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Acta Cryst. (2007). E63, m1917-m1918    [ doi:10.1107/S1600536807028115 ]

Triaqua(4-hydroxypyridine-2,6-dicarboxylato)nickel(II) sesquihydrate

H. Aghabozorg, M. Ghadermazi, J. Soleimannejad and S. Sheshmani

Abstract top

The reaction of nickel(II) nitrate hexahydrate with the proton-transfer compound piperazinediium 4-hydroxypyridine-2,6-dicarboxylate, (pipzH2)(hypydc), where pipz is piperazine and hypydcH2 is 4-hydroxypyridine-2,6-dicarboxylic acid, in aqueous solution leads to the formation of the title complex, [Ni(C7H3NO5)(H2O)3]·1.5H2O. Nickel(II) is coordinated by three donor atoms of the tridentate dianionic ligand, and three water molecules, in a slightly distorted octahedral geometry. The range of H...A and D...A distances, and D-H...A angles indicates the presence of strong hydrogen bonding in this complex, which involves the coordinated and uncoordinated water molecules (one of which lies on a twofold rotation axis), giving a three-dimensional network.

Comment top

The chemical formula and the ORTEP diagram indicate that the cationic fragment (pipzH2)2+ has been missed during complexation and only the anionic species of the starting proton transfer compound has contributed to the complex. This is similar to some other complexes containing only the anionic fragments of their starting proton transfer compounds. The N(1)–Ni(1)–O(7) angle revealed an octahedral axis with 3.73° deviation from ideal linearity, therefore, O(1), O(4), O(6) and O(8) are equatorial positions of the distorted octahedral. Both weak and strong hydrogen bonds with D···A distances ranging from 2.649 (5)to 3.142 (6) Å, are observed in the crystal. The presence of OH group of 4-hydroxypyridine-2,6-dicarboxylate, carboxylate and water molecules in the crystal structure causes the hydrogen bonding network of the system to be more extended, as its hydrogen bonds has an important linking role among the crystal lattice fragments. Also, two halves of the units [Ni(hypydc)(H2O)3], are kept together through hydrogen bonding between water molecules and oxygen atom of carboxylate group. Figures 1 and 2 are shown the molecular structure and packing diagram of this complex, respectively.

Related literature top

In recent years, we have been interested in the synthesis of proton-transfer compounds and have studied their behaviour with metal ions. We have focused on proton delivery from dicarboxylic acids, which are considered to be very good donors. Several proton acceptors were selected and employed. The result was the preparation of several proton-transfer compounds possessing anionic forms of diacid as donors. The application of these compounds in the preparation of metal–organic structures has also been investigated. Some of these metal complexes show the contribution of both cationic and anionic fragments of the starting proton-transfer compound, while others contain only one of these species as ligands (Aghabozorg et al., 2006; Aghabozorg et al., 2006a,b; Moghimi et al., 2005; Sheshmani et al., 2006).

Experimental top

To 20 ml of an aqueous solution of (pipzH2)(hypydc) (584 mg, 2 mmol) was added 10 ml of an aqueous solution of nickel(II) nitrate hexahydrate (290 mg, 1 mmol). Upon standing, crystals were precipitated after 20 days. The pure crystalline complex [Ni(hypydc)(H2O)3]. 2H2O,were decomposed at >400 °C.

Refinement top

Hydrogen atoms were positioned geometrically and refined with a riding model (including torsional freedom for methyl groups), with C—H = 0.95–0.98 Å, and with U(H) constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids.
[Figure 2] Fig. 2. The packing of (I), showing molecules connected by O–H···O hydrogen bonds (dashed lines).
Triaqua(4-hydroxypyridine-2,6-dicarboxylato)nickel(II) sesquihydrate top
Crystal data top
[Ni(C7H3NO5)(H2O)3]·1.5H2OF000 = 1320
Mr = 320.89Dx = 1.859 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C2ycCell parameters from 4075 reflections
a = 14.881 (12) Åθ = 2.7–27.3º
b = 6.878 (6) ŵ = 1.74 mm−1
c = 22.409 (19) ÅT = 150 (2) K
β = 90.049 (15)ºBlock, blue
V = 2294 (3) Å30.43 × 0.34 × 0.07 mm
Z = 8
Data collection top
Bruker SMART 1000
diffractometer		2019 independent reflections
Radiation source: fine-focus sealed tube1567 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.121
Detector resolution: 100 pixels mm-1θmax = 25.0º
T = 150(2) Kθmin = 1.8º
ω scansh = −17→17
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		k = −8→8
Tmin = 0.522, Tmax = 0.888l = −26→26
10569 measured reflections
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)] = 0.057H-atom parameters constrained
wR(F2) = 0.161  w = 1/[σ2(Fo2) + (0.1044P)2 + 2.0879P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max = 0.001
2019 reflectionsΔρmax = 2.09 e Å−3
169 parametersΔρmin = −1.02 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Ni(C7H3NO5)(H2O)3]·1.5H2OV = 2294 (3) Å3
Mr = 320.89Z = 8
Monoclinic, C2/cMo Kα
a = 14.881 (12) ŵ = 1.74 mm−1
b = 6.878 (6) ÅT = 150 (2) K
c = 22.409 (19) Å0.43 × 0.34 × 0.07 mm
β = 90.049 (15)º
Data collection top
Bruker SMART 1000
diffractometer		2019 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		1567 reflections with I > 2σ(I)
Tmin = 0.522, Tmax = 0.888Rint = 0.121
10569 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.057169 parameters
wR(F2) = 0.161H-atom parameters constrained
S = 1.06Δρmax = 2.09 e Å−3
2019 reflectionsΔρmin = −1.02 e Å−3
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 > 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
xyzUiso*/Ueq
Ni10.52210 (4)0.24829 (8)0.63815 (2)0.0155 (3)
N10.6177 (2)0.1265 (5)0.58918 (16)0.0139 (8)
O10.4739 (2)0.2898 (4)0.54619 (14)0.0164 (7)
O20.5152 (2)0.2401 (4)0.45093 (14)0.0186 (8)
O30.7282 (2)−0.0631 (5)0.71543 (14)0.0266 (8)
O40.6134 (2)0.1517 (5)0.70553 (13)0.0201 (7)
O50.83039 (19)−0.0744 (5)0.48988 (13)0.0177 (7)
H50.8737−0.10620.51190.021*
O60.4476 (2)−0.0092 (5)0.64449 (15)0.0242 (8)
H6A0.4428−0.06820.60630.029*
H6B0.38630.02170.63730.029*
O70.4278 (2)0.3656 (5)0.69271 (14)0.0238 (8)
H7A0.43930.48310.71370.029*
H7B0.39920.28430.72130.029*
O80.5778 (2)0.5276 (5)0.63456 (14)0.0214 (7)
H8A0.56010.59380.59920.026*
H8B0.64060.53240.64180.026*
O90.5000−0.2882 (9)0.75000.073 (3)
H9A0.5060−0.21330.71460.088*
O100.7368 (2)0.0525 (5)0.83145 (15)0.0283 (8)
H10A0.68050.01470.81520.034*
H10B0.75870.16790.81330.034*
C10.5283 (3)0.2279 (6)0.5061 (2)0.0183 (11)
C20.6146 (3)0.1338 (6)0.52935 (19)0.0137 (9)
C30.6850 (3)0.0626 (6)0.49478 (19)0.0137 (9)
H30.68180.06630.45240.016*
C40.7612 (3)−0.0153 (6)0.5238 (2)0.0146 (9)
C50.7629 (3)−0.0255 (6)0.5870 (2)0.0172 (10)
H5A0.8129−0.07860.60770.021*
C60.6881 (3)0.0456 (6)0.6176 (2)0.0159 (9)
C70.6769 (3)0.0447 (7)0.6852 (2)0.0173 (10)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0124 (4)0.0218 (4)0.0122 (4)0.0028 (2)0.0006 (3)−0.0001 (2)
N10.0115 (17)0.0175 (19)0.0128 (19)0.0013 (14)−0.0006 (14)−0.0005 (15)
O10.0119 (16)0.0214 (17)0.0158 (17)0.0039 (12)0.0018 (13)0.0003 (13)
O20.0207 (19)0.0224 (18)0.0125 (19)0.0041 (12)−0.0068 (14)−0.0010 (12)
O30.0264 (18)0.040 (2)0.0137 (17)0.0100 (15)−0.0024 (14)0.0013 (15)
O40.0208 (16)0.0279 (19)0.0118 (16)0.0080 (14)0.0007 (12)0.0003 (14)
O50.0127 (15)0.0247 (18)0.0156 (16)0.0069 (12)0.0026 (12)0.0001 (14)
O60.0220 (17)0.0281 (18)0.0226 (18)−0.0020 (13)0.0033 (14)−0.0038 (15)
O70.0232 (17)0.032 (2)0.0161 (17)0.0059 (14)0.0043 (13)0.0009 (15)
O80.0210 (16)0.0252 (18)0.0180 (17)0.0002 (13)−0.0010 (13)0.0020 (14)
O90.145 (8)0.038 (4)0.036 (4)0.0000.035 (5)0.000
O100.0250 (18)0.037 (2)0.0226 (19)−0.0041 (15)−0.0039 (14)0.0024 (16)
C10.022 (3)0.013 (2)0.021 (3)−0.0016 (17)0.004 (2)0.0016 (18)
C20.012 (2)0.016 (2)0.013 (2)−0.0011 (17)−0.0020 (16)−0.0009 (18)
C30.016 (2)0.015 (2)0.010 (2)−0.0022 (16)−0.0007 (17)−0.0002 (17)
C40.014 (2)0.015 (2)0.015 (2)−0.0005 (16)0.0013 (17)0.0010 (18)
C50.015 (2)0.020 (2)0.016 (2)0.0035 (17)0.0000 (18)−0.0002 (19)
C60.013 (2)0.019 (2)0.015 (2)−0.0005 (17)−0.0027 (17)0.0020 (18)
C70.013 (2)0.025 (2)0.014 (2)0.0018 (18)0.0008 (18)0.0001 (19)
Geometric parameters (Å, °) top
Ni1—N11.983 (4)O7—H7A0.9501
Ni1—O72.029 (3)O7—H7B0.9501
Ni1—O82.094 (4)O8—H8A0.9500
Ni1—O62.094 (4)O8—H8B0.9501
Ni1—O42.136 (3)O9—H9A0.9500
Ni1—O12.200 (4)O10—H10A0.9500
N1—C21.342 (6)O10—H10B0.9499
N1—C61.346 (6)C1—C21.529 (6)
O1—C11.283 (6)C2—C31.393 (6)
O2—C11.254 (6)C3—C41.412 (6)
O3—C71.261 (5)C3—H30.9500
O4—C71.282 (5)C4—C51.418 (7)
O5—C41.344 (5)C5—C61.395 (6)
O5—H50.8400C5—H5A0.9500
O6—H6A0.9499C6—C71.525 (6)
O6—H6B0.9500
N1—Ni1—O7176.51 (13)H7A—O7—H7B104.3
N1—Ni1—O894.73 (14)Ni1—O8—H8A111.2
O7—Ni1—O886.10 (14)Ni1—O8—H8B114.5
N1—Ni1—O693.45 (14)H8A—O8—H8B113.5
O7—Ni1—O685.93 (14)H10A—O10—H10B111.5
O8—Ni1—O6171.13 (13)O2—C1—O1124.8 (4)
N1—Ni1—O478.67 (14)O2—C1—C2119.6 (4)
O7—Ni1—O497.90 (14)O1—C1—C2115.6 (4)
O8—Ni1—O493.50 (13)N1—C2—C3121.1 (4)
O6—Ni1—O491.46 (14)N1—C2—C1112.6 (4)
N1—Ni1—O176.72 (14)C3—C2—C1126.2 (4)
O7—Ni1—O1106.71 (13)C2—C3—C4118.8 (4)
O8—Ni1—O188.48 (12)C2—C3—H3120.6
O6—Ni1—O190.07 (13)C4—C3—H3120.6
O4—Ni1—O1155.39 (12)O5—C4—C3118.0 (4)
C2—N1—C6120.9 (4)O5—C4—C5122.5 (4)
C2—N1—Ni1120.8 (3)C3—C4—C5119.5 (4)
C6—N1—Ni1118.2 (3)C6—C5—C4117.3 (4)
C1—O1—Ni1114.0 (3)C6—C5—H5A121.3
C7—O4—Ni1113.3 (3)C4—C5—H5A121.3
C4—O5—H5109.5N1—C6—C5122.3 (4)
Ni1—O6—H6A109.8N1—C6—C7112.7 (4)
Ni1—O6—H6B107.9C5—C6—C7125.1 (4)
H6A—O6—H6B82.7O3—C7—O4126.3 (4)
Ni1—O7—H7A120.8O3—C7—C6118.0 (4)
Ni1—O7—H7B118.8O4—C7—C6115.6 (4)
O8—Ni1—N1—C2−83.2 (3)Ni1—N1—C2—C1−4.7 (5)
O6—Ni1—N1—C293.4 (3)O2—C1—C2—N1−178.2 (4)
O4—Ni1—N1—C2−175.8 (3)O1—C1—C2—N11.9 (5)
O1—Ni1—N1—C24.1 (3)O2—C1—C2—C32.4 (7)
O8—Ni1—N1—C693.3 (3)O1—C1—C2—C3−177.5 (4)
O6—Ni1—N1—C6−90.1 (3)N1—C2—C3—C4−1.1 (6)
O4—Ni1—N1—C60.7 (3)C1—C2—C3—C4178.3 (4)
O1—Ni1—N1—C6−179.4 (3)C2—C3—C4—O5−176.7 (4)
N1—Ni1—O1—C1−2.8 (3)C2—C3—C4—C52.2 (6)
O7—Ni1—O1—C1177.9 (3)O5—C4—C5—C6178.1 (4)
O8—Ni1—O1—C192.4 (3)C3—C4—C5—C6−0.8 (6)
O6—Ni1—O1—C1−96.3 (3)C2—N1—C6—C53.2 (6)
O4—Ni1—O1—C1−2.7 (5)Ni1—N1—C6—C5−173.3 (3)
N1—Ni1—O4—C7−8.3 (3)C2—N1—C6—C7−177.7 (4)
O7—Ni1—O4—C7171.0 (3)Ni1—N1—C6—C75.8 (5)
O8—Ni1—O4—C7−102.4 (3)C4—C5—C6—N1−1.9 (7)
O6—Ni1—O4—C784.9 (3)C4—C5—C6—C7179.1 (4)
O1—Ni1—O4—C7−8.4 (5)Ni1—O4—C7—O3−164.3 (4)
Ni1—O1—C1—O2−178.6 (3)Ni1—O4—C7—C613.6 (5)
Ni1—O1—C1—C21.3 (4)N1—C6—C7—O3164.9 (4)
C6—N1—C2—C3−1.6 (6)C5—C6—C7—O3−16.0 (7)
Ni1—N1—C2—C3174.7 (3)N1—C6—C7—O4−13.2 (6)
C6—N1—C2—C1179.0 (4)C5—C6—C7—O4165.8 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O1i0.841.822.649 (5)167
O6—H6A···O2ii0.951.852.720 (5)151
O6—H6B···O10iii0.951.972.829 (5)149
O7—H7A···O9iv0.951.992.911 (7)163
O7—H7B···O4iii0.951.892.782 (5)156
O8—H8A···O2v0.951.962.852 (5)157
O8—H8A···O5vi0.952.583.123 (5)116
O8—H8B···O10vii0.951.922.867 (5)172
O9—H9A···O60.952.283.142 (6)151
O10—H10A···O6iii0.952.122.829 (5)131
O10—H10B···O3vii0.951.972.893 (5)164
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+1, −y, −z+1; (iii) −x+1, y, −z+3/2; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, −y+1/2, −z+1; (vii) −x+3/2, y+1/2, −z+3/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O5—H5···O1i0.841.822.649 (5)167
O6—H6A···O2ii0.951.852.720 (5)151
O6—H6B···O10iii0.951.972.829 (5)149
O7—H7A···O9iv0.951.992.911 (7)163
O7—H7B···O4iii0.951.892.782 (5)156
O8—H8A···O2v0.951.962.852 (5)157
O8—H8A···O5vi0.952.583.123 (5)116
O8—H8B···O10vii0.951.922.867 (5)172
O9—H9A···O60.952.283.142 (6)151
O10—H10A···O6iii0.952.122.829 (5)131
O10—H10B···O3vii0.951.972.893 (5)164
Symmetry codes: (i) x+1/2, y−1/2, z; (ii) −x+1, −y, −z+1; (iii) −x+1, y, −z+3/2; (iv) x, y+1, z; (v) −x+1, −y+1, −z+1; (vi) −x+3/2, −y+1/2, −z+1; (vii) −x+3/2, y+1/2, −z+3/2.
references
References top

Aghabozorg, H., Ghadermazi, M. & Nemati, A. (2006). Anal. Sci. X, 22, x233–x234.

Aghabozorg, H., Ghadermazi, M. & Sadr-Khanlou, E. (2006a). Anal. Sci. X, 22, x253–x254.

Aghabozorg, H., Ghadermazi, M. & Sadr-Khanlou, E. (2006b). Anal. Sci. X, 22, x255–x256.

Bruker (1998). SADABS (Version 1?), SAINT (Version 6.01), SMART (Version 5.059) and SHELXTL (Version 6.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Moghimi, A., Sheshmani, S., Shokrollahi, A., Shamsipour, M., Kickelbick, G. & &Aghabozorg, H. (2005). Z. Anorg. Allg. Chem. 631, 160–169.

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

Sheshmani, S., Aghabozorg, H., Mohammad Panah, F., Alizadeh, R., Kickelbick, G., Nakhjavan, B., Moghimi, A., Ramezanipour, F. & Aghabozorg, H. R. (2006). Z. Anorg. Allg. Chem. 632, 469–474.