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Acta Cryst. (2008). E64, o1018    [ doi:10.1107/S1600536808012907 ]

Ammonium diphenylphosphinate monohydrate

D. Li, J. Chen and J. Guo

Abstract top

In the title salt, NH4+·C12H10O2P-·H2O, the ion pair and water molecule interact through hydrogen bonds to form a layer structure.

Comment top

The title compound is a by-product when synthesizing 3-Cyanophenyl-amidinium diphenylphosphinate. Within the OPO fragment of the diphenylphosphinate anion, the P—O distances are 1.495 (2) and 1.503 (2) Å. The similar values was reported in the structure of arylamidinium diphenylphosphinate (Guo et al., 2005). The P—O distances indicate that the charge of the diphenylphosphinate anion [Ph2PO2]- is delocalized over the O—P—O framework. There are two types of hydrogen bond, namely P—O···H—N and P—O···H—O. The O—N distances are in the range of 2.752 (3)–2.816 (4) Å. The O—O distance is 2.723 (4) Å.

Related literature top

For other ammonium diphenylphosphinates, see: Guo et al. (2005); Dorn et al. (2001).

Experimental top

1,3-Dicyanobenzene (0.38 g, 3 mmol) and LiN(SiMe3)2 (1.0 g, 6 mmol) were dissolveded in THF (30 cm3) at 0°C. The resultant yellow solution was warmed to room temperature and stirred for an additional 2 h before cooling down to -78°C. Chlorodiphenylphosphine (1.1 cm3, 6 mmol) was then slowly added to the reaction mixture which was stirred at -78°C for an hour before warming up to room temperature and allowed to react overnight. Solvent was then removed in vacuum. The residue was extracted with dichloromethane and the solution was filtered. The solvent of the filtrate was removed in vacuum to give a dark red oilyproduct. The product was dissolved in acetonitrile (30 cm3) and 30% hydrogen peroxide (0.68 cm3, 6 mmol) was added in air. After stirring for 24 h at room temperature, the reaction mixture was filtered. The colorless crystals of compound 3-Cyanophenyl-amidinium diphenylphosphinate were produced first; then colorless crystals of the title compound were obtained. Yield: 0.50 g, 2.1 mmol, m.p. 185–187 °C. 1H NMR (300 MHz, [D6]DMSO): d = 7.27 (m, 6H, Ar),7.61–7.64 (m, 4H, Ar). 13CNMR (75 MHz, [D6]DMSO): δ = 130.7, 130.9,132.7, 134.2, 144.1. 31P NMR (121.5 MHz, [D6]DMSO): δ = 13.3. IR (cm-1,in KBr): 3611m, 3071 b s, 3009 b s, 2833 b s, 1638m, 1483 s, 1400m, 1163vs, 1128vs, 1068m, 1040vs, 1020 s, 962m, 725vs, 694 s, 565vs.

Refinement top

The ammonium and water H atoms were found by using fourier difference map and constrained to their related atoms, with N—H distances in the range 0.88 Å and Uiso(H) = 1.2Ueq(N), O—H distances in the range 0.86 Å and Uiso(H) = 1.2Ueq(O). The phenyl H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL/PC (Sheldrick, 2008); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure, showing the atom-numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. The water molecule was omitted.
[Figure 2] Fig. 2. The infinite chain. The waters and all of H atoms were omitted.
Ammonium diphenylphosphinate monohydrate top
Crystal data top
NH4+·C12H10O2P–·H2OF000 = 536
Mr = 253.23Dx = 1.260 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3307 reflections
a = 15.027 (2) Åθ = 2.6–27.5º
b = 6.4594 (9) ŵ = 0.20 mm−1
c = 15.484 (2) ÅT = 293 (2) K
β = 117.394 (2)ºBlock, colorless
V = 1334.4 (3) Å30.20 × 0.20 × 0.15 mm
Z = 4
Data collection top
Bruker SMART
diffractometer		2341 independent reflections
Radiation source: fine-focus sealed tube2208 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.021
T = 293(2) Kθmax = 25.0º
ω scansθmin = 2.6º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→13
Tmin = 0.798, Tmax = 0.970k = −7→7
6237 measured reflectionsl = −10→18
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.064H-atom parameters constrained
wR(F2) = 0.139  w = 1/[σ2(Fo2) + (0.0434P)2 + 1.1014P]
where P = (Fo2 + 2Fc2)/3
S = 1.22(Δ/σ)max < 0.001
2341 reflectionsΔρmax = 0.35 e Å−3
154 parametersΔρmin = −0.23 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
NH4+·C12H10O2P–·H2OV = 1334.4 (3) Å3
Mr = 253.23Z = 4
Monoclinic, P21/nMo Kα
a = 15.027 (2) ŵ = 0.20 mm−1
b = 6.4594 (9) ÅT = 293 (2) K
c = 15.484 (2) Å0.20 × 0.20 × 0.15 mm
β = 117.394 (2)º
Data collection top
Bruker SMART
diffractometer		2341 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2208 reflections with I > 2σ(I)
Tmin = 0.798, Tmax = 0.970Rint = 0.021
6237 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.064154 parameters
wR(F2) = 0.139H-atom parameters constrained
S = 1.22Δρmax = 0.35 e Å−3
2341 reflectionsΔρmin = −0.23 e Å−3
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
P10.56727 (5)0.36680 (12)0.37497 (5)0.0400 (2)
O10.48666 (15)0.5276 (3)0.33914 (16)0.0547 (6)
O20.54859 (16)0.1704 (3)0.41607 (15)0.0533 (6)
C10.5943 (2)0.3010 (5)0.2762 (2)0.0420 (7)
C20.5828 (3)0.4485 (6)0.2071 (2)0.0598 (9)
H2A0.56170.58140.21190.072*
C30.6028 (3)0.3987 (8)0.1308 (3)0.0797 (12)
H3A0.59500.49800.08430.096*
C40.6340 (3)0.2027 (9)0.1236 (3)0.0830 (13)
H4A0.64670.16940.07190.100*
C50.6465 (3)0.0569 (7)0.1916 (3)0.0749 (11)
H5A0.6685−0.07500.18660.090*
C60.6266 (2)0.1035 (5)0.2679 (2)0.0564 (8)
H6A0.63470.00280.31390.068*
C70.6820 (2)0.4771 (5)0.4685 (2)0.0407 (7)
C80.7658 (3)0.3527 (5)0.5140 (3)0.0627 (9)
H8A0.76330.21620.49400.075*
C90.8532 (3)0.4287 (7)0.5888 (3)0.0774 (12)
H9A0.90910.34340.61840.093*
C100.8579 (3)0.6274 (7)0.6192 (3)0.0716 (11)
H10A0.91610.67700.67090.086*
C110.7768 (3)0.7541 (6)0.5736 (3)0.0703 (11)
H11A0.78060.89130.59320.084*
C120.6887 (2)0.6800 (5)0.4982 (2)0.0534 (8)
H12A0.63380.76770.46760.064*
N10.59203 (18)0.1330 (4)0.61263 (18)0.0504 (6)
H1B0.58620.14700.55340.060*
H2B0.56840.24530.62750.060*
H3B0.55610.02620.61400.060*
H4B0.65530.11380.65450.060*
O30.7070 (2)0.6051 (7)0.7434 (2)0.1340 (16)
H3C0.64620.57140.72780.161*
H3D0.70950.70790.70960.161*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0376 (4)0.0409 (4)0.0432 (4)−0.0016 (3)0.0201 (3)−0.0034 (3)
O10.0422 (11)0.0567 (13)0.0625 (14)0.0058 (10)0.0216 (10)−0.0087 (11)
O20.0611 (14)0.0503 (13)0.0534 (13)−0.0120 (10)0.0305 (11)−0.0035 (10)
C10.0351 (14)0.0484 (17)0.0405 (15)−0.0034 (13)0.0156 (12)−0.0034 (13)
C20.057 (2)0.068 (2)0.0519 (19)−0.0010 (17)0.0231 (16)0.0048 (17)
C30.082 (3)0.108 (4)0.054 (2)−0.006 (3)0.035 (2)0.014 (2)
C40.081 (3)0.123 (4)0.058 (2)−0.008 (3)0.042 (2)−0.018 (3)
C50.072 (2)0.084 (3)0.078 (3)0.008 (2)0.043 (2)−0.021 (2)
C60.0540 (19)0.063 (2)0.0546 (19)0.0080 (16)0.0267 (16)−0.0034 (16)
C70.0421 (15)0.0459 (16)0.0368 (15)−0.0053 (13)0.0205 (12)0.0007 (13)
C80.055 (2)0.051 (2)0.064 (2)0.0025 (16)0.0117 (17)0.0060 (16)
C90.051 (2)0.084 (3)0.071 (2)0.002 (2)0.0048 (18)0.013 (2)
C100.057 (2)0.100 (3)0.0471 (19)−0.025 (2)0.0145 (17)−0.007 (2)
C110.076 (3)0.071 (2)0.067 (2)−0.021 (2)0.034 (2)−0.027 (2)
C120.0528 (18)0.0526 (19)0.0547 (19)−0.0037 (15)0.0247 (15)−0.0121 (15)
N10.0457 (14)0.0514 (15)0.0546 (15)0.0003 (12)0.0236 (12)−0.0039 (12)
O30.0596 (18)0.198 (4)0.106 (2)−0.038 (2)0.0049 (17)0.057 (3)
Geometric parameters (Å, °) top
P1—O11.495 (2)C7—C81.383 (4)
P1—O21.503 (2)C8—C91.381 (5)
P1—C11.804 (3)C8—H8A0.9300
P1—C71.811 (3)C9—C101.358 (6)
C1—C21.384 (4)C9—H9A0.9300
C1—C61.392 (4)C10—C111.364 (5)
C2—C31.384 (5)C10—H10A0.9300
C2—H2A0.9300C11—C121.386 (5)
C3—C41.372 (6)C11—H11A0.9300
C3—H3A0.9300C12—H12A0.9300
C4—C51.360 (6)N1—H1B0.8844
C4—H4A0.9300N1—H2B0.8830
C5—C61.378 (5)N1—H3B0.8823
C5—H5A0.9300N1—H4B0.8782
C6—H6A0.9300O3—H3C0.8585
C7—C121.377 (4)O3—H3D0.8572
O1—P1—O2117.81 (13)C12—C7—P1122.5 (2)
O1—P1—C1108.00 (13)C8—C7—P1119.2 (2)
O2—P1—C1108.59 (13)C9—C8—C7120.9 (3)
O1—P1—C7109.50 (13)C9—C8—H8A119.6
O2—P1—C7106.73 (13)C7—C8—H8A119.6
C1—P1—C7105.56 (13)C10—C9—C8120.3 (4)
C2—C1—C6118.9 (3)C10—C9—H9A119.9
C2—C1—P1119.8 (3)C8—C9—H9A119.9
C6—C1—P1121.2 (2)C9—C10—C11119.8 (3)
C1—C2—C3120.1 (4)C9—C10—H10A120.1
C1—C2—H2A119.9C11—C10—H10A120.1
C3—C2—H2A119.9C10—C11—C12120.5 (4)
C4—C3—C2120.0 (4)C10—C11—H11A119.7
C4—C3—H3A120.0C12—C11—H11A119.7
C2—C3—H3A120.0C7—C12—C11120.3 (3)
C5—C4—C3120.4 (4)C7—C12—H12A119.9
C5—C4—H4A119.8C11—C12—H12A119.9
C3—C4—H4A119.8H1B—N1—H2B109.1
C4—C5—C6120.3 (4)H1B—N1—H3B109.5
C4—C5—H5A119.8H2B—N1—H3B108.2
C6—C5—H5A119.8H1B—N1—H4B109.7
C5—C6—C1120.1 (4)H2B—N1—H4B110.6
C5—C6—H6A119.9H3B—N1—H4B109.7
C1—C6—H6A119.9H3C—O3—H3D111.4
C12—C7—C8118.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O20.881.942.814 (3)170
N1—H2B···O1i0.881.872.752 (3)176
N1—H3B···O2ii0.881.912.764 (3)164
N1—H4B···O3iii0.881.942.816 (4)172
O3—H3C···O1i0.861.892.723 (4)164
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O20.881.942.814 (3)170
N1—H2B···O1i0.881.872.752 (3)176
N1—H3B···O2ii0.881.912.764 (3)164
N1—H4B···O3iii0.881.942.816 (4)172
O3—H3C···O1i0.861.892.723 (4)164
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y, −z+1; (iii) −x+3/2, y−1/2, −z+3/2.
Acknowledgements top

This work received funding from the Shanxi Returned Overseas Scholar Foundation.

references
References top

Bruker (2000). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Dorn, H., Lough, A. J. & Manners, I. (2001). Acta Cryst. E57, o928–o929.

Guo, J., Wong, W.-K. & Wong, W.-Y. (2005). Polyhedron, 24, 927–939.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.