Poly[[diaqua-bis-(μ2-4,4'-bipyrid-yl)cobalt(II)] dinitrate tetra-hydrate].

The title compound, {[Co(C10H8N2)2(H2O)2](NO3)2·4H2O} n , (C10H8N2 = 4,4'-bipyridine = 4,4'-bpy) is a layered coordination polymer built up from a cationic square grid extending in (101) enclosing uncoordinating nitrate ions and water mol-ecules. The Co(II) ion has site symmetry 2 and one of the 4,4'-bpy ligands is generated by twofold symmetry [two N atoms and two C atoms lie on the rotation axis and the dihedral angle between the pyridine rings is 45.66 (5)°]. The other 4,4'-bpy ligand is generated by a crystallographic inversion center. The Co(II) ion exhibits a slightly distorted octa-hedral coordination geometry defined by two O atoms of two coordinating water mol-ecules and four N atoms from four bridging 4,4'-bpy ligands. The structure is consolidated by O-H⋯O, C-H⋯O and C-H⋯N hydrogen bonds.

Related literature

For related structures with 4,4′-bpy ligands, see: Aoyagi et al. (2000 ▶); Felloni et al. (2002 ▶); Jin et al. (2006 ▶); Tong et al. (2000 ▶).

Experimental

Crystal data

[Co(C10H8N2)2(H2O)2](NO3)2·4H2O

M = 603.41

Monoclinic,

a = 18.6093 (19) Å

b = 11.5447 (13) Å

c = 12.1216 (13) Å

β = 95.625 (4)°

V = 2591.7 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.74 mm−1

T = 296 K

0.15 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer

18421 measured reflections

3942 independent reflections

3660 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.083

S = 1.05

3942 reflections

198 parameters

9 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.41 e Å−3

Δρmin = −0.49 e Å−3

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 1995 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813005230/hb7035sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813005230/hb7035Isup2.hkl

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

[Co(C10H8N2)2(H2O)2](NO3)2·4H2O	Z = 4
Mr = 603.41	F(000) = 1252
Monoclinic, C2/c	Least Squares Treatment of 25 SET4 setting angles.
Hall symbol: -C 2yc	Dx = 1.546 Mg m−3
a = 18.6093 (19) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5447 (13) Å	µ = 0.74 mm−1
c = 12.1216 (13) Å	T = 296 K
β = 95.625 (4)°	Block, orange
V = 2591.7 (5) Å3	0.15 × 0.12 × 0.10 mm

Bruker APEXII CCD diffractometer	3660 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.016
Graphite monochromator	θmax = 30.5°, θmin = 3.7°
Detector resolution: 18.4 pixels mm-1	h = −26→26
φ and ω scans	k = −16→12
18421 measured reflections	l = −15→17
3942 independent 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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.083	w = 1/[σ2(Fo2) + (0.0411P)2 + 2.4609P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3942 reflections	Δρmax = 0.41 e Å−3
198 parameters	Δρmin = −0.49 e Å−3
9 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0058 (4)

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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	0.50000	0.74238 (2)	0.75000	0.0160 (1)
O1W	0.56526 (5)	0.74192 (8)	0.89887 (8)	0.0261 (3)
N1	0.59538 (5)	0.74697 (8)	0.65303 (8)	0.0194 (3)
N2	0.50000	0.93206 (11)	0.75000	0.0198 (3)
N3	0.50000	1.54917 (12)	0.75000	0.0216 (4)
C1	0.59232 (6)	0.70962 (12)	0.54799 (10)	0.0261 (3)
C2	0.65075 (7)	0.71019 (13)	0.48560 (10)	0.0286 (3)
C3	0.71766 (6)	0.75068 (9)	0.53140 (10)	0.0196 (3)
C4	0.72032 (7)	0.79164 (13)	0.63952 (11)	0.0289 (3)
C5	0.65925 (7)	0.78805 (12)	0.69653 (11)	0.0282 (3)
C6	0.48157 (7)	0.99302 (10)	0.83731 (10)	0.0229 (3)
C7	0.48067 (7)	1.11296 (10)	0.84048 (10)	0.0237 (3)
C8	0.50000	1.17564 (13)	0.75000	0.0189 (4)
C9	0.50000	1.30435 (13)	0.75000	0.0191 (4)
C10	0.55676 (7)	1.36752 (10)	0.71325 (11)	0.0266 (3)
C11	0.55528 (7)	1.48777 (10)	0.71687 (12)	0.0277 (3)
O1	0.73251 (11)	1.0878 (2)	0.67235 (12)	0.0843 (7)
O2	0.67234 (8)	1.07423 (15)	0.81345 (14)	0.0629 (5)
O3	0.77569 (8)	0.99156 (14)	0.81568 (13)	0.0614 (5)
N4	0.72726 (8)	1.05039 (14)	0.76769 (11)	0.0436 (4)
O2W	0.63340 (8)	1.06829 (14)	0.48099 (11)	0.0546 (4)
O3W	0.84438 (9)	1.06853 (16)	0.53876 (15)	0.0701 (6)
H1	0.54840	0.68170	0.51520	0.0310*
H2	0.64530	0.68350	0.41290	0.0340*
H4	0.76320	0.82160	0.67380	0.0350*
H5	0.66290	0.81570	0.76890	0.0340*
H6	0.46880	0.95260	0.89880	0.0280*
H7	0.46720	1.15130	0.90270	0.0280*
H10	0.59550	1.32940	0.68640	0.0320*
H11	0.59480	1.52800	0.69510	0.0330*
H12	0.5930 (7)	0.6840 (9)	0.9229 (13)	0.0240*
H13	0.5878 (8)	0.8051 (9)	0.9250 (13)	0.0240*
H14	0.6676 (7)	1.0786 (14)	0.5353 (10)	0.0240*
H15	0.6542 (8)	1.0272 (13)	0.4316 (10)	0.0240*
H16	0.8124 (7)	1.0682 (15)	0.5868 (10)	0.0240*
H17	0.8192 (8)	1.0679 (15)	0.4727 (8)	0.0240*

	U11	U22	U33	U12	U13	U23
Co1	0.0164 (1)	0.0132 (1)	0.0193 (1)	0.0000	0.0057 (1)	0.0000
O1W	0.0236 (4)	0.0290 (5)	0.0255 (4)	0.0002 (3)	0.0014 (3)	0.0015 (3)
N1	0.0188 (4)	0.0167 (4)	0.0240 (5)	−0.0001 (3)	0.0084 (3)	−0.0002 (3)
N2	0.0233 (6)	0.0136 (5)	0.0232 (6)	0.0000	0.0060 (5)	0.0000
N3	0.0222 (6)	0.0148 (6)	0.0282 (7)	0.0000	0.0046 (5)	0.0000
C1	0.0183 (5)	0.0369 (6)	0.0238 (5)	−0.0031 (4)	0.0053 (4)	−0.0024 (5)
C2	0.0208 (5)	0.0456 (7)	0.0203 (5)	−0.0038 (5)	0.0062 (4)	−0.0054 (5)
C3	0.0175 (5)	0.0210 (5)	0.0215 (5)	−0.0001 (4)	0.0075 (4)	−0.0002 (4)
C4	0.0213 (5)	0.0377 (7)	0.0291 (6)	−0.0080 (5)	0.0095 (4)	−0.0131 (5)
C5	0.0246 (5)	0.0341 (6)	0.0278 (6)	−0.0069 (5)	0.0116 (4)	−0.0125 (5)
C6	0.0321 (6)	0.0160 (5)	0.0219 (5)	−0.0013 (4)	0.0090 (4)	0.0009 (4)
C7	0.0344 (6)	0.0160 (5)	0.0220 (5)	−0.0016 (4)	0.0099 (4)	−0.0022 (4)
C8	0.0210 (6)	0.0135 (6)	0.0227 (7)	0.0000	0.0042 (5)	0.0000
C9	0.0232 (7)	0.0132 (6)	0.0211 (6)	0.0000	0.0032 (5)	0.0000
C10	0.0257 (5)	0.0161 (5)	0.0401 (7)	0.0027 (4)	0.0136 (5)	0.0021 (4)
C11	0.0256 (5)	0.0168 (5)	0.0428 (7)	−0.0001 (4)	0.0133 (5)	0.0036 (5)
O1	0.0952 (13)	0.1202 (16)	0.0372 (7)	−0.0386 (12)	0.0056 (7)	0.0049 (9)
O2	0.0435 (7)	0.0741 (10)	0.0729 (10)	−0.0014 (7)	0.0144 (6)	0.0011 (8)
O3	0.0455 (7)	0.0733 (10)	0.0632 (9)	0.0023 (7)	−0.0057 (6)	−0.0158 (8)
N4	0.0410 (7)	0.0553 (8)	0.0341 (6)	−0.0193 (6)	0.0017 (5)	−0.0078 (6)
O2W	0.0554 (8)	0.0676 (9)	0.0402 (6)	0.0282 (7)	0.0015 (5)	0.0039 (6)
O3W	0.0645 (10)	0.0731 (11)	0.0726 (11)	−0.0275 (8)	0.0065 (8)	−0.0237 (9)

Co1—O1W	2.0741 (10)	N3—C11	1.3428 (15)
Co1—N1	2.2235 (10)	C1—C2	1.3840 (17)
Co1—N2	2.1898 (13)	C2—C3	1.3934 (17)
Co1—N3i	2.2306 (14)	C3—C4	1.3896 (18)
Co1—O1Wii	2.0741 (10)	C3—C3iii	1.4860 (16)
Co1—N1ii	2.2235 (10)	C4—C5	1.3874 (19)
O1W—H13	0.884 (12)	C6—C7	1.3854 (16)
O1W—H12	0.877 (12)	C7—C8	1.3904 (14)
O1—N4	1.247 (2)	C8—C9	1.486 (2)
O2—N4	1.241 (2)	C9—C10ii	1.3922 (15)
O3—N4	1.229 (2)	C9—C10	1.3922 (15)
O2W—H14	0.878 (13)	C10—C11	1.3893 (16)
O2W—H15	0.882 (14)	C1—H1	0.9300
O3W—H17	0.887 (11)	C2—H2	0.9300
O3W—H16	0.873 (13)	C4—H4	0.9300
N1—C1	1.3402 (16)	C5—H5	0.9300
N1—C5	1.3390 (16)	C6—H6	0.9300
N2—C6ii	1.3432 (14)	C7—H7	0.9300
N2—C6	1.3432 (14)	C10—H10	0.9300
N3—C11ii	1.3428 (15)	C11—H11	0.9300
O1W—Co1—N1	91.74 (4)	C1—C2—C3	120.21 (11)
O1W—Co1—N2	90.15 (3)	C2—C3—C4	115.96 (11)
O1W—Co1—N3i	89.85 (3)	C2—C3—C3iii	121.97 (11)
O1W—Co1—O1Wii	179.71 (4)	C3iii—C3—C4	122.07 (11)
O1W—Co1—N1ii	88.27 (4)	C3—C4—C5	120.29 (12)
N1—Co1—N2	88.64 (2)	N1—C5—C4	123.59 (12)
N1—Co1—N3i	91.37 (2)	N2—C6—C7	123.39 (11)
O1Wii—Co1—N1	88.27 (4)	C6—C7—C8	119.57 (11)
N1—Co1—N1ii	177.27 (4)	C7—C8—C9	121.36 (7)
N2—Co1—N3i	180.00	C7ii—C8—C9	121.36 (7)
O1Wii—Co1—N2	90.15 (3)	C7—C8—C7ii	117.28 (13)
N1ii—Co1—N2	88.64 (2)	C8—C9—C10ii	121.59 (7)
O1Wii—Co1—N3i	89.85 (3)	C8—C9—C10	121.59 (7)
N1ii—Co1—N3i	91.37 (2)	C10—C9—C10ii	116.82 (13)
O1Wii—Co1—N1ii	91.74 (4)	C9—C10—C11	119.69 (12)
H12—O1W—H13	105.5 (12)	N3—C11—C10	123.72 (12)
Co1—O1W—H12	124.5 (9)	N1—C1—H1	118.00
Co1—O1W—H13	121.8 (9)	C2—C1—H1	118.00
H14—O2W—H15	104.3 (13)	C1—C2—H2	120.00
H16—O3W—H17	105.5 (12)	C3—C2—H2	120.00
Co1—N1—C5	121.61 (8)	C5—C4—H4	120.00
Co1—N1—C1	122.19 (7)	C3—C4—H4	120.00
C1—N1—C5	116.20 (10)	C4—C5—H5	118.00
Co1—N2—C6ii	121.60 (7)	N1—C5—H5	118.00
C6—N2—C6ii	116.81 (12)	N2—C6—H6	118.00
Co1—N2—C6	121.60 (7)	C7—C6—H6	118.00
C11—N3—C11ii	116.27 (12)	C6—C7—H7	120.00
Co1iv—N3—C11ii	121.86 (7)	C8—C7—H7	120.00
Co1iv—N3—C11	121.86 (7)	C11—C10—H10	120.00
O1—N4—O2	118.72 (17)	C9—C10—H10	120.00
O2—N4—O3	120.61 (15)	C10—C11—H11	118.00
O1—N4—O3	120.67 (17)	N3—C11—H11	118.00
N1—C1—C2	123.72 (11)
O1W—Co1—N1—C1	156.61 (10)	C11ii—N3—C11—C10	1.48 (17)
N2—Co1—N1—C1	−113.29 (9)	N1—C1—C2—C3	0.3 (2)
N3i—Co1—N1—C1	66.72 (9)	C1—C2—C3—C4	−1.58 (19)
O1Wii—Co1—N1—C1	−23.10 (10)	C1—C2—C3—C3iii	178.01 (12)
O1W—Co1—N1—C5	−23.77 (10)	C4—C3—C3iii—C2iii	−0.44 (18)
N2—Co1—N1—C5	66.34 (9)	C2—C3—C4—C5	1.63 (19)
N3i—Co1—N1—C5	−113.66 (9)	C3iii—C3—C4—C5	−177.96 (12)
O1Wii—Co1—N1—C5	156.53 (10)	C2—C3—C3iii—C2iii	−179.98 (15)
O1W—Co1—N2—C6	−53.00 (7)	C2—C3—C3iii—C4iii	0.44 (18)
N1—Co1—N2—C6	−144.74 (7)	C4—C3—C3iii—C4iii	−179.98 (14)
O1Wii—Co1—N2—C6	127.00 (7)	C3—C4—C5—N1	−0.4 (2)
N1ii—Co1—N2—C6	35.27 (7)	N2—C6—C7—C8	−0.39 (18)
O1W—Co1—N2—C6ii	127.00 (7)	C6—C7—C8—C9	−179.82 (9)
N1—Co1—N2—C6ii	35.27 (7)	C6—C7—C8—C7ii	0.18 (15)
Co1—N1—C1—C2	−179.36 (10)	C7—C8—C9—C10ii	−44.87 (9)
C5—N1—C1—C2	1.00 (19)	C7ii—C8—C9—C10	−44.87 (9)
Co1—N1—C5—C4	179.41 (11)	C7—C8—C9—C10	135.13 (9)
C1—N1—C5—C4	−0.95 (19)	C8—C9—C10—C11	−178.64 (9)
Co1—N2—C6—C7	−179.80 (9)	C10ii—C9—C10—C11	1.36 (15)
C6ii—N2—C6—C7	0.20 (15)	C9—C10—C11—N3	−2.9 (2)
Co1iv—N3—C11—C10	−178.53 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H12···O3Wv	0.877 (12)	1.801 (12)	2.675 (2)	174.2 (14)
O1W—H13···O2Wvi	0.884 (12)	1.790 (12)	2.6744 (18)	178.7 (16)
O2W—H14···O1	0.878 (13)	1.959 (12)	2.827 (2)	170.1 (13)
O2W—H15···O2vii	0.882 (14)	1.906 (14)	2.765 (2)	164.2 (14)
O3W—H16···O1	0.873 (13)	1.908 (13)	2.769 (3)	168.9 (14)
O3W—H17···O3vii	0.887 (11)	2.109 (11)	2.958 (2)	159.9 (15)
C1—H1···O1Wii	0.93	2.54	3.0860 (15)	117
C11—H11···N1iv	0.93	2.58	3.1974 (15)	124
C11—H11···O3viii	0.93	2.46	3.209 (2)	137

Table 1

Selected bond lengths (Å)

Co1—O1W	2.0741 (10)
Co1—N1	2.2235 (10)
Co1—N2	2.1898 (13)
Co1—N3i	2.2306 (14)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H12⋯O3W ii	0.877 (12)	1.801 (12)	2.675 (2)	174.2 (14)
O1W—H13⋯O2W iii	0.884 (12)	1.790 (12)	2.6744 (18)	178.7 (16)
O2W—H14⋯O1	0.878 (13)	1.959 (12)	2.827 (2)	170.1 (13)
O2W—H15⋯O2iv	0.882 (14)	1.906 (14)	2.765 (2)	164.2 (14)
O3W—H16⋯O1	0.873 (13)	1.908 (13)	2.769 (3)	168.9 (14)
O3W—H17⋯O3iv	0.887 (11)	2.109 (11)	2.958 (2)	159.9 (15)
C1—H1⋯O1W v	0.93	2.54	3.0860 (15)	117
C11—H11⋯N1vi	0.93	2.58	3.1974 (15)	124
C11—H11⋯O3vii	0.93	2.46	3.209 (2)	137

Symmetry codes: (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .