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Acta Crystallogr Sect E Struct Rep Online. 2009 March 1; 65(Pt 3): o639.
Published online 2009 February 28. doi:  10.1107/S1600536809006266
PMCID: PMC2968602

tert-Butyl­aminium phosphite

Abstract

In the title compound, C4H12N+·H2PO3 , the components are linked by inter­molecular N—H(...)O and O—H(...)O hydrogen bonds, resulting in a two-dimensional framework.

Related literature

For general background, see: Rao et al. (2000 [triangle]); Wang et al. (2002 [triangle]). For related structures, see: Loub et al. (1978 [triangle]); Smolin et al. (2003 [triangle]).

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Object name is e-65-0o639-scheme1.jpg

Experimental

Crystal data

  • C4H12N+·H2PO3
  • M r = 155.13
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o639-efi1.jpg
  • a = 7.621 (2) Å
  • b = 6.561 (2) Å
  • c = 17.545 (5) Å
  • β = 111.10 (3)°
  • V = 818.5 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 295 K
  • 0.2 × 0.15 × 0.11 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 4275 measured reflections
  • 1524 independent reflections
  • 1332 reflections with I > 2σ(I)
  • R int = 0.023
  • 3 standard reflections every 100 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.030
  • wR(F 2) = 0.084
  • S = 1.06
  • 1524 reflections
  • 103 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.24 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 2008 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006266/hk2620sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006266/hk2620Isup2.hkl

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

Acknowledgments

The authors thank the Natural Science Foundation of Shandong Province (grant Nos. Z2007B01 and Y2006B08).

supplementary crystallographic information

Comment

Recently, compounds containing the phosphorous acid group have attracted much interest because they exhibit some biological activities and the functions of intermediates in the formation of open-framework metal phosphates templated by organic amines (Rao et al., 2000; Wang et al., 2002). Though the structure of H2PO3 ion was described previously (Loub et al., 1978), the ammonium phosphite zwitterion was only reported by Smolin (Smolin et al., 2003). In order to search for new phosphite compounds with higher bioactivity, we synthesized the title compound and report herein its crystal structure.

In the title compound, (Fig. 1), the bond lengths and angles (Table 1) are generally within normal ranges (Smolin et al., 2003). The NH3 group of alkyl is additionally protonated by an H atom of the phosphite ion to give a positively charged molecule. The phosphite ion is shaped like a tetrahedron. The H1P atom is localized at the P atom at a distance of 1.278 (19) Å, which is not involved in hydrogen bonding. The O2-P1 [1.5708 (15) Å] bond is significantly longer than the other P-O bonds of the tetrahedron (Table 1). Phosphite and amine molecules are linked by intramolecular N-H···O hydrogen bonds (Table 2).

In the crystal structure, intermolecular N-H···O and O-H···O hydrogen bonds (Table 2) link the molecules (Fig. 2). Each two orthophosphorous acids are linked by O-H···O hydrogen bonds into channels, while the orthophosphorous acids and amine molecules are linked by N-H···O hydrogen bonds into chains. Then, the chains are linked by N-H···O and O-H···O hydrogen bonds into a two-dimensional framework, as in the phosphates reported by Smolin (Smolin et al., 2003), in which they may be effective in the stabilization of the structure.

Experimental

The title compound was prepared by the reaction of phosphorous acid (0.164 g, 2.0 mmol) and tert-butylamine (0.182 g, 2.5 mmol) stirred in water/ethanol (5:1 v/v) solution (20 ml). Single crystals suitable for X-ray analysis were obtained by recrystallization from water/ethanol (5:1 v/v) solution at room temperature over a period of 3 d.

Refinement

H1N, H2N, H3N (for NH3), H10 (for OH) and H1P (for PH) were located in difference synthesis and refined isotropically [N-H = 0.87 (2)-0.94 (2) Å, Uiso(H) = 0.041 (5)-0.052 (6) Å2; O-H = 0.829 (10) Å, Uiso(H) = 0.063 (7) Å2 and P-H = 1.278 (19) Å, Uiso(H) = 0.046 (5) Å2]. The remaining H atoms were positioned geometrically with C-H = 0.96 Å, for methyl H atoms and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C).

Figures

Fig. 1.
The molecular structure of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A stereoview of the crystal structure of the title compound. Showing the formation of channels and two-dimensional framework. For the sake of clarity, H atoms bonded to C atoms have been omitted. Hydrogen bonds are shown as dashed lines. Color scheme: ...

Crystal data

C4H12N+·H2PO3F(000) = 336
Mr = 155.13Dx = 1.259 Mg m3
Monoclinic, P21/cMelting point: 504.8 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 7.621 (2) ÅCell parameters from 25 reflections
b = 6.561 (2) Åθ = 4–14°
c = 17.545 (5) ŵ = 0.28 mm1
β = 111.10 (3)°T = 295 K
V = 818.5 (4) Å3Block, colorless
Z = 40.2 × 0.15 × 0.11 mm

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.023
Radiation source: fine-focus sealed tubeθmax = 25.5°, θmin = 2.5°
graphiteh = −9→7
ω scansk = −7→7
4275 measured reflectionsl = −21→19
1524 independent reflections3 standard reflections every 100 reflections
1332 reflections with I > 2σ(I) intensity decay: none

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.030H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.084w = 1/[σ2(Fo2) + (0.0424P)2 + 0.222P] where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
1524 reflectionsΔρmax = 0.19 e Å3
103 parametersΔρmin = −0.24 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.040 (4)

Special details

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)

xyzUiso*/Ueq
P10.45578 (6)0.77903 (6)0.40886 (2)0.03180 (18)
H1P0.308 (3)0.691 (3)0.4103 (11)0.046 (5)*
O10.51036 (19)0.66932 (19)0.34600 (7)0.0445 (4)
O20.6124 (2)0.7419 (2)0.49496 (8)0.0496 (4)
H1O0.606 (3)0.829 (3)0.5280 (11)0.063 (7)*
O30.41488 (17)1.00287 (17)0.39392 (7)0.0386 (3)
N10.6062 (2)0.2679 (2)0.32177 (9)0.0334 (3)
H1N0.574 (3)0.389 (3)0.3327 (12)0.048 (6)*
H2N0.544 (3)0.174 (3)0.3436 (11)0.041 (5)*
H3N0.563 (3)0.246 (3)0.2674 (14)0.052 (6)*
C10.9076 (3)0.4138 (4)0.32887 (14)0.0620 (6)
H1A1.04190.40670.35470.093*
H1B0.86400.54270.34100.093*
H1C0.87320.40020.27080.093*
C20.8688 (3)0.2586 (3)0.45276 (11)0.0497 (5)
H2A1.00150.23710.47960.074*
H2B0.80100.15680.47020.074*
H2C0.83610.39140.46650.074*
C30.8674 (3)0.0346 (3)0.33646 (13)0.0538 (5)
H3A1.00000.01130.36280.081*
H3B0.7991−0.06840.35310.081*
H3C0.83440.02920.27830.081*
C40.8178 (2)0.2434 (2)0.36060 (11)0.0372 (4)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
P10.0408 (3)0.0290 (3)0.0292 (3)−0.00216 (17)0.0170 (2)−0.00246 (16)
O10.0689 (9)0.0358 (7)0.0335 (7)0.0069 (6)0.0242 (6)−0.0032 (5)
O20.0685 (9)0.0427 (8)0.0329 (7)0.0185 (6)0.0124 (7)−0.0020 (5)
O30.0508 (7)0.0330 (7)0.0332 (6)0.0054 (5)0.0168 (5)0.0001 (5)
N10.0418 (8)0.0286 (8)0.0317 (8)0.0013 (6)0.0157 (7)−0.0006 (6)
C10.0575 (13)0.0658 (14)0.0668 (14)−0.0160 (11)0.0272 (11)0.0103 (11)
C20.0500 (11)0.0570 (12)0.0375 (10)−0.0032 (9)0.0103 (9)−0.0018 (8)
C30.0512 (11)0.0512 (12)0.0612 (12)0.0124 (9)0.0229 (10)−0.0050 (9)
C40.0369 (9)0.0376 (9)0.0385 (9)−0.0009 (7)0.0153 (8)−0.0001 (7)

Geometric parameters (Å, °)

P1—H1P1.278 (19)C1—H1B0.9600
O1—P11.4958 (12)C1—H1C0.9599
O2—P11.5708 (15)C2—C41.524 (3)
O2—H1O0.829 (10)C2—H2A0.9600
O3—P11.5043 (12)C2—H2B0.9600
N1—C41.516 (2)C2—H2C0.9600
N1—H1N0.87 (2)C3—C41.521 (2)
N1—H2N0.94 (2)C3—H3A0.9600
N1—H3N0.90 (2)C3—H3B0.9600
C1—C41.517 (3)C3—H3C0.9600
C1—H1A0.9600
O1—P1—O2108.54 (8)C4—C2—H2A109.4
O1—P1—O3115.87 (7)C4—C2—H2B109.4
O1—P1—H1P106.1 (8)C4—C2—H2C109.6
O2—P1—H1P106.3 (8)H2B—C2—H2A109.5
O3—P1—O2110.90 (7)H2C—C2—H2A109.5
O3—P1—H1P108.5 (8)H2C—C2—H2B109.5
P1—O2—H1O110.5 (16)C4—C3—H3A109.5
C4—N1—H1N109.6 (13)C4—C3—H3B109.5
C4—N1—H2N111.0 (11)C4—C3—H3C109.5
C4—N1—H3N112.5 (14)H3B—C3—H3A109.5
H2N—N1—H1N106.5 (16)H3C—C3—H3B109.5
H3N—N1—H1N110.8 (17)H3C—C3—H3A109.5
H3N—N1—H2N106.2 (16)N1—C4—C1107.70 (15)
C4—C1—H1A109.6N1—C4—C2107.08 (15)
C4—C1—H1B109.2N1—C4—C3107.52 (14)
C4—C1—H1C109.5C1—C4—C2111.37 (16)
H1B—C1—H1A109.5C1—C4—C3111.79 (17)
H1C—C1—H1A109.5C3—C4—C2111.14 (15)
H1C—C1—H1B109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H3N···O1i0.90 (2)1.93 (2)2.826 (2)173.1 (18)
N1—H2N···O3ii0.94 (2)1.91 (2)2.8425 (19)174.7 (17)
N1—H1N···O10.87 (2)1.94 (2)2.806 (2)173.1 (19)
O2—H1O···O3iii0.83 (1)1.81 (1)2.6339 (17)174 (2)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x+1, −y+2, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HK2620).

References

  • Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Loub, J., Podlahová, J. & Ječný, J. (1978). Acta Cryst. B34, 32–34.
  • Rao, C. N. R., Natarajan, S. & Neeraj, S. (2000). J. Solid State Chem.152, 302–321.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Smolin, Y. I., Lapshin, A. E. & Pankova, G. A. (2003). J. Struct. Chem.44, 511–515.
  • Wang, Y., Yu, J., Shi, Z., Zou, Y. & Xu, R. (2002). J. Chem. Soc. Dalton Trans. pp. 4060–4063.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography