Poly[tetra­kis­(seleno­cyanato-κN)bis­(methanol-κO)tris­(μ-pyrimidine-κ2N:N′)dicobalt(II)]

Wriedt, M.; Jess, I.; Näther, C.

doi:10.1107/S160053681002060X

metal-organic compounds

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Volume 66| Part 7| July 2010| Page m742

doi:10.1107/S160053681002060X

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Poly[tetrakis(selenocyanato-κN)bis(methanol-κO)tris(μ-pyrimidine-κ²N:N′)dicobalt(II)]

Mario Wriedt,^a ^* Inke Jess ^a and Christian Näther ^a

^aInstitut für Anorganische Chemie, Christian-Albrechts-Universität Kiel, Max-Eyth-Strasse 2, 24098 Kiel, Germany
^*Correspondence e-mail: mwriedt@ac.uni-kiel.de

(Received 25 May 2010; accepted 31 May 2010; online 5 June 2010)

In the title compound, [Co₂(NCSe)₄(C₄H₄N₂)₃(CH₃OH)₂]_n, the Co^II ion is coordinated by three N-bonded pyrimidine ligands, two N-bonded selenocyanate anions and one O-bonded methanol molecule in an octahedral coordination mode. The asymmetric unit consists of one Co^II ion, one pyrimidine ligand, two selenocyanate anions and one methanol molecule in general positions as well as one pyrimidine ligand located around a twofold rotation axis. In the crystal structure, the pyrimidine ligands bridge [Co(CNSe)₂(CH₃OH)] units into zigzag-like chains, which are further connected by pyrimidine ligands into layers parallel to (010).

Related literature

For general background, see: Wriedt & Näther (2009a ,b ); Wriedt, Sellmer & Näther (2009a ,b ). For the isotypic structure of a nickel thiocyanato complex, see: Wriedt et al. (2009 ).

Experimental

Crystal data

[Co₂(CNSe)₄(C₄H₄N₂)₃(CH₄O)₂]
M_r = 421.07
Orthorhombic, F d d 2
a = 20.4069 (8) Å
b = 33.0633 (15) Å
c = 8.3750 (3) Å
V = 5650.8 (4) Å³
Z = 16
Mo Kα radiation
μ = 6.36 mm⁻¹
T = 293 K
0.16 × 0.11 × 0.02 mm

Data collection

Stoe IPDS-2 diffractometer
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002 ) T_min = 0.431, T_max = 0.885
18545 measured reflections
3391 independent reflections
3067 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.069
S = 1.16
3391 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ), 1579 Friedel pairs
Flack parameter: 0.057 (13)

Table 1
Selected bond lengths (Å)

Co1—N1	2.191 (3)
Co1—N2ⁱ	2.188 (3)
Co1—N11	2.184 (3)
Co1—N21	2.064 (4)
Co1—N31	2.059 (4)
Co1—O41	2.142 (3)
Symmetry code: (i) $[-x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-AREA; 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/S160053681002060X/hy2313sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002060X/hy2313Isup2.hkl

checkCIF report

Comment top

Recently, we have shown that thermal decomposition reactions are an elegante route for the discovering and preparation of new ligand-deficient coordination polymers with defined magnetic properties (Wriedt & Näther, 2009a,b; Wriedt, Sellmer & Näther, 2009a,b). In our ongoing investigation in this field, we have reacted cobalt(II) nitrate, potassium selenocyanate and pyrimidine in methanol. The crystals obtained were identified by single crystal X-ray determination.

The title compound (Fig. 1) represents a two-dimensional layered coordination polymer, which is isotypic to its corresponding nickel(II) thiocyanate analogue reproted recently (Wriedt et al., 2009). The crystal structure consists of µ-1,3-(N,N) pyrimidine bridged zigzag-like cobalt(II) selenocynate chains, which are further linked by µ-1,3-(N,N) pyrimidine ligands into layers (Fig. 2). Within each layer the Co^II ions are bridged by three pyrimidine ligands and are further terminally coordinated by two N-bonded selenocyanate anions and one O-bonded methanol molecule in an octahedral coordination mode (Fig. 1). The layers are stacked in the direction of the crystallographic b-axis (Fig. 3). The CoN₅O octahedron is markedly distorted with three long Co—N_pyrimidine distances in the range of 2.184 (3) to 2.191 (3) Å, one long Co—O_MeOHdistance of 2.142 (3) Å and two short Co—NCSe distances of 2.059 (4) and 2.064 (4) Å (Table 1). The angles arround the metal centers range between 86.37 (13) to 96.00 (13) and 173.71 (13) to 177.16 (14)°. The shortest intra- and interlayer Co···Co distances amount to 6.0723 (6) and 8.5630 (9) Å, respectively.

Related literature top

For general background, see: Wriedt & Näther (2009a,b); Wriedt, Sellmer & Näther (2009a,b). For the isotypic structure of a nickel thiocyanate complex, see: Wriedt et al. (2009).

Experimental top

Co(NO₃)₂.6H₂O (72.8 mg, 0.25 mmol), KNCSe (72.0 mg, 0.5 mmol) and pyrimidine (20.0 mg, 0.25 mmol) obtained from Alfa Aesar were transfered in a closed snap-vial with methanol (3 ml). After several days at room temperature without stirring, light pink block-shaped single crystals of the title compound were obtained in a mixture with unknown phases.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-AREA (Stoe & Cie, 2002); 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. Structure of the title compound with displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: (i) -x+1, -y+1/2, z+1/2; (ii) -x+3/2, -y+1/2, z.]
	Fig. 2. A single layer in the title compound viewed along the b axis.
	Fig. 3. Packing of the layers in the title compound viewed along the c axis.

Poly[tetrakis(selenocyanato-κN)bis(methanol-κO)tris(µ- pyrimidine-κ²N:N')dicobalt(II)] top

Crystal data top

[Co₂(CNSe)₄(C₄H₄N₂)₃(CH₄O)₂]	F(000) = 3232
M_r = 421.07	D_x = 1.980 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 18545 reflections
a = 20.4069 (8) Å	θ = 2.4–28.0°
b = 33.0633 (15) Å	µ = 6.36 mm⁻¹
c = 8.3750 (3) Å	T = 293 K
V = 5650.8 (4) Å³	Block, light pink
Z = 16	0.16 × 0.11 × 0.02 mm

Data collection top

Stoe IPDS-2 diffractometer	3391 independent reflections
Radiation source: fine-focus sealed tube	3067 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
ω scans	θ_max = 28.0°, θ_min = 2.4°
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	h = −26→26
T_min = 0.431, T_max = 0.885	k = −43→43
18545 measured reflections	l = −11→10

Refinement top

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)] = 0.038	H-atom parameters constrained
wR(F²) = 0.069	w = 1/[σ²(F_o²) + (0.0286P)² + 8.8704P] where P = (F_o² + 2F_c²)/3
S = 1.16	(Δ/σ)_max < 0.001
3391 reflections	Δρ_max = 0.55 e Å⁻³
164 parameters	Δρ_min = −0.35 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1579 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.057 (13)

Crystal data top

[Co₂(CNSe)₄(C₄H₄N₂)₃(CH₄O)₂]	V = 5650.8 (4) Å³
M_r = 421.07	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 20.4069 (8) Å	µ = 6.36 mm⁻¹
b = 33.0633 (15) Å	T = 293 K
c = 8.3750 (3) Å	0.16 × 0.11 × 0.02 mm

Data collection top

Stoe IPDS-2 diffractometer	3391 independent reflections
Absorption correction: numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)	3067 reflections with I > 2σ(I)
T_min = 0.431, T_max = 0.885	R_int = 0.044
18545 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.069	Δρ_max = 0.55 e Å⁻³
S = 1.16	Δρ_min = −0.35 e Å⁻³
3391 reflections	Absolute structure: Flack (1983), 1579 Friedel pairs
164 parameters	Absolute structure parameter: 0.057 (13)
1 restraint

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	0.60574 (2)	0.227474 (17)	0.78759 (6)	0.03270 (12)
N1	0.55104 (15)	0.27269 (10)	0.6504 (4)	0.0360 (8)
N2	0.47521 (15)	0.28919 (10)	0.4458 (5)	0.0382 (7)
C1	0.50711 (17)	0.26316 (13)	0.5388 (6)	0.0374 (9)
H1	0.4979	0.2358	0.5246	0.045*
C2	0.4883 (2)	0.32854 (13)	0.4677 (6)	0.0412 (9)
H2	0.4672	0.3477	0.4048	0.049*
C3	0.5320 (2)	0.34078 (14)	0.5813 (6)	0.0459 (11)
H3	0.5410	0.3681	0.5959	0.055*
C4	0.5623 (2)	0.31226 (13)	0.6730 (6)	0.0434 (10)
H4	0.5912	0.3204	0.7526	0.052*
N11	0.69371 (15)	0.24124 (11)	0.6493 (4)	0.0352 (8)
C11	0.7500	0.2500	0.7228 (7)	0.0372 (12)
H11	0.7500	0.2500	0.8339	0.045*
C13	0.7500	0.2500	0.4059 (8)	0.061 (2)
H13	0.7500	0.2500	0.2948	0.074*
C14	0.6944 (2)	0.24140 (17)	0.4914 (6)	0.0499 (12)
H14	0.6559	0.2355	0.4366	0.060*
N21	0.57994 (17)	0.18287 (12)	0.6270 (5)	0.0434 (8)
C21	0.56005 (17)	0.15562 (13)	0.5553 (5)	0.0381 (9)
Se21	0.53008 (3)	0.114405 (17)	0.44108 (7)	0.06121 (16)
N31	0.63231 (16)	0.26940 (12)	0.9575 (5)	0.0428 (8)
C31	0.63448 (17)	0.29139 (13)	1.0643 (5)	0.0373 (9)
Se31	0.63665 (3)	0.324181 (19)	1.23170 (7)	0.06461 (17)
O41	0.66187 (15)	0.18255 (10)	0.9111 (4)	0.0522 (8)
C41	0.6758 (4)	0.1790 (2)	1.0749 (8)	0.085 (2)
H41A	0.6359	0.1747	1.1328	0.127*
H41B	0.6964	0.2034	1.1118	0.127*
H41C	0.7048	0.1566	1.0918	0.127*
H1O4	0.6862	0.1792	0.8352	0.127*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0252 (2)	0.0341 (3)	0.0388 (3)	−0.0009 (2)	−0.0010 (2)	−0.0043 (2)
N1	0.0287 (15)	0.0336 (18)	0.046 (2)	−0.0015 (13)	−0.0036 (13)	0.0000 (15)
N2	0.0294 (14)	0.0376 (17)	0.048 (2)	−0.0013 (14)	−0.0020 (14)	0.0017 (17)
C1	0.0270 (16)	0.036 (2)	0.049 (2)	0.0006 (15)	−0.0018 (18)	−0.0026 (19)
C2	0.045 (2)	0.033 (2)	0.045 (2)	0.0008 (17)	−0.0001 (19)	0.0031 (19)
C3	0.059 (3)	0.029 (2)	0.049 (3)	−0.0082 (19)	0.003 (2)	−0.0002 (19)
C4	0.048 (2)	0.039 (2)	0.043 (2)	−0.0022 (18)	−0.0087 (19)	−0.0029 (19)
N11	0.0268 (14)	0.0419 (19)	0.037 (2)	−0.0028 (13)	−0.0005 (13)	0.0017 (14)
C11	0.029 (2)	0.050 (3)	0.032 (3)	0.000 (2)	0.000	0.000
C13	0.046 (4)	0.108 (7)	0.030 (4)	−0.001 (4)	0.000	0.000
C14	0.0295 (19)	0.075 (3)	0.045 (3)	−0.005 (2)	−0.0032 (18)	−0.003 (2)
N21	0.0422 (18)	0.040 (2)	0.048 (2)	0.0000 (16)	−0.0047 (16)	−0.0091 (17)
C21	0.0304 (16)	0.043 (2)	0.042 (2)	0.0029 (16)	0.0016 (17)	0.002 (2)
Se21	0.0661 (3)	0.0505 (3)	0.0670 (4)	−0.0056 (2)	−0.0100 (3)	−0.0199 (3)
N31	0.0419 (18)	0.045 (2)	0.042 (2)	−0.0081 (16)	0.0024 (16)	−0.0071 (18)
C31	0.0276 (17)	0.039 (2)	0.046 (3)	−0.0020 (15)	0.0036 (16)	0.003 (2)
Se31	0.0715 (3)	0.0632 (4)	0.0592 (3)	−0.0041 (3)	0.0086 (3)	−0.0256 (3)
O41	0.0456 (16)	0.054 (2)	0.057 (2)	0.0146 (15)	−0.0044 (15)	0.0063 (16)
C41	0.101 (5)	0.071 (4)	0.082 (5)	0.002 (4)	−0.047 (4)	0.007 (3)

Geometric parameters (Å, º) top

Co1—N1	2.191 (3)	N11—C11	1.335 (4)
Co1—N2ⁱ	2.188 (3)	C11—N11ⁱⁱ	1.335 (4)
Co1—N11	2.184 (3)	C11—H11	0.9300
Co1—N21	2.064 (4)	C13—C14	1.372 (6)
Co1—N31	2.059 (4)	C13—C14ⁱⁱ	1.372 (6)
Co1—O41	2.142 (3)	C13—H13	0.9300
N1—C1	1.333 (5)	C14—H14	0.9300
N1—C4	1.342 (5)	N21—C21	1.157 (5)
N2—C1	1.331 (5)	C21—Se21	1.774 (5)
N2—C2	1.341 (5)	N31—C31	1.154 (5)
C1—H1	0.9300	C31—Se31	1.773 (4)
C2—C3	1.366 (6)	O41—C41	1.405 (7)
C2—H2	0.9300	O41—H1O4	0.8139
C3—C4	1.364 (7)	C41—H41A	0.9600
C3—H3	0.9300	C41—H41B	0.9600
C4—H4	0.9300	C41—H41C	0.9600
N11—C14	1.323 (6)

N31—Co1—N21	176.69 (16)	C2—C3—H3	120.6
N31—Co1—O41	89.55 (15)	N1—C4—C3	121.2 (4)
N21—Co1—O41	87.46 (14)	N1—C4—H4	119.4
N31—Co1—N11	90.55 (13)	C3—C4—H4	119.4
N21—Co1—N11	90.75 (14)	C14—N11—C11	116.8 (4)
O41—Co1—N11	87.77 (13)	C14—N11—Co1	122.6 (3)
N31—Co1—N2ⁱ	87.12 (14)	C11—N11—Co1	120.5 (3)
N21—Co1—N2ⁱ	91.27 (14)	N11—C11—N11ⁱⁱ	125.1 (5)
O41—Co1—N2ⁱ	86.37 (13)	N11—C11—H11	117.5
N11—Co1—N2ⁱ	173.71 (13)	N11ⁱⁱ—C11—H11	117.5
N31—Co1—N1	92.13 (14)	C14—C13—C14ⁱⁱ	117.1 (6)
N21—Co1—N1	90.91 (14)	C14—C13—H13	121.5
O41—Co1—N1	177.16 (14)	C14ⁱⁱ—C13—H13	121.5
N11—Co1—N1	89.92 (12)	N11—C14—C13	122.1 (4)
N2ⁱ—Co1—N1	96.00 (13)	N11—C14—H14	118.9
C1—N1—C4	116.4 (4)	C13—C14—H14	118.9
C1—N1—Co1	123.3 (3)	C21—N21—Co1	169.9 (4)
C4—N1—Co1	120.3 (3)	N21—C21—Se21	178.7 (4)
C1—N2—C2	116.8 (4)	C31—N31—Co1	166.0 (3)
C1—N2—Co1ⁱⁱⁱ	124.1 (3)	N31—C31—Se31	178.4 (4)
C2—N2—Co1ⁱⁱⁱ	118.5 (3)	C41—O41—Co1	129.6 (4)
N2—C1—N1	125.9 (4)	C41—O41—H1O4	128.9
N2—C1—H1	117.0	Co1—O41—H1O4	92.4
N1—C1—H1	117.0	O41—C41—H41A	109.5
N2—C2—C3	120.8 (4)	O41—C41—H41B	109.5
N2—C2—H2	119.6	H41A—C41—H41B	109.5
C3—C2—H2	119.6	O41—C41—H41C	109.5
C4—C3—C2	118.9 (4)	H41A—C41—H41C	109.5
C4—C3—H3	120.6	H41B—C41—H41C	109.5

Symmetry codes: (i) −x+1, −y+1/2, z+1/2; (ii) −x+3/2, −y+1/2, z; (iii) −x+1, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Co₂(CNSe)₄(C₄H₄N₂)₃(CH₄O)₂]
M_r	421.07
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	293
a, b, c (Å)	20.4069 (8), 33.0633 (15), 8.3750 (3)
V (Å³)	5650.8 (4)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	6.36
Crystal size (mm)	0.16 × 0.11 × 0.02

Data collection
Diffractometer	Stoe IPDS2 diffractometer
Absorption correction	Numerical (X-SHAPE and X-RED32; Stoe & Cie, 2002)
T_min, T_max	0.431, 0.885
No. of measured, independent and observed [I > 2σ(I)] reflections	18545, 3391, 3067
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.659

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.069, 1.16
No. of reflections	3391
No. of parameters	164
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.35
Absolute structure	Flack (1983), 1579 Friedel pairs
Absolute structure parameter	0.057 (13)

Computer programs: X-AREA (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—N1	2.191 (3)	Co1—N21	2.064 (4)
Co1—N2ⁱ	2.188 (3)	Co1—N31	2.059 (4)
Co1—N11	2.184 (3)	Co1—O41	2.142 (3)

Symmetry code: (i) −x+1, −y+1/2, z+1/2.

Acknowledgements

MW thanks the Stiftung Stipendien-Fonds des Verbandes der Chemischen Industrie and the Studienstiftung des deutschen Volkes for a PhD scholarship. We gratefully acknowledge financial support by the State of Schleswig-Holstein and the Deutsche Forschungsgemeinschaft (Project 720/3-1). We thank Professor Dr Wolfgang Bensch for the opportunity to use of his experimental facilities.

References

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