Hydroxonium 1-ammonio­ethyl­idene-1,1-bis­phospho­nate

Wu, Y.; Yin, D.-L.

doi:10.1107/S1600536808029565

organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1967

doi:10.1107/S1600536808029565

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Hydroxonium 1-ammonioethylidene-1,1-bisphosphonate

Ying Wu ^a ^* and Du-Lin Yin ^b

^aYueyang Vocational Technology College, Yueyang 414000, Hunan, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410017, Hunan, People's Republic of China
^*Correspondence e-mail: wuying6612@126.com

(Received 7 August 2008; accepted 15 September 2008; online 20 September 2008)

The title compound, H₃O⁺·C₂H₈NO₆P₂⁻, contains a disordered H₃O⁺ cation and an NH₃C(CH₃)(PO₃H)₂ anion. The three H atoms of the H₃O⁺ cation are statistically distributed over four positions with occupancies of 0.75, resulting in a pseudo tetrahedron. Multiple N—H⋯O and O—H⋯O hydrogen bonds generate an intricate three-dimensional network.

Related literature

For related literature, see: Bollinger & Roundhill (1993 ); Chai et al. (1980 ); Clearfield (2002 ); Fernández et al. (2003 ); Li et al. (2008 ); Finn et al. (2003 ); Yin et al. (2005 ).

Experimental

Crystal data

H₃O⁺·C₂H₈NO₆P₂⁻
M_r = 223.06
Triclinic, $[P \overline 1]$
a = 5.6379 (5) Å
b = 8.9712 (8) Å
c = 9.2302 (8) Å
α = 102.111 (1)°
β = 100.499 (1)°
γ = 101.342 (1)°
V = 435.22 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 293 (2) K
0.36 × 0.32 × 0.27 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.839, T_max = 0.876
2811 measured reflections
1946 independent reflections
1871 reflections with I > 2σ(I)
R_int = 0.009

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.095
S = 1.08
1946 reflections
113 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.89	2.02	2.798 (2)	145
N1—H1B⋯O2ⁱⁱ	0.89	2.00	2.766 (2)	144
N1—H1C⋯O6ⁱ	0.89	1.93	2.771 (2)	156
O1—H1⋯O3ⁱⁱⁱ	0.82	1.69	2.501 (2)	168
O4—H4⋯O2^iv	0.82	1.84	2.635 (2)	164
O1W—H9⋯O1^v	0.89	2.06	2.923 (2)	164
O1W—H10⋯O5	0.89	1.88	2.737 (2)	164
O1W—H11⋯O6ⁱ	0.88	1.94	2.781 (2)	159
O1W—H12⋯O5^vi	0.89	2.01	2.901 (3)	180
Symmetry codes: (i) x+1, y, z; (ii) -x+2, -y+2, -z+1; (iii) -x+1, -y+1, -z+1; (iv) -x+1, -y+2, -z+1; (v) x, y, z-1; (vi) -x+2, -y+2, -z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808029565/pv2098sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029565/pv2098Isup2.hkl

checkCIF report

Comment top

Phosphonic acids are interesting ligands. They can complex various metal ions and a series of organic-inorganic hydrid materials containing phosphonic acids have been prepared and characterized. Such materials have potential applications in catalysts, sensors, sorbents, magnetic and luminescent materials (Finn et al., 2003). In addition, introduction of some functional groups to phosphonic acids, such as crown ether, –COOH, –OH, –NR₂ or mixed group will modify their complexing ability (Clearfield, 2002). 1-Aminoethylidene-1,1-diphosphonic acid (AEDPH₄) exists as a zwitterion and is inclined to transfer one proton to the amino group (Bollinger & Roundhill, 1993; Fernández et al., 2003; Li et al., 2008 ). Its deprotonation would result in predictable hydrogen aggregates from stronger P—O—H···O—P to weaker C—H···O hydrogen bonds. However, its crystal structure is still unknown (Yin et al., 2005). Herein, we report the structure of the title compound, (I).

The asymetric unit of (I) is built up from one deprotonated AEDPH₄ anion and a disordered H₃O⁺ cation which are linked through OW—H···O hydrogen bonds (Fig. 1, Table 1). Two of the four protons of phosphonates are used in the protonation of one for the amino group, the other for H₃O⁺ cation. The deprotonated AEDPH₃^- anions form two-dimensional (2D) H-bonded layer along the bc-plane. The strongest H-bond is O1—H1···O3ⁱⁱⁱ (with O1···O3 distance 2.501 (2)Å), which links the AEDPH₃^- anions into dimers which form an infinite chain along the b axis by hydrogen bond O4—H4···O2^iv (O4···O2 distance 2.635 (2) Å). Furthermore, three N-H···O H-bonds connect these chains to obtain a 2D layer. The H₃O⁺ anions bond to the adjacent layers with five Ow—H···O bonds and stabilize the structure. The occurence of different hydrogen bond interactions, N—H···O, O—H···O and OW—H···O results in the formation of an intricated three dimensional network (Fig. 2, Table 1).

Related literature top

For related literature, see: Bollinger & Roundhill (1993); Chai et al. (1980); Clearfield (2002); Fernández et al. (2003); Li et al. (2008); Finn et al. (2003); Yin et al. (2005). .

Experimental top

The title compound was synthesized according to the US Patent 4239695 (Chai et al., 1980). It was crystallized unexpectedly when 4,4_'-bipyridine was adding into the AEDPH₄ H₂O solution to synthesize the complex. However, the 4,4_'-bipyridine was not present in the final product.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. Hydrogen bond is shown as dashed line.
	Fig. 2. Partial packing view of compound ( I ), showing the formation of the three dimensional network built from hydrogen bonds. For clarity, H atoms not involved in hydrogen bonding have been omitted. [symmetry codes: (i) 1+x, y, z; (ii) 2-x , 2-y, z ; (iii) x, y , z-1; (iv) 1-x, 1-y, 1-z].

Hydroxonium 1-ammonioethylidene-1,1-bisphosphonate top

Crystal data top

H₃O⁺·C₂H₈NO₆P₂⁻	Z = 2
M_r = 223.06	F(000) = 232
Triclinic, P1	D_x = 1.702 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6379 (5) Å	Cell parameters from 2523 reflections
b = 8.9712 (8) Å	θ = 2.4–29.6°
c = 9.2302 (8) Å	µ = 0.50 mm⁻¹
α = 102.111 (1)°	T = 293 K
β = 100.499 (1)°	Plate, colorless
γ = 101.342 (1)°	0.36 × 0.32 × 0.27 mm
V = 435.22 (7) Å³

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1871 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.009
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.839, T_max = 0.876	k = −9→11
2811 measured reflections	l = −11→8
1946 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	w = 1/[σ²(F_o²) + (0.0451P)² + 0.5124P] where P = (F_o² + 2F_c²)/3
1946 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

H₃O⁺·C₂H₈NO₆P₂⁻	γ = 101.342 (1)°
M_r = 223.06	V = 435.22 (7) Å³
Triclinic, P1	Z = 2
a = 5.6379 (5) Å	Mo Kα radiation
b = 8.9712 (8) Å	µ = 0.50 mm⁻¹
c = 9.2302 (8) Å	T = 293 K
α = 102.111 (1)°	0.36 × 0.32 × 0.27 mm
β = 100.499 (1)°

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1946 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1871 reflections with I > 2σ(I)
T_min = 0.839, T_max = 0.876	R_int = 0.009
2811 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.08	Δρ_max = 0.44 e Å⁻³
1946 reflections	Δρ_min = −0.58 e Å⁻³
113 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
P1	0.64618 (8)	0.73089 (5)	0.49332 (5)	0.01519 (14)
P2	0.58222 (8)	0.83546 (6)	0.19085 (5)	0.01897 (14)
C1	0.7352 (3)	0.7236 (2)	0.3101 (2)	0.0159 (3)
C2	0.6859 (4)	0.5520 (2)	0.2183 (2)	0.0263 (4)
H2A	0.7448	0.5493	0.1268	0.039*
H2B	0.5106	0.5046	0.1924	0.039*
H2C	0.7717	0.4950	0.2784	0.039*
N1	1.0110 (3)	0.79403 (19)	0.34632 (18)	0.0177 (3)
H1A	1.0884	0.7500	0.4126	0.027*
H1B	1.0421	0.8971	0.3866	0.027*
H1C	1.0657	0.7766	0.2612	0.027*
O1	0.8136 (2)	0.63586 (16)	0.57120 (16)	0.0207 (3)
H1	0.7371	0.5435	0.5513	0.031*
O2	0.7185 (3)	0.89740 (16)	0.58704 (16)	0.0234 (3)
O3	0.3743 (2)	0.64928 (16)	0.46080 (17)	0.0218 (3)
O4	0.6364 (3)	1.00594 (17)	0.29828 (18)	0.0267 (3)
H4	0.5123	1.0175	0.3295	0.040*
O5	0.7259 (3)	0.8501 (2)	0.07158 (17)	0.0295 (3)
O6	0.3106 (3)	0.75734 (19)	0.14090 (16)	0.0262 (3)
O1W	1.0469 (3)	0.8192 (2)	−0.1160 (2)	0.0403 (4)
H9	1.0002	0.7549	−0.2088	0.061*	0.75
H10	0.9220	0.8286	−0.0718	0.061*	0.75
H11	1.1434	0.7837	−0.0515	0.061*	0.75
H12	1.1157	0.9206	−0.1025	0.061*	0.75

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0131 (2)	0.0149 (2)	0.0193 (2)	0.00319 (17)	0.00587 (17)	0.00642 (17)
P2	0.0151 (2)	0.0268 (3)	0.0203 (3)	0.00901 (19)	0.00713 (18)	0.01124 (19)
C1	0.0124 (7)	0.0172 (8)	0.0194 (8)	0.0038 (6)	0.0051 (6)	0.0057 (6)
C2	0.0297 (10)	0.0204 (9)	0.0257 (10)	0.0056 (8)	0.0055 (8)	0.0005 (7)
N1	0.0128 (7)	0.0209 (7)	0.0223 (8)	0.0054 (6)	0.0068 (6)	0.0083 (6)
O1	0.0173 (6)	0.0195 (6)	0.0253 (7)	0.0040 (5)	0.0017 (5)	0.0094 (5)
O2	0.0265 (7)	0.0170 (7)	0.0275 (7)	0.0043 (5)	0.0119 (6)	0.0033 (5)
O3	0.0132 (6)	0.0226 (7)	0.0334 (8)	0.0043 (5)	0.0073 (5)	0.0138 (6)
O4	0.0239 (7)	0.0241 (7)	0.0376 (8)	0.0104 (6)	0.0125 (6)	0.0106 (6)
O5	0.0297 (8)	0.0425 (9)	0.0283 (8)	0.0162 (7)	0.0175 (6)	0.0184 (7)
O6	0.0162 (7)	0.0401 (8)	0.0239 (7)	0.0087 (6)	0.0033 (5)	0.0112 (6)
O1W	0.0390 (9)	0.0496 (11)	0.0344 (9)	0.0119 (8)	0.0101 (7)	0.0127 (8)

Geometric parameters (Å, º) top

P1—O2	1.4952 (14)	C2—H2B	0.9600
P1—O3	1.5081 (13)	C2—H2C	0.9600
P1—O1	1.5686 (14)	N1—H1A	0.8900
P1—C1	1.8417 (18)	N1—H1B	0.8900
P2—O5	1.4928 (14)	N1—H1C	0.8900
P2—O6	1.4947 (14)	O1—H1	0.8200
P2—O4	1.5765 (15)	O4—H4	0.8200
P2—C1	1.8497 (19)	O1W—H9	0.8869
C1—N1	1.505 (2)	O1W—H10	0.8852
C1—C2	1.537 (2)	O1W—H11	0.8841
C2—H2A	0.9600	O1W—H12	0.8888

O2—P1—O3	115.72 (8)	C1—C2—H2B	109.5
O2—P1—O1	108.61 (8)	H2A—C2—H2B	109.5
O3—P1—O1	111.06 (8)	C1—C2—H2C	109.5
O2—P1—C1	109.30 (8)	H2A—C2—H2C	109.5
O3—P1—C1	108.25 (8)	H2B—C2—H2C	109.5
O1—P1—C1	103.15 (8)	C1—N1—H1A	109.5
O5—P2—O6	118.42 (9)	C1—N1—H1B	109.5
O5—P2—O4	106.13 (9)	H1A—N1—H1B	109.5
O6—P2—O4	112.40 (8)	C1—N1—H1C	109.5
O5—P2—C1	105.96 (8)	H1A—N1—H1C	109.5
O6—P2—C1	108.21 (8)	H1B—N1—H1C	109.5
O4—P2—C1	104.72 (8)	P1—O1—H1	109.5
N1—C1—C2	107.76 (14)	P2—O4—H4	109.5
N1—C1—P1	106.97 (11)	H9—O1W—H10	113.6
C2—C1—P1	110.19 (13)	H9—O1W—H11	112.2
N1—C1—P2	107.45 (12)	H10—O1W—H11	102.3
C2—C1—P2	109.40 (13)	H9—O1W—H12	120.3
P1—C1—P2	114.79 (9)	H10—O1W—H12	98.6
C1—C2—H2A	109.5	H11—O1W—H12	107.6

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	2.02	2.798 (2)	145
N1—H1B···O2ⁱⁱ	0.89	2.00	2.766 (2)	144
N1—H1C···O6ⁱ	0.89	1.93	2.771 (2)	156
O1—H1···O3ⁱⁱⁱ	0.82	1.69	2.501 (2)	168
O4—H4···O2^iv	0.82	1.84	2.635 (2)	164
O1W—H9···O1^v	0.89	2.06	2.923 (2)	164
O1W—H10···O5	0.89	1.88	2.737 (2)	164
O1W—H11···O6ⁱ	0.88	1.94	2.781 (2)	159
O1W—H12···O5^vi	0.89	2.01	2.901 (3)	180

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

Experimental details

Crystal data
Chemical formula	H₃O⁺·C₂H₈NO₆P₂⁻
M_r	223.06
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.6379 (5), 8.9712 (8), 9.2302 (8)
α, β, γ (°)	102.111 (1), 100.499 (1), 101.342 (1)
V (Å³)	435.22 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.36 × 0.32 × 0.27

Data collection
Diffractometer	Bruker SMART 4K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.839, 0.876
No. of measured, independent and observed [I > 2σ(I)] reflections	2811, 1946, 1871
R_int	0.009
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.095, 1.08
No. of reflections	1946
No. of parameters	113
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.58

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.89	2.02	2.798 (2)	145
N1—H1B···O2ⁱⁱ	0.89	2.00	2.766 (2)	144
N1—H1C···O6ⁱ	0.89	1.93	2.771 (2)	156
O1—H1···O3ⁱⁱⁱ	0.82	1.69	2.501 (2)	168
O4—H4···O2^iv	0.82	1.84	2.635 (2)	164
O1W—H9···O1^v	0.89	2.06	2.923 (2)	164
O1W—H10···O5	0.89	1.88	2.737 (2)	164
O1W—H11···O6ⁱ	0.88	1.94	2.781 (2)	159
O1W—H12···O5^vi	0.89	2.01	2.901 (3)	180

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

Acknowledgements

This work was supported by the Education Department of Hunan Province (0806D094)

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