Tetra­aqua­(2,2′-bipyridine-5,5′-dicarboxyl­ato-κ2N,N′)nickel(II) dihydrate

Yang, H.

doi:10.1107/S1600536809035910

metal-organic compounds

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Volume 65| Part 10| October 2009| Page m1207

doi:10.1107/S1600536809035910

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Tetraaqua(2,2′-bipyridine-5,5′-dicarboxylato-κ²N,N′)nickel(II) dihydrate

Hua Yang ^a ^*

^aDepartment of Chemistry, Mudanjiang Teachers College, Mudanjiang 157012, People's Republic of China
^*Correspondence e-mail: youngflower7799@yahoo.com.cn

(Received 2 September 2009; accepted 5 September 2009; online 12 September 2009)

In the title compound, [Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O, obtained from a basic solution of 2,2′-bipyridine-5,5′-dicarboxylate and nickel(II) chloride in water, the central Ni(II) cation (site symmetry 2) is coordinated by two N atoms from the 2,2′-bipyridine-5,5′-dicarboxylate ligand and four aqua O atoms. The N—Ni—N angle is 78.64 (8)°. Weak but significant π–π stacking interactions exist between the pyridine rings with a centroid–centroid distance of 3.652 (8) Å. In addition, four O atoms of the two carboxyl groups form hydrogen bonds with both coordinated and uncoordinated water molecules, forming an infinite three-dimensional network.

Related literature

For attempts to synthesize 5,5′- and 6,6′-substituted 2,2′-bipyridine derivatives, see: He et al. (2009 ); Karaca et al. (2009 ); Yousefi et al. (2008 ).

Experimental

Crystal data

[Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O
M_r = 408.97
Monoclinic, C 2/c
a = 12.4787 (2) Å
b = 9.8152 (2) Å
c = 12.6533 (2) Å
β = 92.107 (2)°
V = 1548.74 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.31 mm⁻¹
T = 120 K
0.18 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.730, T_max = 0.828
8276 measured reflections
1691 independent reflections
1379 reflections with I > 2σ(I)
R_int = 0.037

Refinement

R[F² > 2σ(F²)] = 0.025
wR(F²) = 0.065
S = 0.98
1691 reflections
138 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H52⋯O3ⁱ	0.837 (10)	2.178 (16)	2.9566 (19)	155 (3)
O2—H22⋯O3ⁱⁱ	0.834 (10)	1.921 (12)	2.7410 (18)	168 (3)
O5—H51⋯O4ⁱⁱⁱ	0.834 (10)	1.913 (11)	2.7286 (19)	166 (2)
O2—H21⋯O4^iv	0.833 (10)	1.852 (10)	2.6831 (17)	175 (2)
O1—H11⋯O4^iv	0.843 (9)	2.650 (17)	3.1740 (18)	121.6 (16)
O1—H11⋯O3^iv	0.843 (9)	2.097 (10)	2.9386 (18)	175.9 (19)
O1—H12⋯O5	0.834 (10)	1.861 (11)	2.688 (2)	171 (3)
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x, -y, z-{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+2; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+2]$ .

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: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809035910/ng2636sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809035910/ng2636Isup2.hkl

checkCIF report

Comment top

2,2'-Bipyridine was used very commonly as ending complexing ligand. Great efforts have been made to synthesize 5,5' and 6,6' position substituted derivatives (He et al., 2009; Karaca et al., 2009; Yousefi et al., 2008). Here we reported the crystal structure of a complexing compound of Ni(II) coordinating to 4,4'dicarboxyl substituted 2,2'-bipyridine derivative.

The central Ni cation coordinated to two N atoms from dianions of one 2,2'-bipyridine-5,5'-dicarboxylate and four O atoms from four waters, forming a distorted octahedral system. Ni(II) cation lies on the twofold axis of the crystal lattice. Two Ni—N bonds were generated by C2 symmetry operation from each other with bond length 2.0706 (14). Four Ni—O bond lengths are nearly equal, two of which 2.0610 (12), and another two 2.0801 (13). Each of two equivalent carboxyl anions has two unequivalent oxygen atoms, C—O bond lengths of which are equalized to be 1.266 (2) and 1.254 (2), respectively. All O atoms of carboxyls formed hydrogen bonds with both complexed waters from another complexing supermolecule and free waters into three dimentional infinite hydrgon bonding network, which stablized the whole crystal structure, along with pi-pi stacking of aromatic pyridine rings.

Related literature top

For attempts to synthesize 5,5'- and 6,6'-substituted 2,2'-bipyridine derivatives, see: He et al. (2009); Karaca et al. (2009); Yousefi et al. (2008).

Experimental top

A solution of 2,2'-bipyridine-5,5'-dicarboxylate (23.2 mg, 0.1 mmol) and NiCl₂.6H₂O (23.8 mg, 0.1 mmol) was added an aqueous solution of NaOH (0.1 mmol/ml) to adjust pH as 7.0–7.5 at room temperature. A small amount of white precipitate was removed from the resulting solution. Prism colorless crystals were obtained by slow evaporation at room temperature over a period of 10 days.

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: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure with atom labels and 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. The packing diagram of molecules, viewed down the b axis, with the weak interactions shown as dashed lines.

Tetraaqua(2,2'-bipyridine-5,5'-dicarboxylato-κ²N,N') nickel(II) dihydrate top

Crystal data top

[Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O	F(000) = 848.0
M_r = 408.97	D_x = 1.754 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8276 reflections
a = 12.4787 (2) Å	θ = 3.1–27.0°
b = 9.8152 (2) Å	µ = 1.31 mm⁻¹
c = 12.6533 (2) Å	T = 120 K
β = 92.107 (2)°	Prism, colourless
V = 1548.74 (5) Å³	0.18 × 0.16 × 0.10 mm
Z = 4

Data collection top

Bruker APEXII CCD area-detector diffractometer	1691 independent reflections
Radiation source: fine-focus sealed tube	1379 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.037
ϕ and ω scans	θ_max = 27.0°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −15→15
T_min = 0.730, T_max = 0.828	k = −12→12
8276 measured reflections	l = −14→16

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0426P)²] where P = (F_o² + 2F_c²)/3
1691 reflections	(Δ/σ)_max = 0.001
138 parameters	Δρ_max = 0.44 e Å⁻³
6 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

[Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O	V = 1548.74 (5) Å³
M_r = 408.97	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 12.4787 (2) Å	µ = 1.31 mm⁻¹
b = 9.8152 (2) Å	T = 120 K
c = 12.6533 (2) Å	0.18 × 0.16 × 0.10 mm
β = 92.107 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1691 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1379 reflections with I > 2σ(I)
T_min = 0.730, T_max = 0.828	R_int = 0.037
8276 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.025	6 restraints
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.44 e Å⁻³
1691 reflections	Δρ_min = −0.33 e Å⁻³
138 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	0.0000	0.27554 (3)	0.7500	0.01072 (11)
O1	0.03285 (11)	0.42083 (13)	0.86619 (11)	0.0142 (3)
H11	0.0898 (11)	0.4670 (18)	0.8664 (17)	0.019 (6)*
H12	−0.0189 (14)	0.475 (2)	0.864 (2)	0.044 (8)*
O2	0.15591 (10)	0.29226 (13)	0.70290 (10)	0.0129 (3)
H21	0.1953 (16)	0.315 (2)	0.7545 (13)	0.032 (7)*
H22	0.184 (2)	0.2274 (19)	0.672 (2)	0.052 (9)*
O3	0.26260 (10)	−0.06943 (12)	1.12935 (10)	0.0145 (3)
O4	0.21890 (10)	0.15053 (12)	1.12590 (10)	0.0166 (3)
O5	−0.12732 (13)	0.60197 (15)	0.83875 (13)	0.0301 (4)
H51	−0.1494 (18)	0.6770 (14)	0.8598 (18)	0.033 (7)*
H52	−0.1726 (19)	0.580 (3)	0.7913 (18)	0.067 (10)*
N1	0.04499 (11)	0.11232 (14)	0.84534 (11)	0.0106 (3)
C1	0.21332 (13)	0.03194 (17)	1.08927 (14)	0.0119 (4)
C2	0.14678 (14)	0.01069 (17)	0.98899 (14)	0.0116 (4)
C3	0.13045 (14)	−0.11715 (17)	0.94398 (14)	0.0119 (4)
H3	0.1595	−0.1960	0.9778	0.014*
C4	0.07152 (14)	−0.12874 (17)	0.84950 (14)	0.0126 (4)
H4	0.0596	−0.2156	0.8180	0.015*
C5	0.03040 (13)	−0.01275 (17)	0.80161 (14)	0.0108 (4)
C7	0.10106 (14)	0.12224 (17)	0.93712 (14)	0.0117 (4)
H7	0.1100	0.2097	0.9683	0.014*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.01160 (18)	0.00978 (17)	0.01056 (18)	0.000	−0.00259 (12)	0.000
O1	0.0113 (7)	0.0133 (7)	0.0177 (7)	0.0017 (5)	−0.0029 (5)	−0.0029 (5)
O2	0.0122 (6)	0.0148 (7)	0.0115 (7)	0.0004 (5)	−0.0030 (5)	−0.0024 (5)
O3	0.0155 (7)	0.0126 (6)	0.0151 (7)	−0.0005 (5)	−0.0059 (5)	0.0034 (5)
O4	0.0203 (7)	0.0133 (7)	0.0156 (7)	0.0013 (5)	−0.0064 (6)	−0.0043 (5)
O5	0.0286 (9)	0.0212 (8)	0.0392 (10)	0.0123 (6)	−0.0167 (7)	−0.0135 (7)
N1	0.0109 (8)	0.0106 (8)	0.0103 (8)	−0.0013 (5)	−0.0011 (6)	0.0005 (6)
C1	0.0101 (9)	0.0143 (9)	0.0113 (9)	−0.0019 (7)	0.0008 (7)	0.0014 (7)
C2	0.0108 (8)	0.0148 (9)	0.0092 (9)	−0.0002 (7)	0.0003 (7)	0.0005 (7)
C3	0.0110 (9)	0.0118 (9)	0.0128 (9)	0.0010 (6)	−0.0007 (7)	0.0020 (7)
C4	0.0132 (9)	0.0108 (9)	0.0140 (9)	−0.0006 (7)	0.0011 (7)	−0.0018 (7)
C5	0.0094 (8)	0.0124 (9)	0.0106 (9)	−0.0006 (6)	0.0009 (7)	−0.0007 (7)
C7	0.0110 (9)	0.0124 (9)	0.0118 (9)	−0.0014 (7)	0.0013 (7)	−0.0015 (7)

Geometric parameters (Å, º) top

Ni1—O2ⁱ	2.0622 (12)	O5—H52	0.837 (10)
Ni1—O2	2.0622 (12)	N1—C7	1.337 (2)
Ni1—N1ⁱ	2.0706 (14)	N1—C5	1.356 (2)
Ni1—N1	2.0706 (14)	C1—C2	1.505 (2)
Ni1—O1	2.0782 (13)	C2—C7	1.388 (2)
Ni1—O1ⁱ	2.0782 (13)	C2—C3	1.390 (2)
O1—H11	0.843 (9)	C3—C4	1.385 (2)
O1—H12	0.834 (10)	C3—H3	0.9500
O2—H21	0.833 (10)	C4—C5	1.380 (2)
O2—H22	0.834 (10)	C4—H4	0.9500
O3—C1	1.266 (2)	C5—C5ⁱ	1.486 (3)
O4—C1	1.254 (2)	C7—H7	0.9500
O5—H51	0.834 (10)

O2ⁱ—Ni1—O2	170.87 (7)	C7—N1—C5	118.59 (14)
O2ⁱ—Ni1—N1ⁱ	89.51 (5)	C7—N1—Ni1	124.87 (11)
O2—Ni1—N1ⁱ	97.57 (5)	C5—N1—Ni1	115.66 (12)
O2ⁱ—Ni1—N1	97.57 (5)	O4—C1—O3	124.20 (16)
O2—Ni1—N1	89.51 (5)	O4—C1—C2	117.49 (15)
N1ⁱ—Ni1—N1	78.63 (8)	O3—C1—C2	118.27 (15)
O2ⁱ—Ni1—O1	84.53 (5)	C7—C2—C3	117.82 (16)
O2—Ni1—O1	89.21 (5)	C7—C2—C1	119.58 (15)
N1ⁱ—Ni1—O1	170.17 (6)	C3—C2—C1	122.59 (15)
N1—Ni1—O1	94.39 (5)	C4—C3—C2	119.54 (15)
O2ⁱ—Ni1—O1ⁱ	89.21 (5)	C4—C3—H3	120.2
O2—Ni1—O1ⁱ	84.53 (5)	C2—C3—H3	120.2
N1ⁱ—Ni1—O1ⁱ	94.39 (5)	C5—C4—C3	119.24 (16)
N1—Ni1—O1ⁱ	170.17 (6)	C5—C4—H4	120.4
O1—Ni1—O1ⁱ	93.34 (7)	C3—C4—H4	120.4
Ni1—O1—H11	121.0 (15)	N1—C5—C4	121.70 (16)
Ni1—O1—H12	106.4 (18)	N1—C5—C5ⁱ	114.53 (10)
H11—O1—H12	108 (2)	C4—C5—C5ⁱ	123.75 (10)
Ni1—O2—H21	109.3 (17)	N1—C7—C2	123.09 (15)
Ni1—O2—H22	119.7 (19)	N1—C7—H7	118.5
H21—O2—H22	109 (2)	C2—C7—H7	118.5
H51—O5—H52	104 (3)

O2ⁱ—Ni1—N1—C7	−99.70 (14)	C7—C2—C3—C4	1.0 (3)
O2—Ni1—N1—C7	74.51 (14)	C1—C2—C3—C4	−177.65 (16)
N1ⁱ—Ni1—N1—C7	172.33 (18)	C2—C3—C4—C5	0.2 (3)
O1—Ni1—N1—C7	−14.65 (15)	C7—N1—C5—C4	0.2 (3)
O1ⁱ—Ni1—N1—C7	127.1 (3)	Ni1—N1—C5—C4	169.99 (14)
O2ⁱ—Ni1—N1—C5	91.22 (12)	C7—N1—C5—C5ⁱ	−178.46 (17)
O2—Ni1—N1—C5	−94.57 (12)	Ni1—N1—C5—C5ⁱ	−8.7 (2)
N1ⁱ—Ni1—N1—C5	3.25 (9)	C3—C4—C5—N1	−0.9 (3)
O1—Ni1—N1—C5	176.26 (12)	C3—C4—C5—C5ⁱ	177.6 (2)
O1ⁱ—Ni1—N1—C5	−42.0 (4)	C5—N1—C7—C2	1.2 (3)
O4—C1—C2—C7	4.6 (3)	Ni1—N1—C7—C2	−167.62 (13)
O3—C1—C2—C7	−173.22 (16)	C3—C2—C7—N1	−1.8 (3)
O4—C1—C2—C3	−176.75 (16)	C1—C2—C7—N1	176.94 (15)
O3—C1—C2—C3	5.4 (3)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H52···O3ⁱⁱ	0.84 (1)	2.18 (2)	2.9566 (19)	155 (3)
O2—H22···O3ⁱⁱⁱ	0.83 (1)	1.92 (1)	2.7410 (18)	168 (3)
O5—H51···O4^iv	0.83 (1)	1.91 (1)	2.7286 (19)	166 (2)
O2—H21···O4^v	0.83 (1)	1.85 (1)	2.6831 (17)	175 (2)
O1—H11···O4^v	0.84 (1)	2.65 (2)	3.1740 (18)	122 (2)
O1—H11···O3^v	0.84 (1)	2.10 (1)	2.9386 (18)	176 (2)
O1—H12···O5	0.83 (1)	1.86 (1)	2.688 (2)	171 (3)

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

Experimental details

Crystal data
Chemical formula	[Ni(C₁₂H₆N₂O₄)(H₂O)₄]·2H₂O
M_r	408.97
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	120
a, b, c (Å)	12.4787 (2), 9.8152 (2), 12.6533 (2)
β (°)	92.107 (2)
V (Å³)	1548.74 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.31
Crystal size (mm)	0.18 × 0.16 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.730, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections	8276, 1691, 1379
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.065, 0.98
No. of reflections	1691
No. of parameters	138
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.33

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H52···O3ⁱ	0.837 (10)	2.178 (16)	2.9566 (19)	155 (3)
O2—H22···O3ⁱⁱ	0.834 (10)	1.921 (12)	2.7410 (18)	168 (3)
O5—H51···O4ⁱⁱⁱ	0.834 (10)	1.913 (11)	2.7286 (19)	166 (2)
O2—H21···O4^iv	0.833 (10)	1.852 (10)	2.6831 (17)	175 (2)
O1—H11···O4^iv	0.843 (9)	2.650 (17)	3.1740 (18)	121.6 (16)
O1—H11···O3^iv	0.843 (9)	2.097 (10)	2.9386 (18)	175.9 (19)
O1—H12···O5	0.834 (10)	1.861 (11)	2.688 (2)	171 (3)

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

Acknowledgements

The author thanks the financial support of Natural Foundation of Heilongjiang Province.

References

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