catena-Poly[[diaqua­bis(thio­cyanato-κN)cobalt(II)]-μ-4,4′-bipyridine-κ² N:N′] 4,4′-bipyridine solvate]

Abstract

In the title complex, {[Co(NCS)₂(C₁₀H₈N₂)(H₂O)₂]·C₁₀H₈N₂}_n, the Co^II ion is located on an inversion centre and is coordinated by two N atoms from the two 4,4′-bipyridine ligands, two O atoms from the water mol­ecule, and two N atoms from two isothio­cyanate ions in a distorted octa­hedral environment. In the crystal, the coordinated water mol­ecules, isothio­cyanate ions and solvent 4,4′-bipyridine mol­ecules are linked by O—H⋯S and O—H⋯N hydrogen bonds into layers parallel to the ab plane.

Related literature

For two-dimensional Mn^II and one-dimensional Cu^II complexes constructed from 4,4′-bipy, see: Yang et al. (2008 ▶); Zhou & He (2008 ▶). For related structures, see: Lu et al. (1997 ▶); He et al. (2006 ▶).

Experimental

Crystal data

• [Co(NCS)₂(C₁₀H₈N₂)(H₂O)₂]·C₁₀H₈N₂

• M _r = 523.51

• Triclinic,

• a = 7.4433 (11) Å

• b = 9.0147 (11) Å

• c = 10.1114 (13) Å

• α = 107.770 (2)°

• β = 103.978 (2)°

• γ = 97.038 (2)°

• V = 612.66 (14) ų

• Z = 1

• Mo Kα radiation

• μ = 0.90 mm⁻¹

• T = 293 K

• 0.20 × 0.20 × 0.20 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; (Bruker, 2001 ▶) T _min = 0.835, T _max = 0.835

• 3522 measured reflections

• 2359 independent reflections

• 2191 reflections with I > 2σ(I)

• R _int = 0.012

Refinement

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.118

• S = 1.04

• 2359 reflections

• 157 parameters

• 3 restraints

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.77 e Å⁻³

• Δρ_min = −0.74 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Co1—N2	2.089 (2)
Co1—O1	2.0964 (19)
Co1—N5	2.1625 (18)

Symmetry code: (i) .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1C⋯N7	0.82 (3)	1.92 (3)	2.732 (3)	171 (3)
O1—H1B⋯S1ii	0.82 (3)	2.52 (3)	3.279 (2)	154 (3)

Symmetry code: (ii) .

supplementary crystallographic information

Comment

For 2-D Mn^II and 1-D Cu^II complexes constructed from 4,4'-bipy see: Yang et al. (2008) and Zhou, et al. (2008). The compound of [Co(4,4'-bipy)(NCS)₂(OH₂)₂].(4,4'-bipy) were reported (Lu, et al. 1997) but the polymeric compound has not been synthesized, so far. Herein, we report the crystal structure of a novel polymeric compound, {[Co(4,4'-bipy)(NCS)₂(OH₂)₂].(4,4'-bipy)}_n. The Co^II ion is coordinated by two N atoms from 4,4'-bipy ligand, two N atoms from isothiocyanate ions, and two O atoms from two water molecule in a distorted octahedral geometry (Fig. 1, Table 1). O(1), N(2), O(1)ⁱ and N(2)ⁱ[symmetry code: -1 + x, y, z] lie in the equatorial plane, with the O(1)—N(2)—O(1)ⁱ—N(2)ⁱ torsional angle of 0.02 (11)°, while the Co atom deviates from the equatorial plane by 0.051 Å. N(5), N(5)ⁱ atoms occupy the axial sites, which are strictly linear due to a symmetry opeartion. The bond lengths and angles of the title complex are similar to the compound {[Co(4,4'-bipy)(ambdc)(OH₂)₂](4,4'-bipy)(DMF)}_n (He et al.,2006). In the crystal packing of (l) are linked by O—H···S and O—H···N hydrogen bonds (Table 2, Fig. 2).

Experimental

A mixture of Co(CH₃COO)₂(0.5 mmol), 4,4'-bipy (0.5 mmol and H₂O (10.00 ml), was placed in a Parr Teflon-lined stainless steel vessel (10 ml), and then the vessel was sealed and heated at 393 K for 3 d. After the mixture was slowly cooled to room temperature, a few red crystals of [Co(4,4'-bipy)(NCS)₂(OH₂)₂].(4,4'-bipy) were obtained.

Refinement

H atoms of water molecule were located in a difference map and refined with O—H distance restraints of 0.82 (3)) Å, and U_iso(H) = 1.5U_eq(O). Other H atoms bonded to C atoms were introduced at calculated positions and refined using a riding model, with U_iso(H) = 1.2U_eq(C), and C—H distances of 0.93 Å.

Figures

Fig. 1.

A part of polymeric chain of CoII octahedra with 4,4-bpy bridging ligand is shown with ellipsoids at the 30% probability level. Symmetry codes used: (i) -x + 1,-y + 1,-z + 1; (ii) x - 1, y, z. (iii)-x, -y, -z.

Fig. 2.

The crystal packing of (I) with hydrogen bonds (dashed lines).

Crystal data

[Co(NCS)2(C10H8N2)(H2O)2]·C10H8N2	V = 612.66 (14) Å3
Mr = 523.51	Z = 1
Triclinic, P1	F(000) = 269
Hall symbol: -P 1	Dx = 1.419 Mg m−3
a = 7.4433 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.0147 (11) Å	θ = 1.0–26.0°
c = 10.1114 (13) Å	µ = 0.90 mm−1
α = 107.770 (2)°	T = 293 K
β = 103.978 (2)°	Block, red
γ = 97.038 (2)°	0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer	2359 independent reflections
Radiation source: fine-focus sealed tube	2191 reflections with I > 2σ(I)
graphite	Rint = 0.012
φ and ωs scans	θmax = 26.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −9→4
Tmin = 0.835, Tmax = 0.835	k = −11→11
3522 measured reflections	l = −12→12

Refinement

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0744P)2 + 0.3257P] where P = (Fo2 + 2Fc2)/3
2359 reflections	(Δ/σ)max < 0.001
157 parameters	Δρmax = 0.77 e Å−3
3 restraints	Δρmin = −0.74 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Co1	0.5000	0.5000	0.5000	0.03359 (17)
S1	0.93240 (12)	0.61882 (16)	0.23801 (12)	0.0837 (4)
O1	0.3666 (3)	0.6731 (2)	0.4436 (2)	0.0453 (4)
H1B	0.251 (3)	0.659 (4)	0.418 (4)	0.068*
H1C	0.403 (4)	0.719 (4)	0.394 (3)	0.068*
N2	0.6824 (3)	0.5256 (3)	0.3768 (2)	0.0467 (5)
N5	0.2992 (3)	0.3143 (2)	0.3142 (2)	0.0365 (4)
C1	0.2050 (4)	0.1832 (3)	0.3238 (3)	0.0439 (6)
H1A	0.2201	0.1757	0.4154	0.053*
C2	0.0868 (4)	0.0590 (3)	0.2048 (3)	0.0433 (6)
H2A	0.0247	−0.0295	0.2172	0.052*
C3	0.0605 (3)	0.0664 (3)	0.0661 (2)	0.0326 (5)
C4	0.1567 (4)	0.2036 (3)	0.0576 (2)	0.0390 (5)
H4	0.1423	0.2157	−0.0322	0.047*
C5	0.2730 (4)	0.3217 (3)	0.1814 (2)	0.0398 (5)
H5	0.3369	0.4115	0.1721	0.048*
C21	0.7868 (4)	0.5654 (3)	0.3206 (3)	0.0439 (6)
N7	0.4547 (4)	0.8112 (3)	0.2551 (3)	0.0652 (7)
C11	0.5596 (5)	0.9552 (4)	0.2955 (4)	0.0664 (8)
H11	0.6222	1.0072	0.3939	0.080*
C12	0.5829 (5)	1.0347 (4)	0.2006 (3)	0.0579 (7)
H12	0.6588	1.1365	0.2356	0.070*
C13	0.4917 (4)	0.9604 (3)	0.0537 (3)	0.0458 (6)
C14	0.3805 (5)	0.8079 (4)	0.0096 (4)	0.0590 (7)
H14	0.3170	0.7522	−0.0881	0.071*
C15	0.3664 (6)	0.7408 (4)	0.1137 (4)	0.0695 (9)
H15	0.2901	0.6397	0.0828	0.083*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Co1	0.0348 (3)	0.0325 (3)	0.0224 (2)	−0.00978 (17)	0.00294 (17)	0.00493 (17)
S1	0.0513 (5)	0.1408 (10)	0.0912 (7)	0.0135 (5)	0.0309 (5)	0.0798 (7)
O1	0.0453 (10)	0.0441 (10)	0.0408 (10)	−0.0031 (8)	0.0058 (8)	0.0172 (8)
N2	0.0450 (12)	0.0515 (12)	0.0351 (11)	−0.0079 (10)	0.0114 (10)	0.0105 (9)
N5	0.0366 (10)	0.0335 (10)	0.0271 (9)	−0.0071 (8)	0.0014 (8)	0.0052 (8)
C1	0.0494 (14)	0.0412 (13)	0.0265 (11)	−0.0144 (11)	0.0032 (10)	0.0067 (10)
C2	0.0469 (14)	0.0385 (12)	0.0303 (11)	−0.0154 (10)	0.0048 (10)	0.0067 (10)
C3	0.0293 (10)	0.0321 (11)	0.0271 (10)	−0.0005 (9)	0.0022 (9)	0.0048 (9)
C4	0.0471 (13)	0.0326 (11)	0.0266 (10)	−0.0036 (10)	−0.0002 (10)	0.0087 (9)
C5	0.0451 (13)	0.0311 (11)	0.0318 (11)	−0.0072 (10)	0.0011 (10)	0.0087 (9)
C21	0.0379 (13)	0.0521 (15)	0.0370 (12)	−0.0010 (11)	0.0043 (10)	0.0180 (11)
N7	0.0780 (18)	0.0692 (17)	0.0740 (18)	0.0243 (15)	0.0358 (15)	0.0466 (15)
C11	0.078 (2)	0.072 (2)	0.0585 (19)	0.0154 (18)	0.0229 (17)	0.0335 (17)
C12	0.0635 (18)	0.0549 (17)	0.0609 (18)	0.0066 (14)	0.0204 (15)	0.0285 (14)
C13	0.0490 (14)	0.0465 (14)	0.0560 (15)	0.0158 (11)	0.0268 (12)	0.0266 (13)
C14	0.073 (2)	0.0491 (16)	0.0597 (18)	0.0059 (14)	0.0237 (16)	0.0255 (14)
C15	0.085 (2)	0.0537 (18)	0.082 (2)	0.0077 (17)	0.033 (2)	0.0361 (17)

Geometric parameters (Å, °)

Co1—N2i	2.089 (2)	C3—C4	1.388 (3)
Co1—N2	2.089 (2)	C3—C3ii	1.486 (4)
Co1—O1	2.0964 (19)	C4—C5	1.374 (3)
Co1—O1i	2.0964 (19)	C4—H4	0.9300
Co1—N5	2.1625 (18)	C5—H5	0.9300
Co1—N5i	2.1625 (18)	N7—C11	1.318 (5)
S1—C21	1.630 (3)	N7—C15	1.330 (5)
O1—H1B	0.817 (18)	C11—C12	1.390 (4)
O1—H1C	0.813 (17)	C11—H11	0.9300
N2—C21	1.151 (3)	C12—C13	1.382 (4)
N5—C5	1.333 (3)	C12—H12	0.9300
N5—C1	1.341 (3)	C13—C14	1.394 (4)
C1—C2	1.378 (3)	C13—C13iii	1.490 (5)
C1—H1A	0.9300	C14—C15	1.382 (4)
C2—C3	1.393 (3)	C14—H14	0.9300
C2—H2A	0.9300	C15—H15	0.9300
N2i—Co1—N2	180.0	C3—C2—H2A	120.1
N2i—Co1—O1	90.16 (9)	C4—C3—C2	116.3 (2)
N2—Co1—O1	89.84 (9)	C4—C3—C3ii	121.7 (2)
N2i—Co1—O1i	89.84 (9)	C2—C3—C3ii	122.0 (3)
N2—Co1—O1i	90.16 (9)	C5—C4—C3	120.3 (2)
O1—Co1—O1i	180.0	C5—C4—H4	119.9
N2i—Co1—N5	88.84 (8)	C3—C4—H4	119.9
N2—Co1—N5	91.16 (8)	N5—C5—C4	123.5 (2)
O1—Co1—N5	90.36 (7)	N5—C5—H5	118.3
O1i—Co1—N5	89.64 (7)	C4—C5—H5	118.3
N2i—Co1—N5i	91.16 (8)	N2—C21—S1	178.8 (3)
N2—Co1—N5i	88.84 (8)	C11—N7—C15	116.2 (3)
O1—Co1—N5i	89.64 (7)	N7—C11—C12	124.3 (3)
O1i—Co1—N5i	90.36 (7)	N7—C11—H11	117.8
N5—Co1—N5i	180.0	C12—C11—H11	117.8
Co1—O1—H1B	121 (2)	C13—C12—C11	119.1 (3)
Co1—O1—H1C	121 (2)	C13—C12—H12	120.4
H1B—O1—H1C	106 (3)	C11—C12—H12	120.4
C21—N2—Co1	169.0 (2)	C12—C13—C14	117.1 (3)
C5—N5—C1	116.7 (2)	C12—C13—C13iii	121.9 (3)
C5—N5—Co1	120.28 (15)	C14—C13—C13iii	121.0 (3)
C1—N5—Co1	122.85 (15)	C15—C14—C13	118.8 (3)
N5—C1—C2	123.3 (2)	C15—C14—H14	120.6
N5—C1—H1A	118.3	C13—C14—H14	120.6
C2—C1—H1A	118.3	N7—C15—C14	124.4 (3)
C1—C2—C3	119.9 (2)	N7—C15—H15	117.8
C1—C2—H2A	120.1	C14—C15—H15	117.8

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

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···N7	0.82 (3)	1.92 (3)	2.732 (3)	171 (3)
O1—H1B···S1iv	0.82 (3)	2.52 (3)	3.279 (2)	154 (3)

Symmetry codes: (iv) x−1, y, z.