Tetra-aqua-(2,2'-bipyridine-5,5'-dicarboxyl-ato-κN,N')nickel(II) dihydrate.

In the title compound, [Ni(C(12)H(6)N(2)O(4))(H(2)O)(4)]·2H(2)O, obtained from a basic solution of 2,2'-bipyridine-5,5'-dicarboxyl-ate 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'-dicarboxyl-ate ligand and four aqua O atoms. The N-Ni-N angle is 78.64 (8)°. Weak but significant π-π stacking inter-actions 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 mol-ecules, 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 = 408.97

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.065

S = 0.98

1691 reflections

138 parameters

6 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.33 e Å−3

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 ▶).

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Ni(C12H6N2O4)(H2O)4]·2H2O	F(000) = 848.0
Mr = 408.97	Dx = 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

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

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(Fo2) + (0.0426P)2] where P = (Fo2 + 2Fc2)/3
1691 reflections	(Δ/σ)max = 0.001
138 parameters	Δρmax = 0.44 e Å−3
6 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···O4iv	0.83 (1)	1.91 (1)	2.7286 (19)	166 (2)
O2—H21···O4v	0.83 (1)	1.85 (1)	2.6831 (17)	175 (2)
O1—H11···O4v	0.84 (1)	2.65 (2)	3.1740 (18)	122 (2)
O1—H11···O3v	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)

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⋯O4iv	0.833 (10)	1.852 (10)	2.6831 (17)	175 (2)
O1—H11⋯O4iv	0.843 (9)	2.650 (17)	3.1740 (18)	121.6 (16)
O1—H11⋯O3iv	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) ; (ii) ; (iii) ; (iv) .