Two derivatives of 1,5-disubstituted tetra­zoles: 1-(4-nitro­phen­yl)-1H-tetra­zol-5-amine and {(E)-[1-(4-ethoxy­phen­yl)-1H-tetra­zol-5-yl]imino­methyl}dimethyl­amine

The geometric features of 1-(4-nitro­phenyl)-1H-tetra­zol-5-amine, C₇H₆N₆O₂, correspond to the presence of the essential inter­action of the 5-amino group lone pair with the [pi] system of the tetra­zole ring. Inter­molecular N-H...N and N-H...O hydrogen bonds result in the formation of infinite chains running along the [110] direction and involve centrosymmetric ring structures with motifs R₂²(8) and R₂²(20). Mol­ecules of {(E)-[1-(4-ethoxy­phenyl)-1H-tetra­zol-5-yl]imino­methyl}dimethyl­amine, C₁₂H₁₆N₆O, are essentially flattened, which facilitates the formation of a conjugated system spanning the whole mol­ecule. Conjugation in the azomethine N=C-N fragment results in practically the same length for the formal double and single bonds.

S1. Comment

5-Aminotetrazoles attract considerable attention because many of them reveal biological activity (Wittenberger, 1994; Schelenz, 2000; Katritzky et al., 2003, and references therein). In particular, the use of 1-aryl-5-aminotetrazoles as anti-inflammatory agents has been described (Enkoji et al., 1970), while 1-nitrophenyl-5-aminotetrazoles have been found to be active in treating and preventing coccidiosis in poultry (Mrozik, 1974). However only two examples of 1-aryl-5-aminotetrazoles have been structurally characterized to date (Lyakhov et al., 2003). In the present work, we report the crystal structure of a new compound, 1-(4-nitrophenyl)-1H-tetrazol-5-amine, (I).

In our previous investigations of 5-aminotetrazoles (Lyakhov et al., 2001, 2003, 2008), the influence of the conjugation of the 5-amino group lone pair with the π system of the tetrazole ring on the geometric features of the molecules in the crystal structures was studied. It is of interest to investigate similar effects in compounds with other N-containing groups, for example with the azomethine fragment. For this purpose, we have also investigated {(E)-[1-(4-ethoxyphenyl)-1H-tetrazol-5-yl]iminomethyl}dimethylamine, (II). This compound has practical importance, being useful as a synthetic intermediate, and as a pharmaceutical and agrochemical agent (Tiŝler, 1983; Granik, 1983; Oshovskii & Pinchuk, 2000), and can be utilized as a tetrazole-containing building block for the synthesis of complex molecules or as a polytopic ligand in bioinorganic, medicinal and supramolecular chemistry. No structural data for tetrazole azomethines are available in the literature.

In both title compounds, the tetrazole ring geometries are similar. The formal double bonds N2═N3 and N4═C5 are the shortest in the ring, while three other ring bonds lie in a rather narrow range (Tables 1 and 3). The tetrazole rings are essentially planar, with the mean deviations of the tetrazole ring atoms from their least-squares plane being 0.0018 (6)Å for (I) and 0.0013 (10) Å for (II). The geometries of the benzene rings are normal. In (I), the benzene and tetrazole rings are essentially non-coplanar, with a dihedral angle of 54.41 (5)°, while in (II) the corresponding dihedral angle has a rather low value of 4.15 (11)°. This non-coplanarity of the rings in (I) may be caused by steric hindrance due to the 5-amino group H atom. This assumption agrees with the essential non-coplanarity of the benzene and tetrazole rings in the molecules of all 1-aryl-5-aminotetrazoles investigated to date (Lyakhov et al., 2003).

Quantum chemical and X-ray investigations of 5-aminotetrazoles (Lyakhov et al., 2001, 2003, 2008) show that the conjugation of the 5-amino group lone pair with the π system of the tetrazole ring results in a planar configuration of the amino group, essential shortening of the exocyclic C5—N_amino bond and, to a lesser extent, elongation of the C5═N4 tetrazole ring bond. Moreover, the hydrogen bonds formed by the 5-amino group in these crystal structures enhance this effect. For all 5-aminotetrazoles studied to date, the length of the C5—N_amino bond lies in the narrow range 1.330 (2)–1.3374 (16) Å (Lyakhov et al., 2001, 2003, 2008; Bray & White, 1979). The data obtained for (I) agree with the above structural peculiarities of 5-aminotetrazoles (Table 1).

The molecules of compound (I) are linked by a combination of N—H···N and N—H···O hydrogen bonds (Table 2) to form polymeric chains running along the [110] direction (Fig. 3). The chain involves two types of centrosymmetric rings with motifs R₂²(8) and R₂²(20) (Bernstein et al., 1995), centred at (1/2+n, n, 1/2) and (1+n, 1/2+n, 1/2), respectively (n = zero or an integer). Only van der Waals interactions are observed between the chains.

The molecule of (II) is essentially flattened, with a mean deviation of the non-H atoms from their least-squares plane of 0.0679 (19) Å. This geometry is favourable for a conjugated system spanning the whole molecule. The same lengths of the formal N5═C14 double and C14—N6 single bonds (Table 3) could be caused by essential conjugation of the N6 atom lone pair with the N5═C14 bond. This conjugation also takes place in solution, as seen in the observed difference in the chemical shifts of signals of formally equivalent N-methyl groups in the ¹H and ¹³C NMR spectra. Thus, two singlets of the same intensity were observed in the ¹H NMR spectrum (2.99 and 3.16 p.p.m.) and two similar methyl signals were observed in the ¹³C NMR spectrum (34.3 and 40.4 p.p.m.), which is indicative of the absence of free rotation around the N6—C14 bond in solution. Analysis of the data presented in the Cambridge Structural Database (Version 5.29 of November 2007; Allen, 2002) show that, in azomethines with the dialkylamino group at the C atom, the relation between the two bond lengths in the N═C—N fragment is rather different, namely the formal double bond may be shorter, equal to or even longer than the formal single bond, which may be caused by the different influence of the fragments bonded to the azomethine N atom.

In (II), the C5—N5 bond (Table 3) is longer than the C5—N_amino bond in 5-aminotetrazoles, which may be an indicative of less conjugation between the lone pair of the azomethine N atom and the tetrazole ring π system in (II) compared with 5-aminotetrazoles. The azomethine fragment is in the E configuration. There are no direction-specific interactions between adjacent molecules in (II).

S2. Experimental

Compound (I) was prepared from 1-(4-nitrophenyl)-1H-tetrazole using the one-pot technique reported by Vorobiov et al. (2006). Single crystals suitable for X-ray crystal structure analysis were grown by slow evaporation from a tetrahydrofurane–benzene solvent system (2:1 v/v) at room temperature.

Compound (II) was prepared from 1-(4-ethoxyphenyl)-1H-tetrazol-5-amine (Vorobiov et al., 2006) as follows. A solution containing 1-(4-ethoxyphenyl)-1H-tetrazol-5-amine (0.01 mol) in methanol (30 ml) was treated with N,N-dimethylformamide dimethyl acetal (0.02 mol). The reaction mixture was boiled under reflux for 2 h, then cooled and kept at 273 K for 10 h. The precipitate which formed was filtered off, washed with cold methanol and dried under reduced pressure (yield 95%, m.p. 421–422 K). Spectroscopic analysis: ¹H NMR (500 MHz, DMSO-d₆, δ, p.p.m.): 1.34 (t, 3H, CH₃), 2.99 (s, 3H, CH₃), 3.16 (s, 3H, CH₃), 4.08 (q, 2H, CH₂), 7.08 (d, 2H, CH_Ar), 7.71 (d, 2H, CH_Ar), 8.57 (s, 1H, CH); ¹³C NMR(125 MHz, DMSO-d₆, δ, p.p.m.): 14.5, 34.3, 40.4, 63.4, 114.8, 124.3, 127.3, 158.2, 158.4, 158.7. Single crystals suitable for X-ray crystal structure analysis were grown by slow evaporation of a benzene solution at room temperature.

S3. Refinement

In (I), H-atom positions were found from the difference Fourier map and all associated parameters were refined freely.

The H atoms in (II) were included in geometrically calculated positions, with C—H = 0.97 Å for the methylene groups, 0.96 Å for the methyl groups and 0.93 Å for the remaining CH groups, and refined using a riding model, with U_iso(H) = 1.5U_eq(C) for the methyl groups or 1.2U_eq(C) for all others.

Computing details

For both compounds, data collection: R3m software (Nicolet, 1980); cell refinement: R3m software (Nicolet, 1980); data reduction: R3m software (Nicolet, 1980); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003) and SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. The asymmetric unit of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The asymmetric unit of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The hydrogen-bonded polymeric chain in (I), running along the [110] direction. Dashed lines show hydrogen bonds. Symmetry codes (i) and (ii) correspond to those in Table 2.

(I) 1-(4-nitrophenyl)-1H-tetrazol-5-amine

Crystal data

C7H6N6O2	Z = 2
Mr = 206.18	F(000) = 212
Triclinic, P1	Dx = 1.540 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8891 (17) Å	Cell parameters from 25 reflections
b = 7.9921 (18) Å	θ = 16.2–20.7°
c = 8.5877 (18) Å	µ = 0.12 mm^−1
α = 68.135 (17)°	T = 295 K
β = 74.049 (17)°	Prism, yellow
γ = 63.135 (18)°	0.48 × 0.44 × 0.42 mm
V = 444.55 (19) Å^3

Data collection

Nicolet R3m four-circle diffractometer	Rint = 0.011
Radiation source: fine-focus sealed tube	θmax = 30.1°, θmin = 2.6°
Graphite monochromator	h = 0→11
ω/2θ scans	k = −10→11
5556 measured reflections	l = −11→12
2605 independent reflections	3 standard reflections every 100 reflections
2338 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	Hydrogen site location: difference Fourier map
wR(F^2) = 0.121	All H-atom parameters refined
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0697P)^2 + 0.0595P] where P = (Fo^2 + 2Fc^2)/3
2605 reflections	(Δ/σ)max < 0.001
160 parameters	Δρmax = 0.19 e Å^−3
0 restraints	Δρmin = −0.28 e Å^−3

Special details

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.

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

	x	y	z	Uiso*/Ueq
N1	0.71575 (11)	0.30355 (12)	0.22691 (10)	0.03411 (19)
N2	0.68183 (14)	0.30624 (14)	0.07743 (11)	0.0432 (2)
N3	0.59130 (14)	0.19458 (15)	0.11762 (12)	0.0447 (2)
N4	0.56081 (12)	0.11715 (13)	0.28830 (11)	0.0394 (2)
N6	0.64696 (17)	0.14419 (17)	0.51962 (12)	0.0509 (3)
H6A	0.585 (2)	0.074 (2)	0.590 (2)	0.061 (4)*
H6B	0.671 (2)	0.222 (2)	0.552 (2)	0.065 (4)*
C5	0.63976 (13)	0.18612 (13)	0.35495 (12)	0.0348 (2)
C7	0.82206 (13)	0.40546 (13)	0.23101 (11)	0.03255 (19)
C8	0.76465 (15)	0.60463 (15)	0.14954 (14)	0.0397 (2)
H8	0.653 (2)	0.678 (2)	0.0916 (19)	0.055 (4)*
C9	0.86768 (16)	0.70270 (15)	0.15807 (14)	0.0418 (2)
H9	0.829 (2)	0.846 (3)	0.098 (2)	0.067 (5)*
C10	1.02302 (14)	0.59757 (14)	0.24793 (12)	0.0357 (2)
C11	1.08440 (14)	0.39851 (15)	0.32524 (13)	0.0387 (2)
H11	1.198 (2)	0.328 (2)	0.3815 (18)	0.053 (4)*
C12	0.98186 (14)	0.30067 (14)	0.31603 (14)	0.0387 (2)
H12	1.023 (2)	0.159 (2)	0.3678 (19)	0.054 (4)*
N13	1.12551 (14)	0.70192 (14)	0.26615 (12)	0.0436 (2)
O1	1.05418 (16)	0.88076 (14)	0.22333 (15)	0.0651 (3)
O2	1.27657 (13)	0.60462 (15)	0.32748 (12)	0.0561 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0359 (4)	0.0384 (4)	0.0364 (4)	−0.0224 (3)	−0.0058 (3)	−0.0088 (3)
N2	0.0513 (5)	0.0533 (5)	0.0382 (4)	−0.0322 (4)	−0.0080 (4)	−0.0108 (4)
N3	0.0510 (5)	0.0543 (5)	0.0440 (5)	−0.0326 (4)	−0.0089 (4)	−0.0130 (4)
N4	0.0418 (4)	0.0452 (4)	0.0437 (4)	−0.0274 (4)	−0.0060 (3)	−0.0125 (3)
N6	0.0727 (7)	0.0668 (6)	0.0381 (5)	−0.0541 (6)	−0.0054 (4)	−0.0089 (4)
C5	0.0347 (4)	0.0368 (4)	0.0397 (5)	−0.0212 (3)	−0.0042 (3)	−0.0097 (3)
C7	0.0331 (4)	0.0371 (4)	0.0349 (4)	−0.0211 (3)	−0.0019 (3)	−0.0109 (3)
C8	0.0406 (5)	0.0373 (5)	0.0468 (5)	−0.0188 (4)	−0.0128 (4)	−0.0082 (4)
C9	0.0471 (5)	0.0351 (4)	0.0499 (5)	−0.0218 (4)	−0.0095 (4)	−0.0097 (4)
C10	0.0372 (4)	0.0433 (5)	0.0384 (4)	−0.0250 (4)	0.0007 (3)	−0.0167 (4)
C11	0.0343 (4)	0.0441 (5)	0.0438 (5)	−0.0209 (4)	−0.0074 (4)	−0.0107 (4)
C12	0.0365 (5)	0.0357 (4)	0.0469 (5)	−0.0191 (4)	−0.0092 (4)	−0.0062 (4)
N13	0.0473 (5)	0.0549 (5)	0.0465 (5)	−0.0328 (4)	0.0026 (4)	−0.0236 (4)
O1	0.0708 (6)	0.0529 (5)	0.0941 (8)	−0.0357 (5)	−0.0096 (5)	−0.0314 (5)
O2	0.0524 (5)	0.0737 (6)	0.0652 (5)	−0.0371 (4)	−0.0107 (4)	−0.0266 (5)

Geometric parameters (Å, º)

N1—C5	1.3516 (12)	C8—C9	1.3897 (13)
N1—N2	1.3722 (12)	C8—H8	0.960 (15)
N1—C7	1.4223 (11)	C9—C10	1.3819 (15)
N2—N3	1.2794 (12)	C9—H9	0.999 (17)
N3—N4	1.3617 (13)	C10—C11	1.3784 (15)
N4—C5	1.3269 (12)	C10—N13	1.4662 (12)
N6—C5	1.3376 (13)	C11—C12	1.3874 (13)
N6—H6A	0.866 (16)	C11—H11	0.966 (15)
N6—H6B	0.873 (18)	C12—H12	0.977 (15)
C7—C12	1.3857 (14)	N13—O1	1.2207 (14)
C7—C8	1.3862 (14)	N13—O2	1.2266 (14)
C5—N1—N2	108.08 (8)	C9—C8—H8	118.9 (9)
C5—N1—C7	130.01 (8)	C10—C9—C8	118.59 (9)
N2—N1—C7	121.85 (8)	C10—C9—H9	122.0 (10)
N3—N2—N1	106.07 (8)	C8—C9—H9	119.4 (10)
N2—N3—N4	111.89 (8)	C11—C10—C9	123.05 (9)
C5—N4—N3	105.93 (8)	C11—C10—N13	117.99 (9)
C5—N6—H6A	116.6 (11)	C9—C10—N13	118.95 (9)
C5—N6—H6B	118.3 (10)	C10—C11—C12	118.27 (9)
H6A—N6—H6B	120.5 (16)	C10—C11—H11	120.8 (9)
N4—C5—N6	126.25 (9)	C12—C11—H11	120.9 (9)
N4—C5—N1	108.04 (9)	C7—C12—C11	119.26 (9)
N6—C5—N1	125.69 (9)	C7—C12—H12	120.4 (9)
C12—C7—C8	122.04 (9)	C11—C12—H12	120.4 (9)
C12—C7—N1	118.43 (8)	O1—N13—O2	123.36 (10)
C8—C7—N1	119.53 (8)	O1—N13—C10	118.45 (10)
C7—C8—C9	118.74 (9)	O2—N13—C10	118.17 (9)
C7—C8—H8	122.3 (9)
C5—N1—N2—N3	−0.32 (11)	C12—C7—C8—C9	−1.96 (16)
C7—N1—N2—N3	177.14 (9)	N1—C7—C8—C9	178.57 (9)
N1—N2—N3—N4	0.48 (12)	C7—C8—C9—C10	−0.18 (16)
N2—N3—N4—C5	−0.46 (12)	C8—C9—C10—C11	2.10 (17)
N3—N4—C5—N6	−178.48 (11)	C8—C9—C10—N13	−176.38 (9)
N3—N4—C5—N1	0.24 (11)	C9—C10—C11—C12	−1.83 (16)
N2—N1—C5—N4	0.04 (11)	N13—C10—C11—C12	176.65 (9)
C7—N1—C5—N4	−177.15 (9)	C8—C7—C12—C11	2.23 (16)
N2—N1—C5—N6	178.77 (10)	N1—C7—C12—C11	−178.30 (9)
C7—N1—C5—N6	1.58 (17)	C10—C11—C12—C7	−0.34 (15)
C5—N1—C7—C12	52.88 (14)	C11—C10—N13—O1	−167.90 (10)
N2—N1—C7—C12	−123.97 (11)	C9—C10—N13—O1	10.65 (15)
C5—N1—C7—C8	−127.63 (11)	C11—C10—N13—O2	10.41 (14)
N2—N1—C7—C8	55.52 (13)	C9—C10—N13—O2	−171.04 (10)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N4^i	0.866 (16)	2.119 (17)	2.9684 (14)	166.8 (15)
N6—H6B···O2^ii	0.873 (18)	2.234 (18)	3.1003 (14)	171.9 (14)
C8—H8···N3^iii	0.960 (15)	2.599 (16)	3.5286 (16)	163.1 (13)
C9—H9···N3^iv	0.999 (17)	2.601 (17)	3.4614 (18)	144.2 (13)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z; (iv) x, y+1, z.

(II) {(E)-[1-(4-ethoxyphenyl)-1H-tetrazol-5-yl]iminomethyl}dimethylamine

Crystal data

C12H16N6O	F(000) = 552
Mr = 260.31	Dx = 1.331 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 8.4150 (16) Å	θ = 11.8–16.8°
b = 17.514 (3) Å	µ = 0.09 mm^−1
c = 8.8300 (14) Å	T = 294 K
β = 93.694 (14)°	Prism, colourless
V = 1298.7 (4) Å^3	0.42 × 0.32 × 0.16 mm
Z = 4

Data collection

Nicolet R3m four-circle diffractometer	Rint = 0.015
Radiation source: fine-focus sealed tube	θmax = 27.6°, θmin = 2.3°
Graphite monochromator	h = 0→10
ω/2θ scans	k = 0→22
3232 measured reflections	l = −11→11
2999 independent reflections	3 standard reflections every 100 reflections
2132 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.047	H-atom parameters constrained
wR(F^2) = 0.154	w = 1/[σ^2(Fo^2) + (0.0867P)^2 + 0.1412P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
2999 reflections	Δρmax = 0.20 e Å^−3
176 parameters	Δρmin = −0.18 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.018 (3)

Special details

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.

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

	x	y	z	Uiso*/Ueq
O1	0.60836 (15)	0.10107 (7)	−0.05248 (13)	0.0593 (3)
N1	0.90038 (15)	0.10695 (7)	0.53214 (15)	0.0487 (3)
N2	0.99266 (18)	0.16831 (8)	0.57485 (17)	0.0599 (4)
N3	1.04928 (19)	0.15516 (9)	0.71189 (18)	0.0638 (4)
N4	0.99730 (19)	0.08718 (8)	0.76300 (17)	0.0586 (4)
C5	0.90459 (19)	0.05731 (9)	0.65058 (17)	0.0487 (4)
C6	0.82460 (18)	0.10513 (9)	0.38218 (18)	0.0464 (4)
C7	0.8559 (2)	0.16369 (9)	0.28342 (19)	0.0532 (4)
H7	0.9245	0.2030	0.3153	0.064*
C8	0.7856 (2)	0.16416 (9)	0.13753 (19)	0.0537 (4)
H8	0.8067	0.2038	0.0717	0.064*
C9	0.68410 (19)	0.10579 (9)	0.08929 (18)	0.0494 (4)
C10	0.6538 (2)	0.04693 (10)	0.18828 (19)	0.0589 (5)
H10	0.5856	0.0075	0.1562	0.071*
C11	0.7236 (2)	0.04624 (10)	0.33395 (19)	0.0576 (4)
H11	0.7031	0.0064	0.3995	0.069*
C12	0.6245 (2)	0.16413 (10)	−0.15256 (19)	0.0562 (4)
H12A	0.7347	0.1698	−0.1766	0.067*
H12B	0.5907	0.2109	−0.1054	0.067*
C13	0.5216 (3)	0.14823 (12)	−0.2941 (2)	0.0689 (5)
H13A	0.5564	0.1020	−0.3400	0.103*
H13B	0.5298	0.1898	−0.3640	0.103*
H13C	0.4129	0.1427	−0.2690	0.103*
N5	0.82387 (16)	−0.01001 (8)	0.64652 (14)	0.0516 (4)
C14	0.82880 (19)	−0.04778 (9)	0.77513 (17)	0.0506 (4)
H14	0.8814	−0.0260	0.8603	0.061*
N6	0.76253 (17)	−0.11498 (8)	0.78837 (15)	0.0538 (4)
C15	0.6815 (3)	−0.15312 (12)	0.6600 (2)	0.0723 (6)
H15A	0.5701	−0.1571	0.6759	0.109*
H15B	0.7254	−0.2033	0.6495	0.109*
H15C	0.6955	−0.1243	0.5693	0.109*
C16	0.7706 (3)	−0.15519 (12)	0.9323 (2)	0.0692 (5)
H16A	0.8253	−0.1242	1.0086	0.104*
H16B	0.8271	−0.2024	0.9224	0.104*
H16C	0.6647	−0.1657	0.9611	0.104*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0727 (8)	0.0533 (7)	0.0502 (7)	−0.0089 (6)	−0.0101 (5)	0.0068 (5)
N1	0.0537 (7)	0.0403 (6)	0.0513 (8)	0.0022 (5)	−0.0031 (6)	−0.0032 (5)
N2	0.0689 (9)	0.0475 (8)	0.0614 (9)	−0.0063 (7)	−0.0093 (7)	−0.0051 (6)
N3	0.0725 (10)	0.0556 (9)	0.0613 (9)	−0.0042 (7)	−0.0124 (7)	−0.0055 (7)
N4	0.0668 (9)	0.0518 (8)	0.0556 (8)	0.0004 (7)	−0.0093 (7)	−0.0037 (6)
C5	0.0520 (8)	0.0459 (8)	0.0475 (8)	0.0089 (7)	−0.0025 (7)	−0.0050 (6)
C6	0.0506 (8)	0.0414 (8)	0.0468 (8)	0.0044 (6)	−0.0009 (6)	−0.0026 (6)
C7	0.0572 (9)	0.0431 (8)	0.0581 (10)	−0.0055 (7)	−0.0048 (7)	0.0002 (7)
C8	0.0603 (10)	0.0453 (8)	0.0550 (9)	−0.0043 (7)	−0.0014 (7)	0.0073 (7)
C9	0.0543 (9)	0.0451 (8)	0.0480 (8)	0.0019 (7)	−0.0034 (7)	0.0009 (6)
C10	0.0715 (11)	0.0476 (9)	0.0557 (9)	−0.0133 (8)	−0.0102 (8)	0.0042 (7)
C11	0.0721 (11)	0.0459 (9)	0.0535 (9)	−0.0099 (8)	−0.0072 (8)	0.0057 (7)
C12	0.0649 (10)	0.0530 (9)	0.0507 (9)	0.0021 (8)	0.0022 (7)	0.0077 (7)
C13	0.0833 (13)	0.0719 (12)	0.0503 (10)	−0.0012 (10)	−0.0041 (9)	0.0076 (8)
N5	0.0623 (8)	0.0456 (7)	0.0460 (7)	0.0023 (6)	−0.0037 (6)	0.0011 (5)
C14	0.0560 (9)	0.0497 (9)	0.0451 (8)	0.0054 (7)	−0.0048 (7)	−0.0025 (6)
N6	0.0639 (8)	0.0526 (8)	0.0441 (7)	−0.0004 (6)	−0.0033 (6)	0.0023 (6)
C15	0.0955 (15)	0.0673 (12)	0.0531 (10)	−0.0223 (11)	−0.0038 (10)	−0.0062 (9)
C16	0.0836 (13)	0.0691 (12)	0.0541 (10)	−0.0005 (10)	−0.0018 (9)	0.0165 (9)

Geometric parameters (Å, º)

O1—C9	1.3701 (19)	C11—H11	0.9300
O1—C12	1.426 (2)	C12—C13	1.500 (2)
N1—C5	1.359 (2)	C12—H12A	0.9700
N1—N2	1.3647 (19)	C12—H12B	0.9700
N1—C6	1.432 (2)	C13—H13A	0.9600
N2—N3	1.292 (2)	C13—H13B	0.9600
N3—N4	1.356 (2)	C13—H13C	0.9600
N4—C5	1.330 (2)	N5—C14	1.313 (2)
C5—N5	1.360 (2)	C14—N6	1.311 (2)
C6—C7	1.382 (2)	C14—H14	0.9300
C6—C11	1.386 (2)	N6—C15	1.448 (2)
C7—C8	1.382 (2)	N6—C16	1.451 (2)
C7—H7	0.9300	C15—H15A	0.9600
C8—C9	1.382 (2)	C15—H15B	0.9600
C8—H8	0.9300	C15—H15C	0.9600
C9—C10	1.386 (2)	C16—H16A	0.9600
C10—C11	1.379 (2)	C16—H16B	0.9600
C10—H10	0.9300	C16—H16C	0.9600
C9—O1—C12	117.53 (13)	C13—C12—H12A	110.2
C5—N1—N2	107.75 (13)	O1—C12—H12B	110.2
C5—N1—C6	133.25 (13)	C13—C12—H12B	110.2
N2—N1—C6	118.98 (13)	H12A—C12—H12B	108.5
N3—N2—N1	106.70 (14)	C12—C13—H13A	109.5
N2—N3—N4	111.15 (14)	C12—C13—H13B	109.5
C5—N4—N3	106.46 (14)	H13A—C13—H13B	109.5
N4—C5—N1	107.93 (15)	C12—C13—H13C	109.5
N4—C5—N5	128.96 (15)	H13A—C13—H13C	109.5
N1—C5—N5	123.11 (14)	H13B—C13—H13C	109.5
C7—C6—C11	119.74 (15)	C14—N5—C5	115.23 (14)
C7—C6—N1	118.37 (14)	N6—C14—N5	122.66 (15)
C11—C6—N1	121.89 (14)	N6—C14—H14	118.7
C8—C7—C6	120.33 (15)	N5—C14—H14	118.7
C8—C7—H7	119.8	C14—N6—C15	121.73 (15)
C6—C7—H7	119.8	C14—N6—C16	121.18 (15)
C9—C8—C7	120.10 (15)	C15—N6—C16	117.07 (16)
C9—C8—H8	119.9	N6—C15—H15A	109.5
C7—C8—H8	119.9	N6—C15—H15B	109.5
O1—C9—C8	124.63 (15)	H15A—C15—H15B	109.5
O1—C9—C10	115.96 (14)	N6—C15—H15C	109.5
C8—C9—C10	119.42 (15)	H15A—C15—H15C	109.5
C11—C10—C9	120.66 (15)	H15B—C15—H15C	109.5
C11—C10—H10	119.7	N6—C16—H16A	109.5
C9—C10—H10	119.7	N6—C16—H16B	109.5
C10—C11—C6	119.74 (15)	H16A—C16—H16B	109.5
C10—C11—H11	120.1	N6—C16—H16C	109.5
C6—C11—H11	120.1	H16A—C16—H16C	109.5
O1—C12—C13	107.44 (15)	H16B—C16—H16C	109.5
O1—C12—H12A	110.2
C5—N1—N2—N3	0.33 (18)	C6—C7—C8—C9	−0.3 (3)
C6—N1—N2—N3	−178.53 (14)	C12—O1—C9—C8	−5.8 (2)
N1—N2—N3—N4	−0.4 (2)	C12—O1—C9—C10	174.13 (15)
N2—N3—N4—C5	0.3 (2)	C7—C8—C9—O1	179.80 (16)
N3—N4—C5—N1	−0.04 (18)	C7—C8—C9—C10	−0.1 (3)
N3—N4—C5—N5	−179.66 (16)	O1—C9—C10—C11	−179.82 (16)
N2—N1—C5—N4	−0.17 (18)	C8—C9—C10—C11	0.1 (3)
C6—N1—C5—N4	178.46 (15)	C9—C10—C11—C6	0.3 (3)
N2—N1—C5—N5	179.47 (14)	C7—C6—C11—C10	−0.7 (3)
C6—N1—C5—N5	−1.9 (3)	N1—C6—C11—C10	−179.83 (16)
C5—N1—C6—C7	−174.68 (16)	C9—O1—C12—C13	−175.63 (15)
N2—N1—C6—C7	3.8 (2)	N4—C5—N5—C14	5.7 (3)
C5—N1—C6—C11	4.5 (3)	N1—C5—N5—C14	−173.87 (14)
N2—N1—C6—C11	−177.02 (15)	C5—N5—C14—N6	−177.18 (15)
C11—C6—C7—C8	0.7 (3)	N5—C14—N6—C15	1.3 (3)
N1—C6—C7—C8	179.86 (15)	N5—C14—N6—C16	179.86 (16)