Bis(pyridine-2-methanol-κ²N,O]bis­(thio­cyanato-κN)cobalt(II)

The Co^II ion in the title complex, [Co(NCS)₂(C₆H₇NO)₂], lies on a crystallographic twofold axis and is in a slightly distorted octa­hedral coordination environment. In the crystal structure, inter­molecular O—H...S hydrogen bonds link mol­ecules to form a two-dimensional network perpendicular to the c axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.008 Å
• R factor = 0.055
• wR factor = 0.170
• Data-to-parameter ratio = 13.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          8

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Co1         (2)       1.76

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

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

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S1. Comment

In recent years there has been considerable interest in metal complexes of hydroxymethyl-pyridine due to the ligands versatile coordination modes and bridging function (Yoo et al., 2000; Yang et al., 2003). As an extension of this work on the structural characterization of hydroxymethyl-pyridine derivatives, we have synthesized here title compound, (I), and report herein its crystal structure.

The complex (Fig. 1) consists of two L^2-(L=(hydroxymethyl)(pyridine) ligands, one Co^II ion and two thiocyanato ligands. The coordination geometry around the Co center is slightly distorted octahedral with a CoN₄O₂ ligand set (see table of geometric parameters). Atom N2 of a thiocyanato ligand and atom O1 of an hydroxymethylpyridine ligand occupy the axial sites. In the crystal structure, intermolecular O—H···S hydrogen bonds link molecules to form a two-dimensional network perpendicular to the c axis (see hydrogen-bond geometry table).

Related literature

For related literature, see: Yang et al. (2003); Yoo et al. (2000).

S2. Experimental

2-hydroxymethylpyridine (0.546 g, 5 mmol) and Et₄NOH with 20% aqueous solution (0.736 g, 1 mmol) were added to a mixture(30 ml) of methanol and acetonitrile (V₁: V₂=2:1) containing cobaltous chlorine hexahydrate(0.476 g, 2 mmol).After the solution was stirred at room temperature for 0.5 h. Potassium thiocyanato(0,486 g, 5 mmol) in 5 ml of methanol was added to the above solution and then further stirred for 2 h. The resulting clear solution was filtered and left to stand at room temperature. Red crystal suitable for X-ray diffraction were obtained by slow evaporation of the solvents within 2 weeks. (m.p.=458 K-459 K). Elemental analysis calculated for C₁₄H₁₄N₄O₂Co_S2: C 42.75, H 3.59, N 14.24%; found: C 42.80, H 3.54, N 14.30%.

S3. Refinement

All H atoms were placed geometrically and treated as riding on their parent atoms with C—H 0.93(pyridine), C—H 0.97 (methylene) Å [U_iso(H) = 1.2U_eq(C)] and O—H 0.82 Å (hydroxyl) [U_iso(H) = 1.5U_eq(O)].

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

	Fig. 1. The molecule structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Atoms labelled with the suffix A are generated by the symmetry operation (-x + 1, y, -z + 1/2). H atoms have been omitted for clarity.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

Bis(pyridine-2-methanol-κ²N,O]bis(thiocyanato-κN)cobalt(II)

Crystal data

[Co(NCS)2(C6H7NO)2]	F(000) = 804
Mr = 393.34	Dx = 1.565 Mg m^−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 2060 reflections
a = 11.371 (10) Å	θ = 2.9–24.0°
b = 8.255 (8) Å	µ = 1.29 mm^−1
c = 17.779 (16) Å	T = 298 K
V = 1669 (3) Å^3	Block, red
Z = 4	0.45 × 0.37 × 0.30 mm

Data collection

Bruker SMART CCD diffractometer	1463 independent reflections
Radiation source: fine-focus sealed tube	1079 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.088
ϕ and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→13
Tmin = 0.594, Tmax = 0.698	k = −8→9
6193 measured reflections	l = −18→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.170	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0972P)^2 + 2.6034P] where P = (Fo^2 + 2Fc^2)/3
1463 reflections	(Δ/σ)max < 0.001
105 parameters	Δρmax = 0.90 e Å^−3
0 restraints	Δρmin = −0.80 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	0.21568 (11)	0.2500	0.0366 (4)
N1	0.6485 (4)	0.2744 (5)	0.1860 (2)	0.0415 (10)
N2	0.5778 (4)	0.0526 (5)	0.3203 (2)	0.0490 (11)
O1	0.4388 (3)	0.4024 (4)	0.16747 (19)	0.0506 (9)
H1	0.3691	0.3971	0.1558	0.076*
S1	0.68424 (13)	−0.17410 (19)	0.41381 (8)	0.0573 (5)
C1	0.5087 (4)	0.4002 (8)	0.1015 (3)	0.0516 (14)
H1A	0.5070	0.5057	0.0776	0.062*
H1B	0.4779	0.3211	0.0663	0.062*
C2	0.6329 (4)	0.3572 (6)	0.1224 (3)	0.0431 (12)
C3	0.7262 (5)	0.4016 (7)	0.0772 (3)	0.0576 (15)
H3	0.7133	0.4607	0.0334	0.069*
C4	0.8373 (5)	0.3579 (8)	0.0975 (3)	0.0593 (16)
H4	0.9008	0.3835	0.0667	0.071*
C5	0.8549 (5)	0.2756 (7)	0.1639 (4)	0.0592 (16)
H5	0.9304	0.2491	0.1799	0.071*
C6	0.7586 (5)	0.2337 (6)	0.2058 (3)	0.0482 (13)
H6	0.7699	0.1746	0.2498	0.058*
C7	0.6233 (4)	−0.0404 (6)	0.3589 (3)	0.0392 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0326 (5)	0.0353 (6)	0.0419 (6)	0.000	0.0008 (4)	0.000
N1	0.045 (2)	0.043 (2)	0.036 (2)	−0.0052 (18)	0.0000 (18)	−0.0067 (19)
N2	0.047 (3)	0.043 (2)	0.057 (3)	−0.004 (2)	−0.003 (2)	0.008 (2)
O1	0.047 (2)	0.054 (2)	0.051 (2)	0.0069 (17)	−0.0007 (17)	0.0056 (17)
S1	0.0566 (9)	0.0564 (9)	0.0590 (9)	0.0030 (7)	−0.0096 (7)	0.0154 (7)
C1	0.053 (3)	0.062 (4)	0.039 (3)	−0.005 (3)	−0.004 (2)	0.004 (3)
C2	0.050 (3)	0.043 (3)	0.037 (3)	−0.010 (2)	0.004 (2)	−0.005 (2)
C3	0.071 (4)	0.062 (3)	0.040 (3)	−0.020 (3)	0.004 (3)	−0.009 (3)
C4	0.052 (3)	0.074 (4)	0.052 (4)	−0.014 (3)	0.021 (3)	−0.014 (3)
C5	0.038 (3)	0.072 (4)	0.067 (4)	−0.007 (3)	0.000 (3)	−0.016 (3)
C6	0.044 (3)	0.045 (3)	0.056 (3)	−0.005 (2)	−0.002 (2)	−0.004 (2)
C7	0.034 (2)	0.039 (3)	0.045 (3)	−0.008 (2)	−0.001 (2)	−0.004 (2)

Geometric parameters (Å, º)

Co1—N2^i	2.039 (5)	C1—C2	1.502 (7)
Co1—N2	2.039 (5)	C1—H1A	0.9700
Co1—N1	2.093 (4)	C1—H1B	0.9700
Co1—N1^i	2.093 (4)	C2—C3	1.381 (7)
Co1—O1^i	2.239 (4)	C3—C4	1.363 (8)
Co1—O1	2.239 (4)	C3—H3	0.9300
N1—C2	1.333 (6)	C4—C5	1.377 (9)
N1—C6	1.344 (7)	C4—H4	0.9300
N2—C7	1.152 (6)	C5—C6	1.369 (8)
O1—C1	1.417 (6)	C5—H5	0.9300
O1—H1	0.8200	C6—H6	0.9300
S1—C7	1.629 (5)
N2^i—Co1—N2	97.4 (2)	O1—C1—C2	109.0 (4)
N2^i—Co1—N1	99.78 (17)	O1—C1—H1A	109.9
N2—Co1—N1	97.81 (17)	C2—C1—H1A	109.9
N2^i—Co1—N1^i	97.81 (17)	O1—C1—H1B	109.9
N2—Co1—N1^i	99.78 (17)	C2—C1—H1B	109.9
N1—Co1—N1^i	153.2 (2)	H1A—C1—H1B	108.3
N2^i—Co1—O1^i	172.34 (15)	N1—C2—C3	121.9 (5)
N2—Co1—O1^i	85.30 (16)	N1—C2—C1	117.1 (4)
N1—Co1—O1^i	86.92 (15)	C3—C2—C1	121.0 (5)
N1^i—Co1—O1^i	74.63 (15)	C4—C3—C2	119.2 (5)
N2^i—Co1—O1	85.30 (16)	C4—C3—H3	120.4
N2—Co1—O1	172.34 (15)	C2—C3—H3	120.4
N1—Co1—O1	74.63 (15)	C3—C4—C5	119.5 (5)
N1^i—Co1—O1	86.92 (15)	C3—C4—H4	120.2
O1^i—Co1—O1	93.0 (2)	C5—C4—H4	120.2
C2—N1—C6	118.3 (4)	C6—C5—C4	118.3 (5)
C2—N1—Co1	118.2 (3)	C6—C5—H5	120.8
C6—N1—Co1	123.4 (4)	C4—C5—H5	120.8
C7—N2—Co1	178.7 (4)	N1—C6—C5	122.7 (5)
C1—O1—Co1	111.0 (3)	N1—C6—H6	118.7
C1—O1—H1	109.4	C5—C6—H6	118.7
Co1—O1—H1	115.4	N2—C7—S1	178.5 (4)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···S1^ii	0.82	2.51	3.296 (5)	161

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