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Acta Cryst. (2009). E65, o757-o758    [ doi:10.1107/S1600536809008563 ]

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

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

Abstract top

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.

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.

Refinement top

Hydrogen atoms were placed in calculated positions and refined as part of a riding model except those of the water molecule which were located in difference Fourier maps and their positions and isotropic displacement parameters refined.

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
[Figure 1] Fig. 1. A view of (C9H28N2O9P2), showing 40% probability displacement ellipsoids and arbitrary spheres for the H atoms.
[Figure 2] 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−·H2OF(000) = 792
Mr = 370.27Dx = 1.497 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 25 reflections
a = 12.604 (5) Åθ = 9–11°
b = 8.249 (2) ŵ = 0.31 mm−1
c = 16.321 (2) ÅT = 298 K
β = 104.56 (4)°Prism, colorless
V = 1642.4 (8) Å30.5 × 0.35 × 0.25 mm
Z = 4
Data collection top
Enraf–Nonius TurboCAD-4
diffractometer		Rint = 0.056
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 2.6°
graphiteh = −16→16
Nonprofiled ω scansk = 0→10
6617 measured reflectionsl = −10→21
3953 independent reflections2 standard reflections every 120 min
2575 reflections with I > 2σ(I) intensity decay: 8%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H 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 parametersΔρmax = 0.32 e Å−3
3 restraintsΔρmin = −0.48 e Å−3
Crystal data top
C9H22N22+·2H2PO4−·H2OV = 1642.4 (8) Å3
Mr = 370.27Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.604 (5) ŵ = 0.31 mm−1
b = 8.249 (2) ÅT = 298 K
c = 16.321 (2) Å0.5 × 0.35 × 0.25 mm
β = 104.56 (4)°
Data collection top
Enraf–Nonius TurboCAD-4
diffractometer		Rint = 0.056
6617 measured reflectionsθmax = 28.0°
3953 independent reflections2 standard reflections every 120 min
2575 reflections with I > 2σ(I) intensity decay: 8%
Refinement top
R[F2 > 2σ(F2)] = 0.049H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.128Δρmax = 0.32 e Å−3
S = 1.00Δρmin = −0.48 e Å−3
3953 reflectionsAbsolute structure: ?
216 parametersFlack parameter: ?
3 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
P10.52437 (5)0.19580 (8)0.19702 (4)0.02151 (17)
P20.79116 (5)0.36565 (8)0.37537 (4)0.02164 (17)
O10.57523 (14)0.0956 (2)0.27473 (12)0.0301 (4)
O20.42447 (15)0.2885 (2)0.21633 (14)0.0332 (5)
H20.43790.38590.22030.050*
O30.60240 (14)0.3112 (2)0.17133 (12)0.0279 (4)
O40.47608 (15)0.0832 (3)0.12059 (12)0.0372 (5)
H40.41550.05090.12330.056*
O50.70615 (14)0.4348 (2)0.41668 (12)0.0312 (5)
O60.77241 (16)0.4361 (3)0.28269 (12)0.0356 (5)
H60.71720.39540.25200.053*
O70.77502 (16)0.1773 (2)0.36442 (15)0.0380 (5)
H70.71130.15770.33940.057*
O80.90532 (14)0.3991 (3)0.42314 (13)0.0358 (5)
O90.59416 (18)0.2150 (3)0.49650 (14)0.0393 (5)
H910.626 (3)0.290 (3)0.476 (2)0.055 (11)*
H920.597 (4)0.226 (6)0.5489 (11)0.13 (2)*
N10.12655 (16)0.3672 (3)0.44120 (13)0.0195 (4)
H1A0.05350.37630.43290.023*
H1B0.15730.43600.48330.023*
N20.40484 (17)0.1521 (3)0.37758 (15)0.0301 (5)
H2A0.41830.19310.33070.045*
H2B0.40930.04450.37640.045*
H2C0.45400.19000.42260.045*
C10.15485 (19)0.4285 (3)0.36124 (16)0.0228 (5)
C20.2733 (2)0.3797 (3)0.36452 (18)0.0268 (6)
H22A0.28920.40530.31080.032*
H22B0.32310.44180.40830.032*
C30.29204 (19)0.2008 (3)0.38261 (17)0.0241 (5)
H30.23830.13950.34000.029*
C40.27523 (19)0.1613 (3)0.46967 (17)0.0233 (5)
H4A0.32530.22560.51210.028*
H4B0.29190.04780.48230.028*
C50.15786 (19)0.1958 (3)0.47367 (17)0.0221 (5)
C60.0747 (2)0.3618 (4)0.28233 (18)0.0404 (8)
H6A0.08660.24750.27810.061*
H6B0.08620.41550.23310.061*
H6C0.00100.38040.28620.061*
C70.1434 (2)0.6124 (3)0.36298 (19)0.0345 (7)
H7A0.07000.64010.36460.052*
H7B0.15890.65800.31310.052*
H7C0.19410.65500.41230.052*
C80.0775 (2)0.0728 (4)0.4223 (2)0.0339 (7)
H8A0.08750.06650.36600.051*
H8B0.00380.10620.41980.051*
H8C0.0908−0.03170.44880.051*
C90.1488 (2)0.1962 (3)0.56518 (17)0.0291 (6)
H9A0.16070.08850.58790.044*
H9B0.07710.23250.56700.044*
H9C0.20300.26790.59820.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0200 (3)0.0239 (3)0.0216 (3)−0.0024 (3)0.0070 (3)−0.0030 (3)
P20.0183 (3)0.0229 (3)0.0226 (4)0.0007 (3)0.0032 (2)−0.0014 (3)
O10.0333 (10)0.0257 (10)0.0286 (11)−0.0049 (8)0.0030 (8)0.0036 (8)
O20.0323 (10)0.0254 (10)0.0473 (13)0.0010 (8)0.0203 (9)−0.0007 (10)
O30.0245 (9)0.0328 (10)0.0272 (10)−0.0066 (8)0.0077 (8)0.0008 (9)
O40.0286 (10)0.0517 (13)0.0333 (12)−0.0120 (9)0.0115 (9)−0.0202 (10)
O50.0281 (9)0.0362 (11)0.0317 (11)0.0093 (8)0.0121 (8)0.0049 (9)
O60.0392 (11)0.0427 (12)0.0228 (11)−0.0127 (9)0.0037 (8)0.0015 (9)
O70.0322 (10)0.0249 (10)0.0506 (14)0.0027 (8)−0.0014 (10)−0.0035 (10)
O80.0209 (9)0.0438 (12)0.0382 (12)−0.0010 (8)−0.0009 (8)−0.0108 (10)
O90.0422 (12)0.0495 (14)0.0278 (12)−0.0122 (10)0.0117 (10)−0.0011 (11)
N10.0193 (9)0.0214 (10)0.0183 (11)0.0005 (8)0.0059 (8)0.0003 (9)
N20.0263 (11)0.0339 (13)0.0335 (13)0.0045 (9)0.0136 (10)−0.0046 (11)
C10.0231 (12)0.0300 (13)0.0154 (12)0.0004 (11)0.0051 (10)0.0048 (11)
C20.0252 (12)0.0308 (14)0.0275 (15)−0.0008 (11)0.0122 (11)0.0038 (12)
C30.0194 (11)0.0283 (13)0.0268 (14)−0.0006 (10)0.0100 (10)−0.0038 (12)
C40.0227 (11)0.0209 (13)0.0263 (14)0.0032 (10)0.0064 (10)0.0010 (11)
C50.0226 (11)0.0194 (11)0.0255 (14)−0.0010 (10)0.0082 (10)−0.0001 (11)
C60.0330 (15)0.061 (2)0.0229 (15)0.0037 (14)−0.0001 (12)−0.0019 (15)
C70.0391 (15)0.0298 (15)0.0374 (17)0.0078 (12)0.0148 (13)0.0118 (13)
C80.0284 (13)0.0279 (14)0.0482 (19)−0.0110 (11)0.0146 (13)−0.0081 (14)
C90.0350 (14)0.0278 (14)0.0280 (15)0.0019 (11)0.0143 (12)0.0071 (12)
Geometric parameters (Å, °) top
P1—O31.5020 (19)C1—C21.534 (3)
P1—O11.515 (2)C2—C31.512 (4)
P1—O41.552 (2)C2—H22A0.9700
P1—O21.5713 (19)C2—H22B0.9700
P2—O81.480 (2)C3—C41.524 (4)
P2—O51.5137 (19)C3—H30.9800
P2—O71.572 (2)C4—C51.524 (3)
P2—O61.582 (2)C4—H4A0.9700
O2—H20.8200C4—H4B0.9700
O4—H40.8200C5—C91.526 (4)
O6—H60.8200C5—C81.527 (4)
O7—H70.8200C6—H6A0.9600
O9—H910.848 (10)C6—H6B0.9600
O9—H920.852 (10)C6—H6C0.9600
N1—C11.523 (3)C7—H7A0.9600
N1—C51.527 (3)C7—H7B0.9600
N1—H1A0.9000C7—H7C0.9600
N1—H1B0.9000C8—H8A0.9600
N2—C31.499 (3)C8—H8B0.9600
N2—H2A0.8900C8—H8C0.9600
N2—H2B0.8900C9—H9A0.9600
N2—H2C0.8900C9—H9B0.9600
C1—C71.525 (4)C9—H9C0.9600
C1—C61.526 (4)
O3—P1—O1114.23 (11)N2—C3—C4110.5 (2)
O3—P1—O4107.88 (11)C2—C3—C4109.8 (2)
O1—P1—O4110.16 (13)N2—C3—H3108.6
O3—P1—O2111.20 (12)C2—C3—H3108.6
O1—P1—O2106.82 (12)C4—C3—H3108.6
O4—P1—O2106.28 (12)C3—C4—C5111.4 (2)
O8—P2—O5113.48 (12)C3—C4—H4A109.4
O8—P2—O7108.97 (11)C5—C4—H4A109.4
O5—P2—O7109.72 (12)C3—C4—H4B109.4
O8—P2—O6109.09 (13)C5—C4—H4B109.4
O5—P2—O6109.58 (12)H4A—C4—H4B108.0
O7—P2—O6105.71 (12)C4—C5—C9110.8 (2)
P1—O2—H2109.5C4—C5—N1109.09 (19)
P1—O4—H4109.5C9—C5—N1105.1 (2)
P2—O6—H6109.5C4—C5—C8111.7 (2)
P2—O7—H7109.5C9—C5—C8109.7 (2)
H91—O9—H92114 (3)N1—C5—C8110.3 (2)
C1—N1—C5120.63 (19)C1—C6—H6A109.5
C1—N1—H1A107.2C1—C6—H6B109.5
C5—N1—H1A107.2H6A—C6—H6B109.5
C1—N1—H1B107.2C1—C6—H6C109.5
C5—N1—H1B107.2H6A—C6—H6C109.5
H1A—N1—H1B106.8H6B—C6—H6C109.5
C3—N2—H2A109.5C1—C7—H7A109.5
C3—N2—H2B109.5C1—C7—H7B109.5
H2A—N2—H2B109.5H7A—C7—H7B109.5
C3—N2—H2C109.5C1—C7—H7C109.5
H2A—N2—H2C109.5H7A—C7—H7C109.5
H2B—N2—H2C109.5H7B—C7—H7C109.5
N1—C1—C7105.7 (2)C5—C8—H8A109.5
N1—C1—C6110.8 (2)C5—C8—H8B109.5
C7—C1—C6109.2 (2)H8A—C8—H8B109.5
N1—C1—C2108.6 (2)C5—C8—H8C109.5
C7—C1—C2110.9 (2)H8A—C8—H8C109.5
C6—C1—C2111.5 (2)H8B—C8—H8C109.5
C3—C2—C1111.4 (2)C5—C9—H9A109.5
C3—C2—H22A109.3C5—C9—H9B109.5
C1—C2—H22A109.3H9A—C9—H9B109.5
C3—C2—H22B109.3C5—C9—H9C109.5
C1—C2—H22B109.3H9A—C9—H9C109.5
H22A—C2—H22B108.0H9B—C9—H9C109.5
N2—C3—C2110.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.821.742.537 (3)163
O4—H4···O5ii0.821.792.538 (3)152
O6—H6···O30.821.832.646 (3)172
O7—H7···O10.821.852.662 (3)173
O9—H91···O50.85 (1)1.97 (1)2.811 (3)170 (3)
O9—H92···O3iii0.85 (1)2.00 (1)2.837 (3)165 (5)
O9—H92···O4iii0.85 (1)2.66 (5)3.256 (3)128 (5)
N1—H1A···O8iv0.901.842.742 (3)176
N1—H1B···O5v0.902.313.168 (3)159
N1—H1B···O8v0.902.333.038 (3)136
N2—H2A···O20.892.052.929 (3)172
N2—H2A···O10.892.513.076 (3)122
N2—H2B···O3ii0.892.072.919 (3)160
N2—H2C···O90.891.882.721 (4)156
C3—H3···O6ii0.982.593.406 (3)141
C4—H4B···O9vi0.972.583.492 (4)158
C9—H9A···O7vi0.962.403.343 (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.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.821.742.537 (3)163
O4—H4···O5ii0.821.792.538 (3)152
O6—H6···O30.821.832.646 (3)172
O7—H7···O10.821.852.662 (3)173
O9—H91···O50.85 (1)1.97 (1)2.811 (3)170 (3)
O9—H92···O3iii0.85 (1)2.00 (1)2.837 (3)165 (5)
O9—H92···O4iii0.85 (1)2.66 (5)3.256 (3)128 (5)
N1—H1A···O8iv0.901.842.742 (3)176
N1—H1B···O5v0.902.313.168 (3)159
N1—H1B···O8v0.902.333.038 (3)136
N2—H2A···O20.892.052.929 (3)172
N2—H2A···O10.892.513.076 (3)122
N2—H2B···O3ii0.892.072.919 (3)160
N2—H2C···O90.891.882.721 (4)156
C3—H3···O6ii0.982.593.406 (3)141
C4—H4B···O9vi0.972.583.492 (4)158
C9—H9A···O7vi0.962.403.343 (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.
Acknowledgements top

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

references
References top

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