Cyclo­hexyl­ammonium acetate–N,N′,N′′-tricyclo­hexyl­phospho­ric triamide (1/1)

Mehrdad Pourayoubi; Mojtaba Keikha; Arnold L Rheingold; James A Golen

doi:10.1107/S1600536812028589

. 2012 Jun 30;68(Pt 7):o2266. doi: 10.1107/S1600536812028589

Cyclohexylammonium acetate–N,N′,N′′-tricyclohexylphosphoric triamide (1/1)

Mehrdad Pourayoubi ^a, Mojtaba Keikha ^a,^*, Arnold L Rheingold ^b, James A Golen ^b

PMCID: PMC3394049 PMID: 22798914

Abstract

In the phosphoric triamide molecule of the title compound, C₆H₁₄N⁺·C₂H₃O₂ ⁻·C₁₈H₃₆N₃OP, the P atom displays a distorted tetrahedral geometry and the cyclohexyl rings adopt chair conformations with the NH groups in equatorial positions. In the crystal, the cations, anions and phosphoric triamide molecules are linked via N—H⋯O hydrogen bonds into a two-dimensional array parallel to the bc plane. The O atom of the P(O) group acts as a double-hydrogen-bond acceptor.

Related literature

For background to phosphoric triamide molecules and for bond lengths and angles in related structures, see: Pourayoubi, Tarahhomi et al. (2012 ▶); Sabbaghi et al. (2011 ▶). For a definition of double-hydrogen-bond acceptor, see: Pourayoubi, Nečas & Negari (2012 ▶). For hydrolysis of compounds containing a C N bond, see: Vollhardt & Schore (1998 ▶).

Experimental

Crystal data

C₆H₁₄N⁺·C₂H₃O₂ ⁻·C₁₈H₃₆N₃OP
M _r = 500.69
Monoclinic,
a = 12.7663 (8) Å
b = 10.9011 (7) Å
c = 21.2791 (13) Å
β = 104.523 (3)°
V = 2866.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 90 K
0.35 × 0.25 × 0.20 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.957, T _max = 0.975
21979 measured reflections
5898 independent reflections
4702 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.119
S = 0.97
5898 reflections
326 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.47 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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 and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028589/ff2071sup1.cif

e-68-o2266-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028589/ff2071Isup2.hkl

e-68-o2266-Isup2.hkl^{(288.7KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O1ⁱ	0.87 (1)	2.14 (2)	3.0049 (18)	171 (2)
N3—H3N⋯O2ⁱⁱ	0.84 (1)	2.05 (2)	2.8837 (18)	173 (2)
N1—H1N⋯O3	0.86 (1)	2.21 (2)	3.0394 (18)	163 (2)
N4—H4NC⋯O1ⁱⁱⁱ	0.89 (1)	2.05 (2)	2.9445 (18)	178 (2)
N4—H4NB⋯O3^iv	0.89 (2)	1.94 (2)	2.7666 (19)	155 (2)
N4—H4NA⋯O2^v	0.88 (2)	1.83 (2)	2.6992 (19)	169 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

Support of this investigation by Ferdowsi University of Mashhad is gratefully acknowledged.

supplementary crystallographic information

Comment

The X-ray determination of the title co-crystal, P(O)(NHC₆H₁₁)₃,(C₆H₁₁NH₃⁺)(CH₃COO^-), (Fig. 1) was performed following to our previous study on synthesis and crystal structure determination of phosphoric triamide compounds (Pourayoubi, Tarahhomi et al., 2012 and Sabbaghi et al., 2011).

The cyclohexyl rings of phosphoric triamide molecule and also in the C₆H₁₁NH₃⁺ cation have the chair conformation and the NH and NH₃⁺ groups are in the equatorial position of the rings. In P(O)(NHC₆H₁₁)₃, the P atom exists in a distorted tetrahedral environment with the P—N bond lengths of 1.6315 (14) Å, 1.6440 (14) Å and 1.6463 (14) Å (for P1—N1). The P═O bond length and the P—N—C bond angles are standard for the phosphoric triamides (Pourayoubi, Tarahhomi et al., 2012 and Sabbaghi et al., 2011).

In the crystal, the oxygen atom of the P═O group acts as a double-hydrogen bond acceptor (Pourayoubi, Nečas & Negari, 2012), forming the P═O···[H—N][H—N] grouping with one N—H unit of a neighboring P(O)(NHC₆H₁₁)₃ molecule and one N—H unit of C₆H₁₁NH₃⁺ cation. Other N—H units of P(O)(NHC₆H₁₁)₃ and N—H units of C₆H₁₁NH₃⁺ are involved in the N—H···O hydrogen bonds with the O atoms of acetate anion. These N—H···O hydrogen bonds form a two-dimensional arrangement parallel to bc plane (Fig. 2).

Experimental

The title co-crystal was obtained fortuitously from a reaction between phosphoryl chloride and cyclohexylamine in acetonitrile at 273 K (4 h) and then the treatment of dibenzylamine at ice bath temperature. The presence of acetate anion is attributed to the hydrolysis of acetonitrile in acidic media of reaction (Vollhardt & Schore, 1998).