4-Ammonio-2,2,6,6-tetra-methyl-piperidinium bis-(dihydrogen phosphate) monohydrate.

In the crystal structure of the title compound, C(9)H(22)N(2) (2+)·2H(2)PO(4) (-)·H(2)O, the H(2)PO(4) (-) anions are hydrogen bonded to each other, forming a ribbon parallel to the b axis. The water mol-ecules connect these ribbons via O-H⋯O hydrogen bonds. The organic cations are attached to the dihydrogen phosphate anions and water mol-ecules through N-H⋯O and C-H⋯O hydrogen bonds, forming an infinite three-dimensional network.

Related literature

For common applications of hybrid compounds, see: Wang et al. (1996 ▶); Coombs et al. (1997 ▶); Masse et al. (1993 ▶). For organic n class="Chemical">phosphates, see: Baoub & Jouini (1998 ▶). For a discussion of the O⋯O distances, see: Kefi et al. (2006 ▶). For P⋯O bond-length data, see: Oueslati & Ben Nasr (2006 ▶). For the [(H2PO4 −)4] subnetwork as a polyanion, see: Kefi et al. (2006 ▶).

Experimental

Crystal data

C9H22N2 2+·2n class="Chemical">H2PO4 −·H2O

M = 370.27

Monoclinic,

a = 12.604 (5) Å

b = 8.249 (2) Å

c = 16.321 (2) Å

β = 104.56 (4)°

V = 1642.4 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.31 mm−1

T = 298 K

0.5 × 0.35 × 0.25 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer

Absorption correction: none

6617 measured reflections

3953 independent reflections

2575 reflections with I > 2σ(I)

R int = 0.056

2 standard reflections frequency: 120 min intensity decay: 8%

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.128

S = 1.00

3953 reflections

216 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.49 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, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008563/wk2099sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809008563/wk2099Isup2.hkl

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

C9H22N22+·2H2PO4−·H2O	F(000) = 792
Mr = 370.27	Dx = 1.497 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.604 (5) Å	θ = 9–11°
b = 8.249 (2) Å	µ = 0.31 mm−1
c = 16.321 (2) Å	T = 298 K
β = 104.56 (4)°	Prism, colorless
V = 1642.4 (8) Å3	0.5 × 0.35 × 0.25 mm
Z = 4

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.056
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.6°
graphite	h = −16→16
Nonprofiled ω scans	k = 0→10
6617 measured reflections	l = −10→21
3953 independent reflections	2 standard reflections every 120 min
2575 reflections with I > 2σ(I)	intensity decay: 8%

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0646P)2] where P = (Fo2 + 2Fc2)/3
3953 reflections	(Δ/σ)max = 0.001
216 parameters	Δρmax = 0.32 e Å−3
3 restraints	Δρmin = −0.48 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	0.52437 (5)	0.19580 (8)	0.19702 (4)	0.02151 (17)
P2	0.79116 (5)	0.36565 (8)	0.37537 (4)	0.02164 (17)
O1	0.57523 (14)	0.0956 (2)	0.27473 (12)	0.0301 (4)
O2	0.42447 (15)	0.2885 (2)	0.21633 (14)	0.0332 (5)
H2	0.4379	0.3859	0.2203	0.050*
O3	0.60240 (14)	0.3112 (2)	0.17133 (12)	0.0279 (4)
O4	0.47608 (15)	0.0832 (3)	0.12059 (12)	0.0372 (5)
H4	0.4155	0.0509	0.1233	0.056*
O5	0.70615 (14)	0.4348 (2)	0.41668 (12)	0.0312 (5)
O6	0.77241 (16)	0.4361 (3)	0.28269 (12)	0.0356 (5)
H6	0.7172	0.3954	0.2520	0.053*
O7	0.77502 (16)	0.1773 (2)	0.36442 (15)	0.0380 (5)
H7	0.7113	0.1577	0.3394	0.057*
O8	0.90532 (14)	0.3991 (3)	0.42314 (13)	0.0358 (5)
O9	0.59416 (18)	0.2150 (3)	0.49650 (14)	0.0393 (5)
H91	0.626 (3)	0.290 (3)	0.476 (2)	0.055 (11)*
H92	0.597 (4)	0.226 (6)	0.5489 (11)	0.13 (2)*
N1	0.12655 (16)	0.3672 (3)	0.44120 (13)	0.0195 (4)
H1A	0.0535	0.3763	0.4329	0.023*
H1B	0.1573	0.4360	0.4833	0.023*
N2	0.40484 (17)	0.1521 (3)	0.37758 (15)	0.0301 (5)
H2A	0.4183	0.1931	0.3307	0.045*
H2B	0.4093	0.0445	0.3764	0.045*
H2C	0.4540	0.1900	0.4226	0.045*
C1	0.15485 (19)	0.4285 (3)	0.36124 (16)	0.0228 (5)
C2	0.2733 (2)	0.3797 (3)	0.36452 (18)	0.0268 (6)
H22A	0.2892	0.4053	0.3108	0.032*
H22B	0.3231	0.4418	0.4083	0.032*
C3	0.29204 (19)	0.2008 (3)	0.38261 (17)	0.0241 (5)
H3	0.2383	0.1395	0.3400	0.029*
C4	0.27523 (19)	0.1613 (3)	0.46967 (17)	0.0233 (5)
H4A	0.3253	0.2256	0.5121	0.028*
H4B	0.2919	0.0478	0.4823	0.028*
C5	0.15786 (19)	0.1958 (3)	0.47367 (17)	0.0221 (5)
C6	0.0747 (2)	0.3618 (4)	0.28233 (18)	0.0404 (8)
H6A	0.0866	0.2475	0.2781	0.061*
H6B	0.0862	0.4155	0.2331	0.061*
H6C	0.0010	0.3804	0.2862	0.061*
C7	0.1434 (2)	0.6124 (3)	0.36298 (19)	0.0345 (7)
H7A	0.0700	0.6401	0.3646	0.052*
H7B	0.1589	0.6580	0.3131	0.052*
H7C	0.1941	0.6550	0.4123	0.052*
C8	0.0775 (2)	0.0728 (4)	0.4223 (2)	0.0339 (7)
H8A	0.0875	0.0665	0.3660	0.051*
H8B	0.0038	0.1062	0.4198	0.051*
H8C	0.0908	−0.0317	0.4488	0.051*
C9	0.1488 (2)	0.1962 (3)	0.56518 (17)	0.0291 (6)
H9A	0.1607	0.0885	0.5879	0.044*
H9B	0.0771	0.2325	0.5670	0.044*
H9C	0.2030	0.2679	0.5982	0.044*

	U11	U22	U33	U12	U13	U23
P1	0.0200 (3)	0.0239 (3)	0.0216 (3)	−0.0024 (3)	0.0070 (3)	−0.0030 (3)
P2	0.0183 (3)	0.0229 (3)	0.0226 (4)	0.0007 (3)	0.0032 (2)	−0.0014 (3)
O1	0.0333 (10)	0.0257 (10)	0.0286 (11)	−0.0049 (8)	0.0030 (8)	0.0036 (8)
O2	0.0323 (10)	0.0254 (10)	0.0473 (13)	0.0010 (8)	0.0203 (9)	−0.0007 (10)
O3	0.0245 (9)	0.0328 (10)	0.0272 (10)	−0.0066 (8)	0.0077 (8)	0.0008 (9)
O4	0.0286 (10)	0.0517 (13)	0.0333 (12)	−0.0120 (9)	0.0115 (9)	−0.0202 (10)
O5	0.0281 (9)	0.0362 (11)	0.0317 (11)	0.0093 (8)	0.0121 (8)	0.0049 (9)
O6	0.0392 (11)	0.0427 (12)	0.0228 (11)	−0.0127 (9)	0.0037 (8)	0.0015 (9)
O7	0.0322 (10)	0.0249 (10)	0.0506 (14)	0.0027 (8)	−0.0014 (10)	−0.0035 (10)
O8	0.0209 (9)	0.0438 (12)	0.0382 (12)	−0.0010 (8)	−0.0009 (8)	−0.0108 (10)
O9	0.0422 (12)	0.0495 (14)	0.0278 (12)	−0.0122 (10)	0.0117 (10)	−0.0011 (11)
N1	0.0193 (9)	0.0214 (10)	0.0183 (11)	0.0005 (8)	0.0059 (8)	0.0003 (9)
N2	0.0263 (11)	0.0339 (13)	0.0335 (13)	0.0045 (9)	0.0136 (10)	−0.0046 (11)
C1	0.0231 (12)	0.0300 (13)	0.0154 (12)	0.0004 (11)	0.0051 (10)	0.0048 (11)
C2	0.0252 (12)	0.0308 (14)	0.0275 (15)	−0.0008 (11)	0.0122 (11)	0.0038 (12)
C3	0.0194 (11)	0.0283 (13)	0.0268 (14)	−0.0006 (10)	0.0100 (10)	−0.0038 (12)
C4	0.0227 (11)	0.0209 (13)	0.0263 (14)	0.0032 (10)	0.0064 (10)	0.0010 (11)
C5	0.0226 (11)	0.0194 (11)	0.0255 (14)	−0.0010 (10)	0.0082 (10)	−0.0001 (11)
C6	0.0330 (15)	0.061 (2)	0.0229 (15)	0.0037 (14)	−0.0001 (12)	−0.0019 (15)
C7	0.0391 (15)	0.0298 (15)	0.0374 (17)	0.0078 (12)	0.0148 (13)	0.0118 (13)
C8	0.0284 (13)	0.0279 (14)	0.0482 (19)	−0.0110 (11)	0.0146 (13)	−0.0081 (14)
C9	0.0350 (14)	0.0278 (14)	0.0280 (15)	0.0019 (11)	0.0143 (12)	0.0071 (12)

P1—O3	1.5020 (19)	C1—C2	1.534 (3)
P1—O1	1.515 (2)	C2—C3	1.512 (4)
P1—O4	1.552 (2)	C2—H22A	0.9700
P1—O2	1.5713 (19)	C2—H22B	0.9700
P2—O8	1.480 (2)	C3—C4	1.524 (4)
P2—O5	1.5137 (19)	C3—H3	0.9800
P2—O7	1.572 (2)	C4—C5	1.524 (3)
P2—O6	1.582 (2)	C4—H4A	0.9700
O2—H2	0.8200	C4—H4B	0.9700
O4—H4	0.8200	C5—C9	1.526 (4)
O6—H6	0.8200	C5—C8	1.527 (4)
O7—H7	0.8200	C6—H6A	0.9600
O9—H91	0.848 (10)	C6—H6B	0.9600
O9—H92	0.852 (10)	C6—H6C	0.9600
N1—C1	1.523 (3)	C7—H7A	0.9600
N1—C5	1.527 (3)	C7—H7B	0.9600
N1—H1A	0.9000	C7—H7C	0.9600
N1—H1B	0.9000	C8—H8A	0.9600
N2—C3	1.499 (3)	C8—H8B	0.9600
N2—H2A	0.8900	C8—H8C	0.9600
N2—H2B	0.8900	C9—H9A	0.9600
N2—H2C	0.8900	C9—H9B	0.9600
C1—C7	1.525 (4)	C9—H9C	0.9600
C1—C6	1.526 (4)
O3—P1—O1	114.23 (11)	N2—C3—C4	110.5 (2)
O3—P1—O4	107.88 (11)	C2—C3—C4	109.8 (2)
O1—P1—O4	110.16 (13)	N2—C3—H3	108.6
O3—P1—O2	111.20 (12)	C2—C3—H3	108.6
O1—P1—O2	106.82 (12)	C4—C3—H3	108.6
O4—P1—O2	106.28 (12)	C3—C4—C5	111.4 (2)
O8—P2—O5	113.48 (12)	C3—C4—H4A	109.4
O8—P2—O7	108.97 (11)	C5—C4—H4A	109.4
O5—P2—O7	109.72 (12)	C3—C4—H4B	109.4
O8—P2—O6	109.09 (13)	C5—C4—H4B	109.4
O5—P2—O6	109.58 (12)	H4A—C4—H4B	108.0
O7—P2—O6	105.71 (12)	C4—C5—C9	110.8 (2)
P1—O2—H2	109.5	C4—C5—N1	109.09 (19)
P1—O4—H4	109.5	C9—C5—N1	105.1 (2)
P2—O6—H6	109.5	C4—C5—C8	111.7 (2)
P2—O7—H7	109.5	C9—C5—C8	109.7 (2)
H91—O9—H92	114 (3)	N1—C5—C8	110.3 (2)
C1—N1—C5	120.63 (19)	C1—C6—H6A	109.5
C1—N1—H1A	107.2	C1—C6—H6B	109.5
C5—N1—H1A	107.2	H6A—C6—H6B	109.5
C1—N1—H1B	107.2	C1—C6—H6C	109.5
C5—N1—H1B	107.2	H6A—C6—H6C	109.5
H1A—N1—H1B	106.8	H6B—C6—H6C	109.5
C3—N2—H2A	109.5	C1—C7—H7A	109.5
C3—N2—H2B	109.5	C1—C7—H7B	109.5
H2A—N2—H2B	109.5	H7A—C7—H7B	109.5
C3—N2—H2C	109.5	C1—C7—H7C	109.5
H2A—N2—H2C	109.5	H7A—C7—H7C	109.5
H2B—N2—H2C	109.5	H7B—C7—H7C	109.5
N1—C1—C7	105.7 (2)	C5—C8—H8A	109.5
N1—C1—C6	110.8 (2)	C5—C8—H8B	109.5
C7—C1—C6	109.2 (2)	H8A—C8—H8B	109.5
N1—C1—C2	108.6 (2)	C5—C8—H8C	109.5
C7—C1—C2	110.9 (2)	H8A—C8—H8C	109.5
C6—C1—C2	111.5 (2)	H8B—C8—H8C	109.5
C3—C2—C1	111.4 (2)	C5—C9—H9A	109.5
C3—C2—H22A	109.3	C5—C9—H9B	109.5
C1—C2—H22A	109.3	H9A—C9—H9B	109.5
C3—C2—H22B	109.3	C5—C9—H9C	109.5
C1—C2—H22B	109.3	H9A—C9—H9C	109.5
H22A—C2—H22B	108.0	H9B—C9—H9C	109.5
N2—C3—C2	110.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1i	0.82	1.74	2.537 (3)	163
O4—H4···O5ii	0.82	1.79	2.538 (3)	152
O6—H6···O3	0.82	1.83	2.646 (3)	172
O7—H7···O1	0.82	1.85	2.662 (3)	173
O9—H91···O5	0.85 (1)	1.97 (1)	2.811 (3)	170 (3)
O9—H92···O3iii	0.85 (1)	2.00 (1)	2.837 (3)	165 (5)
O9—H92···O4iii	0.85 (1)	2.66 (5)	3.256 (3)	128 (5)
N1—H1A···O8iv	0.90	1.84	2.742 (3)	176
N1—H1B···O5v	0.90	2.31	3.168 (3)	159
N1—H1B···O8v	0.90	2.33	3.038 (3)	136
N2—H2A···O2	0.89	2.05	2.929 (3)	172
N2—H2A···O1	0.89	2.51	3.076 (3)	122
N2—H2B···O3ii	0.89	2.07	2.919 (3)	160
N2—H2C···O9	0.89	1.88	2.721 (4)	156
C3—H3···O6ii	0.98	2.59	3.406 (3)	141
C4—H4B···O9vi	0.97	2.58	3.492 (4)	158
C9—H9A···O7vi	0.96	2.40	3.343 (3)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1i	0.82	1.74	2.537 (3)	163
O4—H4⋯O5ii	0.82	1.79	2.538 (3)	152
O6—H6⋯O3	0.82	1.83	2.646 (3)	172
O7—H7⋯O1	0.82	1.85	2.662 (3)	173
O9—H91⋯O5	0.85 (1)	1.97 (1)	2.811 (3)	170 (3)
O9—H92⋯O3iii	0.85 (1)	2.00 (1)	2.837 (3)	165 (5)
O9—H92⋯O4iii	0.85 (1)	2.66 (5)	3.256 (3)	128 (5)
N1—H1A⋯O8iv	0.90	1.84	2.742 (3)	176
N1—H1B⋯O5v	0.90	2.31	3.168 (3)	159
N1—H1B⋯O8v	0.90	2.33	3.038 (3)	136
N2—H2A⋯O2	0.89	2.05	2.929 (3)	172
N2—H2A⋯O1	0.89	2.51	3.076 (3)	122
N2—H2B⋯O3ii	0.89	2.07	2.919 (3)	160
N2—H2C⋯O9	0.89	1.88	2.721 (4)	156
C3—H3⋯O6ii	0.98	2.59	3.406 (3)	141
C4—H4B⋯O9vi	0.97	2.58	3.492 (4)	158
C9—H9A⋯O7vi	0.96	2.40	3.343 (3)	168

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