2-(2,3-Dioxoindolin-1-yl)ethyl 4-(4-nitro-phen-yl)piperazine-1-carbodithio-ate.

In the title compound, C(21)H(20)N(4)O(4)S(2, )the piperazine ring adopts a chair conformation. The 1-ethyl-indoline-2,3-dione system links to one N atom of the piperazine ring via a carbodithio-ate group. The indoline-2,3-dione ring and the nitro-benzene ring subtend adihedral angle of 37.27 (7)°. In the crystal structure, weak C-H⋯O and π-π stacking inter-actions [centroid-centroid distances = 3.534 (5) and 3.797 (5) Å] may help to establish the packing.

Related literature

For the fungicidal activity of dithio­carbamates, see: Farghaly et al. (1999 ▶); Xu et al. (2002 ▶); Ozkirimli et al. (2005 ▶) and for their anti­bacterial activity, see: Chourasia et al. (1999 ▶); Imamura et al. (2001 ▶). For the effective anti­tumor activity of dithio­carbamates, see: Cao et al. (2005 ▶); Gaspari et al. (2006 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C21H20N4O4S2

M = 456.53

Monoclinic,

a = 34.4244 (8) Å

b = 6.8754 (2) Å

c = 17.9938 (4) Å

β = 103.185 (1)°

V = 4146.53 (18) Å3

Z = 8

Mo Kα radiation

μ = 0.29 mm−1

T = 296 K

0.15 × 0.13 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

25340 measured reflections

5843 independent reflections

4309 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.107

S = 1.03

5843 reflections

280 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.18 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 datablocks I, global. DOI: 10.1107/S1600536810030618/zq2052sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030618/zq2052Isup2.hkl

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

C21H20N4O4S2	F(000) = 1904
Mr = 456.53	Dx = 1.463 Mg m−3Dm = 1.463 Mg m−3Dm measured by not measured
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 34.4244 (8) Å	Cell parameters from 8247 reflections
b = 6.8754 (2) Å	θ = 2.3–29.2°
c = 17.9938 (4) Å	µ = 0.29 mm−1
β = 103.185 (1)°	T = 296 K
V = 4146.53 (18) Å3	Block, orange
Z = 8	0.15 × 0.13 × 0.10 mm

Bruker APEXII CCD area-detector diffractometer	4309 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.027
graphite	θmax = 29.8°, θmin = 2.3°
phi and ω scans	h = −45→48
25340 measured reflections	k = −9→7
5843 independent reflections	l = −24→22

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) = 0.107	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0528P)2 + 1.1993P] where P = (Fo2 + 2Fc2)/3
5843 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.18 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.22169 (4)	0.0960 (3)	0.55107 (9)	0.0525 (4)
C2	0.20345 (5)	−0.0339 (3)	0.49616 (10)	0.0586 (4)
H2	0.2133	−0.1597	0.4960	0.070*
C3	0.17055 (5)	0.0221 (2)	0.44143 (9)	0.0522 (4)
H3	0.1585	−0.0664	0.4042	0.063*
C4	0.15485 (4)	0.2101 (2)	0.44084 (8)	0.0418 (3)
C5	0.17505 (5)	0.3391 (3)	0.49705 (9)	0.0529 (4)
H5	0.1660	0.4664	0.4974	0.063*
C6	0.20780 (5)	0.2823 (3)	0.55145 (10)	0.0561 (4)
H6	0.2205	0.3700	0.5884	0.067*
C7	0.10263 (5)	0.1336 (2)	0.32661 (9)	0.0469 (3)
H7A	0.1046	0.0009	0.3453	0.056*
H7B	0.1175	0.1426	0.2870	0.056*
C8	0.05960 (5)	0.1827 (2)	0.29344 (9)	0.0476 (3)
H8A	0.0493	0.0991	0.2500	0.057*
H8B	0.0441	0.1595	0.3313	0.057*
C9	0.07011 (5)	0.5142 (2)	0.33419 (8)	0.0499 (4)
H9A	0.0544	0.4955	0.3721	0.060*
H9B	0.0673	0.6487	0.3175	0.060*
C10	0.11353 (5)	0.4710 (2)	0.36929 (9)	0.0509 (4)
H10A	0.1295	0.5070	0.3335	0.061*
H10B	0.1222	0.5493	0.4149	0.061*
C11	0.12259 (4)	0.8667 (2)	0.12798 (7)	0.0400 (3)
C12	0.13746 (5)	0.7170 (3)	0.17715 (9)	0.0526 (4)
H12	0.1250	0.5962	0.1733	0.063*
C13	0.17187 (5)	0.7545 (4)	0.23274 (10)	0.0698 (6)
H13	0.1826	0.6558	0.2666	0.084*
C14	0.19059 (5)	0.9315 (4)	0.23961 (11)	0.0757 (6)
H14	0.2135	0.9509	0.2779	0.091*
C15	0.17588 (5)	1.0806 (3)	0.19041 (11)	0.0672 (5)
H15	0.1885	1.2012	0.1948	0.081*
C16	0.14155 (4)	1.0463 (2)	0.13361 (9)	0.0483 (4)
C17	0.12020 (5)	1.1645 (2)	0.07061 (10)	0.0509 (4)
C18	0.08641 (4)	1.0341 (2)	0.02587 (8)	0.0436 (3)
C19	0.06096 (4)	0.7055 (2)	0.04397 (8)	0.0415 (3)
H19A	0.0745	0.5833	0.0592	0.050*
H19B	0.0517	0.7040	−0.0111	0.050*
C20	0.02520 (4)	0.7204 (2)	0.07963 (8)	0.0411 (3)
H20A	0.0061	0.6212	0.0573	0.049*
H20B	0.0126	0.8459	0.0665	0.049*
C22	0.04231 (4)	0.4390 (2)	0.19615 (7)	0.0368 (3)
N1	0.12011 (4)	0.26548 (18)	0.38917 (7)	0.0420 (3)
N2	0.05537 (4)	0.38618 (19)	0.26924 (7)	0.0446 (3)
N3	0.25633 (5)	0.0353 (3)	0.60869 (9)	0.0688 (4)
N4	0.08920 (3)	0.86365 (18)	0.06542 (6)	0.0386 (3)
O1	0.27296 (4)	0.1532 (3)	0.65616 (9)	0.0878 (5)
O2	0.26757 (6)	−0.1329 (3)	0.60752 (10)	0.1117 (7)
O3	0.12620 (4)	1.32892 (19)	0.05188 (9)	0.0767 (4)
O4	0.06274 (4)	1.07378 (18)	−0.03291 (6)	0.0592 (3)
S1	0.031276 (12)	0.28227 (6)	0.12387 (2)	0.04687 (11)
S2	0.036236 (11)	0.69395 (5)	0.18228 (2)	0.04120 (10)

	U11	U22	U33	U12	U13	U23
C1	0.0424 (8)	0.0715 (12)	0.0423 (8)	0.0063 (8)	0.0071 (6)	0.0042 (8)
C2	0.0598 (10)	0.0559 (11)	0.0567 (10)	0.0124 (8)	0.0061 (8)	0.0048 (8)
C3	0.0558 (9)	0.0501 (9)	0.0463 (8)	0.0047 (7)	0.0025 (7)	−0.0024 (7)
C4	0.0403 (7)	0.0501 (9)	0.0361 (7)	0.0013 (6)	0.0108 (6)	0.0001 (6)
C5	0.0470 (8)	0.0566 (10)	0.0516 (9)	0.0072 (7)	0.0043 (7)	−0.0127 (8)
C6	0.0455 (8)	0.0718 (12)	0.0479 (9)	0.0012 (8)	0.0047 (7)	−0.0132 (8)
C7	0.0557 (8)	0.0401 (8)	0.0420 (8)	0.0016 (7)	0.0051 (6)	−0.0050 (6)
C8	0.0551 (8)	0.0400 (8)	0.0429 (8)	−0.0050 (7)	0.0011 (6)	0.0027 (6)
C9	0.0687 (10)	0.0426 (9)	0.0328 (7)	0.0089 (7)	−0.0002 (6)	−0.0043 (6)
C10	0.0633 (9)	0.0414 (8)	0.0417 (8)	−0.0043 (7)	−0.0011 (7)	−0.0021 (7)
C11	0.0381 (7)	0.0504 (8)	0.0315 (7)	0.0028 (6)	0.0078 (5)	0.0015 (6)
C12	0.0474 (8)	0.0650 (11)	0.0425 (8)	0.0055 (7)	0.0040 (6)	0.0119 (7)
C13	0.0485 (9)	0.1117 (17)	0.0451 (9)	0.0125 (10)	0.0025 (7)	0.0187 (10)
C14	0.0451 (9)	0.130 (2)	0.0468 (10)	−0.0066 (11)	−0.0011 (7)	−0.0083 (11)
C15	0.0524 (10)	0.0881 (15)	0.0624 (11)	−0.0210 (10)	0.0160 (8)	−0.0200 (10)
C16	0.0455 (8)	0.0548 (10)	0.0470 (8)	−0.0061 (7)	0.0158 (6)	−0.0067 (7)
C17	0.0543 (9)	0.0430 (9)	0.0628 (10)	0.0008 (7)	0.0289 (8)	0.0016 (7)
C18	0.0490 (8)	0.0447 (8)	0.0405 (7)	0.0114 (6)	0.0177 (6)	0.0067 (6)
C19	0.0469 (7)	0.0418 (8)	0.0329 (7)	0.0010 (6)	0.0029 (5)	−0.0030 (6)
C20	0.0401 (7)	0.0442 (8)	0.0348 (7)	0.0019 (6)	−0.0005 (5)	0.0030 (6)
C22	0.0335 (6)	0.0390 (7)	0.0363 (7)	−0.0002 (5)	0.0048 (5)	−0.0025 (5)
N1	0.0470 (6)	0.0385 (7)	0.0374 (6)	0.0021 (5)	0.0032 (5)	−0.0027 (5)
N2	0.0545 (7)	0.0387 (7)	0.0357 (6)	0.0014 (5)	0.0000 (5)	−0.0014 (5)
N3	0.0573 (9)	0.0930 (14)	0.0513 (9)	0.0138 (9)	0.0020 (7)	0.0054 (9)
N4	0.0404 (6)	0.0400 (6)	0.0333 (6)	0.0021 (5)	0.0042 (5)	0.0037 (5)
O1	0.0680 (8)	0.1118 (13)	0.0681 (9)	0.0036 (9)	−0.0170 (7)	−0.0075 (9)
O2	0.1188 (14)	0.1077 (14)	0.0826 (11)	0.0530 (12)	−0.0310 (10)	−0.0040 (10)
O3	0.0829 (9)	0.0482 (7)	0.1107 (11)	−0.0045 (7)	0.0461 (9)	0.0118 (7)
O4	0.0647 (7)	0.0675 (8)	0.0443 (6)	0.0220 (6)	0.0101 (5)	0.0179 (5)
S1	0.0547 (2)	0.0437 (2)	0.0383 (2)	−0.00326 (16)	0.00241 (15)	−0.00880 (15)
S2	0.0496 (2)	0.0381 (2)	0.03489 (18)	0.00262 (14)	0.00753 (14)	−0.00231 (14)

C1—C6	1.368 (3)	C11—C16	1.390 (2)
C1—C2	1.373 (2)	C11—N4	1.4136 (18)
C1—N3	1.452 (2)	C12—C13	1.389 (2)
C2—C3	1.375 (2)	C12—H12	0.9300
C2—H2	0.9300	C13—C14	1.369 (3)
C3—C4	1.400 (2)	C13—H13	0.9300
C3—H3	0.9300	C14—C15	1.374 (3)
C4—N1	1.3899 (19)	C14—H14	0.9300
C4—C5	1.404 (2)	C15—C16	1.395 (2)
C5—C6	1.371 (2)	C15—H15	0.9300
C5—H5	0.9300	C16—C17	1.451 (2)
C6—H6	0.9300	C17—O3	1.211 (2)
C7—N1	1.4635 (19)	C17—C18	1.542 (2)
C7—C8	1.504 (2)	C18—O4	1.2097 (17)
C7—H7A	0.9700	C18—N4	1.3633 (19)
C7—H7B	0.9700	C19—N4	1.4511 (19)
C8—N2	1.462 (2)	C19—C20	1.516 (2)
C8—H8A	0.9700	C19—H19A	0.9700
C8—H8B	0.9700	C19—H19B	0.9700
C9—N2	1.4585 (18)	C20—S2	1.8080 (14)
C9—C10	1.513 (2)	C20—H20A	0.9700
C9—H9A	0.9700	C20—H20B	0.9700
C9—H9B	0.9700	C22—N2	1.3394 (17)
C10—N1	1.4624 (19)	C22—S1	1.6650 (14)
C10—H10A	0.9700	C22—S2	1.7760 (14)
C10—H10B	0.9700	N3—O2	1.221 (2)
C11—C12	1.377 (2)	N3—O1	1.221 (2)
C6—C1—C2	120.64 (15)	C13—C12—H12	121.5
C6—C1—N3	119.78 (16)	C14—C13—C12	122.45 (19)
C2—C1—N3	119.58 (17)	C14—C13—H13	118.8
C1—C2—C3	120.01 (17)	C12—C13—H13	118.8
C1—C2—H2	120.0	C13—C14—C15	120.56 (17)
C3—C2—H2	120.0	C13—C14—H14	119.7
C2—C3—C4	121.14 (16)	C15—C14—H14	119.7
C2—C3—H3	119.4	C14—C15—C16	118.17 (19)
C4—C3—H3	119.4	C14—C15—H15	120.9
N1—C4—C3	121.97 (14)	C16—C15—H15	120.9
N1—C4—C5	121.19 (14)	C11—C16—C15	120.60 (17)
C3—C4—C5	116.79 (14)	C11—C16—C17	107.15 (14)
C6—C5—C4	121.74 (16)	C15—C16—C17	132.16 (17)
C6—C5—H5	119.1	O3—C17—C16	130.71 (17)
C4—C5—H5	119.1	O3—C17—C18	123.61 (17)
C1—C6—C5	119.65 (16)	C16—C17—C18	105.65 (13)
C1—C6—H6	120.2	O4—C18—N4	127.11 (15)
C5—C6—H6	120.2	O4—C18—C17	127.08 (15)
N1—C7—C8	111.19 (13)	N4—C18—C17	105.80 (12)
N1—C7—H7A	109.4	N4—C19—C20	113.34 (12)
C8—C7—H7A	109.4	N4—C19—H19A	108.9
N1—C7—H7B	109.4	C20—C19—H19A	108.9
C8—C7—H7B	109.4	N4—C19—H19B	108.9
H7A—C7—H7B	108.0	C20—C19—H19B	108.9
N2—C8—C7	110.79 (13)	H19A—C19—H19B	107.7
N2—C8—H8A	109.5	C19—C20—S2	115.08 (10)
C7—C8—H8A	109.5	C19—C20—H20A	108.5
N2—C8—H8B	109.5	S2—C20—H20A	108.5
C7—C8—H8B	109.5	C19—C20—H20B	108.5
H8A—C8—H8B	108.1	S2—C20—H20B	108.5
N2—C9—C10	110.25 (13)	H20A—C20—H20B	107.5
N2—C9—H9A	109.6	N2—C22—S1	123.85 (11)
C10—C9—H9A	109.6	N2—C22—S2	114.09 (10)
N2—C9—H9B	109.6	S1—C22—S2	122.04 (8)
C10—C9—H9B	109.6	C4—N1—C10	119.33 (12)
H9A—C9—H9B	108.1	C4—N1—C7	119.01 (12)
N1—C10—C9	112.02 (13)	C10—N1—C7	113.37 (12)
N1—C10—H10A	109.2	C22—N2—C9	126.91 (13)
C9—C10—H10A	109.2	C22—N2—C8	122.69 (12)
N1—C10—H10B	109.2	C9—N2—C8	110.23 (11)
C9—C10—H10B	109.2	O2—N3—O1	122.74 (18)
H10A—C10—H10B	107.9	O2—N3—C1	118.16 (18)
C12—C11—C16	121.17 (14)	O1—N3—C1	119.10 (18)
C12—C11—N4	128.02 (15)	C18—N4—C11	110.53 (12)
C16—C11—N4	110.75 (13)	C18—N4—C19	122.84 (12)
C11—C12—C13	117.04 (18)	C11—N4—C19	126.64 (12)
C11—C12—H12	121.5	C22—S2—C20	103.51 (7)
C6—C1—C2—C3	−0.9 (3)	C5—C4—N1—C10	27.1 (2)
N3—C1—C2—C3	179.84 (16)	C3—C4—N1—C7	−9.1 (2)
C1—C2—C3—C4	−0.6 (3)	C5—C4—N1—C7	173.37 (14)
C2—C3—C4—N1	−175.64 (15)	C9—C10—N1—C4	−161.47 (12)
C2—C3—C4—C5	2.0 (2)	C9—C10—N1—C7	50.45 (17)
N1—C4—C5—C6	175.60 (15)	C8—C7—N1—C4	161.00 (13)
C3—C4—C5—C6	−2.0 (2)	C8—C7—N1—C10	−50.81 (18)
C2—C1—C6—C5	0.8 (3)	S1—C22—N2—C9	172.05 (12)
N3—C1—C6—C5	−179.89 (15)	S2—C22—N2—C9	−9.64 (19)
C4—C5—C6—C1	0.7 (3)	S1—C22—N2—C8	−2.8 (2)
N1—C7—C8—N2	55.31 (17)	S2—C22—N2—C8	175.50 (11)
N2—C9—C10—N1	−54.06 (17)	C10—C9—N2—C22	−116.39 (16)
C16—C11—C12—C13	0.6 (2)	C10—C9—N2—C8	58.99 (17)
N4—C11—C12—C13	177.47 (15)	C7—C8—N2—C22	115.48 (15)
C11—C12—C13—C14	0.2 (3)	C7—C8—N2—C9	−60.14 (16)
C12—C13—C14—C15	−0.5 (3)	C6—C1—N3—O2	178.82 (19)
C13—C14—C15—C16	0.0 (3)	C2—C1—N3—O2	−1.9 (3)
C12—C11—C16—C15	−1.2 (2)	C6—C1—N3—O1	−1.1 (3)
N4—C11—C16—C15	−178.54 (13)	C2—C1—N3—O1	178.16 (17)
C12—C11—C16—C17	175.79 (13)	O4—C18—N4—C11	175.30 (14)
N4—C11—C16—C17	−1.57 (16)	C17—C18—N4—C11	−3.55 (14)
C14—C15—C16—C11	0.9 (2)	O4—C18—N4—C19	−4.8 (2)
C14—C15—C16—C17	−175.21 (16)	C17—C18—N4—C19	176.33 (12)
C11—C16—C17—O3	−178.79 (16)	C12—C11—N4—C18	−173.73 (14)
C15—C16—C17—O3	−2.3 (3)	C16—C11—N4—C18	3.40 (16)
C11—C16—C17—C18	−0.57 (15)	C12—C11—N4—C19	6.4 (2)
C15—C16—C17—C18	175.91 (16)	C16—C11—N4—C19	−176.48 (13)
O3—C17—C18—O4	2.1 (2)	C20—C19—N4—C18	−88.55 (15)
C16—C17—C18—O4	−176.31 (14)	C20—C19—N4—C11	91.31 (16)
O3—C17—C18—N4	−179.08 (15)	N2—C22—S2—C20	172.63 (10)
C16—C17—C18—N4	2.54 (14)	S1—C22—S2—C20	−9.02 (10)
N4—C19—C20—S2	−66.16 (15)	C19—C20—S2—C22	−77.72 (12)
C3—C4—N1—C10	−155.40 (14)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O2i	0.93	2.52	3.252 (2)	136.
C5—H5···O3ii	0.93	2.33	3.125 (2)	143.

Cg	Cg	Cg···Cg (Å)	sym. code
Cg1	Cg2	3.534 (5)	x, -y+1, z+0.5
Cg1	Cg3	3.797 (5)	x, -y+1, z+0.5

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O2i	0.93	2.52	3.252 (2)	136
C5—H5⋯O3ii	0.93	2.33	3.125 (2)	143

Symmetry codes: (i) ; (ii) .