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Acta Cryst. (2012). E68, m1435    [ doi:10.1107/S1600536812044431 ]

Poly[([mu]3-pyridine-4-carboxylato-[kappa]3O:O':N)(pyridin-1-ium-4-carboxylato-[kappa]O)(thiocyanato-[kappa]N)cobalt(II)]

T. Neumann, J. Werner, I. Jess and C. Näther

Abstract top

In the title compound, [Co(C6H5NO2)(NCS)(C6H4NO2)]n, the Co2+ cation is coordinated by one N and two O atoms of three bridging pyridine-4-carboxylate anions, one O atom of one zwitterionic pyridinium-4-carboxylate ligand and one terminal N-bonding thiocyanate anion within a distorted N2O3 trigonal bipyramid. The bridging coordination mode of the ligands leads to the formation of layers parallel to (-101). N-H...O hydrogen-bonding interactions within the layers and S...S contacts of 3.257 (3) Å between the layers lead to the cohesion of the structure.

Comment top

The title compound was prepared within a project on the synthesis and properties of transition metal thiocyanato coordination polymers (Boeckmann & Näther, 2010, 2011; Wöhlert et al., 2011). During our attempts to prepare a one-dimensional coordination polymer based on pyridine-4-carboxylic acid as a co-ligand, crystals of the title compound, [Co(NCS)(C6H4NO2)(C6H5NO2)], (I), were obtained serendipitously and characterized by single crystal X-ray diffraction.

In the crystal structure of (I), the cobalt(II) cation is coordinated by one terminally O-bonded pyridinium-4-carboxylate ligand, one terminally N-bonded thiocyanate anion, one N-bonded µ-1,3,6-bridging pyridine-4-carboxylate and two O-bonded µ-1,3,6-bridging pyridine-4-carboxylate anions (Fig. 1). The coordination polyhedron of the Co2+ cations can be described as a distorted trigonal bipyramid (Fig. 1, Table 1).

The Co2+ cations are µ-1,3 bridged via pyridine-4-carboxylato anions into dimers, which are further connected into layers parallel to (101) (Fig. 2). The Co···Co distance within the dimer amounts to 3.4951 (6) Å. Within the layers N—H···O hydrogen bonding between the bridging pyridine-4-carboxylate anions and the non-bridging pyridinium carboxylate ligands (Fig. 3 and Table 2) is present. A short S···S contact of 3.257 (3) Å between the layers is also observed.

Related literature top

For general background information on the synthesis and properties of transition metal–thiocyanate coordination polymers, see: Boeckmann & Näther (2010, 2011); Wöhlert et al. (2011).

Experimental top

Cobalt thiocyanate and pyridine-4-carboxylic acid were purchased from Alfa Aesar. The title compound was prepared by the reaction of 43.8 mg Co(NCS)2 (0.25 mmol), and 61.6 mg pyridine-4-carboxylic acid (0.50 mmol) in 1.5 mL ethanol at 354 K in a closed 10 ml glas culture tube. After several days pink block-shaped crystals of the title compound were obtained.

Refinement top

The C-H and N-H H atoms were localized in a difference map but were positioned with idealized geometry and were refined isotropically with Uiso(H) = 1.2 Ueq(C,N) using a riding model with C—H = 0.93 Å and N—H = 0.86 Å.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2008); cell refinement: X-AREA (Stoe & Cie, 2008); data reduction: X-AREA (Stoe & Cie, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2011); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. : The coordination environment of the Co2+ cation in the title compound with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry codes: i = -x+1,-y+1,-z+1, ii = -x+1/2, y+1/2, -z+1/2.]
[Figure 2] Fig. 2. : The layers parallel to (101) in the title compound in a projection along the a axis. For clarity, the non-bridging ligands and the thiocyanato anions are not shown.
[Figure 3] Fig. 3. : The N—H···O hydrogen bonding interactions (dashed lines) within the layers in the crystal structure of the title compound.
Poly[(µ3-pyridine-4-carboxylato-κ3O:O':N)(pyridin- 1-ium-4-carboxylato-κO)(thiocyanato-κN)cobalt(II)] top
Crystal data top
[Co(C6H5NO2)(NCS)(C6H4NO2)]F(000) = 732
Mr = 362.22Dx = 1.665 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 12489 reflections
a = 8.7857 (7) Åθ = 2.3–26.0°
b = 13.5401 (8) ŵ = 1.35 mm1
c = 12.2054 (9) ÅT = 293 K
β = 95.740 (6)°Block, pink
V = 1444.67 (18) Å30.18 × 0.13 × 0.04 mm
Z = 4
Data collection top
Stoe IPDS-2
diffractometer
2844 independent reflections
Radiation source: fine-focus sealed tube2353 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.041
ω scansθmax = 26.0°, θmin = 2.3°
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
h = 910
Tmin = 0.808, Tmax = 0.954k = 1616
12489 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0434P)2 + 0.689P]
where P = (Fo2 + 2Fc2)/3
2844 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.46 e Å3
0 restraintsΔρmin = 0.39 e Å3
Crystal data top
[Co(C6H5NO2)(NCS)(C6H4NO2)]V = 1444.67 (18) Å3
Mr = 362.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 8.7857 (7) ŵ = 1.35 mm1
b = 13.5401 (8) ÅT = 293 K
c = 12.2054 (9) Å0.18 × 0.13 × 0.04 mm
β = 95.740 (6)°
Data collection top
Stoe IPDS-2
diffractometer
2844 independent reflections
Absorption correction: numerical
(X-SHAPE and X-RED32; Stoe & Cie, 2008)
2353 reflections with I > 2σ(I)
Tmin = 0.808, Tmax = 0.954Rint = 0.041
12489 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.045H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.46 e Å3
S = 1.13Δρmin = 0.39 e Å3
2844 reflectionsAbsolute structure: ?
199 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
xyzUiso*/Ueq
Co10.55767 (5)0.54579 (3)0.37683 (3)0.04212 (15)
N10.6768 (4)0.5335 (2)0.2453 (3)0.0650 (8)
C10.7529 (4)0.5189 (3)0.1751 (3)0.0569 (9)
S10.85857 (16)0.50015 (10)0.07668 (11)0.0870 (4)
O110.7180 (4)0.3217 (2)0.3482 (2)0.0961 (12)
N111.0561 (4)0.2118 (2)0.6656 (2)0.0602 (8)
H1N1.11550.17970.71330.072*
C111.0285 (5)0.3058 (3)0.6833 (3)0.0691 (11)
H111.07370.33630.74670.083*
O120.7060 (4)0.44642 (18)0.4654 (2)0.0746 (9)
C120.9336 (5)0.3592 (3)0.6092 (3)0.0626 (10)
H120.91410.42550.62190.075*
C130.8682 (4)0.3134 (2)0.5164 (3)0.0472 (8)
C140.9021 (6)0.2159 (3)0.4995 (3)0.0731 (13)
H140.86190.18400.43560.088*
C150.9951 (6)0.1659 (3)0.5768 (3)0.0797 (14)
H151.01550.09930.56670.096*
C160.7540 (5)0.3656 (3)0.4352 (3)0.0585 (10)
N210.0790 (3)0.15794 (17)0.20950 (19)0.0409 (6)
C210.1656 (4)0.1340 (2)0.3023 (3)0.0541 (9)
H210.16870.06820.32430.065*
O210.3758 (3)0.35997 (15)0.50108 (16)0.0480 (5)
O220.3902 (3)0.44629 (15)0.34512 (17)0.0468 (5)
C220.2501 (4)0.2017 (2)0.3666 (3)0.0525 (9)
H220.30690.18170.43110.063*
C230.2502 (4)0.2995 (2)0.3350 (2)0.0392 (7)
C240.1599 (4)0.3245 (2)0.2392 (3)0.0520 (8)
H240.15600.38960.21460.062*
C250.0765 (4)0.2528 (2)0.1808 (3)0.0503 (8)
H250.01490.27140.11770.060*
C260.3462 (4)0.3749 (2)0.3992 (2)0.0397 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0532 (3)0.0318 (2)0.0380 (2)0.00216 (19)0.01220 (16)0.00046 (16)
N10.061 (2)0.0587 (18)0.076 (2)0.0046 (16)0.0107 (17)0.0018 (16)
C10.055 (2)0.0454 (18)0.070 (2)0.0019 (16)0.0022 (19)0.0096 (16)
S10.0904 (9)0.0886 (8)0.0864 (8)0.0032 (7)0.0312 (7)0.0235 (7)
O110.144 (3)0.0572 (16)0.0716 (18)0.0320 (18)0.066 (2)0.0231 (14)
N110.0593 (19)0.0640 (19)0.0532 (17)0.0088 (15)0.0147 (14)0.0118 (14)
C110.078 (3)0.066 (2)0.056 (2)0.016 (2)0.031 (2)0.0079 (18)
O120.100 (2)0.0499 (14)0.0645 (15)0.0289 (14)0.0373 (15)0.0134 (12)
C120.077 (3)0.0465 (18)0.058 (2)0.0028 (18)0.0265 (19)0.0022 (15)
C130.0520 (19)0.0437 (16)0.0430 (16)0.0054 (14)0.0095 (14)0.0023 (13)
C140.105 (3)0.057 (2)0.049 (2)0.030 (2)0.031 (2)0.0147 (17)
C150.109 (4)0.063 (2)0.061 (2)0.037 (2)0.023 (2)0.0084 (19)
C160.072 (2)0.0440 (18)0.0532 (19)0.0084 (17)0.0277 (17)0.0045 (15)
N210.0492 (15)0.0369 (13)0.0350 (12)0.0022 (11)0.0040 (11)0.0004 (10)
C210.080 (2)0.0332 (15)0.0446 (17)0.0082 (15)0.0168 (16)0.0043 (13)
O210.0702 (15)0.0338 (10)0.0367 (11)0.0032 (10)0.0108 (10)0.0008 (8)
O220.0565 (13)0.0368 (11)0.0444 (11)0.0065 (10)0.0086 (10)0.0029 (9)
C220.076 (2)0.0396 (16)0.0373 (15)0.0055 (16)0.0168 (15)0.0026 (12)
C230.0497 (18)0.0340 (14)0.0324 (14)0.0022 (13)0.0037 (13)0.0027 (11)
C240.066 (2)0.0332 (15)0.0518 (18)0.0011 (14)0.0194 (16)0.0025 (13)
C250.063 (2)0.0376 (16)0.0458 (17)0.0009 (15)0.0183 (15)0.0002 (13)
C260.0462 (17)0.0309 (14)0.0402 (15)0.0021 (12)0.0054 (13)0.0014 (11)
Geometric parameters (Å, º) top
Co1—O222.004 (2)C14—C151.364 (5)
Co1—O21i2.004 (2)C14—H140.9300
Co1—N12.010 (4)C15—H150.9300
Co1—O122.097 (2)N21—C251.331 (4)
Co1—N21ii2.146 (2)N21—C211.339 (4)
N1—C11.155 (5)N21—Co1iii2.146 (2)
C1—S11.610 (4)C21—C221.376 (4)
O11—C161.230 (4)C21—H210.9300
N11—C151.316 (5)O21—C261.261 (3)
N11—C111.318 (5)O21—Co1i2.004 (2)
N11—H1N0.8600O22—C261.253 (3)
C11—C121.373 (5)C22—C231.379 (4)
C11—H110.9300C22—H220.9300
O12—C161.242 (4)C23—C241.388 (4)
C12—C131.366 (4)C23—C261.495 (4)
C12—H120.9300C24—C251.373 (4)
C13—C141.374 (5)C24—H240.9300
C13—C161.514 (4)C25—H250.9300
O22—Co1—O21i136.53 (10)N11—C15—H15119.9
O22—Co1—N1102.78 (12)C14—C15—H15119.9
O21i—Co1—N1120.67 (12)O11—C16—O12128.1 (3)
O22—Co1—O1294.28 (10)O11—C16—C13115.8 (3)
O21i—Co1—O1284.54 (9)O12—C16—C13116.0 (3)
N1—Co1—O1290.72 (13)C25—N21—C21116.7 (3)
O22—Co1—N21ii90.97 (9)C25—N21—Co1iii124.0 (2)
O21i—Co1—N21ii91.26 (9)C21—N21—Co1iii119.1 (2)
N1—Co1—N21ii88.66 (12)N21—C21—C22123.3 (3)
O12—Co1—N21ii174.71 (11)N21—C21—H21118.3
C1—N1—Co1173.2 (3)C22—C21—H21118.3
N1—C1—S1179.2 (4)C26—O21—Co1i130.33 (18)
C15—N11—C11121.6 (3)C26—O22—Co1132.53 (19)
C15—N11—H1N119.2C21—C22—C23119.7 (3)
C11—N11—H1N119.2C21—C22—H22120.1
N11—C11—C12120.6 (3)C23—C22—H22120.1
N11—C11—H11119.7C22—C23—C24117.0 (3)
C12—C11—H11119.7C22—C23—C26121.7 (3)
C16—O12—Co1128.6 (2)C24—C23—C26121.4 (3)
C13—C12—C11119.0 (3)C25—C24—C23119.7 (3)
C13—C12—H12120.5C25—C24—H24120.2
C11—C12—H12120.5C23—C24—H24120.2
C12—C13—C14118.7 (3)N21—C25—C24123.5 (3)
C12—C13—C16121.8 (3)N21—C25—H25118.2
C14—C13—C16119.4 (3)C24—C25—H25118.2
C15—C14—C13119.8 (3)O22—C26—O21126.8 (3)
C15—C14—H14120.1O22—C26—C23116.0 (2)
C13—C14—H14120.1O21—C26—C23117.2 (3)
N11—C15—C14120.1 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y+1/2, z+1/2; (iii) x+1/2, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H1N···O11iv0.861.802.561 (4)147
Symmetry code: (iv) x+1/2, y+1/2, z+1/2.
Selected bond lengths (Å) top
Co1—O222.004 (2)Co1—O122.097 (2)
Co1—O21i2.004 (2)Co1—N21ii2.146 (2)
Co1—N12.010 (4)
Symmetry codes: (i) x+1, y+1, z+1; (ii) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H1N···O11iii0.861.802.561 (4)147.1
Symmetry code: (iii) x+1/2, y+1/2, z+1/2.
Acknowledgements top

We gratefully acknowledge financial support by the DFG (project No. NA 720/3–1) and the State of Schleswig–Holstein. We thank Professor Dr Wolfgang Bensch for access to his experimental facilities.

references
References top

Boeckmann, J. & Näther, C. (2010). Dalton Trans. 39, 11019–11026.

Boeckmann, J. & Näther, C. (2011). Chem. Commun. 47, 7104–7106.

Brandenburg, K. (2011). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

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Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.

Wöhlert, S., Boeckmann, J., Wriedt, M. & Näther, C. (2011). Angew. Chem. Int. Ed. 50, 6920–6923.