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

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).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.038
• wR factor = 0.069
• Data-to-parameter ratio = 20.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    Se21   --  C21     ..       5.80 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C31
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600          2

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.95
           From the CIF: _reflns_number_total               3391
           Count of symmetry unique reflns         1812
           Completeness (_total/calc)            187.14%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1579
           Fraction of Friedel pairs measured     0.871
           Are heavy atom types Z>Si present        yes
PLAT083_ALERT_2_G SHELXL Second Parameter in WGHT Unusually Large.       8.87
PLAT917_ALERT_2_G The FCF is likely NOT based on a BASF/TWIN Flack          !
PLAT033_ALERT_4_G Flack x Parameter Value Deviates from Zero .....       0.06
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported   _diffrn_ambient_temperature        293 K
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   7 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   4 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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_MeOH distance 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

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).

S2. Experimental

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.

S3. Refinement

The O-bound H atom was located in a difference Fourier map and its bond length set to a ideal value and finally refined using a riding model. All other H atoms were positioned with idealized geometry and refined using a riding model, with C—H = 0.93 (CH) and 0.96 (CH₃) Å and with U_iso(H) = 1.2(1.5 for methyl)U_eq(C). The absolute structure was determined on the basis of 1579 Friedel pairs.

Computing details

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

	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)]

Crystal data

[Co2(CNSe)4(C4H4N2)3(CH4O)2]	F(000) = 3232
Mr = 421.07	Dx = 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) Å^3	Block, light pink
Z = 16	0.16 × 0.11 × 0.02 mm

Data collection

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

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.038	H-atom parameters constrained
wR(F^2) = 0.069	w = 1/[σ^2(Fo^2) + (0.0286P)^2 + 8.8704P] where P = (Fo^2 + 2Fc^2)/3
S = 1.16	(Δ/σ)max < 0.001
3391 reflections	Δρmax = 0.55 e Å^−3
164 parameters	Δρmin = −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)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Co1—N1	2.191 (3)	N11—C11	1.335 (4)
Co1—N2^i	2.188 (3)	C11—N11^ii	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—C14^ii	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—N2^i	87.12 (14)	C11—N11—Co1	120.5 (3)
N21—Co1—N2^i	91.27 (14)	N11—C11—N11^ii	125.1 (5)
O41—Co1—N2^i	86.37 (13)	N11—C11—H11	117.5
N11—Co1—N2^i	173.71 (13)	N11^ii—C11—H11	117.5
N31—Co1—N1	92.13 (14)	C14—C13—C14^ii	117.1 (6)
N21—Co1—N1	90.91 (14)	C14—C13—H13	121.5
O41—Co1—N1	177.16 (14)	C14^ii—C13—H13	121.5
N11—Co1—N1	89.92 (12)	N11—C14—C13	122.1 (4)
N2^i—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—Co1^iii	124.1 (3)	N31—C31—Se31	178.4 (4)
C2—N2—Co1^iii	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.