Bis(oxonium) tetra­kis(o-toluidinium) cyclo­hexa­phosphate

Marouani, H.; Rzaigui, M.; Al-Deyab, S.S.

doi:10.1107/S1600536810006537

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 66| Part 3| March 2010| Page o702

doi:10.1107/S1600536810006537

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Bis(oxonium) tetrakis(o-toluidinium) cyclohexaphosphate

Houda Marouani,^a ^* Mohamed Rzaigui ^a and Salem S. Al-Deyab ^b

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bPetrochemical Research Chair, College of Science, King Saud University, Riyadh, Saudi Arabia
^*Correspondence e-mail: houda.marouani@fsb.rnu.tn

(Received 16 February 2010; accepted 19 February 2010; online 27 February 2010)

In the title compound, 4C₇H₁₀N⁺·2H₃O⁺·P₆O₁₈⁶⁻, the complete cyclohexaphosphate anion is generated by crystallographic inversion symmetry. In the crystal, the H₃O⁺ ions and the [P₆O₁₈]⁶⁻ anions are linked by O—H⋯O hydrogen bonds, generating infinite layers lying parallel to the ab plane at z = 1/2. These layers are interconnected by the organic cations, which establish N—H⋯O hydrogen bonds with the [P₆O₁₈]⁶⁻ anions.

Related literature

For further synthetic details, see: Schülke & Kayser (1985 ). For related structures, see: Amri et al. (2008 ); Larafa et al. (1997 ); Akriche & Rzaigui (2000 ); Selmi et al. (2009 ); Khemiri et al. (2009 ). For a discussion on hydrogen bonding, see: Brown (1976 ); Blessing (1986 ). For tetrahedral distortions, see: Baur (1974 ).

Experimental

Crystal data

4C₇H₁₀N⁺·2H₃O⁺·P₆O₁₈⁶⁻
M_r = 944.51
Triclinic, $[P \overline 1]$
a = 9.344 (3) Å
b = 10.360 (2) Å
c = 11.537 (2) Å
α = 95.35 (4)°
β = 92.23 (3)°
γ = 116.00 (5)°
V = 995.4 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
6038 measured reflections
5773 independent reflections
3061 reflections with I > 2σ(I)
R_int = 0.025
2 standard reflections every 120 min intensity decay: 10%

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.114
S = 1.01
5773 reflections
278 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H110⋯O9	0.86 (1)	1.62 (1)	2.469 (3)	170 (3)
O10—H210⋯O2ⁱ	0.86 (1)	1.69 (1)	2.550 (3)	177 (3)
O10—H310⋯O6ⁱⁱ	0.86 (1)	1.67 (1)	2.524 (3)	171 (3)
N1—H1A⋯O8ⁱⁱⁱ	0.89	1.86	2.753 (3)	177
N1—H1B⋯O2ⁱ	0.89	1.98	2.853 (3)	168
N1—H1C⋯O5ⁱⁱⁱ	0.89	1.92	2.800 (3)	169
N2—H2A⋯O6^iv	0.89	2.35	3.085 (4)	140
N2—H2B⋯O5ⁱⁱ	0.89	2.02	2.904 (3)	176
N2—H2C⋯O1^v	0.89	1.83	2.710 (3)	170
Symmetry codes: (i) -x+1, -y, -z+1; (ii) x+1, y+1, z; (iii) x+1, y, z; (iv) -x, -y, -z+1; (v) x, y+1, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810006537/hb5337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810006537/hb5337Isup2.hkl

checkCIF report

Comment top

Many cyclohexaphosphates of organic cations and inorganic cations (mono, bi and trivalent) have been synthesized and structurally characterized. But the association of the oxonium cation to this kind of material is very rare. On the other hand, there is only one cyclohexaphosphate of mixed cation (organic-oxonium) (Amri, et al., 2008). In this work, we report the preparation and the structural investigation of a new organic oxonium cyclohexaphospohate, (o-CH₃C₆H₄NH₃)₄(H₃O)₂P₆O₁₈, (I).

The title compound is built up from P₆O₁₈^6- anion, four organic o-toluidinium and two oxonium cations (Fig. 1). The half of the anion, two organic and one oxonium cations constitute the asymmetric unit of (I). The atomic arrangement of the title compound is characterized by the existence of inorganic layers, built by P₆O₁₈^6- ring anions and oxonium cations. Each cyclohexaphosphate group is connected to its adjacent neighbours by six oxonium ions through strong O—H···O hydrogen bonds (Table 1) (H···O = 1.66 Å) (Blessing, 1986); (Brown, 1976). The same phenomenon has been observed for (C₁₀H₁₃NH₃)₄(H₃O)₂P₆O₁₈.3H₂O (Amri, et al., 2008).

It is worth noting that the H₃O⁺ ions exhibit a pyramidal geometry. These layers formed by P₆O₁₈ groups and oxonium ions cross the unit cell parallel to the (a, b) plane at z = 1/2 (Fig. 2). Between these layers, separated by a distance of 11.537 (2) Å, organic cations establish hydrogen bonds to interconnect the different anions. The N(1)H₃ groups produce the internal P₆O₁₈ ring cohesion through hydrogen bonds involving external oxygen atoms of each PO₄ tetrahedron. The other N(2)H₃ groups, link three different rings and so contribute to the interlayer cohesion of this compound. Inside such a structure, the phosphoric ring has an -1 internal symmetry. It develops around the inversion centre located at (0, 0, 1/2), so it is built up by only three independent tetrahedra. The calculated average values of the distortion indices (Baur, 1974) corresponding to the different angles and distances in the PO₄ tetrahedra [DI (OPO) = 0.038; DI (PO) = 0.039; and DI (OO) = 0.012], show a pronounced distortion of the PO distances and OPO angles if compared to OO distances. So, the PO₄ group can be considered as a rigid regular arrangement of oxygen atoms, with the phosphorus atom slightly displaced from the gravity centre.

In this atomic arrangement exist two independent o-toluidinium cations. Interatomic bond lengths and angles of these groups spread respectively within the ranges [1.367 (5)-1.504 (4) Å] and [115.7 (3)-122.8 (3)°]. The aromatic rings are planar with an average deviation of 0.000189 Å and form a dihedral angle of 28.53°. These values are similar to those obtained for the same organic group in other compounds (Larafa, et al. 1997); (Akriche & Rzaigui, 2000); (Selmi, et al., 2009); (Khemiri et al., 2009).

Related literature top

For further synthetic details, see: Schülke & Kayser (1985). For related structures, see: Amri et al. (2008); Larafa et al. (1997); Akriche et al. (2000); Selmi et al. (2009); Khemiri et al. (2009). For a discussion on hydrogen bonding, see: Brown (1976); Blessing (1986). For tetrahedral distortions, see: Baur (1974).

Experimental top

The title compound has been prepared in two steps. In the first one, we prepare Li₆P₆O₁₈.6H₂O according to the process described by Schülke and Kayser (Schülke & Kayser, 1985). From this lithium salt, we prepare an aqueous solution of cyclohexaphosphate acid H₆P₆O₁₈ by passing a solution of Li₆P₆O₁₈.6H₂O (5 g in 100 ml) through an ion- exchange resin in its H-state (Amberlite IR 120). In the second step, at 20 ml of the aqueous solution of H₆P₆O₁₈ freshly prepared, we add drop by drop a solution of o-toluidine (30 mmol in 20 ml of ethanol) under continuous stirring.

In order to avoid the hydrolysis of the ring anion the above reaction is performed at room temperature. The so-obtained solution is then slowly evaporated until1 the formation of pink prisms of (I). The title compound is stable for months under normal conditions of temperature and relative humidity.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1996); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of (I) with displacement ellipsoids drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Symmetry code: i: -x, -y, -z.
	Fig. 2. Projection of the structure of (I) along the a axis.

Bis(oxonium) tetrakis(o-toluidinium) cyclohexaphosphate top

Crystal data top

4C₇H₁₀N⁺·2H₃O⁺·P₆O₁₈⁶⁻	Z = 1
M_r = 944.51	F(000) = 492
Triclinic, P1	D_x = 1.576 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.344 (3) Å	Cell parameters from 25 reflections
b = 10.360 (2) Å	θ = 10–12°
c = 11.537 (2) Å	µ = 0.36 mm⁻¹
α = 95.35 (4)°	T = 293 K
β = 92.23 (3)°	Prism, pink
γ = 116.00 (5)°	0.25 × 0.20 × 0.15 mm
V = 995.4 (4) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
Radiation source: fine-focus sealed tube	θ_max = 30.0°, θ_min = 3.0°
Graphite monochromator	h = −13→13
non–profiled ω scans	k = −14→14
6038 measured reflections	l = 0→16
5773 independent reflections	2 standard reflections every 120 min
3061 reflections with I > 2σ(I)	intensity decay: 10%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.0495P)² + 0.1583P] where P = (F_o² + 2F_c²)/3
5773 reflections	(Δ/σ)_max < 0.001
278 parameters	Δρ_max = 0.33 e Å⁻³
6 restraints	Δρ_min = −0.38 e Å⁻³

Crystal data top

4C₇H₁₀N⁺·2H₃O⁺·P₆O₁₈⁶⁻	γ = 116.00 (5)°
M_r = 944.51	V = 995.4 (4) Å³
Triclinic, P1	Z = 1
a = 9.344 (3) Å	Mo Kα radiation
b = 10.360 (2) Å	µ = 0.36 mm⁻¹
c = 11.537 (2) Å	T = 293 K
α = 95.35 (4)°	0.25 × 0.20 × 0.15 mm
β = 92.23 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.025
6038 measured reflections	2 standard reflections every 120 min
5773 independent reflections	intensity decay: 10%
3061 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.052	6 restraints
wR(F²) = 0.114	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.33 e Å⁻³
5773 reflections	Δρ_min = −0.38 e Å⁻³
278 parameters

Special details top

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

	x	y	z	U_iso*/U_eq
P1	0.19977 (8)	−0.14917 (7)	0.55334 (6)	0.02334 (15)
P2	−0.14713 (8)	−0.25078 (7)	0.56200 (6)	0.02236 (15)
P3	0.28988 (8)	0.16136 (7)	0.62215 (6)	0.02600 (16)
O1	0.2843 (2)	−0.2032 (2)	0.62940 (17)	0.0356 (5)
O2	0.1635 (2)	−0.2086 (2)	0.42722 (15)	0.0313 (4)
O3	0.2961 (2)	0.0217 (2)	0.55757 (19)	0.0398 (5)
O4	0.0375 (2)	−0.1674 (2)	0.60834 (15)	0.0285 (4)
O5	−0.2360 (2)	−0.2181 (2)	0.65479 (16)	0.0306 (4)
O6	−0.1935 (2)	−0.40394 (19)	0.51838 (17)	0.0372 (5)
O7	−0.1447 (2)	−0.1662 (2)	0.45304 (16)	0.0293 (4)
O8	0.2395 (2)	0.1384 (2)	0.74021 (16)	0.0401 (5)
O9	0.4383 (2)	0.2884 (2)	0.6012 (2)	0.0453 (6)
O10	0.7313 (2)	0.3898 (2)	0.64060 (18)	0.0321 (4)
N1	0.9215 (3)	0.0733 (2)	0.74960 (18)	0.0291 (5)
H1A	1.0242	0.0929	0.7486	0.044*
H1B	0.8992	0.1265	0.7023	0.044*
H1C	0.8609	−0.0201	0.7255	0.044*
N2	0.4244 (3)	0.6264 (2)	0.6809 (2)	0.0320 (5)
H2A	0.3811	0.5381	0.6413	0.048*
H2B	0.5279	0.6711	0.6701	0.048*
H2C	0.3755	0.6766	0.6555	0.048*
C1	0.8890 (3)	0.1076 (3)	0.8692 (2)	0.0269 (5)
C2	0.7377 (3)	0.0942 (3)	0.8895 (2)	0.0303 (6)
C3	0.7148 (4)	0.1246 (3)	1.0057 (3)	0.0382 (7)
H3	0.6155	0.1174	1.0236	0.046*
C4	0.8337 (4)	0.1648 (3)	1.0948 (3)	0.0428 (8)
H4	0.8136	0.1824	1.1715	0.051*
C5	0.9816 (4)	0.1791 (4)	1.0705 (3)	0.0453 (8)
H5	1.0629	0.2084	1.1304	0.054*
C6	1.0098 (4)	0.1498 (3)	0.9566 (3)	0.0392 (7)
H6	1.1098	0.1585	0.9394	0.047*
C7	0.6060 (4)	0.0507 (4)	0.7933 (3)	0.0455 (8)
H7A	0.6445	0.1115	0.7325	0.068*
H7B	0.5172	0.0613	0.8240	0.068*
H7C	0.5724	−0.0484	0.7620	0.068*
C8	0.4056 (3)	0.6151 (3)	0.8077 (2)	0.0311 (6)
C9	0.2550 (4)	0.5396 (3)	0.8433 (3)	0.0357 (7)
C10	0.2453 (4)	0.5348 (3)	0.9631 (3)	0.0445 (8)
H10	0.1461	0.4832	0.9906	0.053*
C11	0.3771 (5)	0.6038 (4)	1.0416 (3)	0.0489 (8)
H11	0.3667	0.5987	1.1211	0.059*
C12	0.5246 (4)	0.6802 (4)	1.0034 (3)	0.0536 (9)
H12	0.6139	0.7282	1.0571	0.064*
C13	0.5409 (4)	0.6862 (3)	0.8859 (3)	0.0414 (7)
H13	0.6408	0.7370	0.8592	0.050*
C14	0.1088 (4)	0.4694 (4)	0.7588 (3)	0.0517 (9)
H14A	0.0923	0.5425	0.7232	0.078*
H14B	0.0177	0.4154	0.7996	0.078*
H14C	0.1226	0.4054	0.6995	0.078*
H110	0.6282 (11)	0.348 (3)	0.633 (3)	0.057 (11)*
H210	0.770 (4)	0.331 (3)	0.617 (3)	0.088 (15)*
H310	0.767 (4)	0.464 (2)	0.603 (3)	0.079 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0218 (3)	0.0296 (4)	0.0229 (3)	0.0147 (3)	0.0036 (3)	0.0058 (3)
P2	0.0215 (3)	0.0218 (3)	0.0225 (3)	0.0082 (3)	0.0057 (3)	0.0030 (3)
P3	0.0185 (3)	0.0275 (4)	0.0299 (4)	0.0086 (3)	0.0005 (3)	0.0025 (3)
O1	0.0377 (11)	0.0476 (12)	0.0310 (11)	0.0275 (10)	−0.0009 (9)	0.0066 (9)
O2	0.0350 (10)	0.0473 (12)	0.0210 (9)	0.0265 (9)	0.0047 (8)	0.0049 (8)
O3	0.0369 (11)	0.0293 (10)	0.0565 (14)	0.0154 (9)	0.0238 (10)	0.0090 (9)
O4	0.0213 (9)	0.0425 (11)	0.0216 (9)	0.0142 (8)	0.0045 (7)	0.0026 (8)
O5	0.0236 (9)	0.0344 (10)	0.0308 (10)	0.0099 (8)	0.0107 (8)	0.0020 (8)
O6	0.0477 (13)	0.0247 (10)	0.0369 (12)	0.0136 (9)	0.0109 (10)	0.0026 (9)
O7	0.0198 (9)	0.0364 (10)	0.0312 (10)	0.0102 (8)	0.0027 (7)	0.0139 (8)
O8	0.0379 (11)	0.0550 (14)	0.0246 (10)	0.0191 (10)	−0.0039 (9)	0.0024 (9)
O9	0.0206 (10)	0.0385 (12)	0.0654 (16)	0.0028 (9)	−0.0009 (10)	0.0085 (11)
O10	0.0235 (10)	0.0306 (11)	0.0408 (12)	0.0106 (9)	0.0030 (9)	0.0052 (9)
N1	0.0302 (12)	0.0319 (12)	0.0253 (12)	0.0140 (10)	0.0049 (9)	0.0024 (9)
N2	0.0292 (12)	0.0334 (13)	0.0324 (13)	0.0128 (10)	0.0054 (10)	0.0041 (10)
C1	0.0327 (14)	0.0254 (13)	0.0225 (13)	0.0129 (11)	0.0047 (11)	0.0026 (10)
C2	0.0348 (15)	0.0285 (14)	0.0277 (14)	0.0133 (12)	0.0053 (12)	0.0063 (11)
C3	0.0427 (17)	0.0471 (18)	0.0327 (16)	0.0249 (15)	0.0159 (13)	0.0113 (13)
C4	0.066 (2)	0.0483 (19)	0.0228 (15)	0.0332 (17)	0.0109 (14)	0.0035 (13)
C5	0.052 (2)	0.057 (2)	0.0261 (16)	0.0254 (17)	−0.0059 (14)	0.0004 (14)
C6	0.0339 (15)	0.0509 (19)	0.0329 (16)	0.0194 (14)	0.0021 (13)	0.0026 (14)
C7	0.0324 (16)	0.063 (2)	0.0357 (17)	0.0160 (16)	0.0044 (13)	0.0086 (15)
C8	0.0341 (15)	0.0313 (14)	0.0317 (15)	0.0176 (12)	0.0047 (12)	0.0057 (12)
C9	0.0398 (16)	0.0298 (15)	0.0350 (16)	0.0135 (13)	0.0053 (13)	0.0025 (12)
C10	0.057 (2)	0.0418 (18)	0.0396 (18)	0.0242 (16)	0.0180 (16)	0.0109 (14)
C11	0.069 (2)	0.052 (2)	0.0338 (18)	0.0326 (19)	0.0072 (17)	0.0085 (15)
C12	0.048 (2)	0.071 (2)	0.0391 (19)	0.0263 (19)	−0.0116 (16)	0.0009 (17)
C13	0.0350 (16)	0.0500 (19)	0.0409 (18)	0.0202 (15)	0.0024 (13)	0.0073 (15)
C14	0.0348 (17)	0.049 (2)	0.052 (2)	0.0033 (15)	0.0034 (15)	−0.0024 (16)

Geometric parameters (Å, º) top

P1—O1	1.461 (2)	C2—C3	1.395 (4)
P1—O2	1.491 (2)	C2—C7	1.504 (4)
P1—O3	1.591 (2)	C3—C4	1.374 (4)
P1—O4	1.6075 (19)	C3—H3	0.9300
P2—O6	1.480 (2)	C4—C5	1.367 (5)
P2—O5	1.4830 (19)	C4—H4	0.9300
P2—O7	1.5931 (19)	C5—C6	1.383 (4)
P2—O4	1.594 (2)	C5—H5	0.9300
P3—O8	1.465 (2)	C6—H6	0.9300
P3—O9	1.483 (2)	C7—H7A	0.9600
P3—O3	1.590 (2)	C7—H7B	0.9600
P3—O7ⁱ	1.6035 (19)	C7—H7C	0.9600
O7—P3ⁱ	1.6035 (19)	C8—C9	1.378 (4)
O10—H110	0.862 (10)	C8—C13	1.388 (4)
O10—H210	0.863 (10)	C9—C10	1.393 (4)
O10—H310	0.864 (10)	C9—C14	1.496 (4)
N1—C1	1.470 (3)	C10—C11	1.367 (5)
N1—H1A	0.8900	C10—H10	0.9300
N1—H1B	0.8900	C11—C12	1.369 (5)
N1—H1C	0.8900	C11—H11	0.9300
N2—C8	1.489 (3)	C12—C13	1.375 (5)
N2—H2A	0.8900	C12—H12	0.9300
N2—H2B	0.8900	C13—H13	0.9300
N2—H2C	0.8900	C14—H14A	0.9600
C1—C6	1.370 (4)	C14—H14B	0.9600
C1—C2	1.390 (4)	C14—H14C	0.9600

O1—P1—O2	118.49 (11)	C4—C3—C2	122.3 (3)
O1—P1—O3	110.27 (13)	C4—C3—H3	118.8
O2—P1—O3	106.30 (12)	C2—C3—H3	118.8
O1—P1—O4	108.90 (11)	C5—C4—C3	120.0 (3)
O2—P1—O4	109.44 (11)	C5—C4—H4	120.0
O3—P1—O4	102.21 (11)	C3—C4—H4	120.0
O6—P2—O5	118.69 (12)	C4—C5—C6	119.7 (3)
O6—P2—O7	108.57 (12)	C4—C5—H5	120.1
O5—P2—O7	110.85 (11)	C6—C5—H5	120.1
O6—P2—O4	111.40 (12)	C1—C6—C5	119.4 (3)
O5—P2—O4	106.38 (11)	C1—C6—H6	120.3
O7—P2—O4	99.21 (11)	C5—C6—H6	120.3
O8—P3—O9	121.31 (13)	C2—C7—H7A	109.5
O8—P3—O3	111.13 (13)	C2—C7—H7B	109.5
O9—P3—O3	107.21 (12)	H7A—C7—H7B	109.5
O8—P3—O7ⁱ	106.23 (11)	C2—C7—H7C	109.5
O9—P3—O7ⁱ	107.42 (12)	H7A—C7—H7C	109.5
O3—P3—O7ⁱ	101.72 (12)	H7B—C7—H7C	109.5
P3—O3—P1	137.49 (13)	C9—C8—C13	122.6 (3)
P2—O4—P1	133.83 (12)	C9—C8—N2	119.2 (2)
P2—O7—P3ⁱ	129.82 (12)	C13—C8—N2	118.2 (3)
H110—O10—H210	112 (2)	C8—C9—C10	116.4 (3)
H110—O10—H310	110 (2)	C8—C9—C14	122.2 (3)
H210—O10—H310	110 (2)	C10—C9—C14	121.4 (3)
C1—N1—H1A	109.5	C11—C10—C9	122.0 (3)
C1—N1—H1B	109.5	C11—C10—H10	119.0
H1A—N1—H1B	109.5	C9—C10—H10	119.0
C1—N1—H1C	109.5	C10—C11—C12	120.2 (3)
H1A—N1—H1C	109.5	C10—C11—H11	119.9
H1B—N1—H1C	109.5	C12—C11—H11	119.9
C8—N2—H2A	109.5	C11—C12—C13	120.1 (3)
C8—N2—H2B	109.5	C11—C12—H12	120.0
H2A—N2—H2B	109.5	C13—C12—H12	120.0
C8—N2—H2C	109.5	C12—C13—C8	118.8 (3)
H2A—N2—H2C	109.5	C12—C13—H13	120.6
H2B—N2—H2C	109.5	C8—C13—H13	120.6
C6—C1—C2	122.8 (3)	C9—C14—H14A	109.5
C6—C1—N1	118.0 (2)	C9—C14—H14B	109.5
C2—C1—N1	119.1 (2)	H14A—C14—H14B	109.5
C1—C2—C3	115.7 (3)	C9—C14—H14C	109.5
C1—C2—C7	122.8 (3)	H14A—C14—H14C	109.5
C3—C2—C7	121.5 (3)	H14B—C14—H14C	109.5

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H110···O9	0.86 (1)	1.62 (1)	2.469 (3)	170 (3)
O10—H210···O2ⁱⁱ	0.86 (1)	1.69 (1)	2.550 (3)	177 (3)
O10—H310···O6ⁱⁱⁱ	0.86 (1)	1.67 (1)	2.524 (3)	171 (3)
N1—H1A···O8^iv	0.89	1.86	2.753 (3)	177
N1—H1B···O2ⁱⁱ	0.89	1.98	2.853 (3)	168
N1—H1C···O5^iv	0.89	1.92	2.800 (3)	169
N2—H2A···O6ⁱ	0.89	2.35	3.085 (4)	140
N2—H2B···O5ⁱⁱⁱ	0.89	2.02	2.904 (3)	176
N2—H2C···O1^v	0.89	1.83	2.710 (3)	170

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

Experimental details

Crystal data
Chemical formula	4C₇H₁₀N⁺·2H₃O⁺·P₆O₁₈⁶⁻
M_r	944.51
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.344 (3), 10.360 (2), 11.537 (2)
α, β, γ (°)	95.35 (4), 92.23 (3), 116.00 (5)
V (Å³)	995.4 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.36
Crystal size (mm)	0.25 × 0.20 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6038, 5773, 3061
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.703

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.114, 1.01
No. of reflections	5773
No. of parameters	278
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.38

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1996), SHELXS86 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H110···O9	0.862 (10)	1.616 (12)	2.469 (3)	170 (3)
O10—H210···O2ⁱ	0.863 (10)	1.688 (10)	2.550 (3)	177 (3)
O10—H310···O6ⁱⁱ	0.864 (10)	1.668 (12)	2.524 (3)	171 (3)
N1—H1A···O8ⁱⁱⁱ	0.89	1.86	2.753 (3)	177.3
N1—H1B···O2ⁱ	0.89	1.98	2.853 (3)	168.0
N1—H1C···O5ⁱⁱⁱ	0.89	1.92	2.800 (3)	168.7
N2—H2A···O6^iv	0.89	2.35	3.085 (4)	139.7
N2—H2B···O5ⁱⁱ	0.89	2.02	2.904 (3)	176.2
N2—H2C···O1^v	0.89	1.83	2.710 (3)	169.9

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

References

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Volume 66| Part 3| March 2010| Page o702

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