tert-Butyl­aminium phosphite

Jian, F.-F.; Zhang, J.-L.

doi:10.1107/S1600536809006266

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o639

doi:10.1107/S1600536809006266

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tert-Butylaminium phosphite

Fang-Fang Jian ^a ^* and Jun-Li Zhang ^a

^aNew Materials and Function Coordination Chemistry Laboratory, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: ffj2003@163169.net

(Received 31 January 2009; accepted 20 February 2009; online 28 February 2009)

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 ); Wang et al. (2002 ). For related structures, see: Loub et al. (1978 ); Smolin et al. (2003 ).

Experimental

Crystal data

C₄H₁₂N⁺·H₂PO₃⁻
M_r = 155.13
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.030
wR(F²) = 0.084
S = 1.06
1524 reflections
103 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H3N⋯O1ⁱ	0.90 (2)	1.93 (2)	2.826 (2)	173.1 (18)
N1—H2N⋯O3ⁱⁱ	0.94 (2)	1.91 (2)	2.8425 (19)	174.7 (17)
N1—H1N⋯O1	0.87 (2)	1.94 (2)	2.806 (2)	173.1 (19)
O2—H1O⋯O3ⁱⁱⁱ	0.829 (10)	1.808 (10)	2.6339 (17)	174 (2)
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) -x+1, -y+2, -z+1.

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

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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: C = black, O = red, N = blue, P = green, H = cyan.

tert-Butylaminium phosphite top

Crystal data top

C₄H₁₂N⁺·H₂PO₃⁻	F(000) = 336
M_r = 155.13	D_x = 1.259 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 504.8 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 7.621 (2) Å	Cell parameters from 25 reflections
b = 6.561 (2) Å	θ = 4–14°
c = 17.545 (5) Å	µ = 0.28 mm⁻¹
β = 111.10 (3)°	T = 295 K
V = 818.5 (4) Å³	Block, colorless
Z = 4	0.2 × 0.15 × 0.11 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 2.5°
Graphite monochromator	h = −9→7
ω scans	k = −7→7
4275 measured reflections	l = −21→19
1524 independent reflections	3 standard reflections every 100 reflections
1332 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.084	w = 1/[σ²(F_o²) + (0.0424P)² + 0.222P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
1524 reflections	Δρ_max = 0.19 e Å⁻³
103 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.040 (4)

Crystal data top

C₄H₁₂N⁺·H₂PO₃⁻	V = 818.5 (4) Å³
M_r = 155.13	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.621 (2) Å	µ = 0.28 mm⁻¹
b = 6.561 (2) Å	T = 295 K
c = 17.545 (5) Å	0.2 × 0.15 × 0.11 mm
β = 111.10 (3)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.19 e Å⁻³
1524 reflections	Δρ_min = −0.24 e Å⁻³
103 parameters

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

	x	y	z	U_iso*/U_eq
P1	0.45578 (6)	0.77903 (6)	0.40886 (2)	0.03180 (18)
H1P	0.308 (3)	0.691 (3)	0.4103 (11)	0.046 (5)*
O1	0.51036 (19)	0.66932 (19)	0.34600 (7)	0.0445 (4)
O2	0.6124 (2)	0.7419 (2)	0.49496 (8)	0.0496 (4)
H1O	0.606 (3)	0.829 (3)	0.5280 (11)	0.063 (7)*
O3	0.41488 (17)	1.00287 (17)	0.39392 (7)	0.0386 (3)
N1	0.6062 (2)	0.2679 (2)	0.32177 (9)	0.0334 (3)
H1N	0.574 (3)	0.389 (3)	0.3327 (12)	0.048 (6)*
H2N	0.544 (3)	0.174 (3)	0.3436 (11)	0.041 (5)*
H3N	0.563 (3)	0.246 (3)	0.2674 (14)	0.052 (6)*
C1	0.9076 (3)	0.4138 (4)	0.32887 (14)	0.0620 (6)
H1A	1.0419	0.4067	0.3547	0.093*
H1B	0.8640	0.5427	0.3410	0.093*
H1C	0.8732	0.4002	0.2708	0.093*
C2	0.8688 (3)	0.2586 (3)	0.45276 (11)	0.0497 (5)
H2A	1.0015	0.2371	0.4796	0.074*
H2B	0.8010	0.1568	0.4702	0.074*
H2C	0.8361	0.3914	0.4665	0.074*
C3	0.8674 (3)	0.0346 (3)	0.33646 (13)	0.0538 (5)
H3A	1.0000	0.0113	0.3628	0.081*
H3B	0.7991	−0.0684	0.3531	0.081*
H3C	0.8344	0.0292	0.2783	0.081*
C4	0.8178 (2)	0.2434 (2)	0.36060 (11)	0.0372 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0408 (3)	0.0290 (3)	0.0292 (3)	−0.00216 (17)	0.0170 (2)	−0.00246 (16)
O1	0.0689 (9)	0.0358 (7)	0.0335 (7)	0.0069 (6)	0.0242 (6)	−0.0032 (5)
O2	0.0685 (9)	0.0427 (8)	0.0329 (7)	0.0185 (6)	0.0124 (7)	−0.0020 (5)
O3	0.0508 (7)	0.0330 (7)	0.0332 (6)	0.0054 (5)	0.0168 (5)	0.0001 (5)
N1	0.0418 (8)	0.0286 (8)	0.0317 (8)	0.0013 (6)	0.0157 (7)	−0.0006 (6)
C1	0.0575 (13)	0.0658 (14)	0.0668 (14)	−0.0160 (11)	0.0272 (11)	0.0103 (11)
C2	0.0500 (11)	0.0570 (12)	0.0375 (10)	−0.0032 (9)	0.0103 (9)	−0.0018 (8)
C3	0.0512 (11)	0.0512 (12)	0.0612 (12)	0.0124 (9)	0.0229 (10)	−0.0050 (9)
C4	0.0369 (9)	0.0376 (9)	0.0385 (9)	−0.0009 (7)	0.0153 (8)	−0.0001 (7)

Geometric parameters (Å, º) top

P1—H1P	1.278 (19)	C1—H1B	0.9600
O1—P1	1.4958 (12)	C1—H1C	0.9599
O2—P1	1.5708 (15)	C2—C4	1.524 (3)
O2—H1O	0.829 (10)	C2—H2A	0.9600
O3—P1	1.5043 (12)	C2—H2B	0.9600
N1—C4	1.516 (2)	C2—H2C	0.9600
N1—H1N	0.87 (2)	C3—C4	1.521 (2)
N1—H2N	0.94 (2)	C3—H3A	0.9600
N1—H3N	0.90 (2)	C3—H3B	0.9600
C1—C4	1.517 (3)	C3—H3C	0.9600
C1—H1A	0.9600

O1—P1—O2	108.54 (8)	C4—C2—H2A	109.4
O1—P1—O3	115.87 (7)	C4—C2—H2B	109.4
O1—P1—H1P	106.1 (8)	C4—C2—H2C	109.6
O2—P1—H1P	106.3 (8)	H2B—C2—H2A	109.5
O3—P1—O2	110.90 (7)	H2C—C2—H2A	109.5
O3—P1—H1P	108.5 (8)	H2C—C2—H2B	109.5
P1—O2—H1O	110.5 (16)	C4—C3—H3A	109.5
C4—N1—H1N	109.6 (13)	C4—C3—H3B	109.5
C4—N1—H2N	111.0 (11)	C4—C3—H3C	109.5
C4—N1—H3N	112.5 (14)	H3B—C3—H3A	109.5
H2N—N1—H1N	106.5 (16)	H3C—C3—H3B	109.5
H3N—N1—H1N	110.8 (17)	H3C—C3—H3A	109.5
H3N—N1—H2N	106.2 (16)	N1—C4—C1	107.70 (15)
C4—C1—H1A	109.6	N1—C4—C2	107.08 (15)
C4—C1—H1B	109.2	N1—C4—C3	107.52 (14)
C4—C1—H1C	109.5	C1—C4—C2	111.37 (16)
H1B—C1—H1A	109.5	C1—C4—C3	111.79 (17)
H1C—C1—H1A	109.5	C3—C4—C2	111.14 (15)
H1C—C1—H1B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3N···O1ⁱ	0.90 (2)	1.93 (2)	2.826 (2)	173.1 (18)
N1—H2N···O3ⁱⁱ	0.94 (2)	1.91 (2)	2.8425 (19)	174.7 (17)
N1—H1N···O1	0.87 (2)	1.94 (2)	2.806 (2)	173.1 (19)
O2—H1O···O3ⁱⁱⁱ	0.83 (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.

Experimental details

Crystal data
Chemical formula	C₄H₁₂N⁺·H₂PO₃⁻
M_r	155.13
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	7.621 (2), 6.561 (2), 17.545 (5)
β (°)	111.10 (3)
V (Å³)	818.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.2 × 0.15 × 0.11

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4275, 1524, 1332
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.084, 1.06
No. of reflections	1524
No. of parameters	103
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.24

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL/PC (Sheldrick, 2008), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top

O1—P1	1.4958 (12)	O3—P1	1.5043 (12)
O2—P1	1.5708 (15)

O1—P1—O2	108.54 (8)	O3—P1—O2	110.90 (7)
O1—P1—O3	115.87 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H3N···O1ⁱ	0.90 (2)	1.93 (2)	2.826 (2)	173.1 (18)
N1—H2N···O3ⁱⁱ	0.94 (2)	1.91 (2)	2.8425 (19)	174.7 (17)
N1—H1N···O1	0.87 (2)	1.94 (2)	2.806 (2)	173.1 (19)
O2—H1O···O3ⁱⁱⁱ	0.829 (10)	1.808 (10)	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.

Acknowledgements

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

References

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