Hydroxonium 1-ammonio­ethane-1,1-diyl­diphospho­nate

Li, M.; Wen, W.; Ha, W.; Chang, L.

doi:10.1107/S1600536809008770

organic compounds

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Volume 65| Part 4| April 2009| Page o787

doi:10.1107/S1600536809008770

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Hydroxonium 1-ammonioethane-1,1-diyldiphosphonate

Ming Li,^a ^* Wen Wen,^a Wuzu Ha ^a and Liang Chang ^a

^aDepartment of Chemical Engineering, Wuhan University of Science and Engineering, Wuhan 430073, People's Republic of China
^*Correspondence e-mail: lim@wuse.edu.cn

(Received 9 October 2008; accepted 10 March 2009; online 19 March 2009)

The title complex, H₃O⁺·NH₃C(CH₃)(PO₃H)₂⁻, contains a hydroxonium ion and an NH₃C(CH₃)(PO₃H)₂⁻ anion. The three H atoms of H₃O⁺ form a pseudo-tetrahedron by being distributed over four positions with occupation factors of 0.75. Multiple N—H⋯O and O—H⋯O hydrogen bonds in the crystal structure form an intricate three-dimensional supramolecular network.

Related literature

For the structures of organophosphonates, see: Clearfield (2002 ); Finn et al. (2003 ). For similar bisphosphonates, see: Fernández et al. (2003 ); For complexes with 1-aminoethylidene-1,1-diphosphonic acid, see: Yin et al. (2005 ); Ding et al. (2006 ); Li et al. (2008 ). For the synthesis, see: Chai et al. (1980 ).

Experimental

Crystal data

H₃O⁺·C₂H₈N₂O₆P₂⁻
M_r = 223.06
Monoclinic, P 2₁ /c
a = 7.3372 (6) Å
b = 10.6553 (8) Å
c = 10.6128 (8) Å
β = 97.705 (1)°
V = 822.22 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 293 K
0.36 × 0.27 × 0.18 mm

Data collection

Bruker SMART 4K CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.831, T_max = 0.910
5340 measured reflections
1972 independent reflections
1837 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.097
S = 1.10
1972 reflections
136 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.61 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯O2ⁱ	0.89	1.98	2.809 (2)	155
N1—H1A⋯O5ⁱ	0.89	1.90	2.713 (2)	151
N1—H1B⋯O3ⁱⁱ	0.89	2.01	2.824 (2)	152
O4—H3⋯O3ⁱⁱ	0.73 (4)	1.86 (4)	2.591 (2)	176 (4)
O1—H4⋯O6ⁱⁱⁱ	0.71 (3)	1.84 (3)	2.550 (2)	172 (4)
O1W—H5⋯O5^iv	0.893 (10)	1.954 (15)	2.804 (2)	159 (3)
O1W—H8⋯O1^v	0.888 (10)	2.64 (4)	3.061 (2)	110 (3)
O1W—H8⋯O3^vi	0.888 (10)	2.27 (2)	3.041 (2)	145 (3)
O1W—H6⋯O2^vii	0.896 (10)	1.935 (11)	2.828 (2)	175 (3)
O1W—H7⋯O6ⁱⁱⁱ	0.900 (10)	1.920 (11)	2.815 (2)	173 (3)
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z; (iii) x-1, y, z; (iv) -x+2, -y+1, -z+1; (v) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (vi) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809008770/rn2053sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809008770/rn2053Isup2.hkl

checkCIF report

Comment top

Organophosphonic acids and their compounds have attracted tremendous interest. A series of phosphonate hybrid materials have been prepared and show potential applications in catalysts, sensors, sorbents, magnetic and luminescent materials. Such materials also illustrate a variety of structures from one-dimensional chains, two-dimensional layers to three-dimensional porous frameworks. (Finn et al., 2003). Introduction of some functional groups to phosphonic acids, such as crown ether, –COOH, –OH, –NR₂ or mixed groups will modify their complexing ability and construct a great number of novel phosphonates (Clearfield, 2002). Compared with other phosphonic acids, 1-aminoethylidene-1,1-diphosphonic acid (AEDPH₄) is easier to synthesize. However, little attention has been paid to the structural study of metal-AEDP compounds (Yin et al., 2005; Ding et al., 2006). In our recent paper, it is found that AEDPH₄ is inclined to transfer one proton to the amino group, which is in agreement with Fernández's results on similar bisphosphonates. (Li et al., 2008; Fernández et al., 2003). Deprotonation of it will result in predictable hydrogen aggregates from stronger P—O—H···O—P to weaker C—H···O hydrogen bonds. Herein, we report its structure, (I).

The asymmetric unit of (I)is built up from one deprotonated AEDPH₃ anion and a disordered H₃O⁺ cation, which are linked through four types of Ow-H···O hydrogen bonds (Fig. 1, Table 1). Two of the four protons of phosphonates are used in protonation, one for the amino group, the other for the H₃O⁺ cation. The combination of different hydrogen bond interactions, N-H···O and O-H···O results in the formation of an intricate three dimensional supramolecular network (Fig.2, Table 1).

Related literature top

For the structures of organophosphonates, see: Clearfield (2002); Finn (2003). For similar bisphosphonates, see: Fernández et al. (2003); For complexes with 1-aminoethylidene-1,1-diphosphonic acid, see: Yin et al. (2005); Ding et al. (2006); Li et al. (2008). For the synthesis, see: Chai et al. (1980).

Experimental top

The AEDPH₄ was synthesized according to the US Patent 4239695 (Chai et al., 1980). It was crystallized directly from the AEDPH₄ aqueous solution. When the mixture was heated for 24h, colorless crystals were obtained.

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, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008b).

Figures top

	Fig. 1. The asymmetric unit of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. Partial packing view of compound ( I ), showing the formation of the three dimensional network built from hydrogen bonds. For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.

Hydroxonium 1-ammonioethane-1,1-diyldiphosphonate top

Crystal data top

H₃O⁺·C₂H₈N₂O₆P₂⁻	F(000) = 464
M_r = 223.06	D_x = 1.802 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3640 reflections
a = 7.3372 (6) Å	θ = 2.7–29.8°
b = 10.6553 (8) Å	µ = 0.53 mm⁻¹
c = 10.6128 (8) Å	T = 293 K
β = 97.705 (1)°	Plate, colorless
V = 822.22 (11) Å³	0.36 × 0.27 × 0.18 mm
Z = 4

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1837 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ϕ and ω scans	θ_max = 28.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −9→9
T_min = 0.831, T_max = 0.910	k = −9→14
5340 measured reflections	l = −13→11
1972 independent reflections

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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.097	w = 1/[σ²(F_o²) + (0.0481P)² + 0.8715P] where P = (F_o² + 2F_c²)/3
S = 1.10	(Δ/σ)_max = 0.001
1972 reflections	Δρ_max = 0.40 e Å⁻³
136 parameters	Δρ_min = −0.61 e Å⁻³
4 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: 0.023 (2)

Crystal data top

H₃O⁺·C₂H₈N₂O₆P₂⁻	V = 822.22 (11) Å³
M_r = 223.06	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.3372 (6) Å	µ = 0.53 mm⁻¹
b = 10.6553 (8) Å	T = 293 K
c = 10.6128 (8) Å	0.36 × 0.27 × 0.18 mm
β = 97.705 (1)°

Data collection top

Bruker SMART 4K CCD area-detector diffractometer	1972 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	1837 reflections with I > 2σ(I)
T_min = 0.831, T_max = 0.910	R_int = 0.015
5340 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	4 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.10	Δρ_max = 0.40 e Å⁻³
1972 reflections	Δρ_min = −0.61 e Å⁻³
136 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)
C1	0.9948 (2)	0.56114 (16)	0.24265 (16)	0.0131 (3)
C2	0.9672 (3)	0.62357 (19)	0.36861 (18)	0.0209 (4)
H2A	1.0741	0.6722	0.3993	0.031*
H2B	0.9488	0.5602	0.4299	0.031*
H2C	0.8615	0.6774	0.3556	0.031*
N1	1.0165 (2)	0.66564 (14)	0.14939 (14)	0.0152 (3)
H1A	0.9151	0.7124	0.1391	0.023*
H1B	1.0347	0.6329	0.0750	0.023*
H1C	1.1124	0.7131	0.1792	0.023*
O1W	0.4462 (2)	0.70203 (18)	0.52441 (17)	0.0363 (4)
O1	0.63612 (19)	0.57626 (13)	0.17124 (14)	0.0209 (3)
O2	0.75556 (18)	0.37252 (13)	0.27913 (13)	0.0208 (3)
O3	0.80235 (18)	0.42568 (13)	0.05066 (12)	0.0208 (3)
O4	1.23166 (19)	0.41015 (14)	0.13108 (14)	0.0209 (3)
O5	1.20389 (18)	0.37077 (13)	0.35944 (13)	0.0204 (3)
O6	1.36080 (17)	0.56986 (13)	0.29441 (13)	0.0199 (3)
P1	0.78594 (6)	0.47061 (4)	0.18354 (4)	0.01339 (15)
P2	1.21301 (6)	0.47175 (4)	0.26319 (4)	0.01358 (15)
H3	1.227 (5)	0.456 (3)	0.079 (3)	0.051 (10)*
H4	0.562 (5)	0.568 (3)	0.208 (3)	0.049 (10)*
H5	0.5658 (17)	0.698 (3)	0.554 (3)	0.018 (7)*	0.75
H6	0.386 (4)	0.673 (3)	0.587 (2)	0.018 (7)*	0.75
H7	0.426 (4)	0.663 (2)	0.4485 (15)	0.013 (7)*	0.75
H8	0.422 (5)	0.7827 (13)	0.509 (4)	0.038 (10)*	0.75

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0145 (7)	0.0114 (7)	0.0138 (7)	−0.0006 (6)	0.0032 (6)	0.0007 (6)
C2	0.0254 (9)	0.0214 (9)	0.0164 (8)	0.0030 (7)	0.0042 (7)	−0.0040 (7)
N1	0.0165 (7)	0.0123 (7)	0.0173 (7)	−0.0002 (5)	0.0040 (5)	0.0017 (5)
O1W	0.0356 (9)	0.0393 (10)	0.0331 (9)	0.0008 (8)	0.0010 (7)	−0.0001 (7)
O1	0.0155 (6)	0.0200 (7)	0.0283 (7)	0.0043 (5)	0.0073 (5)	0.0065 (5)
O2	0.0210 (6)	0.0164 (6)	0.0261 (7)	0.0001 (5)	0.0068 (5)	0.0073 (5)
O3	0.0217 (6)	0.0236 (7)	0.0169 (6)	−0.0005 (5)	0.0022 (5)	−0.0037 (5)
O4	0.0248 (7)	0.0184 (7)	0.0201 (7)	0.0019 (5)	0.0051 (5)	−0.0036 (5)
O5	0.0191 (6)	0.0189 (6)	0.0227 (7)	0.0010 (5)	0.0005 (5)	0.0066 (5)
O6	0.0148 (6)	0.0193 (6)	0.0259 (7)	−0.0038 (5)	0.0037 (5)	−0.0049 (5)
P1	0.0127 (2)	0.0124 (2)	0.0152 (2)	−0.00029 (15)	0.00251 (16)	0.00126 (15)
P2	0.0123 (2)	0.0125 (2)	0.0158 (2)	0.00017 (15)	0.00167 (16)	0.00006 (15)

Geometric parameters (Å, º) top

C1—N1	1.512 (2)	O1W—H6	0.896 (10)
C1—C2	1.531 (2)	O1W—H7	0.900 (10)
C1—P1	1.8479 (17)	O1W—H8	0.888 (10)
C1—P2	1.8505 (17)	O1—P1	1.5666 (14)
C2—H2A	0.9600	O1—H4	0.71 (3)
C2—H2B	0.9600	O2—P1	1.4940 (13)
C2—H2C	0.9600	O3—P1	1.5093 (13)
N1—H1A	0.8900	O4—P2	1.5706 (14)
N1—H1B	0.8900	O4—H3	0.73 (4)
N1—H1C	0.8900	O5—P2	1.4914 (13)
O1W—H5	0.893 (10)	O6—P2	1.5106 (13)

N1—C1—C2	106.82 (14)	H5—O1W—H7	109 (3)
N1—C1—P1	108.51 (11)	H6—O1W—H7	118 (3)
C2—C1—P1	108.82 (12)	H5—O1W—H8	106 (3)
N1—C1—P2	106.91 (11)	H6—O1W—H8	111 (3)
C2—C1—P2	109.54 (12)	H7—O1W—H8	106 (3)
P1—C1—P2	115.87 (9)	P1—O1—H4	116 (3)
C1—C2—H2A	109.5	P2—O4—H3	113 (3)
C1—C2—H2B	109.5	O2—P1—O3	116.77 (8)
H2A—C2—H2B	109.5	O2—P1—O1	113.10 (8)
C1—C2—H2C	109.5	O3—P1—O1	107.04 (8)
H2A—C2—H2C	109.5	O2—P1—C1	109.10 (8)
H2B—C2—H2C	109.5	O3—P1—C1	108.44 (8)
C1—N1—H1A	109.5	O1—P1—C1	101.18 (8)
C1—N1—H1B	109.5	O5—P2—O6	116.47 (8)
H1A—N1—H1B	109.5	O5—P2—O4	109.10 (8)
C1—N1—H1C	109.5	O6—P2—O4	109.82 (8)
H1A—N1—H1C	109.5	O5—P2—C1	109.54 (8)
H1B—N1—H1C	109.5	O6—P2—C1	104.71 (8)
H5—O1W—H6	107 (3)	O4—P2—C1	106.71 (8)

N1—C1—P1—O2	−176.13 (11)	N1—C1—P2—O5	177.18 (11)
C2—C1—P1—O2	−60.25 (14)	C2—C1—P2—O5	61.79 (14)
P2—C1—P1—O2	63.66 (11)	P1—C1—P2—O5	−61.75 (11)
N1—C1—P1—O3	55.70 (13)	N1—C1—P2—O6	51.57 (12)
C2—C1—P1—O3	171.58 (12)	C2—C1—P2—O6	−63.82 (13)
P2—C1—P1—O3	−64.51 (11)	P1—C1—P2—O6	172.64 (9)
N1—C1—P1—O1	−56.68 (12)	N1—C1—P2—O4	−64.85 (12)
C2—C1—P1—O1	59.20 (13)	C2—C1—P2—O4	179.76 (12)
P2—C1—P1—O1	−176.89 (9)	P1—C1—P2—O4	56.22 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2ⁱ	0.89	1.98	2.809 (2)	155
N1—H1A···O5ⁱ	0.89	1.90	2.713 (2)	151
N1—H1B···O3ⁱⁱ	0.89	2.01	2.824 (2)	152
O4—H3···O3ⁱⁱ	0.73 (4)	1.86 (4)	2.591 (2)	176 (4)
O1—H4···O6ⁱⁱⁱ	0.71 (3)	1.84 (3)	2.550 (2)	172 (4)
O1W—H5···O5^iv	0.89 (1)	1.95 (2)	2.804 (2)	159 (3)
O1W—H8···O1^v	0.89 (1)	2.64 (4)	3.061 (2)	110 (3)
O1W—H8···O3^vi	0.89 (1)	2.27 (2)	3.041 (2)	145 (3)
O1W—H6···O2^vii	0.90 (1)	1.94 (1)	2.828 (2)	175 (3)
O1W—H7···O6ⁱⁱⁱ	0.90 (1)	1.92 (1)	2.815 (2)	173 (3)

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+2, −y+1, −z; (iii) x−1, y, z; (iv) −x+2, −y+1, −z+1; (v) x, −y+3/2, z+1/2; (vi) −x+1, y+1/2, −z+1/2; (vii) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	H₃O⁺·C₂H₈N₂O₆P₂⁻
M_r	223.06
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.3372 (6), 10.6553 (8), 10.6128 (8)
β (°)	97.705 (1)
V (Å³)	822.22 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.36 × 0.27 × 0.18

Data collection
Diffractometer	Bruker SMART 4K CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.831, 0.910
No. of measured, independent and observed [I > 2σ(I)] reflections	5340, 1972, 1837
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.097, 1.10
No. of reflections	1972
No. of parameters	136
No. of restraints	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.61

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···O2ⁱ	0.89	1.98	2.809 (2)	155.4
N1—H1A···O5ⁱ	0.89	1.90	2.713 (2)	150.9
N1—H1B···O3ⁱⁱ	0.89	2.01	2.824 (2)	152.4
O4—H3···O3ⁱⁱ	0.73 (4)	1.86 (4)	2.591 (2)	176 (4)
O1—H4···O6ⁱⁱⁱ	0.71 (3)	1.84 (3)	2.550 (2)	172 (4)
O1W—H5···O5^iv	0.893 (10)	1.954 (15)	2.804 (2)	159 (3)
O1W—H8···O1^v	0.888 (10)	2.64 (4)	3.061 (2)	110 (3)
O1W—H8···O3^vi	0.888 (10)	2.27 (2)	3.041 (2)	145 (3)
O1W—H6···O2^vii	0.896 (10)	1.935 (11)	2.828 (2)	175 (3)
O1W—H7···O6ⁱⁱⁱ	0.900 (10)	1.920 (11)	2.815 (2)	173 (3)

Acknowledgements

This work was supported financially by the Foundation of Education Department of Hubei Province (No. Q20081705).

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