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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1653.
Published online 2010 June 16. doi:  10.1107/S1600536810021410
PMCID: PMC3006926

Pyrrolo­[2,1-c][1,4]benzodiazepine-5,11-dithione

Abstract

The seven-membered fused-ring in the title compound, C12H12N2S2, adopts a boat conformation (with the two phenyl­ene C atoms representing the stern and the methine C atom the prow). This methine C atom and the tertiary N atom also belong to a five-membered ring, which has an envelope conformation. In the crystal structure, mol­ecules are linked about a center of inversion by pairs of N—H(...)S hydrogen bonds.

Related literature

For background to pyrrolo­[2,1-c][1,4]benzodiazepine-5,11-dione, see: Antonow et al. (2007 [triangle]); Kamal et al. (2007 [triangle]). For a related structure, Neidle et al. (1991 [triangle]).

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Object name is e-66-o1653-scheme1.jpg

Experimental

Crystal data

  • C12H12N2S2
  • M r = 248.36
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1653-efi1.jpg
  • a = 13.9831 (5) Å
  • b = 10.0134 (3) Å
  • c = 8.2670 (3) Å
  • β = 97.089 (1)°
  • V = 1148.68 (7) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.44 mm−1
  • T = 200 K
  • 0.12 × 0.10 × 0.07 mm

Data collection

  • Bruker X8 APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.950, T max = 0.970
  • 14013 measured reflections
  • 3017 independent reflections
  • 2117 reflections with I > 2σ(I)
  • R int = 0.055

Refinement

  • R[F 2 > 2σ(F 2)] = 0.042
  • wR(F 2) = 0.107
  • S = 1.01
  • 3017 reflections
  • 193 parameters
  • 12 restraints
  • All H-atom parameters refined
  • Δρmax = 0.39 e Å−3
  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2008 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810021410/xu2774sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810021410/xu2774Isup2.hkl

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

Acknowledgments

We thank Université Mohammed V-Agdal and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Pyrrolo[2,1-c][1,4]benzodiazepine-5,11-dione is the homolog of a class of compounds that are active against mycobacterium tuberculosis (Kamal et al., 2007). Other C-2 aryl substituted derivatives are cytotoxic (Antonow et al., 2007). The crystal structure of the parent compound has not been reported although that the (11aS)-1,2,3,10,11,11a-hexahydro has bee published (Neidle et al., 1997). The structure of the parent compound is probably similar to that of the isoelectronic dithione (Scheme I, Fig. 1). The seven-membered fused-ring in C12H12N2S2 adopts a boat conformation (with the two phenylene carbons representing the stern and the methine carbon atom the prow). This methine C atom and the tertiary N atom also belong to a five-membered ring, which has an envelope shape. Two C12H12N2O2 molecules are linked about a center-of-inversion by NH···Ocarbonyl hydrogen bonds.

Experimental

Pyrrolo[2,1-c][1,4]benzodiazepine-5,11-dithione (1 g, 4.62 mmol) and phosphorus pentasulfide (2.05 g, 9.24 mmol) are heated in pyridine (60 ml) for 4 h. The pyridine was evaporated under reduced pressure and the residue heated in water (100 ml). The suspension was set aside for a day. The insoluble product was recrystallized from ethanol to furnish colorless crystals (90% yield).

Refinement

The nitrogen- and carbon-bound H-atoms were refined with restraints (C–H 0.95±0.01 Å for the aromatic atoms and 0.99±0.01 Å for the aliphatic atoms; N–H 0.86±0.01 Å). Their temperature factors were freely refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of the molecule of C12H12N2S2 at the 70% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C12H12N2S2F(000) = 520
Mr = 248.36Dx = 1.436 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2753 reflections
a = 13.9831 (5) Åθ = 2.5–26.5°
b = 10.0134 (3) ŵ = 0.44 mm1
c = 8.2670 (3) ÅT = 200 K
β = 97.089 (1)°Prism, colorless
V = 1148.68 (7) Å30.12 × 0.10 × 0.07 mm
Z = 4

Data collection

Bruker X8 APEXII diffractometer3017 independent reflections
Radiation source: fine-focus sealed tube2117 reflections with I > 2σ(I)
graphiteRint = 0.055
[var phi] and ω scansθmax = 28.9°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −18→18
Tmin = 0.950, Tmax = 0.970k = −12→13
14013 measured reflectionsl = −11→11

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107All H-atom parameters refined
S = 1.01w = 1/[σ2(Fo2) + (0.047P)2 + 0.5062P] where P = (Fo2 + 2Fc2)/3
3017 reflections(Δ/σ)max = 0.001
193 parametersΔρmax = 0.39 e Å3
12 restraintsΔρmin = −0.28 e Å3

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

xyzUiso*/Ueq
S10.60817 (4)0.35830 (6)0.60020 (8)0.02972 (16)
S20.92223 (4)0.75918 (6)0.51650 (7)0.02991 (16)
N10.62240 (12)0.61932 (18)0.5884 (2)0.0221 (4)
N20.82707 (11)0.57256 (17)0.6540 (2)0.0196 (4)
C10.65476 (14)0.7511 (2)0.6273 (2)0.0205 (4)
C20.58339 (16)0.8462 (2)0.6410 (3)0.0277 (5)
C30.60718 (17)0.9769 (2)0.6798 (3)0.0318 (5)
C40.70347 (18)1.0143 (2)0.7079 (3)0.0307 (5)
C50.77396 (16)0.9220 (2)0.6894 (3)0.0251 (5)
C60.75250 (14)0.7891 (2)0.6467 (2)0.0191 (4)
C70.83258 (14)0.7001 (2)0.6109 (2)0.0194 (4)
C80.90083 (16)0.4717 (2)0.6291 (3)0.0274 (5)
C90.86119 (16)0.3432 (2)0.6929 (3)0.0284 (5)
C100.80322 (16)0.3926 (2)0.8260 (3)0.0251 (5)
C110.75591 (14)0.5204 (2)0.7555 (2)0.0190 (4)
C120.66077 (14)0.5040 (2)0.6465 (2)0.0205 (4)
H10.5667 (10)0.611 (2)0.534 (2)0.027 (6)*
H20.5176 (8)0.822 (2)0.628 (3)0.034 (7)*
H30.5592 (13)1.0406 (19)0.694 (3)0.030 (6)*
H40.7233 (16)1.1027 (13)0.736 (3)0.032 (7)*
H50.8403 (8)0.948 (2)0.708 (3)0.021 (6)*
H810.9608 (11)0.498 (2)0.697 (2)0.030 (6)*
H820.9116 (16)0.471 (2)0.5138 (14)0.034 (7)*
H910.8196 (14)0.296 (2)0.606 (2)0.029 (6)*
H920.9130 (13)0.281 (2)0.736 (3)0.037 (7)*
H110.7457 (14)0.5865 (16)0.8397 (19)0.017 (5)*
H1010.8467 (13)0.421 (2)0.9245 (19)0.029 (6)*
H1020.7565 (13)0.3271 (18)0.859 (2)0.025 (6)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0233 (3)0.0180 (3)0.0459 (3)−0.0022 (2)−0.0034 (2)0.0011 (3)
S20.0248 (3)0.0352 (4)0.0300 (3)−0.0034 (2)0.0043 (2)0.0035 (2)
N10.0172 (9)0.0175 (10)0.0299 (9)−0.0008 (7)−0.0039 (7)−0.0007 (7)
N20.0172 (8)0.0202 (10)0.0211 (8)0.0010 (7)0.0012 (7)−0.0007 (7)
C10.0238 (10)0.0169 (11)0.0202 (9)0.0007 (8)0.0004 (8)−0.0004 (8)
C20.0244 (11)0.0242 (12)0.0344 (12)0.0036 (9)0.0037 (9)−0.0019 (10)
C30.0360 (13)0.0219 (13)0.0382 (13)0.0085 (10)0.0074 (10)−0.0027 (10)
C40.0455 (14)0.0177 (12)0.0289 (11)−0.0002 (10)0.0041 (10)−0.0019 (9)
C50.0300 (12)0.0222 (12)0.0220 (10)−0.0046 (9)−0.0008 (9)0.0023 (9)
C60.0232 (10)0.0180 (11)0.0157 (9)0.0001 (8)0.0013 (8)0.0009 (8)
C70.0191 (10)0.0229 (11)0.0150 (9)−0.0025 (8)−0.0027 (7)−0.0005 (8)
C80.0224 (11)0.0276 (13)0.0317 (12)0.0081 (10)0.0015 (9)−0.0012 (10)
C90.0259 (11)0.0223 (12)0.0351 (12)0.0073 (9)−0.0042 (10)−0.0028 (10)
C100.0296 (12)0.0187 (11)0.0254 (10)0.0021 (9)−0.0035 (9)0.0012 (9)
C110.0221 (10)0.0162 (10)0.0184 (9)0.0004 (8)0.0016 (8)0.0000 (8)
C120.0203 (10)0.0197 (11)0.0224 (10)0.0019 (8)0.0065 (8)−0.0010 (8)

Geometric parameters (Å, °)

S1—C121.657 (2)C4—H40.947 (10)
S2—C71.665 (2)C5—C61.400 (3)
N1—C121.337 (3)C5—H50.956 (9)
N1—C11.419 (3)C6—C71.489 (3)
N1—H10.855 (10)C8—C91.520 (3)
N2—C71.330 (3)C8—H810.984 (10)
N2—C111.474 (2)C8—H820.984 (9)
N2—C81.476 (3)C9—C101.527 (3)
C1—C21.394 (3)C9—H910.986 (10)
C1—C61.409 (3)C9—H920.986 (10)
C2—C31.379 (3)C10—C111.523 (3)
C2—H20.944 (10)C10—H1010.996 (10)
C3—C41.389 (3)C10—H1020.986 (9)
C3—H30.942 (10)C11—C121.521 (3)
C4—C51.374 (3)C11—H110.984 (9)
C12—N1—C1128.23 (17)N2—C8—C9103.87 (17)
C12—N1—H1113.8 (16)N2—C8—H81107.5 (14)
C1—N1—H1117.1 (16)C9—C8—H81110.5 (14)
C7—N2—C11123.94 (16)N2—C8—H82109.3 (14)
C7—N2—C8123.70 (17)C9—C8—H82116.0 (15)
C11—N2—C8111.65 (16)H81—C8—H82109.2 (19)
C2—C1—C6120.0 (2)C8—C9—C10102.99 (18)
C2—C1—N1116.23 (18)C8—C9—H91110.8 (14)
C6—C1—N1123.69 (18)C10—C9—H91111.3 (13)
C3—C2—C1120.8 (2)C8—C9—H92112.0 (14)
C3—C2—H2118.2 (16)C10—C9—H92112.0 (14)
C1—C2—H2120.9 (16)H91—C9—H92108 (2)
C2—C3—C4119.7 (2)C11—C10—C9103.89 (17)
C2—C3—H3121.1 (15)C11—C10—H101105.2 (14)
C4—C3—H3119.1 (15)C9—C10—H101111.0 (13)
C5—C4—C3119.6 (2)C11—C10—H102113.1 (13)
C5—C4—H4117.6 (15)C9—C10—H102114.2 (13)
C3—C4—H4122.8 (15)H101—C10—H102109.0 (18)
C4—C5—C6122.2 (2)N2—C11—C12107.68 (15)
C4—C5—H5119.9 (14)N2—C11—C10102.94 (16)
C6—C5—H5117.9 (14)C12—C11—C10116.32 (17)
C5—C6—C1117.39 (19)N2—C11—H11109.3 (12)
C5—C6—C7118.44 (18)C12—C11—H11107.4 (12)
C1—C6—C7123.96 (19)C10—C11—H11112.9 (12)
N2—C7—C6116.84 (17)N1—C12—C11113.76 (17)
N2—C7—S2122.59 (16)N1—C12—S1122.01 (15)
C6—C7—S2120.55 (16)C11—C12—S1124.22 (15)
C12—N1—C1—C2−140.9 (2)C5—C6—C7—S2−36.1 (2)
C12—N1—C1—C641.2 (3)C1—C6—C7—S2138.49 (17)
C6—C1—C2—C3−2.6 (3)C7—N2—C8—C9−178.51 (18)
N1—C1—C2—C3179.4 (2)C11—N2—C8—C910.8 (2)
C1—C2—C3—C4−0.9 (3)N2—C8—C9—C10−30.2 (2)
C2—C3—C4—C53.0 (3)C8—C9—C10—C1138.8 (2)
C3—C4—C5—C6−1.6 (3)C7—N2—C11—C1279.1 (2)
C4—C5—C6—C1−1.8 (3)C8—N2—C11—C12−110.28 (18)
C4—C5—C6—C7173.16 (19)C7—N2—C11—C10−157.51 (18)
C2—C1—C6—C53.8 (3)C8—N2—C11—C1013.1 (2)
N1—C1—C6—C5−178.33 (18)C9—C10—C11—N2−31.7 (2)
C2—C1—C6—C7−170.78 (19)C9—C10—C11—C1285.7 (2)
N1—C1—C6—C77.0 (3)C1—N1—C12—C11−6.1 (3)
C11—N2—C7—C6−9.7 (3)C1—N1—C12—S1174.50 (16)
C8—N2—C7—C6−179.26 (17)N2—C11—C12—N1−65.3 (2)
C11—N2—C7—S2171.99 (14)C10—C11—C12—N1179.85 (18)
C8—N2—C7—S22.5 (3)N2—C11—C12—S1114.07 (17)
C5—C6—C7—N2145.61 (19)C10—C11—C12—S1−0.8 (3)
C1—C6—C7—N2−39.8 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···S1i0.86 (1)2.58 (1)3.411 (2)166 (2)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: XU2774).

References

  • Antonow, D., Jenkins, T. C., Howard, P. W. & Thurston, D. E. (2007). Bioorg. Med. Chem.15, 3041–3053. [PubMed]
  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kamal, A., Reddy, K. L., Devaiah, V., Shankaraiah, N., Reddy, G. S. K. & Raghavan, S. (2007). J. Comb. Chem.9, 29–42. [PubMed]
  • Neidle, S., Webster, G. D., Jones, G. B. & Thurston, D. E. (1991). Acta Cryst. C47, 2678–2680.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43 Submitted.

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