Dicyclo-hexyl-ammonium hydrogen phenyl-phospho-nate.

Abstract

In the title salt, [(C(6)H(11))(2)NH(2)](+)·[C(6)H(5)PO(2)(OH)](-), the anion is monodeprotonated and acts as both a hydrogen-bond donor and acceptor. The anions are linked by pairs of O-H⋯O inter-actions, forming inversion dimers with R(2) (2)(8) ring motifs. These dimers are bridged by two dicyclo-hexyl-aminium cations via pairs of N-H⋯O hydrogen bonds, giving R(4) (4)(12) ring motifs, forming chains propagating along [010]. The chains are bridged by C-H⋯O inter-actions, forming a two-dimensional network lying parallel to (101).

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Dicyclohexylammonium hydrogen
phenylphosphonate
Tidiane Diop,a* Libasse Diop,aThierry Marisband Helen
Stoeckli-Evansc
aLaboratoire de Chimie Minerale et Analytique, Departement de Chimie, Faculte ´ des
Sciences et Techniques, Universite ´ Cheikh Anta Diop, Dakar, Senegal,bDepartement
de Chimie, Universite ´ de Montreal, CP 6128, Succ. Centre-Ville, Montreal, Quebec,
Canada H3C 3J7, andcInstitute of Physics, University of Neucha ˆtel, rue Emile-
Argand 11, CH-2000 Neucha ˆtel, Switzerland
Correspondence e-mail: tijchimia@yahoo.fr
Received 30 March 2012; accepted 10 April 2012
Key indicators: single-crystal X-ray study; T = 150 K; mean ?(C–C) = 0.002 A ˚;
R factor = 0.036; wR factor = 0.098; data-to-parameter ratio = 16.5.
In the title salt, [(C6H11)2NH2]+?[C6H5PO2(OH)]?, the anion
is monodeprotonated and acts as both a hydrogen-bond donor
and acceptor. The anions are linked by pairs of O—H???O
interactions, forming inversion dimers with R2
These dimers are bridged by two dicyclohexylaminium cations
via pairs of N—H???O hydrogen bonds, giving R4
motifs, forming chains propagating along [010]. The chains are
bridged by C—H???O interactions, forming a two-dimensional
network lying parallel to (101).
2(8) ring motifs.
4(12) ring
Related literature
For the crystal structure of phenylphosphonic acid, see:
Weakley (1976). For the crystal structure of anilinium
phenylphosphonate, see: Mahmoudkhani & Langer (2002).
For hydrogen-bond motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
C12H24N+?C6H6O3P?
Mr= 339.40
Monoclinic, P21=n
a = 13.3212 (4) A˚
b = 8.9093 (3) A˚
c = 16.0670 (5) A˚
? = 104.385 (1)?
V = 1847.09 (10) A˚3
Z = 4
Cu K? radiation
? = 1.43 mm?1
T = 150 K
0.16 ? 0.12 ? 0.08 mm
Data collection
Bruker Microstar diffractometer
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
Tmin= 0.749, Tmax= 0.892
21802 measured reflections
3456 independent reflections
3221 reflections with I > 2?(I)
Rint= 0.045
Refinement
R[F2> 2?(F2)] = 0.036
wR(F2) = 0.098
S = 1.08
3456 reflections
210 parameters
H-atom parameters constrained
??max= 0.34 e A˚?3
??min= ?0.34 e A˚?3
Table 1
Hydrogen-bond geometry (A˚,?).
D—H???A
O3—H3A???O1i
N1—H1A???O1
N1—H1B???O2ii
C18—H18A???O3iii
C18—H18B???O2ii
Symmetry
x þ1
D—HH???AD???AD—H???A
0.84
0.92
0.92
0.99
0.99
1.75
1.86
1.81
2.52
2.52
2.5920 (13)
2.7520 (14)
2.6897 (15)
3.3019 (16)
3.2693 (16)
175
161
159
136
133
codes:
2;z þ1
(i)
?x þ 1;?y þ 1;?z þ 1; (ii)
?x þ 1;?y;?z þ 1;(iii)
2;?y þ1
2.
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT
(Bruker, 2009); data reduction: SAINT; program(s) used to solve
structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine
structure: SHELXL97(Sheldrick,
SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008);
software used to prepare material for publication: SHELXTL and
publCIF (Westrip, 2010).
2008); moleculargraphics:
Supplementary data and figures for this paper are available from the
IUCr electronic archives (Reference: HB6721).
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem.
Int. Ed. Engl. 34, 1555–1573.
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,
USA.
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,
Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood,
P. A. (2008). J. Appl. Cryst. 41, 466–470.
Mahmoudkhani, A. H. & Langer, V. (2002). J. Mol. Struct. 609, 97–108.
Sheldrick, G. M. (2004). SADABS. University of Go ¨ttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Weakley, T. J. R. (1976). Acta Cryst. B32, 2889–2890.
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.
organic compounds
o1432
Diop et al.
doi:10.1107/S160053681201553X
Acta Cryst. (2012). E68, o1432
Acta Crystallographica Section E
Structure Reports
Online
ISSN 1600-5368

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supplementary materials
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Acta Cryst. (2012). E68, o1432
supplementary materials
Acta Cryst. (2012). E68, o1432 [doi:10.1107/S160053681201553X]
Dicyclohexylammonium hydrogen phenylphosphonate
Tidiane Diop, Libasse Diop, Thierry Maris and Helen Stoeckli-Evans
Comment
In the title salt (Fig. 1), the hydrogen phenylphosphonate anion is unequivocally tetrahedral, with three oxygen atoms and
a phenyl group; O2—P1—O1 116.59 (5)°, O3—P1—C1 104.45 (5)°. The P—O distances are different [1.4870 (10) Å for
P═O, 1.5134 (9) Å for P-O-, and 1.574 (3) Å for bond P-O(H)]. This is similar to the situation in the crystal structure of
the parent phenylphosphonic acid PhPO3H2 (Weakley, 1976), with bond distances of 1.496 Å for P═O and 1.545 Å for P
—O(H).
In the crystal, the anions are linked by a pair of O-H···O hydrogen bonds to form inversion dimers with a ring motif of
R22(8) (Bernstein et al., 1995; Table 1 and Fig. 2). These dimers are linked by two dicyclohexylaminium cations, via pairs
of N-H···O hydrogen bonds forming a ring motif of R44(12), to form chains propagating along [010], as shown in Table 1
and Fig. 2. A similar chain arrangement has been observed in the crystal structure of anilinium phenylphosphonate
(Mahmoudkhani & Langer, 2002). In the title compound the chains are linked by C-H···O interactions to form a two-
dimensional network that lies parallel to (101); see Table 1 and Fig. 2.
Experimental
When dicyclohexylamine was allowed to react with phenylphosphonic acid in an equimolar ratio (1:1) in water, a
precipitate was obtained and filtered [Yield: 83%; M.p: 448 K]. The filtrate was allowed to evaporate at 333 K, giving
colourless block-like crystals of the title compound.
Refinement
The OH and NH2 H atoms could be located in a difference electron density map. For refinement all the H-atoms were
placed in calculated positions and treated as riding atoms: O-H = 0.84 Å, N-H = 0.92 Å, C-H = 0.95, 0.99 and 1.00 Å for
CH(aromatic), methylene and methine H atoms, respectively, with Uiso = k × Ueq(O,N,C), where k = 1.5 for OH and NH2
H atoms, and = 1.2 for other H atoms.
Computing details
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009);
program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97
(Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2008); software used to
prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2010).

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supplementary materials
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Acta Cryst. (2012). E68, o1432
Figure 1
The molecular structure of the title salt. Displacement ellipsoids are drawn at the 50% probability level [an N-H···O
hydrogen bond is shown as a dashed line].

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Acta Cryst. (2012). E68, o1432
Figure 2
A view of the crystal packing of the title salt. The O-H···O and N-H···O hydrogen bonds, and the C-H···O interactions are
shown as dashed cyan lines (see Table 1 for details; H atoms not involved in these interactions have been omitted for
clarity).
dicyclohexylammonium hydrogen phenylphosphonate
Crystal data
C12H24N+·C6H6O3P−
Mr = 339.40
Monoclinic, P21/n
Hall symbol: -P 2yn
a = 13.3212 (4) Å
b = 8.9093 (3) Å
c = 16.0670 (5) Å
β = 104.385 (1)°
V = 1847.09 (10) Å3
Z = 4
F(000) = 736
Dx = 1.220 Mg m−3
Cu Kα radiation, λ = 1.54178 Å
Cell parameters from 10987 reflections
θ = 3.9–69.5°
µ = 1.43 mm−1
T = 150 K
Block, colourless
0.16 × 0.12 × 0.08 mm
Data collection
Bruker Microstar
diffractometer
Radiation source: Rotating Anode
Helios optics monochromator
Detector resolution: 8.3 pixels mm-1
ω scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
Tmin = 0.749, Tmax = 0.892
21802 measured reflections
3456 independent reflections
3221 reflections with I > 2σ(I)
Rint = 0.045
θmax = 70.0°, θmin = 3.9°
h = −15→16
k = −10→10
l = −19→17

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Acta Cryst. (2012). E68, o1432
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.036
wR(F2) = 0.098
S = 1.08
3456 reflections
210 parameters
0 restraints
Primary atom site location: structure-invariant
direct methods
Secondary atom site location: difference Fourier
map
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0485P)2 + 0.5837P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.34 e Å−3
Δρmin = −0.34 e Å−3
Special details
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are
estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the
estimation of distances, angles and torsion angles
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
N1
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
P1
O1
O2
O3
C1
C2
C3
C4
C5
C6
H1A
H1B
H7A
H7B
0.61697 (8)
0.78359 (11)
0.88185 (13)
0.85691 (14)
0.79476 (14)
0.69609 (12)
0.71952 (10)
0.61555 (10)
0.50257 (10)
0.49544 (11)
0.54933 (12)
0.66214 (11)
0.67143 (10)
0.48868 (2)
0.52613 (7)
0.43638 (8)
0.41421 (7)
0.59865 (10)
0.61401 (14)
0.69755 (16)
0.76585 (14)
0.75229 (12)
0.66913 (11)
0.57730
0.58430
0.80310
0.74170
0.08819 (12)
0.20505 (17)
0.17940 (19)
0.1191 (2)
−0.02535 (19)
−0.00267 (17)
0.06220 (15)
0.16079 (14)
0.18592 (16)
0.25630 (18)
0.15792 (18)
0.13042 (17)
0.06407 (15)
0.32919 (3)
0.31140 (10)
0.19710 (11)
0.46904 (10)
0.38079 (15)
0.31648 (17)
0.3597 (2)
0.46728 (19)
0.53178 (18)
0.48883 (16)
0.14630
−0.00320
0.23750
0.28580
0.61698 (7)
0.60436 (11)
0.57279 (13)
0.48160 (12)
0.47509 (11)
0.50547 (9)
0.59617 (9)
0.70110 (8)
0.70178 (9)
0.78668 (10)
0.86212 (10)
0.86139 (9)
0.77601 (8)
0.40858 (2)
0.50502 (6)
0.35992 (6)
0.38831 (6)
0.36779 (8)
0.29338 (10)
0.26150 (12)
0.30332 (13)
0.37773 (11)
0.40993 (9)
0.57380
0.61490
0.66520
0.57010
0.0241 (3)
0.0360 (4)
0.0474 (6)
0.0504 (6)
0.0456 (6)
0.0347 (4)
0.0270 (4)
0.0246 (4)
0.0297 (4)
0.0359 (4)
0.0375 (5)
0.0335 (4)
0.0285 (4)
0.0235 (1)
0.0267 (3)
0.0353 (3)
0.0278 (3)
0.0267 (4)
0.0401 (5)
0.0534 (7)
0.0492 (6)
0.0401 (5)
0.0309 (4)
0.0360*
0.0360*
0.0430*
0.0430*