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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105037522/hj1076sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105037522/hj1076Isup2.hkl
Contains datablock I

CCDC reference: 294337

Comment top

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 NC 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 [N5C19] 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 CN double bond. The N—NC—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 ππ 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.

Experimental top

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%.

Refinement top

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 Uiso(H) = 1.2Ueq(parent), or 1.5Ueq(C) for methyl H atoms.

Computing details top

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 top
[Figure 1] 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.
[Figure 2] 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 top
Crystal data top
C10H15N4O2+·H2PO4Z = 4
Mr = 320.25F(000) = 672
Triclinic, P1Dx = 1.457 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.4822 (5) ÅCell parameters from 17194 reflections
b = 13.6287 (9) Åθ = 2.4–27.9°
c = 14.3131 (9) ŵ = 0.22 mm1
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) Å3
Data collection top
Stoe IPDS 2
diffractometer
5746 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus4086 reflections with I > 2σ(I)
Plane graphite monochromatorRint = 0.096
Detector resolution: 6.67 pixels mm-1θmax = 26.0°, θmin = 1.7°
ω scansh = 1010
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
k = 1616
Tmin = 0.888, Tmax = 0.969l = 1717
18714 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.153H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0663P)2 + 0.6872P]
where P = (Fo2 + 2Fc2)/3
5746 reflections(Δ/σ)max < 0.001
387 parametersΔρmax = 0.58 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
C10H15N4O2+·H2PO4γ = 85.936 (5)°
Mr = 320.25V = 1459.86 (16) Å3
Triclinic, P1Z = 4
a = 8.4822 (5) ÅMo Kα radiation
b = 13.6287 (9) ŵ = 0.22 mm1
c = 14.3131 (9) ÅT = 296 K
α = 63.081 (5)°0.75 × 0.38 × 0.19 mm
β = 81.702 (5)°
Data collection top
Stoe IPDS 2
diffractometer
5746 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
4086 reflections with I > 2σ(I)
Tmin = 0.888, Tmax = 0.969Rint = 0.096
18714 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.153H-atom parameters constrained
S = 1.03Δρmax = 0.58 e Å3
5746 reflectionsΔρmin = 0.39 e Å3
387 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
O10.5771 (3)0.01611 (19)0.76769 (17)0.0615 (7)
O20.5581 (3)0.36525 (17)0.50983 (17)0.0544 (6)
N10.3627 (3)0.2855 (2)0.31563 (18)0.0436 (6)
N20.3266 (3)0.3760 (2)0.22353 (18)0.0455 (6)
H20.33340.44200.21570.055*
N30.2751 (4)0.2564 (2)0.1587 (2)0.0682 (9)
H3A0.24650.24520.10910.082*
H3B0.29990.20160.21550.082*
N40.2435 (4)0.4425 (2)0.0612 (2)0.0592 (8)
H4A0.21460.43270.01090.071*
H4B0.24790.50790.05530.071*
C10.4497 (3)0.2270 (2)0.4845 (2)0.0388 (6)
C20.4159 (4)0.1163 (2)0.5205 (2)0.0434 (7)
H2A0.36410.09540.47930.052*
C30.4574 (4)0.0372 (3)0.6153 (2)0.0491 (7)
H30.43360.03630.63830.059*
C40.5350 (4)0.0685 (2)0.6762 (2)0.0445 (7)
C50.5671 (4)0.1771 (3)0.6451 (2)0.0444 (7)
H50.61640.19720.68780.053*
C60.5250 (4)0.2571 (2)0.5485 (2)0.0400 (6)
C70.6570 (5)0.0130 (3)0.8332 (3)0.0706 (11)
H7A0.67950.05240.89480.106*
H7B0.59010.06130.85410.106*
H7C0.75500.04950.79440.106*
C80.6333 (5)0.3994 (3)0.5725 (3)0.0605 (9)
H8A0.65690.47650.53360.091*
H8B0.73040.35840.59040.091*
H8C0.56350.38630.63610.091*
C90.4096 (4)0.3117 (2)0.3823 (2)0.0418 (7)
H90.41830.38560.36570.050*
C100.2810 (4)0.3568 (3)0.1478 (2)0.0475 (7)
O71.2203 (3)0.77200 (19)0.72792 (17)0.0589 (6)
O80.9715 (3)0.61411 (17)0.54462 (16)0.0548 (6)
N50.9281 (3)0.9117 (2)0.30108 (18)0.0434 (6)
N60.8642 (3)0.9093 (2)0.21770 (18)0.0453 (6)
H60.85170.84780.21650.054*
N70.8342 (4)1.0972 (2)0.1438 (2)0.0635 (8)
H7D0.80731.15770.09300.076*
H7E0.86861.09810.19710.076*
N80.7702 (4)0.9994 (2)0.0591 (2)0.0597 (8)
H8D0.74261.05890.00740.072*
H8E0.76370.93710.05830.072*
C111.0201 (3)0.8032 (2)0.4681 (2)0.0377 (6)
C121.0807 (4)0.8924 (2)0.4736 (2)0.0457 (7)
H121.07700.96190.41690.055*
C131.1461 (4)0.8804 (3)0.5610 (2)0.0481 (7)
H131.18520.94110.56360.058*
C141.1527 (4)0.7764 (3)0.6449 (2)0.0426 (7)
C151.0962 (4)0.6862 (2)0.6419 (2)0.0431 (7)
H151.10260.61670.69830.052*
C161.0293 (3)0.6993 (2)0.5538 (2)0.0394 (6)
C171.2394 (5)0.6666 (3)0.8142 (2)0.0612 (9)
H17A1.29920.67390.86270.092*
H17B1.29520.61840.78820.092*
H17C1.13650.63650.84970.092*
C180.9925 (5)0.5053 (3)0.6264 (3)0.0639 (10)
H18A0.95010.45270.60930.096*
H18B0.93740.49930.69220.096*
H18C1.10390.49080.63250.096*
C190.9504 (3)0.8166 (2)0.3756 (2)0.0409 (6)
H190.92160.75450.37080.049*
C200.8228 (4)1.0037 (3)0.1402 (2)0.0452 (7)
P10.29559 (8)0.68665 (6)0.11636 (5)0.0372 (2)
O30.1869 (3)0.7256 (2)0.19058 (19)0.0587 (6)
H3O0.09360.72550.18150.070*
O40.1964 (2)0.6661 (2)0.04834 (17)0.0545 (6)
O50.4031 (3)0.7887 (2)0.0449 (2)0.0736 (9)
H5O0.49660.77190.05320.088*
O60.3947 (2)0.59011 (16)0.18008 (16)0.0463 (5)
P20.78973 (8)0.68971 (7)0.12923 (6)0.0408 (2)
O90.6818 (3)0.5935 (2)0.2107 (2)0.0729 (8)
H9O0.59300.60140.19190.088*
O100.6932 (3)0.7772 (2)0.0547 (2)0.0877 (11)
O110.9015 (3)0.6343 (4)0.0698 (3)0.0963 (12)
H11O0.99150.65960.05610.116*
O120.8875 (2)0.7239 (2)0.18801 (19)0.0543 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0969 (18)0.0391 (12)0.0421 (11)0.0052 (12)0.0286 (12)0.0062 (10)
O20.0846 (16)0.0336 (11)0.0511 (12)0.0022 (11)0.0319 (11)0.0179 (9)
N10.0591 (16)0.0351 (13)0.0356 (12)0.0025 (11)0.0169 (11)0.0122 (10)
N20.0637 (16)0.0356 (13)0.0384 (12)0.0006 (11)0.0200 (11)0.0139 (10)
N30.114 (3)0.0452 (16)0.0568 (16)0.0074 (16)0.0423 (17)0.0250 (14)
N40.093 (2)0.0457 (16)0.0460 (14)0.0105 (15)0.0359 (15)0.0203 (12)
C10.0476 (16)0.0368 (15)0.0325 (13)0.0019 (12)0.0093 (11)0.0152 (11)
C20.0523 (17)0.0436 (16)0.0368 (14)0.0056 (13)0.0101 (12)0.0183 (12)
C30.066 (2)0.0371 (16)0.0414 (15)0.0091 (14)0.0085 (14)0.0137 (13)
C40.0585 (18)0.0386 (16)0.0321 (13)0.0009 (13)0.0104 (12)0.0107 (12)
C50.0587 (18)0.0434 (16)0.0349 (14)0.0019 (14)0.0152 (13)0.0185 (13)
C60.0512 (16)0.0332 (14)0.0369 (14)0.0030 (12)0.0106 (12)0.0160 (12)
C70.108 (3)0.054 (2)0.0429 (17)0.008 (2)0.0364 (19)0.0066 (15)
C80.080 (2)0.0434 (18)0.073 (2)0.0049 (17)0.0348 (19)0.0329 (17)
C90.0507 (17)0.0372 (15)0.0385 (14)0.0013 (13)0.0107 (12)0.0165 (12)
C100.0591 (19)0.0458 (17)0.0427 (15)0.0010 (14)0.0166 (14)0.0216 (13)
O70.0886 (17)0.0508 (13)0.0470 (12)0.0031 (12)0.0307 (12)0.0245 (10)
O80.0865 (17)0.0348 (11)0.0434 (11)0.0074 (11)0.0286 (11)0.0108 (9)
N50.0580 (15)0.0382 (13)0.0354 (12)0.0090 (11)0.0188 (11)0.0153 (10)
N60.0640 (16)0.0370 (13)0.0394 (12)0.0100 (12)0.0229 (11)0.0178 (10)
N70.106 (2)0.0408 (15)0.0490 (15)0.0177 (15)0.0387 (16)0.0187 (13)
N80.092 (2)0.0459 (16)0.0474 (15)0.0193 (15)0.0378 (15)0.0211 (13)
C110.0421 (15)0.0355 (15)0.0344 (13)0.0046 (12)0.0108 (11)0.0137 (11)
C120.0588 (19)0.0338 (15)0.0426 (15)0.0047 (13)0.0154 (13)0.0137 (12)
C130.063 (2)0.0356 (16)0.0497 (16)0.0018 (14)0.0150 (15)0.0198 (13)
C140.0540 (17)0.0428 (16)0.0365 (14)0.0036 (13)0.0142 (12)0.0206 (12)
C150.0571 (18)0.0358 (15)0.0334 (13)0.0009 (13)0.0121 (12)0.0109 (11)
C160.0477 (16)0.0363 (15)0.0366 (14)0.0008 (12)0.0087 (12)0.0174 (12)
C170.087 (3)0.054 (2)0.0434 (17)0.0062 (18)0.0277 (17)0.0179 (15)
C180.105 (3)0.0334 (17)0.0497 (18)0.0138 (17)0.0233 (19)0.0100 (14)
C190.0492 (16)0.0356 (15)0.0392 (14)0.0055 (12)0.0120 (12)0.0170 (12)
C200.0593 (18)0.0400 (16)0.0373 (14)0.0124 (14)0.0172 (13)0.0169 (12)
P10.0306 (4)0.0380 (4)0.0374 (4)0.0007 (3)0.0113 (3)0.0099 (3)
O30.0435 (12)0.0859 (18)0.0703 (15)0.0042 (12)0.0181 (11)0.0529 (14)
O40.0402 (11)0.0872 (18)0.0503 (12)0.0099 (11)0.0152 (9)0.0419 (12)
O50.0366 (11)0.0469 (14)0.0847 (17)0.0015 (10)0.0162 (12)0.0189 (12)
O60.0416 (11)0.0320 (11)0.0544 (12)0.0023 (8)0.0177 (9)0.0064 (9)
P20.0304 (4)0.0449 (4)0.0466 (4)0.0006 (3)0.0129 (3)0.0180 (3)
O90.0468 (13)0.0571 (15)0.0793 (17)0.0046 (11)0.0302 (12)0.0075 (13)
O100.0455 (13)0.0670 (17)0.0877 (18)0.0144 (12)0.0308 (13)0.0286 (14)
O110.0432 (14)0.183 (4)0.134 (3)0.0069 (18)0.0108 (16)0.133 (3)
O120.0406 (11)0.0653 (15)0.0796 (15)0.0066 (10)0.0148 (11)0.0510 (13)
Geometric parameters (Å, º) top
O1—C41.372 (3)N6—C201.329 (4)
O1—C71.433 (4)N6—H60.8600
O2—C61.354 (4)N7—C201.309 (4)
O2—C81.419 (4)N7—H7D0.8600
N1—C91.279 (4)N7—H7E0.8600
N1—N21.394 (3)N8—C201.328 (4)
N2—C101.335 (4)N8—H8D0.8600
N2—H20.8600N8—H8E0.8600
N3—C101.310 (4)C11—C121.391 (4)
N3—H3A0.8600C11—C161.398 (4)
N3—H3B0.8600C11—C191.459 (4)
N4—C101.324 (4)C12—C131.378 (4)
N4—H4A0.8600C12—H120.9300
N4—H4B0.8600C13—C141.386 (4)
C1—C21.393 (4)C13—H130.9300
C1—C61.400 (4)C14—C151.372 (4)
C1—C91.465 (4)C15—C161.390 (4)
C2—C31.373 (4)C15—H150.9300
C2—H2A0.9300C17—H17A0.9600
C3—C41.385 (4)C17—H17B0.9600
C3—H30.9300C17—H17C0.9600
C4—C51.374 (4)C18—H18A0.9600
C5—C61.397 (4)C18—H18B0.9600
C5—H50.9300C18—H18C0.9600
C7—H7A0.9600C19—H190.9300
C7—H7B0.9600P1—O61.4992 (19)
C7—H7C0.9600P1—O41.501 (2)
C8—H8A0.9600P1—O31.555 (2)
C8—H8B0.9600P1—O51.560 (2)
C8—H8C0.9600O3—H3O0.8200
C9—H90.9300O5—H5O0.8200
O7—C141.368 (3)P2—O101.480 (2)
O7—C171.426 (4)P2—O121.491 (2)
O8—C161.357 (4)P2—O91.547 (3)
O8—C181.433 (4)P2—O111.562 (3)
N5—C191.275 (4)O9—H9O0.8200
N5—N61.395 (3)O11—H11O0.8200
C4—O1—C7116.9 (3)H7D—N7—H7E120.0
C6—O2—C8118.3 (2)C20—N8—H8D120.0
C9—N1—N2113.5 (2)C20—N8—H8E120.0
C10—N2—N1117.8 (3)H8D—N8—H8E120.0
C10—N2—H2121.1C12—C11—C16118.0 (2)
N1—N2—H2121.1C12—C11—C19121.5 (3)
C10—N3—H3A120.0C16—C11—C19120.5 (3)
C10—N3—H3B120.0C13—C12—C11121.8 (3)
H3A—N3—H3B120.0C13—C12—H12119.1
C10—N4—H4A120.0C11—C12—H12119.1
C10—N4—H4B120.0C12—C13—C14118.9 (3)
H4A—N4—H4B120.0C12—C13—H13120.6
C2—C1—C6118.4 (2)C14—C13—H13120.6
C2—C1—C9121.9 (3)O7—C14—C15123.9 (3)
C6—C1—C9119.6 (3)O7—C14—C13115.0 (3)
C3—C2—C1121.5 (3)C15—C14—C13121.1 (3)
C3—C2—H2A119.2C14—C15—C16119.5 (3)
C1—C2—H2A119.2C14—C15—H15120.2
C2—C3—C4119.1 (3)C16—C15—H15120.2
C2—C3—H3120.5O8—C16—C15123.0 (3)
C4—C3—H3120.5O8—C16—C11116.3 (2)
O1—C4—C5123.5 (3)C15—C16—C11120.7 (3)
O1—C4—C3115.2 (3)O7—C17—H17A109.5
C5—C4—C3121.4 (3)O7—C17—H17B109.5
C4—C5—C6119.2 (3)H17A—C17—H17B109.5
C4—C5—H5120.4O7—C17—H17C109.5
C6—C5—H5120.4H17A—C17—H17C109.5
O2—C6—C5123.1 (3)H17B—C17—H17C109.5
O2—C6—C1116.6 (2)O8—C18—H18A109.5
C5—C6—C1120.3 (3)O8—C18—H18B109.5
O1—C7—H7A109.5H18A—C18—H18B109.5
O1—C7—H7B109.5O8—C18—H18C109.5
H7A—C7—H7B109.5H18A—C18—H18C109.5
O1—C7—H7C109.5H18B—C18—H18C109.5
H7A—C7—H7C109.5N5—C19—C11121.2 (3)
H7B—C7—H7C109.5N5—C19—H19119.4
O2—C8—H8A109.5C11—C19—H19119.4
O2—C8—H8B109.5N7—C20—N8121.5 (3)
H8A—C8—H8B109.5N7—C20—N6121.1 (3)
O2—C8—H8C109.5N8—C20—N6117.4 (3)
H8A—C8—H8C109.5O6—P1—O4114.40 (14)
H8B—C8—H8C109.5O6—P1—O3109.89 (13)
N1—C9—C1121.0 (3)O4—P1—O3109.74 (12)
N1—C9—H9119.5O6—P1—O5110.48 (12)
C1—C9—H9119.5O4—P1—O5108.67 (15)
N3—C10—N4121.1 (3)O3—P1—O5103.04 (17)
N3—C10—N2120.9 (3)P1—O3—H3O109.5
N4—C10—N2117.9 (3)P1—O5—H5O109.5
C14—O7—C17117.8 (3)O10—P2—O12116.24 (18)
C16—O8—C18117.8 (2)O10—P2—O9110.25 (13)
C19—N5—N6113.6 (3)O12—P2—O9108.22 (15)
C20—N6—N5118.7 (3)O10—P2—O11109.9 (2)
C20—N6—H6120.6O12—P2—O11108.70 (13)
N5—N6—H6120.6O9—P2—O11102.7 (2)
C20—N7—H7D120.0P2—O9—H9O109.5
C20—N7—H7E120.0P2—O11—H11O109.5
C9—N1—N2—C10178.1 (3)C19—N5—N6—C20174.1 (3)
C6—C1—C2—C31.2 (5)C16—C11—C12—C130.9 (5)
C9—C1—C2—C3178.4 (3)C19—C11—C12—C13179.7 (3)
C1—C2—C3—C40.2 (5)C11—C12—C13—C140.6 (5)
C7—O1—C4—C50.7 (5)C17—O7—C14—C152.9 (5)
C7—O1—C4—C3179.7 (3)C17—O7—C14—C13176.3 (3)
C2—C3—C4—O1177.7 (3)C12—C13—C14—O7179.6 (3)
C2—C3—C4—C51.9 (5)C12—C13—C14—C150.3 (5)
O1—C4—C5—C6177.6 (3)O7—C14—C15—C16179.9 (3)
C3—C4—C5—C62.0 (5)C13—C14—C15—C160.8 (5)
C8—O2—C6—C52.7 (5)C18—O8—C16—C155.0 (5)
C8—O2—C6—C1179.5 (3)C18—O8—C16—C11174.3 (3)
C4—C5—C6—O2177.2 (3)C14—C15—C16—O8179.7 (3)
C4—C5—C6—C10.5 (5)C14—C15—C16—C110.5 (5)
C2—C1—C6—O2178.9 (3)C12—C11—C16—O8178.9 (3)
C9—C1—C6—O20.7 (4)C19—C11—C16—O80.5 (4)
C2—C1—C6—C51.0 (4)C12—C11—C16—C150.4 (4)
C9—C1—C6—C5178.6 (3)C19—C11—C16—C15179.8 (3)
N2—N1—C9—C1178.8 (3)N6—N5—C19—C11178.5 (3)
C2—C1—C9—N110.1 (5)C12—C11—C19—N57.0 (5)
C6—C1—C9—N1169.6 (3)C16—C11—C19—N5173.6 (3)
N1—N2—C10—N32.0 (5)N5—N6—C20—N73.3 (5)
N1—N2—C10—N4178.6 (3)N5—N6—C20—N8176.5 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O60.861.942.780 (3)167
N3—H3A···O10i0.862.483.260 (5)152
N3—H3B···O1ii0.862.593.175 (4)127
N3—H3B···N10.862.332.662 (4)103
N4—H4A···O11i0.862.132.959 (4)161
N4—H4B···O40.862.132.969 (4)166
N6—H6···O120.861.902.736 (3)162
N7—H7D···O4iii0.862.343.177 (4)165
N7—H7E···N50.862.352.678 (4)103
N7—H7E···O7iv0.862.483.060 (4)125
N8—H8D···O5iii0.862.212.976 (3)148
N8—H8E···O100.862.333.173 (5)169
O3—H3O···O12v0.821.742.546 (3)168
O5—H5O···O100.821.682.475 (3)163
O9—H9O···O60.821.742.543 (3)166
O11—H11O···O4vi0.821.732.519 (3)161
C7—H7A···O10vii0.962.423.373 (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) x1, y, z; (vi) x+1, y, z; (vii) x, y1, z+1.

Experimental details

Crystal data
Chemical formulaC10H15N4O2+·H2PO4
Mr320.25
Crystal system, space groupTriclinic, P1
Temperature (K)296
a, b, c (Å)8.4822 (5), 13.6287 (9), 14.3131 (9)
α, β, γ (°)63.081 (5), 81.702 (5), 85.936 (5)
V3)1459.86 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.22
Crystal size (mm)0.75 × 0.38 × 0.19
Data collection
DiffractometerStoe IPDS 2
diffractometer
Absorption correctionIntegration
(X-RED32; Stoe & Cie, 2002)
Tmin, Tmax0.888, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
18714, 5746, 4086
Rint0.096
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.153, 1.03
No. of reflections5746
No. of parameters387
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.58, 0.39

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
O1—C41.372 (3)N7—C201.309 (4)
O1—C71.433 (4)N8—C201.328 (4)
O2—C61.354 (4)C11—C121.391 (4)
O2—C81.419 (4)C11—C191.459 (4)
N3—C101.310 (4)C13—C141.386 (4)
N4—C101.324 (4)C15—C161.390 (4)
C1—C21.393 (4)P1—O61.4992 (19)
C1—C91.465 (4)P1—O41.501 (2)
C3—C41.385 (4)P1—O31.555 (2)
C5—C61.397 (4)P1—O51.560 (2)
O7—C141.368 (3)P2—O101.480 (2)
O7—C171.426 (4)P2—O121.491 (2)
O8—C161.357 (4)P2—O91.547 (3)
O8—C181.433 (4)P2—O111.562 (3)
C4—O1—C7116.9 (3)C14—O7—C17117.8 (3)
C6—O2—C8118.3 (2)C16—O8—C18117.8 (2)
C9—N1—N2113.5 (2)C19—N5—N6113.6 (3)
C10—N2—N1117.8 (3)C20—N6—N5118.7 (3)
O1—C4—C5123.5 (3)O7—C14—C15123.9 (3)
O1—C4—C3115.2 (3)O7—C14—C13115.0 (3)
O2—C6—C5123.1 (3)O8—C16—C15123.0 (3)
O2—C6—C1116.6 (2)O8—C16—C11116.3 (2)
N1—C9—C1121.0 (3)N5—C19—C11121.2 (3)
N3—C10—N4121.1 (3)N7—C20—N8121.5 (3)
N3—C10—N2120.9 (3)N7—C20—N6121.1 (3)
N4—C10—N2117.9 (3)N8—C20—N6117.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···O60.861.942.780 (3)167
N3—H3A···O10i0.862.483.260 (5)152
N3—H3B···O1ii0.862.593.175 (4)127
N3—H3B···N10.862.332.662 (4)103
N4—H4A···O11i0.862.132.959 (4)161
N4—H4B···O40.862.132.969 (4)166
N6—H6···O120.861.902.736 (3)162
N7—H7D···O4iii0.862.343.177 (4)165
N7—H7E···N50.862.352.678 (4)103
N7—H7E···O7iv0.862.483.060 (4)125
N8—H8D···O5iii0.862.212.976 (3)148
N8—H8E···O100.862.333.173 (5)169
O3—H3O···O12v0.821.742.546 (3)168
O5—H5O···O100.821.682.475 (3)163
O9—H9O···O60.821.742.543 (3)166
O11—H11O···O4vi0.821.732.519 (3)161
C7—H7A···O10vii0.962.423.373 (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) x1, y, z; (vi) x+1, y, z; (vii) x, y1, z+1.
 

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