N-(2,4-Dimethoxy­benzyl­idene­amino)­guanidinium dihydrogenphosphate

In the asymmetric unit of the title compound, C₁₀H₁₅N₄O₂⁺·H₂PO₄⁻, there are two protonated amino­guanidinium cations and two dihydrogenphosphate anions. The positive charge on the protonated amidine group is delocalized over the three C—N bonds in a manner similar to that found in guanidinium salts. The amino­guanidinium cations are found to be the E-isomer structures. Intra­molecular inter­actions of the N—H...N type are observed, leading to the formation of five-membered rings. Extensive networks of O—H...O, N—H...O and C—H...O hydrogen bonds stabilize the three-dimensional network. In the crystal structure, π–π inter­actions between the benzene rings, with a distance of 3.778 (2) Å between the ring centroids, also affect the packing of the mol­ecules.

S1. Comment

Aminoguanidine has been reported to be a potent inhibitor of nitric oxide synthase (Griffith & Gross, 1996). Guanylhydrazones (alkylenaminoguanidines, carboximideamidehydrazones, diaminomethylene hydrazones) are condensation products of oxo-compounds with aminoguanidines. This class of compounds has been known for some time (Thiele, 1892) and is of considerable interest, due to the wide variety of different pharmacological activities found with many representatives (Richter et al., 1993a,b). Furthermore, guanylhydrazones are valuable synthetic building blocks for ring-closure reactions, leading to several nitrogen-containing heterocycles (Sarıpınar et al., 2005). Protomeric tautomerism is of much interest in experimental as well as theoretical chemistry, since it is an important reaction in biological processes. Guanylhydrazones can exist in two tautomeric forms (Zoltan et al., 1999). They may undergo proton shifts (tautomerism) rapidly and easily, and the chemical reactivities of the two isomers may be quite different. Molecular assembly in a crystal is predominantly governed by intermolecular forces, conventionally described by strong and directional N—H···O, O—H···O and O—H···N hydrogen bonds (Desiraju, 2002). In molecules having an imbalance of hydrogen-bond donors and acceptors, the deficiency in either donors or acceptors is fulfilled by other types of weak and less-directional forces. Interactions involving the π cloud in aromatic compounds also belong to this category. We present here the complete geometric characterization of the title compound, (I), in the solid state, together with a comparison of the molecular structure with those of related compounds and an analysis of their intermolecular interactions in the crystal network.

The asymmetric unit of (I) consists of two protonated amidinium cations, A (O1/O2/N1–N4/C1–C10) and B (O7/O8/N5–N8/C11–C20), and two dihydrogenphosphate anions, H₂PO₄⁻, A' (P1/O3–O6) and B' (P2/O9–O12). The two independent aminoguanidinium cations have very similar molecular dimensions (Fig. 1 and Table 1); this is also the case for the two dihydrogenphosphate anions, whose geometries are normal (Allen et al., 1987). In the following discussion, parameters for molecules B are quoted in square brackets.

In the aminoguanidine moiety, the N—N bond length is 1.394 (3) Å [1.395 (3) Å], approximating to a pure single bond (1.41 Å; Burke-Laing & Laing, 1976). Similarly, the corresponding N═C bond length of 1.279 (4) Å [1.275 (4) Å] has pure double-bond character (1.27 Å). That the lone-pair electrons on atom N2 [N6] are delocalized through conjugation with the amidine group rather than the N1═ C9 [N5═C19] double bond is also seen in the N2—C10 bond length of 1.335 (4) Å [1.329 (4) Å], which is intermediate between a single and a double bond, and similar to the two C—N bonds in the amidine moieties. Similar C—N bond distances have also been found in a number of inorganic salts containing the guanidinium cation (see, for example, Katrusiak & Szafrański, 1994; Kettmann & Světlík, 2002).

In the cation, the dimethoxyphenyl and aminoguanidine fragments are planar, with maximum deviations of −0.0329 (32) and 0.0268 (25) Å [0.0575 (28) and 0.0674 (24) Å], respectively. The planes of these two moieties make a dihedral angle of 14.10 (15)° [13.46 (15)°], showing that the 2,4-dimethoxybenzalaminoguanidine molecules are almost flat. The 2,4-dimethoxybenzalaminoguanidine molecule can exist in two different configurations, as a E or Z isomer, at the C═N double bond. The N—N═C—C torsion angle is −178.6 (3)° [176.5 (3)°], and this reveals that the molecules have the E isomer structure in (I).

Within the phenyl group in the aminoguanidine A molecule, there are significant differences between bond lengths: C1—C6 [1.400 (4) Å] is slightly longer than C2—C3 and C4—C5 [1.373 (4) and 1.374 (4) Å, respectively]. The remaining bond lengths in the ring are close to the C1—C6 bond length. In addition, the C6—C1—C2 bond angle is 118.4 (3)°, while the rest of the internal angles are almost equal to the normal value of 120° for the intra-ring bond angles of phenyl rings. Similiar differences were also seen in the aminoguanidine B molecule: C11—C16 [1.398 (4) Å] is slightly longer than C12—C13 and C14—C15 [1.378 (4) and 1.372 (4) Å, respectively]. Moreover, the C16—C11—C12 bond angle is 118.0 (3)°, while the remaining bond angles are close to 120°. It is interesting to note that, within the dimethoxyphenyl fragment, the exocyclic C—C—O angles show an unusual pattern compared with those observed for methoxyaryl compounds (Seip & Seip, 1973; Ferguson et al., 1996; Patterson et al., 1998), in which the C—C—O angles cisoid to the substituents are much larger than 120°, while those transoid are very much smaller. At the same time, the C—O—C angles are well in excess of tetrahedral values, consistent with the occurrence of repulsive interactions between the methyl groups and the neighbouring aryl C—H unit.

In the aminoguanidinium cation, an intramolecular N3—H3B···N1 [N7—H7E···N5] hydrogen bond leads to the formation of a five-membered ring (Fig. 1). The crystal structure of (I) is stabilized by a network of N—H···O and O—H···O hydrogen bonds, in which amidine and methoxy groups, as well as H₂PO₄⁻ anions, are involved (Table 2 and Fig. 2). Additionally, there are also C—H···O contacts. The O—H···O interactions formed between the H₂PO₄⁻ anions are quite strong. Among the N—H···O interactions, the strongest is formed by amidine atom N2 [N6]. However, there are also one C—H···O and one N—H···O interactions, in which enol O atoms are involved as acceptors. The anion O atoms are involved as acceptors in different hydrogen-bond interactions, five for A' and four for B', and hence a three-centred contact is formed. Thus, the hydrogen-bond network linking adjacent cations and anions in the crystal structure of (I) is three-dimensional. In addition to these intra- and intermolecular interactions, intermolecular π—π stacking interactions between the benzene ring of one cation and the inversion related ring of the other at (2 − x, 1 − y, 1 − z) are also observed along the a axis, with a distance of 3.778 (2) Å between the ring centroids. Full details of the hydrogen-bonding geometry are given in Table 2.

S2. Experimental

2,4-Dimethoxybenzaldehyde (1.66 g) and aminoguanidinebicarbonate (1.36 g) were refluxed in a boiling water solution (20 ml) of 1 N H₃PO₄ for 1 h and, after cooling, the precipitate was collected, yielding 2.24 g (70%) of 2,4-dimethoxybenzalaminoguanidine phosphate. The crude product was recrystallized from methanol and allowed to dry over P₂O₅ (m.p. 529 K). Analysis calculated for C₁₀H₁₇N₄O₆P: C 37.50, H 5.31, N 17.50%; found: C 37.33, H 5.21, N 17.39%.

S3. Refinement

H atoms were positioned geometrically and treated using a riding model, fixing the bond lengths at 0.82, 0.86, 0.93 and 0.96 Å for O—H, N—H and N—H₂, C—H and aromatic H atoms, and CH₃, respectively. The displacement parameters of the H atoms were constrained as U_iso(H) = 1.2U_eq(parent), or 1.5U_eq(C) for methyl H atoms.

Computing details

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures

	Fig. 1. Views of the two molecules of the asymmetric unit of (I), with the atomic numbering schemes. Displacement ellipsoids are drawn at the 40% probability level and H atoms are shown as small spheres of arbitrary radii. Dashed lines indicate the N—H···N interactions.
	Fig. 2. The molecular packing of (I), showing the intermolecular interactions (dashed lines). For clarity, only H atoms involved in the hydrogen bonding have been included.

N-(2,4-Dimethoxybenzylideneamino)guanidinium dihydrogenphosphate

Crystal data

C10H15N4O2^+·H2PO4^−	Z = 4
Mr = 320.25	F(000) = 672
Triclinic, P1	Dx = 1.457 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.4822 (5) Å	Cell parameters from 17194 reflections
b = 13.6287 (9) Å	θ = 2.4–27.9°
c = 14.3131 (9) Å	µ = 0.22 mm^−1
α = 63.081 (5)°	T = 296 K
β = 81.702 (5)°	Rod, colourless
γ = 85.936 (5)°	0.75 × 0.38 × 0.19 mm
V = 1459.86 (16) Å^3

Data collection

Stoe IPDS 2 diffractometer	5746 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	4086 reflections with I > 2σ(I)
Plane graphite monochromator	Rint = 0.096
Detector resolution: 6.67 pixels mm^-1	θmax = 26.0°, θmin = 1.7°
ω scans	h = −10→10
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −16→16
Tmin = 0.888, Tmax = 0.969	l = −17→17
18714 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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.153	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0663P)^2 + 0.6872P] where P = (Fo^2 + 2Fc^2)/3
5746 reflections	(Δ/σ)max < 0.001
387 parameters	Δρmax = 0.58 e Å^−3
0 restraints	Δρmin = −0.39 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
O1	0.5771 (3)	−0.01611 (19)	0.76769 (17)	0.0615 (7)
O2	0.5581 (3)	0.36525 (17)	0.50983 (17)	0.0544 (6)
N1	0.3627 (3)	0.2855 (2)	0.31563 (18)	0.0436 (6)
N2	0.3266 (3)	0.3760 (2)	0.22353 (18)	0.0455 (6)
H2	0.3334	0.4420	0.2157	0.055*
N3	0.2751 (4)	0.2564 (2)	0.1587 (2)	0.0682 (9)
H3A	0.2465	0.2452	0.1091	0.082*
H3B	0.2999	0.2016	0.2155	0.082*
N4	0.2435 (4)	0.4425 (2)	0.0612 (2)	0.0592 (8)
H4A	0.2146	0.4327	0.0109	0.071*
H4B	0.2479	0.5079	0.0553	0.071*
C1	0.4497 (3)	0.2270 (2)	0.4845 (2)	0.0388 (6)
C2	0.4159 (4)	0.1163 (2)	0.5205 (2)	0.0434 (7)
H2A	0.3641	0.0954	0.4793	0.052*
C3	0.4574 (4)	0.0372 (3)	0.6153 (2)	0.0491 (7)
H3	0.4336	−0.0363	0.6383	0.059*
C4	0.5350 (4)	0.0685 (2)	0.6762 (2)	0.0445 (7)
C5	0.5671 (4)	0.1771 (3)	0.6451 (2)	0.0444 (7)
H5	0.6164	0.1972	0.6878	0.053*
C6	0.5250 (4)	0.2571 (2)	0.5485 (2)	0.0400 (6)
C7	0.6570 (5)	0.0130 (3)	0.8332 (3)	0.0706 (11)
H7A	0.6795	−0.0524	0.8948	0.106*
H7B	0.5901	0.0613	0.8541	0.106*
H7C	0.7550	0.0495	0.7944	0.106*
C8	0.6333 (5)	0.3994 (3)	0.5725 (3)	0.0605 (9)
H8A	0.6569	0.4765	0.5336	0.091*
H8B	0.7304	0.3584	0.5904	0.091*
H8C	0.5635	0.3863	0.6361	0.091*
C9	0.4096 (4)	0.3117 (2)	0.3823 (2)	0.0418 (7)
H9	0.4183	0.3856	0.3657	0.050*
C10	0.2810 (4)	0.3568 (3)	0.1478 (2)	0.0475 (7)
O7	1.2203 (3)	0.77200 (19)	0.72792 (17)	0.0589 (6)
O8	0.9715 (3)	0.61411 (17)	0.54462 (16)	0.0548 (6)
N5	0.9281 (3)	0.9117 (2)	0.30108 (18)	0.0434 (6)
N6	0.8642 (3)	0.9093 (2)	0.21770 (18)	0.0453 (6)
H6	0.8517	0.8478	0.2165	0.054*
N7	0.8342 (4)	1.0972 (2)	0.1438 (2)	0.0635 (8)
H7D	0.8073	1.1577	0.0930	0.076*
H7E	0.8686	1.0981	0.1971	0.076*
N8	0.7702 (4)	0.9994 (2)	0.0591 (2)	0.0597 (8)
H8D	0.7426	1.0589	0.0074	0.072*
H8E	0.7637	0.9371	0.0583	0.072*
C11	1.0201 (3)	0.8032 (2)	0.4681 (2)	0.0377 (6)
C12	1.0807 (4)	0.8924 (2)	0.4736 (2)	0.0457 (7)
H12	1.0770	0.9619	0.4169	0.055*
C13	1.1461 (4)	0.8804 (3)	0.5610 (2)	0.0481 (7)
H13	1.1852	0.9411	0.5636	0.058*
C14	1.1527 (4)	0.7764 (3)	0.6449 (2)	0.0426 (7)
C15	1.0962 (4)	0.6862 (2)	0.6419 (2)	0.0431 (7)
H15	1.1026	0.6167	0.6983	0.052*
C16	1.0293 (3)	0.6993 (2)	0.5538 (2)	0.0394 (6)
C17	1.2394 (5)	0.6666 (3)	0.8142 (2)	0.0612 (9)
H17A	1.2992	0.6739	0.8627	0.092*
H17B	1.2952	0.6184	0.7882	0.092*
H17C	1.1365	0.6365	0.8497	0.092*
C18	0.9925 (5)	0.5053 (3)	0.6264 (3)	0.0639 (10)
H18A	0.9501	0.4527	0.6093	0.096*
H18B	0.9374	0.4993	0.6922	0.096*
H18C	1.1039	0.4908	0.6325	0.096*
C19	0.9504 (3)	0.8166 (2)	0.3756 (2)	0.0409 (6)
H19	0.9216	0.7545	0.3708	0.049*
C20	0.8228 (4)	1.0037 (3)	0.1402 (2)	0.0452 (7)
P1	0.29559 (8)	0.68665 (6)	0.11636 (5)	0.0372 (2)
O3	0.1869 (3)	0.7256 (2)	0.19058 (19)	0.0587 (6)
H3O	0.0936	0.7255	0.1815	0.070*
O4	0.1964 (2)	0.6661 (2)	0.04834 (17)	0.0545 (6)
O5	0.4031 (3)	0.7887 (2)	0.0449 (2)	0.0736 (9)
H5O	0.4966	0.7719	0.0532	0.088*
O6	0.3947 (2)	0.59011 (16)	0.18008 (16)	0.0463 (5)
P2	0.78973 (8)	0.68971 (7)	0.12923 (6)	0.0408 (2)
O9	0.6818 (3)	0.5935 (2)	0.2107 (2)	0.0729 (8)
H9O	0.5930	0.6014	0.1919	0.088*
O10	0.6932 (3)	0.7772 (2)	0.0547 (2)	0.0877 (11)
O11	0.9015 (3)	0.6343 (4)	0.0698 (3)	0.0963 (12)
H11O	0.9915	0.6596	0.0561	0.116*
O12	0.8875 (2)	0.7239 (2)	0.18801 (19)	0.0543 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0969 (18)	0.0391 (12)	0.0421 (11)	−0.0052 (12)	−0.0286 (12)	−0.0062 (10)
O2	0.0846 (16)	0.0336 (11)	0.0511 (12)	0.0022 (11)	−0.0319 (11)	−0.0179 (9)
N1	0.0591 (16)	0.0351 (13)	0.0356 (12)	0.0025 (11)	−0.0169 (11)	−0.0122 (10)
N2	0.0637 (16)	0.0356 (13)	0.0384 (12)	0.0006 (11)	−0.0200 (11)	−0.0139 (10)
N3	0.114 (3)	0.0452 (16)	0.0568 (16)	0.0074 (16)	−0.0423 (17)	−0.0250 (14)
N4	0.093 (2)	0.0457 (16)	0.0460 (14)	0.0105 (15)	−0.0359 (15)	−0.0203 (12)
C1	0.0476 (16)	0.0368 (15)	0.0325 (13)	0.0019 (12)	−0.0093 (11)	−0.0152 (11)
C2	0.0523 (17)	0.0436 (16)	0.0368 (14)	−0.0056 (13)	−0.0101 (12)	−0.0183 (12)
C3	0.066 (2)	0.0371 (16)	0.0414 (15)	−0.0091 (14)	−0.0085 (14)	−0.0137 (13)
C4	0.0585 (18)	0.0386 (16)	0.0321 (13)	−0.0009 (13)	−0.0104 (12)	−0.0107 (12)
C5	0.0587 (18)	0.0434 (16)	0.0349 (14)	0.0019 (14)	−0.0152 (13)	−0.0185 (13)
C6	0.0512 (16)	0.0332 (14)	0.0369 (14)	0.0030 (12)	−0.0106 (12)	−0.0160 (12)
C7	0.108 (3)	0.054 (2)	0.0429 (17)	−0.008 (2)	−0.0364 (19)	−0.0066 (15)
C8	0.080 (2)	0.0434 (18)	0.073 (2)	0.0049 (17)	−0.0348 (19)	−0.0329 (17)
C9	0.0507 (17)	0.0372 (15)	0.0385 (14)	0.0013 (13)	−0.0107 (12)	−0.0165 (12)
C10	0.0591 (19)	0.0458 (17)	0.0427 (15)	0.0010 (14)	−0.0166 (14)	−0.0216 (13)
O7	0.0886 (17)	0.0508 (13)	0.0470 (12)	0.0031 (12)	−0.0307 (12)	−0.0245 (10)
O8	0.0865 (17)	0.0348 (11)	0.0434 (11)	−0.0074 (11)	−0.0286 (11)	−0.0108 (9)
N5	0.0580 (15)	0.0382 (13)	0.0354 (12)	0.0090 (11)	−0.0188 (11)	−0.0153 (10)
N6	0.0640 (16)	0.0370 (13)	0.0394 (12)	0.0100 (12)	−0.0229 (11)	−0.0178 (10)
N7	0.106 (2)	0.0408 (15)	0.0490 (15)	0.0177 (15)	−0.0387 (16)	−0.0187 (13)
N8	0.092 (2)	0.0459 (16)	0.0474 (15)	0.0193 (15)	−0.0378 (15)	−0.0211 (13)
C11	0.0421 (15)	0.0355 (15)	0.0344 (13)	0.0046 (12)	−0.0108 (11)	−0.0137 (11)
C12	0.0588 (19)	0.0338 (15)	0.0426 (15)	0.0047 (13)	−0.0154 (13)	−0.0137 (12)
C13	0.063 (2)	0.0356 (16)	0.0497 (16)	−0.0018 (14)	−0.0150 (15)	−0.0198 (13)
C14	0.0540 (17)	0.0428 (16)	0.0365 (14)	0.0036 (13)	−0.0142 (12)	−0.0206 (12)
C15	0.0571 (18)	0.0358 (15)	0.0334 (13)	−0.0009 (13)	−0.0121 (12)	−0.0109 (11)
C16	0.0477 (16)	0.0363 (15)	0.0366 (14)	−0.0008 (12)	−0.0087 (12)	−0.0174 (12)
C17	0.087 (3)	0.054 (2)	0.0434 (17)	0.0062 (18)	−0.0277 (17)	−0.0179 (15)
C18	0.105 (3)	0.0334 (17)	0.0497 (18)	−0.0138 (17)	−0.0233 (19)	−0.0100 (14)
C19	0.0492 (16)	0.0356 (15)	0.0392 (14)	0.0055 (12)	−0.0120 (12)	−0.0170 (12)
C20	0.0593 (18)	0.0400 (16)	0.0373 (14)	0.0124 (14)	−0.0172 (13)	−0.0169 (12)
P1	0.0306 (4)	0.0380 (4)	0.0374 (4)	−0.0007 (3)	−0.0113 (3)	−0.0099 (3)
O3	0.0435 (12)	0.0859 (18)	0.0703 (15)	0.0042 (12)	−0.0181 (11)	−0.0529 (14)
O4	0.0402 (11)	0.0872 (18)	0.0503 (12)	0.0099 (11)	−0.0152 (9)	−0.0419 (12)
O5	0.0366 (11)	0.0469 (14)	0.0847 (17)	−0.0015 (10)	−0.0162 (12)	0.0189 (12)
O6	0.0416 (11)	0.0320 (11)	0.0544 (12)	−0.0023 (8)	−0.0177 (9)	−0.0064 (9)
P2	0.0304 (4)	0.0449 (4)	0.0466 (4)	0.0006 (3)	−0.0129 (3)	−0.0180 (3)
O9	0.0468 (13)	0.0571 (15)	0.0793 (17)	−0.0046 (11)	−0.0302 (12)	0.0075 (13)
O10	0.0455 (13)	0.0670 (17)	0.0877 (18)	−0.0144 (12)	−0.0308 (13)	0.0286 (14)
O11	0.0432 (14)	0.183 (4)	0.134 (3)	−0.0069 (18)	−0.0108 (16)	−0.133 (3)
O12	0.0406 (11)	0.0653 (15)	0.0796 (15)	0.0066 (10)	−0.0148 (11)	−0.0510 (13)

Geometric parameters (Å, º)

O1—C4	1.372 (3)	N6—C20	1.329 (4)
O1—C7	1.433 (4)	N6—H6	0.8600
O2—C6	1.354 (4)	N7—C20	1.309 (4)
O2—C8	1.419 (4)	N7—H7D	0.8600
N1—C9	1.279 (4)	N7—H7E	0.8600
N1—N2	1.394 (3)	N8—C20	1.328 (4)
N2—C10	1.335 (4)	N8—H8D	0.8600
N2—H2	0.8600	N8—H8E	0.8600
N3—C10	1.310 (4)	C11—C12	1.391 (4)
N3—H3A	0.8600	C11—C16	1.398 (4)
N3—H3B	0.8600	C11—C19	1.459 (4)
N4—C10	1.324 (4)	C12—C13	1.378 (4)
N4—H4A	0.8600	C12—H12	0.9300
N4—H4B	0.8600	C13—C14	1.386 (4)
C1—C2	1.393 (4)	C13—H13	0.9300
C1—C6	1.400 (4)	C14—C15	1.372 (4)
C1—C9	1.465 (4)	C15—C16	1.390 (4)
C2—C3	1.373 (4)	C15—H15	0.9300
C2—H2A	0.9300	C17—H17A	0.9600
C3—C4	1.385 (4)	C17—H17B	0.9600
C3—H3	0.9300	C17—H17C	0.9600
C4—C5	1.374 (4)	C18—H18A	0.9600
C5—C6	1.397 (4)	C18—H18B	0.9600
C5—H5	0.9300	C18—H18C	0.9600
C7—H7A	0.9600	C19—H19	0.9300
C7—H7B	0.9600	P1—O6	1.4992 (19)
C7—H7C	0.9600	P1—O4	1.501 (2)
C8—H8A	0.9600	P1—O3	1.555 (2)
C8—H8B	0.9600	P1—O5	1.560 (2)
C8—H8C	0.9600	O3—H3O	0.8200
C9—H9	0.9300	O5—H5O	0.8200
O7—C14	1.368 (3)	P2—O10	1.480 (2)
O7—C17	1.426 (4)	P2—O12	1.491 (2)
O8—C16	1.357 (4)	P2—O9	1.547 (3)
O8—C18	1.433 (4)	P2—O11	1.562 (3)
N5—C19	1.275 (4)	O9—H9O	0.8200
N5—N6	1.395 (3)	O11—H11O	0.8200
C4—O1—C7	116.9 (3)	H7D—N7—H7E	120.0
C6—O2—C8	118.3 (2)	C20—N8—H8D	120.0
C9—N1—N2	113.5 (2)	C20—N8—H8E	120.0
C10—N2—N1	117.8 (3)	H8D—N8—H8E	120.0
C10—N2—H2	121.1	C12—C11—C16	118.0 (2)
N1—N2—H2	121.1	C12—C11—C19	121.5 (3)
C10—N3—H3A	120.0	C16—C11—C19	120.5 (3)
C10—N3—H3B	120.0	C13—C12—C11	121.8 (3)
H3A—N3—H3B	120.0	C13—C12—H12	119.1
C10—N4—H4A	120.0	C11—C12—H12	119.1
C10—N4—H4B	120.0	C12—C13—C14	118.9 (3)
H4A—N4—H4B	120.0	C12—C13—H13	120.6
C2—C1—C6	118.4 (2)	C14—C13—H13	120.6
C2—C1—C9	121.9 (3)	O7—C14—C15	123.9 (3)
C6—C1—C9	119.6 (3)	O7—C14—C13	115.0 (3)
C3—C2—C1	121.5 (3)	C15—C14—C13	121.1 (3)
C3—C2—H2A	119.2	C14—C15—C16	119.5 (3)
C1—C2—H2A	119.2	C14—C15—H15	120.2
C2—C3—C4	119.1 (3)	C16—C15—H15	120.2
C2—C3—H3	120.5	O8—C16—C15	123.0 (3)
C4—C3—H3	120.5	O8—C16—C11	116.3 (2)
O1—C4—C5	123.5 (3)	C15—C16—C11	120.7 (3)
O1—C4—C3	115.2 (3)	O7—C17—H17A	109.5
C5—C4—C3	121.4 (3)	O7—C17—H17B	109.5
C4—C5—C6	119.2 (3)	H17A—C17—H17B	109.5
C4—C5—H5	120.4	O7—C17—H17C	109.5
C6—C5—H5	120.4	H17A—C17—H17C	109.5
O2—C6—C5	123.1 (3)	H17B—C17—H17C	109.5
O2—C6—C1	116.6 (2)	O8—C18—H18A	109.5
C5—C6—C1	120.3 (3)	O8—C18—H18B	109.5
O1—C7—H7A	109.5	H18A—C18—H18B	109.5
O1—C7—H7B	109.5	O8—C18—H18C	109.5
H7A—C7—H7B	109.5	H18A—C18—H18C	109.5
O1—C7—H7C	109.5	H18B—C18—H18C	109.5
H7A—C7—H7C	109.5	N5—C19—C11	121.2 (3)
H7B—C7—H7C	109.5	N5—C19—H19	119.4
O2—C8—H8A	109.5	C11—C19—H19	119.4
O2—C8—H8B	109.5	N7—C20—N8	121.5 (3)
H8A—C8—H8B	109.5	N7—C20—N6	121.1 (3)
O2—C8—H8C	109.5	N8—C20—N6	117.4 (3)
H8A—C8—H8C	109.5	O6—P1—O4	114.40 (14)
H8B—C8—H8C	109.5	O6—P1—O3	109.89 (13)
N1—C9—C1	121.0 (3)	O4—P1—O3	109.74 (12)
N1—C9—H9	119.5	O6—P1—O5	110.48 (12)
C1—C9—H9	119.5	O4—P1—O5	108.67 (15)
N3—C10—N4	121.1 (3)	O3—P1—O5	103.04 (17)
N3—C10—N2	120.9 (3)	P1—O3—H3O	109.5
N4—C10—N2	117.9 (3)	P1—O5—H5O	109.5
C14—O7—C17	117.8 (3)	O10—P2—O12	116.24 (18)
C16—O8—C18	117.8 (2)	O10—P2—O9	110.25 (13)
C19—N5—N6	113.6 (3)	O12—P2—O9	108.22 (15)
C20—N6—N5	118.7 (3)	O10—P2—O11	109.9 (2)
C20—N6—H6	120.6	O12—P2—O11	108.70 (13)
N5—N6—H6	120.6	O9—P2—O11	102.7 (2)
C20—N7—H7D	120.0	P2—O9—H9O	109.5
C20—N7—H7E	120.0	P2—O11—H11O	109.5
C9—N1—N2—C10	178.1 (3)	C19—N5—N6—C20	174.1 (3)
C6—C1—C2—C3	−1.2 (5)	C16—C11—C12—C13	−0.9 (5)
C9—C1—C2—C3	178.4 (3)	C19—C11—C12—C13	179.7 (3)
C1—C2—C3—C4	−0.2 (5)	C11—C12—C13—C14	0.6 (5)
C7—O1—C4—C5	0.7 (5)	C17—O7—C14—C15	2.9 (5)
C7—O1—C4—C3	−179.7 (3)	C17—O7—C14—C13	−176.3 (3)
C2—C3—C4—O1	−177.7 (3)	C12—C13—C14—O7	179.6 (3)
C2—C3—C4—C5	1.9 (5)	C12—C13—C14—C15	0.3 (5)
O1—C4—C5—C6	177.6 (3)	O7—C14—C15—C16	179.9 (3)
C3—C4—C5—C6	−2.0 (5)	C13—C14—C15—C16	−0.8 (5)
C8—O2—C6—C5	−2.7 (5)	C18—O8—C16—C15	−5.0 (5)
C8—O2—C6—C1	179.5 (3)	C18—O8—C16—C11	174.3 (3)
C4—C5—C6—O2	−177.2 (3)	C14—C15—C16—O8	179.7 (3)
C4—C5—C6—C1	0.5 (5)	C14—C15—C16—C11	0.5 (5)
C2—C1—C6—O2	178.9 (3)	C12—C11—C16—O8	−178.9 (3)
C9—C1—C6—O2	−0.7 (4)	C19—C11—C16—O8	0.5 (4)
C2—C1—C6—C5	1.0 (4)	C12—C11—C16—C15	0.4 (4)
C9—C1—C6—C5	−178.6 (3)	C19—C11—C16—C15	179.8 (3)
N2—N1—C9—C1	178.8 (3)	N6—N5—C19—C11	178.5 (3)
C2—C1—C9—N1	−10.1 (5)	C12—C11—C19—N5	−7.0 (5)
C6—C1—C9—N1	169.6 (3)	C16—C11—C19—N5	173.6 (3)
N1—N2—C10—N3	−2.0 (5)	N5—N6—C20—N7	−3.3 (5)
N1—N2—C10—N4	178.6 (3)	N5—N6—C20—N8	176.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6	0.86	1.94	2.780 (3)	167
N3—H3A···O10^i	0.86	2.48	3.260 (5)	152
N3—H3B···O1^ii	0.86	2.59	3.175 (4)	127
N3—H3B···N1	0.86	2.33	2.662 (4)	103
N4—H4A···O11^i	0.86	2.13	2.959 (4)	161
N4—H4B···O4	0.86	2.13	2.969 (4)	166
N6—H6···O12	0.86	1.90	2.736 (3)	162
N7—H7D···O4^iii	0.86	2.34	3.177 (4)	165
N7—H7E···N5	0.86	2.35	2.678 (4)	103
N7—H7E···O7^iv	0.86	2.48	3.060 (4)	125
N8—H8D···O5^iii	0.86	2.21	2.976 (3)	148
N8—H8E···O10	0.86	2.33	3.173 (5)	169
O3—H3O···O12^v	0.82	1.74	2.546 (3)	168
O5—H5O···O10	0.82	1.68	2.475 (3)	163
O9—H9O···O6	0.82	1.74	2.543 (3)	166
O11—H11O···O4^vi	0.82	1.73	2.519 (3)	161
C7—H7A···O10^vii	0.96	2.42	3.373 (4)	171

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