N⁴-Methyl-N⁴-(2-methyl­phen­yl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine–ethanol–hydrazine (1/0.865/0.135): hydrogen-bonded ribbons containing four independent ring types

N⁴-Methyl-N⁴-(2-methyl­phen­yl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine crystallizes from ethanol as a mixed solvate, C₁₃H₁₄N₆·0.865C₂H₆O·0.135N₂H₄, (I), where the hydrazine has been carried through from the initial preparation. Within the heterocyclic component, the 2-methyl­phenyl substituent is disordered over two sets of sites. There is an intra­molecular C—H...π(arene) hydrogen bond, which may control the mol­ecular conformation of the heterocycle. The heterocyclic mol­ecules are linked by two independent N—H...N hydrogen bonds in a chain containing two types of R₂²(8) ring. The ethanol component is linked to this chain by a combination of O—H...N and N—H...O hydrogen bonds and the hydrazine component by two N—H...N hydrogen bonds, so generating two R₃³(9) rings and thus forming a ribbon containing four distinct ring types.

S1. Comment

We recently reported the structures of nine N⁴-substituted 1H-pyrazolo[3,4-d]pyrimidine-4,6-diamines, some of which crystallized in solvent-free from while others were found to be either stoichiometric monohydrates or stoichiometric hemihydrates: one example only, 4-(pyrrolidin-1-yl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine, crystallized as an ethanol hemisolvate hemihydrate (Trilleras et al., 2008). Where the N⁴ substituent was of the N-aryl-N-ethyl or N-aryl-N-methyl type, compounds (II)–(VI) (see Scheme), the molecular conformations were all very similar and these appeared to be controlled by an intramolecular C—H···π(arene) hydrogen bond with the N⁴-aryl unit as the acceptor. In those compounds which carried no other potential hydrogen-bonding sites in the N⁴ substituent, the molecules were linked into hydrogen-bonded sheets, but in the single example which carried additional hydrogen-bonding capacity in the N⁴ substituent, 2-[4-(6-amino-1H-pyrazolo[3,4-d]pyrimidin-4-yl)piperazin- 1-yl]ethanol, the hydrogen-bonded structure is three-dimensional.

As a continuation of the earlier study, we now report the structure of the title compound as a further example of this class; it crystallizes as a mixed solvate (Fig. 1) and, uniquely in this series, forms only a one-dimensional hydrogen-bonded structure. The heterocyclic compound crystallizes as a mixed solvate containing, in the crystal selected for data collection, 0.865 mol ethanol and 0.135 mol hydrazine per heterocycle corresponding overall to one solvent molecule per heterocyclic molecule. The roles of the two solvent components in the hydrogen-bonding scheme are entirely equivalent (see Table 2). A second form of disorder was found for the methyl group in the 2-methylphenyl substituent, corresponding to a 180° rotation about the bond N14—C11.

The coordination at atom N14 is planar within experimental uncertainty, and the overall conformation is thus definable in terms of just two torsional angles (Table 1): hence the phenyl ring is almost orthogonal to the pyrazole ring with a dihedral angle between these two rings of 89.6 (2)°. Associated with this conformation is a rather short C—H···π(arene) hydrogen bond, whose dimensions (Table 1) are strikingly similar to those of the corresponding interactions in compounds (II) and (V) (Trilleras et al., 2008).

Two independent N—H···N hydrogen bonds (Table 2) link the pyrazolopyrimidine units into a chain containing two distinct R₂²(8) (Bernstein et al., 1995) motifs. The ring atom N1 at (x, y, z) acts as donor to atom N7 at (1/2 - x, 1.5 - y, 1 - z), so forming a centrosymmetric R₂²(8) ring, centred at (1/4, 3/4, 1/2); in addition, the amino atom N16 at (x, y, z) acts as donor to atom N5 at (-x, y, 1/2 - z) so forming a second R₂²(8) ring lying across the twofold rotation axis along (0, y, 1/4). The combination of these two interactions then generates a puckered chain of rings running parallel to the [101] direction (Fig. 2). The solvent molecules lie on the edges of the chain of R₂²(8) rings, but the occupation of a given solvent by either ethanol or hydrazine does not alter the topology of the resulting hydrogen-bonded ring (Table 2). The major ethanol component is linked to the chain by a combination of O—H···N and N—H···O hydrogen bonds forming an R₃³(9) ring, such that a pair of these rings lies on either side of the centrosymmetric R₂²(8) ring, while the minor hydrazine component is linked to the chain by two N—H···N hydrogen bonds. The resulting arrays of three edge-fused rings have R⁴₄(18) peripheries (Fig. 2).

An entirely similar array of edge-fused rings is found in the stoichiometric monohydrate formed by compound (VI) (Trilleras et al., 2008). In this hydrate, the asymmetric unit contains two molecules of the heterocyclic component and two molecules of water, and these are linked into an array of one R₂²(8) and two R₃³(9) rings closely analogous to the corresponding array in compound (I). The principal difference is that in (VI) the array has only approximate, non-crystallographic centrosymmetry and, after formation of this aggregate, there still remain two N—H and two O—H bonds per aggregate which are available to link the aggregates further into chains, which are themselves linked into sheets by a C—H···π(arene) hydrogen bond. In the structures of each of (III)– (VI), which all crystallize either as monohydrates, compounds (III) and (VI), or as hemihydrates, compounds (IV) and (V), it is possible to identify one-dimensional substructures. However, in each such substructure the water component is integral to the chain formation, as it is in the mixed solvate (VII), while in compound (I), the solvent components are pendent from the chain, while doubtless reinforcing its formation.

Isomeric with the heterocyclic component of the title compound (I) is the imidazolyl-1,2,4-triazole (VIII) [CSD (Allen, 2002) refcode FUHHAR; Afshar et al., 1987]. In the structure of (VIII) three independent N—H···N hydrogen bonds, one intramolecular and two intermolecular, link the molecules into a chain of continuous edge-fused rings in which S(6) rings alternate with R₂²(7) rings (Fig. 3).

Related literature

For related literature, see: Afshar et al. (1987); Allen (2002); Bernstein et al. (1995); Boudet & Knochel (2006); Trilleras et al. (2008).

S2. Experimental

Compound (I) was prepared by reaction of the corresponding 2-amino-6-chloro-5-formyl-N⁴-methyl-N⁴- (2-methylphenyl)aminopyrimidine with hydrazine hydrate using the methods previously described (Boudet & Knochel, 2006; Trilleras et al., 2008). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in ethanol.

S3. Refinement

At an early stage in the refinement it became apparent that the 2-methylphenyl substituent was disordered over two orientations: with restraints applied to the two independent C(aryl)—C(methyl) distances, the final refined site occupancies were 0.763 (5) and 0.237 (5). Similarly, it was apparent that the solvent site was occupied primarily by ethanol, but with a second minor component also present; in the initial structure solution, the solvent component appeared as three distinct maxima, all of different sizes. The minor component was modelled as hydrazine, presumably from the initial preparation and carried through the subsequent purification steps. Independent refinement of the two solvent occupancies gave a sum of 0.993 (11); hence, the total occupancy was thereafter fixed at unity. With restraints applied to the C—O and C—C distances in the ethanol molecule, and to the N—N distance in the hydrazine, the final occupancies were 0.865 (11) for ethanol and 0.135 (11) for hydrazine (the hydrazine component was refined only isotropically). An alternative disorder model including methanol as the minor component in place of hydrazine gave marginally higher R values and larger residual densities, but it was rejected (a) because of the unsatisfactorily long C—O distance, 1.552 (16), which resulted despite a DFIX restraint similar to that imposed on the N—N distance in the hydrazine model and (b) because no methanol had been employed either in the preparation or in the crystallization. All H atoms apart from those in the hydrazine and in the minor-occupancy methyl group containing C17A, were located in difference maps; the remaining atoms were placed in calculated positions. Thereafter all H atoms were treated as riding atoms in geometrically idealized positions, such that the methyl groups were permitted to rotate but not to tilt, with distances C—H 0.95 Å (aromatic), 0.98 Å (CH₃) or 0.99 Å (CH₂). N—H 0.88-0.91 Å and O—H 0.84 Å, with U_iso(H) = kU_eq(carrier), where k = 1.5 for the hydrazine, hydroxyl, methyl groups 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: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and 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, with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. A stereoview of part of the crystal structure of compound (I) showing the formation of a hydrogen-bonded chain of rings parallel to [101]. For the sake of clarity the H atoms bonded to C atoms have all been omitted, the minor orientation of the disordered 2-methylphenyl substituent has been omitted, and the minor occupancy hydrazine component has been omitted.
	Fig. 3. A stereoview of part of the crystal structure of compound (VIII) (FUHHAR; Afshar et al., 1987) showing the formation of a chain of edge-fused S(6) and R2^2(7) rings. The original atom coordinates have been used. For the sake of clarity the H atoms bonded to C atoms have all been omitted.

N⁴-Methyl-N⁴-(2-methylphenyl)-1H-pyrazolo[3,4- d]pyrimidine-4,6-diamine–ethanol–hydrazine (1/0.865/0.135)

Crystal data

C13H14N6·0.865C2H6O·0.135N2H4	F(000) = 1271.2
Mr = 298.48	Dx = 1.284 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3539 reflections
a = 16.349 (3) Å	θ = 2.9–27.5°
b = 14.051 (2) Å	µ = 0.09 mm^−1
c = 13.625 (3) Å	T = 120 K
β = 99.308 (18)°	Block, colourless
V = 3088.7 (10) Å^3	0.35 × 0.28 × 0.22 mm
Z = 8

Data collection

Bruker Nonius KappaCCD diffractometer	3539 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2074 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.067
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 2.9°
ϕ & ω scans	h = −21→21
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −18→18
Tmin = 0.964, Tmax = 0.982	l = −17→17
22447 measured reflections

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)] = 0.065	H-atom parameters constrained
wR(F^2) = 0.191	w = 1/[σ^2(Fo^2) + (0.0833P)^2 + 5.1446P] where P = (Fo^2 + 2Fc^2)/3
S = 1.03	(Δ/σ)max = 0.001
3539 reflections	Δρmax = 0.43 e Å^−3
217 parameters	Δρmin = −0.37 e Å^−3
5 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0027 (7)

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.31548 (12)	0.69227 (15)	0.42931 (15)	0.0255 (5)
H1	0.3207	0.7334	0.4786	0.031*
N2	0.37961 (13)	0.66105 (16)	0.38502 (16)	0.0298 (5)
C3	0.34722 (16)	0.60082 (19)	0.31615 (19)	0.0306 (6)
H3	0.3779	0.5674	0.2736	0.037*
C3A	0.26108 (15)	0.59207 (18)	0.31340 (18)	0.0258 (6)
C4	0.19070 (16)	0.54638 (17)	0.25886 (18)	0.0261 (6)
N5	0.11563 (13)	0.56456 (15)	0.28051 (15)	0.0268 (5)
C6	0.10852 (15)	0.62377 (17)	0.35703 (18)	0.0245 (6)
N7	0.16955 (12)	0.66965 (14)	0.41471 (15)	0.0236 (5)
C7A	0.24386 (15)	0.65253 (17)	0.38845 (18)	0.0238 (5)
N14	0.19592 (13)	0.48472 (17)	0.18506 (17)	0.0335 (6)
C11	0.27516 (17)	0.4623 (2)	0.1591 (2)	0.0353 (7)
C13	0.3994 (2)	0.3726 (3)	0.1838 (3)	0.0609 (11)
H13	0.4320	0.3218	0.2153	0.073*
C14	0.4306 (2)	0.4272 (3)	0.1166 (3)	0.0697 (13)
H14	0.4852	0.4159	0.1037	0.084*
C15	0.3839 (2)	0.4986 (3)	0.0674 (3)	0.0613 (11)
H15	0.4054	0.5360	0.0194	0.074*
C12	0.32152 (18)	0.3887 (2)	0.2077 (2)	0.0439 (8)	0.237 (5)
H12	0.3006	0.3507	0.2558	0.053*	0.237 (5)
C16	0.3050 (2)	0.5161 (2)	0.0883 (2)	0.0475 (8)	0.763 (5)
H16	0.2717	0.5648	0.0538	0.057*	0.763 (5)
C12A	0.32152 (18)	0.3887 (2)	0.2077 (2)	0.0439 (8)	0.763 (5)
C17	0.2929 (3)	0.3334 (3)	0.2836 (3)	0.0508 (11)	0.763 (5)
H17A	0.3329	0.2827	0.3055	0.076*	0.763 (5)
H17B	0.2390	0.3051	0.2571	0.076*	0.763 (5)
H17C	0.2871	0.3745	0.3402	0.076*	0.763 (5)
C16A	0.3050 (2)	0.5161 (2)	0.0883 (2)	0.0475 (8)	0.237 (5)
C17A	0.2573 (9)	0.5867 (9)	0.0391 (10)	0.0508 (11)	0.237 (5)
H17D	0.2021	0.5615	0.0130	0.076*	0.237 (5)
H17E	0.2835	0.6101	−0.0161	0.076*	0.237 (5)
H17F	0.2520	0.6391	0.0851	0.076*	0.237 (5)
C18	0.12338 (17)	0.4354 (2)	0.1336 (2)	0.0425 (8)
H18A	0.0856	0.4211	0.1806	0.064*
H18B	0.1405	0.3760	0.1053	0.064*
H18C	0.0950	0.4759	0.0801	0.064*
N16	0.03131 (13)	0.63553 (16)	0.37538 (16)	0.0300 (5)
H16A	0.0220	0.6727	0.4244	0.036*
H16B	−0.0102	0.6061	0.3385	0.036*
O31	0.52762 (15)	0.7307 (2)	0.4846 (2)	0.0358 (9)	0.865 (11)
H31	0.4867	0.7006	0.4547	0.054*	0.865 (11)
C31	0.5747 (3)	0.7694 (5)	0.4132 (5)	0.0745 (19)	0.865 (11)
H31A	0.6095	0.7185	0.3913	0.089*	0.865 (11)
H31B	0.5359	0.7916	0.3542	0.089*	0.865 (11)
C32	0.6253 (6)	0.8449 (7)	0.4513 (7)	0.171 (5)	0.865 (11)
H32A	0.5915	0.8944	0.4758	0.257*	0.865 (11)
H32B	0.6530	0.8714	0.3988	0.257*	0.865 (11)
H32C	0.6670	0.8221	0.5061	0.257*	0.865 (11)
N91	0.534 (2)	0.765 (2)	0.454 (2)	0.065 (7)*	0.135 (11)
H911	0.5713	0.7203	0.4808	0.097*	0.135 (11)
H912	0.4892	0.7347	0.4178	0.097*	0.135 (11)
N92	0.5716 (18)	0.828 (2)	0.386 (2)	0.065 (7)*	0.135 (11)
H921	0.6077	0.8677	0.4238	0.097*	0.135 (11)
H922	0.5994	0.7919	0.3468	0.097*	0.135 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0227 (11)	0.0299 (11)	0.0239 (11)	−0.0012 (9)	0.0041 (9)	−0.0057 (9)
N2	0.0272 (12)	0.0344 (12)	0.0278 (12)	0.0009 (10)	0.0051 (9)	−0.0062 (10)
C3	0.0299 (15)	0.0353 (15)	0.0269 (14)	0.0022 (12)	0.0052 (11)	−0.0064 (11)
C3A	0.0260 (13)	0.0289 (13)	0.0220 (12)	0.0011 (11)	0.0023 (10)	−0.0033 (10)
C4	0.0280 (14)	0.0243 (13)	0.0250 (13)	0.0027 (11)	0.0015 (10)	−0.0024 (10)
N5	0.0275 (12)	0.0276 (11)	0.0246 (11)	−0.0011 (9)	0.0019 (9)	−0.0033 (9)
C6	0.0275 (14)	0.0242 (12)	0.0208 (12)	0.0004 (11)	0.0014 (10)	0.0007 (10)
N7	0.0242 (11)	0.0246 (11)	0.0216 (10)	−0.0007 (9)	0.0024 (8)	−0.0023 (8)
C7A	0.0279 (13)	0.0232 (12)	0.0196 (12)	−0.0001 (10)	0.0012 (10)	−0.0001 (10)
N14	0.0260 (12)	0.0398 (13)	0.0330 (12)	0.0020 (10)	−0.0004 (9)	−0.0161 (10)
C11	0.0287 (14)	0.0414 (16)	0.0344 (15)	−0.0007 (12)	0.0008 (12)	−0.0191 (13)
C13	0.0370 (19)	0.055 (2)	0.084 (3)	0.0068 (17)	−0.0089 (19)	−0.044 (2)
C14	0.038 (2)	0.085 (3)	0.088 (3)	−0.008 (2)	0.015 (2)	−0.053 (3)
C15	0.052 (2)	0.085 (3)	0.051 (2)	−0.019 (2)	0.0199 (17)	−0.034 (2)
C12	0.0337 (16)	0.0398 (17)	0.054 (2)	−0.0005 (13)	−0.0049 (14)	−0.0226 (15)
C16	0.0490 (19)	0.055 (2)	0.0391 (17)	−0.0060 (16)	0.0085 (14)	−0.0185 (15)
C12A	0.0337 (16)	0.0398 (17)	0.054 (2)	−0.0005 (13)	−0.0049 (14)	−0.0226 (15)
C17	0.054 (3)	0.045 (2)	0.050 (3)	0.002 (2)	−0.001 (2)	−0.0061 (19)
C16A	0.0490 (19)	0.055 (2)	0.0391 (17)	−0.0060 (16)	0.0085 (14)	−0.0185 (15)
C17A	0.054 (3)	0.045 (2)	0.050 (3)	0.002 (2)	−0.001 (2)	−0.0061 (19)
C18	0.0325 (16)	0.0486 (18)	0.0435 (18)	−0.0028 (14)	−0.0024 (13)	−0.0266 (14)
N16	0.0249 (12)	0.0364 (12)	0.0285 (12)	−0.0050 (10)	0.0040 (9)	−0.0105 (10)
O31	0.0262 (13)	0.0454 (18)	0.0375 (16)	−0.0121 (11)	0.0108 (11)	−0.0123 (12)
C31	0.064 (3)	0.076 (4)	0.095 (4)	−0.032 (3)	0.047 (3)	−0.020 (3)
C32	0.186 (9)	0.199 (10)	0.143 (8)	−0.123 (8)	0.068 (7)	−0.041 (7)

Geometric parameters (Å, º)

N1—C7a	1.335 (3)	C16—H16	0.9500
N1—N2	1.364 (3)	C17—H17A	0.9800
N1—H1	0.8800	C17—H17B	0.9800
N2—C3	1.310 (3)	C17—H17C	0.9800
C3—C3a	1.408 (4)	C17a—H17D	0.9800
C3—H3	0.9500	C17a—H17E	0.9800
C3a—C7a	1.393 (3)	C17a—H17F	0.9800
C3a—C4	1.418 (4)	C18—H18A	0.9800
C4—N5	1.333 (3)	C18—H18B	0.9800
C4—N14	1.340 (3)	C18—H18C	0.9800
N5—C6	1.353 (3)	N16—H16A	0.8800
C6—N7	1.332 (3)	N16—H16B	0.8800
C6—N16	1.336 (3)	O31—C31	1.441 (5)
N7—C7a	1.343 (3)	O31—H31	0.8400
N14—C11	1.432 (3)	C31—C32	1.393 (8)
N14—C18	1.452 (3)	C31—H31A	0.9900
C11—C16	1.375 (4)	C31—H31B	0.9900
C11—C12	1.387 (4)	C32—H32A	0.9800
C13—C14	1.356 (6)	C32—H32B	0.9800
C13—C12	1.384 (5)	C32—H32C	0.9800
C13—H13	0.9500	N91—N92	1.480 (10)
C14—C15	1.369 (6)	N91—H911	0.9100
C14—H14	0.9500	N91—H912	0.9100
C15—C16	1.387 (5)	N92—H921	0.9100
C15—H15	0.9500	N92—H922	0.9100
C12—H12	0.9500
C7a—N1—N2	111.5 (2)	C16—C15—H15	120.2
C7a—N1—H1	124.3	C13—C12—C11	117.5 (3)
N2—N1—H1	124.3	C13—C12—H12	121.2
C3—N2—N1	105.9 (2)	C11—C12—H12	121.2
N2—C3—C3a	111.2 (2)	C11—C16—C15	119.6 (4)
N2—C3—H3	124.4	C11—C16—H16	120.2
C3a—C3—H3	124.4	C15—C16—H16	120.2
C7a—C3a—C3	104.3 (2)	H17A—C17—H17B	109.5
C7a—C3a—C4	114.7 (2)	H17A—C17—H17C	109.5
C3—C3a—C4	140.9 (2)	H17B—C17—H17C	109.5
N5—C4—N14	117.6 (2)	H17D—C17a—H17E	109.5
N5—C4—C3a	119.7 (2)	H17D—C17a—H17F	109.5
N14—C4—C3a	122.7 (2)	H17E—C17a—H17F	109.5
C4—N5—C6	119.0 (2)	N14—C18—H18A	109.5
N7—C6—N16	118.0 (2)	N14—C18—H18B	109.5
N7—C6—N5	127.0 (2)	H18A—C18—H18B	109.5
N16—C6—N5	114.9 (2)	N14—C18—H18C	109.5
C6—N7—C7a	112.3 (2)	H18A—C18—H18C	109.5
N1—C7a—N7	125.8 (2)	H18B—C18—H18C	109.5
N1—C7a—C3a	107.1 (2)	C6—N16—H16A	120.0
N7—C7a—C3a	127.2 (2)	C6—N16—H16B	120.0
C4—N14—C11	119.8 (2)	H16A—N16—H16B	120.0
C4—N14—C18	121.6 (2)	C32—C31—O31	112.7 (5)
C11—N14—C18	118.5 (2)	C32—C31—H31A	109.1
C16—C11—C12	121.1 (3)	O31—C31—H31A	109.1
C16—C11—N14	119.4 (3)	C32—C31—H31B	109.1
C12—C11—N14	119.5 (3)	O31—C31—H31B	109.1
C14—C13—C12	121.8 (4)	H31A—C31—H31B	107.8
C14—C13—H13	119.1	N92—N91—H911	109.8
C12—C13—H13	119.1	N92—N91—H912	108.9
C13—C14—C15	120.3 (3)	H911—N91—H912	109.5
C13—C14—H14	119.8	N91—N92—H921	108.9
C15—C14—H14	119.8	N91—N92—H922	109.6
C14—C15—C16	119.5 (4)	H921—N92—H922	109.5
C14—C15—H15	120.2
C7a—N1—N2—C3	−0.3 (3)	C4—C3a—C7a—N1	−177.5 (2)
N1—N2—C3—C3a	0.5 (3)	C3—C3a—C7a—N7	179.4 (2)
N2—C3—C3a—C7a	−0.6 (3)	C4—C3a—C7a—N7	1.5 (4)
N2—C3—C3a—C4	176.4 (3)	N5—C4—N14—C11	−179.7 (2)
C7a—C3a—C4—N5	1.2 (4)	C3a—C4—N14—C11	0.4 (4)
C3—C3a—C4—N5	−175.6 (3)	N5—C4—N14—C18	−3.1 (4)
C7a—C3a—C4—N14	−178.9 (2)	C3a—C4—N14—C18	177.0 (3)
C3—C3a—C4—N14	4.3 (5)	C4—N14—C11—C16	−90.0 (3)
N14—C4—N5—C6	177.6 (2)	C18—N14—C11—C16	93.3 (3)
C3a—C4—N5—C6	−2.5 (4)	C4—N14—C11—C12	88.1 (3)
C4—N5—C6—N7	1.5 (4)	C18—N14—C11—C12	−88.6 (3)
C4—N5—C6—N16	−178.0 (2)	C12—C13—C14—C15	−2.4 (5)
N16—C6—N7—C7a	−179.6 (2)	C13—C14—C15—C16	1.3 (5)
N5—C6—N7—C7a	0.9 (4)	C14—C13—C12—C11	1.1 (5)
N2—N1—C7a—N7	−179.1 (2)	C16—C11—C12—C13	1.2 (4)
N2—N1—C7a—C3a	0.0 (3)	N14—C11—C12—C13	−176.9 (3)
C6—N7—C7a—N1	176.4 (2)	C12—C11—C16—C15	−2.3 (4)
C6—N7—C7a—C3a	−2.5 (4)	N14—C11—C16—C15	175.8 (3)
C3—C3a—C7a—N1	0.3 (3)	C14—C15—C16—C11	1.0 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···Cg	0.95	2.52	3.296 (3)	138
N91—H912···N2	0.92	2.05	2.94 (3)	160
O31—H31···N2	0.84	1.93	2.755 (3)	166
N1—H1···N7^i	0.88	1.98	2.859 (3)	177
N16—H16A···O31^i	0.88	2.09	2.949 (4)	165
N16—H16A···N91^i	0.88	2.20	3.05 (3)	163
N16—H16B···N5^ii	0.88	2.24	3.103 (3)	165

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x, y, −z+1/2.