organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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, C21H20N4O4S2, 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 ππ 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[Farghaly, A. O. & Moharram, A. M. (1999). Boll. Chim. Farmaceut. 138, 280-289.]); Xu et al. (2002[Xu, L. Z., Jiao, K., Zhang, S. S. & Kuang, S. P. (2002). Bull. Korean Chem. Soc. 23, 1699-1701.]); Ozkirimli et al. (2005[Ozkirimli, S., Apak, T. I., Kiraz, M. & Yegenoglu, Y. (2005). Arch. Pharm. Res. 28, 1213-1218.]) and for their anti­bacterial activity, see: Chourasia et al. (1999[Chourasia, M. R. & Tyagi, D. (1999). Indian J. Phy. Nat. Sci. 15, 15-21.]); Imamura et al. (2001[Imamura, H., Ohtake, N., Jona, H., Shimizu, A., Moriya, M., Sato, H., Sugimoto, Y., Ikeura, C., Kiyonaga, H., Nakano, M., Nagano, R., Abe, S., Yamada, K., Hashizume, T. & Morishima, H. (2001). Bioorg. Med. Chem. 9, 1571-1578.]). For the effective anti­tumor activity of dithio­carbamates, see: Cao et al. (2005[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.]); Gaspari et al. (2006[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.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

Experimental

Crystal data
  • C21H20N4O4S2

  • Mr = 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)

  • Rint = 0.027

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 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

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2007). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: APEX2 and SAINT (Bruker, 2007[Bruker (2007). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


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 ππ 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 (Rf = 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.

Refinement top

All the H atoms were discernible in the difference electron density maps. Nevertheless, the hydrogen atoms were placed into idealized positions and allowed to ride on the carrier atoms, with C—H = 0.93 and 0.97 Å for aryl and methylene H atoms, respectively, and with Uiso(H) = 1.2Ueq(C).

Structure description 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 ππ 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].

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
[Figure 1] Fig. 1. The title molecule with the atomic numbering scheme. The displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. The packing structure of the title compound. The red dashed lines indicate the intermolecular C—H···O interactions, while the ππ stacking interactions are omitted for clarity.
2-(2,3-Dioxoindolin-1-yl)ethyl 4-(4-nitrophenyl)piperazine-1-carbodithioate top
Crystal data top
C21H20N4O4S2F(000) = 1904
Mr = 456.53Dx = 1.463 Mg m3
Dm = 1.463 Mg m3
Dm measured by not measured
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 34.4244 (8) ÅCell parameters from 8247 reflections
b = 6.8754 (2) Åθ = 2.3–29.2°
c = 17.9938 (4) ŵ = 0.29 mm1
β = 103.185 (1)°T = 296 K
V = 4146.53 (18) Å3Block, orange
Z = 80.15 × 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 tubeRint = 0.027
Graphite monochromatorθmax = 29.8°, θmin = 2.3°
phi and ω scansh = 4548
25340 measured reflectionsk = 97
5843 independent reflectionsl = 2422
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H-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 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C21H20N4O4S2V = 4146.53 (18) Å3
Mr = 456.53Z = 8
Monoclinic, C2/cMo Kα radiation
a = 34.4244 (8) ŵ = 0.29 mm1
b = 6.8754 (2) ÅT = 296 K
c = 17.9938 (4) Å0.15 × 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 reflectionsRint = 0.027
5843 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.107H-atom parameters constrained
S = 1.03Δρmax = 0.27 e Å3
5843 reflectionsΔρmin = 0.18 e Å3
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
xyzUiso*/Ueq
C10.22169 (4)0.0960 (3)0.55107 (9)0.0525 (4)
C20.20345 (5)0.0339 (3)0.49616 (10)0.0586 (4)
H20.21330.15970.49600.070*
C30.17055 (5)0.0221 (2)0.44143 (9)0.0522 (4)
H30.15850.06640.40420.063*
C40.15485 (4)0.2101 (2)0.44084 (8)0.0418 (3)
C50.17505 (5)0.3391 (3)0.49705 (9)0.0529 (4)
H50.16600.46640.49740.063*
C60.20780 (5)0.2823 (3)0.55145 (10)0.0561 (4)
H60.22050.37000.58840.067*
C70.10263 (5)0.1336 (2)0.32661 (9)0.0469 (3)
H7A0.10460.00090.34530.056*
H7B0.11750.14260.28700.056*
C80.05960 (5)0.1827 (2)0.29344 (9)0.0476 (3)
H8A0.04930.09910.25000.057*
H8B0.04410.15950.33130.057*
C90.07011 (5)0.5142 (2)0.33419 (8)0.0499 (4)
H9A0.05440.49550.37210.060*
H9B0.06730.64870.31750.060*
C100.11353 (5)0.4710 (2)0.36929 (9)0.0509 (4)
H10A0.12950.50700.33350.061*
H10B0.12220.54930.41490.061*
C110.12259 (4)0.8667 (2)0.12798 (7)0.0400 (3)
C120.13746 (5)0.7170 (3)0.17715 (9)0.0526 (4)
H120.12500.59620.17330.063*
C130.17187 (5)0.7545 (4)0.23274 (10)0.0698 (6)
H130.18260.65580.26660.084*
C140.19059 (5)0.9315 (4)0.23961 (11)0.0757 (6)
H140.21350.95090.27790.091*
C150.17588 (5)1.0806 (3)0.19041 (11)0.0672 (5)
H150.18851.20120.19480.081*
C160.14155 (4)1.0463 (2)0.13361 (9)0.0483 (4)
C170.12020 (5)1.1645 (2)0.07061 (10)0.0509 (4)
C180.08641 (4)1.0341 (2)0.02587 (8)0.0436 (3)
C190.06096 (4)0.7055 (2)0.04397 (8)0.0415 (3)
H19A0.07450.58330.05920.050*
H19B0.05170.70400.01110.050*
C200.02520 (4)0.7204 (2)0.07963 (8)0.0411 (3)
H20A0.00610.62120.05730.049*
H20B0.01260.84590.06650.049*
C220.04231 (4)0.4390 (2)0.19615 (7)0.0368 (3)
N10.12011 (4)0.26548 (18)0.38917 (7)0.0420 (3)
N20.05537 (4)0.38618 (19)0.26924 (7)0.0446 (3)
N30.25633 (5)0.0353 (3)0.60869 (9)0.0688 (4)
N40.08920 (3)0.86365 (18)0.06542 (6)0.0386 (3)
O10.27296 (4)0.1532 (3)0.65616 (9)0.0878 (5)
O20.26757 (6)0.1329 (3)0.60752 (10)0.1117 (7)
O30.12620 (4)1.32892 (19)0.05188 (9)0.0767 (4)
O40.06274 (4)1.07378 (18)0.03291 (6)0.0592 (3)
S10.031276 (12)0.28227 (6)0.12387 (2)0.04687 (11)
S20.036236 (11)0.69395 (5)0.18228 (2)0.04120 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0424 (8)0.0715 (12)0.0423 (8)0.0063 (8)0.0071 (6)0.0042 (8)
C20.0598 (10)0.0559 (11)0.0567 (10)0.0124 (8)0.0061 (8)0.0048 (8)
C30.0558 (9)0.0501 (9)0.0463 (8)0.0047 (7)0.0025 (7)0.0024 (7)
C40.0403 (7)0.0501 (9)0.0361 (7)0.0013 (6)0.0108 (6)0.0001 (6)
C50.0470 (8)0.0566 (10)0.0516 (9)0.0072 (7)0.0043 (7)0.0127 (8)
C60.0455 (8)0.0718 (12)0.0479 (9)0.0012 (8)0.0047 (7)0.0132 (8)
C70.0557 (8)0.0401 (8)0.0420 (8)0.0016 (7)0.0051 (6)0.0050 (6)
C80.0551 (8)0.0400 (8)0.0429 (8)0.0050 (7)0.0011 (6)0.0027 (6)
C90.0687 (10)0.0426 (9)0.0328 (7)0.0089 (7)0.0002 (6)0.0043 (6)
C100.0633 (9)0.0414 (8)0.0417 (8)0.0043 (7)0.0011 (7)0.0021 (7)
C110.0381 (7)0.0504 (8)0.0315 (7)0.0028 (6)0.0078 (5)0.0015 (6)
C120.0474 (8)0.0650 (11)0.0425 (8)0.0055 (7)0.0040 (6)0.0119 (7)
C130.0485 (9)0.1117 (17)0.0451 (9)0.0125 (10)0.0025 (7)0.0187 (10)
C140.0451 (9)0.130 (2)0.0468 (10)0.0066 (11)0.0011 (7)0.0083 (11)
C150.0524 (10)0.0881 (15)0.0624 (11)0.0210 (10)0.0160 (8)0.0200 (10)
C160.0455 (8)0.0548 (10)0.0470 (8)0.0061 (7)0.0158 (6)0.0067 (7)
C170.0543 (9)0.0430 (9)0.0628 (10)0.0008 (7)0.0289 (8)0.0016 (7)
C180.0490 (8)0.0447 (8)0.0405 (7)0.0114 (6)0.0177 (6)0.0067 (6)
C190.0469 (7)0.0418 (8)0.0329 (7)0.0010 (6)0.0029 (5)0.0030 (6)
C200.0401 (7)0.0442 (8)0.0348 (7)0.0019 (6)0.0005 (5)0.0030 (6)
C220.0335 (6)0.0390 (7)0.0363 (7)0.0002 (5)0.0048 (5)0.0025 (5)
N10.0470 (6)0.0385 (7)0.0374 (6)0.0021 (5)0.0032 (5)0.0027 (5)
N20.0545 (7)0.0387 (7)0.0357 (6)0.0014 (5)0.0000 (5)0.0014 (5)
N30.0573 (9)0.0930 (14)0.0513 (9)0.0138 (9)0.0020 (7)0.0054 (9)
N40.0404 (6)0.0400 (6)0.0333 (6)0.0021 (5)0.0042 (5)0.0037 (5)
O10.0680 (8)0.1118 (13)0.0681 (9)0.0036 (9)0.0170 (7)0.0075 (9)
O20.1188 (14)0.1077 (14)0.0826 (11)0.0530 (12)0.0310 (10)0.0040 (10)
O30.0829 (9)0.0482 (7)0.1107 (11)0.0045 (7)0.0461 (9)0.0118 (7)
O40.0647 (7)0.0675 (8)0.0443 (6)0.0220 (6)0.0101 (5)0.0179 (5)
S10.0547 (2)0.0437 (2)0.0383 (2)0.00326 (16)0.00241 (15)0.00880 (15)
S20.0496 (2)0.0381 (2)0.03489 (18)0.00262 (14)0.00753 (14)0.00231 (14)
Geometric parameters (Å, º) top
C1—C61.368 (3)C11—C161.390 (2)
C1—C21.373 (2)C11—N41.4136 (18)
C1—N31.452 (2)C12—C131.389 (2)
C2—C31.375 (2)C12—H120.9300
C2—H20.9300C13—C141.369 (3)
C3—C41.400 (2)C13—H130.9300
C3—H30.9300C14—C151.374 (3)
C4—N11.3899 (19)C14—H140.9300
C4—C51.404 (2)C15—C161.395 (2)
C5—C61.371 (2)C15—H150.9300
C5—H50.9300C16—C171.451 (2)
C6—H60.9300C17—O31.211 (2)
C7—N11.4635 (19)C17—C181.542 (2)
C7—C81.504 (2)C18—O41.2097 (17)
C7—H7A0.9700C18—N41.3633 (19)
C7—H7B0.9700C19—N41.4511 (19)
C8—N21.462 (2)C19—C201.516 (2)
C8—H8A0.9700C19—H19A0.9700
C8—H8B0.9700C19—H19B0.9700
C9—N21.4585 (18)C20—S21.8080 (14)
C9—C101.513 (2)C20—H20A0.9700
C9—H9A0.9700C20—H20B0.9700
C9—H9B0.9700C22—N21.3394 (17)
C10—N11.4624 (19)C22—S11.6650 (14)
C10—H10A0.9700C22—S21.7760 (14)
C10—H10B0.9700N3—O21.221 (2)
C11—C121.377 (2)N3—O11.221 (2)
C6—C1—C2120.64 (15)C13—C12—H12121.5
C6—C1—N3119.78 (16)C14—C13—C12122.45 (19)
C2—C1—N3119.58 (17)C14—C13—H13118.8
C1—C2—C3120.01 (17)C12—C13—H13118.8
C1—C2—H2120.0C13—C14—C15120.56 (17)
C3—C2—H2120.0C13—C14—H14119.7
C2—C3—C4121.14 (16)C15—C14—H14119.7
C2—C3—H3119.4C14—C15—C16118.17 (19)
C4—C3—H3119.4C14—C15—H15120.9
N1—C4—C3121.97 (14)C16—C15—H15120.9
N1—C4—C5121.19 (14)C11—C16—C15120.60 (17)
C3—C4—C5116.79 (14)C11—C16—C17107.15 (14)
C6—C5—C4121.74 (16)C15—C16—C17132.16 (17)
C6—C5—H5119.1O3—C17—C16130.71 (17)
C4—C5—H5119.1O3—C17—C18123.61 (17)
C1—C6—C5119.65 (16)C16—C17—C18105.65 (13)
C1—C6—H6120.2O4—C18—N4127.11 (15)
C5—C6—H6120.2O4—C18—C17127.08 (15)
N1—C7—C8111.19 (13)N4—C18—C17105.80 (12)
N1—C7—H7A109.4N4—C19—C20113.34 (12)
C8—C7—H7A109.4N4—C19—H19A108.9
N1—C7—H7B109.4C20—C19—H19A108.9
C8—C7—H7B109.4N4—C19—H19B108.9
H7A—C7—H7B108.0C20—C19—H19B108.9
N2—C8—C7110.79 (13)H19A—C19—H19B107.7
N2—C8—H8A109.5C19—C20—S2115.08 (10)
C7—C8—H8A109.5C19—C20—H20A108.5
N2—C8—H8B109.5S2—C20—H20A108.5
C7—C8—H8B109.5C19—C20—H20B108.5
H8A—C8—H8B108.1S2—C20—H20B108.5
N2—C9—C10110.25 (13)H20A—C20—H20B107.5
N2—C9—H9A109.6N2—C22—S1123.85 (11)
C10—C9—H9A109.6N2—C22—S2114.09 (10)
N2—C9—H9B109.6S1—C22—S2122.04 (8)
C10—C9—H9B109.6C4—N1—C10119.33 (12)
H9A—C9—H9B108.1C4—N1—C7119.01 (12)
N1—C10—C9112.02 (13)C10—N1—C7113.37 (12)
N1—C10—H10A109.2C22—N2—C9126.91 (13)
C9—C10—H10A109.2C22—N2—C8122.69 (12)
N1—C10—H10B109.2C9—N2—C8110.23 (11)
C9—C10—H10B109.2O2—N3—O1122.74 (18)
H10A—C10—H10B107.9O2—N3—C1118.16 (18)
C12—C11—C16121.17 (14)O1—N3—C1119.10 (18)
C12—C11—N4128.02 (15)C18—N4—C11110.53 (12)
C16—C11—N4110.75 (13)C18—N4—C19122.84 (12)
C11—C12—C13117.04 (18)C11—N4—C19126.64 (12)
C11—C12—H12121.5C22—S2—C20103.51 (7)
C6—C1—C2—C30.9 (3)C5—C4—N1—C1027.1 (2)
N3—C1—C2—C3179.84 (16)C3—C4—N1—C79.1 (2)
C1—C2—C3—C40.6 (3)C5—C4—N1—C7173.37 (14)
C2—C3—C4—N1175.64 (15)C9—C10—N1—C4161.47 (12)
C2—C3—C4—C52.0 (2)C9—C10—N1—C750.45 (17)
N1—C4—C5—C6175.60 (15)C8—C7—N1—C4161.00 (13)
C3—C4—C5—C62.0 (2)C8—C7—N1—C1050.81 (18)
C2—C1—C6—C50.8 (3)S1—C22—N2—C9172.05 (12)
N3—C1—C6—C5179.89 (15)S2—C22—N2—C99.64 (19)
C4—C5—C6—C10.7 (3)S1—C22—N2—C82.8 (2)
N1—C7—C8—N255.31 (17)S2—C22—N2—C8175.50 (11)
N2—C9—C10—N154.06 (17)C10—C9—N2—C22116.39 (16)
C16—C11—C12—C130.6 (2)C10—C9—N2—C858.99 (17)
N4—C11—C12—C13177.47 (15)C7—C8—N2—C22115.48 (15)
C11—C12—C13—C140.2 (3)C7—C8—N2—C960.14 (16)
C12—C13—C14—C150.5 (3)C6—C1—N3—O2178.82 (19)
C13—C14—C15—C160.0 (3)C2—C1—N3—O21.9 (3)
C12—C11—C16—C151.2 (2)C6—C1—N3—O11.1 (3)
N4—C11—C16—C15178.54 (13)C2—C1—N3—O1178.16 (17)
C12—C11—C16—C17175.79 (13)O4—C18—N4—C11175.30 (14)
N4—C11—C16—C171.57 (16)C17—C18—N4—C113.55 (14)
C14—C15—C16—C110.9 (2)O4—C18—N4—C194.8 (2)
C14—C15—C16—C17175.21 (16)C17—C18—N4—C19176.33 (12)
C11—C16—C17—O3178.79 (16)C12—C11—N4—C18173.73 (14)
C15—C16—C17—O32.3 (3)C16—C11—N4—C183.40 (16)
C11—C16—C17—C180.57 (15)C12—C11—N4—C196.4 (2)
C15—C16—C17—C18175.91 (16)C16—C11—N4—C19176.48 (13)
O3—C17—C18—O42.1 (2)C20—C19—N4—C1888.55 (15)
C16—C17—C18—O4176.31 (14)C20—C19—N4—C1191.31 (16)
O3—C17—C18—N4179.08 (15)N2—C22—S2—C20172.63 (10)
C16—C17—C18—N42.54 (14)S1—C22—S2—C209.02 (10)
N4—C19—C20—S266.16 (15)C19—C20—S2—C2277.72 (12)
C3—C4—N1—C10155.40 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C13—H13···O2i0.932.523.252 (2)136
C5—H5···O3ii0.932.333.125 (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 formulaC21H20N4O4S2
Mr456.53
Crystal system, space groupMonoclinic, C2/c
Temperature (K)296
a, b, c (Å)34.4244 (8), 6.8754 (2), 17.9938 (4)
β (°) 103.185 (1)
V3)4146.53 (18)
Z8
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.15 × 0.13 × 0.10
Data collection
DiffractometerBruker APEXII CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
25340, 5843, 4309
Rint0.027
(sin θ/λ)max1)0.700
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.107, 1.03
No. of reflections5843
No. of parameters280
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C13—H13···O2i0.932.523.252 (2)136.2
C5—H5···O3ii0.932.333.125 (2)143.3
Symmetry codes: (i) x+1/2, y+1/2, z+1; (ii) x, y+2, z+1/2.
ππ interactions (Å)' top
CgCgCg···Cg (Å)sym. code
Cg1Cg23.534 (5)x, -y+1, z+0.5
Cg1Cg33.797 (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).

References

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