2-Amino-4,6-di­methoxy-5-nitro­so­pyrimidine-water (4/3): seven independent molecular components are linked into a three-dimensional framework by six three-centre and eight two-centre hydrogen bonds

In the title compound, 4C₆H₈N₄O₃·3H₂O, the pyrimidine mol­ecules all exhibit a polarized molecular electronic structure; the seven-component asymmetric unit can be selected as a closed cyclic aggregate and the linking of these aggregates can be analysed in terms of translational chain motifs running parallel to [110], [210] and [011], which combine to generate a single three-dimensional framework.

S1. Comment

In 2-amino-4,6-dimethoxypyrimidine, (I), both N—H bonds are involved in the formation of N—H···N hydrogen bonds, so forming a chain of edge-fused rings containing two distinct R²₂(8) motifs (Low et al., 2002). The benzyloxy analogue 2-amino-4,6-bis(benzyloxy)pyrimidine, (II), on the other hand, utilizes only one of the N—H bonds in forming an N—H···N hydrogen bond, again forming an R²₂(8) motif, while the other N—H bond forms an N—H···O hydrogen bond which generates a simple C(6) chain motif; the combination of the ring and chain motifs generates a molecular ladder (Quesada, Marchal et al., 2002). There are no R²₂(8) rings in 2-amino-4,6-bis(benzyloxy)-5-nitrosopyrimidine, (III), the nitrosated analogue of (II) (Quesada, Low et al., 2002). Instead, one N—H bond participates in a three-centre N—H···(N,O) hydrogen bond, while the other forms an N—H···π(arene) hydrogen bond; the overall supramolecular structure is again one-dimensional. Thus, the supramolecular structures of (I)-(III) involve two, one or zero distinct R²₂(8) rings, respectively, containing paired N—H···N hydrogen bonds. Intrigued by the differences in structural behaviour, not only between (I) and (II), but also between (II) and (III), we have now investigated the nitrosated analogue of (I), namely 2-amino-4,6-dimethoxy-5-nitrosopyrimidine, which upon crystallization from acetone, as used for (I) and (III), yields the stoichiometric hydrate 4C₆H₈N₄O₃·3H₂O, (IV).

Compound (IV) (Fig. 1) crystallizes in the non-centrosymmetric triclinic space group P1 with four pyrimidine molecules and three water molecules in the asymmetric unit. Each of the pyrimidine molecules adopts a conformation in which the two methyl C atoms are essentially in the plane of the ring, but directed away from the nitroso substituent, just as in (III) (Quesada, Low et al., 2002). In each of the pyrimidine molecules in (IV), the Nn1—Cn6 and Nn3—Cn4 bonds (n = 1 - 4) are short for their type (Allen et al., 1987) and the Cn2—Nn2 bonds are much shorter than both the Nn1—Cn2 and Cn2—Nn3 bonds (Table 1); in addition, the Cn5—Nn5 bonds are shorter and the Nn5—On5 bonds longer than the corresponding bonds in simple unpolarized Ar—NO compounds. All of these distances point to the charge-separated form (IVa) as an important contributor to the overall molecular-electronic structure.

The seven independent molecular components in (IV) are linked into a three-dimensional framework by a combination of six three-centre hydrogen bonds, of which four are of O—H···(O)₂ type and one each are of O—H···(N,O) and N—H···(O)₂ types, and eight two-centre hydrogen bonds, one each of the O—H···O and N—H···N types and six of the N—H···O type (Table 2). The three-centre systems are, in general, distinctly asymmetric, but most are nearly planar; their angle sums at H range from 340 to 359°, with a mean value of 351°. The D—H···A angles in the two-centre hydrogen bonds range from 149 to 177°, with a mean of 168°, and all are reasonably short, and thus reasonably strong, for their types.

In supramolecular systems such as this, the selection of the asymmetric unit is, to a large extent, arbitrary; however, in (IV), it is possible to select a compact cyclic asymmetric unit bounded by an R⁷₇(38) motif (Fig. 1) which incorporates three of the three-centre hydrogen bonds and five of the two-centre hydrogen bonds, leaving just six hydrogen bonds to link these cyclic aggregates into the continuous framework. The interior of this cyclic unit is occupied by four methoxy groups, one from each of the pyrimidine molecules. Because translation is the only symmetry operation available in P1, the formation of the framework itself can be readily analyzed in terms of just three chain motifs linking the cyclic aggregates.

In the simplest of these chain motifs, the O1 water molecule in the aggregate at (x, y, z) acts as hydrogen-bond donor, via H11, to water atom O3 at (1 + x, 1 + y, z), so generating a chain parallel to the [110] direction (Fig. 2). The second chain motif utilizes two different three-centre hydrogen bonds with which to link the cyclic aggregates; the O2 water molecule acts as hydrogen-bond donor, via H21, to both methoxy atom O36 and nitroso atom O35 in the pyrimidine molecule at (x, 1 + y, 1 + z), while the N42 amino group acts as donor, via H42B, to methoxy atom O16 and nitroso atom O15 at (x, -1 + y, -1 + z), and these three-centre interactions combine to generate a chain running parallel to [011] (Fig. 3). Finally, in the most complex of the chains, the N12 amino group acts as donor, via H12A, to nitroso atom N25 at (2 + x, 1 + y, z), while the N32 amino group acts as donor, via H32A, to methoxy atom O44 at (-2 + x, -1 + y, z), each hydrogen bond thus forming a chain along [210]; additionally, the O3 water molecule acts as donor, via H32, to both N45 and O45 at (-2 + x, -1 + y, z), providing the final component of the [210] chain (Fig. 3). The combination of the [011] and [210] ladders generates a very elegant (122) sheet (Fig. 3), while the combination of [110], [011] and [210] chains suffices to generate a single three-dimensional framework.

S2. Experimental

A sample of (I) was purchased from Aldrich and converted into 2-amino-4,6-dimethoxy-5-nitrosopyrimidine according to the method of Marchal et al. (2002). Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation of a solution in acetone.

S3. Refinement

Compound (IV) is triclinic and space group P1 was assumed and confirmed by the analysis. H atoms were treated as riding atoms, with distances C—H 0.98 Å, N—H 0.88 Å and O—H 1.00 Å. In the absence of any significant anomalous scatterers, the Friedel equivalents were merged; the absolute structure could not be established.

Computing details

Data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; 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. The independent molecular components of (IV), showing the atom-labelling scheme and the linking of the independent components into the cyclic asymmetric unit. Displacement ellipsoids are drawn at the 30% probability level. For the sake of clarity, only those hydrogen bonds which generate the outer R^77(38) ring are shown.
	Fig. 2. Part of the crystal structure of (IV), showing the formation of a chain along [110]. For the sake of clarity, H atoms bonded to C atoms have been omitted. Atoms marked with an asterisk (*) or hash (#) are at the symmetry positions (1 + x, 1 + y, z) and (-1 + x, -1 + y, z), respectively.
	Fig. 3. Part of the crystal structure of (IV), showing the formation of ladders along [011] and [210] combining to form a (122) sheet. Atoms marked with an asterisk (*), hash (#), dollar sign ($) or ampersand (&) are at the symmetry positions (x, -1 + y, -1 + z), (x, 1 + y, 1 + z), (-2 + x, -1 + y, z) and (2 + x, 1 + y, z), respectively.

2-Amino-4,6-dimethoxy-5-nitrosopyrimidine–water (4/3)

Crystal data

4C6H8N4O3·3H2O	Z = 1
Mr = 790.70	F(000) = 414
Triclinic, P1	Dx = 1.563 Mg m^−3
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.9588 (4) Å	Cell parameters from 6738 reflections
b = 7.1984 (4) Å	θ = 2.9–27.4°
c = 17.4239 (11) Å	µ = 0.13 mm^−1
α = 101.181 (2)°	T = 120 K
β = 98.559 (2)°	Plate, blue
γ = 95.360 (4)°	0.20 × 0.20 × 0.04 mm
V = 839.95 (9) Å^3

Data collection

Nonius KappaCCD diffractometer	3638 independent reflections
Radiation source: fine-focus sealed X-ray tube	2498 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.076
ϕ scans, and ω scans with κ offsets	θmax = 27.4°, θmin = 2.9°
Absorption correction: multi-scan (DENZO-SMN; Otwinowski & Minor, 1997)	h = −8→8
Tmin = 0.964, Tmax = 0.992	k = −9→9
10707 measured reflections	l = −22→22

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.140	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0793P)^2] where P = (Fo^2 + 2Fc^2)/3
3638 reflections	(Δ/σ)max < 0.001
504 parameters	Δρmax = 0.32 e Å^−3
3 restraints	Δρmin = −0.38 e Å^−3

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

	x	y	z	Uiso*/Ueq
N11	1.0461 (6)	0.8843 (6)	0.8538 (2)	0.0208 (10)
C12	0.9963 (7)	0.7835 (7)	0.7781 (3)	0.0195 (11)
N12	1.1247 (6)	0.7907 (7)	0.7309 (3)	0.0257 (11)
N13	0.8217 (6)	0.6718 (6)	0.7459 (3)	0.0218 (10)
C14	0.6949 (7)	0.6648 (7)	0.7939 (3)	0.0191 (11)
O14	0.5197 (5)	0.5605 (5)	0.7671 (2)	0.0240 (8)
C141	0.4732 (8)	0.4730 (8)	0.6830 (3)	0.0265 (12)
C15	0.7294 (8)	0.7597 (7)	0.8745 (3)	0.0179 (11)
O15	0.6139 (5)	0.8287 (5)	0.9895 (2)	0.0262 (9)
N15	0.5842 (6)	0.7378 (6)	0.9175 (3)	0.0227 (10)
C16	0.9187 (8)	0.8709 (8)	0.9004 (3)	0.0230 (12)
C161	1.1548 (8)	1.0770 (9)	0.9991 (4)	0.0331 (15)
O16	0.9622 (5)	0.9659 (5)	0.9762 (2)	0.0244 (9)
N21	0.0168 (6)	0.2605 (6)	0.7490 (3)	0.0201 (10)
C22	0.0231 (8)	0.3416 (7)	0.8264 (3)	0.0204 (12)
N22	0.1855 (6)	0.4547 (6)	0.8634 (3)	0.0248 (11)
N23	−0.1189 (6)	0.3222 (6)	0.8711 (3)	0.0212 (10)
C24	−0.2801 (7)	0.2114 (7)	0.8338 (3)	0.0184 (11)
C241	−0.3974 (8)	0.2785 (8)	0.9556 (3)	0.0277 (13)
O24	−0.4264 (5)	0.1860 (5)	0.8731 (2)	0.0243 (9)
C25	−0.3093 (7)	0.1153 (7)	0.7535 (3)	0.0185 (11)
O25	−0.5175 (5)	−0.0782 (5)	0.6516 (2)	0.0247 (9)
N25	−0.4858 (6)	0.0056 (6)	0.7233 (3)	0.0200 (10)
C26	−0.1468 (8)	0.1513 (7)	0.7139 (3)	0.0194 (11)
C261	0.0020 (8)	0.1045 (8)	0.5987 (3)	0.0249 (12)
O26	−0.1656 (5)	0.0698 (5)	0.6371 (2)	0.0227 (8)
N31	−0.0981 (7)	−0.3167 (6)	0.2526 (3)	0.0212 (10)
N32	−0.2559 (6)	−0.3078 (6)	0.3586 (3)	0.0239 (11)
C32	−0.0962 (8)	−0.2551 (7)	0.3313 (3)	0.0194 (11)
N33	0.0519 (6)	−0.1488 (6)	0.3860 (3)	0.0215 (10)
C34	0.2110 (7)	−0.1007 (7)	0.3581 (3)	0.0193 (11)
O34	0.3660 (5)	0.0008 (5)	0.4081 (2)	0.0230 (8)
C341	0.3460 (8)	0.0513 (9)	0.4917 (3)	0.0298 (13)
C35	0.2319 (8)	−0.1465 (8)	0.2768 (3)	0.0204 (12)
N35	0.4031 (7)	−0.0768 (7)	0.2580 (3)	0.0239 (10)
O35	0.4262 (5)	−0.1179 (5)	0.1866 (2)	0.0261 (9)
C36	0.0624 (7)	−0.2615 (8)	0.2260 (3)	0.0193 (12)
O36	0.0703 (5)	−0.3116 (5)	0.1499 (2)	0.0234 (9)
C361	−0.1002 (8)	−0.4246 (8)	0.0976 (3)	0.0270 (13)
N41	0.8734 (6)	0.1885 (6)	0.2813 (3)	0.0197 (10)
C42	0.9329 (7)	0.1611 (7)	0.2100 (3)	0.0182 (11)
N42	0.8068 (7)	0.0500 (6)	0.1504 (3)	0.0243 (11)
N43	1.1060 (6)	0.2345 (6)	0.1939 (3)	0.0205 (10)
C44	1.2283 (8)	0.3395 (7)	0.2559 (3)	0.0172 (11)
C441	1.4523 (9)	0.3745 (9)	0.1675 (3)	0.0292 (13)
O44	1.4008 (5)	0.4173 (5)	0.2467 (2)	0.0233 (9)
C45	1.1857 (8)	0.3770 (8)	0.3346 (3)	0.0209 (12)
N45	1.3313 (6)	0.4828 (6)	0.3914 (3)	0.0214 (10)
O45	1.3037 (5)	0.5177 (6)	0.4626 (2)	0.0268 (9)
C46	0.9977 (7)	0.2940 (7)	0.3418 (3)	0.0204 (12)
C461	0.7494 (7)	0.2398 (8)	0.4176 (3)	0.0241 (12)
O46	0.9452 (5)	0.3241 (5)	0.4129 (2)	0.0221 (8)
O1	1.0196 (6)	0.5837 (6)	0.5724 (2)	0.0323 (9)
O2	0.2974 (6)	0.6369 (6)	1.0270 (2)	0.0329 (10)
O3	−0.3319 (5)	−0.2749 (5)	0.5232 (2)	0.0289 (9)
H12A	1.2396	0.8596	0.7486	0.031*
H12B	1.0962	0.7266	0.6814	0.031*
H14A	0.4585	0.5727	0.6521	0.040*
H14B	0.3506	0.3864	0.6724	0.040*
H14C	0.5792	0.4010	0.6677	0.040*
H16A	1.2551	0.9937	0.9877	0.050*
H16B	1.1769	1.1338	1.0560	0.050*
H16C	1.1621	1.1785	0.9690	0.050*
H22A	0.2825	0.4739	0.8375	0.030*
H22B	0.1962	0.5105	0.9137	0.030*
H24A	−0.2885	0.2302	0.9849	0.042*
H24B	−0.5170	0.2517	0.9771	0.042*
H24C	−0.3671	0.4166	0.9609	0.042*
H26A	0.0231	0.2400	0.5969	0.037*
H26B	−0.0230	0.0272	0.5445	0.037*
H26C	0.1188	0.0697	0.6288	0.037*
H32A	−0.3561	−0.3792	0.3260	0.029*
H32B	−0.2618	−0.2714	0.4093	0.029*
H34A	0.2535	0.1455	0.4984	0.045*
H34B	0.4739	0.1056	0.5239	0.045*
H34C	0.2971	−0.0633	0.5089	0.045*
H36A	−0.1244	−0.5474	0.1131	0.041*
H36B	−0.0765	−0.4466	0.0427	0.041*
H36C	−0.2146	−0.3559	0.1018	0.041*
H42A	0.6936	0.0000	0.1589	0.029*
H42B	0.8364	0.0263	0.1023	0.029*
H44A	1.4455	0.2359	0.1495	0.044*
H44B	1.5857	0.4344	0.1692	0.044*
H44C	1.3604	0.4242	0.1306	0.044*
H46A	0.6526	0.2788	0.3790	0.036*
H46B	0.7215	0.2835	0.4712	0.036*
H46C	0.7427	0.1003	0.4059	0.036*
H11	0.8884	0.6188	0.5528	0.039*
H12	1.0864	0.5611	0.5251	0.039*
H21	0.2654	0.7272	1.0733	0.039*
H22	0.4216	0.6986	1.0155	0.039*
H31	−0.3527	−0.1728	0.5679	0.035*
H32	−0.4589	−0.3604	0.5066	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N11	0.025 (3)	0.020 (2)	0.018 (2)	0.004 (2)	0.0068 (19)	0.0021 (19)
C12	0.018 (3)	0.019 (3)	0.021 (3)	0.003 (2)	0.001 (2)	0.005 (2)
N12	0.021 (3)	0.034 (3)	0.024 (3)	0.003 (2)	0.008 (2)	0.008 (2)
N13	0.021 (2)	0.024 (2)	0.022 (3)	0.008 (2)	0.0034 (19)	0.0051 (19)
C14	0.018 (3)	0.015 (3)	0.024 (3)	0.000 (2)	0.003 (2)	0.005 (2)
O14	0.019 (2)	0.029 (2)	0.020 (2)	−0.0062 (16)	0.0000 (15)	0.0019 (16)
C141	0.026 (3)	0.032 (3)	0.020 (3)	0.002 (2)	−0.001 (2)	0.004 (2)
C15	0.020 (3)	0.015 (3)	0.020 (3)	−0.001 (2)	0.005 (2)	0.007 (2)
O15	0.029 (2)	0.031 (2)	0.018 (2)	−0.0027 (17)	0.0070 (15)	0.0020 (17)
N15	0.026 (3)	0.025 (2)	0.017 (2)	0.003 (2)	0.0050 (18)	0.005 (2)
C16	0.028 (3)	0.023 (3)	0.018 (3)	0.013 (2)	0.001 (2)	0.003 (2)
C161	0.023 (3)	0.041 (4)	0.025 (3)	−0.006 (3)	−0.007 (2)	−0.007 (3)
O16	0.0206 (19)	0.028 (2)	0.020 (2)	−0.0057 (16)	0.0040 (15)	−0.0027 (16)
N21	0.025 (3)	0.021 (2)	0.015 (2)	0.0064 (19)	0.0032 (18)	0.0028 (19)
C22	0.021 (3)	0.016 (3)	0.024 (3)	0.005 (2)	0.001 (2)	0.005 (2)
N22	0.021 (3)	0.031 (3)	0.023 (3)	0.005 (2)	0.0053 (19)	0.004 (2)
N23	0.020 (2)	0.022 (2)	0.022 (2)	0.0047 (19)	0.0038 (18)	0.0050 (19)
C24	0.017 (3)	0.018 (3)	0.022 (3)	0.008 (2)	0.004 (2)	0.004 (2)
C241	0.029 (3)	0.031 (3)	0.020 (3)	0.001 (2)	0.007 (2)	−0.003 (2)
O24	0.0208 (19)	0.032 (2)	0.017 (2)	−0.0004 (17)	0.0047 (15)	−0.0001 (16)
C25	0.020 (3)	0.015 (3)	0.021 (3)	0.005 (2)	0.000 (2)	0.004 (2)
O25	0.024 (2)	0.031 (2)	0.017 (2)	−0.0001 (17)	0.0009 (16)	0.0030 (17)
N25	0.020 (2)	0.020 (2)	0.020 (3)	0.0017 (19)	0.0011 (18)	0.0054 (19)
C26	0.025 (3)	0.016 (3)	0.019 (3)	0.003 (2)	0.004 (2)	0.006 (2)
C261	0.021 (3)	0.030 (3)	0.023 (3)	−0.002 (2)	0.006 (2)	0.004 (2)
O26	0.023 (2)	0.026 (2)	0.017 (2)	−0.0047 (16)	0.0053 (15)	0.0032 (16)
N31	0.027 (3)	0.020 (2)	0.019 (3)	0.004 (2)	0.0084 (19)	0.0068 (19)
N32	0.023 (3)	0.032 (3)	0.017 (3)	0.000 (2)	0.0032 (19)	0.008 (2)
C32	0.017 (3)	0.017 (3)	0.027 (3)	0.008 (2)	0.007 (2)	0.007 (2)
N33	0.026 (2)	0.018 (2)	0.023 (3)	0.0058 (19)	0.0069 (19)	0.0069 (19)
C34	0.018 (3)	0.020 (3)	0.022 (3)	0.006 (2)	0.001 (2)	0.008 (2)
O34	0.024 (2)	0.031 (2)	0.0131 (19)	−0.0001 (17)	0.0029 (14)	0.0037 (16)
C341	0.031 (3)	0.038 (3)	0.015 (3)	0.000 (3)	0.003 (2)	−0.002 (2)
C35	0.026 (3)	0.022 (3)	0.014 (3)	0.006 (2)	0.000 (2)	0.005 (2)
N35	0.019 (2)	0.034 (3)	0.020 (3)	0.004 (2)	0.0053 (19)	0.009 (2)
O35	0.026 (2)	0.031 (2)	0.019 (2)	0.0016 (18)	0.0064 (16)	0.0000 (17)
C36	0.019 (3)	0.024 (3)	0.017 (3)	0.008 (2)	0.004 (2)	0.007 (2)
O36	0.023 (2)	0.032 (2)	0.013 (2)	0.0018 (16)	0.0028 (15)	0.0005 (16)
C361	0.028 (3)	0.030 (3)	0.018 (3)	−0.005 (3)	−0.001 (2)	0.002 (2)
N41	0.016 (2)	0.021 (2)	0.022 (3)	0.0019 (19)	0.0037 (18)	0.0040 (19)
C42	0.020 (3)	0.011 (2)	0.025 (3)	−0.001 (2)	0.004 (2)	0.006 (2)
N42	0.020 (2)	0.021 (2)	0.028 (3)	−0.0078 (19)	0.005 (2)	0.001 (2)
N43	0.017 (2)	0.018 (2)	0.023 (3)	0.0007 (19)	0.0004 (18)	0.0006 (19)
C44	0.019 (3)	0.007 (2)	0.025 (3)	−0.002 (2)	0.001 (2)	0.007 (2)
C441	0.034 (3)	0.035 (3)	0.021 (3)	0.005 (3)	0.013 (3)	0.004 (3)
O44	0.018 (2)	0.027 (2)	0.022 (2)	−0.0061 (16)	0.0057 (15)	0.0016 (16)
C45	0.018 (3)	0.026 (3)	0.020 (3)	0.001 (2)	0.006 (2)	0.006 (2)
N45	0.021 (2)	0.022 (2)	0.020 (3)	0.002 (2)	0.0026 (18)	0.0022 (19)
O45	0.026 (2)	0.035 (2)	0.018 (2)	0.0022 (17)	0.0038 (15)	0.0026 (17)
C46	0.019 (3)	0.018 (3)	0.025 (3)	0.002 (2)	0.004 (2)	0.006 (2)
C461	0.013 (3)	0.031 (3)	0.028 (3)	−0.002 (2)	0.010 (2)	0.004 (3)
O46	0.0206 (19)	0.030 (2)	0.015 (2)	0.0032 (16)	0.0026 (14)	0.0022 (16)
O1	0.030 (2)	0.042 (2)	0.023 (2)	0.0067 (19)	0.0048 (16)	0.0012 (18)
O2	0.032 (2)	0.041 (2)	0.021 (2)	−0.0085 (18)	0.0085 (16)	−0.0007 (18)
O3	0.026 (2)	0.031 (2)	0.026 (2)	−0.0043 (17)	0.0068 (16)	0.0012 (17)

Geometric parameters (Å, º)

N11—C12	1.354 (7)	C34—C35	1.424 (7)
C12—N13	1.370 (7)	C35—C36	1.443 (7)
N13—C14	1.308 (7)	C36—N31	1.328 (7)
C14—C15	1.411 (7)	C32—N32	1.325 (7)
C15—C16	1.437 (8)	C35—N35	1.360 (7)
C16—N11	1.296 (7)	N35—O35	1.259 (6)
C12—N12	1.306 (7)	N32—H32A	0.88
C15—N15	1.360 (7)	N32—H32B	0.88
N15—O15	1.275 (6)	C34—O34	1.335 (6)
N12—H12A	0.88	C341—O34	1.462 (6)
N12—H12B	0.88	C341—H34A	0.98
C14—O14	1.339 (6)	C341—H34B	0.98
O14—C141	1.453 (6)	C341—H34C	0.98
C141—H14A	0.98	C36—O36	1.315 (6)
C141—H14B	0.98	O36—C361	1.453 (6)
C141—H14C	0.98	C361—H36A	0.98
C16—O16	1.340 (6)	C361—H36B	0.98
C161—O16	1.453 (7)	C361—H36C	0.98
C161—H16A	0.98	N41—C42	1.353 (7)
C161—H16B	0.98	C42—N43	1.359 (7)
C161—H16C	0.98	N43—C44	1.323 (6)
N21—C22	1.354 (7)	C44—C45	1.427 (7)
C22—N23	1.359 (7)	C45—C46	1.420 (7)
N23—C24	1.315 (7)	C46—N41	1.316 (7)
C24—C25	1.411 (7)	C42—N42	1.328 (7)
C25—C26	1.439 (7)	C45—N45	1.361 (7)
C26—N21	1.314 (7)	N45—O45	1.263 (6)
C22—N22	1.328 (7)	N42—H42A	0.88
C25—N25	1.369 (7)	N42—H42B	0.88
N25—O25	1.255 (6)	C44—O44	1.322 (6)
N22—H22A	0.88	C441—O44	1.460 (7)
N22—H22B	0.88	C441—H44A	0.98
C24—O24	1.327 (6)	C441—H44B	0.98
C241—O24	1.437 (6)	C441—H44C	0.98
C241—H24A	0.98	C46—O46	1.326 (6)
C241—H24B	0.98	C461—O46	1.459 (6)
C241—H24C	0.98	C461—H46A	0.98
C26—O26	1.335 (6)	C461—H46B	0.98
C261—O26	1.453 (6)	C461—H46C	0.98
C261—H26A	0.98	O1—H11	0.9981
C261—H26B	0.98	O1—H12	0.9992
C261—H26C	0.98	O2—H21	0.9992
N31—C32	1.353 (7)	O2—H22	1.0001
C32—N33	1.355 (7)	O3—H31	0.9994
N33—C34	1.317 (7)	O3—H32	0.9983
C16—N11—C12	117.1 (5)	C32—N32—H32B	120.0
N12—C12—N11	118.1 (5)	H32A—N32—H32B	120.0
N12—C12—N13	116.2 (5)	N32—C32—N31	116.6 (5)
N11—C12—N13	125.8 (5)	N32—C32—N33	115.8 (5)
C12—N12—H12A	120.0	N31—C32—N33	127.6 (5)
C12—N12—H12B	120.0	C34—N33—C32	115.0 (5)
H12A—N12—H12B	120.0	N33—C34—O34	119.2 (5)
C14—N13—C12	115.6 (5)	N33—C34—C35	124.9 (5)
N13—C14—O14	119.5 (5)	O34—C34—C35	115.9 (4)
N13—C14—C15	124.4 (5)	C34—O34—C341	116.6 (4)
O14—C14—C15	116.1 (4)	O34—C341—H34A	109.5
C14—O14—C141	117.5 (4)	O34—C341—H34B	109.5
O14—C141—H14A	109.5	H34A—C341—H34B	109.5
O14—C141—H14B	109.5	O34—C341—H34C	109.5
H14A—C141—H14B	109.5	H34A—C341—H34C	109.5
O14—C141—H14C	109.5	H34B—C341—H34C	109.5
H14A—C141—H14C	109.5	N35—C35—C34	117.0 (5)
H14B—C141—H14C	109.5	N35—C35—C36	129.6 (5)
N15—C15—C14	117.9 (4)	C34—C35—C36	113.4 (5)
N15—C15—C16	128.1 (5)	O35—N35—C35	118.1 (4)
C14—C15—C16	114.0 (4)	O36—C36—N31	119.6 (5)
O15—N15—C15	117.6 (4)	O36—C36—C35	117.3 (5)
N11—C16—O16	119.3 (5)	N31—C36—C35	123.1 (5)
N11—C16—C15	123.1 (5)	C36—O36—C361	118.1 (4)
O16—C16—C15	117.5 (5)	O36—C361—H36A	109.5
O16—C161—H16A	109.5	O36—C361—H36B	109.5
O16—C161—H16B	109.5	H36A—C361—H36B	109.5
H16A—C161—H16B	109.5	O36—C361—H36C	109.5
O16—C161—H16C	109.5	H36A—C361—H36C	109.5
H16A—C161—H16C	109.5	H36B—C361—H36C	109.5
H16B—C161—H16C	109.5	C46—N41—C42	116.6 (5)
C16—O16—C161	115.3 (4)	N42—C42—N41	115.3 (5)
C26—N21—C22	115.3 (4)	N42—C42—N43	117.9 (5)
N22—C22—N21	116.8 (5)	N41—C42—N43	126.8 (5)
N22—C22—N23	115.6 (5)	C42—N42—H42A	120.0
N21—C22—N23	127.5 (5)	C42—N42—H42B	120.0
C22—N22—H22A	120.0	H42A—N42—H42B	120.0
C22—N22—H22B	120.0	C44—N43—C42	115.3 (5)
H22A—N22—H22B	120.0	O44—C44—N43	120.1 (5)
C24—N23—C22	115.3 (5)	O44—C44—C45	116.2 (4)
N23—C24—O24	119.1 (5)	N43—C44—C45	123.7 (5)
N23—C24—C25	124.2 (5)	O44—C441—H44A	109.5
O24—C24—C25	116.7 (5)	O44—C441—H44B	109.5
O24—C241—H24A	109.5	H44A—C441—H44B	109.5
O24—C241—H24B	109.5	O44—C441—H44C	109.5
H24A—C241—H24B	109.5	H44A—C441—H44C	109.5
O24—C241—H24C	109.5	H44B—C441—H44C	109.5
H24A—C241—H24C	109.5	C44—O44—C441	117.4 (4)
H24B—C241—H24C	109.5	N45—C45—C46	129.8 (5)
C24—O24—C241	117.6 (4)	N45—C45—C44	115.7 (5)
N25—C25—C24	117.2 (5)	C46—C45—C44	114.5 (5)
N25—C25—C26	128.8 (5)	O45—N45—C45	118.6 (4)
C24—C25—C26	114.0 (5)	N41—C46—O46	118.5 (5)
O25—N25—C25	118.6 (4)	N41—C46—C45	123.1 (5)
N21—C26—O26	118.8 (4)	O46—C46—C45	118.4 (5)
N21—C26—C25	123.6 (5)	O46—C461—H46A	109.5
O26—C26—C25	117.6 (4)	O46—C461—H46B	109.5
O26—C261—H26A	109.5	H46A—C461—H46B	109.5
O26—C261—H26B	109.5	O46—C461—H46C	109.5
H26A—C261—H26B	109.5	H46A—C461—H46C	109.5
O26—C261—H26C	109.5	H46B—C461—H46C	109.5
H26A—C261—H26C	109.5	C46—O46—C461	116.8 (4)
H26B—C261—H26C	109.5	H11—O1—H12	105.6
C26—O26—C261	116.7 (4)	H21—O2—H22	105.3
C36—N31—C32	115.9 (4)	H31—O3—H32	105.5
C32—N32—H32A	120.0
C16—N11—C12—N12	−178.1 (5)	C36—N31—C32—N32	179.5 (4)
C16—N11—C12—N13	1.4 (8)	C36—N31—C32—N33	−2.0 (7)
N12—C12—N13—C14	179.6 (4)	N32—C32—N33—C34	178.8 (4)
N11—C12—N13—C14	0.1 (8)	N31—C32—N33—C34	0.3 (7)
C12—N13—C14—O14	179.3 (4)	C32—N33—C34—O34	−178.6 (4)
C12—N13—C14—C15	−1.4 (7)	C32—N33—C34—C35	2.3 (7)
N13—C14—O14—C141	−5.4 (7)	N33—C34—O34—C341	0.1 (7)
C15—C14—O14—C141	175.3 (4)	C35—C34—O34—C341	179.2 (4)
N13—C14—C15—N15	−179.4 (5)	N33—C34—C35—N35	176.6 (5)
O14—C14—C15—N15	−0.1 (7)	O34—C34—C35—N35	−2.4 (7)
N13—C14—C15—C16	1.2 (7)	N33—C34—C35—C36	−2.8 (7)
O14—C14—C15—C16	−179.5 (4)	O34—C34—C35—C36	178.1 (4)
C14—C15—N15—O15	−177.8 (4)	C34—C35—N35—O35	178.9 (4)
C16—C15—N15—O15	1.6 (8)	C36—C35—N35—O35	−1.7 (8)
C12—N11—C16—O16	179.1 (4)	C32—N31—C36—O36	−178.4 (5)
C12—N11—C16—C15	−1.6 (8)	C32—N31—C36—C35	1.3 (7)
N15—C15—C16—N11	−179.0 (5)	N35—C35—C36—O36	1.2 (8)
C14—C15—C16—N11	0.4 (8)	C34—C35—C36—O36	−179.4 (4)
N15—C15—C16—O16	0.4 (8)	N35—C35—C36—N31	−178.5 (5)
C14—C15—C16—O16	179.8 (4)	C34—C35—C36—N31	0.8 (7)
N11—C16—O16—C161	−0.3 (7)	N31—C36—O36—C361	0.8 (7)
C15—C16—O16—C161	−179.6 (5)	C35—C36—O36—C361	−179.0 (5)
C26—N21—C22—N22	−179.2 (5)	C46—N41—C42—N42	178.3 (4)
C26—N21—C22—N23	0.2 (8)	C46—N41—C42—N43	−1.5 (7)
N22—C22—N23—C24	179.4 (4)	N42—C42—N43—C44	−178.1 (4)
N21—C22—N23—C24	0.0 (8)	N41—C42—N43—C44	1.7 (7)
C22—N23—C24—O24	−179.5 (4)	C42—N43—C44—O44	179.9 (4)
C22—N23—C24—C25	0.5 (7)	C42—N43—C44—C45	−0.4 (7)
N23—C24—O24—C241	−1.6 (7)	N43—C44—O44—C441	−3.0 (7)
C25—C24—O24—C241	178.3 (4)	C45—C44—O44—C441	177.3 (5)
N23—C24—C25—N25	−179.8 (5)	O44—C44—C45—N45	−2.4 (6)
O24—C24—C25—N25	0.3 (7)	N43—C44—C45—N45	177.9 (5)
N23—C24—C25—C26	−1.1 (7)	O44—C44—C45—C46	178.9 (4)
O24—C24—C25—C26	178.9 (4)	N43—C44—C45—C46	−0.8 (7)
C24—C25—N25—O25	178.5 (4)	C46—C45—N45—O45	−0.2 (8)
C26—C25—N25—O25	0.1 (8)	C44—C45—N45—O45	−178.7 (4)
C22—N21—C26—O26	178.5 (4)	C42—N41—C46—O46	−179.9 (4)
C22—N21—C26—C25	−0.9 (7)	C42—N41—C46—C45	0.0 (7)
N25—C25—C26—N21	179.7 (5)	N45—C45—C46—N41	−177.5 (5)
C24—C25—C26—N21	1.3 (7)	C44—C45—C46—N41	1.0 (7)
N25—C25—C26—O26	0.3 (8)	N45—C45—C46—O46	2.4 (8)
C24—C25—C26—O26	−178.1 (4)	C44—C45—C46—O46	−179.1 (4)
N21—C26—O26—C261	1.9 (6)	N41—C46—O46—C461	−1.3 (6)
C25—C26—O26—C261	−178.6 (4)	C45—C46—O46—C461	178.8 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H12···O45	1.00	2.00	2.957 (5)	159
O1—H12···O46	1.00	2.35	2.977 (5)	120
N42—H42A···O35	0.88	2.13	3.011 (6)	177
N32—H32B···O3	0.88	2.12	2.962 (6)	161
O3—H31···O25	1.00	2.04	2.941 (5)	149
O3—H31···O26	1.00	2.12	2.882 (5)	132
N22—H22A···O14	0.88	2.31	3.183 (6)	172
N22—H22B···O2	0.88	2.00	2.855 (6)	165
O2—H22···O15	1.00	1.73	2.719 (6)	171
O2—H22···N15	1.00	2.23	3.090 (6)	143
N12—H12B···O1	0.88	1.95	2.825 (6)	177
O1—H11···O3^i	1.00	1.82	2.817 (5)	170
O2—H21···O36^ii	1.00	2.08	2.834 (5)	131
O2—H21···O35^ii	1.00	2.16	2.951 (5)	135
N42—H42B···O15^iii	0.88	2.43	2.991 (6)	122
N42—H42B···O16^iii	0.88	2.46	3.337 (6)	173
N12—H12A···N25^iv	0.88	2.24	3.027 (6)	149
O3—H32···O45^v	1.00	1.78	2.767 (5)	168
O3—H32···N45^v	1.00	2.32	3.145 (6)	139
N32—H32A···O44^v	0.88	2.23	3.108 (6)	175

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