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Acta Crystallogr Sect E Struct Rep Online. 2009 September 1; 65(Pt 9): o2300.
Published online 2009 August 29. doi:  10.1107/S1600536809033856
PMCID: PMC2969954

2-Amino­pyridinium diphenyl­phosphinate monohydrate

Abstract

In the crystal of the title hydrated salt, C5H7N2 +·C12H10O2P·H2O, the cations, anions and water mol­ecules connected by N—H(...)O and O—H(...)O hydrogen bonds into a layer along the bc plane; the phenyl rings protrude into the space between the layers. The dihedral angle between rings of anion is 86.1 (1)°.

Related literature

For bidentate ligands with both hard (nitrogen) and soft (phosphorous) donors, see: Espinet & Soulantica (1999 [triangle]); Jeffrey & Rauchfuss (1979 [triangle]). For the use of diphenyl­phosphinic acid in the extraction of trivalent lanthanide cations and as a flame retardant in the ep­oxy resins used in printed circuit boards, see: Almeida (1974 [triangle]); von Gentzkow et al. (1996 [triangle]); Huber et al. (1998 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o2300-scheme1.jpg

Experimental

Crystal data

  • C5H7N2 +·C12H10O2P·H2O
  • M r = 330.31
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o2300-efi1.jpg
  • a = 15.2716 (19) Å
  • b = 9.979 (2) Å
  • c = 11.7671 (15) Å
  • β = 103.073 (10)°
  • V = 1746.8 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.17 mm−1
  • T = 295 K
  • 0.60 × 0.35 × 0.21 mm

Data collection

  • Stoe IPDS-II diffractometer
  • Absorption correction: analytical (X-SHAPE; Stoe & Cie, 2007 [triangle]) T min = 0.813, T max = 0.965
  • 8165 measured reflections
  • 2972 independent reflections
  • 1660 reflections with I > 2σ(I)
  • R int = 0.097

Refinement

  • R[F 2 > 2σ(F 2)] = 0.054
  • wR(F 2) = 0.130
  • S = 1.02
  • 2972 reflections
  • 214 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.21 e Å−3
  • Δρmin = −0.20 e Å−3

Data collection: X-RED (Stoe & Cie, 2007 [triangle]); cell refinement: X-AREA (Stoe & Cie, 2007 [triangle]); data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2001 [triangle]); software used to prepare material for publication: PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033856/ng2622sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809033856/ng2622Isup2.hkl

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

Acknowledgments

This work was supported by a grant from the University of Tehran.

supplementary crystallographic information

Comment

Bidentate ligands containing both hard (nitrogen) and soft (phosphorous) donor atoms are extremely fruitful in both homogenous catalysis and coordination chemistry (Espinet & Soulantica, 1999). Because of having both hard and soft donor atoms, they are called hemilabile ligands (Jeffrey & Rauchfuss, 1979). Diphenylphosphinic acid and its derivatives have been widely used because of their variety of applications. It has been extensively used for extraction of trivalent lanthanide cations and as a flame retardant in epoxy resins that are used in printed circuit boards (Almeida, 1974; Huber, et al., 1998; von Gentzkow, et al., 1996).

The molecular structure of (I) and the atom-numbering scheme are shown in Fig. 1. In this work, attempting to get a new hemilabile bidentate ligand, we obtained pyridinium-2-amine di(phenyl)phosphinate monohydrate, which was unexpectedly produced due to the breaking of P—N bond, probably due to its sensitivity to air and humidity. In the crystal structure, there are three discrete moieties in the asymmetric unit (phosphinic acid, pyridine ring and one water molecule) that are in contact by several hydogen bonds, making a well defined motif. There are also C—H···π interactions between phophinate and pyridinium groups between neighboring motifs. Two P—O bonds are slightly different in distances, (P1—O1 = 1.507 Å and P1—O2 = 1.498 Å), that can be due to the hydrogen bonds between the nitrogen atoms of pyridinium rings to the phosphinate molecules (N1—H1A···O1 and N2—H13···O2, 2.655 (4) and 2.881 (4) Å, respectively, see Table 1). The motifs are in contact by hydrogen bonds in bc plane, making sheets in which these sheets are held together by van der Waals interactions (see Fig. 2 & 3).

Experimental

Synthesis was carried out under argon atmosphere at 0°C, by dropwise addition of neat chlorodiphenylphosphine (3.32 g, 15.04 mmol) to a THF solution of 2-aminopyridine (1.41 g, 15.04 mmol) and triethylamine (1.568 g, 15.5 mmol). The mixture was warmed slowly to room temperature, followed by 24 h stirring. Triethylamine hydrochloride precipitates were then filtered off. Removing the excess solvent under reduced pressure, leads to a pale yellow oily product, that was solidifies by solving in benzene and stored in fridge. The obtained solid (0.100 g, 0.359 mmol) together with stoichiometric quantity of sulfur (0.011 g, 0.359 mmol) in toluene were refluxed for 30 minutes and the resulting solution was dried. Recrystallizing in hot toluene afforded colorless needle crystals.

Refinement

All H atoms (except water molecule) were positioned geometrically [C—H = 0.93Å and N—H = 0.86 (1)Å] and refined using a riding model, with Uiso(H)=1.2Ueq(C & N). The H atoms for the water molecules were located from electron density map and refined with a tight restraint of the O-H bond length of 0.95 (2) Å, while keeping the H···H distance at a value corresponding to the H-O-H angle 104o.

Figures

Fig. 1.
Molecular structure of (I), with 50% probability displacement ellipsoids. H atoms are shown as circles of arbitrary radii.
Fig. 2.
A packing diagram of (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C5H7N2+·C12H10O2P·H2OF(000) = 696
Mr = 330.31Dx = 1.256 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 8165 reflections
a = 15.2716 (19) Åθ = 2.5–25.0°
b = 9.979 (2) ŵ = 0.17 mm1
c = 11.7671 (15) ÅT = 295 K
β = 103.073 (10)°Needle, colorless
V = 1746.8 (5) Å30.60 × 0.35 × 0.21 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer2972 independent reflections
Radiation source: fine-focus sealed tube1660 reflections with I > 2σ(I)
graphiteRint = 0.097
[var phi] oscillation scansθmax = 25.0°, θmin = 2.5°
Absorption correction: analytical (X-SHAPE; Stoe & Cie, 2007)h = −18→17
Tmin = 0.813, Tmax = 0.965k = −11→11
8165 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.05P)2] where P = (Fo2 + 2Fc2)/3
2972 reflections(Δ/σ)max < 0.001
214 parametersΔρmax = 0.21 e Å3
3 restraintsΔρmin = −0.20 e Å3

Special details

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)

xyzUiso*/Ueq
P10.23381 (6)0.38907 (9)0.28738 (7)0.0566 (3)
O10.19470 (14)0.3089 (2)0.37261 (18)0.0684 (6)
O20.16905 (13)0.4311 (2)0.17762 (16)0.0679 (6)
C10.2857 (2)0.5359 (3)0.3623 (3)0.0549 (8)
C20.3479 (2)0.5264 (4)0.4676 (3)0.0719 (10)
H50.36560.44190.49750.086*
C30.3843 (3)0.6372 (4)0.5292 (3)0.0856 (11)
H40.42620.62790.59970.103*
C40.3587 (3)0.7608 (5)0.4863 (4)0.0922 (12)
H30.38290.83670.52750.111*
C50.2982 (3)0.7738 (4)0.3836 (4)0.1035 (14)
H20.28050.85890.35520.124*
C60.2622 (3)0.6628 (4)0.3205 (3)0.0831 (11)
H10.22170.67360.24910.100*
C70.3262 (2)0.2968 (3)0.2542 (3)0.0544 (8)
C80.3694 (2)0.3417 (3)0.1706 (3)0.0674 (9)
H100.34870.41820.12780.081*
C90.4430 (2)0.2742 (4)0.1497 (3)0.0769 (10)
H90.47150.30620.09330.092*
C100.4746 (2)0.1605 (4)0.2111 (4)0.0815 (11)
H80.52470.11590.19740.098*
C110.4311 (3)0.1143 (4)0.2928 (3)0.0859 (11)
H70.45140.03670.33430.103*
C120.3575 (2)0.1808 (3)0.3147 (3)0.0728 (10)
H60.32870.14770.37050.087*
N10.02673 (18)0.3481 (3)0.3918 (2)0.0648 (7)
H1A0.08010.33700.38110.078*
N2−0.00790 (19)0.4687 (3)0.2200 (2)0.0800 (9)
H130.04560.45580.21050.096*
H14−0.04580.51420.16950.096*
C13−0.0324 (2)0.4193 (3)0.3131 (3)0.0638 (9)
C14−0.1181 (2)0.4384 (4)0.3339 (3)0.0765 (10)
H18−0.16050.48880.28220.092*
C15−0.1392 (3)0.3836 (4)0.4294 (4)0.0877 (12)
H17−0.19630.39650.44300.105*
C16−0.0765 (3)0.3082 (4)0.5071 (4)0.0874 (12)
H16−0.09140.26900.57190.105*
C170.0058 (3)0.2930 (4)0.4874 (3)0.0789 (10)
H150.04890.24420.53970.095*
O30.16544 (17)0.0543 (2)0.44385 (19)0.0746 (7)
H3A0.163 (2)0.059 (3)0.5239 (12)0.090*
H3B0.181 (2)0.1430 (16)0.426 (3)0.090*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0523 (5)0.0634 (6)0.0563 (5)0.0041 (4)0.0170 (4)0.0055 (4)
O10.0624 (14)0.0753 (15)0.0752 (13)−0.0004 (11)0.0318 (12)0.0181 (12)
O20.0537 (13)0.0925 (17)0.0555 (12)0.0113 (12)0.0084 (11)0.0058 (11)
C10.0520 (19)0.059 (2)0.0570 (19)0.0083 (16)0.0193 (16)0.0046 (16)
C20.083 (3)0.065 (2)0.065 (2)0.003 (2)0.010 (2)0.0038 (19)
C30.090 (3)0.088 (3)0.075 (2)0.000 (3)0.011 (2)−0.011 (2)
C40.083 (3)0.077 (3)0.119 (4)−0.004 (2)0.026 (3)−0.026 (3)
C50.102 (4)0.055 (3)0.140 (4)0.011 (2)0.000 (3)0.007 (3)
C60.087 (3)0.060 (2)0.095 (3)0.011 (2)0.005 (2)0.012 (2)
C70.0497 (19)0.056 (2)0.0580 (18)0.0007 (15)0.0127 (16)−0.0038 (16)
C80.060 (2)0.075 (2)0.071 (2)0.0017 (18)0.0221 (18)−0.0022 (18)
C90.063 (2)0.092 (3)0.083 (2)−0.011 (2)0.031 (2)−0.023 (2)
C100.062 (2)0.092 (3)0.092 (3)0.017 (2)0.020 (2)−0.027 (2)
C110.084 (3)0.080 (3)0.093 (3)0.024 (2)0.020 (2)−0.004 (2)
C120.070 (2)0.076 (3)0.075 (2)0.011 (2)0.0208 (19)0.004 (2)
N10.0588 (18)0.0722 (19)0.0668 (17)0.0040 (15)0.0214 (15)−0.0004 (15)
N20.0641 (18)0.107 (2)0.0696 (19)0.0141 (17)0.0156 (16)0.0089 (17)
C130.061 (2)0.072 (2)0.059 (2)−0.0053 (19)0.0153 (19)−0.0150 (18)
C140.056 (2)0.099 (3)0.076 (2)0.005 (2)0.0184 (19)−0.012 (2)
C150.065 (3)0.113 (3)0.094 (3)0.002 (2)0.037 (2)−0.018 (3)
C160.083 (3)0.105 (3)0.087 (3)0.001 (2)0.046 (3)0.004 (2)
C170.084 (3)0.082 (3)0.075 (2)0.000 (2)0.027 (2)0.005 (2)
O30.0917 (17)0.0687 (15)0.0640 (14)−0.0134 (14)0.0191 (13)−0.0017 (12)

Geometric parameters (Å, °)

P1—O21.498 (2)C10—C111.367 (5)
P1—O11.508 (2)C10—H80.9300
P1—C11.800 (3)C11—C121.379 (5)
P1—C71.801 (3)C11—H70.9300
C1—C61.376 (4)C12—H60.9300
C1—C21.383 (4)N1—C131.341 (4)
C2—C31.370 (5)N1—C171.355 (4)
C2—H50.9300N1—H1A0.8600
C3—C41.356 (5)N2—C131.329 (4)
C3—H40.9300N2—H130.8601
C4—C51.351 (5)N2—H140.8600
C4—H30.9300C13—C141.398 (4)
C5—C61.376 (5)C14—C151.353 (5)
C5—H20.9300C14—H180.9300
C6—H10.9300C15—C161.387 (5)
C7—C81.377 (4)C15—H170.9300
C7—C121.386 (4)C16—C171.337 (5)
C8—C91.379 (5)C16—H160.9300
C8—H100.9300C17—H150.9300
C9—C101.373 (5)O3—H3A0.954 (10)
C9—H90.9300O3—H3B0.953 (10)
O2—P1—O1116.01 (13)C8—C9—H9119.5
O2—P1—C1109.03 (14)C11—C10—C9118.7 (3)
O1—P1—C1107.64 (13)C11—C10—H8120.7
O2—P1—C7110.68 (13)C9—C10—H8120.7
O1—P1—C7108.71 (14)C10—C11—C12121.1 (4)
C1—P1—C7104.06 (14)C10—C11—H7119.5
C6—C1—C2117.0 (3)C12—C11—H7119.5
C6—C1—P1121.6 (3)C11—C12—C7120.4 (3)
C2—C1—P1121.3 (2)C11—C12—H6119.8
C3—C2—C1122.2 (3)C7—C12—H6119.8
C3—C2—H5118.9C13—N1—C17122.7 (3)
C1—C2—H5118.9C13—N1—H1A118.7
C4—C3—C2119.3 (4)C17—N1—H1A118.7
C4—C3—H4120.4C13—N2—H13120.3
C2—C3—H4120.4C13—N2—H14119.7
C5—C4—C3120.1 (4)H13—N2—H14120.0
C5—C4—H3119.9N2—C13—N1119.7 (3)
C3—C4—H3119.9N2—C13—C14122.9 (3)
C4—C5—C6120.9 (4)N1—C13—C14117.5 (3)
C4—C5—H2119.5C15—C14—C13120.0 (4)
C6—C5—H2119.5C15—C14—H18120.0
C1—C6—C5120.5 (4)C13—C14—H18120.0
C1—C6—H1119.8C14—C15—C16120.5 (4)
C5—C6—H1119.8C14—C15—H17119.7
C8—C7—C12118.3 (3)C16—C15—H17119.7
C8—C7—P1120.9 (2)C17—C16—C15118.9 (4)
C12—C7—P1120.8 (2)C17—C16—H16120.5
C7—C8—C9120.6 (3)C15—C16—H16120.5
C7—C8—H10119.7C16—C17—N1120.4 (4)
C9—C8—H10119.7C16—C17—H15119.8
C10—C9—C8120.9 (4)N1—C17—H15119.8
C10—C9—H9119.5H3A—O3—H3B104 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O10.861.802.655 (4)175
O3—H3A···O2i0.95 (2)1.79 (2)2.743 (3)175 (3)
O3—H3B···O10.95 (2)1.80 (2)2.744 (3)171 (3)
N2—H13···O20.862.022.881 (4)176
N2—H14···O3ii0.862.042.853 (4)157

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2622).

References

  • Almeida, I. G. D. (1974). J. Radioanal. Chem.22, 21–28.
  • Brandenburg, K. (2001). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Espinet, P. & Soulantica, J. K. (1999). Coord. Chem. Rev.193, 499–556.
  • Gentzkow, W. von, Huber, J. & Kapitza, H. (1996). US Patent No. 5 587 243.
  • Huber, J., Kapitza, H. & Kleiner, H.-J. (1998). US Patent No. 5 811 188.
  • Jeffrey, J. C. & Rauchfuss, T. B. (1979). Inorg. Chem.18, 2658–2666.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]
  • Stoe & Cie (2007). X-AREA, X-RED and X-SHAPE Stoe & Cie GmbH, Darmstadt, Germany.

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