Tetra-kis(2-amino-5-chloro-pyridinium) di-hydrogen cyclo-hexa-phosphate.

In the crystal structure of the title compound, 4C5H6ClN2 (+)·H2P6O18 (4-), the [H2P6O18](4-) anions are interconnected by O-H⋯O hydrogen bonds, leading to the formation of infinite ribbons extending along the a-axis direction. These ribbons are linked to the organic cations, via N-H⋯O and C-H⋯O hydrogen bonds, into a three-dimensional network. The six P atoms of the [H2P6O18](4-) anion form a chair conformation. The complete cyclohexaphosphate anion is generated by inversion symmetry.

Related literature

For properties of hybrid materials, see: Ozin (1992 ▶); Teraski et al. (1987 ▶). For related structures containing cyclo­hexa­phosphate rings, see: Bel Haj Salah et al. (2014 ▶); Khedhiri et al. (2007 ▶, 2012 ▶); Amri et al. (2009 ▶); Abid et al. (2012 ▶). For bond lengths in pyridine, see: Bak et al. (1959 ▶); Hemissi et al. (2010 ▶); Toumi Akriche et al. (2010 ▶); Akriche & Rzaigui (2005 ▶); Janiak (2000 ▶). For the preparation of cyclo­hexa­phospho­ric acid, see: Schulke & Kayser (1985 ▶).

Experimental

Crystal data

4C5H6ClN2 +·H2O18P6 4−

M = 994.11

Triclinic,

a = 9.199 (3) Å

b = 9.304 (2) Å

c = 11.327 (3) Å

α = 74.98 (3)°

β = 85.17 (2)°

γ = 75.20 (2)°

V = 905.1 (5) Å3

Z = 1

Ag Kα radiation

λ = 0.56087 Å

μ = 0.35 mm−1

T = 293 K

0.32 × 0.22 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

11291 measured reflections

8865 independent reflections

5387 reflections with I > 2σ(I)

R int = 0.020

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.155

S = 1.02

8865 reflections

305 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.82 e Å−3

Δρmin = −0.65 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: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814003584/fj2662sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814003584/fj2662Isup2.hkl

CCDC reference: 987420

Additional supporting information: crystallographic information; 3D view; checkCIF report

4C5H6ClN2+·H2O18P64−	Z = 1
Mr = 994.11	F(000) = 504
Triclinic, P1	Dx = 1.824 Mg m−3
Hall symbol: -P 1	Ag Kα radiation, λ = 0.56087 Å
a = 9.199 (3) Å	Cell parameters from 25 reflections
b = 9.304 (2) Å	θ = 9–11°
c = 11.327 (3) Å	µ = 0.35 mm−1
α = 74.98 (3)°	T = 293 K
β = 85.17 (2)°	Rectangular, colorless
γ = 75.20 (2)°	0.32 × 0.22 × 0.15 mm
V = 905.1 (5) Å3

Enraf–Nonius CAD-4 diffractometer	Rint = 0.020
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.1°
Graphite monochromator	h = −15→15
non–profiled ω scans	k = −15→15
11291 measured reflections	l = −18→3
8865 independent reflections	2 standard reflections every 120 min
5387 reflections with I > 2σ(I)	intensity decay: 1%

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0798P)2 + 0.0876P] where P = (Fo2 + 2Fc2)/3
8865 reflections	(Δ/σ)max = 0.001
305 parameters	Δρmax = 0.82 e Å−3
0 restraints	Δρmin = −0.65 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	0.31788 (5)	0.39966 (6)	0.59770 (5)	0.0246 (1)
P2	0.09221 (5)	0.22559 (6)	0.68658 (5)	0.0249 (1)
P3	0.21377 (5)	0.64715 (6)	0.38126 (5)	0.0261 (1)
O1	0.39658 (19)	0.4679 (2)	0.67218 (19)	0.0454 (6)
O2	0.40900 (17)	0.29457 (17)	0.52877 (14)	0.0335 (4)
O3	0.20301 (19)	0.5379 (2)	0.51466 (15)	0.0455 (5)
O4	0.20430 (16)	0.32887 (17)	0.69374 (13)	0.0297 (4)
O5	0.08853 (19)	0.11700 (18)	0.80701 (15)	0.0375 (5)
O6	0.12380 (17)	0.16793 (19)	0.57518 (15)	0.0353 (4)
O7	0.06189 (16)	0.64266 (17)	0.32794 (16)	0.0359 (5)
O8	0.33616 (16)	0.56632 (18)	0.30855 (14)	0.0333 (4)
O9	0.21174 (18)	0.80107 (18)	0.39100 (17)	0.0407 (5)
Cl1	0.26706 (10)	0.37124 (10)	−0.05308 (6)	0.0606 (3)
N1	0.0267 (2)	0.1302 (2)	0.18049 (17)	0.0341 (5)
N2	−0.0748 (3)	0.1321 (3)	0.3732 (2)	0.0430 (7)
C1	0.0017 (3)	0.1920 (2)	0.2777 (2)	0.0319 (5)
C2	0.0596 (3)	0.3211 (3)	0.2711 (2)	0.0382 (7)
C3	0.1390 (3)	0.3761 (3)	0.1712 (2)	0.0396 (7)
C4	0.1628 (3)	0.3061 (3)	0.0732 (2)	0.0377 (6)
C5	0.1044 (3)	0.1844 (3)	0.0791 (2)	0.0376 (6)
Cl2	0.71034 (11)	0.24071 (11)	−0.00108 (7)	0.0685 (3)
N3	0.4844 (2)	0.2016 (2)	0.31254 (19)	0.0370 (6)
N4	0.3444 (2)	0.0352 (2)	0.4197 (2)	0.0387 (6)
C6	0.4320 (2)	0.0752 (2)	0.3261 (2)	0.0298 (5)
C7	0.4751 (2)	−0.0097 (2)	0.2364 (2)	0.0325 (6)
C8	0.5622 (3)	0.0394 (3)	0.1400 (2)	0.0373 (6)
C9	0.6083 (3)	0.1751 (3)	0.1271 (2)	0.0405 (7)
C10	0.5705 (3)	0.2533 (3)	0.2150 (2)	0.0434 (7)
H1A	0.483 (5)	0.441 (5)	0.680 (4)	0.113 (17)*
H1	−0.010 (3)	0.041 (3)	0.186 (3)	0.047 (8)*
H2	0.041 (3)	0.362 (3)	0.333 (3)	0.053 (9)*
H2A	−0.089 (3)	0.046 (4)	0.382 (3)	0.044 (8)*
H2B	−0.083 (4)	0.164 (4)	0.433 (3)	0.055 (9)*
H3A	0.174 (3)	0.469 (4)	0.162 (3)	0.055 (9)*
H5	0.107 (3)	0.139 (4)	0.021 (3)	0.053 (9)*
H3	0.457 (4)	0.247 (4)	0.363 (3)	0.054 (9)*
H4A	0.319 (3)	0.082 (3)	0.471 (2)	0.033 (7)*
H4B	0.312 (4)	−0.053 (5)	0.425 (3)	0.075 (11)*
H7	0.442 (3)	−0.106 (3)	0.249 (3)	0.044 (8)*
H8	0.592 (3)	−0.006 (3)	0.082 (2)	0.031 (6)*
H10	0.607 (4)	0.340 (4)	0.218 (3)	0.058 (9)*

	U11	U22	U33	U12	U13	U23
P1	0.0202 (2)	0.0277 (2)	0.0285 (2)	−0.0090 (2)	0.0034 (2)	−0.0097 (2)
P2	0.0230 (2)	0.0271 (2)	0.0294 (2)	−0.0115 (2)	0.0022 (2)	−0.0111 (2)
P3	0.0231 (2)	0.0274 (2)	0.0304 (2)	−0.0090 (2)	−0.0001 (2)	−0.0093 (2)
O1	0.0284 (7)	0.0669 (11)	0.0609 (12)	−0.0270 (8)	0.0119 (7)	−0.0393 (10)
O2	0.0306 (7)	0.0335 (7)	0.0360 (8)	−0.0039 (6)	0.0058 (6)	−0.0135 (6)
O3	0.0387 (8)	0.0452 (9)	0.0345 (8)	0.0062 (7)	0.0107 (7)	0.0020 (7)
O4	0.0297 (6)	0.0388 (7)	0.0294 (7)	−0.0210 (6)	0.0047 (5)	−0.0129 (6)
O5	0.0454 (9)	0.0366 (8)	0.0343 (8)	−0.0224 (7)	−0.0015 (7)	−0.0028 (6)
O6	0.0351 (7)	0.0438 (8)	0.0376 (8)	−0.0184 (6)	0.0078 (6)	−0.0226 (7)
O7	0.0243 (6)	0.0320 (7)	0.0589 (10)	−0.0077 (5)	−0.0042 (6)	−0.0224 (7)
O8	0.0254 (6)	0.0452 (8)	0.0339 (8)	−0.0124 (6)	0.0046 (5)	−0.0158 (7)
O9	0.0367 (8)	0.0351 (8)	0.0601 (11)	−0.0175 (6)	−0.0027 (7)	−0.0196 (7)
Cl1	0.0841 (5)	0.0739 (5)	0.0387 (3)	−0.0499 (4)	0.0169 (3)	−0.0155 (3)
N1	0.0451 (10)	0.0335 (8)	0.0322 (9)	−0.0198 (8)	0.0038 (7)	−0.0142 (7)
N2	0.0648 (14)	0.0380 (10)	0.0362 (10)	−0.0264 (10)	0.0150 (9)	−0.0182 (9)
C1	0.0409 (10)	0.0271 (8)	0.0313 (10)	−0.0126 (8)	0.0012 (8)	−0.0100 (7)
C2	0.0574 (14)	0.0313 (10)	0.0330 (11)	−0.0199 (10)	0.0031 (10)	−0.0127 (8)
C3	0.0558 (14)	0.0339 (10)	0.0365 (11)	−0.0217 (10)	0.0022 (10)	−0.0120 (9)
C4	0.0482 (12)	0.0406 (11)	0.0300 (10)	−0.0220 (10)	0.0017 (9)	−0.0086 (9)
C5	0.0477 (12)	0.0426 (11)	0.0323 (10)	−0.0222 (10)	0.0044 (9)	−0.0169 (9)
Cl2	0.0848 (6)	0.0781 (5)	0.0483 (4)	−0.0413 (5)	0.0239 (4)	−0.0125 (4)
N3	0.0453 (10)	0.0351 (9)	0.0389 (10)	−0.0173 (8)	0.0078 (8)	−0.0190 (8)
N4	0.0389 (10)	0.0384 (10)	0.0450 (11)	−0.0143 (8)	0.0103 (8)	−0.0197 (9)
C6	0.0299 (9)	0.0282 (8)	0.0343 (10)	−0.0084 (7)	−0.0007 (7)	−0.0114 (7)
C7	0.0354 (10)	0.0296 (9)	0.0368 (10)	−0.0082 (8)	−0.0022 (8)	−0.0147 (8)
C8	0.0414 (11)	0.0421 (11)	0.0333 (11)	−0.0111 (9)	0.0019 (9)	−0.0177 (9)
C9	0.0447 (12)	0.0461 (12)	0.0333 (11)	−0.0171 (10)	0.0064 (9)	−0.0107 (10)
C10	0.0554 (14)	0.0379 (11)	0.0444 (13)	−0.0242 (10)	0.0065 (11)	−0.0127 (10)

Cl1—C4	1.718 (3)	N3—C6	1.350 (3)
Cl2—C9	1.722 (3)	N3—C10	1.361 (3)
P1—O2	1.4612 (17)	N4—C6	1.310 (3)
P1—O1	1.501 (2)	N3—H3	0.78 (4)
P1—O3	1.5816 (19)	N4—H4B	0.93 (4)
P1—O4	1.5804 (17)	N4—H4A	0.80 (3)
P2—O4	1.5981 (17)	C1—C2	1.416 (4)
P2—O7i	1.6082 (17)	C2—C3	1.352 (3)
P2—O5	1.4758 (18)	C3—C4	1.402 (3)
P2—O6	1.4744 (18)	C4—C5	1.357 (4)
P3—O3	1.5989 (18)	C2—H2	0.87 (3)
P3—O9	1.4599 (18)	C3—H3A	0.98 (4)
P3—O7	1.5823 (17)	C5—H5	0.87 (3)
P3—O8	1.4979 (17)	C6—C7	1.415 (3)
O1—H1A	0.78 (5)	C7—C8	1.351 (3)
N1—C5	1.353 (3)	C8—C9	1.401 (4)
N1—C1	1.347 (3)	C9—C10	1.353 (4)
N2—C1	1.317 (3)	C7—H7	0.99 (3)
N1—H1	0.96 (3)	C8—H8	0.86 (2)
N2—H2A	0.82 (4)	C10—H10	0.96 (4)
N2—H2B	0.80 (3)
O1—P1—O2	118.53 (10)	C6—N4—H4A	123.5 (19)
O1—P1—O3	106.68 (11)	C6—N4—H4B	117 (2)
O1—P1—O4	102.68 (10)	N1—C1—N2	119.7 (2)
O2—P1—O3	112.61 (10)	N2—C1—C2	123.0 (2)
O2—P1—O4	114.52 (10)	N1—C1—C2	117.3 (2)
O3—P1—O4	99.74 (9)	C1—C2—C3	120.3 (2)
O4—P2—O5	108.10 (10)	C2—C3—C4	119.9 (3)
O4—P2—O6	110.40 (9)	C3—C4—C5	119.5 (2)
O4—P2—O7i	98.08 (9)	Cl1—C4—C3	120.7 (2)
O5—P2—O6	119.81 (10)	Cl1—C4—C5	119.78 (19)
O5—P2—O7i	108.31 (10)	N1—C5—C4	119.6 (2)
O6—P2—O7i	109.93 (10)	C1—C2—H2	117.0 (19)
O3—P3—O7	99.05 (10)	C3—C2—H2	123 (2)
O3—P3—O8	109.32 (10)	C2—C3—H3A	121.8 (19)
O3—P3—O9	109.78 (11)	C4—C3—H3A	118.2 (19)
O7—P3—O8	105.20 (10)	C4—C5—H5	126 (2)
O7—P3—O9	111.56 (10)	N1—C5—H5	114 (2)
O8—P3—O9	119.86 (10)	N3—C6—C7	117.59 (19)
P1—O3—P3	134.02 (13)	N3—C6—N4	120.0 (2)
P1—O4—P2	132.54 (10)	N4—C6—C7	122.37 (18)
P2i—O7—P3	126.34 (11)	C6—C7—C8	119.8 (2)
P1—O1—H1A	121 (3)	C7—C8—C9	120.5 (2)
C1—N1—C5	123.4 (2)	C8—C9—C10	119.4 (2)
C5—N1—H1	119.3 (19)	Cl2—C9—C8	119.51 (19)
C1—N1—H1	117.3 (19)	Cl2—C9—C10	121.1 (2)
C1—N2—H2A	121 (2)	N3—C10—C9	119.5 (2)
H2A—N2—H2B	117 (3)	C6—C7—H7	117.6 (18)
C1—N2—H2B	119 (3)	C8—C7—H7	122.6 (18)
C6—N3—C10	123.1 (2)	C7—C8—H8	124.7 (18)
C6—N3—H3	115 (3)	C9—C8—H8	114.7 (18)
C10—N3—H3	122 (3)	N3—C10—H10	116 (2)
H4A—N4—H4B	120 (3)	C9—C10—H10	125 (2)
O1—P1—O3—P3	89.53 (18)	C5—N1—C1—C2	0.6 (4)
O2—P1—O3—P3	−42.1 (2)	C1—N1—C5—C4	0.8 (4)
O4—P1—O3—P3	−163.97 (16)	C10—N3—C6—N4	−177.2 (2)
O1—P1—O4—P2	−174.03 (14)	C10—N3—C6—C7	2.8 (3)
O2—P1—O4—P2	−44.19 (17)	C6—N3—C10—C9	−0.8 (4)
O3—P1—O4—P2	76.27 (15)	N1—C1—C2—C3	−1.3 (4)
O5—P2—O4—P1	144.47 (14)	N2—C1—C2—C3	179.1 (3)
O6—P2—O4—P1	11.66 (17)	C1—C2—C3—C4	0.7 (4)
O7i—P2—O4—P1	−103.18 (15)	C2—C3—C4—Cl1	−178.5 (2)
O4—P2—O7i—P3i	159.29 (13)	C2—C3—C4—C5	0.7 (4)
O5—P2—O7i—P3i	−88.53 (15)	Cl1—C4—C5—N1	177.8 (2)
O6—P2—O7i—P3i	44.08 (16)	C3—C4—C5—N1	−1.4 (4)
O7—P3—O3—P1	134.37 (16)	N3—C6—C7—C8	−1.8 (3)
O8—P3—O3—P1	24.7 (2)	N4—C6—C7—C8	178.1 (2)
O9—P3—O3—P1	−108.72 (17)	C6—C7—C8—C9	−1.0 (4)
O3—P3—O7—P2i	102.22 (14)	C7—C8—C9—Cl2	−176.3 (2)
O8—P3—O7—P2i	−144.80 (13)	C7—C8—C9—C10	3.0 (4)
O9—P3—O7—P2i	−13.34 (18)	Cl2—C9—C10—N3	177.2 (2)
C5—N1—C1—N2	−179.8 (3)	C8—C9—C10—N3	−2.1 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5ii	0.96 (3)	1.78 (3)	2.736 (3)	177 (3)
O1—H1A···O8iii	0.78 (5)	1.66 (5)	2.418 (3)	165 (5)
N2—H2A···O6ii	0.82 (4)	2.02 (4)	2.844 (3)	173 (3)
N2—H2B···O9i	0.80 (3)	2.29 (3)	3.000 (3)	149 (4)
N3—H3···O2	0.78 (4)	2.03 (3)	2.781 (3)	161 (3)
N4—H4A···O2	0.80 (3)	2.57 (3)	3.179 (3)	134 (2)
N4—H4A···O6	0.80 (3)	2.16 (3)	2.827 (3)	142 (3)
N4—H4B···O9iv	0.93 (4)	1.95 (4)	2.852 (3)	162 (3)
C5—H5···O5v	0.87 (3)	2.51 (3)	3.322 (3)	157 (3)
C10—H10···O1iii	0.96 (4)	2.42 (4)	3.262 (3)	146 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5i	0.96 (3)	1.78 (3)	2.736 (3)	177 (3)
O1—H1A⋯O8ii	0.78 (5)	1.66 (5)	2.418 (3)	165 (5)
N2—H2A⋯O6i	0.82 (4)	2.02 (4)	2.844 (3)	173 (3)
N2—H2B⋯O9iii	0.80 (3)	2.29 (3)	3.000 (3)	149 (4)
N3—H3⋯O2	0.78 (4)	2.03 (3)	2.781 (3)	161 (3)
N4—H4A⋯O2	0.80 (3)	2.57 (3)	3.179 (3)	134 (2)
N4—H4A⋯O6	0.80 (3)	2.16 (3)	2.827 (3)	142 (3)
N4—H4B⋯O9iv	0.93 (4)	1.95 (4)	2.852 (3)	162 (3)
C5—H5⋯O5v	0.87 (3)	2.51 (3)	3.322 (3)	157 (3)
C10—H10⋯O1ii	0.96 (4)	2.42 (4)	3.262 (3)	146 (3)

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