Tetra-aqua-(2,2'-bipyridine-κ²N,N')nickel(II) sulfate.

The asymmetric unit of the title complex, [Ni(C₁₀H₈N₂)(H₂O)₄]SO₄, consists of a complex [Ni(bipy)(H₂O)₄]²⁺ cation (bipy = 2,2'-bipyridine) and a non-coordinating [SO₄]²⁻ anion. The Ni(II) atom is six-coordinated in a distorted octa-hedral geometry defined by the two N atoms of the bipy ligand and four water O atoms. The crystal structure contains extensive classical O-H⋯O hydrogen bonds, which link the ions into a two-dimensional array in the ab plane. Layers are connected into a three-dimensional supra-molecular structure by C-H⋯O inter-actions.

Related literature

For the structures and properties of coordination complexes with bipy as a ligand, see: Graaf & Sousa (2010 ▶); Baruah et al. (2007 ▶); Schubert & Eschbaumer (2002 ▶); Harvey et al. (1999 ▶); Damrauer et al. (1997 ▶); Healy et al. (1984 ▶)

Experimental

Crystal data

[Ni(C10H8N2)(H2O)4]SO4

M = 383.02

Orthorhombic,

a = 12.3035 (7) Å

b = 11.6560 (7) Å

c = 20.7112 (10) Å

V = 2970.2 (3) Å3

Z = 8

Mo Kα radiation

μ = 1.49 mm−1

T = 298 K

0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD area detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.707, T max = 0.755

11218 measured reflections

3626 independent reflections

3024 reflections with I > 2σ(I)

R int = 0.045

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.092

S = 1.07

3626 reflections

231 parameters

12 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.58 e Å−3

Δρmin = −0.70 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681202538X/tk5105sup1.cif

Supplementary material file. DOI: 10.1107/S160053681202538X/tk5105Isup2.cdx

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681202538X/tk5105Isup3.hkl

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

[Ni(C10H8N2)(H2O)4]SO4	F(000) = 1584
Mr = 383.02	Dx = 1.713 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 12.3035 (7) Å	µ = 1.49 mm−1
b = 11.6560 (7) Å	T = 298 K
c = 20.7112 (10) Å	Block, blue
V = 2970.2 (3) Å3	0.25 × 0.20 × 0.20 mm
Z = 8

Bruker SMART APEX CCD area detector diffractometer	3626 independent reflections
Radiation source: fine-focus sealed tube	3024 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
Detector resolution: 8 pixels mm-1	θmax = 30.5°, θmin = 2.0°
ω and φ scans	h = 0→17
Absorption correction: multi-scan (SADABS; Bruker, 2003)	k = 0→16
Tmin = 0.707, Tmax = 0.755	l = 0→19
11218 measured reflections

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0322P)2 + 3.2213P] where P = (Fo2 + 2Fc2)/3
3626 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.58 e Å−3
12 restraints	Δρmin = −0.70 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	0.05162 (2)	0.72886 (2)	0.655841 (16)	0.01042 (10)
S1	−0.25226 (4)	0.98567 (4)	0.69683 (3)	0.01034 (14)
O1	−0.10901 (13)	0.73405 (14)	0.62681 (9)	0.0138 (4)
N1	0.07768 (16)	0.56644 (16)	0.61777 (11)	0.0128 (4)
C1	0.0689 (2)	0.4662 (2)	0.64883 (14)	0.0162 (5)
H1	0.0453	0.4665	0.6915	0.019*
O2	0.20770 (14)	0.72708 (14)	0.69286 (9)	0.0133 (4)
N2	0.09637 (16)	0.77000 (16)	0.56277 (11)	0.0134 (4)
C2	0.0934 (2)	0.3618 (2)	0.62007 (14)	0.0184 (6)
H2	0.0871	0.2937	0.6431	0.022*
O3	−0.00380 (14)	0.67614 (14)	0.74609 (9)	0.0150 (4)
C3	0.1271 (2)	0.3612 (2)	0.55698 (14)	0.0208 (6)
H3	0.1440	0.2923	0.5366	0.025*
O4	0.04198 (14)	0.89878 (14)	0.68080 (10)	0.0170 (4)
C4	0.1357 (2)	0.4641 (2)	0.52378 (14)	0.0178 (5)
H4	0.1576	0.4651	0.4808	0.021*
O5	−0.25137 (14)	0.85952 (13)	0.70127 (9)	0.0172 (4)
C5	0.11122 (18)	0.56556 (19)	0.55584 (13)	0.0128 (5)
O6	−0.13912 (13)	1.02854 (14)	0.69611 (8)	0.0142 (4)
C6	0.11779 (18)	0.67945 (19)	0.52374 (13)	0.0133 (5)
O7	−0.30835 (14)	1.02193 (14)	0.63785 (9)	0.0157 (4)
C7	0.1406 (2)	0.6931 (2)	0.45869 (14)	0.0185 (6)
H7	0.1578	0.6300	0.4332	0.022*
O8	−0.30946 (13)	1.03373 (13)	0.75434 (8)	0.0137 (4)
C8	0.1376 (2)	0.8021 (2)	0.43219 (14)	0.0201 (6)
H8	0.1508	0.8130	0.3884	0.024*
C9	0.1145 (2)	0.8947 (2)	0.47183 (14)	0.0214 (6)
H9	0.1122	0.9687	0.4552	0.026*
C10	0.0950 (2)	0.8751 (2)	0.53642 (14)	0.0174 (6)
H10	0.0801	0.9375	0.5629	0.021*
H1A	−0.134 (3)	0.6650 (17)	0.6270 (18)	0.048 (11)*
H2A	0.233 (3)	0.6601 (17)	0.7021 (14)	0.030 (9)*
H3A	−0.0628 (19)	0.636 (3)	0.7451 (17)	0.042 (11)*
H4A	0.092 (2)	0.937 (3)	0.7005 (15)	0.040 (10)*
H1B	−0.152 (3)	0.778 (2)	0.6482 (16)	0.041 (11)*
H2B	0.220 (3)	0.773 (2)	0.7246 (14)	0.048 (12)*
H3B	0.046 (3)	0.639 (3)	0.766 (2)	0.071 (15)*
H4B	−0.0191 (18)	0.934 (3)	0.6840 (17)	0.039 (10)*

	U11	U22	U33	U12	U13	U23
Ni1	0.00799 (13)	0.01272 (14)	0.0105 (3)	0.00003 (10)	0.00070 (11)	−0.00085 (11)
S1	0.0079 (2)	0.0117 (2)	0.0114 (4)	0.00052 (17)	0.0005 (2)	−0.0002 (2)
O1	0.0087 (7)	0.0155 (7)	0.0173 (12)	−0.0007 (6)	−0.0004 (7)	−0.0022 (7)
N1	0.0111 (9)	0.0163 (9)	0.0109 (15)	−0.0006 (7)	−0.0008 (8)	−0.0005 (8)
C1	0.0152 (11)	0.0184 (11)	0.0149 (18)	−0.0010 (9)	−0.0010 (9)	0.0009 (9)
O2	0.0111 (7)	0.0148 (7)	0.0139 (12)	0.0004 (6)	−0.0015 (7)	−0.0002 (7)
N2	0.0094 (8)	0.0162 (9)	0.0146 (14)	0.0007 (7)	0.0011 (8)	−0.0004 (8)
C2	0.0163 (11)	0.0163 (10)	0.0227 (19)	0.0002 (9)	−0.0029 (10)	0.0012 (10)
O3	0.0112 (8)	0.0205 (8)	0.0132 (12)	−0.0009 (6)	0.0008 (7)	0.0023 (7)
C3	0.0189 (12)	0.0195 (11)	0.024 (2)	0.0035 (9)	−0.0010 (10)	−0.0055 (10)
O4	0.0098 (8)	0.0171 (8)	0.0241 (13)	0.0013 (6)	−0.0022 (7)	−0.0062 (7)
C4	0.0171 (11)	0.0221 (11)	0.0143 (18)	0.0030 (9)	0.0027 (10)	−0.0046 (10)
O5	0.0198 (9)	0.0115 (7)	0.0204 (12)	0.0015 (6)	0.0071 (7)	0.0001 (7)
C5	0.0080 (9)	0.0179 (10)	0.0126 (17)	−0.0005 (8)	0.0000 (9)	−0.0010 (9)
O6	0.0083 (7)	0.0191 (8)	0.0153 (12)	−0.0020 (6)	0.0005 (6)	−0.0008 (7)
C6	0.0091 (9)	0.0172 (10)	0.0137 (17)	0.0006 (8)	0.0020 (8)	0.0011 (9)
O7	0.0159 (8)	0.0187 (8)	0.0125 (11)	0.0025 (6)	−0.0041 (7)	−0.0019 (7)
C7	0.0149 (11)	0.0250 (11)	0.0157 (19)	−0.0006 (9)	0.0013 (10)	−0.0012 (10)
O8	0.0115 (7)	0.0159 (7)	0.0137 (12)	−0.0003 (6)	0.0025 (7)	−0.0005 (6)
C8	0.0160 (11)	0.0304 (13)	0.0139 (18)	−0.0021 (10)	0.0033 (10)	0.0049 (11)
C9	0.0161 (11)	0.0243 (12)	0.024 (2)	−0.0006 (9)	0.0015 (10)	0.0105 (11)
C10	0.0154 (11)	0.0166 (10)	0.0201 (19)	0.0028 (9)	0.0053 (10)	0.0027 (10)

Ni1—O4	2.0504 (17)	C2—C3	1.371 (4)
Ni1—N2	2.061 (2)	C2—H2	0.9300
Ni1—O1	2.0667 (17)	O3—H3A	0.864 (18)
Ni1—O2	2.0679 (17)	O3—H3B	0.862 (18)
Ni1—N1	2.0757 (19)	C3—C4	1.387 (4)
Ni1—O3	2.0824 (19)	C3—H3	0.9300
S1—O7	1.4653 (19)	O4—H4A	0.861 (18)
S1—O5	1.4732 (16)	O4—H4B	0.861 (18)
S1—O6	1.4791 (17)	C4—C5	1.390 (3)
S1—O8	1.4926 (18)	C4—H4	0.9300
O1—H1A	0.862 (18)	C5—C6	1.487 (3)
O1—H1B	0.862 (18)	C6—C7	1.386 (4)
N1—C1	1.338 (3)	C7—C8	1.384 (4)
N1—C5	1.347 (3)	C7—H7	0.9300
C1—C2	1.388 (3)	C8—C9	1.386 (4)
C1—H1	0.9300	C8—H8	0.9300
O2—H2A	0.862 (17)	C9—C10	1.378 (4)
O2—H2B	0.863 (18)	C9—H9	0.9300
N2—C10	1.341 (3)	C10—H10	0.9300
N2—C6	1.355 (3)
O4—Ni1—N2	91.51 (8)	C6—N2—Ni1	115.37 (16)
O4—Ni1—O1	89.41 (7)	C3—C2—C1	118.7 (2)
N2—Ni1—O1	88.66 (8)	C3—C2—H2	120.7
O4—Ni1—O2	88.28 (7)	C1—C2—H2	120.7
N2—Ni1—O2	95.80 (8)	Ni1—O3—H3A	114 (2)
O1—Ni1—O2	175.03 (8)	Ni1—O3—H3B	111 (3)
O4—Ni1—N1	170.30 (8)	H3A—O3—H3B	109 (3)
N2—Ni1—N1	79.38 (8)	C2—C3—C4	119.4 (2)
O1—Ni1—N1	93.66 (7)	C2—C3—H3	120.3
O2—Ni1—N1	89.32 (7)	C4—C3—H3	120.3
O4—Ni1—O3	92.28 (8)	Ni1—O4—H4A	125 (2)
N2—Ni1—O3	174.58 (7)	Ni1—O4—H4B	122 (2)
O1—Ni1—O3	87.52 (7)	H4A—O4—H4B	110 (3)
O2—Ni1—O3	88.18 (7)	C3—C4—C5	118.9 (3)
N1—Ni1—O3	97.03 (8)	C3—C4—H4	120.6
O7—S1—O5	110.09 (10)	C5—C4—H4	120.6
O7—S1—O6	109.72 (10)	N1—C5—C4	121.9 (2)
O5—S1—O6	109.32 (10)	N1—C5—C6	115.8 (2)
O7—S1—O8	109.57 (10)	C4—C5—C6	122.3 (2)
O5—S1—O8	109.16 (10)	N2—C6—C7	122.0 (2)
O6—S1—O8	108.96 (10)	N2—C6—C5	114.7 (2)
Ni1—O1—H1A	108 (3)	C7—C6—C5	123.3 (2)
Ni1—O1—H1B	117 (3)	C8—C7—C6	119.1 (2)
H1A—O1—H1B	109 (3)	C8—C7—H7	120.5
C1—N1—C5	118.4 (2)	C6—C7—H7	120.5
C1—N1—Ni1	126.97 (18)	C7—C8—C9	119.0 (3)
C5—N1—Ni1	114.57 (15)	C7—C8—H8	120.5
N1—C1—C2	122.8 (3)	C9—C8—H8	120.5
N1—C1—H1	118.6	C10—C9—C8	118.8 (2)
C2—C1—H1	118.6	C10—C9—H9	120.6
Ni1—O2—H2A	115 (2)	C8—C9—H9	120.6
Ni1—O2—H2B	116 (3)	N2—C10—C9	123.0 (2)
H2A—O2—H2B	110 (3)	N2—C10—H10	118.5
C10—N2—C6	118.1 (2)	C9—C10—H10	118.5
C10—N2—Ni1	126.14 (18)
O4—Ni1—N1—C1	158.1 (4)	C1—C2—C3—C4	0.0 (4)
N2—Ni1—N1—C1	178.5 (2)	C2—C3—C4—C5	0.8 (4)
O1—Ni1—N1—C1	−93.6 (2)	C1—N1—C5—C4	0.5 (3)
O2—Ni1—N1—C1	82.5 (2)	Ni1—N1—C5—C4	177.86 (18)
O3—Ni1—N1—C1	−5.6 (2)	C1—N1—C5—C6	179.2 (2)
O4—Ni1—N1—C5	−19.0 (6)	Ni1—N1—C5—C6	−3.5 (2)
N2—Ni1—N1—C5	1.39 (16)	C3—C4—C5—N1	−1.1 (4)
O1—Ni1—N1—C5	89.34 (16)	C3—C4—C5—C6	−179.7 (2)
O2—Ni1—N1—C5	−94.63 (16)	C10—N2—C6—C7	1.7 (3)
O3—Ni1—N1—C5	177.28 (16)	Ni1—N2—C6—C7	174.92 (19)
C5—N1—C1—C2	0.4 (3)	C10—N2—C6—C5	−176.5 (2)
Ni1—N1—C1—C2	−176.60 (18)	Ni1—N2—C6—C5	−3.2 (3)
O4—Ni1—N2—C10	−9.6 (2)	N1—C5—C6—N2	4.5 (3)
O1—Ni1—N2—C10	79.7 (2)	C4—C5—C6—N2	−176.9 (2)
O2—Ni1—N2—C10	−98.1 (2)	N1—C5—C6—C7	−173.6 (2)
N1—Ni1—N2—C10	173.7 (2)	C4—C5—C6—C7	5.0 (4)
O3—Ni1—N2—C10	124.8 (7)	N2—C6—C7—C8	−2.4 (4)
O4—Ni1—N2—C6	177.75 (17)	C5—C6—C7—C8	175.5 (2)
O1—Ni1—N2—C6	−92.87 (17)	C6—C7—C8—C9	1.6 (4)
O2—Ni1—N2—C6	89.33 (17)	C7—C8—C9—C10	−0.2 (4)
N1—Ni1—N2—C6	1.11 (16)	C6—N2—C10—C9	−0.1 (4)
O3—Ni1—N2—C6	−47.8 (8)	Ni1—N2—C10—C9	−172.58 (19)
N1—C1—C2—C3	−0.7 (4)	C8—C9—C10—N2	−0.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···O5	0.86 (2)	1.90 (2)	2.754 (2)	173 (3)
O1—H1A···O7i	0.86 (2)	1.83 (2)	2.683 (2)	173 (4)
O2—H2B···O5ii	0.86 (2)	1.87 (2)	2.728 (2)	174 (3)
O2—H2A···O8iii	0.86 (2)	1.97 (2)	2.800 (2)	162 (3)
O3—H3B···O6iii	0.86 (2)	1.89 (2)	2.736 (2)	168 (4)
O3—H3A···O8i	0.86 (2)	1.98 (2)	2.840 (2)	172 (3)
O4—H4B···O6	0.86 (2)	1.86 (2)	2.712 (2)	172 (3)
O4—H4A···O8ii	0.86 (2)	1.90 (2)	2.760 (2)	174 (3)
C8—H8···O6iv	0.93	2.55	3.310 (3)	139

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O5	0.86 (2)	1.90 (2)	2.754 (2)	173 (3)
O1—H1A⋯O7i	0.86 (2)	1.83 (2)	2.683 (2)	173 (4)
O2—H2B⋯O5ii	0.86 (2)	1.87 (2)	2.728 (2)	174 (3)
O2—H2A⋯O8iii	0.86 (2)	1.97 (2)	2.800 (2)	162 (3)
O3—H3B⋯O6iii	0.86 (2)	1.89 (2)	2.736 (2)	168 (4)
O3—H3A⋯O8i	0.86 (2)	1.98 (2)	2.840 (2)	172 (3)
O4—H4B⋯O6	0.86 (2)	1.86 (2)	2.712 (2)	172 (3)
O4—H4A⋯O8ii	0.86 (2)	1.90 (2)	2.760 (2)	174 (3)
C8—H8⋯O6iv	0.93	2.55	3.310 (3)	139

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .