Anilinium dihydrogen phosphate

The triclinic structure of the title compound, C₆H₈N⁺·H₂PO₄⁻, with three symmetry-independent structural units (Z′ = 3), is formed of separate organic and inorganic layers alternating along the b axis. The building blocks of the inorganic layer are deformed H₂PO₄ tetra­hedra assembled into infinite ladders by short and hence strong hydrogen bonds. The anilinium cations forming the organic layer are not hydrogen bonded to one another, but they are anchored by four N—H...O crosslinks between the dihydrogen phosphate chains of adjacent ladders. Two H atoms of each –NH₃ group then form one normal and one bifurcated N—H...O hydrogen bond to the P=O oxygens of two tetra­hedra of one chain, while the third H atom is hydrogen bonded to the nearest O atom of an adjacent chain belonging to another dihydrogen phosphate ladder.

S1. Comment

Anilinium dihydrogen phosphate, (I), belongs to the class of substances that are studied as promising proton conductors, and of which the several important physical properties have roots in the presence of specifically spatially arranged hydrogen bonds of suitable energies. The salt provides a convenient model for proton-conducting materials based on dihydrogen phosphates of organic cations that can form organic ionic plastic crystals (Pringle et al., 2010), and for proton-conducting membranes involving similar building blocks like the membranes employing poly(benzimidazole-co-aniline) (Bhadra et al., 2010).

As the presence of water in the structures of proton-conducting salts usually undesirably decreases their chemical stability and makes them unsuitable for applications at elevated temperatures (Kroupa & Fuith, 1993), where various superprotonic and plastic phases are expected to exist, we have attempted to prepare a compound chemically related to anilinium dihydrogen phosphate monohydrate (Anderson et al., 2006) but crystallizing without water. This work was undertaken in order to determine the geometry of the hydrogen bonds, which can prove crucial for understanding the mechanism of proton transfer.

The atom-numbering scheme of the anilinium cations and dihydrogen phosphate anions of (I) is shown in Fig. 1. The structure is formed of separate organic and inorganic layers alternating along the b axis (Fig. 2). The building blocks of the inorganic layer are deformed H₂PO₄ tetrahedra with two narrow groups of O—P—O bond angles (median values ~105 and ~ 111°) and with the P—O bond lengths falling into two groups (Table 1); the protonated P—O vertices show the expected lengthening compared with the other, presumably P═O, bonds (Blessing, 1986; Mahmoudkhani & Langer, 2002; Demir et al., 2003; Smrčok et al., 2009; Balamurugan et al., 2010; Kaman et al., 2011; Marouani et al., 2011). Examination of the geometry of the anilinium cations forming the organic layers shows that the values of the bond distances, bond angles and torsion angles have expected values (Elmokhtar et al., 1995).

The dihydrogen phosphate anions of (I) are assembled into infinite `ladders' by short and hence strong hydrogen bonds (Fig. 3 and Table 2). The hydrogen bonds with atoms O6 and O10 acting as donors have the shortest O···O separations and, according to the standard classification, they fall within the range for very strong hydrogen bonds, while the other O—H···O hydrogen bonds are ranked as moderately strong hydrogen bonds (Jeffrey, 1997). Considering the flexibility of this arrangement, it is suggested that proton mobility would not be enabled just by simple proton transfer along the O—H···O hydrogen bonds, but also by some reorientational movements of the H₂PO₄ tetrahedra.

The bond lengths and angles in the anilinium cations of (I) are all normal for this moiety. The anilinium cations act as triple donors of N—H···O hydrogen bonds, crosslinking the dihydrogen phosphate chains of adjacent ladders (Fig. 4). Two H atoms of each –NH₃ group form one normal and one bifurcated N—H···O hydrogen bond to the double-bonded O atoms of two tetrahedra of a chain, while the third H atom bonds to the nearest O atom of an adjacent chain. The bifurcated N—H···O hydrogen bonds have recognizable major and minor parts and, in addition to their different lengths, also have very different N—H···O hydrogen-bond angles (Table 2).

In line with the individual N···O separations, these hydrogen bonds formally belong to three groups. Firstly, three rather short and thus strong bonds with N···O separations in the range 2.743 (3)–2.791 (2) Å, secondly five medium-strong hydrogen bonds lying in the range 2.818 (2)–2.924 (2) Å, and finally four weaker hydrogen bonds with the largest N···O separations, viz. 2.965 (2)–3.296 (2) Å. Considering the unimodal distribution of well defined N···O contact distances (Kumara Swamy et al., 2001), the N···O distances of the first and third groups are among those found less frequently, being either significantly shorter or longer than the mean value. The values in the second group agree well with those most frequently reported. Due to the various bonding opportunities, the range of N···O contact distances is noticeably broader in (I) than in chemically related structures, e.g. bis(4-hydroxyanilinium) dihydrogen diphosphate monohydrate (Soumhi & Jouini, 1995), 2-aminopyrimidinium dihydrogen phosphate monohydrate (Marouani et al., 2011), p-phenylazoanilinium phenylphosphonate (Mahmoudkhani & Langer, 2002) or tris(methylammonium) hydrogen phosphate dihydrogen phosphate (Fábry et al., 2006).

Considering the strength of the N—H···O hydrogen bonds in (I), it can be assumed that their dynamics have an impact on proton mobility along the strong O—H···O hydrogen bonds and vice versa. The strength of both O—H···O and N—H···O hydrogen bonds is also documented by the absence of standard ν(OH) and ν(NH) bands in the IR spectrum of (I) and their replacement with a diffuse asymmetric band rising slowly from ~2000 cm^-1 and ending sharply at ~3600 cm^-1. Despite favorable centroid–centroid distances between the phenyl rings, their mutual orientations effectively prevent the formation of π–π interactions.

Related literature

For related literature, see: Anderson et al. (2006); Balamurugan et al. (2010); Bhadra et al. (2010); Blessing (1986); Demir et al. (2003); Elmokhtar et al. (1995); Fábry et al. (2006); Jeffrey (1997); Kaman et al. (2011); Kroupa & Fuith (1993); Kumara Swamy, Kumaraswamy & Kommana (2001); Mahmoudkhani & Langer (2002); Marouani et al. (2011); Pringle et al. (2010); Smrčok et al. (2009); Soumhi & Jouini (1995).

S2. Experimental

Aniline (99.8%, Acros) was purified via the preparation of anilinium chloride as follows. Raw aniline was mixed with 2 M HCl with cooling and the solution filtered through active carbon. The filtrate was concentrated in vacuo and crystallization of anilinium chloride was carried out in a refrigerator. The crystals were filtered off and washed with a small amount of cold water. The wet product was dissolved in water subsequently alkalized by the addition of NaHCO₃, and the mixture was extracted with chloroform four times. The organic phases were collected, washed once with water and dried using anhydrous Na₂SO₄. After filtration, the solution was evaporated in vacuo, providing purified aniline. This was mixed with ~0.03 M H₃PO₄ (Lachema, pure 85%), the concentration of which was determined by titration on methyl orange, in a 1:1.5 molar ratio. The resulting mixture was stirred with heating at 313 K and further diluted in order to dissolve the small amount of salts formed immediately upon mixing. Finally, the solution was filtered and the filtrate was left to crystallize very slowly in air at room temperature.

S3. Refinement

Aromatic H atoms were refined isotropically with U_iso(H) = 1.2U_eq(C), and their positions were constrained to an ideal geometry using an appropriate riding model (C—H = 0.95 Å). For the NH₃ groups, C—N—H angles (109.5°) were kept fixed, while the torsion angles were allowed to refine with starting positions based on the circular Fourier synthesis averaged using the local threefold axis, with U_iso(H) = 1.2U_eq(N) and a constrained N—H distance of 0.98 Å. The positions of the H atoms of the dihydrogen phosphate anions were constrained to an ideal geometry, keeping the O—H bond length fixed at 0.84 Å, and with U_iso(H) = 1.2U_eq(O).

Computing details

Data collection: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); cell refinement: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT (Nonius, 1998) and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: PLATON (Spek, 2009).

Figures

	Fig. 1. The atom-numbering scheme for (a) the dihydrogen phosphate anions of (I) and (b) the anilinium cations of (I). Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The unit-cell packing in (I), viewed along the c axis. All H atoms have been omitted for clarity.
	Fig. 3. A view of part of the crystal structure of (I), showing the spatial arrangement of the dihydrogenphosphate anions. Symmetry codes are defined in Table 2.
	Fig. 4. Detail of the N—H···O hydrogen bonds in (I). Symmetry codes and bond labels are defined in Table 2.

anilinium dihydrogen phosphate

Crystal data

C6H8N^+·H2PO4^−	Z = 6
Mr = 191.12	F(000) = 600
Triclinic, P1	Dx = 1.531 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8040 (3) Å	Cell parameters from 6381 reflections
b = 10.4220 (4) Å	θ = 1.0–29.1°
c = 14.0890 (6) Å	µ = 0.31 mm^−1
α = 86.418 (2)°	T = 150 K
β = 75.8890 (19)°	Prism, colourless
γ = 83.016 (2)°	0.18 × 0.18 × 0.05 mm
V = 1243.71 (8) Å^3

Data collection

Nonius KappaCCD area-detector diffractometer	6720 independent reflections
Radiation source: fine-focus sealed tube	3848 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromator	Rint = 0.067
Detector resolution: 9.091 pixels mm^-1	θmax = 29.2°, θmin = 1.5°
ω and ϕ scans	h = −12→11
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −14→13
Tmin = 0.919, Tmax = 0.987	l = −19→19
23949 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.144	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0674P)^2] where P = (Fo^2 + 2Fc^2)/3
6720 reflections	(Δ/σ)max < 0.001
334 parameters	Δρmax = 0.35 e Å^−3
0 restraints	Δρmin = −0.57 e Å^−3

Special details

Experimental. crystal was coated by epoxy to avoid decomposition

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
N21	0.4345 (2)	0.34092 (16)	0.24020 (14)	0.0181 (4)
H21A	0.5187	0.3731	0.1988	0.022*
H21B	0.4212	0.3719	0.3010	0.022*
H21C	0.3464	0.3657	0.2178	0.022*
C24	0.5156 (3)	−0.0672 (2)	0.25426 (18)	0.0237 (5)
H24	0.5339	−0.1589	0.2574	0.028*
C23	0.6250 (3)	0.0074 (2)	0.27262 (18)	0.0242 (6)
H23	0.7188	−0.0336	0.2880	0.029*
C26	0.3514 (3)	0.1269 (2)	0.22638 (17)	0.0222 (5)
H26	0.2581	0.1681	0.2105	0.027*
C25	0.3795 (3)	−0.0067 (2)	0.23134 (18)	0.0245 (6)
H25	0.3044	−0.0575	0.2189	0.029*
C21	0.4620 (3)	0.1992 (2)	0.24504 (16)	0.0165 (5)
C22	0.5984 (3)	0.1416 (2)	0.26871 (17)	0.0213 (5)
H22	0.6726	0.1927	0.2820	0.026*
N11	0.2303 (2)	0.67911 (16)	0.07871 (14)	0.0227 (5)
H11A	0.2532	0.6444	0.0185	0.027*
H11C	0.1441	0.6463	0.1173	0.027*
H11B	0.3138	0.6592	0.1064	0.027*
C12	0.0596 (3)	0.8820 (2)	0.12359 (18)	0.0215 (5)
H12	−0.0161	0.8336	0.1657	0.026*
C11	0.1978 (3)	0.8205 (2)	0.06882 (17)	0.0185 (5)
C15	0.2807 (3)	1.0225 (2)	−0.00053 (18)	0.0257 (6)
H15	0.3561	1.0707	−0.0430	0.031*
C14	0.1429 (3)	1.0856 (2)	0.05387 (18)	0.0239 (6)
H14	0.1237	1.1772	0.0485	0.029*
C13	0.0330 (3)	1.0161 (2)	0.11607 (18)	0.0250 (6)
H13	−0.0612	1.0600	0.1538	0.030*
C16	0.3090 (3)	0.8887 (2)	0.00678 (18)	0.0235 (5)
H16	0.4036	0.8448	−0.0304	0.028*
N31	0.1103 (2)	0.32682 (16)	0.56741 (14)	0.0190 (4)
H31A	0.0221	0.3568	0.5465	0.023*
H31B	0.1953	0.3597	0.5274	0.023*
H31C	0.0992	0.3518	0.6297	0.023*
C31	0.1335 (3)	0.18453 (19)	0.56522 (17)	0.0171 (5)
C32	0.2686 (3)	0.1239 (2)	0.50684 (17)	0.0219 (5)
H32	0.3477	0.1730	0.4689	0.026*
C33	0.2871 (3)	−0.0100 (2)	0.50437 (18)	0.0241 (6)
H33	0.3794	−0.0533	0.4642	0.029*
C35	0.0364 (3)	−0.0179 (2)	0.61801 (18)	0.0230 (5)
H35	−0.0429	−0.0669	0.6559	0.028*
C36	0.0155 (3)	0.1162 (2)	0.62099 (17)	0.0211 (5)
H36	−0.0773	0.1599	0.6603	0.025*
C34	0.1716 (3)	−0.0808 (2)	0.56031 (18)	0.0234 (5)
H34	0.1854	−0.1726	0.5590	0.028*
P2	0.64036 (7)	0.58964 (5)	0.10131 (4)	0.01612 (15)
O8	0.69915 (17)	0.44627 (13)	0.10256 (12)	0.0200 (4)
O7	0.47842 (18)	0.62076 (15)	0.16555 (11)	0.0222 (4)
O6	0.62779 (18)	0.64060 (15)	−0.00346 (11)	0.0218 (4)
H6	0.7087	0.6115	−0.0448	0.026*
O5	0.76183 (19)	0.66961 (14)	0.12767 (13)	0.0256 (4)
H5	0.8084	0.6256	0.1662	0.031*
P1	0.01352 (7)	0.43251 (5)	0.23218 (4)	0.01665 (15)
O1	0.04333 (18)	0.37131 (16)	0.33073 (12)	0.0236 (4)
H1	−0.0377	0.3877	0.3759	0.028*
O2	−0.09881 (19)	0.34451 (14)	0.20354 (13)	0.0262 (4)
H2	−0.1517	0.3873	0.1678	0.031*
O4	−0.06423 (19)	0.57018 (14)	0.24377 (12)	0.0249 (4)
O3	0.17167 (18)	0.42110 (16)	0.16157 (12)	0.0259 (4)
P3	0.31410 (7)	0.58161 (5)	0.43387 (4)	0.01555 (15)
O11	0.15413 (17)	0.59907 (14)	0.50322 (11)	0.0202 (4)
O10	0.28992 (17)	0.64087 (15)	0.33341 (11)	0.0217 (4)
H10	0.3749	0.6287	0.2906	0.026*
O12	0.38487 (18)	0.44141 (14)	0.42566 (11)	0.0198 (4)
O9	0.43146 (18)	0.66515 (14)	0.46195 (13)	0.0238 (4)
H9	0.4796	0.6217	0.5000	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N21	0.0184 (10)	0.0185 (9)	0.0176 (11)	−0.0028 (8)	−0.0040 (8)	−0.0017 (8)
C24	0.0312 (14)	0.0171 (11)	0.0208 (13)	−0.0040 (10)	−0.0015 (11)	−0.0025 (10)
C23	0.0266 (13)	0.0238 (12)	0.0213 (14)	−0.0014 (11)	−0.0054 (11)	0.0027 (10)
C26	0.0206 (13)	0.0253 (12)	0.0221 (14)	−0.0050 (10)	−0.0063 (11)	−0.0017 (10)
C25	0.0258 (13)	0.0233 (12)	0.0262 (14)	−0.0099 (11)	−0.0052 (11)	−0.0041 (11)
C21	0.0192 (12)	0.0173 (11)	0.0117 (12)	−0.0021 (9)	−0.0005 (9)	−0.0027 (9)
C22	0.0217 (13)	0.0233 (12)	0.0209 (13)	−0.0069 (10)	−0.0067 (10)	−0.0004 (10)
N11	0.0283 (11)	0.0193 (10)	0.0231 (12)	−0.0010 (9)	−0.0113 (9)	−0.0027 (8)
C12	0.0225 (13)	0.0213 (12)	0.0216 (14)	−0.0059 (10)	−0.0056 (11)	0.0009 (10)
C11	0.0215 (12)	0.0185 (11)	0.0180 (13)	−0.0008 (10)	−0.0101 (10)	−0.0022 (9)
C15	0.0301 (14)	0.0275 (13)	0.0207 (14)	−0.0125 (11)	−0.0055 (11)	0.0060 (11)
C14	0.0334 (15)	0.0170 (11)	0.0249 (14)	−0.0033 (11)	−0.0140 (12)	0.0011 (10)
C13	0.0210 (13)	0.0275 (13)	0.0267 (15)	0.0015 (10)	−0.0073 (11)	−0.0045 (11)
C16	0.0209 (12)	0.0295 (13)	0.0198 (13)	−0.0021 (10)	−0.0041 (10)	−0.0028 (10)
N31	0.0223 (10)	0.0168 (9)	0.0194 (11)	−0.0027 (8)	−0.0078 (9)	0.0006 (8)
C31	0.0198 (12)	0.0142 (10)	0.0191 (13)	−0.0006 (9)	−0.0085 (10)	−0.0013 (9)
C32	0.0211 (13)	0.0230 (12)	0.0206 (14)	−0.0046 (10)	−0.0022 (10)	0.0005 (10)
C33	0.0239 (13)	0.0239 (12)	0.0230 (14)	0.0040 (10)	−0.0047 (11)	−0.0062 (10)
C35	0.0228 (13)	0.0227 (12)	0.0249 (14)	−0.0080 (10)	−0.0063 (11)	0.0020 (10)
C36	0.0208 (12)	0.0222 (12)	0.0202 (13)	−0.0019 (10)	−0.0047 (10)	−0.0010 (10)
C34	0.0294 (14)	0.0161 (11)	0.0261 (14)	0.0003 (10)	−0.0102 (11)	−0.0027 (10)
P2	0.0171 (3)	0.0173 (3)	0.0143 (3)	−0.0025 (2)	−0.0044 (2)	0.0005 (2)
O8	0.0240 (9)	0.0160 (8)	0.0224 (9)	−0.0021 (7)	−0.0103 (7)	−0.0006 (7)
O7	0.0217 (9)	0.0281 (9)	0.0144 (9)	0.0006 (7)	−0.0012 (7)	0.0003 (7)
O6	0.0195 (9)	0.0285 (9)	0.0146 (9)	0.0026 (7)	−0.0019 (7)	0.0017 (7)
O5	0.0309 (10)	0.0173 (8)	0.0345 (11)	−0.0061 (7)	−0.0189 (8)	0.0049 (7)
P1	0.0171 (3)	0.0191 (3)	0.0140 (3)	−0.0027 (2)	−0.0044 (2)	0.0007 (2)
O1	0.0188 (9)	0.0339 (9)	0.0149 (9)	0.0040 (7)	−0.0021 (7)	0.0027 (7)
O2	0.0279 (10)	0.0174 (8)	0.0393 (11)	−0.0042 (7)	−0.0198 (8)	0.0028 (8)
O4	0.0337 (10)	0.0192 (8)	0.0261 (10)	0.0015 (7)	−0.0171 (8)	−0.0024 (7)
O3	0.0221 (9)	0.0402 (10)	0.0146 (9)	−0.0056 (8)	−0.0024 (7)	0.0010 (7)
P3	0.0169 (3)	0.0159 (3)	0.0141 (3)	−0.0019 (2)	−0.0042 (2)	0.0002 (2)
O11	0.0190 (8)	0.0245 (8)	0.0156 (9)	−0.0013 (7)	−0.0018 (7)	0.0005 (7)
O10	0.0178 (8)	0.0312 (9)	0.0134 (9)	0.0032 (7)	−0.0022 (7)	0.0023 (7)
O12	0.0234 (9)	0.0167 (8)	0.0211 (9)	−0.0004 (7)	−0.0091 (7)	−0.0033 (7)
O9	0.0248 (9)	0.0173 (8)	0.0345 (11)	−0.0048 (7)	−0.0163 (8)	0.0021 (7)

Geometric parameters (Å, º)

N21—C21	1.468 (3)	N31—H31B	0.9100
N21—H21A	0.9100	N31—H31C	0.9100
N21—H21B	0.9100	C31—C32	1.377 (3)
N21—H21C	0.9100	C31—C36	1.384 (3)
C24—C25	1.384 (3)	C32—C33	1.387 (3)
C24—C23	1.389 (3)	C32—H32	0.9500
C24—H24	0.9500	C33—C34	1.385 (3)
C23—C22	1.389 (3)	C33—H33	0.9500
C23—H23	0.9500	C35—C34	1.383 (3)
C26—C21	1.383 (3)	C35—C36	1.390 (3)
C26—C25	1.384 (3)	C35—H35	0.9500
C26—H26	0.9500	C36—H36	0.9500
C25—H25	0.9500	C34—H34	0.9500
C21—C22	1.382 (3)	P1—O1	1.5588 (16)
C22—H22	0.9500	P1—O2	1.5631 (16)
N11—C11	1.471 (3)	P1—O3	1.4972 (16)
N11—H11A	0.9100	P1—O4	1.5133 (16)
N11—H11C	0.9100	P2—O5	1.5574 (15)
N11—H11B	0.9100	P2—O6	1.5623 (16)
C12—C11	1.378 (3)	P2—O7	1.5007 (16)
C12—C13	1.390 (3)	P2—O8	1.5211 (15)
C12—H12	0.9500	O6—H6	0.8400
C11—C16	1.379 (3)	O5—H5	0.8400
C15—C14	1.381 (3)	O1—H1	0.8400
C15—C16	1.388 (3)	O2—H2	0.8400
C15—H15	0.9500	P3—O9	1.5632 (15)
C14—C13	1.381 (3)	P3—O10	1.5607 (16)
C14—H14	0.9500	P3—O11	1.5034 (16)
C13—H13	0.9500	P3—O12	1.5169 (15)
C16—H16	0.9500	O10—H10	0.8400
N31—C31	1.473 (3)	O9—H9	0.8400
N31—H31A	0.9100
C21—N21—H21A	109.5	C31—N31—H31A	109.5
C21—N21—H21B	109.5	C31—N31—H31B	109.5
H21A—N21—H21B	109.5	H31A—N31—H31B	109.5
C21—N21—H21C	109.5	C31—N31—H31C	109.5
H21A—N21—H21C	109.5	H31A—N31—H31C	109.5
H21B—N21—H21C	109.5	H31B—N31—H31C	109.5
C25—C24—C23	119.4 (2)	C32—C31—C36	122.1 (2)
C25—C24—H24	120.3	C32—C31—N31	119.60 (19)
C23—C24—H24	120.3	C36—C31—N31	118.2 (2)
C22—C23—C24	120.6 (2)	C31—C32—C33	118.8 (2)
C22—C23—H23	119.7	C31—C32—H32	120.6
C24—C23—H23	119.7	C33—C32—H32	120.6
C21—C26—C25	118.7 (2)	C34—C33—C32	120.2 (2)
C21—C26—H26	120.7	C34—C33—H33	119.9
C25—C26—H26	120.7	C32—C33—H33	119.9
C24—C25—C26	120.9 (2)	C34—C35—C36	120.5 (2)
C24—C25—H25	119.6	C34—C35—H35	119.8
C26—C25—H25	119.6	C36—C35—H35	119.8
C22—C21—C26	121.8 (2)	C31—C36—C35	118.3 (2)
C22—C21—N21	118.68 (19)	C31—C36—H36	120.9
C26—C21—N21	119.5 (2)	C35—C36—H36	120.9
C21—C22—C23	118.7 (2)	C35—C34—C33	120.0 (2)
C21—C22—H22	120.7	C35—C34—H34	120.0
C23—C22—H22	120.7	C33—C34—H34	120.0
C11—N11—H11A	109.5	O7—P2—O8	113.31 (9)
C11—N11—H11C	109.5	O7—P2—O5	111.56 (10)
H11A—N11—H11C	109.5	O8—P2—O5	109.98 (9)
C11—N11—H11B	109.5	O7—P2—O6	105.17 (9)
H11A—N11—H11B	109.5	O8—P2—O6	111.52 (9)
H11C—N11—H11B	109.5	O5—P2—O6	104.90 (9)
C11—C12—C13	118.8 (2)	P2—O6—H6	109.5
C11—C12—H12	120.6	P2—O5—H5	109.5
C13—C12—H12	120.6	O3—P1—O4	113.47 (9)
C12—C11—C16	121.6 (2)	O3—P1—O1	105.27 (9)
C12—C11—N11	119.47 (19)	O4—P1—O1	111.71 (10)
C16—C11—N11	118.9 (2)	O3—P1—O2	111.15 (10)
C14—C15—C16	120.1 (2)	O4—P1—O2	110.25 (9)
C14—C15—H15	119.9	O1—P1—O2	104.54 (9)
C16—C15—H15	119.9	P1—O1—H1	109.5
C15—C14—C13	120.2 (2)	P1—O2—H2	109.5
C15—C14—H14	119.9	O11—P3—O12	113.11 (9)
C13—C14—H14	119.9	O11—P3—O10	105.43 (9)
C14—C13—C12	120.2 (2)	O12—P3—O10	111.58 (9)
C14—C13—H13	119.9	O11—P3—O9	111.69 (9)
C12—C13—H13	119.9	O12—P3—O9	109.80 (9)
C11—C16—C15	119.0 (2)	O10—P3—O9	104.87 (9)
C11—C16—H16	120.5	P3—O10—H10	109.5
C15—C16—H16	120.5	P3—O9—H9	109.5
C25—C24—C23—C22	0.4 (4)	C11—C12—C13—C14	0.7 (3)
C23—C24—C25—C26	0.1 (4)	C12—C11—C16—C15	−0.1 (3)
C21—C26—C25—C24	−0.2 (3)	N11—C11—C16—C15	−178.1 (2)
C25—C26—C21—C22	−0.3 (3)	C14—C15—C16—C11	0.1 (3)
C25—C26—C21—N21	−180.0 (2)	C36—C31—C32—C33	−0.3 (3)
C26—C21—C22—C23	0.7 (3)	N31—C31—C32—C33	−178.9 (2)
N21—C21—C22—C23	−179.6 (2)	C31—C32—C33—C34	−0.4 (3)
C24—C23—C22—C21	−0.8 (3)	C32—C31—C36—C35	0.6 (3)
C13—C12—C11—C16	−0.3 (3)	N31—C31—C36—C35	179.2 (2)
C13—C12—C11—N11	177.8 (2)	C34—C35—C36—C31	−0.2 (3)
C16—C15—C14—C13	0.2 (4)	C36—C35—C34—C33	−0.5 (4)
C15—C14—C13—C12	−0.6 (4)	C32—C33—C34—C35	0.8 (4)