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In the title compound, C2H8N+·C12H11O5P2, pairs of hydrogen diphenyl­diphospho­nate anions form dimers across a twofold axis, with two symmetric O...H...O hydrogen bonds [O...O = 2.406 (3) and 2.418 (3) Å]. The 12-membered ring thus formed has crystallographic 2 and quasi-222 symmetry. Cations on either side of the ring form N—H...O hydrogen bonds to the four extraannular O atoms, with N...O distances of 2.765 (2) and 2.748 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106009528/hj1093sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106009528/hj1093Isup2.hkl
Contains datablock I

CCDC reference: 609419

Comment top

As part of our interest in preparing and characterizing bridging methylene phosphine complexes, the title compound was isolated during the synthesis of Ph(H)PCH2P(H)Ph by Stelzer's reaction (Langhans & Stelzer, 1987), during which the order of addition of dimethylformamide and water was reversed.

The chemically significant species, [(CH3)2NH2]2[(C6H5)2P2O5H]2, (I), consists of two hydrogen diphenyldiphosphonate anions fused into a P4O6H2 ring by two short hydrogen bonds (Fig. 1 and Table 2), both apparently symmetric, with their H atoms centrally located on a twofold axis. While we cannot rule out the possibility that these hydrogen bonds involve disordered H atoms, with half-occupied sites slightly off the twofold axis, difference maps (see Fig. 2) show no elongation of the density along the O···O lines. The O—H distances are quite long, approximately 1.2 Å. Steiner & Saenger (1994), by examining O—H···O hydrogen-bonded structures determined from low-T neutron-diffraction data, noted a smooth lengthening of the O—H distances in the donors with a shortening of the O···O distance. Although their data set contained no instances of hydrogen bonds across symmetry elements, they found a minimum O···O distance of ca 2.39 Å, with equal O—H and H···O distances at that distance. Thus, the symmetric hydrogen bonds observed in (I) are in accordance with the findings of Steiner & Saenger (1994). In (I), the P1—O3 and P2—O5 distances (Table 1) to O atoms involved in the symmetric hydrogen bonds are intermediate in length between the PO distance, 1.506 (2) Å, and P—OH distances, 1.536 (2) and 1.554 (2) Å, in benzenephosphonic acid (Mahmoudkhani & Langer, 2002).

The four remaining O atoms, viz. O2, O4 and their symmetry equivalents, accept hydrogen bonds from two cations on either side of the plane. The P O distances are typical of double bonds (Corbridge, 1974).

The structure of the same dimerized anion has been reported at 213 K, with a complex palladium cation (Kingsley et al., 2001), but with asymmetric ordered hydrogen bonds [O···O = 2.424 (3) Å]. That dimer lies on an inversion center rather than a twofold axis, so that symmetry does not require either disorder of the H-atom positions or a symmetric hydrogen bond. In the presence of Pd, uncertainties in H-atom positions are rather large; the reported O—H distance is 1.02 (6) Å and the H···O distance is 1.43 (6) Å. Thus, the deviation of the H-atom position from the O···O mid-point is of marginal statistical significance, and that hydrogen bond may approach the apparently symmetric one observed in the title compound.

Experimental top

Phenyl phosphine (19.75 g, 0.180 mol) was added to CH2Cl2 (7.63 g, 0.090 mol) with stirring in an ice-cooled Schlenk flask. To this mixture was added degassed water (150 ml). Dimethylformamide (56 ml) was syringed into the mixture and the solution turned cloudy. Degassed 56% KOH solution (27 ml) was added slowly by canula over a period of 20 min, and stirring was continued for 10 h. The reaction mixture separated into two layers, and the organic layer was extracted three times with pentane (50 ml). The pentane was removed by distillation, and the remaining residue was separated by fractional distillation, yielding the starting material, phenyl phosphine. The second fraction, collected at 307 K, was the title compound, and shiny white crystals formed by sublimation.

Refinement top

N– and O-bound H atoms were individually refined, except that the Uiso(H) values for the former were set at 1.2Ueq(N). All C-bound H atoms were placed in calculated positions with C—H distances of 0.93 Å [please check; these distances are not given in the CIF] and Uiso(H) values of 1.2 or 1.5 times Ueq(C), and thereafter treated as riding. A torsional parameter was refined for each methyl group.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: HKL SCALEPACK (Otwinowski & Minor 1997); data reduction: HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The structure of (I), showing the atomic numbering scheme and displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. Fourier difference maps showing the two symmetric hydrogen bonds. The peak heights at the H-atom positions are approximately 1 e Å−3.
dimethylammonium hydrogen diphenyldiphosphonate top
Crystal data top
C2H8N+·C12H11O5P2Dx = 1.369 Mg m3
Mr = 343.24Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41cdCell parameters from 5490 reflections
Hall symbol: I 4bw -2cθ = 2.5–32.5°
a = 13.110 (3) ŵ = 0.28 mm1
c = 38.751 (8) ÅT = 102 K
V = 6660 (3) Å3Fragment, colorless
Z = 160.33 × 0.30 × 0.18 mm
F(000) = 2880
Data collection top
Nonius KappaCCD (with Oxford Cryostream)
diffractometer
5654 independent reflections
Radiation source: fine-focus sealed tube4268 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.052
ω scans with κ offsetsθmax = 32.6°, θmin = 3.1°
Absorption correction: multi-scan
HKL SCALEPACK (Otwinowski & Minor 1997)
h = 1919
Tmin = 0.887, Tmax = 0.951k = 1414
33359 measured reflectionsl = 5756
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)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095 w = 1/[σ2(Fo2) + (0.0434P)2 + 1.9071P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
5654 reflectionsΔρmax = 0.33 e Å3
212 parametersΔρmin = 0.31 e Å3
1 restraintAbsolute structure: Flack (1983), 2590 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.21 (8)
Crystal data top
C2H8N+·C12H11O5P2Z = 16
Mr = 343.24Mo Kα radiation
Tetragonal, I41cdµ = 0.28 mm1
a = 13.110 (3) ÅT = 102 K
c = 38.751 (8) Å0.33 × 0.30 × 0.18 mm
V = 6660 (3) Å3
Data collection top
Nonius KappaCCD (with Oxford Cryostream)
diffractometer
5654 independent reflections
Absorption correction: multi-scan
HKL SCALEPACK (Otwinowski & Minor 1997)
4268 reflections with I > 2σ(I)
Tmin = 0.887, Tmax = 0.951Rint = 0.052
33359 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.095Δρmax = 0.33 e Å3
S = 1.02Δρmin = 0.31 e Å3
5654 reflectionsAbsolute structure: Flack (1983), 2590 Friedel pairs
212 parametersAbsolute structure parameter: 0.21 (8)
1 restraint
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
P10.52537 (4)0.67758 (4)0.249946 (11)0.01640 (11)
P20.45614 (4)0.67403 (4)0.320250 (11)0.01822 (11)
O10.48821 (11)0.73281 (9)0.28514 (4)0.0209 (3)
O20.63740 (11)0.66309 (11)0.24934 (4)0.0221 (3)
O30.45930 (11)0.58222 (11)0.24646 (4)0.0214 (3)
H3O0.50000.50000.2462 (13)0.052 (12)*
O40.34640 (11)0.64784 (11)0.32035 (4)0.0238 (3)
O50.53197 (11)0.58649 (11)0.32417 (4)0.0225 (3)
H5O0.50000.50000.3225 (14)0.063 (13)*
C10.48281 (16)0.76549 (16)0.21795 (5)0.0173 (4)
C20.54905 (17)0.79951 (17)0.19240 (5)0.0268 (5)
H20.61970.78380.19360.032*
C30.5109 (2)0.85702 (19)0.16494 (6)0.0360 (6)
H30.55560.87970.14720.043*
C40.4086 (2)0.8810 (2)0.16339 (6)0.0391 (6)
H40.38300.91900.14440.047*
C50.3431 (2)0.85021 (19)0.18920 (6)0.0335 (5)
H50.27320.86910.18840.040*
C60.37934 (16)0.79167 (17)0.21639 (5)0.0240 (4)
H60.33400.76930.23390.029*
C70.48755 (17)0.76661 (15)0.35222 (5)0.0207 (4)
C80.41877 (17)0.78648 (17)0.37900 (5)0.0247 (4)
H80.35190.75860.37830.030*
C90.4485 (2)0.84715 (18)0.40669 (6)0.0321 (6)
H90.40220.86040.42500.039*
C100.5459 (2)0.88815 (18)0.40747 (6)0.0323 (6)
H100.56680.92800.42670.039*
C110.6129 (2)0.87149 (17)0.38045 (6)0.0307 (5)
H110.67850.90230.38080.037*
C120.58478 (18)0.81019 (16)0.35295 (5)0.0247 (5)
H120.63140.79780.33470.030*
N1A0.74007 (13)0.50925 (16)0.28364 (6)0.0242 (3)
H1N0.701 (2)0.554 (2)0.2727 (7)0.029*
H2N0.702 (2)0.465 (2)0.2948 (6)0.029*
C1A0.8031 (2)0.4524 (2)0.25843 (6)0.0375 (6)
H1A10.84150.39900.27040.056*
H1A20.85070.49940.24720.056*
H1A30.75870.42120.24100.056*
C2A0.7989 (2)0.5673 (2)0.30947 (7)0.0391 (6)
H2A10.84060.61880.29780.059*
H2A20.84330.52060.32230.059*
H2A30.75180.60100.32550.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.0185 (3)0.0146 (3)0.0161 (2)0.00160 (18)0.0011 (2)0.00010 (19)
P20.0237 (3)0.0143 (3)0.0166 (2)0.00020 (19)0.00092 (19)0.00039 (19)
O10.0323 (8)0.0144 (6)0.0161 (5)0.0019 (6)0.0015 (6)0.0007 (6)
O20.0181 (7)0.0233 (8)0.0251 (7)0.0017 (6)0.0029 (6)0.0045 (6)
O30.0214 (8)0.0143 (8)0.0285 (8)0.0004 (5)0.0008 (6)0.0015 (6)
O40.0243 (8)0.0206 (8)0.0265 (7)0.0007 (6)0.0002 (6)0.0047 (6)
O50.0258 (8)0.0141 (7)0.0277 (8)0.0001 (5)0.0028 (6)0.0020 (6)
C10.0215 (11)0.0139 (10)0.0164 (9)0.0021 (7)0.0032 (7)0.0015 (7)
C20.0270 (12)0.0252 (13)0.0281 (11)0.0054 (9)0.0033 (9)0.0036 (8)
C30.0518 (18)0.0322 (14)0.0241 (11)0.0062 (11)0.0055 (10)0.0107 (10)
C40.0552 (19)0.0296 (14)0.0324 (13)0.0069 (12)0.0143 (11)0.0097 (10)
C50.0329 (14)0.0292 (13)0.0386 (12)0.0073 (9)0.0160 (10)0.0020 (10)
C60.0207 (11)0.0209 (11)0.0304 (11)0.0003 (8)0.0029 (8)0.0015 (8)
C70.0284 (12)0.0152 (10)0.0185 (9)0.0022 (8)0.0043 (8)0.0015 (7)
C80.0298 (12)0.0200 (11)0.0242 (10)0.0040 (8)0.0028 (8)0.0009 (8)
C90.0486 (16)0.0264 (13)0.0214 (10)0.0145 (11)0.0024 (9)0.0026 (9)
C100.0510 (17)0.0194 (12)0.0266 (11)0.0077 (10)0.0163 (10)0.0051 (9)
C110.0389 (14)0.0191 (12)0.0342 (12)0.0030 (9)0.0152 (10)0.0039 (9)
C120.0339 (13)0.0194 (11)0.0208 (9)0.0012 (8)0.0045 (8)0.0049 (8)
N1A0.0206 (9)0.0191 (10)0.0328 (8)0.0015 (7)0.0039 (9)0.0075 (7)
C1A0.0374 (15)0.0314 (15)0.0437 (14)0.0055 (11)0.0083 (11)0.0069 (10)
C2A0.0406 (16)0.0328 (15)0.0439 (13)0.0097 (11)0.0187 (11)0.0087 (11)
Geometric parameters (Å, º) top
P1—O21.4811 (15)C7—C121.397 (3)
P1—O31.5269 (16)C7—C81.399 (3)
P1—O11.6190 (16)C8—C91.391 (3)
P1—C11.782 (2)C8—H80.9500
P2—O41.4791 (16)C9—C101.385 (4)
P2—O51.5260 (15)C9—H90.9500
P2—O11.6193 (17)C10—C111.384 (4)
P2—C71.782 (2)C10—H100.9500
O3—H3O1.2028 (15)C11—C121.385 (3)
O5—H5O1.211 (3)C11—H110.9500
C1—C21.390 (3)C12—H120.9500
C1—C61.401 (3)N1A—C2A1.475 (3)
C2—C31.397 (3)N1A—C1A1.481 (3)
C2—H20.9500N1A—H1N0.89 (3)
C3—C41.379 (4)N1A—H2N0.88 (3)
C3—H30.9500C1A—H1A10.9800
C4—C51.378 (4)C1A—H1A20.9800
C4—H40.9500C1A—H1A30.9800
C5—C61.387 (3)C2A—H2A10.9800
C5—H50.9500C2A—H2A20.9800
C6—H60.9500C2A—H2A30.9800
O2—P1—O3117.14 (8)C12—C7—P2120.22 (17)
O2—P1—O1111.66 (9)C8—C7—P2119.56 (17)
O3—P1—O1105.66 (8)C9—C8—C7119.8 (2)
O2—P1—C1112.48 (9)C9—C8—H8120.1
O3—P1—C1106.88 (9)C7—C8—H8120.1
O1—P1—C1101.69 (8)C10—C9—C8119.8 (2)
O4—P2—O5117.31 (8)C10—C9—H9120.1
O4—P2—O1111.43 (9)C8—C9—H9120.1
O5—P2—O1105.81 (8)C11—C10—C9120.5 (2)
O4—P2—C7112.39 (10)C11—C10—H10119.8
O5—P2—C7107.00 (9)C9—C10—H10119.8
O1—P2—C7101.54 (9)C10—C11—C12120.3 (2)
P1—O1—P2124.96 (8)C10—C11—H11119.8
H3O—O3—P1118.9 (3)C12—C11—H11119.8
H5O—O5—P2118.3 (4)C11—C12—C7119.7 (2)
P2—O5—H5O118.3 (4)C11—C12—H12120.1
C2—C1—C6119.71 (19)C7—C12—H12120.1
C2—C1—P1120.48 (16)C2A—N1A—C1A114.59 (19)
C6—C1—P1119.45 (15)C2A—N1A—H1N106.7 (17)
C1—C2—C3119.5 (2)C1A—N1A—H1N109.9 (16)
C1—C2—H2120.3C2A—N1A—H2N107.5 (16)
C3—C2—H2120.3C1A—N1A—H2N107.8 (17)
C4—C3—C2120.3 (2)H1N—N1A—H2N110 (2)
C4—C3—H3119.8N1A—C1A—H1A1109.5
C2—C3—H3119.8N1A—C1A—H1A2109.5
C5—C4—C3120.5 (2)H1A1—C1A—H1A2109.5
C5—C4—H4119.8N1A—C1A—H1A3109.5
C3—C4—H4119.8H1A1—C1A—H1A3109.5
C4—C5—C6120.0 (2)H1A2—C1A—H1A3109.5
C4—C5—H5120.0N1A—C2A—H2A1109.5
C6—C5—H5120.0N1A—C2A—H2A2109.5
C5—C6—C1120.0 (2)H2A1—C2A—H2A2109.5
C5—C6—H6120.0N1A—C2A—H2A3109.5
C1—C6—H6120.0H2A1—C2A—H2A3109.5
C12—C7—C8119.8 (2)H2A2—C2A—H2A3109.5
O2—P1—O1—P289.86 (13)C4—C5—C6—C11.2 (3)
O3—P1—O1—P238.52 (13)C2—C1—C6—C50.8 (3)
C1—P1—O1—P2149.99 (12)P1—C1—C6—C5172.32 (17)
O4—P2—O1—P188.63 (13)O4—P2—C7—C12171.69 (16)
O5—P2—O1—P139.93 (13)O5—P2—C7—C1258.15 (18)
C7—P2—O1—P1151.52 (13)O1—P2—C7—C1252.53 (18)
O2—P1—C1—C210.3 (2)O4—P2—C7—C815.89 (19)
O3—P1—C1—C2119.55 (18)O5—P2—C7—C8114.26 (16)
O1—P1—C1—C2129.91 (17)O1—P2—C7—C8135.06 (16)
O2—P1—C1—C6176.58 (16)C12—C7—C8—C91.8 (3)
O3—P1—C1—C653.52 (19)P2—C7—C8—C9170.63 (17)
O1—P1—C1—C657.02 (18)C7—C8—C9—C100.5 (3)
C6—C1—C2—C31.8 (3)C8—C9—C10—C111.8 (3)
P1—C1—C2—C3171.24 (18)C9—C10—C11—C122.6 (3)
C1—C2—C3—C40.8 (4)C10—C11—C12—C71.2 (3)
C2—C3—C4—C51.2 (4)C8—C7—C12—C111.0 (3)
C3—C4—C5—C62.2 (4)P2—C7—C12—C11171.42 (16)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O3i1.2028 (15)1.2028 (15)2.406 (3)179 (5)
O5—H5O···O5i1.211 (3)1.211 (3)2.418 (3)174 (5)
N1A—H1N···O20.89 (3)1.89 (3)2.765 (2)170 (3)
N1A—H2N···O4i0.88 (3)1.89 (3)2.748 (3)165 (3)
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC2H8N+·C12H11O5P2
Mr343.24
Crystal system, space groupTetragonal, I41cd
Temperature (K)102
a, c (Å)13.110 (3), 38.751 (8)
V3)6660 (3)
Z16
Radiation typeMo Kα
µ (mm1)0.28
Crystal size (mm)0.33 × 0.30 × 0.18
Data collection
DiffractometerNonius KappaCCD (with Oxford Cryostream)
diffractometer
Absorption correctionMulti-scan
HKL SCALEPACK (Otwinowski & Minor 1997)
Tmin, Tmax0.887, 0.951
No. of measured, independent and
observed [I > 2σ(I)] reflections
33359, 5654, 4268
Rint0.052
(sin θ/λ)max1)0.758
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.095, 1.02
No. of reflections5654
No. of parameters212
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.33, 0.31
Absolute structureFlack (1983), 2590 Friedel pairs
Absolute structure parameter0.21 (8)

Computer programs: COLLECT (Nonius, 2000), HKL SCALEPACK (Otwinowski & Minor 1997), HKL DENZO (Otwinowski & Minor 1997) and SCALEPACK, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
P1—O21.4811 (15)P2—O51.5260 (15)
P1—O31.5269 (16)P2—O11.6193 (17)
P1—O11.6190 (16)P2—C71.782 (2)
P1—C11.782 (2)N1A—C2A1.475 (3)
P2—O41.4791 (16)N1A—C1A1.481 (3)
P1—O1—P2124.96 (8)
O2—P1—O1—P289.86 (13)O4—P2—O1—P188.63 (13)
O3—P1—O1—P238.52 (13)O5—P2—O1—P139.93 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3O···O3i1.2028 (15)1.2028 (15)2.406 (3)179 (5)
O5—H5O···O5i1.211 (3)1.211 (3)2.418 (3)174 (5)
N1A—H1N···O20.89 (3)1.89 (3)2.765 (2)170 (3)
N1A—H2N···O4i0.88 (3)1.89 (3)2.748 (3)165 (3)
Symmetry code: (i) x+1, y+1, z.
 

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