Bis(3-ammonio-methyl-pyridinium) cyclo-tetra-phosphate.

In the title compound, 2C(6)H(10)N(2) (2+)·P(4)O(12) (4-), which involves a doubly protonated 3-ammonio-methyl-pyridinium cation and a cyclo-tetra-phosphate anion, the cyclo-tetra-phospho-ric ring is arranged around an inversion center and the organic entity alternates with it, forming hybrid ribbons parallel to the b axis. The crystal structure is stabilized by a three-dimensional network of N-H⋯O and weaker C-H⋯O hydrogen bonds.

Related literature

For properties of hybrid materials, see: Aakeröy et al.(1989 ▶); Sankar et al. (1993 ▶); Teraski et al. (1987 ▶); Vaughan (1993 ▶); Centi (1993 ▶); Ozin (1992 ▶). For related structures containing phospho­ric acid rings, see: Aloui et al. (2003 ▶); Hemissi et al. (2005 ▶); Averbuch-Pouchot & Durif (1991 ▶); Durif (1995 ▶). For bond lengths in pyridine, see: Bak et al. (1959 ▶). For hydrogen bonding, see: Blessing (1986 ▶); Brown (1976 ▶); Soumhi & Jouini (1996 ▶). Cyclo­tetra­phospho­ric acid was produced from Na4P4O12·4H2O, which was prepared according to the Ondik (1964 ▶) process.

Experimental

Crystal data

2C6H10N2 2+·P4O12 4−

M = 536.20

Triclinic,

a = 7.849 (2) Å

b = 8.384 (2) Å

c = 9.448 (2) Å

α = 113.24 (2)°

β = 98.73 (3)°

γ = 108.76 (3)°

V = 512.4 (2) Å3

Z = 1

Ag Kα radiation

λ = 0.56083 Å

μ = 0.23 mm−1

T = 293 K

0.35 × 0.3 × 0.15 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

7923 measured reflections

5005 independent reflections

3963 reflections with I > 2σ(I)

R int = 0.012

2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.101

S = 1.08

5005 reflections

145 parameters

H-atom parameters constrained

Δρmax = 0.49 e Å−3

Δρmin = −0.47 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: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810008056/dn2541sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810008056/dn2541Isup2.hkl

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

2C6H10N22+·P4O124−	Z = 1
Mr = 536.20	F(000) = 276
Triclinic, P1	Dx = 1.738 Mg m−3
Hall symbol: -P 1	Ag Kα radiation, λ = 0.56083 Å
a = 7.849 (2) Å	Cell parameters from 25 reflections
b = 8.384 (2) Å	θ = 9.0–10.7°
c = 9.448 (2) Å	µ = 0.23 mm−1
α = 113.24 (2)°	T = 293 K
β = 98.73 (3)°	Prism, colourless
γ = 108.76 (3)°	0.35 × 0.3 × 0.15 mm
V = 512.4 (2) Å3

Enraf–Nonius CAD-4 diffractometer	Rint = 0.012
Radiation source: Enraf–Nonius FR590	θmax = 28.0°, θmin = 2.2°
graphite	h = −13→13
non–profiled ω scans	k = −14→14
7923 measured reflections	l = −6→15
5005 independent reflections	2 standard reflections every 120 min
3963 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.049P)2 + 0.1514P] where P = (Fo2 + 2Fc2)/3
5005 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.47 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
O4	0.14028 (12)	0.17020 (14)	0.16858 (12)	0.02591 (17)
O2	0.20484 (12)	0.04327 (13)	−0.08942 (12)	0.02816 (18)
O1	0.07961 (14)	0.30061 (15)	−0.02599 (13)	0.03096 (19)
O3	0.41615 (12)	0.37060 (14)	0.12629 (14)	0.0328 (2)
O5	−0.09804 (14)	0.30451 (14)	0.25390 (12)	0.02842 (18)
O6	0.01424 (14)	0.12073 (17)	0.37735 (13)	0.0330 (2)
P1	0.21242 (4)	0.23999 (4)	0.04410 (4)	0.02125 (7)
P2	−0.03708 (4)	0.15037 (4)	0.23497 (4)	0.02013 (7)
N2	0.71399 (14)	0.34670 (15)	1.01546 (13)	0.02438 (18)
H2A	0.7405	0.3187	1.0954	0.037*
H2B	0.6259	0.3920	1.0259	0.037*
H2C	0.8188	0.4345	1.0204	0.037*
N1	0.37134 (15)	0.21366 (16)	0.52122 (14)	0.0284 (2)
H1	0.2559	0.1902	0.4771	0.034*
C1	0.41069 (16)	0.17716 (18)	0.64460 (16)	0.0259 (2)
H1A	0.3140	0.1291	0.6824	0.031*
C4	0.6907 (2)	0.3225 (2)	0.53050 (17)	0.0320 (3)
H4	0.7847	0.3727	0.4913	0.038*
C6	0.64164 (17)	0.17070 (18)	0.85588 (16)	0.0264 (2)
H6A	0.5287	0.0744	0.8515	0.032*
H6B	0.7369	0.1203	0.8456	0.032*
C2	0.59489 (16)	0.21046 (16)	0.71693 (14)	0.02293 (19)
C5	0.5057 (2)	0.28559 (19)	0.46376 (16)	0.0309 (2)
H5	0.4735	0.3106	0.3784	0.037*
C3	0.73527 (17)	0.28345 (19)	0.65771 (16)	0.0288 (2)
H3	0.8598	0.3064	0.7034	0.035*

	U11	U22	U33	U12	U13	U23
O4	0.0190 (3)	0.0374 (5)	0.0315 (4)	0.0132 (3)	0.0114 (3)	0.0233 (4)
O2	0.0190 (3)	0.0275 (4)	0.0306 (4)	0.0079 (3)	0.0068 (3)	0.0089 (3)
O1	0.0281 (4)	0.0376 (5)	0.0413 (5)	0.0170 (4)	0.0131 (4)	0.0284 (4)
O3	0.0174 (3)	0.0290 (4)	0.0409 (5)	0.0034 (3)	0.0105 (3)	0.0109 (4)
O5	0.0331 (4)	0.0325 (4)	0.0273 (4)	0.0199 (4)	0.0114 (4)	0.0157 (4)
O6	0.0267 (4)	0.0532 (6)	0.0328 (5)	0.0175 (4)	0.0104 (4)	0.0320 (5)
P1	0.01556 (11)	0.02324 (13)	0.02726 (14)	0.00693 (9)	0.00856 (10)	0.01444 (11)
P2	0.01707 (11)	0.02625 (13)	0.02125 (13)	0.00966 (10)	0.00632 (9)	0.01460 (11)
N2	0.0213 (4)	0.0309 (5)	0.0267 (4)	0.0122 (3)	0.0078 (3)	0.0180 (4)
N1	0.0235 (4)	0.0314 (5)	0.0285 (5)	0.0109 (4)	0.0019 (4)	0.0152 (4)
C1	0.0198 (4)	0.0305 (5)	0.0293 (5)	0.0101 (4)	0.0065 (4)	0.0167 (5)
C4	0.0303 (6)	0.0337 (6)	0.0281 (6)	0.0080 (5)	0.0117 (5)	0.0146 (5)
C6	0.0250 (5)	0.0289 (5)	0.0287 (5)	0.0123 (4)	0.0054 (4)	0.0172 (4)
C2	0.0197 (4)	0.0245 (5)	0.0235 (5)	0.0091 (4)	0.0047 (4)	0.0114 (4)
C5	0.0360 (6)	0.0298 (6)	0.0248 (5)	0.0116 (5)	0.0055 (5)	0.0143 (5)
C3	0.0201 (4)	0.0345 (6)	0.0284 (6)	0.0092 (4)	0.0073 (4)	0.0137 (5)

O4—P2	1.5992 (10)	N1—C5	1.3393 (19)
O4—P1	1.6057 (10)	N1—H1	0.8600
O2—P2i	1.6044 (14)	C1—C2	1.3875 (17)
O2—P1	1.6085 (11)	C1—H1A	0.9300
O1—P1	1.4766 (10)	C4—C5	1.372 (2)
O3—P1	1.4781 (12)	C4—C3	1.389 (2)
O5—P2	1.4739 (10)	C4—H4	0.9300
O6—P2	1.4824 (10)	C6—C2	1.4990 (17)
P2—O2i	1.6044 (14)	C6—H6A	0.9700
N2—C6	1.4894 (18)	C6—H6B	0.9700
N2—H2A	0.8900	C2—C3	1.3875 (18)
N2—H2B	0.8900	C5—H5	0.9300
N2—H2C	0.8900	C3—H3	0.9300
N1—C1	1.3345 (17)
P2—O4—P1	136.26 (6)	C5—N1—H1	118.9
P2i—O2—P1	134.03 (6)	N1—C1—C2	120.46 (12)
O1—P1—O3	120.41 (7)	N1—C1—H1A	119.8
O1—P1—O4	110.99 (6)	C2—C1—H1A	119.8
O3—P1—O4	106.65 (6)	C5—C4—C3	118.82 (13)
O1—P1—O2	111.42 (7)	C5—C4—H4	120.6
O3—P1—O2	105.82 (7)	C3—C4—H4	120.6
O4—P1—O2	99.36 (6)	N2—C6—C2	111.53 (10)
O5—P2—O6	119.04 (7)	N2—C6—H6A	109.3
O5—P2—O4	112.23 (6)	C2—C6—H6A	109.3
O6—P2—O4	105.42 (6)	N2—C6—H6B	109.3
O5—P2—O2i	106.33 (6)	C2—C6—H6B	109.3
O6—P2—O2i	109.45 (7)	H6A—C6—H6B	108.0
O4—P2—O2i	103.28 (6)	C3—C2—C1	117.98 (11)
C6—N2—H2A	109.5	C3—C2—C6	120.87 (11)
C6—N2—H2B	109.5	C1—C2—C6	121.15 (11)
H2A—N2—H2B	109.5	N1—C5—C4	120.20 (12)
C6—N2—H2C	109.5	N1—C5—H5	119.9
H2A—N2—H2C	109.5	C4—C5—H5	119.9
H2B—N2—H2C	109.5	C2—C3—C4	120.36 (12)
C1—N1—C5	122.18 (11)	C2—C3—H3	119.8
C1—N1—H1	118.9	C4—C3—H3	119.8

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6	0.86	1.77	2.6294 (18)	175
N2—H2A···O5ii	0.89	1.88	2.7079 (17)	154
N2—H2B···O3iii	0.89	2.02	2.7350 (17)	137
N2—H2C···O1iv	0.89	2.08	2.831 (2)	141
C1—H1A···O6v	0.93	2.55	3.381 (2)	149
C4—H4···O5vi	0.93	2.48	3.281 (2)	144
C5—H5···O4	0.93	2.60	3.256 (2)	128
C6—H6B···O1ii	0.97	2.44	3.117 (2)	127

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6	0.86	1.77	2.6294 (18)	175
N2—H2A⋯O5i	0.89	1.88	2.7079 (17)	154
N2—H2B⋯O3ii	0.89	2.02	2.7350 (17)	137
N2—H2C⋯O1iii	0.89	2.08	2.831 (2)	141
C1—H1A⋯O6iv	0.93	2.55	3.381 (2)	149
C4—H4⋯O5v	0.93	2.48	3.281 (2)	144
C5—H5⋯O4	0.93	2.60	3.256 (2)	128
C6—H6B⋯O1i	0.97	2.44	3.117 (2)	127

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