Diaqua­(2,2′-bipyridine-6,6′-dicarboxyl­ato)nickel(II)

Hu, S.; Wen, S.P.; Hu, H.-M.; Liu, L.

doi:10.1107/S1600536811016400

metal-organic compounds

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Volume 67| Part 6| June 2011| Page m718

doi:10.1107/S1600536811016400

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Diaqua(2,2′-bipyridine-6,6′-dicarboxylato)nickel(II)

Shui Hu,^a ShiPeng Wen,^a Huai-Ming Hu ^b ^* and Li Liu ^a ^*

^aKey Laboratory of Carbon Fiber and Functional Polymer, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China, and ^bCollege of Chemistry and Materials Science, Northwest University, Xi'an 710069, People's Republic of China
^*Correspondence e-mail: chemhu1@nwu.edu.cn, liul2001@yahoo.com.cn

(Received 28 April 2011; accepted 30 April 2011; online 7 May 2011)

In the title compound, [Ni(C₁₂H₆N₂O₄)(H₂O)₂], the Ni^II atom (site symmetry 2) displays a distorted cis-NiN₂O₄ octahedral coordination geometry with two N atoms and two O atoms of the tetradentate 2,2′-bipyridine-6,6′-dicarboxylate ligand in the equatorial plane and two water molecules in axial positions. The complete dianionic ligand is generated by crystallographic twofold symmetry. In the crystal, a two-dimensional supramolecular structure parallel to (001) is formed through O—H⋯O hydrogen-bond interactions between the coordinated water molecules and the O atoms of nearby carboxylate groups.

Related literature

For transition metal complexes with the title ligand, see: Knight et al. (2006 ); Duan et al. (2009 ); Wang et al. (2009 ). For lanthanide metal complexes with the title ligand, see: Bunzli et al. (2000 ); Wang et al. (2010 ).

Experimental

Crystal data

[Ni(C₁₂H₆N₂O₄)(H₂O)₂]
M_r = 336.93
Orthorhombic, P c c n
a = 7.1056 (9) Å
b = 11.3608 (15) Å
c = 15.3334 (19) Å
V = 1237.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.60 mm⁻¹
T = 296 K
0.24 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.766, T_max = 0.857
6269 measured reflections
1274 independent reflections
1098 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 1.06
1274 reflections
102 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Selected bond lengths (Å)

Ni1—N1	1.9975 (19)
Ni1—O3	2.0553 (18)
Ni1—O1	2.1335 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3A⋯O2ⁱ	0.81 (2)	1.90 (2)	2.708 (2)	176 (3)
O3—H3B⋯O2ⁱⁱ	0.83 (2)	1.95 (2)	2.772 (3)	172 (3)
Symmetry codes: (i) $[-x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z]$ ; (ii) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811016400/hb5864sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811016400/hb5864Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811016400/hb5864Isup3.cdx

checkCIF report

Comment top

Pyridyl carboxylic acid is an important class of organic ligands and has been widely used in coordination chemistry. 2,2'-Bipyridine-6,6'-dicarboxylate ligand is coordinated woth transition metal (Duan et al., 2009; Knight et al., 2006 and Wang et al., 2009) and lanthanide metal ions (Bunzli et al., 2000 and Wang et al., 2010). Herein, we report crystal structure of a new nickel complex with 2,2'-bipyridine-6,6'-dicarboxylate ligand.

The atom-numbering scheme of (I) is shown in Fig. 1. The Ni^II atom displays a distorted octahedral coordination geometry with two N atoms and two O atoms of 2,2'-bipyridine-6,6'-dicarboxylate in equatorial plane and two water molecules in apical positions. A two-dimensional supramolecular structure is formed through hydrogen interactions between the oxygen atoms of coordination water molecules and the oxygen atoms of carboxylate groups [O3—H3A···O2ⁱ, 2.708 (3) Å, 176 (3) °, symmetric code i: (-x - 1/2, -y + 3/2, z); O3—H3B···O2ⁱⁱ, 2.772 (3) Å, 172 (3) °, symmetric code ii: (-x, y - 1/2, -z + 1/2)].

Related literature top

For transition metal complexes with the title ligand, see: Knight et al. (2006); Duan et al. (2009); Wang et al. (2009). For lanthanide metal complexes with the title ligand, see: Bunzli et al. (2000); Wang et al. (2010).

Experimental top

The title compound was prepared by the reaction of Ni(NO₃)₂ with 2,2'-bipyridine-6,6'-dicarboxylic acid (H₂bpdc) in a water solution. Ni(NO₃)₂.6H₂O (0.2 mmol) and H₂bpdc (0.2 mmol) were dissolved in 25 ml deionized water and adjusted the pH to 7 with 0.05 mol L^-1 NaOH aqueous solution. After one week, green blocks were obtained. Elmental analysis for C₁₂H₁₀N₂NiO₆ calculated: C 42.78, H 2.99, N 8.32%; found: C 42.57, H 2.89, N 8.46%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids. Atoms labelled with the suffix A are at the symmetry position (-x + 1/2, -y + 3/2, z).
	Fig. 2. View of a two-dimensional supramolecular structure constructed through hydrogen bonding interactions in (I). Hydrogen atoms of carbon atoms have been omitted for clarity.

Diaqua(2,2'-bipyridine-6,6'-dicarboxylato)nickel(II) top

Crystal data top

[Ni(C₁₂H₆N₂O₄)(H₂O)₂]	F(000) = 688
M_r = 336.93	D_x = 1.808 Mg m⁻³
Orthorhombic, Pccn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ab 2ac	Cell parameters from 1650 reflections
a = 7.1056 (9) Å	θ = 3.2–25.2°
b = 11.3608 (15) Å	µ = 1.60 mm⁻¹
c = 15.3334 (19) Å	T = 296 K
V = 1237.8 (3) Å³	Block, green
Z = 4	0.24 × 0.16 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1274 independent reflections
Radiation source: fine-focus sealed tube	1098 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 26.4°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.766, T_max = 0.857	k = −13→14
6269 measured reflections	l = −10→19

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0405P)² + 0.5888P] where P = (F_o² + 2F_c²)/3
1274 reflections	(Δ/σ)_max < 0.001
102 parameters	Δρ_max = 0.48 e Å⁻³
2 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

[Ni(C₁₂H₆N₂O₄)(H₂O)₂]	V = 1237.8 (3) Å³
M_r = 336.93	Z = 4
Orthorhombic, Pccn	Mo Kα radiation
a = 7.1056 (9) Å	µ = 1.60 mm⁻¹
b = 11.3608 (15) Å	T = 296 K
c = 15.3334 (19) Å	0.24 × 0.16 × 0.10 mm

Data collection top

Bruker APEXII CCD diffractometer	1274 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1098 reflections with I > 2σ(I)
T_min = 0.766, T_max = 0.857	R_int = 0.036
6269 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	2 restraints
wR(F²) = 0.082	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.48 e Å⁻³
1274 reflections	Δρ_min = −0.23 e Å⁻³
102 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

	x	y	z	U_iso*/U_eq
Ni1	0.2500	0.7500	0.16327 (3)	0.02540 (16)
N1	0.0931 (3)	0.80137 (16)	0.06211 (12)	0.0285 (4)
O1	0.0167 (2)	0.83346 (15)	0.22531 (11)	0.0360 (4)
O2	−0.2446 (2)	0.93408 (18)	0.19595 (16)	0.0517 (6)
C1	−0.1035 (3)	0.8756 (2)	0.17424 (18)	0.0348 (6)
C2	−0.0683 (4)	0.8569 (2)	0.07707 (17)	0.0332 (6)
C3	−0.1808 (4)	0.8936 (2)	0.0083 (2)	0.0464 (7)
H3	−0.2934	0.9332	0.0182	0.056*
C4	−0.1204 (5)	0.8695 (3)	−0.0750 (2)	0.0563 (9)
H4	−0.1951	0.8915	−0.1221	0.068*
C5	0.0486 (5)	0.8132 (2)	−0.09017 (18)	0.0506 (8)
H5	0.0894	0.7982	−0.1467	0.061*
C6	0.1564 (4)	0.7796 (2)	−0.01856 (16)	0.0348 (6)
O3	0.1216 (2)	0.58888 (16)	0.17647 (13)	0.0380 (5)
H3A	0.009 (3)	0.584 (3)	0.1803 (18)	0.046*
H3B	0.169 (4)	0.545 (2)	0.2135 (15)	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0254 (3)	0.0293 (3)	0.0215 (2)	0.00250 (16)	0.000	0.000
N1	0.0341 (11)	0.0256 (10)	0.0260 (11)	−0.0004 (9)	−0.0053 (9)	−0.0005 (8)
O1	0.0336 (9)	0.0402 (10)	0.0343 (10)	0.0040 (8)	0.0046 (8)	−0.0040 (8)
O2	0.0263 (10)	0.0466 (12)	0.0821 (15)	0.0055 (8)	−0.0004 (9)	−0.0232 (11)
C1	0.0248 (12)	0.0269 (12)	0.0526 (17)	−0.0047 (10)	0.0005 (12)	−0.0078 (11)
C2	0.0316 (13)	0.0217 (12)	0.0464 (16)	−0.0021 (10)	−0.0109 (11)	−0.0021 (10)
C3	0.0437 (15)	0.0291 (14)	0.067 (2)	−0.0016 (11)	−0.0276 (15)	0.0050 (13)
C4	0.073 (2)	0.0378 (16)	0.059 (2)	−0.0073 (15)	−0.0407 (18)	0.0134 (14)
C5	0.085 (2)	0.0380 (16)	0.0289 (15)	−0.0094 (16)	−0.0177 (15)	0.0061 (11)
C6	0.0530 (17)	0.0261 (12)	0.0252 (12)	−0.0045 (11)	−0.0073 (12)	0.0018 (9)
O3	0.0259 (9)	0.0364 (10)	0.0519 (12)	0.0001 (8)	0.0044 (9)	0.0117 (8)

Geometric parameters (Å, º) top

Ni1—N1ⁱ	1.9975 (19)	C2—C3	1.387 (4)
Ni1—N1	1.9975 (19)	C3—C4	1.375 (5)
Ni1—O3ⁱ	2.0553 (18)	C3—H3	0.9300
Ni1—O3	2.0553 (18)	C4—C5	1.381 (5)
Ni1—O1ⁱ	2.1335 (16)	C4—H4	0.9300
Ni1—O1	2.1335 (16)	C5—C6	1.392 (4)
N1—C2	1.329 (3)	C5—H5	0.9300
N1—C6	1.339 (3)	C6—C6ⁱ	1.491 (5)
O1—C1	1.254 (3)	O3—H3A	0.806 (18)
O2—C1	1.247 (3)	O3—H3B	0.827 (17)
C1—C2	1.526 (4)

N1ⁱ—Ni1—N1	78.11 (11)	O2—C1—C2	117.8 (2)
N1ⁱ—Ni1—O3ⁱ	95.10 (8)	O1—C1—C2	116.4 (2)
N1—Ni1—O3ⁱ	93.67 (8)	N1—C2—C3	120.6 (3)
N1ⁱ—Ni1—O3	93.67 (8)	N1—C2—C1	112.1 (2)
N1—Ni1—O3	95.10 (8)	C3—C2—C1	127.3 (3)
O3ⁱ—Ni1—O3	168.70 (11)	C4—C3—C2	117.8 (3)
N1ⁱ—Ni1—O1ⁱ	77.45 (7)	C4—C3—H3	121.1
N1—Ni1—O1ⁱ	155.48 (8)	C2—C3—H3	121.1
O3ⁱ—Ni1—O1ⁱ	90.40 (7)	C3—C4—C5	121.4 (3)
O3—Ni1—O1ⁱ	84.56 (7)	C3—C4—H4	119.3
N1ⁱ—Ni1—O1	155.48 (8)	C5—C4—H4	119.3
N1—Ni1—O1	77.45 (7)	C4—C5—C6	118.2 (3)
O3ⁱ—Ni1—O1	84.56 (7)	C4—C5—H5	120.9
O3—Ni1—O1	90.40 (7)	C6—C5—H5	120.9
O1ⁱ—Ni1—O1	127.04 (9)	N1—C6—C5	119.5 (3)
C2—N1—C6	122.5 (2)	N1—C6—C6ⁱ	112.53 (14)
C2—N1—Ni1	119.11 (17)	C5—C6—C6ⁱ	127.93 (19)
C6—N1—Ni1	118.41 (17)	Ni1—O3—H3A	121 (2)
C1—O1—Ni1	114.88 (15)	Ni1—O3—H3B	115 (2)
O2—C1—O1	125.7 (3)	H3A—O3—H3B	108 (3)

N1ⁱ—Ni1—N1—C2	−178.6 (2)	Ni1—N1—C2—C3	−179.86 (17)
O3ⁱ—Ni1—N1—C2	−84.19 (18)	C6—N1—C2—C1	−177.4 (2)
O3—Ni1—N1—C2	88.68 (18)	Ni1—N1—C2—C1	1.8 (3)
O1ⁱ—Ni1—N1—C2	176.75 (16)	O2—C1—C2—N1	175.2 (2)
O1—Ni1—N1—C2	−0.59 (17)	O1—C1—C2—N1	−2.6 (3)
N1ⁱ—Ni1—N1—C6	0.53 (13)	O2—C1—C2—C3	−3.1 (4)
O3ⁱ—Ni1—N1—C6	94.98 (18)	O1—C1—C2—C3	179.2 (2)
O3—Ni1—N1—C6	−92.15 (18)	N1—C2—C3—C4	0.6 (4)
O1ⁱ—Ni1—N1—C6	−4.1 (3)	C1—C2—C3—C4	178.7 (2)
O1—Ni1—N1—C6	178.57 (19)	C2—C3—C4—C5	−1.5 (4)
N1ⁱ—Ni1—O1—C1	3.7 (3)	C3—C4—C5—C6	1.0 (4)
N1—Ni1—O1—C1	−0.96 (16)	C2—N1—C6—C5	−1.6 (4)
O3ⁱ—Ni1—O1—C1	94.04 (17)	Ni1—N1—C6—C5	179.24 (19)
O3—Ni1—O1—C1	−96.09 (17)	C2—N1—C6—C6ⁱ	177.8 (2)
O1ⁱ—Ni1—O1—C1	−179.58 (17)	Ni1—N1—C6—C6ⁱ	−1.4 (3)
Ni1—O1—C1—O2	−175.4 (2)	C4—C5—C6—N1	0.6 (4)
Ni1—O1—C1—C2	2.1 (3)	C4—C5—C6—C6ⁱ	−178.7 (3)
C6—N1—C2—C3	1.0 (4)

Symmetry code: (i) −x+1/2, −y+3/2, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱⁱ	0.81 (2)	1.90 (2)	2.708 (2)	176 (3)
O3—H3B···O2ⁱⁱⁱ	0.83 (2)	1.95 (2)	2.772 (3)	172 (3)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₁₂H₆N₂O₄)(H₂O)₂]
M_r	336.93
Crystal system, space group	Orthorhombic, Pccn
Temperature (K)	296
a, b, c (Å)	7.1056 (9), 11.3608 (15), 15.3334 (19)
V (Å³)	1237.8 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.60
Crystal size (mm)	0.24 × 0.16 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.766, 0.857
No. of measured, independent and observed [I > 2σ(I)] reflections	6269, 1274, 1098
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 1.06
No. of reflections	1274
No. of parameters	102
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.23

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Ni1—N1	1.9975 (19)	Ni1—O1	2.1335 (16)
Ni1—O3	2.0553 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2ⁱ	0.806 (18)	1.904 (18)	2.708 (2)	176 (3)
O3—H3B···O2ⁱⁱ	0.827 (17)	1.950 (17)	2.772 (3)	172 (3)

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

References

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Bunzli, J.-C. G., Charbonniere, L. J. & Ziessel, R. F. (2000). J. Chem. Soc. Dalton Trans. pp. 1917–1923. Google Scholar
Duan, L., Fischer, A., Xu, Y. & Sun, L. (2009). J. Am. Chem. Soc. 131, 10397–10399. Web of Science CrossRef PubMed CAS Google Scholar
Knight, J. C., Amoroso, A. J., Edwards, P. G. & Ooi, L.-L. (2006). Acta Cryst. E62, m3306–m3308. Web of Science CSD CrossRef IUCr Journals Google Scholar
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Wang, H., Su, H., Xu, J., Bai, F. & Gao, Y. (2009). Acta Cryst. E65, m352–m353. Web of Science CSD CrossRef IUCr Journals Google Scholar
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doi:10.1107/S1600536811016400

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