7-(4-Methoxy-phen-yl)-5-methyl-9-phenyl-7H-pyrrolo[2',3':4,5]pyrimido[1,6-d]tetrazole.

The title compound, C(20)H(16)N(6)O, is composed of a tetra-zolo ring and a 4-methoxy-phenyl and a benzene-substituted pyrrole ring at the 7 and 9 positions fused to a pyrimidine ring in a nearly planar fashion [maximum deviation of 0.018 (1) Å for the fused ring system]. A methyl group at the 5 position is also in the plane of the hetero cyclic system. The dihedral angle between the mean planes of the benzene and 4-methoxy-phenyl rings is 40.4 (2)°. The dihedral angles between the mean planes of the pyrimidine and the benzene and 4-methoxy-phenyl rings are 15.6 (5)° and 52.6 (7)°, respectively. A weak intra-molecular C-H⋯N hydrogen bond inter-action, which forms an S(7) graph-set motif, helps to establish the relative conformations of the tetrazolo and benzene rings. In the crystal, weak inter-molecular C-H⋯O, C-H⋯π and π-π stacking inter-actions [centroid-centroid distances = 3.5270 (16), 3.5113 (16), 3.7275 (17) and 3.7866 (17) Å] link the mol-ecules into a two-dimensional array obliquely parallel to (101) and propagating along the b axis.

Related literature

For the biological activity of fused tetra­zolopyrimidines, see: Wilkinson (1992 ▶); Omer et al. (1991 ▶); Schram et al. (1975 ▶). Fused pyrimidines with a halogen at the 2- or 4- position seem to be more labile towards a nucleophilic substitution reaction with reagents such as piperadine, piperazine, morpholine, hydrazine and azides, forming potent bi- and triheterocycles, see: Dave & Shah (2000 ▶, 2002 ▶); Peinador et al. (1992 ▶); Schneller & Clough (1992 ▶); Shishoo & Jain (1992 ▶). For the importance of the reduction of tetra­zolopyrimidines via azido­lysis in the development of synthetically important 4-amino­pyrimidines, see: Shishoo & Jain (1992 ▶); Hand & Backer (1984 ▶). For nucleophilic substitution reactions in pyrrolo[2,3-e] pyrimidines, see: Dave & Shah (2002 ▶); Ali & Swealan (1992 ▶). For related structures, see: Jotani & Baldaniya (2007 ▶, 2008 ▶); Hou et al. (2009 ▶); Baldaniya & Jotani (2008 ▶); Malone et al. (1997 ▶). For the synthesis, see: Shah (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For tetrazolo ring formation, see: Bourgurgnon et al. (1975 ▶); Robba et al. (1975 ▶).

Experimental

Crystal data

C20H16N6O

M = 356.39

Monoclinic,

a = 13.738 (2) Å

b = 7.032 (3) Å

c = 19.4350 (3) Å

β = 110.217 (2)°

V = 1761.9 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.47 × 0.35 × 0.2 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.96, T max = 0.98

42323 measured reflections

5137 independent reflections

3694 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.129

S = 1.04

5137 reflections

247 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.20 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: SIR2004 (Burla et al., 2003 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-32 and PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809053653/gw2072sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809053653/gw2072Isup2.hkl

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

C20H16N6O	F(000) = 744
Mr = 356.39	Dx = 1.344 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5176 reflections
a = 13.738 (2) Å	θ = 2.2–31.3°
b = 7.032 (3) Å	µ = 0.09 mm−1
c = 19.4350 (3) Å	T = 293 K
β = 110.217 (2)°	Plate, yellow
V = 1761.9 (8) Å3	0.47 × 0.35 × 0.2 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	5137 independent reflections
Radiation source: fine-focus sealed tube	3694 reflections with I > 2σ(I)
graphite	Rint = 0.030
ω and φ scan	θmax = 30.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −19→19
Tmin = 0.96, Tmax = 0.98	k = −4→9
42323 measured reflections	l = −27→27

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.045	H-atom parameters constrained
wR(F2) = 0.129	w = 1/[σ2(Fo2) + (0.0656P)2 + 0.2469P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
5137 reflections	Δρmax = 0.29 e Å−3
247 parameters	Δρmin = −0.20 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0104 (12)

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.

	x	y	z	Uiso*/Ueq
N1	0.49323 (7)	0.66669 (14)	0.35550 (5)	0.0364 (2)
N2	0.64444 (8)	0.71967 (13)	0.46114 (6)	0.0390 (2)
N3	0.60830 (8)	0.78499 (13)	0.56626 (5)	0.0387 (2)
N4	0.63253 (10)	0.82763 (16)	0.63905 (6)	0.0503 (3)
N5	0.54477 (10)	0.84057 (18)	0.64892 (6)	0.0553 (3)
N6	0.46241 (9)	0.80796 (15)	0.58676 (5)	0.0461 (3)
O1	0.67511 (8)	0.63011 (14)	0.14173 (5)	0.0557 (3)
C1	0.54006 (9)	0.70521 (14)	0.42843 (6)	0.0342 (2)
C2	0.46308 (9)	0.72839 (14)	0.45931 (6)	0.0322 (2)
C3	0.36448 (9)	0.70460 (14)	0.40206 (6)	0.0331 (2)
C4	0.38831 (9)	0.66682 (16)	0.34039 (6)	0.0372 (2)
H4	0.3383	0.6437	0.2933	0.045*
C5	0.67850 (10)	0.75945 (15)	0.53047 (7)	0.0400 (3)
C6	0.50261 (9)	0.77276 (14)	0.53513 (6)	0.0350 (2)
C7	0.79065 (11)	0.7757 (2)	0.57366 (8)	0.0538 (3)
H7A	0.8307	0.7651	0.5408	0.081*
H7B	0.8109	0.6735	0.6102	0.081*
H7C	0.8044	0.8991	0.5986	0.081*
C8	0.25890 (9)	0.71760 (15)	0.40362 (6)	0.0348 (2)
C9	0.17475 (10)	0.73306 (18)	0.33836 (7)	0.0437 (3)
H9	0.1867	0.7361	0.2931	0.052*
C10	0.07452 (11)	0.7441 (2)	0.33822 (8)	0.0531 (3)
H10	0.0183	0.7540	0.2931	0.064*
C11	0.05569 (11)	0.7407 (2)	0.40303 (9)	0.0572 (4)
H11	−0.0134	0.7493	0.4030	0.069*
C12	0.13717 (12)	0.7249 (2)	0.46801 (9)	0.0559 (4)
H12	0.1242	0.7217	0.5129	0.067*
C13	0.23768 (11)	0.71372 (18)	0.46865 (7)	0.0444 (3)
H13	0.2932	0.7032	0.5141	0.053*
C14	0.54240 (9)	0.65119 (16)	0.30183 (6)	0.0352 (2)
C15	0.50818 (9)	0.76648 (17)	0.24049 (6)	0.0409 (3)
H15	0.4533	0.8542	0.2348	0.049*
C16	0.55355 (10)	0.75407 (18)	0.18782 (7)	0.0437 (3)
H16	0.5294	0.8320	0.1454	0.052*
C17	0.63448 (9)	0.62818 (17)	0.19641 (6)	0.0397 (3)
C18	0.66942 (9)	0.51457 (18)	0.25825 (7)	0.0430 (3)
H18	0.7254	0.4291	0.2646	0.052*
C19	0.62275 (9)	0.52564 (17)	0.31077 (6)	0.0413 (3)
H19	0.6461	0.4467	0.3530	0.050*
C20	0.75810 (14)	0.5043 (3)	0.14708 (10)	0.0782 (6)
H20A	0.8168	0.5324	0.1918	0.117*
H20B	0.7795	0.5207	0.1043	0.117*
H20C	0.7354	0.3728	0.1488	0.117*

	U11	U22	U33	U12	U13	U23
N1	0.0378 (5)	0.0443 (5)	0.0276 (5)	0.0018 (4)	0.0121 (4)	−0.0010 (4)
N2	0.0382 (5)	0.0396 (5)	0.0362 (5)	0.0018 (4)	0.0092 (4)	0.0011 (4)
N3	0.0492 (6)	0.0345 (4)	0.0271 (5)	−0.0023 (4)	0.0064 (4)	0.0001 (3)
N4	0.0663 (8)	0.0509 (6)	0.0272 (5)	−0.0076 (5)	0.0080 (5)	−0.0035 (4)
N5	0.0717 (8)	0.0613 (7)	0.0300 (6)	−0.0110 (6)	0.0139 (5)	−0.0068 (5)
N6	0.0620 (7)	0.0495 (6)	0.0284 (5)	−0.0074 (5)	0.0175 (5)	−0.0042 (4)
O1	0.0641 (6)	0.0690 (6)	0.0459 (5)	0.0180 (5)	0.0340 (5)	0.0111 (4)
C1	0.0401 (6)	0.0329 (5)	0.0285 (5)	0.0015 (4)	0.0105 (4)	0.0016 (4)
C2	0.0406 (6)	0.0288 (4)	0.0272 (5)	0.0002 (4)	0.0118 (4)	0.0018 (4)
C3	0.0388 (6)	0.0327 (5)	0.0278 (5)	0.0006 (4)	0.0115 (4)	0.0016 (4)
C4	0.0365 (6)	0.0436 (6)	0.0298 (5)	0.0000 (4)	0.0095 (5)	−0.0017 (4)
C5	0.0437 (7)	0.0334 (5)	0.0373 (6)	0.0010 (4)	0.0069 (5)	0.0014 (4)
C6	0.0458 (6)	0.0289 (5)	0.0293 (5)	−0.0020 (4)	0.0115 (5)	0.0017 (4)
C7	0.0451 (7)	0.0510 (7)	0.0520 (8)	−0.0023 (5)	−0.0001 (6)	−0.0040 (6)
C8	0.0407 (6)	0.0320 (5)	0.0326 (6)	−0.0005 (4)	0.0137 (5)	−0.0007 (4)
C9	0.0426 (7)	0.0532 (7)	0.0346 (6)	0.0003 (5)	0.0124 (5)	−0.0012 (5)
C10	0.0404 (7)	0.0647 (8)	0.0496 (8)	0.0015 (6)	0.0096 (6)	−0.0037 (6)
C11	0.0430 (8)	0.0684 (9)	0.0646 (10)	−0.0028 (6)	0.0244 (7)	−0.0089 (7)
C12	0.0543 (8)	0.0711 (9)	0.0512 (8)	−0.0043 (7)	0.0297 (7)	−0.0068 (6)
C13	0.0464 (7)	0.0536 (7)	0.0349 (6)	−0.0008 (5)	0.0161 (5)	−0.0016 (5)
C14	0.0369 (6)	0.0420 (5)	0.0277 (5)	−0.0006 (4)	0.0124 (4)	−0.0023 (4)
C15	0.0381 (6)	0.0512 (6)	0.0327 (6)	0.0103 (5)	0.0113 (5)	0.0035 (5)
C16	0.0448 (7)	0.0550 (7)	0.0312 (6)	0.0087 (5)	0.0129 (5)	0.0090 (5)
C17	0.0416 (6)	0.0474 (6)	0.0337 (6)	0.0020 (5)	0.0174 (5)	0.0000 (4)
C18	0.0451 (7)	0.0448 (6)	0.0426 (7)	0.0110 (5)	0.0195 (5)	0.0049 (5)
C19	0.0472 (7)	0.0433 (6)	0.0348 (6)	0.0075 (5)	0.0158 (5)	0.0069 (4)
C20	0.0943 (13)	0.0825 (11)	0.0864 (12)	0.0367 (10)	0.0674 (11)	0.0245 (9)

N1—C1	1.3661 (14)	C8—C9	1.3942 (17)
N1—C4	1.3680 (15)	C9—C10	1.3783 (18)
N1—C14	1.4294 (14)	C9—H9	0.9500
N2—C5	1.2951 (16)	C10—C11	1.371 (2)
N2—C1	1.3567 (15)	C10—H10	0.9500
N3—C6	1.3691 (16)	C11—C12	1.372 (2)
N3—N4	1.3699 (14)	C11—H11	0.9500
N3—C5	1.3819 (17)	C12—C13	1.379 (2)
N4—N5	1.2879 (17)	C12—H12	0.9500
N5—N6	1.3591 (16)	C13—H13	0.9500
N6—C6	1.3254 (15)	C14—C19	1.3768 (16)
O1—C17	1.3606 (13)	C14—C15	1.3828 (16)
O1—C20	1.4183 (17)	C15—C16	1.3730 (17)
C1—C2	1.3942 (16)	C15—H15	0.9500
C2—C6	1.4178 (15)	C16—C17	1.3854 (17)
C2—C3	1.4351 (15)	C16—H16	0.9500
C3—C4	1.3730 (15)	C17—C18	1.3835 (16)
C3—C8	1.4640 (16)	C18—C19	1.3825 (16)
C4—H4	0.9500	C18—H18	0.9500
C5—C7	1.4824 (18)	C19—H19	0.9500
C7—H7A	0.9800	C20—H20A	0.9800
C7—H7B	0.9800	C20—H20B	0.9800
C7—H7C	0.9800	C20—H20C	0.9800
C8—C13	1.3920 (17)
C1—N1—C4	107.82 (9)	C10—C9—H9	119.3
C1—N1—C14	126.90 (10)	C8—C9—H9	119.3
C4—N1—C14	124.89 (9)	C11—C10—C9	120.20 (14)
C5—N2—C1	116.55 (11)	C11—C10—H10	119.9
C6—N3—N4	108.19 (10)	C9—C10—H10	119.9
C6—N3—C5	125.97 (10)	C10—C11—C12	119.60 (13)
N4—N3—C5	125.83 (11)	C10—C11—H11	120.2
N5—N4—N3	105.27 (10)	C12—C11—H11	120.2
N4—N5—N6	112.98 (11)	C11—C12—C13	120.58 (13)
C6—N6—N5	105.53 (11)	C11—C12—H12	119.7
C17—O1—C20	118.22 (10)	C13—C12—H12	119.7
N2—C1—N1	122.92 (10)	C12—C13—C8	120.93 (13)
N2—C1—C2	128.74 (10)	C12—C13—H13	119.5
N1—C1—C2	108.33 (10)	C8—C13—H13	119.5
C1—C2—C6	113.45 (10)	C19—C14—C15	120.24 (10)
C1—C2—C3	107.80 (9)	C19—C14—N1	121.15 (10)
C6—C2—C3	138.71 (11)	C15—C14—N1	118.61 (10)
C4—C3—C2	104.68 (10)	C16—C15—C14	119.92 (11)
C4—C3—C8	124.54 (10)	C16—C15—H15	120.0
C2—C3—C8	130.77 (10)	C14—C15—H15	120.0
N1—C4—C3	111.35 (10)	C15—C16—C17	120.19 (11)
N1—C4—H4	124.3	C15—C16—H16	119.9
C3—C4—H4	124.3	C17—C16—H16	119.9
N2—C5—N3	119.19 (11)	O1—C17—C18	124.85 (11)
N2—C5—C7	122.47 (12)	O1—C17—C16	115.35 (10)
N3—C5—C7	118.33 (11)	C18—C17—C16	119.78 (11)
N6—C6—N3	108.03 (10)	C19—C18—C17	119.91 (11)
N6—C6—C2	135.87 (11)	C19—C18—H18	120.0
N3—C6—C2	116.10 (10)	C17—C18—H18	120.0
C5—C7—H7A	109.5	C14—C19—C18	119.94 (11)
C5—C7—H7B	109.5	C14—C19—H19	120.0
H7A—C7—H7B	109.5	C18—C19—H19	120.0
C5—C7—H7C	109.5	O1—C20—H20A	109.5
H7A—C7—H7C	109.5	O1—C20—H20B	109.5
H7B—C7—H7C	109.5	H20A—C20—H20B	109.5
C13—C8—C9	117.35 (11)	O1—C20—H20C	109.5
C13—C8—C3	122.51 (11)	H20A—C20—H20C	109.5
C9—C8—C3	120.13 (10)	H20B—C20—H20C	109.5
C10—C9—C8	121.33 (12)
C6—N3—N4—N5	−0.45 (12)	C5—N3—C6—C2	0.47 (15)
C5—N3—N4—N5	179.34 (10)	C1—C2—C6—N6	179.44 (12)
N3—N4—N5—N6	0.33 (14)	C3—C2—C6—N6	1.9 (2)
N4—N5—N6—C6	−0.08 (14)	C1—C2—C6—N3	−0.34 (13)
C5—N2—C1—N1	179.05 (10)	C3—C2—C6—N3	−177.88 (11)
C5—N2—C1—C2	0.35 (17)	C4—C3—C8—C13	165.29 (11)
C4—N1—C1—N2	−178.52 (10)	C2—C3—C8—C13	−15.64 (17)
C14—N1—C1—N2	−5.42 (17)	C4—C3—C8—C9	−14.18 (16)
C4—N1—C1—C2	0.41 (12)	C2—C3—C8—C9	164.89 (11)
C14—N1—C1—C2	173.51 (10)	C13—C8—C9—C10	0.00 (17)
N2—C1—C2—C6	−0.04 (16)	C3—C8—C9—C10	179.50 (11)
N1—C1—C2—C6	−178.89 (9)	C8—C9—C10—C11	0.3 (2)
N2—C1—C2—C3	178.25 (10)	C9—C10—C11—C12	−0.5 (2)
N1—C1—C2—C3	−0.60 (11)	C10—C11—C12—C13	0.4 (2)
C1—C2—C3—C4	0.54 (11)	C11—C12—C13—C8	−0.2 (2)
C6—C2—C3—C4	178.17 (12)	C9—C8—C13—C12	−0.05 (17)
C1—C2—C3—C8	−178.67 (10)	C3—C8—C13—C12	−179.54 (11)
C6—C2—C3—C8	−1.0 (2)	C1—N1—C14—C19	55.88 (16)
C1—N1—C4—C3	−0.06 (13)	C4—N1—C14—C19	−132.14 (12)
C14—N1—C4—C3	−173.33 (10)	C1—N1—C14—C15	−123.61 (12)
C2—C3—C4—N1	−0.30 (12)	C4—N1—C14—C15	48.36 (16)
C8—C3—C4—N1	178.97 (9)	C19—C14—C15—C16	0.85 (18)
C1—N2—C5—N3	−0.24 (15)	N1—C14—C15—C16	−179.66 (11)
C1—N2—C5—C7	178.70 (10)	C14—C15—C16—C17	−0.88 (19)
C6—N3—C5—N2	−0.17 (16)	C20—O1—C17—C18	1.4 (2)
N4—N3—C5—N2	−179.92 (10)	C20—O1—C17—C16	−179.88 (14)
C6—N3—C5—C7	−179.15 (10)	C15—C16—C17—O1	−178.74 (12)
N4—N3—C5—C7	1.10 (16)	C15—C16—C17—C18	0.1 (2)
N5—N6—C6—N3	−0.22 (12)	O1—C17—C18—C19	179.42 (12)
N5—N6—C6—C2	179.99 (12)	C16—C17—C18—C19	0.70 (19)
N4—N3—C6—N6	0.42 (12)	C15—C14—C19—C18	−0.04 (18)
C5—N3—C6—N6	−179.37 (10)	N1—C14—C19—C18	−179.52 (11)
N4—N3—C6—C2	−179.74 (9)	C17—C18—C19—C14	−0.73 (19)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···N6	0.95	2.38	3.2159 (18)	146
C12—H12···O1i	0.95	2.57	3.3902 (17)	144
C7—H7B···Cg4ii	0.96	2.90	3.620 (2)	132
C7—H7C···Cg4iii	0.96	2.69	3.554 (2)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯N6	0.95	2.38	3.2159 (18)	146
C12—H12⋯O1i	0.95	2.57	3.3902 (17)	144
C7—H7B⋯Cg4ii	0.96	2.90	3.620 (2)	132
C7—H7C⋯Cg4iii	0.96	2.69	3.554 (2)	150

Symmetry codes: (i) ; (ii) ; (iii) . Cg4 is the centroid of the C8–C13. ring.