4-Ammonio-2,2,6,6-tetra­methyl­piperidinium bis­(dihydrogen phosphate) monohydrate

Mrad, M.L.; Akriche, S.; Rzaigui, M.; Ben Nasr, C.

doi:10.1107/S1600536809008563

organic compounds

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ISSN: 2056-9890

Volume 65| Part 4| April 2009| Pages o757-o758

doi:10.1107/S1600536809008563

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4-Ammonio-2,2,6,6-tetramethylpiperidinium bis(dihydrogen phosphate) monohydrate

Mohamed Lahbib Mrad,^a Sameh Akriche,^a Mohamed Rzaigui ^a and Cherif Ben Nasr ^a ^*

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna, Tunisia
^*Correspondence e-mail: cherif_bennasr@yahoo.fr

(Received 3 February 2009; accepted 9 March 2009; online 14 March 2009)

In the crystal structure of the title compound, C₉H₂₂N₂²⁺·2H₂PO₄⁻·H₂O, the H₂PO₄⁻ anions are hydrogen bonded to each other, forming a ribbon parallel to the b axis. The water molecules connect these ribbons via O—H⋯O hydrogen bonds. The organic cations are attached to the dihydrogen phosphate anions and water molecules 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 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]_n subnetwork as a polyanion, see: Kefi et al. (2006).

Experimental

Crystal data

C₉H₂₂N₂²⁺·2H₂PO₄⁻·H₂O
M_r = 370.27
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.049
wR(F²) = 0.128
S = 1.00
3953 reflections
216 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.49 e Å⁻³

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⋯O8^iv	0.90	1.84	2.742 (3)	176
N1—H1B⋯O5^v	0.90	2.31	3.168 (3)	159
N1—H1B⋯O8^v	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⋯O9^vi	0.97	2.58	3.492 (4)	158
C9—H9A⋯O7^vi	0.96	2.40	3.343 (3)	168
Symmetry codes: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1; (vi) -x+1, -y, -z+1.

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 ).

Supporting information

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

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

checkCIF report

Comment top

The combination of organic molecules and inorganic materials was the starting point for the development of new hybrid compounds having many practical and potential applications in various fields, such as biomolecular sciences, catalysis, fuel cells, liquid crystal-material development and quadratic nonlinear optics (Wang et al., 1996; Coombs et al., 1997; Masse et al., 1993). Among these hybrid compounds, organic phosphates are particularly interesting owing to the specific H-bond schemes that they can present in their infinite networks (Baoub & Jouini, 1998). We report here the synthesis and the crystal structure of a new member of this family, the compound (C₉H₂₈N₂O₉P₂). As shown in Fig. 1, to ensure charge equilibrium the organic species is doubly protonated at N1 and N2 nitrogen atoms. Thus, the structure associates to each 4-ammonio-2,2,6,6,-tetramethylpiperidinium cation two dihydrogen phosphate anions and one water molecule. The two H₂PO₄^- are crystallographically independent. They form, via H-bonds a repetitive motif of four member (H₂PO₄^-)₄ (Fig. 2). The organic cations and the water molecules are attached to these units via (O—H···O), N—H···O and C—H···O hydrogen bonds to perform a three dimensional infinite network. An examination of the anionic entity shows that the O···O distances involved in hydrogen bonds [2.537 (3) to 2.662 (3) A°] are close to the O···O distances in the H₂PO₄^- tetrahedra [2.469 (3) to 2.536 (3) A°], so one could consider the [(H₂PO₄^-)₄]_n subnetwork as a polyanion (Kefi et al., 2OO6). The detailed geometries of H₂P(1)O₄^- and H₂P(2)O₄^- entities show that the P···O distances significantly are shorter [1.480 (2) to 1.515 (2) A°] than the P···OH distances [1.552 (2) to 1.582 (2) A°], which is in full agreement with those observed in such anions in other organic dihydrogenomonophosphates [Oueslati and Ben Nasr, 2006].

Related literature top

For common applications of hybrid compounds, see: Wang et al. (1996); Coombs et al. (1997); Masse et al. (1993). For organic 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]_n subnetwork as a polyanion, see: Kefi et al. (2006).

Experimental top

Crystals of the title compound have been prepared in a Petri dish by adding 50 mmol of concentrated orthophosphoric acid (Fluka, 85%, d = 1.7) to 25 mmol of 4-Amino-2,2,6,6-tetramethylpiperidine (Acros) dissolved in ethanol. After agitation, the resulting solution has been slowly evaporated at room temperature until the formation of single crystals suitable for X-ray structure analysis and these remained stable under normal conditions of temperature and humidity.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); 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).

Figures top

	Fig. 1. A view of (C₉H₂₈N₂O₉P₂), showing 40% probability displacement ellipsoids and arbitrary spheres for the H atoms.
	Fig. 2. Projection of (C₉H₂₈N₂O₉P₂) subnetwork along the b axis.

4-Ammonio-2,2,6,6-tetramethylpiperidinium bis(dihydrogen phosphate) monohydrate top

Crystal data top

C₉H₂₂N₂²⁺·2H₂PO₄⁻·H₂O	F(000) = 792
M_r = 370.27	D_x = 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

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.056
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.6°
Graphite monochromator	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 top

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(F_o²) + (0.0646P)²] where P = (F_o² + 2F_c²)/3
3953 reflections	(Δ/σ)_max = 0.001
216 parameters	Δρ_max = 0.32 e Å⁻³
3 restraints	Δρ_min = −0.49 e Å⁻³

Crystal data top

C₉H₂₂N₂²⁺·2H₂PO₄⁻·H₂O	V = 1642.4 (8) Å³
M_r = 370.27	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.604 (5) Å	µ = 0.31 mm⁻¹
b = 8.249 (2) Å	T = 298 K
c = 16.321 (2) Å	0.5 × 0.35 × 0.25 mm
β = 104.56 (4)°

Data collection top

Enraf–Nonius TurboCAD-4 diffractometer	R_int = 0.056
6617 measured reflections	2 standard reflections every 120 min
3953 independent reflections	intensity decay: 8%
2575 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.049	3 restraints
wR(F²) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 0.32 e Å⁻³
3953 reflections	Δρ_min = −0.49 e Å⁻³
216 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O8^iv	0.90	1.84	2.742 (3)	176
N1—H1B···O5^v	0.90	2.31	3.168 (3)	159
N1—H1B···O8^v	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···O9^vi	0.97	2.58	3.492 (4)	158
C9—H9A···O7^vi	0.96	2.40	3.343 (3)	168

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z+1/2; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₉H₂₂N₂²⁺·2H₂PO₄⁻·H₂O
M_r	370.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.604 (5), 8.249 (2), 16.321 (2)
β (°)	104.56 (4)
V (Å³)	1642.4 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.5 × 0.35 × 0.25

Data collection
Diffractometer	Enraf–Nonius TurboCAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6617, 3953, 2575
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.049, 0.128, 1.00
No. of reflections	3953
No. of parameters	216
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.49

Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.74	2.537 (3)	163.1
O4—H4···O5ⁱⁱ	0.82	1.79	2.538 (3)	151.6
O6—H6···O3	0.82	1.83	2.646 (3)	172.1
O7—H7···O1	0.82	1.85	2.662 (3)	172.6
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···O8^iv	0.90	1.84	2.742 (3)	176.4
N1—H1B···O5^v	0.90	2.31	3.168 (3)	158.5
N1—H1B···O8^v	0.90	2.33	3.038 (3)	135.8
N2—H2A···O2	0.89	2.05	2.929 (3)	171.5
N2—H2A···O1	0.89	2.51	3.076 (3)	121.9
N2—H2B···O3ⁱⁱ	0.89	2.07	2.919 (3)	159.7
N2—H2C···O9	0.89	1.88	2.721 (4)	155.9
C3—H3···O6ⁱⁱ	0.98	2.59	3.406 (3)	140.8
C4—H4B···O9^vi	0.97	2.58	3.492 (4)	157.6
C9—H9A···O7^vi	0.96	2.40	3.343 (3)	168.2

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) x, −y+1/2, z+1/2; (iv) x−1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x+1, −y, −z+1.

Acknowledgements

We acknowledge the support provided by the Secretary of State for Scientific Research and Technology of Tunisia.

References

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Volume 65| Part 4| April 2009| Pages o757-o758

doi:10.1107/S1600536809008563

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-Ammonio-2,2,6,6-tetra­methyl­piperidinium bis­­(di­hydrogen phosphate) monohydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-Ammonio-2,2,6,6-tetramethylpiperidinium bis(dihydrogen phosphate) monohydrate