2-(5-Fluoro-2,3-dioxoindolin-1-yl)ethyl 4-methyl­piperazine-1-carbodithio­ate

Wang, Y.; Lin, H.-H.; Cao, S.-L.

doi:10.1107/S1600536811052494

organic compounds

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ISSN: 2056-9890

Volume 68| Part 1| January 2012| Pages o94-o95

doi:10.1107/S1600536811052494

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2-(5-Fluoro-2,3-dioxoindolin-1-yl)ethyl 4-methylpiperazine-1-carbodithioate

Yao Wang,^a Hui-Hui Lin ^a and Sheng-Li Cao ^a ^*

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: slcao@cnu.edu.cn

(Received 21 November 2011; accepted 6 December 2011; online 10 December 2011)

In the title compound, C₁₆H₁₈FN₃O₂S₂, the methylpiperazine 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 carbodithioate group. In the crystal, each molecule is linked to its neighbors within the ( $[\overline{1}]$ 03) plane through weak C—H(methylene)⋯O, C—H(aryl)⋯O and C—H(methylene)⋯S interactions. Perpendicular to this plane molecules are connected through intermolecular short N⋯π(pyrrole ring) contacts [N⋯C centroid = 3.232 (2) Å], another set of C—H(methylene)⋯O interactions and through short contacts between carbodithioate 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_r = 367.45
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.100
S = 1.04
3861 reflections
217 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.20 e Å⁻³

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) -x+1, -y+1, -z+1; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{5\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811052494/zl2432sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536811052494/zl2432Isup3.cml

checkCIF report

Comment top

Indoline-2,3-dione and its derivatives are well known for their broad spectrum biological and pharmacological properties including anticonvulsant (Bhattacharya & Chakrabarti, 1998), anti-inflammatory (Sridhar et al., 2001) and anxiogenic (Medvedev et al., 1996) activities. On the other hand, dithiocarbamates also exhibit a large range of biological activities such as fungicidal (Ozkirimli et al., 2005) and antitumor activities (Cao et al., 2005; Gaspari et al., 2006). In an attempt to obtain compounds that might also exhibit antitumor properties, but possibly with increased potency and selectivity, we designed and synthesized the title compoud (C₁₆H₁₈N₃O₂FS₂), which consists of an indole core with a dithiocarbamate side chain (Scheme 1). In the present context, we report the crystal structure of the new compound.

In the crystalline structure of the title compound, the 1-methylpiperazine ring adopts a chair conformation, while the indoline-2,3-dione ethyl moiety is linked to one of the N atoms of the piperazine ring via the carbodithioate group, with the ethyl group in a trans-conformation (N1—C9—C10—S2 torsion angle of 175.74 (11)°, Fig. 1). This trans-conformation differentiates the title compound from the related compound 2-(2,3-dioxoindolin-1-yl)ethyl-4-(4-nitrophenyl)piperazine-1-carbodithioate reported by us recently (Wang et al., 2010), which was found to have a gauge-conformation with an N4(pyrrole)—C19—C20—S2 torsion angle of 66.16 (15)°. Through weak C13—H13B(methylene)···O2ⁱ, C—H(aryl)···O1ⁱⁱ and C12—H12B(methylene)···S2ⁱⁱⁱ interactions each molecule is linked to its neighbors within the (-1 0 3) Miller plane (Table 1 and Fig. 2). Perpendicular to this plane molecules are connected through intermolecular short N···π (pyrrole ring) contacts, another set of C—H(methylene)···O interactions (Table 1) and through short contacts between carbodithioate sulfur atoms and the pyrrole rings (C11═S1···Cg1^iv, Table 2). A short contact is observed between the nitrogen atom N1 and the π-electron desnity of the pyrrole ring, with an N3···Cg^v (Cg = C5-C6-C7-N1-C8, (v) = -x+1.5, y+0.5, -z+1.5) distance equal to 3.232 (2) Å, which is shorter than the van der Waals distance (3.40 Å) on the basis of Pauling's value for the half thickness of phenyl rings (1.85 Å) (Malone et al.,1997) and the van der Waals radius of N (1.55 Å) (Bondi, 1964). It is comparable to the N(pyrazinyl)···centroid(pyrazinyl) distance of 3.05 Å in {[Ni(L)(NO₃)₂]}_∞ (L = bis(2-pyraylmethyl)sulfide) reported by Black et al. (2007). Regarding the C11═S1···π contact (Table 2), the C═S bond is almost parallel to the pyrrole ring with a C11═S1···Cg1(pyrrole) angle equal to 86.42 (2)°, a contact mode similar to that of the C═O···π (pyridyl) contact in Cu(L)₂(BF₄)₂ (L = 2,6-pyridinediylbis(3-pyridinyl)methanone) reported by Wan et al. (2008).

Related literature top

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 top

A suspension of 1-methylpiperazine (2.4 mmol), carbon disulfide (0.72 mL, 12 mmol) and anhydrous potassium phosphate (0.51 g, 2.4 mmol) in N,N-dimethylformamide (15 mL) was stirred at room temperature for 30 minutes. Then, 1-(2-bromoethyl)-5-fluoroindoline-2,3-dione (2 mmol) was added and stirring was continued for 3.5 h. The reaction mixture was poured into water (100 mL) and the resulting precipitate was separated by filtration and further purified by column chromatography on silica gel with dichloromethane/methanol = 95:5 (v/v) as the eluent to give the title compound (R_f = 0.44, m.p. 472.2-473.2 K; yield 78%). After two weeks, the orange crystals of the title compound were deposited by slow evaporation from a solution of dichloromethane/N,N-dimethylformamide 1:1 (v/v) at room temperature.

Computing details top

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

Figures top

	Fig. 1. The title molecule with the atomic numbering scheme. The displacement ellipsoids of the non-hydrogen atoms are shown at the 30% probability level.
	Fig. 2. The intermolecular C—H(aryl)···O, C—H(methylene)···S and C—H(methylene)···O interactions of the title compound within the (-1 0 3) Miller plane. View perpendicular to this plane.
	Fig. 3. View down the b direction of the stacking structure of the title compound. All weak non-covalent interactions are omitted for clarity.

2-(5-Fluoro-2,3-dioxoindolin-1-yl)ethyl 4-methylpiperazine-1-carbodithioate top

Crystal data top

C₁₆H₁₈FN₃O₂S₂	F(000) = 768
M_r = 367.45	D_x = 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

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3861 independent reflections
Radiation source: fine-focus sealed tube	3058 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
CCD area detector scans	θ_max = 27.6°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker 2007)	h = −13→13
T_min = 0.658, T_max = 0.746	k = −20→20
18809 measured reflections	l = −11→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0506P)² + 0.3797P] P = (F_o² + 2F_c²)/3
3861 reflections	(Δ/σ)_max = 0.001
217 parameters	Δρ_max = 0.22 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₆H₁₈FN₃O₂S₂	V = 1689.96 (12) Å³
M_r = 367.45	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.0258 (4) Å	µ = 0.34 mm⁻¹
b = 15.9925 (6) Å	T = 296 K
c = 11.0016 (5) Å	0.30 × 0.30 × 0.20 mm
β = 106.656 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	3861 independent reflections
Absorption correction: multi-scan (SADABS; Bruker 2007)	3058 reflections with I > 2σ(I)
T_min = 0.658, T_max = 0.746	R_int = 0.031
18809 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.04	Δρ_max = 0.22 e Å⁻³
3861 reflections	Δρ_min = −0.20 e Å⁻³
217 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···Cg1^iv	1.67 (1)	3.40 (1)	3.695 (3)	86 (1)

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+5/2, y+1/2, −z+3/2; (iv) −x+5/2, y+3/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₈FN₃O₂S₂
M_r	367.45
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	10.0258 (4), 15.9925 (6), 11.0016 (5)
β (°)	106.656 (3)
V (Å³)	1689.96 (12)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker 2007)
T_min, T_max	0.658, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	18809, 3861, 3058
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.100, 1.04
No. of reflections	3861
No. of parameters	217
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.20

Computer programs: APEX2 (Bruker, 2007), APEX2 and SAINT (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+5/2, y+1/2, −z+3/2.

C═S···π-electron ring interactions (Å) top

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

Symmetry code: (i) -x+2,-y+1,-z+1. Cg1 is the centroid of N1-C8-C5-C6-C7 (pyrrole).

Acknowledgements

The authors are grateful to the National Natural Science Foundation of China (project No. 20972099) and the Beijing Municipal Commission of Education for financial support.

References

Bhattacharya, S. K. & Chakrabarti, A. (1998). Indian J. Exp. Biol. 36, 118–121. CAS PubMed Google Scholar
Black, C. A., Hanton, L. R. & Spicer, M. D. (2007). Inorg. Chem. 46, 3669–3679. Web of Science CSD CrossRef PubMed CAS Google Scholar
Bondi, A. (1964). J. Phys. Chem. 68, 441–51. CrossRef CAS Web of Science Google Scholar
Bruker (2007). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, S. L., Feng, Y. P., Jiang, Y. Y., Liu, S. Y., Ding, G. Y. & Li, R. T. (2005). Bioorg. Med. Chem. Lett. 15, 1915–1917. Web of Science CrossRef PubMed CAS Google Scholar
Gaspari, P., Banerjee, T., Malachowski, W. P., Muller, A. J., Prendergast, G. C., DuHadaway, J., Bennett, S. & Donovan, A. M. (2006). J. Med. Chem. 49, 684–692. Web of Science CrossRef PubMed CAS Google Scholar
Malone, J. F., Murray, C. M., Charlton, M. H., Docherty, R. & Lavery, A. J. (1997). J Chem. Soc. Faraday Trans. 93, 3429–3436. CrossRef CAS Web of Science Google Scholar
Medvedev, A. E., Clow, A., Sandler, M. & Glover, V. (1996). Biochem. Pharmacol. 52, 385–391. CrossRef CAS PubMed Web of Science Google Scholar
Ozkirimli, S., Apak, T. I., Kiraz, M. & Yegenoglu, Y. (2005). Arch. Pharm. Res. 28, 1213–1218. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sridhar, S. K. & Ramesh, A. (2001). Biol. Pharm. Bull. 24, 1149–1152. Web of Science CrossRef PubMed CAS Google Scholar
Wan, C. Q., Chen, X. D. & Mak, T. C. W. (2008). CrystEngComm, 10, 475–478. Web of Science CSD CrossRef CAS Google Scholar
Wang, Y., Wan, C.-Q., Cao, S.-L. & Zheng, T. (2010). Acta Cryst. E66, o2243. Web of Science CSD CrossRef IUCr Journals Google Scholar