Tetra-kis(3,5-xylidinium) dihydrogen cyclo-hexa-phosphate dihydrate.

In the title compound, 4C(8)H(12)N(+)·H(2)P(6)O(18) (4-)·2H(2)O, the complete cyclo-hexa-phosphate anion is generated by inversion symmetry. Crystal cohesion and stability are supported by electrostatic inter-actions which, together with N-H⋯O and O-H⋯O hydrogen bonds, build up a three-dimensional network.

Related literature

For related structures, see: Khederi et al. (2001 ▶); Rayes et al. (2004 ▶); Amri et al. (2008 ▶); Janiak et al. (2000 ▶). For a discussion on hydrogen bonding, see: Brown (1976 ▶). For tetra­hedral distortions, see: Baur (1974 ▶). For the preparation of cyclo­hexa­phospho­ric acid, see: Schülke & Kayser (1985 ▶).

Experimental

Crystal data

4C8H12N+·H2P6O18 4−·2H2O

M = 1000.61

Monoclinic,

a = 17.254 (3) Å

b = 11.763 (5) Å

c = 11.556 (2) Å

β = 106.41 (3)°

V = 2249.9 (11) Å3

Z = 2

Mo Kα radiation

μ = 0.32 mm−1

T = 293 K

0.35 × 0.20 × 0.01 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

10097 measured reflections

9844 independent reflections

5567 reflections with I > 2σ(I)

R int = 0.039

2 standard reflections every 120 min intensity decay: 11%

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.141

S = 1.02

9844 reflections

295 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.50 e Å−3

Δρmin = −0.51 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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/S1600536809054452/hb5267sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809054452/hb5267Isup2.hkl

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

4C8H12N+·H2P6O184−·2H2O	F(000) = 1048
Mr = 1000.61	Dx = 1.477 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 17.254 (3) Å	θ = 6.3–10.1°
b = 11.763 (5) Å	µ = 0.32 mm−1
c = 11.556 (2) Å	T = 293 K
β = 106.41 (3)°	Prism, colourless
V = 2249.9 (11) Å3	0.35 × 0.20 × 0.01 mm
Z = 2

Enraf–Nonius CAD-4 diffractometer	Rint = 0.039
Radiation source: Enraf Nonius FR590	θmax = 35.0°, θmin = 3.0°
graphite	h = 0→27
non–profiled ω scans	k = −18→0
10097 measured reflections	l = −18→17
9844 independent reflections	2 standard reflections every 120 min
5567 reflections with I > 2σ(I)	intensity decay: 11%

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) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0664P)2 + 0.0078P] where P = (Fo2 + 2Fc2)/3
9844 reflections	(Δ/σ)max = 0.001
295 parameters	Δρmax = 0.50 e Å−3
3 restraints	Δρmin = −0.51 e Å−3

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.

	x	y	z	Uiso*/Ueq
P1	0.00136 (3)	0.52037 (4)	0.73695 (4)	0.02425 (10)
P2	0.09276 (3)	0.68827 (4)	0.63729 (4)	0.02327 (10)
P3	0.13602 (3)	0.55149 (4)	0.45087 (4)	0.02452 (10)
O1	−0.04452 (9)	0.43770 (12)	0.62693 (12)	0.0358 (3)
O2	−0.05542 (9)	0.55967 (13)	0.80125 (13)	0.0383 (3)
O3	0.07729 (8)	0.46237 (12)	0.80005 (12)	0.0331 (3)
O4	0.01792 (9)	0.62742 (15)	0.66154 (17)	0.0516 (5)
O5	0.06005 (9)	0.77774 (12)	0.54796 (13)	0.0355 (3)
O6	0.15290 (10)	0.71634 (14)	0.75342 (13)	0.0463 (4)
O7	0.13336 (10)	0.58897 (13)	0.58091 (12)	0.0411 (4)
O8	0.18549 (10)	0.63572 (15)	0.40517 (15)	0.0470 (4)
H8	0.1563	0.6703	0.3476	0.071*
O9	0.16580 (8)	0.43352 (11)	0.46188 (12)	0.0299 (3)
O1W	0.10923 (9)	0.23683 (13)	0.55367 (13)	0.0350 (3)
H2W	0.1207 (13)	0.3026 (12)	0.534 (2)	0.049 (8)*
H1W	0.0587 (6)	0.226 (2)	0.535 (2)	0.051 (8)*
N1	0.15651 (10)	0.26040 (14)	0.80220 (14)	0.0286 (3)
H1A	0.1545	0.1974	0.8438	0.043*
H1B	0.1444	0.2439	0.7240	0.043*
H1C	0.1211	0.3107	0.8146	0.043*
N2	0.13845 (10)	0.97750 (14)	0.54343 (15)	0.0330 (3)
H2A	0.1291	1.0056	0.4692	0.050*
H2B	0.1225	1.0275	0.5899	0.050*
H2C	0.1111	0.9129	0.5408	0.050*
C1	0.23806 (11)	0.30866 (16)	0.84216 (16)	0.0277 (3)
C2	0.26029 (13)	0.38692 (18)	0.76896 (19)	0.0374 (5)
H2	0.2242	0.4077	0.6958	0.045*
C3	0.33672 (15)	0.4345 (2)	0.8052 (2)	0.0442 (5)
C4	0.38869 (14)	0.4024 (2)	0.9153 (2)	0.0448 (5)
H4	0.4401	0.4342	0.9397	0.054*
C5	0.36648 (13)	0.3244 (2)	0.9902 (2)	0.0389 (5)
C6	0.28937 (12)	0.27755 (18)	0.95214 (18)	0.0338 (4)
H6	0.2726	0.2255	1.0007	0.041*
C7	0.3613 (2)	0.5219 (3)	0.7259 (3)	0.0738 (10)
H7A	0.3367	0.5936	0.7336	0.111*
H7B	0.3438	0.4974	0.6434	0.111*
H7C	0.4190	0.5301	0.7505	0.111*
C8	0.42344 (16)	0.2895 (3)	1.1093 (2)	0.0611 (8)
H8A	0.4552	0.2259	1.0973	0.092*
H8B	0.3930	0.2683	1.1638	0.092*
H8C	0.4584	0.3519	1.1428	0.092*
C9	0.22502 (12)	0.95537 (16)	0.59349 (17)	0.0301 (4)
C10	0.26548 (14)	0.99879 (18)	0.70482 (18)	0.0376 (5)
H10	0.2387	1.0454	0.7460	0.045*
C11	0.34615 (15)	0.9726 (2)	0.7550 (2)	0.0457 (5)
C12	0.38358 (15)	0.9013 (2)	0.6916 (2)	0.0508 (6)
H12	0.4376	0.8823	0.7253	0.061*
C13	0.34264 (15)	0.8571 (2)	0.5790 (2)	0.0454 (5)
C14	0.26241 (14)	0.88654 (19)	0.5298 (2)	0.0391 (5)
H14	0.2340	0.8598	0.4540	0.047*
C15	0.3918 (2)	1.0199 (3)	0.8766 (3)	0.0760 (10)
H15A	0.4073	1.0970	0.8674	0.114*
H15B	0.4392	0.9749	0.9101	0.114*
H15C	0.3579	1.0179	0.9296	0.114*
C16	0.3838 (2)	0.7769 (3)	0.5129 (3)	0.0766 (10)
H16A	0.3464	0.7193	0.4731	0.115*
H16B	0.4293	0.7419	0.5695	0.115*
H16C	0.4021	0.8186	0.4542	0.115*

	U11	U22	U33	U12	U13	U23
P1	0.0263 (2)	0.0223 (2)	0.0234 (2)	0.00168 (17)	0.00594 (16)	0.00207 (16)
P2	0.0260 (2)	0.01997 (19)	0.02237 (19)	−0.00016 (16)	0.00439 (16)	−0.00186 (15)
P3	0.0315 (2)	0.0211 (2)	0.01944 (19)	0.00324 (17)	0.00459 (17)	−0.00015 (15)
O1	0.0347 (7)	0.0350 (7)	0.0313 (7)	0.0121 (6)	−0.0010 (6)	−0.0107 (6)
O2	0.0436 (8)	0.0418 (8)	0.0324 (7)	0.0089 (7)	0.0154 (6)	−0.0037 (6)
O3	0.0305 (7)	0.0324 (7)	0.0315 (7)	0.0082 (6)	0.0007 (5)	0.0033 (5)
O4	0.0324 (8)	0.0516 (10)	0.0708 (11)	0.0029 (7)	0.0147 (8)	0.0358 (9)
O5	0.0356 (7)	0.0252 (6)	0.0419 (8)	0.0001 (6)	0.0045 (6)	0.0094 (6)
O6	0.0525 (10)	0.0407 (9)	0.0335 (8)	0.0069 (7)	−0.0078 (7)	−0.0156 (6)
O7	0.0591 (10)	0.0392 (8)	0.0218 (6)	0.0212 (7)	0.0061 (6)	−0.0037 (6)
O8	0.0470 (9)	0.0448 (9)	0.0454 (9)	−0.0054 (8)	0.0066 (7)	0.0210 (7)
O9	0.0348 (7)	0.0230 (6)	0.0306 (6)	0.0049 (5)	0.0073 (5)	−0.0017 (5)
O1W	0.0338 (8)	0.0331 (8)	0.0359 (7)	−0.0025 (6)	0.0064 (6)	0.0061 (6)
N1	0.0291 (8)	0.0261 (7)	0.0294 (7)	−0.0014 (6)	0.0061 (6)	−0.0001 (6)
N2	0.0352 (9)	0.0279 (8)	0.0350 (8)	−0.0015 (7)	0.0085 (7)	0.0026 (7)
C1	0.0264 (8)	0.0258 (8)	0.0294 (8)	−0.0014 (7)	0.0055 (7)	−0.0015 (7)
C2	0.0392 (11)	0.0373 (11)	0.0323 (10)	−0.0051 (9)	0.0044 (8)	0.0045 (8)
C3	0.0442 (12)	0.0455 (13)	0.0428 (12)	−0.0135 (10)	0.0122 (10)	0.0040 (10)
C4	0.0312 (11)	0.0496 (13)	0.0508 (13)	−0.0097 (10)	0.0067 (10)	−0.0007 (11)
C5	0.0313 (10)	0.0422 (12)	0.0380 (11)	0.0008 (9)	0.0015 (8)	−0.0005 (9)
C6	0.0322 (10)	0.0350 (10)	0.0324 (9)	−0.0008 (8)	0.0059 (8)	0.0036 (8)
C7	0.071 (2)	0.080 (2)	0.0672 (19)	−0.0334 (17)	0.0143 (16)	0.0215 (16)
C8	0.0433 (14)	0.078 (2)	0.0486 (14)	−0.0039 (13)	−0.0086 (11)	0.0127 (13)
C9	0.0334 (9)	0.0254 (8)	0.0316 (9)	−0.0034 (7)	0.0091 (7)	0.0019 (7)
C10	0.0438 (12)	0.0372 (11)	0.0306 (9)	0.0016 (9)	0.0087 (9)	−0.0024 (8)
C11	0.0446 (12)	0.0513 (14)	0.0341 (11)	−0.0006 (11)	−0.0003 (9)	−0.0010 (10)
C12	0.0362 (12)	0.0537 (15)	0.0579 (15)	0.0039 (11)	0.0057 (11)	0.0023 (12)
C13	0.0438 (12)	0.0412 (12)	0.0558 (14)	−0.0026 (10)	0.0217 (11)	−0.0076 (11)
C14	0.0423 (12)	0.0380 (11)	0.0377 (10)	−0.0082 (9)	0.0124 (9)	−0.0095 (9)
C15	0.070 (2)	0.090 (2)	0.0484 (15)	0.0066 (18)	−0.0148 (14)	−0.0129 (16)
C16	0.0589 (18)	0.082 (2)	0.098 (3)	0.0113 (17)	0.0369 (18)	−0.028 (2)

P1—O2	1.4619 (15)	C3—C7	1.515 (3)
P1—O3	1.4744 (14)	C4—C5	1.388 (3)
P1—O4	1.6024 (16)	C4—H4	0.9300
P1—O1	1.6187 (15)	C5—C6	1.392 (3)
P2—O5	1.4706 (15)	C5—C8	1.505 (3)
P2—O6	1.4832 (15)	C6—H6	0.9300
P2—O4	1.5692 (16)	C7—H7A	0.9600
P2—O7	1.5930 (15)	C7—H7B	0.9600
P3—O9	1.4728 (15)	C7—H7C	0.9600
P3—O8	1.4980 (16)	C8—H8A	0.9600
P3—O7	1.5790 (14)	C8—H8B	0.9600
P3—O1i	1.5859 (15)	C8—H8C	0.9600
O1—P3i	1.5859 (15)	C9—C14	1.371 (3)
O8—H8	0.8200	C9—C10	1.377 (3)
O1W—H2W	0.847 (9)	C10—C11	1.383 (3)
O1W—H1W	0.846 (9)	C10—H10	0.9300
N1—C1	1.466 (2)	C11—C12	1.387 (4)
N1—H1A	0.8900	C11—C15	1.510 (3)
N1—H1B	0.8900	C12—C13	1.393 (3)
N1—H1C	0.8900	C12—H12	0.9300
N2—C9	1.465 (3)	C13—C14	1.384 (3)
N2—H2A	0.8900	C13—C16	1.512 (4)
N2—H2B	0.8900	C14—H14	0.9300
N2—H2C	0.8900	C15—H15A	0.9600
C1—C2	1.376 (3)	C15—H15B	0.9600
C1—C6	1.377 (3)	C15—H15C	0.9600
C2—C3	1.384 (3)	C16—H16A	0.9600
C2—H2	0.9300	C16—H16B	0.9600
C3—C4	1.386 (3)	C16—H16C	0.9600
O2—P1—O3	121.63 (9)	C4—C5—C8	121.8 (2)
O2—P1—O4	106.02 (10)	C6—C5—C8	120.0 (2)
O3—P1—O4	111.25 (9)	C1—C6—C5	119.6 (2)
O2—P1—O1	109.87 (9)	C1—C6—H6	120.2
O3—P1—O1	106.24 (8)	C5—C6—H6	120.2
O4—P1—O1	99.66 (10)	C3—C7—H7A	109.5
O5—P2—O6	120.50 (10)	C3—C7—H7B	109.5
O5—P2—O4	106.25 (9)	H7A—C7—H7B	109.5
O6—P2—O4	109.92 (11)	C3—C7—H7C	109.5
O5—P2—O7	111.32 (9)	H7A—C7—H7C	109.5
O6—P2—O7	104.90 (9)	H7B—C7—H7C	109.5
O4—P2—O7	102.57 (10)	C5—C8—H8A	109.5
O9—P3—O8	115.72 (10)	C5—C8—H8B	109.5
O9—P3—O7	106.50 (8)	H8A—C8—H8B	109.5
O8—P3—O7	108.87 (10)	C5—C8—H8C	109.5
O9—P3—O1i	113.06 (8)	H8A—C8—H8C	109.5
O8—P3—O1i	108.80 (9)	H8B—C8—H8C	109.5
O7—P3—O1i	103.02 (9)	C14—C9—C10	121.9 (2)
P3i—O1—P1	125.79 (9)	C14—C9—N2	118.34 (18)
P2—O4—P1	137.54 (11)	C10—C9—N2	119.63 (18)
P3—O7—P2	136.74 (10)	C9—C10—C11	119.6 (2)
P3—O8—H8	109.5	C9—C10—H10	120.2
H2W—O1W—H1W	111.4 (19)	C11—C10—H10	120.2
C1—N1—H1A	109.5	C10—C11—C12	118.5 (2)
C1—N1—H1B	109.5	C10—C11—C15	120.4 (2)
H1A—N1—H1B	109.5	C12—C11—C15	121.1 (2)
C1—N1—H1C	109.5	C11—C12—C13	122.0 (2)
H1A—N1—H1C	109.5	C11—C12—H12	119.0
H1B—N1—H1C	109.5	C13—C12—H12	119.0
C9—N2—H2A	109.5	C14—C13—C12	118.4 (2)
C9—N2—H2B	109.5	C14—C13—C16	120.5 (2)
H2A—N2—H2B	109.5	C12—C13—C16	121.2 (2)
C9—N2—H2C	109.5	C9—C14—C13	119.6 (2)
H2A—N2—H2C	109.5	C9—C14—H14	120.2
H2B—N2—H2C	109.5	C13—C14—H14	120.2
C2—C1—C6	121.79 (18)	C11—C15—H15A	109.5
C2—C1—N1	118.35 (17)	C11—C15—H15B	109.5
C6—C1—N1	119.83 (17)	H15A—C15—H15B	109.5
C1—C2—C3	119.47 (19)	C11—C15—H15C	109.5
C1—C2—H2	120.3	H15A—C15—H15C	109.5
C3—C2—H2	120.3	H15B—C15—H15C	109.5
C2—C3—C4	118.8 (2)	C13—C16—H16A	109.5
C2—C3—C7	119.8 (2)	C13—C16—H16B	109.5
C4—C3—C7	121.4 (2)	H16A—C16—H16B	109.5
C3—C4—C5	122.1 (2)	C13—C16—H16C	109.5
C3—C4—H4	118.9	H16A—C16—H16C	109.5
C5—C4—H4	118.9	H16B—C16—H16C	109.5
C4—C5—C6	118.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8···O6ii	0.82	1.71	2.421 (2)	144
O1W—H2W···O9	0.85 (1)	2.01 (1)	2.831 (2)	164 (2)
O1W—H1W···O5i	0.85 (1)	2.00 (1)	2.829 (2)	165 (2)
N1—H1A···O9iii	0.89	2.03	2.910 (2)	170
N1—H1B···O1W	0.89	1.89	2.769 (2)	169
N1—H1C···O3	0.89	1.93	2.738 (2)	151
N2—H2A···O3ii	0.89	1.94	2.801 (2)	161
N2—H2B···O2iv	0.89	1.97	2.768 (2)	148
N2—H2C···O5	0.89	1.83	2.719 (2)	175

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8⋯O6i	0.82	1.71	2.421 (2)	144
O1W—H2W⋯O9	0.85 (1)	2.01 (1)	2.831 (2)	164 (2)
O1W—H1W⋯O5ii	0.85 (1)	2.00 (1)	2.829 (2)	165 (2)
N1—H1A⋯O9iii	0.89	2.03	2.910 (2)	170
N1—H1B⋯O1W	0.89	1.89	2.769 (2)	169
N1—H1C⋯O3	0.89	1.93	2.738 (2)	151
N2—H2A⋯O3i	0.89	1.94	2.801 (2)	161
N2—H2B⋯O2iv	0.89	1.97	2.768 (2)	148
N2—H2C⋯O5	0.89	1.83	2.719 (2)	175

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