Bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate at 292 and 150 K

The title compound, 2C₈H₂₀N⁺·HSO₄^-·H₂PO₄^-, was crystallized in a desiccator over P₄O₁₀ from a water solution of stoichiometric amounts of tetraethyl­ammonium hydroxide and sulfuric and phosphoric acids. The compound is deliquescent. The structure contains two symmetry-independent cations in nearly the same conformation, as well as two symmetry-independent anions, the central atoms of which are equally occupied by P and S. The anions are interconnected by short O...O hydrogen bonds into one-dimensional chains. The distances and angles between some of the methyl or methyl­ene groups and anionic O atoms indicate the presence of C-H...O hydrogen bonds. The structure was determined from data at 292 (2) and 150 (2) K. These room- and low-temperature structures are virtually the same, with the exception of the localization of the H atoms that participate in the symmetry-restricted O...O hydrogen bonds. A differential scanning calorimetry experiment indicated no phase transition below the temperature at which the compound started to decompose (353 K), down to 93 K.

S1. Comment

To date, no structure of either tetraethylammonium dihydrogenphosphate or hydrogensulfate, or of tetraethylammonium with mixed dihydrogenphosphate/hydrogensulfate anions, has been studied [Cambridge Structural Database (CSD), April 2002 release; Allen, 2002]. Furthermore, until now, no structure of an organic compound with mixed dihydrogenphosphate/hydrogensulfate anions has been included in the CSD. Other reasons for the synthesis of the title compound, (I), were, firstly, to compare the architecture of the interbonded anions in compounds that contain large (e.g. tetraethylammonium, tetramethylammonium or Cs⁺) and small (e.g. K⁺) cations. Secondly, we wished to characterize plausible phase transitions in (I). For example, in tetramethylammonium hydrogensulfate, [N(CH₃)₄]HSO₄ (Speziali & Chapuis, 1991), three phase transitions were detected. In some cases, phase transitions at elevated temperatures can lead to superprotonic phases in related compounds. The above-mentioned [N(CH₃)₄]HSO₄ can be given as such an example. This compound is reported to be a superprotonic conductor above 450 K (Blinc et al., 1984). On the other hand, CsHSO₄·CsH₂PO₄ (Chisholm & Haile, 1999) can be given as an example of a superprotonic conductor with mixed dihydrogenphosphate/hydrogensulfate anions. The onset of the transition to the superprotonic phase in the latter compound takes place at 334 K (Chisholm & Haile, 1999). The ability for proton conduction depends, inter alia, on the structure of the anionic moiety as well as on the cation size. For example, while the above-mentioned CsHSO₄·CsH₂PO₄ is a superprotonic conductor, the closely related compound KHSO₄·KH₂PO₄ is not. The latter compound was found to be either strictly isostructural (Averbuch-Pouchot & Durif, 1980; Fábry et al., 2002) with CsHSO₄·CsH₂PO₄ or to exist as a superstructure (Stiewe & Kemnitz, 2000). \sch

The interatomic distances and angles in the cationic moities of (I) are normal. Both tetraethylammonium cations (Fig. 1) have a similar conformation; the unit-weight r.m.s. fit on the non-H atoms of both molecules resulted in 0.024 and 0.031 Å for room and low-temperature data, respectively (Spek, 2002). Application of the instructions SAME and DELU with their default values (SHELXL97; Sheldrick, 1997) for both tetraethylammonium cations in the refinement of either the room- and low-temperature data resulted in almost the same coordinates and displacement parameters within standard uncertainty as in the corresponding refinements where these restraints were not applied.

The very large tetraethylammonium cations are situated in cavities formed by the zigzag anionic chains. The cations are interconnected by short O···O hydrogen bonds (Tables 2 and 4; Fig. 2). In addition to the O—H···O hydrogen bonds that are discussed below, there are a number of relatively short C—H···O contacts. Some of these conform to the geometrical criteria for C—H···O hydrogen bonds (Desiraju & Steiner, 1999). The latter contacts are also listed in Tables 2 and 4. It is of interest that the H atoms from the methylene groups tend to be closer to the O atoms than those from the methyl groups.

As stated above, the anions are interconnected by the hydrogen bonds, thus forming one-dimensional chains. These chains are parallel to [110] (Fig. 2) and are arranged in a hexagonal packing. The non-equivalent anions differ by their hydrogen bonding. There are two symmetry-restricted hydrogen bonds that connect a pair of anions with the central P2/S2 atom. A symmetry-free O2···O3 hydrogen bond links another pair of symmetry-equivalent anions with the central P1/S1 atom. Another symmetry-free hydrogen bond, O1···O5, links both pairs of symmetry-nonequivalent anions. The sites that can be occupied by H atoms from the OH groups indicate - under the assumption that all the sites are fully occupied by the hydroxyl H atoms - that the ratio of the sulfate and phosphate anions is 1:1. It should be noted that stoichiometric considerations exclude a higher content of P than of S because there would then be no room left for the excess H atom.

In order to determine the ratio of P/S, an electron microprobe analysis was carried out, using a Jeol JXA-733 (Jeol Ltd., Tokyo, Japan) with a Kevex Quantum energy-dispersive spectrometer (Delta Class Analyzer; Kevex Instruments, San Carlos, California, USA - company no longer trades)]. The experiment was performed on a sample that had previously been dissolved and then dried, in order to create a thin film that was easier to handle than a hygroscopic bulk crystal sample. The dry precipitate was covered by a graphite layer 30–40 nm thick. The energy of the impinging electron beam was 8 K eV, the current was 4 nA, and the scanned area was 0.3 × 0.2 mm. The measurement was performed in five regions. The standards used were sfalerite ZnS (for S) and apatite (for P). The problem of the present analysis is that the light elements H, C, N and O are difficult to account for accurately. Therefore, the weight concentrations of P and S were calculated by the ZAF (please define) method (Philibert & Tixier, 1968), while the concentrations of the remaining elements that corresponded to the results of the structure analysis were kept fixed during the iterative calculation. The contents of P and S were found to be 1.04 (2) and 0.95 (2), respectively. If we estimate a total analytical error of ~5%_rel, which is commonly accepted, we can conclude that the assumed ratio of 1:1 for P and S is valid, and is therefore in accordance with the highest number of H atoms that can be accommodated into the structural model. Thus the electron microprobe analysis shows that the structure most probably contains an equal number of dihydrogenphosphates and hydrogensulfates.

Another observation is that the chains are composed of two different pairs of anions. This fact would rather support the idea that the dihydrogenphosphates and dihydrogensulfates should this be hydrogensulfates? are unequally distributed between the indpendent anionic sites. In order to elucidate this hypothesis, several models with different substitutions of P and S were refined. However, the best indicators of refinement yielded an unrealistic model, where the central anionic atoms were composed of P only, while the worst result yielded a model with the central atoms composed of S only. Also, refinement of both models where one of the central atoms was either P or S resulted in refinement indicators comparable with those of the model with the central atom composed purely of the S. The constrained refinement of occupation by P and S at both sites occupied by the central anionic atoms was unstable for both structure determinations at the two temperatures.

On the other hand, there arguments that favour occupational disorder of the anions at both anionic sites. Firstly, the electron density of both central atoms is about the same. Moreover, the distances between the central atoms (P/S) and neighbouring O atoms correspond excellently to the P/S—O distances observed, for example, in KHSO₄·KH₂PO₄ (Averbuch-Pouchot & Durif, 1980). Finally, the distribution of the H atoms is intimately dependent on the composition of the central atoms of the anionic pairs, i.e. whether the anions are rather dihydrogenphosphates or hydrogensulfates; according to the acid strengths, a dihydrogenphosphate anion should be a hydrogen-bond acceptor, while a hydrogensulfate should be a donor.

All the H atoms could be distinguished in the difference Fourier maps, although those maxima that were assigned to the hydroxyl H atoms were the least prominent, being as low as ~0.3 e Å⁻³ (the H atoms were then fixed to the pertinent O atoms). It is important that, for the 150 K data, atoms H1O and H5O involved in the O1···O5 symmetry-unrestricted hydrogen bond were invariably found disordered, irrespective of whether the central anionic atoms were assumed to be P or S. The difference Fourier maps calculated by JANA2000 (Petříček & Dušek, 2000) showed a build-up of saddle-like smeared electron density in the region of atoms O1 and O5, with two peaks. [JANA2000 uses unweighted |F_obs|, in contrast to SHELXL97 (Sheldrick, 1997).] This particular hydrogen disorder concerning the H atoms on O1 and O5 serves as another piece of evidence that occupationally disordered dihydrogenphosphates and hydrogensulfates are present in both anionic sites of (I).

With regard to these facts, a model with equal distribution of P and S at each site was chosen. The H-atom positions, however, should be taken with some reserve.

The hydroxyl atoms H6O and H7O are involved in the respective symmetry-restricted hydrogen bonds. The refinement based on the room-temperature data resulted in localization of these latter H atoms just at the mid-point between the O atoms, in contrast to the refinement based on the low-temperature data. This is in accordance with the observation of Wilson (2001), who studied an adduct of urea and phosphoric acid (1:1) by neutron diffraction between 150 and 335 K. He found that the H atom in a short symmetry-free hydrogen-bond (~2.40 Å long) tends to move with increasing temperature towards the centre of the hydrogen bond.

Although the hydrogen bond between atoms O2 and O3 is symmetry-unrestricted, the pertinent atom HO3 is closer to the centre of this hydrogen bond at room temperature. This can be compared with the structure of K₄(HSeO₄)₃(H₂PO₄), which was determined from neutron diffraction data by Troyanov et al. (2000).

The main difference in the anionic arrangement between (I) and other compounds with known mixed phosphate/sulfate anions, such as KHSO₄·KH₂PO₄ (Averbuch-Pouchot & Durif, 1980), NH₄SO₄·NH₄H₂PO₄ (Averbuch-Pouchot, 1981), CsHSO₄·CsH₂PO₄ (Chisholm & Haile, 1999), α-Cs₃(HSO₄)₂(H₂PO₄) (Haile et al., 1995) and β-Cs₃(HSO₄)₂[H_{2 − x}(P_{1 − x},S_x)O₄] (x ~0.5; Haile et al., 1998; Haile & Klooster, 1999), consists of the existence of interbonded anion chains in the latter compounds, while in (I), these chains are one-dimensional.

Differential scanning calorimetry [Perkin Elmer DSC 7, Pyris Software (PerkinElmer Instruments, 2001), m = 22 mg, temperature interval 93–398 K, scanning rate 10 K min⁻¹] showed an anomaly (hump) indicating the start of decomposition at 353 K. It did not show any reproducible anomaly indicating a structural phase transition.

S2. Experimental

Compound (I) crystallized in a desiccator over P₄O₁₀ from a water solution of stoichiometric amounts of tetraethylammonium hydroxide and sulfuric and phosphoric acids.

S3. Refinement

Atoms P1/S1 and P2/S2 were assumed to occupy the same respective sites and to have the same respective anisotropic displacement parameters [instructions EXYZ and EADP in SHELXL97 (Sheldrick, 1997)]. The occupancy of each S atom and ? Something missing here? was considered to be the same (1/2). The methylene and methyl H atoms were constrained by instructions AFIX23 and AFIX137 (SHELXL97), respectively. The anionic H atoms were constrained by the instruction AFIX3 (SHELXL97). This means that all the H atoms were assumed to ride on the atoms they were attached to. In addition, the methyl groups were assumed to rotate along the C—C bonds and to maintain tetrahedral angles. The methylene geometry was also idealized with the same C—H distances. Isotropic displacement parameters of the H atoms were assumed to be 1.2 times that of the pertinent C or O atom for methylene and anionic H atoms, respectively, and 1.5 times that of the parent C atom for methyl H atoms.

Computing details

For both compounds, data collection: COLLECT (Nonius, 1997-2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997). Molecular graphics: ORTEPIII (Burnett & Johnson, 1996) for (I); PLATON (Spek, 2002) for (II). For both compounds, software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the independent molecules of (I) at 150 K. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Fig. 2. A view of the structure of (I) at 292 K, projected along the monoclinic b axis. The structure at 150 K is virtually the same, except for the disorder of atoms H6O and H7O, which are involved in the symmetry-restricted hydrogen bonds O6···O6 and O7···O7, respectively. The tetraethylammonium cations are symbolized by large circles. The right-hand side of the picture shows the anionic chains only.

(I) bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate

Crystal data

2C8H20N^+·HSO4^−·H2PO4^−	F(000) = 1984
Mr = 454.56	Dx = 1.303 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 20021 reflections
a = 28.0787 (6) Å	θ = 1.0–27.5°
b = 11.8671 (2) Å	µ = 0.25 mm^−1
c = 14.1533 (2) Å	T = 292 K
β = 100.739 (1)°	Plate, colourless
V = 4633.46 (14) Å^3	0.40 × 0.20 × 0.05 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	4578 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.029
Graphite monochromator	θmax = 27.5°, θmin = 3.7°
Detector resolution: 9.091 pixels mm^-1	h = −36→36
ω scans	k = −15→15
17929 measured reflections	l = −18→18
5298 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.123	w = 1/[σ^2(Fo^2) + (0.0535P)^2 + 3.5454P] where P = (Fo^2 + 2Fc^2)/3
S = 1.10	(Δ/σ)max = 0.001
5298 reflections	Δρmax = 0.32 e Å^−3
262 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
110 constraints	Extinction coefficient: 0.0024 (5)
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
P1	0.788396 (15)	0.72685 (4)	0.14130 (3)	0.03634 (14)	0.50
S1	0.788396 (15)	0.72685 (4)	0.14130 (3)	0.03634 (14)	0.50
O1	0.84180 (4)	0.72473 (13)	0.18577 (9)	0.0512 (3)
H1O	0.8701	0.7480	0.1423	0.061*	0.50
O2	0.77983 (5)	0.63771 (11)	0.06363 (9)	0.0510 (3)
O3	0.77836 (6)	0.84127 (11)	0.09330 (11)	0.0611 (4)
H3O	0.7495	0.8510	0.0183	0.073*
O4	0.76006 (5)	0.70756 (14)	0.21609 (10)	0.0590 (4)
P2	0.955566 (14)	0.76511 (4)	0.11642 (3)	0.03452 (13)	0.50
S2	0.955566 (14)	0.76511 (4)	0.11642 (3)	0.03452 (13)	0.50
O5	0.90187 (4)	0.77781 (13)	0.07714 (9)	0.0514 (3)
H5O	0.8770	0.7576	0.1264	0.062*	0.50
O6	0.96063 (5)	0.67043 (10)	0.19045 (9)	0.0471 (3)
H6O	1.0000	0.6718	0.2500	0.057*
O7	0.97263 (5)	0.87372 (11)	0.16893 (9)	0.0528 (3)
H7O	1.0000	0.8668	0.2500	0.063*
O8	0.98127 (6)	0.74207 (14)	0.03844 (11)	0.0617 (4)
N1	0.62202 (5)	0.46714 (11)	0.66987 (9)	0.0333 (3)
C1	0.59295 (6)	0.35941 (14)	0.65326 (13)	0.0431 (4)
H1A	0.5842	0.3466	0.5845	0.052*
H1B	0.6135	0.2973	0.6806	0.052*
C2	0.63844 (7)	0.48972 (16)	0.77639 (12)	0.0448 (4)
H2A	0.6575	0.5585	0.7839	0.054*
H2B	0.6100	0.5027	0.8046	0.054*
C3	0.59162 (6)	0.56803 (14)	0.62977 (13)	0.0423 (4)
H3A	0.5644	0.5742	0.6629	0.051*
H3B	0.6111	0.6355	0.6441	0.051*
C4	0.66512 (6)	0.45188 (15)	0.62014 (13)	0.0407 (4)
H4A	0.6841	0.3884	0.6494	0.049*
H4B	0.6531	0.4331	0.5532	0.049*
C5	0.54729 (8)	0.35759 (19)	0.69520 (18)	0.0618 (6)
H5A	0.5554	0.3696	0.7634	0.093*
H5B	0.5316	0.2858	0.6826	0.093*
H5C	0.5258	0.4162	0.6663	0.093*
C6	0.66807 (9)	0.3972 (2)	0.83225 (15)	0.0640 (6)
H6A	0.6486	0.3305	0.8310	0.096*
H6B	0.6787	0.4209	0.8976	0.096*
H6C	0.6958	0.3812	0.8036	0.096*
C7	0.57227 (8)	0.5645 (2)	0.52305 (16)	0.0639 (6)
H7A	0.5988	0.5648	0.4891	0.096*
H7B	0.5522	0.6292	0.5047	0.096*
H7C	0.5535	0.4972	0.5075	0.096*
C8	0.69790 (7)	0.55294 (19)	0.62406 (18)	0.0596 (5)
H8A	0.6806	0.6137	0.5882	0.089*
H8B	0.7257	0.5338	0.5967	0.089*
H8C	0.7083	0.5757	0.6898	0.089*
N2	0.87497 (5)	0.54033 (11)	0.43096 (9)	0.0347 (3)
C9	0.84074 (6)	0.63965 (14)	0.42113 (13)	0.0417 (4)
H9A	0.8278	0.6512	0.3534	0.050*
H9B	0.8591	0.7064	0.4446	0.050*
C10	0.89679 (7)	0.51758 (17)	0.53560 (13)	0.0499 (5)
H10A	0.8711	0.4930	0.5682	0.060*
H10B	0.9197	0.4559	0.5383	0.060*
C11	0.84855 (7)	0.43328 (15)	0.39276 (14)	0.0466 (4)
H11A	0.8713	0.3711	0.4036	0.056*
H11B	0.8234	0.4184	0.4297	0.056*
C12	0.91399 (6)	0.57015 (15)	0.37404 (13)	0.0405 (4)
H12A	0.8985	0.5897	0.3090	0.049*
H12B	0.9311	0.6364	0.4026	0.049*
C13	0.79871 (8)	0.6284 (2)	0.47399 (19)	0.0649 (6)
H13A	0.7795	0.5641	0.4499	0.097*
H13B	0.7791	0.6951	0.4640	0.097*
H13C	0.8110	0.6188	0.5415	0.097*
C14	0.92234 (9)	0.6160 (2)	0.58990 (15)	0.0678 (6)
H14A	0.9478	0.6415	0.5584	0.102*
H14B	0.9359	0.5932	0.6544	0.102*
H14C	0.8996	0.6761	0.5915	0.102*
C15	0.82562 (9)	0.4356 (2)	0.28745 (17)	0.0667 (6)
H15A	0.8037	0.4982	0.2752	0.100*
H15B	0.8081	0.3667	0.2707	0.100*
H15C	0.8504	0.4432	0.2495	0.100*
C16	0.95046 (8)	0.47772 (19)	0.36924 (16)	0.0572 (5)
H16A	0.9636	0.4521	0.4331	0.086*
H16B	0.9761	0.5063	0.3397	0.086*
H16C	0.9348	0.4161	0.3319	0.086*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0330 (2)	0.0390 (2)	0.0353 (2)	−0.00173 (15)	0.00178 (16)	−0.00125 (16)
S1	0.0330 (2)	0.0390 (2)	0.0353 (2)	−0.00173 (15)	0.00178 (16)	−0.00125 (16)
O1	0.0342 (6)	0.0718 (9)	0.0446 (7)	−0.0047 (6)	−0.0001 (5)	0.0162 (6)
O2	0.0664 (9)	0.0395 (7)	0.0433 (7)	0.0082 (6)	0.0007 (6)	−0.0043 (5)
O3	0.0688 (9)	0.0389 (7)	0.0625 (9)	−0.0007 (6)	−0.0211 (7)	−0.0032 (6)
O4	0.0466 (8)	0.0821 (10)	0.0514 (8)	−0.0092 (7)	0.0172 (6)	−0.0086 (7)
P2	0.0320 (2)	0.0391 (2)	0.0309 (2)	−0.00340 (15)	0.00188 (15)	0.00306 (15)
S2	0.0320 (2)	0.0391 (2)	0.0309 (2)	−0.00340 (15)	0.00188 (15)	0.00306 (15)
O5	0.0344 (6)	0.0741 (9)	0.0426 (7)	−0.0017 (6)	−0.0009 (5)	0.0183 (6)
O6	0.0465 (7)	0.0431 (7)	0.0456 (7)	−0.0093 (5)	−0.0072 (5)	0.0104 (5)
O7	0.0656 (9)	0.0377 (7)	0.0476 (7)	−0.0056 (6)	−0.0087 (6)	0.0032 (5)
O8	0.0580 (9)	0.0823 (11)	0.0485 (8)	0.0079 (7)	0.0196 (7)	−0.0010 (7)
N1	0.0331 (7)	0.0320 (6)	0.0359 (7)	0.0034 (5)	0.0089 (5)	−0.0056 (5)
C1	0.0455 (9)	0.0345 (8)	0.0498 (10)	−0.0032 (7)	0.0099 (7)	−0.0100 (7)
C2	0.0475 (10)	0.0508 (10)	0.0366 (8)	−0.0040 (8)	0.0089 (7)	−0.0115 (7)
C3	0.0370 (8)	0.0358 (8)	0.0553 (10)	0.0090 (7)	0.0121 (7)	−0.0027 (7)
C4	0.0371 (8)	0.0445 (9)	0.0434 (9)	0.0112 (7)	0.0151 (7)	−0.0019 (7)
C5	0.0499 (11)	0.0556 (12)	0.0840 (15)	−0.0133 (9)	0.0230 (10)	−0.0069 (11)
C6	0.0653 (13)	0.0824 (16)	0.0417 (10)	0.0066 (12)	0.0029 (9)	0.0051 (10)
C7	0.0584 (13)	0.0676 (14)	0.0614 (13)	0.0224 (10)	0.0000 (10)	0.0074 (11)
C8	0.0426 (10)	0.0591 (12)	0.0818 (15)	0.0003 (9)	0.0241 (10)	0.0024 (11)
N2	0.0382 (7)	0.0315 (7)	0.0360 (7)	0.0033 (5)	0.0106 (5)	0.0072 (5)
C9	0.0419 (9)	0.0341 (8)	0.0500 (9)	0.0083 (7)	0.0105 (7)	0.0083 (7)
C10	0.0614 (11)	0.0530 (11)	0.0361 (9)	0.0175 (9)	0.0111 (8)	0.0125 (8)
C11	0.0487 (10)	0.0340 (8)	0.0607 (11)	−0.0041 (7)	0.0195 (8)	0.0015 (8)
C12	0.0409 (9)	0.0419 (9)	0.0413 (9)	−0.0013 (7)	0.0144 (7)	0.0076 (7)
C13	0.0534 (12)	0.0591 (13)	0.0889 (16)	0.0146 (10)	0.0306 (11)	0.0077 (11)
C14	0.0714 (14)	0.0811 (16)	0.0454 (11)	0.0183 (12)	−0.0033 (10)	−0.0073 (11)
C15	0.0639 (14)	0.0629 (14)	0.0686 (14)	−0.0144 (11)	−0.0001 (11)	−0.0108 (11)
C16	0.0495 (11)	0.0641 (13)	0.0629 (12)	0.0119 (9)	0.0233 (9)	0.0105 (10)

Geometric parameters (Å, º)

P1—O4	1.4559 (14)	C5—H5A	0.9600
P1—O2	1.5123 (13)	C5—H5B	0.9600
P1—O1	1.5145 (12)	C5—H5C	0.9600
P1—O3	1.5210 (14)	C6—H6A	0.9600
P2—O8	1.4528 (14)	C6—H6B	0.9600
P2—O5	1.5140 (12)	C6—H6C	0.9600
P2—O7	1.5201 (13)	C7—H7A	0.9600
P2—O6	1.5247 (12)	C7—H7B	0.9600
N1—C1	1.511 (2)	C7—H7C	0.9600
N1—C2	1.516 (2)	C8—H8A	0.9600
N1—C3	1.518 (2)	C8—H8B	0.9600
N1—C4	1.5198 (19)	C8—H8C	0.9600
C1—C5	1.510 (3)	C9—H9A	0.9700
C2—C6	1.509 (3)	C9—H9B	0.9700
C3—C7	1.508 (3)	C10—H10A	0.9700
C4—C8	1.507 (3)	C10—H10B	0.9700
N2—C9	1.511 (2)	C11—H11A	0.9700
N2—C10	1.518 (2)	C11—H11B	0.9700
N2—C12	1.518 (2)	C12—H12A	0.9700
N2—C11	1.519 (2)	C12—H12B	0.9700
C9—C13	1.516 (3)	C13—H13A	0.9600
C10—C14	1.505 (3)	C13—H13B	0.9600
C11—C15	1.510 (3)	C13—H13C	0.9600
C12—C16	1.511 (3)	C14—H14A	0.9600
C1—H1A	0.9700	C14—H14B	0.9600
C1—H1B	0.9700	C14—H14C	0.9600
C2—H2A	0.9700	C15—H15A	0.9600
C2—H2B	0.9700	C15—H15B	0.9600
C3—H3A	0.9700	C15—H15C	0.9600
C3—H3B	0.9700	C16—H16A	0.9600
C4—H4A	0.9700	C16—H16B	0.9600
C4—H4B	0.9700	C16—H16C	0.9600
O4—P1—O2	112.59 (9)	H5B—C5—H5C	110
O4—P1—O1	109.16 (8)	C2—C6—H6A	110
O2—P1—O1	107.55 (8)	C2—C6—H6B	110
O4—P1—O3	112.57 (10)	H6A—C6—H6B	110
O2—P1—O3	107.99 (7)	C2—C6—H6C	110
O1—P1—O3	106.69 (8)	H6A—C6—H6C	110
O8—P2—O5	109.97 (8)	H6B—C6—H6C	110
O8—P2—O7	112.02 (9)	C3—C7—H7A	110
O5—P2—O7	107.26 (8)	C3—C7—H7B	110
O8—P2—O6	112.80 (9)	H7A—C7—H7B	110
O5—P2—O6	106.54 (7)	C3—C7—H7C	110
O7—P2—O6	107.96 (7)	H7A—C7—H7C	110
C1—N1—C2	111.08 (13)	H7B—C7—H7C	110
C1—N1—C3	111.06 (13)	C4—C8—H8A	110
C2—N1—C3	106.15 (12)	C4—C8—H8B	110
C1—N1—C4	106.29 (12)	H8A—C8—H8B	110
C2—N1—C4	111.15 (13)	C4—C8—H8C	110
C3—N1—C4	111.20 (13)	H8A—C8—H8C	110
C5—C1—N1	115.11 (14)	H8B—C8—H8C	110
C6—C2—N1	115.35 (15)	N2—C9—H9A	109
C7—C3—N1	115.17 (14)	C13—C9—H9A	109
C8—C4—N1	114.95 (14)	N2—C9—H9B	109
C9—N2—C10	111.28 (13)	C13—C9—H9B	109
C9—N2—C12	106.20 (12)	H9A—C9—H9B	108
C10—N2—C12	111.06 (13)	C14—C10—H10A	108
C9—N2—C11	111.07 (13)	N2—C10—H10A	108
C10—N2—C11	106.26 (13)	C14—C10—H10B	108
C12—N2—C11	111.04 (13)	N2—C10—H10B	108
N2—C9—C13	115.22 (14)	H10A—C10—H10B	108
C14—C10—N2	115.33 (16)	C15—C11—H11A	109
C15—C11—N2	115.24 (15)	N2—C11—H11A	109
C16—C12—N2	114.65 (14)	C15—C11—H11B	109
P1—O1—H1O	121	N2—C11—H11B	109
P1—O1—H5O	119	H11A—C11—H11B	108
P1—O3—H3O	121	C16—C12—H12A	108.6
P2—O5—H1O	116	N2—C12—H12A	108.6
P2—O5—H5O	117	C16—C12—H12B	108.6
P2—O6—H6O	114	N2—C12—H12B	108.6
P2—O7—H7O	118	H12A—C12—H12B	107.6
C5—C1—H1A	109	C9—C13—H13A	110
N1—C1—H1A	109	C9—C13—H13B	110
C5—C1—H1B	109	H13A—C13—H13B	110
N1—C1—H1B	109	C9—C13—H13C	110
H1A—C1—H1B	108	H13A—C13—H13C	110
C6—C2—H2A	108	H13B—C13—H13C	110
N1—C2—H2A	108	C10—C14—H14A	110
C6—C2—H2B	108	C10—C14—H14B	110
N1—C2—H2B	108	H14A—C14—H14B	110
H2A—C2—H2B	108	C10—C14—H14C	110
C7—C3—H3A	109	H14A—C14—H14C	110
N1—C3—H3A	109	H14B—C14—H14C	110
C7—C3—H3B	109	C11—C15—H15A	110
N1—C3—H3B	109	C11—C15—H15B	110
H3A—C3—H3B	108	H15A—C15—H15B	110
C8—C4—H4A	109	C11—C15—H15C	110
N1—C4—H4A	109	H15A—C15—H15C	110
C8—C4—H4B	109	H15B—C15—H15C	110
N1—C4—H4B	109	C12—C16—H16A	110
H4A—C4—H4B	108	C12—C16—H16B	110
C1—C5—H5A	110	H16A—C16—H16B	110
C1—C5—H5B	110	C12—C16—H16C	110
H5A—C5—H5B	110	H16A—C16—H16C	110
C1—C5—H5C	110	H16B—C16—H16C	110
H5A—C5—H5C	110
C1—N1—C2—C6	57.0 (2)	C9—N2—C10—C14	−55.3 (2)
C1—N1—C3—C7	−60.5 (2)	C9—N2—C11—C15	61.3 (2)
C1—N1—C4—C8	177.25 (16)	C9—N2—C12—C16	−176.18 (16)
C2—N1—C3—C7	178.64 (17)	C10—N2—C11—C15	−177.53 (17)
C2—N1—C4—C8	−61.8 (2)	C10—N2—C12—C16	62.7 (2)
C2—N1—C1—C5	60.4 (2)	C10—N2—C9—C13	−58.4 (2)
C3—N1—C4—C8	56.27 (19)	C11—N2—C12—C16	−55.3 (2)
C3—N1—C1—C5	−57.5 (2)	C11—N2—C9—C13	59.8 (2)
C3—N1—C2—C6	177.85 (16)	C11—N2—C10—C14	−176.37 (16)
C4—N1—C1—C5	−178.61 (16)	C12—N2—C9—C13	−179.37 (17)
C4—N1—C2—C6	−61.1 (2)	C12—N2—C10—C14	62.8 (2)
C4—N1—C3—C7	57.6 (2)	C12—N2—C11—C15	−56.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2^i	1.22	1.30	2.5125 (18)	178
O1—H1O···O5	1.13	1.44	2.5636 (19)	174
O5—H5O···O1	1.10	1.46	2.5636 (19)	175
O6—H6O···O6^ii	1.26	1.26	2.518 (2)	179
O7—H7O···O7^ii	1.26	1.26	2.513 (2)	173
C1—H1A···O5^iii	0.97	2.53	3.431 (2)	155
C1—H1A···O8^iii	0.97	2.60	3.397 (2)	140
C2—H2A···O1^iv	0.97	2.61	3.459 (2)	147
C2—H2A···O3^iv	0.97	2.55	3.358 (2)	140
C2—H2B···O7^iv	0.97	2.83	3.722 (2)	154
C3—H3A···O7^v	0.97	2.67	3.555 (2)	152
C3—H3A···O7^iv	0.97	2.84	3.710 (2)	150
C4—H4A···O4^vi	0.97	2.45	3.344 (2)	154
C4—H4B···O5^iii	0.97	2.85	3.694 (2)	146
C5—H5C···O7^v	0.96	2.91	3.796 (3)	154
C6—H6C···O4^vi	0.96	2.60	3.536 (3)	166
C7—H7B···O8^v	0.96	2.62	3.472 (3)	148
C8—H8B···O2^vi	0.96	2.63	3.446 (3)	143
C8—H8C···O4^iv	0.96	2.96	3.687 (3)	134
C9—H9A···O1	0.97	2.63	3.486 (2)	148
C9—H9A···O4	0.97	2.54	3.428 (2)	152
C10—H10A···O2^vi	0.97	2.99	3.850 (3)	149
C10—H10B···O5^vi	0.97	2.89	3.553 (2)	127
C10—H10B···O6^vi	0.97	2.70	3.396 (2)	129
C11—H11B···O2^vi	0.97	2.53	3.467 (2)	163
C12—H12A···O1	0.97	2.67	3.544 (2)	151
C12—H12A···O6	0.97	2.81	3.339 (2)	116
C12—H12B···O8^ii	0.97	2.75	3.604 (2)	148
C13—H13A···O2^vi	0.96	2.88	3.480 (3)	121
C14—H14A···O8^ii	0.96	2.88	3.833 (3)	174
C15—H15A···O4	0.96	2.83	3.760 (3)	164
C15—H15B···O4^iii	0.96	2.72	3.615 (3)	155
C16—H16B···O6^ii	0.96	2.72	3.600 (3)	152
C16—H16B···O6	0.96	2.85	3.462 (2)	123

Symmetry codes: (i) −x+3/2, −y+3/2, −z; (ii) −x+2, y, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+3/2, −y+3/2, −z+1; (v) x−1/2, −y+3/2, z+1/2; (vi) x, −y+1, z+1/2.

(II) bis(tetraethylammonium) hydrogensulfate dihydrogenphosphate

Crystal data

2C8H20N^+·HSO4^−·H2PO4^−	F(000) = 1984
Mr = 454.56	Dx = 1.333 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 52330 reflections
a = 27.9460 (4) Å	θ = 1–30.0°
b = 11.7480 (2) Å	µ = 0.26 mm^−1
c = 14.0590 (2) Å	T = 150 K
β = 100.971 (9)°	Plate, colourless
V = 4531.35 (18) Å^3	0.40 × 0.20 × 0.05 mm
Z = 8

Data collection

Nonius KappaCCD area-detector diffractometer	5957 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.032
Graphite monochromator	θmax = 30.1°, θmin = 1.5°
ω scans	h = −38→39
21366 measured reflections	k = −16→16
6641 independent reflections	l = −19→19

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.113	w = 1/[σ^2(Fo^2) + (0.0418P)^2 + 4.9683P] where P = (Fo^2 + 2Fc^2)/3
S = 1.17	(Δ/σ)max = 0.002
6641 reflections	Δρmax = 0.42 e Å^−3
262 parameters	Δρmin = −0.47 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
110 constraints	Extinction coefficient: 0.0041 (3)
Primary atom site location: structure-invariant direct methods

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	Occ. (<1)
P1	0.788068 (12)	0.72553 (3)	0.14371 (2)	0.01815 (9)	0.50
S1	0.788068 (12)	0.72553 (3)	0.14371 (2)	0.01815 (9)	0.50
O1	0.84219 (4)	0.72455 (10)	0.18843 (7)	0.0252 (2)
H1O	0.8583	0.7588	0.1563	0.030*	0.50
O2	0.77975 (4)	0.63591 (9)	0.06425 (8)	0.0263 (2)
O3	0.77701 (4)	0.84178 (10)	0.09629 (8)	0.0318 (3)
H3O	0.7534	0.8478	0.0251	0.038*
O4	0.75978 (4)	0.70381 (11)	0.21938 (8)	0.0295 (2)
P2	0.954872 (12)	0.76676 (3)	0.11583 (2)	0.01711 (9)	0.50
S2	0.954872 (12)	0.76676 (3)	0.11583 (2)	0.01711 (9)	0.50
O5	0.90063 (4)	0.77993 (10)	0.07599 (7)	0.0252 (2)
H5O	0.8788	0.7637	0.1139	0.030*	0.50
O6	0.95988 (4)	0.67221 (9)	0.19190 (7)	0.0233 (2)
H6O	0.9909	0.6713	0.2391	0.028*	0.50
O7	0.97259 (4)	0.87764 (9)	0.16741 (7)	0.0259 (2)
H7O	0.9895	0.8693	0.2229	0.031*	0.50
O8	0.98078 (4)	0.74116 (11)	0.03704 (8)	0.0300 (2)
N1	0.62218 (4)	0.46676 (10)	0.67255 (8)	0.0170 (2)
C1	0.59298 (5)	0.35760 (12)	0.65487 (10)	0.0217 (3)
H1A	0.5845	0.3447	0.5856	0.026*
H1B	0.6135	0.2949	0.6829	0.026*
C2	0.63855 (5)	0.48924 (13)	0.78028 (10)	0.0220 (3)
H2A	0.6575	0.5589	0.7883	0.026*
H2B	0.6099	0.5018	0.8084	0.026*
C3	0.59167 (5)	0.56910 (12)	0.63232 (10)	0.0211 (3)
H3A	0.5643	0.5751	0.6654	0.025*
H3B	0.6113	0.6372	0.6473	0.025*
C4	0.66559 (5)	0.45142 (12)	0.62264 (10)	0.0207 (3)
H4A	0.6846	0.3870	0.6518	0.025*
H4B	0.6535	0.4331	0.5550	0.025*
C5	0.54669 (6)	0.35625 (14)	0.69596 (13)	0.0306 (3)
H5A	0.5546	0.3676	0.7648	0.046*
H5B	0.5307	0.2842	0.6823	0.046*
H5C	0.5255	0.4161	0.6668	0.046*
C6	0.66855 (6)	0.39551 (15)	0.83642 (11)	0.0305 (3)
H6A	0.6489	0.3283	0.8355	0.046*
H6B	0.6796	0.4196	0.9022	0.046*
H6C	0.6962	0.3791	0.8072	0.046*
C7	0.57221 (6)	0.56607 (15)	0.52416 (12)	0.0318 (3)
H7A	0.5989	0.5694	0.4902	0.048*
H7B	0.5511	0.6300	0.5060	0.048*
H7C	0.5543	0.4968	0.5077	0.048*
C8	0.69879 (5)	0.55389 (14)	0.62777 (13)	0.0303 (3)
H8A	0.6814	0.6159	0.5926	0.045*
H8B	0.7265	0.5351	0.5998	0.045*
H8C	0.7095	0.5756	0.6942	0.045*
N2	0.87608 (4)	0.54112 (10)	0.43346 (8)	0.0177 (2)
C9	0.84137 (5)	0.64136 (12)	0.42390 (10)	0.0207 (3)
H9A	0.8284	0.6538	0.3557	0.025*
H9B	0.8597	0.7088	0.4484	0.025*
C10	0.89830 (6)	0.51751 (13)	0.53883 (10)	0.0253 (3)
H10A	0.8727	0.4910	0.5714	0.030*
H10B	0.9218	0.4563	0.5412	0.030*
C11	0.84964 (5)	0.43258 (12)	0.39497 (11)	0.0231 (3)
H11A	0.8727	0.3700	0.4057	0.028*
H11B	0.8245	0.4171	0.4323	0.028*
C12	0.91523 (5)	0.57195 (12)	0.37597 (10)	0.0202 (3)
H12A	0.8995	0.5927	0.3107	0.024*
H12B	0.9327	0.6383	0.4054	0.024*
C13	0.79905 (6)	0.62850 (15)	0.47633 (13)	0.0323 (3)
H13A	0.7798	0.5636	0.4512	0.048*
H13B	0.7792	0.6957	0.4667	0.048*
H13C	0.8113	0.6180	0.5443	0.048*
C14	0.92333 (6)	0.61806 (16)	0.59432 (11)	0.0334 (4)
H14A	0.9481	0.6468	0.5618	0.050*
H14B	0.9380	0.5945	0.6587	0.050*
H14C	0.8998	0.6768	0.5978	0.050*
C15	0.82623 (6)	0.43508 (15)	0.28849 (12)	0.0327 (3)
H15A	0.8044	0.4988	0.2762	0.049*
H15B	0.8084	0.3659	0.2717	0.049*
H15C	0.8511	0.4422	0.2502	0.049*
C16	0.95165 (6)	0.47809 (14)	0.37000 (12)	0.0284 (3)
H16A	0.9651	0.4514	0.4340	0.043*
H16B	0.9774	0.5070	0.3402	0.043*
H16C	0.9356	0.4164	0.3320	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.01650 (16)	0.02007 (17)	0.01703 (16)	−0.00126 (11)	0.00103 (11)	−0.00087 (12)
S1	0.01650 (16)	0.02007 (17)	0.01703 (16)	−0.00126 (11)	0.00103 (11)	−0.00087 (12)
O1	0.0161 (4)	0.0366 (6)	0.0216 (5)	−0.0027 (4)	0.0001 (4)	0.0083 (4)
O2	0.0350 (6)	0.0204 (5)	0.0220 (5)	0.0039 (4)	0.0018 (4)	−0.0024 (4)
O3	0.0352 (6)	0.0214 (5)	0.0316 (6)	0.0009 (4)	−0.0121 (5)	−0.0032 (4)
O4	0.0219 (5)	0.0431 (7)	0.0247 (5)	−0.0063 (5)	0.0077 (4)	−0.0044 (5)
P2	0.01522 (15)	0.02059 (17)	0.01448 (15)	−0.00188 (11)	0.00018 (11)	0.00156 (11)
S2	0.01522 (15)	0.02059 (17)	0.01448 (15)	−0.00188 (11)	0.00018 (11)	0.00156 (11)
O5	0.0167 (4)	0.0381 (6)	0.0192 (5)	0.0001 (4)	−0.0004 (4)	0.0079 (4)
O6	0.0226 (5)	0.0231 (5)	0.0213 (5)	−0.0044 (4)	−0.0033 (4)	0.0052 (4)
O7	0.0314 (5)	0.0206 (5)	0.0218 (5)	−0.0037 (4)	−0.0049 (4)	0.0017 (4)
O8	0.0270 (5)	0.0410 (7)	0.0235 (5)	0.0031 (5)	0.0083 (4)	−0.0012 (5)
N1	0.0160 (5)	0.0179 (5)	0.0174 (5)	0.0014 (4)	0.0037 (4)	−0.0026 (4)
C1	0.0216 (6)	0.0190 (6)	0.0247 (7)	−0.0015 (5)	0.0045 (5)	−0.0060 (5)
C2	0.0231 (6)	0.0260 (7)	0.0170 (6)	−0.0016 (5)	0.0038 (5)	−0.0053 (5)
C3	0.0191 (6)	0.0189 (6)	0.0256 (7)	0.0051 (5)	0.0051 (5)	−0.0013 (5)
C4	0.0178 (6)	0.0238 (7)	0.0218 (6)	0.0055 (5)	0.0072 (5)	−0.0002 (5)
C5	0.0246 (7)	0.0280 (8)	0.0412 (9)	−0.0050 (6)	0.0117 (6)	−0.0041 (6)
C6	0.0297 (7)	0.0394 (9)	0.0216 (7)	0.0028 (7)	0.0025 (6)	0.0029 (6)
C7	0.0295 (7)	0.0348 (9)	0.0288 (8)	0.0126 (6)	−0.0006 (6)	0.0025 (6)
C8	0.0208 (7)	0.0311 (8)	0.0413 (9)	0.0002 (6)	0.0118 (6)	0.0006 (7)
N2	0.0191 (5)	0.0176 (5)	0.0168 (5)	0.0021 (4)	0.0050 (4)	0.0033 (4)
C9	0.0207 (6)	0.0174 (6)	0.0242 (6)	0.0043 (5)	0.0051 (5)	0.0037 (5)
C10	0.0317 (7)	0.0274 (7)	0.0169 (6)	0.0082 (6)	0.0049 (5)	0.0060 (5)
C11	0.0251 (6)	0.0175 (6)	0.0283 (7)	−0.0019 (5)	0.0090 (5)	0.0005 (5)
C12	0.0199 (6)	0.0218 (6)	0.0202 (6)	−0.0004 (5)	0.0069 (5)	0.0037 (5)
C13	0.0267 (7)	0.0313 (8)	0.0426 (9)	0.0082 (6)	0.0158 (7)	0.0052 (7)
C14	0.0350 (8)	0.0400 (9)	0.0222 (7)	0.0097 (7)	−0.0025 (6)	−0.0049 (6)
C15	0.0311 (8)	0.0317 (8)	0.0323 (8)	−0.0064 (6)	−0.0011 (6)	−0.0041 (6)
C16	0.0250 (7)	0.0318 (8)	0.0308 (8)	0.0069 (6)	0.0117 (6)	0.0061 (6)

Geometric parameters (Å, º)

P1—O4	1.4636 (11)	C5—H5A	0.9600
P1—O2	1.5204 (11)	C5—H5B	0.9600
P1—O1	1.5235 (10)	C5—H5C	0.9600
P1—O3	1.5253 (12)	C6—H6A	0.9600
P2—O8	1.4653 (11)	C6—H6B	0.9600
P2—O5	1.5207 (10)	C6—H6C	0.9600
P2—O7	1.5268 (11)	C7—H7A	0.9600
P2—O6	1.5298 (10)	C7—H7B	0.9600
N1—C1	1.5148 (17)	C7—H7C	0.9600
N1—C2	1.5196 (17)	C8—H8A	0.9600
N1—C3	1.5196 (17)	C8—H8B	0.9600
N1—C4	1.5233 (16)	C9—H9A	0.9700
C1—C5	1.514 (2)	C9—H9B	0.9700
C2—C6	1.512 (2)	C10—H10A	0.9700
C3—C7	1.515 (2)	C10—H10B	0.9700
C4—C8	1.513 (2)	C11—H11A	0.9700
N2—C9	1.5153 (17)	C11—H11B	0.9700
N2—C10	1.5188 (17)	C12—H12A	0.9700
N2—C11	1.5208 (18)	C12—H12B	0.9700
N2—C12	1.5224 (16)	C13—H13A	0.9600
C9—C13	1.515 (2)	C13—H13B	0.9600
C10—C14	1.512 (2)	C13—H13C	0.9600
C11—C15	1.516 (2)	C14—H14A	0.9600
C12—C16	1.514 (2)	C14—H14B	0.9600
C1—H1A	0.9700	C14—H14C	0.9600
C1—H1B	0.9700	C15—H15A	0.9600
C2—H2A	0.9700	C15—H15B	0.9600
C2—H2B	0.9700	C15—H15C	0.9600
C3—H3A	0.9700	C16—H16A	0.9600
C3—H3B	0.9700	C16—H16B	0.9600
C4—H4A	0.9700	C16—H16C	0.9600
C4—H4B	0.9700
O4—P1—O2	112.65 (7)	C2—C6—H6A	110
O4—P1—O1	109.26 (6)	C2—C6—H6B	110
O2—P1—O1	107.40 (6)	H6A—C6—H6B	110
O4—P1—O3	112.41 (7)	C2—C6—H6C	110
O2—P1—O3	108.00 (6)	H6A—C6—H6C	110
O1—P1—O3	106.85 (6)	H6B—C6—H6C	110
O8—P2—O5	110.11 (6)	C3—C7—H7A	110
O8—P2—O7	111.83 (7)	C3—C7—H7B	110
O5—P2—O7	107.38 (6)	H7A—C7—H7B	110
O8—P2—O6	112.76 (7)	C3—C7—H7C	110
O5—P2—O6	106.47 (6)	H7A—C7—H7C	110
O7—P2—O6	108.01 (6)	H7B—C7—H7C	110
C1—N1—C2	111.18 (11)	C4—C8—H8A	110
C1—N1—C3	111.23 (10)	C4—C8—H8B	110
C2—N1—C3	105.94 (10)	H8A—C8—H8B	110
C1—N1—C4	106.00 (10)	C4—C8—H8C	110
C2—N1—C4	111.39 (10)	H8A—C8—H8C	110
C3—N1—C4	111.21 (10)	H8B—C8—H8C	110
C5—C1—N1	114.77 (11)	N2—C9—H9A	109
C6—C2—N1	115.18 (12)	C13—C9—H9A	109
C7—C3—N1	115.08 (11)	N2—C9—H9B	109
C8—C4—N1	114.75 (11)	C13—C9—H9B	109
C9—N2—C10	111.37 (11)	H9A—C9—H9B	108
C9—N2—C11	111.13 (10)	C14—C10—H10A	109
C10—N2—C11	105.94 (11)	N2—C10—H10A	109
C9—N2—C12	106.29 (10)	C14—C10—H10B	109
C10—N2—C12	111.08 (10)	N2—C10—H10B	109
C11—N2—C12	111.11 (10)	H10A—C10—H10B	108
N2—C9—C13	115.15 (11)	C15—C11—H11A	109
C14—C10—N2	115.07 (12)	N2—C11—H11A	109
C15—C11—N2	115.11 (12)	C15—C11—H11B	109
C16—C12—N2	114.51 (11)	N2—C11—H11B	109
P1—O1—H1O	112	H11A—C11—H11B	108
P1—O3—H3O	120	C16—C12—H12A	109
P2—O5—H5O	120	N2—C12—H12A	109
P2—O6—H6O	116	C16—C12—H12B	109
P2—O7—H7O	115	N2—C12—H12B	109
C5—C1—H1A	109	H12A—C12—H12B	108
N1—C1—H1A	109	C9—C13—H13A	110
C5—C1—H1B	109	C9—C13—H13B	110
N1—C1—H1B	109	H13A—C13—H13B	110
H1A—C1—H1B	108	C9—C13—H13C	110
C6—C2—H2A	109	H13A—C13—H13C	110
N1—C2—H2A	109	H13B—C13—H13C	110
C6—C2—H2B	109	C10—C14—H14A	110
N1—C2—H2B	109	C10—C14—H14B	110
H2A—C2—H2B	108	H14A—C14—H14B	110
C7—C3—H3A	109	C10—C14—H14C	110
N1—C3—H3A	109	H14A—C14—H14C	110
C7—C3—H3B	109	H14B—C14—H14C	110
N1—C3—H3B	109	C11—C15—H15A	110
H3A—C3—H3B	108	C11—C15—H15B	110
C8—C4—H4A	109	H15A—C15—H15B	110
N1—C4—H4A	109	C11—C15—H15C	110
C8—C4—H4B	109	H15A—C15—H15C	110
N1—C4—H4B	109	H15B—C15—H15C	110
H4A—C4—H4B	108	C12—C16—H16A	110
C1—C5—H5A	110	C12—C16—H16B	110
C1—C5—H5B	110	H16A—C16—H16B	110
H5A—C5—H5B	110	C12—C16—H16C	110
C1—C5—H5C	110	H16A—C16—H16C	110
H5A—C5—H5C	110	H16B—C16—H16C	110
H5B—C5—H5C	110
C1—N1—C2—C6	57.24 (15)	C9—N2—C10—C14	−54.46 (16)
C1—N1—C3—C7	−60.37 (15)	C9—N2—C11—C15	61.39 (15)
C1—N1—C4—C8	177.49 (12)	C9—N2—C12—C16	−175.48 (12)
C2—N1—C3—C7	178.70 (12)	C10—N2—C11—C15	−177.49 (13)
C2—N1—C4—C8	−61.46 (15)	C10—N2—C12—C16	63.22 (15)
C2—N1—C1—C5	60.81 (15)	C10—N2—C9—C13	−58.89 (16)
C3—N1—C4—C8	56.47 (15)	C11—N2—C12—C16	−54.45 (15)
C3—N1—C1—C5	−56.99 (16)	C11—N2—C9—C13	58.98 (16)
C3—N1—C2—C6	178.21 (12)	C11—N2—C10—C14	−175.42 (12)
C4—N1—C1—C5	−178.00 (12)	C12—N2—C9—C13	180.00 (13)
C4—N1—C2—C6	−60.74 (15)	C12—N2—C10—C14	63.82 (16)
C4—N1—C3—C7	57.53 (15)	C12—N2—C11—C15	−56.75 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O2^i	1.09	1.42	2.5132 (15)	175
O1—H1O···O5	0.80	1.80	2.5635 (15)	158
O5—H5O···O1	0.90	1.66	2.5635 (15)	175
O6—H6O···O6^ii	0.99	1.53	2.5107 (19)	177
O7—H7O···O7^ii	0.84	1.70	2.527 (2)	169
C1—H1A···O5^iii	0.97	2.50	3.4087 (17)	155
C1—H1A···O8^iii	0.97	2.57	3.3590 (18)	139
C2—H2A···O1^iv	0.97	2.56	3.4204 (19)	147
C2—H2A···O3^iv	0.97	2.49	3.3109 (18)	142
C2—H2B···O7^iv	0.97	2.78	3.6746 (18)	154
C3—H3A···O7^v	0.97	2.63	3.5119 (17)	152
C3—H3A···O7^iv	0.97	2.80	3.6699 (18)	150
C4—H4A···O4^vi	0.97	2.39	3.2774 (17)	153
C4—H4B···O5^iii	0.97	2.80	3.6488 (17)	146
C5—H5C···O7^v	0.96	2.84	3.729 (2)	155
C6—H6C···O4^vi	0.96	2.54	3.488 (2)	168
C7—H7B···O8^v	0.96	2.58	3.445 (2)	150
C8—H8B···O2^vi	0.96	2.60	3.4142 (19)	142
C8—H8C···O4^iv	0.96	2.92	3.621 (2)	131
C9—H9A···O1	0.97	2.59	3.4560 (17)	149
C9—H9A···O4	0.97	2.51	3.3925 (18)	151
C10—H10A···O2^vi	0.97	2.98	3.8475 (19)	149
C10—H10B···O5^vi	0.97	2.90	3.5319 (19)	124
C10—H10B···O6^vi	0.97	2.65	3.3392 (17)	128
C11—H11B···O2^vi	0.97	2.51	3.4491 (18)	164
C12—H12A···O1	0.97	2.62	3.5047 (17)	152
C12—H12A···O6	0.97	2.75	3.2969 (17)	116
C12—H12B···O8^ii	0.97	2.69	3.5413 (18)	147
C13—H13A···O2^vi	0.96	2.83	3.424 (2)	121
C14—H14A···O8^ii	0.96	2.86	3.817 (2)	178
C15—H15A···O4	0.96	2.76	3.698 (2)	166
C15—H15B···O4^iii	0.96	2.71	3.615 (2)	157
C16—H16B···O6^ii	0.96	2.71	3.5903 (19)	153
C16—H16B···O6	0.96	2.82	3.4266 (19)	122

Symmetry codes: (i) −x+3/2, −y+3/2, −z; (ii) −x+2, y, −z+1/2; (iii) −x+3/2, y−1/2, −z+1/2; (iv) −x+3/2, −y+3/2, −z+1; (v) x−1/2, −y+3/2, z+1/2; (vi) x, −y+1, z+1/2.