Bis(oxonium) tetra-kis(o-toluidinium) cyclo-hexa-phosphate.

In the title compound, 4C(7)H(10)N(+)·2H(3)O(+)·P(6)O(18) (6-), the complete cyclo-hexa-phosphate anion is generated by crystallographic inversion symmetry. In the crystal, the H(3)O(+) ions and the [P(6)O(18)](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 inter-connected by the organic cations, which establish N-H⋯O hydrogen bonds with the [P(6)O(18)](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+·P6O18 6−

M = 944.51

Triclinic,

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[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.114

S = 1.01

5773 reflections

278 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.38 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

4C7H10N+·2H3O+·P6O186−	Z = 1
Mr = 944.51	F(000) = 492
Triclinic, P1	Dx = 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

Enraf–Nonius CAD-4 diffractometer	Rint = 0.025
Radiation source: fine-focus sealed tube	θmax = 30.0°, θmin = 3.0°
graphite	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 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(Fo2) + (0.0495P)2 + 0.1583P] where P = (Fo2 + 2Fc2)/3
5773 reflections	(Δ/σ)max < 0.001
278 parameters	Δρmax = 0.33 e Å−3
6 restraints	Δρmin = −0.38 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)*

	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)

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

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···O8iv	0.89	1.86	2.753 (3)	177
N1—H1B···O2ii	0.89	1.98	2.853 (3)	168
N1—H1C···O5iv	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···O1v	0.89	1.83	2.710 (3)	170

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⋯O6iv	0.89	2.35	3.085 (4)	140
N2—H2B⋯O5ii	0.89	2.02	2.904 (3)	176
N2—H2C⋯O1v	0.89	1.83	2.710 (3)	170

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .