Hydrogen bonding in 2-amino-4,6-dimethoxypyrimidine, 2-benzylamino-4,6-bis(benzyloxy)pyrimidine and 2-amino-4,6-bis(N-pyrrolidino)pyrimidine: chains of fused rings and a centrosymmetric dimer

Molecules of 2-amino-4,6-di­methoxy­pyrimidine, C₆H₉N₃O₂, (I), are linked by two N-H...N hydrogen bonds [H...N 2.23 and 2.50 Å, N...N 3.106 (2) and 3.261 (2) Å, and N-H...N 171 and 145°] into a chain of fused rings, where alternate rings are generated by centres of inversion and twofold rotation axes. Adjacent chains are linked by aromatic [pi]-[pi]-stacking interactions to form a three-dimensional framework. In 2-­benzylamino-4,6-bis(benzyloxy)pyrimidine, C₂₅H₂₃N₃O₂, (II), the mol­ecules are linked into centrosymmetric R(8) dimers by paired N-H...N hydrogen bonds [H...N 2.13 Å, N...N 2.997 (2) Å and N-H...N 170°]. Molecules of 2-amino-4,6-bis(N-pyrrolidino)­pyrimidine, C₁₂H₁₉N₅, (III), are linked by two N-H...N hydrogen bonds [H...N 2.34 and 2.38 Å, N...N 3.186 (2) and 3.254 (2) Å, and N-H...N 163 and 170°] into a chain of fused rings similar to that in (I).

S1. Comment

4,6-Dialkoxypyrimidines are key intermediates for the synthesis of a wide range of alkoxy and amino substituted O⁶-benzyloxy-5-nitrosopyrimidines (Marchal et al., 1998, 2000; Quesada et al., 2000), which are important as potential, or proven, in vitro inhibitors of the human DNA-repair protein O⁶-alkylguanine-DNA-transferase (Chae et al., 1995; Quesada et al., 2002). Here, we report the molecular and supramolecular structures of two examples of this class of pyrimidine, 2-amino-4,6-dimethoxypyrimidine (I) and 2-benzylamino-4,6-bis(benzyloxy)pyrimidine (II). \sch

Compound (I) could, in principle, adopt a conformation having C_2v (mm2) molecular symmetry. In the event, the conformations of the two independent methoxy substituents are such that there is no exact molecular symmetry, although there is approximate C_s (m) symmetry (Fig. 1, Table 1). The C—N distances in (I) span the rather small range 1.331 (2)–1.355 (2) Å, with no significant bond fixation within the pyrimidine ring (Table 1). In this respect, the molecular-electronic structure of (I) is markedly different from those in a large number of analogous pyrimidines carrying a 5-nitroso substituent, where highly polarized structures are the norm (Low et al., 2000; Low, Cannon et al., 2001; Low, Moreno et al., 2001; Quesada et al., 2002).

The amino group in (I) acts as a double donor in N—H···N hydrogen bonds, while the two ring N atoms act as the acceptors. The O atoms play no part in the intermolecular aggregation (Table 2). Amino atom N2 at (x, y, z) acts as a hydrogen-bond donor, via atom H2A, to atom N1 at (-x, 1 - y, 1 - z), so generating a centrosymmetric R₂²(8) ring centred at (0, 1/2, 1/2). This amino atom N2 at (x, y, z) also acts as a donor, this time via atom H2B, to atom N3 at (-x, y, 1/2 - z), so producing a second R₂²(8) motif, generated by the twofold rotation axis along (0, y, 1/4). Propagation of these two hydrogen-bonding motifs by inversion and rotation generates a chain of fused rings running parallel to the [001] direction (Fig. 2). The supramolecular structure can alternatively be viewed as a molecular ladder, in which paired C₂²(6) chains form the uprights and the C2—N2 covalent bonds form the rungs, so that the full graph-set designation is C₂²(6)[R₂²(8)][R₂²(8)].

Two chains of this type, related by the C-centring operation, run through each unit cell, along the lines (0, 1/2, z) and (1/2, 1, z), and the parallel chains are linked by aromatic π···π stacking interactions to form a three-dimensional continuum. The pyrimidine rings of the molecules at (x, y, z) and (1/2 - x, 1/2 - y, 1 - z) have parallel planes separated by 3.319 (2) Å; the centroid separation is 3.412 (2) Å and the centroid offset is only ca 0.79 Å (Fig. 3). In this manner, the chain along (0, 1/2, z) is linked to each of the chains along (1/2, 0, z), (1/2, 1, z), (-1/2, 0, z) and (-1/2, 1, z), so forming a continuous bundle of chains.

In compound (II) (Fig. 4), the atoms C27, C47 and C67 are also nearly coplanar with the pyrimidine ring, and the conformation of the alkoxy groups is similar to that in (I) (Fig. 4, Table 3), although the phenyl groups each add two further rotational degrees of freedom. As in (I), there is no evidence of bond fixation or charge separation in the pyrimidine ring (Table 3). With only one N—H per molecule available for N—H···N hydrogen-bond formation, the supramolecular structure of (II) is much simpler than that of (I). The molecules are linked by the hydrogen bonds into centrosymmetric dimers (Fig. 5, Table 4), and there are no aromatic π···π stacking interactions, so that the supramolecular aggregation consists simply of one finite zero-dimensional dimer per unit cell, with no direction-specific interactions between these units.

We also report here the structure of the closely-related compound 2-amino-4,6-bis(N-pyrrolidino)pyrimidine, (III). We have recently investigated the structure of the 5-nitroso analogue, (IV) (Quesada et al., 2002). However, not only were the crystals of (II) should this be (IV)?, obtainable only as a partial hydrate, of consistently poor quality [indeed, analogues of (IV) containing other secondary amino substituents cannot be crystallized at all], but the structure of (IV) was characterized by pseudosymmetry between the two independent molecules, by multiple disorder, both in the orientations of the two nitroso groups and in the conformations of the four independent pyrrolidine rings, and by partial occupancy of each of the two independent water sites. Because of the poor diffraction data and the multiple disorder, no meaningful conclusions could be drawn about the intramolecular structural parameters for (IV), although the supramolecular structure, which takes the form of centrosymmetric six-molecule aggregates, was readily established.

In compound (III) (Fig. 6), by contrast, the intramolecular distances and angles are all well defined (Table 5). The four C—N distances within the pyrimidine ring, as well as the three exocyclic C—N distances involving three-connected C, all lie within the rather narrow range 1.346 (2)–1.359 (2) Å. This range of values is somewhat higher than the mean value of 1.333 Å for pyrimidines in general (Allen et al., 1987) but, overall, the C—N and C—C distances within the pyrimidine ring of (I) should this be (III)? are consistent with aromatic delocalization, with no significant bond fixation. At each of N4 and N6, the sum of the bond angles indicates planar N, consistent with the C4—N4 and C6—N6 distances (Allen et al., 1987), and typical of amino N bonded to an aromatic or heteroaromatic ring. While the pyrrolidine rings exhibit the puckered conformation characteristic of saturated five-membered rings, there is no evidence, either from difference maps or from the displacement parameters, for any positional disorder of the C atoms in these rings. The CNC₂ planes centred on N4 and N6 are only very slightly twisted out of the plane of the pyrimidine ring (Table 5). The overall conformation of the molecule of (III) is very close to having local twofold rotational symmetry. This is illustrated not only by the torsion angles within the pyrrolidine rings (Table 5) but, perhaps more strikingly, by the location of the H atoms in these rings (Fig. 6). However, a search for possible additional symmetry revealed none.

The supramolecular structure of (III) takes the form of a chain of fused rings, similar to that found in (I). The amino group acts as a double donor in the intermolecular N—H···N hydrogen bonds, where the acceptors are the two ring N atoms (Table 6); the planar pyrrolidine N atoms play no part in the supramolecular aggregation. Amino atom N2 at (x, y, z) acts as a hydrogen-bond donor, via atom H2A, to ring atom N1 at (x, 1 - y, -z), so forming an R₂²(8) motif centred at (0, 1/2, 0). This amino atom N2 at (x, y, z) also acts as a donor, via atom H2B, to ring atom N3 at (-x, y, 1/2 - z), so forming a second R₂²(8) motif, this time generated by the twofold rotation axis along (0, y, 1/4). The combination of these two distinct R₂²(8) motifs, the one containing atoms N1 and N2 and the other containing atoms N2 and N3, generates a chain of fused rings running parallel to the [001] direction (Fig. 6), generated by inversion centres at (0, 1/2, n/2) (for n = zero or integer) and twofold axes along (0, y, 1/4 + n/2) (n = zero or integer). Two of these chains run through each unit cell, but there are no direction-specific interactions between adjacent chains. In particular, the π···π stacking interactions found in (I) are absent from the structure of (III). We note that this type of supramolecular aggregation would be possible even if the molecules of (III) had been located on twofold rotation axes.

It is of interest to compare the conformations and supramolecular aggregation in compounds (I) and (II) with those in the related compound, (V) (Quesada et al., 2002), which is analogous to (I) in containing an unsubstituted amino group, and to (II) in containing two benzyloxy substituents. In (V), where the conformation of the alkoxy substitutents is identical to those in (I) and (II), hydrogen-bonded R₂²(8) dimers precisely analogous to those in (II) are linked into a molecular ladder by N—H···O hydrogen bonds, with atom O4 as the acceptor. By contrast, the O atoms in (I) and (II) play no role in the hydrogen bonding, as noted above. Likewise, the supramolecular structures of (I), (III) and (V) can be contrasted with that of 2-aminopyrimidine, (VI), itself (Scheinbeim & Schempp, 1976; Furberg et al., 1979). The molecules of (VI) act as double donors and double acceptors of N—H···N hydrogen bonds and two motifs are generated, by a centre of inversion and by a glide plane, leading to the formation of sheets.

S2. Experimental

A sample of (I) was purchased from Aldrich. For the synthesis of (II), (I) (19.3 mmol) was added to a stirred solution of sodium benzylate (96 mmol) in toluene (100 ml). The resulting mixture was heated under reflux, with stirring, for 60 h. Diethyl ether (30 ml) and toluene (15 ml) were then added and the mixture was filtered through silica gel. The silica gel was washed with toluene (3 × 40 ml) and diethyl ether (3 × 40 ml), and the filtrate and the washings were pooled together. After removal of the solvent, the oily residue was dissolved in a hexane-ethyl ether mixture (60:40 v/v) and cooled. The product, (II), precipitated at 253 K and was collected by filtration, washed with hexane and dried in vacuo (yield 70%, m.p. 355 K). Analysis, found: C 75.2, H 5.8, N 10.6%; C₂₅H₂₃N₃O₂ requires: C 75.5, H 5.8, N 10.6%. Spectroscopic analysis: ¹H NMR (DMSO-d₆, δ, p.p.m.): 4.46 (d, 2H, N—CH₂, J = 6.02 Hz), 5.27 (s, 4H, O—CH₂), 5.45 (s, 1H, C5—H), 7.29 (m, 15H, Ph), 7.75 (t, H, NH, J = 6.59 Hz, exchanges with D₂O); ¹³C NMR (δ, p.p.m): 44.1, 66.7, 78.1, 126.4, 128,2, 136.8, 140.4, 161.2, 170.8. For the synthesis of (III), pyrrolidine (21.3 mmol) and triethylamine (18.3 mmol) were added to a stirred solution of 2-amino-4,6-dichloropyrimidine (Aldrich; 6.1 mmol) in n-butyl alcohol (40 ml). The resulting mixture was heated under reflux, with stirring, for 56 h. After filtration and removal of the solvent, hot ethyl acetate (100 ml) was added, and the product, (III), was filtered off (yield 68%, m.p. 497 K). Analysis, found: C 61.7, H 7.9, N 29.9%; C₁₂H₁₉N₅ requires: C 61.8, H 8.2, N 30.0%. Spectroscopic analysis: ¹H NMR (DMSO-d₆, δ, p.p.m.): 1.85 (m, 8H, CH₂), 3.27 (m, 8H, N—CH₂, partially obscured by solvent DMSO-d₆), 5.31 (s, 2H, NH₂, exchanges with D₂O); ¹³C NMR (δ, p.p.m.): 24.6, 45.7, 73.2, 161.3, 161.6. Crystals of (I), (II) and (III) suitable for single-crystal X-ray diffraction were grown by slow evaporation of solutions in acetone, methanol and dichloromethane-ethyl acetate (1:1 v/v), respectively.

S3. Refinement

Compounds (I) and (III) are monoclinic and the systematic absences permitted space groups C2/c and Cc. For each, C2/c was chosen and confirmed by the analysis. Compound (II) is triclinic; space group P1 was selected, and confirmed by the analysis. H atoms were treated as riding, with C—H = 0.95–0.98 Å and N—H 0.88 Å.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997) for (I), (III); SMART (Bruker, 1997) for (II). Cell refinement: DENZO-SMN (Otwinowski & Minor, 1997) for (I), (III); SMART for (II). Data reduction: DENZO-SMN (Otwinowski & Minor, 1997) for (I); SHELXTL (Bruker, 1997) for (II); DENZO-SMN for (III). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).

Figures

	Fig. 1. A view of the molecule of (I) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. Part of the crystal structure of (I) showing formation of a chain of fused rings along [001]. The atoms marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (-x, y, 1/2 - z), (-x, 1 - y, 1 - z), (x, 1 - y, z - 1/2) and (x, 1 - y, 1/2 + z), respectively.
	Fig. 3. Part of the crystal structure of (I) showing the aromatic π···π stacking interaction which links the [001] chains. The atoms marked with an asterisk (*) are at the symmetry position (1/2 - x, 1/2 - y, 1 - z).
	Fig. 4. A view of the molecule of (II) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 5. Part of the crystal structure of (II) showing formation of a centrosymmetric dimer. The atoms marked with an asterisk (*) are at the symmetry position (2 - x, -y, 1 - z).
	Fig. 6. A view of the molecule of (III) showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 7. Part of the crystal structure of (III) showing formation of a chain of fused rings along [001]. The atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (-x, 1 - y, -z) and (-x, y, 1/2 - z), respectively.

(I) 2-Amino-4,6-dimethoxypyrimidine

Crystal data

C6H9N3O2	F(000) = 656
Mr = 155.16	Dx = 1.429 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1642 reflections
a = 12.3971 (5) Å	θ = 2.9–27.4°
b = 8.3608 (5) Å	µ = 0.11 mm^−1
c = 14.5237 (7) Å	T = 120 K
β = 106.585 (3)°	Block, colourless
V = 1442.75 (13) Å^3	0.20 × 0.15 × 0.05 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	1642 independent reflections
Radiation source: fine-focus sealed X-ray tube	1090 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.066
ϕ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 2.9°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −16→14
Tmin = 0.978, Tmax = 0.994	k = −9→10
5248 measured reflections	l = −17→18

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.132	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0727P)^2] where P = (Fo^2 + 2Fc^2)/3
1642 reflections	(Δ/σ)max < 0.001
102 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame).

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

	x	y	z	Uiso*/Ueq
N1	0.14019 (11)	0.48401 (17)	0.48098 (9)	0.0206 (4)
N2	−0.01762 (11)	0.37392 (19)	0.37859 (10)	0.0285 (4)
N3	0.14982 (11)	0.31903 (17)	0.34783 (9)	0.0205 (4)
C2	0.09446 (13)	0.3937 (2)	0.40367 (11)	0.0196 (4)
O4	0.32450 (9)	0.26690 (14)	0.32742 (8)	0.0244 (3)
C4	0.26097 (13)	0.3388 (2)	0.37614 (11)	0.0200 (4)
C41	0.27005 (15)	0.1574 (2)	0.25231 (12)	0.0266 (4)
C5	0.31797 (13)	0.4311 (2)	0.45409 (11)	0.0209 (4)
O6	0.29165 (9)	0.59379 (15)	0.58250 (8)	0.0253 (3)
C6	0.25158 (13)	0.5009 (2)	0.50419 (10)	0.0205 (4)
C61	0.41058 (14)	0.6223 (2)	0.61287 (13)	0.0307 (5)
H2A	−0.0576	0.4195	0.4126	0.034*
H2B	−0.0511	0.3154	0.3282	0.034*
H41A	0.2195	0.0873	0.2749	0.040*
H41B	0.3270	0.0925	0.2347	0.040*
H41C	0.2265	0.2176	0.1961	0.040*
H5	0.3973	0.4451	0.4717	0.025*
H61A	0.4505	0.5200	0.6270	0.046*
H61B	0.4296	0.6889	0.6708	0.046*
H61C	0.4329	0.6774	0.5616	0.046*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0176 (8)	0.0247 (8)	0.0192 (7)	0.0026 (6)	0.0048 (6)	−0.0002 (6)
N2	0.0161 (8)	0.0425 (10)	0.0265 (8)	0.0012 (7)	0.0051 (6)	−0.0114 (7)
N3	0.0207 (8)	0.0233 (8)	0.0185 (7)	0.0011 (6)	0.0071 (6)	0.0008 (6)
C2	0.0196 (9)	0.0207 (10)	0.0186 (8)	0.0022 (7)	0.0055 (7)	0.0038 (7)
O4	0.0221 (7)	0.0297 (7)	0.0224 (6)	0.0025 (5)	0.0081 (5)	−0.0049 (5)
C4	0.0208 (9)	0.0219 (10)	0.0186 (8)	0.0050 (7)	0.0077 (7)	0.0055 (7)
C41	0.0307 (10)	0.0255 (10)	0.0258 (9)	0.0012 (8)	0.0114 (8)	−0.0046 (8)
C5	0.0153 (8)	0.0248 (10)	0.0222 (8)	0.0006 (7)	0.0047 (7)	0.0003 (7)
O6	0.0191 (7)	0.0349 (8)	0.0213 (6)	−0.0007 (5)	0.0046 (5)	−0.0076 (5)
C6	0.0210 (9)	0.0223 (10)	0.0173 (8)	0.0016 (7)	0.0042 (7)	0.0006 (7)
C61	0.0174 (9)	0.0414 (12)	0.0303 (10)	−0.0002 (8)	0.0018 (8)	−0.0118 (8)

Geometric parameters (Å, º)

N1—C2	1.338 (2)	O6—C61	1.433 (2)
C2—N3	1.355 (2)	N2—H2A	0.8800
N3—C4	1.331 (2)	N2—H2B	0.8800
C4—C5	1.386 (2)	C41—H41A	0.9800
C5—C6	1.375 (2)	C41—H41B	0.9800
C6—N1	1.332 (2)	C41—H41C	0.9800
C2—N2	1.342 (2)	C5—H5	0.9500
C4—O4	1.342 (2)	C61—H61A	0.9800
O4—C41	1.437 (2)	C61—H61B	0.9800
C6—O6	1.3492 (19)	C61—H61C	0.9800
C6—N1—C2	115.64 (13)	H41A—C41—H41C	109.5
C2—N2—H2A	120.0	H41B—C41—H41C	109.5
C2—N2—H2B	120.0	C6—C5—C4	115.24 (15)
H2A—N2—H2B	120.0	C6—C5—H5	122.4
C4—N3—C2	114.49 (14)	C4—C5—H5	122.4
N1—C2—N2	117.07 (14)	C6—O6—C61	117.00 (13)
N1—C2—N3	126.64 (14)	N1—C6—O6	112.34 (13)
N2—C2—N3	116.28 (15)	N1—C6—C5	123.70 (15)
C4—O4—C41	117.81 (12)	O6—C6—C5	123.96 (15)
N3—C4—O4	119.56 (15)	O6—C61—H61A	109.5
N3—C4—C5	124.27 (15)	O6—C61—H61B	109.5
O4—C4—C5	116.17 (14)	H61A—C61—H61B	109.5
O4—C41—H41A	109.5	O6—C61—H61C	109.5
O4—C41—H41B	109.5	H61A—C61—H61C	109.5
H41A—C41—H41B	109.5	H61B—C61—H61C	109.5
O4—C41—H41C	109.5
C6—N1—C2—N2	179.80 (15)	N3—C4—C5—C6	1.6 (2)
C6—N1—C2—N3	0.1 (2)	O4—C4—C5—C6	−178.70 (14)
C4—N3—C2—N1	1.1 (2)	C2—N1—C6—O6	179.78 (13)
C4—N3—C2—N2	−178.68 (14)	C2—N1—C6—C5	−0.4 (2)
C2—N3—C4—O4	178.40 (14)	C61—O6—C6—N1	−178.95 (15)
C2—N3—C4—C5	−1.9 (2)	C61—O6—C6—C5	1.3 (2)
C41—O4—C4—N3	−6.5 (2)	C4—C5—C6—N1	−0.3 (3)
C41—O4—C4—C5	173.81 (15)	C4—C5—C6—O6	179.44 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1^i	0.88	2.23	3.106 (2)	171
N2—H2B···N3^ii	0.88	2.50	3.261 (2)	145

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

(II) 2-Benzylamino-4,6-bis(benzyloxy)pyrimidine

Crystal data

C25H23N3O2	Z = 2
Mr = 397.46	F(000) = 420
Triclinic, P1	Dx = 1.272 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8083 (6) Å	Cell parameters from 4785 reflections
b = 12.3104 (13) Å	θ = 1.8–29.0°
c = 15.7260 (16) Å	µ = 0.08 mm^−1
α = 68.549 (2)°	T = 120 K
β = 85.978 (2)°	Needle, colourless
γ = 82.737 (2)°	0.14 × 0.05 × 0.04 mm
V = 1037.81 (19) Å^3

Data collection

Bruker SMART 1000 diffractometer	4785 independent reflections
Radiation source: fine-focus sealed X-ray tube	3697 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.010
ϕ scans, and ω scans with κ offsets	θmax = 29.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −7→7
Tmin = 0.989, Tmax = 0.997	k = −13→16
6639 measured reflections	l = −20→19

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0612P)^2 + 0.0805P] where P = (Fo^2 + 2Fc^2)/3
4785 reflections	(Δ/σ)max < 0.001
271 parameters	Δρmax = 0.25 e Å^−3
0 restraints	Δρmin = −0.22 e Å^−3

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

	x	y	z	Uiso*/Ueq
N1	1.06020 (18)	0.15079 (9)	0.43312 (7)	0.0245 (2)
C2	0.9040 (2)	0.14975 (10)	0.37413 (8)	0.0234 (2)
N2	0.81278 (19)	0.04843 (9)	0.39253 (7)	0.0279 (2)
C27	0.6332 (2)	0.03365 (11)	0.33940 (8)	0.0261 (3)
C21	0.7221 (2)	−0.00571 (10)	0.26110 (8)	0.0231 (3)
C22	0.5881 (2)	−0.07097 (11)	0.23235 (8)	0.0275 (3)
C23	0.6605 (2)	−0.10549 (11)	0.15896 (9)	0.0328 (3)
C24	0.8691 (2)	−0.07512 (12)	0.11369 (9)	0.0334 (3)
C25	1.0057 (2)	−0.01108 (12)	0.14225 (9)	0.0317 (3)
C26	0.9327 (2)	0.02341 (11)	0.21554 (8)	0.0272 (3)
N3	0.82976 (18)	0.24202 (8)	0.29875 (6)	0.0249 (2)
C4	0.9258 (2)	0.33947 (10)	0.28374 (8)	0.0238 (3)
O4	0.85807 (15)	0.43613 (7)	0.21106 (6)	0.0280 (2)
C47	0.6792 (2)	0.42567 (11)	0.15532 (9)	0.0321 (3)
C41	0.6113 (2)	0.54692 (11)	0.08775 (8)	0.0278 (3)
C42	0.7715 (3)	0.60873 (13)	0.02532 (11)	0.0409 (3)
C43	0.7082 (3)	0.72002 (13)	−0.03715 (11)	0.0454 (4)
C44	0.4837 (3)	0.77170 (12)	−0.03714 (10)	0.0392 (3)
C45	0.3238 (3)	0.71142 (13)	0.02456 (10)	0.0396 (3)
C46	0.3856 (2)	0.59913 (12)	0.08676 (9)	0.0334 (3)
C5	1.0904 (2)	0.35194 (10)	0.33882 (8)	0.0257 (3)
C6	1.1484 (2)	0.25220 (10)	0.41456 (8)	0.0237 (3)
O6	1.29228 (15)	0.24744 (7)	0.48017 (6)	0.0284 (2)
C67	1.3823 (3)	0.35596 (11)	0.47016 (9)	0.0338 (3)
C61	1.5029 (2)	0.34046 (10)	0.55579 (8)	0.0264 (3)
C62	1.3964 (2)	0.38608 (11)	0.61912 (9)	0.0280 (3)
C63	1.5120 (3)	0.37561 (11)	0.69647 (9)	0.0332 (3)
C64	1.7358 (2)	0.32039 (11)	0.71061 (9)	0.0347 (3)
C65	1.8430 (2)	0.27374 (12)	0.64840 (10)	0.0355 (3)
C66	1.7265 (2)	0.28324 (11)	0.57154 (9)	0.0320 (3)
H2	0.8652	−0.0127	0.4397	0.033*
H27A	0.5340	0.1092	0.3143	0.031*
H27B	0.5343	−0.0248	0.3807	0.031*
H22	0.4449	−0.0923	0.2633	0.033*
H23	0.5667	−0.1499	0.1399	0.039*
H24	0.9185	−0.0981	0.0633	0.040*
H25	1.1497	0.0093	0.1116	0.038*
H26	1.0274	0.0673	0.2347	0.033*
H47A	0.5433	0.3942	0.1940	0.039*
H47B	0.7393	0.3720	0.1230	0.039*
H42	0.9273	0.5743	0.0253	0.049*
H43	0.8199	0.7608	−0.0801	0.054*
H44	0.4401	0.8484	−0.0795	0.047*
H45	0.1687	0.7468	0.0249	0.048*
H46	0.2725	0.5581	0.1288	0.040*
H5	1.1575	0.4230	0.3256	0.031*
H67A	1.2535	0.4200	0.4589	0.041*
H67B	1.4928	0.3774	0.4173	0.041*
H62	1.2431	0.4248	0.6094	0.034*
H63	1.4371	0.4065	0.7398	0.040*
H64	1.8158	0.3145	0.7630	0.042*
H65	1.9964	0.2352	0.6583	0.043*
H66	1.8002	0.2503	0.5293	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0330 (5)	0.0203 (5)	0.0203 (5)	−0.0065 (4)	−0.0032 (4)	−0.0059 (4)
C2	0.0304 (6)	0.0205 (6)	0.0201 (5)	−0.0048 (5)	−0.0013 (5)	−0.0075 (5)
N2	0.0402 (6)	0.0199 (5)	0.0222 (5)	−0.0094 (4)	−0.0091 (4)	−0.0023 (4)
C27	0.0303 (6)	0.0233 (6)	0.0243 (6)	−0.0088 (5)	−0.0026 (5)	−0.0057 (5)
C21	0.0271 (6)	0.0169 (5)	0.0217 (6)	−0.0023 (5)	−0.0078 (5)	−0.0015 (4)
C22	0.0299 (6)	0.0247 (6)	0.0260 (6)	−0.0081 (5)	−0.0049 (5)	−0.0046 (5)
C23	0.0461 (8)	0.0262 (7)	0.0279 (6)	−0.0101 (6)	−0.0085 (6)	−0.0085 (5)
C24	0.0446 (8)	0.0274 (7)	0.0271 (6)	0.0002 (6)	−0.0030 (6)	−0.0093 (5)
C25	0.0284 (6)	0.0323 (7)	0.0296 (7)	−0.0019 (5)	−0.0005 (5)	−0.0061 (5)
C26	0.0274 (6)	0.0247 (6)	0.0275 (6)	−0.0041 (5)	−0.0068 (5)	−0.0056 (5)
N3	0.0324 (5)	0.0193 (5)	0.0218 (5)	−0.0053 (4)	−0.0045 (4)	−0.0046 (4)
C4	0.0309 (6)	0.0191 (6)	0.0203 (6)	−0.0023 (5)	−0.0010 (5)	−0.0059 (5)
O4	0.0378 (5)	0.0181 (4)	0.0256 (4)	−0.0051 (4)	−0.0107 (4)	−0.0022 (3)
C47	0.0411 (7)	0.0227 (6)	0.0307 (7)	−0.0063 (5)	−0.0142 (6)	−0.0042 (5)
C41	0.0355 (7)	0.0226 (6)	0.0256 (6)	−0.0041 (5)	−0.0099 (5)	−0.0072 (5)
C42	0.0337 (7)	0.0290 (7)	0.0494 (9)	−0.0022 (6)	−0.0051 (6)	−0.0015 (6)
C43	0.0456 (9)	0.0336 (8)	0.0448 (9)	−0.0112 (7)	−0.0049 (7)	0.0031 (7)
C44	0.0516 (9)	0.0231 (7)	0.0382 (8)	−0.0018 (6)	−0.0217 (7)	−0.0028 (6)
C45	0.0378 (7)	0.0342 (8)	0.0469 (8)	0.0060 (6)	−0.0136 (7)	−0.0156 (7)
C46	0.0377 (7)	0.0339 (7)	0.0286 (7)	−0.0040 (6)	−0.0035 (5)	−0.0109 (6)
C5	0.0347 (7)	0.0187 (6)	0.0234 (6)	−0.0082 (5)	−0.0031 (5)	−0.0051 (5)
C6	0.0297 (6)	0.0229 (6)	0.0200 (6)	−0.0063 (5)	−0.0017 (5)	−0.0082 (5)
O6	0.0403 (5)	0.0219 (4)	0.0230 (4)	−0.0114 (4)	−0.0085 (4)	−0.0041 (3)
C67	0.0506 (8)	0.0252 (6)	0.0265 (6)	−0.0170 (6)	−0.0090 (6)	−0.0046 (5)
C61	0.0326 (6)	0.0216 (6)	0.0247 (6)	−0.0114 (5)	−0.0025 (5)	−0.0048 (5)
C62	0.0293 (6)	0.0215 (6)	0.0316 (7)	−0.0060 (5)	−0.0022 (5)	−0.0064 (5)
C63	0.0482 (8)	0.0250 (6)	0.0285 (7)	−0.0104 (6)	0.0007 (6)	−0.0104 (5)
C64	0.0466 (8)	0.0259 (7)	0.0298 (7)	−0.0120 (6)	−0.0142 (6)	−0.0030 (5)
C65	0.0272 (7)	0.0272 (7)	0.0466 (8)	−0.0065 (5)	−0.0068 (6)	−0.0048 (6)
C66	0.0340 (7)	0.0276 (7)	0.0341 (7)	−0.0084 (5)	0.0068 (6)	−0.0106 (5)

Geometric parameters (Å, º)

N1—C2	1.3466 (15)	C47—H47A	0.9900
C2—N3	1.3582 (15)	C47—H47B	0.9900
N3—C4	1.3227 (15)	C41—C42	1.3831 (19)
C4—C5	1.3925 (17)	C41—C46	1.3833 (19)
C5—C6	1.3863 (16)	C42—C43	1.384 (2)
C6—N1	1.3342 (15)	C42—H42	0.9500
C2—N2	1.3424 (15)	C43—C44	1.377 (2)
N2—C27	1.4495 (15)	C43—H43	0.9500
C4—O4	1.3516 (14)	C44—C45	1.370 (2)
O4—C47	1.4522 (14)	C44—H44	0.9500
C6—O6	1.3530 (14)	C45—C46	1.390 (2)
O6—C67	1.4470 (15)	C45—H45	0.9500
N2—H2	0.8800	C46—H46	0.9500
C27—C21	1.5172 (17)	C5—H5	0.9500
C27—H27A	0.9900	C67—C61	1.5005 (17)
C27—H27B	0.9900	C67—H67A	0.9900
C21—C22	1.3886 (16)	C67—H67B	0.9900
C21—C26	1.3923 (17)	C61—C62	1.3872 (18)
C22—C23	1.3910 (18)	C61—C66	1.3894 (18)
C22—H22	0.9500	C62—C63	1.3872 (18)
C23—C24	1.383 (2)	C62—H62	0.9500
C23—H23	0.9500	C63—C64	1.381 (2)
C24—C25	1.3854 (19)	C63—H63	0.9500
C24—H24	0.9500	C64—C65	1.382 (2)
C25—C26	1.3900 (18)	C64—H64	0.9500
C25—H25	0.9500	C65—C66	1.3871 (19)
C26—H26	0.9500	C65—H65	0.9500
C47—C41	1.5042 (17)	C66—H66	0.9500
C6—N1—C2	116.12 (10)	C41—C42—H42	119.5
N2—C2—N1	116.63 (10)	C43—C42—H42	119.5
N2—C2—N3	117.54 (10)	C44—C43—C42	120.14 (14)
N1—C2—N3	125.83 (11)	C44—C43—H43	119.9
C2—N2—C27	123.94 (10)	C42—C43—H43	119.9
C2—N2—H2	118.0	C45—C44—C43	119.33 (13)
C27—N2—H2	118.0	C45—C44—H44	120.3
N2—C27—C21	114.73 (10)	C43—C44—H44	120.3
N2—C27—H27A	108.6	C44—C45—C46	120.80 (13)
C21—C27—H27A	108.6	C44—C45—H45	119.6
N2—C27—H27B	108.6	C46—C45—H45	119.6
C21—C27—H27B	108.6	C41—C46—C45	120.26 (13)
H27A—C27—H27B	107.6	C41—C46—H46	119.9
C22—C21—C26	118.55 (11)	C45—C46—H46	119.9
C22—C21—C27	119.33 (11)	C6—C5—C4	114.53 (11)
C26—C21—C27	122.11 (10)	C6—C5—H5	122.7
C21—C22—C23	120.98 (12)	C4—C5—H5	122.7
C21—C22—H22	119.5	N1—C6—O6	112.10 (10)
C23—C22—H22	119.5	N1—C6—C5	123.60 (11)
C24—C23—C22	119.95 (12)	O6—C6—C5	124.24 (10)
C24—C23—H23	120.0	C6—O6—C67	116.37 (9)
C22—C23—H23	120.0	O6—C67—C61	109.25 (10)
C23—C24—C25	119.68 (12)	O6—C67—H67A	109.8
C23—C24—H24	120.2	C61—C67—H67A	109.8
C25—C24—H24	120.2	O6—C67—H67B	109.8
C24—C25—C26	120.23 (12)	C61—C67—H67B	109.8
C24—C25—H25	119.9	H67A—C67—H67B	108.3
C26—C25—H25	119.9	C62—C61—C66	118.87 (11)
C25—C26—C21	120.61 (12)	C62—C61—C67	120.71 (12)
C25—C26—H26	119.7	C66—C61—C67	120.39 (12)
C21—C26—H26	119.7	C61—C62—C63	120.57 (12)
C4—N3—C2	115.00 (10)	C61—C62—H62	119.7
N3—C4—O4	118.75 (10)	C63—C62—H62	119.7
N3—C4—C5	124.90 (11)	C64—C63—C62	120.07 (12)
O4—C4—C5	116.34 (10)	C64—C63—H63	120.0
C4—O4—C47	116.87 (9)	C62—C63—H63	120.0
O4—C47—C41	106.83 (10)	C63—C64—C65	119.89 (12)
O4—C47—H47A	110.4	C63—C64—H64	120.1
C41—C47—H47A	110.4	C65—C64—H64	120.1
O4—C47—H47B	110.4	C64—C65—C66	119.99 (12)
C41—C47—H47B	110.4	C64—C65—H65	120.0
H47A—C47—H47B	108.6	C66—C65—H65	120.0
C42—C41—C46	118.45 (12)	C65—C66—C61	120.59 (12)
C42—C41—C47	121.14 (12)	C65—C66—H66	119.7
C46—C41—C47	120.41 (12)	C61—C66—H66	119.7
C41—C42—C43	121.02 (13)
C27—N2—C2—N3	−3.0 (2)	C67—O6—C6—C5	2.1 (2)
C47—O4—C4—N3	1.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1^i	0.88	2.13	2.997 (2)	170
C66—H66···N1^ii	0.95	2.58	3.516 (2)	170

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

(III) 2-amino-4,6-bis(N-pyrrolidino)pyrimidine

Crystal data

C12H19N5	F(000) = 1008
Mr = 233.32	Dx = 1.308 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 2485 reflections
a = 12.5654 (8) Å	θ = 2.2–27.6°
b = 13.2735 (8) Å	µ = 0.08 mm^−1
c = 14.2279 (9) Å	T = 120 K
β = 93.090 (2)°	Prism, colourless
V = 2369.6 (3) Å^3	0.3 × 0.2 × 0.2 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	2485 independent reflections
Radiation source: fine-focus sealed X-ray tube	2109 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
ϕ scans, and ω scans with κ offsets	θmax = 27.0°, θmin = 2.2°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −16→15
Tmin = 0.975, Tmax = 0.990	k = −16→17
7257 measured reflections	l = −15→17

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.117	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0753P)^2 + 0.6604P] where P = (Fo^2 + 2Fc^2)/3
2485 reflections	(Δ/σ)max < 0.001
154 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. The program DENZO-SMN (Otwinowski & Minor, 1997) uses a scaling algorithm [Fox, G. C. & Holmes, K. C. (1966). Acta Cryst. 20, 886–891] which effectively corrects for absorption effects. High-redundancy data were used in the scaling program, hence the `multi-scan' code word was used. No transmission coefficients are available from the program (only scale factors for each frame).

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

	x	y	z	Uiso*/Ueq
N1	0.14234 (7)	0.42768 (7)	0.04220 (6)	0.0167 (2)
C2	0.08934 (9)	0.41017 (8)	0.12032 (8)	0.0169 (3)
N2	−0.01134 (8)	0.44606 (8)	0.12240 (7)	0.0226 (3)
N3	0.12512 (7)	0.36133 (7)	0.19908 (6)	0.0177 (2)
C4	0.22452 (9)	0.32333 (8)	0.19736 (8)	0.0168 (3)
N4	0.25920 (7)	0.27045 (8)	0.27487 (7)	0.0210 (3)
C41	0.19010 (9)	0.24157 (9)	0.34986 (8)	0.0200 (3)
C42	0.25113 (10)	0.15405 (9)	0.39630 (9)	0.0247 (3)
C43	0.36722 (10)	0.18595 (10)	0.38874 (9)	0.0248 (3)
C44	0.36740 (9)	0.23140 (9)	0.28994 (8)	0.0203 (3)
C5	0.28893 (9)	0.33753 (8)	0.12149 (8)	0.0181 (3)
C6	0.24377 (9)	0.39189 (8)	0.04469 (8)	0.0163 (3)
N6	0.30145 (7)	0.41109 (7)	−0.03098 (7)	0.0190 (2)
C61	0.41069 (9)	0.37530 (9)	−0.03849 (8)	0.0193 (3)
C62	0.44028 (10)	0.41074 (9)	−0.13600 (8)	0.0228 (3)
C63	0.36687 (9)	0.50100 (9)	−0.15631 (8)	0.0216 (3)
C64	0.26383 (9)	0.47094 (9)	−0.11223 (8)	0.0188 (3)
H2A	−0.0398	0.4794	0.0738	0.027*
H2B	−0.0484	0.4360	0.1723	0.027*
H41A	0.1190	0.2200	0.3240	0.024*
H41B	0.1814	0.2976	0.3947	0.024*
H42A	0.2360	0.0901	0.3623	0.030*
H42B	0.2334	0.1461	0.4628	0.030*
H43A	0.4158	0.1273	0.3950	0.030*
H43B	0.3885	0.2365	0.4374	0.030*
H44A	0.4207	0.2861	0.2871	0.024*
H44B	0.3827	0.1794	0.2426	0.024*
H5	0.3595	0.3118	0.1218	0.022*
H61A	0.4142	0.3010	−0.0336	0.023*
H61B	0.4589	0.4051	0.0114	0.023*
H62A	0.4272	0.3570	−0.1835	0.027*
H62B	0.5161	0.4311	−0.1355	0.027*
H63A	0.3970	0.5631	−0.1270	0.026*
H63B	0.3550	0.5120	−0.2249	0.026*
H64A	0.2238	0.5309	−0.0926	0.023*
H64B	0.2178	0.4305	−0.1565	0.023*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0156 (5)	0.0198 (5)	0.0148 (5)	0.0000 (4)	0.0009 (4)	0.0007 (4)
C2	0.0159 (5)	0.0186 (5)	0.0161 (6)	−0.0027 (4)	0.0003 (4)	−0.0009 (4)
N2	0.0161 (5)	0.0349 (6)	0.0172 (5)	0.0040 (4)	0.0034 (4)	0.0079 (4)
N3	0.0152 (5)	0.0231 (5)	0.0147 (5)	−0.0005 (4)	0.0009 (4)	0.0016 (4)
C4	0.0182 (6)	0.0173 (5)	0.0148 (5)	−0.0023 (4)	−0.0007 (4)	−0.0001 (4)
N4	0.0162 (5)	0.0288 (5)	0.0183 (5)	0.0021 (4)	0.0023 (4)	0.0070 (4)
C41	0.0205 (6)	0.0244 (6)	0.0149 (6)	−0.0020 (5)	0.0005 (4)	0.0031 (4)
C42	0.0292 (7)	0.0246 (6)	0.0203 (6)	−0.0008 (5)	−0.0002 (5)	0.0053 (5)
C43	0.0252 (7)	0.0264 (6)	0.0225 (6)	0.0037 (5)	−0.0027 (5)	0.0047 (5)
C44	0.0176 (6)	0.0234 (6)	0.0197 (6)	0.0029 (5)	−0.0001 (4)	0.0005 (5)
C5	0.0154 (5)	0.0210 (6)	0.0179 (6)	0.0024 (4)	0.0017 (4)	0.0011 (4)
C6	0.0175 (6)	0.0162 (5)	0.0151 (6)	−0.0011 (4)	0.0016 (4)	−0.0020 (4)
N6	0.0173 (5)	0.0249 (5)	0.0152 (5)	0.0049 (4)	0.0038 (4)	0.0037 (4)
C61	0.0163 (6)	0.0237 (6)	0.0181 (6)	0.0033 (4)	0.0040 (4)	0.0004 (4)
C62	0.0215 (6)	0.0283 (6)	0.0191 (6)	0.0021 (5)	0.0068 (5)	0.0009 (5)
C63	0.0203 (6)	0.0282 (6)	0.0166 (6)	0.0001 (5)	0.0028 (4)	0.0028 (5)
C64	0.0190 (6)	0.0229 (6)	0.0144 (6)	0.0002 (4)	−0.0004 (4)	0.0016 (4)

Geometric parameters (Å, º)

N1—C2	1.3464 (15)	C43—H43A	0.9900
C2—N3	1.3506 (14)	C43—H43B	0.9900
N3—C4	1.3484 (15)	C44—H44A	0.9900
C4—C5	1.3965 (16)	C44—H44B	0.9900
C5—C6	1.4035 (15)	C5—H5	0.9500
C6—N1	1.3588 (14)	C6—N6	1.3540 (15)
C2—N2	1.3537 (15)	N6—C64	1.4602 (14)
N2—H2A	0.8800	N6—C61	1.4619 (14)
N2—H2B	0.8800	C61—C62	1.5296 (16)
C4—N4	1.3590 (14)	C61—H61A	0.9900
N4—C44	1.4601 (14)	C61—H61B	0.9900
N4—C41	1.4625 (15)	C62—C63	1.5300 (16)
C41—C42	1.5230 (16)	C62—H62A	0.9900
C41—H41A	0.9900	C62—H62B	0.9900
C41—H41B	0.9900	C63—C64	1.5219 (16)
C42—C43	1.5283 (18)	C63—H63A	0.9900
C42—H42A	0.9900	C63—H63B	0.9900
C42—H42B	0.9900	C64—H64A	0.9900
C43—C44	1.5298 (16)	C64—H64B	0.9900
C2—N1—C6	115.03 (10)	C43—C44—H44B	111.1
N1—C2—N3	127.63 (10)	H44A—C44—H44B	109.1
N1—C2—N2	117.50 (10)	C4—C5—C6	116.39 (10)
N3—C2—N2	114.87 (10)	C4—C5—H5	121.8
C2—N2—H2A	120.0	C6—C5—H5	121.8
C2—N2—H2B	120.0	N6—C6—N1	117.06 (10)
H2A—N2—H2B	120.0	N6—C6—C5	120.30 (10)
C4—N3—C2	115.58 (10)	N1—C6—C5	122.64 (10)
N3—C4—N4	115.80 (10)	C6—N6—C61	122.82 (9)
N3—C4—C5	122.65 (10)	C6—N6—C64	124.58 (9)
N4—C4—C5	121.55 (10)	C61—N6—C64	112.58 (9)
C4—N4—C41	123.39 (9)	N6—C61—C62	103.98 (9)
C4—N4—C44	123.91 (10)	N6—C61—H61A	111.0
C41—N4—C44	112.62 (9)	C62—C61—H61A	111.0
N4—C41—C42	102.22 (9)	N6—C61—H61B	111.0
N4—C41—H41A	111.3	C62—C61—H61B	111.0
C42—C41—H41A	111.3	H61A—C61—H61B	109.0
N4—C41—H41B	111.3	C61—C62—C63	103.80 (9)
C42—C41—H41B	111.3	C61—C62—H62A	111.0
H41A—C41—H41B	109.2	C63—C62—H62A	111.0
C41—C42—C43	102.61 (9)	C61—C62—H62B	111.0
C41—C42—H42A	111.2	C63—C62—H62B	111.0
C43—C42—H42A	111.2	H62A—C62—H62B	109.0
C41—C42—H42B	111.2	C64—C63—C62	103.56 (9)
C43—C42—H42B	111.2	C64—C63—H63A	111.0
H42A—C42—H42B	109.2	C62—C63—H63A	111.0
C42—C43—C44	102.87 (9)	C64—C63—H63B	111.0
C42—C43—H43A	111.2	C62—C63—H63B	111.0
C44—C43—H43A	111.2	H63A—C63—H63B	109.0
C42—C43—H43B	111.2	N6—C64—C63	102.86 (9)
C44—C43—H43B	111.2	N6—C64—H64A	111.2
H43A—C43—H43B	109.1	C63—C64—H64A	111.2
N4—C44—C43	103.14 (9)	N6—C64—H64B	111.2
N4—C44—H44A	111.1	C63—C64—H64B	111.2
C43—C44—H44A	111.1	H64A—C64—H64B	109.1
N4—C44—H44B	111.1
C6—N1—C2—N3	−0.43 (17)	N3—C4—C5—C6	−1.63 (16)
C6—N1—C2—N2	178.66 (9)	N4—C4—C5—C6	178.90 (10)
N1—C2—N3—C4	−2.19 (17)	C2—N1—C6—N6	−177.58 (9)
N2—C2—N3—C4	178.70 (9)	C2—N1—C6—C5	2.18 (16)
C2—N3—C4—N4	−177.32 (9)	C4—C5—C6—N6	178.52 (10)
C2—N3—C4—C5	3.17 (16)	C4—C5—C6—N1	−1.23 (17)
N3—C4—N4—C44	−174.24 (10)	C5—C6—N6—C64	−176.89 (10)
N3—C4—N4—C41	9.39 (16)	N1—C6—N6—C61	−178.70 (9)
C5—C4—N4—C44	5.27 (17)	C5—C6—N6—C61	1.53 (17)
C5—C4—N4—C41	−171.10 (11)	N1—C6—N6—C64	2.88 (16)
C4—N4—C41—C42	158.93 (11)	C6—N6—C61—C62	177.59 (10)
N4—C41—C42—C43	35.48 (12)	N6—C64—C63—C62	33.10 (11)
C41—C42—C43—C44	−40.59 (12)	C64—C63—C62—C61	−35.97 (12)
C42—C43—C44—N4	29.44 (12)	C63—C62—C61—N6	24.55 (12)
C43—C44—N4—C41	−7.37 (13)	C62—C61—N6—C64	−3.82 (13)
C44—N4—C41—C42	−17.80 (13)	C61—N6—C64—C63	−18.54 (12)
C4—N4—C44—C43	175.92 (11)	C6—N6—C64—C63	160.02 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1^i	0.88	2.38	3.2538 (14)	170
N2—H2B···N3^ii	0.88	2.33	3.1862 (13)	163

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