4-[2-(Hydrogen phosphonato)-2-hydroxy-2-phosphonoethyl]pyridinium

Wang, F.-L.; Yuan, R.-X.; Xie, J.-M.

doi:10.1107/S1600536811011408

organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page o1025

doi:10.1107/S1600536811011408

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4-[2-(Hydrogen phosphonato)-2-hydroxy-2-phosphonoethyl]pyridinium

Feng-Lei Wang,^a Rong-Xin Yuan ^a,^b ^* and Ji-Min Xie ^a

^aCollege of Chemistry & Chemical Engineering, Jiangsu University, Zhenjiang, 212013, Jiangsu, People's Republic of China, and ^bCollege of Chemistry & Materials Engineering, Jiangsu Laboratory of Advanced Functional Materials, Changshu Institute of Technology, Changshu, 215500, Jiangsu, People's Republic of China
^*Correspondence e-mail: wflchem@hotmail.com

(Received 19 March 2011; accepted 28 March 2011; online 31 March 2011)

The title compound, C₇H₁₁NO₇P₂, exists as a zwitterion in which the positive charge resides on the protonated pyridyl N atom and the negative charge on one of the two phosphate groups. In the crystal, adjacent molcules are linked by O—H⋯O and N—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For metal complexes of phosphonic acids, see: Ma et al. (2008 , 2009 ).

Experimental

Crystal data

C₇H₁₁NO₇P₂
M_r = 283.11
Monoclinic, P 2₁ /n
a = 10.083 (2) Å
b = 9.4713 (19) Å
c = 11.708 (2) Å
β = 94.87 (3)°
V = 1114.1 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 K
0.3 × 0.25 × 0.2 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) T_min = 0.880, T_max = 0.92
11137 measured reflections
2548 independent reflections
2093 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.117
S = 1.02
2548 reflections
174 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O2ⁱ	0.81 (2)	2.06 (2)	2.816 (3)	156 (3)
O4—H4A⋯O7ⁱ	0.81 (2)	1.77 (2)	2.574 (3)	176 (4)
O5—H5A⋯O2ⁱ	0.82 (2)	1.66 (2)	2.477 (3)	175 (4)
N1—H2A⋯O7ⁱⁱ	0.82 (2)	1.93 (2)	2.741 (3)	171 (4)
O6—H6A⋯O3ⁱⁱⁱ	0.81 (4)	1.67 (4)	2.476 (3)	175 (4)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011408/ng5136sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811011408/ng5136Isup2.hkl

checkCIF report

Comment top

Metal diphosphonates have been extensively studied for the diversity structures. Monomeric, dimeric, polymeric, two-dimensional layers to three-dimensional frameworks are all featured among these complexs Ma et al., 2008; Ma et al., 2009). Because diphosphonates have capabilities to stabilize transition metals in a wide range of oxidation states. The title compound was synthesized and characterized by X-ray crystal structure analysis.

There are some intermolecular hydrogen bonds in the structure of the title compound (Fig. 1 and Table 1). The intermolecular hydrogen bonds [O1—H1A···O2ⁱ, O5—H5A···O2ⁱ and O4—H4A···O7ⁱ; symmetry code: -x+3/2, y-1/2, -z+1/2] bridge the molecules through head-to-tail into a one-dmensional chain. These chains are linked to two-dimensional structure through hydrogen bonds [N1—H2A···O7ⁱⁱ; symmetry code: x+1, y, z]. The hydrogen bonds [O6—H6A···O3ⁱⁱⁱ; symmetry code: x-1/2, -y+1/2, z-1/2] connected the layers into a three-dimensional network (shown in Fig. 2).

Related literature top

For metal complexes of phosphonic acids, see: Ma et al. (2008, 2009).

Experimental top

The title compound was synthesized by reaction of 4-pyridine acetic acid hydrochloride (0.520 g, 3 mmol) and phosphite (0.711 g, 8.7 mmol) in chlorobenzene (15 mL). The solution was stirred while phosphorus trichloride (0.64 g, 4.7 mmol) was added drop by drop and the temperature should control between 110-120 ^oC with vigorous stirring for 4 hours. The crude product was concentrated in vacuo. White block crystals formed in high yield by recrystallization.

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear (Rigaku/MSC, 2005); data reduction: CrystalClear (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Spek, 2009).

Figures top

	Fig. 1. A view of the compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level. [Symmetry code A = 1-x, y, 1/2-z].
	Fig. 2. Hydrogen bonds connected three-dimensional structure of the title compound (Carbon-bond H atoms were omitted for clarity).

4-[2-(Hydrogen phosphonato)-2-hydroxy-2-phosphonoethyl]pyridinium top

Crystal data top

C₇H₁₁NO₇P₂	F(000) = 584
M_r = 283.11	D_x = 1.688 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 10067 reflections
a = 10.083 (2) Å	θ = 3.4–27.6°
b = 9.4713 (19) Å	µ = 0.42 mm⁻¹
c = 11.708 (2) Å	T = 293 K
β = 94.87 (3)°	Block, colorless
V = 1114.1 (4) Å³	0.3 × 0.25 × 0.2 mm
Z = 4

Data collection top

Rigaku Mercury diffractometer	2548 independent reflections
Radiation source: fine-focus sealed tube	2093 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.3°
dtfind.ref scans	h = −13→13
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −12→12
T_min = 0.880, T_max = 0.92	l = −15→15
11137 measured 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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0537P)² + 1.150P] where P = (F_o² + 2F_c²)/3
2548 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.30 e Å⁻³
5 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₇H₁₁NO₇P₂	V = 1114.1 (4) Å³
M_r = 283.11	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.083 (2) Å	µ = 0.42 mm⁻¹
b = 9.4713 (19) Å	T = 293 K
c = 11.708 (2) Å	0.3 × 0.25 × 0.2 mm
β = 94.87 (3)°

Data collection top

Rigaku Mercury diffractometer	2548 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	2093 reflections with I > 2σ(I)
T_min = 0.880, T_max = 0.92	R_int = 0.051
11137 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	5 restraints
wR(F²) = 0.117	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.30 e Å⁻³
2548 reflections	Δρ_min = −0.29 e Å⁻³
174 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.

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 > 2sigma(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	0.66199 (6)	0.19546 (7)	0.09909 (6)	0.01961 (18)
P2	0.87076 (6)	0.20407 (7)	0.30954 (6)	0.01825 (18)
O1	0.88791 (18)	0.0416 (2)	0.12393 (16)	0.0229 (4)
H1A	0.846 (3)	−0.021 (3)	0.151 (3)	0.041 (10)*
O2	0.81307 (19)	0.3435 (2)	0.34177 (16)	0.0277 (4)
O3	1.01876 (18)	0.1862 (2)	0.33689 (16)	0.0275 (5)
O4	0.79155 (19)	0.0847 (2)	0.36597 (16)	0.0258 (4)
H4A	0.827 (4)	0.008 (3)	0.370 (3)	0.059 (12)*
O5	0.58172 (19)	0.0799 (2)	0.1556 (2)	0.0327 (5)
H5A	0.613 (4)	0.000 (2)	0.157 (3)	0.069 (14)*
O6	0.6632 (2)	0.1660 (2)	−0.02975 (18)	0.0341 (5)
H6A	0.619 (4)	0.218 (4)	−0.072 (3)	0.059 (13)*
O7	0.60449 (17)	0.33631 (19)	0.12698 (17)	0.0269 (5)
N1	1.3345 (2)	0.3264 (3)	0.1400 (2)	0.0362 (6)
H2A	1.4152 (19)	0.334 (4)	0.143 (3)	0.058 (12)*
C2	1.2820 (3)	0.2028 (3)	0.1039 (3)	0.0331 (7)
H2	1.3374	0.1275	0.0894	0.040*
C3	1.1465 (3)	0.1875 (3)	0.0883 (2)	0.0279 (6)
H3	1.1097	0.1020	0.0625	0.033*
C4	1.0641 (3)	0.2998 (3)	0.1109 (2)	0.0221 (6)
C5	1.1232 (3)	0.4260 (3)	0.1492 (3)	0.0334 (7)
H5	1.0705	0.5024	0.1662	0.040*
C6	1.2600 (3)	0.4372 (4)	0.1618 (3)	0.0413 (8)
H6	1.2999	0.5220	0.1855	0.050*
C7	0.9147 (2)	0.2907 (3)	0.0868 (2)	0.0234 (6)
H7A	0.8954	0.2725	0.0055	0.028*
H7B	0.8777	0.3826	0.1023	0.028*
C8	0.8396 (2)	0.1788 (2)	0.1534 (2)	0.0166 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0118 (3)	0.0169 (3)	0.0293 (4)	0.0002 (3)	−0.0028 (2)	−0.0001 (3)
P2	0.0170 (3)	0.0162 (3)	0.0213 (3)	0.0004 (3)	−0.0001 (2)	−0.0024 (3)
O1	0.0193 (9)	0.0172 (10)	0.0326 (10)	0.0020 (8)	0.0050 (8)	−0.0043 (8)
O2	0.0302 (10)	0.0183 (10)	0.0349 (11)	0.0020 (8)	0.0048 (8)	−0.0068 (8)
O3	0.0193 (10)	0.0355 (11)	0.0265 (10)	0.0036 (8)	−0.0060 (7)	−0.0050 (9)
O4	0.0287 (11)	0.0186 (10)	0.0310 (10)	0.0019 (8)	0.0082 (8)	0.0040 (8)
O5	0.0167 (10)	0.0234 (12)	0.0577 (14)	−0.0027 (8)	0.0011 (9)	0.0076 (10)
O6	0.0316 (11)	0.0390 (13)	0.0294 (11)	0.0093 (10)	−0.0116 (9)	−0.0025 (10)
O7	0.0161 (9)	0.0177 (10)	0.0466 (12)	0.0012 (8)	0.0018 (8)	−0.0016 (8)
N1	0.0154 (12)	0.0549 (18)	0.0386 (15)	−0.0072 (12)	0.0046 (10)	−0.0016 (13)
C2	0.0199 (14)	0.0435 (19)	0.0368 (16)	0.0047 (13)	0.0074 (12)	0.0006 (14)
C3	0.0225 (14)	0.0300 (16)	0.0319 (15)	−0.0022 (12)	0.0060 (11)	−0.0039 (12)
C4	0.0180 (13)	0.0260 (14)	0.0229 (13)	−0.0027 (11)	0.0051 (10)	0.0022 (11)
C5	0.0240 (15)	0.0265 (16)	0.0507 (19)	−0.0058 (12)	0.0094 (13)	−0.0057 (14)
C6	0.0262 (16)	0.043 (2)	0.055 (2)	−0.0144 (15)	0.0074 (14)	−0.0112 (16)
C7	0.0144 (12)	0.0248 (14)	0.0311 (14)	−0.0015 (11)	0.0021 (10)	0.0059 (12)
C8	0.0129 (11)	0.0129 (12)	0.0236 (12)	0.0017 (9)	−0.0004 (9)	−0.0007 (10)

Geometric parameters (Å, º) top

P1—O7	1.5015 (19)	N1—C2	1.339 (4)
P1—O6	1.535 (2)	N1—H2A	0.815 (19)
P1—O5	1.543 (2)	C2—C3	1.371 (4)
P1—C8	1.855 (2)	C2—H2	0.9300
P2—O2	1.5038 (19)	C3—C4	1.388 (4)
P2—O3	1.5090 (19)	C3—H3	0.9300
P2—O4	1.563 (2)	C4—C5	1.392 (4)
P2—C8	1.844 (3)	C4—C7	1.512 (3)
O1—C8	1.440 (3)	C5—C6	1.379 (4)
O1—H1A	0.806 (18)	C5—H5	0.9300
O4—H4A	0.811 (18)	C6—H6	0.9300
O5—H5A	0.821 (19)	C7—C8	1.551 (3)
O6—H6A	0.81 (4)	C7—H7A	0.9700
N1—C6	1.328 (4)	C7—H7B	0.9700

O7—P1—O6	114.23 (12)	C2—C3—H3	120.0
O7—P1—O5	108.10 (12)	C4—C3—H3	120.0
O6—P1—O5	109.93 (13)	C3—C4—C5	118.2 (2)
O7—P1—C8	112.34 (11)	C3—C4—C7	121.6 (2)
O6—P1—C8	103.49 (12)	C5—C4—C7	120.1 (2)
O5—P1—C8	108.59 (11)	C6—C5—C4	119.8 (3)
O2—P2—O3	116.23 (11)	C6—C5—H5	120.1
O2—P2—O4	107.85 (11)	C4—C5—H5	120.1
O3—P2—O4	111.15 (11)	N1—C6—C5	119.7 (3)
O2—P2—C8	108.99 (11)	N1—C6—H6	120.2
O3—P2—C8	106.16 (11)	C5—C6—H6	120.2
O4—P2—C8	105.97 (11)	C4—C7—C8	117.8 (2)
C8—O1—H1A	112 (2)	C4—C7—H7A	107.9
P2—O4—H4A	116 (3)	C8—C7—H7A	107.9
P1—O5—H5A	117 (3)	C4—C7—H7B	107.9
P1—O6—H6A	117 (3)	C8—C7—H7B	107.9
C6—N1—C2	122.5 (3)	H7A—C7—H7B	107.2
C6—N1—H2A	120 (3)	O1—C8—C7	107.8 (2)
C2—N1—H2A	117 (3)	O1—C8—P2	108.77 (16)
N1—C2—C3	119.8 (3)	C7—C8—P2	111.14 (17)
N1—C2—H2	120.1	O1—C8—P1	109.33 (16)
C3—C2—H2	120.1	C7—C8—P1	105.54 (16)
C2—C3—C4	119.9 (3)	P2—C8—P1	114.04 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.81 (2)	2.06 (2)	2.816 (3)	156 (3)
O4—H4A···O7ⁱ	0.81 (2)	1.77 (2)	2.574 (3)	176 (4)
O5—H5A···O2ⁱ	0.82 (2)	1.66 (2)	2.477 (3)	175 (4)
N1—H2A···O7ⁱⁱ	0.82 (2)	1.93 (2)	2.741 (3)	171 (4)
O6—H6A···O3ⁱⁱⁱ	0.81 (4)	1.67 (4)	2.476 (3)	175 (4)

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

Experimental details

Crystal data
Chemical formula	C₇H₁₁NO₇P₂
M_r	283.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.083 (2), 9.4713 (19), 11.708 (2)
β (°)	94.87 (3)
V (Å³)	1114.1 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.42
Crystal size (mm)	0.3 × 0.25 × 0.2

Data collection
Diffractometer	Rigaku Mercury diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2005)
T_min, T_max	0.880, 0.92
No. of measured, independent and observed [I > 2σ(I)] reflections	11137, 2548, 2093
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.117, 1.02
No. of reflections	2548
No. of parameters	174
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.29

Computer programs: CrystalClear (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O2ⁱ	0.806 (18)	2.06 (2)	2.816 (3)	156 (3)
O4—H4A···O7ⁱ	0.811 (18)	1.765 (19)	2.574 (3)	176 (4)
O5—H5A···O2ⁱ	0.821 (19)	1.657 (19)	2.477 (3)	175 (4)
N1—H2A···O7ⁱⁱ	0.815 (19)	1.93 (2)	2.741 (3)	171 (4)
O6—H6A···O3ⁱⁱⁱ	0.81 (4)	1.67 (4)	2.476 (3)	175 (4)

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

Acknowledgements

This work was supported by a start-up grant from the CSLG (No. KY10657) and by the Natural Science Fund of Jiangsu Province, China (No. 08KJB150001).

References

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