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

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

doi:10.1107/S160053681000869X

. 2010 Mar 13;66(Pt 4):o805. doi: 10.1107/S160053681000869X

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

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

PMCID: PMC2983952 PMID: 21580640

Abstract

In the title compound, C₁₉H₁₄N₆O, the fused 12-membered tetrazolo/pyrimidine/pyrrole ring system is almost planar (r.m.s. deviation = 0.013 Å). The 4-methoxyphenyl and phenyl substituents on the pyrrole ring are both twisted with respect to the fused-ring system [dihedral angles = 25.39 (18) and 36.42 (18)°, respectively]. Intramolecular C—H⋯N interactions occur. In the crystal, molecules pack into layers in the ac plane and these are connected along the b axis via C—H⋯π and π–π [centroid–centroid separation = 3.608 (3) Å] interactions.

Related literature

For background to the biological activity of fused tetrazolopyrimidines, see: Shishoo & Jain (1992 ▶); Desai & Shah (2006 ▶). For related structures, see: Jotani et al. (2010a ▶,b ▶); Shah et al. (2010 ▶). For semi-empirical quantum chemical calculations, see: Stewart (2009 ▶).

Experimental

Crystal data

C₁₉H₁₄N₆O
M _r = 342.36
Orthorhombic,
a = 9.3537 (7) Å
b = 23.6045 (19) Å
c = 7.1543 (6) Å
V = 1579.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.967, T _max = 0.981
16155 measured reflections
1666 independent reflections
1344 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.142
S = 1.12
1666 reflections
236 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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/S160053681000869X/hb5355sup1.cif

e-66-0o805-sup1.cif^{(20.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681000869X/hb5355Isup2.hkl

e-66-0o805-Isup2.hkl^{(80.4KB, hkl)}

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

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

Cg1 is the centroid of the C14–C19 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯N4	0.93	2.50	3.257 (5)	138
C15—H15⋯N5	0.93	2.57	3.020 (5)	111
C11—H11⋯Cg1ⁱ	0.93	2.91	3.684 (5)	141
C13—H13c⋯Cg1ⁱⁱ	0.96	2.72	3.459 (5)	134

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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, Chennai, India, for the X-ray data collection.

supplementary crystallographic information

Comment

Interest in fused tetrazolopyrimidines relates, in part, to their biological activities (Shishoo & Jain, 1992; Desai & Shah, 2006). In continuation of complementary structural studies (Jotani et al. 2010a; Jotani et al. 2010b; Shah et al. 2010), the synthesis and X-ray crystal structure determination of the title compound, (I), are reported herein.

The molecule of (I) comprises a central pyrimidine ring (N1,N5,C1–C4) to which is fused a tetrazolo ring (N1–N4,C2) and a di-substituted pyrrole ring (N6,C3–C6), Fig. 1. These atoms form a plane with dihedral angles formed between the pyrimidine and the tetrazolo and pyrrole rings being 0.1 (3) and 1.5 (3) °, respectively; the dihedral angle formed between the tetrazolo and pyrrole rings is 1.6 (3) °. The r.m.s. deviation of the 12 non-hydrogen atoms comprising the fused ring system is 0.013 Å. The presence of intramolecular C–H···N interactions, Table 1, are noted and these result in the formation of S(6) and S(7) rings. The 4-methoxyphenyl and benzene substituents on the pyrrole ring are not co-planar with the fused-ring system as seen in the C3–C6–C7–C8 and C4–N6–C14–C15 torsion angles of 24.2 (9) and -39.1 (7) °, respectively.

In the crystal packing, the molecules pack into layers parallel to (0 1 0) with connections between the layers provided by C–H···π, Table 1, and π–π interactions between the five-membered tetrazolo and pyrrole rings [Cg(N1–N4,C2)···Cg(N6,C3–C6)ⁱ = 3.608 (3) Å, angle between planes = 5.0 (3) ° for i: 1-x, -y, -1/2+z], Fig. 2.

The Semi-empirical Quantum Chemical Calculations were performed on the experimental structure using the MOPAC2009 programme (Stewart, 2009) to optimize the structure with the Parametrization Model 6 (PM6) approximation together with the restricted Hartree-Fock closed-shell wavefunction; minimizations were terminated at an r.m.s. gradient of less than 0.01 kJ mol^-1 Å^-1. The most significant difference between the experimental and calculated structures is found in the relative orientation of the 4-methoxyphenyl ring with respect to the pyrrol ring to which it is bonded. This is quantified in the C3–C6–C7–C8 torsion angle of 38.9 ° cf. 24.2 (9) ° in the experimental structure. The orientation of the pyrrole-benzene ring remains unaffected.as seen in the (torsion angles is C4–N6–C14–C15 torsion angle of -38.8 ° cf. -39.1 (7) ° (experiment).

Experimental

To a well stirred mixture of 5-(4-methoxyphenyl)-7-phenyl-4-chloro-7H-pyrrolo[2,3-d]pyrimidine (5 mmol) and Aliquat 336 (0.5 mmol) in toluene (25 ml) was added sodium azide (6 mmol) in water (5 ml). The reaction mixture was stirred under reflux conditions for 1.5 h. Thereafter, the two phases were separated. The aqueous phase was extracted with toluene and the combined organic layers were washed with water. The excess solvent was distilled off under reduced pressure. The obtained solid was dried to yield (I) which was crystallized from dioxane to obtain the final product (70 % yield, m.pt. 489–491 K). The crystals used for X-ray crystallography were obtained by slow evaporation from the an ethanol solution of (I).