2-(2,3-Dioxoindolin-1-yl)ethyl 4-(4-nitro­phen­yl)piperazine-1-carbodithio­ate

Wang, Y.; Wan, C.-Q.; Cao, S.-L.; Zheng, T.

doi:10.1107/S1600536810030618

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 9| September 2010| Page o2243

https://doi.org/10.1107/S1600536810030618

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2-(2,3-Dioxoindolin-1-yl)ethyl 4-(4-nitrophenyl)piperazine-1-carbodithioate

Yao Wang,^a Chong-Qing Wan,^a Sheng-Li Cao ^a ^* and Tingting Zheng ^a

^aDepartment of Chemistry, Capital Normal University, Beijing 100048, People's Republic of China
^*Correspondence e-mail: sl_cao@sohu.com

(Received 26 July 2010; accepted 31 July 2010; online 11 August 2010)

In the title compound, C₂₁H₂₀N₄O₄S_2,the piperazine ring adopts a chair conformation. The 1-ethylindoline-2,3-dione system links to one N atom of the piperazine ring via a carbodithioate group. The indoline-2,3-dione ring and the nitrobenzene ring subtend adihedral angle of 37.27 (7)°. In the crystal structure, weak C—H⋯O and π–π stacking interactions [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_r = 456.53
Monoclinic, C 2/c
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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.107
S = 1.03
5843 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.18 e Å⁻³

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

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: https://doi.org/10.1107/S1600536810030618/zq2052sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810030618/zq2052Isup2.hkl

checkCIF report

Comment top

Dithiocarbamates represent a broad spectrum of biological activities such as fungicidal (Farghaly et al., 1999; Xu et al., 2002; Ozkirimli et al., 2005) and antibacterial effects (Chourasia et al., 1999; Imamura et al., 2001). Dithiocarbamates were also proved to have in vitro and in vivo effective antitumor activities (Cao et al., 2005; Gaspari et al., 2006). In an effort to obtain new and more potent antibacterial and antitumor compounds, we synthesized the title compound, a kind of novel dithiocarbamate derivative. Here, we report the crystal structure of the title compound.

The X-ray crystal analysis shown that the piperazine ring adopts a chair conformation. The indole-2,3-dione ring and the nitrobenzene ring exhibit a dihedral angle of 37.27 (7)° (Fig.1). Considering the molecule with a U shape conformation, two molecules arrange in a face-to-face mode interacting through intermolecular hydrogen bonding (C13—H13···O2ⁱ (nitro) = 2.52 Å, D···A 3.252 (2) Å, D—H···A 136.2°). The dimers are further stacked through π–π and C—H···O intermolecular interactions: C5—H5···O3ⁱⁱ (dione) = 2.33 Å (D···A 3.125 (1) Å, D—H···A 143.3°) and the centroid-centroid distance between the C1—C2—C3—C4—C5—C6 (benzene) and C11ⁱⁱⁱ—C16ⁱⁱⁱ—C17ⁱⁱⁱ—C18ⁱⁱⁱ—N4ⁱⁱⁱ (pyrrole) rings is 3.534 (5) Å, and the distance between the C1—C2—C3—C4—C5—C6 (benzene) and C11ⁱⁱⁱ—C12ⁱⁱⁱ—C13ⁱⁱⁱ—C14ⁱⁱⁱ—C15ⁱⁱⁱ—C16ⁱⁱⁱ rings is 3.797 (5) Å. The packing structure is shown along the a axis in Fig.2 [symmetry codes: (i) –x+0.5, -y + 1/2, -z + 1; (ii) x, -y + 2, z + 1/2; (iii) x, -y + 1, z + 1/2].

Related literature top

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 top

A suspension of 1-(4-nitrophenyl) piperazine (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 min. Then, 1-(2-bromoethyl) indoline-2,3-dione (2 mmol) was added and the stirring was continued for 30 min. The reaction mixture was poured into water (100 ml) and the resulting precipitate was separated by filtration and purified by column chromatography (CC) on silica gel with dichloromethane/methanol = 95:5, v/v, as an eluent, to give the title compound (R_f = 0.79, dichloromethane/methanol = 95:5, v/v; m.p. 252–254°C; yield 90.6%). The orange crystals of the title compound were obtained by slow evaporation from a solution of dichloromethane/N,N-dimethylformamide 50:50 (v/v) at room temperature.

Structure description top

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).

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 are shown at the 50% probability level.
	Fig. 2. The packing structure of the title compound. The red dashed lines indicate the intermolecular C—H···O interactions, while the π–π stacking interactions are omitted for clarity.

2-(2,3-Dioxoindolin-1-yl)ethyl 4-(4-nitrophenyl)piperazine-1-carbodithioate top

Crystal data top

C₂₁H₂₀N₄O₄S₂	F(000) = 1904
M_r = 456.53	D_x = 1.463 Mg m⁻³ D_m = 1.463 Mg m⁻³ D_m 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

Data collection top

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

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0528P)² + 1.1993P] where P = (F_o² + 2F_c²)/3
5843 reflections	(Δ/σ)_max < 0.001
280 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₁H₂₀N₄O₄S₂	V = 4146.53 (18) Å³
M_r = 456.53	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 34.4244 (8) Å	µ = 0.29 mm⁻¹
b = 6.8754 (2) Å	T = 296 K
c = 17.9938 (4) Å	0.15 × 0.13 × 0.10 mm
β = 103.185 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	4309 reflections with I > 2σ(I)
25340 measured reflections	R_int = 0.027
5843 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.03	Δρ_max = 0.27 e Å⁻³
5843 reflections	Δρ_min = −0.18 e Å⁻³
280 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₂₁H₂₀N₄O₄S₂
M_r	456.53
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	34.4244 (8), 6.8754 (2), 17.9938 (4)
β (°)	103.185 (1)
V (Å³)	4146.53 (18)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.15 × 0.13 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	25340, 5843, 4309
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.700

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.107, 1.03
No. of reflections	5843
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.18

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—H13···O2ⁱ	0.93	2.52	3.252 (2)	136.2
C5—H5···O3ⁱⁱ	0.93	2.33	3.125 (2)	143.3

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

π–π interactions (Å)' top

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

^* Cg1, Cg2 and Cg3 are the centroids of the C1-C2-C3-C4-C5-C6 (benzene), C11-C16-C17-C18-N4 (pyrrole) and C11-C12-C13-C14-C15-C16 rings, respectively.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (project No. 20972099) and the Beijing Municipal Commission of Education (project No. KM200710028008).

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