7-Amino-5-methyl-2-phenyl-6-(phenyl­diazenyl)pyrazolo[1,5-a]pyrimidine crystallizes with Z' = 2: pseudosymmetry and the formation of complex sheets built from N-H...N and C-H...[pi](arene) hydrogen bonds

The title compound, C₁₉H₁₆N₆, crystallizes with Z' = 2 in the space group P2₁/n. The two mol­ecules in the selected asym­metric unit are approximate mirror images of one another; most corresponding pairs of atoms are related by an approximate half-cell translation along [100]. Each mol­ecule contains an intra­molecular N-H...N hydrogen bond and the mol­ecules are linked into complex sheets by a combination of two inter­molecular N-H...N and four C-H...[pi](arene) hydrogen bonds. Comparisons are made with some other 7-amino­pyrazolo[1,5-a]pyrimidines.

S1. Comment

Fused pyrazole derivatives are of potential value in a wide range of drug, pesticide and new materials applications (Elguero, 1984, 1996) and, associated with a synthetic study of these systems, we report here the structure of the title compound, (I) (Fig. 1). This compound was prepared rapidly and in high yield by means of a cyclization reaction between 5-amino-3-phenyl-1H-pyrazole and 3-amino-2-phenyldiazenyl-2-butenenitrile (3-amino-3-methyl-2-phenyldiazenylacrylonitrile), mediated by microwave radiation under solvent-free (green) conditions (see Scheme). Compound (I) shows unexpected crystallization behaviour and an interesting supramolecular structure.

Compound (I) crystallizes with Z' = 2 in the space group P2₁/n; it is convenient to describe the independent molecules containing atoms N11 (Fig. 1a) and N21 (Fig. 1b) as molecules of types 1 and 2, respectively. The presence of two independent molecules necessarily introduces some flexibility into the choice of the asymmetric unit, but for (I) it is possible to specify a compact asymmetric unit in which the two independent molecules are linked by two C—H···π(arene) hydrogen bonds (Table 2, Fig. 2). With the exception of the ortho- and meta-positions of the terminal phenyl rings, the coordinates of corresponding pairs of atoms in the two molecules in the selected asymmetric unit are approximately related by the transformation (1/2 + x, y, z). In each of the two molecules, the skeletons between atoms Cn21 and Cn61, where n = 1 or 2 (Fig. 1), are close to planarity, as indicated by the relevant torsion angles (Table 1). However, while the torsion angles describing the orientations of the phenyl rings have similar magnitudes in the two independent molecules, the corresponding pairs of values have opposite signs, indicating that the two molecules in the selected asymmetric unit are approximate, but not exact, mirror images of one another. The combination of the approximate translational relationship between these molecules and their approximate conformational enantiomerism precludes the possibility of any additional symmetry. The differences in the hydrogen-bonding behaviour of the two molecules, discussed below, further confirms the absence of any additional crystallographic symmetry.

The bond distances within the pyrazolo[1,5-a]pyrimidine unit of compound (I) are very similar in the two independent molecules (Table 1), and they are consistent with a more marked degree of bond fixation with alternating single and double bonds between atoms Nn1 and Nn7 (n = 1 or 2) (see Scheme). This geometry may be contrasted with that found in the simpler analogues, (II) (Portilla, Quiroga, Cobo et al., 2006), (III) and (IV) (Portilla, Quiroga, de la Torre et al., 2006), and (V) (Portilla et al., 2007), which exhibit naphthalene-type delocalization. In addition, the exocyclic C—N bonds Cn7—Nn7 (n = 1 or 2) are very much shorter in compound (I) than in the analogues (II) to (V), where the corresponding distances range from 1.330 (2) Å for one of the molecules in (III) to 1.3705 (19) Å in (V). The short exocyclic C—N distances in (I) may be associated both with the more strongly localized electronic structure of the pyrazolo[1,5-a]pyrimidine unit in (I), and with possible delocalization into the phenyldiazenyl substituent: the distances Nn61—Nn62 (n = 1 or 2) are long for their type [mean value (Allen et al., 1987) 1.222 Å, upper quartile value 1.227 Å], while the bonds Cn6—Nn61 are much shorter than the bonds Nn62—Cn61, suggesting some contribution to the overall electronic structure of (I) from the polarized form (Ia). On this basis, the short intramolecular N—H···N hydrogen bonds (Table 2) can be regarded as charge-assisted hydrogen bonds (Gilli et al., 1994).

The molecules of compound (I) are linked into complex sheets by a combination of two N—H···N hydrogen bonds and four C—H···π(arene) hydrogen bonds (Table 2). The formation of the sheet can readily be analysed in terms of two ladder-like substructures, each of them one-dimensional.

In one of the substructures [then] formation of the ladder-type structure depends upon the combination of the intermolecular N—H···N hydrogen bonds with the two C—H···π(arene) hydrogen bonds within the asymmetric unit. Type 1 molecules which are related by the n-glide plane at y = 0.25 are linked by an N—H···N hydrogen bond to form a C(6) (Bernstein et al., 1995) chain running parallel to the [101] direction, and an entirely similar chain is formed by the type 2 molecules. Within each pair of molecules, one each of types 1 and 2, at any given symmetry position, the molecules are linked by two C—H···π(arene) hydrogen bonds. Hence, the substructure parallel to [101] takes the form of a molecular ladder (Fig. 3), in which the uprights are formed by the C(6) chains of N—H···N hydrogen bonds and the treads are formed by the paired C—H···π(arene) hydrogen bonds.

The second substructure is built solely from the four C—H···π(arene) hydrogen bonds, with the type 2 molecule acting as a fourfold donor of hydrogen bonds and the type 1 molecule as a fourfold acceptor (Table 2). This difference in donor and acceptor behaviour between the two independent molecules, which is evident only for the C—H···π(arene) hydrogen bonds, not for the N—H···N hydrogen bonds, is a further indication of the absence of any additional crystallographic symmetry. Each of the aryl rings in the type 1 molecule acts as a double acceptor, with one donor atom bonding to each face of each ring, with H···Cg···H angles of 173 and 176° at the centroids of the rings (C121–C126) and (C161–C166), respectively. The type 2 molecule at (x, y, z) acts as hydrogen-bond donor, via C226 and C262, to the type 1 molecule at (x, y, z), and via C223 and C265 to the type 1 molecule at (-1 + x, y, z), so forming by translation a molecular ladder running parallel to the [100] direction (Fig. 4): here the uprights of the ladder are provided by the hydrogen bonds, and the treads are provided by the molecules themselves. The combination of the molecular ladders along [100] and [101] generates a sheet of considerable complexity, which lies parallel to (010).

It is of interest briefly to compare the hydrogen bonding, and hence the supramolecular aggregation, in compound (I) with that in the analogous 7-aminopyrazolo[1,5-a]pyrimidines (II)–(V) (see Scheme), none of which contains any phenyl groups. Whereas the intermolecular N—H···N hydrogen bonds in compound (I) generate two independent C(6) chains, in each of compounds (II)–(V), pairs of molecules are linked by pairs of N—H···N hydrogen bonds to form dimeric units containing R²₂(10) motifs. In compounds (II) (Portilla, Quiroga, Cobo et al., 2006), (IV) (Portilla, Quiroga, de la Torre et al., 2006) and (V) (Portilla et al., 2007) the dimers are formed from pairs of molecules related, respectively, by a twofold rotation in space group C2, by inversion in space group P2₁/c, and again by a twofold rotation, this time in space group P4₁2₁2 (or P4₃2₁2). In compound (III), which crystallizes with Z' = 2 in space group P1 (Portilla, Quiroga, de la Torre et al., 2006), the two molecules in the asymmetric unit are linked by two independent N—H···N hydrogen bonds to form an R²₂(10) dimer having no crystallographic symmetry. Further hydrogen bonds, of N—H···O and O—H···N types, link the molecular components in compounds (II) and (IV) into three-dimensional framework structures, while N—H···N hydrogen bonds alone suffice to form a three-dimensional framework in compound (V). In compound (III), four independent N—H···N hydrogen bonds link the molecules into a ribbon containing three types of hydrogen-bonded ring, one of R²₂(1) type and two of R⁴₄(14) type. Thus, no two compounds in this rather closely related series (I)–(V) exhibit similar crystallization characteristics, in terms of the combination of Z' value and space group, and no two adopt the same hydrogen-bonded supramolecular structure.

Related literature

For related literature, see: Allen et al. (1987); Bernstein et al. (1995); Elguero (1984, 1996); Gilli et al. (1994); Portilla et al. (2007); Portilla, Quiroga, Cobo, Low & Glidewell (2006); Portilla, Quiroga, de la Torre, Cobo, Low & Glidewell (2006).

S2. Experimental

Equimolar quantities (1 mmol of each component) of 5-amino-3-phenyl-1H-pyrazole and 3-amino-2-phenyldiazenyl-2-butenenitrile were intimately mixed, and the mixture was placed in an open Pyrex glass flask, in the absence of solvent and irradiated in a domestic microwave oven for 5.0 min at 800 W. The resulting solid material was extracted with ethanol; after removal of the solvent, the product, (I), was recrystallized from dimethylformamide to give orange crystals suitable for single-crystal X-ray diffraction. Yield 85%, m.p. 501–502 K. NMR (DMSO-d₆) δ(H) 2.75 (s, 3H, CH₃), 6.90 (s, 1H, 3-H), 7.40 (t, 1H, 64-H), 7.43 (t, 1H, 24-H), 7.48 (t, 2H, 63-H), 7.52 (t, 2H, 23-H), 8.05 (d, 2H, 62-H), 8.07 (d, 2H, 22-H), 8.98, 10.25 (2 s, 2H, NH₂); δ(C) 22.2 (CH₃), 93.8 (C3), 117.8 (C6), 121.9 (C62), 126.9 (C22), 129.1 (C23), 129.5 (C24), 129.6 (C63), 129.7 (C64), 133.0 (C21) 140.0 (C7), 149.0 (C3a), 153.2 (C61), 157.2 (C2), 161.5 (C5). MS (70 eV) m/z (%) = 328 (100, M⁺), 313 (23), 77 (19).

S3. Refinement

All H atoms were located in difference maps and then treated as riding atoms in geometrically idealized positions, with C—H distances 0.95 Å (aromatic and pyrazole) or 0.98 Å (CH₃) and N—H distances 0.88 Å, and with U_iso(H) = kU_eq(carrier), where k = 1.5 for the methyl groups, which were permitted to rotate but not to tilt, and 1.2 for all other H atoms.

Computing details

Data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures

	Fig. 1. The independent molecular components of compound (I) showing the atom-labelling scheme: (a) the type 1 molecule and (b) the type 2 molecule. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The two independent molecules in the selected asymmetric unit of compound (I) showing the two C—H···π(arene) hydrogen bonds within the asymmetric unit. For the sake of clarity, the H atoms not involved in the motif shown have been omitted.
	Fig. 3. A stereoview of part of the crystal structure of compound (I) showing the formation of a hydrogen-bonded molecular ladder along [101] built from N—H···N and C—H···π(arene) hydrogen bonds. For the sake of clarity, the H atoms bonded to C atoms not involved in the motifs shown have been omitted.
	Fig. 4. A stereoview of part of the crystal structure of compound (I) showing the formation of a hydrogen-bonded molecular ladder along [100] built from C—H···π(arene) hydrogen bonds only. For the sake of clarity, the H atoms not involved in the motifs shown have been omitted.

7-Amino-5-methyl-2-phenyl-6-(phenyldiazenyl)pyrazolo[1,5-a]pyrimidine

Crystal data

C19H16N6	F(000) = 1376
Mr = 328.38	Dx = 1.399 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5790 reflections
a = 9.6342 (13) Å	θ = 2.8–25.5°
b = 33.216 (5) Å	µ = 0.09 mm^−1
c = 9.747 (3) Å	T = 120 K
β = 90.237 (18)°	Block, orange
V = 3119.1 (11) Å^3	0.42 × 0.35 × 0.27 mm
Z = 8

Data collection

Bruker Nonius KappaCCD diffractometer	5790 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	3135 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.083
Detector resolution: 9.091 pixels mm^-1	θmax = 25.5°, θmin = 2.8°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −40→40
Tmin = 0.963, Tmax = 0.976	l = −11→11
35111 measured reflections

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)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.169	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0796P)^2 + 0.6417P] where P = (Fo^2 + 2Fc^2)/3
5790 reflections	(Δ/σ)max = 0.001
453 parameters	Δρmax = 0.30 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	0.9643 (2)	0.19922 (7)	0.3597 (2)	0.0276 (6)
C12	1.0217 (3)	0.17050 (8)	0.4384 (3)	0.0255 (7)
C13	1.1054 (3)	0.18643 (8)	0.5425 (3)	0.0289 (7)
H13	1.1557	0.1718	0.6099	0.035*
C13A	1.1004 (3)	0.22703 (8)	0.5280 (3)	0.0271 (7)
N14	1.1599 (2)	0.25773 (7)	0.5994 (2)	0.0293 (6)
C15	1.1279 (3)	0.29420 (8)	0.5599 (3)	0.0262 (7)
C16	1.0351 (3)	0.30280 (8)	0.4488 (3)	0.0236 (7)
C17	0.9756 (3)	0.27132 (8)	0.3752 (3)	0.0253 (7)
N17A	1.0132 (2)	0.23391 (6)	0.4168 (2)	0.0247 (6)
C121	0.9933 (3)	0.12820 (8)	0.4096 (3)	0.0251 (7)
C122	0.9534 (3)	0.11519 (8)	0.2798 (3)	0.0301 (7)
H122	0.9450	0.1342	0.2075	0.036*
C123	0.9258 (3)	0.07523 (9)	0.2542 (3)	0.0329 (8)
H123	0.8979	0.0668	0.1651	0.039*
C124	0.9389 (3)	0.04737 (9)	0.3587 (3)	0.0322 (8)
H124	0.9205	0.0197	0.3416	0.039*
C125	0.9785 (3)	0.05970 (9)	0.4873 (3)	0.0331 (8)
H125	0.9869	0.0406	0.5595	0.040*
C126	1.0061 (3)	0.09980 (8)	0.5121 (3)	0.0306 (7)
H126	1.0343	0.1080	0.6013	0.037*
C151	1.1909 (3)	0.32832 (8)	0.6368 (3)	0.0320 (7)
H15A	1.2529	0.3178	0.7082	0.048*
H15B	1.1173	0.3444	0.6793	0.048*
H15C	1.2439	0.3453	0.5736	0.048*
N161	1.0050 (2)	0.34280 (7)	0.4329 (2)	0.0277 (6)
N162	0.9216 (2)	0.35349 (7)	0.3375 (2)	0.0283 (6)
C161	0.8929 (3)	0.39540 (8)	0.3421 (3)	0.0262 (7)
C162	0.9128 (3)	0.41864 (8)	0.4602 (3)	0.0322 (8)
H162	0.9467	0.4066	0.5421	0.039*
C163	0.8829 (3)	0.45889 (8)	0.4567 (3)	0.0342 (8)
H163	0.8953	0.4747	0.5370	0.041*
C164	0.8351 (3)	0.47670 (9)	0.3382 (3)	0.0353 (8)
H164	0.8164	0.5048	0.3360	0.042*
C165	0.8147 (3)	0.45357 (9)	0.2232 (3)	0.0354 (8)
H165	0.7811	0.4657	0.1412	0.043*
C166	0.8424 (3)	0.41321 (9)	0.2256 (3)	0.0320 (8)
H166	0.8264	0.3974	0.1459	0.038*
N17	0.8868 (2)	0.27531 (7)	0.2735 (2)	0.0301 (6)
H17A	0.8523	0.2538	0.2330	0.036*
H17B	0.8617	0.2995	0.2458	0.036*
N21	0.4633 (2)	0.19800 (6)	0.3930 (2)	0.0262 (6)
C22	0.5395 (3)	0.16958 (8)	0.4525 (3)	0.0258 (7)
C23	0.6456 (3)	0.18547 (8)	0.5346 (3)	0.0271 (7)
H23	0.7127	0.1708	0.5861	0.032*
C23A	0.6330 (3)	0.22632 (8)	0.5256 (3)	0.0256 (7)
N24	0.7018 (2)	0.25744 (7)	0.5854 (2)	0.0255 (6)
C25	0.6599 (3)	0.29393 (8)	0.5543 (3)	0.0243 (7)
C26	0.5487 (3)	0.30206 (8)	0.4629 (3)	0.0224 (7)
C27	0.4770 (3)	0.27018 (8)	0.4010 (3)	0.0235 (7)
N27A	0.5217 (2)	0.23275 (6)	0.4381 (2)	0.0244 (6)
C221	0.5081 (3)	0.12718 (8)	0.4265 (3)	0.0240 (7)
C222	0.3780 (3)	0.11625 (8)	0.3779 (3)	0.0297 (7)
H222	0.3096	0.1364	0.3627	0.036*
C223	0.3467 (3)	0.07638 (8)	0.3512 (3)	0.0320 (7)
H223	0.2573	0.0692	0.3176	0.038*
C224	0.4450 (3)	0.04725 (9)	0.3735 (3)	0.0353 (8)
H224	0.4242	0.0198	0.3547	0.042*
C225	0.5741 (3)	0.05784 (9)	0.4231 (3)	0.0364 (8)
H225	0.6418	0.0376	0.4395	0.044*
C226	0.6056 (3)	0.09733 (8)	0.4489 (3)	0.0306 (7)
H226	0.6952	0.1043	0.4826	0.037*
C251	0.7317 (3)	0.32750 (8)	0.6253 (3)	0.0277 (7)
H25A	0.8191	0.3177	0.6649	0.041*
H25B	0.6724	0.3379	0.6986	0.041*
H25C	0.7512	0.3490	0.5595	0.041*
N261	0.5194 (2)	0.34228 (6)	0.4425 (2)	0.0251 (6)
N262	0.4167 (2)	0.35093 (6)	0.3658 (2)	0.0269 (6)
C261	0.3950 (3)	0.39322 (8)	0.3541 (3)	0.0259 (7)
C262	0.4950 (3)	0.42174 (8)	0.3849 (3)	0.0289 (7)
H262	0.5844	0.4138	0.4162	0.035*
C263	0.4630 (3)	0.46190 (9)	0.3695 (3)	0.0323 (8)
H263	0.5316	0.4817	0.3890	0.039*
C264	0.3337 (3)	0.47375 (9)	0.3265 (3)	0.0344 (8)
H264	0.3123	0.5016	0.3185	0.041*
C265	0.2353 (3)	0.44540 (8)	0.2950 (3)	0.0370 (8)
H265	0.1460	0.4535	0.2640	0.044*
C266	0.2659 (3)	0.40522 (8)	0.3082 (3)	0.0301 (7)
H266	0.1978	0.3856	0.2857	0.036*
N27	0.3737 (2)	0.27343 (7)	0.3138 (2)	0.0285 (6)
H27A	0.3342	0.2517	0.2801	0.034*
H27B	0.3438	0.2974	0.2889	0.034*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.0293 (15)	0.0249 (14)	0.0287 (14)	0.0010 (11)	−0.0006 (11)	−0.0020 (11)
C12	0.0238 (17)	0.0247 (16)	0.0281 (17)	0.0023 (13)	0.0042 (13)	0.0015 (13)
C13	0.0307 (18)	0.0288 (17)	0.0272 (17)	0.0008 (14)	−0.0057 (14)	0.0023 (13)
C13A	0.0261 (17)	0.0287 (17)	0.0264 (17)	0.0033 (14)	−0.0020 (14)	0.0012 (14)
N14	0.0300 (15)	0.0265 (14)	0.0313 (15)	0.0006 (11)	−0.0035 (12)	−0.0017 (11)
C15	0.0266 (17)	0.0274 (17)	0.0246 (17)	0.0019 (13)	−0.0008 (13)	−0.0006 (13)
C16	0.0260 (17)	0.0217 (16)	0.0230 (16)	0.0023 (13)	0.0000 (13)	−0.0031 (12)
C17	0.0264 (17)	0.0222 (16)	0.0272 (17)	0.0015 (13)	0.0023 (14)	0.0025 (13)
N17A	0.0260 (14)	0.0230 (14)	0.0251 (14)	0.0002 (11)	−0.0010 (11)	−0.0020 (11)
C121	0.0220 (17)	0.0257 (16)	0.0277 (17)	0.0023 (13)	0.0002 (13)	−0.0003 (13)
C122	0.0265 (18)	0.0282 (18)	0.0356 (19)	0.0046 (14)	−0.0036 (14)	0.0068 (14)
C123	0.0311 (19)	0.0366 (19)	0.0309 (18)	−0.0005 (15)	−0.0014 (14)	−0.0060 (15)
C124	0.0290 (18)	0.0245 (17)	0.043 (2)	−0.0027 (13)	0.0022 (15)	0.0026 (15)
C125	0.0340 (19)	0.0323 (18)	0.0330 (19)	0.0026 (15)	−0.0002 (15)	0.0071 (15)
C126	0.0287 (18)	0.0318 (18)	0.0311 (18)	0.0013 (14)	−0.0001 (14)	0.0010 (14)
C151	0.0351 (19)	0.0291 (17)	0.0317 (18)	−0.0012 (14)	−0.0037 (14)	−0.0008 (14)
N161	0.0258 (15)	0.0291 (14)	0.0284 (15)	0.0005 (11)	−0.0012 (12)	0.0021 (11)
N162	0.0287 (15)	0.0261 (14)	0.0300 (15)	0.0031 (11)	−0.0030 (12)	−0.0003 (11)
C161	0.0264 (17)	0.0210 (16)	0.0311 (18)	−0.0006 (13)	−0.0004 (14)	−0.0005 (13)
C162	0.0330 (19)	0.0306 (18)	0.0329 (18)	−0.0004 (14)	0.0021 (14)	0.0002 (15)
C163	0.0310 (19)	0.0284 (18)	0.043 (2)	−0.0011 (14)	0.0014 (15)	−0.0074 (15)
C164	0.0320 (19)	0.0248 (17)	0.049 (2)	0.0012 (14)	0.0012 (16)	0.0012 (15)
C165	0.036 (2)	0.0353 (19)	0.0353 (19)	0.0049 (15)	−0.0005 (15)	0.0045 (15)
C166	0.0334 (19)	0.0352 (19)	0.0274 (18)	0.0014 (14)	0.0011 (14)	0.0017 (14)
N17	0.0362 (16)	0.0217 (13)	0.0323 (15)	0.0014 (11)	−0.0136 (12)	0.0007 (11)
N21	0.0281 (14)	0.0217 (14)	0.0289 (14)	0.0015 (11)	−0.0016 (11)	−0.0023 (11)
C22	0.0238 (17)	0.0261 (16)	0.0273 (17)	0.0023 (13)	0.0016 (13)	−0.0015 (13)
C23	0.0273 (18)	0.0248 (17)	0.0291 (17)	0.0052 (13)	−0.0046 (14)	0.0014 (13)
C23A	0.0246 (17)	0.0293 (17)	0.0228 (16)	0.0010 (13)	−0.0018 (13)	0.0014 (13)
N24	0.0262 (14)	0.0248 (14)	0.0255 (14)	−0.0014 (11)	−0.0041 (11)	−0.0013 (10)
C25	0.0260 (17)	0.0251 (16)	0.0217 (16)	0.0036 (13)	−0.0009 (13)	−0.0010 (13)
C26	0.0241 (17)	0.0216 (16)	0.0215 (16)	0.0020 (13)	0.0008 (13)	−0.0020 (12)
C27	0.0235 (17)	0.0226 (16)	0.0244 (16)	0.0034 (13)	0.0018 (13)	0.0001 (13)
N27A	0.0256 (14)	0.0226 (14)	0.0249 (13)	−0.0014 (11)	−0.0029 (11)	−0.0015 (11)
C221	0.0257 (17)	0.0219 (16)	0.0245 (16)	−0.0001 (13)	0.0006 (13)	0.0015 (12)
C222	0.0335 (19)	0.0310 (18)	0.0244 (17)	0.0018 (14)	−0.0023 (14)	0.0037 (13)
C223	0.034 (2)	0.0298 (18)	0.0320 (18)	−0.0061 (15)	−0.0030 (14)	−0.0003 (14)
C224	0.044 (2)	0.0248 (17)	0.0368 (19)	−0.0024 (15)	0.0038 (16)	−0.0033 (14)
C225	0.032 (2)	0.0273 (18)	0.050 (2)	0.0047 (15)	−0.0005 (16)	−0.0010 (15)
C226	0.0292 (18)	0.0277 (17)	0.0350 (18)	0.0008 (14)	−0.0021 (14)	−0.0025 (14)
C251	0.0280 (17)	0.0271 (16)	0.0278 (17)	−0.0002 (13)	−0.0033 (13)	−0.0026 (13)
N261	0.0269 (15)	0.0248 (14)	0.0236 (14)	0.0042 (11)	−0.0016 (11)	0.0009 (10)
N262	0.0266 (15)	0.0253 (14)	0.0288 (14)	0.0030 (11)	−0.0001 (12)	0.0008 (11)
C261	0.0313 (18)	0.0230 (16)	0.0232 (16)	0.0018 (13)	0.0012 (13)	0.0027 (13)
C262	0.0322 (19)	0.0292 (17)	0.0253 (17)	0.0003 (14)	−0.0015 (14)	−0.0002 (13)
C263	0.037 (2)	0.0260 (17)	0.0335 (19)	−0.0028 (14)	0.0004 (15)	−0.0013 (14)
C264	0.037 (2)	0.0247 (17)	0.041 (2)	0.0039 (15)	0.0038 (16)	0.0024 (14)
C265	0.032 (2)	0.0315 (18)	0.048 (2)	0.0077 (15)	0.0026 (16)	0.0077 (15)
C266	0.0277 (18)	0.0282 (17)	0.0344 (18)	0.0007 (14)	−0.0013 (14)	0.0049 (14)
N27	0.0277 (15)	0.0222 (13)	0.0354 (15)	0.0027 (11)	−0.0119 (12)	0.0005 (11)

Geometric parameters (Å, º)

N11—C12	1.342 (3)	N21—C22	1.328 (3)
C12—C13	1.398 (4)	C22—C23	1.399 (4)
C13—C13A	1.357 (4)	C23—C23A	1.365 (4)
C13A—N14	1.359 (3)	C23A—N24	1.358 (3)
N14—C15	1.308 (3)	N24—C25	1.313 (3)
C15—C16	1.430 (4)	C25—C26	1.417 (4)
C16—C17	1.390 (4)	C26—C27	1.399 (4)
C17—N17A	1.356 (3)	C27—N27A	1.364 (3)
N17A—N11	1.363 (3)	N27A—N21	1.357 (3)
C13A—N17A	1.388 (3)	C23A—N27A	1.384 (3)
C17—N17	1.314 (3)	C27—N27	1.311 (3)
C16—N161	1.369 (3)	C26—N261	1.380 (3)
N161—N162	1.277 (3)	N261—N262	1.270 (3)
N162—C161	1.420 (3)	N262—C261	1.425 (3)
C12—C121	1.458 (4)	C22—C221	1.462 (4)
C13—H13	0.9500	C23—H23	0.9500
C15—C151	1.487 (4)	C25—C251	1.483 (4)
C121—C126	1.379 (4)	C221—C226	1.382 (4)
C121—C122	1.390 (4)	C221—C222	1.387 (4)
C122—C123	1.376 (4)	C222—C223	1.383 (4)
C122—H122	0.9500	C222—H222	0.9500
C123—C124	1.382 (4)	C223—C224	1.371 (4)
C123—H123	0.9500	C223—H223	0.9500
C124—C125	1.371 (4)	C224—C225	1.379 (4)
C124—H124	0.9500	C224—H224	0.9500
C125—C126	1.379 (4)	C225—C226	1.370 (4)
C125—H125	0.9500	C225—H225	0.9500
C126—H126	0.9500	C226—H226	0.9500
C151—H15A	0.9800	C251—H25A	0.9800
C151—H15B	0.9800	C251—H25B	0.9800
C151—H15C	0.9800	C251—H25C	0.9800
C161—C166	1.368 (4)	C261—C266	1.379 (4)
C161—C162	1.398 (4)	C261—C262	1.383 (4)
C162—C163	1.368 (4)	C262—C263	1.377 (4)
C162—H162	0.9500	C262—H262	0.9500
C163—C164	1.375 (4)	C263—C264	1.371 (4)
C163—H163	0.9500	C263—H263	0.9500
C164—C165	1.373 (4)	C264—C265	1.370 (4)
C164—H164	0.9500	C264—H264	0.9500
C165—C166	1.367 (4)	C265—C266	1.373 (4)
C165—H165	0.9500	C265—H265	0.9500
C166—H166	0.9500	C266—H266	0.9500
N17—H17A	0.8800	N27—H27A	0.8800
N17—H17B	0.8800	N27—H27B	0.8800
C12—N11—N17A	103.1 (2)	C22—N21—N27A	103.6 (2)
N11—C12—C13	112.4 (2)	N21—C22—C23	112.5 (2)
N11—C12—C121	119.9 (3)	N21—C22—C221	119.7 (3)
C13—C12—C121	127.7 (3)	C23—C22—C221	127.8 (3)
C13A—C13—C12	106.3 (3)	C23A—C23—C22	105.9 (2)
C13A—C13—H13	126.8	C23A—C23—H23	127.1
C12—C13—H13	126.8	C22—C23—H23	127.1
C13—C13A—N14	132.7 (3)	N24—C23A—C23	133.3 (3)
C13—C13A—N17A	105.4 (2)	N24—C23A—N27A	121.5 (2)
N14—C13A—N17A	121.9 (2)	C23—C23A—N27A	105.2 (2)
C15—N14—C13A	116.5 (2)	C25—N24—C23A	117.0 (2)
N14—C15—C16	123.6 (3)	N24—C25—C26	123.6 (2)
N14—C15—C151	117.5 (2)	N24—C25—C251	116.4 (2)
C16—C15—C151	118.8 (2)	C26—C25—C251	120.0 (2)
N161—C16—C17	125.8 (3)	N261—C26—C27	124.8 (3)
N161—C16—C15	114.3 (2)	N261—C26—C25	115.4 (2)
C17—C16—C15	119.7 (2)	C27—C26—C25	119.8 (2)
N17—C17—N17A	119.3 (2)	N27—C27—N27A	119.0 (2)
N17—C17—C16	125.4 (3)	N27—C27—C26	126.1 (3)
N17A—C17—C16	115.2 (2)	N27A—C27—C26	114.9 (2)
C17—N17A—N11	124.2 (2)	N21—N27A—C27	124.0 (2)
C17—N17A—C13A	123.0 (2)	N21—N27A—C23A	112.8 (2)
N11—N17A—C13A	112.8 (2)	C27—N27A—C23A	123.2 (2)
C126—C121—C122	118.1 (3)	C226—C221—C222	118.6 (3)
C126—C121—C12	120.3 (3)	C226—C221—C22	121.6 (3)
C122—C121—C12	121.7 (3)	C222—C221—C22	119.8 (3)
C123—C122—C121	121.2 (3)	C223—C222—C221	120.7 (3)
C123—C122—H122	119.4	C223—C222—H222	119.6
C121—C122—H122	119.4	C221—C222—H222	119.6
C122—C123—C124	119.7 (3)	C224—C223—C222	119.7 (3)
C122—C123—H123	120.2	C224—C223—H223	120.1
C124—C123—H123	120.2	C222—C223—H223	120.1
C125—C124—C123	119.9 (3)	C223—C224—C225	119.8 (3)
C125—C124—H124	120.1	C223—C224—H224	120.1
C123—C124—H124	120.1	C225—C224—H224	120.1
C124—C125—C126	120.1 (3)	C226—C225—C224	120.5 (3)
C124—C125—H125	120.0	C226—C225—H225	119.7
C126—C125—H125	120.0	C224—C225—H225	119.7
C121—C126—C125	121.2 (3)	C225—C226—C221	120.5 (3)
C121—C126—H126	119.4	C225—C226—H226	119.7
C125—C126—H126	119.4	C221—C226—H226	119.7
C15—C151—H15A	109.5	C25—C251—H25A	109.5
C15—C151—H15B	109.5	C25—C251—H25B	109.5
H15A—C151—H15B	109.5	H25A—C251—H25B	109.5
C15—C151—H15C	109.5	C25—C251—H25C	109.5
H15A—C151—H15C	109.5	H25A—C251—H25C	109.5
H15B—C151—H15C	109.5	H25B—C251—H25C	109.5
N162—N161—C16	119.0 (2)	N262—N261—C26	117.5 (2)
N161—N162—C161	111.8 (2)	N261—N262—C261	112.5 (2)
C166—C161—C162	119.4 (3)	C266—C261—C262	119.9 (3)
C166—C161—N162	117.8 (3)	C266—C261—N262	116.3 (2)
C162—C161—N162	122.8 (3)	C262—C261—N262	123.8 (3)
C163—C162—C161	119.4 (3)	C263—C262—C261	119.0 (3)
C163—C162—H162	120.3	C263—C262—H262	120.5
C161—C162—H162	120.3	C261—C262—H262	120.5
C162—C163—C164	120.7 (3)	C264—C263—C262	120.9 (3)
C162—C163—H163	119.6	C264—C263—H263	119.5
C164—C163—H163	119.6	C262—C263—H263	119.5
C165—C164—C163	119.4 (3)	C265—C264—C263	119.9 (3)
C165—C164—H164	120.3	C265—C264—H264	120.1
C163—C164—H164	120.3	C263—C264—H264	120.1
C166—C165—C164	120.5 (3)	C264—C265—C266	120.0 (3)
C166—C165—H165	119.8	C264—C265—H265	120.0
C164—C165—H165	119.8	C266—C265—H265	120.0
C165—C166—C161	120.5 (3)	C265—C266—C261	120.3 (3)
C165—C166—H166	119.8	C265—C266—H266	119.9
C161—C166—H166	119.8	C261—C266—H266	119.9
C17—N17—H17A	120.0	C27—N27—H27A	120.0
C17—N17—H17B	120.0	C27—N27—H27B	120.0
H17A—N17—H17B	120.0	H27A—N27—H27B	120.0
N17A—N11—C12—C13	−0.2 (3)	N27A—N21—C22—C23	−0.1 (3)
N17A—N11—C12—C121	179.9 (2)	N27A—N21—C22—C221	−179.3 (2)
N11—C12—C13—C13A	−0.2 (3)	N21—C22—C23—C23A	0.4 (3)
C121—C12—C13—C13A	179.8 (3)	C221—C22—C23—C23A	179.6 (3)
C12—C13—C13A—N14	179.6 (3)	C22—C23—C23A—N24	177.2 (3)
C12—C13—C13A—N17A	0.5 (3)	C22—C23—C23A—N27A	−0.6 (3)
C13—C13A—N14—C15	−177.3 (3)	C23—C23A—N24—C25	−178.9 (3)
N17A—C13A—N14—C15	1.7 (4)	N27A—C23A—N24—C25	−1.4 (4)
C13A—N14—C15—C16	0.4 (4)	C23A—N24—C25—C26	−0.2 (4)
C13A—N14—C15—C151	179.6 (2)	C23A—N24—C25—C251	177.3 (2)
N14—C15—C16—N161	173.8 (3)	N24—C25—C26—N261	−180.0 (2)
C151—C15—C16—N161	−5.4 (4)	C251—C25—C26—N261	2.7 (4)
N14—C15—C16—C17	−1.0 (4)	N24—C25—C26—C27	0.3 (4)
C151—C15—C16—C17	179.7 (3)	C251—C25—C26—C27	−177.0 (2)
N161—C16—C17—N17	4.1 (5)	N261—C26—C27—N27	1.0 (5)
C15—C16—C17—N17	178.4 (3)	C25—C26—C27—N27	−179.2 (3)
N161—C16—C17—N17A	−174.7 (2)	N261—C26—C27—N27A	−178.7 (2)
C15—C16—C17—N17A	−0.4 (4)	C25—C26—C27—N27A	1.1 (4)
N17—C17—N17A—N11	−0.2 (4)	C22—N21—N27A—C27	179.2 (2)
C16—C17—N17A—N11	178.7 (2)	C22—N21—N27A—C23A	−0.3 (3)
N17—C17—N17A—C13A	−176.4 (3)	N27—C27—N27A—N21	−1.8 (4)
C16—C17—N17A—C13A	2.5 (4)	C26—C27—N27A—N21	177.9 (2)
C12—N11—N17A—C17	−176.0 (2)	N27—C27—N27A—C23A	177.6 (3)
C12—N11—N17A—C13A	0.5 (3)	C26—C27—N27A—C23A	−2.7 (4)
C13—C13A—N17A—C17	175.9 (2)	N24—C23A—N27A—N21	−177.6 (2)
N14—C13A—N17A—C17	−3.3 (4)	C23—C23A—N27A—N21	0.6 (3)
C13—C13A—N17A—N11	−0.6 (3)	N24—C23A—N27A—C27	2.9 (4)
N14—C13A—N17A—N11	−179.9 (2)	C23—C23A—N27A—C27	−178.9 (2)
N11—C12—C121—C126	−156.0 (3)	N21—C22—C221—C226	159.6 (3)
C13—C12—C121—C126	24.0 (4)	C23—C22—C221—C226	−19.5 (4)
N11—C12—C121—C122	24.1 (4)	N21—C22—C221—C222	−20.3 (4)
C13—C12—C121—C122	−155.8 (3)	C23—C22—C221—C222	160.6 (3)
C126—C121—C122—C123	0.7 (4)	C226—C221—C222—C223	−0.6 (4)
C12—C121—C122—C123	−179.5 (3)	C22—C221—C222—C223	179.3 (3)
C121—C122—C123—C124	−0.5 (4)	C221—C222—C223—C224	0.2 (4)
C122—C123—C124—C125	0.4 (4)	C222—C223—C224—C225	0.4 (4)
C123—C124—C125—C126	−0.4 (4)	C223—C224—C225—C226	−0.8 (5)
C122—C121—C126—C125	−0.8 (4)	C224—C225—C226—C221	0.4 (4)
C12—C121—C126—C125	179.4 (3)	C222—C221—C226—C225	0.2 (4)
C124—C125—C126—C121	0.6 (4)	C22—C221—C226—C225	−179.6 (3)
C17—C16—N161—N162	−4.6 (4)	C27—C26—N261—N262	2.6 (4)
C15—C16—N161—N162	−179.1 (2)	C25—C26—N261—N262	−177.1 (2)
C16—N161—N162—C161	175.2 (2)	C26—N261—N262—C261	179.0 (2)
N161—N162—C161—C166	160.1 (3)	N261—N262—C261—C266	−161.5 (2)
N161—N162—C161—C162	−20.6 (4)	N261—N262—C261—C262	18.9 (4)
C166—C161—C162—C163	−0.8 (4)	C266—C261—C262—C263	0.3 (4)
N162—C161—C162—C163	179.9 (3)	N262—C261—C262—C263	179.8 (2)
C161—C162—C163—C164	−0.7 (4)	C261—C262—C263—C264	1.0 (4)
C162—C163—C164—C165	1.3 (5)	C262—C263—C264—C265	−1.6 (4)
C163—C164—C165—C166	−0.5 (5)	C263—C264—C265—C266	0.8 (4)
C164—C165—C166—C161	−1.0 (5)	C264—C265—C266—C261	0.5 (4)
C162—C161—C166—C165	1.7 (4)	C262—C261—C266—C265	−1.0 (4)
N162—C161—C166—C165	−179.0 (3)	N262—C261—C266—C265	179.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N17—H17A···N14^i	0.88	2.29	2.972 (3)	134
N17—H17B···N162	0.88	2.08	2.691 (3)	125
N27—H27A···N24^i	0.88	2.30	2.953 (3)	131
N27—H27B···N262	0.88	2.05	2.656 (3)	125
C223—H223···Cg1^ii	0.95	2.95	3.701 (3)	137
C226—H226···Cg1	0.95	2.84	3.537 (3)	132
C262—H262···Cg2	0.95	2.89	3.609 (3)	134
C265—H265···Cg2^ii	0.95	2.89	3.625 (3)	136

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