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Acta Cryst. (2007). E63, m2348-m2349    [ doi:10.1107/S160053680703869X ]

catena-Poly[[diaquanickel(II)]-[mu]-2-hydroxyphosphonatoacetato]

J. Li, D.-P. Dong, C.-Y. Huang, Z.-G. Sun and Y.-Y. Zhu

Abstract top

The title compound, [Ni{HO3PCH(OH)CO2}(H2O)2]n, was prepared by a hydrothermal reaction. The octahedral coordination geometry of NiII is made up of one phosphonate O atom, one hydroxyl O atom, two carboxylate O atoms and two water molecules. This architecture is further stabilized by a number of O-H...O hydrogen bonds involving the protonated hydroxyl groups, carboxylate O atoms, a phosphonate O atom and coordinated water molecules.

Comment top

Metal phosphonates have been of increasing interest in the past decade due to their potential applications in the fields of catalysis (Sharma & Clearfield, 2000), ion exchange (Clearfield, 1988), proton conductivity (Alberti et al., 1992), gas and liquid separations (Riou et al., 2000), biology (Nonglaton et al., 2004), and organic molecule sorption (Clearfield, 1998). Great efforts have been devoted to the syntheses of novel inorganic–organic hybrid materials based on metal phosphonates, which exhibit a variety of structures such as one-dimensional chains, two-dimensional layers, and three-dimensional network. To the best of our knowledge, however, reports on nickel phosphonates are rather scarce (Hix & Harris, 1998; Song et al., 1999; Modi et al., 2005).

The title compound (I) crystallizes in the orthorhombic space group Pbca. The molecular structure of (I) is shown in the Fig. 1. Each Ni atom adopts distorted octahedral coordination geometry with the six oxygen atoms from the two equivalent L3− (L = O3PCH(OH)CO2) anions and two coordinated water molecule. The values of the Ni—O bond lengths and O—Ni—O angles are in the range of 2.0329 (19)–2.0888 (19) Å and 78.81 (7)–177.88 (8) °, respectively. This architecture is further stabilized by a number of O—H···O hydrogen bonds involving the protonated hydroxyl oxygen atoms, carboxylate oxygen atoms, phosphonate oxygen atom, and coordinated water molecules (see Table 1, Table 2 and Fig. 2).

Related literature top

For related literature, see: Alberti et al. (1992); Clearfield (1988, 1998); Hix & Harris (1998); Modi et al. (2005); Nonglaton et al. (2004); Riou et al. (2000); Sharma & Clearfield (2000); Song et al. (1999).

Experimental top

A mixture of 0.27 g (1.0 mmol) NiSO4·6H2O, 1.0 ml (4.0 mmol) 2-hydroxyphosphonoacetic acid (48.0 wt %) and 0.04 g (1.0 mmol) NaF (as a mineralizer) was dissolved in 8 ml of deionized water, and then 1,4-butylenediamine was added with stirring to adjust the pH of the mixture. The mixture (pH = 4.5) was sealed in a 23 ml Teflon-lined stainless steel autoclave, and then heated at 413 K for 72 h. Colorless block crystals were obtained, washed with distilled water, and dried in air at room temperature.

Refinement top

During refinement, carbon bound H atoms were placed in calculated positions and allowed to ride on the parent atom, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C). Oxygen bound hydrogen atoms were located from difference Fourier maps and refined with distance restraints.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I), showing displacement ellipsids at the 30% probability level.
[Figure 2] Fig. 2. View of the packing of (I) with the unit cell outlined along the b axis, showing the stacking of compound (I). H atoms have been omitted for clarity.
catena-poly[[diaquanickel(II)]-µ-2-hydroxyphosphonatoacetato] top
Crystal data top
[Ni(C2H3O6P)(H2O)2]Dx = 2.320 Mg m−3
Mr = 248.76Mo Kα radiation
λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 2474 reflections
a = 8.6776 (9) Åθ = 2.4–28.2º
b = 9.7953 (10) ŵ = 2.96 mm−1
c = 16.7592 (16) ÅT = 295 (2) K
V = 1424.5 (2) Å3Block, green
Z = 80.20 × 0.09 × 0.07 mm
F000 = 1008
Data collection top
Bruker APEXII CCD
diffractometer		1398 independent reflections
Radiation source: fine-focus sealed tube1204 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.030
T = 295(2) Kθmax = 26.0º
ω scansθmin = 3.4º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		h = −10→10
Tmin = 0.589, Tmax = 0.820k = −11→12
7058 measured reflectionsl = −12→20
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.025H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.068  w = 1/[σ2(Fo2) + (0.0411P)2 + 1.2128P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1398 reflectionsΔρmax = 0.41 e Å−3
121 parametersΔρmin = −0.48 e Å−3
4 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C2H3O6P)(H2O)2]V = 1424.5 (2) Å3
Mr = 248.76Z = 8
Orthorhombic, PbcaMo Kα
a = 8.6776 (9) ŵ = 2.96 mm−1
b = 9.7953 (10) ÅT = 295 (2) K
c = 16.7592 (16) Å0.20 × 0.09 × 0.07 mm
Data collection top
Bruker APEXII CCD
diffractometer		1398 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		1204 reflections with I > 2σ(I)
Tmin = 0.589, Tmax = 0.820Rint = 0.030
7058 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0254 restraints
wR(F2) = 0.068H atoms treated by a mixture of
independent and constrained refinement
S = 1.05Δρmax = 0.41 e Å−3
1398 reflectionsΔρmin = −0.48 e Å−3
121 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
xyzUiso*/Ueq
Ni11.12817 (4)−0.00201 (3)0.134842 (19)0.01264 (13)
P10.79917 (7)0.13589 (7)0.13742 (4)0.01399 (17)
O10.7275 (2)0.27285 (19)0.12260 (11)0.0205 (4)
O20.9474 (2)0.10843 (19)0.09274 (10)0.0190 (4)
O30.6732 (2)0.0253 (2)0.11674 (12)0.0227 (4)
H3A0.7113−0.05110.11980.034*
O40.7059 (2)0.14671 (17)0.28985 (10)0.0165 (4)
H4A0.70190.22940.29730.025*
O50.81452 (19)−0.09508 (17)0.31593 (10)0.0149 (4)
O61.00059 (19)−0.08174 (17)0.22600 (11)0.0152 (4)
O71.2642 (3)0.0773 (2)0.04608 (12)0.0287 (5)
H7A1.316 (3)0.150 (2)0.053 (2)0.034*
H7B1.294 (4)0.037 (3)0.0042 (13)0.034*
O81.0632 (2)−0.17173 (19)0.06738 (11)0.0180 (4)
H8A1.044 (3)−0.154 (3)0.0186 (8)0.022*
H8B0.9736 (17)−0.194 (3)0.0817 (17)0.022*
C10.8399 (3)0.1148 (3)0.24425 (15)0.0131 (5)
H1A0.92280.17760.25940.016*
C20.8903 (3)−0.0304 (3)0.26311 (15)0.0134 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0133 (2)0.0128 (2)0.0118 (2)0.00033 (12)−0.00064 (12)0.00038 (12)
P10.0154 (3)0.0132 (3)0.0134 (3)0.0021 (3)0.0003 (3)0.0013 (2)
O10.0215 (10)0.0165 (10)0.0235 (10)0.0046 (8)−0.0004 (8)0.0036 (8)
O20.0180 (9)0.0251 (10)0.0137 (10)0.0071 (8)0.0018 (8)0.0035 (8)
O30.0240 (10)0.0189 (10)0.0251 (11)−0.0024 (8)−0.0054 (9)0.0021 (8)
O40.0216 (9)0.0090 (9)0.0190 (10)0.0020 (7)0.0069 (8)0.0007 (7)
O50.0166 (9)0.0117 (9)0.0166 (9)−0.0003 (7)0.0032 (7)0.0021 (7)
O60.0146 (9)0.0136 (9)0.0173 (10)0.0015 (7)0.0032 (7)0.0011 (7)
O70.0370 (12)0.0299 (12)0.0192 (11)−0.0115 (10)0.0092 (10)−0.0022 (9)
O80.0183 (9)0.0212 (10)0.0144 (9)−0.0011 (8)−0.0011 (8)−0.0011 (8)
C10.0140 (12)0.0133 (13)0.0122 (13)0.0007 (10)0.0032 (10)0.0005 (9)
C20.0129 (12)0.0152 (13)0.0120 (13)−0.0019 (10)−0.0037 (10)−0.0017 (10)
Geometric parameters (Å, °) top
Ni1—O5i2.0314 (17)O4—Ni1ii2.0422 (17)
Ni1—O22.0322 (18)O4—H4A0.8200
Ni1—O62.0419 (17)O5—C21.271 (3)
Ni1—O4i2.0422 (17)O5—Ni1ii2.0314 (17)
Ni1—O72.052 (2)O6—C21.247 (3)
Ni1—O82.0881 (19)O7—H7A0.852 (10)
P1—O11.4996 (19)O7—H7B0.846 (10)
P1—O21.5123 (19)O8—H8A0.850 (10)
P1—O31.578 (2)O8—H8B0.843 (10)
P1—C11.837 (3)C1—C21.521 (3)
O3—H3A0.8200C1—H1A0.9800
O4—C11.426 (3)
O5i—Ni1—O2173.98 (7)P1—O3—H3A109.5
O5i—Ni1—O687.48 (7)C1—O4—Ni1ii116.37 (14)
O2—Ni1—O692.57 (7)C1—O4—H4A109.5
O5i—Ni1—O4i78.82 (7)Ni1ii—O4—H4A126.6
O2—Ni1—O4i95.17 (7)C2—O5—Ni1ii118.09 (16)
O6—Ni1—O4i89.40 (7)C2—O6—Ni1129.43 (17)
O5i—Ni1—O790.37 (8)Ni1—O7—H7A121 (2)
O2—Ni1—O789.47 (8)Ni1—O7—H7B127 (2)
O6—Ni1—O7177.68 (8)H7A—O7—H7B111 (3)
O4i—Ni1—O789.31 (8)Ni1—O8—H8A114 (2)
O5i—Ni1—O894.45 (7)Ni1—O8—H8B108 (2)
O2—Ni1—O891.56 (7)H8A—O8—H8B99 (3)
O6—Ni1—O887.37 (7)O4—C1—C2109.16 (19)
O4i—Ni1—O8172.66 (7)O4—C1—P1109.94 (16)
O7—Ni1—O893.68 (8)C2—C1—P1111.29 (17)
O1—P1—O2115.47 (11)O4—C1—H1A108.8
O1—P1—O3106.88 (11)C2—C1—H1A108.8
O2—P1—O3111.01 (11)P1—C1—H1A108.8
O1—P1—C1110.00 (11)O6—C2—O5122.9 (2)
O2—P1—C1107.41 (11)O6—C2—C1119.6 (2)
O3—P1—C1105.67 (11)O5—C2—C1117.5 (2)
P1—O2—Ni1125.40 (10)
Symmetry codes: (i) x+1/2, y, −z+1/2; (ii) x−1/2, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1iii0.821.802.621 (3)173
O8—H8B···O1iii0.843 (10)1.902 (11)2.741 (3)173 (3)
O4—H4A···O5iv0.821.752.573 (2)177
O7—H7A···O8v0.852 (10)2.049 (11)2.901 (3)178 (3)
O7—H7B···O3vi0.846 (10)2.135 (14)2.958 (3)164 (3)
O8—H8A···O2vi0.850 (10)1.921 (12)2.756 (3)167 (3)
Symmetry codes: (iii) −x+3/2, y−1/2, z; (iv) −x+3/2, y+1/2, z; (v) −x+5/2, y+1/2, z; (vi) −x+2, −y, −z.
Table 1
Selected geometric parameters (Å, °) top
Ni1—O5i2.0314 (17)P1—O21.5123 (19)
Ni1—O22.0322 (18)P1—O31.578 (2)
Ni1—O62.0419 (17)P1—C11.837 (3)
Ni1—O4i2.0422 (17)O4—C11.426 (3)
Ni1—O72.052 (2)O5—C21.271 (3)
Ni1—O82.0881 (19)O6—C21.247 (3)
P1—O11.4996 (19)C1—C21.521 (3)
O5i—Ni1—O2173.98 (7)O6—Ni1—O7177.68 (8)
O5i—Ni1—O687.48 (7)O4i—Ni1—O789.31 (8)
O2—Ni1—O692.57 (7)O5i—Ni1—O894.45 (7)
O5i—Ni1—O4i78.82 (7)O2—Ni1—O891.56 (7)
O2—Ni1—O4i95.17 (7)O6—Ni1—O887.37 (7)
O6—Ni1—O4i89.40 (7)O4i—Ni1—O8172.66 (7)
O5i—Ni1—O790.37 (8)O7—Ni1—O893.68 (8)
O2—Ni1—O789.47 (8)
Symmetry codes: (i) x+1/2, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3A···O1ii0.821.802.621 (3)173
O8—H8B···O1ii0.843 (10)1.902 (11)2.741 (3)173 (3)
O4—H4A···O5iii0.821.752.573 (2)177
O7—H7A···O8iv0.852 (10)2.049 (11)2.901 (3)178 (3)
O7—H7B···O3v0.846 (10)2.135 (14)2.958 (3)164 (3)
O8—H8A···O2v0.850 (10)1.921 (12)2.756 (3)167 (3)
Symmetry codes: (ii) −x+3/2, y−1/2, z; (iii) −x+3/2, y+1/2, z; (iv) −x+5/2, y+1/2, z; (v) −x+2, −y, −z.
Acknowledgements top

This research was supported by grants from the Natural Science Foundation of Liaoning Province of China (grant No. 20062140) and the Education Department of Liaoning Province of China (grant No. 05 L214).

references
References top

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