12-(4-Chloro­phen­yl)-7-methyl-10-phenyl-3,4,5,6,8,10-hexa­aza­tricyclo­[7.3.0.02,6]dodeca-1(9),2,4,7,11-penta­ene

Rina D Shah; Mukesh M Jotani; Edward R T Tiekink

doi:10.1107/S1600536810048373

. 2010 Nov 27;66(Pt 12):o3305. doi: 10.1107/S1600536810048373

12-(4-Chlorophenyl)-7-methyl-10-phenyl-3,4,5,6,8,10-hexaazatricyclo[7.3.0.0^2,6]dodeca-1(9),2,4,7,11-pentaene

Rina D Shah ^a, Mukesh M Jotani ^b,^‡, Edward R T Tiekink ^c,^*

PMCID: PMC3011633 PMID: 21589583

Abstract

The 12 non-H atoms defining the triple-fused-ring system in the title compound, C₁₉H₁₃ClN₆, are almost coplanar (r.m.s. deviation = 0.023 Å). The chloro-substituted ring is almost effectively coplanar with the central atoms [dihedral angle = 6.74 (13)°], but the N-bound benzene ring is not [dihedral angle = 54.38 (13)°]. In the crystal, supramolecular chains along the a axis sustained by C—H⋯π and π–π [centroid–centroid distance between N₄C and C₄N five-membered rings = 3.484 (2) Å] stacking occur. A very long C—Cl⋯π contact is also seen.

Related literature

For biological activity of imidazoles, see: Yohjiro et al. (1990 ▶). For related structures, see: Jotani et al. (2010a ▶,b ▶). Semi-empirical quantum chemical calculations were performed using MOPAC2009, see: Stewart (2009 ▶).

Experimental

Crystal data

C₁₉H₁₃ClN₆
M _r = 360.80
Orthorhombic,
a = 6.9459 (5) Å
b = 9.7010 (8) Å
c = 24.0382 (16) Å
V = 1619.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.40 × 0.22 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.928, T _max = 0.975
8751 measured reflections
1677 independent reflections
1405 reflections with I > 2σ(I)
R _int = 0.047

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.096
S = 0.98
1677 reflections
236 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810048373/hb5751sup1.cif

e-66-o3305-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810048373/hb5751Isup2.hkl

e-66-o3305-Isup2.hkl^{(80.9KB, hkl)}

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

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

Cg1 and Cg2 are the centroids of the C14–C19 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7a⋯Cg1ⁱ	0.96	2.62	3.509 (5)	154
C17—Cl1⋯Cg2ⁱⁱ	1.74 (1)	3.61 (1)	4.423 (4)	106 (1)

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

Acknowledgments

The authors are thankful to the Department of Science and Technology (DST), and the SAIF, IIT Madras, India, for the X-ray data collection.

supplementary crystallographic information

Comment

The crystal structure of the title compound, (I), was examined in connection with on-going structural studies of imidazoles (Jotani et al., 2010a; Jotani et al., 2010b), which are known to possess a wide spectrum of biological activities such as herbicidal, anti-bacterial, anti-fungal, etc. (Yohjiro et al., 1990).

In (I), the 12 non-hydrogen atoms comprising the three ring fused system are co-planar with a r.m.s. deviation of 0.023 Å [max. and min. deviations = 0.033 (3) Å for atom N1 and -0.039 (4) Å for C3]. Whereas the chloro-substituted benzene ring is co-planar with the fused ring system [the C2–C3–C14–C15 torsion angle = -173.1 (4) °], the N-bound benzene ring is twisted out of the plane [the C1–N1–C8–C9 torsion angle = -54.0 (6) °]. Other features in the molecule match recently determined literature precedents (Jotani et al., 2010a; Jotani et al., 2010b)

The presence of C—H···π, Table 1, and π–π interactions between five-membered rings [ring centroid(N1,C1–C4)···ring centroid(N3–N6,C6) = 3.484 (2) Å with an angle of inclination = 2.2 (2) ° for i: 1/2 + x, 1/2 - y, 1 - z] lead to supramolecular chains along the a axis. The major interactions involving the Cl atom are of the type C—Cl···π, Table 1, which serve to connect molecules along the b axis.

Semi-empirical Quantum Chemical Calculations were performed using the MOPAC2009 programme (Stewart, 2009) to optimize the experimental structure with the Parametrization Model 6 (PM6) approximation together with restricted the Hartree Folk closed shell wavefunction; the minimizations were terminated at a r.m.s. gradient less than 0.01 kJ-mol^-1 Å^-1. These calculations gave an optimized structure which had different conformations for the chloro-substituted and the N-bound benzene rings, as seen in the C2—C3—C14—C15 and C1—N1—C8—C9 torsion angles of 146.1 and -38.5 °, respectively.

Experimental

To a well stirred mixture of 2-methyl-4-chloro-5-(4-chlorophenyl)-7-phenyl-7H-pyrrolo[2,3-d]pyrimidine (5 mmol) and Aliquat 336 (0.202 g, 0.5 mmol) in toluene (25 ml) was added sodium azide (0.390 g, 6 mmol) in water (5 ml). The reaction mixture was stirred under reflux conditions for 1–1.5 h. Thereafter, the two phases were separated, the aqueous phase was extracted with toluene (15 ml) and combined organic layers were washed with water (10 x 2 ml) and passed through anhydrous sodium sulfate. The excess of solvent was distilled under reduced pressure. The oily residue was treated with cold methanol. The obtained solid was filtered, dried, and crystallized from dioxane to yield colourless blocks; m.pt: 251–253 K.