C3	1.357 (2)	C14—C15	1.509 (2)
C1—C8	1.382 (2)	C14—H14A	0.9700
C1—C2	1.389 (3)	C14—H14B	0.9700
C1—H1A	0.9300	C15—H15A	0.9700
C2—C3	1.373 (3)	C15—H15B	0.9700
C2—H2A	0.9300	C16—H16A	0.9600
C3—C4	1.379 (2)	C16—H16B	0.9600
C4—C5	1.379 (2)	C16—H16C	0.9600
C11—S2—C10	103.29 (7)	C9—C10—S2	112.11 (11)
C7—N1—C8	110.95 (12)	C9—C10—H10A	109.2
C7—N1—C9	122.35 (14)	S2—C10—H10A	109.2
C8—N1—C9	126.50 (13)	C9—C10—H10B	109.2
C11—N2—C12	122.86 (13)	S2—C10—H10B	109.2
C11—N2—C15	120.31 (13)	H10A—C10—H10B	107.9
C12—N2—C15	114.61 (12)	N2—C11—S1	124.34 (11)
C13—N3—C14	107.92 (13)	N2—C11—S2	113.37 (11)
C13—N3—C16	110.97 (14)	S1—C11—S2	122.29 (8)
C14—N3—C16	110.77 (14)	N2—C12—C13	111.44 (14)
C8—C1—C2	117.62 (14)	N2—C12—H12A	109.3
C8—C1—H1A	121.2	C13—C12—H12A	109.3
C2—C1—H1A	121.2	N2—C12—H12B	109.3
C3—C2—C1	120.51 (15)	C13—C12—H12B	109.3
C3—C2—H2A	119.7	H12A—C12—H12B	108.0
C1—C2—H2A	119.7	N3—C13—C12	110.78 (14)
F1—C3—C2	118.80 (16)	N3—C13—H13A	109.5
F1—C3—C4	118.20 (16)	C12—C13—H13A	109.5
C2—C3—C4	123.00 (16)	N3—C13—H13B	109.5
C3—C4—C5	116.40 (15)	C12—C13—H13B	109.5
C3—C4—H4A	121.8	H13A—C13—H13B	108.1
C5—C4—H4A	121.8	N3—C14—C15	111.70 (14)
C4—C5—C8	121.70 (14)	N3—C14—H14A	109.3
C4—C5—C6	130.89 (14)	C15—C14—H14A	109.3
C8—C5—C6	107.41 (13)	N3—C14—H14B	109.3
O1—C6—C5	130.57 (15)	C15—C14—H14B	109.3
O1—C6—C7	124.27 (15)	H14A—C14—H14B	107.9
C5—C6—C7	105.15 (12)	N2—C15—C14	111.42 (13)
O2—C7—N1	126.86 (15)	N2—C15—H15A	109.3
O2—C7—C6	127.14 (15)	C14—C15—H15A	109.3
N1—C7—C6	106.00 (13)	N2—C15—H15B	109.3
C1—C8—C5	120.76 (14)	C14—C15—H15B	109.3
C1—C8—N1	128.76 (14)	H15A—C15—H15B	108.0
C5—C8—N1	110.48 (13)	N3—C16—H16A	109.5
N1—C9—C10	111.95 (14)	N3—C16—H16B	109.5
N1—C9—H9A	109.2	H16A—C16—H16B	109.5
C10—C9—H9A	109.2	N3—C16—H16C	109.5
N1—C9—H9B	109.2	H16A—C16—H16C	109.5
C10—C9—H9B	109.2	H16B—C16—H16C	109.5
H9A—C9—H9B	107.9
C8—C1—C2—C3	0.2 (3)	C7—N1—C8—C1	178.77 (17)
C1—C2—C3—F1	179.83 (18)	C9—N1—C8—C1	−6.3 (3)
C1—C2—C3—C4	0.3 (3)	C7—N1—C8—C5	−0.9 (2)
F1—C3—C4—C5	−179.72 (18)	C9—N1—C8—C5	174.01 (15)
C2—C3—C4—C5	−0.1 (3)	C7—N1—C9—C10	−80.2 (2)
C3—C4—C5—C8	−0.4 (3)	C8—N1—C9—C10	105.47 (19)
C3—C4—C5—C6	−179.75 (19)	N1—C9—C10—S2	175.74 (11)
C4—C5—C6—O1	1.0 (4)	C11—S2—C10—C9	87.13 (13)
C8—C5—C6—O1	−178.4 (2)	C12—N2—C11—S1	−168.35 (14)
C4—C5—C6—C7	−179.90 (19)	C15—N2—C11—S1	−6.2 (2)
C8—C5—C6—C7	0.70 (19)	C12—N2—C11—S2	11.7 (2)
C8—N1—C7—O2	−179.46 (18)	C15—N2—C11—S2	173.86 (12)
C9—N1—C7—O2	5.4 (3)	C10—S2—C11—N2	178.69 (12)
C8—N1—C7—C6	1.28 (18)	C10—S2—C11—S1	−1.28 (13)
C9—N1—C7—C6	−173.87 (15)	C11—N2—C12—C13	−150.62 (16)
O1—C6—C7—O2	−1.3 (3)	C15—N2—C12—C13	46.3 (2)
C5—C6—C7—O2	179.54 (18)	C14—N3—C13—C12	63.3 (2)
O1—C6—C7—N1	177.94 (19)	C16—N3—C13—C12	−175.16 (16)
C5—C6—C7—N1	−1.21 (18)	N2—C12—C13—N3	−55.4 (2)
C2—C1—C8—C5	−0.7 (3)	C13—N3—C14—C15	−62.61 (18)
C2—C1—C8—N1	179.63 (17)	C16—N3—C14—C15	175.73 (14)
C4—C5—C8—C1	0.9 (3)	C11—N2—C15—C14	151.30 (15)
C6—C5—C8—C1	−179.65 (16)	C12—N2—C15—C14	−45.1 (2)
C4—C5—C8—N1	−179.43 (16)	N3—C14—C15—N2	53.36 (19)
C6—C5—C8—N1	0.04 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13B···O2i	0.97	2.50	3.225 (2)	131
C12—H12A···O2ii	0.97	2.61	3.385 (2)	137
C15—H15B···O2ii	0.97	2.62	3.383 (2)	136
C1—H1A···O1iii	0.93	2.70	3.282 (3)	121
C2—H2A···O1iii	0.93	2.67	3.275 (2)	124
C12—H12B···S2i	0.97	2.97	3.866 (3)	155
C11—S1···Cg1iv	1.6673 (15)	3.403 (2)	3.695 (3)	86.43 (6)

C═S···Cg	C···Cg	S···Cg
C11═S1···Cg1i	3.695 (3)	3.403 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13B⋯O2i	0.97	2.50	3.225 (2)	131
C12—H12A⋯O2ii	0.97	2.61	3.385 (2)	137
C15—H15B⋯O2ii	0.97	2.62	3.383 (2)	136
C1—H1A⋯O1iii	0.93	2.70	3.282 (3)	121
C2—H2A⋯O1iii	0.93	2.67	3.275 (2)	124
C12—H12B⋯S2i	0.97	2.97	3.866 (3)	155

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