catena-Poly[[diaqua­bis(thio­cyanato-κN)cobalt(II)]-μ-4,4′-bipyridine-κ2N:N′] 4,4′-bipyridine solvate]

Yao, R.; Wang, D.E.

doi:10.1107/S1600536809023265

metal-organic compounds

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Volume 65| Part 7| July 2009| Page m813

doi:10.1107/S1600536809023265

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catena-Poly[[diaquabis(thiocyanato-κN)cobalt(II)]-μ-4,4′-bipyridine-κ²N:N′] 4,4′-bipyridine solvate]

Rufu Yao ^a ^* and Dong E. Wang ^b

^aDepartment of Chemistry, Hefei Teachers College, Hefei, Anhui 230061, People's Republic of China, and ^bThe Department of chemistry, Kashgar Teachers College, Kashgar, Xinjiang 844000, People's Republic of China
^*Correspondence e-mail: yaorufu@sina.com

(Received 30 March 2009; accepted 17 June 2009; online 24 June 2009)

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, $[P \overline 1]$
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) Å³
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[F² > 2σ(F²)] = 0.042
wR(F²) = 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

Table 1
Selected bond lengths (Å)

Co1—N2	2.089 (2)
Co1—O1	2.0964 (19)
Co1—N5	2.1625 (18)
Symmetry code: (i) -x+1, -y+1, -z+1.

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) x-1, y, z.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023265/kp2215sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809023265/kp2215Isup2.hkl

checkCIF report

Comment top

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)ⁱand 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).

Related literature top

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 top

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.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. A part of polymeric chain of Co^II 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).

catena-Poly[[diaquabis(thiocyanato-κN)cobalt(II)]-µ-4,4'- bipyridine-κ²N:N'] 4,4'-bipyridine solvate] top

Crystal data top

[Co(NCS)₂(C₁₀H₈N₂)(H₂O)₂]·C₁₀H₈N₂	V = 612.66 (14) Å³
M_r = 523.51	Z = 1
Triclinic, P1	F(000) = 269
Hall symbol: -P 1	D_x = 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 top

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

Refinement top

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(F_o²) + (0.0744P)² + 0.3257P] where P = (F_o² + 2F_c²)/3
2359 reflections	(Δ/σ)_max < 0.001
157 parameters	Δρ_max = 0.77 e Å⁻³
3 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Co(NCS)₂(C₁₀H₈N₂)(H₂O)₂]·C₁₀H₈N₂	γ = 97.038 (2)°
M_r = 523.51	V = 612.66 (14) Å³
Triclinic, P1	Z = 1
a = 7.4433 (11) Å	Mo Kα radiation
b = 9.0147 (11) Å	µ = 0.90 mm⁻¹
c = 10.1114 (13) Å	T = 293 K
α = 107.770 (2)°	0.20 × 0.20 × 0.20 mm
β = 103.978 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2359 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	2191 reflections with I > 2σ(I)
T_min = 0.835, T_max = 0.835	R_int = 0.012
3522 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	3 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.77 e Å⁻³
2359 reflections	Δρ_min = −0.74 e Å⁻³
157 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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···S1^iv	0.82 (3)	2.52 (3)	3.279 (2)	154 (3)

Symmetry code: (iv) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Co(NCS)₂(C₁₀H₈N₂)(H₂O)₂]·C₁₀H₈N₂
M_r	523.51
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.4433 (11), 9.0147 (11), 10.1114 (13)
α, β, γ (°)	107.770 (2), 103.978 (2), 97.038 (2)
V (Å³)	612.66 (14)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.90
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1997)
T_min, T_max	0.835, 0.835
No. of measured, independent and observed [I > 2σ(I)] reflections	3522, 2359, 2191
R_int	0.012
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.118, 1.04
No. of reflections	2359
No. of parameters	157
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.77, −0.74

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—N2ⁱ	2.089 (2)	Co1—O1ⁱ	2.0964 (19)
Co1—N2	2.089 (2)	Co1—N5	2.1625 (18)
Co1—O1	2.0964 (19)	Co1—N5ⁱ	2.1625 (18)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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) x−1, y, z.

References

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He, H. Y., Zhou, Y. L. & Zhu, L. G. (2006). Chin. J. Inorg. Chem. 22, 142–144. CAS Google Scholar
Lu, J., Paliwala, T., Lim, S. C., Yu, C., Niu, T. & Jacobson, A. J. (1997). Inorg. Chem. 36, 923–927. CSD CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, Y. Q., Li, C. H., Li, W., Chen, Z. M. & Wang, Y. (2008). Chin. J. Inorg. Chem. 24, 1365-1368. CAS Google Scholar
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