N-[2,4-Dioxo-3-aza­tricyclo­[7.3.1.05,13]trideca-1(13),5,7,9,11-pentaen-3-yl]thio­urea

Rashad Al-Salahi; Mohamed Al-Omar; Mohamed Marzouk; Seik Weng Ng

doi:10.1107/S1600536812021812

. 2012 May 19;68(Pt 6):o1811. doi: 10.1107/S1600536812021812

N-[2,4-Dioxo-3-azatricyclo[7.3.1.0^5,13]trideca-1(13),5,7,9,11-pentaen-3-yl]thiourea

Rashad Al-Salahi ^a, Mohamed Al-Omar ^a, Mohamed Marzouk ^a, Seik Weng Ng ^b,^c,^*

PMCID: PMC3379385 PMID: 22719583

Abstract

In the two independent molecules in the asymmetric unit of the title compound, C₁₃H₉N₃O₂S, the azatricyclotridecapentaene ring system is approximately planar with r.m.s. deviations of 0.022 and 0.033 Å. The urea unit connected to the fused rings is approximately perpendicular [dihedral angles = 82.4 (1) and 82.7 (1)°]. In the crystal, the molecules associate by N—H⋯O hydrogen bonds, forming a chain running along the a axis. The crystal studied was a non-merohedral twin with a fractional contribution of 49.6 (1)% for the minor domain.

Related literature

For background to the class of antitumor drugs, see; Pessoa et al. (2010 ▶). graphic file with name e-68-o1811-scheme1.jpg

Experimental

Crystal data

C₁₃H₉N₃O₂S
M _r = 271.29
Triclinic,
a = 4.5861 (2) Å
b = 11.0475 (4) Å
c = 22.5594 (9) Å
α = 89.196 (3)°
β = 88.073 (3)°
γ = 81.128 (3)°
V = 1128.61 (8) Å³
Z = 4
Cu Kα radiation
μ = 2.58 mm⁻¹
T = 100 K
0.25 × 0.10 × 0.03 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.565, T _max = 0.927
14869 measured reflections
7974 independent reflections
7060 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.065
wR(F ²) = 0.196
S = 1.11
7974 reflections
345 parameters
H-atom parameters constrained
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812021812/bt5920sup1.cif

e-68-o1811-sup1.cif^{(30.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812021812/bt5920Isup2.hkl

e-68-o1811-Isup2.hkl^{(390.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812021812/bt5920Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.88	2.35	3.074 (3)	140
N2—H2⋯O1ⁱⁱ	0.88	2.33	2.993 (3)	132
N3—H31⋯O2ⁱⁱⁱ	0.88	2.09	2.912 (3)	154
N5—H5⋯O3ⁱⁱⁱ	0.88	2.55	3.301 (3)	144
N5—H5⋯O3^iv	0.88	2.52	2.988 (3)	114
N6—H61⋯O4ⁱ	0.88	2.21	3.015 (3)	152

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We thank the Research Center of the College of Pharmacy College and Deanship of Scientific Research of King Saud University, and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

supplementary crystallographic information

Comment

1-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)thiourea is a powerful antitumor drug that is synthesized from phthalic anhydride and thiosemicarbazide (Pessoa et al., 2010). The title compound (Scheme I) is synthesized by using naphthalic acid anhydride in place of phthalic anhydride.

The crystal structure features two independent molecules. The azatricyclo-trideca-pentaene fused-ring is flat; the urea unit connected to the fused-ring is approximately perpendicular [dihedral angle 82.4 (1), 82.7 (1) °] (Fig. 1). Each independent molecule associates by an N–H···O hydrogen bond into a dimer; adjacent dimers are linked by N–H···O hydrogen bonds to form a chain running along the a-axis of the triclinic unit cell (Table 1).

Experimental

Naphthalic acid anhydride (2.2 mmol, 0.44 g) was dissolved in glacial acetic acid (15 ml). A solution of thiosemicarbazide (2.8 mmol, 0.26 g) in glacial acetic acid (10 ml) was added. A solid formed immediately. The solid was collected, washed with water and ether. The compound was recrystallized from a mixture of toluene and DMF to yield colorless crystals.