Symmetric hydrogen bonding in dimethylammonium hydrogen diphenyldiphosphonate

Article abstract of DOI:10.1107/S0108270106009528

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) A]. 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) A.

Full text of DOI:10.1107/S0108270106009528

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
130 K, R > 0.06),noted a smooth lengthening of the OÐH
distances of the donors with a shortening of the OÁ Á ÁO
distance. Although their data set contained no instances of
hydrogen bonds across symmetry elements, they found a
ISSN 0108-2701
Ê
minimum OÁ Á ÁO distance of ca 2.39 A, with equal OÐH and
HÁ Á ÁO distances at that distance. Thus, the symmetric
hydrogen bonds observed in (I) are in accordance with their
®ndings. In (I), the P1ÐO3 and P2ÐO5 distances (Table 1) to
O atoms involved in the symmetric hydrogen bonds are
Symmetric hydrogen bonding in
dimethylammonium hydrogen
diphenyldiphosphonate
intermediate in length between the
Ê
P
O
distance
[1.506 (2) A] and the PÐOH distances [1.536 (2) and
Ê
1.554 (2) A] in benzenephosphonic acid (Mahmoudkhani &
Langer, 2002).
Brandy H. Courtney, Booker W. O. Juma, Steven F.
Watkins,* Frank R. Fronczek and George G. Stanley
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).
Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803-1804,
USA
Correspondence e-mail: swatkins@lsu.edu
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
Received 8 February 2006
Accepted 14 March 2006
Online 13 April 2006
Ê
[OÁ Á ÁO = 2.424 (3) A]. That dimer lies on an inversion center
In the title compound, C2H8N+ÁC12H11O5P2 , pairs of
hydrogen diphenyldiphosphonate anions form dimers across
a twofold axis, with two symmetric OÁ Á ÁHÁ Á ÁO hydrogen
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 palladium, uncertainties in
H-atom positions are rather large; the reported OÐH distance
is 1.02 (6) A and the HÁ Á ÁO distance is 1.43 (6) A. Thus, the
deviation of the H-atom position from the OÁ Á ÁO mid-point is
of marginal statistical signi®cance, and that hydrogen bond
may approach the apparently symmetric one observed in the
title compound.
Ê
bonds [OÁ Á ÁO = 2.406 (3) and 2.418 (3) A]. The 12-membered
ring thus formed has crystallographic 2 and quasi-222
symmetry. Cations on either side of the ring form NÐHÁ Á ÁO
hydrogen bonds to the four extraannular O atoms, with NÁ Á ÁO
Ê
Ê
Ê
distances of 2.765 (2) and 2.748 (3) A.
Comment
As part of our interest in preparing and characterizing brid-
ging methylene±phosphine complexes, the title compound, (I),
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 signi®cant species, [(CH3)2NH2]2[(C6H5)2-
P2O5H]2, 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 OÁ Á ÁO lines. The OÐH distances are
Figure 1
Ê
quite long, approximately 1.2 A. Steiner & Saenger (1994), by
The structure of (I), showing the atomic numbering scheme and
displacement ellipsoids at the 50% probability level. Dashed lines
indicate hydrogen bonds.
examining OÐHÁ Á ÁO hydrogen-bonded structures deter-
mined from low-temperature neutron-diffraction data (T <
o268 # 2006 International Union of Crystallography
DOI: 10.1107/S0108270106009528
Acta Cryst. (2006). C62, o268±o270

organic compounds
Figure 2
Fourier difference maps showing the two symmetric hydrogen bonds viz. (a) O3ÐH3OÁ Á ÁO3i and (b) O5ÐH5OÁ Á ÁO5i (see Table 2). The peak heights at
3
Ê
the H-atom positions are approximately 1 e A
.
Table 1
Selected geometric parameters (A, ).
Experimental
ꢀ
Ê
Phenylphosphine (19.75 g, 0.180 mol) was added to CH2Cl2 (7.63 g,
0.090 mol) with stirring in an ice-cooled Schlenk ¯ask. To this mixture
was added degassed water (150 ml). Dimethylformamide (56 ml) was
added via syringe to 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, phenylphos-
phine. The second fraction, collected at 307 K, was the title
compound, and shiny colorless crystals formed by sublimation.
P1ÐO2
P1ÐO3
P1ÐO1
P1ÐC1
P2ÐO4
1.4811 (15)
1.5269 (16)
1.6190 (16)
1.782 (2)
P2ÐO5
P2ÐO1
P2ÐC7
N1AÐC2A
N1AÐC1A
1.5260 (15)
1.6193 (17)
1.782 (2)
1.475 (3)
1.481 (3)
1.4791 (16)
P1ÐO1ÐP2
124.96 (8)
O2ÐP1ÐO1ÐP2
O3ÐP1ÐO1ÐP2
89.86 (13)
38.52 (13)
O4ÐP2ÐO1ÐP1
O5ÐP2ÐO1ÐP1
88.63 (13)
39.93 (13)
Table 2
Hydrogen-bond geometry (A, ).
Crystal data
C2H8N+ÁC12H11O5P2
ꢀ
Ê
Mo Kꢀ radiation
Cell parameters from 5490
re¯ections
Mr = 343.24
Tetragonal, I41cd
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
a = 13.110 (3) A
ꢁ = 2.5±32.5ꢀ
Ê
Ê
O3ÐH3OÁ Á ÁO3i
O5ÐH5OÁ Á ÁO5i
N1AÐH1NÁ Á ÁO2
N1AÐH2NÁ Á ÁO4i
1.2028 (15)
1.211 (3)
0.89 (3)
1.2028 (15)
1.211 (3)
1.89 (3)
2.406 (3)
2.418 (3)
2.765 (2)
2.748 (3)
179 (5)
174 (5)
170 (3)
165 (3)
1
c = 38.751 (8) A
ꢂ = 0.28 mm
T = 102 K
3
Ê
V = 6660 (3) A
Z = 16
Dx = 1.369 Mg m
Fragment, colorless
0.33 Â 0.30 Â 0.18 mm
0.88 (3)
1.89 (3)
3
Symmetry code: (i) x ‡ 1; y ‡ 1; z.
Data collection
Nonius KappaCCD diffractometer
(with an Oxford Cryosystems
Cryostream cooler)
33359 measured re¯ections
5654 independent re¯ections
4268 re¯ections with I > 2ꢄ(I)
Rint = 0.052
Ê
positions, with CÐH distances of 0.95 A and Uiso(H) = 1.2Ueq of the
attached C atom, and thereafter treated as riding. All methyl H atoms
Ê
were placed in calculated positions, with CÐH distances of 0.98 A
! scans with ꢃ offsets
Absorption correction: multi-scan
(SCALEPACK; Otwinowski
& Minor, 1997)
ꢁmax = 32.6ꢀ
and Uiso(H) = 1.5Ueq of the attached C atom and thereafter treated as
riding. A torsional parameter was re®ned for each methyl group.
Data collection: COLLECT (Nonius, 2000); cell re®nement:
h = 19 ! 19
k = 14 ! 14
Tmin = 0.887, Tmax = 0.951
l = 57 ! 56
SCALEPACK (Otwinowski
DENZO (Otwinowski
& Minor, 1997); data reduction:
Minor, 1997) and SCALEPACK;
Re®nement
&
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.043
wR(F2) = 0.095
S = 1.02
5654 re¯ections
212 parameters
w = 1/[ꢄ2(F2o) + (0.0434P)2
+ 1.9071P]
program(s) used to solve structure: SIR97 (Altomare et al., 1999);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); soft-
ware used to prepare material for publication: SHELXL97.
where P = (F2o + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.33 e A
3
Ê
0.31 e A
Áꢅmin
=
The purchase of the diffractometer was made possible by
grant No. LEQSF(1999±2000)-ESH-TR-13, administered by
the Louisiana Board of Regents.
H atoms treated by a mixture of
independent and constrained
re®nement
Absolute structure: Flack (1983),
2590 Friedel pairs
Flack parameter: 0.21 (8)
The two OÐHÁ Á ÁO hydrogens occupy twofold positions; posi-
tional parameter z and the Uiso value were re®ned for each atom. The
positions of the NH hydrogens were re®ned, with Uiso(H) = 1.2Ueq of
the attached N atom. All aromatic H atoms were placed in calculated
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: HJ1093). Services for accessing these data are
described at the back of the journal.
C2H8N+ÁC12H11O5P2
o269
ꢁ
Acta Cryst. (2006). C62, o268±o270
Courtney et al.

organic compounds
Kingsley, S., Vij, A. & Chandrasekhar, V. (2001). Inorg. Chem. 40, 6057±6060.
Langhans, K. P. & Stelzer, O. (1987). Chem. Ber. 120, 1707±1712.
Mahmoudkhani, A. H. & Langer, V. (2002). J. Mol. Struct. 609, 97±108.
Nonius (2000). COLLECT. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,
Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M.
Sweet, pp. 307±326. New York: Academic Press.
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o270 Courtney et al. C2H8N+ÁC12H11O5P2
Acta Cryst. (2006). C62, o268±o270
ꢁ