Poly[diaqua-bis-(μ-4,4'-bipyridine-κ(2) N:N')bis-(ethane-1,2-diol-κO)bis(μ-sulfato-κ(2) O:O')dicobalt(II)].

In the title compound, [Co2(SO4)2(C10H8N2)2(C2H6O2)2(H2O)2] n , there are two crystallographically independent Co(II) ions, each of which lies on a twofold rotation axis and has a slightly distorted octa-hedral environment. One Co(II) ion is coordinated by two N atoms from two bridging 4,4'-bipyridine (4,4'-bipy) ligands, two O atoms from two sulfate ions and two O atoms from aqua ligands. The second Co(II) ion is similar but with ethane-1,2-diol ligands in place of water mol-ecules. The sulfate anions act as bridging ligands to link two adjacent Co(II) ions together, leading to the formation of linear ⋯Co1Co2Co1Co2⋯chains along the a axis. Adjacent chains are further bridged by 4,4'-bipy ligands, which are also located on the twofold rotation axis, resulting in a two-dimensional layered polymer extending parallel to (001). In the crystal, the layers are linked by extensive O-H⋯O hydrogen-bonding inter-actions involving the O atoms of the water mol-ecules and ethane-1,2-diol mol-ecules, resulting in a three-dimensional supra-molecular network.

Related literature

For isostructural compounds, see: Zhong et al. (2011 ▶); Zhong (2013 ▶). For metal complexes with the 4,4′-bipyridine ligand, see: Tong & Chen (2000 ▶); Croitor et al. (2011 ▶); Lu et al. (2006 ▶, 1998 ▶); Luachan et al. (2007 ▶); Prior et al. (2011 ▶); Zhong & Qian (2012 ▶). For background to coordination polymers, see: Cui et al. (2002 ▶); Sarma et al. (2009 ▶); Zhang et al. (2010 ▶).

Experimental

Crystal data

[Co2(SO4)2(C10H8N2)2(C2H6O2)2(H2O)2]

M = 782.53

Monoclinic,

a = 11.124 (2) Å

b = 22.792 (5) Å

c = 12.066 (2) Å

β = 95.51 (3)°

V = 3045.2 (11) Å3

Z = 4

Mo Kα radiation

μ = 1.30 mm−1

T = 223 K

0.35 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury CCD diffractometer

Absorption correction: multi-scan (REQAB; Jacobson, 1998 ▶) T min = 0.722, T max = 1.000

8573 measured reflections

3453 independent reflections

3047 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.078

S = 1.05

3453 reflections

214 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.44 e Å−3

Δρmin = −0.49 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813006685/mw2105sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813006685/mw2105Isup2.hkl

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

[Co2(SO4)2(C10H8N2)2(C2H6O2)2(H2O)2]	F(000) = 1608
Mr = 782.53	Dx = 1.707 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C2yc	Cell parameters from 6960 reflections
a = 11.124 (2) Å	θ = 3.3–27.5°
b = 22.792 (5) Å	µ = 1.30 mm−1
c = 12.066 (2) Å	T = 223 K
β = 95.51 (3)°	Block, pink
V = 3045.2 (11) Å3	0.35 × 0.25 × 0.20 mm
Z = 4

Rigaku Mercury CCD diffractometer	3453 independent reflections
Radiation source: fine-focus sealed tube	3047 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 28.5714 pixels mm-1	θmax = 27.5°, θmin = 3.3°
ω scans	h = −12→14
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −24→29
Tmin = 0.722, Tmax = 1.000	l = −15→15
8573 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029	H-atom parameters constrained
wR(F2) = 0.078	w = 1/[σ2(Fo2) + (0.0484P)2 + 0.1682P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3453 reflections	Δρmax = 0.44 e Å−3
214 parameters	Δρmin = −0.49 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0044 (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
Co1	0.0000	0.379656 (12)	0.7500	0.01469 (10)
Co2	0.5000	0.378829 (12)	0.7500	0.01552 (10)
S1	0.26448 (3)	0.397753 (16)	0.89235 (3)	0.01772 (11)
O1	0.38920 (10)	0.37753 (4)	0.88224 (9)	0.0201 (2)
O1W	0.02400 (11)	0.37527 (4)	0.57750 (10)	0.0236 (3)
H1WA	0.0685	0.3970	0.5413	0.035*
H1WB	−0.0438	0.3770	0.5386	0.035*
O2	0.18890 (10)	0.37997 (5)	0.78736 (9)	0.0200 (2)
O3	0.21712 (11)	0.36754 (6)	0.98602 (10)	0.0294 (3)
O4	0.26137 (11)	0.46083 (5)	0.90508 (12)	0.0374 (3)
O5	0.34406 (10)	0.37517 (5)	0.63828 (10)	0.0242 (3)
H5	0.2817	0.3772	0.6691	0.036*
O6	0.19241 (10)	0.43332 (5)	0.47373 (10)	0.0309 (3)
H6A	0.2014	0.4678	0.4567	0.046*
N1	0.0000	0.47277 (8)	0.7500	0.0187 (4)
N2	0.0000	0.28541 (8)	0.7500	0.0189 (4)
N3	0.5000	0.47291 (8)	0.7500	0.0179 (4)
N4	0.5000	0.28432 (8)	0.7500	0.0215 (4)
C1	0.07997 (14)	0.50339 (7)	0.69724 (13)	0.0215 (3)
H1A	0.1369	0.4829	0.6609	0.026*
C2	0.08205 (14)	0.56396 (7)	0.69408 (13)	0.0211 (3)
H2A	0.1381	0.5833	0.6547	0.025*
C3	0.0000	0.59596 (10)	0.7500	0.0192 (4)
C4	0.06167 (15)	0.25465 (7)	0.83143 (14)	0.0239 (3)
H4A	0.1053	0.2751	0.8886	0.029*
C5	0.06372 (15)	0.19388 (7)	0.83470 (14)	0.0234 (3)
H5A	0.1075	0.1746	0.8933	0.028*
C6	0.0000	0.16175 (9)	0.7500	0.0179 (4)
C7	0.56963 (15)	0.50386 (7)	0.82523 (14)	0.0269 (4)
H7A	0.6188	0.4834	0.8787	0.032*
C8	0.57272 (15)	0.56448 (7)	0.82805 (14)	0.0260 (4)
H8A	0.6234	0.5837	0.8821	0.031*
C9	0.5000	0.59664 (9)	0.7500	0.0170 (4)
C10	0.41224 (18)	0.25359 (8)	0.78999 (19)	0.0387 (5)
H10A	0.3495	0.2740	0.8182	0.046*
C11	0.40926 (17)	0.19292 (8)	0.79184 (18)	0.0388 (5)
H11A	0.3459	0.1737	0.8214	0.047*
C12	0.5000	0.16078 (10)	0.7500	0.0204 (4)
C14	0.31776 (15)	0.35169 (8)	0.52895 (14)	0.0269 (4)
H14A	0.2479	0.3261	0.5275	0.032*
H14B	0.3857	0.3285	0.5093	0.032*
C15	0.29304 (16)	0.40015 (8)	0.44611 (14)	0.0293 (4)
H15A	0.3633	0.4253	0.4464	0.035*
H15B	0.2765	0.3838	0.3720	0.035*

	U11	U22	U33	U12	U13	U23
Co1	0.01344 (16)	0.01259 (15)	0.01800 (17)	0.000	0.00121 (11)	0.000
Co2	0.01370 (17)	0.01303 (15)	0.01967 (17)	0.000	0.00082 (12)	0.000
S1	0.01530 (19)	0.0186 (2)	0.0190 (2)	0.00168 (14)	0.00014 (13)	−0.00353 (14)
O1	0.0145 (5)	0.0238 (6)	0.0218 (6)	0.0020 (4)	0.0012 (4)	−0.0004 (4)
O1W	0.0201 (6)	0.0301 (6)	0.0209 (6)	−0.0032 (5)	0.0029 (5)	0.0025 (4)
O2	0.0147 (5)	0.0267 (6)	0.0185 (6)	−0.0003 (4)	0.0009 (4)	−0.0023 (4)
O3	0.0198 (6)	0.0491 (8)	0.0196 (6)	−0.0006 (5)	0.0031 (5)	0.0040 (5)
O4	0.0347 (7)	0.0207 (6)	0.0548 (9)	0.0068 (5)	−0.0059 (6)	−0.0131 (6)
O5	0.0176 (6)	0.0351 (7)	0.0198 (6)	0.0006 (5)	0.0016 (5)	−0.0034 (5)
O6	0.0283 (6)	0.0273 (6)	0.0380 (7)	0.0006 (5)	0.0080 (5)	0.0119 (5)
N1	0.0192 (9)	0.0150 (8)	0.0215 (10)	0.000	0.0003 (7)	0.000
N2	0.0194 (9)	0.0147 (9)	0.0221 (10)	0.000	−0.0002 (7)	0.000
N3	0.0175 (9)	0.0147 (8)	0.0214 (10)	0.000	0.0016 (7)	0.000
N4	0.0212 (9)	0.0140 (9)	0.0295 (11)	0.000	0.0036 (8)	0.000
C1	0.0209 (7)	0.0184 (7)	0.0258 (8)	0.0009 (6)	0.0046 (6)	−0.0005 (6)
C2	0.0216 (7)	0.0176 (7)	0.0247 (8)	−0.0007 (6)	0.0058 (6)	0.0016 (6)
C3	0.0212 (11)	0.0161 (10)	0.0199 (11)	0.000	0.0000 (8)	0.000
C4	0.0271 (8)	0.0184 (7)	0.0245 (8)	0.0006 (7)	−0.0055 (7)	−0.0017 (6)
C5	0.0279 (8)	0.0182 (8)	0.0224 (8)	0.0011 (7)	−0.0063 (6)	0.0007 (6)
C6	0.0171 (10)	0.0174 (10)	0.0193 (11)	0.000	0.0024 (8)	0.000
C7	0.0312 (9)	0.0179 (8)	0.0292 (9)	0.0020 (7)	−0.0097 (7)	0.0015 (7)
C8	0.0314 (9)	0.0183 (8)	0.0258 (9)	−0.0008 (7)	−0.0099 (7)	−0.0019 (6)
C9	0.0170 (10)	0.0146 (10)	0.0198 (11)	0.000	0.0034 (8)	0.000
C10	0.0356 (10)	0.0181 (8)	0.0670 (14)	0.0013 (8)	0.0280 (10)	−0.0010 (8)
C11	0.0358 (10)	0.0178 (8)	0.0679 (14)	−0.0026 (8)	0.0314 (10)	−0.0002 (8)
C12	0.0217 (11)	0.0164 (10)	0.0229 (11)	0.000	0.0010 (9)	0.000
C14	0.0271 (8)	0.0273 (9)	0.0258 (9)	0.0018 (7)	0.0009 (7)	−0.0082 (7)
C15	0.0283 (9)	0.0386 (10)	0.0219 (9)	−0.0008 (8)	0.0072 (7)	0.0001 (7)

Co1—O2	2.1064 (12)	C1—C2	1.381 (2)
Co1—O2i	2.1064 (12)	C1—H1A	0.9300
Co1—N1	2.1223 (19)	C2—C3	1.3924 (19)
Co1—O1Wi	2.1262 (12)	C2—H2A	0.9300
Co1—O1W	2.1262 (12)	C3—C2i	1.392 (2)
Co1—N2	2.1480 (19)	C3—C12iii	1.477 (3)
Co2—O5	2.0938 (13)	C4—C5	1.386 (2)
Co2—O5ii	2.0938 (13)	C4—H4A	0.9300
Co2—O1	2.1081 (12)	C5—C6	1.3943 (19)
Co2—O1ii	2.1081 (12)	C5—H5A	0.9300
Co2—N3	2.1443 (19)	C6—C5i	1.3943 (19)
Co2—N4	2.1540 (19)	C6—C9iv	1.484 (3)
S1—O4	1.4465 (13)	C7—C8	1.382 (2)
S1—O3	1.4641 (13)	C7—H7A	0.9300
S1—O1	1.4781 (12)	C8—C9	1.390 (2)
S1—O2	1.5072 (12)	C8—H8A	0.9300
O1W—H1WA	0.8500	C9—C8ii	1.390 (2)
O1W—H1WB	0.8500	C9—C6v	1.484 (3)
O5—C14	1.428 (2)	C10—C11	1.384 (2)
O5—H5	0.8200	C10—H10A	0.9300
O6—C15	1.417 (2)	C11—C12	1.381 (2)
O6—H6A	0.8200	C11—H11A	0.9300
N1—C1i	1.3389 (18)	C12—C11ii	1.381 (2)
N1—C1	1.3389 (19)	C12—C3vi	1.477 (3)
N2—C4i	1.3409 (19)	C14—C15	1.497 (2)
N2—C4	1.3409 (19)	C14—H14A	0.9700
N3—C7	1.3366 (19)	C14—H14B	0.9700
N3—C7ii	1.3366 (19)	C15—H15A	0.9700
N4—C10	1.329 (2)	C15—H15B	0.9700
N4—C10ii	1.329 (2)
O2—Co1—O2i	179.61 (6)	C7ii—N3—Co2	121.85 (10)
O2—Co1—N1	89.80 (3)	C10—N4—C10ii	116.4 (2)
O2i—Co1—N1	89.80 (3)	C10—N4—Co2	121.80 (11)
O2—Co1—O1Wi	90.41 (5)	C10ii—N4—Co2	121.80 (11)
O2i—Co1—O1Wi	89.60 (5)	N1—C1—C2	123.21 (15)
N1—Co1—O1Wi	92.70 (3)	N1—C1—H1A	118.4
O2—Co1—O1W	89.60 (5)	C2—C1—H1A	118.4
O2i—Co1—O1W	90.41 (5)	C1—C2—C3	119.78 (15)
N1—Co1—O1W	92.70 (3)	C1—C2—H2A	120.1
O1Wi—Co1—O1W	174.60 (6)	C3—C2—H2A	120.1
O2—Co1—N2	90.20 (3)	C2—C3—C2i	116.8 (2)
O2i—Co1—N2	90.20 (3)	C2—C3—C12iii	121.59 (10)
N1—Co1—N2	180.0	C2i—C3—C12iii	121.59 (10)
O1Wi—Co1—N2	87.30 (3)	N2—C4—C5	123.32 (15)
O1W—Co1—N2	87.30 (3)	N2—C4—H4A	118.3
O5—Co2—O5ii	175.44 (6)	C5—C4—H4A	118.3
O5—Co2—O1	88.75 (5)	C4—C5—C6	119.89 (15)
O5ii—Co2—O1	91.18 (5)	C4—C5—H5A	120.1
O5—Co2—O1ii	91.18 (5)	C6—C5—H5A	120.1
O5ii—Co2—O1ii	88.75 (5)	C5—C6—C5i	116.6 (2)
O1—Co2—O1ii	178.39 (6)	C5—C6—C9iv	121.68 (10)
O5—Co2—N3	92.28 (3)	C5i—C6—C9iv	121.68 (10)
O5ii—Co2—N3	92.28 (3)	N3—C7—C8	123.75 (15)
O1—Co2—N3	90.81 (3)	N3—C7—H7A	118.1
O1ii—Co2—N3	90.81 (3)	C8—C7—H7A	118.1
O5—Co2—N4	87.72 (3)	C7—C8—C9	119.93 (15)
O5ii—Co2—N4	87.72 (3)	C7—C8—H8A	120.0
O1—Co2—N4	89.19 (3)	C9—C8—H8A	120.0
O1ii—Co2—N4	89.19 (3)	C8ii—C9—C8	116.4 (2)
N3—Co2—N4	180.0	C8ii—C9—C6v	121.82 (10)
O4—S1—O3	111.80 (8)	C8—C9—C6v	121.82 (10)
O4—S1—O1	110.55 (7)	N4—C10—C11	123.51 (17)
O3—S1—O1	109.10 (7)	N4—C10—H10A	118.2
O4—S1—O2	109.84 (7)	C11—C10—H10A	118.2
O3—S1—O2	108.02 (7)	C12—C11—C10	120.31 (17)
O1—S1—O2	107.40 (7)	C12—C11—H11A	119.8
S1—O1—Co2	132.83 (7)	C10—C11—H11A	119.8
Co1—O1W—H1WA	127.6	C11ii—C12—C11	116.0 (2)
Co1—O1W—H1WB	110.5	C11ii—C12—C3vi	122.02 (11)
H1WA—O1W—H1WB	102.6	C11—C12—C3vi	122.02 (11)
S1—O2—Co1	130.19 (7)	O5—C14—C15	110.40 (14)
C14—O5—Co2	133.90 (10)	O5—C14—H14A	109.6
C14—O5—H5	109.5	C15—C14—H14A	109.6
Co2—O5—H5	113.0	O5—C14—H14B	109.6
C15—O6—H6A	109.5	C15—C14—H14B	109.6
C1i—N1—C1	117.17 (19)	H14A—C14—H14B	108.1
C1i—N1—Co1	121.41 (10)	O6—C15—C14	109.59 (14)
C1—N1—Co1	121.41 (10)	O6—C15—H15A	109.8
C4i—N2—C4	116.96 (19)	C14—C15—H15A	109.8
C4i—N2—Co1	121.52 (10)	O6—C15—H15B	109.8
C4—N2—Co1	121.52 (10)	C14—C15—H15B	109.8
C7—N3—C7ii	116.29 (19)	H15A—C15—H15B	108.2
C7—N3—Co2	121.85 (10)
O4—S1—O1—Co2	−77.34 (11)	O1—Co2—N3—C7	78.37 (10)
O3—S1—O1—Co2	159.32 (8)	O1ii—Co2—N3—C7	−101.63 (10)
O2—S1—O1—Co2	42.47 (10)	O5—Co2—N3—C7ii	−12.85 (10)
O5—Co2—O1—S1	−28.26 (9)	O5ii—Co2—N3—C7ii	167.15 (10)
O5ii—Co2—O1—S1	156.30 (9)	O1—Co2—N3—C7ii	−101.63 (10)
N3—Co2—O1—S1	64.00 (8)	O1ii—Co2—N3—C7ii	78.37 (10)
N4—Co2—O1—S1	−116.00 (8)	O5—Co2—N4—C10	−65.05 (12)
O4—S1—O2—Co1	−71.63 (10)	O5ii—Co2—N4—C10	114.95 (12)
O3—S1—O2—Co1	50.55 (10)	O1—Co2—N4—C10	23.74 (12)
O1—S1—O2—Co1	168.10 (7)	O1ii—Co2—N4—C10	−156.26 (12)
N1—Co1—O2—S1	69.57 (8)	O5—Co2—N4—C10ii	114.95 (12)
O1Wi—Co1—O2—S1	−23.13 (9)	O5ii—Co2—N4—C10ii	−65.05 (12)
O1W—Co1—O2—S1	162.27 (8)	O1—Co2—N4—C10ii	−156.26 (12)
N2—Co1—O2—S1	−110.43 (8)	O1ii—Co2—N4—C10ii	23.74 (12)
O1—Co2—O5—C14	−150.40 (14)	C1i—N1—C1—C2	−0.83 (11)
O1ii—Co2—O5—C14	27.99 (14)	Co1—N1—C1—C2	179.17 (11)
N3—Co2—O5—C14	118.84 (14)	N1—C1—C2—C3	1.6 (2)
N4—Co2—O5—C14	−61.16 (14)	C1—C2—C3—C2i	−0.77 (10)
O2—Co1—N1—C1i	−134.02 (9)	C1—C2—C3—C12iii	179.23 (10)
O2i—Co1—N1—C1i	45.98 (9)	C4i—N2—C4—C5	−0.20 (12)
O1Wi—Co1—N1—C1i	−43.61 (9)	Co1—N2—C4—C5	179.80 (12)
O1W—Co1—N1—C1i	136.39 (9)	N2—C4—C5—C6	0.4 (2)
O2—Co1—N1—C1	45.98 (9)	C4—C5—C6—C5i	−0.19 (11)
O2i—Co1—N1—C1	−134.02 (9)	C4—C5—C6—C9iv	179.81 (11)
O1Wi—Co1—N1—C1	136.39 (9)	C7ii—N3—C7—C8	−0.21 (13)
O1W—Co1—N1—C1	−43.61 (9)	Co2—N3—C7—C8	179.79 (13)
O2—Co1—N2—C4i	−133.47 (9)	N3—C7—C8—C9	0.4 (3)
O2i—Co1—N2—C4i	46.53 (9)	C7—C8—C9—C8ii	−0.19 (12)
O1Wi—Co1—N2—C4i	136.13 (9)	C7—C8—C9—C6v	179.81 (12)
O1W—Co1—N2—C4i	−43.87 (9)	C10ii—N4—C10—C11	0.26 (17)
O2—Co1—N2—C4	46.53 (9)	Co2—N4—C10—C11	−179.74 (17)
O2i—Co1—N2—C4	−133.47 (9)	N4—C10—C11—C12	−0.5 (3)
O1Wi—Co1—N2—C4	−43.87 (9)	C10—C11—C12—C11ii	0.24 (15)
O1W—Co1—N2—C4	136.13 (9)	C10—C11—C12—C3vi	−179.76 (15)
O5—Co2—N3—C7	167.15 (10)	Co2—O5—C14—C15	−111.40 (14)
O5ii—Co2—N3—C7	−12.85 (10)	O5—C14—C15—O6	−60.27 (18)

D—H···A	D—H	H···A	D···A	D—H···A
O6—H6A···O4vii	0.82	1.89	2.6866 (17)	165
O1W—H1WA···O6	0.85	1.86	2.6980 (17)	168
O1W—H1WB···O3i	0.85	1.93	2.7237 (18)	154
O5—H5···O2	0.82	1.84	2.6122 (17)	156

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H6A⋯O4i	0.82	1.89	2.6866 (17)	165
O1W—H1WA⋯O6	0.85	1.86	2.6980 (17)	168
O1W—H1WB⋯O3ii	0.85	1.93	2.7237 (18)	154
O5—H5⋯O2	0.82	1.84	2.6122 (17)	156

Symmetry codes: (i) ; (ii) .