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Acta Cryst. (2008). E64, m398    [ doi:10.1107/S1600536807065129 ]

Bis[1-hydroxyethylidenediphosphonato(1-)](1,10-phenanthroline)nickel(II) monohydrate

X. Zhang, C. Ge, X. Zhang and Q. Liu

Abstract top

In the mononuclear title compound, [Ni(C2H6O7P2)2(C12H8N2)]·H2O, the NiII atom (site symmetry 2) is bonded to two phosphate-based O,O'-bidentate chelate ligands and one N,N'-bidentate 1,10-phenanthroline ligand, resulting in a slightly distorted cis-NiN2O4 octahedral geometry. In the crystal structure, pairs of complexes are linked by double hydrogen bonds, forming a one-dimensional chain-like structure. Aromatic [pi]-[pi] stacking interactions [centroid-centroid separation = 3.768 (2) Å] and further hydrogen bonds generate a two-dimensional structure. The water O atom also lies on a crystallographic twofold axis.

Comment top

Metal–phosphonate compounds are of current interest due to their fascinating topologies and novel physical properties (e.g. Song et al. 1999; Xiang et al. 2007).

In the title compound, (I), the NiII ion with site symmetry 2, is chelated by four oxygen atoms from two phosphate-containing O,O-chelate ligands and two nitrogen atoms from an N,N-chelating 1,10-phenanthroline (phen) ligand to generate a cis-NiN2O4 distorted octahedral coordination geometry (Fig. 1, Table 1).

Intermolecular hydrogen bond interactions (Table 2) occur between the phosphate ligands Each complex is connected with its neighbours by hydrogen bonds to form one-dimensional chain (Fig. 2). Aromatic π-π stacking interactions with distance between ring centroids of 3.768 (2) Å extend the width of the chain. Water molecules between those chains act as bridges to generate two dimensional structure through further O-H···O hydrogen bonds

Related literature top

For related literature, see: Song et al. (1999); Xiang et al. (2007).

Experimental top

1,10-Phenanthroline (1 mmol), Ni(NO3)2.6H2O (2 mmol), 1-hydroxyethylidenediphosphonic acid (0.2 ml) and ethanol/H2O (v:v = 1:3, 40 ml) were mixed. The resulting mixture was heated and stirred for 4 h and the solution was filtered. By slow evaporation of the solvent, blue blocks of (I) were obtained after several months.

Refinement top

The water H atoms were located from difference maps and their positions freely refined with Uiso(H) = 1.5Ueq(O). The other H atoms were geometrically placed (C—H = 0.93–0.97 Å, O—H = 0.82 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. View of the molecular structure of (I), showing displacement ellipsoids drawn at the 30% probability level. H atoms are omitted for clarity. Atoms with the suffix A are generated by the symmetry operation (-x, y, 1/2 - z).
[Figure 2] Fig. 2. Two-dimensional structure of (I) formed by π-π stacking interactions between hydrogen bonded chains.
Bis[1-hydroxyethylidenediphosphonato(1-)](1,10-phenanthroline)nickel(II) monohydrate top
Crystal data top
[Ni(C2H6O7P2)2(C12H8N2)]·H2OF000 = 1360
Mr = 664.95Dx = 1.850 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C2ycCell parameters from 542 reflections
a = 17.108 (2) Åθ = 2.8–24.7º
b = 18.572 (2) ŵ = 1.16 mm−1
c = 7.5142 (9) ÅT = 293 (2) K
β = 90.164 (2)ºBlock, blue
V = 2387.5 (5) Å30.22 × 0.20 × 0.18 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2268 independent reflections
Radiation source: fine-focus sealed tube1857 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.043
T = 293(2) Kθmax = 25.7º
ω scansθmin = 1.6º
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −20→20
Tmin = 0.770, Tmax = 0.819k = −14→22
6424 measured reflectionsl = −8→9
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difmap and geom
R[F2 > 2σ(F2)] = 0.045H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.041P)2 + 5.7735P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2268 reflectionsΔρmax = 0.53 e Å−3
187 parametersΔρmin = −0.32 e Å−3
3 restraintsExtinction correction: none
Primary atom site location: structure-invariant direct methods
Crystal data top
[Ni(C2H6O7P2)2(C12H8N2)]·H2OV = 2387.5 (5) Å3
Mr = 664.95Z = 4
Monoclinic, C2/cMo Kα
a = 17.108 (2) ŵ = 1.16 mm−1
b = 18.572 (2) ÅT = 293 (2) K
c = 7.5142 (9) Å0.22 × 0.20 × 0.18 mm
β = 90.164 (2)º
Data collection top
Bruker SMART CCD
diffractometer		2268 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1857 reflections with I > 2σ(I)
Tmin = 0.770, Tmax = 0.819Rint = 0.043
6424 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0453 restraints
wR(F2) = 0.101H atoms treated by a mixture of
independent and constrained refinement
S = 1.06Δρmax = 0.53 e Å−3
2268 reflectionsΔρmin = −0.32 e Å−3
187 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
H2A0.093 (2)0.050 (3)0.236 (8)0.07 (2)*
H6A0.0606 (18)0.256 (3)0.852 (6)0.044 (15)*
O1W0.00000.0069 (3)0.75000.0356 (11)
O70.03755 (15)0.11993 (14)0.5280 (4)0.0245 (6)
H70.00460.14550.48000.037*
O50.17574 (14)0.28983 (14)0.5476 (3)0.0220 (6)
Ni10.00000.27786 (4)0.25000.01343 (19)
P10.13862 (5)0.15397 (5)0.27824 (13)0.0161 (2)
P20.10427 (5)0.24696 (6)0.59910 (12)0.0157 (2)
O30.07673 (14)0.19644 (14)0.1833 (3)0.0192 (6)
O40.02826 (14)0.27551 (13)0.5233 (3)0.0159 (6)
N10.07336 (17)0.36185 (17)0.1867 (4)0.0175 (7)
O20.13487 (17)0.07260 (16)0.2226 (4)0.0295 (7)
O10.22184 (14)0.17731 (16)0.2446 (4)0.0265 (7)
O60.10100 (15)0.24085 (17)0.8048 (3)0.0257 (7)
C50.0390 (2)0.4269 (2)0.2147 (5)0.0177 (8)
C10.1439 (2)0.3607 (2)0.1143 (5)0.0219 (9)
H10.16740.31640.09310.026*
C20.1846 (2)0.4237 (2)0.0684 (5)0.0293 (10)
H20.23380.42100.01640.035*
C80.1142 (2)0.1545 (2)0.5157 (5)0.0177 (8)
C60.0362 (3)0.5580 (2)0.2142 (6)0.0347 (11)
H60.06050.60160.18890.042*
C40.0760 (3)0.4923 (2)0.1766 (5)0.0258 (9)
C70.1711 (2)0.1109 (2)0.6265 (6)0.0293 (10)
H7A0.15330.10910.74750.044*
H7B0.22180.13300.62250.044*
H7C0.17430.06280.57980.044*
C30.1510 (3)0.4888 (2)0.1011 (6)0.0317 (11)
H30.17760.53100.07340.038*
H1WA0.014 (5)0.036 (3)0.669 (8)0.14 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1W0.042 (3)0.025 (3)0.040 (3)0.000−0.001 (2)0.000
O70.0212 (14)0.0220 (15)0.0303 (17)−0.0014 (12)0.0010 (12)0.0085 (13)
O50.0159 (13)0.0305 (17)0.0198 (14)−0.0035 (12)0.0005 (11)−0.0011 (12)
Ni10.0139 (3)0.0141 (4)0.0122 (3)0.000−0.0011 (3)0.000
P10.0134 (5)0.0183 (5)0.0165 (5)0.0021 (4)−0.0013 (4)−0.0034 (4)
P20.0128 (5)0.0219 (6)0.0124 (5)0.0008 (4)−0.0010 (4)−0.0011 (4)
O30.0180 (13)0.0239 (15)0.0156 (14)0.0043 (11)0.0016 (11)−0.0013 (11)
O40.0153 (13)0.0201 (14)0.0122 (13)0.0008 (11)−0.0010 (10)−0.0008 (11)
N10.0176 (16)0.0212 (18)0.0136 (16)−0.0013 (14)−0.0031 (13)0.0015 (13)
O20.0306 (17)0.0215 (16)0.0365 (18)0.0042 (14)0.0010 (14)−0.0063 (14)
O10.0150 (13)0.0427 (18)0.0218 (15)−0.0044 (13)0.0006 (11)−0.0085 (13)
O60.0179 (14)0.0456 (19)0.0134 (14)0.0072 (13)−0.0002 (12)−0.0013 (13)
C50.028 (2)0.013 (2)0.0125 (19)−0.0014 (16)−0.0047 (16)−0.0007 (15)
C10.0205 (19)0.026 (2)0.019 (2)−0.0005 (17)−0.0023 (16)−0.0004 (17)
C20.023 (2)0.043 (3)0.022 (2)−0.009 (2)0.0021 (17)0.005 (2)
C80.0162 (18)0.017 (2)0.020 (2)0.0003 (15)−0.0008 (15)0.0045 (16)
C60.051 (3)0.015 (2)0.038 (3)−0.009 (2)−0.007 (2)0.0020 (19)
C40.037 (2)0.021 (2)0.019 (2)−0.0084 (19)−0.0071 (18)0.0027 (17)
C70.026 (2)0.034 (3)0.028 (2)0.0110 (19)−0.0049 (18)0.006 (2)
C30.037 (3)0.028 (3)0.030 (2)−0.014 (2)−0.003 (2)0.005 (2)
Geometric parameters (Å, °) top
O1W—H1WA0.85 (6)N1—C51.360 (5)
O7—C81.464 (4)O2—H2A0.84 (2)
O7—H70.8200O6—H6A0.83 (4)
O5—P21.511 (3)C5—C41.400 (5)
Ni1—N12.059 (3)C5—C5i1.438 (7)
Ni1—N1i2.059 (3)C1—C21.406 (6)
Ni1—O3i2.065 (3)C1—H10.9300
Ni1—O32.065 (3)C2—C31.362 (6)
Ni1—O42.109 (2)C2—H20.9300
Ni1—O4i2.109 (2)C8—C71.514 (5)
P1—O31.499 (3)C6—C6i1.352 (9)
P1—O11.510 (3)C6—C41.426 (6)
P1—O21.569 (3)C6—H60.9300
P1—C81.834 (4)C4—C31.405 (6)
P2—O41.514 (3)C7—H7A0.9600
P2—O61.551 (3)C7—H7B0.9600
P2—C81.836 (4)C7—H7C0.9600
N1—C11.326 (5)C3—H30.9300
C8—O7—H7109.5P1—O2—H2A119 (4)
N1—Ni1—N1i81.47 (17)P2—O6—H6A116 (3)
N1—Ni1—O3i177.81 (11)N1—C5—C4122.9 (4)
N1i—Ni1—O3i96.34 (11)N1—C5—C5i117.3 (2)
N1—Ni1—O396.34 (11)C4—C5—C5i119.8 (2)
N1i—Ni1—O3177.81 (11)N1—C1—C2122.6 (4)
O3i—Ni1—O385.85 (14)N1—C1—H1118.7
N1—Ni1—O495.88 (11)C2—C1—H1118.7
N1i—Ni1—O485.92 (11)C3—C2—C1119.0 (4)
O3i—Ni1—O483.84 (10)C3—C2—H2120.5
O3—Ni1—O494.41 (9)C1—C2—H2120.5
N1—Ni1—O4i85.92 (11)O7—C8—C7107.8 (3)
N1i—Ni1—O4i95.88 (11)O7—C8—P1105.4 (2)
O3i—Ni1—O4i94.41 (9)C7—C8—P1112.6 (3)
O3—Ni1—O4i83.84 (10)O7—C8—P2107.7 (2)
O4—Ni1—O4i177.63 (14)C7—C8—P2111.9 (3)
O3—P1—O1115.74 (16)P1—C8—P2111.03 (19)
O3—P1—O2110.59 (16)C6i—C6—C4121.2 (2)
O1—P1—O2105.64 (16)C6i—C6—H6119.4
O3—P1—C8107.32 (15)C4—C6—H6119.4
O1—P1—C8112.24 (16)C5—C4—C3117.2 (4)
O2—P1—C8104.79 (17)C5—C4—C6119.0 (4)
O5—P2—O4114.45 (15)C3—C4—C6123.8 (4)
O5—P2—O6109.01 (15)C8—C7—H7A109.5
O4—P2—O6111.53 (14)C8—C7—H7B109.5
O5—P2—C8109.23 (16)H7A—C7—H7B109.5
O4—P2—C8106.25 (16)C8—C7—H7C109.5
O6—P2—C8105.99 (17)H7A—C7—H7C109.5
P1—O3—Ni1135.93 (15)H7B—C7—H7C109.5
P2—O4—Ni1124.60 (14)C2—C3—C4120.0 (4)
C1—N1—C5118.2 (3)C2—C3—H3120.0
C1—N1—Ni1129.7 (3)C4—C3—H3120.0
C5—N1—Ni1111.9 (2)
Symmetry codes: (i) −x, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O70.85 (6)1.93 (6)2.758 (5)166 (6)
O2—H2A···O1Wii0.84 (4)1.91 (4)2.748 (4)175 (6)
O6—H6A···O4iii0.83 (4)1.82 (4)2.644 (3)171 (5)
O7—H7···O40.822.472.894 (4)113
O7—H7···O3iv0.822.082.889 (4)169
Symmetry codes: (ii) −x, −y, −z+1; (iii) −x, y, −z+3/2; (iv) −x, y, −z+1/2.
Table 1
Selected geometric parameters (Å) top
Ni1—N12.059 (3)Ni1—O42.109 (2)
Ni1—O32.065 (3)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O1W—H1WA···O70.85 (6)1.93 (6)2.758 (5)166 (6)
O2—H2A···O1Wi0.84 (4)1.91 (4)2.748 (4)175 (6)
O6—H6A···O4ii0.83 (4)1.82 (4)2.644 (3)171 (5)
O7—H7···O40.822.472.894 (4)113
O7—H7···O3iii0.822.082.889 (4)169
Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+3/2; (iii) −x, y, −z+1/2.
Acknowledgements top

This project is supported by the Natural Science Foundation of the Education Bureau of Liaoning Province.

references
References top

Bruker (2001). SMART, SAINT, SADABS and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Song, H.-H., Zheng, L.-M., Lin, C.-H., Wang, S.-L., Xin, X.-Q. & Gao, S. (1999). Chem. Mater. 11, 2382–2388.

Xiang, J., Li, M., Wu, S., Yuan, L.-J. & Sun, J. (2007). J. Mol. Struct. 826, 143–149.